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108 ABSTRACTS OF CHEMIOAL PAPERS. M i n e r a1 o g i c a 1 Chemistry. A Graphitic Schist from Co. Donegal. By RICHARD J. Moss (Scient. Yroc. Roy. Dublin Soc., 1893,8, N.S., 206--207).-A graphitic schist from Glendown, Letterkenng, with a lustre like graphite, bnt of a grayish tint, gave on analysis H20 H20 (on Ash (at 100'). ignition). C. 5. (less 0 for S). Total. Sp. gr. 0.98 3.68 3.15 4.03 87-89 99.73 2.662 The ash gave, together with traces of manganese and nickel, SiO,. Also,. Fe,O,. CaO. MgO. Na20. K20. Total. 58.91 19.87 7.40 4-86 1.63 3.54 3.73 99.94 L. J. S. Wurtzite from Mies, Bohemia. By FRIEDRICH BECKE (Tsc~. Xin. Mitth., 1894, 14, 278--279).-Botryoidal and stalactitic schalen- blende from near Mies, gave on analysis (by Heinisch) S. ZII. Cd. Fe. Gangue. Total. Sp.gr. 30.23 65.84 1.02 0.45 1.11 98.65 3.672 This deficiency of about l$.per cent. is also t o be noticed in the previous analysis by Gerstendorfer (Ber. Akad. Wien, 99). In the above analysis, the atomic ratio Zn, &c. : S = 1.030 : 0.945, and for the excess of zinc, &c., is calculated 1-36 per cent. of oxygen ; this would correspond with a mixture of 39.9 per cent. of voltzite (Zn,S,O), and 60.1 per cent of wnrtzite. Under the microscope, however, there is no indication of such a mixture, and the substance consists of fibres giving straight extinction, and wit'h positive double refraction. L. J. S. Artificial Cinnabar. By J. A. IPPEN (Tsc~L. Mi%. Mitth., 1894,14, 114-120) .-Powdered cinnabar heated wit.h sodium snlphide in a sealed tube at 80°, gave crystals of cinnabar, and also a black deposit containing small, black crystals of cinnabar.In another experiment,MINERALOQICAL CHEMISTRY. 1.09 where black precipitated mercuric sulphide was exposed t,o sunlight for two months in a sealed tube with sodium sulphide, the tempera- ture never exceeding 45O, small, well-developed crystals of cinnabar were formed; with hydrochloric acid under the same conditions no cinnabar was formed. Cinnabar is shown to be slightly soluble in sodium carbonate solution. L. J. S. Nickeliferous Pyrites. By WILLIAM 11. GOODWIN (Canadian Rec. Sci., 1893, 5, 346--347).-1n the Murray mine, Sudbury, Ontario, are grey nodules of a nickel ore resembling mispickel in colonr and appearance. Analysis gave Be. Ni (and C o ? ) . S. Insol.Total. 37.45 4-82 44.25 9-92 96.45 Calculated to BeS, and NiS2, the analysis shows an excess of 3.33 per cent. of iron, which is accounted for by t,he presence of the associated magnetite, pyrrhotite, and hornblendic matrix. Skleroklase (Sartorite) from Binn. By HEINRICH RAUMHAUER (Ber. Akad. Berlin, 1895, 243--852).-The results of the measure- ment of four crystals from the Binnenthal are given, numerous new forms being noted. L. J. S. Aiialysis of one small crystal gave S. Pb. As. Total. Sp. gr. 25.26 46-08 26-28 97.62 5-05 The formula deduced is 3(PbS,As2Sy) + 2PbS,As,S3, this being near to von Waltershausen’s formula in which there is 3.124, instead of 3 of the first molecule. vom Rath’s formula, PbS,As,S3, is the one usually accepted. L. J. S. Safflorite from Nordmark, Sweden. By S.A. HJALMAR SJ~GREN (BUZZ. Geol. Inst., Upsala, 1894, 2, 68-7l).-This mineral occurs at the Kogrufva, in a dolomitic calcite, and associated with chondrodite, tremolite and blende. It is tin-white, and usually massive, but sometimes in crystals ; the crystallographic constants, which have not before been determined for this mineral, are given. Sp. gr. 7-41. Analysis by Mauzelius gave Fe. c o . Ni. As. S. Pb(+Cu). Total. 15.28 12.99 0.20 71.13 0.68 0.33 100.61 This gives the formula (Fe,Co)As,, or uearly FeAs,,C oAs,. Although the composition is half way between that of safflorite and lollingite, the author considers this mineral to belong to the former, as the crystals differ from those of the latter. By AUGUSTIN A. DAMOUR (Bull. SOC. fran.Min., 1894,17, 151--153).-This opal, from Fiora, Tuscany, is either white and translucent, with a satiny and pearly lustre (Analysis I), or white and opaque (11). On heating, it gives off acid water, which etches glass ; when powdered and moistened it also gives an acid reaction. L. J. S. Fiorite.110 ABSTRACTS OF OHEMICAL PAPERS. Both before and after ignition, it is almost wholly dissolved by caustic potash. H20 and SiF4. A1203 and SiO,. (Low on ignition). Fe20J. Total. Sp. gr. I. 96-70 8-90 0.40 100-00 2.17 11. 96.59 3.10 0.31 100.00 2.19 This suggests that fiorite has been formed by the action of water on silicon fluoride, some hydrogen silicofluoride being enclosed in the separated silica. L. J. S. Artificial Martite. By CHARLES FRIEDEL (Bull. Xoc. >an.Mia., 1894, 17, 150--15l).-Martite is now usually considered to be haematite pseudomorphous after magnetite. On heating crystals of magnetite, weighing 0.4499 gram, over the blowpipe for four or five hours, there was a gain in weight of 0.0158 gram (calculated for change from Fe30a to Fe203 = 0*0155). By this treatment, the crystals have lost their magnetic properties, but are only slightly changed in outward aspect, having become slightly rough on the surface, and of a gray colour. The material has therefore been transformed from magnetite to hEmatite. L. J. 8. Pyroaurite from the Mossgrufva, Nordmark, Sweden. By S. A. HJALMAR SJ~GREN (Bull. Geol. Imt., Upsala, 1894,2,59--63).-Pyro- aurite occurs in the manganiferous dolomite of this mine as t h i n , yellow to yellowish-brown, crystalline scales with a round or hexagonal outline.The crystal angles we near to those of chalcophanite, but the crystals are hexagonal with pyramidal hexahedrism ; optically uniaxial, with optical anomalies. On heating, the minera.1 is infusible, and retains its yellow colour ; after ignition, i t is strongly magnetic, before, only slightly so ; sp. gr. 2.07 ; analysis by Mauzelius, on a small amount of material dried at lo$", gave Fe20,. NnO. MgO. H20. Insol. TO!^ 22.0 4.5 34.8 36.1 0.5 9'7.9 This agrees nearly with the pyroa.urite formula., with part of tohe Mg replaced by Mri, namely, Fe,03,6(Mg,Mn)0,15H,0 ; some of the iron may be ferrous. L. J. S. Artificial Crystallised Carbonates. By Lkolu BOURGEOIS (B.ttlZ. Xoc. fran. Min., 1894, 17, 79--81).-The author points out that his humid methods for producing crystallised carbonates, such as calcite, strontianite, &c.(Abstr., 1887, 22l), are identical with those of Bunsen (Annulen, 1847, 65, 71). L. J. S. Fluid Enclosures in Gypsum. By 8. A. HJALMAR SJOGREN (BzdZ. Geol. I n s t . , Upsala, 1893, 1, 277-281, and Geol. F O Y . Forb., 1893, 15, 136).-In large crystals of gjpsum from Girgenti, Sicily, large fluid enclosures were present ; from the largest cavity, 3 C.C. of a neutral liquid were obtained, hydrogen sulphide escaping from the cavity at not very great pressure. The liquid contained 4-02 per cent. of solids, which had the composition (anal. b y Mauzelins)MINERALOGlCAL CEINMISTRY. 111 &SO,. Sn,SO,. CaS04. NnC1. MgC1,. 3.7 11.4 9.7 66.2 9.0 This is compared with sea water and with the water of the Kaiser- quelle at Aix-la-Cbapelle.Two views have been put forward t o account, for the origin of the sulphur of the Sicilian deposits : one supposes it t,o have been formed by the reducing action of organic matter on gypsum in isolated lagoons ; the other, that it has been deposited with the gypsum from spring waters containing hjdrogen sulpbide ; the latter view is sup- ported by the above analysis. Artificial Anhydrite. By REINHARD BRAUXS (Jah~b. f. ilIiiz., 1194, ii, 257--264).-Anhydrite has been artificially formed by fusing together calcium snlphate and chloride, and by heating gypsum i n sealed tubes with chlorides, or by digesting it with hot sodium chloride solution ; these processes would, however, not account for the formation of the large beds of anhjdrite found in nature.In the author's experiments, a large drop of a sat,urated solution of sodium and potassium chlorides is placed on a microwope slide, at. its side a drop of calcium chloride solution, and, opposite this, ;I drop of magnesium sulphate solution ; the two drops are then brought into contact by a narrow path, rrnd allowed to evaporate. As diffu- sion takcs place, small prisms of anhydrite are deposited, and, here and there, gypsum. On removing the salt crystals and adding water, the anhydrite citystals are immediately corroded, and gradually dis- appear, and, on allowing this mixture to evaporate, gjpsum, and not anhydrite, crystals are formed. I n case the amount of water added is not, enough to completely dissolve the anhydrite, gypsum crystals are deposited around the corroded forms ; or sometimeP, when the gypsum crystals do not grow on the surface of the anhydrite, but near to it, they may be seen to grow a t t,he expense of the anhydrite.Calcium sulphate is, therefore, one of those substances which crys- tallise irom saline solutions in compounds poor in water, such solu- tions having the same effect as a n increase in temperature. Instances of a relation similar to that of gypsum and anhydrite, are epsomite and kieserite, and glauberitc: and thenardite ; moreover, the second members of e3ch of these pairs crjstallise together in nature from saline solutions. L. J . S. L. J. S. Serpierite, Lautite, and Pseudobrookite. By AUGL'ST FRENZEL (Tsch.Min. Miftlc., 1894, 14, 221--130).--er~iti.ite.-This mineral, which accurs a t Laurion, Greece, in bushy groups of blue, ortho- rhombic c r ~ s t a l s , has not before been analgsed. Sp. gr. 2.52 ; analysis give CuO. ZnO. CRO. SO,. H,O. Total. 36.12 13-95 8-00 24-29 16-75 99.11 Formula: Y(CuO,ZnO,CaO),SO, + 3H20. A t lob" 1.26 per cent. of water is given off ; at 285" the powdered mineral becomes black. 3azctite.-A new find of this mineral has been mode a t t.he old locality, Lauta, Marienberg, Saxony ; i t occurs a s radiating aggre-112 ABSTRACTS OF CHEMICAL PAPERS. gates, and, from its appearance, it cannot be a mixture, as has been supposed. Analysis gave cu. As. 8. Total. Sp. gr. 36.10 45.66 17.88 99.64 4.91 This leads to the formula previously adopted by Frenzel, namely, CnAsS.Pseudobrookite.-The formula which has been derived for the natural mineral is 2Fe20,3Ti0, ; but to the artificial mineral has been given the formula, Fe,0,Ti02 (Abstr., 1893, ii, 18). Analysis of the material from the original locality, Aranyer Berg, Transylvania, gave (Frenzel) I and (Traube) 11. Some of the previous analyses show 12 per cent. of silver. Ti02. Fe203. MgO. Si02. Total. I. 41.27 54.24 2-09 1.66 99.26 11. 41.46 56.45 1.0 1.29 100.20 Deducting magnesia and silica as representing admixed szaboite, these analyses give the formula 2Fe203,3Ti02. Experiments of Traube's are given by which he tested the methods of separating TiO, and Fe203. L. J. S. Hautefeuillite, a New Mineral from Bamle, Norway, By LPopom MTCHEL (Bull. 8oc.fran. Min., 1893, 16, 38--40).-In the greyish apatite veins in the gabbro of Odegiirden, are greenish nodules consisting of a mixture of wagnerite and apatite, in which the new mineral was found together with crystals of apatite, pyrites and monazite. The colourless, transparent, monos.ymmetric crystals form lamellar and radial aggregates : cleavage parallel to the plane of sym- metry perfect ; sp. gr. 2.435 ; plane of the optic axes parallel to the plane of symmetry, 2E about 88', 2V = 54' 23' for yellow light. Analysis gave P,05. MgO. CaO. H20. Total. 34.52 25.12 5.71 34.27 99-62 Thin gives the formula (Mg,Ca)3(P0,)2 + 8H20. from bobierrite in containing calcium, and in the optical characters. L. J. S. The mineral differs Caryinite. By S. A.HJALMAR SJOGREN (Bull. Geol. Inst., Upsala, 1894, 2, 113-118).-The only previous analysis of this mineral has been shown to have been made on impure material, the specimens having been mixed with calcite and berzeliite, iiito the latter of which caryinite is readily altered. A new find of the mineral a t the old locality, Llngban, Sweden, has rendered it possible to analyee pure, fresh material, and to determine, by means of the cleavage and optical characters, that the mineral is orthorhombic. The massive, nut-brown mineral occurs in fissures with schefferite, rhodonite and hedyphane ; sp. gr. 4.29 ; analysis by Mauzelius, on material dried at l l O o , gave h.05. P20,. PbO. FeO. MnO. MgO. BaO. CaO. 49-78 0.19 9.21 0.54 18.66 3-09 1-03 12.12 K20. Na20. H20. Total.0*;37 5.1 6 0.53 100.68MINERALOQlOAL OHEMISTRT. 113 Also traces of V,O,(?) and C1. If the water exists with the bases as H,, the formula deduced is 10R0,.3As,O5; if, however, it exists in the group 2(HO-R") the formula is 3R0,As,05. The original analysis of' this mineral showed neither alkalis nor water. Compare soda-berzeliite below. L. J. S. Soda-berzeliite from Lhngban, Sweden. By S. A. HJALNAR SJ~GKEN (Bull. Geol. Inst., Upsaln, 1894, 2, 118-121) .-This new variety of berzeliite differs from berzeliite in outward appear- ance by it8 orange-yellow to fire-red colour; it is usually massive, but sometimes occurs as crystals (icositetrahedra). Sp. gr. 4.21. Analysis by Manzelius gave As20,. V205. FeO. MnO. CuO. MgO. K20. Na20. H20. Total. 52.90 0.24 0.38 21-41 18.34 0.72 0.09 5.05 0.40 99.53 together with traces of ,Cb205 and C1, and about + per cent.of in- soluble matter. This analysis is very similar to that of caryinite (see preceding abstract), and in the same manner according as the water is assumed to be combined with the acids or the bases the formula deduced is 10R0,3As2O5, or 3RO,A8,O6 respectively. As these two minerals differ crystallographically, berzeliite being cubic and caryinite orthorhombic, they may have different forrnulm (10R0,3AszO5 and 3RO,As,O,), or they may have the same formula and be dimorphous, or thirdly the presence of lead in caryiiiite may be essential. Igelstrom's pyrrhoarsenite (Abstr., 1895, ii, 76) resembles soda- berzeliite in some respects. Lbgbanite from the Sjiigrufvrt, Sweden.By S. A. HJALMAR SJOGREN (Bull. Geol. Inst., Upsala, 1894, 2, 96-97).-This mineral, before only known from the Lingban mines, has been found at the Sjo mine in a mixture of rhodonite, manganopbyllite, braunite and calcite ; it is generally in lamellar masses, but sometimes shows hex- agonal outlines and a distinct basal cleavage. In very thin spliiitera, i t is sub-translucent with a red colour; sp. gr. 460. Analysis by Mauzelius gave Sb20s. Fe20B. Si02. Mn02. MnO. CaO. MgO. IT@. Total. 0. 12.51 13.98 12.82 24.36 32-22 2.40 1.11 0.52 99.92 309 This gives the ratio SbO, : Fe203 : RO, : RO = 0.087 : 0,177 : 1 : 1.07. As before (Abstr., 1893, ii, 421) the oxides E ' O and RXVO2 may be brought together as R"',03, and the substances considered as an iso- morphous mixture of the three groups in the formula mSb203 + nFe203 + pR"RLV03, where, in this case rr~ : n : p = 10 : 20 : 115. The fairly constant amount of SgO, shown in previous analyses would, however, t e l l a gainst this improbable isomorphous mixture.The mineral here analysed closely resembles in arpearance and composi- tion Sjogren's B type of lingbanhe from Langban, and may be re- presented by the empirical f o'rmula S b203,9Mnz03,5 NnSiO,, whilst the A type from Lingban may be represented by S b20J,10~~n,03,S1\InSiOj, L. J. s.114 ABSTRACTS OF CHEMIOAL PAPERS. where MnzOj is partly replaced by Fe20j, and MnSiO, by CaSiO, and MgSiO,. L. J. S. Apophyllite from Algeria. By Lcms C T E w r c , (Hall. SOC. ft-an. Jfi7z., 1894, 17, lL-28).-1n an altered andesite at Bou Serdoun, Collo, are cavities, contaiuing apophyllite and other minerals.The crystals show optical anomalies ; analyses gave Si02. CnO. MgO. K20. NhO. H,O. Total. Sp. gr. 52.32 25.30 0.57 4.83 0.80 16-66 100.48 2.372 At 100Othere is a loss of 0.33 per cent. of water ; fluorine was absent (Abstr., 18941, ii, 421). The associated minerals and the rock are described a t length. Prolectite, a New Mineral of the Humite Group. By S. A. HJALMAR SJOGREN (Bull. Ceol. Inst., ITpsala, 1894, 2, 99--105).-Two fragments of crystals from Nordmark, Sweden, wera found to differ from the other brownish-grey humite minerals OF the same locality in their crystal angles and optical characters : the crystallographic constants are approximately cc : b : c = 1.0803 : 1 : 1.8862 ; /3 = 90' ; the vertical axis (c) is, therefore, one-third of that of clinohumite.Penfield and Howc (Abstr., 1894, ii, 241) have predicted the existence of a member of the humite group having the composition L. J. S. M ~ ~ ~ ~ ( F , o H ) I , s ~ o , , and the axial ratios a : b : c = 1.086 : 1 : 1.887 ; /3 = 93". Owing to Composition of Chondrodite, Humite and Clinohumite, fromNordmark. By S . A. HJALMAR SJOGRES (BUZZ. GeoZ. Inst., UpsaZa, 1894, 2, 39--54).-1n a previous paper (BUZZ. Geol. Inst., Upsala, 1892, 1, 16-40) are given the results of the crystallographic and optical measurements of these minerals from a new locality, tbe Kogrufva, Sweden ; the mode of occurrence and associations are strikingly similar to those at the Tilly Foster Iron Mine, N.Y.Seven duplicate analyses by R. Mauzelius, lead to the same formulm as those given by Penfield and Howe (Abstr., 1894, ii, 241). Potas- sium, sodium, and titanium were found in small quantities, and there is a slight variation in the amount of water showa in t h s analyses, owing, when too high, to the partial alteration of th3 mineral to serpentine, and, when too low, to the difficulty OE driving off all the water. On heating chondrodite in dry hydrogen chloride (Clarke's method), the amount of magnesium rendered soluble, agreed with that required by the assumption of the existence of the group MgOH. Structural forrnuh. showing the relation to olivine are given. L. J. S. Soda-richterite from Lgngban, Sweden. By S. A. HJALMAK SJOGKEN (Bull. Geol. Inst., Upsala, 1894, 2, 71-77).-This mineral occurs with rhodonite in rather coarsely crystalline, columnar aggre - gates of an azure-blue or gray to grayish-violet colour. The cleavago lack of material, the mineral has not been analysed.L. J. s. The ratio of F:OH was always about 1 :l.MINERALOGICAL CHEMISTRY. 113 angle of 56" 27', and the optical characters show i t t o belong to the hornblende group. I gives the analysis by Mauzelius of the blue variety, sp. =I*. 3.05, and IL of the grdyish-violet, sp. gr. 3.10. Total. I. 56.25 0.15 6-49 5.44 21.89 1.60 6.17 1.56 0.15 99.64 11. 54.76 0.21 12.71 5.83 17-83 1.65 4.02 2.77 0.09 99.82 Calculating fhc water, which only goes off at a high temperature, as H2 with the metals, the analyses redace to the metasilicate formula. A sample oE the blue variety lost 3.37 per cent.on igni- tion, and from the powder was extracted by soda solution 13.38 per cent. of SiOz, this corresponding with 3.99 pel- cent. of water in H',SiOs. The above analyses do not reduce to the formula, CaMg3Si,Ol2, sometimes given for non-nluminous amphiboles. The original richterite of Breithaupt is shown to have been wrongly described. L. J. S. New Analyses of Chloromelanite. By AUGUSTIX A. DAMOUK (BUZZ. Xoc. fran. Min., 1893, IS, 57--59).-Several ancient stone axes with a density varying from 3.55 to 3.60 were seen to contain varying amounts of garnet in the dark green matrix ; the latter, on being separated, gave the following analyses. SiO,. A1203. Fe,O,. CaO. MgO. Na20. Total. Sp. gr. Mexico.. . . 56.57 17.21 8.86 4.44 2-12 10.70 99.90 3-37 Antioch... . 55.01 9.99 10.09 12.00 3-23 7.48 99.80 3.36 Carcassonne 57.75 14.85 9.52 3.15 1.81 11.76 98.87 3.40 Si02. FeO. MnO. CaO. MgO. K20. NazO. H20. I?. (1eesOforF). Lyons . . . .. 56.00 13.19 1390 3.71 1.88 10.75 99.43 3.43 Chloromelanite may be considered to be a ferruginous jadeite ; both these minerals, after fusion, are decomposed by hot hydro- chloric acid without gelstinisation. The association of garnet wi tll chloromelanite constitutes a rock resembling eologite. Andradite Garnet from Algeria. By LOUIS GENTIL (Bull. SOC. $-an. Nii?~.., 1894, 17, 269-272).-This garnet occurs near Cape Rou-Geroune, Constantine, in a vein of hEmatite and quartz with ilvaite, limestone, green pyroxene, and perhaps bustamite. The small dodecahedra1 crystals are yellowish to dark brown, and show optical anomalies.It is easily attacked by hot, strong hydrochlorio acid ; analysis gave L. J. 8. Fe20,. Al,O,. CaO. Mn. MgO. KZO. Total. :36*03 30.94 0.27 32.58 trace 0.48 0.17 100.47 This gives the usual formula 3Ca0,Fe,03,3Si0,. On ignition, there is a loss of 1.60 per cent., probably due to reduction. L. J. S. Artificial Zgirine. By HELGE BACKSTROM (Bull. SOC. fyan. Jfin.% 1893, 16, 130-133) ,-A leucite-phonolite rich in hauyne was fused and allowed to cool slowly for three days ; the colourless glass thus produced coiitained microlites of oligoclase and nepheline, and11G ABSTRAOTS OF CHEMICAL PAPERS. numerous crystals of a yellow pyroxene, which agree in their optical characters with sgirine. A mixture of quartz, ferric oxide, and sodium carbonate, in the proportions given by the aegirine formula, when treated i n the same way, gave a mass largely consisting of prismatic crystals of Egirine, with some yellow glass, hzmatite scales, and probably felspar. Composition of Canadian Limestones and Dolomites, By BERNARD J.HARRINGTON (Caiuldian &ec. Sci., 1894, 6, 27-32).-Thc author gives analyses of 18 lim estones and dolomites from various By CONSTAXTIN KLEMENT (Bull. SOC. Belge Geol., 1895, 9, 3-23, and Tsch. Min. Mitth., 1895, 14, 526 -544) .-After reviewing the different theories of the origin of dolomite, the author points o u t that dolomite deposits are often in the form of coral reefs, and that corals con- sist of aragonite. His experiments show that solutions of mag- nesium salts act much more readily on aragonite than on calcite.When powdered aragonite (crystals, corals, and artificial) is. warmed with magnesium sulphate in a concentrated solution of sodium chloride, tbe action begins at about 60°, and increases with the tem- perature, until at 91' there is a maximum yield of about 42 per cent. of magnesium carbonate. Experiments were made with solutions of different concentrations, and of different salts. It is shown, by the action of dilute acids, that the product formed consists of a mechani- cal mixture of calcium and magnesium carbonates ; but owing to the tendency of dolomite to crystallise, such a mixture would be gradually converted into dolomite. The conditions of these experiments would be those which exist in the isolated lagoons of coral islands.L. J. S. geological horizons in Canada. rA. J. s. Process of formation of Dolomitic Rock. L. J. s. Lower Carboniferous Volcanic Rocks of East Lothian. By FREDERICK H. HATCH ([Trans. Roy. Xoc., Edin., 1893, 37, 115-126).- Several analyses are given of the lower, basic lavas (basalts free from felspar), of the upper, more acid lavas (trachytes), and of the material filling the volcanic vents ; all being of lower carboniferous aFe.. I is of the limburgite of Whitelaw Hill; it is composed of olivine, augite, magnetite, glassy matter, and probably nepheline ; sp. gr. 3.03. I1 is of the phonolite of the volcanic vent of Traprain Law ; this consists of sanidine, nepheline, and green soda-augite, the nepheline beiug largely converted into zeolites ; sp.gr. 2.588. Si02. TiO,. A1303. Fe203. FeO. MnO. CaO. MgO. 11. 56.8 0.5 19.7 2.2 3.5 0.2 2.2 0.4 I. 40.2 2.9 12.8 4 0 10.4 - 10.4 11.9 Loss on N+O. K20. ignition. Total. I. 2.7 0.8 3.4 99.5 11. 4.3 7.1 2.5 99.4 Limburgite has not before been recorded in the British Isles, and phonolite only a t the Wolf Rock. L. J. S.MINERALOGICAL CBEMISTRY. 117 Borolanite, an Igneous Rock. By J. J. HARRIS T E A L L ~ ~ ~ JOHN HORNE (Trans. Roy. Soc., Edin., 1893, 37, 163--178).-This intru- sive, igneous rock, from near Loch Borolan in Sutherland, consists priucipally of orthoclase and melanite garnet, with plagioclase, pyroxene, biotite, and alteration products of nepheline; it is thus related to the clEolite-syenites. I gives a bulk analysis of the rock, and I1 the portioii soluble in hydrochloric acid.111 is OE a peculiar blue substance which is decomposed by acids, and is probably the alteration product of a member of the sodalite group. SiO?. TiO,. SO,. A1,0,. Fe20,. FeO. MnO. BnO. CaO. I. 47.8 0.7 0.4 20.1 6.7 0.8 0-5 0.8 5.4 3.9 3.2 A - 2 11. 69.3 - - 16.8 - - TTT. 36.1 - s.9 28.4 - - - - Loss on XgO. X'n,O. K20. ignition. Total. I. 1.1 5.5 7.1 2.4 99.3 111. -- 16.2 1.8 - 91.6 IT. o.:~ 4.6 1.7 2.4 w o L. J. S. Analyses of Augite and Nepheline-leucite. tephrite from Bohemia. By J. E. HIRSCH (Tsch. Min. Mitth., 1894, 14, 95-113). -Fourteen analyses of various igneous rocks from the Bohemian Mittelgebirge are given. I is of a nepheline-leucitc-tephrite from Falkenberg, and I1 of the large augite crystals of the same rock; both analysed by F. Pfohl. SiO,. TiO,. P20,. &03. Fe2O3. FeO. 3 h O . CaO. I. 47*S3 2.27 1-33 16.09 4.32 3.G2 trace 10.68 TI. 45-67 0.62 - 9.04 7.46 2.00 - 21-78 H20 (com- MgO. K20. Na,O. bined). Moisture. Total. Sp. gr. I. 5-53 4-05 4.46 0.24 0.05 100.47 2.858 11. 12.09 0.56 1.25 0.31 - 100.78 3.37 The spectroscope showed Sr and Li in I. Argon and Helium in Mineral Waters. By CH. BOUCHAED (Compt. rend., 1895, 121, 398--394).-The gas evolved from the sulphur waters of the Pyrenees consists mainly of nitrogen. The gas from the spring at RaillBre, however, contains argon and helium, and that from the two springs at Bois contains helium, and apparently another element also, the spectrum of which is characterised by red and orange-red lines. Composition of Water of the Pacific. By CAMILLE CHABRIB ( B ~ t l . SOC. fran. Min., 1894,17, 220-222).-A sample of water taken from the surface of the Pacific a t " latitude 12 hours north of Paris," contained, in a litre, 24-27 grams of chlorine and 3.056 grams oE SO,. Bromine and iodine are absent or present only in traces. The water L. J. S . C. H. B. YOL. LXX. ii. 10118 ABSTRACTS OF CHEMIOAL PAPERS. is neutral, and has a sp. gr. of 1.028 at 26'. in this water is greater than that in the water of other oceans. The asmount of chlorine L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8967005108

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

113 Organic Chemistry. Action of Heat on Ethylene. By VIVIAX B. LEWES (PYOC. ROY. SOC., 1895, 57,394-404).-'rhe apparatus and methods of analysis were the same as described in the previous paper (Abstr., 1894, i, 4.Sl), except that a platinum tube mas used as the decomposing chamber, and a gas coinbustion furnace as the source of heat. The experiments show : (1) That the initial decomposition of ethylene by heat is very rapid, but that this primary decomposition is only very slowly completed, owing to secondary react.ions, which tend to re-form ethylene. Thus when only 1 in. of the platinum] tube was heated, $0 per cent. of the ethylene was decomposed, and with 18 in. heated only 93.7 per cent. (2) That increase in the rate of flow of the gas through the platinum tube diminishes tlie decomposition when the heated area is small, but has very little effect when the heated surface is large.(3) That dilution has but little effect on the decompositiou ; and (4) that the decomposition of ethylene is mainly due to Yadiant heat. J. J. S. Combination of Mercuric Cyanide with Bromides and with Iodides. By RAOUL VARm (C'ompt. rend., 1895,121, 398-400, and 499-502 ; compare this vol., ii, 88 and 148). Double Decompositions between NIercuric Cyanide and Salts of Alkali and Alkaline Earth Metals. By RAOUL VARET (Conzpt. rend., 1895, 121, 501-502).-Fluorides, chlorides, sulphates, nitrates, carbonates, acetates, and picrates of the metals of the alkalis or alkaline earths do not interact with mercuric cyanide. Bromides behave fiimilarly, but there is a slight exchange of acids and bases.Iodides, on the other hand, interact, and the change is Iimited by the formation of salts of the type Hg(CN),,M"(CK),,HgI,. With the sulphides there is complete double deconiposition. There is more or less complete decomposition when the acid in combination with the other salt displaces (when in the free state) hydrocganic acid from the mercuric salt ; if this is not the case, there is no appreciable inter- action. C. H. B. Calcium Cyanate, a Nitrogenous Manure. By C.\MrLLE: FAURE (Compt. r e d , 1895, 121, 463).--Calciuni cyanate can be pre- pared in large quantities in the electrical furnace, limestone and carbon being first heated at 1500°, then at 2500°, in presence of excess of nitrogen, and finally at 2500' in a current of air.Alcoholates. By HENRI LEXCOEUR (Conzpt. rend., 1893, 121, 691-692) .-Solutions of sodium ethoxide in ethglic alcohol, and the products obtained by evaporation, have thc following vapour pressures z t 60". Saturated solution, 138 mm. ; product nearly dry, 13.5 mm. ; prodoct EtNaO + 1-7 EtOH, 60 mm. ; prodact EtNaO + 0.8 EtOH, C. H. B. VOL LXX. i. k114 ABSTRACTS OF OHEWOAL PAPERS. 56 n m . ; effloresced product, 54 mm. ; almost pure EtNaO, less than 18 mm. A compound EtNaO + 2EtOH is therefore well defined by its vapour pressure a t 60'. The vapour pressure varies as follows ; a t 40", 14 mm. ; at 60°, 57 mm. ; at 80°, 172 nim. In a dry atmosphere at the ordinary temperature, sodium ethoxide alcoholate effloresces, and yields sodium ethoxide.Similar observations on solutions of sodium hydroxide in alcohol gaye the following results a t 100". Fused product, NaOH + ShtOH, mow than 300 mm.; product partially solidified, more than 300 mm. ; solid product, NaOH,EtOH? 215 mm. ; effloresced product, 207 mm.; ditto, 200 mm. ; almost pure NaOH, less than 30 mm. A compound NaOH + EtOH is therefore defined ; its Tapour pressure is 35 mm. at 76" ; 207 mm. a t 100' ; 275 mm. a t 105'. When sodium hydroxide is dissolved in boiling alcohol, and the solution is cooled, it deposits small scales, which seem to have the composition NaOH + 3EtOH ; they alter very rapidly in mcist air, melt easily, and give off alcohol when heated. These compouuds are true aICo- holates of sodium hydroxide. RROCHET (Comnpt. rend., 1895, 121,648-650).-The action of chlorine on normal propylic alcohol in the cold results in phenomeila similar to those observed with methylic and isobutylic alcohols.In the end the liquid separates into an upper layer consisting of water, hydro- chloric acid, unaltered alcohol, and cbloropropaldehyde, and a lower layer consisting of unsymmetrical dich Zoropmp ylic ether, CHMe Cl*CHCI- O*CH2* CHoMe, a colourless, very mobile liquid, with a characteristic and very per- sistent odour. It boils at 80" under a pressure of 15 mm., and at 176O under 762 mm. ; sp. gr. a t 15"/4O = 1.129 ; refractive index nD = 1.447 at 16". When boiled with water, the dichloropropylic ether yields a mixture of a-chloropropaldeh~de and chlorodipropylic propiona], C Me C 1,- CH ( 0 P r ) 2.a-Clllornp,,opaldehyde, after being dried by treatment with an equal volume of sulphuric acid at -goo, is a colour.less, very mobile liquid, which boils at 86" under a pressure of 755 mm. ; sp. gr. a t 1S0/4" = 1.182* ; rcfractive index nD = 1.431 at 17". It does not yield cyjstals of a, polynicride in contact with sulphuric or hydrochloric acid, but, there is some evidence that it very slowly polymerises in contact with a small quantity of hyclrocliloric acid. When oxidised with potassium permanganate, with addition of alkali, it yields acetic, carbonic, and hydrochlor.ic acids. Chlomdipropylic propioizal is obtained by the action of water o r propylic alcohol on dichloropropylic ether. It is a colourless, mobile liquid, which boils a t 203' uiidcr a pressure of 7.55 mm., and, li1-e acetals, is very stable; sp.gr. a t 1s0/4O = 0.990; refractive index ~ z D = 1.430 a t 16". C. H. B. Action of Chlorine on Normal Propylic Alcohol. By ANDRB C. H. B. Trimethylenic Glycol as a Bye-product in the Glycerol Manu- By ART HI:^: A. NOYES and WILLARD H. WATKINS (J. dnzer. factura.ORGANIC OHEMISTRY. 115 ChenL. SOC., 1895, 17, 890--891).-The authors have succeeded in isolating trimethylenic glycol from a specimen of glycerol of low specific gravity. This was probably formed, before saponification, by the fermentation of the glycerol present in the fat. The presence of this glycol in glycerol used for nitroglycerol manufacture might be a. souwe of danger, owing to its violent reaction with nitric acid. J. J. S . Pentaglycol : a Dihydric Alcohol synthesised from Formalde- hyde and Isobutaldehyde.By M. AJ'EL and BERNHAHD Tor,r,Ess (AnnaZeit, 1895, 289, 36-46; compare Abstr., 1894, i, 353).- P e n tag Z y col iodh ydrin, C HJ C Me,*C H2.0 H , is obtained by hen t i ng pentaglycol with hydriodic acid and phosphorus for t w o hours ; it is a pale yellow oil! which boils at 60" in a vacuum. Methylenepenta- 0 g7ycoZ, C,H,o<O>CH2, boils at 126'. M. 0. F. Boiling Point of Nitroglycerol. By C o m m r s A. LORRY DE BRUY?; (Rec. ! h v . Chim., 1895,14, 131--133).-The author refers to the value obtained by Champion (Compt. rend., 1871, 73, 42) for the boiling point of nitroglycerol, aud criticises the method adopted by this chemist. A small quantity of nitroglycerol, contained in a boiling flask, was heated in a bath of glycerol to 160°, under a pressure of 15 mm., the pressure being diminished by means of a water pump. No nitro- glycerol distilled over under these conditions, but the substance commenced to volatilise.The author believes that if a mercurg pump had been emplojed, the nitroglycerol would have distilled. This negative result renders it certain that the boiling point of nitro- glycerol a t the ordinary temperature cannot be 185", as stated by Champion. Champion and Lorm have published values for the vapour pressure of nitroglycerol, according to which the boiling point of the compouiid would be below 200'; these are likewise not in acsord with the author's experience. A. R. L. Compounds of Formaldehyde with Polyhydric Alcohols. By M.SCHULZ and BERKHA~CD TOLLENS (AnnuZen, 1895, 289, 20-34; compare Abstr., 1894, i, 4%).-The compounds dealt with i n this paper have been already described by the authois (Zoc. cit.), the cl2;ss name formal being used instead of formacetal. 1 4 . 0. F. Penta-erithrytoldibenzal. By M. APEL and BERNHARD Tor.LLeh-s (Aimalen, 1895, 289, 3 6 - 3 5 ; compare Abstr., 1894, i, 353).-Diben- zyZidenepentcc-erit/~r~toZ, C5H80A(C7H6)2, melts at 160'. 11. 0. F. A nhydro-enneaheptitol from Formaldehyde and Acetone. By M. APEL and BERXIURD TOLLENS (Aanalen, 1895, 289, 4Ci--.il; compare Abstr., 1894, i, 353).-The authors have already described anhydro-eizneaheptitol, OH*CH(C[CH,*OH],), (Zoc. cif.), and a more detailed account of the properties of the substance is now supplicd. M.0. F. I6 %116 ABSTRACTS OF CHEMICAL PAPERS. Action of Dilute Alkalis on the Carbohydrates. By CORS E L l u s A. LOBRY DE BRUYN (Rec. Trav. Chim., 1895,14,156-165).-When a 4 per cent. aqueous solution of ordinary glucose (500 c.c.) is treated with normal potassium hydroxide solution (10 c.c.), the optical activity diminishes, until at the end of 135 hours i t has sunk approxi- mately t o zero, at which it remains constant. The solution is now fouud to require only about one-third the calculated quantity of acid to neutralise it ; the neutral solution still remains optically inactive. The Ea,me result is obtained when glucose is treated at the ordinary temperature with a more concentrated solution of potassium hydr- oxide ; the author separated ordinary glucose from the neutrdised product.Other bases, notably ammonia and barium hydroxide, behnre towards glucose in the same manner. Xylose and galactose likewise rndergo a change in rotatory power when treated with dilute alkalis. A. R. L. Action of Alkalis on the Sugars. Reciprocal Transformation of Glucose, Fructose, and Mannose. By CORNELIUS A. LOBRY DE BRUYN and W. ALBERDA VAN EKEKSTEIK ( R e c . Trav. Chim., 1895, 14, 201-216, and Ber., 1895, 28, 3078--3082).-The optically inactive syrnp which is obtained by the action of potassium or sodium hydr- oxide, or ammonia on glucose, is also formed by the action of calcium hydroxide, sodium, or potassium carbonate, or magnesium oxide. When, however, the action is prolonged, calcium hydroxide leads to the formation of saccharinic acid, which is not the case with potas- sium or sodium hydroxide (compare Kiliani, Bey., 1882, 15, 2960).The speed with which the optical activity is attained is dependent on the temperature and concentration of the solution ; the most favour- able temperature being 70". Glucose (100 grams) dissolved in water (400 c.c.) and treated a t this temperature with calcium hydroxide (5 grams), is transformed in a few honrs. The calcium is readily precipitated by passing a current. of carbonic anhydride through the solution. By this transformation, glucose is, in part, converted into mannose, which was isolated and estiniatcd by meaiis of its iiisoluble phenylhydrazone, and, in part, into fructose; a certain portion of the glucose remains unaltered, whilst another portion is converted into acids.Fructose is also partially converted into glucose and mannose on being similarly treated with alkalis or alkaline earths, whilst mannose is, in like manner, partially convei ted in tc glucose and fructose. The authors' results are drawn up in the form of a table. This reciprocal transformation is conditioned by it state of equi- librium which may be represented by the symbol Glucose - fructose - mannose. Actual equilibrium is never established, however, becanse simul- taneous decomposition into acids occurs. Galactose is not formed in this reaction. As an explanation of the mechanism of the changes which occur during this transformation, i t is suggested that the two end groups in the molecule of glucose, -CH(OH).CHO, first combine with a molecule of watei-, which is subsequently split of€ in such a manner that theORGANIC CHEMISTRY.117 0 A complex -CH*CH*OH results, which then passes, by intramolecular transposition, into t.he complex -CO*CH2*OH, which exists in the ordinarily accepted formula for fructose. By an inverse change, fructose may be assnmed to give rise to the complex -C€I*CH*OH, stereoisonieric with that above mentioned, which, by addition and loss of water, would give mannose; or the two end groups in the molecule of fructose, by addition and loss of water, may be assnmed which, by intramole- to be converted into the complex O< I cnlar transposition, may give rise to the complex -CH(OH).CHO. The reciprocal transformation of the three sugars evidentlg plays a r8Ze in the chemical changes which occur in the tissues o€ plants.The reaction demonstrates the necessity of observing caution in draw- ing conclusions from experiments on the sugars made in alkaline solutions. Thus it was long thought that mannitol was the alcohol corresponding with glucose, because that alcohol is one of the products formed by reducing glucose with sodium amalgam ; this was, however, disproved by E. Fischey. The reaction also explains tbe facf that the technical invert sugar syrups, after the treatment witah lime, are almost optically inactive, instead of being laevorotatory. An investigation of certain " foreign syrups " has shown that they contain notable quantities of mannose. \/ 0 CH, CH-OEL' A. R. L. Sugars richer in Carbon from Galactose. By EMIL FISCHER (AnnaZeic, 1895, 288, 139-157 ; compare Abstr., 1890, 597).- a-Galaheptonic acid is the gnlactosecarboxylic acid obtained by Maquenne aud Kiliani.Galactose (100 grams) is dissolved in warm water (150 grams) and treated at 0" with hydrogen cyanide (28 c.c.), a few drops of aqueous ammonia being also added ; after remaining a t 0' during 24 hours, a quantity of the amide amounting to 25 per cent. of the material employed may be renioved by filtration, it further separatioii taking place during two following days. The amide is dissolved in boiling aqueous barium hydroxide and heated until ammonia is no longer perceptible ; the hot liquid is then exactly neutralised with sul phuric acid, boiled with animal charcoal, filtered and evaporated. The gyrup is then heated for several days in a por- celain basin on the water bath with successive quantities of alcohol, and by this treatment yields t,he lactone (Zoc.cit.), which crystal- lises from methylic alcohol in long needles, melting at 151" (corr.) after softening at 14'2"; at 20' it has the specific rotatory power [ a ] D = - 52.3'. The pkenylhydrazide dissolves in 25 parts of boiling water, and crystallises in colourless, lustrous needles ; it becomes brown and evolves gas a t 226" (corr.) when rapidly heated. a-Gataheptose is prepared by reducing the lactone in ice-cold solu- tion with sodium amalgam; it is obtained as a sweet, colourless syrup on decomposing the hydrazone with benzaldehyde. The sugar118 ABSTRACTS OF CHEMICAL PAPERS. is extremely soluble in water, but dissolves with great difficulty in absolute alcohol ; the aqueous solution is feebly Izevorotatory, and is not fermented by yeast.The phenylhydi-azoue dissolves in 30 parts of boiling water, and crystallises in colourless needles ; it evolves gas and melts a t 205' (corr.). Tbe osazof2e dissolves in 200 parts of boiling alcohol, and crystallises in yellow needles; it melts and decomposes a t 224' (corr.). a-Galahpptitol is obtained by reducing a-galaheptose with sodium amalgam in a solution neutmlised with sulphuric acid ; it crjstal- lises in colourless needles and melts at 187-188' (corr.). The sub- stance is very readily soluble in water and has T, sweet taste, but dis- solves with difficulty in absolute alcohol ; in a concentrated solution of borax at 20°, it gave [a]D = -4.35".Gala-oafoizic acid is obtained from a-galaheptose by means of hydrogen cyanide. On decomposing the amide with aqueous barium hydroxide, the Zactone is formed, meltin5 a t 225-228' (corr.); at 20' it, dissolves in 'LO parts of water, but is scarcely soluble in abso- lute alcohol; the aqueous solution gives [a], = 4- 64.0' at 20'. The phenylhydrazide is colourless, and melts and decomposes at 233' (corr.) ; the barium salt is crystallinc and anhydrous. Gala-octose crystallises i n colourless lustrous leaflets containing 1H20, and melts at 109-111' (corr.) ; i t is strongly 1Eevorotntol.y. The l~henylhydrasone crystallises in slender leaflets and melts a t 205-210" (corr.) ; the osazone forms slender Sellow needles iii- soluble in water, and melts at 226-231' (corr.), Gala-octitol crystallises from 90 per cent.alcohol in slender needles, aud from water in colourless, rectangular plates; i t melts at 230-252' (corr.), does not reduce Fehling's solution, and is tasteless. p-Galaheptonic acid is obtained from the brown mother-liqnor con- taining the amide of the a-acid ; the action of water and pyridine at 235-140° converts it into the a-modification. The phenyZhyd~.aziJe dissolves in 4 parts of boiling water, and separates in colourless crystals melting at 185'; the aqueous solution a t 20' gave [ a j D = p- Galaheptose crystallises in prisms and melts and decomposes at 195-199O (corr.) ; 10 minutes after preparing an aqueous solution at 20Oit gave [a]= = -22*5', the final reading after 24 hours being [aID = -554.4" at the same temperature.The dibasic acid obtained from a-plaheptonic acid has been de- scribed by Kiliani ; a t 20' the aqueous solution gave (a]o = + 15.08". The acid obtained from P-galaheptonic acid by oxidation with nitiic acid is a syrup; the calcium salt contains 2H20, which is lost at 130°, and the solution in hydrochloric acid is dextrorotatory. Ammonical Derivatives of Milk Sugar, Maltose, Galactose, Xylose, Arabinose, and Rhamnose. By CORNEL~US A. LORRY DE BRIJYN and FREDERIK H. VAN LEENT (Rec. Tmv. Chim., 1895, 14, 134-149, and Ber., 1895, 28, 308S-3084; compare Abstr., 1894, i, 221 ; 1895, i, 7 and 640).-Di*y gaseous ammonia has no action on ordinary hydrated milk sugar, or on its anhydride a t the ordinary temperature. A concent,rated solution in aqueous ammonia exhibits - 6.32'.M. 0. F.ORGAXIC CHEMISTRY. 119 t h e normal rotation a t first ; the rotation diminishes, however, after some days, but the ultimate value cannot be determined on account of the darkening of the solution. Lacfose ammonia, C,zHz,01,,NH,, an additive compound analogous to aldehyde ammonia, is obtained when ordinary hydrated milk sugar is dissolved in methyl alcoholic ammonia, and the solution concentrated after being kept for 11-18 days. It readily loses ammonia both in the dry state, and also when its aqueous solution is distilled ; in the latter case about half the ammonia passes over, the remainder being retained by the coloured substances which are pro- duced. Determinations of the molecular weight of lactose ammonia by the cryoscopic method indicate that the substance is partially dis- sociated in dilute solutions.The author failed to obtain salts of the compound. Xaltosanaine, CI,H2,0,0*NHzI is best obtained by dissolving hydrated maltose in alcoholic ammonia; it melts and decomposes at 165O, and loses the whole of its ammonia when boiled with dilute sulphuric acid. When galactose is dissolved in methylic alcoholic ammonia two com- pounds are formed :-galactosamine ammonia, C6HII05*NHz,NHTa, which melts at 113--114', and galnctosainine, C6Hl1O5*NHZ, which melts and decomposes at 141'; the crystals of the latter can be kept in an ordinary desiccator without losing ammonia. If either of the com- pounds is boiled with dilute sulphuric acid, an amount of acid is neutralised corresponding with the combined ammonia.Xylosamine, C5H9Oa-NHz, melts and decomposes at about 130O. Am binosamine, CaHgOa*NH2, me1 ts a t about 124'. Rhamnosccnzine methylic alcoholate, (C6Hl10,*N H&,MeOH, is ob- tained by dissolving rhamnose in methylic alcohol; it may be recrystallised from methylic alcohol, and melts a t about 116*, but it commences to lose ammonia below, this temperature, The ethyEic alcoholate melts a t 80' with the loss of alcohol and some ammonia. The authors have as yet failed to obtain crystalline ammoniacal derivatives from mannose and glucoheptose. Action of Diastase on Isomaltose. By CARL J. h C T N E R (Chent. Centr., 1895, i, 91 ; from Zeit. ges. Ernuzu., 1894, 17, 378 ; compai*e this vol., i, 4).-The author has previously stated that isomaltose is readily converted by diastase i n t o maltose.Further observations have shown that the process is not complete ; in one case only 30 p e ~ cent. was changed. Experiments seem to show that isomaltose, obtained by the action of oxalic acid on starch, is not acted on at all by diastase. The author thinks that this may probably be accounted for by assnming that there are two stereoisomcric isomaltoses. Isomaltose. By EMIL FISCHER (Ber., 1895, 28, 3024-3028 ; compare Abstr., 1892, 412, and Brown and Morris, Trans., 1895, 709). -0st (Chem. Zeit., 1895, No. 67) has stated that Fischer's synthetical isomaltose is merely impure maltose ; in reply, the author states that his isomaltose is quite different from maltose, as it is not fermented by yeast, nor yet by the enzymes of yeast.Isomaltosazone is best A. R. L. *J. J. S.120 ABSTRACTS OF OHEMICAL PAPERS. recrystallised first from water, and, finally, several times from ethylic acetate ; it cannot be obtained in the pure state by cryatallisation from alcohol, the method employed by Ost. The melting point lies betmeen 140' and 155O, according to its purity. Isomnltose, after treatment with yeast and after dialysis, yields an osazone, which melts a t 2 5 8 O , and has a specific rotatory power [ajD = +7O. The author has not succeeded i n obtaining the pure carbohydrate. Action of Heat on Starch dissolved in Glycerol. By KARL ZULKOWSBI and BOH. FXANZ (Bied. Centr., 1895, 24, 557-558 ; from Bey. Oest. Ges. Fod. Chem. Ind., 16, 120--127).-When pure potato starch is heated with glycerol a t 190°, soluble staych is produced ; this is precipitated by alcohol, and by lime and baryta.It changes back to ordinary starch when kept either i n the dry state, or in concentrated aqueous solution. Soluble starch gives a splendid indigo coloration with iodine solution. Erythrode&in is formed when starch and glycerol are heated at 200' until the product gives a cherry colour with iodine ; it is then precipitated with alcohol and washed with alcohol. It is a white, sandy powder, which is not hygroscopic, and is only precipitated from its aqueous solution by baryta after the addition of alcohol. AcJwoodeahh is produced by heating the mixture a t 210° until the product 110 longer gives a red colour with iodine ; it is hygroscopic, and the solution is coloured distinctly brownish-yellow by extremely dilute iodiiie solution. When the heating at 210' is more prolonged, a pro- duct is obtained which is soluble in alcohol, but is precipitated on adding saturated baryta solution until sti*ongly alkaline ; the product consists of two substances, one a transparent, hygroscopic mass, very like gum arabic, soluble in strong alcohol, the other less transparent and hygroscopic, and soluble only in dilute alcohol. Erythrodextrin and achroodextrin reduce distinctly, but feebly, whilst the products soluble in alcohol do not reduce a t all.The rota- torypower of the partially purified substances was found to be as follows :-Soluble starch, 188.3 ; erythi-odextrin, 181.0 ; achroodex- trin, 173.5 ; products soluble in dilute and in strong alcohol, 151.5 and 98.9 respectively.Action of Oxalic acid on Inulin. By GEORC DijLr, (Client. Zeit., 1895, 19, 166 and 216--217).-The object of this i*esettrch was to find out whether the dextrin compounds (levulins) produced during the hjdrolysis of inulin with dilute sulphuric acid are really intermediate products in the inversion of the inulin into levulose, or are secondary products of reversion. The molecular weight of pure inulin was found to be 2950, which agrees with tho formula, (C6HloOb)ls, or (CsHlo05),s + H,O, and the rotatory power to be A table is giyea, showing the molecular weights and rotatory powers of varying mixtures of inulin and levulose. As tlw result of numerous experiments made with varjing quanti- ties of oxalic acid, the author concludes that no intermediate dextrin- like substances (levulins) are formed, so that, beyond doubt, the J.J. S. N. H. J. M. [UJD = -40".ORGANIC CHEMISTRP. 121 levulins produced by the action of dilute sulphuric acid on indin are really reversion products of lerulose. Directions for preparing crystalline levulose by the action of oxalic acid on innlin are given. It is further shown that if oxalic acid is allowed to rlct on lerulose for some time under Pressure, a substance, C6HS03, which is a deriva- tive of furfuraldehyde, is obtained. Sorbose also gives the same product (compare Kiermayer, this vol., i, 144). By SIEGAIUNL~ GABRIEL and ROBERT STELZKER (Ber., 1895,28,2929-2938; compare Abstr., 1888,G68).-When bromethyl- amine hydrobromide, prepared by heating bromethylphthalimide with hydrogen bromide and acetic acid, is treated with 33 per cent.potasli, and the resulting solution is distilled, a solntion of vinylamine is obtained, from which the free base separates when solid potash is added. The base boils a t 55-56', fumes in the air, has a strongly ammoniacal smell, mixes with water, attacks tbe skin, and has a sp. gr. = 0.8321 at 24". The oxalate, C2H5N,C2Hz04, forms slender needles, is readily soluble in water, and melts and decomposes at 11 5". When an aqueous solution of vinylamine is heated for some houm a t loo", the base undergoes alteration, ft syrupy mass being left after evaporation, from which crystalline salts cannot be obtained. Alcohol does not produce a similar change.Iodethyltrimetli ylamnioniuin iodide, CHzI*CH,*NMe3T, is formed by the action of methylic iodide on the base. The melting point, of this substance, stated by Schmidt a s 230-231', varies with the rate a t which the substance is heated. Vinylaniine combines with great vigour with carbon bisulphide, thi- being formed. This substance azoline p-hydrosulphide, SH*C< is converted by nitrous fumes into thz'a ;07yZ ti-szilphide, J. J. S. Vinylamine. N*$!H, S *CH2' which forms yellow crystals melting at 79-81'. Benzoic chloride converts vinylsmine into benzovinylanzide, C,H,*NHRz ; it is an oil, which solidifies in a freezing mixture, melts a, little above 0" and is partially converted by distillation into it-phenyloxa~zoline, a tarry residue being left.Benzovinylamide combines very readily with the halogen acids. Beizzo-P-iod eth y Eanzide, CH,I*CH,*NH Rz, crystallises in yellowish plates, and melts a t 110". Bromethyl- benzamide is converted by aniline into benzopheizylethy lened~amiite, NHPh*CH,*CH,*NHBz, .which melts at 127". The pZatinochloi*iJe melts and decomposes at about 205". When boiled with benzoic chloride, it, is converted into dibenzopheizyl.ethyleizediamiiie, melting at 147.5'- Benzoph e n y Z p q y Zenediamine, NHPh* C HMe*CH2.N H Bz, is obtained from @-bromopropylbenzamide in a similar manner. I t crystallises in small needles, and melts at 110-111".128 ABSTRACTS OF OHEMICAL PAPERS. Vinylamine unites with phenylic thiocarbimide to form vinyl- phenglthiocarhamide, C2H3*NHCS.NHPh, which crptallises in snow- white needles, and melts at 80".When heated with fuming hydro- chloric acid a t looo, it is converted into the isomeric n-phenylethylene- which forms compact, pointed p- f hiocarbamide, NHPh*C< prisms, and melts a t 160'. TTinyZ~henyZcal.bamide, C2R3*NH*CO*NHPh, is formed by the combination of vinylamine with phenylic cnrbimide ; it crystallises in campact, lustrous needles melting a t 82-83'. When it is heated with hydrochloric acid, it is converted into P-chlorethyl- phenylcarbamide, C2H,Cl*NH*CO*NHPh, which crptdlises in colour- less scales, and melts a t 124'; and this, when boiled with water, passes into n-phen ylet hy len e- +-carba?nide, NHPh*C<o which forms colourless, vitreous needles, and melts at 119-120'. P-Chloy- ctliylphenylcarbamide ireacts in a different manner with alcoholic potash, ethylenephenylcarbamide being produced.A. H. N-YH, S -CH2' N*CH2 Partial Oxidation of some Secondary and Tertiary Amines. By R. N. DE HAAS (Rec. Tmu. Chiin., 1895, 14, 166--189).-The object of this research was to follow the process of oxidation of certain secondary and tertiary amines when they are treated with an insufficient quantity of different oxidising agents. The quantity of oxidising agent was 60 adjusted that for one moleoular proportion of a secondary amine there was one equivalent of available oxygen, and for one molecular proportion of a tertiary amine there was either one or two equivalents of available oxygen. The formation of either am- monia o r nitrogen was not noticed, but the reactions may be expressed by the following equations.NHR2 + 0 = z NHZR + (I - Z) NHRZ + . N& + 0 = a'NH2R + y'NER2 + (1 - Z' - $)NR, + . . . . NR, + 2 0 = 2NHZR + y'NHH, + (1 - 2 - 2/')NR, + . . . . . . The author has endeavoured to determine the values of the unknown quantities x and y in these equations. The oxidising agents employed were potassium permanganate and potassium ferricyanide, and the following amines were investigated. Dimethylamine, diethylamine, dipropylamine, diisobutylamine, diamylamiae, dibenzylamine, tri- methylamine, triethylamine, and tripropylamine. The results aye drawn up in two tables. A. R. L. Constitution of Hexamethylenetetramine. BF PAUL DUDEN and MAX SCHARFF (Annaleii, 1895, 288, 218-252 ; compare Abstr., 1895, i, 325).-Hexamethyleuetetrsmine has been represented by numerous formulae, and the author advocates a special expression, which consists of a symmetrically constructed tetrahedron having a nitrogen atom at each apex and a CH, group situated medially on each edge.When dinitrosopentaniethylenetetramine is suspended in cold water and agitated with sodium amalgam, diamidopen tamethylenetetrauiineORGANIC CBEBIISTRY. 123 is prodnced, b a t the substance bas not been isolated. On adding benzaldeliyde to the liquid, however, dibenzylidei2ediamidopenta- T)Lethylenetetra?ni?ze, C,H,,N,(N-N:CHPh),, is formed ; i t crystallises from alcohol in long, silky needles, exhibiting feebly green fluores- cence, and melts at 226-227'. Boiling concentrated alkalis are without action on the substance, but i t dissolves i n cold, dilate acids, giving rise to formaldehyde, ammonia, hjdrazine, and benz- aldehyde.Diorl hohyd1.oxybenz~lidenediamicIoyentamet~ylenetet~~~~~~~e is ob- tained by adding sslicylnldehyde to a solution containing the base ; it crystallises from chloroform and ether in lustrous, white needles, and melts at 213'. It dissolves in alkalis, and is resolved into form- aldehyde, ammonia, hydrszine, ar,d salicylaldehyde by warm mineral acids. Di~netnnif~o'iestxylidenediamidopenfamethylenetetrnmine is obtained from metanitrobenzaldehyde and the base ; it crystallises from alcohol in lustrous, golden yellow needles, and melts at 134'. Dicinnamylidesiedianaidopentamethylenetetramine crystallises from alcohol i n palo yellow lustrous leaflets, and melts at 207'.Reduction of tri ni troso t rime th y lenetri amine wit h sodi urn amal %am gives rise to a liquid containing triamidotrirnethylenetriamine. The triorthohydrozybenzylidene derivative of this base crystallises from a mixture of chloroform and ether in long, white needle^, and melts at When a freshly prepared solution of diazobenzene chloride is added t o well cooled, aqueous hexamethylenetetramine, a compound, CI7H2,N8, is formed, which crystallises from benzene in yellowish- brown leaflets, and melts and decomposes at 228'. It is indifferent towards boiling alkalis, but when treated with dilute acids i t yields nitrogen, ammonia, aniline, and formaldehyde. No evolution of gns attends the dissolution of ice-cold concentrated hydrochloric acid, the diazobenzene residue being eliminated.139-1 40". Bisparanitrodiazobenzenepentamethy Eenet etramin e, C,H,,N,(N*N :N*C,H,*NO2),, is obtained by mixing diazotised paranitraniline with hexamethylene- tetramine at the temperst u1.e of melting ice, formaldehyde being eliminated. It dissolves with great difficulty in common solvents, but crystallises from hot ethylenic bromide in yellow needles, and melts and decomposes at 244'; it is indifferent tomnrds boiling alkalis, but is resolved by dilute acids into nitrogen, ammonia, para- nitraniline, and formaldehyde. Bisme tnnitrod iazo benzeiiepentamethy lenetriamine cry s t alli ses from a mixture of alcohol and chloroform in lustrous, yellowish-green plates, and melts, evolving gas, a t 184' ; nitrogen, ammonia, metanitrani- line, and formaldehyde are iormed under the influence of dilute acids.Sodium pentamethylenetetranainebisdinzobenzenesulphonate, is only sparingly soluble in cold, but readily in hot, water; a,124 ABSTRACTS OF CHEMIOAL PAPERS. portion of the water is given off at looo, whilst above this tempera- ture the salt becomes yellow and decomposes. The d u e ? . salt, is amorphous, and the coppel. and ?$ic/ieZ salts crystallise in minute needles ; the bariirnz salt, containing 3H20, becomes anhydrous at looo. When aqueous hexamethylenetetramine is agitated with soda and benzoic chloride, two compounds are formed, one of which, dissolv- ing in ethylenic bromide, consists of the tribsnzoyl derivative of tri- methylenetriamine ; it melts at 220-221°, and when gently heated yields formaldehyde, ammonia, and benzoic acid.The second pro- duct, which does not dissolve in ethylenic bromide, is the tribenzoyl derivative of diamidodimetfhylamine ; it crystallises .in rhombohedra, and melts at 266-267", yielding; the same products as the foregoing substance when treated with mineral acids. M. 0. F. Reactions of Formaldehyde. By T. H. LEE (Chmn. News, 189.5, 72, 153-1 54) .-Formaldehyde reduces permanganate imme- diately, and is itself oxidised to carbonic anhydride and water ; it also reduces potassium ferricy anide, hot Fehling's solution, and cold alkaline mercuro-potassium iodide, rtl though neither nmmoniacal copper sulphate nor mercuric chloride is affected in this manner by it. It deepens the colour of hot ferric chloride, and the solution, after cooling and re-heating, yields with ammonia a precipitate of basic ferric formate.Formaldehyde precipitates silver from its am- moniacal solution, both iu the specular and pulverulent forms. D. A. 1;. Organo-metallic Compounds. By ERNST BPCKMAPFN aud G. SCHLIEBS (Annulen, 1895,289,71-90 ; compare Abstr., 1692, 169).- The authors have endeavoured to ascertain the molecular weight of the sodium derivatives of certain ketones and alcohols by the ebullio- scopic method. Examining camphor, menthone, deoxybenzoin, and acetophenone, dissolved in ether or benzene, they find that the sodium derivatives of these compounds appear to have molecular weights amounting to three or four times the value calculated from their empirical formuk ; the determinations are not in agreement with definite chemical expressions, being appreciably dependent on the nature of the solvent, and the authors regard it as probable t h a t a state of equilibrium exists between the dissociating action of the scl- vent and the tendency to associate exhibited by the molecules of the sodium derivatives.The sodinm derivative of menthol is bimolecular, whilst ethylic and isopropylic alcohols, dimethylethylcarbinol, and phenol yield compounds of simple molecular structure ; the sodium derivatives of ethylic acetoacetate and ethylic rnalonate are also unimolecular in alcoholic solution. The volume of hydrogen liberated on adding sodium to a solution of ethylic acetoacetate or ethylic malonata in ether is in exact agree- ment with the amount required by theory ; when acetone is treated in t h i s way, a quantity amounting to 4.5 per cent.of the available hydrogen is liberated (compare Freer, Abstr., 1894, i, 6s). M. 0. F.ORGANIU CHEMISTRY 12.5 Behaviour of Thioacetic acid with Salt Solutions. By N. TARUGI (Gazzetfa, 1895, 25, i, 341-352 : compare Schiff and Tarugi, Abstr., 1895, ii, 84) .-After washing with carbon bisulphide to re- move free sulphur, the white precipitate obtained on adding thioacetic acid to solutions of niercuric chloride in the cold, is found to be mercuric chlo3'oszdphide, 2HgS,HgCI,, not mercuyic thioacetate as previonsly stated ; i t is an amorphous powder, soluble only in nitro- hydrochloric acid. If mercuric nitrate is employed in place of the chloride, a white precipitate of mercuric riitrosulphide, 2HgS,Hg( X0j)2, is deposited ; this is a whiLe, amorphous powder, which is blackened by soda or ammonia, and is soluble in nitro1iydroch:oric acid, bnt not in other acids.dfercuric thioacctate, Hg( SAC),, therefore, does not seem to have been previously obtained ; it may be prepared by slowly adding thioacetic: acid to alcoholic mercuric acetate in the cold, when a white precipitate, immediately changing to minute, transparent, yellow crystals, is deposited. This, ou washing with carbon bisulpli- ide and crystallising from chloroform, is obtained in beautiful, white scales ; it is soluble in hot benzene or chloroform, and, on treatment with concentrated nitric acid or hoh hydrochloric acid, yields the nitrosnlphide or riitrocliloride described above, whilst, with sulphuric acid, i t yields the double compound, 3HgS,HgS04.The thiowetate is converted into mercuric sulphide by ammonium sulphide, or by hot potash or soda, whereas hot ammonia gives rise to the acid compozmd, Hg2S€II,NOAc. Mercuric thioacetate is soluble in nitrohydrocliloric acid, and is reduced to mercury by stannous chloride. It is accom- panied in its preparation by a basic tlhioacetate, KgO,Hg(SAc),, which can be separated by taking advautage of its insolubility in hot chloro- fo1.m or benzene ; it is a red, amorphous powder, insoluble in nitric or hydrochloric acid, but soluble in nitrohydrochloric acid. On adding thioacetic acid to a copper salt in cold, neutral solution, it green precipitate is deposited which rapidly blackens during filtration ; the filtrate slowly deposits red flocks of cup]-ic thioacetate, CU(SAC)~, which is not affected by air or light, is soluble in nitric acid, and is converted into the sulphide by hydrochloric acid, dilute sulphuric acid, ammonia, soda, or ammonium sulphide, Cadmium salts in cold solution yield a precipitate of cadmiunL thio- acetate, Cd(SAc)z, with thioacetic acid ; it is a white, amorphous powder, soluble in mineral a d s , and is converted into the sulphide by ammonia or ammonium sulphide.On adding thioacetic acid to solutions of sil-rer salts, a red precipi- tate is obtained which soon changes into the black silver sulphide ; it is probably silver thioacetate. A mixture of lead thioacetnte, P ~ ( S A C ) ~ , and sulphur is deposited on adding thioacetic acid t o neutral lead solutions; thencw salt is it white ciytalline substance which is converted into the sulphate by nitric acid, and into sulphide by ammonia, soda, or ammonium sulph- ide.Very dilnte solutions of lead chloride give, i n the cold, a red precipitate of lead chZoyosuZphide, PbCI2,:3PbS, from which boiling water extracts lead chloride. W. J. P.126 ABSTRACTS OF CHEJIZCAL PAPERS. Synthesis by means of Ethylic Cyanacetate. By C. TIMOTHEE KLOBB (Comyt. reird., l895,121,463--465).-When ethylic or methylic a-cyan-/$ benzoylpropionate is mixed, in molecular proportion, with potassium hydroxide in 5 per cent. solution, and the mixture is acidified at once with sulphuric acid, and extracted with ether, cyan- yltenacylucetic acid (a.cyan-@- benzoylpropionic acid), COPh*CH,*CH(CN).COOH + H,O, is obtained. It crystallises from hot water in white, nacreous plates which melt a t 69", lose their water in a dry vacuum, and then melt a t 99-100'. The sodium salt crystallises with 3H20 in prisms very soluble in water and alcohol ; the silver salt is white and insoluble ; the pheiiylhydrazine compound melts at 113O. When boiled for a long time with a large excess of potassium hydroxide, cyanphenacjlacetic acid yields phenacylacetic acid, COPh*CH2*CH,COOH, which melts at 116O, and is identical with the P-benzoylpropionic acid of Kues and Paal. Methylic u-cyano-P-benzoyl-a-methylpropionate forms slender needles which melt a t 113' ; ethylic a-cyaizo-P-benzoyl-a-ethylpropionate crystallises from carbon bisulphide in large, rhombic prisms which melt a t 64' ; methylic a-cyano-/3-benzoyl-a-benzylpropSonate melts at 13.3-134'.Attempts t o displace the hydrogen by benzoyl were unsuccessful, a result analogous to that obtained by Haller with alkylic cy anace toac e t at es . E thylic sodiocyanacetate and chloracetone in presence of absolute alcohol, yield etiiylic cyanacetonylacetate (a-cyan-P-acetylpmpionate), an amber-colonred liquid, which boils a t 160-171' under a pressure of 24 mm. ; sp. gr. = 1.100 at 1 6 O . Tt dissolves in alkalis and in concectrated hydrochloric acid ; its phenylhydrazone forms white needles which melt a t 144'. Methylic sodiocynnacetate in presence of methylic alcohol yields the corresponding methyl compound which boils a t 159-166' under a pressure of 26 mm.; sp. gr. = 1.148 a t 1 6 O . Its phenylhydrazone melts at 137-138'. Action of Sulphur on Unsaturated Aliphatic Compounds, By JULIUS ALTSCHVL (ZeiC. ungw. Chem., 1895, 535--542).-The first part of this paper consists of a re'sume'of the work done by Henriques (Cheni. Zeit., 1893,636), Weber (ibid., 1894,112), Anderson (Annalen, 63, 370), Benedikt and Ulzer (ilIonatsh., 1887, 208). Saturated fatty acids, such as stearic acid, when heated with sulphur for some time a little above their melting points, are not appreciably acted on ; in order to deconipose such an acid, it must be heated with sulphur to a t least 200'. Hydrogen snlphide is then evolved and sub- stitution products, resembling those obtained by Benedikt, are formed, An unsaturated acid, such as olejic acid, behaves quite differently ; when heated with 10 per cent.of sulphur for some time at 130-150°, complete solution ensues and chemical combination takes place with- out the evolution of hydrogen sulphide. All unsaturated compounds behave in exactly the same manner with sulphur, and within the same range of temperature. The author has proved that combination with sulphur does actually take place, since t h e products formed by the action of sulphur on fatty oils, when hydrolysed with alkali, yield soaps, and these when acidified yield acids which contain sulphur C. H. B.OROANIO CHEMISTRY. 127 chemically corribined ; the hydrolysis is best) carried out a t low tem- peratures with alcoholic potash, as when hydi*olysed a t fairly high temperatures, hydrogen sulpbide is eliminated, and salts of acids free from sulphur are ohtained (compare Henriques). Tile sulphur additive compounds, just like the oxidation products, of the fats, unite with sulphur chloride, SZCI2.The fatty oils which are most readily oxidised, namely, those which most readily form additive compounds with oxygen, are also the compoiinds which most readily unite with sulphur. Sulphur chloride does not readily unite with those sulphur additive compounds which are difficult to prepare. The nature of the sulphur additive compounds varies greatly with the nature of the oil and the temperature at which the operation is carried out. Ole‘ic acid apparently unites with 1 atom of sulphur. a t moderate temperatures, whereas many glycerides form varying products (probably mixtures)bwhich are largely influenced by the temperature at which the action takes place.Thiorufic and Thiocarbacetoacetic acid. By OSKAR EMMERLIS(; (Ijer., 1895, 28, 2882--2888).-The analysis and cryoscopic deter- mination of the molecular weight of thiorufic acid lead to the formu1,z C2,HZ&08, instead of the simpler formula, CloH14S304, which was ascribed to this substance by Oppenheim and Norton (Be,,., 10, 701) ; the salts have corresponding formuh, the sodium salt being C21H26Na2S608. When this sodium salt js treated in the cold with aqueous soda, hydrolysis takes place, an6 a new acid is formed, which is very readily soluble in water, and melts a t about 173’. This sub- stance has the formula c 1 5 H ~ 6 s 6 ~ g , and is pentabask, the barium suZt having the formula (C15HnS60~1)2B%.The autho1.s pi opose to give tlie name thiom1Jic acid to this new compound, the original acid of Oppenheim and Norton being known as etherthiorz& rccid. Ethylic thiocarbacetoacetate was also first prepared by Oppenheim and Norton, who ascribed t o it the constitution CS:CAc.COOEt. This formula is confirmed by the fact that when the substance is heated in alcoholic solution with lead oxide, malunic acid is formed, lead sulphide and acetic acid being also produced. Ethylic thiocnrb- acetoacetate yields a dibronzo-derivative, which crystallises in thick, yellow needles, and melts at, 171°, as well as a tl,ibronio-del.i~ati~~, which ci-ystallisea in lustrous yellow plates melting at 1 8 0 O .The latter of these also yields malonic acid when it is treated with lead: oxide, and this reaction proves the presence of 2 methyl group in the original substance. In the preparatiou of ethylic thiocn~lsacetoacetate, a small amount of ethjlic malonate, which is probably derived froni a partial decomposition of this compoulld, is always produced. Action of Sodium Hydroxide on Allylmalonic, Allylacetic, and Ethylidenepropionic acid. By JOHN G. Si’EsztiIt (J. A.lner. Chem. SOC., 1895, 17, 1--32).--The greater part of this work been previously published (compare Fittig a n d Spenzer, Abstr., 1195, i, 204). It is shown that y6-unssturxted acids behave very differently from p-1-acids when boiled with sodium hydroxide solution. Allylmalonic acid is not acted on when treated iu J.J. S . A. H.128 ABSTRACTS OF CHEMICAL PAPERS. this way, and allylacetic acid yields only a trace of an acid whose barium salt is soluble in alcohol, b u t the exact composition of whicll could not be determined. Sodium ethylidenepropionate, on the othel- hand, is readily converted into sodium propylideneacetate. In the preparation of ethylidenepropionic acid by the destructive distillation of niethylparaconic acid, the distillate contains ralerolactone, methJI- citrnconic acid, methylitaconic acid, and unaltered methyl paraconic acid. The author gives methods for the separation of each constituent. Action of Zinc and Ethylic Bromisobutyrats on Acetone. Synthesis of Tetramethyiethylenelactic acid. By S EHC;IL'S REFORMATSKY and 13.PLESCONOSSOFP (Ber., 1895, 28, 2838-2841).- Ethylic bromisobutyrate and acetone, in molecular proportion, arc added t o zinc, the mixture is cooled xith water, and after a week is heated at 60-7U' during two hours, water is added, the liquid is acidified with sulpltnric acid, and the oil removed, washed, dried, and fractionated. The first portion consists chiefly of ethylic isobuty- rate, the second portion (b. p. 150-200") when redistilled, yields ethylic p-hydroxytstramethylpropionate, OH*CAfe,*CMe2*CO0 Et (tetra- methylethylenelactate), which is a thick, ycllow liquid, boiling at 196-197' ; it has a pleasant odour, and is insoluble in water. The free acid, prepared by hydrolysis of the ethjlic salt with barium hydroxide, crytallises in plates, melts at 152-153', previously decreasiug in rolume, and boils and in part dccornposes a t 192-193'.By the action of sulphuric acid, dimethglisopropylcarbinol and tetramethyl- et.hglene are formed ; liydriodic acid yields tetraniethyletbylic iodide. The yield of acid is 25 per cent. of the theoretical. The barium salt forms stellate crystals which become pulverulent when dried. The calcium salt crptallises in plates, the si1z;er scdt in short, lustrous prisms, and the lead salt in tetragonal prisms ; the sodium and z i m salts have also been prepared ; all are readily soluble in water. Action of Zinc and Ethylic Bromisobutyrate on Isobutalde- hyde. Synthesis of Secondary /j-Hydroxy-acids. By SERGIUS REFORMATSKY (Ber., 1895, 28, 2842-2847).-1t has been previously shown (Abstr., 1887, 717) that etbylic chlorncetate and zinc yield, with ketones, tertiary P-hydroxy acids, but no corresponding com- pounds are formed with aldehydes, the action proceeding so slowly that the latter are in part oxidised and in part undergo condensation. Ethylic bromisobutyrate reacts more quickly, and, with aldehydes, yields secondary /%hydroxy-acids.The ethylic salt and aIdehTde are mixed i n molecular proportion, and added to the zinc in a reflux apparatus, the flask is allowed to remain in a cold water bath during 7-9 days, then heated at 60-70" for 1-3 hours ; after 24 hours, the product is treated successively with water and dilute sulphuric acid, and the oily layer removed and purified. J. J. S. J. B. T. Xi hy lic p- h y d rosy -%-dime t h y1-P- isoprop y lpropiona f e , CHMe,*CH(OH)-CMe,*COOEt, is a yellow, viscid liquid with a pleasant odour, and is iiisolnble i n water; it boils at 169' (140 ma.) and at 221-222' (738.5 mm.).ORGAN10 CHEMISTRY.129 The acid crptallises in lustrous prisins, melts a t 92", and is optically inactive; at 19", 2.03 parts dissolve in 100 of water. The yield is 58 per cent. of the theoretical. The molecular weights of both corn- pounds mere determined by the cryoscopic method in benzene. The salts are all readily soluble in water with the exception of the copper compound ; the calciicm salt crystallises in prisms. The acid (m. p. 111-112°) prepared by Hantzsch and Wohlbruck by the action of sodium on ethylic isobutyrate is diisopropyloxalic acid, not the above hydroxydimethSlisopropylp~opionic acid, but the latter has been pre- viously obtained by Fossek by oxidising the aldol condensation pro- duct of isobutnldehyde.When distilled with dilute sulphuric acid (1 : 5 ) , the above acid yields carbonic anhydride, dimethylisopropyl- ethylene, and a neutral compound, which is probably a Zuctone, ,O ; i t boils a t 209--91lo, melts a t 525-53.Z0, and its C H2* CMe2 forination is probably preceded by that of the unsaturated &-acid. By the action OE hydriodic mid 011 the propionic acid, the same lactone is formed together with lieptylic iodide (?) in small quantity. pe,-co, J. R. T. Formation of Carbon Chains. 11. Conjugated Ethereal Malonates. Ey Cmr, A. BISCHOFF (Ber., 1895, 28, 2824--28&5; compare this vol., i, 8P).-Hitherto only compounds of tlie types , have been prepared from ethylic alkylsodiomalonates and methylenic iodide, etllylenic bromide, and trimethylenic bromide respectively.The diffi- culty of obtaining methylenic bromide in quantity has, for the pre- sent, restricted the quantitative investigation of the reaction t o the second and third type ; thc results are in complete accord with the dyriamicnl theory whicli indicates that the linking slioulci be effected more readily in tlie 1r.tter (position 1-7) tlian in the former (posi- tion 1-6) case. (1) Ethylenic bromide with ethyZic alkyl~rLalonates.-The malonate wag mixed with alcoholic sodium ethoxide, arid ethylenic bromide added; after boiling during 10 hours more ethylenic bromide was added, the boiling continued during seven hours, and this treatment repeated until the liquid was no longer alkaline.The normal com- pound was never formed in any considerable quantity, the products being mixtures of the original ethylic salt and the bromo-derivative, CX(COOEt),*CH,*CH,Br. A portion of the ethylic salts undergo hydrolysis, and the sodium derivatives thus formed dissolve in the crude product4 and decompose during the distillation, forming gaseous substances ; this was most marked in the case of ethylic isobutyl- malonate. The following ethylic alkylmalonates were employed : Methyl-, ethyl-, propyl-, isopropyl-, isobutyl, isoamyl-, and allyl- , Experiments were also made with mono-, di-, and tri-niethyleth~4enic bromides; in no case is the reaction normal, but, with trimethyl- ethylenic bromide, for example, the ethylic mslonates combine, and trimethylethylene is formcd.1 2 3 4 5 1 2 3 4 5 6 1 2 3 4 5 6 CO*CX*C.~X co . co*~x-c~c*~x*co~ co*~x*c*c*c.~x~&o bo co ' co co ' co co J 1 I 1 VOL. L X L i. I130 ABSTRACTS OF CHEMICAL PAPERS. (2) T.ri?izcflLylenic br*omii,le w i f l b eth ylic sotlionialo,aatf~ aid ethylic sodiomethylinalon,ate .r.espccti.t.ely.-In both t hese cases, normal pro- ducts were obtained and identified by analysis and observation of their boiling point. The substituhion of aliylic tyibromide for trimethyl- enic bromide gives rise to abnormal products. From carbon tetra- chloride and ethylic sodiomalonate, a compound containing onlF two mnlonyl radicles was obtained. Chabri6 has described a compound with four mdicles, C[CH(COOEtr)2],, but a repetition of his experi- ments does not confirm the statement ; ethylic ethanetetracarb- oxylate and an orange-yello\v sodiunl compoz~iid.(COOEt),C:C:C(COO?Sa)COOEt or (COOE t ) $32 (OE t) *C h'a( C 0 0 Et),, are formed (cornpare %elinsky and Doroschewsky, Abstr., 1895, i, 129). Expeiiments with etliylic sodio- and disodio-malonate and tetra- chloro-, and tetraiodoethyleue show that the action proceeds according to the equation 4CHNa(COOEt),+C2TI = 4Nal+ C,H, + CH(COOEt)z*CH(COOEto)2+ C(COOEt)2:C(COOEt)z ; the quantity of acetylene formed is p~actically the same from both the sodium compounds, and is about twice as great as from an equivalent quan- tity of sodium ethoxide ; the substitution of xylem for alcohol as the solvent has little influence on tho reaction.Negatire results were obtained with the two sodium compounds and hexnchlorethane and hexachlorobenzenc. Full experimental details are given in the paper. J. H. T. Trimethylpimelic acid. By NICOLAI I). ZEJ~TSSKY and A. REFOR- MATZKY (Bey., 1&95, 28, 2%3--2945) .--A mixture of ethylic cyano- propionate and dibromobntane, CHMeBr*CH2*CH2Br (Demjmow, Abstr., 1895, i, lgl.), \vas treated with sodium ethoxide ; the resulting ethylic dicyatLot?-imethylpi?nelate, COOEt*CMe( CN)*CH31e*CH2*CH,*CMe (C N) *C 00 Et, boils :tt 232-233O under 20 mm. pressure. When i t is boiled with sulphuiic acid, it becomes hydrolysed, and loses carbonic anhydride, and trimethylpimelic acid, COOH*CKMe*CHMe*CH,.CH,.C HMo-COOH, is obtained ; this boils at 213-215' under 15 mm.pi.essui-e. When the calcium salt is distilled with excess of calcium hydroxide, that fraction of the distillate which boils a t 190-191' consists mainly of t rimeth ylketohe;2.nmeth?ilelie, CH:<CH2-cHMe>C0. This has a sp. gr. = 0.9129 at lS"/4', and smells of peppermint ; in moist ethereal solution, it is reduced by sodium to the alcohol, which boils at 193-195' under 747 mm. pressure, has a fjp. gr. = 0.9119 a t 1 i o / 4 O , and smells like menthol. C. F. B. CHMe-CHJle Alloisomerism. By ARTHUR ~ \ ~ ~ ~ c E A E I , (J. p r . Chem., 1895, [2], 62, 289-325 ; compare Abstr., 1S91, 1184; 1893, i, 142, 144).-ORQANlO CHEMISTRY. 131 This, and the four succeeding papel's, are dei-oted to the exposition of facts and theories which are at variance with van't Hoff's stereo- chemical hypothesis and with Wislicenus's argnnients in support thereof.The best methods for obtaining bromine additive compounds of unsaturated acids are dealt with. Citl.adibromop?J,.ota,.ta,.ic: a?&hy&ide, CJH4BrZ03, is ffi yellowish oil, and is prepared by exposing a mixture of the calculated quantities of citraconic anhydride and bromine to sunlight. Bromoiusllejic acid was prepared by three methods, each of which is described, and was found to be identical in each case, and Petri's conclusion with respect to Kekulk's results (Abstr., 1879, 373) is con- firmed ; the acid melts at 136--138O, not 128" (Eoc. cit.). A similar investigation into the methods for prepaying byornof umaric acid led to a similar conclusion ; the acid melts a t 185-186O, not 177-178'.Details of the behaviour of the lead and silver salts of both these acids are giren. By takicg advantage of the difference i n solubility of the hydrogen potassium salts of these acids (100 parts of water a t 14' dissolve 4-04 parts of the bromofumarnte and 23.8 parts of the bronio- maleate), it was shown that when dibromosuccinic acid is boiled with water (Zoc. cit.), about 2-3 per cent. of bromofumaric acid is pro- duced, together with bromomaleic acid, b u t the converse production of bromomale'ic acid together with bromofumaric acid, when isobronio- succinic acid is boiled with water, could not be proved. According t o the generally accepted configuration for bromonialeic and bromofumaric acids, the former should lose hydrogen bromide more readily than the latter, these elements being plane-symmetrical in bromomalejic acid ; experiments were accordingly made with chloro- niale'ic and chlorofumaric acids, in which equal weights were treated with a slight excess of caustic potash under the same conditions, and the amount of potassium chloride formed was determined in each case after the lapse of a certain time.It was found that at lo', in the course of 4s hours, about 48 times as much hydrogen chloride was eliminated from chlorofumaric acid as from chloromale'ic acid under similar conditions ; eyen a t looo, this difference is still to he noticed after the lapse of 15 miniites, the ratio of decomposability being, how- ever, much smaller, namely, l : 1.2 instead of l : 48. In the same way, i t was shown that in the course of 24 hours a t loo, brorno- iumaric acid lost 18 times as much hydrogen bromide as bromomale'ic acid did.If the facility with which halogen hydride is eliminated from these acids is to be regarded as indicative of p1ane.qmmett.y of structure, then the above experiments show that bromofurnaric acid is p lane-sy m m e t rical. Another argument advanced by Wislicenus for plane-symmetry in an acid is that such a configuration must be indicated by easy elimina- tion of carbonic anhydride from the salts of the acid. Accordingly, a comparison was made between the amoniit of carbonic anhydride lost by equal weights of silver bromofumarate and silver bromo- maleate respectively, when heated a t 100" in aqueous solution, and it was found that in two hours silver bromomsleate lost 4.3 times as much carbonic anhydride as silver bromof umarzite did.When the 1 2132 ABSTRACTS OF CHEJIMICAL PAPEhS. same iiiethod was applied to silvey bromomesaconate and silver bromo- citraconate, i t was found that in 16 hours a t 105' the bromomesaconate had lost 3.68 per cent. of cai-bonic anhydride, and the bromocitra- conate 7.11 per cent. Bromoinale'ic acid yields fumaric acid when reduced by zinc dust, even in absence of alkalis, which are known to partially convert male'ic into fumaric acid ; so, also, bromocitraconic acid yields mesa- conic acid, even in the absence of alkalis. Bandrowski's statement (Ber., 1882, 15, 2695) that chlorofumaric acid is obtained when hydrogen chloride reacts with acetylenedicarb- oxglic mid is confirmed ; this is contrary to Wislicenus's interpre- tation of van't Hoff's hypothesis. By adding a strong soltition of potassium thiocyanate to one of maleic acici, fumaric acid i+ precipitated ; but t h i s conversion does not admit of a similar interprctatioii to that applied by Wislicenus to the conversion effected by mineral acids (Riiurnl.Anord., 29). Isodi- broinosuccinic acid is converted into dibromosuccinic acid when heated with a saturated solution of hydrogen bromide at 100Oin a sealed tube. A. G. B. Relative Ease of Elimination of Carbonic Anhydride from the Silver Salts of the p-Chlorocrotonic acids. By ARTRUR MICHAEL and T. H. CLARK ( J . p r . Chem., 1895, [2], 52, 326--330).- Silver P-chlorallocrotoiiate is deconiposed with elimination of carbonic anhydride more easily than ifi silver 6-chlorocrotonate.P-Chlorallo- crotonic acid yields p-chlorocrotonic acid when heated with hydro- chloi*ic acid. Ethylic dibromofumarate loses halogen more easily than ethylic dibromomaleate does. A. G. B. Alloisomerism. By AR.nIvR NICIIAEL and GEORG T1sso.r (J. pr. C'hma., 1895, [2], 52, 331--343).--.It has been shown already (Abstr., 1893, i, 142) that dichlorosuccinic acid yields chlorofumaric acid u-hen i t loses hydrogen chloride ; wben heated with acetic anhydride, horn- ever, it yields chloromale'ic acid, and this, by reduction with zinc, is converted into f umaric acid. Wheii sodium dichloromccinate is Iteated in aqueous solution for half an hour, i t is converted into sodium chloromaleate, a result which renders it possible that when excess of alkali is used (Zoc.cit.), the production of chlorofumaric acid is due to the further action of this alkali on chloromale'ic acid. Dichlorosuccinic acid yields both racemic acid and inactive tartaric acid when its halogen atoms are replaced by hydrosyl groups, in this resembling dibroniosuccinic acid. Bromomesaconic acid (Abstr., 1894, i, 441%) melts at 217-218', and dissolves easily in water, alcohol, acetic acid, and ethylic acetate, but only very sparingly in benzene and cliloroform. Mesadichloropyrotartaric acid yields the same products when heated with water as are obtained from citradichloropyrotartaric acid under the same conditions (Abstr., 1893, i, 142). Citradichloropyrotartaric acid does not yield the so-called hydroxycitraconic acid when heated with bnrytrt water (Morawski, J.pr. Chem., [a], 11, 446). The behariour of xeronic anhydride and of aconitic acid and itsORGANIC CHEMISTRY. 133 ethereal salts towards halogens was studied, without any very definite rcsul ts. A. G. B. The Laws of Alloisomerism and their Employment in Classifying Unsaturated Organic Compounds. By ARTH u it MICHAEL ( J . pr. Chem., 1895, [2], 52, 344--365.-The following rules constitute a summary of the modes of formation, reactions, and sta- bility of alloisomeric compounds as elucidated by the experiments of the author and his fellow-workers. 1. If two unsaturated monhnlogen acids are obtainable from one saturated a/.?-dihalogen acid, they will be alloisomeric a-deimivatives.2. The maleino'id modifications of unsaturated compounds are more easily soluble, of lower melting point, and more volatile than the corresponding fumaroid modi6cations. 3. Of two halogen-free, alloisomeric, unsaturated acids, that of lower melting point will be converted into the fumaroid modification, of higher melting point, by being heated with water, mineral acids, 01- halogens. 4. The lower melting, maleino'id form of an ap-unsatuisated a-halo- gen acid passes into the higher melting, fumaroiid form when heated, and when under the influence of mineral acids. 5. Fumaroid derivatives from ap-unsaturated halogen-free mono- basic acids of the ethylene series, formed by the replacement of /3-hydrogen by a negative atlorn or radicle (halogen or carboxyl), are converted by heat, either entirely 01' in part, into the corresponding malei n oYd modifications.6. The maleino'id modifications referred t o in 5, are converted, entirely or partly, into the furnardid modifications when heated with mineral acids. 7. If the halogen is present in tohe a- as well as in the /+position in alloisomeric ap-unsaturated ethylene compounds, the influence of each position is exerted, and such compounds are partially converted into each other when heated. 8. The addition of 1 mol. of halogen hgdride to an xp-unsaturated acid of the acetylene series directly produces, either entirely or in great part, a P-halogen acid of the higher melting fumaroid form. 9. The higher melting, fumaroiid modification of two alloisomei*ic, ap-unsaturated, a- or p-halogen acids of the acetylene series yields halogen hydride more easily than does the lower melting maleinold modification.10. A mixture of two alloisomeric additive products is formed when bromine is added to a9 acetylene derivative containing a negative radicle in the place of hydrogen, but the fumaroid modification will be directly formed in the larger proportion. 11. Of two alloisomeric ap-dibromethylene derivatives, the fumarojid modification yields a halogen-free acetylene derivative by loss oE bromine more easily than the maleinoid niodification does. 12. By the addition of bromine to both modificntioiis of an a/?-nnsaturated a-bromo-acid, the same unsaturated tribronio-acid is obtained. 13. Both alloisonieric modifications of an q'3-unsatumted a-ha!ogcu134 ABSTRACTS OF CHENICAL PAPERS.fatty acid yield wholly, or in great part, the same halogen-free acid, namely, the higher melting f umaro'id modification, when the halogen is replaced by hydrogen. 14. The silver salts of alloiaomeric, ag-unsaturated P-halogen acids of the ethylene series are decomposed by water with formation of silver acetylide, or silver alkylacetylide, carbonic anhydride, and silver halo'id. This decomposition takes place more readily in the case of a maleinoid form thau in the case of a fumaroid form. 15. By separation of halogen from the two modifications of a saturated a@-dihalogen acid 01' its ethereal salt, the fumaro'id modi- fica,tion of the correspoiiding unsaturated acid, or its ethereal salt, is formed. 1G. By the elimination of 1 mol. of hydrogen bromide from the product of the addition of bromine to a fumnro'id fatty acid of the ethylene series, there is produced, for the major part, a maleinoid a-brorno-acid ; contrariwise, a funiaroid bromo-acid is the chief pro- duct of a similar change in an allo-ap-dibromo-acid.I n the case of the corresponding chloro-acids, the eliniination of hydrogen chloride yields a mixture of both a-chloro-acids. 17. No generalisation is yet possible concerning the stability of saturated alloisomeric ap-dibromo-fatty acids towards mineral acids. 18. Chlorine and bromine are not necessarily equivalent elements i n an alloisomeric sense, so that the behaviour of a chlorinated deriva- tive cannot be deduced from that of a brominated derivative.19. Ring-formation is a periodic function of the chain-length. 20. The relative positiveness and negativeness of an unsaturated carbon atom is dependent on its absolute distasce from the other atoms of the molecule, so that the " positive-negative rule " (Abstr., 1889, 1140) is applicable for the ascertainment of the position of such atoms. A table of maleino'id and Pumaro'id modifications of ap-unsaturated alloisomeric compounds is given, together with detailed examples of the foregoing rules. The untenable character of the W islicenns-van't Hoff configura- tion is then discussed. A. G. €3. Alloisomerism: Remarks on the Work of Bischoff, Wislicenus, and Van% Hoff. By ARTHUR &!ICHAEL (J. pr. Chem., 1895, [el, 52, 365472) .-A controversial paper. Influence of Substitution on the Course of the Reactions of and M.HERSCHKOWITSCH (AnuaZen, 1895, 289, 52--58).-1n view of the attention which has been recently directed to tho influence of substitution on chemical behaviour, the authors have investigated the action of phosphorus pentachloride on alkylic salts of substituted acetonedicarboxylic acids. It has been shown by von Pechmann, that towards this agent ethylic acetonedicarboxylate exhi bits the behaviour of alkylic salts of normal ketonic acids, and the authors have found that the ethylic salts of mono- and di-methylacetonedi- carboxylic acids, and of mono- and di-ethylacetoriedicarboxglic acids Ketones. By PAVEL I W . PETRESKO-KRI'L'SCHENKO, L. PISSSRSCHEWSKY,ORGANIC CHEIIISTRY. 135 aye also vigoi*onsly atkacked by phosphorons pentachloride.This :tgent acts 011 ctliylic lrimetlhylacetonedicarboxylate, whilst ethylic triethylacetonedicarboxjlate is indifferent towards it, this difference in behaviour being due to the respective masses of the substituents. Ethylic fetraiiaethlllacetoi~edicarbozylnte boils a t 116-152', under a pressure of %5 mm. ; it is indifFerent towards phosphorus pentachloride, which has no action 011 ethylic tetreth;-lacetonedicarboxylate. Whilst the behaviour of ethylic acetoacetate towards phosphorus pentachloride is normal, derivatives containing one or two alkylic substituents nndergo chlorination. Influence of Substitution on the Course of the Reactions of Ketones. By PAWL Iw. PETKENKO-~RI'~SLHESKO and S. EPHF~USSI (Aiznalen, 1895, 289, 5&--61 ; compare the foregoing abstract).- Generation of licat marks the combination of phenylhydraziue with ethylic moiiomethylacetonedicarboxylate and ethjlic monet hylace- tonedicarboxylate, action being less energetic in the case of the latter salt.The hydrazone of ethylic monomethylacetonedicarbox~~ate crjstnllises from dilute alcohol in lustrous plates, and melts at 129-130' ; when hydrolysed with caustic soda, i t yields the hydra3ojie of the acid, which melts and evolves carbonic anhydride a t 168-169c, 31. 0. F. yielding n pyrazolone derivative. $1. 0. F. Action of Carbon Tetrachloride on Methylic Sodiomalo- nate., By NICOLA~ D. ZKLINSKT and A. PORCHGNOW (Eer., 1895, 28, 29 4&-2947).--\Y hen carbon tetrachloyide acts on niethylic sodic- malonate, CflN,z(C!0031e)z, in the presence of sodium met.hoxide, a substance is formed which melts a t 136-137O.It appears to have the composition OH*C [CH( COOMe)2]3. C. 3'. B. Dihydroxytrimethylglutaric acid. By NICOLAI I). ZELINSKI arid L. TSCHCGAEW (Ber., 1893, 28, 2940--2942).-Methyl acetyl- acetone, CHMe(CRIeO)2 (Dunstan and Dymond, Trans., 1891,428), was converted by means of hydrocyanic acid into a witrile, which yielded dilqtlroxgt riinethylglzttal-ic acid, CH Me[ CiMe (OH) *COOH]?, when hydrolyoed with hydrochloric acid in the cold. The nitrilc melts at 124-125'. The acid melts atl 83-86', and easily loses 1 mol. of water, forming a lactonic acid, which melts at 119-120' ; when distilled under atmospheric pressure, it yields a solid dilactone. It is remarkable that the lactonic acid very readily unites with water, re-forming t lie dihydi*osy- acid.C. F. B. Isopropylglutolactonic acid ; Constitution of Tarpenylic acid. By RuDoLrH FITTIG and ADOLE. WOLFF (Annulen, 1895, 288, 176-191) .-The authors' investigation having shown that isopropyl- glutolactonic acid, CHXc2*C(COOH) <o "CO, bears no re- CH *CH semblance to terpeiiylic acid, the constitution of the latter substance is probably 1-epresented by &he formnla I >CH-CH,.COOH, an O*CMe, CO*CH213G ABSTRACTS OF CHEMICAL PAPERS. expression which was first advocated by Wallach, and has been recently supported by Schi yver. pel- Dibro?nisoheptoic ncitl, CHM%*C HB r*CH BrCH,-C OOH, is ob- taiiied by adding bromine to n solution of f-3y-isoheptenic acid in carbon bisulphide, the operation being carried on in diEused daylight a t 0' i n absence of moistme ; it melts a t 102-103", and crgstallises in transparent, colourless plates belonging to the monosymmetric system, a : b : c = 0.732 : 1 : 0.641 ; /3 = 67' 15'.When heated during 21 hours with water in a reflux apparatus, the acid is con- verted into isoheptenolactorie and hydroxyisoheptolactonc (Abstr., 1895, i, 207), 6-dimeth3-llevalinic acid being formed a t the sanie time (Eoc. cit.) ; the cnlcirm salt of this acid contains 3$H,O, and the silver salt is indifferent towards light. IsopropylgliLtolactanic acid is obtained by sdding a Concentrated solution of 6-dimetli3.llerulinic acid to finely powdered potassium cyanide, allowing the mixture to remain a t the ordinary temperature during 24 hours, and adding concentrated hydrochloric acid while the liquid is kept cool with ice ; it melts a t 67-68".The acid sepa- rates from a mixture of ether and petroleum i n small, monosFm- metric crystals ; it is very soluble in water, bat does not crystallise from the aqueous solution. The barium salt contains 2H20, and crystallises in monosymmetric prisms ; the calcium salt contains 2&H,O, and the silver salt is indifferent towards light and heat. The amide is an intermediate product formed in hydrolgsing the cyan- hydrin with hydrochloric acid ; it crystallises from water in lustrous, transpment prisms belonging to the monosymmetric system; a : 2, : c = 0.i771: 1 : 0.76382 ; /3 = 54" 34'. When isopropylglutolactonic acid is heated with aqueous alkalis, salts of isopropylhjdroxjglutaric acid are produced.The barium salt is anhydrous ; the cnlcizim salt contains 3H,O, and the silver salt Aconitic acid from Adonis vernalis. BJ- N. ORLOE'F (Chern. Cent,.., 1895, i, 202; from Phnrm. Zeit. IJuss., 33, 771).-Adonis %el*- nalis gives better yields than either Aconitim or l3;Ipicisstuur. After sweral drops of concentrated lead acetate solutiou have been added to the aqueous extract, and tlie precipitate formed has been removed, excess of the reagent is added, and the precipitate collected, well washed, and decomposed bj- dilute sulphuric acid. The filtrate is conceutiated, and extracted with ether; after evaporation of the ether, the aqueous solution of aconitic acid is decolorised by means of animal charcoal. J.J. S. . is amorphous. 31. 0. E'. Formation of Citric acid by the Oxidation of Cane Sugar. By EDKIN F. Hicss (Chem. News, 1895, 72, 165--166).--Phipson dissolved a few grams of cane sugar in water, to which a few drops of sulphuric acid had been added, and poured in a rather strong solution of potassium permanganate ; in a short timc, a t summer tem- perature, the solution became clear and colourless. When t h i s was ncutralised with ammonia a i d calcium chloride added? there was no precipitate in the cold, but, 011 licnting, ci.ystal1inc calcium citrateORGANIC CHEMISTRY. 137 separated ; with large quantities of permangaiiate, oxalic acid was also produced. The author of the present note has repeated and also varied t h e experiment, using acid aboi-e and below 1 per cent.; with the former a precipitate is obtained both in cold and hot solution, b u t with the latter, only in the hot solution, the precipitate in all cases being cal- cium sulDhate without R trace of orzanic acid. When nitric acid was I " used instead of aulpliuric acid, no precipitate mas obtained. D. A. L. Citric and Tartaric acids from Cane Sugar. By THOJIA~ 11. PHIPSON (Chein. Ne7us, 1895, 72, 190-191 and 257).-The failure of others to obtain citric acid from cane sugar (compare preceding abstract) is attributed by the author to the use of insufficient perman- ganate, of which a quantity not less than the weigli t of the sugar should be used ; temperature and thc character of the acid used are also stated to play an important part.Noreover, he finds that when a solution of equal weights or" sugar, nitric acid, and potassium permanganate, after being left for 24 hours in the cold, is neizti.aliscc1 with calcium carbo- nate, a copious precipitate containing cdciuni tartrate is obtained, and the clear solution, on boiling, yields a further precipitate, which is calcium citrate. Saccharic acid and formic acid have also been obtained in these reactions by the acthor. Citric acid from Cane Sugar. By ALFRED B. SEARLK and ARWLD R. TANKARD (Cltem. &-ezus, 189.5, 72, 235, 268).-Hicks' (see above) results confirm previous work of the authors, who have since endeavoured to obtain citric acid in accordance with the method set, forth by Phipson (preceding abstract), using equal weights of cane sugar, nitric acid (sp.gr. 1-42>, and permanganate, the latter being added in strong solution. They did not obtain citric acid, but when sulphuric acid was used instead of the nitric acid, calcium sul- phate was obtained as in their previous experiments. Hydrazides of Substituted Amido-acids ; Fumaryl hydrazide. By RUDOLF RADEKHAVSEN ( J . y r . Chem., 1895, [2], 52, 433-454).- The method adopted for the preparation of ethylic salts of substi- tuted amido-acids containing an acid radicle consists in warming ethylic amidoacetate hydrochloride with an acid anhydride and anhydrous sodium carbonate, the change occurring in the sense of the equation 2NHz*CHf,*C'OOEt,HC1 + (R*CO),O + NaCO, = ZR-CO-NH-CH,*COOEt + 2NaCl+ 2H20 + CO,. An acidic chloride may be substituted for the anhydride, but if the sodium carbonate is omitted, the yield is very small.In this way, ethylic hippurate, ethylic acetylamidoacetate, ethylic succinylamidoacetate, and etliylic ph t halylamidoacetate have been prepared, and details of the necessary opwations are given. E thylic succiny laniidoacetate was prepared by Haller and Arth, who named it ethylic succinirnidoacetate (Abstr.. 1887, C,H,*y:N.CHz*COOEt 1031); the author ascribes to i t the formula I GO-0 and a similar constitution to ethylic phtlinlyl~midoacetate. I). A. L. D. A. I,. >a 3s ABSTRACTS OF CHEMICAL PAPERS. .4cetcL,12irloncetol~!/~l~~~;de, NHAc*CH,*CO*NH*NH,, is prepared by 111 i x iiig t lie calculated qusn ti ties of e thy1 ic ace t,amidoace tate and ihydrazine hydrate, dcohol and water being eliminat’ed ; i t forms long, prismatic crystals, melts a t 1 1 5 O , and dissolves fairly easily in alcohol and water, but not in ether.During its preparation some diacet- .u ~nidoncetoh ydrazide, (NHAc*CH,-CO),N,H,, is formed, and remains undissolved by alcohol ; this compound is a white, crystalline powder, which is somewhat ~oluble in water, and melts and decomposes a t 250’. n e w yl ideneacetamidoacetoh ydrazide, NHAc*CH,*C 0-NH*N :CHPh, from acetarnidoacetohydrazide and benzaldehyde, crystallises in lustrous lamina, melts a t 1 9 8 O , and dissolves in alcohol. With nitrous acid, acetsrnidoacetohydrazide yields a mhi te compound, which probably consists in part of the corresponding azide, but readily breaks up, with elimination of nitrogen and the fornzation of a com- yound which is regarded as acetamidoncet~lcccrba~~il, NHAc-C H,*N:CO ; the investigation of this compound is not yet completed.The react ion bet ween e t h ylic succinam idoacetnte and hyd raziii e hydrate does not yield the corresponding hjdrazide, but a coi)ipo1m7, C8H1,N60,, which fbrms colourless crystals and dissolves freely in water, but only sparingly in alcohol ; it forms a white condeiisation product with benzaldehgde, and may therefore be supposed to contain the group (N*NH,)” or (NH*NH,)’. Ethylic phthalylamidoacetate yields phthalylhydrazide (Absti-., 1895, i, 354) when treated with hjdrazine hydrate. Ethylic p henylamidoacetate and hydiazine hydrate yield phenyl- amidoacetohydrazide, NHPh*CH2*CO*NH*NH2, which crystallisee in large, tmnsparent tables, melts at 126*5’, and dissolves freely in warm alcohol and water, but only sparingly in ether; it reduces Fehling’s solution.Benzylidemphenylamidoacetohydrazide, NHPh*CH,*CO*NH*N:CHPb, erystallises in white needles and melts at 176’. IsopropyZideuepheql- nmidoacetohydl.azide, NHPh*CH,*CO*NH*N:CMe, crystallises in white needles and melts at 183’. Nit rosopheny lamidoacet y lazoi m ide, NO-NP h* C Hz* C 0 *NS, is formed, together with nitrosodiphenylamine, when phenylamidoacetohydr- azide (1 mol.) is treated in the cold with sodium nitrite (2 mols.) and glacial acetic acid ; it crystallises in slender, yellow needles, melts at 41-42’, and dissolves in cold alcohol, ether, benzene, and acetone, but not in water. Fzcmary llydruzide, C2H, (C O*NH*NH,),, is prepared from dimethyl ic fumarate and hydrazine hydrate ; it crystallises in lustrous, colour- less laminae, becomes yellow at 200°, melts and decomposes at 2203, and dissolves somewhat freely in hot water, very sparingly in alcohol, and not a t all in ether.Isop~op y I idenrjkma r -y lh ydrazitle, C,H, ( C 0 *N H*N:CMe2) ,, forms white crjstals and melts at 220’ ; when treated with benzaldehyde, i t yieldsORQXSIG CEEMISTRY. 139 the corresponding beiazylidene derirative, C,H,(CO*NH*K:CHPh),, which crystallises in white lamina and decomposes at about 280". Fumnrylazoinzide, C2H2(C0*N3),, has been prepared in the usual manner as a colourless, crystalline compound, but it explodes when dried. By heating it with absolute dcohol, nitrogen is eliminated, and ethylic fuma?ylcarbamate, C2H,(NH*COOEt)2, is obtained ; this forms small, yellow needles, which bcconie dark when heated, and melt and decompose at 220" ; it is a neutral compound, and dissolves freely in water, alcohol, ether, acids, and alkalis.(Ber., 1895, 28, 2766--2773).-The author replies to Le Bel's criti- cisms (Absti.., 1895, i, 585) on his previous work (Abstr., 1895, i, 450). On treating Meti's d-isopropyl phenylglycol lic acid with phos- phorii s peii tachloride, inactive ch lorisopro py 1 phenylace tic acid, me1 t- ing at 82', was obtained, but by operating more carefully with I-isopropylphenylg1ycollic acid, a cEextrochlorisopropylp~eti?flacetic acid, melting at 75-76", and having the specific rotation [ x ] D = +23.33 in a 3 per cent.benzene solution, was isolated ; evidently the active glycollic acid very readily becomes racemic when the hydroxyl group is exchanged for chlorine. On brominatiiig aspaixgine by passing nitric oxide through its dilute sulphuric acid solution containing potassium bromide and bromine, lcevo b romosuccinamic acid, N H,.C 0.C H2* C K B r.C 0 OH, is readily obtained ; it forms large crystals melting at 146'. and has the specific rotation [a]D = -67.12', -67*57', and -44.3' iu alcohol, ethylic acetate, and 20 per cent. sulphuric acid solutions respectively. When further treated with bromine and nitric oxide in acid or alkali solution, i t yields Zceecobromosuccinic acid, which crystnllises in striated prisms melting and decomposing at 173', and has the specific rota- tions of [aID = -72.6' to - 72.7' and -67.92" in ethylic acetate and alcohol respectively ; it is less soluble in the ordinary reagents than its known racemic isomeride.The mefhylic salt boils at 130" under 22 mm. pressure, and has the rotation [aID = -46' in a 50-mm. tube ; the dextro-isomeride boils at 126' under 18 mm., and has the rotation [a]D = +48*3' in a 50-mm. tube ; the discrepancies are due to the readiness with which these compounds change into inactive methylic fumarate on distillation, The author has repeated and confirmed Piria's and Pasteur's statements respecting the convcmion of aspnra- gine and aspartic acid into l~vomalic acid, and Tilden and Mar- shall's observation (Trans., 1895, 494) that asparagine yields lavo- chlorosuccinic acid when treated with nitrosyl chloride.Lawoasparagine can therefore be converted into laevobromo- or chloro-succinic acid, and also (Abstr., 1893, i, 25U) into the dextro- rotatory isomerides of these compounds ; the somewhat remarkable result is thus obtained, that by treating an optically active substance containing only one asymmetric carbon atom with inactive reagents at relatively low temperatures, either optical isomeride of the sub- A. G. B. Optically Active Halogen Compounds. By PAur, WALDEN stance formed may be obtained a t will. w. J. P.140 ABSTRACTS OF CHEMICAL PAPERS. Thiosinamine (Allylthiocarbamide) and its Halogen Additive Products. By J. GADAMF:~~ (A).cR. €'harm., 1895, 233, 646-684) .- A substance, C4H8N2S,2ApNOs, iiiay be obtained by adding excess of a, 10 per cent.solution of silver nitrate to a dilute aqueoiis or alcoholic solution of allylthiocarbamide, acidified with a drop of nitric acid, and is deposited, after a short time, in the form of grey, matted needles. It was obtained in an impure state by Falke (Diss., 1893). When dissolved in water, it decomposes, and the solution subsequently deposits a new c O m p ? d , C4HsN2S,AgNO3, which ciystallises from water in long, silky needles. Picric acid displaces one molecnlnr pro- portion of nitric acid from these compounds, the szibstances formed having the compositions C4H7N2SAg,CGK3N307,AgNO3, and CiH7..IN2SAg,C&W&& respectively ; they are amorphous, but the former becomes crystalline spontaneously. A cornpoz6nd, CaH8N2S,HgC12, is obtained by the action of mercurous cbloride on an aqueous solution of allylthiocarbamide, or bey the action of allylthiocarbamide on the compound C4H8N,S,'LHgC1,.It crjstallises in large prisms, which hare the remarkable property of being half transparent, half opaque. The interaction of allylthiocarbamide and mercliric cyanide yields the compounds 5C4HsN28,Hg(CN)2, forming large, shining crystals resembling those of mercuric cyanide, and 2C4H8N2S,Hg( CN),, which is obtained as grey, microcr.ystalliiie aggregates. Cuprous chloride yields the compounds C4HaN,S,CuCI, first obtained by F a k e (Zoc. cit.), and (CAHaNYS)3,C~2C12, which forms small, shining cry st als. When allylthiocarbamide is triturated with mercury, it yields mer- curic sulphide and a new compound, which is a yellowish mass, soluble in alcohol, and melting a t 79-80".With allylthiocarbamide, copper and silver yield compounds of unknown constitution. M~lhylall~lthiocai.bamide dibromide, CBHION2SBr2, is formed on mixing alcoholic solutions of methylailylthiocarbamide and bromine. It forms large, white crystals, very soluble in water, and melts a t 145-146" ; the picrats melts a t 181-182". The chlorobromide, C,H,N,SBrCI, obtained from the dibromide by the action of silver chloride, is readily soluble in water, and melts a t 120-123". The ;iEatiiaocltZoride is obtained as large, yellow, nodular aggregates ; the uiwochloritle is crystailine, me1 ts at 80", and dissolves sparingly in water. DinzethyluZZyZt1,iocarbumide is obtained on mixing alcoholic allyl- thiocarbimide and dimethylamine i n molecular proportion ; it is a liquid, crystallising only a t the temperature produced by a mixture of solid carbonic anhydride and ether.The dib?-ontide, which crystallises i n large, white needles, melting a t 207~S--208°, is very soluble in water, dissolving less readily in alcohol ; tbe chlowbrornide forms large, transparent, colourless crystals, and melts at 191-192". The ,tzcrochlo?-ide is deposited as a red oil, which gradually becomes crys- talline ; i k melts at 70". The platinochloride is more readily soluble, and crystallisea in shining, yellow needles.ORGANIC CEEMISTRT. 141 ,-IlIylthiocarbamide combines with trimethylamine at a temperature of 150-1 GO", forming a n oily liquid. Trinaet h yldlylthiocarha 111 icle dibromide is an indistinctly crystalline mass, which is insoluble in alcohol, and yields a, pale yellow platinocl/loride.Dimetb~lallylthioca~bamide unites with silver nitrate, and with cupi*ous chloiide. The silver cowpowad, C6H.:12NzS,Ag~03, crystallises in needles, and yields a well crystallised picrate. The copper compozind, C6H12N2S,CuCI, was obtained i n small, brownish crystals. Both com- pounds yield metallic sulphides when heated with aqueous ammonia, On mixing alcoholic solutions of dimethjlallylthiocarbamide and mercuric chloride, a voluminous precipitate is produced. When triturated with mercury in presence of alcohol, dimethylallyl- thiocarbamide is attacked, and a stable mercury cowpound is formed, together with mercuric sulphide. T tie author regards it a s highly probable that dimethylallylthiocarb- amide has the constitution NMez*C(SH):N*C,Hj.A. L. Thio-Compounds of the Uric acid Group. By EMIL FISCHER and LORENZ ACH (Annnlen, 1895, 288, I j7--176).--Thiouranzil, prepared in the following manner. Potash is added to uric acid (60 grams), snspended in warm water (2,400 c.c.) until a cleai- solution is obtained ; this is diluted with water (1,400 c.c.), treated with a freshly prepared solution of animo- nium sulphide (1,000 c.c.), and heated for 5-6 hours at 155-160". Ttie clear liquid thus obtained, on cooling, deposits the ammonium derivative of thiouramil, and a further quantity of the product is nbtained by removing ammonia and amnionium snlphide, and rapidly evaporating the solution, which is then acidified with glacial acetic acid.Thiouramil dissolves in 500-600 parts of boiling water, and separates in minute leaflets or prisms as the liquid cools ; it is readily soluble i n concentrated sulphuric acid, and is precipitated on diluting the liquid with water. Solations in cold alkalis rapidly become red when exposed to the air. Cold concentrated nitric acid and the warm dilute acid act on thiouramil, giving rise to sulphuric acid and alloxan ; thiouramil gives the murexide reaction, which can also be obtained by the use of chlorine water as the oxidising agent. A fir splinter is at once stained orange when immersed in a neutral or acid solution of thioummil. Chlorides of the heavy metals yield a white precipitate with an aqueous solution of thionramil ; silver nitrate gives rise to a gelatinous precipitate, which becomes black when heated, or on treat- ment w i t h ammonia.The potassium derivative crystallives in yellowish needles or prisms containing 1H20, which is lost a t 130" ; the s o d i ~ n ~ derivative also forms yellow needles containing 1H,O, which is lost at 1 0 5 O . The ammonium derivative crystallises in lustrous, golden- yellow leaflets, dissolving with difficulty in cold water arid ammonium sulphide. When heated with hydrochloric acid for four hours at 150°, thiouramil is converted into a mixture of ammonium chloride and glycocine hydrochloride. M e t k yZthiouramiZ, C5N3H7SO2, is ob- tained by agitating methylic iodide with a solution of the potassium derivative in water ; it crystallises from hot water in stellar aggre-142 ABSTHACTS OF OHEMICAL PAPERS.gates of needles, and darkens at 230' when rapidly heated, nielting and decomposing at 252-253' (uncorr.). The neutral solution does not stain fir-wood, but colour is developed in the fibre on adding hydrochloric acid ; it gives the murexide reaction when oxidised wit11 chlorine water. The methyl derivative dissolves readily in hot mineral acids, and also in cold alkalis and alkali Carbonates ; on adding alcohol to the solution in caustic soda, the sodiiim derivative separates in minute, slender needles. Nitric acid oxidises the methyl derira- tive yielding alloxan, and when the substance is heated with hydro- chloric acid for four hours at I 50°, carbonic anhydride, ammonia, and me th jlic mercap t an are produced.Ethenylfhioum?niZ, CsN3H5S02, is obtained by heating the ammonium derivative in a reflux apparatus with acetic anhydride ; it dissolves in 210-220 parts of boiling water, from which it separates in needles, melting, when rapidly heated, a t 220-221O (uncorr. j. The substance dissolves in hot glacial acetic acid, concentrated mineral acids, and hot dilute alkalis, the codiam derivative being precipitated in slender needles on adding alcohol t o the solution in caustic soda; silver nityate forms a gelatinous pre- cipitate when treated with the solution in ammonia, and this con- sists of the silrer derivative, which crystaliises from hot animonia in minute, slender prisms. The ethenyl derivative gives the murexide reaction. Arzirilic acid, C4H,N,03, is obtained by treating an a1 k a h e solution of uric acid 1vit.h a large excess of ammonium sulphide which has been kept for many months; a mixture of compounds is formed, and after treating this product with dilute nitric acid at 50-60°, azurilic acid is separated i r i the form of its silver derivative.If rapidly heated, the substamce becomes colouixd a t 245O, and decom- poses a t 275", when the odour of hydrogeu cyanide becomes percep- tible. It dissolves in 55 parts of hot water, from which i t crystallises on cooling, and is also soluble in alcohol. It is readily soluhle in alkalis and alkali carbonates, the solution in caustic soda yielding the sodium derivative on adding alcohol; it gives the innrexide reaction. tained by boiling an aqueous solution of potassium cyanate with thio- iiramil ; it crystnllises in prisms, and contains 1H20, which is lost at, 130'.The acid is solnbie in hot water, but dissolves with difficulty in boiling alcohol ; alkalis and alkali carbonates dissolve it readily, and when silver Eitrate is added to the solution in ammonia, a colour- ICSP, gelatinoils precipitate. is formed, becoming black when heated. Staining of fir-wood is only effected after prolonged boiling, b u t the murexide reaction is easily produced. OxaZyZdithioicramiZ, C202(C4H*N,S02)2, is obtained by adding the foregoing acid to fused oxalic acid, and heating the clear liquid until the oxalic acid is removed ; i t is a crystalline powder, dissolving in 400 Darts of hot water, and is slowly converted into oxalic acid and thio;~nmil undcr the iukuence of ho< concentrated alkalis.p-Met hy 1 t 1iiopseudoul.ic acid, C 0 <NH N H . c ( S ~ ~ ~ ~ o ~ isORGANIC CHEXISTRY. 143 produced when the methyl derivative of thiouramil is heated on the water bath with an aqueous solution of potassium cjanate ; it crjs- tallises from hot water in colourless needles, and when rapidly heated darkens at 290°, and decomposes at 350". The acid is soluble in 400 parts of hot water, but dissolves with great difficulty in alcohol ; in alkalis, it is readily soluble, the metdlic derivatives being decom- posed by glacial acetic acid, and therefore differing from those of p-thiopseudonric acid, which are indifferent towards this agent. The acid gives the murexide reaction ; the siZz:es. derivative is soluble in ammonia, and the potassizcm derivative crystallises in pale yellow needles, becoming darker 011 exposure to air.TlLiodinaethyl.lcrnIlzil, CO <NMc N"e*c(SH)>C*NH2, Co is obtained by heating dimethyluric acid, dissolved in ammonia, with fi+eshly prepared ammonium sulphide for two hours a t 155-140" ; when rapidly heated, it begins to undergo change above 200', and is completely decomposed about 300'. It dissolves in 70 parts of hot water, and crystal- lises in colourless needles, which become green in the a h ; it is readily soluble in hot alcohol, and crystallises in slender prisms. It dissolves readily in alkalis and alkali carbonates, and in other respects resembles thiouramil. 11. 0. F. Hydrazides and Azides (Azoimides) of Carbonic acid.By THEODOR Cunrrrns and KARL &IDEXREICH (J. p7.. Chent., 1895 [2], 52, 454-489 ; compare Abstr., 1894, i, 166) .-Semicarbazide hydro- chloride melts a t 175' (Abstr., 1894, i, 165). Carbamic azoimide (cxrbaminazoimide, Abstr., 1895, i, 252) melts a t 97'. Ca~bohydmtide, previously called carbazide (Absti.., 1894, i, 166), melts at 152"; its hydroclLZode, CO(NH*NH2),,2HC1, melts a t 21OQ, and its sdphate mclts and decomposes at 218'. A tliacetyE de~izwfirh was prepared. Carbazoimide has already been described as carbonyl nitride (Abstr., 1895, i, 12) ; attention is called to the analogy of it's reactioiis t o those of carbonjl chloride. 'the silver derivcttive of methenj Icarbo- hydrazide, C2H3N40Ag, is a white powder, stable in light. BIethylic azoimidoca~bo~zate, N3.CU2*Me, is prepared by treating am- monium azoimide with methylic chlorocarbonate in ethereal solution.I t is a coloui.le~s liquid, and boils a t 102', but is liable to explode a t this temperature. The hydrazine salt of dicarbsmide (Zoc. cit.) melts a t 197"; the silrer salt,, C2H3N402Ag, is a white powder stable in light. Hydyazitre thiocyanate, N2H5SCN, is prepared by decomposing hydrazine sulphate mith barium thiocyanate ; it crystallises in tablets, melts a t 80°, and dissolves freely in water and alcohol. When heated in a sealed tube at 100" for 4-5 hours, it yields hydrazidothio- ccwbonarnide, NH,*CS*NH-NH-CS*NH,, which crystallises from hot water in long, colourless prisms, and melts at 214--215c ; one pal t dissolves in 418.5 parts of water a t 83'.The remainder of the compounds described in this paper hare already received notice in the pIaces quoted. A. G. B.144 ABSTRACTS OF CEEMICAL PAPERS. A Derivative of Furfuraldehyde irom Laevulose. By JOSEPH KIERMIAYER (Chenz. Zeif., 1&9Fi, 19, 1003-1005 ; compare Dull, this 1-01., i, 121).-The product obtained by Dull, by the action of osalic acid on laevulose is shown by the author to be a derivative o€ furfur- aldehyde. It is most readily prepared from cane sugar, as the glucose produced by inversion is not acted on. A 30 per cent. aqueous solution of cane sugar is heated with 0.3 per cent. oxalic acid fol- 3 hours mder a pressure of three atmospberes ; the mixture is neu- tralised with calcium carbonate, treated with basic lead acetate, anti then extracted with ether or ethylic acetate.The aldehyde forms a colourless syrup, which rapidly turns yellow on exposure to the air. It is readily soluble in water, alcohol, and ethylic acetate, more spaiingly in ether. It begins to boil aiid froth at B O O , but even when the temperature has reached 200' only a slight distillate is obtained, and this consists of furfuraldehyde ; on further heating, however, it is completely decomposed, and cannot be distilled even under di- minished pressure. I t s alcoholic solution gives a deep scarlet colora- tion with thymol and sulphuric acid, and a deep red with phloro- glucinol. Both are extremely delicate reactions. It acts as a strong reducing agent towards ammoniacal silver nitrate and Fehling's solution. The author considers it is probably P-hydr.ory-6-methyl- furfzualclehyde, OH*CaOHMe*COH. Thepl~en!jlh ydrazoite forms golden- yellow crystals and melts at 138', the anti-abdoxinze melts a t 77-78", and i f allowed to remain for some time in alkaline solution is con- verted into the syn-aldoxime, which melts at 10F. The syn-aldoxime is converted back again into the anti-compound when heated for 30 mins.at 115-120'. The author shows that a similar treatment converts furf ur-syn-aldoxime into furfur-anti-aldoxime. When the aldehyde is oxidised by ammonincal silver nitrate, i t yields P-hydrox!l-~-~tethybpyromiicic acid, OH*C40HhIe*COOH ; this is readily soluble in water, sparingly in ether, melts at 148O, and a t the same time undergoes decomposition. I t s solution is coloured yellow by ferric chloride.The silver salt crystallises with lH,O in colourless prisms, it is sparingly soluble in water, and readily blackens on exposure to light. The coppel. and calcium salts are also described. The benzoyb deriwfice, CsH503*COPh, crystallises in long needles, melts at 5 5 O and is readily soluble in etbylic acetate, benzene, and alcohol. When the aldehyde is heated with oxalic acid and water under a presslire of three atmospheres, it is converted into levulinic acid. Reasons for considering the aldehyde as a p-hydroxy-compound are given. When the pure aldehyde is allowed to remain over snlphuric acid, in the course of it few days i t loses water and forms methylfiL~ji6r- aldehyde oxide, O( C,0HMe.COH)2 ; this oxide is also obtained by the distillation of the aldehyde.It crpt,allises in long feathery needles, melts at 112", is sparingly soluble in hot water and in ether, and insoluble in benzene and acetic acid. The aqueous solution readily reduces aminoniacal silver nitrate and Fehling's solution, and gives colorations with phenols. The auilids, (C,H,O:NPh),O, forms colourless plaies and melts a t 124", the pheny Zhydrazone,ORQANIC CHEJIISTRY. 145 (C,H,O:N*NHIPh),O, mt:lt,s a t 139O, and the .yn-aZdoz:im a t 167-168'. 'rhis oxime is soluble in ethylic acetate aiid acetone, only spni-ingly i l l chloroform, ether, and benzene, a i d niore readily in hot dilute alcohol than iii concentrated. Soi*binose, when heated with aqueous oxalic acid, also yields the same methylhydroxyfiu~furaldebyde. Dextrose, on the other hand, is not acted on by n 0.5 per cent.solutioii of oxalic acid, lactose be- 11 aves siinil aibly . J. J. S. Synthesis of /3-Methylpentamethylenecarboxylic acids. By WILH ELM EULER (Ber., 1895, 2952--2959).-Pyrotartaric nitrile, CN*CHNe*CH,-CN (Claw, AnmEen, 191, 33), is obtained by heat- ing ally lie iodide with potassinm cyanide in alcoholic solution and fractionating the product; it boils a t 240-260", or at 130-140° iiiider 20 mm. pressui'e, but the yield of it is only 5 per cent. of the wcight of the allylic iodide, the chief product of the reaction being /j-ethoxybutyronitrile. By reducing it with sodium in alcoholic solution it is converted into the (liarnine (Oldach, Abstv., 1887, 7:3.?), the dihydrochlori~lr of which melts a t 144-145".IVhen this salt is deconiposecl, in ice-cold solution, with the equivalent quantity of silver nitritcb, and the filtered solution slowly distilled unti 1 the temperatiire ibeaches 140", /j-nzd hyltct minetliyleiie glycol, OH.CH,*CH~le*CH2*CH~.0H is obtained, together with an oil boiling between 70" and 1:W" ; the latter is probably a mixture of the unsatura- ted alcohols, OH*CH,*C HMe*CH:CH, and CH2:Ci\le*CH,*CH2*OH, as it foi-ms a t Z i b r v , ) z o - a ~ t Z i f i ~ ~ ~ ( ~ ) i i p o ~ ~ ~ i d , and also a wzoi~ncefat~ boiling a t 120-130" ; R hydrocarbon, CH2:CJIe*CH:CH2, is probably formed in adclition. Thc glycol boils a t 11.5-1:30" undei. 20 mm. pressure ; \v]len it is saturated with Iiyclrogen homide at 0' and then heated at 110", i t yields p-l)zetlllllteti.anzethylPlLe dilronzitle.If this is heated \vith ethylic disodionialonrtte in alcoholic solution, and the fraction of the nroduct, that boils above 1:35" under 1s wni. nressure is Iiydroly$ed with 10 per cent. aqueous alcoholic potash, /3-?thLylpmt,c- i t i c t h l l l e i l l ~ d i c o r . ~ o x ~ ~ ~ c acid, I >C(COOH),, is obtained. CHZ-CH, CH31e-CH2 'l'his melts at 140-142", and then loses cai*bonic anhj-tlride, the 7 1 2 0 1 ~ 0 - crirboxy2ic acid finally distilling over a t about 220". Of the Iattcr only it few drops were obtained, although 8 kilos. of allylic iodide were worked up ; its caZc*i?tm salt, with 5H20, and the s;larr salf wei'e, howcver, prepaved and nnalysed. C. F. R. New treatment of the Benzene Problem: Derivatives of Thymotic acid.By GEORG HEYL and VICTOR MEYEI: (Be?.., 1895,28, 2776-2798).-1n order to obtain soine insight into the constitution of the benzoic acids, aud, therefore, of the aromatic compounds, the etheri- tication of certain fatty acids has been studied on the same lines as t,hat of the substituted benzoic acids. Acids such as aconitic acid, VOI,. LXX. i . 112 COO H-CH,*C( COOH):CII.COOH,146 ABSTRACTS OF OHEMICAL PAPERS. and tricarballylic acid, COOH*CH,*CH(COOH)*CH~*COOH, readily yield tri-ethereal salts when treated with alcohol and hydrogen chloride a t Go, whilst the corresponding aromatic acid, heiniinelli tic acid, does not yield a tri-salt under these circumstances. This shows that the reaction characteristic of aromatic acids does not hold with others containing the same groups, since the three carboxyl gi-oups of their acids are adjacent.The aromatic acids may be supposed to contain either the group COOH*C<c or CO0H.C-C, according to the benzene formula which is accepted. The authors, therefore, next studied the etherifi- cation of certain fatty acids which also contain these groups. Tri- phenylacrylic acid, COOH*C<~~i’2, contains the first whilst the second is present in triphenylacetic acid, COOH-CPhs. The essential point is, that the group C0OH.C is connected with tertiary carbon atoms; the phenyl group is chosen simply because the carbon atom which is directly cornbined with the group COOH*C is a tertiary one. Neither of these acids is completely etherified by dcoholic hydrogen chloride in the cold, triphenylacrylic acid yielding 22.3 per cent., and triphenylacetic acid only 3.45 per cent.of ethereal salt. When treated with hjdrogen chloride in boiliug alcoholic solu- tion, the triphenylacrylic acid gives 97 per cent. of ethereal salt, whilst triphenglacetic acid only gives 22.3 per cent. ; the behaviour of triphenylacetic acid is therefore precisely analogous to that of a diorthosubstituted benzoic acid. It follows that substances which contain the group COOHC-C behave, in this respect, as aromatic substances, whilst those which. contain the group COOH*C<c do not. - Triphenylacrylic acid may be prepared from benzophenone chlo- ride and benzylic cyanide, as already described (Abstr., 1895, i, 542), or by heating benzophenone chloride with niethylic phenyl- acetat,e.I n this case, it is accompanied by n small amount of d@henylindone, which forms dark orange-red crystals, and melts a t 150-151’. Triphenylpropionic acid is readily etherified by boiling alcoholic hydrogen chloride, LO that the characteristic behaviour of triphenylscetic acid is not merely due to the presence of three phenyl groups. The authora have also endeavonred t o resolve nitrotliymotic acid, N02*CsHMePr(OH)*C‘OOH, and formjlthymotic acid, C H O-C6HMePr ( OH) C 00 H, which contain six different groups, into optically active constituents, but without success. Similar experiments with metahydroxybenzoic acid also gave a negative result. Nztrothymotic acid is obtained by the direct nitration of thymotic acid, and crptallises in yellowish plates, melting a t 173-175O.C /c ‘C / c ‘C CORGANIC CHEMISTRY. 147 E'o?.i)zyZth?~lllizotic acid is prepared by heating thymotic acid with chloroform and aqueous soda. It melts a t 180-1853. A. H. The Benzene Problem. By JULIUS W. BKCHI. (Ber., 1895, 28, 2981-298G).-The authoi. thinlis that no definite conclusions respect- i n g the stiwcture OF the benzene ring can be drawn from the work of Hey1 and V. Meyer (preceding abstract). By means of figures, it is shown, that from stereoclit.mical considerations triphenylacetic acid would probably be difficult to etherify. J. S. Action of Nascent Bromine on Benzene Derivatives. By WILHELJI VAGBEL (J. p r . Chmz., 1895, [2], 52, 417-423; compare Abstr., 1891, i, 94, 453).-Arnido- and hydroxy-derivatives, be they primary, alkylised or acetyliscd, when united directly to the nucleus, possess, beyond all other substituents, the property of facilitating the entrance of bromine in place of nucleal hydrogen.The bromine always takes the ortho- and para-positions with regard to tht? NHz- and OH-groups. None of the usual substituents-such as CH3, KOz, halogen, SO,H, COOH, N:NR, N:NCl-prevents the entrauce of bromine, should the substituent itself occupy the ortho- or para- position to NH2 or OH. Except<ions are NH, and OH themselres ; these in the ortho- or para-position to each other hinder bromination, and the action of bromine effects oxidation. The carboxyl and sulphor,ic groups are displaced by bromine when they are in the ortho- or para-position to an arnido- or bydroxj- group. This tendency remains when another substituent (for example, CH3 or NO,), is in the meta-position with respect to the said groups.An S03H or COOH group in the meta-position rela- tively to NH, or OH is not displaced by bromine. Alkylised or acetylised OH and NH, groups exert a smaller orien- tating influence on bromine. The dialkylised amido-group shows this t o n greater extent than the nionalkylised group. A. G. B. Note ( Synthesis of Aromatic Hydrocarbons). By PA r I , JANNAWH (Uer., 1895, 28, 2823) .-In order to avoid clashing with Tohl (this vol., i, IS), the author points out the direction in which he is pursuing his researches on the substituted benzenes. Symmetrical Trinitrobenzene. By CORNELIUS A; LORRY DE BEUTN and FREDERIK H. VAK LEENT (Rec. Tmc. Chim., 1895, 14, 150-155 ; compare Abstr., 1895, i, 574).-When the calculated qunntitg (1 mol.) of a very concentrated solution of potassium hydroxide is added to a solution of symmetrical trinitrobenzene in 96 per cent.metbylic alcohol, red crystals of a substance are deposited after a time, whilst dinitroanisoyl remains dissolved in the mother liquor. The new substance has the composition represented by the formula CCeH3(N0,)3,DleOK], + HzO. If heated on platinum foil, i t detonates violently, and, when treated with dilute acids, sym- metrical trinitrobenzene is regenerated. When sodium hydroxide was used instead of potassium hydroxide, no analogous crystalline A. H. m 214s -4BSTRACTS OF CHEMICAL PAPERS. derivative could be isolated, although the solution became rcd. I f (:thyiic :iicohol is snbstitutecl for inethglic alcohol, the reducing action of the fol.mer is so p e a t tliat h o \ ~ 11, aiiio~yhoiis coir,pounds are alone prod lice d .A. R. L. Phenylnitromethane (exo-Nitrotoluene). By AR YOLD I?. HOLI,I;NAN (Rec. Tmr. China., 1895, 14, 121--130).-The observations on the boiling point of phenylnitroniethane (phenylnitromethane, Abstr., 1895, i, 455) hare been confirmed by Gabriel in a communication to the author, who has prepared phenylnitromethane by the method previously described by hiinself (lor. cit.), and also by Gabriel's method (Abstr., 1884, 902). The products had the same boiling point in both cases, and gave a benzenazo-derivative melting a t 101O. The action of one equivalent of bromine on exo-niti-otoluene fur- nishes a mixed product.Exo-nitrotoluene dissolves in concen trat,ed sulphuric acid, but the product soon resinifies. E,~onzetadiniti.o~oZziene, NO?*C6HI*C&*NO~, is obtained when phenylnitroniethane is dropped into cooled nitric acid of sp. gr. 1.5 (7 parts), care being taken that the temperature does not exceed loo during the reaction. The new compouiid is colourless, melts at 94", and is soluble in the usual solvents, but crystallises best from glacial acetic acid. Its constitution is proved by the fact that it yields nietan i t ro ben zoi c acid 011 treat men t with a1 kt11 in e peim angan at e. T 11 e sodiziin and potassiuut derivativcs a1.e red, and crjstallise in needles ; tlieir solutions are faintly alkaline towards litmus, and are decolorised on addition of an acid, yielding the parent componnd.Inasmuch, however, as exometadinitrotoluene is a strong acid it cannot be used as an indicator. The solutions of the alkali salts give, with silver nitrate, a gelatinous precipitate, which hlackens on being heated ; with copper sulphate (heated), blue triclinic crystals ; with lead acetate, a yellowish-white precipitate, and wit11 mercnric chloride a white, amorphous precipitate. An addit ice c m a p i u d , N01*C6HI*CH2*NO?,~H1.Hz0, sepayates in yellow, silky needles, when an alcoholic solution o f esometadinitro- toluene is treated with alcoholic ammonia, ether being subsequently added. It dissociates very readily, becoming white on exposum to the air for* a single day. From the mother liquor obtained in the preparation of exoinetadi- nitrotoluene, an isomeric substance was isolated, which also mas found to yield metanitrobenzoic acid on oxidation ; the specimen aiialysed nielted between 65" and 80".The colouy of the alkali salts of this snbstance is yellow, and is only slowly discharged when a solution is tixeated with an equivalent of acid, exornetadinitrotoluene then separating. The phcnornenon can be explained by assuming that the yellow anions are tyansfornied into colourless tautomeric anions. l)etem:iiiations of the molecular conductivity of the solution during its change of colonr, which diminishes in proportion as the colou~ vanishes, lead to the same conclusion. It seems probable, therefore, that exometadinitrotoluene exists in two modifications, onc of which-that forming yellow salts-contains the group NOH.A. R. Ti0 RGXS L C C H E bI I ST RY. 149 Ozotoluene. 11s A ~ ~ o I . I , H I,: K I . : s . ~ K I ) (CO)~I/. r ~ d . , 1S95, 121, 6.5 1-452) .-Tlie action of ozone on commercial toluene yields :: hlack, taiq-, acid, lion-exp1osii.e product, but if after the action of t h e ozone lias continued from 10 to 1.2 hours, the tolneiie is separated, washed with alkali, redistilled, and again heated with ozone a t O', it vields ozotolzicne, C7Hs06, a white, translucent, gelatinous substance. ivliicli becomes white and opaque if t h e tolueiic is evaporated ill :i ciirreiit of air. I n dry air, it begins to decompose at 8' or lo', and i l l moist air i t is decomposed a t onct'. It detonates when heated 01. striick, but less maclily tlinn ozobenzene (Absti.., 1895, i, 593).111 (.elitact witli concentrated aqueous potash, i t decrepitates briskly, but. unlike ozobenzeiie, it does not explode in contact, with ainnionia 01' concentrated sulpliuric acid. Water decomposes it with dcvelopnieii t of lieat and formattion of formic and benzoic acids, a resnlt n-liic.11 shows that the benzene nucleus remains intact. I'iire ortlioxylene, when treated wit,li ozone a t O", likewise yields a white explosive coinpouiid, similar to ozobenzene and ozotolueiie. C. H. Jj. Conversion of Nitriles into Amides by Hydrogen Peroxide. HJ- J. DE~SI.:I:T ( J . pr. C'heni., 1193, ['L], 52, 431--!&32).--Thc aiithoi, has applied Kaciziszewski's method (Abstr., 1885, 496) to snnd1.y niti.iles, and has obtained fair jields of the cori*espondiiig nmides froin benzoiiiti-ile, benzylic cyanide (in alkaline soliit,ion), paratoluc- nitri le, and P-iiaph thoiiit rile.Propionitrile and 2-naph thonitri 1 ~ - y n ~ c veq- poor yiclds, wliilst ortliotoluonitrilc was not conrei,tcci a t all. A. C ; . I<. An Abnormal Tribromo-derivative of Pseudocumen 01. Bj- KARL A L K E I ; ~ (Be?.., 18'35, 28, 2888-2902 ; compare the two follow- in.. absti.actsj.-'l'lie remaikable reactions of the tribroino.dei.irati\-~ of~i'seudccumeiiol, which arc described in tohe two followiiig abstract>, seem t o be best explnincld 11)- the foi.iiiuln C31e<CBr:C (OBr )>C31c.. CAle - --Cur, Tlie nietliosy-coni~,ound lvould tlieii receive the forniuln the metlioxy-group having, by molecular cliangc, been substituted for ail atom of hydrogen of the niethjl group, whilst this atom of' Iiydrtl- gen goes to form t h e hydroxyl group, w b i d i these derivatives 011 doubtedly contain.The f o r i n u h of the remaining derivatives r t i v given along with their special description. A. H. An Abnormal Tribromo-derivative of Pseudocumenol. 1 3 ~ KAKL AUWEI:S aiid J. J ~ A I ~ \ Y I : I ) E L (Ber., 1S95, 28, 2902-2910 ; COIL- p a r e foregoing abstract) .-Pseadocumenol yields two broino-deriw- tives which coutain the biaornine atoms in the nucleus (Keutci., Rer., 11, 29). I n addition t o these, n t1iii.d compound can be obtniiied 1)y ti.cnting the phenol nitli bromine and acetic acid. This substance, t l i l ~ i . o m o p s e z ! t l o ~ ~ i n ~ ~ ~ ~ ~ l iiro7tLi(le, C6Afe,l3r,*O R r , crystallises in large, d:it needles, and melts at.125-12Gq. I t does ILot dissol1;e imniediatelJ- i::150 ABSTRACTS OF CHEMICAL PAPERS. alkalis, b u t is decomposed by them after n time. The bromine atom very readily enters into reaction, and the substance pr.oduced is decom- posed b-j- alcohols if left i n contact with them ; by silrer nitrate, w i t h format,iox of silver bromide ; and by potassium iodide, iodine being I i berat e d . D ibTomo nzethocypsezidocz~~~2ei~ol~ OH- C ,Me2B r,. C H,. OMe, i I) obtained by boiling the tribromo-derivat ivc with methylic alcohol. It crystallises in matted, silky needles, melts a t 9l.-92', and is readily soluble in alkalis, forming solutions from which i t is repvxipitated by acids, even after boiling.This substance contains a hydroxpl group, and yields a beizzoate which crystallises in fascicular gronps of silky needles melting a t 120'. Etho~~dibi.omopsezidoc~rrneno1 closelp resembles the methoxy-compound, and crystnllises in silky needles melting a t 85-87". The benzoate also forms needles, and melts at. ~1O9--11O7. The tribromo-derivative also reacts with aniline to form a compo?r.iztd of the formula OH*C6Me2Br2CH2*NHPb, which ci.jstallises in idhomboid forms, and melts a t 134--134*5'. This substance forms salts. both with alkalis and acids ; t h e sodiiim salt crptallises in silky needles, which are very readily soluble in waterl and are decomposed by carbonic anhydride. The salts with acids are crptalline, and almost insoluble in cold water, scarcely soluble in hot >vatel* ; the bron2ide melts at about 20O0, t h e rnhloride a t about 205', the n i f m f e with cle- coniposit.ion at about 172", and the a,ilphate indefinitcly from 1%j-150°; t h e acetute, which c~-ystallises in prisms Iiaring an ada- mantine lustre, melts at 223-22.5'. The piperidiije contpfiwzd from t h e trihromo-derivative foi-ms concentric groups of slender, white needles melting at 91'; i t resembles the aniline derivatire, but i t s salts with acids are somewhat more i*eadily soluble in \vatel*.The byomide melts at 207-208' ; t h e bewxate c y t a l l i s e s in small needles melting at 136*5--137*.5'. When i t is heated on the i\-n.ter bath, piperidine is given off, whilst tetycthI.omodihl/dl.oa.ytet~.cci,z~f h ylsfilbwc, C,H,(C6Me,Br,*OH)2, remains ; this ccjstallises in matted needles, melts at 232*5--234', i s readily soluble i n alkalis without decom- position, but only very sparingly in the oydinary solvents.The ethiit ether forms lustrous plates, and melts at 171-172.5' ; its moleculnr weight, determined by the cryoscopic method, agrees with the formula C,H2,13r,02. A. H. An Abnormal Tribromo- derivative of Pseudocumenol. By KART, ALWEKS and S. AVERY (Rer., 2895, 28, 2910-2923 ; compai*e t h e foregoing abstracts).-When the tribromo-deriratire of pseudo- cumenol is brought into contact with dimethylaniline, the bromide of t h e dimethglaidine derivative sepal-ates in the form of lea€-like ci*ys- tals melting at 234-236'. The free bcrse, OH*C8Me,Br,*C H:NMe,Ph, crystallises in transparent needles melting at 124', and resembles the aniline compound in i t s general properties.The I~ydr*ocltioritle crystallises i n nacreous plates melting a t 216--220'- ; the tiitrate melts at 20U0, and t h e szclphate at 86---90"; all these salts are iiisoluble in water, and are &composed by boiling watei.. The beiizoate melts a t 156-156'. The presence of the hydroxyl group in this compound is further shown by the fact t h a t i t unites with phenylcarbimide to form a y h e n y h r e t k a u a tlericatirc,ORGANIC CHEMISTRY. 151 NHPh*C0O*C,~,Ie,B1,~.CH:NJIe,Ph7 which melts a t 18G-169O. When the tribromo-derivatire is treated with pyridine, the hydro- Lrornide of a p yridine derivative, OH*C&~e,Br,.C H2*C5NE5Bi*, is formed ; this is insoluble in water, melts a t 234-236', and crystallises with lHzO from an acetic acid solntion of hydrogen bromide.When it is treated with alkalis, the corresponding base is not liberstled, but a yellow szibstame, which is ver.7 unstable, is produced ; this has the formula C9H8Br,0*C5NH5 $. 2H,O, and, when heated with aqueous alkalis, yields tetrabromodihydroxytetramethylstilbene, identical with that obtained by heating the piperidine derivitive on the water bath (compare the foregoing abstract). When the yellow compound, however, is heated alone on the water bath or boiled with water, it yields dihromohydi.oxy~~sezidoc.z~~~aeiao I, 0 H*C,Me,Bi;*CH2*0 H. The same substance can be more conveniently prepared by boiling t h e tribromo-derivative itself with aqueous acetic acid or aqueous acetone.It crystallises from benzene in lustrous white needles, and melts a t 166' ; it unites with some difficulty with phenylcarbimide, fbrming a compound, C9H,BrZO*O*CO*NHPh, which is a white, crjs- tJalline powder melting a t 135'. Potassium ferricyanide oxidises the hydroxy-derivative, forming an insoluble substance which has the formula (C,H,Hr,O),, and melts at 200-20.5° ; the constitution of this product has not yet been ascertained. The cfher of dibro- ?)zol2ydroz?/psezcdoc.llmenoZ, (OH*Cs~~e,Br2*CHz),0, is formed when the hydroxy-compound is boiled with acetic acid and, indirectly, when the tribromo-derivative is dissolved in acetic acid, water added to the hot solution, and the whole boiled. It crystallises in slender, silky needles, and melts a t 252'; it is readily solnble without decom- position i n aqueous alkalis, and yields a diacetate, which melts a t 216".The acetate of dibromohydl.oa~p~e?idoczi~~e~Lol is formed along with the ether when the tribromo-derivative is heated with aqneona acetic acid, and may also be prepared by boiling the same substance wibh glacial acetic acid and sodium acetate, and by treating the liydroxy- compound with acetic anhydride. It is insoluble in water, readily soluble in other solvents, and melts indefinitely at about 113". When hoiled with aqueous acetone, it yields dibromohyclroxypaeudociimenol. When it is shaken, or ground up with dilute aqueoiis soda, on the other hand, i t yields tet rabromodihydroxytetramethjlstil bene (com- pare foregoing abstract).The tri brorno-derivative is reduced by zinc and glacial acetic acid, with formation of dibromopseudocumenol and the acetate of hydroxydibromopseudocumenol, accompsnied by a small amount of a substance melting a t 270-272', the constitution of which has not been ascertained. A. H. Derivatives of Benzoylcarbinol and of Diphenacyl. Sy VICTOR FRITZ (Bey., 1895, 28, 3028-30:34; compare Hunaeus and Zincke, Abstr., 1876, 223; E. Fischer, Ew., 20, 822; 26, 2400; Abstr., 1895, i, 440).-Benzoylmetbylic phenplic ether, C H2Bz*OPh (Mohlau, Abstr., 1883, 332), d3es not reduce Fehling's solution, and is not decomposed at 100" by aqueous alcohol containing 5 per ccnt.152 ABSTRACTS OF CEEMICAL PAPERS. of hydrogen chloride. The o;cii/ze crjstallises in small, coluurless pris:ns) melts a t 113-114" (uncorr.), and is readily soluble in alcohol, etlier, benzene, and alkalis. The plLenyZllydi.azoize is readily soluble in etlier and benzene, more sparing17 in cold alcohol ; i t melts at S5-8i", and readiiy turns browii on exposure to t h e air.BeuzoyZmethyZic p-izaphthyZic ether, CH2Bz*O*CloH7, obtained by t lie action of broniacetophenone on the sodium derivative of /3-naphthol, crystallises in sinall, colourless needles, and melts at 104-106;' (uncorr.). Towards Fehling's solution and hydrochloric acid, i t behaves i n exactly the same way as the pheiiylic ether. The oxime melts at 144-145". GisefhyZbe~zxoyZca~~bi~zoZ was prepared by the ethylation of henzoyl carbinol (Fischer, Abstr., 1895, i, 440) ; i t crystallises i i i colourless prisms, inelts at 190-192", and is readily soluble in hot alcohol or ether.B~~o?nodiphenacyZ, C:OPh*CHBr*CH,*COPh, is obtained by tlie action of sodium and alcohol on ail ice-cold solution of bromacetophenone in alcohol ; i t crjstallises in sniall, colourless, glistening needles, melts a t 161-162", and is only sparingly soluble i n alcohol and ether. When treated with alcohol and zinc dust, it yields diphenacpl (Kapf and Pad, Abstr., 1889, 147 ; Notling and Kohii, Abstr., 1886, 349; Clans and Werner, Abstr., 18S7, 827), and with alcohol and sodium amalgam yields a compound C16H1902. This crystallises i i t colourless needles, melts at 93-94', is readily soluble in alcoliol, ether, and benzene, and sublimes when heated above its melting point.It niay also be obtained by the reduction of diphenacyl itself wit11 sodium amalgam, and is probably diplzei, yZteti.n?,zetli~ZeILe~lycol, C,H,( C H Ph*OH)z. J. J. S. New Salts of Guaiacol. By H. DGBOIS ( C h z . Celtf,.., 1S95, i, 'LO9 ; from ,4poth. Zeit., 9, 952).-(:uaiucoZ succiiiufe, ci*jstallises in fine, silky needles, melts a t 13G", is insoluble in watcr, sparingly soluble in alcohol or ether, but readily i n chloroform, ace- tone, or hot light petroleum. Bromine readily forms substitutioii products. I t is best prepared by dissolving guaiacol in slight exce*b of sodium hydroxide solution, cooling to O", and then adding tl:e requisite quantity of succinic chloride while keeping well stirred. Giiaiacol PhosphCrte, PO(o*C,H,*O~le),, crystallises in hard, c o l o u r l e ~ ~ plates, melts at 98", is readily soluble in chloroform and acetone, I I I ! ~ insoluble in water, ether, and light petrolenm. It is readily hy- drolysed by aqueous potash a t 150°, and may be distilled under diminished pressure without decomposing.Triresorcinol. By OSWALD HES~E (AnnaZe;a, 1895, 289, 61-70).- The hydrochloride of triresorcinol, C18HI,04,HCI, is obtained by heating resorcinol (4 giams) with glacial acetic acid (&6 c.c.) and fuming hydrochloric acid (4 c.c ) i n sealed tubes a t 85" for 72 hours ; it COR- tains 1H,O, which is ieniored a t 120°, and crystnllises in small piisnis which have a fire-red reflex and appear yellow by transmitted light. It i s almost insoluble in organic aolrents, but dissolves readilj- i l k J.J. S.0 R C; A S IC C H E J1 I ST R 1- . 15;5 ;ilkalis arid alkali carbonates, forming jellowish-red solutions wliicl;, 011 dilution, exhibit intense, green fluorescence. Trircsorcl'iiof, 0 HDC6HI.0.CGH4.0*CGH~*OH, obtained by prolonged treatment of t h e hplrochloridc! with boiliiig water, crystallises in short pi*isnis wliich colltain B$HzO, and hRye a dark, bluish-red reflex, appearilly ~ ~ 1 1 0 ~ by tmnsmitted l i g h t ; i t becomes anhjdrous a t 160°, ancl decoinposes above 130" without previously melting. Although t.lie substance dissolves sparingly in comnion solvents, the soliitioiis ex- Iiibit intense green fluorescence ; i t dissolvcs in alkalis and alkali c:trbonates, cottou, wool, aiid silk being dyed yellow by t,hesc solu- tions. The hy17-0bro~,tirl~~, (C1,HI,0,),,5HI3r, is obtained by ti*eatiiig the solution in glacial acetic acid with concentrated hydrobromic :icid; it is anhydrous, and, altliougll scai-cely soluble in cold water, i t imparts a n intense green fluorescence t o this medium.The rZicicef!/l <Icrivative crystallises iu brownish-red leaflets which melt and dcconi- pose at 26O-2iO0. lj ~*onzofrireso~ci?~o I h y d r o t w 11 1 itle, C ,,H 313 r04 , H B i*, is obtained 13)- ,zdctin,a bromine to a solution of triresorcinol in hot acetic acid and inimediat,ely removing t lie cryst,als which se1xwat.e ; i t contains 1H2O, and is decomposed by boil iiig u-ltter, jield ing b r w w t riwsorcino Z, \vliicli dissolves readil? in boiling \vatel*, and exlii bits an intense gi*ecii fluorescence in solution. If excess of bromine is eiiiploIe(1, the siibstniice is redissolved, ancl a conzpoz~?~d is forniecl having tlic composition (C,,H,,Br,0,),,3H13r ; this is readily soluble in boiling ivater, yieldiiig a n intense bluisb-violet solution, whilst alkalis and ammonia develop a purple-violet coloration.Il'ef~.u~~'o~r~of,.i,.esol.c.irLol, C,sHI,)Bi*40J, is obtained b j dissolving the foregoing compound in aqueous sodiuiii hydrogen carbonate ancl treating the liquid with iiitric acid ; i t i s insoluble in cold water, and only sparinglj soluble i l l t Iic boiling liquid, yielding a bluish-violet solntion. After removiiiy tlie two pi*oducts already mentioned, as obtained on brominating tri- resorcii~ol, the liquid contains ltepta~7.o?iloct.ireso,.ci?~oZ, CleHiBri04, :I ciwmine-red compound having a bluisli reflex ; i t contains 2iH20, and is insoluble in water, dissolving readily, however, in orgaiiic so1veiit.i.Alkalis, alkali carbonat'es, and ammonia give rise to bluish-violet solutions which dye wool, cotton, and silk the same shade. Bart11 and Wcidel (Abstr., 1878, 61) have obtained diresowino1 and te traresorciiiol by the action of concentrated liydrocliloi*ic wit\ 0 1 1 resorcinol, mid the formation of resacetoplienone and resacettlii or ncetofluoresce'in u n d w tlie influence of glacial acet,ic acid, has beel: also recorded. 91. 0. E'. Action of Potassium Hydroxide and Ethoxide on Quinone. 13s CHAKLES As.1 K E (Conrpf. rend., 1895, 121, ~ 3 0 - - - . % ~ ) . - ~ ~ ~ 1 ~ l'otassinm ethoxide is added to a dilute solution of quinone in ethei., :t green compound, C6H,KOz+EtOH, is precipitated.It is stable i t t clry air or d i y oxygen, but rapidly alters i n nioist air. The action of corlcentiatecl alcoholic potash on quiiioiie develops :I large quantity of heat. JI ith a very dilute alcoholic solution of q u i - none, n mixture of a blne and a yellowish-bro\vn compound is obtaii:ed. The careful addition of alcoholic potnsh to n very d i l u t e154 ABSTRACTS OF CHEMICAL PAPERS. ethereal solution of quinoiic in an atmosphere of hydrogen yields a crystalline blue precipitate of the composition Cc€T,KO, + H,O. I t alters rapidly in presence of moist ail* or oxygen, or in contact with water or alcohol. Attempts to obtain a dipotassium derivative of quinone we1.e n o t completely successful, and the compound seems to be very unstable.A product with a composition corresponding with a compound of one molecule of dipotassium quinone with two inolecules of alcohol is obtained on adding a large quantity of ethey to a mixture of an alcoholic soluticw of quinone with excess of alcoholic pokasli. C. H. B. Peroxidised Potassium Derivatives of Quinone. BJ- CHARLES As,rm (Compt. rend., 1895, 121, 559-561 ; compare this w l . , i, 18). --Peroxidised dipotas.sii~m guiiioue, c6T(?o6, a blackish, crJ-stalline, rwy hygiwscopic compound, is obtained by mixing alcoholic solutions of quinone and potassiuni hxdrosicle, heating the mixture at i O - 7 5 O , and passing a current of dry oxygen through i t for eight to ten hours ; i t is very solnble in, and is decomposed by, water. The same prodcct is obtained even in presence of a large excess of the alkaii. Peroxi- dised potassium q t i i ~ m e , CtiKH06, is a black compound obtained b y dissolving the preceding conipound in watw and adding sufficient, alcohol t o bring the alcoholic strength of the mixture iip t o abont iOo, or by passing oxygen through a solution of quinone in a dilute iiqueous solution of slightly more than the calculated quantity of potash, and afterwards adding the alcohol.If yuinol is dissolved iu alcohol containing three molecular pro- portions of potassium hydroxide, and treated with oxygen at i@--T5O, i t likewise jields the compound C6K206. The aqueous solutions of these potassium deiivativee, when iiiixed with an acid, yield a black precipitate which is under inrestigatioii. These resuits iiidicate that only two of the hydrogen atoms in quinone can be displaced hy a metal, and hence afford furthei.eridence of the diketonic character of qiiinotie.C. H. B. Action of Sodium Alkyloxides on Chloranil. Acetals derived from Substituted Quinones. By C. LORING JACKSON and H. 8. GMNDLEY (Anier. Chenz. J., 1893, 17, 6133-658 ; compare this vol., i, 19) .--DichZo,.o~Zietho.~~pic,iitone tetrethylncetd, C,C: I,( OE t)6, is formed in smalI quantity by the action of ethylic iodide on silver dichlorodi- ethoxyquinone hemiacet a1 ; after the diclilorodiet~hox~quino~e has beeii removed by treatment with dilute alcoholic soda, the acetul crystallises from light petroleum in large white,rhombic prisms orquadratic plates: i t melts a t 101-102', and sublimes a t 260-275' without decomposing.Wheii heated with sulphnric acid (sp. g ~ . = 1*44), it is hydrolysed, diclilorocliethoxyquinone aud, in sinall quautity, chloranilic acid being formed. More dilute acid, alkali, either aqueous or alcoholic, a n d l)i.omine are without action 011 the acetal. DichZo,.odietkoxyiiiiiio,ie di- i,!.,izo?lZdietl~yZacetccl, C,Cl,(OEt),(OBz),, is obtained by the action of henzoic chloride on the sodium salt of the hemiscetal suspended in alcohol ; i t is not formed i n presence of ether, nw by t h e action of benzoic chloride alone a t 1003 on either the hemiacetal or the sodiiirriORGANIC CHEMISTRY. 155 salt. The com- pound crystallises in short, thick, coloiirless prisms, melts a t 170", does iiot react with soda, hyclroxylarnine, cr zinc dust and glaciai acetic acid.Hjdmxylamine hydrochloride and dichlorodiethoxyquinone readily combine, forming a black crystalline compound. When the above acetal is heated with sulphuric acid (sp. gr. = 1-44>, a compound is formed which is probably the oxide of dichlorodiethon.yrl~iillol2e tlibenzonte, C6C1,0(OEt),( O h ) , , or that of dichlo~oquiiaoiie he?zzoyl- thylacetal ; i t crystallises in well-developed besagonal prisms, melts a t 14P, and, with aniline, gives two or inore compounds which will be described later. When reduced with hydriodic acid, a corn- pound, OH*C,C'I,(OEt) (OBz)?, is formed ; this crystallises in prisms, melts at 164", and is being further investigated. Dichlo~odiefhomy- p i i z o l &benzoate, c6c1,( OF!t),( OBz)?, prepared from sodinm dichlnro- diethoxyquinol and benzoic chloride, crystallises in long prisms, melts a t 215", and dissolves in hot concentrated siilphuric acid, b u t is not changed by hjdrochloi-ic acid, nitric acid, or alkali.The yield is about 66 per cent. of the theoretical. Dich lorodimet hoxy puinone dibeizzo yld imeth y lacelul, C,C 1, (OJle) (0 Bz),, prepared like the corresponding ethoxy-derivative (see above), crys- tallises In colourless plates, nielts a t 193", and, when heated with dilute sulphuric acid, yields the on.itle of dichlorodi7,2ethoi,yqlli?701 dibewoale, C6C1,(OMe),( OBz),O, which crystallises in rhombic prisms, me1 ting at 205-206". Dichlo~otlietho~yy~~iiroi~ e diethy Zaceta 1 ethyl ic dicnrbonate, C6C1,(OEt),(OCOOEt)2, prepared from the sodium salt of the heniiacetal and e t h ~ l i c chlorocarbonate, crystallises in colourless, flat prisms melting at 122-123°.~et,.upheno~ypi~i7zone, C,(OPh),O,, is readily obtained from di- chlorodiphenoxyqninone and potassiuni phenoxide in aqueous solu- tion ; it is also formed from potassiuni phenoxide and chloranil in aqueous solution, and from sodium phenoxide and dichlorodiphenoxy- quinone suspended in benzene, but in presence of alcohol, the di- ethoxydiphenoxy-derivative is obtained ; it crystallises from benzene in red prisms, and melts a t 229-230". It is not changed by sulphu- rous acid at looo, nor by sulphuric acid (sp. gr. = 1.44) ; hydriodic acid and stannous chloride in acid solution reduce i t slowly, and i t clissolves in concentrated sulphuric acid (sp.gr. = 1.83). Dipheuoxy- tinilic ncitl, C,( OPh),( OH j,O,, formed by heating the preccdiiig corn- pound with soda (1 : 4), crystallises in thick, lustrous, dark reddish- brown rectangular plates, softens a t about 27G0, and melts at about 2'76". Acids are without action on it. The sodizm salf forms black crystals which dissolve in water yielding a purple coloured solution. Tet,.aphe?zo.z.~g.1iiriol, C6(0Ph),(OH),, is obtained when tetra- phenoxyquinone is reduced by means of zinc dust and glacial acetic acid ; it crystallises in colourless, well developed, thick, rhombic plates, commences to decompose at 210°, and melts at 219-220". Diethox yd@henoxyqu inofie, C,( C)Et),( OPh),O,, is formed from di- ch~orodip~~enoxyquinone and sodium phenoxide in absolute alcoholic solution (see above) ; it crystallises in long, silky, orange-jellom156 ABSTRACTS OF CHEMICAL PAPERS, stellate iicedles, and melts a t 128'.The yield is poor. Dimetliony- cli~l&eiLon.~/q/fi,io}~c, CG(OMe)2(OPh)20L, preFared from tetraphenosx- quinone and sodium methoxide, ciytallises in long, golden-yellon-, prismatic needles, ancl melts at 171'. It is soluble in dilute soda ; witli sodium methoxide dissolved in metliylic alcohol, i t becomes white, dis- solws in water, and, on the additioniof dilute acid, n white, amorphons precipitate is prodnced which soon deconiposes. A hemiacetal is prob- ably formed, but i t is mnch less stable than that derived from the dichloroquinone. DL'L~onzod~~l~celzon~yqz~i~zzo~ze, C,Br,(OPh),O,, is pre- pared by the intei-action of sodiuin phenoxide and bromanil in alco- holic solation, but probably a n aqueous solution wonld be preferable ; i t crystdlises in short, blunt, orange-red needles, melts at 2G6-26io, and is reduced by zinc dust and glacial acetic acid t o the colour- less q~iinul.Towards acids i t is stable. Bromanil reacts with sodium pheuoxicle in alcoholic solution like chloranil in aqueous solntioii. ljibi-onzodir,i etlzozyq ciinoue tliwicthylheiu i n c e t d , C$r, ( OMe)l (OH) ?, foi iiied from dibroniocliphenoxyquinone anti sodium methoside, is white, amoi*pIious, and melts a t 178-188° ; as i t then becomes red, it is probably converted into dibroniodimethox~~yuinone; the sanie change is produced by dilntc snlphuric acid 01' dilute hjdrocliloric acicl.C f I t l o l . o d ~ 7 ~ ~ s z o , ~ , y ~ / ~ ; ~ ~ o 7 l e , C,HCl(OPh),02, is formed by the actioii of potassium plienoxide on trichloroquinone in aqueous solution ; it crystallises in long, slender, oval, orange-coloured plates, melts at 169-170", and, when treated with sodium niethoxide, water, and dilute acid successively, it yields a n unstable hemiacetal. Sodium ethoxide i n alcoholic solution, when mixed with quinone dissolved i n ether, gives a heavy, flocculent, dark green precipitate, which is de- composed by alcohol mid water ; when dried in air, i t ignites spoil- tantously at t h e ordinary temperature, b u t if diicd in hydrogeii, and then exposed to nir, i t is stnblc u p to 4b0, but then burns like tinder ; i t is not a homogeiieous substance, and in its production the constituents react i n iiiolecular proportion.l'he same compound, together n i t h plienol, appears to be fornied by tlic action of sodiuni etlroxidc 011 phenoquinone. In order to ascertain whether pheiio- ciuinone is a bemiacetd, t h e action of sodium phenoxide on quinone \\as investigated ; in presence of light petideum a dark green pre- cipitate is funlied ; TI ith benxeiie 3s solyetit, the precipitate is pink, niid heconies dark gieen when heated ; jii ethereal solution, a dalli red, crjstalline componiid is deposited ; after removal of the ether, the yesiclue readily dissolves in water with a slight green colour, and, when acidified, a dark ised, crystalline substance is precipitated i i i smnll quantity.Action of Bromine on Metanitraniline. By Himin- L. ~ ~ € I l ; L L ~ R (Amer. Chena. J., 1895, 17, G97--701).--The chief product formed by tile action of bromine, in glacial acetic acid solution, 011 metnnitrmiline is bi.o,i:onit,.ai2iZiiie [NH, : KOz : Br = 1 : 3 : 6j, whic.li cq-stnllises in bright yellow needles melting a t 139-140 . Its constitution is shown br the formstion of p trabromonitrobenx~ne The subject is still under investigdtion. J . B. T.ORGIAXIC CEEJIISTRT. 157 w11cn i t is treated with etbylic nitrite, and oE dib~~oiiioiiitroben;ei~c [NO, : 131. : Br = 1 : 3 : 41 by means of Sandmeyer's reaction. The compound is volatile with steam, is less basic than the isomeridc LNH, : NO, : BY = 1 : 3 : 43, and, with strong acids, forms salts which ;Lre deconiposed by water.The yield is 87.5 pey cent. of the nitraniline rinployed ; and by using metnnitracetylanilide. this is increased to 11 1 per cent. The hydi*ochZoi*ide crystallises in coloui-less, I i ~ s t r o i ~ s scales melting and decomposing at about 'LOO". The sulphnfr is deposited in broacl. thin, colourleFs, lustrous plates. The ncetyl tlcricntiue crgs- tallises in colourless, silky needles melting a t 180'. l'i*ibi*omoiiiti*- aniline [NH, : NOz : 13r3 = 1 : ;3 : 2 : 4 : G] is formed together with the preceding compound ; tlie yield is 19 and 107 per cent. oE the aniline and acetanilide respectively. Aniliiie, under the nbore conditions, yields chiefly di- and tri-homo-derivatives, and when monobronio- deiivatives are formed, they are para- and not principally oitho- compounds ; in this instance, therefore, tlie nitro-group in the meta- position exerts a protective influence, and affects the position of the substituting at oms.*J. B. T. A Correction (Brornination of Acetanilide and Acetopara- tolnidide). By WILHELXI VAI:IIEL (Be/-., 1895, 28, 3059).-TIie anthor points out that his observation regarding the broniination of acetanilide and acetoparatoluidide (Abstr., 1894, i, 19) is ident,ical with that recorded by Blacher (Be).., 1895, 28, 2359). $1. 0. I?. Orthamidobenzylamine. By MAX BUSLIH ( J . PI- Chem., 1695, [2], 52, 373-416 ; compare Abstr., 1893, i, 306--,307).-X. With k', R RL RN E R .-Ortho,t ifrobeiLa~lor.thocl~lora,?~iline, IS0,.C6H4*CH,*N H*C6H4C I, is prepared by heating orthoiiitrobenzylic chloride with orthochloy- aniliiie (2 mols.) foi- f i r e hours in alcoholic solution, and is precipi- tated by adding water to the solution.It cq-stallises in yellow needles, melts at 6i0, and dissolves easily in tlie usiial solvents ; the hydl.ocltZo?.ide forms white needles, and melts at 172'. By rednction with zinc and acetic acid, the nitro-compound yields o l f l ~ n wicZobei~zg2- c,r.tltocl~lora;ziline, which crystallises in aggregates of yellowish needles, melts at. 58O, and dissolves readily in ether and benzene, aud in warm alcohol ; the h~yl~.ochlc~ritle forms colourless needles, nielts a t 1.5;2?, and is soluble it1 water. (Abstr., 1894, i, 146): crystallises in white, silky lamine, which become leddish on exposure to light, melt at 200°, and dissolre sparingly in the usual solvents.Reduction by means of sodium in alcohol converts it into 3-phenyltetrahydroquinazoline, and oxidation by mercuric: oxide in alcohol a t 150' converts i t into ~ 3 ' - 0 ~ t h 0 ~ l ~ Z 0 ) . o ~ 7 ~ ~ ~ ~ which crptallises in colour- h yl vo 1 t t iw w'o 1 im, N- YO c 6 H ~ < c H,*N.~,;H&~ 9158 ABSTRACTS OF CHEMICAL PAPERS. less lamina?, melts at 207', and dissolves in alcohol and, sparingly, in ethylic acetate. XI. With FRASCIS E. ~RA~ClS.-01.t~io~~it?.obenzy~mefachlo?.a?2ilz,~e forms ello ow crystals, melts at 59O, and dissolves easily in glacial acetic acid, alcohol, ether, and beuzenc, but sparingly in light petroleum, and not a t all in water. Orthaiizidobenzylmetnciilo~anili~~t. is an oil; its hydrochloyide crystallises in white laminse, melts a t 1:37-138', and is sparingly soluble in water, although freely soluble i n alcohol.during the reduction of orthonitrobenzylmetachloraniline, crystal- lises in large, white laniinse, melts a t l l O o , and dissolves easily in ether, benzene, and chloroform, but only sparingly in cold alcohol. 3'-~Ietnchlor~phen~l~l~iofet~cchydroqz~inazoli~ae crystallises in colour- less, vitreous needles, melts a t 198-199', and is sparingly soluble save in glacial acetic acid and chloroform ; reduction only affects the chlorine, 3'-phcnglthiotetrilhydl.oquinazoline being formed. - Met cx ch lorop hen yldili ydyo-P-p henofrinziiae, C,H, <N -r CH2*N*C,H,C1' pzred by the action of amylic nitrite on an alcoholic solution of orthamidobenzylinetachloraniline hydrochloride, crystallifies in yellow needles, melts and evolves gas a t 146-147', and dissolves easily in benzene, ether, and hot alcohol, sparingly in light petroleum. XII.With C. Vo LK E s IKG .--0 rt honi troben z y 1 parac h loraniline has been already described (Abstr., 1894, i, 210) ; the hydrochlmide melts at 170-172" ; the sulphate is described. Oythamidobeirz~lpayacl~loy- awiline crystallises in lustrous, white needles, melts a t 89-90', and is freely soluble in most organic solvents; a kydyochloyide and a Jihydrochloride are described. The benzylidene derivative, CHP h:N*C6H4-C H,*NH*C,H,CI, f orrn ed by heating orthamidobenzylparachloraniline with benzaldehyde in alcohol, crystal1 ises in stellate groups of white needles, melts a t 115-116', and dissolves easily in hot benzene and alcohol, but only sparingly in ether or light petroleum.The orthohydroxybemylidene derivative crystallises in stellate groups of yellow prisms, melts a t 124O, and is soluble in the usual solvents. The metaizit?.obenz2/lidene derivative melts a t 8 6 O , and is sparingly soluble in alcohol, ether, and chloroform, more so in benzene and glacial acetic acid, and insoluble in light petroleum. O~thaceta~~iidobenzylpa~achlora~ailine, NHAc*C6Hr.CH,*NH*C6H~cl, prepared by heating the base with acetic anhydride, crystallises in long, colourless prisms, melts a t ISSO, and dissolves freely in hot benzene, chloroform, and carbon bisulphide. 3 ' - Parachbropheny 1 t hiotst rali ydToq u imzoline cry stallises in lus trous, white laminae, melts at 228", and is soluble in the usual solvents, except carbon bisulphide and boiling glacial acetic acid. Parachlow .phen yldihydro-P-phenotriazine crystallises in yellow laminse, and also in thick crystals ; it melts at 134O, and dissolves easily in benzene and chloroform, but only sparingly in ether or light petroleum ; theORGANIC CHEMISTRY. 159 hydrochloricle, CI,H,,N,CI.HCI, melts and explodes a t 103", and is soluble in alcohol, but is dissociatzd by water; the platinochloridc, ccuyochlode, and p i c m t e are described. Pa ,-achlorophen y lo 1st h onit rob e m y hi t rosnmine, ~O,.C,H~*CH,.~-!NO)*C~H~~I, crptallises in yellow, transparent prisms, melts a t loo", and dissolves freely in benzene, glacial acetic acid, and hot alcohol, but only sparingly in ether or light petroleum.Ynyarh 7o,.oph~?zylo~.tlianzidoGe~azylh,ydl.azi~le, n'H,*C,H,.CH,*N(r\'H2)*C*H,Cl, forms crystals, and melts a t 9.3' ; it dissolves in most solvents, and yields a beizzy Zidene derivative, CH Ph:N *C,H,*CH2*PU'(N:C HPh)CsH,C 1, when heated with benzaldehyde and alcohol ; this crjstallises in long, felted ncedleg7 melts a t 150', and dissolves eaqily in ether, benzene, carbon bisulphide, and chloroform, bnt only sparingly in alcohol. XIII. With FH. H~~h';~~.-Orthamidobenzglparabromaniline has been already described (hbstr., 1894, i, 210) ; the dihydrochloyidr melts at 99-94O, and the malate a t 127" ; the benzylidene derivative ! b e 1 2 z y l i d e l l e o r t h a m i d o ~ e i a ~ y ~ ~ r ~ b , , o n t n , l i Z e ~ crystallises in stellate groups of white needles, melts at 122", and dissolves freely in chloro- form, caybon bisulphide, and glacial acetic acid, but only sparingly in ether, alcohol, benzene, or light petroleum ; the orthohynro~.ybenz2/Zi- rleize derivative crystallises in yellow prisms, melts a t 143-14F0, and is soluble in most solvents ; the pai.aiiif,.obenzylidti~ze derivative melts at, 14407 and is sparingly soluble in the usual solvents, except glacial acetic acid and benzene.Orthacetanzidobenzylpm-a broinniziline crys- tallises in colourless prisms, mclts at lYSO ; it is easily soluble in benzene and chloroform, but very sparingly in ether. and light petroleum. 3'- T'crra~,.omo~7tenyllietoteti.ali~droq~in~zoli~ie7 from carbonyl chloride and orthamidobenzjlparabromaniline, crystallises in transparent, quadratic tablets, melts a t 226O, and is sparingly soluble i n alcohol, ether, carbon bisulphide, and light petroleum, but freely in boiling benzene, glacial acetic acid, and chloroform.Pni.abronzophenylthio- t e t m hydroqzcinazoline forms long, colourless, four-sided prisms, me1 ts at 234", and dissolves easily in arnylic alcohol. P a ~ L Z brom oplt eny ld ihydro- p-p henotriaziue cryst allises in lustrous, yellow lamince, melts a t 1 6 4 O , and dissolves freely in benzene, alcohol, ether, chloroform, and carbon bisulphide, sparingly in light petro- leum, and not a t all in water; the liydi-ochloride melts a t 105-10GC ; the yhtiuochloride (m. p. 191'), aurochloi-ide (m.p. 108-109"), and pictxte (m. p. lOC;"), are described. Pnr~ab~o~~to~he~zylo~~thonitro~e~i~ylrlit rosamine, K0,*CtiH,*CH2*N( NO)*C,H,Br, formed by the action of nitrous acid on orthonitrobenzylparabrom- aniline, crystallises in microscopic tables, melts at 167O, and dissolves easily in the usual solvents, except light petroleum. Pumbromo- yhe?Lylorthamidobenzylhydi.aziiie crystallises in lustrous tables, melts at 119-120°, and dissolves freely in the usual solvents, except light3 GO -4BSTRACTS OF CHEY LCAL PAPERS. petroleum ; the />mlnte melts a t ; the hLl)/.zylidpne derivative, CH Ph:N*C,H,*CH,.N(N:CHPh).C,H,Br, crystallises in l o ~ ~ g , co]Ot,r- lcss pyisms, melts a t 171", mid dissolves in most solvents. XLV. With PAL'L HARTV iw. - ~ ~ r t l ~ a n z i d o b e i a r y l p n ~ ~ a p h e t ~ ~ ~ from oythonitrobenzylparaphenetidine (lo(*.c i f . ) , crystallises ill nacreous laminae, melts at 78', and dissolrtbs in alcohol, ethel., bell- zene, chloroform, and glacial acetic acid ; the hydrochloride, s:cLlplzutt: (m. p. loo"), oxalate (m. p. 132'), bruylillene derivative (m. p. 1:370), and o,.tJLolzyd~.oz~beizzyZideiie derivative (m. p. 94"), a1.e desclsibed. cry s t a1- :3'- Plie?iet~~lJietotef r a h ~ d i ~ o q u i w a ~ o l i ~ t c , lises in colourless needles, and melts a t 223'; it dissolves in glacial acetic acid, ethylic acetate, and chloroform, sparingly in ether and benzene, and not at all in water or light petroleum. 3'-Pheizctylthio- tefrahyd,.opi,ina~oZii~e crystallises in wlii te, silky needles, melts a t %8", and dissolves sparingly in the usual organic solvents, but not in ether, light petroleum, or water.3'-Paraphenetyltetrahydroquin- azoline melts a t 129", not 124" (loc. cit.). Pal.apl~enefyEdiJiyd,.o-p-phenoti.iazisae crystallises in yellow laminx, melts a t 144O, and is soluble in the usual solvents, except light, petroleum ; the hydrochloride (m. p. ll~5°),ylntinochloride, aurocldoridr, I~ydmb~ornide (m. p. 104"), and picrate are described. XV. With F. BRVSXER and Run. BrRh-.-Orthonif,.oben,-yZo/.fhrd?2i3i- dine, N0,*C6H,.CH,*?U'HDC6H,*o~le, forms brilliant, thick, orange-red ciystals, and nielts a t 8U". OrthamicSobe12,-ylorthallisidiite crystallises in colourless needles, and melts at 99" ; the dihydrochloride melts a t 175-176'. h o - o r t h obeiuy Zort Ir m h i d i n e , ( o~re*C6H,*NHgcH,*C,H,),N,, ci-ys tal- lises in orange needles, nielts at 150--151°, and dissolves easily in benzene, sparingly in ether.NH-70 CSH%H,* N-C,H,*OIEt' O1.thol~ytlroa.yhciLzyl ideiteo rflm mi(lobriuy1ort Ii n iiisidirLe, 0 H.C6HI~CH:N*C6HI*CH2.NH*CsHI*O~Ie, from salicylnldehyde and ortlia~nidobenzglorthanisidine, crystallises in yellow, silky needles, and melts a t 79". 3 ' - O ~ t 7 ~ o n ~ e t h o l e y p l i e ~ z ~ j l ~ e t ~ t ~ t ~ n h y ~ r o q ~ ~ i ~ ~ n ~ ~ ~ l ~ ~ i r melts at 21i-21Sa, alld .j'-o,.tho?izetlLo~~y~l~enylthio~e~~ulLy~~.oq~iii~a~i)l~n~ at 237". XVI . With PAU L HA RT \i \ \ \ .--0 rt h nmido b e n q l p ti r m i s i d ilie me1 t s at 82O ; pai.anisylclihydro-~-iuhenot,.iclzine inel ts a t 139" ; both dissolve in most, solvents ; the hydrochlwidr, platiitochlnr~it7e, and pici*cctr (m.p. 125") of the triazine are described. XVIl . With F R . Br~.~No.-orf7inniidobewzyl-=c-naplithIJlni,ziiit,, NH,*C6H4.CH2*N H*C ,,H7, crystillises in Iustrms, reddish laminze, melts at 134', and dissolves in beiizene easily, and in alcohol, ether, and l i g h t peti~oleum with difficulty ; the solutions have a bluish-red fluorescence ; the &hydro- chloride, the s d p h a t e , C,,H,,N,( H2S04),, the benzylidene derivative (m. p. 107"), and the orthohydi.ox~benrylirlene derivative ( i n . p. 162") are described. 3'-x-~~cphth~ltl~iot3t,.a2Lyl71.r,rl~iiti~i;~lii~~ crystdlises in coloiirless,ORGANIC CHEMISTRY. 161 lnstrous laminae, melts a t 255", and dissolves easily in xylene, amylic alcohol, and chloroform ; the 1'-methyl derirative, C6€€4< KMe* S CH? -NGH,' formed by the action of methylic iodide on tlie quiaazolini, c ~ y s k - lises in white needles ; its hydriodide blacltens and melts at 21'2"., XVIII. With FR. BRAN ~.-Ortho~itrobeic~~l-/j-naphthyZaniinc, from fi-naphthylamine and orthoiiitrobenzylic chloride, crystallises in lustrous, red lamin~e, melts at 162", and dissolves in the usual solvents, sare chloroform ; the hydrochloride is described. Orth- ai,~idobeiixyZ-P-iaaphthyla?ni?ie forms white, lustrous lamins, melts at, OO", and dissolves like the a-compound ; the benzyZidene derivative (ni. p. 122O), ortlioh~droxybenx~lidei~c derivative (ni. p. lli"), and methylene derivative (ni. p. 153-158") are dcscribed.Orthoacet- nntidobei~zyl-~-acetoltnphthalide, NH~c.CGH,*CH,.NAc.CIoH,, forms coloiirless, thick ciystals, melts at 11 6", and dissolves sparingly in (+her, benzene, and glacial acetic acid, but not in light petroleum. 3 ' - ~ - N a p h t h ~ Z f ~ s i o t e t ~ a h y d ~ o ~ u i i ~ a ~ ~ l i n e crystallises in thick, colour- less lamine, melts a t 280", and dissolves freely in glacial acetic acid and amylic alcohol ; the l'-methyi! derivative melts at 140°, and its hydyiodide decomposes and inelts at 249". Orthonitrobeihz yl-p-izaphthyl~Litrosainine crystallises i u dark yellow, thick laminae, melts at 102", and dissolves freely in benzene, glacial acetic acid, and chloroform. 0 y t 1 ~ ~ 7 2 id0 benry l-P- nap ht h y l h y d r a z i w , prepared by the reduction of the nitrosamine, crystallises in slender iieeclles, and meits at 76" ; its orthohyd?.ox2!benzylidene derivative, OH*C6H4.CH:N*CoH4*C H,*N (N:CH*Cs H4*OH)*C loH,, crystallises in yellow, felted needles, melts at 176", and dissolves freely in benzene, glacial acetic acid, and chloroform.Derivatives of Dimethylparatoluidine. By JOHANNES PINNOW (Ber., 1895, 28, 3039-4045 ; compare Abstr., 1895, i, !%).-Orthonitro- pa~.atol~Lme~hyl?~it~osnmiiie is obtained by adding aqueous sodium nitrite to orthonitrodime t hylparatol uidine dissolved in hydrochloric acid ; it crystallises from alcohol in yellow needles or prisms, and me1t.s at 55". Orthoniti.o,izethylparatoluidine is formed when methyl- pwatoluidine is nitrated in sulphuric acid solntion, the liquid being subseqiiently treated with sodium nitrite at 0" ; it crystallises in red needles or prisms, melting at 57", and the acctyl derivative crystallises in slender, yellow needles melting at 128-128.5".Methylorthonitro- psrrictolyZnityamine is isolated from the liquid containing orthonitro- paratoljlmethylnitrosamine ; it crystallises from acetone in red prisms with green reflex, and melts at 184*5--18.5*5" (uncorr.). An ethereal extract of the liquid, when treated v i t h sodium carbonate, yields diieit rod ime th y lparatoluidin e, w hie h c rys ta 11 ises from a1 co hol in red, lustrous leaflets, and melts at 103.5-104°. I~~etanitrodiiiaethy~a?.atoluidisLe is also formed by the action of nitzous acid on dimethylparatoluidine, and is obtained as a dark red oil, which does not solidify at - 15".Amidodimetl~!l~aratoluil2ine, produced when the nitro-compound is reduced with tin and hydro- chloric acid, is a colourless oil, which boils a t 234" (uncorr.) under a pressure of 759 ma. ; the hydrochloride and mercurichloride A. G. B. VOL LXX. i. 11162 ABSTRACTS OF CHEMICAL PAPERS. melb at 192-193' and 205-206O respectively, whilst the picrate crystallises from alcohol in brownish-yellow prisms, and melts a t 150.5O. The action of boiling acetic anhydride durinq four hours converts the base into met hglethenyltolulglenamidine (Niementowski, Abstr., 1887, 937) ; the acetyl derivative of amidodimet~hylparntolu- idine is obtained by the action of glacial acetic acid during eight hours, and melts a t 111*5-112*5°. The phertylthiocarbainide crystallises in prisms, and melts a t 153-154' (uncorr.).In addition to amidodimethylparatoluidine, reduction of metanitro- dimethylparatoluidine gives rise to a compound which crystallises in white needles, and yields a picrate, cry stallking from amylic alcohol i n yellow leaflets, and melting a t 254.5' (uncorr.). When nitrous gas is led into a solution of dimethylparatoluidine in nitric acid, met hyldinitrotolylnitrosamine (Gattermann, Abstr., 1885, 975) is formed ; it is also obtained by the action of nitric acid on methyltolylnitrosamitie dissolved in glacial acetic acid. M. 0. F. Synthetical Use of Iodine Chloride. By M. KERSCHUAUM (Be?,., 1895,28, 2798-2804) .-us-Metaxylidine is converted by 1 mol. of iodine chloride, ICl, into orthoiodometaxylidi~te, [Me2 : NH, : I = 1 : 3 : 4 : 51 ; the base crystallises in colourless needles, melting at 65'. The hydrochloride is only sparingly soluble in water, whiIst the iritrate and sulphate are more readily soluble.The acetyl compourld forms lustrous white plates melting at 85'. The nitrile crystallises in yellowish needles, and melts at 135'. It has not yet been found possible to convert this substance by hydrolysis into an acid. When 2 mols. of iodine chloride react with metaxylidine, the iodo- derivative is accompanied by a small amount of tetramethylortho- diamidodiphenyl [Me4 : (NH2)2 = 3 : 5 : 3' : 5' : 2 : 2'1, which is formed from the xglidine by condensation. It crystallises in small, rhombic tablets, melts at 180°, and may be distilled in small quantities, almost without decomposition. The hydrochloride and sulphate are readily soluble ; the suitrate is sparingly soluble, and cr-ystallises in large, white prisms.The diacetyl compound forms small plates, and melts at 2 1 0 O . The base can readily be diazotised, and yields colouring matters with a- and ,%naphthol, &c. Tetranzethyld~henyli?~aide (tetra- ._TI methylcnrbazole), CsH2Me2<N -_ H>C6H2Me2, is formed when the t.et razo-solution is treated with potassium sulphide. It crystallises i u small plates, melts a t 128-129', and, like carbazole, forms a yellow solution in sulpliuric acid, turned green by nitric acid. It is iusolable in water, but readily soluble in alcohol, &c. The picrate forms reddish- browh needles. No analogous compounds have been obtained from other bases by the action of 2 mols.of iodine chloride. A. H. Amido-derivatives of Paraxylene. By FXANZ LUSTIG (Ber., 1895, 28, 2986--.29'34) .-Paramethylbenzylphthalimide, and paraxylylcne-exo-diphthalimide were obtained by treating withORGANIC CHK:MlSTRY. 163 potassium phthalimide the mixture of mono- nud di-bromoparaxylenes with the dibromide [ C6H,Me*CH2Br atid C,H,(C HIaBr)2] obtained by the bromination in sunlight of cold paraxylene ; they were separated by extraction with cold carbon bisulphide in which the monophtha- Iimide alone is soluble. The monophthalimide yields paramethyl- benzylphthalamic acid when hydrolysed with alcoholic potash, and paramethglhenzylamine when hydrolysed with a mixture of acetic and concentrated hydrochloric acids at 150-160''.Paramethylbenzyl- amine picrate melts a t 204" (Krober, Abstr., 1890,968, gives 194-199'), the acetyl derivative at 107-108' (Krober, 106.5"), and the benzoyl compound a t 137" (Krober, 125'). Metnnitropara?nethlllben~~lbenzamide, NO2.C6H3~~e*CH?.NEIBz, is ob- tained when the above benzoyl derivative is dissolved iu sulphuric acid, and then treated with a mixture of nitric a i d sulphnric acids. It crystallises iu colourless needles, melts at 145-147", and when hydrolysed with hydrochloric acid, yields benzoic acid and nitropara- wethylbenzy lainine hydrochloride ; the platixochloride, (No,*C,H,.NH,),,H,PtCl~, forms an orange red, crystalline powder, and decomposes at 231" ; the picrate crystallises in short, bright yellow needles, and meits and decomposes a t 211'.The benzojl compound, when reduced with ziiic and hydrochloric acid, according to Gabriel and Jansen's method (Abstr., 1890, 1442), yields ?netanLidopa.ram~~ylbe.lzxylbenxa.l?zide, which crystallises from water iri colourless needles, and melts at 113-115'. Since it is not converted into au anhydride by heating to 300", noF by distillation, i t is probable that the amide group is not in the ortho-position relatively to the CH2*NHBz-group. The arnido-compound must therefore be NH2*C,H3M.e*CH,~NHBz [= 3 : 4 : 13. The hydroc?iloricZe decom- poses aiid melts a t 237': the picrate turns browii, and melts at 170-171 ", and the chromate forms yellowish-red needles, which decompose a t 80". The beiizoyl compound, when hydrolysed with hydrochloric acid at 150°, yields m e t a m i d o p a r u n ~ c t l y l ~ e ~ ~ ~ y l a ~ ~ ~ hydrochloride ; this crystallises in colourless needles, melts with decomposition at 285", and yields a picrate, which also decomposes at 285'.Paraxylylene-exo-diphthalimide, C,H,(CH2*N:C8H,02)2, is iiisoluble in alcohol, ether, chloroform, benzene, and acetic acid, but crystallises from nitrobensene i n small, white needles ; i t melts at 279-280°, and, when hydrolysed with alcoholic potash, yields paraxyEyZerLe-exo- diphtlialamic acid, C6H,( CH2*N H*co*c,H,*cOoHj,, which, when heated t o 279", loses water, and is ronverted back again into the diphthalimide. Nitroparaxylene-exo-diphthalimide crystallises from nitrobenzene in colourless needles, and melts at 253-255'. Paraxylylene-exo-diamine hydrochloride, C6H4( CH2*NB2,HC1), + l&HIaO, obtained by the hydrolysis of the diphthalimide with con- centrated hydrochloric acid.crystallises in colourless needles ; the plalinocldoride decomposes at 250°, and the picrate, which crystallises in large, orange needles, at 232". n 2The tetrucetyl derirati.t.e, C6U4( CH2*NAcJ2, crystallises in colour- less needles and melts at 194', and the dibeuzoy1 derivative at Nit ropayaxy 1 y 1 ene- exo-diainitie h?jd r.ochlo ric7e, ob tai 11 ed from the nit ropi~raxylglene-exo-di p h thnl imi d e, c 1-3' s tal li ses with 1 t H,O, and decomposes when heated foi- some time a t 160'. The platiizochloricle decomposes a t 295", and the p i c m t e a t 237'. Nitroparax!jlyZene-exo-cZibenznmicle, obtained by the action of benzoic chloride on the nitro-base, crystallises in colourless needles, and melts a t 210*5-211'.J. J. S. 193-194'. Amido- derivatives of Diphenylarnine and their relation to Indamines and Azines. By RUDOLF NIF:IXKI (Ba-., 1895, 28, 2969-2981).-1. With KARL Ar,\f R N I ~ X D E R . - - ~ : 4-Dinitrodiphen3;I- arnine, NHPh*c,H,(NT),),, is best reduced by iron filings and 2 per cent. hydrochloric acid, the liquid being tinally treated with excess of sod i u m carbon ate. The d i am i do- co m po u i i ti for DI s b 1-0 w 11 is h need I e s and melts a t 130"; its salts are rcrg unstable ; it does not condense to an azine, exhibits the hehnviour of ;i met%-diamine, and yields a colourless diacetlyl dericatire me1 ting at 188". Warm alcoholic am- monium sulphide reduces the dinitro-compound partially to red izitra112idodi~henyZaiiiirie, NHPh*C,H,(NH,)*NO, [ 1 : 2 : 41 ; this melts a t 125", and yields a monacetyl derirntire melting at 163-164O.Nitrous acid converts i t into zt yellowish azimidt., N02*CGH3<- N>N, which melts at 107", and can be reduced with stannous chloride to the colourless amido-dei*ivatioe, which melts a t 159" and forms a platino- chloride, and n monacetyl derimtirc melting a t 266'. 11. With CARL SIMOlv.-1 : 2 : 4-Diamidodiphenylamine is oxidised by manganese dioxide in vci*j dilute ammoniacal solution to a yellow- ish-brown compound, C1tHIONzO, of undetermined constitution, melt- i n g a t 152'. 2 : 4 - D i n i t r o - 4 ' - h y d ~ o z ~ d ~ ~ i e n ~ l a i ~ i i ~ ~ e , cGH3( NO2),*NH*C6HA*OH, was prepared by the action of paramidophenol on dini trochlorobenzene ; it, is red, and melts at 190"; its yellow nionacefyl derivafiue melts a t 229'.It can be reduced by stannous chloride to the diaiiiido-cor~pound, which forms a rather unstable mono?ycZi*ochloride and readily oxidises in the presence of air to the dark-coloured diamidoindophenol, C,H,(NH,),*N:C,H~:O + 2H20 [(,NH2J2 : OH = 2 : 4 : 4'1, which melts a t 13.3' when anhydrous. If the hydrochloride is oxidised with manganese peroxide, yellow nniidohyd,.o.ryphcnazine, NII,*CeH,<~> C6H,*OH {NH, : OH = 3 : 3'1, is obtained; this melts at 268', its greenish- yellow diacetyl derivative at 258". 2 : 4- Dinmido-2'-h2/droxydzphenyl- anzine was prepared by reducing the correspondirlg dinitro-compound ; i t was not isolat,ed on account of its extreme instability, but was a t once oxidised, when it yielded 0.Fischer and Hepp's red 3-nmido- Bi phenazine, N&*C6H3< I >CeH4, melting a t 265'. N NPh N 111. With OTTO BA~R.-T be red dinitrodiphenylamine obtained byORGAN10 CHEMISTRY. 165 Witt (Ber., 11, 758) is shown t,o be the 2 : 4'-dinit,ro-componnd, N02*C6H4*NH*CEH4*N02. It can be made froin I : 4-mononitrodi- phenylamine, and so contains one nitro-group in the para-position ; that the second is in the ortho-position is shown by the conversion into a phcnazine, and other reactions described below. Partially reduced, it yields a nitramido-compound, which is reddish-brown with R shimmer of blue, and melts a t 144' ; this yields a, yellow wonacetyl derivative melting at 178"; with nitrous acid, i t yields a, yellow d r o a z i m i d e melting a t 2 3 9 O , that can be reduced with stannous chloride to a colonrless ctmido-compound melting at 134*5', the nam- c m t y l derivative of which melts at 200'.The diamido-compound obtained by complete reduction of dinitrodiphenylamine (Nietzki aiid Witt., Ber., 12, 1399) readily oxidises to the rcd nmidophenazine melting at 265'. Its acetyl derivative, when heated a t 120" wibh strong hydrochloric zcid, does not regeiiei*ate the diamido-base, as wns formerly supposed, but yields the ethenyl dericative, the acetyl derivative of which melts at 219'. IV. The following general conclusions are drawn as to the behaviour of the amidodiphenglamines.(1) To get an indamine, the para-posi- tions in both benzene nuclei must be occupied. (2) Azines are formed when a para-position is occupied in one nucleus, and an ortho-position in the other, and no iiidalnine is then formed as an intermediate pro- duct. If one nucleus has 110 substituting groups, or only one in the rneta-position, neither Ltn indamine nor an azine is formed. (3) 1f the ortho-positions in both nuclei are occupied, one of the occupying groups (NH, or OH) is lost, when the phenazine is formed. C. F. B. Preparation of Orthophenylenediamine. By OSCAR HINSBERG and FRITZ I(6,vrG (Bcr., 1395, 28, 2947).-Fifty grams OC orthonitr- aniline is dissolved in 100-150 C.C. oE boiling alcohol, 40 C.C. of 20 per cent. aqueous caustic soda added, and then zinc dust is intro- duced fairly rapidly in small portioiis a t a time.When the addition of zinc dust seems to produce no further action, 10 C.C. more caustic soda is :added, and tho addition of zinc dust continued as befow ; this proceeding should bc repeated ouce o r twice. I n about an hour, the reddish-jcllow colour of the solution will have changed to a pale brown, and the action will be complete. The solution is then filtered, the residue extracted twice with boiling alcohol, and the filtrate and washings evaporated in a current of hydrogen until all the alcohol has been driven OK The residue of orthophenylenedi- amirie is broken up when cold, dried on a porous plate, and distilled ; the yield is 90 per cent. of the theoretical. Other amidonitro-com- pounds can be reduced conveniently in the same manner ; not, how- ever, alkyl derivatives of orthonitraniline.C. F. B. Action of Ethylic Orthoformate on Primary Aromatic By X. WALTHER (J. pr. Chem., 1895, [23,52,429-430).- Amines.166 ABSTRAOTS OF CHEMICAL PAPERS. This reaction yields amidines very easily a t the temperature of the water bath in the majority of cases (compare Claisen, this vol., i, 91). The following were obtained : MethenyZdiphenl/Zamidine, silvery laniinze or prisms, m. p. 138-139". Metlienyldiortl~onitrophenylamidine, bril- liant, golden needles, m. p. 124--.12.3". n~etheiayZdimetanitrophenyE- nmidine, soft, felted needles, m. p. 19€!--199". Methen yldipayanityo- phenylaniidine, golden lamin=, m. p. 236--23i". Methenyldiorthotolyl- amidine, lnstroas, white laminae, or thick, transparent crystals, m.p. 149'. Jlethenyldiparatolylamidine, white laminae or large, transparent prisms, m. p. 141' ; the acetate cryatallises in wbite needles. Formazyl hydride, obtained by the action of ethylic orthoformate on pheayl- hjdrazine, forms violet crystals, m. p. 115"; from light petroleum, it separates as a red, crystalline mass (containing petroleum of crystal- lisation), which melts at 114'. Methenyldimetn b1.onzopI~en?llarnidin(J7 silvery lamina or stout prisms, m. p. 135". Methenyldityihomo- phenybamidine, long, white needles, m. p. 78". The compound from arnidoazobenzene forms long, brownish-red prisms or slender needles, and melts at 191-193"; that wit.h picramic acid is a moss-green powder, melting at 183-184', and is sbsolutely insoluble.A. G. B. Quinazine and Oxazine Colouring Matters. By RICHARD M~HLAU and KARL UHLMANN (AnnaZcn, 1895, 289, 90-130 ; compare Abstr., 1892, 887, and 1893, i, 44).-The authors accept the modifica- tion in the nomenclatnre of these colouring matters which has been put forward by Nietzlti and Bossi (loc. cit.), and they also adopt the expressions azime and azone for indamine and iridophenol derivatives respectively ; thus reference is made to phenylene-blue and a-naph- thol-blu e as nmidodiphena zime and d i methylamidophen onapht h- nzone. Dibromoclin2etl,7JIamidod~p~e~zazone, O:CsH~Brz:N*~GB,.NMe,, ob- tained by adding dimethylaniline (2 niols.) t o an alcoholic solution of dibromoquirioneclilorimide saturated a t 30", separates in green prisms which appear blue by transmitted light; when heated on platinum foil, it decomposes without undergoing fusion.The dye is insoluble in water, but dissolves sparingly in cold alcohol and ether, yielding greenish-blne s01utions, whilst hot alcoI101, aniline, and pyri- hine dissolve it readily. DimetLylamidodibromodiphenazone is hydro- lysed by boiling dilute hydrochloric acid, yielding ammonia, dimethjl- aniline, dibromoparamidophenol, dibromoquinone, mid quinone, whilst boiling caustic soda gives rise to hydroxydibromodiphenazone and dime thy 1 nni 1 in e. 4 3, 5 1 4 SodiiLon dibyomodipheii mo?? e-cjrt I( 01) ydi*ozycarboxylate, 4 3, 5 1 4 3 O:CGHzBrz:N*C,H,( ONa) *C 0 ONa, obtained on agitating dibromoquinonechlorimide (15 grams) dis- solved inether (300 c.c.) with n solution (135 c.c.) containing 5 grams of salicylic acid and 4.4 grams of caustic soda in 100 C.C.of water ; it dissolves readily in water and alcohol, ~ i e l d i n ~ c blue liquids, but is in- soluble in ether. Concentrated sulphuric acid dissolves it, formingORGAN10 CHEMISTRY. 167 an orange-yellow solution, which becomes purple, and ultimately colourless, on dilution with water. The acid is liberated in the form of a brownish-red powder, which dissolves sparingly in water and chloroform, being readily soluble in acetone, alcohol, and ether. Dibromodihydroxydiphenylam'necn~boxyZic acid, 4 3, 5 1 4 3 OH*C,H2Br,*NH*CsH3( OH) *COOH, the leuco-derivative of tho foregoing compound, is obtained from it by reduction with grape sugar or zinc and alkali ; it crystallises from acetone in needles, and melts and decomposes at 209".The substance is insoluble in water and chloroform, dissolving in ether, alcohol, pyridine, and acetone ; the solution i n caustic soda rapidly undergoes oxidation when exposed to air. The soditbm derivative of dibromohyc71.oxynaphtl~adiphenazone, 4 3, 5 1 4 0 : C6H$r2:N*CloH6*0 Na, produced by the action of dibromoquinonechlorimide on an alka- line solution of a-naphthol, crystallises in blue needles with green reflex; i t yields a blue solution with water and alcohol, but is inso- luble in ether. When the sodium derivative absorbs carbonic anhy- dride, dibromohydroxynaphthadiphenazone is produced ; this melts at 201' without decomposing. Hot dilute mineral acids resolve it into dibromoparamidophonol, dibromoquinone, and 1 : 4-amidonaphthol.Dibromo hydroz ypheny lhydroxynaphth y 1 nmine, the leuco- derirntive of the foregoing compound, is obtained by reducing it in alcoholic solu- tion with grape sugar and caustic soda; it crystallises in lustrous, white leaflets, and decomposes at 152' without melting. ClOH5<:> C6H3*& ez, is prepared by adding nitrosodimethylmetamidophenol hydrochloride (17 grams) to a boiling 10-15 per cent. solution of a-nnphthylamine hydrochloride (10 grams) in acetic acid containing 20 per cent. of water ; this operation yields the hydrochloride, which crystallises from boiling water acidified with a few drops of hydrochloric acid, in small needles; it appears green by transmitted, and violet by reflected light.The dye forms a blue solution in water, alcohol, and pyridine, and the solution in concentrated sulphuric acid is orange-red, becoming green and blue successively on dilution with water; owing to its coustitutional relation to the well-known dye, the authors refer to it as " methyl Nile blue." The base is liberated when caustic soda is added to the dye suspended in absolute alcohol until the colour is changed from blue to red; it crystallises in reddish-brown needles which contain water, and become anhydrous a t 120'. It decomposes before melting, and yields fluorescent liquids with common organic solvents. Keduction with zinc and hydrochloric acid converts the base into the zincochZoride of the lenco- derivative, dimeth yldiamidonaph thaphenoxazine, I Dimet ?A ylamidop henonap htli ozazime, 2 2168 ABSTRACTS OF CHEMICAL PAPERS.which crystallises in greenish-white needles ; i t is rapidly oxidised ou exposure to air. 4 k 4 Diethy Iumidophenonfiphtlioxazime, NH:C,oH,<O > C6H3*NEt2, which 2 the authcrs refer to as " ethyl Nile blue," is prepared from nitrosu- diethylmetamidophenol ; i t is obtained as the hydrochloride, which crjshllises in lustPous, green needles, appcaring blue by transmitted light; the salt is sparingly soluble in cold water, but dissolves readily in hot water, alcohol, and pyridine, yielding a blue solutiotl. The base crystallises in green needles, which are brown by transmitted light; it is insoluble in water, but dissolves in common organic sol- vents, yielding fluorescent liquids. Reduction with zinc and hydro- chloric acid gives rise to the zincoch Zoride of the leuco-derivative, crystallising in white needles, which dissolve in water and are readily oxidised on exposure to air.Tetramethylumidodiphenorazimium chloyide, 1 4 N 4 NMe2C l:C6H,e0> C6H3*NMe2, is obtained by adding nitrosodimethylmetamidophenol hydrochloride (20.2 grams) to a boiling solution of dimethylmetamidophenol (13.7 grams) in glacial acetic acid (150 grams) ; owing to its high degree of solubility in water, i t is convenient to convert the cliloride into the iodide by gradually adding hydrochloric acid in quantity sufficient to liberate the requisite amount of hydriodic acid from potassium iodide, and treating the boiling liquid with an aqueous solution of this salt. The iodide crystallises in blue needles having a green reflex, and contains lHzO, which is removed in a \vacuum ; the solu- tionb: in water, acetone, and chloroform are blue, and exhibit stroug brownish-red fluorescence.Tetrethy lamidodip hefiozazinziunt iodide is prepared from nit roso- diethylmetamidophenol hydrochloride by treating the chloride in the manner described ; it crystsllises from alcohol in blue needles having a vivid green reflex. The solutions of the iodide resemble tbosc of the foregoing methyl derivative. DimethyZamid~pl~~?zo~aaph~lzoaazo)le, 6:C,,H,<N>C,H3*~Me2, is ob- tained by adding nitrosodirnethylmetamidophenol hydrochloride (40 grams) to a boiling solution of a-naphthol (20 grams) in glacial acetic acid (200 grams) ; i t melts a t 244O, and crystallises from hot pyridine in large, green, lustrous prisms, which appear brownish-Ted in transmitted light.The dye is insoluble in water, but dissolves in common organic solvents, forming chei-ry-red solutions which exhibit scarlet fluorescence ; the solutions iu petroleum arid benzene are yellowish-red, and exhibit green fluorescence. The hydyochloride crystallises in blue needles. Diethylanzidophenonapl~thoxazone melts at 205", and cryst allises 2 1 0 2ORGANIC CHESIISTRP. 165 from hot pyridine i n prisms which appear brownish-rcd by trans- mitted, green by reflected, light ; the solutions of the dye in orgnnic solvents resemble those of t!ie foregoing methyl derivasive. It dia- solves in concentrated sulpliuric acid with a reddish-brown colors- tion, which becomes blue on dilution, and the solution in concen- trated hydrochloric acid is yellowish-brown, and yields a blue Iwecipitate when diluted with water.The absorption spectra of the foregoing dyes have beeii examined, and are collected in a diagram which appears in the original paper. 31. 0. F. Action of Hypochlorous acid on Diazo-compounds. By THEODOR ZINCK E (Ber., 1895, 28, 29 i8-'L951).-Paradiazobeiizene- sulphonic mid can be oxidised with a solution of bleaching pomdet., the solutions being kept cool with ice, to an acid, SO,H.C,H,.N,O,H ; evidence of the formation of intermediate products mas obtained. The acid crystallises in reddish-yellow needles, which explode feebly when heated; the sodium, with H,O, barium, and d v e r salts are respectively brownish-red, yellowish-white, and brownish-yellow.The acid possibly has the constitution, S03H*C6H,*N(OH).N0,, but i t is reduced by stannous chloride to Nietzki and L e ~ ~ h ' s di;miido- benzeuesulphonic acid (Abstr., 1889, 144). C. F. B. New Base from Isobutylidenephenylhydrazine. By KARL BRUKNER (&Ionatsh., 1895, 16, 849--865).-Wliilst investigating the action of alcoholic zinc chlo~ide on isobutylidenepheiiylliydrazine (compare Abstr., 1895, i, 475), the author has isolated a new base by means of its compound with zinc chloride (Cl,,HllN)2,ZnC12 + 4 EtHO. This ciystallises in pale yellow, hexagoniil plates, inelts at 170--172O, dissolves readily i n benzcne, alcohol, crid ether, and niay be reprecipitated by the addition of light petroleum ; it, is tlecom- posed by water: anci, wlien heated, jields dimet!ijlindolc. The free base, (C,oH,lN),, is obtained by tlic additioii of potassinm hydmxitle t o a solution of the above-described conipound with zinc chloide, nud subsequent extraction with ether and recrystallisation from hot benzene.It dissolvcs in all ordinary oiganic solvents, and in mineral acids, and melts a t 215-216O. The picrate, Cl,,Hi1N,C6H3N307, is sparingly soluble in ether, biit dissolvcs readily in alcohol and benzene, crjst allises in rhombic scales, and mclts at 134-135.5". The Lromo-derivative, Cl0€T,OEB~,, melts a t l80--18lo. By the action of sodium amalgam on the base, another base of tlie formula C,,H13N or C,,H,,,N is obtahied; this cr-jst:lllises i n long needles, iuelts at :go. aiid fer~iis a platinocl~loride, wliicl: melts and deconi- poses a t 205". G.1'. 111. Preparation of Ketones from Aromatic Propenyl (GH : CHMe) Derivatives. By CARL HELL (Ber., 1895, 28, 2835--2838).--l'he compounds previously obtained from sodium ethoxide and isoeugenol ethyl and methyl ether dibromides (Abstr., 1895, i, 657) are not alcohols, OH*CR:CHRlle or CHR:CMe*OH, but ketones, R.CO*CH,Me, as the7 readily yield phenylhydrazones; that from t h e ethyl ether melts170 ABSTRACTS OF OHEMICAL PAPERS. a t S6--87", whilst the rnethyZ derivative melts a t 1U2-103°. By the action of bromine on the ketones, monobroinoketones are formed. Anethoi'l dibromide and bromanetho51 dibromide, by the action of chromic anhydride and glacial acetic acid, yield bromo-ketones, which are also formed when the products of the interaction of sodium ethoxide, anethoil dibromide, and bromanethoil dibromide respec- tively are brominated ; these compounds are therefore a-ketones.The conversion of an aromatic propenylic dibromide into an a-ketone by means of sodium ethoxide takes place in four stages : (1) R*CHBr*CHBrMe = R*CBr:CHMe + HBr, (2) R*CBr:CHMe +NaOEt = R*C(OEt):CHMe + KaBr, (3) RC(0Et):CBMe + H,O = RG(0H):CHMe + EtOH, (4) R*C(OH):CHMe = R.CO*CH2Me. J. B. T. Etherification of Aromatic Acids. By VICTOR MEYER (Ber., 1895, 28, 2773-2775).-In examining the constitution of aromatic acids by the etherification method, it is impossible to carry out the process in all cases at a low temperature, because some acids, which are only slight'ly soluble in alcoholic hydrogen chloride, do not, undergo the reaction under these conditions. Moreover, the method of etherificacion by means of a current of hydrogen chloride passed into a boiling alcoholic solution cannot be generally used, because the characteristic differences in the behavionr of acids are often not shown when this process is employed.All simple acids, which do not contain more than two phenyi groups, behave in the characteristic wily when they are boiled for 3-5 bours with alcohol containing 3 per cent. of hydrcgen chloride (Fischer'a method). More complex acids must be treated i n solution in boiling alcohol with a current of hydrogen chloride. Several of the methyl derivatives of benzoic acid appear to behave in a n exceptional manner, which is at present undergoing investigation.A. H. Diamidobenzoic acids. By CARL HAEUSEHMANN and H. TEICHMANX (J.pr. Chem., 1895, [2], 52, 428-429; compare Abstr., 1895, i, 531). --E'thyZic-2 : 5-din.midobenzonte is prepared from ethylic 2 : 5-dinitro- benzoate in the manner already described (Zoc. cif.). It is n yellowish powder, melts at 50.5-51°, and dissolves somewhat easily in hot water, and very easily iii alcohol and benzene. In dilute ethereal solution, it has a greenish fluorescence. The hydmchloride, C6H3(NH2),*CO0Et,2HCl, and sulpltate are described. A. G. B. Products of the Reduction of Phenylbutyrolactone and Phenylparaconic acid. By RUDOLPH FITTIG, ADOLF WOLFY, and JOHN SHIELDS (Annulen, 1895,288,203-209).-When phenylbutyro- lactone is reduced with hydriodic acid, phenylbutjric acid is formed ; this substance melts a t 51.7", and not a t 47*5", a s stated by J a p e .The calcium salt contains 3H20, and ci-ystallises from water in long zeedles ; i t undergoes no change at 120". Sodium amalgam has butORQANIO CHEMISTRY. 171 a slight action on a hot acid solution of phenylbutyrolactone ; acetic acid and zinc dust give rise to a small proportion of phenylbutyric acid, 85 per cent. of the lactone employed being recovered unchanged. Tin and hydrochloric acid give rise to phenylbutyric acid, which is, for the most part, converted into the ethylic salt, the reaction being studied in alcoholic solut,ion; 37 per cent. of the lactone remains unaltered . Hydriodic acid converts phenylparaconic acid into benzylsuccinic acid, phenylbutyric acid being also formed as a secondary product.M. 0. F. Action of Sodium Ethoxide on Phenylbutyrolactone. By RUDOLPH FiTTrG, ADOLF WOLPF. and RUDOLPH LESSER (Annalen, 1895, 288,192-202 ;'compare Abstr;, 1892, 813).--D~he~yldib~tyrolactone~ is obtained by heating phenylbutyro- co ? $: H 2.C H, C HPh.0 >C:C<CB,-CHPh' lactone with sodium ethoxide and alcohol for 15-18 hours in a reflux apparatus ; it crystallises from alcohol in rosette4 of colourless needles, arid melts a t 83-84'. The substance is unsaturated, and gives rise to three distinct compounds on treatment with bromine in carbon bisnlphide solution ; they melt at log', 150-151", and 117-118° respectively. Diphenyloxetonecarboxy lic acid, CzoHzoO,, is obtained by heating the dilactone with aqueous sodium hydroxide and some alcohol ; i t decom- poses at 147-148'.The barium salt decomposes above loo", the calcium salt is anhydrous, and the silver salt becomes only slightly coloured on exposure to light. Diphenyloxetone, C,9H2002, is produced on heating the foregoing acid with dilute hydrochloric acid in a reflux apparatus, and is also slowly formed when water alone is used ; it, is a neutral oil, which undergoes slight decomposition when heated. Diphenyloxetone dissolves readily in organic sulvents, with the exception of petroleum, which precipi- tates it completely from the solutim i n benzene ; i t does not reduce an ammoniacal silver solution, and yields no solid derivative with sodium hxdrogen sulphite. Action of Ethylic Iodide on Potassium p-Resorcylate.By GEORG GRECOR (Jlonatsh., 1895, 16, S81--89~).--~tho~~-/3-resorcylic acid, C,K,O,*OEt, is formed, together with several neutral substances, by the action of ethylic iodide on potassium ,%resorcylate in alcoholic solution. I t crjstallises in white needles, melts a t 154O, and is sparingly soluble in cald water, but dissolves more readily i n hot water, alcoliol, ether, and benzene. Tlie sodilim salt, C,H,NaO' + H20, crjstallises in scales ; tlie barizim salt is anhydrous, and crystal- lises in small needles ; the silrei. salt contains 10HzO ; the lend salt, (CgHg04)2Pb + 8H20, and other salts are also described. From the behnviour of the ethylic salt towards dilute potassium hydroxide solution, the authoi- concludes that the formula is 31.0. F. CHz*CO c o < ~ ~ - - ~ ~ > CHz'C(oEt) CGOOH or OEt.C<cH.C,>C-COOH,1'72 ABSTRACITS OF OHEMIOAL PAPERS. being derived from the secondary tertiary form, and not from t h e bi-tertiary form of resorcinol. He also suggests that the acid formed by the action of ethylic iodide on potassium-f3-resorcyl~te perhaps consists of two isomeric acids, which are not easily separated (corn- pare Tiernann and Parrisius, Abstr., 1831, 271). G. T. M. Halogen Derivatives of the Sulphonamides. By J. H. KASTLE ( A m e r . Chem. J., 1893,17, 704--708).-Dichlorobenzetiesulphonamide is readily prepared by dissolving beiizctiesulphonarnide in the smallest quttntit1 of soda (1 : LO), a rapid current of chlorine is passed through tlie solution, and the first portion of precipitabe, which contains much unchanged sulphonamide, is removed, tlie filtrate treated wish chlorine, tlic crude product washed wit,h hot water by dccnntation, dissolved in alcohol, and precipitated by t.he addition of water.It is extremely stable. When heated at about l;Oo, i t is resolved into chlorine, nitrogen, hydrogen chloridc, and benzenesulphonic chloride, the latter being produced in almost theoretical quantity. By the action of bromine wst e r on parac~iloroLenzenesulphollamide in soda solution, a yellow crjstalline d i b ~ o m i d e is formed. J. 13. T. Formation of Indigo in Plants of the Order Indigofem.. Bg C. J. VAS LOOKERFN and P . J. VAX DER VEEN (Landw. V e r s z ~ I i ~ : Stat., 1895, 46, 249--258).-See this vol., ii, 207. Coloured Aromatic Thioketones.By LvDwrG GATTE RMAXS (ller., 1895, 28, 2S69--28T'7).--Yaradimcthoxythiobenzophe~io~ie, C S ( C G H ~ * O ~ ~ ~ C ) ~ , is prepared by the interaction of anisoil, thio- mrbonjl chloride, and aluminium chloride. and crystallises from alcohol in long, ds1.k blue needles melting a t 115'. Solutions of tlie kct,one a r e of : L bluish-violet colonr ; its constitution is shown by its conversion into ~imet~oxybenzophcnone [CO OMe = 1 : 41 when treated with alcoholic potash. Attempts to prepare derivatives of the tliio-ketone wwc uiisuccessful on account of the readiness with which the sulphur is elimin~ted. P a r a d i e t h o ~ ~ t h i o b e r ~ ~ ~ ~ ~ e ? z ~ n e , CS (C,H,*OEt),, prepared in n similar nianncr from pheneto'il, crystallises in sky blue plates, melts at 11 8-119", and.with alcoholic potiish, is converted into paradi- et hoxybenzophenone. The molecular weight was determined by t h e cryoscopic method in naphthalene solution. Parndipropxythio- bc~zzopl~eno~te, C S(C6H4*OPra)p, from propoxybenzenc, crjstallises in blue plates and iiiclts a t 105-1C6'. Puradipi.o~oxybe?i~0~72enoizc, CO(C,H,*OPra),, formed by the action of alcoliolic potash on t h e pre- cedixg ccmpouiid, crystallises in colourless plates, and melts at 1-27'. 'l'lie ozime is deposited in colourless needles nielt,ing a t 113'. Diethozy- dirnethyZfhiobe),zoph~none, CS(CGH,n/le*OEt), [Me : OEt = 1 : 21, prc- pared from ortlioetboxymethyl benzene, me1 t s at 117-1 1S0, and gives a violet solution in alcohol, from wliich i t is deposited in olive-green needles with a steel-blue reflex ; from light petrolenm it crystsllises i n elongated steel-blue crgstsls.Diethoxydimethyl- benzophemne, CO(CGH,Me*O~t), [Me : OEt = 1 : 21, crystallises inOROANlC CHEMISTRJ-. l'i3 colourless, silky, lustrous needles melting a t 105-106°. Dimethowy- c7imeth2/Z~lriobet,zop~/enone, CS(CG€I,Me*OMe), [Me : OMe = 1 : 2 1: could not, be ccmpletely separated from the ketone, with which it appears t o cryst(a1lise ; the long, strel-blue needles obtained from its solution in light petroleum, dis3olre with a violet coloration, and m (3 1 t a t 1 14". [Cl:OMe = 1 : 21, from orthochloraniso'il, crystallises in moss- green needles, melts at 178-179", and dissolves with a violet colour. The h.eto?te, CO(C6H,C1*OMe),, crystallises in colourless needles, and melts at 183-184".UiL'l2lorotlietho.ryt~iiobenrophenoize, CS(C,H,Cl*OEt), [Cl : OEt = 1 : 217 crystallises in dark green needles, melts at 141-142", and jields blue-violet solutions. The ketone, CO(C6H,CI*OEt)27 ciystaliises in colonrless needles, and melts at 182-123". Dibroi~zodi.nzethot~th~ob~n~ophenne, CS(C6H3Br*OMe)2 [Er : OMe = 1 : 21, from orthobromaniso'il, dissolves in alcohol with i t violet coloui*, and crystallises mith ditficulty in dark green needles melting at 189-190". The keforLe, CO(C6H3Br.0~~e)Z, crystdhses in coloui-less needles melting at 180-181". The precediug tkioketones, when heated at 200-220" with finely divided copper, in an atmosphere of carbonic anhydride, yield cupric sulphide and derivatives of tetrapheiiyletb~lene. l'etrnmeth~sytetra- phenylefhy7eiie, C2(C6H,*O~e)~, from paradimethoxSthiobenzophenonc., crystsllises from glacial acetic acid in colourless needleswith a pale blue fluorescence, melts a t 181- 18.Lo, and, in presence of bromine vapour or lead peroxide, yields a blue compound which has not yet been isolated.By the further action of lead peroxide at the ordinary teni- perature, the conipound O< I , is obtained, it forms long, colourless crystals melting at, 188-189". Tetrethoxytetmphenyl- efhylene, C2( C6HdOE1,)~, resembles the met hoxp-derivative, crystallises in long needles with an intense green fluorescence, melts a t 120-121", and, when reduced with sodium in alcoholic solution, yields tetr- cthoxytet~~~henyZetha.lze, C,H,(C,H,*OEt),, which crpstallises in colour- less needles melting at 163--164".l'etrclpropoxytetr~~~~en?llethylcne, Cz(C6Hd*OPra)J, from dipropoxythiobenzophenorie, crystnllises in green, fluorescent needles, melts at 139-140°, and becomes blue when oxidised. T~tranzefhoxytetraii~eth~ltet~aphen~lethyleiie, Cz(C6H3hle*O&Ie)4 [Me : OMe = 1 : 21, cqstalliscs in fluorescent needlcs melting at 195" ; the corresponding ethoxy-dmiratke, C,(C,H,~fe*OEt),, is deposited from a mixture of p j ridine and alcohol in green, fluorescent plates melting at 214' ; both compounds become blue when oxidised. Tetrachlorotet~umetholr.ytetra- phenyZethyZeize, CP(C6H3C1-Ohle)4 [c1 : OMe = 1 : 21, crjstsllises from glacial acetic acid in coloiirless needles nieltiiig at 257". The ethoxy- dcrivatirr, C:,(C,€I,CI.OEt),, is deposited from benzene in colou~leEs, feathery crystals melting at 258-259". Neither of these coniponnds becomes blue when osidised.The compound, C2(C6H4-Nh!te2),, is prepared by the action of copper on the corresponding thioketone and crjstallises from acetone, on the addition of alcoliol, in greenish- J ellow needles, Jrom benzene in highly lustrous prisms, melting at Dic hloTodii i i et h OR: y t hi0 b enzoph enone, c s ( C, H,C 1 OM e ) c (C6H,*Ohle), C(C6EIdo0Me)?174 ABSTRACTS OF CHEMICAL PAPERS. 310-315'. It is a strong base, which dissolves readily in dilute acids, and, on adding lead peroxide to its acetic acid solution, gives a dull, unstable violet coloration. Bergreen prepared a reddish-brown oil by the interaction of benzene, thiocarbonyl chloride, and aluminium chloride ; this experi- ment has been repeated, but a blue, oily liquid, consisting of a mixture of ketone and thioketone was obtained; these could not be separated.Other attempts to prepare thiobenzophenone by the action of hydrogen sulphide on benzopheuoneanilide, to which a little hydrogen chloride had been added, and by the interaction of phos- phorus pentasulphide in benzene solution, and benzophenone, were also unsuccessful ; the latter method gave a product containing 50 per cent. of the thioketone, as shown by the production of tetra- phenylethylene, which is not formed by heating copper with benzo- phenone. The colour of tbe above thioketones, aud also that of thiacetophenone, shows that the group CS is a chromophore.J. B. T. By GUIDO GOLDSCHMIEDT and FKAKZ SCHRANZBOFEK (Monntsh., 1895, 16, 807- 827) .-Thepken ylhydrazone of fluorenone (diorthodiphenylene ketone) is obtaiued when an alcoholic solution of fluorenone is heated in a water bath with a slight excess of phenylhgdraziile, and the product, is subsequentsly acidified with acetic acid. On cooling, the compound separates in beautiful, yellow needles, and these, when recrystallised from alcohol form long prisms which melt atd 151-151*5". When dry chlorine is led into a solution of the ketone in chloroform, the following two well characterised chlorinated derivatives arc ob- tained :-ChloroJEuorenone cr~stallises from dilute alcohol in long, yellow needles, melts at 115', and forms a phenylhydmzone which melts at 139-141'.p-Dic7iZoroPuoreno)ie crystallisex from alcohol i n beauti- ful, long, yellow needles, melts a t 188--189' (compare Hodgkinson and Matthews, Trans., 1883, 165), and forms a phenglli ydrazone, Hydrazones of Fluorenone and its Derivatives. CI,H,Cl,N,HPh, which crystallises in yelIow needles, and melts a t 185-1%". /3-X b,.omo~uorelaonepheiiylhydrazone melts a t 190'. 6-DibTornoJluorenone melts at 262', is yellow, and forms a phenylhyd~azone melting at 252". n'L'tro~uoreiionephenylhydrazone melts a t 210-214'. a- DinitrofEuorr- ?ro?te2lhenyllL~drazone melts a t 257-258'. /3- Dinitroj€uIwewone forms yellow needles, melts a t 2dO0, and yields aphenylhydrazone melting at The results obtained i n t h i s investi,aation, taken in conjunction with the fact that ellagic acid, a fluorenone derivative, does not yield a hydrazone, have not thrown light on the formation of hydrazones, as expected by the authors.The Phthalein Groups. By RICHARD MEYEIC and HEISRICH MEVER 277-2828, G. T. M. (Ber., 1895, 28, 2959-$96%).iExperiments undertaken to ascertain whether quinolphthalein, CO<- C6H4 ->C<C,tr,toH,>O, 'eH3(OH) is related to fluoran, gave a negative result,, and i t was fouzd impossible to decideORCIANIC CHEMISTRY. 175 as to t,he structure of this substance. When it is heated with strong aqueous ammonia, it yields a colourless irnido-compound, an imido-group having been sabstituted for one of the oxygen atoms ; this compound decomposes above 3 10' withcut melting. The phthale'in further yields a colourless &benzoate melting at 252-253".Substitution Products of the Carbonates and Phosphates of dhphthol and p-Naphthol : Preparation of 1 : 4-Chloronaph- tho1 and 1 : 4-Bromonaphthol. By F R ~ D ~ R I C REVERDIN and HUGO KA(JFFMANN (Bey., 1895, 28, 5049-3058 ; compare Abstr., 1895, i, 151).-4-Nitm-a-~aaphthylic caybonate, (N0,*C,oH,*O)2C0, is obtained by the action of nitric acid on a-naphthylic carbonate dissolved in glacial acetic acid ; according to the quantity of the diluent employed, it is obtained in a form which crystallises from benzene in pale yellow needles melting at 148", or as the modification separating in yellowish needles which melt a t 2 1 2 O . Both substances yield 1 : 4-nitronaphthol when hydrolysed with alcoholic potash, and in the case of the niodifi- cation melting at 148", a-naphthol is produced at the same time.The dichEoricZe of a-naphthylic carbonate (CloH,CI,O),CO, is formed when chlorine is led into a cold solntioii of a-naphthylic carbonate in benzene or carbon tetrachloride ; it crystallises in white needles, which melt and decompose at 200'. 4-Chlo~o-a-naphthylic carbonate is pro- duced when this substance is distilled or treated in chloroform solution with bases or acetic anhydride ; i t is also obtained by passing chlorine into a hot solution of a-naphthylic carbonate i n glacial acetic acid or a cold solution of this substance in carbon tetrachloride containitlg 5 per cent. of antimony trichloride. The compound is sparingly soluble in most solvents, and crystallises from benzene in white needles, which melt at 2213".1 : 4-ChZo~onaphthoI is obtained by hydrolysing chloro-a-naph thylic carbonate with alcoholic potash ; at 100' i t sublimes in long, white needles, melting a t 116', and is readily solid.de in organic solvents. A blue precipitate is formed when bleaching powder or ferric chloride is added to the neutral aqueous solution, and its bebaviour in alkaline solution towards chloroform, carbon tetrachloride, and formaldehyde, resembles that of naphthol ; it reacts with sodium nitrite and hydro- chloric acid, and yields dyes with diazo-compounds. Tbe acetyl deriva- tive melts a t 44", aiid the picrate a t 171'. 1 :4-Chloronaphthol develops a, blue coloration with dimethylparaphenylenediamine ; 1 : 2 : 4-di- chloronaphthol is produced when chlorine is passed into the solution in glacial acetic acid.4-Bromo-a-naphthylic carbonate crystallises from benzeue and melts at 214O. When hydrolysed with alcoholic potash, it yields 1 : 4-bromo- naph.thol, which melts at 127-12$-', and yields spicrafe and an acetyi derirative which melt a t 167" aud 51' respectively ; 1 : 4-bromonaph- tho1 has also been obtained by the action of boiling water on diazotised 1 : 4-bromonaphtbylamine, and when treated with bromine in glacial acetic acid solutionit yields 1 : 2 : 4-dibrornonaphthol, which melts at 105.5'. The behnviour of a-uaphthylic phosphate (m. p. 149-150') closely resembles that of a-naphthylic carbonate, and the substance yields a C. F. B.176 ABSTRACTS OF OHEMIOAL PAPERS. sulphonic acid, the sodium salt of which, on hydrolysis, yields 1 : 4- naph tholsulphonic acid and sul p honaph thy1 phos ph' !nate.l-nromo-~-naphfhllEic carbonate is obtained by the action of phos- gene on an alkaline solution of 1 : 2-bromonaphthol ; it ci*~-stallises from ethylic acetate in white needles, and melts at 188-189°. 1 -Iotio-P-?i(rphth ylic cnrboiin te crystal lises in \v hite needles, which become yellow on exposuye to ail*, and melt a t 188-1&9". Paranthracene or Dianthracene. A Polymeric Modification of Anthracene. By WILTJAM Rt. ORNCORFF Hnd F. K. CAMERON (Arne?-. Chem. J., 1S95, 17, 658--681).-The paranthracene was pre- pared by the action of sunlight on anthracene suspended in benzene and xjlene ; the operation is expedited by shaking occasionally to remove deposited material from the glass.The product was purified by extract,ion with alcohol, ethylic acetate, and benzene, and the residue crjstallised rcpe:itedly from benzene in an extrnction appa- ratus. l)imethylaiiline is unsuitable as a solvent. Paranthracene crystallises in thin plates, which arc fully described, belonging to the ortho-ibhonibic system n : b : c = 0.6762 : 1 : 1.5731 ; i t melts a t 242--244", being quantitatively coiiverted into antliracene ; the same change takes place by prolonged heating aloiie a t 230-235", or in boil- ilig naplithdene (21 S o ) , arid partially in boiling dimethylaniline (192*), and in aniline (182'). The compound does not fluoresce either in solution or in the solid statc. The sp. gr. = 1.265 a t 27"/4", and that of anthrncene = 1.250 ; the following numbers express the solubility of paranthracenc i n the solvents (100 parts) a t their respective boiling points : ethyIenic bromide, 0.22i3 ;.pyridine, 1.106 : aniso'il, 1.46; plieneto'il, 1.3. The molecular weight was determined by the boiling point method in the above solvents ; the values are, in ethylenic bromide, 179-346, average of 10 determinations, 285 ; in pyridine, ;317-397, average of 9 determinations, 3.54 ; in aniso'il, 331-397, average of 13 determinations, 362 ; in phenetoil, 329-396, average of 8 determinations, 355. Elb's conclusion that the mole- cular weight of paranthracene is twice t h a t of anthracene is thus confirmed, and it is saggested that t h i s should be expressed by the name dianthracene. Attempts to prepare paranthracene by dropping a little of it into nielted nnthracene a t 215-5240': by the action on it of hydrogen chloride, either aqueous or alcoholic, a t 220' ; by treatment of anthra- cene dibromide with zinc dust; by heating anthracene with sodium amalgam and alcoliol, or with sodium and benzene, were all unsuc- cessful.Anthraquinone, dihjdroanthracene, dichloranthracenc, phenanthrene, retene, camphor, and phenjlacridine were unchauged after exposure to light during several weeks ; anthranol, in benzene solution, under these conditions, yielded an almost colourless product, which becomes browu and melts a t 265-270" ; it is insoluble in boil- ing alkali and less soluble iii other media than anthranol. Acridine, in solution, when exposed to sunlight, gave a, pale yellow, crystalline compound, which could not be dissolved, and which does not form salts with acids ; when rapidly heated, it melts a t 276", when slowly heated it volatilises, without melting, a t %0°, and, in both cases, is M.0. P.ORGlAKIC CHEMISTRY. 177 convci-ted i n t o acridine ; the same change is produced by prolonged boiling in rarious liquids. Graeba and Liebermsnn’s formula is accepted for anthrscene, with the modification that if von Baeyer’s centric formula is adopted for benzene and its carboxylic acids, the benzene nuclei in anthraceue must, from its synthetical forqation, be repmsented in the same manner ; the stability of anthraquinone and dihydroanthracene towards oxidising and reducing agents respectively is in accord with this.The difference in behaviour of anthracene and phenanthracene support the view that the former contains two benzene nuclei and two ./-carbon atoms (paraffindid residue), and that t h e latter contains three benzene nuclei. With the above modifica- tions, Linebarger’s formiila for paranthracme is accepted ; its forma- tion is ascribed to the tendency to form rings of six members, the para-linkage of the ycar’oon atoms being resolved. By EDR-A~~D KREJIERS (Asner. C‘hem. J., 1895, 17, 692-697) .--The limoiiene employed boiled a t 174*5--175O, and was prepared by the fractionation of commercial ‘‘ carvene ” ; [a]:: = + 120*466O, whilst the value given by Wnllnch and Conradi is 106.8 . The specific rotatory power of limonene solutions of varying content, in ordinary and absolute alcohol, chloroform, and glacial acetic acid, was determined ; in the case of absolute alcohol and chloroform, the rotatory power decreases with fair regularity as the proportion of solvent rises. For solutions containing 10, 50, and 90 per cent.[a],, = 1L3*43U3 and 115.673’; 115.690’’ and 117.604° ; 118.036’and 118.733O respectirely. The fractions boiling a t 172+5-177° have all a lower refractive power than limonene except the one boil- ing at 174-174.5O, for which [a]D = 1.20 672’. Lirnonane bydro- chloride, when treated with water in a sealed tube at the ordinary temperature, is slowly converted into terpene hydrate, which, when heated abore its melting point, i 3 resdved into terpene. When exposed t o air, the oily mother liquid darkens, and the crystals gradually dissoIve in it.Nitration of Menthone. By MICHAEL I. KONOYALOE’P (Compt. T e d . , 1895, 121, 652-653).--Nitric acid of sp. gr. 1.075 acts very readily on menthone, CloHlsO, in sealed tubes at looo, and yields nitro- menthone, NO2*ClOH1,0, a yellowish liquid with an odour recalliug that of menthone. It boils arid slight!y decomposes at 135-140’ under a pressure of 15 mm. ; sp. gr. = 1.0856 a t Oo and 1.0591 a t ZOO. It is insoluble in water, concentrated hydrochloric acid, and sodium carbonate solution, and only slightly soluble in concentrated aqueous potash. With sodium ethoxide in presence of alcohol, nitromenthone yields il salt which, when decomposed by sulphuric acid, gives A liquid acid of the composition C,,H,,R’O~. It boils and slightly dc- composes at 190-195’ u d e r a pressure of 13 mm., and dissolves readily in sodium wrbonate solution, but not in water or Lydro- chloric acid.When reduced, nitromenthone yields a basic compound, and it seems to have the constit.ution J. B. T. Limonene and its Derivatives. J. B. T. {CPr.NO2: C O : CBz : CHMe : CH, : CH, = 1: 2 : 3 : 4: 5: 63, VOL. r.xx, i. 0178 ABSTRAOTS OF OHEBIICAL PAPERS. the constitution of the nitro-acid being CHMe2*CH ( SOZ)*CH,*CH,*CHMe*C H2*C 0 OH. C. H. R. Action of Silver Oxide on Dibromomenthylamine. Menthyl- hydrazine. BgNrc. KIJXE~G (J. pr. Ghem., 1895, [2], 52, 424-426). -Menthoneiizentlt?$hydrmone, CloHlgN*N:CloH'18, is produced by adding moist silver oxide to dibromomentliylamitie, warmiug at 50-60°, and extracting with ether.It crystallises in long, greenish-yellow needles, and melts a t 92-93'. It is laevorotatory in solution ([z]~ - - -36G.5O). Boiling dilute hydrochloric acid converts it into menthoue and menth yf hy d raziiie hydrochloride, C ,,H 19N2H3C1, iv hich dissolves in water, alcohol, and ether, and is kevorotatory ( [ x ] ~ = -46.05'). nr:1ithyZhyd,.azine is a liquid which boils at 235-240°, and by oxidation yields menthnize, CIOHZ0, which boils between 165-169". A. G. B. Action of Hydroxylamine on I-Dibromomenthylamine. By NIC. KIJNER (J. pr. Chem., 2895, [2], 52, 426427).-The author has published (J. Russ. Chenz. SOC., 1894, 26, ii, 132) the result of the reaction between hydroxylaniitie hydrochloride and iiibi-omo- meuthyla~nine. The change occurs in the sense of the equation CI0Hl9*NBr2 + NHz*OH = CI,H,,Br + N2 + H20 + HBr.It is poiiit,ed out that this reaction is analogous to that between hydroxylamine and diclilorornetlijlamine, to which nttei tion has just been called by Bamberger and Renauld (8bstr., 1895, i, 494). A. G. B. Partial Synthesis of Camphor : Constitution of Camphoric acid and Camphorone. By JULICS BrtEDr and &I. VON ROSEX~ERG (Annalen, 1895, 289, 1---14).-Honzocamnpl~o,-ic acid is the name by which the authors refei- to hydroxycamphocarboxvlic acid, C11H1804, obtained by Hallei- (Dissertatiow, Nanry, 1879, 29) on hydrolysing cganocamphor with aqueous caustic potash ; the siluer salt is a white powder dissolring with difficulty i n Mttter, and the calcinm salt contains 7H20, which is lost at 140'.When the dry calcium salt of homocamphoric acid is distilIed in an atmosphere of carbonic anhydride, camphor is produced in y uantity amounting to 70 per cent. of the theoretical yield ; camphor obtained in this way is in every respect identical with ordinary dextro-camphor. The authors discuss the constitution of cnmphoric acid and cam- phcwone. M. 0. F. Tiemann's Formulae for Camphor and Campholenic acid. By JULIUS BREDT (Annaleit, 1895, 289, 15-1Y).--The author draws attention to the identity of his expression for the constitution of camphor (Abstr., 1894, i, 141) with the formula advocated by Tiemann (Abstr., 1895, i, 426 and 675). Etherification and Hydrolysis. By JULIUS W, BKGIIL (Be,.., 1895, 28, 2868-2869).-A4 question of priority with Wegscheider (this vol., i, 95) as to the discovery of the fact tlist, by the action of 11.0. F.ORGANIC OHEMISTRY. 179 hydrogen chloride and alcohol, the carboxyl group which is most readily etherified is subsequently also the most easily hydrolysed ; this was shown three years ago by the author in the case of cam- pboric acid. J. B. T. Acids formed by Oxidation of inactive Campholenic acid. By AUGusTE B~HAL (Compt. rend., 1895, 121, 465-468).-The acid, C6HloOr, obtained by the action of nitric acid on inactive campholenic acid (this vol., i, 55) is identical with the unsymmetrical dimethyl- snccinic acid, COOH*CMe2*CH2*COOH, obtained by the interaction of ethylic bromisobutyrate and ethylic sodiomalonate. I t melts at 143-144'; its anhydride melts at 22', and yields with aniline an nnilide melting at 185', whilst the corresponding imide, obtained by the action of heat, melts at 86".I t would seem to follow that €he acid C7H1204 (Zoc. cit.) is a trimethylsuccinic acid or one of the dimethylglutaric acids, in which the two methyl groups are attached to the same carbon atom. The behavionr of hydroxycamphoronic acid on heating indicates that i t proba bly has the constitution CO OH*(3Mez*C H (C H,*CO OH) 2. C. H. B. Synthesis of a New Ketonic acid. By E. BURKER (Compt. rend., 2895, 121, 607--610).-The action of camphoric anhydride on ben- zene in presence of aluminium chloride, if the temperature is not allowed to rise too high, yields nn acid which, when purified, has the composition ClaHLoOz, and forms small, nacreous, white crystals melt- ing at 135-137", and boiling at 320' under a pressure of 760 mm., or at 250" in a vacuum.Its molecular weight in solution in benzene is 232. It is almost insoluble in water, and very slightly in light petroleum, but dissolves readily in other organic solvents. The alkali salts crystallise, and are decomposed by carbonic anhr- dride. The barium salt forms small, white, nacrems crystals con- taining 9H,O. The ethy7ic salt, Cl,Hl,OzEt, dissolves very readily in light petro- leuni, from which it separates in large monoclinic crystals. The niethylic: salt also crystallises from light petroleum in long mono- clinic needles, which melt at 85-86". Both are decomposed at once by sulphuric acid, but are very slowly attacked by alkalis. The anhydride is readily obtained by the action of acetic anhydride, but not by the action of acetic chloride; i t forms small, white ciystalg which melt at about 135', and are only slowly attacked by alcoholic potash. The anzide forms long, silky, white needles which melt at 77", and dissolve i n boiling water; i t is very slowly attacked by alcoholic potash.The phenylhydraside forms long needles wliicli melt at 156'. The formation of this compound is readily explained by Friedel's formula for camslioric acid, but not by any formula which assume3 I I the presence of &two COOH groups. represented as C H P r < ~ ~ ~ ~ ~ > C P h * O H . Its constitution is therefore C. H, B. 0 2180 ABSTRACTS OF OHEMICIAL PAPERS. Digitalin ( ‘ I Digitalinum VerUm ”). By HEINRICH I(rLIAx1 ( A d & .Pharm., 1895, 233, 698-699).-’l’he author has succeeded in obtain- ing digitalin in a crystalline form by dissolving one part of the pnre glucoside in two parts of boiling 85 per cent. methylic alcohol. The temperature of the solution is then allowed to fall gradually t o 45‘, a t which point it is maintained ; the substance is deposited in the fonn of white needles, in part aggregated to nodular masses. From a more dilute solution (1 in lo), the temperature of which is allowed t o fall from the boiling point to the ordinary temperatui-e, a small quantity of the substance is deposited wholly in the form OE stellar aggregates of needles. A. L. Root of Aristolochia Argentina. Bg OSWALD HESSE (Arch. Pharm., 1895,233, 664--697).-0n account of its acid properties, the name aristolochic acid is suggested for Pohl’s ‘‘ aristolochine ” (Abstr., 1892, 874), the latter name being reserved for the alkaloid obtained from Aristolochia argentinu.The author has obtained from the root of this plant a starch-like substance, a resin, an ethereal oil of high boiling point, palmitylphytosterin, C42H7402, aristolin, C15H28O3, the isomeric aristinic and aristidinic acids, CleHI3N0,, nristolic acid, C,,H,,NO, or ClSH,3N07, and the alkaloiid aristolochine (compare Abstr., 1892, 894). The ethereal extract of the root is saturated with gaseous am- monia, and filtered from tho resulting precipitate. The filtrate is neutralised, separated from ainmonium and aristolochine salts, and evaporated. ‘l’lie residual, oily mass partially crystallises, the liquid portion on distillation yielding a colourless, highly refractive oil, having a disagreeable odour.Light petroleum separates the crystal- line mass into soluble palmitylphytosterin and an insoluble sub- stance-uristoiin, Cl5H2803, probably an alcohol ; it crystallises from alcoliol in spherical aggregates of minute needles, and dissolves readily in ether and in hot alcohol. It melts and decomposes at 265’. The precipitate produced by ammonia consists of a mixture of the a mmoniuni salts of aristinic, aristidinic, and aristolic acids, of which the first-named preponderates, and may be separated by means of its potassium salt, which is precipitated from solution on adding R slight excess of alkali. Aristinic acid, cl8~13N07, crystallises from acetic acid in greenish-yellow leaflets or needles which melt and decompose at about 275O, at higher temperatures evolving yellowish vapours which condense to form a yellow sublimate.When it is fused with potash, amlnonia is evolved. It forms two series of salts, a normal and a basic; the former alone have been obtained in a crystalline form. The potas+ztnz salt, C,3€€JV07K,2H20, forms small red crystals, but wheu anhydrous is yellow. The sodium salt resembles that of potas- sium. The aminoiLiunz salt crystallisea in red needles. The bayium, (C18H,2N0,),Ba + 2H20, calciunz, ( C18H12N07)2Ca + 4H20, copper, (C,,H,2N0,)2Cn + 3H20, lead, ( C J E E - I ~ ~ N O ~ ) ~ ~ ~ + 2H20, and siluer salts, Cl8HI2NO7Ag, crystallise in small, orange needles. The methyEic salt, C18H,,NOiMe, forms yellow needles, and melts at about 230’.ORGANIC CHEMISTRY.181 The potassiuni salt of aristidinic acid is separated from that of aristolic acid by adding to the solution a large excess of potash, in which the former salt is insoluble. Aristidiuic acid, C18Hl,NO;, is solubIe i n acetic acid and in alcohol ; it forms small, greenish-yellow crystals which darken at 230", and melt at 260'. AristoZic acid, C,,H,,N07 or ClbHl3NO7, is readily soIuble in ether, acetic acid, and hot alcohol, and crystallises from the latter i n small, orange-red needles, which darken at 2 2 3 O , and melt a t 260-270'. These thres acids and aristolochic acid dissolve in warm sulphurio acid, forming beautiful dark green solutions ; this appears to indicate that these substances are closely allied in consthution.It is possible that aristolochic acid is the next higher homologne of aristinic acid, and that aristidinic acid is methylaristolochic acid. The latter view is supported by the circumstance tliat aristidinic acid appears to contain a methoxyl group. A. L. Chlorophyll. By EDWARD SCHUSCK and LEO &hRCHr,EwsKI (Annalen, 1895, 288, 209-218 ; compare Abstr., 1804, i, 341, and 1895, i, 296) .-The authors, having already established analytically the composition of phyllotaonin (loc. cit.), confirm the expression, C~oH40Ns06, by ebullioscopic determinations of the molecular weight. Phyllotaonin is indifferent towards hydroxylamine, and has no re- ducing action on Fehling's solution or an ammoniacal solution of silver ; tbis behaviour indicates that phyllotaonin and chlorophyll are not aldehydic in character. Owing to the opacity of dilute solutions containing ethylphyllotaonin, it is not possible to determine whether this substance is optically active ; the authors consider, however, that this is probably the case, because phyllotaonin forms monosymmetric crystals which exhibit hemihedral faces.When ethylphyllotaonin is distilled from zinc dust, a, small quan- tity of an oil is produced which becomes brown on exposure to the atmosphere, and yields a red powder when treated with hot, dilute hydrochloric acid ; moreover, the vapoirr which is evolved by phyllo- taonin, when heated in a dry tube, qroduces an intense red stain on a fir splinter which has been moistened with hydrochloric acid.These facts are recognised as indicating relationship betweec chloro- phyll and pyrroline; Nencki and Sieber have recorded a similar observation in connection with hzematoporpbyrin. The remaining portion of the paper is devoted to criticism of Gtard's investigation of lucern (Abstr., 1895, i, %9), the results of &I* 0. F. The Yellow Colouring Matter of Autiilmn Leaves. By GEORO STAAYS (Ber., 1895, 28, 28O7-28o9) .-The yellow colouring matter which may be extracted from autumnal leaves by boiling alcohol is not identical with phylloxanthin, and is called by the author auiunzni- xaiztltin. Prom whatever source the yellow colouring matter is de- rived, its alcoholic solution gives, with potash, a reddish-brown precipitate, which dissolves in water or acids.The potassium com- pound has been obtained in minute crjstals, but has not been nnaljsed. The autumnixantbine itself has not been obtained crystal- which the authors regard as erroneous.182 ABSTRACTS OF CHEMICAL PAPERS. line. When its alcoholic solution is slowly added to boiling hydro- chloric acid, a red solution is formed. Pelageine. By ARTHUR B. GEJFFITHS and C. PLATT (C'onyit. ~ e ~ d . . 1895, 121, 451-452) .-The violet pigment of the medusa dissolves with the fats in alcohol and ether. The filtered solution is evapo- rated to dryness, treated with sodium hydroxide, and the pigment extracted with. carbon bisulphide. It is an amorphous product of the composition CZOH1,N07, insolcble in water, soluble in alcohol, ether, and ethylic acetate, and very soluble in carbon bisnlpliide. The solutions show no characteristic absorption bands.When ex- posed to light, the pigment is decolorised. The Four Santonous acids. By AMERICO AXDREOCCI (Gnzzetfn, 1895, 25, i, 452-568).-1n alcoholic solution, santonin lia3 the specific rotation [aID = -173, the rotlation increasing to -176.5 in 80 per cent. alcohol, whilst when dissolved i n 38 per cent. hydro- chloric acid or hydrobromic acid (sp. gr. 1-38), thc value of [aID becomes -340 aud -345 respectiveIy, although the santonin is precipitated unchanged by addition of water; the increase in rota- tion is probably due to the conversion of the ketonic group into a :C(OH)X group, by addition of water or of the halogen k1yd.de. The behaviour of santonic acid is similar; in 100 and 50 per cent.alcohol it has the specific rotations [a]D = -42.1 and-74.1 respec- tively, and i n 9.5 and 38 per cent. hydrochloric acid [ a ] D = -87.9 and - 138.6 respectively. - > C 0, i 5: obtained together with metliylisodesmotroposantonin, by the action of sodium methoxide and niethylic iodide on desmotroposantonin, A. H. C. H. B. CHMe N e t h y Mesm of voposan i onin, 0 Me* C 12H13< CHMe OH*C12H,,<O ->co ; it crystallises in long needles melting at 152-153', has the specifio rotation [a]D = + 91.9 in absolute alcohol, and dissolves sparingly in the usual solvents. It behaves like an alkylated phenol and is but slowly converted by boiling alkalis into methyldesmotroposantonic acid. The corresponding ethyl derivative, C1,Hz203, is similar in preparation mid properties ; i t crystallises in long needles melting a t 168" and has the specific rotation [ a ] ~ = + 114.0 to 114.2 in absolute alcohol.The benzyl derivative also, prepared by the action of sodium ethoxide and benzylic chloride, crjstallises in needles melting a t 182", and has the specific rotation [aID = + 102.6. Isodesmotroposnntonin crystallises in needles melting at 187-188", and in absolute alcohol has the specific rotation [ a ] D = +f28.8. It >CO, on yields ?,zethylisotZesrnotl.oposanfonin, OMe*C,H,,<O treatment with sodium methoxide and methylic iodide ; this crystal- lises in needles melting at 111--112", and in alcohol has + 118.2. The corresponding ethyl compound crystnlliaes in hemi. morphic, monoclinic prisms melting at 82"; a : b : c = 0.2718 : 1 : 0.2556; f3 = 80" 20'; it is very soluble in ether, chloroform, or alcohol, and CHMeORGANIC CHEMISTRY.183 in the latter Rollition has the specific rotation, [ a ] D = + 129.6. The corresponding bet2zyZ derivative crystallises in small needles inelting at S2O, and has [ z ] D = + 136.5 in alcoholic solution. Dex troeantonons acid (compare Cannizzaro and Carnelutti, Absti-., 1883, 77) melts at 179-180" and distils unchanged at 200-2260' under 5 inm. pressure ; i t has the specific rotation, [aID = + 74.9 i n alcoholic solution, and has the normal molecular weight in freezing acetic acid. I f santonin is yeduced with tin and boiling hydrochloric acid, less snntonous acid is obtained, but yrl.I.ndimeth?llet?~yloctJ~ycll.o- qzaplttlialene, C,,H,,Me,Et, is formed ; when pnrified from an additive compound with hydrogeu chloride by fractionation from sodium, i t is a limpid colourless oil which boils at 247-24s' under ordinnry pressure, and gives the normal vapour density by V.Meyer's method. Methylic dextrosantonite (compare Cannizzaro and Carnelutti, 7oc. cit.), melts at 86", ancl has the specific rotation [a]D = +84*9 in alcohol. The etliylic salt gives [a], = +71.0 in alcohol, and the crysta.ls phosphoresce when crushed, whilst the benzoyl derivative, OBz*C12H,t*CHMe*COOEt, melts a t 75' and gives [a]D = +59.9. Dext romethy Zsantono u s acid, ORie*C12 Rll. CHMe*C 0 OH, is prepared by the action of sodium methoxicle and methylic iodide on dcxtro- saiitonous acid or its ethylic s a l t ; its ethylic salt' crystallises in prisms melting at 116--117O, is soluble in alcohol, ether, light petro- leum, or cold alkaline carbonates ancl has the specific rotation [a]= = + 78.2, in alcoholic solution.Uextro-ethylsantonous acid melts a t 120°, and its etbylic salt has the specific rotat,ion [ a ] D = + 70.5 in alcohol. Etli ylic de.ztl.obromosaiitoirite, OH*C,,HliBr*COOEt~, prepared by brominating ethylic dextrosantonite, forms beautiful hemihedrat orthorhombic crystals melting at 86", and is very soluble in ether, alcohol, or ethylic acetate ; if has the specific rotation [a]D = +68*2 in alcohol. It is precipitated unchanged from its solution in potash by carbonic anhydride, but if the solution is heated or kept, a niixturc of two isomeric dextrobromosantoiious acids is obtained.a-Dextm byornosantonous acid, Cl5HI9BrO3, is very soluble in ether, frcm which it crystallises, with $Et,O, in tablets which melt for the first time at 110', and after solidification R t 115-116'; the pure acid has the specific rotation [ a ] D = + 69.7 in alcohol. p.Destl.ob,.omosantonous acid, is hparingly soluble i n ether, crystallises in pyramids melting at 159-160', and has the specific rotation [ x ] D = + 61-9. On treatment with alcohol and hydrogen chloride, the a-acid yields the ethylic salt from which it is prepared, whilst the /3-isomeride gives a viscous uiicrystallisable mass. No crystalline products were obtained on oxidising dextrosantonous acid with permanganate, ferricyanide, or chromic acid, and on boiling the acid with iodine in acetic acid solution, a green amorphous sub- stance having the composition of a dimethylnaphthaquinonepropionic acid, Cl5HI104, was formed; this dissolves in water, alcohol, and alkalis giving fluorescent solutions.On boiling dextrosantonous acid with dilute acetic acid and ferric chloride, dextvodisantonozcs acid, COOH*CHMe.C I2Hl3(0H)*Cl2Hl3( OH)*CHMe*COOH, is formed ; it cqstallises in small needles melting at 250-250-5", is soluble in184 ABSTRACTS OF OHEMIOAL PAPLRP. alcohol, acetic acid, or alkali carbonates, and has the specific rotn- tion, [a]= = +S9.5 in alcohol, and the normal moleculnr weight in freezing zcetic acid. Its diethy7ic salt, prepared by means of alcohol and hydrogen chloride, crgstallises in colonrless prisms melting at 1 8 3 O , and depresses the freezing point of benzene normally.The two methylic salts melt at 158" and 215O, but were not analyaed. A comparison of the rotatory powers of the laiwosantonous acid, prepared by reducing isodesmotroposantonin (Abstr., 1834, i, 205) with those of its dextro-isomeride, shows that the two substances are enantiomorphous ; when crystallised together they yield the inactive isosantonoua acid melting at 153-155O. Methylic Zcevosantoizite crystallises in large prisms melting at 86O, and is very soluble in alcohol, ether, or light petroleum. The ethplic salt crystallises in large, hemimoi-phic, monoclinic prisms which melt at 116-117' and become phosphorexent when crushed ; u : b : c = 0.5628 : 1 : 0,6959 ; the specific rotation in alcohol is [a]= = -70.4. EthyZic Zcevobenzoylsantoizite crystallises in long needles melting a t 75', and has the specific rotation [a]D= -59.8 in alcohol, that of its dextro-isomeride being + 59.9.Ethylic lcevos~diosaiztoiiite be- haves just like the destro-compound. Lievo??2etla~Zsaiato420lls acid, O~~e.C,,H1l*CH~~e.COOH, is prepared by the action of sodium methoxide and methylic iodide on I~vosan- tonous acid, or by reducing methylisodesmotroposantonin with zinc dust and acetic acid ; it crystallises in pyramids melting at 116--117O, and is very soluble in ether. Ethylic Ecevo-ethylsantoizite also prepared from l~evosantonous acid, crystallises in needles melt- i n g a t 31-32', and has the specific rotation [&ID = -70.3; the acid crystallises in colourless needles melting at 120', and has the specific rotation [aID = - 53.1.L~~;ob~izzylsantonous acid is obtained as a gum. On brominating ethylic laevosantonite in carbon tetrachloride solution, ethylic Zmobi omosaiztonite is obtained in large, hemihedral, orthorhombic crystals, which melt at 86", and are enantiomorplious with those of the dextro-isomeride ; a : b : c = 0 5317 : 1 : 1.0649 ; it has the specific rotation [aID = - 68.5, and on hydroljsis yields hco-a-bronzosantonozis acid, which crystallises with gEt,O, inelts at 110-11lo and 115-116° like its dextro-isomeride, and has the specific rotation [a]D = -69.4. Lcwodisantonozis acid crystalises in needles melting a t 250-250.5", and has the specific rotation [aID = -e5*8. The behariour and properties of these I~evorotatorj- sub- stances are very siinilar to those of their dextro-isomerides.The isosantonous acid of Cannizzaro and Carnelutti (Zoc. cit.) is identical with the raccrnic santonous acid obtained by crystalliving equal weights of dextro- and lcevo-santonous acid together, and melts at 153O. The nzefhyIic salt melts a t 110~5-111°. Racemic ethylic gantonite crystallises in small, colonrless, anorthic crystals which me1 t at 125O, and do not become phosphorescent like those of its active isomerides when crushed ; a : b : c = 1 6891 : 1 : 0.7930 ; a = 92" 59', = 112' 3',../ = €!5O 25'; cryoscopic determinations show i t to be dissociated inio its components i n acetic acid solution. Racemic ethylic benzoylsantonite melts at 89". Rn cem ic 112 e t Ir y lsa 21 fun ous n cid cry s t a1 1 ises in sm a1 1 p r i sins me1 t ingORQANIC OHEMI STRY.185 at 135--135*5O, and the corresponding ethyl compound melts at 14$-145', not at 143', as previously stated ; racernic ethylic homo- santonite, 0 H.C,,H,,Br*CHMe.COOEt, melts at 10&-106', and on hydrolysis yields mcentic a-tro?itosnlzto?aozcs acid which me1 ts a t 193-195O. I7tactiz.e disantonom acid crystallises in sma?l pyramids melting a t 243-244". Methyldesmotroposantonous acid melts a t 107-108° and has the specific rotation [aID = -48.9 ; the corresponding ethyl compound, OEt-Cl,Hl,*CHMe*COOH, crystallises in large, anorthic prisms melt- i n g at 127', and has tlie specific rotation [a;]D = -47.2 in alcoholic solution ; a : b : c = 1.1269 : 1 : 0.6013 ; a = 69' 40', p = 130' 47', = 119" 52'.The elhylic salts of both these acids are viscous liquids. B f ~zzyZdesnzotro~~osa~.~tonoz~s acid, C,H,0*ClzH,4*C HMe. CO OH, pre- pared by reducing benzyldesmotroposantonin with zinc dust atid acetic acid, cqstallises in prisms melting at 120-1?1', and has the specific rotation [ a ] D = -39.3 in alcohol. Methylic desmotroposantonite (Abstr., 1894, i, 205) has the specific rotation [a]= = -41.8 in alcoholic solution ; the sodizrm derivative of this and the corresponding ethylic salt are white powders. d l e t h y Zic bronzodesmotroposantonite, OH* C,zH13Br*CH13r*C OOMe, pre- pared by direct brominatioo, is a syrupy liquid which when hydrolysed with potash yields hromodesmot roposnntonous acid ; it cryatallises with ether or petroleum, in needles melting a t 92', and han the specific rotation [a]= = -50.4 in alcohol.Desnzot.1.opodisantoizous acid, COOH*CHMeClzH1,( OH)*C1,H1,( OH)*CHMe.C OOH, is prepared by oxidising desmotroposantonous acid with ferric chloride; i t crystallises in laminm melting a t 254-%5', and has the specific rotation [alD = -64.5 i n alcohol. On heating desmotroposantonous acid a t 295-305", a resinous anhydride is obtained which, when precipitated from its sodium carbonate solution by hydrochloric acid, yields l~vosantonous acid. When fused with potash, each of the four santonous acids breaks up quantitatively yielding hydrogen, propionic acid, and the same para- diniet liyl-p-naph tho1 (compare Cannizzaro and Carnelu t t i, Gazzet/a, 13, 3 8 5 ) ; it crystallises in lustrous needles melting at 135--136j", and boils a t 315-316' under 760 rnm.pressure ; its methyl deriva- tive crystallises in prisms melting at 68O. The same dimethyl- naphthol is obtained, together with propionic acid and hydrogen bromide on fusing dextro-a-bromosantouolis acid with potash ; if the mixture is fused f o r only a short time, an ill-defined acid, which pro- bably has the constitution OH*C,Hl,*CHMe*COOH, is obtained. The author conclcdes that the four santonous acids are stereoisome- H*y :CMe*fl-CH,*FH, OH*C:CMe*C*CH,* CH-CHAIeCO OH. rides having the constitution * * The two carbon atoms indicated by italics are asymmetric and of different kinds ; therefore foor optically active and two rncemic ssntonous acids should exist. Representing the asymmetric carbon atom of greatest optical activity by A, and that of lesser by I?, dextro-186 ABSTRACTS OF CHEMICAL PAPERS.and kevosautonous acids should contain + A +B and - A --B re- spectively, whilst desmotroposaiitonous acid should contain --A +B; I he racemic santonous acid should be compounded of + A + T: and - A -I?. W. J. Y. Pyridine Periodides. By ALBERT B. PREscow and P. F. TROW- RRIDGE ( J . Amsr. Chent. SOC., 1895, 17, 859--869).-Pyridine methyl pentiodide, C6NH5,MeI,14, is obtained by adding an alcoholic solution of pyridine methiodide to a solution of the requisite quantity of iodine in alcohol. After recrystallisation from alcohol, it forms long, greenish-black needles, arid melts a t 47.5'. P y r i J i n e methyl diiodide forms reddish-brown needles and melts at 91.5'.The crystals are rery sfable ; after eight months, no appre- ciable decomposition was observable. The triiodide forms fine, dark red needles, is perfectly stable, and melts at 50'. Dipyi*idiwe dimethyl enneniodide, (C,NH,,CHJ),I,, crystallises in greenish-black, lnstrous needles, and melts at 44". The octaiodide is still under inres- tigation. Pyridilte tetraiodide, obtained by adding to pyridine an alcoholic solution of iodine until a precipi- tate ceased to form, crptallises in fine, dark green, lustrous needlcs; i t is readily soluble in alcohol, ether, and chloroform, less readily in benzene, melts a t 85", and is less stable than the compounds previously described. The authors hare also prepared Dafert's pjridine hydrogen pent- iodide (Abstr., 1883, 980) ; tho analyses agree with tho formula C6JYH6,HI,14.The melting point is given as 85" (Dafert gives 89'). The paper concludes by giving instructions for the estimation of iodine in periodides. Pyridine ethyl triiodide melts at 49'. J. J. S. The Pyridine Series. By ARTHUR PHILTPS (Asznalen, 1895, 288, 253-265 ; compare Abstr., 1893, i, 727, and 1894, i, 301).-The main facts recorded in this paper have been already described (Eoc. cit.). 31. 0. F. Mercuroquinoline Compounds. By LEONE PESCI (Gazzet ta, 1895, 25, i, 394--406).-QuiiioZine memurk chloride, 2C9NHi,HgC12, is prepared by mixing alcoholic solutions of quinoline and mercuric chloride ; it crystallises i n colourless, thin needles or small rhombo- hedra, decomposes a t 250--200', and is insoluble in cold water.On mixing the proper proportions of quinoline and mercuric chloride in alcoholic solution, a salt of the composition 2CgNH,,2HgC1, may be obtained; it ci-ystallises i n microscopic prisms and is soluble in boiling alcohol. On heating the first salt described above with qnino- line hydrochloride in aqueous soln tion, a s d t of the composition 1 1C,NHi,5HgCl,,HCi is obtained ; it crystallises in colourless, trans- parent, anorthic prisms melting a t 1-43", and is soluble in boiling alcohol. A salt of the composition 7C9NH,,3HgC12,HC1, which crys- tallises in thin, colourless needles, was 2lso prepared. A compound of !he composition 2C9NH7,HgC12,PtC14 is deposited as a jellow, amorphous powder on mixing solution8 of quinolineORGlANIC OHEMISTRY. 187 miercuric acetate and hydrogen platinochloride ; it melts and decorn- poses at 140-141°. QuirLoline mercuric witrate, 2CgNH7,Hg( N03)2,2H20, prepared by treatiug the corresponding acetate with potassium nitrate, crystal- lises in colourle~~, transparent prisms, melting and decomposing at 1!33--184O.Quinoline mercuw'c sqbbphate, 2C0NH7,HgSO4, separates in colourless octahedra on adding quinoline t o mercuric sulphate solntion ; it melts and decomposes at 140-142'. QuinoZine mercuric acetnle, 2CgNH7,Hg(OAc)2,2H20, separ<ites i n large, transparent, orthorhombic crystals on cooling a solution of quinoline in mercuric acetate solution; it is soluble in chloroform, benzene, or water, and is most soluble in water at 40°, for above this temperature the solution becomes turbid and deposits an oily sub- stance.I t melts a t 148", and is decomposed by boiling water, giving mercuric oxide, quinoline, and a salt of $he composition 2 CgNH,, 2 Hg( OAC) p ; the latter crystallises in colourless needles melting at 1 5 6 O , and may be also prepared by mixing quinoline and mercuric acetate solution in the proper proportion. Quino1in.e mercuric oxalate, 2C9NH7,HgC204, prepared by the interaction of the corresponding acetate and potas- sium oxalate, crystallises in colourless laminae, melting and decompos- ing at, 177-1 78". The above compounds niny be regarded as salts of pcino7ine nzercuric hydroxide, 2CgNH,,Hg(OH),, a solution of which can be readily pre- pared by treating the corresponding sulphate with barium carbonate ; the solution is colourless, and has a strongly alkaline reaction towards litmus, but is indifferent ton-ards phcnolphthale'in.The pure base could not be isolated, for, on evaporating the solution, quinoline and mercuric oxide separate ; the base in solution reacts quantitatively with sodium thiosulphate, yielding quinoline, mercuric thiosulphate, and caustic soda ; with potassium iodide, giving quinoline, mercuric iodide, and caustic potash; and with ammonium bromide, giving quinoline, mercuric b~omide, and ammonia. W. J. P. Synthesis of Quinolne Derivatives from Anthranilic acid and Aldehydes. By STEFANIEMENTOWSK~ and B. ORZECHOWSKI (Ber., 1895, 28, 2809-2822 ; compare Abstr., 1894, i, 427).-Acet- aldehyde reacts readily with anthranilic acid to form ethylideneaiitlzr- anilic acid, COOHCGH4*N:CHMe, which, however, could not be obtained quite pure, as it partially decomposes when recrys tallised.T~ichlorethy Ziderzeantlzrnr~ilic acid is obtained from chloral and anthr- anilic acid; i t crystallises in rhombic tablets, melts a t 152O, and is decomposed by boiling water into anthranilic acid and chloroform. Propylideneaizthrunilic acid is a yellow powder which melts at 113'. When this compound or its constituents are heated on the water bath, 3'-~net7zyl-2'-etl~y7puinoline-l-carbntylic acid is formed ; it crystallises in pale yellow needles or plates, melting at 221'. This substance is accompanied by nteth~ZethyZacrolei;na?tthranilic acid, C 0 0 H*CsH4-N: C H*CMe:C HE t,188 ABSTRACTS OF CHEMICAL. PAPERS. which is a yellow, amorphous mass, and is converted into the fore- going substance when its alcoholic solution is preserved.The carb- oxylic acid, on distillation, yields the 3'-methyl-'L'-ethylquinoline described by Doebner and Miller (Abstr., 1884, 1376). This is. accompanied by other products, which have not yet been examined. Oenanthaldehyde reacts with anthranilic acid at the ordinary temperature to form a polymeric hepty lideneanthranilic acid, C28H38N204, which melts at 183', and is converted into the com- pouiid, C14HlgN02, when it is heated for some time at its melting point; the latter crystallises well and melts at 93'. When it is heated with a strong acid or an alkali, it is converted into 3'-ccmy2-2'- hezy lqziinoline-1-cnl.bosyEic acid, which crystallises in rhombic tablets melting at 69'.The hydrochEoride is formed when hydrogen chloride is passed into an ethereal solution of beptylideneanthranilic acid. The carboxylic acid may also be obtained by heating heptylidene- anthranilic acid with acetic anhydride. Oxygen is absorbed from the ail- and acetanthranilic acid formed. On distillation, the acid yields 3'-amyl-8'-hexylquinoline. 4'-H~d~o~y-3'-anzyZqui~aoZine is formed in small amount when beptylideneanthranilic acid is heated at 200' in a sealed tube, and forms broad, silky needles, melting at 85'. The author has also obtained a substance of the formula C,,H,,N,O, by the condensation of oenanthaldehyde and anthranilic acid under conditions which have not been precisely defined. I t crystallises in yellow needles melting at 243'.Compounds of Antipyrine (Dimethylphenylpyrazolone) with Dihydric Phenols. By GUSTAVE PATEIN and E. DUFAU (Compt. rend., 1895, 121, 532-534) .-Catecholdiantipyrine is obtained by mixing aqueous solutions of its constituents ; it forms colourless crystals, which melt at 78-79', and are very soluble in alcohol and chloroform, slightly soluble in ether or water. With ferric chloride solution, a greenish- black coloration is produced. Guaiacol o r methylcatechol combines with only one molecular proportion of antippine, and veratrol or dimethyl- catechol does not combine with it at all. Resorcinol combines with only one molecular proportion of antipyrine, and the product, which melts at 103-104", gives a blood-red coloration with ferric chloride. Quinol, like catechol, combines with two molecular proportions of antipyrine, and the product ci-ystallises in colourless needles, which melt at 127-128' and are very soluble in boiling water or alcohol, slightly soluble in ether, arid soluble in, but decomposed by, chloro- form.With ferric chloride, a deep red coloration is produced, changing., after a time, to pale red. In presence of the slightest excess ok quinol, decolorisation is instantaneous, and quinhydrone is precipitated. These products cannot be regarded as mere molecular combinations, and it is probable t h a t combination takes place between the hydroxyl groups and the nitrogen which is i n connection with the methjl group in the antipyrine, this nitrogen becoming quinquivnlent. I t is noteworthy that the ortho- and para-dihydric phenols combine with 2 mols.of antipyrine, whereas the metadihydric phenol combines only with one, and this power of combination disappears in A. H.ORQANIC CHEMISTRT. 189 proportion as the hydroxyl groups are displaced by a metal or an alkgl radicle. C. H. 13. Diphenylisoxazole. By CARL GOLDSCHJIIDT (Ber., 1895, 28, 2.340) .-Benzylideneacetophenone dissolved in ether is converted by chlorine into beizzylideszeacetophenone up-dicldoride, CHPhC1-C HC1- COP b, which melts at. 113'. This substance reacts with hydroxylamine t o form diphenylisoxazole, IT< CPh*gH , which crystallives in nacreous 0-CPh plates, melting a t 141'. This compound and phenylmethylisoxazole are converted by alcoholic ammonia at 250' into crystalline bases, an account of which will shortly be published.Action of Hydroxylamine on Ethylic Benzylideneaceto- acetate. By EMIL KNOEVENAGEL and W. RENNER (BeT., 1895, 28, 2994-3000 ; compare R. Schiff, this vol, i, 8S).-Hydroxylnmine hydrochloride in alcoholic solution reacts with ethylic benzylidene- acetoacetate when warmed for some 30 mirutes on the water bath, the, chief product being r-methyl-p-benzylideneisoxazolone (m. p. 142'). When treated with hydroxylamine hydrochloride in the cold, ethylic benzylideneacetoacetate yields the hydrochloride of the above met hy1 benzylideneisoxazolone ; this readily loses hydrogen chloride when suspended i n alcohol, and, when warmed with a 10 per cent. sodium hydroxide solution, yields a substance which is probably the hitherto unknown labile form of oa:imidobt!iLti/Eicleneacetoacetic acid, A.H. Me *g*$XCHPh * H0.N COOH I t melts a t l S 6 O , readily dissolvcs in alkalis, but is ~ _ _ insoluble in water, benzene, and light petroleum. Methyl benzyliclene- isoxazolone itself does not yield this acid when warmed with alkalis, but is conipletely decomposed. The ammonium salt forms colourless crystals, melts a t 194--196O, and is readily soluble in water. The acid may be reconverted into methylbenzglideneisoxazolone either by treatment with an alcoholic solution of hydrogen chloride in the cold, or with aqueous hydrogen chloride at iOOo.- It is possible that the acid in question may have the constitution ?Me = N COOH*CHCHP~>~- When an alcoholic solution of ethylic benzylideneacetoacetate is Created with free hydroxylamine at the ordinary t empera.ture, a different product is obtained.This melts at 104-106°, and is readily soluble i n alcohol, benzene, and light petroleum, but insoluble in water and ether ; its constitution has not yet been determined. J. J. S. A Synthesis of 3 : 5-Methylphenylpyrazole. By CARL GOLD- SCHMIDT (Ber., 1895, 28, 2952). -When phenylmethylisoxazole is heated with alcoholic ammonia at 240°, oxygen is replaced by the imido-group, and 3 : 5-methylphenylpyrazole (Sjollema, Abstr., 1894, i, 546) is obtained. c. F. u.190 ABSTRACTS OF CHEMICAL PAPERF. Synthesis of Biazoline Derivatives. By MAX J3usctr (Be,.., 1895, 28, 2635-2647).-Phenylthiocarbazinic acid, in the form of the potassium salt or an ethereal salt, reacts with aldehydes to cHz'yH.Pli eizylthiobiazol iiz e CH:N produce derivatives of thiobiazoline, S < CHZ-NPh , fmmed by the action of formalde- S<CrsH,:& 7~ y ti rosu lph id e , . I hycle on the potassium salt of phenylthiocarbazinic acid, crptal- lises in druses of compact, white plates melting a t 112'. It readily dissolves i n aqueous alkalis, and is decomposed by boiling with them into formaldehyde and phenylthiocarbazinic acid. Pheuylthiobiazo- line b i d p h i d e , (C,H,SN&3,, is formed by the actioli of ferric chloride on the hgdrosulphide, and crystallises in lasirous, orange plates, melting a t 135'. The bisulphide undergoes a characteristic decom- position when i t is heated to 130°, or when its chloroform solntion is preserved, the hydrosulphide being formed, together with p h e q Ziso- dithiobiaaolone, NPh< CH-? I This substance crystallises in narrow, greenish plates, and melts and decomposes at 190".It is insoluble in cold alkalis, but dissolves on warming. yielding a solution from which phenylthiocarbazinic acid is deposited on the addition of an acid. X e thy lpheny 1 t hio t iazoline hydrosdphide, S < , is prepared from acetaldehyde, and forms large, feathery plates, melting at 132'. The potassizcrn salt forms lustrous, white plates, and is readily soluble in water and alcohol. The bisulphide crystallises in orange-coloured plates, melting a t 140'. N- CS' CHMe*yPh C(SH):N - C Ifem N-C3 Met lay& he ny bisod it hiob iaxol one, NPh < I 9 crystallises in fasci- cular groups of light yellow plates, which melt at 216".It does not appear to be converted into niet.hylphenylthiobiazoline hydrosulphide by reduction. It unites with methylic iodide to form a substance of the. formula, C,H,N,S2,MeI, which crystallises in long, lustrous needles, melting a t about 180O. D iphen y 1 t hiob iazoline .7L yd rosulp 11 id c, S < CHPh* fi'pll, is prepared C(SH)*N from benzaldehyde, and crys tallises in almost colourless, rhombo- hedral ci-ysttlls, which melt at 156.5". The sod,itbm salt, C,rH,IN,$2Na + 3Hz0, forms silvery plates, and the potas.&uiu salt white needles. Bip hen y 1 t hio biazolin e iize t hosu @ hide , C ,,H SN2* S Me, is obtained by the action of methylic iodide on the hydrosulphidc, or hy the con- densation of benzaldehyde with methylic phenylthiocarbazinate.It crystallises in faintlp yellowish-green needles, rnelhing a t 93-94". T h e bisuZpliide is tt lustrous brown crystdine potrvder, melting at 138". c PI1- s Dipheizy lisod it hio biazolone, NPli <Ar-- bs, forms orang e-coloured crptals, melting at 22'3-224'.ORGANIC CHEMISTRY. 191 Met h y lic p h e I LIJ It hioca b a z inat e, NH P ha NH* C S S Me, forms f as c ic u 1 a i= groups of flat needles, melting at 135'. It dissolves without chaupe in dilute alkalis. and is much more stable than the acid. 0 With formaldehyde, i t produces p hen yl t hiobiazoline met Iioszdph ide, I , which crystallises in long needles, melting a t ' <C(SMe):N CHZ-NPh :34!--35". tliiobiazoline methosulphide described above. With benzaldehyde, the methylic salt forms the diphenyI- A.H. Constitution of Heteroxanthine. By MARTIS KR~:GE R and G EORG SALOMON (Zeit. physiol. Chern., 1895, 21, 169--285)--See this vol., ii, 200. Water of Crystallisation of Morphine Hydrochloride and of Morphine. By WILHELM GSHLICH (Arch. Phann., 1895, 233, 631--645).-Results of the estimation of water of crystallisation i n carefully purified morphine show that at 100" it lost from 0.017 to 2.53 per cent. in weight, and at 120" decomposed slightly, the final loss amounting to 5-89-6.34 per cent. This result is not in agreement with those of Dott (Abstr., 1888, 506) and Dietericli (Hey. Ann., 1888), who record instances of a loss of the total water a t loo", and a loss in weight at 1203 of 6.39-6-56 per cent. Estimations made with morphine hydrochloride showed a loss in weight varying from 13.02 to 14% per cent.The number calculated from the usually accepted formula, CI,H19TSOy,HCl + 3HzO, being 14.38. The author concludes that specimens of morphine hydrochloride, as described by the German Pharmacopcea, containing from 14.5-15 per cent. of water, are of the rarest occurrence. A. L. Papaveraldoxime. By ROCERT KIRSCH (Nonatslz., 1895, 16,828- 848).--The oxime obtained from Goldschmiedt's papnveraldine (com- pare Abstr., 1887, 163) consists of two stereoisomerides, of which one crystallises in verg slender, microscopic needles, and melts at 335' ; the other crystallises in large, flat prisms, and melts a t 254". From cikher of these stereoisomerides, by interaction with hydrochloric acid under suitable conditions, the following four hydroclilorides cau be prepared :-A wionok ydl.ochZoride, CzoHz,,Nz05,HC1 + 3H20, which forms small, needle-shaped, yellow crystals ; a monohydi.ochlorille, C20HzoN205,HC1 + 10H,O, which crystallises in coloudess, rhombic prisms, sinters a t 90", and melts and decomposes at 220-225"; a dihydwchloride, C20H.LoNz06,2HC1 + 12H20, which crystall ises in yellow, silky, flat needles, melts in its water of crystallisation at 80-8fi0, evolves gas at log", again solidifies a t a higher tempera- ture, and finally melts and decomposes at 210-230'; and a dihydro- clJoride, C20H20NZ05,2 HC1 + 4HI0, which crystallises in yellow, rhombic plates, melts a t 93", evolves gas a t l l O o , and completelv decomposes a t 210". All these hydrochlorides when heated at LIOo, lose water, or water and hydrogen chloride, and form the same au- hydrous monohydrochloricXe.Attempts to ascertain the configorstion of the stereoisomeric papaveraldoximes led to no certaiu results.192 ABSTRACTS OF CHEMICAL PAPERS. When reduced with sodium amnlRzm in acid solution, papaverald- oxime is converted into papavemldylnntine, [(Olle)2 : N : CH = 2 : 3 : 2' : 1' and CH : (OMe), =. 1 : 3 : 41, a yellowish-brown oil, of vanilla-like odour, which solidifies in an exsiccator to a, yellowish-brown mass melting at 80-85". G. T. M. History of Aconitine. By MARTIN FREUSD (Bet.., 1895, 28, 2.537-2539 ; compare Abstr., 1895, i, 254).-The author tabulates the results of his analyses of aconitine and some of its derivatives, and compares them with the uumbcrs calculated from the formula proposed by himself, and from that proposed by Wright and adopted by Duu- stan.He considers that the results establish the correctness of his formula. A. H. Chemistry of Ipecacuanha. By BEYJAMIN H. PAUL and ALFRED J. COWNLEY (Pharm. J. Trans., 1894, [3], 25, 111-115, 373-374, 690-692).-The authors' earlier conclusion (Abstr., 1894, i, 155) as to the exist,ence of at least two alkalojids in the substance known as emctine, is confirmed. The separation and properties of these alkalojids are now described. One is a base insoluble in caustic alkalis, and nncrystallisable, for which it is proposed to retain the natne ef enzetine ; its formula is C,,H2,N02 ; the other, cep7iaeZine, C,,H,,N02, is soluble in caustic alka!i, and obtainable in a crystalline form.These were separated from ipecacuanhs by extraction with alcohol, precipitation with basic lead acetate, evaporation of the filtrate to dryness, and treatment of the residue with dilute acid ; the solution was mixed with ether, animonia added in slight excess, and shaken, and from the separated ethereal solution, dilute snlphuric acid took up the emetine, which was precipitated by soda in excess, and snb- jected to further treatment, in order to entirely remove the other base. The alkaline solution, when acidified and then shakm with ether and ammonia, gave cephaeline. Emctine melts at 68", is amorphous, strongly alkaline, aiid colourless, but turns yellow when exposed to light. It is soluble in alcohol, ether, chloroform, or beuzene, but only sparingly so in hot light petroleum or in watei..Of its s a h only the chloride and nitrate could be obtained in a crys- talline state. Cephaeline is colourless, but, like emetine, is turned yellow by exposure to light: it is less soluble in etber, and cold light petroleum dissolves it very sparingly, whilst the hot liquid dissolves more of it, b u t on cooling, deposits it again in A flocculent form. It melts iu a capillary tube at 96-98", loses weight a t ZOOo when heated in the open, and at 120" is changed, without melting, into a brown substance. The salts of cephaeline much resemble those of the other base, but its platinochloride is of a much darker yellow colour than the corresponding emetine salt. In the second paper is noted the facility with which the chlorides of each base can be obtained as crystals from solutions containing excess of hydrochloric acid.The authors also criticise certainOKOANIC CHEhlISTKY. 193 ~ ~ s u l t s published by Kunz-Kranse (Abstr., 1895, i, 118) as quite incompatible with their own observations. 'l'hc remairiing paper aiiiiounces the isolation of a third alkalo'itl frcm ipecitcu:t:ihit. It exists in relatively small quantity, is cIi,zrac- teristd hy very sparing solubility i n ether, a!id remains in the am- ~noniacnliquor from which einetin and cephaeline have been extractecl by etber. I t can he obiailled in pale yellow, prismatic: crystals which melt a t about 138'. Enietine, cephaeline, and their salts are already supplied commercially as medicines.E. R. Deliquescent Alkaloid from Lupinus albus. By ARTURO SOLDAlNI (G'uzzetfa, 25, 1895, i, 352--364).-The high melting h j dmbromicle of the deliquescent alkaloi'd obtained from t h e see& of Lzipiniis a l L m melts and decomposes at 233--234", not at 224--'221i0, AS previously stated (Abstr., 1893, i, 739) ; i t has t h e specific rota- tion (z]D = -5.G" in :L 25 per cent. aqueous solution. 'I'he pZutiw- chloride, ( C',H,,KO)I,H2PtC16 + 2hH?O, is obtained as a, red, crystalline powder, and when anhydrous decomposes a t 202-203° ; the auro- chloride docoinposes at ahouk 163', and is iwluced by boiling with water. The hyrl~ochZo~*irlc crjstdlises i n thin, piGtnat ic needles which decompose at 16.,", is insolub'e in cold a!coliol, a n d is 1;e~o- rotatoi-y in solution.'l'h base seems therefore to be distinct from its isonicride, tropinc. The alcoholic mother liquors obtained during the preparation of the above hydrolsroniide contail1 t w o bases whicbh (a11 be separated l).y fractional crystallisation OE their platin~cl~lor~ides. One of those yields R hydrnchloridP, soluhlt! i n alcohol, which gives a ci~ystslline p!atinochb 7 i J e (C?,H1NO),,H,PtCI6 ; the other yields a crystalline hyd/*ochZori'de, C,H,,NO,HCI, meltit g a t 1 7 P , and is insoluble in n 1 CCI 1x0 1, JV. J. P. Extraction of Alkaloids from t h e Seeds of Lupinus albus. By ARTURO SOLDAIM (Gazzeita, 1893, 25, i, ~65--380).--Tlie hc s t method of Reparatang the a:kalo'ids froin Lupinus albus is to treat the aqueous extract of the lupine meal with lime, estrnct with petroleum, and then to extract the latter solution with dilute hjdrochloric acid ; the acid solntion yields the crude mixture oE Iijdrochlorides on eva- pc,ration.The deliquescent alkalo'icl is less soluble i n petroleum than the crystalline one, and t h e bases may be separatoct by crystallisation from this solvent. Other methods of extrnct,ing the alkalo'ids a r e referred to, dcpending on the use of basic lead acetate, Meyer's reagent, alcoholic hydivchloric acid, and ctialysis. Formation of Arginine from Protei'd Substances. Ry SvEiJ G. H EDIK (Zeit. physiol. Chem., 1595, 21, 155-168 ; compare Abstr., 1895, i, 160).-The substance previously obtdned by the author from horiiy substance is proved to be identical with Schulze and St eiger's arginine (Abstr., 188G, 725). Besides tlie compounds men- tioned by Sohulze and Steiger, tlie author descrit es t h e com- pouiids AgS03,C6HllN102 + $H,O, AgNO:(:CGH,,N,O,,HNO,, and C,.€I,,N,O,,BH NO,. The snlplrat c and oxalate could not be obtained W. J. P. J O L . LXX. i. Y191 ABSTRACTS O F CHEMICAL PAPERS. in a crystalline form. various sources are giveq. Methods for tho preparation of qrginiiic from Horn yields a t lesst . , . , - , . , , . , , Conglutin yields a t 1wMt . . . . . . . . U, Albumin (from yolk of egg) yiulds at least., . , . *. . . * , . . . . . , . . , . . 9 9 Albumin (from white of egg) yields at least.. . . . . . . . . , . . . , . , . , . . V t Dry blood serum . . . , , . . . . , . , * 0.7 . 4 1 9 Crtse'in . * . . . .. . , , * . . . . , , . . , . . , 3 ) 2.25 pel' cent, of arginine. 2.75 2.3 0.8 02.5 Glue * ? .. .. ) ) . . * , . * PGO ,, 1 , ,* #, The argi~ine is liest i-olntc>.cl irr the form of the silver s:llt9 AgNOA,C,H,,N,O2 + $H20, as this io very ~paringlg soluble in water, care must be taken that the silver salt AgN03,C,H,N,0,,EfNQ, i s not, formed, as this i s i?eadily soluble. To aoootnplish this, tile phosphotungstic acid prepipitate is treated with bgriuni hydroxide, the excess of hydroxide is removed by slightly aQidifying w i t h sulphuric acid, and then the sulpburio m i d is ezactly precipitated with barium hydroxide, and the strongly aIkaliiie filtrate tr?eated with silver nibrate, when tbe sparingly soluble silver salt is thrown down, Anhaloniurn LewlnIi and other Cacti, By LOUIS LEWN (Chem, Cantr., 1895, i, 219-220; from Arch. B:.r*y, Pathol,, 34, 374--391),--Crystals of aqbalonine are biaxial and optically active, and belon to the rhombic system. Antdonine dissolves in water, and chloroform, $c. The free base may be distilled without undergoing decomposition ; it sinlers a t 74", and is cclrnpletely fused at '77*.5°. The F-ydroehkwide, CI1Hl5NO3, HC I, which tats tes oligbtly bitter, melts and decoiuposw at 254-255'; it is sparingly poluble in cold waker, readilg in hot, crystallises from water more readily than the alkaloid, $he solution being laevorotatory, and is coloured yellow hy sulphuric acid ; [aJP = -40 56" in alcoholic solution. Nitric acid gives first :L pqle red, which ghangesl to a blood red, and, on warmingq to a yellow coloration, The phtinochloride, (C,,H,,NO,),, H2PtGl6, is cq-stalline. I n s n i ~ l l doaes, anhalouinc pr?oduces reflex Srri tability, and in larger doses, refleg tetanus; tbe fatal dose f o r rabbits is 0 ~ 1 G - O . ~ gram per kilo, of body weight. The sqme base may also be obtained from Anhalopiurn Jpu~daizians~m, J. J. S, J. J. S. gives an a 7 kttlirio reaction ; it is also rendily soluble iu alcohol, ether, Lithofeiiic aaid. By E. J~NGER and A, &,mm (Beis., 1855, 28, 3045--304!9).-~~ithofellic acid, C2nHSOj, bas been sbuclied hy Goebel, Wohler, Hoster, Grattola, and Strecker; it is obtained frcm gall- &ones, and when crystrtlliscd from alcohol melts at 199" (uncoi*r.), When an alcoliolic solution of lithofellic arid is heated with squeous barium hydroxide for several hours i n a reflax appnratqs, ethylio Etlcohol is eliminated, and qn unsaturated acid, CIPHaDUS, is produced ; it crystallises in ngcreon~ scalefi, and nielts atr 152", LithojeZlolactoize, C2DH3qOs, i s obtained by hsa tirig an rtlctoholic soln- tion of litbofellio acid with concentrated hydrochloric acid 011 the0 R U A N IC C H E M 1 ST It Y. 195 water bath ; i t is a, colou1*less vi3cous oil, which boils nt 243-2483 under a p~.essui.e o€ 16 mm. The molecular refraction 11[ = 91 99. Aqiieous barium hydiwxide converts t h e lactone into tbe unsaturated acid, and this snbstgiice also yields a lactone which boils a t 275-280° under a pressure of 60 mm, M. 0, F. Emulsin from Fungi, Ry Earrr,e l3. BOURQUELOT mid H. HERISSEY (Compt, rend., 1895, 121, ~3--695).--Bsyergillus niyer wac culti- vated in Raulin's fluid, and when i t had fructitied, the liquid was drawn off, tho residue washed s e v e ~ a l times with distilled water, and finally allowed to remain in contact with distilled water for several daj8, the solution of emnlbin thus obtair?ed being used for the experiments. This solution hydi?olyses amygdalin, salicin, coniferin, arbutin, eiixulin, helicin, popnlin, and pbloridzin, bEt has no aotion on solanin, hesperidin, convallamarin, convolvulin, jalapin, and putassium atract,ylate. Uiililte the emulsiu of almonds, it has no hydroljsing nation on milk sugar, and it also differs in acting, albhough very slowly, on populin and phloridzin, The juice expressed from Y o l y p o ~ z ~ s suZphreu.9, &c,, which grows on moet of the Grdinary trees, Iias similar hjdrolysing properties, and ncte readily on amygdalin, esculin, arbutin, coniferin, and salicin, but has no effeot on milk sugar. It follows from these and previous observations (Abstr., 1894, ii, 63, log), that fungi all contain the same enlnlsin, but the evidence is not. yet sufficient to decide whether it is or is not identical with the emulsin from bitter almonds, c, N. B. Engyrnes of Certain Yeastcr. By BMIL FIWWR and PAur, LINDNU'ER (Be?., 1895, 28, 3034--3039).--The authors give details of 24 experiments intended to throw light on the question whether the fermentation of polysacoharides is preceded by hydrolysis. They find that melibiosle is hydrolysed by extracts of the yeasts (Frohberg and Saaz) of bottom fermentation; the extracts were prepared by digesting with water a t 33" for 20 hours specimens whioh were dried for three daya in air a t 20--25', having been previously drained on porous earthenwave. As thwe types also induce hydroljsio when employed in the moist state, it is evident that the hydpoljtic ctnxyme is not a result of dwiccation. Melibiose, horrever, is: indieercnt towards the Froliberg and Saaz types of top ferinentabioii yeast, neither the fresh product nor an aqueous extt'aot ot tbe dried yeast etftcting hydrolysis of the sugar ; this observation contradicts the statement of Scheiblep and Mittelmeier (Abstr., 1890, 2%), who recorded the complete hydrolysis of melibiose by the Rgency of invertin, an enzyme which is present in the typos indicated, More- over, the authors have repeated the experiment of Soheihler and Xittelmeier with a negative result, and are led, therefore, t o the con- clusion that the specimen of invertin which these investigator8 eniployed wau contamiiiated with other enzymes of beer yeast. An aqueous extract of desiccated Jfonilia c m d i d n has no action on cane sugar, but the dried produot contains a hydrolytic enzyme mhictli is, therefore, insoluble in water ; a frzsh specimen of the moist yeayt19G ADSTRACTS OF CRE3fTCAL PXPERS. also hydrolyses cane sugar, although less actively than t h e dried sub- stance. All three preparations OE this yeast, however, have a marke(l hydrolytic action on maltose. Sacchrtyotnyces apiczclatus, whether dry or fresh, is without hydrolytic action on c ~ i i e sugar. I n the course of these expeiiments, thymol and toluene have bcen employed as anaesthetic agents to prohibit fermentation. M. 0. F. Liquefaction and Saline Digestion of Gelatin. By A . DASTRE and N. FLORESCO (Conzpt. wnd., 1895, 121, 615--617).--The liquefac- tion of gelatin, or loss of the pon er of gelatinisation, is brought about by the prolonged 01' repeated acf ion of boiling water, the brief action of water a t a high temperature. the action of certain saline solutions, and also, a s is woll known, by the a d i o n of liquefying bacteria, and by gastric or pancreatic digestion. Gelatinisation begins to be apparent with solutions coiitaining 0-7.5 part of gelatin in 100; solutions containing 5 to 10 parts per 100 are strong solutions in which the phenomona o m be easily fol- lomedi, wnilst solutions containiiig 2.3 parts per 100 may be regarded as of medium concentr. t ' ion. "lie liquefaction is due to the con~ersioii of the gelatin, by com- bination with water, into gelafose 01- protogelatose, which is charac- terised by the fact that i t will not gehtinise and is not precipitated by a, satura.ted suluticin of sodium chloride, complete liquef'actiou COY- responding with complete coiivei~aion into gelatose. The smne change is produced by liquefying bacteibia. Contrary t o the usual belief, comparatively short exposures of gelatin to such temperatures as 110 -120' causes a partial conversion of gelatin into gelntose with consequent IOSS of gelatinising power, and there is little doubt that any contact with wartri water do6.s affect the gelatin, although the eifect may not be at once appreciabltb. I n contact, with certain saltg, such as alkali chlorides or iodides, gelatin gradually lose8 it., power of solidifying. With solutions con- taining only 1 part of salt per 100, t h e effeet on t h e gelatin is shown by the greater t i m e required for gelatinisation and the lower con- sistency of the jelly. With 10 parts of salt per 100 liquefaction i s complete, a i d the ,ge!ntin is entirely converted into gelatose whatever the proportion of gelatin used, It i s noteworthy, however, that with alkali tliiorides, t l i t A change is never complete, To this phenomenon the authors give the name saline digegtio)?, because i t is identical in its results with psfiaic nrid pancreatic digestion, and is produced under similar conditimc, that is to say, by prolonged coiitxct at a moderate temperatui-e, such as $ i t 0 , but not by short exposure to a high tem- peratnre snch as 100-120°. C, H. B.

ISSN:0368-1769    

DOI:10.1039/CA8967000113

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

118 ABSTRACTS OF CHEMIOAL PAPERS. P h y s i o 1 o gi c a1 C h em i s tlr y. Respiratory Metabolism. By WILHELM FKLEHKE and H. KIONKA (P$iiger’s Archiv, 1895, 92, 201 -248).-Geppert and Zuntz (ibid., 42, 189) have shown that during muscular work, in spite of the in- creased respiratory exchange, the blood gases remain practically unaltered. They consider that this constancy is regulated by nervous action, and one of the questions investigated in the present research is the discovery of the nerve channels, and the results of dividing them. Rabbits and dogs were used; muscles were thrown into tetanus by electrical stimulation, and the expired air and blood gases analysed by Znntz’s methods. Observations are also recorded on body weight and temperature. The result of cutting the nerves of the tetanised muscles is that mu,scular work causes a fall in the amount of oxygen in the aortic blood; there is also a small diminution in the amount of carbonic anhydride.But when the vagi are also divided, there is a marked rise in the latter gas, and a fall in the amount of oxygen; the vagi are supposed to be the chief nervous channels in question, experi- ments leading to the conclusions that it is on tohe vagal terminations in the lungs that the venous blood specially acts, and thus secondarily on the respiratory centre, and further that the diminution of oxygen is a more important factor in exciting dgspnoeic fiymptoms than i n - crease of carbonic anhydride. On the other hand, i t appears to be the increase of carbonic anhydride in the muscular substance which excites the sensory nerves of muscle, and so reflexly influences the respiratory mechanism.The question of dyspnma due to work is discussed at length ; other subjects treated are Cheyne-Stokes respirations, and the very similar periodicity of respiratory activity occurring in morphine poisoning. The blood gases and respiratory activity appear to bear no constant relationship to each other ; thus the animal may breathe when the arterial blood has much oxygen and little carbonic anhydride, and the pauses may occur when the opposite condition of the blood gases is present. Fatigue of the respiratory centre is also dismissed as an explanation of the phenomena ; the real explanation is left an unsettled problem. W. D. H. Action of Salts on the Gastric Digestion of Fibrin, and ofAcids on the Saline Digestion of Fibrin.By A. DASTRE (Compt. rend. Soc. Biol., 1894, 7i8-779 ; compare Abstr., 1895, ii, 300).-The proteo- lytic action of acidified pepsin is prevented by concentrated salts like sodium or ammonium chloride : the proteolytic action of concentrated saline solutions is prevented by acidification. W. D. H.PHY SIOLOQICAL CHEMISTRY. 119 Oxidising Power of the Blood. By J. E. AHELOUS and G. BIARNES (Compt. rend. A ~ O C . BWZ., 1894, 536-538, 799-801) .-Sali- cylaldehyde is not oxidised to salicylic acid by the air, or by dist,illed water, or physiological saline solution a t 37". The acid is, however, formed when defibrinated blood or serum is added at this temperature, although this does not occur at the temperature of the air.The amount of oxidation varies with the blood of different animals, and is attributed to a specific ferment, which is destroyed by boil- ing. Certain organs (testis, thyroid, adrenals, thymus, kidney, liver, lung, and spleen) possess the same power, which is lost when vitality is destroyed ; it is not shown by muscles, brain, or pancreas. W. D. H. Action of Blood-serum on Glycogen and on Maltose. By ~ B ~ J L E E. BOL'RQUELOT and EUG~NE GLEY (Compt. rend. Soc. Biol., 1895, 247-250) .-Blood serum has a saccharifying action on glyco- gen, the action being more energetic than that of saliva ; the sugar formed is not, however, maltose but dextrose. W. D. H. Formation of Glycogen in the Animal Organism, By MAURICE KAUFMAKN (Compt. rend.Soc. BioZ., 1895, 277--280), and by A. DASTRE (ibid., 280--283).-The first paper discusses the origin of glycogen : the author believes that in man and the higher animals, it originates solely in the liver, and that the glycogen in the blood and ekewhere is derived from the liver, and not formed i n the cells where it can be detected. The second paper discusses the same question with the opposite conclusion, maintaining the doctrine tbat glycogen is fixed, not cir- d a t i n g . W. D. H. Glycogen in Lymph. By A. DASTRE (Conipt. rend. SOC. Biol., 1895, 242-247).-Lymph contains 0.097 part of glycogen per 1000. After 24 hours, it is destroyed in the lymph by a diastatic ferment. Glycogen is present in the cells, but not, in the plasma. W. D. H. Thyreo-antitoxin.By SIGMUND FRANKEL ( Wieney wed. Blatter, 1895, No. 48).-After removal of proteid and gelatinous matter from thyroid extract, the physiological substance which possesses curative powers remains unprecipitated, and so far as experiments have gone as yet, is identical with a substance of the formula C6HllN305, called provisionally, thyreo-antitozin, which can be crystallised out by con- .centration ; it is very hygroscopic. It produces rapidity of pulse, but no fall of blood pressure, and when administered to animals deprived of their thyroids it delays the onset of death, and abolishes the nervous symptoms ; it does not, however, prevent death. W. D. H. Uropo'ietie Diastase. By CH. RICHET (Compt. rend. SOC. BioZ., 1894, 525-528) .-The alcoholic precipitate of extract of liver con tains two ferments, the activity of which is destroyed by boilinfl; when added t o liver extracts, the changes produced are a diminution of glycogen, and an increase of urea.W. D. H. 10-2120 ABSTRACTS OF CEEMICAL PAPERS. Composition of the Milk of Various Animals. By Anc;usro PIZZI (Stuz. Sper. Agrar., 1894, 26, 615-639).-The volatile, fatty acids of milk from various sources, and the points of fusion and solidification of the butter were determined with the following results. Wollny 31. p. of Solidification number. butter. of butter. Woman ........ 1.42 32.0" 22.5' Goat,.. ........ 28.60 36.5 31.0 Sheep .......... 32.89 29.0 12.0 Buffalo. ........ 28-18 38.0 29.0 Sow ........... 1.65 28-0 12.0 The Wollny numbers are also given foi. the following butters: Mare's, 11.22 ; ass, 13.09 ; rabbit, 16.06 ; bitch, 1.21 ; cat, 4-40 ; and rat, 2.97.The odour, colour, and taste, &c., of the butter are described. The following percentage results were obtained with the milk of (I) sheep, (2) goats from the Appenines, (3) buffalos, and (4) rabbits. Sp. gr. Albumin at 15'. Water. Fat. and case'in. Lactose. Ash. 1. 1.0413 80.425 9.66 4.44 4.37 1.10 2. 1.0326 86-73 5-35 3-64 3.60 0.66 3. 1.0332 82.20 '7.95 4.13 4-75 0.97 4. 1.0493 69.50 10.45 15.54 1.95 2-56 Determinations of volatile fatty acids in the colostrum obtaineti from cows a t successke periods, showed increased amounts as the conversion into normal milk proceeds. Sterilisation of Milk and the Lactic Fermentation. By PALL CAZENEUVE (BzcZZ. SOC. Chim., 1895, [3], 13, 502-509).-The milk i q sterilised by heating it in boiling water in screw-stoppered bottles, which are capsuled with tin, and completely immersed in the water, the air escaping t'hrough capillary orifices in the capsules subsequently closed by compression.As the bottles cool, the capsules and necks are coated with solid paraffin to eliminate all possibility of t h e entrance of air. Of the various samples of milk subjected to this treatment, some fresh, some about to turn sour, and some actually putrescent, none underwent further change-even when kept for days a t 35'. The lactic ferment seems to be attenuated and, to a large extent, de- stroyed by the process, for the sterilised samples remained for the most part unchanged after the admission of sterilised air, and did not give rise to colonies when sown in a gelatin medium.Milk thus treated is stated to be more digestible than new milk, and has not the objectionable colour or taste of milk boiled in an open vessel, or that sterilised at higher temperatures. The process. has been tried on the commercial scale. JN. W. N. H. J. 31. Protei'da of Normal Urhe. By ~ R L A. H. &roRNEB (Skand, drchiv PhysioZ., 1895, 332--437).-Although hcalthy human urine f o rVEGETABLE PHY SIOLOOY AND AGRICULTURE. 121 pvactical purposes contains no prote'id, yet there is prote'id matter present in extremely small quantities. For the purpose of ascertain- ing its nature, each experiment required many litres, often $0 or 90 litres of urine. This prote'id or proteyd-like material is contained partly in suspension in the ordinary mucous cloud or nubecula, and partly in solution.The research naturally, therefore, divides itself into two parts. The conclusions drawn in reference to the nubeculn are the following. The sediment of normal urine contains a specific member of the mucin group, named zriine-rnucoid, which probably originates from the mucous membrane of the urinary passages. It has the percentage cornposit.ion: C, 49.4, N, 12.74, S, 2.3, and is readily soluble in am- monia. From its solutions, i t is precipitable by acetic and other acids, find is only slightly soluble in excess of the acid. Its solution is lcevorotatory (a, = -62--67'), and it reduces alkaline copper solution slightly ; after boiling with hydrochloric acid, however, it is strongly reducing.It gives the prote'id colour-reactions. With a-naphthol and concentrated mlphuric acid, it gives no carbohydrate reactions. I t contains neither phosphorus (nucleic acid) nor conjugated sulphuric acid (chondroitin-sulphuric acid). I n many particulars it agrees with the ovomucoid of eggs. The soluble pi-ote'id in urine is chiefly serum-albumin ; bat some is precipitabh by acetic acid ; and this part consists of a nucleo-proteyd. Precipitated with the proteiid, chondroitin-sulphuric acid is constantly present; this is considered to originate in the kidneys where its presence has been previously shown. The relative amounts of albumin and this acid are variable; t h u s there is no compound between them. In some cases, taurocholic acid is present i n small quantities. W. D. H. Excretion of Creatinine during Regular Work on a Mixed Diet. By EDWIN ACKERMANN (Conzpt. rend. Soc BioE., 1894, 659- 660).-The experiments made on a man on a mixed diet, and doing regular work, show that, in the mean, the daily output of creatinine is 1-254 gram or 0.017 gram per kilo. of body weight. The amount is lessened by rest,. W. D. H. Resistance of Invertin to Heat. By Rouss~ (Compt. rend. SOC. Biol., 1895,400-402) .-The fever-producing property of invertin is not destroyed by temperatures between 100' and 150°, although it is lessened. The diastatic property of the same substance also is simply attenuated, and not completely destroyed by the same temperatures. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8967005118

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

VEGETABLE PHY SIOLOOY AND AGRICULTURE. 121 Chemistry of Vegetable Physiology and Agriculture, Mannitol Fermentation in Sicilian Wines. By G. BASILE (Staz. Sper. Agrw., 1894, 26, 451497).-Sicilian wines are subject to an abnormal fermentation, which, in some years, cause8 very great122 ABSTRACTS OF OHEMIOAL PAPERS. loss, the chief product of this fermentation being mannitol produced from the glucose ; it is generally the red wines which are attacked rather than the white wines, and it is chiefly in hot', dry seasons that this fermentation prevails. The bacterium ferment which produces mannitol, shows the Brownian motions when anagrobic, but is inert when aarobic ; and although it may coexist with the alcoholic fer- ment, it does not predominate until the alcoholic ferment loses its activity.The action of the mannitol ferment may be hindered by racking off the wine when the glucose has been ectirely consumed by t,he alcoholic ferment ; or the wine may be pasteurised, and resown with the alcoholic ferment. N. H. J. M. Action of Metallic Salts on the Lactic Fermentation. By ALLYRE CEASSEVANT (Compt. rend. Xoc. Biol., 1895,140-142 ; com- pare Abstr., 1894, ii, 6S).-Salts of magnesium, sodium, lead, gold, and copper, when added to milk in small quantities, produce an acceleration of the lactic fermentation, especially at the commence- ment. With gold and copper this, in time, is converted into a hindering action. Mixtures of the salts produce a similar action. W. I). H. Chemistry of the Barley Plant. By CHARLES F. CROSS, EDWARD J.BEVAN, aud CLAUD SMITH (Ber., 1895, 28, 2604--2609).-The plants were grown during 1894-95 on two of the plots at the Royal Agricultural Society's experimental station at Woburn, one plot being regularly manured, the other left entirely without manure. Samples of the plants were gathered at various periods and analysed, the dried residue, permanent fibre, and the furfuraldebyde obtained from both the dried residue and the permanent fibre being estimated. The results show that the difference in the treatment of the two soils has only a slight influence on the composition of the plant. The atmo- spheric conditions aff ecf tbe results very materially, especially the amount of permanent fibre. In the comparatively wet Beason of 1894 this increased in quantity throughout the whole period, whilst in 1895, the sunny spring of which was followed by wet weather, the amount of permanent fibre became less after the middle of July, and again diminished towards the end of August.The furfuroids appear to be accumulated as the growth of the plant proceeds, chiefly in the stable or cellulose-like form; at the same time, as shown by the diminution which occurred during the last period of 1895, they are able, when reqaired, to contribute to the necessities of the plant during ripening. A. H. Tannin Colouring Matters of Red Grapec. By L. SOSTEGKI (Stuz. Sper. Agrar., 1894, 27, 400413).-The red colouring matter obtained by concentlading wine on a water bath, adding hydrochloric acid, and allowing the mixture to remain overnight, was separated into two portions-one soluble in alcohol, the other insoluble.The former contained C = 56.62, H = 5-00 per cent., the latter C = 57.62, H = 4.70 per cent. The reactions of the two portions, which are fully described, indicate the presence in both of catechol andANALYTICAL CHEMISTRY. 123 phloroglucinol. The soluble sabst,ance seems to contain some other aromatic compound. More colouring matter was obtained from the residue left on dis- tilling the alcoholic extract of the marc of grapes ; after precipita- tion by water, the substance wits washed with hot water, treated with ether, redissolved in alcohol and again precipitated. The reactions much resembled those of the other two products. When heated with sulphuric acid (15 per cent.) at 130' for 12 hours, a compound con- taining rather more hydrogen than those mentioned above was obtained (C = 55.77 and 55.88; H = 6.30 and 6.18 per cent.). The results generally point t o the presence of catechol and 1-esorcino1, possibly also of quinol. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA8967005121

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. Analytical Chemistry. 123 Arrangement for Washing Precipitates with Boiling Water. By FRANK I?. JEWETT (J. Amer. Chem. SOC., 1895,17, 517-518)-- The water is boiled i n a wash-bottle fitted with a trebly perforated indiarubber cork, the steam escaping through an open clip. When n precipitate has to be washed, the clip is closed, and the pressure of the steam a t once drives the water through a tube bent at right angles, connected by a few inches of rubber tubing to ajet, which is wound about with a strip of non-conducting material, and may, there- fore, be easily handled. The bottle is also connected with an inverted flask fitted with a tube to allow escape of air. If the pressure should beconie too great, the steam simply forces the boiling water into the inverted flask.On reopening the clip, the water immediately returns to the lower flask. L. DE K. Estimation of Perchlorate. By D. ALBERT KREIDER (Zeit. anorg. Chem., 1895,10,277-288, and Amer. J. Sci., 1895, [3], 50,287-297)- -Potassium perchlorate, when boiled with potassium iodide and phos- phoric acid, is not reduced until the temperature reaches 215--220°, at which temperature metaphosphoric acid is formed ; if, however, metaphosphoric acid is employed, reduction takes place at 200°, and the author has attempted to employ this reaction for the estimation of perchlorate. The best results are obtained by gradually adding the potassium iodide to the mixture heated at about 300" in a current of carbonic anhydride, but the error amounts t o from 2 to 5 per cent. A number of experiments are described in which the perchlorate is melted with potassium iodide and an indifferent compound, and the metaphosphoric acid allowed to act on the mixture, but in no case could accurate result,s be obtained. When potassium perchlorate is fused with aluminium sodium chlo- ride, A12C16,2NaCI, chlorine is liberated, which is estimated by absorp- tion in potassium iodide; the reaction must take place in an atmo- sphere of carbonic anhydride. The results obtained are, however, only accurate to from 1 to 5 per cent.I24 ABSTRACTS OF OHEMXCAL PAPERS.An accarate estimation of perchlorate is effected by estimating the oxygen evolved when tbe salt is heated at 400’ ; this is effected by treating the gas with concentrated hydriodic acid in the presence of a, slight, excess of nitric oxide, the liberated iodine being titrated with a decinormal solution of arsenious acid.A full description of t.he apparatus employed is contained in the original paper; great care must be taken to exclude air, and this is effected by means of carbonic anhydride. In order to insure a steady evolution of oxygen from the perchlorate, the latter is covered with a layer of sodium potassium carbonate, the gas being collected in a suitable flask, and then gradually introduced into a flask containing a known quantity of concentrated hydriodic acid containing nitric oxide ; meanwhile great care must be taken to shake the mixture without intermission, as otherwise higher oxides of nitrogen will be formed. A constant error of +0.0003 gram of potassium perchlorate must be allowed for, but otherwise the results are accurate. If other oxidising compounds besides perchlorate are present, they are reduced by a reagent which is indifferent to pel-chloratc, and the filtered solution then evaporated to dryness, and the residue treated as above.The method is also applicable to the estimation of oxygen in air, and in all cases There oxygen is evolved. Qualitative Analysis of Mixtures of Sulphites, Carbonates, The saline mixture is placed in a small flask furnished with a tap- funnel and deliverj tnbe, and the sulphurous and carbonic anhydrides, expelled by the gradual addition of, and finally boiling with, dilute Iiydrochloric acid, are passed through tl solution of pchassium chro- mate containing potash free from sulphates and carbonates.If, at the end of the operation, the acid liquid is turbid with sulphur, the mixture must have contained a thiosulphate, whilst, if sulphates are present, these must hare been present as such in the original solu- tion. The presence of sulphates in the chromate solution, after warm- iog and acidifying with dilute hydrochloric acid, points, on the other hand, to that of snlphites in the original substance, provided no thiosulphate was present, whilst an effervescence ou adding the acid to the chromate solution can only be due to the decomposition of a1 kali carbonate. JN. W. Reduction of Selenious and Selenic acids by Hydriodic acid. By FRANK A. Gooca and W. G. REYNOLDS (Zeit. anorg. Chent., 1895,10, 248-252; and Amer.J. Sci., 18’35, [3], 50, 249-252).- Muthmann and Schafer’s method (Abstr., 1893, ii, 318) of estimating denions acid by reducing it with hydriodic acid and titrating the liberated iodine with thiosulphate is not accurate except under special conditions, but accurate results can be obtained if the iodine is removed from the sphere of action as it is liberated. The mixture of selenious acid, potassium iodide, and hydrochloric acid is distilled, and the iodine collected in a Will-Vareutrapp absorption appnratns ; a small quantity of iodine, however, always remains in the distillation flask, and this must also be titrated with thiosulphate. Not more than 0.2 gram of selenium dioxide is used for each estimation, and 3 grams E. C. R. and Sulphates. By LEOPOLDO GIACOMELLI (L’OTOS~, 1895,18,155) .-ANALPTICAL CHEMISTRY.125 of potassium iodide dissolved in 100 C.C. of water; a large excess of hydrochloric acid is without inflnence on the reaction. Selenic acid is reduced by potassium iodide and hydrochloric acid much more slowly than selenious acid, and the reaction takes place quantitatively only in the presence of a large excess of hydrochloric acid. By employing the distillation method, accurate results are obtained. Reduction of Selenic acid by Hydrochloric acid. By FRANK A. GOOCH and P. S. EVANS, jun. (Zeit. anorg. Chem., 1895, 10, 253-255, and Amw. J. Sd., 1895, [33, 50, 400402).--Selenic acid is completely reduced to selenious acid by heating with hydrochloric acid under certain conditions ; chlorine is liberated, and can be esti- mated by means of potassium iodide and thiosulphate.The concen- tration of the hydrochloric acid is very important; with a solution containing less than 10 per cent. by volume of hydrochloric acid of sp. gr. = 1.2, no action takes place after five minutes’ heating. Accn- rate results are obtained by employing a solution containing one-third of its volume of hydrochloric acid of sp. gr. 1.8, and continiiing the distillation until one-third of the total volume in the distillation flask has passed over. Not more than 0.2 gram of selenic acid must be used for each determination. I f the strength of the hydrochloric acid is allowed to reach 50 per cent., selenium comes over in the distillate. Reduction of Selenic acid by Potassium Bromide in Acid Solution.By FRANK A. GOOCH and W. S. SCOVILLE (Zeit. anorg. Chem., 1895, 10, 256-256, and Amer. J. Xci., 1895, [S], 50, 402-404).- Selenic acid is reduced to selenious acid by distillation with potassium bromide and sulphuric acid, the completeness of the action depending on the amount of potassium bromide employed, the strength of the sulphuric acid, and the concentration of the solution during the distillation. When the distillation is continued too long, selenium is liberated, and if an excess of potassium bromide is used, it is difficult to remove the liberated bromine from the distillation flask before the reduction to selenium takes place. The best results are obtained by employing 0.25 gram of selenic acid, 20 C.C. of dilute sulphuric acid (1 : l), 1 gpam of potassium bromide, and a total volume of 60 C.C.; the distillation is carried on until the reduction to selenium conimences, which is usually the case when the solution in the distillation flask measures about 35 C.C. The bromine in the distillate is estimated in the usual manner. E. C. R. E. C. R. E. C. R. Estimation of Nitrogen in Fertilisers containing Nitrates. By H. C. SHERMAN ( J . Amer. Chem. SOC., 1895, 17, 567-576).- After studying the various methods for the estimation of nitrogen in manures containing nitrates, the author arrives at the following conclusions. The official (American) methods are perfectly trust- worthy if the directions are followed closely and the digestion with acid is continued for a short time after the mixture has become prac- t ically colourless.In analysing samples containing a considerable amount of chlorides, it is, however, advisable to use zinc-dust and to cool the acid mixture before adding it to the sample. It is best to126 ABSTRAOTS OF OHEMIOAL PAPERS. digest for some time at the ordinary temperature before adding the zinc. If the amount of nitric nitrogen is very large, the boiling must be continued a long time, or else a little permanganate must be added to complete the action. Estimation of Small Quantities of Phosphoric acid by the Citrate Method. By E. G. RUNYAN and HARVEY W. WILEY ( J . Amer. Chem. Soc., 1895, 17, 513--514).-When the amount of phosphoric acid is below 10 per cent., the very convenient and accurate citrate process fails to give resulta corresponding with those obtained by the molgbdate method.The authors now advise adding a known amount of phosphoric acid, for instance, a solgtion of calcium phosphate of known strength, in order to bring the strength of the sample up to between 15 and 30 per cent. The results, after allowing, of course, for the added phos- Some Conditions affecting the accuracy of the Estimation of’ Potash as Potassium Platinochloride. By A. L. WIKTOX ( J . Amer. Chem. Xoc., 1895,17,453466) .-The author has investigated the conditions under which potassium platinochloride is obtained, and has tabulated the results. The most interesting result, from an analytical point of view, is that the precipitate obtained by adding platinic chloride to a concen- trated solution of a potassium salt consists chiefly of radiating crystals, a characteristic form having six arms, formed by the inter- section at right angles of three bars.Numerous globular cavities in the crystals shorn that, during their rapid formation, mother liquor is inclosed; the compound is therefore difficult to free from water, retaining some even a t 160’. On the other hand, the compound formed by mixing dilute solutions of the two metals, and then evaporating, crystallises in octahedrons, generally attached to one another, forming crystalline plates ; these crystals are comparatively free from cavities, and become very nearly anhydrous after drying for three hours at looo. Estimation of Lime in Soil. By G. BASILE and E. DE CELLIS (Stuz. Sper. Agrar., 1894, 27, 115--156).-1n determining the amount of lime in soil, the magnesium carbonate should also be estimated and the physical condition of the carbonates examined ; the nature of the predominating rocks of the surrounding country may have to be taken into account in forming an opinion as to the availability of the lime.Calcirnetry should be employed in conjunc- tion with direct estimation of lime and of magnesia if present. The error in the calcimetric method increases with soils rich in lime. Carbonic anhydride is best determined by weighing, employing Schrotter’s or a similar apparatus. For calcimetry, Scheibler’s appa- ratus is the best; Bernard’s method is uot recommended, but that of Houdaille and Sbmichon deserves attention. N. H. J. M. Volumetric Estimation of Zinc, and a New Indicator for Ferrocyanides. By GEORGE C.STONE (J. Amer. Chem. Soc., 1895, 17, 473-477).-The thoroughly oxidised solution of the ore is L. DE K. phoric acid, will then be quite trnstworthy. L. DE K. L. DE K.ANALYTICAL CHEMISTRY. 12’7 mashed into a 500 C.C. flask, and barium carbonate, suspended in water, is added until the precipitate of iron and aluminium hydr- oxides rapidly settle. After making up to the mark, the liquid is filtered, and aliquot portions are taken for titration. The author prefers titrating the manganese only, by means of the well-known permanganate method ; the joint amount of zinc and manganese is titrated by means of potassium ferrocyanide. It was found necessary to obtain a suitable indicator, as both copper sulpbate and uranium acetate act on the manganous ferro- cyanide; ferric chloride was also quite unsuitable.A very weak solution of cobalt nitmte is free from this objection; it must be applied a s follows : A drop of i t is placed on a white porcelain plate and a drop of the solution under treatment is added so that the drops touch but do not mix. The slightest excess of ferrocyanide is indi- cated by a faint greenish zone. L. DE K. Volumetric Estimation of Copper. By MATTEO SPICA (S’tax. S’er. Agrar., 1894, 26, 393-600) .-The copper solution is titrated with a solution of potassium ferrocyanide (containing K4FeCy6 + 3aq = 0.0845691 per cent.), paper prepared with ferric chloride being employed as indicator. The method gave results agreeing well with those obtained by the electrolytic process, whilst Borntrager’s method (Abst.r., 1894, ii, 120) was found to be unsatisfactory.The presence of nickel does not greatly affect the result if the quantity is small ; but any error from this source may be avoided by first precipitating the copper as sulphide, dissolving the latter in a little nitric acid, treating with ammonia and titratiug. This process has the further advantage of rendering it unnecessary to precipitate the iron with ammonia. A table of results obtained by the new method is given. N. H. J. M. Qualitative Separation of the Metals of the Iron Group. By C . L. HARE ( J . Amer. Chem. SOC., 1895, 17, 537-539).-T1he solution is mixed with ammonium chloride, and precipitated with excess of ammonia; after warming and filtering, the precipitate is boiled with aqueous soda, in which the alumina dissolves, and may be identified by acidifying and reprecipitating with ammonia.Thc insoluble residue is again boiled with soda, adding a few C.C. of hydrogen peroxide ; a yellow solution indicates chromium, this is acidified with acetic acid, and the presence of chromium confirmed by means of lead acetate. The insoluble residue is fiaally tested for iron by the ferrocyanide test. The ammoniacal solution is mixed with ammonium sulphide (free from polysulphide), warmed, and filtered, and the precipitate formed is treated with cold, dilute, hydrochloric acid to dissolve manganese and zinc, whicb are separated as usual ; the iiisoluble residue is then dis- solved in nitro-hydrochloric acid, and after espelling the excess of the latter by heating, tartaric acid is added, and then a large excess of aqueous soda.From this solution the cobalt is precipitated by a, current of hydrogen sulphide, and the precipitate may be further128 ABSTRACTS OF OEEMICAL PAPERS. recognised by the borax bead test. On acidifying the alkaline solu- tion, nickel sulphide separates, and may then also be tested with borax. Qualitative Separation of Chromium from Iron. By LEOPOLDO GIACOMELLI (L’Orosi, 1895, 18, 48-49).-The methods usually cm- ployed in the separation of chromium from iron in systematic quali- tative analysis, yield unsatisfactory results when the relative amount of chromium is s~uall, as the salts of the latter are liable to be carried down with the ferric hydroxide, or retained by the ferric oxide.The chromium is best separated by oxidising the ammonia precipitate containing only the mixed ferric, chromium, and aluminium hydr- oxides with a few drops of nitric acid, and a crystal or two of potas- sium chlorate ; the precipitate should be fairly well dried in a capsule before the addition of the oxidising agent, and the heating with the latter continued until the evolution of chlorinous fumes ceases. The chromium being thus oxidised to chromic acid, the iron and alumina can be precipitated as hydroxides with ammonia from the aqueous solution, and separated by means of caustic soda in the usual way, whilst the chromic acid can be recognised in the filtrate by means oE L. DE K. lead acetate after acidification with acetic acid. JN. w. Estimation of Benzene in Illuminating Gas.By WILLIAM A. NOYES and W. N. BLINKS ( J . Amer. Ckem. Soc., 1894, 16,697-698). -One hundred C.C. of gas is measured i n a Bunte burette, best with a side tube or bottle attached below, so that the gas is brought to atmospheric pressure. The water is then completely removed from the cup above, and the water in the burette is driven down to the lower stopcock as usual, for the introduction of reagents. Two or three C.C. of absolute alcohol is poured into the cup, and allowed to enter the burette 1 C.C. at a tlirne, care being taken that the walls of the burette are thoroughly moistened with it. After withdrawing the alcohol in the usual manner, 2 or 3 C.C. of water is admitted ttbave and withdrawn below, and more water is then admitted until the gas is brought to the original pressure.The difference between the two readings represents the benzene vapour which has been absorbed by the alcohol. L. DE K. Densimetric Estimation of &Glucose in Urine. By THEODOR LoHNsTEIN (pfE$ge?*’s 8 ~ c h i v , 1895, 62, 82-110) .-The mukiplicntor i n Roberts’ method of sugar estimation is not a constant, but varies with the specific gravity of urine free from sugar, with the percentage of sugar, and with the temperature. The removal of the yeast also makes a difference. Ifp = amount of sugar, t = temperature at which the sp. gr. is taken, S’ = sp. gr. of urine free from sugar, p = percentage volume, f = Robert’s factor, and the yeast remain in suspension. f = 234 - -+ ( p - 3) + 2 ( t - 20) + 487 S’ - 1.02)ANALYTICAL CHEMISTRY.12 9 From this equation i t follows that if p varies from 0 to 10, t from 15" to 25", and s from 1.01 to 1.03, f will vary from 222.3 to 244. There is thus a possible error of 5 per cent., although for most average cases the number 234 is pretty near. If S, = sp. gr. of the urine + yeast before fermentation, sz = 9 , ,, after * > tl and t2 = the resiective temperatures a t Khich S, and S, are observed. y1 = volume of original urine. V., = ,, urine after the addition of yeast, p = [S, - S, + 0.002 (tl - t z ) ] x 234 if t2 lies between then 15' and 20°, and = [S, - S? + 0.003 (tl - t,)] x 234 if t2 lies between 20" and 2.5'. s, - S? s, = s2 + ____ also 6 ' A better value f o r p is the following. S, and S, should be known to three decimal places.By such equatiom, the percentage of sugar can be est,imated to 0 1 per cent. The Polarising Microscope and Zeiss' Refractometer applied to Butter Analysis. By CARLO BESANA (Staz. 8per. Agray., 1894, 26, 601--G04).--By means of the polarising microscope, 5 per cent. of margarine in butter can be detected ; but butter which has been melted, and old butter, give rise to an appearance similar to that caused by margarine, so that the method can only be utilised for establishing the purity of butter. As regards Zeiss' refrsctometer, determinations should be made at a definite temperature (35" is convenient), as rise of teniperature lowers the refractive indices ; the temperature should be maintained constant during the experiment by means of a current of water. One hundred and eight samples of butter gave at this temperature the average result = 46, the maximum and minimum limits being respectively 47 and 44.8. Commercial margarine showed from 50 to 51 ; cocoa fat, 38.2 ; olive oil, 57 ; and sesame oil, 62.No effect, on the result seemed to be caused by the butter being rancid. Con- sidering the comparatively slight differences in the refractive indices of butter and margarine, a considerable admixture of the latter has but little effect on the result. Samples of butter which give results lower than 46 may be considered genuine ; in others, the volatile acids should be determined. N. H. J. 31. W. D. H. Estimation of Volatile and Insoluble acids in Butter. By W. H. BEAL (J. Arne?.. Chem. Xoc., 1894, 16, 673-676).--2*5 grams130 ABSTRACTS OF OHEMICAL PAPERS.of the clear butter fat is introduced into a long, narrGw, 200 C.C. Erlenmeyer flask. Saponification is accomplished by adding 2 C.C. of aqueous potash (1.-2), and 5 C.C. of 95 per cent. alcohol and boiling, using a reflux condenser ; five minutes is amply sufficient. The spirit must then be removed by means of a filter pump (Nilson, Abstr., 1889, Sol). The soap is dissolved in 30 C.C. of hot water, and decomposed with 20 C.C. of 20 per cent. phosphoric acid; the volatile acids are then driven off i n a. current of steam generated by boiling about 700 C.C. of water i n a litre flask, but in order to prevent accumulation of liquid in the Erlenmeyer flask, the contents of the latter should be kept boiling by means of a spirit lamp. The cooling apparatus consists of a deep trough, through which pass one or more glass spirals, fitted by india-rubber corks, and the distillate is collected in a wide-month Erlenmeyer flask, marked at 500 c.c., and carrying a funnel with a small filter.The distillate ia finally titrated, as usual, with N/10 soda and phenolphthaleYn. When the distillate amounts to 500 c.c., it may be taken for granted that all the volatile acids have passed over, but by may of extra precaution another 50 c c. may be distilled off and titrated separately. To collect the insoluble acids, the condenser and connections aro rinsed back with boiling water into the distilling fiask ; after cooling, the acid liquid is filtered through the same filter, and the washing and cooling is repeated until all the phosphoric acid is removed.The filter is then extracted with boiling alcohol, which is allowed to run into the distilling. flask. After expelling the alcohol and drying the fatty acids at looo, they are weighed. L. DE K. Untrustworthiness of Creamometers for the Estimation of Fat in Pasteurised Milk. By PAUL CAZENEUVE and E. HADDON (BUZZ. SOC. Chim., 1895, [3], 13, 500-502).-It is generally admitted that the cream in boiled milk cannot be accurately estimated by means of the creamometer, but no exact experiments seem to have been made on this point, nor any with milk sterilised by the well- known methods. The authors find that milk sterilised by Past-eur's method at 7&75", or go", yields, at most, half its cream, even after 27 hours, b u t that, when sterilised at 100' or 115' by Cazeneuve's method (this V O ~ ., ii, l20), out of contact with the air, it, yields practically the whole of its cream in the usoal way. The boiling of milk in the open air probably causes the oxidation and partial coagulation of the casein, and SO leads to the retention of the fat. JN. W. Estimation of Urea in Blood and Tissues. By MAURICE KAUF- MANN (Cmpt. rend. SOC. BioZ., 1895, 145--147).-Gr6hant's method of estimat,ing urea consivts in extracting the blood or tissues wit11 alcohol, evaporating the alcoholic extract, and decomposing the urea in the residue with Millon's reagent (" mercure nitreux ") into equal volumes of carbonic anhydride and nitrogen in the vacuum of a mer- curial pump. The results are described as very satisfactory. Other extractives are not thus broken up.W. D. H.ANALYTICAL CHEMISTRY. 131 Estimation of Urea in Animal Organs and Liquids. Ry BERNHARD SCH~KDORFF (P'iiger's Archiv, 189.5, 62,1-57).-After a review of previous work on the subject of the estimation of urea,, experiments are recorded which led to the following conclusions. The amido-acids, glycocine, alanine, lencine, sarcosine, taurine, tyrosine, metamidobenzoic acid, and aspartic acid give off all their nitrogen wben treated by the Kjeldahl process. They are not precipitated by a mixture of phosphotungstic and hydrochloric acids ; when heated with phosphoric anhydride at 150°, they do not give off nitrogen ; at 230°, however? they give off all their nitrogen, except taurine, for which a temperature of 240' is necessary ; and when heated with an alkaline solution of barium chloride at 150°, only traces of carbonic anhydride, coming within the limits of experimental error, are evolved.Urea is completely decomposed into carbonic acid and ammonia by four and a half hours' heating at 150'. By heating with phosphoric anhydride at 150', it yields all its nitrogen ; by heating at 150" with alkaline solution of barium chloride in a sealed tube, the full amount of carbonic anhydride is obtained. The substances of the uric acid group (uric acid, allantoin, allo- xantine, caffeine, xanthine, guanine) are insoluble in absolute alcohol, and are, with the exception oE allantoin and alloxantine, completely Precipitated from their solutions by the mixture of phosphotungstic and hydrochloric acids. Creatine is almost insoluble in absolute alcohol, and is not precipi- tated by the acid mixture (see below).On heating R solution for ten hours with dilute acetic acid, it is converted into creatinine, and is then precipitable by the acid mixture to the extent of 74 per cent. By heat- ing with phosphoric anhydride at 150°, it yields 1 mol. of ammonia, splitting up into methylhydantoin and ammonia. By heating with alkaline barium chloride solution, it splits up into sarcosine and urea, SO that, therefore, on analysis, 1 mol. of carbonic anhydride and 2 mols. of ammonia are obtained. Ry heating with phosphoric anhy- dride a t 150', creatine yields 1 mol. of ammonia, and with alkaline barium chloride solution at 150', 1 rnol.of carbonic: anhydride, whilst urea under the same circumstances yields 2 mols. of a,mmonin and 1 mol. of carbonic anhydride respectively. I n estimating urea by this method, i t is necessary that creatine should be absent, Creatinine is conipletely precipitable from an aqueous solution by a mixture of phosphotungstic and hydrochloric acid. By heating with alkaline barium chloride solution at 150°, it behaves like creatine, but with phosphoric anhydride there is only an incomplete decomposition. The method devised from such experiments for the estimation of urea in blood and other animal fluids is as follows: the proteid and extractives are first precipitated by the acid mixture. In the case of organs, these are finely minced, and extracted with alcohol; the extract, after acidification with acetic acid, is evaporated to dryness a t 50°, and the residue taken up with alcohol and again evaporated to dryness.The residue is then taken up with hot water, and the acid mixture added. In either case, the precipitate produced132 ABSTRACTS OF CHEMICAL PAPERS. filtered off, the filtrate made alkaline with powdered lime, and in it the total nitrogen, the nitrogen evolved by heating at 150’ with phosphoric anhydride, and the carbonic anhydride obtained by heat- ing with alkaline barium chloride solution at 150’ are estimated, and the results compared ; there should be 1 mol. of carbonic anhydride to 2 mols. of ammonia. The acid mixture has the following composition : 100 C.C. of hydro- chloric acid (sp. gr.1*124), or an equivalent quantity of sulphuric acid, is placed in a litre flask, which is t>hen filled up with phospho- tungatic acid solution. Detection of Creatinine in Urine. By WILLIAN OECHSNER DE CONINCK (Compt. rend. SOC. Bid., 1895, lll--112).-The coloi.ation produced in pathological urine by the addition of sodium nitroprusside and sodium hydroxide may be due not only to creatinine but also to acetone. W. D. H. W. D. El. Morphine Reactions. By GUSTAVE B RUYLANTS (Bull. SOC. Chim., 1895, [3], 13, 497--500).-1n addition to the well-known vioiet coloration with sulphomolybdic acid, a green coloratiorr may be pro- duced by varying the conditions of reaction. In either case, the alkaloid is dissolved in concentrated sulphuric acid ; to obtain the violet coloration, a drop of the cold solutiop is mixed on a white tile with a drop of the reagent (0.01 gram of ammonium molybdate per c.c.), whilst, to obtain the green coloration, the morphine solution is previously heated for a few minutes on a water bath. Both colora- tions are changed to orange by the addition of a crystal of nitre. Similar colour reactions are given by the other opium alkalo’ids. The iodic acid test may be modified by adding the solid acid to a solution of morphine in concentrated sulphuric acid a t 100’ ; a lilac coloration is formed, changing to red and slowly disappearing ; or, with larger quantities of iodic acid, a red coloration is produced at, once. JN. W. Estimation of Albumin in Cow’s Milk. By L. L. VAN SLYKE (J. AnLer: Chein. SOC., 1894, 16, 712-’il5).-Estimation of Casein.- Ten grams of milk is diluted with 90 C.C. of water a t 40-42’, mixed with 1.5 C.C. of 10 per cent. acetic acid, and the mixture sbirred with a glass rod and allowed to remain for about five minutes. The coagulated csse’in having been first washed by decantation, and then a few times on a filter, the filter axid contents are treated for nitrogen by the Kjeldahl process. The author uses the factor 6.25 for the calculation of the nitrogen to casein. Estimation of Albumin.-The filtrate from the casein is placed in a boiling water bath for 10 or 15 minutes. The precipitate, after washing, is then also treated by Kjeldahl’s method. The same factor is used. Remaining Nits.ogenous Compounds.-The author prefers to take these by difference, by subtracting from the amount of total nitrogen compounds (determined by Kjeldahl’s method) t,he sum of the case’in and albumin. L. DE I(.

ISSN:0368-1769    

DOI:10.1039/CA8967005123

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

General a n d P h y s i c a l Chemistry, Refractometric Observations. By JAX F. EIJKMAN (Eec. TTav, Chim., 1895, 14, 185-202; compare Abstr., 1894, ii, 173j.-The author has determined the refractive indices for the hydrogen lines a and p and A of a large number of organic substances, each being examined a t two temperatures differing by SOo to 125". A t high temperatures, Gladstone and Dale's molecular refraction formula gives too low values, whilst Lorenz's expression gives too high values; it should therefore be possible to obtain a moleciilar refraction formula which should give concordant values a t all tempera- tures. By calculating from the experimental numbers now obtained, the author finds that the results are best represented by the expres- sion (n2 - l)M/(n + 0*4), in which n is the refractive index, and M the molecular volume, and he therefore proposes to take this expres- sion as the molecular refraction.If the new formula is employed, the agreement between the observed and calculated inolecular refrac- tions becomes very close, and tlie dispersion equivalent for the increment oE an homologous series, CHP, acquires a constant value. W. J. I?. Molecular Origin of the Absorption B_ztnds of Salts of Cobalt and Chromium. By ALEXANDIIF, L. ETARD (C'ompt. rend., 1895, 120,1057-1060) .-Violet solutions of chromium sdphate and nitrate, and of chrome alum, exbibit a fine absorption band in the red, X = 678-6iO. Addition of a nitrite changes the colour of these solutions to lilac, and an arsenate turns them green, but the above characteristic band remains in the absorption spectrum, and is only shifted a little towards the red, X = 687-680.Chromic acid in concentrated solution also shows this band. On the other hand, anhydrous chromjl chloride, potassium chromate and dichromate,. and roseochromic sulpliate give no distinct band. The blue chromium potassium oxalate gives absorption bands in the red a t X = 700-693 and X = 732-729. The red solution of cobalt sulphate giws a band, h = 654-650, and the red solution of cobalt chloride a band, X = 667-642. If these solutions are turned blue by heating and adding a little con- centrated hydrochloric acid, two additional bands appear in the red, but the bands of the red solutions still remain visible. The author concludes that the absorption bands of the chromium and cobalt compounds are not due to the atoms of the metals, but to the internal arrangement of the molecules.As these absorption spectra resemble in character those of the mre earth and of uranium compounds, the hypothesis that each band in the spectrum of a rare earth corresponds with some element, is not iieceesarily true. Anomalous Rotatory Dispersion of M'alic acid. By RAFFAELB NASIKL and G. GENNARI (Gazzetta, 1895, 25, i, 41 7-438) .-Employing a Landolt-Lippich polarirneter, fitted with the ray-filters recently H. C. VOL. LXX. ii. 11134 ABSTRACTS OF CHEMICAL PAPERS. described by Landolt (Abstr., 1895, ii, 1): the authors haye examined the rotatory dispersion of malic acid dissolved in various solvents, under different conditions of concentration and temperature ; the mean wave-lengths, ,up, in millionths of a millimetre of the various rags employed, are 665.9, 591.9, 553.0, 448.5, and 448.2.I n a 4.6 per cent. aqueous solution a t 20": the specific rotation for all these rays is a h v o one; for red light of p,u =665*9, the value [a] = - 1-87', whilst for p,u = 448.2 [p] = -2.51'; as the concentration increases, the temperature remaining the same, the solutions become more and more dextrorotatory, until i n a 72.8 per cent. aqueous solution, the values of [a] for the above wave-lengths become + 1.80" and + 6.39' respectively. At intermediate concentrations, the solutions become inactive for one or other wave-length of light, although the particular solution for which [a] = 0 for light of one wave-length is strongly active towards a different coloured light.As the temperature of the solution rises, the value of [a] becomes more negative; thus a t 7" a 33.24 per cent. aqueous solution has a specitic rotation of [a] = 3-0.44" for the ray ,up = 665.9, and- of +2*63O for the ray pp = 448.2, whilst a t 41.5' these rotations become -5.96' and -5.84' respectively. The addition of boric acid to the solution acts in the same way as n rise in temperature. Malic acid has nearly the same specific rota- tion in both methylic and ethylic alcohols, and the variation in rotation with varying concentration is of much the same kind as when water is the solvent; the solutions are, however, much more laevorotatory than aqueous solutions. The ,satno seems to hold for propylic alcohol and acetone, although the laevorotation is not so high as when the solvent is methylic or ethylic alcohol.A number of solutions of sodium malate were examined, showing t h a t the specific rotations f o r light of various wave-lengths change in much the same way as with the acid itself. The dispersion coefficients of aqueous solutions of malic acid change very irregularly with the concentration, wbilst those for sodium malate vary much less with the concentration. After a full discussion of these anomalies, the authors are unable to furnish any explanation of them ; they can hardly be due to changes in the degree of ionisation, malic acid being so slightly dissociated in aqueous solution. There is also no evidence indicating the existence of hydrates or polymerides in solution, as cryoscopic determinations show that, in concentrated aqueous solutions malic acid has the normal molecular weight.New Examples of the Superposing of the Optical Effects of Two Asymmetric Carbon Atoms. By PHILIPPE A. GUYE and C. UOUDET (Compt. reic.d., 1895, 121, 827-829).-The amylic amyl- acetate of the formula CHMeEt*CH,-CH,*COO*CH,*CHMeEt contains two asymmetric carbon atoms, each of which should behave towards polarised light as though the rest of the molecule were inactive (Abstr., 1895, ii, 149). The authors have prepared compounds of the above formula from ( a ) a mixture of dextrorotatory amylacetic acid and racemic amylic alcohol, ( b ) a mixture of racemic amylacetic W. J. P. * i kGENERAL AND PHYSICAL CHEMISTRY.135 acid and lsvorotatory amylic alcohol, and (c) a mixture of the dextrorotatory acid and the lt-evorotatory alcohol. The first com- pound has the rotation [ a ] ~ = +4.36, and the second [a]D = +2*54. Theoretically, therefore, that of the third should be +4*36 +1*54 = +5*90, and the number actually found was [a]= = +5*64, in close agreement with the theory. The amylic amylmalonate, CHMeE t*CH,*CH(COO*CH2*CHSleEt),, contains three asymmetric carbon atoms. Compounds of this formula were prepared from ( a ) dextrorotatory amj-lmalonic acid and racemic amylic alcohol, ( b ) racemic amylmalonic acid and hvorotatot-y amylic alcohol, and ( c ) dextrorotatory amylmalonic acid and ltzvorotatory amylic alcohol. The first compound has the rotation [a]D = +6-10, and the second [a]= = t3.48.The rotation of the third should therefore be +9*58, and the number actually found was [ a ] , = + 9-68,. the hheory being thus again confirmed. H. C. By PAUL WALDEN (Zeit. physikal. Chem., 1895, 17, 245-266).-The product of asymmetry, P, of a substance containing four groups of molecnlay weights gl, g,, gs, and g4 attached to one asymmetric carbon atom, is obtained from the equation ., ., Optically Active Derivatives of Succinic acid. omitting the constant term ( 1 sin a)G, the product of asymmetry is supposed by Guye and his supporters (Abstr., 1893, ii, 561) to be a measure of the rotatory powers of optically active organic substances. The author has prepared a large number of derivatives of malic and succinic acids, and shows that in the several series of cornpounds thus obtained, the product of asymmetry does not, in most cases, even indicate correctly whether the specific rotation of a substance will increase or decrease when the mass g of one of the four groups is altered by substitution.Thus the specific rotations [aJD, and the molecular rotations [MI,, of many of the substances mentioned in the accompanying table should be negative in sign, judging by the products of asymmetry, whilst others which should be either Izevo- rotatory or inactive are highly dextrorotatory. An inspection of the table shows that the ethereal salts of malic acid are dextrorotatory, the specific rotation rising as the mass of the nlkyl group increases, until the maximum is attained a t about the propylic salt ; the amides are more lzevorotatory than the salts, and their specific rotation increases with the mass of the substituted amidogen.The alkylic salts of the substituted malic acids are 13evo- rotatory, and have about double the specific rotations of the parent alkylic malates ; the derivatives of chlorosuccinic and bromosuccinic acids prepared from ltwo-derivatives of mdic acid are all highly tlextrorotatory, and the specific rotations of the bromo-compounds are higher than those of the corresponding chloro-derivatives. Iso- merides, or two compounds which contain groups of approximately the same mass, although of different kind, hare not the same rota- tory powers. Two substances of the same molecular weight., differ- 11-2136 ABSTRAOTS OF CHEMICAL PAPERS. Substance.Dimethylic malate.. . . . , Dietliylic ,) . . . . . a Dipropylic ,, . . . . . . Diisopropylic malate.. . , Diisobutyric ,, . . .. Dicaprylic ,, . . . . Dimethylic acetylnialate ,, propionjlma lot0 ,, butjrojlma- late ,, isobutyrojl- malate ,, isoraleropl- malate ,, cliloracetjl- malate ,, broinacetyl- late Diam ylic ,, . . . a Diethylic acetjlmalato . . ,) propionyliiia- late , , hu t j roy lm alatc ,) isobutyrojlms. late ,, isowJc~ojliiia- late ,, bromacetylma- late ,, bromopropio- ii y 1 ma late ,, broruobutjroyl malate . ,, bromisobutj- royliiialate ,, ethoxgsuccin- ate ,, ch1or:tcetj 1- Dipropylic acetylmalate . nisla t e late late malate ,, butj1.o~lllla- ,, iaocalerojlma ,) broniacetgl- Diisobutjric sect) linalatt ,, butyrojlma ,, isoraleroyl- ,, bromacetgl- late maln t e mlilnt e - 6-85' - 10 '18 -.11 '62 - 10 '41 -1L.14 - 9.92 - 6-92 - 22 -92 - 22 *94 - 22 -44 -22 '36 - 22 *39 - 23 '80 - 22 -40 - 22 *52 - 22 *20 - 22 -22 - 21 -99 - 22 *07 - 22 -48 - 22 '48 - 24 -76 - 22 '57 - 1.44 - 22 *85 - 23 -52 - 22 -40 - 21 -68 - 22 '24 - 2 1 -88 - 21 -68 -19 -91 - 20 *38 1.2317 - 19.35 - 25 '32 -22.69 - 27 -39 - 27 '19 - 24.77 -46'76 - - 52 -07 - 51 '86 - 55 -07 - 55 -56 - 63 -38 - 52 '25 - 54 -6% - 57 9s - 57 -17 - 60 '46 - 69.92 - 73 -05 - 83 *93 - 76 '50 - 3-13 - 59 '40 - 69 -26 - 64 '50 - 65 -47 - 76 -41 - 63 '01 - 68 '52 - 65 -70 - 74 'SO 1 -1294 1 *0745 1 -076 1 -0418 1.079 0.9761 1.1975 1'1317 1 *12% 1 -1034 1 *3862 1 -5072 1 *1168 1 '0938 1 * 0736 1 *(I688 1 *0605 1.3936 - 1 '3325 1 -3059 1 '2850 1 .I015 1 *0724 1.1566 1 -0417 1 a0263 1.3150 1 * 0362 1 '0146 1 -0045 1 -2022 - n.-- 1 '4&25 1 *4362 1 *4380 1 -4392 1 '4438 1 -4500 1.4318 - - 1 -4342 1 *4310 1 *4350 1.4530 1 '4680 1 *4295 1 -4305 1 *4315 1 -4285 1 -4338 1 '4610 1-43.61 1 *A568 1'4520 1.4320 1.4315 1 -4465 1 '4348 1 -4352 1,4608 1'4330 1.4352 1 -4353 1 -4520 -__ Observ -- 34 '78 44 *oo 53-26 62 -14 71-48 98 -57 44 -17 53 '41 53 -35 58 - 18 49 -35 52 -20 53.61 58 9 9 62 5'5 62.65 67 *26 61 '24 66 -31 '70 -68 - - 71 -17 54 '10 62 -82 67 *9R 72 '11 76 -81 $0 -71 72 '32 81 -30 85 -78 82 *36 R. Calc. -- 34 -98 44 -18 53 -40 62 -60 71 -80 99 -4.2 44 -52 - - 53 -73 53'73 58 *34 49-48 52 -41 53 '73 58 -33 62 -94 62 *94 67 *55 61 *61 66 '22 $0 -82 $0 -82 53 *55 62 '94 67 -83 72 -1.5 76 -75 70 -82 72 -15 81 '35 85 9 6 80 -03GENERAL AND PHYSICAL CHEMISTRY.137 Substance. Chlorosuccinic chloride. . Dimethylic chlorosuccin- Diethy1 ic chlorosuccinate Dipropylic ,, Diisobutyric chlorosuc- Diamylic chlorosuccinate Dimethylic brornosuccin- Diethylic bromosuccinate Dipropylic bromosuccin- Diisobutyric broinosuc- ate cinate ate ate cinate C a b + 20 -53 + 41 '42 + 2'7 '50 +25-63 + 21 '57 + 21 '56 + 51 '18 + 4.0 *96 +38-05 + 23'66 W I D . --- + 55 -93 + 74 -76 + 57 -33 + 60 -61 + 5'7 *05 + 63 '07 t 114 -37 t 103 *63 t 106 *9 + 72 -80 d. 1 '5003 1 '2555 1.1493 1 '0925 1 '03.24 1 *0319 1 .i5050 1.3550 1 -3010 1,2394 n. -- 1 *4840 1 -4436 1 -4372 1 a 4 4 1 2 1 '44.03 1 a4436 1 -4618 I *4550 1 -4592 1 * 4580 R. 3bserv. 36.12 33 -16 47 -55 57 -19 66 *20 75 -24 41 *32 50 -66 59-07 68 -03 CdC.-- 35 -73 38.40 4'7 '61 56 '82 66.03 73 -23 41 -33 50.24 59 *74 68 -94 - ently distributed in the two cases between the four molecular groups, have sometimes nearly the same, and sometimes very different rotatory powers; in some cases, a considerable a,lteration in the mass of a gvoup causes only a very small change in the rotatory power. In addition to the specific and molecular rotations of the various substances determined at 20°, the table gives the densities d, at 20' referGed to water at O', and the refractive indiccs n, for the D line at 20°, together with the observed and calculated molecular rotations R, obtained from Gladstone's formula. JV, J. P. Optically Active Derivatives of Rhenylacetic acid : Optical Superposition. By PAUL WALDEN (Zeit.y h y s i k d Chein., 1895, 17, 705-7'24 ; compare preceding Abstr.) .-Starting with mandelic acid, in which the four groups attached to the asymmetric carbon atom have the masses 77, 45, 17, and 1, the author has prepared and ex- amined the rotatory powers of a number of derivatives in mliich the masses of the above four groups vary; from the data thus obtained, the author shows that, as in the case of the malic acid derivatives, the product of asymmetry affords no criterion of the rotatory power, and deduces conclusions similar to those stated in the preceding ab- stract. The carboxyl group in mandelic acid is of practically the same mass as the group CONHZ in mandelamide, so that these two substances should have almost the same rotatory power. Table I, however, shows [a]a to be very different in the two cases.Similarly, tartaric dianiicie has a specific rotation in water or saturated boric acid solution of [ a ] ~ = 4-108' to 109.4", whilst for tartaric acid The very different specific rotations possessed by ethylic mandelate in acetone and carbon bisulphide solations seem not t o be due to a difference in molecular weight, as this snbstance depresses the boiling point of the two solvents normally. [ a ] D = +14*93.185 ABSTRACTS OF CHEMICAL PAPERS. Substance. ---- Mandelic acid . . . . , . . Mandelamide . . . . . . . . Methylic mandelate . . Ethylic ,, .. Isobutyric ,, .. Methylic acetylmande, Amylic Y Y ' * late mandela te mandela te ,, propionyl- Ethylic propionyl- ,, raleroylman- delute Acetylmandelic acid..Phenylchlometic anid ,, chlor. ide Methylic phenylchlor- Ethylic phenylchlor- PropyIic phenylchlor- Amylic phenylchlor- Phenylbromacet,ic acid Methylic phenylbrom- Ethylic phenylbrom- Isobutyric phenyl- Phenylbromacetic bro- acetate acetate acetate acetate acetate acetate broniacetat e mide TABLE I. Calu. - 153 *lo in H,O. . . - 66.7 ,, COMe, -110.2 ,, COMe, - 123 * 12 liquid . . . -100'73 ,, . .. - 96'46 ,, . .. -146.37 ,, . .. -135'5 ,, ... -113.7 ,, ... - 97.06 ,, . .. - 156 *4 in COMez. + 158 * 3 ,, CS, . . . . + 107 -55 liquid . . . + 25-19 ,, . .. + 23-94 ,, ... + 23.41 ,, . ,. + 45 -4 in CGH,. . . + 28 -82 liquid . . . + 16-56 ,, . .. +131*8 ,, CsHs a . + 9.77 ,, * I . -t 44.53 ,( . * . - 148 *Oo in COMe, -214.1 in CS,. - 88.8 ,, COMe, - -145 '0 ,, CS,.- - 110 in CHCI, . . -117 ), csp + 131 -3 in CS,.. , . I + 26 '39 in CSn.. . Ca!D. -180.0" in CS?. -129 in CS?. t 107.9 in CHCI,. In order to test the principle of " optical superposition," which states that the seve~al optically act.ive groups in a given molecule act additively and in such a way that the specific rotation of a sabstance becomes the algebraic sum of the specific rotations of two of its stereoisomerides, the authoy has examined a number of suitable salts and obtained results which are summarised in Table 11. The density d, the molecular rotation [MI,, and the specific rotation [a]D, of each series of three salts was determined ; the last column contains the specific rotation of the third salt of each series calculated as the sum of the specific rotations of the first and second.The specific rota- tions of lavo-amylic laevo-lactate is thus the sum of the specific rotations of inactive amylic leevo-lactate and lavo-amylic inactive lactate ; the agreemeut, as will be seen, is very close.GENERAL AND PHYSICAL OHEMIISTRY. TABLE 11. i-amylic Z-lactate.. ................ 1- ,, i- ................... I- .. 1- .................... i-amylic 1-mandelate .............. 1- 3 1 i- ,7 1- $ 9 1- ,, .............. .............. f i-amylic d-phen~lchlorscetate ...... ,, 7 5 ...... I:: 1; 2 ...... 1 1 - .. i- .................. i-diamylic Z-malate ................ Lr- .. 1- .................. i-diamylic d-chlorosucciiiate ........ 1- ), i- ........ I. ), d - ........ 7 9 , i-diamylic d-tartrate ..............I - ,, racemate I. .. d-tartrate .............. ............... -( Cl. 0 -9719 0 *9672 0 -9667 1 -0531 1 -0520 1 -0530 1 -0828 1 -0832 1 -0826 1 .om0 1 -0180 1 -0176 1 '0319 1 *0314 1 -0303 1 '0637 1 -0640 1 -0636 [ Af] D. - 10 -21C + 4-22 - 6.29 - 214 '14 + 6-12 - 208 '72 + 56'03 + 7.79 + 64.42 - 27-19 - 18-85 + 67.03 + 10.98 + 73.53 -- - - - 139 Observ. -- - 6 ' 3 8 O + 2-64 - 3.93 - 26 '46 + 2-76 - 94 -02 + 23 -31 + 3'23 + 26 -79 - 9'92 + 3'50 - 6.88 + 2 1 -56 + 3.75 + 25 *15 + 14 -10 i- 3.37 + 17,73 W. J. P. Optically Active Halogen Compounds. By PAUL WALDEN (Ber., 1895, 28, 2766--2773).-See this vol., i, 139. The Birotation of Glucose. By HEINRICH TREY (Zeit. yhysikal. Chenz., 1895, 18, 193-218) .-The birotation phenomena of glucose were investigated in aqueous and other solutions, both the anhydride and the hydrate being employed. I n solutions in methylic and ethylic alcohol, birotation occurs as in water, but more slowly, whilst also the final valh3 is hig!ier than in aqueous solution, both initial and final values being higher in ethylic than in methylic alcohol.By the addition of water to the alcoholic solution, the retrogression was accelerated and the final value also reduced to an extent correspond- ing with the quantity of water added. Chemically indifferent com- pounds cause a retardation in the methylic alcohol solution of the anhydride, and a slight increase of the end value. I n aqueous solu- t'ions of both anhydride and hydrate, acids cause an acceleration, the effects in t h k respect being in the same order as the aflinity con- stants.By the addition of hydrogen chloride, even in small quanti- ties, to the methplic alcohol solution, the rotation was reduced to zero, this being probably due to decomposition. By the solution in water of the amorphoiis residue left on evaporating an alcoholic solntion, the end value of the rotation was at once obtained, and the author considers that his experiments indicate that the explanation of the birotation is t.0 be sought for, not in the hydration of the compound,140 ABSTRACT3 OF CHEMICAL PAPERS. but in a change from a crystalline to an amorphous variety, or in some such alteration of the molecular configuration. (Compare also Levy, Abstr., 1895, ii, 586.) L. M. J. Theory of the Decomposition of Racemic Compounds.By CHR. WIKTHEIC (Bey., 1895,28,300O-3U2~).-T he aut’lior enunciates a general theory respecting the decomposition of racemic compouiids into their optically active constituents either by means of active bases or by crystallisation. The theory only holds good for com- pounds in the solid state or in saturated or supersatumted solutions, The atoms or groups attached to the asymmetric carbon atom of one molecule are supposed to have certain affinities for the corresponding atoms or groups in a second molecule, These affinities the author terms “ secondary,” and supposes they are of two kinds. For example, in the case of a compound containing an asymmetric carbon atom to which hydrogen and hydroxyl me attached, the affinity between the H and H, or between OH and OH, is termed “ racemic ” affinity, and that between H and OH “ contrary ” affinity.If, under given cir- cumstances, the racemic affinities of a compound are greater than the contrary affinities, it will be found impossible to split up the compound into its active constituents by the above means ; in order to bring about such a decomposition, energy, either thermal or chemical, must be sup- plied to the system. Under a certain set of conditions there will always be an equilibrium between the two secondary affinities. It is shown &hat the theory agrees with the facts hitherto known regarding the decomposition of racemic compounds, and the paper concludes with an index to the literature of the subject. J. J. S. Flames and Illuminating Gases. By C. BOHN (Zeit.physiktil. Chem., 1895, 18, 219--239).--The form of Bunsen burner devised by T e c h (Abstr., 1892, 768) was used for the experiments. The ap- pearance of the flame is first described, five parts being recognised- (1) the inner cone surrounded by (2) the mantle, around which lie (3) the outer cone with (4) its border, above which is (5) the cap. The variations in the several parts according to the air supply is recorded, and then the spectroscopic examination. The cap gave n feeble continuous spectrum with 110 red and but little blue; the border also gave a continuous spectrum with the red feebly cle- veloped ; that of the outer cone was also continuous, dark and bright lines being absent, and the red being well deyeloped. The mantle, however, gave a band spectrum with well-marked green and indigo or violet bands, and under some circumstances a blue stripe also, and a dark band close to the D lines.The inner cone appeared to give a feeble band spectrum, most probably, however, due to the mantle. The author considers the mantle t o be the place of explosive combus- tion and of the greatest development of energy, although not neces- sarily the hottest part of the flame. Sulphur, hydrogen, carbon bisulphide (by a wick), and carbonic oxide mere also burnt, and for all these flames, the spectra were continuous. The measurements of the band spectra .are recorded, the results being compared with those obtained by Swan. The spectroscopic measurements are alsoGENERAL AND PHYSICAL CaEBlISTR T. 141 recorded in the case of Geissler tubes containing various carbon com- pounds, and the author concludes that the discontinuous spectra of carboniferous gases are not identical, the cliffereuces being greater than those occasioned by alterations of temperature and density.It is hence not possible to define a carbon band spectrum, and even sharp- ness of the less refrangible cdge of the bands, and gradual fading of the more refrangible edge, does nct exist with all carbon compounds. Cause of Luminosity in the Flames of Hydrocarbon Gases. By VIVIAN B. LEWES (Proc. Roy. Xoc., 1895, 57, 4,50--468).-Accord- ing to the " solid part,icle '' theory of luminosity, i t is to be expected that the luminosity of different flames of the same size and burning from the same kind of jet, would be governed (1) by the tempera- ture of the flame; (2) by the number of carbon particles in a given area.I n order to determine the temperatures of different flames, the author has made use of a very small and thin Le-Chatelier thermo- couple. Preliminary experiments showed that the diameter of the wire seriously affected the temperature recorded, and the author concludes $hat the temperatures indicated by the finest wires which can be used without fusing are probably 100--200' too low. The following results were obtained. L. M. J. Acetylene. Ethylene. Coal gas. Non-luminous zone.. . . . . 459' 952" 1623' Commencement of lumin- osity . . .. .. .. .. . . . . .. 1411 1340 1658 Near top of lnniinous zone 1517 1865 2116 As regards luminosity, however, the three gases stand in exactly the reverse order; and as there appears to be no apparent relation between the temperature of the flame, or the probable number or carbon particles contained in it, and its illuminating value, it is sug- gested that the luminosity must be in great part governed by some thermochemical changes taking phce in the flame and yet not, appre- ciably affecting the average temperature.It is thought that as acetylene is formed when hydrocarbons are burnt, and as i t is an endothermic substance, the heat liberated during its decomposition endows the carbon particles with a high incandescence. In sup- port of this view, the author shows that acetylene, when decom- posed by a detonator or merely by strongly heating it in a glass tube, develops light. It is also shown that acetylene, when largely diluted with hydrogen, carbonic oxide, carbonic anhydride or nitrogen, burns with a non-luminous flame (compare P.E'ranklaiid, Trans., 1884, 30 and 227). It has been found possible to make such mixtures burn with luminous flames by externally increasing the tem- perature. The luminosity of a flame, therefore, depends not so much on the percentage of acetylene in the gas, but rather as to whether there are many points at which the temperature is su6cientlg high to bring about decomposition of the acetylene. The flame of alcohol contains as much acetylene as a good coal gas flame, and yet is non-, or only142 ABSTRACTS OF CHEMICAL PAPERS. slightly, luminous, because the temperature is too low to decompose the acetylene. When burnt in oxygen, the flame becomes brightly luminous, owing to the increase in temperature.Cyanogen, which is even more endothermic than acetylene, burns with a non-luminous flame. This is due to the fact that cyanogen requires a much higher temperature before it is decomposed, and i t is shown that when suffi- ciently strongly heated, it can be made to burn with a luminous flame. J. J. S. Red and Yellow Mercuric Oxides. By WILHELM OSWALD and THOR MARK ( Z e d . physikal. Chem., 1895,18, 159-160) .--The experi- ments of Varet proved the identity of the heats of formation of the two mercuric oxides, hence the total energies are equal for these com- pounds (Abstr., 1895, ii, 305). A galvanic cell of mercury-red oxide -caustic potash-yellow oxide-mercury, was found by the author to give no E.M.F., whilst, also, no change of the E.M.F.of various cells occurred when red and yellow oxides replaced one another. Hence, the author points out, the free energyof the two forms are alsoequal, and the compounds are not isomeric but identical. L. M. J. Peroxide Electrodes. By O L ~ N FREEMAA’ TOWER (Zeit. physikal. Chem., 1895,18,17-50) .-Examination of varions peroxide electrodes showed those of lead, silver, and thallium t o be unavailable, as with the first a long time is necessary before a constant E.M.F. is obtained, whilst the two peroxides last mentioned are unstable and readily acted on by dilute acid solutions. Manganese peroxide, being free from the above disadvantages, was therefore selected for the experiments. The E.M.F. with this electrode is given by the formula n ~ ~ 7 r = Rt log (C,C$/Cm~CoQ), where C, + Co are the concentrations of the manganese and hydroxyl ions respectively, the other letters having the usual significance.k/C, may be substituted for C,,, and the formula reduces to In acid solutions, C, x CH being constant. 7 = -0.0286 log (CmCH4/CmCH4). Experiments were made with solutions of varying nitric acid and manganoua nitrate conient ; the observed and calculated results show satisfactory agreement, the differences being probably due to incom- plete dissociation. As t,heoretically indicated, the effect of the salt concentration was found to be four times t h a t of the acid. Experi- ments were also made with phosphoric, malonic, tartaric, formic, acetic, salicylic, orthamidobenzoic, mono-, di-, and tri-chloracetic acids, the concordance between the observed and calculated numbers being again, for the most part, satisfactory. The influence of temperature was next determined.This, in the case of nitric and sulphuric acids, is very slight., rather more for phosphoric and the chlorrtcetic acids, and very marked with acetic, formic, and tartaric acids. No reason for these differences is, however, indicated. The determination of the E.M.F. is also employed for the determination of the degree of dissociation of the sodium salts of 16 organic acids at varying concentrations, and the results compared with those obtained by Trevor (Abstr., 1893,GENERAL AND PHYSICAL CHEMISTRY. 143 ii, 62). The only cases in which satisfactorp agreement is not obtained are those of the phthalates and isophthalates, where the author finds the former salt to be the more highly dissociated.Barium salts were also employed in a few cases, and the dissociation is determined for acid snlphates of potassium, magnesium, sodium, aluminium, and copper, hydrogen sodium selenate, and dihydrogen sodium phosphate. I n a1 kaline solutions, the electrolyte is a solution of Mn(OH),, hence C,,, >: C,Z = k, and C,C$ = 3i/C,,L, hence Z- = -0°.0286 log (Co2jC2). The availability of the formula is shown by experiments with potas- sium, sodium, barium, strontium, calcium, and ammonium hydr- oxides. By the use of a perfectly neutral solution, the dissociation o€ pure water is obtained as 4.4 x lo+, a number which, although of the same degree of magnitude, is smaller than that which has been obtained by other methods.IJ. M. J. Potential Differences between Metals and Electrolytes. B y GEORG MEYER (Ann. Phys. Chem., 1895, [2], 56, 680-699).-Roth- mund (Abstr., 1823, ii, 35) has calculated the E.M.F. of various cells from his electro-capillary measurements of the potential differences between the metals and electrolytes composing them, and in a number of cases the values thus obtained do not agree with those directly measured. The author has repeated, and, in general, confirmed Rothmund's measurements. He therefoi-e concludes that the E.M.F. of a cell M, I F, I F2 I M2, composed of the metals M, and M, and the electrolytes F, and Fa, is not given by the difference between the forces necessary to produce the maximum surface tension of polarisa- tion of M, in F1 aud of M, in Fz.The potential difference between the two metals and two electrolytes must be taken into account', and to the difference of E.M.F. above spoken of must be added the potential difference between two dropping electrodes, which, contain- ing MI, and Mz, are respectively placed in the electrolytes F, and F,. It is only when this last term approaches zero i n value that it can be neglected . H. c. Electro-capillary Properties of Dilute Sulphuric acid. By A. GOUY (Compt. Tend., 1895, 121, 765-768)-'l'he author has made a number of determinations of the relationship between the height h of the column of mercury balanced by electro-capillary forces, and the difference of potential V between the mercury and the electrolyte, using solutions of sulphuric acid of various concentrations as the electrolyte.The ralues of h decrease vith the coucentration of the solution, but, in the more concentrated solutions, exact measurements become impossible, owing to the occurrence of electrolpsis. The second derived function d'hldV? is always negative, so that the curve of h has no point of inflexion, and does not tend to any limiting value. 'l'he actual value of the function is not constant, but is subject to complex variation. H. C. The Passage of Electricity through Gases. By OTHO LEHMANN (Zeit. yhysikal. Chew ., 1895,18, 97-11 7).-Experiments are described on the electric discharge through various gases, vacuum tubes,144 ABSTRACTS OF Cl3JZMICAL PAPXRS.mixed gases with different forms of elcctrodes, and the discharge iii a strong magnetic, field. The paper is illustrated by a number of figures of discharge phenomena, aiid the author considers the views of Goldstein aiid Hertz, that the discharge takes place iirto the ether and not into the gas, to be erroneous. Relation between the Di-electrical Constants of Gases and their Chemical Valency. By ROBERT LANG (Ann. Phys. Chem., 1895, [2], 56, 534-545).-Between the dielectrjcal constant, I<, of a gas, that of the ether being unity, and the sum of the valencies of the atoms in the molecule of the gas, s, the author finds that there is the following general relationship. I < - 1 ~ loG = 123. L. 31. J. S This relationship does not always hold if. the simple chemical molecule of the gas is taken, but, in such cases, the assumption is made that a number of theso molecules are combined to form a com- plex group, when agreement is obtained.The values of I< are taken tor 0" and 760 mrn. pressure. The term dielectricaE valency constcmt is proposed f a - the constant, the value given abore for this being provisional only. H. C. Determination of High Resistances. By MARGARET E. &fA4LT131' (Zeit. physikal. Chem., 1895,18, 133--158).-A method for the deter- mination of high electrolytic resistances is described, previous methods being considered unsatisfactory. A Wheatstone bridge is employed with four carefully calibrated adjustable electrolytic resistances, and when a balance is obtained, the unknown resistance is placed in one arm (1) in series (2) parallel, and that resistance again adjusted for a balance.F u l l details of bhe construction, calibration, and working of the instruments are given in the paper. Comparison of numbers obtained with those due to Kohlrausch indicates the availability of the method. Experiments are recorded with a solution of hydrogen chloride in ether a t its critical temperature, the resistance increasing from 641 divisions a t 20' to 24,180 a t .197", a t which temperature critical phenomena were observed. Solutions of trichloracetic acid in ether, and of potassium chloride in water, were also examined a t high temperatures. The former gave a continuous decrease until 75O, when the resistance commenced to increase ; with the latter salt, the resistance decreased regularly to 297".The method is stated t o be available for the determination of the conductivity of pure water, but no measurements are recorded. L. M. J. Determination of some Conductivities. By A. E. BACR (Zeit. physikal. Chem., 1895, 18, 183--184).-The Conductivity of tetrazole compounds was first examined with the following results : Tetrazole, CN4H2, , L L ~ ~ ~ ~ = 37.96 ; amidotetrazotic acid, CZHGNIO, plOgl = 11.61 ; sodium azotetrazole, C2N,,Na2,5H,O, = 103.6 ; sodium amidotetr- azotate, CH,N,Na,SH,O, plmi = 93.27. The conductivities of the chlor- ates of caesiuni, rubidium, and potassium were fouild t c be 137.5,134*9, and 129.9 respectively (ploz4), and hence, taking the ion velocity ofGENERAL ASD PHYSICAL CHEMISTRY.145 potassium as 70.6 and pm = + 3, the following ion velocities are obtained: Rb, 75.6 ; Cs, 78.2 ; Clod, 62.3. The ralues of the Yeloci- ties of the inetdlic ions were also determined by means of the chlorides aich the results Rb, 76.5; CS, 79.3. L. M. J. The Dilution Law of Salts. By JACOBUS H. VAN'T HOFE' (Zeit. p7~ysikaZ. Ohem., 1895,18, 300-304) .-Rndolphi found (Abstr., 1895, ii, 490) that the relation between the molecular conductivity and the instead of by Ostwvald's expression X: = The author v ( l - X7./A.-)* shows that in Rudolphi's experiments a slightly -be;& constancy of (X,i'h,)4 d v ( l - h4Am)' k is obtained by the. expression ---e--- -__- which leads imme- diately to t h e equation ci3/cs2 = constant where ci and c.* are the concentrations of ions and non-dissociated substance respectively, although, as the author points out, the physical interpretation is not very clear.L. 31. J. Specific Heat of Mercury between 0" and 30". By ADOLFO BARTOLI and ENRICO STRACCIATI (Gazzettn, 1895, 25, i, 380-388). -After a summary of the work previously done, the authors give an account of their determination of the specific heat of mercury between 0" and 30" made by cooling a mass of platinum, previously heated in a steam bath, in Titer, and in pure mercury, successively; using the values for the specific heat of water pre- yiously obtained b.y them (Abstr., 1895, ii, 5 ) , the specific heat of mercury between 0" and 30' is given by the equation in \vhich T is the temperature for which the specific heat C is ibequired. The numbers agree well with those obtained b,y Naccari and by Winkelmann. Specific Heats of Platinum, Silver, Tin, Lead and Copper.By Auor,~o RAR'l.OL1 and EXRICO STRACCL4TI (Gazzetta, 1895, 25, i, 359-393 ; compare preceding abstract) .-The authors have obtained. the following values for the specific heats of various metals between 15" and 100" as the means of a large number of measurements ; the values are referred t o water a t 15", and the impurities are given in percentages. C = 0.033583 + 0~00000117 T - 0-0000003T2, W. J. I?. PIatinuin (containing traces of Ir) ............ 0.63223s Silver ( ,, 0.047 Cu and 0.016 Au) . . 0.056250 Tin ( ,, 0.030 Fe and 0.008 Pb) . . 0.055550 Lead ( ,, 0.030 T1 and traces of other metals) .............. 0.030887 Copper ( ,, 0.12 Sn and 0.12 Au) ....0.093392 9 1 ( ,, 0.005 Sn and traces of other inetalsj ........ 0.093045 W. J. P.'146 ABSTRACTS OF CHEMICAL PAPERS. Latent Heats of Vaporisation of Ketones and other Carbon Compounds. By WLADIMIR F. LOCGDININE (Compt. rend., 1895, 121, 556-558).-1n the following table, column I contains the boiling point under a pressure of 760 mm., colnmn I1 the latent heat of vaporisation, arid column 111 the ralne of the constant in Trouton's expression MS/T = constant, where M is the molecular weight, S the latent heat of vaporisation, and T the boiling point on the scale of absolute temperatures. I. 11. 111. Dipropyl ketone ............ 163*90° 75.94 Cnl. 20.76 Methyl butyl ketone.. ....... 127.61 82.91 .. 20.70 Diethyl ketone.. ...........102.46 90.54 ,, 20- 74 Methyl isopropyl ketone.. . . 94-04 88.67 ,, 20.78 Nethyl ethyl ketone. ........ 79-54 103.44 .. 21.13 Decane .................... 159.45 60.83 .. 19-98 Octane (normal). ........... 124.90 70.92 ,, 29-32 Diethylic carbonate ......... 126.28 72.80 .. 21-53 Dimethylic carbonate. ....... 90.30 87.87 .. 21.76 These results, with those of previous observers, show that in each group of compounds the value of MS/T is almost constarit, whilst i t differs considerably i n different groups. Ostwald has already pointed out that this expression makes it possible to calculate the latent heat of vaporisat'ion with a probable error of not more than 15 per cent. Since, however, the variations in its value are very small in a group of homologous and isomeric compounds, the latent heats of vaporisation of all the memhers of a series can be calcu- lated with an error of not more that 1 to 1.5 per cent., when the Talue has been experimentally determined f o r one member of the series.C. H. B. Determination of Transition Points. By A. E. BAUR (&it. physiknl. Chem., 1895, 18, 180-182) .-The transition temperature was determined by the electrical method of Cohen and Bredig (Abstr., 1894, ii, 407) in the change Na,HP04,12Hz0 - Na2HPOJ,7Hz0, and the method mas used to investigate the cause of the colour change experienced by the solution of the double salt HgIz,2AgI at about 50'. The transition temperature in the first case was found to lie between 36.5 and 36.8, whilst in the second case the colour change from yellow to red is due to t,he formation of mercuric iodide owing to the decomposition of the double salt.L. M. J. Improved Calorimeter for the Application of the Method of Mixtures. By F. A. WATERMAN ( P M . Mag., lb95, [ 5 ] , 40, 413- 4 21).--For the purpose of avoiding the radiation correction in the determination of the specific heat of solids by the method of mixtures, Hesehus has suggested that the calorimeter cup be introduced into the bulb of an air thermometer and maintained a t a constant tem- perature by the introduction of a sufficient amount of cold water, ofGENERAL AND PHYSICAL CHEMISTRY. 147 known temperature, immediately after the introduction of the heated solid. By this means, both the radiation correction and the water eqnivalent of the calorimeter cup are aroided, the heat received by the cold water being equal to that giveu out by the heated sub- stance. The author has constructed a calorimeter on the above principle.The water cooler and dropper is supported upon a vertical rod in such a manner that i t may be quickly turtied about the rod as an axis, and may deliver water directly to the calorimeter cup. An electric heater is supported upon a second vertical rod and may be turned about t,he rod as an axis until it is directly over the calorimeter cup, allowing the heated body to be transferred directly to the cup. A summary of some trial determinations made with this apparatus is given, showing that it gives concordant results. H.. C , Thermal Unit. By ERNEST H. GRIPFJTHS (Phil. Mag., 1895, [ 5 ] , 40, 431-454).-The capacity for heat, of water, has been invariably adopted in defining the thermal unit,, and its capacity at O", 4', 15O, and its mean capacity from 0' to looo, have been variously selected as standards by different observers, This selection is unfortunate, as at present our knowledge of the comparative value of these standards is vague, and comparison of the results of the different investigators becomes impossible. 'J'he range 10' to 30" is of particular import- ance, as the majority of thermal determinations are expressed i n terms of the capacity of water at some point within this range, and as a consequence great attention has been devoted to i t ; but in spite of this, a comparison of the results of those observers whose work appears to be most worthy of attention, shows that a discrepancy which may be as great as 1 in 300 exists between their results.Even greater uncertainty attaches to the determination of the " mean calorie," as the determinations of the ratio of the mean calorie t o the thermal unit at 15O, give results varying from 1.013 to 0-99.57, H difference of Z part in 60. I t appears, therefore, that the endeavours to establish the heat capacity of water as the standard of calori- metric measnrements have, so far, not, met with success, It has been pointed out by Gray, that even if the specific heat oE water was accurately known it would not, for any reason, be arith- metically commensurable with any other definite physical quantity, but i t would be a purely arbitrary quantity. But it is evident that the ideal thermal iinit should be n natural, not an arbitrary, one, and have some real relation with other units of energy.Further, it should not be dependent on the observations or conclusions of any one investigator ; i t should be of a convenient magnitude, and should cause as little disturbance as possible in the numerical values result- ing from our present system of thermal measurements. The author proposes that the value of this ideal unit should be first defined, that value being some convenient multiple of an absolute unit. A first approximation could then be made to the physical unit thus selected, and this improved, if necessary, by subsequent measurements. It is proposed that the unit adopted should be a thermo-dynamic one, and that this ideal unit should be tcrmed a ''Howland." The name148 ABSTRACTS OF OHEMIOAL PAPERS.“ Therm ” is taken to indicate the quantity of heat required to raise 1 gram of water (measured in vacunm) through 1” of the nitrogen tbermometer a t a temperature to of that thermometer. The Rowland should be of such a magnitude that a therm a t some convenient temperature would be its heat equivalent. The parkicular therm which is the exact equivalent of a Rowland could be denoted by the phrase “ standard theym.” (This paper was read a t the 1895 meeting of tho British Associa- tion. The consideration of the whole matter has been referred to the Committee on Electrical Standards.) Heats of Combination of Substances in the Liquid and Solid Conditions. By P. SPEXCER U.PICKERIKG (PhiZ. Hug., “51, 39, 510) .-The author has investigated several so-called molecular com- pounds to ascertain whether, as in the case of the monhydrate o€ sulphuric acid, their heats of formation were the same in both solid and liquid conditions. Their heats of combinatioii as liquids were deter- mined directly, and the value for the solids deduced indirectly from the heats of fusion of the constituents and compounds. The heat ca- pacities of the substances in both conditions had also to be determined i n order to reduce the heats of fusion to the same temperature. The heat of combination thus calculated is, however, the true heat of combination only if the heat of fusion of the compound is equal to the sum of those of its constituents, and the results obtained by the author prove that this is not the case, the heat of fusion of the compound being generally the smaller quantiiy.The true heat, of combination in the solid condition can, therefore, not be obtained. The substances investigated were : Compounds of sulphuric acid, pinacone, stannic bromide, and sodium hydroxide with water ; benzene with azobenzene ; and dinitro- and meta-dinitrobenzene with naph- thalene. The existence of the two last-mentioned compounds was investigated and established by series of f reeaing point determina- tions ; so also was the existence of the octobydrate of stannic bromide, which had not before been isolated. s. u. P. combination of Mercuric Cyanide with Iodides. By h o u r , VARET (Compt. r e d . , 1895, 121, 499-501).-l’he first column gives the heat of dissolution of the salt in water; the second, the heat developed on mixing solutions of mercuric cyanide and the particular iodide ; and the third the heat of formation of the solid salt from its proximate constituents (solid salts and liquid water).H. (3. 1. 2. 3. Hg(CN),,2NnCN7Hg1,,4H,O. . . . -22.8 +5.3 +24*7 C d . Hg;(CN)?,BNH,I,HgT,,~H,O . . . . -23.5 +4*5 +15*0 ,, Hg(CN),.2LiCN,Hg12,7H,0 . . . . - 20.7 +5*5 +50*0 ,, Rg(CN),,Ba(CN),.Hg12,6H20 . . -22.0 +5*3 +31.6 ,, Hg(CN),,Xr(CN),,HgI,,~~*O . . -21.8 $5.5 +41.8 ,, Hg(CN),,Ca(CN),,HgI,,/H,O . . -22.4 +5.5 +49*5 ,, Hg(CN),,nlg(CN),Hg1,,8HzO . . -20.0 f 5 . 3 + 69.1 ,, Hg(CN),,Cd(CN),,HffI,,8H20 . . -22.5 +2*0 +17*3 ,, At 30”, the solutioiis of the iodocyanides, unlike those of the chloro-GENERAL AND PHYSICAL CHEMISTRY.149 cyanides and bromocjanides (this 1-01., i, 3 ; ii, SS), are strongly alkaline to litmus, and give the isopurpnrate reaction with picric acid, and hence it iollows that they contain salts of the type Hg(CN),, M”(CN),,HgI,. The conversion o€ the system SHg(CN), + M”12, into Hg(CN), + M’(CN), + HgL, absorbs about -9.3 Cal. in solution, whilst the heat of formation of the double cyanides, Hg(CN),,M”( CN),, is + 12.4 Cal., and their union with yellow mercuric iodide develops f 2.3 Gal. Lithium, Magnesium, and Copper Cyanides. By RAOUL VARET C. H. B. (Compt. relid., 1895,121, 598-599) .--Lithizhm Cyanide.-The heat of neutralisation of hydrocjanic acid solution by lithia is +5*85 Cal., and hence Li sol. + CN gas + Aq = I i C N diss ... develops +65*12 Cal.Magnesitm C‘yaszide.-The heat of neutralisation [Mg(OH),] is Mg sol. + 2CN gas + aq. = Mg(CN)a Cuprotss CIJ ankle. Hg(CN), diss. + CuJ, sol. = Hg12(red) Cu,O sol. + 2HCN diss. = Cu2(CN), sol. +3.0 Cal., and hence diss. ............................. develops +112*0 C d . + Cu2(CN), ...................... develops +12-8 Cal. + H20 liq. ........................ 9 , +28*8 9, Cu, sol. + 2CN gas = Cu2(CN), sol.. ... > 7 +29.8 9 , Hydrogen cyanide displaces hydrogen chloride from cuprous salts with development of +13*6 Cal., and hydrogen bromide with de- velopment of +10.8 cal., but is displaced by hydrogen iodide with development of +3*2 Gal. These phenomena are analogous to those observed by Berthelot with mercuric oxide, and by the author with mercurous oxide ; but whereas mercuric and mercurous oxides behave similarly, cupric oxide differs from cnprous oxide in that the heats of neutralisation of tha former by hydrogen chloride, homide, and iodide are practically identical.Depression of the Melting Point of Sodium Sulphate by the addition of Foreign Substances. By RICHARD L~WENHERZ (Zeit. physikal. Chem., 2895, 18, 70--90).--Tlie effect of non-electrolytes in lowering the melting point of sodium sulphate was first determined, urea, glycocine, cane sugar, formamide, and glycerol being employed, atid the mean value for the depression constant so obtained was 32.6. The effect of sodium Palts was next investigated, and, as might be expected, they behaved practically as non-electrolytes, sodium phos- phate giving the highest value (37*8), whilst the results indicate that the formula of sodiuni persulphate is NaJ3,0e.By the addition of sulphates (those of potassium, ammonium, and lithium), a double depression constant results. This may due either to dissociation into K and KSO, ions, since neither of these is present in the solvent, or t o an interaction ; K,SO, + Pu’a2S04 = 2KNaSOI. Potassium chloride C . H. B. VOL. LXX. ii. 12I50 ABSTRACTS OF CHEMICAL PAPERS. and nitrate gave double values, which may he explained either I)y dissociatiou 01- interaction with the sodium sulphate, whilst potassium chromate and potassium carbonate gave depression constants equal to three times the normal, and capable of a similar explanation. By the determination of the solubility of sodium sulphnte in (1) wa,fer, and in (2) a solution of urea, the temperature of transition to the anhydride was found to be (1) 32.46, (2) 29-26, the numbers obtained by the direct determinations being 33.39 and 29.26.The depression constant is calculated by use of the forrnula 16 = 0*02I’W/, and by Raoult’s tension law, the values 36 and 33.8 being so obtained. L. M. J. Pressures of Saturation of Oxygen. By THADDEUS ESTREICH ER (Phil. Mag., 1895, [5], 40, 454---463).--Tlic author has measured the temperatures of the saturul ed rapour of oxygen under pressures lower than one atmosphere by ineans of a hydrogen thermometer. Three series of determinations were made, and the results, which alee generally in close agreement with one another, are given in separate tables i n the paper. The value of f i n the Van der Wad’s formula was calculated and compared with that given by a number of other associating and non-associating liquids a t low pressures (compare Guye,.dbstr., 1895, ii, 153). The mettn value for oxygen is about 2-45. The author finds that the value of f always d.ecreases with increase of temperature, both for associating and non-associating substances. The association of the molecules of the liquid has an influence o n j , but is not, the only reason of its increasing. Of 10 ethereal salts, six have values of f much higher than 3-06, although, according to Ramsay and Shields, they are not associated. Perhaps there is some relationship with the molecular weight, as the highest of the alcohois examined, isobutylic alcohol, has the highest f.Thermal Properties of Vapours : Alcohol Vapour and its Relationship to the Laws of Boyle and Gay-Lussac. By ANGELO BATELLI (Ann. Cliirn. Phys., 1895 [7], 5, 2563--875).--The pressui e of saturated ethylic alcohol vspour shows a t high tempern- ture n behaviour similar to that which the author has observed in several other substances, the pressure increasing as candensation proceeds and the liquid accumulates. The maximum pressures between the temperatures -16’ and 240’ may be represented by thc formula of Biot, the values of the constants being H. C. logp = n + bzt + c p , n = 5.0751023 b = 0.0435271 The critical constants obtained from the isothermal curves are : tc = 241.4”, pc = 47,348 mm., and vC = 4.38 C.C.The coefficients of dilatation of alcohol vapour under constant pressure increase as the temperature diminishes, this taking place the more rapidly the nearer +#he vnpour is to the point, of liquefaction. The absolute log b = 2.6387597 log a = 0.00336681 = -4-0217800 10g c = 0.6044184 iogp = i . ~ g s w o i ~GENERAL AND PHYSICAL GELEMISTRY. 151 values of the coefficients and their variations between the same limits of temperature increase with the increasing pressure of the vapour. From the isochoric curves, the values of dp/pdt, the co- efficient of pressure change a t constantl volume, were calculated. The coefficieiit decreases with rising temperature, the variations becoming more mayked the smaller the volume. As the volumes increase, the absolute value of the coefficient diminishes.The formula of Clausius in the modified form, applies very closely to the results obtained with alcohol. Vapour Pressure of Concentrated Solutions of several Salts, especially Lithium and Calcium Nitrates. By JOHN WADDELL (Chem. News, 1895, 72, 201--203).-Into a wide-mouthed, closely stoppered bottle of about 200 to 300 C.C. capacity three small test- tubes were introduced, one of which contained water or alcohol, and each of the others one of the salts to be experimented with. After some experience had been gained, the liquid was frequently added directly to the salts, arid the third test-tube dispensed with. The salts were taken in molecular proportions, weighed in milligrams, but 1, 2, or 4 mols. of one salt were taken to 1 mol.of the other, the numbers obtained being all so reduced as to show the quantity of liquid taketi up per molecule of each salt. Experiments were first made with calcium and lithium nitrates. If a curve is plotted whose ordinates are the quantities of water ab- sorbed respectively by the lithium and the calcium nitrate, it does not differ very much from a straight line, although it is slightly con- cave towards the axis of the lithium nitrate. The ratio of the water absorbed by the lithium nitrate to that absorbed by the calcium nitrate ramged from about four-fifths to five-sixths. As, if all the molecnles of each salt were dissociated into their ions, there would be the same vapour pressure when the amouut of water absorbed per molecule by the lithium and calcium nitrates is in the ratio 2 : 3, it may be assumed that the lithium nitrate is dissociated to a greater extent than the calcium nitrate.When alcohol was employed as the liquid to be absorbed, there was less uniformity than in the case of water. Each molecule of lithium nitrate absorbs approximately four- fifths as much alcohol as each molecule of calcium nitrate. This condition would be fulfilled if all the lithium nitrate were dissociated, and one quarter only of the calcinm nitrate inolecules. A series of experiments was instituted for t'he purpose of comparing the nitrates of the calcium group of metals among themselves and with lithium nitrate. This has not been quite completed, but there seems to be little doubt from what has been done, that barium nitrate is the most absorbent, that the calcium salt comes nest, and that the stron- tium compound, instead of being intermediate between the others, is less absorbent than either.A series of experiments was also made in which the metal was the same, but the salt radicle varied, the halo'id H. C. salts of potassium being chosen for this pnrpose. The bromide and 12--2152 ABSTRACTS OF CHEMICAL PAPERS. iodide both absorb enough water to make a solution while the chlo- ride is still in the solid condition, but when the vaponr pressure from the bromide and iodide comes to be as great as that of the saturated solutiolz of the chloride, it remains constant until the chloride is all dissolved. Therefore, the three salts absorb nearly the same amounts of water, and it appears that these salts are very nearly equally dissociated, even in rather concentrated solutions, but if any- thing, the bromide is more dissociated than the others. Experiments on the resistance of the solutions showed that the amount of dissociation of calcium nitrate is about 45 per cent.as great in a concentrated as in a dilute solution, whilst the amount of dissociation in the case of the lithium salt is about 83 per cent. Determination of the Molecular Weights of some Inorganic Substances. By HEINRICH BILZ (Chem. Centr., 1895, i, 770-771 ; from Math. natw. Mitt. Berlin, 1895, 35--38) .-The author has determined the density of some of the elements at a very high temperature by means of an apparatus made of a highly refractory porcelain. The ex- periments with arsenic, thallium, cadmium, and zinc were made at 1732-1748'.The density of arsenic vapour was found to be 5.30-5-54, the theory for As2 being 5.2. The dissociation at this high temperature was not greater in hydrogen than in nitrogen. Thallium showed a density of 14-77, theory for TI, requiring 14.11. Cadmium had a density of 4.34-4-38, theory requiring 3.87 for Cd. Zinc had a density of 2.64, theory requiring 2.25 f o r Zn. Iridium and tin did not evaporate at these high temperatures. Arsenic trioqide has, be tween 500-770", a density corresponding with the formula AsdOs. The same diminishes with a higher tem- perature, and has, at 1732", the value 7.32, theory for As,03 requir- ing 6.84. It seems that, above 1770', only molecules of the com- pound AszOs can exist.The increase in the boiling point of aqueous solutions of both varieties of arsenious anhydride showed that decom- position into 2 mols. of arsenious acid, H3As03, had occurred. The solution of the crystallised variety of arsenious anhydride in nitro- benzene seems, on the other hand, to contain unaltered As406. Attempts were made to estimate the vapour density of the alkali metals and of magnesium, but constant values could not be obtained although any action of the metals on the porcelain vessel was By CHARLES T. BLANSHARD (Chem. News, 1895, '72, 230-231, 237-238). --Continuing his observations in reference to t.he genesis of the ele- ments (Abstr., 1895, ii, 340), the author now points out that the specific volumes in certain homologous series of organic compounds offer parallels to various conditions that obtain with the atomic volumes of series of related elements.D. A. L. H. C. prevented. L. DE & Specific Volume and the Genesis of the Elements. Molecular Volumes. By ISIDOR TRAUBE (Ber., 1895, 28, 2722- 2728 ; compare Abstr., 1895, ii, 209).-The author compares the ob- served and calculated values (Abstr., 1895, ii, 70) of thc molecularGENERAL AND PHYSICAL CHEMISTRY 153 solution volumes of a large number of organic compounds of very different types, and finds a very close agreement between them ; he gives a revised table of atomic solution volumes for the non-metallic elements, and states that the molecular contraction volume per gram- molecnle of substance dissolved in water shodd be 13.5 C.C.instead of 12.2 as previously given. The molecular solution volume is not a pnrely additive property, but a highly constitutive one, the atomic solution volumes for the various types of oxygen, carbon, nitrogen, sulphur, &c., in organic compounds having very different values ; the presence of a benzene or hexamethyleue ring in the molecule decreases the molecular solution volume of the compound by 8.1 C.C. The molecular solution volume is not simply the sum of the atomic solution volumes of the atoms forming the molecule, as an expansion always occurs during the formstion of a substance ; this “ molecular dilatation” is approximately the same for all substances, and is 12.4 C.C. per gram molecular weight for the gram molecular volume in aqueous solution at 15’; to obtain the n~olecular yolume this number 12.4 must naturally be increased by the addition of 13.5 C.C.; the molecular contraction volume for water thus becomes 25.9 C.C. W. J. P. Molecular Volumetric Determination of Molecular Weights. By ISIDOR TRAURE (BeT., 1895, 28, 2728-2730 ; compare preceding abstract) .--Prom a single specific gravity determination of an aqueous solution containing 0.5-3 per cent. of a substance, the molecular solu- tion volume of the latter can be calculated, and a correct molecular weight assigned to the substance, using the equation (Abstr., 1895, ii, 70)- v, = nt + ng/d - nqia = ZytC f 12.4. The influence of iouic dissocia.tion and of the presence of the various types of ring present i n the substance must, of course, be taken into consideration.In determining the molecular weight of an acid, it is usually con- venient to nentralise the solution with standard soda, using phenol- phthalejin as an indicntor, and to then determine the molecular solu- tion volume of the sodium salt, which in so dilute a solution is practically wholly dissociated. The molecular solution volume of sodium metamidobenzoate determined in a 3.030 per cent. aqueous solution was found to be 89.1 c.c., whilst the calculated valne is 89.2 C.C. ; very accurate results may therefore be obtained. Molecular-volumetric Method of Determining the Molecular Weight and Constitution. By ISIDOR TRAUBE (Ber., 1895, 28, 2924-2928) .-The author gives the following formula for calculat- ing the molecular volumes of the hydrocarbons at 15’.W. J. P. where ZnC is the sum of the products of the atomic volumes and the number of atoms present, and p , (1, T are respectively the number of rings, of double, and of triple linkings. The atomic volume of carbon is 9.9, of hydrogen 3.1, the decrement for each hexamethylene154 ABSTRACTS OF CHEMICAL PAPERS. ring 8.1, for each benzene ring 13.2, for each double iinking 1.7, and f o r each triple linking 2 x 1.7 = 3.4. The molecular volumes of 80 hydrocarbons calculated bF this formula are given in the paper arid compared wit,h those obtained directly from the specific gravities. The agreement between the two series is excellent, and in no case is a greater difference than 6.3 C.C. observed. Since doubling the molecular weight would cause a difference of 25.9 c.c., the applica- tion of the method t o the determination of molecular weights is evi- dent (compare Abstr., 1895, ii, 209).Initial Rates of Osmosis of certain Substances in Water and in Liquids containing Albumin. By W. S. LAZARUS-BARLOW (J. Physiol., 1895, 19, 140--166).-See this vol., ii, 196. H. C. Correct Formulae for Osmotic Pressure, Changes of Solu- bility, Freezing Point and Boiling Point ; and Heats of Solu- tion and Dilution in Dissolved Dissociated Substances. By J. J. VAN LAAR. IT. (Zeit. yhysikal. Chem., 1895, 18, 245-282).- The author investigates, thermodynamically, the above formulae, and obtains theoretically the following results. If a strongly dissociated compound is added to a dilute solution of a feebly dissociated sub- stance with one common ion, the dissociation degree of the former remains almost unaltered, that of the latter compound being dimi- nished.When also there is one ion common, the solubility of the compound is lowered, the least soluble undergoing the greatest relative change. Non-electrolytes do not affect the solubility, neither are they affected in this respect. When there is no conitnon ion, the effects are more complicated, and frequently undetermined. In the case of partition coefficients between water and other solvents: it is seen that, owing to the ions being absent in the other solvents, the apparent, partition coeEcient increases with dilution. The effect of association of the solvent molecules on the formuh deduced here and in the former paper (1895, ii, 107) is considered, and, where necessary, alterations for this given.It is also shown that the vapour pressure of water is not influenced by the presence of indifferent gases, and that the validity of Dalton's law is limited to the cases where the volume is great. The Absorption of Nitrous Oxide in Water and in Salt Solutions. By VICTOR GORDON ( Z e i f . physikal. Chem., 1895, 18, l-l6).-The author has determined the absorption coefficient of nitrous oxide in solntions of chlorides of potassium, sodium, lithium, calcium and strontium, and snlphates of potassium, sodium, lithium, and magnesium. The experiments were in each case performed for three or more concentrations, and at five different temperatures, ranging from 8.1' to 22*3O, and interpolation formule* are giveu for each solution examined.The lowering of the absorption coefficient appears to be proportional t o M3, where M is the number of gram f It is noticeable that these interpolation €ormule are in all cases of the form a = a - pt + yt2 indicating, if the formula holds for extrapolation, a minimum at the temperature /3/2y, which in almost all cases lies between 34" and 49'. L. M. J.GESEKAL A N ) PHYSICAL CHEMISTRI’. 155 molecules of dissolved salt per litre, so that (a-aS)/W = const., a and a, heiiig the coefficient in water and tlie solution respectively. The value of the constant decreases as the temperature rises, and raries with different salts. For analogous salts, however, the con- stants are nearly equal, whilst the value for bivalent salts is double that for univalent salts.L. $1. J. The Partition Coefficients of Solutions in Liquid and Solid Substances. By JACOBUS h1. VAN BEMWELEN (Zeit. physikal. Chew., 1895, 18, 331-334).-The results and conclusions of G. C. Schmidt (Abstr., 1895, ii, 39) are contested. Neither in silicic acid nor in any other substance experimented with by the author, did he find the absorption took place in accordance with Henry’s gaseous law ( c * / c ~ = const., where c2 and c1 are the concentrations of dissolved substance in the liquid and solid respectively). The partition coe6cient was in all cases not constaut, but a complex function of the concentration, and dependent on the temperature and modification of tlie colloid. The coefficient is onIy approximately constant, when t,he concentration is small, so that the author considers Schmidt’s conclusions erroneons.L. M. J. Note by Abstractor.--The partition coefficient should, however, only be constant when the solid absorbent, that is, the colloid, remains of the same modification, and only for dilute solutions, as in strong solutions Henry’s law coulcl not be expected to hold. Self-recorded Breaks in the Properties of Solutions. By P. SPKNCER U. PICKERING (Phil. Mag., [ 5 ] , 40, 472--476).-By running n continuous stream of sulphuric acid into water in a calorimeter, and making a chart of the niotion of the thermometer, either by photo- graphy or by taking successive readings, a diagram is obtained which reproduces automatically the sudden changes of curvature shown by the author’s heat of dissolution determinations (Trans., 1890, 127).By adjusting the initial temperature suitably, the figures obtained are rectilineal, and the breaks become as clearly visible as those which are made on starting or stopping the stream of acid. 8. U. P. Cryoscopic Relations of Dilute Solutions of Cane Sugar and Ethylic Alcohol. By HARRY C. JONES (Phil. Mag., 1895, [5], 40, 383-393 ; and Zeit. ph ysikal. Chm., 1895, 18, 283-293).- Nernst and Abegg (Abstr., 1895, ii, 155) have attributed the high results obtained by the author for tlie molecular lowering of the freezing point in dilute cane sugar solutions to the use of a jacket a t a much lower temperature than the freezing point of the solution. The experiments have therefore been repeated, using a freezing mixture from 0.3’ to O.PO colder than the freezing point of the solution.A large volume of solution (1100 c.c.) was employed, thus diminishing ~ery.greatly the effect of disturbing influences from without. The stirring was carried out so gently that errors from this source could not have assumed any appreciable dimensions. The results obtained are as follows.156 ABSTRACTS OF CHEMICAL PAPERS, Grams in litre. Normal. Lowering found. Gram-mol. lowering. 3.8875 0*01136 04251 2.21 7.775 0.0227 0.C475 2.09 1.5-550 0.0455 0.0915 2-01 23325 0.0682 0,1333 1.95 31.100 0.0909 0.1734 1.91 The molecular lowerings are throughout somewhat lower than those obtained in former determinations, but they are still far above the theoretical value. Dilute solutions of ethylic alcohol gave similar results, and the author does not find sufficient justification for the conclusion that non-electrolytes in fairly dilute solutions give lowerings which conform to the equation t = 0.02 T2/W.Relations between the Cry oscopic Behaviour of the Phenols and their Constitution. By KARL AUWERS (Ber., 1895, 28, 2878-2882).-Although, as the result of former investigatioris (Abstr., 1894, ii, 133 ; 1895, ii, 41), the author was led to conclude that the cryoscopic behaviour of the phenols in benzene solution was normal, certain irregularities observed with paracresol and pzra- nitrophenol rendered this conclusion doubtful. The author has, therefore, submitted this point to the test of further experiment, but, as many of the phenols are only very slightly soluble in benzene at the freezing point, naphthalene has been substituted for benzene as R solrent.Forty-eight phenols were examined in all, namely, phenol and 6 of its homologues, 5 halogen derivatives, 9 nitrophenols, 8 hydroxyaldehydes, 14 yhenolcarboxylic acids, and 5 polybasic phenols. The acids were used in the form of their methylic or ethylic salts. The examination of these substances shows that the cryoscopic behaviour of the phenols is largely dependent on their constitution. Phenols, where substitution is in the ortho-position, exhibit the normal cryoscopic behaviour, but para-substituted phenols behave abcormally. The meta-compounds occupy a position between the ortho- and para-, but rather resemble the para-compounds i n their behnvionr. Among the substituting groups, the influence of the aldzliydic group *CHO is the most marked, and then in decreasing order of influence follow the carboxslkylic group *COOR, the nitro-group, the halogens, and, lastly, the alkylic groups.The influence of ortho-substitution is stronger than that in the metn- or para-position, so that if a phenol contains the same substituting group in both the ortho- and paya-positions, the cryoscopic behaviour of the substance will probably be nearly normal. No exceptions to the above regularities have as yet been met with, and it is suggested that the cryoscopic behaviour of a phenol may aid materially in the determiriation of its constitution. H. C. Cryoscopic Behaviour of Substances having Constitutions similar t o that of the Solvent.By EMANUELE PAT ERN^ (Garzetta, 1895, 25, i, 411--417).-Garelli and Montsnari (Abstr., 1895, ii, 205) showed that the phenols when dissolved in the corresponding hydro- carbons give abnormal depressions of the freezing points, and conclude that this is due to the close chemical relationship existing between H. C.GENERAL AND PHYSICAL CHEMISTRY. 157 the solvent and the dissolved substance ; the author shows, however, that this similarity of coiistitution is not the onIy cause of a small depression of the freezing point, but that the chemical nature of the dissolved substance has also to be considered. Thus, phenol behaves abnormally, whether dissolved in benzene or in paraxplene ; para- xylenol also gives abnormal freezing point depressions both in paraxylene and benzene soltltions ; the similarity of constitution of the solvent a,nd dissolved substance seems ir- these cases to be without effect,.Determinations of the depression in freezing point caused by phenol and benzylphenol in diphenylmethane solution show that phenol behaves fairly normally and benzylphenol quite abnormally, as would be expected from Garelli and Montanari's conclusion. W. J. P. Freezing of Solutions at Constant Temperature. By ALBERT COLSON (Compt. Tend., 1895, 120, 991-993).-An increase of pressure raises the freezing points of liquids which contract during solidification, whilst, on the other hand, the presence of dissolved foreign matter lowers the freezing point in inverse proportion t o the molecular weight of the dissolved substance.The author has endeavoured to ascertain experimentally whether any relation exists between the molecular weight of the dissolved substance and the pressure required to maintain the freezing point of the solvent constant. The solvent selected was benzene freezing at 5.i'. The results are given in the following table. Dissolved substance. M. p . t . P. Henzoic acid .. . . .. . . 122 2.5 0.53O 98 mm. Acetic acid.. .. . . . , .. 60 2.5 1.16 232 ,, Naphthalene ... . . . I I . . 128 2.5 1.06 219 ,, Pmadichlorobenzeue.. 137 2.5 092 180 ,, Paradichlorobenzme.. 137 5.0 1.85 410 ,, I\letadinit,robenzene .. 168 3.0 0.98 225 ,, Here 31 is the molecular weight of the dissolved substance, p the number of grams dissolved in 100 grams of benzene, t the depression of the freezing point, and P the pressure in mm.in Amagat's apparatus required t o iaaise the freezing point of the solution t o that of the solvent (5 mm. on this scale correspond with about 1 atmos.). It mill be seen that in the case of benzoic and acetic acids there is no direct relationship between the pressurea corresponding with a particular freezing point depression and the molecular weights of the acids. On the other hand, if we consider three of the soiutions in which the depression of the freezing point is about lo, we find that the pressure which may be regarded as equivalent t o a depression of 1' is in each case about the same, thus : acetic acid, 232/1*16 = 200 ; naphthalene, 219/1.06 = 206 ; chlorobeuzene, 180j0.92 = 194. H. C. Influence of Chemical Constitution of Organic Compounds 011 their capability of forming Solid Solutions.By FELICE GAHELL~ (Zeit. physiknl. C'henz., 189.3, 18, 51-60).-The paper contains further examples of abnormal depressions of the freezing point occurring when solvent and dissolved substancs are closely158 ABSTRACTS OF CHEJIICAL PAPERS. allied in constitution. Cumarone, indole, and indene in naphthalene give too high values for the molecular weight, as do diphenylene oxide and [j-naphthoquinoline in pheiianthrene, phenanthroline in the same soivent giving a normal result. Dithienyl gives an abnormal depression in diphenyl, but normal in benzene, whilst metauicotine gires a normal value in diphenyl, a result in accord with the views of Pinner (Abstr., 1894, i, 388; 1895, i, 116). The regularity observed in the cyclic compounds is markedly modified by the presence of side chains, thus methylpyrroline gives a normal depres- sion in benzene, as do pyrroline and thiophen in paraxylene, whilst aa-dimethylpyrroline and aa-dimethylthiophen give abnormal values in paraxylene.I n acetophenone, acetylpyrroline and acetothienone give, as expected, abnormal depressions. I n benzoic acid as solvent, a-pyrrolinecarboxylic acid, a-thiophencarboxylic acid, ortho- and rneta-hydrosybenzoic acids, and ortbamidobenzoic acid give abnormal depressions, whilst those caused by parahydroxybenzoic and f urfuran- carboxylic acids are normal, those due to meta- and para-amido- benzoic acids being nearly so. In phenol, the three dihydroxy- benzenes are slightly abnormal, whilst in resorcinol the ortho- and para-compounds give normal Talues.Some fatty compounds are also examined : maleic anhydride in snccinic anhydride giving an abnormal result, whilst those of olejic acid in stearic acid, butyric acid in crotonic acid, apiole and dihydro-npiole in isapiole are normal. I n a short note on Beckmann’s work (Abstr., 1895, ii, 383), the author does not consider that the abnormal results of iodine in benzene solution can be due to the forniatiofi of a solid solution. L. If, J. The Velocity Law of Polymolecular Reactions. By ARTHUI.: A. NOYES (and WALTER 0. SCOTT) (Zeit. physikal. Chein., 1895, 18, 118--132).-For the determination of the order of a chemical reaction, the constancy of tlie velocity constant is not alone suffi- cient, but comparison should be made of the constants, a t a definite stage of the action, obtained in independent experiments with different initial concentrations.Examined thus, i t is seen that the action between hydrogen iodide and hydrogen peroxide is of the second order (see Magnaniui, Abstr., 1892, llO), whilst the same holds foy the action between hydrogen iodide and bromic acid. According to Schwicker’s experiments (Abstr., 1895, ii, 213), the decomposition of potassium hypoiodite is, if in the presence of free iodine, of the first order, b u t no definite conclusion can be drawn if alkali is in excess. The reaction between ferric and stannous chlorides is, however, of. the third order, as is the poly- merisation of cyanic acid. An explanation of tlie first three cases, may be that the reaction takes place in two or more stages, of which the first alone takes an appreciable time.For example, HI + H20, = HI0 + H20; HI0 + HI = H,O + I,. In the last two cases, van’t Hoes law, that the order is determined by the number of interacting molecules, is obeyed. A Reversible Reaction of the First Order. By FRITZ W. KESTER (Zeit. plysikaE. Chem., 1895, 18, 161-179) .-The reversible L. M. J.OEXEItAL AND PHYSICAL CHEJIISTRY. 159 N15 acid. Salicin hydrolysis. change of hexachlor-~-keto-/3-pentene 2 hexachlor-~-keto--,-pentene is considered. The estimation of the compounds is effected yeadily, owing to the slight solubility of the anilide of the p-compound. The /%compound was heated a t 210°, and the quantity of the y-compound estimated hourly, the final state being reached when the quantity was 0.386, whilst the value of l / t log l/(l + c'/c):c raried from 0.055 t o 0.035.The change from the y-compound to the p- was examined a t the same temperature, the final stage being reached when 0.623 of the p-compound was formed, a number agreeing exactly with the prcvious results. Experiments in different atmospheres showed that siuall quantities of aqueous vapour hare a high accelerative influence, the same obtaining to a sinaller extent f o r hydrogen chloride. An increase in temperature to 237.5" caused the relocity to increase tenfold, but the final ratio was only slightly altered, 0.63 to 0.65. At 300°, equilibrium was \-cry speedily reached, the final ratio being 0.85. L. M. J. Velocity of the Hydrolysis of Salicin by Acids.B y Arrmir A. NOPES and WILLIAM J. HALL (Zeit. physilial. Chem., 1895,18,240- 244) .--The investigatioiis were undertaken to determine whether the hydrolysis of a glucoside is in accordance with the reaction law. whicli obtains for the inversion of cane sugar, &c. Salicin was employed for the purpose, the formation of either saligenin or saliretin during the reaction being immaterial, as both are inactive. A 5 per cent. solution was first employed, the rotation of which was - 12-32', and when completely hjdrolysed + 6*00", the ratio being hence 0.487 = c. If the reaction takes place according to the equa- tion dT/dt = k(A - x), the ralue for the constant X; is given by l / t log { (ca, + a,)/(ca, + a ) ) , where a, is the initial rotation, cc1 that at the arbitraryzero of time, and a that after time t.The values thus obtained for k are in close accord, the greatest variation being about 8 per cent., and the reaction therefore, like the sugar inversion, is of the first order. The relative effects of the acids follow the same order as their effects in sugar inyersion, as is seen in the folloving table. Sugar inversion. Hydrochloric. .......... Sulphuric .............. Oxalic ................. Malonic. ............... 1000 499 223 45 1000 536 186 31 L. 11. J. Molecular Symmetry and Asymmetry. By PAUL GROTH (Ber., 1895, 28, 25lO--Z511) .-The generally accepted statement, con- tradicted by Ladenburg (Abstr., 1F95, ii, 489), that when the molecule of a substance contains no plane of symmetry, the substance exhibits enantiomorphism, is quite correct, for planes of symmetry are of two kinds, namely, simple and compound.A figure possesses a plane of simple or direct symmetry when it gives a superposable image on1 ti0 ABSTRACTS OF CHEMICAL PAPERS. reflection from that plane, whilst i t possesses a plane of compouiid or indirect symmetry when a superposable image is only obtained after reflection and rotation through 180' about the normal to the plane. Diketopiperazine, the example quoted by Ladenburg, possesses a plane of compound symmetry, and, therefore, cannot exhibit enantiomorphism ; the application of the term pseudosym- metry to such a case is undesirable, this term being already used in another way. The author points out that the whole question of the symmetry of geometrical figures is now worked out in crystallogra,phic text-books in such a way as to be immediately applicable to all problems con- cerning molecular symmetry, W.J. P. Size of Crystalline Molecules. By AKDREAS FOCK (Ber., 1895, 28, 2734--2742).--Nernst has shown (Abstr., 1892, 560) that when an aqueous solution, coiitaining c1 and cz molecules of two isomor- phous salts per unit volume, is in equilibrium with a solid solution composed of xl and x2 molecules per cent,. of the same two salts respectively, the ratios C J X , and cz/x2 ave constant for all concentra- tions if the niolecular weights of the two salts are the same in both the liquid and the solid solutions ; if, however, the molecular weight in the solid state is times that in the liquid state, TZ being greater or less than unity, then Cl?t/xl and c ~ ~ / z z are constant.If ionic dis- sociation occurs, the number of molecules in the liquid solution changes, and this alteration must be allowed for in using the above constants ; but inasmuch a s the extent of the electrolytic dissociation of two salts having a common ion, in aqueous solubion, is the same, the above ratio should remain practically constant when the solubility of the two salts in molecules per unit volume is nearly the same; if the dissociat,ioa is slight, i t can of course also be disregarded. Disregarding dissociation, therefore, the 'autlhor has calculated the values of the above ratios taking the pairs of isomorphous salts in- vestigated by Bluthmann and Kuntze (Abstr., 1895, ii, 7 ) and shows that potassium dihgdrogen phosphate and arsenate have the same molecular weight both in solution and in the crystalline state.Potas- sium pernianganate and perchiorate and rubidium permanganate have, however, twice the molecular weight when solid that they have when liquid. The author contends that Mu thmann and Knntze's numbers for the equilibrium between potassium and rubidium pernianganates and their aqueous solution show that the two salts crystallise together in all proportions, and not between very narrow limits as stated in the paper quoted above. TV. J. P. Running together and Healing of Crystals. By OTHO L E H w m v (Zeit. physikal. Chew, 1895, 18, 91-95) .-On warming potassium oleate, or even ordinary soap, on a microscope slide with insufiicient alcohol for its complete solution, and allowing the slide to cool, pointed tet,ragonal octahedra separate ; these crystals are 0.1 - 0.3 mm. in length and each usually consists of a string of several individual crystals; they arc best observed by using alcohol colourad red byGENERAL AND PHYSICAL CHEMISTRY. 161 some dye which is not taken up by the deposited crystals. When, by moving the cover-slip two of these crystals are so brought into contact that their long diameters become perpendicular, or in approximately the position of twinning, the sharp end of the one crjstal merely flattens itself against the mass of the other ; if, however, by manipulating the cover slip, the crystals be moved until their longer axes are at about 60°, the smaller crystal turns OF its own accord until in a parallel position to the larger one, and then the two crystals so join together as to form one homogeneous whole. The tendency which deformed soft crystals, such as these, have, towards again assuming a regular form, may be also observed by crushing one of the larger crystals of potassium oleate into small detached fragments by pressure on the cover slip ; the small frag- ments soon become of quite symmetrical form. The processes involved in these changes are obviously the same as those by which a broken crystal becomes whole, or heals itself when immersed in its crystallising solution ; in the latter case, the surface tension of the solid mass can only act through the agency of the solu- tion, whilst with soft crystals like the above, the surface tension of the solid is suEcientlp powerful to cause the arraugement of the fragments in parallel orientation. W. J. P. Convenient Forms of Laboratory Apparatus. By D. ALRER'L KREIPER (Amer. J. Sci., 1895, [3], 50, 132--134).-The author de- cribes a simple form of JzotJilter. The jacket consists of an inverted flask, the bottom of which has been removed, the top of the funnel fits into this opening, and the neck is closed by a stopper containing per- forations for the stem of the funnel, and for the steam and waste pipes. An improved form of the ordinary Banse.12 valve is also described. It consists of a stout glass tube sealed at one end and drawn out in the middle with au opening in the constriction, a piece of rubber tubing containing a smooth slit is placed over this. The collapse of the rnb- ber, which is so common in the Bunsen valve, is thus rendered impos- sible. The valve works much better when lubricated with glycerol. A convenientfowepump may be constructed by adjusting two of the valves just described to the opposite extremities of a T-tube, whilst the third limb is enlarged so :ts to permit the attachment of a large a d stout piece of rubber tubing closed a t one end; this tube being alternately compressed and released by the hand. A New Refractometer. By CARL PULFRICH (Zeit. physikal. Chem., 1895, 18, 294--299.-The author has devised some improvements on the older form of his well-known refractometer so that the in- strument is now a\-ailable for the determination of the refractive index and dispersion not only for sodium light, but also for the C, F, and G lines. A heating arrangement is a130 added for the inveatiga- tion of liquids at various temperatures, and of compounds which have high melting points, whilst the new instrument is also adapted for use as a differential refractometer-that is for the direct deter- mination of the refractive index or dispersion of one solid or liquid with respect to a second. J. J. S. L. M. J.

ISSN:0368-1769    

DOI:10.1039/CA8967005133

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

I n o r g a n i c Chemistry. Possibility of the Occurrence of Hydrogen and of Methane in the Atmosphere. By FRANCIS C. PHCLLIPS (J. Anzer. Chem. XOC., 1895, 17, 801-809).-Since hydrogen and methane are largely evolved during the decay of organic matter under water, and since, by the gradual erosioii of rocks, quantities of natural gas are being constantly liberated, the author thinks it is quite probable that both these gases may exist in the atmosphere. Experiments made a t Mount Washington, New Hampshire (7,000 ft. above sea level) gave negative results, but it is suggested that experiments should be made a t much greater altitudes, as, since hydrogen and methane are both very light, they would tend to form a zone resting on the heavier gases of the atmosphere. The author recommends the use of anhydrous palladium chloride for the detection of traces of hydrogen in a, mixture of gases.Free hydrogen reduces this salt in the cold, forming hydrogen chloride, which can be tested for by means of silver nitrate. J. J. S. Combination of Hydrogen with Oxygen. By VICTOR MEYER and WILHELJI RAuJi (Ber., 1895, 28, 280&2807).-When heated in sealed bulbs for 10 days, at 300°, hydrogen and oxygen do not appear t o combine at all, but when the heating is continued a t the same temperature for 65 days (300-305") the amounts of water formed in three bulbs were 9.5 per cent., 0.4 per cent., and 1.3 per cent. When heated at 100" even for 218 days and nights, no water appears to be formed. The authors consider that these experiments confirm the theoretical view that combination actually takes place between hydrogen aud oxygen a t the ordinary temperature, but at so slow a rate tbat no appreciable amount of water is formed during a measur- able period.A. H. Hydrogen Peroxide. By JULIUS W. B R ~ ~ H L (Ber., 1895, 28, 2847-2866) .-A detailed historical account of the discovery and investigation of hydrogen peroxide is given. The specimens employed were prepared by distilling nnder diminished pressure the commercial article after the addition, if necessary, of a little barium hydroxide to remove silicic acid and salts of the heavy metals ; the purest prepara- tion boiled at 69.2" (26 mm.). The stability increases with the concen- tration, specimens containing 95-100 per cent. H,O, are scarcely changed after 5-7 weeks, if direct sunlight is excluded, the surface reduced as much as possible, and the containing vessel kept smooth ; prolonged shaking favours decomposition, and the compound cannot be conveniently transported by train.Guncotton is the best medium for the filtration of hydrogen peroxide, asbestos causes rapid decom- position, and wool readily ignites. Surface action is entirely excluded if the vessel is coated with paraffin ; the optical constants given belowINORGANIC CHEMISTRY. 163 were determined with prisms treated in this manner, as ground glass causes immediate decomposition of the hydrogen peroxide. If the hydrogen peroxide is isolated by the help of ether, great care is required during the distillation ; on one occasion, a specimen pre- pared in this manner smelt strongly of ozone, an oily substance remained which did not volatilise at loo", had no smell, and detonated feebly when a drop was placed on platinum in a flame, but the intro- duction into it of a sharp-edged, glass rod caused a violent and disas- trous explosion.Four series of determinations of the optical constants were made, of which the follow- ing values, for the molecular refraction and dispersion, are regarded as the most accurate. $%la = 5.791 ; mSa = 5.817 : By - $Ha = 0.136, the calculated values for the formula HO*OH = 5.18,5*32, and 0.10 respectively. The corresponding values for oxygen are as follows. The sp. gr. is 1.4584 at 0°/4", and 1.4378 at 20°/40. ma. B X ? . B y - $Ha. Oxygen in water (20). . . . . . . . 2.968 l3.212 0.036 ,, hydrogen peroxide.. 3.591 3.717 0.055 , , molecular 02, liquid.3.959 3.964 0.069 This increase in the values of molecular oxygen probably denotes the presence i n it of one or more double linkings, and, from its analogy to sulphur, oxygen is probably quadrivalent. I n support of this view, the compounds Ag40 and HCIOJIe, are cited ; the latter is known both as gas and liquid; the formation of hydrogen per- oside from nascent hydrogen and molecular oxygen, its decomposition by means of nascent oxygen, and its resolution int9 water and mole- cular oxygen are also mentioned. Reference is made to the optical constants of carbonic oxide, which have been shown bg the author to be higher than those calculated from the formuls C:O ; this com- pound 11.e regards as CjO, all other organic oxygen compoundb being " unsaturated " in the same sense as bivalent sulphur derivatives, and compounds OE trivalent phosphorus and nitrogen (compare Tafel, Xbstr., 1894, ii, 448).- >, 7 , 4.09 gaseous - J. B. T. Constitution of Water and the Cause of its Dissociating Power. By JULIUS W. B R ~ H L (Ber., 1895, 28, 2866-2868 ; and Zeif. physikal. Chenz., 1895, 18, 514-518) .-Assuming the quadrivalency of oxygen (cornpare preceding abstract), water must be an unsaturated compound; to this cause is referred its great dissociating powel- both for molecular aggregates and single molecules, its readiness i n combining with other substances, and the ease with which it forms molecular aggregates. The fact that most substauces me more or less hygroscopic and soluble i n water is cited in further proof.The organic compounds which most closely resemble water in these pro- perties, such as the alcohols, ketones, ethereal salts, acids, &c , also contain oxygen, and their dissociating power generally decreases a3 the molectilar weight rises and the content of oxygen falls. The hydrocarbons and their haloid substitution products have little or no dissociating power. J . B. T.164 ABSTRACTS OF CHEMICAL PAPERS. Separation of Tellurium from Copper Residues. By CABELL WHITEHEAD ( J . Amer. Chem. Xoc., 1895, 17, S49-855).-All copper produced from American sulphide ores contains tellurium. A method for the estimation of this tellurium has already been given (Abstr., 1895, ii, 289). I n the electrical refining of copper, the washings from the gold residues contain the tellurium as tellurous oxide or sulphate.The tellurium may be obtained from these either by pre- cipitation with copper or by passing sulphurous anhydride through the solution, I t may be finally purified by distillation in hydrogen. When a solution of sodium tellurite is added to a solnticjn of an ammonium salt, a white precipitate of tellurous anhydride is thrown down, which becomes granylar on boiling. A small amount of tel- lurium or of some metal which can be precipitated by sulphurous anhydride remains in solution; this soluble portion is still under investigation. Potassium ferrocyanide does not react with tellurium chloride at once, bat, after a few hours, Prussian blue is formed. When tellurium is heated with aluminium, the two combine with explosive violence, forming a chocolate coloured, difficultly fusible compound, which has the composition Al,Te,.It is hard and brittle, and can readily be ground to powder ; when exposed to moist air, i t is decomposed, and hydrogen telluride is slowly evolved; wher: thrown into water, it is rapidly decomposed. Tellurium is readily deposited by an elect'ric current either from a,n acid or alkaline solution. I t has been found possible to separate tel- lurium from copper by adding an excess of sodium hydroxide and about 3 grams of potassium cyanide for each gram of copper present, and passing an electric current through the solution; when the tellurium is thrown down as a black, non-adherent precipitate, which can readily be filtered off; the solution can then be slightly acidified with sulphuric acid and the copper estimated in the usual way by electrolysis.J. J. S. Action of Gaseous Hydrogen Chloride on Salts of the Elements of the Fifth Group of the Periodic System. By EDGAK F. SNITH and JOSEPH G. HIRBS (J. Arne?.. Chem. Soc., 1895, 17, 6$2--686).-The authors find that sodium nitrate, when heated in a current of hydrogen chloride, is completely converted into sodium chloride. Phosphates are not decomposed, in so far that no phos- phorus chloride is given off; but arsenates of sodium, magnesium, and lead are completely converted into chlorides, whilst the arsenic is entirely volatilised (as chloride or ? oxychloride), and may be col- lect.ed in a bulb apparatus filled with water.When acting on sodium vanadate, the vanadium is expelled as oxychloride. L. DF: I(. Action of Gaseous Halogen acids on the Salts of the Elements of the Fifth Group of the Periodic System. By EDGAR F. SMITH and FRED L. MEYER ( J . Amel.. Chem. Soc., 1895, 17, 7S5-739).- Sodium nitrate is completely converted into the corresponding fluoride by the action of hydrogen fluoride at 250". Phosphates are not attacked. Vanadates are but partially decomposed, and even at aINORGANIC CHEMISTRY. 165 high temperature only about one-half of the vanadium is expelled, The same result was obtained with arsenates. When working with hydrogen bromide, it is found that sodium nitrate is completely converted into the corresponding bromide. Phosphates are not acted on.Sodium vanadate is strongly, but not completely, attacked with formation of vanadium oxy bromide. Arsenates are completely decomposed, a1 1 the arsenic being volatili sed as bromide. Using hydrogen iodide, the experiment with sodium nitrate could not be brought to a satisfactory conclusion, owing to the formation of some explosive bye-products. Phosphates are not acted on. Arsenates are, no doubt, completely decomposed, but exact proof is wanting, as explosive compounds are also formed and interfere with a correct analysis. The action of the gaseous halogen acids on antimony, columbium, and tantalnm is also mentioned, but no analytical details me given. Data for the Ascertainment of the True Atomic Weight of Carbon. By J. ALFRED WANKLYN (Chem. News, 1895,72,164-165). -Arguments are adduced in favour of a reversion to 6 for the atomic weight of carbon (compare this vol., i, 1,2).Reasons are also assigned for doubting whether Schorlemmer’s hydride of hepkyl (this Journal, 1863, 216) was not a mixtui-e of hydrocarbons. L. DE K. D. A. L. Varieties of Graphite. By HEmr ~IOISSAN (Compt. rend., 1895, 121, 540-542) .-The autlior has examined specimens of graphite from various localities, mainly with a view of ascertaining which are intumescent, like the graphite obtained by dissolving carbon in metals a t very high temperatures, and which are non-intumescent, like the graphite produced by the effect of a high temperature alone on any other form of carbon. Ceylon, intumesceiit ; after purification by treatment with fused potash and with hydrofluoric acid, it contains no form of carbon but graphite.Tico?deroga, intumescent. Green- riZZe, intumescent. Bowowdale, non-intumescent, but decrepitates when heated, and gives off about four times its own volume of gas, consisting mainly of hydrocarbons and hydrogen mixed with some air. Omesnack (Greenland), crystalline, but non-intumescent. iWugrazc (Bohemia), and Xcharzbach (Bohemia), also cr-ystalline but non-intu- mescent.. Australia, non-crystalline and non-intumescent. Helium and its Place in the Natural Classification of Ele- mentary Substances. By HENRY WTLDE (Phil. Mag., 1895, [ 5 ] , 40, 466471).-The autlior has examined the spectrum of helium obtained by the distillation method from Norwegian clhveite, pitch- blende, and other minerals containing uranium, more especially some heavy, zimoniferous sand, containing uranium, which is found in large deposits on the coast of Brazil, and which is a relnt,irely abundant source of helium.The result of these experiments confirms the author’s pre- vious conclusim, that the differences in the determinations by dif- ferent observers of the wave-lengths of the components of tlle characteristic yellom line, are due to the influence of pressure aiid C. H. B. VOL. LXX. ii. 13161; ABSTRACTS OF OHEMlCAL PAPERS. diffusion with other gases in varying the width of spectral lines on the more refrangible side of the spectrum. This shows that, within certain limits, the distance between the components of D3 is not to be ttaken as the criterion of the identity of chromospheric and terrestrial helium.In the author’s classification of elementary substances in multiple proportions of their atomic weights, each series or family is considered to be condensations of the typical elements H, H,, H3, H4, H5, €I6, H, (Ohem. News, 36, 66, 96, 107). The properties of helium indicate that it is the typical element H3 a t tlie head of the uneven series H3%. H. C. Estimation of Argon. By TH. SCHLGSING, jun. (Compt. rend., 1895, 121, 604-606).--Purther experiments have shown that the error in the estimation of argon by the author’s method (this voi., ii, 219) amounts to about 0.7 per cent. of the argon to be estimated, arid is not due to any action of the steel, porcelain, asbestos, copper, or cupric oxide on the argon. When the magnesium is not heated, the loss is about 0.25 per cent., and-when i t is heated, the loss is from 0-5 to 1.0 per cent., arid increases with the duration of the experiment and the pressure of the argon in the apparatus.The following estimations were made with the air of Paris collected 10 metres above the soil. Sep. 25. Sep. 26. Sep. 30. Oct. 1. Oct. 4. Mean. air . . . . . . . . . 0.9369 0.9349 0.9367 0,9325 0.9363 0.935 nitrogen . . , . 1.185 1.183 1.185 1.180 1.185 1.184 Per 100 vols. of Per 100 vols. of Other estimations were as follows. Per 100 vols. Per 100 vola. of air. of nitrogen. Air in Normandv at a height of 305 metres. . Air round the Eiffel Tower at a height of 300 metres. .. . . . . .. .. .... .. .. .. .. .. .. Air in the gnlloi*g of an iron mine... . . . . < . 0.9343 1.182 0.9328 1.180 0.9354 1.183 0.934 1.182 -_ The differences are of the same order as the errors of experiment, a d it would seem that the proporbion of argou in the atmosphere is as constant as that of oxygen or nitrogen. Making the correc- tion of 0.7 per cent). as above, the numbers for normal air become 0.941 and 1.192. Calcnlation of the difference in density between pure nitrogen and atmospheric nitrogen mixed with argon gives 0.0063, whilAt Rayleigh and Ramsay found 0.0067. The following estimations were made in the gas drawn from various oils. Argon per 100 vols. of nitrogen. A t a depth of 0.20 mm. in the soil of a pine wood . . . 1.170 ,, ,, 0.40 ,, ,, of an arablefield.. 1.169 ,, ,, 0.40 ,, ,, of an arablefield.. 1-155 ,, ,, 0.40 ,, very light garden soil... . 1,118INORGANIC CHIEMLSTKY. 167 The lower proportion of argon is probably due to the fact that it is considerably more soluble in water than nitrogen is. C. H. 13. Solubility of Silver Halogen Salts in various Solvents. By ERNST COHEN (Zeit. physikal. Chem., 1895, 18, 61-69).--'rhe ex- periments of Valenta (Abstr., 1894, ii, 4L8) on the solubility of the silver salts of halogen acids in sodium thiosulphate and i n potassium cyanide, indicate that the solubility is not that deducible from the equations (I) SNa&O, + 2AqCl = (AgS2O3Na),,N~S2O, + 2NaCL and (11) 2KCN + AgCl = KAg(C"), + KCl. The author has, therefore, examined these solubilitu phenomena with the following results. (1) Silver chloride, if not in excess, dissolves in sodium thiosulphate i n accordance with equation I.(2) If the silver chlor- ide is in excess, the less soluble sait, (AgS203Na)2, is formed. (3) If not in excess, silver chloride dissolves in pot,assium cyanide solution in accordance with equation 11. (4) Excess of the silver salt causes the double salt to be partly decomposed, with formation of silver cyanide and potassium which cram react in the reverse sense until equilibrium is reached, KAg(CX)2 + AgCl Z SAgCN + KCI. Valenta's results were due to the fact that he operated witli H, large excess of tlie silver halo'id L. M. J. Preparation of Lime and Strontia Crystals. By G. BR~~GEI,- IIIAKN (Zeit. a?m-g. Chern., 1895, 10, 41 5--433).-'l'he author has already shown that the alkaline earths can be obtained in crystals by melting and decomposing hheir nitrates by means of heat.The con- ditions necessary for the formation of good crystals are that the crucible be heated to the necessary teniperature only 011 one side ; that perfectly dry calciiim nitrate be employed, and that the crucible he tightly covered during the decomposition so that the air and furnace gases are excltded. Crystals of lime, measuring 1.6 cm., and of strontia, 5.5 inm. in length, have been obtained. A complete description, with drawings, of the furnaces employed, is given in the original paper. The lime crystals are prepared in porcelain crucibles, the strontia crystals in platinum crucibles. The crystals must be carefully preserved in air-tight vessels, dried with pieces of lime and strontia.On exposure to air, they turn dull, but may be brought t o their former brightness by heating with dry lime or strontia. Normal Calcium Chromite. By E. ~ F A U (Compt. rend., 1895, 121, 689--691).-A mixture of 115 grams of chroniic oxide and 45 grams of calcium oxide was heated in the electric fiirnace with a current of 700 amp6res and 50 volts. The product is a mixtiire of yellow lamellae, similar to those obtained by Moissan by heating chromium and calcium oxides in the electric arc, and green, acicular crystals, which are found in the hottest parts of the furnace, and are, therefore, stable at high temperatures. The product is heated with hoiling, concentrated, hydrochloric acid until nothiiig more dissolves. The residue consists of lustrous green, prismatic needles of the normal chromite, CaO,CiD2O3; sp.gr. = 4% at 1P; hardness about 6' The crysfals are not attacked by fluorine in the cold, but on gently E. C. R. 13- 2168 ABSTRAUTS OF UHEMICAL PAPERS. heating an energetic action takes place with incandescence. Chlorine attacks t,he chromite slowly a t a bright red heat, but bromine, iodine, a,nd sulphur arc without action a t the softening point of glass, and water vapour has no effect at a bright red heat. At the softening point of glass, the chromite burns brilliantly in oxygen, with forma- tion of calcium chromate and chromic oxide. Hydrofluoris and hydrochloric acids and concentrated nitric and sulphuric acids have no action on the chromitc, but dry, gaseous hydrogen fluoride and hy- drogen chloride decompose it at a red heat.Fused potnssiumnitratte or chlorate o r hydroxide, or fused alkali carbonates readily attack the chromite. In composition, the chromite is identical with that obtained by Gerber by heating calcium chloride with potassium dichromate. C. H. B. Preparation of Pure Beryllium Oxide from Emerald. Bg PAUL LEBEAG (Compt. rend., 1895, 121, 641-643).-'11he emerald is first fused with twice its weight of ca!cium fluoride in a plumbago crucible by means of a coke fire, and the fused mass is poured into water. A friable product is thus obtained which is very energetically attacked by sulphuric acid, even in the cold. When evolution of silicon fluoride ceases, the residue is strongly heated until sulphuric anhydride is given off freely, and then thrown into water i u small quantities at :t time.The clear liquid is decanted, concentrated, partially neutralised with potassium carbonate, and allowed to cool, when the greater part of the aluminium separates as alum. An impure berglliuin ammonium carbonate is obtained from the mother liquor by treating it with ammonia and ammonium carbonate. Another plan is to heat the ellierald in a carbon tube in the electric furnace ; a large quantity of silica is volatilised, and the residue, which contains only about 30 per cent. of silica, breaks up into powder as it cools. This basic silicate is decomposed by acids, and is treated with a mixture of hydrofluoric and suIphuric acids. The impure beryllium ammonium carbonate is dissolved in nit& acid, the iron precipitated by a small quantity of potassium ferrocyanide, the excess of ferrocyanide removed by means of copper nitrate, and the excess of copper by hydrogen sulphide.The solution is then mixed with ammonia, and the precipitate allowed to remain i n the liquid for three or four days, so that the alumilia may polymerise and become insoluble iu ammonium carbonate. The liquid is theu decanted, and the pre- cipitate treated with a concentrated solution of ammonium carbonate which slowly dissolves the beryllia. The filtered soliltion is boiled, and the well washed precipitate is dissolved in nitric acid, the soh- tion evaporated to dryness, and the residue strongly heated. The beryllia thus obtained shows the spectra of no other metals. C. H. B. Purification of Beryllium Salts.By EDWARD HART (J. Amer. Ohen?. Soc., 1895, 17, 604--C;05).--'fhe process depends on the fact that on adding sodium carbonate to an impure solution of beryllium sulphnte, any iron and aluminium are precipitated first.INORQANIO CHEMISTRY, 169 The powdered beryl is fused with pot assium-sodium carbonate, ground and washed with water, mixed with sulphuric acid, and evaporated to render the silica insoluble. The bulk of the aluiiiiniurn is then removed as alum by adding potassium sulphate, and, after oxidising any iron with potassium chlorate, it is, together with tho rcmainiiig alun:iuinm, precipitded by the cautious addition of sodium carbonate. After filtering, the berJllium is precipitated a s carbonate. L. DE K. Beryllium Carbide. By PAUL LEBEAU (Compt.rend., 1895, 121, 496--499).-Pure beryllium oxide was intimately mixed with hnIf its weight of sugar-carbon and a small quantity of oil, and heated i n the electric tube furnace for eight to ten minutes with a current of 950 amphres and 40 volts. Less powerful currents yield a nitride or products containing nitrogen and carbon. The beryllium carbide obtained under these conditions forms trans- parent, yellow-brown, microscopic crystals, similar to those of alurni- ilium carbide, which i t also resembles in chemical properties. The crystals scratch quartz easily ; sp. gr. = 1.9 a t 15'. The carbide is readily attacked by chlorine at a dull red heat, with formation of beryllium chloride and a residue of amorphous carbon and graphite. Bromine behaves similarly at a somewhat higher tern- perature, but iodine has no action even at 800'.Oxygen produces superficial oxidation a t a dull red heat, sulphur vapour attacks it. ilelow 1000°, but phosphorus and nit'rogen have no appreciable action at dull redness. Dry hydrogen fluoride attacks the carbide with incandescence below a red heat, with formation of fluoride and libera- tion of carbon ; hydrogen chloride behaves similarly, but with less energy. In contact with water 01' dilute acids, the carbide is slowly decomposed, with liberation of methane ; thc change occurriug rapidly and completely in contact with a hot concentrated sodium or potassium hydroxide solution. It reduces concentrated boiling sulphuric a$id, hut is only slowly attacked by concentrated nitric o r hjdrochloric acids, although hot hydrofluoric acid dissolves it rapidly.Fused potassium hydroxide decomposes it w i t h incandescence, potassium nitrate and chloratc are without action, but potassium permanganate and lead peroxide oxidise i t readily. The carbide has the composition Be,C, (Be = 13.8), and no other carbide seems to exist. C. H. B. Beryllium Carbide. By LOUIS HENRY (Conipt. rend., 1895, 121, 600--601).-1t does not follow that because the beryllium carbide described by Lebeau (preceding abstract) is generally similar in its properhies to aluminium carbide, it must be analogous in composition. Magnesia and silica are both in many respects similar to alumina. The analyses of t,he carbide quoted by Lebeau agree closely with the formula CBc,, and the apparent analogy between this compound and aluminium carbide cannot be allowed to over-ride the great weight of the ot'her experimental evidence in fixing the va1enc.y gf b e r y l l i k c.H. 8.170 ABSTRACTS OF CHEMICAL PAPERS. Constitution of Metallic Bases. By NICOLAI KCRNAKOFF ( J . pr. Chem., 1895, [2], 52, 490--528).-1n continuation of his previous paper (Abstr., 1895, i, 499): the author treats of the compounds in which ammonia replaces water of crystallisation, either wholly or in part, and reviews the theories which have been advanced in explana- tion of the existence of metallic ammonia salts of the general forni MX,,nNH3. These theories fall into three classes-( 1) the ammo- nium theory, depending on the pentad nature of nitrogen ; (2) the theory which regards the haloid or other acid radicle in the irietallic salt as unsaturated ; ( 3 ) the theory of higher types of metallic COUI- pouuds as expounded by MendelBeff.In connection with the last, the author quotes some results which he has obtained while investi- gating the refraction coefficient of solutions of the compounds PtC1,,4NH3, K2Pt,C14, Na,PtCJ,, and PtCI,(NOs)2,4NHB. None of the theories to which reference is made can, in the autlior’s opinion, hc regarded as furnishing the basis for R generalisatiori as to the consti- tution of the metallic bases, although each serves to throw light on the subject,. A. G. B Mechanical Properties of Alloys of Copper and Zinc. H g GEORGES CHARPY (C‘ompt. rend., 1895, 121, 494-496).-Alloys of popper and zinc, containing from 0 t o 50 per cent.of the latter, were rolled and hammered in t,he cold until they were brought to a condition of maximum brittleness, and broke with practically no deformation. They were then annealed a t varions temperatures and subjected to tension and compression. F6r the crude cast alloys, the resistance depends on the temperature of casting and on the rate of cooling ; it increases when the metal is cast near its melting point, and when the mould is arranged so as to produce rapid solidificn- tion. The temperatures of annealing may be divided into four zones, which vary with the composition of the alloy. The first, or zone of no mzncaling, extends to about 350” €or red copper, but the masi- mum limit falls as the proportion of zinc increases. The second, or zone of cariable anneuling, in which the degree of annealing varies continuously with the temperature, I S alniost unrecognisable for copper, but iis range increases with tlie proportion of zinc, and for an alloy containing 40 per cent.of zinc it extends almost from the ordinary temperature LIP to the melting point’. In the third, or zone of constant annealing, the effect on the mechanical properties is prac- tically constant ; the zone extends from about 400’ to 1,000” for copper, but diminishes a s the proportion of zinc increases. In all three zones, annealing lowers the resistance and increases the exten- sion before breaking. The fourth zone comprises high tempcratnres near the melting points, and in these the metal undergoes deterioration or is “burnt,” and both the resistance and the extension are reduced.The range of this zone seems to depend on the proportion of im- purities present. The resistance t o tension increases with the proportion of zinc up to about 43 per cent., and then falls r a p i d l ~ ; the elongation beforeINORGANIC CHEMISTRY. 171 breaking also increases with the proportion of zinc up to about 30 per. cent., and then falls rapidly. The most useful alloys are those which contain from 30 to 43 per cent. of zinc; a high proportion of zinc corresponds to a higher resistance, and a high proportion of copper to a greater elongation before breaking. C. H. B. Oxidation of some Gases with Palladinised Copper Oxide. By EDWARD D. CAMPBELL (Amer. Chem. J., 1895, 17, 681-692).- The palladinised copper oxide was prepared as follows :--(l) Coppel.was alloyed with palladium (1 per cent.), care being taken to cool the molten mass as quickly as possible ; the alloy was then annealed, divided into small pieces, and oxidised in the tube. I n the determina- tions given below, this oxide was employed. (2) Finely divided oxide, prepared by the preceding method, was mixed with gum, pressed into wire, and ignit'ed. (3) Palladium (3 grams) was dissolved in aqua regia, and the solution, after removal of the excess of acid, mixed with finely divided copper oxide (300 grams) ; the stiff paste was dried a t 120°, finely ground, mixed with gum, pressed into wire, and ignited. The temperatures given below are the initial combustion temperatures when the palladinised copper oxide is employed, those in brackets are the values obtained with pure copper oxide. Hydrogen 80--8S0 (175-180'), carbon monoxide 100-105" (100-105°), ethylene 240- 250" (315-325'1.propylene 220--230° (2'70-%Oo), isobutylenc 270-280O (320 -330°), methane no combustion at 455'. Acetylene, unlike the preceding gases, does not burn directly; at 395-400°, only + of the carbon and 8 of the hydrogen are oxidised, the remainder. forms a black deposit in the tabe. Full details are given of the appa- ratus employed, and the quantity of the various gases burnt per hour at different temperatures is also t,abulated. J. B. T. Action of Hydrochloric acid on Copper. By RODOLPHE ENGEL (Compt. rend., 1895, 121, 528-530).-Hydrocbloric acid saturated a t 15' attacks copper somewhat rapidly with evolution of hydrogen, and the evolution of gas becomes tumultuous if the copper is previously immersed in it dilute solution of platinum chloride.No action takes place with a solution of a sp. gr. so low as 1.083, which corresponds with the composition HCl + 10H,O. When the liquid is saturated with cixprons chloride, the action becomes very slow, even though the quantity of free acid present may considerably exceed the minimnm limit just specified. Similar phenomena are observed with zinc and tin. A rise of temperature increases the action, and vice cersd, doubtless in consequence of the variations in the solubility of the cuprous chloride. At the ordinary temperature, equilibrium is only established after a very long period. When gaseoua hydrogen chloride is passed into water containing copper and cuprous chloride, the acid is rapidly decomposed, not- withstanding the presence of the copper salt, and i t follows that anhydrous hydrogen chloride is always decomposed by copper.C. H. B.17 2 ABSTRAOTS OF CHEMICAL PAPERS. Action of Nitric Oxide on certain Salts. By H. A. AUUSX and GILBERT J. FOWLER (Chem. Areu*s, 1895, 72,163) .-The substances wci-e exposed in a stream of nitric oxide a t the ordinary temperature and at gradually increasing temperatures, and were weighed a t iiitervals of temperature. Lead dioxide, and also manganese dioxide, yields basic nitrate with but a trace of nitrite ; with lead oxide, the action Commences :Lt 15' and reaches a maximum a t 130" ; with manganese oxide, the action is not so rapid, and is a t its highest at 216'.Moist silver oxide yields equivalent parts of nitrite and free metal a t the ordinary temperature, whilst a t higher temperatures the dry oxide yields silver and silver nitrate. Silver permanganate is attacked at t!:e ordinary temperature, but at 80" the action is very sharp ; the products being silver, silver oxide and nitrate, manganese dioxide, with little OF no manganese nitrate. Potassium permanganate is not appreciably attacked below loo', but vigorously a t 190°, yielding potassium nitrate and manganese oxide. Potassium chlorate, and also barium chlorate, yield chlorine and oitro- gon peroxide a t the ordinayy temperature ; the percentage of chlorine in the gaseous product being below that required to form nitrosyl or nitroxyl chloride ; the solid product is the nitrate, with a trace of per- chlorate, but no chloride. Silver chlorate also yields chlorine in abundance, but a t the same time a large proportion of silver chloride is formed.Potassium iodate commences to evolve iodine at 80", and a t 110' the evolution is rapid; nitrate without iodide remains. Silver iodate, 011 the other hand, a t about l l O o , yields silver iodide without any evolution of iodine. Potassium perchlorate a t above 200' yields abundance of chlorine, leaving a residue of nitrate with a small quantity of chloride ; this is atiributed to secondary reactions resulting from the high temperature. Barium periodate behaves in a similar manner. Lead chromate is not attacked a t above 400°, but above 300' silver chromate yields silver, silver nitrate and nitrite, and chromic oxide.Silver sulphate is slightly attacked at the highest temperature. Mixing lead o r manganese dioxide with lead nitrate caused the action to take place a t a lower temperature than when either the oxide or salt was separately exposed to nitric oxide. D. A. L. Tempering of very hard Steel. Bg FLORIS OSMONI) (Compt. vend., 1895, 121, 684-686).-1f a bar of cementation steel in which the proportion of carbon varies continuously from, say, 0.35 per cent. at one end to 1-70 per cent. at the other, is given a very high temper, it is found that it can be scratched by a needle up to 0.70 per cent. of carbon, cannot be scratched with a highcr proport,ion up to 1.3 per cent., b u t beyond this point can again be scratched.Microscopic examination shows, howeveiv, tha.t the more carbonaceous part is not homogeneous, but contains two constituents : A, which is scratched by glass and orthoclase, although not by a needIc; and B, which is scratched by apatite and perhaps by fluorspar. On a well-polished gurface, B is silver-white, whilst A is greyish. The action of iodine solution or of dilute nitric acid sliows that the mass consists of poly-1NORGlAMIC CHEMISTRY. 173 hedra, sometimes separated, sometimes not, by the carbide Fe3C. Generally, A is distributed iii pointed lamella: parallel with two direc- tions which remain constant for each polyhedron, whilst B forms the matrix. Both A aiid B contain carbon. The constituent A is identical with that which is almost the only constituent of tempered steel containing 1 per ceut.of carbon. The proportion of B incieaszs with the proportion of carbon lip to about 1.6 per cent., and beyond this point the carbide Fe3C-(?) separates in increasing quantities. In order to obtain the maximuin proportion of B, the steel must be heated to a t least lOOO", although nothing is gained by going bejond llOOo, and cooled as rapidly as possible, either in ice-cold water or in yery cold mercury, otherwise the carbide Pe3C separates. Under favourable conditions, the metal will be a mixture of d and B, in approximately equal quantities. Such a, mixture is comparatively feebly magnetic, whilst a bar of the same metal heated a t 800' and cooled in water a t 15' is strongly magnetic, and retains perniariently a higher proportion of the magnetisation imparted to it.It would seem that B is not magnetic. The metal containing equal parts of ,4 and B cannot be filed, and breaks without bending, as much by reason of the presence of the hard and brittle constituent A as because of the want of cohesion between the polyhedra. It is, however, slightly malleable. The properties of B seem to be similar to those of highly nickeli- ferous and manganiferous steels, which contain iron in the allotropic form y, stable above 860". C . H. B. Reduction of Iron Oxides by Carbonic Oxide. By ISAAC BRAITHWAITX (Chem. News, 1895, 72, 211).-At a low red heat, c:irbonic oxide is found to be oxidised more readily by ferric oxide tlian by triferric tetroxide, whilst ferrous oxide is still less active.Conversely, carbonic anhydride is reduced more quickly by iron than by ferrous oxide, and not at all by triferric tetroxide. D. A. L. Action of Silicon on Iron, Chromium, and Silver. By HENRI MOISSAN (Ccmpt. rend., 1895, 121, 62l-G26) .-&-on silicide, SiFe2, is obtained (1) by heating iron to the softening point of porce- 1i1in in a porcelain dish brasqued with silicon. (2) By heating iron with one-tecth its weight of silicon in a crucible in the electric fixmace for four minutes with a u arc from a current of 900 amphres and 50 volts. With a higher proportion of dicou, the product is not attacked by acids. (3) By heating in the electric fnrrince a mixture of ferric oxide with excess of silicon, silica being volatilised. In all cases, the product is treated with nitric acid diluted with four times its volume of water.The iron silicide forms small, magnetic, prismatic crystals, with a metallic lustre; sp. gr. = 7-00 at 22". I t s melting point is higher than that of cast iron and lower than that of wrought iron. Hydro- fluoric acid attacks it readily, and hence it is not identical with the silicide which Hahn described BS not attacked by this acid. Hydro- chloric acid slowly attacks the finely powdered silicide ; nitric acid174 ABSTRACT8 OF CHEMIOAL PAPERS. has no nction, but aqua regja decomposes it, with formation of silica. The gaseous hydracids attack it a t temperatures varying from dull to bl ight redness. Potassium nitrate and chlorate, a t their melting point., have no action on it ; fused alkali carbonates attack it sloml~, and a fused mixture of a nitrate and a carbonate decomposes i t readily.When cylinders of soft iron are embedded in crystals of silicon and hea,ted at the temperature of a good forge, the silicon penetrates to the centre of the cylinders, although the iron does not fuse, and a silicide is formed. This result is a further proof that silicon has a distinct vapour tension below its melting point. Cliromium silicide, SiCr2, is obtained (I) by heating chromium in a dish lined with silicon at a temperature somewhat above 1200' in :I current of hydrogen. (2) By heating pure chromium with 15 per cent. of its weight of silicon in a carbon crucible in a n electric fuimace for nine minutes with an arc from a current of 900 amperes and 50 volts.( 3 ) By heating in the electric furnace for ten minutes wit!i an arc from a current of 950 amperes and 70 volts, a mixture of 60 parts of silica, 200 parts of chromic oxide, and 70 parts of sugav- carbon. The product is treated with cold concentrated hydrofluoric acid, the temperature being kept down, if necessary, by the addition of water. The silicide forms small, prisrnat.ic crystals, very similar in properties to the iron silicide, but less easily attacked by hydrofluoric acid, and more easily by fused potassium nitrate. It scratches quartz, and even corundum, quite easily. Silver, when heated with silicon in the electric furnace, dissolves a considerable quantity, but the silicon separates as the metal COO~P, and no silver silicide ig obtained, nor does the silver retain any silicon.Some crystals of carbon silicide are often formed. It follows that (1) solid silicon may unite with 5t solid metal by reason of its vapour tension, in a manner analogous to cementation ; ( 2 ) liquid silicon unites with a, liquid metal; and (3) silicon may dissolve in a liquid metal, forming either a very unstable compound or no compound at all, and being liberated in a crystalline d a t e as the metal solidifies. C. H. B. Some Alloys of Iron with Molybdenum, Tungsten, and Chromium. By JAMES S . DF: BEKNEVILLE ( J . Amer. Chem. Xoc., 1894, 16, 735--757).-The a,lloys of iron with the metals of the tungsten group have been examined ; they were prepared by melting down cast iron with the metals a t a white heat in a small Fletcher's furnace working with a blast, this temperature being maintained for one hour. Whereas unalloyed molybdenum is practically infusible in furnaces worked with a, blast, its iron alloys fuse a t a much lower temperature.Molybdenum alloys, containing 16.6 and 29.8 per cent. of the metal, were prepared, and tungsten alloys containing 46.5 and 17 per cent. of tungst'en, whilst with chromium, only a single alloy, contain- ing 7 per cent. of that metal, was prepared. The physical propertie8 of these alloys were noted, but the especial object of the investigation was the action of the weak solvent', silver nitrate, on tho alloys, together with their behaviour with liquid and fused solvents. TheINORGANIC C HEMISTRF. 175 more important conclusions drawn from the results thus obtained are : That these alloys, by their resistznce to chemical reagents, their hardness and increased specific gravity, indicate a chemical union between the const,it,uents.That in these alloys a number of com- pounds are present, some of Khich are more stable than others, the latter class being readily attacked by weak solvents. ‘I’hat these com- pounds are distributed with considerable uniformity t.hrougliout the mass of the alloy, segregation being the exception, not the rule, and that their freezing points must be approximately the same, pTeventiiig the segregation of alloys of gre:it density in any one portion of the alloy ; that the more stable of these alloys are definite chemical coin- pounds; that? the less stable may be definite compounds, or of the nature of cryohydrates, or with one of the constituents present in the mixture in a state analogous to that of ice in a frozen salt solut,ion, in which water i s in excess.J . J . S. Two Definite Carbides of Iron with Chromium (Molyb- denum and Tungsten). By JAMES S. DE BENNEVILLE (J. Arne,.. Chew. $oc., 1895, 17, 791--801).-In the course of his work on ternary alloys of iron with chromium, molybrlenum, and tungsten, the author prepared two definite carbides. These were obtained from chromiuni alloys, and only from those two in which chromium was the predominant metal. They formed well defined crystals, differing i n form and reactions from the matrix i n which they were embeddetl. The separation of the crystals was effected by the action of nitric acid, which left them intermixed with a little silica.This was removed its silicon fluoride, and, after washing with water and subsequently with alcohol, the crystals mere obtained free from impurity. They are remarkably inert, not being acted 011 by hydrochloric, nitric, or liydro- fluoric acid. Concentrated salphuric acid slowly decomposes then], leaving a black residue ; they are readily decomposed :it a red heat by chlorine, bromine, or iodine, but their analysis is best effected by fusing with a mixture of sodium carbonate and hydroxide, and potss- Pium nitrate. The results obtained were Fe. Cr. 110. W. C. Total. I. 46.39 46.23 2-01 - 5.53 1 O O - l G 11. 47-24 :35*4.2 - 11-39 5.9.5 100.00 J. J. S. The Ferrates. B.y CLAUDE A. 0.ROSELL ( J . Amey. Chem. SOC., 1895, 17, 760--769).-!l’his paper opens with a short history of the ferrates, mentioning the work of Stahl, Ekeberg, Becquerel, FremF, Denham Smith, Rose, and Bloxam. The author has attempted to prepnre sodium ferrate in the dry way, accoi-ding to Stahl’s method, by calcining ferric oxide with sodium hydroxide, carbonate and nitrate, and with mixtures of &odium hydroxide and nitrate, and also with sodium nitrate and carbonate, but in rain. Sodium peroxide was also tried, and, when the resulting mixture was treated with ice instead of water, a solution of sodium fsrrate w a s obtained. Attempts to obtain iron dioxide by176 ABSTRAUTS OF GBEMIOAL PAPERS. t,he action of an alkaline ferric solution on the solution of the ferrate, 01' by the addition of barium ferrate to ,z solution of ferric chloride, p ro ve d u s el e ss .The most stablo ferrate is the barium compound, BaFeO, + H,O ; whereas calcium ferrate is readily soluble in water, the barium com- p o n d is insolulile; before drying, if, is readily decomposed by all acids, eren carbonic, but after drying i t is not so readily acted on. An alkali sulphate decomposes bayinm ferrate, if i t has not been dried, with t!ie formation of barium sulphate and ferric hydroxide, oxygen bcing set free. I t is further shown, that the emerald green solution obtained by Fremy on passing hydrogen sulphide t!irough a solution of sodium ferrate, is due t o the presence of manganese. The question a s to whether ferrates more closely resemble chromakes or manganates is discussed.So far at3 their oxiclising properties are concerned, they resemble tl:e mangRnates ; a fewate wil1 readily oxidise nitrites, tartrates, 2nd glycerol ; the soluble ferrntes are also reduced by oxalates, alcohol, urea, ether, ammonia, &c., and by most soluble organic compounds, with the exception of the acetates. The simplest method for preparing solutions of sodium or potassium ferrate is to pass chlorine into n solution of the corresponding hydroxide, containing ferric hydi-oxide in suspension. Nickel and Cobalt Silicides. By VIGOUROUX (Compt. yemi., 1895, 121,686-688).-When nickel or cobalt is heated with 10 pcr cent. of silicon in a current of hydrogen, in a reverberatory furnace, combina- tion takes place, w i t h formation of a crystalline product more fusible than the metal.Similar results are obtained by heating the silicon xild the metal in a Doulton crucible ill an oxyhydrogen furnace. Heating silicon with the oxides of the metals in either form of furnace does not yield a pure product. The best results are obtained by heating the metals with 10 per cent. of silicon, in carbon crucibles in the electric furnace, until the greater part of the excess of t h e metal is volatilised. Tlie prodnct is treated with very dilute nitric acid. The silicides, SiNi, or SiCoz, are perfectly crjstallised, and have a metallic appearance, and a steel-grey colour ; they arc more fusible than the metal or silicon, and are stable at the highest temperatures. Tlie sp. gr. of the nickel siiicide is 7.2 a t 17", and that of the cobalt silicide 7.1.Fluorine attacks them with incandescence a t the ordi- nary temperature, and chlorine has the same effect a t a red heat; bromine and iodine are less energetic in their action. Dry hydrogen fluoride and hydrogen chloride attack them at a red heat, and hydro- gen bromide and iodide behave similarly. Hydrofluoric acid dissolves them readily, but the other hdoiid acids act very slowly ; aqua regia, however, decomposes the powdered substances completely. Watei- has no action on the crystals, but water vnpour attacks them at a dull red beat. Oxygen or air oxidises the finely powdered silicides a t a red heat. Solutions of alkali liyvdroxides are without effect, but fused alkali carbonates or mixtures of carbonates and nitrates decompose them readily.C. H. B. J. J. S.INORGANIC CHEMISTRY. 177 New Solvents of Perchromic acid. By WtLLIm M. GROSVENOR, Jun. (J. Amer. Chew. SOC., 1895, 17, 41--43).--The author finds that ethylic acetate and valerate, amylic valerate, amylic chloride, amylic butyrate, formate, and acetate all dissolve percbromic acid, yielding blue solutions similar to that given by ether. Carbon bisulphidc, benzene, light petroleum, turpentine, castor oil, wintergreen oil, bergamot oil, paraffin, chloroform, carbon tetrachloride, toluene, nitrobenzene, and aniline do not dissolvc it. The solution in ethylic acetate is the most stable, bnt eren that, turns colourless after 23 hours, The author does not Agree with Griggi (Xbstr., 1893, ii, 233) in stating that the solution in amjlic alcohol is more stable than that in ordinary ether.J. J. S. Uranium Oxynitride and Uranium Dioxide. By EDGAR F. SMITH and J. MERRITT MATTHEWS (J. b i e r . Chem. SOC., 1895, 17, 686-688) .-To prepaye the oxpitride, uranyl chloride was ylmed in a porcelain boat and heated in a current of dry ammonia, when: at a cornparati rely low temperature, the material assumed a dark coloui*, and copious fumeH of nrnmonium chloride were evolved; the heat was then raised and continued until no more fumes were given off, and n dull black residue free from chlorine was left. This, when fused in a nickel crncit~le with potassium hydroxide, slowly evolved am- monia. When introduced into solution of silver nitrate, brilliant crystals of metallic silver were formed.When heated in a sealed tube with dilute sulpliuric acid (1-2), complete solution ensued, and titration x i t h potassium permanganate showed t h a t 6.83 per cent. of dioxide was Isresent. An estimation of the uraniurx and the nitrogen gave figures closely corresponding with the formula ~~*,N*O,,. I n order to obtain the dioxide, the authors heated the oxide, UsOe, with a large excess of ammtmium chloride in ft porcelain crucible, which was placed in a larger Hessian one, and the whole surrounded with charcoal closely packed; the crucibles were heated i n a wind furnace a t R white heat for about six hours. The reddish-brown residue was free froni chlorine and nitrogen; the percentage of uranium was found to be 88-12 per cent. When heated over a Bunsen flume, i t changed gradually, but completely, into uranonrnnic oxide.L. DE I(. Alloys of Copper and Tin. By FR~TZ FOERSTPR (Zeit. anoyg. Chenz., 1895, 10, 309-319).-The author has prepared alloys of copper and tin containing from 1 to 28 per cent. of copper. These alloys, when broken in coarse Ibieces and treated with cold, fuming, hydrochloric acid, yield, R grey, lustrous, crystalline residue toll- sisting of hard, brittle lamell~e. I n the case of the alloy coiitaining only 1. per cent. of copper, minute, lustrous needles were also obtained. These crystalline residues are only slightly attacked by ammonia, and very slowly oxidised by dilute nitric acid. They precipitate copper from neutral solutions of its salts, although much more s!owly than pure tin, but do not' precipitate copper from a solution of cuprous chloride in Iiydrochloric acid.The composition of the residues yaries178 ABSTRAWS OF CHEMICAL PAPERS, from 38.52 per cent. Cu and 61.42 per cent. Sn to 55.95 per cent. Cu and 43.67 per cent. Sn. The residue, containing 55.95 per cent. of copper, when treated with stronq hydrochloric acid for 2-3 days, yielded a residue containing 61.47 per cent. Cu and 38.88 per cent. Sn. These residues probably contain mixtures of two compounds of the cwmposition Cu,Sn and CuSn. The residues obtained from the alloys poorest iii copper have the same composition as those obtained from those portions of an alloy richer in copper which remain fluid lotlgest. that is, the crystals first deposited are richer in copper than those obtained a t a! lower temperature from the mother liquor.The residues richest in tin begin to decompose when heated above 300°, whereby drops of tin or of a dilute solution of copper in tin are sepn- i-ated : this can be dissolved out by treating the mixture with hydro- ctlloric acid, and the residue thns obtained approaches the compound (:u,Sn in coinposition (see also Le Chateliei., Abstr., 1895, ii, 351). E. C. R. Action of Hydrogen Peroxide on Fluorides and Oxy- fluorides. By AUGUSTO Plccmr (Zeit. anorg. Chem., 1895, 10, 438- 445) .-Potassium ~LEuol.oz?/~el.titaIzate, Ti02F1,,2KFl, is obtained rnixed with the fluorotitacate when a hot solution of potassium fluorotitatiate, TiFl4,2KF1.H2O, is treated with hydrogen peroxide. When this pre- cipitate is dissolved i n hydrogen peroxide and the mixturc! neutralised with sodium peroxide, a crystallisation richer i n Auoroxypertitanate is obtained, but the salt cannot be obtained pure.A fairly pure product is obtained as a gel!om, crystalline powder. when a cold soiution of triainmoniutn fluoroxypertitanate, Ti02P1,,3NH‘,E’I, is pre- cipitated with potassium chloride. When a solu- tion of amnionium fluorotitanate is treated with hydrogen peroxide in the presence of ammonia and ammonium fluoride, the salt, TiO2FI2.3NHJ?I, is obtained as a yellow precipitate. It crystallises from water in small, yellow octahedra. It i s also obtained by treating a solution of titanic acid in sulphuric acid with barium peroxide, then with ammonia until a permanent precipitate is formed, and finally precipitating wit,h neutral ammonium fluoride.It is also obtained by :illowing ammonium fluorotitanite, TiFI,,SNH,FI, washed with a con- centcrated solution of ammonium fluoride, and moistened with alcohol to oxidise in the ail.. A small quantity of the salt, 2TiO,P1,,3NH,Fl, ci.ystallising iri yellow needles, is also obtained. If the solution of the salt obtained by the last method is mixed with ammonium fluoride, R crjstnlliue precipitate of the salt Ti02FI,,SNH,FI, is obtained. Prom the results here obtained and the author’s previous work (Zeit. ano?*g. Chem., 1, 51, and 2, 21), the action of hydrogen per- oxide on the oxyfluorides of molybdenum, tungsten, and niobium, and on the fluorides of tantalum and titanium can be expressed by the following eqnations.Mo02F12 + H202 = MoO3F1, -I- H20. W02P1, i- Hz02 = WOJ% + H2O. NbOFi3 +H202 = Nb0,F13 + H,O. TaF15 + H20z = Tn02FJ, + 2HFl. TiFI4 + H20, = TiO,Fl, + fLHF1. The fluoroxyanhydrides of the type of hydroger. peroxide AmmmiwrL .fluoi.ox~pe,.titaizates, mTi02Fl,,nNH4F1.INORGANIC CHEMISTRY. 179 react with metallic fluorides, whereby compounds are formed come- sponding with those obtained from the fluoroxyanhydrides and the fluoranhydrides of the type of water. The fluoroxy-salts of the type of hydrogen peroxide are analogous in composition and crystalline form to those of the type of water. They can be obtained i n ana- logous ways, but differ from the latter in colour, in the ease with which they give u!, part of their oxygen and in the property they 1)ossees of reducing potassium permanganate in acid solution.E:. c. K. Double Fluorides of CEesium and Zirconium. By HORACE L. WELLS and H. W. FOOTE (Zeit. auorg. Chem., 1895, 10, 434-437). -The double salts are prepared by mixing the solntions of tlie fluorides in various proportions in the presence of more or less hydro- fluoric acid, and then evaporating the mixture to crystallisation. The salt, 2CsF,ZrF4, is obtained by employing an excess of czsium fluoride. It crystalliaes in large, hexagonal tablets, and can be recrystallised wi t,hout decomposition. Thc salt, CsF,ZrF4 + HzO, is obtained in the presence of larger ynnntities of zirconium fluoride. I t separates in monoclinic crystals, mid can be wxryststllised without decomposition. The salt, 2CsF,SZrF4 + 2H,O, is obtained in tlic pi-esence of a l a q e excess of zirconium fluoride.It separates from the solution in small, sparingly soluble crystals, and when recrystallised is partially converted into the 1 : 1-salt. E. C. R. Action of Phosphorus Pentachloride on Zirconium and Thorium Dioxides. Bv EDGAR F. SMITH and HARRY €3. HARKIS (J. Amer. Chem. Soc., 1895, 17, 654--656).-The work WAS under- takeii to complete the investigation commenced by Weber. The dioxides of zirconium aud thorium were introduced into hard glass tubes together with the equivalent of phosphorus penta- chloride ; tbe tubes being then exhausted and sealed. After heating for eight hours at 190°, a complete change was observed, ;I crystal- line mass and dilops of phosphorus oxychloride being scattered through the tube.After opening the tube at, both ends, the contents were heated in a current of clilorine, part of the tube being heated iii an air bath a t 190°, when large, transparent crystals collected in the projecting cold part of the tube. Analysis proved them to consist of the corresponding chlorides. L. DE K, Iridio-ammonium Compounds. By WILHELM P A i m A E i t (Zeit. nn0l.q. Chem., 189.5, 10, 320-386; see also Abstr., 1889, 352, and 1891, 402 and 1165).-When iridium chloride is treated with am- monia in an ordinary reflux apparatus, about 4 s per cent. of a double salt of the composition 1r(NH3)&I3 is obtained, together with the pen tanline c hlorochloride, a te tramine corn pound, Ir( N H3)&CI3, H@, and the aquopentamine chloride, Ir(NH3)50H2C13.When 50 C.C. of a solution of' iridium tyichloride, containing 5 grams of metal mixed with 150 C.C. of 25 per cent. ammonia, is heated in a Lintuer's180 ABSTRACTS OF CHEMIOAL PAPERS. pressure flask a t 100' for 10 hours, the following products are ob- tained. Iridium hydroxide corresponding with 0.11 gram of metal. This is separated by filtration, and the filtrate evaporated on the water bath to dryness, whereby all the aquopentamine chloride is converted into pentamine chlorochloride. The dry residue is treated with cold water, whereby animonium chloride and the tetramine chloride are dissolved. The residue insoluble in cold water is dried on the water bsth and treated with cold concentrated sulphuric acid, whereby chlorosulphate is formed, and any double salt (about 1 gram) which is present, remains undissolved.The sulphuric acid solution is finally treated with fuming hydrochloric acid, and the pentamine chloride filtered off. Iridiopentamine chlorochloride, Ir(NH3)5ClC12, has already been described (Abstr., 1891, 402). The red coloration of the salt pre- pared as above is due to a very minute trace of iridium tri- chloride, which can be separated by treating the hot aqueous solution with hydrogen sulphide. It crj-stallises in yellowish-white octahedra; when heated a t high tclmpcratures, it yields metal, ammonium chloride, and ammonia ; it is completely precipitated from its aqueous solution by hjdrochloric acid. The chlorh ydroxide, Ir(KH3)5CI(OH)2, is obtained by treating thc chlorochloride with freshly prepared silver oxide.It is very stable, absorbs carbonic anhydride from the air, and is slowly decomposed when boiled with water. It is also obtained by warming the chloro- chloride with sodium hydroxide on the water bath. The acid chloro- s u b h a t e , 41r(NH3),C1S04 + 3HzS01 + 3H,O, is obtained by dissolving the chlorochloride (1 gram) in concentrated sulphuric acid (2 c.c.) and then adding water (10 c.c.). It crystallises in lustrous, bright yellow prisms, is easily soluble in water, and has an acid reaction. The chlorodithio?Late, Tr(NH3)5CIS206, is obtained by adding barium di- thionate to a cD1d saturated solution of the chlorochloride. It crys- tallises in long, six-sided prisms, and with lHzO in thick, four-sided prisms. The chloroxalate, Ir(NH3),C1C204, crystallises in slender, white needles. Tridiopentamine chZorochZoYhidife, 31r(NH3),CIC12 + 21rC13, is ob- tained by mixing the solution of the chlorochloride with one of the trichloride as a flocculent precipitate, and from the remaining solu- tion as a crystalline, yellow powder on evaporating it on the water bath.It is only slowly attacked by sulphuric acid a t 110", and is decomposed by heat, yielding iridium, ammonium chloride, and hydrogen chloride. The pentamine chloro-salts here mentioned, together with thorn previously described, are neutral, with the ex- ception of the acid sulphnte and the nitrite which has an alkaline reaction. Iridiopenfamine bromobromide, Ir( NH3),BrBr2, has been pre- viously described. It is best obtained by boiling the pentarnine chlorochloride with potassium hydroxide for about five hours, when the aquopentamine hydrate is formed.The solution is saturated with 50 per cent. hydrobromic acid, whereby a white, crystallinc? precipite of the aqnopentamine bromide, Ir(NH3),0H2Br3, is obtained, and, by heating the solution of the latter salt on the water bath, i t is 7.4 grams are obtained.INORQANIC CHEJJISTRP. 181 converted into the broniobromide. This crystnllises in yellow, iahombic Iwisms, t~ : b : c = 0.9752 : 1 : 1.5637, is soluble in 352 psrts of i v a t e r a t 12*5', and has a sp. gr. of 3.245 at 16.5'. 'l'he byomonitrite crystaliises iu yellow, rhombic prisms, a : b : c = 0.969 : 1 : 1.53.3, and is isomorphous with the pentarnine chloronitrite. Tridiope?~t(iminc iodoiodide, 11~(NH~)~ll~, is obtained by heating the aquopentnmine hydrate at 100'.It crystallises in thick six-sided prisms and octahedra, belonging to the rhombic system a : 2, : c = 0 993 : 1 : 1.552, is soiuble in 770 parts OF water a t 1 4 O , and 50 parts of boiling water, and has the sp. gr. of 3,586 at 15.5'. I)* idioy P 1 i t a mi 11 e n it rat o i t rate, T r ( N H3) 5N 03( S 0 j) ?, i s o b t:t i ned by 1ie;Lting the aquopentamine nitrate at 100'. I t crystallises in micro- scopic, quadratic tablets, explodes when heated, dissolves in 349 p;wts of water at 16' and i n 40 parts of boiling water, and has the sp. g r . of 2.510 at 18.5'. Tridioaquopentnmine chloride, Ir(NH3),0H,C13, the aquopentamine bromide and the aquopen tamine nitrate have already been described.Ti-idioaquopciztamiize iodide, prepared in a similar way to the above ::quopentarnine salts, is a white, crystalline powder, having a yellowish- brown fluorescence ; it is converted into the pentamine iodide when heated, dissolves in 15 parts of water, and has the sp. gr. of :!*.?53 at 14'. The apopentnmitze chloriridite, Ir(NH,),OH,C I3,IrCl3, is obtained by adding iridium trichloride to a solution of the aquo- pentarnine chloi4e in dilute hydrochloric acid. It is a yellowish- brown, crystalline precipitate, insoluble in water, and is not attacked By eold, concentrated sulphuric: acid. Iridiohexantir~e chEoride, Ir(NH&Cl9, is obtained by heating the pentanline chlorochloride (2 grams) with 25 per cent. ammonia (20 c.c.) in a sealed tube at 140' for 48 hours. The product is evaporated to dryness with hydrochloric acid, dissolved in water, and the filtered sDlution precipitated with sodium pyrophosphate. The washed precipitate of iridiohexamine sodium pyropliosphate is dissolved in dilute hydrochloric acid and precipitated with nitric acid, whereby the hexaminc nitrate is obtained. The nitrate is then evaporated to dryness two or three times with hydi*ochloric acid, and the solution of the product cooled with ice and precipitated with ice- cold, fuming hydrochloric acid. It crystallises in large, co1ourless, six-sided prisms belonging to the monosymmetric system a : b : c = 0.5843 : 1 : 0.6502 ; /3 = 57' 31', and gives measurements very closely agreeing with those of Klein's luteocobalt chloride (Annulen, 166,188). It is soluble in 4.5 to 5 parts of water, and has the sp. gr. of '2.4335 a t 15.5'. The hexamine hydroxide, Ir(NH,!,(OH)3, is obtained in soh- tion by treating the preceding salt with silver oxide. The solution is strongly alkaline, displaces ammonia froni ammonium salts, and gives precipitates of the metallic hydroxides with solutions of alumi- nium and zinc salts. On exposure to air, it is converted into the carbonate which crystallises in crusts of microscopic six-sided tablets. Tlie 7ie;l:anzine bromide, Ir(NH3)6?3r3, obtained by precipitating a solution of the nitrate with hydrobroniic acid, crystallises in colour- less six-sided prisms similar to thsse of the hexamine chloridc ; it is soluble in 28-30 parts of water, and has the sp. gr. of 2.942 at TOL. LXL ii. 14l S 2 ABSTRACTS OF CHEMICAL PAPERS. 15.5'. The hezanziize iodide, Ir(ltu'H3)cT, is obtained by treating tl~e hexamiiie hjdroxide with excess of hjdriodic acid. I t c~ystdliees j i s yellowish, lustrous tablets and pyramids, gives off iodine vaponrs wV17cq~ heated, is soluble in 91 parts 01 water a t 1 8 O , and has the sp. gr. of 3.291 at, 16.5'. The hexanzine niti~rfe, Ir(NH3)6(N03)3, crystallises it) large, quadratic tabIets belonging to the tetragonal system a : 7) = 1 : 1.042, and isomorphous with the luteocobalt nitrate ; it is soluble iii 59 parts of water at 1 4 O , and bas the sp, gr. of 2.395 at 15' Iyidio- heleainine fewicyanide, Ir(NH3)6Fe(CN)6, is obtained by adding potas- sium ferricyanide to a solution of the hcxnmine chloride in hydrochloric acid. It crystallises in orange-red prisms, and is ver-y sparingly soluble i n water. Iridiohexaniine chlorin'dite, Ir(NH3)& 13,1rC13 is obtained as an amorphous, yeilowish precipitate which is greyish-yellow when dry: From dilute solutions, it separates in small, quadratic tablets. It is insoluble i n cold water, is attacked by concentrated culphuric acid a t 190°, and, when boiled with it, yields a clear, bright yellow solution. The reactions of the yarious classes of salts a r e described i n detail in the original paper. The solutions of the hexamine salts are neutral. E. C. R .

ISSN:0368-1769    

DOI:10.1039/CA8967005162

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

1s2 ABSTRACTS OF CHEMICAL PAPERS. M i n era1 o gi c a 1 Chemistry. Native Sulphur in Michigan. By W. H. SHERZER (Arne?.. J. Sci., 1895, [33, 50, 246-248) .-In a band of carbonaceous limestoric in the Upper Helderberg Limestone of Monroe Co., are cavities con- taining calcite, celestite, sulphur, and rarely selenite. In the sailit' quarry is a stream of water highly charged with hydrogen sulphide, from which sulphur is now being deposited. It is suggested that the hydrogen sulphide has been derived from pyrites, marcasite, &c., or, perhaps, from the organic matter in the neighbouring rocks. Black Carbonado from Brazil. By HENRI MOISSAN (Compt. rend., 1895, 121, 449-450).-A specimexi of carbonado found in t h e province of Babia, Brazil, weighed 630 grams (or 3073 carats), nlld is the largest that has yet been found.It is rounded in form, has 8 full black colour, and resembles in the character of its surface, &c., t.he microscopic grains of carbon obtained from ingots of silver or i1.011 compressed by sudden external cooling. Itl is somewhat porous, and originally weighed 3167 carats, bat lost about 19 grams during exposure to ail. f o r t w o months. Graphite from a Pegmatite. By HEKRI MOISSAN (Compt. rend., I&!%, 121, 538--541).-An American pegmatite, containing 12.77 per cent. of graphite, was decomposed by means of hydrufluoisic acid. The graphite was thus obtained in flexible, lustrous lamellze, the sur- facts of which Fhowed strim in the form of equilateral triangles ; it began to burn in oxygen at 690°, and left 5.01 per cent.of ash, which consisted mainly of silica., alumina, and calcium oxide, with only a L. J. S. C. H. B.3ILNERALOOICAL CEENISTRT. 183 trace of iron. The graphite w\.ns intumescent liIcc that obtained by dissolving carbon in metals. Jlowover, when treated with nitric acid and potassium chlornte, it increases enorrtiously in volume. Microscopic examination of the pgmat ite proved that the faces of the crystals of quartz OL' feisyar in contact with the Iamell3e of graphite showed triangular strice precisely similar to the strix! on the 1amelI;lc. It follows that tbe graphite must have been pre-existent in hhe material from which the pegmatite was formed, and when the latter solidified, the graphite rrns compressed between the crystals of quartz 01- felspar.Gallium and Indium in a Blende from Peelwood, N.S.W. By J. Boow KIRKLAXD (Ausfi*aZim A4ssoc. AJv. Sci., Fourth &port, [I8921 1893, 266--267).-A peculiar, grey zinc ore from the abovc locality showed by the spectroscope the lines of gallium and indium. Crude chlorides of these metals have been extracted. Analysis of the ore gave C. H. B. SiO,. Pb. Fc. Cu. Zn. S. Total. 6.05 16-71 11.06 5.00 29.77 29.21 97-70 L. J. S. The Senarmontite of Nieddoris, and the Minerals which accompany it, Arite, Breithauptite, Gersdorffite, and Smaltite. By DOMENICO LOVISATO (Jnlrrlj. f. Min., 1895, ii, Ref., 230-231 ; from Atti E. Acc. Lima+, Rend., 1894, 3,82-89).--The nickel ores of Nied- (loris, in the miriing district of Arbus, Sardiuia, consist of a mixture of several minerals.Of these a light red mineral gave analysis I ; this agrees with arite, and has the formula 9RAs + 5RSb. A dark red ore gave IT, this agreeing with the formula RAs + 4RSb, and is thus a, mixture consisting principally of breit hauptite. A dark, black mineral gave 1111, agreeing with the formula (Ni,Fe,Co),( S,As,Sb),, which comes near t o gersdorffite, with, perbaps, some admixed ullrnannite. The silver-white portion of the ores gave I V (with 2-14 per cent. of gqngue), agreeing with the formula (N i,Fe,Co)As2, and corresponding with smaltite (or chloanthite). S. As. Sb. Ni. Co. Bi. Fe. Zn. Pb. Total. I. 0.85 29.82 26-57 36.81 3.91 0.99 0.98 trace - 9993 11. 1.00 8-49 2S.63 60.07 3.6.5 1.55 1-81 - - 100*13 111. 13.72 44-78 3.11 35.12 0.91 2.36 - - 100.00 IV.2.94 58.76 1-06 9.85 7.65 - 9-86 0.72 6.33 97.17 IV contained in addition 2.14 of gangue. Senarmoutite and valentinite occur with these ores. Hercynite from Valtellina. By GOTTLOB ED. LIXK (Ber. Akad. Berliu, 1893, 47--53).-1n xn altered gabbro, from near the Italian- Swiss frontier, are large, black, fine-grained masses, ccxitaiuing black grains of a spinel, sometimes showing octahedral faces, together with plagioclase, biotite, sillimanite, corundum, rutile, and a yellowislt metallic ore. In sections, the spinel is green and transparent, arid often encloses what appears from the analyses to be pyrrhotite. On L7- 2 L. J. S. 14-2184 ABSTRACTS OF CHEllIOAL PAPERS. cyushing the mass some hydrogen sulphide is given off. h a l y s i s of thc magnetic spinel and pyrrhotite gave I; I1 is the same neglecting impurities ; sp.gr. of the pure material, 4.0108. ,41,03. Fe203. FeO. MgO. SiOc. Fe. S. Total. 59-62 3.10 25-30 9.38 1.59 1-79 1.02 101.80 61-21 3.18 25.98 9.63 - -- - 100~00 This gives R,Oj: RO = 6200: 6016, the FeO being too low. Hercynite can only be distinguished from other green spinels by ana- lysis. L. J. S. Northupite, a new Mineral. By WARREN &I. FOOTE (Arne).. J. SC;., 1895, [3], 50, 480--48l).-This was found by C. H. Northup, in clay a t Borax Lake, California, as regular octahedra., of a dirty white t o dark brown colour. Cleavage imperfect ; brittle, with uneven frdcture ; H = 3.5-4. There are regularly arranged enclosures, pi.obably of organic matter. When heated, the mineral blackens, and gives off a burnt odour, with violent decrepit.ntion, owing to uiechanically enclosed water ; easily fusible.Qualitative analysis shows i t to be a double chloride and carbonate of sodium and i ~ a p e s i u r n , together with traces of phosphoric acid, silica, iron, calcium, and organic matter. Boiling water decomposes the mineral with separation of basic magnesium carbonate. Nature of Stinkstone (Anthraconite). By WILLIAM SKEY (T~ans. N.Z. Inst., 1893, 25, 379-380).-The smell of stinkstone is usually considered to be due to bituminous matter; the author, how- ever, considers that in most cases it is due to hydrogen sulphide, this gas being supposed t o be occluded in the free state i n the limestone, it not being given of€' a t a red heat. Analysis of a light grey stone, free from bituminous matter, gave Siliceous Organic L.J. S. CaC03. MgC03. FeO. CaS04. matter. matter. H,O. IT,S. Total. 59-40 0.93 0.21 trace 42.44 0.21 0.89 0.31 99.39 L. J. S. Optical Properties of Lithiophilite and Triphylite. By SAMUEL L. PRNFIELD and JULIUS H. PRATT (Arner. J. Sci., 1895, [S], 50, 387-390) .-As iron replaces manganese in the passage from lithio- philite (LiMnP04) to triphylite (LiFePOJ, it is shown that there is an increase in the refractive indices, and a gradual change in the size of the optic axial angle, as is seen in the following table, which gives part of the measurements obtained for sodium light. Locality. ~- Brancliville, Conn. . . . . ¶, 9 9 ,, .... ), .... #rafton, N.H.. . . . . . . . Rabenstein, Bavaria. . . FeO per cent.-.- 4 -24 9 -42 13 *63 26 -58 35 -05 - I 1 OVer Plane of optic axes.MINERALOGICAL CElERlISTRY. 185 The optically positive mineral from Grafton has for thallium light '2V = 21' 5s' in the plane (OOl), and for lithium light 2V = 15" 3' in the plane (100). Litliiophilite is optically positivc, and the acute bisectrix is perpendicular to (010) ; the Rabenstein triphylite is optically negativc, nncl the acute bisectrix is perpendicular to (001). On plotting ft curve, it is seen that a furtlier increase in the amount of iron would cause 2V to become zero again, this time negative, with the optic axis perpendicular to (001) ; arid as the pure com- pound LiFePOJ (which is not known) is approached, it lnsy be expected that the optic: axis would open out in the plane (010).L. J. S. Genesis of Natural Phosphates and Nitrates. By k. J. ARMAND GAuirrEn (Jczh~b. f. X n . , 1895, ii, Ref., 2i6-279 ; from Albit. tles dliws, 1894, [9], 5, 1-53).-After describing the phospbntes of the Grotto of Minerva, Dept. H6rault (*4bstr., 1893, ii, 419, 5i7), tlie author points out that there are three modes oE occurreuce oE commercial phosphates : (1) in igneous rocks and gneissea ; (2) in beds and veins, where they have been deposited from solutioii ; ( 3 ) nodu:es and earthy depo5its associated with calcium sulphate and carbonate, and nitrogenous organic matter, these being o€ animal and vegetable origin, and include guano deposits and those of t,he Grotto of Minervn. Here the ammonium phospliate, formed by tlie decomposing nnim:il matter, acts on limestone, giving calcium phosphate and amnloniuill carbonate ; the latter with limestone, in connection with nitrifjiiig ferments, producing calcium nitrate.T n an experiment, a warn1 ammoniacal solution of ammonium phosphate acted on an excess of chalk ; the product contained 11-28 Ca,(PO,), and 82.78 per cent. OF clibasic calcium phosphate, or brushite (CaHPOa,2B,0). Similar reactions take place in the presence of clay ( h h t r . , 1893, ii, 526). 'the formation of phosphates and nitrates are thus connected ; in the presence of sodium chloride, large nitre deposits, such as those OE Peru, might be formed. Phosphates from Algeria. Phosphatic Rock at Bougie having the Composition of a Superphosphate. By H. MAL~~OI' and A. MALBOT (Compt. relid., 1695, 121, 443-445) .-Analyses are given of several Algerian phosphatic deposits ; they consist mainly of mixtures of calcinm and magnesium phosphates and carbonates, only traces of the phosphates being soluble in water, 01- in anrnoniurn citrate solution.The deposit at Uougie, howcver, consists of a hard, wd, internal portion, surrounded by a white, friible substance, tlic coinposition being as follows. L. J. S. LOSS Loss at Soluble at 130'. dull rednes?. Y20s. SO3. SiO?. White substance.. 7*!13 21.42 33.50 1.51 traces Red substance.. . . 12.20 9.87 14.42 2 53 0.37 Fc203 and Alto3. CaO. MgO. Insoluble. White substance., , . . . 4-33 25.51 0.28 14.00 Red aubstance.. . .. . . . 16.35 4.37 0.35 52-07186 ABSTRACTS OF OHEBIICAL PAPERS. In the case of t h e white substance, 13.29 p i g cent.of pliospho~ic: nnliydride is soluble in water, 3 5 1 is insoluble in vater, but solublc in ammonium citrxte soli?tioii, and t h c i.cinsiiiiiig 11.70 pel’ cent. soluble i n dilute acids ; in the case of the red substance, 2.03 per cent. is so:uble in water, and tlic remaining 12-39 per cent. is soluble in ammonium citrate solution. When phosphoric acid is dii*ectly precipitated by magnesia mixtnre i n presence of amrnoniuni citrate froni solutioix containing organic: n;ntter, the results are too low. The m p n i c matter, as n rule, is incotupletely destroyed by evaporating with nitric acid, and the sub- stnnco should be heated at dull rediiess i n contact with air. Inter- mediate precipitation with ammonium molybdate avoids t h e error arising from the presence of organic! matter.Kentrolite from Lgngban. By GUSTAV Fr,rsrc (,7&.b. f. U i n . , 1895, ii, Ref., 240 ; from Uikang Vet. Akad. Hand. (Stockh.), 1691, 16, ii, No. 4).--B1ack, orthorhombic crystals of kcntrolite occur with Bi.;iunite, richterite, barytes, and caIcite at LHngban, Sweden. Analpis gave !SO2. 1111~0~. Fc20,. PbO. MnO. CaO. Total. Sp. gr. C. H. B. 17-68 16.59 5-58 55-72 3-05 0.91 99 53 6.068 Thc forinuln is given as R2“Si04 + E2’”Si05, whele RI” is P b : &In: Ca = 33 : 3 : 2, and R”’ is llii : F e = 3 : 1. Thorium and Yttrium Minerals of Norway. B-y LUDWIG SCHMELCK (Zeit. a m p . Chenz.,1~95,542-513).--Theexternal characters, blowpipe reactions, action of acids, and approximate thoris and gttrin, psrcentages, aye given of I he wrious Norwegian minerals, which :ire nsed f o r the extraction of these oxides for incandescent lights : thesc minerals are t horite and oraugite, reschynite, euxenite, fcrgusonite, gadolinite, orthite, monazite, senotitne, and lreilhauite. The COIN- mercial thorite and orangite usunlly do not contain more than 45 and 60 per cent.of thoris i*espectively. Analyses of Beryl. By J A l r E s S . DE B m ? J w I r , L E ( J . Awer. Chem. Soc., 1894, 16, 65-66) .-In the following a.nnljses special attention was paid t o the alkalis. IT, apple green, Black Nt., Buncombe Co., N.C. 111 and IV, light peen, Ac xorth, N.H. L. J. S. L. J. S. I, dull yellow, from Faliluo, Sweden. SiO,. -4l2O3. Fe,O,. Fe3. MgO. CaO. K20. Cs,O. Ns20. I. 64.02 16-44 0.68 12-91 0.23 0.50 2.76 - 0.2;; 11. 66.24 17.64 1.36 11.06 0.09 0 36 0.30 - 0.60 111.65-23 17-72 1.35 12.37 0.37 0.61 0.3; - 0.53 1V. 66.53 17.11 0.Y4 12.24 0.20 0.45 0.22 0.12 0.97 Li,O. T120. P,O,. Total. Sp. gr. 1. 005 1.76 0.26 99.86 2.713 11. 0.14 2.06 0 78 1 O O G 3 2.746 111. O$6 1.49 0.14 100.22 2.714 IV. 0.17 1.49 trace 100.45 2.730 L.MINERALOGICAL C HEMTSTRT, 187 Analyses of t'ne Emerald. By PXL LEBEAU (Compt. T e d . , 1595, 121, G01-603).-An analysis was made of an average sample of %bout 30 kilos. of emerald from the neighbourhood oE Limoges. The emerald was in lsrge, cr1st:Lllisecl fragments, and showed, as a iule, little colom ; it contniiicd manganese, phosphoric acid, titanic acid, and free fluorine, which have not previously been observed in emeralds from this locality.Loss 011 SiO? AJ2O3. EeO. Fe,O,. 3111~0~. XgO. CaO. P,05. ignition. 65-93 16.25 14-27 1.05 0.12 0.58 0.16 0.10 1.44 with traces of alkalis and of Ti02. Some of the crystals contain veins of a dark coloured substawe, and when powdered, or when treated with concentrated sulphut*ic acid, evolve a gas which lias the odour of ozone. Becqnerel and Rloissan have shown that the odour of ozone observed in the case of the fluorspar from Quinci6, under similar conditions, is due to the presence of free fluorine, which decomposes the moisture of the air. It would follow that the Limoges emeralds contain free fluorine or a perfluoride, and this is confirmed by the fact that the gas evolved by &he action of sulphuric acid etches glass. C. H. B. Optical Properties of some Compact and Earthy Silicates.By ALFRED LACROIX (Compt. rend., 1895, 121, 737--739).-The fol- lowing ill-defined minerals, which appear to the eye to be compact 02 earthy, were all found, on examination under tlie microscope, to show an acute negative bisectrix, with an optic axial angle of varying size, perpendicular, or nearly so, to a good lamellar cleavage ; these charac- ters being analogous to those of the micas, it may be assumed that these minerals are monosymmetvic : chrome-ochre, glauconi te, cela- donite, charnosite, berthierine, bavalite, akinite, talc, meerschsum, clays related to halloysi te (severite, leazinite) and montmorillonite (confolensite, delanouite), and nontronite (pingnite and gramenite). Opal, Andalusite, Tourmaline, Sillimanite, Cordierite, Pin- guite, and Hoeferite from Bohemia.By FRIEDRICH KAwm (Tsch. .Win.. Mitth., 1893, 14, 483--525).-0pnl occurs in a pegmntite vein in the gneiss near Pisek. it beicg shown t o have been derived. together with some kaolin, from the felspar. 1 is the analysis or t h e yeEow opal, sp. gr. 2.294, and I1 of the bluish-white, sp. gr. 2.313. L. J. S. Alkalis H,O. SiO,. d1203, Fe,O,. CaO. Mn0. XgO. [cliff.]. Total. L---d I. 5.77 84.86 6-56 trace trace 2-21 [0.60] 100.00 11. 5.35 90.62 i3.18 trace - 1.02 trace 100.17 Both are completely decomposcd by hot hydrochloric acid, but only incompletely by aqueous potash, the insoluble portion (22.47 per cent. for the yellow, and 3288 f o r the bluish-white) containing, besides opal, small quantities of kaolin, quartz, mica,, limonite, limnatite, psilomelane, felspar, noiitronite and chalcedony.Andahsite, in rose- t o hyacinth-red, columnar masses, in a peg-158 ABSTRACTS OF CHEMICAL PAPERS. matite vein near Cejov, gave analysis 1 f o r thc dark, and I1 f o r the light coloured. The powder is rose-red, the colour becoming lighter on ignition. Secondni-y cordierite is intimatelj- associated Tyith tile andalusite. 111 is the analysis of n, w r y similar andalusite from n pegmatite vein near Sedlitx. Si02. AIz03. Fe,O:+ Loss (HZO). &O. Total. Sp. gr. 100.77} 3.119 I. 38.1.5 60.11 1.52 0.9'3 - 11. 38.52 60.59 0.99 - L-r---J 100.10 111. 37.34 60.84 1-40 1-27 trace 100.85 3,122 The varying quantity of silica, which is somewhat in excess of that 1-equired by the formula A1203,Si02, and the presence of water may indicate commencing decomposition.IToum?aZiize.-A part+ analysis of the ljlack tourmaline, associntect with the ariclalusite of Cejov, gave H,O. SIC,. AI2O3. FeO. MnO. M',nO. CnO. Total. 2.24 38.01 :31*72 12.47 trace 2.05 small quantity 86.49 It is intimately associated ,;it11 what appears to be scconda1.p- muscovite. Sp. gr. 3.166. Sillimctnite occurs in the cordierite rock of Humpoletz in places where the effects of pressure on the rock are evident. The fine, colourless ueedlrs form a silver-white t o yellowish aggregate. mhicli has a silky lustre, and a hardness as low as 2 to 4. Analysis I is of the finely fibrous variety ; 11, of the more coarselg crystallinr, which is closely associated with quartz.Loss 011 SiO?. A1,0,. Fc,O,. C'aO. ignition. Total. Sp. gy- T. Si.11 60.54 1mce 0.38 2.40 100.43 3.15;f Although the excess of silica' i n TI is best explained by the presence of quartz, it may, perhaps, indicate an appro:di to AI,(Si04), (w6r- thite ?)- 11. 43.12 55.81 - 0.42 0.99 100.34 - Coydierite, from the cordierite rock of Humpoletz, gave Si02. AIz03. Fez03. PeO. MgO. MnO. Loss (FT,O). Total. Sp. gr. 50.13 32.11 2.24 6-37 8-47 0.32 0.99 100.63 2.696 This gives the formula H,0,6(Mg,Fe)0,6(Al,,Fe,)03,15Si02 ; or, if the water be neglected ( ~~g,Fe)z(A1,Fe)lSi,Ole. Piiaguite, of a, yellowish-green colour, occurs i n earthy masses with kaolin and sandy iron-ochre in a weathered Ecliist a t Spaniom, near Taus ; it is supposed to have been produced by tbe action of sulphuricz acid, derived from pyrites, on felspsr.The mineral, on a fresh frnc- ture, is greenish, and has a fatty appearance. H = 1 ; sp. gr. 2.767. It fuses with difficulty to :L black, magnetic slag; i t is completely clecomposcd by concentrated sulphuric acid. The incan of two analyses of air-dried material gave Loss on Fe20e3 (and n 22-48 41.33 35.10 0.75 1.01 100.61 ignition (H20). 8i02. little FcO). A120,. CaO. Total.MINERALOQICAL CHEMISTRY. 189 A t l l O o , 16.53 per cent. of water IS given off; a t 250°, 17.09 per cent. Fcrmula, Fe20j,3SiOr,ciH20, o r 2Fe20,,,GSi0,,3H,0 + SAq. Jl’oefe~ite, this new mineral from I G t z , near Rakonitz, has mncli tlle same mode of occurrence and origin as the pinguitc clcscribtd above. It is earthy and OE a siskin-green colour with fatty lustre, H = 1-3.It is difficultly fusible to a black, magnetic slag ; it is only partly clecouiposed by strong snlphuric acid, and iiot a t all by 113-drochloric acid 01’ by aqueous potash. The material was purified 1)s means of dilute acid, and after being air dried, gave on nnalysis Fe203 (ancl a Loss 011 Loss at SiO,. little FeO). AI,O,. ignition. Total. 120’. sp. gl’. 36.14 45.26 1.11 18.15 100.Gti 0.99 2.27 35.88 46.64 18.20 lOO*id 3.79 2-41 I”1ormiila 2Fe20,,4Si0,,7H20. The points in which the minei a1 differs from nontronite, pinguite, and other chloropals are given. Schrauf’s analysis of chloropnl from Mugrau is reduced to a mixture of hoeferi te and Ca0,3 Si 0,,4H20. L-- ----J L. J. S. Zeolites of the Syenite near Dresden. By E.ZSCHAU (Abh. Ges. Issis, 1894, (1893), 90--105).--The modes of occurrence of tlie n r i o u s zeolites found in connection with the sgeuite of the Plaucn- sclier Grund are described i n detail. Brick-red, granular lantnontite gave analj-eis I ; this red mineral does not Iose water and crumble, :IS the white does. Of the eight analyses given for analcite, I1 is of the massive, red mineral, and 111 of the white and crystalline. Red radiated natrolite gave I V ; sp. gr. 2.243-2.266. SiO,. A120,. Fe203. CaO. Na2C). H20. Total. I. Laumontitc.. . . . . 53.88 20.73 trace 9.28 1.97 13.96 99.82 11. Analcite (red). . . . 58.16 20.43 little 0*:37 11.43 8.iO 99.18 111. Do. (white).. 57.32 20.90 trace 0.31 11-45 9-18 99-16 117. Natrolite.. . . . . , , 48.04 26.17 trace 0*9G 13.96 9.91 99.04 Isomorphism of the Felspars (Albite-Anorthite).By FR. \VPILLERAX‘T (Compt. rend., 1895, 121, 740-741).-As the optic axial angles calculated f o r the felsprrs, on the assumption that they are isomorphom mixtures of albite and anorthite, do not agree with t h e obserwd values, i t is comidered that the albite and anorthite mo!e- cules are chemically combined. L. J. S. L. J. S. The Leucite-nepheline Group. By CARL F. RAMYFLSBEI~C; (Bcr. Akad. Berlin, 1892, 543--56l).-‘l‘he minerals here considered form two dimorphous groups, represented by the cubic leucite ancl the hexagonal nepheline. Nost are orthosilicrttes, but leucite, pollucite (and nepheline partly, as here shown) w e metasilicstes ; these and other differences in the composition and formilla of these iso- morphons groups find a n analogy in tbe felspars.The formuln: here given for pollucite, leucite, kaliophilite, euci-yptite, aud Doelter’s artificial soda-nepheline are the nsunl ones. In nepheline, where the190 ABSTRAUTS OF OHEMICAL PAPERS. hilica is in excess of thc orthosi1ic;tte forinuln, the ratio A1 : Si = 1 : 2.4 is assumed, giving the foimuln RliAl,4Si16060, OY, as I< : Nn is often as 1 : 5 , G(N~,A1,Si,O,),~,AI:Si,Ol?. This combination of ;in orthosilicate (soda-neplieline) with anot1ic:- salt (the nietasilic,it3 leucite) is what occurs iu the sodalite group. This formula also explains the observed alteration of leucite in to sanidine and nephelinc as follows : 13R2AlzSi& (leucite) = R,4A11iSi160Go (nepheline) + tiK,hl,Si,O,, (orthoclase).Cancriuite (with davyne) is written as an isomorphous mixture of carbonate and silicate, as was done for the very similar artificial silico-carbonate (Abstr., 1887, l d ) , ]lamely, x (R’*S i 0,) , y (Ca,S i0,) ,x (A 1,s i30,,), where R’ represents N a mid H, 2nd S i represents Si and C in varying amounts; o = 22. Sodalife is written as the isomorphous mixture NsCl ,Ns,Si04, Al,Si,O,, ; liere the ralio C1 : Si is 1 : 4, it iiiay also be 1 : 3. EIormulce on the same lines are given for liaiiync, nosean, and the hexagonal micro- sommite, the last being 3 (4 R C 1, R, S 0, ?3 R., S i 0 4 , 3 -41 .) S i 3O + 2 ( 2CaC12,CaS04,3CazSiO~,3A14Si,0,?). Laxtibite, from Brogger and Biickstrijm’s analysis, is deduced fis NaC1,4NaS,,10SazS0~,10NalAl,Si401G, with palat of the sodium re- placed by calcium ; deducting the artificial ultramarine from this, tho hauyne formula is ari-ivec! at.L. J. S. Ilvaite, Harmotome, Opal, Danaite, Scheelite, Chromiferous Muscovite, Gersdorffite, Nickeliferous Pyrrhotite from Canada. By G. CHRISTIAN HOFFMAXN (Beport Geol. Stc~cey, Canada, 1892, 5, ii, It, I-72).-IZvnife, iron-black, associated with calcite, tremolite, and andradite, from Barclay Sound, Vancouver Island ; sp. gr., 3.859. SiO?. A1,OJ. Fr203. PeO. pVIi!O. CaO. MgO. H20. Total. 29-81 0.16 18.89 3!2*5U 2-82 13-82 0.30 1.62 99.32 €€a?-motmze, small ciydzils 011 calcite, from O’Connor, Ontario ; sp. gr., 2.39. $SO2. k1203. BaO. CaO. K20. Sa,O. H20. !total. 46.36 17-16 21.18 2.25 2 ? 14.54 101.49 OpaZ, cornnion, white, o r greenish, from basaltic breccias at Ssvoiia bltn., B.C.; sp.gr., 2.012, after ignition, 2.083. It is nearly all soluble in caustic potash, the residue consisting of SiO, 0.76, A1,0, 0.23, FezOs 0.26, CaO 0.35, MgO 0.23, alkalis ? 0.09 = 1.92 per cent. On ignition, there is a loss of 7-00 per cent. of water; of this, 3.25 per cr211t. is lost over sulphuric acid ; the material dried over acid gains 6-75 per cent. in n moist atmospherc, and the original material gains 3.28 under similar conditions or when immersed in vater. After ignition, water is not re-absorbed,MINE RXLOQ ICAL CHEMISTRT. 191 Dnizal'to, Insssivc, steel-gi*cy, nssncinted with nickelifcrous p j r r l i n - An analysis by ti,. A. ;I. titc ttt Grahnm, Ontario: s?. g:."., .>.983. Johnston gave, after deducting, - i s 1 7 7 per cent.of quartz, AS. S. Fc. c'o. Xi. Sb. Au, Totai. 42-22 18.84 :3;3*:23 4.09 0.93 0.60 trace 100.00 8chceZite, in pale wine-yellow ci*ptals, associated with hsmati te, p p b o t i t e , pyrites, and quartz at. Harlow, Quebec, gave on analj-sis by Johnston, \TO3. CaO. Fc,O,. SOL. Total. Sp. p. 79.90 19.37 0.73 0.29 100.26 6.059 Chwn{ferozrs miiscocite, massive, Imigh t emerald-green, from Mnta- watchan, Renfww Co., Ontario, gave on analysis by P. G. Wait ; sp. gr., 2-93. SiO,. A1303. Fe,O,. Cr,O,. 31110. CaO. JIgO. K20. Ka20. II,O. Total. 4:3.72 35-51 2.94 1.26 0.26 4.46 1-33 8.88 0.39 3.68 10246 Gersdoi:$iife, massive, o r :is crystals (octahedra or cuho-octahedra), steel-grey, associated with niccolite, pyrrhvtite, &c., a t Denisoi?, Ontario ; sp.gr., 6.231. Analysis by Johnston gave, after deducting 1i3.55 per cent. of quartz, As. S. Xi. Fe. Co. Cu. Total. 46-96 16.71 2G*:3.1! i.90 2.01 0.10 100.00 XickeZij'ei*ozi.s Pyi-rhotitc.--Tlie yesults of the examination of SO nickel ores are given ; most of these are pyrrhotite with an average o f about 2 per cent. of Ni (vai-ies from a, trace t o 4.13 per cent.) ; cobalt is absent, o r piwent only in traces (in one case there is 0.17 per cent.). Numerous analyses arc given of various ores, waters, &c., in t,he report. IA. J. s. The Wide-spread Occurrence of Barium and Strontium in Silicate Rocks. By \VrLr,Iaar F. HILLERRAND ( J . Amer. Chem. Eh., 1894, 16, 81-82).-Attention is drawn to the fact that the detailed rock analyses made in the labomtory of the United States Geological Survey often show the presence of barium and strontium, usually below 0.1 per cent.of each, but sometimes a little more, as in some rocks from Montana and Co~lomtdo (compare next page). L. J. S. Banded Gabbros of SBye. By Sir ARCHIBALD GEIKIE and J. J. HARRIS TEALL (Quart. Jow?~. QwZ. Soc., 1S94, 50, G45--660).- Analyses, by J. H. Playel*, are given of various portions of the banded pbbros of Druim an Eidline. I is of a light caloured hind mainly composed of labradorite, also u-it11 augite, nralitic hornblende, aud ir!agnetite. 11, a dark b~iid composed of augite, m:rgueti te, and labradorite. I1 I, :I thin, ultrsbnsic band mainly composed of augitc a n c l magnetite. The titminni is present in the magnetite, but not as an intergrowth of ilmenite.192 ABSTRACTS OF CHEMICAL PAPERS. Si02.Ti02. A1,03. Fe203. FeO. FeP,. Mn oxide. CaO. MgO T. 52.8 0.5 17.8 1.2 4.8 - 12.9 4.8 Ir. 40.2 4.7 9-5 9.7 12.2 0.4 0.4 13.1 8.0 111. 29.3 9 2 3.S 17.8 18.2 0 4 0*:3 10.0 8 . i Na20. K20. Loss on ignition. Total. $41,. gr. I. 3.0 0.5 1.2 99.5 2.91 11. 0.8 0.2 0.5 99.7 3.36 111. 0.2 0.1 1-0 99.8 :3*t37 This rariation is supposed to be due to the intrusion of a hetcro- geneous magma. L. J. S. Igneous Rock of Yogo Peak, Montana,. U r WALTI;R H. WKEIF nntl LOUIS V. PIRSSON (Anzer. J. Bci., 1SY5, [3], 50, $G7-4i9).-!l'he inassire, granular, igneous rock of Yogo Peak, which consists mair.1.y of uugite and orthoclase, shows a prcgrcssive diffei*entintioii along the nxis of the mass ; :it one end of the rock is a syenitc: (and.I), aud as the ferro-magnesian minerals and tlie basicity increase, it passes through the new types y o p i t e (anal. 11) and ~ h ~ ? ~ l i i ~ i t e ( a n d . 111). Apatite, sphene, iron ore, hornblende, oligoclasc o r anclesine, wi(1 biotite arc always present, but in varying amounts in the different, types; in the sjenite, there is a little quartz, and in thc shonkinitc a little olivine. Yogoite is defined as a rock having about equal amounts of orthoclase and angite (including othcr ferro-magncsiaii minerals), there being a predoininance of orthoclasc in sjenite, and of nugite in the slionkinite type; tlie last nitnie was first given by ttic authors (BUG. G'(oZ. SOC. dmer., 1895, 6, 400-422) to a rock frorii Square Butte, Montana (anal.IV). The extreme members of this ,c eries would be sanidinite and pyroxenite. SiO.,. TiO,. A1203. Cr,O,. Fe.,O,. FcO. MnO. MgO. CaO. BaO. I. 61.65 0.56 15.07 trace 2.03 2.25 0-09 3.67 4.61 0.27 11. 54-42 0.80 14.28 trace 3.32 4-13 0.10 6-12 7.72 0.32 111. 48.98 1.44 12.29 trace 2.88 5.77 0.0s 9.19 9-65 0*4:3 11'. 46.73 0.78 10.05 - 3.55 S.20 0.28 9.68 13.22 1i.d. SrO. Na,O. R20. Li20. (at IlO'). (abore 110'). P2O;, Total. I. 0.10 4.3.3 4.50 trace 0.26 0.41 0.33 100.1 .-I 11. 0.13 3-44 4.22 trace 0.22 0.38 0.59 100*1!~ 111. 0.08 2.22 4.96 trace 0.2G 0.5G C.98 F, 0.22 99.99 IV. n.d. 1.81 3.76 trace 1-24 1-51 C1, (3-18 1009i By R. SPKIGH I- (Trans. N.2. Inst., 1893, 25,367-3i5).-This rock show s in anal3 sis 1 n compara,tively large silica percentage considering the large amount of olivinc present; augite is present only in small quantity; sp.gr., 2.68. IT20 1120 L--- ---J L. J. S . Olivine-andesite of Banks Peninsula, N.Z. The porphjritic labradorite fclspar gaye I1 ; sp. gr,, 2.719.MINERALOGllCAL CHEMISTRY. 193 Loss 011 SiO.,. Bl,O,. Fc,O, + PeO. CaO. MgO. Na,O. RzO. ignition. Total. T. 55.12 20.41 7.74 5.35 2-75 3.80 2.50 3.13 100*80 IT. 55.3 26.3 1.8 11.4 - 5.30 trace - 100.1 L. J. S. By PATRICK X~RSHALL (Ti*a)zs. N.Z. Im/., 1894, 26, 368-387) .-This rock occin*:: in the volcanic system of Banks Peninsula; it is of a very light colour, with large porphyritic crystals of plngioclase, and in vesicles numerous clear, glassy crystals of tridyniite ; ferro-magnesian minerals are rare 01' absent, but magnetite is abundant, and there is no interstitial glass.I and I1 are the extremes, as regards silica percentage, of the five analyses given; sp. qr., 2.351-2.415. Calcu- lated from the analyses, there must be 29 per ceut. of free silica, which is supposed to exist as tridymite in the ground mass ; 2'3.95 per cent. of the rock is dissolved by boiling aqueous soda, but of this 35-05 per cent. is alumina. 111 gives the analysis of the felspar, which includes a narrow border of orthoclase round the plagioclase. Analysis of the associated basic and intermediate volcanic rocks are g I ven. SiO,. A1203. Fe,O,. FeO. CaO. MgO. K20. Na,O. H,O. Total. Tridymite-trachyte of Lyttelton, New Zealand. I. 73.07 13.75 2.55 - 3.27 0.99 2.46 4.60 - 100.69 T I . 71.09 15-45 1.05 0.34 3.25 0.89 2.35 4.81 0.07 99.75 311.60.56 22.05 - - 7.25 - 3.54 7.93 - 101.33 I and I1 have traces of MnO, and I tracs of P,O,. 1;. J. S. Meteorite from Moonbi, Tamworth, N.S.W. By JOHN C. H. MINGAYE (Joum. a d Proc. Roy. SOC., N.S W., 1893, 27, 82--83).- This meteorite, weighing 29 Ibs., gave on analysis .91*350 7.886 0.564 trace 0-003 trace 0.068 trace Fe. Ni. Co. Cu. Sn. Cr. C (graphite). C(combined). SiO,. S. P. 0. Total. Sp. gr. 0.039 nil 0.21'7 trace 100.127 7.833 L. J. S. By EDWIN E. HOWELT, (Amer. J. Sci., 1895, [3], 50, 252--254).-The Cherokee meteorite was found in 1894 near Cherokee Mills, Cherokee Co., Georgia ; weight, 154 lbs. Widmanstitten figures are strongly marked; analysis I by H. N. Stokes. The Losttown meteorite, found in 1868 in the same county, is of different appearance and composition, having only 3.36 per cent.of nickel. The Cherokee and El Capitan Meteorites. Fe, Ni. CO. CU. Si. P. S. C. Total. I. 91.96 6.70 0.50 0.03 trace 0.11 0.01 trace? 99.31 11. 90.51 8.40 0.60 0.05 trace 0.24 trace - 99.80 T h e El Capitan meteorite was found i n 1893 on the northern slope of the E l Capitan range, New Mexico; weight. nbonf 61 lbs.194 ABSTRACTS OF OIIEMICAL PAPERS. Analysis I1 by H. N. Stokes. '- fiery ball " seen in the neighbocrliood i n 1882. 48G).-Meteoric iron from Kendall Co., Texas, was found to contain amorphous cai-boil, but ~eitliei- graphite nor diamond ; a specimen from Newstead, in Scotland, contains amorphous carbon and graphitc. but no diamond; one from the Sierra de DCesa, in Chili, contains a small quantity of graphite which seems to hare been subjected to moderate pressure, but neither diamond nor amorphous carbon ; another from Toluca-Xiquipilso, in Mexico, contair,s no carbon a t all ; the iron from Novy-Urej, Krasnoslobodsk, Russia, IWS found to con- tain amorphous carbon and black diamond, as Jerofecff aiid Latchinolt' have nlrendy stated.A further examination of the iron from C a k n Diablo, confirms the :.uthor's earlier statement., that t h i s nieteorite contains black diamonds, a i ~ c l i t is the only meteorite in which the author has found amorphous carbon, graphite, and diamond together. Water from Lake Corangamite, Victoria. Bg AhDREjv W. CRAIG avd N. T. &I. WxLshioltc (Australiccn Assoc. Adu. Sci., 4th Repo9.f. 3893 [l892], 270--d71).-Sp.gr. = 1.035; analjsis gaye in parts I)cr 1000, It is suggested that this may be ihe L. J. S. Meteorites. By HEXIU Aro1ss.m (Compt. ?Y d., 1895, 121, 483- C. H. B. Tof a1 bases. Ca. Mg. K. Na. SO,. C1. Br. as sulphates. 0.063 1.272 0 387 16.145 0.i58 27.312 0.102 57.276 Hydrogen su3phide and carbonic anh-jdride vere also prescnt. The water was specially examined for rare alkalis, but, only lithium, potas- &urn, and sodium were found in the concentrated mother liquor. Water from Nashville, Illinois, and from the Soap Lake, Washington. By GEORGE STCIGER (Bull. U.S. Geol. Swcey, 3893, No. 113, 113).-Water from the " American Carlsbad Spring," at Nashville, Illinoi~, contained in one million parts 4262.31 parts of solids consisting o f : SiO,, 0.29 ; SO4, 39-76 ; COs, 26.80 ; C1, 0.57 ; Al2O3, 0.08 ; Ca, 10.02 ; Ng, 6.51 ; Na, 15.97 = 100.00.Hypothetical combinations : NaCI, 0 95 ; Na2S0,, 45.15 ; MgS04, 9.01 ; MgC03, 16.47 ; CaC03, 25.05 ; A1203, 0.08 ; Si02, 0.29 = 1OO.UO. Water from the Soap Lake, Washington, contabed in one million parts 28194.57 parts of solids consisting of : Si02, 0.40; SO4, 15847 ; CO,, 34.13 ; GI, 12.50; Ca, trace ; Mg, 0.04 ; Na, 37.27 ; H (bicarbon- ate), 0.19 = 100.00. Hypothetical combinations : NnCI, 20.61 ; Na,SOd, 22-59 ; Na2C03, 40.22 ; NaHC03, 35-65 ; MgHzC206, 0.23 ; SiOs, 0.40 = 100.00. The water is rjtrongly alkaline, and contains come organic matter. By WILLIAM F. HILLEBRAND (Bull. U.S. Gtol. S w u e y , 1893, KO. 113, 114). --4 thermal spring near Taw; sp. gr. 1.G0273 a t 1S.4'. In parts per million were found : SiOz, 60.8 ; SO4, 151.0; PO4, 0.2; C 0 3 , 2153.5 ; B,03,,4'6 ; CI; 231.4 ; F, 5.2 ; Fe203, 1.6 ; AI,O3, 0.5 ; Ca, 22-8 ; L. J. S. L. J. S. Analysis of Water from Ojo Caliente, New Mexico.PHYSIOLOQICAL CEEAIIIS YRY. 195 Sr, 1.4; Mg, 9.5 ; K, 31.4; X:I, 995.1; Ti, 3.41 = 3671.4. The lijpotlieticnl conibinntioiis nrc : Lic'I, 0.62 ; KCI, 1.7(i ; KaCI, 9-01 ; Wn,BB,O7, 0 16 : NaqSOi, G.59 ; Na,CO,, 54.49 ; Ca,P,O,, 0.01 ; CaF',, 0 3 2 ; CaC03, 1.27 ; SrC03, 0.07 ; RfgCO.j, 0.98 ; SiO , 1.78 ; Fe203, 0.05 ; AI,O,, 0.01 ; CO, (bicarbonate), 22.8s = 100.00. Also ti-aces of arsenic, nitrates, iodine (P), baricni, and ammonia. No organic matter, titanium, bromine, manga,nese, OF sulphides. L. J. S. BJ- 11'. PXRAIL:NTIEIL (Conzpt. ?*end., 1895, 121, GS4--645).-3Iaiiy of the mineral waters in the neighbourhood of Clermont contain small quantities of volatile bituminous matter i~ecognisable only by its smell and taste, and all these waters contain ammonia. The water of n spring at Grassion, from tlic bituminous limestone, has the follow- ing composition per litre :-Residue at 180°, 4.;iOO ; total GO?, 4.S70 ; C1, 0.075 ; SO3, 0.016 ; SiO,, 0.050 ; CaO, 0.330 ; MgO, 0.155 ; K,O, 0.026 ; Na,O, 2 036 ; L&O, 0.001 ; Al,O:,O 004 ; NH3,0.006 ; no traces of i r m , arsenic, nitrates, or non-volatile organic matter. Three other springs contaixed the following quantities of smmoriin per litre :-3Gdecins, 0.0010 ; la Vallihi*e, 0.0002 ; artesian well, 0*0040. The water of the spring a t Fziy de In Poia. contains as much a s 0.0454 gram of ammonia iier litre. There is some evidence that Bituminous Mineral Waters containing Ammonia. " part of the nitrogen is present in the form of oyganic amines. C. H. B.

ISSN:0368-1769    

DOI:10.1039/CA8967005182

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

PHYSIOLOQICAL CEEAIIIS YRY. Physiological Chemistry. 195 Respiration in Marine Invertebrates. By HORACE M. VERSON ( J . Physiol., 1895,19,18-70).-0bservations relating to the respiratory exchanges in many of the lower marine invertebrates are described. An appendix treats of the composition of the gases and salinity of Eea water. The respirator-y activity of these animals is small as compared w i t h that of fishes. The more lowly the animal, as a rule, the greater is the increased effect produced by a rise of temperature, moreover, the respiratory activity varies inversely as the size of the ariimnl. Cap- tivity produced opposite effects in different animals. The respiratory quotients are higher, as a rule, than in warm-blooded animals, and generally become greater than unity on asphyxiation; in one case (Amphioxus) it rose to 4 45.This is probably due to the rapid onset of decomposition. Calculated on the amount of soIid in their bodies, the respiration of these lower marine animals is enormous, usnally greater than in man. Thus C'estzis and Salpa contain respectively only 0.24 and 0.26 per cent. of solids; other transparent animals 0.4 to 0.6; Ainp1tiod.u.s 12-8, and the fish Helioszis, 22.3. During captivit,y, pelagic animals rapidly get smaller, and the respiratory quotients, as a rule, increase. The rhythm of the Medwa Yltizostonza is not affected by tempernturc to196 ABSTRACTS OF OHEMICAL PAPERS. PO great an extent as the respiratory activity. decreases during activit,y. The rhythm rapidly W. D. H. Gas Formation in the Human Stomach.By ERxsfr WrssEr, (Zeit. physiol. Chw2., 1895, 21, 234--252).-Six cases were investi- g:ited, and very exhaustive tables are given of the analyses of the gases removed from the stomach, and also of those which formed in the stomach contents af tei- removal. G. Hoppe-Seyler’s method of analysis was employed. The fermentation and the presence of sarcina? are by no means interdependent. The gases found were those of swallowed air, plus a large excess of carbonic anhydride and of hydrogen. W. D. €I. Exchange of Liquids between Blood and Tissues. By J. B. LEATIIES (J. Physiol., 1895, 19, 1--14).--The conclusions to which the experiments recorded lea2 are : Changes in the osmotic pressure of the blood are compensated, with extreme rapidity, by the transfer of liquid from tissues to blood, or from blood to tissues, when the kidneys are excluded from the circulation.There is no evidence that the vessel walls play other than the part of a passive membrane in this interchange of liquids. Tbey cannot be said to have the power of actively regulating the composition of the circulating blood. The osmotic pressure of the lymph from the thoracic duct is always slightly above that of the blood. This slight difference is not affected by alterations in the osmotic pressure of the blood, and is more easily accounted for by metabolism in the tissues than by any active func- tion of the vessel walls. W. D. H. Initial Rates of Osmosis of certain Substances in Water and in Liquids containing Albumin. By W. S. IJAZARCB-BARLOW (J.Yhysiol., 1893, 19, 140--166).-The osmometer used, a new one, is described and figured. (1) The ratio between the initial rates of osmosis of glucose, sodium chloride, and urea in equimolecular solutions is not the same as the ratio between their final osmotic pressures, or the ratio between the differences of their freezing points and that, of water. The prac- tical bearing of this conclusion is that i t is impossible to state, from n determination of their freezing points, that one solution i; hypertonic, isotonic, o r hypotonic as regards anotlier solution of a different composition a t pressures within the limits possible in tho animal body, This can only be determined by experiment in eacli case. (2) The ratio between the initial rates of osmosis of glucose, sodium chloride, and urea in equimolecular solutions differs according as the membrane is composed o€ peritoneum or copper ferrocyanide.The importance of the membrane as a factor has been previously insisted on by Graham and L. Meyer. (3) I n the case of the peritoneal membrane, thc initial rate of rsmosis of the three substances named is diminished by the presence of even small quantities of albumin. (4) With t,he same membrane in watery or albuminous solutions, The conclusions arrived at are.PHYSIOLOQICAL CHEXISTRT. 197 the initial rate of osmosis of glucose is greater than that of sodium chloride ; that of urea being the smallest. Intravascular Injection of Peptone. By E R m s r H. STARLING ( J . PA ysiol., 1895, 19, 15-17) .-The present experiments do not confirm Gley’a statement (Arch.de Yhysiol., 1895, 711) that in dogs, a.fter ligature of the portal lymphatics, the injection of “ peptone ” has no effect on the blood. Gley’s results are explained by sup- posing that he dealt with an accidental aggregation of immune dogs. Absorption of Iron Salts. By H. W. F. C. WOLTERING (Zeit. physiol. Chem., 1895, 21, 186--233).-1n att.empting a solution of this vexed question, the method adopted was to estimate the amount of iron in the liver and other organs, not in the urine, as in the work of many previous investigators. The animals used were mice, dogs, and rabbits. I n some control experiments, manganese was given instead of iron, the sulphates being the salts used. Microscopic investigation showed a greater amount of iron in those animals to which iron had been given ; this was confirmed by quantitative analysis.The iron of the liver is contained in part in the nncleo-proteid of that organ. I n the blood of the animals, the amount of hEmoglobin and the number of red corpuscles increases. Effect of Feeding Cows with Whale and Herring Meal, especially as regards Milk Production. By JOHN SEBEBLIEN (Landzo. Vtmuchs-Stat., 1895, 46, 239-308) .-Experiments were made in which groups of 10 carefully selected cows were fed with and without whale meal. I n the preliminary period (of one month), in which both groups were fed alike, the food was as follows:- Turnips (80), straw chaff (go), hay (40), rape cake meal, linseed cake meal, and malt germs (each 10 kilos.). During the next period (10th Januaryto 1st March, l894), whale meal was given to the second group in increasing amounts (5 to 15 kilos.), whilst the food of the first group remained much the same as in the preliminary period.During the third period of three weeks, the food of both groups was the same (without whale meal). The effect of whale meal was to raise the yield of milk by 6 per cent. or more during the period in which it waa given; but there was no after esect. It made no difference whether 0.5 kilo. of whale meal was given o r 1.5 kilo. (the cake being i n this case reduced by 1 kilo.). The percentage of fat was not altered by the whale meal when this was given 8s additional food, but was lowered when an extra quantity was given in the place of cake. The absolute amount of f a t was increased during the first period of whale meal feeding, but sank during the last period (with increased quantity of whale meal) to the amount produced in the preliminary period.As regards live weight, there was practically no difference in the two groups. The results of very numerous experiments made in Denmark indi- cate that the composition of milk remains constant with different foods, and, in the author’s experiments, very abnormal amounts of prote’in produced merely a lowering of the percentage of fat. It W. D. H. W. D. H. W. D. H. VOL. LXX. ii. 15198 ABSTRACTS OF CHEMICAL PAPERS. seems probable that the increase in fat observed when cows arc turned out to grass, is due rather to the more natural way of living than t o the difference in the composition OE the food.The experiments with herring meal were chiefly t o ascertain whether any taste was imparted to the milk and butter. The 1-csults showed t h a t the meal had no effect either on the taste, or on the keeping qualities o f the milk and butter ; and the chemical examination of the butter produced from COWS fed with whale meal, showed no alteration in the Wollny numbers or in the Kijttstorffer numbers ; and there was no depression in the iodine numbers, showing that there is no direct migration of the whale meal oil into the milk. The evidence obtained from agriculturists as regards the taste and keeping properties of the butter is in favour of whale meal. Digestibility and Nutritive Value of Pumpkin Seed Cake and Buckwheat Grain.By A. WICKE and HUGO WETSKE (Landw. Versuchs-Stat. 1895, 46, 371--382).-Two full grown shepp were fed for three periods of 16 days with (I) hay (I kilo.), (11) hay (900 grams), and air-dried pumpkin seed cake (100 grams), and (111) hay (800 grams), and air-dried buckwheat (300 grams) respectively. During the second eight days of each period, the faxes and urine were collected and examined. The following numbers show the percent- ages of the different constituents (1) of pumpkin-seed cake (sheep No. I), and (2 and 3) of buckwheat (sheep Nos. 1 and a), which were digested. N. H. J. M. Dry Organic Crude N-free matter. matter. Protei'n. Fat. fibre. extract. Ash. 1. 83.15 88-55 84.73 104.69 118-76 42.74 56.19 2. 74-22 74.55 79.73 92.37 40.21 77-56 62.04 3. 67-37 67.65 69.76 108.87 7.94 74.03 30.93 The high results obtained in the case of fat and crude fibre (over loo), are ascribed to the difficulties and defects of the method.The results show, however, that pumpkin seed cake is a highly digestible food, about 85 per cent. of the protein and the whole of the fat being digested. As regards the experiments with buckwheat, the results (2) obtained with sheep No. 1 are the more trustworthy. They shorn that in buckwheat all the constituents (except the crude fibre) are very digestible, i n part more digestible than those of the cereals. It is possible, however, that the employment of both foods i n larger quantities might give less favourable results; in the case of pumpkin seed, owing to the high percentage of fat, N. H. J. M. Pigments of the Pieridae.By F. GOWLAND HOPKINS (P~oc. ROY. SOC., 1894, 57, 5-6).--l'he wing scales of the group of butterflies known as the whhe Pieridae, cotitaiti uric acid ; those of the yellow Pieridze contain, as their pigment, a yellow derivative of uric acid, which the author has obtained synthetically by heatiiig uric acid with water in sealed tubes a t high temperatures. This yellow pigment the author terms Lepidotic acid, and its coustitution is still undeio investi- gation. J. J. S.PHTSIOLOCIICAL CHEMISTRY. 199 Constancy of the Freezing Point of Milk and other Organic Liquids. By J. WISTER (Cowpt. relid., 1895, 121, 696--698).- Cryonietric observations show that milk atid blood serum are equi- moleciilar, and their molecular concentration is the same i n all the animals examined.This seems to be true, also, of other liquids derived from animal oipnisms. The constancy of the freezing point of milk affords a valuable means of testing its purity ; its spontaneous aitera- *ions rapidly lower the freezing point, whilst the addition of water raises it. Experiments with milk from various sources show that the values of A, the reduction in the freezing point, vary between 0.55 and 0.57, whilst the values f o r the number of gram-molecules per 100 grams of water, n, vary between 0.297 and 0.308. In a large majority of cases, including all the specimens of human milk, the value of A was 0.55, and that of 12 0.0297. The corresponding values for blood serum from several different animals vary between exactly the same limits.From these results, it is possible to consider the effect8 of various solutions on living blood, independently of the nature of the dissolved substance. If the molecular concentration of the solution is not equal t o that of thc serum, it will produce either a dissolution of the sus- pended red and white corpwcles, or a precipitation of dissolved fibrin and other constituents. It follows that the blood corpuscles and .fibrin must be regarded as having the function of regulating the mole- cular concentration of the blood sex-urn, just as undissolved ci-ystals maintain a saturated solution at the point of saturation. C. H. B. Vernix Caseosa. By W. G. RUPPEL (Zeit. physiol. Chcnz., 2895,21, 122--133).-This secretion of the f e t a l skin contains 35 per cent.of water, and 14 per cent. of substances soluble in ether. The remainder consists of proteid and ash, in which calcium, magnesium, sodium, potassium, and phosphoric anhydride, but only traces of chlorinc were recognised. Attention was, however, particularly directed to the ethereal extract. I n it glycerol and oleic and palmitic acids were found, but the chief interest centres round the discovery of isocholesterol i n it. In this, the secretion is similar to the fat of sheep's wool. Absence of Sugar from Normal Urine proved by a New Method. By SIR GEORGE JORNSON (Plzarrn. J. Trans., 1893, [3], 25, 603--605).-1f 4 C.C. of normal urine is placed in a test tube of about half an inch diameter, a n equal volume of a saturated aqueous soh- tion of picric acid added, and then 2 C.C.of liq. potass= (P.B.), an orange-red colour instantly appears as a result of tbe incipient reduc- ing action of creatinine at the ordinary temperature. If the liquid be heated and kept at the boiling pnint for about a minute, the colonr deepens, and appears bright red through the test tube, held up t o the light. If an aqueous solution of glucose, containing 2 grains to the ounce, be treated in like manner, the liquid will be so dark that no light will be visible across the full diameter of the tube. The solution af glucose ceases to give any coloration when i t is diluted beyond 1 part in 10,000 : but the creatinine reaction continues until the diln- W. D. H. 15-2200 ABSTRACTS OF CHEMICAL PAPERS. tion reaches 1 part in 200,000. The extreme delicacy of the latter reaction affords a method of detecting a small quantity of glucose in the presence of creatinine by comparing the colorations produced by known quantities or dilutions. Poisonous Effects of Acetylene.By NwroR GRBHANT (COWL& rend., 1895, 121, 564-566 ; by MARCELLIN BERTHELOT, ibid., 566 ; and by HENRI MOISSAN, ibid., 566).-A mixture of 20 vols. of acetylene, pre- pared from calciutn carbide, 20.8 vols. of oxygen, aud 59.2 vols. of nitrogen was breathed by a dog for 35 minutes without any marked disturbance, and 100 C.C. of the blood was found to contain 10 C.C. of acetylene. With 40 vols. of acetylene, the proportion of oxygen remaining the same, a dog died in less than an hour, owing to failure of the heart's action, and 100 C.C. of blood contained 20 C.C.of acetylene. With 79 rols. of acetylene and 21 vols. of oxygen, the poisonous effects were still more strongly marked. It follows t,hat acetylene may be fatally poisonous when present in proportions as high as 40 per cent. by volume. A mixture of coal gas with air and oxygen containing 20.8 per cent, of the latter and 1 per cent. of carbonic oxide was nearly fatal to a dog after i t had been breathed for about 10 minutes, and 100 C.C. of the dog's blood contained 27 C.C. of carbonic oxide. It follows that acetylene is much lees poisonous than ordinary coal gas. Berthelot,, in some experiments made many years ago, i n conjunc- tion with Claude Bernard, found that acetylene, when present to the extent of a few per cents. by volume, is without injurious effects on birds.The poisonous properties often attributed to this gas, as pre- pared by the older methods, are probably due t o the presence of carbonic oxide or hydrogen cyanide. Moissan finds that when acetylene is prepared from pure calcium carbide, and is purified by being liquefied, it has a very pleasant, ethereal odour, and can be breathed in small quantity without evil effects. If, however, the calcium carbide has been prepared from coal and impure lime, it may contain calcium sulphide and phosphide, and the acetylene prepared from it then has a, very disagreeable odonr. Constitution of Heteroxanthine and its Physiological Action. By MARTIN K ~ C ~ ~ G E R and GEORG SALOMON (Zeit.physio2. Chem., 1895,21, 169--185).-Frorn 10,000 litres of human urine, 13 grams of xanthine, 12.5 grams of paraxanthine, and 7.5 grams of heteroxanthine were obtained.The author's experiments show that heteroxanthine is a methyl- xanthine, having the constitution NH.CH:y"Me> I GO, for i t yields carbonic anhydride (2 mols.), carbonic oxide (1 mol.), ammonia, (3 mols.), and sarcosine (1 mol.), when hydrolysed by acids, whilst further methylation converts i t into caffeine. On injection into frogs, tlie principal symptom is increased contrac- tility of the voluntary muscles ; in mamma.ls, similar convulsions are seen, After iniection, it cannot be found in the urine, and is there- R. R. ' C. H. B. C O*NH*C=N fore probably acmost completely oxidised in the body. ' W. D. H.VEGETABLE PHYSIOLOGY AND AORICULTURE. 20 1 Derivatives of Hydraetine and Narcotine. By EDJIUSD FALK (virc?mio’s A ~ c h i r , 1895, 142,360-379). -Meth~lhydi*astarnide pro- duces, in both cold and warm-blooded animnls, peripheral paralysis. 1x1 larger doses, i t paralyses the heart; it dilates the vesscls, lowers the blood pressure, and causes death by cessation of respiration. Nethylhydrastimide acts on the muscular tissues producing para- l y s i s preceded by cramps ; even in small doses i t weakens the heart. There is dilatation of vessels, and death occurs, as in the former case. Methyltiat-cotamide produce8 a narcotic stat’e by acting on the cerebrum, and there is paralysis of a peripheral nature. Very large doses are necessary to affect the heart ; there is fall of blood pressure. Respiration is first quickened, then becomes slower, and finally ceases. Methjlnarcotimide is a narcotic, but paralysis is incomplete and accompanied by a stage of muscular cramp ; on the heart, however, its paralysiug action is inore marked. It is a local aiwsthetic at the seat of application. There is fall of blood pressure. Respiration rises during the convulsions, but in the narcotic stage falls, and finally ceases. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8967005195

出版商:RSC    

年代:1896

数据来源: RSC

摘要:

Organic Chemistry. Sodium Nitroferrocyanide. By KARL A. HOFMANS (Zeit. anorg. Chem., 1896, 11, 31-36; see also this vol., i, 69).-A compowzd, Fe(CN)5Na,S0, + 9Hz0, is obtained by adding sodium nitroferro- cyanide (20 grams) to a 40 per cent. solution of sodium hydrogen sulphite (50 grams), neatralising with sodium hydroxide, and nddiug 20 C.C. more of a 10 per cent. solution of sodium hydroxide, The intensely yellowish-red solution is evaporated in a vacuum over sulphuric acid, and the red crystals of the compound, after sepa- rating them from the sodium sulphate, recrystallised, taking care that the solution is not heated above 30'. It crj-stallises i n long, thin, pale yellow needles, does not yield ammonia when heated with sodium hydroxide, gires a yellowish-green solution with hydrochloric acid, and then evolves sulphurous anhydride, a beautiful red colora- tion when boiled with hydroxylamiue and sodium hydroxide, it bluish-white precipitate with ferrous sulphate, and a dark blue pre- cipitate with ferric chloride.It remains entirely unaltered when treated with sodium hydrogen sulphi te. When treated with iodine, the ferro-compound is converted into a ferri-compound, and with permanganate in acid solution, i t yields a ferri-compound and sul- phate. When treated with hydrogen peroxide, it remains for the most part unaltered. When treated with nitrous acid or nitric oxide, i t yields sodium nitroferrocyanide. By ARNIJLF SCHERTEL (Ber., 1896, 29, 20$-205).-These salts can be prepared very easily by dissolving well washed and freshly precipitated platinum sulphide in a solution of the corresponding cyanide, and concentrating the colourless solution; PtS2 + 5KCN = &Pt(CN), + K2S + KCNS.KZPt(CN),,SH2O, and BaPt(CN),, were so prepared. If com- mercial potassium cyanide, which a t the present time (in England also ?) is nearly half sodium cyanide, is used, crystals of the salt KNaPt(CN),,3H20 are obtained, and, from the mother liquor of these, crystals of N%Pt(CN)d. Organic Compounds containing Quadrivalent Oxygen. By F. ZECCHINI (Guzxetta, 1895, 25, ii, 56-63) .-Friedel (Abstr., 1875, 1245) obtained a liquid boiling at -lo to -3' by the action of dry hydrogen chloride on dry methylic alcohol at -20" which was so Enstable at ordinary temperatures that it could not be ascertained whether it consisted of the compound MeOH,HCI, containing quadri- valent oxygen.The author has repeated Friedel's experiment, and has also investigated the action of methylic iodide on methylic ether at -18'; in the latter case, a liquid is obtained by distillation, which boils a t 0' to lo, and contains iodine, but does not lend itself to further examination. Determinations of the depression of the freezing points of various K. C. R. Preparation of Platinocyanides. C. 2'. B. VOL. LXX. i. 4198 iIBSTRACTS OF CHEMICAL PAPERS. solvents by mixtures of methylic ether with hydrogen chloride or methylic iodide seem to indicate that at the temperature of the freezing solvent no combination exists. By HUGO ERDMANN and P. HUTH (J. pr. Chem., 1896, [2], 53, 43-46 ; compare Tiemann and Semmler, Abstr., 1895, i, 646).-Rhodiiiol and geraniol will combine with dibasic acids to form acid ethereal salts ; such a compound with cam- phoric acid has been analysed.R h o d i d diphenylwethane, NPh2*CO*0C1,,H1,, crystallises in long, silky, felted needles, and melts at 83-84". This compound has been obtained from rhodinol, geraniol, and reuniol, a s well as from German and Turkish rose oil. It is thus proved that "reuniol " is identical with rhodinol, so that this name must be erased from scientific literature (compare Hesse, Abstr., 1895, i, 186). W. J. P. Rhodinol or Geraniol. A. G. B. Composition of Wool Fat. By L. DARMSTAEDTER and ISAAC LIFSCH~TZ (Ber., 1895, 28, 3133-3135).-0n hydrolysing wool fat, the authors obtained ail alcohol, CIoHzoO, which melts at 105-109", and appears to be unsaturated ; an nlcohoZ, CllHzzO, which crystal- lises in needles, and melts at 82-87", has been also isolated.The authors regard these alcohols as lower homologues of lanolinic alcohol (Marchetti, Abstr., 1895, i, 408). Reduction of Pseudonitroles to Ketoximes. By ROLASD SCHOLL and KARL LAXDSTEISER (Bey., 1896, 29, 87--90).-1n order to throw light on the structure of the pseadonitroles, the authors have submitted propylpseudonitrole to reduction ; employing free hydroxylamine and potassium hydros-ulphide, they obtained acet- oxime in each case. M. 0. I!'. M. 0. F. Pseudonitroles and Dialkyldinitromethanes. By GEORG BORX (Ber., 1896, 29, 90-102; compare the foregoing abstract, and Abstr., 1895, i, 445) .-The resemblance between iiitrosobenzene aid the pseudonitroles, and the reduction of the latter t o ketoximes with hydroxylamine or potassium hydrosulphide, lead the author t o advocate V.Meyer's expression for the structure of pseudo- nitroles, which represents them as nitro-nitroso-compounds ; more- over, oxidation of the pseudonitroles gives rise t o dialkyldinitro- methanes, and these also, when reduced, yield ketoximes. Diethyldinityonzethane, CEt(NO,),, is obtained by oxidising nmyl-P- pseiidonitrole with chromic acid in glacial acetic acid ; it is a colonrless liquid, which boils at 207-208O under a pressure of 723 mrn., and has an agreeable, camphor-like odour. Ethylprop ylpseudonitrole (am yl- a-pseu donityole) , NO.CMe( NO,).CH,Et, is prepared by submitting an ethereal solution of methylpropylket- oxime to the actiou of a current of nitric peroxide ; i t is a deep blue oil, which becomes green and decomposes in sunlight, and yields brown gas when heated a t 59'.Oxidation, with chromic acid, in glacial acetic acid solution, gives rise to methylpropyldinitromethane, a colourless oil,ORGANIC CHEMISTRY. 199 which boils a t 20i*5--209*5' undcr a pressure of 723 nini., and has 8 pleasant odour 1-esembling that of camphor. as- Dinzei hl/Zpropy~se2idoi.litro le (iaoa?izy~seudon,itrile), NO.CMe(NO,)*C BMe2, is a blue oil, which decomposes at 60'; on oxidation it yields methyl- Cso~ropyZdiiLitl.ontethnne, a pale green liquid, which solidifies in a mix- ture of ice and salt, and boils at 205-207' under a pressure of 724 mm.Diethylpl-op ylpseudonitrole (hepty lpseudonitrole) , CH,Et.C( NO) (NO,) *C B,E t , separates from ether in white 1-hombohedm, which melt, forming a blue liquid, and evolving gas, at 72-73' ; during the preparation of this substance, the nitrimine is formed (compare Zoc. cit.), together with a mixture of dipropyl ketone and dipropyldinitron7ethane. The latter substance is also obtained by the oxidation of diethylpropyl- pseudonitrole ; it is a colourless oil, which has an agreeable, camphor- like odour, and boils at 220-221'. Oxidation of the pseudonitrole is also attended with regeneration of dipropyl ketone, and reducticn with free hydroxylamine or alkali hydrosulphides gives rise to dipropylketoximc. Tet~~anzetliyl~~ropylpsezido~zitroZe, CHMe2.C(NO) (N02)*CHMe,, is n pungent, blue oil, which decomposes at 54'; oxidation converts i t into diisc)p?.opyZdinitromethu?ae, which boils and partly decomposes a t 203-207' under a pressure of 717 mrn.Diisopropyl ketone is also produced by oxidation of the pseudonitrole. JIethyE ol-etlzy?propyl ketozime, CHEt2*CMe:NOH5 is a colourlees liquid, which boils a t 186-188.5' (uncorr.) under a pressure of 71.2 mm. The action of nitric peroxide gives rise to a green oil con- sisting of the impure pseudonitrole, which decomposes at 67', and when oxidised yields methyl-a-ethylpropyldinitromethane; this substance is a yellow oil, which boils at 211-219' under a pressure of 722 mm. dm y l~ roy y lpse udou it role (oc ty 1 - a-pseudonit rol e ) , N O-CMe( NO2)*CH2-C5Hll, obtained from methyl hexgl betoxime, is a blue oil, which decomposes at 53-53', and solidifies in a freezing mixture ; oxidation converts it into methylhezylainitro?nethane, a yellowish-brown oil, which decom- poses a t 180', yielding methyl hexyl ketone.M. 0. F. p-Ethoxybutylamine and PpEthoxybutylamine. By S . BOOK- MAN (Ber., 1895, 28, 3111-3121 ; compare Abstr., 1895, i , 190).- When ethylic chloro-sec-butylic ether, CH,CI*CHEt*OEt, is heated in sealed tubes with alcoholic ammonia for three hours at 140', P-ethoxy- butjlamine and di-/3-ethoxybutylamine are produced. p-Ethozybutyla?~zine, OEt*CHEt.CH,*NH,, is a highly refractive liquid, which boils a t 139-141°, and has a sp. e;r. = 0.8505 at 16" ; i t readily absorbs atmospheric carbonic anhydride, and dissolves sparingly in water.The hydyochloride crystallises i n white plates, and the yla.tinochZo?.ide is extremely soluble in water ; the -picrate crystallises from hot water in lemon-yellow needles, and melts at 156'. The phe?LyZtliiocurbam icle crjstallises in lustrous, white needles, and melts at 94'. 9 2290 ABSTRACTS OF CHEMICAL PAPERS. @-Chlorobutylamii~e is obtained in the form of the hyds.ochloyide by heating [%ethoxybutylaminf: (2 grams) with fuming hydrochloric acid (20 c.c.) for 24 hours at 150-160"; the picrate melts a t 1 4 2 O , and the pZatiiaochZovide crystallises in yellow leaflets. When heated i n sealed tubes at 100' with aqueous alkali, the hydrochloride of t h e base yields a-crotylaniine (compare Abstr., 1892, 33). /3- Bro )no bzity lamin e hydro bi*om ide is f orrned when /I- ethoxy butyl- amine is heated with hydrobromic acid; the picrate melts a t 150-151', and decomposes at 210".When an aqueous solution of the hydrobromide is agitated with alkali and beiizoic chloride, the benzoyl derivative is produced, aud this yields P-p-etli ylphenyloxazoline, when submitted to the action of a current of CH2<N----CPh' steam while in cont'act with alkalis. The picrate of this base crys- tallises in long needles, and meltjs a t 168'. is obtained by the action of carbon bisulphide on the hydrobromide of /3-bromo- butylamine in presence of alkali ; oxidation with bromine water converts this substance into the /+ethyZtrtzcrine, HS0,*CHEt*CH2*NH2, which crystallises from water, and decomposes at 285'. Di-P-etkozybz{tylamine, NH(CH,*CHEt*OEt),, is a feebly refractive liquid, which boils at 230°, and has a sp.gr. = 0.87 at 16'. The ltydrochloride is white ; the aurochloride is orange, and melts a t 113" ; the picrate is yellow, and melts a t 83-85' ; and the nitrosanzine is a riscous oil which boils at 259' ; when heated wiQh fuming hydro- chloric acid, the base yields a substance which is probably di-@- ehlorobutylamine, the azwochloride of which melts at 170-171°. An nnsaturated base (probably consisting of dicrotylamine) is obtained on heating di-/%ethoxjbutylamine with hydrobromic acid a t 140°, and d i s t i l h g with potash the hydrobromide thus obtained ; the picrate crystallises in yeilow prisms, melts at 172--173O, and decom- poses at 2.25'. , rpEthozybutyEumine is obtained by reducing the nitrile of ychloro- butyric acid with sodium and a,lcohol, butylamine being formed a t the same time; it boils a t 14S0, and has an ammoniacal odour. The oxalate melts at 198--200', the platinocldoride a t 190°, and the thio- cmbamide at 91-99'.Fuming hydrochloric acid a t 150' converts the base into ethylic chloride and y-chlorobutylamine. Alkyl Derivatives of Ethylenediamine. By PAUL ScmErom (Bey., 1895, 28, 3072-3078 ; compare Ilinsberg, tihis vol., i, 47).- Diphenylsulphonethylenediamine, C2H4(NH*S02Ph),, was prepared by Hinsberg's reaction (Bbstr., 1892, 64) from ethylenediarnine and benzenesulphonic chloride, and was converted by marming with methylic iodide and aqueous-alcoholic soda into dipheity Zsz~lphonedi- m e t hy Zeth y Zenediantine, C2H4( MA1e.S 02Ph) ?, me1 ting at 13 1'.This, b y heating with strong hydrochloric acid, was hydrolysed, yielding di- ?~zethyZethylenediamiiae, C2H4(NHMe),, the hydrocJdoride of which me1 ts. and decomposes at 235-%36' ; the 01-ange-red platiizochlo~ide, with 4H,O, darkens when anhydrous at 20S", and melts and decomposes at! CHE;t*? CHEt-7 N--C*SH' P-Ethylthiazoline ~~-lty&-oszclpphide, CH2< __ M. 0. F.ORGANIC CHEMISTRY. 201 209' ; the yellow aii~ochlo.riclt: crystallises with H?O ; the ycllompic~*atc melts at 213--216*. The base itself, a diacid one, was prepared by dis- tilling the hydrochloride with powdered potassium hydroxide and soda- lime from a copper retort ; i t boils at 119', and has a sp. gr. = 0.848 at 4O, and 0.828 at the ordinary temperature (water at 4' = 1) ; it attracts water and carbonic anhydride from the air, and, with nitrous acid in concentrated solution, i t yields yellowish-green dirnethylet?iyl- enedinitrosamine, C2H4( NMe*XO>?, melting at 60--tilo, showing that it is a di-secondary, arid not a primary-tertiarj- base.The analogous ethyl derivatives were also prepared before the publication of Hinsberg's paper. Diethylethylenediamine boils a t 149-1 50° ; the orange-red platifiochtoride melts at 223-224', and the azwochloride at 220' ; the diizidrosnmine was obtained as a yellowish- green oil which decomposed on heating. Ethylenediamine forms a fne?.cziroc?Lloric?e, C2H4 NH2)2,2HC1,HgCI2, which melts at 297'. _FiTe~~nrrLethylethy~ene~ia~~~~~oni~i~~~ chloride, C2H4(NMe,C1),, was prz- pared by the action of silver chloride on the iodide (Hofmann, Jahresbericht, 1859, 386) ; the platinochloride blackens at 260', and melts and decomposes at 286' ; the picyate melts at 2 6 2 O .Lysidine. By ALBEET LADEXBL-RG (Be).., l895,28, 3068-3070).- If lysidine, C2H4< >CMe (-4bst~., 1895, i, 73), is shaken with benzoic chloride and potassium carbonate, i t yields ncefodibeizzo- ethylenediami?ie, NHBz*C2E14*NAcBz, melting at 113 --114', and when this is shaken with sodium hydroxide, it is converted into dibenzo- ethylenediamine, C2H4(NHRz)2, melting at 244' ; this is very sparingly soluble in alcohol, and its formation can be used to defect lysidine in a 0.1 per cent. solution (which must of course con- tain no ethylenediamine) ; it is only necessary to shake the solution with benzoic chloride and sodium hydroxide.When lysidine hydrochloride is submitted to dry distillation, it is decomposed into ammonium chloride and niethy lie cyanide ; acetylene, or a polymeride of that substance, is presumably formed in addition, but no proof of this could be obtained. c. F. €3. NH C. F. B. Preparation of Ethereal Salts. By EMIL FISGHER. and ARTHUR SPEIER (Ber., 1895, 28, 3252--3258) .-The experiments detailed below show that the use of mineral acid in excess is fi-equently uunecessary, and sometinies decreases the yield of ethereal salt. The yield of ethylic benzoate prepared by the ordinary method with hydrogen chloride and sulphuric acid is 73 and 76 per cent. respec- tively, but, when benzoic acid is boiled with alcohol (2 parts) con- taining hydrogen chloride (3 per cent.), the yield is 76 per cent., and with sulphuric acid (10 per cent.), after heating during three hours, the yield is 90 per cent.of the theoretical. I n the following table, the yield refers to the purified salt ; only the authors' best results are given, but these could probably often be improved if the conditions were modified. Absolute ethylic alcohol \\-as always employed, and the solution boiled, unless otherwise stated.%02 ABSTRACTS OF CHEXICAL PAPERS. Acids. ---- a-Naphtlioic, 10 grams. ..... Phcnylacetic, 10 ........ Cinnamic, 15 grams ........ Crotonic, 5 grams .......... Mandelic, 5 grams.. ........ Salicylic, 10 ............ .. 10 ............ Glycollic, 10 ............ Lerulinic, 10 ............Succinic, 10 ............ .. 10 ............ Fnmaric, 10 ............ Citric, hydrated, 10 grams.. . Phthalic, anhydride, 10 grains Terephthalic, 3 grams. ...... Malic, 10 grams.. .......... Tartaric, 20 grams.. ........ Muck, 5 gmnis ............ .. 5 .............. Mineral acid. Hours boiled. --- 4 4 5 4 4 4 4 4 4 4 4 4 4 50* 4 4 ; 4 1 12 i 24" I Yield per cent. 74 -8 87 '0 89.7 54 '3 67 ' 5 54 '0 54 '51. 65 '8 76-5 73 -9 53 -9 68 -2 67 '3 63 -3 74.7 $0 *5 72 -8 47 '3 90 * 8t A considerable loss of ethylic glycollate occurs, on account of its great volatility ; it has not been previonslg prepared from the free acid. The use of mineral acid is not advantageons in the preparation of ethylic pyruvate ; the best yield is obtained by heating the acid and alcohol at 100'.The use of a sealed tube for the etherification of terephthalic acid is necessary, as, with a reflux apparatus, violent. bumping occurs. Limpricht has stated that mucic acid is not etheri- fied by the action of hydrochloric acid, or sulphuric acid, and alcohol ; the methylic salt, prepared in a sealed tube, is obtained at once in a high state of purity. These results show that, in order to obtain the best yield, the quantity of mineral acid used for the etherification must be determined for each acid separately. The advantages of dilute acid are as follows: it is easier to use, the product is more readily purified, loss of alcohol is rednced to a minimum, and com- pounds may be prepared which are attacked by concentrated mineral acids. J. B.T. Diethylacetylenic Dipropionate. By FRAXCESCO AXDEKLISI (Gazzetta, 1895, 25, ii, 46-57).-Klinger and Schmitz (Abstr., 1891, 890) showed that sodium acts on butyric and isovaleric chlorides, with t.be formation not of dibutyryl and diisovaleryf, but of dipropyl- xcetylenic dibutyrate and diisobutyrylacetylenic diisovalerate ; t h e refiction proceeds in the same way with propionic chloride. Sodium wire acts slowly on an ethereal solution of propionic chloride, axid the ethereal liquid, on distillation, yields a yellow oil, which, after washing with sodium carbonate, drying with potassium carbonate, and distilling under reduced pressure, gives diethylncefylenic d;i3~o- pioiznte, CO~:t.O.CEt:CEt.O*COEt. It is a faintly odorous, yello.cr.ish, t- MetliFlic salt. * Heated at 100" in a srnlcd tubc.ORGANIC CEEMISTRY.203 oily liquid, which boils at 108-109' under a pressure of 10 mm., is decolorised on exposure to light, and has the densities 1.0083'7 a t 5-6"/4' and 0.99032 at 28*1'/4'. On hydrolysis by hot alcoholic potash, it behaves in a manner analogous to its higher homologues, and yields propyroih, COEt.CHEt.OH, which can be purified by dis- tillation under reduced pressure ; this boils at 132-135' under 227 mm. pressure, and has a density of 0.94288 at 16.6'/4'. The densities of butymin and isovaleroin are 0.9466 and 0.90256 at 16.7O/Po and 1 7*P0/4' respectively. Dipropylttcetylenic dibutyrate has a sp. gr. = 0.94324 at 20°/4", and diisobutylacetylenie diisovalerate a sp. gr. = 0.91320 at 20°/4'. All the above substances give normal molecular weights by the cryoscopic method.Hydroxylamidoisobutyric acid. By GwrAy M ~ X C H (Ber., 2996, 29, 62--65).--When pure acetoxime, CMe,:N.OH, is allowed to remain with a slight excess of anhydrous hydrogen cyanide in closed vessels at the ordinary temperature, monoclinic crystals of Ityd~o~y8- nmidoisobut~ro.izitriEe, CN*CMe,*NH*OEE, are formed ; this substance melts at 98.5'; its hydrochEoritZe melts and decomposes at 210'. The best way of hydrolyaing it, is to dissolve it in concentrated sulphuric acid, dilute with two-thirds as much water, and heat for a few hours a t 80-85' ; in this way, hyd~o~~yZami~oisobuty,.ic acid, C 00H*CMe2*NH*OH, is obtained, melting and decomposing at 168'. Optically Active Valerie acid. By 0. SCH~~TZ and WILHELU MABCKWALD (Ber., 1896, 29, 52-59).-a-Methylbutyric acid, C BMeEt*COOH, was synthesised by Conrad and Bischoff's method (Annulen, 204, 151), and an endeavour was made to separate it into its optically active components by fractional crystallisation of its brucine salt-the only salt amongst those tried that was a t all suitable for the purpose.Even then the separation was extremely difficult ; for the two optical isornerides, although hemimorphous, are not enantiomorphous, as usual, but are actnally isomorphous with each other and with the inactive (racemic) salt. The Z-acid, the brucine salt of which is the less soluble, was finally obtained with a rotation a~ = -16.3' in a tube 100 mm. long, which rotation was not increased by further crystallisation, but the d-acid could not be obtsined with a greater rotation than aD = +loo, and doubtless still contained some I-acid admixed.The brucine salts of both acids have the corn- position C:5H1002,C23H2SN204 + 3H,O; that of the Z-acid softens a t 95" and melts at 100'; wben anhydrous, it softens at 80" and melts at, 88" to a turbid liquid, which becomes clear at 94' ; that of the d-acid softecs at 93' and melts at 95"; when anhydrous, it melts at 60-63'. The E-acid is like the inactive acid, in that i t boils at 173-174', does not solidify at -80°, has sp. gr. 0.954 at Oo/Oo? 0.93-4 at 20'/4', and 0.926 at 30'/4' (inactive, 0.936 at 20°/4'), and forms very similar salts. The calcium salt, with 5Hz0, or l+H,O after drying in the air for two months, and the zinc salt of the Z-ttcid are less soluble in hot than in cold water ; 100 C.C.of an aqueons solution of the silver salt at 16" W. J. P. C. F. B.204 ABSTRACTS OF CHEMICAL PAPERS. contains 0.675 gram of the salt, whereas 100 parts of water dissolves 1.182 parts of the corresponding inactive salt at 20'. I'he rotation of the Z-acid at 20" and 30' is given for light of different wave- lengths. An attempt was made to prepare from the active acid, by t.he action of bromine at a low temperature in the presence of phosphorus, an active acid, CBrMeEkCOOH, which would have no hydrogen atom united directly with the asymmetric carloon atom. The sub- stance actually obtained was optically inactive, and identical with the mouobromo-acid prepared by Backing (AnnnZen, 204, 23) by brom- inating inactive methylethylacetic acid a t 150-160'; it is an oil, and boils at 140' under 50 mm.pressure. C. F. R. Action of Sulphur on Unsaturated Fatty Compounds. By ROBERT HENRIQUW (Zeit. ungw. Chem., 1855,691-692).-The author's experiments prove that a true combination of sulphur with fats 01' fatty acids exisis. In one experiment, colza oil was fused with excess of sulphur for three hours, and after cooling, the liquid was filtered. It showed, on analysis, 3.99 per cent. of sulphur. A portion of it was now saponified with cold alcoholic soda in the presence of light petroleum, and the fatty acids were separated by hydrochloric acid. Some of the sulphur apparently existed in a free or loosely combined state, and had formed sodium sulphide, but the bulk was combined with the fatty acids, which shawed 5-23 per cent.of sulphur. Treatment with hot alcoholic soda, however, removed the -greater part of this sulphui; but the fatty acids still retained 1.93 per cent. The experiment with sulphuretted linseed oil was more satisfactory. A sample, containing 8.53 per cent. of sulphur, yielded, by the cold process, fatty acids containing 6.62 per cent. ; by tthe hot process, acids containing 5-58 per cent. of sulphu~. Brown " fuctis " was next tried. A sample containing 15.48 per cent. of sulphur, gave, by the cold process, wids containing 15.20 per cent.; by the hot process, acids containing 14.14 per cent. of sulphur. L. DE K. Preparation of some Cobalti-Compounds. By S. P. L. SOREN- SON (Zeit. anory. Chew,., 1896, 11, 1--5).-Potassium cobaltioxalate, K,Co,( C,04),,SHz0, previously obtained in small quantities by Kehr- mann (Abstr., 1891,1189), is easily prepared in the following manner : A mixture of cobalt carbonate (25 grams), a saturated solution of potassium oxalate (250 c.c.), and a saturated solution of oxalic acid (200-230 c.c.), is heated on the water bath until all the cobalt car- bonate is dissolved.It is then cooled to 40°, oxidised with lead peroxide (30 grams), and then cooled and gradually mixed with acetic acid (50 c.c.), and filtered. 'I'he filtrate is precipitated, stirring constantly, with successive portions of alcohol, filtered, and the precipitate washed with absolute alcohol. The product is dissolved in the least possible quantity of water and again precipitated with alcohol.About 55-60 grams of the pure salt is obtained. Ammonium cobaltioxalate i s prepared in a similar way, but using a more concentrated solution, ae the salt is much more soluble both inORGAXIC CHEMISTRY. 805 water aid in alcohol. The author is engssged in studying the properties of these salts, and especially their behaviour towards ammonia. E. c. FL. Hydrolysis of the Alkyl Substitution Derivatives of Ethylic NIalonate. By EDVARD I. HJELT (Bey., 1896, 29, 110-ill).-- When the alkyl substitution derivatives of ethylic malonate arc! treated at 16' with a decinorrnst solution of soda in '36 per cent. alcohol, 1/20 of a gram-molecule of the compound being present per litre, ii; is found that, without exception, the dialkyl derivatives are mnch more slowly hydrolysed than the nionalkyl derivatives. The rate of hydrolysis, moreover, does not appear to depend on the strength of the acid.The experiments included ethylic malonxte, together with the fol- lowing derivatives : e thgl-, propyl-, isopropyl-, isobutyl-, allyl-, bcnzyl-, dimethyl-, diethyl-, diallyl-, and allylisopropyl-. The author considers that these phenomena are to be explained by stereochemical considerations. A. H. Interconversion of Optical Antipodes. By PAUT, WALDEN (Ber., 1896, 29, 133--138).-The author has previously shown (this VO~., i, 139) that asparagine can be converted into I-bromosuccinic acid by the action of bromine and nitrous oxide, and into d-bromo- succiriic acid by treating t.he maIic acid prepared from the asparagine with phosphorus pentabromide.By passing nitrous oxide into a sul- phuric acid solution of aspartic acid, to which potassium bromide and bromine hare been added, I-bromosuccinic acid separates, and niay be extracted with ether. A good yield is got thus, but a practically theoretical yield of I-chlorosuccinic acid may be obtained by passing chlorine and nitrous oxide into a hydrochloric acid solution of aspartic acid in the cold, the acid being extracted with ether. Both I~evo- a d dextro-isomerides are thus obtained from the same source at the ordi- nary temperature. After a number of abortive attempts, the I-bromosuccinic acid was converted into I-malic acid by warming its Ctqueous solution with freshly precipitated silver oxide ; d-chlorosuccinic acid was similarly converted into d-nialic acid.Both samples of malic acid had the proper specific rotations. It was further shown that d-malic acid can be converted into its I-isomeride in the same way that the latter can be converted into the formei. Consequently, starting with I-nialic acid, d-chlorosuccinic acid can be directly prepared, and by displacing the chlorine in this by hydroxyl, d-malic acid, the optical isomeride of the material used, is obtained ; this may then be converted into I-chlorosuccinic acid, which, in turn, yields E-malic acid again. W. J. P. A Homologue of Asparagine and Derivatives of Homo- aspartic acid. By W~LHELM KORXER a.nd ANGELO MENOZZI (Red Accad. Lincei, 1893, ii, 368-374 ; compare dbstr., 1890, 869).-On heating the diethylic salts of citraconic, mesaconic, and itaconic a.cids in sealed tubes with alcoholic ammonia a t 105-llOo, derivatives of206 ABSTRACTS OF CHEMICAL PAPERS.the same homoaspartic acid, COOH*CMe(NH,)*CH,X?OOH, are ob- tained. Ethylic citraconate, by this treatment, deposits homoaspartic diantide, C5HllN302; it crystallises in small needles melting at 175O, and when boiled with barium hydroxide, evolves ammonia and loses its alkaline reaction, yielding barium homoaspartate. The liquid from which the diamide separates contains homocwparagiize, NH,*C 0 *CMe ( NH,) *C H2* C 00 H, which crystallises in large, efflorescent, orthorhonibic plates, contain- ing 2H20, and is optically inactive ; a : b : c = 0.695 : 1 : 2.414. It gives off ammonia when boiled with alkalis, and has feebly acid pro- perties ; the copper salt (C,H,N203)2Cu,H,0, crystallises in small, blue tablets, which lose water a t 130-135", becoming violet.Diethylic mesaconate, or diethylic itaconate, when heated with alcoholic ammonia, deposits homoaspartic monamide, C5H8N202, which crystallises in colourless needles melting at 195'. On boiliug with barium hydroxide, ammonia is evolved, and a barium salt is formed, from which homoaspartic acid may be obtained; it crystallises in transparent, hemihedral, orthorhombic prisms with 1H20, and, when anhydrous, melts at 166.5-167'; a : b : c = 0.658 : 1 : 1.211. The solution is optically inactive, but the crystals are hemihedrally developed, so that the two active isomerides may be separated. W. J. P. Preparation of a%-Dimethylglutaric acid from the Corre- sponding Hydroxy-acid.BY SERGIUS REFOHYATSICY (Ber., 1895,28, 3262-3265 ; compare this vol., i, 128) .-p-~~drozy-aa-dimeth~Z- glutaric acid, C 0 0H.C HMe* CH (OH) *CHMe*C 0 0 H, is prepared by the action of ethylic bromopropionate and et.hylic formate on zinc ; it crjstallises iu needles, and melts at 135-136', but the liquid only becomes transparent at 141O. The electrolFtic conductivity k = 0.0108, puv3 = 350. The ethylil: salt is oily, almost colourless, boils a t 270-271", and i8 most readily converted into the acid by means of barium hydroxide. The anhydride melts at 108-109', and is crys- talline. When reduced by means of hydriodic acid, the hydroxy-acid is converted into fumaroxd aa-dimethylglutaric acid, but i t melts at 145--145*5O, not at 140-141°, as stated by Auwers (Abstr., 1895, i, 209), no maleinoid acid is formed. Auwers (Zoc.cit.) referred the production of this isomeride by Zelin- sky's method, to the fact that it is prepared from ethylic a-cyanopro- pionnte, which contains an asymmetric carbon atom; as ethylic a-bromopropioriate also contains one, this view requires modification. J. B. T. Reactions of Tartaric acid and Alkali Tartrates. By LOUIS MAGKIER DE LA SOURCE (C'ompt. rend., 1895, 121, 774-776).--Potas- sium hydrogen tartrate is readily soIuble in a concentrated solution of potassium acetate, and hence a small quantity of tartaric acid added to such a solution produces no precipitate. Precipitation, however, takes plme a t once if acetic acid is added, and is also accelerated by the addition of alcohol and et.her.Acetic acid partially decomposes alkali tartrates if a mixture of the two is allowed t o A caEcium salt has also been prepared.ORGANIC OHEMISTRY. 207 evaporate, and conversely, a hydrogen tartrate partially decomposes an alkali acetate. The residue left after spontaneous evaporation is n mixture of normal tartrate, acetate, and hydrogen tartrate. A iiiixture of 1 mol. of taytnric acid and 2 mols. each of acetic acid and normal alkali tartrate, loses 95 per cent. of the acetic acid on spon- taneous evaporation, and this is increased to 97 or 97.5 per cent. when the proportion of tartaric acid is doubled or trebled. Calcium sulphate decomposes normal alkali tartrates completely, but hydrogen tartrates only incompletely, whether in presence of water or dilute alcohol.Its action on normal tartrates is not affected by the presence of potassium acetate, but its act.ion on the hydrogen tartrates ceases to be limited in presence of the acetatz. Tartaric acid partially displaces sulphuric acid from potassium sulphate, and hydrochloric acid from pot)assium chloride, these acids being partially expelled when the solution is evaporat,ed to dryness nnd heated. Under similar conditions, however, sodium chloride loses only a minute quantity of hydrochloric acid. C. H. B. Easy Method of Preparing Laevorotatory Tartaric acid. By WILHELM MAI~CKWALD (Ber., 1896, 29, 42-43).-A boiling aque- ons solution of raceniic acid is treated with half the cinchonine necessary to form the acid salt, and water is added until a clear soh- tion is obtained, which is then allowed to cool ; after remaining for a day, the cinchonine I-tartrate, which has crystallised out, is iiitered of'f.The mother liquor deposits the d-tartrate, which is filtei-ed off after two days ; this second mother liquor is divided into two halves, and these are neutralised, the one with sodium hydroxide, the other with ammonia, filtered f rorn precipitated cinchonine, mixed, and con- centrated ; sodium ammonium d-tartrate crystallises out 011 cooling, and this crystallisation is allowed to go on until the mother liquor has become inactive or feebly laerorotatory. The last mother liquor is woilked up for racemic acid, which can be used over again, 2nd the (1- and I-tartrates obtained above are converted into the corresponding acids in the usual way.C. F. B. Nitrocarbamide, Nitro-urethane, and Nitram ide. By JoIiAxxE:: THIELE and AR~HUR LACHMAS (An?zcLZet?, 1895, 288, 267- 31 1 ; compare Abstr., 1894, i, 399) .-Nitrocarbamide is strongly acidic, liberating acetic acid from its salts. The pntassizm deriyative is readily soluble in water, and the silver derivative crystallises i n minute prisms dissolving readily in nitric acid and ammonia; the m z e ~ c ~ w ~ derivative is very soluble in hydr.ocliloric acid, dissolving with difficulty in nitric and sulphuric acids, and it yields nitrocarb- amide when treated with ammonium snlphidc. NO,*NH*CO*NHEt, is obtained by adding ethylic nitrate to a solution of ethylcarharnide in sulphuric acid ; i t crystallises from ether in long needles and melts a t 150-131°.It dissoli-es readily in hot water, and is sparingly soluble in cold; Itydrolgsis with potash gives rise to cthylamine. The nn2i~oiiium and potaFs1'mz derivatives are hygroscopic ; the eilcei- derivative crystal- lises in white leaflets. n-;t).oefh?Jlca?.bamide,208 ABSTRACTS OF CHEMICAL PAYERS. Nitro-urethane (Zoc. cit.) is prepared by treating a solution of urethane in snlphuric acid with ethylic nitrate at 0' ; i t decomposes a t 140O. The potassiwt derivative crystallises from water in large, rhombic prisins, and the merczwy derivative is a white powder dis- solving readily in hydihochloric acid ; the deer derivative crystallises in aggregates of minute needles, and with methylic iodide vields iiitPomet~1iylurethane (coinpare Abstr., 1895, i, 445).Ethyl ic benzylidenehydm=inecu rboxylat e, C H Ph:NiNH* C OOE t, is obtained by reducing nitro-urethane and agitating the product with benzaldehyde ; it crystallises from dilute alcohol in long needles .melting at 135-186', and the potassimn cierivative is unstable in aqueous solution. The hy droch Zoi*ide of e t h y 1 ic hy drazinecarbox y 1 ate is obtained from the beiizglidene derivative by the action of warm hydrochloric acid; i t is readily soluble in water and alcohol, and separates in yelIowish leaflets on adding ether to the solution in methylic alcohol. The rnewury derivative of nitramide (Abstr., 1894, ii, 412) is an un- stable substance dissolving readily in hydrochloric, but only spaiaingly in nitric acid; the actioE of hot water gives rise to red mercuric oxide. Nitrosocarbamidc, NH,*CO*NH*NO, is obtained in solntion when nitrocarba.mide is reduced with ziiic dust and caustic soda ; the liquid develops an intense purple coloration with ferrous sulphate, and effervesces above 0'.Nitroso-u~etha?ze, NO*XH*COOEt, is produced on reducing the ammonium derivative of nitro-uret,hane with zinc dust and acetic acid ; i t crystallises from petroleum iu beautiful needles, and melts and decomposes completely at 51-52', yielding aldehyde, It gives Liebermana's reaction, and does not develop a colour with ferrous sulphate and caustic soda ; the aqueous solution effervesces vigorously when treated with acids or alkalis, yielding ethylic alcohol, carbonic anhydride, and nitrogen.The silver derivative is yellow, and ex- plodes when heated ; the potassizm derivative crystallises in yellow needles, and the anzmoizizcnz derivative in yellow leaflets. Potassium permanganate oxidises nitroso-urethane to nitro-urethane, and rbm- monia converts it into urethane, whilst aniline gives rise to phenyl- urethane. Potassiwn nitrosocarbnnicrte, NO*NK*COOK, is obtained from nitroso-urethane by the action of potash dissolved in inethylic alco- hol ; it is a yellow powder, which explodes violently when brought in contact with water, but is perfectly stable in dry air. M. 0. F. Preparation of Sernicarbazide. By JOHASKES THIELE and CARL HEWER (Annalen, 1895, 288, S11---313).-The unstable character of nitrosocarbamide seriously diminishes the yield of semicarbazide ob- tained by the reduction of nitrocarbamide; under couditions which lead to the immediate reduction of nitrosocarbamide, however, 50 per cent.of the quantity required by theory may be obtained. The zinc chloride coin2302~nd of acetone-semicarbazone, (CSZ e,:S.NH*CO*NH,),,ZiiCl*,ORGANIC CHEMISTRY. 200 is obtained by adding sodiam acetate and acetone t o nitrosocarbamide 1-educed in acetic acid solution by nieans of zinc dust mixed with powdered ice ; it crystallises from water in slender needles, and melts and decomposes at 196'. Ammonia converts the substance into acetonesemicarbazone, which may then be employed as n source of semicarbazide. M. 0. F. Cyanuric acid from Hydroxyoxamide. By HUGO SCHIFF and U. MOXSACCHI (Annahz, 1895, 288, 313-318, and Gcu., 25, ii, 446-450) .- EycE~or y Eoxa n2 ide, 0 H*NH- C 0 C 0 - N HZ, is ob t ai n ed by the action of hydroxylaniine on ethylic oxamate, and appears to be ideiitical with oximamidoxalic acid, NH,*C(NOH)*COOH, descpibed by Holleman (Abstr., 1894, i, 571) ; the aqueous solution develops an in tense red coloration with ferric chloride.Acetoayozamide, OAc*NH*CO*CO*NH,, is obtained by the action of acetic anhydride on the foregoing compound, and ciyhdlisea in nacreous leaflets me1 t- ing at 172-174O ; the substance is indifferent towards ferric chloride, and, when heated at 100-110' with acetic nuhydride, gives rise to cyanuric acid, an intermediate compoitiid, nieltiug at 218', being also formed. Phenylhydrozyloxamide, OH*NH*CO*CO*KHPh, is formed when ethylic phenyloxitmate is hjdrolysed with alcoholic hydroxylamine , it crystallises in leaflets and melts at 159'.The acetyl derivative melts at 182--183O, and does not 3-ield cpnuyic acid. M. 0. F. Action of Hydroxylamine on Succinic Anhydride. *By GIORGIC) ERRERA (Gazzetta, 1895, ii, 23-37) .-On adding B U C C I ~ W anhydride to an alcoholic solution of hydroxylamine, hydrozylanzins succiqlhydroxamic acid separates as a semi-solid mass. On mixing the anhydride with an alcoholic solution of hydroxylamine and sodium ethoxide, and adding ammonia and barium chloride, the Aarizm salt, (C*H6N04)2Ba, of succinylhydroxamic acid is obtained ; it crystttl- lises in small, coloarless prisms, and gives a K-iolet, colour with ferric chloride ; the hydrogen barizm salt, C4H,N0,Ba,4H20, crystallises in lamin=.Succinyllzydrozamic acid, 0H.C (NOH) *CH2*CH,*CO0 H, can be obtained from these salts as a deliquescent, viscous iiquid ; on heating with acetic chloride, it yields ~ ~ c c i i ~ ~ l a c e t o r y l a r n i ~ ~ e , >N*OAc, which sepamtes from benzene i n lustrous, colour- yH2*CO less, orthorhombic crystals melting at 129-130°; a : b : c = 0.99826 : 1 : 0.45945. On crystallisation from hot water, it undep- goes partial hydrolysis yielding a syrupy solution from which suc-cinlyl- Iqdroxylamine crystallises when the latter is evaporated over sulphuric acid. On addiog alcobolic ammonia to the alcoholic solution of this amine or its acetyl derivative, an anzmonizm compound CH2*CO is deposited ; it crystallises in colonrless, monoclinic prisms, melts and decomposes at 175', and is very soluble in water.Ou boiling with soda, it yields succinylhydroxamic acid. W. J, P.210 ABSTRACTS OF CHEMICAL PAPERS. The Hexamethylene Series. Synthesis of Nononaphthere. By NIcor,.u D. ZELINSKT and A. fiftE1"OltJfAwKY (Ber., 1396, 29. 214--215).--Trirnethylhexamethylene alcohol, prepayed synthetically from trimethylpimelic acid (this vol., i, 130), yields, when reduced, a saturated hydrocarbon, CBH18, which boils a t 142-144", has a sp. gl.. = 0.7307 at lSo/4*, and yields tribromopsendocumene when treated v i t h bromine in the presence of aluminium bromide. This h-j-dro- carbon, 1 : 2 : 5-trimethglhexamethyleiie, is thus nothing eke than hexahydropseudocumene ; it may be regarded as a synthetical nono- naphthene.The nononaphthene, obtained from Caucasian naphthn by niIarkownil;off and Oglobin and by Konowaloff, is probably ;t mixture containing some hexahydropseudocumene ; only 7 per cent. of it can be converted into tribromopseudocumene. 1 : 5-Diketones. By Emi KNOEVEKAGEL (AnnuZen, 1893, 288, 321-360 ; compare Abstr., 1893, i, 419, and 1893, i, 48).--Ethylic is0 buty lidenediacetoa ce tate, C H PI@ ( C H Ac*CO OE t) 2, is obtained by adding diethylamine or piperidine (1 gram) to a mixture of ethylic metoacetate (100 grams) and isobutylaldehyde (28 grams) cooled at Oo, four cqual quantities of the base being subsequently added at intervals of 10 to 12 hours, while the temperature of the liquid is maintained between 0' and - 10" ; i t forms lustrous, colourless crystals, and melts at 117'.Ethylic 3 : 5-methyl~sop~opyl-A2-ketotetrahydroben~ene-4 : 6-dicad- oxylate, CMebCH -'CH(CooEt)'CHPd> CH-COOEt, is produced when acids and alkalis act on the foregoing sitbstance ; distillation gives rise to isomeric ethylic 3 : 5-methylisopropyl-Az-ketotetrahydrobenzerie- monocarboxylatea, the mixture forming a pale yellow oil, which boils at 170' under a pressure of 17 mm. (compare Hagemann, Abstr., 1893, i, 393). Ethylic 3 : 5-~nethyEisop~opyE-A2-ketotetraliyd~~be~zzene-~- cayboxytate is isolated from this mixture by means of its insolubility in caustic soda ; it boils at 161O and 170' under pressures of 11 mm. and 17 mm. respectively, and the alcoholic solution is indifferent towards ferric chloride. Ethylic 3 : 5-methylisopropyl-A2-ketotetra- hydyobenzene-~-cu?.boxylnte is soluble in caustic soda ; it boils at 1 6 6 O and 170' under pressures of 14 mm.and 17 mm. respectively, and develops an intense reddish-violet coloration with ferric chloride. Hydrolysis of these two ethylic salts converts them into the corre- sponding acids, which spontaneously lose carbonic anhydride, yielding 3 : 5-nt et hy lisop rop y 1- A2-ketot et rn h y dro b enze H e, or met acarup hor, C. F. B. this substance is also formed when ethylic isobutylidenediaceto- acetate is heated for two hours rtt 110' (compare Abstr., 1893, i, 419, and 1894, i, 575). Etliylic isovalerylideaediacetoacetate, CH2Pi+*CH( CHSc*COOEt),, is obtained from ethylic acetoacetate and isovaleraldehyde by means of piperidine or diethylamine ; it crystallises from dilute alcohol, and melts at 134-235'.When heated with water for five hours in ttORGIANIC CHEMISTRY. 211 reflux apparatus, it yields ethylic 3 : 5-meth!,lisobutyl-Az-ket~tet~.ah~/di.o- benzene-4 : 6-dica~bo~yZate, a colourless liquid, which boils at 186-188" under a pressure of 20 mm. ; the mime ci~ystallises in small, white needles, which melt at 108-109', and yields a bmzoyl derivative, crgstallising from dilute alcohol in leaflets, and meltiiig at 157-158O. When ethylic 3 : 5-methylisobutyl-Ah,-ketotetrahydrobei~zene-4 : 6- dicarboxylate is hydrolysed with 20 per cent. sulphuric acid, a mix- ture of etbylic salts is obtained, boiling at 167-'L69° under a pressure of 20 mm., and these are separated by the method adopted for the isopropylic derivatives.&?thy Zic 3 : 5-met?~ylisobutyl-A~-ketotetrahyd~o- benzeize-6-carboxylate fornis a phenylhydmzone, which crystallises from alcohol in small, white needles, and melts a t 162-163O. Ethylic 3 : 5- methylisobutyl-Acl?-ketotetrali~~robcnzenzene-~-~ff~box!~late yields an oxime, which melts at 101-103°, and gives rise to a, benzoyl derivative melting at 146-148'. 3 : 5-n/~ethyli~ubutyl-~~-32efoteti*a~ ydrobenzene is produced when ethylic isovalerylidenediacetoacetate is heated with alcoholic potash for 2-3 hours, and i t is also obtained by hydrolysing the foregoing ethylic mono- and di-carboxylates ; the ketone has an agreeable odour, and boils a: 146-143' and 130' under pressures of 22 mm. and 10 mm. respectively. The olrime cry stallises in colourless needles, melting at 92-9&O, and gives rise to a benzoyl derivative, which crystallises in lustrous leaflets, and melts at 138-140'.The y h e q l - hydrazone crystallises from alcohol in silky needles, and melts at 3 : 5-~lethyZisobzctyZplrenol is obtained by adding bromine to a solu- tion of the ketone in carbon bisulphide, and, after. removing the solvent, heating the product at 220'; i t boils a t 142-144' under a pressure of 20 nim., and is indifferent towards ferric chloride. The tribro~zo-derivative, C,,H,,OBr,, crystallises in white needles, and melts at 128-130'. 149-1 51'. Ethylic oenanthylidenediacetoace fate, CH,R/Ie.[CH,~,*CH(CHAc*COOEt),, crystallises from petroleum in white, lustrous needles, and melts at 71' ; i t is readily converted into ethylic 3 : 5-r)iethylhexyl-A2-icetotetra- hydrobenzene-4 : 6-dicarboxylafe, which boils at 195-196' and 202- 204O under pressures of 9 mm.and 17 mm. respectively. The ozime of the latter etliylic salt is produced when hjdroxylnrnine acts on the former ; i t melts at 116--118O, and yields a benzoyl derivative, which crystallises in colourless, lustrous leaff ets, and melts at 165-166'. Btltylic 3 : 5-methylhexyl-A~-ketotetrahydr~benzene-4-carboylate is separated by means of its insolubility i n caustic soda from the mixture of isomerides obtained on hydrolysing the foregoing othylic dicarb- oxylates ; i t is indifferent towards ferric chloride, and yields an oziliie melting at 109-111@, which gives rise to a berrzoyl derivative, melting at 157-159'. &'thyEic 3 : 5-methylhexyl- Ai,-ketutetrahydrobeizzene-6- carboxyzate is also separated from the mixture, which boils at 186- 188' under a pressure of 18 mm.; it develops a dark violet coloration with ferric chloride, and yields a phenylhydrazone, which crystallises in orange-yellow needles, and melts at 146-147O.212 ABSTRACTS OF CHEMICAL PAPERS. 3 : 5-~I~thyllze~~l-Az-ketoteti.a72ytll~ze~~e is the final product arising from hydrolysis of the foregoing ethylic salts; it has a bitter taste and agreeable odour, and boils at 166-168' under a pressure of 22 mm. The orime melts at 103-t03", and yields a benzoyl derivative, which crystallises in white, lustrous leaflets, and melts at 150-152'. The pheuylhydrazoize crystallises in silky needles, and melts at 157-159'. 3 : 5-Methylhexylphenol boils at 160-162' under a pressure of 18 mm., and is indifferent towards ferric chloride ; the triblwno- derivative, C,,H,,OBr,, me1 ts at 137-139' Ethylic BenztlEidenebisacetonedica?.boxylate, CHPh[ CH(CO0E t j*C O*CH,*COOE t],, is obtained by the action of benzaldehyde on ethplic acetonedicarb- oxylate, employing diethylamine, piperidine, or ammonia as the con- densing agent ; i t crystallises from alcohol in white, silky needles, and melts at 146O.Although water is eliminated very readily, an individual ketotetrahydrobenzeiie derivative has not been isolated by distillation ; successive treatment with sodium ethoxide and aqueous potash, however, converts it into 3 : 5-methylphenyl-iiz-ketotetmbydl.o- benzene (Abstr., 1395, i, 50).E thy lie meih?/leiLebisacetonedicnrbolcylnte, CHz[ CH(COOEt)*CO*CH,*COOEt],, is prepared from formaldehyde and ethylic acetonedicarboxylate, diethylnmim being used as the condensing agent; i t melts at 105'. Hydro1 y sis converts it into 3-me t hy 1- &-ke totetrahydrobenzene, iden- tical with the substance obtained on hydrolysing ethylic 3-met hyl-A,= ketotetrahydrobenzene-4 : 6-dicarboxylate (Zoc. cit.). Ethylic ethytidenebisacetonedicarboxylate, CHMe[CH(COOEt)*CO*CH2*C0OEt],, obtained from acetaldehyde, ethylic acetonedicarboxylate, aid diethyl- itmine, crystallises i n white, silky needles, and melts a t 115' ; hydro- lysis with 20 per cent. sulphuric acid converts it into 3 : 5-dimethyl- A,- ke tot etrah y drobenzene. E i h y l i c isobutylidenebisacetoi~eaicarboxy ~ute, CHP@[CH( COO E t) *CO*CH,*COOEt],, melts at 104' ; on hydrolysis, i t yields 3 : 5-methylisoprop~l-A2-keto- tetrahydrobenzene.Ethylic iso~aleryliae?iebisacet~nedica1.bozylate melts at US', and yields 3 : 5-rnethylisobutyl-A2-ketotetrahydrobenzene when hydrolysed. Zthylic oeiaai2.th ylidenebisacetoiiedica?.boxylate melts a t 12S0, and yields 3 : 5-methylhexyl-A2-ketotetrahydrobenzene on hydrolysis. M. 0. F. Derivatives of Chlorodihydrobenzene. By CH. GLXDLICH and EMIL KKOEVENAGEL (Bey., 1896,29,169-171; compare .Abstr., 1895, i, 86 and 654).-When 1 : 3-met5yiisopropylc~clohexanone (3 : 5-methyl- isopropyl-&ketotetrabydrobcnzene) is treated in chloroform solution wit11 phosphorus pentachloride, hydrogen chloride is given oft, and 5-ehk~rodil~yd~ot)~etacyme?ze (1 : 3 : 5-methylisopropglchlorocyclohexadi- ene) is formed.This distils over at 106' under a pressure of 15 mm.ORGANIC CHEMISTRY. 213 as a cohnrless. limpid oil ; i t is transformed back into the ketone by the action of 95 per cent. sulphuric acid. On treatment with bromine and quiuoline, it yields 5-ehEorometucy~nene, which distils under atmo- spheric pressure at 222-223'. 5 : 2, : 4 : 6-ChZol.otrinilro?e~~c~~zene, obtained by the action of nitric acid on the preceding compound, forms colourless crystals, melts a t 124-1 25', sublimes on heating, and smells intensely of musk. The trinitro-compound, with aniline, yields 2 : 4 : 6 : 5-trinitroanilido- iizetucywene, which melts at, 155' ; whilst with alcoholic ammonia i t yieIds 2 : 4 : 6-t~initro-1 : 3 : 5 - ~ y ? & d i ? ~ , which melts at 103-104'.j-Cl~lol-odiJLydrometais~b~Lt~l~~t~ene (1 : 3 : 5-methylisobutylchloro- cyclohexadiene) is obtained by the action of phosphorus pentachloride on methylisobutylcyclohexanon (Annulen, 288,336). It is a strongly refractive liqnid, and distils at 113-115' under a pressure of 15 mm. When treated with bromine or quinoline, it yields 5-chlorometaiso- butyZtol?cene, which distils under atmospheric pressure at 23 4-235'. 5- Clilo~o.metahezyldihydrotol2~elze (1 : 3 : 5-metl~ylhexylchlorocyclo- hexndiene) boils at 148-151)' under a pressure of 25 mm., and with bromine and quinoline yields 5-chtorometa?~ex~ZtoZuene, which distils under atmospheric pressure at 273-275O. The Benzene Problem. By VICTOR NEVER (Ber., 1895, 3195- 3196).-This is a reply to criticisms by Bruhl (this vol., i, 147) on the paper by Hey1 arid V. Meyer (ibid., 145).As regards the ques- tion of priority between Briihl and Wegscheider (Abstr., 1895, i, 593, and 449) concerning the hydrolpis of etbereal salts, the author points out that Conrad and Briickner were the first to draw attention to the rules regulating the hydrolysis, and to compare the results of hydrolysis with those of etherification, The Benzene Nucleus. By W i L H E m VAUBEL (J. pr. Chem., 1895, [23, 52, 548--555).-The author shows that his configuration for benzene (Abstr., 1894, i, 325) is in accord with the following facts. (1) Metanitraniline hydrochloride is the most stable of the nitraniline hydrochlorides (Lellmnnn, Abstr., 1885, 251 j.(2) Am- monia reacts with ortho- and para-bromonitrobenzene to form nitranilines, but not with metabromonitrobenzene (Schopff, Abstr., 1892, 335; P. Fischer, ,ibid., 331 ; Lobry de Bruyn, Abstr., 1891, 428). (3) Ortho- and para-nitraniline react with ammonia to form the corresponding nitrophenols ; metanitraniline does not so react. (4) Ammonia reacts with ortho- and para-nitranisoyl to form the corresponding nitranilines, but not with metanitranisoil. (5) Of the nitranilines the meta-compound combines most readily with phenyl- thiccarbimide. (6) Ortho- and para-xyleue are readily oxidised to the corresponding toluic acids, metaxylene far less readily. (7) Hy- drochloric acid at high temperatures converts ortho- and para- hydroxybenzoic acids into phenol, but not the meta-acid.(8) Of the nitrobenzaldehydes, the me ta-compound is more easily oxidised by nitric acid than is the ortho-compound. (9) Netahydroxybenzoic acid is reduced to the corresponding alcohol by sodium amalgam, in which respect i t differs fronr both its isomerides. I n the same connection, the author quotes Sudborough on the VOL. LXX. i. r J. J. S. J. J. S.214 ABSTRAOTS OF OHEMIOAL PAPERS. substituted benzoic chlorides and the hydrolysis of nitriles and amides (Trans, 1895, 587, 601). Some speculations concerning the manner in which naphthalene tetrachloride yields four dichloronaph- thalenes according to the treatment to which it is subjected, conclude the paper. A. G. R. By C. LORING JACKSON and M. H. IT'CNER (Ber., 2895, 28, 3063-3066).- This substance was prepared by the diazo-reaction from the corre- sponding 4-amido-componnd ; it forms yellowish prisms, and melts at 118" ; with aniline it yields, in the cold, 3 : 5 : 4-dinit?.uniZidotoZzle.ile, which is orange-yellow and melts at 169'.The bromo-compound does not react with ethylic sodiomalonate, and is oxidised only with difficulty, dichromnte and sulphuric acid converting it into 4 : 3 : 5- bmmodinitrobenzoic acid. This forms colonrless plates, and melts a t 181O; the bromine atom in i t is much more easily replaced than in t,be case of the preceding compound; on warming with ammonia, it is converted into the 4-amido-compound (chrysanisic acid) ; with aniline, it yields the orange-yellow 3 : 5 : 4-dinitroanilidobenzoic acid melting at 236O, and with ethylic sodiomalonate, it gives ethyZic 2 : 6 : 4-di7tit~o- cadox hen ZmuZon a te, C OOH*CsH, (NO,)z*Cj H( C OOEt),, which melts at 176 , With most of these substances sodium ettioxide forms unstable coloured substances, possibly addinq itself on to the nitro-groups ; certainly the other groups are not displaced.New Series of Quinono'id Derivatives. By TEEODOR ZINCKE (Ber., 1895, 28, 3121-312?).--Wheii tetrachloroparacresol is oxi- dised with nitric acid, a single atom of oxygen is taken up, giving rise to the formation of the hydroxy-compound, 4 : 3 : 5-Bromodinitrotolnene and its Derivatives. P C. F. B. this change may be compared with the conversion of the ketone C(oMe)z*CC1 C*OH into tho dihydroxy-compound co<ccI=ccl~ (Abstr., 1894, i, 232).I t is probable that hydroxydibromopseudocu- menol (Auwers, this vol., i, 151) is a member of the new class of derivatives, being represented by the formula the tribromide from which it is obtained having the constitution 'O<CBr:CMe CMe:CBr>CMeBr. Oxidation of di bromopseudocumenol, however, yields a hydroxy-derivative which is isomeric and not Preparation of Trichlorotoluquinone. By Kmr, ELBS and E. BRUNKSCHWEILER ( J . pr. Chem., 1893, [23, 52, 559-560).-20 grams of orthotoluidine is dissolved in the necessary quantity of dilute iden tical with the compound described by Auwers. M. 0. F.ORGANIC OHEMISTRY. 215 hydrochloric acid, and '700 C.C. of crude concentrated hydrochloric acid is added, and, in the course of an hour, 190 grams of dry, powdered sodium dichromate are added.The temperature is kept below 30-40°, and, after two hours, the mixture is heated for half an hour on the water bath, then diluted with a litre of water and filtered. The contents of the filter are washed into a flask with a little strong hydrochloric acid, and heated for an hour on the water bath; water is again added, the whole is filtered, and the solid Once moly washed with dilute hydrochloric acid into the flask. Several grams of dichrornnte are now added, and, after warming for a quarter of an hour, the solid matter is filtered and washed. After two treat- ments witch alcohol, the residual dirty yellow powder is crystallised from benzene. In this way, 20 grams of toluidine yield 16-17 grams of tricblorotoluquinone.Aniline may be similariy converted into chloranil. A. G. B. Synthesis and Constitution of Eugenol. By CHARLES MOU- REAU (Compt. rend., 1895, 121, 721---723).-The action of allylie iodide on dimethylcathechol (veratrol), c6H4( OMe)*, yields methyl- eugenol identical in physical and chemical properties with the natural product*. Some methylic iodide, catechol, and guaiacol we formed at the same time. The methyleugenol, when boiled with alcoholic potash, is converted into isomethyleugenol ; with chromic mixture, it yields methylvanillin and methylvanillic acid, and with potassium perrnanganate, it yields the same acid [ COOH : OMe : OH = 1 : 3 : 41. These results confirm the constitution generally ascribed to eugenol. C. H. B. Orthonitrobenzylic Mercaptsn. By SrEGivum GABRIEL and ROB.STELZNER (Bey., 1896, 29, 160-165; compare Abstr., 1895, 432).-Orthonitrobenzylic carbaminthiolate, when boiled with 10 times its weight of 20 per cent. hydrochloric acid, yields orthonitrober~zy~k hydrosuZphide, NO2*C6H4*CH2*SH, to- gether with a small quantity of orthonitrobenzylic sulphide ; the former may be separated by steam. distillation, as it is readily volatile. By exposing a concentrated solution of the mercaptan in methylic alcohol to low temperatures, it is obtained in long, yellow needles, which hare a characteristic odour, and melt at 42-44'. The author thinks that his compound is identical with Jahoda's nitrobenzylic bisulphide (m. p. 47') (Abstr., 1890, 487), since the true bisnlphide, according to Cassirer (Abstr., 1893, 16), melts at 112-113'.This bisulphide may easily be obtained from the hydrosnlphide by treatment with a solution of iodine. The hydrosulphide, when treated with 8 33 per cent. solution of potassium hydroxide, yields phenoisothiazole and nitrobenzylic bisulphide ; zinc chloride also gives the same thiazole. dfethylic orthonitrobenzylic sulphide, N02*C6a4*cH[,*sMe, is obtained by dissolving the hydrosulphide in methylic alcohol, and treating the mixture with sodium methoxide and methylic iodide ; i t is a thick, yellowish oil, and, on heating i t with methylic iodide at looo, is r 2216 ABSTRACTS OF GEEMIGAL PAPER$. decomposed, yielding ni trobenzyl ic iodide, trim eth y Is ul ph i ne iodide, and a third substance which melts at 67-70'. Methylic orthonmidobeizzylic sulphide, obtained by the action of zinc dust and acetic acid on the nitro-compound, is A, colourless oil, which boils at 277-278", and does not solidify at -18".The hydrochloride crystallises in long, colourless needles ; its acetgl derivative, NHAc*C,H6*S%fe, melts at loso, and its benzoyl derivative at 118'. J. J. S. Action of Hypobromous acid and Hypochlorous acid on Acid Anilides. By E. E. SLOSSON (Bey., 2895, 28, 3263--3270).- Acetobromami~tobenzene, NBrPhAc, mixed with acetoparabromanilide, is obtained by the action of alkaline hypobromite solution on tlcet- anilide at 0' ; the liquid is acidified with boric acid, when the compound is deposited in rectangular, yellowish plates, melting at 75-SCO. It is unstable, and in presence of moisture is converted into acetoparabrom- anilide ; the change is instantaneous at its melting point or when it is boiled with water; it liberates iodine from potassium iodide and nitro- gen f t-om ammonia, and in stability'ismidway between the corresponding chloro- and iodo-derivatives.For?nobl.o?nnmidobenzene, HCO*NPhBr, resembles the preceding compound in general properties, and is formed in a similar manner from formanilide ; it is deposited in yellow crystals melting at 55-37'. The above preparations contained about 10 and 20 per cent. respectively of the parabromanilides. Sodium hypochlorite gives a better yield of acetochloramidobeazeae than bleaching powder and hydrochloric acid ; it was therefore dmployed in the preparation of tho compounds described below. HCO*NPhCI, crystallises from ether or dilute acetic acid in colourless plates, melts at $ 3 4 4 O , is not reduced to formanilide by the action of ammonia, hydriodic acid, or alcohol, and is not changed when heated alone at 100'.I . l ' o r m o p a ~ ~ c h E o r a n ~ ~ ~ ~ e , H ~ ~ * ~ ~ ~ is prepared by heating the preceding compound with hydrochloric acid, or from parachloraniline and formic acid, and is deposited in eolourless crys- tals melting at 101'. Benzochlommidobenzene, NC 1P hBz, crystallises from light petroleum in needles melting at 78-80". The action of an alkali does not cause intramolecular rearrangement (exchange of position between the haloid and radicle ; Beckmann's reaction) in any of the above haloid amideg, although compounds of the analogous type RCO*NHX (X = C1 or Br) react i n this manner with the greatest readiness ; the cause of this difference in behavionr is being investigated. ;E'om?ochZorainidobenze)Le, J.B. T. Thioaldolaniline and Aldehyde-green. By WILHELM VON MILLER and JOSEF PLOCHL (Ber., 1896, 29, 59-61).-Recognising that substances containing the group >C:N- readily form additive products, the authors thought i t possible that this group might directly take u p hydrogen sulphide or sulphur, As a matter oE Fact, aldolanilide, OH*CHMe*CHz*CN:NPh (Abstr., 1894, i, 414), could not be mRde to unite simply with hydrogen sulphide ; but, by heating it in absolute alcoholic solution with crystallised ammonium sulphide,ORGANIC CHEMISTRY. 217 a white substance, OH*CHMe-CH2*CH<rPh, was obtained ; this S melts at 92", and t u r n s yellowish when kept for a time. The sulphur in aldehyde-green doubtless exists therein combined in much the same fashion.C. IF. B. Thiodiazo-derivatives. By ARTHUR R. HAXTZSCH and HANS FREESE (Ber., 1895, 28, 3237--3251).-The thiodiazo-derivatives described below were all prepared by the action of phenylic hydrosulphide on diazonium salts in alkaline solution. The diazo-ethers, RN:NOR, are now generally recognised as iso-derivatives, and these are probably '( anti " compounds, bat as all efforts to prepare " syn " isomerides have been unsuccessful, this is not absolutely proved. The fhio-ethers am more stable than the oxy-ethers, and do not combine with naph- thols either in alkaline or alcoholic solution ; they are also probably '' anti " compounds, but attempts to prepare isomerides were unsuc- cessful.The slow combination of naphthol and diazosulphanilic acid thio-ether ia probably caused by the regeneration, under the influ- ence of water, of some diazosulphanilic acid. The diazo-ethers are yellow and stable at 0'; alkalis and dilute acids are without action on them ; with concentrated acids, their components are regenerated ; they form unstable additive products with hydrogen chloride, and, when heated, explode and yield nitrogen ; when warmed with water, nitrogen and a sulpbide, ItSPh, are formed, but hydrolysis also occurs, and consequently a phenol and phenylic hydrosulphide, or its oxida- tion product, phenylic bisulphide, are also produced. Diazo t enzefh et hiop 12 e n y 1 ether, P h N : N* S P h , prepared from ph en y 1 ic hydrosulphide and diazonium chloride at -5O, is oily and unstable.A ~ z t ~ p u r a c h l o ~ o d ~ a z o b e ~ z z e ~ z e t ~ ~ ~ ~ e ~ y l ether, CsH4Cl*N:N*SPh, prepared from parachlorodiazonium chloride and phenylic hydrosulphide, crys- tallises from ether at 0' in yelIow, rectanguIar plates melting st 60-62'; the yield is 84 per cent. of the theoretical. The ether, unlike the oxygen derivative, is only very slowly attacked by glacial acetic acid, and the product does not combine with ,&naphthol; it is readily soluble in presence of sodium methoxide, but at low temperatures undergoes no further change. When heated with alcohol, nitrogen, parachlorophenylic sulphide, and phenylic bisulphide are formed.During the preparation of the ether, a highly unstable compound, possibly the " s p " derivative, is formed if the liquid is cooled so that a portion freezes ; i t evolves nitrogen below Oo, arid on one occasion exploded nt this temperature while still moist. PnrabromocZiazobenze?ze- fhiophenyl ether, C6H,Br*N:N*SPh, from parabromodiazonium chloride, crystallises in dark, reddish-brown plates, melts a t &", and is less stable than the chloro-derivative ; the yield is about 30 per cent. of the theoretical. Pui.iododiazobenzeneth~~p~enyl ether is even less stable than the bromo-derivative, and is prepared in a, siniilar manner. 0rthochlorodiazobe)zzenet~io~henyl ethey, evolves no nitrogen during its preparation ; like the preceding compound, it is oily. Dichlorodiazo- benze~zethiophenyl ethey, C,H,CI,*N:N*SPh [N : C1: C1 = 1 : 2 : 41, crys- tallises in golden plates, and melts at 55-56', The corresponding dibromo- and diiodo-derivatires and tr~bromodiazobe~zzenethio~he~tyL2 18 ABSTRACTS UF OHEMIOAL PAPERS.ether, C,H,Br,*N:X*SPh [Br, = 2 : 4 : 61, are difficult to purify, and apparently are liquid at 0". Antiparanitrodiaxobenze?aethiophenyl ether, N0,*C6H,:N:N*SPh, crys- tallises from warm alcohol in golden plates, melts at 96-97', and is the most stable compound of this class hitherto prepared ; a8 the oxy- ether is similarly characterised, the nitro-group appears to be specially favourable to the production of compounds possessing the anti-con- figuration. Antinitrodiazobenzene hydroxide does not react with phenylic hydrosulphide, but the sodium salt (sodium nitrophenyl- nitrosamine) yields the diazo-thio-ether and sodium hydroxide when treated with phenylic hydrosulphide in alcoholic solution.Paranitro- benzenediazonium perbromide is formed by the action of bromine on the thio-ether ; with iodine, paranitroiodobenzene is probably formed, whilst iodine chloride yields a compound which melts at 150-156', and is possibly nitrochloriodobenzene. S yn-sodium diazosuZpli a nilate t hiophenyl e f her, S 0,Na. CsH,*N:N*S Ph, is readily prepared by the interaction of phenylic hydrosulphide and diazosulphanilic acid in alkaline solution at O', but unless alkali is present in considerable excess the reaction proceeds slowly ; it crystal- lises in yellow plates, and, when dry, is stable at the ordinary tempera- ture, and in aqueous solution at 0' ; the yield is about 80 per cent. of the t.heoretica1.The silver salt is dark brown, and, like the sodium salt., immediately decomposes into its constituents when acidified with hydrochloric acid. The "anti" sodium salt does not react with phenylic hydrosulphide. The diazophenols combine with pbenylic hydrosulphide in neutral, alkaline, aud acid solution, but the yro- ducts were not investigated on account of their great instability. When the free diazophenols, prepared by the action of silver oxide on the hydrochlorides, are treated at 0' with hydrogen sulphide, com- pounds are formed which probably are additive products of bydro- gen sulphide and diazophenol bydrosnlphide, OH*C6H,*N:N*SH,H2S.The para-compound crystallises in deep red, microscopic needles, melts and decomposes at 74-73', is unstable above O', and decorn- poses in contact with indifferent solvents, such a s chloroform, light petroleum, and part.icnlarly ether, into sulphur, nitrogen, hydrogen snlphide, and probably phenol. The oytho-derivative resembles the preceding compound, melts at 69-70', and may be purified by dissofv- ing it in cold glacial acetic acid and precipitating with ice-cold water. By EUQEK BAMBEBGER and E. KRAUS (Ber., 1896, 29, 272-286 ; compare Hantzsch and Freese, preced- ing Abstr.) .-Diparanitrodiazobenzelze suli&de, J. B. T. Thiodiazo-derivatives. NO,*CsH*NS*NCeH*N02, N N is prepared by tlie action of hydrogen sulphide at Oo, on aqueous paranitrodiazobenzene chloride solution which has been almost neutralised with soda; the product is treated with ammonia to remove any diazomercaptan hydrosulphide (see below) ; i t crystal- lizes from acetone, on the addition of ice-cold water, in sulphur-yellow, lustrous needles, which explode at 89', and also when pressed,ORGANIC OHEMISTRY.219 or when treatcd with concentrated sulphuric acid or nitric acid vapour; and, on one occasion, when i t was gently heated on the water bath while covered with a large amount of light petroleum. It is insoluble in alkali a t the ordinary temperature, aud when heated, decomposes ; concentrated alcoholic potash decomposes i t at the ordinary temperature ; in acetone solution, it gives a violet-red coloration with soda, probably caused by the formation of a formazyl- derivative.Lead acetate added to the diazosulphide in alcoholic solution gives lead sulphide ; i t combines instantaneously with a-naphthol when warmed more slowly a t the ordinary temperature, giving an orange-yellow coloration changing to violet with alkali ; with a-naphthylamine the sulphide, in acet,ic acid solution, gives imme- diately a violet coloration, and it also combines directly w1t.h alkaline &naphthol. With resorcinol, a characteristic violet-red coloration is produced. Benzene reacts a t the ordinary temperature with the diazo- sulphide forming paranitrodipheny1,:paradinitrophenylic bisulphide, sulphur, and nitrogen ; the reaction takes place in two stages, nitro- diphenyl, nitrogen, and hydrogen sulphide are first formed, aud the latter converts a portion of the diazo-sulphide into dinitrophenyl- bisnlphide.Toluene and pyridine react like benzene, paranitro- phen y ltolyl and parani tropheny lpyridine, respectively, being pro- duced, together with dinitrophenylic bisulphide and sulphur. ParaiLitrodicrzobeizzene ?,Les.ca~tanhydrosulyhide, N02*CBHA*N (SH)*NII*S€€, is prepared by the action of hydrogen sulphide at O-' on aqueous para- nitrodiazobenzene chloride solution, in presence of hydrogen chloride in excess ; it is purified by dissolving itl in ammonia and continuously adding the solution to well cooled acetic acid, the precipitate is then crystallised from light petroleum, or from acetone by the addition of ice-cold water. It forms red, metallic, histrous needles with a blue refiex, melts at So, is decomposed when heated with alcohol or acetone, readily dissolves in alkalis and ammonia, and is reprecipitsted by acids.It does not combine with phenols in presence of either alkali or acid. The molecular weight was determined by the cryoscopic method ; the yield is about 50 per cent. of the nitraniline employed. The Eead salt is pale red, but becomes brown with a bronze lustre when dry; the siEuer salt is brownish-red and so011 blackens ; the wzercwic salt, Hg(N<~(c6H4*K0z)>S)~, is pale orange-yellow and crystalline. When heated, the mercaptan hydi*osulphide solidifies immediately after me1 ting, the fiolid then consisting of paranitraniline, paranitrophenyl- hydraziue, dinitrophenylic bisu Iphide, and sulphur, whilst hydrogen sulphide, nitrogen, and, in small quantity, nitrobenzene are evolved.The same result is obtained by boiling the mercaptan hydrosulphide for a considerable time with light petroleum or alcohol. The first stage in this decomposition probably consists in a resolution of the mercaptan hydrosulphide into nitrodiazobenzene mercaptan and hydrogen sul- phide, the latter then reduces a portion of the foriiier to nitrophenyl- hydrazine, nitraniline, and sulphur, whilst the remainder of the mercap- tan is oxidised by the air to nitrogen and dinitrophenylic bisulphide; the Hg ---220 ABSTRAOTS OF OHEJIICAL PAPERS. last compound is formed by the action of air on the mercaptan hydro- sulphide in ammoniacal solution, and also by the action of iodine ; it melts at 180*5", a.nd not at 168-173"as stated by Leuckart.Benzene and toluene react with the mercaptan hydrosulphide like alcohol, but in addition, nitrodipheny 1 and ni trop henyl tolyl respectivelj, are formed. Diparanitrodiazobenzene bisulphide, S2(N:N*C6H4*N02)2, is prepared like the above mercaptan hydrosulphide, except that the treatment with hydrogen sulphide is prolonged, the hydrosulphide is removed from the product by treating it with ammonia, and the residue is extracted at 0" with acetone in which the bisulphide dissolves more readily than the monosulphide. It is purified in a similar manner to the latter, crystallises in lustrous, pale sulphur-yellow needles or plates, tuelts and decomposes at 120-123*, does not explode, and is stable at the ordinary temperature, but decomposes when heated with acetone, ~lcohol, or benzene.The bisulphide dissolves in alkali only when hoiled, gas is evolved and the solution becomes reddish-brown ; in alcoholic or acetone solution, i t gives a claret coloration with alkali ; with a-naphthylamine, a violet-red coloration is slowly produced ; with a-naphthol and alkali, a dark brownish-red coloration is obtained which changes slowly to violet. With resorcinol, the mono- and bi- sulphides react almost identically, whilst with benzene, the bisulphide yields the same products as the monosulphide, but the action pro- ceeds less readily. Isoparanitrodiazobenzene hydroxide, with hydro- gen sulphide, yields, at - 10°-Oo, paranitraniline and paranitro- phenylhydrazine. Dinitrodiazobenzene sulphide, in presence of sulph- uric acid, is converted by the action of hydrogen sulphide into the bisulphide, and the mercaptan hjdrosulphide ; this confirms the authors' view that, with nitrodiazobenzene, the hydrogen sulphide first yields the monosulphide, a part of the latter being then converted into bisulphide, and part into the bydrosulphide.As yet the pre- ceding formula? cau only be regarded tts provisional. J. B. I'. Salts of Phenylhydrazine and of a-Methylphenylhydrrine. By SIRO GRIMALDI (Zeal. Accad. Lincei, 1893, i, 483-491) .-PhenyZ- hydrazine hydriodide, NH Ph-NH,,HI, crystallises in white scales or needles melting at 120-122', and is readily soluble in water, alcohol, or acetone, giviug neutral solutions; its solubility in water is in- creased by the addition of alkali iodides.With potassium iodide and magnesium iodide, it yields double salts of the compositions C,H,N,,HI,XI, and ( CsH8N2,HI)2,Mg12. The ItydroJluoride, NHPh*NHZ,HF, crystallises in lustrous, white laminm, and is solub!e in water or alcohol; its solubility in water is increased by adding alkali fluorides and its aqueous solution is neutral to test papers. It can be easily sublimed unchanged, and forms double salfs of the compositions CGH8N2,HF,KF ; CsH8N2,HF,NaF ; C6H8N2,HF,LiF, and which crystallise in white lamice and are very soluble in water.ORGANIC CHENISTRT. 221 a-Methylpheiiylhydrazine hydroJEuoYide, NMePh*NH,,HF, crystal- lises in colourless lamina?, and is very soluble in water. W. J. P. Constitution of Dicyanophenylhydrazine and Bladin’s Tri- azole Compounds. By AMERICO ANDREOCCI (Real.Accad. Lincei, 1593, ii, 302-310).-The author replies to Barnberger and de Gryter’s criticisms (Abstr., 1894, i, 23) of his previous work (Abstr., 1892, 636). W. J. P. Migration of the Diazo-Group. By C. SCHRAUBE and M. FR~TSCH (Ber., 1896, 29, 287-294) .-Diazosnlphanilic acid and paratoluidine hydrochloride at 0’ yield sulphanilic acid and diazo- paratolnene chloride, as Griess has previously shown; the course of the reaction may be followed by means of alkaline @-naphthol solu- tion, with which the diazotoluene forms an insoluble compound ; it is complete after 24 hours, but the presence of hydrochloric acid in large excess completely prevents the change. In neutral solution, the above compounds immediately yield the diazoamido-derivat ire, C6H,~e*N:N*NH*CsH40S03H, in the form of a yellow tolicidine salt ; the sodium salt crystallises in long, thin, pale-yellow plates; the disodium salt is deep yellow; the cnlcitciii salt is pale yellow, and crystalline ; the bariurrL salt is sparingly soluble.When treated with acids, the sodium salt yields sulphanilic acid and diazotoluene chloride. In alkaline solution, dinzosulphanilic acid and para- toluidine yield a diazoamido-derivative of sulphanilic acid and diazo- smidotolu&, the tariuin salt, N < ~ & ~ : ~ : ~ > B a , of the former, being crystalline. With less alkali, the mixed diazoamido-compound (see above) is also formed. Dinzotoluene chloride and sulphanilic acid are without action in presence of mineral acids, hut, with sodium sulphanilate, the reaction is normal, whilst the two sodium salts yield the two diazoamido-compounds. Paranitrodiazobenzene chloride and paratoluidiae readily yield a diazoamido-derivative in acid solu- tion, but in presence of a large excem of acid, the diazo-group migrates and the reaction may be readily followed by testing portions of the liquid with a-naphthyhmine hydrochloride in hydrochloric acid solution.In neutral or faintly acid solution, the diazoamido-deriva- tive is formed, and is quickly resolred by hydrochloric acid into para- diazotoluene and paranitraniline. The migration of the diazo-group resembles the formation of diazoamido-derivatives, as in both cases the imido-group combines with the most negative radicle, and the diazo- group with the positive one. Following V.Meyer, the interaction of diazosulphanilic acid and paratoluidine in alkaline solution is re- garded a s taking place in several stages, an additive Compound, C6Hi,Me*NH*N(OH)oNH*C6H,.S0,H, being first formed, which com- bioes with a second molecule of diazosulphanilic acid forming a com- pound C,H4Me*NH.N~OH)~N(CBH~*S03H)*N(OH)~NH*C6H,~corresponding with von Pechmann’g bisdiazobenzene anilide ; and, finally, this is resolved into diazoamidosulphanilic acid and diazotoluene222 LIBSTRACTS OF OHEMIGAL PAPERS, which, with the remaining toluidine, yields diazo-amidotoluene. The results obtained with diazotoluene and sulphanilic acid in alkaline solution are explained in a similar manuer. d. 5. T. Action of Nitrosobenzene on Amido-compounds.By ECGEX BAMRERGER (Ber., 1896, 29, 102-104 ; compare Mills, Trans., 1895, 925).--The author has studied the behavionr of numerous amido- compounds towards nitrosobenzene, bases of both the aromatic and the aliphatic series having been included in the investigation, the results of which will be shortly published. According to Xills (loc. cit.), phenylhydrazine gives rise to azo- benzene when treated wI’ tli nitrosobenzene, Walther having obtained aniline ; the author, however, has observed the production of diaao- h y dyoxyamidobenzene, P h N:N*N( OH) P h, crystal 1 ising in pale yellow, silky needles, which melt at 126-1227’. This substance is also ob- tained from diazobenzene and phenylhydroxylamine, which are formed when the compound is treated with acids.Analogous diazohydroxy- amido-compounds have been obtained from /3-benzylhydroxylamine and /3-methylhydrosylamine, namely, d.lazobenzenehydrozyamidobenzyl, PhN:N*N(OH)*CH,Ph, which melts at 105’, and parmitrodiazoben- z e n e h y d r o w y n ~ z i d o ~ ~ e t ~ a ~ ~ ~ , NO,*C,H,*N:N*N(OH)Me, which crystal- lises in silky, golden-yellow needles, and melts at 2 2 8 O . M. 0. F, Influence of Methyl Groups in the Ortho-position in hinder- ing the Formation of Oximes. By FRITZ BAUM (Bey., 1895, 28, 3207-3212) .-Hantzscti (Abstr., 1891, 36) has shown that both ketones and aldehydes, in which substitution has taken place in the two ortho-positions with respect to the carbongl group, do not- yield oximes. Peith and Uavies (-4bstr., 1892, 314) have also shown that acetyl- niesitylene yields no oxime, but at highel.temperatures reacts with hydroxylarnine hydrochloride, according to Beckmann’s reaction, yielding acetomesidide. The author has investigated the action of hydroxylamine hydrochloride on dibenzoylmesitylene, mono- and di- acetylisodurene, acety lpentamethylbemene, and mesitylglyoxylic acid, and finds that no oxime is formed in any case; mesitylglyoxylic acid, however, gave cjanomesitylene (m. p. 53’). Ethylic mesityl- glyoxylate yields a compound which may be an oxime, and which is being subjected to further investigation. Acetylmesitylene, mono- and di-benzoylmesitylene, and propionyl- mesitylene, when treated with phenylhydraziae, yield no hydrazones. When acetylmesitylene is added to concentrated nitric acid, di- 912 esity ldinitmwc yl, CsH2Me3*C0*$1:N0 is obtained ; it crystallises in CbH,Me,*CO*C:NO’ large, yellowish needles; melts at 141°, and, when boiled with alco- holic soda, yields mesitylcarboxylic acid.J. J. S. Action of Hydroxylamine on Methylic Phthalate. By G~ORGIO ERRERA ( G a z e f i n , 1895, ii, 21-25> .-Hydroxylamine actsORGAN10 0HEMISTRT. 228 on methylic phthafate undei, P-arious conditions, yielding phthalyl- hydroxylamine, from which phthal ylacefozylanzine, CO <$:> C:N*OAc, is readily prepared ; this crystallises in monoclinic plates melting at 181', and is sparingly soluble in alcohol or water; a : Z, : c = 1.97784 : 1 : 1.11035 ; p = 85O 48'. It is hydrolysed by boiling with water, yielding acetic acid and phthalylhydroxylamine ; the latter gives a, crystalline ammonio-derivative, which is very soluble in water, and readily loses ammonia in the air, giving phthalylhydroxylnmine.ri-Carbodiphenylimide. By CARL ScmLr, (Ber., 1896, 29, 270- 271).-Von Miller and Plochl have suggested (Abstr., 1895, i, 415) that r,-carbociipheiiylimide is a mixture of the liquid a-, and the crystalline, p-compounds ; in opposition to this view, the following facts are advanced. (1) With light petroleum, the surface of the y-com- pound becomes granular, and is slowly converted into the /3-form ; the change corresponds exactly with that which takes place when vitreous arsenious anhydride passes into the crystalline modification, and is also slowly produced by gentle heating, during which no a-imide is vola- tilised.(2) Miller and Plochl have shown that a concentrated benzene solution of the p-imide, at about the freezing point of benzene, con- tains, a t the most, only traces of the a-compound ; such a solution, after concentration under certain conditions, yields only the amor- phous 7-compound. (3) When intimately mixed, the a- and p-com- pounds give a white, opaque mass, which is only viscid if it contains 4 parts of the a-imide. The ?-modification occasionally changes slowly nnd spontaneously into crystals consisting of needles and plates; it can scarcely be a solid solution, as such should, from analogy, be crystalline and not amorphous. Action of Succinic acid on Paramidophenol and its Ethers, By ARXALDO PIUTTI (Be?.., 1896, 29, 84436) .--Parah ydrozyphenyl- >N*CsH,*OH, is obtained by fusing succinic szcccinimide, acid with paramidophenol in molecular proportion ; it crystallises in lustrous, colourless prisms, and melts at 275-276'.Hot potash converts it, into pamhydroxyphenylsuccinamic acid, which dissolves in water, alcohol, and acetic acid, and melts a t 1S1-1723 ; the barizm and alkali salts are readily soluble in water, the Eead and siher salts are crystalline, aud the copper salt is insoluble in water. Paramethonyphen~ylsuccinimide is produced on heating paranisidine hydrochloride OP methacetiii with succinic acid at 290", and crystal- lises in colourless, prismatic needles, which melt a t 162-163O ; hydrolysis gives rise to paramethozyy,henn2/lszcccinamic acid, which crystallises from water, and melts a t 156--157'.Paretho~~.yphenylsuccin~mide ( pyrantine) is obtained by fusing SUC- cinic acid with phenacetin, or with paraphenetidine hydrochloride ; it crystallises in colourless,. prismatic needles, and melts at 155O. Succinic acid and phenetidine are formed when the substance is W. J. P. J. B. T. SHZ*CO CH2*C0224 ABSTRACTS OF CHEJflCAL PAPERS, treated with hot hydrochloric acid, and fusion with potassium hydro- gen sulphate brings about the same result; coloration is developed by nitric acid, chromic acid, chlorine water, and ammonia, whilst fusion with potash, and treatment of the aqueous extract with a solution of calcium hypochlorite, yields a red liquid. Parethozy- phenylsuccinamic acid is obtained by hydrolysing the foregoing derivative ; it crystallises from hot water in nacreous leaflets, and melts at 160-161O.The sodium salt is the soluble form of pyran- tine, and possesses valuable pliysiological properties which recom- mend its application as a febrifuge. M. 0. F. Action of Phenylic Isocyanate on Amido-acids. By CARL PAAL and FRITZ GANSER (Bey., 1895, 28, 3.227-3234; compare Abstr., 1894, i, 332).--fn continuation of their work on amido-acids, the authors have studied the action of phenylic isocyanate on the alkali salts of the three amidocinnamic acids, of dphanilic acid, and sarcosine. Ortlrophenylztl.eidocinnn?izic acid, NHPhDCO*NH*C,H**CH:CH'COOH, crptallises in very small, felted needles, melts at 236O, is insoluble in water, only sparingly sol nble in chloroform, carbon bisulphide, and ether, but readily in hot alcohol and acetic acid.The alkali salts are not soluble in concentrated, alkaline liquids ; the silver salt forms an amorphous mass, which is practically insoluble in water, and is extremely sensitive to light. The ethplic salt crystallises in needles, melts at 1 1 2 O , and is readily soluble in most organic solvents. When the acid is reduced with sodium amalgam and water, it yields ortho- yhenylureidophenylpropio?tic acid, which melts at 168", and is readily soluble in hot alcohol, acetone, and ethylic acetate. The dibromide, NHPh.CO-NH*U6H4*CHBr.CHBr*Co~H, melts at 227O, and is readily soluble in alcohol and ethylic acetate, but only sparingly in most other organic solvents. 2Metapheizylureidocinnamic acid me1 ts at 249O, and is more sparingly soluble in most solvents than the ortho-acid.The etlqlic salt crys- tallises in needles, melts at 198", and is readily soluble in chloro- form and ethylic acetate. The ammoitium, sodium, and siiver salts resemble those of the ortho-acid. The dibrmnide crystallises in small plates, and melts a t 2 4 0 O . Metnphenylureidophenylpropionic acid melts at 180'. Paraphen~lureidocinnamic acid crystallises in brilliant glistening needles, and melts at 2 5 2 O ; the ethylic salt melts a t 20P0, and the dibromide begins to decompose a t 3.65'. PQraphen?llureidophenyE propioi~ic acid melts at 218*, and is practically insoluble in ether. Para~henyHzcrez'~obenze~~$u~ho~~c acid, NHPh*CO*NH*CsH,*SO,R, obtained from sodium sulphanilate and phenylic isocyanate, crystal- lises in colonrless needles or prisms, and begins to decompose at 270', but is not completely melted at 300'. It is practically insoluble in ether, chloroforni, and benzene, but readily in ethylic alcohol, acetone, and acetic acid.The calcium salt crystallises from its hot aqueous solution in glistening, rhombic plates, which contain 3$H20.ORGANIC CHE3IISTRY. 225 The barium salt is anhydrous, and is only sparingly soluble in hot water. The silver salt ci-ystallises from hot water in large prisms, and is not deeolorised by exposure to light. The ethylic salt c r p - tallises in colourless needles, melts at 155O, and is readily soluble in ether, alcohol, acetone, &c. a b-MethzJ~lieny lureidoacetic acid, NH P h*C O*NMe*C H2*C OOH, cry% tallises in needles, melts a t 102*, and is insoluble in ether and chloro- form, but readily dissolves in sodium hydroxide, boiling water, ethylic acetate, and water.The silver salt could not be obtained ; the ethylic salt crystallises in small needles, and melts at 75". J. J. S. Derivatives of Metadibromoparahydroxybenzaldehyde. By CARL PAAL and G. KROMSCHROL~ER (Bey., 1895, 28, 3234-3236; compare this vol., i, 40) .-The dibromohydroxybenznldehyde [Br, : OH = 3 : 5 : 41, pi.eviously described, readily combines with aniline to form dibronzoparali ydrox~benzyZ~deneu~~i~~ne, 0 H*C,H,Br,*CH:NPh. It is readily soluble in warm alcohol and in most organic solvents, crys- tallises in compact, red crystals, or from alcohol iu small, metallic, violet coloured plates containing alcohol of crystallisation.It melts at 147". 211etadibroinoparahydrox y benzy l i d e i z e p a ~ n t o l u i ~ ~ ~ e crystallises from its alcoholic solution i n plates, which are characterised by a blue, metallic histre, and melts at 15'1'. il.lktadibromo~aral~ydroxybenzWlidene-a-nnphth~lami~~e crystallises in yellowish needles, rne1t.s at 146", and does not combine with alcohol. n~etadibromopnrahyd.l.o~~henzaldoxime crystallises in short, white needles, melts at 19P0, and is readily soluble in alcohol, ether, and ethylic acetate. Illetadibl.omoparahydroxyZle?.tzoic acid, obtained by the oxidation of the aldehyde with potassium permanganate (1 per cent;. solution), crystallises in colonrless needles and melts at 268". J. J. S. Isomerism of Trithioaldehydes. By EMTL W~RNER (Bei.., 1896, 29,139-16@).-Baumann and li'romrn (Abstr., 1889, 852 ; 1890, 2.5 and 26 ; 1891,1008 and 1050) have shown that benzsldehyde, anis- aldehyde, methyl- and isobutylsalicyl-aldehyde, cinnamaldehyde, and furfuraldehyde each yield two stereoisomeric trithioaldehydes, a lower melting, or a-, form, and a higher melting, or p-, form, Kopp (Abstr., 1894, i, 128) Eound that the three hydroxybenzaldehydes yield, each, one trithio-derivative, which he termed the B-modifi- cation, as i t was not changed by the action of iodine.The author has repeated some of Kopp's experiments, and has arrived at similar results. Thus, with parabydroxybenzaldehyde under the most vary- ing conditions, only a single trithio-compound could be obtained ; i t crystallises with 2 mols.of benzene (Kopp states 3 mols.), which it partially loses on exposure to the air, and melts at 215". Parabenzylo~ybenzaZdehyde, obtained by shaking the hydroxynlde- hyde in strong alkaline solution with the requisite quantity of benzylic chloride, ci*ystsllises in short needles, melts at 7 2 O , and is readily soluble in alcohol, chloroform, benzeue, and ether. If hydrogen226 ABSTRACTS OF OHEMICAL PAPERS. sulphide is passed into an alcoholic solution to which atcoholic hydro- gen chloride has been added, a- trit hiopaya benzy Zoxybenzaldehyde is obtained ; it crystallises in colotirless needles, melts at 12i0, and is sparingly soluble in alcohol and ether, but readily in chloroform, beuzexie, and acetone. When treated with iodine, it passes into the P-modification, which also crystallises in colourless needles, melts a t 198--199", contains 2 mols.of benzene of crystallisation, and is more sparingly soluble in all solven3s than the a-compound. By using 2 vol. of alcoholic hydrogen chloride to 1 vol. of a, 5 per cent. solution of the benzylbenzaldehyde, about equal quantities of the a- and p-modifications are obtained. Vanillin yields only one tn'thiovaniZZin, which melts at 235-237O, and is only sparingly soluble in alcohol, benzene, and ether, more readily in chloroform and acetone ; when the ciytals are boiled with benzene, they take up 2 mols. of benzene of crystallisation. Trith{o- benzoyZz.anillin, obtained by the action of benzoic chloride on trithio- vanillin, crystallises in colourless needles, begins to sinter at 155O, and melts at 164'.Benzoytvanillin melts at 75", and is readily soluble in alcohol, chloroform, and ether. Methylvanillin yields two isomeric trithio-derivatives, which may be separated by means of benzene. a-TrithiomethylvnniZZin crystal- lises in small needles, melts at 168", and is extremely readily soluble in benzene, but only sparingly SO in alcobol ; when treated, in benzene solution, with iodine, it is transformed into the @compound, which crystallises with 2 mols, of benzene or thiophen, and melts at 220O. a-Trithiqpiperonal cryst.allises in small, colourless needles, melts a t 183O, is sparingly soluble in alcohol or ether, and readily in chloro- form, acetone, and benzene. /3-Tq.ithiopiperonal melts at 236O, and is more sparingly soluble than the a-compound .Trithiogentisic aldehyde apparently exists in one form only ; this crystallises in small, white needles, melts and decomposes at 190°, and is very readily soluble in alcohol. a-Trithiodimefhylgentisic aldehyde is n colourless, crystalline powder, melts at 95-96', and is readily soluble in benzene, acetone, and chloroform. The /%compound crystallises Gith 2 mob. of benzene and melts at 180". It is practically insoluble in alcohol, and only sparingly soluble in chloroform. a-TrithiocumaZclehyde crystallises in long, white needles, and melts at 165" ; the /!j-eompotmd could not be obtained directly, but only by the action of iodine on the a-isomeride; it crystallises with 3 mols. of benzene, and melts at 205". a-Tm'thiometato72laldel~~d~ crystallises in white needles and melts a t 144" ; the p-isomeride crystallises in white, glistening needles, which contain 3 mols.of benzene, and melts at 225". a-Trithioivltratolualdehyde melts at 149-150°, and the p-cornpowid a t 180' ; the latter cryst,allises with 3 mols. of benxeue. a-Trithio-ov%obromobenzaldehyde melts a t "So, is only sparingly fioluble in alcohol, but readily in ether, benzene, chloroform, and acetone ; the p-isomeride melts at 155O, and crystallises with 1 mol. of benzene. a-Trithiopara~omobenxaldeh yde is readily soluble in benzene, andORGANIC CHEMISTRY. 227 crystallises in small needles, which melt at 174n. The P-compouizd crystallises with 1 mol. of benzene, melts at; 203", and is more spar- ingly soluble than the a-isomeride.Metanitrobenzaldehyde yields a trithio-derivative, which melts a t 180-190"; it was found impossibie to purify the compound, as it is insoluble in all organic solvents. Orthonitrobenzaldehyde gave a similar result. Metsnitrocumaldehyde gave only one t,.itkio-dei*ivative, which melts at 118", and is not acted on by iodine. Metanitroanisaldehyde melts at 72", whereas Einhorn and Grabfield (Abstr., 1888, 478) give 83.5" as the melting point. A dinitroanisaldehyde, melting at 8 6 O , was also obtained. Trithiollzetanitroanisazdehyde is a yellowish, crys- talline powder, and melts a t 108" ; the t.).ithiot~initl.oaZdeh?/de melts at 188", is readily soluble in benzene, chloroform, and acetone, but only sparingly in alcohol or ether. The author summarises his results as follows.1. Substitnted aromatic aldehydes yield two stereoisomeric trithio. derivatives only when the substituting groups are of a positive or indifferent nature. Aldehydes with negative substituting groups yield one trithio-aldehyde, namely, the [3-modification. If the negative character of the hydroxyl group of a phenolic aldehyde is changed by methylation, &c., then the resulting compound yields two isomeric trithio-derivatives. 2. All a- trithioaldehydes may be converted into the /%modifications by means of iodine. 3. The trithioaldehydes are most easily obtained from phenolic aldehydes or aldehydes containing negative groups ; if positive groups are present, polymerides of high molecular weight are apt to be formed. J. J. S. Metadihydroxyphenyl Ketones.By ADOLPH CLAUS and M. HUTH (J. pr. Chem., 1896, [2], 53, 39-42).--By acetylating the alkylic ethers of resoreinol (by treating them with acetic chloride and aluminium chloride in carbon bisulphide), it is possible to obtain, according to the conditions of the experiment, the dialkyloxyaceto- phenone, the alkyloxy h ydrox 7 ace tophenone, or dih ydroxyacetop henone itself. The compound last mentioned melts a t 178', and is therefore not identical with that (m. p. 142O) obtained by Neneki and Siebep (Abstr., 1881, 591) from resorcinol by acting on it with glacial acetic acid and zinc chloride. This lack of identity extends to the derivatives of the two compounds, as will be seen from the following list of melt- ing points. Nencki and Sieber. phenone... . . . 142' 178O Claw and Huth. Dihydrox yaceto- Oxime therefrom 202" (decomposes) 223-225' (decomposes). Oxime therefrom 1 2 2 O 240" (decomposes). The authors note a curious interchange between these two corn- Monethyl ether.. 48" 1 0 8 O Diethyl ether. . . 68-69' 1 5 2 O228 ABSTRACTS OF CHEMICAL PAPERS. pounds and their derivatives, which seems to betoken an alteration of orientation, brought about by thc influence of the nlkyl groups. The identity of composition and molecular weight of the two dihydroxjacetophenones has been established. Introduction of two Acetyl Groups into Aromatic Hydro- carbons. By FRITZ BACN and VICTOR MEYER (Ber., 1895,28,3212- 3215).-Hitherto it has been found impossible to introduce two acetyl groups into ai-omntic hydrocarbons by the Friedel-Crafts method, but the anthors show that a diacetyl derivative of durene may be obtained if the action is carried on without prolonged heating, and i n the presence of an excess of acetic chloride ; if, however, the mixture is heated for some time, as in the usual Friedel-Crafts synthesis, t h e rnonacetyl derivative alone is obtained.Benzene and mesitylene apparently do not yield diacctyl derivatives under similar conditions. Diacefyldurene melts at 178O, distils between 323 and 32ti0, and crjs- tallises from ether in glistening, six-sided plates. Diacetylisodztrene melts at 121' and distils at 312-37". AcetyEisodztrene is an oil, and boils at 255-260O. DipropionyEdurene melts at 176' and boils at 330-335'. Prop'onyZdureiie melts at 79" and distils at 265-2'10".The authors have not yet proved that the second cLcety.1 group does not replace one of the methyl groups of dcrene. J. J. S. Formation and Hydrolysis of Ethereal Salts. By VICTOR METER (Ber., 1895, 28, 3197-3201; compare Abstr., 1894, i, 243, 463; 1895, i, 93, 228, 466).-The author now shows that phenyl- acetic acid is much more readily etherified than bertzoic acid. Thue, a solution of phenylacetic acid i n methglic alcohol, containing on1.T 3 per cent. of hydrochloric acid, yields 50 per cent. of ethereal salt after five minutes; benzoic acid under the same conditions yields no trace of ethereal salt. This points to the fact that the two methyleno hydrogen atoms in phenylacetic acid exert no restraining influence on the formation of ethereal salts, whereas the two methin hydrogen atoms in benzoic acid do.The relationship between the formation of ethereal salts and the hydi-olysis of the corresponding nitriles is not so simple as it is gene- rally considered. For instance, tripheiiylacetic acid is etherified with difficulty and triphenylacrylic acid readily, but the nitrile of the foismer acid is much more easy to hydrolyse than that of tbe latter. It has been previously shown that mesity lformic (mesitylenecayb- oxylic) acid, when treated for 12 hours in the cold, yields no ethereal salt, whereas, at the boiling point of the alcohol, a considerable amount of ethereal salt, is formed. It is now shown that, if hydrogen chloride is kept passing through a solution of this acid in methylic alcohol (at Oo) during a week, no less than 26 per cent.is converted into the ethereal salt, and, at the end of two weeks, 46 per cent. Symmetrical trinitrobenzoic acid, when treated in the same way for a week, gave only 0.7 per cent. of ethcreal salt. The mono-substituted derivatives of benzoic acid, in which the substituting groups were CH3, CI, Br, I, and NO,, have been investigated, and, in each case, the ortho-acid A. G. B.0 Ra ANIC CHEMTSTR Y. 229 was the one which took longest to etherify, and the corresponding ethereal salt the one most difficult to liydrolyse. Other rtlcoliols besides methylic alcohol have been tried, and yield siini tar results. J. J. S. A New Phenomenon in the Formation of Ethereal Salts by the action of Alcohol and Hydrogen Chloride on Aromatic Acids. By A.SHC'KOFF (Ber., 1895, 28, 3201--3202).-The authoi has studied the action of methylic alcohol and hydrogen chloride on benzoic and phetiylncetic acids ; he finds that a given concentration of the hydrogen chloridcj gives the maximum of ethereal salt in R, given time, and tha4 a-stronger or weaker alcoholic solution of the hydrogen chloride yields smaller quantities of ethereal salt. Thus a t Oo phenylacetic acid gives a, maximum of methylic salt when treated with a solution containing 40 grams of hydrogen chloride to 100 of methylic alcohol ; at 2Z0, benzoic acid gives a, innximum of ethereal salt with 50 parts of hydrogen chloride to 100 of alcohol. Heinrich Goldschmidt suggests that the more concentrated solu- tions of hydrogen chloride in alcoliol readily form the alkylic chloride and water, and that it is the water thus formed which has a retarding influence on the formation of ethereal salts.J. J. S. Etherification by means of Alcoholic Hydrogen Chloride. By HEINRICH GOLDSCHWIDT (Ber., 1895, 28, 3218--3227).-The author has made experiment3 on the velocity of etherification of benzoic acid, by means of alcohol, in the presence of varying quanti- tics of hydrogen chloride; the results show that the velocity of etherification in the case of dilute solutions of hydrogen chloride is proportional to the concentration of the hydrogen chloride, but the addition of even sniall quantities of water retards the velopity to a considerable extent. Hydrogen bromide has very much the same influence on the velocity of etherification as hydrogen chloride, but picric acid has far less influence.Substituted benzoic acids are etherified a t different rates by alcoholic hydrogen chloride; in all caqes, the ortbo-substituted acids are much more slowly etherified (V. Meyer, this vol., i, 228). As a rule, substitution in the meta- position increases the velocity, except i n the case of the nitro-group, and para- are more slowly etherified than mets-compoands. The author also confirms V. Meyer's statement that phenylacetio acid is mme easily etherified than benzoic acid. Formation of Ethereal Salts from Acids and Alcohols. By I~UDOLF WEGSCHEIDER (Bey., 1895, 28, 3127-3128 ; compare Abstr., 1895, i, 499).--l'he action of methylic alcohol on hemipinic acid, in pre- sence of an eighthpnrt of itsvolume of concentrated sulphuric acid gives rise to t8he p-monomethylic salt ; etherification by means of aulphnric acid has, therefore, the same result as when hydrogen chloride is eniployed, and the author in consequence holds the view that in the former ease also etherification depends on the intermediate production of an additive compound.When equal volnmes of methylic alcohol and sulphuric acid are wed, the normal salt of hemipinic acid is J. J. S. VOL. LXS. i. S230 ABSTRACTS OY CHEMIOAL PAPERS. formed ; symmetrical tribromobenzoic acid is also partially etherified when thus treated, although, under the conditions first described, the last-named acid yields no ethereal salt. There is no appreciable formation of ethereal salt when a mixture of methylic alcohol and sulphuric acid acts on hydrogen potassium hemipinate during a, short period.When hemipinic acid is heated with methylic alcohol at looo, a-monomethylic hemipinate is produced, probably owing to the inter- mediate formation of the anhydride, RS this substance is obtained in small quantity when hemipinic acid is heated at 100°, benzoic acid, moreover, yields no ethereal salt under these conditions. The formation of the a-modification in the absence of sulphuric acid or hydrogen chloride clearly indicates that the effect produced by these agents is not due to dehydrating action. Pseudophenylacetic acid. By EDUARD BC'CHNER (Bey., 1896, 29, 106-109).-The author proposes to apply the names pseudophenyl- acetic acid,. pseudotolylacetic acid, &c., to the acids which are obtained by the action of ethylic tliazoacctate on the aromatic hydrocarbons, and are isomeric with phenylacetic acid, &c.,&'odium pseudophertyl- acetate is obtained as a crystalline pomTder by the action of sodium ethoxide on the ethylic salt. 'It cannot be recrgstallised, gradually increases in weight when preserved in dry air, and is at once oxidised by potassium permanganate. Like the etbylic salt and the amide, it forms a cherry-red solution in concentrated sulphuric acid, the colour gradually changing to indigo-blue. Psez&dophe?z ylacetainide crystallises from water i n large, vitreous tablets, which melt at 141°, When hydrolysed by aqueous soda, it yields an unsaturated acid, which melts at about 71°, and does not give the characteristic reaction of the amipe with sulphuric acid.Sodium pseudotolylacetate closely resembles the corresponding salt of pseudophenylacetic acid. Pseudo- folylacetic acid unites with fonr atoms of bromine to form an unshablc tetrabromide, which loses hydrogen bromide when kept, a solid substance being left, which has the formula CsHsBr,O,. This corn- pounci cannot be recrptallised, but may be reprecipitated from its solution in alkalis; it melts a t 80-85O. The corresponding deri- vative of pseudophenylacetic acid me1 ts att 84-86O. When pseudo- tolylacetic acid is passed through a red-hot tube, about 10 per cent. of paraxylene is formed. Pseudophenjlacetic acid yields about 7 per cent. of terephthalic acid when oxidised with nitric acid, whilst t h i s acid is accompanied by benzoic acid when alkaline potassium per- manganate is used.The constitution of pseudophenylacetic acid is best represented by the formula COOH*CH< I which admits of a simpler explmabion of the reactions of the acid than that proposed by V. Meyer (Ber., 1890, 23, 617), in which the COOH*CH group is attached at the para- instead of the ortho-positions. By ADOLPH CLAW (S. p ~ . Chem,, 1895, [el, 52, 529- 532).--In reference to V. Meyer's recent publica- %ion (this vol., i, 170), the author draws attention to the work which M. 0. F. C H* CH: $: H CH*CH:CH' A. H. Tetramethylbenzoic acids.ORGANIC OHEMISTRY. 231 haa been done by himself and his pupils on the oxidation of the methyl duryl ketones (Ahstr., 1888, 275; 1889, 50). Attempts to purify the tetramethylbenzoic acids then described have succeeded to 8ome extent, and it is shown that the 2 : 3 : 5 : 6-acid melts at 127*, not 109" (loc.cit.). The oxidation of symmetrical tetramethylbenzoic acid by perman- ganate yields, under all conditions, dimethylbenzenetr*icarboxylic acid, whilst similar treatment of asymmetrical tetramethylbenzoic acid yields a dicarboxFlic acid, in which the new carboxyl group is in the para-position, for by distillation with soda-lime it gives pseudo- cumene. Details of this research will follow shortly. Contrary to Victor Meyer's rule, all three acids are equally easily etherified by hydrogen chloride in niethylic and ethylic alcohol. The methylic and ethylic salts of symmetrical tetramethylbenzoic acid are crystalline, the former melting a t 79-41", and the latter at 47-48', The methylic and ethylic salts of the other acids are viscid oils.Some criticisms of V. Meyer's paper are given. Action of Ammonia on Ethylic Benzoylacetate. A. G. B. By CARL GOLDSCHMIDT (Bey.: 1896,29,105) .-Ammonia unites with ethylic ben- zoylacetate to form an additiveproduct, COPh*CH,*COOEt,NH,, which crystallises from alcohol in plates, having a sating lustre, and melting at 178". It sublimes when heated, and yields ammonia when treated with aqueous soda. Methylamine converts ethglic benzoylacetate into a white compound which gradually loses water and changes into ethylic P-methylinzido~henylrop~onate, NMe:CPh*CH,*COOE t. A. H. Regularity in the Decomposition of Aromatic Ketonic Acids. By FELIX MUHR (Ber., 1895,28, 3215-3218).-Victor Meyer has pre- viousIy shown (Abstr., 1895, i, 467) that symmetrical trimethyl-& benzoylpropionic acid is decomposed by hydriodic acid into mesitylene and snccinic acid.The author shows that the same decomposition may be brought about by heating the acid for five hours at 150" with hydrochloric acid. Parametliylbenzoylpr~pio~iic m i d , obtained by the action of a soh- tion of toluene in carbon bisulphide on succinic anhydride in the presence of aluminium chloride, melts a t 117", and is not decomposed when heated with hydrochloric acid at 150". Benzoylpropionic acid also is not acted on. Metadimethylbenaoy lpropionic acid (obtained from metaxylene), crys- tallises in colourless needles, melts at 106", and is completely decom- posed into metaxylene and succinic acid when heated with hydro- chloric acid.OrthodinzethylBen~o?lErpropionie acid melts at 105", and is not decom- posed under the usual treatment. Paradimethylbenzoylpropionic acid melts a t 62", whereas Clam gives 84" as the melting point, and is partially decomposed when heated at 150" with hydrochloric acid. Asymmetrical trimethylbenzoylipropionic acid (from pseudocuniene) melts at 98O, and is also partially decomposed when heated with hydro- chloric acid. s 2232 ABSTRACTS OF CHEMICAL PAPERS. Symmetrical tetrametliylbenzoylpropionic acid (from durene) melts at 117', and is decomposed in a similar manner, pentamethylbenzoylpro- p'ionic acid (white plates melting a t 104'), is also decomposed, whereas et hylbenzo y lpropionic acid, which crys tallises in slender, 1 u s trow needles, and melts at 90°, yields only traces of its decomposition products.Orthometlr y leth y 1 benzoy lpropionic acid, which €or ms very long, slender, lustrous needles melting at 78', and isopl.o~ylbenzoy~roptionic acid, crystallising in needles meltJng at 72', are both practically unacted on when heated with hydrochloric acid at 150', and about 50 per cent. of paramethylisopropylbenzoylpropionic acid (colourless plates melting at 70') is decomposed, after heating for nine hours a t 200" with hydrochloric acid. From these results it follows that only those acids are decomposed in which the side chain containing the carboxylic group is in the ortho- position relatively to one or both of the alkyl groups.By EMIL KXOEVENAGEL (Ber., 1896, 29, 172-174).--Ethylic acetoacetate and benzaldehyde in molecular proportion are mixed, cooled at - 5 O , piperidine (1 gram), diluted with two parts of alcohol, is added, and the liquid allowed to remain rtt the same temperature during 12-24 hours; the crystals are then separated and purified. The yield is 95 per cent. of the theoretical, and 100 grams of ethylic acetoacetate cau be conrenientlp eniployed at once. The action probably takes place in two stages, benzylidenedipiperidine, CHPh(C,NH,,),, is first formed, and reacts with the ethylic acetoacetate, piperidine being regenerated. Diethy lamino acts like piperidine. At the ordinary temperature, ethylic benzylidenediacetoacetate alone is formed from ethylic acetoacetate and beuzaldehyde. Tautomerism of the Orthaldehydic Acids.By CARL LIEBER- MANN (Ber., 1896, 29, 174-183) .-Opianic acid semicarbazone, COOH*C6H2( OMe),*CH:N*NH*COgNH2, is readily prepared by the action of opianic acid, in glacial acetic acid solution, on semicarbazide in aqueous solutiou ; on the addition of water to the glacial acetic acid solu- tion, it crystallises out in lustrous needles, melting at 1 8 i O . It quickly dissolves at the ordinary temperature in soda, and i n concentrated, but not in dilute, hydrochloric acid ; if the acid solution is immediately diluted, the compound is reprecipitated. When heated with glacial CO * r H CH:N * acetic acid, tlie semicarbazone yields opiazone, CsH2(OlMe)2< whilst boiling wl th concentrated hydrochloric acid converts the semi- carbazone into normethylopiazone, HO*C6H2(OMe) < :i.rH.Methylic n.opianate semicarbazone, C100Me*C6H2(0Me),.CH:NHC0.NH,, pre- pared from methylic n-opianate and semicarbazide, crystrtllises in needles, melts at 204', and is insoluble in cold soda. Ethylic 9-opianate slowly reacts with semicarbazide, and yields opianic acid semicarb- azone (see above) ; evidently the salt is slowly hydrolysed by the water, and the free acid then condenses with the carbazide. J. J, S. Preparation of Ethylic Benzylideneacetoacetate. J. B. T.ORCtANIC OHEMISTRY. 233 Pht halaldeh yd ic acid semicarbuzone, co 0R*C6H4* c H:N*NH* C O*NH2, prepared, like the opianic derivative, from phthalaldehydic acid, crysbnllises in needles, melts a t 202', dissolves in cold soda, and when boiled with glacial acetic acid, is converted into phthalazone.Opianic acid and phthalaldeliydic acid combine i n alcoholic solution, with various primary and secondary bases. The resulting compounds crystallise readily, are insoluble in soda at the ordinary temperature, and are resolved into their components when boiled with baryta water, and by the action of alcoholic, and generally of aqueous, hydrogen chloride, the latter giving first yellow compounds. Opianic acid a-n~ph- RA at 212'. The P-naphthylamide melts a i 213', dissolves, and gives an orange-red coloration with concentrated sulphuric acid, and, by the prolonged action of soda, (10-15 per cent.), is converted into the sodium salt, COONa*C6H2(OMe)2~CHtl:N*CloH7, which crystal- liseg in long plates ; the free Opi~n-P-~apht~~ylarn~c acid, prepared by the cautious additiou of acetic acid to the sodium salt, is unstable, and melts and decomposes a t 195-000'.Hydrochloric acid gives a yellow coloration, wliiali rapidly disappears, probably indicating the formation of a hydrochloride, subsequent additions of acid momen- tarily restore the colour, and, finally, the greater portion of the sub- stance dissolves. The methylic salt, COORle*C6H2(0Me),*CH:NCloH,, is prepased from methylic n-opianate and P-naphthylamine ; i t crys- fallises in plates, and melts at 131'. The ethylanih'de, crjstallises in plates, melts at 116--117O, and, by the action of ammonia, is resolved into its components. The tetrahydropuinolide, co--- C6&(OMe)2<CH (cyNH,,)>O, is sparingly soluble, and me'tts at 180'. The tetrahydroquinaldide, C6H2( OMe)2<CEI(C NH >0, melts a t 180", gives a yellow coloration with sulphuric acid, and is only slowly decomposed by ammonia. Phthalaldehydic acid tetrah ydropuiiml- ide, C6H~<cH~cyNH,,)>0, crystallises in needles, and melts at 164-165'.The preceding results sliow that towards semicarbazide, opianic acid nnd phthaldeliydic acid react as true aldehydic acids, COOH*R*CHO ; to wards primary or secondary amines they react as hydroxyphthalidcs, R'<CH(OH)>O, if the amides are of medium basicity, but they do not react with feeble bases such a8 diphenylamine, nor with strong ones like piperidine, as in this case the tendency towards salt formation is tsoo great. Tertiary amines are without action on the aldehydic acids.It is possible that when opianic acid is dissolved in alcohol, some q-ethylic salt is formed, but this ex- planation of the results is scarcely satisfactory, as the p-ethylic salt is without action on P-naphthylamine under the conditions co - 10 12 co-- co--234 ABSTRAOTS OF OHEMIOAL PAPERS. described above, and the naphthylamide is formed if acetone or hot water is employed as solvent in place of alcohol. Probably the salt, CHO*R*COO*NH,R, is first formed, which, by condensation, is con- '''? CHINER' and then from this by vcrted into the closed chain, R"< the action of alkali, the salt COONa*R*CH:NR,, is produced. This is in accordance with the behaviour of the p-naphthylamide, and explains the difference between the primary and secondary amines; it is possible that the formulae given above for the amides may require amendment in this sense.S. B. T. Ethylic 2 : 4 : 6-Trinitrophenylmalonate. By C. LORIKG JACKSON and J. I. PHJNNEY (Bey., 1895, 28,3066-3067).-In addi- tion to the form that melts at 58' (not 59", as previously stated), there is a form which crystallises differently and melts at 64O ; this can be obtained from a solution of the first form by sowing in i t some of the crystals tbat melt at 64'. The authors have not yet been able to convert this second form into tho first, nor have they succeeded in again preparing the first by the action of picryl chloride on ethylic sodiomalonat e. Ethylic t~rinitrophenylmalonate, UsH2( N02),*CH (COOEt)2, IS - con- rerted by nitric acid into the white nitrite, melting at 109' ; prolonged heating with nitric acid oxidises i t to the farfronate, C6H2(N02)3*C(OH)(COOEt),, which melts at 117' ; and hydrolysis with dilute sulphuric acid converts it into 2 : 4 : 6-trinitt-o- phenylacetic acid, CH2(N02),*CH,*COOH, which melts alt 1 61°, and, when crystaliised from alcohol or water, loses carbonic anhydride and yields symmetrical trinitrotoluene.Condensation of Simple Ketones with Ethylic Succinate and with Ethylic Pyrotartrate in the presence of Sodium Eth- oxide. By HANS SYORBE (Ber., 1895, 28, 3191-3195; compare Abstr., 1895, i, 142 and 4lO).-In continuation of his work, the author has investigated the products formed by the condensation of benzophenone with ethylic succinate under the influence of sodium ethoxide.The chief product is ethyylic hydTogen diphenyZitaconate, CPhz:C(COOEt)*CH2*COOfl or CPh,:C (COOH)*CHz*COOEt; it melts nt 124.5--125*5', is not hydrolysed by boiling with hydrochloric acid, but with alkalis gives y-diphenylitaconic acid, which melts and decom- poses at 168-169'. A solution of bromine in chloroform has no action on the acid, but bromine in the Dresence of water convert8 i t CeHz (NO2)3*C (NO2) (c OOE t)2, C. E'. B. COOH*$lBr.CPh2 CH2*C0 - i n to p- brom 0- y d i p 71 enyi$aTaconic acrid, >0, which melts at 166.5O with liberation of gas. Wheu reduced, the bromo- acid yields diphenylparaconic acid, and, when boiled with water, the corresponding aconic acid. N o acid isomeric with diphenylitaconic acid could be isolated from the products of the action of benzophenone on ethylic succinate.Benzophenone, when treated with ethylic pyrotartrate in a similarORGANIC CHEMISTRY. 233 manner, gave ethylic hydrogen a-metkyl--pdiphett y litaconate, which melts at 143.5-144.5'. When hydrolysed, the ethylic salt yields the corresponding acid, CPh,:C( COOH)*CHMe*COOH, which melts and decomposes at 179-180'. Dibenzyl ketone and ethylic succinate, in the presence of sodium ethoxide, gave the monethylic salt of the dibasic acid, The acid melts at 146-147', and the ethylic hydrogen salt at The author is at present engaged in tryiug to find ont the constitu- Sulphamic acids of the Aromatic Series. By CARL PAAL and H. JANICKE (Bsr., 1895, 28, 3160-3167 ; coinpare Abstr., 1894, i, 365) .-Ammonium phenylsulphamatct, NHPh*S03*NH4, crystallises in white, satiny plates melting at 152'.Orthotoluidine amidosul- phonate forms colourless prisms which melt a t 131O. Ammonium orthotolylsulphamate crystallises in concentrically grouped, white needles which melt at 241'. Pnratoluidine amidosulphonate forms lustrous plates me1 ting at 139'. Ammonium paratolylsulphamate c:*ystallises in lustrous, white plates melting at 215'. Paratolylsulph- amic acid, C6H4Me*NH*S03H, crystallises in concentrically grouped, white needles which melt indefinitely at 175-190'. When the aque- ous solution is heated for some time, toluidine sulphate is formed. Sodium nitrite reacts with the aqueous solution to form a white, crys- talliiie salt, which is probably the corresponding sodium nitrosamine- sulphonate.a-Naphthylamine amidoszdphonute crystallises in lustrous plates. Ammonium a-naphthylsulphamate melts a t 245'. a-Naphthyl- sulphamic acid cr*ystallises in colourless, flat needles which melt and decompose at 272'. as- Met16 y lpheit ylhydrazine amidcsu &phonate crystal- lises in lustrous, white plates melting at 106°,whilst the correspondiDg a ~ m n onium met hy lpheny 1 h y d yazinesulphona te, NMe P h*N H*S 03*NH4, melts :kt 217'. as - Diphenylhydrazine amidoszclphonate melts at 120--121°. It has not been found possible to convert this salt into the carresponding ammonium sulphamnte. Amylamine anzidoszclpho7~- at@ crystallises in large, transparent tablets and melts at 185O. Amyl- amine amylsulphamnte, C5HII*N~*SO3H,NHZ*C5Hll, is obtained by heating the nmidosulphonate with an excess of amylamine at 190- 200°, and forms lustrous plates melting at 110'.Isatin. EDWARD SCEUNCK and LEO MARCHLEWSKI (Bey., 1896, 29, 194-203).-When acetylisatin is warmed with 1 : 2-phenylene- diamine in alcoholic sotution, amidoacetylphenimeisatin, No isomeric acid was obtained. C(CH2Ph),:C (COOH)GH,*COOH. 127.5-129". tion of the ethylic hydrogen dipheuylitaconate mentioned above. J. J. S. A. R. NAc<g$!> C:N*CsH4*NH2, * is formed ; this melts at 285-286' (not 260-261'), and is soluble both in acids and in alkalis. Prolonged boiling with alkaline hydr- oxides-converts it into yellow 2-amidopheni.rneisatin,2313 ABSTRACTS OF UEEMICAL PAPERS. which melts at 260-261°, and dissolves both in alkalis aiid in acids, yielding even a crjstallised hydrochloride.This substance yiclds azo- dyes ; boiling with acetic anhydride converts i t into the acetyl deriva- tive described above ; and the action of acids-the mere crystallising from hot acetic acid suBces-gives rise to the formation of the sub- >C6H1, previously obtained from isatin :tnd 1 : 2- stance I phenylenediamine, and called isatohydropheiiazine (this vol., i, 96), but which it is now proposed to name itidophenazine ; the scheme of numbering proposed for the derivatives of indophenazine will be found ad joined. CsH4* y:N NH -C:N 4 N 4" 1' 3-Hethylindopheizazine is obtained from methylisatin and ortho- phenylenediamine ; it is yellow, and melts at 2-48' ; its white 1'-ucetyl derivative melts at 2 0 4 O .1 : 3-Dibromindophenazine, from dibromisa- tin, is orange coloured, and melts a t 275"; its l'-acetyZ deriuatircz is yellow. Nitroindopheizazine, from nitroisatin, is yellowish-brown, and has not melted at 305'; its acetyl derivative is yellow. Acetylisatin, unlike isa tin itself, yields ;I diozime, which melts and decomposes at 240". Displacement of Isodiazo-groups by Cyclic Radicles. 11. By OTTO WHLIXC; (Be,.., 1896, 29, lG5-169 ; cornpare Rbstr., 1895, i, 182 and 290).--The author fitids that in the paranitrophenylpyri- dine, described in his previous pnpcr (7oc. c i t . ) , the nitrophenyl group isin the a- and not in the yposition as stated. Sodium nitrophenglnitrosamine and iiitrobenzene react in the presence of acetic acid to form 4 : 4'-dinitrodiphenyl (m.p. 233"; compare Fittig, AnnuZen, 124, 276) and 2 : 4'-dinitrodiphenyl. The nitrophengl toluene, of melting point 103-104° (compare Bambergcr and also Kuhling, Abstr., 1695, i, 182, 289), is probably the dipara- compound, and the oily isomeride probably the orthopara-compound. ParanitrophenylLe,Lzoic acid, [? 4' : 41, is obtained on oxidising t,he solid nitrophenyltoiuene with excess of potassium permaiiganate ; it crystallises in colourless needles, melts at 222-225', and is only sparingly soluble jn water, but readily in hot alcohol. When reduced with tin and hydrochloric acid, it yields para?nidoiwhenyZbenzoic acid hydrochloride. The f r e e acid, NH2*C6H4*CSHI*COOH [P 4' : 41, crys- tallises in small needtes or thin plates, melts and decomposes at 106-110°, and is only sparingly soluble in hot water.Paramido-a-phen yi@ yridine hydrochloride, NH2*C6HA*C5NH4,2HC I, obtained by the reduction of the corresponding nitro-compound, forms a colourless, microcrystalline powder, arid the picrate crystallises in C. F. If.ORGAN10 0 HEMISTRY 237 vellow pi-isms which melt at 2 1 0 O . The base itself crjstallises in small, khite plates which rapidly turn red, and melts at 101-102°. Whet) the hydrochloride, in alcoholic solution, is treated with sodium nitrite, i t yields 2-phenylp~ridi;ie (compare Skraup and Cobenzl, Abstr , 1883,1015). Sodium nitrophenylnitrosamine and quinoline condense in the presence of acetic acid to Eorm paranI:trophon2/Iquiiioline, whicli separates from its alcoholic solution in the form of yellow, crystalline aggregates, and melts a t 158--260°.It is soluble in strong acids, yielding yellow solu tioiis. Paranit7-ophenyZnayIr thalene, obtained by a similar method, crystal- iises in bright orange needles, melts at 129O, and is practically insolublc in water, but ibeadily soluble in ether. Formation of Phenylparatolylmethane by the Action of Sodium on Parabromotoluene. By MAX WEILER (Bey., 1896, 29, 121-114).- -When parabrorno- or pariodo-toluene is treated with sodium, a certain amount of toluene is produced dong with hydro- carbons of' high boiling point., t w o substances being formed, one of which is identical with paraditolyl. The second has not j-et been obtained pure; it is contained i t ] the fraction boiling a t 286--293O, and yields paratoluic acid when oxidised with excess of chromic anhydride.If, however, it is oxidised with the calculated amount of chromic anhydride, it is converted into a ketone, which yields an oxime melting at 145-150°, and is probably yaratolyl p!imy1 ketone. The second hydrocarbon must, therefore, be phenylparatolylmethane. J. J. S. A. H. Phthale'ins. By JOSEP HEKZIG and Hass MEYE& ( 5 e r . , 1895, 28, 3258-3261) .-By tlie action of methylic iodide on phenolphthaleh in alkaline solution, 85-90 per cent. of the lrrctone dimethylic ether is formed ; this is scarcely compatible with Friedlander's forniula for the sodium salt. Several theories of its formation are discussed ; a t present8, the authors, following von Baeyer, suggest that the decolorisa- tion of phenolphthalezn solution by means of alkali in excess, is due to the formation of a salt of the acid C20H1605; the regeneration of the colour, when the liquid is heated, being caused by the dissociation of this h a l t .Friedlander has described the acetyl derivative of phenolplithale'in oxime as insoluble in alkali ; but tliis is inconsistent with his formula for i t ; the bubstance prepared by him appears to be A mixture of two or three compouads, and is being further investi- gated. Quinoidal fluorescein ethyl ether yields a motmcetyl derivative which crptallises i n highly coloured, yellowish-brown needles melting a t 188-190". Nietzki and Schroeter prepared yellow fliiorescein ethylic ether by the hydrolysis of the quinoidal diethylic derivative, and found that it gives il colourhss, acetyl compound ; this work has been repeated, and it is found that both the diethylic and ethylic! acetyl derivatives, when treated with alcoholic potash and acidified, give a yellow precipitate, the supernatant liquid being fluorescent.On extrachion M i t h ether, the solid dissolves, and, alter the ether is removed, a white, somewhat nnstable compound is obtaiiied ; this gradually becomes ello ow by repeated recrystallisation, but t h e238 ABSTRACTS OF CHEMICAL PAPERS. change is more rapid when the substance is heated, and, at 250°, i t melts, forming an orange-coloured liquid. The subject is being further in ves tigatsd. J. B. T. Phthaleins. By JOSEF HERZIG and HANS METER (Ber., 1896, 29, 138--139).-ln their preceding paper, the authors failed to mention that Haller and Guyot (Ahstr., 1895, i, 376) had already obtained the lactone diethyl ether of phenolphthaleh.The authors do not agree with those authors' views as to the quinoidal constitiition of the alkali salts of the plithnle'ins. By 1 .- ited J. J. S. Constitution of the Alkali Salts of Phenolphthalein. AUGUSTIN BrsTRzYctir arid K. NENCKI (Bet-., 1896, 29, 13 with benzoic chloride, according to Schotten's method, When phenolphthalein is dissolved in aqueous potash a 3lJl- phenolphthalein, CO<oG-> c H, C(C6H4*OB~)2, is formed. It crystal- lises from benzene with 1 mol. of the solvent, in small, colourless prisms, melts when pure at 169O, and is insoluble in dilute alkalis. The potassium salt derived from phenolphthalein, therefore, reacts in aqueous solution as though it had the formula and not the alternative quinoidal formula, suggested by Bernthsen.A. H. Diphe n ylene Ketone and Pseudodiphenylene Ketone. O:C, H4:C (C,H**OK)*C,H4*COOK, By WILHELM KERP (Ber., 1896, 29, 2'28-233).-The anthor has investi- gated the red compound (pseudophenylene ketone) obtained, together with phenglene ketone, on distilling calcium diphenate (Fittig, Annalesa, 166, 373; 193, 117; Schmidh and Schultz, ibid., 207, 345). The distillate forms a yellowish-red, crystalline mass of the formula CI2H8:CO. The t n o compounds may be separated by means of dilute alcohol ; the red compound crystalliaes from its ethereal solution in dark red, compact crystals, melts at 85O, and has the same percentage composition as diphenylene ketone (m.p. 83-83p). Both have the same molecular weight, and the pseudo-ketone can readily be converted into the ordinary ketone either by exposure to direct sun- light for several hours, or by treatment with boiling dilute alcohol, steam, or warm sodium ethoxide. In all these decompositions, how- ever, a second red compound is formed, but only in very srunll quantities; it is still solid ah 250°, and is insoluble in alcohol, ether, acids, and alkalis. If heated with alcohol at 300°, the pseudo-ketone is converted into fluorene alcohol. Both the ketone and pseudo-ketone yield tbe same fluorene alcohol on reduction ; they also give the same oximes, and on fusing with potash the same phenyl- benzoic acid ; these results are, beyond doobt, due to the conversion of the pseudo-ketone into the ordinary ketone.On treatment with zinc chloride, the oxime, which melts at 195"ORGANIC CHEMISTRY. 239 (Spiegler, Abstr., 1884, 1182, 192'), yields phenanthridone (Pictet, Chern. Zeit., 1894, 1822), and on reduction is converted into diphenyl- enernethylami?te, CIaHls:CH*NH, ; the latter crystallises in colourless needles, melts at 161°, and is moderately solub!e in warm water. Ammonium formate reduces both ketones, yielding a mixture of hydro- carbons, among which are, probably, diphenyl and fluorenc. Accord- ing to Schultz (Annaleit, 203, 103), the ordinary ketone yields a mononitro-derivative when treated with cold, fuming, nitric acid and a dinitro-derivative (rn. p. 290') with warm acid; the author shows that the pseudo-ketone with ice cold nitric acid vields a dinitru- which cryshallises in srnall, yellowish needles, melts i t 310", arid is insoluble in most solvents.J. J. S. Hydroxybenzylideneacetophenone. (Phenyl Orthohydroxy- styryl Ketone). By HERMBNX BABLICH and STANISLAUS VON KOSTA- NECKI (Ber., 1896,29,233-236).-0rthohydroxybenzyZideneacetophenone i8 best obtained by dissolving salicylaldehyde (1 part) and acetophenone (1 part) i n alcohol (6 parts), and then treating with sodium hydroxide (1. part) dissolved in n small quantity of water. After 24 hours, the mixture is poured into water, when orthohydroxy benzylidenediaceto- phenone (see next page) is thrown down ; orthohydroxybenzylidene- acetophenone remains in solution as its sodium salt, and may be pre- cipitated on tbe addition of acid ; after thoroughly washiiig, and re- crysta!lising from alcohol, i t forms yellow plates, and melts and decomposes at 153-155'.It dissolves in dilute sodium hydroxide, yielding a yellowish-red solution, and, on adding concentrated alkali to this, the sodium salt separates in the form of orange-coloured needles. The acetyl deriratire, OAc*C6H4*CH:CH*COPh, crystallises in small plates, and melts at 68-69'; when dissolved in chloroform, it readily takes up two atoms of bromine, forming orthacefo~llb~nzyZidei2euc~~o- pheizone dibyornide, which is sparingly soluble in alcohol, crystallises in colourless prisms, and melts a.t 134-135'. Met~h~d~o~ybenzy~ideneace~ophenone cr~stallises in colourless plates, melts at 159-16U0, and is t-cadily soluble in alcohol, benzene, and chloroform, somewhat more sparingly in ca.rbon bisulphide ; its acetyE derirative melts fit 102-103', and the dibronzide of the latter at 170-171".The dibromide can be reconverted into metacetoxyhenzyl- idem acetophenone by treatment with copper powder. Parah ydrox!lbenzylidenencetophenone forms yellowish crystals, melts at 182-183.5°, and dissolves in dilute alkali, yielding a deep yellow solution. Its acetyE derizmtive melts at 129-131', and the dibromide of this at 148'. J. J. S. Phenyl a-Coumaryl Ketone. By STAXISLAUS VON KOSTANECKI and Josw TAMBOR (Bsr., 1896, 29, 2%'-239).-When ortliacet- oxybenzylidenelacetophenone dibromide (see preceding abstract) is dissolved in alcohol, the warm solution treated with strong potash solution, and then poured into water, a crystalline precipitate is obtained.This has the composition C1JH,o02, distils at 360' without240 ABSTRACTS OF CEEMIaAL PAPERS. decomposition, melts at 91', and dissolves in concentrated sulphuric acid, yielding a yellow, non-fluorescent solution ; when fused with potash, it yields coumarone and benzoic acid, C,,H,,O, + H,O = C8H60 + Ci;H5*COOH, its constitution is, therefore, that of p h e i ~ y l a-couma t y 1 ketone, CsH,< cs>C OCO P h , Pard oZy 1 I ) rthohyd~ozystyry l ketone, 0 H*csH,*C H:C H*C 0 C6H4SIy, !nay be obtained from salicylaldehyde and methyl paratolyl ketone In the same way as orthohydroxybenzjlidene acetophenone Prom sali- cylic aldehyde and acetophenone (set! preceding abstract) ; it forms yellowish plates, melts a t 1 5 2 O , and is soluble iti alkalis aud concen- trated sulphuric acid.I t s acetyl dei-iuative melts at 112', and the dibromide of this at 136-137'. The latter compound, when dis- solved in alcohol and treated with concentrated potash, yields part&- ; this melts at 9So, and yields coumarone and paratoluic acid when fused with potash. J. J. S. Action of Aldehydes on Ketones. ]By ARNOLD CORNELSOX :tnd SrANrsLAus VON KOWANECKI (Ber., 1896, 29, 240-244 ; compare Schmidt, Abstr., 1881, 573, Claisen and Ponder, Abstr., 1884, 1166). -In the condensation of salicylaldebyde with acetone or with aceto- phenone, it is necessary to use a much more concentrated solution of sodium hydroxide than in the usual condensations of aldehydes with ketones. With acetophenone and salicylaldehyde, besides the.ort ho- hydroxybenzylideneacetophenone (compare Bablich and Kost anecki, preceding page), the authors have obtained a second compound which crystalliees from alcohol in colourless needles, and is quite insoluble in alcohol, the amount formed increasing with the amount of alkali used i n the condensation.It can also be obtained by the action of acetophenone (1 mol.) on orthohydroxybenzylideneacetophenone in the presence of alkali, and is, beyond doubt, orthoh?/d,.oxybe?zzil- idenediacetophenone, OH*C;,H,*CH( CH,*COPh),. It is best prcparvd by the action of salicylaldehjde (1 part) on acetophenone (2 parts) dissolved in alcohol (10 parts), and then adding a solution of 2 parts of sodium hydroxide in 2 parts of water.After recrystal- lisation from alcohol, it forms thin prisms, which melt a t 131'; i t is readily soluble in dcohol, benzene, and chloroform, but insoluble in alkalis. When boiled with an alkali, it is decomposed into nceto- pheuone arid salicylaldehjde. 0 t d y t a-cozcmaryi ketone, C ~ & < C ~ > C * C O * C ~ H & ~ 0 Its ncetyl dei*ivatice, 0 Ac* C6H1* C H ( C H2*C OP h) 2, ci*ystalli~es in colourless needle$, and melts at 83-84°. Orthohyd~o~~cybenzylident.b~srneth~lparatoly1 ketone, OH*C6H1* CH (C HI,-C0.CfiH4Me),, was obtained as a bye-product in the preparation of paratolyl liy- droxystyryl ketone (compare Kostanecki and Tambor, preceding abstract). It crystallises in colourless prisms, and me1 ts at 131-132c its acetyl derivative melts at 953.ORQANIO OHEMISTRP.241 B~v~iaorthohydrox~bc~zzyl~de~z ediacetophenone, OH*C16H,BroCH(CH,*COPh), [OH : Br = 2 : 53, is formed as a bye-product in the preparation of bromorthohydrosy- benzylideneacetophenone (compare Kosfanecki and Oppel t, following abstract) ; it crystallises i n colourless needles, and melts at 158-15g0-: its acetyl deg.i2*nfic*e melts a t 107O. J. J. S. Derivatives of Orthohydroxybenzylideneacetophenone (Phenyl Orthohydroxystyryl Ketone). By S'rANTsLAus VON KOSTA- KECEI and EUGEN OPPELT (Ber., 1896, 29, 244--249).--5 : 2-Rromo- hydroxybenzy Eideneacetophenone, OH*C6H3Br*CH:CH*C O P h, is obtained by the action of bromosalicylaldehyde (8 parts) on acetophenone (5 parts) in the presence of an alkali. A small quantity of the cor- responding diacetophenone is formed at the same time (compare preceding abstract).It crystallises from its alcoholic solution in yellowish plates, melts and decomposes at 1 6 8 O , and is soluble in both alkalis and strong sulphuric acid. The sodium salt i s readily soluble in water, but, on the addition of more alkali, separates out in the form of glistening, red needles. The neetyl deriuative, obtained by the action of acetic anhydride and anhydrous sodium acetate, forms glistening needles, melts at 133.5--135°, and yields n dibroml'cic which melts at 158-1fiOo. 5 : 2-B~ometho~rybenzylidenencsto~helzone,OEt.CGH3Br~CH~C~~COPh, may be obtained by boiling an alcoholic solution of the brom- hydroxy-compound with ethylic iodide and potassium hydroxide ; it. may also be obtained from bronaethoxybenzylideneacetophenone dibromide, by treating it with a paste of freshly precipitnted metallic copper, but is best prepared from the ethylic ether of salicylic acid and acetophenone under the influence of an alkali.It forms yellowish needles, melts at 98-100°, and is readily soluble in warm alcohol. The dibromide may be obfained either by the addition of two atoms of bromine to the ketone, or by the actionof bromine on a solution of the crude ethylic ether of orthohydroxybenzylidensacetophenone in carbon bisnlphide. Ortho bromopheq 2 a-wozc~i~ ar yl ketone, C6H3B r< EG> Co C 0 Ph, is ob- tained when the bromacetoxybenzylideneacetophenone dibromide is suspended in warm alcohol and then treated with concentrated alkali. It crystallises in yellowish needles, and melts at 136-138O.It crystallises in plates, and melts at 16.5'. J. J. S. Action of Diphenylene Di-isocyanate on Amido-compounds. Bp H. LLOYD SNAPE (Chew. News, 1896, 73, 3?).-when diphenylene dicyanate, obtained by heating benzidine hydrochloride in a current of phosgene gas, is treated in ethereal solution with gaseous am- monia, it yields diphenylenedicarbamide (H. Schiff, Abstr., 1878, 669) ; whilst, if an ethereal solution of aniline is used, dipheayldi- phenylenedicarbamide is formed, identical with that produced from benzidine and phenylic isocyanate (B. Kiihn, Abstr., 1885, 979). D. A. L.242 ABSTRAOTS OF OHEMIOAL PAPERS. Diphenyldiphenylene-ethylene. Br VICTOR KAUFMANN (Ber,, 1896, 29, 73-76) .-~)iy~ienyldiphenylene. ethylene, Q"'>C:CPh2, is CiiEf4 obtained by heating benzophenone chloride and fluorenc in molecular proportion at 320-330" for 5-10 minutes ; it melts a t 229*5", and crystallises from benzene in colourless leaflets or needles contain- ing the solvent.Reduction of the arnylic alcohol solution with sodium amalgam gives rise to dil3henylciiphenyleile-ethane, which crys- tallises from benzene in leaflets containing 2 mols. of the solvent ; it melts at 217-218'. The picrate of diphenyldiphenylene-ethylene crystallises from benzene in yellow needles, and melts at 198O. Behaviour of Stilbene Dibromide and of Tolane Dibromide with Sodium Benzenesulphinate and Sodium Phenylmercapt- ide. By ROBERT OTTO (J. pr. Chem., 1896, [a], 53, 1-19 ; compare Abstr., 1895, i, 286, 485).-Neither stilbene dibromide nor the corre- sponding tolane derivative is converted into a sulphone by sodium benzenesnlphinate ; instead, stil bene dibromide yields stilbene, and p-tolane dibrornide yields tolane ; tolane and b e n d were obtained when a-tolane dibrornide was employed. Stilbene and tolane are the products of the action of sodium phenylmercaptide on the aforesaid dibromides.A. G . B. M. 0. F. Connection between Colour and Constitution in the Tri- phenylmethane Dyes. By WILHELM VAUBEL (J. p. Chem., 1896, fa], 53, 4 7 4 8 ; compare Abstr., 1895, i, 55-56).-The author defends his views concerning the relation of the colour of triphenyl- methane dyes and their constitution against the criticism of Richard Meyer in the Juhrbuch dsr Chemie, 1894. Hydrocarbons of High Molecular Weight produced by the action of Sodium on Bromobenzene.By MAX WEILER (Ber., 1896, 29, 115-118; compare this POL, i, 237).--The formation of hydrocarbons of high molecular weight appears to be a normal accompaniment of the action of sodium on brominated aromatic hydrocarbons. The product of the action of sodium on bromobenzene yields UI series of compounds which boil above 342", and of wliich the molecular weight exceeds 200. A number of crystalline substances has been isolated from the various fractions, but no attempt has yet been made to ascertain the constitution of the products. By RICHARD MOHLAU and FELIX KEIEBEL (Ber., 1895, 28, 3089-3096 ; compare Abstr., 1894, i, 138).--l-Naphthaleneazo-2-hydroxy-3-naphthoic acid forms deep red crysfals with a greenish-yellow surface lustre, and decomposes at 182".1 : 2 : 3-amidohydroxynaphthoic acid forms yellow, rhombic prisms, and decomposes at 205.5" ; it can also be obtained by rednc- ing von Kostanecki's 1 : 2 : 3-uitrosohydroxynaphthoic acid (Abstr., 1894, i, 91) with stannous chloride. 1 : 2 : 8-Dihydroxynaphthoic acid melts and decomposes a t 220.5" (not at 207") ; its yellow ethylic and methylic salts melt respectively at 84-84.5" and at 95-96' (for A. G. B. A. H. 1 : 2 : 3-Dihydroxynaphthoic acid.ORGANIC OEEMISTRY. 245 the latter substance compare Gradenwitz, Abstr., 1894, i, 605). When this acid is oxidised with nitric acid of sp. gr. 1.2, it yields 1 : 2-naphtha- quinoiae-3-carboxyEic acid, which crystallises in orange-red monoclinic prisms, and decomposcs at 154' ; its methylic salt, prepared by oxida- tion of the correspondiiig dihydroxy salt,, is orange-red, and begins to decompose at 12l0, melting at 1~39---140'(compare Gradenwitz, loc.cit.). 2 : 3-Amidonaphthoic acid. By RICHARD M~~HLAU (Be.., 1895, 28,. 3096-3099 ; compare Abst,r., 1894, i, 138).-This acid is best obtained by heating the sodium salt of the corresponding hydroxy- acid with ammonia in an autoclave a t 260-280O; i t melts a t 214O, (not at 211-212') ; the colourless 2-ucetamitlo-derivative melts at 238O, the yellow .methylic salt nt 115-115*5. When a mixture of 2 : 3- amidonapthoic and 2 : 3-hydroxynaphthoic acids with ammonia atid zinc chloride is heated at 260-280°, a yellow dinaphthncridone, C,HG<NH>C~oH6, melting above 300', is formed.C. F. B. c. F. €3. co Constitution of 2 : 3-Hydroxynaphthoic acid and its Deriva- tives. By RICHARD MOHLAU (Ber., 1895, 28, 3100-3101).-2 : 3- Hydi*oxyna2hthoic acid is coloured and so are its salts, but when the hydroxylic hydrogen is replaced, colourless compounds are formed. The same is true of the hydroxy-, amido-, and sulphonic derivatives of this acid. The colourless compounds may be regarded as derived CH:Ci]*OH the coloured ones CH:CCOOH ' from the true hydroxy-acid, CGH1< CH2*QO CH: CGOOH' from the desmotropic isomeride, C6H4< In the same way, the colourless salts of 2 : hmidoiiaphthoic acid are to be regarded as derived from the normal acid, CH:Y*NH, C 6 H d < ~ H:C.COOH ; the acid itself and its salts, being coloured yellow, from the desmo- tropic form, CGH,< >o* CH,.Ci]:NH C H2*Q:NH2 CH: C*CO or c6&< CH: C*COOH C. F. B. Constitution of 2 : 3-Hydroxynaphthoic acid. By MARTIN SCHOPFF (Ber., 1896, 29, 265-270) .-Mohlau has recently sug- gested (preceding abstract) that 2 : 3-hydroxynaphthoic acid is really a keto-derivative [CH, : CO : COOH = 1 : 2 : 31 ; the author reached the same conclusion some time ago, chiefly from a study of the action of phenylhydraziiie on the acid. When heated at 130-140°, they combine, ammonia, water, and pheizylnaphthy Iccrrbazolecarboxylic acid, C1,HllN02, being formed ; the latter crystallises in yellowish- green needles, melts at 325', and is very sparingly soluble. The ethylic salt crystallises in yellow needles, melting at 175'. The sodium Ralt is deposited in silvery, lustrous plates, and becomes yellow a t 100'. The barium, magnesium, and calcium salts are yellow and sparingly soluble.The acetyl derivative is crystalline, insolnble in alkali, and244 ABSTRACTS OF' CHEMICAL PAPERS. remains numelted at 350'. Pheri2ylnaphthylcarbazole is formed by dis- tilling the acid with zinc dust, in a current of hydrogen ; it crystallises from light petroleum, melts at l'tOo, and, in solution, has a hlue flooi*escence; n pine splinter, treated with tlie carbazole and then with hydrogen chloride, is eoloured violet. The picrate is crystal- line, The rizitroso-derivative crystallises in small, yellow needles, melts at 132", gives Liebermann's reaction, and produces a green coloration with concentrated sulphuric acid.The ucetyl derivative c~ystalIises in silvery, lustrous plates, and melts at 142'. The benzoyl derivative is deposited in slender, colourless needles, melting a t 170'. The reactioii between phenjlhydraxine and the naphthoic acid probably takes place in two stages, a hydrazone, COOH*C,oH,:N*NHPh, being first formed, and then the carbazoiecarboxylic acid, I I Some 1 : 2'-Derivatives of Naphthalene. C kl*C6H4- g-QeH4 C(COOH)*C--NH J. B. 1'. By PAUL FRIED- LAERDEK and s. ZtNUERG (Be?.., 1896, 29, 37-42).--The sodium hydrogen and bankm ltydrogeriz salts, both with GH20, of h ydroxydi. sulphonayhthoic acid [OH : COOH : !SOJ3)2 = 1 : 2 : 4 : 2'1 (Ktinig, Abstr., 1889, 729) are described. When the acid is fused with sodium hydroxide nt 220--240°, it is converted into 1 : 2' : 4-tZihydyoxy- sulpho-2-~tapl~fltoic acitl, the sodiiirn hydrogen, and acid aniline salts of which were prepared; heRting with 50 per cent.sulphuric acid at 140' converts this acid into 1 : 2'-dChydrozy-2-naphthoic acid, which melts and decomposes x t 217", and the barium salt of which crystal- lises with 4H20. The latter acid, when boiled with aniline, yields 1 : S'-dihydroxynaphthalene (Emmert, Abst r., 1888, 57), nieltirig at 175' ; concentfated aqueous ammonia converts it at 200-210° into 1 : 2'-naphtbylenediamine ; al: 170-180° into 2' : 1-amidonaphthol (Abstr., 1802, 1234), the acsfyl deyivatice of which melts at 210-211°. 'I'he isomeric 1 : 2'-amidonaphthol was prepared by heating 1 : 2'- naphthylaminesnlp'honic acid with sodium hydroxide a,t 250-260O ; it forms pale, brownish needles, and decomposes above 200'; its ctceLyZ deyimtiz.e melts atl 165'.Menthol. By ERXST J ~ ~ K G E R and A. KLAGES (Ber., 1896.29, .314-- C. F. B. CH2*CHMe *vH2 ' CH2*CHPrfl*CH*OH 318).-In orclei= to establish the formula I for menthol (compare Abstr., 1893, i, 359), the authors have converted menthone into dichlorohexahydrocymene, and by elimination of hydrogen chloride obtained chlorotetrahydrocymene, which probably CH *CC1 has t.he constitution CHMe< cH:,CH2>CPrfl ; treatment with bro- mine and quinoline converts this substance into S-chlorodihydro- cymeue, from which 3-chlorocymene is obtained, the chlorine atom occupying the position originally assumed by the hydroxyl group in menthol. ] t i order to identify the cymene derivative thus obtained, the two chlorocymenes have been prepared and characterised.2-Chlorocymene is produced by the chlorination of cymene obtained from camphor ; i t boils at 117.5' under a pressure of 35 mm., and at9RGANIC CHEMISTRY. 245 P1-fi-216° under atmospheric pressut-e. The sp. p. = 1,017, and the rzfractive index 12n = 1.51118 at 17'. ~ - C h l o r o c ? ~ n t ~ n e - 5 - s u l ~ l ~ o ~ ~ i ~ acid crystallises from benzene in colour- less needles, and melts at 135-1.36' ; the bnrizsnz salt ci-ystallises in leaflets which contain water, and the chloride, anzide, and nniZide melt at 68-69', 191--192', and 18 1' respectively. ;!-Clilorocymene is obtained by the action of phosphorus penta- ehloiside on thymol; it boils a t 214", has sp.gr. = 1.018, and the refractive index w,D = 1.51796. The sidphoizanzide crystallises from dilute alcohol in nacreous leaflets, and melts at 168' ; the bari?cm salt of the sulphonic acid crystallises i n needles, mid contains 4?H[,o. Ciiloyotetrahyclrocymene, CloH&I, is produced by the action of phosphoric chloride on menthone (Abstr., 1892, Stj7), and quinoline converts its bro mo-der i va tive in to c hZorodihylx7mc ymene, C loH& 1, which boils at 112' under a pressure of 35 mm., and 212' under atmospheric pressure ; this substance has the sp. gr. = 0.990, and the refractive index nD = 1.49712. Treatment of chlorodihydro- cymene with bromine (1 mol.), and distillation of the product with quinoline, yields 3-chlorocymene, in every respect identical with the substance adready described.Hexahydrocymene, which is readily produced by the addition of sodium to an alcoholic solution of chlorohexahydrocymece (menthylic chloride), is identical with menthonaphthene, described by Berken- lieim (Abstr., 1892, 866), and also with the menthane of Wagner (Abstr., 1894, i, 469). Orientation in the Terpene Series : Carone and Pinene. Bg ADOI.E' vos BAEPER (Bey., 1896, 29, 3-26 ; compare Abstr., 1895, i, .549).-The evidence afforded by Wagner (Abstr., 1894, i, 469), and more recently by Wallacli (Abstr., 1895, i, 547), in favour of repre- senting terpineol by the formula CMe<cH,,CH, CH CHz>CH*CMe,*OH, has demanded a re-modelling of the author's system of orientation in regard to almost all menibers of the terpene series excepting those of the terpinolene group.Whilst admitting tbe accuracy of Wagner's formula for terpineol, terpin, limonene, carvone, and dihydrocarvone, Tiemann and Semmler regard pinene as having the constitutiou C!H------- C H 2 5 C (Abstr., 1895, i, 428), basing this hypothesis on the behaviour of pinonic acid towards oxidising agents (Abstr., 1895, i, 477). The author, however, has oxidised pinene in the manner indicated by these investigators, and obtained pinonic acid in a form which, although having the empirical formula CI0HI6O3, and boiling at the temperature observed by them, becomes crystalline very readily, and, on oxidation with alkali hypobromite, jields a dibasic acid of the composition C,Hl,04, to which he refers as pinic wid. This behaviour is not in agreement with the foregoing expres- sion, and pinene must, therefore, be represented by the formula M.0. F. ,C&- 'CMe,*CHhle' ,CH2-CH. CH/ CH,< )CXez, already advocated by Wagner (Zoc. cit.). \CMe-CH YOL. LXX, i. t24 6 ABSTRACTS OF OHEMXCAL PAPERS. T b e production of li ydrobromodi hy drocttr vone arid h ydroxy te t ra- hydrocmvone, by the addition of the elements of hydrogen bromide and of water to carone, meets with explanation if the constitution of the latter substance is expressed by the formula I > CILIez (compare Abstr., 1895, i: 551) ; this view removes the author's objec- tion t o Bredt's formula for camphor, which he now regards as more probable than the expression advocated by Tiemann (Abstr., 1895, i, 428). The conversion of carvone, limonene, terpineol, pinene, nitroso- pinene, and isocarvoxime into hydrochlorocarroxime by a method described in t.he present paper, is regarded as justifying the classifi- cation of these substances in one natural group.It has been already mentioned that hydroxytetrahydrocarvone is formed by the addition of the elements of water to carone. Carone- bisnitros~lic acid. also. when dissolved in alcohol artd submitted t o CHMe*CO*Q H CH2-C H2* CH the actio; of a current of steam, yields 8-hydl.oleytet~ahydroea~vonebis- ?zifrosy& ffcid, OH*C>fe2*CH<CH CH2*CH2>CMe*X202H2, 2- co which crystal- lises from dilute methylic alcohol in rhombic plates, and melts and evolves gas at 184'. Glacial acetic acid saturated with hydrogen brom- ide converts it into b i.onioteti.ah?l~?.ocal.~one bisnitrosy lic acid, c&f e2Br* C6H,(iMe*N202H2, which also crystallises in rhombic plates, and melts and decomposes ab 130' ; treatment with alcoholic potash regenerates caronebisnitrosylic acid.Hydrozyca?*one is obtained from bisnitrosocarooe dichloride and hydrobromodihydrocarvone dibromidc by the action of caustic. soda ; it boils at 125-135' under a pressure of 20 mm., and forms a crystalline sodium derivative. Hydroxycarone and ketoterpine, ob- tained by agitation with sulphuric acid, will be more fully described. Oxidation of eucarvone with potassium permanganate has led to the formation of asymmetric dimethylsuccitiic acid. When the a- and j3-modifications of d-limonene nitrosochloride are treated with alcoholic hydrogen chloride, active hydrochlorocarv-- oxime is produced ; the inactive modification is obtained, however,.from hydroclilorodipentene uitrosochloridc, terpineol nitrosochloride, pinene nitrosochloride, and nitrosopinene. The active hydrobromo- carroxirne is produced when a-dextrolimonene nitrosochloride is treated w i t h ethereal hydrogen bromide, whilst pinene nitrosochloride and terpineol nitrosochloride yield the inactive modification ; eucar- Tone, however, is indifferent towards this agent. On oxidising pinene, according to the method adopted by Tiemann and Semmler (Abstr., 1895, i, 477), the chief product obtained by the author is or-pinonic acid, C,,H,,O,, which melts a t 103-105', and boils at 180-187O under a. pressure of 14 mm. ; the oxime crystal- lises in large, transparent plates or prisms, and melts at 150', whilst t h e plie?tylhydmzonr~ crystallises from dilute alcohol in lustrous, colourless leaflets, which melt and decompose below 100'.This result is not in a p e m e n t with the observations of the above-men-ORGAN10 CHEJIISTRY. 241 tioned investigators, who obtained liquid pinonic acid, which boils at the same temperature as the solid modification, and yields two iso- meric oximes, melting a t 125’ and 160° respectively. A crystalline acid which the author calls nopic acid is another product of the oxidation of pinene, but it is not formed when the pure hydrocarbon is employed; it is isomeric with pinonic acid, but, unlike this sub- stance, it is not ketonic. Nopic acid melts at 125O, and the sodiujlt salt is spariugly soluble in water.Tiemann and Senimler have observed that pinonic acid is indif- ferent towards alkali hypobromite (loc. cit.) ; a-pinonic acid, how- ever, is readily oxidisod by this agent, yielding pinic acid, C,H,,Oa, which crystallises from water in long prisms, and melts at 101--102*5°. Pinic acid is dibasic, but does not form an anhydride under the influence of boiling acetic chloride ; the solution is slowly oxidiscd by potassium pernianganate on the water bath, but is indifferent towards i t at the ordinary temperature. Hydrobrornic acid has no action on pink acid at looo, and the aqueous solution is optically inactive. M. 0. F. Orientation in the Terpene Series. Menthone snd Tetra- hydrocarvone. By ADOLF TON BAEYER [and EGGEN OEHLER] (Ber., 1896, 29, 27-37 ; compare Abstr., 1894, i, 522, and 1895, i, 549).- 2 : 6-Dimethyl-3-oximidoctanoic acid, the open chain acid derived from nitrosomenthone by the addition of the elements of water, melts a t 1 0 3 O (compare Eoc.cit.). 2 : 6-L)inzet~yloctan-3-onoic acid, obtained by treating it witb boiling dilute acids, boils at 186--167° under a pressure of 20 mm. ; the semicarbazone crystallises in prisms and melts at 152O. Isobut?lrylmethylF:etqpentamethylene (I : 4-?izethylisobutoylcyclo~enta~ze- is formed when the ethylir: salt CH,-FO C K,*CH*CO*CHMe,’ %one), CHMe< of the foregoing acid is heated with sodium and xylem for three hours at 120-lYOo ; it is a colourless oil, boiling at 1L5-116° under a pressure o€ 25 mm., and develops a red coloration in alcoholic solu- tion with ferric chloride ; the copper derivative crystallises in bright green, silky needles, and compozmds are also formed with sodium hydrogen sulphite and ammonia.The dioxime crystallises in small needles, and melts at 144O. On heating the diketone with aqueous potash, the ketonic acid is regeuemted. 2 : 6-Dimetkyloctan-3-oloic acid, CHhle,*CH(OH)*CH,~CH2*CHMe*CH,*COOH, is obtained by heating 2 : 6-dirnethyloctan-3-onoic acid with absoluto alcohol and sodium ; the silver salt cryst,alliscs in lustrous leaflets, and the lactone boils a t 155-165O under a pressure of 25 mm. On oxidising the acid with potassium permanganate, P-niethyladipic acid is formed. 5-XsopropyZheptan-2-onoic acid, CH,*C O*CH,*CH,*CHPrfl*CH,-C OOH, is obtained by the action of amylic nitrite and hydrochloric acid OIL tetrahydrocarvone, the product being hydrolysed with dilute sulpfi- uric acid; it forms colourless crystals, melting at 40°, aud boils at t t - f248 ABSTRACTS OF CHEMICAL PAPERS.192O under a pressure of 20 mm. The senzicarbazoize melts at 152--153", and the oxiine at 75-78' ; the phe~tylhyd~azone crystallises in golden ncedles and melts a t 1 0 2 O , and the etiiylic salt boils at 143-146O nnder a pressure of 12 mm. AcetylpropyIketot:,e?atanaeth?jle?re (1 : 4-acety~~soyroy~~cyc~oye?ztan-2- is obtained from tbe foregoing ethylic salt one), CHAc< by means of sodium and xylene; it is a sweet, colourless oil, which boils at 130-132O under a pressure of 25 mm, The coyper derivative crystallises in light green needles, and the dioxirne melts at 163'; hydrolysis of the diketone gives rise to the original acid.When bisnitrosotetrahydrocarvone is treated with ethereal hydrogen chloride, tetrahydrocarvonebisnitrosylic acid is formed, crystallising in leaflets, which melt and decompose at 82" ; the oxinze of bisnitroso- teti*ahydrocarvone is also produced, and melts at 75-77", In pre- paring the bisnitrosylic acid, a chlorinated ketone is formed, which yields a new terpenone, CIoHIsO, when treated with sodium acetate and acetic acid ; the semicarbuzone melts at 222-223". Isopropylheptanonoic acid is also formed when tetrahydrocarvone is gently oxidised with potassium permanganste ; more vigorous action gives rise to isopropylsuccinic acid. 'O-YH2 CH2*CH Prs' M.0. F. The Terpones and Camphor. By FERDINAND TIEMANN (Ber., 1896, 29, 219-131).-The author reviews the course of his recent investigations, and discusses the changes attending the conversion of camphoroxime into campholenonitrile. Iu the light of von Baeyer's work (this vol., i, ?46), the oily pinonic acid obtained by Tiemann and Semmler (Abstr., 1895, i, 478) on oxidising pinene is regarded as a mixture of isomerides; a similar mixture is produced when a-dihydroxydihydrocampholenic acid (m. p. 144') is distilled, and this fact is considered favourable to the pinene formula already advocated by Tiemann and Semmler (Zoc. cit.). M. 0. F. Bromo-derivatives of the Camphor Series. By ANGELO ANGELK and E. RIMINI (Gazzetta, 1895, 25, ii, 162-164; compare Abstr., 1895, i, 382).-The authors ascribe to ordinary bromocamphor, to the isomeride melting at 113", obtained by the action of hydrogen bromide on camphenone, and to monobromocamphenone, the following constitutions respectively : C;H13<co >CHBr, C7HI3eCo >CHz, CH C'Br C,H13<gG>CBr.These constitutions are in agreement with Bredt's _ - formula for camphor. W. J. P. Ledum-camphor. By EDVARD I. HJELT (Uer., 1893, 28, 3087- 3089).-The stearoptene contained in oil of wild marsh rosemary, ob- tained from the leaves of Ledum palustre (Abstr., 1882, 346), has the moleciilar formula C1JHzf260 ; Rizza's analysis had already indicated this. It is t h u s a camphor of the sesquiterpene series ; it melts at 104-105° and b,?il,s at 282-283O; it dissolves in alcohol to the extent of 10.4ORGANIC DHENISTRY.249 per cent. at 17*5O, and the solution is feebly dextrorotatory, [a]j = 7.98 ; it is a poison, affecting the central nervous system. Warming with dilute sulphuric acid on the water bath suAFices to make it lose water and yield the sesquiterpene ledene, CljHZI, which is an oil boiling at 255O, and rapidly acquiring a, greenish tinge. On account of the ease with which the camphor loves water, it is difficult to get the hydroxyl group to react ; neitther benzoic chloride nor phenylic isocyanate form derivatives, but the chloride, CI,H2,CI, can be obtained as a yellowish oil by the action of successive small quantities of phos- phorus pentachloride on a solution of the camphor in light petroleum ; heating with quinoline converts t h i s chloride into ledene.C. F. B. Ammoniacum. By H. Luz (A&. Pharm., 1395, 233, 540-550). -The sample examined contained 4 5 per cent. of water, 69 per cent. of resin, 22.7 per cent. of substances soluble in water, and 3.5 per cent. of substances, other than resin, insoluble in water. A consider- able amount of salicylic acid was present, but no aldehydes or ter- penes. Normal bu tyric and valeric acids were also present, largely in combination with a resin alcohol, ammoresinotannol, C18H30O3, a choco- late-brown, tasteless, and odourless powder, insoluble in water, but soluble in alkalis and acids. Ammoresinotannol is oxidised by nitric acid l o styphnic acid. The resin consists essentially of ammoresino- tannol salicylate. The acetgl derivative, C18H29A~03, is a brown powder, soluble in acetone, &c.The benzoyl derivative is similar, The gum of gum aminoniacum appears to contain calcium arabinate. JN. Wr. Conversion of Acetylacetone into Pyrroline Derivatives. By CARLO U. ZANETTI (Real. Bccad., Lincei, 1893, i, 324-327).- 3 : 5-Diacetyl-2 : 4-dimethylpysroline, NH<CAc:CMe , is formed on adding potassium nitrite to a cooled acetic acid solution of acetyl- acetone, and then reducing the product with zinc dust; on filtering and neutralieing with sodium carbonate, the base separates, and is ultimately obtained in colourless, flattened needles, melting at 136". It is soluble in most organic solvents, and is a very feeble base ; the nzirochloride, C,oHl~N0z,HAuC14, melts at 120-130° with previous decomposition, and is decomposed by water.On heating the base with potash and benzaldehyde, it yields 3 : 5-dicinna?noyl-2 : 4-dimethyl- pywoZine, C2*H2,N02, which crptallises in nodular groups of small needles, melting at 215-216". Nitrosoacetylacetone, (COMe)&:NOH, the intermediate product in the preparation of the above pyrroline, may be isolated by adding sulphuric acid to a potash solution of acetylacetone containing potas- sium nitrite, and then extracting with ether; on evaporating the ethereal solution and recrystallisiug, i t is obtained in flattened needles or scales, melting at 75". It is soluble in water, alcohol, or ethylic acetate, but only sparingly so in benzene or petroleum. On heating sodioacetylacetonc, suspended in ether, with iodine, a szcbsta?zce, CIoHIIOI, is obtained, which melts at 186-187", and is CMe:QAc possibly symmetrical tetracetylethane, w.J. P.250 ABSTRACTS OF CHEMICAL PAPERS. Synthesis of Pyridine Derivatives by the Action of Ethylic Acetoacetate on Aldehydes in Presence of Ammonia. By Ronmr SCHIFF and P. PROSIO (Gazzetta, 1895, 25, ii, 65-90).-On gradually adding alcoholic ammonia to %I mixture of ethylic aceto- acetate and commercial formaldehyde solution, heat is generated, and Griess and Harrow's ethylic dihydrolutidinedicarboxylate, melting at 176-183' (Abstr., 1888, 1313), is slowly deposited ; the action pro- ceeds in accordance with the equation 2C6H,,03 + H-COH + NH, = C13H19N04+3&0, and a 95 per cent. yield is obfained. The same substance is deposited immediately on adding the requisite amoiint of a, bydrochloric acid solution of formaldehyde to a, mixture of ethylic acetoacetate and alcoholic ammonia, so that the action proceeds both in acid and in alkaline solutions ; the ethereal salt has neither acid nor basic properties, and, when heated with hydrochloric acid, yields ethylic lntidinedicarboxylate, melting at 7 2 O , but no hydrogen is evolved as stated by Griess and Harrow (Zoc.cit.), the effervescence being due to carbonic anhydride and ethylic chloride. The same con- version may be effected by saturating an absolute alcoholic solution of ethylic dihydrolu tidinedicarboxylate with dry hydrogen chloride, evaporating the alcohol, and adding sodium carbonate, when ethylic lutidinedicarboxylate separates. The alkaliue mother liquor contains ethylic 2 : 6-dimethyl-l : 4-dih~di~opyridiiae-3-carbox.1~late, CMe:C(COOEt) NR<C&-CH> CH2 i t is extracted by ether, and is ultimately obtained as a yellowish oil of coniine-like odour, which distils unchanged at 235", and is more soluble in cold than in hot water.The ylalinochlwide, (C l,Hl;N02)2,H2Pt~~,, crystallises in yellow needles melting at 140', and the compound with mercuric chloride, CloH15N02,HgC12, is a yellow powder insolcble in water. The salt i R readily hydrolysed by potash yielding the corre- sponding acid, of which the hydrochloride, C6H1~N02,RCl, forms small glassy crjstals, whilst the platinochloride, (C,H,,NO2)2,H,PtCI,,2H,O, crystallises in small red prisma, which lose their water at 120'. On heating ethylic dihydrolutidinedicarboxylate with alcoholic potash, ammonia is evolved, and, on adding water and extracting with ether, Knoevenagel's tetrahydroketotoluene (Abstr., 1895, i, 48), which boils at 192-19io, is obtained ; it, is doubtless formed by iso- meric change occurring in CH:CMe x2<CH:CMe substance of the constitution which should be first produced from the dicarboxylate.Tbe alkaline mother liquors, when exactly neutralised, deposit Z2~tidinedical.buxyEic acid, C,H9N0,; this crptallises from boiling water in thin, white needles having a very high melting point, and is only sparingly soluble in alcohol or ether. The same acid may be prepared fromORGANIC CHEXISTRY, 251 the sodium salt obtained by the action of sodinm ethoxide on ethylic lut idinedicarboxylate.Nitric acid (sp. gr. 1.36-1.40) dissolves ethylic dihydrolutidinedi- carboxylnte with slight rise of temperature. and, after neutralisation, the product yields ethylic lutidinedicarboxylate crystallising in com- pact scales, which melt a t '72" and become electrified by friction. Ou leaving the dihydrolutidinedicai*boxylate in contact with fuming hydrochloric acid, and then neutralising with sodium carbonate, a substance is deposited which crjstnllises in long, lustrous needles melting at 71-72", but which does not become electrified by fric- tion. On recrystallisation from boiling solvents, however, this labile substance beconies converted into the above stable modification, which is easily electrified ; if, however, instead of crystallising the precipi- tate obtained by adding carbonate, it is merely washed and dried, it is found to be a11 imido-base isomeric with the original so-called ethylic dihydrolutidinedicarboxylste, and melts a t 38-60'.This base, et h?/Zic isodih y dyolutidin edica rbomy late, has t lie cons tit u tion NH<CMe~C(COOEt)>CHZ, CMe'C (C 0 OE t ) and is very yeadily oxidised by expo- sure to the air 01' by heating with alcohol, giring ethylic 1u;idinedi- earboxylate. C Me: C (GO OE t) No'N<C~e:C(COOEt)>CW?' crystallising with $H,O in yellow needles which melt a t 52*, and lose water a t 115'; by reduction with stannous chloride and am- monia, it yields another base, C13Hl9NOJ, which cryatalliaes with +H,O, and melts at 88'. Ethylic lntidinedicsrboxylate gives a nitroso-derivative, but has basic properties, and thus gives a picrate, C,,H,,ryTO,,C,rr,(NO,)3.OH, which separates in long, yellow crystals melting at 118-119° ; the original ethylic salt and its isomeride are found to have double the normal molecular weight by the boiling point method.The authors conclude that the original e thylic dihydrolntidinedi- carboxylate melting at 176-183" is wrongly named ; it contains no pyridine nucleus, but is an open chain compound of the constitution CH,:C(COOEt)*CMe:N*C hfe:CH*COOEt. This compound, by the migration of one hydrogen atom, readily yields the closed chain imido-base, m hicb is termed ethylic isoditrydrolutidinedicarboxylate, It readily yields a nitroso-deriratire, " - and has the constitution NH<cM CMe:C(COi)Et) :COOEt)>CHZ. This com- i e pound is readily oxidised on exposure tb air, yielding the labile form of ethylic lutidinedicnrboxylate melting at 72", t.0 which the consti- tution N/Ze:C(COoEJ)\CH must be assigned ; this unstable form, on recrystallisation, then assumes the stable form which be- comes electric on rubbing, aiid has the constitiition NeCMe: C (C 0 0 Et) yCH* W.J. P. By WILHELX KOENIGS (Ber., 1895, 28, 3148-3150 ; compare the following ab- \CMe:C( COOEt)/ CMe*C (COOEt) Dicarboxylic acids of the Piperidine Bases.232 ABSTRACTS OF CHEMICAL PAPERS. stract).-A number of the dicarboxylic acids of the piperidine bases have been synthetically prepared in order to throw light on the con- stitution of cincholeuponic acid, which is obtained by the oxidation of the quinine alkaloids.I n addition to those described in the succeedirig abstract, the following compounds have heen exnniined. The hydrochloride of l~exal~yd~ocinchom~?~onic acid me1 ts and decom- poses at 257O, whilst the hydrochloi*ide of heaahydrolepidinic acid melts and decomposes at 222". No attempt has yet been made t o resolre these acids into opticaliy active constituents. A. H. Reduction of Quinolinic acid. By EM[L Bwmom (Be),., 1895, 28, 3151-3160 ; compare the foregoing abstract).--When quinolinic acid, in dilute alcoholic solution, is reduced with sodium amalgam, it yields the lactone of 6-hydroxybutane-q/6-tricarboxylic acid (Pd- mutter, Abstr., 1893, i, 176) ; whilst, if it is dissolved in boiling amylic alcohol and treated with metallic sodium, it is converted into nipecotinic acid, carbonic anhydride beiug lost at the temperature of the experi- ment.On the other hand, asrain. reduction with metallic sodium and I '2 I 4: H2.C Hz.7 H-C 0 0 H CH2*NH*CH*COOH ' ethylic alcohol yields ~en.ahy~~op7~iizolinic acid, the product obtained is a mixture of two geometrically isomeric acids, which can be separated by means of their nitroso-compounds. Which OF these acids is the &-form, and which t'he cis-h-am-form, has not yet been definitely decided. (1) One of the nitroso-acids is orily sparingly soluble in cold water; i t is, however, readily solubIo in hot water, crystallises in large compact crystals, and melts and decomposes a t 154". The bariz6nz salt is very readily soluble in water, whilst the siluer salt is only sparingly soluble.This nitroso-acid may be resolved into two optically active constituents by the fractional ci*ystallisation of its strychnine salt. The new acids thus obtained, and the hexa- bydroquinolinic acids prepared from them, scarcely diff 'er from the racemoid forms, except in optical activity; they will shortly be more fully described. The hydrochloride of he~ah?ldropuiiaoli~zic acid, obtained by the action of concentrated hydrochloric acid on the nitroso-acid, forms slender, white needles, melting and decompos- ing a t 221°, whilst the awochLo&Ze melts at 185'. The free acid separates from water in compact, white crystals melting a t 235' ; it is scarcely soluble in alcohol and other organic solvents. The hydro- chloride of metlzylic hen.ahydi.oquinolinufe melts and decomposes a t 166-1 67".(2) The more readily soluble nit rosohexahy droquinolinic acid was not itself isolated, but when decomposed with Irydrochloric acid it y iel d s the hydrochloride of li exahydrop t~iiiol it& acid, which melts a t 2 3 9 O , and, unlike the isonieric salt just described, is only sparingly soluble in concentrated hydrochloric acid. The msrnchlo- ride melts and decomposes at 195". The free acid nielts a t 227O, and is much more readily solublc in water than its isotneride ; i t lias hitherto only been obtained as a glassy mass. The hydroc1,loride melting at 239' is completely converted into the isomeric salt, melt- i n g at 221°, when it is dissolved in amylic alcohol, treated with sodium, isolnted in the form of a nitroso-acid, and finally re-obtainedORUANIO CHEMISTRY.253 from this compound by the action of hydrochloric acid. The hydro- chloride of nzethy lic 1re~ahydroqiii.lzolilzafe melts and decomposes a t 189-1Y0°, whilst the cormsponding ethylic derivafire melts and de- composes at 20-1-205'. Hexahydroquinolinic acid acts towards bases as a monobasic acid, whilst the nitroso-acid is dibasic. It has so far proved inipossible to resolve the acid melting a t 227" into optically active constituents, although since the groups com- bined with its two asymmetric carbon atoms are dissimilar, it should, like the isorueride, be capable of such resolution. A. H. Optically Active 2-Pipecolines and '6 Isopipecoline." BJ- WILHELM MARCKWALD (Bey., 1896, 29, 43-51).-Inactive synthetical 2-pipecoline can be separated into its active components by adding d-tartaric Rcid and concentrating, when d-2-pipecoline d-hydrogen tar-trate crystallises out.From the mother liquor, the base is set free, and then made to crjstallise with I-tartaric acid, when 1-2-pipecoliue E-hydrogen tartrate crystallises out. This process is repeated, tl- and 2-tartaric acid being used alternately to effect crystallisation ; an almost quantitative separation can thus be effected. These two hydro- gen tartrates both have the composition C6H13N,cdB606 + 2H20 ; both melt at 65-66'or, when anhydrous, at Ill-l12',and both form mono- clinic crystals, which are enantiomorphous but otherwise identical ; a : b : c = 1.1698 : 1 : 1.74'77; /3 = 81' 20'. The hydrochlorides, cadmioiodides, platinochlorides, aurochlorides, picratcs, and ditbiocarh- amates, (C,I3[,,N0Cs*sH.C6H,,K), melt respectively at 190" (205'), 147c 141-142' (1'26') ; the numbers given in brackets are the meltiug points of the corresponding salts of inactive 2-pipecoline. I-2-Pipe- coline, liberated from its I-hydrogen tartrate prepared as above, has il rotation a D = -32*Oo, in a tube 100 rnm.long, and is of the same magnitude as that of the d-isomericte; it had not hitherto been obtained pure. d-2-Pipecoline I-hydrogen tartrate rtnd 7-2-pipccoline d-hydrogen tartrate both crystallise with H,O ; both melt a t 45-46', and when anhydrous at 126'. 2-Pipecoline hydrogen racemate can be prepared from inactive 2-pipecoline ancl racemic acid, or from d-2-pipecoline d-hydrogen tartrate and I-2-pipecoline I-hydrogen tartrate, or from d-2-pipecolinc I-hydrogen tartrate and I-2-pipecoline d-hydropi tartrate.I t crystal- lises with H20 in monoclinic crystals; a : b : c = 2.670 : 1 : 1.36s; /3 = 85' 46.5' ; and melts at 85'. Ladenburg's statement (Abstr., 1894, 306) that ,z new substance, isopipecoline, is obtained when d-2-pipecoline hydrochloride is dis- tilled with zinc dust, is incorrect; what really happens is a partial conversion of d- into I-pipecoline. If I-pipecoline chloride is boiled in an atmosphere of h~~lrogeii, it undergoes it partial conversion into the d-isomeride. C. I?. B. (131"), 194' (186*), 133-132" (118-119°), 116-117" (127--128"), a-Naphthylpiperidine. By Jmrw ABEL (Ber., 1&95, 28,3106- 311 1 ; compare Abstr., 1890, 1002).-a-Naphthylpiperidine (loc. c i f . )254 ABSTRACTS OF OHEMIaAL PAPERS. i s formed when piperidiiie (8.5 grams) is heated with a-naphthol (14.4 prams) at 250-260' for 6 - 5 hours; i t is a pale yellow oil which boils a t 215' under a pressure of 35 mm., and exhibits a beauti- ful blue fluorescence. The hjdrochloride forms colourless crystals melting at 178-179' ; the awochZoride melts at 128-129", and the picyate ciytallises in yeltow needles, and melts at 179-180"; the ferrocyanide separates in colourless crystals, and the mercuyichloride is amorphous. ~ e t l . a h y d l . o - a - ? z a p h t h ~ ~ ~ ~ ~ e ~ i ( l ~ ~ ~ ~ is obtained by adding a solution of a-naphthylpiperidine (15 grams) in dry amylic alcohol (200 grams) tJo molten sodium (25 grams) ; it is a pnle, yellow oil which boils at 218' under a, pressare of 63 nim., and reduces cold, alcoholic silver nitrate. The h~jdrochlode crystallises with difficulty, and the mer- czo*ichZo~*ide is aiuorphons, the Jcer~ocyuizide beiitg obtained in white crystals ; the plafi~tocl~lotitle forms small, Iusti*ous crystals, melting at 190-192', and the awoch!wide crystallises in golden-yellow leaflets, and melts at 14s-149'.Oxidation of tetrahydro-a-naph- tliylpiperidine with potassium permanganate i n presence of alkali gives rise to adipic acid. M. 0. F. 2 : 3- and 3 : 4-Dibromoquinoline. By ADOLPH Crms [aiid, in part, KARL LODHOLZ and FRITZ HIRSCHHRUNN] (J. p r . Chem., 1896, l2], 53, 25-88).--2 : 3-Dibromoquinoline melts at 68", and 3 : 4- dibroinoquinoline at 135", not 95' and 124" respectively as previonsly stated (Abstr., 1890, 172).3 : 4-L)ibromoquinoliiie plntii~oc7~toride and metlhiodide are described. The bromiuation of 3 : 4-dibromoquinoline hydrobromide in chloro- form solution produces 3 : & : S'-tl.ibromogzcinoline, which melts at 149O, and was formerly described as 3 : 4 : 4'-tribromoquinoline (Abstr., 1894, i, 47:3) ; tlhe yZati?zochloiide is described. 3 : 4 : l-Dibromoititrol/ziii2oliste is the sole product of the nitration of 3 : 4-dibromoquinoline in the usual manner; it sublimes in the form s f lustrous needles aiid melts a t 152" : its basic properties are veyy feeble ; the platinochloride is described. 2 : 3-Dibromoquinoline differs from the 3 : 4-derivative in its volatility in steam a t atmospheric pressure ; its platinocldoride and ethiodide are described. 2 : 3 : l-Dibi.omo?~itl.opziino?i~~e is the more abundant product when 2 : 3-dibrumoquixioline is nitrated without warming ; it sublimes in nearly colourless, lustrous crystals, melts at 1 9l0, and dissolves freely in ether and chloroform, but only sparingly in alcohol, and not at all in water; the plafiwchloride is described, but no methiodide could be obtained.The corresponding nnzido-derivative crystallises in colour- less, slender needles, and melts at 68'. 1 : 2 : 3-T~ibl.o??zogziinol~)ie is prepared from 2 : 3 : 1-dibromamido- quinoliue through the diazo-reaction ; it crystallises in colour- less needles, melts a t 8A3, and does not easily sublime ; the hydro- chloyide and plati?~ochloride are described.2 : 3 : 4-I)ibl.onzo?iit?.o~ui?io~i?le is the more abundant product of the nitration of 2 : 3-dibromciquinoline when the temperature is raised ; it is more soluble in alcohl than is the accompanying 2 : 3 : 1-derivative,ORGANIC CHEMISTRY. 255 and crystallises and sublimes in colonrless needles melting at 165'. The qjd&-lide is easily prepared (compare the 2 : 3 : 1-derivative), and melts and decomposes at about 250-252O. The platiltochlo~ide is described. The corresponding amido-derivative crystallises in small, colourless needles, and melts at 119'. 2 : 3 : 4-Tribromoquir~oline, prepared like the 1 : 2 : 3-derivative, crys- tallises and sttblimes in colourless needles, and melts at 124'. 2 : 3 : 3'-TribromogziinoEine is prepared by the Claw-Collischonn niethod (bromination of the appropriate dibroinoquinotine hydrobro- mide in chloroform solution) from 2 : 3-dibromoquinoline ; i t sublimes in lustrous, colourless prisms, aiid melts at 116.5'.The pEntinoc7aloii.ide and the wiethiodide are dcscribed. A. G. B. Action of Bromine on Para- and Ortho-Hydroxyquinoline. By ADOLPH CLAUS and HANS HOWITZ ( J . pr. Chem., 1895, [2], 52, 532-547).-The authors have previously stated that the red dibro- mide obtained by adding bromine (2 atoms) to 4 : 3-bromhydrosy- -quinoline hydrobromide suspended in chloroform decomposes when exposed to air, with loss of hydrogen bromide and formation of a dibromo-3-hydroxyquinoline. This statement is incorrect ; the com- pound merely loses the two at.oms of bromine, the original 4 : :3- bromohydroxyquinoline being left.1 (3 2) :4 : 3' : 3-Tribi*omhyclroxy~~i~ia~~l~~e is obtained when the fore- ,going dibromide, or a mixture of 4 : 3-bromohydroxyquinoline with bromine (2 mols.) is heated in a sealed tube at 200--250°. It crys- tallises in slender, silky, colourless needles, melts at 257", and dissolves very sparingly in mineral acids aiid i u alcohol, but freely in warm glacial acetic acid. Oxidation by potassium permanganate converts it into 3-bromopyridinedicarboxylic acid and 3-bromonicotinic acid ; this settles, to some extent, its orientation. 2 : 4 : l-Dibromohydroxyq&oline hpdmbvmide separates as a yellow .crystalline precipitate when bromo- 1-hydroxyquinoline is brominated in chloroform solution ; it melts at 250°, and sublimes slowly i n the form of slender needles; when warmed with water, it yields the corresponding base, which separates in crystalline flocks, and melts at 196'. When this dibromhydroxyquinoline is brominated i n chloro- form, the dibromide of the hydrobromide is precipitated in yellow needles or prisms, which melt at 160---170°, the molten mass rapidly losing bromine ; in water, this compound loses hydrogen bromide without loss of its bromine.By heating the dibromide in a sealed tube a t P5Oo, 2 : 4 : 3' : 1-tri~1~omhpdro~~yquinoline may be obtained ; it is at first a yellow powder, but sublimes in colourless needles, which melt, a t 169-170O ; oxidation with pernianganate converts i t into 3-bromopyridinedicarboxylic acid. The authors regard this tribrom- hydroxyquinoline as identical with that obtained by Clam and Heer- mann by the action of phosphorus pentabromide 011 1 : 4hjdroxy- quinolinesulphonic acid (Abstr., 1891, 82).A. G. B. 3-Ethoxyquinoline. By C. GRIMAUX (Compt. regid., 1895, 121, 749-751).-3-Etho~yquinoZirz.e or p i n e t h o i t , C,NH6*OEt, is an oily256 ABSTRAOTS OF OHEMIOAL PAPERS. liquid obtained by the action of glycerol and sulphnric acid on ethyl phenyl ether. J t boils at 290-292' without decomposing, and with inorganic acids forms crjstalline salts, the solutions of which show fluorescence similar to that of quinine. The nitrate crystallises in needles melting at 165'. The salts with organic acids are decomposed by water. The nitro-derivative is not obtained by the action of nitric acid alone, but is prepared by adding nitric acid to a solution of the base in sulphuric acid, arid treating the product (the nitrate of the nitro-derivative) with potassium or sodium hydroxide, or by adding the nitrate of the base to sulphnric acid, diluting with water, and precipitating with ammonia.It melts at I lo', crptallises in needles or in flat rhombdidal prisms according to the conditioris, and has feebly basic properties. The anzido-derivative crystallises from boil- ing water in snlphor-yellow prisms containing 1 mol. HzO, and, when anhydrous, melts at 110". With acids, it forms red monacid salts, which dye silk a pate yellow ; the diacid salts are colourless. The diazo-derivative yields coloured compounds. 3-Ethoxyquinoline is without any effect even in the simplest inter- mittent fevers, and has no antipyretic properties.Action of Orthoaldehydic acids on Quinaldine in Presence of Zinc Chloride. By K. NENCBI (Uer., 1896, 29, 187-190 ; compare M. Nencki (Abstr , 1894, i, 518).-Pl~thalidyZquinaldine, C9NH6*CH2*cH<c6~>c - 0, is prepared by heating aqueous solution of plithaldehydic acid aad quinaldine, in molecular proportion, with zinc chloride during eight hours ; the product is extracted with dilute hydrochloric acid, and the solution treated with soda ; the precipi- tate crystallises from alcohol in colourless needles, and melts at 104'. The platinochboride, ( C,,H,,0,N),,H2PtCI,, is yellow and crystalline ; the aztroclilcrride has also been prepared. Diphthalidylguiizaldine, C,NH6*CH(CH<~~>CO)2, is obtained, along with the preceding cornpound, and can be separated from it by means of its insolubility in hydrochloric acid ; i t crystallises from absolute alcohol in needles, and melts at 192'.The combined yield is 50 per cent, of the theo- retical, including 10 per cent,. of the diphthalidyl. Phthalidyl- dinzet~~ylquinaldine, C,NH,&fez*CH2*CH<~ d>CO, [Mez = 1 : 31, prepared from phthaldchydic acid and dimethylquinaldine, crystal- lises in colourless needles, melts a t lltj", and is insoluble in dilute alkali. DiphthaliLE~ldinaetlzylquinaldine, CgNH4Me2*CH(CH <"%> - CO),, C. H. B. C H is colourless, crystalline, melts at 2 2 4 O , and is foimied in small quantity together with the preceding compound. Opianytclinzethyl- guiitaldine, CsNH,Me~*CH,.CH<C6H2(o~~e~>C0 --- [Me2 = 1 : 31, prepared from opianic mid and 1 : 3-dimethylquinaldine, crystallises in colourless, slender needles, melts at 1 3 2 O , and dissolves in alkaliORGANIC GHEM 18 TRY.257 (30 per cent.) only after prolonged boiling. The pZafinochEo,ride, (Cz,H,,O,K),,HzPtCls, forms yellow crystals. The formul;r! given to the above compounds accord with their insolubility i n alkali, and i n their formation the aldehydic acids react as hjdroxyphthalides {compare Liebermann, this vol., i, 232). J. B. T. Derivatives of Piperazine. Ry G. ROSDALSIX (J. p r . Chenz., 1896, [2], 53, 19--24).-Ethylic pipermine-1 : 4-dica~baxylutc, is prepnrcd by shaking an aqueous solut2ion of piperazine with ethylic chlorocai*bonate and potash, and extracting with ether ; it crystallises in needles, melts at 4 2 O , boils at 3W, and dissolves in the usual solvents - Piperaxine.1 : 4-dicarboxylnmide, C4N2H,(CONH2),, is precipitated when cold concentrated solutions of piperazine hydroct~loride and potassium cyanate aye mixed ; it crystallises from hot water in lustrous, rhombic crystals, aud from boiling alcohol i n short prisms; i t is insoluble in ct her and benzene.The correspondiag aitilide, C,N,H,(CO*NHPh),, is an amorphous, insoluble substance, pFecipi- tatcd by adding phenylic isocyanate to an aqueous solution of piperazine. Tri-carbon ylpiperazine, (C,N,H,:CO),, separates as an amorphoiis precipitate when carhonyl chloride is passed into an alkaline solu- tion of piperazitie ; it is insoluble in the usaal solrents.(C4N,H8<cO> CsH,),, is an amorphous precipitate, formed when phthalic chloride is added to an alkaline solution of pi perazine. Pipeyazine-1 : 4-diphenyEsuEphone, C4N2H,( S 02Ph) 2, from benzene sulphonic chloride and piperazine, is an amorphous precipitate. 1 : 4-Afet hylenepiperazine, C4N2f3[,:CH2, from piperazine and form- aldehyde, is a, white precipitate, insoluble in water, alcohol, ether, benzene, and caustic soda, and decomposed by dilute acids into the parent substances. Piperazine ethylic oxalate, C4N2H,,,(COO€€*COOEt)z, is obtained by heating hydrated piperazine with ethylic oxalate in alcoholic solution ; it crystallises from water in thick prisms, and melts at 181'. Alcoholic ammonia converts this compound into piperazine oxamate, C4N2H,,,( COOH*CONH,),, which crystallises in monoclinic tables. 1 : 4-Diet7~ozal?/lpi~era,-i~ze, c4N2H8( CO*COOEt)2, is obtained when anhydrous piperazine and ethylic oxslate are heated together in abso- lute alcohol ; it is sepamted from other products by boiling benzene, and melts a t 215' (compare Schmidt and Wichmann, dbstr., 1892, The eo~t~pound, CI6H,N2O4, is formed when ethylic acetoacetate and piperazine are warmed together ; it crystallises in white, felted needles, melts at 140°, and dissolves sparingly i x ether and benzene, but not i n water.CO Tri-p7~tha7ylpiperazilze, 210).258 ABSTRACTS OF CHEMICAL PAPERS. Carbonic anhydride produces a crystalline precipitate, C,H,,,N20,, in an alcoholic solution of pipel-aziae. A. G. B. Steric Hindrances to Chemical Reactions.Ry P,\YEf, I\\*- PETRESKO-KRITSCHESKO (Ber., 1895, 28, 3203-3207 ; compare this 1-01., i, 134). The ethereal salt, formed by the action of phenyl- hydrazine on ethylic methylace tonedicarboxylate, is shown to have the cons ti tution, C 0 < NPi'*N>CoCH2*COOEt, HMe since the acid forinea on hydrolysk loses carbonic anhydride when heated, and yields Know's dime thy1 p henylpyrazolone, c 0 <CHMe->CMe, on distil lation in a vacuum. The author criticises some of the conclusions drawn by V. Meyer (this vol., i, 145) from his work on the etherification of triphenyl- acetic and triphenylncrylic acids. In contradistinction to V. Meyei-, the author regards the phenyl-group as equivalent to a primary, rather than to a tertiary, radicle.This conclusion is supported by reference to the author's own work, and also to that of Meyer and of Lean. Victor Meyer, in an appended note, states that he does not agree with all the author's conclusions. J. J. S. NPh*N Aromatic Homologues of Ethylenediamine, By FRANZ Ftirw and HCGO ARNSTEIN (Uer., 1895,28, 3167-3181 ; compare Abstr., 1895, i, 274) .-The dibenzoyf compound of phenylethylenediamine, when heated in a current of hydrogen chloride at 240°, is converted into 'L : 4- - - CPh:r which crystallises in hard, CH,*CHPh' t l ~ ~ l ~ e n . y l d i h y d ~ o ~ l ~ o x a l i n e , NH< colourless prisms, melting at 78'. Diacetophenylethylened iamine crys- tallises in snow-white plates, melting a t 152'. The thiocai*bamafe melts and decomposes at 97". of the .base, CHPh<CH2*NH2*S €3' P?ienyletlyEenethiocarba?nide crystallises in white plates, and melts at 184'. The diarniiie does not yield a well characterised product with ethylic oxalate or benzaldehyde, but readily reacts with benzile, forming 2 : 3 : 5-t~lpl~enyl-S : 6-dil~yd~opyi*uzine, N<CH,.CHPh>N, NH*vS CPh-GPh which crystallises in bronze-coloured plates, melting at 149'. Phenyl- pheitanth,.apyrazine, !?Ph*N:? crystallises in silky, yellow needles, CH-N:C*C,Hi melting at 190'. Diphenylethylenediamine forms a bitartrate, which crystallises in fascioular groups of needles, melting with decomposition at 165-166". The fractional crystallisation of this salt from warm water resnlted in the separation of its t w o optically active components, the dextro- rotat'o1.y base forming the more readily soluble salt.The two com- ponents have not yet been completely separated. An attempt to convert the racemic form of t.he base into hydrobenzoin by means of Phenyl-/3-n~~'htl~ayyYazirce melts at 187'.0 RUAXEIC CHEMIST RT. 259 the action of sodium nitrite, resdted i n the production o€ a very small amount of isohydrobenzoh, which must therefore be the racemic form of this compound. Small amounts of isodiphenyl- hydroxyethylamine and of diphenylncetaldehyde were also obtained in the same reaction. Diaceto2,henylethyZenedia?,tine is n white poivder, which melts above 3 6 0 O . The dibenzoyl-co?,~po?c~Id melts at 287'. ~ ~ i n i i i . o d i b e n z o d ~ ~ e n y 1 - ethylenediantine m;ty be obtained by direct nitration, and forms n yellow powder, melting at 137' with decomposition.The dibenzoyl- cornDound is remai-knblv sta.ble, and can only be convei-tcd into an anhidro-base by hydroien chloride at 260'. 2 : 4 : 5-T~iphenyZ-4 : 5- prepared as just described, is NH-CHPh dihy drogl yoxa line, CPhG N-6 R-h' isomeric with amarine, and melts at l.75'. 2 : 4 : 5-Methyldipl~~~ayl- 4 : 5-dil~yd~~oqZyoxaE~~.ite, ?HPh*NH>CBfe, may be prepared in a simi- CHPh-N' lay manner, and melts at 162O. D~henZlZethyknrti~u~.bnl,zido crystal- lises in colourless needles, and melts above 360'. The ditliiocarbantide melts aiid decomposes at 192O. Dipheny7ef hy7eiiedianzine thiocarb- antate is a light yellow, crystalline powder, which melts at 132". D~phenylethylenetl~o~ar~a~~de is obtained by the distillation of the foyegoing compound, and is a white, granular powder, melting at The base unites with two molecular proportions of ethylic oxalate, forming an additive compound, which melts at 164O.When heated with ethylic oxalate, on the other hand, a compound of the formula, is obtained in white crystals, melting yHPh*NH CHPh*NH "'COOEt' and dccomposing at 242'. The dibeitaylit7eue derivatke of the base melts at 152'. Diphenylethylenediamine reacts with b e n d to form teti*aphenylpyrazine. With phenanthraquinone, it yields the corn- C Ph*N*C *CsHt' pound, 2 : 3-diphenylphenanthrapyi.a~i~~e, tallises in slender, light-brown needles, melting at 265O. 183-184O. OEt $Ph*Y!?'96H4 which crys- A. H. Pyrazolone. By LUDWIG KXORI~ (Ber., 1396, 29, 249-259 ; com- pare ron Itothenberg, Abstr., 1893, i, 180, 367, 422, 611, and 729 ; 1894, i, 349, 350, and 622 ; 1895, i, :302, 571, and 686 ; Ruhernann, Abstr., 1894, i, 476).--The author points out that the pyrazolone described by Ruhemann has properties ent.irely different from those of the pyrazolone described by von Rothenberg, and as the possibility of isomerism is theoretically impossible, one of the statements must be wrong.The t w o formulm given by Ruhemsnn for pyrazolone and isopyrazolone, the author considers, represent desmotropic forms of the same substance. The author has prepaped pyrazolone from hydr- mine hydrate and ethylic formylacetate, and finds that it agrees in all its properties with the substance described by Ruhemann, and he therefore concludes that the oily substance (b.p. 156-157') described by \-on Rothenberg can only be a solution of pjrazolone, and not the2 ti0 ABSTRACTS OF CHEMICAL PAPERS, pure substance, especially a s it shows no analogy in its qenernl pro- perties to 1 : 3-phenylmethyl-5-pyrazolone and 3-niethyl-5-pyrazolone, which have been previously prepared. Pyrazolone, as obtained by the action of hydrazine sulphate on the sodium salt of ethylic formylncetnte in the presence of free alkali, crgstallises from toluene or xylene in minute needles, begins to sinter at 160°, and melts at 163-164' ; it has no odour, is readily soluble i n water and alcohol, but only sparingly in ether. It has reducing properties, is coloured reddish-brown by ferric chloride, and is only slightly volatile with steam.Wlien heated, i t sublimes, a t the same time undeygoing decomposition. It is further characterised by possess- ing both acid and basic properties ; solutions of pyrazolone cannot be titrated with litmus as an indicator, since the litmus is turned blue when only about 3/10ths of the theoretical quantity of alkali has been added. An oily and extremely hygroscopic hydrochloride may he obtained, but it gives no precipitates with either platinum or gold chloride. I n coutradistinction to von Rothenberg's compound, i t is not decomposed when heAed with coucenti*ated hydrochloric acid at 1 00". The sodium salt may be obtained as a solid, hygroscopic residue on evaporating a solution of pyrazolone i n the I-equisite quantity of sodium hydroxide solution. The solution of the sodium salt yields precipitates with silver nitrate, barium chloride, cobalt sulphute, nickel sulphate, copper sulphate, and mercuric chloride solutions.4-Benz?llidenepyrazol~?~e, CJf2H,O:CHPh, crystallises in minute, orange coloured needles, and melts at ZOOo; whereas Rothenberg describes it as a semi-solid mass of a purple-red colour. cO-~-:N*OH 4. Isonit rosopyrazdone, NH<N : CH , crystallises from its aqueous solutions in long, hair-like needles, or in small, compact, yellow prisms ; it me1t.s at 1)30-181°, and, at the same time, under- goes decomposition. According to Ton Rotbenberg, it crystallises in brown needles and melts at 87". The silver salt forms deep red, felted needles. CO*$!:N*NHPh NI CH The hydrazone, NH< , crptallisee in orange coloured plates, and melts at 196' (Hothenberg gives 185').The parutolyZ- hydrazone melts and decomposes at 223" (Rothenberg, 219'). The author thinks that his componnds are identical with those described by von Rotheuberg, but that the lattei. were by no means pure. Pyr- azolone, prepared by Ruhemann's met,hod (Trans., 1595, 1008), gives derivatives identical with those described above. J. J. S. Metallic Double Salts of Antipyrine (Dimethylphenylpyrazo- lone). By LEOPOLD VAN ITALLIE (Ned. Tydschr. Phar3n., 1895,7,295- 296) .-Antipyrinc zinc chlokde, (Cl~H~2N20),,ZnC12.-If aqueous soh- +ions of zinc chloride and antipyrine are mixed in molecujar propor- tion, oily gIobules are formed, which first become pasty and afterwards crystalline. The salt is also obtained by slowly evaporating a mixture of zinc chloride The crystals are anhydrous, and melt at l55O.ORGANIC CHEMISTRY.261 and antipyyine in alcoholic solution, or by mixing this solution with ether. The corresponding iodide forms well-defined crystals, showing double refraction, and the bromide colourless crystals, moderately soluble in water. On adding a solution of mercurous nitrate to an alcoholic solution of antipyrine, a greyish-black deposit is obtained, consisting of a, compound of antipyrine m ith both mei-curous and mercuric nitrates, The amount of combined mercury is, however, very variable, and there is always a small quantity of metallic mercury in the precipi- tate. L. BE K, Quinacridine. By STEFAN NiEMENTOWSKI (Ber., 189 6, 29,76433). -The condensation of phloroglnciiiol with ant hranilic acid yields a, derivative of quinacridine, the name given by the author to a base, the structure of which resembles that of anthracene or phenan- threne.tained. by heating phloroglucinol with anthranilic acid at 150" for 15-20 minutes, and then at 200-230' for 1-2 hours; it remains solid at 370', becoining black at 420'. This substance is insoluble in the usual organic solvents, but crystallises in minute cubes from phenol and phenylhydrazine ; the solution in concentrated sulphuric acid is yellow, and exhibits green fluorescence. The ncetoxypuin- ncridone is amorphous, and undergoes no change at 360'. The trinity0 . derivative is insoluble in organic solvents and dissolves in alkalis ; it decomposes and becomes black at 270-280". oxyquinacridone is distilled from zinc dust ; it crystallises from benzene in colourless leaflets, and melts at 2 2 1 O .A ConzpouwZ, which is probably an isomeride, is also formed, crystallising from the mother liquor and melting at 213' ; it forms a platinochloride, resembling that of acridine, and this base is also produced when hydroxyacridone is submitted to the treatment indicated. Tetrahydroquinact-idine, C20H&2, is obtained by reducing qnin acri- dine in alcoholic solution with sodium amalgam ; it crystallises from benzene in golden-yellow leaflets, and melts at 272@, softening at 255@. Acetic anhydride dissolves it with the production of an intense blood- red solution, which deposits quinacridine on cooling ; fhe solution in boiling benzene is yellow, and exhibits a beautiful, green fluorescence.Methyldioxytriapine (Acetoguanamide), By A. 0 STROGOVIC H $1. 0. F. (Annulen, 1895, 288, 318-3211 .---diZefhyldioeytriazine, identical with acetoguanamide, described by Nencki (Bey., 1876, 9, 234), is obtained by heating acetylurethane (6 grams) with carb- VOL. LXX. i. 262 62 ABSTRACTS OF CIEEXICAL PAPERS. amide (2.7 grams) for six hours tat 140-150°, etltylic acetate being formed at the same time. The Irydroclzloride crystallises in needles, and the pZatiizochZoritZe is yellow j the silrer derivative is white, and the lead derivative is crystalline. Dilute nitric acid converts methyl- dioxytriazine into cyanuric acid, and bromine gives rise to a tribronzo- derivative, wli ich yields cyanuric acid and bromoform when treated with boiling water.Br. 0. F. a : p-Dimethyloxazole. By ADOLF SCH~JFTAN (Ber., 1895, 28, , can be obtained from c CMe*O 3070-3O71) .-This substance, B< chloracetone and acetamide, contrary to Lewy's statement (Abstr., 1888, l l O l ] , by heating them in the proportions of 14 : 1 parts by weight for eight hours at 110--12/3'; much of the acetamide remains unchanged, however. It is a coIourless liquid, with an odour like that of pyridine and hardly distinguishable from that of a : pdimethyl- thiazole ; it boils at 108' ; its hydrochloride, platinochloride. (decompos- ing at 1 9 6 O ) , aurochloride, and merctwochloride (melting between 82-90'> mere prepared. CMc:QH C. F. B. New Synthesis of Oxazoles. By EUIL FISCHER (Bey., 1896, 29, 205-214).--When hydrogen chloride is passed into a cooled ethereal solution of benzaldehydecyanhydrin and benzaldebyde, the hydro- , crjstallises out.This chloride of p ; ti-diplienylozcixole, O< melts and decomposes at 160-165" ; water decomposes it,, precipitat- ing the oxazole, which melts at 74' and boils just above 360"; the melhiodide me1t.s and decomposes at 196' (corr. 2Olo), and has the character of a quaternary base. The oxsznle, in acetic acid solution, is oxidised by chromic acid to phenylgl?foxy I-henzanzide, CPh:FH CPhX CP h O-KH-C 0 * C P h 0, which melts att 142-143' (corr. 146'). When reduced with sodium in boiling a!coholic solution, the oxazole yieIds be?zzylpAeraylh~droxy- ethylamine, CH,Ph.NEf.CEi,*CHPh*OH, which melts at 1OO-10lo (corr.104O), and distils without decomposing. The hydrochloride of this base melts at 220" (corr. 226'); the nitrosamine melts a.t 93* (corr. 95'), and does not give Liebermann's reaction. The base is reduced by hydriodic acid at 140-150° to be.nzylphenliEeth?ilamine, CH2Ph*NK*CHz*CH2Ph, which boils at 327-328" undcr 750 mm. pressure ; the h j ~ d r i ~ d i d e melts at 227' (corr. 233'), the hydrochloride a t 26&266", and the sulphate at 186-187O (corr. 191-192O). Tbis base is more conveniently prepared by reducing with sodium in boiling alroholic solution the condensation product of benzylamine with phenylacetaldehyde. /3 : p-Diphenyloxazole can also be prepared by warmin benzamide with crude phenylbromacetaldehyde, CHPbBr*CHO. %his last is itself obtained by brominating a cooled cldoroform solution of phenyl- acetaldehyde, and distilling off the chloroform in a vacuum; the product can'be distilled under 1 rnm.pressure.ORGANIC CHEMISTRY. 263 The cyanhydrins of aliphatic aldehydes do not yield oxazoles in the manner described above. Acetaldehyde cyanhydrin and benz- aldehyde, if left in ethereal solution containing 2 per cent. of hydro- gen chloride, condense to benz2llidenelacta.)nide, OH*CHMe*CO*N:CHPh, which melts at 130-131° (corr. 133-134O). C. F. B. Synthesis of Caffeke. By EMIL FISCHER and LORENZ ACH (Ber,,'1895,28,3135-3143 ; compare this vol., i, 12).-The synthesis of caffe'ine is effected by means of the following operations : (1) Pro- duction of dimethylbarbituric acid from malonic acid and dimethyl- carbamide ; (2) conversion of dimethylbarbituric acid into dimethyl- violuric acid under the influence of nitrous acid; ( 3 ) reduction of dimethylvioluric acid to diniethylnmmil, and transformation of the 1at.ter into dimethylpseudouric acid by means of potassium cyanate ; (4) conversion of dimethylpseudouric acid into ydirnethylnric acid (toc.cit.) ; (5) formation of chlorotheophylline by the action of phos- phorus pentachloride on -/-dimethyluric acid ; (6) reduction of chloro- theophglline to theophylline, and conversion of the latter into caffeine. Chtorot heoph y 11 ine, rilre*CC':?"H>CO, is obtained by Beating an intimate mixture of ydiniethyluric acid, phosphorus pentachlorido (2 parts) and phosphorus oxychloride (4 parts) in sealed tubes at 150" for 2$ hours; it crystnllises from acetone in aggregates of colourless needles, which melt and decompose about 300".It is very sparingly soluble in chloi-oform, but dissolves more freely in acetone, and is readily soluble in hot alcohol; i t dissolves in 150 parts of boiling water, forming an acid solution, and is readily soluble in ammonia, alkalis, and concentrated mineral acids. Chlorine water produces the change characteristic of xrtnthiae and its derivatives. The sodium and silvep. derivatives crystallise i n slender, white needles, the latter substance being insoluble i n water, and gradually becoming dark when exposed to light. When chlorotheophgllirie is reduced with hydriodic acid, theophylline is produced (Kossel, Abstr., 1888, 1114) ; the action of methylic iodide on the silver derivative gives rise to chlorocsff eine.Bromotheophy ZZiiie is formed when a mixture of phosphorus penta- bromide and phosphorus oxychloride acts on ydimettiyluric acid, chlorotheophylline being produced at the same time; it is also ob- tained by heating theophylline with bromine for four hours at 100" and subsequently a t 1-50". Bromotheopltylline separates from alcohol in colourless crystals, and melts and decomposes at 315-320' (uncorr.) ; it is very sparingly soluble i n hot water, b u t dissolves readily in ammonia and alkalis. Hydriodic acid readily converts it into theophylline. Dimethyl barbituric acid is converted into the sodium derivative of dimethylvioluric acid by adding a concentrated solution of sodium nitrite to an aqueous solution of the acid at GO" ; the sodium derivative contains 3Hz0 (compare Andreasch, Abstr., 1895, i, 337), which is removed at 115".Anhydrous dimethylvioluric acid melts at 141', and C 0 -NMc*Cz N2 64 ABSTRACTS OF OEEMICAL PAPERS. in the hydrated condition at 124O (compare Zoc. cit., and Techow, Abstr., 1895, i, 84). If. 0. F. Morphine. By E. VONGERICHTEN (Ber., 1896, 29, 65--68).-Thc author considers that there is much evidence to show that morphine must have the nitrogen atom attached directly t o a carbon atom of the benzene ring. He explains the decomposition of methylmorphi- methine ruethohydroxide, when its aqueous solution is evaporated, by the equation C18H2cMeN0,,Me*OH = NMe, + C15H1002 + C2H4 + 2H,O. The compound C,5H,o0, is a phenanthrene derivative, and it yields a tetzabromo-deyiuative, C,,H,Br,O,, which me1 t s at 290". Synthesis of an Isomeric Narcotine.By CARL T. LLEBERMANN (Ber., 1896, 29, 183-187) .-Opianic acid and hydrocotarnine are mixed in molecular proportion and introduced into sulphuric acid (about 73 per cent.) free from nitrites, the liquid is well cooled, and after 12 hours diluted with ice-cold water, the unaltered opianic acid is removed, and on the addition of soda isona?.cotiize, CnH2,NO7, is pre- cipitated ; it crystallises from alcohol in colourless needles or prisms, melts a t 19=b0, and is insoluble in alkalis. With pure concentrated sulphuric acid, a carmine coloration is obtained, the production of which may also be used as a test for the presence of opianic acid, cotarnine, or hydroco tarnine.The yield is excellent. When boiled with baryta water, the sa74 . [C,2H14N03-CH(O13)~CsH2(0Me)2*COO]zBa, is formed, from which isonarcotine is regenerated by sucees- sive treatment with sulphuric acid and soda. The hydrochloride, C2,H2,NO7,HCI + 2Hz0, is crystalline, readily soluble, and with- out physiological action on rabbits. The hydrobromide is more sparingly soluble than the hydrochloride ; the hydriodide is practi- cally insoluble in cold water, and, like the nityate, crystallises in colourless needles. The platinochloride and azwoclrloride are yellow. Attempts to synthesise narcotine from meconine and cotarnine, or hydrastine from meconine and hydrastinine, and from opianic acid and hydrohydrastinine have hitherto been unsuccessful. Eydyocotarninephthalide, CG%< CH(CnH,,NO,) >o, is prepared, in a similar manner to isonarcotine, from hydrocotarnine and yhthaJ- aldehydic acid ; it crystallises from alcohol, melts at 193O, gives a pale yellow coloration with concentrated sulphuric acid, and, in alcoholic solution, has an alkaline reaction.The plntinochloride is pale yellow and flocculent. The hydriodide, C20HP,,N0,,HI, crptallises in needles, and, like the nitrate, is sparingly soluble. Replacement of the Hydroxyl Group of the Cinchona, Alkaloids by Hydrogen. By WILHELM KOENIGS (Bey., 1895, 28. 3143-37 48).--Whea cinchonine chloride is dissolved in dilute sulph- uric acid and treated with iron filings, a small amount of cinchene is formed along with deoxycinchonine, C19H22N2, in which the chlorine atom of the cinchoniue chloride is displaced by hydrogen.The base C. F. B. CO --- J. B. T.ORGANIC CHEMISTRY. 265 melts at 90-92', and dissolves in alcohol, the solution being strongly dextrorotatory. It is not identical with dihydrocinchene. Wheii heated with hydrobromic acid, additive products alone are formed, whilst with phosphoric acid, a little lepidine is produced. On oxida- tion with potassium perrnanganate in acid solntion, it does not yield cinchoninic acid, but a product which appears to be derived from deox y cinchotenine, C 16N,,N 2 0 2 . Deox ycouc hiniiz e, C 20H2*N20 4- 2H20, prepared from conchinine chloride, crystallises in the asymmetric system, and melts a t 80-82". It is readily soluble in 10 per cent. aqueous tartaric acid, and does not yield apoquinine when heated with hydrobromic acid, an additive compound being the sole product. The base is thus sharply distinguished from conchinene, which melts at the same temperature.The alcoholic solution of the base is strongly dextrorotstory, and has a deep violet-blue fluorescence. A U Resolution of Tropinic acid. By RICHARD WILLSTATTER (Ber., 1895, 28, 3271-3292 ; compare this vol., i, G5).-i-Tropinic acid was prepared from tropine by Merling'a method ; the yield is 30-38 per cent., that of LZ-tropinic acid, from ecgonine, is 29 per cent. Both acids, when titrated, give values indicating their monobasicity ; phenolphthalein was employed as indicator. Methylic i-tropinnte, C8H,,N0,1fIea, is prepared by the action of hydrogen chloride on tropinic acid and methylic alcohol, and is a colourless, ociourless, neutral oil; it boils at 268-272', and is in part decomposed; potas- sium permanganate reacts slowly with it ; when hydrolysed, tropinic acid is regenerated.The yield is 70-90 per cent. of the acid employed, but it is smaller if hydrogen bromide or sulphuric: acid is used. The auroch2oride is oily. The picrate crystallises i n small, orange-yellow, qusdmtic prisms, melts a t 121°, and is conveniently used for the purification of the methylic salt. itlethylic d-tropinate resembles the inactive compound ; its picrnfe crystallises iu long, thin needles melting at 120-121'. Methylie i-tropinate ndhiodide, C,H,,N04Me2,MeT, is formed only slowly, and crystallises with 4H,O from methylic alcohol in higfily refractive, long prisms, from water in thin, prismatic aggregates, me3 t- ing and decomposing at 172", whilst, from ether, anhydrous, slender, nacreous plates are deposited.The uwrochloride of the methochloride crptallises in thin, slender, golden, lustrous plates, and melts at 116-117'. When treated with silver oxide. the above methiodide FH,CH+ H-y o yields a betaine derivative, the awo- COOMe*CK CH2*NMe2*0 ' chloride of which crystallises in long, orange-yellow needles me1 ting at about, 182'. Dimethylie d-tropinate methiodide crystallises in colour- less plates and needles, which melt and decompose a t 177". The aurochloide of the methochloride crystallises in microscopic, quadratic plates and needles melting at 1 14* ; the corresponding derivative of the betahe, is deposited in slcnder needles, which melt and decompose at 195'. Hofmann has shown that dimethylpiper~lammonium iodide is decomposed by alkali into hydriodic acid arid dimethylpiperidine ; methylic i-tropinate methiodide behaves in a similar manner ; when266 ABSTRACTS OF OHEMIOAL PAPERS. heated a t 70-80" for two minutes with potassium carbonate, it J ields nzethylic i-met11 yltropitrate, Nhfe2*CH :C (C 0OM.e) CH2* C Hz*C H2* C 0 ONe, which is a faintly coloured, oily liquid with an extremely feeble alkaline reaction; it boils at 280' (corr.), and decomposes in part under the ordinary pressure ; potassium permanganate is instan- taneously decolorised. The yield is about 90 per cent. of thc theo- retical. When fused with potash, first at 160°, and finally a t 240-250°, it is converted into adipic acid, formic acid, dirncthylamine, and, in small quantity, acetic acid. The yield of adipic acid is about 60 per cent. of the theoretical. Methylic i- and d-tropinate methiodide and iuethylic d-methyl tropinnte react in the same manner. Metlzylic i-me t h y 1 tropinate p latinochloride, (C HloXO&, H2P t C 16, cry s t alli ses in orange-red, prismatic aggregates, and in well developed, highly refractive needles from water and hydrochloric acid respectively, and melts at 147-148'. The aurochloride is oily ; the picrate is deposited in long, transparent, amber-coloured crystals me1 ting at about 'i7-iS'. Methylic i-rnetliyltropinate methiodide crystallises in spherical, aggregated prisms melting a t 131-132c ; if deposited from alcohol, they contain +H20. The aurochloride of the mefhochloride, forms well developed golden prisms melting at 1 1 8 O , whilst the cor- responding mmornethylic derivative, C9H,~&IeNO4,MeAuCI4, ci-ystal- lises in sulphur-yellow, prismatic aggregates, which soften at about 100'. 211etlz ylic d-mefhyltropinate mefhiodide resembles the inactive isomeride, and melts at 121-182'. When methylic i- and d-niethyltropinate methiodides are boiled with soda they yield trimethylamine, pipery lenedicarbozy lic acid, CH2:C (C00H)*CHtI,*CH2:CH*COOH, and hydriodic acid, whilst a portion is resolved into its constituents ; the reaction corresponds with that by which Hofrnann prepared piperjlene, CH,:CH*CH,.CH:CH,, from the compound obtained by the complete methylatiou. of pipe- ridine. The acid crystallises from water in long, silky needles and prisms, melts at 169O, decomposes carbonates readily, rapidly decolorises potassium permanganate solution, and is di basic ; the electrolytic conductivity, K = 0.0116, pca = 354. The yield is 75 per cent. of the theoretical. The silcer sait, C,H604Ag,, i s deposited in slender, microscopic pibisms ; under the same conditions, A' 1 .2-pentenedicarboxylic acid yields a characteristic hydrogen silver salt. The basic copper saltl is greenish-blue; the lead salt white and flocculent ; the zinc salt is granular ; the cadmium salt is crystalline. ~et?.abroi~zo~i~e~ylenedicarboxylic acid, CiH,04Br,, crystal- lises from formic acid in colourless prisms, melts and decomposes at 218*, is stable towards potassium permanganate, and is rapidly decomposed by alkalis. The formation of this compound shows that piperylenediearboxylic acid contains two double linkings, but their position remains undetermined. P~opylic i-tropinate is prepared in tlie same way as the methylic sdt, which it resembles in general properties; the methiodide is oily;ORQANIC aHEMISTRT. 267 the aurochloride of the methochlo~ide, CBH,,PrazNO~,~~eAuCI,, crystal- lises in slender, sulphur-coloured needles, and melts a t 103O. When the above methiodide is treated with potassium carbonate, it yields pyopylic i-nzethyltropinute, the nzethiodide of which crystnllises in lmtrous, stelIate needles and prisms melting at 116--117*; when i t is heated with soda, piperylenedicarboxylic acid rcnd trimethylamine are pro- duced. The formation of the above methylic and propylic tropinate methiodides shows that fropinif acid contains a tertiary nitrogen atom, as indicated by Merling’s formula ; Ladenburg’s formula indicates the presence of a secondary nitrogen atom. The production of sdipic acid from metbyltropinic acid, described above, is probably preceded by that of formyladipic acid, OH*CH:C(COOH)*CH,*C H,-CH,*COOH, which is then further hydrolgsed to adipic and formic acids. The monobasicity of tropinic acid suggests that it may be a betaine derirati ve, but the methylic arid pi-opylic salts have not this constitution, since t,he latter, after complete methylation, yields trimethylamine, and not dime th y lpropylamin e. J. B. T. Cactus Alkaloids. 11. By ARTHUR HEFFTER (Ber., 1896, 29, 216-229 ; compare Abstr., 1895, i, 12Oj.-The formula, CI3Hl9NO3, is now assigned to pellotine, and its mercu?-oclrloride has been pre- pared. Its third oxygen atom must existl i n the form of hydroxyl, for it yields an oily monobeitzoyl derivative, the platinochloride and aurochloride of which were prepared. When boiled with methylic iodide and methyl-alcoholic potash, the alkaloid yields meth.t/Zpellotine methiodide, ClrHz,N03,MeT, melting at 225O ; from this, the chloride and platinochlon’de were prepared ; the quaternary anzmonimn base itsel € forms hygroscopic crystals which melt at 185‘. No well defined pro- ducts were obtained by heating the alkaloid with hydrochloric acid ; in one experiment, the compound- C,,H,,N( OH)2*OMe---pellotine with one of its two methoxyl groaps replaced by Iiydroxyl--was obtained, aud characterised by means of its yellow picrate, which melts at 9 3 O . Of tbe products obtained by distilling the alkaloid with soda lime or zinc dust, only t.rimethylamine could be identified ; of the products of iis oxidation, only oxalic acid. A1 kaloids of An liaEo?> itc m L e w inii, Hennin gs ( LophopiLora Lewinii, Rushy).-The dried “ discs ” ($cheiben) of this cactus are used by the Indians of N. Mexico for the preparation of an intoxicant, and arc brought into commerce under the name of “Muscale buttons ” (from Spanish Mezccil, a kind of brandy made from various species of Agave). They were extracted with 70 per cent. alcohol, and the residue obtained by evaporating this extract was extracted with ether and then with chloroform. The chloroforrn dissolved an alkaldid which was named mezcaline, whilst the ether dissolved several alkalojids, and by crystallising their sulphates, the sulphnte of one, nnhaloaidine, was obtained mixed with some mezcaline sulphate. The2 68 ABSTRACTS OF CHEMIC,AL PAPERS. mother liquor was treated with barium chloride, and the hydrochloride of anhalonine (Lowin, this vol., i, 194) then obtained from it, From the final mother l i q u o ~ , the mercurochloride of another alkaloi'd, lophophovine, was obtained and eventually convcrted into the crystal- lised hydrochloride. Mezcaline, CI,Hl,NOs, melts at 151'; it contains three methoxyl groups. The suZphate has the compositiou ( C~lHl,N03>z,H2S04 + 2H20 ; the yellow platinochloride is anhydrous. Anhalodine, ClZH15KO3, melts at 16ci0, and contains two methoxyl groups ; the hydi*ochlul-ide is lsvorotatory in solution ; the yellowish- red platiizochloride is anhydrous. Anhalonine, CI2HI5NO3, melts at 85.5' (Lewin, 77.5") ; it contains one methoxyl group. .Lophophori?ze, CI3H1,NO3, was not obtained crystallised ; the yellow platinochlol-ide is anhydrous. All give the same colour reactions, identical with those of pellotine. The following percentages of the pure, alkalo'ids were obtained from the drug : mezcaline, 6.3 ; anhalonidine (with a, little mezcaline), 5.3 ; anhalonine, 3.0 ; Iophophorine, 0.5. C. F. B, Pectase. By GARRIEL BERTRAND and ALFRED MALLEVRE (Compt. rend., 121, 726-728).-See this vot., ii, 267. The Separation of Lysine. By EDMUXD DRECHSEL (Bev., 1895, 28, 3189---3190).-Lysine may be isolated from the products of the decomposition of casein by hydrochloric acid, by converting it. first into the dibenzoyl C O I Z I ~ O U U ~ , lysuric acid. This is then purified by the re~rystallisat~~oii of its acid barium salt, from which the pure lysine can readily be liberated. 2C,H,2Bz,N202 + (CsHiiBzzNzOz)zBa,, A. H.

ISSN:0368-1769    

DOI:10.1039/CA8967000197

出版商:RSC    

年代:1896

数据来源: RSC