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iUINERALOGICAL CIIEMISTSY. 75 Mineralogical Chemistry. Critical Review of Methods of Determining Minerals. By JOSEPH W. RICHARDS (Chenz. News, 1897, 76, 114-11 6, 139-140).- The author comments on Dana’s, Weissbach’s, Von Kobell’s and Fuch’s schemes f o r determining minerals, and concludes that the best scheme should regard the physical properties as suggestive before, and con- Jrnzatory after, the chemical composition, the true determinative factor, has been ascertained. By his scheme, the following is the order of tests. (1.) Test met,allic and malleable minerals, for metals. (2.) Test specifically light and black minerals, for hydrocarbons. (3.) Test minerals having any taste, for salts. (4.) Test minerals with metallic, adamantine, and resinous lustre, in open tube and otherwise, for sul- phur, arsenic, antimony, selenium, tellurium.(5 .) Test other minerals for silica, and then test as required, (6) for phosphates and borates, (7) for carbonates, (S) for sulphates, (9) for volatile acids. (10.) Then try open tube tests. (11.) Bead tests for weak acids, chromium, vanadium, &c. (12.) Blowpipe tests. 10, 11 and 12, in some cases, would probably be done in test 4. Experimental Petrogeny. By KARL B. SCHI~IUTZ (Jaiwb. f. Min., 1897, ii, 124--155).-A summary of this paper has already been given by Doelter (Abstr., 1897, ii, 54 ; compare also Abstr., 1897, ii, 329). L. J. 5. Amber. By PAUL DAHMS (Juiwb. f. Mi%., 1897, ii, Ref., 273-274 ; from Schriften naturforsch. Ges. Dai2xig, 1897, 9, l-l9).-The com- mercial clarificatioh of cloudy amber by heating in oil depends on the pores of the amber becoming filled with oil.Mineral and albuminous matters are extracted from the amber, and a little phosphoric acid is taken up from the crude oil. According to the author’s determina- tions, amber contains. D. A. L. ( a ) A resin soluble in alcohol, with melting point 105”. ( b ) A resin soluble in ether, but insoluble in alcohol, m. p. 1 4 6 O . ( c ) A resin soluble in alcoholic potash, m. p. 175”. (d) Succinin, 44-60 per cent. ( e ) Succinic acid, 3.2-8-2 per cent. The soluble portion represents the original balsam of the amber tree, and the succinin is an alteration product of this. I n the dry clarifi- cation of amber, by heating it in sand for some time, the soluble resins76 ABSTRACTS OF CHEMICAL PAPERS.melt and fill the pores ; the same result is brought about a t the ordi- nary temperature after a long interval of time. L. J. S. [Blende, Ankerite, Galena.] By GEORGE J. BINNS and GEORGE HARROW (Trans. Fed. Inst. Mining Eng., 1897, 13, 252-255).-The following minerals are found in the coal-measures a t Netherseal Colliery, Leicestershire. Blende, as small, black crystals, lining cracks in bands and nodules of clay-ironstone, gave on analysis Minerals from Netherseal Colliery, Leicestershire. Zn. Fe. Ca. Mg. Cd. S. Total. 63-20 2.11 0.50 0.36 trace? 33.91 100*08 ilnkerite occurs as indistinct rhombohedra, associated with the blende, and also with galena ; it is white, but changes to buff on exposure to the air ; analysis gave CaCO,. FeCO,.MgCO,. Gangue. Total. 53.0 23.3 20.8 1.1 98.2 Galena, from clay filling a fault-fissure, gave PbS. FeS. ZnS. Gangue. Total. Sp. gr. 98.42 0.27 0.41 0.46 99.56 7.39 Hartley and Ramage have detected copper, silver, iron, sodium, and Barytes, calcite, and copper pyrites are also . found. Minerals of the Harz. [Blende, Stibnite, Jamesonite, Orthite, Axinite.] ‘By OTTO LUEDECKE (Zeit. Kryst. Xifi., 1897,29, 176-192). -The author here recapitulates a l l . the original matter contained in his recent book, Die Minerale des Hc6rxe.s (Berlin, 1896) ; this deals mainly with occurrences and crystallographic determinations. The following new analyses are given. potassium in this galena by spectroscopic methods. L. J. S. Blench from Clausthal gave, on analysis by Reinicke, Zn.Fe. Pb. S. sio,. 64.25 2.25 0.03 33-13 0.5 1 This gives the ratio (Zn,Fe,Pb) : S = 1 : 0.9. Stibnite from Wolfsberg was found to contain nothing but antimony It would, therefore, be useful for the determination of Jccmesonite, in compact, felty masses of capillary crystals, from and sulphur. the atomic weight of antimony. Schwenda gave, on analysis by G. Baumert, Pb. Sb. S. Fe. 49.57 28.53 19.84 0-53 Orthite, in crystals, from quartz veins in gabbro a t Barenstein, gave SiO,. CaO. MgO. (Ce,La,Di),O,. (Al,Mn,Fe),O,. Sp. gr. 29.05 5.67 0.52 21.56 29.29 3.784 Axinite, in crystals, from crystalline limestone a t Radauthal, gave Baumert results agreeing with the formula H,R”20Si,,0,,,R”1,Si90,,. SiO,. CaO. FeO. MgO. MnO. Fe,O,. AI,O,. B,O,. K,O. H,O. 39’26 29-70 3.65 1.81 2‘80 2‘62 14.46 4‘91 0.25 1 2 2 L.J. S.MINERALOGICAL CI I EMISTRY. 77 Identity of Chalcostibite (Wolfsbergite) and Guejarite. By SAMUEL L. PENFIELD and AUGUST FRENZEL (Anaer. Journ. SCi., 1897, 4, 27-35 ; and Zeit. KTyst. Min., 1897, 28, 598).-Chalcostibite was first described, from Wolfsberg, in the Harz, in 1835, as being ortho- rhombic and having the composition Cu,S,Sb,S,. I n 2879, Cumenge (Abstr., 1881,517) gave the name guejarite to an orthorhombic mineral from Guejar-Sierra, Spain, which had, according to his analysis (I), the composition Cu2S,2Sb,S,. The later crystallographic determinations made by Laspeyres (Abstr., 1892, l%4) on the Wolfsberg mineral agreed completely with those previously obtained for guejarite ; and from a re-examination of Cumenge’s original material, the present authors have established the identity of chalcostibite and guejarite which was suggested by this agreement.Analyses by Frenzel, made on measured crystals of “guejarite,” gave the results under 11,111, and IV, these agreeing closely with the formula Cu,S,Sb,S,, the percent- age composition of which is givenunderV1. For these analyses, every crystal was first qualitatively tested for copper, in order to make certain that no stibnite crystals were present, since this mineral, as noticed by Cumenge himself, closely resembles chalcostibite in colour, lustre, the perfect pinacoidal cleavage, and in crystal habit. The excess of antimony in Cumenge’s analysis (I) was probably due to the presence of stibnite. r. 11. 111. 1 v.v. VI. S ......... 25.0 26.28 - 26-13 26-20 25.87 Sb ...... 58-5 48.86 48.50 48.44 48-45 48.50 Cu ...... 15.5 24.44 25.92 25.23 24.72 25-63 P b ...... trace 0.58 - 0.32 Fe ...... 0.5 0.42 - 0.49 Zn ...... - - - - - - - - 0-1 8 - - - 99.5 10058 100.78 99-37 100.00 - - Sp. gr .... 5-03 4.96 Chalcostibitie has recently been found at the Pulacayo mine, Huan- chaca? Bolivia, where it occurs with tetrahedrite, pyrites, and quartz. Analysis of crystals gave the results under V (Frenzel). These crystals, being very perfect and rich in terminal planes, have enabled accurate determinations of the crystallographic constants of chalcostibite t o be made ; Penfield finds a : b : c = 0.5312 : 1 : 0.63955, the perfect cleavage being taken as parallel to the basal plane, and the elongated striated zone as the macroaxis 6.L. J. s. [Bournonite from Bolivia.] By AUGUST FRENZEL (Zeit. A7ryst. $fin., 1897,28, 607--609).-The veins of the Pulacago silver mine, at Huanchaca, are in a trachytic quartz-porphyry, and contain the follow- ing minerals : quartz, pyrites, tetrahedrite, blende, galena, copper pyrites, rarely stibnite, stephanite, chalcostibite (precedibg abstract), and bournonite, together with traces of bismuth and tin compounds. Tetrahedrite is the piincipal ore ; it contains up to 10 per cent. of VOL. LXXIV. ii. 675 ABSTRACTS OF CHEMICAL PAPERS. silver. times embedded in the tetrahedrite ; analysis gave Bournonite occurs as small, bright, columnar crystals, some- Pb. cu. Ag. Fe. Zn. S b. S. Total. 40.88 12.70 trace 0.40 0.14 24.78 20.50 99.40 L.J. S. Composition of some Tellurium Minerals. By WILHELM MUTHMANN and E. SCHR~DER (Zeit. li'qjst. Min., 1897, 29, 140-145). -The authors have examined specimens of tetradymite with the idea of determining the amount of selenium which has been shown by several previous analyses to be present in traces. Full details of the methods of analysis are given in the paper. Tetradymite from Orawicza, Hungary, gave I and 11, after deducting about 11 per cent. of gangue ; it occurs as greyish-white scales with copper pyrites and tetrahedrite in calcite ; selenium is absent. Tetradymite in distinct crystals from Schubkau, Hungary, gave 111, IV, and V ; sp. gr. 7,0946; traces of selenium are present. All these analyses agree with the formula 2Bi,Te,,Bi,S, = Bi,Te,S.I. 11. 111. I v. V. Vl. VII. S 4.51 4-47 4.20 4.35 4.39 9.31 9-40 Bi 58.93 59.34 60.36 59.98 60.34 79.31 78%2 Te 35.30 35-56 35.25 35.35 35.68 12.82 12.66 98-74. 99.37 99-81 99.68 100.41 101.44 100.88 ------- A tellurium mineral from Cumberland, analysed by Rammelsberg in 1853, gave VI and VII, corresponding with the formula Bi,S,Te or Bi(S,Te). The irregular masses are grey in colour with a nietallic lustre, and have a perfect cleavage in one direction. On the cleavage surface, there are cracks intersecting at 60°, and the thermal con- ductivity figure is a circle, so that the crystal system is rhombohedra1 as in tetradymite. The formula, in which bismuth is bivalent, is analogous to that of karelinite (Bi,O,S). This new mineral is named grunlingite. L.J. S. By ALFRED BERGEAT (Jcblwb. f. Him. 1897, ii, 109--123).-The older lavas of the volcanic island of Stromboli, in the Lipari Islands, are andesites, whilst the newer are basaltic in character. A leucite rock, namely, leucite- basanite, is described. Good mineral specimens are rare on the island ; besides augite crystals and thin plates of haematite, only the following is described. The mineral, of which the following analysis by Hilgenstock is given, occurs as dull crusts of a dark, blne-grey colour on lava. This crust is composed of small, regular octahedra, often arranged in groups parallel to a cubic axis, and then having the appearance of tetragonal prisms terminated by pyramids. The mineral resembles haematite in the colour of the powder, but differs from it in being strongly magnetic.The sp. gr. of the crystals is 4.995, and of the powder, after separating tridymite and plagioclase, 5.247. On fractures, and in thin Sp. gr. 7.321. [Cubic Ferric Oxide] from Stromboli.MINERALOGICAL CHEMISTRY. 79 sections, the crystals are seen t o enclose much hEmatite as thin plates arranged parallel to the octahedral faces. Al,03 (probably Fe,O,. FeO. RlgO, MnO. from plagioclase). Gangue. Total. 94-68 2-67 0.17 0.25 1.48 99-25 This description suggests martite, but the author is inclined to regard the mineral as magnesoferrite (RlgO,Fe,O,) enclosing much hamatite. L. J. s. By J. MILNE CURRAN (Journ. and PYOC. Boy. Xoc. X.X.W., 1897, 30 (for 1896), 214-285). -In this paper, which is illustrated by eight plates, the modes of occurrence and characters of all the known precious stones from New South Wales are described.A complete bibliography and historical sketch are added, together with some methods for the dis- crimination of rough stones. Diumond is found in the drift a t three localities, the most important being Bingara. Sapphire chiefly occurs in the tin-bearing drifts of the Emmaville and Tingha districts; it has also been found in basalt. Ruby is very rare in the colony. Emeruld occurs near Emmaville in a decomposed felsitic matrix associated with topaz, fluorite, mispickel, cassiterite, &c. Transparent crystals gave, on analysis by J. Petrie, Precious Stones of New South Wales. SO,. A1,0,. BeO. CaO. MgO. Na,O. H,O. Total. Sp. gr. 65.20 17.80 14.40 1.00 0.64 0.34 0.62 100.00 2.73 Rare alkalis could not be detected spectroscopically.Topux is abundant in the tin-bearing drifts and granites of the northern part of the colony. Analysis of bluish-white, transparent material from Emmaville gave, Total SiO,. A1,0,. CaO. F. (less 0 for F). Sp. gr. 30.29 60.90 0.40 15.05 100.30 3.60 Red pyrope (anal. I) occurs near Bingara in a basic, holocrystalline, granular rock (anal. 11) composed of pyroxene and felspar; the garnet is surrounded by a kelyphite border. SiO,. A1,03. Fe,O,. FeO. MnO. CaO. MgO. K,O,Na,O. H,O. Total. Spgr. Garnet is common, but good stones are rare. I. 39'57 23.68 0'18 10.04 3.76 8.76 14'45 - - 100'44 3'743 II. 42'4 18'4 10'4 - trace 16'6 8'5 2'5 1'2 100.0 3'1 I I I . 49'80 9-90 8.64 - - 15'80 16.86 - - 100~00 - Anal.I11 is of large phenocrysts of augite from an olivine-basalt dyke containing garnets, from near Harden. Turquoise occurs as thin crusts and concretionary masses in a dark, carbonaceous shale, containing pyrites, from near Bodalla. It is of a good sky-blue colour, but on exposure becomes greenish owing to loss of water. Apalysis gave, P,O5. A1,0,. Fe,O,. CaO. CnO. SiO,. II,O. Total. Sp. gr. 31.90 36,236 1.264 1-70 '7.45 0.50 21.00 100.05 2.67 6-280 ABSTRACTS OF CHEMICAL PAPERS. Opal is well known from White Cliffs, where it occurs in Upper Cretaceous sandstones; the silica has been derived from beds of organic (diatomaceous and radiolarian) origin. Zircon, beryl, nephrite, cordierite, serpentine, malachite, and various varieties of quartz are also described.Pseudogrtylussite from Holland. By F. J. P. VAN CALKER Zeit. Kryst. Mirz., 1897, 28, 556-572).-S,yheroida1 groups of crystals, closely resembling t,he well-known pseudomorphs from Sangerhausen, in Thuringia, and other localities, have been found embedded in alluvial clay a t Onderdendam in the province Groningen. The pyramidal cryst,als are of a yellowish colour, and the surfaces are rough and curved ; in the interior, they show a cellular aggregate of differently orientated calcite grains. Analysis shows the presence of S9.9462 per cent. of calcium carbonate. L. J. S. CaO. MgO. A1,0,. Fe,O,. RTa,O. u20. 50.6281 0.5000 1.8657 1.2985 0.2718 0.1086 SO,. GO,. SO,. (clay). (at 100"). (on ignition). Total. 0.1426 40.4659 0.3689 2,3804 0.7704 1%011 1@0*6020 Insol.H,O H2O Pseudogaylussite is also recorded from Kwadyk and Friesland in Holland. A review of the literature of these pseudomorphs is given, and the evidence supplied by t,he chemical composition and external form discussed. No definite conclusion is arrived at as to what was the original mineral, which has been variously assumed t o be gaylussite (Breithaupt, 1 S36), celestite (Des Cloizeaux, 1843), gypsum (Kenngott, 1870), anhydrite (Groth, lS78), and a hypothetical tetragonal chloro- carbonate of calcium (Dana, 1884). The author has failed to detect strontium by spectroscopic methods; and the presence of a little sodium carbonate and the porous structure of the pseudomorphs seem t o suggest that gaylussite mas the original mineral. Several measured angles are given, but, owing to the roughness and curvature of the faces, the variations are considerable, and they compare equally well with both gaylumite and celestite.[Pyromorphite, Mimetite, &c.] fiom Broken Hill, N.S. W. By CHARLES W. MARSH (Tyans. Australian Inst. Mining Eng., 1897, 4, 13S-l59).-Cerussite is remarkable for the variety of crystalline aggregates produced by twinning. Pyronzolyhite, occurring in crystalline aggregates, gave analyses 1-111. A lemon- to orange-yellow variety called ' I chromo-phosphate " contains some chromic acid as well as arsenic. L. J. S. PbO. P,O,. Rs,05. V,O,. C1. Total. I. Brown ............ 81.9 14.4 0.8 - 1.9 99.0 11. White ............ 80.8 14.6 2.3 - 2.2 99.9 IV. Yellow ............ 74.7 1.2 21.4 - 2.8 100.1 V. White ............74.2 5.7 17.6 - 3.4 99.9 VI. Red ............... 73.9 1.S 18.2 3-6 2.1 99.6 111. Straw-yellow ...... 79.3 13.2 6.2 - 1-1 99.8MINERALOGICAL CHEMISTRY. 81 Mimetite crystals gave analyses IV-TI. The bright yellow is the most pure, sometimes containing only a trace of phosphoric acid; the lighter coloured and greenish specimens contain more phosphoric acid, whilst those coloured red and brown contain vanadium and graduate into vanadinite. WzcZJenite occurs as orange-yellow, orange-red, and deep red crystals, the last containing some chromic acid. Stolxite occurs as smoky -grey, yellowish, and reddish tetragonal crystals, and in long, thin plates. [The last, of which figures are given, is probably identical with raspite (this vol., ii, 32)l. Several rare minerals are also mentioned as occurring a t Broken Hill : namely, hedyphane, phosgenite, lanarkite, leadhillite, matlockite, percylite, linarite, minium, jordanite, sartorite, boulangerite, and jamesonite.Anglesite and galena are also described. L. J. S. Gypsum Deposits of Nottinghamshire. By ARTHUR T. MET- CALFE (Tmns. Feed. Inst. Jfining Engineers, 1896, 12, 107-1 14)- Bands of gypsum are abundant in the upper marls of the Keuper beds of Nottinghamshire aud Derbyshire ; it is worked as an orna- mental stone, and for the manufacture of plaster of Paris. The composition of an ordinary sample is, Siliceous caso,. CaC03. Oxide of iron. matter. H,O. Total. 77.37 0-83 0.50 0.30 2 1.00 100~00 Anhydrite sometimes occurs in the centre of masses of gypsum. L. J. S. [Analysis of Soda-mica].By FRANZ EIGEL (Zeit. liryst. illin., 1897, 29, 169 ; from Jahresber. des F. B. Gymnasiums urn Seckauer Diocesan-KnabensemincLr, for 1894-5). -White mica from a '( sericite- mica-schist " consisting essentially of quartz and mica, from near Pollau, Styria, gave, on analysis, SO,. h1,0,. CaO. Na,O. K,O. H,O. Total. 51.43 32.11 traee 11.80 1.29 5.67 102.30 L. J. S. The optic axial angle is large. The amount of soda is much higher than shown in any previous analysis. Composition of Comendite. By SOLIMANN BERTOLIO (Jabb. f. Min., 1897, ii, Ref. 292 ; from Rend. R. Accad. Lincei, 1896, [y], 5, (a), 150-152. Compare Abstr., lS97, ii, 55).-The zgirite-liparite from S. Pietro in Sardinia has been called comendite ; a specimen richer in alkalis, and with less quartz than usual, gave analysis I.Sp. gr. 2.57. Some of the felspar is schillerised, but still clear; an- alysis I1 shows it to be anorthoclase; sp. gr. 2.58-2-59. The amphibole, which resembles arfvedsonite, gave I11 ; sp. gr. 3.33. SiO,. Al,03. Fe,O,. FeO. MnO. CaO. MgO. Ii,O. Na,O. Total. I. 68'5 14.5 1.0 3.0 - trace 0-1 3.0 9.2 99.3 11. 66-1 18'2 trace - 0.1 - 3.5 11.4 99.3 111. 49.10 5.50 4-20 27.70 0.50 0'13 0.17 1460 10.50 99-40 L. J. S.82 ABSTRACTS OF CHEMICAL PAPERS. Sodalite-trachyte from the Siebengebirge. By WILLY BRUHNS ( V e h rzccturhist. Ver. Bonn, 1896, 35, 39-56).--The peculiar rock from Kuhlsbrunnen, in the Siebengebirge, has of ten been described and is usually called an zgirite-trachyte; it is now shown to contain sodalite, to which the cellular structure of the weathered rock is due.I n the fresh rock, the sodalite is present in clear, colourless, isotropic grains; it dissolves easily in dilute nitric acid, yielding a clear solu- tion, without any separation of gelatinous silica. The portion of the rock soluble in dilute acid gave analysis I ; besides sodalite, this would only include a little glass and magnetite. A partial analysis (11) of the augite needles confirms the reference, made on optical grounds, to =@rite. The felspar is all sanidine; magnetite is abundant, and a glassy base is rare ; analysis of the fresh rock gave the results under 111. LOSS 011 SiO,. ALO,. Fe,03. FeO. M110. CaO. MgO. K,O. Na,O. C1. ignition. Total. I. 34'2 31.2 trace - - nil. nil. nil. 27'9 7.5 - 100.8 [I.- 2 28 notdet. - little nil. 10 - - - -+ 111. 63'61 16'34 4.30 2.08 trace 1.42 0'37 5.54 6-21 0'18 0.77 100.82 Detailed descriptions and analyses are given of hachytes from other localities, which were examined on account of their similarity in appearance to the Kuhlsbrunnen rock ; no sodalite was, however, found in these. L. J. 8. Contact-metamorphism of Phyllites. By K. DALMER (Jahrb. f. -#in., 1897, ii, 156--158).-At Schneeberg, in Saxony, a phyllite composed of 24.93 per cent. of chlorite and 75.07 of muscovite has been altered into a rock containing andalusite 31.1, muscovite and biotite 68.9 per cent. ; the two rocks, as shown by analyses I and I1 respectively, have essentially the same composition. SiO,. A1,03. Fe,O,. FeO. MgO. CaO. K,O. Na,O. H,O. I.39.49 34.47 5.86 5.74 1.85 0.25 5.38 1.17 55'8 11. 39.00 34.85 6-18 6.15 2.09 0.46 6.18 1.67 3.47 I n this change, as represented by the following equation, part of the muscovite of the phyllite has been altered to andalusite, and the potassium silicate and silica so liberated have, with chlorite, formed biotite ; 40Si0,,20R,0,,2R0,4K~O,2Na~O,12H,O (muscovite) + 6Si02,6R,0,,SR0,10H,0 (chlorite) = 12AI,SiO, (andalusite) + 18Si0,,6R,O,,lOR0,3K,0,3H,O (biotite) + 1 6Si0,,8R,03, 3(Na,K),0,5H20 (potash-soda mica) + 14H,O. At Rothschonberg, in Saxony, a phyllite is altered into a rock com- posed of muscovite, biotite, and quartz ; analyses show the presence OF more free silica in the phyllite than in the altered rock, so that here biotite has been produced from chlorite and quartz, the potassium having been supplied by the muscovite.From chlorite or muscovite with quartz, cordierite may be produced. By EMIL W. C'OHEN ( A m . k. k. nccturhist. Hof- museums Wieien, 1897, 12, 42-62).-New analyses of the Nennt- mannsdorf (Saxony), Lion River (S. Africa), Prambanan (Java), and L. J. S. Meteoric Iron.PI-IYSIOI,OGICAL CHEMISTRY. 83 Chesterville (S. Carolina) irons gave the results under I, 11, 111 and I V respectively ; these differ from previous analyses in showing the presence of cobalt, It is pointed out that in octahedral irons, as in Lion River and Prambanan, the amount of Ni + Co is 8-11 per cent. The Zacatecas (Mexico) iron gave analysis V ; in t,he hydrochloric acid residue, there is an undetermined phosphide of nickel containing a relatively large amount of copper and but little iron.The minera- logical composition of this iron is given as Kickel- Schreiber- Dnubr6e. Chromite Nickel Undet. iron. site. Troilite. lite. and silicate. Carbon. phosphide ? residue. 94.34 3.54 0.26 0-10 0.21 0.03 1.08 0.44 A new analysis of rhabdite from the See-Lasgen iron (compare Abstr., 1897, ii, 57) gave VI, from which (Fe,Ni,Co) :P = 3.109 : 1. The Bischtu be (Russia) iron has the mineralogical composition, Nickel-iron Chromite Undet. Nickel-iron. phosphide. Carbon. and silicate. residue. 96-97 2.52 0.09 0.01 0.41 The schreibersite, together with a little rhabdite from this iron, gave analysis VII, agreeing with (Fe,Ni,Co),P, and the flexible plates of tsnite gave VIII. The present results differ considerably from Kislakowsky's (Sbstr., 1892, 418), who found 17.90 per cent. of olivine and anorthite. A new analysis of cohenite from the Wichita Co. (Texas) iron gave, after deducting about 8 per cent. of schreibersite, the results under IX, agreeing with the formula (Co,Ni,Fe),C ; the variations shown in previous analyses are to be explained by the presence of tzenite. An iron carbide from the telluric iron of Ovifak (Greenland) gave analysis X, showing it to be probably identical with the meteoric cohenite. Fe. Ni. Co. P. C. Cr. S. Insol. Total. Sp. gr. I. 94.33 5.48 0.71 0'29 - nil. - - 100'81 7'8241 IV. 93'15 5-82 0.73 0'34 - - - - 100.04 7'8738 II. 92.06 7'79 0'69 0'05 - - - - 100'59 - 111. 90'03 9-39 0.97 0.16 - - - - 100.55 - V. 92.09 5.98 0.91 1-02 - 0.74 0.18 0.04 100'96 - VI. 46'32 38.06 0.94 14'89 - nil. - 0.94 101.15 - VII. 66'19 18'47 0'43 15.58 - - - 0.07 100'74 - VIII. 62.19 35'90 0.35 0'92 0.75 - - - 100.11 - IX. 90.80 2.37 0'16 - 6.67 - - - 100'00 7'3236 X. 92.73 0.95 0'39 - 5.93 -- -- - 100~00 - L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8987405075

出版商:RSC    

年代:1898

数据来源: RSC

摘要:

Pl~Y8IOI~OGIChL CH EMISTltY. Physiological Chemistry. 83 Metabolism during Muscular Work in Dogs. By NATHAN Zumz (PJEuger’s A~chiv., 1897, 68, 191-21 l).-All mammals hitherto investigated need, in normal work, nearly the same amount of chemical energy per work unit, somewhat more than a third of the available84 ABSTllACTS OF CHEMICAI, I’APEHS. energy appearing as external work, whilst the remainder is changed into heat. I n pulling work, the useful effect of the transformed energy is somewhat smaller than in climbing, and diminishes with increase of work. The horizontal movements of the animal’s own body require, for equal weights moved through the same distance, somuch the more work the smaller the animal is. The relationship between the work and the transformation of energy is nearly proportional to the super- ficial area of the body.Solubility of Paracasein in Artificial Gastric Juice. By W. LINDEMANN ( V~YC~OW’S Archiv., 1897, 149, 51-65).-Previous re- searches on cnseinogen (here called casein) have shown that the residue obtained on gastric digestion is small, and with excess o€ gastric juice is absent (Salkowski). I n the present investigation, casein (here called paracasein) was em- ployed, and the powdered proteid subjected to the action of gastric jnice (in some experiments, however, it was previously dissolved in a minimal quantity of alkali) ; a residue was found in all cases, varying from 0.15 to 10.07 of the substance taken, but the percentage usually obtained was 3 or 4. Casein is, therefore, less digestible than caseinogen; the residue is smaller the larger the amount of digesting fluid employed ; the quantity of acid in the mixture has some influence, but the duration of the digestion beyond 34 hours has none.Origin of Fat from Proteid. By EDUAED PFLUGER (PJEiigeY’s Arclziv., 1897, 68, 176-1 go).-A further polemical contribution to a much discussed subject ; the author does not believe in the origin of f a t from proteid, and seeks to shorn from the experiments of those workers who do believe in it, that their conclusions are incorrect. W. D. H. W. D. H. W. D. H. Fat of Muscle: Estimation of Fat in Animal Substances. By ELLY BOGDANOW (PJriiger’s Archiv., 1897,68, 408-430; 431-433). -The principal point made out is that, in the later extractions of muscle with ether, the fat obtained is different from that obtained in the first extracts, and that the fat obtained last is very rich in free fatty acids; this confirms the observations of Dormeyer, who used an entirely different method.The method here used is explained a t full length, with wood-cuts of the apparatus employed. Extraction of animal tissues with ether does not, however, extract all the f a t ; more goes into solution on subsequent extraction with boiling 90 per cent. alcohol. The largest yield is obtained by a five days extraction with alcohol in a Soxhlet’s apparatus, after the finely divided material has been allowed to remain a day under ether. The experiments in this direction are not complete, but it is hoped that this simple method will give results equally trustworthy with those obtained by Dormeyer’s more complicated process.By LEOPOLD JOLLY (Compt. rend., 1897, 125, 538-539).-The ordinary molybdic acid solution in dilute nitric acid serves for the detection of phosphates in animal tissues, to which, if they contain phosphoric acid or its salts, a yellow colour is imparted. No similar coloration is produced by macerating W. D. H. Biological History of Phosphates.PHYSIOLOGICAL CHEMISTRY. 85 the same tissues with nitric acid of the same strength. The author’s observations show that many tissues, even after being macerated for some time with dilute acetic acid or dilute nitric acid, retain phos- phoric acid which can be detected by means of the molybdic reagent in the manner indicated. It follows t h a t the association of the tissues with this part of the phosphoric acid must be of a very intimate charac ter .C. H. B. Catechol-like Substance in the Suprarenal Capsules. By OTTO VON FORTH (Zeit. physiol. Chem., 1897, 24, 142--158).-This paper gives an account of attempts to isolate the substance which has been known since Vulpian’s researches to exist in the medulla of the suprarenal capsules and gives a greenish colour with ferric chloride. The author does not appear to have been any more successful in these attempts than his predecessors ; he describes the material as catechol-like, but admits that it contains nitrogen. By CARL THORE (GRAF) MORNER (Zeit. pJ~ysioZ. Chena., 1897, 24, 125--137’).- The scales of various fishes were investigated, and the organic ground substance was found to be not wholly composed of collagen, about a fifth of it consisting of :another albuminoid named icJbthgZepidin, which differs from collagen in containing loosely united sulphur, from keratin in its small percentage of sulphur (1*09), and from elastin by its smaller resistance t o chemical reagents.Composition of Sow’s Milk, with Special Regard to the Amount of Fat. By 31. PETERSEN and FR. OETKEN (Bied. Centr., 1897, 711-713 ; from il-lilchxeit., 1896, 665).-The examination of seventeen samples of sow’s milk, from Oldenburg, and of a few other samples, showed that the amounts of fat and dry matter are greater than in cow’s milk. The following percentage results are given. Fat, 2.4 to 12.1 ; dry matter (average of four samples), 20.4 ; proteids, 3.8 to 5.3 ; sp.gr. (one sample only) = 1.0128. The high percentage of fat (average of 22 samples = 6.6) is in accordance with previous results. By ERICH HARNACK (Zeit. pJ~ylsi01. C’hem., 1897, 24, 115-124).-By administer- ing to men or dogs small, medicinal doses of tannin or gallic acid, the quantity of gallic acid in the urine is very small, but the greater amount is contained in the fsces. It is probable that some of the gallic acid which passes into the urine is decomposed, and traces of pyrognllol are found, if, in searching for it, the acidified urine has been evaporated ; if the evaporation is omitted, pyrogallol is never found. Pgrogallol is highly poisonous, and is not formed in the organism. On giving larger doses of gallic acid, more passes into the urine, especially if alkalis are given as well.By feeding on free tannin, none passes into the urine; but it is found after giving a freshly-prepared solution of tannin in alkali. For the isolation of tannin, the salting-out method by saturated sodium chloride solution, and precipitation by solution of gelatin or albumin W. D. H. The Organic Ground Substance of Fish Scales. W. D. H. N. H. J. M. Physiological Action of Tannin and Gallic Acid.S6 ABSTRACTS OF CHEiMiChL PAPERS. free from globulin, is recommended. The separation of small quantities of pyrogallol and gallic acid is only possible when the solubility of the former in boiling benzene is made use of. By THEO. KLIKGXAN ( V~YC~OW'S Archiv., 1897, 149, l2-22).-A number of previous workers have noticed that the most marked effect of the administra- tion of naphthalene is an opacity of bhe lens and other degenerative changes in the eye-ball.I n the present research on rabbits, naphtha- lene dissolved in liquid paraffin was given by the stomach; in the urine, phenol was found corresponding to about a tenth of the naphthalene given. The animals were killed a t varying intervals ; in the early stages, an irido-cyclitis was found, which is believed to be the starting point of the subsequent eye-changes in the cornea, lens, and retina. The priniary lesion is not in the retina, as Panas considered, W. D. H. Physiological Action of Eucaine B. (4-Benzoyloxy-trans- 2 : 2 : 6-trimethylpiperidine). By GAETANO VINCI (?'h'ChOW'S Archiv., 1897, 149, 217-235).-The action of eucaine B. (4-benzoyloxy-t~an,s- 2 : 2 : 6-trimethylpiperidine) is similar to that of eucaine, previously described (ibid., 145), and of cocaine. Locally, i t dilates the blood- vessels, although in smaller measure than does eucaine, and it also enlarges the pupil. Anaesthesia is produced, as with cocaine and eucaine, by direct contact with the sensory nerve-endings. There is an action on the central nervous system, and a curare-like paralysis of the motor and vagus nerve-endings; this is attributed t o the absence of the COO13 group, and is not observed with eucaine and cocaine, which contain that group. Eucaine 13 has an antiseptic action ; it is less soluble than the other drugs, but is cheaper and an equally good local anzsthetic. W. D. H. [Physiological Action of Naphthalene.] W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA8987405083

出版商:RSC    

年代:1898

数据来源: RSC

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S6 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture, Nature of Fermentative Changes in Natural and Polluted Waters, and in Artificial Solutions, as Indicated by the Com- position of the Dissolved Gases. Part IV. Humus: Its Formation and Influence in Nitrification. By WALTER E. ADENEY (Trans. Boy. Dublin, SOC., 1897, [ii], 6, 269-281. Compare Abstr., 1896, ii, 322).-The author gives reasons for adopting the terms, carbon oxidation and nitrogen oxidation or nitrification, t o respectively denote the two stages by which organic substances succes- sively undergo complete aerobic bacterial fermentation in waters. With the adoption of these terms, the author proposes the classification of all fermentable substances into (1) carbon-oxidisable substances, or all fermentable organic substances which have not undergone carbon- oxidation ; and (2) nitrifiable substances, or ammonium compounds, and organic compounds which have suffered carbon-oxidation.The author has described the changes which result from these twoVEGETABLE PHYSIOLOGY AND AGRICULTURE. 97 stages of fermentation, in his previous communication. The object of the experiments now recorded has been to ascertain the fermentative properties of the humus of ordinary cultivated soils, and thereby t o complete the information already published (Zoc. cit.) on the fermenta- tive properties of the nitrifiable organic substances which are to be found in natural waters. The humus employed in these experiments was obtained from a large heap of wet refuse matter, which consisted of the solid matters t h a t had been separated from sewage and mixed with freshly precipitated man- gmese peroxide in about equal proportions. The heap was allowed to ferment for about three months, a t the expiration of which time the peroxide was found to be completely reduced and converted into manga- nese carbonate.The organic matters, which at this time amounted to about 8 per cent. of the air-dried mass, were also found to have under- gone a practically complete first-stage fermentation or carbon oxidation, and to have all the properties of the humus of ordinary cultivated soil. That the reduction of the peroxide to carbonate of manganese can be brought about by bacterial fermentation, has been shown by McWeeney, who found that, when freshly precipitated manganese peroxide was kept in sterilised liquid media, it remained unchanged, but that when the same media were seeded with small pieces of the fermented refuse matters above referred to, a rapid and abundant growth of living organisms ensued, and the complete reduction of the peroxide to carbonate quickly followed.The author records a number of experiments with this humus, which show that it possesses fermentative properties similar to those which he has already shown peaty colouring matters and fermented organic matters to possess, the most characteristic property of which is t o determine the nitric fermentation of ammonium compounds. The possible changes which nitrifiable substances, to be met with in natural waters, may undergo are summarised as follows. 1.When the nitrifiable organic substances are freshly formed, and are present in comparatively large quantity in a water, the formation of a volume of carbonic anhydride, in proportion to the volume of oxygen consumed, and the formation also of a quantity of nitrous or of nitric acid, or of both, but in small quantities, may attend the earliest stage of fermentative change they may undergo. 2. A t subsequent stages, the volume of carbonic anhydride formed is not so large, and the quantity of inorganic nitrogen products, nitrous or nitric acid, becomes more marked, in proportion to the oxygen consumed. 3. At a still later stage, a t the completion of which all the ammonia becomes fermented, little or no carbonic anhydride may be formed, but, on the contrary, a little may become “fixed”; the inorganic nitrogen product consists then of nitric acid solely.4. When little or no ammonia is present, freshly formed nitrifiable organic matters may undergo a t first a slow change, during the first steps of which distinct amounts of carbonic anhydride and of oxygen may be formed and consumed, respectively ; small quantities of nitric acid are formed at the same time. 5. But, after these earlier steps of change, the fermentation becomes88 ABSTRACTS OF CHEMICAL PAPERS. slower, and finally so slow as to be scarcely appreciable; still, the results are the formation of carbonic anhydride and nitric acid, and the con- sumption of a proportionatelysmall volume of oxygen. W. E. A. Fermentation Phenomena. By ALFRED STAVENHAGEN (Bey., 1897,30, 2422-2433).-A solution prepared from yeast by Buchner’s method (Abstr., 1897, ii, 154), but filtered through a Chamberland filter, was found to be perfectly sterile and possessed all the properties of that prepared by Buchner, except that it did not cause the slightest fer- mentation with cane-sugar, glucose, or milk-sugar.The author con- siders that the acknowledged presence of micro-organisms in the solution obtained by Buchner is sufficient to invalidate his experiments on the fermentation of sugar without yeast cells. A. H. Chemical Characteristics of the Woody Matter of the Oak. By PAUL METZGER (Biecl. Centr., 1897, 26, 678-679 ; from Inaug. Diss. Mztnich, Heilbronn, 1896).-The sap-wood and heart-wood of oak both contain the same tannin, the composition of which agrees fairly well with Bottinger’s formula, Cl5Hl6Oll.The tannin of the bark, however, seems to be present in a partly decomposed condition, and to contain phlobaphen. Both tannins must be considered as glucosides, as they are converted by boiling with dilute acids into phlobaphen, gallic acid, and glucose. Phlobaphen, C3,H3,Ol,, is capable of taking up twelve acetyl groups. Free gallic acid was found in the bark, sap-wood, and heart-wood of all ages. All three parts of the wood contain the same fats (the glycerol ethers of palmitic, stearic, cerotic, and oleic acids), oxalic, malic, and tartaric acids, cholesterol, cane-sugar, and pentosans. Starch occurs in the sap-wood and in the heart-wood, but not in the bark. The amount of ash in the bark decreased from the root to the top, but increased in the sap-wood and heart-wood.The phosphoric acid in the bark increased towards the top, but diminished in the sap-wood and heart-mood; there was only an increase of phosphoric acid in the sap-wood of the newest shoots. Chlorine could not be detected in any of the ashes. N. H. J. M. Effect of Humus on the Percentage of Nitrogen in Oats. By HARVEY W. WILEY (Landw. Versuchs.-Stat., 1897, 49, 193-202).-A number of experiments, extending over three years, are described, in which oats were grown in large pots containing peaty soil, without manures and with a variety of manures, The soil contained, on the average, less than 10 per cent. of mineral matter, over 2.5 per ceut. of nitrogen, and very little potash and phosphoric acid.The best of the soils employed mas free from nitrifying organisms, but contained ammonia organisms in a fairly active condition. The most striking result obtained was the high percentage of nitro- gen in the produce, amounting to about 25 ’per cent. more than is found in oats grown on ordinary arable land. This increase i s mainly in amide nitrogen and not in proteid nitrogen, and is, at least in part, due to direct absorption, from the soil, of nitrogenous matter which hasANALYTICAT, CHEMISTRY. 89 not been nitrified. amide nitrogen of the produce. The following average results show the total and Grain and chaff. Straw. Roots. Total N. N. as amides. Total N. N. as amides. Total N. N. as aniides. The amount of proteid nitrogen remained within the limits of the usual amounts obtained on ordinary soil. Potash and nitrogenous manure, in the amounts applied, had no appreciable effect on the amount of produce. Phosphates raised the yield and, a t the same time, lowered the percentage of nitrogen, probably owing t o the increased crop rather than to any injurious action of the phosphates. The three phosphatic manures employed (Florida phosphate, basic slag, and superphosphate) had almost the same effect on the amount of produce. N. H. J. M. 2.63 0.35 1.99 0.70 1.45 0.32

ISSN:0368-1769    

DOI:10.1039/CA8987405086

出版商:RSC    

年代:1898

数据来源: RSC

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ANALYTICAT, CHEJZISTRY. 89 Analytical Chemistry. Use of the Electrometer as Indicator in the Titration of Acids and Bases, By WILHELM BOTTGER (Zeit. physikal. Chem., 1897, 24, 263--30l).--Behrend (Abstr., 1893, ii, 3S7) :has shown that an electrometer may be used to determine the end point in mercury titrations, a chain being employed of the type : mercury 1 mer- curous nitrate I mercurous nitrate I mercury. The author shows that a similar method may be used in the titration of acids and bases, if a hydrogen electrode be employed, the form used by the author being made of gold electrolytically coated with palladium, the E. M. F. being determined by the aid of a capillary electrometer and a Clark 01- Weston normal cell, Titrstions were made of solutions of hydrochloric, isobutyric, tartaric, phosphoric, arsenic, and carbonic acids, and of sodium hydroxide, aniline, ammonia, and a mixture of sodium hydroxide with benzylamine. The E.M. F. was found, after the addition of each C.C. of the neutralising liquid, and in a second experiment after each drop, in the neighbourhood of the point of neutralisation. Curves are constructed with the number of C.C. added as ordinates, and the E. M. F. as abscism. The form of the curve depends on the dissociation con- stant of the acid, but in all cases i t ascends, at first slowly, then very rapidly, then again slowly, an almost vertical part indicating the neutral point. I n all the cases considered, the form of the curve is the same as that obtained theoretically from the equation r = 0*0002T.logC2/C,, where C, and C, are the ion concentrations of the hydrogen, although the absolute values of the E.M. F. may not agree always with those obtained from the curve. For the weak acids, the method is also available, whilst with phosphoric and arsenic acids the points corre- sponding with the formation of the compounds NaH2P04 and Na2HP04 and the corresponding arsenic salts are indicated. With arsenious and boric acids, the point where one-third of the hydrogen is displaced90 ABSTRACTS OF CHEMICAL PAPERS. is seen on the curve. The availability of the method for weak orgnnic acids is also proved, and the author points out that the agreement of the results with the theoretical deductions may be also taken as a further proof of the validity of the theory.Estimation of Perchlorate in Sodium Nitrate. By F. WINTELER (Chem. Zeit., 1897, 21, 75-76).-Ten grams of the sample of “Chili saltpetre ” is introduced into a tube containing 10 C.C. of fuming nitric acid and a little silver nitrate. The tube is then sealed and heated for 5 hours a t 230’. The silver chloride thus formed is afterwards weighed. Any chlorine existing as chloride or chlorate must be determined and allowed for. Separation of Bromine from Mixtures of Bromides and Chlorides. By HENRI BAUBIGNY and PAUL RIVALS (Contpt. rend., 1897, 125, 527--530).-When bromine is liberated from dissolved bromides by the action of cupric sulphate and potassium permanganate, the collection and direct estimation of the bromine is difficult. Dis- tillation with water vapour is inconvenient, owing to the large volume of condensed liquid, but the bromine can readily be carried over i n a current of air and absorbed in a dilute solution of an alkali. The salt to be analysed and the copper sulphate are dissolved in a flask with a neck 160 mm.long, and the permanganate is then added. The con- denser tube and the tube carrying the current of air pass through a stopper which is ground into the neck of the flask. Thealkali solution (3 or 5 per cent.) is contained in an inclined absorption tube consisting of a series of bulbs connected by short, narrow tubes and the absorption is complete even when 2250 C.C. of air per minute is passed through the liquid in the flask from a tube 3 mm. in diameter. The liquid in the flask may be heated by means of a water bath to any desired tem- perature, and, in order to compensate for evaporation, the air may first be saturated with water vapour by bubbling i t through water contained in a flask heated in the same water bath.When all the bromine has been expelled and absorbed, the liquid in the absorption tube is mixed with some sulphurous acid, then with silver nitrate solution, and finally with nitric acid in moderately large excess ; the liquid is boiled for some time, and the precipitated silver salt dealt with in the usual way. Estimation of Sulphur in Iron. By OTTO HERTING (Chem. Zeit., 1897, 21, 87).-The author states that the results obtained by Wiborgh’s colorimetric process are untrustworthy, as the quantity directed to be taken for analysis is far too small, The best results are obtained by Wood’s cadmium process, the sulphur in the cadmium precipitate being titrated by means of iodine.De Koninck’s proposal of adding a little stannous chloride when dissolving the sample in hydrochloric acid, so as to prevent oxidation of the hydrogen sulphide, is considered by the author to be superfluous, although i t must be admitted that the action proceeds in a more Estimation of Sulphur in Pyrites by means of Sodium Dioxide. By CHARLES GLASER (Chem. Zeit., 1897, 21, 40-41).- When pyrites is oxidised by heating it with sodium dioxide, the melt, L. M. J. L. DE K. C. H. B. steady and regular way (Abstr,, 1895, ii, 528). L. DE K.ANALYTICAL CHEMISTRY, 91 on being treated with water, sometimes deposits a blackish powder which contains ferrous sulphide.The author now states that, in such a case, the experiment need not be rejected; it is only necessary to add a little more of the sodium dioxide to ensure complete oxidat ion When testing pyrites rich in sulphur, there is no necessity for rendering the silica insoluble before precipitating with barium chloride, but excess of the latter should be avoided. L. DE K. Estimation of Mixed Sulphides, Sulphites, Sulphates, and Thiosulphates. By FRED W. KICHARDSON and HENRY E. AYKROYD (J. Soc. Chenz. Id., 15, 171--173).-0ne portion of the solution is devoted to the estimation of sulphates, the neutral solution having been acidified with 5 grams of tartaric acid,is precipitated in the cold by barium chloride ; the thiosulphates remain undecomposed, and the precipitate contains only some barium sulphate with some sulphite, the latter being removed by treatment with hot dilute hydrochloric acid and washing with hot water.From another portion of the solution, the salphides are precipitated by ammoniacal zinc chloride. The filtrate from the zinc sulphide is then coloured with methyl-orange, and N/10 sulphuric acid run in until the change in the indicator shows that the sodium sulphite has been converted into sodium hydrogen siilphite. The mixture is now made up to a known volume and employed for titrating a measured quantity of N/10 iodine solution, after which the acidity developed is ascertained by titration with N/lO sodium hydroxide. In accordance with the equation NaHSO, + H,O + I2 = NaHSO, + 2H1, each molecule of sodium sulphite originally present will require three molecules of sodium hydroxide to restore neutrality.The excess of iodine above that consumed by the sulphite is calculated into thiosulphate. The results obtained in analysing a solution of known composition were very close. M. J. 8. Estimation of Phosphorus in Iron and Steel. By OTTO NERTING (Chenz. Zeit., 1897, 21, 13S-l39).--The author did not get satisfactory results with Carnot’s method of direct weighing of the molybdate precipitate ; moreover, no better results were obtained with Mauermann’s process, in which the precipitate is dissolved in standard ammonia and the excess titrated with standard acid, using corallin as indicator. A colorimetric met hod proposed by Namias, based on the blue coloration developed when dissolving the yellow precipitate in sodium thiosulphate, gives good results, but offers no special advantage over Emmerton’s permanganate process.The latter process has been slightly modified by the author. One gram of pig-iron is dissolved in 50 C.C. of nitric acid of 1.135 sp. gr., heated to boiling, and mixed with 20 C.C. of a solution of potassium permanganate (8 grams per litre) ; after boiling for 2 minutes, a saturated solution of ammonium oxalate is added drop by drop until the brown manganese precipitate has redissolved. After boiling for another 2 minutes, 5 C.C. of nitric acid of sp. gr. 1.42 is added, the liquid filtered, and the insoluble matter washed twice with hot water; as soon as the temperature has fallen to 65”, the liquid is poured into a beaker98 ABSTEACTS OF CHEMICAL PAPERS.containing 100 C.C. of molybdate solution, heated a t 60°, and well stirred. The precipitation of the phosphoric acid is complete in 15 minutes ; the bulk of the liquid is now poured off, and the precipitate washed on a filter with acid ammonium sulphate solution (10 grams ammonium sulphate, and 20 C.C. of sulphuric acid in 1 litre of water) until all the iron is removed. The precipitate is then dissolved off the filter by means of dilute ammonia, and filtered into an Erlenmeyer flask containing 10 grams of granulated zinc ; dilute sulphuric acid (1 : 2) is added in excess, and the whole heated for 8 minutes. It is then filtered through a quick filter containing a few pieces of zinc, and the filtrate a t once titrated with permanganate ; the strengih of the permanganate expressed in iron, multiplied by 0.01 64, represents the phosphorus. When testing wrought iron or steel, 5 grams of the sample is dissolved in 90 C.C.of nitric acid of 1.135 sp. gr., and 10 c c. Estimation of Citrate-Soluble Phosphoric Acid in Basic- Slags. By 0. BOTTCHER (Chem. Zeit., 1897, 21, 168--169).-The author states that, if the solution of the basic-slag in Werner’s ammonium citrate solution is mixed with a sufficiency of magnesium mixture and well agitated in a shaking apparatus for half an hour, the precipitation of the phosphoric acid is complete. If, however, the liquid is not then at once filtered, a gradual separation of silica will By PIERRE NOLF (Zeit. physiol. Chem., 1897, 23, 505--520).-The author shows that “ (1.) Normal ammonium carbonate, or a mixture of ammonium chloride and sodium carbonate, yields a considerable quantity of carbamic acid when treated by Drechsel’fi method.(2.) The same is true of am- monium hydrogen carbonate, or a mixture of pure sodium hydrogen carbonate and ammonium chloride. (3.) An aqueous solution of free carbonic acid and ammonium chloride gives a similar result. (4.) Instead of ammonium chloride, other ammonium salts can be used ; for example, the nitrate, oxalate, or acetate.” Both dilute (I : 600) and comparatively concentrated solutions were experimented with. The presence of carbamic acid was detected by shaking,.preferably a t Oo, first with a little lime, and again after adding calcium chloride; the liquid was now either filtered and sealed up in a glass tube, when the gradual appearance of a turbidity indicated the presence of calcium carbamate, or it was filtered into alcohol, the residue digested with ammonia, and the oxtract also filtered into alcohol, the precipitate that formed in the alcoholic liquid being examined after the lapse of half an hour, to see whether it had the characteristic form of calcium carbamate.It is concluded that not only the reactions of carbamic acid, but calcium carbamate itself, will be obtained by Drechsel’s method, wherever ammonium carbonate is present in solution, or free carbonic acid side by side with an ammonium salt.” A quantitative estimationis only possible when i t is a solution of the calcium salt that is being dealt with; the amount of ammonium carbamate present in an alkaline solution is purely a matter of chemical equi- librium.(2, F. B. acid of 1.42 sp. gr. is afterwards added. L. DH K. take place and the results will be untrustworthy. L. DE K. Detection of Carbamic Acid.ASALYTICAL CHEN ISTlIY. 93 Estimation of Free Alkali and Alkali Carbonate in Soaps, with and without the use of Alcohol. By WILLIAM WALTKE (Chem. Zeit., 1897, 21, 137).-The author states that soap should not be dried before extracting with alcohol, as the caustic alkali is then to a, serious extent converted into carbonate by the carbonic anhydride from the air. Better results are obtained by dissolving 5 grams of the sample in 75 C.C. of absolute alcohol contained in an Erlenmeyer flask fitted with a soda-lime tube to prevent carbonic anhydride from entering the flask; after dissolution has-been completed by the aid of a gentle heat, the liquid is filtered inside a water oven, the insoluble matter washed a few times with hot absolute alcohol, and the free a1 kali then titrated with NjlO sulphuric acid, using phenolphthalein as indiaator.To estimate any alkali carbonate, the insoluble residue is dissolved in cold water, and also titrated with the acid, this time using methyl-orange as indicator. The free alkali can be estimated by dissolving 5 grams of the sample in 250 C.C. of hot water freefrom carbonic anhydride, and pouring this solution slowly into 100 C.C. of a 5 per cent. solution of barium chloride. The free alkali in the filtrate is then titrated as before. Another 5 grams of soap is then dissolved in 15 C.C.of water and nearly dried on a sand bath with constant stirring, passing a current of carbonic anhydride over the mass all the time. After drying at l l O o , the residue is weighed to ascertain the amount of moisture; the carbonic anhydride is then estimated by means of a Geissler's apparatus, and after allowiiig for the amount absorbed by the free alkali, the difference is calculated into Ry T. J. BAKER (Chem. News, 1897, 7S, 167).- Weighing the precipitate oh- tained with hydrochloric acid, also fusing the impure silver chloride with sodium carbonate and nitre, give iinsatisfactory results ; therefore, the author boils about 50 C.C. of the solution with a slight excess of nitric acid, filters, washes, and dries the precipitate, wraps it and the filter ash together in assay lead, and then cupels.Separate Estimation of Alumina and Iron Oxide in Phos- phates. By F. LICHTSCHLAG (Chem. Zeit., 1897, 21, 264-265).- Two grams of the sample is fused with 8 grams of sodium carbonate for 20 minutes, then quickly cooled, and the product, which can readily be detached from the platinum crucible, is put into a beaker, the crucibe being rinsed with dilute hydrochloric acid, which is then used t o dissolve the melt. When the latter is completely dissolved, the solution is neutralised in a 200 C.C. flask with aqueous soda, heated to boiling, 30 C.C. of a 20 per cent. solution of aqueous soda is added, and the whole heated for 15 minutes. When cold, the liquid is made up to the mark, and 75 C.C. is poured off through a quick filter ; as soon as 50 C.C.has collected, it is mixed with excess of hydrochloric acid, a few drops of sodium phosphate solution are added, and, after boiling, the alumina is precipitated as phosphate by adding a very slight excess of ammonia. The residue on the filter is dissolved in 1iydro:bloric acid, which is VOI,. LXXIV. ii. 7 The estimations may also be made without using alcohol. alkali carbonate. L. DE K. Estimation of Silver in Silver Plating Solutions. D. A. L.94 ABSTRACTS OF CHEMICAL PAPERS. then added to the contents of the flask ; after adding some more acid, the liquid is introduced into a 500 C.C. flask and the iron reduced at 70" by means of zinc. When cold, the liquid is made up to the mark, and the titration proceeded with as Fresenius directs.L. DE K. By LEOPOLD SCHNELDER (Chern. Zeit., 1897, 21, 41).-The sample is dissolved in nitric acid, and the solution, diluted with twice its volume of water, is boiled and mixed with pure lead peroxide, when the manganese is instantly oxidised to permanganic acid. After filtering through as- bestos, the filtrate is titrated with a standard solution of hydrogen per- oxide until colourless. The hydrogen peroxide solution is standardised against a known weight of potassium permanganate dissolved in dilute Estimation of Chromium in Chrome Ore and Ferrochro- mium. By ERNEST H. SANITER (J. Soc. Chenz. Ind., 15, 155-158). -This paper is partly controversial. The author has modified Clark's process (Trans., 1893, 1079) and claims, in opposition to Rideal and Rosenblum (J.80c. Clzena. Ind., 14, 1017), that chrome ore ground only '' moderately finely " in an agate mortar can be completely de- comjosed in 3 minutes. A nickel capsule 2 inches wide and 1 inch deep is used. 0.5 gram of the chrome ore and 3 grams of sodium dioxide are mixed in the capsule, which is then held by tongs in a Bunsen flame. As soon as the mass begins to melt, a circular motion is given to the capsule to prevent the ore from settling. The tempera- ture should be just below a visible red. When cold, the capsule is placed in a large basin and filled with cold water, and after the melt has dissolved it is rinsed with hot water. The solution, diluted to about 300 C.C. with hot water, is then coloured pink by adding potassium permnnganate ; 100 C.C.of dilute hydrochloric acid (1 : 1) is now gradually added, and the solution boiled until clear; 150 C.C. more hot water is added and the boiling continued for 10 minutes, by which time all chlorine is expelled. The cooled solution, now measur- ing 500 c.c., is titrated with ferrous sulphnte and dichromate. At this dilution, the nickel present, derived from the nickel capsule used, does not interfere with the titration. Ferrochromium is crushed until the whole sample passes through a sieve of 10,000 meshes to the square inch. For 0.3-0.5 gram of sub- stance, 4 grams of sodium dioxide and 0.75 gram of barium peroxide are taken, and the process is the same as before, except that a larger quantity of potassium permanganate is added, to prevent reduction of chromate by the barium peroxide.[SAMUEL RIDEAL and SIGMUND G. ROSENBLUM], criticising the paper, state that they were unable to get complete decomposition in one fusion unless the chrome ore was very finely ground ; that some sodium dioxide always remained a t the end of the fusion and reduced some chromate on acidifying unless previously decomposed by boiling, for which 10 minutes sufficed; that the addition of barium peroxide is both useless and a source of complications, and that it is better to filter from nickel oxide than to trust to dilution for masking the brown colour it gives with ferricyanide. M. J. S. Estimation of Manganese in Steel and Iron. nitric acid. L. DE K.ANALYTICAL CH EMLSTRY. 55 Estimation of Chromium in Ferrochrome and Chromium Steel.By Jos. SPULLER and A. BRENNER (Chem. Zeit., 2897, ii, 3-4). -Assay o f Pe~rochrorne.-O*35 gram of the finely powdered sampie mixed in a hemispherical silver dish with 2 grams of dry powdered sodium hydroxide and covered with 4 grams of sodium dioxide, is heated until the mixture begins to melt, when, as a consequence of the strong chemical action, the whole mass soon becomes liquefied. The dish is then again heated for 10 minutes over a powerful burner, and 5 grams of sodium dioxide is cautiously added, stirring all the while with a silver spatule. After heating for 30 minutes more, another 5 grams of sodium dioxide is added and the heating continued for 20 minutes, when a final 5 grams of the dioxide is added.When cold, the silver basin is placed in a deep porcelain dish and filled with water ; when the lixiviation is completed, which takes a few minutes only, the silver dish 'is lifted out and well rinsed with hot water. A brisk current of carbonic anhydride is then passed through the liquid for half an hour, the whole allowed to cool, introduced into a litre measure, and made up to the mark with water. After shaking and filtering, 250 C.C. is taken and the chromic acid titrated by Schwarz's method. I f the solution of the melt appears green, it is advisable to add first a few C.C. of potassium permangannte solution, and then some more sodium dioxide, when a pure yellow liquid will be obtained. Assay of Chrome-steel.-Two grams of the sample is dissolved in 20 C.C.of warm hydrochloric acid contained in a porcelain dish, 10 C.C. of dilute sulphuric acid (I : 1) is added, and the whole evaporated to dryness; hhe residue is then transferred to a hemispherical silver dish and heated with 2 grams of sodium hydroxide and 5 grams of sodium dioxide, until the sulphates are decomposed and the mass begins to cake. A strong heat is now applied and another 5 grams of the dioxide is added. When the mass begins to fuse, it is well stirred with a silver spatula, and after 20 minutes another 5 grams of sodium dioxide is added ; after another 20 minutes, when the oxidation is com- plete, a further addition of 5 grams of the soda is made and the maFs is allowed to cool. The melt is then extracted as in the former case, but the liquid is made up to 500 C.C.only, and 250 C.C. of the filtrate (1 gram of sample) is taken for the titration of the chromium. In this case, the authors prefer titrating according to Zulkowsky's method; the liquid is put into a long, narrow beaker, mixed with 10 C.C. of a 10 per cent. solution of potassium iodide, and acidified with pure hydrochloric acid. To another beaker containing 20 C.C. of a solution of potassium dichromate (0.9833 gram per litre), 250 C.C. of water is added, then 10 C.C. of a 10 per cent. solution of potassium iodide and a little hydrochloric acid. After being left for 15 minutes i n a dark place, both liquids are titrated with solution of sodium thio- sulphate containing 4.96 grams of the salt per litre. The amount of chromium being known in the one solution, the quantity contained in the other is readily calculated.L. DE K. Estimation of Nickel in Nickel-steel. By Jos. SPULLER (Chem. Zeit., 1897, 21, 243-244).-If the samples contain at least 1 per k n06 ABSTBACTS OF CHEMICAL PAPERS. cent. of nickel, the amount may be tolerably accurately estimated by dissolving 2 grams in 60 C.C. of nitric acid of sp. gr. 1.2, boiling until the nitrous fumes are expelled, and precipit,ating the iron by adding an emulsion of zinc oxide; the green 6ltrate is then collected in a suitable colorimeter, which may be improvised by using a beaker of about 7 cm. diameter placed on white glazed paper. I n a similar beaker is placed the filtrate obtained by dissolving 2 grams of a standard sample of nickel steel, removing the iron as before ; on comparing the tints, the amount of nickel in the commercial sample can readily be estimated.L. DE K. Separations with Alkali Acetates, 11. Nickel from Iron. 111. Cobalt and Manganese from Iron. By HARRY BREARLEY (Chenz. News, 1897, 76, 49-51, 165-167. Compare Abstr., 1896, ii, 676).--NickeZf~om Iro.n.-The substance is dissolved in hydrochloric acid and oxidised with nitric acid, or, if only a small quantity, or no carbon is present, it is dissolved in nitric acid directly, diluted, cooled, an alkali carbonate added until a slight permanent precipitate is formed, and then 10 C.C. of acetic acid. The liquid is diluted to about a litre with hot or cold water, 10 to 12 C.C. of ammonium (sodium) acetate solution added for each gram of iron in solution, adding more if no turbidity appears on heating to near the boiling point.If turbidity appears too soon, the heating is stopped when the precipitate becomes flocculent and the solution nearly colourless, and if the precipitation is slow after the turbidity has appeared at the boiling point, the heating is prolonged. An aliquot part of the liquid is filtered through asbestos, cooled, neutralised, a measured quantity of dilute ammonia added, arid the liquid then titrated with potassium cyanide and silver iodide. For a rapid result, or when there is sufficient ferric hydroxide to interfere, excess of cyanide is run in, the liquid filtered through asbestos, and titrated back with silver nitrate. By using ammonia salts, as much as 0.8 gram of nickel to 1 gram of iron may be estimated; the usual small amounts of manganese or chromium do not matter, but copper and larger amounts of manganese, chromium and aluminium must be removed.Large quantities of ammonia cause error, but the acetate, chloride, and nitrate do not do so appreciably. The last two, however, lessen the amount of alkali required to neutralise the iron solution and lower the temperature a t which turbidity appears and also deepen it ; whereas the sulphate, chloride, and nitrate lessen the turbidity in the order given. Artificial alizarin can be used as an indicator when neutralising the free acid; it gives a purple coloration in the presence of silver iodide, which changes to pink when the latter is dissolved. Cobalt ccnd iron. can be separated as in the preceding case of nickel; its presence in the solution causes a variable and transitory darkening on the addition of cyanide, and, moreover, the silver iodide dissolves before all the cobalt is saturated. Therefore, the titration has to be modified, and the cyanide, which is standardised with cobalt in this case, is rnn in in excess and after a while titrated back with silver nitrate.I n manganese separations, and, in fact, in all these separations, the acetates should be used as sparingly as possible. D. A. L.ANALYTICAL CHEMISTRY. 97 Analysis of Alloys of Tin, Antimony, and Copper. By GUSTAVE W. THOIIPSON (2 SOC. Chem. Ind., 15, 179--lS2).-Com- mercial alloys of the above metals frequently cont'ain, in addition, phosphorus, arsenic, bismuth, cadmium, nickel, and cobalt.The course of the analysis will naturally be modified by the absence of one or more of the metals, but the following method applies to cases where all are present. The alloy (1 gram) is dissolved in 100 C.C. of a solu- tion made up as follows :-20 grams of potassium chloride in 500 C.C. of water, 400 C.C. of concentrated hydrochloric acid, 100 C.C. of nilzic acid of 1.4 sp. gr. After concentrating to 50 c.c., the solution is cooled, precipitation of the lead chloride is completed by adding 2 vols. of 95 per cent. alcohol, and the precipitate, after being washed with a mixture of alcohol and hydrochloric acid (4 : l), is dissolved in ammonium acetate, precipitated as chromate, and weighed. The filtrate from the lead chloride is evaporated to dryness, heated for 20 minutes with 10 C.C.of po'tassium hydroxide (1 : 5) and 20 C.C. of 3 per cent. hydrogen peroxide (the object of which is to prevent separation of sulphur with the antimony sulphide), then mixed with 10 grams of ammonium oxalate, 10 grams of oxalic acid, and 200 C.C. of water, and treated with hydrogen sulphide for 45 minutes a t a nearly boiling temparature ; this precipitates copper and antimony (also bismuth, cadmium, and partially nickel and cobalt), but leaves the fin in solution. After expelling hydrogen sulphide from the filtrate, the tin (with traces of nickel and cobalt, and also of iron, if present) is precipitated by electrolysing the solution for 12 hours with a current of 0.5 ampere. The copper and antimony sulphides are separated by heating with potassium hydroxide, the copper is converted into nitrate and titrated with potassium cyanide in ammoniacal solution (or precipitated electrolytically if in large amount), whilst the antimony, after being converted into antimonic chloride by boiling with hydro- chloric acid and potassium chlorate, the excess of chlorine being ex- pelled and the sulphur filtered off, is reduced to trichloride by adding potassium iodide, and estimated from a titration of the iodine liberated.Arsenic accompanies the antimony, and is best estimated in a separate portion by distilling the hydrochloric acid solution with sodium thio- sulphate. Bismuth, cadmium, nickel, and cobalt sulphides would remain with the copper sulphide after separation of the antimony. Phosphorus is best estimated by Dudley's method.For the minuter details of the operations, and for simple methods suited only to special alloys, the original should be consulted. M. J. S. Estimation of Organic Matter by Chromic Acid. By JOSEPH BARNES (J. SOC. Chem. lnd., 15, 82-84).-With the view of super- seding the old permanganate method of ascertaining the amount of oxygen absorbable by the organic matter in a water by a process in which the oxidation should be more energetic, the author has employed a hot mixture of chromic and sulphuric acids. The solutions used are : one containing 6.2 grams of potassium dichromate and 50 C.C. of concentrated sulphuric acid per litre, a solution of ferrous sulphate containing about 36 grams of the crystallised salt with 200 c.c of sulphuric acid per litre, and a permanganate solution.To make an98 ABSTRACTS OF CHEMICAL PAPERS. estimation, 50 C.C. of the water is mixed with 25 C.C. of concentrated sulphuric acid and 10 C.C. of the chromate solution, and is heated on the water bath for 1 hour. It is then rapidly cooled, 10 C.C. of the ferrous solution and 500 C.C. of cold-water are added, and the excess of ferrous iron is titrated with the permenganate. Another method is described in which permanganic acid is used : 100 C.C. of the water is mixed in a stoppered bottle with 10 C.C. of dilute sulphuric acid (I : 2) and 10 C.C. of permanganate solution (4 grams per litre) ; and the bottle is lkept at 21’ for two and a half hours. An excess (10 c.c.) of ferrous sidphate is then added, and the excess titrated by a weaker permanganate solution (1 C.C.= 0.0005 gram of oxygen). A table is given showing the amount of oxygen absorbed by various organic matters in each process. The results are purely empirical, and are influenced (but in opposite directions) by variations in the amount of organic matter taken. M. J. S. By MILORAD R. JOVITSCHITSCH (Bey., 1897, 30, 2431--2432).-Mineral acids, such as sulphuric, nitric, and hydro- chloric acids, reduce Fehling’s solution, especially if the reaction be carried out in only slightly alkaline solution, the reduction being probably due to the decomposition of the tartaric acid by the mineral acid present; it is this, probably, which renders it necessary to carry out the tests with Fehling’s solution in a strongly alkaline solution. J.F. T. Blank experiments are required in both methods. Fehling’s Solution. Gravimetric Estimation of Sugars by Fehling-Allihn’s Pro- cess. By GOTTWALT AMBUHL (Chem. Zeit., 1897, 21, 137-138).- The author has analysed 38 samples of wine, 4 of honey, and 4 of urine by the above process, and has tabulated the results. The table shows that there is no necessity to reduce the cuprous oxide to metallic copper, as a direct weighing of the former gives Estimation of Furfuraldehyde by Means of Phloroglucinol. By CONSTANTIN COUNCLER (Chem. Zeit., 189’7, 21, 2--3).-The author (Abstr., 1895, ii, 144) states that i t is of great importance to use phloroglncinol free from diresorcinol. Unless the amount of furfur- aldehyde is very small, it is advisable to take an aliquot part only of the distillate for precipitation.The amount of furfuraldehyde yielded on distilling a sample of brown coal with hydrochioric acid was no less than 0 22 per cent., corresponding with 0.408 per cent. of pentosan calculated on the dried Colour Reactions of Pyruvic Acid, By LOUIS SIMON (Con@. 9-end., 1897, 125, 534-536).-See this vol., i, 64. Estimation of Fat in Animal Substances. By ELLY BOGDAKOW (P’uger’s Archiu., 1897, 68, 431--433).-See this vol., ii, 84. The Iodine Number of Fats and Oils. By HUGO SCHWEITZER and EnnL E. LUNGWITZ (J. Xoc. Chenz. Ind., 14, 1030-1035)- The authors have already proved (Abstr., 1896, ii, 398) that in Hubl’s sufficiently accurate results. L. DE K. sample. L. DE I<.ANALYTICAL CHEMISTRY.99 process, substitution, as well as addition, of iodine occurs. They now show that the use of methylic alcohol, recommended by Fahrion, whilst i t does not affect the total amount of iodine absorbed, increases the proportion employed in substitution. When the mercuric chloride is omitted, the iodine absorption consists chiefly, or, in the case of methylic alcohol, entirely, of substitution, but the proportion of substitutive iodine is not diminished by using more mercuric chloride than in Hubl’s standard reagent. I n chloroform and ethylic ether solutions, substitution also occurs t o a large extent ; but in carbon bisulphide and carbon tetrachloride solutions the absorption is additive only. Mercuric bromide, whether in ethylic or methylic alcohol, gives more substitution than mercuric chloride.Various other metallic chlorides were tried, employing ethylic alcohol solutions. With manganous chloricle (or bromide), cobalt chloride, and nickel chloride, very little sub- stitution occurred, but the total absorption was low and variable. By working with carbon bisulphide solutions, in the presence of mer- curic chloride, and at an elevated temperature (50-79”) in stoppered bottles and therefore under pressure, the iodine absorption may b e made to exceed that produced by Hubl’s normal process, being a t the same time a purely additive one. I n the case of oleic acid, the absorp- tion exceeds that theoretically required, and this raises doubts as t o the constitution of oleic acid. 31, J. S. Recognition of Margarine by means of Dimethylamidoazo- benzene.By ALFRED PARTHEIL (Chem. Zed., 1897,21,255-256).- In order to detect the presence of small quantities of margarine in butter, it has been proposed by Soxhlet to order all margarines to be mixed with a small quantity (1 : 100,000) of phenolphthalein. Any one would then be able to recognise adulterated butter by the reddish colour when the sample is mixed with a little soda. The use of phenolphthalein is, however, objectionable for many reasons, and the author now proposes to use dimethylamidoazobenzene dissolved in oil instead. Analysis of Fats : Estimation of Unsaponifiable Matter. By JULIUS LEWKOWITSCH (J. Xoc. Chem. h d . , 15, 13--14).-The pro- cesses in use may be classed under two heads : extraction of the soap solution with ether or light petroleum, and extract,ion of the dry soap by solvents.With certain oils, such as shark-liver oil, and some kinds of whale oil, both methods are unsuitable when petroleum is used, since the unsaponifiable matter is sparingly soluble in the cold petroleum, and at the same time much soap dissolves. The latter may be removed by washing the petroleum solution with 50 per cent. alcohol, but it is safer to use ethplic ether as the solvent, and correct for any dissolved soap by incinerating the residue left on evaporation and estimating the alkalinity of the ash. Analysis of Fats: Wool Wax, By JULIUS LEWKOWITSCH (J. Xoc. Chem. Ind., 15, 14-15).-Wool fat (Yorkshire grease) contains a considerable proportion of free fatty acids and true waxes, with a small quantity of free alcohols.The neutral portion, for which the author proposes the name “wool wax,” is now obtainable in This turns red on adding dilute sulphuric acid. L. DE K. 31. J. 5.100 ABSTRACTS OF CHEMICAL PAPERS. commerce. A specimen yielded 51.8 per cent. of unsaponifiable matter soluble in ether, also easily soluble soaps, and sparingly soluble soaps. The unsaponifiable matter had a melting point of 46-4So, iodine number 26.35. From its gain in weight when boiled with acetic anhydride (8.26 per cent.), cetylic alcohol must be almost absent, and the iodine number shows that there cannot be much cholesterol present. When heated a t 250" with soda-lime, 80 per cent. of the alcohols was recovered unchanged, only 6 per cent. of fatty acids, of melting point ,51-53", being recoverable from the soap formed.The easily soluble soaps from the original substance yielded 25.5 per cent. of fatty acids, in which the presence of lactones was demonstrated. The sparingly soluble soaps also yielded fatty acids and lactones amounting to 26 per cent. The iodine values, &c., of these fractions are given, but no conclusions are drawn from the admittedly incomplete experiments. Estimation of Resin in Fats and Soaps.-By JOHN LANDIN (Chem. Zed., 1897, 21, 25). The author has not succeeded in getting accurate results by using Gladding's silver process or Cornette's brine met hod. The following modification of the Twitchell-Wilson process is recom- mended :-Three grams of the isolated fatty acids is dissolved in 30 C.C. of absolute alcohol contained in a flask surrounded by cold water, and dry hydrogen chloride is then passed through the solution for 45 minutes ; this converts the fatty acids into the corresponding ethylic salts, whilst the resinous acids remain unaltered.The mixture, in a separating funnel, is now treated with 125 C.C. of hot water, and shaken with 75 C.C. of light petroleum to dissolve the resin. The aqueous layer is then drawn o$, and the petroleum solution shaken with a mixture of 0.5 gram of potassium hydroxide, 5 C.C. of alcohol, and 50 C.C. of water, to remove the resin; from the alkaline solution, the resin acids are liberated by acidifying with hydrochloric acid, By EUSTACE H. GAKE (J. SOC. Chem. Ind., 15, 95-96). The process suggested by Allen was found t o give either identical or higher yields, a, purer product, and greater facility of execution than the method of Paul and Cownley, which is usually employed (Abstr., 1888, 539).The following slight modifica- tion is preferred. Six grams of the finely powdered tea is boiled with 600 C.C. of water for 6 or 8 hours in a reflux apparatus ; 4 grams of lead acetate is then added, the boiling continued for 10 minutes longer, and the decoction filtered. 500 C.C. of the filtrate is evapo- rated to 50 c.c., and the excess of lead is removed by sodium phos- phate, Finally, the liquid is concentrated to about 40 c.c., and the caffeine extracted by shaking five times withchloroform. Opium Assay. By DAVID €3. DOTT (J. SOC. Clhem. h d . , 15, 91--94).-The British Pharmacopda process for the estimation of morphine is vitiated by several erroneous features, especially the sub- division of the solution, the great dilution, the large amount of alcohol, and the drying a t 100".Squibb's process, official in the United M. J. S. collected on a tared filter, dried, and weighed. L. DE K. Estimation of Caffeine in Tea. 31. J. S.ANALYTICAL CHEMISTRY. 101 States, is more satisfactory, but is not free from objections. The author proposes two processes: (A.) Exhaust 10 grams of opium with alcohol of 0.92 sp. gr., evaporate to one-fourth, dilute this with half its volume of water containing 0.05 gram of ammonium oxalate, the object of which is to decompose the calcium meconate. Add ammonia until the liquid remains just perceptibly acid. After an hour, filter, concentrate to 8 c.c., transfer to a 100 C.C.flask by means of 2 C.C. of water, and 3 C.C. of alcohol, add 2.5 C.C. of ammonia (0.96 sq. gr.), and 25 C.C. of ether. Cork the flask, and shake occasionally during an hour. After 18 hours, decant the ether, collect the precipitate on a tared filter, wash with morphinated water, dry, wash with chloroform, and dry at 60°, a t which temperature the precipitate has the formula 8C17H#0, + 9H,O. For method B, which is more expeditious, but gives a less pure precipitate, see Abstr., 1896, ii, 283. It is very free from impurities. AX. J. S. Estimation of Alkaloids. By E. H. FARR and ROBERT WRIGHT (Phamn. J. Yruns., 1897, 58, 202--203).-The estimation of morphine in opium by the official process of the British Pharmacopceia gives good results whec carried out as follows.The very finely powdered opium (14 grams) is rubbed into a uniform paste with freshly slaked lime ( 6 grams) and water (40 c.c.), then 100 C.C. more water is added and the mixture stirred occasionally for half an hour; 104 C.C. of the filtered mixture, which is supposed to represent 10 grams of opium, is shaken for half an hour with ammonium chloride (4 grams), ether (50 u.c.), and rectified spirit (11 c.c.), and then allowed to remain for 12 hours, It is essential that the proportion of alcohol should not be too high, as otherwise more morphine is retained in the mother liquor. The ethereal layer is then removed and the mixture again extracted with 20 C.C. of ether, t o ensure the removal of all substances soluble in that liquid ; finally, the crystals of morphine are collected on tared filters, mashed with a little distilled ,water, dried first by pressing between filter paper, then a t a gentle heat, and finally a t 96-lOO", until a constant weight is obtained. The opium must be i n a very fine powder, as otherwise a loss of morphine occurs amounting some- times to 5 per cent.It is also advantageous to finish the drying of the morphine a t 110"; some samples which were examined by the authors after drying at lOO', lost from 1.6 to 6-61 per cent., when heated a t 110'. The loss of morphine in the mother liquors amounts to 0.1 gram for every 100 C.C. of the filtrate. For the estimation of morphine in tincture of opium, the details are as follows : 80 C.C.of the tincture is evaporated to 20 C.C. at a low temperature, treated with freshly slaked lime (3 grams), and made up to 85 c.c.; 50 C.C. is then filtered into a 4 oz. bottle fitted with an accurately-ground stopper, and mixed with ammonium chloride (2 grams), ether (30 c.c.), and alcohol ( 5 c.c.). After the mixture has been shaken for half an hour and allowed to remain 12 hours, the layer of ether is removed by means of a pipette and the mixture shaken with 15 C.C. more ether, this being removed by means of a pipette, and filtered through tared filter papers. The filter is washed with a little ether, the residual ether allowed to evaporate, and then the102 ABSTRACTS OF CHEMICAL PAPERS. crystals of morphine are washed on to the filter, and washed with mor- phinated water until the washings are colourless. The crystals, after drying a t a gentle heat, are heated a t 110’ for one hour and weighed.0.3 gram of the crystals is dissolved in a slight excess of N/10 sulphuric acid, and the excess of acid estimated by N/10 soda solution, using litmus paper as indicator. To the amount of anhydrous morphine in the total weight of the crystals as indicated by the titra- tion, 0-05 gram is to be added. The combined weight multiplied by 2 will be the percentage of morphine in the tincture. The results agree well with those obtained by Dott’s and by Teschemacher and Smith’s processes. The official process for the estimation of water in alkaloids consists in drying them by the heat of boiling water; in the case of morphine, a s shown above, this temperature is not sufficient.I n the case of the cinchona alkaloids and the salts of quinine, however, perfect desicca- tion may be obtained if sufficient time is given, but much time is saved by drying a t 120’. Alkaloidal residues and extractive matters should always be dried in a flat-bottomed dish, so as to allow them to spread out in a thin layer. The authors corroborate the statement of Cownley that Quiniitce sulphus (official sulphate of quinine) gradually loses water of crystallisa- tion on exposure to the air, until but 2 molecules are retained ; also the anhydrous salt rapidly absorbs water, 1 gram on exposure to the air absorbed 0.015 gram of water in 7 minutes. They suggest that the sulphate with 2H,O should replace the one now official in the British Pharmacopceia.Quiniw iiydrochloq*as, when dried, is more hygroscopic than the sulphate, 0.686 gram, on exposure to the air, absorbed 0.017 gram of water in 6 minutes, and in 3 hours was converted into the salt with 2H,O. E. C. R. New Methods of Testing Indigo. By B. WJLLIAM GERLAND (J. Xoc. Chenz. Ind., 15, 15--17).-The process most in use, depending on reduction and the weighing of the recovered indigotin, is un- trustworthy, since part of the indigotin is lost, and that which is recovered is very impure. The author makes use of the solubility of indigotin in hot nitrobenzene, and its almost complete separation on cooling (see Abstr., 1890, 311). The following simple extraction apparatus is employed, A te5t-tube 200 mm. long and 40 mm. diameter is clamped above a lamp.Centrally within if, the filter, consisting of a thin glass tube 45 mm. long and 20 mm. diameter, over the lower end of which calico, on which is placed a little paper pulp, is wired, is hung from a tube 8 mm. in diameter and 500 mm. long, which serves as a reflux condenser, and passes through a funnel resting on the mouth of the test-tube. It is connected with an aspirator, the action of which prevents escape of nitrobenzene vapour, and also the recondensa- tion of any steam. Twenty-five C.C. of nitrobenzene, saturated in the cold with indigotin, is placed in the test-tube, and, by careful regulation of the flame and aspirator, the extraction of 0.5 gram of indigo is complete in 4-1 hour. The crystallised indigotin is collected on an extracted, weighed filter, washed with benzene, and dried.It still contains 3-6 per cent. of impurities, from which it can be freed byANALYTICAL CHEMISTRY. 103 prolonged treatment with hydrochloric acid and hydrogen peroxide, being thereby rendered fit for weighing or for titration by Bernthsen’s hyposulphite process. Owing to the solubility of indirubin in cold nitrobenzene, the total colouring matter is underestimated to the extent of about 0.1-0.2 per cent. By heating indigo with sulphuric acid of 1-67 sp. gr. (40 C.C. to 0.5 gram) in a water bath for an hour, the idigotin is wholly converted into the monosulphonic acid, which dissolves, and can be separated from the residue by filtering through a sand filter with suction, and washing with acid of the same strength heated to 100’.On diluting the solution with 2 or 3 volumes of water, the monosulphonic acid is completely precipi- tated. It is best to collect it on a sand filter, and wash with water con- taining 20 per cent. of SO,. It is then dried and digested at 100Owith concentrated sulphuric acid, whereby it is converted into the disulphonic acid, which can be readily removed from the filter by water. I t still, however, contains coloured impurities which vitiate the titration with hyposulphite. But if the raw indigo has been digested for some time in the cold with hydrochloric acid and hydrogen peroxide, then boiled, washed with boiling water and dried before treatment with sulphuric acid, the sulphindigotic acid is sufficiently pure to give good results 011 fitration. The titration apparatus resembles that used by Tiemann and Preuss (Abstr., lSS0, 138). The indirubin is estimated as indigotin, and the results are 0.3-0.4 per cent. higher than those obtained by the nitrobenzene process. M. J. S. By BRUNO TACKE(C~~~. Zeit., 1897,21,174-175).-The direct estimation of humic acid is impracticable on account of the colouring matters contained in the soils, but the author has devised an indirect process based on the decomposition of calcium carbonate by humic acid. The apparatus consists of a generating flask furnished with a trebly perforated cork, through which pass three tubes; one of these is con- nected with a constant hydrogen apparatus, the second is fitted to an indiarubber tube with a screw-clamp, whilst the third is connected with a Pettenkofer’s absorption tube. The sample is put into the generating flask with 100 C.C. of boiled water, and a current of purified hydrogen is passed through the liquid for an hour to expel all the air ; the absorption tube is then filled with 100 C.C. of N/lO soda, and an emulsion of calcium carbonate is introduced through the indiarubber tube. The current of hydrogen is kept up for 3 hours, when the contents of the absorption tube are titrated with NjlO hydrochloric acid, after adding barium chloride to precipitate the carbonate. The diminution in alkalinity represents the amount of carbonic anhydride given off by the calcium carbonate. Although more carbonic anhydride is given off when the mixture is heated, the author thinks that the amount evolved in the cold is Modification of Stutzer’s Process for Estimating Proteids in Substances Rich in Starch. By HEINRICH C. TRYLLER (Chem. Zeit., 1897, 21, 54)-The sample is treated according to Stutzer’s Estimation of Free Humic Acid in Peaty Soils. the true measure of the humic acid in the soil. L. DE K.104 ARSTHACTS OF CHEMICAL PAPERS. directions, but after adding the alum and the emulsion of copper hydroxide, it is allowed to cool to 65O, and 10 C.C. of a 20 per cent. malt-infusion is added. This rapidly liquefies the starch and facilitates the filtration. The residue on the filter is then tested for nitrogen by Kjeldahl’s process, allowance being made for any nitrogen contained in the malt solution and the filter paper. L. DE K.

ISSN:0368-1769    

DOI:10.1039/CA8987405089

出版商:RSC    

年代:1898

数据来源: RSC

摘要:

101 Organic Chemistry. Determination of the Number of Isomeric Paramns of the Formula C?2H2.it+2. By FELIX HERRMANN (Bey.., 1897,30,2423-2 126). -The author describes in outline a somewhat simpler method than those adopted by Cayley and Losanitsch for the determination of the number of isomeric paraffins of the formula ClzH2,a+2. Decomposition of Heptane and Octane at High Tempera- tures. By R. A. WORSTALL and A. W. BURWELL (Amer. Clzena. J., 1897, 19, 815--845).-For this investigation, ordinary crude 63" naphtha of sp. gr. = 0.7310 at 15", consisting practically of heptane and octane, was employed ; the greater portion passed over between 100" and 120'. When gas was manufactured from this material by the Pintsch pro- cess, the tar which condensed in the hydraulic main was equivalent to about 25 per cent, of the oil used; i t had a sp.gr. = 0,9369 at 15'; by the action of bromine, 34.48 per cent. was added, and 18.88 per cent. substituted. It was found that 100 parts of heptane and octane yielded 25 parts of methane, 26 of olefines, 13 of acetylene, 12.5 of benzene, 3.0 of toluene, 3.0 of xylenes, &c. (120-200°), 4.5 of aromatic hydro- carbons (200-300"), 3.3 of aromatic hydrocarbons (above 300°), 3.6 of naphthalene, 1.3 of anthracene, 0.1 of phenanthrene, 0.1 of chrysene, about 0.01 of fluoranthrene (?), 0.01 of phenols. Naphthenes, thiophen, and diphenyl were absent, and no paraffins other than the original heptane and octane were present. About 10 per cent. of a liquid was deposited during the compression of the gas under 15 to 17 atmospheres.This consisted of hydrocarbons of low boiling point, about 6 per cent. being unsaturated hydro- carbons boiling at 20-78", 80 per cent. benzene, and 10 per cent. toluene and xylene, but no paraffins other than the original heptane and octane were present. The gas was made up of 11.8 per cent. of nitro- gen, 11.3 of acetylene (and ethylene?), 15.5 of other illuminants, 18.4 of hydrogen and 42.9 of methane. 1000 cubic feet of gas was obtained from 16 gallons of oil. It would seem, judging from these results, and those described by Letny, by Berthelot, and by Norton and Noyes, that all hydrocarbons, under similar conditions of temperature, yield the same products. If such is the case, then Schulze's theory of the formation of coal-tar hydro- carbons from phenols cannot be correct.Similarly, explanations such as those of Berthelot and Haber, which assume t h a t the paraffins first split up into simpler molecules, are confronted by the facts that these lower hydrocarbons are not found among the products, and that hydro- carlooils which do not belong t o the paraffin group yield the same products as the paraffins. Composition of Scottish Paraffin Oil. By FRIEDRICH HEUSLER (Ber. 1897,30, 2743--2752).-The fraction boiling below 110" contains paraffins, 42 per cent,. ; naphthenes, 10 ; aromatic hydrocarbons, 7.3,and VOL. LXXIV. i. i H. C. E. W. W.102 ABSTRACTS OF CHEMICAL PAPERS. ethylene, &c., 39 ; the paraffins and naphthenes were determined in the manner described below, the arom.ttic hydrocarbons as dinitrotoluene ; the total amount of saturated hydrocarbons was also determined by boiling some of the swmyle for 1 hour with about 7.5 per cent.of aluminium chloride w nd distilling over the hydrocarbons with steam. I n the case of Saxon lignite, the corresponding numbers were 16, 4, 45, and 31 per cent. The small quantity of aromatic hydrocarbons found in this may have been formed by pyrogenic reactions from t h e fatty hydrocarbons present, but this cannot be true of the much larger quantity coiltained in the Scotch oil, since only a small amount of benzene would bt. formed a t the comparatively low temperature of the retorts in which the shale is distilled. The Scotch paraffin shale then, unlike the Saxon lignite, probably contains considerable quantities of aromatic compounds ready formed ; it is, further, most probahly of ariinial origin, whilst the lignite is vegetable.The paraffins in the oil boiling below 180' were estimated by treat- ing a sample with cooled fuming nitric acid, and measuring the residue ; it amoilnted to 40-44 per cent., boiled a t 149--154', had sp. gr. : 0.730 at 15', and coutained C, 84.4; H, 15.8 per cent,, which agrees well with C,H,,. The paraffins arid rjaphthenes were separated in company by treating the oil successively with somewhat diluted sul- phuric acid, strong sulphuric acid, and fuming sulphuric acid ; the residue was fractionated, and the analyses and specific gravities of the fractions showed t h a t they contained about 20 per cent. of naphthenes. The presence of benzene, toluene, metaxyleue, and cumene, and the absence of naphthalene, were also proved.El hylene hydrocarbons were separated by adding bromine untii immediate decolorisation no longer ensued ; the chief fraction of the bromides formed (from the fraction of the oil boiling a t 60-70') boiled at 87-95" under 15-16 mm. presmre, had a sp. gr. = 1.623 at 15', and coutained C, 29 1 ; H, 4.8 ; Br, 66.2 (between C,H,,Br, and C6Hl2Er2, and nearer the latter). The nitriles of fatty acids were detected by boiling the oil with solid caustic potash ; the solid product was separated from the oil, and dissolved in water ; pyrrolines were driven off by steam-distillation, and the phenols removed after saturation with carbonic anhydride, t h e fatty acids being then set free with sulphuric acid.These, from a fraction of the original oil boiling a t 120-170", boiled a t 193-236', and contained C, 61.3 ; H, 10.1 (between C,H,,O, and C,H,,O, and nearer the latter). The oil also contains sulphur (0.29 and 0-23 per cent. in the fractions 130-140' and 170-180' respectively), probably in the form of thiophen derivatives. C. F. B. Bivalent Carbon : Chemistry of Methylene. By JOHN U. NEF (Anncden, 1897, 298, 202-374. Compare Abstr., 1896, i, 71).-The theoreticd portion of this paper is divided into six chapters, dealing with (1) the behaviour of unsaturated compounds, (2) the dissociation of saturated into unsaturated compounds, (3) the polymerisation of unsaturated compounds, (4) the condensation law, (5) the dissociation of condensation products into their original constituents, and (6) the methylene problem.The author recognises two classes of unsaturated substances, namely,ORGANIC CHEMISTRY. 103 (A) those which contain a double or treble linking between two neigh- bouring atoms, as, for example, ethylene, chlorine, acetylene, oxygen, the aldehydes, ketones and fatty acids, the alkylic cyanides, R*CiN, the nitroparltfhs, O:NR:O, nitric acid, 0: N(OH):O, sulphuric acid, O:S(OH),: 0, the alkylic cyanates, and the thiocyanates ; and (B) those which contain an unsaturated atom, a n atom, that is, which does not display its maximum valency, this class being typified by ammonia and the amines, methylene and its products of substitution, such as C:O, C:N*R, C: N-OH, thio-ethers, SR,, alkylic chlorides, and imidogen, :NH.The process of saturation is not essentially different in the two classes, involving dissociation of the substsnccs with which unsatu- rated compounds form additive products ; the substances (C) which undergo dissociation in this way are acids, ammonia derivatives, derivatives of water and of hydrogen sulphide, halogens, hydrogen, acidic chlorides, alkylic haloids, and halogen derivatives of metals and non-metals. Members of a further group of compounds (D) are frequently dissociated with even greater readiness than those last enumerated ; such are hydrocarbons, olefines, acetylene, and alkyl- acetylenes, compounds containing carbonyl, nitriles, nitro-compounds, methylpyridines, and methylquinolines, benzene, and the products of its substitution.It is represented that dissociation of a compound in this sense resolves it into hydrogen or halogen, and the residual complex. The factors which determine the existence of an unsaturated sub- stance are very numerous, and in some cases obscure, but the character and mass of radicles contained in a compound have great intluence on its stability ; saturation is assisted in many cases by light, heat, elec- trical influences, and also by the action of acids, alkalis, water, and finely divided metals, The author considers i t unnecessaiy t o regard these agencies as catalytic, attributing their influence t o mechanical causes ; they probably exert a dissociating influence on members of the foregoing classes, convertiug their components into the nascent state, in which condition they enter into combination, or undergo polymeri- sation.I t is noteworthy that a polymeride is fre,luently resol! ed into the compound from which it is formed by the very agency which gives rise to its production. Cases in which addition has been followed by spontaneous decompo- sition of the additive product have occurred with great persistence during the last few years, and the circumstance throws considerable doubt on the validity of the substitution hypothesis, It is conceivable t h a t the process usually called substitution, in reality consists of dis- sociation of the radicles in which substitution is regarded as occurring, followed by addition to the substituent, the additive product being sufficiently unstable to lose spontaneously halogen hydride or water, as the case may be.The compounds which readily undergo this form of dissociation, or, in cclmruon language, the compounds which readily undergo substitution, are those comprised in class D. The readiness with which dissociation into hydrogen and hydrocarbon occurs, followed by addition to a n unsaturated substance, is particularly influeuced by the presence of negative radicles a,nd atoms, and by the existence of double or treble linkings ; i t is also increased by those agencies, such i 2104 ABSTRACTS OF CHEMTCAL PAPERS. as light and heat, which have been already recognised as exerting a favourable influence on dissociation, polymerisation, and addition phenomena. It is necessary t o distinguish clearly between polymerisation and condensation.Polymerised products are those which arise from the com- bination of free valencies in the same substance, such as benzene from acetylene ; condensed products, on the other hand, are formed by the addition of members of class D to the unsaturated substances of A and B. It is possible to divide the majority of the condensation processes to which carbon compounds are liable into (I) ethylene condensation, (2) carbonyl condensation, and (3) methylene condensation. The first of these groups comprises the reactions of ethylic malonate, benzylic cyanide, deoxybenzoin, ethylic cyanacetate, and malononitrile, with alkylic haloids in which the alkylic radicle is ethyl or a higher homo- logue ; the condensation of acetaldehyde to aldol, and of ethylic acetate t o ethylic sodioacetoacetate also belong to this group, which includes the Friedel-Crafts reaction of hydrocarbons with aluminium chloride and alkylic haloid in which the alkylic group is ethyl or a higher homologue.The second division embraces all condensations of benz- aldehyde, in acid solution, with phenols, tertiary aromatic amines, and ethylic malonate, the production of ethylic benzoylacetate from ethylic benzoate, sodium ethoxide, and ethylic acetate, and the condensation of ethylic oxalate with ethylic acetate, acetone, acetaldehyde, and benzylic cyanide ; also the condensation of acidic chlorides with benz- ene, of phthalic anhydride with benzene, ethy lic malonate, benzylic cyanide, quinaldine, and phenol, and of carbonic anhydride with phenols and the salts of substituted acetylenes.The third group includes the production of cinnamic acid from benzaldehyde, acetic anhydride, and sodium acetate, the condensation of benzaldehyde with ketones, aldehydes, and ethereal salts under the influence of sodium ethoxide or dilute caustic soda, the condensation of ethylic formate with et,hylic acetate, acetone, and acetophenone, the conversion of formaldehyde into a-acrose and p-acrose, the condensation of benzylic alcohol, benzhydrol, and aromatic hydrocarbons under the inff uence of concentrated sulphuric acid, and the Friedel-Crafts reaction when carried out with methylic chloride. The behaviour of benzene towards nitric and sulphuric acids is regarded by the author as the result of the addition of the dissociated hydrocarbon t o the unsaturated molecule of the acid, followed by elimination of water from the product ; similarly, the conversion of the hydrocarbon into bromobenzene is traced to the addition of the dissociated molecule to the unsaturated bromine molecule, Bri Br, when t h e additive compound, HBr: BrC6H5, is produced, and spontaneously yields hydrogen bromide and bromobenzenc.It is pointed out that the same agents which induce condensation are instrumental in dissociating the product into its constituents. Ethylic acetoacetate, for instance, is resolved by sodium ethoxide into ethylic acetate, whilst mesitylic oxide, phorone, and ethylic ethylidene- malonate yield acetone, acetaldehyde, or ethylic malonate when heated with water or acids. A n investignt,iori of numei*ous well-known derivatives of acetyleneORGANIC CHEMISTRY.105 has shown the author that these must be divided intcj two classes, (1) those derived from acetylene, CHiCH, usually characterised by agree- able odour and no marked chemical activity, and (2) derivatives of cccetglidene, CH,: C , which are poisonous, have a n intensely disagreeable odour, are in some cases spontaneously inflammzble, and generally exhi b i t great chemical activity. Behrend's di-iodacetylene, Sabandeff's monobromacetylene, and Wallixch's nionochloracetylene are regarded as members of the latter cIass, and are referred to as di-iodacetylidene, ~,aonobromacetyliclerLe, and ntonoc~~lorcLcet?llidesLe, respectively. It is prob- able, also, that the metallic derivatives of acetylene belong to this group.The experimental part oE the paper comprises three divisions, which deal respectively with (I) reactions of nascent diphenylmethylrne and phenylmethylene, (I I) reactions of benzaldehyde, nascent hydroxy- phenylmethylene and acetoxyphenylmethylene, and (ILI) the chemistry of acetylidene. I.-According t o Friedel and Balsohn, diphenylmethy lic bromide yields benzhydrol and benzhydrol ether when heated with water. The author finds, however, t h a t treatment with cold water during two weeks completely resolves diphenylmethylic bromide into hydrogen bromide and benzhydrol, whilst beuzhydrol ether is formed on heating the bromide with 5 parts of water for 2 days on the water bath, if the hydrobromic acid is neutralised with alkali. It has been repre- sented by Zincke and Thorner that benzhydrol ether has the constitu- tion expressed by the formula FP"Z>O, because it is produced when CPh, benzhydrol is heated a t its boiling poigtfor sometime ; from the following facts, however, it is necessary to regard the substance as a true ether of the formula (CHPh,),O.Benzhydrol ether yields benzhydrol acetate (2 mols.) when treated with a mixture of cold glacial acetic (9 parts) and concentrated sulphuric (2 parts) acids : alcohol (10 parts) and coucen- trated sulphuric acid (2 parts) convert it, when gently heatjell, into benz- hydro1 ethyl ether : the solution in benzene is converted by concentrated sulphuric acid or by phosphoric anhydride into triphenylmethane. More- over, the two expressions diEer from one another by two a t o m oE hydrogen, and it has been shown by Klinger and Lonnes (Abstr., 1896, i, 687) that benzhydrol ether has the empirical formula C,,H,,O.When benzhydrol ether is distilled rapidly under atmospheric pres- sure, it undergoes dissociation into diphenylmethylene and water, which associate in part on cooling; slow distillation gives rise to benzophenone and diphenylmethane, a small quantity of benzh ydrol ether being found in the distillahe. This observation is not in agreement with Linnemann's statement. Benzhydrol ether, however, boils at 267" under a pressure of 15 mm., without decomposing. On heating benzhydrol or benzhydrol ether in a distillation flask, either alone or in a n atmosphere of carbonic anhydride, water is eliminated, and after 3-5 hours, the products consist principally of benzophenone and tetraphenylethane, along with a small proportion of diphenylmethane. The changes involved are regarded by the author as taking place on the following lines.Benzhjdrol is first dissociated into diphenylrnethylene and water, just as formic acid yields carbon monoxide and water when heated at 167' ; the rnethylene derivative106 ABSTRACTS OF CHEMICAL PAPERS. then unites with the benzhydrol w:hioh is in excess, yielding benz- hydro1 ether. The latter slowly dissociates at 300' into diphenyl- methylene (2 mols.) and water, which reunite to form benzophenone, with liberation of hydrogen ; the decomposition of water by nascent diphenylmethylene, :CPh,, is attributed to the great affinity for oxygen which bivalent carbon exhibits.If water is in part removed from the sphere of action, diphenylmethylene undergoes polymerisation, yielding tetraphenylethylene, which is reduced by the nascent hydrogen ; but if water is not removed, no trace of tetraphenylethnne is produced, and the benzhydrol ether undergoes reduction, yielding diphenyimethnne. The same intermediate product, diphenylmethylene, is formed when benzilic acid is dissociated a t 180-ZOO'; as in the foregoing case, it decomposes the vater which is present, yielding benzophenone, whilst the hydrogen thus liberated reduces unchanged benzilic acid to diphenyl- acetic acid (compare Klinger and Standke, Abstr., 1889, S85). To the production of diphenylmethylene may also be attributed the formation of tetraphenylethylene and tetraphenylethme when benzhydrol ace- tate and benhydrol benzoate are heated a t 300'.The uniform production of resinous polymerides which attends the treatment of benzylic derivatives with such agents as zinc dust or concentrated sulphuric acid, is attributed to the intermediate liberation of phenylmethylene, which then undergoes polymerisation. Thus zinc dust eliminates halogen hydride from benzylic bromide and benzylic chloride at lZO', the copper-zinc couple producing this effect on the former substance a t ordina~y temperatures, and in each case a dsrk- yellow resin of the formula (C7H& is produced; if, however, the halogen derivative is dissolved in an indifferent medium, the action is much milder, and the products are toluene and dibenzyl.This differ- ence in behaviour is regarded as being due to the fact that, in the first case, a large proportion of phenylmethylene molecules are set free simultaneously, and then undergo polymerisation to complex molecules ; Gn the other hand, dilution with a n indiflerent medium renders the dissociation much more gradual, and gives rise to polymerides of much smaller molecular weight. The same observations apply to derivatives of benzhj drol and benzylic alcohol. Benzhydrol, benzhydrol ether, benzhydrol ethyl ether, benz- hydro1 acetate, and benzhjdrol benzoate are all converted into red polymerides of diphenylmethylene under the influence of aluminium chloride, phosphoric anhydride, and concentrated sulphuric acid. The effect of introducing a diluent which is not an indifferent substance is similar to that produced in the Friedel-Crafts reaction, which meets with explanation on the dissociation basis developed in the paper.For instance, triphenylmethane is produced from a mixture of benzhy drol and benzene under the influence of phosphoric anhydride or concen- trated sulphuric acid, and the hydrocarbon is also obtained from a solution of benzhydrol ether or benzhydr ol acetate in benzene. Friedel and Balsohn have observed that, whilst alcoholic ammonia converts diphenylmethylic bromide into benzhydrol ethyl ether, the aqueous base gives rise t o benzhydrylamine, CHPh,*NH,, and di- benzhydrylamine, NH(CHPh,),. This is explained on the assumption t h a t diphenylmethylene takes up alcohol more readily than ammonia,ORGANIC CHEMISTRY.107 and ammonia more readily than water, and i t is pointed out that the preference of unsaturated compounds for alcohol before water has been alreadyexhibited in thecasesof ethyliccyanimidocarbonate (A bstr., 1896, i, 72), cyanogen chloride, and cyanogen bromide, Although benzylic chloride yields benzyl ethyl ether under the influence of alcoholic potash, orthonitro- and paranitro-benzylic chlorides give rise to the correspond- iug stilbene derivatives in quantitative amount ; similarly, chloro- benzylic cyanide and bromobenzylic cyanide are converted into dicyano- stilbene. The behaviour of ethylic bromocyanacetate is, however, more remarkable. Ethylic b~*ornocyanacetate, CN*CHBr*COOEt, obtained by treating ethylic cyanacetate with bromine (1 mol.) at 150°, boils at 116' under a pressure of 25 mm.'When dissolved in ether, and treated with metallic sodium, ethylic sodioaceto kcetate, ethylic sodiocyan- acetate, or aniline, it is converted exclusively into ethylic dicyano- ficmcwate, COOEt- C(CN):C(CN)*COOEt, which crgstallises from benzene or alcohol in colourless needles, and melts at 122'. The substances enumerated may be regarded as dissociating ethylic bromocyan- acetate into hydrogen bromide and ethylic cyanomethylenecarboxylate, COO E t *C( CN) 1, which then undergoes polymerisation. Ethylic bromomnlonate, on the other hand, yields exclusively ethylic ethanetetracarboxylate, (COOEt),CH-CH(CO0E t)2, when treated with ethylic sodiomalonate in absolute ether, no trace of the ethylene- tetracarboxylste, (COOE t),C: C(CO0E t)2, being produced.This may be due t o the initial dissociation of ethylic bromomalonate into hydro- gen bromide and the methylenic derivative, :C(COdEt),, which then unites with ethylic malonate, set free from the sodium derivative by the halogen hydride. The behaviour of ethylic malonate towards unsaturated compounds gives some support t o this view; for in- stance, Claisen has shown that ethylic ethylidenemalonate yields ethylic ethylidenedimalonate when heated with ethylic malonate at ZOO", and by the action of benzylic cyanide on phthalic anhydride, Gabriel ob- tained the compound, C,H, < z $ e > O . The foregoing facts have led the author to modify the views which have been previously expressed regarding the action of alkylic haloids on such compounds as ethylic sodiomalonste (Abstr., 1892, 140 ; 1893, i, 628).Instead of assuming that halogen hydride is first liberated, and that no direct displacement of sodium takes place (Zoc. c i t . ) , the following explanation is put forward. When ethylic malonate is con- verted into ethylic methylmalonate by the action of methylic iodide on ethylic sodiomalonate, the alkylic iodide undergoes dissociation into methylene and hydrogen iodide, the latter removing the metal from ethylic sodiomalonate ; the ethylic malonate which is thus liberated is then free to take up methylene,, yielding ethylic methylmnlonate. Sup- port is lent to this view by the fact that ethylic ethylmalonate is readily produced from ethylic malonate and ethylic: iodide and zinc, which also induces the introduction of two ethylic groups; it is more probable that the metal dissociates ethylic iodide into hydrogen iodide and ethylene, which is then absorbed by the ethereal salt, than that a zinc derivative of ethylic malouate is formed as an intermediate pruduct.It is noteworthy that, whilet treatment of ethylic malonate with ethylic1.08 ABSTRACTS OF CHEMICAL PAPERS. iodide (1 mol.) and sodium ethoxide gives rise to a mixture of ethylic ethylmalonate and ethylic diethylmalonate in which the former pre- ponderates, and ethylic ethylcyanacetate is produced in greater quantity than ethylic diethylcyanacetate when sodium ethoxide and ethylic iodide (1 mol.) act on ethylic cyanacetate, treatment of the last-named substance, on the other hand, with benzylic chloride (1 mol,) and sodium ethoxide yields more ethylic dibenzylcyanacetate than ethylic benzylcyanacetate.The author explains this phenomenon by attribut- ing to ethylic malonnte a greater capacity for dissociation than that exhibited by ethylic ethylmalonate, whilst ethylic benzylcyanacetate is regarded as undergoing dissociation with greater readiness than ethylic cyanacetate. On these lines, it is possible to account for the fact that ethylic ethylmalonate does not condense with acetaldehydc and benzaldehyde, differing in this respect from ethylic malonate. It is probable also that the behaviour of benzylic cyanide and of deoxybenzoin towards alkylic haloids in presence of sodium ethoxide depends on the dissociation of the haloid into halogen hydride and alkylene, which is then absorbed by the benzylic cyanide and deoxy- benzoin respectively. The same principle may be applied to the reactions of benzylic cyanide, ethylic malonate, ethylic cyanacetate, deoxy benzoin, and primary and secondary nitroparaffins, with nitrous acid, amylic nitrite, and phenyldiazonium chloride. The production of amines from ammonia and alkylic haloids may be also brought into this category.Reverting to the action of metals on alkylic haloids, which has been investigated by Frankland, Wiirtz, and Fittig, the author points out that his hypothesis gains support from the fact that, in most cases, the product consists of a mixture of hydrocarbons. For instance, when sodium acts on methylic iodide in ether a t looo, methane, ethane, and ethylene are produced, This is readily explained on the assumption that methylic iodide is first dissociated into methylene and hydrogen iodide, which yields nascent hydrogen by the action of the metal, in quantity insufficient to convert the methylene entirely into methane ; a part, therefore, becomes partly hydrogenised to methyl, which polymerises, a small proportion, however, escaping reduction and under- goiug polymerisation, yields ethylene.As regards the mechanism of Fittig’s synthesis of benzene homologues, it is maintained that when a halogen derivative of benzene is treated with methylic iodide and sodium, the benzene compound dissociates into hexacarbon tetrahydride, C,H,, and halogen hydride, whilst the methylic iodide yields metbylene and halogen hydride.The metal liberates nascent hydrogen from the latter in quantity insufficient (in the absence of water) to reduce the unsaturated products further than phenyl and methyl respectively ; they therefore unite, forming toluene. 11.-In an alcoholic solution of ethylenic dibromide, the latter may be regarded as existing in two conditions of dissociation, namely, ethylene and bromine, or vinylic bromide and hydrogen bromide ; according as zina dust or alkali is present, either of these conditions asserts itself. The author claims to have shown that ethylidene di- hydroxide, CHMe*CH(OH)2, may undergo dissociation in three direc- tions, represented by vinylic alcohol, GH,:CH*OH, acetaldehyde, CHMe:O, and hydroxyethylidene, :CMe*OH ; /3-propylidene dihydr-ORGANIC CHEMISTRY.109 oxide, however, exhibits only two-fold dissociation into acetone and P-hydroxypropylene, CH,: CMe- OH, w-dihy droxytoluene into CHPh :O and :CPh*OH, whilst ortbucetic acid, CMe(OH)3, is resolved into acetic acid, or dihydroxyethyleue, C'H,:O(OH),. Chloral hydrate, however, undergoes four-fold dissociation, into (1) chloral and water, (2) hydroxytrichlorethylidene, CCI,*C(OH):, (3) dichloracetylidene hydroxide, CCl,:U(OH),, and hydrogen cliloride, and (4) chloroform and dihydroxyrnetliylene, :C( OH),. Benzylidene dirtcetste, CHPh( OAc),, is prepared by heating benz- aldehyde with equal weights of acetic anhydride and glacial sicetic acid in a reflux apparatus a t 150-180" for a short time, and submitting the product to distillation under a pressure of 20-30 mm.; i t melts at 46") and boils at 154" under a pressure of 20 mm. It is noteworthy that the compound is not produced by the action of acetic anhydride on benzaldehyde when the former is free from acetic acid ; moreover, the anhydride prohibits the dissociation which benzylidene diacetate under- goes when exposed to the air during a prolonged period. A boiling solution of caustic soda acts very slowly on the substance, which is converted into cinnamic acid when heated with sodium acetate, either alone or in presence of glacial acetic acid ; cold concentrated sulphuric or nitric acid resolves i t into benzaldehyde and acetic acid. The production of berizylidene diacetate is explained by assuming t h a t benznldehyde first forms with acetic acid the additive compound OH*CHPh*OAc, which dissociates into acetic acid and nascent benz- aldehyde ; the latter then dissociates acetic anhydride, producing benzylidene diacetate by addition.Beizsoic ncetic peroxide, AcO-OBz, is obtained by exposing a mixture of benzaldehyde and acetic anhydride (2 mols.) to the air until the liquid is free from aldehyde ; in diffused light, this effect is produced in 43 days, exposure to sunlight for 20-25 days being generally sufficient. The oily product is agitated with 3-3 parts of cold concentrated nitric acid, which resolves benzoic acetic oxide into benzoic and acetic acids, and converts benzylidene diacetate into acetic acid and benzaldehyde ; the liquid is then poured into water, extracted with ether, and the ethereal extract agitated with caustic soda, dried, and evaporated, the product being treated once more with concentrated nitric acid.I t crystallises in colourless, transparent needles, and melts at 37--39", exploding with considerable violence a t S5-100". It is possible t o avoid the simultaneous production of benzoic acetic oxide by exposing benzaldehyde and acetic anhydride (1 part) mixed with sand (20 parts) t o diffused daylight for 4 days in porcelain basins; the mass is extracted with ether, and the extract washed with sodium carbonate. Benzoic acetic peroxide has a marked odour of ozone, decolorises a solution of indigo-sulphuric acid, and liberates iodine froin potassium iodide. Cold dilute caustic soda slowly converts i t into benzoic acid, sodium peroxide, oxygen, and benzoic peroxide, whilst sodium car- bonate, although acting more slowly, gives rise to a greater proportion of benzoic peroxide ; i t sets free chlorine from concentrated hydro- chloric acid, and is decomposed Iny concentrated sulphuric acid in an explosive manner I t s behaviour in general appears to indicate a tendency t o dissociate into benzoic acetic oxide and ozone.110 AESTRACTS OF CHEMICAL PAPERS.Metanifrobenxoic acetic peroxide, AcOQ CO*C,HqNO?, is prepared by dissolving benzoic acetic peroxide in fuming nitrlc acid and pouring the liquid into water after an interval of 15 minutes ; i t crystallises from methylic alcohol in colourless needles, and melts a t 68'. Acetic peroxide AcO*OAc, was first obtained by Brodie from barium peroxide and acetic anhydride, as an oil.It is more conveniently prepared by mixing hydrogen peroxide with acetic anhydride (2 mols.) at - 1 Oo, allowing the liquid to remain below 30' during 6 hours, diluting with ether, and then agitating with a 10 per cent. solution of sodium carbonate ; the ethereal portion is dried and carefully evaporated, the residue being distilled with extreme caution under reduced pressure. Acetic peroxide forms transparent crystals and melts a t 30'; it boils at 63' under a pressure of 21 mm., and explodes with great violence when heated above looo, or on vigorous agitation. The odour is indis- tinguishable from that of ozone, and it probably owes its oxidising and explosive character to ready dissociability into that substance and acetic anhydride ; if kept in loosely closed vessels, it is completely con- verted into acetic anhydride and acetic acid a t the end of four months, and treatment with caustic soda rapidly yields acetic acid and sodium peroxide.Berthelot's ethylic peroxide, obtained by the action of ozone on ether, consists principally of acetic peroxide (compare also Vanino and Thiele, Abstr., 1896, i, 597). Biphenglformal peroxide Jbydrate, O,(CHPh*OH),, is obtained by treating benzaldehyde (10 grams) with hydrogen peroxide ( 3 grams) in three portions, the temperature of the liquid being maintained below SOo; i t melts a t 60-62", and is insoluble in cold ether and petroleum. Both in the solid state and when treated with sodium car- bonate, it is dissociated into benzaldehyde and hydrogen peroxide with- out the formation of bonzoic acid ; cold acetic anhydride converts it into acetic peroxide, acetic acid, and benzaldehyde.Ozone! acetic peroxide, and benzoic acetic peroxide have all the same odour, which is due either to atomic oxygen produced by their disso- ciation, or to the ozone formed from ordinary oxygen under the oxidising influence of atomic oxygen. The readiness with which the acidic derivatives of hydrogen peroxide dissociate into oxides and atomic oxygen suggests similar behaviour on the part of hydrogen peroxide itself, which would yield water and atomic oxygen; but it is well known that the substance dissociates also into nascent hydrogen and molecular oxygen, and this double dissociation affords an explanation of the simultaneously reducing and oxidisicg character of hydrogen peroxide.Prom this point of view, slow combustion in presence of water may be regarded as taking place in the following stages : (1) decomposition of water by the combustible material, (2) conversion of atmospheric oxygen into hydrogen peroxide by the nascent hydrogen produced, (3) dissociation of hydrogen peroxide into water and atomic oxygen, which then exerts direct oxidising action. Atmos- pheric oxygen never undergoes direct absorption. Just as zinc, iron, lead, and phosphorus become oxidised at much lower temperatures in presence of caustic soda than when oxygen and water alone are present, so benzaldehyde, under the influence of caustic alkali, yields hydrogen, benzylic alcohol, and benzoic acid.This probablyORGANIC CHEMISTRY, 111 depends on initial prodiiction of w-dihydroxytoluene, which uiidergoes dissociation into phenylhydroxymethylene ; the hydrogen liberated by the action of the latter substance on water reduces a portion of the aldehyde to benzylic alcohol, whilst the phenylhydroxymethylene takes up hydroxyl, the product becoming dissociated into benzoic acid and water. Similarly, formaldehyde yields methylic alcohol and formic acid. I n this connection, the author emphasises the enormous import- ance of water in oxidation phenomena. The oxidation of aldehydes, ketonic alcohols, aldebydic alcohols, and members of the sugar group, depends, broadly speaking, on dissociation into a methylene derivative, which liberates nascent hydrogen from the water present ; the nascent hydrogen then reduces the oxidising agent.I n the same way is explained the production of formic and acetic acids along with alkali nitrite from nitroglycerol under the influence of alkalis, the formation of hydrogen along with formic and acetic acids on heating glycerol with solid potash, and the violently explosive character of nitroglycerol and methylic nitrate. Amongst numerous cases with which the author illustrates his hypothesis is the phenomenon of fermentation. Organised ferments, or the enzymes which constitute their active principle, are regarded as capable of inducing dissociation of the sugar mo!ecule ; the methylene derivative thus produced decomposes water, setting free nascent hydrogen. Although, theoretically, a molecule of glucose is capable of dissociating in many different ways, a directive influence is exerted by the ferment, just as the dissociation of ethylenic dibromide is con- trolled by zinc dust or alkali.Although phenylhydroxyrnethylene is capable of decomposing water and alcohol, these substances are not attacked if compounds are present which undergo dissociation more readily ; such are acetaldehyde, acetone, acetophenone, ethylic acetate, benzylic cyanide, and ethylic malonate. It has been shown that benzylidene diacetate yields cinnamic acid when heated with sodium acetate a t 180", and it is on the inter- mediate formation of the first-named substance t h a t the production of cinnamic acid from benzaldehyde, acetic anhydride, and sodium acetate depends.Benzylidene diacetate is dissociated by sodium acetate into phenylacetoxymethylene, t o which acetic acid then adds itself; elimination of acetic acid from the product gives rise t o cinnamic acid. It is shown experimentally that nascent benzaldehyde is not capable of adding acetic acid or the anhydride, and the synthesis in question is therefore ascribed to phenylacetoxymethylene; it cannot, however, be settled definitely whether it is acetic acid, sodium acetate o r acetic anhydride which unites with the nascent p heny lace toxy me t hy lene. The conversion of benzaldehyde into benzoin is traced as follows. Alcohol with benzaldehyde forms the additive compound, OH* CHPh-OEt, which, under the influence of potassium cyanide, is dissociated into alcohol and phenylhydroxymethylene ; the later polymerises to the ethylene derivative, OH- CPh: CPh-OH, t o which alcohol is added and then eliminated from the product, yielding benzoin.The deleterious effect of sodium ethoxide is due to the fact t h a t the additive compound112 ABSTRACTS OF CHEMICAL PAPERS. of benzoin and alcohol, OEt* CPh(OH)*CHPh*OH, yields benzaldehyde under the influence of that subskance. Eenzaldehyde owes its conversion into hydrobenzamide, in the first place, to the production of the additive compound, OH* CHPh*NH, ; this undergoes dissociation into water and phenylamidomethylene, which polymerises to diamidostilbene, the latter becoming added to benzaldehyde, and yielding hydrobenzamide. I n the condensation of acetaldehyde to aldol by means of acids and alkalis, the author recognises vinylic alcohol as a n intermediate pro. duct.An aqueous solution of acetalllehyde may be regardpd as containing ethylidene dihydroxide, C HMe(OH)2, which, on elimination of water, becomes dissociated into three products, acetaldehyde, hydroxyethylidene, and vinylic alcohol ; the List-named substance then undergoes ethylene condensation with ethylidene dihydroxide, yielding aldol and water. The basic merczwy derivative of vinylic alcohol, (C,H,O),Hg,HgO, is produced when a n aqueous solution of acetaldehyde is added to freshly precipitated mercuric oxide, and agitated with sodium carbonate or caustic soda ; it is a white powder which gradually decomposes in the desiccator, yielding acetaldehyde, which is immedi- ately produced under the influence of dilute hydrochloric or sulphuric acid.The action of acet'ic and benzoic chlorides is very vigorous, and bromine converts i t into substitution products of acetaldehyde. The formation of ethylic acetoacetate, and of condensation products of acetone with acids and ammonia, must be also regarded as due to ethylene condensation. The oi.tho-compound, COOEt* CH,. C(OEt),* ONa, obtained from ethylic mnlonate and sodium ethoxide, loses alcohol and yields the ethylene derivative, ethylic sodiomalonate, COOEt* CH : C(OEt)*ONa (compare Abstr., 1892, 140). Similarly, from ethylic acetate and sodium ethoxide, arises the ethylene derivative, CH,: C(OEt)*ONa, which is incapable of free existence, and therefore unites with ethylic acetate, acetone, or acetophenone, forming the sodium derivative of ethylic acetoacetate, acetylacetone, or benzoylacetone respectively.It has been now for many years generally accepted that the produc- tion of ether from alcohol and concentrated sulphuric acid at 140' depends on the initial production of ethyl hydrogen sulphate, which undergoes double decomposition with a second molecule of alcohol, yielding ether and sulphuric acid. The author, however, prefers to regard the change as involving dissociation of ethyl hydrogen sulphate into sulphuric acid and nascent ethylene, which is then absorbed by the alcohol present; the production of ether from ethylic iodide and sodium ethoxide is explained on similar lines. The presence of nascent ethylene harrnonises with the formation of large quantities of ethyljc chloride when ethylic alcohol is treated with sulphuric acid and sodium chloride, although very little is produced when alcohol is heated with hydrogen chloride ; moreover, whilst i t is possible to actually separate methylic alcohol and concentrated nitric acid by distillation, the pre- sence of concentrated sulphuric acid at once gives rise t o methylic nitrate, owing to the dissociation of the methyl hydrogen sulphate into methylene, which then unites with nitric acid.ORCIANIC CHEMISTRY.113 The slow combustion of dry ether t o acetaldehyde, acetic acid, and hydrogen peroxide, the production of ethylic peroxide under the influ- ence of ozone, and the recognition of divinyl ether as a product of spontaneous decomposition, now meet with analogous explanation. With regard to divinyl ether, which was supposed by Poleck and Thummel t o be vinylic alcohol (Abstr., 1890, 118), it must be men- tioned that its identity is not fully established ; as, however, a solution of mercuric chloride in hydrogen potassium carbonate yields no preci- pitate, it cannot be vinylic alcohol.The production of formaldehyde and formic acid along with hydrogen peroxide, acetaldehyde, and acetic acid (Legler, Abstr., 1886, 327), when the combustion of ether is effected at 260-500°, depends on the formation of ethylene, which is dissociated into methylene ; the latter burns to hydrogen peroxide and dihydroxymethylene, which further oxidation converts into ortho- formic acid. The compound, (C,HG04)S, obtained by Legler, arises from formaldehyde and hydrogen peroxide, and is therefore regarded as formal peroxide hydrate, O,(CH,* OH),.The exclusive production of formaldehyde when ethylene is burnt in oxygen at 400' is also explained on the assumption that the hydrocarbon is dissociated into met hylene. I n this connection, the author describes an attempt to produce free methylene. Methylenic iodide is slowly converted into formaldehyde when heated with mercury in air at looo, and the same product is formed on heating the methylene additive compounds, CH,,HgI, and CH,,Hg,I,, in air. If, however, the operation is carried out in an atmosphere of nitrogen at lSOo, ethylene is the sole product'. Methylene is probably liberated, and, in the absence of an oxidising agent, under- goes polymerisation.It is well known that the slow oxidation of animal and vegetable matter, aud many carbon compounds, is associated with the production of hydrogen peroxide and active oxygen, and is also accompanied by phosphorescence phenomena (Radziszewski, Abstr., 1881, 488). It has been already pointed out that the two-fold dissociation of hydrogen peroxide can give rise to both atomic oxygen and hydrogen, and the author maintains that the phosphorescence phenomena are clue t o the formation of methylene by dissociation of the organic matter, the hydrocarbon undergoing combustion in moist air in a manner resem- bling the ignition of phosphorus and other spontaneously inflammable si i bstances. 111.-Tetrabromethylene, CBr,: CBr,, is obtained by adding bromine (3 mols.) to silver acetylide suspended in waber, the liquid being con- tinuously agitated meanwhile; i t melts at 56O, and boils at loo", lr)4O, and log", under pressures of 15 mm., 20 mm., and 25 mm., respectively.Asymmetric tlibi-onzovinyl etheq-, CBr,: CH- OEt, is prepwed by heat- ing tetrabromethylene with alcohol in which sodium (4 mols.) has been dissolved ; the product may be separated into two fractions, the por- tion boiling at 72-73' under a pressure of 33 mm. consisting of ethylic bromacetate and dibromovinyl ether. On tresting the mixture with ammonia, ethylic bromacetate is converted into bromacetarnide, leaving dibromovinyl ether undissolved ; the latter boils at 75-76",114 ABSTRACTS OF CHEMICAL PAPERS. under a pressure of 30 mm.Concentrated nitric acid converts dibromo- vinyl ether into ethylic clibromacetate. Cold alcoholic sodium ethoxide (1 mol.) gives rise to ethylic bromactetate, but ethylic ethoxyacetate is produced with excess of the agent. Asymmetric dibromovinyl ether is ideutical with the dibromovinyl ether obtained by Sahanheff from acetylene dibromide and alcoholic potash ; i t s production from tetrabromethylene is explained by as- suming its dissociation into bromine and dibromacetylidone, CBr,: C, which takes up alcohol. Acetylene dibromide, on the other hand, is dissociated in two clirections, (1) into hydroger?. bromide and bromace- tylidene, CHEr: C, and (2) into acetylene and free bromine, which immediately unites with bromacetylidene, forming tribromethylene, CHBr: CBr,! ; the latter is dissociated by alkali into hydrogen bromide and dibromacetylidene, which takes up alcohol, yielding dibromovinyl ether.Di-ioducetylidene, CI, : C, prepared by treating tetriodethylene with alcoholic sodium ethoxide (2 inols.), crybtallises from petro- leum in needles melting a t 81'; it is also produced by the action of sunlight on tetriodethylene, and by the action of iodine on silver acetylide suspended in ether. The substance has been hitherto re- garded as di-iodacetylene, CI:CI, and is also formed when alcoholic potash acts on acetylene di-iodide, CHI: CHI, acetylene being liberated ; this change is analogous to the conversion of acetylene dibromide into acetylene and dibromovinyl ether. Di-iodacetylidene is very volatile, and has the odour of phenylic isocyanide, its vapour attacking the eyes ; it is readily soluble in all organic solvents excepting petroleum.Slow oxidation in neutral solution converts it iuto carbonic oxide and tetriodethylene (compare Biltz, Abstr., 1897, i, 390), but the process is completely checked by the addition of caustic alkali. Tvi-iodovirzylic nityate, CI,: CX- 0-NO,, is obtained on dissolving di-iodacetylidene in cold, fuming nit1 ic acid, which liberates carbonic anhydride and iodine ; i t cryslallises from a mixture of benzene and petroleum in yellow needles, and melts at 109- 110'. When di-iodacetylidene is heated alone at 80-100', it explodes violently, yielding iodine and carbon, but the solution in alcohol, glacial acetic acid, or petroleum, is not completely decomposed when heated with finely divided metals a t 100' for 12 hours, although i t gives rise to tetriodethylene, Acetylene is formed when di-iodacetyli- dene is reduced with sodium amalgam or sulphuric acid and zinc dust, and the hydrocarbon is also produced in small quantity along with carbonic oxide when the substance is treated with alcoholic sodium ethoxide at 100' ; excess of the latter agent gives rise to a mixture of ethylic iodacetate and ethylic ortluiodacetnte, CH,I*C(OEt),, which is a colourless,.pungent oil, and boils at 93' under a pressure of 14 mm.Asymnzetrzc dibromodi-iodethylene, CI,: CBr,, is prepared by adding bromine (1 mol.) dissolved in chloroform to a solution of di-iodace- tylidene in the same medium ; it crystallises from glacial acetic acid in yellowish leaflets, and melts a t 95'.Alcoholic sodium ethoxide eliminates bromine from the compound, yielding di-iodacetylidene. B~ornc~cetyliclene, CHBr: C, is identical with hromacetylene, preparedORGANIC CHEMISTRY. 115 by Sabanbeff from acetylene dibromide, by treating it with alcoholic soda, It boils at - 2 O , and burns spontaneously in air, yielding hydrogen bromide, carbon, carbon monoxide, and carbonic anhydride ; in a very limited atmosphere, combustion is slow, and acetylene dibrom- ide is produced. The vapour is poisonous, and has the odour of phosphorus vapour ; moreover, its solutims in dilute nitric acid, water, or alcohol, which have the odour of ozone, exhibit phosphorescbnce during many days, and give ozone reactions.Although bromacetyl- idene acts vigorously with halogens and halogen hydrides, it is indigerent towards ethylic hypochlorite. ByorrLacetylidene di-iodide (di-iodacetylidene hydrobromide, or a s p - m e t ~ i c di-iodob?.ometkyZene), CHBr: CI,, is obtained by passing brom- acetylidene into an ethereal solution of iodine ; it boils a t 104' under a pressure of 10 mm. Alcoholic sodium ethoxide, or potash, converts it into di-iodncetylidene, which is also produced under the influence of alcoholic sodium phenoxide and alcoholic potassium acetate (at 100') ; in this respect, it resembles ethylic bromocyanacetate, from which hydrogen bromide is eliminated under similar conditions. Di-iodace- tylidene hydrobromide, however, undergoes no change when heated with sodium acetace and a small quantity of glacial acetic acid a t 150' during 12 hours, and it is also indifferent towards silver acetate a t 1 00'.Tri-iodobromethylene, GI,* CBrI, is a bye-product in the preparation of the foregoing substance, and remains as a crystalline residue in the distilling flask ; i t crystallises from glacial acetic acid in yellowish leaflets, and melts a t 135'. Alcoholic sodium ethoxide, or potash, converts it into di-iodacetylidene, which is also produced under the influence of sunlight. The paper concludes with a discussion of the general behaviour of trihaloid and tetrahaloid derivatives of methane, and of certain phases of molecular rearrangement, on the lines already laid down. M. 0. F. Action of Sulphuric Acid on Goal Gas. By P. FRITZSCHE (J.pr. Chem., 1897, 56, 258--265).-Berthelot (this Journal, 1876, ii, 183) has shown that when coal gas is passed through concentrated sulphuric acid, brown coloured substances are formed consisting of condensation products of substituted acetylenes, The author now shows that the nature of the products varies with the coal gas examined and in no case is the formation of these substances so simple as Bert helot's experiment suggested, Coal gas freed from benzene and hydrogen sulphide was treated with concentrated sulphuric acid in iron vessels under a pressure of about 4 atmospheres. Prom the oily product thus obtained crystals separated on cooling, which proved to be the iron salt of a sulphonic acid. By treating all the oil with caustic soda, considerable amounts of the sodium salt of the same acid mere obtained, and from this the copper, sodium, anmonium, iron, and culciuna salts were prepared.The free m i d , liberated from the copper salt by treatment with hydrogen sulphide, forms white crystals readily soluble in water, is very stable, not being acted on by hot concentrated sulphuric acid,116 ABSTRACTS OF CHEMICAL PAPERS. and appears to be the sulphonic acid of a substance having the formula C,,H,,O. This may probably be cedar camphor, a supposition sup- ported by the fact that camphors, as a rule, form st'able sulphonic acids. At least one other substance of similar constitution exists in the mother liquor from the sodium salt, and will be further investigated. A. W. C. Preparation of Bromonitromethane. By JOSEPH TCHERKIAC~ (Rev., 189'7, 30, 2588).-Bromonitromethane can readily be prepared by dissolving 15 grams of nitromethane in baryta water, cooling with ice and adding the solution to 39 grams of bromine covered with pieces of ice; the excess of bromine is then removed by sulphurous acid and the liquid distilled, when 1s grams of the pure compound is obtained.A. H. By GUILLAUME L. J. DE CHALRIOT (AwY. Chem. J., lS9'7, 19, 877--8'78).-1n reference to the preparation of this substance by Biltz (Abstr., 1897, i, 389), the author states that he obtained i t some years ago in preparing ethylene tetriodide by Maquenne's method, using calcium carbide instead of barium carbide. The alcoholic washings of the crude tetriodide were diluted with water, when acetylene di-iodide was precipitated together with some oily matter.It crystallised from alcohol or ether in long, transparent needles and melted a t 82'. By adding iodine to a solution of acetylene in potassium hydroxide solution, no ethylene tetriodide was forined, but a white precipitate was produced which crystallised from benzene in needles; it has a very pungent odour and attacks the mucous mem- brane especially of the eyes. A similar compound prepared with bromine is a n oil which takes fire spontaneously on exposure t o the air and has a very disagreeable odour. Regularities in the Boiling-points of Isomeric Aliphatic Compounds. By NICOLAI A. MENSCRUTKIN (Bey., lS97! 30, 2784-2791).-When the boiling points of the various amylic and hexylic alcohols are compared amongst each other, the same regularities are observed as with the constant of velocity of reaction (this vol.,i, 119), the normal compounds having the higher boiling point, which is lowered by the introduction of side chains, according to their position, size, and number, in the manner already described.The alcohols are peculiarIy favourable for such a comparison, because 1 he greatest difference of boiling point exhibited by a set of isomerides is larger than in the case of other compound^, :tnd, moreover, increases with the number of carbon atoms present. But similar regularities can be observed with other compounds of the type X*[CH2In*CH3 and their isomerides, where X = I, CK,* COO, NH,, or COOH ; and also with compounds of the type X.[CH2],,*X and their isomerides, where X=Br, OH, or CH,.2 : 4-Hexadi-inediol-1 : 6. By ROBERT LESPIEAU (Compt. rend., 1896, 123, 1295-1~96).--OH*CH,*CiC~CiC*CH,*OH, is obtained when the copper derivative of propargylic alcohol is oxidised with potassium ferricyanide and the product treated with ether, It is a colourless, erystalline solid melting a t 11 1-1 12' and turning Acetylene Di-iodide. E. W. W. C. F. B.ORGANIC CHEMISTRY. 117 yellow or rose-coloured under the action of heat or light. It dissolves in water, alcohol, ether, and acetic acid. The most suitable agent for purification is boiling benzene, from which i t crystallises on cooling. At - 15', i t combines with 4 atonis of bromine. I t s glycolic nature was proved by converting it into the diacetin. The diinethyEic ether, OMe*CH,* CiC*CiC*CH,*OMe, is obtained when methyl propargyl ether is oxidised.It is a colourless liquid which turns brownish-red on exposure to light ; it melts at - go, distils a t 104*5-105~5' under a pressure of 12-13 mm., has the sp. gr. = 0.9969, and at - 15' com- bines with 4 atoms of bromine. J. J. S. New Synthesis of Glycerol and of Dihydroxyacetone. By OSCAR PILOTY (Be?.., 1897, 30, 3161-3169. Compare Abstr., 1897, i, 453).-Whea bromine acts on an aqueous solution of dihydroxy- acetoxime (Zoc. cit.), nitrous oxide is eliminated, and dihydroxyacetone produced ; reduction of the ketone with sodium amalgam converts i t into glycerol, a step which completes the synthesis of that substance from formaldehyde. The different stages by which the synthesis is effected are the following.Nitromethane converts formaldehyde into teritary nitrotrihydroxybutane, NO,* C(CH,* OH),, which on reduction yields hydroxylaminotrihydroxybutane, OH*NH* C (CH,. OH), ; oxi- dation with mercuric oxide eliminates formizldehyde from this substance, giving rise to dihydroxyacetoxime, 0H.N: C(CH,* OH),, which is then treated in the iuanner already indicated, Dihydroxyacetone, CO( CH,* OH),, is prepared by adding bromine (15 grams) to a solution of dihydroxyacetoxime (10 grams) in water (100 c.c.), the temperature being allowed to rise to 40'; by a method of purification which is detailed i n the original paper, the ketose is obtained as a white solid, which crystallises from much boiling acetone in A&, prismatic plates melting at 65-75'. Dihydroxyacetone dis- solves with extraordinary readiness in water, and tastes sweet, producing a cooling sensation on the tongue ; it exerts vigorous reducing action on cold Fehling's solution, and when a 1 per cent.solution is boiled with the agent, the reduction effected is equal to that produced by an equal weight of grape sugar under the same conditions. The ketase, however, is not fermented by yeast. When the aqueous solution is treated with phenylhydrazine and acetic acid, the plienylosazone is produced, crystallising from benzene in elongated, prismatic leaflets melting at 132'; this compound was obtained by E. Fischer and Tafel (Abstr., 1888, 1264) from glycerose, and by Piloty and Rue (Abstr., 1897, i, 454) from dihydroxyacetoxime. The sodium hyds*ogen sulplde compound crystallises from dilute alcohol in stellate gi.oups of slender needles.Dihydroxyacetone is reduced to glycerol by means of sodium amalgam in an aqueous solution of aluminium sulphate. If the syrup from which dihydroxyacetone is first separated remains for some time without being sown with a crystal of the substance, a compound separates in minute crystals, and when recrystallised from alcohol, melts at 155'; it has a sweet taste, reduces hot Fehling's solution, and appears to be identical with the substance obtained from dihydroxyacetone when an attempt is made to crystallise it from alcohol. Another compound is produced when the solution of di- VOL. LXXIV i. k11 8 ABSTHACTS OF CHEMICAL PAPERS. hydroxyacetone is evaporated i n a vacuum a t 65-70° ; it is a white solid, resembling crude starch, and is insoluble in absolute alcohol.It dissolves very slowly in boiling water, and yields, with dilute acids, a turbid liquid which reduces cold, alkaline copper oxide. These two substances are doubtless polymerides or anhydrides of dihydroxyacetone. The author discusses the part which is played by formaldehyde in the chemistry of vegetable physiology. Reactions of Potassium Ferricyanide with Glucose and their Application to Volumetric Analysis. By N. TARUGI and G. NICCHIOTTI (Gccxxetta, 1897, 27, ii, 13 1--153).-The authors shorn that t h e reaction between potassium ferricyanide and glucose in boil- ing potash solution depends on the concentration; the reaction is represented in normal solutions by the equation 10 K,FeCy, + 17KI30 + 2C,H,,O, = 10K4FeCy, + 2K2C0, + 2C,H30,K + 12H,O + C,H,,07K, in N/ 10 solutions by the equation 10K3FeCy, + 21KHO+ 4C,H,,O, = 10K,FeCyG + C,H,,07K + 8C,H,02K + 2KHC0, + 46H20, and i u N/40 solutions by the equation 10K,FeCy, + 19KHO+5C6H,,0, = 10K4FeCy, + 5C,H,,07K + 4KHO + 1 OH20.The course of these reactions was followed by determinations of the velocity of reaction. Working with solutions of either of these three concentrations, with potash, glucose, and potassium ferricyanide, if the concentrations of two of the solutions are known, that of the third can be determined. By W. ALBEBDA VAN EKENSTEIN (Coinpt. rend., 1897, 125, 71 9).-The caroubinose described by Effront (Conzpt. ?*end., 1897, 125, 309) is identical with the d-mannose de- scribed by the author (Abstr., 1896, i, 272). The bigher rotatory power observed by Effront is probably due to the presence of products of incomplete saccharification, possibly a bihexose derived from two mannose groups.C. 13. B. Biological Production of Levulose from Mannitol. By CAMILLE VINCENT and B ~ N ~ D I C T DELACHANAL (Conapt. rend., 1897, 125, 716-717).-When the ferment of sorbose is cultivated in a mineralised peptone solution containing 3 per cent. of mannitol, the mannitol is oxidised and converted into levulose. This change is the converse of the production of mannitol from levulose by the action of sodium amalgam. C. H. 13. Humin Formation from Sugar on Oxidation with Potas- sium Permanganate. By H. VON FEILJTZEN and BERNHARD TOLLENS (Bey., l897,30,2581--2584).-The authors do not agree with Benni's conclusions, and find that the brown precipitate formed by the oxida- tion of sugar with potassium permanganate has nothing to do with humin substance, but consists for the most part, of oxide of manganese and potassium hydroxide, and contains only 0.5-0.7 per cent.of carbon. J. F. T. Hydrolysis of Starch by Diastase. By PAUL PETIT (Conzpt. ?.end., 1897, 125, 355--357).-Starch was hydrolysed at 70" with precipitated diastase (1 per cent.) until the colour with iodine no longer changed. M, 0. F. W. J. P. Caroubinose and d-Mannose.ORGANIC CHEMISTRY. I19 Normal Y B a [a- €thy 11 aP aa The red colorutioii thus obtained could only be destroyed by the additiou of larger quantities of diastase. The liquid which gave the red coloration was concentrated, and after cooling, fermented with yeast ; after filtration and concentration a syrup was obtained, which mas precipitated with alcohol, purified, washed and dried thoroughly. The last traces of sugar were removed by extracting with absolute alcohol in a Soxhlet tube for 8 hours.Dcxtrin D as thus obtained is a white, non-hygroscopic powder; its composition is probably (C,H,oOj)3, i t s specific rotatory power u,,= + 176*4", and its reducing power J%= 14.93. It gives no osazoce, and yields glucose when hydrolysed by boiling for about 3 hours with dilute hydrochloric acid; when boiled for a shorter time, a mixture of glucose with a biose is obtained, the osazcne of the latter melting a t 1S0--1Slo. The action of diastase on dextrin D has also been studied.J. J. S. 8302 3807 3783 3886 3790 3537 2985 2759 1257 1240 1189 P-2 314 270 Aliphatic Carbon Chains. By NICOLAI A. MENSCHUTKIN (Ber., 1897, 30, 2775--S784).-This paper gives t h e results of an investiga- tion, the details of which have been published in J. Russ. phys.-chenz. Soc., 29, 444. The velocity of reaction of primary amines with allylic bromide in fifteen times their weight of benzene and at 100' has beenexamined; the values of the constantof velocityk = ( A - $x)/(A - x ) t are tabulated below. As regards nomenclature, the Greek letter indicates the position of the side chain (which, with but one exception, is methyl) ; thus NH,* CHMe* CHMe* CH, is up-amylamine. ~ Jlethyl- ~ Ethyl- ~ Propgi- ~ Butyl- ~ h n y l - ~ Hesyl- ninine.smine. amines. amines. ainines. amine. Iuspection of the table shows t h a t the formation of a carbon chain by the change from methylamine to ethylamine is attended by a marked diminution of the constant. Once a chain is formed, however, the elongation of this chain, so long as it remains primary, has but little effect on the constant, the normal primary aliphatic amines, with the exception of methy lamine, having approximately the same constant. The introduction of a side chain lowers the constant, and the more so the nearer it is to the amido-group; in the one case of methyl, as compared with a-methyl (amylamine), i t is seen t h a t the elongation of a side chain produces a further diminution of the velocity of reaction. The introduction of a second side chain further diminishes the velocity, and in the same manner as before, a minimum value of the constant being obtained when both side chains a r e in the a-position.I;. 2120 ABSTRACTS OF CHEMICAL PAPERS. The old measurements of the rate of etherification of aliphatic alcohols show the same regularities, the hydroxyl group here replacing the amido-group of the amines. Action of Hydrogen 8ulphide and of Carbon Bisulphide on Trimethyltrimethylenetriarnine. By MAKCEL DEL~PINE (Ann. China. Phys., 1896, [vii], 9, 119--133).-This work has been published previously in an abridged form (see Abstr., 2597, i, 456). By J OHANNES THIELE and WILHELM OSBORNE (Ber., 1897, 30, 2867-Z869).-By the action of potassium cyanide on diazoguanidine nitrate, there is obtained, beside much amidotetrazole, ditmoguanidine cyunide, Ni C*N:N*NH* U(NH,):NH ; this is a yellowish substance which decomposes above ZOO"; in it the CN group can be converted into CO-NH,, C(NH,):NH, C(NH,):NOH, COOEt, stc., by the usual methods. These are the first aliphatic diazo- amido-compounds that have been obtained. ~o~*nzccnzidodiccxoccmiclo foiwzanzidine, NH,* CO *N: N*NH* C( NH,): NH, crystallises with 1H,O in yellow needles which explode a t 140'; the colourless hyclrocldo&le explodes a t 141'.EthyZic formurnidineclinxo- mzidofornzate, COOEt*N:N*NH* C(NB,):NH, is yellow, and melts at 162'. Both of these substances unite with sulphurous acid in the cold, and the products, NH, CO*NH* N( S0,H) *NH *C( NH,) :NH and COOEt*NH.N( SO:,H) *NH*C(NH,) :NH, must be regarded as deriva- tives of prozan, NH,*NH-NH,.It was not possible, howerer, to isolate prozan from them; unlike hydrazine, it seems to be very unstable. C. F. B. Action of Sodium on Methyl Propyl Ketone and on Aceto- phenone. By PAUL C. FREER and ARTHUR LACHMANN (Anzer. Chenz. J., 1897, 19, 878-89O).-The action of sodium on a dilute solution of methyl prop91 ketone in ether gives rise to a white, flocculent preci- pitate of the formula C,H90Na, hydrogen being evolved ; this substance is fairly stable in dry air, but is decomposed by water. As it is probably of a complex nature, like the analogous sodium acetone, the action of sodium suspended in ether on LZ mixture of the ketone with benzoic chloride was investigated ; the product was treated with alkali, which dissolved a large quantity of benzoic acid, and a trace of an undetermined fatty acid.Dibenaoylnzethyl Propyl Ketone, CHEz,*COPr or OH*CPh:CBz-COPr. --This melts a t 1 1 5 O , is almost insoluble in cold alcohol and ether, and is best purified by dissolving i t in boiling alcohol, from which it sepa- rates in white, amorphous flakes. It gives an intense red coloration with ferric chloride, is soluble in alkalis and alkali carbonates, and is slowly precipitated from such solutions by carbonic anhydride. By varying the strength of the alcohol from which it is crystal- lised, and the rate of cooling, the melting point of the product varies between 101' and 115'; in some cases, also, i t gives only a very faint ferric chloride reaction. This may be due to the exist- ence of two modifications analogous to that of Claisen's similarly constituted dibenzoylacetylmethane (Annulen, 291, 73).It is only very slowly hydrolysed by alkalis. It gives several products with phenyl- hydrazine, one of which forms long needles, and melts at 110'. C. F. B. J. J. S. Derivatives of Proean.ORGAN10 CHEMISTRY. 121 The original ethereal solution contains the benzoyl compounds of inethyl propyl ketone and of methyl piwpyl carbinol, and the iso-ketone CH,:CPr*OH, seemingly in the form of its hydrogen chloride com- pounds. The action of benzoic chloride on sodium methyl propyl ketone would thus appear t o be similar t o i t s action on sodium acetone, and the sodium compound would have the constitution represented by the formula ONa* C Pr : CH,.By the action of sodium on a mixture of benzoic chloride and aceto- phenone under conditions similar t o those described in the previous reaction, the authors obtained di- and tri-benzoylmethane from the alkaline extract, whilst the ethereal solution, on fractionation under 14 mm. pressure, yields a n oil containing acetophenone and chlorinated derivatives, The thick tarry residue, on saponification with potash, gives benzoic acid and tribanzolymethane, and with dilute sulphuric acid at 160°, benzoic acid, acetophenone-pinacone, and a ketone which boils at 180-152O under 14 mm. pressure. This ketone contains chlorine, gives a deep red coloration with ferric chloride, is insoluble in alkalis, and reacts with phenylhydrazine. The reaction is, there- fore, similar t o that with methyl propyl ketone, except t h a t no iso- ketone benzoate is formed.Hence sodium acefophenone has a constitution represented by the formula ONa*CPh:CH,. The action of sodium on mesityl oxide was also investigated, but no definite results were obtained. Diethyl ketone in ethereal solution is attacked by sodium with liberation of hydrogen, forming a white sodium compound, which seems t o be more stable than sodium acetone or sodium methyl propyl ketone, but resembles them i n properties. E. W. W. By CARL D. HARRIES and FRITZ LEHMANN (Be?., 1897, 30, 2726-2737. Compare Abstr., 1897, i, 2ll).-It has been several times observed t h a t unsaturated ketonesdiff er considerably from saturated onesin their behaviour towards hydroxylamine. The authors, for instance, have shown t h a t phorone gives rise t o three substances, none of which is the normal oxime (Zoc.cit.), and three hydroxylamine derivatives have been also obtained from benzylideneacetophenone (Claus, Abstr., 1807, i, 189) ; Tiemann has found that isocamphorone yields hydroxylaminodi hydrocamphorone- oxime under the influence of alcoholic hydroxy lamine when the ketone is in excess (Zoc. cit., i, 200), and Knoevenfigel, generalising from the behaviour of ketones of the tvpe RCO*CR:CHR, has shown that they Action of Hydroxylarnine on Phorone. U L .I FHR* CHR CR = fi>O are converted into derivatives of the constitution (compare Abstr., 1896, i, 189). Returning to their study of the action of hydroxylamine on pborone, the authors find t h a t treatment with a cold solution of the base in absolute alcohol gives rise t o triacetonedihydroxylamine, OH*NH* CMe,* CH,* CO*CH,. Cll!le,-NH* OH, the anhydride, CO<g%: ~ ~ ~ : ~ ~ > O , being formed if the liquid .G .G is warmed with water and free alkali ; triacetonehydroxylamine, CO<:2: gg:>NOH, described in the previous paper (Abstr., 1 897,122 ABSTRACTS OF CHEMICAL PAPERS, i, 2 1 a), is produced by the action of hydroxylamine (1 mol.) on phorone in presence only of free sodium ethoxide ; this is analogous to the con- version of phorone into triacetoneaniine, CO<c!H~. CH * CMe c,fe:>NH, tinder the influence of ammonia.Triacetonedih yclroxylanzine, OH*NH* CMe,* CH,. CO*CH,* CMe,*NH* OH, is obtained by adding a solution of free hydroxylamine (2 mols.) in 400 c c .of niethylic alcohol to 50 grams of phorone dissolve6 in 100 C.C. of the same medium ; after 4 days, the liquid is diluted with ether (2 vols.), filtered, and treated with anhydrous oxalic acid (33 grams) dissolved in ether, the oxalate which is thus obtained being finally dissolved in dilute hydrochloric acid and mixed with potassium carbonate. The bise is a colourless, syrupy liquid, which boils at 135' under a pressure of 20 mm., without undergoing decomposition if small quantities are manipulated ; i t dissolves readily in water, and is very soluble in alcohol, ether, light petroleum, and benzene. It has a vigorous reducing action on cold Fehling's solntion, and is feebly alkaline towards turmeric ; prolonged treatment with boiling water is without influence on the substance.The hydrochloride crystallises from a mixture of absolute alcohol and ether in hygroscopic leaflets ; it begins t o melt a t 11 Go, and effervesces at 130". When the aqueous solution is boiled in a reflux apparatus, the hydrochloride of triacetone- dihydroxylamine anhydride is produced. The oxalate, prepared in the manner described, crystallises from dilute alcohol in small prisms ; it melts and effervesces at 165O. The dinitroso-derivative, obtained by adding sodium nitrite to a n aqueous solnt8ion of the hydro- chloride, crystallises in leaflets, and is decomposed by concentrated caustic soda, which liberates gas. The compound is acidic in character, and does not reduce Fehling's solution ; i t fails t o give Liebermann's reaction.The anhydride of triacetonedihydroxylamine, >o, CH,*CMe,*NH Co<CH,. CMe,*NH has been already described (Zoc. cit.), and is prepared by heating phorone with free hydroxylamine (2 mols.) and a few C.C. of concentrated caustic soda, in a reflux apparatus, until the liquid has no action on Fehling's solution ; the I~yd~obron?,ide and hydrioclide crystalhe i n stellar aggregates of leaflets, the oxaZate forms long needles, the TUUYO- chloride leaflets, and the plcatinocldokle prisms. When the dihydroxylamine derivative or its anhydride is reduced with zinc dust and hydrochloric acid, triacetonediamine is produced, identical with the compound obtained by Heintz from acetone and ammonia; the base boils a t 95" under a pressure of 1 2 mm., and the aqueous solution, when boiled alone or with hydrochloric acid, yields triacetonamine. The zinc double salt crystallises from water in largo plates containing water of crystallisation which is lost at 110' ; it decomposes at 208'.The dioxalate crystallises in small white needles, and melts and effervesces at 189'. If the redaction of the dihydroxylamine derivative and its anhydride is carried out with sodium amalgam and dilute sulphuric acid, trince- tonenlkadinmine, NH,* CMe,* CH,* CH(OH)*CH,* CMe,-NH,, is pro-ORGANIC CHEMISTRY. 123 duced ; this crystallises from ether in rhombic prisms, melts at 98-99", and boils at 205-210". Triacetonehydroxylamine, CO<CH2' CH;CMe, CMe2>N* OH, is prepared by allowing phorone, dissolved in methyfic alcGhol, t o remain with free hydroxylamine (1 mol.) and free sodium methoxide (1 mol.) for several days, until the reducing action of the liquid on Fehling's solution is but slight (compare Zoc.cit.) ; the hydriodide crystallises from a mixture of alcohol and ether in yellowish prisms, becomes brown a t 170°, and melts at 180'. The benxoyl derivative crystallises from light petroleum in needles, and melts at 117'. Reduction with sodium amalgam in acid solution converts triacetonehydroxylamine into the base, C,H,,NO,, which crys- tallises in leaflets, melts a t 56-57', and boils at 225-235"; the aurochloride crystallises in lustrous, golden prisms. Triacetone- hydroxylamine induces temporary paralysis of the spinal nerves. Experiments on the behaviour of mesitylic oxide towards hyclroxyl- amine have led to the production of three monhydroxylamine deriva- tives.M. 0. F. Ketonic Acetates. By A. COLLET (Conzpt. rend., lS97, 125, 354-355. Compare Hunnius, Abstr., 1878, p. 147).-An alcoholic solu- tion of the brominated ketone is warmed with a slight excess of pure dry potassium acetate, and after removal of the potassium bromide the alcohol is distilled off on the water bath and t h e residue poured into cold water. The oily product is then separated, dried, and distilled under diminished pressure. a-BenxoyZethyZic acetate, CH,*COO*CHMeBz, obtained from Gromo- propionyl benzene, is a yellow oil with a n aromatic odour; it is insoluble in water, but dissolves in alcohol or ether ; its sp. gr. = 1.11, and it distils at 158-160" under a pressure of 20 mm.a-Benxoylpropylic acetate, CH,*COO*CHEtBz, boils at 164-170" under a pressnre of 25-30 mm. a-BenxoyZisopropyZic acetate, CH,*COO*CHMe,Rz, boils at 135-140' (at 15-20 mm.). When hydrolysed with dilute soda or with baryta water, these acetates yield yellow liquids having the characteristic properties of acetols. J. J. S. By N. TARUGI (Gccxxettu, 1897, 27, ii, 153--166),-At a low temperature andin presence of snf- ficient sodium carbonate to neutralise tbe hydrochloric acid produced, arsenic trichloride acts on thioacetic acid in accordance with the equation 2MeCOSH +AsC13 = (MeCOS), AsCl + 2HC1. The compound of the composition (RleCOS),AsCl is a yellowish liquid, of sp. gr. = 1,102, which begins to deposit arsenic trisnlphide at 5', and decomposes at lower temperatures on exposure t o light; it is more stable when dissolved in alcohol, ether, chloroform, or carbon bisulphide.On prolonged boiling, thioacetic acid and arsenic tri-iodide interact with formation of arsenic sulphiodide, AsSI, a crystallir.e, yellow powder insoluble in the ordinary solvents; it is decomposed by alkali hydxoxides in accordance with the equation 3AsSI+ 12NaHO = Na,AsS3 + 2Na,AsO, + 3NaI + 6H,O, and is identical with the product The oxulate also forms prisms, and melts at 85". Thio-organic Compounds of Arsenic.124 ABSTRACTS OF CHEMICAL PAPERS. obtained by heating arsenic sulphide with iodine or arsenic trioxide. The reaction by which arsenic sulphiodide is produced, namely, AsI, + MeCOSH + H,O = Ad31 + MeCOOH + 2H1, is a reversible one.At lorn temperatures, thioacetic acid reacts with arsenites in accordance with the equation 2MeCOSH +- Na,AsO:: = (iUeCO),S + NaAsOS + 2NaHO ; a t ordinary temperatures, arsenic trisulphide is precipitated. I n presence of iodine and a t a low temperature, thioncetic acid and arsenites react with formation of a heavy oil of the composition (MeCOS),As2S3 ; this is insoluble in water or organic solvents, slowly solidifies to a yellow mass, and when boiled with water yields acetic acid and arsenic trisul phide. This additive conapound is also obt,ained by the action of acetic sulphide on arsenic trisulphide at ordinary temperatures. When the liquid substance is treated with gaseous ammonia, a compound of the composition [NeCOS*As( NH,)],S, is obtained a s a yellow powder which is sparingly soluble in cold organic solvents, but dissolves in mineral acids with immediate precipitation of arsenic trisulphide; it is converted into a substance of the com- position [I\leC'OS*As(OH)],S, by suspending i t in cool dilute acetic acid and adding potassium nitrite.On treating the additive com- pound with an alcoholic solution of aniline, a substance of the composition [MeCOS*As(NHPh)],S, is obtained as a yellowish powder ; a similar compound is obtained with paratoluidine. Both give the above dihydroxy-compound when treated with nitrous acid, and the toluidine derivittive yields dehydrothiotoluidine wben treated with dilute hydrochloric acid. W. J. P. y-Ketonic Acids. By CLEMENTE MONTEMARTINI (Gnzxettn, 189 7, 27, ii,' 176-184.-0n treating P-methyllevulinic acid with methylic iodide and sodium ethoxide, the author did not obtain PP-dimethyl- levulinic acid as was hoped, but a mixture of up-dimethylglutaric acid and methylsucrinic acid.On treating ethylic levulinate or a- or p- methjllevulinate with i-nethylic iodide and sodium ethoxide, a mixture is ultimately obtained which can be separated into two substances boiling at 100-1 10' and 300--210° ; the fraction boiling a t 100-1 loo gives semicarbazones identical with those of the origical materials in the case of the a- and ,B-methyllevulinatas, but not in the case of ethylic levulinate. The semicai-bc~~o?ze, C,H,,N,O, of ethylic levulinate melts at 150°, whilst that from the ethylic levdinate recovered from the met hylation melts a t 141' ; similarly, the respective hydmxones melt a t 108" and 95-96'.The levulinic acid used was prepared from levulose and the discordant melting points are perhaps explained by Berthelot's observation (Conzpt. rend., 181ri, 123, 341) that such levulinic acid is a mixture of two acids. W. J. P. Dibasic Acids. By L. ~ T A I X ( A m . C'him. Phys., 1896, [vii], 19, 356--407).-The author finds the best method of obtaining adipic acid to be Crum Brown and Walker's electrolytic method. Aclipic chloride, C,H,( COCl),, after several fractionations under reduced pressure, forms a colourless liquid distilling at 125-1 28" under a pressure of 11 mm., but undergoing slight decomposition a t the same time. AdipicORGANIC CHEMISTRY. 125 co anhydyide, C,H,<CO>O, is obtained by the action of the chloride, diluted with a few cubic centimetres of anhydrous ether, on sodium aclipate ; i t crystallises from benzene in small, mammillated masses melting a t 95-100'; a small quantity of the same compound is obtained when adipic acid is boiledwith acetic chloride for several hours.Adipic chloride reacts with benzene in the presence of aluminium chloride, yielding 1 : 6-di~ulzenyl~~exanedlione-1 : 6, COPh* [CH,],*COPh, which crystallises from alcohol in yellowish needles melting a t 102-103' ; the corresponding dioxinae melts at 216-218'. Ammonia reacts with a benzene solution of adipic anhydride, yielding adip- amide and aclipamic acid, the latter of which crystallises in microscopic needles melting at 125-130". The author has attempted to prepare diacetylpirnelic acid, CH,(CHAc*CH,*COOH),, by the condensation of formaldehyde with ace topropionic acid in the presence of diethylamine, but without success.Concise details are given for the separation of suberic and azelaic acids. Suberic cldoyide, COCl- [CH,],*COCl, decomposes t o a small extent when distilled under diminished pressure; i t is an oil boiling a t 162-163' under 15 mm. pressure ; the anhydride (compare Anderlini, hbstr., 1894, i, 499) is obtained by the action of the chloride on sodium suberate and crystallises in minute needles melting a t 65-66' (Anderlini, 52-63'). Dibenxoylhexcme (1 : 8-di~he?a?/loctccneclio~e-l : 8) melts at 83-85' and its dioxime at 192-193'. o-Benxoylheptok acid, COPh*[CH,],.COOH, is also obtained in the preparation of the dibenzoyl compound ; it crystallises in brilliant plates melting a t 78', and is but sparingly soluble in water.Subercmide melts at 216' and subeyamic acid, obtained together with the amide by the action of dry ammonia on a benzene solution of the anhydride, crystallises in needles melting at 125-127' (compare Arppe, Zed. f. Chem., 1865, 300). Axelaic cldoride, C,H,,(COCl),, is a colourless liquid boiling at 165' under a pressure of 13 mm., but is partially decomposed a t the same t h e . The anhydride melts at 56-57" (Anderlini gives 52-43'). Dibenxoylheptane, COPh-[CH,]7-COYh, separates from alcohol in colourless crystals melting at 44') and yields a dioxinze which could not be obtained in a pure state. Axelanzide, CONH,*C7H,,*CONH,, melts a t 172', and axetarnic m i d , CONH,*C7H,,*COOH, at 93-95'.Sebamic acid, CONH,-[CH,],-COOH melts a t 170', and sebamide at 208'. The author points out that substituted succinic acids readily yield anhydrides, that oxalic, malonic, and substituted malonic acids do not yield anhydrides under any conditions, and that glutaric acid, sub- stituted glutaric acids, adipic, suberic, azelaic and sebacic acids yield anhydrides, but not very readily. Substituted Succinic Acids. By KARL AUWERS (Anncden, 1897, 298, 147-181. Compare Abstr., 1896, i, 639).-The author has continued the investigation of asymmetric and symmetric methyl- ethylsuccinic acids, and has established the identity of the former with isopimelic acid obtained from amylene bromide (compare loc. cit.), J.J. S .126 ABSTRACTS OF CHEMICAL PAPERS, Tertiary butylmalonic acid and t'he two stereoisomeric &dimethyl- glutark acids are the only members of the group of 24 isomeric acids having the formula C7H,,04 which have not been yet characterised. (Compare Montemartini, Abstr., 1896, i, 667). 1. [With R. FRITZWEILER].-T~~ symmetrical methylethylsuccinic acids are prepared by the action of sodium an a mixture of ethylic methylmalonate and ethylic a-bromobutyrate, the details of the method, and the means by which the products are isolated, being described in the original paper. The fumaroid form crystallises from hot water in long, flat needles melting at 180" when heated with moderate rapidity, and a t 177--179" when the temperature rises slowly ; if rapidly heated, it melts a t 182", and water is eliminated a t 190".It dissolves readily in al-obol, ether, and acetone, and with difficulty in chloroform, being insoluble in petroleum ; 3.05 parts dissolve in 100 parts of water a t 17". Metallic salts yield precipitates when added to a solution of the sodium salt, and calcium chloride gives rise to a crystalline salt when the liquid is boiled; the calcium salt obtained from the acid and calcium carbonate crystallises in colourless, anhydrous leaflets, being evidently different from the salt obtained by Bytschichin and Zelinsky, which contains 5H,O. The malenoid acid crystallises from water in stellate aggregates of slender, lustrous needles, melts a t 101-1 OZ", and loses water at 160". It is readily soluble in organic solvents, excepting petroleum, which dissolves i t with difficulty ; 16.1 parts dissolve in 100 parts of water at 13'.Metallic salts give rise to pre- cipitates, and calcium chloride produces a heavy precipitate in the cold solution, distinguishing this form from the fumaroid acid ; the calcium salt contains 1H,O. The malenoid acid is obtained when the fumaroid mcclification is boiled for 3 hours, or heated a t 210-220" during 8; hours ; it is also produced in quantity amounting to 10 per cent. when the fumaroid acid is heated with 18 per cent. hydrochloric acid at 180-190' during 14 hours, the reverse action taking place with much greater readiness. The paratolilic acid of the fumaroid acid crystallises from dilute alcohol in colourless, slender needles, and melts at 175-1 76" ; the pamtolil also forms needles, and melts a t 109-110".Another com- pound is produced when an attempt is made to prepare the tolil a t high temperatures ; it crystallises from petroleum, and melts a t 86-89'. The anilic acid and ccnil melt a.t 164-1 65" and 103-104" respectively. The paratolilic acid of the malenoid form crystallises from dilute alcohol in lustrous leaflets, and melts a t 147-148O; thepurutolil is identical with the derivative prepared from the fumaroid acid. The ccnilic acid and P-napJ~tl~iZ melt a t 139-140" and 159-160" respec- tively; the alnil is identical with the compound obtained from the fumaroid acid. 11. [With R. F~r~zw~I~ER].-Asymrnetric methylethylsuccinic acid crystallises from water in transparent, lustrous prisms belonging to the rhombic system, and melts a t 103-104"; in every particular, its properties agree with those ascribed t o isopimelic acid, obtained by Bauer and Hell from amylene bromide. The anilic acid and unil melt a t 168-169" and 60-61" respectively ; the parcctolilic acid andORGANIC CHEMISTR,I'.12'7 paratolil melt at 162O and 64--65' respectively, whilst the P-nuphtkilic acid and P-rzuphthil melt at 179" and 96-97' respectively. 111. [With F. I\IAYER].-A specimen of amylene boiling at 29-35', when converted into the bromide, then into the cyanide, and the latter hydrolysed, yielded a small proportion of isopropylsuccinic acid melting a t 11 6" ; the pcimtolilic cicid crystnllises from dilnte alcohol, and melts at 143-144". IV. [With F. BETTERIDGE.] --Etl~yZic a-b~omoIaui*inate is a colourless oil which boils at 170.-174" under a pressure of 11 mm, When heated with finely divided silver at 150" during 5& hours, and the product hydrolysed, it yields bidecplsuccinic cccid, the two isomerides being readily separable by petroleum.Thefumaroid modification which dissolves but sparingly in petroleum, crystallises in white needles melting at 134". The ndenoid form is readily soluble, and separates in slender prisms melting at 74'. By PAUL WALDEN and 0. LUTZ (Zer., 1897, 30, 2795-279S).-l-Bromo- or I-chloro-succinic acid, which yields I-malic acid when treated with silver oxide, under- goes a gradual change of rotation when it is heated with 12 per cent. methyl alcoholic ammonia at 40-45". When the dextrorotation has attained a maximum (after 10-12 hours), a substance can be isolated which melts at 122-124', and has [.ID = + 27.6 to + 29.2" (c = 20 - 1) in aqueous, = +4O*S' in 75 per cent.alcoholic solution; the com- 35. 0. F. Interconversion of Optical Antipodes. position O<~~->CH-CH,-COONH, is assigned t o it. BY treating NH, this with the equivalent quantity of dilute hydrochloric acid, the free acid can be obtained ; this melts at 148', and has the rotation [ u ] ~ = + 9*7"(c = 3) in aqueous solution ; the constitution, is assigned t o i t ; with ammonia, it regenerates the original compound. By boiling it, or i t s ammonium salt, with barium hydroxide, the barium salt of d-malic acid is obtained. I n a similar manner, I-malic acid can be obtained from d-bromo- or d-chloro-succinic acid Law of Etherification of Unsymmetrical Aliphatic Di- carboxylic Acids.By RICHARD ANSCHCTZ (Bey., 1897, 30, 26 5 2-2 65 4. Compare following abstract). --Hydrogen a-eth y lic mesaconate (Ioc. cit.), melting at 42', obtained by the action of alcohol and hydrogen chloride on mesaconic acid, is readily hydro- lysed by alkalis ; the P-ethylic salt, however, which melts at 67-63', yields the acid with difficulty when treated with hydrolytic agents. Jts preparation from ethylic methylacetoacetate, by the introduction of 2 atoms of bromine followed by treament with barium carbonate and boiling XTater, indicates the constitution COOEt*CMe:CH*COOH, the a-salt being represented by the formula COOH*CMe:CH*COOEt. The author therefore concludes that when etherification of an un- symmetrical dicarboxylic acid is effected by means of alcohol and hydrogen chloride, the alkylic radicle is introduced more readily into t h a t carboxylic group which is attached t o a tertiary carbon atom than into one combined with quaternary carbon.According t o this C. F. B.128 ABSTRACTS OF CHEMICAL PAPERS, generalisation, the hydrogen orthoethylic and hydrogen alloethylic salts of carnphoric acid are represented by the expressions, CH,* CH* COOEt CH; CH* COOH and I )CMe, CH; CMeeCOOH CH; CMe*COOEt respectively, a Lonclusion at which Bredt 'has already arrived from other data. The author prefers the terms a-salt and s-salt to ortho- and allo- respectively, the a-salt being the one which is most readily produced. M.0. E. Preparation of Ethereal Salts. By RICHARD ANSCHUTZ and JULIEN DRUGMAN (Bey., 1897, 30, 2649-3652. Compare E. Fischer and Speiei., Ahstr., 1896, i, 201)-The authors point out that the method of preparing ethereal salts described by Fischer and Speier (Zoc. cit.) can be advantageously modified by submitting the crude salt to direct dist8illation under considerably reduced pressure, excess of alcohol being previously removed by the same process. IIydrogen a-methylic itaconnte, CH,:C(COOH)*CH,*COOMe, crystal- lises from methylic alcohol and melts at 67"; i t boils a t 149" under a pressure of 1 2 mm. Hydrogen. a-ethyZic itnconccte melts a t 45", and boils at 153" under ft pressure of 12 mm. Hydrogen ethylic fumarate melts at 6 6 O , and boils a t 147' under ft pressure of 16 mm.Hyd?-ogen a-methylic mesaconate, COOH*CMe:CH*COOMe, melts at 36", and boils at 145" under a pressure of 15 mm. ; hydrogen a-ethylic mesueonate melts at 42", and boils at 150" under a pressure of 15 mm. Hydrogen P-metTLyZic mesaconate, COOMe*CMe:CH*COOH, melts at 61-62", M. 0. F. By WOLF VON LOEBEN (Annalen, 1897, 298, 181--187).-Three of the four theoretically possible methyluric acids have been already prepared, and in the case of two of these, the P- and y-acids, the constitution has been recognised as that of 9-methyl-2 : 6 : 8- trioxypurine and 7-methyl-2 : 6 : 8-trioxypurine respectively (compare Ber., 1897, 30, 55'7). The a-methyluric acid, first obtained by Hill, is either 1 -methyl-2 : 6 : 8-trioxypurine or 3-methyl-2 : 6 : %trioxypurine, whilst &methyluric acid is described in the present paper ; the position of the methylic group in the latter acid, however, cannot be defined until the constitution of methylisodialuric acid, from which it is obtained by condensation with carbamide, has been determined.Methylisodinluric acid, C,H,N ,06, prepared by oxidising methyl- isobarbituric acid with bromine water, is very readily soluble in water and separates in rosette-like aggregates. Barium hydroxide gives rise t o a violet precipitate, &Methyluric acid, C,H,N,O,, is obtained by heating methyliso- dialuric acid with carbamide and concentrated sulphuric acid at 100" and pouring the liquid into cold water; i t separates from 500-600 parts of hot water in colourless, microscopic prisms containing 1H,O, which is removed at 150".It gives the murexide reaction, and &Methyluric Acid,ORQANIC CHEMISTRY. 129 oxidation with lead peroxide converts i t into methylcdkantoin, C5H8N403 melting a t 246' ; the methylallantoin obtained by Hill from a-methyluric acid melts a t 225'. &Methyluric acid dissolves in 527 parts of hoiling water, a-methyluric acid requiring 262 parts. Oximes of Hexahydrobenzophenone and Hexahydropropio- phenone. By W. SCHARVIN (Be?.., 1897, 30, 2862-2865. Compare Abstr., 1897, i, 612, mherefos. 158' veacl 155" as the melting point of hexahydrobenzophenone a-oxhe).-This a-oxime in ethereal solution reacts but slowly with phosphorus pentachloride, and the product is only slowly acted on by water ; the final product was identified as benzoylhexamethyleneamine, C,H,,*NH*C'PhO (von Eaeyer, &4bstr.., 1834, i, 175).This is difficult to hydrolyse, but boiling with acetic anhydride converts it into acetylhexamethyleneamine. The p-oxime reacts much more readily with the pentachloride, and the product is readily converted by water into J~exa~iydroben~anilic2e, C,H,; CO *NHPh, together with some hexahydrobenzoic acid and aniline ; this anilide is readily hydrolysed by strong sulphuric acid. I n consequence of these reactions, the following configurations must be assigned to the two liexahydrobenzophenone oximes f M. 0. F. C,H,,* 5 *Ph 0H.N C,H,,* *Ph N* OH a-Oxime. M. p. 155". @-Osime. M. p. 111". ~exccr~~d?.olrro~iopJ~enone, C,H,, COEt, mas obtained by the action of hexahydrobenzoic chloride (1 mol.) on zinc ethide (2 mols.) ; it boils at 195O, and does not form an additive compound with sodium hydrogen sulphite.Only one ozime could be obtained from i t ; this melts a t 7 2 - - 7 3 O , Pnd) in the Eeckmann reaction, yields a product melting a t 8S0, which must be propionohexametJqZenecmide, C,H1,*NH* COEt, for i t can be hydrolysed to propionic acid and hexamethyleneamine. The oxime must, therefore, have the configuration C'jH1l*E *Et. 0H.N C. F. B. The Benzene Nucleus. IX. Ey WILHELM VAUBEL (J. p a . C'hem, 1897, 56, 266--27l).-The author shows that the change of eugenol into isoeugenol, and also the structure of diketochlorides and allied substances described by Zincke (Abstr., 1897, i, 507), may be sat,is- factorilj explained by his benzene configuration.By WILLIAM R. ORNDOI~FF, G. L. TERRASSE, and D. A. MORTON (Arne?.. Chenz. J., 1837, 19, 845-870).- The authors, from a careful examination of anethoil and its isomerides, have arrived a t the following conclusions. (1) Eijkman's methylchavicole and Grimaux's estragole have t<hesame molecular weight, and are metamerides of anethoil. The results of the investigation of these compounds by diff erent chemists indicate their identity. (2) Liquid metanethoil also has the same molecular weight as anethoil ; horn its chemical behaviour, in which i t closely resembles anethoil, and also from its physical properties, it is to be A. W. C. Anethoil and its Isomerides.130 ABSTRACTS OF CHEMlCAL PAPERS. regarded as a stereoisorneride of methoil, and is probably the trauu- (3) Anisoin, the resinous polymeric compound, H- E*C,H,- OMe (p) Me-C-H modification of anethoil, acts as a colloid towards solvents such as ethylic acetate, acetone, and benzene. (4) Solid met-anethoil and the liquid iso:methoil both have a molecular weight twice that of anethoil, and hence should be named solid dianethoil and liquid dianethoil respec- tively.As they both behave like saturated compounds, they are possibly derivatives of tetramethylene. (5) By heating anethoil under pressure a t 250-275", it is transformed into isoanethoil, the methylic ether of paracresol and the methylic ether of parapropylphenol, the tendency under these conditions being apparently to form saturated compounds. I n determining the molecular weights of liquids such as anethoil by means of the boiling point method with the apparatus devised by Orndorff and Cameron (Abstr., 1895, ii, 480), the condenser tube was contracted a little below the point where the solvent condensed and ran back into the flask, so that when thin glass bulbs containing the liquid were dropped into the upper part of the condenser, they broke on reaching this point, or, if not, could be broken by means of a rod.This method is said to be more convenient and more accurate than that recommended by Beckmann. The authors have also suggested names for anethoil and its isomerides more in accordance with the suggestions of the Geneva Conference and with the present state of knowledge. For example, liquid met-anethoil is named l'-propenylphenol-4-methyl ether.Action of Nitrogen Chloride on Aniline, Methylaniline, and Dirnethylaniline. By W. HENTSCHEL (Bey., 189'7, 30, 2643-2649). -When aniline is treated in molecular proportion with a solution of nitrogen chloride in benzene, a rise of temperature occurs, and trichlor- aniline is produced; this compound is also formed when chlorine is passed into aniline hydrochloride suspended in benzene. Acetanilide is converted into parachloracetanilide on agitation with a benzene solution of nitrogen chloride. ~~.iciLZorornet~~?/ZaniZi~~e, CtiHaCls*NHMe, is prepared by passing chlor- ine into benzene containing methylaniline hydrochloride in suspension, and is also formed when the base is treated with nitrogen chloride dissolved in benzene; i t melts a t 38*5", and boils at 256'.The hyZrochZoride crystallises in prisms, and softens above 100" ; the pkatinochloricle forms large, pale-yellow crystals. Oxidation of tri- chloromet h ylaniline hydrochloride with a sulution of chromic acid gives rise to trichloraniline, the azo-compound being produced when excess of the oxidising agent is employed ; the azoxy-derivative is formed if the process is applied to warm solutions. The action of nitrogen chloride on dimethylaniline yields a co~~~poumZ, C24HllN2Cl19., which crystallises from light petroleum and melts a t 117O; i t is insoluble in water, but is somewhat readily soluble in common organic solvents. When the compound is heated alone, hydro- gen chloride is eliminated in quantity amounting to 18 per cent. of the substance taken. M.0. F. E. W. W.ORGANIC CHEMISTRY. 131 Formation of Chains. XX. Chloranilines. XXI. Nifrani- lines. XXII. Nitrotoluidines. By CARL A. BISCHOFF (Be?.., 1897, 30,2760-2764; 2764-2768; 2769 -2775. Compare this vol., i, 73).- The reacting substances, C,H,R'R"*NH, (2 mols.) and CHtLBr*COOEt (1 mol.), were heated for 4 hours a t 100' (sometimes a t 125-130'; tho numbers referring to this temperature are given in brackets in the table below), and the percentage extent to which the condensa- tion had taken place was estimated by weighing the hydrobromide, C,H,R'R"*NH,,HBr, that had separated, after washing it with warm ether. From the ethereal filtrate, unchanged amine could be re- moved by passing in gaseous hydrogen chloride and filtering, and from this second filtrate the product of the condensation was isolated by fractional distillation or by crystallisation.When the extent of the reaction was very small a t the temperatures mentioned, special exporiments were made a t higher temperatures for the sole purpose of isolating some of the product. I n the table below is given the per- ceutage amount of condensation between the amines and ethereal a-bromo-salts there enumerated ; the numbers for the methylanilines (toluidines) are taken from a previous investigation, and are inserted here for purposes of comparison. E thylic salt. Bromopropionste Phenylacetate . . . Isobutyrate . . . . . i9 (8'7 '7 9 (23 - '1 (88. 14 (82' (42, - 0 (42) (3) .5 (60) - The author draws attention to the effect of the different groups in the different positions, in promoting or hindering the condemation j it is impossible to quote his remarks in full, however, and the regu- layities are, moreover, apparent on inspection of the table given.Here, as often previously, substitution in the ortho-position is frequently found to hinder the condensation most, whilst in the meta-position it has the most favourable influence. The following new ethylic s dts are described :-CChlol'ciiLiZido-a-z~t,o- pionates, C, K,Cl*NH*CHlllle.C!OOEt : o ~ t l ~ o boils a t 2SO-2S5', metcc a t 2SS-294' (melting at 40-3'), pa1'c~ a t 300-306°. Cldoru~ailido-a- pheizylcccetates, C,H4C1*NH*CHP1i*C00Et : o ~ t h o melts at 53 --54O, meta a t 88 -88.5", pura a t 87%". - i~iiti.nnilitlo-ay?.opio,zates, NO2- C,H;NH. CHMe. CciOEt, yellow ; ortho melts a t 142.5', irzetu a t 203O, pai-a at S6-S7' ; purunitr~nilido-a-~)ro~~ionic mid (with H,O) is yellow, melts at 147", and is hygroscopic when anhydrous.132 ABSTRACTS OF CHEMICAL PAPERS.Nitrcc.lziZido-a-z~r~en?/lncet CI tes, N 0, C, H, N H CHP h CO OE t , yellow ; ortho melts at 69-69*5", r n e t a at 83-84', pcwa a t 120-120.5". Para.lzit~anilido-P-iso butyrate, NO,'* C,H,*NH CH, CHMe COOEt, is yellow, and melts at 74'.-Nit~otol~iclido-a-pro3Jlioncctes, NO,* C,H,Me*NH* CHMe* COOEt, [NO, : Me : N H = 3 : 1 : 41 yellow, melts at 62O; [Z : 1 : 41 at 64' ; [5 : 1 : 21 at 103- 104'. n'iti*otoluidido-ap~e~yZc~cetates, NO,* CtiH,Me*NH*CHPh* COOEt ; [3 : 1 : 41, yellowish-red, melts at 106'; [5 : 1 : 21, yellow, at 118.3'. Niti*otolzcidido-isobuty~.ccte [2 : 1 : 41 is yellowish and melts at 80".C. F. B. Conversion of Amines into Phenols. By JACOB MEYER (Bey., 1897, 30, 256&-2569).-The observation t h a t metaphenylenedianiine evolved considerable quantities of ammonia and methy lamine on methyl- ation led t o the general study of the behaviour of aromatic amines when treated with acids at high temperatures, and it was found that when the base was heated in a closed tube with either 1.15 per cent. hydrochloric acid, 20 per cent. sulphuric acid, solution of zinc chloride, &c., at 160-250", a considerable quantity of the corresponding phenol was produced, the yield increasing with the temperature, although at high temperatures considerable quantities of resinous products were at the same time formed.Thus on heating 6 grams of metaphenylene- diamine with 20 per cent. hydrochloric acid at 180', 2 grams of resorcinol was produced, whilst from t e trame thy lmetapheny lenediamine 30 per cent. of resorcinol was obtained. Derivatives of Paramidodimethylaniline [Dimethylpara- phenylenediamine]. By JOHANNES PINNOW and E. KOCH (Be?.., 1897, 30, 8860-2861).-W hen acetamidodimethylparaphenylenediamine is heated with methylic iodide in benzene solution for 10 hours at loo", the acid radicle is not expelled, as in the case of the formamido-com- pound (Abstr., 1 S94,2S1), but the compound ,MeI,NMe,* C,H,*NHAc, melting at 226', is formed. When this is treated with alcoholic lead acetate, the lead bromide first removed and then the rest of the lead by precipitation with hydrogen sulphide, and the filtrate finally evapo- rated down with hydrochloric acid, trii,2et~~yZparamidop~~eny~i~~ chloikle hyd7*ochZoride, MeCI,NMe,* C,H, *NH,,HCI, melting a t 21 9', is obtained ; this has been used for the preparation of azo-dyes soluble in water.J. F. T. C. F. B. Combination of Metallic Acetates with Phenylhydrazine. By JOSEPH MOITESSIER (Conzpt. vend., 1897, 125, 611-612).--Zinc, cadmium, manganese, and cobalt acetates combine with phenylhydra- zine to form compounds of the formula R,BN,H,Ph where R represents one molecule of tho metallic acetate. Nickel acetate under similar conditions yields the compound Ni(C2H,0,),,3N,H,Ph. The compounds are obtained by boiling the powdered salt with a n alcoholic solution of phenylhydrazine for about 15 minutes and then filtering.The zinc compound forms rhomboidal plates which melt at 135O; the cadmium compound, elongated prisms melting at 121" the manganese compound, monoclinic prisms melting at 97" ; the cobalt compound crystallises in rose-coloured prisms which melt belowORGANIC CTTEMISTRP. 133 125' ; and the nickel compound forms greenish-blue prisuis which do not melt a t 260'. All the salts decompose readily when heated. They dissolve in water, alcohol, or chloroform, but not in ether, and their solutions give the- reactions of the metallic salt and phenylhydrazine. C. H. B. Combination of Phenylhydrazine with Metallic Salts. By JOSEPH MOITESSIER (Compt. rend., 1897, 125, 714-716. Compare Abstr., 1897, i, 561, 562).-In addition to the compounds containing one molecular proportion of metallic salt and two molecular proportions of phenylhydrazine, nickel chloride, nickel sulphate, and cobalt bro- mide form compounds with 5 mols.of phenylhydrazine, whilst cobalt chloride and cobalt sulphate form compounds with 4 mols. They are obtained by the action of a large excess of phenylhydrazine on the metallic salt, and are only slightly soluble in alcohol or water in the cold and practically insoluble in ether or chloroform, They give the reactions of phenylhydrazine and the metallic salt that they contain, and they lose phenylhydrazine at 100". NiC1,,5N2H,Ph forms long, blue, rhomboidal lamellae, CoCl,, 4N,H,Ph forms prismatic crystals, CoBr2,5N2H3Ph forms rhombic prisms, CoS0,,4N2H,Ph short prisms, and NiS0,,5N2H,Ph also cry stallises in prisms.Lithium chloride yields the compound LiC1,2N2H3Ph, which crys- t a k e s in deliquescent, rhomboidal lamellae, and the halogen salts of the metals of the calcium group also yield compounds which will be described subsequently, . Amidoazimidobenzene. By JOHANNES PINNOW and E. KOCH (Ber. 1897, 30, 2850-2860).-Methylaniline was converted into di- nitromethylaniline by nitration with a mixture of dilute nitric and sulphuric acids ; this mas reduced with alcoholic ammonium sulphide to nitroamidomethy laniline, N0,:CGH3(NH,)-NHMe, and this, by treat- ment with sodium nitrite in dilute nitric acid solution, waB converted into nitromethylazimidobenzene, N02*C,H,<i&:>N (Zincke and Helmert, Abstr., 1896, i, 300). By reducing this with tin and hydrochloric acid, urn~dornetl~ylaximi~obenxene, NH,*C,H,:N,Me, is ob- tained ; this melts at lSOo, the hydrochlode (with 2HCl), hydrobromide, suZphate (with 4H,SO,) and yellow picmte (with C,H,N,O,) a t 249", 2 3 7 O , 2924 and 237" respectively, the mono-acetyl and -benxoyZ deriva- tives at 237" and 228.5'.The cnrbarnide, NH,*CO*NH*C,H,:N,Me (from the hydrochloride and phenylic cyanate), phenylcnrbmide, NHPh CO *NH* C,H3 :N,Me, and p?~en~Ztl~iocurbarnide (from the base and phenylcarbimide or phenyl- thiocarbimide) were also prepared ; of these, the last melts at 227---228", the others remain unmelted at 300". When amidomethylazimidobenzene hydrobromide (20 grams) is heated with methylic alcohol (22 grams) for 16 hours at 130-1 35O, y$low dimethylamidomethylazimidobenzene methobromide, NMe,* C,H,.N,Me,MeBr, melting at 262", is obtained ; the corresponding chloride and yellowpicrate melt at 205" and 169-1 70".From the mother liquor of the bromide, by displacing the bromine by chlorine and adding mercuric chloride, a trimeth ylmethylazimido- C. H. B. VOL. LXXIV. i . 1134 ABSTRACTS OF CHEMICAT, PAPERS. phenylium compound, HHgCl,,hleCl,NMe,*C,H,:N,Me, melting at 195', is obtained. If a relatively much smaller amount of methylic alcohol (0.8 gram per 5 grams of the hydrobromide) is used in the methylation, only a small quantity of a yellowish-brown nitroso-com- pound melting and decomposing a t 150.5 -151.5" (presumably methyl- azimidophenylm et hylni trosamine, NO*NMe*C,H,: N,Me), is formed when the product is treated with nitrous acid, so that the methylation probably begins with the addition of MeBr to the N,Me group.Dimetl~yZamidomethyZaxim~~obe n xene (methyllaximidonimethyIccnili.ne), NMe,*C,H3:N3Me, is obtained by heating the above-mentioned metho- bromide with ammonia of sp. gr. =0*91 for 9-10 hours a t 180-185", extracting with ether, evaporating the extract, dissolving the residue in hydrochloric acid, and precipitating with mercuric chloride ; it melts a t 90°, the mercwrochloride (with HCl,HgC12) at 174--175O, and the pierate (with 2C,H3N,07) at 180-181°. By dissolving the base in hydrochloric acid, cooling the solution, and adding sodium nitrite, a nitro-derivative is obtained, meth~Zaxirnidonit~~od~~ethyZar~~Z~ne, No2>C H c N > N [N:NMe:NMe2:N0,= 2: 3:5:6].NMe, 6 2 NMe This is orange-red, and melts at 1 4 1 O ; dilute aqueous potash liberates dimethylamine, and acetic acid precipitates from the solution a yellowish-brown nitroso-compound melting at 19 lo, which is presumably methylazimidonitrophenylmethylnitrosamine. Reduc- tion with zinc dust and acetic acid converts the nitro-compound into met~yluzimidoamidodimethyZ~n~ll~ne, NH,*C,H,(NMe,):N,Me, the xincochloride of mhich(with HCl,ZnCl,) melts at 276'; this base gives the phenazine reaction, from which it follows that the amido- and di-methyl- amido-groups must be in the ortho-position relatively to each other. Both amidomethylazimidobenzene and its dimethyl-derivative yield colouring matters with diazobenzenesulphonic acid ; in this respect, the substitution of methyl for imido-hydrogen in amidoazimidobenzene has had no effect.C. F. B. Intramolecular Rearrangement of Isoaldoxime Ethers. By CARL NEUBAUER (Arznalen, 1897,298, 187--201).-1t has beeen shown that when the nitrogen benzyl ether of paranitrobenzaldoxime, in alcoholic solution, is heated with a very small quantity of sodium ethoxide, a part undergoes conversion into the nitrogen paranitrobenzyl ether of benzaldoxime, the action being reversible ; a similar change on the part of the benzyl ether of metanitroisobenzaldoxime is, how- ever, not reversible, whilst the benzyl ether of isoanisaldoxime is in- different to the conditions described. The author has prepared other isoaldoxime ethers, and submitted them t o the influence of alcoholic sodium ethoxide.Berzxylisocinnumaldoxime, CHPh:CH*CH< N*CH2Ph, I is obtained b heating cinnamaldehyde with P-benzylhydroxylamine hydrochloride (19 mol.) and sodium hydrogen carbonate in alcohol; it crystallises from dilute zllcchol in lustrous, light yellow leaflets, and melts a t 130'. 0ORGANIC CHEMISTRY. 135 BeszzyZortAock lei-is0 benxnlclox iuie, C,II,Cl* CH<T ' cry s t allises Benxyloi.t7Lo?Lit~oisobe.nxalclosi7ne, NO,-C,H,.CH< I H2Ph, crystal- lises from very dilute alcohol in yellowish needles, and melts a t 0 from petroleum in cubes, and melts a t 56'. 0 1 25- I 2 6". Benxyliiaetnizitroisoci~zznn.nzalcloxi?ne, NO,-C,,H,~CH:CH~CH< N*CH,Ph I 0 9 separates from benzene in yellow, lustrous leaflets, and melts a t 123'. ~ e ? a ~ ~ ~ ~ a r r c ~ z ~ d ? .o x ~ ~ s o b e n ~ c 6 ~ i ~ o x ~ ~ ? z e , OH*C,H,* CH< N I CH,", crys- 0 tallises from dilute alcohol in long, colourless needles, and melts at 203". ~-Dil~c~raclTLZorod~b~nx~l?~y~roxylcc~~~nc, (C',H,Cl*CH,),N*OH, is ob- tained by heating pnrachlorobenzylic chloride (2 mols.) in alcohol with hydroxylamine hydrochloride and sodium carbonate in a reflux ap- paratus; it crystallises from alcohol in white needles, and melts a t 121-1 22". Pnrcccldoro benx y~parach~~~~~sobenxccldoxi~ae, CGH,C1.CH<~'CH,'C~H4c1, 0 is prepared from dichlorodibenzylhydroxylamine by oxidation with potassium dichromate and glacial acetic acid ; it crystallises from alcohol in lustrous, white plates, and melts at 1413. p- Parachloro berzxp Zhyclroxplc~mine, C,H,Cl* C H,*N Ha OH, obtained by passing steam into a solution of parachlorohenzylparachlorisobenz- aldoxime in 20 per cent.hydrochloric acid, crystallises from light petroleum in beautiful, long needles, and melts at 87-88'. The hydro- chloride melts a t 165--166". Pccrac~ilo~obe~zxylisobenxaZdox~~~ae, CHPh<XeCH2* C6H4C1, crystal- Benxylparaci&wiso benxaldoxime, C,H,Cl*CH<r CH2Ph, separates from dilute alcohol in long, prismatic needles, and melts at 12lC. Of the foregoing ethers, parachlorobenzylisobenzaldoxime and benzyl- parachlorisobenzaldoxime undergo molecular rearrangement. A convenient method of preparing P-benzylhydroxylamine consists in heating a mixture of acetoxime and benzaldehyde (1 mol.) with an equal volume of 75 per cent. acetic acid in a reflux apparatus.lises from dilute alcohol in rhombic leaflets, and melts at 125-126". 0 3%. 0. F. Vinylideneoxanilide. By HANS VON PECHMANN (Ber., 1897, 30, 2791-2794).-This substance, I >C:CH,, which is formed when glyoxime-N-phenyl ether (Abstr., 1897, i, 75) is heated with acetic anhydride, is more conveniently prepared by boiling oxanilide with CO*NPh CO*NPh 1 2136 ABSTRACTS OF CHEMICAL PAPERS, acetic anhydride and sodium acetate. It melts a t 208-210°, de- colorises permanganate immediately, and reacts with bromine at 0" in chloroform solution ; in the latter case, however, hydrogen bromide is given off, and the product, which melts a t 189' and decolorises permanganate, is bvomovinylideneoxcnilide, C,N,Ph,O,: CHBr. Al- coholic hydrochloric acid decomposes it into its components, whilst al- coholic potash hydrolyses i t to oxalic acid and ethenyldiphenylamidine, NPh:CMe*NHPh.Bromovinylideneoxanilide is hydrolysed by al- coholic potash to oxanilic acid, aniline, a little oxanilide, and presumably bromacetic acid. c. F. R. Dyeing with (( Substantive" Dyes. By LBO VIGNON (Compt. rend., 1897, 125, 357-360).-As the result of various experiments, the author arrives a t the following conclusions. The fixation of sub- stantive dyes (for example, congo-red) on cotton is a chemical process, since the chemical composition of the dyes influences the fixation t o a remarkable degree. Diamines (with the exception of orthophenylene- diamine) and hydrazines are readily fixed, even when the amido-groups are substituted. Diphenyl, azobenzene, ammonia, hydroxylamine, and aromatic amines are not fixed.The dyeing of cotton is due to the presence of the group =N*R*N= or simply =N*N= ; it is probable that the fixing of the dye is due to the conversion of triad nitrogen into pentad, by the addition of cellulose molecules. This conclusion is supported by the fact that benzidene and tetramethyl- benzidene, in both of which nitrogen is tervalent, can be fixed. But tetrnmethylbenzidene dimet hyliodide, C,N,,(NMe,I),, in which nitrogen is quinquevalent, can not. Some Organic Compounds containing Inorganic Radicles. By C. A. AUGUST MICHAELIS (Ber., 1897, 30, 2821-2822. Compare the following abstracts).-The radicles SeC1, and TeCl, can readily be introduced into various classes of organic compounds, the derivatives of the ketones, such as (l-"h*CO*CH2),SeCI, being of special interest.It is worthy of remark that the compounds of bismuth in which the metal is quinquevalent are more stable than those in which it is ter- vnlent. A. H. By C. A. AUGUST MICHAELIS and FRANZ KUNCKELL (Bey., 1897, 30, 2823-2828. Compare the foregoing abstract, and Abstr., 1895, i, 341).-SelenonaphthyZ methyl ethev, (MeO-C,,H,),Se, obtained by adding selenyl chloride to an ethereal solution of a-naphthyl methyl ether, forms a crystalline mass melting a t 138". The corresponding @-compound crystallises in needles, melting at 162". Seleno-a-nchphthyl ethyl ether forms small, lemon-yellow needles, melting a t 1 4 9 O , whilst the @-compound crystallises in pure white needles, and melts a t 176".Selenyl chloride also reacts with phenols to form similar compounds. Selenophenol, Se(C6H4* OH),, forms a brittle, yellow mass soluble in alkalis. XeZeno-P-naphthol crystallises in small plates, which have a reddish lustre and melt a t 186". Xelenylyesowinol, SeO[C,H,(OH),],, has only been obtained in the form of a reddish-brown, brittle mass, which melts between 170" and 173". Selenium tetrachloride readily reacts with ketones t o form compounds which still contain 2 atoms of chlorine. DichEcroseZenocccetone J. J. S. Organic Selenium Compounds.ORGANIC CHEMISTRY. 137 ( COMe*CH,),SeCl,, crystallises in white needles, which melt at 82" and emit a vapour which attacks the mucous membrane. It decomposes when kept, and is decomposed by boiling water, with separation of selenium, I)ichZorosekenocLcetol,henone, (COPh* CH,),SeC12, which is much more stable than the acetone derivative, crystallises in white needles; these melt at 122O, and can be preserved without undergoing any alteration. With dilute aqueous soda, this compound yields acetophenone and selenious acid, but when warmed with more concentrated soda, selenium is deposited.With phenylhydrazine, it yields a resinous mass. A. H. Organic Tellurium Compounds. By E. RUST (Bey., 1897, 30, 2 8 2 8-2 8 34, Compare the foregoing abstracts). -Tellurium tetra - chloride crystallises from ether in long yellow needles containing 1 mol. of the solvent. Dicl~ZorotekZuyoccnisoil, (OMe*C,H,),TeCl,, obtained by the action of the tetrachloride on anisoil, crystallises in small, yellow needles melting at 190°.When its solution in hydro- chloric acid is evaporated with platinum chloride, yellowish-brown needles of the pkatinocldoride, (OMe*C,H,),TeCl,,PtCl,, are obtained. Dihydruxytekluroa~~isoik, (OAle* CGH,),Te(OH),, is obtained as an amor- phous, white powder on dissolving the dichloro-compound in dilute aqueous soda and acidifying with acetic acid ; when heated, it decom- poses without melting and dissolves both in acids and alkalis. The oxide, (OMe*C,H,),TeO, appears to be formed when the hydroxide is gently heated, but has not been obtained pure. ~ibi*onzotelkuyoanisoik, (O~fe*C,H,),TeBr,, prepared by dissolving the hydroxide in hydro- bromic acid, crystallises in yellow needles, and melts at 183.5'. ~~-~odotekkuro~~n~so~k, crystallises in reddish-brown, lustrous plates, melting at 1 70°, whilst the nitrate forms colourless, compact crystals melting a t 127-1 2S0, and is soluble in water.Dicl~loi.otelZuro~he,.letoik, (OEt*C,H,),TeCl,,. crystallises in yellow needles, which melt a t 1 S5". The cdihydroxy-derivative is an amorphous, white powder ; the dibromo- derivative crystallises in yellow needles melting a t 183". The nitrute crystallises in colourless plates, and melts a t 120". Tellurium tetra- chloride combines with phenol in ethereal solution to form an additive compound, TeCl4,2PhOH ; this is a yellow, crystalline mass, which becomes brown at 182-183". When the tetrachloride is heated with phenol, hydrogen chloride is evolved, but tellurium separates out. No crystalline products could be obtained by the action of the tetrachloride on naphthol, but with resorcinol, reaction takes place, and dichloyotel- Euroresorcinol, [cGH,(OH),],TeCl,, is produced ; this forms small, yellow crystals melting at 188-1 89".The corresponding dihydroxy-compound is a white, amorphous powder. Like the corresponding selenium compound, tellurium tetrachloride readily reacts with ketones. BichZovo- tek~u~oacetopltenone, (COPh*CH,),TeCl,, crystallises in slender, yellowish- white needles, which melt at 186-187" ; potassium permanganate converts it into tellurous acid and chloracetophenone. The tetra- chloride does not react with bromacetophenone. I)icl~korotelZu~op~~g- m k y k methyl ketone, (ORSe*C,H,* CO*CH,),TeCl,, crystallises in small, white needles melting at 1 goo.Dic~lorotelEuro~cc?.ato~~~ metJ$ ketone forms small, white needles melting and becoming green a t 200'. A. IX,138 ABSTRACTS OF CHEMICAL PAPERS. Antimony Derivatives of Anisoil and Phenetoil. By CARL LijLOFF (Bey., 189 7,30,2 8 34-2843).-TrianispZstibine, (OMe*C,H,),S b, may be prepared by the action of sodium on a mixture of bromanis- oil and antimony trichloride dissolved in benzene, or by the action of brornanisoil on a n alloy of antimony and sodium. I t crystallises in well-developed, colourless rhombohedra melting at lS0*5-1S1° ; hot concentrated hydrochloric acid converts i t into anisoil and antimony trichloride. Alcoholic mercuric chloride added to its solution in chloroform, produces a white, crystalline precipitate of the compound, (OMe*C,H,),Sb,HgCl,, which decomposes without melting at 385'; when this is boiled with alcohol, i t yields paranisylmercuric chloride, HgCl*C,H,* OMe (Michaelis and Rabinerson, Abstr., lS90, 1269).I'rianisylstibine dichloride, (OMe*C6H,),SbCl,, is formed when alcoholic cupric chloride is added to a chloroform solution of the stibine, cuprous chloride being also formed. It crystallises from benzene in large prisms with 1 mol. of the solvent; these melt at 82-83', whilst the pure substance melts at 11 6-1 17". Frianisylstibine dibromide, (OMe*C,H,),SbBr,, formed by the direct union of the stibine with bromine, crystallises in thin plates melting at 123" ; it also separates from benzene in prisms containing 1 rnol. of the solvent and melting at 81-82". The di-iodide forms yellow, monosymmetric plates, which me1 t at 11 6' ; the nitvate, which can be prepared by the action of silver nitrate on the bromide in alcoholic solution, cry stallises in short, slender needles, which melt and decompose at 217'.Trianisylstibine oxide, (OMe*C,H,),SbO, ob- tained by the action of alkalis on the halogen conipounds, forms crystal- line crusts melting at 191O; acids convert it into the salts described above. Chlorine acts energetically on the stibine, resinous products being formed. When the chlorination is effected in a well-cooled chloroform solution, however, cZicl~lo?.anis?/lstibine t~ichloride, (OMe* C,H,C1,),SbC13, is produced, which forms colourless crystals melting at 184'; tri- chloranisoil, [OMe :,CIS = 1 : 2 : 4 : 61, is also produced in the reaction.Dichloranisylstibic mid, ( Ollle*CGH,C1,),SbO~OH, formed by the action of water on the foregoing compound, is a white, amorphous powder which melts and decomposes at 228-229", and is insoluble in water and alcohol, but dissolves in aqueous soda and in alcoholic hydrogen chloride. Trip?tenetyZstibine, (OE t*C,H,)3Sb, crystallises in nodular aggregates of needles melting at 82-83", and is decomposed by hydrochloric acid into phenetoil and antimony trichloride. The mercurochloride, (OEt*C,H,),Sb,HgCI,, is a white, crystalline, insoluble powder which decomposes at 225'. Parat?.i~iie~c?elylstibins dichloricle crystallises with difficulty and melts a t 84O; the dibromide crystallises in slender, asbestos-like needles melting at 1 1O-11lo ; the di-iodide in prisms melting a t 121-1 22", whilst the nitrate separates in crystalline crusts which melt at 151-152'.The corresponding oxide could not be obtained. Chlorine produces a mixture of chlorinated diphenetylstibine chlorides, which are decomposed by water. A. H. Some Aromatic Bismuth Compounds. By ARNOLD GILLJIEISTER (Ber., 1897, 30, 2843-2850. Compare the foregoing abstractb).- Bismuthtriphenyl does not appear t o form a di-iodide, since when it isORGANIC CHEMISTRY. 139 acted on by iodiue, o r when tlie chloride is treated with potassium iodide, bismuthodiphemjl iodide, Ph,BiI, is produced ; this crystallises in yellow needles melting at 133O, and is decomposed by alcohol, bismuth- oxyiodide being formed. Bismuthotriphenyl is completely decomposed by a mixture of nitric and sulphuric acids, whereas the dichloride and the nitrate can readily be nitrated, Bismuthodinitrotriphenyl dinitrate, (NO,.C6H4),PhBi(N0,),, obtained by the action of nitric and sulphuric acids on the nitrate, crystallises in flat, lustrous, yellowish prisms, which explode feebly a t about 150O. The corresponding dichloride is precipitated when hydrochloric acid is added t o a solution of the nitrate in acetic acid ; i t crystallises in slender, white needles which melt at 136O, and detonate slightly when rapidly heated. Ortho- bisnzuthotritolyl, Bi( C,H,Me),, obtained by the action of orthobromo- toluene on an alloy of bismuth with sodium, crystallises in colourless rhombohedra, which are isogonous with those of calc spar and melt at 128.5" ; it is decomposed by hot conceiitrated hydrochloric acid, toluene being formed.The dichloride, (C,H,Me),BiCl,, formed by the direct combination of bismuthotritolyl with chlorine, forms white, rhombic crystals melting a t 160". The dibvomide crystallises in yellow needles which melt a t 125", and gradually decompose on exposure t o the air. The nitvate also forms rhombic crystals, and decomposes suddenly when heated. Parabismu8thotrixylyl, ( C,H,Me2),Bi, forms snow-whi te, matted needles which melt at 194.5' and are decomposed when heated with hydrochloric acid ; the dichloride melts at 367.5' and the dibromide at 130O. Parabismuthotricumyl forms lustrous, rhombohedra1 tablets melting at 159O;- the dichloyide melts a t 208", and the dibromide a t 150'. Pseudocumene and mesitylene derivatives could not be obtained.Parabismuthotrianisyl, (OMe*C,H,),Bi, was obtained in small quantity from bromanisoil in the usual way. It forms lustrous cubes, melts at 190°, and is at once decomposed in the cold by hydrochloric acid. This compound is accompanied by paradianisyl, ( OMe*C6H4)2, which crystal- lises in colourless, lustrous plates melting a t 172", and readily sublimes. Hydriodic acid converts it into paradiphenol. Bismuthotrianisyl di- bromide crystallises in yellow needles melting at 103", and is very stable. Chlorine converts the trianisyl compound into bismuthotri- cldoyanisyl dichloride, (OMe*C,H,Cl),BiCl,, which melts a t 133". Para- bismuthotq*iphenetyl forms monosymmetric prisms melting at 73". No halogen derivatives could be obtained.A. H. Halogen Derivatives of Phenyl Methyl Ketone. By A. COLLET (Compt. rend., 1897, 125, 717-719).-Chloracetic chloride and brom- acetic chloride in presence of aluminium chloride and carbon bisulphide act readily on chlorobenzezie and bromobenzene, yielding dichloro-, dibromo-, or chlorobromo-derivatives of phenyl methyl ketone, Para- chlorophenyl chloromethyl ketone melts at 101-102°. Gautier obtained the same compound by the action of chlorine on parachlorophenyl methyl ketone. Parabromophenyl chloromethyl &tone melts at 116-1 17" ; parachlorophenyl byomomethyl ketone at 96-96 *5O ; and puvabrornophenyl bromomethyl Feetone at 109-1 09.5'. All these derivatives crystallise in slender, colourless needles and140 ABSTRACTS OF CHEMICAL PAPERS, dissolve in alcohol, especially on heating, When oxidised, the acetyl group is removed and parachloro- or parabromo-benzoic acid is obtained.Ethylic Quinoltetracarboxylic Acid from E thylic Acetone- dioarboxylic Acid. By HANS VON PECHMANN and LUDWIG WOLMAN (Bey., 1897, 30, 2569--2571).-After ethylic diacetylsuccinic acid had been synthesised by the action of iodine on the sodium compound of ethylic acetoacetate, a similar experiment was tried with the disodium compound of ethylic acetonedicarboxylate, and it was found that, under the conditions of experiment, 2 mols. of the disodium compound condensed, forming 4 mols. of sodium iodide and the corresponding diketohexamethylene compound. The latter, however, is oxidised a t the moment of its formation by the free iodine present, and converted into et hylic quinoltetracarboxylic acid melting a t 133 -1 33 5".C. H. B. J. F. T. Decomposition of Alkyl-sulphonates by Water, Acids, and Salts. By J. H. KASTLE, PAUL MURRILL, and Jos. C. FRAZER (Amer. Chem. J., 1897,%C),894--001).-1n continuation of Kastle and Murrill's previous work on the saponification of alkyl sulphonates by alcohols (Abstr., 1895, i, 370), the authors have determined the velocity of the decomposition of ethylic parabromobenzenesulphonste by water, alcohol, acids, and salts. I n the case of water and aqueous solutions, complete mixture was effected by adding acetone. The progress of the action was deiermined from time to time by titrating with standard alkali, and in the case of the halogen acids and salts it was found necessary also to estimate the quantity of halogen which had not entered into reaction, by means of silver nitrate, since not .only is the sulphonate de- composed by the water, but ethylic haloid is also formed.A. S. Loevenhart has obtained ethylic iodide in quantity by the action of potassium iodide on ethylic parabromobenzenesulphonate in solution in alcohol or acetone, The velocity of the action in the case of water was found to be 3.5 times as great as for ethylic alcohol, whilst acids and salts were found to react much more rapidly than water alone, Rise of temperature causes a great increase in the velocity of decomposition, hydrochloric acid, for instance, at 98' effects as much decomposition in 20 minutes as it does in 10 days at the ordinary temperature.I n some cases, the distribution of decomposition between the acid and the water was independent of temperature ; with hydrochloric acid a t the ordinary temperature, 72 per cent. of the sulphonate was decoinposed by the acid and 16 per cent. by the water, whilst at 98O, 71 per cent. was de- composed by the acid and 16 by the water. Hydrochloric, hydro- bromic, and hydriodic acid bring about the same amount of decomposi- tion, and this is the case also with magnesium chloride and calcium chloride. E. W, W. By OSCAR HINSBERG (Ber., 1897, 30, 2803-2S05).-Benzenesulphinic acid (which has al- ready been shown to unite mith substances of quinonoid structure, form- ing sulphones ; Abstr., 1896, i, 684) unites also with tetramethyldi- Benzenesulphinic Acid as a Reagent.ORGAN 1C C H E iCl ISTRY.141 amidobenzhydrol in dilute hydrochloric acid solution (when the latter substance must be formulated NMe,* C6H4* CH: C6H4:NMe,Cl), yield- ing an additive compound, presumably NMe,* C6H,* CH,* C,H,(NMe,) *SO,Ph. This melts at 194", is stable to acids and alkalis, and is oxidised by potassium permanganate and dilute sulphuric acid to a ketone that contains sulphur, presumably NMe,* C6H,* CO*C6H,(NMe2)*S0,H. C. F. B. Paratoluenesulphinic Acid. By F. ARTHUR H~LSSIG (J. pr. chenz., 1897,56, 213-241. Compare next abstract, and Abstr., 1896, i, 684). -When ammonia is passed into a solution of paratoluenesulphinic acid in alcoholic or ethereal solution, the ammonium salt of the acid is obtained, which crystallises from alcohol in colourless needles melting and decomposing at 175".If the reaction takes place in benzene solu- tion, the ammonium salt of paratoluenesulphonic acid and paratoluene- disulphoxide are formed. Presumably, the ammonia acts first as a re- ducing agent, whereby 2 molecules of the sulphinic acid each give up a hydrogen and an oxygen atom, and the two SO groups become changed to SO,*S, a third molecule becoming oxidised to the sulphonic acid. Aromatic amines react with paratoluenesulphinic acid, giving salts which, when strongly heated, yield blue to red violet resins, from which the colouring matters could not be isolated. The aniline salt crystal- lises in colourless needles melting a t 118' ; the orthotolwidine salt in colourless needles melting at 124" ; theparatoluidine salt in needles melt- ing a t 140°, and the metaxglidene salt'in white needles melting a t 129.5'.With phenylhgdraxine, a salt is obtained as colourless, asbestos-like needles melting at 159-160" with decomposition j and with hyd~axine hydrate, a salt as glistening leaflets melting partially at 107", and de- composing entirely a t 140". ~heny~arato~uenesu~p~~c6x~de, C,H,Me*SO,*NH*NHPh, is prepared by the action of phenylhydrazine on paratoluenesulphonic chloride ; it crys- tallisesfromalcohol in beautiful needles melting and decomposing at 155'. When treated with sodium hydroxide, it is converted into benzene, nitrogen, water, and sodium paratoluenesulphinate ; at the same time, a red, crystalline substance melting at 65" is obtained, but in quantity too small for further investigation.The same sulphazide is also produced together with parcttoluenedisulphoxide when paratoluenesulphinic acid is acted on with phenylhydrazine hydrochloride. By the action of hydrazine hydrochloride on paratoluenesulphinic acid, paratoluenedisulphoxide is obtained, together with a substance crystallising from alcohol in clear needles and melting at 1 8 0 . 5 O with decomposition. Its aqueous solution reacts feebly acid, and reduces ammoniacal silver nitrate a t ordinary temperatures. It yields a benxoyE derivative crystallising from alcohol in needles melting and decompos- ing a t 209.5', but the constitution of this substance has not so far been satisfactorily determined. Phenylmethylhydrazine and paratoluenesul- phinic acid give rise t o a saZt crystallising from :tlcohol in silken needles melting at 126@ ; this, when treatedtvithhydrochloric acid, is transformed into a substance of the composition C,,H,4S,0,N4.Neither by this re-142 ABSTRACTS OF CHEMICAL PAPERS, action nor by the action of phenylrnethylhydrazins on paratoluonesul- phonic chloride could the corresponding sulphazide be obtained. Free hydroxylamine reacts with paratoluenesulphinic acid, giving rise to paratoliienesulphonamide, and the hydroxylamine salt of the acid as an intermediate product. The action with P-dibenzylhgdroxylamine is com- plax; the products are benzaldehyde, paratoluenedisulphoxide, benzyl- isobenzddoxime, parcctoluenesuZp?&ic acid P-benxylhydroxylamine form- ing mother-of-pearl, glistening leaflets melting a t 176O, and the P-dibenxyl- hydroxylanaine salt as small crystals melting a t 156'.By melting acetoxime or a-benzaldoxime with paratoluenesulphinic acid, the ammonium salt of the acid and paratoluenesulphonamideare pro- duced; but if the action take place in acetic acid solution, with acetoxime, paratoluenedisulphoxide and ammonium paratoluenesulphonate are formed, and with benzaldoxime a condensation product insoluble in alcohol, ether, and benzene, and soluble only with decomposition in acetic acid ; it melts at 1 2 4 O , and is converted by dilute alkalis into benzaldehyde, paratoluenesulphonamide, and paratoluenesulphinic acid. A. W. C. Derivatives of Paratoluenesulphinic Acid. By ERNST VON MEYER (J. pr. chem., 1897, 56, 272. Compare preceding abstract, and Abstr., 1896, i, 684)-A preliminary note on the compounds formed by the action of certain diazo-compounds on paratoluenesalphinic acid.The substance, N2Ph* SO2* C,H,Me, forms beautiful, yellow crystals melting a t 94.5'. When acted on by aniline, methyl-, or dimethyl- aniline or quinoline in alcoholic solution, it is converted into a sub- stance of the composition C,oH20Sz04N2, which is probably diparatolyl- suZphone phenylhydraxine ; this forms white needles melting a t 198'. A. W. C. A Transformation of Tetrahydropyrone Derivatives. By PAWEL Iw. PETRENKO-KRITSCHENKO and D. PLOTNIKOFF (Ber., 1897, 30, 280 1-2803).-When acetonedicarboxylic acid is mixed with three times the quantity of benzaldehyde, the product shaken withdilutesoda, and the solution, after being freed from excess of benzaldehyde by extrac- tion with ether, is acidified, di~henyZtetrcc~~ydro~~roned~c~rbox~Z~c acid, C O < ~ ~ ' ( ~ ~ ~ { : ~ ~ ~ ~ > O , separates as a semi-solid mass.It gradually loses carbonic anhydride, and the product is diphenyltetra- hydropyone, CO<cHf. cHph>O ; this melts a t 131'. When its CH *CHPh alcoholic solution is warmed with a few drops of hydrochloric acid, dibenzylideneacetone, CO(CH: CHPh),, is formed. Action of Tetrazodiphenyl Chloride on Benzene, By E. CASTELLANETA (Ber., 1897,30,27 99-280 I).-Tetrazodiphenyl chloride, ~l.N,*C,H,*C,H,*N,*Cl, is prepared by dissolving benzidine in absolute alcohol, passing in gaseous hydrogen chloride, adding a-mylic nitrite a t 5", and then ether; it explodes at 106--1OSO or when struck, and keeps well in the dry state.When it is heated on the water bath with excess of benzene and a little aluminium chloride, i t yields a mixture of payachloropuradip?Lenylbenxene, C,H4C1* C,H,Ph, melting at 220--220*5O, with paradichlorodiphenyl, C6H,C1* C,H,Cl, the latter of C. F. B.ORGANIC CHEMISTRY. 143 which is rather niore soluble in alcohol than the first ; no biphenyl- diphenyl, C,H,Ph* C,H,Ph, is formed. Aromatic Hydroxyketones. By EMILIO NOELTING and ALFRED MEYER (Ber., 1897, 30, 2590-2595).-2 : 3 : 4 : 3' : 4'-Pentahyclroxy- benxopheno?ze, C,H,(OH),* CO*C,H,(OH), obtained by heating proto- catechuic acid with pyrogallol and zinc chloride a t 140-145", crystallises with 2H20 in slender, light yellow needles, and melts when dry a t 192-193".Concentrated sulphuric acid converts it into protocatechuic acid and decomposition products of pyrogallol. An isomeyic compound, [(OH), = 3 : 4 : 5 : 3' : 4'1, is produced when gallic acid is heated with catechol and zinc chloride ; it also crystallises in light, yellow needles with 2H20, but melts a t 266" ; like its isomer- ide, i t yields protocatechuic acid when heated with sulphuric acid. This reaction shows the constitution of the two compounds. 2 : 4 : 3' : 4'-Tetrah~droxybenzop?~enone, CO[C,H3(0H),],, obtained from protocatechuic acid and resorcino1,forms brownish-yellow crystals contain- ing 2H20, and melts a t 199". 2 : 3 : 4-Trihyhoxyp?~enyl3-~~yclroxy-/3-naph- thyl ketone, OH* G,,H6- CO*C,H,(OH):,, is prepared from /3-hydroxy- naphthoic acid and pyrogallol ; it forms small, yellow crystals melting at 287-289". When heated with resorcinol and zinc chloride, /3-hydroxynaphthoic acid yields a substance which is probably a mix- ture of the ketone with hydroxyxanthone formed from it by loss of water.Pentahydroxy- and tetrahydroxy-benzophenone have been previously described in the German Patent No. 72446, belonging to the Hochst company. A. H. New Method of obtaining Colouring Matters of the Malachite-Green Series. By EMILIO NOELTING (Bey., 1897, 30, 2588-2590).-Benzanilide and i t s derivatives usually react with ter- tiary aromatic amines in presence of phosphorus oxychloride to form derivatives of dialkylamidobenzophenones. (German Patent, 41 751). When, however, a hydroxy-group is present in the ortho-position in the benzoic acid residue the reaction takes another course, and a com- pound of the malachite-green series is produced.Thus salicylanilide and dimethylmiline react t o form a green colouriny matter which on reduction yields the leuco-base obtained by 0. Fischer from salicyl- aldehyde and dimethylaniline (Abstr., 1882, 392). Orthocresotic ani- lide yields a similar cornpound, whereas the anilides of meta- and para- hydroxy benzoic acid and of orthonitro- and orthamido-benzoic acid yield no compound of this class. A green colouring matter is also formed from the anilide of orthohydroxynaphthoic acid. By CHRISTOPH RIS and CARL SIMON (Ber., 1897,30, 261 8--2620).-Sodium paradinitrodibenzyl- disulphonate can readily be prepared by the action of aqueous soda and sodium hypochlorite on sodium paranitrotolueoeorthosulphonate ; it crystallises in colourless needles, and deflagrates a t a high tempera- ture.Alkalis convert it into yellow substances, and it appears probable that the yellow substance described by Bender (Abstr., 1895, i, 287) as potassium paradinitrodibenzyldisuIphonate is in reality such a decomposition product. A. H. C. F. B. A. H. Paradinitrodibenzyldisulphonic Acid.144 ABSTRACTS OF CHEMICAL PAPERS. Anilineazo-a-Naphthol. By OTTO N. WITT and JENS DEUICHEN (Ber., 1897, 30, 2655-2667. Compare Abstr., 1894, i, 606).-In many respects the behaviour of anilineazo-a-naphthol is inconsistent with the view that it is the exact analogue of hydroxyazobenzene. I t s resistance to ordinary methods of alkylating phenols, for instance, and the pronounced basic character of the colouring matter and its ethers, serve to differentiate it from the type in question.The general method of preparing azo-colouring matters is not the most suitable for the production of anilineazo-a-naphthol, as the unmodified process gives rise also to a disazo-compound; this bye-product is not formed, however, if the operation is carried out in alcoholic solution. An ice-cold solution of diazobenzene chloride, prepared from 93 grams of aniline dissolved in 200 C.C. of concentrated hydrochloric acid and 250 C.C. of water, is added to a cooled solution of 155 grams of a-naph- tho1 in 2000 C.C. of alcohol, anilineazo-a-naphthol hydrochloride being slowly deposited from the liquid; the azo-compound is obtained by dis- solving the hydroch1oride:along with potassium acetate in boiling glacial acetic acid, from which it separates in reddish-brown crystals with green reflex. The potassium derivative forms large, red- dish-brown crystals, with feeble metallic lustre.The conq2ound, C32H22N402, arising from elimination of two hydrogen atoms from 2 molecules of snilineazo-a-naphthol, is prepared by the action of oxidising agents such as ferric chloride and potassium dichro- mate, which when added to a solution of the potassium derivative, pre- cipitate a mixture of unaltered colouring matter and the product of its oxidation ; it is also obtained by the action of nitrosodimethylaniline, and by protracted treatment with boiling glacial acetic acid, in which it is insoluble.(Compare Fischer and Hepp, Abstr., 1892, 1476.) The substance forms deep red crystals, and melts and decomposes a t 245-246' ; i t is insoluble in ordinary media, and is devoid of basic properties. The solution in cold concentrated sulphuric acid is violet,. The acetyl derivative crystallises from toluene in lustrous, orange-red, dichroic needles, and melts a t 264-265O. When the oxidation product from anilineazo-a-naphthol is reduced with tin and hydrochloric acid, diparamidonaphthol is produced, and when the hydrochloride of this base is oxidised with concentrated nitric acid, dinaphthupwinone, C20Hlo04, is obtained ; it begins to decompose at 270°, and yields P-dinaphthyl when heated with zinc dust. The com- pound obtained by oxidising anilineazo-a-naphthol, therefore, has the constitution NPh :N* C,,H,(OH)*C,,H,(OH) *N:NPh.It has been already stated that the new colouring matter forms a violet solution in concentrated sulphuric acid. If the liquid is gently heated i t becomes blue, and when poured into water yields a dark brown precipitate, which becomes orange on treatment with soda; the con&- pound, C,,H20N40, obtained by this method is purified by precipitating its solution in phenol with alcohol, and subsequently crystallising from boiling xylene. It forms lustrous, orange-red crystals, and melts at 290--291", when decomposition begins ; the substance is insoluble in dilute acids mid alkalis, and the solution in concentrated sulphuric acid is blue. Reduction converts i t into the cryst'alline Iiydrochloride It melts a t 206'.of a new compound. M. 0. P.ORCANTC CHEMISTRY, 145 A General Reaction of Aromatic Quinones. 11. By SIEGFRIED BLUMENFELD and PAUL FRIEDLANDER (Bev., 1897, 30, 2563-2568. Compare Abstr., 1897, i, 473).-There are only two possible ways of formulating a substance formed by the condensation of a quinone with a phenol without elimination of water, for either the product is a hydroxy-derivative of a hydrocarbon, or the two rings are joined by means of oxygen, thus forming a hydroxy-derivative of an ether ; for instance, the product of condensation of a-naphthaquinone with pyro- gallol may be either a pentahydroxyphenylnaphthalene or a tetra- hydroxyphenyl naphthyl ether. Since, on investigation, this compound was found to yield a tetracetyl derivative, the latter formula is evi- dently the correct one.2 : 3-Dihydroxyphenyl l : 4-dihydroxy-2-maphthyl ether, C,,H,(OH),* O*CGH,(OH),, formed by the condensation of a-naph- thaquinone with pyrogallol in glacial acetic acid solution, crystallises from the latter in pale grey needles melting and decomposing at 240-246', the tetracetyl derivative crystallises from glacial acetic acid in colourless needles melting at 165-1 70°, whilst the benxoyl derivative forms white needles melting at 203-205'. Dihydroxydi-a-naphthyl ether, CloN5(OH),~0*CloH7 [(OH), : 0 = 1 : 4 : 21, formed by the condensation of a-naphthaquinone with a-naphthol, crystallises in colourless needles melting at 240--245O, the. diucetyl derivative crystallises from glacial acetic acid and softens a t 240°, remaining, however, solid at 300'. P-Naphthaquinone, on condensation with pyrogallol, yields 2 : 3-di- hydroxyphenyl 1 : ~-diT~ydroxynap?~thyl ethel; C,,H,(OH),*O*C,H,(OH)~, which, after recrystallisation, melts a t 242--245', and the tetracetyl derivative at 184-1 SS0 ; with a-naphthol, P-naphthaquinone yields 1 : 2-dihydroxydinaphthyl ether, C,oH,(OH),*O*C,,H7, which does not show a sharp melting point the dzacetyl derivative melts at 220'.P-Naphthaquinone and resorcinol produces 3-hydroxyphenyl 1 : 2-di- hydroxynaphthyl ether, Cl0.H5(OH),* O-C,H,*OH ; this separates from its glacial acetic acid solution on dilution with water and melts at 236-240'. The triacetyE derivative melts at 169-1'70'. Benzoquinone combines with a-naphthol and resorcinol, forming in the first case trihydroxydiphenyl ether, C,H,(OH),* O*C,H,(OH) [(OH), : 0 : OH = 1 : 4 : 1' : 3'1, which crystallises with difficulty and yields a benxoyl compound which separates from alcohol in white needles me1 ting at 188-1 9 1'.J. F. T. Isomeric Change of Dihydrocarvone into Carvenone. By IWAN L. KONDAKOFF and TH. GORBUNOFF (J. pr. chem., 1897, 56, 248-257).-When a solution of As,,-dihydrocarvone in light petrol- eum is saturated with hydrogen bromide, the former substance is converted into carvenone. During the reaction a small amount of a bromo-derivative is formed, which, on treatment with zinc dust, is com- pletely converted into the same carvenone, boiling at 232-233' at 758 mm. It has a sp. gr.=0*921 at 2Oo/2O0, and a refractive index n, = 1,47664 a t 20°, corresponding with a molecular refractive index of 46.63 (calculated 46.76).Dihydrocarvone takes up the elements of hydrogen chloride when treated with the latter in acetic acid sclution. The chloroketone formed boils a t 155.5-157' at 15 mm. ; has R sp. gr. = 1,0266 at 2Oo/2O0; a146 ABSTRACTS OF CHEMICAL PAPERS. refractive index n, = 1,47877, and is lsvorot,atory ; aD = - 11.72. When heated on the water bath for 2 hours with alcoholic soda, i t loses completely the elements of hydrogen chloride, yielding carone boiling at 101-102' at 15 mm. It has a sp. gr. =0*9575 a t 21'121" ; a refractive index 12D = 1.47664, and is dextrorotatory ; aD = + 174.36". It is readily oxidised on treatment with potassium permanganate.The investigation is proceeding. a. w. c. Menthonecarboxylic Acid and Menthonedicarboxylic Acid. By GIUSEPPE ODDO (Gaxxetta, 1897,27, ii, 97-1 16).-On treating men- thone in absolute ethereal solution with sodium wire, a large part of the metal is rapidly dissolved, whilst the remainder only dissolves on pro- longed ebullition ; 1 atom of sodium requires 1s molecules of meuthone for its solution. The liquid is saturated with carbonic anhydride, cooled with powdered ice, and the two layers separated ; the ethereal solution, besides menthol and menthone, contains Beckmann's men thopinacone (Abstr., 1897, i, 248). On acidification with hydrochloric acid, the aqueous layer deposits an oil which can be extracted with ether; the ethereal solution, on evaporation, yields a mixture from which light petroleum extracts menthonecarboxylic acid, and leaves Briihl's menthonedicarb- oxylic acid (Abstr., 1892, 200).The petroleom extract is washed with sodium carbonate solution, and the latter acidified and extracted with ether ; on evaporating this ethereal solution, menthonemonocarboxylic acid is obtained. Menthonecu~boxylc acid, FH2* CHMe* FH' 'OH, is a heavy, colour- CH; CHPr CO less, nearly odourless oil, which ;ields menthone when heated with dilute sulphizric acid; it is sparingly soluble in water, and its solution turns violet with ferric chloride. The silver salt, CloH170*COOAg, is a floccu- lent, white precipitate. On treating the acid with sodium nitrite and acid a t ordinary temperatures, isonitrosomenthone, CH,* I CHMe* ?:NOH CH; CHPr* CO ' is obtained, together with a reddish oil insoluble i: alkalis, which is 7H2* CHMe* 70 .iso- probably an orthodiketone of the constitution CH; C HPr co ' nitrosomenthone is a n oil which gives a yellow sdution in alkalis. On reduction with zinc dust and acetic acid in dilute alcoholic solu- tion, it yields menthoneamine, YH2' CHMe* ?H*NH2, as an oil smelling CH9* CHPr CO like camphoramine ; the hydrochhride crystallises in colourless prisms melting at 181-183", and the platinochlovide in red prisms which melt and decompose a t 175-180" ; apparently it yields thymol on heating. Menthonedicarboxylic acid, which has the constitution CH, . CHMe-$lH* COOH bH,* CPr(COOH)* CO 7H2* CHMe- ?(C OOH), or CH,. CHPr CO 9 melts at 140-141' with decomposition, not a t 128-5O, as stated by Briihl (Zoc.cit.) ; when treated with diazobenzene chloride, it yields a compound which crystallises in dark-red crystals melting a t 126-128O. W. J. P.ORGANIC CHEMISTRY. 147 Borneols and their Ethers. By JULES MINGUIN (Compt. Tend., 1896,123, 1296--1298).-A method is described for separating dextro- borneol from lzevoisoborneol in the mixture obtained by the reduction of camphor. The author is of opinion that the phenomenon observed by Mont- golfier on the etherification of a mixture of dsxtroborneol and laevo- isoborneol, and on subsequent hydrolysis, nbmely, an increase in the dextrorotatory power, is not due to a partial conversion of the Z-iso- borneol into d-borneol, but is due to the fact that borneol is more readily etherified than isoborneol.Camphoquinone. By OTTO MANASSE and ERNST SAMUEL (Bey., 1897, 30, 3157-3161. Compare Abstr., 1897, i, 290j.-The acid CloH160, is obtained by dissolving finely-powdered camphoquinone in 15 parts of concentrated sulphuric acid, which is cooled and agitated during the process ; after a short interval, the new substance is pre- cipitated by pouring the liquid on toice. It dissolves with great difficulty in cold water, but is soluble in 20 parts a t 60', separating from the solution in slender needles melting at 67-68'; it contains 1H20, which is removed in the desiccator or on exposure to a temperature of 50', the anhydrous acid, which is very hygroscopic, melting a t 97-98". The acid is readiiy soluble in common organic solvents, excepting petroleum, from which i t crystallises in long, slender needles melting at 97-98'; it is monobasic in character, and exhibits the properties of an aldehyde or ketone, producing a metallic mirror when boiled with water and silver oxide, and developing a reddish-violet coloration with a sulphurous acid solution cf magenta.It is somewhat stable towards potassium permanganate, and resists the action of boiling 50 per cent, sulphuric acid, but is readily oxidised by a solution of bromine in caustic soda. The oxime crystallises from chloroform in glistening leaflets, and melts a t 163-164'; i t is readily soluble in acids and alkalis, but dissolves with some difficulty in water. The phenylhydraxone crystallises from dilute alcohol, and melts a t 123-124O.The semicarbaxone separates from alcohol as a microcrystalline powder and melts at 217-218'; it dissolves readily in sodium carbonate, and the alcoholic solution reddens litmus. When camphoquinone is exposed to the vapour of bromine, it is converted into the compound, C,oH,,Br303, which crystallises from benzene in lustrous prisms and melts a t 197-198'. If bromination is carried out by adding bromine to the quinone until: action ceases, and heating the product on the water bath, the compound, CloH,2Br203, is produced; this, which crystallises from alcohol in long, lustrous needles, and melts at 137-138', is not identical with z-dibromo- camphoric anhydride. M. 0. F. Camphor Compounds. By GIUSEPPE ODDO (Gaxxetta;, 1897, 27, ii, 117--131).--0n heating camphoquinone with hydrazine hydro- chloride in acetic acid solution, biscamDhanonaxine, J.J. S. is obtained ; it crystallises in colourless scales melting at 217-218",145 ABSTRACTS OF CHEMICAL PAPERS, is hydrolysed by fuming hydrochloric acid, and is ident'ical with Angeli's azocamphanone (Abstr., 1895, i, 61). Camphoquinone and hydriodic acid do not react in presence of red phosphorus at 115-125', but at 150' the quinone is wholly converted into camphoric acid. Bromocamphocarboxylic acid does not react with nitrous acid, but, under similar conditions, camphocarboxylic acid yields isonitroso- camphor (Abstr., 1893, i, 422) ; the bromo-acid should therefore contain the group -CBr(COOH)* CO- and its ready conversion into bromocamphoric acid indicates that the bromine is attached to the same carbon atom in both acids.a-Dibromocsmphor is converted by sodium in boiling ethereal solu- tion into monobromocamphor and a dibromodisumphoi-, C,,H,,Br,O, ; the latter crystallises in thin, white needles melting a t 128-129', and slowly decomposes with evolution of hydrogen bromide. Under similar conditions, P-dibromocamphor loses both bromine atoms, yield- ing a substance not yet examined. I n connection with the recent sitting of the Brunswick Natuil- forscherversammZung respecting the constitution of camphor, the author concludes that it is not yet possible to definitely state the constitution of this substance. Conversion of Sulphocamphophenol into Dinitrocresol. By PAUL CAZENEUVE (Compt. rend,, 1896, 123, 1293-1 295)-The com- pound previously obtained by the action of cold fuming nitric acid on the two sulphonated camphophenols and described as a tetranitro- derivative, C,H,O(NO,),(SO,)(OH), (Abstr., 1890, 1153), is now proved to be the dinitro-orthocresol [Me : OH : (NO,), = 1 : 2 : 3 : 51 pre- viously obtained by Nevile and Winther (Trans., 1880, 631).W. J. P. J. J. S. Asymmetrical Alkylphenylhydrazines md some of their Derivatives. By C. A. AUGUST MICHAELIS (Ber., 1897, 30, 2809-2821. Compare Bei-., 20, 2485).-The hydrochlorides of the asymmetrical alkylphenylhydrazines can readily be freed from phenyl- hydrazine hydrochloride by recrystallisation from chloroform or benzene, in which the latter is either insoluble or only sparingly soluble. [With G. Ro~~s~~.]--a-YhenyZethylhydraxirze, NH,*NEtPh.-This is best prepared by the action of ethylic iodide on sodium phenylhydr- azine (Abstr., 1889, 1158).It boils a t 237' (corr.) and has a sp. gr.=1.018 a t 15'. It readily reacts with pyruvic acjd to form a derivative which on heating with hydrochloric acid at 60' yields ethylindolecarboxylic acid (E. Fischer and 0. Hess, Bev., 17, 565). When this acid is heated a t 190-195', carbonic anhydride is evolved and l'-ethylindoZe, C,H,<:g>CH, produced ; the latter boils at 252-253' (corr.) and has a sp. gr. =1*2563 at 15O. Its picrate crystallises in red needles and melts a t 105'. Dichlorethyloxkdole, C,H4<gE>C0, obtained by the action of sodium hypochlorite on ethylindolecarboxylic acid, crystallises in yellowish prisms meltinga t 56" ; dibromethyloxindole crystallises in yellow prisms melting a t 95-96".Water converts these halogen derivatives into ethyl- $-isatin, whilst aqueous soda yields sodium ethyl-$-isatate, NHEt* CRHd* CO* COONa. - A N-NNEt- Ethyldioxindole, C6H4KCH coH)>CO, which can readily be prepared by the reduction of ethyl-$-isitin, crystallises in colourless prisms which soften at 143O and melt at 154-155'. 1'-Zthyloxindole, C,H4<E::>C0, obtained by the reduction of dibromethyloxindole, crystdlises' in needles arid is probably identical with that prepared by Baeyer and Comstock by the ethylation of oxindole (Abstr., 1883, 1130). a-PiLe~~~i.opylh?/drazine, N H2*NPrPh, which boils a t 247' (corr.) and has a sp. gr. = 0.9471, reduces Fehling's solution only very slowly in the cold and has an odour which resembles that of onions.l'-I'ro- pylindolecarboxylic acid, C,H,<ZF>C* COOK, prepared in a similar manner to the ethyl compound, crystallises in white needles which melt a t 170', and then sublime and decompose into carbonic anhydride and 1'-propyzindole ; the latter is a colourless oil, which boils a t 265" (corr.) and has a sp. gr. = 1-0559 a t 15'. Its picrate forms red needles melting a t 67". Dichlol.opropyloxi.li3dole crystallises in yellowish needles melting a t 67" ; the dibromo-derivative forms prisms melting at 97'. 1'-Propyl-$-isatin crystallises in slender, bright-red needles melting at 72". Barium propyl-$-isatate, obtained by the action of baryta water 011 dichloropropyloxindole, crystallises in silky, yellow needles.The p-oxime, C,H,<C(N. - NPr oHi>CO, - melts at 88", and does not yield indigo when treated with ammonium sulphide. Propyldioxindole crystallises in yellow needles melting at 70". Propyloxindole forms colourless crystals melting a t 68-69'; bromine water added to its solution precipitates a bromine compound melting at 125'. [With R . ILMER,] -1soprop y Zpheny l h y draxine , NPh( CHRIe), NHg prepared in a similar manner to the ethyl compound, boils at 236 and has a sp. gr. =0*9588 a t 15'. 1'-lso~.o~ylindoZecccl.boxylic acid melts a t 183", and the correspondirlg indole boils at 250" and forms a picrate which me1 ts a t 7 6O. NPhPr*NH*C6H2( NO&, formed by the action of picrylic chlorlde on isopropylphenylhydrazine in alcoholic solution, crystallises in brownish-red needles melting a t 156". It readily dissolves in aqueous alkalis, but no salts of it could be prepared. It is not acted on by mercuric oxide, and in this respect differs from trinitrophenylhydrazine, which is thereby converted into an azo-compound.Dinitrohydrazoisopropy lbenzene, NPhPr-N H* C,H,(NO,),, obtained by the action of chlorodinitrobenzene on the hydrazine, crystallises in brownish-red needles which are insoluble in aqueous alkalis, a-Yhenylisobutylhydraxine boils a t 245', and has a sp. gr. = 0.9633 at 15". l'-lr,obutylindoEecarboxylic acid crystallises in white, silky needles melting at 152". 1'-Isobutylindole boils at 260', and does Tkirzitroh ydraxoisopropylbenxene, VOL. LXXIV. i. ?? 1150 ABSTRACTS OF CHEMICAL PAPERS, not form a crystallisable compound with picric acid. Trinitrohydr~cxo- isobutylbenxene, C,H,*NPh*NH* C6H2(N0,),, crystallises in red needles, melts a t 105', and dissolves in alkalis; the dinitro-derivative also crystallises in red needles and melts a t 15 lo.a-Phe?zyZ~~oc~~~yZ~y~raxine boils at 262', and has a sp. gr. =0*9680 at 15'. l'-Isoam?/lindolecccrb- oxylic acid melts a t 122', whilst the corresponding indole boils at 376' and does not form a solid picrate. Triniti*ohydraxoisoamylbenxene forms red needles melting a t 58', whilst the dinitro-compound crystal- lises in bright yellow needles, and melts a t 104'. A. H. 4'-Arnidoquinoline. By ADOLPH CLAUS and WALTHER FROBENI US (J. pr. chern., 1897, 56, 181-204. Compare Abstr., 1894, i, 617).- 4'-AmidopuinoZine, prepared by a method already described, melts at 70' after recrystallisation from the ordinary solvents ; it contains 1H20, which it loses at loo', and then melts a t 154'.It is easily soluble in alcohol, but less readily so in ether and benzene. The hydrocidoride crystallises in small, colourless leaflets very readily soluble in water, and remains unchanged when heated to 300'; the plcctinocldo~ide forms orange-colour ed needles containing 2H,O i the nitmte crystallises in small needles which melt at 214' after driving off 1H20 ; and the dichronzate crystallises in bunches of long, orange- red needles which decompose on exposure to air or on heating to 207'. On warming the base with methylic iodide a t a temperature of 50-60°, it is completely transformed into the metlziodide, which crystallises from alcohol in colourless needles melting at 224" ; the ~nethocldoride, prepared by treating the me thiodide with silver chloride, crystallises in colourless needles melting at 310' ; the metho-clichromate crystal- lises in orange-red needles, becoming brown on exposure to air, and melting a t 225O with decomposition, whilst the ethioclide crystallises in colourless needles melting a t 232".When 4-amidoquinoline methiodide is treated with moist silver oxide or concentrated potash, small amounts of the ammonium hydroxide base are formed, and in their behaviour towards these re- agents the quaternary 4'-amidoquinoline compounds take up a position intermediate between the para- and ortho-alkoxyquinoline derivatives. (Compare Claus and Howitz, Abstr., 1891, i, 1252.) 4'-AcetamidopuinoZine, NHAc*C,H,N + H,O, crystallises from water in colourless, glistening needles, melts at 172', and sublimes without decomposition.The methioclide, formed by heating the base with methylic iodide in sealed tubes a t 120', crystallises from alcohol 'in yellow leaflets, becoming black on heating to 250', and melting at 291' with decomposition. Claus and Howitz have already shown that when 4'-amidoquinoline is treated with sodium nitrite in hydrobromic acid solution, no diazo- derivative is obtained, but only 3'-bromo-4'-amidoquinoline, and also, as is now proved, 3'-bromoquinoline melting a t 29-30'. 3'-lodo-4'-amidoquirzolirze, prepared in a similar manner, cry stallises from water in colourless needles containing 1H,O and melting a t 197'.4'-lodopuinoZine is obtained in small quantities when 4-amidoquinoline is diazotised in concentrated sulphuric acid solution and the pro- duct treated with potassium iodide. It is insoluble in cold water,ORGANIC CHEMlSTRY. 151 readily soluble in alcohol and ether, crystallises in colourless needles or prisms melting at 97", and sublimes without decomposition. The plntinochloride crystallises in orange-red needles, decomposing when heated to 185' with elimination of iodine ; and the methiodide separates from water in bunches of reddish-yellow needles which decompose when heated to 251'. By the action of nitric acid alone, 4'-amidoquinoline does not yield a nitro-compound, but the nitro-derivative of kynurine. Nitro-4'- amidoquinoline may, however, be produced by gradually adding 4'-amido- quinoline sulphate t o well cooled fuming nitric acid ; it crystallises from water in long, yellow needles containing lH,O, and decomposes when heated to 207".I n all probability, the nitro-group is in the S'-position of the pyridine ring, as the substance is easily dissolved by alkalis ; the sodium compound forms small, colourless needles. It is very feebly basic, for although the hydrochloride may be obtained as colour- less needles by adding the calculated amount of hydrochloric acid to an alcoholic solution of the base, it is immediately dissociated in presence of water. The plcdinochloride forms orange-red crystals, which decom- pose at 210', and are at once dissociated in presence of water.The nitro-derivative is indifferent towards alkyl halogen compounds and does not form a diazo-compound. Dinitr0-4'-anzidoqz~inoliize, prepared by treating 4'-amidoquinoline with a mixture of nitric and sulphuric acids, crystallises from dilute alcohol in golden-yellow needles which decompose suddenly when heated to 203'. It does not form salts with acids, neither does it com- bine with methylic iodide, or give a diazo-compound. The plcctino- chloiside can be obtained with difliculty, but it dissociates immediately in presence of water. During the nitration, a second substance is formed in small amount crystallising from dilute alcohol, and decomposing at 285". I t s nature and composition will be furt,her investigated, but it appears to be represented by one of the two formulae C1,Hl,N7O7 or C,,H,,N707.A. W. C. 2'-Amidoquinoline. By ADOLPH CLAUS and S. SCHALLER (J. pr. c?mvh., 1897, 56, 204-212. Compare preceding nbstract).-Z'-A),zido- puinoline is prepared by heating 2'-chloroquinoline, ammonium carbonate and ammonium hydroxide in sealed tubes for 6-6 hours at 200-210', and is separated from the carbostyril formed a t the same time by treatment with benzene, in which the latter is insoluble. It crystallises from water in large, colourless or slightly yellow leaflets, melts at 1 2 5 O , is readily soluble in ether, alcohol, and benzene, almost insoluble in chloroform and light petroleum, and sublimes readily in large, glistening, iridescent crystals ; in contact with alkalis, i t is converted into carbostyril. The platinocldoritle forms glistening orange-yellow crystals containing 2H,O ; the nzethiodide crystallises from alcohol in colourless needles and from water in prismatic crystals melting at 245O, and the metlr,ochloride forms silken needles melting a t 265'.The methiodide differs markedly from the corresponding derivative of 4'-amidoquinoline in giving with moist silver oxide a considerable 17L 2152 ABSTRACTS OF CHEMICAL PAPERS, quantity of the quaternary ammonium hydroxide base. This subject will be treated more fully in a subsequent paper. A. W. C. Action of Aromatic Amines on Certain Unsymmetrical Ketonic Compounds. By LOUIS SIMON (Ann. Chinz. Phys., 1896, [vii], 19, 433-536. Compare Abstr., 1893, i, 552; 1894, i, 509; 18115, i, 594, and 1896, i, 85).-Aniline reacts with pyruvic acid in the presence of ether, yielding three products, ( 2 ) anilpyruvic acid NPh:CMe*COOH, (2) 2'-methylquinoline-4'-carboxylic acid (aniluvi- tonic acid), and (3) a colourless, crystalline compound, C17HI,N,0,, melting at 190' and having the composition OH*CHMe*CH,-C( :NPh)*CO*NHPh, or NHPh* CHMe CH,*C1( :NPh) COOH.Other primary aromatic bases react in the same manner. With pyruvic acid, paratoluidine yieldsparcctoZiZ~~ruvic acid melting a t 127O, 3 : 2'-di.nzethyZquinoline-4'-carbox~Zic acid melting a t 265O, and the compound C,,H,,N,O,, forming white crystals and melting a t 238' ; orthotoluidine yields orthotolilpyrzcvic w i d melting at 137', 1 : 2'- dinaet?~yZquinoZine-4'-ca~6ox~Zic acid melting at 252', and the compound CI,H,,N,O, melting a t 232' ; whilst metaxylidine yields metaxylil- pyruvic acid melting at 137-1 38O, a trinzet?~yZquinoZi~~~-4'-cu~boxyZic acid [?Me, = 1 : 3 : 2'1 melting a t 212O, and the compound C,,H2GKi202 melting a t 232'.P-Naphthylnmine in like manner gives P-maaphthi2p~ruvic cccid melting at 132O, a compound melting a t 232', and as Doebner and others have already shown, P-naphthyluvitonic acid. The compounds with aniline have already been prepared by Boettinger, who, however, ascribed somewhat different constitutions to them. The products formed from aniline and the ethereal salts of pyruvic acid have already been described (Abstr., 1896, i, 85). a-Naphthylamine does not react with pyruvic acid. By HERbiANN METZNER (AnszaZen, 1891, 298, 374-390. Compare Schott, Abstr., 1896, i, 'IOO).-Ethylic phenacetylmalonate is converted into benzyl methyl ketone when heated with hydrochloric acid (sp. gr.= 1.1) for several hours; alcoholic potash resolves it into phenylacetic acid. Concentrated aqueous ammonia gives rise to phenylaceta.mide and malonamide, and aniline, which acts less rapidly, converts it into phenylacetanilide. J. J. 8, Ethylic Phenacetylmalonate. - - Zic benxy Zisoxccxo Zonecar6oxy Zate, O< R=F*GH'2Ph - is prepared COO CHGOOEt' by heating ethylic phenacetglmalonate dissolved in 60 per cent. alcohol with hydroxylamine hydrochloride and sodium carbonate on the water bath; it softens a t 124", and melts a t 143". The alcoholic solution gives a deep red coloration with ferric chloride, but does not reduce boiling Fehling's solution.The silver derivative is white, and the nniline compound melts and decomposes a t 160'. On heating ethylic phenacetylmalonate with phenylhydrasine, Schott obtained ethylic 1 : 5 : 3-phenylbenzylpyrazolone-4-carboxylate (Zoc. cit.); if, however, the salt is heated with a solution of the base in glacial acetic acid, 1 : 5 : 3~1~enyzbenxyZpyrc6xo~one,ORCIANTC CHEMISTRY. 153 NHPh* g*CH,Ph N<CO--CH 9 is produced, and crystallises in plates melting at 131-134". It develops a deep red coloration with ferric chloride, but does not give Eiilow's reaction for hydrazides. Ethylic 1 : S-dih~d~*ox~nuphthcclene-2-carboxyZccte is obtained by dis- solving ethylic phenacetylmalonate in concentrated sulphuric acid, and pouring the liquid into cold water ; i t crystallises from dilute alcohol or acetic acid in yellowish needles, and melts a t 83-84', The alcoholic solution gives a blue coloration with ferric chloride.The dicicetpl derivative crystallises in slender, white needlw, and melts a t 64'. The diurnine, which is produced in small quantity when the substance is heated with aqueous ammonia a t looo, melts at 168-172", and its solution becomes coloured in consequence of oxidation, The moncmilide derivative crystallises from acetic acid in rhombic plates, and melts at 185". The dibs.orno-derivative crystallises in yellow needles, and melts a t 159-160' ; the alcoholic solution gives a blue coloration with ferric chloride, 1 : 3-D~hyds.oxynccphthcclene-~-cccrbox~Z~c cccid is prepared from the ethylic salt by heating it with aqueous baryta at SO", hydrogen being passed through the solution during the operation ; it crystallises from water in clusters of yellowish needles, and melts a t 145O, when it evolves carbonic anhydride. The silver salt has been analysed.When the acid is boiled with water, it is converted into 1 :3-dibydroxy- naphthalene (Friedliinder and Riidt, Abstr., 1896, i, 569). 31. 0. F. Salts of Phenylphenazonium and Phenylnaphthophenazon- ium and their Reaction with Alkalis and Amines. By FRIED- Compare Abstr., 1897, i, 172). - Phenylphenazonium dichromate, (C1,Hl,N,),Cr,O7, forms small, ochre-yellow prisms ; the platinochloricle is a sparingly soluble, brownish-yellow, crystalline powder, and the aurochloride a heavy, ochre-yellow precipitate ; the chloride has only been obtained in solution ; the iodide is a brown, crystalline precipitate, and the rnercurocldoride and picrate are also crystalline precipitates. Phenylphenazonium ferric chloride is converted by aqueous soda into nposafranone, ClsH12N,0, identical with the product obtained by Jaubert (Abstr., 1895, i, 219).Alcoholic ammonia converts phenyl- phenazonium ferric chloride into aposafranine chloride, RICH KEHRMANN and IT. SCHAPOSCHNIKOFF (Bey., 1897, 2620-2628. The hydro-derivative of the phenazonium compound, C,H,<Nph>C,H4, NH is also formed, but, is rapidly oxidised by the oxygen of the air, and is thus reconverted into the original phenazonium derivative, which then again reacts with the ammonia, all the original substance being finally converted into aposafranine, or decomposed by secondary reactions.Di~zethyZa~osafrani?ae nitrate, NPu3[e2* C 6 H 3 < z E > C 6 H , , ob- tained by acting on the phenylphenazonium ferric chloride with154 ABSTRACTS OF CHEMICAL PAPERS, dimetliylumirie and precipitating with sodium nitrate, crystallises with $H,O in thick prisms with n bronze lustre. The plc~tinochloride forms lustrous granules, and the tlichomccte n brownish-violet, crys- talline powder. The salts give bluish-green solutions in sulphuric acid, which become violet on t'he addition of water. Aniline converts the phenylphenazoninm ferric chloride into the phenylaposafranine chloride previously obtained by Fischer and Hepp (Abstr., 1897, i, 6 3 6). This is accompanied by ccszili~op~en~lka~osnfranine chloride, which crystallises in granules with a green, metallic lustre.The salts of phenylnaphthophenazoninm are converted by concentrated soda into rosindone, O<i 110 5 :? and by ammonia into rosinduline chloride, NPh-C,H: " * C,H4<Nph~>C10HS*NH2. Dimethylamine produces salts of di- methylrosindulino, which readily decompose in alkaline solution with formation of rosindone and dimethylamine. The nitrate, -- N- NMe2 '1OH5gNph(NO )3>C,H4 9 crystallises with $H,O in prisms with a greenish lustre. chloride and clicl~ronznte are sparingly soluble, crystalline precipitates. The platino- A. H. Salts of Phenylisonaphthophenazonium and the Action of By FREDERICH KEHRMANN and WILHELM HELWIG Compare Abstr., lS97, i, 107, 172).- Amines on them. (Rer,, lS97, 30, 2629-2636. formed, together with a small amoiint Gf phenylnaphthophenazonium hydroxide, by the conden sation of P-naphthaquinone with amidodi- phenylamine.Some of its salts have already been described. The double ferric chloride crystallises in lustrous, orange-yellow plates melting at 200.5" ; the nitrate forms reddish-yellow, compact crystals, which melt and decompose a t 229' ; theplatinochloride is an orange-red, crystalline powder ; the aurochloride melts at 240°, and the dichromate is a scarlet- red powder. The salts of phenylisonaphthophenazonium are converted into amido-derivatives by alcoholic ammonia. 3-Amidop?~enyliso- nap~~tho~~~enaxonium chloride (isorosinduline chloride, No. 4), crystallises in violet-red needles which dissolve in water, forming a magenta-red solution, from which aqueous soda precipitates the free base ; the platinochloricle crystallises in violet needles, and the nitrate in flat prisms with a coppery lust re.3 -Dimethglarnid ophen ylisonaphtho - phenccxoniurtz nitrate (dimethylisoroainduline nitrate), C,,H,,,N3* NO,, is obtained by the action of dimethylamine on the isonaphthophenazo- nium salts. It crystallises in indigo-blue prisms with a coppery lustre, and melts with decomposition a t 220O. The aurochloricle forms blue crystals which melt and decompose at 200-203" ; the plntinochloride also forms blue crystals, 3- Phen ykamidophennylisonaphthophenaxoniurnORGANTC CHEMTSTRY. 155 cJdoi+Ze (phenylisorosinduline chloride), prepared by heating the double ferric chloride with aniline, is a heavy, crystalline powder almost insoluble in cold water ; its platinociiloride is an insoluble, blue, crystal- line precipitate.The position of the nmido-group in these derivatives has not been definitely ascertained, but from the analogy of the phenylnaphtho- phenazonium compounds it is probable that it takes up the para-posi- tion relatively to the azine nitrogen atom. A. H. The Fifth Isomeride of Rosinduline. By FRIEDRICH KEHRMANN and O.FEDER (Ber., 189 7, 30,2637-2641 ).-Nitrorosinduline eldoride, . . N- 1 2 ;H2 c, oH~<NPhCl>CaH3*Nb2, obtained by heating ni trainidodi- phenylamine hydrochloride with oxynaphthaquinonimide in alcoholic solution (Rademacher, These, Berlin), is a heavy, dark red, crys- talline powder with a greenish lustre.A number of derivatives of this compound have been prepared and will be described by Rademacher in another communication. When t'his substance, in acid solution, is treated with sodium nitrite, and then with alcohol, hydrogen is subatituted for the amido-group, and salts of 4-nitrophenyl- naphthophenazoniurn are formed. C,2H,,N,02C1 + FeCI,, is at reddish-brown, sandy, crystalline powder. The nitrate forins green, metallic looking-needles, The aqueous solutions of both this and the other salts decomposes when warmed, nitrorosindone being deposited. The chloride crgstallises with 2H20 in green needles; the platino- chloride, nurochloride, and dichromate are insoluble crystalline pre- cipitates. The nitro-compound can readily be converted by reduction into the corresponding amido-derivative, isorosinduline chloride (No.5), C,,H,~~~hC1>C,H,'NB,, which crystallises in long, lustrous, black- violet needles, and is readily soluble in water ; the nitrate crystallises with 1H,O, and is almost insoluble in dilute nitric acid ; the platino- chloride forms bluish-black, insoluble needles. Triazine Derivatives from Chrysoidine and from Orthamido- azotoluene. By EimLIo NOELTING and F. WEQELIN (Bey., 1897, 30, 2595-2604).-Diamidoazo-compounds react with benzaldehyde in a similar manner t o monamido-compounds (Goldschmidt and Rosell, Abstr., 1890, 614), triaziue derivatives being formed, which are capable of undergoing the diazo-reaction. The double f e w i c chloride, A. H. The trinxine from chrysoidine and benzaldehyde, N-NPh N*CHPh' NH,-C,H,<' I is a yellowish powder, solutions of which rapidly become brown in the air.The sulphate is sparingly soluble. The acetyl derivative is a white powder which melts a t 216'; the benxoyl derivative melts at 221'. The triazine readily forms diazo-salts, which yield red colouring matters with P-naphthol, resorcinol, and other phenols and amido-compounds. Fuming sulphnric acid converts the triazine into a mixture of156 ABSTRACTS OF CHEMICAL PAPERS, sdphonic acids, which have an extremely sweet taste. The sulpho- triazines obtained from sulphonated chrysoidines all have this sweet taste, whereas the compound from chrysoidine and benzalclehydemeta- sulphonic acid has a bitter taste. When the amido-group of chrysoidine- parasulphonic acid is replaced by hydrogen, the salts of the resulting acid, which crystallises in needles, also have a smeet taste.These thiee acids are all insoluble in cold water, spariqly soluble in hot water. The triaxine from chrysoidine and orthonitrobenzaldehyde, C19H15N502, crystallise in yellow tablets, melts and decomposes a t 118-1 1 9 O , and on reduction yields an cunido-compound, which melts and decomposes a t 204'. The triaxine from metanitrobenzaldehyde forms yellow crystals which melt and decompose at 204-205". The amido-compound melts and decomposes at 187". The trinxine from parsnitrobenzaldehyde forms red crystals which melt and decompose at 211', and are less soluble than those of the ortho-compound. The amido-derivative melts a t 220'. The colouring matters formed from the azo-derivatives of these three amidotriazines with amidonaphtholsulphonic acid G,[NH, : OH : SOt3H = 1 : 1' : 3'1, and amidonaphtholdisulphonic acid H,[NH, : OH : (SO,H), = 1 : 1': 3 : 3'1 have also been examined. They dye cotton without mordants violet to blue, but are not fast to acids. The ortho-com- pounds have the least colouring power, the para-compounds the greatest.The triaxine from orthamidoazotoluene and orthonitrobenzaldehyde, C2JHi,N,0,, crystallises in yellow needles melting at 230'. The trzaxzne from the metnnitrobenzaldehyde forms yellowish needles melting a t 228O, whilst that from the para-compound melts a t 264'. Metahydroxybenzaldehyde yields a triuxine, C,,H,,N,O, which crys- tallises in white needles me1 ting at 265'. Metasulphobenzaldehyde yields a triaxirte, C,,H3,N,S0,, which is a crystalline powder. Phthalic anhydride does not yield analogous compounds with amidoazotoluene, but simply forms an acid derivative.A. H. Dimethylconiine. By MARTIN MUGDAN (Annalen, 1897, 298, 131-147. Compare Abstr., 1894, i, 555)-It has been pointed out (Zoc. cit.) that whilst the optical activity of dimethylconiine appears to condemn the formula CHPr:CH*[CH,],*NMe,,. its abnormal behaviour towards hydrogen chloride renders the expression CH,:CH* CH,*CH,* CHPr*NMe, equally improbable ; the constitution of the base has been therefore - - - CH -CH expressed by the formula NMe,* CH<CHzpr.bHf. The author, how- CH,. YH2 ever, finds that dimethylpentamethenylamine, NMe,. CH< CH,-CH,' which should resemble in behaviour the Ligher homologues, dimethyl- or-pipecoline and dimethylconiine, differs from them greatly.Di- methylconiine, moreover, obtained by distilling dimethylconium hydroxide, can be resolved into three fractions which exhibit marked differences in optical activity, and from a study of the behaviour of crude dimethylconiine towards hydrogen iodide, i t appears thatORGANIC CHEMISTRY. 157 methylconiine is present in the base. Tn addition to this substance, the crude base consists of two isomeric dimethylconiines, yielding the two corresponding dihydrodimethylconiines on reduction ; one of these products has been identitied as normal dimethyloctylamine. It is shown, therefore, that when dimethylconium hydroxide is sub- mitted to distillation, change proceeds in three directions.I n the first place, methylic alcohol is eliminated, giving rise t o a small quantity of methylconiine ; when, however, water is separated, scission occurs between nitrogen and the 2-carbon atom on the one hand, giving rise to dimethylconiine of the formula CH,:CH* CH,* CH,*CHPr*NMe,, whilst on the other hand the base of the formula CHPr:CH*[CH,],*NMe, is produced when scission occurs between nitrogen and the 6-carbon atom. Dimethylperatamethenylamine, NMe,* CH<CH,. bH,, is prepared from pentamethenylarnine by the action of methylic iodide, and conver- sion of the substituted ammonium iodide into the ammonium chloride, which is then distilled a t 330'; it is a colourless base having the odour of trimethy lamine, and boils a t 133.5-1 35'.Unlike pentamethenyl- amine, it is scarcely soluble in water ; the hydrochloride crystallises from acetone in colourless, hygroscopic leaflets. Both the original base and the dirnethyl derivative are coloured by one drop of an alcoholic solution of iodine, whilst the latter is immediately decolorised by dimethylconiine. Dry dimethylpentamethenylsmine hydrochloride absorbs hydrogen chloride, which causes it to liquefy, but the halogen is completely removed by water, which is not the case with hydrochloro- dimethylconiine hydrochloride, The aurochlorides of dimethylpiperidine, dimethylpipecoline, and dimethylconiine, moreover, differ from the aurochloride of dimethylpentxmethenylamine in their unstable char- acter, the solution of the last-named salt undergoing no change when boiled. When dry hydrogen iodide is passed into dimethylconiine, it is found that, in addition to methylconiine, the base consists of a mixture of two isomerides ; the hydviodicle of one crystallises in short prisms and melts at 220°, whilst the Ihydyiodide of the other, which is produced in four times the amount, is more readily soluble in a mixture of alcohol and ethylic acetate, from which it crystallises in thick needles and melts a t 151-152'.A 10 per cent. solution of the former salt has a = 5*2O, whilst the hydriodide of lower melting point has a = 0.36'. The derivatives of the latter salt closely resemble those of dimethyl- conium iodide, and the chloride on distillation yields a base which boils a t 173°5-1'770, and has the odour and formula of methyl- coniine. Dinaet?~yldil~ydroconiine, C,,H,,N, obtained by reducing the pro- duct of the action of hydrogen iodide on dimethylconiine, with zinc dust and glacial acetic acid, has the odour of the base from which it is derived ; it boils a t 1S4-186', has the sp.gr. = 0,7795 at 14'/4', the refractive index nLD = 1.4288, and the rotation angle a= 3.6' in a 1 decimetre tube. The aurochloride crystallises in elongated leaflets, and is stable in solution ; the platinochloride melts at 11 7". Methylic iodide gives rise to a mixture which melts a t 166q and cansists of the CH,* CH,I58 ABSTRACTS OF CHEMICAL PAPERS. naetkiodide which melts a t 139-141°, and the somewhat niore readily soluble nzethiodide melting a t 190" ; the former of these has beeii identified with trimethyloctylammonium iodide which melts a t 139-141°, whilst the pZccti~aoc7~Zo~icle and ccuwchloi-ide melt a t 240') and 9 1 -93O respectively.M. 0. F. Derivatives of Theobromine. Action of Chloroform on Phenylhydrazine. By HEINRICH BRUNNER and HEINRICH LEINS (Bey., 1897, 30, 2584-2587).-The p~opyZ, isopropyl, butyl, and amyZ derivatives of theobromine were obtained by heating silver theo- bromine with the corresponding iodide, All these substances form crystalline granules melting above 270". Van der Slooten (Abstr., 1897, i, 382) has prepared a series of alkyltheobromines by the action of alkyl iodides on an alcoholic solution of potassium theobromine, and in this way has obtained compounds of comparatively low melting point, ,which differ from those just described.Nitro-theobrolmine NO,* CrH7N,0,, obtained by the direct action of nitric acid on theobromine, forms LZ pale yellow, micro- crystalline powder, which can be sublimed. The corresponding anaido-compound is sparingly soluble in alcohol and can a.lso be sublimed. When chloroform is heated or allowed to stand with phenyl- hydrazine, the hydrochloride of the latter is produced. No carbophenyl- hydrazine appears t o be formed. A. H. New Decomposition of Theobromine. By EMIT, FISCHER and FRITZ FRANK (Bey., 1897, 30, 2604-2618).-When theobromine is suspended in chloroform and treated with chlorine, i t is converted into an unstable substance rich in chlorine which separates in crystals but decomposes even in dry air. Its composition has not been ascertained.When t'his substance is treated with water it yields CO SJMe theobyomuric acid, COOH*NH*CO*NMe* C<N-co , which crystal- lises from lukewarm water in small, colourless needles or prisms, melts with evolution of gas a t about 181" (corr.), and does not reduce ammoniacal silver oxide or give the murexide reaction. It readily undergoes etherification, yielding ethereal salts, which are also formed by the action of alcohols on the chlorine derivative ; the athylic salt forms compact, colourless prisms terminated by pyramids, and melts at 212" (corr.); the methylic salt also crystallises well and melts at 199-200' (corr.). Hot water decomposes theobromuric acid with evolution of carbonic anhydride and formation of the niethylcaybamide salt of maethylpavabawic acid ; this melts at 127-128" (corr.), decomposes a t about 1 9 5 O , and is converted by alkalis into methyl- carbamide and oxalic acid, whilst hydrochloric acid decomposes it with formation of the carbamide and methglparabanic acid.It can readily be obtained by the union of its constituents, and is also formed when methylcarbamide is heated with ethylic oxalate at 100'; this reaction affords a new synthesis of methylparabanic acid. The constitution of theobromuric acid has not been definitely ascertained. Hydriodic acid converts both the free acid and it,s ethereal salts intoORGANIC CREMISTRY. 159 the n?ahydde o f h?/~rotheob1.o~?lzcric m i d , C7H,N,0,i, which crystallises in long, colourless needles and melts and decomposes at 264' (corr.) ; it dissolves in alkalis, forming salts of hydrotheobromu& acid, C7H,*N405, which separates when these solutions are acidified, and crystallises with 1H,O in long, colourless, matted needles.The acid becomes anhydrous a t 1 lO'and then melts and decomposes at 23l0(corr.). It is reconverted by 20 per cent. hydrochloric acid into the anhydride. The ethylic salt crystallises in matted needles melting a t 206-207' (corr.). Dilute baryta water converts hydrotheobromuric acid into carbonic anhydride, methylamine, and theui-ic acid, C,H7N,0, ; the latter is readily soluble in hot water, crystallises in rhombic prisms, melts and decomposes a t about 254' (corr.). It reduces ammoniacal silver oxide and is decomposed by excess of alkali; the constitution of the acid has not been ascertained.When et'hylic theobromurate is dissolved in concentrated hydro- chloric acid, a compound is formed which dissolves in water, with evolrition of gas and formation of carbonyldimetl~ylca~bnmicle, CO(NH*CO*NHMe),. This substance, which can be obtained by the action of phosgene on dimethylcarbamide, is a granular, crystalline powder melting a t 199-200' (corr.). It is not precipitated from a warm aqueous solution by mercuric nitrate, and gives no coloration with copper sulphate in alkaline solution ; these two reactions distinguish it from carhonyldicarbamide. It dissolves without change in cold dilute aqueous alkalis, but on boiling is decomposed with formation of methylcyanuric acid. Nitrous acid converts it into nitrosoca~bonyZdimethyZcas.balmide, C,H,N,O,.KO, which is a yellow, flocculent precipitate that cannot be recrystallised, and is decomposed by hot water with formation of met h y lc yanuric acid and met h y lbiuret .Methylc yamuric acid, C4HbN303, crystallises with 1H,O in thin plates, and when dry melts at 296-297' (corr.) ; it sublimes readily and can be distilled in small quantities, yielding a very penetrating vapour. When treated with aqueous potash and methylic iodide, it is converted into trimethylic isocyanurate. Jfelhylbiuret, C,H7N,0,, crystallises in prisms, melts at 165-166' (corr.) and yields a reddish-violet coloration with a dilute alkaline solution of copper sulphate. The nitroso-derivative is an almost colourless powder, which melts and decomposes at about 135'. A. H. Ketones of the Tropine Group.VIII. Constitution of Tropine. BYRICHARD WILLSTATTER (Bev., 1897,30,2679-2719. Compare Abstr., 1897, j, 304, and 1896, i, 655, 707).-The fact that condensation of tro- pinone with benzaldehyde gives rise to a dibenzylidene derivative (Abstr. , lS97, i, 304), has led the author to reconsider the evidence which sup- ports Merling's formula for tropine, with the result that it now appears necessary t o submit this expression to very considerable modification. In 1891, Merling first represented the constitution of tropine by the formula /CH,-CH,\ /CH2- CH,\ CH -CH(OH)*CH,-CH, or CH--CH,*CH(OH)-CH, \CH,--NM/ \cH,--NM~160 ABSTRACTS OF CHEMICAL PAPERS, the position of the hydroxylic group being uncertain ; accordingly, tropinone, the ketone obt.ained by oxidising tropine with chromic nnhjdride, was regarded by Willstiitter as having the structure CH-GO-CH,-CH (Abstr., 1836, i, 327).It was to be expected from the behaviour of camphor and menthone towards benzaldehyde in presence of hydrogen chloride, that tropinone would yield a benzylidene derivative analogous to benzylidenecamphor and benzylidenementhone ; as already stated, however, the product is dibenzylidenetropinone, and this circumstance is regarded by the author as indicating the presence of the group -CH,* CO*CH,- in the ketone. I n addition to the behaviour of tropinone towards aldehydes, support is lent to this view by the action of ethylic osalate, amylic nitrite, and diazobenzene chloride. It is known that the introduction of acidic radicles into ketones by means of sodium ethoxide affords a method of determining the number of methylenic groups in immediate connec- tim with carbonyl, acetone, for instance, first yielding ethylic acetone- oxalate, COMe*CH,*CO*COOEt, and then ethylic xanthochelidonate, CO(CH,* CO*CO@Et), ; similarly, tropinone is converted by ethylic oxalate and sodium ethoxide, first into ethylic tropinoneoxalate, C,H1,NO*CO*COOEt, and subsequently into ethylic tropinonedioxalate, C8H,,NO(CO*COOEt),. Again, when amylic nitrite acts on tropinone under the influence of hydrogen chloride dissolved in glacial acetic acid, di-isonitrosotropinone, C8H,,N,0,,. is produced, affording strong evidence of the presence of two methylenic groups attached to carbonyl ; the compound produced in this manner may be regarded as the 1 : 3-di- oximeof tropnnets.ione, the 1 : 2 : 3-triketone of the tropine series.Further- more, diazobenzene in acetic acid solution converts tropinone into the compound C,,H,,N,O, which constitutes the 1 : 3-diphenylhydrazone of tropanetrione. J n the author’s estimation, these observations establish the existence of the group, IC*CH,* CO*CH,* Ci, in tropinone, the corresponding alcohol complex, iC*CH,* CH(OH)*CH,* Ci, being present in the two isomeric bases tropine and $&opine. There are only three formulze for tropine which fulfil this condition, namely, I YHz YH*OH, 1 YMe YH*OH) and NMe/CH CH-OH, all of which admit CH2- CH-CH, CH-CH, of the presence of the complex, iC*NMe*CH(CH,R)*, in tropidine. The third expression is excluded, however, because i t does not account for the production of dihydrobenzaldehyde from tropinone methiodide and sodium carbonate (Will~tat~ter, Abstr., 1896, i, 327) ; nor does it agree with the formation of normal adipic acid on oxidation of tro- pilene (Ciamician and Silber, Abstr., 1896, i, 397), and by treatment of methylic. tropinate metbiodide with potash (Willstatter, Abstr., 1896, i, 266).The latter consideration leads the author to abandon also the second of the above formulae, and he therefore expresses tropine and /CH2 CH2\ \CH,*NiUe / CH,-yH-YH, NMe-CH-CH, CH,-- YH-YH, vH-yH2 \,I IORGANIC CHEMlGTRY. 161 tropinone by the formula? CH2 -7H-yH.2 CH2-FH-FH2 ~ 7~~ FH~OH, and 1 FH, 70 NMe-CH--CH, NMe-CH-CCR, respectively. According to this view, tropnn, the name by which the author distinguishes hydrotropidine, 1 YH, $X2, is a cyclic conihina- tion of n-methylpyrrolidine with hexahydrobenzene, the periphery of the ring being composed of 6 carbon atoms and 1 atom of nitrogen; and as the two constituent members of the combination have 3 carbon atoms in common, tropine must be looked on as a hexahydrophenol in which the rqeta-substituents are linked.From this conception of the structure of tropine, there follow the alternative formulzle, CHg-yH-YH, NMe-CH-CH, CH,-YH-GH CII,-$?H--flH, and I YHY y H 9 01' 1 YHz EH, NISle-CH-CH, NMe-CH-CH for tropinic acid and tropidine respectively, the former in each case being the one which the author regards as the more probable. Tropinic acid and tropidine being, as it were, the points of contact of the atropine and cocaine groups, it follows that ecgonine and anhydroecgonine are likewise derivatives of tropan, and the formula.? for these substances put forward by Einhorn and Tahara (Abstr., 1893, i, 377) will therefore require modification in this direction.The modified view of the structure of tropine emphasises the analogy between the bases of this series and those derived from the rind of pomegranate root. It also becomes clear that the n-methylpyrrolidine ring is common to all the alkaloids of the atropine and cocaine groups (compare Liebermann and Cybulski, Abstr., 1895, i, 310). CH, -YH -?:NOH Di-isonitrosotropinone, [ $!H2 70 , is prepared in the form NMe-CH -C:NOH of hydrochloride by dissolving tropinone (20 grams) in amylic nitrite (40 grams), and treating the cooled solution with glacial acetic acid (1 20 grams) previously saturated with hydrogen chloride at 0' ; the hydrochloride which separates is washed with acetic acid and with alcohol, and treated in aqueous solution with sodium acetate, or with caustic soda followed by acetic acid.Di-isonitrosotropinone crystallises from water in bright yellow, transparent prisms, and decomposes with slight explosion a t 197'; it is both basic and acidic, the aqueous solu- tion reddening litmus. It does not give Liebermann's reaction, and develops a reddish-brown coloration with ferric chloride, whilst ferrous sulphate colours the aqueous solution an intense green; alkaline and acid solutions of potassium permanganate are immediately decolorised by162 ABSTRACTS OF CHEMICAL PAPERS, the substance, which does not, however, reduce Fehling's solution.Alkaii hypochlorites readily oxidise the nitroso-compound, the yellow colour of the solution in alkalis being completely destroyed ; oxidation with nitric acid gives rise to a pyrroline derivative. The hydrocl~lo~ide, prepared in the manner described, crystallises from water in lustrous, rhombohedra1 plates; it becomes brown a t 200' and decomposes with explosion a t 260'. The hydrobronzicle, which crystallises from water in bright yellow, lustrous prisms, becomes brown a t 200' and explodes at 253'. The non no-silver derivative forms minute needles, is insoluble in water, resists the action of light, and explodes when heated ; the silvey derivative is dark-brown and crystalline.The dibenxoyl derivative crystallises from dilute acetic acid in slender, long needles, and melts and decomposes at 172'; when boiled with caustic soda, it yields ammonia, hydrogen cyanide, and pyrroline-bases, and it is also decom- posed by boiling glacial acetic acid. The anhpdride of di-isonitrosotropinoneoxime (tri-iionitrosotropan), C,H,N-C: N b(HoHj.b.N>O,j~ obtained by heating a solution of di-isonitrosotrop- inone in alkali with excess of an alkaline solution of hydroxylamine, and then acidifying with glacial acetic acid ; the furazan crystallises from alcohol in long, silky needles, and explodes a t 185-186'. The aqueous solution gives a brown coloration with ferric chloride. The hydrochloride cry stallises from water in six-sided plates, and decomposes vigorously at about 220' ; the benxoyl derivative crystallises from alcohol in small, lustrous needles, and melts a t 150-152O. The action of phenylhydrazine on di-isonotrosotropinone is somewhat complicated, and gives rise to two substances. The compound C,,H,,N,,O,, obtained from the free nitroso-compound, crystallises in reddish-yellow, six-sided plates, and melts a t 1'77-178' ; the compound, C2,H,,N,0, arises from di-isonitrosotropinone hydrochloride, and crystallises in orange-red leaflets which melt and decompose at ~?.ibronzaceto~yt~~opinone, CsH9NOBrd*OAc, is prepared by digesting a solution of tatrabromotropinone (Abstr., 1896, i, 709) in warm glacial acetic acid with silver acetate, the liquid being filtered after an interval and diluted with water ; it crystallisat3 from alcohol in short, highly refractive prisms, if deposited slowly in quadratic plates, and melts at 148'. Tropantrione diphenylhyraxone, C,H,,N,O, is prepared by adding diazobenzene chloride to a solution of tropinone in dilute acetic acid and maintaining the temperature of the liquid a t 0' during 3 hours ; the acetate separates when the solution is allowed to evaporate spon- taneously, and on decomposing this salt with caustic soda the diphenylhydrazone is obtained. It crystallises from absolute alcohol in rosette-like aggregates of dark-red, microscopic needles, and melts and decomposes a t 130'; it separates in long, slender needles con- taining chloroform of crystallisation when the acetate is boiled with a mixture of chloroform and absolute alcohol. The diphenylhgdrazone is a colouring matter, dyeing wool an orange-red ; the solution in concen- trated sulphuric acid is bluish-violet and in hydrochloric acid reddish- 224-225'.ORGANIC CHEMISTRY. 163 violet, both liquids becoming red on dilution with water (compare von Pechmann and Jenisch, Abstr., 1892, 161). Etlqlic tropinoneozcclnte, C,HllN<?H'C 'OoE t, prepared from co tropinone and ethylic oxalate (1 mol.) under the influence of sodium et hoxide (2 mols.), crystallises from absolute alcohol in colourless, highly refractive, six-sided plates and melts at 169*5", when it decom- poses; the aqueous solution gives a deep cherry-red coloration with ferric chloride, and when boiled with acetic acid and sodium acetate yields a brown solution. The plcctinochZos*ide forms red, microscopic leaflets containing 3H,O, and melts and decomposes a t 194--195O ; i t iEi scarcely soluble in cold water, and 'is decomposed by the boiling liquid, giving rise t o tropincne platinochloride. The hpdrochloride of tropinoneoxalic acid is produced on boiling the ethylic salt with con- centrated hydrochloric acid, and crystallises from alcohol in stellate aggregates of lustrous prisms ; it melts and decomposes a t 194O, and gives a deep cherry red coloration with ferric chloride. Isonitrosotropinoneoxalie acid, Y,H,N--FH*CO*COOH, is obtained C(NOH)*CO by dissolving ethylic tropinoneoxalate with amylic nitrite (1 mol.) in glacial acetic acid, and treating the solution with glacial acetic acid saturated a t 0" with hydrogen chloride ; the product separates in bright yellow needles and prisms, but is very unstable. Ferric chloride develops a brown coloration, and the solution in alkalis is intense yellow. Ethylic tropinonedioxalate, C,H,,NO( GO* COOEt),, is prepared by dissolving ethylic tropinoneoxalate in ethylic oxalate (2 mols.), and adding sodium ethoxide (2 mols.), free from alcohol, to the solution ; after some hours, the liquid is treated with water, agitated with ether, and the aqueous portion removed and acidified with acetic acid. The salt crystallises from alcohol in yellow, transparent prisms, separating from methylic alcohol in yellow, pleochromatic plates ; it melts and decomposes a t 176". Bifu~urylidenetvopinone, C,H1,NO(C,H,O),, is prepared by cautiously adding a solution of tropinone (1 mol.) and furfuraldehyde (2 mols.) in ether to the same medium containing sodium ethoxide (2 mols.) in suspension; it crystallises from absolute alcohol in canary- yellow prisms, and melts a t 138'. The solution in concentrated sul- phuric acid is of an intense violet-red, becoming yellow on dilution with water, which precipitates the sulphate in slender, lustrous needles ; it decolorises bromine and an acid solution of potassium permanganate. It differs from dibenzylidenetropinone in its property of dyeing wool greenish-yellow. The hydi*ochZoride, which crystallises in aggregates of microscopic prisms, melts and decomposes a t 237-238" ; the methiodide crystallises from water in yellow, pleochromatic plates, and melts .at 281°, when it decomposes. Although dibenzylidenetropinone was prepared in the first instance from tropinone and benzaldehyde under the influence of hydrochloric acid,caustic soda may be also employed as the condensing agent. If, how- ever, sodium ethoxide is used, the dibenzylidenetropinone is obtained164 ABSTRACTS OF CHEMICAL PAPERS, mixed with the compound C22H23B02, arising from condensation of tropinone with benzaldehyde (2 mols.) involving the elimination of only 1H,O; it contains 4H,O, which is removed a t 70', and it melts and decomposes a t 115". The solution in concentrated hydrochloric acid is deep red, and remains cherry-red on dilution. The methiodide crystallises from alcohol in prisms, and melts a t 186-187°, when it decomposes. M. 0. F. By OTTO FISCHEH. (Ber., 1897, 28, 2481-2489. Compare A bstr., 1885, 821, and 1889, 730)-Harmaline has been shown to be dihydroharmine ; both it and harmine are optically inactive in acetic acid solution. The oxidation of harmaline, C13Hl,N,0, to harmine, C,,H,,N,O, is best 'eff ected with potassium permanganate in dilute sulphuric acid solution. Methylharmine melts a t 209O ; its Ihydrochloride and flesh-coloured platinochloride, ( C13HllMeN,0),,H,P tC1, + 2H,O, were prepared ; it unites with more methylic iodide, yielding a quaternary iodide, Cl,H,lMeN,O,MeI, which reacts with silver nitrate, forming the crystalline nitrate ; the platinocldoride and auro- chloride of this quaternary base were also prepared. Acetylhnrmuline, C,,H,,AcN,O, can be prepared by dissolving harmaline and fused sodium acetate in acetic anhydride, heating cautiously to 60°, and then setting it aside ; it melts a t 204-205'. Methylharmdine, prepared from harmaline methiodide by boiling it with baryt,a water, melts and decomposes at 162O, and will unite with more methylic iodide. Dihydroharmaline is best prepared by reducing harmnline with sodium in boiling amyl-alcoholic solution ; its acetyl and benxoyl derivatives, Cl,H1,AcN,O, &c., melt at 239' and 158-159' respec- tively. Harmine and harmaline are oxidised to harminic acid, ClQH,N,04, by chromic acid in boiling acetic acid solution, or by nitric acid, the same product being obtained when harmol, dichloroharmine, or nitroharmine is oxidised. This acid reacts with normal alkali like a monobasic acid, but with resorcinol, like a dibasic acid, forming a fluor- escein. It reacts with methylic iodide and aqueous potash, yielding ntethylharminic acid, C1,HTMeN,O, which can also be obtained by the oxidation of metbylharmine, and which blackens between 260' and 280' when heated; with ethylic iodide, it yields ethylharminic acid, Cl,H7EtN,04, which blackens at 280". Apoharmine, formed from harminic a c ~ d by the loss of 2 mols. of carbonic anhydride, yjelds a yellow picrate melting at 247" ; boiling concentrated nitric acid con- verts it into a derivative, C,H7(N02)N2, which melts and decomposes a t 270°, and is soluble in alkalis; with methylic iodide, it yields the hydriodideof naethylapoharmine, C,H7MeN2, which base melts a t 77-78", and yields a yellow platinochloride which decomposes a t 260O. Harmine and Harmaline. c. P. I).

ISSN:0368-1769    

DOI:10.1039/CA8987400101

出版商:RSC    

年代:1898

数据来源: RSC

摘要:

105 General and Physical Chemistry. New Lines in the Speotra of Oxygen and Thallium. By HENRY WILDE (Compt. rend., 1897, 125, 708-709).-When a power- ful electric spark condensed by means of a small Leyden jar is passed from thallium electrodes through air under a pressure of 20 atmos., three red lines are seen which are not visible when a similar spark is passed through nitrogen from platinum electrodes. Two of the lines, 7760 and 7160, are due to oxygen, and the third, 6955, to thallium. The oxygen line, 7160, is useful for detecting the presence of oxygen when separating argon from air by the sparking method. The con- clusion of Stas, that the high temperature spectrum of thallium consists of a single line only, was due to the fact that he did not use a sufficiently powerful arc.The spectrum of thallium is the same whether observed in nitrogen or in air and therefore the lines and bands cannot be attributed, as Stas supposed, to thallium oxide. C. H. B. Fluorescence and Chemical Constitution. By RICHARD E. MEYER (Zeit. physikal. Chern., 1897, 24, 468-508).-The fluorescence of organic compounds may be regarded as due to the presence of certain atomic groups which remain unchanged in the various fluorescent derivatives ; these the author terms fluorphol-es or fluorphoric groups. I n order, however, that the fluorescence may be developed, it is further necessary that the fluorphore be situated between two heavy atomic groups, usually benzene nuclei. I n the derivatives of fluoran (Abstr., 1892, 970) embracing the fluoresceins, aaphthofluorans, rhodamines, &c., the fluorphore is the pyrone group, which, although not fluorescent itself, becomes so in the diphenyl derivatives.The xanbhones contain the same fluorphore, and the xanthens, its reduction product, and in all these groups of compounds the effect of substitution is very marked. In general, the entrance of heavy atoms or groups into the benzene nuclei diminishes the fluorescence, the effect being largely dependent on both nature and position of the substituent; thus the presence of hydroxyl groups in a position other than that of the fluorescein hydroxyls destroys or greatly weakens the fluorescence of the fluoran and xanthone compounds. In the anthracene group, only its direct derivatives, and not those of antbraquinone, are fluorescent. The acridine compounds contain the fluorphore CH/--\N and the effect of the position of the substituent is here also very marked, benzoflavine which contains both amido-groups in the " fluorescein position " being far more strongly fluorescent than €he isomeric chrys- aniline.The substitution of sulphur for oxygen in the pgrone ring does not destroy its fluorphoric character, as the thiopyrone derivatives also exhibit weak fluorescence. The azine, oxazine, and thiazine rings also act as fluorphores in the phenazines, phenazoxines and thiodi- pheny lamine compounds, which include many important fluorescent dyes as mauveine, the safranines and allied naphthalene compounds, \-/ VOL. LXXIV. ii 8106 ABSTRACTS OF CHEMICAL PAPERS, the indulines, Lauth's violet, and methylene-blue, which exhibits, although previously unrecorded, a reddish-violet fluorescence.The solvent has also a direct influence, as some compounds fluoresce strongly in some solutions, but not a t nil in others, and t'his difference is not always capable of being explained by diwociation changes. L. 31. J. Conductivity of Electrolytes for very rapid Electrical Vibrations. By J. A. ERSKISE ( A m . Phys. Chem., lS97, [ii], 62, 454--459).-For libratious of the period 1 *3 x los, the conductivity of the electrolytes examined agrees closely with that determined by Kohlrausch with the constant current,. H. C. By PAUL RIVALS (Conzpt. rend., lS9'7, 125, 574--576).-The author has deter- mined, by Bouty's method, the electrolytic conductivity of solutions of trichloracetic acid at 16" for degrees of dilution comprised between Y = 1 litre and I/= 128 litres, with tile following results.Values of v. p 10-7. Talues of V . p. 10-7. Values of V. p10-7. 1 litre 178.3 4 litres 260.6 16 litres 289.5 2 litres 226.4 6 litres 268.5 32 litres 304-3 3 litres 247.5 S litres 279.0 128 litres 317.0 p can be represented as a function of v, either by a parabolic formula, or more simply as a linear function of I / JF Electrolytic Conductivity of Trichloracetic Acid. Values of \'dues of Va,lues of p= 331.7 x (1 - 0*463/ JF). If p, the limit of conductivity, has the value pZ =331*7 x 10-7 and m=p/p.,, then m represents the proportion of acid dissociated and wz = 1 - 0.4631 JF Consideration of these i esults, together with the author's earlier determinations of the heat of dilution of trichloracetic acid a t various concentrations, shows that the lieat of dissolution and the degree of dissociation are both linear funciions of I/ Ji or, in other words, the heat of dilution is proportional t o the fraction of acid dissociated, The molecular heat of electrolytic dissociation of trichloracetic acid is + 4.17 Cal., and the heat of neutrdliv~tion by potassium hydroxide calculated on this basis by means of Ostwitld's formula agrees closely with the experimental value.Resistance and Specific Heat of some Oxides and Sulphides of Iron. By ANTAL ABT (Ann. Phys. ClLem., 1897, [ii], 62, 474--481).-Prisms were cut of the follou ing minerals, of the length i n centimetres and cross-section in square millimetres given below, and the resistance 1' in ohms of each prism directly measuied, and from this the resistance w for a prism of 1 centimetre length and 1 square centimetre arm calculated in each case.The results are given in the table on following page. The great difference in the magnetites is mainly due to the silica which they contain, as the resistance of quartz is very high. C. H. B.GENERAL AND PHYSICAL CHEMISTRY. 107 Mineral. Pyrrhotite ....................... Magnetite ........................... Haematite .......................... Nickel ore from Dobsina ......... ~~ Mineral. SiO, Fe S --- 4'42 57'68 37'66 5.72 68.10 - 2-13 67'15 - - - - Nickel ore N, ... Pyrrhoti te P, ...... ? > > 3 N, *.. n .. r 2 ...... Chalcopyrite ...... Pyrites ..........Magnetite M,. ..... .. M, ...... .. M, ...... .. M, ...... .. M, ...... .. M, ...... , , M ,...... .. M, ...... .. M, ...... Haematite H, ..... ,, H, ..... Siderite ............ .. H, ...... Locality. Dobsina A l s d j i i a 01 i i i i p o s Felsobinya Moravi tza J > ,, > I 1, 9 ) 9 ) > J 9 7 9 9 Kakukhegy (Hargitta) Moravitxa Dobsina Length. 4.961 9'970 10.310 10'030 14.600 0.375 14.596 14.610 0.086 0.083 0'082 9.948 4.981 16'630 14.590 4.987 0.115 14'475 10~000 Area. 28.136 172'922 196 *ooo 196.000 196*000 317.803 19G*OOO 196 -000 295.333 2 59 '3 39 257.732 193.000 23'619 201 -640 196 .OO 0 24-682 54.780 177'956 196'000 0.069 0.043 0.044 0.052 0.758 1.085 52560 80.250 2 860 12.451 45'608 8550.000 36500.000 36500 + 36500 + 29000 -000 1309.182 36500 f 36500 -000 0'0082 0'0074 0'0084 0 *0102 1'0176 9'2000 7~0600 10.7600 97'8900 3 87 -6 400 1433 '5100 1684.5500 1714'TlOO 4400 + 4900 + 1430'5200 6214*6400 6500 + 71 54 '0000 The specific heats, c, of the following minerals were determined, their composition being a t the same time ascertained by analysis.0 - 25.93 28 -78 - C 0.1539 0'1655 0.1745 0.1040 H. C. Theory of Solutions. By BRONISLAW PAWLEWSKI (Ber., 1897,30, 2805--2807).-The melting points of mixtures of paradibromobenzene and metachloronitrobenzene follow the normal course, th eutectic point 35.7' occurring with the mixture containing 32.99 per cent. paradibromobenzene, and 67.01 per cent. metachloronitrobenzene. Mixtures of paradibromobenzene and parachloronitrobenzene, on the other hand, are abnormal in their behaviour, as three distinct minima occur on the melting point curve.No explanation of this hehaviour can be given. H. C . Influence of Molecular Association on the Reduction of the Freezing Point and the Osmotic Pressure of Solutions. By HOLLAND CROMPTON (Ber., 1897, 30, 2720--2725>.-By combining the relation rd/?'=0*099x/cc (Trans., 1897, 925) with t h e van't Hoff equation for the reduction of the freezing point E=0*02Y2/r, for monomolecular compounds E/Td = 0.2, and for associated compounds E/Td = 0.2alz. Tables are given of the values of E/Td which show a 8-2108 ABSTRACTS OF CHEMICAL PAPERS. fair agreement with theory in the case of the monomolecular com- pounds, but discrepancies are observed among the associated compounds, To account for the latter, the view is advanced that van’t Hoff’s equs- tion should be modified when the solvent used is associated, and that for associated as well as for monomolecular solvents, E/Td = 0.2.H. C. Densities of Easily Liqueflable Gases. By ANATOLE LEDUC (Compt. rend., 1897, 125, 571--573).-The following results were obtained. Carbonic anhydride.. 1.5287 Chlorine.. .......... 2.491 Nitrous oxide ......... 1,5301 Ammonia ......... 0.5971 Hydrogen sulphide ... 1.1895 The author’s previous determinations have given 1,2692 for hydrogen chloride and 2,2639 for sulphurous anhydride. All these determina- tions the author regards as less exact than those that he has made with gases difficult to liquefy. For example, the condensation of the gas on the walls of the glass vessel introduces an error the magnitude of which cannot be calculated. Dissociation of Saline Hydrates and Analogous Compounds.By HENRI LESCCEUR (Ann. Cl~im. Yhys., 1896, [vii], 19, 213-234, 416-432 and 537-550. Compare Abstr., 1889, 815; 1893, ii, 364; 1894, ii, 343, and 1895, ii, 269).-The following have been examined : Lithium, cadium, manganese, cobalt, nickel, ferrous and uranium sulphates ; strontium, magnesium, zinc, cadmium, manganese, cobalt, nickel, copper, bismuth, and uranium nitrates ; potassium carbonate, potassium hydrogen carbonate, borax, normal potassium oxalate, potassium ferrocyanide, and sodium thiosulphate. The author points out the necessity of crystallising the sulphates from a perfectly neutral medium, as minute quantities of free sulphuric acid change the nature of the hydrates formed.The same applies to the nitrates. Compound precipitated by addition of sulphuric acid. C. H. B. Hydrate formed fyom neutral solution. Sodium sulphate.. ....... Na2S0, + 10H,O.. .... Slight turbidity only. Potassium ,, ......... K,SO, ................. KHSO,. Magnesium ,, ........ MgSO, + 7H,O ...... Slight turbidity. Manganese ,, ........ MnS0,+5H20 ...... MnS0,+H20. Ammonium ,, ......... (NH,),SO, ............ NH,HSO, Zinc ,, ......... ZnSO,+ 7H,O ...... ZnS0,+H20. Cadmium ,, ......... CdSO, + 4H,O., . . . . . . CdSO, + H,O. Ferrous ,, ......... FeSO, + 7H20.. ....... FeSO, + H20. Nickel ,, ......... NiSO, + 6H,O.. ....... NiSO, + H20. Cobalt ,, ......... CoSO, + 7H,O.. ....... CoSO, + H,O. Uranium ,, ......... U02S0, + 3H,O ......UO,SO, + H20. another in the fact that they yield hydrates MSO,+H,O. hydrate, as a rule, is only dissociated at a fairly high temperature. the hydrate, CuSO, + 3H,O, a t looo, has a tension of 525 mm. The sulphstes, with the exception of sodium sulphate, resemble one This The hydrate CaS0,++H20 begins to dissociate at about loo”, andGENERAL AND PHYSICAL CHEMISTRY. PO9 The maximum tensions at 20’ of saturated solutions are Zinc sulphate about 15.3 mm. Cobalt sulphate about 13.7 mm. Copper ,, ,, 15.2 ,, Cadmium ,, 9 , 12.9 9 , Ammoniumsulphate ,, 14.8 ,, Lithium ,, 9 , 12.4 9 , Magnesium ,, ,, 14.5 ,, Sodium , , 7 , 12.0 $ 9 Nickel ,, ,, 14.4 ,, Uranium ,, Y, 10.8 9 , Potassium ,, , , 14.4 ,, , Manganese,, ,. 11.8 ,, The most common hydrate met with among the nitrates is that with 6H,O.A second type is with 3H,O which is generally formed by the dehydration of the first type. The maximum tensions, a t 20°, of saturated solutions are Potassium nitrate about 15.0 mm. Zinc nitrate about 9.6 mm. Strontium ,, ,, 14.6 ,, Calcium ,, (4H,O) ,, 9.3 ,, Barium 9 , ,, 14.8 ,, Cobalt ,, ,, 9.3 ,, Sodium ,, ,, 11.15 ,, Nickel ,, ,, 8.5 9 ) Ammonium ,, 9 , 9.1 9 , Copper 9 , 9 , 7.9 9 , Uranium ,, ,, 12.2 ,, Manganese nitrate ,, 7.4 ,, Cadmium ,, 7 , 10.0 9 , J. J. S. By ISIDOR TRAUBE (Arm Phys. Chem., 1897, [ii], 62, 490--506).-1f in one litre of the co-volume of any liquid there are present N gram-molecules, as the author has shown in previous papers, the pressure mill be 22.38N atm. If we imagine water and a sugar solution separated by a semi- permeable membrane, the water containing N molecules per litre co- volume and the sugar solution N molecules of water to v molecules of sugar, the v molecules may, according t o the author’s view, be con- sidered t o enter into unstable union with a molecules of water, thus producing the observed contraction in volume, and the number of water particles which will enter the membrane from the two opposite sides will be 11’: ( N - av).Hence on the side of the solution the pressure will be less than that on the side of the water by 22.38 av atm. If a= 1 the observed pressure accords with the van’t Hoff theory, and, therefore, the diminution in pressure on the side-of the solution, due to the union of the dissolved substance and the mater, is the osmotic pressure.Poynting (Phil. Mag., 1896, [v], 42, 289) has already shown that, assigning this origin t o the osmotic pressure, the majority of the ob- served relations are a t once accounted for. The exceptions observed in the case of electrolytes are explained by variations in the value of a, and it is unnecessary to assume electrolytic dissociation in these instances. H. C. Causes of Osmotic Pressure and of the Simplicity of the Laws of Dilute Solutions. By WILLIAM SUTHERLAND (Phil. Mag., 1897, [v], 44,493-498).-The reasons usually assigned for the fact that the laws of the osmotic pressure of a solute in a solvent are the same as if the solvent were annihilated and the solute left as a perfect gas, are quite inadequate, because they would apply to any selected lot of the molecules of a solvent, and therefore to all the molecules, with the result that the laws of a perfect gas mould have Osmotic Pressure and Electrolytic Dissociation.PI0 ABSTRACTS OF CHEMICAL PAPERS.t o hold for all fluids down t o and in the liquid state (compare Speyers, Abstr., 1897, ii, 247). The answer t o the problem is to be found in a closer study of the semipermeable membrane. If we seek to picture t o ourselves how a membrane allows water molecules to pass, but not sugar molecules, our simplest conception of i t s structure is that of a mesh, amidst the threads of which the water molecules are packed in such a manner a s t o give way before one another almost as in ordinary water, whilst the sugar molecules are held back by the mesh.Thus the mesh forms a solid or quasi-solid framework through which water can pass with high viscous resistance, whilst the sugar molecule is absolutely blocked. Now if the framework turns back the sugar molecules, it must take the force of their blows and shield the water molecules from them. If, then, we suppose a semipermeable membrane separating water and a dilute solution of sugar in water, the sugar molecules are to be regarded as replacing some water molecules, but their collisions on the water in the membrane are rendered inoperative by the shielding action of the framework, so that the water mole- cules in the membrane receive more impacts on the side of the pure water than on the side of the solution, and therefore water flows through the rnembrane, until in the solution there is enough excess of hydrostatic pressure established t o compensate for the inoperative im- pacts of the sugar molecules; this inequality of pressure which can be hydrostatically balanced is the osmotic pressure.If the number of sugar molecules per unit volume is n and their mean velocity v, and the number of times a unit plane is crossed in the same direction by molecules per second is nui6, then, taking unit area on the surface of the semipermeable membrane in contact with the dilute sugar solution, each molecule in being turned back receives momentum %nu, so t h a t the whole pressure taken by unit area of the meshes of the membrane is nrnv2/3. Thus for the osmotic pressure we find the same expression as for the gas pressure of the sugar molecules if the water were annihilated and the sugar remained as a perfect gas.H. C. Real a n d Apparent Freezing Points and the Freezing Point Methods. By MEYER WILDERMA" (Phil. Mag., 1897,. [v], 44, -459 -486).-See Abstr., 1896, ii, 290. 11. Ethyl Derivatives. By HUGO SCHIFF and U. MONSACCHI (Zeit. physikul. CI~ern., 1897, 24, 513-521).-The authors have extended their previous researches (Abstr., 1897, ii, 89) to the ethyl derivatives of ammonium chloride, and have determined the expansion during the dis- solution of ethyl-, diethyl-, triethyl-, and tetrethyl-ammonium chlorides. For all these salts, expansion occurs during aqueous dissolution ; in a 65 per cent. solution of ethylammonium chloride, this expansion reaches 0.07 of the volume of the mixed constituents.The curves for specific gravity against concentration and expansion against concentration are given, those for the monoethyl derivative being seen to agree very closely with t h a t for ammonium chloride itself. For tetrethylammo- ilium chloride, a maximum expansion occurs when the concentration is about 50 per cent. The effect of dissolution in alcohol was only Expansion during the Dissolution of Ammonium S a l t s .GENERAL AND PHYSICAL CHEJIISTRY. 111 examined in the case of clietbylitmmoniuw chloride, and here a contrac- tion occurred. L. 31. J. Compressibility of Salt Solutions. By HEPU'RI GILBAULT (Zed. physikcd. C'hem., 18'37, 24, 385-440. Clomp,ire Abstr., 1892, 766).- For the determination of the cmipressibility a t temperatures not far removed from t h a t of the atmosphere, a modification of Cailletet's method was employed, tohe difference being the use of a gold-coated platinum mire inserted in the neck of the piezometer to indicate the contraction instead of gilding the interior of the piezometer itself.Researches with water and solutioils of iron salts indicate the avail- ability and accuracy of the method. For high temperatures, the author used a cylindrical tube immersed horizontally in a bath of glycerol, the pressures being in all case$ taken with a hydrogen mano- meter. I n order to extend the observations to teinpernt ures approaching the critical value., experiments n7ere mad2 wit11 solu:,ions of benzoic acid and of borneol iu ether, and of resorcinol in ethylic alcohol, and the criticd data of the v'irious soluticns were therefore first determined, curves of critical temperature, and critical pressure, against molecular concentration being given.The mixture law of P,Lwlewski is not obeyed, since at lorn concentrations a small quantity of sslt causes a relatively great alteration of the critical tempernture or pressure, the curves becoming nearly perpadicular to the axis of concentration. The curves for the solutions of borneol and OE bcnzoic acid are alniost iden- tical, so that the author concludes that the change of critical tempera- ture is only dependent on the rno1ecul;tr concentration and not on the nature of the dissolved substance. Tables are first given for the volumes, at various pressures, of ether and ethereal solutions of benzoic acid at 139*5--812*1°, and of water and aqucou' solutions of potassium iodide at 20' ; and in all cases the compressibility decreases with in- crease of pressure.Van d a Waals' expression is insufficieut, and the author finds that the expreabion giving the best agreement with the experimental numbers is v =-: - l/M.klog(p - A ) + Bp -/- C where A, B, C and k are constants at constant teniperatwe. The calculated and ob- served values are found t o agree well for pressures up to 250 atmospheres in the case of aqueous solutions at ordinary temperatures, and ethereal and alcoholic solutions near their critical teni2eratures. The influence of temperature on the compressibility of ethereal and alcoholic solutions mas next conbidered, and the author obtains the following expression for the comprecsibility coefficient, c.! - b +p/r y = (8 - Y')/ T+ cZ(p - a)/r where 8 is the absolute critical temperature, r the critical pressure, and CL, d, and b constants.This expression gives satisfactory agree- ment with the observed numbers for all the solutions examined. As tho values a, b, and d are identical for solvent and solution, it is evi- dent t h a t the law of corresponding states applies t o the solutions, since the compressibility depends only on the ratiosp/r and 0/T. In the above case, the compressibility increases with tlie t ernpersture, but with water at ordinary temperatures the reverse obtains, and the author finds the temperature of minimum mean compressibility (1-300 atms.) to be112 ABSTRACTS OF CHEMICAL PAPERS.about 63.5'. I n the case of salt solutions a t low concentrations, similar results are found, but a t certain concentrations the compressibility remains practically constant over a considerable range of temperature. To investigate the effect of concentration, solutions of sodium chloride were employed ; the compressibility decreases as the concentration in- creases, but the curve is not a straight line, being slightly convex to both axes. The author gives the term '' molecular compressibility " t o the volume decrease of the solution containing the same number of molecules as 100 grams of water ; and assuming complete dissociation of the dissolved substance and the value 18 as the molecular weight- of water, obtains the equation (logp,, - logp)d/cc = k where puo and p ar9 the molecular compressibilities of water and solution, d is the density, u the ion concentration, and k a constant dependent only on the nature of the dissolved substance.This constant appears t o be connected with the molecular volume contraction on dissolution in much water, as the magnitudes of both constants are in the same order for a series of 18 salts examined, and a formula connecting the two constants is given. L. M. J. Equilibrium in Solutions with Three Components :-,&Naph- thol, Picric Acid, and Benzene. By BASIL B. KURILOFF (Zed. ph,yoikc%ccZ. CJuwn., 1897, 24, 441--467).-In the equilibrium of the above system, the following solid phases may occur, /3-naphthol, picric acid, benzene, ,&naphthol picrate, and benzene picrate ; pre- liminary experiments indicated the absence of any ternary phase.The transition point of the P-naphthol picrate on the p-naphthol side is 11l0, and on the picric acid side 116", that of benzene picrate being 84.3" ; hence, representing the equilibrium as usual in the equilateral triangle, the isothermals above 116" are complete curves with the binary solid phase of the naphthol picrate. Between 111" and 84", they form three portions corresponding with the phases /?-naphthol, P-naphthol picrate, and picric acid, whilst below 84' the last portion corresponds with the phase benzene picrate. Three quintuple points occur where three solid phases co-exist, namely, (1) picric acid, P-naph- tho1 picrate, and benzene picrate ; (2) benzene picrate, P-naphthol picrate, and benzene ; and (3) P-naphthol, ,@naphthol picrate, and benzene, and the temperatures and composition of solution a t these points are given with the complete isothermals a t various different temperatures.L. M. J. [Formation and Changes of Solids.] By F. WALD (Zeit. physikal. Clzem., 1897,24,509-512).-1n a paper on the formation and changes of solids, Ostwald states that, during a transition from a particular state to one of greater stability, the change is not necessarily t o the most stable, but to the nearest (Abstr., 1897, ii, 308). The author discusses this statement, and considers i t is not based upon sufficient theoretical foundations to be given as a general law. L. M. J. Velocity and Rate of Recombination of the Ions of Gases exposed to Rontgen Radiation, By E.RUTHERFORD (Phil. Mag., 1897, [v], 44, 422--440).-Air which has been exposed t o Rontgen radiation preserves the power of discharging positive and negativeINORGANIC CHEMISTRY. 113 electrification a short time after the rays have ceased. The duration of the after-conductivity of air and other gases has been investigated, and from the data thus obtained, the velocity of the ions through various gases has been determined. The following table gives the times, T, for the number of ions to fall to half their original number. Gas. T in seconds. Conductivity. Air= 1. Hydrogen ..................... 0.65 ........................ 0.5 Air ........................... 0.3 ........................ 1 Hydrogen chloride ......... 0.35 ........................ 11 Carbonic anhydride.. ....... 0 95 1 ........................ 1 -2 Sulphurous anhydride.. .... 0.45 ........................ 4 Chlorine ..................... 0.18 ........................ 18 There seems to be no close connection between the values of 2" and the conductivities, although, as a general rule, it may be taken that the value of 2' diminishes with increase of conductivity. The value of 5" for the same gas was found to depend largely on the intensity of the radiation; and the presence of finely-divided matter, liquid or solid, affects the duration of the after-conductivity. The velocities of the ions were found to be independent of the amount of ionisation of the gas, and, with the exception of chlorine, to follow the inverse order of the densities. The velocity of t,he hydrogen ion through hydrogen is nearly four times as fast as the velocity of the oxygen ion in oxygen. The ions of sulphurous anhy- dride gave the slowest velocity, being only about one-tenth of that of hydrogen. H. C. Table of the Elements arranged with the Atomic Weights in Multiple Proportions. 125, '707). By HENRY WILDE (Compt. ?-end., 1897, [Boring Holes in Glass.] By H. JERVIS (Chem. News, 1897, 76, 211--212).-Holes may be bored in glass by making a stellate group of cross scratches with the point of a three-cornered file, and then working out the glass with the sharp corners of a newly-broken end of such a file, most conveniently fitted in a brace. I n all cases the tool must be moistened with turpentine. D. A. L.

ISSN:0368-1769    

DOI:10.1039/CA8987405105

出版商:RSC    

年代:1898

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 113 Inorganic Chemistry. Influence of Hygroscopic Substances on the Combination of Hydrogen and Oxygen. By MARCELLKN P. E. BERTHELOT (Conzpt. rend., 1897, 125, 675 -679).-Hydrogen chloride has no appreciable influence 0x1 the combination of oxygen and hydrogen at 100' or at 280'. Boron fluoride. seems to slightly retard combination, but this result is probably due to alteration in the surface of the glass, which is somewhat strongly attacked. Sulphurous anhydride is without114 BBSTKACTS OF' CHEMICAL PAPERS. influence at loo", but at 280", although the volume of the hydrogen remains unchanged, a notable quantity of oxygen is absorbed, and alkali sulphates are Formed from the alkalis in the glass. I n presence of sulphuric acid at 280", all the hydrogen is absorbed, and part of the sulphuric acid is reduced.A small qnnntity of oxygen also disappears, probably because it combines with the sulphurous anhydride. Phosphoric anhydride seems to be without influence on the com- bination of hydrogen and oxygen at any temperature up to 280", and even at this temperature the absorption oE the water as fast as it is formed has no marked influence on the rate of combination. (Com- pare Abstr., 1897, ii, 548.) By REINHOLD HEINEICH (Ann. Agron., 1897, 23, 485-486 ; from Ber. Lasadu). Vewuchs-Stat, Rostock, 1894, 2, 10)-The ammonia present in the air was absorbed by means of dilute hydrochloric acid in glass vessels 5 cm. high and 10 cm. in diameter, which were protected from rain. Ammonia was determined monthly. The greatest amount (4.06 1 milligrams) was found in June, the lowest (0.854 milligram) in February.Taking the different seasons, the amounts were : winter, 2.912 ; spring, 6,712 ; summer, 9.766, and autumn, 4.678 milligrams. The total amount for the year was 24.066 milligrams. Preparation of Nitrogen Chloride. By W. HENTSCHEL (Bey., 1897, 30, 2642. Compare Abstr., 1897, ii, 404 and 4i'i).--Attempts to modify the method of preparing nitrogen chloride from ammonium chloride by substituting bleaching. powder for sodium hypochlorite have hitherto been unsuccessful, owing to the liberation of gas from the solution. This difliculty is overcome by employing hydrochloric acid, which prevents evolution of gas. d 10 per cent. solution of nitrogen chloride in benzene is prepared in the following manner.3000 C.C. of a solution of bleaching powder, containing 22.5 grams of active chlorine per 1000 c.c., is gently agitated in a stoppered flask of 5000 C.C. capacity, and cautiously treated with a 10 per cent. solu- tion of hydrochloric acid until a portion OF the solution no longer yields gas when mixed with excess of a 20 per cent. solution of ammo- nium chloride. About 300 C.C. of the dilute acid is usually required for this purpose, and when the proper quantity has been added, the liquid is treated with 300 C.C. of a 20 per cent. solution of ammo- nium chloride, and then vigorously agitated with 300 C.C. of benzene during 30 seconds, the liquid meanwhile bein$ protected from light ; the benzene is separated from the aqueous liquid, and transferred to a folded filter containing 20 grams of crushed calcium chloride.C. H. B. The Ammonia of the Atmosphere. N. H. J. M. 35. 0. F. Action of Sulphur on Silicides. Production of Silicon. By GU~LLAUME J. L. DE CHALMOT (Amer. Chern. J,, 1897, 19, 8'71-877).- The author finds that the combined silicon of the copper silicide previously described by him (Abstr., 1897, ii, 262), may be partially liberated by acting on it with sulphur; the action begins a t 200-250" and may be completed at 270-280". Cuprous or cupricINORGANIC CHEMISTRY. 115 sulphido is produced according to the quantity of sulphur used, and a little silicon sulphide is also formed; above 300°, however, the liitter is obtained in larger quantity. The percentage of free silk in in two alloys containing originally 19-21 and 1.22 per cent.was increased t o 25.77 and 7.27 respectively, by heating with sulphur at temperatures below 290". Manganese silicide is much less readily attacked by snlphur ; below 300°, there is practically no action, whilst at the boiling point of sulphur, although some silicon sdphide is formed, no free silicon is liberated. Chromium silicide is not attacked by sulphur at 300", but at 450" some action seems t o occur, although no silicon is liberated. Iron silicide containing 29.51 per cent, of combined, and n o free, silicon is not attacked by boiling sulphur. Metallic Carbides which are Decomposed by Water. By HENRI &rOTSSAN (Ann,. chinz. Phys , 1896, [ vii], 19, 302--337).-A r5sumZ of previoud papers. Compare Abstr., 1894, ii, 450 ; 1896, i, 633 ; ii, 364, 419, 422, 423, 650.By HENRI MOISSAN (Ann. Chim. Phys , 1896, [vii], 19, 133--144),--The whole of this work has been published previously. Compare Ahstr., 1893, ii, 507, 532; 1894, ii, 42, and 1895, ii, 164. By HENRY WILDE (Compt. ?*end., 1897, 125, 649--651).-Undor low pressures a t - 76", and at 20 atmos., nitrogen does iiot yield the spectrum of argon, nor argon the spectrum of nitrogen, even if the discharge is continued for several hours. The author discusses the possible positions of argon and helium in his systematic arrangement of the elements according to their atomic weights. C. H. B. Lithium Chloride Solutions. By GEORGES LEMOINE (Compt. vend., 1897, 125, 603-605).-The sp. gr. at 0" of solutions of lithium chloride of various concentrations is as follows. Weight of salt in 100 grams of solution ...4.26 12.18 22.2 32.5 41.4 43.2 Sp. gr. ..................... 1.026 1.073 1.133 1.203 1.267 1.282 These results are more accurately represented by two right lines, than by a continuous curve, and there seems t o be a modification in the constitution of the solution from about 13 gram-molecules per litre t o about 6 gram-molecules per litre, or from LiC1+3H2O to about LiCl + 8 H,O. Gram-molecules of LiCl per litre ...... 12 9 6 3 1 0.5 Heat of dilution, starting from 12 Heat of dissolution taking 8.4 Cal. as E. W. W. J. J. S. Volatilisation of Refractory Substances, J. J. S. Atomic Weights of Argon and Helium. The heats of dilution at 10' are as follows. gram-molecules per litre ............0 1.3 2.2 2.8 3.1 3.2 Cal. maximurn .............................. 5.2 6.5 7.4 8.0 8.3 8.4 ,,I16 ABS'I'RAC'I'S OF CHEMICAL PAPERS. There is no development of heat beyond 7iC1+ 116H,O, and the results are practically the same a t 20" as at 10". The heat of dilution increases regularly with the quantity of water. Litlhn chloride and rnethylic alcohol :- Temperature ................................... lo 23" 50" Ratio of the weight of salt t o the weight of the saturated solution .................. 0.26'2 0.27 0.30 Weight of salt in 100 grams of solution.., 5.2 14.5 22.1 sp. gr. at 21.5" ................................ OaS36 0.910 0.974 Sp. gr. at 0" ...................................... 0.854 0.926 0.988 Gram-molecules of LiCl per litre ...........5 3 1 0.5 Molecules of MeOH per molecule of LiCl 4.7 7.9 24 48 Heat of dilution at 18" from 5 gram-mole- cules per litre ................................. 0 1.5 2.6 3.0 Cal. Heat of dissolution taking 10.9 as maximum 7.9 9.4 10.5 10.9 Cal. There is no development of heat beyond LiCl + 48MeOH. Lithium chloride uizd ethylic alcohol.-Determinations of s,olubili ty gave Temperature ........................... 1.6" 5.7" 13.0" 25.0" 40.6' 62.6" Ratio of weight of salt t o weight of its saturated solution ......... 0.14 0.14 0.13 0.14 0.15 0.18 These results are represented by two right lines which intersect at a low angle, at a point corresponding with 30°, the more inclined por- tion leading slowly t o the melting point of the salt. The solubility decreases, progressively in the order : water, methylic alcohol, ethylic alcohol, amylic alcohol.Weight of salt in 100 grams of solution ...... 5.2 Sp. gr. at 14.2 ....................................... 0.839 0.S71 0.903 Sp. gr. at 0" .......................................... 0.851 0.881 - Gram-molecules of LiCl per litre ............... 3 2 1 0.5 Molecules EtOH per molecule LiCl ............ 5.4 S.3 16.9 35 10.1 14.6 Heat of dilution from 3 gram-mols. per litre 0 -- 2.1 2.6Cal. Heat of dissolution taking 11.7 as maximum 9.1 11.2 11.5 Cal. C. H. B. By C. A. ALFRED LOTTERMOSER and ERNST VON MEYER (J. pr. cJt,em., 1897, 53, 241--247).--The authors propose t o study quantitatively the action OF various reagents on colloidal silver. They find that acids precipitate it from solution in the " molecular " state, time and dilution being of great importance; also with different acids widely different results are obtained, as is seen from the results of quantitative experiments already completed.Colloidal silver is not precipitated by small amounts of sodium chloride or hydrochloric acid in presence of albumin. Apparently no silver albuminate is formed, but further details of these experiments, as also of those on the action of salts and the halogens on colloidal silver will be given subsequently. By HENRI MOISSAN and P. WILLIAMS (Compt. rertd., 1897,125, 629--643).--Calcium boride is best obtained by heating an intimate mixture of 1000 parts of - Colloidal Silver. A. W. C. Calcium, Barium, and Strontium Borides.INORGANIC CHEMISTRY. 117 calcium borate, 630 parts of aluminium and 200 parts of sugar carbon in a carbon crucible for 7 minutes with a current of 900 a'mphres and 45 volts. The aluminium completely reduces the calcium borate, whilst the carbon prevents the formation of aluminium oxide.The product is broken up and heated successively with dilute hydrochloric acid, boiling concentrated hydrochloric acid, water, ether, toluene, and hydrofluoric acid. The calcium boride has the composition CaB, and forms transparent, microscopic cubic or rectangular crystals which scratch rock crystal, and even rubies ; sp. gr. = 2.33 a t 15". It is not altered when heated to redness in hydrogen, is attacked by fluorine in the cold, with incan- descence, by chlorine a t a red heat, and also, but more slowly, by bromine and iodine.When heated in air, i t does not burn below a bright red heat, and it is attacked by sulphur vapour under the same conditions. Nitrogen does not attack it even at loo", and it is not decomposed by water under pressure a t 250°, and even in a current of steam st higher temperatures decomposition is very slow. Gaseous halogen hydracids attack the boride at a dull red heat, but their solutions have no action on i t ; dilute sulphuric acid also does not attack it, but the concentrated acid is reduced. Ammonia is without action on the boride a t the softening point of glass. On the other hand, oxidising agents, whether fused or in solution, attack it readily Strontium boride, SrB,, is obtained in a similar way and has similar properties, but is not attacked by fluorine in the cold ; sp.gr. = 3-28 a t 15". Barium boride, BaB,! is also obtained in the same may, and its properties are similar ; it forms small but very regular crystals which scratch rubies, but not diamonds ; sp. gr. = 4.36 at 15". The yield of boride is greater than with calcium or strontium. C. H. B. By TASSILLY (Comj~t. ~eilzd., 1897, 125, 605-607).-Precipitated magnesium hydroxide yields n o oxybromide when heated tvitlh solutions of magnesium bromide. If, however, 5 grams of magnesium oxide previously heated a t a low temperature is added gradually to an almost boiling solution of 145 grams of magnesium bromide in 300 grams of water, and the solution is again heated, finally, to 150", and then filtered and allowed to cool, the oxy- bromide, MgBr2,3MgO+ 12H,O separates after about 15 days in small, acicular crystals which act on polarised light and show longitudinal extinction.When heated a t 120' in dry air free from carbonic anhy- dride, the crystals lose 6H20. The oxybromide alters when exposed to air, and absorbs carbonic anhydride; i t is decomposed by water, alcohol, and most other reagents. Basic Magnesium Salts. No definite oxyiodide could be obtained under similar conditions. Zinc Hydroxide in Precipitation. C. H. €3. By VERNON J. HALL (An2er. CJ6em. J., 1897, 19, 901--912).--The author has studied the precipita- tion of zinc hydroxide by means of potassium hydroxide solution, with reference to its effect in carrying down chlorine. When used in the ratio 2KH0 : ZnC12,no chlorine is found in the precipitate, whereas with118 ABSTRACTS OF CHEMICAL PAPERS.1$KHO, 7.4 per cent. of the total chlorine is obtained in the precipitate, and t'he quantity decreases as the proportion of potassium hydroxide is diminished. When the ratio is 5-SKHO : ZnC12, no chlorine is carried down. Experiments made on precipitation in presence of potasbium sulphate led to results similar to those obtained in the case of the precipitation of ferric hydroxide (Abstr., 1897, ii, 408). Increase of concentration tends to diminish the quantity of zinc precipitated and to increase the quantity of chlorine in the precipitate, whereas in the case of ferric hydroxide both the quantity of ferric oxide and chlorine in the precipitate decrease with increased concentration ; in both cases, however, rise of temperature greatly reduces the quantity of metallic oxide and chlorine thrown down.By FRBDERIC SCHLAGDENHAUFFEN (Compt. Illend., 1897, l25,573--574).-When water is allowed to remain in cohtact with filings of crude English or Chili copper for several days, it yields a yellow precipitate if acidified with hydrochloric acid and treated with hydrogen sulphide, the precipitate being more abundant if the copper and water are heated a t 100". If the same filings are afterwards treated with potassium hydroxide solution or dilute hydro- chloric acid, both arsenic and antimony are found in the solution. Further, if the filings are heated in a current uf carbonic anhydride, x mixture of arsenic and antimony oxides sublimes. Some other speci- mens of crude copper gave a sublimate which contained selenium, whilst E.W. W. Impurities in Crude Copper. - - - one specimen gave a sublimate of lead sulphide in cubical crystals. C. H. B. Solubility of Lead in Ammonia, By HERMANN ENDEMANN (Amer. Chem. J., 1897, 19, 890--893).--Strong ammonia does not dissolve litharge, although Karsten states that lead dissolves in ammonia, forming a dark yellow solution. If lead be immersed for a day in strong ammonia solution (29 per cent.), there is no apparent change, but the solution contains some lead ; if left for a longer time, the lead becomes coated with an orange, and later with a rust-coloured, precipitate, whose dark colour quickly fades if the precipitate is detached from the metal. After three days, the ammonia contains 0.0139 per cent.of lead, and if the action be allowed to continue for weeks, a white precipitate, which appears to be lead hydroxide mixed with oxides of other metals, is formed on the bottom and sides of the vessel. After drying, this precipitate contains only 0.15 per cent. of ammonia. Weak ammouia solution (2.9 per cent.) brings about a more rapid oxidation, for in 24 hours a white precipitate is formed on the glass, and on the surfaces of the liquid aud the lead, and during the next 48 ]lours i t rapidly increases in amount. The bearing of these observations on the manufacture of ammonia solution in lead-lined tanks, and the contamination of potable waters, is briefly discussed. E. W. W. Researches on Aluminium. By HENRI MOISSAN (Ann. Chim.Phys., 1896, [ vii], 19, 337-356).--A rSsunk of work previously published. Compare Abstr., 1894, ii, 450 ; 1895, ii, 226 ; 18'36, ii, 301, 338 and 601. J. J. S .INORGANIC CHEMISTRY. 119 Chromium Arsenate. By N. TARUGI (Gaxxettcc, 1897, 27, ii, 166- 175).-Schweit zer ascribed the composition, K ,Cr,As,O,,,~OH,O, to the compound obtained by treating potassium chromate with arsenious acid. The author considers that, a t ordinary temperatures, the salt has the constitution [Cr(OH)4:As04],Cr(OH)4,4K2HA~O~,12H~0, after heating at 60" the constitution (Cr.0,: As0,),Cr0,,4K2HAs0,, 1 OH,O, whilst by heating a t 120" the 10H,O is expelled; these constitutions are assigned on the basis of determinations of water of crystallisation. The compound of the composition K8Cr,As60,0H4, obtained a t 1 ZOO, is a green powder which, when boiled with potash, yields a pale green sub- stance of the composition K,CI.,AS,O,~, 1 2H,O, to which the constitution (K,As04* CrO,* O),Cr02 is assigned ; when boiled with potassium hydrogen arsenite solution, it yields a substance of the composition K7As,Cr,0,,,24K,0 and the constitution [Cr(K2As04):Khs04* O],Cr(KAsO4),24H,O.This, on boiling with potash, yields the compound [Cr( HO)2(K,As0,).0]2Cr(HO)2, which on heating a t 150" is converted into a compound of the constitu- tion [CrO(K2AsO4)*O],Cr0 ; on treating the latter with potassium hydrogen arsenite, it yields a substance of the Constitution [Cr(K,AsO,) :AsO,]Cr,, which is readily oxidised by potassium ferricyanide with formation of chromium nmenite, As0,iCr*As04:Cr:As0,* Cri AsO,, as a dark green powder.W. J. P. By RODOLPHE C. ENGEL (Compt. Tend., 1897,125, 65 1-654).-The author gives a rtsurnS of the recorded observations concerning stannic and metastannic acids. and of the results of his Stannic Acids. own invezigations (Abstr., 1897, ii, 376, and this vol., ii, 29). C. H. B. Action of Nitric Acid on Tin. By RODOLPHE C. ENGEL (Cornpt. Tend., 1897, 125, 709-'711).-The white product of the action of nitric acid on tin has been variously described as stannic acid (Gay Lussac), metastannic acid (Berzelius, Fremy), stannic nitrate (Monte- martini), and hasic stannic nitrate (Walker), The author finds that the nature of the product depends on the conditions under which it is formed. If nitric acid of sp. gr. 1-42 is diluted with different propor- tions of water, kept a t 0", and a stick of tin immersed in 200 C.C. of the liquid, the products are ( a ) with 1 vol. of nitric acid and 2 vols. o r more of water, stannous nitrate ; (b) with equal volumes of water and acid, stannic nitrate, the liquid finally becoming syrupy; and (c) with undiluted acid, stannic nitrate, which, however, is precipitated, be- cause it is insoluble in moderately concentrated nitric acid. Stannic nitrate is, however, readily decomposed by water or by a rise of temperature, the first product being stannic acid mixed with a small proportion of metastannic acid, the proportion of the latter increasing, however, if the substance remains in contact with water, or if it is dried. The limiting compound in the cold is metastannyl stannate. When metastannyl stannate is boiled with water, the conversion120 ABSTRACTS OF CHEMICAL PAPERS. into metastannic acid proceeds further, and parastannic acid is also formed in gradually increasing quantity (this vol., ii, 29). Pure meta- stannic acid yields parastannic acid when boiled with water ; the latter may perhaps be regarded as aninternal anhydride of the former. Metastannic acid is not formed by the direct action of nitric acid on tin ; the substance described by Berzelius was in reality parastannic acid. C. H. B.

ISSN:0368-1769    

DOI:10.1039/CA8987405113

出版商:RSC    

年代:1898

数据来源: RSC

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120 ABSTRACTS OF CHEMICAL PAPERS. Mineralogical Chemistry. Native Iron in the Coal Measures of Missouri. By EUGENE T. ALLEN (Amer. J. Ski., 1897, [iv], 4, 99--104).-Very few well-authen- ticated occurrences of terrestrial iron, which may not possibly be artificial or meteoric, have been described. It has been stated to be found in igneous rocks, in river sands, and in connection with car- bonaceous matter. Analysis I is of native iron from a boring in sandstone (containing 30.90 per cent. of calcareous cement and 1.27 per cent. Fe,?,) a t Cameron, Clinton Co. The iron occiirs in irregular fragments weighing on an average 0.5 gram, the largest weighing 45.4 grams; it is soft (H=4), very malleable, and on the fresh frac- ture almost silver-white. A well-marked, laminated cleavage is present, but no Widmanstatten figures are brought out by etching. Analysis I1 is of pieces of iron from a grey clay (containing 79.32 SiO, and 1.67 Fe per cent.) in a boring passing through sandstone and lignite a t Weaubleau, Hickory Co.I11 is of iron from fire-clay (con- taining 65.25 SiO, and 3.62 Fe per cent.) in a boring, passing through a coal bed, a t Holden, Johnson Co. Ye. SiO,. C. P. Cu,Ni,Co. Sp. gr. 11. 99.39 0.31 not det. 0.13 - 7.58, 7-83, 7-88 I. 99.16 0.37 0.065 0.207 Nil 7*63-7.73, 7.43 111. 97.10 1.65 not det. 0,176 - 7.49 These specimens of iron, when first extracted from the matrix, are tarnished, but are free from rust ; they are very soft, and contain no nickel. The depth (35-51 feet) a t which they occur excludes the possibility of. meteoric origin ; their occurrence in coal measures is suggestive of reduction. Composition of Pre-Carboniferous Coals.By W. HODGSON ELLIS (Chem. News, 1897, '76, 186--188).-1n anthraxolite from five different localities, the percentage of ash ranged between 0.72 and 48.37, whilst the extreme variations in the percentage of the other constituents, calculated on the dry, and ash-free substance, were : carbon, 90.5 and 97.1 ; hydrogen, 0.5 and 6.2; oxygen, 1.6 and 55,which numbers support the view that anthraxolites result from the meta- morphosis of bitumen. D. A. L. Identity of Andorite, Sundtite, and Webnerite. By GEORGE T. PRIOR and LEONARD J. SPENCER ( N h . Mag., 1897, 11, 286-301 ; and Zeits. Kryst. Min., 1898, 29).-Andorite was described in 1892 as L.J. S.MINEKALOGICAL CHEMISTRY. 121 an orthorhombic mineral from Felsobhnya, Hungary, having the compo- sition 2PbS,Ag,S,3Sb,S3 (Abstr., 1895, ii, 21). Sundtite from Oruro, Bolivia, was shortly afterwards described as being orthorhombic, with the formula (Ag,,Cu,,Fe)S,Sb,S, (Abstr., 1893, ii, 382). Webnerite, also from Ornro, was described as an argentiferous zinckenite with the composition 2h(PbS,Sb2S,) + Ag,S,Sb,S, (Abstr., 1895, ii, 170). A new analysisof measured cs.ystaZsfrom the original sundtite specimen gave the results under I, agreeing closely with the f orniula 2Pb3,Ag2S,3Sb2S3, and thus showing, when considered in connection with the crystallo- graphic measurements, the identityof sundtite with andori ta. Measure- ment of a rough crystal from the original specimen of welonerite also proves the identity of this mineral with andorite.The results of the original analysis of webnerite agree just as closely with the more simple formula 2PbS,Ag,S,3Sb,S3 as with the formula given above, especially when the copper is taken as replacing silver. Pb. Ag. Cn. Fe. Sb. S. Total. sp. gr. I. 24.10 10.94 0.68 0.30 41.31 22.06 99.39 5.377 11. 21.81 11.73 0.73 1.45 41.76 22.19 99.67 5-33 A description is also given of andorite “from Hungary,” which Occurs with quartz, pyrites, fluorite, chalybite, &c., in small crystals closely resembling freieslebenite in appearance ; analysis of measured crystals gave the results under 11. Alunite and cassiterite are de- scribed as being associated with Bolivian andorite. The characters of andorite are summarised as follows : orthorhombic with a : b : c = 0.6771 : 1 : 0.4458 ; the number of observed crystal forms is 42.Colour, dark steel-grey, with brilliant, metallic lustre ; opaque. Streak black and shining ; powder dull. There is no cleavage, and the fracture is smooth and conchoidal ; brittle. Sp. gr. = 5-35 ; H = 3$. Since there is no crystallographic relationship between andorite and the orthorhombic zinckenite (PbS,Sb,S,), and the monosymmetric miargyrite (Ag,S,db,S,), i t is pointed out that andorite must be a double salt, 2(PbS,Sb,S,) + Ag,S,Sb2S3 = PbAgSb3S6. [ Stannite from Bolivia.] By ALFRED W. STELZNER (Zeit. deutsch. geoZ. Ges., 1897, 49, 97, 131).-1n a paper (pp. 51-142) on the silver- tin ores of Bolivia, it is pointed out that the mode of occurrence of cassiterite in Bolivia is quite different from that in other parts of the world, where it occurs in association with boron and fluorine minerals at granite contacts. I n Bolivia, on the other hand, i t occurs in ordi- nary mineral veins with sulphide ores, and is sometimes associated with stannite and other sulphostannates. At Potosi, stannite occurs with pyrites, tetrahedritc, and rnispickel in cubic crystals with tetrahedral development ; the colour is steel-grey with a yellowish tinge, and the streak is black.Analysis by E. Ziessler of massive material, containing some blende and pyrites, gave, after deducting 6.96 per cent. of gangue, L. J. S. S. C U . Sn. Fe. Zn. Ge. Total. Sp. gx. 29.00 29.00 27.50 13.75 0.75 nil 100.00 4.495 Heated in a closed tube, it decrepitates and gives off much sulphur L, J.S. VOL. Lxxlv. ii. 0 in which it differs from ordinary stannite.122 ABSTRACTS OF CHEMICAL PAPERS. Distribution of Titanic Oxide upon the Earth. By FRANCIS P . DUNN~NQTON (Chenz. Xews, lS97, 76, 221-222. Compare Abstr., 1392, 79l).--Titanic oxide has been found in 34 samples of soil from various parts of the worlcl and also in the borings from a deep well extending to a depth of 4490 ft. The quantity varied from 2.33 to 0.09 per cent. in the air-dried soil, the average being 0.515 per cent. when the exceptionally rich sample (from St. Helena) containing 2.33 per cent. is omitted. By SAMUEL L. PENFIELD and H. W. FOOTE ( A ~ L Y . J. Sci., 1897, [iv], 4, 108-1iO ; and Zeit. Kyyst. Min., 1897, 28, 506--597),-The formula of ilrnenite has been written as (Fe,Mg)O,TiO, and as (Fe,Ti),O,.The mineral crystallises in the rhombohedraLteLnrtohedra1 division of the hexagonal system and the length of the vertical axis, 1.385, is not between those of hsematite (1 ~359) and artificial titanium sesquioxide (1 *316), neither of which show the tetartohedrism of ilmenite ; this, together with the fact that the amount of Ti20,, never exceeds that of Fe203, tells against the isomorphous mixture as given in the second formula. The presence of magnesia in many ilmenites can also not be accounted for by this formula. The largest amount of magnesia found in any ilmenite is shown in Rammelsberg's analysis of material from Wartvick, New York, but as this has been suggested to be due to impurities, two new analyses have been made of a crystal from this locality; the mean is SiO,.TiO,. FeO. MgO. MnO. Fe,O,. Total. Sp. gr. 0.37 57.29 24.15 15.97 1-10 1.87 100.75 4,345 Here the ratio R0,:RO is very close to l:l, thus indicating the existence of the molecule RO,TiO,. Since Fe,O, + Ti,O, =. 2Ti0, + 2Fe0, i t cannot be told by chemical means whether all the titanium exists as TiO,, but RS MgO,TiO, is present it is best to assume that FeO,TiO, is also present, and not (Fe,Ti),O,. In the published analyses of ilmenite, where Ti0,:RO = 1 : 1, there is often an excess of Fe203, and it is reason- able to suppose that the hsematite molecule, Fe20R or FeFeO,, is capable of mixingwith the ilmenite molecules, FeTi0,and MgTiO,, just as calcite and sodium nitrate are practically isomorphous.By SAMUEL L. PENFIELD and H. W. FOOTE (Anzey. J. Sci., 1897, [iv], 4, 105-108; and Zeit. Kryst. Min., 189'7, 28, 592).-Bixbyite mas found by M. Bixby in cubic crystals implanted on topaz and decomposed garnet and rhyolite at about 35 miles south-west of Sinipson, in Utah. The cubes are occasionally modified by the trapezohedron (211). The coIour is brilliant black with metallic lustre, and the streakis black. H = 6-6.5 ; sp. gr. = 4.945. The mineral fuses at about 4 and becomes magnetic. The fine powder is difficultly soluble in hydrochloric acid, and rrom the amount of chlorine evolved the available oxygen was calculated. The mean of two very close analyses is D. A. L. Composition of Ilmenite. L. J. S. Bixbyite a New Mineral.SiO,. A1,0,. Pe,O,. TiO,. MnO. MgO. Availxhle 0. Total. 1-21 2.53 47.98 1.7'0 42.05 0.10 4.3s !)9*95 The silica and alumina are due to the presence of topaz. Two forumlseMI N E 11 A LO C; 1 C' A L C! H EfiI I S'I'KY . 123 are possible, Fe,O,,llh,O, and FeO,MnO,. Tf the mineral is an iso- morphous mixture of Fe203, Xn,O, and Ti,O,, as in the first formula, it would be expected to be ihomboliedrnl and to belong to the hzematite group. The second formula, which shows a relation to the cubic perofskite, (CaO,TiO,), is the one adopted ; sinnll quantities of MgO aud MnO replace FeO, and there is a little TiO, with the MnO,. The mineral is therefore to be regarded as a ferrous salt of manganous acid, H,MnO,, corresponding with the manganese salt, braunite, MnMaO,.The associated topaz is crystallo~rnphically described ; i t is some- times opaque owing to the enclosure of minute quartz crystals. L. J. S. Composition of Hanllinite. By SAMUEL I;. PENFIELD (Arne?.. J. Sci., 1897, [iv], 4, 313--316; and Zed. lirryst. Min., 1897, 28, 588. Compare Abstr., 1891, .20).-I-Iaiulinite was described in 1890 as rhombohedral crystals occurring with heiderite and bertrandite a t Stoneham, Maine ; only n few small crystals were found, so an analysis was not possible. The mineral has now been found with apatite, herderite, and bertrnndite on felspsr and muscovite in Oxford CO., Maine. The small crystals are rhombohedral or prismatic in habit ; rr' = 88' 41'. For the analysis, a whole specimen was powdered and the hamlinite separated by a heavy liquid, the accompanying apatite was then dissolved in dilute acid ; the hamliiiite so obtained, of sp.gr. 3.159-3.283, when examined under the microscope, appeared to be pure. Total (less) P,O,. AI,O,. Fe,O,. SrO. BaO. H,O. F. SiO,. K,O. Na,O. Ofor F. 28'92 32-30 0'90 18'43 4'00 12.00 1'93 0'98 0'34 0'40 99.37 Deducting silica, alkalis, &c., as felspar and mica, this agrees closely with the formula Al,Sr(OH)iP,07, or [A1(OH),],(SrOH)P,07, in which strontium and hydroxyl are partly replaced by barium and fluorine respectively. This is the first mineral pyrophosphate that has been described, neither has a phosphate of strontium or barium been before observed. The associated bertrandite is crystallographically described. L. J. S. The mean of four partial analyses is Monazite from Idaho.By WALDEMAR LINDUREN (Arne?.. J. Xci., 1897, [iv], 4, 63-64).-The gravels and sands of the gold placers in the granite area of 'c Idaho Basin " contain, in the heavy residues, ilmenite, zircon, garnet, and monazite; the monazite is present in considerable quantity as yellowish or brownish grains. The crude material, with about 70 per ceut. of monazite, contains about 48 per Tripuhyite, a New Antimonate of Iron from Brazil. By EUGEN HIJSSAK and GEORGE T. PRIOR (Min. Mcbg., 1897, 11, 302-303).-- This new mineral is found as dull, Freenish-yellow fragments in asso- ciation with lewisite (Abstr., 1895, 11, 508) and derbylite (Abstr., 1897, ii, 410) in the cinnabar-bearing gravels a t Tripuhy, Minas Geraes. Thin sections show an aggregate of translucent, highly refractive, and strongly doubly-refracting grains, which are biaxial and of a bright cent.of cerium oxides, and 1.20 per cent. of thoria. L. J. 8. 9-2124 ABSTRACTS OF CHEMICAL PAPERS. canary-yellow colour. A few minute flakes, probably of muscovite, is the only impurity present. The streak is canary-yellow. When heated, the mineral is infusible, and gives off antimony fumes, leaving a residue of ferric oxide. It is insoluble in hydrochloric and nitric acids. Sp. gr. 5.82. Analysis gave Undet. Sb20,. FeO. CaO. SiO,. A1,0,. TiO,. (alkalis?). Total. 66.68 27.70 0.82 1.35 1.40 0.86 (1.19) 100.00 Assuming the iron to be ferrous, this agrees with the formula 2Fe0, S b,O,. Bltidite from the Punjab Salt Range. By FREDERICK R.MALLET (Min. Mag., 1897, 11, 311-31 'I).-GOOd crystals of blodite occur in the salt beds a t the Mayo mines and a t the Varcha mine; in external form and optical characters, they agree closely with the Stassfurt mineral. The crystals are colourless and usually transpa- rent, but are sometimes clouded by fluid inclusions. The mean of two analyses is L. J. S. MgO. Na,O. so,. H,O. NaC1. Total. 11.97 18.53 47.82 21.54 0.07 99.93 This agrees closely with the usual formula, MgSO,,Na,SO, + 4H,O. Between 85" and 120", it loses 2H,O, and the remainder begins to go ofl at about 125". Blodite has probably been formed by the interaction of magnesium sulphate (kieserite) with rock salt. [Cupro-scheelite frod New South Wales.] By GEORGE W. CARD (Records Geol. Survey N.X. W., 1897, 5, 122).-Cupro-scheelite occurs, associatod with bornite and copper carbonates, a t Upper Timby, near Yeoval.It is usually of a greenish tint, but is sometimes white, and has a waxy appearance ; rectangular outlines can be distinguished. Analysis gave WO,. MOO,. CaO. MgO. Fe,O,. Al,O,. CuO. CO,. H,O. Gangue. Total. 57.73 trace 14.40 0.22 2-98 trace '7.08 1.56 2-55 13.04 99.56 Deducting gangue, this corresponds with WO,, 66.7 ; CuO, 8.18 per cent. Apophyllite from South Africa. By J. A. LEO HENDERSON (Min. Mag., 1897, 11, 318-322).-1n the so-called '' blue-ground " of the farm Koppiesfontein near Jagersfontein, Orange Free State, apophyllite occurs as embedded octahedral crystals showing only the form p{111). The crystals are almost colourless or feebly yellow ; sp.gr. 2.371. Cleavage flakes show in polarised light a division into four sectors with biaxial characters. Analysis by Riihrig gave the results under I. No fluorine is given off when the mineral is'treated directly with sulphuric acid, but it may be obtained from the ammonia precipitate of the hydrochloric acid solution of the mineral (compare Abstr., 1896, ii, 369). L. J. 5. Stolzite from Broken Hill is also described. L. J. S. SiO,. A1,0,. Fe203. FeO. CaO. MgO. K,O. Na,O. H,O. F. NH,. Total. hP_J 1. 51.16 1.60 - 25.44 0.29 3.35 0.43 16.73 1.04 0.11 100.15 11. 34-35 15-44 3.55 14.80 10-11 7.16 - - 11.34 - - -MIXERALOGICAL CHEMISTRY. 125 The occurrence of apophyllite as embedded crystals is somewhat unusual; the matrix is a soft, talcose, Serpentine-like mass, which gave the results under I1 ; it is compared with the Kimberley " blue- ground," L.J. s. Psewdomorphs from Northern New York. By CHARLES HENRY SNYTH, JUNR. (Amer. J. Sci., 1897, [iv], 4, 309-312).- Pseudomorphs of pyroxene after wollastonite occur a t Diana, Lewis Co. ; here there has been an addition of magnesia. The crystals of scapolite and pyroxene in the limestone of Gouverneur, St. Lawrence Co., are sometimes altered to aggregates of a brown mica, probably phlogopite. Cases are cited in which garnet and epidote are apparently the alteration products of scapolite. Serpentines of Davos. By JOHN BALL (Inaug. Diss. Zurich, 1897, 47 pp.).-As shown by its mode of occurrence and by the results of contact-metamorphism, the serpentine of Davos in Switzerland has been derived from a lherzolite which was intruded into the surround- ing gneisses, dolomites, and schists.In the least altered rock (anal. I ) , olivine, enstatite and diallage are present, together with picotite, accessory rutile, and rarely hornblende, The most altered rock from the margins of the mass gave analysis 11. White steatite (anal. 111) occurs in lenticular patches and veinlets in the schists near the ser- pentine. Ophicalcite from the Calcareous schists at the serpentine contact gave IT ; it consists of fragments of altered serpentine with secondary hornblende in a calcite matrix. SiO,. Also,. Cr20,. Fe,O,. FeO. CaO. MgO. H,O. CO,. Total. Sp. gr. I. 41.83 5.46 0.45 1.13 2.73 2.26 34.64 10.54 - 99.04 2.78 11. 39.95 1.86 0.23 3.37 3.57 - 35.63 13.87 - 98.48 2.61 L.J. S. 111. 63.96 - - - 2.03 - 29.51 5.34 - 100.84 - IV. 32.96 3-15 - 3.26 1.90 12.76 2S.71 8.26 8.69 99.69 2.73 The associated rocks are described in detail; these are schistose whilst the serpentines are shattered. [Leucite Rocks in Wyoming.] By WHITMAN CROSS (Anae79. J. Xci., 1897, [iv], 4, 115--141).-1t was in the Leucite Hills, in south- western Wyoming, that leucite was first discovered in America, in 1871 ; here there is a lava flow of leucite rock, of which two new types are dis- tinguished and named Wyomingite and ordenite. Wyomingite is a compact, reddish-grey rock with a marked schistose structure owing to the parallel arrangement of small, reddish flakes of mica, this being the only mineral visible in hard specimens. Under the microscope, i t is seen t o consist of phlogopite flakes in a ground-mass of small leucite crystals and diopside microlites ; apatite, biotite, and residual glass are also present in small amount.From analysis I, the mineralogical composition is calculated as L. J. 5. Free silica. Leucite. Koselite. Diopsicie. Phlogopite. Accessories. 18.7 26.1 8.7 18.8 19.9 7.8 The presence of so large an excess of silica is difficult to explain, since Ordenite (anal. 11) has, with the exception of a vesicular structure there is no quartz, &c., to be seen in the thin sections.126 ABSTRACTS OF CHEMICAL PAPERS. the same outward appearance as vyomingite ; here leucite and sanidine predominate as compared with phlogopite, diopside, and a peculiar amphibole ; apatite and biotite are also present in small amount.Madupite (anal. 111) is the name given to a rock, probably a lava, from Pilot Butte, 15 miles east of the Lencite Hills ; it is a dull, felsitic- looking rock with numerous reddish specks of phlogopite. Under the microscope are seen diopside, phlogopite, and probably perofskite in a brownish, glassy base. A s calculiLted from the analysis, this base has the composition of leucite. Phlogopite from Wyomingite gave analysis IV, and V is of cliop- side from tvyomingite and mndupite. The rock analyses (1-111) by W. F. Hillebrand are interesting, on account of the large number of determined constituents. I n connection with these rocks, the classificn- tion of leucite rocks is discussed. SiO,. TiO,. ZrO,. R1,0,. (Ce,Di),03. Ch.,O,.Fe,O,. FeO. MnO. CaO. SrO. BaO. 1. 50.23 2.27 - 11-22 0'03 0.10 3.34 1'84 0.05 5.99 0'24 1'23 II. 54.17 2.67 0.22 10.16 - 0.05 3.34 0'65 0.06 4-19 0'18 0'59 III. 42'65 1.64 - 9'14 0.11 0.07 5.13 1.07 0'12 12'36 0'33 0.89 IV. 42.56 2-09 - 12.18 - 0'73 2.73 0.90 - 0-20 - 1'00 V. 50.86 3.03" - nil - - 1-19 1'82 0.03 23.32 - - H,O H,O (at (above Total (less MgO. K,O. Na,O. Li,O. 110") 110"). P,05. SO,. C1. F. CO,. 0 for I?). Sp.gr. I. 7'09 9-81 1.37 trace 0.93 1.72 1.89 0-74 0.03 0'50 - 100*40 2.779 11. 6'62 11-91 1'21 ,, 0'52 1-01 1.59 0'16 0'06 0.36 0.49 100.04 2'699 111. 10.89 7.99 0'90 ,, 2.04 2'18 1.52 0.58 0 4 3 0'47 - 99'91 2.857 V. 17.42 0.42 0.76 - 0.31 - - - - - 99'16 3.290 -+ IV. 22-40 10.70 0'44 ,, 2-35 0.06 - - 2.46 - 99'77 - * Ti0,f P,05. I1 contains a trace of nickel. Nitre (anal. VI, by L. G. Eakins) and nitratine (anal. VII) occur as These minerals are possibly crusts in exposed cavities in these rocks. of volcanic origin, as is sal ammonisc at Vesuvius. N,Oj I<,O. Na,O. [cnlccl.]. CaO. SO,. H,O. NaCI. Total. VI. 44.91 - [51'49] 1.09 1-59 0.63 0'16 99.87 VII. 4.97 32.09 [61*58] 0'2.1- 0'33 0'68 trace 99.89 L. J. S. Mineral Water from Buda. By LUDWIG ILOSVAY DE NAGY ILOSVA (Foldtani Koxlony, 1896, 26, 293-300).-Water from the Mathias Hunyady spring, No. 111, near Buda, in Hungary, gave the following results on analysis, It is colourless, and has a slight alkaline reaction and a bitter taste. Sp. gr. 1.03295 a t 20'. I n parts per 1000 : SiO,, 0.0109 ; Fe20,,A1,0,, traces ; Mg, 3,0033 ; Xa, 5.3993 ; K, 0.3511 ; Ca, 0.4136 ; SO,, 22.3805 ; (21, 1-31 1 I) ; €ICO:j, 0.6846 = 33.5552 ; free CO,, 0.0335. This is compared with other bitter waters from the neighbourhood of Buda ; those nearer the town contain more chlorine. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA8987405120

出版商:RSC    

年代:1898

数据来源: RSC

摘要:

VEGETABLE PHYSIOLOGY AND AGRICIJLTURE. 127 Physiological Chemistry. Length of Time during which Food remains in the Digestive Apparatus of Rabbits. By HUGO WEISKE (Landw. Versuchs-Stat., lS97,48, 375-379).-Six rabbits of the same litter, about four months old, received, for 12 days, 60 grams of air-dried oats ; they were then fed on hay ad Zibituna, killed at different intervals, and the contents of their stomachs examined. The first was killed 3 hours after feeding with hay commenced, the second 6 hours, the third, fourth, fifth and sixth, 9, 12, 24 and 48 hours respectively after the commencement of liay feeding. The results showed that, under the conditions of the ex- periment, the grain was sufficiently digested in about two days t o enable the excrement to be collected for the purpose of feeding experiments on the utilisation of foods.Effect of Increasing Amounts of Fat in Food on the Utilisa- tion of the Food Constituents. Ey A. WICKE and HUGO WEISICE Landw. Versuchs-Stat., 1897, 48, 390--400).--T~vo sheep were fed for 24 days as follows. No. -1 received during the whole period 1 kilogram of hay and 0.25 kilogram of linseed cake per day, whilst No. 2 received 0.75 and 0.2 kilogram of hay and cake respectively. For the first week no other food was given, but during the second, third, and fourth periods of the experiment, No. 1 had 60, 120, and 180 grams of olive oil, and No. 2, 50, 100, and 150 grams of olive oil per day. The results are given in tables showing the amounts of dry matter, proteid, fat, crude fibre, &c., in the food and in the faxes, and the amounts (actual and per cent.) digested.Even in the fourth period, when the amount of oil given was very large, the oil was mostly digested and resorbed; and the digestibility of the fat of the food, and also, but to a less extent, the dry matter of the food, was increased. The digestibility of the proteids remained about the same, whilst the digestibility of the crude fibre was increased, and that of the nitrogen-free extract substances diminished, under the influence of oil, On the whole, however, the results showed that large amounts of oil have no great effect on the digestibility and resorption of food constituents. N. H. J. M. N. H. J. M. Chemistry of Vegetable Physiology and Agriculture. Alcoholic Fermentation without Yeast Cells. Ey EDUARD BUCHNER and KUDOLF RAPP (Beis., 1897, 30, 2668-2678.Compare Abstr., 1897, ii, 380).-The authors are convinced that the yeast ex- tract described in previous papers does not owe its fermentative pro- perties to micro-organisms, because passage through a Chamberland filter, which arrests bacteria, does not impair i t s activity. Moreover, it is128 ABSTRACTS OF CHEMICAL PAPERS. found that a specimen of the extract, which time has rendered power- less to ferment, acquires but feeble activity when treated with 1 gram of living yeast, and becomes quite inactive if potassium arsenite is also added, whereas a freshly prepared extract rapidly induces fermentation. If the fermentative capacity of the yeast extract is due to micro- organisms, it would be expected that the activity of the liquid would increase with lapse of time, owing to the reproduction of the agents ; very rapid deterioration occurs, however, when the extract is kept for 2 days, when it loses the fermentative property.Zymase is not pro- duced by quiescent yeast ; a specimen of fresh yeast which yields an active extract when submitted a t once to pressure, gives rise to an in- active liquid if pressed after an interval of 3 days. This circumstance probably affords an explanation of the previously observed fact that specimens of yeast from some breweries failed to yield an extract con- taining zymase. The paper contains a description of the method by which the yeast extract is most conveniently obtained, and further observations have been made regarding the nature of its active enzyme, zymase, Its be- haviour towards hydrocyanic acid resembles tlhat of other enzymes, this agent checking the fermentative activity of zymase, and also des- troying the power of the original yeast extract to cause effervescence when mixed with hydrogen peroxide, Applying Meissl's method of determining the fermentative power of yeast, the authors have studied the fermentative power of yeast extract under various conditions ; tables have been compiled which embody the results of their experiments on the influence of temperature, antiseptics, time, and the concentration of the sugar solution employed. Yeast extracts from different sources have been also compared.M. 0. F. Oxidising Ferments (Oxydases). By GABRIEL BERTRAND (Ann.Agy'on., 1897, 23, 285-399. Compare Abstr., 1896, i, 534 ; ii, 61 and 5'71 ; 1897, ii, 117, 338, 493; this vol., i, 53).-Jt was previously observed that the ash of laccase contains manganese. It is now shown t h a t the activity of the laccase varies with the amoiint of manganese present. Three samples (each 0.2 gram) which, in presence of 50 C.C. of 2 per cent. quinol solution, absorbed in 14 hours 19.1, 15.5, and 10.6 C.C. of oxygen, contained respectively 0.159, 0.126, and 0.098 per cent. of manganese. It, was not found possible to remove the manganese from prepara- tions of laccase, but by altering the mode of preparation the author was able t o obtain a sample almost free from manganese. This sample, with quinol, absorbed only about 0.3 C.C. of oxygen, whilst the addition of manganese sulphate (Mn = 0.001 gram) induced an absorption of 4.3 C.C.of oxygen. Other sulphates (iron, aluminium, cerium, zinc, copper, calcium, magnesium, and potassium) had no effect. Direct experiments with a number of manganese salts showed that they all had the property of fixing free oxygen in presence of quinol, although in very different degrees, Solutions mere prepared contain- ing quinol 1 per cent., and manganese 0.1 per cent. The solutions ( I 00 c.c.) contained in 250 C.C. flasks were kept in agitation far a time,VEGETABLE PHYSIOLOGY AND AGRICULTURE, 129 and the amount of oxygen absorbed ascertained. bers show the amounts of gas absorbed by each salt : The following num- Nitrate. Sulphate. Chloride. Formate. Benzoate.1.5 1% 1.8 7.4 15.3 Acetate. Salicylate. Lactate. Gluconate. Succinate. 15.7 16.3 17.6 21.6 22.1 In some cases, a crystalline precipitate (quinhydrone) separated : with the gluconate in 2 hours, but much later with the salicylate. N. H. J. M. Vegetation with and without Argon. By TH. SCHLOESING, jun. (Cornpt. rend., 1897,125, 71 9-722).--0ats and feather-grass (Houque Zaineuse) respectively were grown in confined volumes of ordinary air and air deprived of argon, the ratio CO,/O, being determined in each case, and the general appearance, behaviour, &c., of the plants observed. The conclusion drawn from the experiment is that argon has no appre- ciable influence on vegetation. Researches on Germination. By F. VICTOR JODIN (Ann. Agyon., 1897, 23, 433-471.Compare Giglioli, Abstr., 1897, ii, 423).-Peas, kept under ordinary conditions, retain from 0.1 to 0.3 gram of water per gram of dry matter, an amount which is sufficient to determine gradual changes which finally result in loss of germinating power. Peas (3.452 grams) kept in air over mercury and exposed t o light, in 4; years absorbed 2.4 C.C. of oxygen, and produced 1.8 C.C. of carbonic anhydride ; the peas no longer germinated. In absence of light, there was no action during the same period, and the seeds germinated normally. Of nine peas which were kept immersed in mercury for over 10 years, two germinated almost normally; two others germinated, but not satisfactorily, whilst the remaining five failed to germinate completely. A number of peas, weighing 3.694 grams, were kept in air saturated with water a t 20-23'. In 10 days, the weight of the seeds increased to 5.602 grams, but there was no germination.Thirteen days later, the weight increased to 6.143 grams, and 15 peas germinated, whilst six did not. No more of the peas germinated, and the weight, 37 days after the commencement of the experiment, was 5.650 grams. The results show that the minimum of hydration a t which germination takes place is about 0.9 per grain of seed. In the next experiments, sterilised peas were kept under glass shades closed with mercury, and the composition of the air ascertained from time to time. A few C.C. of sterilised water was present, t o enable gerrni- nation to take place. Similar experiments mere made with peas with insufficient moisture for germination (hydration = 0.331 to 0.737).The results (which are given in detail in tables) show that the peas which could not germinate, owing to the amount of water present being insufficient, showed a respiratory activity, apparently similar to, and sometimes exceeding, that of the peas which germinated. With regard to the effect of an excess of carbonic anhydride on germination, peas and cress did not germinate when kept in an atmos- phere of CO, 7 58-3, 0, = 26.6, and N, = 15.1 per cent. After being 17 days in this atmosphere, all the peas were killed, but most of the C. H. B.130 ABSTRACTS OF CHEMICAL PAPERS. cress germinated when surrounded with ordinary air. Peas, however germinate in presence of 7 per cent. of carbonic anhydride, and pro- duced, in 13 per cent.of the gas, rootlets 2-3 mm. long; in presence of 50 per cent. of carbonic anhydride, peas rapidly lose the power of germinating, although they absorb oxygen and give off carbonic anhydride. The first stages of germination, resulting in the production of a rootlet 2-3 times the diameter of the pea, can take place without the intervention of an appreciable amount of oxygen. Subsequently, oxygen is necessary ; the oxygen must be in the uncombined state, and is not available either in the form of nitrates or of hydrogen peroxide. The reduction of nitrates, during germination, observed by Boussingault was, no doubt, due to the action of microbes (Ay~onomie, 7, 130. Com- pare also Godlewski, Abstr., 1S97, ii, 583). By BENGT JONSSON (Ann.Agron., lS97, 23, 491 ; from Konigl. Lcmdt. Akad. Hcmdl., 1896, 35, 95).-Lyttkens considers that the arsenic present in super- phosphates may sometimes explain the bad effects occasionally observed. Arsenic acid is injurious t o germination, and arsenious acid is much more injurious than arsenic acid. The author's experiments gave discordant results. I n some cases arsenic acid was favourable to germination, but this is attributed to its destructive action on the microbes present on the surface of the seeds. Mean Molecular Weight of the Soluble Matter in Germi- nating Grain. By LBON ~ ~ A Q U E K N F , (Cornpt. q-end., lS97, 125, 576-579).-The grain was allowed to germinate. in presence of dis- tilled water for a definite time, and was then crushed and pressed, the freezing point of the liquid and t h e quantity of dissolved solid matter in it being determined either with or without previous dilution with water as the case might require.From the data thus obtained, the mean molecular weight of the dissolved matter was calculated. I n the case of rye, after germinating eight days, it was 445 ; after twelve days, 203 ; and after thirty days, 167 : in the case of peas, after eight days, 306 ; after fifteen days, 199, and after forty days, 112 : in the case of white lupin, after fifteen days, 239 ; after twenty-two days, 226 ; and after forty days, 137. Although the molecular weights dif'ter widely i n the case of different plants, it is clear that, for the same species, the mean molecular weight of the soluble matters diminishes as germina- tion proceeds, It would follow that the transformation of the reserve matter in the seed does not consist, as is generally supposed, simply of a conversion of amylaceous substances into sugars, and of proteids into simple amides.Glucose and asparagine are probably the ultimate terms of the transformation, but, their formation is preceded by that of soluble intermediate products. I n the cases of peas and lupins, for example, no glucose can be detected in the soluble products after eight days germination. Similar determinations of the mean molecular weight of dissolved substances in the juice of different parts of green wheat soon after flowering gave the following results. Near the root, 176 ; middle of plant, 194 ; near the ear, 215. The molecular weight of the soluble N.H. J. 31. Influence of Arsenic on Germination. N. H. J. 31.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 131 matter therefore increases as i t ascends the plant, and gradually ap- proaches the point where it mill ultimately be stored up in the seed, Experiments showed that the osmotic pressure was practically the same in all parts of the plant. S u b s t i t u t i o n of Arsenic Acid for Phosphoric Acid in the Nutrition of Plants. By JULIUS STOKLASA ( A m . Agyon., 1897, 23, 471-477).-Oat8s mere grown in nutrit8ive solutions (l), without phosphorus or arsenic, (2), with phosphoric acid (0.00142 per cent.) and arsenic acid (as sodium salt, 0.0023 per cent.), (3), with phosphoric acid (0.0142 per cent.), and (4), with arsenic acid (0.0023 per cent.) but without phosphoric acid.C. H. B. The following results were obtained : Average lmgtli Dry produce & -\ Number Lecithin roots. stems. roots. stems, &c. seeds. of seeds. in leaves. em. em. grams. grams. grams. per cent. 1. 9.3 36.2 0.63 2.96 - - 0.38 2. 33.2 95.4 4.6 13.65 6.85 347 1.46 3. 35.6 96.7 4.8 14.38 7.32 368 1.35 4. 18.5 49.3 1.02 4.84 - - 0.41 Furfuralde- hyde in leaves. per cent. 8.1 1 s.43 8-09 10.27 The plants of series 4 (with arsenic) developed better than those of series 1, but the flowers soon dried up and the leaves mere bluish-green. I n presence of phosphoric acid, arsenic acid had no injurious effect. It was previously shown that chlorophyll formation (and consequently assimilation of carbon) depends on the presence of lecithin, a compound containing phosphorus, produced by the interaction of glycerophosphoric acid, choline, and chlorophyllanic acid.I n these ex- periments, the leaves produced under the iofluence of arsenic acid contained only about the same amount of lecithin as in series 1. On further examining the leaves, i t was found that those of series 1,2, and 3 contained chlorophyll grains, often accompanied with starch, whilst those of series 4 contained chlorophyll grains but no starch. I n absence of phosphorus and arsenic, the leaves were yellow. Furfuroids were produced in largest quantity under the influence of arsenic acid alone (they were determined as furfuraldehyde. See table). I n favouring the formation of furfuroids, arsenic acid increases the developwent of assimilating organs.Whilst 0.02 per cent. of arsenic acid is injurious t o vegetation, as little as 0.0002 per cent. of arsenious acid is sufficient t o destroy plants. N. H. J. M. Transformation of Sugars into Oil in the Olive. By C. GERBER (Compt. rend., 1897, 125,658-661).-The respiratory quotient CO,/O, for olives is less than unity when they are young, and when, as Luca has shown (Cou2pt. ~encl., 1861 and 1862), they contain a high propor- tion of maiinitol and a very low proportion of oil. It becomes greater than unity when they are large and when they change to violet-red, and at this period Luca found that the proportion of mannitol diminishes, whilst that of oil increases. Since the olives contain neither citric, tartaric, nor malic acid, and no alcoholic fermentation132 ABSTRACTS OF CHEMICAL PAPERS.goes on in the fruit, it follows that the excess of the respiration quotient above unity indicates that the oil is being formed a t the expense of the mannitol. Quantity of Pentosans and other Carbohydrates in Peat. By H. VON FEILITZEN and BERNHARD TOLLENS (Ber., 1897, 30, 2571-2576).-The formation of furfuraldehyde from vegetable matter on distillation with hydrochloric acid cannot be taken as a certain indication of the presence of pentosans, since other substances such as glycuronic acid, &c., yield it under the same conditions. The quantity of pentosans present in the peat was determined by the Kriiger-Tollens method, the largest quantity being found in the upper layers, and decreasing with the depth, the amount being roughly inversely proportional to the carbon present.The quantity of cellulose also decreases with the depth, the amount present in a sample of Sphccgnum cuspidcctunz a t the surface being 21.11 per cent., at 20-100 cm. deep, - 15-20 per cent., and a t 100-200 em. deep, - 6-87 per cent. On hydrolysing the peat, mannose, galactose, levulose, and pentoses were detected in the product. Fermentation of Peat. By H. VON FEILITZEN and BERNHARD TOLLENS (Bey., 1897, 30, 2577--2581).-Experiments were carried out with the object of obtaining alcohol from peat by hydrolysing with sulphuric acid and fermenting the glucoses thus formed with yeast. The following table shows the results obtained. Ferment- Alcohol Alcohol C. H. B. J. F. T. - Sngar before Pent- fesmentation.oses. able. theory. found. Speckener Moor I. (20-100 em.) ...... 27.87 14'49 13'38 6'84 6.79 11. (100-200 em.) ... 22.71 11.08 11'63 5'94 5.46 111. (200-300 cm.) ... 11'22 6.67 4-55 2.33 1.48 The upper, least decomposed, peat layers yield, therefore, more alcohol than the lower dark coloured layers rich in carbon. Composition of Oats. By BALLAND (Compt. ?*end., 1897, 125, 579-582. Compare Abstr., 1896, ii, 64)-There is no relation between the mean weight of the grains, the weight of grains per hectolitre, and the colour of the oats, nor between these factors and the proportion of cellulose, fat, and inorganic matter in the oats. As a rule, however, in the case of Russian oats, the white contain a higher proportion of nitrogen than the black. There are also no definite relations between the weights of the ash (inorganic matter), cellulose, fat, and nitrogen, except that in the same species a maximum of cellulose always coincides with a reduced proportion of nitrogen. There are no general relations between the weight of the kernel or of the husk and the mean weight of the grains or the weight of grain per hectolitre; white oats often give less kernel than black oats, but the contrary is the case with Russian oats.The ratio of kernel to husk varies greatly in different localities ; in hot climates, the proportion of husk is always high, although its composition is the same as in temperate climates, whereas the proportion of nitrogen in the kernel is much higher in hot climates than in temperate. Algerian oats contain as much or more nitrogen than the best oats from some European J.F. T.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 133 localities, although they contain a considerably higher proportion of husk. For oats of the same species, the nutritive value increases with the weight of the kernel. The composition of a n alcoholic extract of oats varies greatly with the concentration of the alcohol; with absolute alcohol, fats only and no nitrogenous matters are dissolved, but with more and more dilute alcohol the proportion of nitrogenous matter dissolved increases. No alkaloid is present, and the irritant properties observed by Sanson (Abstr., 1884, 914) are probably due to an essential oil present in small proportion. The high proportion of f a t in oats, combined with the proportion of nitrogenous matter and phosphates, makes them a more complete food for men and animals than either whezt, barley, or rye.Whole oats can be kept, for several years without any appreciable change in their composition, but when they are crushed changes take place, the acidity rises rapidly, and the fats undergo alteration. The composition of oats varies greatly according to latitude and climate ; even with the same species in the same district the composition varies with the season. Analyses of a thousand varieties of oats grown or imported into France in the years 1893-1897 show that the variations are of the following order :-Water, 9.80 to 17.00 ; nitrogenous matter, 7-10 to 14.13 ; fats, 2.89 t o 6.82 ; sugars and starches, 56-95 to 64.32 ; cellulose, 7.02 to 12.24; ash, 1.88 to 6.90 per cent.Weight of the kernel, 61.00 to 79.50; and weight of the husk, 20.50 to 39.00 per cent. Composition of the Seeds and Etiolated Seedlings of Lupinus angustifolius, L. By M. MERLIS (Lnndw. Tersuchs-Stat., 1897, 48, 419-45d).-The following summary shows the amounts of the different constituents, (I), in 100 parts of the dry seeds freed from husks; (2) in the corresponding amount (72.212 parts) of dry etiolated plants, 15 days old; and (3) the loss or gain. Mean weight of 100 grains, 1.80 to 4.32 grams. C. H. B. Insol- Nuclein, Glyce- Choles- Celln- N-free Aspara- N. Proteids. &c. Lnpeose. rides. Lecithin. terol. lose. extract. gine. 1. 6.61 36-18 0.88 11-34 7'48 2'20 0'20 1.58 27.89 0 2 . 6.56 7.63 1.53 0 1'62 1-14 0.46 8'44 11.77 18-17 3.-0.05 -28.55 +0*65 -11.34 -5'86 -1'06 +0'26 +6*86 -16.12 +18'17 Under nuclein, &c., indigestible nitrogenous substances are included, and under glycerides, free fatty acids. The amounts of ash were. (1) 3.51, (2) 3.83, and (3) +0*32 parts. The seeds contained, besides the above, 0.31 per cent. of alkaloids. The etiolated seedlings were found to contain leucine, amidovaleric acid, and choline. Arginine was not present unless in traces. Phenyl- a-amidopropionic acid was probably present in very small amounts. The results show, in the first, place, that the total nitrogen of the seeds and of the seedlings is practically the same, and that germina- tion is not accompanied with loss of nitrogen. The proteids break up, yielding asparagine, amido-acids, and batqes.The carbohydrates of the seeds diminished considerjbly, the lupeose (P-galactan) disappeaxing completely after 8-9 days, whilst there was a great increase of cellu- lose. The increase in ash may be due to the action of water on the134 ABSTRACTS OF CHEMICAL PAPERS. glass, or to the production of sulphates in the breaking up of the proteids. I n order to ascertain to what extent the constituents of the cotyledons are utilised during the development of seedlings, the amounts of the different seeds freed from husks were compared with the amounts in the cotyledons of seedlings 24 weeks old. The following are the amounts (in grams) in (1) 1000 seeds (dry matter = 102.0 grams), and (2) 2000 cotyledons (dry matter = 21.59 grams).N. Proteids. Crude fat, Lecithin. Cellulose. extract. Ash. 1. 6.64 37.14 7.04 2.26 1.77 28.17 3.36 2. 1.67 1-92 0.94 0.25 2.01 3.54 1.19 The results show that the reserve proteids, the fat and lecithin, are almost entirely consumed in 2 4 weeks, whilst most of the nitrogen- free extract also disappeared. With regard to the decomposition of proteids during the growth of etiolated seedlings, the nitrogen in different forms was determined a t intervals of three days. The following results show the amounts in 100 parts of dry seeds and in the corresponding amounts of seedlings a t the different dates. Insol. K-free Nitrogen. - I Dry As As as- Inphosphotungstic I n 6.14 - 0.48 - Seedlings, 3 days 96.08 5.56 0.49 0.45 0.1 1 9 , 6 ,, 89.20 3-19 1.93 0.49 1.00 9 ,, 82.73 2.38 3.19 - - ,, 1 2 ,, ’75.80 1.93 3.75 - I matter.proteids. parxgine. acid precipitate. difference. Seeds ............... 100 9 , ,, 15 ,, 72-72 1.49 3-85 0.45 0.8-2 ,, 18 ,, 70.69 1-51 4.23 0.43 0.34 The rapid decomposition of proteids in the early period of growth is in accordance with the observations of Prianischnikoff (Abstr., 1895, ii, 124 ; compare E. Schulze, Vierteljalwsclur. naturforsch. Ges. Zurich, 1894, 264). The increase of asparagine in the last period, when there was no corresponding decrease of proteids, would seem to indicate a transformation into asparagine of other products of the decomposition of proteids. This would lend support to the view that asparagine is not a primary product from proteids. N. H. J. M. Losses and Chemical Changes in Vegetable Foods when kept for a long time at High Temperatures.By HUGO WEISEE (Lanclw. Versucl~s-Stat., 1897, 48, 379-389).--8 number- of glass jars were filled with hay and heated in a water oven. Half of the jars were left open, whilst the other half were closed after moistening the contents with distilled water. The hay was analysed in its original condition, and at intervals of a month, for 6 months. The dry hay gradually became light brown, whilst the moistened hay soon acquired a d a ~ k brown colour. There was a progressive loss -of dry substance in both cases, but much more with the damp than with the dry hay. The amounts of ether extract and of crude fibre diminished, whilst the proteids, and especially the non-nitrogenous extract, increased.VEGETABLE PHYSIOLOGY AND AGRICULTURE.135 There was, however, a very great decrease of digestible proteids ; whilst the original hay contained 1.21 per cent. of digestible, and 0.76 per cent. of indigestible, nitrogen, the dry hay contained, after 6 months heating, digestible, 0.46 ; indigestible 1.72 per cent., and the damp hay, digestible 0.25, indigestible 2.04 per cent. Heating f o r 4 days had practically no effect on the digestibility of the proteids. N. H. J. M. Action of Potassium Chloride on the Lime Resources of the Soil. By CHARLES A. GOESSMANN (Hc& Pxpey. Stat. Nccss. Agric. toll. Bull., 38, 1896, 14-16).-Experimental plots which had for years received potassium chloride yielded crops of unhealthy appearance. After an application of slaked lime (500-600 lbs.per acre), the suc- ceeding crop was healthy. Analyses of the drainage from each plot a t the end of the season, showed the presence of a larger amount of lime in the case of plots which had received potash in the form of chloride, than where potassium sulphate had been applied. It is concluded that when land containing limited amounts of lime is manured with potassium chloride, lime should be directly applied from time to time. It is safer t o apply potassium chloride to deep soil with a free subsoil, than to a shallow soil with a compact clay subsoil. I n the latter case, there is a possibility of an excessive accu- mulation of calcium and magnesium chlorides near the roots of the plants. N. H. J. M. By MAX SCHMOEGER (Lcc7tclw. VersuclwStn;t., 1897, 48, 41 3--418).--Basic slag (5 grams) was fused with precipitated silica (0.6 gram) and the phos- phoric acid determined in the product, as well as in the original slag, and in the slag fused without silica. The following results were ob- tained :- Remarkable Observation on Ignited Basic Slag P,O,. 0 Citrate-solnble SiO,. Total per cent. per cent. per cent. of total. Original slag ..................... 2.23 20.1 9 48.4 Fused with silica ............... 12.07 17-80 83.5 Fused without silica ......... 2.25 19-87 20.1 The fused samples were ground more finely than the original slag before analysis. Whilst fusion without silica resulted in a gain i n weight (0.5 per cent.), when fused with silica the substance lost about 0.6 per ceat. in weight owing to evolution of carbonic anhydride. Two other samples of slag were ignited with and without silica. With silica, there mas, as before, an increase in soluble phosphoric acid. Withoat silica, there mas also a distinct increase, instead of a decrease, in soluble phosphoric acid, and there was a decrease instead of an increase in weight. (Compare G. Hoyermann, Die C'it~*atloslich- keit d. PL?osphors&iui.e in, Thomasnzehl.) N. H. J. AT.

ISSN:0368-1769    

DOI:10.1039/CA8987405127

出版商:RSC    

年代:1898

数据来源: RSC

摘要:

136 ABSTRACTS OF CHEMICAL PAPERS. Analytical Chemistry, Four New Methods of Measuring Gases. By OTTO BLEIER ( B e y . , 1897, 30, 2753--2759).-A new compensation method is first described, in which i t is not the standard gas, but the gas under examination, that is kept constant in volume, or is adjusted to a known fraction of its original volume. The apparatus in the figure, which is designed for the analysis of ordinary air, is surrounded by a water-jacket. A is filled with the gas to be examined and holds 100 C.C. down to the mark a, 79.5 C.C. down to the mark b. B contains the standard volume of a i r ; i t holds 100 C.C. down to c, and the space between c and d contains 1 C.C. and is gradu- ated in 0-01 C.C. Both vessels having been filled, to GG and c respectively, a t the atmo- spheric pressure, their upper extremities are connected by means of the capillary tube shown in the figure; there is a drop of liquid in the centre of this, which drop will remain in the centre if the two stop-cocks (h, and 1 ~ ~ ) be opened.After absorption of the carbonic anhydride, the liquid is brought to its original levels (a and c ) in A and B, and the two stop- cocks are opened, There is now a slightly diminished pressure in A, owing to the absorp- tion that has taken place, and consequently the drop of liquid moves towards A ; the liquid in c, d is lowered until the drop comes back to its original position. If the volume from c to the point to which it has been lowered is 0.15 c.c., then the percentage of 100 carbonic anhydride is 0.15 x ___ 100.15' The oxy- gen is now absorbed, and the same process is again gone through, except that the liquid in A is brought to the level b instead of cb (ah = 20.5 c.c.).Supposing the final level in cd to be 0.53 c.c., then the percentage of oxygen is 20.5 + 0.53 x - ~ ~ - 79'5 100.5 3' The advantage of this method is that the measurements are made with great accuracy, and, further, all under approximately the same pressure, so that the use of water is permissible. A special apparatus is required, however, for the analysis of &any particular gas, as measurements can only be made in the neighbonrhood of those percentages with which the fixed marks on A correspond. The apparatus 6gured can also be used for Compensation measure- ments in the ordinary way, the gas under examination being the one of which the volume is accurately measured.This gas is then con-ANALYTICAL CHEMISTRY. 137 tained in B which it fills to d, the volume down to this point being now 100 C.C. ; A now contains the standard volume of air, and is filled only to b under atmospheric pressure. After absorption of carbonic anhydride, the percentage absorbed is measured by the rise in d, c, when the drop of liquid has been adjusted to its initial position in the capillary tube. I n measuring the oxygen absorbed, the level in A must be brought to a. A combination of the two methods may also be adopted, both pipettes being graduated below ; the second method is used first, as far as the apparatus allows, and then the first method. An arrangement is next described which permits of measurements of volume by means of pressure readings.The pipette, which is en- closed in a water-jacket, consists of 5 bulbs, each approximately of 20 c.c., on the narrow connecting-tubes of which marks are placed, one between each pair of bulbs; the volume of the pipette down to each of these marks is accurately known. I n connection with this measur- ing pipette, there is a movable reservoir and a graduated manometer tube which is clamped in position and extends about 60 em. above and below the lowest mark of the pipette ; a t the same levels as this mark and those above it, marks are drawn on the manometer. The gas is first compressed to the lowest mark and the pressure noted in the manometer ; after the absorption of one of the constituents, the pressure is again noted, the volume being adjusted to the same mark, or, if that is impossible, to one above it.This apparatus can be used with water, This is enclosed in a water-jacket, and consists of two parallel vertical branches. One branch is a cylindrical tube, graduated, and holding 20 C.C. from the uppermost to the lowermost graduation; the other consists of 4 bulbs, with marks, one on the constriction below each bulb ; the volume from the uppermost graduation on the other tube to these marks is known accurately, and is approximately 20, 40,60, and 80 C.C. The two branches are joined in one piece at the top by a con- necting tube to which the glass stop-cock for the admission of the gas is also fused ; at their lower ends, the two branches are connected with a movable reservoir, by means of a three-way tube and india-rubber tubing.I n measuring the gas, the liquid is first driven up to one of the marks (whichever is suitable), the india-rubber tubing below this is closed by a spring clip, and then the reservoir is adjusted so that the level of the liquid is the same in it as in the graduated branch of the pipette; the volume of the gas is then read off. Separation and Estimation of Chlorine and Bromine in a Mixture of Alkali Salts. By HENRI BAUBIGNY and PAUL RIVALS (Conipt. rend., 1897, 125, 607-610).-When estimating bromine by expelling it from solutions of bromides by the combined action of cupric sulphate and potassium permanganate (this vol., ii, go), the concentration of the liquid is an important factor; if the solution is dilute, a relatively larger quantity of copper sulphate must be added in order t o ensure complete liberation of the bromine.Provided that an excess of permanganate is present, the exact proportion of it has little influence on the accuracy of the result. Direct experiments show that chlorides are not decomposed under the conditions specihed, provided Lastly, a measuring pipette with resorve spaces is described. C. F. B. VOL. LXXIV. ii. 10138 ABSTRACTS OF CHEMICAL PAPERS. the quantity in 100 C.C. of liquid containing 15 to 16 grams of crystallised copper sulphate and 0.7 to 0.8 gram of potassium per- manganate is not equivalent to more than the 0.250 gram of sodium chloride ; under these conditions, however, the whole of the bromine is liberated.The time required for complete elimination of the bromine is practically unaffected, within ordinary limits, by the proportion of bromide present, but the last traces of the bromine are somewhat difficult to expel. Detection of Traces of Bromine by Means of Fluorescein. By HENRI BAUBIGNY (Compt. Tend., 1897, 125, 654-657).-Paper prepared with a somewhat concentrated solution of fluorescein in acetic acid is placed in the mouth of the vessel, or in a tube leading from the vessel from which the gas or vapour supposed to contain bromine is issuing. The presence of even minute quantities of bromine is indicated by the appearance on the paper of pink streaks, due to the formation of eosin. The method is not applicable to mixtures of sinall quantities of free bromine with large quantitiesof free chlorine, but in the case of a mixture of chloride and bromide the bromine can be liberated by means of copper sulphate and potassium permnnganate.Estimation of Phosphorus in Steel, Iron, and Iron Ores. By JULIUS OHLY (Chem. News, 1897, '76, 200--201).-Two grams of steel are dissolved by heating with 45 C.C. of nitric acid of sp. gr. = 1.16, 5 C.C. of saturated potassium permanganate solution is added, and the whole boiled until the pink colour disappears; five or six drops of saturated sugar solution is then dropped in to dissolve the precipitate, avoiding excess, and the whole cooled t o 60". It is then shaken with 5 C.C. of ammonia until clear, 30 t o 40 C.C. of molybdate solution is added, the whole well shaken, filtered, washed six times, and the flask mixed with 2 per cent.nitric acid, then with 2 per cent. potassium nitrate. The filter and precipitate are returned to the flask, the precipitate dis- solved in 25 c-.~. of standardised sodium hydroxide, and three or four drops of phenolphthalein added to the solution, which is then titrated with nitric acid, standardised against steel having a known percentage of phosphorus. The measurement of the bulk of the molybdate precipitate, and so C. H. B. C. H. B. - - indirectly of the phosphorus, in a Goez tube -is also suggested. D. A. 1;. Estimation of Nitrogen in Guano. By V. SCHENKE (Chenz. Zeit., 1897, 21, 490).-The author has proved by a series of analyses that the nitric nitrogen contained in guanos is best calculated from the difference between the total nitrogen and that obtained by Kjeldahl's process.Haselhoff's water extraction method gives untrustworthy results, although better results may be obtained by using cold water (compare Estimation of Phosphoric Acid as Phosphomolybdic Anhydride. By WOY (Chem. Zeit., 1897, 441-443, 469-472).- The following reagents are required. A solution of 120 grams of ammonium molybdate in 4 lit,res of water; a solution of 340 grams of this vol., ii, 36). L. DE K.ANALYTICAL CHEAllS'l'lt Y. 1.39 ammonium nitrate in 1 litre of water ; nitric acid of 1.153 sp. gr. ; a washing solution containing 200 grams of ammonium nitrate and 160 C.C. of the nitric acid (sp. gr. 1.153) in 4 litres. The sample is dissolved in sulphuric acid, made up t o a definite bulk, and a n aliquot part, representing about 0.5 gram of material, is neutralised with ammonia and mixed with 10 or 20 C.C.of nitric acid; after adding 30 C.C. of the ammonium nitrate solution, the liquid is heated t o boiling, and a slight excess of the molybdate solution is added, 5 C.C. of which is equivalent to about 1 per cent. of phos- phoric acid in the sample. The precipitation is complete within 15 minutes, and the deposit iscollected and washed with 50 C.C. of the hot washing solution To purify it, it is dissolved in 10 C.C. of an 8 per cent. solution of ammonia and then mixed with 20 C.C. of the ammonium nitrate, and also 1 C.C. of the molybdate solution. After heating t o boiling, 20 C.C. of hot nitric acid is added to reprecipitate the compound.It is then collected in a Gooch's crucible, and after being washed with the acid ammonium nitrate, it is ignited at a dull red heat, The black residue contains exactly 3.946 per cent. of phosphoric Toxicological Detection of Arsenic. By E. FRICKE (Chem. Zeit., 1897, 21, 303).-When using Marsh's test, it sometimes happens that very slight mirrors are obtained which, however, may consist of carbon. I n order t o positively say whether arsenic is absent, the author recommends the following process. The decolorised solution is, as usual, treated with hydrogen sulphide, the precipitate which forms is dissolved in ammonium sulphide, the solution evaporated to dryness and the residue fused with sodium car- bonate and nitrate ; the melt is then dissolved in water, evaporated with sulphuric acid, and the residue dissolved i n water and again treated with hydrogen sulphide.Owing to the complete absence of organic matter, any yellow coloration o r precipitate points t o the presence of arsenic, but if the liquid remains clear, arsenic is certainly absent. To ascertain whether the yellow precipitate is really arsenic Detection of Thioxyarsenic Acids. By LEROY W. MCCAY (Chern. Zeit., 1897, 21, 487).-A dilute solution of sodium orthomono- thioxyarseniate gives with strontium chloride a white, amorphous pre- cipitate of the corresponding strontittm salt which soon becomes crystalline, whilst if barium chloride is added to the dithioxy-salt of sodium, the corresponding barium salt is produced. I n this way, the two arsenical compounds may be separated by first removing the mono- compound with strontium chloride and then precipitating the di-salt by barium chloride.The mono-compound may also be utilised for separating calcium from Titration of Sodium Thiosulphate with Iodic Acid. By CLAUDE P. WALKER (Amer. J. Sci., 1897, 4, 235-242).-Riegler has stated t h a t sodium thiosulphate may be titrated by means of iodic acid, using starch as indicator; directly all the thiosulphate is anhydride. L. DE K. it must be tested in the Marsh's apparatus. L. DE K. barium. L. DE K.140 ABSTRACTS OF CHEMICAL PAPERS. converted into tetrathionate and iodide, the addition of more iodic acid liberates iodine and gives rise to a blue coloration. By a long series of experiments, the author has proved that the reaction between iodic acid and sodium thiosulphate is so indefinite in its nature and so influenced by time, dilution, and mass, that the method proposed by Estimation of Carbon Bisulphide in Alcohol.Carbon Tetra- chloride, &c. Purification of Carbon Tetrachloride and &. New Compound of the same. By W. SCHMITZ-DUMONT (Chem. Zed., 1897, 21, 487-488, 510--511).-The usual process is t o boil the spirit with potassium hydroxide dissolved in alcohol, the potassium xanthate thus produced being estimated in various ways. The author prefers oxidising it with potassium permanganate in an alkaline solution, and estimating the sulphuric acid thus produced." The results are, however, generally a trifle low; the following method is better: 10 C.C.of the sample is heated with 20 C.C. of alcoholic solution of lead acetate and 10 C.C. of normal alcoholic potash for 20 minutes at 50-60'; the lead sulphide formed is then collected, and the sulphur converted into sulphuric acid by means of nitric acid and bromine. Another process is given, based on the formation of silver snlphide; 10 C.C. of the sample is mixed with 50 C.C. of a 5 per cent. alcoholic solution of silver nitrate and 5 C.C. of aniline, and the whole is then heated for half a n hour a t 60'; t h e silver snlphide thus obtained is afterwards fused with sodium nitrate and carbonate, t o convert the sulphur into sulphate. Carbon tetrachloride may be freed from carbon bisulphide by dissolving a quantity of potassium hydroxide, more than sufficient to decompose the carbon bisulphide, in 100 C.C.of alcohol, and adding this t o a litre of the chloride. After heating for half an hour a t 60°, the xanthate is precipitated by adding water, and the liquid is repeatedly washed with water until free from alcohol. To free the tetrachloride from any trichloride, it is first dried over potassium hydroxide and then distilled over paraffin. The author has found that, on prolonged contact, carbon tetra- chloride and phenylhydrazine yield silky needles of the composition [* NOTE BY ABSTRACTOR.-In reference to the oxidation of sulphur in an alkaline solution by means of permanganate, compare Abstr., 1895, ii, 184.1 By HARRY BREARLEY (Chem. News, 1897, '76, 189--191).-To avoid the uncertainty connected with the ordinary method in which the discharge of colour is taken as the final stage, the author suggests rnnning in cyanide until this stage is reached, then adding potassium iodide and titrating back to a permanent turbidity with silver nitrate.H e finds in this case also (compare Davies, Chem. News, 1888, 58, 131) that the use of sodium carbonate instead of ammonia is advantageous, inasmuch as increasing volume of liquidi or quantity of alkali, or copper, or cyanide, or the presence of alkal chlorides, nitrate, or acetates seriously derange the titration in the latter, bat, n'ot i a the former case (compare Thomson, Riegler is quite impracticable. L. DE K. ( C,H5*NH*NH2),HC1. L. DE K. Cyanide Titration of Copper.ANALYTICAL CHEMISTRY. 141 Chew. Art?tus, 1880, 33, 152, and J.J. and C. Beringer, Abstr., 1884,113), except with nitrates, and this can be overcome by using greater excess of sodinm carbonate ; nitrates, acetates, and sulphates, however, but not chlorides, cause a more or less inky solution that masks the turbidity due to the silver iodide, but the addition of sodium chloride cures this defect. I n the presence of ferric iron, the usual method is useless, the modified method successful, whilst in the presence of aluminium or manganese the results accord with the usual titr&on. Besides manganese, nickel, cobalt, zinc, mercury, silver, gold, platinum, and palladium interfere with the reaction. Estimation of Mercuric Salts. By LVDWIG VANINO and F. TREUBERT (Bey., 1897, 30, 2808-2809. Compare Abstr., 1897, ii, 601).-'l'he solution is mixed with excess of commercial hydrogen per- oxide (containing hydrochloric acid), phosphorous acid is added, and the whole is warmed on the water bath until the precipitate of mercurous chloride has clotted ; this precipitate is collected on a tared filter, dried a t 1 0 5 O , and weighed.In five experiments, the percentage of Hg found was 73-82-74.01 ; calculated 73.85. Phosphorous acid may thus be used as a reducing agent, instead of hypophosphorous acid ; the hydrogen peroxide prevents a further reduction to metallic mei-cury, which other- wise would take place a t the temperhture of the water bath. D. A. L. C. F. B. Analysis of White Paints. By GUSTAVE W. THOMPSON (J. Soc. Chem. Ind., 1896, 15,432-434, 791).-The pigments most frequently met with in the white paints of commerce are white lead, lead sulphate, zinc oxide, the so-called '' sublimed white lead," which consists of lead sulphate with varying proportions of lead and zinc oxides, barytes, cal- cium sulphate, calcium carbonate, china clay, silica, zinc sulphide, and lead sulphite. For extracting the oil, the author prefers '' C.P. benzol" although any of the usual solvents may be used ; sufficient organic matter may remain, however, to render valueless any direct estima- tion of combined water. The exact course of the quantitative analysis will depend on tbe results of a previous qualitative examination, in which the solubility of all lead compounds (except sulphite), zinc oxide, and calcium salts in boiling acid ammonium acetate is mainly to be de- pended on.The methods recommended for the estimations are in the main those of the ordinary text-books ; onlp the special methods are, therefore, noticed here. White lead is calcula teed according to circum- stances either from a carbonic anhydride estimation, or from the lead soluble in acetic acid, the arbitrary formula, 2PbCO,,PbH,O,, being adopted. For the separation of lead compounds (other than sulphite) from barytes, china clay, &c., their solubility in acid ammonium acetate is made use of. Lead sulphate may be regarded as insoluble in acetic acid, and be thus separated from lead oxide and white lead. Since a mixture of lead sulphate and calcium carbonate cannot be treated with water without the occurrence of double decomposition, calcium sulphate cannot be dissolved out from a mixture of the three substances.The total calcium must be estimated in one portion, and another portion b s treated with a cold mixture of 9 parts of 95 per cent. alcohol and 1 part of nitric acid (sp. gr. = 1.4), which dissolves the calcium car-142 ABSTRACTS OF CHEMICAL PAPERS. bonate and leaves the calcium sulphnte. A gram of the sample is treated four times with this solvent, for 20 minutes each time, and the decanted and filtered liquids are evaporated to dryness. The residue is heated with excess of strong sulphuric acid until fumes appear, then dissolved in acidified ammonium acetate, freed from lead and zinc by hydrogen sulphide, and the calcium estimated as usual. Separation of Aluminium from Beryllium by the Action of Hydrochloric Acid.By FRANKE 8. HAVENS (Arne?.. J. Xci., 1897, [iv], 111--114, and Zeit. anorg. Ch., 16, 15--18).-The author, in a previous communication (Abstr., 1897, ii, 2 3 2 ) , has proved that alumina may be completely separated from iron oxide by dissolving in hydrochloric acid, adding an equal bulk of ether, and saturating it with hydrogen chloride. The aluminium is then completely precipitated as chloride, which, after being washed with a mixture of acid and ether saturated with hydrogen chloride a t 15", is converted into oxide by ignition with mercuric oxide. The author now states that the process is equally applicable in the presence of beryllium. After removing the aluminium as described, the filtrate is evaporated to dryness and the residue is converted into nitrate by evaporating with nitric acid.This, on strong ignition, leaves pure beryllium oxide. M. J. S. The test analyses show the great accuracy of the process. Assay of Carbonated Manganiferous Minerals. By N. DEVISSE (Chem. ~Vews, 1897, 76, 21 2-2 13).- Manganese, w6en preci- pitated in the presence of oxidising agents, tends to form compounds of the general formula 5&1n02,M0 ; MO being manganous, zinc, cal- cium or other oxide : for example, by adding l equivalent of permanga- nate to four equivalents of manganous chloride, neutralising theliberated acid, all the manganese is precipitated in this form, as shown in the equation 4MnC1, + Mn208K2 + 3H,O = 5Mn02,Mn0 + 2KC1 + 6HC1. The presence of zinc or lime salts might in this way affect gravimetric results, hence volumetric methods are advocated, and if precipitated zinc oxide is added prior to the treatment with permanganate in Volhard's method, then the chlorides need not be transformed into sulphates.D. A. L. Estimation of Iron and Aluminium in Mineral Phosphates, Manures, Alum, &c. By ROBERT T. THoblsoN (.I 8oc. Chern. Ind., 1896, 15, 868-S69).-1n an earlier paper on this subject (Abstr., 1887, 302), the precipitation of iron and aluminium phosphates, free from calcium, from a solution containing calcium phosphate, was effected by ammonium acetate strongly acidified with acetic acid. Gladding (Abstr., 1897, ii, 125) adopts the same method, with the condition that the solution be heated to 60°, but in either case several reprecipitations may be necessary to ensure complete absence of cal- cium from the precipitate.This difficulty appears to be a direct result of the presence of ammonium acetate, and the author, therefore, now reverts to his '' neutralisation " method, which consists in the cautious addition of ammonia to the hydrochloric acid solution of the mixed phosphates, until sensitive blue lacmoid paper indicates that only a L. DE K.ANALYTICAL CHEMISTRY. 143 minute trace of free acid remains. One part of aluminium phosphate requires 3 parts, and 1 part of ferric phosphate 12. parts of free phos- phoric acid to hold i t in solution, so that with care in the neutralisation the precipitation of both is practically perfect, whilst the precipitate is completely free from calcium. The aluminium and iron phoqphates so precipitated will be normal phosphates if the solution contained a t least 1.5 times the theoretical proportion of phosphoric acid, otherwise they will be basic.This normal composition, and also the gelatinous condition, will be retained if the precipitate is washed with a 1 per cent. solution of ammonium nitrate containing 0.3 gram of ammonium dihydrogen phosphate per litre, this solution being, if necessary, care- fully made neutral to methyl-orange by the addition of phosphoric acid. Although the portion of this solution retained by the drained precipitate will leave i t s phosphoric acid when the precipitate is ignited, the error is too small to be of importance. Should the sub- stance under analysis contain calcium fluoride, the evaporation of its hydrochloric acid solution to dryness with nitric acid will eliminate the fluorine.The nitric acid should not be added until the hydrochloric acid solution has been filtered from any pyrites which the substance may contain, because this mineral is left unaffected in the manu- facture of superphosphate, and its iron should, therefore, be reported separately . The above process serves equally well for the separation of aluminium and iron from nickel, cobalt, zinc, manganese, and magnesium. M. J. S. Separations with Alkali Acetates. IV. Chromium from Iron. V. Aluminium and Copper from Iron. VI. Zinc from Iron. By HARRY BREARLEY (Chem. News, 1897, 76, 175-177, 210-211, 222-224. Compare Abstr., 1897, ii, 588, and this vol., ii, 96).- Chromium cannot be separated quantitatively from iron by means of sodium acetate either when much or little acetate or free acid is used, although the separation is better when the larger quantities are em- ployed, especially with plenty of strong acetate.The separation, too, is better in the case of a chrome steel containing from several tenths t o 2 or 3 per cent. of chromium than i t is from solutions having 0.1 gram of chromium to I gram of iron. The imperfect separation isattributed to the formation of iron chromates, and it seems that aluminirirn forms similar compounds with iron, since no useful separation of aluminium from iron can be effected by alkali acetates, whether in the presence of much, little, or no acetic acid, or dissolved hydroxide. A much larger quantity of acetate is required to completely precipitate the iron in the presence of much aluminium, some of which is also precipitated.These factors might interfere with some of the separations, but in the case of steel there is usually a harmless amount of aluminium and as much as 60 C.C. of acetate and 10 per cent. of aluminium does not greatly upset the nickel and iron separation when 0.1 gram of nickel is present, but under such circumstances this separation would be ren- dered more perfect by using large amounts of ammonium chloride and less acetate ; the use of alkali chromate is likewise mooted for this purpose.144 ABSTRACTS OF CHEMICAL PAPERS. The separation of copper from irou by acetate is not quantitative, the presence of free acid, however, favours accuracy, although much acetate has the contrary effect, whilst Schwarzenberg’s method is effec- tive for this separation.To estimate copper in steel or iron compounds containing less than 0.5 per cent., the procedure when using sodium cyanide titration is as follows: 5 to 10 grams is dissolved in dilute sulphuric acid, the solution treated with hydrogen sulphide or prefer- ably, with sodium thiosulphate, but only in slight excess, and the liquor poured off through a filter. The precipitate is washed by decantation, and after being mixed with the residue from the ignition of the filter paper, is heated with 10 to 20 C.C. of nitro-hydrochloric acid and potassium chlorate ; when all but sulphur is dissolved, the solution is cooled, diluted, neutralised, made alkaline with sodium carbonate, and titrated with sodium cyanide,as described by the author (thisvol.,ii, 140).The separation of zinc from iron can also be completely effected by the acetate method. In all the separations by this method, it is t o be rernetnbered that the phosphoric acid is precipitated with the iron acetate; that the tem- perature at which the turbidity appears should be recorded; that cooling the solution before adding the acetate is only necessary when any large excess of acetate is used; that the decomposition of acetates on heating accounts for the presence of free acetic acid in the case of ferric acetate, and may account for some of the imperfect separations recorded by the author; that, knowing the amount of acid used for dis- solving, the necessary quantity of alkali required for neutralising may be added a t once and the rest several C.C.a t a time until there is an unmistakably permanent turbidity, which turbidity is dissipated by adding 10 or 12 C.C. of acetic acid, but, on diluting with hot water and heating, should reappear a t about 90°, otherwise a few C.C. of dilute acetate should be added ; in this way, nickel in a nickel steel may be determined with great rapidity, D. A. L. Estimation of Nickel and Zinc as Phosphate. By JOHN CLARK (J. Soc. Chem. Ind., 1896, 15, 866-868).-Experience has confirmed the value of the ammonio-phosphate process devised by Dirvell and modified by the author (Abstr., 1880, 2S7; 1884, 498 ; 1890, 1470) for the separation of cobalt from nickel, but the estimation of the nickel in the filtrate is less satisfactory.By adding dilute hydrochloric acid to the cold or moderately warm liquid until i t is neutral or nearly neutral to test-paper, the nickel is precipitated as the double phosphate of the formula NiNH,PO, + 6H,O ; this loses rather more than 5H,O at looo, and on ignition is converted into nickel pyrophosphate. It is slightly soluble in water, but if 20 per cent, of alcohol is added after neutralisation, and the precipitate is washed with cold water contain- ing 10 per cent. of alcohol, the loss is unimportant. If the above process i s applied to a mixture of cobalt and nickel salts in which the cobalt exists in the cobaltic state, the nickel only is precipitated. For this purpose, the solution containing the metals as chlorides is mixed with 10 times as much ammonium phosphate as the weight of metal present, and is heated for a few minutes with hydrochloric acid and a considerable excess of bromine.While free bromine is still present,ANALYTICAL CHEMISTRY. 145 the solution is supersaturated with ammonia and heated with hydrogen peroxide ; it is then cooled, neutralised with dilute hydrochloric acid as above, and stirred. Alcohol is added, and after several hours the pre- cipitate is collected and washed as above. When much cobalt is present, it may be desirable to re-dissolve in hydrochloric acid, add ammonium phosphate, oxidise, and reprecipitate as before. I n this way, 1 part of cobalt may be detected and estimated even when ac- companied by 200 parts of nickel. The above method applied to an ammoniacal solution of zinc chloride, containing enough ammonium chloride to form a double salt, precipitates the whole of the zinc as ZnNH,P04.This can be washed with cold water, is anhydrous after drying over sulphuric acid, but bears ignition (apart from the filter) without loss of zinc. To apply this method to zinc ores, the iron, alumina, and manganese are removed by ammoniacal hydrogen peroxide, and most of the calcium by am- monium carbonate added to the hot alkaline liquid. The rest of the calcium and the magnesium are thrown down when the ammonium phosphate is added,‘ but this precipitate is free from zinc. M. J. S. Assay of Chrome Ore. By ELWYN WALLER (J. Xoc. Chem. Ind., 1896, l5,436--437)-The author reports his experience of the fusion of chrome ore with sodium peroxide in nickel crucibles (see Trans., 1893, 1079, and this vol., ii, 94).About 0.5 gram of ore in impalpable powder was weighed into a nickel crucible (35 mm. in diameter at the top, 30 mm. deep, and weighing 9-12 grams) and well mixed with about 2 grams of dry powdered sodium peroxide. The mass was fused by a small flame and after being kept in tranquil fusion for 8-10 minutes, the temperature was raised to a visible red heat, the crucible being moved for 1 minute in such a way as to give a rotatory motion to its contents. The cooled melt was dissolved in boiling water (50-80 c.c.), the solution boiled for 5 minutes to decompose excess of peroxide, some of which was always found t o be present, then filtered, acidified with sulphuric acid, and after dilution to 600-700 C.C.titrated with standard thiosulphate (30 grams per litre), with the ad- dition of potassium iodide (1.5-2 grams)&and starch towards the end. Decomposition of the ore was complete ; a single experiment with ore ground only until it would pass through a ‘‘ 60-mesh ” sieve indicated that the method would probably serve for such coarse ore. Employ- ment of a shallow basin instead of the crucible resulted in imperfect decomposition. The crucible lost 0.02-0.05 gram at each fusion. The use of a larger proportion of peroxide or a higher temperature caused a stronger attack of the crucible. Heavier crucibles than the above lost proportionally more, By JOHN CLARK (J. SOC. Chern. Ind., 1896,15,255-257).-1f antimony o r an antimony ore is dissolved in hydrochloric acid with the assistance of iodine, the oxidation does not proceed beyond the stage of trichloride, and after boiling off the excess of iodine, the solution is at once fit for titration by Mohr’s method, using iodine solution in presence of an excess of alkali tartrate and sodium hydrogen carbonate.Should it be found M. J. S. Estimation of Antimony in Ores and Metals. 11146 ABSTRACTS OF CHEMICAL PAPERS. on adding starch (aFter the boiling and cooling) that a trace of free iodine remains, this can be cautiously removed by adding sodium sul- phite. Since, in acid solution, tin is oxidised to stannic chloride by iodine, i t has no effect on the result. Lead is also inert, but in the presence of copper the results are too low; in this case, as also in presence of iron, it becomes necessary t o precipitate the metals as sul- phides and dissolve out, the antimony sulphide by potassium hydroxide.The reprecipitated antimony sulphide is then dissolved by hydrochloric acid and iodine. Arsenic would also vitiate the results, but i t can be removed by repeatedly boiling down with copious additions of strong hydrochloric acid. M. J. 5. Assay of Electro-plating and Gilding Solutions. By ALFRED H. ALLEN (Chem. News, 1897, 76, 199).-Whilst approving Baker’s method (this vol., ii, 93), the author prefers one he has long used, in which 20-50 C.C. of the plating solution, largely diluted with water and heated to boiling, is treated with hydrogen or ammonium sulphide, and the washed precipitate mixed with excess of bromine water, any sulphur i n the residue being oxidised by the use of a small quantity of bromine. Boiling water is then added and the silver bromide washed, dried, fused, and weighed.Electro-gilding or silvering solutions are evaporated in a porcelain crucible to a syrupy consistency, and mixed with red lead or litharge; the mass dried, heated a short time a t moderate redness, and the button cupelled, or, in the case of gold, treated with nitric acid, if preferred. D. A. L. Preparation of Water Free from Ammonia. By JOSEPH BARNES {J. SOC. Chern. Irzd., 1896, 15, 254--255).-Distilled water can be com- pletely freed from ammonia by adding a little bromine and boiling for a few minutes, More rapid is the action of alkaline hypobromite in the cold.Enough bromine is added to the water to give it a perceptible tint, and then a drop of sodium hydroxide solution ; after ten minutes, a little potassium iodide is added to remove the undecomposed hypo- bromite, and the water is then fit for use in the estimation of ammonia by Nessler’s test. By MAXIMILIANO DENNSTEDT (Rev., 1897,30,2861-2962. Compare Abstr., 1897, ii, 432).-1n analysing compounds containing nitrogen and halo- gen by the author’s method, the percentage of halogens is often found too high, because the silver retains oxides of nitrogen. After the silver boat has been weighed once, it should be heated in a Bunsen flame till the silver haloids melt, and reweighed, any silver nitrate or nitrite is thus destroyed. It is well t o do this in all cases, even when the sub- stance analysed contains no nitrogen. Formaldehyde as a Reagent.By HERMANN ENDEMANN (2 Xoc. Chem. Ind., 1896, 15, 791-7!32).- Substances of the phenol class combine with formaldehyde, forming colourless compounds which be- come coloured on treatment with concentrated sulphuric acid. To obtain the reaction, the phenol is dissolved in commercial formalin, the solution evaporated nearly to dryness at a low temperature, and M. J. S. Simplified Organic Analysis (Supplementary Obsei-vation). C. I?. B.ANALYTICAL CHEMISTRY. 147 The solid. Magenta-coloured .............................. Red ............................................... Brown, with claret shade. .................... Orange to orange-red ........................ Violet, quickly brownish-violet ............Scarlet-red ..................................... Brown ............................................. Faintly fawn-eoloured (due to imparity 2) Green ........................................... Green, then black .............................. Red Red, then brown .............................. No reaction ................................................ ....................................... concentrated sulphuric acid added. recorded, The following reactions have been The solution. Magenta-coloured. Magenta. - - - Orange. Brown. Brown. Green. - - - - Phenol ...... Salicylic acid Eugenol ...... Carvacrol ... Guaiacol ..... Resorcinol ... Quinol ...... Thymol ..... a-Naphthol B-Naphthol Pyrogallol ... Haematein ... Tannin ...... Other aldehydes afford similar reactions, but the colours are different. Silk which has been treated with formaldehyde to render the sericin insoluble gives a different reaction with sulphuric acid (rich brown, passing through olive-green to green as moisture is absorbed) from that of silk not so treated. Washing the treated silk with hot water prevents the colour reaction from being obtained.Fehling’s Solution. By J. E. GEROCK (Ber., 1897,30,2865-2867). -The author has tested Siegfried’s statement (quoted by Jovitschitsch, this vol., ii, 98) that Fehling’s solution undergoes a spontaneous reduc- tion when alkaline sulphates, chlorides, or nitrates are dissolved in it, and found it to be erroneous. The essential constituent of a Fehling’s solution is a compound of the type R* 0 Cue 0 M’ or (R 0 Cu O)2M‘, where M’ is an alkali, M’ an alkaline earth, and R is an organic radicle not too readily oxidised.The author has used a solution in which the metal was barium and the organic substance salicylic acid. Reactions of Potassium Ferricyanide,with Glucose and their Applications to Volumetric Analysis. By N. TARUGI and G. NICCHIOTTI (Gaxxetta, 1897, 2’7, ii, 131--153).-See this vol., i, 118. Optical Analysis of Urine and Exact Estimation of Proteids, Glucosides, and Non-fermentable Saccharine Materials. By FR~DERIC LANDOLPH (Compt. rend., 1896, 123, 1301--1302).-Smlla amounts of sugar are best estimated by fermentation. When the sugar in urine is more than 10 grams per litre, it may be determined by the saccharimeter. The direct reduction coefficient can only be obtained with boiled and filtered urine, as otherwise a certain quantity of cuprous oxide remains in suspension ; two indirect reduction coefficients should be determined.( 1 ) The coefficient of the original urine after treatmentl with mineral acid, and (2) the coefficient of the boiled and filtered urine when treated in the samc manner. The difference between these coefficients gives the amount of mucin, &c., M. J. 8. C. F. B.148 ABSTRACTS OF CHEMICAL PAPERS. present, and the difference between the direct and indirect coefficients of the boiled and filtered urine gives the amount of glucosides. J. J. S. Estimation of Diabetic Sugar. By FR$D&RIC LANDOLPH (Compt. rend., 1897, 125, 612--613).-The polaristroborueter alone indicates the real quantity of active diabetic sugar in a solution. The coefficient of reduction gives double or treble the amount of sugar indicated by the polaristrobometer. Determinations by the method of fermenta- tion give results which vary greatly with the time that has elapsed between the end of the fermentation and the reading off of the volume of carbonic anhydride (compare Abstr., 189’7, ii, 5”12). C. H. B. Quantitative Separation of Cellulose-like Carbohydrates in Vegetable Substances. By WILHELM HOFFMEISTER (Landw. Versuchs- Stat., 1897,48, 401-411. Compare Abstr., l890,581).-To separate the hemicelluloses, celluloses, and the constituents of lignin without essential change, the substance, after being freed from fat, is extracted with dilute hydrochloric acid and ammonia, and the residue frequently agitated f o r a day or two with 5-6 per cent. caustic soda solution, It is then diluted, the extract poured off, neutralised with hydro- chloric acid, treated with sufficient alcohol, and the hemicellulose filtered, dried, and weighed. The residue from the soda extract is washed on a filter with hot water, and extracted with Schweizer’s reagent. When the final residue (lignin) is subjected to prolonged extraction with boiling dilute ammonia (a suitable apparatus is described, with sketch) until the ammonia is no longer coloured, a residue is obtained which mostly dissolves in Schweizer’s reagent, and on repeating the process the residue is found to consist largely of mineral matter. The dissolved cellulose-like substances often contain considerable amounts of pentosans. According to the nature of the substance, the extraction with ammonia may take weeks, or months, or even longer; the ammonia extracts of hard woods (as Lignurn uitce), and of cork, are dark brown, and give an odour of vanilla when evaporated down. The residues, which are insoluble i n water, but redissolve in ammonia, have the properties of humic acids. Other vegetable substances, when ex- tracted, yielded, besides humic acids, a compound, C6H702, soluble in alcohol and chloroform, but insoluble in water, ether, and benzene ; pre- parations from different sources melted between 200’ and 210’. N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA8987405136

出版商:RSC    

年代:1898

数据来源: RSC