摘要:

100 ABSTRACTS OF CHEMWAL PAPERS. Mine ra 1 o gic a1 C h e mi stry Gases Enclosed in Coal and Certain Coal Dusts. F. G. TROBRIDGE (J. SOC. Chenz. Ind. 1906 25 1129-1 130).-Analyses are given of the gases extracted at the ordinsry temperature and at looo from the coal of the Busty Seam at Eirtley Co. Durham. Separate dltts have been obtained for (1) bright coal ; (2) ‘; dant ” ; (3) surface d u s t ; (4) dust from timbers. The bright coal not only yields the largest volume but also the largest proportion of combustible gas. The combustible gas from the bright cod and from t h e ‘‘ dant ” consists almost entirely of methane whereas t h a t from the dust appears t o contain higher hydrocarbons. The analytical data confirm the observa- tion made by Bedson t h a t oxygen and nitrogen t h e former pre- ferentially are absorbed by coal on exposure to the air.Analyses of t h e gqs occluded in coal and dust from the Fernie Mine (B.C.) are also com mu n icat ed . H. M. I). Chalcopyrite Crystals from Japan. WILLIAM E. FORD (Amer. J Sci. 1907 [iv] 23 59-GO).-A crystallographic description isMINERALOGICAL CHEMISTRY. 101 given of peculiar wedge-shaped and lath-shaped crystals of chalcopyrite from Arakawn Japan; t.hey owe their unusud development to the symmetrical suppression of C ~ I tain faces. JACOB BECHENKAMP (Si,!x.-Bez.. phys.-wed. Ges. Wiirxburg 1906) has examined similar crystals from the same locality and concludes that they belong to the pyramidal (hemimorphic) class of the orthorhombic system and that the higher symmetry more usually exhibited by chalcopyrite is the result of twinning.L. J. S. Formation of Quartz and Tridgmite in Silicate Fusions. P. D. QUENSEL (Centr. Min. 1906 728-737).-A continuation of pre- vious work (this vol. ii 34). A mixture of oligoclase and quartz heated with an equal amount of tungstic oxide for six hours a t 900" resulted in the formation of quartz ; the same mixture at 1200" gave only glass. Amorphous silica with five parts of sodium tungstate heated for six hours a t 1200" gave tridymite ; a t lower temperatures only a glass was formed. The melting point of tridymite was deter- mined to be about 1560° that is about 100" lower than that cf quartz. Diagrams illustrate the temperature limits of the formation and stability of quartz tridymite and silicic acid (compare Day and Shepherd Abstr.1906 ii 770). L. J. S. Crystal Measurements. CARL HLAWATSCH (Zeit. Ifiyst. Min. 1907,42 587-595).-The results of goniometric measurements are given of the following raspite from Broken Hill New South Wales ; R triclinic rhodonite-like slag of unknown origin and composition ; and dibromohydroxydeoxybenzoin C~~~Yh*CO*~,,H,Br,*OH,B,O. The slag crystals have D = 3-44 and were found t o contain much manganese; they are therefore assumed to belong to the triclinic group of slag materials with the composition (Mg,Fe,Mn)SiO studied by J. H. L. Vogt and the name '' vogtite '' is proposed for them L. J. S. Nepouite a new Hydrated Silicate of Nickel and Magnesium. E. GLASSER (Conzpt. rend. 1906 143,1173-1175).-'I'he new mineral is from Nhpoui in New Caledonia and is met with a s a fine cryst,alline powder or as an incrustation in nickelferous peridotite.The colour varies with the percentage of nickel from bright green to pale yellowish-green. The hardness is 2-3. The minute crystals have the form of hexagonal plates or are vermiform with a six-sided cross- section ; they have a distinct basal cleavage and prismatic cleavage as in the chlorites. The crystals are optically negative with a small axial angle; the acute bisectrix is nearly perpendicular to the basal cleavage ; birefringence 0.036- 0-038. The following analyses (Ia IVa and V a by F. Pisani) give the formula 3(Ni,Mg)0,2Si0,,2H20; nickel and magnesium replace each other in all proportions. The mineral is near to but distinct from garnierite noumeite and connari te.102 ABSTRACTS OF CHEMICAL PAPERS.SiO,. 1. 32-84 Id. 32.30 11. 33.03 111. 35.05 IV. 40.07 IVn. 41.1 V. 32'36 V r c . 32.50 NiO. MgO. 49-05 3.64 49.75 3.75 46.11 6'47 39.99 11.80 18-21 29-84 18-1 30.0 50.70 3.00 50.20 3'47 FcO. CaO. 1-90 0.50 1.65 n. d. 2.20 trace 1.22 0-58 0-25 0.53 n. d. 11. d. 0'62 trace 0.83 11. d. A1,0,. H,O. Total. Sp. gr. 0.97 9'64 98.54 0.89 10.48 98'82 } 3'24 1'39 10'61 99.81 3-18 1.13 10.05 99.82 2.69 n. (1. n. d. - J 2'47 0.69 12.31 99-68 1 3.20 0.72 11.98 101'60 1 0.82 10'20 98.02 J L. J. S. Chemical Composition of Amphibole. SAMUEL L. PENFIELD and F. C. STANLEY (Amel*. J. Sci. 1907 [iv] 23 23-5l).-The following analyses (the results quoted are in each case the means of the duplicate analyses) were made on carefully-sel6cted and pure material with the object of deducing a general formula to express the wide variations in composition which are exhibited by the several varieties of amphibole. I Tremolite large white crystals from Richville near Gouverneur New York ; 11 tremolite white bladed crystals from Lee Massachusetts ; 111 actinolite dark green crystals in talc from Greiner Tyrol ; IT actinolite dark green crystals from Russell St.Lawrence Co. New York ; V actinolite dark olive-green crystal from Kragerii Norway ; VI actinolite dark greenish- black crystals of unusual habit from Pierrepont St. Lawrence Co. New York; VII hornblende black crystal from Renfrew Ontario Canada ; VIIT hornblende black crystals from Edenville Orange Co. New York ; I X hornblende (" hudsonite ") black and massive from Cornwall Orange Co.New Pork (fluorine determination addcd to the analysis given by 8. Weidman Abstr. 1903 ii 436) ; X hornblende small greenish-black crystale from Monte Somma Vesuvius ; XI basaltic hornblende black crystals from Bilin Bohemia ; XII hornblende light lorown cleavage masses from Grenville Quebec Canada (compare B. J. Harrington Abstr. 1904 ii. 52). Total (less 1,oss 0 for SiOz. TiOz. &O:+ Fe.303. FeO. b h 0 . MgO. CxO. KaO. Nn20. TT20. F2. at 110". Fa). Rp. 61'. 1 57.45 - 1'30 0'1s 0.22 0,07 24.85 12'83 0'5.1. 0.67 1.16 0.77 0.09 !r!t.ST 2.997 11. 57'69 0'14 1-SO 0.00 0'55 trace 24.12 13'19 0.22 0-48 1.3; 0.37 0'10 100'07 'L'USO 111. 56.25 0.00 1'24 0.78 5.50 0'4s 21.1!1 12'0s 0.25 0.19 1%1 0'04 - 9!IW 3.(147 1%'.54.50 0'10 2'515 2'50 4'76 tELCC 20.30 12'0s 0.24 0 3 2 1.60 0.77 0-11 100-33 Y.OC~2' V. 51.86 1*2G 4'3G 2.5s 5-46 0 3> 1!).4S 10"l 0'35 2.1.5 1.21 0'46 0.13 100'02 3.137 VI. 52.31 0.2s 2.139 3.09 G.68 0.70 1!).27 11% 0.60 0% 1'42 O'!U 0'08 100'20 3'111 VII. 43'76 0% S'33 0.90 10.47 0.50 12%3 9.54 1-28 3-43 O%S 1.82 0.10 99.73 3.2!)) VIII. 41 09 1'46 11'G'L 4.67 14.32 0.25 11.17 11.52 0.95 2-49 0-61 O'SO 0'0s 99.63 3.285 IX 36'SC; 1'04 12'10 7.41 23'35 0.77 1.!10 10'5!) 3'20 1'20 1'30 0.27 - !r!)*sy - 0.30 12.99 7% 10'73 1.00 11.47 12'01 2.30 1.70 0.71; 0.50 0-12 100.23 3-283 I'M 17.58 7.25 2'1s t,r:rce 14.15 ll'!)~; 1.0s B - l r i 0.41 0'30 0'13 100'45 3 226 1.20 11'37 0'42 0'12 0.39 21.11 12.71 1.69 2'51 0%; 'L.7ti - W.!IO 3.110 These analyses show that fluorine and water must be regarded as essential const,ituents of amphibole.The identity in crystalline form of the several varieties of the group suggests that a complex metasilicic acid HSSi4Ol2 or perhaps €I16Si8024 must have a controlling influence (mass effect) on the isornorphous replacement of the bases and basic radicles; for this amphibole acid a ring formula is suggested which is referred to as an amphobole ring. The hydrogen atoms of the acid are considered to be largely replaced by the bases K"O and by K,O Na,O,MINERALOGICAL CREMTSTRT. 103 H,O and F whilst the sesquioxides are introduced in the form of the basic radicles [R1*',O(OH F)J1 and [R1r120,R11Na2]11. The analyses (1-111) of the simpler varieties tremolite and actinolite give very closely the metasilicate ratios without the assumption of any complex radicles.I n all the analyses calcium oxide replaces one-fourth of the hydrogen atoms of the acid. L. J. S. Crystallographic Observations on Certain Minerals of Brosso and Traversella. LUIGI COLOMRA (Atti R. Accad. Lincei 1906 [v] 15 ii 636-644).-The author gives the results of measurements of crystals of villarsite which is crystallographically identical with olivine ; siderite [c = 0-81841 ; chalcopyrite [C = 0.986451 ; blende ; galena ; arsenical pyrites ; tetrahedrite ; cerussite [a b c == 0.60960 1 0.722551. T. H. P. Yttrocrasite a new Yttrium-thorium-uranium Titanate. WILLIAM E. HIDDEN and CHARLES H. WARREN (Amer. J. Xci. 1906 [iv] 22,515-519).-The crystal examined was found in Burnet Co.Texas not far from the well-known gadolinite locality in Llano Co. It weighed 60 grams and had a thin dull brown coating; on a fresh surface the material is black with a bright pitchy lustre and an uneven to small conchoidal fracture resembling polycrase or euxenite in appearance. The crystal is orthorhombic its hardness is 54-6 and D4.8043. Under the microscope thin splinters are pale yellow to coIourless and transparent; in polarised light i t is seen to consist of a mixture of isotropic and feebly birefringent material with sometimes a minute spherulitic structure. The mineral thus appears to have resulted by the alteration of an originally anhydrous species. The material is infusible before the blowpipe ; i t is easily decomposed by bydrofluoric acid and by strong boiling sulphuric acid.Details of the method of analysis are given. The results obtained by Warren are TiO,. (P,Er),O *. Ce,O Bc. Fe20,. WO,. U03. UO,. Tho,. PbO. 49'72 25.67 2.92 1'44 1.87 0'64 1.98 8-75 0'48 hliiO. CaO. CO,. II,O. H,O (hygiosc.). Total. 0.13 1-83 0.68 4'36 0.10 100'37 .t * Mol. wt. 268'4. Helium and nitrogen could not be detected. t Also x little Cb,O and traces of Ta205 SiO MgO. The analysis gives the ratios H,O R"O(Ca0 &c.) Rrr1203( Y,O &c.) RLV02(Th0 c h . ) TiO Rsc. = 6 1 3 1 1 6 . The mineral is therefore essentially a hydrous titanate of yttrium earths and thorium and for i t the new name y%rocmsite is pro- posed. The total radioactivity of the mineral TVRS found by 13. B. Boltwood to correspond to 10% of thorium and 2*080/ of uranium.L. J. 5. Volcanic Materials from the Gulf of Naples. RAM~N LLORD Y GAMBOA (Anal. Fis. Quim. 1906 4 193-2;02).-The analysis of certain almost colourless and transparent round crystals gathered on104 ABSTRACTS OF CHEMICAL PAPERS. the shore of Torre del Greco in the Bay of Naples gave the following result SiO,. Al,On. K,O. Na,O. Loss. 55.40 22-85 11'10 9 -20 1.45 100 00 The formula deduced from these numbers is KNaA12(Si03)4 showing that the mineral is one of the leucite group so often found in modern volcanic rocks. The volcanic origin of these crystals was demonstrated by the fact that on some were still t o be found adherent black nodules of lava. A specimen of Vesuvian lava ejected from the principal crater on October 31st 1905 and collected on the following clay gave the fol- lowing analysis SiO,.FeO. A1,0,. CaO MgO. Na,O. 48.050 10'300 19 -500 7 '600 3-024 6 -360 Smaller quantities of K20 Li,O CI P,O and loss amounted together to 4.566%. G. T. M. Composition of Volcanic Ash collected at Ottajano Vesuvius on April 14th 1906. G. COSYNS (Bull. SOC. chim. Belg. 1906 20 159-162).-The ash lost when completely dried at l l O o 0.28% of water and 0.03% of hydrogen chloride. 1.68% was soluble in water a t 1 5 O and this consisted of sodium chloride (0.761%) calcium sulphate (0*854%) magnesia alumina silica ferric chloride &c. From 3-4% of the dust was magnetic and this portion con- sisted of ma,gnetic oxide of iron (945%) titanium dioxide (2.1 l%) lime silica kc. 3.4%. The mashed powder had the following com- position SiO Fe,Os. CaO. Al&. RlgO. N+O. K20 Mi10. Cr,O,,. TiO,. P,O,. 48-65 16.25 11'21 14.76 3.94 3'19 2.53 0.02 0.009 0.115 0.6 Also traces of As F K Zn Ti Te C1 S. The mineral composition therefore would appear to be augite (50%) leucite (40%) biotite magnetite &c. (10%). When extracted with chloroform or ether the ash yielded 0.002% of Silvestri's " vaselin " ; when heated to a high temperature i t fused swelled and evolved reducing gases. T. A . H.

ISSN:0368-1769    

DOI:10.1039/CA9079205100

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

104 ABSTRACTS OF CHEMICAL PAPERS. Physiological Chemistry. Resistance of Mammalian Red Corpuscles towards Hzemo- lytic Agents. D. RYWOSCII (Pfliiyer’s Arclriv 1907 116 229-251). -The resistance of the fresh and washed red corpuscles towards numerous hamolytic agents (water saponin chloroform acetone &c. ) was investigated. The results obtained with the corpuscles fromPHYSIOLOGICAL CHEMISTRY. 105 various animals are arranged in columns in order of resistance. Every column shows a different order; even the fresh and the washed corpuscles give different results. Sero-mucoid in Blood. H. W. BYWATERS (Proc. PhpioZ. Soc. 1906 iii-iv. J. Physiol. 35).-Pavg has shown that the carbo- hydrate yielded by mncoids is greater after acid hydrolysis than after hydrolysis with 10% alkali.The non-coagulable proteid of blood behaves in this way and this fact as well as its non-diffusibility lends support t o Zanetti’s view that it is a mucoid (sero-mucoid) and not a proteose. The amount of sero-mucoid carbohydrate expressed as dextrose in grams per litre of blood was found to vary from 0.07 to 0 08 in the fasting dog from 0.097 to 0.11 when fed on bread or milk and from 0.18 to 0.24 when fed on dog-biscuit; that is to say an increase occurs after a diet consisting largely of carbohydrate. If the sero-mucoid is concerned in the transport of carbohydmte this is what mould be expected. Fate of Cholesterol and its Esters in the Animal Organism. HUGO PRIBRAM (Biochern. Zeit. 1906 1 41 3-424).-The resistance of the red corpuscles towards the hzmolytic action of such substances as saponin is believed t o be due to the materials of which their membranes are composed.Cholesterol is one of these and fluids con- taining cholesterol protect the corpuscles from hzmolysis. So far as the present experiments go these views are supported. The main con- clusion drawn however is that feeding an animal on cholesterol or its esters increases the amount in the blood-serum and this is believed to be mainly in the form of free cholesteiol. Photo-biological Sensitisera and their Proteid Compounds. GUN” BUSCK (Bioehm. Z e d 1906 1 425-540).-A complete review of previous work is given and a number of experiments are described from which the following conclusions are drawn. An intense light rich in rays of &orb wave-length is capable of destroying red blood- corpuscles.The negative results previously obtained are attributed to the source of light being too feeble. The substance contained in blood serum nlexin which acts as a poison to I’urccnmeium may be destroyed by exposure to ultra-violet light but may be sensitised by means of light of greater msve-length. The addition of various photobiological sensitic.ers such as deriv- atives of fluorescein and sodium dichloroanthracenedisulphonate to mammalian blood produces various alterations in the properties of the blood and of the sensitiser. Thus the property of coagulating may be diminished or completely destroyed as may also the action of the alexin of the serum on l’arummiun8. The presence of the serum is also capable of diminibhing or completely destroying the character- istic behaviour of the sensitisers to micro-organisms animal tissues toxins and enzymes the effect being most pronounced in the case of organised structures.Many of the chemical and physical character- istics of the sensitisers are also affected by the seium. Different sera produce somewhat different results the effect being most marked with a serum of feeble ‘‘ alkalesence.” Glue gum arabic starch peytone W. D. H. W. D. H. W. D. H.106 ABSTRACTS OF CHEMICAL PAPERS. theobromine and glycine do not produce the same effects as serum but egg-albumin does. The action of the sensitisers is ascribed to the formation of com- pounds with the albumins of the sercm these compounds having properties very different from those of their components. The eosin- serum compound is insoluble in water but dissolves i n serum in acid alkaline or neutral solution; i t also dissolves in alkali or in dilute acid and may be precipitated by means of ammonium sulphate.J. J. S. Blood-pigment of Thalassochelys Cor ticata. FHANZ BARDACHZI (Zeit. phgsiol. Chenz. 1906 49 465-471).-The blood- pigment of this turtle appears to give the same physical constants as the hzemoglobin of mammals. W. D. H. Action of Alkalies Lithium Salts and Lithium Water on the Gastric Secretion. 31. MAYEDA (Biochem. Zeit. 1907 2 332-338).-The investigation was undertaken in view of the action certain mineral waters possess of increasing digestion. By experiments on dogs with a Pawloif fistula it was shown that; alkalis stimulate the secretion and that lithium salts and mineral water containing lithium are specially efficacious in this direction.W. D. H. Influence of Physostigmine Euphthalmine and Dionine on the Gastric Secretion. ill. PEWSNER (Biocheiia. Xed. 1907 2 339-343).-Pawloff’s discovery of secretory nerves of the stomach has rendered the action of alkaloids on the secretion of special interest. Physostigmine acts like pilocarpine in increasing the secretion ; euphthalmine falls into the atropine group in diminishing it. Dionine a derivative of morphine stimulates the secretion ; it however acts more rapidly than Gorphine ; its narcotic action is less. W. D. H. The Inhibition of Peptic Digestion by Combining the Free Hydrochloric Acid with Amphoteric Amino-compounds.‘HERMANN JASTBOWITZ (Siochem. Xed. 1906 2 157-172).-The addition of amphotoric amino-compounds to pepsin-hydrochloric acid inhibits its fermenting properties. The substances used were glycine alanine glutamic acid and Witte’s peptone and of these glycine alanine and peptone produce the greatest effect. The inhibition is due to the removal of part of the hydrochloric acid in combination with the amino-compounds. J. J. 8. The Relationship of Pepsin and Rennin in the Child’s Stomach. JULIUS WOHLGEMUTH and H. ROEDER (Biochem. Zeit. 1907 2 421-427).-There is no truth in the statement that the child’s stomach membrane yields an excess of rennin in proportion t o pepsin. The rennetic and peptic activity are parallel. Pawloff’s view that the two actions are due to one complex substance is thus confirmed.W. D. H.PHYSIOLOGICAL CHEMISTRY. 107 Digestion of Proteids. W. GRIMMER (Biochsm. Zed. 1906 2 118-1 43)-A number of details regarding acidity of stomach contents alkalinity of intestinal contents and amounts of digestive products in different parts of the alimentary canal a t different periods are given. The observations mere carried out on herbivora mainly horses. Absorption occurs in the stomach as peptone and in the small intestine as peptone and crystalline cleavage products. W. D. H. Digestion and Absorption in the Stomach. G. LANG (Biochem. Zeit. 1906 2 225-242).-The experiments were made on dogs and the proteid given was fibrin appropriate fistulae rendered possible the examination of the material in the stomach or leaving it.The main result was that on the average 30% of the fibrin was undissolved; of the remaining TO% 60% was in solution mainly as yroteose and the remaining 10% was not recovered and had presumably been absorbed. W. D. H. Physiology of the Digestive Tract. I. ALOIS KREIDL (PJiiger’s Archiv 1907 116 159-162). 11 111. ALBERT MULLER (ibid. 163-1 70 1 7 1-185).-The papers mainly relate to the muscular tissue removal of which produces in dogs remarkably little effect ; there is hypersecretion and hyperacidity in the stomach During digestion in the normal dog no free hydrochloric acid was found ; the acid which reaches its highest value on a flesh diet is all combined. W. D. H. Chemistry of Digestion. VII. Gastro-lipase. E. S. LONDON (Zeit. physioZ. Client. 1906 50 125-128).-1n a dog with an ordinary gastric fistula fat is split to the extent of 17-23%.If the operation is a pyloric fistula and is perforrried so as to prevent any return of the intestinal contents and secretions into the stomach this is reduced to 2 4 5 % . W. D. H. Activation of Trypsin in Man. JULIUS WOHLGEMUTH ( Biochem. Zeit. 1906 2 264-270).-Several observers have stated already that the human pancreatic juice contains trypsinogen not trypsin ; this is confirmed in the present case in which the juice was obtained from a fistula. Experiments with the juice in uit9.o show that tryptic action is doubled in the presence of bile Liver juice has a still greater eEect but whether this is due to bile is uncertain. Activation was also pro- duced by glycine alanine and leucine feebly by tyrosine and not a t all by glutamic and aspartic acids.W. D. H. Milk Curdling Ferment in Human Pancreatic Juice. JULIUS WOHLGEMUTH (Biochem. Zed. 1907 2 350-356).-Human pancreatic juice contains a rennetic ferment mainly in the form of pro-ferment. Its activation by intestinal juice or by hydrochloric acid runs parallel to th0 activation of trypsin. W. D. H.108 ABSTRACTS OF CHEMICAL PAPERS. Fermenta and An tiferments. MARTIN JACOBY (Biochem. Zed. 1906 2 144-147).-Fibrin filaments soaked in trypsin and then well washed retain some of the enzyme so that they rapidly dissolve in an alkaline fluid. If placed in dilute hydrochloric acid they do not and the acid di5solves out the trypsin from them. Inhibition of the action of enzymes which have been absorbed by fibrin can be brought about by the antiferments of blood-serum.Pepsin and trypsin rapidly render t,rausparent blood-serum which has been rendered cloudy by dilution and boiling. W. D. H. Ferments and Antiferments. 111. MARTIN JACOBY (Biochem. Zeit. 1906 2 247-250. Compare this vol. ii 38 and preceding abstract).-The betiaviour of sodium carbonate to pepsin precipitates is similar to that of dilute hydrochloric acid to trypsin precipitates ; thus pepsin is readily removed from fibrin masses by treatment with very dilute sodium carbonate solution. The presence of an antipepsin in blood serurii has been demoustrated by the flock method and the antipepsin is present even after the serum had been subjected to dialysis. J. J. S. Digestion in Animals.V. A n Absorption Dog. E. S. LONDON. VI. Proteid and Carbohydrate Digestion in the Alimentary Tract. E. S. LONDON and W. W. POLOWZOWA (Zeit. physiol. Chenz. 1906 49 324-385 ; 326-396. Compare Abstr. 1906 ii 778).-The first paper is mainly concerned with experimental methods in the preparation of intestinal fistulae in dogs for the purpose of studying absorption. The second is a n elaborate study of the different stages in digestion and absorption in various parts of the alimentary canal using dogs prepared in such ways. The various degrees of digestion arid absorptive activity for proteids and carbohydrates are stated nuinerically and in curves. Digestion i s greatest for carbohydrates in the lower ileum for proteide in the upper ileum. Absorption stated in milligrams Fer square centimetre diminishes as the food passes from the small into the largo intestine I n the stomach no absorption of proteids or carbohydrates occurs Absorption of carbohydrates is a t a maximum in the duodenum of proteids in the jejunum.Particulars are also given as to the amount of juices secreted. The proteid of bread is better absorbed than egg- white because of the greater porosity of the bread not because of t h e carbohydrate admixture W. I). H. Lactase and the Adaptation of the Intestine to Lactose. R. H. ADERS PLIMMER (J. PhysioZ. 1906 35 20-31).-No evidence of the adaptation of the intestinal secretion t o the administration of lactase was discoverable. Dif-ferent animals vary a good deal in the amount of lactase formed a t different periods of life.W. D. H. Actioh of Non-proteid Nitrogen Compounds on Animal Metabolism. OSKAH. KELLNER (I’j!iiye?*’s ArcJ~iv 1907 116 203-206. Compare Abstr. 1906 ii 690).-Polemical. W. D. H.PHYSIOLOGICAL CHEMISTRY. 109 Trimethylamine as a Normal Product of Metabolism and its Estimation in Urine and Faces. FILIPPO DE PILIPPI (Zeit. yhysiol. Chern. 1906 49 43 3-456).-Trirnethylamine derived from the choline group of substances is a normal product of metabolism in animals and ‘men. Directions for estimating it in the distillate of urine and fzeces are given. W. D. H. Importance of Individual Amino-acids in MetaboliBm Addition of Tryptophan to Zein. EDITH G. WILLCOCK and F. GOWLAND HOPKINS (J. PJqlsioZ. 1906 35 88-102).-When zein is the only nitrogenous food given t o young mice they soon die.If tryptoplian which is absent from zein is given in addition the survival of the animals is greatly prolonged and it adds to their well-being althorigh they also ultimately die and growth is not main- tained. The addition of tyrosine (already present in zein) in equiva- lent amounts has no such effect.. It is suggested that the tryptophan is directly utilised as the normal precursor of some specific harmone or of some substance essential to life. W. D. H. Action of Asparagine in Animal Metabolism. CURT LEHMANN (f’fziiger’s A~chiv 1906 115 448-45 1 ). Action of certain Amino-substances in the Metabolism of ‘Carnivora. W. VOLTZ (ibid. 452-455. Coinpate Abstr. 1906 ii 560). -Polemicxl agaiost Kellner. W. D. H. Nuclein-metabolism.ALFRED sCHITTEN€mLit and JULIUS SC‘HMID (Zeit. p J ~ p i o l Chem. 1906,50 30 -35. Compare this vol. ii 41).-Previous researches have shown that the complicated process of uric acid formation occurs in different organs with different inten- sities in v;trir)us animals. Thus it occurs in the spleen of the ox and not that of the pig; giiannse and adenase are both present in the ox liver but only guanshe in the rabbit’s liver &c. (Jones and Austrian). On such a hypothebis the formation of uric acid is difficult to explain and the absetlce of purine bases in the urine in appreciable quantities shows that they do not circulate freely in the blood but must be changed somewhere. I n the preseut research gunnase was found in the pig’s spleen adenase i n the rabbit’s liver arid similar ferments in other organs of mbbit cat human beings &c.A number of negative results mere however also obtained and the suggestion is made that the preparation of the extracts may be at fault or non-activation of the ferments may explain 1 he results. W. D. H Human Chyle. J. MOLYNEUX HAMILL (J. Physiul. 1906 35 151-1(;2~.-Hi~man chj le collected from a surgical case is bluish- white and becomes yellower as the fat increases ; i t is alkaline and clots rapidly but the clotting is prevented by oxalates. As much as 4 litres were sometimes obtained in twelve hours. I t s average composition was solids 3.87%; ash 0.83%; fat 1.3% (very variable) ; total nitrogen 0.36% ; extractive nitrogen 0.01 %. 4.2 grams of lecithin and 5.2 grams of cholesterol were found in every 100 grams of etsher extract.Lipase and amylase were present. The largest amount of VOL. XCII. ii. 8110 ABSTRACTS OF CHEMICAL PAPERS. fat occurs six hours after a meal. fats is greater in the chyle than in the food. mouth raises the ether-soluble phosphorus of the chyle. given by the mouth is not found in the chyle. The ratio of the higher to the lower Lecithin given by the Petroleum W. D. H. Human Chyle. TORALD SOLLMANN (Amer. J. Physiol. 1907 17 487-491).-The chyle was collected from a surgical wound in the neck; at first the flow was continuous; eight days later the amount obtained was abcut 300 c c. in the twenty-four hours after which the flow gradually ceased as the mound healed. A t the time the present observations were made the amount collected varied from 0.1 to 14 C.C. every five minutes.I t s appearance was creamy except after a fast when it was almost clear. I t s composition was water 92.76 to 92.89%; solids 7.11 to 7.25%; ash 0 6%; sodium chloride 0.68% ; proteids 1.85% (but variable) ; chloroform extract 0.07% and ether extract 1.93%. The fat is unusually low in ammount. A single dose of potassium iodide had no effect on ttie rate of flow ; i t appeared in the urine eight to twenty minutes later but was not found in the chyle until three hours later J there is however some doubt concerning the correGtness of the analysis made before that time. None was found in either fluid twenty-seven hours later; it dis- appears at the same time i n both. Sodium salicylate and santonin after administration mere not discovered in the chyle. It coagulated readily IV D.H. Cerebro-spinal Fluid. FRENKEL-HEIDEN (Biochent. Zed. 1906 -2 188 -lS9).-The total proteid in human cerebro-spinal fluid removed by lumbar puncture in various diseases varied from 0.35 to 3 per 1000. It was highest in a case of progressive paralysis and in another of tubercular meningitis but these are cases where the amount is small in both diseases. The amount of non-proteid nitrogen is relatively high and may even be greater than that of proteid nitrogen. Ammonia is absent but the most abundant non-proteid nitrogenous substance is stated to be urea. W. D. H. The Cause of the Electrotonic Excitability of Nerve. JACQUES LOEB (Pfliiger’s Archiv 1907 116 193 -202).-A theory based on the physical work of the author and his colleagues.W D. H. Action of Inorganic Salts on the Nerves of the Isolated Mammalian Heart. WILLIAM H. HOWELL and W. W. DUKE (J. Physiol. 1906 35 131-1 50).-An isolated cat’s heart perfused with Locke’s solution is sensitive to the stimulation of the accelerator nerves for some hours. An increase of calcium chloride to certain concentrations (described in full) produces similar effects and of sodium or potassium chlorides the opposite. The action of the accelerator nerves is within certain limits favoured by the calcium increase but the opposite effect of potassium chloride was not marked. Increase of calcium in the circulating fluid had no distinct eifect on the inhibitory influence of the vagus nerve. W. D. TT.PHYSIOLOQICAL CHEMISTRY.11 I The Normal Heart Rhythm and the Artificial Rhythm Pro- duced by Sodium Chloride. A. J. CARLSON (A,mey. J. Pl~ysiol. 1907 17 478-486).-Further experiments on the heart of Linzulus in special reference to the mode of conduction of the cardiac rhythm. W. D. H. Occurrence of Bromine in Normal Human Organs. EGON PRIBRAM (Zeit. yhysiol. Chem. 1906 40 456-464).-The brain liver spleen and thyroid of nien contain normally no appreciable amounts of bromine. Composition of Flesh on Different Nutriments. MAX MULLER (Pjiigey’s Archiw 1907 116 207-228).-Experiments on dogs on different diets are recorded with special reference to what happens t o proteid food and how in the body it is split into a nitrogenous and a carbon rich residue ; and how far the latter serves for fat formation.W. D. H. W. D. H. Method of Combination of Creatine in Muscle. FUMICHTKO URANO (Beitr. chern. Physiol. Path. 1907 9 104-1 15).- Muscle contains about 0.4% of creatine; a man weighing 60 kilos. will there- fore have from 90 to 100 grams of creatine in his muscles. Creatine like creatinine is easily dialysable but it does not pass readily into the surrounding lymph and blood. The present experiments on freshly killed muscle show that i t does not readily diffuse out; the same is true for the dialysable phosphoric acid compounds in the muscles. Both must be combined in the muscular protoplasm. This view is con- firmed by Folin’s observation that creatine given with the food is partly retained in the body’ presumably because the muscles have the power of fixing it.Effect of Adrenaline on the Hepatic and Muscular Glycogen. I(. AGADSCHANIANZ (Biochern. Zeit. 1906 2 148-153).-The muscles oE animals heated with adrenaline are free from glycogen. The results on the liver were conflicting. Gatin-Gruzewska’s methods for obtaining glycogen were employed. HORACE M. VERNON (J. Physiol. 1906 35 53-87).-The experiments described on the excised kidney of rabbits and cats prepared with oxygenated saline solution show that the iuitial gaseous metabolism which at first is as great as in the living animal rapidly dwindles. The influence of various other factors including certain chemical reagents is also described. The tissue proteids in the course of the experiments were dissolved out by the perfusing liquid without affecting the tissue respiration the latter therefore apparently depends on nun-Ditrogenous side chains of the ‘‘ biogen ” (Verworn) molecules.The Ferments of the Placenta. M. SAVAR~ (Beitr. clbern. Physiol. Path. 1907 9 141-1 48).-The placenta causes the disappearance of glyoxylic acid as Schloss showed that the liver also does but its activity is less than that of the liver although greater than that of brain and W. D. H. W. I). H. Tissue Respiration. W. D. H. 8-2112 ABSTRACTS OF CHEMICAL PAPERS. muscles. Its action in causing the coagulation of fibrinogen solutions may be due to the blood i t contains. It also has proteolytic de- amidising and ereptic action which possibly are the result of post- mortem changes. Its oxydase and diastatic action appears to be related t o its metabolism.W. D. H. Action of Drugs on the Uterua. ARTHUR R. CUSHNY (J. Physiob. 1906 35 l-l9).-Methods are described for obtaining graphic records of uterine movements ; these are increased by stimulation of the hypogastric nerves ; and a similar effect is produced by nicotine and by adrenaline ; pilocarpine antagonises inhibition and is anta- gonised by atropine. Quinine aloin and barium chloride also increase the movements; alcohol has little or no effect and that of chloroform and ether is very slight. The results obtained with ergot were the same as those described by Dale. W. D. H. Causes of the Coloration of Animal Fibres. WILHELM SUIDA (Zeit. physiol. Chem. 1006 50 174-203. Compare Abstr. 1905 i 714; 1906 i 445).-The behaviour of various dyes such as para- magenta crystal-violet magenta methylene blue crystal-ponceau orange 11 and fast-yellow and of mordants towards various amphoteric substances has been examined.The substances used include gljcine alanine leucine tyrosine phenylalanine sarcosine pheng lglycine phenylglycine-phenylglycine phenylaminodiacetic acid phenylglycine- o-car boxylic acid a-naphthy lglycine creatine arginine nitrate hist- idine hydrochloride cystine aspartic acid asparagine glutamic acid hydrcjchloride tryptophan oxanilic acid aminodiphenyloxamic acid anthranilic acid acetylanthranilic acid methyl anthranilnte m - and p-sminobenzoic acids and ~minophenylpyrazolonecarboxylic acid. Only those compounds yield insoluble derivatives with both basic and acid dyes which contain aphenyl radicle attached to the nitrogen atom and which exhibit about equal basic and acidic properties.Tryptophan yields no precipitates and arginine nitrate and histidine hydrochloride behave in a characteristic manner The behaviour of carbamide biuret phenylcarbamide alloxan alloxanthin uric acid caffeine guanidine carbonate triphenylguanidine aniline p-aminophenol and of aminoguanidine nitrate towards djes has also been studied. Sparingly soluble coloured salts of guanidine are readily obtained that from crystal-ponceau having the composition rhe authors think it probable that the property possessed by certain animal fibres of combining with both acidic and basic dyes is due to the presence of different complexes in the molecule since on hydrolysis it is found that certain of the hydrolytic products can fix acid dyes whilst other of the products fix basic dyes.Further experiments with wool and silk indicate that these act selectively towards given dyes and that silk is more decidedly acidic than w 001. C*?%O,?N 6S4' J. J. 8. Staining of Fat by Basic Aniline Dyes. J. LORRAIN SbiITH (J Path. Bact,. 1907 11 415-420).-Fatty acids unite with thePHYSIOLOGICAL CHEMISTRY 113 colour base in aqueous solution but neutral fats fail to do so. Shaking a neutral fat with carbon dioxide gradually decomposes it and staining of the liberated fatty acid then occurs. That a ferment in the tissues may aid the action is suggested but the question is left unsettled. The hydrolysing action of carbon dioxide occurs also with carbohydrates.The carbol-fuchsin method of staining tubercle bacilli is really a form of fat-staining. W. D. H. Poeitive Heliotropism produced by Acids espwially Carbon Dioxide and Negative Heliotropism produced by Ultra- violet Light. JACQUES LOEB (Pjuger’s Amhiv 1906,115 564-581). -The experiments recorded were performed on various copepods volvox and other low organisms and the main results are con- tained in the title. The explanation adopfed is on physico-chemical lines as opposed to the teleologico-anthropomorphic’ standpoint ,of some authors. W. D. H. Formation of Lactose. FRANCIS H. A. MARSHALL and J. M. KIRKNESS (Biochem. J. 1906 2 1-6).-The experiments recorded on guinea pigs indicate that the removal of the mammary g1:tnds does not produce glycosuria after a subsequent parturition and that at sucha time there is normally no increase of dextrose in the blood such as one would anticipate mere Bert’s hypothesis that lactose is formed from dextrose correct.Giycosuria may sometimes occur in normal animals The sugar in the urine is then dextrose; if lactose is present its amount is insignificant. Such glycosuria is probably comparable to p 1st-operation glycosuria and neither it nor t h e gly cosuria which occurred in Porcher’s experiments after removal of the mammary glands dnring lactation can be regarded as supporting Bert’s views. Tne hormone which excites the mammary glands must act solely on these organs and not on the liver or other organs in addition; i t is quite inactive i n the absence of the mammary glands and is ineffective in causing them to regenerate.Shattock’s state- ment that these glands do not elaborate any internal secretion necessary for the growth of the fetus is confirmed. W. D. H. Opsonins in Milk. GERMAN SIMS WOODHEAD and W. A. MITCHELL (J. Path. Bact. 1907 11 408-414).-Opsonins occur in milk in greAter relative quantity than in the blood. .It is possible that this may play a part during milk feeding of infants in imparting to them passive immunity against tuberculosis. W. D. H. CARL ICAIsERLINa (Biochem. Zeit. 1907 2 312-318).-The concretion wa3 found in the interior of an Echinococcus cyst in the liver of a man. I t was found to consist of fat and bilirubin. W. D. H. Unusual Bilirubin-concretion in the Liver. Effects of Ligature of One Ureter.FRANCIS A. RAINBRIDGE (J. Path. Bad. 1907 11 421-425).-Miss Amos’s statement that this operation results i n hydronephrosis is confirmed. There ie temporary loss of weight’ but no permanent ill effects. The secretory114 ABSTRACTS OF CHEMICAL PAPERS. p w e r of the kidney for nitrogenous substances is not entirely lost even two months later. The initial pressure in the ureter is low but bears no relation to blood pressure. No evidence of absorption was obtained even when potassium iodide was introduced at a pressure of 50-80 mm. of mercury into the renal pelvis. W. D. H. Metabolic Balance of Nitrogen and Sodium Chloride. M LETULLE and MLLE. M. POMPILIAN (Compt. rend. 1906 143 1188-1 191 ).-In generid the quantity of nitrogen and sodium chloride excreted varied with the amounts ingested.The need f o r the two substances presents individual differences in different people. W. D. H. Methylguanidine in Urine. W. ACHELIS (Zeit. physiol. Chem. 1906 50 10-20 ; FRIEDRICH KUTSCHER ibid. 21).-Methylguanidine is a constant constituent in the urine of man horse and dog. I n the last named animal dimethylguanidine is probably also formed. It pro- bably arises from creatine ; but abundant administration of creatinine into the intestine and subcutaneous injection of methylguanidine pro- duces no appreciable rise of the latter substance in the urine. I n a creatine-free diet if creatinine is given only a part reappears as such in the urine. Hutscher awards Achelis priority in the discovery. Diurnal Variatims in Uric Acid Excretion.JOHN B. LEATHES (J. Physiol. 1906 35 125-130).-Two experiments on man are described in which a uniform purine-free diet was taken one with a high the other with a low nitrogen intake. Theamount of creatinine is independent of the nitrogen intake but special attention is directed to the fact that the excretion of this substance is greater during the day especially in its early hours than during the night. The same variations are even more marked in tho case of uric acid. This is not a sign that the kidney is less active at night for the excretion of total nitrogen is as high as or even higher than durhg the daytime. The discussion of the meaning of the variation is postponed nntil more experiments are performed. W. D. H. W. D. H. Colloidal Nitrogenous Substances Insoluble in Alcohol in Urine.ERNST SALKOWSKI (Chem. Centr. 1906 ii 1622; from Bert?. Elin. Woch. 42 No. 51 52).-The quantity of nitrogen contained in the precipitate obtained from urine by means of alcohol has been found to be equal t o 3.5% of the total nitrogen of nornial urine whilst in pathological urines it amounted to 8-9% and in a case of acute atrophy of the liver to 28.1%. I n theze determinations the precipitata was not dissolved and reprecipit ated. The nitrogenous constituents of the precipitate which are soluble in water do not permeate a colloidal membrane and the solutions do not give the biuret the Millon or the Adarnkiewicz reaction. Further experiments showed that the precipi- tate formed by alcohol in a solution prepared by dialysing normal urine consisted of at least two substances which contained different quanti- ties of nitrogen and could be separated t o a certain extent by means ofPHYSIOLOGICAL CHEMISTRY.115 animal charcoal. The substAnce which is present in the larger pro- portion and is not abeorbed by the charcoal is readily hydrolyeed by acid but is not attacked by ptyalin; it is probably a carbohydrate which contains nitrogen and is a constituent of that portion of the alcohol precipitate which is soluble in water but does not pass through a colloidal membrane. It appears probable that the excess of extractive material or ‘‘ colloidal nitrogen ” in pathological urines is connected with the presence of this substance and it is possible that in many cases in nhich an increased quantity of phenols has been detected this Influence of N u t r i t i o n on t h e Excretion of Bile Salts and Cholesterol.EDWARD H. GOODMAN (Beitr. Chem. Plqpiob. Path. 1907 9 91-103).-The experiments were made on a dog with a biliary fistula. The administration of blood C O F ~ U F C I ~ S meat and egg- white increased the total amount of bile and usually that of cholic acid secreted. Administration of cholic acid greatly increased the amount in the bile. The excretion of the cholesterol ran parallel t o that of the cholic acid. Brain in the food greatly increased the amount of cholesterol in the bile but did not raise the amount of cholic acid more than white of egg did Cholesterol does not appear to be a pre- cursor of cholic acid. A N e w Nitro-prusside Reaction in Urine.V. ARNOLD (Zeit. phyiob. Chem. 1906 49 397-405).-The urine passed after taking meat or meat extract gives the following reaction. If a drop of 4% sodium nitroprusiide solution is added to 10-20 C.C. of the urine and then 5-10 C.C. of a 5% solution of sodium or potassium hydroxide the result is a pure violet colour which rapidly becomes purple and in the course of a minute passes through broRnish-red into yellow. The reaction occurs most markedly one o r two hours after taking the meat or beef-tea and is entirely absent if such food is abstained from. The reaction is different from that given by creatinine or the acetone group of substances. It is not due to indoleor methyl mercaptan. The substance to which i t is due is not volatile.If the urine is deeply coloured the best result is obtained after previous decolorisation by animal charcoal. substance also plays a part. E. w. w W. D. H. W. D. H. Chemistry of Cancer. IV. Indole in the Stomach in Car- cinoma. ALBERT ALBU and CARL NEUBERG (Biochem. Zeit. 1906 l 541-543. Compare Abstr. 1906 ii 875).-Normally indole is found only in the faxes and as indoxyl in the urine. It was found i n the stomach contents in a case of carcinoma of that organ. This is believed to originate by autolytic action from the cancerous tissue. W. D. H. Cystinuria. 11. ADOLF LOEWY and CARL NEUBERG (Biocliem. Zeit. 1907 2,438-454. Compare Abstr. 1906 ii 103).-The observations were made on the same patient as before. At the time of the first research he had passed cystine crystals for eighteen years; since then a cystine cdlculus had formed.The administration of other amino- acids than those used before was undertaken. He was not capable of116 ABSTRACTS OF CHEMICAL PAPERS. burning &cine completely but passed 20% of it in the urine. Glycyl- glycine was then given a dipeptide which is unaffected by pancreatic juice; this behaved as in a normal person about 10% being passed in the urine and part of this as glycine. Polypeptides behaved in the same way. Glutokyriri was given but neither i t nor ite cleavage products (arginine lysine glutamic acid glycine) were found in the urine; there were traces of monoarnino-acids in the urine but it is question- able whether they originated from the glutokyrin given. The cleavage products (abiuretic) of 105 grams of fibrin were then given. In healthy men these are completely burnt but in the patient the amount of cystin passed increased and a basic substance probably histidine was found in the urine.The urine contained no tyrosine tryptophan o r glycine. The meaning of these results is discussed several possible explanations being put forward. Similar results were obtained with other cystinuric patients but the observations are not so complete. Glycaemia and Glycosuria. E. L~EFMAN and K. STERN Bioclmn. &it. 1906 1 299-308).-Various observers give the normal percentage of sugar as varying from 0.05 to 0.33%. The ques- tion of method is important and Knapp’s is regarded as the best. The blo0:d of twenty normal men was examined; the mean found was 0.086% the highest heing 0.105 the lowest 0.005.I n comparison with this a number of bloods from diabetic cases were examined ; in some cases the percentage rose t o 0.5 or even more than 1 in most it was more than 0.2 and even a small excess over the normal (0.1 15) led to the appearance of sugar in the urine. This mas not however always the case and percentages of 0.16 or even 0.18 did not cause glycosuria or the sugar in the urine was very small in amount. This is attributed t o ‘‘ tolerance,” the most marked cause of which (external tolerance) depends on the permeability of the urinary filter to sugar. In certain febrile cases especially pneumonia t h i s tolerance even if dextrose is administered in large quantities is very marked. JULIUS WOHLGEMUTH (Bio- chenz.Zeit. 1906 1 332-338).-The majority of observers agree that the amount of amino-acids in normal urine is negligible but there is a difference of opinion as to whether or not they are increased in amount in gout. Glycine is the acid t o which most attention has been directed. Kionka believes thak excess of glycine in the blood is the deter- mining cause of an attack of gout. The present observations on a patient who had suffered for thirty-seven years fi,om the disease lend no support t o this theory. The best method of detecting glycine is stated to be the naphthylcarbimide method of Neuberg and Manasse. The urine gave no evidence of the presence of amino-acids. Forty-five grams of glycine were then given by the mouth ; 0 5 gram was recovered in the urine but no attack of gout ensued.Twenty-five grams of leiicine were given and none passed into the urine. Thirty-five grams of inactive alanine were then given ; the d-alanine mas completely burnt in the body and of the Z-alanine only 1 8 grams was recovered in the urine. Such observations show there is no diminution in a gouty person of the power to burn and utilise amino-acids W. D. H. W. D. H. Amino-acid Metabolism in Gout. W. D. H.PHYSIOLOGICAL CHEMISTRY. 117 Experimental Leucocytosis. W. HENWOOD HARVEY (J. PhysioZ. 1906 35 115-118).-The leucocytosis which follows the injection of pilocarpine muscarine and barium chloride is a lym phocytosis of purely mechanical origin and is due to the contraction of the spleen and lymphatic glands produced by the drugs mentioned.It is inhibited by atropine. A similar lymphocytosis follows excitation of the splenic nerve. W. D. H. The Urine in Rabies. CH. PORCHER (Biochem. Zeit. 1306 2 29 1-306).-The observations were made on goats infected with rabies material. Glycosuria is a constant symptom and the Qccurrence of siigar in the urine and of Negri’s corpuscles in the nerve centres go together. W. D. H. Action of Nickel Salts on the Animal Organism. W. S. DZIERGOWSKY SIMON K. DZIERGOWSKY and N. 0. SCHUMOFF-SIEBER (Biochem. Zeit. 1906 2 190-21S).-The amount of nickel dissolved from cookingvessels by various acids and various foods was estimated and the results given in tables. Such admixture is harmless simply because the metal is not absorbed. The experiments were made on dogs.W. D. H. Fate of the Cresols in the Organism and their Influence on the Metabolism and Intestinal Putrefaction of Carnivora. D. JONESCU (Biochem. Zsit. 1906 1 399-407).-50 to 53% of m-cresol 65 to 70% of o-cresol and 7 3 to 76.5% of p-cresol are burnt in the orgaoism ; their relative toxicity varies inversely with these numbers. They cause a decrease in the animonium salts of the urine in dogs. The cresols are excreted mainly as ethereal sulphates and to a m a l l extent in combination with glycuronic acid. The amount in the latter combination increases with their toxicity and increases also on feeding with carbohydrates. W. D. H. The Influence of Inosite on the Frog’s Heart. FRITZ SACHS (P’iiger’s Archiu 1906 115 550-554).-1nosite added to Ringer’s solution used for perfusion experiments in the cold-blooded (frog’s) heart has a favourable influence on its beat even more so than sugar has W.D. €I. Physiological Behaviour of Inosite. PAUL MAYER (Biochem. Zeit 1907 2 S93-403).-1nosite is widely distributed in animal and vegetable tissues; it is not found in the urine and i n diabetes it is equally well destroyed in the body and has no influence on the sugar output. The present research shows i t has no effect on glycogen formation. After large doses in men and rabbits a small amount passes unchanged into the urine especially if it is given subcutaneously. It does not cause the formation of lactic acid. The urine however sometimes contains a dextrorotatory organic acid which yields n barium salt soluble in water and insoluble in alcohol but was not identified.W. D. H.118 ABSTRACTS OF CHEMICAL PAPERS. Behaviour of Starch in the Organism. GIUSEPPE MOSCATI (Zeit. physiol. Chem. 1906 50 73-96).-Starch solutiona can be introduced without harmful results in animals either subcutaneously or intravenously. Starch does not leave the body by the various secretions or excretions but is incorporated in various organs and converted into glycogen. W. D. H. Physiological Action of Periplocin. JOHANN FEIGL (Biochem. Zeit. 1907 2,404-414).-Periplocin is a glucoside derived from plants of the genus Pcriploca used in Africa as an arrow-poison. It pro- duces paralytic symptoms and is specially powerful as a heart poison. W. D. H. Behaviour of Phytin in the Organism. OSKAR HORNER (Biochem. Zeit.1907 2 42&-434).-The experiments on dogs and rabbits were undertaken t o ascerttin the value of phytin (anhydro- oxymethylenediphosphoric acid Posternack Abstr. 1903 ii 607 6SO) as a phosphorised food. After it is given the phosphoric acid of the urine (in the dog) rises somewhat (from 0.87-1.0 to 1-31-1.43) and that of the faxes from 0.2 to 4.7. It is calculated that 35% is ab- sorbed. Similar results mere obtained in the rabbit but the experi- ments are incomplete. W. D. H. Behaviour of Acetylglucosamine in the Animal Body. KURT MEYER (Beitr. chem. Physiol. Path. 1907 9 134-140).-Acetyl- glucosamine given by the mouth to rabbits soon killed the animals; during the few days they lived nitrogenous katabolism was increased ; the sugar in the urine was increased glycosuria having been produced by phloridzin but the conclusion that the material administered gave rise to sugar is put forward with reserve.W. D. H. Physiological Action of Arecoline. HUGO MEIER (Biochem. Zeit. 1907 2 415-420).-This alkaloid from the Areca nut falls into the nicotine-pilocarpine group so far as its physiological action is con- cerned. All these produce paralytic which may be preceded by con- vulsive effects by acting both on the central and peripheral parts of the nervous system. I n nicotine poisoning the central action in pilocarpine poisoning the peripheral action is the more prominent the two are about equal in the case of arecoline. ' W D. H. Poisoning by Carbon Monoxide. G. G. NASNITH and D. A. L. GRAHAM (J. Physiol. 1906 35 32-52).-Guinea-pigs living in a dilute carbon monoxide atmosphere are able by increasing the quantity of haemoglobin and the number of their red corpuscles to' maintain an oxygen-carrying capacity equal to that which they originally possessed.There is also an increase in the eosinophil and pseudo-eosinophil leucocytes. Different doses cause however different histological changes in the colourless corpuscles which are described in full. W. D. H.PHYSIOLOGIICAL CHEMISTRY. 119 Cause of the Poisonous Action of a Pure Sodium Chloride Solution and of the Removal of the Action by Potassium and Calcium. JACQUE~ LOEB (Biochem. Zeit. 1906 2 81-1 lo),-A solution of pure sodium chloride isotonic with sea water is a t least four times as poisonous for fertilised eggs of sea urchins as for non- fertilised eggs.The same holds good for solutions of other neutral salts and the sudden increase in poisonous properties is probably due t o the increased velocity of certain chemical reactions caused by the fertilisation. For the development of fertilised eggs of St~ongylo- centrotus puqnwatus an initial concentration of > 10 -6n hydroxyl ions is necessary. The hydroxyl ion concentration of sea water lies between 10-6 and lO-5n. The poisonous nature of a solution of pure sodium chloride of slightly acid reaction increases with the concentration of the hydroxyl ions. When the initial concentration of the hydroxyl ion in a pure sodium chloride solution is that favourable for development the eggs are rapidly destroyed yielding two cytolytic forms (compare Abstr.1906 ii 694). The transformation of the eggs into one form is retarded by the addition of cdcium and the other transformation by the addition of potassium. Hence both are necessary to destroy the poisonous action of pure sodium chloride solution If the concentration of the hydroxyl ions is below that necessary for the development of the eggs the addition of potassium cyanide to or removal of oxygen from the sodium chloride solution does not affect the poisonous action. If the hydroxyl ion concentration > 10-6 then the withdrawal of oxygen or the addition of potassium cyanide retards the black ” cytolysis haemolysis. J. J. S. Amylene Hydrate [tevt.-Arnyl Alcohol] as a Poison. 8. LOEWENSTEIN (Bioci~em. Zeit. 1906 2 lll-l17).-As much as 30 grams of pure amylene hydrate was administered to a patient in a single day without serious effect ; the main results mere increased secretion of mucous liquid in the throat and formation of large blisters on the feet. None of the ordinary effects of poisoning with amyl compounds was observed. I t s narcotic action is attributed t o the presence of the ethyl group as triethylcarbinol is a most pronounced hypnotic. J. J. S. Modiflcations of Toxine. J. MORGENROTH and 0. ROSENTHAL (Biochem Zeit. 1907 2 383-392).-The changes which toxins undergo for instance into toxoids undoubtedly occur but no correct idea of the chemical processes involved is forthcoming. Toxoids cannot be reconverted into toxins. I n the present experiments the poison of the Crotalus named haemorrhagin was investigated ; it receives its name from the capillary hzemorrhages which are the constant sign of its action. The addition of dilutie hydrochloric acid annuls its toxicity; 0.2 C.C. N/400 hydrochloric acid added to 5 C.C. of a solution of the poison was found to be sufficient for this purpose. Neutralisation of the acid does not restore the toxicity. W. D H,

ISSN:0368-1769    

DOI:10.1039/CA9079205104

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

105 Organic Chemistry. Melting Points of Hydrocarbons Homologous with Methane. D. E. TSAKALOTOS (Compt. rend. 1906 143 1235-1236).-When the boiling points of the members of a homologous series are plotted against the number of carbon atoms tho curve thus obtained is smooth (Young Abstr. 1905 ii 231) but the m. p. curve siniilnrly con- structed shows a number of zigzags (maxima and minims) and in the case of the hydrocarbons of the methane series the curve is irregular from C9H20 to C15,Hs1 and then becomes regular up to C60€1122. The melting points of the hydrocarbons between the limits C1,H3 and C,,Hl can he calculated from the formula An=[85 - 0*01882(n - 1)2]/(32- I) where An is the difference between the m. p. of one hydro- carbon of the series and that of its next higher hornologue and n is the number of carbon atoms in the molecule.I n the original are tabulated the experimental and calculated values of the known hydro- carbons of the rriethane series between the values n = 16 and 7~ = 60 and with the exception of the hydrocarbon C35H72 there is a very close agreement between the two sets of values. M. A. W. Preservation of Chloroform. PIERRE BRETEAU and PAUL Wooa (Con@. re?m?. 1906 143 1193-1195).-Chloroform exposed to air and light decomposes into hydrogen chloride and phosgene ; and the latter is very toxic. It is essential for the surgeon that chloroform should be pure and impurities of the kind indicated are best detected by cougo-red which is turned blue. This succeeds when silver nitrate gives no trace of piecipitate.W. D. H. Conversion of Conine into Dichloro- and Dibromo-Octanes JUL~US VON BHAUN and E. SCHMITZ (Ber. 1906 38 4365-4369).- The action of phosphorus penta-chloride or -bromide on benzoylconine leads to the formation of dicldoro-octune b. p. 105-10T0/16 mm. and of dibronio-octaqie b. p. 123-129O/11 mm. iespectively which should have from their method of formation the composition CH,X*[ICHql3.CHXPra. Conine derivatives cannot be re-formed from these substttnces ; only one-half of the halogen is displaced by the action of bemylamine or of potassium cyanide. c. 5. Synthesis of Halogenated tert.-Alcohols by Means of Organo-magnesium Compounds. Mdlle. R. DALEBROUX and HENRI WUYTS (Bull. SOC. chirn. Belg. 1906 20 156-158. Compare Henry Abstr. 1906 i 133 and Susskind ibid.).-Ethyl chloroacetate (1 mol.) reacts with magnesium ethyl bromide (3 mols.) in presence of ether to form a complex which on treatment with water fuxnishes cl~Zorometl~yZdiethyZcarb~~~oZ CH2Cl*CEt,*OH a slightly viscous liquid b.p. 70"/20 mm. Di5 1.0267 When distilled with a slight excess of VOL. XCII. i. i106 ABSTRACTS OF CHEMICAL PAPER§. CEt potassium hydroxide it yields aa-diethylethylene oxide O<bEt,,' a mobile liquid with a slight odour of mint b. p. 107O Di' 0.8403. Ethyl P-iodopropionate reacts similarly with magnesium ethyl bromide forming y-iodo-aa-dielhylpro~yl alcohol CH21*CH,*CEt2*OH a slightly viscous liquid with a characteristic odour. This O K ~ dis- tillation over potassium hydroxide yields aa-diethylpropylene oxide C H < ~ ~ ~ 2 > 0 a colourless mobile liquid with an odour sirnul taneously recalling those of anise and of mint; b.p. 12S-13Oo. T. A. H. Bu tyrolac t one and as-Dime t h y lsucci n ic Glycol [a- Methyl- pentane-u&diol]. LOUIS HENRY (Comnpt. rend. 1906 143 1221-1235. Compare Houben Abstr. 1904 i 334)-Butyro- lectone (Abstr. 1886 216) reacts with magnesium methyl iodido in the presence of dry ether to form 6 rnethyliuentccne-a6-diol OH*C~le,~CH,~CH,*CK,.OK which is a viscous colourless odourless liquid with a bitter-sweet taste b. p. 158"/65 mrn. or 222OJ77.1 mm. (corr.). It contains both the tertiar,y arid primary alcoholic groupings and Peacts ( 1 ) with acetyl chloride to form the cJdorocccetin Clte,C1*CH,.C~,*CH2~0~c (g-cJzloro-6-~~ethylpe~t~~ acetate) a colourless mobile liquid with a disagreeable odour.b. D. 132"/70 mrn. or 190°/?47 min. with erolu- J . tiww of hydrogen chloride; 'and (2) with hilute sulphuric acid CBle,*$X (15%) to form its oxide (2 2-dimethyZtetrcthydrofura~) O<ca,-CAd a colourless mobile liquid b. p. 95"/756 Dim. Ethyl y-chlorobutyrate CH,Cl*CH,,CH ,*CO,Et yields with mag- nesium methyl bromide the cldorohydrin (a-cJ~loro-6-nzetl~yIpe.ntane-6-ol) OH-CMe,*CH;CH,.CH,Cl which decomposes on heating into 2 2-di- met h ylte tra h y d ro f uran and a-chloro-6-metlzyl- A?-anzy lene C,Vle,:CH-CH,*CH,Cl b p. 135O; and is converted by the action of fuming hydrochloric acid or acetyl chloride into tho dicJdoroJhydriir (as-clichloro-6-naetl~~Z~entarze) I 4 CMe,Ui*C€I,*CH,~CH,Cl b. p. 179-1 SOo,' which does not ~o'iidifg at - SO".I T . A. W. Influence of Radiolea on the Character of the Residual Valencies of Oxygen WLADINIR TSCHELINZEFF (Compt. rend. 1906 143 1237-1239. Compare Abstr. 1905 ii 802; 1906 ii 334; Blaise Abstr. 1901 i 317).-The author has measured the thermal effects Q and 4 corresponding with the combination of an ttlkyl magnesium iodide with two successive molecular proportions of an OEt .................. 8.63 6'16 12.60 12.79 EtO*C,II ........... 6.15 5-93 12.12 12.08 EtO*U,H,(iso) ...... 6-84 5-37 11.40 11 *21 EtO*C,H,,(iso) ...... 6.17 5.47 11-73 11 '64 O(C,H,,),(iso) ...... 5.91 4 54 10'31 10-45 PhOMe ............... YhOEt - - - !?* cf. &. Q=q+q'. - - - - ..............OBGFANXC CHEMISTRY 104 ether also the value Q of its direct combination with 2 rnols.of the ether ; the alkyl magnesium iodide employed was C,H,*MgI and the results are tabulated on p. 106. These figures show that in the aliphatic ethers the replacement of one radicle by another (with the exception of tlie isoamyl group) has very little effect on the charactor of the residual valewies of the oxygen atoms; but in the case of the aromatic radicles the nature of the redction is quite different there being practically. no theriiisl effect accompanying the addition of one phenyl group. M. A. W. Complex Ether-Oxides. MARCEL SOMMELET ( A 72%. Cftinz. Phys 1906 [viii] 9 484-576).-A detailed account of the preparation and properties of the a-glycol ethers of the types OH*Clt,~CH,*OX and OH*CRR'aCH,-OX and of @-glycerol ethers of the type OH*CR(CH,-OX) and of the aldehydes of the respective types CR,H*CHO CRK H-CHO and CH,:CR.CHO derived from them.Certain of these compounds have already been described in two earlier papers (Behal and Sommelet Abstr. 1904 i 223 ; and Sommelet this vol. i 2l) and will therefore only be referred to in this present abstract in the cases where their physical constants have been amended or extended. Alkyl esters of ethoxyacetic acid are readily prepared by the action of the corresponding alcohol on ethoxyacetic acid in t h e presence of hydrochloric acid; isobutyl ethoxyacetate OEt*CH,*C0,C4Hn b. p. 186'/755 mm. (corr.) ; isoamyZ ethoxyucetate OEt~CH,*CO,CY,H, b. p. 204-205O/756 mm. ; be.lzxyl et~oxyucetute OEt CI-I,*CO,CH,Ph b. p. 155*/2l mm. ; pZielzyZ ethoxpcetccte obtained by the action of phenol on ethoxyacetyl chloride in pyridine solution b.p. 139'//18 mm. ; etkoxycccetic anhydride (OEt-CH,*CO),O b. p. 142 -143*/125 mm. E'thoccyucetylu-ceto.ILe OEt *CH,=CO*CH,*COMe prepared from acetone and ethyl ethoxyacetate by tlie Claisen condensation is a colourless oil b. p. 83-84'/13 mni. ; its copper derivative forms blue needles m. p. 149". ~tJ1o:~yacetylmetl~~Zc~ceto,ie OEt* C . 4 9 CO*CHMe-COMe prepared by the action of methyl iodide on the sodium derivative of ethoxy- acetylacetone in sealed tubes at 125O is a pale yellow liquid b. p. 103-105°/15 mm. ; ethoxyucetylethylacetone b. p. 116'/15 mm. Of the ketones of the type R*CO*C€I,*OEt (Sbstr. 1904 i 222) pre- pared by the actionof organomagnesiumcompounds on the corresponding cyanoalkyloxymethanes (this vol.i 22) the densities and amended boil- ing points are given and the semicarbazones described. Ethoxyucetons- eeemicarbaxone OEt.CH,*CMe:N*NH*CO*NH2 forms prismatic needles m. p. 96' (compare Leonardi and Franchis Abstr. 1903 i 788). a-Ethoxybutanone b. p. 55'/24 urn. or 62*5'/33 mm. ; DF 0.914 ; the wmicctrbctxone m. p 87". a-Ethoxypentanone b. p. 6U0/11 rnm. or 64-65O117 mm. -Di* 0.9218 ; the senaicarbaxone m. p. S7O. a-Etltoxy- Brnethyl'entanone b. p. 67.5-68*5O/14 mm. or 73-74'/20 mm. and lli6 0.89 12 ; the semicui*buxone m. p. 11 9'. a-Ethoxy-€-met hylhexanone b. p 88'/13 mm ; the seriaicurbazone m. p. 89". w-Sthoxyacetophenone i 2108 ABSTRACTS OF CHEMICAL PAPERS. ozime OEt*CH,Ph:NOH crystdlises from ether or petroleum in prisms m.p. 55' ; the senzicarba :one m. p. 128'. The densities of the a-glycol ethers OH*CR,*CH,*OX already described (Abstr. 1904 i 222) are as follows OH*CMe,*CH,*OEt Di5 0 8786 ; OH*CEt,*CH,*OEt Di5 0.8961 ; OH*C(C,H7),*CH,*OEt Dis 0.8716 ; OH*C(C,H,,),-CH2-( )Et D:5 0 8595 ; OH*C)Ph,*CH,*OEt Di9 1.094. I n addition t o the a-glycol etllera of the type OH*CRR'*CH,-OX previously mentioned (Abstr. 1904 i 222) the following are described a - ethoxy - p - methylbutane - /3 - 01 OEt.CH,*CMe(OH)*C,H b. p. 14S-149°/763 mm. 0.S825 ; a-ethoxy-P-methylpentune-p-ol OEt*CH,*CMe(OH)*CH,*Et b. p. 167-168' Di6B 0.8767 ; a-ethouy- P-ethylpentane-P-ol b. p. 182-183' or 77'/13-14 mm. and not l$0-1S4° as previously stated 0.8786 ; a-etl~oxy-6-rnetl~yl-P-e~~hyl- pentane-P-ol OEt*CH,*CEt(Oli)*CH,Prfi b.p. 97'/26 mm. or 93'/22 mm. DY'5 0.8731 ; a-ethoxy-P-methyloctane-p-ol b. p. 102-105"/ 11-12 mm. Up 0.5665 ; a-ethoxy-P-methylnonane-P-ol b. p. 118-1 19"/11 mm. Ui6' 0.S6S5 ; a-ethoxy-j3-methylundecane-p-ol OEt*CH,*CMe(OH)-C,H, b. p. 152-153'/19 mm. Di6'5 0.8623. P-Glycerol ethers of the typv OH.CR(CH,*OX) are prepared by the condensation of the ethereal salt of the corresponding acid and the chloromethyl alkyl ether in the pre3ence of magnesium and a little mercuric chloride. p-EthyZgZycerol ay-diethyl ether OH*CEii( CH,*OEt) b. p. 84-S6'/20 mm. or 195"/71;5 mm. (corr.) Di6'5 0,9503. P-Propyl- glycerol ay-dietlhyl ether OH*4:Pra(CH,*OEt)2 b. p. 97'/ 16 mm. or 210°/760 mm D16 0.9195. j3-isoRutyZglyce?-ol ay-diethyl etlhey C,H,*C(CII,*OEt),*OH b.p. 11 1-112'/23 mm. or 215'/760 mm. D:65 0.9077. 6-isoButyZgZyceroZ ay-di/,ropyZ ~~~L~~,C,H,*C(CH,*O*C,H~),*OH b. p. 139-14Oc/22-23 mrn. '0.893s. j3-isoButyZgZyceyoZ ay-diisobutyl ether C,HS.C(CH,*O*C,II,),.OU b. p. 145-147O/18 mm. Di6'6 0.8766. /3 isoButylgZycero1 ay-diisoamyl e l m C,II,* C(CII,*O*C,H,,),*OH b. p. 162'/12 mm. or 178'/25 mm. D',"' 0.S785. P-n-AmylgZyce~oZ ay-diethy2 ether C,H,,*C(CH,.OEt),.OH 1 ~ . p. 11 S-119"/13 mm. D 0.9029. /3-IIexytglycsrol ay-diethy2 ether C,Hl3*C(CH,- 0 Et),*OH b. p. 135-136'/15 rnrn. Di615 0.901:;. P-DecenylgZycerol ay-diethyl ether CloHl,*C(OH,*OEt),*OH b. p. 1 30°/12 mm. Dy5 0.9. ,!3 0ctylgZyces.ol ay-claethyl etlher C,H,7*C(CH,.01 .t);OH b. p. 160°/15 mm. Dy5 0 8949. /3- BenxylgZycei*oZ ay-diethy1 etR I r C H Ph.C( CH,*OEt)2* OH b.p. 174'/14 mm. Dp5 1.0091. I n addition t o the aldehydes of the typesCR,H*CHOandCRR H-CHO previously mentioned (Rbstr. 1 i104 i 222)) certain of their derivatives and some new members of the series are described. a-Etliyl- butaldehyde oxhe has b. p. 95 134 rnm. and the semicus*buxorze m. p. 93-94'. a-Propylvaleraldehytle has D:j 0,8347 the ozime b. . p. l26'/47 mm. and the semicarb;txone m. p. 100-101'. a-isoA4mylzso- heptaldehyde has Di6 0.8261 i he oxime b. p. 153'/29 mm. u-h'thyl- isohexaldehycle C H .CHEt*CH( ) b. p. 154-155O ; the setnicccrbccxone m. p. 97-98.6. a-Metl~yEo,.taldel~y~e C,H,*CHMe CHO b. p. 82-83"/20 mm. ; the scmicctrbn 0728 m. p. 78-80O.ORGANIC CHEMISTRY. 109 The following a-alkylacraldehydes were obtained by the action of anhydrous oxalic or pure (crystallisable) formic acid on the corre- sponding P-alkylglycerol ay- dialkyl ethers.a- Eth y kacraldeh yde CH, CEt CHO yields a crystalline semicar baaone m. p. 192.5'. a-Z'rop~lacrcckdehyde CH,:CPra*CHO b. p. 116-118' ; the semicarbmone m. p. 153'. a-isoRutylacrcLZtleh?lde CH,:C(C,H,)*CHO b. p. 133" fornis the semicarbazone m. p. 184' and yields isobutyl- acrylic acid b. p. 118-120'/26 mm. on oxidation with silver oxide. a-f!mylncrcckdeh?/de CH,:C(C,II,,)*CHO b. p. 59"/13 mni. ; the semicarbccxone in. p. 154.5'. a-NexyZac?*aZdehyde CH,:C(C,I-I,,)*CHO b. p. 78'/15 mm. yields the semicurbaxoize m. p. 156' and a crystalline compound mi t h sodium hydrogen sul phi t e. CH,:C(C,H ?)* CHO b. p. 104~5-106°/14 mm. and the semicarbazone in.p. 141.5'. ~ K e i z x y l - cccraldehycle CH,:C(CH,Ph)*CHO b. p. 118-120'/13 mm. and the semicarbazone m. p. 159'. a- Octylacruldelqde M. A. W. Esterifhation of Arsenious Anhydride by Alcohols and Phenol. VICTOR AUGER (Conzpt. rend. 1906 143 907-909. Com- pare Abstr. 1902 i 255).-Arsenious oxide is not volatile in steam but is volatile in the vapour of methyl alcohol with the formation of methyl arsenite. Owing to the hydroIytic action of the water formed during the esterification the reaction is :i balanced one and the extent to which arsenious oxide is esterified bj. met.hy1 alcohol and its homo- logues was determined by heating the alcohol with excess of crystal- line arsenious oxide i n a sealed tube at 160-18O0 and estimating the arsenic in a portion of the cooled liquid by means of iodine the difference between this quantity and the amount of arsenious oxide dissolved by the same quantity of alcohol in the cold representing approximately the amount of ester formed.I n the case of methyl alcohol and arsenious oxide the equilibrium stage is reached in the cold in fourteen hours when 5.16% of ester is formed ; after three hours a t 150° 6.5% of ester is formed but after eighteen hours this has diminished to 5%. I n the case of ethyl alcohol 1.2% of ethyl arsenite is formed on heating and the corresponding numbers for propyl isopropyl isobutyl and isoamyl alcohols are 1.153 0.1 12 0.36 and 0.1 9 respectively. It is possible t o isolate the alkyl arsenites either by fractional dis- tillation in the case of isobutyl or isoamyl alcohol or by removing the water from the alcohol and aqueous distillate by means of calcium carbide in the case of the other alcohols and the following alkyl arsenites were thus formed prop9l arsenite As(OC?H~)~ b.p. 217'; n-bzctyl arseizite As(OC,HJ3 b. p. 263' ; and isobutyl arsenite As(OC,H,) b. p. 242'. Phenyl arsenite is formed when phenol is heated with excess of arsenious oxide. M. A. W. Constitution of the Salts of Glucinum w i t h the Fatty Acids and the Valency of Glucinum. BORIS GLssnrA" (Chenz. z e i t 1907 31 8-9).-According to Tanatar (Abstr. 1904 ii 335) the110 ABSTRACTS OF CHEMICAL PAPERS. composition of the volatile glucinum compounds described by Urbain and Lacombe (Abstr. 1909 i 132) should be expressed by the formula Gl,OR in which glucinum is quadrivalent and not by the formula GI40R in which this element is bivalent.The present author haw- ever regards these substances as salts of bivalent glucinum with anhydrides of ortho-fatty acids. It is assumed that acetic acid can act as an octo-basic acid by the elimination of 5 mols. of water from 6 mols. of ortho acid 6CH,*C(OH) = (CH,C),O,(OH) + 5H20 and the glucinum salt is regarded as n normal salt of this acid. P. H. (-Bromoheptojc Acid. JULIUS VON BRAUN (Be?*. 1906 39 4362- 4 3 6 5 ) . - ~ - - r h e n o x y ~ e ~ ~ o ~ c acid OPh*CH2*[CH,],*C02H m. p. 56- 55' is obtained qnantitatively by hydrolysing the nitrile pre- pared from (-phenoxjhexyl iodide ; the silver salt is a white crystal- line powder decomposed only slowly by light.The acid and hydro- bromic acid react at 80" to form ultimately c-bromoheptoic acid CH,Br*[CH,];C02H m. p. 30-31' b. p. 165-167'/12 mm. which distils almost unchanged between 280' and 300° and by treatment with hot water yields a hydroxy-acid which does not tend to form an eight- membered lactone ring (compare Baeyer and Villiger Abstr. 1900 Action of Reagents for the Aldehydic Fonotion on Ethyl Glyoxalate. LOUTS J. SIMON and G. CIIAVANNE (Compt. rend. 1906 143 904-907. Compare Abstr. 1906 i 636).-Ethyl glyoxylate condenses with phenylhydrazine hydroxylamine or semicarbazide in the normal manner of compounds containing the aldehyde grouping and the following compounds have been prepared. (1) The phenylhydrazone NHPh*N:CH-CO,Et readily obtained by the action of pheoylhydrazine hydrochloride on ethyl glyoxylate forms pale yellow triclinic crystals ni.p. 131° can be distilled under reduced pressure a t l f O ' and is identical with the compound obtained by von Pechmann from diazo- benzene acetate and ethyl sulphohydrazimethylenecarboxylate (AFstr. 1896 i 678; compare also Reissert Abstr. 1895 i 460). The potassium salt N,HPh:CH*CO,K,~C,HS.OH is crystalline ; the acid N,HPh:CH*CO,H has m. p. 141° when heated slowly or 163' on a mercury bath (Reissert Abstr. 1895 i 460). (2) The oxime OH*N:CH*CO,Et crystallises from ether and light petroleum in long hard needles m. p. 3 5 O b. p. 115"/15 mm. or 110-111°/12 mni. is identical with ethyl isonitrosoacetate obtained by Bouveault and Wahl by the action of nitrosylsulphuric acid on ethyl acetate (.Abstr.1904 i 546) and on hydrolysis with dilute potassium caibonate yields the acid OH*N:CH*CO,H which decomposes a t 130-140° according to the rate of heating (Bouveault and Wahl Zoc. c i t . ) ; the amide (NOH):C?H*CO*NR forms colourless transparent rhombic plates which decompose at; 126' (compare Ratz Abstr. 1904 i 857). (3) The semicadaxone NH2*CO*NH*N:CH*C0,Et has m. p. 228O (decomp.) ; the acid decomposes a t 258' on a mercury bath (Bouveault and Wahl give 240° Abstr. 1004 i 547). NH,*CO-NH*N:CH* CO-NET forms a coarse white mass decomposing at 217-218" i 328). c. s. The amida M. A. W.ORGANIC CHEMISTRY. 111 Ricinoleic Acid. ADOLF G R ~ N (Ber. 1906 39,4.400-4408 born- pare Goldsobel Abstr. 1895 i 81 ; Walden ibid. i 125 ; Behrend ibid.i 647).-A study of the dihydroxystearic acids obtained from ricinoleict acid with a view t o the elucidation of the relations existing between oleic ricinoleic and dihydroxybtearic acids. When ricinoleic acid is treated with sulphuric acid a t - 5 O and the sulphuric esters hydrolysed the product obtained consists of 12.6% of ricinoleic acid 6.4% of dihydroxystearic acid and 81% of the anhydro- compound C H3,(0H),*C0.0* C,7H,,(OI€)*C02H the latter being easily converted into the acid by alcoholic potash. Juillard's acid m. p. 67-69' (Abstr. 1 S95 i 82) is a mixture and by repeated recrystal- lisation is resolved into four acids one m. p. 120° only occurring i n small qiiantities ; the other three ai-e dihydroxystearic acids. Dihydroxyscteccric mid C,7H,,(OH),-C0,€€ m.p. 108' crystallises from alcohol in mow-white crystalline aggregates and is optically inactive. Between the other two acids there is a very close concexion as the d-OX dihydroxystearic ctcid CH,.[CH,]~*a white crystalline powder m. p. 90° [.ID -+ 6.45' in alcohol is oon- verted into the d-1-acid white waxy spherical crystalline aggregates m. p. 69*5O optically inactive in alcoholic solution spontaneously or on heating a t 130-1409 The diacetactes are bright yellow mobile oils that obtained from the d-acid giving uD + 10' in 25% alcoholic solution. That the acid is an as-dihydroxy-derivative is shown by its conversion in to a pyrrole derivative. A- RTO~O-BL ~ l ~ ~ ~ ~ ~ r ~ x ~ s t ~ c ~ r i c acid CH,*[CH,]~*CH~r*CH,*CH(OH)*~€I(OII).[CH,]~*CO,H prepared by the action of phosphorus pentabromide on ricinoleic acid (compare Kasansky Abstr.1900 i 426) and oxidation of the bromo- oleic acid so obtained by potassium permanganate is a thick pale yellow oil which yields a solid benzoyl derivative. The bromine atom is firmly attwhed to the carbon and attempts to reduce this compound to a dihydroxystearic acid failed. Reduction by zinc and hydrochlorio acid of the iodo-derivative obtained by digestion with calcium iodide a t looo gave stearic acid. An attempt to reduce bromo-oleic acid was also unsuccessful. W. R. Behaviour of Chloroform towards Methylene and Methenyl Groups. ARTHUR K i j ~ z aud W. Z~RNIG (J. pr. Chem 1906 [ii] 74 425-448. Compare Oppenheim and Pfaff this Journal 1 S74 !27 1162 ; 1875 28 1261.Conrad and Guthzeit Abstr. 1883 311. Clnisen Abstr. 189.7 i 592. Errera Abstr. 1898 i 298; 1901 i 43 ; 1903 i 265. Coutelle Abstr. 1906 i 139).-Acetylacetone dikelohydrindene and malononi trile react with sodium ethoxide and chloroform in a similar manner t o ethyl acetoacetate or ethyl malonate whereas chloroform and sodium ethoxide do not react with benzyl cyanide or below 1 OOO with deoxybenzoin ; a t higher temperatures the last substance is reduced to stilbene. In compounds containing two or three halogen atoms attached ta the same carbon atom the first and second halogen atoms may be sub- stituted sticcessively by the action of ethyl sodioalkylmalonntes. The112 ABSTRACTS OF CHEMICAL PAPERS. third halogen atom is exceedingly inactive PO that the halogen free compounds CH[CR(C02Et)2]s cannot be formed by the action of chloroform on ethyl alkylmalonates or of ethyl sodioalkylmalonates on ethyl chloromethylenebisalkylmnlonates (compare Auwers and Keil Abstr.1903 j 620). Only small amounts of the corresponding aldehydes have been obtained and that with difficulty by the hydrolysis of the ethyl dichlorometl~ylalkylmnlonates. The action of ethyl sodionmlonate on ethyl beazyl~licnrboxyglut- aeonate leads to the formation of only a small amount of ethyl benzyl- ma1 on ate. When treated with chloroform in absolute alcoholic solution sodiomalononitrile yields metJ~e?L?/lbismaZononitl.ileniono~~n~?zo-et~,~l etlier C( CN ), CH* CH( CN)* C( OEt) NH gH20 or CH(CN),*CH:C(CN)*C(Ol~t):NI~,~H20 which is precipitated by light petroloum from its solution i n benzene i n small yellow crystals m.p. 244' (decoinp.). Acetylacetone reacts with sodium ethoxide and chloroform in abso- lute alcoholic solution in a sealed tube a t 130" forming 5-hydroxy- 2 4-diacetyltoluene (Claisen loc. cit.). The action of sodium ethoxide and chloroform on diketohydrindene in absolute alcoholic solution leads t o the formation of methenyl- bisdiketohydrindene (Errers Abstr. 1903 i 265). Xthyl iodonzet~~yletJ~?/Znzcclonate CH,I*CEt( CO,Et) is formed by the action of an excess of methylene di-iodide on ethyl sodioethylmalonate in absolute ethereal solution; it is obtained as a colourlees oil b. p. 137-138°/12 mm. which gradiially becomes red. Ethyl metJL~ldichEorol?zetJL~l~~~c~Zonat~ CHCI,*CMe(CO,Et) and eth$ cl~Zo~~omethylenebisrr~etJ~yZnzc~Zoizccte CHCl [ CMe(C0 Et),] are formed together by the action of chloroform on ethyl sodiornethylmalonate and are separated by fractional distillation The dichloro-ester is a transparent white oil b.1). 129'/12 inm which yields small amounts of silver chloride when heated with silver oxide and water in a sealed tube at 100'. The monochloro-ester forms a yellomoil b. p. 171-173" 12 mm. I n the same manner are formed etJqZ cJicAZoron7etJLyZpro~~ZntciloncLte CECI,*CPr(CO,Et) b. p. 266-158O/16 mm. ; ethyl cJdoi*omethyZene- bispropylmnlonate CHCl[CPr(CO,Et),J b. p. 210-213"/12 mm. ; ethyl dichlorometlqlbenxylmdonate CHCI,*C(CO,Et),*CH,Ph b. p. 207-309'/16 mm. and 4 9 2 cJ~lor.orneth~lenebisbenz~lmaloriate CHCl[C(COEt);CH,Ph] b.p. 263-265'/1 4 mm. The action of chloroform and sodium ethoxide on ethyl chloro- malonate in absolute alcoholic solution a t 120' leads to the formation of ethyl ethanetetracarboxylate. G. Y. Condensation of Ethyl Oxalacetate and Ethylcyanoacetate in the presence of Piperidine. CH. SCHMITT (Compt. rend. 1906 143 912-913. Compare Abstr. 1905 i,.508).-Ethyl oxalacetate condenses with ethyl cyanoncetate in the presence of piperidine t o form ethyl a-cyanopropylene-apy-tricarbox&te CY0,Et *CH;C(CO,Et) C(CN)*CO,Et which crystallises from benzene in needles in. p. 75" has a neutralORGANIC CHEMISTRY. 113 reaction and is isomeric with the acid compound obtained by Errera and Perciabosco by the action of dilute alkali on ethyl isoiminocsrboxy- aconitate (Abstr.1902 i 116) which probably has the constitu- tion CO,Et*CH(CN)*C(CO,Et):CH(CO,Et) (compare Rogerson and Thorpe Trans. 1881 39 631). Ethyl oxalacetste reacts with ethyl sodiocyanoacetate to form the cornpou?~d CN *CNa( CO,Et)*C(CO,E t) :CH( CO,Et which yields aconitic acid when treated with hydrochloric acid ethyl 2 6-dihydroxypyridine-4 5-dicsrboxylate . (ethyl dihydroxycincho- meronate) when treated with cold concentrated snlphuric acid and 2 6-dihydroxypyridine-4-carboxylic acid (citrazinic acid) on treatment with alcoholic potassium hydroxide. \I. A. W. Tetrabromo-derivative of Methyl E thy1 Ketone. PASTLREAU (Compt. r e ~ d . 1906 143 967-969. Compare Abstr. 1905 i 572). -MetlqZ etlbyl ketone peroxide formed by the action of hydrogen peroxide on the ketone in dilute acid solution reacts with bromine in presence of water a t the ordinary temperature yielding oxygen and the tetrabromo-deriTrative of the ketone.The reaction is completed on the water-bakh. Bronzornethyl PP/3-lrib~onzoethyZ ketoize C€I,Hr* CO*GH,* CBr crystal- lises from boiling 95% alcohol in white octahedra m. p. SOo has an irritating odour and is insoluble in water. When boiled with aqueous potassium carbonate in a reflux apparatus it yields acetol and acetic and formic acids. The formation of acetol must result from the decomposition of intermediately formed hydroxyacetoacetic acid OH* CH,* COO C H,* C0,H. G. Y. Compounds of Ketones with Ammonia. Methyl Propyl Ketone Ammonia. CARL THOMAE and HERNANN LEI^ (Arch. PJ~ccrsn. 1906 244 664).-MethyZ propyZ keto7Le nvzmonia C,,H,,N or CMePr(N:CMePr) was obtained as a n oil by the method already employed in the preparation of analogous compounds (hbstr.1905 i 509) ; the yield mss 22% of the theoretical. C. F. B. Physico-Chemical Investigations on Glycogen. FILIPPO BOTTAZZI and G. D’ERRICO (PJuger’s Archiv 1906 115 359-385).- The viscosity of glycogen solutions increases gradually with the con- centration for dilute solutions but as the solution becomes more concentrated the viscosity suddenly increases enormously with the concentration thus pointing to some physical change in the nature of the solution. A curve is given showing the relationship between the viscosity and temperature for 10% and 20% solutions. No distinct breaks are noticeable. The electrical conductivity of a solution of glycogen containing electrolytes first increases with the concentration attains a maximum then rapidly decreases and finally slowly diminishes.The melting point falls as the concentration increases but the curve shows no characteristic breaks. Saliva under suitable conditions reduces the viscosity of glycogen solutions owing to its fermenting action on the carbohydrate. The114 ABSTRACTS OF CHEMICAL PAPERS. effect is the most pronounced at the bcginning of the disstatic action and in concentrated solutions. If the saliva is first boiled and the diastatic ferment destroyed no appreciable effect on the viscosity is noticeable. J. J. S. FRIEDRICH KUTSCHER (Zeit. physiol. Chem. 1906 49 484. Compare this vol. i 31).-When novaine is distilled with bariiim hydroxide the whole of the nitrogen is eliminated as trimethyl- amine.The residue contains a characteristic decomposition product which is probably crotonic acid. Hydrogenation by Catalysis of Hexarnethylenetetramine. GIUSEPPE GRAM-CRISTALDI (Gnzzettcc 1906 36 ii 505-51 1) -Hexa- methylenetetramine volnt ilisev without decomposing especially in 8 current of hydrogen and snlulimes on the cooler parts of the tube [S. DI FRAN( o the crystals formed are rhombic drcahedra helonging t o the regular system (compare Wolil Abstr. 1886 860)]. When a mixture of the base with reduced nickel is heated a t 80' in a curyent of hydrogen reduction takes place in the sense of the equation N(CH,NCH,) + 9H = NMe + 3Nif + 3CH T. H. P. Oxalylaminoacetic Acid A Product of the Oxidation of Glycylglycine.ADOLF KRAEMER (Ber. 1906 39 4385-4388. Compare Pollak Abstr. 1 905 i 750).-Pollak's statement that oxalyl- aminoacetic acid is formed when a cold aqueous solution of glycyl- glycine is oxidised by calcium permanganate is confirmed a s t h e calcinm salt prepared by Pollak's method is found t o be identical with the salt obtained from Kerp and Unge1's ethyl oxalylamicoacetate (Abstr 1897 i 269). The salt C,H,O5NCa,4H,O crystallises in white rhombic plates. The statement however t h a t this acid is hydrolysed by hydrochloric acid into nnimonia and acetic and oxalic acids is con- troverted the products obtained being oxalic acid and glycine; the latter was isolated in the form of the hydrochloride of the ester; acetic acid could not be detected.Novaine. W. D. H. W. R. Glutamjne. ERNST SCHULZE (Landw. Versuclrs-Stut. 1906 65 237-24 6).-Earlier results obtained with glutamine from sugar beet (Schulze and Bosshard Abstr. 1885 759) indicated t h a t the substance has no appreciable rotatory Fower. Sellier (Abstr. 1904 i 372) has recently examined a preparation which gave [a] + 6.15'. New results with seven preparations of glutamine from mangolds pumpkins mustmd and brake-fern varied froui [a]? + 1.9 to + 9.5". The variations and the former negative result are attiibuted t o the presence of varying amounts of racemic glutamine. Solutions of glutamine can be distilled with magnesia at 40' without liberation of ammonia. When boiled with water alone glutamine yields a considerable amount of ammonia ; whilst by boiling in presence of magnesia nearly the whole of the nitrogen of the CO*NH group is converted into ammonia in two hours.Electrolysis of Aqueous Acetone and Pyridine Solutions c f Thiocyanates. Part I. STEVENSON BINNIKCI and F. MOLLTO PERKIN (T~ans. Farnday Soc. 1906 2 94- 97)-On electrolysing a N. H. J. M.ORGANIC! CHEMISTRY. 115 20% solution of ammonia thiocyanate in water with a current density at the anode of ten amperes per square decimetre a yellow colouring matter is obtained in 15-20% yield. In the experiments the cathode was rotated within a cylindrical anode and i t was found necessary t o remove the colouring matter continuously from the surface of the anode by means of brush-like appendages attached t o the cathode. The sub- stance does not appear t o be identical with canarine.It blackens when heated with pyridine. When alkaline solutions are electrolysed the yellow substance is not formed. Acetone solutions of ammonium thiocynnste also give rise t o a n orange-yellow su bstanre when electroly sed. This substance dissolves in boiling solutions of alkali hydroxides and is reprecipitated as a brown flocculent substance on acidifying wi? h sulphuric acid hydrogen sulphide being evolved. It is not acted on by strong nitric acid at the ordinary temperature. On boiling with pyridine a part of i t dissolves and the remainder turns black. Pyridine solutions of the thiocranate remain clear during electro- lysis but a n orange-yellow substance is precipitated when the solution is poured into ten times its volume of water The substance dissolves in boiling alkali is reprecipitated by sulphuric acid and dissolves in nitric acid from which i t is reprecipitated on the addition of water.When a lead anode is used in the pyridine solution the metal dissolves and on pouring the solution into water light brown crystals of lead thiocyanate separate. The product is readily soluble in pyridine. H. Ril. D. Cyanogen Bromide. THOMAS EWAN (J. Soc. CAern. Ind. 1906,25 1130-1133).-1n connexiou with the use of cyanogen bromide as a reagent for the extraction OF gold from refractory ores the author has measured the velocity of the reactions H BrOg + 5HBr + 3HCN = 3BrCN + 3HBr + 3H,O HBrOQ + 2HBr + 3HCN = 3BrCN + 3H,O HBrO -+ 5IIBr = 3Br2 + 3H,O. Solutions containing sodium bromate bromide and cyanide in qunn tities corresponding with these equation; mere heated at 25" and the reaction started by addition of a quantit,y of hydrochloric acid sufficient to neutralise the cyanide and liberate the bromic and hydrobromic acids.After measured intervals of time the reaction was stopped by the addition of a n excess of sodium hydroxide which conyerts the cyanogen bromide into cyanate and bromide ; the unchanged cyanide was then titrated with silver nitrate and potassium iodide as indicator after which the solution was acidified excess of potassium iodide added and the iodine liberated by the unchanged broinic acid was titrated. Assuming that the strong acids are completely dissociated and the hydrocyanic acid undissociated i t is found that the experimental data satisfy the velocity equation - dC,,,3T/dt = k[C,.]2[Cn,,][GB,03.] in which the bracketed symbols denote the concentration of the bydrogen bromide and bromate ions respectively. The values obtained for k in the three reactions are practically identical and warrant the conclusion that no secondary change of importance takes place.The interaction between bromic and hydrobrornic acids determines therefore the rate of the reaction between bromate bromide and cyanide.I16 ABSTRACTS OF CHEMICAL PAPERS. When sulphuric acid is used instead of hydrochloric acid the rabe of change is considerably smaller but this can in all probability be accounted for by the smaller hydrogen dissociation. Cganogen bromide has no action on hydrocyanic acid but reacts quickly with potassium cyanide according to the eqrration CWBr + KCN = KBr + C,N,.With alkali hydroxides carbonates and water reaction takes place according to the equation CNBr + 20H‘= Er’+ CXO’ + H,O. Quantitative measurements of the yield of cyanogen bromide under different conditions show that this approximates to the theoretical value the more closely the cxperirnental conditions approach those indicated by the study of the react’ion velocities. UI. M. D. Preparation of Calcium Cyanamide. FREDRIIL CARLSON (Chem. Zeit. 1906 30 126 l).-The calcium chloride used in Polzeniusz’s method for the preparation of calcium cyanamide (D.R.-P. 1901 163320) can with advantage be replaced by calcium fluoride; the product is not hygroscopic and can be kept without dcterioration for a long time.c f . s. Additive Compounds of Organic Haloids with Silver Nitrate. ROLAND SCHOLL and WILIIELM STEINKOPF (Ber. 1906 39 4393-4400).-The compounds of nitriles with metallic salts greatly resemble hydrates. Although a solution of silver nitrate in acetonitrile yields only silver nitrate on evaporation it has been found possible to isolate additive compounds from halogen derivatives of acetonitrile. The halogen atoms share in the forniation of these compounds. A double compound of sil vey nitrate and iodoacetonitrile AgNO,,CH,I*CN is obtained together with nitric oxide and silver iodide when a solu- tion of silver nitrite in acetonitrile is addcd carefully to zt mixture of iodoacetonitrile and acetonitrile at O’ or in a pule state when the iodoacetonitrile is added drop by drop to a well-stirred aqueous silver nitrate solution.It forms almost colourlezs crystals probably ortho- rhornbic m. p. 121’ and may be recrystallised from water a t 50° but is decomposed into its constituents by boiling water. When distilled i t yields cyunometlqb nitrate CN*CH,*O*NO a colourless oil b. p. 69-70°/1 3 mm. (slight decomp.) exploding when quickly heated. XiEvey x zit rate-bronzorccetonitrile AgN03,CH,Br*CN crpstallises in small almost colourless plates when the aqueous solution is quickly cooled. It sinters and decomposes a t 110’. Silver nitrute-methybene iodide AgN0,,CH,f2 is a white crystalline powder m. p. 80-81* and only slightly stable. Chloroacetonitrile does not yield a n additive com- pound and methyl iodide ethyl iodide iodoform and ethyl iodoacetate give Fanto’s silver iodide-nitrate (Abstr.1903 ii 648). The paper concludes with a discussion of the natiire of these com- pounds from the standpoint of Werner’s theory of supplementary valency (Abstr. 1902 ii 554) and their importance in the theory of the intoraction of organic haloitls and silver nitrate (compare Euler Abstr. 1906 i 789 ; Burke and Ttonnan Trans 1904 85 555). w. K.ORGANIC CHEMISTRY 117 New Method of Forming Organic Compounds of Phosphorus. J. RERTHAUD (Compt. rend. 1906 143,1166-1167). -By the action of white phosphorus (1 atom) on methyl or ethyl alcohol (2 mols.) in a sealed tube a t 250' the chief product is the corresponding tetra-alkylphosphonium hydroxide to the extent of 20-30% of the phosphorus employed ; the other products are phosphoric acid the alkyl phosphinic acids and hydrogen phosphide together with a small quantity of the alkylphosphines in the case of methyl alcohol but in the case of ethyl alcohol the quantity of ethyl- phosphine corresponds with 20% of the original phosphorus.M. A. W. Chlorination in Organic Chemistry in presence of Thallous Chloride. VICTOR THOMAS (Cdmpt. rend. 1907 144 33-34. Com- pare Abstr. 1898 i (340; 1899 i 26 676)-Thallous chloride acts similarly to ferric chloride in the chlorination of aromatic hydro- carbons and their haloid derivatives. Benzene gives a mixture of chlorobenzenes. Bromobenzene gives the series of chlorobromo- benzenes C,H,,-,,,,,,BrCI but no evidence was obtained of the dis- placement of bromine by chlorine.From p-dibromobenzene the same series of chlorobromobenzenes C,HtG_ (7L+1)IBrCln is obtained one atom of bromine being displaced. I n particular the trichlorobromobenzene m. p. 138O is described. Iodobenzene invariably gives a complex mixture of chloroiodobenzenes. Iodine is displaced from only a very small proportion of the iodobenzene if a t all. Among the products isolated are the three isomeric chloroiodobenzenes and a tvichloroiodo- benzene m. p. 106 -107O. The latter gires a mononitro-derivative m. p. 57*5-58" probably identical with that described by Istrati (BuEI. SOC. Xci. Buccwest 2 S) and two polynitro-derivatives. (1) White or very light yellow needles m. p. 177" probably a dinitro-compound. (2) Golden-yellow lamelh resembling lead iodide very volatile but melting when thrown on a surface previously heated to 279O probably a trinitro-compound.No intermediate additive products could be isolated. Thallous chloride is useless in the chlorination of acetic acid. E. IX. 1-Chloro-2 4 6-tri-iodobeneene. W. V. GREEN (Amer. Chern. J. 1906 36 600-604).-1-ChZos.o-2 4 6-tri-iodobenzene C,l<,C113 pre- pared from 2 4 6-tri-iodoaniline by the diazo-reaction crys- tallises from a mixture of alcohol and benzene in faintly pink pyramidal-ended slender prisms m. p. 119-120". When treated with sodium ethoxide it gives up some of its iodine thus differing in behaviour from the analogous chlorotribromobenzene. Nitric acid converts it into 1-cl~loro-2 4 6-tri-iodo-3 5-dinitrobenxene which crystal- lises from a mixture of benzene and light petroleum i n yellowish-white needles m. p.266-269'. T. H. P. The Sixth Di-iodonitrobenzene. GEOKG KORNER and ANGELO CONTARDI ( A t t i €i!. Accud. Lincei 1906 [v] 15 ii 577-5179 Com- pare Abstr 1906 i 641)-1 2-D.i-.iotZo-3-.liitroBenxelze prepnred by a118 ABSTRACTS OF CHEMICAL PAPERS. method similar to that used for the synthesis of 1 2-dibromo-3-nitro~ benzene (Zoc. cit.) crystallises from alcohol in bundles of long needles m. p. 110*2O is markedly greener than its isomeridea and dissolves in ethyl acetate. 2 4-Di-iodo-6-nitroccndine crystallises from alcohol in slender orange- yellow needles m. p. 152". 6-Iodo-2-nitroaniline crystallises from alcohol in orange-red needles or scales m. p. 122".T. H. P. The Sixth Tribromonitrobeneene and some of its Derivatives. GEORG K~KNER aud ANGELO CONTAXUI (Atti ll. Accad. Lincei 1906 [ v] 15 ii 580-585).-3 4 5-I'ribrornoaceta~ziEide~ C,H,Br,*NHAc prepared by the action of bromine on 3 6-dibromoacetanlllde in acetic acid solution crystallises from ether i n slender white needles rn. p. 3 4 5-l'lib~onzo-2 -nitroucetaniZide N0,*C6HBr,*NHAc obtained by the action of sulphuric and nitric acids on 3 4 5-tribromoacetanilide crystallises from alcohol or benzene in needles and from ethyl acetate in mamillary masses of white prisms m. p. 229--230°. 3 4 5-l\*ib~orno-2-~~itrocclLiline NO,*C,HBr,*NH crystallises from alcohol in orange-yellow needles and from ethyl acetate in tufts of shining yellowish-red needles m.p. 134'. 1 2 3-!Z'ribronzo-4-r~itroberixene C,,H,Br,*N O prepared either by the action of ethyl nitrite 011 3 4 5-trihromo-2-nitroaniline in alcoholic solution under pressure or by direct nitration of 1 2 3-tribromo- benzene crystallises from alcohol in faintly green satiny needles m. p. 85*4" and dissolves readily in benzene ether or ethyl acetate. 2 3-0ibronao-6-izitl'o~~).~iZiize NO,*C,H ,Br2-NH2 prepared by the action of alcoholic ammonia on 1 2 3-tribrumo-4-nitrobenzene crystal- lises from ethyl acetate in bundles of lauceolated fiittened dichroic needles which appear red in reflected and yellow in transmitted light m. p. 149". 2 3 4-~~.ibi.oinoaniZine C,H2Br,*NH2 prepared by the reduction of 1 2 3-tribrorno-4-nitrobenzene by means of stannous chloride and hydrochloric acid is a feeble base crystallising from aqueous alcohol in white lamella? m.p. 100.6". 2 3 4-Zi.ib~.onzocccetcciziZ~~e7 C H Br,*NHAc crystallises from alcohol in flattened white needles m p. 160'. Nitration of 1 2 3-tribromo-4-nitrobenzene with a mixture of concen- trated sulphuric and nitric acids a t 139' yields (1) 1 8 3-tribromo- 4 ; 5-dinitrobenzene (compare Jackson and Fiske Abstr. 1902 i 362) ; (2) 1 2 3-ti-ibromo-4 6-dinitrobenxene CoHBrs(NOJ2 which crystal- lises from alcohol in greenish-yellow flat needles or prisms m. p. 150'. 2 3-Dibromo-4 6-dinitroaniZine C,HBr,( N02)2*NH2 obtained on treating 1 2 3-tribromo-4 6-dinitrobenzene with alcoholic ammonia crystallises in sulphur-yellow needles m. p. 2 19O. 2 5 5-2 5 6".6 2. T. H. P. A New Method of Reductoin. I. THEODOR WEYL (Ber. 1906 39 4340-4343).-Hydrogen phosphide obtained from water and redORGANlC CHEMISTRY. 119 phosphorus acts as a reducing agent when nascent. Thus when a mixture of nitrobenzene red phosphorus and water is heated at looo under pressure for several hours the nitrobemen? is reduced to aniline I n successive experiments the yield of aniline was 24.8 31.7 32.5 64.0 41.7 86.2 and 55.5% respectively the duration of heating being 8 8 9 12 28 35 and 42 hours. The phosphorus is partly converted into phosphorous and phosphoric acids. When a mixture of nitrobenzene red phosphorus aud water is heated a t 110-115" only very little aniline is formed ; ammonia however is formed in considerable amount. The reduction of nitrobenzene t o aniline is represented by the equation 3C6H,*N0 + 4PH = 3C,H,.NH + 2H3P03 + 2P.A. McK. Reduction of Nitrobenzene by Aliphatic Alcohols in Light. GIACOMO L. C'IAMICIAN and PAUL SILBER (Uer. 1906 39 4343-4344). -Aniline and paracetaldehyde do not yield quinaldine in the light even after one year's exposure ; moreover. tho formdtion of quinoline bases in the reduction of nitrobenzene by aliphatic alcohols in light is pre- vented almost entirely by the absence of acids (compare Abstr. 1906 Ammonium and Sodium Sulphides as Partial Reducing Agents for Aromatic Dinitro- and Polynitro-compounds KURT BRAND (J. yr. Chem. 1906 [ ii] 74 449-472).-A systematic investigation of the reduction of aromatic polynitro-compounds by means of sodium sulphide has been undertaken as accounts of the method occur chiefly in patents and are somewhat scattered in chemical literature.I n the present paper the work of previous authors whose stateaents are in many cases contradictory is reviewed and the results of the investigation so far obtained are described. The reduction of ni-dinitrobenzene with ammonium hydrogen sul- phide dissolved in a mixture of alcohol and ethyl acetate a t 5" leads to the formation of mnitrophenylhydroxylnmine (Abstr. 1906 i SO) or with sodium sulphide in boiling alcoholic solution to the formation qf di-nz-nitroazoxybenzene anJ a small amount of m-nitroaniline whilst on reduction with sodium sulphide in alcoliolic solution in pre- sence of ethyl acetate the chief product is m-nitroaniliue only small amounts of the azoxybenzene being formed (de Bruyn and Blanksma Abstr.1901 i 460; Blanksma ibid. 461). When boiled with 1 mol. of sodium d i d p h i d e in alcoholic solution m-dinitrobenzene is almoat completely reduced the product consisting of m-nitroauiline in a jield of S7"lO and di-m-nitrodzoxybenzene in a yield of 5.5'/ of the dinitrobenzene but with 8 mol. of sodium disulphide 38'/ of the dinitro-compound is regained unchanged m-nitroaniline being formed to the extent of 35% and di-m-nitroazoxybenzene t o the extent of 47O/ of the dinitrobenzene (compare Blanksma Zoc. cit. ; Kunz Abstr. 1903 i 813). I n boiling alcoholic solution m-dinitrobenzene is reduced almost quantitatively by sodium pentasulphide forming m-nitroaniliue or by sodium hydrogen sulphide forming m-nitroaniline and traces of di-rn-nitroazoxgbenzene.2 6-Dinitrotoluene is reduced by sodium hydrogen sulphide in i 10). c. s.120 ABSTRACTS OF CHEMICAL PAPERS. alcohol ic-et h y 1 acetate solution forming 6 -nit ro-2 -aminot 01 uene together with traces of 2 6-tolylenediamine ; 2 4-dinitrotoluene is reduced similarly t o 2-nitro-4-aminotoluene together with smaller quantities of 4-nitro-2-aminotoluene the total yield of nitroamines amounting t o 80% of the theoret,ical. The action of sodium hydrogen sulphide on 2 4-dinitroaniline leads to tho formation of 4-nitro-o-phenylenedinmine and traces of nitro- p-phenylenediamine or on picric acid to the formation of picramic acid. G. Y. The Two Modifications of o-Nitrotoluene. IWAN VON OSTROMISSLENSKY (Zeit.yhysiknl. Chem. 1906 57 341-348).-When freshly-distilled o-nitrotoluene is rapidly cooled to - 20" it solidifies sometinies to the labile a-modification (m. p. - 10*56O) sometimes t o the stable P-modification (m. p. - 4.14"). Superheating of the vapour during distillation favours the subsequent separation of the /3-modifi- cation. Another method for preparing the latter is to cool the liquid substance to -50" or -60"; the primary crystallisation from the cooleJ liquid consists of the a-modification but after a short time this changes spontaneously into the P-modification. A t all temperatures not too close to the melting point of the a-modification the change a .- /3 takes place so that the two modifications are monotropic. It is probable however that the transition point is close to the melting point of the a-furm.The freezing point depression constants are found to be for the a-form 50.8 ; for the p-form 71 -8. The molecular weights of iodine and sulphur dissolved in the p-form are found by the freezing point method t.0 correspond with I and S - Sll respectively. Allied substances existing in two modifications (the m. p's. of which are A' apart) are o-chlorotoluene (A = 5*SG) o-toluidine (A = 5") o-chlorophenol (A = 7") o-broinotoluene (A = 5.1'). The two modi fications of o-chlorotoluene are enantiotropic ; a t - 50" the change a - p takes place at - 17" the change P -3 a ; the transition tempera- ture lies therefore between - 17" and - 50'. J. C. P. Nitration of Aniline and of certain of its Derivatives J.BISHOP TINGLE and F. C. BLANCK (Amei-. Chem. J. 1906 38 605-610).-Sttempt,s~ts were made to nitrate aniline (or aniline nitrate) directly by the action of 99% nitric acid free from nitrous acid but although carbamide mas added t o decompose any nitrous acid formed and the reactions were carried out in platinum vessels immersed in a freezing mixture it mas found to be impossible to keep the tempera- ture sufficiently low tarry or carbonaceous products being always formed. Nitriz acids of 50.7 1-75.33% concentrations give with aniline a pink solid stable at Oo the colour being instantly dischrtrged by the addition of a little water or aniline. Slight excess of acid increased or restored the colour and if the added acid mere sufficiently concen- trated the pink colour darkened until it became black the whole mass gradually charring and sometiiiies incandescing. Wibh nitric acids ofORGANIC CHEMISTRY.121 concentrations up to ’75*33% any charring produced is due to attack of the aniline nitrate and not of the nitrate. The readiness of nitration of aniline by means of nitric and sulphuric acid hence cannot be due to “protection” of the amino-group by the sulphuric acid as this group is equally well ‘( protected ” in aniline nitrate. Experiments were also made on the action on anilines substituted in the amino-group of 80% nitric acid (D 1.46) in presence of acetic oxalic trichloroacetic or 92% sulphuric acid (D 1.83). The results show that the position assumed by the entrant nitro-group is definitely influenced both by the acid present with the nitric acid and by the amino-substituent.T. H. P. Preparation of Simple Aromatic Cyanamides. PAUL PIERRON (BUZZ. SOC. chim. 1906 [iii] 35 1197-1204).-The method of pre- paration described by Cloez and Cainizzaro (Compt. rend. 1851 32 62) gives good results in the case of naphthalene derivatives whilst a modification of that proposed by Hofmann (Bey. 1869 2 600 and 1870,3 264) furnishes better results in the case of benzene deriva- tives especially when the desulphuration of the thiocarbamides is accomplished by the use of cupric sulphate in place of litharge. m-l’olylcyanacmide prepared from m-tolylthiocarbamide by the modi- fication of Hofmann’s method referred to is a viscous nearly colour- less liquid which in contact with water forms a hydrate (m.p. 27’) (compare Heller and Bauer Abstr. 1902 i 444) and in contact with hydrochloric acid furnishes m-tolylcarbamide (m. p. 142’). a-Naphthylcyanamide and the isomeric P-compound were prepared hy Cloez and Cannizzaro’s method cyanogen bromide being employed instead of cyanogen chloride. m-Ethoxyphenylcyunnmide was also pre- pared by this method alcohol :being employed as a solvent for the m-ethoxyaniline in place of ether. It crystallises in colourless needles m. p. 57O and is readily hydrolysed by acids t o the corresponding carbamide which crystallises in colourless flattened needles m. p. 112”. m-Ethoxyphenylcnrbamide is also readily obtained by the action of potassium cyanate on m-aminophenetole hydrochloride. o-Bromopheny Zcpunamide similarly obtained cry stallises in brilliant slender colourless needles m.p. 94O and by boiling its solution in alcohol with hydrochloric acid is transformed into the corresponding carbamide which crystallises in colourless flattened needles m. p. 302* and by repeated evaporation with hydrochloric acid furnishes ammonia 0- bromoaniline and carbon dioxide. m-Bvornophenylcyan- amide similarly obtained from m-bromoaniline crystallises from benz- ene in brilliant colourless lamellae m. p. 84O is readily soluble in alcohol and less so in ether and with acids yields m-bromophenyl- carbamide (compare Folin Abstr. 1897 i 470). p-Bromophenplcyan- amide prepared from p-bromoaniline crystallises in colourless long slender prismatic needles m. p. 112O is very soluble in alcohol fairly so in ether less so in chloroform and slightly so in water; it is readily soluble in alkalis and insoluble in dilute acids.Hofmann’s method is not applicable t o the preparation of the bromophenylcyanamides owing to the difficulty of preparing the neces- sary thiocarbamides. T. A. H. VOL. XCII. i. J:122 ABSTRACTS OF CHEMICAL PAPERS. Influence of Certain Substituting Uroups on the Oxida- tion of Tertiary Aminas to Amine Oxides. EUGEN BAMBERGER and LEO RUDOLF (Ber. 1906 39 4285-4293. Compare Abatr. 1902 i 364 ; Bamberger and Tschirner Abstr. 1899 i 347).-The amount of amine oxides formed by the oxidation of tertiary aromatic bases by means of Caro's acid varies with the alkyl groups attached t o the nitrogen atom and with the absence or presence and position of methyl groups in the benzene nucleus.I n comparative experiments 10 grams each of dimethylaniline dimethy1.p-toluidine dimethyl-o- toluidine diethylaniline urn-dimethylxylidine and dimethylmesidine yielded 11.1 10.9 7-16 6-89 0 and 0 grams respectively of the cor- responding amine oxides; in a second series of experiments in more dilute solixtion of 10 grams each of dimethylaniline dimethyl-s- toluidine dimethyl-p-toluidine diethylaniline diethyl-o-toluidine and diethyl-p-toluidine 0.0 6.35 0.3 6.43 8.84 and 6-18 respectively remained unoxidised; whilst in a t'hird series of 10 grams each of diethyl-o-toluidine and diethyl-p-toluidine 8.7 and 5.8 grams respec- tively remained unchanged. The oxidation takes place more easily with dimethyl- than with cliethyl-aniline is hindered by the presence of an o-methyl group and is prevented by the presence of two o-methyl groups.The action of methyl sulphate on mesidine leads t o the fdrmatioii of dimethyl- and methyl-mesidines which are separated by conversion of the latter into its cccetyl derivative C,H,Mti,=NMeAc ; this crystal- lises in glistening prisms ni. p. 51-51*5" b. p. 150-150*5"/13 nim. Dimethylmesidine is colourless b. p. 213-3-213*5O/716 rum. 0905 (Hofmann Ber. 1872 5 718 b. p. 213-214' D 0*9076) but after treatment with Caro's acid is slightly yellow Dq12 0.9016. urn-Dimethylxyiidine prepared together with urn-methylxylidine by the action of inethyl sulphate on urn-xylidine is colourless b. p. 192*5-192*8O/716 mm. or 76*8-77.Z0/11 min. Die“ 0.912 (b.p. 196' D 0.9296 Hofmann Zoc. cit. 712 ; b. p. 195-196' Friedlander Abstr. 1899 i 350) but after treatment with Caro's acid is yellow D:''z 0.914. Contrary to Friedliinder's statement (Zoc. Zoc.) the base does not react with nitrous acid. G. Y. Asymmetric Nitrogen XXVI. Optically Active Phenyl- benzylmethylethyl Ammonium Bases. EDGAR WBDEKIND and EMANUEL FR~LICH (Bey. 1906 38 4437-4442. Compare Abstr. 1906 i 161 162).-The values [MI +17*3 for the active cation NMeEtPh*C,H obtained by Wedekind (Bey. 1907 37 2727) and [MI +19*3 obtained by H. 0. Jones (Trans. 1904 85 225) appear too low in view of the values [M] + 285 for the active cation NMePrPh'C7H and [MI - 279 for the corresponding isobutyl base (compare Abstr. 1905 878). Yheiny~benxyZ~netl~yZethyZa~,znaonium bromide forms prisms m.p. 158-159' ; it was not found possible t o resolve it by crystallisaticn of the d-bromocarnphorsulphonate. IJy continued fractional crystallisa- tion af a large quantity of the d-camphorsulphonate a fraction [MID .t 116.1' was obtained equivalent t o [MI 1-64.4" for the cation NMeEtPh- C,H,.ORGANIC CHEMISTRY. 123 The ammonium iodide prepared from this fraction had La] + 41.4' in alcohol and did not alter when kept ; in chloroform [a] + 56-54 sutoracemisation quickly set in. E. F. A. Preparation of 8- Hexanitrodi-m-xylylamine. JAN J. BLANKSMA (Rec. trav. chim. 1906 25 373 -375).-5-B~o~20-3 4 6,trinitro-m- xylene which forms colourless crystals m. p. 224' is obtained by nitrating 5-bromo-m-xylene ; when heated with m-xylidine in alcoholic solution i t yields 2 4 6-trinitro-di-1 3 5-xylylamine which on nitration is converted into s-hexnniti-odi-1 3 5-xylylamine7 m.p. 222'. This substance separates from chloroform in glistening crystals which contain 1 molecule of the solvent. P. H. Hydroxamic Acids. RAYMOND MARQUIS (Cornpt. rend. 1906 143 1163-1165. Compare Abstr. 1905 i 524).-Thiele and Pickard (Abstr. 1900 i 29) explain the formation of symmetrical disubstituted carbamides from the alkali salts of the dihydroxamic acids (Lossen Abstr. 1894 i 415) on the assumption that the acid undergoes the Beckmann rearrangement with the formation of a carb- imide which is converted into the cnrbsmide by the action of water. The author has examined the behaviour of hydroxarnic acid towards reagents which induce the Beckmann rearrangement and finds that in certain cases the reaction is normal.Thus benzhydroxamic acid yields phenylcarbamide when treated with thionyl chloride in the presence of boiling benzene and salicylhydroxamic acid when similarly treated yields oxycarbanil (Ransom Abstr. 1891 i 415) the acetyl derivative of which has m. p. 91' [Kalckhoff gives 95' (Abstr. 1883 734) and Bender gives 97.98' (Abstr. 1887 37)]. Phenyl-p-tolylcarbamide obtained by the condensation of phenyl- carbamide and p-toluidine m. p. 218O then solidifies and melts sharply at 221O [Paal and Valvolxem (Abstr. 1894 i 621) give 212" and Dixon (Trans. 1901 79 103) gives 215'1. Phenylcarbamy Zbenxhydroxuinic acid 0 H* C Ph NO CO N H Ph ob- tained by the condensation of phenylcarbsmide and benzhydroxamic acid in pyridine solution crystallises from alcohol i n small needles m.p. 309-21 0' ; pl~e.raylcarbamylsulicyli~ydroxam~c acid OH*C,H,*C(OH):NO* CO*NHPh crystallises from benzene and alcohol in flat pearly needles m. p. 18l0 which rapidly redden in the light. M. A. W. Preparation of Aromatic Thiocarbamides by the Hydrogen Peroxide Method. JULIUS VON BRAUN and ERICH BESCHKE (Ber. 1906 39 4369-4378. Compare Abstr. 1900 i 644; 1902 i 271). -Continuing the work on the mechanism of the reaction between primary aromatic amines and carbon disulphide in the presence of hydrogen peroxide the authors have applied the method in the follow- ing cases m- and p-Toluidine p-cumidine 1 3 4-xylidine and p-aminobenzyl cyanide react within a few minutes.Dicu?.lzyltl~iocarb~6~~~i~e has m. p. 149' ; w-dicyanoditolylthiocarbamide m. p. 19 lo is insoluble in alcohol . k 2124 ABSTRACTS OF CHEMICAL PAPERS. 0- and y-Chloroanilines react after two days whereas the meta-iso- meride undergoes a rapid conversion into the carbamide. m-Bromo- aniline readily yields the curbamide m. p. 128" whilst p-bromoaniline and p-iodoaniline require many hours. p-Anisidine and p-phenetidine react as readily as aniline itself o-anisidine only very slowly. Methyl anthranilate and ethyl p-aminobenzoate yield the correspoud- ing carbarnides after inany days but they have not yet been examined Decomposition of Dinitrophenyl Thiocyanate. OSCAR HINSBEIW (Be?.. 1906 39 433 1-4332).-According to Austen and Smith (Abstr. 1886 693) diriitrophcnyl thiocyanate obtained by the action of potassium thiocyanate on 4-bromo-1 3-dinitrobenzeno forms dinitrophenyl mercaptan m.p. 1 9 5 O when warmed with con- centrated sulphuric acid. According t o the author this observation is not correct since the product of the action in question is not uniform but a mixture of 2 4-dinitrophenyl mercaptan m. p. 131° and 2' 4'- tetranitrodiphenyl disulphide. The observation of Austen and Smith that when dinitrophenyl thiocyanate is warmed with a mixture of concentrated sulphuric acid and filming nitric acid a tetranitrodiphenyl sulphide m. p. 245" is produced is also erroneous. Use of Compounds of Bases with Sulphurous Acid as Photographic Developers. AUGUSTE LUMIXRE LOUIS LUMIBRE and ALPHONSE SEYEWETZ (Bull.8oc. chim. 1906 [ iii] 35 1204-1207). -Compounds of this type with p-aminophenol p-methylaminophenol and p-phenylenediamine have been obtained (1) by the action of sulphiir dioxide on the free bases suspended in warm water (2) by cooling warm solutions of the bases in " liquid commercial sodium bisulphite " (40%) or (3) by heating p-methylaminophenol sulphate with a solution of anhydrous sodium sulphite to which one-fourth of its volume of sodium hydrogen sulphite had been added. The product 100H*C6H,=NH,,H,S0 obtained with p-aminophenol occurs in white crystals having a faint odour of sulphur dioxide arid does not become brown on exposure to air. The compound 60H*C6H,*NI-IMe,H,SO~ yielded by p-methylamino- phenol occurs in small white crystals is stable in air has no odour of sulphur dioxide and has m.p. 87" evolving sulphur dioxide. The compound 9C6H4(N€€2)2,H2S03 obtained from p-phenylenedi- amine forms small white crystals having a feeble odour of sulphur dioxide is stable in air and has m. p. 1 3 7 O evolving sulphur dioxide These three substances are comparable as developers with the three bases from which they are derived and the solubility in water of the p-methylaminophenol product enables it to be used as a developer by the addition of sodium sulphite. Action of Bromine and Chlorine on Phenols. Substitution Products $-Bromides and $-Chlorides. XX. Action of Bromine on o-Cresol. THEODOR ZINCKE and A UCUST VON HEDENSTROM (AnnaZen 1905 350 269-287. Compare Abstr. 1906 i 739).-o-Cresol reacts completely. c.s. A. McK. T. A. H.ORGANIC CHEMISTRY. 125 readily with the calculated quantities of bromine alone or in presence of iron in chloroform or carbon tetrachloride solution forming mono- di- tri- and tetra-bromo-derivatives. The acetpl derivative of 5-bromo-o-cresol (Claus and Jackson Abstr. 1889 128) is an oil. The acetyl derivative of 3 5-dibromo.o-cresol (loc. cit.) crystallises in glistening needles m. p. 62". crystallises from light petroleum in long colourless needles m. p. 79"; t h e ucetyl derivative crystallises in glistening needles m. p. 72-73O. Ibtrabron7o-o-cresoZy C,MeBr;OH crystallisex in glistening needles m. p. 205"; the acelpl derivative forms glistening needles m. p. 154'. The action of sodium nitrite on these bromo-o-cresols in glacial acetic acid solution leads to the formation of bromonitro-derivatives. 5-Bromo- and 3 5-dibromo-o-cresols yield 5-bromo-3-nitro-o-cresol (Wroblewski this Journal 1874 27 52).4 5-Dib~omo-3-~zitro-o-cresoZ C7H,0,NBr formed from 3 4 5-tri- bromo-o-cresol crystallises in yellow needles m. p. 14 1" (decomp.). 4 5 6-l'ribronzo-3-nitro-o-cresol NO,*C,MeBr,*OH formed from tetrabromo-o-cresol crystallises in yellow monoclinic prisms m. p. 156' (deconip.). The action of bromine on 5-bromo- or 3 5-dibromo-o-cresol a t 170" leads to the formation of 3 5-dibromo-o-cresol $-bromide or C,H,OBr,*CH,Br (Auwers and Buttner Abstr. 1899 i 36). 3 4 5-Tribromo-o-cresol $-bromide C7H40Br4 formed by heating the tribromo-creeol with bromine in a sealed tube in the water bath crystal- lises in monoclinic needles or prisms m.p. 134O reacts only very slowly with alkali hydroxides and when shaken in ethereal solution with dilnte alkali hydroxides forms a white amorphous polymeric metluJ- enequinone. Reduction of the $-bromide with zinc and hydrogen bro- mide in glacial acetic acid solution leads to the formation of 3 4 5- tri bronio-o-cresol. The acetyL derivative OAc*C,HBr3* CH,Br forms glistening needles m. p. 137'. 3 4 5-~,.ibromo-2-i~yd~.oxy6enx?/l alcohol OH* C,HBr,*CH,*OH pre- pared by boiling the +-bromide with aqueous acetone crystallises in stellate aggregates of needles m. p. 141" ; the diacetyl derivative crystallises in glistening needles m. p. 92'. OH*C,HBr,*CH,*OMe prepared by boiling the $-bromide with methyl alcohol crystallises in glistening needles m.p. 81-42"; the ucetyl derivative forms white needles 133. p. 90-91'. When boiled for a few minutes with acetic acid and sodium acetate the +-bromide forms the acetyl derivative C,H,OBr,*CIi,* OAc which crystallises in glistening needles m. p. 130-1 31° on hydrolysis yields tribromohydroxybsnzyl alcohol and forms the diacetyl derivative of this when heated with sodium acetate and acetic anhydride. Tetrahomo-o-cresol $-bromide C,HOBr4*CH2Br or OH *C,Br,* CH,Br formed by heating the tetrabromocresol with bromine in a sealed tube at looo crystallises in colourless needles m. p. 156" yields a white amorphous poduct when shaken with ether and a dilute alkali hydr- 3 4 5-(or 3 5 6-)T?.ibronzo-o-cresoZ C6HMeBr,*OH OH*C,H,Br,*CH Kr c 1H904Br3 9 The methyl ether,126 ABSTRACTS OF CHEMICAL PAPERS.oxide and if shaken with benzene a n d a dilute alkali hydroxide forms the amorphous substance and a yellow solution which on evaporation deposits a yellow !residue probably the o-met hylenequinone. The acetyl derivative OAc*C,Br,*CH,Br formed by boiling the +-bromide with acetic anhydride crystallises in small hard needles m. p. 156'. Tetra- bromo-o-hydroxybenxyl cilcohol C7H702Br4 crystallises in small needles m. p. 158' (decomp.) ; tbe dimetyl derivative Cl1H8O48r4 crystallises in glistening needles m. p. 138-1 39'. The methyl ether CgH6O2Brq forms white needles m. p. 94-95O ; the acetyl derivative forms glisten- ing needles m. p. 98-99'. The ace@ derivative C,HOBr,*CH,*Ohc,. prepared by boiling the +bromide with glacial acetic acid and sodium acetate forms white needles m.p. 133O on hydrolysis yields tetrabromo-o-hydroxybenzyl alcohol and the diacetate of this when boiled with acetic anhydride and sodium acetat'e. G. Y m-Tolyl Ether and Derivatives. ALFRED N. COOH (Amer. Chem. J. 1906 36 543-551 Compare Gladstone and Tribe Trans. 1882 41 Il),-Alecminium m-tolyloxide prepared by the action of commercid aluminium on m-cresol is a brittle grey to black translucent solid having a vitreous lustre and a conchoidal fracture. When dist,illed in a vacuum it yields a small quantity of m-cresol and a large proportion of a substance b. p. 240'130 mm. but under ordinary pressure it gives m-cresol m-tolyl ether a solid b. p. about 300' (uncorr.) and a red liquid b. p.about 360'. m-Tolyl ether has b. p. 290.5-291.5O and D21 1.0323 and its viscosity is 1.333 a t 1 5 * 5 O 1.194 a t 30° 1.166 at 40° and 1.139 at 50'; itsviscosityis hence 9.4% greater than that of phenyl ether (1.095) a t 30° in spite of its lower specific gravity. It is volatile in a current of steam. Chromic acid in glacial acetic acid oxidises it to a white powder in- soluble in a1 kalis. Dibromo-m-tolyl ether O(C,H,BrMe) is a white crystalline substance m. p. 4S0 b. p. 250"/15 mm. and 340-350' (uncorr.) at ordinary pressure. Tetil.abs*orno-m-toZ31 ether is a pale yellow sticky viscous substance crystallising in nodular aggregates b. p. 260-270°/35 mm. O( C6H3&Te 'NO,) separates from alcohol in yellow crystals m. p. 112-113°. Diamino- m-tolyl ether hydrochloride O(C,H,&Xe*NH,,HCl) was prepared and also the free base.O(C,H,Br,Me) Dinitro-m-toEyl ether T. H. P. Nitration of Meta-Substituted Phenols. JAN J. BLANKSMA (Proc. K. Akad. Wetemch. Amsterdam 1906,9 278-280).-The nucIear hydrogen atoms in m-nitrophenols containing a hydroxyl methyl methoxy- or ethoxy-group or chlorine or bromine in position 5 are readily substituted by three atoms of bromine by treatment with bromine water or by three nitro-groups by nitration by nitric acid (D 1.52) and sulphuric acid. The tetranitro-compounds separate from a mixture of these acids in colourless crystals turn yellow in the presence of water have a bitter taste and an acid reaction and areORGANIC CHEBITSTRY. 127 explonsive. If the phenolic hydrogen atom is replaced by methyl only two nitro-groups can be introduced.By boiling water tetranitro-m-cresol m. p. 175' is conyerted into trinitro-orcinol whilst tetrnnitroresorcirzoI m. p. 152" chlorotetranitro- phenol m. p. 147' or bronzotetrccnitiwo~henol m. p. 157' yield trinitro- phloroglucinol. 5-Nitroresorci.ilol has m. p. 1/58' and the ethyl ether m. p. 80"; the tetranitro-methy2 and ethyl ethem have respectively m. p. 115O and 110' ; 3-c~~lol.o-5-nitro~~e?~oZ m. p. 147O and t h e bromo-compound m. p. 145'. c. s Synthesis of &Halogen Ethers and of a8-Dihalogen Deriv- atives of Butane. JULIUS VON BRAUN and ERICE BESCHKE (Bey. 1906 39 4357-4362).-a8-Dichloro- or -dibromo-butane can be obtained in 10% .yield by reducing succinonitrile with sodium and alcohol benzoylating the product and treating the resulting mixture with phosphorus pentachloride o r pentabromide.Benzo-6-phenoxy butylamide (compare this vol. i 80) and phos- phorus pentachloride in molecular quantities react to form ultimately a-chloro-s-phenoxyb~tane CH,Cl*CR CK,*CH OPh wbic h is a colour- less refractive pleasant-smelling liquid b. p. 147'/12 mm. and reacts with sodium phenoxide to form Grignard's a6-diphenoxybutane (Abstr. 1904 i 494). a&Dichlorobutane C,H8Cl b. p. 5&-/58'/12 mm. is obtained from the preceding chlorinated ether and concentrated hydrochloric acid above 130". a-Ioclo-6-phenoxybutane CH,f*[CH,],*CH,*OPh obtained from the chlorinated ether and sodium iodide in alcoholic solution forms white leaflets xn. p. 43-44O b. p. 155-160'/15 mix. and is changed quantitatively by hydriodic acid a t 100' into as-di-iodobutane as-Dibromobutane cannot be obtained from phosphorus penta- bromide and benzo-8-phenoxybutylainide but is prepared readily from as-diphenoxy butane and hydrobromic acid at 130-1 40".c s. Constitution and Colour of Nitrophenols. HUGO KAUFFMANN (Ber. 1906 39 4237-4242. Compare Abstr. 1900 i 480; 1901 i 318; 1906 i 577; Kauffmann and Franck Abstr. 1906 i 841).- A reply to Hantzsch (Abstr. 1906 i 353 533 ; Ley and Hantzsch i6id. 790). Nitroquinol dimethyl ether is a very stab10 substance and its yellow colour carnot be attributed t o the presence of nitro- quinol. I t s solution in light petroleum is colourless but deposits yellow crystals. Free nitroquinol dissolves in light petroleum to a yellow solution.G. Y. HUGO KAUFFMANN and IMANUEL FRITZ (Ber. 1906,39,4243-4248. Compare Kauffmann Abstr. 1906 i 577 ; preceding abstract ; Hantzsch Abstr. 1906 i 353 833).- When prepared by nitration of quinol dimethyl ether nitroquinol dimethyl ether contains traces of a hydrolytic product probably the monometliyl ether which is removed comp'tetely on recrystallisation from alcohol. The pure dimethyl ether is yellow and is unchanged on Nitroquinol Dimethyl Ether.128 ABSTRACTS OF CHEMICAL PAPERS. addition of an alkali hydroxide whereas 0.007 gram of the hydro- lytic product dissolved in 1 litre of water gives a distinct change of colour. The solubility of the dimethyl ether in water is diminished by the addition of sodium carbonate. It yields only traces of hydro- lytic products when treated at the laboratory temperature with con- centrated or boiled with dilute sulphuric acid ; a substonce crystallising in orange-red needles m.p. 79-80" is formed on boiling with aqueous or alcoholic alkali hydroxides. The diinethyl ether is hydrolysed only slowly by aluminium chloride in boiling light petroleum or benzene solution and is decomposed in boiling toluene solution. Methylene and Other Derivatives of m-Dihydroxybenxenes. A. LUTHER (Arch. Pharm. 1906 244 561-568).-Methylenedi- resorcinol CH,[C,H,(OH),] is broken down by prolonged boiling with zinc dust and aqueous sodium hydroxide ; the formation (in about 20% yield) of cresorcinol C,H,hfe(OH) [Me (OH) = 1 2 41 and resorcinol was ascertained by first treating the product with sodium nitrite and nitrous oxide then oxidising with nitric acid of D 1-3 and finally crystallising from water when dinitroresorcinol m. p.Z42' and dinitrocresorcinol m. p. 90° crystallised in succession. Cresorcinol forms a ~20120- and a di-benxoyl derivative m. p. 115-116" and 83' and a diacetyl derivative b. p. 293-295'; with bromine in chloroform solutions it yields dibromocresorcinol C7H602Br2 m. p. 86-87' with bromine and water tetrccbro~nocresorcinol C7H4O2Br2 m. p. 99-100° and in chlxoform solution with gaseous chlorine tetra- chlorocresorcinol C7H4O2Cl4 m. p. 69-70" which yields dichloro- cresorcinol C7H602C12 111. p. 78-79' when reduced with stannous chloride and hydrochloric acid ; with diazoaminobenzene in alcoholic solution it condenses to the scarlet cresorcinolbisazobenzene m.p. 211-212O; and with formaaldehyde it yields methylenedi- cresorcinol M p. 195-200°. The last substance CH,[C,H,Me(OH),] is broken down by reduction wit,h zinc dust and aqueous sodium hydroxide t o xylorcinol C,H,Me,(OH),[Me (OH) = 1 3 4 61 and cresorcinol which can be separated by fractional crystallisation from hot benzene. Xylorcinol which can crystallise with 1H,O forms a dibenxoyl derivative m. p. 155' ; with bromine in chloroform solution it yields bromoxylorcznol C,HgO,Br m. p. 119-120°; with diazoaminobenzene it does not condense ; with formaldehyde and dilute sulphuric acid it yields metl~?/ZeneclixyZorci.nol C17H2004 m. p. 25 lo which crystallises with 1 H,O. The last substance is not attacked by zinc dust and aqueous sodiunz hydroxide.The same is true of methylenedis-4 6-dihyclroxy-1 2 3- trimethylbenzene Ci9He4O4 m. pa 228" which was obtained from 4 6-dihydrosy-1 2 3-trimethylbenzene (Simon Abstr. 1904 i 406) and formaldehyde in the presence of dilute sulphuric acid. G. Y. C19H1602N4 C. F. B. Action of Organo-Magnesium Haloids on Acetylenic Alde- hydes and Ketones. Acetylenic Alcohols. &laumcE BRACHIN (Bull. Xoc ohim. 1906 [ iii] 35 11 63-1 179).-Phenylpropiolaldehyde,ORGANIC CHEMISTRY. 1213 obtained by condensing the sodium derivative of phenylacetylene with ethyl formate (compare Moureu and Delange Abstr. 1901 i 581) reacts with magnesium methyl 'odide in presence of ether forming the additive compound CPhiC*C&e*OMgI,Et,O a yellowish-white de- liquescent powder which when suspended in ether and the mixture poured into water containing acetic acid decomposes forming phenyl- acetylenemethylcarbinol CPhiC*CHMe*OH (compare Moureu and Desmots Abstr.1902 i 289) which hasb. p. 132-134'/16 mm. D 1.0449 Dlq2'6 1,0363 nz 1.57305 and reacts with mercuric chloride in alcohol yielding the product CPhiC*CH:Me*OHgCl which crystallises in faintly yellow prismatic needles has m. p. ill" and on hydrolysis with dilule sulphuric acid regenerates the parent alcohol. Phenylpropioaldehyde reacts with magnesium ethyl bromide forming a-p~~e.lzyl-Aa-penti7~ene-y-ol CPhiC*CHEt*OH a faintly yellow oil having b. p. 141-143"/15 mm. D 1.0298 Di3 1.0138 and 92h3 1.5633. With magnesium propyl iodide phenylpropiolaldehyde yields u-phenyZ-Aa- hexinene-y-ol CPhiC*CHPr*OH an amber-coloured oil which has b p.149-152"/17 mm. D 1.0180 and decomposes when kept. a-Phenyl-E- methyl-Aa-hexinene-y-ol CPhiC*CH(OH)-CH,*CHMe similarly ob- tained by means of magnesium isobutyl iodide is a slightly coloured oil has b. p. 149-151"/16 mm. and Do 1.0148. With phenyl magnesium bromide ay-diphenylpropinyl alcohol CPhiC*CHPh-OH is obtained ; it is a colourless oil has b. p. 208~5-209~5°(corr.)/15 mm. D 1.1127 Di7'05 1.0964 and ng'5 1.61'73 (compare Moureu arid Desmots Zoc. cit.). The additive product CPhIC*CHPh*OMgBr,Et,O initially formed in the foregoing reaction is crystalline. No acetylenic alcohols are formed when amylpropiolaldehyde reacts with organo-magnesium haloids. Propionylphenylacetylene CPhiC*COEt (compare Moureu and Brachin Abstr.1904 i 95) reacts with magnesium methyl iodide in presence of ether forming a crystalline product which on decomposition by water yields the tert.-alcohol CPhiC*CXeEt*OH and this on distillation furnishes phenyZ6utenyZacetyZene CPhiC*CEt:CH or CPhiC*CMe:CHMe. This is a colourless liquid with a geritniol-like odour has b. p. 113-115°/15 mm. Do 0.9452 D'; 0.93 and lzg 1.5828. Butyrylphenylacetylene CPh C* COPr (Zoc. cit.) reacts with mag- nesium ethyl bromide forming 13henylacetyZene-ethyZpropylccarbinol CPhiC*CEtPr*OH which has b. p. 155-157"/16 mm. and Do 0.9885 T. A. H. Stigmasterol a new Phytosterol from the Calabar Been. ADOLF WINDAUS and A. HAUTH (Ber. 1906 39 4378-4384).- Phytosterol (m. p. 130) prepared according to Hesse's directions (Abstr.1878 850) is shown not t o be a single substance as success- ive extractions by solvents result in the m. p. of the residue being gradually raised. The bromine additive prdduct obtained from the acetate is easily resolved into two different bromides by fractional crystallisation from glacial acetic acid alcohol acetone or ether By careful treatment with zinc dust and acetic acid the unsaturated acetates are recovered and the alcohols obtained by hydrolysis with130 ABSTRACTS OF CHEMICAL PAPERS. alcoholic potash. They have a constant m. p. and behave as chemical entities ; SO% of the mixtura consists of phytosterol identical with the pbgtosterol obtained from germinating wheat and with sitosterol (Buritin Abstr. 1898 i 7 2 ; Ritter Abstr 1902 i 446).The remainder consists of a n alcohol stigmasterol C,,H,,O,H,O or C3,H,o0,H,0 with in. p. 170" [u] -45.01" in chloroform and [u] - 44.67' in ethyl ether ; i t is isomorphous with phytosterol forms mixed crystals with it and gives the same colonr reactions. The crude phytosterol obtained froin rape-seed oil is also a mixture one constituent of which contains one double linking whilst the other has two double linkings ; these substances are very similar in proper- ties to stigmasterol. Stigmasterol acetate tetrubromide U,,H500,Br4 (or C,,H5,0,Br,) is prepared by acetylating the crude phytosterol and then treating the ethereal solution of the dry acetate with a solution of bromine i n acetic acid ; the tetrabromide separates in small crystals whilst the ph y tos t erol acetate d i bro i n i de remains in solution.When recrystal- lised from amixture of chloroform and alcohol it forms four- or six- sided plates m. p. 21 1-21 2". Stignzuste~ol acetate crystallises from alcohol in rectangiilar plates m. p. 141' ; a cryoscopic determination agrees with the formula C,,H,oO,. The pi*opionrde crgstallises from alcohol in prisms m. p. 122" ; the pi-opionate telmbromide m. p. 20Z0 is similar t o the corresponding derivative of the acetate. The benzoate m. p. lGOO crystallises from a mixture of chloroform and alcohol in rectangular plates the cJdoride C,,H,,Cl or U,,H,,Cl from alcohol in prisms m. p. 95" and the chloride tetrabronzide melts and decomposes at 180'. W. R. Transposition of Hydrobenzoin ; Study of Alkylhydrobenz- oins and some Trisubstituted Aromatic Glycols. MARC TIFFENEAU and DORLENCOURT (Conzpt.re7td. 1906 143 1262-1244). -Aromatic trisubstituted glycols of the types OH*CHPh*CRPh*OH and OH*CHPh*CRR*OH yield the aldehydes CHO*CPh,R and CHO-CPhR respectively when treated with siilphuric acid and not the ketones as previously stated (Abstr. 1906 i 724 965). These trisubstituted (tertiary) aromatic aldehydes do not combine with alkali hydrogen sulphites or give a colour reaction with Schiff's reagent but they are oxidised by silver oxide t o form the corresponding acid CPh,R*CO,H or CPhR,-C0,H. acr-Diphenyl~ropalcl~hyde obtained by the action of sulpburic acid on methylhydrobenzoin does not crystallise b. p. 187-191'/22 mm. 174-17S0/12 mm. or 301-364'/760 mm. Do" 1.087; the oxinte m.p. 123O yields a nitriZe b. p. 310-313"; the semicccrbaxone has m. p. 122". a~-Dipheny~propionic acid m. p. 173" (Thiirmer and Zincke Abstr. 1879 322) is obtained when the aldehyde is oxidised by means of silver oxide ; and the oxide C3,H3*0 m. p. 121-122" is prepared by the action of magnesium phenyl bromide. ~~-DiphelzyZbu~aZde7~~de obtained from ethylhydrobenzoin has b. p. 312-316' yields an oxime m. p. 128-129" and a semicarbazom m. p.ORGANIC CHEMISTRY. 131 167* and is oxidised to aa-diphenylbutyric acid m. p. 170-17lo (Klingemann Abstr. 1893 i 590). a- Phen yZ-p-methy~ropccne-aLp-dioZ OH* CHPh* CMe,*OH m. p. 5 6O obtained by the action of magnesium methyl iodide on methyl phenyl- glycollate is converted by the action of sulphuric acid into a-phenyE- a-methylpropul~ely~e b.p. 105-1 10°/l 4 mm. which yields a-phenyl- a-methylpropionic acid on oxidation and forms a semicarbaxone m. p. 176'. a-Pke?zyE-P-etlyZbutccne-ap-dioZ m. p. 89" b. p. 163 -1 65"/20 mm. or 275-280"/760 nim. is partially converted by the action of sulphuric acid into a-phenyl-a-ethylbutaZdehyde b. p. 135-140°/26 mm. or 235-23So/760 mm. Do 0.978 which forms a semicarbaxone M. p. 178-1 79". M. A. W. Application of the Grignard Reaction to Ethyl Aspartate. CARL PAAL and ERICII WEIDENKAFF (Ber. 1906 39 4344-4346. Compare Abstr. 1905 i 436; 1906 i 236 583).-The reaction be- tween ethyl ethyl-i-aspartate and excess of magnesium phenyl bromide in ether at Oo leads to the formation of r-p-arnino-aa88-tetraphen?$butane- as-diol OH*CPh2*CH(XH2)*CH2-CPh2*OH m.p. 149-150° which separates from dilute alcohol in white leaflets and forms sparingly soluble salts ; the hydrochloride has m. p. 235" and the nitrute 168". c. s. The Six Isomeric Dinitrobenzoic Acids ARNOLD F. HOLLEMAN and K. A SIRKS (Proc. K. Akad. Wetensch. Amsterdam 1906 9 280-286).-When m-nitrotoluene is nitrated by nitric and sulphuric acids at 50° 3 4-dinitrotoluene is obtained together with smaller quantities of 2 3-dinitrotoluene and of 3 6-dinitrotoluene ; the three isomerides are separated by fractional distillation in a vacuum and freezing the distillate. The corrected solidifying points of the dinitro- toluenes of the benzoic esters and of their ethyl esters are tabulated ; also Dill for the toluenes and the esters. The dissociation constants and the velocity of esterification of the dinitrobenzoic acids have been measured with results in accordance with expectation ; the dissociation constants cannot be calculated correctly from those of the monosubstituted acids by Ostwald's rule.For a detailed criticism of the results the original paper must be consulted. c'. s. Action of Nitrous Acid on p-Dimethylamino- and p-Diethyl- amino-benzoic Acids. OSKAR BAUDISCH (Ber. 1906,39,4293-4300). -The author has reinvestigated the action of nitrous acid on p-dimethylaminobenzoic acid and contrary to the statement of Bischoff (Abstr. 1889 511) found it to lead to the formation of p-nitrodime thy laniline p-ni trosome t h ylaminobenzoic acid and m-nitro- p-dirnethylaminobenzoic acid. p-Nit,r.osometlyZaminobenxoic acid NO*NMe*C,H,*CO,H crystallises from toluene or alcohol in glistening straw-colonred needles m.p. 2 17" gives Liebermann's reaction and when boiled with concentrated hydrochloric acid yields p-methylaminobenzoic acid which is formed132 ABSTRACTS OF CHEMICAL PAPERS. also by the action of methyl sulphate on p-aminobenzoic acid (Johnston Proc. 1905,21 156). 3-Nitro-Cdimethylaminobenzoic acid crystallises from toluene or chloroform in glistening golden-yellow needles m. p. 222-223° does not give Lieberrnann's reaction gives a red coloration changing through violet and bluish-green to dark red when reduced with zinc and hydrochloric acid and treated with ferric chloride and forms a hydro- chloride which is readily decomposed by water (compare Noelting and Demant Abstr.1904 i 424). The action of sodium nitrite on p-diethylaminobenzoic acid in hydro- chloric acid solution leads t o the formation of 4-nitrosoethylamino- benzoic acid 4-nitronitroeoethylauiline 3-nitro-4-ethylaminobenzoic acid 3-nitro-4-diethylaminobenzoic acid and 4-nitrodiethylaniline in amounts varying with the quantity of sodium nitrite and the concen- tration of the hydrochloric acid employed. The original must be con- sulted for the method of separating the products. 4-nTitrosoethyZa~inobellxoic acid NO*NEt*C,H4*CO2H crystallises from alcohol in glistening straw-coloured needles m. p. 193-.194O and gives Liebermann's reaction. 3-Nitr~-4-eti~yZaminobenxoic acid NHEt*C,H,(NO,)*CO,H crystal- lises from light petroleum in glistening,.golden-yellow needles m. p. 239-240 forms a colourless szclpliate whlch is readily decomposed by water and when reduced with zinc and hydrochloric acid and treated with ferric chloride gives a dark red coloration or with sodium nitrite a dark red flocculent precipitate. 3-n7i'tro-4-dietA?/Z~minobenxoic acid NEt,*C,H,(NO,)*CO,H crystal- lises from light petroleum in glistening reddish-yellow needles m. p. 117" and gives a d k k red coloration when reduced with zinc and hydrochloric acid and treated with ferric chloride. G. Y. Action of Potassium Bypochlorite on Cinnamamide. R. A. WEERMAN (PYOC. I!. Akad. JfTetecnscla Amsterdam 1906 9 303-304).- When an alcoholic solution of cinnamamide (2 mols.) is treated with potassium hypochlorite (1 mot.) in which the free alkali has been neutralised j u s t before use a carbamide CHPh:CH*NH*CO*NH-CO.CH:CHPh is obtained which separates from glacial acetic acid in needles m.p. 225-226'. c. s. Hydroxytoluic Acids. I. 4-Hydroxy-o-toluic Acid. TIIEODOE ZINCKE and H. FISCHER (AnnaZen 1906 350 247-265. Compare Jacobson Abstr. 1881 599 ; Kalle & Co. D.R.-I?. 81484 91201 ; Einhorn Abstr. 1900 i 439).-The behaviour of 4-hydroxy-o-toluic acid towards bromine has been investigated from the point of view of its character as a derivative of p-cresol. The action of bromine on 4-hydroxy-o-toluic acid with or without glacial acetic acid as solvent a t the laboratory temperature and finally at 60-65' leads to the formation of 3 5-dibronao-4-hydroxy-o-toluic acid OH*CGHMeBr,*C02H which crystallises from benzene in slender needles from acetic acid in stout needles m.p. 141" and forms a white crystalline silver salt. The acety? derivative crystallises in slenderORGANIC CHEMISTRY. 133 needles m. p. 125'; the methyl ester forms long white needles m. p. 108-1 09O. A monobromo-4-hydroxy-o-toluic acid cannot be obtained a part of the acid remaining unchanged when insufficient bromine for the formation of the dibromo-derivative is employed 3 ; 5 6-Tribi*omo-4-?~yd~ox~-o-toEuic acid OH*CMeBr,*CO,H prepared by heating 4-hydroxy-o-toluic acid or its dibromo-derivative with bromine on the water-bath crystallises from hot benzene or water in glistening needles m. p. 193-1 94* decomposes slowly on prolonged boiling with aqueous sodium carbonate forms a silvey salt which blackens on exposure to air and is converted by concentrated nitric acid into a brornodinitro-acid crystallising in long needles and com- mencing to decompose a t 200O.The acetyl derivative of the tribromo- acid crystallises in short monoclinic prisms m. p. 1 7 6 O . 3 ; 5 6-T~ib~on~o-4-hydroxy-o-toluic acid +-bromide (3 ; 5 ; 6 w-tetra- bromo-4-h~droxy-o-toluic m i d ) UO<C,r:C(Co2H) CBr == CBr>CH*CE2Br or OH*C,Br,(C0,H)*C€€2Br formed by heating the tribromo-acid with an excess of bromine in a sealed tube a t 120-125° crystallises in long white needles m. p. 1 6 8 O and when treated with acetic anhydride and concentrated sulphuric acid yields an acetyl derivative OAc*CBBrS(C0213)*CH2Br ; this crystallises in stout glistening needles m. p. 198-199" and is converted by aqueous sodium carbonate into tr ibr oino- 4-?6pd~ox yph t T~al ide .When treated with methyl alcohol and concentrated sulphuric acid the tetrabromo-acid yields 3 5 6 - ~ i b r o ~ o - 4 - h y d r o ~ ~ - ~ -naethoxy-o-toluic acid OH*C,Br,(CO,H)*CH,-OMe which crystallises from benzene in stout colourless needles m. p. 145-146" or from dilute acetic acid in glistening prisms containing H2Q m. p. 114-115O; it dissolves unchanged in aqueous sodium carbonate and is converted by acetic anhydride and sulphuric acid into the wetyl derivative of the phthalide. The action of boiling acetic anhydride and sodium acetate on the tetrabromo-acid leads to the formation of the phthalide and a sandy sparingly soluble substance rn. p. above 260° which is formed also on heating the tribromomethoxy-acid above its melting point.(ret~~a6romo-4-~~ydr~ox~-o-toluic acid perbromide (C,N,O,Br,),Br pre- pared by hesting the tetrabromo-acid with an excess of bromine at 135-140° or with bromine in carbon tetrachloride solution forms glistening red needles is moderately stable a t the laboratory tempera- ture is decolorised by acetone sodium hydrogen sulphite or sodium hydroxide and yields the tetrabromo-acid when heated when dissolved in ether or when boiled with benzene. 3 5 6- Trr.ib~orno-4-hydl.oxyphtiLalide OH* C G B r < ~ ~ > U prepared by the action of 10% sodium carbonate solution on the tetrabromo-acid or by boiling the acid with aqueous acetone erystallises in glistening needles rn. p. 207O remains unchanged when heated with hydrogen bromide or with aniline and forms a sodium salt crystallising in long white needles.The cccetyE derivative crystallising in glistening needles m. p. 222-223".134 ABSTRACTS OF CHEMICAL PAPERS. Tri6romo-4-~ydl.oxyphthccZideccnily OH*C6Brg<:2>NPh formed by the action of aniline on tetrabromo-4-hydroxy-o-toluic acid crystallises in glistening needles m. p. 220° ; the acetyl derivative C,,H1,O,NBra forms broad glistening needles m. p. 225-226'. The nitro-4-hydroxy-o-toluic acids formed by nitration of 4-hydroxy- o-toluic acid (Einliorn Zoc. cit.) are separated by boiling with methyl- alcoholic hydrogen chloride when 3-nitro-4-hydroxy-o-toluic acid m. p. 197" remains unchanged whilst 5-nitro-4-hydroxy-o-toluic acid rn. p. I6Oo is converted into its methyl ester C,H,O,N crystallising in yellow leaflets m.p. 99'. 3-Nitro-4-acetoxy-o-toZutc acid forms long broad almost colourless leaflets m. p. 139-140'. 5-Brorrzo-3-n~trc;-4-~~ydroxy-o-toZuic acid OH*C6HMeBr(N02)oC0,1-f formed by the action of nitric acid or sodium nitrite on 3 5-dibromo- 4-hydroxy-o-toluic acid or by the nitration of 3-nitro-4-hydrox~-o-toluic acid crystallises in stout yellow needles m. p. 208" forms character- istic anzmonium sodium bariam and silver salts and is reduced by tin and hydrogen chloride in methyl alcoholic solution forming 5-bromo- 3-amino-p-cresol or by zinc dust in neutral solution or by alkali sulphides forming 5 - bro nao- 3 -unaino- 4 - hydvoxg-o-t oluic acid OH* C,HMeBr(NH,) *CO,H. This crystallises in colourless needles m.p. 179-1 SOo becomes brown on exposure t o air in alkaline solution and yields a sparingly soluble diazo-derivative. The diacetyl derivative C12Hl105NBr crystallises in long needles m p. 189-190°. G. Y. Tyrosamines. ARMAND GAUTIER (Bull. Xoc. c?iim. 1906 [ iii] 35 1195-1 197).-Water extracts from codfish livers which have been allowed t o ferment spontaneously a mixture of amylamine and like sub- stances with tbree buses represented by the formulze C,H,ON C,HllON and O,H,,ON which form colourless needles or lamellae and when heated at 220' sublime slightly and decompose. They are bitter possess a-slight non-ammoniacal odour are alkaline t o test-paper and give all the characteristic colour reactions of tyrosine. It is suggested that these bases are derived from tyrosine and its next two lower homologues by the loss of a molecule of carbon dioxide.The most abundant of the three bases is that having the formula C,H,,ON which on the above assumption is p-hydroxyphenylethylamine. It is soluble in 95 parts of water at 15" crystallises in the cold but blackens by oxidation On exposure to air. Its salts are neutral and bitter the ZLydrochZoride and sulplmte form hygroscopic spangles or needles and the plutinichloride is yellow and readily soluble. All three tyrosamines are but slightly toxic. Similar products have been obtained by Leger (Abstr. 1906 i 204 761) and by Brieger. T. A. H. Isomerism of Ethylcoumaric and Ethylcoumarinic Acids. ARTHUB MICHAEL and ARTHUR B. LAMB (Amer. Chem. J. 1906 36 552-580).-The question whether coumaric and coumarinic acids are spacial or structural isomerides has not been conclusively decided but spacial modifications of ths hydroxycinnamio acids are undoubtedlyORGANIC CHEMISTRY 135 capable of existence. Cinnamic acid is changed into ullocinnamic acid by converting it into phenylpropiolic acid adding hydrogen bromide t o this and reducing the bromocinnamic acid thus obtained.A similar series of operations with ethylcoumaric acid is found t o yield ethyl- coumsrinic acid a n observation which argues strongly t h a t the relation between these acids is similar t o that existing between the stereo- isomeric cinnamic acids. I n the reduction of P- bromo-o-ethoxyaZZocinnamic acid no indications are given of the formation of an acid corresponding with isocirinamic acid.The method given by Ebert (Abstr. 1883 471) for the preparation of ethylcoumarinic acid from coumarin a n absolute alcoholic solution of sodium ethoxide and ethyl iodide gives the isomeric ethylcoumiric acid; if however the absolute alcohol is replaced by 96% alcohol a good yield of ethylcoumarinic acid is obtained. Ebert's conclusion (Zoc. cit.) that the addition of bromine t o ethylcoumaric and t o ethyl- coumarinic acid yields the same dibromide is confirmed. Using the method given by Claus (Aiznaleiz 1892,260,2) for the pre- paration of etboxyphenylpropiolic acid the authors were unable t o obtain an acid free from traces of halogen which could only be removed by conversion of the acid into the calcium salt followed by digestion with 50-60% alcohol and reconversion into the acid.The acid obtained in this may has m. p. 115*5-116°; Ebert gave 114". The action of hydrobromic acid on ethoxyphenylpropiolic acid yields (1) ethylbromocoumaric acid m. p. 120° with the bromine atom in the P-position t o the carboxyl group; (2) a small proportion of a n mid C,,H,,03 crystallising from a mixture of acetone and light petroleum in white needles m. p. 211-212-5'. The reduction of P-bromonllocinnamic acid in alcoholic solution by means of zinc dust yields mainly aZZocinnamic acid together with cinnamic acid and a n acid with tt very low melting point. When reduced in this way bromo-P-ethylcoumaric acid is converted almost entirely into ethylcoumarinic acid the proportion of ethylcoumaric acid yielded being small; ethylmellilotic acid could not be detected among the products of the reduction and cannot be formed in other than very minute quantities.up- D i b l . o n z o - P - b r o n i o e l ~ ~ o ~ ~ ~ l L e ~ ~ ~ ~ ~ . o ~ ~ ~ o n i ~ acid OEt°C,H3Br*C,H2Br,* C02H prepared by the action of bromine (4 atoms) on ethylcoumarinic acid in chloroform solution separates from toluene in colourless rectangular crystals and from a mixture of acetone and light petroleum in short slightly rliombic needles ni. p. 1 S.3-183' (decomp.). The action of bromine (4 atoms) on ethylcoumaric acid yields a gummy residue which when dissolved in alcohol and treated with sodium hydroxide and the solution acidified gives bromo-o-ethozypl~enyl- JwopioZic ctcid OEt*C,H,Br*CiC*CO,H crystallising in needles m.p. 134-136". The gummy residue hence consists principally of a tribromo-derivative of ethylcoumaric acid or of bromo o-ethoxyphenyl- dibromopropionic acid. This evidence of t h e dissimilarity of the corresponding products derived from ethylcoumarinic and ethyl- coumaric acids requires confirmation since Perkin found t h a t the two136 ABSTRACTS OF CHEMICAL PAPEKS. methyl acids gave the same bromo-o-rnethoxyphenyldibromopropionic acid. The action of bromine vapour in excess on ethylcoumaric acid yields ap-~ibromo-p-dibromoethoxyp2ien~ll23ro~io~z~c acid OEt C,fS,Br2*C,H,Er2*C0,1E mhich crystallises from toluene or light petroleum in thin rhombic plates m. p. 1S3-184° Ethylcoumarinic acid probably yields the same acid but the product could not be purified.When treated with a solution of chlorine in carbon tetrachloride ethylcoumarinic acid yields the ~ 0 ~ 7 ; n o ~ l n ~ ~ OEt*C,H,*C,H,Cl* CO,H which separates from ligkt petroleum in crystah m p. 130-131O. Ethylcoumarinic acid is not acted on by alcoholic solution of sodium ethoxide but heating with dilute mineral acid converts it into etbyl- coumaric acid (compare Perkin Trans. 1877 31 358) as also doex treatment with iodine in carbon disulphide solution. T. E. P. Replacemen% of the Bydroxyl of some Carbinols by the Group -CH,*CO,H. XOBERT B'OSSE (Compt. rend. 1906 143 914-916).-~P-Disubstituted propionic acids are readily obtained by the condensation of mczlonic acid and secondary aromatic carbinols which contain the group -OMe :O,:CNc or -NTVle according to the equation :CH*OH + CH,(CO,€€) = €I,O + CO + :CH*CE,*CO,€€ and the following acids were thus prepared (1) P-~hen~l-P-p-nzelioxy- plsenyl~ropioniccccid O ~ e .C H * C H P h . C H ~ * C ~ ~ m. p. 121.5-1 22.5" ; (2) p-p-melhoxypheizyZ-P-a-i~~p~~thyZprr.opionic acid O.Me*CGH,*CH( C&17) CI12~C0,H and its p- ~ o Z ~ ~ ~ ~ ~ e Onire C €I,*CH ( C CH 0 N H C,? melts at 176-1 77" ; ( 3 ) j3-phenyl-P-3 ; 4-dioxyrmethyleizeple~ylpro~ao~~ic acid CR,O,:C,H,.CHPh*CH,*CO,H m. p. 155-156° ; (4) p-3 4-dioxy- metlL~lerLe~?Lei2yZ-~-a-nc~~~~tlLyZ;nropionic acid m. p. 2 0 5 O ; ( 5 ) p-3 4-dioxymethyleneplienyl-~-p-tolylpropionic acid CH20,:C,€-I,*CH(C1H;)*CfiE,*C0,H m. p. 16 1" ; (6) P-pfienyE-P-p-cZi- methyZuminopheny Zpropiolnic acid NMe,* c1GE.14* CEfPh* CH,* CO H m.1). 1 84.5' ; (7) ~-p-dirrzet~~yZmmino~henyZ-~-a-na~~~thyEprop~onic acid Ni\lle20C,H,.CH(C,oH7).CH,*C0,H m. p. 1 8 3 O the silver Zectd and cuZciuna salts have been propared ; (8) pP-Ji-P-vEimet/LyZccininophenyl- propionic cccid CH(C,fT,*NMe,),*CH,.CO,€I m. p. 222-230° the potassium soc.titcm cdcium lead 6cwi2bm and siEver salts have been prepared. Most of the acids described form white amorphous silver salts. 3%. A. W. CH20, CGH CH( H 7) OH2* CO,H Nitration of Phthalic Acid and of isoPhthalio Acid. ARNOLD F. HOLLEXAN and J. HvrsINaA (Proc K. Akacl. Wetenscfr,. Amsterdam 1906 9 286-a92).-&-Nitroisophthalic acid obtained by nitrating isophthalic acid crystallises with lH,O and has m. p. 4-~itroisopht~ia~ic acid is obtained by oxidising the corresponding xylene prepared by nitrating xylene at 0' with nitric acid of D 1.48 with an alkaline solution of potaasium permangauate. It has m.p 2459 2 55-25 6'.ORGANIC CHEMISTRY. 137 2-Nitroisophthalic acid obtained by oxidising the corresponding nitroxylene crystallises in needles m. p. 300'. The quantitative nitration of pbthalic acid requires three weeks at 30° and yields 495% of a- and 50.5% of P-nitrophthalic acids. Under similar conditions isophthalic acid yields 96.9% of the 5-nitro- and 3.1% of the 4-nitroisophthalic acids the proportious being ascertained by solubility determinations. c'. s. Santonin. EDGAB WEDEEIND (AT& Pharm. 1906,244,623-639). -The oxonium salts of santonin (compare Abstr. 1905 i 211) with ferrocyanic and ferricyanic acids C,5€I180,,H4Fe( CN) and C15H180,,H,Fe(CN) respectively were analysed ; the cobalticysnide which is distinctly crystalline mas not analysed. A sodium smtoninsulphonate C,,H,,O,=SO,Na [a] - 1 0*25' was ob- tained by heating chlorosantonin (Abstr.1905 i 212 529) with aqueous sodium sulphite for several hours at 140-150'; the purest sample prepared contained 96*5O/,. The substance is not a vermifuge. With hydroxylamine santonin yields a product 111. p. 92-96' which contains AT 9.3'/ corresponding approximately with two atoms of nitrogen in the molecule. The substance is not a dioxime however for when it is heated with dilute mineral acids it yields not santonin but a resinous product which contains nitrogen Concentrated hydrochloric acid either at the ordinary temperature or at 60° converts santonic acid partially into desmotroposantonin. The paper contains a short statement of the modern views of the constitution of santonin and of some of its derivatives.C. F. €3. Action of Light on Oximes. ROBERTO CIVSA (Atti R. Accad. Lincei 1906 [ v ] 15 ii 721-728. Compare Ciamician and Silber Abstr. 1904 i 16 I).-The author confirms Goldschmidt's observation (Abstr. 1904 i 250) that the oxime m. p. 121-122" obtained directly from m-nitrobenzaldehyde is the anti-oxime which when transformed by the Beckmann method yields the syn-oxime m. p. The oximes of m-nitroanisaldehyde and p-chlorobenznldoxime behave normally towards light and are transformed into the corresponding syn-oximes. anti-Benzaldoxime and anti-piperonaldoxime however remain unchanged so that the presence of a negative group in the molecule of the aldehyde appears necessary for the passage from the anti- to the syn-oxime. syn-Benzaldoxime is converted almost entirely into the ctnti-oxirne on exposure to light but with syn-nz-nitrobenzaldoxime 5 3% remains unchanged after six months.m-Nitroanisaldehyde prepared by Wijrner's mebhod (Abstr. 1696 i 225) has m. p. S6-S7O. N0,*C,H,(O~~e)~CH:N,H~C,€14~N0 separates from a mixture of alcohol and acetone in yellow crystals m p. 244'. The oxime NO,*C,H,(OMe)*CH:NOH is deposited from alcohol in silky white acicular crystals m. p. 170'. The syn-oxime prepared by Beckmann's method crystallises from benzene in fairitly yellow needles m. p. 16s-170'. The benxyl derivative of the unti- 1 18-1 19".I t s p-nitro~~~sn~lh?/dl*axone VOL. XCII. i. 1138 ABSTRACTS OF CHEMICAL PAPERS. oxime NO2*C,H,(OMe).CH:N0=CH~Ph separates from alcohol in shining white needles m. p. 124' and the corresponding ayn-derivative crystallises from alcohol in slender yellow noedles m. p. 195'. unti-p-Chlorobenealdoxime has m. p. 1 lo' and the syn-compound m. p. 14G0 (compare Erdmann and Schwechten Abstr. 1891 448). T. H. P. Methyl p-Tolyl Ketone. CARL THOMAE and HERMANN LEHR (Arch. Phawn. 1906 244 651-652).-Some details are given of the preparation of this ketone from acetyl chloride toluene and aluminium chloride and carbon disulphide (2) (Claus and Riedel Abstr. 1886 642) C. F. B. CARL THOMAE (Arch. Phnrm. 1906 244 641-642. Compare Abstr. 1905 i 509 also 684 718).-A paper introductory to those with which the following two abstracts deal.Ketone ammonias are hydrolysed readily to ketones and ammonia by dilute aqueous acids. Alcoholic picric acid removes NIX forming monoaxo-ketone nnzmonias ; when these are dis- tilled they lose 1 mol. of a hydrocarbon aliphatic or aromatic yielding trialkyl derivatives of pyridine which sometimes can be obtained directly from the ketones by heating these strongly with alcoholic ammonia in closed vessels The yields obtained from the ketones are small amounting to but a few per cents. of the theoretical ones. Compounds of Ketones with Ammonia. C. F. B. Compounds of Ketones with Ammonia. Action of Ammonia on Acetophenone. CARL THOMAE (Arch. Pharm. 1906 244 643-651).-The crude product of the action of ammonia on acetophenone a t the ordinary temperature after spontaneous evapora- tion of the ammonia and of most of the alcohol was diluted with ether mixed with coarsely powdered ice and shaken with a slight excess of dilute (1 9) hydrochloric acid ; from the ethereal solution which con- tains much unaltered ace tophenone acetophenone ammonia hydro- chloride separates.This was suspended in much alcohol and the mixture was shaken with solid potassium hydroxide until the reaction was faintly alkaline ; the liquid was filtered and the alcohol allowed to evaporate at the ordinary temperature ; the residue was stirred with a little alcohol and the crystals drained and recrystallised from alcohol ; the yield was small. Thus obtained acetophenone ccnzmoniu CMePh( N :CMePh) or C,,H,,N (molecular weight determined ebullioscopically in benzene) has m.p. 1 1 5 O ; it reacts like a tertiary base with benzenesulphonyl chloride. It is not decomposed rapidly by water but if a few drops of hydrochloric acid are added hydrolysis to acetophenone and ammonia begins at once; in consequence the hydrochloride was not obtained in the pure state nor could a platinichloride be prepared. With picric acid in alcoholic solution acetophenone ammonia yields yellow monomo-acetophenone ammonia picrute C2,H2,N ,C6HsO7Na elimination of NH taking place; t h i s pelts at 210.5'. The corre- spondiog hydrochloride is present in the aqueous portion of the aqueous-OBGANIC OHEMISTRY 139 ethereal mixtuiw from which the acetophenone ammonia hydrochloride separated.The base is formed in larger yield when an alcoholic solutiwa of acetophenone is saturated with ammonia in the cold and then heated at 150-180° for twenty-seven hours i n sealed glass tubes (under these circumstances no acetophenone ammonia is formed); it was only obtained in an oily or pasty condition. When crude monoazo-acetophenone ammonia is distilled it yields triphenylpyridine (acetophenine) C,,H ,N with elimination of CH,. From the ethereal portion of the aqueous-ethereal mixture already mentioned (which contains much unchanged acetophenone) a crystalline substance of another type containing no nitrogen was obtained by distillation ; it is undergoing investigation. C. F. B Compounds of Ketones with Ammonia. Action of Amrr,onia on Methyl p-Tolyl Ketone.CARL THOXAE and €€ERMA” LEHR (Arch. Phamz. 1906 244 653-664).-The method of manipulation and the products obtained were of a similar character to those in the case of acetoplienone (compare preceding abstract). MethyE p-tolyl ketone ummonia C6€f ,Me*CMe(N CMe* C,H,Me)2 or C,7H30N2 (molecular weight determined ebullioscopically in benzene) hss m. p. 1 1 1 O ; the p Z ~ t i ~ i c ~ Z ~ ~ ~ ~ e C,7H30N,,H,PtCl has m. p. Monoaxo-methyl p-tolyZ ketone ammoniapicrute C,7H,7N,C,H,07N has m. p. 2 1 1 O . The base is not formed in appreciable quantity when the ketone is heated strongly with alcoholic ammonia. I n these circumstances ~~ethyZditoZ?l~yridi~~e C,,HI9N (molecular weight determined ebullioscogically i n benzene) is formed correspond- ing with elimination of NH and C6H5Me from tho ketone ammonia ; it has m.p. 97.5’; the picrate U20H119N,C6H307NB m. p. 211° is bydrolysed by water as also is the chloride. A smltll quantity of a substance of m. p. 1 7 6 O was also obtained; possibly this wss tritolyl- pyridine resulting from elimination of NH and CH from the ketone ammonia. A crystalline product free from nitrogen was obtained as in the case of acetophenone. C. F. B 2 03-20 4’. Reaction Between Unsaturated Compounds and Organo- Magnesium Compounds. X. Reactions with a-Methylcin- namic Acid. ELMER P. KOHLER (Amer. Chem. J. 1906,36,529-538. Compare Abstr. 1906 i 753).-The author has studied the inter- actions between a-methylcinnamic acid and organo-magnesium com- pounds in order to determine the influence exerted on the action by a ‘ I positive” group in the a-position of unsaturated esters.The results obtained with benzylidenepropiophenone are exactly analogous with those yielded by benzylideneacetophenone (Abstr. 1904 i 595). The results given in the present paper show that Blaise and Courtot’s interpretation of the course of the reaction between Grignard’s reagent and methylacrylic acid (Abstr. 1905 i 257) as a direct union of the reagent to the double linking between carbon atoms is erroneous. The formation of a certain amount of saturated ketone in the action between the mehhylacrylic acid and magnesium 2 2140 ABSTRACTS OF CHEMICAL PAPERS. methyl iodide is due to &addition thus (1) CH,:CMe*CO,Et + MgMeI = CH,:CMe*COMe + MgI*OEt ; (2) UH,:CMe*COMe -k MgMeI = CMeE t:CMe*O.MgI and this + H,O = CMeEt:CMe*OH I CHMeEt COMe.The first action between methyl a-methylcinnamate and an organo- magnesium derivative invariably consists in the replacement of methoxyl by a hydrocarbon residue an unsaturated ketme being formed. When an excess of the reagent is present the uusaturated ketone reacts immediately with a second molecule forming either the magnesium derivative of a tertiary alcohol by addition to carbonyl or the derivative of an unsaturated alcohol by aA-addition. When the magnesium derivative is carefully decomposed with iced acid the resulting ethereal solution on heating gives only an unsaturated ketone but when it is evaporated a t a low temperature in a stream of moist air or oxygen a peroxide is formed. 'l'his behaviour is peculiar to unsaturated alcohols obtained by a&-addition to ketones with tt hydrocarbon residue in the a-position.ayy-l'r~p12erLyl-P-metli~~~o~en~l benzoate OBz*CPh:CMe*CHPh pre- pared by the action of benzoyl chloride on the intermediate magnesium derivative obtained in the interaction of magnesium phenyl bromide and methyl a-methylciausmate crystallises from a mixture of ehloro- form and alcohol in needles in. p. 122'. CHPb 2* C Br Xe *COP h prepared by the action of bromine on the magnesium derivative of triphenylmethylpropenol crystsllises from a mixture of ether and light petroleum in large lustious plates m. p. 9 3 O . cr) stal- ayy-ITriplLer~yl-P-metl~~lpropenol pc'woxide lises from a mixture of ether and light petroleum in coloiirless needles m.p. 12'i0 has the noimal molecular weight in boiling ethyl ether and when pure is stable at t'he ordinary temperature. When heated on a steam-bath or melted it explodes giving benzoic acid s-tetraphenyl- ethane and a small proportion of diphenylmethane the first two OF these products being also obtained on warming the peroxide with concentrated alcoholic potassium hydroxide. If however the peroxide is added slowly to cooled dilute alcoholic potassium hydroxide it yields the intermediate a - h y d r o x y - ~ ~ - d i ~ h e ~ ~ ~ Z - u - ~ ~ ~ l ~ ~ l ! p ~ ~ o CHPh,*CNe(OH)*COPh which crystallises from a mixture of acetone and alcohol in colourless plates m. p. 18So has the normal molecular weight in boiling ether and is also obtained when dilute potassium hydroxide solution is gradually added to a cooled solution of a-bromo- &9-diphenyl-a-methylpropiophenone. Methyl a-rnethylcinnamate reacts with 2 mold. of magnesium methyl iodide eveu when the l&ter is slowly added t o excess of the ester the product being a-~)l~nyl-py-dinzetl~yl!butcccliene CHPlLCMe:CMe:C!H b.p. 165'/30 mm. Intramolecular Atomic Tranapoaitions. 1V. Aromatio Oximes. P. J. MONTAGNE (Rec. trav' chim. 1996 25 376-378. Compare Abstr. 1905 i 445).-The fact that 4 4'-Jichlorobenzo- a-Bromo-&3-diphetb yE-a-metli?lEpropio~~l~e~~oT~e CHPh,* ?Me* OH* CPh -0' T H. P.ORGANIC CHEMISTRY. 141 phenone after undergoing the Beckmann transformation yields on hydrolysis p-chlorobenzoic acid and p-chloroaniline shows that the rearrangement does not involve any change in the point of attachment of the ketonic carbon atom to the aromatic nucleus.P. H. Intramolecular Atomic Transpositions. V. Conversion of 4 4 ’ 4” 4”’-Tetrachlorobenzopinacolin s - 4 4’ 4” 4”‘- Tetraphenylethane. P. J. MONTAGNE (Rec. tmv. chim. 1906 25 379-410. Compare Abstr. 1905 i 58 445 524).-The theory put forward by Klinger and Lonnes (Abstr. 1896 i 691 692) t o explain the transformation of P-benzopinacolin into s-tetra- phenylethane first described by Thiirner and Zincke (Abstr. 1578 425) necessitates a change in tho carbon atom by which the aromatic nucleus is attached. The results obtained in the present communication refute this theory since there is no alteration in the positions of tho chlorine atoms when 4 4’ 4” 4”‘-tetrachlorobenzo- pinacolin is converted into 4 4‘ 4” 4”’-tetracblorntetraphenylethane.I n the interaction of 4 4’-dichlorobenzophenone with p chlorobenzoyl chloride in the presence of aluminium chloride (Ahstr. 1902 i 472) the yield which in bright daylight is 75-80% may be increased t o 90% or more in the presence of direct sunlight; i n addition t o 4 4’-dichlorobenzophenone some 2 4’-dichlorobenzophenone is formed thus disproving L3eilstein’s rule that only para-substituted derivatives are formed during a Friedel and Critft condensation. 4 .l‘-DichZoro- diphen?yZmthane ot-hined by reducing 4 4’-dichlorodiphenylmethane with hydrii>dic acid and amorphous phosphorus crystallises from light petroleum in large flattened monoclinic crystals [u b c = 1 -8365 1 1.6586 ; p = SSo45’] m.p. 55’. 4 4‘ 4” 4’”-Tetrachlorobenzo- pinacone (Abstr. 1905 i 445) can in the absence of sunlight be prepared by reducing dichlorobenzophenone with zinc and sulphuric acid. The reducticn of 4 4’ 4 4”’-tetrachlorobenzopinacolin with hydriodic acid and amorphous phosp1ior:is yields in addition to 4 4’ 4” 4’”-tetrachlorotetraphenylethnne R substance of the molecular formula C,,H,,CI which crystallises from light petroleum i n slender needles m. p. 215-5’ or from benzene in triclinic prisms C7GH18C14,2C6H6 [ a b c = 1.0792 1 0.9831 ; a= 131’54’; p=118°50~; y = 74O414’1. A quantitative yield of diphenylcarbinol was obtained by adding successively 25 grams of benzophenone and 30 grams of zinc powder to a boiling solution of 25 grams of potassium hydroxide in 200 C.C.of pure alcohol. Intramolecular Atomic Transpositions. VI. Conversion of a-4 4‘ 4‘’ 4”-Tetrachlorobenzopinacolin into the @Variety. P. J. XONTAGNE (Rec. trav. chin%. 1906 25 411-414. Compare Abstr. 1905 i 58 445- 524)-On reducing 4 4’-dic.hlorobenzo- phenone by means of zinc dust and acetic acid in presence of dilute sulphuric acid for eight days only a 1-ery small quantity of 4 4’-di- chlorodiphenylcarbinol is ohtained the main product of the reaction being 4 4’-dichlorodiphenyhnethnne and a-4 4’ 4“ 4-tetrachloro- into P. H. Y I “ benzopinacolin O< C(C~jH4c1)2. I The latter crystallises from light p d rol- C(CGH4C1) 2I42 ABSTRACTS OF CHEMICAL PAPERS. eum in small needles m. p. 235O (decomp.).On oxidation with chromic acid i t yields 4 4’-dichlorohenzophenone and when heated with acetyl chloride a t 300’ it is converted into /3-4 4’ 4 4”’-tetrachlorobenzo- pinacolin C( CBH4C1),=CO*C,H,Cl ; boiling alcoholic potassium hydroxide breaks it up into p-chlorobenzoic acid and 4 4’ 4”-trichlorotriphenyl- methane showing that during the migration of the group C,EC,Cl- necessitated by the change from the a- to the /?-variety the relative position of the chloride atom has not been altered and accordingly that the aromatic nucleus must be attached by the same carbon atom both before and after the transposition. The Alkaline Reduction of p - and m-Nitrobenzophenones. PAUL CARR-O (Compt. rend. 1907 144 34-35).-l‘he m- and p-nitro- benzophenones were prepared by the condensation of the corresponding nitrobenzoyl chlorides with benzene in the presence of aluminium chloride.m-Nit?ioberzxop?~e.o~~p~~enyl?~ydra~one crystallises in yellow needles m. p. 11 Go ; the corresponding p-nitro-compound forms small reddish-orange crystals m. p. 1429 p-Nitrobenzophenone when boiled with zinc and alcoholic soda gives first a mixture of azo- and azoxy- benzophenone which cannot be separated. By continued reduction the ketonic group is attacked. Reduction of this mixtiire with ammonium hydrosulphide gives p-hyd?inxobenxol;thenone COPh*C,H,*NH*NHDC,H,* COPh which crystallises with H,O in white needles m. p. Z 30’ ; the anhydrous substance has m. p. 162O. On oxidation with mermric oxide it gives p-axoberzxophenome N,(C,H4-COPh) which forms red lamellae m.p. 219”. The phenylhydraxone forms small bright red crystals ni. 1). 130’. nz-Nitrobenzophenone gives by similar reduction m-azoxybenzo- phenone (Elbs and Wogrinz Abstr. 1903 i 635). Ammonium hydro- sulphide reduces this to an oily compound which cannot be purified and is oxidised by mercuric oxide to nz-azobenzophenone (Elbs and Wogrinz Zoc. cit.). Continued reduction of the m-azoxybenzophenone results in the attack of the ketonic group and the breaking u p of the molecule. The results are analogous to those observed in the reduction of m- and p-nitrobenzyl alcohols ( Abstr. 1905 i 889). o-Aminobenzophenone Derivatives. FRITZ ULLMANN and WALTER DENZLER (Be?-. 1906 39 4332-4339. Compare Abstr. 1903 i 176).-The authors have prepared a series of o-nminomethoxy- benzophenones by condensing arylsulplioneanthranilic chlorides with the methyl ethers of the three dihydroxy-benzenes pyrogallol and t h e two naphthols respectively.The behaviour of the resulting o-amino- ketones on diazotisation is also described. P. H. E. H. p-~olzce,zeszclphone-Z-anzino- 2’- 5 ‘-dimethox~fe?~~opl~enone C,H7*S0,* N IT*C,H,-CO* C,H,*( OMe)2 obtained by the addition of quinol dimethyl ether and aluminium chloride to p-toluenesulphoneanthranilic chloride crystallises in colourless leaflets m. p. 156O. When warmed with a mixture of equal parts of concentrated sulphuric acid and glacial acetic acid i t forms ~-amino-2’ 5’-dimet~~o~~be?axop?~enone C,,Hl,O,N which separates from a mixture of ether and light petroleum in amber-coloured crystals m.p. 98’. When the latter compound is diazotised and the resultingORGANIC CHEMISTRY. 143 solution heated %m&hoxyxanthone m. p. 131° is obtained which is converted into 2-hydroxyxanthone when warmed with aluminium chloride. p-Tolwnesulphone - 2 - ami?zo - 2' 4'- tlimetl7LoxybenxoprTLeizone~ obtained from resorcinol in similar manner separates from a mixture OE benzene and light petroleum in glistening needles m. p. 139'. On saponifica- tion it forms 2-amino-2 4'-dimetrTLoxybenxophenona which crystnllises in yellow stellate needles m. p. 138'. When diazotised as in the pre- ceding case i t forms 3-methoxyxanthone7 which is readily converted into 3 - hydroxyxanthone. p- To Zuemnssu lphone- 2-un7ino-3 4'-dimethoxybenxophenon~ obtained from veratrol has m.p. 1 2 5 O and resembles its isomerides. It forms 2-amino-3' 4'-dimetrTLoxybenxoiuheno?ze which separates from a mixtiire of benzene and light petroleum in yellow needles m. p. 74" and when diazotised forms a mixture of dimethoxyJuo?*enone U1,HI,O m. p. 164' and 2-hydroxy-3'-4'-dimethoxybenzophenone. p-Tolzcenesulpho~~e-2-amino-2' 3' 4'-trimethoxybenxophenone ~2,H,,O,NS obtained by the condensation of pyrogallol trimethyl ether with p-toluenesulphoneanthranilic chloride separates from alcohol in colonr- less glistening scdes m. p. 1 9 0 O . When the product obtained on saponification is dinzotised it forms 3 4-dimethoxy~anthone C,,H,204 which separates from a mixture of benzene and light petroleum in yellow needles m. p. 1 5 5 O and gives a green fluorescence with con- centrated sulphuric acid.p-ToZuenesuZlr?hone-2-uminophenyl ~ - ~ e ~ h o x y ~ a ~ h ~ h y Z ketone C,,H2,O,NS obtained by the condensation of p-toluenesulphoneanthranilic chloride with a-naphthyl inethyl ether separates from alcohol in colourless leaflets m. p. 192'. When'saponified it forms 2-aminophenyl a-methoxy- muphthp Z ketone C18H1,02N which separates from dilute alcohol in yellow glistening crystals m. p. 147" and on diazotisation forms a-methoxynaphthuJuorenone C,,H,,02 which crystallises from alcohol in orange-red needles m. p. 183' and forms a yellowish-green solution with concentrated sulphuric acid. Z-~ydroxyphe~ayZ a-nFethoxynccphthyl ketone Cl,H1,O crystallises from dilute alcohol in yellow leaflets m. p. 124'. p-2'0 Zueneszt Zphone- 2 - c6rr~inopiie.n y 1 /I-rnethoxynuphthy Z ketone C,,H2,0*N87 obtained from P-naphthyl methyl ether separates from alcohol in glistening crystals m.p. 1 8 1 O . When heated with concen- trated sulphuric acid in the usual manner it undergoes srilphonation as well as saponification forming 2-aminopherayl P-methoxynuphthyk ketone- sulphonic acid C,,H1,O,NS which separates in yellow crystals. When diazotised the latter yields a product the solution of which in sulphuric acid is yellow and exhibits a green fluorescence and is accordingly a xanthone derivative. 1 2-Phenon~~htAax;cridons C17H,,0N obtained by heating p-toluene- eulphone-2-aminophenyl P-methoxynnphthyl ketone with hydrochloric acid a t 150-1 SOo separates from pyridine in brownish-yellow needles m.p. 383'. Its alcoholic solution exhibits a blue fluoremence; its solu- tion in concentrated sulphuric acid is yellow and exhibits a bluish- green fluoroscence. A. McK.144 ABSTRACTS OF CHEMICAL PAPERS. Triquinoyl. FRANZ HENLE (Annalen 1906 350 330-343. Compare Nietzki and Benckiser Abstr. 1885 779 1127 ; Nietzki and Bchmidt Abstr. 1888 690 943).-Triquinoyl is readily soluble in moderately concentrated solutions of sodium potassium ammonium calcium barium or magnesium chloi ide potassium iodide or potassium or sodium nitrate a t the ordinary temperature but is only sparingly SO in alkali sulphates and is insoluble in mercuric chloride solutions. It may be purified by solution in hot aqueous sodium chloride from which on cooling more than 60% separates m.p. 98O or after recrys- tallisation from dilute nitric acid m. p. 100’ (decomp.). These solutions of triquinoy 1 decompose slowly at the laboratory temperature more quickly when heated evolving carbon dioxide and forming rhodizonic acid. The solution in aqueous barium chloride yields a red together with a volume of barium salt carbon dioxide corresponding with the equation 7C,O + 6H,O = 6C6H,0 + 6C0 ; the red salt is only slowly decomposed by boiling water forming barium rhodizonate and chloride. The formation of this salt serves for the characterisation of triquinoyl. The action of barjta on triquinoyl i n aqueous solution leads to the formation according to the conditions of four salts a red salt C,0,,3H20,3baOH and three white salts C60,,4H20,5baOH ; C,06 4H20,4baOH and C,,06 3IJ,0,4 baOH respectively.The results obtained cn titration of triquinoyl with baryta agree with the com- positions of the salts C,0,,4H20,5baOH and C60,,4H,0,4baOH. When treated with hydrochloric or snlphuric acid the red salt yields carbon dioxide and rhodizonic acid whilst the white salts form carbon dioxide and a sjrup which reduces silver nitrate and Fehling’s solutions in the cold. Triqninoyl is soluble in acetic anhydride in presence of traces of Concentrated sulphuric acid in ether when sbaken with phosphcrus pentoxide or in methyl alcohol in preseoce of traces of hydrogen chloride. On evaporation in a vacuum a t 20° the methyl alcoholic solution yields crystalline triquinoyl but. if first shaken with anhydr- ous sodium sulphate a yellow syrup which readily decomposes evolving carbon dioxide and forms crystalline triquinoyl only on addition of water The action of sodium acetate on the methyl alcoholic solution leads to the formation of sodium rhodizonate ; the action of anhydrous ammonia on the ethereal or methyl alcoholic solution leads to that of a blackish-red substance which is converted by water into ammonium rhodi zon a t e.Anhydrous triquinoyl C,06 which must be present in the ethereal and methyl alcoholic solutions is formed also together with silver bromide when silver rhodizonate is treated with bromine in ethereal solution. G. Y. ?(OH),* C( OH),-~*O*BnCI C(OH),*C(OH)2.C*0.FaC!l’ Buchu camphor. IWAN L. KONDAKOFF (Chem. Zeit. 1906 30 1090-1091 and 1100-1 l01).-Polemical. The author maintains that the results published by Semmler and McKenzie (Abstr.1906 i 373) are in the main a repetition of his own (Abstr 1905 i 798).ORGANIC CHEMISTRY. 145 The paper contains a historical summary of the work which has been done on t,his subject. P. H. Components of Ethereal Oils. I. Resolution of the Bicyclic Triocean System in Sabineneand Tanacetone. 11. A New Series of Terpenes (cycZoPentadienes). FRIEDRICII Tv. SEMfifLBR (Be?.. 1906 39,441 4-4428).-From tanacetone both cyclohexane and cyclopentane derivatives can be obtained whereas in the case of bicydic hydro- carbons only the conversion into terpinenes or limonenes both cyclo- hexane derivatives,is known. It has hithei to not been possible to break the three-membered ring in the bicyclic triocean system of sabinene and obtain a cyclopentane derivative.By the action of formic acid on sabinene a product is obtained which is separated into two fractions on distillation. The one a formate C1,H,802 b. p. 102-106'/10 mm. aD +14'15' (100 mm.) n 1.4745 D20 0.975 yields on hydrolysis an alcohol C,,H,,O b. p. 93-96'/11 mm. r~ 1.48033 D20 0.926 a hich forms a dihydrocbloride m. p. 51-52' identical with that formed on acting cn sabinene with acetic acid and hydrogen chloride and probably identical with terpinene dihydrochloride. On oxidation with pcrmangsnat P the alcohol forms a glycerol C,OHISOB b. p. 175-177O/10 mm. which crystallises from chloroform and is perhaps identical with the glycei 01 obtained by Biltz ( A bstr. 1899 i 535) from origanol (21-niethylisopropylcyclo- hexenol).The formate on distillation with quirioline forms a terpene C10H16 F. p. 174-177' n 1.479 D20 0.839. The alcohol C10H180 is thus a mixture of dimethylisopropylcyclopentenol and origauol. The secoiid product of the action of formic acid on sabinene is a terpene CIOHIO b. p. 50-54'/10 mm. 169-173"/760 mm. n 1.47 I)"' 0 829-0.831 aD + 13-14' (10 mm. tube) M.R. 45.71 which constants point to its being a cpclopentadisne. E. F. A. Sandarac. ALEXANDER TSCEIIRCH and MAX WOLFF (Arch. Pimrnz. 1906 244 684-712. Coinpare Tschirch and Balzei; Abstr. 1S96 i 493 ; Henry Tracs. 1901 1144).-The resin examined had D 1.071 acid number 141 and saponification number 166. Some of i t was sub- mitted to dry distillation among the products acetic acid was de- tected but not butyric acid or acetic acid; attempts to isolate retene were unsuccessful.From an ethereal solution of the resin lolo aqueous ammonium carbonate extracted amorphous sandaracic acid C22H34O3 in 2*3O/ yield ; m. p. 186-188O (decomp.) has acid number 163 (corresponding with monobasicity) and saponification number 175 and does not contain met hovy 1. With lolo aqueous sodium carbonate acids were then extracted in 87'10 yield. The bulk of these consisted of an amorphous acid of which the lead salt is insoluble in alcohol salndaracinolic acid C24H3,jO3 ; this decomposes a t 265-275° has acid numher 160 (corresponding with monabasicity) and saponification number 163 does not contain methoxyl and forms with acetic anhydride a product that yields acetic acid when hydrolysed.Mixed with this acid is a small quantity of146 ABSTRACTS OF CHEMICAL PAPERS another sundarucopimaric acid C,,H,,O ; this is crystalline has m. p. 1 70° acid number 187 (corresponding with monobasicity) saponification number 194 and iodine number 140 (addition of 31 reqnires 126) ; i t forms an amorphous silver salt containing Ag 26*5°/o; it does not con- tain methoxyl or form an acetyl derivative. Prom the later portions of sodium carbonate solution used in the extraction when they were allowed to remain a crystalline sodium salt sepzrated in yield equal to 0.7O/ of the resin; this melted at 83-S5O dissolved in benzene as well as in water and contained Na T*7"/,; the corresponding silvev salt contained Ag 22*4°/0; the acid decomposed a t 146-14S0 con- tained C 71-76"/ H 9.4'/ and seemed to undergo slowly a trans- formation of which the bittei.principle which also occurs in the resin itself is a product. From the remaining ethereal solution aqueous potassium hydroxide even of 50"/ strength did not extract aaything. The ether was dis- tilled off and the residue steam-distilled when an essential oil of b. p. 152-159" distilled over in 1 .3°/0 yield while amorphous sandaracoresen C22H3602 of m. p. 57" remained in 3.3"/ yield; the resin appears to undergo spontaneously a slow transformation of which acid and essen- tial oil are products. The acids obtained are optically inactive even before the treatment with alkali. C. F. B. Molecular Weight of Elaterin. ARMAND BERG (Compt. rend. 1906 143 1161-1163.Compare Abstr. 1898 ii 447; 1906 i 596).-Chiefly polemical against Pollak (Abstr. 1906 i 973). Further evidence in favour of the formula C2,H,,07 for elaterin is afforded by the results of the analyses of the sodium cudmium and copper salts of elateric acid. M. A. W. Reduction of the Furan Nucleus. MAURICE PADOA and U. PONTI (Atti R. Accad. Lincei 1906 [v] 15 ii 610-615. Compare Absts. 1906 i 530).-When mixed with hydrogen and passed over reduced nickel heated a t about 190° furfuraldehyde vapour yields mainly furfuryl alcohol together with small proportions of more highly hydrogenated compounds. To obtain larger quantities of the latter furfuryl alcohol itself mas reduced in the above manner the products then obtained being 2-methylfuran 2-methyltetrahydrofuran a-methyl-n-butyl alcohol and inethyl propyl ketone.When passed ovei- reduced nickel heated at about 270° furfur- aldehyde vapour is decomposed into carbonic oxide and furan. T. H. P. Ethyl Pyromucylacetate [ Furfuroylacetate]. HENRY A. TORREY and JOAQUIN E. ZANETTI (Amer. Chem J. 1906,36,539-543). -Ethyl furfuroylacetate prepared by Sandelin's method (A.bstr. 1900 i 305) is a pale yellow heavy oil b. p. 143-146°/10 mm. Its oxime C,0H,-C(NOH)*CH2*C02Et crystallises from aqueous alcohol in long silky needles m. p. 131-132O. C,OH,* C(N2H- CO*NH2)*CH2* CO,Et Crystallises from alcohol in flat rhombic plates m. p. 142-144'. Its semicarbaxone,ORGANIC CHEMISTRY. 147 Acetyl-l-phe~yl-3~u~ylpyrazolone C1,H,02N,Ac crystallises from light petroleum in flat. faintly yellow prisms m.p. 69-72?'. Benxoyz- l-phenyl-3-ficrylpyra~olone C13H,0,N,Bz crystallises from aqueous alcohol in white needles m. p. 113-114q and dissolves in alcohol or ether. Nitroso- 1 -phen yl-3 - fuy ylpyraxolone C ,H,O,N,*NO separates from aqueous alcohol as a bright red amorphous hygroscopic precipi- tate softens at about 170° and decomposes at 183-184'. T. H. P. The Pyran Series. 11. Condensation of Ethyl Oxalacetate with Cyclic Aldehydes. H. GAULT (Bull. SOC. chirn. 1906 [iii] 35 1264-1275. Compare Abstr. 1904 i 762; 1906 i 300).- This series of ket,oarylparaconic esters has been obtained by condens- ing ethyl oxalacetate with cyclic aldehydes (1) by Wislicenus' method (Abstr. 1893 i 146 and 714) condensation by means of hydrogen chloride or (2) by condensation in presence of diethylamine the diethylamine derivative being first obtained in the latter case All the esters give red colorations with ferric chloride and are soluble in aqueous solutions of alkali carbonates from which they are re- Drecigitated unchanged on the addition of acids.L A v E thy1 ketophenylparaconate CO< Co*(?H'Co2Et m. p. 104-105° 0-CHPh (compare Wislicenus loc. cit.) furnishes a dietlqlccmine derivative which is formed when benzaldehyde is CO<O- CHPh condensed with ethyl oxnlacetate in presence of diethylamine and stmarates from alcohol in colourless crystals m. p. about 160' C( O*NH,Et,) ?* C02Et ' CO*$!H*CO,Xt co<O-CH*C,H *OMe' (decomp.). Ethyl ketoccn~sy~parccconmte " % similarly obtained from anisaldehyde separates from benzene or dilute alcohol in crystals m.p. 96". The diethylamine derivative forms colourless crystals m. p. about 160' (decomp.). Ethyl keto-o-nitrophenyl- paraconate similarly prepared from o-nitrobenzaldehyde separates from alcohol in colourless crystals m. p. 115". The diethylamine derivative forms small faintly yellow crystals m. p. about 165' (decomp. ). Ethyl keto-m-nitropJLenylparnconate separates from benzene or alcohol in crystals m. I>. 96O and yields a diethylamine derivative which is faintly yellow m. p. about 165" (decomp,). Ethylkcto-p- Ibydroxyphenylpuvaconute m. p. 1 8 4 O crystallises from alcohol ; the diethylamine derivative separates from dilute alcohol in crystals and melts and decomposes about 165'. When ethyl oxalacetate is condensed with salicylaldehyde in presence of hydrogen chloride there is formed ethyl saliceylideneoxaZ- acetate hydrochloride CO,Et*CO*C(CO,Et):CH*C,H,*OH,HCI m.p. 9S0 which crystallises from light petroleum; it readily loses HC1 when warmed alone or when treated in the cold with potassium carbonate or potassium hydrogen carbonate yielding the free ester which is obtained directly when the condensation is effected in presence of piperidine or diethylamine The ester separates from dilute alcohol in crystals m. p. 91O; its alcoholic solution is not coloured by ferric chloride T. A. H.148 ABSTRACTS OF CHEMICAL PAPERS. The Pyran S e r i e s . 111. Condensation of Ethyl Oxalacetate with Aliphatic Aldehydes. H. GAULT (Bull. SOC. chim. 1907 [ iv] 1 21-32).-Aliphatic aldehydes condense with ethyl oxalacetate in presence of piperidine t o form the corresponding ethyl alkylidene- bisoxalacetates CHR[CH(C0,Et)*CO*C02Et]2. These are crystalline solids and combine with a molecule of water to form hydrates which are dei ivatives of tet rahydropyran thus C0,E t $23- Cf3R.$?H Cj02Et CO,Et C(OH)*O-C(OH)*CO,Et' Alcoholic solutions of these hydrates give cz red coloration with ferric chloride on warming and furnish mono yhenylhjdrazones and monoscmicarbxzones of the following constitution CO,Et.~H-CHR-~H*C'O Et CO,Et*C( OH).NR'*C(OH)*CO,Et' where R1 may be -XHPh or NH*CO*CH and are hydrolysed by dilute acids forming aediketonic acids and by cold sulphuric acid forming the cor; espoiiding bisoxalacetic dianhjdrides CBR(CH<g:r); which in contact with water are transformed into the corresponding nnstable di-fi-ketonic acids ; these readily lose carbon dioxide and form uc-diketopimelic acids (compare Abstr.1904 i 762 ; 1906 i 300). Ethyl methylenebisoxalacetnte obtained from forma'ldehjde by the general method (Zoc. cit.) furnishes a hydrate m. p. about 1 1 2 O which trystallises from dilute alcohol and is slightly soluble in cold brlt readily so in hot alcohol. The Tqdrosulphide obtained by treating a solution of the ether in alcohol with hydrogen sulphide crystallises from ether on addition of light petroleiini in small needles m. p. 11 8" and is regarded as having a constitution analogous t o t h a t of the hydrate. Both the hydrate and hydrosulphide regenerate ethyl methylenebisoxalacetate when heated at 1 1 0".The monophenyl- hydraxone m. p. 1 4 3 O obtained by the action of phenylhydrazine on the hydrate dissolved in alcohol crystallises from dilute alcohol and is coloured red by ferric chloride on warming. The anhydrous ether furnishes a d i ~ j ~ ~ e n y l ~ ~ ~ d r a x o n e m. p. 2 1 lo which separates from acetone in woolly crystal#. Tbe nzonosesnicarbccxo~2e yielded by the hydrated ether crystallises from boiling water; m. p. 167" (clecomp.). Meth~lenebisoxc~acetotet~~c~~c~nzide m. p. about 170" (decomp.) is produced when either the ether or its hydrate dissolved in alcohol is treated with dry ammonia ; i t is coloured red by ferric chloride. Methylenebisoxa Zacetotetra benxylccmidedibenxylimicli! obtained by con- densing benzylamine with the anhydrous ether crystallises from boiling acetone and has m.p. 216-217". CO-CH*CO*CO Methylenebisoxa Zacetic diasahydride represented by the formula 0 1 CH I 0 I or OH,(CH<~'*~*) 7 I 1 I co.0 2 CO*CO*CH-CO of which the second is preferred is produced on treating ethyl methylenebisoxalacetate with sulphuric acid. It is very unstable andORCIANIC CHEMISTRY. 149 in contact with (t minute quantity of water a t 0' forms a crystalline monohydrate which when allowed to dry in the air loses carbon dioxide but when drie3 over sulphuric acid undpr reducad pressure regenerates the dianhydride. The latter with excess of water dissolves and passes into the unstable diketonic tetracarboxylic acid which decomposes rapidly giving rise to diketopimelic acid (Abstr. 1905 i 763).The dianhyclride on treatment with aniline yields a dianilide w'hich also decomposes readily forming the dianilide ol dike topimelic acid. Tile latter acid is also prodwed directly by boiling the di- anhydride with dilute acids. T. A. H. Constituents of the Leaves of Carpinus Betulus. Ellagic Acid and Tannic Acids. KARL ALPERS (Arch Fharrn. 1906 244 575-601).-The author sums up the results of his investigation as follows. Tho leaves of the hornbeam (Curpinus BetuEus L.) contain a glucoside from which ellsgic acid is eliminated very resdily even in the extraction of the leaves with 40% alcohol. Neither glucosides nor aldehyde could be detected. Methyl alcohol and acetone as well as ethyl alcohol dissolve ellagic acid to an appreciable although slight extent ; in all other of the usual solvents eliagic acid is practically in- soluble.Ellagic acid chars a t 450-480' without first melting. The shape of its crystals varies ; under the microscope i t appears to consist of short rhombic prisms and long prismatic needles. The constitution of ellagic acid probably is best expressed by Graebe's formula (Abstr. 1903 i 262) ; the water that air-dried ellsgic acid loses a t 100' possibly is anhydride water and not water of crystallisation; in that case the air-dried acid might be regarded as hexahydroxydiphenyldicarboxylic acid and the acid after d r j i n g a t 100" as the dilactone of this as represented by Graebe's formula. The tannin of hornbeam leaves has much similarity with ellagi- tannic acid (Lowe &it. amd. CJ~ein.1875 14 3 5 ) ; i t yields gallic acid when bydrolysed. No glucosidic character could be detected in the tannin ; in this respect i t differs from the tannin of myrobalans of nlgarobilln and of divi-divi pods. c. F. €3. Behaviour of Alkaloid Salts and of other Organic Sub- stances with Regard to Solvents. Reducing Action of Alkaloids. A. SIMMER ( A ~ c h . I'l~urrn. 1906 244 672-684).- Aqueous solutions of Siilt of the alkaloids containing 0.4% of the base were percolated with solvents ; so also were solutions containing. the same percentage of alkaloid with excess of acid. Tho stronger the base the less of it passed into the organic solvent chloroform dissolved out hardly appreciable amounts of nicotine and atropine ; more veratrine strj chnine brucine codeine cocaifie and mcrphine ; and still more narcotine papaverine colchichino caffeine and anti- pyrine. I n the presence of excess of acid the amount of the stronger alkaloids extracted was much diminished ; if the salt itself is soluble in chloroform the amount of i t extracted increases up to a certain point with the excess of free acid if this be hydrochloric hydrobromic or nitric ; if it be sulphurio qhosphoric citric or tartaric of which the alkaloid salts are insoluble in chloroform none of the alkaloid is150 ABSTRACTS OF CHEMICAL PAPERS.dissolved out provided in the case of the last two acids that the excesg of them is considerable. Similar experiments were made with the sodium derivatives of picro- toxin santonin coussein cantharidin and salicylic acid with and without excess of sodium hydroxide.I n the absence of the latter all but cantharidin passed into the chloroform in appreciable quantity ; in the presence of sodium hydroxide only coussein and picrotoxin and of these but traces Experiments were also made with benzene and ether in both of which alkaloids and alkaloid salts am less soluble than in chloro- form with carbon tetrachloride and in the case of morphine with tlruyl and isobutyl alcohols. Xany of the numerical results are tabulated. When an alkaloid mixed with chloroform and water was percolated with chloroform for eight hours in the cases of brucine veratrine strychnine atropine and cocaine the chloroform was found to contain chloride equivalent to an amount of the alkaloid decreasing in the order named from 1.7% to 0.2% of the whole ; in other cases there was no such action.The action of certain alkaloids and their salts in ~V/200 alcoholic or aqueous solution on various oxidisiiig agents was studied namely silver nitrate gold chloride mercuric chloride ferric salts acid permanganate solution &c. Morphine is particularly active as a reducing agent atropine and cocaine we10 the only ones that did not reduce per- manganate appreciably. The salts did not reduce silver nitrate o r mer- curic chloride ; with gold chloride this difference between the alkaloids and their salts was not manifested to the same extent,. Formation of formic acid could not be detected. C. F. B. The Thalleioquinine Reaction. HERMANN BUHNE~~ (Arch. P/harrn. 1906 244 602-622).-An attempt to throw light on the nature of the thalleioquinine reaction.As the reaction is given not only by quinine but also by cupreine it would seem that the reaction must be attributed t o the p-hydroxyyuinoline group. I n the first phase the action of chlorine water converts this into a dichloroketone in the second phase this is converted by ammonia into a quinoniinine colouring matter. The constitution of the chlorine substitution pro- ducts obtained from p-quinanisole and quinine where the containecf phenol group is methylated is a matter for further research. 5 5-Dichloro-6-ketoquinoline G',H,ONCI (Abstr. 1905 i 828) yields 5-chloro-6-hydroxyquinoline C,H,ONCI when it it boiled with dilute alcohol; when it is heated with aniline in alcoholic solution a t 50° it yields 5-c~~loro-6-hydroz;?l-8-n~~ilinequinoZine C,5Hl10N2C1 m.p 127-12So which forms both yellow and dark browu crystals ; when a solution of it in dilute alcohol is mixed a t once with an excess of ammonia it yields dark blue amorphous 0 0 -NH colloidal thallezoquinoline C,,H1,O2N pro- the annexed constitution 1. 1 1 1 analogous with that of thalleioquinine. It is \/ \/\/ essential that an excess of ammonia be added N N a t once; when ammonia is added gradually /v<.N./\/\ bably having the precipitate obtained is brown. vORGANIC CHEMISTRY. 151 The urine of a dog to which quinoline had been administered was found to be coloured green by ammonia after it had been boiled with hydrochloric acid. The presence of 5 6-quinolinequinone was detected ; and it was found by a special experiment that this substance like the dichloroketoquinoline reacts with ammonia to form thalleioquinoline. 0.F. B. Constitution of Hordenine. EUGENE L$GER (Compt. rend. 1906 143 91 6-918).-The author has shown already that hordenine has the formula OH*C&H4;CH,*CH,*NMe (Abstr. 1906 i 204 761) and in the present paper it is shown that the bydroxyl group is in the para-position because 117hen the acetyl derivative of hordenine is oxidised by potassium permanganate p-acetoxybenzoic acid is formed. Hordenine is therefore p-hydroxyphenylethyldirnethylamine. M. A. W. A F i f t h Methylmorphimethine LUDWIG KNORR and HEINRICH H~RLEIN (Ber. 1906 39 441 2-4414).-The fifth or € - ~ ~ e ~ ~ ~ y Z 9 methine is obtained as a laworotatory oil by the action of boiling sodium hydroxide on +-codeine methiodide ; the hydrochloride crystallises in large glistening cubes m.p. 150' (decomp,) the rnethiodide in needles m. p. 195-200" whilst ~cetyZ-c-methylmorphi.)netl~i.ne nzethioclide forms sparingly soluble needles m. p. 205-210°. E. F. A. Conversion of Chlsrocodide into $-Codeine. LUDWIG KNORR and HEINRICH HOBLEZN (Ber. 1906 39,4409-441 I).-By acting on chlorocodide with water at 140-150° Gohlich (Abstr. 1893 i 675) showed that codeine was formed. On adding however acetic acid to an emulsion of ehlorocodide and warm water the substance obtained is identical with Merck's +-codeine (Abstr. 1891 1121). The hydr- iodide m. p. 260-265' crystallises in glistening plates ; the methiodide rn p. 270" also forms large glistening plates.The hpdriodide of acetyZ-$+codeine separates in opaque an b ydrous crystals decomposing a t 285O. E. F. A. Cyclic Imines. 111. JULIUS VON BRAUN CARL XULLER and ERICH BESCHKE (Ber. 1906 39,4347-4357. Compare Abstr. 1905 i 826 ; this vol. i 2S).-I-Alkylpiperidines are obtained in good yield from ac-dibromopentane (1 mol.) and primary amines (3 niols.) (compare Abstr. 1904 i 841). Pentccmet~~~Eenepiper~di~iu~ bromide CH2<CH2*CH C"~*CH,>NB~<CH~*'H,>C~~ CH;CH2 which the author terms di'$eridinium bromide obtained from ac-di- bromopentane and piperidine in nearly quantitative yield in chloroform solution forms a snow-white crystalline mass. The p Z c ~ ~ ~ ~ ~ i c ~ ~ Z o r i d C,,H,,NPtCI darkens a t a%" rn. p. 245O (decomp.). E- P%pweridino-Aa -pentme ( 1 -ccmylenepiperid ine) C,H,,N*CH,.UH,*CH2*CH:CH2 b.p. 201-202O obtained by the action of moist silver oxide on the preceding bromide is a colourless liquid with a basic odour; the152 ABSTRACTS OF CHEMICAL PAPERS. pEotinichZoride has m. p. 99-101O; the picrate 93-94* and the methiodide 159". By treatment with concentrated hgdrobromic acid at Oo it yields 1 -6-bromoccmyZpipe~*idine C,H,,N*C,H,,Br the picrote of which has m. p. 122". The free base is very unstable changing readily into Scholtz and Friemehlt's pentizmethylene-2-methylpyrror- idinium bromide (Abstr. 1899 i 541). Pentamethylenepiperidinium bromide reacts extremely slowly with concentrated ammonis at 2 2 5 O forming a triacid base (1201~4,NB b. p. 185-187"/22 mm. of which the hydroc?doride the platanichloride m.p. 229' (decornp.) and the aecriclzloricle m. p. 170-171" are described. c. s. Action of Grignard's Reagent on certain Indolenines. GIUSEPPE PLANCHER and C. RAVENNA (Atti R. Accad. Lincei 1906 [v] 15 ii 555-561).-\Vhen 2 3 3-trimethylindolenine or 2 3 3 5-tetramethyliudolenine is treated with Grignard's reageat it is transformed into the corresponding dimolecular polymeride the compound behaving as if it had the tautomeric methyleneindoline - formula C,H,<:\R>C:CH,. A s the pure indolenines undergo polymerisation of themselves Grignsrd's reagent here plays the part of a catalyst. Under the action of mngne3iurn phenyl bromide or magnesium methyl iodide 2 3 3-trimethylindolenine yields the polymeride (CllH3N)2 which separates from alcohol in pale yellow crystals m.p. 132" and is reconverted into the unimolecular base if heated above its melting point; with nitrous acid in acetic acid solution it gives the oxime of 2 3 3-trimethylindolenine; if the polymeride is dis- solved in very dilute hydrochloric acid and the solution immediately rendered alkaline it is reprecipitated i n :L flocculent condition but generally the liquid base is attained. Magnesium methyl iodide also acts on 2 3 3 5-tetramethyl- indolenine converting it into the polpvieride (C12H15N)2 which separ- ates from alcohol or light petroleum in pale yellow crystals m. p. 11 1-1 la0 and is less readily polyrnerised than the polymeric 3 3 3-ti-i- me thy1 derivative. The interaction of magnesium phenyl bromide and 2-methyl-3 3 di- ethylindolenine also yields a solid base.The action of magnesium phenyl bromide on acetophenoneanilide gives a comp0'1c~zd CPh,Me*NHPh (?) m. p. 94-96O. T. H. P. New Method of Preparation of 1-Methylindole. ORESTE CAHRASCO and MAURICE PADOA (Atti R. Accccd. Lincei 1906 [v] 15 ii 729-731. Compare Abstr. 1906 i 695).-On passing dimethyl- o-toluidine drop by drop through a tube containing reduced nickel heated at 300-330° part of the base yields 1-methylindole and part undergoes demethylation giving rise to me thyl-o-toluidine o-toluidine and probably methane. By mixing the dimethyl-o-toluidine with hydrogen before passing i t over the heated nickel the yield of 1-methylindole is raised from 6 to 24%; the yield of indoleORGANIC CHEMISTRY.153 from methyl-o-tohidine (Zoc. cit.) is raised in the same way from 6 to 8%. Under the above conditions ethyl-o-toluidine yields a small proportion of a product of an indolic character probably 2-methylindole. T. H. P. Action of Chloroform and Potassium Hydroxide on Scatole [&Methylindole]. ALEXANDER ELLINCER and CLAUDE FL AMAND (Ber. 1906 39 4388-4390. Compare Abstr. 1906 i 696)- 3-Chloro-4-methylquinoline is formed by the action of chloroform and potassium hydroxide on 3-methylindole in alcoholic solution (Magnanini Abhr. 1887 1113). The constitution of the chloro- methylquinoline was determined by heating the base with formal- dehyde in a closed tube at loo' and oxidising the resulting methylol compound with nitric acid D 1.4 3-chZoroqui.noZine-4- cavboxytic acid C,H,< mas obtained m.p. 262-263' C(C0 H):yCl N- CH' (decomp.). The position of the chlorine atom was established by heating the acid 2-5' above its temperature of decomposition when 3-chloroquinoline was formed. The combined action of chloroform and alkali therefore consists in the introduction of the CCl residue between positions 2 and 3 in the indole nucleus. The ni. p. of 3-chloroquinoline aurichloride is 183" not 173' as previously stated (ZOC. cit.). W. R. 1-Hydroxy-2-phenylindole. ANGELO ANGELI and FXANCESCO ANGELICO ( A t t i R. Accad. Lincei 1906 [v] 15 ii 761-767. Compare A bst r. 1 9 04 5 2 6) .-1 -BenxoyZoxy-2-phenyy Zindole i separates from alcohol in white crystals m. p. 100". 3-Nitroso- 1 -hydroxy-2-phenylindole C,H,< NO>CPh (Zoc.cit.) yields (1) an acetyl derivative Cl6HI2O3N2 crystallising from alcohol in yellow needles m. p. 140"; (2) a benxoyl derivative C,,H,,O,N crystallising from alcohol in slender rose-coloured needles m. p. 163' (decomp.) ; (3) an ethyl derivative C,,H,,O,N which separates from light petroleum in orange-coloured crystals m. p. 96". Reduction of 3-ni troso- 1 -hydroxy-2-phenylin dole by means of alcohol hydroxyl- ainine or hydrazine yields ordinary nitrosophenylindole whilst zinc in presence of either acetic acid or ammonium chloride converts it into 3-amino-3-phenylindole. Oxidation of 3-nitroso- 1-hydroxy-2-phenylinclole with chromic acid gives a substance C,H4<No>CPh (Zoc. cit.) which crystallises from alcohol in shining red plates m. p. 1 8 6 O and has all the properties of a ketone; reduction of this substance by means of hydroxylamine yields nitrosophenylindole whilst zinc and acetic acid convert it into a compound C,,€I,,ON which crystallises f rorn benzene in green needles m.p. 225" and is probably 3-hydroxy-2-phenylindole. C(N0H) CO T. H. P. VOL. XCI1. 1. Yt 1.154 ABSTRACTS OF GHEMEAL PAPERS. ELPyrazolones. 11. AUGUST MICRAELZS (Annalm 1906 350 288-329. Compare Abstr. 1905 i 377).-The 5-pyrazolones yield reddish-yellow isonitroso-derivatives whilst the action of sodium nitrite on 3-pyrazolones leads t o the formation of green nitroso-compounds ; on oxidation both series yield strongly acid nitropyrazolones. On reduction the isonitroso-5-pyrazolones form unstable aminopyrazolones (Knorr Abstr.1887 678) whereas the 4-amino-3-pyrazolones ob- tained from the nitroso-3-pyrazolones are stable. The 4-amino-3- pyrazolones are highly reactive substances which in their chemical behaviour closely resemble the primary aromatic amines. I n the present paper a large number of derivatives of 4-amino-1- pheny l-5 - met h y 1- 3-pyrazolone and of the corresponding 1 -pt ol yl-corn - pound are described as are also a number of 4-alkyl-3-pyrazolones. Whilst in some reactions 5-pyrazolones behave as carbonyl compounds 3-pyrazolones always react in the hydroxylic form. Nitroso- and Amino-derivatives of S-Py~axolones.-[ With PAUL KoTE~~~~~.]-4-Nitroso-~-p~enyl-5-~ethyl-3-pyrazolone (Abstr. 1905 i 244) forms a hydrochloride C,,I'190N,*N0,HC1 which crystallises in slender yellow needles m.p. 206O and is not decomposed when heated with water or alcohol. 4 -Nitro- 1-phen yL 5-methy Z-3-pyrccxolone NPh<cMe NH-(?o C.NO prepared by the action of concentrated nitric acid on the nitroso-coLpound in glacial acetic acid solution forms yellow crystals m. p. 222" and dissolves in dilute alkali hydroxides forming a yellow solution; it is obtained also as a by-product in the preparation of the nitroso-com- Pound. pared by reducing the 4-nitroso-compound with zinc and acetk acid crystallises in glistening white leaflets m. p. 1 8 2 O becomes red when exposed to air while moist but is stable when dry reduces Fehling's solution a t the laboratory temperature or ammoniacal silver nitrate when heated and gives a red t o reddish-brown coloration with bleaching powder solution.The hydrochloride C1,H,,ON,,€ICl forms white leaflets m. p. 222' ; the picrate C,,H,,ON,,C,H,(NO,),=OH forms brownish-yellow needles m. p. 195' (decornp.). The amine forms condensatioiz products with the following aldehydes and ketones R = C,N,HOPhMe. With benzaldehyde R*N:CHPh small yellow crystals m. p. 248' ; anisaldehyde R*N:CH*C,H,*OMe slightly blue leaflets m. p. 245' ; cinnamaldehyde R*N:CH*C,H,Ph yellow leadets m. p. 232" ; acetophenone CPhMe(NHR) slender yellow needles m. p. 296' becoming brown ; benzophenone CPh,(NHR) yellow leaflets m. p. 301° becoming brown ; pyruvic acid CO,H*CMe(NHR) glistening white leaflets m. p. 299' becoming brown - - v NH-70 NPh<CMe:C*NHAc' 4-Acetylanaino- 1 -phenyl-5-methyl- 3 -pyraxolone crystallises in slender white needles m.p. 233'. The 4;forrn~Zurnirm-ORGFANIC CHEMISTRY. 155 compound C,,W,ON,*NH*COH crysballises in white needles m. p. 197'. forms colourless crystals m. p. 176'. 4-Benxeiaesu~hon~llccnzino-3- su lphonoxy- 1 -phenyl-5 -meth ylpyrccxole SO,Ph*O*C,N,PhMe*NH*SO,Ph forms large transparent crystals m. p. 171'. NH-$!O CMe CON :SO' crystallises in yellow leaflets m. p. 12Eio and is decomposed when heated with aqueous alkali hydroxides. 4-TiLionyl~mino-l-phe~iyl-5-metJ~yl-3-py~azolone NPh< separates from alcohol in small crystals m. p. 221° is soluble in aqueous alkali hydroxides and is decomposed by hot mineral acids forming phenylthiocarbimide and the 4-aminopyrazolone. Bis-l-phem$- 6-rnet~y~-~-~yrccxo~ony~-~-thio~~6rbamide cs NH* c< '*-TH) forms small white crystals m.p. 2 6 5 O becoming brown. ( CMwNPh 2) . - iY H-$!O CMe C*N,Cl' formed by diazotisation of The diazo-chloride NPh< the 4-aminopyrazolone crystallises i< colourless needles decomposes a t lZOo gradually becomes red on the surface and gives reactions similar to those of diazobenzene chloride. It coudes with B-n-nanhthol in alkaline solution forming 4-Pnc6ph tholaxi- 1 -pItengl-'5 -niekyl-3- which crystallises in small pyraxolone NH-YO NPh<CMe C- N; C ,H; OH' yellowish-red leaflets m. p. 4213. " The diazo-chloride forms with resorcinol a dark brownish-red precipitate soluble in an excess of alkali hydroxides with salicylic acid an orange-red precipitate and with anilino or dimethylaniline a dark red solution yielding a dark red to reddish-brown precipitate on addition of sodium acetate 4-Azo-1 -phenyZ- 5 -methpl- 3-pyrccxolone N2( C,N,HOPhMe) 2 formed by the action of the 4~amino-3-pyrazolone on its diazo-chloride separates as a yellowish-red crystalline powder m.p. 160" ; the Iydrocldorids C2,H,,0,N,,2HCl crystallises in red leaflets m. p. 126'. 4-lodo- 1 -phengI-5-methy I- 3-pyraxolone NPh<CBTe:CI NH-?o prepared by boiling the 4-diazo-chloride with aqueous potassium iodids forms small yellow crystals m. p. 207'. 4 -Damethy lamino- 1 pherzyl-5-rnethyZ- 3 -p yraxolone NH-$!O NPh<CITe:c*NMei formed with development of heat by the action of methyl iodide methyl alcohol and potassium hydroxide on the hydrochloride of the ??8 2156 ABSTRACTS OF CHEMICAL PAPERS.4-arnino-S-pyrazolone crystallises in matted slender white needIes m. p. 18S0 is soluble in dilute acids 01' alkali hydroxides and when heated on the water-bath with methyl iodide yields dimethylamino-3-anti- pyrine (4-dimsthykamino-1-phenyl-2 5-dirnethyZ-3-p~raxolone; 3-pyram- '<gBfe-Nph C'C(NMe2)>CYMe which is also obtained by the action of methyl sulphate on the 4-amino-3-pyrazolone. It crystallises in slightly yellow needles in. p. 74'. When heated with methyl iodide under pressure a t loo" it forms the nzethiodide C,N20PhMe2~NMe,I which crystallises in white leaflets m. p. 1 2 6 O and when boiled with silver chloride in aqueous solution yields the metJLochZoride ; this when heated loses methyl chloride and forms dimethylamino-3-antipyrine.The methiodide of 4-dimethylamino-l-phenyl-5-methyl-3-pyrazolone NH-(?o formed by boiling the amino-base with methyl NPh<C~e C*NMe,I' iodide and methyl alcohol crystallises in white leaflets m. p. 216". NH-Y 0 CMe N O N O ' 4-Nitroso-1 -p-to1?/1-5-nzeti~yl-3-~yr~~olone C,H,* N< pared by the action OF sodium nitrite on the 3-pyrazolone in glacial acetic acid solution forms small green crystals m. p. 167"; the hydrochloride C,,H,lO,N,,HC1 crystallises in slender yellow needles m. p. 235". 4-Nitro-l-p-tolyl-B-naetJ~yZ-3-pyraxolone C,,H,,0N2*N0 crystallises from alcohol in slender white needles m. p. 1903. 4-Amino-I-p-tolyl-5-naetl~yk-3-~~r~6xolone C,,H1,ON2*NH2 m. p. 249' crystallises from chloroform and has a red lustre ; the hydrocldode CilHI,ON,,HCl forms slightly red crystals m.p. 291". Condensation products of the amine with the following aldehydes and ketones are described ; R = C,,H,,ON,. With benzaldehyde CHPh:NR small colourless crystals m. p. 233' ; anisaldehyde O&le*C,H,*CH:NR m. p. 235" ; cinnamddehyde CHPh:CH*CH:NR yellow prisms m. p. 217" ; acetophenone CPhRkfNHR) small glistening leaflets m. p. 302" ; benzophenone CPh,(NHR)2 white leaflets m. p. 3053 (decomp.) ; pyruvic acid CO,H*CMe(NHR),~ white crystals decomposing a t 303". C 1H,,0N2*N H Ac crystallises in slender needles m. p. 244" The Jibenxoyl derivative OBZ*C,,H,~N,*NHBZ foyms slender colourless needles m. p. 193". The dibenxenesu@honyl deyivative forms colourless cryst,als m. p. 159". 4- PhenyEtl~iocal.bnnaido- 1 -p-tolyl-5 -naethyl-3 -pyraxoZone C H I 0 N N I€ C S N 13 P h m. p.220° crystallises from alcohol. 4-Diazo-1 -p-tolyl-5-~nelJ~yl-3-ioyraxolone chloride C,,H,,ON,*N,Cl does not decompose when its aqueous solution is evaporated on the water- bath ; it couples with P-naphthol forming a dark red crystalline ccxo- dye C,,H,,O,N m. p. 228'. The diazo-chloride also couples with dimethylaniline salicylic acid and resorcinol forming dark red dyes. 4- Benxeneaxo- 1 -phenyE- and 4-Benxeneaxo- 1 -p-t olyl-5 -nzetiLylpyraxole.- [With PAUL Ko~~~~1~~~.]-4-Benzeneazo-~-phenyl-5-methylpyrazole 4 - Acet y Eamino- 1 -p- tolyl- 5 - naetJql- 3 -pyraxo Zone,ORGANIC CHEMISTRY. 157 cannot be obtained by reduction of 3-chloro-4-benzeneazo-l-phenyl-5- methylpyrazole but is formed when 4-benzeneazo-l-pheny1-5-methyl-3- pyrazolone is heated with phosphorus pentasulphide at 220-230° ; the hydrochZoride C1,H,,N,,HC1 forms dark red needles m.p. 138' and gradnally decomposes at the laboratory temperature. 4-Benxeneaxo-1 -p-toly1-5-methylpyra;xole C,1H,,N2*N,Ph formed by heating 4-benzeneazo-l-p-tolyl-5-methyl-3-pyrazolone with phosphorus pentasulphide a t 220-230° separates from light petroleum in yellowish-red crystals rn. p. 102' ; the hydrochloride CI7H,,N,,HCl forms yelloaish-red needles m. p. 156' and readily decomposes 4-AZkyl-3-pyraxolone.-[With ALEXANDER DRET.YP.]-~ -Phenyl-4 5- dimethyt-3-pyrccxoZone NPh< NH-(?o is prepared by the action of CMe:CMe' phosphorus trichloride on a mixture of acetylphenylhydrazine and ethyl metbylacetoacetate; it forms small white needles m.p. 254". The benxenesu@honyI derivative NPh<N- -Y*0*802Ph crystallises in colourless needles m. p. 97". CMe:CMe N = FCl 3-ChZoro-1 -phenpZ-4 ; 5-dinaethyl;llyrtcxoZe NPh< CMe:C&,le prepared by the action of phosphorus oxychloride on the pyrazolone at 210' under pressure is obtained as a white crystalline mass m. p. 34' b. p. 181°/15 mm. is slightly volatile in m current of steam and when heated with methyl iodide in a sealed tube at 100° vields 3-iodo-1- Nii'eI:yI ~ h i c h CMe=CMe' plzenyl-4 5-dimethylpyraxolium methiodide NPh< crystsllises in slightly yellow needles m. p. 2 1 7 O . iMethyZ-3-antipyrirze CMegN Ph *vMe>O prepared by heating the CMe*C- pyrazolone with an excess of methyl iodide in a sealed tube at looo crystallises in white leaflets m.p. 97' and gives a red coloration with forms white ferric chloride. The lzydriodide needles m. p. 1 7 6 O and on recrystallisation from water yields the KMeI :?*OH NPh<CMe=CMe ' NPh-cMe C (OH) C Me' m. p. '75". Tho crystalline s i t 'h Mef> C.0 .N Ble< C Me=-CMe picrate C,,H,,0N2mO* C,H,(NO,) forms yillo& needles m. p. 103'. The chZoride C,,H,,N,Cl ni. p. 94' is very hygroscopic. fl ''e>S for me d by the act ion of C&le c -- potassium hydrogen sulphide on the iodopyrazole hydriodide in aqueous solution or from the antipyrine chloride by Michaelis and Besson's method (Abstr. 1904 i 78O) separates from water in white crystals m. p. 103" and gives a yellow precipitate with sulphurous acid in concentrated solution ; the methiodide C,,H17N,SI forms white crystals m.p. 175". Afet?qL 3 -t hiopyrine OMe<N -3- Thiomet i y I- 1 -pheny I - 4 ; 5-dimeth ylpyrccxo Ze (met h y 1 - $-3 -t hiop yrine) FgSMe prepared by heating the preceding methiodide N = NPh<C%fe CMe158 ABSTRACTS OF CHEMICAL PAPERS. under reduced pressure crystallises in long white needles m. p. 40° b. p. 205-20S0/20 mm. 1 -PhenylE- 5 -methyl- 4-etlqZ- 3-pyraxoZone prepared by the action of phosphorus oxychloride and acetylphenylhydrazine on ethyl ethyl- acetoacetate forms white needles m. p. 172'. The following sub- stances derived from this pyrazolorie are described. The benzene- sdplmnyl derivative C121X 3N2* O*SO,Ph forms slender needles m. p. 74O7 The S-ciJoroiuyrazole C12Hi3N2Cl forms yellow needles m. p. 92'.The snethiodide of the 3-iodopyrazole C13H1GN212 m. p. 196'. Ethgl-3-ccntiyyrine C M e < ~ ~ ~ ~ f l ~ > O forms white prisms m. p. 64'; the iqdriodide C ,H,,0N2,HI m. p. 175" when recrystallised from water loses half o! its hydrogen iodide and yields the salt C,GH,,O,N,T m. p. 130° which has a constitution analogous to that of the come- spoilding methyl-3-antipyrine derivative. The picrate forms large yellow crystals m. p. 83". C13T'1,0N,,C,H,0(N02) Etl~yl-3-tZiio~~l.ine NPh-NMe "eQ,,,_&>S crystallises in slender needles m. p. 120' ; the naethiodide forms white crystals m. p. 108". ~ t l ~ ? / Z - ~ - 3 - t h i o ~ ~ ? / r ~ n ~ (3-tl~iometlt,yl- l-~han~l-5-rneth~Z-4-e~l~yl~y~~c~~oZe) C1,HI3N;SMe forms a colourless oil b p. 160-165"/12 mm. C,,H,,N,S,MeI G.Y. o-Carboxylic Azo-compounds and their Transformation into 3-Hydroxyindazyl Derivatives. PAUL FREUNDLER (Comnpt. rend. 1906 143 909-911).-The author has shown (Abetr. 1906 i 544) that benzene-o-azobenzoic acid is converted into chloro-3-hydroxy-2- phenylindazole by the action of phosphorus pentachloride or t hionyl chloride The meta- and para-isomerides under similar conditions yield the normal acid chlorides. The benzene-o-azochlorobenzoic acid obtained by oxidising chloro-3-hydroxy-2-phenylindazole is identical with benzene-2-azo-5-chlorobenzoic acid obtained synthetically as follows. ~~etlt,yZ-3-ci~Zoroacet~Zanti~~ani~ate m. p. 127') obtained by the action of sodium hypochlorite on methyl acetylanthranilate yields 5-cl~lo~o-antl~ranilic acid m. p. 21 1-21 2') CO,H*C,H,Cl*NH,[Cl NH CO,H= 5 2 11 on hydrolysis which is converted into y -chloroaniline when heated a t 200' ; niethyl-5-chloroc~1~ti~r~~~ilc~te m.p. 69" b. p. 168-170°/22 mm. condenses with nitrosobenzene to form methyl benzene-2-azo-5-chloro- benzoate and the corresponding acid is identical with the oxidation product of 5-chloro-3-hydroxy-2-phenylindazole C7N2H,PhC1*OH. Benzene-2-azo-5-chlorobenzoic acid yields a dichloro-3-hydroxy-2- phenylindazole m. p. lS6-187' by the action of phosphorus penta- chloride in which the second chlorine atom probably occupies position 7. 3-H?ldroz?l-Z-;uT~ela~lindccxole C$N,H,Ph-OH m. p. 216-217' can be prepared from the ncetal derivative of benzene-3-azobenzoic acid by the action of dilute sulphuric acid. The lactone of 3-hydroxy-o-indazyl- benzoic acid (Abstr.1904 i 667; Carre Abstr. 1906 i 705) can beORGANIC CHEMISTRY 159 obtained by reducing o-nitrobenzyl alcohol in alkaline medium OF by the action of heat on o-hydrazobenzoic acid or o-azobenzoic acid ; or by the action of acetic acid on o-azoxybenzaldehyde (Bamberger private communication). M . A. W. Condensation of Hydrazines with Acetylenic Nitriles. General Method of [Synthesising Pyrazolonimines [5-Imino- pyrazolines]. CHARLES MOUREU and I. LAZENNEC (Compt. rend. 1906 143 1239-1242. Compare Abstr. 1906 i 702-956).- Phenylpropiolonitrile condenses readily with hydrazine hydrate in alcoholic solution to form 5-imino-3-phenylpyrazoline9 identical with the compound obtained by Seidel (Abstr. 1899 i 138) by the action of hydrazine hydrate on cyanoacetophenone ; it is probable that the hydrazone NH,-N:CPh*CH,-CN or NH,*NH*CPh*CH*CN is first formed and subsequently converted into the isomeride imino- pyrazoline and this explanation of the reaction is supported by tbe fact that as-diphenylhydrazine condenses with phenylpropiolonitrile to form the diphenylhydrazone NPh,*NH-CPh:CH*CN identical with the hydrazone prepared by Seidel (Zoc.cit.) by the action of cyanoaceto- phenone on diphenylhydrazine. 5-lmino-3-amyZ- pyraxoline m. p. 414 b. p. 205-208°/18 mm. (corr.) and the picrate m. p. 142-1 44". 5-lmino-1 -phenyZ-3-amyZpyraxoZine b. p. 23L-233"/18 mm. (corr,) Di0 1.047. 5-Imino-3-hexyZpyruxoZine m p. 32O b. p. 214-217"/18 mm. (corr.). 5-Imino-3-phenyZpy~*axoZine m. p. 125-126O ; the Icydrochloride m. p.78-80°; the pZatinichZoride m. p. 225O (decomp.) ; the picrate m. p. 202-203' (corr.). 5-Imino-1 3-di- phenylpyrazoline m. .p. 127-129O (compare Seidel Abstr. 1899 i 138); the hydrochloride is dissociated by excess of water and the platinichloride decomposes at 153-1 55O. The following iminopyrazolines were prepared. M. A. W. 5-Hydroxy-l 2 3-triazole. OTTO DIMROTH and HANS AICKELIN (Ber. 1906 39 4390-4392. Compare Curtius and Thompson this vol. i 95).-MethyZ l-o-p-dinitrophenyZ-5-tricmoZone-4-car6oxyZate C H ( N 0 ) * N < ~ ~ ~ = . c o 2 ~ e prepared by the nitration of the ester at - 5' with fuming nitric acid crystallises from glacial acetic acid in white needles m. p. 195' and is explosive. When this compound is heated with a methyl alcoholic solution of ammonia a t looo for ten hours in a sealed tube 2 :4-dinitroaniline and the ammo~~ium salt of methyl 5-hydroxytriaxole-4-carboxglate SJ N=== NH<C(ONH4):c*C0,Me' are formed The barium salt (C4H,03N3),Ba,5H,0 crystallises in long colourless needles.The ester crystallises in colourless aggre- gates and is easi'ly soluble in water the solution giving with ferric chloride an intense brownish-red coloration indicating an enolic constitution. By hydrolysing with barium hydroxide and acidifying,160 ABSTRACTS OF CHEMICAL PAPERS. a solution of 5-hydroxytriazole-4-carboxylic acid is obtained and its alkaline solution with a diazotoluene salt yields 4-tolueneazo-5-hydr- oxytriazole (Curtius and Thompson ibid.). PHILIPPE BARBrER and PAUL SISLEY (Bull.Xoc. cJ~im. 1906 [iii] 35,1278-1282. Compare Abstr. 1906 i 51 989),-The method employed is essentially that used by Fischer and Hepp (Abstr. 1903 i 134) which consists in condensing p-amino- azo-compounds under the influence of heat. When a mixture of p-aminoazobenzene and its hydrochloride is heated i n phenol at 14O-1fiO0 s-a?ziZinopiLenosafrcc?zine is produced ; it is a black microcrystalline powder with a bronze sheen. It cannot be obtained by condensing aniline with s-phenosafranine. Jt dyes mordanted cotton and silk in bluish-violet shades. The mechanism of the reaction is represented as follows Ph*N,=C,H,:NH + W. R. Formation of s-Safranines. NH:C,H,(NHPh):NH. -t Ph*N2*C,H4*N:C,H,(NHPh).NH + NH,- C,I€,<iz>C,H,(NHPh) :NH. This reaction is possible because in p-aminoazobenzene there is relatively to the amino-group an ortho-position free which permits the introduction of the aniline residue.This is not the case when p-aminoazotoluene is used as a starting point and consequently when this substance is condensed in the manner just described the product obtained is s- tolusccfrmbze which after purification forms reddish- brown crystals with a metallic sheen. Along with the tolusafranine there is produced a violet coloiiring matter which after prolonged heating is converted into a red dye and a reddish-yellow substance which appears to be o-azotoluene. p -Amin c azoben Zen e condenses with ben zeneazo-a-naphth ylamine in the manner described to form ?znp?~t~a~7LenosaJ~unine which can be purified by recrystallisation from warm water.I t s hydrochloride forms slender brown needles with a bronze sheen. It dyes mordanted silk 2nd cotton a fine red with shades more bluish than those given by the pheno- and tolu-safranines. PHILIPPE BARBIER and PAUL SISLEY (Zd. SOC. chim. 1906 [iii] 35 1282-1 285. C'ompare Abstr. 1906 i 51 989 and preceding abstract).-When a mixture of p-diamino- azobenzene hydrochloride and aniline hydrochloride in alcohol is heated in an autoclave atl 160-170° two products are formed the one having the reactions and properties of as-phenosafranine and the other which is a dark microcrystalline powder with a metallic sheen is as-n~ailinopJ~enosa~,anine C,,HI 9N5. It gives fine bluish -violet shades on silk and cotton rnordanted with tannin and tartar emetic.The mechanism of the reaction which gives rise to as-anilinopheno- safranine is supposed to be the following 2C,H,*NH2+ NH :C6H3( *NH*C H,*NH,):NH -.+ T. A. H. Formation of as-Safranines. v z y H ?( NH Ph) :NU C 6H,* N*C,H4*NH2 + NH -t- 2H2.ORGANIC CHEMISTRY 161 p-Diuminoaxotolueme obtained by careful reduction of p-nitro-o- toluidine when condensed with o-toluidine as just described furnishes as-tolusafrocnim C,,H,,N which is crystalline has a metallic sheen and gives superb rose-red shades on silk or cotton the tones being always more bluish than those of the corresponding phenosafranine. The pkatinichloridee is a crystalline powder with a metallic lustre. T A. H. Action of Alkali Hydroxides on s-Tribrornodiazobeiizens. ELJGEN BAMBERGER and E.KRAUS (Ber. 1906 39 4248-4252. Com- pare Orton Trans. 1903 83 796 ; 1905,87 99; Haatzsch Abstr. 1903 i 665).-3 5-Di6romo-2-aminop~~enol OH*C6K2Br2*NH is pro- pared by the action of aqueous sodium hydroxide on diazotised 2 4 6-tribromoaniline and reduction of the resulting quinonediazide with stannous chloride and glacial acetic acid in hydrochloric acid solution or by hydrolysis of dibromo-o-phenetidine by means of aluminium chloride ; it crystallises in long glistening colourl~ss broad needles m. p. 145" is readily soluble in aqueous alkali hydr- oxides and forms a hydrochloride wliich crystallises in glistening needles is sparingly soluble in water or dilute hydrochloric acid and is decomposed by much boiling water. The base gives with alcoholic ferric chloride a violet coloration rapidly becoming brown and deposits a flocculent precipitate ; with calcium hypochlorite i t gives a brownish- red coloration becorning reddish-brown or in dilute acetic acid solu- tion a violet coloration becoming brown and forms a dark brown flocculent precipitate.3 5-Dibromo-o-quinonediazide prepared by the action of nitrous acid on tho dibromoaminophenol crystallises from ether in glistening orange-yellow prisms or from light petroleum in compact yellow needles m. p. 130' (decornp.) and can be recrystallised from water but decomposes on prolonged boiling; it couples with the naphthols or resorcinol in alkaline or with a-naphthylamine in acetic acid solution. When boiled with hydrobromic acid and copper powder the quinaoe- diazide yields 2 3 5-trib~*omopJleizol C6H,Br,*OH which crystallises from light petroleum in glistening needles m.p. 91.5-92,5O is readily volatile in a current of steam gives a brownish-violet colora- tion with alcoholic ferric chloride and forms a voluminous crystalline precipitate (2 3 4 5-tetrabromophenol?) with bromine water. GI-. Y. 3 6-Dihydroxyquinonebisdiazoanhydride. FRANZ HENLE ( AnnaEen 1906 350 344--367).-The substance obtained by Nietzki and Eenckiser (Abstr. 1885 779 1127) as a residue on dissolving crude triquinoyl in sulphurous acid and considered by these authors to be di-iminodiquinoyl is now shown to be 3 6-dihydroxyquinonebis- >N. This like the diazo-anhydride diazoanliydride N< of tetronic acid as a colourless syndiazoanhydride resembles ethyl diazoacetoacetate anhydride (Wolff Abstr.1903 i 203) whilst on the other hand it forms a sulphonate as does the yellow o-diazo- phenol. o * ~ - c o * p " c *co c 0162 ABSTRACTS OF CHEMICAL PAPERS. 3 6-Dihydroxyquinonebisdiazoanhydride is obtained also as an in- soluble residue when crude triquinoyl is extracted with aqueous sodium chloride or in a 70-80% yield by the action of sodium nitrite on diaminotetrahydroxybenzene hydrochloride in SO% sulphuric acid solution ; it crystallises slowly from nitric acid D 1.4 in long white prisms detonates at 12B0 becomes yellow on exposure to light is decomposed by prolonged boiling with water forming a cherry-red solution and yields diaminotetrahydroxybenzene hydrochloride when reduced with stannous chloride and fuming hydrochloric acid.I n sodium carbonate solution the bisdiazoanhydride couples with It-salt P-naphthol or resorcinol but not with phenol giving an intense violet-red coloration which becomes blue and fluorescent on addition of dilute sodium hydroxide red on addition of acetic acid and is destroyed by hot sulphuric acid. Z’etrasodiunz 3 6-dih ylclroxyquinonebisdiaxosuZp~onate C60,( ONa),(N2*S03Na)3 3H@ formed with development of heat by the successive action of sodium hydrogen sulphite and sodium hydroxide on the bisdiazoanhydride crystallises in orange-yellow leaflets loses 3H,O slowly in a vacuum over sulphuric acid is very hygroscopic when anhydrous and is decomposed evolving gas when heated with water or dilute acids. With an excess of aniline the bisdiazoanhydride forms an udditive compound probably C,O,(OH),(N,*NHPh) which is obtained as a dark red crystalline powder and decomposes into its generators slowly over sulphuric acid in a vacuum more quickly when treated with organic solvents or acids. A similar cornpound is obtained on adding the bisdiazoanhydride to fused a-naphthylamine. The action of concentrated aqueous ammonia on the bisdiazo- anhydride leads to the formation of 3 6-dio~yguir~one6istriaxe.12 - - (?) which crystallises in colourless prisms NHi-0 N:y k= N>C602<().NH-% m. p. 1 6 7 O decomposesoabove its melting point and detonates when quickly heated. It is decomposed by aqueous sodium hydroxide and when treated with concentrated aqueous or methyl-alcoholic hydro- chloric acid or with hydrogen chloride in ethereal solution evolves 4N and yields a substance C,H,0,N2Cl,,2H,0.5-Nitro-3 ; 6-dihyroxyquznonedtaxoc~nhydride N N OH* C,O,(NO,)<O >N 4H,O or OH= C,O,( NO,)<# 4 H,O prepared by the action of nitrosulphuric acid on 5-nitro-2-amino- tetrahydroxybenzene hydrochloride in cooled SO% sulphuric acid solu- tion crystsllises in lemon-yellow leaflets or long thin needles m. p. 70° decomposes above 100’ or when heated with a solvent and detonates when heated rapidly ; it is decomposed by concentrated aqueous ammonia or alkali hydroxides but with dilute sodium carbonate and diIute ammonia forms highly explosive yellow salts. When treated with ethereal ammonia 4 6-dibromo-2-diazophenol is partially decomposed evolving gas whilst 4 6-dinitro-2-diazophenol forms a voluminous red product which decomposes slowly in contact with ethereal ammonia rapidly when exposed to air.ORGANIC CHEMISTRY.163 Chlorotriketocy clopentune co<c€€"*co CC1'Y*oH,H20 is formed when 3 6-dihydroxyquinonebisdiazoanhydride is bailed with 20/ h y drochloric acid; it crystallises from moist chloroform in nodular aggregates of colourless needles m. p. 72-74' loses H,O over sulphuric acid in a vacuum or when boiled with chloroform and calcium chloride forming a white hygroscopic crystalline powder m. p. 119'. It is a strong monobasic acid is decomposed by concentrated alkali hydroxides reduces ammoniacal silver solutions and behaves towards bromine and potassium permanganate as a n unsaturated substance The sodium C,H,O,ClNa,~H,O and ummoniuna C,H,O,Cl*NH salts are described.The acetate C7H504Cl forms colourless crystals m. p. 57' ; the semi- curbaxone C,H,O,N,Cl is obtained as an infusible white crystalline precipitate. When heated with bromine water chlorotriketocgclo- pentane is converted into chloropentabromoacetone m. p. 9 9 O (m. p. 92O EUGBNE GRANDMOUGIN and H. LEmmN (Ber. 1906 39 43s4-4385).-Iiexanitrohydraxobe?zcelze prepared either by heating picrylhydrazine and picryl chloride for four hours at 120' or by heating a n alcoholic solution of picryl chloride (2 mols.) hydrazine hydrate (1 mol.) and potassium hydroxide (3 mols.) forms bright yellow needles m. p. 201'. The monopotassium salt dissolves in acetone to a deep red solution whilst the solution of the dipotassium salt is blue.Eexanitroaxobenxene prepared by the oxidation of the above compound with nitric acid D 1.3 crystallises from glacial acetic acid in red prisms m. p. 215'. Anthranil. X. A New Reduction Product of o-Nitrobenz- aldehyde. EUGEN BAMBERGER (Bey. 1906,39,4252-4276. Compare Eamberger and Elger Abstr. 1904 i 93; Heller Abstr. 1906 i 5S5).- In the reduction of o-nitrobenzaldehyde a new intermediate product has been found to be formed between o-hydroxylaminobenzaldehyde and anthrani1.-[ With E. W. REMMERT.]-If o-nitrobenzaldehyde is shaken with ether and aqueous ammonium chloride in a freezing mixture while zinc dust is added gradually there is formed aproduct which for the present is termed agnotobenxaldehyde. constitution NO,* C,H,*CH( OH)*N( OH).C,H,* COH or O[ N( OH) *C6H4* COH] ; of these the latter is preferred. It crystallises in glistening white needles m. p. 94' if heated slowly from 65O or 98-5-99' if heated rapidly from 8 5 O and decomposes slowly a t the ordinary temperature more quickly when treated with cold dilute sulphuric acid or when boiled with water. It gives with alcoholic copper acetate a deep brown coloration rapidly becoming a dirty green cuprous oxide being precipi- tated reduces Fehling's solution and when treated with 17% aqueous sodium hydroxide and ice becomes orange-red changing to yellow and forms o-azoxy benznlclehyde o-azobenzoic acid o-nitrobenzaldehy de o-ni tro benz y 1 alcohol o -ni t ro hen zoic acid traces of o-aminoben zaldehyde and 2-car box3 benxeneccxox ~-2'-benxy I CL Zcohot.Hantzsch Abstr. 1889 854). G. Y. Hexanitroazobenzene. W. R. C14H1205N2 7 It may have the164 ABSTRACTS OF CHENICAL PAPERS. Agnotobenzaldehyde does not form an N-aldoxime ether whereas o-nitrobenzaldehyde condenses with phenylhydroxylamine forming the N-aldoxime ether N0,*C6H,<-O->NPh which crystallises in slender yellow needles m. p. 93.5'. When reduced with aluminium amalgam and water in presence of ether agnotobenzaldehyde yields anthranil and o-aminobenzyl alcohol ; with phenylhydrarine in cooled pyridine solution it forms o-nitrobenz- aldehydcphenylhydrazone m. p. 156*5-157' together with the pro- duct C,,H,,ON obtained by Buhlmann and Einhorn by the action of phenylhydrazine on anthranil (Abstr. 1901 i 94). o-Azoxybenzsldehyde ON,(C,H,*COH) (compare Bamberger and Demnth Abstr.1902 i 95) crystallises from alcohol in golden- yellow needles m. p. 115*5-119° when rapidly heated from 110" intumesces at 130-140° and yields a sublimate of slender needles ; it reduces silver nitrate only slowly in amrnoniacal solution but rapidly in presence of sodium hydroxide. crystallises in light orange needles m. p. 185.5-186' (decomp.). The action of direct sunlight on o-azoxybenzaldehyde in acetone solu- tion lends to the formation of the Eccctone of o-indazolylbenzoic acid C H *C-0 \CO which crystallises in lemon-yellow needles with N N - C6H4/ bronze lustre m. p. 295'. The lactone is formed also together with o-azobenzoic acid (Maier Abstr. 1902 i 192) by oxidation of 0-azo- benzaldehyde with chromium trioxide in glacial acetic acid solution.CH The dipTiengZhyldraxone ON,(C,H4*CH:N2HPh) I6 ,,4 I 2'- Benxpl ciZcoTiol-u,-ox?j-2-6enxoic acid OH* C H;C,H,*N,O C,H CYO,H crystallises from water or alcohol in strongly refracting small hard almost colourless prisms m. p. 160--161' forms a lemon-yellow solix- tion in water or alcohol and has an acid reaction. coppe? (C~4Hl104X,)2Cu and Zeccd (C1,H1104N2),Ph salts are described. 2'-~e~axccZdeTq~dea;zoxy-2-benxoic acid CO,H* C6H4*N20*C6H4*COH? pre- pared by oxidation of the alcohol with potassium dichromate in dilute sulphuric acid solution crystallises in golden-yellow needles m p. 1 79-lSOo (decomp.) and reduces silver nitrate and Fehling's solutions on prolonged boiling in presence of sodium hydroxide. The phenpl- ILpdTacone C0,H*C,H,~N,0*C,H4*CH:N,HPh crystallises in orange- red leaflets with bronze lustre m. p.156'; the sodium salt forms golden-yellow leaflets. On prolonged boiling with potassium dichromatc in dilute sulphuric acid solution 2'-benzyl alcohol-azoxy-2- benzoic acid o r its aldehyde yields o-azoxybenzoic acid. G. Y. The sibver CI*HlIO4%% Oxidation of Aminoindazoles and a Remarkable Method of Formation of Dichloroindazole. EUGEN BAMBERGER and S. WILDI (Ber. 1906,39 42$6-4285).-Whilst indazoles containing a n amino-ORGANIC CHEMISTRY a 165 group in the pyrazole nucleus are converted by various oxidising agents in acid solution into 4-hydroxy-/3-phenotriazine (Bamberger and v. Goldberger Abstr. 1S99 i 170; Bamberger ibid. 543) 3-aminoindazole is oxidised by potassium ferricyanide or atmospheric oxygen in alkaline solution yielding 3 3'-azoindazole ,v% ,CfA N- C*N,*C,-/N \NH' NH ammonia and a small amount of a brown cccid.3 3'-AeoindaxoZe C14HloN6,C2H60y crystallises from alcohol in dark red gpstening needles with intense green lustre m. p. 229.5" (corr.) and gives a light blood-red coloration with concentrated sulphuric acid. It dissolves in aqueous alkali hydroxides forming a bluish-red solution dyes silk and wool in an acid bath a rose colonr and is readily reduced by zinc dust forming 3-aminoindazole. The kti-ate C,,H,,N,,BHNO forms slender red needles with green lustre. The diacetyl derivative N2(C7H4N,Ac) crystallises in slender orange needles m. p. 2 10' (corr,) gives with concentrated sulphuric acid a dark blue coloration becoming red on addition of water and is readily hydrolysed by dilute alkali hydroxides. The dibenxoyll derivative CB8HlSO2NB crys tallises in glistening needles m.p. 195-196' (corr.). Azoindazole reacts with aniline at the laboratory temperature form- ing 3-aminoindazole 3-benzeneazoindazole and a substance (axoindazole hydrate ?) C,,Hl20N which crystallises in glistening bronze needles m. p. 338.5". 3-Benzeneazoinduzole m. p. 190-5-1 92.5' (corr.) is identical with the dye obtained by Bizmberger (Zoc. cit.) by the action of diazo- benzene chloride on indazole. 3-Amino-5 7-dimethyl- aud 3-amino-5-me thyl-indazole are oxidised by atmospheric oxygen in aqueous alkaline solution i n the same manner as is 3-amiiioindazole Along with the corresponding dye 3 3'-ccxo- 5 5'-dirnethyZinduxoZe forms an cccid which crystallises in glistening colourless needles m. p.about 160". The red coloration formed on shaking these substances with air in alkaline solution constitutes an ex tremelv delicate reaction for 3 -aminoindttzoles. .I C H BichZoroindaxoZe C,H,Cl,<~->NH is formed together with indazole a substance which is soluble in cold dilute sodium hydroxide and a sparingly soluble indifferent substance (trichloroindazole 1 ) by the action of alkali hydroxides on an o-diazotoluene salt. It crystal- lises in matted white needles in. p. 242-242.5OY sublimes in woolly nezdles is only slightly volatile in a current of steam has feeble basic properties and is soluble in boiling dilute sodium hydroxide (compare Abstr.1899 i 720). G. Y. Diazo-compounds from p-Phenyle nediamine with Hetero- cyclic Side-chains. CARL BULOW and FRITZ BUSSE (Ber. 1906 39 3861-3868. Compare Abstr. 1906 i 717).-EthyZ p-acetykccmino- benxeneaxobenzoylacetate NH Ac* CGH,*N,*~H(COPli)*CO,E t obtained by condensing a diazo-salt of acetyl-p-phenylenediamine wihh a n166 ABSTRACTS OF CHEMICAL PAPERS. alcoholic solution of ethyl benzoylwtate crystallises from alcohol in yellow needles m. p. 95*6'. The ester reacts with an aqueous alcoholic ammonia solution yielding the amide NHAc*C,H,*N,*CH( COPh)*CO*N€€ in the form of pale yellow needles m. p. 252'. Phenvlhvdrazine reacts with an acetic acid solution of the ester . I d yielding 4-p-c~cetylaminobenxeneccxo-1 ; 3-di23henyl-5-pyrc~~ol~ne) N- I C P h ~ ~ ~ ~ ~ ~ ~ ~ ~ ~ NPh*C(OH) which crystallises from' dilute acetic acid in red needles readily soluble in most organic solvents and in dilute alkalis but insoluble in ether light petroleum or water.4-p-Aminobenzeneaxo-1 5-diphenyl- 5-pyruxolme C,,H170N obtained by hydrolysing the acetyl derivative with sodium hydroxide solution crystallises from alcohol in reddish- brown needles m. p. 208-209". The diazo-chloride derived from this amine reacts with an alcoholic solution of ethyl acetoacetate in the presence of sodium acetate yielding etlLyZ 1 3-cliphenyZ-5-pyraxoZone 4-ccxo benxene-P-axocccetocccetate N=z= h P h *C(OH) N C6H,*N CH Ac C0,E t \ I which crystallises from alcohol in pale red needles m. p. 195-196" (decomp. ). I ' 1 3- Diphenyl- 5 -pymxoZone-4-axobenzene - p- 4'-a~o-l'-pl~enyl-3'-rnethyE- 5'-pyraxolone ~C.N2*C,H,*N,*C~C(OH) .APh obtained CMe=N -- --CPh NPh*C(OH) by the action of phenilhydrazine on the preceding cokpound may be recrystallised from hot benzene or by solution in hot nitrobenzene and precipitation with acetic acid. It forms reddish-brown plates with a green metallic lustre m.p. about 270" (decomp.). The constitution of the last -mentioned compound has been estab- lished by its formation by the following stages l-phenyl-3-methyl-5- pyrazolone-4-azobenzenediazo-chloride -+ ethyl l-13~e.nyl-3-naetl~~Z-5- pyraxolone-4-azobenzefie-p-4'-rmobenxoylmetate C27H2404N6 m. p. 203" -+ l'-phenyl-3'-methyl-5'-pyrazolone -4 - azobenzene -p- 4'-azo - 1 3-di- phen yl-5-pyrazolone. J. J. S. Reduction of Nitroazo-compounds with Sodium Hypo- sulphite.EUahNE GRANDMOUGIN ( B e y . 1906 38 3929-3932. Compare Abstr 1906 i 716 967).-The reduction of nitroazo-com- pounds with sodium hyposulphite does not always proceed normally ; o-nitroazo-compounds in particular are only partially reduced whilst azoimino-oxides are also formed. Benzeneazosalicylic acid undergoes normal reduction with formation of aniline and 5-nminosalicylii acid. m-Nitrobenzeneazosalicylic acid is reduced to aminosalicylic acid and m-phenylenediamine whilst p-nitrobenzeneazosalicylic acid yields aminosalicylic acid and p-phenylenediarnine. o-Nitrobenzeneazophenol on reduction with sodium hyposulphite forms p-~~~rox~p~eny~c6zoim~~~obenxerze oxide C,H,<ho>N * c H,*OH N-ORGANIC CHEMISTRY 167 which crysfallises in cohurless needles rn.p. 232-233'; its acetyl derivative separates from dilute alcohol in needles m. p. 1 7 6 O . When p-hydroxyphenylazoiminobenzene oxide is reduced by stannous chloride -\T IY it forms p-hydroxyphenylbenzotriazole C H < 1 >N*06H,*OH which i i 4 N separates from alcohol in colourless needles m. p. 219'. A. MaK. Digestion of Egg and Serum Proteids by Papain D. JONESCU (Biocl~m. Zeit 1906 2 177-187).-Digestion of the proteids named with papain stops short at peptone; amino-acids are nob found. Coagulated egg-white and fibrin are not digested at all The influence of temperature is discussed ; reversibility of action was not discovered and the questions of pro-ferment and activation suggested. W. D. H. Albumin Extracted from Fished Eggs and a comparison of it with the Vitellin of Hens' Eggs.LOUIS HUOOUNENQ (Con~pt~ vend. 1906 143 693-694. Compare Abstr. 1906 i 324).-T1he albumin extracted from the eggs of Clupea Imrengus and called clupeovin by the author yields on hydrolysis arginine hiatidine lysine tyrosine leucine aminovaleric acid alanine serine phenylalanine and aspartic acid; it follows therefore that the vitellin obtained from the eggalbumin of birds or fishes is formed of the same compounds associated in comparable if not almost identical proportions (Abstr. 1906 i 85 776). Occurrence of isoLeucine in Casein. R. WEITZENBOCK (Moncctsh. 1906 27 831-837).-The first phosphotungstate pre- cipitate obtained from a large amount (3 kilos) of casein contains leucine isoleucine (Ehrlich Abstr. 1904 i 56) and small amounts of arginine histidine lysine and probably aminovaleric acid and pheny lalanine.If the phosphotungstate precipitate is distilled with aqueous potassium hydroxide and the distillate evaporated with hydrochloric acid and redistilled with aqueous bary ta leucine and isoleucine are present in the final distillate and can be separated by Ehrlich's met hod. G. Y. M. A. W The Homogeneous Nature of Hamatin and Attempts to Remove Iron from Blood-colouring Matter. RICHARD TON ZEYNEK (Zeit. physiol. Chem. 1906 49 472-481. Compare Abstr. 1900 i 71 l).-Hsmin obtained by the pepsin-hydrochloric acid method closely resembles hgmin obtained by other methods. It may be crys- tallised from acetic acid and the analytical data agree fairly well with the formula C3,H,,0,N,C1Fe. When the blood-colouring matter is left in contact with pepsin- hydrochloric acid for some months the yield of crystallised hzmin is small and considerable amounts of residues are left in the pyridine- chloroform solutions but the percentage of iron is not reduced. €€;emin prepared by the pepsin-hydrochloric acid method is more readily decomposed by dilute acid or by water at 180' than is ordinary168 ABSTRACTS OF CHEMICAL PAPERS. haemin. It is also more readily decomposed when a feeble electric current is passed through its alkaline solution. When a suspension of hsemin in sulphurous acid solution is exposed to light the aqueous liquid becomes purple-red in colour and shows the characteristic bands of hzmstoporphyrin. The iron has been removed from the hEmin and is contained in the solution in the ionic state. J. J. S. Nucleic Acids. XI. PHCEBUS A. LEVENE and JOHN A. MANDEL (Zeit. physiol. Chen2. 1906 49 262-265. Compare Abstr. 1906 i 468).-The nuclein substance obtained from the egg oft the shell-fish Gadas ceglejnus appears to be a mixture of ichthulic and nucleic acids It yields on hydrolysis the purine bases guanine and adenine the pyrimidine bases cytosine and uracil. It gives a positive orcinol reaction but the yield of lzvulic acid is very small W. D. H. Composition of Nucleic Acids of Thymus and Herring-roe. HERNANN STEUDEL (Zeit. plysiol. Chem. 1906 49 406-409. Com- pare Abstr. 1906 i 125).-The four nitrogenous components of these nucleic acids seem to be present in molecular proportion. They are guanine adenine cytosine and thymine. W. D. H. Cleavage of Gelatin. PEKEBUS A. LEVENE and WALLACE A. BEATTY (Zeit. physiot. Chent. 1906,49 347-251 252-261. Cornpare Abstr. 1904 i 357 ; 1906 i 469).-The following are the percentage amounts of cleavage products obtained from gelatin glycine 19.25 ; alanine 3.00 ; leucine 6.75 ; a-proline 6.25 ; oxyproline 6.4 ; phenylalanine traces ; aspartic acid absent and glutamic acid 1-75 W. D. H. Cerebrone. 111. F. K~TAGAWA and HANS THIERFELDER (Zeit. physiol. Chern. 1906 49 286-292. Compare Abstr. 1906 ii 183). -A new method for the separation of cerebrone is described. I n a 5O/ solution in 75"/ chloroform [a] + 7.6. Sphingosine mas the name Fiven by Thudiclium t o a basic cleavage product of his phrenosin. was prepared but its relationship to sphingosine is a t present uncertain. W. I). H. I n the present research a base with the formula C,,H,,W Diffusion of Enzymes through Cellulose Membranes. ALB. J. J. VANDEVELDE (Biochem. Zed. 1906 1 408-41 2).- Leune's cellulose membrane and pig's intestinal membrane were em- ployed. Invertase does not diffuse through the former but easily diffuses throngh the latter. Naltase rennet and blood-catalase behave like invertase. Zymase diffuses through neither but the isolated enzyme was not employed only yeast cells. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9079200105

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

120 ABSTRACTS OF CHEMICAL PAPERS. Chemistry of Vegetable Physiology and Agriculture. Coagulation of Milk by Bacillus coli communis. C. JOCELYN O’HEHIR (J. Puth. Bact. 1907 11 405-407).-The coagulation of milk by this bacillus is due to the production of acid probably lactic acid. Attempts to isolate any coagulative enzyme failed. W. D. H. Action of the Bulgarian Ferment on Milk. GABRIEL BERTRAND and GUSTAVE WEISWEILLER (Ann. Inst. Pnsteur 1906 20 977-990). -The lactic organism isolated from ‘‘ yoghourt ” or curdled Bulgarian milk (compare Cohendy Compt. rend. SOC. Bid. 1906 60) acts with varying intensity on the three chief constituents of milk. It dissolves about one-tenth of the casein a small part of which is used to build up its cells and it also hydrolysesthe fat to a very slight extent.By the aid of a lactase which is doubtless an endo-lsctase it hydrolyses almost the whole of the lactose afterwards transforming the resultant dextrose and galactose into a mixture of I- and d-lactic acid in which the latter predominates. Resides the lactic acid which may amount to 25 grams per litre small quantities of succinic acetic and probably formic acids are forme 1. The volatile products contain neither alcohol acetone nor acetylmethylcarbinol. T. H. P. Propionic Acid Fermentation in Emmentaler Cheese. ED. YON FREUDENREICH and ORLA JENSEN (Centr. Bukt. Par. 1906 ii 17 529-546).-Most of the propionic acid in Emmentaler cheese is pro- duced from lactates by specific propionic acid bacteria ; acetic acid and carbon dioxide are also produced the latter being the chief cause of the formation of cavities in the cheese. I n addition to the pure propionic acid fermentation there is generally also a pure acetic acid fermentation of calcium l;rctate in’duced both by propionic acid and lactic acid bacteria.N. H. J. M. Coagulation Produced by Borates. Agglutination of Yeast. 11. HENRLVAN LAER (Bull. Xoc. china. Belg. 1906 20 277-28S).- The quantity of borax necessary to induce coagulation in certain yeasts is difficult to determine owing to the rapidity with which de- coagulation occurs. The quantity of borax required is greater for dead than for living yeast and the granules formed are larger and denser the greater the quantity of borax employed. Dead yeast preserved for some time under aseptic conditions is less readily coagulated than freshly killed yeast ; this is due probably t o the formation of anti-coagnlating acids in the preserved yeast without bacterial intervention. Coagulation by borax is greatly favoured by the presence of free sodium hydroxide and to a just perceptibly less extent by ammonia solution T. A H.VEGETABLE PHYSIOLOGY AND AGRLCULTURE.121 Source of the Succinic Acid formed during Alcoholic Fermentation. RUDOLF KUNZ (Zeit. Ncchr. Genussm. 1996 12 641 -645).-The experiments described prove that the succinic acid formed during the fermentation of sugar by yeast. is derived from the substance of the yeast and is probably a decomposition product of the latter. It is not formed from the sugar. w. P. s. Action of Alkaline Phosphates on Cells and Ferments. THOMAS BOKORNY (Chem.Zeit. 1906 30 1249-1250. Compare Abstr. 1 895 ii 174).-1nfusoi-ia rotifers and similar micro-organisms are killed immediately by a 5% solution of di+odium hydrogen phos- phate or more slowly by a. 2.5% solution whilst a 1% solution does not affect the mobilit'y of the organisms in twenty-four hours. The action of the dipotassium salt is more marked. Pressed jeast commences to putrefy in ten days in R 10% solution of disodium bydrogen phosphate in five days in a 15% solution or in eight days in x solution containing 10% each of the disodium and dipotassium hydrogen phosplmtes. Microscopic examination of these solutions shows that numerous living bacteria are present but that the yeast cells are destroyed. Yutrefaction does not comuience in eight days in a 15% solution of the dipotassium salt.Fermentation and culture experiments with these solutions after three days and before putrefaction show that the yeast cells and the zymase are destroyed but that the invertaee is more resistant!. As zymase invertase and maltase are killed by a 1% but not by a 0 5% solution of sodium hydroxide the dialkali hydrogen phosphates must be hydrolysed in 15% solution to the extent of a t least 1%. G. Y. Genesis of Proteid by a Pathogenic Microbe. J. GAL~MARD and L. LACOMNE (C'onzpt. rend. 1906 143 1182-1184. Compare Abstr. 1906 ii 695).-The microbe of " green diarrhea ' was grown in a medium the only nitrogenous constituent of which was glycine. Growth occurred as in ordinary broth and a t the end of 119 days Lome glycine was recovered but the greater part had been utilised i n the formation of the proteid of the mici*obe's protoplasm ; i he properties of the proteid resemble those of a mucoid.A fatty material was also formed which is probably lecithin. W. D. H. Chemical Studies of the Cell and it8 Medium. I. Liquid Culture Media. AMOS W. PETERS (Amer. J. Phpiol. 1907 17 443-478).-The physical and chemical properties of culture media are considered. Special attention is directed to phenolphthalein acidity methyl-orange alkalinitmy total salts and estimation of individual salts electrical conductivity oxygen consumption and organic nitrogen. The biological aspects of the question are postponed. W. D. H. Distribution of Hydrogen Cyanide in the Vegetable Kingdom.MAURITS GRESHOFF (A?&. Pharm. 1906 244 397-400 665-672).-A list of plants which yield hydrogen cyanide is given with indications of whether they are known to yield benzaldehyde also or a substance analogous with this or with acetone. C. P. B.122 ABSTRACTS OF CHEMICAL PAPERS. Composition of Juices Extracted from Roots. G USTAVE ANDRI~ (Cmpf. rend. 1906 143 972-974).-The nmounts of extract nitrogen and ash were determined in the root-juices of different plants obtained under pressures of 3 12.5 and 25 kilos. per square centi- metre. It was found that the density of the juices diminished as the pressure under which they were obtained increaPed. The relation however between the amounts of ash and extract and of nitrogen and extract showed very slight variations.Distribution of Vicianin and its Diastase in Leguminous Seeds. GABRIEL BERTRAND and MLLE. L. RIVK~ND (Compt. rend. 1906 143 970-978 ; compare this vol. i 68).-Nesrly all the seeds examined (about sixty varieties) were found to contain the diastase which acts on vicianin. The following do not contain appreciable amounts Cussia $sluh Cercctonicc silipun Galegcc oflcinalis Lathyrus syluestris GEeditschia tricccados Lupinus albus Xophora japoniccs Vicia navbonensis. Vicianin was only found in one species Vicia (V. ccngustjfolicc and T. macrocarpa). The only seeds which were found to contain neither the glucoside nor the diastase mere those of Vicia nurboizensis. N. H. J. M. N. H. J. M. Function of Iodine in Marine Algae. FRANCESCO SCURTI (Gaxsetta 1906 36 ii 619-625).-The author's experiments on Sa!rgassuin Zinifolium and Cystoseircc discors show that the proportion of iodine contained in them varies with the state of development of the algze reaching its maximum in spring when maturation commences and its minimum in autumn ; the percentage of ash is greatest when maturation is at an end.The amount of iodine present decreases rapidly if the algae are left in the sea. Brown algae contain a greater proportion of iodine than green algz From these results it is concluded that iodine holds in algae the place held by chlorine in the phnnerogams and that it acts therefore as an excitant of the reproductive phase. T. H. P. Principles of Atractylis Gummifera (Sicilian Masticogna). FRANCESCO ANGELICO (Gcczzettcc 1906 36 ii 636-644.Compare Le Franc Compt. r e n d 1868,67 936 and 1873 76 438).-From the latex of Atmctptis guminVera the author has separated (1) a pale yellow highly elastic caoutchouc yielding when treated with nitrous anhydride a nitrosite CloH1507N2 which is deposited from a mixture of ethyl acetate and ether as a yellow powder decomposing at about 165'; (2) a small quantity of a subetaizce separating from methyl alcohol in white crystals which soften a t about 165" and have m. p. about 173'. From the root which is poisonous he has isolated the potassium atractilate C,,H,,O,,S,K of Le Franc (Zoc. cit.) which crystallises from aqueous alcohol in shining white needles loses valeric acid a t 160' and chars a t 190". This compound which is the poisonous principlo of the root {ives a characteristic reaction with sulphuric acid.When it is heated with the acid an odour of valeric acid is at once observable and the colour of the liquid passes through wine-red toVEGETABLE PHYSIOLOGY AND AGRICULTURE. 123 bromnislc-red; if left at rest for a few minutes the liquid gradually assumes a violet colour and after some hours this colour disappears and a violet crystalline powder is deposited. The potassium compound is a complex glucoside in which sulphuric acid exists in the form of a com- pound ester. When hydrolysed by heating with dilute sulphuric or hydrochloric acid potassium atractilate yields (1) sulphuric acid ; (2) valeric acid ; (3) a pentose and (4) a colloidal acid substance which is readily soluble in methyl or ethyl alcohol gives a pale reddish-violet coloration with concentrated sulphuric acid and decomposes when it is melted.If the hydrolysis is effected by means of alkali acidification of the liquid causes the deposition of a substance which separates from methyl alcohol in small white crystals melting a t 168". The fatal doses of potassium atractilate are given for several animals. T. H. P. Presence of Prulaurasin in Cotoneaster Microphylla. HENRI HERISSEY (J. Yhama. Chirn. 1906 [vi] 24 537-539. Compare Abstr. 1906 i 31).-Yrulsurasin was obtained from branches with leaves of Cotoneaster naicrophylla. N. H J. M. Enzymes in the Spores of Fuligo Varians. HEINRICH SCHROEDER (Bielr. chena. P/~ysioZ. Pcith. 1907 9 153-1 67).-The enzymes presetlt in the spores of this variety of tan fungus are a milk curdling ferment a proteolytic ferment a catalnse and a tyrosinase. The material gives the guaiacum reaction.W. D. H. Glucosides of the Jaeminacem Syringin and Jasmiflorin. J. VINTILESCO (J. I'har77a. Chim. 1906 [vi] 24 529-536).- Jccsrninunz nuclzjorum contains several glucosides including syringin and probably a glucoside having a rotatory power of about uD - 145O to which the name jccsnLz@iiz is given. Syringin was also obtained in a pure state from J. fi*ucticccns. N. H. J. M. Chemical Composition of Linaria Vulgaris. TIMOTH~E KLOBB and A. FANDRE (BuEI. SOC. chim. 1906 [iii] 35 1210-1220. Compare Walz Jch. pliarm. 1853 43 :*nd Schlagdenhauffen and Reeb J. PITLcLT~Iz. Alsace-Lorraine 1901 and 1902).-Tbe flowers on extraction with light yetroleinn yield (I) a saturated hydrocadon which may have the formula C,,H,,,C26H64 or C,,H,,.It crystallises from ether in fine nacreous lamella+ m. p. 5i0 and when heated a t 100" exhales the odour of melted paraan. (2) A substance which crystallises from alcohol in nacreous hexagonal plates m. p. 1 3 8 O and gives the characteristic reactions of a phytosterol. By extracting the flowers with alcohol mannitol was obtained and in addition Zinarin Cl4H1,O7 (linaric acid of Schlagdenhauffen and Reeb) which slowly crystallises from glacial acetic acid in colourless microscopic needles xn. p. 2 6 5 O is readily attacked by oxidising agents and when boiled with Fehling's solution furnishes a distillate containing Zinarodin C,H o02 which may be purified by redistillation and then has m.p. 36.5" and sublimes a t a higher temperature.124 ABSTRACTS OF CHEMICAL PAPERS. When first prepared it has an aromatic odour simultaneously recalling those of anise and of Tonquin beans but this disappears on purifica- tion though the pure substance develops the odour on heating at 100' When dissolved in warm nitric acid a white precipitate separates after a time which crystallisea from ether in slender needles Linarodin does not recolour Schiff's reagent and separates unchanged on cooling its solution in warm sodium bisulphite solution. The whole plant deprived of roots on extrachion with light petroleum jields a hydrocarbum which was not obtained free from oxygenated substances This crystsllises from ether in hexagonal or rhombic lamell= m.p. 57". Digestion and Secretory Activity in the Endosperm of Ricinus. D. BRUSCRI ( A t t i R. ACCLLCI. Lincei 1906 [v] 15 ii 563 -567).-The tndosperms of Ricinus cummunis removed from non- germinated seeds are incapable of initiating autodigestion. But even if germination has oily just cotnrnenced prior to the separation of the endosperms the latter undergo autodigestion the fat and conteuts of the aleiirone cells greatly dirriinishing the starch disappearing firstly from within the nucleus and then from the whole cell and the sugar accumulating in the neighbonrhood of the cellulosic walls. Sin( e i n the germination of Ricinus starch is not found in the endosperm the first product of digestion of the isolated endosperms must be assumed to be not starch but sugar which not being absorbed by the embryo is converted into starch so that the sugar in the cell may be prevented from increasing beyond the allowable limit.Subsequently when the endoaperm has consumed the reserve of albumin and oil the starch disappears again. The products of autodigestion are allowed to exude into the surrounding liquid in which appear dextrose sucrose phos- phoric acid calcium and magnesiutn. The amounts of these substances emitted into the liquid ale influenced to n marked extent by the pre- sence in solution of various compounds. Presence of Allantoin in and Absence of Solanine from Tobacco Seeds. FRANCESCO SCURTI and F. PERCIABOSCO (Gazxettcc 1906 36 ii 626-632. Compare Starke Abstr. 1902 ii 166).-The authors show that tobacco seeds do not contain solanine but that theycon- tain (1) allantoin this being the first occasion on which this substanve has been observed in seeds; (2) a higher cdcohol C,,F€,,O of the cholesterol group which sel arates from alcohol with +H,U in colourless nacreous crystals m.p. 134-135O ; when shaken with sulphuric acid its chloroform solution turns first blood-red and then cherry-red ; i t absorbs more than 2 atoms of iodine per mol. and i t forms an ncetyl derivative which separates from alcohol as a crystalline powder m. p. 130". T. H. P. Influence of the Valency of Metals on Toxicity. HENRI MICHEELS (Compt. rend. 1906 143 1181-1 182).-Wheat germinates better in solutions of sodium cbloride if calcium chloride in small amounts or an equivalent amount of salts of other bivalent metal are added to it.T. A. H. T. H. P. The results confirm those of Loeb on animal organisms. W. D. H.VEGETABLE PHYSIOLOGY AND AGRICULTURE. 125 Redpction of Nitrates in Musts and Winem F. ROSSI and FRANCESCO SCURTI (Gaxxetta 1906 36 ii 632-635).-Egger (Abstr. 1885 848) has shown that unadulterated wines when tested with a sulphuric acid solution of diphenylamine give no indication of the presence of nitrates (compare Borgmann A bstr. 1888 753). Formento (Stax. sper. agrar. ital. 1889 17,158) Leone (Gaxxeita 1895 25 433) and others have asserted that this depends not on the absence of nitrates from the muht but on a process of denitrification occurring either during the fermentation or as a consequence of the action of micro-organisms always present in wine.The authors find however that no such destruction of added nitrates occurs during either fermenta- tion of grape must or storing of wine provided that proper conditions of fermentation or storage are maintained. Only when the must or wine undergoes secondary changes does any destruction of nitrates take place. As all well water contains small quantities of nitrates its addition to wine as an adulterant may be detected by means of a sulphuric acid solution of diphenylamine. Presence of Boric Acid i n Genuine Sieilian Wines. E. AZZARELLO (Gaxxetta 1906 36 ii 5'75 -587).-The author has examined spectroscopically the ashes of 84 samples of Sicilian wines all of which were found to contain boric acid. I n six cases quanti- tative estimations of the amount of the acid gave from 0.0191 to 0-0410 gram per litre. Lecithans of Wine.GIUSEPPE PLANCHER and A. MANARESI (Gazxetta 1906 36 ii 481-492).-From the results of their own investigations and those of other workers on different wines the authors conclude that all wines contain lecithans (compare Koch Abstr. 1903 i 301) the amount of which largely determines the nutrient value of wine. Contrary to the statement of Weirich and Ortlieb (Abstr. 1904 ii 304) i t is found that no relation exists either between the proportions of total phosphorus and lecithans present in wines or between the contents of alcohol and lecithans. With the exception of the stones the parts of the grape richest in lecithans are those adhering to the skin. Pasteurisation of the wine at 65-'70° has no destructive action on the lecithans; at higher temperatures the lecithans are decomposed to some extent without undergoing complete destruction which is indeed not effected by concentrating the must over an open fire to about three-quarters of its volume (compare Weirich and Ortlieb Zoc. cit.).AUGUSTE TRILLAT (Compt. rend. 1906 143 1244-1247).-The bitterness sometimes acquired by the red wines of Bourgogne has been attributed to secretions of microbes and to decomposition of the colouring matter of the wine. It is probably due to the production of resins from aldehyde and ammonia. Diseased wines were found to contain both compounds in considerable amounts ; and it was found that certain wines soon acquired the bitter taste after addition of very small quantities of acetaldehyde and ammonia.T. H. P. T. H. P. T. H. P. Bitterness of W-ines. N. H. J. M. VOL. XCJI. ii. 9126 ABSTRACTS OF CEXMICAL PAPERS. Influence of Light on the Nitrogen of ‘wheat. J. DUMONT (Compt. rend. 1906 143 1179-1181).-The more refrangible r a p are those which are most efficacious in producing migration of nitro- genous material especially gluten in wheat grains during maturation. They provoke or favour the formation of proteid and so are of physio- logical importance. W. D. H. BALLAND (Compt. rend. 1906 143 969-970).-A rZsum5 of the results of 600 determinations of phosphoric acid in cereals vegetables fruit meat eggs &c. recently published in Les Aliments. THEODOR PFEIFFER PAUL EHREN- BERG and E. REICHENBACH (Chem. Centr. 1906 ii 1624-1625 ; from Mitt.Lccndw. Inst. K. Univ. Breslau 3 899-927).-For soil investi- gations the object of which is to obtain a nitrogen-balance large numbers of nitrogen estimations are essential. The soil samples can be dried without loss of nitrogen after addition of dilute acid. Warmbold’s statement that abundant fixation of free nitrogen takes place in sterilised soils was not confirmed. No results have as yet been published which indicate any notable activity of nitrogen-fixing bacteria in soils under practical conditions ; existing evidence rather points the other way. Distribution of Phosphorus in Foods. N. H. J. M. Nitrogen Fixation in Soils. N. H. J. M. Soils of the Northern Portion of t h e Great Plains Region The Second Steppe. FREDERICK J. ALWAY (Amer. Chem.J. 1906 36 580-594).-The large yields of grain obtained in the Canadian North- west have been erroneously attributed to the constant supply of water furnished by the melting ice stored in the soil (Crookes Pres. Address Brit. Assoc. 1898). It is shown that the high yields are due to moisture stored during the previous summer and not to the frost of the preceding winter as the soil of the southern portion does not at any depth remain permanently frozen. The surface soils are rich in nitrogen and the subsoils very rich in carbonates; both surface and subsoils contain plenty of potassium and phosphoric acid. The yields of cereals vary with the rainfall of the crop season but show a still closer relation to the total available moisture. With favourable conditions of moisture the surface soil is usually rich enough to produce very large yields. The relative fertility of difforent areas seems to depend on the nature of the subsoil.N. H. J. M. Removal of Black Alkali ” by Leaching. FRANK K. CAMERON and H. E. PATTEN (J. Amer. Chem. Xoc. 1906 28 1638-1649).- Neutral salts such as chlorides in the presence of carbonates can be removed comparatively readily and completely from the soil. Con- tinued leaching of “ black alkali ” soils results in increased rapidity of percolation and a reduction of the amount of normal carbonates in the soil water owing to a great extent to their conversion into hydrogen carbonates. The latter are at first rapidly removed; sub- sequently very small amounts are found in the soil water and theANALYTICAL CHEMISTRY.127 decrease is then so slow that the amount remains practically constant for an indefinite period Both the time and the amount of water necessary for reclaiming ‘ I black alkali ” soils are probably much greater than in the case of ‘‘ white alkali.” N. H. J. M. Amount and Composition of Drainage Waters Rain Dew and Canal Water Collected During the Years 19034 1904-5 1905-6. W. H. MORELAND (Rep. Cawnpore Agric. Stat. for the year ending June 30,1906 33-29).-Four drain gauges similar to those at Itothamsted (Abstr. 1882,890) were constructed a t Cawnpore in 1903. The area is in each case 1/1000 acre (6 ft. x 7.26 ft.) and the depth 36 inches and 72 inches the intention being t o have two permanently uncropped and two cropped when sufficient comparative records have been obtained without vegetation. The soil has for some years been regularly manured and cropped Nitrogen as nitrates and ammonia is determined in mixed samples of the drainage twice a month and the present paper contains the full results from June 1904 to Oct. 1905 ; also analyses of rain-water and dew 1904-5 (compare Abstr. 1906 ii 487) and canal-water. The results for the twelve months June 1904 to May 1905 obtained with one of the 36-inch and one of the 72-inch gauges both uncropped are as follows :- Depth Rain- Drainage. N per million N per acre of soil. fall. inches. as NH as N,OS as NH as N,O inches. inches. lb. Ib. 36 49.20 32.57 0.06 11.10 0.31 56.7 72 97 21.78 0.07 21-61 0.32 106.5 The small amounts of ammonia are attributed to dew deposited on the funnels below the soil N. H. J. M.

ISSN:0368-1769    

DOI:10.1039/CA9079205120

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

ANALYTICAL CHEMISTRY. 127 Analytical Chemistry. The Autolysator. New Apparatus for Continuous Auto- matic Gas Analysis. HUGO STRACHE RUD JAHODA and U. QENZKEN (Chem. Zeit.; 1906 30 1128-1130).-1n the diagram showing the principle of the apparatus Kl is a capillary tube which communicates with the differential pressure gauge MI the lower end of which is connected through the stopcock H t o a filter-pump. By regulating the stopcock H a steady flow of gas through the tube X I can be maintained as shown by the reading of the pressure gauge M,. The gas enters the apparatus by a tube E' which is connected t o a similar capillary K' and gauge Mz. So long as none of the gas is absorbed by the reagents contained in the vessels A or A the 9-2128 ABSTRACTS OB CHEMICAL PAPERS. pressures indicated by the two gauges will be identical; when how- ever absorption takes place a proportionately larger volume of gas will be drawn through K2 and accordingly the gauge M2 will register a larger difference of pressure. If the constancy of the flow of gas through Kl is regulated automatically by the stopcock H the per- centage of gas being absorbed may be directly read off the gauge M2 L -+ .+== xt ‘I provided it has been graduated accordingly beforehand. Variations in the pressure indicated by the gauge Mz are automatically recorded in the form of a curve drawn on a revolving cylinder by a pen floating on water which moves up and down in obedience to the alteration of level in the gauge. The recording apparatus is inserted between the points P and P2. Burette Arraeement.P. PANNERTZ (Zeit. anal. Chem. 1906,45 751-754).-The apparatus is a modification of the one described by Plemming (Chem. Zeit. 1904 28 818). The chief improvement consists in the fact that a Woulf bottle containing the standard liquid and holding the burette and the air-tube is substituted for the flask with a doubly-perforated cork. A three-way stopcock is employed which renders possible a connexion or disconnexion between the reservoir outer air and the elastic ball. For further particulars the P. H. illustrations in the original should be consulted. L. DE K. Apparatus f o r Dissolving and Evaporating to Dryness. CONSTANTIN ZENGELIS (Zeit. and. Chem. 1906 45 758-760).-The apparatus which admits of rapid evaporation without risk of loss by spirting consists of a 300-400 C.C.Phillips’s beaker with spout and furnished with two holes opposite each other about 3 cm. from the top. The rim is bent inwardly and during the heating a watch-glass is placed over it concave side downwards. This watch-glass has a hole throughANALYTICAL CHEMISTRY. 129 which passes a glass rod which is expanded at one place so that the rod will be held up by the watch-glass with its drawn-out point about 1 cm. from the bottom of the beaker. The beaker should be heated on a sand-bath or an asbestos plate. L. DE K. Determination of the Caloriflc Power of Gases and Volatile Liquids. E. GOUTAL (Ann. Chim. anal. 1906 12 1-3).-The com- bustion of gaseous hydrocarbons becomes imperfect in presence of too large an excess of oxygen; in practice therefore several trials should be made with varying amounts of oxygen.When determining the calorimetric power of liquid combustibles these are weighed in sealed glass bulbs through the drawn-out points of which passes the usual iron conducting-mire. The bulb is placed in the porcelain capsule suspended in the bulb and the usual course is that the points are broken before closing the apparatus in order to admit the oxygen. The author however recommends not breaking the points but using a source of electricity more powerful than that furnished by the bichromate battery which is generally sold with the apparatus the glass bulb then being fractured within the closed appar- atus. On account of the somewhat violent action a platinised bomb should be employed or otherwise a non-enamelled one made of ferro- nickel.The combustion will now be always complete. L. DE K. Fluorine in Mineral Waters. P. CARLES (Compt. rend. 1907 144,37-39).-Fluorine has been detected in a large number of mineral waters of Bourbon by evaporating several litres adding calcium acetate collecting and washing the calcium fluoride and decomposing by sulphuric acid in a platinum capsule covered with a glass plate. Minute directions are given in the original paper. The amounts of fluorine were estimated by comparison of the etched glass with a series of glasses etched by varying amounts of sodium fluoride under the same conditions. E. H. Estimation of Uncombined Sulphur. E. BERGER (Compt. rend. 1906 143 1160-1 161).-Uncombined sulphur is readily and rapidly oxidised to sulphuric acid by the action in the cold of fuming nitric acid containing a little potassium bromide.For the estimation of un- combined sulphur the author recommends adding 10 C.C. of fuming nitric acid and 0.5 to 1 gram of pure potassium bromide to a weighed quantity of the substance containing 0.1-0*2 gram of sulphur ; after some minutes evaporating to dryness on a water-bath and precipitating the sulphuric acid with barium chloride all traces of nitric acid having previously been removed by the usual process. M. A. W. Micro-chemical Detection of PhoBphorue. F. H. SCOTT ( J . physiol. 1906 35 119-124).-Acids readily remove most of the phosphorus from nuclein compounds in some soluble form but not as inorganic phosphates. The whole principle of the methods of Lilien- feld Monti and Maclzllum is therefore wrong and all deductions as t o the distribution of phosphorus compounds (other than inorganic130 ABSTRACTS OF CHEMICAL PAPERS.orthophosphates) by the use of these methods are regarded as value- less. W. D. H. Separation of Arsenic from Copper as Ammonium Mag- nesium Arsenate. FRANK A. GOOCH and M. A. PHELPS (Amer. J. Xci. 1906 [iv) 22 488-492).-A series of experiments showing that even very small quantities of arsenic if present in the higher state of oxidation may be estimated accuratelyin the presence of much copper as ammonium magnesium arsenate which may then be collected in a Gooch crucible and converted into pyroarsenate. I n order to obtain correct results the hydrochloric solution should be poured with constant stirring into an excess of magnesium mixture which may if necessary be placed in a freezing mixture.The preci- pitate always retains copper from which it may be freed by a repreci- pitation; if more than 0.005 gram of arsenic is present it is necessary to reprecipitate two or even three times. I;. DE K. Different Behaviour of Organic and Inorganic Compounds of Arsenic towards Reagents and Estimation of Arsenic in the Urine. C. E. CARLSON ( Z e d . physiol. Chem. 1906 49 410-432).- I n cases of arsenical poisoning the urine should be examined the best results being obtained by electrolpis. Arsenic occurs in the urine as arsenious or arsenic aeid. I n animals it is obtained after breathing hydrogen arsenide. Organic arsenic compounds used as medicaments appear to pass through the organism without producing the toxic effects of inorganic compounds ; this. at any rate is true for cacodylic acid and its salts.The greater part appears unaltered in the urine ; another part is reduced in the stomach liver and intestine to a volatile cacodyl oxide which leaves the body mainly by the expired air. W. D. H. Copper Spirals for Use in Combustions of Nitrogenous Substances. K.ARL HEYDENREICH (Zeit. anal. Chem. 1906 45 741-745).-Copper spirals reduced in a current of hydrogen may be freed from traces of this gas by heating in a current of carbon dioxide for about half an hour and then placing them in a vacuum over calcium oxide and sulphuric acid. Reduction with methyl alcohol vapour instead or hydrogen cannot be recommended as a deposit of carbon is likely t o form on the surface; in one experiment not less than 0.0972 gram of carbon dioxide was formed on heating ten copper spirals so prepared in a current of oxygen.Attention is called to the hygroscopic properties of the spirals. L. DE K. Phosphomolybdic Acid as a Reagent for Potassium. A. RCHLICHT (Chem. Zeit. 1906 30 1299-1300).-When ammonium phosphomolybdate is fused with sodium carbonate and nitrate and the resulting mass dissolved in water and acidified with nitric acid a solution is obtained which gives a distinct yellow precipitate with even very dilute solutions of potassium salts. L. PE K,ANALYTICAL CHEMISTRY. 131 Assay of Barium Peroxide. A. LOB (Chem. Zeit. 1906 30 1375).-0ne gram of the sample is dissolved in 50 C.C.of N/2 hydro- chloric acid preferably with addition of 20 C.C. of 10% manganous sulphate and then titrated with "N/4 permanganate (1 C.C. = 0*0221 gram peroxide). This process agrees very well with the iodometric method which is carried out as follows 0.5 gram of the sample is dissolved in a stoppered flask in 50 C.C. of water and 5 C.C. of hydro- chloric acid (D 1.124) 20 C.C. of 10% potassium iodide are added and the liberated iodine titrated with standard thiosulphate. The peroxide cannot be titrated with permanganate in sulphuric acid solution as the barium sulphate formed occludes large quantities of the peroxide which escape the reaction. L. DE K. Volumetric Estimation of Zinc. JOSEPH A. MULLER (BUZZ. SOC. chim. 1907 [iv] 1 13-16).-This process is based on that of Pouget (Abstr.1899 ii 695). The zinc solution is neutralised with ammonia sodium acetate is added and the mixture slightly acidified with acetic acid is saturated with hydrogen sulphide. The excess of the latter is eliminated by heating the mixture to 50' and passing a rapid current of carbon dioxide. Hydrochloric acid is added to dissolve the zinc sulphide and then a known volume of standard iodine solution. The mixture is shaken vigorously for several minutes and the excess of iodine titrated with sodium thiosulphate solution. Details are given of the preliminary treatment necessary in applying this method of estimation to zinc in ores. T. A. H. Rapid Estimation of Mercuric Chloride in Very Dilute Solutions. Josh R.CARR~CIDO (Anal. Fis. Qwim. 1906,4,314-316). -When ammonia is added drop by drop t o a mercuric chloride solu- tion containing one part of the salt in 10,000 of water a white ring is formed which increases in thickness as the ammonia penetrates the dilute solution. This alteration in the size of the ring is due to the solubility of mercuriammonium chloride in excess of ammonia. Similar appearances are observed with solutions of the following con- centrations 1 in 20,000 and 1 in 30,000; but the limit is reached when the strength is reduced to 1 in 40,000 as only a very faint ring is obtained. By the use of standard solutions of mercudc chloride this process furnishes a means for estimating colorimetrically the amount of mercuric chloride in dilute solutions. Sodium chloride does not interfere but hydrochloric acid or ammonium chloride must be absent because in the presence of either of these reagents the mercuric ammonium chloride and the ammonium chloride combine to form the double salt NH,HgCl,NH,Cl which is deposited as a sandy crystalline precipitate without giving rise either to a ring or a turbidity.G. T. M. Iodometric Estimation of Basic Alumina and of Free Acid in Aluminium Sulphate and Alums. SETH E. MOODY (Amer. J. Sci. 1906 [ iv] 22 483-487).-Fifteen grams of the material are dissolved in water the insoluble matter is collected and the filtrate diluted to one litre. Twenty-five C.C. are then boiled in a suitable132 ABSTRACTS OF CHEMICAL PAPERS. apparatus with potassium iodide-iodate mixt ure and the resulting free iodine is collected into a receiver containing potasaium iodide.After slightly acidifying with dilute sulphuric acid the solution is titrated as usual with thiosulphate. The residual liquid in the distilling flask is filtered and the precipitate which contains besides alumina ferric oxide and zinc oxide is collected and examined further by the usual gravi- metric process. In other aliquot portions of the solution are estimated the ferrous and ferric oxides by titration and also any zinc by electrolysis. From the amount of iodine liberated and the alumina found the quantity of free snlphuric acid and free alumina respectively may be readily calculated due allowance being made oE course for the presence of ferrous and ferric iron also for ammonia and zinc.In calculating it should be remembered that 1 mol. of alumina = 61 1 mol. of ferric oxide=61 1 mol. of ferrous oxide=21 5 mols. of zinc oxide=81 1 mol. of ammonia = 11 and 1 mol. of sulphuric acid = 21. L. DE I(. Titration of Ferrous Salts with Alkali Hypoiodite. ERWIN RUPP and M. HORN (Arch. Pharm. 1906 244,571-575).-By the use of potassium hydroxide instead of sodium potassium tartrate (Abstr. 1903 ii 244) the experiments can be shortened. A measured quantity of the ferrous solution is mixed with a liberal excess of N/10 iodine solution and approximately iV o r 5% aqueous potassium sodium hydroxide is added with shaking until the mixture has a distinctlyalkaline reaction (the volume required will be about one-third that of the iodine solution). After a few minutes half as many grams of oxalic acid (or less well as many C.C.of glacialacetic acid) are added as there were C.C. of N alkali used. After five to ten minutes more the mixture is diluted to about 100 C.C. and titrated with N/10 thio- sulphate solution with starch solution as indicator until the blue colour has disappeared and does not return immediately. The method is applicable in the presence of ferric and even of man- ganous salts but not in the presence of ammonium salts. EUGENIO PIRERUA ALVAREZ (Ann. Chim. anal. 1906 11 445-446).-1f a drop of a 1% solution of cobalt chloride or sulphate is added to a large excess of boiling very strong aqueous sodium or potassium hydroxide a blue solution is obtained. This is no doubt caused by the formation of a compound of the alkali with cobaltous oxide (CoO,K(,) for on diluting with water the hydroxide is regenerated and the blue colour vanishes.In presence of much nickel a precipitate is formed having an azure colour but this must not be confounded with the compound obtained on adding aqueous alkali to a cobalt solution in the cold for this precipitate which turns a rose colour on heating gives a blue solution if heated C. F. B. Useful Reaction for Cobalt. with a large excess of alkali. L. DE K. Detection and Estimation of Sodium Chloride in [Com- mercial] Tin Chlorides. PAUL HEERMANN (Chem. Zeit. 1907 31 27-28).-To a portion of the solution D 1.5-1.7 is added fourANALYTICAL CHEMISTRY. 133 times the bulk of alcoholic hydrochloric acid prepared by saturating 99.5% alcohol with hydrogen chloride.As little as 0.1% of sodium chloride m y thus be detected and when the amount exceeds 1% the liquid gives a copious crystalline precipitate. If aqueous hydro- chloricacid is used no precipitate is formed unless the sodium chloride exceeds 1%; if 96% alcohol is employed no deposit is obtained until the sodium chloride present is about 644%. The precipitate formed by the alcoholic acid may be collected and washed free from chlorides with absolute alcohol then dissolved in water and titrated as usual. L. DE K. Direct Estimation of Antimony. HERBERT W. ROWELL (J. Soc. Chem. Imd. 1906 25 1181-1183).-The method depends on the oxidation of antimonious to antimonic chloride by potassium bromate in the presence of hydrochloric acid and is a modification of a process described previously by Nissenson and Siedler (Abstr.1903 ii 697). One gram of the finely-divided alloy is dissolved in 25 C.C. of concen- trated hydrochloric acid and 5 C.C. of a saturated solution of bromine in hydrochloric acid and the excess of bromine is expelled by heating the mixture. Three or 4 grams of sodium sulphite are next added to reduce the antimony and the solution is evaporated to a volume of about 10 C.C. If more than 3% of arsenic is present 20 C.C. of concentrated hydrochloric acid and 5 C.C. of saturated sulphurous acid are added and the liquid is boiled down again. To the concen- trated solution 20 C.C. of concentrated hydrochloric acid and 40 C.C. of hot water are added and the whole is boiled for one minute t o remove traces of sulphur dioxide.The solution is then titrated with N/20 potassium bromate solution using methyl-orange as indicator. The bromate solution is standardised on arsenious chloride solution. During the titration the solution should be kept at a temperature of not less than 60° and the bromate solution must be run in drop by drop with constant stirring. Lead zinc tin silver and chromium have no influence on the estimation but the presence of large quantities of calcium and ammonium salts tends to make the results too high. If copper is present it must be removed before carrying out the titra- tion; for this purpose the alloy is evaporated with nitric acid the mixed oxides of antimony and tin are collected on a filter dried and fused with sodium hydroxide.The fused mass is then dissolved in hydrochloric acid and the estimation continued as described. w. P. s. Estimation of Golumbiurn and Tantalum in the Presence of Titanium. CHARLES H. WARREN (Amer. J. Sci 1906 [iv] 22 520-522).-Tho author confirms Noyes’s statement that repeated fusion with potassium pyrosulphate does not only dissolve titanium but also notable traces of columbium and tantalum oxides. Osborne’s process oxidation of the lower oxides of titanium and columbium with permanganate and subsequent colorimetric estimation of the titanium by means OF hydrogen peroxide was found to be very unsatisfactory. Up to the present no satisfactory process is known t o the author L. DE K,134 ABSTRACTS OF CHEMICAL PAPERS. Estimation of Small Amounts of Ethyl Alcohol.MTLAN J. STBITAR (Zeit. physiol. Chem. 1906 50 22-29. Compare Abstr. 1904 ii 686 ; Nicloux Abstr. 1905 ii 181 ; Landsberg Abstr. 1904 ii 499).-The ethyl alcohol contained in solutions of about 1 to 1.5% may be estimated by the iodide method (Abstr. 1904 ii 686). The method may also be used for determining the ethoxy-groups in esters ; these are hydrolysed with potassium hydroxide the ethyl alcohol distilled over and diluted to the required strength. When the per- centage of alcohol is below 0.5 the experimental error is greater. J. J. S. Determination of the Densities of Alcohols by means of their Critical Temperatures of Solution. LBON CRISMER (BUZZ. Xoc. chim. Belg. 1906 20 294-305. Compare Abstr. 1903 ii 10). -Vandam has proposed to apply the results obtained by the author (Zoc.cit.) to the determination of the critical temperature of solutions of butters in alcohol having D15'5" 0.7967. In the present paper the data employed by Vandam are criticised since they are not in accordance with those previously recorded by the author and the precau- tions which must be taken in preparing alcohol and light petroleum to be used in making determinations of this kind are described. It is shown that (1) unless recourse is had to the use of a thermostat the results obtained in determining the density OF alcohol by means of a Westphal balance or a pyknometer are unsuitable for use in standardising a light petroleum to be employod for the determination of the critical solution temperature of an alcohol; (2) the best and simplest method of determining the density of a commercial alcohol is to ascertain its critical solution temperature in light petroleum pre- viously standardised by means of anhydrous alcohol ; (3) in each case it is safer to determine a second point on the curve of critical solution temperature in order to verify its concordance with the data previously recorded; and (4) light petroleum once standardised may be pre- served unchanged for several years in stoppered flasks kept in the dark.T. A. H. The Allen-Marquardt Process for the Estimation- of Higher Alcohols. EDWARD A. MANN and C. E. STACY ( J . Xoc. Chem. I r d 1906 25 1125-1129).-The results of an investigation of this method show that in order to obtain complete oxidation of the amyl alcohol and the recovery of the valeric acid it is necessary t o perform the oxidation in pressure bottles ; the use of a reflux apparatus tends to cause loss of valeric acid through incomplete condensation.Trust- worthy results are obtained only when the extraction with carbon tetrachloride is carried out at temperatures below 15.5'. Above this temperature the solubility of ethyl alcohol in carbon tetrachloride and subsequent formation of acetic acid during the oxidation render it impossible to calculate the amount of the higher alcohols from the titration. Since serious loss of valeric acid occurs in drying the barium salts for the estimation of the combining weights of the acids the higher alcohols must be estimated by titration all the acidity beingANALYTICAL CHEMISTRY. 135 calculated as valeric acid.The titration for “mineral acids” is unnecessary and introduces errors. w. P. s. New Method for the Estimation of Glycerol in Wines. CH. BILLON (Rev. intern. falsif. 1906 19 57-58).-A mixture of alcohol and ethyl acetate is employed in place of the usual alcohol- ether solvent for extracting the glycerol from the wine residue. Fifty C.C. of the wine are rendered alkaline with milk of lime and evaporated to the consistency of a paste. The latter is transferred to a 100 C.C. flask by the addition of several successive small quantities of alcohol using not more than 20 C.C. altogether and the whole is made up t o a volume of 100 C.C. with ethyl acetate. After mixing the solution is filtered and a known volume of the filtrate evaporated the residue being then dried at a temperature below 70’ and weighed.I n the case of sweet wines 50 C.C. are evaporated with lime the residue is extracted with boiling alcohol so as to obtain 100 C.C. of alcoholic solution. This is again evaporated the syrupy residue is taken up with 10 C.C. of alcohol and sufficient ethyl acetate to make the volume 50 c.c. the solution is filtered and a portion of the filtrate evaporated as described previously. w. P. s. The Values of Different Colour Reactions of Pentoses. FRITZ SACHS (Biochem. Zed. 1906 1 383-398).-Various methods for the detection of pentose in urine were compared; the principal difficulty appears to be that glycuronic acid gives similar reactions. Salkowski and Blumenthal’s orcinol reaction is recommended for clinical use if prolonged boiling is avoided.Jolles’ method with sodium acetate and phenylhydrazine appears to be of little value and Neumann’s modified orcinol test is regarded as of value only as a confirmatory test. W. D. H. Detection of Pentoses in Urine. ADOLF JOLLES (Biochem. Zeit. 1906 2 243-244. Compare Abstr. 1906 ii 203).-The author gives details of his method which make it certain and defends it from Sach’s criticisms (preceding abstract). FRITZ SACHS (ibid. 245-246) replies ; he adheres to his opinions. W. D. H. A Colour Reaction of Reducing Sugars with Alkaline m-Dinitrobenzene. CHAVASSIEU and ALBERT MOREL (Compt. rend. 1906 143 966-967).-m-Dinitrobenzene gives a violet coloration with nldoses and ketoses in moderately alkaline solution. The reagent prepared by adding 35 C.C.of a 33% sodium carbonate solution to a solution of 1 gram of m-dinitrobenzene in 100 C.C. of alcohol is slightly rose-coloured in consequence of the presence of dinitrothiophen (compare Meyer and Stadler Abstr. 1885 141). The violet coloration is formed in fifteen minutes if 10 C.C. of the reagent is added to 20 C.C. of a 1% aqueous solution of maltose lactose galactose or arabinose or in two and a half hours with a 0.1% solution of these carbohydrates. Laevulose givcs the violet coloration in two to three minutes in a 1% or in lesc; than ten136 ABSTRACTS OF CHEMICAL PAPERS. minutes in a 0.1% solution; hence by this reaction laevulose can be detected in the presence of other carbohydrates. Sucrose glycogen the albumins the albumoses amides including carbamide and creatine do not give colorations with alkaline m-dinitrobenzene but the aldehydes and ketones which are not alcohols and which give a red coloration (Bittd Abstr.1897 ii 468) as also uric acid which gives a violet coloration must be removed before the aldoses and ketoses are tested for. This reaction which is as delicate and characteristic as those usually employed for the detection of the reducing sugars serves also for the approximate colorometric estimation of these substances. G. Y. Estimation of Reducing Sugars. GABRIEL BERTRAND (Bull. Xoc. chim. 1906 [ iii] 35 1285-1 299).-Four solutions are used each of which for the quantities of salt named below is made up to one litre (a) cupric sulphate 40 grams; (b) sodium potassium tartrate 200 grams and sodium hydroxide 350 grams; ( c ) ferric sulphate 50 grams and sulphuric acid 200 grams; ( d ) potassium permanganate 5 grams.The quantity of sugar solution used should be 20 C.C. and contain from 0.01 to 0.09 gram of the sugar; to this 20 C.C. each of solutions a and b should be added and the mixture boiled for three minutes reckoned from the time that tho first bubbles of steam appear. The cuprous oxide is collected in a Soxhlet tube dissolved in a known quantity of solution c and the ferrous sulphate thus produced titrated by means of solution d (compare Wolff Abstr. 1906 ii 57). Tables showing the quantities of copper equivalent to integral amounts (between 10 and 100 mg.) of the principal reducing sugars are given in the original.Gravimetric Eetimation of Sugar by Means of Fehling’s Solution. W. KELHOFER (Zeit. anal. Chem. 1906 45 745-746).- A number of experiments are communicated to show the accuracy of the author’s recent tables (Abstr. 1906 ii 311) for the estimation Estimation of Sugar. IVAR BANG (Biochem Zeit. 1906 2 271-290).-A comparison is made of the author’s method with others. He claims that his titration method is as accurate as gravimetric methods and much more expeditious. The method is titration with a copper solution to which a small amount of hydroxylamine is added ; at the end point the mixture becomes colourless. T. A. H. of invert sugar. L. DE K. W. D. H. Estimation of Dextrose with Fehling’s Solution containing large excem of Alkali. FRANCISCO P. LAVALLE (Chem. Zeit.1906 30 1301-1302).-Objection has been made to the author’s method (Abstr. 1905 ii 588) on account of the reoxidation of the alkaline cuprous oxide solution. This may however be prevented by working in an atmosphere of ammonia generated in the Erlenmeyer flask itself by the addition of a little ammonium chloride The flask is fittedANALYTICAL CEEMISTRY. 13’1 with a doubly-perforated cork; through one hole passes the tube connected with the burette containing the dextrose solution and through the other a tube connected to a U-tube containing pumice moistened with sulphuric acid to absorb the ammonia. 1;. DE K. The Value of Almbn’s Bismuth Test and the Worm-Muller Copper Test for Sugar in Urine. OLOF HAMMARSTEN (Zeit. pphysiol. Chem. 1906 50 36-’72).-The recent remarks of Pfluger on the comparative uselessness of t.ests for sugar except that of Worm- Miiller have led the author to a complete and critical examination of the bismuth test with the result that the value of the latter is largely vindicated.W. D. H. The Usefulness of the Hammarsten-Nylander and Worm- Muller Sugar-tests. EDUARD PFLUGER (PfEGger’s Arcltiv 1907 116 265-282).-Polemical against Hammarsten (preceding abstract). W. D. H. Use of Polarised Light for the Microscopical Detection of Rice Starch and Maize Starch in Wheat Flour. G. GASTINE (Compt. rend. 1907 144 35-37. Compare Abstr. 1906 ii 587).- A small quantity of the flour is moistened with a drop of water spread on a glass plate dried at a low temperature and the drying finished by a few moments’ exposure at 120-130° or longer at 100’ only.The preparation is then mounted in Canada balsam and examined in simple polarised light and in polarised light modified by a plate of gypsum giving the red of the first order. I n both cases the starch cells have a characteristic appearance. In the dark field of simple polarised light the amylaceous grains or fragments of rice flour including several cells appear brilliantly illuminated with a granite-like texture. I n chrom- atically polarised light the blue and clear orange tints formed at the edge of the hilum in crossed positions form a characteristic linear net- work. Maize flour gives a reticular appearance of much larger mesh. Millet buckwheat darnel and many other starches even the smallest such as exists in the beet-seed have an analogous appearance.The lenticular grains of wheat starch do not show this appearance. The method has the advantage over that previously described of allowing the use of objectives of lower power. The statement made in many micrographical works that rice starch does not polsrise light is contradicted. E. H. Nessler’s Reagent as a Test for Gums. JEAN VAMVAKAS (Ann. Chim. anal. 1907,12,12-13).-The author has obtained the following results. Almond trree gum-A concentrated solution of this gum gives with Nessler solution in the cold a cream-coloured gummy precipitate. The same reaction is also obtained at the boiling heat. Tartaric acid prevents the precipitation. Gum arabic.-A 30% solution gives in the cold a dirty grey emulsion and a grey deposit is formed after some time.This precipitate is formed immediately on boiling but tartaric acid almost completely prevents the reaction.138 ABSTRACTS OF CHEMICAL PAPERS Gum tragacanth.-This gives no reaction whatever with Nessler solution. On adding tartaric acid before the Nessler solution and then boiling a slight dirty orange-coloured deposit is formed after some time. L. DE I(. A New Apparatus for the Estimation of t h e Volatile Acids in Wine. HANS BOETTICHER (Zeit. anal. Chem. 1906 45 755-758).- The distilling flask has the form of an elongated cylinder thus forcing the steam to traverse a deeper column of liquid than is the case with the apparatus usually employed. The vapours before entering the worm condenser pass first through a bulb connected with a slanting bent tube. The wine (50 c.c.) is introduced into the cylinder by means of a side tubulus with a ground stopper and to prevent frothing a few drops of olive oil are added. Steam is now passed through and the wine is vigorously boiled until the 200 C.C.of distillate required are collected. The bottom of the cylinder is placed in a semi-spherical wire gauze of 25 C.C. content ; a special mark thus becomes superfluous. L. DE K. Differentiation of the Two Pharmaceutical Benzoic Acids. H. CORMIMBOEUF and L. GROSMAN (Ann. Chirn. and. 1906 11 462-464).-A reply to Belloni (ibid,) who states that there is nothing novel in the process recommended by the authors (Abstr. 1906 ii 636). The authors admit that various pharmacopaeias recommend testing the samples for chlorine by heating with calcium Carbonate but this is by no means so efficacious as the author’s process with anhydrous sodium carbonate which moreover is carried out on a much larger quantity of the substance.Contrary to Belloni’s statement the authors have also never met with a natural benzoic acid which gives the organic chlorine reaction. I n no pharmacopceia however is mention made of the characteristic odour noticed on heating the natural product with solution of sodium carbonate. L. DE K. Separation of Salicylic Acid and ‘‘ Saccharin ” from Food Materials. GIUSEPPE BONAMARTINI (Rev. intern. FuZsiJ 1906 10 39-43).-Bromine precipitates salicylic acid quantitatively from its solution but as the precipitate has not a definite composition it is impossible to calculate the amount of salicylic acid from the weight of the bromine precipitate.On the other hand “saccharin” is not precipitated by bromine and consequently can be tested for in the filtrate from the bromine-salicylic acid preeipi tate. I n cases where it is desired to test for both salicylic acid and ‘‘ saccharin ” in liquids containing other substances which are precipitated by bromine as for instance in beer and wine it is necessary to evaporate the liquid and extract the residue with a mixture of ether and light petroleum. The residue obtained on the evaporation of the solvent is then dissolved in water and treated with bromine to separate the salicylic acid from the “ saccharin.” w. P. s.ANALYTICAL CHEMISTRY. 139 Occurrence of Salicylic Acid in Tomatoes HENRI PELLET (Ann.China. anal. 1907 12 10-.12).-The author agrees with Ferreira da Silva that the presence of 10 mg. of salicylic acid in 1 kilo. of tomatoes should not be regarded as indicating adulteration as it occurs naturally although only in traces. L. DE K. Optical Behaviour and some other Properties of the most important Animal Fats. M. A. KAKUSIN (Chem. Zeit. 1906 30 1247-1249. Compare Abstr. 1905 ii 619 802; 1906 i 951. Neuberg Abstr. 1906 i 923).-The results of measurements of the sp. gr. by means of the Gintl-Rakusin pyknometer or in the case of solid fats by the apparatus previously described (Abstr. 1905 ii 303) and of the optical activity of twenty-four fats of animal origin are tabulated and discussed. The sp. gr. of animal fats rarely exceeds 0.930 at 15'; the high results obtained with butter and commercial lanolin are caused by the presence of water.When dried by the action of anhydrous sodium sulphate in ethereal solution butter has D; 0.9300 lanolin D: 0.9289. Spermaceti has Di% 0.8922. Most animal fats are optically inactive but cod liver oil is laevorota- tory and lanolin dextrorotatory. In concentrations greater than 1 in 1600 oleum corn% cemi and oleum nnimale Dippeli are opaque to polarised light. G. Y. Detection of Cocoanut Oil and Margarine in Butter. LUCIEN ROBIN (Ann. C'him. anal. 1906 11,454-462).-Five grams of tho butter-fat are boiled in the reflux apparatus with 25 C.C. of alcoholic potassium hydroxide for five minutes 17 C.C. of water are added and the excess of alkali titrated with alcoholic N/2 hydro- chloric acid.A blank experiment having already been made the saponification number is calculated as usual. A sufficient quantity of the acid is now added to liberate completely the fatty acids and 56.5 vol. % alcohol is added until the volume occupies nearly 150 C.C. The whole is then cooled with constant shaking so as to prevent the formation of a solid fatty cake. After making up exactly to 150 c.c. the liquid is filtered and 50 C.C. are titrated as usual; the result is f u t t y acids soluble in 56.5 vol. % alcohol. Another 50 C.C. are heated in a water-bath until 15 C.C. are left. The acids insoluble in water float and are washed four times with water at 60". The acids are then dissolved in a mixture of 2 parts of alcohol and 1 part of ether and titrated with N/10 potassium hydroxide; the result is fatty acid insoluble in water but soluble in dilute alcohol.The water-soluble acids are then found by difference. A large number of experiments with pure and adulterated butters are recorded. These show that a butter is undoubtedly adulterated with cocoanut oil if (1) the water-soluble figure is below 5.92 and if the relation insoluble/soluble x 10 equals at least 13. (2) If when this figure is above 5.92 the sum of the relation figure and the alcohol- soluble figure exceeds 30. The amount of adulteration may be calculated approximately as follows. A relation figure of 13-15 = 10% of cocoanut oil ; 15-20 show 15% ; 20-25 20% and 85-30 25%. If a butter is adulterated with margarine the water-soluble figure is140 ABSTRACTS OF CHEMICAL PAPERS below 5.92 and the relation figure below 13.tion the standard 6.15 may be employed. For purposes of calcula- If both margarine and cocoanut oil are present the table in the The Constants of Bog-Butter found in the Peat in Ireland. LIONEL G. RADCLIFFE and W. H. XADDOCKS (J. Soc. Chem. Ind. 1907 26 3).-The specimen to which the following figures refer was found about 4 ft. below the surface and was probably some hundreds of years old. It was a crumbly cheese-like substance and numerous cows' hairs were interspersed throughout the mass leading to the conclusion that the substance was originally butter which had been placed in the peat water to preserve it The figures obtained were m. p. 46.5-49.5"; total fatty matter 98%; DA?," 0.8390 ; butyrometer number 23.5 at 50'; acid number 201.9 ; saponification number 324.1 ; acetyl number 2.2 ; Reichert-Meissl number 1.2 ; insoluble fatty acids 98.5% ; iodine number (Wijs) 10.0.The non-fatty matter contained nitrogen and original article will give valuable information. L. DE K. was most probably casein. w. P. s. Estimation of Formaldehyde in Milk. PREDERIC W. RICHARD- SON (J. SOC. Chem. Imd. 1907 26 3-4).-'Che method is based on the formation of a violet colour when sulphuric acid is added t o milk containing formaldehyde a qualitative test devised originally by Hehner. Four C.C. of concentrated sulphuric acid containing 0.05% of ferric sulphate are added drop by drop with constant stirring to 5 C.C. of the milk. The mixture is then diluted to a volume of 50 C.C.by the addition of 50% sulphuric acid when a solution is obtained which is sufficiently clear to be examined in a colorimeter. w. P. s. Estimation of Preservatives in Milk. HERBERT S. SHREWS- BURY (Analyst 1907 32 5-13).-B'orrnaZdehyde. - The method proposed is based on that described previously by Liverseege (Abstr. 1901 ii 483). Ten C.C. of the milk and 7 C.C. of dilute ferric chloride-sul- phuric acid are mixed in a stoppered tube and left for about fifteen hours. The dilute acid is prepared by mixing 3.5 C.C. of 5.4% ferric chloride 40 C.C. of water and 100 C.C. of concentrated sulphuric acid. The coloration produced is compared with that obtained in comparison tubes containing known quantities of formaldehyde these standards being also left overnight.Boric acid.-Seventy C.C. of the milk after the addition of 7 C.C. of 12% sodium hydroxide solution are evaporated to dryness and the residue is ignited to a white ash. The latter is dissolved in hot water and a few drops of hydrochloric acid and the solution is transferred t o a 100 C.C. flask Phenolphthalein is now added and then alternately sodium hydroxide solution and 5.6% calcium chloride solution until a slight excess of both is present. The whole is made up to a volume of 100 C.C. and filtered. The filtrate is acidified with hydrochloric acid using methyl-orange as indicator boiled neutrdised with sodium hydroxide glycerol is added and the solution titrated with 3/10 sodium hydroxide using phenolphthalein as indicator. If the fjltrate requires more than 1-5 C.C.of N,IO sodium hydroxide the phosphate precipitateANALYTICAL CHEMISTRY. 141 is redissolved in hydrochloric acid the aolution is diluted rendered just alkaline with sodium hydroxide filtered and the boric acid in the filtrate titrated as described above. This process is repeated until the filtrate requires less than 1-5 C.C. of N/10 sodium hydroxide. The number of C.C. of N/10 sodium hydroxide required to neutralise all the filtrates when multiplied by the factor 0.0062 expressee the quantity of boric acid in grams. w. P. s. Estimation of Methylfurfuraldehyde. KONRAD FROMHERZ (Zeit. physiol. Chem. 1906 50 241-249. Compare Jager and Unger Abstr. 1903 ii 187 456).-Methylfurfuraldehyde yields a precipitate CI0HsO4N2 with barbituric acid in the form of minute yellow needles and plates which dissolve sparingly in water cold alcohol ether or acetone but readily in dilute alkalis yielding colour- less solutions Its solubility in 100 C.C.of 12% hydrochloric acid is 2.29 mg. The amount of methylfurfur- aldehyde ( M ) in a solution may be calculated from the formula M= $(B + n x 0*000023) where B = the weight of precipitated methyl- furfuraldehydebarbituric acid and n = the total number of C.C. of solution. A mixture of furfuraldehyde and its methyl derivative may be estimated by means of barbituric acid. For the separation of the two aldehydes by Ellett and Tollens' method (Abstr. 1905 ii 210) it is advisable to filter fourteen to sixteen hours after precipitating. After twenty-four hours the methylfurfuraldehyde-glucoside can no longer be completely removed by alcohol.J. J. S. It decomposes at about 2609 Some Methods of Estimating Nitriles and Carbylamines. H. GUILLEMARD (Compt. rend. 1906 143 1158-1 160).-Metallic cyanides react with alkyl iodides to form a mixture of the correspond- ing alkyl nitrile and carbylamine (isocyanide) and in the present paper various methods of estimating each isomeride are described. The carbylamines (isocyanides) are readily decomposed in the cold by the action of bromine water or alkali hypobromites with the formation of one equivalent of carbon dioxide ; further the carbylamines decom- pose aqueous solutions of oxalic acid in the cold with the formation of equal volumes of carbon dioxide and carbon monoxide and either of these reactions can be employed for the estimation of carbylamines in the presence of the isomeric nitrile as neither bromine water nor oxalic acid have any action on the alkyl nitriles. i n practice the author employs the following method whereby the nitrile and the carbylamine resulting from the action between an alkyl iodide and a metallic cyanide in a sealed tube are each estimated.The contents of the tube are distilled in the presence of a concentrated solution of potassium cyanide made alkaline with potassium carbonate the distillate which contains ammonia and a little hydrocyanic acid in addition to the nitrile and carbylamine is again distilled in the presence of potassium carbonate which removes the hydrocyanic acid ; the second distillate is treated with a known volume of standard sulphuric acid whereby the ammonia is neutralised and the carbyl- amine decomposed into the corresponding formamide ; the ammonia is VOL.XCII. ii. 10142 ABSTRACTS OF CHEMICAL PAPERS. determined by estimating volumetrically the excem of sulphuric acid ; the nitrile is separated from the mixture by distillation hydrolysed by heating in a sealed tube at 150' for three hours with 50% sulphuric acid and the resulting ammonium salt estimated in the usual way; and the formamide in the residual liquid is similarlv estimated after hydrolysis by boiling with concentiated sulphuric kid. M. A. W. Folin's Method for the Estimating of Urea. E. PROVAN CATHCART (Proc. physiol. Xoc. 1906 viii-ix ; J. Physiol. 35).- Folin's method gives accurate results and is expeditious.Uric acid- and hippuric acid-nitrogen are not affected. Allantoin appears t o be the only substance in urine likely to give rise to an error but as it only occurs in traces the error is negligible. W. D. H. Estimation of Urea in Urine. A. CHRUSTALEFF (Chem. Celztv. 1906 ii 1361-1362; from Bull. Akad. St. Petersburg [v] 22 121-123).-The Folin-MFrner process is recommended as it is not influenced by the presence of other nitrogenous substances. L. DE K. Estimation of Guanidine Carbonate and its Application in Analysis. HERMANN GROSSMANN and BERNHARD SCHUCK (Chem. Zeit. 1906 30 1205-1206).-Guanidine carbonate now easily procurable is a strong alkaline carbonate which can be titrated with standard acid. Solutions of copper nickel and cobalt are precipitated in the cold b u t on heating they are slightly redissolved.Aluminium solutions give a precipitate soluble in large excess of the reagent ; the alumina is reprecipitated on adding ammonium cbloride but not by ammonia. I n the absence of ammonium salts guanidine carbonate makes a convenient reagent for the quantitative precipitation of cad- mium zinc and manganese less so for magnesium. The precipitates are readily washed and collected. Aluminium sulphate and guanidine sulphate form a double salt which however is not identical with an ammonia alum. L. DE K. Reactions of Boric Acid with Opium Alkaloids. C. R,EICHARD (Chem. Centr. 1906 ii 1290-1291 ; from Pharrn. Zeit. 51,817-818). -A mixture of boric acid and narceine moistened with water and evaporated t o dryness turns yellow ; on adding hydrochloric acid and again evaporating the mass turns brown.Papaverine behaves like narceine but narcotine although at first giving the yellow colour turns a dark grey. Thebaine gives a green colour gradually changing to grey or black. Codeine gives a green colour changing to a dirty brown ; morphine behaves very similarly. L. DE K Microscopic Reactions of Pyramidone. F. WEEHUIZEN (Ohm. Centr. 1906 ii 1628-1629 ; from Pharm. Weekblad 43,1105-1106). -When a solution of iodine in potassium iodide is added t o a 1% solu- tion of pyramidone which has been cautiously acidified with dilute sulphuric acid a reddish-brown precipitate is formed the colourANALYTICAL CHEMISTRY. 143 of which changes after a time or on agitation t o dirty yellow.The precipitate appears under the microscope to consist of yellow prisms and more slender needles. When a dilute solution of bromine in potassium bromide is added drop by drop to a solution of a small quantity of pyramidone in a few drops of dilute sulphuric acid a green coloration is formed which changes successively t o violet red and yellow. After shaking the solution and allowing it to remain for some time it becomes colourless and a white precipitate is formed which consists of irregularly arranged needles which are loager and more slender than those of the iodine-potassium iodide precipitate. A solution of 1 part of pyramidone in 400 of water which has been made acid with dilute sulphuric acid gives a white precipitate with Mayer's reagent ; the precipitate after remaining for some time appears to consist of triangular crystals.A white precipitate is also formed by adding potassium cadmium iodide to a 1% solution of pyramidone ; it is made up of rosette-like aggregates of crystals and of 4- and 6-sided plates The white precipitate formed by mercuric chloride consists of feathery needles. A solution of sodium-palladium chloride forms a yellow precipitate which consists of needles arranged in some cases in X- or Y-shaped clusters. E. W. W. Colour Reactions of some Organic Compounds. EUGENIO PIRER~A ALVAREZ (Ann. Chim. anal. 1907 12 9-10).-0~05-0~1 gram of the substance and 0.2-0.3 gram of sodium peroxide are put into a porcelain capsule with 5 C.C. of alcohol and after four to six minutes 15 C.C.of water are added. The following colorations are pro- duced. Ernodin gives an intense rose colour turning yellow on addition of a few drops of acetic acid. Chrysarobin a wine-lees colour not destroyed by dilution with water but turning yellow on addition of acetic acid. 1 2-Dihydroxyanthraquinone a very beautiful bluish- violet colour not destroyed by addition of water; with acids the liquid turns intensely yellow. Alizarin from madder turns very strongly violet and becomes orange on adding acids. 1 2 4-Tri- hydroxyanthraqwinone gives an intense reddish-violet colour turning cherry -red on adding water. Ch~ysoplunic acid gives a cherry-red colour which becomes brighter on dilution. Rosolic acid an intense purple colour not destroyed by water.Purpurin a beautiful intense rose colour not destroyed by dilution. Anthragallol a persistent dark blue nearly black. Dihydroxybenxoquinone a maroon-yellow turning red on dilution with water. Ellagic acid gives a maroon-black turning yellow on dilution. L. DE 'EC. Detection of Indican in Urine. FRANCISCO P. LAVALLE (Chew. Zed. 1906 30 1251).-To 10 C.C. of urine are added 2-3 C.C. of hydrochloric acid containing 5 grams of ferric chloride per litre and while cooling 2-3 C.C. of pure sulphuric acid are added drop by drop. The solution is then shaken with a little chloroform and the blue colour due to sulphindigotic acid is noticed. This reaction is much more delicate than €hose of Obermayer Heller and others. L. DE K.144 ABSTRACTS OF CHEMICAL PAPERS. Adsorption Analysis and Uhromatographic Methods.Employment for Chlorophyll. M. TSVETT ( C h . CenCr. 1906 ii 1286; from Ber. deut. bot. Get?. 24 384-393).-Many dyes dissolved in light petroleum benzene xylene carbon tetrachloride or carbon disulphide are precipitated by powdered substances from which they may be extracted by alcohol ether acetone or chloroform. There is further an adsorption series in which the substances can replace each other in the adsorption compound. When a mixed solution as for instance chlorophyll dissolved in carbon disulphide is filtered through a column of precipitated calcium carbonate the dyes are precipitated but mutually replace each other and arrange themselves according to the adsorption series in the direction of the stream. If any zone is not pure it can be extracted and the adsorption repeated until the desired degree of purity is attained. C . J. REICHARDT (Chem. Cenntr. 1906 ii 1290; from Pharm. Zeit. 51 518-519).-After testing for albumin in the usual way by boiling with a few drops of nitric acid 3 C.C. of pure sulphuric acid and 3 C.C. of saturated ferrous sulphate solution are put into a test tube and after mixing 6 C.C. of urine are gently poured over it. If dark-coloured rings are formed the urine contains albumoses peptones biliary colouring matters -&c. N. H. J. M. Preliminary Testing of Urine. L. DE K. Tabloid Test for Enzymes for the Rapid Control of Pasteurised Milk. BRU~RE (J. Pharm. Chim. 1906 [vi] 24 488-493).-The reagent consists of tabloids of (a) a mixture of crystallised guaiacol and lactose and ( b ) sodium perborate which are added to the sample of milk under examination. It has an alkaline reaction in solution and gives with fresh milk a salmon coloration which immediately changes to garnet red whereas milk which has been pasteurised above SOo or boiled gives no coloration whatever. The colorationis due to the oxydase of the milk which in the case of cow's milk is at a maximum activity between 40' and 50° is stopped by cold and is .normal at about 15'. Old milk after keeping some days loses its power of giving a coloration probably owing to the development of lactic acid as the addition of sodium hydrogen carbon- ate generally restores the activity of the enzyme. Milk containing vegetable ferments gives an orange or brown coloration whilst milk preserved by the addition of peroxide yields the red coloration on the addition of the guaiacol and lactose tabloids only. E. F. A.

ISSN:0368-1769    

DOI:10.1039/CA9079205127

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

145 General and Physical Chemistry Refractive Indices of Gases at the Temperature of the Room and of Liquid Air. KAHL SCHEEL (Ber. deut. phys. Ges. 1907 5 24-36).-The refractive index of hydrogen nitrogen and air has been measured for a series of wave-lengths by the interference method at 16' and at the temperature of liquid air. The data obtained at 16' are reduced to 0' by means of the formula n - l/d = const. The variation of (n - l ) l O 7 with the wave-length X (expressed in terms of p) is given by the formula hydrogen 1358.3 + 9*05/h2 ; nitrogen 2906.1 + 22*47/h2 ; air 28'70.5 + 16*23/A2. In order t o test the constancy of the expression n - I / d over the temperature interval 0' to - 190° it is employed to calculate the density of hydrogen and nitrogen a t - 190° using the experimentally determined values of the refractive index a t 0' and - 190'.The calculated values differ from the experi- mental numbers by 0.4%. Whether this is due to the inconstancy of n- l/d or to experimental errors is not known. I n any case the formula can be employed to calculate the densities of gases at low temperatures with considerable accuracy. H. M. D. Refraction in Compound Gases. JULES AMAR (Contpt. end. 1907 144 260-261).-Understanding by the refraction 12 the index N diminished by unity and defining atomic refr.ccction as the quotient of the refraction of a simpler substance by its atomicity the author formulates the rule The yefraction of cc compound QCCS is the sum of the refractions of the atoms which compose the molecule. He shows that allowing for the observed refractions having been taken with different rays for possible polymerisation of the gas and for discrepancies in the refractions observed for the same gas by different authors the calculated values for hydrogen chloride nitric oxide ammonia and water vapour agree fairly well with those observed.The same rule gives fairly good results when used to calculate the refraction of one component of a compound gas from the refractions of the gas and of the other component. The value so obtained for carbon in carbon dioxide when applied to the calculation of the refraction of methane gives a result agreeing moderately well with that observed. Sulphur vapour gives a value four times as great as that calculated from the refraction of sulphur dioxide thus indicating that under those conditions sulphur is tetratomic.E. H. Valency Molecular Refractions and Volumes. Refraction Sterers. I. ISIDOR TRAUBE (Ber. 1907 40 130-139),-1t is pointed out that when Briihl's values for the inolecular refractions (for the u hydrogen line) of several homologous series of saturated carbon compound are divided by the total number of valenciea present in the VOL. XCII ii. 11146 ABSTRACTS OF CHEMICAL PAPERS. molecule a constant (0-78-0*80 mean 0487) is obtained which is termed the refraction stere. Abnormal values are obtained for compounds which readily associate for example methyl alcohol acetaldehyde acetone formic and acetic acids ethyl formate methyl acetate formamide and various nitro-derivatives. Compounds with an equal number of valencies for example propyl alcohol and propionic acid ethyl ether and ethyl acetate n-pentane and isovaleraldehyde have the same molecular refraction. The method can be used for .determining the valency of R particular element in certain of its compounds Thus oxygen appears to be bivalent and not quadrivalent. The relationship between atomic volumes valencies and the electron theory of matter is discussed.The values obtained for Ma/0*787 in the case of certain elements and their simple derivative for example hydrogen oxygen nitrogen water hydrogen peroxide hydrazine ammonia &c are in all cases except that of nitrogen higher than the number of valencies present. The expression valon is introduced to represent the electron or group of electrons present at each valency point.The conclusion is drawn that in organic compounds composed of carbon hydrogen oxygen nitrogen &c. the valon volumes are practically proportional to the inner volumes of the atoms and the atomic and valonic volumes of the different elements are practically multiples in the ratio of the valencies of the atoms. Temperature Radiation of Iodine Vapour. CARL FREDENHAGEN (Yhysikal. Zeitsch. 1907 8 89-91).-A quartz tube containing iodine was heated at about 1250' in an electrical furnace. One end of the tube projected from the furnace into an iron box which was heated by means of a Bunsen burner. By varying the temperature of the projecting portion of the tube the pressure of the iodine vapour could be conveniently increased or decreased.Under these conditions the temperature of the radiating iodine vapour was quite uniform and in all cases a completely continuous emission spectrum was observed. The banded emission spectra obtained by previous observers are attributable to temperature differences in the radiating vapour. This conclusion is confirmed by the author's own experiments in which iodine vapour contained in a quartz tube heated by means of a Bunsen burner was examined. The difference between the two emission spectra obtained under these different conditions is supposed to be due to the displace- ment of the equilibrium in the dissociating iodine vapour when its temperature is not uniform and the general conclusion is drawn that a system in equilibrium can only give rise to a continuous emission spectrum.H. M. D. Temperature of the Incandescent Carbon Particles of Luminous Flames. RUDOLF LADENBURG (Chenz. Cerctr. 1906 ii 1707-1 708 ; from PhpGAaZ. Zeitsch. 7 697-700).-1n order to determine the temperature of the incandescent particles of a flame by means of the emission curve the relationship of the absorption of the J. J. S.GENERAL AND PHYSICAL CHEMISTRY. 147 particles to wave-length must be known. Experiments made with a Hefner lamp 'and an acetylene flame burning in a steatite double burner have shown that both flames have strong selective absorption and that the temperature of the carbon particles is 1405' and 1842O respectively. The temperature OF the flames determined by means of the optical pyrometer and corrected for absorption are 1421" and 1820O respectively.When the correction for reflection is applied the value of the temperatures is raised by loo to 20'. E. W. W. Absorption Spectra of Certain Salts in Aqueous Solution as Affected by the Presence of Certain other Salts with Large Dehydrating Power. HARRY C. JONES and HORACE S. UHLER (Amer. Chem. J. 1907 37 126-195).-The absorption spectra of solutions of cobalt chloride copper chloride and copper bromide and of solutions containing these substances mixed in various proportions with calcium chloride calcium bromide or aluminium chloride have been recorded by means of a direct reading spectroscope. Photographic records of the absorption bands and the changes in the position of these bands when varying amounts of one or another dehydrating agents are added to the coloured solutions have also been obtained.These changes are illustrated by a number of photographic plates. For a description of the apparatus employed and the detailed results obtained the original must be consulted. The general conclusions to be drawn from the study of the absorption spectra will appear in a later paper. H. M. D. Absorption and Fluorescence in Band Spectra and the Ultra-violet Fluorescence of Benzene. JOHANNES STARK ( P h ysikal. Zeitsclh. 1907 8 81-85).-From the known facts relative to fluor- escence phenomena and spectral absorption bands the author concludes that fluorescence is always determined by absorption in a band spectrum. The absorption spectrum of all fluorescing substances is a banded spectrum.The generalisation has been tested and confirmed by experiments on benzene which shows seven absorption bands in the ultra-violet region between 271 and 233 pp. The source of light employed was a mercury lamp of quartz glass the benzene being con- tained in a quartz tube and a spectroscope with quartz lenses was used in the examination of the fluorescence spectra. The absorption bands and the fluorescence bands both decrease in intensity as the wave- length increases. When carbon in the benzene ring is replaced by oxygen sulphur or nitrogen analogous changes are produced in the intensity and position of the bands of the absorption and of the fluorescence spectrum. The question of the connexion between fluor- escence and chemical constitution thus appears to be the same as that between absorption and constitution.Variations of the Absorption Bands of Crystals of Tysonite in a Magnetic Field. JEAN BECQUEREL (Corn@. rend. 1907 144 132-134. Compare Abstr. 1906 ii 317).-The absorption spec- trum of tysonite like that of xenotime is modified by means of a magnetic field. When the crystal has its optic axis parallel H. M. D. 11-2148 ABSTRACTS OF CHEMICAL PAPERS. with the magnetic field and the luminous rays are i n the same direc- tion excitation of the magnetic field causes the displacement of some of the bands of the absorption spectrum to an extent indopendent of the width of the band. The displacement is in opposite sense in the two spectra corresponding with rays circularly polarised in opposite directions and although smaller than with xenotime is of the same magnitude as the Zeernan effect and is clearly visible.The explanation suggested previously that certain bands correspond with positively electrified particles and others with electrons is maintained. When the luminous rays are normal to the magnetic field the extent of t,he displacements is not independent of but is lessened by an increase in the width of the band. Emphasis is laid on the fact that the second crystalline substance which has been found to give this displacement like the first is anexception to the general law for gases and vapours in which all the rays correspond with negative electrons. E. H. Designation of Optical Antipodes as d- and I-Compounds. EMIL PISCHER (Bey. 1907 40 102-106).-An adverse criticism of a paper by Rosanoff (J.Arner. Chem. Xoc. 1906 28 114). In those cases where the prefixes cl- and I- refer to cornpounds which are not dextrorotatory and lzvorotatory respectively but are related in configuration to compounds which are dextrorotatory and laevorotatory the author proposes the nomenclature d'- and It-. Thus laevulose is designated as d'-fructose and the naturally occurring dextrorotatory xylose as E'-xylose. A. McK. Increase and Reversal of Rotation. 11. Salts of the Type of Potassium An.timony1 Tartrate. HEEMANN GROSSMAN (Zeitsclb. physikal. Chem. 1907 57 533-2556. Compare Abstr. 1906 i 799). -Of the corresponding antimonyl boryl and arsenyl tartrates the first is the inost stable and the last is the least stable. When sodium hydroxide is added to potassium antimonyl tartrate the specific rotation assumes a large negative value probably owing to the forma- tion of complexes in which the hydrogen also of the hydroxyl groups is replaced by sodium.The addition of sodium hydroxide to potassium boryl tartrate leads to a marked reduction of the positive rotation without actually causing reversal of the sign so that lavorotatorp complexes are probably present t o a limited extent especially in con- centrated solution The addition of sodium hydroxide to sodium arsenyl tartrate seems to cause complete resolution into neutral tartrate and optically inactive sodium arsenite. It is noteworthy that sodium and ammonium arsenyl tartrates examined alone are both found to exhibit the phenomenon of mutarotation.The free complex acids Sh(C4H5O&,H( AsO)C,H,O and H(BO)C,EE,% are markedly hydrolysed on progressive dilution ; under these con- ditions the rotation of the antimony compound incr6ases that of the arsenyl and boryl cornpounds falls. The relative stability of these compounds in presence of acids and alkalis is similar t o that of the salts. Addition of sodium hydroxide causes reversal of the sign of rotation in the case of the antimony compound only.GENERAL AND PHYSICAL CHEMISTRY. 149 The tendency of malic acid to form complexes with antimonious arsenious and boric acids is notably weaker than that of tartaric acid. All the complexes formed with inalic acid are readily resolved by acids and alkalis. Reversal of rotation occurs in the case of the antimony complex only and it may be induced by the addition of sodium hydroxide or hydrochloric acid.Aluminium salts are found to have a considerable effect in increasing the lzevorotntion of rnalic acid. J. C. P. Some Points of Chemical Philosophy Involved in the Discovery of Radium and the Properties of its Com- binations. HENRY WILDE (Hem. Munchester Pld. Xoc. 1907 51 (l) No. 2 l-l4).-From the constant differences in the atomic weights of the elements in the first and second groups in which mercury and lead are respectively incorporated as the elements of highest atomic weight and from the regular alternation of light and heavy metals in the two series so obtained the author concludes that the atomic weight 2f radium is 184 and its specific gravity about 5. The radioactive properties of radium are supposed to be dependent on its combination with electronegative elements and would not be exhibited by metallic radium.Just as calcium strontium barium and zinc in the metallic condition do not exhibit the phosphorescence of their sulphur compounds so radium plays a similar subordinate part in respect of its radioactivity when combined with electronegative elements. The author does not agree with the view that higher mem- bers of different series of elements undergo transformiition into eacli other directly and doubts whether the distinction made between elementary substances and compounds has a real foundation in nature. H. M. D. Decay of Radium A R and C. 1907 [iv],22 399-400).-Polemical. (this vol. ii 4). PAUL GRUNER (Ann.Plysik. A reply to H. W. Schmidt H. M. D. Theory of the Radioactive Disintegration of Matter. PAUL GRUNER (Arch Sci. p l q s . ncct. 1907 [iv] 23 5-25. Compare Abstr. 1905 ii 367 368 666 792; 1906 ii 139 259 322 413 415 416 514 527 593 719 721).-A rEsum6 of current theory on the subject. E. H. Composition of Thorianite and the Relative Radioactivity of its Constituents. ERNST 3. BUCRNER (Jah7-6. Radioakt. Elek. 1907 3 372- 380).-The author has supplemented previous analyses of thmianite by a minute examination of the various group pre- cipitates and has also deterruined the distribution of the radioactivity of the mineral amongst its various constituents. A table is given containing the percentage amounts of these constituents the radio- activity of each and the fraction of the total activity of the mineral contributed by each constituent.The activity of t'horianite is 83.3 when the value for standard uranium oxide is equal to 100. Nearly the whole of the activity is due to the constituents of the mineral150 ABSTRACTS OF CHEMICAL PAPERS. which dbsolve in boiling concentrated nitric acid. Whilst the mam ratio of the soluble and insoluble portions is 40 1 that of the radio- activity is about 300 1. Ip the case-of those constituents which are met with in the soluble and insoluble portions of the mineral the activity of the soluble fraction is much greater than that of the insoluble fraction. All the separate fractions obtained in the analysis were found to be radioactive with the exception of alumina. This Beems to indicate that the active constituent of the iron group is insoluble in excess of alkali hydroxide.One gram of thorianite yields 8.2 C.C. of helium at 0' and 760 mm. H. M. D. Radioactive Properties of Uranium. MAX LEVIN (Chem. Centr. 1906 ii 1757-1758 ; from Physikd. Zeitsch. 7 692-696).- Attempts to obtain a second radioactive product from uranium have failed but since the experiments were only continued for six months very slow changes may possibly have escaped observation. Precipi- tates of silver sulphide silver chloride copper pulphide bismuth sul- phide and lead sulphide did not carry down any active substances from solutions of uranium salts and precipitation by aniline toluidine hydroxides carbonates and phosphates failed to extract any new sub- stance Electrolysis with varicus electrodes and under different electromotive forces also gave negative results but the radium may be concentrated however from solutions of uranium salts by this method.When uranium oxide is placed in a cavity of the anode carbon of an arc the uranium which is deposited on the cathode shows a constant a-ray activity and an increasing P-activity hence it is evident that a state of equilibrium has not been attained; the activity of the residual uranium oxide remains unchanged. Uranium X may be separated by boiling with soot and 90% of this substance is also precipitated by animal charcoal ; the metal left after cal- cination is almost pure uraninm X . Radium is not precipitated by boiling with animal charcoal. Fractional crystallisation also failed to yield a new product but the activity of thelast crystals was found to be abnormal.E. Jb. W. Radioactivity of the Wieabaden Thermal Springs. FERDI- NAND HENRICH (Zeitsch. angew. Chem. 1907 20 49-51. Compare Abstr. 1905 ii 6 221)-The gas obtained from the Koch and Schfitzenhof springs contains radium. emanation and helium. Com- parative measurements have been made of the radioactivity of a number of different natural waters. P. H. Secondary Rayls Produced by Very Feeble Rontgen Rays. WILHELM SEITZ (Chert&. Centv. 1906 ii 1708 ; from f'hy~ikal. Zeitsch. 7 689-692).-Very feeble Rontgen rays produce secondary rays which have however a very slight aclion on a photographic plate and are strongly absorbed. The power of penetration of these rays lies between that of the original Rontgen rays on the one hand and that of the cathode rays produced by the Rontgen rays on t h e other.The secondary rays are but slightly decreased by charging the reflector,GENERAL AND PHYSICAL CHEMISTRY. 151 and are not affected by a magnetic field. I n addition to the extra- ordinarily feeble Rontgen rays which constitute the major portion the secondary rays also contain electrons. The ratio of the energy of the cathode rays t o that of the clecondary rays hasbeen determined by means of calorimetric and electric measurements and found to increase with the tension. E. w. w. Spectral-analytical Observations on Canal Rays in Com- pound Gases. s. KINOSHITA (Physikal. Zeitsch. 1907 8 35-38).- The canal rays were produced in cylinders of from 4 to 6 cm.diameter with aluminium electrodes about 16 cm. apart with a voltage of from 1600 to 3000 volts. It was found that the canal rays cause dissocia- tion of compound gases those examined being acetylene nitrous oxide carbon dioxide and coal gas. The rays cause the emission of the line or band spectra of the constituent elements whilst also band spectra of compounds were observed simultaneously. The line spectra exhibit the Doppler effect. The author considers that the canal ray particles are positive ions and on the assumption that the carbon line 4267.5 is produced by a positive univalent carbon ion the velocity 3.06 x 107 cm./sec. a t 7000 volts is deduced. The band spectra exhibit no Doppler effect and it is hence probable that the molecules cannot attain the high velocity of the canal-ray particle without decomposing.L. M. J. Mea,surement of Inaccessible Potentials by Means of Inter- mediary Potentials. L. LOJMARANTA (Zeitsch. Elektrochem. 13 33-34).-A platinum electrode immersed in a solution containing arsenious and arsenic acids has no definite potential but in presence of iodine and iodine ions a definite value is quickly attained. The method has already been used by Maitland in the case of solutions of Ferrous and ferric ions (Abstr. 1906 ii 328). The method also yields good results with mixtures of chromic acid and a chromic salt and of a thio- sulphate and a tetrathionate. Solutions of sulphuric and sulphurous acids and of hydrogen sulphide containing free sulphur gave less definite results.T. E . RICHARD ABEGG (Zeitsch. Elektrochem. 1907 13 34-35).-Loimaranta (preceding abstract) has observed that it is only necessary to have a considerable quantity of one of the intermediary substances in eolution since it acts as a reservoir from which the other may be produced if necessary. I n principle i t is possible t o use any change occurring at an electrode as an inter- mediary. For a change such as copper -+ copper ions however the potential to be measured must be near that of copper in a normal solution of its ions otherwise the copper would dissolve Completely or the ions would be almost completely precipitated from the solution. The two cases occur with strong oxidising agents on the one hand or strong reducing agents on the other. I n the second case the electrode would be very easily polarised especially by currents tending to precipitate the metal. The fact that platinum is not readily polarised even in strongly reducing solutions supports the view that it behaves as a hydrogen electrode.Intermediary Pothtials. T. E.152 ABSTRACTS OF CHEMICAL PAPERS Electrical Conduativity of Mixtures of Bromine and Bthyl Ether. WLADIMIR A. YLOTNIKOFF (Zeitsch. physikal. Chem. 1906 67 502-506).-Solutions of bkomine in ethyl ether have a very low conductivity but solutions of ether 'in bromine exhibit a conducting power which is not far short of that possessed by concentrated aqueous salt solutions. Ethyl ether and bromine form a crystalline compound and the conductivity is probably due to the presence of such a com- pound in solution ; the maximum value of the conductivity is found for a mixture containing 11.5% of ether the composition of which corresponds approximately with the formula OEt2,Br,. Between the solutions of bromine in ether and those of ether in bromine there is a range of concentration over which mixtures of the two substances form two liquid phases.J. C?. P. Transport Numbers of Potassium Hydroxide in Concen- trated Solutions. GUNNAR NORDSTR~M (Zeitsch. Elektrochm. 1907,13 35-3S).-Calling x the number of molecules of potassium hydroxide per molecule of water in the solution the transport number of the potassium (1 -n) is (1 -n)-0*232 -0.11 x at 18O. This formula holds good between x = 0.017 and x = 0.14 that is between 5 and 30%. The result is used to calculate the change in the E.2Cf.F.of the Edison accumulator due to changes of concentrabion of the potassium hydroxide during charging and discharging. T. E Migration of the Ions in the Electrolysis of a Fused Mixture of Two Salts. RICHARD LORENZ and W. RUCKSTUHL (Zeitsch. unorg. Chenz. 1907 52 41-47. Compare Abstr. 1904 ii 699).-The experiments with a fused mixture of lead and potassium chlorides described in the former paper have been repeated with practically identical results. It is shown in addition that the tendency to the formation of complex anions containing lead increases with the propor- tion of potassium chloride present. G. S. Temperature of Solid Carbon Dioxide and its Mixtures with Ether and Alcohol at Different Pressures. JOHN ZELEKY and ANTHONY ZELENY (Chena.Centr. 1906 ii 1723 ; from Physikal. Zeitsch. 7,716-719).-The measurements of the temperatures of the following cooling agents were made by means of a nickel-iron thermocouple the boiling point of ethylene ( - 103.9') and the temperature of a mixture of carbon dioxide and alcohol under ordinary pressure ( - 7s-34') being taken as fixed points. When the carbon dioxide gas is continuously removed from pure carbon dioxide snow the temperature sinks con- siderably and may even show a decrease of 15' but the addition of ether or alcohol renders the temperature independent of the removal of gas; alcohol is not however so effective as ether. Solid carbon dioxide and the mixtures mentioned have the same temperature a t any given pressure. Under normal pressure a difference of 1 cm.pressure causes a difference of temperature of 0*17' but at 2 cm. pressure the effect is twenty times as great. Measurements were made between pressures of 2 cm. ( - 116.7') and 84 cm. ( - 77-00"). E. W. W.GENERAL AND PHYSICAL CHEMISTRY. 153 Relation between Development of Heat and Maximum Work in the Gase of Gondensed Systems. WALTHER NERNST (Xitxungs6er. K. Akad. Wiss. Berlin 1906 933-940. Compare Abstr. 1906 ii 727 ; also van’t Hoff Abstr. 1904 ii 381 ; BrBnsted Abstr. 1906 ii 339 834).-If the second law of thermodynamics is expressed in the form A - &= T’ (dA/dT) and the hypothesis is made that the curves representing the variation of A and Q with temperature are tan- gential to each other a t the absolute zero then the following forhauls may be deduced Q = Q0 + Pl’2 + yT3 ; A = Qo - PT2 -y/2.T3. The applicability of these formula? is tested in several cases with satis- factory res (11 t s. J. C. P. Comparison between Chemical Phenomena Determined by a Heating resulting from purely Calorific Causes and those due to a Heating produced by Electrical Actions [Electricity]. MARCELLIN BERTHELOT. (Compt. rend. 1907 144 53-55).-A con- sideration of the sources of error that may arise by considering as purely thermal in origin the changes that occur in gases &c. raised to a high temperature by the passage of a n electric current through a metallic wire carbon rod &c. Thermochemistry of Nitrogen. J. C. THOMLINSON (Chem. News 1907,95,50-51).-A theoretical paper in which the heats of formation of hydrogen peroxide ozone hydrogen cyanide acid cyanogen ammonia nitrous oxide nitric oxide and nitrogen dioxide are discussed the object being to see if it is possible t o deduce thermochemical equivalents for nitrogen in various forms of combination.Thermochemistry of Neodymium. CAMILLE MATIGNON ( A m . Chim. Phys. 1907 [viii] 10 104-118).-Many of the facts recorded in this paper have been given already (Abstr. 1905 ii 505; 1906. ii 675). The heat of solution of Nd,O in dilute hydriodic acid is 106.1 Cal.; that of Ndl in water is 48.9 Cal.; of Nd2(S04) 36.5 Gal.; of Nd,(S04),,5H,0 8.3 Cal. and that of Nd,(SO,),,SH,O 5.7 Gal. The heats of formation of tlie oxides and principal salts of neodymium and of the alkali and alkaline earth metals are tabulated and compared in the original and the conclusion is drawn that neodymium is intermediate in properties between magnesium and calcium.The data available show that the oxides of the alkali metals should be decomposed when heated with metallic neodymium and on the contrary the halogen salts of neodymium should be decomposed by the alkali metals (Abstr. 1901 ii 602) whilst the haloid salts of magnesium should be decomposed by neodymium. It is possible that this simi- larity of neodymium to calcium and magnesium may be regarded as supporting Wyrouboff’s view that the rare earth metals are bivalent although the resemblance of lithium t o the alkaline earth metals has never been regarded a s indicating t h a t lithium is bivalent. M. A. W. W. H. G. T. A. H. Van der Waals’ Equation and the Liquid State.PETRU BOGDAN (Ann. Xci. Univ. Jassy 1907 4 151-161).-In a previous154 ABSTRACTS OF CHEMICAL PAPERS. paper (Ann. Xci. Univ. Jassy 1906 3 35 ; compare also Abstr. 1906 ii 274) i t has been shown that the lowering of the vapour tension of a solvent brought about by the solution of a substance in it is due to association between the molecules of the solvent and those of the solute and a proof of van’t Hoff’s formula from the standpoint of the kinetic theory was given. I n the present paper this proof is given in tl more extended and rigorous form the only assumption made being that the vapour tension above a solution is less than that above the solvent which is iu accordance with experimentally-ascertained fact. The association hypothesis is introduced only to explain the lowering of the vapour pressure of solutions osmotic pressure and to interpret the influence of certain substances on the solubilities of others.The proof is independent of the view t’aken of the constitution of solutions and is equally applicable whether the liquid is polymerised or not. T. A. IT. Exact Calculation of Molecular Weights of Gases. DANIEL BERTHELOT (Compt. rend. 1907 144 76-79. Compare Abstr. 1898 ii 502 ; 1899 ii 207 404).-In a memoire “ Sur les thermometres L gaz!” published in 1902 in Travawx dw Bureuu International des Pods et Mesuyes the author showed that the values of a and 6 of van der Waals’ equation are represented by a= A 27 ~ 2 - = T 273.1 64 p c 0*00000020712 r,3 ; 6 = - 9 - RTC- -- - 0*00025746Tc when the unit of Pc 1% pc Pc pressureis that of the atmosphere the unit of volume that of a gram- molecule of a perfect gas a t Oo and 1 atmos.; and that the molecular weight of a gas can be calculated indirectly from the relation H= 32(1 - Ak)d/(l- A’:) where A:= ~ / 1 - E and 6 =(a - b) and Al and A’ refer to the gas under consideration and oxygen respectively. The atomic weights of hydrogen nitrogen and carbon and chlorine obtained by the direct (Abstr. 1898 ii 502) and indirect methods of calculation are as follows N. 0. *& From From From From From H. N,. NO. N,O. CO. CO,. C1. Direct calculation ... 1.0077 14.007 13’997 13.9995 12.007 12.0026 35.479 Indirect ... 1.0076 14.008 13’998 14‘002 12.007 11.991 35.486 31. A. W. Calculation of the Compressibility of Gases at About Atmospheric Pressure by Means of the Critical Constants.DANIEL BERTHELOT (Compt. rend. 1907 144 194-197).-Tn order to obtain tho “limiting densities” of gases (which give their exact molecular weights) from their normal densities the latter must be multiplied by thefactor(1 -Ai),whereAi= (a - b)/[l-(a - b ) ] . By means of van der Waals’ equation a = 0.000005656 TZ/pc b = 0.0004578 Tc/pc. The author makes use of the values a. = aJT= 0~000000020712 TZ/pc,GENERAL AND PHYSICAL CHEMISTRY. 155 b = 0.00025746 Tc/pc and shows that the latter values agree better than the former with those obtained with the experimental number a - b 2-(1 - 2(a - 6))(1 - 3(a - 6)) The author adversely criticises the corrections applied by Guye to A’ - for H N CO Of NO C O N,O and HCI.van der Waals’ constants. E. H. Molecular Weights of Different Gases Calculated by the Method of Limiting Densities. DANIEL BERTHELOT (Compt. rend. 1907,144,269-272. Compare preceding abstracts).-The molecular weights of hydrogen nitrogen carbon monoxide and dioxide nitrous oxide hy drt bgen chloride ammonia and sulphur dioxide are calculated according to the author’s method of limiting densities described pre- viously (Abstr. 1898 ii 502) by help of the densities and compressi- bilities of the gases observed by different workers. The values obtained for hydrogen chloride and sulphur dioxide place the atomic weight of chlorine between 35.454 and 35 478 and that of sulphur between 32.050 and 32.064 thus agreeing well with the results obtained by chemical analyses. The greater part of the paper is directed to a mathematical discussion of the formuls to be used in calculating the coefficients of deviation from Boyle’s law.E. H. Surface Tension of Aqueous Solutions. 11. G ~ Z A ZEMPL~N (Ann. Physilc. 1907 [iv] 22 391-396. Compare Abstr. 1906 ii 728).-The author’s view that the temperature coefficient of molecular surface energy has the same value for aqueous solutions as it has for pure liquids is found t o be supported by the surface tension numbers recently obtained by Grabowsky and Pann for thirteen aqueous salt solutions of various concentrations a t 10’ and 30’. When the electro- lytic dissociation of the solute is taken into account in the calculation of the molecular weight of the solution the mean value of the tem- perature coefficient is 2.09 with a maximum deviation of 0.48; if the dissociation is neglected the values are 2-54 and 0.74 respectively.The results indicate that the degree of association of water remains unaltered when electrolytes are dissolved in it. H. M. D. Adsorption in Solutions. HERBERT FREUNDLICH (Zeitsch. physikal. Chem. 1906 57 385-470j.-The author has studied the extent to which various substances dissolved in water and other solvents are adsorbed by charcoal. It is found that well-defined equilibria are reached very rapidly from either side. The adsorption isotherm for dilute solutions formed from various solvents and various solutes is given by the formula X = u/m.log,a/(a - x) = k(a/v)-l/n where v is the volume of the liquid m is the amount of charcoal c1 is the total quantity of dissolved substance x is the quantity adsorbed k and n are constants which depend on the temperature and the nature of the dissolved substance.For a given temperature a given solute and a given value of a/v X is a constant the value of which remains the same for different values of m. For a given temperature the exponent l/n varies only between 0.5 and 0.8 in spite of variation of solvent,156 ABSTRACTS OF CHEMICAL PAPERS. solute and adsorbing material (qilk cotton and wool as well as char- coal). The adsorption isotherm does not apply to aqueous solutions of strong electrolytes or to solutions of substances which yield hydroxyl ions. I n aqueous solution inbrganic salts and acids are but sparingly adsorbed by charcoal ; the adsorption of fatty acids aromatic sulphonic acids and salts of organic acids generally is considerable whilst the adsorption of aromatic acids other than sulphonic acids of chlorine bromine and phenylthiocarbamide is very marked indeed.The adsorption in organic solvents is generally slight. When the organic acids are arranged in the order of the extent to which they are adsorbed by charcoal the order is practically the same as when silk is taken as the adsorbing substance (see Appleyard and Walker Trans. 1896 69 1334). The extent of adsorption is but little affected by alteration of temperature. Incidentally it was found that a number of reactions are acceletated in presence of charcoal such as the oxida- tion of formic citric and mandelic acids and of glycerol the reaction between chlorine or bromine and water and the esterification of organic acids in alcoholic solution ; a decomposition of phenylthiocarb- amide by charcoal was also detected.Hydroxyl ions have the effect of causing a suspension of the charcoal which is cleared by the addition of electrolytes. The general relation of adsorption phenomena to other properties of solutions is discussed a t length and the conclusion is reached that these phenomena can be referred back to alterations in the surface tension between solid and liquid so that substances which lower the surface tension must be adsorbed and vice versd In harmony with this view it is shown that negative adsorption is very rare and very small when i t does occur.Marked adsorption is to be observed only in solvents which have a high value for the surface tension between solid and liquid and in such cases the extent to which solutes are adsorbed increases as their surface tension diminishes. One notable consfquence involved in the adsorption isotherm namely the marked increase of the surface concentration while the concentration in the solution is still small may be referred back to the fact that small quantities of a solute are relatively much more effective than large quantities in lowering the surface tension. J. C. P. Endothermic and Exothermic Dissociation Processes. JOHANNES J. VAN LAAR (Zeitsch. physikal. Chew$. 1907,57 633-639)- With any dissociation process it would be possible a t a given temperature to have heat either absorbed or developed by starting with proportions of the reacting substances on one side or the other of the equilibrium point.That is without some rule as to the direc- tion of the reaction which is considered the change might be either endothermic or exothermic. If however a dissociation process is strictly defined as a process in which simple molecules are produced from more complex ones then i t may be shown that almost all dis- sociation processes are endothermic Very few (for example 20 -+ 30,) are exothermic and these must all become endothermic finally at high temperatures for although the absorbed heat of dis-GENERAL AND PHYSICAL CHEMISTRY. 157 sociation is negative a t the ordinary temperature it increases with rise of temperature and ultimately becomes positive.Substances which Possess more than one Stable Liquid State and the Phenomena Observed in Anisotropic Liquids. FRANS M. JAEGER (Proc. K. ,4katL. Wetensclh. Arnsterdccnt 1907 9 472-483. Clompare this vol. ii 78).-The substances dealt with are cholesteryl heptoate nonoate laurate myristate palmitate and stearate which were prepared by melting together equal parts by weight of cholesterol and fatty acid and then purifying by fractional crystallisation from mixtures of ether and alcohol or ether and ethyl acetate. The heptoate and laurate crystallise in long hard needles; the other esters were obtained as flexible tabular crystals. Most of these esters have three stable liquid phases but in the case of the stegrate only labile anisotropic liquid phases may occur.The laurate is interesting in that it can be heated a few degrees above its melting point without melting and it is considered probable that in all these peculiar substances phenomena of retardation play a great r6Ze. The visible changes that accompany alteration of temperature and the appearance of the substances under the microscope are recorded in detail and the observations show that the spherolite structure of the solid phase is of great importance in the transformation of a super- cooled anisotropic liquid into the solid phase. This is further borne out by some observations made with phytosteryl acetate and propionate. Irreversible Phase-transitions in Substances which may Exhibit more than One Liquid Condition. FRANS M. JAEGEE (Z'roc.K. Aknd. llretensch. Arnsterdunt 1907 9 483-492. Compare this vol. ii 78 and preceding abstract).-There are probably no known substances which exhibit under the microscope the phenomena characteristic of anistropic liquids so well as a-phytosteryl butyrate isobutyrate valerate and isovalerate the second and third of these substances being specially suitable for the purpose. Retardation phenomena are very marked in the various transitions and the behaviour particularly of the two valerates can only be described as a gradual transformation solid Z liquid in which there is intermediate realisation of an indefinite number of anistropic liquids. It is pointed out that supercooled ferric chloride hexahydrate like many of the substances which yield fluid crystals crystallises in spherolites the formation of these being preceded by the differentiation of the supercooled liquid into an aggregate of liquid globules.J. C. P. J. C. P. J. C. P. Kinetics of the Formation of Ethers by the Action of Abso- lute Alcohol on Alkyl Sulphates. ROBERT KREMANN ($fOnC6tSh. 1906 27 1265-1273). -The formation of sulphuric acid and ethyl ether by the action of absolute alcohol on ethyl sulphnte takes place in two stages ethyl hydrogen sulphate being formed as the inter- mediate product. In such reactions the velocity constants of the two stages usually differ markedly; in this case a t 57" the velocity of the second stage is only 1/10,000 that of the first. The velocity of the158 ABSTRACTS OF CHEMICAL PAPERS. first stage caq be measured therefore by determining the increase in the acid titre which is proportional to the ethyl hydrogen sulphate formed.In the presence of an excess of alcohol the reaction is unimolecular and the velocity constant k calculated by means of the equation k = l/t.loga/u - x remains constant during the whole stage. The re- action has been studied with methyl and ethyl sulphates and methyl ethyl and propyl alcohols. A t 5 5 O i h e reaction of methyl sulphate with methyl alcohol has k = 10.9 x 10-3; the reaction with ethyl alcohol has k= 7.7 x At the same temperature the reaction of ethyl sulpbate with methyl alcohol has k = 3.5 x 10-3; with ethyl alcohol k = 2a.15 x 10-3 and with propyl alcohol k = 1.9 x As was to be expected the velocity constant diminishes with increasing molecular weights of the reacting substances.I n experiments a t other temperatures the reaction of ethyl sulphate with ethyl alcohol had a t 57" the constant k=0.0027 and at 65" k = 0.0046 which gives a temperature coefficient of 2.1 for loo. The reac ion of methyl sulphate with methyl alcohol at 31.5' has k=0-00082 and at 44" k=0*0032. From this the temperature co- efficient for 10' is calculated by means of the equation kt+,,/kt = 1010b to be 3.0 or slightly higher than the normal value. and with propyl alcohol k = 6 0 x 10-3. G. Y. Esterification of Aminobenzoic Acids by Means of Alcoholic Hydrogen Chloride. ANTON RAILAN (Monutsh. 1306,27,997-1044. Compare Abstr. 1906 ii 659).-The rate of esterificat'ion of the three aminobenzoic acids by alcoholic hydrogen chloride has been determined in the manner described previously for determining the rate of esterifi- cation of benzoic acid and found in presence of only traces of water to increase more rapidly 'than the total concentration of the hydrogen chloride and probably also more rapidly than the excess of hydrogen chloride over that necessary for the formation of the hydrochloride of the amino-acid.This behaviour is more marked in the case of 0- than with m- orpaminobenzoic acid the rate of esterification of these two acids by means of N/3 to 2/3N alcoholic hydrogen chloride being approximately proportional to the concentration of the excess of the hydrogen chloride. On esterification of m-aminobenzoic acid in 0*05-0*06N solution with aqueous alcoholic hydrogen chloride the relation of the velocity constant to the amount of water and of the excess of hydrogen chloride present is represented by the expression 1 /k = 0.87 + 2 1*35/c' + 6.7 1 ~ / c ' ~ ) w ~ when the molecular concentration of the water lies between w =Om02 and w=1.15 and that of the excess of hydrogen chloride is between c' = 0.1 and c' = 0.6 ; with c' = 0.6 the expression applies also to solutions with w = 2.5.The relation of the velocity constant to the concentration of the excess of hydrogen chloride and to the amount of water present is represented in the case of p-aminobenzoic acid by the similar expres- sion l/k = 1Oo1O + 16*27/c' + 0.6692/d2 + ( - 155.5 + 111-13/~' + 3~077/c'~)w + ( - 33-05 + 55*8/c' + 8-136/d2)w2 which applies to solutions with w = 0.02 - 1.34 and c' 3 0.1 - 0.6 or with c' = 0.6 and 0.6088/~'' + (75.62 - 43.09,'~' + 2 2 .6 6 1 ~ ' ~ ) ~ + (-223.0 + 190.5/~' -GENERAL AND PHYSICAL CHEMISTRY. 159 w = 2.4. With about N/3 hydrogen chloride and absolute alcohol the concentration of the p-aminobenaoic acid may be 0 -09N. The hydrolysis of ethyl o- and p-aminobenzoates takes place so slowly as to be negligible in comparison with the rate of esterification. When the action of only the excess of the hydrogen chloride is taken into account the esterification of the aminobenzoic acids resembles closely that of benzoic and the nitrobenzoic acids. G. Y. Boric Acid Amy1 Alcohol and Water. PAUL M~~LLER and RICHARD ABEGG (Zeitsch. phgsikal. Chem. 1907 57 513-532).-The existence of polyborates i n concentrated solutions of boric acid and sodium hydroxide is confirmed but the relationships of these are com- plicated and it is probable that even in dilute solutions several complexes exist side by side.Addition or removal of boric acid seems to affect chiefly the amount of polyborate and only slightly the amount of free boric acid in the solution. By partition experiments in which sodium chloride solutions of various concentrations were shaken up with amyl alcohol it has been shown that in amyl alcohol charged with water there exists a hydrate of the alcohol and it is probable that the hydrate contains 3 molecules of water to 1 molecule of alcohol. I n reaching this con- clusion the authors suppose that the active masses of the free com- ponents of the hydrate are negligibly small in comparison with that of the compound I n aqueoiis amyl alcohol saturated with boric acid there exists not only the aforementioned hydrate but also a com- pound containing 2 molecules of alcohol and 1 molecule of boric acid.The influence of hydroxy-compounds such as lactic acid glycerol and mannitol on the solubility of boric acid in water has been studied and the results obtained throw light on the chemical nature of t h i s influence. When the solubility of boric acid in mixtures of water and methyl alcohol water and ethyl alcohol &c. is determined it is found that the curves representing the variation in solubility with cbanging composition of the solvent mixture all exhibit a minimum. When a C alcohol is part of the solvent the minimum occurs at a smaller percentage of water than when the alcohol present contains n + 1 atoms of carbon.In the case of alcohols not completely miscible with water the tempera- ture coefficients of the reciprocal solubility are opposite in sign for the two phases. J. C. P. Solubilities in Mixed Solvents. IV. Solubilities of Certain Mercury Salts. WALTER HERZ and G. ANDERS (Zeitsch. anorg. CJLem. 1907 52 164-172. Compare Abstr. 1904 ii 709 ; 1905 ii 510 709 ; Sherrill 1903 ii 534).-The solubilities of mercury halides and cyanide have been determined at 25' in the following binary solvents containing the components in varying proportions methyl alcohol and water ethyl alcohol and water and ethyl acetate and water The solubility in methyl alcohol and water increases with the pro- portion of alcohol for the bromide iodide and cyanide but shows a160 ABBTHACTS OF CHEMICAL PAPERS maximum for the chloride at 1 mol.water to 2 mols. alcohol. The observed solubility L is in almost eve* case less than I that calcu- lated from the composition of the solution on the assumption that the components exert their effect independently. Except in the case of the iodide the values of L-Z attain a maximum at intermediate concentrations. I n mixtures of ethyl alcohol and water the solubility increases with the proportion of the former except in the case of the cyanide. In this case also L - I is negative but attains a maximum only for the chloride. Owing to the limited mutual solubility of ethyl acetate and water only a few experiments were carried out with this mixture but in some instances a small change in the composition of the solvent greatly altered the solvent power.With the object of determining whether there is a connexiun between the positions of the maxima of the viscosity curves of the systems and those of L - I several series of viscosity measurements were made but no simple relation between the two properties was discovered. G. S. Intrinsic Movement of Particles in Colloidal Solutions. THE SVEDBERG (Zeitsch. Elektrochem. 1906 12 909-910).-The author’s observations (this vol. ii 17) led him to the conclusions that the amplitude of vibration of a particle is proportional to the time of vibration that is the particles move with constant mean speed and that the curve representing the amplitude as a function of the viscosity of the solution is hyperbolic.He now finds that both these results have been deduced from purely theoretical considerations by Einstein (Ann. Phys. 1905 [iv] 17 549; 1906 19 289). T. E.. New Apparatus for Sublimation. V. SCKWORZOFF (Zeitsch. anyew. Chem. 1907 20 109).-l’he apparatus consists of a small test-tube provided with a porous stopper made of chalk unglazed porcelain or parchment. The substance to be sublimed is placed in this tube which is then introduced into a wider tube the lower end of which can be immersed in an oil or metal bath of known temperature; the upper part of the outer tube is surrounded by a water jacket. The apparatus can be used for subliming very small quantities of material and since the outer tube can be exhausted the sublimation can be carried out under diminished pressure.Improved Liebig’s Condenser. HENRY R. ELLIS (Chern. News 1907 95 52).-A simple device for improving the efficiency of a Liebig’s condenser when used as a reflux for very volatile liquids. It consists in the insertion of a second smaller condenser within the middle tube of a Liebig’s condenser. P. H. W. H. G. A New Desiccator for the Drying of Gases. I\I. I. KUSNETZOFF (J. 122css. Phys. Chem. Soc. 1906 38 ii 453-454).-The apparatus resembles an ordinary potash gas pipette without a side tube but the re- servoir is connected to the pipette by meitus of a removable indiarubberINORGANIC CHEMISTRY. 161 cork. Phosphoric oxide is first introduced into the pipette ; it is then connected with the reservoir which contains mercury and after exhausting the last traces of air by means of a pump the gas to be dried is introduced. Z. K. Apparatus for Crystallising and Filtering in Indifferent Gases. WILHELM STEINKOPF (Ber. 1907 40 400-403. Compare Beckmann Annalen 1892 266).-An apparatus is described i n which substances can be crystallised and filtered by means of a Qooch crucible in an atmosphere of hydrogen or any other gas. J. J. 8. A New Centrifugal Apparatus for Laboratory Use. TH. KORNER (Chem. IZev. Pelt. Ham. I d . 1907 14 34-35).-The apparatus consists of a circular drum having a capacity of from 150 to 500 c.c. and mounted so as t o be capable of being rotated at a high speed. A hole is provided a t the top of the drum through which while the contents are being submitted to centrifugal action is lowered one limb of a siphon made of narrow brass tubing. This end of the tube is bent a t a right-angle so that the velocity of the liquid forces a portion of it through the siphon whence i t is discharged into a receptacle. The siphon is only lowered into the drum when it is considered that separation of solid substances has been attained. The apparatus is suitable for the clarification of solutions of tanning materials &c. w. P. s.

ISSN:0368-1769    

DOI:10.1039/CA9079205145

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

INORGANIC CHEMISTRY. 161 Inorganic Chemistry. The Constitution and Configuration of Inorganic Com- pounds. ALFRED WERNER (Ber. 1907 40 15-69).-A lecture delivered before the German Chemical Society. A. McK. Decomposition of Hydrogen Peroxide Solutions. AUGUST FISCHER (Pharnz. Centr-h. 1907 48 57-65 79-84).-An investi- gation of the decomposition of aqueous solutions containing 1 to 25% of hydrogen peroxide at 15" ZOO and 25'. The solutions were prepared by dilution of a 30% solution (Merck's Perhydrol) and i?i is shown that this is accompanied by a slight decomposition (0.1 to 0.3%); further that under the above conditions a t 15' and 30° solutions containing 6 t o 8% of hydrogen peroxide decompose most rapidly (roughly 50% in 6en days); a t 2 5 O those containing 2 to 10% of hydrogen peroxide with approximately equal rapidity (roughly 65% after ten days).Increase of concentration above 6% at 15' and 20° and above 10% a t 25' is accompanied by an increase in stability. Various factors such as the presence of dust the quantity of solution in the bottle &c. influence the rate of decomposition. Decomposition apparently ceases when the pressure of oxygen within the bottle is VOL. XCII. ii. 12162 ABSTRACTS OF CnEMICAL PAPERS. sufficiently great. The decomposition is prevented to a large extent and to about the same degree by the presence of very small quantities of hydrochloric and sulphuric acids; phosphoric acid is not quite SO effective but is better than boric acid. Contrary to Arth’s state- ment (Chem. Zeit. 1901,568) oxalic acid does not decompose hydrogen peroxide but when present in quantities varying between 0.1 and 2% prevents decomposition to a greater degree than either hydrochloric or sulphilric acid.Dry Method for the Generation of Oxygen from Sodium Peroxide. HAROLD J. TURNER (Amer. Chem. J. 1907 37,106-107). -In reactions depending on the action of water and apt t o become violent salts containing water of crystallisation may with great advantage be used in place of water. When a mixtnre of fused sodium peroxide and crystalline sodium sulphate or carbonate is gently warmed oxygen is evolved in a steady stream. The prepara- tion of small quantities of the gas for laboratory or lecture purposes can be conveniently effected in this way. A similar method has been adopted recently for the decomposition of calcium carbide on a large scale.Continuous Apparatus for Preparing Pure Oxygen for Use in Organic Analysis. ALPHONSE SEYEWETZ and POIZAT (Compt. rend. 1907 144 86-87).-A steady evolution of oxygen under sufficient pressure for use in organic combustions is obtained when a solution of 25 grams of potassium permanganate in 500 C.C. of water and 50 C.C. of concentrated sulphuric acid is allowed to flow from a dropping funnel into a litre flask containing 500 C.C. of hydrogen peroxide (10 vol.). The longer limb of a siphon passes through the coxk of the flask and is bent in such a way that the permanganate solution drops on to the tube instead of directly into the peroxide solution; by this means a steadier flow of oxygen is obtained.The siphon serves to empty the Bask and to introduce a fresh charge. The oxygen thus obtained contains traces of chlorine from the hydro- chloric acid which is a common impurity of hydrogen peroxide and of ozone. M. A. W. W. H. G. E. G. Preparation of Ozone by Electrolysis. FRAKZ FISCHER and KARL MASSENEZ (Zeitsch. anorg. Clbem. 1907 52 202-218. Com- pare McLeod Trans. 1886,49,591 ; Kremann Abstr. 1904 ii 24).- The paper contains the description of an electrolytic method by which oxygen containing a very high proportion of ozone can be obtained without destruct ion of the electrodes. The apparatus is made of glass and consists of two side cathode compartments and a middle anode compartment. The latter contains two glass tubes bent towards each other at their lower ends and joined by a narrow platinum tube which serves as electrode and is kept cool by a continuous current of water being passed through the interior.The arrangements for collecting and analysing the gases are given in detail. I n agreement with McLeod (Zoc. cit.) it was found that sulphuricINORGANIC CHEMISTRY. 163 acid D 1*075-1*1 gave the best results and a current density of 58 amperes per sq. cm. proved most efficient. The chief iaprovement in the method is as to the best size and shape of the anode and in the observation that when the anode surface is rendered smooth or (' polished " by electrolysing for a short time with strong acid i t gives much higher yields of ozone. I n the final form the platinum tube was sealed over completely and then a thin strip 6 mm.long and 0.4 mm. broad exposed. I n this way long contact of the ozone with the platinum surface (which decomposes the gas) is avoided and a gas containing a little over 17% of ozone by weight is obtained the electrode remaining unaffected even after long use. G. S. Thermal Relationships between Ozone Nitric Oxide and Hydrogen Peroxide. 11. FRANZ FISCHER and HANS MARX (Ber. 1907 40 443-458. Compare Abstr. 1906 ii 845).-In continua- tion of former work (Zoc. cit.) the authors have studied the influence of the temperature of the Nernst filament used the influence of the form of the aperture t,hrough which the air was passed and the influence of the temperature of the air passed through the slit. With increase of the temperature of the filament the concentration of ozone in the air increases in the manner demanded by theory.The temperature of the filament on the side on which the air was blown was determined by the light emission per square millimetre. When moist air is used the temperature of the filament has a similar effect on the yield of hydrogen peroxide so that it is experi- mentally established both for ozone and hydrogen peroxide that. the concentration of these endothermic products increases with the temperature. The form of the aperture through which the air is blown has an important influence on the yield of gases. A. double aperture is most efficient . The highest concentration of ozone obtained by blowing air on the filament was 0.03% by weight calculating on air and 0.13% by weight calculating on the oxygen contained in the air.The influence of the temperature of the air blown on to the filament is slight up to 60'. When warm air at about 60' is used the ozone yield falls to about SO% of the value obtained by using air at about 5'. If 96% oxygen is blown on to the filament instead of air the influences of the experimental conditions are analogous t o those which obtain in the case of air. If the oxygen is moist the yield of ozone is very considerably diminished whilst hydrogen peroxide is formed. The maximum yield of ozone in the cases where oxygen is used is attained when the rate of flow of the oxygen is slow. A. McK. Synthesis of Hydrogen Sulphide. JAROSLAV MILBAUER (Ann. Chim. Phys. 1907 [viii 1 10 125-129).-Hydrogen was passed over melted sulphur (alone or mixed with a catalytic agent) maintained ut R constant temperature and the amount of hydrogen sulphide formed 12-2164 ABSTRACTS OF CHEMICAL PAPERS.per hour was estimated by means of staadard iodine solution. It mas found that the rate of formation of hydrogen sulphide was not accelerated by the presence of the sulphide of any one of the following metals silver gold mercury thallium arsenic molybdenum platinum or by metallic mercury or palladium but was increased by platinum black or red phosphorus The acceleration in the latter case is possibly due to the occurrence of the following reactions P2S5 + 8H2 = ZPH + 5H2S and 2PH + 45 = P2S + 3H2S. The rate of formation of hydrogen sulphide by the action of hydro- gen on sulphur alone increases continuously with rise of temperature but in presence of red phosphorus the maximum rate is attained a t 2 1 8 O after which it diminishes up to 278".The rate of formation in the case of sulphur and hydrogen alone is greater when the sulphur. has been heated almost to boiling and then cooled to 278O which indi- cates as Bodenstein has shown (Abstr. 1899 ii 638) that the transformation S 4S takes place more slowly than 5 2s. T. A. H. Preparation of Hydrogen Sulphide. HENRI FONZES-DIACON (BUZZ. Xoc. chim. 1907 [iv] J 36-37. Compare Abstr. 1900 ii 405).-Aluminium sulphide A12S is prepared by closely packing a mixture of powdered aluminium and sulphur in a crucible lined with magnesia and igniting the mixture by means of lighted magnesium ribbon. The sulphide is placed in a dry flask provided with a stopper carrying (1) a tap funnel from which water can be allowed to drip slowly on the sulphide ; (2) a mercury manometer and (3) a leading tube with a stop-cock.The evolution of hydrogen sulphide can be stopped almost at once by cutting off the supply of water and closing the delivery tube. T. A. H. Formation of Hyposulphites. EUGBNE GRANDMOUGIN (Bull. Xoc. ind. MuZhouse 1906 76 351-356).-The use of iron for the reductmion of sodium hydrogen sulphite on a commercial scale (Schiitzenberger Compt. rend. 1869 69 200) is not very successful. The action of sodium on sulphur dioxide in presence of ethyl ether or alcohol (Abstr. 1904 ii 250) is very slow and gives a very bad yield. Sodium at its melting point does not appreciably combine with dry sulphur dioxide and does not act on liquid sulphur dioxide at - loo but when kept for fifteen days in liquid sulphur dioxide in a sealed tube at 20° a small quantity of sodium hyposulphite is formed.Sodium acts on concen- trated solutions of sodium hydrogen sulphite with explosive violence and more slowly on more dilute solutions but in neither case is any hyposulphite formed. Sodium amalgam readily reduces solutions of sodium hydrogen sulphite to the hyposulphite but the method is not valuable industrially. Calcium has no action on liquid sulphur dioxide b u t readily reduces solutions of the hydrogen sulphite to the hyposulphite. The stability of sodium hyposulphite solutions is increased bg adding alkali hydroxides sodium sulphide o r reduced indigo (compare Meyer Abstr.1903 ii 285). E. H.INORGANIC CHEMISTRY. 165 Colloidal Selenium. P. I. KHOLODNY (J. Rugs. Phys. Chem. SOC. 1906 38 ii 127-147).-The solutions of colloidal selenium used by the author were prepared by dissolving in water the red selenium precipitated on reducing selenium dioxide by means of sulphur dioxide (compare Schulze Abstr. 1886 302). Such solutions are blood-red but if sufficiently diluted with water assume an orange tint. They are moderately stable and only slightly opalescent and are considerably more transparent than silver solutions of corresponding concentration. The precipitation of the selenium from a 1.5% solution by means of various acids alkalis and salts was investigated. The density of colloidal selenium mas determined by taking advantage of the observa- tion that when its solution is treated with carbon disulphide the latter removes the whole of the selenium from solution. If then A represents the weight of the colloidal selenium solution B the weight of the solution of the same volume of the impurities alone M the weight of the colloidal selenium 8 the density of the solution of the impurities and x the required density of the colloidal selenium A = B + M - M6/x.The application of this method to colloidal solutions containing from 5 to 10% of selenium gives a constant value DS 4.26-4.27 for colloidal selenium. The constancy of this value for solutions of different concentrations indicates that the solution of the selehium occurs without diminution of the total volume of solvent and solute.The above value for the density of colloidal selenium agrees with that given by various authors for the density of amorphous selenium. T. H. I?. Absorption of Nitrogen and Hydrogen by Aqueous Solu- tions. GUSTAV VON H~FNER (2eidsch.physikaZ. Chenz. 1907 57 611- 625)-The absorption coefficients of nitrogen and hydrogen in solutions of dextrose laevulose arebinose erythritol aminoacetic acid a-aminopropionic acid carbamide and acetamide hsve been determined. On the whole the extent to which the absorption coefficiont falls away from the value for pure water is proportional to the absolute weight of the solute present. The chief exceptions to this rule occur in the cases of acetamide and the two amino- acids. J. C. P. Hydrazoic Acid [Azoimide].LOUIS M. DENNIS and HELEN ISHAM (Bey. 1907 40 458-468).-The authors describe the pre- paration of anhydrous azoimide by the action of sulphuric acid on potassium trinitride. The various precautions taken to minimise the danger from explosion are given in detail. The azoimide so obtained which is practically pure (99*94%) has m. p. - 80' and b. p. 3 7 O the latter value being in accordance with that quoted by Curtius and Radenhausen (Abstr. 1891 524). It is a colourless mobile liquid at the ordinary temperature and may be kept in a sealed tube for several days without undergoing decomposition. The authors did not find that azoimide exploded spontaneously on any occasion. The explosion is extremely violent when the acid is shaken or when it is strongly heated.166 ABSTRACTS OF CHEMICAL PAPERS.The vapour density determined at a temperature 2 5 O above the boiling point indicated the unimolecular formula HN for szoimide. A. McK. Products Formed from Carbon Nitrogen and Carbonates of the Alkaline Earths. OTTO EUHLING (Ber. 1907,40,310-319).- An examination of the relative quantities of cyanide and cyanamide obtained by heating sugar charcoal ( 3 atoms) with the pure carbonates of barium strontium and calcium (1 mol.) in a stream of moist or dry nitrogen free from carbon dioxide and oxygen a t temperatures varying from 900° to 1400O. The results obtained show that the tendency to take up nitrogen falls with decreasing atomic weight. A t 1050- l l O O o barium carbonate gives 23.4% of cyanide and 1.6% of cyanamide; strontium carbonate at 1200-1 250° 1.4% and 0.8% respectively and calcium carbonate at 1350-1400° does not form a trace of either.The effect of adding the corresponding chloride to the mixture is to increase the percentage of the cyanide and cyanamide. The paper contains a summary of the patent literature bearing on the subject. W. R. Solubility of Carbon in Barium and Strontium Carbides. H. MOREL KAHN (Compt. rend. 1907 144 197-199. Compare Abstr. 1906 ii 538).-When barium carbide in a charcoal crucible is subjected t o a current of 550-600 amperes at about 90 volts for six minutes it takes up from 1.25% to 1.50% of carbon and the amount increases with time until after eleven minutes from 5.40% to 6920% of carbon is dissolved. On longer heating the rariations in the amount of carbon dissolved are considerable and do not depend on the solubility of the carbon.Under the same conditions strontium carbide dissolves 1.3% to 1.5% of carbon in six minutes and 6.15% to 6.25% in ten minutes. The results are entirely similar to those obtained with calcium carbide. E. H. Methods of Investigation of Silicate Fusions. CORNELIUS DOELTER (Centr. Min. 1907 1-2).-An answer to the remarks of Day and Shepherd (Abstr. 1906 ii 770) on the methods employed for the determination of the melting points of silicates. It is main- tained that the optical method leads to as accurate results as the thermal method. L. J. S. Preparation of Pure Helium by Filtration of the Gases from Cleveite through a Quartz Diaphragm. ADRIEN JAQUEROD and F. LOUIS PERROT (Compt.rend. 1907,144 135-136. Compare Abstr. 1905 ii lo).-Quartz is quite impermeable to all gases except hydrogen helium and perhaps carbon monoxide up to 1067". This is the basis of a method of obtaining pure helium from the cleveite gases. The latter together with about 5% of oxygen (for the oxida- tion of hydrogen and carbon monoxide) is introduced into the annular space between a platinum cylinder and a quartz bulb placed within it at rather more than atmospheric pressure. When the apparatus is heated to about l l O O o and the quartz bulb evacuated heliumINORGANIC CHEMISTRY. 167 diffuses through. The method although very slow effects almost complete purification spectroscopic examination of the gas showing the red hydrogen line only faintly and the nitrogen bands not at all.E. H. Two Chemical Compounds each containing Three Metals. ERNST JANECHE (Zeitsch. physikal. Chem. 1906 57 507-51O).-A study of freezing-point curves for systems of thiee metals has led to the recognition of the compounds NaKHg (m. p. 1 8 S O ) and NaCdHg (m. p 325'). J. C. P. Lithium Subchloride. ANTOINE GUNTZ (Ann. Chim. Phys. 1907 [viii] 10 13-23. Compare Abstr. 1896 ii 299 358).-The pro- duct obtained by heating lithium chloride with lithium in it current of hydrogen is not as previously supposed by the author lithium subchloride Li,Cl but a mixture of lithium hydride and chloride. Attempts to prepare the subchloride have been made (1) by heating a mixture of lithium hydride and chloride a t 880" under reduced pressure; (2) by heating a mixture of lithium chloride and lithium in presence of argon and (3) by heating a mixture of lithium and lithium chloride in a hermetically sealed steel crucible plunged in a bath of melted calcium chloride.The products obtained were analysed and in no case could the formation of the subchloride be definitely established although the results obtained are compatible with the view that small quantities of the salt may have been formed. Similar results have been obtained by Guntzand Baesett in the case of calcium (Abstr. 1906 ii 540). Bunsen's failure to obtain rubidium by the electrolysis of the chloride was probably due t o the formation of rubidium hydrids and not to the production of rubidium subchloride as he supposed. The dissociation of an alkali hydride when dissolved in the chloride of the same metal may under certain conditions give rise t o a finely-divided deposit of the metal and the formation of a coloured product which may be mistaken for the subchloride (compare Wohler and Kasarnowski Abstr.1906 ii 22). T. A. H. Solubility of Alkaline Earths in their Molten Chlorides KURT ARNDT (Bey. 1907 40 427-431).-The experiments were carried out in an Heriius crucible electric furnace for 110 volts and 2 amperes provided with a Le-Chatelier pyrometer and a rheostat. The determinations were made in two ways by heating the chloride and its corresponding oxide in a platinum or porcelain crucible and estimating the % of alkali in the saturated fused mass or by studying the cooling curves and so obtaining the equilibrium between solvent and solute.In round numbers 1 molecule of calcium strontium and barium oxides are dissolved by 7,3 and 2 molecules of their respective chlorides. In the case of the barium chloride mixed crystals containing 17.7% BaO were isolated. Fluorspar has practically no influence on the solubility of lime i n calcium chloride. W. R. Bleaching Powder. EUGEN SCHWARZ (Zeitsch. angew. Cltem. 1907 ZO 138-143).-The author discusses the views recently published on168 ABSTBACTS OF CHEMICAL PAPERS. the composition of bleaching powder (compare Ditz Abstr. 1899 ii 26 ; 1901 ii 239; 1902 ii 656 ; Winteler Abstr. 1903 ii 145; 291 ; Tiesenholt Abstr. 1902 ii 562 ; 1906 ii 163). Strontium hydroxide ’in the solid state and in solution is shown to be analogous with calcium hydroxide in its behaviour .towards chlorine. A strontium bleaching powder cannot be obtained containing such a high proportion of ‘‘ bleaching ” chlorine as ordinary bleaching powder but in other respects the products are practically identical. The action of chlorine monoxide on calcium chloride has been studied. The amount of water present influences the reaction to a great extent anhydrous calcium chloride not being attacked whereas with 30% of water calcium hypochlorite is first produced which under prolonged action of the chlorine monoxide is converted into chlorate. A sample of the product containing a high percentage of hypochlorite is stable in dry air is not decomposed readily by carbon dioxide when dry but fairly readily when moist. A “synthetic” bleaching powder prepared by mixing some of this product with calcium chloride and containing roughly the same percentage of ‘‘ bleaching ” chlorine as commercial bleaching powder when treated with moist carbon dioxide gives off slowly an amount of chlorine corresponding with that present as hypochlorite only whereas ander the same treatment the com- mercial product parts with 80% of its bleaching chlorine.The author therefore concludes that bleaching powder is not a mere mixture of calcium chloride and calcium hypochlorite but consists principally of the compound CaOCI,; carbon dioxide acts on this liberating hypochlorous acid which in the nascent state reacts with the chloride portion of the molecule converting this into hypochlorite which is susceptible to further decomposition by the carbon dioxide.W. H. G. Two New Ammonium Calcium Sulphates. JOR. D’ANs (Ber. 1907 40 192-194. Compare Abstr. 1906 ii 751; Ditte this journal 1877 i 440 ; Bell and Taber Abstr. 1906 ii 352).- Ammonium pentacalciuna sulphate Ca,( NH,),( SO,),,.H,O prepared by boiling calcium sulphate with 30% aqueous ammonium sulphate in a reflux apparatus crystallises in strongly refracting prisms and closely resembles tbe analogous potassium salt (van’t HOB Abstr. 1904 ii 561). On boiling calcium sulphate with 40% aqueous ammonium sul- pbate ammonium dicalcium sulphate Ca,(NH,)2(S0,) is formed ; this crystallises in pentagonaldodecahedra and decomposeson prolonged boiling with the mother liquor forming syngenite and ammonium pentacalcium sulphate or in contact with the cooled mother liquor forming syngenite.Both OF these new double salts are decomposed by water. G. Y. Reversible Action of Oxygen on Magnesium Chloride. FRITZ HABER (Zeitsch. ccnorg Chem. 1907 52 127-128).-A com- parison of the papers published simultaneously by Moldenhauer (this vol. ii 85) and by Haber and Fleischmann (ibid. ii 84) on the equilibrium between magnesium chloride and oxygen has made it clear that the partial pressures and constants in the table given by theINORUANIC CHEMISTRY. 169 latter observers do not correspond. Although the general results oE the investigation are not thereby affected a recalculation of the observations and if necessary a repetition of some of the bxperiments are rendered necessary ; the proper values will be communicated later. It is pointed out that the so-called "concentrations" of the re- acting gases given in Moldenhauer's paper are really partial pressures expressed in hundredths of an atmosphere.Solubility of the Hydrates of Magnesium Bromide and Iodide. BORIS N. MENSCHUTKIN (Zeitschr. anory. Chem. 1907 52 152-158. Compare Abstr. 1906 i l31,132,552,943).-Magnesium bromide hexahydrate was obtained pure by decomposing the dietherate with water and its solnbility,in water determined from 0" to its melt- i n g point 164'. The solubility at 18" agrees exactly with that found by Mylius ?nd Funk (Abstr. 1897 ii 442) but not with the value ob- tained by Etard (Abstr. 1894 ii 442). The solubility curve is com- pared with those of the Corresponding alcoholates (Zoc.cit.). Magnesium iodide octahydrate Mg12,SH20 was obtained by the action of water on the corresponding dietherate and its solubility in water determined from 0' to its melting point 43.5". The solubility of the hexabydrste the stable solid phase above 43*5O has been deter- mined from the latter temperature to 215". Of the three hexahydrates the chloride is the least and the iodide the most soluble. G. S. G. S. Behaviour of Magnesium Hydrogen Carbonate when its Solution is Boiled. R. RINNE (Chern. Zeit. 1907 31 125-126).- Magnesium hydrogen carbonate was prepared by the action of carbon dioxide on pure magnesia suspended in distilled water. Aqueous solutions of this magnesium carbonate were found not to deposit a.11 their dissolved magnesia even on boiling for some time.P. H. Solvent Action of Water on Zinc in Brass. JOHANNEY H. ABERSON (Chenz. JVeekbZad 1907 4 32-34).-The solvent action of soft water on the zinc in the brass gauzes and their supports in the reservoir-filters a t Wageningen was investigated. The corrosion rendered the supports very brittle due to their transformation into &n outer crust and an inner core which mere only feebly united. Some- times the core was wanting. The brass gauze was also corroded. Analysis of the outer crust showed a deficiency in zinc of about 6% and of the gauze a deficiency of about 27% and a corresponding increase in the percentage of copper it1 each case. The zinc was estimated as oxide and the copper electrolytically. The author attributes the action to the softness of the water the surface of the alloy not being coated with carbonate.The oxygen present con- tinually renewed by pumping converted the zinc into oxide which then dissolved as zinc hydrogen carbonate. The solution of the zinc mas also facilitated by electrolytic action due to soldered joints. The author has noticed the solvent action of this water on zinc and lead and considers that filters for very soft water should be constructed without brass. A. J. W.170 ABSTRACTS OF CHEMICAL PAPERS. Zinc-Tliallium and Zinc-Iron 4lloye. A. vox VEGES ACK (Zeitsch. anorg. Chem. 1907 52 30-40. Compare Heycock and Neville Trans. 1897,71 383).- Zinc and thallium have only a limited mutual solubility. At its melting point zinc dissolves about 2.5% of thallium the melting point of the former metal being thus lowered about 3'; at the melting point of thallium the latter metal dissolves about 5% of zinc and its melting point is lowered about 4'.The mutual solubility curves could not be determined owing to the thermal effects on admixture being very slight. There is no indication of chemical combination between the two metals and they show practically no tendency to form mixed crystals. The freezing points of alloys of zinc anci iron up to about 24% of zinc have been determined and indications of the existence of the compounds FeZo and FeZn7 have been obtained. From alloys containing 11-24% of iron there is a primary separa- tion of crystals of unknown composition which react a t 777' with the fused mass to form the compound FeZn,.The latter separates primarily from alloys containing 4-11% of iron but when the temperature falls t o 662' it reacts with the fused mass to form the compound FeZn7. The two compounds seem to be miscible to a slight extent in the solid form. The compound FeZn forms a series of mixed crystals which are saturated when 7.3% of iron is present. Below 442O the saturated mixed crystals react with the fused mass to form another series of mixed crystals extending from 0*7-'7.3% of iron. The results were confirmed by microscopic examination. Alloys containing 0*7-11% of iron become harder and more brittle with increase in the amount of the latter metal ; those contain- ing over 5% of iron are porous. The compounds FeZn and PeZn,. are also porous and very brittle. G.5. Action of Carbon Dioxide on Metallic Hydroxides. PAUL N. RAIKOW (Chem. Zeit. 1907 31 55-57 87-89. Compare Abstr. 1905 ii %).-Carbon dioxide is passed into the mixture obtained by adding t o a normal solution of metallic salt a quantity of potassium hydroxide sufficient to convert about one-fifth of the metal into hydroxide; the increase in weight due t o combination of carbon dioxide with the metallic hydroxide is then observed. Under these conditions magnesium hydroxide is converted completely into the hydrogen carbonate zinc and cadmium hydroxides into normal carbon- ates mercuric oxide chiefly into the normal carbonate a small quantity of an acid carbonate also being formed ; neither mercurous oxide nor glucinum hydroxide combines with carbon dioxide in the latter case probably owing to the formation of a soluble basic glucinum sulphate stable towards carbon dioxide Freshly precipitated glucinum hydr- oxide suspended in water is however under the same treatment appareptly converted into the basic carbonate BeCO 3 Be(OH) Aluminium chromium and ferric hydroxides do not combine with carbon dioxide under this treatment whereas zirconium lanthanum cerous and ceric hydroxides are converted into the respective normal carbonates ; although cerous carbonate is usually described as being white that obtained under tbese conditions is yellow ; thallous hydr-INORGANIC CHEMISTRY. 171 oxide j8 converted completely into the hydrogen carbonate ; yttrium hydroxide into the basic carbonate 3~2(C03),,2Y(OH) and not into the normal carbonate obtained by Gleve by passing carbon dioxide into water containing yttrium hydroxide in suspension ; ferrous and manganous hydroxides are converted chiefly into their respective normal carbonates a small quantity of an acid carbonate also being formed in each case.Freshly precipitated aluminium chromium and ferric hydroxides when suspended in water do not combine with cEtrbon dioxide. W. H. G. Action of Carbon Dioxide on Metallic Hydroxides. PAUL N. RAIKOW (Chern. Zeit. 1907 31 141-143. Compare preceding abstracts).-An excess of carbon dioxide converts nickel hydroxide into a carbonate of the formula Ni,H,(CO,) ; this substance is fairly soluble in a solution saturated with carbon dioxide but as this gas escapes from the solution the carbonate is thrown out.An analogous experiment carried out with a cobalt salt led to no definite result. Freshly precipitated copper hydroxide suspended in water is not acted on by carbon dioxide in the absence of air. Cuprous hydroxide is first converted into a carbonate of the formula Cu,H(CO,) which however subsequently decomposes completely. Silver only gives a normal carbonate. Freshly precipitated lead hydroxide is converted by an excess of carbon dioxide into normal lead carbonate. The investigation has brought to light the existence of new types of carbonates namely the 1/4 saturated nickel carbonate N$H2(CO3)4 and the 3/4 saturated NICOLAI S. KURNAKOFF and A. N. KUSNETZOFF (Zeitsch. unorg. Chemn,. 1907 52 173- 185. Compare Abstr. 1900 ii 277 ; Heycock and Neville Trans.1889 55 673).- The investigation of the system cadmium-sodium by thermal and microscopic methods shows that the metals form two compounds of the respective formuls NaCd and NaCd,. The freezing-point curve of the system shows two maxima a t 384O and 33-3 atom. % and 363' and 14.25 atom. % of sodium respectively corresponding with the compounds NaCd and NaCd as well as three eutectic points at 95.4' and 99.3% 351' and 19*2% and 291' and 5.5 atom. % of sodium respectively. From 14.3 to 17% of sodium 8 series of mixed crystals separates. The compound NaCd occurs in well-formed octahedral crystals has DSo 5.669 and is only slowly acted on by water; its crystallographic constants have also been determined. The compound NaCd occurs in cubic crystals. G. S. copper carbonate Cu,H(C03),.P. H. Cadmium-Sodium Alloys. Preparation of Pure Praseodymium Compounds. N. A. ORLOFF (Chem. Zeit. 1907 31 115).-A method for separating praseo- dymium completely from lanthanum. The praseodymium compound containing lauthanum only as impurity is boiled with a solution of potassium. permanganate and mercuric oxide to which a solution of cerium chloride is then gradually added. The precipitate obtained consists of the higher oxides of cerium and praseodymium whilst the172 ABSTRACTS OF CHEMICAL PAPERS. lanthanum remains in solution. from the cerium by any of the usual methods. The praseodymium is then separated W. H. G. Separation of the Earths of the Yttrium Group. ANTON BETTENDORFF (Annulen 1907 352 88-1 lO).-After separating the oxides of tbe cerium group from the mixed oxides obtained from orthite the residue is treated with formic acid and the formates so produced are separated by repeated fractional crystallisation into three principal fractions which give oxides possessing the equivalents RO= 120.0 91.7 and 80.5 respectively.The earth R”O = 120.0 dissolved in nitric acid and freed from traces of didymium and samarium by using potassium sulphate (corn[ are Bettendorff Abstr. 1890 S5l) gave by partial precipitation with dilute ammonia a brown oxide (RO = 121.57) and a very light yellow oxide(R0 = 119*90) in other word9 the nearly pure oxides of terbium and gadolinium. ‘By repeated partial decomposit’ion of the nitrates of the oxide (RO = 91.7) two fraction? RO = 82.0 and .RO = 103.4-105.0 were finally obtained ; the chloride of the fraction RO = 83.0 gave an intense yttrium spark-spectrum ; the concentrated solution of the nitrates of the oxides KO = 103*4-105*0 gave by treatment with sodium sulphate sparingly soluble double sulphates of a yellow oxide RO = 119-120 practically identical with that obtained above from the formstes least soluble in water (RO = 120.0).From the fraction RO = 80.5 by using Rowlandts method . namely systematic pre- cipitation from the acidified solution of the nitrates a white oxide RO = 75.17 was obtained finally ; since a solution of its nitrate did not show any absorption band in its spectrum i t is probably pure yttrium oxide. The mixture of oxides obtained from gadolinite after separation of the oxides of the cerium group could not be further separated by fractional crystallisation of tbe double sulphates ; by employing von Welsbach’s oxide method of separation however the following fractions were obtained ytterbium material erbium material and yttrium material.From the ytterbium material (RO = 130*75-131*8) by fractional precipitation with ammonia were obtained three fractions RO= 131.0 131.5 131.8 ; i t is at present impossible to say which represents the purest ytterbium compound. From the erbium material using von Welsbnch’s method the following fractions were obtained RO = 129*0-127.0 ; 126.5 123.0 and 120.0. As the ytterbium is gradually separated by fractional precipitation with ammonia from the fraction RO = 127-129.0 the oxide loses its rose-red colour becoming yellowish-brown RO = 126.5 ; the author therefore concludes that the rose-red oxide (RO = 126.63 R”’=166.0) usually supposed t o be erbium oxide is an impure ytterbium oxide coloured red by an oxide of smaller equivalent weight and stronger ‘basic properties probably thulium oxide ; thulium is present in large quantities in the fraction RO = 127-129.The oxides It0 = 126.5 were not further separated. The oxides RO = 119-124 gave what appeared to be an oxide with the constant value RO= 124.7 but t h i s could not be .further investigated owing t o the small quantity obtained. Since the absorption spectrum of the1 N ORCf A N I C CH EM ISTR r. 173 nitrate solution of this fraction RO = 119-124 shows not only the presence of erbium but also of holmium whereas the absorption spectrum of the solution of the nitrate of the terbium oxide .obtained from orthite shows the presence of holmium and not erbium it follows that holmium is separated much more readily from erbium by means of a supersaturated solution of sodium sulpbate than by partial precipitation with ammonia. By using Bowland's method (Abstr.1894 ii 449) it was possible t o obtain from the yttrium material (RO = 81.4) a yttrium oxide RO = 76.0 containing however traces of didymium; by treating the nitrate o€ this oxide with potassium sulphate it was possible to free it from didymium ; the oxide then had the value RO = 75.33 ; this value remained unchanged even after further treatment by Rowland's method. The spectrum of the sulphate of the yttrium oxide (RO = $5.16) from orthite although very similar is not identical with that of the sulphate of the yttrium oxide (RO = 75.33) from gadolinite ; this latter oxide appears to contain the oxide of a yet unknown element.Double Ammonium Lead Chlorides. HARRY W. FOOTE and L. H. LEVY (Anzer. Chem. J. 1907 37 119-123).-The ammonium lead chlorides which crystallise from aqueous solutions a t 25' have been examined by heating weighed quantities of ammonium chloride and lead chloride with a known quantity of water allowing t o crystallise at 25O and then to ensure equilibrium shaking for several days in a thermostat at the same temperature. The solubility data indicate that the only double salt has the composition NH4C1,2PbCI,. No evidence was obtained of the existence of the double salts 2NH4C1,PbCI and NH,Cl,PbCI,,H,O which have been described previously.H. M. D. Double Czesium Lead Bromides. HARRY W. FOOTE (Amer. Chem. J. 1907 37 124-126).-The conditions of formation of the known double bromides of cssiurn and lead have been determined at 25O by solubility measurements. The following are mean values for the composition of the aqueous solutions satorated with respect to the compounds in the first column W. H. G. % CsBr % PbBr in solution in solution PbBr .t CsBr,ZPbBr2 ......... 0.28 ......... 0.32 CsBr,2PbEr2 + CsBr,PbBr ......... 17.75 ......... - CsBr,PbBr + 4CsBr,PbBr ......... 36.80 ......... - 4CsBr,PbBr2 + CsBr ......... 54.43 ......... - CsBr ......... 55.23 - ......... H. M. D. Action of Carbon Dioxide on Aqueous Solutions of Lead Acetate. ARTUR ALTMANN (Zeitsch.anorg. Chem. 1907 52 219-288).-Solutions of lead acetate from N/50 to 2 N were precipitated by excess of carbon dioxide a t intervals of temperature from O-lOOo and the precipitates analysed. The proportion of the salt precipitated (as normal carbonate) decreases with rise of tempera- ture and increased concentration of the acetate.174 ASSTRACTS O$ CBlZMICAL PAPERR. From solutions heated at looo for some. time in a reflux apparatud the normal carbonate is precipitated but when the heating is carried out in such a way that the acetic acid set free by hydrolysis accord- ing to the equation Pb(C12H302)2 + H,O = OH*Pb*C2H,02 + C2H,02 is allowed to escape the precipitate obtained with carbon dioxide from dilute solutions consists of the basic salt 2PbCO,,Pb(OH) whilst from strong solutions mixtures of the latter salt and normal carbonate are precipitated G.S. Alloys of Copper and Nickel. W. GUERTLER and GUSTAV TAMMAN? (Zeitsch. anoyy. Chem. 1907 52 25- 29. Compare Gautier Abstr. 1806 ii 646).-The freezingpoint ciirve of copper-nickel alloys falls regularly from the melting point of nickei to that of copper indicating that the metals form a continuous series of mixed crystals; the curve is slightly concave t o the axis of composition. Pure nickel has a transition point at 320" above which i t is no longer magnetic ; the transition temperature is progressively lowered by addition of copper and occurs a t about 30" when 42% of the latter element is present The deductions from the freczing-point observations are borne out by a microscopic examination of etched surfaces ; even in slowly-cooled alloys however the mixed crystals are not quite homogeneous.G. S. Electrolytic Formation of Copper Peroxide. ERICH MULLER and FRITZ SPITZER (Zeitsch. Elektrochem. 1907 13 25-37).-When a solution of cupric oxide in a very concentrated solution of sodium hydroxide is electrolysed a yellow substance is formed at the anode which behaves like a peroxide. The same substance is produced when 12N sodium hydroxide is electrolysed with a copper anode at low temperatures with a current density of about 0.2 ampere per sq. cm. The ,substance decomposes into oxygen and copper oxide and cannot be obtained in a pure state. By comparing the loss of weight of the anode with the quantity of electricity used and the quantity of oxygen evolved it is found that the copper dissolves in the tervalent condition ; the substance may therefore be Cu,O,.T. E. Cuproua Metaphosphate. VICTOR AUGER (Compt. rend. 1907 144 199-200).-When metaphosphoric acid heated to dull redness is added t o excess of copper turnings contained in a platinum capsule provided with a lid and heated to a similar temperature the copper dissolves with evolution of hydrogen and the mass becomes brown. The latter is immediately oxidised by air but if the mass is poured off from the unattacked copper into a platinum crucible and protected from air on cooling it deposits lamellae of copper in weight equal to that subsequently found in the residual mass in the form of cupric phosphate.The cuprous metaphosphate formed is thus stable at a red heat but decomposes on cooling into cupric metaphoaphate and copper. If the fused mass of cuprous metaphosphate dissolved in excess of metaphosphoric acid is allowed to fall in small drops into methylI~ORGTANIC CHEMISTRY'. 175 chloride transparent vitreous pale yell0 w beads of cuprous meta- phosphate dissolved in excess of metaphosphoric acid are obtained. These can be kept in a sealed tube for some days but gradually become reddish-brown and opaque. The change occurs immediately on warming. E H. A New Silicide of Manganese Described. by Gin. PAUL LEBEAU (Compt. ?*end. 190'7 144 S5-S6).-Polemical against Gin. The crystalline manganese silicide described by Gin (this vol. ii 02) is probably an impure specimen of the compound SiMn discovered by Vigouroux (Abstr.1896 ii 249) and reproduced by the author (Abstr. 1904 ii 343). M. A. W. Colloidal Ferric Hydroxide. IV. Preparation of Colloidal Ferric Hydroxide in Presence of Barium Nitrate Potassium Chloride and Potassium Nitrate. A. 'V. DUMANSKY (J. Rum Phys. Chem. Xoc. 1906 38 595-596. Compare Abstr. 1905 ii 714). -The author regards colloidal solutions of ferric hydroxide as emulsions of very small bubbles the walls of which consist of the colloidal sub- stance and the contents either of the solution used or in some cases OF water. Where the walls OF the bubbles are impermeable to the salt in solution they are pressed together and so precipitated by the increased osmotic pressure caused by raising the concentration of the salt.If however these colloidal membranes are pervious to the salt no such precipitation occurs the added salt being distributed between the solutions inside and outside of the bubbles. The author has indeed prepared colloidal ferric hydroxide solutions containing per litre 8-69 grams OF barium nitrate or 2.152 grams OF potassium chloride or about 4 grams of potassium nitrate. T. H. P. Preparation of Small Q u a n t i t i e s of Chromium for Lecture Experiment &c. J. OLIE JUN. (Chenh. Centr. 1906 ii 1755 ; from Chem. TKeekbZad 3 662-663).-1n order t o demonstrate the preparation of chromium 50 grams of potassium dichromate which has been melted and powdered is mixed with 1 s grams of well-dried aluminium powder and 20 grams of this powder incorporated with 100 grams of a mixture of 160 grams of dry aluminium powder with 450 grams of calcined chromium oxide.The mass is ignited by means of a mixture of barium peroxide and aluminium powder and magnesium ribbon. The yield varies from 50 to 75% and is better when larger quantities are used. I n the latter case the proportion of the first mixture may be reduced to 10 to 15 grams. E. W. W. Chromium Boride. EDGAR WEDEKIND and K. FETZER (Ber. 1907 40 297-301. Compare Hoissan Abstr. 1894 ii 464; Binet du Jassoneix ibid. 1907 ii 3 0 ; Tucker and Moody Trans. 1902 81 lfj).-This is a n extension of the inquiry into the synthetic use of the aluminothermic process for the combination OF metals and metalloids (Abstr. 1905 ii 322). Whereas pure chromium boride cannot be prepared from a mixture of boron and chromium oxide in an electric furnace as the carbon cannot be removed it is obtained as a silver176 ABSTRACTS OF CHEMICAL PAPERS.white crystalline powder when boron and chromium thermite are caused t o interact. The excess of chromium is removed from the powdered regulus by treatment with dilute hjdrochloric acid followed by nitric acid and finally aqua regia. Chromium boride CrB is more difficult to fuse than chromium and has D17 5.4 and hardness 8. Acids or alkalis have no action on tho boride even hydrofluoric acid alone or when mixed with nitric acid. It is only slightly attacked by molten sodium hydroxide potassium nitrate or potassium chlorate ; sodium peroxide however oxidises it with incandescence to borate and chromate.When heated in oxygen t o a red heat the boride only undergoes a very slight change in colour. Chromium boride has weak magnetic properties. W. R. Action of Silicon Tetrachloride on Chromium. &:MILE VIGOUROUX (Compt. rend. 1907 144 83-85. Compare Abstr. 1906 ii 32 287 451).-Silicon chloride is decomposed by prolonged heating in contact with pure chromium a t 1200° yielding chromous chloride and the chromium silicide Cr3Si (compare Lebeau and Figueras Abstr. 1903 ii 486) 60 grams of chromium yielding 15 grams of the silicide. M. A. W. Proportion of Chlorine Precipitated by Silver Salts from Solutions of the Green Hydrate of Chromium Chloride. J. OLIE JUN. (Zeitsch. anorg. Chem. 1907 52 48-61).-The paper consists mainly of a discussion of the results of Weinland and Koch (Abstr.1904 ii 488) on the influence of the nature and concentration of the silver salt and the nature of the free acid on the proportion of chlorine precipitated by silver salts from solutions of the green hydrate of chromium chloride with some additional observations. According to Werner only one-third of the chlorine should be pre- cipitated by silver salts whereas Weinland and Koch who always used at least 3 equivalents of the silver salt in neutral solution found that more than 2 equivalents of chlorine were precipitated. The author has used smaller proportions of silver salts and finds that even 2.1 1 equivalents of silver nitrate precipitate 2 equivalents of chlorine. Whereas the silver salts of strong acids only partially precipitate the chlorine the silver salts of weak acids precipitate the 3 equivalents almost completely; this is ascribed to the action of the latter class of salts in removing hydrogen ions.The action of neutral salts such as sodium and ammonium nitrates on precipitation by silver nitrate is slight in small concentration but a large amount of these salts greatly increases the proportion of chlorine thrown down. Strong acids at first cause a decrease in the proportion of chlorine precipitated until in certain concentrations only 1 equivalent is affected; stronger solutions cause an increase in the amount pre- cipitated. It is suggested t h a t the great effect of strong acids and neutral salts when present in considerable concentration is due to direct exchange of the chlorine in the positive nucleus for other groups.Weak acids have a much smaller effect. G. S.INORGANlC CHEMISTRY. 177 Dehydration of the Isomeric Hydrates of Chromium Chloride. J. OLIE JUN. (Zeitsch. anorg. Chem. 1907 52 62-67).- According to Werner the green hydrate of chromium chloride has 4 molecules of water of constitution and 2 of water of crystallisation whereas the 6H,O of the violet chloride is water of constitution. Werner's dehydration experiments have been repeated at the ordinary temperature and the results confirmed. Further the green salt was heated in a vacuum over sulphuric acid the temperature being gradually raised to 100'. Under these circum- stances the salt did not melt ; on long continued heating it lost rather more than 4H20 as well as a little hydrogen chloride and left a dark violet residue of the approximate composition Cr2C150H,4H,0 which dissolved in water to form a solution almost identical in appearance and behaviour with that of the original green salt.The violet salt heated under the same conditions lost rather less than 4H20 and left a residue of approximately the same composition as that obtained from the green salt G. S. A Chromium Sulphate in which the Acid is Entirely Masked and the Equilibrium of Chromic Solutions. ALBERT COLSON (Compt. rend. 1907 144 79-81).-When a slightly acid solution of commercial chromium sulphate is allowed t o evaporate spontaneously after several months' exposure to sunlight (Abstr. 1906 ii 74) a mixture of violet and green salts is obtained from which the sulphate Cr2(S04)3,6H,0 can be isolated by the action of alcohol in the form of transparent green leaflets insoluble in absolute alcohol and sparingly soluble in 70% alcohol ; it is identical with the sulphate obtained from a chromic acid solution saturated at - 4' with sulphur dioxide (Abstr.1906 ii 233). A cold solution of chromium sulphate is therefore an equilibrium mixture of the violet sulphate and the three green sulphates Cr2(S0,),,6H,0 ; Cr2(S04),(OH)(S0,H) and Cr2S04(OH),(S04H),. M. A. W. Condensed Chromic Sulphates. ALBERT COLSON (Compt. rend. 1907 144 206-208. Compare Abstr. 1905 ii 94 ; Recoura Abstr. 1896 ii 27).-The equilibrium indicated in the following quation 2Cr2(S0,J3 + H,O.= H,SO + Cr40(S04) is only relatively stable and the pentasulphate Or,O(SO,) is acted on by boiling water with momentary production of a fresh quantity of acid thus Cr,O(SO,) + H,O = Cr,O,(SO,) + H2S04.This is proved by the repeated boiling of a N/lO solution of the normal green sulphate Cr2(S04)3,10H20 cooling very rapidly and then adding baryta solution. Measurement of the heat developed shows that each successive boiling after the first liberates sulphuric acid according to the second equation. Prom its exceedingly slow rate of dissolution incold water and from its cryoscopic behaviour the author considers that the green sulphate obtained by Wyrouboff (Abstr. 1902 ii 665) by drying the violet sulphate a t 110' has not the formula Cr,(S0,),,5H20 attributed to it by that author but is a condensed sulphate. By drying the powdered violet sulphate at 90' for twelve hours i t loses 11H,O and the pro- VOL.XCII. ii. 1 3178 ABSTRACTS OF CHEMICAL PAPERS. duct is much more rapidly dissolved by cold water than is the sulphate dried a t l l O o . A cryoscopic determination showed that the lowering of the freezing point of the solution obtained is approximately half that given by the normal sulphate containing the same amount of S 0 Q r S 0,. $k SO chromium. The formula is suggested for thegreen SO, Cr SO,* Cr SO sulphate. E. H. Dichromate and Chromate. JULIUS SAND and K. KAESTLE (Zeitsch. anorg. Chem. 1907 52 101-103. Compare Abegg and Cox Abstr. 1904 ii 662 ; Sand and Eisenlohr following abstract).-Ategg and Cox consider that a dichromate solution contains mainly Cr0:’ ions and undissociated chromic acid the proportion of Cr207/1 ions being small.The authors adduce evidence to show that the acid resulting from the hydration of chromium trioxide is a t least of medium strength and suggest that in dichromate solutions there is a hydrolytic equilibrium Cr,O,” + H,O ZZ 2Cr0,“ + 2H. The experi- ments have however not led to a. conclusive result. If the above equilibrium exists in solution the expression k = [Cr0,1‘]2[H.]2/[Cr20,”] must be constant. To test this point the concentration of hydrogen ions in solutions of potassium dichromate and in solutions of the same salt partially neutralised with potassium hydroxide have been measured by their action on a mixture of potassium iodide and iodate as already described. The reaction will be representod by the ionic equation 3Cr2Oi’ + 51’ + 10; = 6Cr0,“ + 312 and is accelerated by Ha ions.The ‘‘ constant,” calculated on the above assumptions gave values which were not even approximately equal. This deviation is not due to the direct action of dichromate on potassium iodide,,as the rate of reaction between these sabstances is much slower than the main reaction. The disturbance is probably due to the catalytic effect of some product formed during the reaction. For this reason the equilibrium constant cannot be accurately determined but an approximate estimate gives k= 1-5 x 10-13 a t 2 5 O from which it can be calculated that a 0*1N solution of potassium dichromate is hydrolysed to the extent of 0.18%. The constant k,,. of the equation d[12]/dt = kl[ H*]2[I’]2[10,] required for the determination of k was determined directly ; i t haa the value 1.6 x lo1’ a t 2 5 O .G. s. Polymolybdates. I. Progressive Neutralisation of Com- mercial Ammonium Molybdate. JULIUS SAND and F; EISENLOHR (Zeitsch. anorg. Chem. 1907 52 68-86).-Junius (Abstr. 1905 ii 825) has shown that commercial ammonium molybdate has the formula (NH,),,Mo,,O,,. The authors in the course of an investiga- tion of the progressive neutralisation of the salt by sodium hydroxide have obtained evidence that a t least one intermediate polymolybdate ion Mo6O2;’ is formed before the bivalent orthomolybdate ion MOO,” is reached. Ammonium molybdate seems to undergo ionisation normally (NH,),oMo120al = 1 ON H,* + MO~~O,?~’. On progressive neutralisationINORGANIC CHEMISTRY.179 there are two possibilities (1) in the original solution there may be a hydrolytic equilibrium M 0 ~ ~ 0 ~ ~ 1 0 ’ + 7H20 ZI? 12Mo0,” + 14H* in which case the gradual addition of sodium hydroxide will remove the H* ions and in all stages of the process there will be equilibrium between Mo,,O,,’O’,MoO; and H- ions in varying proportions ; (2) there may be one or more intermediate polymolybdate ions. Experi- ment shows that the second alternative is correct and the composition of one polgmolybdate has been determined by an electrochemical method (this abstract) and by a kinetic method (succeeding abstract). It is pointed out that if a simpler polymolybdate is formed during neutraIisation the curve representing the hydrogen ion concentration plotted against the amounts of sodium hydroxide added must show R break. To test this point the B.N.R.of a polymolybdate solution in which the hydrogen ion concentration remained constant throughout the experiment was measured against a corresponding solution to which gradually increasing amounts of sodium hydroxide were added and a distinct break in the curve was observed. From the position of the break it was estimated to occur when one of the two equations M 0 ~ ~ 0 ~ ~ 1 0 ’ + 60H’ = 2Mo60,;’ + 3H20 or Mo120,110’ + 60H’ = 4Mo,O11’“’ +3H,O is satisfied. The form of the curve is in favour of the first equation and this view was confirmed by a kinetic method (see succeeding abstract) There are indications that a second polymolybdate ion is formed in the course of neutralisation and the matter is being further investi- gated.G. S. Polymolybdates. 11. Action of the Iodide-Iodate Mixture on Ammonium Molybdate. JULIUS SAND and F. EISENLOHR (Zeitsch. anorg. Chem. 1907 52 87-1 00. Compare preceding abstract).-In the former paper evidence has been adduced to show that the com- plex ion of ammoDium molybdate is partially hydrolysed in solution according to the equation 2Mo,02,s’ + 6 He ; in the present paper this view is confirmed and the determination of the numerical value of k = [ No,0,~’]2[H~]~/[Mol,0,,10’] described Dushman (Abstr. 1904 ii 718) has shown that the rate a t which iodine is liberated from a mixture of potassium iodide and iodate in acid solution is proportional to the iodate ion concentration and to the square of the iodine and hydrogen ion concentrations.As this affords a convenient means of measuring hydrogen ion concentrations the rate at which iodine was liberated from mixtures of potassium iodide and iodate with ammonium molybdate was determined. Whilst no constant value for k is obtained on the assumption that Mo301F ions are present (compare previous abstract) good constants are obtained on the view that M000228’ ions take part in the equilibrium. The numerical value of k at 2 5 O is 3.80 x 10 31 from which it can be calculated that a 0.01 molar solution of ammonium molybdate is hydrolysed to the extent of 0.19% and is 1.17 x loA4 normal with regard to hydrogen ions. G. S . Thorium Chloride Oxychloride Hydride and Nitride. CAMILLE MATIQNON and MAWEL DEL~PINE ( A m .Chim. Phys. 1907 [viii] 10 130-144).-This paper gives a fuller account of work + 3 H,O 13-2180 ABSTRACTS OF CHEMICAL PAPB:#S. already partly recorded (Abstr. 1901 ii 106 ; compare also Abstr. 1901 ii 60; Kruss ibid. 1897 ii 456; Rosenheim Samster and Davidsohn ibid. 1903 ii 601 ; lllatignon and Bourion ibid. 1904 ii 340; Moissan and Martinsen ibid. 1905 ii 531). Anhydrous thorium tetrachloride may be prepared by heating thoria strongly in a porcelain tube and passing over it a current of carbon monoxide and chlorine but more rapidly by heating the oxide to a temperature below t h a t of the melting point of thorium tetrachloride in the vapour of carbon tetrachloride. The principal by-product of the reaction is oarbonyl chloride but small quantities of hexachloroethane and tetra- chloroethylene are also produced probably due to the decomposition of the carbon tetrachloride under the influence of heat.I n the foregoing reaction thorium oxychloride ThOCl appears to be produced as an intermediate product and may be isolated by stopping the reaction wben the product contains thorium tetrachloride and thoria in the ratio 8 or 9 1 and treating this with absolute alcohol when a residue of the oxychloride in small colourless needles is obtained. It is soIuble in water without decomposition but is slowly attacked by alcohol with the elimination of a small quantity of chlorine. The anhydrous oxychloride on exposure t o air absorbs moisture and is converted into the hexahydrate described by Rosenheim Samster and Davidsohn (Zoc.cit.). The latter under reduced pressure forms the pmtuliydrate ThOC1,,5H20 and this dehydration appears to proceed further with the eventual formation of a trihydrate. It was found impossible to prepare pure thorium by reducing thoria with sodium (compare Moissan and Honigschmidt Abstr.; 1906 ii 678). Thorium hydride ThH is not rapidly decomposed by water o r hydrochloric acid in the cold; i t is completely dissociated a t 390' under atmospheric pressure The heat of formation deduced in- directly (compare Matignon 1899 ii 273 ; 1905 ii 235) is 21.4 Cal. whence it appears that it is more easily dissociated than the hydrides of barium lithium and calcium. Thorium nitride Tb,N prepared by heating thorium strongly in a current of nitrogen is a yellowish maroon powder infusible at a red heat and is decomposed slowly by cold and immediately by warm water liberating ammonia.It is not dissociated even a t a red heat in a vacuum but burns in the air with incandescence but without the sparkling brilliance of thorium. The nitride described by Kohlschutter (Abstr. 1901 ii 598) is not decomposed by water or acids and his suggestion that it is a polymeride of the foregoing is scarcely tenable as it is lighter in colour and since it has not been obtained free from thoria it is probably an-oxynitride of the formula Tb,N205. T. A. H. Decomposition of Antimony Hydride. ALFRED STOCK FRANZ GOMOLKA and HANS HEYNEMANN (Ber.,. 1907 40 532-570. Com- pare Stock and Guttmann Abstr. 1904 ii 246).-The rate of decomposition of antimony hydride in glass vessels in the presence of an antimony mirror has been determined from the increase of pressure at constant volume a correction being applied for the molecular attraction of the hydride which causes a deviation fromINORGANIC CHEMISTRY.181 Boyle’s law of 12.6 mm. at 25’ and 760 rnm. With a given vessel and a mirror deposited a t 150’ the initial velocity of reaction is fairly constant but in successive experiments in the same vessel the initial velocity is constant only after the superposition of three mirrors upqn one another. The authors confirm Stock and Guttmann’s observation that the activity of a n antimony mirror is determined largely by the nature of the surface but deny that the activity is dependent on the concentra- tion of the hydride from which the mirror is produced.The authors contend that their measurements are thoee of a chemical reaction and not of diffusion phenomena because the temperature coefficient is 2.050 between 15’ and 35O and 1.909 between 25” and 35’; the temperature coefficients of chemical reactions lie between 2 and 3 at the ordinary temperature. The addition of hydrogen does not affect the rate of decomposition and under given conditions the relative velocity of the reaction is nearly proportional to the square root of the concentration of the antiiriony hydride. I n the presence of oxygen the antimony mirror is poisoned corn- pletely f o r several hours ; then i t recovers and the reaction proceeds with increased velocity. The mirror is unaffected by oxygen in the complete absence of antimony hydride; hence the poisoning is due t o oxidation not of the mirror itself but of the hydride or of some compound formed intermediately by which a layer of oxide is formed and destroys contact between the hydride and the catalyst.The “revivifying” of the mirror may be due to the reduction of this oxide by the antimony hydride; the increased velocity of the reaction is not due to the water so produced but may be consequent on changes in the surface of the catalyst caused by successive oxidation and redixction. Black antimony (compare Stock and Siebert Abstr. 1906 ii 34) is not poisoned by oxygen and is changed into the ordinary metallic mirror after the decomposition of the antimony hydride has been in progress for a few minutes. Photographs of antimony mirrors produced under different condi- tious are given. c. s. Theory of the Decomposition of Antimony Hydride ALFRED STOCK and MAX BODENSTEIN (Bey. 1907 40 570-575. Compare preceding abstract).-The results (Zoc. cit.) agree with those calculated by means of the equation M=aCP where M is the quantity adsorbed C the concentration of the hydride and a and y constants dependent on the nature of the substance arid the temperature. The decom- position of antimony hydride is probably a slow chemical reaction modified by adsorption phenomena. c. s. Peroxides of Bismuth. V. ALEXANDER GUTBIER and R. BUNZ (Zeitsch. anorg. Chem. 1907 52 124-126. Compare Abstr. 1906 ii 174 234,551 678).-Lorch (Inaug. Diss. Munzch 1893) claims to have obtained sodium metabismuthate by the action of sodium peroxide and chlorine on bismuth hydroxide a t the temperature of a freezing mixture The authors have repeated his experiments and find that182 ABSTRACTS OF CHEMICAL PAPERS. the products are brown in colour completely soluble in concentrated nitric acid continue to lose alkali on washing and contain compara- tively little active oxygen. They consider that derivatives of bismuthic acid” cannot be obtained in the presence of sodium hydroxide. G. S.

ISSN:0368-1769    

DOI:10.1039/CA9079205161

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

169 Organic Chemistry. A New Octane [&Methylheptane]. LATEIAM CLARKE (Bey. 1907 40 352-355).-This is the fourth octane t o be prepared; the three at present known are m-octlane di-isobutyl (PE-dimethylhexane) and y-methylheptane. The synthesis was accomplished by first preparing ethyE P-amy?acetoacetate C H3*CO*CH(CHMePra)*CO2Et from /3-iodo- pentane and ethyl sodioacetoacetate; the oil b. p. 2 2 6 O has a characteristic almond-like odour. On hydrolysis with 10% potassium hydroxide 6-met~~yZ-P-he~tano~ze CH3-[CH,],*CHMe*CH,*CO*CH,,- is obtained as an oil b. p. 156". The ketone on being reduced with sodium in the presence of ether and water gives &vnethyZ-P-heptanol CHMe*Pra-CH,*CHMe*OH an oil b. p. 168" and a pinacone b. p. 285-290". P-Iodo-8-methylheptane was obtained but not isolated by the reduction of the alcohol by hydrogen iodide at loo" and on replacing the iodine by means of zinc and hydrochloric acid 6-methyl- heptane was obtained as a colourless almost odourless mobile oil b.p. 1lSO. W. R. Preparation of Tetra- and Hexa-chloroethanes from Acetyl- ene. SALZBEBOWERR NEU-STASSFURT (D. R.-P. 17406S).-The direct addition of chlorine to acetylene takes place with explosive violence carbon being eliminated and hydrogen chloride formed owing to the great affinity of this halogen for hydrogen. The catalytic processes hitherto in yogue are not entirely satisfactory but the difficulties of this chlorination are overcome by passing acetylene into sulphur chloride i n the presence of iron powder or some iron compound When the mixture is cooled tetrachloroethane is produced and when heated to boiling ( 13S0) hexachloroethane is obtained.The former product is isolated by distillation alone or in steam whilst the latter crystallises from hot sulphur chloride and is collected and either sublimed distil led or recrystallised from alcohol. When the absorption of acetylene slackens the mixture is saturated with chlorine and in this way by alternating with acetylene and chlorine the process is rendered continuous. I n the absence of the catalyst the sulphur chloride has no action on the acetylene. G. T. M. Preparation of Methyl and Ethyl Iodides. WEINLAND and K. SCIIMID (D. R.-P. 175209).-Although dry potassium chloride yields methyl chloride on heating with methyl sulphate yet potassium bromide and iodidn when similarly treated do not undergo a like change methyl bromide is not the exclusive product and methyl iodide is not obtained by this process.It has now been found that by slowly adding methyl or ethyl sulphate t o a warm concentrated aqueous solution of an alkali iodide the alkyl iodide is produced quantitatively. G. T. AT* VOL. XCII. i. m170 ABSTRACTS OF CHEMICAL PAPERS. Application of the Principle of Partition. VIII. Constitu- tion of the Hexyl Iodide obtained from Mannitol. ARTHUR MICHAEL and ROBERT N. HARTMAN (Bee.. 1907,40 140-146. Com- pare Erlenmeyer and Wanklyn Zeitsclh. C?bem. 1863 6 564; Combes and Le Bel Abstr. 1893 i 246).-From theoretical considerations the conclusion is drawn that the hexyl iodide from rnannitol con- tains a considerable amount of P-iodohexane and a certain amount of y-iodohexane but little or no a-iodohexane.The amounts of the p- and y-iodo-derivatives actually found were respectively 65-60% and 35-40%. The hexyl iodide mas prepared by Domac's method (Abstr. 1881 1113) and purified by distillation under reduced pressure. It was transformed into tho acetate by means of silver acetate and glacial acetic acid. One hundred and ten grams of hexyl iodide gave 18 grams of hexene and 42 grams of hexyl acetate b. p. 150-15s'. The acetate on hydrolysis gave 26 grams of hexyl alcohol b. p. 136-140° which when oxidised by Lieben's method gave 17.8 grams of ketone. When analysed by the semicarbazide method this indicated the presence of some 60% of P-hexanone. J. J. 8.aa-Dichloroisopropyl Alcohol and the Preparation of Di- chloroacetaldehyde. ALFRED WOIIL and H. ROTH (Bey. 1907 40 212-218. Compare Jocitsch and Faworsky Abstr. 1S99 i 786 ; Fourneau and Tiffeneau Abstr. 1905 i 591 ; Hiiring Abstr. 1905 i 903; Oddo and Mameli Abstr. 1904 i 280).-The authors have attempted to prepare dichloroisopropyl alcohol by reduction of tri- chloroisopropyl alcohol but unsuccessfully as the reaction proceeds beyond the first stage. Reduction of the trichloro-alcohol by means of zinc dust and glacial acetic acid in cooled aqueous solution leads to tho formation of aa-dichloropropylene or by means of sodium and boiling absolute alcohol to the formation of ethyl a-ethoxypropionsto b. p. 73'142 mm. When treated with zinc ethyl in cooled ethereal solution in an atmosphere of carbon dioxide dichloroacetone evolves gas and yields a mixture of chlorinated products b.p. 35-50' and 50-57"/19 mm. The action of magnesium te2.t.- butyl bromide prepared by slowly adding magnesium t o tert.-butyl bromide in ethereal solution on dichloroacetone leads to the formation of isobutylene. Dichloroacetaldehyde is prepared in a 70.8% yield by heating dichloroacetal with benzoic anhydride and concentrated sulphuric acid at 1'70-180" and finally at 200". When treated with magnesium methyl bromide in cooled ethereal solution it yields tEichZoroisop!ropyZ aZcohoZ OH*CI'IMe*CHCI b. p. 146-148*/765 mm. G. Y. Synthesis of Alcohols by Means of Organomagnesium Compounds. 111. MICHAEL I. KONOWALOFF H. ISIILLER and TINTSCHENKO (J.Russ. I'hys Chena. Xoc. 1906 38 ii 447-44s. Compare Abstr. 1904 i 496 ; Grignard Abstr. 1900 i 382).- Me~J~yZet?~~Ztert.-am~Zcc~rbiizol or s-h?/dro~y-yys-tri~~~t~~~Zibe~ane Chlle,Et 'CMeE t-OH prepared by the action of mothyl ethyl ketone on magnesium P-bromo-ORGANIC CHEMISTRY. 171 P-methylbutane has m. p. '165-166' D;I 0.8323 ng 1.43407 is only sparingly soluble in water but absorbs it rapidly and has the ordinary odour of a tertiary alcohol. In the synthesis ol alcohols by Grig- nard's method the ketone or aldehyde employed is often itself reduced to the corresponding alcohol ; thus Eenchone when treated with magnesium ethyl iodide yielded chieff y fenchyl alcohol whilst tert.- bromobutane and pentane with benzophenone gave 385% of benz- hydro1 or its ester Z .K. Preparation of P-Ulycols from Aldols by the Action of Organomagnesium Compounds. ADOLF FRANKE and MORITZ KOHN (Moncctsh. 1906 27 1097-1128. Compare Abstr. 1905 i 11 1 ; Lieben Abstr. 1896 i 403).-~/3-Dimethylbutane-ay-diol formed together with pentylene giycol which on oxidation yields hydroxypivalic acid by the action of magnesium methyl iodide (2 mols.) on formylisobutaidol is identical with Fossek's glycol (Abstr. 1884 37). P/3-Dimethylpentane-uy-diol formed by the action of magnesium ethyl iodide (2 mols.) on formylisobutddol m. p. 60-63' (55' Abstr. 1905 i 111) b. p. P12-l14°Jll mm. could not be completely purified. The glycols described in this paper have been prepared by the action of organomagnesium compounds on aldole. Pull details are given as to the methods of purification which are mostly complicated and tedious.y-Phenyl-P/3-dimethylpropane-apl-diol (Smoboda and Fossek Abstr. 1891 31) is formed together with diphenyl by the action of magnesium phenyl bromide on forinylisobutaldol. [With EUGEN T~1~~.]-Acetaldo1 is obtained in a 55% yield by the action of aqueous potassium hydrogen carbonate on acetaldehyde below loo ; witk magnesium methyl iodide it forms pentane-py-diol b. p. 201-202"/748 mm. (Poray-Koschitz Abstr 1904 i 363) j the diphenylcarbamute C19H2204N2 forms a white powder m. p. 141'. The action of magnesium ethyl iodide on acetaldol leads to the formation of hexane-P6-dioZ OH*CHMe*CH2-CHEt*OH which is obtained as a viscid oil b p. 103'/11 mm. or 210-211°/750 mm. (con-.). The diplienylcurbamate C20H24O4N2 m.p. 144" ; the diucetccte b. p. 101-102°/13 mm. or 211'/750 mm. (partial decomp.). The product of the action of magnesium phenyl iodide on acetaldol yields on distillation diphenyl and a-piLenytbutane-ay-dioZ OH*CHPh*CH,*CHMe*OH which forms a white crystalline powder m. p. about 73.5' b. p. 162-164O/11 mm. ; the diacetate C14H1804 is a transparent mobile liquid b. p. 157O/10 mm. which decomposes partially when boiled under atmospheric pressure. [With KARL ZwI~u~~.]-Propa~do~ is obtained from propaldehyde in a 70% yield by Lieben's method. It reacts with magnesiumrnethyl iodide forming y-methyEhexane-P6-dioZ OH*CHEt*CHMe*CHMe*OH which is obtained as a colourless viscid oil b. p. 112*8*/9 mm. ; the diacetate CllH2004 forms a transparent mobile liquid b.p. 103.5-105*5"/11 mm. n 2172 ABSTRACTS OF CHEMICAL PAPERS 6-Methyl?~e~ta.12e-y~-diol OH* CHEt CHMe*CHEt*OH formed from propaldol and magnesium ethyl iodide is obtained as a transparent odourless liquid b. p. 120-123°/14 mm. ; the dicccetccte C12H2204 is a mobile transparent liquid b. p. 11 2-1 13'/13 mm. a-Phenyl-,8 - meth&entame-ay - diol OH*CHEt*CHMe*CHPh*OH formed together with benzene and diphenyl from magnesium phenyl iodide and propaldol is obtained as a transparent extremely viscid substance b. p. 169-173O/14 mm. which solidifies to a white mass when cooled with solid carbon dioxide and alcohol and cannot be completely purified. The diacetate C16H220 is a mobile transparent oil b. p. 169.5-170°/14 mm. which has a pleasant odour. Aldol Pentaerythrose and the Action of Copper Acetate on the Hexoses.A. F. MCLEOD (Amer. Chem. J. 1907,3'7 20-50). -It has been shown by Tollens (Abstr. 1892 1.27; 1893 617) that considerable quantities of pentaerythritol can be obtained by the con- densation of acetaldehyde (1 mol.) with formaldehyde (4 mols.). From a consideration of Nef's work i t is probable that this change is effected by the following successive reactions involving the inter- mediate formation of hy dracrylaldehyde Pp-dihydroxyisobutaldehyde and pentaerythrose G. Y. 30HaCI-T + H.CH,*CBO -+ OH*CH2*CH2*CH0 + OH*CH -+ C(CH,*OH),.CHO + :CH.OH + 2H20 -+ OH*CH(OH) + CH(CH,-OH),*CHO + :CH*OH -+ C(CH,*OH),*CHO. C(CR,*OH),*CS,*OII. The present investigation has been carried out with the object of obtaining experimental proof that the condensation does take place in the stages indicated. It has been found that considerable quantities of pentaerythrose can be isolated and indications have been obtained of the presence of relatively large amounts of P@-dihydroxyiso- butaldehyde in the reaction product Further it is shown that mixtures of hydracrylaldehyde (1 mol.) and formaldehyde (2 mols.) in presence of traces of sodium hydroxide give an almost quantitative yield of pentaerythrose. Experiments with acetaldehyde have shown that when this compound is left in eontact a t t,he ordinary temperature with solutions of sodium or calcium hydroxide of concentration below 0-1% little or no condensa- tion of the aldehyde occurs.The conditions under which the best yields of aldol and of crotonaldehyde can be obtained from acetaldehyde have been carefully studied.Acetaldehyde cannot be regenerated from aldol or crotonaldehyde by treatment with water with very dilute alkalis or with acids in sealed tubes a t 100'. Under these conditions aldol is readily transformed into crotonaldehyde which in turn is converted into insoluble yellow volatile and non-volatile oils and finally into aldehyde-resin. The behaviour of acraldehyde and of hydracrylaldehyde towards alkalis has been investigated. Nef's statement (Abstr. 1905 i 4) that crotonaldehyde is formed under these conditions is incorrect. The addition of traces of any alkali to a cold aqueous solution of acraldehyde results in the formation of an insoluble amorphous polymeride which decomposes at 94-95' and is analogous t o that173 ORGANIC CHEMISTRY.obtained by Nef by the action of barium hydroxide. These polymerides are neutral to sodium carbonate but dissolve in 10% sodium hydroxide and after heating the solution for a short time at 100" and adding the calculated quantity of hydrochloric acid yield a light brown amorphous substance of high melting point of about half the molecular weight of the original polymeride. On treating hydracrylaldehyde with sodium hydroxide an insoluble polymeride is not formed in the cold but on further treatment as in the previous case an insoluble polymeride is produced. A quantitative estimation has been made of the amounts of cuprous oxide carbon dioxide and of formic glycollic and oxalic acids formed from 100 grams of &dextrose d-lzvulose or d-galactose when heated for eight hours on the water-bath with excess of copper acetate solu- tion but the results so far obtained are not sufficiently complete to enable a theory of the oxidation of hexoses to be put forward. Experiments on the action of copper acetate solution on form- aldehyde and on formic glycollic and oxalic acids have led to the following conclusions. The formic and carbonic acids obtained on oxidising the hexoses are not produced as the result of the decomposi- tion of the oxalic acid formed as an intermediate product; the oxalic acid is not produced by an oxidation of glycollic acid and the formation of carbonic acid is not due to the oxidation of formic acid.E. G. Synthesis of Natural Erythritol.ROBERT LESPIEAU (Comnpt. rend. 1907 144 144-146. Compare Abstr. 1905 i 566).-The inactive erythrolactone previously described proves to be a racemic mixture for on treating it in the presence of water with an equivalent quantity of brucine and fractionally crystallising the product a separation (probably incomplete) into hrucine salts of rotatory power varying from - 25.3' to - 34" is effected. The salt of rotatory power - 25.3" gives a lactone of rotatory power - 35". When the lactone is reduced by sodium amalgam (containing 2.6% of sodium) in a solution kept slightly acid a syrup is obtained which with phenylhydrazine gives not erythrosazone but a hydrazide identical with that obtained directly from the lactone. This syrup on keeping for three months deposits crystals identical with natural erythritol. The identity was established by the melting point both alone and when mixed with the natural substance by analysis and by the production of a dibenzoylacetal m.p. 195-l96Oy identical with that described by Fischer. E. H. Preparation of Alkyl Ethers. TH. VAN HOVE (Bull. Accd roy. Belg. 1906 650- 668).-By heating propyl alcohol or isoamyl alcohol with quinoline hydrochloride in closed tubes a t 180" during six days the author has obtained a mixture of products containing in each case the corresponding alkyl ether alkyl chloride and di- and tri-slkyl quinolines. The yield of pure propyl ether so obtained is 35% of the theoretical and of the isoamyl ethyl 53%. When these alcohols are heated with quinoline alone under the above conditions no change occurs whence it appears that the reaction which takes place in the178 ABSTRACTS OF CHEXAICAL PAPERS.pt.e%enae of quinoline hydrochloride is due t o the hydrolpis of this sdb the hydrochloric acid liberated forming the dkyl chloride which then reacts in part with the alcohol and in part with the quinoline. The alkylquinohes produced are separated by conversion into the pierate& DipaptJqzlinoline b. p. 329O (corr.) yields a crystalline piorats m. p 189-190O. Fripropylguinnoline b. p. 348" (corr.) fwnishes a crysballine picrate m. p. f3d0. A third amorphous basic produet is obtained in this reaction which also yields an amorphous picrate. From the mixture of bases obtained in the reaction with isoamyl alcohol diisoamylquindine p.cra#e was obtained in slightly fluorescent t u b m. p.180°. In this reaction also B small amount of amyleae is formed. Ethyl aa-Dichloroisopropyl Ether and Dibromoacet- aldehyde. PAUL FREUNDLER (Compt. rend. 1907 144 272-273)- By condensing dibromoacetaldehyde with magnesium methyl iodide the author obtains a liquid denser than water which he considers to be aa-dibromoisopropyl alcohol. This however is much less stable than the corresponding dichloro-compound obtained by Wohl (this vol. i 170) undergoing partial decomposition when distilled and its examination was not proceeded with. Ethyl aa-diohlmoisopropyl ether CHCI,*CHMe*OEt formed as a by-product in the preparation of trichlorobutyric acetal (this vol. i 13) is liquid b. p. 145-146'. When heated with lead oxide and water in a sealed tube at 1 80-200° it gives not P-ethoxypropaldehyde but a mixture of ethyl chloride (or ethyl alcohol) and lead propionate.It is suggested that the propionic acid arises from an internal trans- YHMe first formed and that in any case CH*OH' position of the oxide O< the reaction contradicts Nef's theories on ethylidenic dissociation whilst Ieading to the conclusion that it will not be possible to obtain lsctaldehyde from an aa-dichloro-P-hydroxypropyl derivative as a starting point. E. H. Butylene Nitrosite and Bu tylenediamine. NICOLAUS J. DEMJAWOFF (Bey. 1907 40 245-246).-When nitrous fumes are passed into a well-cooled ethereal solution of butylene butylene nitrosite (C,H,O,N,) m. p. 103-104O is precipitated in cohurless glistening prisms.From the ethereal residue after reduction with tin and hydrochloric acid butaldehyde and butyZenedicsmi7te C,H,(NH,) are obhined ; the hydrochloride platinichloride aurichloride and picrate of the latter are described. c. s. Btructura of Phosphorous Acid and its Derivativera. 111. The Oompounds of the Tervdent Phosphorus Derivatives wikh the Monohalogen Uompounds of Clopper. ALEXANDER E. ABBUWF (J. Ruos. Phys. CAem. SOC. 1906 38 ii 293-319. Com- pare this VO~. i 8).-Corulpounds of the type CuX,P(OR) (where X abnds €or a halogen R for Et Ph &c.) have been prepared by the gradual addition of an equivalent weight of copper halide to a weighed quantity of the phosphorous ester. On warming gently the copper salt dissolves completely and the solution cryatallises immediately on isoAmy1 ether b.p. 1 7 2 * 2 O has D*g"2 0.7'767. T. A. H.ORGANIC CHEMISTRY. 175 cooling. Most of the salts thus formed are nearly insoluble in ether and ethyl and methyl alcohols but they are readily soluble in chloro- form and ethyl bromide. When exposed to the air they decompose but they can be preserved indefinitely in a sealed tube in an atmo- sphere of carbon dioxide. Pure water has no action whilst nitric acid oxidises them rapidly. The following compounds have been pre- pared. Methyl compounds CuCl,P(OMe) m. p. 190-1 92' ; UuBr,P(OMe) m. p. 180-182'; CUI,P(OM~)~ m. p. 175-177' can only be obtained at temperatures above 100"; at a low temperature the szcbstarace CuI,2P(OMe) m. p. 69-70' is formed. Ethpl com- pounds are formed with greater difficulty.CuCl,P(OEt) is a colourless oily unstable liquid which does not solidify at - 18'; CuBr,P(OEt) m. p. 27-2s'; CuI,P(OEt) m. p. 109-110° are soluble in most organic solvents and are fairly stable in air. PvopyZ compounds CuI,P(OPra) m. p. 64-65' the chloride and bromide are liquids difficult to purify ; CuCl,P(OPrP) m. p. 1 1 2-1 14'; CuBr,P(OPrp) m. p. 149-150O; CuI,P(OPrfJ) m. p. 184-1S5' are soluble in most organic solvents but are very unstable. Phenyl compounds CuCl,P(OPh) m. p. 95-96O strongly refractive ; CuC1,2P(OPh) m. p. about 70° ; CuBr,P(OPh) m. p. 90*5-91*5' ; CuBr,2P(OPh) m. p. 73-74O; CuI,2P(OPh) m. p. 73-76 ; CuI,P(OPh) has not been obtained isoButyZ compounds CuC1,P(OC,H,)3 prepared from the esters P(OC,H,) P(OC,H,),*OH was not obtained pure but the corresponding compounds CuCl,P(OC,H,),,P(OPh) m.p. 54-55" and CuBr,P(OC4H9),,P(OPh) m. p. 58-59'? were prepared in a pure state. Copper cyanide compounds have been prepared in an impure form ; they exhibit a tendency t o polymerise. TriethyZphosphine compounds CuCl,PEt m. p. 103-1 04' and Cu1,2PEt3 m. p. 37-39' are also described; the latter yields CuI,PEt3 on heating. Cuprous chloride bromide and iodide are also dissolved by the chloroanhydrides of phosphorous acids of the type P(OR)CI and by P(OPh),Cl,P(OMe),Cl yielding crystalline substances. Phosphorous tribromide or chloride reacts with cuprous bromide forming the substance CuBr,PBr which could not be purified. It is insoluble in practically all solvents and fumes strongly in air yielding hydrogen bromide cuprous bromide and phosphorous acid.None of the derivatives of quinquevalent phosphorus reacts with the cuprous halogen compounds even when the substances are heated together for several days at 250O. Since neither phosphorous acid nor its acid derivatives form compounds with the cuprous halides the phosphorus in this acid must be quinquevalent and the structure of the acid must consequently be represented thus O:P<gH)2 and the derivatives O:P<(,0R)2. Z. K. Acetyl Nitrate. AM& PICTET and EUGIBNE KHOTINSKY (Compt. rend. 1907 144 210-212).-AcetyZ nitrccte CH,*CO*O*NO is obtained by dissolving nitric pentoxide in acetic anhydride; it is separated from excess of acetic anhydride by distillation under reduced pressure If the mixture of acetyl nitrate and acetic176 ABSTRACTS OF CHEMICAL PAPERS.anhydride is heated a t the ordinary pressure it undergoes a violent reaction at 60° with evolution of nitrous fumes and formation of tetranitromethane. Acetyl nitrate is a colourless very mobile and hygroscopic liquid b. p. 22*/70 mm. which fumes strongly in air and explodes violently on rapid heating. Analysis was effected by decomposition with water and estimation of the nitric and acetic acids formed. It reacts with alcohols giving nitric or acetic esters accord- ing to the nature of the alcohol and the temperature. Aniline is converted into a mixture of molecular quantities of acetanjlide and aniline nitrate. It is a very powerful nitrating agent towards aromatic compounds benzene toluene anthracene and thiophen being nitrated below 0'.With substituted benzenes it has a tendency to give ortho- rather than para-nitro-derivatives. Thus toluene gives ten times as much o-nitro- as p-nitro-toluene. Acetanilide gives solely o-nitroacetanilide. E. H. Hydrolyisis of Sodium Palmitate. DAVID HOLDE and F. SCHWARZ (Ber. 1907 40 88-92. Compare Cohn Zeitsch. o;lelztZ. Chem. 1905 11 58 ; Abstr. 1906 ii 5 8 ; Schwarr Abstr. 1905 ii 657).-The authors dispute Cohn's views on the hydrolysis of sodium palmitate. Palmitic acid (0-5-1 gram) was dissolved in 20 C.C. of aqueous "/2 alkali and the excess of alkali titrated with N/2 hydrochloric acid. It was shown that in aqueous solution 100% of palmitic acid cannot be formed in this manner by Cohn's method using phenolphthalein ; that is that the amount of excess of alkali and the amount of alkali obtained by the hydrolysis of the salt cannot be separately dis- tinguished by this method.c. L. RETRIER (Ber. 1907 40 256-257. Compare Abstr. 1887 233).-The separation of dierucin from rape oil occasionally occurs before refining (compare Marcusson Abstr. 1906 i 924; Lewkowitsch this vol. i lo) due possibly to a reaction between trierucin and water caused by fermen- tation. c. s. A. McK. Occurrence of Dierucin in Rape oil. A-Chloro-7-valerolactone and some Related Compounds. HERNANN LEUCHS and OSKAR SPLETTST~PSER (&v. 1907 40 301-310).-Whilst the chlorine of ethyl 6-chloro-y-valerolactone-a- carboxylate is replaced by hydroxyl on warming with alkali (Traube and Lehmann Abstr. 1901 i 501) at 0' hydrolysis occurs the chlorine for the most part remaining intact.The hydrolysis is effected much better however by hydrochloric acid when a 90% yield of BchEoro- . - y -vaZeroZactoae CH2Ci*(?H*CH2*(?H2 is obtained as a colourless 0-co almost odourless oil of b. p. 132-1 35*/12 mm. D1* 1.625 sparingly soluble in sodium carbonate. It dissolves in ammonia forming a salt of chlorohydroxyvaleric acid and when this solution is heated at 100' €or one hour in a sealed tube Emmerling's 3-hydrouy-6-piperidone is formed (Abstr. 1900 i 16). 6 - ( ~ ) - ~ r ~ p h t ~ ~ c c ~ e ~ ~ e ~ u ~ ~ ~ is obtained in good vctlerolactone C',,H7*S0 *NI!€*CH2-~H*C'H,. ?€I2 co 0-ORGANIC CHEMISTRY. 177 yield by heating the hydroxypiperidone for three hours with Nsodium hydroxide (2 mols.) and then shaking the solution with /3-naphthalene- sulphonic chloride (2 mols.) dissolved in ether and 2 mols.more of the alkali. The lactone precipitated from its sodium salt by acid crystallises from 50% alcohol in small rectangular plates m. p 143-144' (corr.); it dissolves easily in sodium hydroxide but is insoluble in sodium carbonate. 3-Hydroxy-1-methyl-6 -piperidone $!H2*CH(0H)*7H2 obtained by NMe-CO-CH,' heating the chlorovalerolactone with aqueous meth;llamine in a sealed tube at loo" is a thick colourless oil b. p. 193-195'/13 mm. It is characterised by forming the P-napl~t~alenesuZphona~~ino-com- pound C,,HI7O,NS crystallking in very small hexagonal plates m. p. 82-83". yo O-- I The dikcctorze CH,* YH* CH,*YH derived from y-6dihydroxypro- pylmalonic acid was isolated in small quantity from the product OF the hydrolysis of ethyl chlorovalerolactonecarboxylate. If however the sodium salt in alcohol is heated in a closed tube at 100" for four hours and the residue left after evaporation of the alcohol boiled with hydrochloric acid a 14% yield of the dilactone is obtained; it forms colourless prisms m.p. 1'79-180" (corr.). An ester cannot be prepared by heating it with an alcoholic solution of hydrogen chloride nor is it soluble in alkali carbonates although it is easily soluble in alkali hydroxides. y&Dihydroxypropylmalonamide obtained by heating the dilactone in a methyl alcohol solution of ammonia for twenty minutes crystallises in slender prisms m. p. 168-169' (corr,). That Traube and Lehmann'a amide (m.p. 140° loc. cit.) was impure is proved by the fact that both the dilactone and ethyl 6-hydroxg-y-valerolactonecarboxylate give the same bisplbenyl- hydrcwide C,,H,,O,N crystallising in colourless needles m. p. 2 14' (corr. decomp.). OF-- CO 0-- Yo O-- b0 The dilactone CH,. FH*CH,*CBr of a-bromo-ys-dihydroxypropyl- malonic acid prepared by heating a solution of the parent di-lactone in hydrobromic acid and bromine (2.2 mols.) in a sealed tube a t 70" for one hour crystallises from alcohol in hexagonal plates m. p. 186-187' (corr.). When however the dilactone is heated with 4.4 mols. of bromine at 85O for four to five hours aa8-tribromo-v- I CH2Br*YH*CH,*~Br2 is the product obtained crystal- co 0- valeyolactone lising from aqueous alcohol in aggregates of needles m.r. 84-85'. W. R. Desmotropic Forms of Ethyl Acetoacetate at Lcw Tem- peratures. HANS STOBBE (Anizalen 1907,352,132-14S).-By work- ing at low temperatures ( - 78" to - 64') and using the characteristic178 ABSTRACTS OF CHEMICAL PAPERS. red coloration which is obtained with ferric chloride when a definite quantity of the ketonic form of ethyl acetoacetate has changed into the enolic form it has been possible to show that the velocity with which the ketonic form changes into the enolic is greatest in amyl alcohol becoming smaller in the following alcohols in the order given butyl ethyl methyl. For example the red coloration appears in the case of nmyl alcohol in thirty-nine secs. and in the case of methyl alcohol in fifty-six secs. after the addition of equal quantities of the ester to equal volumes of the respective alcoholic solutions a t - 78' containing ferric chloride in equal concentration. Since methyl alcohol possesses the greatest and ainyl alcohol the smallest dielectric con- stant it is obvious that the velocity of the change of the ketonic into the enolic form is greatest in the least dissociating medium. This result is contrary to that usually observed with the one exception discovered by Dimroth (Abstr.1905 i 98). It is further shown in agreement with Traube (Abstr. 1896 i 593) but in contradiction to Briihl (Abstr. 1905 i 407) that the proportion of the enolic form present is greater in alcoholic solutions than in the undissolved ester. Determination of the Molecular Weight of Ethyl Aceto- acetate in Freezing Chloroform.HANS STOBBE and ERNST MULLER (Anrzalen 1907 352 147-151).-The apparatus employed was a slightly modified form of the ordinary Beckmann's apparatus. The constant for chloroform m. p. - 6 2 O using ethyl benzoate as the solute was found to be 499. The mol. weight found for ethyl aceto- acetate showed it to be unimolecular in freezing chloroform. The authors therefore consider it probable that the ester is also uni- molecular in alcoholic solutions at - 78' and that the slow rate with which the ketonic form of the ester changes into the enolic form at this temperature is not due to the formation of associated molecules but W. H. G. merely to the low temperature (compare preceding abstract). W. H. G. New Synthesis of Ethyl 7-Chloroacetoacetate. M.PICHA [completed by EICHARD DOHT and S. WEISL] (Monatsh. 1906 27 1245-1 349).-The action of aluminium amalgam on ethyl chloro- acetate in presence of traces of alcohol leads with development of heat to the formation of ethyl y-chloroacetoacetate ethyl alcohol and hydrogen chloride ; the temperature of the reaction must not be allowed to rise above 120'. The y-chloroacetoacetate is isolated in the form of its copper derivative m. p. 163' (corr.) (168' Lespieau Abstr. 1899 i 243) from which it is obtained by heating with dilute sulphuric acid. G. Y. Preparation of &3-Disubstituted Glycidic Acids. GEORGE DARZENS (D.R.-P. 174279).-Disubstituted glycidic acids having the general formula ~ R R ~ C H * C O H are readily obtained by con- densing a ketone with a halogenated ethyl acetate in the presence of an alkaline reagent and then hydrolysing the resulting ester.A mixture of methyl nonyl ketone and ethyl chloroacetate was treated with alcoholic sodium ethoxide ; ethyE mst~LyZnonylql~cid~t~ 0-ORGANIC CHEMISTRY. 179 thus obtained was distilled under reduced pressure b. p. 165-170°/ 16 mm. Ethyl p-tolylmethylglycidate (b. p. 160-164'/16 mm.) and ethy2 benxylm&hylglycidate (b. p. 1'75-180°/1 6 mm.) were obtained re- spectively from p-tolyl methyl ketone and benzyl methyl ketone. G. T. M. Disubstituted Ethyl Acetoacetates and Malonates. HANS MEYER (Monatsh. 1906 2'7 1083-1096. Compare Abstr. 1906 i 137 358).-It has been shown puiwiously that whilst methyl dimethyl- and methylethyl-malonates are converted into the corresponding diamides by the action of aqueous ammonia methyl diethyl- and ethyl dimethyl-malonates remain unchanged.The action of ammonia on a number of other compounds of similar structure has been investigated with the object of throwing light on the relation of the stability of the system CRR"R"'*CO,Alk to the nature of the groups R' R" and R"'. Ethyl diethylacetoacetate remains unchanged when shaken with aqueous ammonia but under the same conditions methyl dimethyl- ethyl methylethyl- and ethyl dimethyl-acetoacetates yield the corre- sponding amides. Dimethylacetoacetamide COMe*CMe,*CO*NH m. p. 120-121' crystallises from water or methyl alcohol. Methylethylacetoacetamide COMe*CMeEt*CO*NH2 separates from water i n compact crystals m.p. 123-124'. The preparation described as commercial ethyl dimethylacetoacetate is usually the methyl ester (compare Peters Abstr. 1891,109'7) which has the hydrolysis constant k = 2.25 at 25' (Goldschmidt and Oslan Abstr. 1900 i 373); the ethyl ester which must be prepared in two distinct stages the intermediate ethyl methylacetoacetate being carefully fractionated has the hydrolysis constant k = 0.75 at 25". Methyl diethylacetoacetate is hydrolysed partially by aqueous ammonia bat does not form the amide. On the other hand methyl and ethyl ethylacetoacetates react with aqueous ammonia forming the amide in a few hours and ethyl benzylacetoacetate undergoes the reaction in two days forming the amide whilst methyl benzylaceto- acetate m. p. 291-293' (corr.) dissolves only in aqueous ammonia in six days the product obtained on evaporation being identical with benzylmethylacetamide m.p. log" prepared by the action of thionyl chloride and ammonia on benzylmethylacetic acid m. p. 275-277'. Ethyl diallylmalonate does not react with aqueous ammonia ; the methyl ester b. p. 235' (corr.) which is obtained on boiling the acid with methyl alcohol and sulphuric acid as an oil having an odour of pears dissolves slowly in ammonia and if evaporated after five days yieldsdiallylmalonamide C(CH,*CH:CH,),(CO*NH,) m. p. 201-202'; this gives the biuret reaction decolorises potassium permangannte in sodium carbonate solution and yields ammonia when treated with cold aqueous potassium hydroxide. Ethyl methylpropylmalonate does not react with ammonia in aqueous solution ; the methyl eater b.p. 206-209° yields methylpro~lmalor- amide m. p. 182' ammonium methylpropylmnlonate and ethyl methyl- propylmalonamate (?) m. p. 67' subliming.180 ABSTRACTS OF CHEMICAL PAPERS. Whilst ethyl benzylmethylmalonate does not react with aqueous ammonia ethyl benzylmalonate rapidly forms the amide m. p. 225'. Methyl 6enxylmethplmalonute crystallises in large plates m. p. 63" has a pleasant odour and is converted by ammonia into benxylmethyl- malonnmide which crystallises in needles m. p. 202-203O and gives the biuret reaction Methpl cetglmalonate m. p. 44" crystallises from ether and does not react with ammonia. Methyl triphenylacetate m. p. 182" is formed quantitatively by the action of diazomethane on the acid; it does not react with ammonia in aqueous solution a t 120° but when heated at 180' explodes.The action of aqueous ammonia on ethyl diethylrnalonate for several months leads to the formation of a clear solution ; this on evaporation leaves a syrupy residue which when heated yields ethyl diethyl- malonate and ammonium diethylmalonate in accordance with the equation 2C02Et*CEt,*C0,NH = CEt,(CO,Et) + CEtj,(C02NH,),. G. Y. Carbon Suboxide. 11. OTTO DIELS and GEORG MEYERHEIM (Ber. 1907 40 355-363. Compare Abstr. 1906 ii 227).-It has been found that carbon suboxide is formed when methyl benzyl or phenyl malonates as well as ethyl malonate are heated with phosphoric oxide ; ethyl oxalacetate and ethyl metlianetricarboxylate also yield it. The most interesting reaction studied however is that of malonic acid itself as in addition to its giving acetic acid and carbon dioxide (the known fission of an aa-dicarboxylic acid) it alsogives a 10-12% yield of carbon suboxide whsn heated a t 140-150" and serves as the most convenient method of preparing the compound. A description of the apparatus is given.When conducted through a heated constricted tube carbon suboxide forms a characteristic metallic mirror like that given by arsine. At low temperatures the suboxide is stable and the change into the dark red product at 0-15" due to polymerisation is hastened by traces of impurity. This polymeride or mixture of polymerides is very hygroscopic ; with cold water heat is developed an eosin-red solution is formed carbon dioxide being evolvedat the same time.On heating the polymerised product carbon monoxide carbon dioxide and carbon suboxide are obtained. Heating the suboxide to a higher temperature or working with larger quantities results in an evolution of carbon monoxide and dioxide ; the residue probably a complicated mixture contains more carbon than the suboxide. The authors consider that carbon suboxide is to be represented as a malonic anhydride OC:C:CO and not as the lactone of P-hydroxy- Carbon suboxide has m. p. - 107" and D! 1.11. propionic acid C e g i > O (Michael Abstr. 1906 ii 442). Dehydracetic acid is formed when acetic anbydride is heated with phosphoric oxide. W. R. Action of Reducing Agents on Cholic Acid. ALFRED EKBOM (Zeitsch. physz'ol. Chenz. 1906 50 97-124).-Vahlen's conclusion (Abstr.1897 i 648) that deoxycholic acid is formed by the reduction ofORGANIC CHEMISTRY. 181 cholic acid with alkaline reducing agents has not been confirmed; in all cases unaltered cholic acid was obtained. It is probable that the acid used by Vahlen contained a reduction product. When heated with acetic acid or with zinc dust and acetic acid cholic acid yields a mixture of mono- and diacetyl derivatives which may be obtained as a flocculent precipitate on the addition of water. These acetyl derivatives do not give Mylius's reaction. H. GAULT (Bull. SOC. chim. 190'7 [iv] I 40-48. Compare this vol. i 148).-Ethyl ethylidenebisoxukuce- tatehydrate CHMe[CH(CO,Et)~CO*CO,Et],,H,O m. p. about 11 ZO obtained by condensing acetaldehyde with ethyl oxalacetate as already described (loc cit.) crystallises from dilute alcohol and gives a colora- tion with ferric chloride on warming.The anhydrous ester could not be isolated. The monopl~enyl?~yd?waxo?ie m. p. 135O crystallises from alcohol ; the monosemiccwbaxone m. p. 185O crystallises from boiling water. Cold sulphuric acid hydrolyses the hydrated ester forming etl~ylidenebisoxalacetic dinnhydvide CH Me ( CH< ~ ~ ~ o ) ~ which forms a very soluble hydrate with cold water and on warming with water decomposes evolving 2 mols. of carbon dioxide and forming diketo- methylpimelic acid ; a similar decomposition of the dianhydride is brought about by alcohol whilst aniline furnishes a dianilide which decomposes on contact with water forming the dianilide of diketo- methylpimelic acid.Boiling dilute mineral acids convert the hydrated ester directly into diketornethylpimelic acid. Etihyl propylidenebisoxalacetate hydrute m. p. 1 18O is prepared similarly from propaldehyde and ethyl oxalacetate. The anhydrous ester could not be isolated. The monop~enyEhydr~6xone m. p. 129O crystallises from dilute alcohol and t,he r)zonoSemiccIrbuxo9ze m. p. 1 60° separates in crystals from the same solvent. Proyylidenebisoxalucetic dianhydride m. p. about 170" (decomp.) obtained on treating the hydrated ester with cold sulphuric acid and with cold water yields the corresponding unstable tetra-acid which rapidly decomposes yielding diketoethylpimelic acid. With alcohol the dianhydride yields ethyl diketoethylpimelate and with aniline the corresponding dianilide which readily decomposes forming the dianilide of diketoethylpimelic acid. The latter acid is produced in minute quantities when the hydrated ester is boiled with dilute mineral acids.Ethyl hept?lbidenebisoxaZacetate hydrate J. J. S. The Pyran Series. IV. C,Hls* CH [ CH( C0,Et) CO*CO,Et],,H,O m. p. 115" obtained from heptaldshyde (aenanthaldehyde) and ethyl oxalacetate crystallises from dilute alcohol and when heated at 110' decomposes without yielding the anhydrous ester. The monophenyl- hydrazone m. p. 115-116O crystallises from dilute alcohol and the monosemicwbazone m. p. 153O crystallises from ether or from a mixture of this solvent with light petroleum. Heptylidenebisoxalacetic dianhydride m. p. 89-goo obtained by the action of cold sulphuric acid on the hydrated ester is less stable than its lower homologues furnishes a very unstable hydrate with cold water and is decomposed by warm water forming diketohexylpimelic acid whilst alcohol and182 ABSTRACTS OF CHEMICAL PAPERS.aniline furnish similarly the diethgl ester and the dianilide of the same acid respectively. Diketohexylpimelic acid is not produced when ethyl heptylidenebisoxalacetate hydrate is boiled with dilute mineral acids. T A. H. The Action of Aluminium Alkyloxides on Aldehydes. Corn- plex Elthereal Condensations considered BEI a New Form of Aldehyde Condensation. Y. E. TISTSCHENKO (J. Euss. W q s . Chem. Xoc. 1906,38 ii 355-418).-A historical survey of previous work on condensation is given. By the prolonged action of a small quantity of dry aluminium ethoxide on dry paraformdldehyde at the ordinary tem- perature a mixture of ethyl and methyl formates are formed.Alumi- nium or magnesium methoxide with the same aldehyde yield chiefly methyl formate together with a little formic acid and possibly the com- pound MgfO*CH( OlsIe),],. Benzaldehyde behaves similarly benzyl benzoate being the chief product ; the main course of ths reaction being lowing substances are formed by the interaction of aluminium ethoxide and acetaldehyde. Ethyl acetate aldol crotonaldshyde ethyl alcohol ethyl P-hydroxybutyrate and its acetyl derivative mono- and diacetyl derivatives of PS-dihydroxybutane crotonic acid and possibly also para- acetaldehyde and acetal. 'She main product is however ethyl acetate but in the presence of water considerable quantities of aldol are also formed.As the amount of aluminium ethoxide employed is i:icreased the amount of aldehyde remaining Unchanged diminishes mliilst the amount of ethyl acetate formed increases until the mixture contains 15% of ethoxide after which any further addition of the latter diminishes the yield of ester. The temperature at which the experi- ment is performed exerts but little influence on the course of the reaction. About 80% of the ethoxide remains unchanged the rest being converted into aluminium hydroxide or possibly into more corn- plex alkoxide compounds of aluminium. 2CH,O = H*CO,*CH ; BC,H,*CHO = C6H,*C0,*C€I,*CG~5. The fol- Z. K. Preparation of Aldehydes containing a Secondary Alkyl Group QEORGES DARZENS (D.R.-P.174239. Compare preceding abstract).-Aldehydes having the general formula CHRR*CHO can be obtained from the /3P-substituted glycidic acids by heating these sub- stances either alone or in the presence of water. MetJLylnon?llacetccldeh~de C,H,,-CMe*CHO b. p. 1 19-f22'/1 G min. obtained by heating in a vacuum at 120° the glycidic acid produced from methyl nonyl ketone and ethyl chloroacetatfe furnishes a semi- carbazone m. p. 101-102'. p-Methylhydratropaldehyde b. p. 1 O7-l0So/19 mm. was obtained by heating p-tolylmethylglycidic acid with water a t 150' j it furnishes a semicarbazone m. p. 159-160'. Ethyl benzylmethylglycidate when hydrolysed yields an acid which when heated at 140° in ft vacuum gives rise to P - ~ f L e n y Z - a - r n e t ~ ~ y l b ~ t ~ Z ~ e ~ ~ ~ ~ CH2Ph*CHMe*CH0 b.p. 129-130°/19 mm. it yields a semicarbszone m. p. 7 0 - 7 2 O . Many other aldehydes of this series have been prepared in a similar manner. G. T. M.ORGANIC CHEMISTRY. 183 Condensation Product of Ethoxyacetaldehyde with Acet- aldehyde. BRUNO EISSLER and ALEXANDER POLLAK (Monatsh. 1906 27,1129-1 144 ; Abstr. 1905 i 683)-Ethoxyacetaldehyde condenses with acetaldehyde in presence of anhydrous potassium carbonate forming p-hydroxy-y-ethoxybutaldehyde OEt*CH,*CH(OH)'CH,*CHO which is obtained as a yellow viscid oil b. p. 122-125O/18 mm. gives the aldehyde reactions and when oxidised with alkaline potassium per- manganate yields ethoxyacetic and oxalic acids. When heated with anhydrous sodium acetate at 1 20-130° the aldol yields y-ethoxycroton- aldehyde OEt*CH,*CH:CH*CHO which forms a transparent liquid b.p. 157' and combines with 1 niol. of bromine. The aldol is oxidised by potassium permanganate in neutral solution forming ,f3-hpdroxy-y- ethoxpbutyrz'c acid OEt*CH,*CH(OH)*CH,*CO,H which is isolated in the form of its culciuin salt (C,H,,0,)2Ca. The g l p o l OEt*CH,*CH(OH)*CH,*CH,*OH b. p. 210°/760 mm. is prepared by reduction of the aldol with aluminium amalgam. G. Y. Fermentability of Methylglyoxal. PAUL n ! b Y m (Biochem. Zeitsch. 1907 2 435-437. Compare Buchner and Meisenheimer (Ber. 1906 39 3201).-Methylglyoxal in 1,2 or 5% aqueous solution is not fermented by living yeast cells. J. J. 8. Unimolecular and Termolecular Glyoxal. CARL HARRIES and PAUL TEMME (Bey. 1907 40 165-172).-A unimolecular glyoxal CHO-CHO is obtained when commercial glyoxal (Debus's polyglyoxal) is heated with phosphoric oxide and the product collected in a vessel surrounded with a mixture of solid carbon dioxide and ether or with liquid air care being taken to prevent the admission of atmospheric moisture. It forms golden yellow crystals m.p. 15' and b. p. 51"/776 mm. or 50°/742 mm. I t s vapour has an intense green colour and condenses to a green liquid which changes to yellow on cooling. The odour is similar to that of formaldehyde and the vapour burns with a violet flame. Even at low temperatures it polymerises to an insoluble pwaglyozal and in the presence of small amounts of water this change occurs instantaneously. The glyoxal dissolves in an excess of water and the molecular weight determined by the cryoscopic method indicates that in such a solution the aldehyde is still uni- molecular.A termolecular glyoxal is obtained when cinnamaldehyde ozonide is warmed with water a t 60-70". It dissolves readily in water and may be obtained from the aqueous solution by evaporating at 25-30' after the removal of benzaldehyde benzoic acid &c. If the temper- ature is raised above 30' a polymeric modification resembling the commercial product is obtained. The termolecular compound forms a yellow amorphous mass insoluble in ether ; it changes colour a t 175' and decomposes at about 200'. I t s aqueous solution is distinctly acid and also reduces Fehling's solution. I t s aqueous or alcoholic solutions yield derivatives of the unimolecular glyoxd ; the clisen-~icarbccxone C4HsO2N6 crystallises i n rhombohedric prisms ; the phenylosazone has184 ABSTRACTS OF CHEMICAL PAPERS. m.p. 167-168" ; the diphenylosazone 203O and the phenylmethyl- osazone 221'. The tetruetlql acetal CH(OEt),*CH(OEt) is a mobile liquid b. p. 88-89O/14 mm. sparingly soluble in water J. J. S. Preparation of an Unsaturated Aldehyde from Formyliso- butacetaldol and an Attempt to Condense Formylisobut- acetaldol with Formaldehyde. HANS BUSCH and KLARA GOLDEN- TEAL (Monatsh. 1906 27 1157-1166. Compare Weis Abstr. 1905 i 17; Schachner ibid. 171).-In one experiment the action of acetic anhydride and sodium acetate on formylisobutacetaldol led t o the formation of only a small amount of the unsaturated 8-acetoxy- aldehyde OAc*CH,*CMe,*CH:CH*CHO which is obtained as a yellow oil b.p. 83"/16 mm. reduces ammoniacal silver solutions and formrJ a n additive product with bromine C,€I1,O3I3r2. In another experiment two products mere obtained ; the tetra-acetate OAc*CH2*CMe,~CH(OAc)*CH,*CH(OAc) which forms a colourless mobile liquid b. p. 83-90°/12 mm. and the diacetccte OH*CH,*C3~e2*CH(OH)*CH,*CH(OAc) which is a slightly yellow more viscid liquid b. p. 137-138O/12 mm. When heated with potassium carbonate in an atmosphere of carbon dioxide in a refliix apparatus a t 110-115° the aldol yields the acid C7H1,03 which is obtained in yellow crystals m. p. 104-105" and f o r m an additive compound with bromine ; the calcium salt (C7Hli0,),Ca forms white crystals The corresponding unsaturated ddehyde C,H1,02 is prepared by heating the aldol with potassium carbonate in an atmosphere of carbon dioxide in a sealed tube a t 110' ; i t crystallises in slender yellow needles m.p. 49-50' sublimes at 65"/15 mm. gives the aldehyde reactions forms an additive compound with bromine and is oxidised on exposure to air yielding the preceding acid. The condensation of the aldol with formaldehyde in potassium carbonate solution leads to the formation of Plj-dimethyltrimethylene glycol (Just Abstr. 1896 i 403). G. Y. Preparation of the Corresponding Aldol from E thoxyacet- aldehyde. WALTER FRIED (dlonatslh. 1906 27 1251 -1258. Corn- pare Kliiger Abstr. 1905 i 683 ; Eissler and Pollak this vol. i 183). :The action of potassium carbonate on ethoxyacetaldehyde and iso- butaldehyde in concentrated aqueous solution leads to the formation of a mixture of aldols b. p.112-115°/18 mm. The aldol of ethoxyncetaldehyde CP-hydiwoxy-ay-diet~oxybutuldei~~~~ OEt*CH,*CH(OH)*CH(OEt)*CHO prepared by the action of potassium carbonate on ethoxyacetaldehyde in concentrated aqueous solution cooled by ice is obtained as a mobile transparent liquid b. p. 115-1 17O/lS mm. which gives the aldehyde reactions and when heated with anhydrous sodium acetate in a current of carbon dioxide at 120-1 30' yields the msaturccted aldehyde OEt*CH,-CH:C(OEt)*CHO b. p. 148' ethereal solution an additive compound with two atoms of bromine. G. Y. This reduces ammoniacal silver solutions and forms inORGANIC CHEMISTRY. 185 Peroxide of Methyl Ethyl Ketone. PASTUREAU (Compt.rend. 1907 144 90-93).-Methyl ethyl ketone pe?*oxide C8H1604 obtained as a thick colourless oil when methyl ethyl ketone is treated with hydrogen peroxide in the presence of sulphuric acid has D16 1,042. possesses an agreeable odour is stable at the ordinary temperature but very explosive when heated above looo and cannot therefore be distilled even under reduced pressure. When distilled with steam under reduced pressure i t yields a mixture of constant b. p. 48'/80 mm. or 56"/130 mm. It is completely reduced to methyl ethyl ketone by the action of nascent hydrogen in the cold ; explodes violently when placed in contact with concentrated sulphuric acid and is partially transformed into the original ketone and acetylmethylcarbinol by the action of dilute su1pLIiiric acid.It yields the tetrabromo-derivative of methyl ethyl ketone CH,Br*CO*CH,*CBr when treated with bromine. The acid mother liquor from which the peroxide is separated in the above preparation contains acetylmethylcarbinol CHMeAc. OH which yields the yellow osazone m. p. 243" and the blood-red osotetrazone (von Pechmann Abstr. 1888 1287). M. A. W. Transformation of Aldehydes into Ketones by Means of Diazomethane. FRITZ SCHLOTTERBECK (Ber. 1907 40 479-483). -The author has studied the formation of ketones from aldehydes by means of diazomethane. Furodiazolea are probably formed as inter- mediate products thus R*CHO + CH,N -+ ReCH<G,2.# -+ R-CO*CH + N,. Methyl hexyl ketone was obtained from heptaldehyde acetophenone from benzaldehyde and methyl isobutyl ketone from isovaleraldebyde the ketones having been identified in each case by means of their semi- carbazones. A.McK. 0-N New Synthesis of a-Diketones. LEO TSCHUGAEFE" (Ber. 1907 40 186-187).-Diacetyl and dipropionyl are formed by the action of magnesium methyl and magnesium ethyl bromides respectively on vinylideneoxnnilide (von Pechmann Abstr. 1898 i 135). iZrickel diethplglyoxinziize Ni(NO:CEt*CEt:N*OH) has also been prepared and crptallises in orange-red needles. G. Y . Solubility of Sucrose in Water in Presence of Invert- sugar. HENRI PELLET and CH. FRIBOURQ (Chern. Centr. 1906 ii 1722 ; from BuEI. Assoc. China. Sucr. Dist. 24 304-315).-Experi- ments have shown that a eaturated solution of sucrose can dissolve invert-sugar and that a saturated solution of crystalline sucrose can after inversion dissolve sucrose I n a saturated solution containing eaual weights of sucrose and invert-sugar 1 part of water holds 3.2 of dry substances in solution a t 29" whilst under similar condi- tions in a solution of pure sucrose 2-18-2.22 are dissolved by 1 part of water.Asolution of invert-sugar saturated with sucrose at 29O contains 69 parts of sucrose per 100 of invert-sugar and 3.9 of dry substances are dissolved by 1 part of water VOL. XCII. 1. 0186 ABSTRACTS OF CHEMICAL PAPERS. The viscosity of a saturated solution of sucrose increases in propor- tioii to the quantity of invert-sugar contained in it. Cellulose. HERMANN WICHELHAUS and WALTHEE VIEWEG (Bey. 1907 40 441-443).-The view that in mercerising cellulose only the cuticle of the fibre is removed (compare Frankel and Friedlander Mitt.K. I<. I'eclm. Getverbenaus. TVien 1898 326) is incorrect. By comparing the esters of nitric and iuenzoic acids derived from the natural and rnercerised cellulose the change is shown to be chemical in character. The yield of benzoate obtained from 100 parts of cellulose by the action of benzoyl chloride and sodium hydroxide is E. W. W. Before. After mercerising. Cotton wool . . . . .. . . . .. . . . . Flax . . . . . I . . . . . . . 112 121 139 137 Again although the % of nitrogen in the nitrates derived from cotton cotton wool or flax both before and after treatment is practically constant (13%) the products are chemically different as the portion soluble in a mixture of alcohol and ether is increased by mercerisa- tion.W. R. Constituents of Lignocelluloses which Yield Furfuraldehyde and Methylfurfuraldehyde. KOW~~AD FROMHERZ (Zeitsch. phgsiol. Cltmz. 1906 50 209-240).-Lignocellulose has been prepared from the wood of the aspen (Populus t.r.emuZa) by Lange's method the yield being 55%. Certain of the constituents which yield furfuraldehyde and methylfurfuraldehyde are dissolved when heated with water under pressure at 150". These constituents probably resemble the '' furoids " obtained by Cross and Bevan from straw. The mannans and galactans are also dissolved during this process. Dextrose could not be detected and l ~ v u l o s e was present in small quantities only. Part of the furfuraldehyde is derived from the cellulose of the wood and is formed mainly from oxidised groups.The cellulose also yields methylfurfuraldehyde whereas cellulose from filter pa per when heated with water under pressure yields only the minutest traces of this aldehyde . The yields of furfiiraldehyde from lignocellulose or cellulose and the yield of methylfurfuraldehyde from rhamnose decrease with the process of heating whereas the yields of methylf urfuraldehyde from the lignocellulose and cellulose of the wood increase up to a certain point on heating with water. J. J. S. Some Reactions of Sodamide. Lours MEUNrER and E. DESPARMET (Compt. rend. 1907 144 273- 275).-The action of sodamide on polyhaloid derivatives of the hydrocarbons is very similar t o that of alcoholic potash. With ethylene dibromide i t gives acetylene.With chloroform the reaction is slower in commencing but becomes explosive bromoform reacts similarly and even more violently ; if however powdered sodairiide is added in small quanti- ties t o excess of chloroform and the latter warmed slightly ammonia isORGANIC CHEMISTRY 187 evolved and a mixture of sodium chloride and cyanide precipitated. This reaction can be expressed by an equation CHC13+4NaNH,= NaCN + 3NaC1+ 3NH3 precisely similar to that for the prepara- tion of the carbylamines. Moreover chloroform diluted with anhydrous benzene when heated with aniline (1 mol.) and sodamide (3 mols.) gives phenylcarbylamine thus NH,Ph + CHCI + 3NaNH = 3NaCl+ 3NH3 +- PhNC. Sodamide can be employed for the preparation OF sodium derivatives (compare Alexeeff Journ.Rum. Pl~ys. Chim. SOC. 1902 34 526 ; Titherley,Proc. 1902,18 186; Haller Abstr. 1905 i 214; and Claisen and Feyerabend Abstr. 1905 i 286). Aniline diphenylainine and diazoaminobenzene readily give sodium derivatives. Addition of diphenylamine in ethereal solution to benzyl chloride in the same solvent containing a slight excess of sodamide causes a vigorous reaction with evolution of ammonia and formation of diphenylbenzyl- amine. Ethyl malonate when treated in cold benzene solution with sodamide forms a transparent jelly probably consisting of the additive compound N H,* C( OEt) (ONa) CH,* CO,Et which when heated evolves ammonia and gives the sodium derivative CHNa(CO,Et),. When anhydrous acetaldehyde is added to sodamide covered with dry ether a white crystalline precipitate stable in dry air is formed whilst ammonia is evolved and combines with the aldehyde forming aldehyde-ammonia.The evolution of ammonia can only be explained by the dehydration of the aldehyde and formation of the sodium derivative of the corresponding imine CH3*CH0 + 2NaNH2 = CH,*CH:NNa + NaOH + NH,. The crystalline precipitate is there- fore probably a mixture of aldehyde-ammonia and the sodimino- derivative. This explanation agrees with Delepine’s work on LEO TSCHUGAEFF (Ber. 1907 40 173-181. Compare Abstr. 1904 i 478; 1905 i 865; 1906 i 814).-The capacity of a number of primary secondary and tertiary amines to form complex compounds with copper silver platinum and nickel salts in #/LO solution has been investigated qualitatively and found to diminish as the number of N-hydrogen atoms substituted is increased.On addition of methyl- ethyl- n-propyl- isopropyl- n-butyl- isobutyl- tert.- butyl- sec.-butyl- n-amyl- isoamyl- terL-amyl- or vinyl-amine to aqueous copper chloride copper hydroxide is precipi- tated and dissolves on addition of a n excess of the amine forming the characteristic blue solution ; with camphylamine fenchylamine or thujylamine the addition of alcohol is necessary for coruplete solution of the blue compound which may be extructed with ether chloroform or benzene. The red compounds (Su),Cu,Sa [Su = C,H,(CO),N ; a = an amine] is formed on addition of succiniinide to the blue solutions. Under the same conditions secondary amines such as diethyl- di-n-propyl- di-isobutyl- di-isoamyl- and dibenzyl-amine dissolve only small quantities of the precipitated copper hydroxide whilst this is aldehyde-ammonia (Abstr.1895 i 462). E. H. Relative Stability of some Metalammine Compounds. 0 2188 ABSTRACTS OF CHEMIGAL PAPERS. completely irisoluble in tertiary amines trimethyl- triethyl- tri-78- propyl- triisobutyl- and triisoamyl-amines which do not form complex metallic compounds in either aqueous or alcoholic solution. On pro- longed contact with trimethylamine copper hydroxide is converted into the black oxide. The aliphatic amines react in the same manner with dilute silver nitrate forming a black precipitate of silver oxide which is dissolved by an excess of the primary amines. Camphylamine forms with silver oxide n crystalline compound which is soluble in alcohol. The primary aliphatic ainines form complex compounds with silver succinimide with development of heat (compare Landsberg Abstr.1883 476). Benxylanaine silver succininzide (Su)Ag,CH2Ph*NH crystallises from alcohol in nacreous leaflets and commences to become brown in a sealed capillary tube at 160° m. p. about 190' (decomp.). Silver oxide precipitated by addition of secondary or tertiary amines to dilute silver nitrate is dissolved by an excess of the secondary amines to a less extent than is copper hydroxide whilst it is almost insoluble in excess of the tertiary amines in which even silver chlorid2 is barely soluble. The behaviour of silver salts with pyritline and quinoline bases is completely analogous with that of the copper salts (Jcrgensen Abstr.1886 857). Whilst the action of primary aliphatic amines on potassium platini- chloride in aqueous solution leads to the formation of platoso-diamine chlorides and platoso-diamine platinosochlorides (Jorgensen loc. cit.) tertiary amines precipitate metallic platinum slowly at the ordinary temperature or quickly on boiling trimethylamine yielding an odour of acetaldehyde. With nickel salts and aliphatic amines there have been obtained in addition to the succinimide compounds derived from primary amines (Su)2Ni,2a (Abstr. 1906 i 814) only an unstable devivative of dimet hy lam i n e. [With J. Su~~~~a~z:]-Tetramethj~ethy~enediamine does not form complex compounds with nickel salts (compare Werner Abstr. 1899 i 856; Kurnakoff Abstr. 1900 i 209).The difference of the behaviour of the pyridine bases from that of the aliphatic secondary amines is discussed and considered to support Euler's views on the formation of complex ions (Abstr. 1904 ii 379). G. Y. S tereoisomeric Diaquodieth ylenediaminecobalt Salts. ALFRED WERNER [and in part G. JAN'ISCH] (Ber. 1907 40 262-271).-l'he salts of this series are obtained init.ially from complex ethylene- diarnioecobalt compounds which are formed by atmospheric oxidation of aqueous cobalt nitrate or sulphate in the presence of ethylene- diamine and which will be described in a future paper. cis-niarluodieth?jlenediu~ninecobult chloride g$Co en,]C13,2H,0 is oLtained by triturating the preceding compounds with hydrochloric acid saturatad at no or from hydroxouquodiethyleizediaminecobaltORGANIC CHEMISTRY.189 bromide in a similar manner. ('' Hydroxo " indicates the hydroxyl group in direct union with the metallic atom.) This basic bromide lsp en,]Br,,H,O is precipitated in red crystals by the addition of pyridine and powdered potassium bromide to the syrup obtained by the evaporation of an aqueous solution of dinitratodiethylenediaminecobalt nitrate (A. Lieben. Pestschrijl 21 1). cis-l)iuguodieth~lenedi~minecobaEt bromide is obtained by the sage 'mechods as <he chloride. The two salts form red crystals and are extremely soluble in water forming solutions with an acid reaction. At 115' the salts lose 4H,O the chloride forming cis-dichlorodieth ylenediamine co balt chloride (violeochloride) and a small quantity of the green ti-am-isomeride whereas the bromide yields chiefly trans-dibromodiethylenediaminecobalt bromide ( praseobromide).The cis-diaquo-chloride or bromide in boiling aqueous solution is converted by hydrochloric or hydrobromic acid into trams-dichloro- diethylenediaminecobalt chloride or the corresponding bromide whilst potassium hydroxide converts them in to cis-hydroxoaquodiethylene- diaminecobalt chloride (or bromide). The configuration of the two salts is ascertained by treating them with sodium nitrite and acetic acid whereby an unstable dinitrito- diethylenediaminecobalt salt [(ON*O),Co en,]X is obtained which changes into 1 2- dinitrod iethylenediaminecobal t nitrite. trans-Biapuodiethylenediarninecobult chloride H2°Co en2 C1,,2H20 cw H,O 1 and the corresponding byomide [( H2O),C0 en2] Brg 2H,O are obtained by treating 1 6-hydroxoaquodiethylenediamineco balt bromide (com- pare following abstract) with the concentrated halogen acid or from Werner and Brztunlich's di-isothiocyanodiethylenediaminecobalt thio- cyanate (Abstr.1900 i 86) in the following way. An aqueous solu- tion of the thiocyanate is heated with potassium hydroxide cooled and treated with hydrobromic acid ; the reddish-brown precipitate of 1 6 - hydroxoaquodiet hylenediaminecobalt t hiocyanate is dissolved in 50% acetic acid and treated with sodium nitrite whereby 1 6-di- nitritodiethylenediaminecobalt thiocyanate is obtained which by tritura- tion with concentrated hydrochloric or hydrobromic acid yields the required salt. The trans-diaquo-chloride forms glistening reddish- brown needles the bromide violet-brown leaflets. Both contain 2H,O which is lost readily.By stronger heating the chloride is converted mainly into the dichlorovioleo-chloride whilst the bromide yields only the dibromopraseo-bromide. c. s. Theory of Hydrolysis and Stereoisomeric Hydroxoaquo- ALFRED WERNER (Bey. 1907 40 diethylenediaminecobalt Salts. L\ I .4 obtained by the addition of pyridini or less suitably of potassium190 ABSTRACTS OF CHEMICAL PAPERS. hydroxide to an aqueoue solution of cis-diaquodie0hylenediaminecobal~ chloride is a brownish-red crystalline powder and is reconverted into the diaquochloride by concentrated hydrochloric acid. From an aqueous solution of the substance which has been heated a t 1 1 5 O before solution triethylenediaminecobalt salts and ethylenediamine- cobalt salts can be obtained. cis-Hudroxoaauodiethvlenedic~mine~o~c~~t bromide is obtained (1) like the" preceding-compound; (2) by treating trans- dichlorodiethylenediaminecobalt chloride (praseo-chloride) with con- centrated potassium hydroxide and neutralising the resulting solution with cold concentrated hydrobromic acid; (3) in a similar manner from cis-dichlorodiethylenediaminecobmlt chloride (violeo-chloride) It forms a red crystalline powder and possesses properties similar t o those of the chloride.The iodide [{;\ g(;bCo en211,,H,0 is obtained in small brownish- L-\ I Y red needles by treating an aiueous solution of cis-diaquodiethylene- diaminecobalt bromide with pyridine and powdered potassium iodide. [-:I :Po en2 S,O crystallises in slender violet- The ditlionate red needles and is prepared by adding pyridine and saturated sodium dithionate to the solution of the syrup obtained by the evaporation after prolonged boiling of an aqueous solution of dinitratodiethylene- diamin ecobalt nit rate.1 [{;; .,$Go ent]C1 trans-Hydroxoapuodiethylenediami~~ecobalt chloride is obtained from aqueous trans-diaquodiethylenediaminecobalt chloride in pearly-bluish -red leaflets by the addition of potassium hydroxide or less readily in needles by the addition of pyridine. (l) Ho Co en Br2 is obtained similarly or better by The bromide [(6) H,O boiling an aqueous solution of cbe cis-compound for two minutes with potassium hydroxide and neutralising the well-cooled solution with hydrobromic acid.It is a light red crystalline powder ; the cryoscopic method in aqueous solution indicates the presence of three ions 1 [g%Coen21 and 2Br. L L The iodide [[;I en2 I is obtained in pearly reddish-brown leaflets by decomposing an aqueous solution of brans-diaquodiethylene- diaminecobalt chloride with concentrated potassium hydroxide followed by the addition of potassium iodide. Ho Coen S,O obtained by the addition of saturated sodium dithionate to an aqueous solution of brans-hydroxo- aquodiethylenediaminecobalt chloride crystallises in glistening red needles. The salts of the cia- and tram-hydroxoaquodiethylenediaminecobalt 1 Lw H20 I The dithionate,ORGANIC CHEMISTRY. 191 series have a faintly alkaline reaction but do not precipitate silver oxide from silver nitrate solution or absorb carbon dioxide ; mineral acids convert them into salts of the diaquo-series.They are as a rule sparingly soluble in water but dissolve readily in the presence of acetic acid forming solutions from which metallic salts precipitate the corresponding hydroxoaquo-salt The properties of these salts of the basic diethylenediaminecobalt series those of Pfeiff er's pyridine chromium compounds (Abstr. 1906 i 531) and those even of Jorgensen's pentarnmine and tetrammine cobalt and chromium salts (Abstr. 1883 554; 1891 1385; 1898,.ii 226) cannot be rationally interpreted by Jorgensen's theory that the hydroxyl group is linked to a water molecule thus po;TNa&$25 dK!* By the author's theory the formation of hydroxoaquo- from diaquo- compounds is represented [e.2C02g] X + C,NH = [en,CoHo ]X + C,NH,*HX H2O and the tendency for the reverse change to occur en2CoH20 X + HX' = en,CoHaO x serves to account for many of the properties of the hydroxoaquo-salts An attempt is made to explain the formation and reactions of HO1 L H201X' hydroxo-salts by the aid of the ionic hypothesis.c. s. Synthesis of a- Amino- y-hydroxybutyric Acid. EMIL FISCRER and HERBERT BLUMENTHAL (Ber. 1907 40 106-1 13).-a-Bromo-y phenoxye~h~Z~aZonic acid OPh C H2* CH CBr (CO,H) obtained by the gradual addition of bromine t,o an ethereal solution of y-phenoxyethyl- malonic acid (prepared according to Perkin Bentley and Haworth Trans. 1896 69 165) sepnrates from benzene in rhombic crystals m. p. 1413" (corr.) with evolution of gas.When heated at 150-155Oit evolves carbon dioxide and is converted into a-bromo-y-phenoxybutyric acid OPh*CH,*CH,*CHBr*CO,H which separates from a mixture of etherand light petroleam in stellate prisms and has m.p. 101*5°(corr,) a-Amino-y-phenoxybutyric acid OPh*CH20CH,*CH(NH,)*C02H obtained by agitating the preceding compound with aqueous ammonia and then either allowing the mixture to remain a t the ordinary temperature for four to five days or heating in a closed vessel for three hours a t looo separates from water in colourless needles m. p. 233" (decomp.). When boiled with strong hydrobrornic acid phenol and a-amino- y-hydroxybutyric acid OH*CH,* CH2* CH(NH,)* CO,H are formed the latter readily passing into its lactone which crystallises out in the form of its hydrobromide.U - A ~ ~ n o b u t ~ r o ~ a c ~ o n ~ hydrobromide C,H,02NBr separates from alcohol in glistening almost colourless pyramids m. p. 227' (corr.) (decomp.) ; when treated with silver car- bonate it forms aither the lactone or the free acid according to the con- ditions. a-Anaino- y-hydroxybutyric acid OH* CH,*C€X,*CH(NH,)*CO,H crystallises from aqueons alcohol in silky colourless needles m. p. 187" (corr.) (decomp,) it has a very faint acid reaction towards litmus Its copper salt forms dark blue prisms Its hydrochloride C,H,O,NCl,H,O,192 ABSTRACTS OF CHEMICAL PAPERS. separates from aqueous alcohol in prisms ; when dehydrated it has m. p. 201-203O (corr.) (decornp.). a-Aminobutyrolactone may be obtained in the crude form as an oil by the addition of potassium carbonate to an aqueous solution of a-aminobutyrolactone hydrobromide ; on exposure a t the ordinary tem- perature it solidifies being converted into di-/3-hyitroxyethyldiketo- pipratxine OH*CH,* C H ~ = C H < ~ ~ .NH>CH=CH CH,* OH which crystallisesfrom alcohol ; it softens at 185' and has m. p. 192" (corr.). In aqueous solution it is neutral and does not form acopper salt. The substance is possibly a mixture of two stereoisomerides. a-Benaoylamino-y-lbydroxybutyric acid OH* CH,*CH,* CH( NHBz)* C02H prepared by the addition of benzoyl chloride and sodium hydroxide to a-aminobutyrolactone hydrobromide separates from water in colourless needles. which soften at 117" and have m. p. 121" (corr.). Itsaqueous solution gives an acid reaction and when boiled for several minutes is converted into a-benxollZa7,ainobzctyroZccctolze Ci,HliO,N which separates in hard crystals ; it softens a t 137' and has m.p. 142' (corr.). Action of Acid Anhydrides on Creatine and on Greatinine. Compare A. McK. F. URANO (Beitr. chena. Physiol. Path. 1907 9 183-184. Erlenmeyer junr. Abstr. 1895 i 31 O).-Be.lzxoyZcreutilzine is formed when benzoic anhydride is heated with creatine at 120" or with creatinine at 150". It crystallises from 95% alcohol in pale yellow needles m. p. 1S7O. PhthaZy Zdicreat ine C H4[ CO NH* C( NH) *NMe* CH,*CO,HI2 obtained by heating phthalic anhydride with creatine or creatinine a t 140" for ten hours crystallises from alcohol in slender colourless needles m. p. 2 12'. J. J. S. EMIL FISCHER (Ber.1907 40 489-50s. Compare Walden Abstr. 1896 i 205; 1898 i 127 178; 1899 ii 53S).-The results of Walden's experiments on the chacge of an active substance into its antipode without the intermediate formation of the racemic form can be formulated by the scheme (NOC1) (PCU I--+ I-a-Chlorosuccinic acid 5:; d-malic acid C,Hl,O2N3 Walden's Inversion. I I Z-Aspartic acid I-+ Z-Malid acid c.d-a-chlorosuccinic acid (N20,) (KOH) The inversion must be caused by the action of the silver oxide or of the potassium hydroxide (or phosphorus pentachloride) ; Walden regards the latter as producing an optically normal reaction that is one without change or configuration. If this be so either nitrosyl chloride or nitrous acid must cause inversion by its action on Z-aspartic acid.Similar inversions have been performed by the author with alanineORGANIC CHEMISTRY 193 (Abstr. 1905 i 692) leucine (Abstr. 1906 i 808) and phenyl- alanine (NOBr) (NH,) -+ Z-Bromopropionic acid - 9 d-Alanine I- Alanine t- d-Bromopropionic acid +- I “HJ (NOBr) The active a-bromopropionic acid or its ester is converted into the amino-acid of the same sign by aqueous or liquid ammonia or by potassium phthalimide whereas by the action of nitrosyl bromide d-alanine and its ester yield bromopropionic acid and ester of opposite signs. d-Alanine -+ I-bromopropionic acid d-Alanine ester -+ d-bromopropionic ester. This result which has been observed in the case of other amino-acids indicates that optical inversion is caused by the action of nitrosyl chloride or bromide.Walden’s contention that potassium hydroxide or phosphorus penta- chloride causes an optically normal reaction is supported by his own observation that active haloid acids and their esters are changed into hydroxy-acids and esters of the same sign by the former whereas d-l‘actic acid or its ester yields d-chloropropionic acid by the action of the latter. Moreover aqueous dkhloropropionic acid is converted by silver oxide into E-lactic acid (Purdie and Williamson Trans. 1896 69 837) whilst natural d-alanine yields d-lactic acid by the action of nitrous acid (Fisher and Skita Abstr. 1901 i 783). The author con- firms these results by showing that I-bromopropionic acid is converted into d-lactic acid by silver oxide or carbonate and into I-lactic acid by dilute potassium hydroxide.The ester of I-bromopropionic acid does not react with silver oxide a t low temperatures ; I - bromopropionylglycine however yields a sub- stance which is hydrolysed to I-lactic acid. The action of silver oxide on an haloid acid and its esters is similar to that of nitrosyl bromide on active hydroxy-acids and their esters. Little can be said a t present concerning the nechanism whereby optical inversion is produced. Walden regards the abnormal reac- tions caused by silver or mercuric oxide as due t o the formation of unstable additive products by the decomposition of which a change of configuration is rendered possible Evidence of the formation of addi- tive compounds has been obtained by the author in a few cases which are described below. The new ’compounds recorded are Ethyl 1-a-phthulylulanine C,H,<CO>N.CHMe*C02Et GO containing about 43% of the racemic form is obtained by heating ethyl I-a-bromo- propionate and powdered potassium phthalimide for five hours at 125’ t o prevent racemisation as much as possible {compare Gabriel and Colman Abstr.1900 i 358) ; it has m. p. 58-60’ and [UF 7-15’ in alcoholic solution.294 ABSTRACTS OF CHEMICAL PAPERS. Phthalyl-d-atanins C6H,<;>N*CHMe*CO,B m. p. 150-151° (corr.) softening a t 1 3 9 O is obtained by heating d-alanine and phthalic anhydride for seven hours a t 120-125'; it separates from hot water in small quadrangular leaflets has [ a 3:' - 17.84' in alcoholic solution and yields d-alanine by hydrolysis with 20% hydrochloric acid ; the ethyl ester has m.p. 54-56" (corr.) and [a]S - 12.46'. By the action of excess of bromine on ethyl d-alanine or ethyl E-leucine in a minimal quantity of 20% hydrobromic acid in a freezing mixture red oils are obtained which seem to consist of additive com- pounds of bromine and the ester ; they are decomposed by nitric oxide yielding respectively ethyl d-a- broinopropionate aiid ethyl d-a-bromo- isoh exoat e. Ethyl 1-a-bromoisohexoute prepared from I-a-bromoisohexoic acid obtained from I-leucine and nitrosyl bromide has b. p. 49-54'/0*5 mm. [ a ] ? - 43*1° and contains some of the racemic form 1-a-Bronzopropionylglycin~ CHMeBr*CO*NH*CH,*CO,H m. p. 120" (corr.) is obtained conveniently from glycirie and I-a-bromopropionyl chloride ; it crysiallises in large prisms [a] - 35.27' in aqueous and - 46.6' in alcoholic solution.By treatment with water and silver car- bonate it yields at first slender needles of a silver salt but after long keeping and evaporation a v'iecous liquid is obtained probably consist- ing of the active lactylglycine which by hydrolysis yields 1-lactic acid. r-Lactylglycine OH.CHMe*CO*NH*CH,*CO,X prepared from ?*-a- bromopropionylglycine in a similar manner has m. p. 108.5 -109.5' (corr.). c. s. Aminolactaldehyde. ALFRED WOHL and H. SCHWELTZER (Bey. 1907 40 92-102).-a-ChZoro-P-T~ydroxypropuldeh~de methyl acetal OH*CB,-CHCl*CH(OMe) best obtained by preparing the requisite hypochlorous acid by passing a current of chlorine into an aqueous solution of sodium hydrogen carbonate and then adding acraldehyde dirnethyl acetal (compare Abstr.1898 i 555) has b. p. 97-9S0/11 mm. Its benxoyl derivative has b. p. 68'/0*25 mm. a-C'hloro-P- benxoylh?Jdroxyp?.opa~dehyd~ ethyl acetul OBz CH2 CHCl°CH( OEt) has b. p. 128"/0*3 mm. The constitution of a-chloro-P-hydroxypropaldehyde methyl acetal is indicated by its behaviour on oxidation with alkaline potassium permanganate when the potassium salt of the acid CO,H.CHCl*CH(OMe) is formed. By the action of methyl iodide the latter salt was con- verted into the methyl ester CO,Me*CHCl*CH(OMe) b. p. 86'/11 mm. The corresponding etlql ester CO,Et*CHCl*CH (OEt) has b. p. 116-117°/11 mm. Aminolactaldehyde methyE acetcd NH,*CH,*CH(OH)*CH(OMe) ob- tained by heating a mixture of a-chloro-P-hydroxylpropaldehyde methyl acetal and sodium iodide with methyl alcoholic ammonia at 120° for forty-eight hours has b.p. 1 0 0 - l l l o / l l mm and separates from ethyl acetate in needles m. p. 55-58',ORGANIC CHEMISTRY 195 Amiraolactaldehyde ethyl acetal NH,*CH,*CH(OH)*CH(OEt)2 has b. p. 120-121°/14 mm. Amirtokactakdehyde hydrochZmGZe NH,~CH,~CH(OH)~CWO,HCl ob- tained by the action of fuming hydrochloric acid on aminolactaldehyde methyl acetal crystallises in needles and begins to decompose a t 137'. It reduces both Fehling's solution and ammoniacal silver nitrate. Its semicarbaxone CH,(NH,Cl)* CH(0H) *CH :N*NH* CO*NE 2MeOH is hygroscopic softens at 72O and has m. p. 74-75'. Its plcctinichloride begins to decompose at 155'. When aminolactaldehyde hydrochloride is oxidised by bromine it forms isoserine.When aminolactaldehyde hydrochloride is dissolved in ethyl alcohol and a few drops of chloroform are added and the ~iiixture agitated for twenty-four hours at the ordinary temperature with diethylambe anhydrobisamiiioEactaldehyde (isoserine uldehyde) [ NH,* CH,* CH( OH)*CH N CH,=CH(OH)*CHO] is obtained RS a white powder. The aqueous solution of the latter compound gives an alkaline reaction ; it reduces ammoniacal silver nitrate and boiling Pehling's solution and begins to decompose at 1 2 5 O . When its molecular weight is determined by the cryoscopic method in aqueous solution values are obtained for a termolecular compound ; after standing two days the values indicate a bimolecular structure and finally after five days a unimolecular structure. Dilute hydro- chloric acid converts the anhydro-compound either in its unimolecular or in its termolecular form a t the ordinary temperature into the aminoaldehyde hydrochloride.A. McK. Constitution of Cyanic Acid. I?. CARLO PALAZZO and EDUARDO CARAPELLE (Chem. Centr. 1906 ii 1723-1724 ; from Ests-. Giorm. Sci. Nat. Econ. 26. Compare Nef Abstr. 1896 i 71).-Since the action of diammethane (compare Meyer Abstr. 1906 i 108) on cyanic acid yields a derivative of a carbamide the author concludes that free cyanic acid is not tautomeric but has the formula O:C:NH and that its salts are also carbimides. The action of the acid on diazo- methane is somewhat energetic. When the ethereal solution of the acid a t - 1 2 O is poured into the ethereal solution of diazomethane at - 5" and the mixture treated with dry ammonia methylcarbamide NH,*CO*NHMe m.p. 101-102' is the main product. Diazoethane yields ethylcarbamide ; methyl ethylcarbamate NHEt CO,Me b. p. 96-100°/50 mm. 70-73"/19 mm. (compare Klobbie Rec. trav. chirn. 1888 7 355) is also formed from the methyl alcohol which always accompanies diazoethane (compare von Pechmann Abstr. 1899 i 134). E. W. W. Preparation of Cyanoacetylcarbamide and its Alkyl and Amy1 Derivatives. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 175415).-It has been found that cynnoacetylcarbamide and its derivatives can be readily obtained by condensing cyanoacetic acid and carbamide or one of its alkyl or acyl derivatives with an acid anhydride. A mixture of carbamide cyanoacetic acid and acetic196 ABSTRACTS OF CHEMICAL PAPERS.anhydride when warmed on the water-bath furnishes pure cyano- acetylcarbamide. Methylcarbamide cyanoacetic acid and propionic anhydride give cyanoacetylmethylcarbamide. Dimethylcarbamide cyanoacetic acid and acetic anhydride yieId cyanoacetyldimethyl- carbamide whilst phenylcarbamide cyanoacetic acid and benzoic anhydride give rise t o cyanoucetyI~henylcurbccmide (m. p. 2 16'). G. T M New Synthesis of Fulminic Acid. The Formation of Fulminic Acid from Aloohol and Nitric Acid. HEINRICH WIELAND ( B e y . 1907 40 418-422).-When methylnitrolic acid is boiled for a short time with dilute nitric acid and silver or mercuric nitrates the corresponding salt of fulminic acid crystalIises out ; the by-products of the interaction are formic acid nitrous oxide carbon dioxide ammonia and a small quantity of nitrous acid and nitric oxide.The interaction of nitric acid and alcohol is explained by the following scheme CH,*CH,*OH -+ CH,*CHO -+ CH(:NOH)*CO,H -+ NO,*C(:NOH)*CO,H -+ NO,mC(:NOH)H -+ HNO + C:NOH. The experimental support for the above hypothesis is as follows. Wohler (Abstr. 1905 i 418) found aldehyde a more suitabIe agent than alcohol for the preparation whilst the formation of methyl- nitrolic acid from isonitrosoacetic acid has been accomplished by Ponzio (Abstr. 1903 i 453). W. R. Iron-Cyanogen Compounds. IV. KARL A. HOFMANN [with H. ARNOLDT and H. HIENDLMAIEK] (Annulem 1907 352 54-72).- With the object of showing the truth of the former statement (Abstr. 1906 i 75) that the blue *iron-cyanogen compounds formed either from ferric salts and ferrocyanide or ferrous salts and ferricyanides are derivatives of potassium ferrocyanide in which potassium is either wholly or partly replaced by tervalent iron the reduction of mixed solutions of ferric salts and potassium ferricyanide has been studied. I t has been further shown that those compounds believed by several investigators to be ferrous cyanide are really complex iron-cyanogen compounds.The compound Fe,C,N,H,2 $H20 is obtained by treating a solution containing molecular proportions of potassium ferricyanide and ferric alum with hydrogen peroxide; since this compound differs only from that obtained by treating soluble Prussian blae with dilute acid in the percentage of water present it is evident that soluble Prussian blue contains the ferrocyanide complex.When a solution containing potassium ferricyanide and ferric chloride is acted on by free hydroxylamine soluble Prossian blue alone is formed; from this i t follows that soluble Turnbull's blue is ideDtica1 with soluble Prussian blue ; in other words Turnbull's blue is not a ferrous ferricyanide. Ferrous cyanide is not obtained by add- ing ammonia to a solution containing ferrous chloride and prussic acid ; the precipitates thus obtained on oxidation are converted into complex substances in which the atomic ratio of iron to carbon isORGANIC CHEMISTRY. 197 1 3 and not 1 2 as it would be were the original precipitate ferrous cyanide. The compoulzd Fe,C6N,NH,,1 +H,O is obtained by oxidising the precipitate formed by the interaction of ferrons chloride (1 mol.) hydrocyanic acid ( 6 mols.) and ammonia (4 mols.) and similarly the compound Fe,~,N,H,2H20 when the proportions ferrous chloride (1 mol.) prussic acid (6 mols.) and ammonia (2 mols.) are used.These compounds are blue powders decomposed by 4% ammonia in four minutes at 15’’ insoluble in water soluble however in a saturated aqueous solution of oxalic acid. Similar compounds were obtained by using hydroxglamins instead of ammonia When the compound Fe,C,N6H2 obtained by boiling an aqueous solution of hydroferrocyanic acid with exclusion of air is oxidised a blue compound Fe,C,N,H,H,O insoluble in water oxalic acid and ammonium oxalate solutions is formed. Although similar to Williamson’s violet it differs from it in that it is decomposed by ammonia.Attempts to prepare a Williamson’s violet containing sodium were unsuccessful. The compound Fe,C,N,K obtained as a residue in the preparation of hydrocyanic acid is also formed by heat- ing a solution of potassium ferrocyanide with excess of oxalic acid. All soluble blue iron-cyanogen compounds of the general formula FeC6N6FeMe,xH,0 are reduced by ammonium oxalate in direct sun- light to a yellowish-white substance which is converted by hydrogen peroxide into Monthier’s blue (Berzelius Jahresb. 27 173). The latter compound Fe,C,N,NH,,H,O is however best prepared by oxidising with hydrogen peroxide the green precipitate obtained by acting on a solution containing potassium ferrocyanide ammonium chloride and ammonia with fine iron wire; it dissolves in water and oxalic acid forming blue solutions not however in ammonium tartrate solution; it is precipitated from its aqueous solution by ammonium oxalate and is decomposed by 4% ammonia in five to seven minutes.It is therefore very similar to the blue iron-cyanogen compound obtained from an acidified solution containing potassium ferrocyanide (1 mol.) and a ferrous salt (1 mol.) (compare Abstr. 1905 i 756). A com- pound of the same formula Fe2C,N6NH,,H,0 is obtained by oxidising in a neutral solution the compound formed by the reduction of Prussian blue with hydrogen sulphide. Robiquet [Dammer Hand- buch 111. (1893) 3641 considered the substance obtained by reducing Prussian blue with hydrogen sulphide to be ferrous cyanide but this cannot be correct since by oxidation in neutral solution only an OXY- cyanide and not the above compound Fe,C,N,NH,,H,O should be obtained.W. H. G. Conditions of Stability of the Carbylamines. H. GUILLEMARD (Compt. rend. 1907 144 141-143. Compare this vol. ii 141).- When a mixture of excess of ethylcarbylamine with a small quantity of ethyl iodide is kept at the ordinary temperature for a prolonged period a brown crystalline additive compound 2EtNC,3Et17 may be isolated by distillation in a vacuum. It is very soluble in water and organic solvents and is easily decomposed by heat by acids and by alkalis ; with the latter the products include diethylamine and alkali1 98 ABSTRACTS OF CHEMICAL PAPERS. oxalate. If the action takes place at a high temperature a h r r y product apparently either a mixture of the above compound and a polymeride of the carbylamine or a compound of this polymeride with ethyl iodide is obtained The carbylamines are instantly destroyed by normal alkp 1 sulphntes and by those sulphovinates which are not strictly neutral.They combine with metallic cyanides giving compounds the stability of which varies with the cyanide employed but all are dissociated by heat. The silver compound AgNC,CNEt which can be considered as the ethyl ester of hydroargentocyanic acid dissociates into silver cyanide and ethyl carbylamine below 140'. Above 140' a mixture of nitrile and carbylamine is formed the proportion of nitrile increasing with rise of temperature The silver compound when heated to 160' in asealed tube for four hours is completely converted into silver cyanide and the nitrile.When the carbylamines are heated in sealed tubes the molecular weight rises gradually a t temperatures from 100' to 160' and falls between 160" and 240° whilst the quantity of nitrile formed increases regularly from 140Oto 240° at which temperature the conversion into nitrile is complete. Hence it follows that on heating the carbylamine polymerises first and the product dissociates into carbylamine and nitrile the proportion of the latter increasing as the temperature is raised because the reaction is not reversible. A small quantity of the polymeride was isolated as a very explosive oily substance which from a cryoscopic determination appears t o be termolecnlar. The conclusion is drawn that in their preparation the carbylamines may combine with the alkylating agent and under the action of heat may give rise to nitriles after polymerisation or combination with the cyanide.E. H. Complex Compounds of Oxalenediamino-oxirne. LEO TSCHUBAEFF and JAC. SURENJANZ (Bey. 1907,40,281-185. Compare Abstr. 1905 i 743 ; 1906 i 814).-0xalenediamino-oxime which resembles on the one hand the ethylenediamines i n having two amino- groups in the ap-position to each other and on the other hand the a-dioximes in having two oxime groups in the same relative positions has as was to be expected a strong tendency to the formatioc of two series of complex metallic compounds. I n the present paper the nickel compounds are described. The action of slightly more than 2 mols.of oxalenediamino-oxime on nickel acetate (1 mol.) in aaueoas solution. or on other nickel salts in I 1 presence of ammonia pyridine or ammonium acetate lends to the formation of the compound N~(OXH)~,~H,O which crystallises in orange-red needles Ioses 2H20 a t i l O o and decomposes with explosive violence at about 270'. It dissolves in dilute mineral acids or acetic acid forming a blue solution is decom- posed by an excess of mineral acid gives a brownish-red coloration with concentrated aqueous alkalis yields nickel sulphide when treated with hydrogen or ammonium sulphide and on solution in aqueousORGANIC CHEMISTRY. 199 potassium cyanide forms oxalenediamino-oxime and potassium nickel cyanide. I n concentrated solution and in presence of acetic acid 1 mol.of nickel chloride reacts with 3-4 mols. of oxalenediamino-oxime forming the chloride Ni(OxH,),Cl which crystallises in bluish-violet needles decomposes suddenly a t 230° and is moderately stable in acid solutions ; towards ammonium sulphide excess of mineral acid or potassium cyanide solution it behaves in the same manner as the orange-red compound into which it is converted by the action of water. Both chlorine atoms are ionised being removed as silver chloride on addition of silver nitrate. The nitrate Ni(OxH,),(NO,) forms bluish-violet prisms behaves towards reagents in the same manner as the chloride and yields the whole of its nitric acid as nitron nitrate on addition of nitron acetate solution (Busch Abstr. 1900 ii 282). The structures of the two nickel compounds are discussed and concluded to be NH,* Q=NObNi<N O=S*NH and NH,*C:NOH* NOH:C-NH ..NH2*$X NOH respectively.G. Y. Study of a Case of Isomerism among the Oxmium Gom- pounds of Grignard and Baeyer. WLADIMIR TSCHELINZEFF (Conzpt. rend. 1907 144 8S-9O).-If the oxonium derivatives obtained by the condensation of organomagnesium compounds with ethers possess the structure suggested by Eaeyer (Abstr. 1902 i 355) isomerides of the types OR,X*MgR’ and ORR‘X-MgR should be possible and the author has prepared a series of compouuds in which R=C,H and R’=C,K C,H9 C5Hll or C,H by adding one equivalent of the ether to the organomagnesium compound in benzene solution and has measured the heat developed when the compounds are decomposed by water Ethylmagnesiumethylpropyloxoniuni iodide OEtPrI*MgEt obtained from ethyl propyl ether and magnesium ethyl iodide has a heat of decomposition 62.3 cal.and the isomeride propyl- magncsiumdiathyloxcium iodide OEt,I*MgPr has 62.5 citl.; sitnilarly ethylmagnesiumethylisobutyloxonium iodide C4H,*OEtT.*1111gEt has 58.7 cal. and isobutylmagnesiumdiethyloxonium iodide has 60.2 cal. ; e t h y lmagnesiu m e th ylisoamy loxonium iodide C,H * 0 E t I MgE t yields ethane when decomposed by water with a heat development of 62.9 cal. whilst the decomposition of isosmylmagnesiumdiethyl- oxonium iodide OEt,I*Mg*C,H, is not accompanied by any evolution of gas and the heat equivalent is 60.5 cal. ; ethylmagnesiumphenyl- ethylosonium iodide OEtPhIOMgEt is decomposed by water with evolution of ethane and a heat equivalent of 62.1 cal.and phenyl- magnesinmdiethyloxonium iodide OEt,I*MgPh yields benzene on decomposition with water and a heat equivalent of 59.2 cal. No conclusions as to the possible isomerism among the oxonium derivatives can be drawn from the results of the thermochernical investigntion given above as the thermal values are practically200 ABSTRACTS OF CHEMICAL PAPERS. identical but the nature of the products of decomposition show that the compounds do show isomerism of the type suggested by Baeger. M. A. W. P-Mercuridipropionic Acid. EMIL FISCHER (Ber. 1907 40 386-389. Compare Pesci Abstr. 1901 i 624).-This work mas undertaken to fill a gap in the organo-mercuric derivatives amongst which previously no compounds of the fatty acids have been described. Ethyl P-merczLridiiuropionate Hg(CH,*CH,* CO Et) prepared by shaking ethyl /3-iodopropionate with sodium amalgam in cooled ethereal solution is obtained on evaporation of the ethereal solution in a vacuum as a yellow oil having an unpleasant 0dou.r.The acid Hg(CH,*CH,*CO,H) formed by shaking the ester with N-sodium hydroxide crystxllises from water in slender colourless odourless prisms m. p. 148.5-149.5' (corr.) can be titrated with sodium hydroxide in presence of phenolphthalein is readily decomposed by halogens or strong acids and yields with iodine mercuric iodide with a limited amoiin t of boiling hydrobromic acid a crystalline substance which may be 61.omomercuripropionic acid or with an excess of hydro- bromic acid mercuric bromide; when warmed gently with iodine in aqueous potassium iodide solution mercuridipropionic acid yields a dark crystalline periodide.P-Mercuridipropionic acid is decomposed by water a t 100' yielding propionic acid and the anhydride of 6-hydroxymercuripropionic acid CH2* yH2 which separates in colourless crystals becomes grey at about 1 90° gradually decomposes a t higher temperatures and is soluble in dilute alkalis or warm dilute acids. The copper lead and silver salts are described. Hg<*-CO G. Y. The Benzene Nucleus its Reactivity and the Valency Strength of its Substituting Groups and of Carbon. JULIUS OBERMILLER (J. p r . Chem. 1907 [ii] 75 1-61. Conipare Flurscheim Abstr. 1905 i 614).-The argument of this theoretical paper is based on the following conceptions of valency.(1) The valencies of an atom are the directions in which the force constituting the total affinity of the atom acts. The valencies act in straight lines but may be diverted t o a certain extent. The valency of an atom is the number of directions in which the affinity acts and the number of valencies of other elements which must be aeutralised in the formation of a chemical compound. (2) The total affinity of the atom varies for different elements and is not proportional t o the valency that is the average affinities of the valencies of the atom are different for different elements. (3) It is not necessary in a chemical compound that the total aEnity of an atom should be completely neutralised; any excess of affinity expresses itself in the so-called secondary valencies partial valencies indirect linkinga &c.(4) The valencies of a multivalent atom may vary in strength the distribution of the total aEnity of the atom depending chiefly on the strength of the valencies neutralised.ORGANlC CHEMISTRY. 201 (5) The mutual attraction of chemical affinities is to be considered as a special case of mass attraction m.m‘/r2. The force forming the linking is the product of the two valencies which are mutually neutra-lised and which are not necessarily of the same strength. (6) The affinity necessary for the formation of a given linking is constant within certain limits outside OF which unstable compounds are formed or combination does not take place ; this necessary affinity varies for different combinations of atoms and depends on the manner i n which the remaining valsncies of the atoms concerned are occupied.It follows that in a combination of two atoms the affinity of the one atom must be the greater the less that of the second valency forming the linking. In the combination AB the afinity required of B in consequence of that of A to make the combination is termed the “ valency need-B” of the atom A and the possibility of measuriDg i t is discussed. It is suggested that the ‘cvalency need-C” of the carbon atom is greater than the affinity of the average carbon valency when it follows that in the centric formula for benzene which agrees best with the above conceptions of valency with the direct formation of substitution compounds and the nature of partially reduced benzene derivatives more than half of the total affinity of the six carbon atoms is required for the formation of the ring and after expenditure of sufficient affinity for the union with the six hydrogen atoms there remains for the centric valencies less afinity than is necessary for the formation of true C-C linkings ; the centric valencies are considered to be of the nature of pseudo-para-linkings.If now one of the hydrogen atoms is substituted by a group requiring a greater carbon affinity for combina- tion the remaining three valencies forming the two ortho- and the one para-linkings of the carbon atom to which the new group is attached must be weakened with the effect of rendering the two 0- and the p-hydrogen atoms less firmly attached to the nucleus and therefore more reactive.It is for this reason that the introduction of a second substituting group tends to take place in the 0- and p-posi tions. Meta- substitution is considered t o be a consequence of steric hindrance. The stability of a benzene derivative must diminish with increasing ‘ I valency need ” of the substituting group hence the great stability of benzene is in agreement with the order of “ valency need-C” represented by the series given below. These considerations are shown to apply also to the orientation of substitution in pyridioe naphthalene and anthracene and to the mutual influence on each other of two or more substituting groups as modified by their relative positions in the benzene nucleus. If the orientation of a group is influenced in two directions by two substituting groups already present in the benzene nucleus the influence of the stronger of these will predominate to the greater extent the more the two groups differ in ‘‘ valency need-C” and the more easily the introduction of the third group takes place.That the stronger substitution group is that with the greater ‘‘valencp need” follows from the above exposition of the affinity equilibrium of the benzene nucleus and its disturbance by substitution. From considera- tion of a number of cases of substitution it is shown that the VOL XCII. i. 23202 ABSTRACTS OF CHEMICAL PAPERS. ‘‘ valency need4 ” diminishes from N”’ to H in the series N”’ GIv NO SO,H OH NH CI(Br) CH H. The “ valency need-C ” of carbon being greater than the average affinity of a carbon valency the stability of methane and its homo- logues results from the small “valency need-C” of hydrogen on the other hand for the same reason whilst in tetranitromethane sufficient carbon affinity is at the disposal of each nitro-group hexa- nitroet,hane must be unstable if capable of existence (compare Hantzsch Abstr.1906 i 617). The properties of acetylene and of the cyanogen group the existence of both tetraphenylmethane and triphenylmethyl and the instability of two hydroxyls when attached to the same carbon atom are discussed from the author’s point of view. G. Y. [Oxidation of Aromatic Hydrocarbons and their Derivatives with Manganese Disulphate.] BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 175395).-Manganese disulphate Mn(S04)? in acid solution has the property of oxidising the methyl group of.toluene and its homologues and derivatives in such a way that aldehydes and finally carboxy-acids are obtained. The mangaaous sulphate resulting from the oxidation can be readily reconverted into the disulphate by electro- lytic oxidation. Toluene when oxidised a t 40-50’ furnishes an almost quantitative yield of benzaldehyde and when the oxidation is effected at a higher temperature with a further quantity of manganese disulphate benzoic acid is obtained finally. Benzyl alcohol and chloride may also be oxidised in this manner to yield benzaldehyde and even benzoic acid. G. T. M. Oxidation of Substituted Aromatic Hydrocarbons. FARB . WERHE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 174238).- o-Chlorotoluene is readily oxidised to o-chlorobenzaldehyde when sus- pended in 60-65% sulphuric acid at 50’ and treated gradually with cerium dioxide the temperature being slowly raised to 90’.The product now contains a white pasty mass of cerous sulphate mixed with o-chlorobenzaldehyde and a small quantity of o-chlorobenzoic acid the yield of aldehyde being 66%. The 0- and p-nitrotoluenes are similarly oxidised a t 80-85’ but in this case more of the corresponding nitrobenzoic acids are produced. The anthracenesulphonic acids are readilv oxidised in this way to a~thraquinonesu~pho~ic acids even at the ordinary temperature. “ G. T. M The Two Modifications of o-Nitrotoluene. EMIL KNOEVENAGIEL (Bw. 1907 40 508-517. Compare Abstr. 1903 i 785).-The existence of o-nitrotoluene in two forms (compare Ostromisslensky this vol.i 120) had been discovered by Schmidt and Berndt in 1903 in the Griesheim-Elektron works. The author also showed in 1904 that the =-form (m. p. - 9.4’) is transformed exothermally at low tempera- tures into the /3-form (m. p. -3.6’). The two modifications exhibit differences in the liquid as well as in the solid state and are therefore regarded as chemical isomerides and as instances of motoisomerism.ORGANIC CHEMISTRY. 203 The author proceeds to develo his theory of motoisomerism. The fact nitrobenzene determined five hours after distillation is attributed by the author to motoisomerism. that the viscosity of freshly (P ietilled nitrobenzene differs from that of c. s. Nitro-derivatives in t h e Menthane Series.111. MICHAEL I. KONOWALOFF (J. Russ. Phys. Chem. 15'oc. 1906 38 i 449-453. Compare Abstr. 1904 i 5 13).-Menthane was heated with nitric acid D 1.1 at 115-120° in a sealed tube. Three crystalline dinitro-corn- pounds were obtained melting respectively at 98-1 00' 92-953 and 75- 85O. The firxt fraction yielded dinityomenthane C,,H,,(NO,) probably N0,*CMe<CH2.cH2 cH2'CH2>CH*CMe2*N02 m. p. 107~5-108~5°. It is readily soluble in benzene sparingly so in ether and does not distil but commences to decompose at 210". Zinc dust and acetic acid reduce i t to the corresponding diarnine probably NH2*CM4CHO. CH2'CH2>CH*CMe,*NH2 CH0 b. p. 231-233' D 0,9263 f)A7*' 6.9108 ng'5 1.47955 a colourless liquid which does not solidify a h - 8". The hydrocidoride and suZphate are described.The cli6enxoyZ derivative C,,H,,(NHBZ)~ m. p. 232.5 -233*5O crystallises from alcohol in small needles. Z . I(. [Nitration of 3 4-Dichlorobenzenesulphonic Acid.] AKTIEN- QESELLSCHAFT FUR ANILIN-FABRIKATION (D. R.-P. 175022. Compare Abetr. 1904 i 1065).-The nitration product of 3 4-diehlorobenzene- sulphonic acid in concentrated sulphuric acid is poured on to ice and the nitro-sulphonic acids salted out in the form of their sodium salts. The mixed salts when redissolved in water and allowed to crystallise yield a crop of the less soluble sodium 4 5-dichloro-2-nitrobenzene- sulphonate whilst an isomeric salt of the nitro-sulphonic acid contain- ing the nitro-group either in position 3 or 6 remains in the mother liquors. The calcium barium and zinc salts of the latter acid are generally more soluble than those of 4 5-dichloro-2-nitrobenzene- sulphonic acid. On reducing the mixture of these two nitro-acids with iron and dilute acetic acid the corresponding amino-sulphonic acids are obtained.4 5-Dichloroaniline-o-sulphonic acid is by far the less soluble and is precipitated from an acidified solution of its sodium salt. The isomeric acid remains in the mother liquors and is obtained on concen- tration. When successively diazotised and treated with alkali one of the chlorine atoms of this more soluble acid is replaced by hydroxyl showing that the amino-group was originally in the ortho-position to one of the chlorine atoms It is on account of this reaction that the nitro-group is assumed to enter position 3 or 6.G. T. M. Unsaturated Acids of the Sorbic Series and their Con- version i n t o Cyclic Hydrocarbons. 111. OSCAR DOBNER (Ber. 1907 40 146-147).-The hydrocarbon C,H; previously termed cyclooctadiene (Abstr. 1902 i 598) is not identical with Willstatter P 2204 ABSTRACTS OF CHEMICAL PAPERS. and Veraguth's cyclo-octadiene (Abstr. 1905 i 515). As the latter possesses the properties of an unsaturated compound it is probable that the hydrocarbon obtained from P-vinylacrylic acid has the con- stitution ?H2'FH*C]H'?H2 and is termed tricyclooctane. CH,*CH*CH*CH,' J. J. S. Unsaturated Acids of the Sorbic Series and their Conver- sion into Cyclic Hydrocarbons. IV. OSCAR DOBNER and G. SCHMIDT (Beg*. 1907 40 148-152. Compare Abstr. 1902 i 598; 1904 i 149 and preceding abstract).-When the yellow modification of cinnamylidenemalonic acid is heated with anhydrous barium hydroxide it yields phenylcydobutene m. p. 25O b. p. 118-122°/ 13 mm. together with a considerable amount of diphenyltricyclo- octane b. p. 204-206°/10 mm. and a small amount of a hydrocarbon C,,H,,. The last is a viscous liquid and is not attacked by bromine or permanganate. The colourless cinnamylidenemalonic acid m. p. 178" ( Liebermann Abstr. 1895 i 470) when treated .in the same manner yields con- siderable amounts of diphenyltricyclooctane and small amounts of the hydrocarbon C3,H3 together with diphenyldicyclohecane QHPh*$?H*C]H CHPh*CH*CH,' m. p. 56O b. p. 212-2150/12 mm. and an unsaturated hydrocarbon a-phenyl-AaY-butadiene CHPh:CH-CH:CH b. p. 93-95'/12 mm.the tetrabromide of which melts at 150' (Klages Abstr. 1902 i 669 ; Itiiber 1903 i 471). Synthesis of Aldehydes and Ketones from as-Disubstituted Ethylene Glycols and their Ethers. A Correction. RICHARD STOERMER (Ber. 1907 40 488-489).-1t was stated (Abstr. 1906 i 581) by the author that when phenoxyditolylethylene was heated with alcoholic potassium hydroxide at 240° di-p-tolylethylene was formed toget her with the correspond in g et hoxy-compound. D i p tolylet h y lene was described as an 'oil b. p. 186'/20 mm. This oil is however a mixture of ditolylethylene and ditolylmethane. Di-p-tolylethylene had previously been described correctly by Bistrzycki and Reintke as a solid m. p. 61'. J. J. S. A. McK. Pentaphenylethane and Hexaphenyletbane. ALEXEI E.TSCHITSCHIBABIN (Ber. 1907 40 367-369. Compare Abstr. 1905 i 125; Flurscheim ibid. 614; Hantzsch Abstr. 1906 i 6 17).-Gomberg and Cone's pentaphenylethane (Abstr. 1906 i 82l) m. p. 178-179" (decomp.) determined in an atmosphere of carbon dioxide which behaves at the ordinary temperature as a saturated hydrocarbon when heated alone or in nitrobenzene solution decomposes into tetra- phenylethane and triphenylmethyl and absorbs oxygen. When heated with hydrogen chloride in benzene solution at 150' with exclusion of air it yields tetraphenylethane triphenylmethane and triphenylmethyl chloride. The decomposition in question must result from a wealrening of the linking between the diphenylmethyl and theORGANIC CHEMISTRY 205 triphenylmethyl groupe of the pentaphenylethane ; this behaviour resembles closely that of triphenylmethyl which consequently is con- sidered to be hexaphenylethane.Schmidlin’s supposed stable hexa- phenylethane (this vol. i 26) was probably impure tetraphenylethane. The experimental results described are opposed to Vorlander’s view that two hexaphenylethanes a stable and a labile form are capable of existence. G. Y. Condensation of cycZoHexanone. CARL MANNICH (Ber. 1907 40 153-1 58).-cycZoHexanone yields condensation products in much the same manner as aliphatic ketones (compare Wallach Abstr. 1896 i 5 7 2 ; 1897 i 425). A condensation similar to the formation of mesitylene from acetone occurs when cyclo- /\ bexanone is boiled for some ten to twelve hours with its I I own weight of concentrated sulphuric acid and 2.5 times \/\/\ its weight of methyl alcohol.The product dodecahydro- I 1 triphenylene the yield of which is some 6% crystallises /(/\/ from benzene in large compact prisms m. p. 232-233O. It may be sublimed in an atmosphere of carbon dioxide or hydrogen When heated with fuming nitric acid at 180’ it yields mellitic acid. Other products formed during the condensation are a ketone C,,H,,O probably identical with that obtained by Wallach (Zoc. cit.) and yielding a sernicurbcczone m. p. 275-17’i0 and a ketone C,,H,,O b. p. 214-217O/15 mm. The latter condenses with guanidine and the condensation product yields a picrate C,,H,,O,N m. p. 203’ (decomp.). J. J. S . I Triphenylene. CARL MANNICH (Ber. 1907 40 159-1 65).- Triphenylene is formod when dodecahydrotriphenylene (preceding ab- stract) is distilled with zinc dust in an atmosphere of /\ hydrogen.It may be isolated in the form of its picrate. II I The hydrocarbon crystallises from benzene or alcohol in \/\/\ colourless needles m. p. 198-1985°. A better yield is I ’ obtained when the dodecahydro-compound is passed over I\/\/ a layer of copper in an atmosphere of carbon dioxide at II I 450-500’. When completely oxidised it yields mellitic \/ With chromic acid it is oxidised t o a mixture of quinones and with fuming nitric acid yields a t,,Oinitra-derivative C,,H,( NO,) which crystallises from nitrobenzene in pale yellow slender needles and darkens at 335’ without melting. The hydro- carbon is identical with the triphenylene obtained in minute quantities by Schmidt and Schultz (Abstr.1881 435). J. J. S. I I acid. Use of Acetic Anhydride in Nitrating. KENNEDY J. P. ORTON (Ber. 1907 40 370-376. Compare Trans. 1902 81 806; Witt and Utermann this vol. i 27).-Nitric acid for use in nitrating in acetic anhydride is freed from nitrous acid by treatment with a limited quantity of carbamide nitrate. Nitroamines are obtained in a 90% yield together with nitro-corn-206 ABSTRACTS OF CHEMICAL PAPERS pounds and diazo-salts from aniline8 having one or both o-hydrogen atoms present if the amine dissolved in glacial acetic acid is run into a mixture of acetic anhydride and nitric and glacial acetic acids cooled in ice-water The presence of nitrous acid is necessary to the nitra- tion of dialkylanilines intermediate nitroso-derivatives probably being formed.Nitrotoluene has been prepared in a quantitative yield by nitration of toluene in presence of acetic anhydride; results are quoted showing that the function of the acetic anhydride is to combine with the water present in the nitric acid and formed during the reaction. Under the same conditions benzoic acid yields m-nitrobenzoic acid. G. Y. Electrochemical Reduction of o-Nitroacetanilide. KURT BRAND and EDWARD STOHR (Be?.. 1907 40 364. Compare this vol. i loo).-References are given to two other o-nitrosoanilines which had been overlooked by the authors. W. R. Phenylbiurets and the Biuret Reaction. HUGO SCITIFF (Annulen 1907 352 73-87. Compare Abstr. 1902 i 429).-By acting on phenylbiuret with aniline Weith (Abstr. 1878 141) obtained a compound which he describes as diphenylbiuret; it is shown that this compound is really s-diphenylcarbamide. When heated in sealed tubes with carbonyl chloride dissolved in toluene the latter substance is converted into s-diphenylbiuret.Pickard and Carter (Trans. 1901 79 841; 1902 81 1563) by acting on acetylphenyl- hydroxyloxamide with dilute ammonia obtained a compound which they tholight to be phenylbiuret ; this substance is really as-phenyl- biuret ; it crystallises in silvery scales m. p. 3 67O and does not give the biuret reaction; at the same time %he following by-products are formed monophenylcarbamide oxanilide s-diphenyl biuret and ammonium oxanilate. When s-diphenylcarbamide is heated with carbamide cyanuric acid is formed together with only small quantities of biuret and monophenylcarbamide ; that only small quantities of the last are obtained is probably due t o the fact that when heated this compound is partially converted into carbamide ands-diphenylcarbamide.The author’s original supposition (compare Abstr. 1897 i 144) that asymmetrically substituted biurets even when only one of the amido- hydrogen atoms is substituted do not give the biuret reaction although true in most cases has not been found to hold good in all cases. After mentioning the cases in which his proposition fails the author concludes by putting forward the suggestion that only those reactions which are obtained with amino-amides or diaulides derived from the parent substances biuret oxamide and malonamide with copper or nickel salts should be known as biuret reactions.W. H. G. Action of Phosphorus Pentabromide on Phenol Ethers. LOUIS HENRY (Ber. 1907 40 243-244).-A claim for priority (compare Ber. 1869 2 710 ; Autenrieth and Muhlinghaus this vol. i 31). 0. s,ORGANIC CHEMISTRY. 207 Isomerism of the Salts of Nitrophenols and the Existence of Metaquinonoid Compounds. ARTHUR HANTZSCH (Ber. 1907 40 330-351. Compare Abstr. 1906 i 352 353).-Two series of coloured alkali salts of nitrophenols have been prepared one yellow the other red ; the red salts are usually unstable and could not be obtained pure. Colourless 2 4 6-tribromo-3 5-dinitrophenol how- ever gives a yellow and a red potassium salt of the same composition and of the same molecular weight and electrical conductivity. Although many of these salts crystallise with water or alcohol their colour is not dependent on the water or alcohol of crystallisation as this may be removed from the red or yellow potassium salts of tribromonitrophenol without any alteration in colour.The fact that the. red ammonium salt of o-nitrophenol when dehydrated is yellow and the orange-yellow potassium salt red whereas,precisely the reverse is the case with the corresponding salts of 2 6-dinitro-p-cresol shows that these are the stable salts under these conditions and that isodynamic change has occurred during the dehydration. The author concludes that the two series of differently coloured salts obtained from colourless nitro- phenols have different constitutions and that their colour is independent of the alkali metal present as all the yellow and all the red salts are almost of the same colour intensity.The yellow and red salts are morphologically different (compare Rabe Abstr. 1901 i 697) and generally either the red or the yellow salt is alone formed but with m nitrophenols orange salts are obtained which are of the nature of solid solutions of the red and yellow varieties. The nitro-group not conferring colour on a compound i t follows that the real nitrophenols should be colourless and their salts must possess the constitution represented by either of the two formuls As an analogous series of coloured salts of dinitroparaffins has been prepared the change in colour from red to yellow and conversely cannot be due to changes in the nature of the benzene ring.Again the isomerism existing amongst these salts is not due to one salt being represented in constitution by the first and the other by the second formula otherwise benzene derivatives free from nitrogen should give also yellow and red salts. This is not the case (compare Abstr. 1906 i 856) and these salts are concluded to be structurally identical; they are therefore stereoisomeric and are represented by syn- and anti- configurations. By analogy with the red and yellow salts of benzene diazosulphonates the red salt is given the syn-formula (I) the yellow the anti-formula (11) thus The determination of the actual configuration is not yet possible. The existence of two classes oE coloured m-nitrophenol salts is held808 ABSTRACTS OF CHEMICAL PAPERS. t o be a proof of their metaquinonoid character although metaquinones are possibly not capable of existence.[With N. Rosa~o~~.]-The m. p. of 2 4. 6-tribromo-3 S-dinitro- phenol is 1 8 8 O not 194' (compare Jackson and Warren Abstr. 1894 i 176) and its acetyl derivative forms colourless needles m. p. 164'. The separation of the orange mixed potas8ium salt NO,. CBrs<XoqK EtOH into the lamon-yellow and red isokerides must be carried out in absolutely dry solvents. By addition of dry ether and benzene to an alcoholic solution and spontaneous evaporation in a vacuum over sulphuric acid the yellow salt crystallises out first. From the mother liquor the mixed salt is next precipitated and finally the vermilion- red salt is obtained. After recrystallising the salts two or three times a yield of 2% of the yellow salt and 4 4 5 % of the red is obtained. The two salts are microcrystalline and their solutions are yellow and dark orange respectively ; the solutions gradually change in colour due to isodynamic change.When in N/10 solution the yellow solution freshly prepared absorbs light up to a wave length of 508 the dark orange to 523 whereas the orange mixed salt gives absorption up t o 521. By following the change in the spectroscope the yellow solution had changed its absorption from 508 to 519 in ten hours and in 2.5 months the less unstable red solution from 528 to 523. There is therefore in the equilibrated orange mixture roughly 66% of the red salt. The cczsium salts are the only alkali salts in addition to the potassium capable of separate existence and can be separated into a yellow and red variety from the orange mixture.The red salt is much less stable than the corresponding potassium salt. The sodium salt prepared either at the ordinary temperature or at - 75" is yellow and gives a yellow aqueous solution the lithium and unstable amsnonium salts are also yellow. The following metals give mixed salts rubidium barium cuZcium thallium as also the pyridine salt. The potassium salt is the only salt of 3 5-dinitrophenol to give an indication of two forms as it alters its colour on heating to 100'; the mixed orange salt could not be separated. The rubidium salt is orange ; the barium light orange ; the sodium lithium anrmonium and silvar salts are pure yellow. [With E. BoRCHERs.]-The potassium and sodium salts of m-nitro- phenol are yellow at low temperatures but change in solution at 0' into the red salt.These salts could not be isolated. An ethereal or benzene solution of 1 mol. of m-nitrophenol and 1 mol. of ammonia is practically colourless but excess of ammonia precipitates the orange- coloured ammonium salt. The potassium and sodium salts of o-nitrophenol when prepared at low temperatures are lemon-yellow but these salts are very unstable giving immediately the scarlet salts a t - 75" with excess of ethoxide. The yellow ammonium. salt is only stable at low temperatures; at the ordinary temperature it is orange and scarlet plates have been These salts are also labile in the solid state. These salts in solution do not show isodynamic change.ORGANIC CHEMISTRY.209 obtained from solid o-nitrophenol (compare Merz and Ria Ber. 1886 10 1752). On t h e other hand the salts of p-nitrophenol behave differently from those of o-nitrophenol. The red salts are the exception; at low temperatures yellowish-white salts are obtained. The ethyl ester of 2 6-dinitro-p-cresol is colourless. The potassium and sodium salts of this cresol are orange-yellow and orange when anhydrous; when hydrated they are red. The ammonium salt is red when anhydrous and orange-yellow when hydrated ; the cassium barium and calcium salts are anhydrous and orange-yellow the silver salt is red (compare Stadel Abstr. 1883 662). Pentarnethylenediumine picrate when first prepared is red but in a desiccator it becomes yellow. At - 80' ammonium picrate is red at the ordinary temperature yellow.When prepared in benzene or ether solution the potassium salts are vermilion-red the potassium salt becoming yellow. The sodium salt is more stable but by washing with alcohol below 0" it also becomes yellow. Acyl Derivatives of 0- and p-Aminophenol. J. BISHOP TINGLE and L. F. WILLIAMS (Amr. Chem. J. 1907 37 51-71).- o-Benzoylaminophenyl benzoate m. p. lSO' prepared by the action of benzoyl chloride on o-acetylaminophenol crystallises in white slender needles. The following compounds of o-aminophenol are also described. p-Nitro benzoyl-o-nrninoplnol NO,. C,H,*CODNRa C,H,. OH m. p. 220' forms small yellow crystals ; its p-nztrobenzoata NO,. C,H,mCOmNH*C,H,*C)m CO* C,H,-NO rn. p. 2 19" light feathery cryE!als.m-Nitrobanxoyl-o-aminophenol m. p. 206O forms small yellow crystals; the m-nitrobenzoata m. p. 188O light flaky plates. BenzenesulpAonyl-o-aminophenol S0,Ph-N H C,H,*OH m. p. 141' forms small white needles ; its benzenesulphonate S0,Ph NH C,H,m O-SO,P h m. p. 134" (not 81-83' Georgescu Abstr. 1900 i 344) faintly red columnar crystals. p-Acetylaminophenol m. p. 166' (not 179" Morse Abstr. 1878 4 16) when treated with acetyl chloride yield8 the acetate previously obtained by Ladenburg (Abstr. 1877 i 305) by a less convenient method. p-Acety laminophenol shows a different behaviour with benzoyl chloride from that of the corresponding o-derivative and yields p-acetylaminophenyl benzoate NHAc~C,H,*OBz m. p. 166.5' which forms white feathery crystals (compare Reverdin this vol.i 37). The following compounds of p-aminophenol have also been prepared. p-Benzoylaminophenol m. p. 227.5" (not 205-207' as stated by Smith Abstr. 1892 i 490). p-Nitrobenxoyl-p-aminophnol NO,~C,H,~CO~NH*C,H,*OH m. p. 258' forms small lust,rous orange- red monoclinic crys tah ; its p-nitrobenzoate NO,. C,H,e CO NH *C,H,~ 0 CO C,H,-NO m. p. 264' light yellow microscopic crystals. m-Nitrobenxoyl-p- uminophnol m. p. 2 15 -216' forms light yellow slender needles ; its m-nitrobenzoate m. p. 264-265" a light grey powder. By the action W. R.210 ABSTRACTS OF CHEMICAL PAPERS. of benaenesulphonic chloride on p-aminophenol benaenesulphonyl-p- aminuphenol is produced but the di-benzenesulphonyl derivative de- scribed by Georgescu (Zoc. cil.) could not be obtained.Experiments have been made at O' at the ordinary temperature and at 240-250' with the objeat of obtaining tribenzoyl derivatives of 0- and p-aminophenol but without success. E. G. Preparation of Thio-derivatives of Quinol and its Chloro- compounda BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 175070). -Potassium quinolthiosulphonate separates as a colourless crystalline powder on adding aqueous sodium thiosulphate to a warm acetic acid solution of p-benzoquinone and subsequently salting out with potassium chloride. The corresponding memaptan SHmC,H3(OH) m. p. 119-120° is obtained in colourless needles on reducing the preceding compound with zinc*dust and an acid. The sodium derivative of the mercaptan on treatment with iodine furnishes the disulphide m.p. 185'. The mercaptan and benzoquinone together form the rnono- eulphide m. p. 22 i-229'. Quinolthiosulphonic acid on oxidation with potaEsium dichromate yields the corresponding quinonethio- sulphonic acid. Potassium a-quinoldithiosuZphonate obtained from benzoquinone and a larger proportion of sodium thiosulphate is very soluble in water but dissolves only sparingly in alcohol. The mercaptan forms colourless leaflets m. p. 190-192'. Potassium P-quinolthiosulplhonate isomeric with the preceding salt was obtained by dissolving benzoquinonethiosulphonic acid in dilute acetic acid a t 65-70' and pouring this solution into aqueous sodium thiosulphate at 10'; on adding potassium chloride the moderately soluble potassium salt separated and when crystallised from water formed white needles The mercaptan forms white needles m.p. 165-1 66'. These two quinoldithiosulphonic acids when oxidised by acidified dichromate yield the corresponding benzoquinonethio-acids. Potassium quinoltetrathio~ulphonic acid is the ultimate product of the action of excess of thiosulphate on quinol or benzoquinone in the presence of oxidising agents ; it forms white felted needles sparingly soluble in cold and readily so in hot water. 2 6 -DichZoroquinol-3-thiosulpiionic acid from dichloroquinol and sodium thiosulphate forms soluble yellowish-white needles ; the mercaptan has m. p. 171-178'. I t is readily oxidised to the cor- responding quinone. Potassium 2 6 -dicAloroquin.o2ditAiosu2phonate oxidises to a quinone and yields a mercaptan m. p. 225'.~enzoy~puino~me~captan C,If,(OH),'S'CO*C,H obtained by mixing benzoquinone and thiobenzoic acid in ethereal solution; m. p. 158-169'; the tribenzoyl derivative C6H3(OBz)=SBz m. p. 116-118'. &uinoZ zanthate C,H,(OH),~S~CS-OEt produced by the interaction of benzoqninone and potassium xanthate is a green crystalline powder m. p. 75-79'. Thio-derivatives of quinol were also obtained by the interaction of benzoquinone with thiocyanic and trithiocarbonic acids. G. T. M.ORGANIC CHEMISTRY. 211 Lupeol. N. H. COHEN (Proc. K. Akad. Wetensch. Amsterdam 1906 9 466-470. Compare Likiernik Abstr. 1891 551 1446; Romburgh Abstr. 1904 i 905).-Sack's alstol (Biss. Gottingen 1901) is not a pure syibstance. The benzoate formed by the action of benzoyl chloride and pyridine on lupeol obtained from djelutung crystallises in slender flat needles m.p. 273-274' (corr.) has [.ID +60-75' in chloroform solution and on hydrolysis yields lupeol crystallising in long needles m. p. 215O (corr.). When treated with bromine in a mixture of glacial acetic acid and carbon disulphide the benzoate yields two rnonobromo-deriv- atives C38H5302Br of which the less soluble in acetone separates from ethyl acetate in stout crystals m. p. 243O has [a] +44.g0 in chloro- form solution and on hydrolysis forms benzoic acid and a homo- alcohol. The more readily soluble isomeride crystallises from acetone in leaffets. The action of bromine on lupeol in carbon disulphide solution leads to the formation of a monobromo-derivative C,,H,90Br which crystal- h e s in needles m.p.- 185' (corr.) and has [a] + 3-8" in chloroform solution. Lupeol is oxidised by Kiliani's chromic acid mixture (Abstr. 1908 i 46) yielding Zupeone C,,H,80 which forms rhombo-dipyramidal crystals m. p. 170" (corr.) has [ aID + 63.1' in chloroform solution and is reduced t o lupeol by sodium and alcohol; hence if lupeone contains an ethylene linking this cannot be in the up-position to the carbonyl group. The osime C,1H,90N crystallises in soft white needles m. p. 278.5' (decomp.) and has [a] +29.5' in chloroform solution The action of bromine on lupeone in glacial acetic acid solution leads to the formation of hydrogen bromide and a dibrr-omo-deriv- ative C,,H,,OBr which crystallises in hard needles m. p. 254O (decomp.) and has [a]= + 2 1.4O in chloroform solution. The cyano- hydrin C3,H,SON formed by the action of hydrogen cyanide on lupeone in ethereal solution in presence of a trace of ammonia crystal- lises in stout needles m.p. 194' (decomp.) and when treated with 1 mol. of hydrogen chloride and 1 mol. of ethyl alcohol yields a product m. p. 235". Neither lupeol nor its acetate is oxidised by potassium perman- ganate in boiling acetone solution whilst the benzoate and lupeone in benzene solution a t 40' are not acted on by Kiliani's chromic acid mixture ; at higher temperatures lupeorie forms acid products which cannot be crystallised. When oxidised with potassium permanganate in sulphuric acid solution lupeol yields a mixture of products from which lupeone alone has been isolated ; the action of alkaline perman- ganate on lupeol leads to complete oxidation.The product C33H5003 obtained by oxidation of lupeol acetate with chromic acid in acetic acid solution does not redden blue litmus but can be titrated with alcoholic potassium hydroxide in presence of phenol- phthalein and on hydrolysis yields a product C31H5003 which crystallises in needles m. p. 263-265" and behaves towards litmus and phenol- phthalein in the same manner as the acetyl derivative. The hydrolysis product forms a potussium salt crystallising in needles and yields a The most probable formula for lupeol is C,,H,,O.212 ABSTRACTS OF CHEMICAL PAPERS. dicccatyl derivative C,,H,O which is formed also directly from the oxidation product. Lupeol and lupeone both give the reaction for unsaturated corn- pounds with Hiibl's iodine reagent G.Y. Cholesterol. VIII. ADOLF WZNDAUS (Ber. 1907 40 257-261. Compare Abstr. 1906 i 580).-The oxidation of cholesterol in benzene solution by alkaline potassium permanganate leads to the formation of a crystalline neutral substance C27H,603 m. p. 236O wbich does not react with hydroxylamine or phenylhydrazine yields a dimetale C31H5005 m. p. 187O and a dipropionate C3,Hp,0 m. p. 166-167' and by oxidation with chromic and acetic acids is con- verted int,o a dihto-compound Cz7H4,03 m. p. 253' ; this is isomeric with Mauthner and Suida's oxycholestendiol (Abstr. 1897 i 31) and like the later yields oxycholestenone by truatment with dehydrat- ing agents. This behaviour indicates that the substance C,?H,,O contains three bydroxyl groups ; a possible formula is suggested.c. 8. Unsaturated Compounds. IV. Action of Hydroxylamine on Ethyl Cinnamate. THEODOR POSNER (Ber. 1907,40 218-230. Compare Abstr. 1904 i 160; 1905 i 279; 1906 i 955; Ley Abstr. 1898 i 657 ; Tingle Abstr. 1900 i 544 ; 1905 i 930).- The action of hydroxylamine on methyl or ethyl cinnamate in cooled methyl-alcoholic solution is much more complicated than that on cinnarnic acid and leads to the formation of P-hydroxylaminodihydro- cinnamhydroxamoxime hydrate OH *NH- CHPh- CH,-C(N Hm OH),-OH which when purified by solution in aqueous ammonia and reprecipitation by evaporation of the ammonia at the ordinary temperature is obtained as a white crystalline powder m. p. 118-119° or after aome days in a vacuum desiccator 126' (decomp.) and has strong basic but only feeble acid properties ; it gives white precipitates with lead acetate and mercuric chloride and with copper sulphate a blue precipitate which on treatment with hydrogen sulphide yields chiefly P-aminodihydro- cinnamic acid together with a yellow sparingly soluble mbstanca m.p. 1 7 4 O containing only 4.9% of nitrogen. I n aqueous solution in contact with air at the ordinary temperature the hydroxamoxime hydrate is converted partially into 3-phenylisooxaxolone whereas when boiled with ammonia in an open dish on the water-bath it yields P-hydroxylaminodihydrocinnamic acid and only traces of 3-phenylieo- oxazolone. The hydroxamoxime hydrate is converted by boiling water into P-aminodihydrocinnamic acid obtained in a 52% yield or by alcoholic hydrogen chloride a t Oo into P-ethoxylaminodihydrocinnamic acid or by the action of sodium nitxite in cooled dilute sulphuric acid solution into P-dihydroxydihydrocinnamic acid.The action of benzoyl chloride on the hydroxamoxime hydrate in pyridine solution leads t o the formation of three products (a) dibenz- hpdroxam ic acid ; ( b ) di benzoy l-p-ir. ydrox y Zaminodih y drocinnamh y dr- oxamic acid OBz- NH-C H Ph- CHzmC(OH) :N- OBz or m. p. 136-137' which crystallises from alcohol and (cj a hexa- OBz*NBz-CHPh-CH,-C(OH):N~OH,ORGANIC CHEMISTRY. 213 benzoyl derivative OBz-NBz~CHPh*CH,*C(NBz-OBz),~OH which cry- atallises from methyl alcohol in needles m. p. 100-101'. Resin Acids from Conifers. VI. ALBERT VESTEBBERG. (Ber. 1907 40 120-123. Comparo Abstr.1906 i 92 ; Mach ibid. 1893 i 582; 1895 i 384).-Titrations of abietic acid with standard alcoholic potassium hydroxide using phenolphthalein as indicator agree with the formula C,,H,,O and not with C,,H,,O (compare Levy Abstr. 1906 i 870). When oxidised with sodium hypobromite by Diels and Abderhalden's method (Abstr. 1903 i 819) a small amount of an acid crystallising in needles m. p. 199O was obtained together with a non-crystalline acid. d-Pimaric acid distils at 282'/15-20 mm. and is not racemised during the process. Dinitriles and Amy1 Nitrite. JARL LUBLIN (J. p. C$em. 1906 [ii] 74 499-531. Compare Abstr. 1904 i 890; Meyer Abstr. 1895 i 582 ; Euler Abstr. 1903 i 298 ; Euler and Euler A bstr. 19G4 i 146)-When amyl nitrite is added in excess to p-toluacetodinitrile in ethereal solution a blue coloration and a dark blue to red sometimes white precipitate are formed ; when boiled for twenty-four hours the mixture yields (a) the ammonium salt of a-isonitroso-p-nitrosoimino-p- tolupropionitrile NO-N:C(C H,)*C(CN)*NONH which crystallises in white needles m.p. 156O (decomp.) detonates when heated evolves ammonia with aqueous alkalis and gives a transient blue coloration with acids ; the silver C1,HIO,N,Ag and barium (C,,H702N4)iBa salts of the isonitrosonitroso~m~nonitrile were analysed ; and (b) the oxime C,H,Me*CO-C(CN):NOH which is formed also by the action of heat mineral acids or acetic acid on the preceding ammonium salt or of nitrous acid on benzoylacetonitrile. This separates from benzene in small slightly yellow crystals m.p. 130.5-13 lo and is hydrolysed only slowly by boiling aqueous sodium hydroxide The action of hydroxylamine -hydrochloride on the oxime in dilute alcoholic solution leads to the formation of isonit~*oso-p-toZ~Ziso- G. Y. J. J. S. * I OH-N ?*GO C,H,Me* C=N oxaxolone >0 which crystallises in lemon-yellow needles m. p."l3?j.5O (decomp.) gives with sodium carbonate solution a stable with aqueous sodium hydroxide a transient red coloration being converted into a substance crystdlising in white needles m. p. about 95' (decomp.). When treated with hydroxylamine hydrochloride and sodium carbonate in aqueous alcoholic solution the oxime yields a product which forms white crystals m. p. 1 7 2 O and may have the con- stitution cN*y:N>O whilst if an excess of hydroxylamine is C,H,Me*C:N employed i i ihe ireaction the product forms white crystals m.p. 101-102° (decomp.) and is probably the dioxime C,H,Me*C(NOH)-C( NOH)-CN ; it gives with ferric chloride a red with hydrogen chloride or amyl nitrite in ethereal solution a blue coloration and slowly changes into the preceding substance m. p. 172'.214 ABSTRACTS OF CHEMICAL PAPERS. The ammonium salt of a-isonitroso-p-nitrosoiminophenylpropio- nitrile C,H90,N prepared together with iaonitrosocyanoacetophenone by the action of amyl nitrite on benzacetodixiitrile crystallises in white leaflets m. p. 152-152-5' (decomp.) detonates when heated and is identical with the product of the interaction of nitrous acid and benzacetodinitrile (Mey er Zoc. cit.). The action of hydroxylamine hydrochloride on the oxime leads to the formation of isonitrosophenyl- oxazolone and ammonia.The ammonium salt of a-isonitroso-p-nitrosoiminobutyronitrile formed from amyl nitrite and diacetonitrile crystallises in white needles or leaflets m. p. 122'; an oxime corresponding with isonitroso- cyanoacetophenone could not be isolated. p-Tolupropionitrile acetopropionitrile and Haller's imino-ether CH,Bz*C(OEt):NH (Abstr. 1887 &326) do not react with amyl nitrite in ethereal solution. The oxime C!,H,Me~C(NOH)~CH,-CN prepared by Probst's method (Diss. Leipzig 1894) m. p. 150-151" is converted by hydrogen chloride in ethereal solution into a chlorinated substance which evolves ammonia when boiled with aqueous Liodium hydroxide and with ethereal amyl nitrite yields a blue solution and on evaporation a small amount of aprodwt m.p. about 205O. The crystalline substance m p. 105 -1 08' (9 6O Burns Abstr. 1893 i 314) formed by the action of hydroxylamine hydrochloride on diacetonitrile evolves ammonia when treated successively with hydrogen chloride in ethereal solution and aqueous sodium hydroxide. The action of ethereal amyl nitrite on phenylisooxazoloneimide (Obrkgia Abstr. 1892 324) and treatment of the product with aqueous sodium hydroxide leads to the formation of a red substance cPh.C(NoH)>C:NH m. p. 63O (decomp.) 0 >C:NmNO or M -- G. Y. 8":=; which forms a resin when evaporated with ether. ERNBT YON MEYER (J. p. Cham. 1906 [ ii] 74 532. Compare preceding abstract).-The product of the action of hydroxylamine on toluacetodinitrile (Probst Dies.Leipzig 1894) m. p. 151' is hydrolysed by alcoholic hydrogen chloride forming p-tolyl cyanomethyl ketone m. p. 1 06' hydroxylarnine and traces of ammonia. The statements of Burns on the formation of an oxime from diacetonitrile (Abstr. 1893 i 314) are confirmed. [Dinitriles and Amy1 Nitrite.] a. Y. Acetophenone-o-carboxylic Acid. SIEGMUND GABRIEL (Ber. 1907 40 71-83).-Gabriel and Michael found (Abstr. 1878 229) that when acetophenone-o-carboxylic acid (1 mol.) is acted on by bromine in glacial acetic acid solution a t loo' the m9nobromo- derivative CO,H~C,H,=CO-CH,Br was not obtained but the com- pound C,H,BrO containing 1 mol. of water less than the mono- bromo-derivative and having the property of uniting with 1 mol.of bromine was formed. Gabriel showed subeequently (Abstr. 1884 1176) that the latter compound was bromomethylenephthalide. The author has now continued the study of the action in question. o-Bromoacetop~norce-o-car~oxyZ~c acid C0,H-C,H,-CO~CH2Br pre-ORGANIC CHEMISTRY. 215 pared by the addition of bromine to a solution of acetophenone- o-carboxylic acid in glacial acetic acid on a water-bath and then evaporating the praduct under diminished pressure at about 60' separates from chloroform in snow-white glassy needles or oblong plates m. p. 127-128'. When heated with a solution of hydrogen bromide in glacial acetic acid for one hour at 100' in a sealed tube w-bromoacetophenone- o-carboxylic acid forms bromomethylenephthalide (Zoc. cit.) according to the equation CO,H~C,H,-CO*CH,Br - H,O = C6H,@:E3O if the solution is evaporated on the water-bath. If however the solution is allowed t o evaporate spontaneously methylenephthalide dibromide (Zoc.cit.) is formed according to the equation C O e f 9 C C H B r + HBr = CO<!f2>CBr-CH2Br. I t s methyl ester crystallisesin prisms m. p. 61-62'. Ilp?roxyrneth ylanephthalide COcfA>C CHe OH (or f ownyl- phthcdide COefA>CHmCHO) is obtained as snow-white needles m. p. 147-1 48" when o-bromoacetophenone-o-carboxylic acid is boiled with water and the solution is allowed t o evaporate spontaneously ; it is identical with the compound C,H,O already described by Michael and Gabriel (Zoc. cit.). It forms a yellow solution with alkalis and reduces Fehling's solution in the cold.By t h e action of a mixture of fuming hgdriodic acid and a little phosphonium iodide it forms the compound C18Hlo05 having the probable formula O(CH:C<;~~co) 9 m. p. 240' (decomp.) ; it is an anhydro-compound being formed accord- ing to the equation 2C,H,O -H,O = C18Hlo05. The presence of a hydroxy-group in hydroxymethylenephthalide is also indicated by its behaviour on esterification with methyl alcohol according to the hydrogen chloride method when methoxymethylene- plithnlide C O ~ o ~ > U C H - O M e is produced ; the latter separates from alcohol in needles m. p. 75'. That a double linking is present in the molecule of hydroxy- methylenephthalide is attested by its behaviour on bromination. When acted on by bromine in chloroform solution it forms formylbromophthaZide C O c g D C B r - C H O which separates from alcohol in hexagonal plates m.p. 85-86'. In certain reactions however hydroxymethylenephthalide behaves as if it were an aldehyde. For example it forms an oxime COef>CHmCH:h'-OH which crystallises in silky needles m. p. 147-152" the acetyl derivative of which has m. p. 154-155'. The phenyllhydraaone C O ~ f ~ C H ~ C H N ~ N H P h obtained from hydroxymethylenephthalide and phenylhydrazine forms yellow needles m. p. 180'. C H216 ABSTRACTS OF CHEMICAL PAPERS. Similarly hydrazine hydrate forms the azine C1,H1,O,N which crystallises in yellow needles and begins to decompoee at about 220O. The compound C,,H,,O,N obtained by the action CM potassium cyanide on o-bromoacet ophenone-o-carboxylic acid forms a brown powder m.p. 223'. .It reduces Fehling's solution in the cold. o-Dibromoacetophenone-o-carboxylic acid CO,H*C,HpmCoDCHBr prepared by the action of bromine (2 mols.) on a solution of aceto- phenone-o-carboxylic acid in glacial acetic acid separates from chloro- form in tetragonal colourless plates m. p. 131-132'. Its rnethyZ eater separates from alcohol in hexagonal plates or oblong prisms m. p. 112'. By the action of hydroxylamine on o-dibromoacetophenone- o-carboxylic acid both the halogen and the ketonic oxygen of the latter are replaced with the formation of p~t~aZonaldehydecarbox~Zic ucid dioxime anhydride CO<C6H4' 8 'CH:N'oH which crptallises 0-N from glacial acetic acid in silky needles m. p. 163'. The behstviour of o-dibromoacetoDhenone-o-carboxvlic acid towards phenylhydrazine is analogous phthr;lonaldehydecarbojcylic acid osaxone adydvide being formed; the latter compound F,H,*fi-CH:N,HPh CO-N,Ph separates from glacial acetic acid in silky needles m.p. 228'. When o-dibromoacetophenone-o-carboxylic acid is boiled with water i t is converted into phthalidecarboxylic acid COef*CH*CO,H melting at 152' and identical with the product obtained by Zincke and Schmidt. I n this action phthalonaldehydic acid CO,H* C,H,-CO* CHO was possibly first formed and then underwent molecular rearrangement into its isomeride. DibrornomethylenephthaEic2e CO<zr*C:CBr obtained by the action of concentrated sulphuric acid on w-dibromoacetophenone- o-carboxylic acid separates from alcohol in needles m.p. 139-140'. Its unsaturated nature is demonstrated by its behaviour towards bromine when tetrabromomethyl~hthalide C O c f D C B r * C B r is produced; the latter separates from a mixture of benzene and ethyl acetate in glistening pyramids which melt and decompose at 160-1 6 1 '. A. McK. Catecholcarboxylic Acids. ANTON PRAXMAREB (Mmatsh. 1906 2'7 1199-1209).-Contrary to Miller's statement (Anrurlen 1883 22€),113) the action of ammonium carbonate on catechol at 130-140' under pressure leads to the formation of catecholcarboxylic acid only ; protocatechuic acid cannot be found in the product. The same result is obtained on heating catechol with glycerol and potassium hydrogen carbonate in a current of carbon dioxide at 180' for twelve to sixteen hours or at 210' for six t o eight hours.Catecholcarboxylic acid C7H60,,$H,0 m. p. 240° decomposes,ORGANIC CHEMISTRY. 217 evolving carbon dioxide a few degrees above its melting point. The barium (C H50,),Ba,4H,0 (5H20 Miller Zoc. cit.) and calcium (24H,O) satits and the ethyl ester m. p 130.5' (63-64' Schmitt and Hahle Abstr. 1891 1366) are described. The methyl ester of the dimethyl ether m. p. 5 7 - 5 O (47' Fritsch Abstr. 1898 i 663) is prepared by the action of methyl iodide and potassium hydroxide on the acid in methjl alcoholic solution. The action of bromine on catecholcarboxylic acid in absence of a solvent leads to the formation of tetrabromocatechol or in ethereal solution t o the formation of this together with dibyomocaecholcwboxylic mid C7H404Br2 which is soluble in water a t 80'.Catecholdicarboxylic acid is formed together with a small amount of catechol by heating the monocarboxylic acid with glycerol potassium hydrogen carbonate and a little sodium sulphito in a current of carbon dioxide at 210' for six hours. A product which gives the green coloration of protooatechuic acid with ferric chloride is obtained on heating catechol with sodium h j drogen carbonate and glycerol at a temperature not above 139". G. Y. Ethyl Benzoylglyoxylete. ANDRB WAHL (Cornpt. rend. 1907 144 212-214. Compare Abstr. 1904 i 556).-EthyZ benzoyl- glyoxglate COPhmCOmCO,Et prepared by passing nitrous anhydride into a mixture of ethyl benzoylacetate and acetic anhydride dissolved in ether is an orange-yellow liquid mobile when freshly prepared and without distinctive odour b.p. 150-153'/13 mm.; D8 1.188 It com- bines with water and alcohol developing much heat and forming colourless hydrates aud alcoholatee which do not crystallise. By adding a few drops of piperidine to a molecular mixture of ethyl benzoylglg- OXJ late and ethyl benzoylacetate the author has obtained a compound Cl,H,20,,C,1Hlo0 forming white needles m. p. 109-1 loo and probably identical with t b a t obtained by Sachs and Wolff (Abstr. 1904 i 876) and having m. p. 91.5'. Ethyl benzoylglyoxjlate forms a monozime identical with ethyl ~sonitrosobenzoy!acetate and hence having the constitution COPhmC( :NOH)-CO,Et; a dioxime is notformed. CriPmer's method gave a small quantity of a crystalline substance which showed the reaction of oximinophenylisooxa zolone o<N=yph CO - CN-OH The ester reacts with o-phenylenediamine forming ethp? 2-pAenyZquin- oxnEiize-3-cccrbozyZa~e which crystallises in slender white needles m.p. 65-66' It gives a disemicnvbazone C13H,60,N,,H,0 light yellow needles m. p. 185-190' and a dianilide C23H2203N2 small yellow needles m. p. 127'. E. H. Condensation Products of Dibromophthalic Acid. ~ I L E SBVERIN (Ann. Sci. Univ. Jcbssy 1907 4 141-150).-B1ost of the work recorded in this paper has been published already (Abstr. 1906 i 508). 3 6 -Dibromo-a-o-diet hylamino benzoyl benzoic acid NEt2~C,H,*CO*C6H,Br,~C0,H VOL. XCII. i. Q218 ABSTRACTS OF CHEMICAL PAPERS. prepared as alrddy described (loc. cit.) furnishes an ethyl mter m. p. 145O which crystallises with alcohol ; the nitroso-derivative NO*NEt,*C,H,*CO*CBHaBrB.CO,H m. p. 155O crystallises in yellow needles. On reduction of the benzoyl- benzoic acid the corresponding dibromodiethylaminobenzylbenxoic mid is produced which separates from alcohol with difficulty in colonrless needles m. p. 2 4 7 O and when warmed with sulphuric acid at 66' furnishes 1-dietliylanrino-5 8-dibrornoantliraquinone which sublimes in red needles m. p. 198'. Behaviour of Phenolphthalein toward8 Highly Concentrated Alkali Hydroxides. BENJAMIN M. MARGOBCHES (Zeitsch. angew. Chern. 1907 20 181-191 and 226-231).-Alkaline solutions containing phenolphthalein may be decolorised by the addition of very concen- trated solutions of alkali hydroxides and to a less extent by the addition of lithium hydroxide.Such solutions recover their pink coloar on warming or on dilution; as the colour is however not instantaneously restored by dilution the phenomenon cannot be com- pletely explained by dissociation. The paper contains a very full account of the various theories which have been put forward with regard to the constitution of phenolphthalein and its use as an indicator. P. H. Compounds from Lichens. XVI. WILHELM ZOPF (A-nnabn 1907 352 1-44. Compare Abstr. 1906 i 672).-The lichen Ramalina subfarinacea contains d-usnic acid [a] + 492.5' to the extent of 3% and 3 to 34% of salazinic acid; the product obtained by the action of acetic anhydride on the latter acid has already been described as salazinaric acid (Zopf Abstr. 1905 i 789) but is now thought to be the acetyl derivative of salazinic acid C,,H1,Oll ; its mol.weight was determined cryoscopicallp in benzene and found to be 455 Hesse's formula for salazinic acid C,,H,,Ol (Abstr. 1901 i 595) cannot therefore be correct. In addition to d-usnic acid ([a] + 495.5') Ramulincc scoputorurn is found to contain a new acid ecopuZolr.ic acid Cl,Hl,Og which crystal- lises in white needles m. p. 260" (decomp.). The acetyl derivative C,lH18010 crystalhes in white needles m. p. 235-236". Rarnalinn KuZEensis contains about 0.1% of d-usnic acid [a] + 461.94 and 2% of kullerzsisic acid C,,H,,O, a substance not yet met with in any other lichen ; it crystallises in white needles and carbonises a t 260'. Only d-usnic acid das obtained from Ramalina minuscula whilst R. LandroZnsis contains in addition to about 0.5% of d-usnic acid about 0.1% of landroewin which crystallises from benzene in small rhombic plates.The lichen Rainalina obtusata (R. minuscula var. obtusata R. dilace- rata var. obtusata) contains only small quantities of d-usnic acid [a] + 474.2" together with two new acids Ramalinellic acid crystallises from acetone in small needles m. p. 169O. Obtusutic acid crystallises in needles m. p. 191'. CZadoniu jimbriata var. simplex obtained from Daun in Eifel was found to dii€er from a Cladomia fimblr.iatn var. eirnplex obtained from tho Dortmund-Ems Canal near Miinster i. W in that the first con- T. A. H.ORGANIC CHEMISTRY. 219 tained fumaroprotocetraric acid together with Gmbriatic acid whereas the latter lichen besides these two acids also contained atranoric acid; it is therefore probable that they are specifically differetit.Fimbriatic acid crystallises from ether in leaflets m. p. 98-99'; it reduces potassium permanganate immediately in alkaline solution. The lichen Cladoniafimbriata var. cornuto-radiata contains only fumaro- protocetraric acid. Hesse obtained from this lichen called wrongly by him C. Jimbriata var. chordah (compare Abstr. 1901 i 149) protocetraric acid and not fumaroprotocetraric acid probably because he employed sodium hydrogen carbonate to extract the acids from the lichen and thus decomposed the fumaroprotocetraric acid into f umrtric and protocetraric acids. Closely related to this latter lichen is Cladonicc pityea var. cladomorpha since this also contains only fumaroproto- cetraric acid.Cladoniu spuamosa var. denticollis contains squamatic acid but not usnic acid. Ckdonia silvatica var. condensata besides 1-usnic acid [a] - 499.5' contains a substance which since it is relatively soluble in cold benzene and ether is not fumaroprotocetraric acid ; as the latter acid together with d-usnic acid is present in the typical C. silvatica (Zopf Abstr. 1906 i 673) C . silvatica var. condensata cannot be regarded as a variety of C. silvatica but must either be regarded as a variety of C. alpestris or better be named simply C. condensata. Cladoniu verticillata var. aubcervicornis contains about 1% of fumaro- protocetraric acid and a small quantity of atranoric acid; there is also present a small amount of a red pigment cervicornin a red amorphous substance coloured blue by strong sulphuric acid and violet to violet- brown by potassium and sodium hydroxides.Cladonia chlorophtea contains furnaroproto'cetraric acid together with cidoropi~maic acid which crystallises in leaflets m. p. 169' (decomp.). Cladonia gracilis var. chordcclis contains only fumaroprotocetraric acid ; C. crispata var. gracilesceias contains only squamatic acid. The same acid is also present in C. squamosa var. rnultibmchiata f. pseudo- crispata and c. squamosa var. multibrac~~iata f. Iurfacea. Hypogyrnnnia fayinacea contains about 0.5% of atranoric acid together with about 4.5% of fwinacinic acid C,,H,,O ;. this acid crystallises in white needles m. p. 202-203'; its mol. weight was determined in acetone ; it does not taste bitter.When heated with acetic anhydride a substance m. p. 156-157' is obtained. It is possible that this acid is identical with Hesse's physodic acid (Abstr. 1898 i 679). W. H. G. Derivatives of Methylvanillin [2 :4-Dimethoxybenzaldehyde]. FRITZ JULIUSBERG (Bey. 1907 40 119-120).-2 4-Dimethoxybenz- aldehyde obtained by methylating vanillin by means of sodium ethoxide and methyl iodide ha8 m. p. 47'. 2 4-Dimethoxybenxaldehyde- phenylhydraxone C,H,(OMe),*CH:N*NHPh has m. p. 12 1'. 1 2-Bimethoxy-4-benxaldoxime C,H,(OMe),-CH:N*OH obtained by the action of hydroxylamine on the aldehyde softens at 87' and has m. p. 90'. 1 ; 2- Dimathoxy- 4- benzy lamine hydrochloride C6H3( OMe),-CH,*NH,,HCl P 2220 ABSTRACTS OF CHEMICAL PAPERS. obtained by tohe reduction of the preceding oxime with sodium amalgam and acetic acid has m.p. 257-258'. Influence of Cyclic Linking on Reactivity. PAVEL PETRENKO- KRITSCHENKO (J. p. Chena. 1907 [ii] 75 61-64. Compare Abstr. 1900 i 421 ; 1901 i 506; 1903 i 440 ; ibid. tii 719; 1905 i 355 742 ; 1906 ii 341).-The author replies to Stewart and Baly (Trans. 1906 89 489) that the relations which he has observed (loc. cit.) to exist between the velocity of reaction and the structure of ketones are corhpletely analogous to those found by Menschutkin in the case of aliphatic and aromatic alcohols and amines in which all possibility of tautomerism is excluded. The author compares his theoretical views which have been de- scribed previously (Zoc. c k ) with those of Menschutkin (Trans. 1906 89 1532). G.Y. OTTO WALLACH (Ber. 1907 40 70-71. Compare Abstr. 1906 i 514).-The chEwide C,,H,,OCl obtained by passing a current of dry hydrogen chloride into cyclohexanone forms colourless crystals m. p. 41-43'. On rise of temperature it loses hydrogen chloride and forms cyclo- hexene-2-cyclohexunone ')={) 1 which on reduction forms the A. McK. Condensation Products from cpcZoHexanone. 0 OH \/ \ /)A saturated a.lcoho1 cyclohexyZ-2-cyclohexunoZ I I I b* P- \/ \/ 265-270° m. p. 30-31'. The latter compound when warmed with hydriodic acid forms the completely hydrogenated diphenyl dicyclo- hexyl C6Hll*C6Hll already described by Borsche and Lange (Abstr. 1905 i 765). Benxylidenecyclohexanone) C6H,0:CHPh has m. p. 53". Bibenzyl- idenecyclohexanone C,3H140 has m. p. I 16-1 18'. By the action OF hydroxylamine on monobenzylidenecyclohexanone a compound of m.p. 104' crystallising in needles is obtained. A. McK. Synthesie of Derivatives of cgcZoHexane. 3 3-Dimethyl- and 3 3 6-Trimethyl-cyclohexanones. GUSTAV BLANC (Compt. rend. 1907 144 143-144. Compare Abstr. 1906 i 399).-The anhydride UH2<Egr!:<<gE>0 obtained from PP-dimethylpime- lic acid by the action of acetic anhydride loses carbon dioxide on slow distillation at the ordinary pressure and gives the 3 3-dimethylcyclo- hexanone already described by Ldser (Abstr 1899 i 743). This compound forms a semicarbazone crystallising in needles m. p. 203' (Lbser gives 198'). On reduction by means of sodium and absolute alcohol it gives the alcohol CH2<c,,-cH CMe2*CH2>CH*OH obtained by Crossley and Renouf (Trans.1905 8'7 1487).ORGANIC CHEMISTRY. 221 Similarly slow distillation of PPc-trimethylpimelic anhydride gives 3 3 6-trimetl~~lcyclohexanolze CH2<CEI,'CHMe CMe2-cH,>C0 a mobile liquid b. p. 186O of strong menthone-like odour. The semicurbaxone has m. p. 170O. E. H. Change of 2-isoNitroso- 1 - ketohydrindene into Eomo- phthalamic Acid. WALTER PETERS (Bey. 1907 40 240-24l).- The oxime is unchanged by cold hydrochloric and acetic acids is oxidised to phthalic acid by nitric acid and is converted by concen- trated sulphuric acid a t Oo into Gabriel's homophthalamic acid (Abstr. 1887 726). c. s. Condensation of Cinnamyl Chloride with o-Gresol. GUSTAV NEURATH (Monatsh. 1906 27 1145-1156. Compare Feuerstein and Kostanecki Abstr.1898 i 370 ; Kostanecki and Tambor Abstr. 1899 i 704).-p-l€ydroxy-m-toZyl alyryl ketone (4-hydroxy-3'-methyL chalkone) OB*C,H,Me*CO*CH:CHPh prepared by the action of cinnamyl chloride and aluminium chloride on o-cresol in nitro benzene solution or by heating o-cresol with cinnamic acid and zinc chloride at 2004 crystallises from water in reddish-yellow nacreous needles m. p. 137" (corr.) and is soluble in aqueous alkalis. The ucetyl derivative C,,H,,O crystallises in needles m. p. 72' (corr. j ; the oxirne CI6Hl6O2N forms a ruby-red crystalline mass m. p. 49' (corr.). The dibromide OH*C,H,MewCO*CHBr~CHPhBr formed by the action of bromine on the unsaturated ketone iu ethereal solution separates in yellowish-red crystals m. p. 135' (corr.). 0- u u. I. Condensation of Terephthalaldehyde with Ketones.HANS YON LENDENFELD (Monatsh. 1906 27 969-980. Compare Thiele and Winter Abstr. 1900 i 500 ; Thiele and Giinther and Thiele and Falk Abstr. 1906 i 750).-The condensation of terephthalaldehyde with ketones in hot alcoholic potassium hydroxide solution leads to the formation of unsaturated ketones or in cooled glacial acetic acid solution in presence of hydrogen chloride to that of the corresponding hydrogen chloride additive products. Terephthalaldehyde and acetophenone yield a mixture of p-aldehyde- benzylideneucetophenone COH*C,H,*CH:CH*COPh which crystallises from methyl alcohol in slightly yellow needles m. p. 125O and forms a yellow solution in concentrated sulphuric acid and terephthalylidene- diacetophenone C6H,[CH:CH-C0Phl2 which crystallises from chloro- form in yellow hexagonal plates m.p. 200-201° and is insoluble in methyl alcohol. With phenylhydrazine the latter substance forms Aldols are not formed. p-phekylenebis- 1 ; 3-diphenil-4 >-&hydropyrazoZe NPhaN c6H4(OH<CH,.8Ph)4 which crystallises in colourless needles m. p. 300' (slight decornp.) and gives Knorr's pyrazoline reaction. The additive product C,H,[CHCl~C€€,-COPb] crystallises from nitrobenzene in colourless needles m. p. 194-195' and at 160-17O0222 ABSTRACTS OF CHEMICAL PAPERS. gradually decomposes yielding terephthalylidenediacefophenone and hydrogen chloride. The condensation product of terephthalaldehyde with phenyl ethyl ketone C,H,[C!H:CMe*COPh] crystallises from alcohol in colourless hexagonal leaflets m.p. 162' and reacts with phenylhydrazine forming a product which crystallises from pyridine in yellow needles sinters at 245' and is decomposed to a clear liquid at 254'. The hydrogen chloride additive product 0 H4[ CHCl*CHMe* COPh] crystallises from benzene in long rhombic plates decomposing at 240' yielding the unsaturated ketone. p- TolpZ p-aZdehydo6enxy lidenerne fhyl ketone COH*CGH,* CH CH*CO*C,H formed from a molecular mixture of terephthalaldehyde and p-tolyl methyl ketone crystallises in small matted yellow needles m. p. 130'. The phenylhydraxone C,,H2,0N2 forms red needles m. p. about 224'. The diketone C,H,tCH:CH*CO*C7H7I2 formed from 1 mol. of terephthalaldehyde and 2 mols. of p-tolyl methyl ketone crystallises from alcohol in needles m.p. 236-238' gives an orange-red coloration with concentrated sulphuric acid and reacts with phenyl- hydrazine in glacial acetic acid solution forming an amorphous product which gives the pyrazoline reaction The hydrogen chloride additive product C6H4[CHC1*CH,=CO*C7H71 crystallisrs in colourless needles m. p. 228-230' and yields the unsaturated diketone when heated in a vacuum at 170°. p-MedhoxyphenoZ p-aZ~ehydobenayZidsneme~~~Z ketone COH*U,H,*CH:CH*CO*C,H,*OMe obtained by the interaction of terephthalaldehyde and anisyl methyl ketone in molecular pi oportions crystallises in large yellow needles m. p. 121' ; the phenylhydraxone C93H2002N2 crystallises in reddish- yellow needles m. p. 208' (decornp.). The diketone C,H,~CH:CH*CO*C,H,*OMe] forms large yellow leaflets m.p. 250' and gives a red coloration with concentrated sulphuric acid. The product formed by the action of hydrogen chloride on terephthalaldehyde and anisyl methyl ketone in glacial acetic acid solution is identical with that obtained by the condensation in presence of alcoholic potassium hydroxide. G. Y. Halogen Derivatives of 1 3 4TriketocycZopentane. 111. PRANZ HENLE (A?zncden lgCl'7 352 46-53. Compare Abstr. 1907 i 144 161).-Tetrahalogen derivatives of 1 3 4-triketocyclo- pentane cannot be prepared by the direct bromination or chlorination of chlorotriketocyclopentane ; they are however obtained by acting on either tribromotriketocyclopentane or chlorodibromotriketocyclo- pentane with phosphorus pentachloride ; phosphorus pentabromide does not react like phosphorus pentachloride ; it replaces a hydroxyl group by bromine so that from tribromotriketocyclopentane tetrabromodiketo- cyclopentene is obtained.Chlorodibromotriketocyclopentane may be prepared by acting on chloro-1 3 4-triketocyclopentane dissolved in thionyl chloride with bromine. When treated with phosphorus pentachloride it givesORGANIC CHEMISTRY. 223 tvichlorobromo-1 3 4-triketocyclopentane C503C13Br which crystnllises in faintly yellow plates m. p. 85'. Tribromo-1 3 4-triketocycZopentane is converted by phosphorus pentachloride into dichlorodibrorno-1 3 4-triketocyclopentane which crystallises in yellow prisms m. p 102'. With phosphorus pentabromide however tetmbromo-1 3-dzrEetocyclopentene CS02Br4 is obtained which crystsllises in yellow needles rn.p. 142'. By heating dichlorodibromo-1 3 4-triketocyclopentsne with phos- phorus pentachloride in sealed tubes at 280 -300° octachlorocyclo- pentene C,Cl is formed identical with that described by Zincke (Abstr. 1890 1256). c503cprp W. H. G. Constitution of the a- and ,&Additive Compounds of Alcohols and Tetrabromo-o-benaoquinone. C. LORING JACKSON and ROBERT D. MACLAURIN (Amer. Chem. u?,190'7 37 S7-106).-Jackson and Porter (Abstr. 1903 i 266 ; 1904 i 254) have described two series of additive compounds 2C,Br,02 R-OH obtained by the com- bination of tetrabromo-o-benzoquinone with alcohols. The a-compounds are formed by the direct action of alcohols on the quinone at the ordinary temperature and are converted into the P-compounds by the action of hot dilute sodium hydroxide or by means of acetic anhydride. Further work on these substances has been carried out by Jackson and Carlton (Abstr. 1905 i 907) and by Jackson and Husse (Abstr.1906 i 288). Further investigation has led t o the conclusion that the a- and P-compounds have respectively the constitutions expressed by the fol- lowing formula Br Br Br Br The reasons for adopting these formulae in preference to those previously assigned to these compounds are fully discussed and are based chiefly on the facts that the regulated action of acetic anhydride converts the a-benzyl compound into the P-compound and that the p compounds are remarkably stable. I n accordance with these formulz the a- and P-methyl compounds are termed respectively octabromo-l-metlioxy-l'-hydroxy-o-quino-l-monoxide and octabromo- 1 -met hoxy- 1 '-hy droxy -0-qui no- 1 2 2-trioxide.On adding a considerable quantity of sodium hydroxide solution to hexac hloro-o-quinocat echo1 ether C,C 1,02 C6C1202 an additive com- pound C,,CI6O4,NaOH separates in purplish-black short stout needles. If however sodium hydroxide is added drop by drop t o a warm mixture of hexachloro-o-quinocatechol and water hexachloro- dihydroxgcatechol ether and sodium chloroanilate are produced. It is evident that the former product is formed from the tetrachlorocatechol resulting from the decomposition of the hexachloro-o-quinocatechol224 ABSTRACTS OF CHEMICAL PAPERS. ether since on warming tetrachlorocatechol with dilute sodium hydruxide hexachlorodihydroxycstechol ether is produced.When hexabromo-o-quinocatechol ether is left in contact with dilute sodium hydroxide sodium bromoanilate is formed. It has been shown by Jackson and Porter (Abstr. 1904 i 256) that by the action of heat on tetrabromo-o-quinone bromine is liberated and hexabromo-o-quinocatechol ether is produced. It is now four d that tetrachloro-o-quinone is decomposed similarly by heat with formation of hexachloro-o-quinocatechol ether. The /3-rnethyl compound 2C,Br,O,,CH,*OH is more stable towards sodium ethoxide than the a-compound but is gradually decomposed with formation of catechol and sodium bromide. By the action of hydroxylamine on the a-methyl compound it is converted quanti- tatively into the P-compound. If the a-methyl compound is shaken with acetic anhydride for fifteen minutes and then left for several hours an isomeric y-compound m.p. 225O is produced which crystallises in yellow plates and is more soluble in organic solvents than the /3-compound. By the action of warm acetic acid on the y compound there are successively produced a white substance rn. p. 138-140° a second compound m. p. 195' and finally hexabromo-o- quinocat echo1 ether. E. G. Preparation of 1 -Aminoanthraquinone and its N-Alkyl or Acyl Derivatives. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 175024).-When heated with aqueous ammonia or methyl- amine anthraquinone-a-sulphonic acid is converted respectively into 1 -am inoa nthraq uin one or 1-me thy1 arninoan thraquinone. With p-tolu- idine this sul phonic acid yields 1p-toluidinoanthraquinone. G.T. &I. Preparation of Arylaminoanthraquinones. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 175069)-The halogenated benzenes interact readily with t'he aminoanthraquinones in presence of an acid-fixing agent to form arylaminoanthraquinones. Thus p-chloro- nitrobenzene and 1-aminoanthraquicone yield 1-p-nitroaniliaoanthra- quinone and 1 4-diaminoanthraquinone and p-dichlorobenzene give rise to 1 4-di-p-chloroanilinoanthraquinoiie. "he colour reactions of these and other arylaminoanthraquinones are tabulated. G. T. M. Preparation of Aldehydes of the Anthraquinone Series. BADISCIIE ANILIN S SODA-FABRIK (D.R.-P. 174984).-Although ow-dichloromethylanthraquinone does not yield an aldehyde on treatment with alkalis or water a t high temperatures yet it undergoes this change on heating with concentrated sulphuric acid either alone or with addition of boric acid.P-Annl?trciquinoneal~e?L~de is obtained in this may from w-dichloro- p-nzethylau thraquinone or the corresponding bromine compound. 1 -Chlo~o-P-anthraquinoneaZdehyde is produced by the interaction of l-chloro-2-met~hyla11thiaquinone and sulphuric and boric acids at 130'. 4-Bromo-1 -FLydroxy-P-ccntliraqu~nonealde~~ycle is prepared in this way from 4-ww-tribromo- I-hydroxy-2-methylanthraquinone. G. T. M.ORGANIC CHEMISTRY. 225 Meso-derivatives of Anthrrtcene. FELIX KAUFLEIZ and W. SUCHANNEK (Ber. 1907 40 5 18-532).-Anthranol and diazobenzene chloride form a substance which may be regarded either as a benzene- azoanthranol from its forming alkali salts or as an anthraquinone- phen ylhydrazone from its colour its ready decomposition into zinthra- quinone and phenylhydrazine and its formation from dibromoanthrone and phenylhydrazine.9-Aminoanthracene reacts with diazonium salts i n A similar manner. m. p. 182-183°,'is"obtained from the potassium salt of anthranol and diazobenzene chloride in alkaline solution or from 1 0-dibromoanthrone and phenylhydrazine ; i t separates from toluene in red needles forms a potassium salt which exhibits bluish-red fluorescence in solution and is converted by boiling alcoholic sulphuric acid into anthraquinone and phenylhydrazine. lO-p-Nitrobenxenechxoant?wanoZ m. p. 238-240° .is prepared in a similar manner to the preceding compound and exhibits similar properties.Anthvaquinone-10- p-dimethylaminoannil CO<$3>C:N C,H4*NMe2 m. p. 138-139' is obtained from anthranol and p-nitrosodimethyl- aniline ; it separates from light petroleum in bluish-black glistening needles and by hydrolysis yields anthraquinone and dimethyl-p- Dhenvlenediamine. 6 4 9 - kmino - 10 - benzeneazoanthracene (ccnt~raquinoneinii~~phe~~l~y~azone) C,H4<VNH2)>C H C( :NH)- C(N,Ph) 6 4 Or CoH4<C(:N.N~Ph)>C6H4 Pa 182-1840 is obt'aiied ;n the form of the hydrochloride by the action of diazobenzene chloride on 9-aminoant hracene in cold alcohoiic solu- tion; i t forms large brown crystals and is changed by 3% alcoholic hydrogen chloride into anthraquinone ammonia and phenylhydrazine ; tho hydrochloride C2,H,,N,,€ICl forms red crystals with green reflex.9-Amino-1 O-p-nitB.obenffeneazoanthracene C2OHI4O2N4 m. p. 239-240° forms yellowish- bro wn 1 eafle t s. The p-dinzethylaminoanil of anthFaquinoneimide NH C<3;4>C N*C6H,* NMe m. p. 1 18-1 2 4 O is obtained from 9-arninoanthracene and p-nitrosodi- methylaniline in alcoholic solution ; it crystallises in black leaflets or prisms and is converted by 1% acetic acid in alcohol into anthra- quinonedimethylaminoanil and by 1% alcoholic hydrogen chloride into anthraquinone ammonia and dimethyl-p-phenylenediamine. Attempts to diazotise 9-aminoanthracene lead to the formation of anthraquinone and a basic substunce which appears to be diamino- dianthryl C,,H2,N,; the best yield is obtained by diazotising with nmyl nitrite and sulphuric acid in alcoholic solution.The basic sub- stance is nearly colourless darkens at 192' has m. p. 201-202° yields anthraquinone by oxidation with chromic and acetic acids and 6 4226 ABSTRACTS OF CHEMICAL PAPERS. forms well-defined - di-acid salts ; the nitrute C28H2,N2,2HN0,,3H20 forms colourless needles ; the hydrobromide C2,H2,N2,2RBr,5H20 forms stout crystals. c. s. [Dianthraquinonylamine.] FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 174699).-Halogenat ed anthraquinones con- dense with aminoanthraquinones under the influence of metallic salts to form complex secondary amines. A dianthrccquinon~lccmint having the annexed formula is readily prepared by heating together co CO for fifteen hours 2-chloroanthra- /\,/\/~NH\,/\,/\/\ quinone 1 -aminoanthraquinone I I 1 I I I I j naphthalene anhydrous sodium \,/\/\/ \/\/\/ acetate and cupric chloride.The co CO product which is obtained i n well-defined crystals having a metallic lustre dissolves in concentrated sulphuric acid to a greenish- blue solution and. may be crystnllised from aniline or nitrobenzene. G. T. M. Preparation of Anthracene Derivatives. BADISCHE ANILTN- & SODA-FABRIK (D.R.-P. 4 75067).-2 2-Dimethyl-1 1‘-dianthraquinonyl and its derivatives which co - co are prepared from l-chloro-2- A/\/\Me Me/\/\/\ rriethylanthraquinone and its I 1 j derivatives by the action of copper powder are now found I. co to undergo a further con- densation in the presence of dehydrating agents. The substance represented by the formula I loses 2H,O and becomes converted into the compound 11 /\/’\/ \/\/\ co GO which is insoluble in water dilut‘e acids and alkalis but dissolves in concentrated sul- phuric acid to a blue solution and may be obtained from its solution in nitrobenzene as a brown crystalline powder.4 4’-Dichloro-2 2’-dimethyl-l 1’-dianthra- quinonyl .and 2 4 2’ 4’-tetramethyl-1 1’- dianthraquinonyl furnish similar condensa- tion products. G. T. M. The Constituents of Ethereal Oils (Ber. 1907,40,432-440. Compare this vol. i 11)-I y- and a-Fencholenic acids. -The a-fencholenic acid obtained from fenchone oxirne by the action of dehydrating agents and hydrolysis (Cockburn Trans. 1899,75,501) and that from bromofenchone by the action of alcoholic potassium hydroxide (Czerny Abstr. 1900 i 675) are not identical although their amides and hydrochlorides melt a t the same temperature.The acid derived from bromofenchone is called FREDERICH w. SEMMLERand KONRAD BARTELTORGANIC CHEMISTRY. 227 y-f"wAoZenic acid CIoHlsO2,and has b. p. 145-146O/lO rqm. D20 1-0087 nD 1.47838 aD + 52O.30' (100 mm.). The ccmmoltium salt m. p. 125" when heated at 180' under pressure yields the amide m. p. 113-1143 which does not depress the melting point of the amide from a-fencho- lenic acid. Reduction of the acid with hydrogen iodide and red phosphorus at 180' under pressure gives n mixture of hydrocarbons C,H or C10H20 b. p. 4S0/20 mm. D20 0.7794 nD 1.43155 and an acid b. p. 280" in a vacuum. When heated under pressure a t 160" with alcoholic potassium hydroxide the rotation of y-fencholenic acid falls t o aD + 43O or on treatment with acids to + 41.65O ; it also falls when kept for three months but it never becomes as low as that of a-fencholenic acid [.ID 32O.35'.y-Fencholenic acid in benzene solution and water when treated with ozone and then distilled in a vacuum gives a monobasic ketonic acid C8HI2O3 in quantitative yield b. p. 185-187"/10 mm. D2S 1.121 nD 1.47936 aD + 22O.30' tube (100 mm.) in 25% alcohol solution. The semicarbaxone C,H,,O,N m. p. 1 90° crystallises from methyl alcohol. When oxidised with alkaline potassium permanganate an acid b. p. 210-215"/S mm. (decornp.) is obtained. On the other hand no ketonic mid could be isolated when a-fencholenic acid is oxidised by ozone the product obtaiued has b. p. 140-230°/10 mm. the chief fract,ion b. p.210-215". This behaviour shows that a- and y-fen- cholenic acids are not identical but if y-fencholenic acid is treated with acid or alkalis and then oxidised with ozone not a trace of ketonic acid can be isolated the product has b. p. 140-230°/10 mm. When shaken with dilute sodium hydroxide for one hundred days the lactone from y-fencholenic acid of b. p. 122-123"/9 mm. and m. p. 77-78" (Czerny Zoc. cit.) gives hydroxydil~ydrofe~cholenic acid C10H1803 m. p. 105-107" which is monobasic and yields a soluble silver and a sparingly soluble copper salt. The lactone is regenerated along with an unsaturated acid b. p. 143"/10 mm. probably a-fen- cholenic acid by treatment with dilute sulphuric acid. This lactone is identical with that obtained from the a-acid as it shows no depression in m.p. when mixed with it and also on reduction with sodium and alcohol yields the same glycol C,,H2,02 b. p 158-161°/11 mm. m. p. 58-60'. The following constants of bromofenchone have been redetermined (compare Czerny Zoc. cit. and Balbisno Abstr. 1901 i 89) b. p. 125-130°/10 mm. D22 1.3005 nD 1.50605 uD + 10-12" (100 mm.). A reply to Kondakoff (A bstr. 1906 i 520). A table is also given showing how by the use of Semmler's formula for fenchone these compounds are derivable that of y-fencholenic acid is Constitution of Fenchone.-Polemical. CO,H*CMe,*?H-Q:CHMe CH;CH W.R. Terpineol of Majorana Oil. OTTO WALLACH and FRIEDRICH BODECHER (Bey. 1907 40 596-600).-0n oxidising the terpineol fraction of majorana oil (compare this vol. i 65) with permanganate a ketone is formed of which the semicarbaxone melts at 145-146'.The glycerol CloH17(OH)3 is more sparingly soluble i n chloroform and crystallises otherwise than the isomeric trioxyterpane ; on further228 ABSTRACTS O f CHEMICAL PAPERS. oxidation it gives rise to acids CloH1806 m. p. 205-206' and 188-189° which form Inctones m. p. 63-64' and 72-73're- spectively. On shaking the terpineol fraction of majorana oil with sulphuric acid cis-terpinene hydrate m. p. 11 7O and terpinene-terpine m. p. 137q are obtained along with mixed crystals of these two sub- stances m. p. 108' (about). The paper concludes with the discussion of a formula for terpineol. E. F. A. Combination of Glycuronic Acid with Optical Antipodes. ADOLF MAGNUS-LEVY (Biochem.Zeitsch. 1907 2 319-331).-Experi- ments made on dogs and rabbits indicate that both d- and I-borneol and d- and I-camphor readily combine with glycuronic acid and the animal organism appears to be incapable of differentiating between the stereoisomerides. Inactive methylethylpropylcarbinol as it com- bines with d-glycnronic acid during its passage through the organism is not resolved into active components. I-CarnphorgIycuronic acid C,,H,,O is most readily isolated from the urine of dogs fed with I-camphor by conversion into its strychnine salt C,7H,o0,,N2,BH,0 m. p. 189-195' (decomp.). The free acid contains water of crystallisation and melts between 120' and 130'. When hydrolysed with 10% sulphuric acid the complex glycuronic acid yields 1-campl~orol CloH1602 m.p. 207-210' (not sharp) [a] - 32-93' ; its semicarbazone melts and decomposes at 235-240'. Sodium l-borneoZyZ?jcuronate Cl,H,,07Na,H,0 has [a] - 66-45'. Hydroxycamphorglycuronic acid C €€2408,H20 obtained from the urine of a dog fed on Manasse's hydroxycamphor (oxaphorj m. p. 212-213' crystallises from water in glistening plfites m. p. 13S0 and the sodium salt has [aID -32.7'. When hydrolysed it yields hydroxycamphor. J. J. S. Boiling Point and the Nature of Dipentene. OTTO WALLACH (Ber. 1907 40 600-606).-The author had shown previously that whereas dipentene prepared as pure as possible has b. p. 177-178° i-limonene prepared by mixing d- and I-limonenes has b. p. 175- 176" (compare Abstr. 1888). Semmler's criticisms (Be?.. 1906,39,4427) have led him again to purify very carefully dipentene dihydrochloride heat this with aniline and remove the aniline by steam distillation the liquor being rendered acid by oxalic acid.The carefully purified dipentene had b. p. 177-178' for the greater part of the distillate and 10 grams yielded but 8.5 grams of solid tetrabromide whereas i-limonene yielded 10 grams under like conditions. It is considered that dipentene contains another hydrocarbon which cannot be separated from it by distillation and which perhaps represents $-limonene. E. F. A. Terpinenes OTTO WALLACU (Ber. 1907 40,575-584).-By the interaction of terpinene dihydrochloride and potassium hydroxide (compare this vol. i 64) a terpineol Cl,H17*OH and a terpin m. p. 136*5-137*5O are obtained along with von Baeyer's y-terpineol (m.p. G9') and cis-terpine (m. p. 117") and trans-terpine (m. p. 156'). ClOH16(OH)2,ORGANIC CHEMISTRY. 229 y-Terpineol yields a mixture of cis- and trans-terpines on shaking with acids as also though more slowly when acted on by potassium hydroxide. The terpins obtained above therefore; probably originate from y-terpineol. The terpin (m. p. 137') is easily obtained by shaking the corresponding terpineol with sulphuric acid (compare following abstract). It has b. p. 250° and crystallises in optically inactive characteristic plates. Terpinene nitrosite when reduced in glacial acetic acid solution at first at 0' and subsequently at the temperature of the water-bath yields a considerable quantity of carvenone. A still better yield of carve- none is obtained on reducing under the same conditions terpinenenitrole- piperidide (m.p. 231-232OJ ; whereas the semicarbazone oxamino- oxime and benzoate of the oxime of the compound obtained all agree with the corresponding carvenone derivatives the oxime has always a lower m. p. The paper concludes with a discussion of this reaction and a further consideration of the constitution of terpinene. E. F. A. Sabinene and its Relationship t o Terpinene. OTTO WALLACH (Ber. 1907 40 585-595).-The paper is largely of a polemical nature being a reply to Semmler (this vol. i 145). Attention is again directed to the high value of the molecular refraction of sabinene due possibly to the presence of a methylene group in a semicyclic ring. The same solid dichloride is formed whether sabinene is treated with hydrogen chloride in acetic acid or in moist ethereal solution ; in dry ether no formation of hydrochloride takes place just as in the case of limonene.In carbon disulphide solution sabineno forms a monohydrochloride b. p. 87-92O/12 turn. D 0,982 nz 1.4824 which does not yield a sparingly soluble nitrosate but forms a nitroso- cldoride decomposed by bases into iaitroZc6mines. This monohydro- chloride is converted by hydrogen chloride in acetic acid solution into the dichloride. Sabinene when shaken with sulphuric acid yields a terpin C,,H,,(OH) m. p. 437O and a terpineol Cl,H17*OH b. p. 209-212' D 0,9265 n'," 1.4785 which forms a dichloride Cl,Hl,,2HCI m. p. 52O and is converted by permanganate into the glycerol already described (this vol. i 64) from cardamom and majorana oils.The author claims priority over Semmler (Zoc. c d . ) on these points. E. F. A. IWAN SCHINDELMEISER (Chem. Centrr. 1906 ii 1764; from Apoth.-Zeit. 21 927-928).-A sample of peppermint oil from Tambow which had D19 0.908 [a]D -2l048' and n D 1.46108 mas soluble in 4 parts of 70% and in 0-5 of 95% alcohol. The oil golidified when cooled with sodium chloride and ice for a long time. The aqueous solution of an aldehyde which distilled at 115-120' when treated with silver oxide yielded an acid the silver salt of which contained 61% of silver. The oil contained i-pinene and more I-limonene than d-limonene but neither phellandrene nor menthene was present (compare Andr6eff and Andres Abstr. 1892 i 723). Cineol was separated by means of syrupy phosphoric acid Ruslsian Peppermint Oil.230 ABSTRACTS OF CHEMICAL PAPERS.and 16.36% of E-menthone [alD - 23O4*5' was isolated. The oil yielded 51.22% of a mixture of free I - and &menthols in which the former was present in the greater quantity and 4.8% of the menthyl esters of acetic and baldrianic acids calculated as acetate. A small quantity of R sesquiterpene was also obtained but paucity of material prevented identification. E. W. W. a- and p-Amyrins from Bresk. N. H. COHEN (Pvoc. K. Akad. Vetensch. Amsterdam 1906 9 471. Compare Romburgh and Cohen Abstr. 1906 197 ; Vesterberg Abstr. 1891 165).-a-Amyrin m. p. 186' (corr.) has now been obtained from bresk or djelutung; it has [.ID + 82.6' in chloroform or + 88.2' in benzene solution. The acetate m. p.2'24-225' (corr,) has [.ID +75*8' in chloroform solution; the benzoate m. p. 195' (corr.) ; the cinnanzccte crystallises in small hard needles m. p. 178' (corr.) P-Amyrin cinnamute crystallises from acetone in small needles m. p. 241' (corr.). G. Y. DAVID B. DOTT ( P l ~ ~ r m . J. 1907 [iv] 24 79).-Salicin is soluble to the extent of 1 part in 24 parts of water at 25O. E. G. Solubility of Salicin. Elaterin. FRANZ VON HEMMELMAYH. (Monatsh. 1906 2'7 I1 67-1 182. Compare Abstr. 1906 i 973 ; Thorns Chem. Zeitsch. 1906,923 ; Pollak Abstr. 1906 i 973).-The analytical results ob- tained by the author and by Berg (Abstr. 1906 i 596) with elaterin diacetylelat erin bromoelaterin ela terin diphen y 1 h y drazone and elateridin are tabulated and found t o agree best with the formula C,,H,,O for elaterin to which in agreement with its properties is now ascribed the extended formula C,,H2,(CO),(OH)2.0Ac.The formula for elateridin derived from this should contain two hydroxyl groups ; as however elateridin forms only a monoacetyl derivative which is not identical with elaterin its molecule must undergo some isomeric change during its formation. The bromo-derivative of elaterin C24H3306Br prepared by the action of bromine on elaterin in glacial acetic acid solution forms a yellow amorphous powder m. p. 112' but decomposes at 118'. The diacetyl derivative C,,H,,O,Ac m. p. 124'. The diphenylhydrazone CS6H4604N4 forms a yellow amorphous mass commences t o sinter at 158' and decomposes and evolves gas a t 170'. Elateridin C,,H,,O which sinters at 130' m.p. 140-150' gives a reddish-brown coloration with alcoholic ferric chloride and is soluble in aqueous potassium hydroxide only with difficulty. The monoacetyl derivative C?,H,,O,Ac formed by boiling elateridin with acetic anhydride and sodium acetate is obtained as a yellow amorphous mass sinters at 130° m. p. 140-150°. Elateric acid C,,H,,0,,1~H20 m. p. 70-80' ; the methyl ester C,,H,,O,Me m. *p. 85-90". When boiled with phenylhydrazine and acetic acid in alcoholic solution elateric acid forms a resinous compound C,,H,,O,N or C2SH4006N2 which sinters at 125O m. p. about 140O.ORGANIC CHEMISTRY. 231 Oxidation of elaterin with chromium trioxide in glacial acetic ticid solution leads t o the formation of a product which sinters at looo m.p. 115-120° and dissolves without change i n aqueous potassium hydroxide or carbonate. G. Y. Dyeing and Ionisation. LOO TICINON (Compt. Tend. 1907 144 81-83).-The author has shown previously (this vol. i 102) that the chemical activity of textile fibres of animal origin towards acids bases or salts increases with the dilution and consequently with the electrolytic dissociation of the solutions employed ; in the present paper it is shown that the electrolytic dissociation of dyes except in the case of picric acid increases with the dilution of the solution and also with the temperature ; the experiments were conducted on solu- tions of roccellin orange 11 magenta and picric acid and the results are tabulated in the original M. A. W. Process of Dyeing Animal Textile Fibrers.111. P. GELMO and WILHELM SUIDA (Monatsh. 1906 27 11 93-1 198. Compare Abstr. 1905 i 714; 1906 i 445).-The experiments described in this paper were performed with the same wool as was employed in the previous series. Samples of the wool were boiled with alcoholic sulphuric hydrochloric and phosphoric acids and thoroughly washed ; half of each was titrated with N/10 sulphuric acid N/10 hydrochloric acid and N/lO ammonia respectively ; the remaining half samples were boiled with aqueous ammonium carbonate and then titrated. Ammonia hydrochloric acid and sulphuric acid were absorbed in the propor- tions after treatment with alcoholic sulphuric acid NH 1034HCl 1*83H2S0,/2 ; after treatment with alcoholic hydrochloric acid BH3 4*4HCl 4*62H2S0,/2 ; or after treatment with alcoholic phosphoric acid NH3 3.95HCll 4*34H2SO,/2.After the further treatment with ammonium carbonate these three samples absorbed ammonia hydrochloric acid and sulphuric acid in the proportions NH 12.5HC1 13*4H2S0,/3 ; NH 8HC1 8*9H2S0,/2 ; and NH 5.46HCl 6*01H2SO,/2 respectively. The results of a number of dyeing experiments showed that after treatment with alcoholic acids wool gives intense shades with acid but only weak shades with basic dyes. This effect was least pronounced in the wool treated with phosphoric acid. A sample of wool treated with hydrogen chloride in absolute alcohol and thoroughly washed with alcohol and water was not dyed by basic dyes but with acid dyes gave intense shades fast to soaping. Wool treated successively with alcoholic hydrogen chloride and ammonium carbonate was dyed feebly by basic but intensely by acid dyes tho shades being removed almost entirely by soaping.N/10 ammonia N/10 hydrochloric acid and N/10 sulphuric acid were absorbed by wool which had been treated with 1% of its weight of sodium nitrite in the proportion NH 5.9HCl 7*1H2S0,/2 or by wool treated with a 1% solution of sodium nitrite in the proportion NH3 2.12HCl 2*69H2SOJ2. Wool treated with even traces of232 ABSTRACTS OF CHEMICAL PAPERS. nitrous acid has no affinity for coal-tar dyes but on exposure to light becomes yellow to intense brownish-orange depending on the amount of nitrous acid the shades being rendered more intense by addition of alkali hydroxides. No difference could be detected in the behaviour in a neutral dje- bath of untreated wool and wool treated with phosphorus trichloride.G. Y. Sulphur Dyes. HEHMANN WICHELHAUS [and in part VIEwEa] (Bw. 1907 40,I26-129).-Many natural non-nitrogenous colouring matters such an brazilin haematoxylin maclurin ouxanthone &c. are transformed into sulphur dyes when heated with sulphur in the absence of air hydrogen sulphide and to a certain extent sulphur dioxide being evolved. The dyes dissolve in sodium sulphide solution yielding brown t o black tones. Artificial phenolic dyes of the type of gallacetophenone aurin and fluorescein may be transformed into sulphur dyes by a similar process. A stable dye containing 27% of sulphur is formed when fluorescein or a mixture of phthalic anhydride and resorcinol is fused with salphur at 250-280° for six to eight hours.Similar products may be obtained from di- and tetra-chlorophthalic acids. J. J. 5. Oximes of Methylfurfuraldehyde. K. FROMHERZ and WIL~XELM MEEGEN (Ber. 1907 40 403-406).-When methylfurfuraldehyde is treated with hydroxylamine according to Goldschmidt and Zanoli's method (Abstr. 1892 i 1433) a product is obtained which is regarded as a mixture of the syn- and mati-aldoximes. When crystallised from light petroleum it melts at 51-52O but when repeatedly recrystal- lised it yields a small amount of pure syn-nzstl~~lfurficraZdon:ime C6H702N in the form of colourless glistening needles m. p. 110". The same compound may also be obtained by converting the mixture of oximes into the hydrochloride and decomposing this with alkali.The phenylmrbimide derivative C,0H1203N2 exists in two modifications a yellow labile form m. p. 101' (decomp.) and a colourless stable form m. p. 106-109°. The pure ccnti-oxime has not been obtained. J. J. S. Mixed Anhydrides of Tannic and Cinnamic Acids. FARBWERKE VORM. MEISTER LUCIUS S= BRUNING (D.R.-P. 173729)-A product containing mono- and di-acetyltannic-cinnamic anhydrides is obtained by heating together a t 100° acetic anhydride tannic acid and cinnamic acid and gradually adding phosphorus pentachloride to the mixture. The heating is continued until the prodnct yields neither cinnamic nor tannic acid on treatment with warm water; the mixture is then washed successively with cold and hot water until the filtrate has a neutral reaction.The residue which is dried at 4 5 O is soluble in alcohol and reprecipitated in an amorphous form by water. Although stable in hot water the mixed anhydrides are hydrolysed by dilute alkalis. G. T. M.ORGANIC CHEMISTRY. 233 Pyrone Hydroperbromides. ARTHUB HANTZSCH and 0. DENSTORFF Compare Abstr 1906 i 745).-Raply to (Bw. 1907 40 241-243. Feist (Abstr. 1906 i 974). c. s. Substituted Rhodanic Acids and their Aldehyde Con- densation Products. V. RUDOLF ANDREASCH (Moncatsh. 1906 27 1211-1222. Compare Abstr. 1903 i 855; 1904 i 444; 1905 i 930 933).-The action of ethyl chloroacetate on ammonium phenyl- dithiocarbazinate (Heller and Bauer Abstr. 1902 i 444) leads t o the formation of ethyl phenyldithiocarba~i?~acetate NHPh*N H*CS*S*CH,*CO,Et which crystallises in long needles m.p. 108-109' and 3-unilino- rhodanic acid NHPh*N< Co'~Hz. This forms yellow granular crys- cs- tals m. p. 1 2 5 O and is less soluble in alcohol than the carbazinate from which it is formed by heating a t looo or by boiling with glacial acetic acid and acetic anhydride. The following condensation pro- ducts of phenylrhodanic acid and aldehydes NHPh*N< CO*$XCHR are formed by heating the rhodanic acid or the ethyl carbazinate with the aldehyde and glacial acetic acid. R = P h slender yellow needles m. p. 195'; R=*C,H,*OH (0) yellow pointed needles m. p. 170-173' ; R = *C,H,*NMe2 ( p ) microscopic scarlet needles m. p. 219' ; R = *C,OH yellow needles m. p. 168'. Bargellini's work on the condensation of aldehydes with rhodanic acids (Abstr.1906 i 383 536) is criticised. The action of ethyl chloroformate on ammonium phenyldithio- carbamate in alcoholic solution leads to the formation of phenyl- thiocarbamide carbzcmide carbanilide and a substance m. p. below 1 OOO. Ethyl chlorocarbonate and ammonium phenyldithiocarbamate interact forming phenyl thiocarbimide carbon oxysulphide and ammonium chloride. G. Y. cs-s Substituted Rhodanic Acids and their Aldehyde Con- densation Products. VI. ALOIS WAGNER (Monatdi. 1906 27 1233-1244. Compare Abstr. 1903 i 855; 1904 444; 1905 i 930 933 and preceding abstract).-Andreasch and Zipser having suggested the use of rhodanic acids in the estimation of furfur- aldehyde the author has investigated the suitability of some higher substituted rhodanic acids but found this to be less than that of phenylrhodanic acid.When pure the rhodanic acids now described do not condense with aldehydes even in presence of glacial acetic or concentrated sulphuric acid ; the condensation products are obtained however from the crude e t hy 1 su hsti t ut ed dit hiocarbaminace tates formed as intermediate products in the action of ethyl chloroacetate on the substituted dithiocarbamates. 3 - a-Naphtlb y lrh odan ic u c id C ,H N< cs-s ''*? H2 prepared together with s-di-a-naphthylcarbamide by the action a t 100' of ethyl chloro- VOL. XCII. i. r234 ABSTRACTS OF CHEMICAL PAPEKS. acetate on ammonium a-napht hyldithiocarbamate obtained from a-naphthylamine carbon disulphide and concentrated aqueous ammonia crystallises in colourless tetragond.1 leaflets m.p. 167-1 689 Ethyl a-naphthyldithiocarbaminacetute NHPh*CS*S*CH,*CO,Et is formed if the action of ethyl chloroacetate on ammonium a-naphthyl- dithiocarbamate takes place below 100' ; it crystallises in large white needles m. p. 81'. 3-a-Naphthyl-5 -be?zxylidenerhodanic acid crystallises in long yellow needles m. p. 159O. The furfurylidene derivative is obtained as an oil. The corresponding P-napht hyl and p-ethoxyphenyl compounds were prepared in the same manner. 3-P-Naphtr~ylr~~odanic acid C13HgONS2 formed together with 8-di-P-naphthylthiocarbamide crystallises in microscopic brown pointed needles m. p. 180-1 90'. Ethyl P-naphthyldithiocarbamin - acetate C,,H,,O,NS crystallises in needles m. p. 83". 3-P-Naphtly~?- 6-benx~lidenerhodacnzc ucid C,,H,,0NS2 crystallises in microscopic yellow leaflets m.p. 2 0 2'. 3 -/I -iVaph t hyl- 5 furf ur y lidenerhodanic acid C,,H7"<(Ys4 C0*C:CH'C4H30 crystallises in slender yellow needles m. p. 208". 3-p-Ethoxyphenylrhodunic acid OEt*CGH4*N< crystallises in long yellowish-white needles m. p. 180-188". The 5-benxylide?ze derivative C,,H,,O,NS Porms long sulphur-yellow needles m. p. 212-214". The Bfurfurylidene derivative C14H130,NS2 crystallises in long chrome-yellow needles m. p. 197". cs-8 G. Y. Derivatives of Hordenine. Euahm L~GER (Compt. rend. 1907 144 208-210. Compare Abstr. 1906 i 204 '761 ; this vol. i 151).- The following derivatives of hordenine acting (1) as a tertiary amine (2) as a phenol and (3) as both amine and phenol are described. The nor.maZ tartrate ( Cl0H,,ON),,C4H,O6 anhydrous needles ; the hydrogen tartrate C,,H,,0N,C4HG06 anhydrous needles ; hordenine methochloride (C,oHl,ON),MeCI anhydrous needles ; hordenine ethochloride C,oH,,ON,EtCl anhydrous needles ; hordenine ethobromide C,oHl,ON,EtBr square plates ; hordenine ethiodide C,,H,,ON,EtI anhydrous prismatic needles ; bmxoylhordeninne hydrochlomde CloH14BzON,HCl an hydr- ous needles ; benzoylhordenine hydrobromzde CloH14BzON,EBr brilliant rectangular lamells ; cinnamoylhordenine long slender needles m p.55.S0 (corr.) (partial decomp.) but forming stable salts which crystallise easily ; cinnamoylhordenine hydrochloride prismatic needles ; anisylhordenine hydrochloride large efflorescent plates. Methylhordenine methiodide OMe C,H4-[C H2],*NMe31 Blender white felted needles containing 1+H,O. C,~H~~(CgH~O)ON,HC11,H,O C,,Hl,(C,H702)0N,HC1,H,O E.H.ORGANIC CHEMIS'I'HY. 235 Prepasation of Acetyl Derivatives of Morphine Bases. KNOLL Jt Co. (D.R.-P. 17506S).-By treating morphine bases with sulphoacetic acid or a mixture of acetic anhydride and sulphuric acid a series of new acetyl derivatives has been obtained. Triacetylmor- p7~ine m. p. 206-208°; diacetyZcodeine m. p. 145-146' and di- 6enxo~ZacetyZi)~orphine (from dibenzoylmorphine) m. p. 166-1 68' are described. G. T. M. Behaviour of Chlorocodide on Reduction. LUDWIG KNORR and HEINRICH HORLEIN (Ber. 1907 40 376-377. Compare Gohlich Abstr. 1894 i 431 ; Vongerichten and Miiller Abstr. 1903 i 57 1).- On reduction with sodium and ethyl or amyl alcohol or with tin or zinc dust and hydrochloric acid chlorocodide yields deoxgcodeine which crystallises in shining leaflets loses &H,O above loo' m.p. about 126' (decomp.) when quickly heated ; the anhydrous substance is vitreous. It forms crystalline salts ; the I~ydrochloride separates C1,H2,02N7$H,0 froin alcohol in prisms m. p. about 165' (decomp.). G. Y. Melting Point of Cotarnine. DAVID B. DOTT (PAu7.m. J. 1907 [ iv 1 24 78-79).-Freshly prepared cotarnine purified by crystal- lisation from benzene has m. p. 125' (decomp.). When the crystalline base is heated on the water-bath it loses weight equivalent to more than 1 mol. H,O and then melts at 100'. It is therefore considered that the m. p. of cotarnine is of little value as a test for purity. E. G. Preparation of Cotarnine Phthalates.KNOLL dk Co. (D. K.-Y. I 75079).-Cotur?~ine phthaZccte m. p. 102-105° is obtained by mixing 237 parts of cotarnine and 83 parts of phthalic acid in aqueous or methyl alcoholic solution and concentrating under reduced pressure. Cotarnine hydrogen phthalate produced by mixing alcoholic solution of sodium hydrogen phthalate and cotarnine hydrochloride is obtained from the solution after removing sodium chloride in well-defined yellow crystals m. p. 115O. The normal salt when recrystallised from alcohol tends to decompose into the acid salt and free base. G. T. 33. Narceine. MARTIN FREUND [and BESCHKE] (Ber. 1907 40 194-204. Compare Freund and Frankforter Abstr. 1894 i 58).- The author has repeated the alkylation of narceine by the action of methyl and ethyl iodides on sodium narceine and confirms Tambach and Jiiger's statement that the alcohol used as solvent is without influencs on the nature of the product (Abstr.1906 i 879) ; contrary however to these authors' view it is found that the product of methyl- ation m. p. 208-209' is the narceinium methiodide methyl ester CO,Me*C,H,(OI1Ie),CO.CH2*~~H(OMe)(<~>CH2)~~H2*C~2*~Me~and not methylnarceinium methiodide whilst similarly the product of ethylation ( + H,O) m. p. 141' or ( + C2H,0) m. p. 181. is narceinium ethiodide ethyl ester C02Et*C20H200,*NilIe,EtI and not ethylnar- r 2236 ABSTRACTS OF CHEMICAL PAPERS. ceinium ethiodide. The formuls given by Tambach and Jager for the remainder of their products of narceine must be altered in the same sense.Narceinium methiodide formed by heating narceine with methyl iodide at looo and described previously as a resin (Freund and Frank- forter loc. cit.) crystallises from water in needles rn. p. 207" and when boiled with aqueous alkalis yields trimethylamine and narceonic acid m. p. 217" (20So loc. eft.). The product formed by heating narceine with methyl sulphate and alcohol (Tambach and Jiiger) is narceinium hydrogen methosulphate C,~H,70,N,MeHS0 which is decomposed by water forriiing narceine. f h e action of 1 mol. of methyl sulphate on sodium narceine leads t o the formation of the sodium salt of methylnarceinium metho- sulphate C02Na~C,,H,,0,*NMe3*S0,Me which on treatment with hydrochloric acid yields narceinium methochloride C0,H*C,,H,,00*NMe3Cl m. p.243O; this is converted by potassium iodide into the methiodide m. p. 207". The product m. p. 184-186' of the action of 2 mols. of methyl sulphate on sodium narceine is the udditive compound of methyl sulphate and narceine methyl ester; i t is converted by potassium iodide into the methyl ester of narceinium methiodide which is insoluble in aqueous alkalis. Xthyl sulphate (1 mol.) and sodium narceiiie yield sodium nay- ceiniuni ethosulphate which on treatment with hydrochloric acid forms narceinium ethochloride C02H*C,,H,,0,~NMe2EtC1 m. p. 231"; this is converted by boiling aqueous alkalis into narceonic acid. The base m. p. 175-177' obtained from the ethochloride is probably the betaine C,oH2,0,<~-Me6,Et ''->O. The ethochloride is converted by alcoholic hydrogen chloride :nto narceinium ethochloride ethyl ester C0,Et*C20H,o0,*NMe,EtCI m.p. 218-219' which is formed also by the action of silver chloride on the ethyl ester of narceinium ethiodide ; this yields narceonic acid when boiled with aqueous alkalis. The product (m. p. 191-193" Tambach and Jager Zoc. cit.) of the action of ethyl iodide on narceine ethyl ester is narceinium ethiodide ethyl ester m. p. 181" when recrystallised from alcohol. The action of sodium methoxide on narceine ethyl ester in methyl alcoholic solution leads to the formation of narcindonine C12H1603N*CH<~~>C6H,(OMe)2 1 4H20 which is formed also together with narceine by the action of sodium methoxide on aponarceine (compare Freund and Michaels Abstr. 1895 i 630; Eibner Abstr.1906 i 588); it crystalliaes in red prates m. p. 168-169' loses 1&H20 a t l l O o and then has m. p. 174". Tambach and Jiiger's ccponarceine is considered t o be probably the -O- lactone C,2€i,,0,N*CH:C<C (oMe)2>C0. G. Y. G 2 Preparation of Narceine and Homonarceine Derivatives. KNOLL 9t Co. (D.R.-P. 174380).-The alkali derivatives of narceineORGANIC CHEMISTHY. 237 and homonarceine or the corresponding compounds with the alkali earth metals when treated with methyl or ethyl sulphate give rise to new alkyl derivatives of these bases in which the carboxyl group is still unesterified. Narceine dissolved in N-sodium hydroxide and treated with methyl sulphate furnishes a base the salt of which crystallises from alcohol m. p. 242'. This compound when esterified with alcoholic hydrogen- chloride yields an ester ILgdrochZoride m.p. 21 4-2 16' ; plotini- chloride rn. p. 220'. Narceine and ethyl sulphate give rise to a similar base hy&ochZofide M. p. 231'; hyd?*ochZoride of ethgl ester m. p. 219'. The base from homonarceine and methyl sulphate has the following derivatives Iqdrochloride m. p. 231 -232'; platinichloride m. p. 181-182'; hyds.ocTdoyide of ethyl ester m. p. 212-214'. Homonarceirie and ethyl sulphate give a similar ethyl derivative hydrochloride m. p. 21 lo. G. T. M. Tertiary and Quaternary Bases from Piperidine. 11. SIEGMUND GABRIEL and JAMES COLMAN (Bw. 1907 40 424-427. Compare Abstr. 1906 i 881 ; Gabriel and Stelzner 1896 i 702; Horlein and Kneisel 19 0 6 i 4 5 8) .- 1 -y-iY.ydrox ypropyZpipes.idi ne C,H,,N-[CH,],*CH,*OH obtained by heating 2 parts of tri- rnethylenechlorohydrin with 4 parts of piperidine for one hour a t the temperature of the water-bath and then liberating the base with potassium hydroxide is a colourless oil b.p. 225-228'/759 mm. The base is precipitated from its aqueous solution by potassium hydroxide. The hg'clrochloride is precipitated from alcoholic solution by acetone as a crystalline hygroscopic powder m. p. 151' ; the aurichloride forms golden-yellow hexagonal plates m. p. 69-70' When heated with hydrochloric acid at 150' the base is converted into 1-y-chloropropyl- piperidine. By repeated fractionation of the portion distilling at 200-300° obtained in the interaction of the quaternary salt and potassium hydroxide (Eoc. cit.) an oil b.p. 224-227' was isolated and identified as 1-y-hydroxypropylpiperidine. The chief product of this interaction dipiperidinopropyl ether is formed either by the condensation of the 1 -y-chloropropylpiperidine and y-hydroxy base or by dehydration of the base. 1 -6- CI~Zo?.obutyZpipe~idine I~ydrochloride C,H,,N* [ CH,14C I ,HCI crys- tallises ffom acetone in colourless needles m. p. 167'. W. R. Nitroso-derivatives of Cyclic Acetone Bases. MORITZ KOHN and FRANZ WENZEL (Jfonatsl~ 1906 27 981-986. Compare Heintz this Journal 1877 ii 428 ; Fischer Abstr. 1884 1290 ; Antrick Abstr. 1885 502).-Nitroso-derivatives have been obtained from vinyldiacetonamine isobutylidenediacetonamine and benzylidenedi- acetonamine by the action of potassium nitrite on the hydrochloride of the base in aaueous solution 1 -Nitroso- 2 2 6-trimethy Zpiperidone (?.Litrosoviit~Zdiacet onamin E ) CO<CH2'CHMe>N*NQ CH,-CMe2238 ABSTRACTS OF CHEMICAL PAPERS.crystallises from dilute methyl alcohol in light yellow rhombic plates [a b c= 0.9878 1.0932 1 rn. p. or a b c = 0.6585 0,7288 11 58 -59'. ~~ 2 2 - B imetly l- 6 is opropyEpipe&don e (i so bu t y Z idened i m e t o numine) co<C H,*CHPra C H,-C Me >NH prepared by boiling isobutaldehyde i i t h diacetonamine oxalate i n alcoholic solution is obtained as a slightly yellow oil b. p. 115'1 23 mm. The aziricldwide CloH190N,HAuCl was analysed. The nitroso- derivative C,,H,,ON*NO crystallises in light spears m. p. 5 1-52O. 1 -Nitroso- 6-phe~yl-2 ~-dimetlLyZ~i~~eridone (nitrosobenxylidenediuceton- amine) Co<(lH2 CH2*CHPh>NoN0 -CMe2 forms large yellow rhombic crystals [a b c = 0.6465 0.7286 11 m.1). 66-68O.- G. Y. Hydroxoaquodipyridinediammincobalt and Diaquodipyr- idinediammincobalt Salts. ALFRED WERNER (Bey. 1907 40 4 6 8 -479) .-Hydroxouquodipyridinediccmmincoba Ztich Zoride [Epo c0 giH3)JC12 obtained by the addition of dichlorodiaquodiammincobaltichloride [GIa Co (OH& Cl to a mixture of potassium chloride water and pyridine at 0" separates as a pink crystalline deposit with a nacreous lustre. Its aqueous solution is brownish-red gives a feebly a1 kaline reaction with litmw and quickly decomposes the odour of pyridine becomiog perceptible. When potassium bromide potassium thio- cyanate &c. are added to a freshly-prepared solntion the correspond- ing hydroxoaquo-salts are precipitated.I (NW2 Hy droxoaquodipyridinediunmainco ba lti bromide Co Q2 p2 [.,q (NH3)Z is a violet-red microcrystalline salt. It may also be obtained by the addition of potassium bromide to diaquodipyridinediammincobalti- chloride by the treatment of the diaquo-bromide with water or by the precipitation of the aqueous solution with a little hydrobromic acid and by washing the diaquo-bromide with alcohol. The nitrate crystal- lises in bluish pale-red needles ; the thiocyanate forms violet-brown needles. The dzthionate forms reddish- brown leaflets with a. metallic lustre. Biaquodippidinediam.nzincoba Ztichloride [(H20h (20 $~3)plCJ,92H,09 (NH3)2 1 obtained by the action of concentrated hydrochloric acid on hydroxo- aquodipyridinediammincobaltichloride forms a grey crystalline powder and may be obtained also as ruby-red crystals or as greenish- grey or yellowish-brown prisms.When heated a t 60° it is converted into the compozcnd [ C1 Co C1 which is a chocolate-coloured powder; its ~olution in water is brownish-red and gives an acid reaction.ORGANIC CHEMISTRY. 239 When an aqueous solution of diaquodipyridinediammincobalti- chloride is heated with concentrated hydrochloric acid chlorine is evolved. When however concentrated hydrochloric acid is added to the solid salt dic~lorodipyridinediccmmincobaltonitrate - - [Cl c o gfQ-JNO89 separates in dark green leaflets. pw) c0 pH 3 ) 2- j ~ ~ ~ o obtained by the action of concentrated hydrobromic acid on hydroxo- aquodipyr<dinediammincobaltichloride fckrns yellowish-brown ieaflets. Its aqueous solution is brownish-red and shows an acid reaction.The sulphate [(H,O) Co PNYHs)zlz(S0~),,2H,R01. separates in brownish-violet leaflets. Its aqueous solution is red and shows an acid reaction. The nitrate [(H20)2 Co PY2 (NH,) ] (N0,),,2H20 forms red crystals. The dithionde [ ( K20) Co (NH,)2 JS20,),,2H,0 is a brown crystalline powder. Mercury Salts of Isatin and of 1 3-Diketohydrindene. WALTER PETERS (Ber. 1907 40 235-24O).-The author's aim is the preparation of N- and of 0-metallic derivatives of isatin and of C-' and 0-derivatives of 1 3-diketohydrindene (compare Hantzsch Abstr. 1903 i 662). Mercuryisatin obtained in 95% yield by decomposing a boiling alcoholic solution of isatin with concentrated aqueous mercuric acetate is a dark red glistening substance which dissolves in alkalis to a yellow solution ; consequently it has the constitution A.McK. py2 1 When an aqueous solution is treatid with potassium hydroxide and subsequently neu tralised a precipitate of o-mercuriccmi~zobenxoylformic acid C,H,<E%:2H is obtained in glistening white or grey leaflets containing 2H20 which is lost a t looo the substance turning red; at higher temperatures isatin is formed. An attempt to prepare the potassium salt of the preceding acid by passing carbon dioxide into an alkaline solution of mercury isatin resulted in the co-Go> formation of the substance C,H4<NH.Hg . 0-metallic derivatives of isatin have not-been prepared. When an aqueous or alcoholic solution of sodio-1 3-diketohydrindene is treated with excess of mercuric chloride a light yellow substance C,H,<~~>CH~H~CI is obtained which is changed by sodium carbonate into a white - hydroxide C,H,<gE>CH* Hg *OH.c. 5.240 ABSTRACTS OF CHEMICAL PAPERS. Iadolinones. KARL BRUNNER (Monatsh. 1906 27 1183-1192. Compare Abstr. 1897 i 100 ; 1898 i 90; 1905 i 468 ; Bchwarz Abstr. 1903 i 853).-A list is given of the indolinones which have been prepared by heating hydrazides with calcium oxide aud two new members of the group are described. isoButylryl-o-tol ylh ydraxide C,H X H*NH* COO CHMe2 formed by heating o-tolylhydrazine with isobutyric acid a t 1 30° crystallises in leaflets m. p. 93" tind when heated with calcium oxide a t 190-200" is converted into 3 3 7-trimethylindoZine-2-one C H 3 M e < ~ ~ ~ > C 0 which crystallises in colourless rhombic leaflets m.p. 150° b. p. 285- 295" is soluble in concentrated mineral acids or aqueous alkalis and gives a transient intense carmine-red coloi ation with manganese dioxide or potassium dichromate in concentrated sulphuric acid solution ; the silver derivative CllHl,ONAg forms microscopic prisms. The homo-derivative C,,H,,ON Br formed by the action of hydro- brouiic acid on the indolinone crystallises in rectangular leaflets isoButy.r.yl-p-tolyZl~ydraxide prepared from isobutyric acid and p-toly€hydrazine cryst allises in white leaflets m. p. 147-1 4 8 O and when heated with calcium oxide at 220-240" yields 3 3 5-trimethyl- indoline-2-one C,,H,,ON ; this crystallises from dilute alcohol in leaflets m.p. 144-145' or in needles m. p. 140" when rapidly heated when slowly heated m. p. 144-145O. It dissolves in hot concentrated sodium hydroxide and deposits the sodium derivative in long needles on cooling ; the silver derivative C,,H,,ONAg is gelatinous. The brorno-derivative C,,H,,ONBr crystallises in long prisms m. p. 21 4". m. p. 179-180". G. Y. A New Indolinol. GUIDO JENISCH (Monatal~ 1906,27,1223-1232). -Brunner (Abstr. 1898 i 384 682; 1900 i 360) has shown that indolinium bases having an alkyl group in the position 2 lose water forming 2-methyleneindolines but that the +-ammonium base or indolinol is obtained if position 2 is occupied by hydrogen. This is now found to be the case with 2-arylindolinium bases.2-PhenyZ-1 ; 3 3-trimethyZ-2-indolinoZ C,H4<gE:>CPh*OH is formed by the snccessive action of alcoholic stannous chloride and potassium hydroxide on the condensation product of phenyl isopropyl ketone and as-phenylmethylhydrazine or by the action of magnesium phenyl bromide on 1 3 3-trimethylindolinone in ethereal-benzene solution ; it crystallises in almost colourless leaflets m. p. 101-102° and dissolves readily in dilute mineral acids forming solutions which slowly became red on exposure to air. C,?H,,N Cl,FeCl forms yellowish-green crystals ; the platinichloride (C,~H,,NCI),PtCl m. p. 216-21 6.5" ; the picrate C,,H,,O,N m. p. 139-140'. The +-base remains unchanged when boiled with concentrated hydrochloric acid or heated with zinc chloride at 120° but is oxidised by alcoholic potassium permanganate and with hydrobromic acid in hydrochloric acid solution yields a crystalline product m.p. 191". Theferrichloride G. Y.ORGANIC CHEMISTRY 241 Mechanism of the S y n t h e s i a of Quinoline Derivatives. Lours J. SIMON (Compt. rend. 1907 144 138-140. Compare Abstr. 1906 i 887 888).-A theoretical paper discussing possible mechanisms of the synthesis of quinoline derivatives. E. H. /3-Chloroethyl Ketones and Alkyl Vinyl Ketones. Method of Synthesising 4-Alkylquinolines. EDMOND E. BLAISE and M. MAIRE (Compt. rend. 1907 144 93-95. Compare Abstr. 1906 i 142).-4-Alkylquinolines can be readily prepared by heating 1 mol. of a P-chloroethyl ketone with 2 mols. of aniline in alcoholic solution on a water-bath in this case the aniline hydrochloride which is one of the products of the reactions serves t o effect the formation of a cyclic compound from the open chain compound first formed and in fact P-anilinoethyl ekhy 1 ketone yields the corresponding quinoline when heated with aniline hydrochloride.4-Ethglquinoline b. p. 134'/9 mm. yields cinchoninic acid on oxidation and differs from the compound described by Reher (Abstr. 1887 279) which was probably impure; 4-n-p~opylquiitoline has b. p. 159'/16 mm. I n view of the fact that phenolic amines form compounds with vinyl ketones owing t o the presence of the ethylenic linking in the ketone the authors suggest that Skraup's quinoline synthesis may be repre- sented by the equations CH,:CH*CHO -+ NHPh*CH,*CH,*CH:NPh + NU,Ph + H,.IT. A. W. Alkylation of Pyridones. HANS MEYER (Monatsl~ 1906 27 987-996. Compare Abstr. 1906 i 108 604).-The action of diazo- methane on kynurine in ethereal solution in presence of a small quantity of methyl alcohol leads to the formation of 4-methoxy- quinoline together with a small amount of the +-methyl ether. The hydrochloride of 4-methoxyquinoline crystallises in long colourless needles m. p. 164-1 66' (decomp.). Kymwine auricltloiicle forms slender lemon-yellow needles m. p. 2 17" (decomp.). 4-Methoxy-2-methylquinoline formed by the action of diazomethane on 2-methylkynurin0 crystallises in white needles m. p. 62" (82O Conrad and Limpach Abstr.. 1877 679). the action of p-toluidine in presence of alcohol at the laboratory temperature on ethyl formylphenylacetate obtained by treating ethyl phenylacetate with ethyl formate and sodium in ethereal solution and heating the resulting ethyl a-phenyl-P-p-toluidinoacrylate at 300".It crystallises from alcohol in long white glistening needles m. p. 315'. When treated with a large excess of diazomethane it yields only a small amount of the 0-methyl ether C,H,NPhMe*OMe which separates from methyl alcohol in needles m. p. 117'. 4-Me thox y-2 -methyl- and 4-methoxy-3-phen y l- 6-me t hy lquinoline yield methyl iodide readily and quantitatively when heated with hydriodic acid ; the corresponding 4-ethoxyquinolines have been242 ABSTRACTS OF OHEMICAL PAPERS. prepared and their behaviour in this respect compared (see Gold- schmiedt. this vol.. i. 30). * I I m.p. 40-41° C( OE t) YH 4-Ethoxy-2-methylquinoline CSHI<N - CMe' b. p. 290° prepared by heating 4-chloro-2-methylquinoline (Conrad and Limpach loc. cit.) with sodium ethoxide and absolute alcohol under pressure at 130° reacts only slowly with hgdriodic acid and when treated according t o the Herzig-Meyer method of estimating N-alkyl groups yields about 40% of the theoretical amount of silver iodide. pre- C(0Et):yPh -CH ' 4-Chloro-3-p7t,e~ayl-6-nzethylquinoline C,H,Me<N pared by the action of phosphorus pentachloride and oxychloride on the hydroxyquinoline crystallises in white needles m. p. 94O and when heated with sodium ethoxide and absolute alcohol a t 100' is converted into theO-ethyl ether; this is obtained as an oil and yields ethyl iodide quantitatively when heated with hydriodic acid.G. Y. New Carbaeoles. WALTHER BORSCHE and M. FEISE (Beq.. 1907 40 378-386).-This investigation undertaken with the object of preparing homologues of carbazole by the Friedel-Craft reaction has led to the formation of carbazyl methyl ketones and by oxidation of these to that of carbazolecarboxylic acids. The position assumed by the acetyl- and carboxyl-groups respectively has not been determined. Attempts to do so were unsuccessful in consequence of the stability of 3-methylcarbazole (Delktra and Ullmann Abstr. 1904 i 2'70) towards oxidising agents. Two new formations of 3-methylcarbazole are described. Diacetylcavbaxole formed by the action of C,H. 1 ) 4 acetyl bromide and aluminium chloride on 9 -acetylcarbazole in anhydrous carbon disulphide solution is obtained as a brown crystal- line precipitate m.p. 104'. The oxirne C16H1402N2 crystallises from alcohol or ethyl acetate in white nodular aggregates m. p. 1'72O. Hydrolysis of the diacetyl compound with boiling alcoholic sulphuric acid leads to the formation of cai*bax?il methd ketone wG u4 which crystallises from alcohol or toluene in whit,eleaflets m. p. 227' ; the sernicarbcmone crystallises in colourless scales m. p. above 360' ; the oxirne C,,H,,ON,I forms glistening colourless leaflets m. p. 253'. Cinnamoylcarbaxole NH< c6H30ComCH~cHph I prepared by the action C,HA of benzaldehyde and sodi;m= ethoxide on the methyl ketone in alcoholic solution crystallises in small yellow needles m. p. 282'. formed by heating the methyl ketone with fused potassium hydroxide crys tallises in slender Carbaxolecarboxylic mid NH< 1 C6H4ORGANIC CHEMISTRY.243 colourless needles m. p. 320-322' ; the ethyl ester C,,H1,02N forms colourless leaflets m. p. 184'. a'-Nitro-Q-met hyldiphenyl amine (Jacobson and Lisch ke A bstr. 1899 i 276) is prepared by hydrolysis with concentrated hydrochloric acid in a sealed tube a t 130-140" of p-tolnidine 3-nitro-4-p-toluidino- benzenesulphonate formed by boiling p-toluidine 4-chloro-3-nitro- benzenesulphonate with p-toluidine. The benzoyl derivative of ptolyl-o-phenylenediamine CzoHlsON crystallises in colourless needles m. p. 143-144". 1-p-ToZyZ-! 2 3-benzoti-inxole N<z(c7H7)>C6H4 formed by the action of sodium nitrite on p-tolyl-o-phenylenediarnine in hydrochloric acid solution crystallises in colourless needles m.p. 84-85' and on distillation yields 3-methylcarbazole. The hydrochloride of 2-amino-4-methyldiphenyiamine formed by the action of bromobenzene on nitrotoluidine in nitrobenzene solution and reduction of the resulting product crystallises in colourless needles m. p. 200-201° ; the base NHPh*C,H,Me*NH crystallises in glistening needles m. p. 140'. The benxoyl derivative C,,H,,ON crystallises from alcohol in colourless needles m. p. 161'. -1 -P~~enyl-S-~aetjLyl-l 2 3-benzot~iazole N<zs>C,H3Me prepared by the action of nitrous acid on the preceding base crystallises from a mixture of benzene and light petroleum in small glistening prisms m. p. 117' and on distillation yields 3-methylcarbazole.9-Acetyl-3-1nethylcarbaxoZe NAc<beH3 prepared by heating 3-methylcarbazole with acetic anhydride at 220-240' is obtained as an oil which reacts with acetyl bromide and aluminium chloride C H M e . forming 9 acetyl-3-methylcccrbaxyl methyl ketone C,H,*COMe ' this crystallises in yellow needles m. p. 131' and on hydrolysis with sulphuric acid yields 3-methylcarbaxyl methyl ketone C H Me 6 4 NAc< I ' $?,HPe NH<C,II,* COMe' which crystallises in white nodules m. p. about 200'. C'H3Me formed by fusing 9-acetyl-3-methylcarbazyl methyl ketone with potassium hydroxide crgstallises in colourless scales which darken above 220° m. p. 265'. G. Y. NH<bG€€3.Co2H' 3-Meth ylcar baxolecarboxylic acid Estimation of Loosely Combined Methylene Uroupe. EMIL VOTO~EK and VIKTOR VESELY (Ber.1907 40 410-414)- Methylene derivatives which contain the methylene group attached to oxygen of aliphatic compounds or those containing the methylene groups attached to nitrogen readily react with a glacial acetic acid solution of carbazole in the presence of hydrochloric or sulphuric acid yielding insoluble products. It is claimed that the compound m. p. 202-203O obtained by Morgan (Trans 1898 73 550) by the action244 ABSTRACTS OF CHEMICAL PAPERS. of formaldehyde on P-naphthylamine cannot have the constitution suggested as it does not react with carbazole. The product obtained by the action of formaldehyde on carbazole has the composition Carbazole and dimethylene gluconic acid yields a crystalline product %oH2P2- CgaH,,N2 m. p. above 280".J. J. S. Nitro-derivatives of P-Naphthaquinoline. HANS HEPNER (Monatsh 1906 27 1045-1068. Compare Haid Abstr. 1906 i 605 ; Claus and Resseler Abstr. 1898 i 331).-On nitration at 70-80" by Claus and Kramer's method (Abstr. 1885 908) s-naphthaquinoline yields a dinitro-derirat ive which forms microscopic needles m. p. 249'" ; when recrystallisecl from concentrated hydrochloric acid i t forms a hydrochloride which crystallises in prismatic needles m. p. 249" evolving hydrogen chloride and decomposes on treatment with water. Nitration of P-naphthaquinoline a t the laboratory temperatnre leads to the formation of a mononitro-derivative m. p. 173" which is identical with Claus and Besseler's comDound (Zoc. cit.). C,,H7N(NO,),,HCI I prepared 'C Ii yH C,NH ' Diamino-P-naphthapuinoline C1,H2(NH,),< reduction of the dinitro-compound with stannous chJloridJe and hydro- chloric acid crystallises in yellow microscopic needles m.p. 249' ; the hydroc?doride C13H7N(NH,),,2HC1 forms dark red needles remains unchanged a t 300° but at higher temperatures decomposes without melting and when recrystallised from concentrated hydro- chloric acid forms an unstable trihydrochloride ; the suZphate nitrate Cl,H7N(NH2),,2HN0 and stannochloride C,,H7N (NH,) 2HC1,2SnC12 are described. On oxidation with potassium permanganate or chromic acid in sulphuric acid solution the base yields quinoline-5 6-dicacl-boxylic acid C,H,N( C02H),,H20 which crystallises in almost colourless rhombic leaflets sinters at 233* m. p. 238-241' (decomp.) and is stable towards oxidising agents.A number of salts are described ; the lead C,H,N(CO,H),Pb,~H,O and basic copper salts were analysed. The hydrochloride C,H,N( CO,H),,HCl forms strongly refracting colourless prisms ; the nit?-ate C,H,N( CO,H ),,HN03,Hz0 crjstallises in needles m. p. 208-2 10' (decomp.) ; the pZcctinichZoride [CgH5W(C02H),],,H,PtC1 forms yellow needles and gradually decomposes when heated. G. Y. '1 SH7"( H2)2 ,H2S04,H20 ; Cg HSN (CO2H) ,CUT CU( OH)pHzO Constitution of o-Tolidine. GUSTAV SCHULTZ GEORG ROHDE and F. VICARI (Annnlen 1907 352 111-131. Compare Abstr. 1904 i 532).-Proof is given that o-tolidine is 4 4'-diamino-3 3'-ORGANIC CHEMISTRY. 245 dime t hyldiphen y 1. Sodium bisdiaxo-o-dit olyleu Zphoizat e is obtained by adding sodium sulphite to a cold diazotised solution of o-tolidine in sulphuric acid; it crystallises in white needles which when heated decompose without melting.This substance when reduced by stannous chloride and hydrochloric acid is converted into o-tolidinedihydraxine hydrochloride which crystallises in yellow needles; thefree buse is obtained as a greyish- white precipitate by decomposing the hydrochloride with sodium carbonate or sulphite; it could not be obtained in a crystalline form; by warming it with an alcoholic solution of benzaldehyde a yellow substance is obtained ; with acetone a grey substance is obtained. By distilling a mixture of o-tolidinedihydrazine with copper acetate 3 3'-dimethyldiphenyl Cl4EI4 is obtained ; it is a colourless oil b. p. 286-287O/713 mm.which solidifies at - 16' to a white crystalline mass m. p. +5-?". The same compound is obtained by the action of sodium on nz-iodotoluene in ether therefore in o-tolidine the methyl groups occupy the 3 3'-positions. 3 3'-Dimethyldiphenyl is converted by a mixture of nitric and siilphuric acids into 4 4'-dinitro-3 3'-dimethyldiphenyI CIQHl2O4N2 which crystallises in faintly yellow needles m. p. 228'. When reduced with sodium sulphide it is converted into 4-nitro-4'-amino- 3 S'=dimethyldiphenyl which crystallises in yellow needles m. p 142-143' ; o-tolidine is obtained from the latter compound bg reduction with tin and hydrochloric acid in alcoholic solution. That in o-tolidine 'the amino-groups occupy the 4 4'-positions is shown by the fact that the same dichlorodiphenyldicarboxylic acid is obtained both from o-tolidine and from benzidinedicarboxylic acid.I n the latter substance the 4 4'-positions of the amino-groups has been definitely proved. Dichloro-3 3'-dimethyldiphenyl obtained by Sandmeyer's reaction froin 0- tolidine may be oxidised to dichlorodiphenyldicarboxylic acid ; the acid has m. p. 323-324' and its methyl ester m. p. 134'. When heated above 3 2 4 O carbon dioxide is evolved and 4 4'-dichlorodiphenyl is formed. W. H. G Hydroxy-derivatives of Malachite-Green. EMIL VOTO~EK and J. JEL~NEK (Ber. 1907 40 406-410. Compare Noelting and Gerlinger Abstr. 1906 i 610). - o -MethoxyZeucomaZuchite-green C,,H,,ON obtained from anisaldehyde and dimethylaniline crystal- lises from alcohol in colourless prisms m.p. 106O and when oxidised yields a green dye with a red fluorescence. The corresponding ethoxy- derivative melts a t 125' and also yields a green dye. The Zeuco-base C24H260,N2 from piperonal and dimethylaniline melts at 109-1 10' and yields a bluish-green dye. Anisole and tetramethyldiamino- benzhydrol yield a leuco-base C,,H280N m. p. 1 5 5 O which is oxidised to a blue dye. It dyes cotton mordanted with tannin a greenish-blue but this changes to violet on the addition of alkalis. The correspond- ing Zeuco-base from phenetole melts at 165' and yields a dye which gives a blue colour on mordanted cotton. The addition of alkali produces a violet colour. Guaiacol and tetramethyldiaminobenzhydrol yield a Zeuco-base which forms pale rose-coloured crystals m. p.246 ABSTRACTS OF CHEMICAL PAPERS.-1 34-1 3 5 O . @-Naphthol and tetra- methyldiaminobenzhydrol yield a leuco-base which could not be iso- lated in a crystalline form. The corresponding dye is pure blue in colour. The acetyl derivative of the leuco-base C29H3002N2 melts at 136" and yields a green dye. The corresponding dye is blue. J. 8. 5. 3-Phenyl-1 -methgl-5-pyrazolone. AUGUST MICHAELIS (An?zccle?a 1907 352 152-21 'I).-Although l-phenyl-3-rnethyl-5-pyrazolone and its derivatives have been studied extensively the isomeric 3-phenyl- 1-methyl-5-pyrazolone had not been investigated to any extent. The two isomerides,although different physically are very similar chemically differing chiefly in their behaviour towards benzaldehyde with which substance 1 -phenyl-3-methyl-5-pyrazolone alone gives n crystalline benzylidene derivative.From 3-phenyl-1-methyl-5-pyrazolone an anti- pyrine has been prepared which the author calls isoantipyrine the isomeride previously known by this name being called 3-antipyrine ; all three isomeric antipyrines behave similarly physiologically the 3-antipyrine being the most poisonous. [With WILHELM RASSMANN.]-B~ heating 3-phenyl-5-pyrazolone dissolved in benzene with phosphorus oxychloride in sealed tubes at 190-200° 5-cl~loro-3-pl~e~~~l~~yrazoZe is formed ; it crystallises in white needles m. p. 142O but sublimes below this temperature and distils undecomposed a t 295Oj760 mm.; soluble both in strong acids and dilute alkalis ; the silver salt C,H,N,ClAg and hydrochloride C,H7N,Cl,HC1 m. p. 131° decomposed by water into its compoaeiits have been prepared.5-Chloro-3-phenylpyrazole when heated with phosphorus pentachloride in sealed tubes at 120' is converted into 4 5-dichloro-3pi~en~lp~/ruxole m. p. 95-96'? whilst with bromine in acetic acid solution i t gives 5-cldoro-4-bromo-3-pheny~yraxoZe which crystallises in white needles m. p. 90". . A cc1 7 N N P1.1 4-Benxeneaxo-5 -chloro-3 -phenylp yraxole NH< ,cannot N r C P h be directly obtained from 5-chlol-o- 3-phenylpyrazole ; it is prepared by acting on 4-benzeneazo-3-phenyl-5-pyrazolone with phosphorus oxy- chloride and crystallises in red needles M. p. 192' ; the chlorine atom cannot be replaced by hydrogen as is possible with other benzeneazo- chloropyrazoles. By acting on 5-chloro-3-phenylpyrazole with a mix- ture of nitric and sulphuric acids 5-cl~lor0-3-nitrophenyZpy~axole is obtained ; it crystallises in yellowish-green needles m.p. 180" ; that the nitro-group is present in the phenyl radicle is shown by the fact that on brominating this compound 5-cldoro-4- bromo-3-nitrophenyl- pyraxole yellow needles m. p. 130° is formed the same compound being obtained by nitrating 5-chloro-4-bromo-3-phenylpyrazole. [With HUGO ~)oRN.]-A better yield of 3-pherlyl-l-methyl-5-pyra- zolone is obtained from 3-phenyl-5-pymzolone by using methyl sulphate instead of methyl iodide (compare von Rothenburg Abstr. 1895 i 686) ; that the compound has the formula assigned to it is supported by the fact that it is obtained by the condensation of inethylhydrazine with ethyl benzoylacetate ; further since its isonitroso-derivative is red itORGANIC CHEMISTRY.247 is undoubtedly a 5-pyraz done the nitroso-derivatives OF 3-pyrazolones being green. The following salts have been obtained in a crystalline form hydrochloride CloH100N2,HCl H20 ; suZphate and nitrate C1,Hl00N2,HNO,,H,0. On treatment with nitrous acid 3-phenyl-I-methyl-5-pyrazolone is converted into 4-isonitrosoS-phenyl- N=yPh crystallising in orange 1 -methyl-5 -r,y-axolone leaflets m. p. 162'; it dissolves in alkalis and gives the Lieberniann's reaction. 4-Benzeneazo-3-phenyl-l-methyl-5-pyraxoZone is produced by the interaction of 3 - phenyl- 1 -me th y l-5 - py razolone with diazo benzene chloride ; it forms orange needles in. p. 158' ; when heated with phos- phorus oxychloride in sealed tubes at 120' it is converted into 4- benxestel;cxo-5-c?~Zoro- 1 -methyZ-3-phen ylpymcxole which f orins yellow needles m p.94'; the chlorine cannot be replaced by hydrogen by the action of tin and hydrochloric acid. When 3-phenyl-1 -methyl 5-pyrazolone is heated with phosphorus oxychloride at 160' it is con- verted into 5-chZoro-3-ph~nyZ-l-methylpyraxole which is obtained also by heating 5-chloro-3-phenylpyrazole with methyl iodide in sealed tubes at 100' ; it crystallises in white leaflets m. p. 62'. When heated with excess of methyl iodide for several days the nzethiodide ~lOH,,ON,,H,SO,,2H,O NMe<CO-C:N*OH' NMe<CCI=CH NMel:?ph forming colourless needles m. p. 167" is obtained together with a periodide C,,H,,N,ClI,T which forms dark reddish- violet leaflets 1-11.p. 105"; the periodide is also formed by adding iodine to the methyl iodide derivative ; the hydrocldoride ClOH,N2Cl,HC1 m. p. 954 and ptatinichloride m. p. 193O were prepared. An isomeric 3-chZoro-5-~?~enyZ-I-~nnet~~yk pyraxole is obtained either by methylating 5-chloro-3-phenylpyrazole in alcoholic solution or by eliminating methyl chloride from anti- pyrine chloride by the action of phosphorus oxychloride ; it crystal- lises in white needles m. p. 76". When heated with potassium hydrogen sulphide the methyl iodide derivatives of either of these isomerides give the same thiopyrine and with alkalis they yield the same anti- pyrine. The formula given t o the compound has not been definitely proved. When heated with phosphorus pentachlorde in sealed tubes at 140° or treated in acetic acid solution with bromine 5-chloro- 3-phenyl-l-methylpy razole is converted respectively into 4 5-dichloro- 3-phnyl-1 -naet?qZpyraxoEe which forms transparent crystals m.p. 25.5' b. p. 3 17'/760 mm. ;and 5-cldoro-4-bromo-3-~heptyl-l-methylpyra- xole white needles m. p. 65". A perbromide CloH8N,C1Br3 is ob- tained by adding excess of bromine-to a solution of 5-chloro-3-phenyl- 1-methylpyrttzole in light petroleum; it is a yellow powder m. p. 103" and is converted by sodium hydroxide into the preceding com- pound M. p. 65". Iodine in the presence of iodic acid converts 5-chloro-3 -phen y l- 1 -methylpyrazole i n to 5 -chloro-4-iodo - 3 -pheia y2- 1 -methylpyrazole white needles m. p. 105'. (C,oH9N,C1)2H,PtCI 2H,O,248 ABSTRACTS OF CHEMICAL PAPERS.isoAntipyriw (2 ; 5-oxy-3-phenyl-1 ; 2-dimsthylpyraxoZe) ,C=CH \N Me=CP)h may be prepared either by heating 3-phenyl-1-methyl-5-pyrazolone (1 mol.) with methyl iodide (1 mol.) in a sealed tube a t 100' or from 3-phenyl-5-pyrazolone by heating with methyl iodide ; it forms white crystals which soften a t 98' and completely liquefy at 1 0 8 O and differs from Knorr's antipyrine in that it is hygroscopic and gives with mercuric chloride a precipitate which dissolves only with great difficulty on heating whereas with antipyrine the precipitate dissolves immediately on warming slightly. The following salts of isoantipyrine have been prepared ; the hydrochtoride N M e >O I N MeCl YPh NMe<c(oH)zCH ' white needles m. p. 207" ; ?hydroiodide CllH120N2,HI H,U crystalline powder m.p. 100-1 18' (decomp.) ; hydroferrocganide yellowish-white powder ; hydroferricyanide yellow needles m. p. 1 2 2 O (decomp.) ; .picrate CllHl,0N2,C,H,07N yellow needles m. p. 142". When zsoantipyrine 1s treated with bromine in chloroform a perbromide m. p. 187' (decomp.) is formed ; the latter on treatment with water gives rise to 4-bromoisoantip~rine crystallising in white leaflets m. p. 1'79O; by the action of nitrous acid isoantipyrine is converted into 4-nitroao-isoantipyrine which crys t allises in emerald-green leaflets F p. 215" (decomp.) ; it is decomposed by warm sodium hydroxide ; its hydrochloride Cll€Il102N3,HGl crystallises in orange needles m. p. 162" ; by treating isoantipyrine in strong hydrochloric acid with an excess of sodium nitrite it is converted into 4-~itroisoantip~rin~ crystallisiag in yellow prisms m.p. 143" (decomp.). 4 4'-BenzyZidenedi-isoantipyrine CHPh( C,N,PhMe,O) is produced by the condensation of isoantipyrine (2 mols.) with benzaldehyde (1 mol.) in the presence of a little strong hydrochloric acid; it crystallises in white leaflets containing 2H,O ; m. p. 70" when hydrated or 213' when anhydrous it gives no coloration with ferric chloride. (C,,H,,ON2)2,H*Fe(CN),; 5-C?~toro-3-~?~enyl-I -methylpyraxole ( I 6 isoAntipyrine chloride I)) -p N M e < z z C P h ' obtained by the action of phosphorus oxychloride on isoantipyrine is a white hygroscopic powder containing when precipitated from alcoholic solution by ether 2H20 m. p. 70° or when anhydrous m.p. 130'; it gives a faint red coloration with ferric chloride and when heated decom- poses into 3-chloro-5-phenyl-1-methylpyrazole and methyl chloride ; when treated with picric acid i n alcoholic solution the 2-chlorine atom is replaced the compound formed C,lH12N,Cl*O* C6H,(N0,) crystallises in yellow leaflets m. p. 155" ; the same chlorine atom of isoantipyrine chloride may be replaced by iodine by treatment with potassium iodide ; the pkutinichloride (C,oH9N,CH8Cl),PtCI,,2H,0 m. p. 21 4' ; and mercurichloride CliH12N2Cl HgCl m. p. 136" are crystalline.ORGANIC CHEMISTRY. 249 isoZ'hiopyrine NMe >S 1 is obtained by treating 'Cisoanti- (NDBe CPh pyrine chloride " with potassium hydrogen sulphide ; it crystallises in long needles m. p. 178* and is coloured yellow by sulphurous acid ; on one occasion an isomeride m.p. 162O of similar properties was obtained but could not again be prepared. crystallises in needles m. p. 155-162' ; the pkatinbchloride is a red powder m. p. 231'; mercurichloride C,,H,,N,S,HgCl a white crystalline powder m. p. 224' ; hydroiodide C,,H,,N,S,HI forms monoclinic crystals m. p. 13 1' ; the methiodide C,,H,,N,S,MeI,H,O crystallises in needles m. p. 1025O. The hydrochloridt C,,H,,N,S HC1 (Cl,H,2N,S)2 €3 ,PtCI 6'2H20 N Me / \ isoZ'hiopyrine trioxide ~*so2*o*fJ bxe prepared by heating '( isoanti- pyrine chloride " with a solution of sodium sulphite forms fan-shaped crystals m p. 291'. $-is0 Thiopyrine (5-methyZtbioE-3-phenyl-l-methylpyruxole) is obtained by distilling tho methyl iodide derivative of isothiopyrine; it is a colourless liquid b.p 184'/10 mm. and combines with methyl iodide at loo' forming the coinpound from which it is prepared; its ?hydrochloride Cl,H,,N,S,HC1,H,O forms white needles m. p. 106O or when anhydrous m. p. 158' ; platinichloride yellow needles m. p. 2( 14' ; hydroiodide C,,H,,N,S,HI,H20,- m. p. 174'. When +-isotbiopyrine is acted on by nitrous acid 4-natroso-J/- isothiopyrine is formed ; it crystallises in green needles m. p. 137'. The isomeric $-thiopyrine gives under the same conditions 4-nitroso- I)- t hio p yrine NPh<C(soile):C*No' which forms dark green leaflets m. p. 96'. CH-CPh (C,] H1,N25),,H,PtC1,,IUI,O N == ?Me [With THOMAS VON DER HAGEN.1-iSoSeienopyrine C Z C H \NMe:CPh' NMe/ >Sel is formed by the interaction of '' isoantipyrine chloride " with potassium hydrogen selenide ; it crystallises in white needles m.p. 1 98' and gives no coloration with ferric chloride but with sulphurous acid a temporary yellow coloration is produced ; it does not readily form salts with acids crystsllising unchanged from hydrochloric acid ; the platinichlmide is a brown powder which commences to decompose at 150' and does not melt at 300' ; the mercurichloride is a white powder m. p. 200' NMeIZCPh (decomp.) ; the methiodide NMe<C(SeMe).bH cry stallises with 8H,O m. p. 152' ; the corresponding kthiodide C1,Hl2N2Se,EtI forms anhydrous crystals m. p. 118'. Dichloroieosele72opyriiLe C,,H,,N,Cl,Se is formed by passing chlorine VOL. xcI1. i 5250 ABSTRACTS OF ClMMICAL PAPERS.into a chloroform solution of isoselenopyrine; it is a light yellow powder m. p. 163' (decomp.). By the action of bromine isoselmpyrine tetrabromide CllH,2N2Br4Se is obtained in golden-brown needles m. p. 108' ; when repeatedly evaporated with water it is converted into isoselenopyrine dibromide Cl1RI2N2BrSe2,. which forms golden-yellow needles m. p. 2 1 5 O and on t-eatment with sodium carbonate is con- verted into isoselenopyrine. iso-$-XeZenopyrine ( 5 -naethyZselenoE -3-phenyZ-1 -rnethylpyraxole) is formed by the Combination of methyl iodide with isoselenopyrine in ether ; it is a light yellow liquid b. p. 196-197O/15 mm. ; it combines with chlorine to form a dichloride a yellowish-green powder m. p. 161'; the dibromide rn. p. 177' when heated with a solution of sodium carbonate is converted into 4-bromoiso-1,b-seZenopyrine m.p. 129' ; the hycE~ocldo&Ze of iso-+-selenopyrine C,,Hi,N2Se,HC1 forms white needles m. p. 1 06" ; the pZatinicl~loi.icle (C,,H,,N,Se),,H,PtCIG is a reddish-brown powder and does not melt at 300'. On treatment with nitrous acid iso-$-selenopyrine gives 4-nitrosoiso-+-thiopyri~~e which crystallises in green needles m. p. 136". [With HANS WREDE.]-By the reduction of 4-isoni troso-3-phenyl-1- methyl-5-pyrazolone with zinc dust in acetic acid solution 4-amino-3- phenyZ-1-methyl-5-pyyaxolone is produced ; it cannot be obtained in the free state since it at once oxidises t o isorubazonic acid ; its hydrochloride forms white needles m. p. 175" (decomp.). The base condenses readily _ . N Z f l P h CO *CH*N:CHPh' with aldehydes ; the benxylidene derivative NNe< crystallises in yellow needles ni.p. 227'; the o-liydroxybenxylidene deriv- ative C,,H,ON,*N CH C,H,* OH cry stallises in faintly yellow prisms decomposing a t 230" ; the p-n2ethorcybenx~Eidelze derivative crystallises in yellow needles m. p. 220' (decomp.) and the p-nitrobenxylidene derivative commences to decompose a t 250' ; fugurylzdene and cinnnm?/Zide.rze derivatives melt at 180' and 152O-respectively. C(0H) y- N 7-CO N ==CPh CPh:N> NMe is obtained isonubaxonic acid N M ~ < by the oxidation of 4-amino-3-phenyl-l-methyl-5-pyrazolone with ferric chloride ; it crystallises i n dark red needles m. p. 1138" ; it forms violet-colourcd salts with alkalis ; treatment with phenyl- hydrazine gives benzeneazo-3-phenyl-l-methyl-5-pyrazolone. 4-A~1ainoisoc~ntipyrine C,,H,,ON is obtained by the reduction of 4-nitrosoisoan tipyrine with zinc dust and acetic acid or stannou3 chloride and hydrochloric acid ; i t forms large white stable crystals m.p. 1 0 9 O ; the hyZrocUoricle C~lH130N3,HCI crystallises in white needles m. p. 2 10' ; the stnnnochloride (C,,H,,ON,),,SnCl forms thick white crystals which are decomposed by hydrochloric acid when concerit rated with the precipitation of 4-aminoisoantipyrine hydro- chloride ; the sutphute C,,H,,0N,,H,S04 m. p. 205O and picrate yellow prisms decomposing at 1 65" were also prepared. Aminoisonttti- pyrine ~rzuco6~*onaate C~lH130N3,(:4H20QBr2 is a yellow powdey iu. p. 115' obtained by mixing together solutions of its components.The following Condensation products of 4-sminoisoantipyrine with various aldehydes and ketones were prepared. Q11 RisON C,jH2 (N O2)3 OH,ORGANIC CHEMISTRY. 251 ,NMe:CPh Benxylideneuminoiso~nt~p~~ne NMe/ >O I crystallises \C=UN:CH*Ph in yellow prisms m. p. 15 1 " ; o-hydroxybenxylideneaminoisoantipyrine yellow needles m. p. 173" ; p-methoxybenxylideneaminoisoantipy~ine yellow needles m. p. 177" ; p-nityobenxylidene derivative m. p. 155" ; cinnarnylidene derivative colourless prisms m. p. 151" ; ethyl aceto- acetate derivative colourless crystals m. p. 14 lo and acetophenone derivative colourless prisms m. p. 167". E'o.l.mybaminoisoantipy~~ne C,,H,,ON,*NH* COH crystallises in colour- l e s rhombic plates m. p. 209' ; cccetylaminoisoantipyrine forms colour- less prisms m.p. 253" ; benxoybaminoisoanti~yrine crystallises in colour- less crystals m. p. 234'; a dibenzoyl derivative could not be prepared. BenxenesuIp?mnylaminoisoantipyrine Cl,Hi,ON,*NH~SO,Ph crystal- lises in needles m. p. 245'. s-~~-isoccnt~pyi~ylthiocccrbam~~e CS(NH*C,N,Me,PhO) obtained by heating aminoisoantipyrine in alcoholic solution with carbon disul- phide crystallises in white prisms m. p. 225'. By heating 4-amino- isoan tipyrine with phenylthiocarbimide in alcoholic solution phenyl- isoantipyrylthiocarbarnide NHPh*CS*NH*C,,H,,ON is obtained cry- stallising in white needles m. p. 2 10". isoA.ntzp~ryluret~~ccize NMetCPh NMe' >O I \C==C-NH*CO,Et ' forms colourless crystals m. p. 190". Although the diazo-derivatives of pyrazoles and pyrazolones are stable no diazo-derivative of amino- isoantipyrine could be isolated ; however a freshly-diazotised solution of aminoisoantipyrine gives with P-naphthol the dye NMe/ >O I NMe:CPh \c == ON N-c,,,H~*oH ' a red crystalline substance clissolving in concentrated sulphuric acid with a violet colour.prepared by acting on aminoantipyrine with either methyl iodide-or methyl sulphate ; it forms monoclinic crystals ni. p. 118' ; the picrate C,,H,70N,,C,H,(N0,),.0H crystallises in yellow leaflets m. p. 166" ; the methiodide forms colourless needles m. p. 1 97". Diethyluminoiso- antipyrine obtained by acting on aminoisoantipyrine with ethyl sulphate is a colourless oil. By heating aminoisoantipyrine with ethylene bromide at 1 40" both di-isoantipyyinediethylenediarnine C,H,N,(Cl,HllON,) white crystals m.p. 300' and di-isoantipyiine- etkylenediamine C,H,N,( C,,H,,ON,) white needles in. p. 132' are obtained ; the picrate of the latter crystallises in yellow needles m. p. 148". isoAntipyrine-red (isorubctxonic acid methochboride) _ . CO-$! :N*$?X=C(OH) NMe<NMeC1:CPh CPh NMeCl >NMe is formed by the oxidation of aminoisoantipyrine in aqueous solution s 2252 ABSTRACTS OF CHEMICAL PAPERS. with ferric chloride and the subsequent addition of concentrated hydrochloric acid ; it crystallises in red needles m. p. 207O and dis- solves readily in water forming red solutions ; the colour of the solu- tion is destroyed by reducing agents and alkalis ; strong alkalis pre- cipitate from concentrated solutions of the substance a yellow crystal- line powder m.p. 159O which seems to be di-isoantipyrylomine NH(C,,H,,ON,) ; the hydroc?doride of this base is therefore the leuco-base of iaoantipyrine-red into which substance it is converted by oxidising agents. Alttipyrine-red (rubaxonic acid methochloride) >NPh C(0H) F*N=?-- co NPh<NMeC1:CMe CMe :NClMe m. p. 215') is obtained in similar manner from aminoantipgrine; it closely resembles isoantipyrine-red ; its violet solution in water gives with strong sodium hydroxide diantipyryEanaire NH( C,,H1lON,) m. p. 104'. That the isoantipyrine- and antipyrine-reds have the formulae assigned to them is very probable since antipyrine-red may also be prepared by methylating rubazonic acid with methyl sulphate. W. H. G. 1 -Phenyl-5-methylpyraeole. RICHARD STOERMER (Ber.1907 40 484-488).-The author has shown previously (Abstr. 1904 i 181) that pyrazolones are reduced to pyrazoles by means of phosphorus tribromide. This method is now considered to be the most convenient one for the preparation of pyrazoles ; for example l-phenyl-3-methyl- pyrazole may be obtained i n theoretical yield from 1 -phenyl-3-methyl- pyrazolone. 1 -Phenyl-5-methylpyrazole CIOHIONS obtained by the reduction of l-phenyl-5-methyl-3-pyrazoIone with phosphorus tribromide has b. p. 263*5"/762 mm. and is an oil with an odour recalling that of quinoline. When oxidised by permanganate it forms l-phenylpyr- azole-5-carboxylic acid m. p. 183'. 1-Phenyl-5-methylpyrazole pbutinichloride has m. p. 198-199O ; the aurichhride has m.p. 124-125' ; the picrate has m. p. 97-98' ; the methiodide has m. p. 256-257" ; the ethiodide has m. p. 208". The properties of 1-phenyl-5-methylpyrazole and its salts are con- trasted with the results quoted by previous investigators. A,. McK. Acetylacetonebenzyl-o-carboxylic Acid and its Condensa- CARL Bij~ow and MAX DESENISS (Ber. 1907 40 Compare Bulom Abstr. 1887 144; Bulow and Koch tion Products. 187-192. Abstr. 1 904 i 32 1 ).-Acetylctcetone- y- benxyl-o-carboxybic acid CH( COMe)2*CH,*C,,H,*C0,H formed with development of heat by reduction of pht halylacetylacetone with zinc dust and acetic acid crystallises in needles sinters at BO" m. p. 97" is hydrolysed by boiling 20% potassium hydroxide yielding benzylacetone-o-carboxylic acid and when treated with ammonia in cooled absolute alcoholic solution forms ammonium acetylacetonebenxyl- o-carboxybote m.p. 140-150° which loses ammonia when boiled with water.ORGANIC CHEMISTRY. 253 The action of hydroxylamine hydrochloride and sodium acetate on acetylacetone-y-benal-o-carboxylic acid in aqueous acetic acid solution leads to the formation of 4-o-carboxybennyl-3 5-dimethyZiso-oxaxole ~ i ~ ~ ~ C * C H * C H * C O H which separates in white crystals m. p. 1 17-11 So. 4-o-Carboxybenxyl-3 5-dimethylpyrazoZe SJH-CMe N-CMe >C* CH,* C,H,*CO,H H20 prepared by boiling acetylacetonebenzyl-o-carboxylic acid with semi- carbazide acetate in alcoholic or with hydrazine in glacial acetic acid solution crystallises in needles loses H20 at 100-110"; m. p. 180'. 1 -PhenyZ-4-o-carboxybenzyl-3 5-dirnetlcylj1yrccxole rPh*CMe N = CMe >C* CH,*C,H;CO,H formed from phenylhydrazine and acetylacetonebenzyl-o-carboxylic acid separates from alcohol in transparent crystals m.p. 217-218°. G. Y. Preparation of 5 5-Dialkylbarbituric Acids. EMANUEL MERCK (D. R.-P. 1741 78).-When heated with concentrated acids (sulphuric hydrochloric benzenesulphonic and naphthalenetrisulphonic acids) the dialkylmalonuramides yield 5 5-dialkylbarbituric acids. I n this way diethylmalonuramide when heated with excess of concen- trated sulphuric acid a t 100-110' gives rise to 5 5-diethylbarbituric acid. G. T. M. Preparation of 2-Imino-4 6-dioxy-mono- and di-6-alkyl- pyrimidines. CHEMISCHE FABRIK AUF AKTIEN (vorm. E. Schering) (D. R.-P. 1?4940).-Although barbituric acid is not readily alkylated in alkaline or dilute alcoholic solutions yet 2-imino-4 6-dioxypyrim- idine (malonylguanidine) furnishes a good yield of alkyl derivatives.The interaction of 1 mol. of ethyl iodide in presence of potassium hydroxide gives rise to 2-imino-4 6-dioxy-5-ethylpyrimidine whilst 2-imino-4 6-dioxy-5 5-diethylpyrimidine is formed when 2 mols. of dkyl iodide are employed. The yield of the latter product is however improved by alkylating in two stages. G. T. &!I Indoleaminopropionic Acid and its Halogen Derivatives. The Tryptophan Reaction. CARL NELJBERC and NIKOLAUS POP- OWSKY (Biochem. Zeitsch. 1907 2 357-382. Compare Hopkins and Cole Abstr. 1901 i 310).-Pure tryptophan (indoleaminopropionic acid) may be obtained somewhat more readily from fibrin than from casein by Hopkins and 'Cole's method.From 600 grams of dried material 8 grams of tryptophan were obtained. It is a convenience to ccmbine the preparation of tyrosine with that of tryptophan. The reddish-violet coloration obtained by the addition of chlorine or bromine water to tryptophan attains a maximum when the amount of2.54 ABSTRACTS OF CHEMICAL PAPERS. halogen is equivalent to 4 atoms per gram-mol. of tryptophan. When concentrated solutions are used red amorphous precipitates of mono- halogen derivatives C,,H,,02N,Br and C,,H,,O,N,CI are obtained. The compounds dissolve in amyl alcohol or ether yielding reddish- violet solutions and both decompose at about 280'. Excess of halogen converts the red compounds into yellow perhaloids C,,H1,02N,Br and C,,H,,O,N,Cl which contain two of the three halogen a t o m only loosely combined.The contradictory results obtained by previous authorities are due to their having worked with mixtures of the yellow and red com- pounds. No trace of sulphur is contained in the pure coloured substances. The nitrogen in tryptophan and its derivatives may be estimated by Kjeldahl's process. J. J. S. Preparation of Quinazoline from o-Nitrobenzddehyde J. D. RIEDEL (D. R.-P. 174941. Compare Abstr. 1904 i 1060; 1905 i 944).-The following operations afford a ready means of preparing quinazoline a substance hitherto obtained only with some difficulty. o-Nitro6er~xyEidenedifornzumide NO,*C,H,*CH(NH*CHO) produced by passing hydrogen chloride into a mixture of o-nitr9benzaldehyde (1 part) and formamide (2 parts) at 40-50° is soluble in hot water and alcohol but insoluble in ether ; stellar aggregates of prisms m.p. 177-178O. Quinazoline is obtained from this diformamide by reducing it with zinc dust and dilute acetic acid. G. T. M. Di-p-dimet hylamin oindigotin. MARTIN FREUND and ADOLF WIRSING (Ber. 1907 40 204-206).-p-DimethyZuccminop~enylglycino- nitrile NMe,* C,H,*NH*CH;CN prepared by the action of hydrogen cyanide and formaldehyde on dimet hyl-p-phenylenediamine in alcoholic solution a t 100' under pressure crystallises in colourless needles m. p. 80-Slo and is hydrolysed by boiling aqueous potassium hydroxide forming p-dimethykuminophenylglycine NMe,*C,H,*NH*CH,-CO,H m.. p. 152-183° ; the potccssiurn salt C,,H,,O,N,K crystallises in glistening scales commences t o decompose at B O O and is melted at 30s'.When added to fused sodamide the potassium salt forms di-p-dii?.2ethylaminoindigotin NMe; C H,<g!>C C<pi>C,H3*NMe which separates from water as a green flocculent substance does not melt or sublime when heated forms bluish-green solutions in organic solvents or blue solutions in dilute hydrochloric or concentrated sulphuric acid dyes wool green i n acetic acid solution or in presence of sodium hydrogen sulphite and forms sparingly double salts with zinc mercuric and platinic chlorides. G. Y. Preparation of 5-Hydroxynaphthaminobenzaldehydine- 7-sulphonic Acid. I,EOPOLD CASSELLA & Co. (D.R.-P. 175023. Compare Abstr. 1906 i 989).-Hydroxynaphthaminobenzaldehydine-ORGANIC CHEMJSTRY.255 /N:C,R 8~~H/\()-~. C H,R' \/\/ aulphonic acids having the general formula where R and R are dissimilar radicles may be prepared by con- densing 1 2-diamino-5-hydroxynaphthalene-7-sulphonic acid with the bisulphite compound of an aldehyde whereby an intermediate product is obtained which can then be further condensed with a molemle of a second aldehyde. The bisulphite compound of m-aminobenzaldehgde was condensed with the sulphonic acid and the intermediate product condensed with the bisulphite compound of benzaldehyde. The final product is a yellow amorphous substance sparingly soluble ih alcohol or water and having both acidic and weak basic properties. It combines with diazo-compounds and is readily diazotised giving an insoluble diazo- derivative which is reddened by alkalis.OH G. T. M. Indanthrene and Flavanthrene. 111. The Halogen Deriv- atives of Indanthrene. ROLAND SCIIOLL HANS BERBLINBER and co c1 JOHANNES MANSFIELD (Ber. 1907 40 320-325. Compare Abstr. 1904 i I 10).-4-Cldoroanthraqui~onazine pre- pared by the oxidation of 4-chloro- indanthrene with nitric acid D 1,285 \\ 1 \/\/\ on the water-bath has a greenish-yel- I I I I low colour somewhat darker than anthra- \/\/\/ quinonazine. /\A/'\ I I 1 \)\A& co 4 ; 4'-DichZoroindant?~r~n~ is obtained as a blue powder when the monochloro-derivative is heated for three hours a t 180' with hydrochloric acid. 4-Bromoindanthrene C,,H,,O,N,Br prepared by heating anthra- quinonazine with hydrobromic acid D 1-47 for two hours at 150' in in a closed tube crystallises from quinohe in slender blue needles with a copper-red reflex.It is oxidised to 4-bro?noanthraqzci.ltonaxine C28H1104N,Br by nitric acid D 1.285. It is greenish-yellow and dissolves more easily in concentrated sulphuric acid than the parent azine. 4-4'-Di6romoindanthrcne C,sHl,C)4N,Br2 prepared similarly to the dicliloro-derivative is blue and has not been obtained quite pure. 4 4-0ibk80moant?~raquinonaz~ne 3 $-dibvomide C28H1004N2Brq is prepared by heating indanthrene with bromine in a sealed tube a t 100' for six hours. The dark green base is converted into 3 4 4'-tri- bronzoindanthrene C28Hli04N2Br3 by boiling quinoline and crystallises in slender blue needles. W. R. Indanthrene and Flavanthrene. IV. Action of Nitric Acid on Indanthrene. ROLAND SCHOLL and JOHANNES MANSFIELD (Ber.1907 40 326-329).-Boiling dilute nitric acid D 1.24 oxidises ipdanthrene to anthraquinonazine but when boiling acid is employed a256 ABSTRACTS OF CHEMICAL PAPERS. nitrodinitrosotrihydroxy- 'or tetrani4rotetrabydroxyanthraquinonazine is obtained according t o the conditions. Nitrodinitrosotrih ydrox yanthraquinonaxine C,,H,O,,N obtained by boiling 1 part of indanthrene with 12 to 15 parts of nitric acid D 1.4 for twelve hours is a yellow crystalline powder when crys- tallised from concentrated nitric acid or nitrobenzene ; it dissolves in sulphuric acid with a yellowish-red colour. The sodium salt is black. The compound is of the nature of a nitro- or nitroso-phenol as it dissolves in aqueous sodium carbonate ; no nitro- or nitroso-group is attached to an azine nitrogen atom as boiling phenol is without action.The constitution provisionally assigned OH CO NO is as here given. On reduction with excess of dilute sodium hydrogen sulphide a t 70-80° triuminotri- hydroxyindanth~elne C2,H1707NR is ob- tained and crystallises from nitro- CoNIj/\,?/\ benzene in violet-black needles ; the HOI I 1 I hydyochloride is yellow and the base is sparingly soluble in hot dilute sodium I'etrunitrotetrah~droxyunthl.aquinon- axine CqH,O,,N is obtained by boiling indanthrene in a mixture of fuming nitric acid D 1.5 and sulphuric acid and yields on redriction with sodiuni hydrogen sulphide tetra-aminotetrah~droxyindanthrene Nitrodinitrosotrihydroxynnthraquinonxzine dyes cotton sub- stantively a wine red but t h e two amino-compounds are of no technical value as dyes for vegetable fibres.I I "\/\& \/\/\/ NO co hydroxide. '2Sa 18°8N 6' W. R. Indanthrene and Flavnntbrene. V. Reduction Products of Indanthrene. ROLAND SCHOLL WILHELM STEINKOPF and A. KABACZNIK (Ber. 1907 40 390-394. Compare Abstr. 1904 i 109 110 and preceding abstracts).-The blue substance formed by reduc- tion of indanthrene by means of sodium hydrogen sulphite in aqueous sodium hydroxide solution and termed commercially " indanthrene S," is the disodium derivative of N-dihydt 0-1 2 1' 2'-anthraquinoue- anthrahyd roquinonnzine (d ih y droindanthrene) C6H4<~~>C6H2<~~>c6H2<CiONa) co NH 7(ONa)>C 6 H 4' When treated with benzoyl chloride and sodium hydroxide it yields a C(OBz) '' dibermoyl derivative C6H,< >C6H2< - >C,H,< CO N H y(oBZ)>C H co N H which is obtained as a n insoluble blue crystalline pow&.The yellowish-brown substance formed by reduction of indanthrene by means of sodium hydrogen sulphite and zinc dust is the tetra- sodium derivative of htetrahydroindanthrene ; it cannot be isolated in consequence of the ease with which i t is oxidised yielding finally indanthrene. The tetrabenxoyl derivative 'ORGANIC CHEMISTRY. 257 formed by the action of benzoyl chloride and sodium hydroxide on the reduction product is obtained as a brownish-yellow microcrystalline powder m. p. above 300° which . dissolves in chloroform benzene +-cumene or ethyl benzoate forming a solution with green fluorescence.G. Y. Indanthrene and Flavanthrene. VI. Action of Quinoline and Acyl Chlorides on Indanthrene. ROLAND SCBOLL and HANS BERBLINGER (Ber. 1907,40 395-400. Compare preceding abstracts). -The action of benzoyl chloride on indanthrene in boiling quinoline solution leads to the formation of the tetrabenzoyl derivative of tetra- hydroindanthrene which when heated yields a sublimate of benzoic acid and dissolves in alcoholic potassium hydroxide forming a blue solution depositing indanthrene on dilution and exposure t o air. It is oxidised by concentrated nitric acid yielding the ?titl.de of tetrabenzoyl- anthrahydroquinonazine which forms an indigo-blue solution and is hydrolysed on heating with the acid forming a soluble brown anthra- quinonazine. When boiled with quinoline the tetrabenzoyltetrahydro- indanthrene is converted slowly into anthranonazine.Tetra-acetyl-N-dihydroanthrahydroquinonaxine is formed slowly by boiling indanthrene with acetyl chloride and quinoline in glacial acetic acid solution ; it crystallises in microscopic brownish-yellow needles dissolves in organic solvents forming reddish-yellow solutions with green fluorescence and is converted into dihydroindanthrene by the action of alcoholic potassium hydroxide. On prolonged boiling with quinoline it yields anthranonazine which is formed more rapidly by the action of acetyl chloride on indanthrene in boiling quinoline solu- tion in the absence of aceticacid. The formation of 0-acyl derivatives of a reduced indanthrene instead of substitution of tho imine hydrogen atoms must result from increased stability of these when in proximity to carbonyl groups (compare Ahstr.1904 i log) as is the case with the hydroxyl-hydrogen of the aldol of diacetyl (von Pechmann Abstr. 1895 i 647). The reducing action of acid anhydrides or acyl chlorides on quiuones and similar substances has been observed in other cases ; thus methylene-blue is converted into the acetyl derivative of the leuco-compound when heated with acetic anhydride and sodium acetate a reaction which takes place also with thiazine and oxazine dyes (compare Japp and Graham Trans. 1881 39 174). G. Y. Action of Hydrogen Sulphide on Rosaniline and Phenylated Rosanilines. RUDOLF LAMBRECHT (Ber. 1907 40 247-255. Compare Abstr. 1905 i 243).-The action of hydrogen sulphide on rosanilines is explicable on the assumption of the intermediate forma- tion of a hydrosulphide :C:C,H,:NH,*SH ; attempts t o isolate such a compound however lead to the formation of a quinonoid oxidation product of unknown constitution.I n acid or neutral alcoholic solution hydrogen sulphide reduces p-rosaniline to the leucaniline ; excess of ammonium hydrosulphide produces triaminotriphe.rcylc~rbothio1 C,,H,,N,S. The carbothiol forms colourless solutions in mineral acids but loses hydrogen sulphide in2.58 ABSTRACTS OF CHEMICAL PAPERS. alcohol-acetic acid solution It dissolves in alcohol to an intensely magenta coloured solution by the evaporation of which a quinonoid substance is obtained ; a similar gFeenish-red glistening substance is formed when the carbothiol is heated at 140'.TricminotritoZyZccwbot?iioZ C,,H,,N,S obtained from new magenta in a similar manner to the preceding compound yields the carbinol base by treatment with alkalis and in alcoholic solution is converted into quinonoid products. p-Rosaniline-blue (Kalle & Co.) treated with hydrogen sulphide in alcoholic solution yields triphenylp-leucaniline m. p. 1 8Z0 whereas excess of ammonium hydrosulphide produces the carbinol base C(C6H,*NHPh),*OH. Diphenylamine-blue is an lmpure triphenyl-p-rosaniline since by treatment with alcoholic hydrogen sulphide it yields impure triphenyl- p-leucaniline rn. p. 1'78'. Rosaniline-blue is reduced to the Zeuco-compound CH(C,H,.NHPh),*C?H6.0NH m. p. 11 6" by alcoholic hydrogen sulphide and yields the carbinol base by treat- rnent with excess of ammonium hydrosulphide. c.s. Urazoles. VIII. Sale of Tautomeric Compounds. SALOMON F. ACREE (Amer. Chem. J 190'7 37 71-85).-This paper deals with the behaviour of the metallic salts OF tautomeric acids. The relations between the concentration of solutions of such salts and the equilibrium constants are discussed. It is considered that all syntheses analogous t o the ethyl acetoacetate synthesis depend on the reactions of tauto- meric salts. Thus in the formation of ethyl acetoacetate from ethyl acetate and sodium ethoxide a sodium salt of ethyl acetate is formed which exists in two tautomeric forms. The sodium salt (2) reacts vigorously with the ethyl acetate present and ethyl acetoacetate is formed in accordance with the following scheme CH,*CO,Et + C,H,*ONa ?$ + U,H,*OH.1 (2) CH ,Na*CO,Et C'H,*CO,Et + CH,Na.CO Et -+ CH,*C(ONa)(OEt)*CH,- C0,Et ( l)CH, C( ONa) *OEt t- --+ CH3*C(ONa):CH*C02Et + C,H;*OH. It is well known that when the silver salts of certain aniides are treated with alkyl halides a t the ordinary temperature oxygen ethers are formed principally whilst the potassium salts at higher tempera- tures yield chiefly the nitrogen compounds. The theories which have been advanced by Comstock Wheeler Nef and Michael to account for such reactions are discussed and shown to be inadequate. In place of these the following hypothesis is brought forward. '' A salt of a tautomeric compound react,s with an alkyl halide or other reagent and forms two compounds because the tautomeric salt is really a mixture of two tautomeric salts in equilibrium each of which reacts with the alkyl halide in independent side reactions.This reaction may in certain cases be complicated by the simultaneous rearrangement of one OF the reaction products into t,he other or into some other product. ' 'ORGANIC CHEMISTRY. 259 This theory is supported by the results of experiments which have been carried out with a view of ascertaining the conditions of equi- librium which exist in solutions of salts of 1 -phenyl-4-methylurazole. When a salt of this urazole is heated wit.h ethyl iodide in solution in tlilute alcohol ether or benzene a mixture of 3-ethoxy-1-phenyl- - - - N=y *OEt CO-NMe ' 4-met hylurazole NPh< and 1 -pheny 1-4-methyl-%ethyl- NEt*?o is produced.CO-NMe' urazole NPh< The proportions in which these two compounds are formed varies with the salt employed. Thus in dilute alcohol (40%) 90% of the N-ethyl and 10% of the 0-ethyl derivatives are produced. I n the same solvent the barium salt gives 93.5% of the former and 6.5% of the latter whilst the sodium salt yields 58.7% of the 0-compound and 41.3% of the N-compound. The silver salt in ether gives 35% of the N-ethyl and 65% of the 0-ethyl derivatives. The determination of these ratios a t 22') 60° and 90' shows that each is nearly constant or the two side reactions have approximately the same temperature coeficient. Neither of the two derivatives undergoes rearrangement into the other under any of the conditions studied. The proportions in which the two compounds are produced vary not only with the salt and the solvent employed but also with the particular alkyl halide used; thus whilst in dilute alcohol (40%) at 60° the potassium salt reacts with ethyl iodide in one hour to the extent of 30*35% and 90% of the product consists of the N-ethyl derivativo ; the same salt reacts with ethyl bromide under the same conditions to the extent of 22*5% and the N-ethyl derivative forms 87.7% of the product.E. G. Triazoles. MAX BUSCH (J. pr. Chem. 1906 [ii] 74 533-549. Compare Abstr. 1906 i 11 5)-An attempt to prepare acylendoimino- triazoles by the action of formic acid on benzoylaminodiarylguanidines failed as the action leads to the formation of the colourless feebly basic 5-aminotriazoles formed previously by heating the acylamino- guanidines (Busch and Bauer Abstr.1900 i 414). Triaxoles from 6enxoyZami.lzodia~y~guanidines.-CWith HERM. BRANDT.]-T~~ action of carbodiphenylimido o i benzhydrazide in benzene solution a t 50' leads to the formation of benzoylaminodi- phenylguanidine and 5-anilino- 1 2-diphenyl-I 2 3-triazole which are separated by conversion of the slightly acid guanidine into its soluble sodium salt. When oxidised with alcoholic ferric chloride benzoyl- aminodiphenylguanidine yields a blue product which is probably the mo-compound NHPh* C( N Ph) N :NRz. The anilinotriazole which is the chief product of the action of carbodiphenylimide on benzhydrazide in boiling benzene solution is formed also by heating benzoylaminodiphenylguanidine with 'formic acid in a sealed tube a t 170'; it yields only traces af aniline and benzoic acid when heated with concentrated hydrochloric acid under pressure at 200'.The following tolyl compounds are prepared in the same manner. Be~xoyl~minodi-o-tolylguanidine C,H7-NH* C(N *C7H7).NH*NHBz,263 ABSTRACTS OF CHEMICAL PAPERS. crystallises from alcohol in nodular aggregates m. p. 1 5l0 intumescing and when heated above its melting Doint. forms water and >N*C,H which If ?C(NHC7H,) N====CPh 5-0-toluidino-2-phenyl- 1-0- to Z,yltriaxole is obtained as a white crystalline powder m. p. 142'. Benaoykaminodi-p-tolylgu~~~idin~ C,,H,,ON forms yellow trans- parent prisnis m. p. 190° intumescing. 5-p-ToZuidino-2-phenyl-l-p-tolyZtrinzo~e C,,H,,N crystallises in glistening spears m. p. 196'.The action of carbodiphenylimide on semicarbazide leads to the formation of ammonia carbon dioxide hydrazodicarboxylamide tri- phenylguanazole and triphenylguanidine. endo1minotriaxoZes.-[ With HERM. Blt ANDT.] -p-Bromoanilinodi- phenylguanidine NHPh*C(NPh)*NH*NH*C6H4p prepared from p-bromophenylhydrazine and carbodiphenylimide IS obtained as a white crystalline powder m. p. 141'. When boiled with formaldehyde in alcoholic solution it forms 3-anilino-4-phenyl-1-p-bron~ophenyl-4 5- NPh which crystallises in dihydro-1 2 4-i!riaxole sheaves of needles m. p. "ii0 and on successive treatment with sodium nitrite and nitric acid in glacial acetic acid solution yields the sparingly soluble nitrate of 4-phenyl- 1 -p-bromophenyl-3 5-endo- anilo-4 5-dihydro-1 2 4-triazole C2,,H,,N4Br,HNO3 crystallising in slender needles ; the free base (bronzoniti*on) I YPh >NPh crystallises in stout glistening needles m.p. 223 (decomp.); the nitrate is slightly more the hydrochloride and sulphccte less soluble than the corresponding nitron salts. a-2lraphthyZarninodiphenyZguanidirZR C,3.H20N prepared from a-naphthylhydrazine and carbodiphenylimide crystallises from benzene in colourless leaflets containing benzene of crystallisation m. p. 1 4 3 O and is oxidired by mercuric oxide in alcoholic solution yielding the axo-compound NHPh*C(NPh)*N N*Cl0H7 which forms deep bluish-violet glistening needles m. p. 148'. When heated with formic acid a t 180' the aminoguanidine yields 4-p~enyZ-l-a-nap~thyZ- 3 5-endoindo-4 5-dihydvo-1 ; 2 4-triazoZe which crystallises in yellow leaflets m.p. 212' ; the nitrate C,,H1,O,K5 forms a microcrystalline powder m. p. 219' and is much more easily soluble than nitron nitrate. P-Na~hthylaminodipphenylgzcalzidine crystallises in needles m. p. 1 5 2 O ; the am-derivative forms dark violet glistening prisms m. p. 1 7 2 O and dissolves in alcohol forming a red solutiori which gradually becomes colourless in consequence of the formation of chloronaphthyl- diphenylaminoguanidine (compare Abstr. 1906 i 465). Phenyl-P- naphth y ZendoaniZodih ydrotriaxole crys tallises in I ight yellow leaflets m. p. 205' (decomp.) ; the nitrate crystallises in slender needles m. p. 238* and is only slightly less insoluble than nitron nitrate; the hydrochloride and sulphate are also only sparingly soluble.4 5-DiphenyZ-1-bcnzyl-3 5-endoando-4 5-dihydro-l ; 2 4-friasoZe C( N HPh)-> N(C H Br)*CH N=-= 7-\ N ( C6Hp:r) C H-'ORGANIC CHEMISTRY. 261 N F T NPh )NPh formed by the action of benzoyl chloride on benzylaminodiphenylguanidine crystallises from alcohol in slender yellow needles m. p. 186' ; the nitrate C,7H,,N,,HN0 crystallises in needles m. p. 239' and is comparatively soluble in water. N(CH,Ph)*bPh' I 4-Phenyl-1 -benxyl-3 5-endoanilo-4 5-dih~dro-l 2 4-triaxoEe N=,==-= 7-\ I YPh )NPh is obtained by heating benzylaminodiphenylguanidine with form- aldehyde - in alcoholic solution and oxidising the resulting dihydro- triazole with sodium nitrite in glacial acetic acid; it forms yellow crystals m. p. 129'; the nitrate is only sparingly soluble in water.Action of Carhodi-imides on 4-Phanylsemicarbaxide.-lWith Gusmv BLUME.]-T~~ action of carbodiphenylimide on 4-phenylsemicsrbazide in benzene solution leads to the formation of 1-diphenylguanyl-4- phenykemkc6rbazide [phenylcarbarnyldiphenylguanidine] NHPh*C(NPh)*NH*NH*CO*NHPh which crystallises in slender white needles m. p. 171' (decomp.) and is soluble in dilute mineral acids or acetic acid ; the product of its decomposition when heated is 3-anilino-4-phenyl-5-triazolone (Abstr. 1902 i 574). Di-o-tolylguanyl-4-phenylsemicarbaxide C,,H,,ON formed from di-o- tolylcarbimide and 4-phenylsemicarbazide crystallises in white needles m. p. 164O decomposing with formation of aniline and 3-o-toluidino-4- N(CH,Ph) * C H ' - ~:c(NHc7H7)>N*C,H.7 which crystallises from o-tolyl-5-triaxolon/~e co NH- alcohol in colourless prisms m.p. 183' and has feeble basic and acid properties. G. Y. Behaviour of the Group N*C*N towards Acylating Agents. 11. GUSTAV HELLER (Ber. 1907 40 114-119. Compare Abstr. 1904 i 942).-The author has studied the behaviour on benzoylation of tetrazole as a type of a cyclic compound containing the group N-C-N and containing more than two nitrogen atoms. When a mixture of equal amounts of ethyl alcohol and concentrated sulphuric acid is slowly added to a mixture of ethyl formazylcarboxy- late ethyl alcohol and amyl nitrite ethyl diphenyltetraxoZiumca~*bozyla;te ethomlphate C,,H,,O,N,S separates as glistening needles m. p 214-215O (decomp.). When a mixture of dilute nitric acid and potassium permanganate is added to its aqueous solution heated t o 75' it is oxidised to tetrazole. When tetrazole in pyridine solution is acted on by benzoyl chloride it forms in addition to a dark yellow non-crystalline substance diben- zoylcarbamide m.p. 210'. Tetrazole alone however is acted on by benzoyl chloride when heated at looo with evolution of nitrogen and formation of dibenxoylhydraxine which separates from alcohol in fine needles m. p. 237'. Dibenzoylhydrazine is also formed by the inter- action of benzoyl chloride and 1 2 4-triazole. A. McK.262 ABSTRAWS OF CHEMICAL PAPERS. 1 2 4 5-Tetrazin e. TEEODOR CURTIUS AUGUST DARAPSKY and Emsr M~LLER (Ber. 1907 40 84-88. Compare Curtius Abetr. 1889 369; Hantzsch and Lehmann Abstr. 1901 i 132; Curtius Darapsky and Muller Abstr.1906 i 939 ; this vol. i 21).-The authors had previously shown that the acid formerly described by Curtius and by Hantzsch and Lehmann as bisazoxyacetic acid is in reality I 2 4 5-tetrazine-3 6-carboxylic acid CO,H-C<~ N*N N > ~ * ~ ~ ~ . It is now shown that when this acid is heated the product obtained is not bisazoxymethane as described by Hantzsch and Lehmann but is rfee from oxygen and is 1 2 4 5-tetrazine. When 1 2 4 5-tetrazine-3 6-carboxylic acid is heated with dry sand a t about 160° a purple vapour is evolved which condenses as red crystals. By heating the latter with barium oxide 1 2 4 5-tet~axine CHG?~:~>CH is obtained as glistening purple pyramids m. p. 99'. (The bisazoxymethane of Hantzsch and Lehmann is described as having m.p. 75O.) The absorption spectra of its vapour and of its solutions were examined. Its solutions in water alcohol and in other solvents are bright red and may be boiled for some time without undergoing decomposition. When 1 2 4 5-tetrazine is dissolved in concentrated hydrochloric acid the solution is a t first deep red but nitrogen is soon evolved and the solution becomes colourless. When hydrogen sulphide is passed into a solution of 1 2 4 5-tetr- azine in water or in benzene the dark red colour gradually disappears and sulphur is deposited; the red colour is restored when dilute acetic acid and sodium nitrite are added. When the tetrazine is reduced i t forms a dihydro-derivative which is readily reoxidised to the tetrazine. Emeraldine.W. NOVER (Bey. 1907 40 288-297).-A new green electrolytic reduction product of nitrobenzene is formed in small quantities at a nickel gauze cathode when the cathode electrolyte is either a 50% solution of sodium hydrogen sulphate or a hydrofluosilicic acid solution of D 1.3. Its constitution mas determined by preparing it either by oxidising p-aminodiphnnylamine with ferric chloride or nitrosobenzene or by shaking P-phenylhydroxylamine with sodium hydrogen sulphate. It is alscl prepared by the polymerisation of phenyl- quininedi-imide with acids (compare Caro Chenz. Zeit. 1896,21 840). By treatment of the green salt so obtained with sodium hydroxide and crystallisation from a mixture of light petroleum and xylene emeraldine (G6H5N2)$ is obtained as a blue amorphous substance giving a carmine-red coloration with concentrated sulphuric acid.The formation of emeraldine in the cell is supposed to be due to the following changes N*N A. McK. Ph*NO -+ Yh*NO -3 Ph*NH.OH -+ PB*NH I I IORGANIC CHEMISTRY. 263 Preparation of o-Hydroxyazo-derivatives. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 175827).-Diazotised o-amino- phenol and its derivatives containing neither nitro nor sulphonic groups do not readily couple with 1 8-dihydroxynaphthalene-3 6-disulphonic acid in the presence of aqueous alkali hydroxides. When however the conpling is effected in the presence of milk of lime the reaction pro- ceeds smoothly and a good yield of the pure product is obtained. The disulphonic acid is employed in the form of its disodium salt and t h t calcium hydroxide emulsion and the diazo-solution are added success- ively.The mixture is left for some hours i n order that the condensa- tion may be completed and the azo-derivative is freed from the calcium hydroxide by means of acid and then salted out in the usual way. The patent contains a table giving the properties of the azo-dyes prepared by this method from seventeen derivatives of o-aminophenol. Hyposulphites. IV. Action of Sodium Hyposulphite on Diazo-Salts. EUGBNE GRANDMOUGIN ( B e y . 1907 40 422-423. Compare Abstr. 1906 i 716 967; this vol. i 166).-When a solu- tion of diszobenzene sulphate or chloride is added to a cold well- stirred suspension of sodium hyposulphite in water a mixture of diazo- benzeneimide and benzenesulphonphenylhydrazide (in.p. 164*5O not 148-150’; compare W. Konigs Abstr. 1S77 219) is precipitated ; sodium phenylhydrazine-P-sulphonate the chief product of the reaction is obtained from the mother liquor. Phenol and a small quantity of phenyl disulphide n r e formed when warm hyposulphite solution is used. [The Orientation of Sulphonated Chlorotoluene-azo-P- naphthols and their Lake-forming Properties.] BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 175378 and 175396).-6-Chloro-p-toluidine- 5-sulphonic acid furnishes a sparingly soluble diazo-derivative which when coupled with ,&naphthol? y.ields an azo-dye forming very sparingly soluble calcium barium aluminium and lead salts. These salts have a brilliant scarlet hue which is affected neither by acids nor alkalis and is very fast to light.The following isomerides 5-chloro-p-toluidine-3- sulphonic 4-chloro-o-toluidine-5-sulphonic and 5 - chloro-o-t oluidine-3 - sulphonic acids give coloured salts which on account of their great solubility in water and their sensitiveness to scouring agents cannot be employed as lakes. The following bases 4-chloro-m-nitroaniline 6-nitro-4-nz-xylidine and 2 5-dichloro-p-toluidine when diazotised and combined with P-naphthol- 3 6-disulphonic acid yield azo-dyes giving insoluble dark red barium salts suitable for lakes. This property is found t o be generally true of all derivatives of aniline which contain two substituent groups or atoms i n positions adjacent to one another. The patent contains a table of bases which have been examined from this standpoint.G. T. M. W. R. G. ‘I?. 31. Goloured Hydrazinesulphonic Acids. J ULIUS “ROGER and CEORG YUTTKAMIMER (Bey. 1907 40 206-2 12. Compare Abstr 1904 i 118; 1906 i 120 993 994 ; Farbenfabiiken vorm. F. Bayer264 ABSTRACTS OF CHEMICAL PAPERS. & Co. D.R.-P. 163447).-The red azobenxene-p-hydrazinesulphonic acid N,Ph*C,H,*NH*NH*SO,H prepared previously by passing a current of sulphur dioxide through a cooled solution of diaxobenzene sulphate has now been synthesised (a) by the action of diazotised 21-8rninoazobenzene on potassium sulphite in cooled aqueous potassium carbonate solution and reduction of the resulting stable potassium azobenzenediazosulphonate N,Ph-C,H,*N2*S0,K by means of am- monium sulphide and ( b ) by passing a current of sulphur dioxide into 'an aqueous solution of diazotised p-aminoazobenzene. 2 3'-Dimethylazobenzene-4-hydrazinesulphonic acid has been pre- pared in the same manner from 4-amino-2 3'-dimethylazobenzene by diazotisation conversion into potassium 2 3'-dimethylazobenzene- 4-diazosulphonate and reduction of this with ammonium sulphide.The resulting hydrazinesulphonic acid forms a p-toluidine salt m. p. 154') which is identical with that obtained from the product of the action of sulphur dioxide on diazotised nz-toluidine. C H ,Me*N,*C,H,Me*N SO,K prepared by the action of potassium sulphite on diazotised 4'-amino- 2 3-dimethylazobenzene is obtained as an orange-red precipitate and when reduced with aqueous ammonium sulphide yields the reddish- brown 2 3'-di~nethylaxobe~~xene-4'-hydi~axinesulphonic ucid C,H4~e*N,*C6H ;M e*NH*NH*SO,H. This forms yellow alkali and aminorzium salts reduces ammoniacal silver solution and when heated with aromatic aldehydes in sulphuric acid and alcohol gives a bluish-violet coloration.The coloured hydrazinesulphonic acids condense with ketones in alcoholic-sulphuric or glacial acetic acid solution forming coloured sulphates from which ammonia liberates the crystalline hydraxones. Potassium 2 3'-dimethylaxobenxene-4'-diaxosuZphonate G. Y. [An Azopyrazolone Derivative.] FARBWERKE VORM. MEIYTER LUCIUS & BR~~NING (D.R.-P. 175290).-nz-Xylidine-o-sulphonic acid when diazotised and coupled with phenylpgrazolonesulphocarboxylic acid yields an azosulphocarboxylic acid which surpasses tartrazine in its tinctorial properties and in fastness to light.The new acid is precipitated from alkaline solutions by mineral acids and sodium chloride. G. T. M. Extractives of Muscle. VI. Identity of Ignotine and Carnosine. WLADIMIR GULEWITSCH (Zeitsch. physiol. Chem. 1906 50 204-20S).-Kutscher's ignotine (Zeitsch. Nahr. Genussm. 1905 10 528) is identical with carnosine (Abstr. 1900 i 516); both melt and decompose a t 241-245'. Extractives of Muscle. VII. Compounds of Carnitine. R. KRIMBERG (Zeitsch. physiol. Clbern. 1907 50 361 -373. Compare Abstr. 1905 i 726).-Carnitine yields two double salts with mercuric chloride. The one C7H,,0,N,2HgC1 m. p. 196-197' is formed when alcoholic solutions of the base or its carbonate and of mercuric chloride are mixed ; it crystallises well and is sparingly soluble in water.The other U7H,,0,N,HC1,6HgC12 is obtained from solutions con- J. J. S.ORGANIC CHEMISTRY. 266 taining an excess of hydrochloric acid usually as an oil which slowly crystallises ; it is more readily soluble than the other mercurichloride from which it can be separated by fractional crystallisation. The compound with 2 mols. of mercuric chloride can be made use of for the isolation of carnitine. Carnitmne phosphotungstate cry stallises in fan-shaped aggregates of needles. The hyd?.ochloi*icle is very hygroscopic and is Iaworotatory. The aurichloride C7H,,0,N,AuC1 crystallises in pale-yellow needles and orange-coloured needles and prisms m. p. 150. The nitrate is also very hygroscopic. The formula 0- co NMe3<cH2.c H( OH)>CH is suggested for the base. J. J. 5. Caseinokyrine. 111. MAX SIEGFRIED (Zeitsch. physiol. Chem. 1906 50 163-173. Compare Abstr. 1905 i 104).-Further examination has shown that the specimens of caseinokyrine previously obtained were pure. The fact that Skraup and Witt’s preparations (Abstr. 1906 i 916) were not pure is due to the fact that they did not follow the details of the author’s method of purification. The carbamino-reaction (hbstr. 1905 ii 333 ; 1906 i 144) has been employed in the case of caseinokyrine and the ratio COJN found to be 1/2*25. For the products of hydrolysis the ratio is 1/1-5. J. J. S. Light Absorption of Hamoglobin. HANS ARON and FRANZ MULLER (Zeitsch. physiol. Chem. 1907 50 443-444).-Polemical against R. von Zeynek (this vol.i 167). W. D. H. The Gradual Hydrolysis of the Oxyhzemoglobin of the Horse. HUGO KIRBACII (Zeitsch. physiol. Chem. 1906 50 129-162. Compare Siegfried Abstr. 1905 i 104).-A basic complex globino- kyrine analogous to Siegfried’s caseinokyrine has been isolated from the products obtained by the hydrolysis of pure recrystallised horse’s oxyhsmoglobin with 12% sulphuric acid a t 37-46’. It may be pre- cipitated by means of phosphotungstic acid and purified by conversion into the sulphate; the yield of crude sulphate varying from 50 to 60 grams per 10 litres of blood. Neither phosphotungstate nor sulphate could be obtained in a crystalline form. The base and its sulphate dissolve readily in water and the base is insoluble in ether and prac- tically insoluble in alcohol; it gives the biuret but not Millon’s reaction.The sulphate is optically inactive and gives the Congo- reaction. The mean analytical data obtained from several pure specimens are C 34.26 ; 33 5.89 ; N 15.08 ; 8 10.95 and 0,33*73%. When hydrolysed with 33.3% sulphuric acid the sulphate yields histidine arginine lysine and glutamic acid. Of the total nitrogen in the hydrolytic products the proportions due to the bases and to the amino-acids have been determined and also the proportions due t o each product of hydrolysis. The results agree with the view that the nitrogen in the kyrine is distributed between 2 mols. of histidine 1 of arginine 2 of lysine and 4 of glutamic acid. J. J. S. VOL. XCII. i 1266 ABSTRACTS OF CHEMICAL PAPERS. Preparation and Analysis of Nucleic Acids.XII. Nucleic Acid from the Spermatozoa of the Shad. (Alosa). PHCEBUS A. LEVENE and JOHN A. MANDEL (2eitsch.physioZ. Chem. 1906 50 1-10 Compare Abstr. 1906 i 125 468 ; this vol. i 168).-The nucleicacid from the spermatozoa of the shad contairjs C 36.2'7; H 5.00; N 15.96 and P 8.11%. I n the estimation of purine bases much smaller yields of guanine are obtained when the copper nucleate is hydrolysed instead of the free acid. The purine bases isolated were adenine guanine thymine ; and in addition cytosine and lsevulic acid were obtained. J. J. S. IVAR BANG (Zeitsch. physiol. Chem. 1907 50 442).-Polemical against Steudel (Abstr. 1904 i 837 ; 1905 i 398 ; 1906 i 125 ; this vol. i 168). Peptones from Albumins. 11. Peptones Derived from Blood Albumin and Precipitated by Potassium Mercury Iodide.HENRY S. RAPER (Beity. Chem. Physiol. Path. 1907 9 168-182. Compare Stookey Abstr. 1906 i 327).-The potassium mercury iodide peptone precipitate obtained after blood albumin had been fermented with pepsin and sulphuric acid for six weeks was extracted with water in which some two-thirds dissolved B the residue A dissolved completely in 5% ammonium carbonate solution. A portion of B dissolved in alcohol Bu but a considerable amount was insoluble Bp. The phenylcarbimide derivative from fraction A was prepared and resolved into three separate fractions by conversion of the carbamide into its sodium salt and precipitating this with carbon dioxide and extracting with hot alcohol. The fraction Aa was insoluble in alvohol Ah separated out a t O" and Ac was obtained on removal of the alcohol.The m.p.'s are respectively 203-205' 178-180' and 169-1 70". From p-bromophenylcarbimide a bromo- derivative corresponding with fraction Ab mas prepared. The per- cen tage composition agrees with the formula C64H89018N16Br3 m. p. 184-185". The bromo-derivative correspondiug with the fraction Ac has the composition C,,H,,O,N,Br m. p. 173-175'. The phenylcarbimide derivative Ac when hydrolysed with con- centrated sulphuric acid yields lysine proline leucine tyrosine aniline ammonia glutamic acid a base m. p. 231-233' and a product m. p. 110- I12' and soluble in ether. From fraction B two phenylcarbimide derivatives were obtained. The one BU is sltluble in 10% alt.ohol and has m. p. 167-169'. None of the compounds could be obtained in a crystalline form.Nucleic Acids from the Thymus. W. D. H. J. J. S. Protarnines and Histones. ALBRECEIT KOSSEL and H. PRINGLE (Zeitsch. p/ysioZ. Chenz. 1906 49 301-321. Compare Abstr. 1905 ii 467).-The simplest protamines are those of the salmine group (salmine clupeine scombrine) ; 8/9ths of the nitrogen present is in the form of arginine the remaining 1/9th as monoamino-acids; alanine serine aminovaleric acid and proline. Two or more of these mono-acids may be present. As arginine contains 4 atoms of nitrogen it follows that 1 molecule of monoamino-acid is present toORGANIC CHEMISTRY. 267 every 2 molecules of arginine and such protamines are therefore dkrginyl compounds. Reasons are given for believing that the link- age is symmetrical thus uab’ uab” uubl” where a is arginyl and b’ b” b”‘ monoamino-groups.The protones obtained as the first cleavage products from these protamines also contain 8/9ths of their nitrogen in the form of arginine. Diarginylalanine will have the molecular weight 401 diarginylserine 41 7 diarginylproline 427 and diarginylaminovaleric acid 429. The boiling point and freezing point methods of determination gave the molecular weight of the protones as from 419 to 423. It therefore appears that the protones are mix- tures of the diarginyl compounds just enumerated. By the action of nitrous acids on this mixture ornithine is split off from which it is argued that the symmetric arrangement is probably b a a rather than n a 6 or a b a. It is only by considering such simple cases that the study of more complex proteids becomes possible. I n histones arginine is again the most abundant cleavage product (24% to 26% of the total nitrogen) and lysine comes next (7% to 8%). From various histones the substance called histopeptone was prepared by peptic digestion ; this yields the same proportion of arginine but it appears to be a chemical unit not a mixture as the protones are. The method of obtaining this substance by thg silver-bnryta method is given. Globin is not regarded as a histone. W. D. H. Histopeptone. T. KRASNOSSELSRY (Zeitsch. physiol. Chem 1906,4Q 322-323).-Attempts to obtain histopeptone (see preceding abstract) from various vegetable proteids failed. It was however obtained by Kossel’s method from various animal organs namely from the testes of the cod and the spleen. The percentage of nitrogen in the former preparation was 19.5 in thelatter 19.7. Kossel found it to be 19-9 in the histopeptone prepared from thymus. Histopeptone was also obtained from liver lymph glands intestinal mucous membrane and red marrow. The most abundant yield was from the spleen the least from the liver. Action of Ultra-violet Light on Invertase. A. JODLBAUER and HERMANN VON TAPPEINER (Chem. Centr. 1906 ii 1512; from Arch. Llin. Med. 87 373-388. Compare Abstr. 1906 ii 917).- Comparative experiments are recorded on the amount of destruction of invertase by ultra-violet light in atmospheres containing oxygen and in the presence of gases free from oxygen in the presence and absence of materials such as sulphites which absorb oxygen ; in the pre.3ence and absence of fluorescent materials &c. The destruction which occurs in the absence of oxygen as for instance in atmospheres of hydrogen or nitrogen is less than when oxygen is present but 1s not due to the presence of traces of oxygen. The presence of oxygen is not a condition for the biological action of light. Lactic Acid Fermentation. REGINALD 0. HERZOG (Zeitsch. yhyeiob. Chem. 1906 49 482-483).-Polemical against Buchner and Meisen- heimer (Abstr. 1906 i 919). W. D. H. A Case of Specific Adsorption af Enzymes. SVENG. HEDIN (Bio-&em. J. 1907 2 112-116).-The a- and P-proteases in ox-spleen W. D. H. W. D. H.268 ABSTRACTS OF CHEMICAL PAPERS. are adsorbed in the same proportions by charcoal; kieselguhr adsorbs the former but probably not the latter at all. Influence of Temperature on the Work of the Proteolytic Enzyme and the Zymase in Killed Yeast Cells. ANNA PETRUSCHEWSKY (Zeitsch. physiol. Chem. 1907 50 251-262).-The experiments recorded confirm the statement t h a t tho proteolytic ferment (endotryptase) separated from yeast cells destroys zymase and the destruction of the latter is the more complete the more energetic the action of the former is. Zymase is not yet obtainable in a pure condition and therefore observations on the physicochemical laws that regulate its action are not possible. The harmful action of it on endotryptase can be lessened by working a t low temperatures or by the addition of strong solutions of sugar. W. D. H. W. D. H. Extraction by Caseinogen of Trypsin Adsorbed by Charcoal. SVEN G. HEDIN (Bz'o-chem J. 1907,2 Sl-88).-A solution of caseinogen in 0.2% sodium carbonate solution extracts trypsin which has been adsorbed by charcoal. Usually in less than thirty minutes at 20° the extraction comes to an end; the final amount extracted rises with the temperature and with the amount of caseinogen used up to a certain limit beyond which the amount extracted is independent of the amount of caseinogen. The amount of water present makes no difference. The results support the view t h a t proteids combine dith trypsin before they are broken up by it. W. D. H. Behaviour of Peroxydase towards Iodine. ALEXIS BACH (Bw. 1907 40 230-235. Compare Abstr. 1904 ii 3lO).-As the oxidis- ing action of hydrogen peroxide on hydriodic acid aromatic amines and phenols is increased by the presence of peroxydase from horse-raddish roots or other vegetable sources according to the theory of specific ferment action the peroxydase should consist of at least three enzymes. All attempts however either by fractional precipitation by means of alcohol or acetone or by destroying part of the peroxydase by means of iodine to obtain a peroxydase incapable +of increasing the activity of hydrogen peroxide towards all three classes of substances have been unsuccessful. The effect of iodine on the influence of peroxydase on the oxidation of phenols by hydrogen peroxide has been studied quantitatively in the case of pyrogallol. With peroxydase extract the maximum formation of purpurogallin increases to a certain extent with tne amount of iodine present diminishing on addition of larger quantities of iodine ; this points to the presence of the zyrnogen the conversion of which into the active peroxydase is accelerated by addition of iodine. Precipitated peroxydase on the other hand does not contain zymogen since its influence on the oxidation of pyrogallol by hydrogen peroxide is not increased by addition of iodine. G. Y.

ISSN:0368-1769    

DOI:10.1039/CA9079200169

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

182 ABSTRACTS OF CHEMICAL PAPERS. Miner a 1 ogical C he mi stry. Fumarole Action. 11. FERDINAND HENRICH (zeitsch. angew. them. 1907 20 179-181. Compare Abstr. 1906 ii 685)-In extension of his previous experiments the author has found that on passing a slow current of steam over a mixture of sand and sodium or potassium chloride heated to bright redness an appreciable quantity of these salts is volatilised. This fact serves to account for the presence of sodium or potassium chloride on the surface of fumaroles. P. H Cinnabar from Sonoma Go. California ; Gypsum and Calcite from Terlingua Texas. ARTHUR SACHS (Centr. Mi?%. 1907 17-1 9).-CrystalIographic descriptions are given of these minerals. L. J. S. Uranium Ores from German East Africa. WILLY MARCKWALD (Cent?.. Min. 1906 761--763).-Enclosed in sheets of mica from Luk- wengule in the Uruguru Mountains Morogoro district are crystals of pitchblende which are largely altered t o a yellow uranyl carbonate.Analysis I is of the pitchblende and I1 of the uranyl carbonate for which the name rutherfordine after E. Rutherford is proposed (not to be confused with rutherfordite from Rutherford Co. North Carolina) U,Os. UO,. PbO. FeO. CaO. Si02. H,O. CO,. Gangie. Total. Sp. gr. I. 87.8 - 7-5 1.0 2.1 0.3 0.5 0'2 99'4 8-84 11. - 83.8 1.0 0'8 1.1 - 0.7 12.1 0.8 100.3 4'82 Analysis I1 corresponds with the formula UO,CO,. The carbon dioxide is not. expelled below a temperature of 300° Anhydrous uranyl carbonate has not before been met with in nature nor has it been prepared artificially; attempts to obtain it from the ammonium double salt were unsuccessful.The radioactivity of this pitchblende and of the rutherfordine is about 20% higher than that of pitchblende from Joachimsthal. L. J. S. Apatite and Milarite from Switzerland. KARL Busz (Centr. dlirt. 1906 753-761).-A crystallographic description is given of adularia quartz milarite and apatite from a new occurrence on the Rhone Glacier. The perfectly developed crystals of the apatite are pale violet in colour ; a c = 1 0.7335. The following analysis by K. Walter provesPEYSIOLOGICAL CHEMISTRY. 183 the material to be an almost pure fluor-apatite. Determinations of the refractive indices are given P20,. (Al,Fe),03. MnO. CaO. MgO. K20. Na,O. H,O. F. C1. Ofor F. Sp. gr. 41-44 0.94 0.39 54-80 0.14 0.45 0:53 0.22 2.93 trace 100*61 3.195 Total less L.J. S . Constitution of Biotite. KARL DALMER (Centr. Min. 1907 51-58. Compare Abstr. 1898 ii 440).-Tschermak’s theory which explains the composition of biotite by assuming mixtures of muscovite and olivine molecules is discussed; the author finds it necessary to consider the olivine to be hydrated. Biotites are divided chemically into (1) normal biotites (mixtures of muscovite and olivine molecules) including anomite haughtonite protolithionite meroxene and lepido- melane ; (2) acid biotites or phengite-biotites (mixtures of phengite and olivine or of phengite muscovite and olivine molecules) including phlogopite and zinnwaldite. GUSTAV REINANN (Jahrb. Min. 1907 13eiZ.-Bd. 23 9 1-162).-Detailed descriptions are given of the forms of 160 crystals.The optical and pyro-electrical characters were also investigated. L. J. S. Order of Separation in Silicate Fusions. RUDOLF FREIS (Jahrb. Miltz. 1907 Be&!.-Bd. 23 43-90).-Mixtures of two or three of the minerals diopside anorthite olivine nepheline orthoclase and magnetite were fused and the melting points of the glasses and of the crystallised products were determined. In the latter the order of separation of the minerals was magnetite olivine diopside anorthite diopside nepheline orthoclase ; this being the same order as given by Rosenbusch for igneous rocks except that in the fusions diopside separated after as well as before anorthite. An accumulation of certain materials in the fusions is suggestive of magmatic differentiation. In these silicate fusions dissociation takes place and the laws of dilute solutions are not applicable. L. J. S. Tourmaline from Brazil. L. J. S.

ISSN:0368-1769    

DOI:10.1039/CA9079205182

出版商:RSC    

年代:1907

数据来源: RSC

摘要:

PEYSIOLOGICAL CHEMISTRY. Physiological Chemistry 183 Artiflcial Parthenogenesis by Momentary Elevation of Temperature. RALPH S. LILLIE (Proc. Amer. physiol. Soc. 1906 xvi-xvii ; Arne?.. J. Physiol. 18).-Exposure of star-fish eggs to 34-3S0 for from 30 to 120 seconds is followed by apparently normal development. W. D. H. Chemistry of Cell Division Maturation and Fertilisation. ALBERT P. MATHEWS (Amer. J. Physiol. 1907 18 89-lll).-The paper is highly speculative. The chemical basis of cell division is184 ABSTRACTS OF CHEMICAL PAPERS. probably a process of respiration the astral 6gure being a localised region at the centre of which there is intense reduction ; an oxydase and free oxygen are other factors concerned. Temperature and Carbon Dioxide Excretion in Rats kept in Very Moist or Very Dry Atmospheres.JOHN J. R. MACLEOD (Amer. J. PhysioE. 1907 18 l-l3).-The harmful effect of a warm humid atmosphere on man as compared with dry air of the same temperature is well known to experience but has never been accurately investigated to any extent. The present research on rats showed that in these animals which do not depend greatly for heat regu- lation on evaporation from the body surface little or no deleterious effect of humidity could be observed. Such animals however are not able to withstand hot dry atmospheres SO well as man can. W. D. H. W. D H. Contact Action in Biological Chemistry. Enzyme and Plasma. THOMAS BOKORNY (Chem. Zeit. 1907 31 139-141).-A variety of reactions which are effected by organised ferments or by enzymes may also be brought about by means of inorganic catalysts.The efficiency of an inorganic catalyst may be impaired by certain substances but can as a rule be restored by suitable treatment whereas a ferment once poisoned is completely destroyed The phenomena of respiration and assimilation are regarded as examples of enzyme action. P. H. The Sugar in Blood and Tissues. EDWARD S. EDIE and D. SPENCE (Bio-chem. J. 1907 2 103-1 1 l).-The blood with aseptic precau- tions is dialysed against saline solution for 40-50 hours in an ice chamber and the sugar in the dialysate estimated by a gravimetric copper method. The sugar is present (1) as free sugar (2) in com- bination with proteid or lecithin and (3) as polysaccharide. The method although lengthy is regarded as more trustworthy than others such as the mercury precipitation method.The corpuscles are dovoid of sugar. W. D. H. Oxydases ia Blood. WALTHER EWALD (PJEiger’s Archiv 1907 116 334-346).-A discussion of the work of others on the three oxydases described in blood precedes the experimental portion of the paper. The three enzymes are a-oxydase which oxidises easily oxidis- able substances ; peroxydase which activates intermediate peroxides and so oxidises substances difficult of oxidation ; and superoxydase (catalase or hzemase) which serve as a protective means of the body cells against the too great activity of peroxydases. This is the view of Bach and Chodat which is regarded as untenable by the author. Cyanide poisoning is shown to lessen the amount of catalase and to increase the readiness with which oxyhaemoglobin is reduced.W. D. H. Action of Serum and Tissue Extracts on Blood Coagula- tion. LEO LOEB (Proc. Amer. physiol. Soc. 1906 xvii; Amer. J. Phpiol. 18)-Both the congulin of tissue extracts and the thrombinPHYSIOLOGICAL CHEMISTRY. 185 of serum are believed to act independently on fibrinogen. This conclu- sion is drawn mainlyfrom observations OR invertebrate blood but it is unlikely that there is any essential difference between this and verte- brate blood although in the latter case complications arise from the presence of substances in the serum which accelerate or hinder the action of tissue coagulins. Influence of Lecithin on Digestive Ferments. SIEGIMUND KUTTNER (Zeitsch. physiol. Chern. 1907 50 472-496).-The results obtained by the addition of lecithin emulsion to an artificial gastric digest appear to be very varying ; the methods adopted were numerous and included that with Mett’s tubes.The general conclusion is drawn that the influence of lecithin below certain limits is beneficial ; above these it hinders protein-hydrolysis. The same conclusion is drawn in reference t o trypsin. The favouring influence of lecithin on the fat- splitting enzyme of pancreatic juice is more marked. Occurrence of Indole in Human Gastric Contents. HERMANN STRAUSS (Biochem. Zeitsch. 1907 3 26-39).-In reference to the discovery of indole in the gastric contents by Albu and Neuberg in cases of gastric cancer the author points out that he once found it in a case of stenosis in which the putrefactive process occurred in the stomach.He has since searched f o r it but never found i t in similar cases. I n the author’s case as in cancer there was subacidity of the gastric juice. The Occurrence of Erepsin in the Pancreas. HORACE M. VERNON (Zeitsch. physiol. Chcm. 1907 50 440-441).-Polemical against K. Mays (this vol. ii 38). The Lipase of Intestinal Juice. W. BOLDYREFF (Zeitsch. physiol. C’hem. 1907 50 394-413).-Lipase is present in pure intestinal juice. It acts better on emulsified than on non-emulsified fats. It is weaker than pancreatic lipase ; its action is not favoured by the presence of bile and but little weakened by the presence of antiseptics. W. D. H. The Value of Betaine in the Sheep. W. VOLTZ (Pcfliier’8 Archiv 1907 116 307-333).-1f betaine is given to a dog the total nitrogen in it is excreted the same day.I n herbivora (sheep) it is retained longer in the body. I n these animals contrary to what is found i n carnivora betaine is split up in the body and some of the non-nitrogenous portion is not excreted in the urine ; it is possible that this is harmful. W. D. H. W. D. H. W. D. H. W. D. H. W. D. H. Katabolism of Glycine in Badly Nourished Conditions of the Infant. LUDWIG F. MEYER and HANS RIETSCHEL (Biochem. Zeitsch. 1907 3 31-44).-In normal conditions glycine is completely burnt in the body. I n the present investigation it was added to the food of infants suffering from malnutrition. They show a diminution of the power to utilise glycine ; i n some cases acidosis and glycosuria occurred also.The condition is regarded as one in which the oxidative energy of the body is lessened. W. D. H.186 ABSTEACTS OF CHEMICAL PAPERS. Creatine and Creatinine in Human Metabolism. KJ. OTTO AF KLERCKER (Biochem. Zeitsch. 1907 3 46-87. Compare Abstr. 1006 ii 295).-Any biological relationship between these two bases is questionable. If given to an animal they are excreted in the urine unchanged and of the two creatinine is the more readily eliminated. Urinary creatinine is wholly of endogenous origin ; its relationship to the muscular creatine has not been proved and is considered uncertain. Folin has come to much the same conclusions. W. D. H. The Mechaniem of Proteid Assimilation. CH. INAGAICI (Zeitsch. physioZ. Chent. 1907 50 449-471).-Nucleo-histone unites with proteoses in a salt-like way so long as it is in a free or dissociated condition so t,hat i t is possible that proteoses introduced into the blood stream may be fixed by the cell substance in this way No evidence of any such fixation was found in the blood itself.W. D. H Sparing Action of Gelatin. J. R. MURLIN (Proc. Amsr. physiol; Xoc. 1906 xii-xiii ; Amer. J. Phgsioh. 18).-Lusk and Nolan showed that in diabetes gelatin may yield up to 60%of its weight as dextrose. The present research was made to determine to what extent this carbonaceous part of the gelatin molecule will account for its proteid- sparing action but the conclusion is arrived a t that this action is entirely accounted for by its nitrogenous constituents. W. D. H The Replacement of Proteid by Gelatin.PETER RONA and W. MULLER (Zeitsch. physioh. Chem. 1907 50 263-280).-The sparing- action of gelatin is one of the oldest known facts in reference to meta- bolic investigations. Its power t o replace other proteids is limited and this is now explicable because i t lacks the tyrosine and tryptophan groups Kaufmann (Abstr. 1905 ii 735) is one of the latest to determine the extent of sparing-action and the present experiments like his were made on dogs but in this case the addition of the missing groups did not increase the value of the gelatin. W. D. H. Action of Vegetable Cathartics on the Isolated Centre of a Jelly-Fish. JOHN 16. MACCALLUM (J. Riol. Chem. 1907 2,385-390). -Various vegetable purgatives stimulate the isolated central portion of PoZyorci~is t o contract rhythmically.There is however no proof that this region is free from nerves and so no conclusion can be drawn that the purgatives act on the muscular tissue alone. W. D. H. Nutrition of the Excised Mammalian Heart. CHARLES C. GUTHRIE and F. H. PIKE (Arne?.. J. P?qsioh. 1907 18 14-38)- Defibrinated blood and serum were found superior to saline solutions for keeping the excised heart beating. A certain degree of capillary pressure appears also to be essential. A strip of cat’s aorta behaves very like a strip of ventricle. W D H.PHYSIOLOGICAL CHEMISTRY. 18’7 Cause of the Staircase Phenomenon. FREDERIG S. LEE (Proc. Amer. physiol. SOC. 1906 xviii-xix ; Ammer. J. Physiol. 18)-The staircase phenomenon in muscle is due to the accumulation of fatigue products namely carbon dioxide mono-potassium phosphate and sarcolactic acid.W. D. H. Creatinine and Creatine in Meats and their Products. HARRY S. GRINDLEY and H. S. WOODS (J. Biol. Chem. 1907 2 305-326).-Folin’s colorimetric method was employed. Contrary to C. 5. Johnson’s statement fresh meat contains only the faintest trace of creatinine. The results of creatine estimation in various fresh meats are given in tabular form. Similar determinations are given for various meat extracts ; in these the proportion of the two substances varies very much. W. D. H. Formation of Fat in Animals Fattened for Slaughter. GEORGE T. KEMP and L. D. HALL (Proc. Amer. physiol. Soc. 1906 xix; Amer. ..L Physiol. 18).-The fat was never found microscopically within the sarcolemma; still very lean flesh yields more fat by extraction than can be accounted for by the adipose tissue revealed by the microscope.No support was found in favour of the view that toughness of meat is due to the thickening of the sarcolemma. W. D. H. Chemical Examination of Human Bone-Marrow under different Pathological Conditions. JULIUS WOHLGEMUTH (Chem. Centr. 1906 ii 1770; from Arbeit. Path. Inst. Berlin).-The pre- sence of albumoses and principally of deutero-albumoses and a nucleo- proteid which contained a considerable quantity of phosphorus has been detected in a number of samples of human bone-marrow When the aqueous extract was made faintly acid with acetic acid a precipitate was formed which after washing dissolving in ’ sodium carbonate and reprecipitating formed a snow-white powder which gave a moderately strong reaction with orcinol-hydrochloric acid ; it contained 45.01% C 5.91% H 14.21% N 1*780/ P and 0.315% S.E. w. w The Change Produced in Milk by Sodium or Potassium Hydroxide. FRIEDRICH KRUGER (Zeitsch. physiol. Chem. 1907 50 293-302).-Gautier and Morel have recently pointed out that the addition of potassium or sodium hydroxide to milk causes a red coloration. The present paper points out that the reaction was described by the author twelve years ago. The best result is obtained when the milk contains 1-2% of sodium hydroxide. All attempts to separate the colouring matter have failed but the presence of both caseinogen and lactose is necessary for its production An elevated temperature increases the rapidity of its appearance. W.D. H Bile in Human Milk. J. L. B. VAN DER MARCK (Pharm. Weekblnd 1907 44 153-155).-The author has detected bile in a sample of human milk from a patient who developed jaundice after188 ABSTRACTS OF CHEMICAL PAPERS. each confinement. The milk was a deep yellow colour with a green fluorescence. After thirty minutes it had separated into a deep yellow fatty layer and an almost colourless aqueous liquid. The percentage of solid residue was 13.1 including 7.14% of fat 2.09% of lactose 0.124% of ash and 3.746% of proteids. The fat contained urobilin and a smaller amount of bilirubin but the aqueous liquid was wholly free from them. A. J. W. [Alleged] Formation of Free Nitrogen During Intestinal Putrefaction. AUGUST KROGH (Zeitsch. physiol.Chem. 1907 50 289-292. Compare Schittenhelm and Schroter Abstr. 1904 ii 139 ; Oppenheimer ibid. 361 ).-Free nitrogen is not found in intestinal putrefaction. W. D. H. The Effect of Amino-Acids on the Elimination of Acetone Derivatives. L. BORCHARDT and F. LANUE (Beitr. chew,. P?ysioZ Path. 1907 9 116-133. Compare Borchardt Abstr. 1906 ii 312 ; Embden Salomon and Schmidt Abstr. 1906 ii 375).-Glycine alanine and asparagine tend to reduce the amount of acetone eliminated from the organism both in the urine and in the breath. Glutamic acid does not tend to increase the amount of acetone whereas leucine produces a considerable increase in the acetone eliminated. In all cases the amount in the breath was less than that in the urine. J. J. S. Phenolglycuronic Acid.ERNST SALKOWSKI and CARL NEUBERG (Biochem. Zeitsch. 1907 2 307-31 l).-Neuberg and Naimann’s syn- thetical phenolglycuronic acid (Abstr. 1905 i 412) is identical with the acid obtained from the urine of a sheep to which 500 grams of phenol had been administered at the rate of 5 grams per day. The phenolglycuronic acid may be separated from the benzoic and hippuric acids which are also formed by means of cold water in which it is readily soluble. J. J. 5. Occurrence of Bile Acids in Fmces under Normal and Pathological Conditions. HANS URY (Chem. Centr. 1906 ii 1682 ; from Arb. Path. Inst. Berlin).-Normal faeces do not contain taurocholic or glycocholic acid and cholic acid if present occurs only in extremely small traces. The bile acids and i n some cases their de- composition products can be detected however in pathological excre- ments which have an abnormal consistency but the quantity is small.B. w. w. Influence of Work in Phloridzin Diabetes. GRAHAM LUSH (Proc. Amer. physiol. SOC. 1906 xii ; Amer. J. Physiol. 18).- Mechanical effort in a fasting dog made diabetic by phloridzin only slightly increases proteid metabolism but leads to a slight increase in the sugar output which may be derived from the residue of glycogen present in the animal. W. D. H,PH‘JtSIOLOCfICAL CHEMISTRY. 189 Diastatic Ferment in the Tissues in Diabetes. FRANCIS A. The liver and muscles of diabetic men and depancreatised cats contain a diastatic ferment but whether in greater amount than usual was not ascertained. Its activity is not increased by the addibion of a boiled extract OF pancreas.W. D. H. BAINBRID~E and ARTHUR P. BEDDARD (Bio-chem. J. 1907,2,89-95)- Sometimes it is present in the blood also. Treatment of Diabetes by Secretin. NELLIS B. FOSTER ( J . Biol. Chem. 1907 2 297-304).-No benefit was observed in treating cases of diabetes with secretin. This coincides with the statements of Bainbridge and Beddard (Abstr. 1906 ii 786) as opposed to those of Moore and his colleagues (ibid. ii. 186 787). W D. H. Treatment of Diabetes by Secretin. HENHY D. DAHIN and C. C. RANSOM (J. Biol. Chem. 1907 2 305-307).-One case only is described; the use of secretin lessened the output of sugar slightly but this was not permanent nor so great as in Moore’s cases. W. D. H. Pharmacological (‘ Action at a Distance.” ALBERT P.MATHEWB (Amer. J. Physiol. 1907 18 39-46).-Metallic silver and copper in tho neighbourhood of echinoderm eggs cause them to put on fer- tilisation membranes. Mercury (when the eggs are sensitive) iodine and bromine cause the same result. Iron nickel lead tin platinum gold and probably hydrogen wero ineffective. Membrane formation is followed by liquefaction; this occurs only on the side toward the metal and away from the metalloid. This is explained on an electrical hypothesis positive ions being driven away fxom and negative ions attracted to the metallic wire. W. D. H. Pharmacological Action of Ammonium Salts. ALBERT P. MAT HEW^ (Arne?.. J. Physiol. 1907 18 58-63).-Although the pharmacological action of most salts is ionic in the case of ammonium salts their characteristic stimulating action is due to the amount of undissociated ammonium hydroxide present and probably to the nascent ammonia formed from the latter.I n this case there has therefore to be taken into account non-ionic or rather twin-ionic action such as that caused by f>NH particles Perhaps the activity of free alkaloids is due t o similar causes. W. D. H. Rhythm of Turtle’s Sinus Venosus in Isotonic Solutions of Non-Electrolytes. HAROLD E. EUGERS (Amer. J. Physiol. 1907 18 64-70).-Isotonic solutions of sugar urea and glycerol stimulate the turtle’s sinus venoms as they do the heart of Limulus. They act depressingly on the cardiac muscle of Limulus and this is regarded as support to the neurogenic theory for the vertebrate heart. The action of these substances on heart tissue is through the osmotic factor.W. D. H.190 ABSTRACTS OF CEEMICAL PAPERS. Relation of Antitoxin to the Globulin of Blood-Serum. The Leucocyte Reaction during Immunisation with Diph- theria-Toxin. J. C. G. LEDINGHAX (J. Hygiene 1907 7 65-91 9%-100).-During the immunisation with diphtheria-toxin of a horse which finally failed to yield high-grade antitoxic serum the globulin of the blood showed no tendency to increase. A slight rise in total proteid was due to albumin. Tbe failure of the horse was probably related to the initial high globulin-content of its blood. I n a goat the rise in total proteid affected mainly the albumin fraction. In the case of a horse which yielded a high-grade serum the globulin and especially the euglobulin fraction progressively increased.The pseudo- globulin contains most of if not all the antitoxin but it is possible this holds good when the antitoxin content is steadily rising. I n the goat the antitoxin in the two kinds of globulin may vary a t different periods in the course of immunisation. The increase in polynuclear leucocytes which follows the injection of large and increasing amounts of diphtheria-toxin is merely an evidence of efficient cell-stimulation and is not necessarily accom- panied by increased formation of antitoxin. W. D. H. Tetanus-Toxin Antitoxin and Brain Emulsions. L. NOON (J. Hggiene 1907 7 101-104).-The affinity of brain matter for tetanus-toxin is specific as is that of antitoxin. A solution of pure toxin is easily rendered innocuous by treatment with brain matter but if a small dose of antitoxin has been added to the toxin some hours beforehand treatment with brain matter no longer suffices t o render the solution atoxic. The free toxin is removed and a toxic compound of toxin and antitoxin was isolated. Both brain-toxin combinations and antitoxin-toxin compounds dissociate with more or less rapidity unless in the presence of enough free toxin (and free brain or anti- toxin) to maintaiu the state of equilibrium. Consequently to obtain a neutral mixture a large excess of brain or antitoxin must be added beyond. the combining equivalent. The dissociation is thus reduced until free toxin is no longer recognisable. W. D. H.

ISSN:0368-1769    

DOI:10.1039/CA9079205183

出版商:RSC    

年代:1907

数据来源: RSC