i. 113 Organic Chemistry. Preparation of Aluminium Ethoxide. FARBWERKE YORN. MEISTER LUCIUS & BRUNING (D.R.-P. 286596; from J . SOC. Chenz. Itid. 1915 34 1168).-Dry alcohol is t,reated with alumin- ium in the presence of a very small quantity of mercuric chloride (as a catalyst) and in the preseace or absence of alkyl haloids o r iodine. The mixture is then distilled under reduced premure when a dist'illate freel from mercury is obtained. J. C. W. Preparation of 7-Me thylbutinol and its Homologues. FARBENFABRIKEN VORM. F. BAYER & Co. (D.R.-P. 285770; from J . SOC. Chem. Ind. 1915 34 1167).-The alkali compounds of acetylene o r its homologues are treated with acetone o r its homo- logues in an inert medium. J. C. W. Simple and Mixed Alkyl Phosphates. W. A. DRUSHEL ( A mer.J . Sci. 1915 [iv] 40 643-648).-Trialkyl phosphates were prepared'by the action of phosphoryl chloride on the corresponding sodium alkyloxides in suspension in dry ether. Contrary t o state- ments in the literature they were all up to triisobutyl phosphate found t o be distdllable in a vacuum without decomposition. Al- though stable towards cold AT/ 10-hydrochloric acid they were readily hydrolysed by aqueous barium hydroxide and from the barium salts of the dialkyl hydrogen phosphates produced mixed trialkyl phosphates were obtained by the silver salt method. The hydrolysis of the mixed trialkyl phosphates by barium hydroxide proceeds in two directions simultaneously and not as stated by Lossen and Kohler (A. 1891 1013) by the removal of one of the alkyl groups which occurs twice to the exclusion of the group that occurs only once so that the praduct contains e3ter.s of the types HRR'PO and HR,PO,.Tables are given showing the effect of various alkyl groups on the velocity constants of the hydrolysis of simple and mixed trialkyl phosphates by hydrochloric acid a t looo. The following physical constants are given for the phosphoric esters Trimethyl b. p. 197O/760 mm. D22 1.200; triethyl b. p. 215O/ 760 mm. DZ2 1'056; tripropyl b. p. 131°/15 mm. D22 1.007; tri- isobutyl b. p. 152O/15 mm. D22 0.965; dimethylethyl b. p. 203O/ 760 mm. D22 1.161 ; dimethylpropyl b. p. 116O/15 mm. D22 1'180; methyldipropyl b. p. 129O/20 mm. D22 1.059; diethylpropyl b. p. 130°/20 mm. D22 1.077; eithyldipropyl b. p. 145O/20 mm. D22 1.025.G. F. M. The Mechaniem of the Action of Tribasic Sodium Pb osphate on the a-Monochlorohydrin of Glycerol. 0. BAILLY (Compt. rend. 1915 161 677-680).-A critical investigation of the interaction of trisodium phosphate and glycesol monochlorohydrin in which VOL. cx. i. fi. 114 ABSTRACTS OF CflEMICAL PAPERS. the author shows that the changes are not so simple as that stated by King and Pyman (T. 1914 105 1238) (1) Na3P0 + CH,Cl*CH(OH)*CR,*OH = NaCl + P0,Na2*CH,*CH(OH)*CH~*OH The two substances were mixed in equiinolecular proportions the mixt-ure being kept a t 18" and a t definite int<ervals determinations were made of the sodium chloride formed of the trisodium phos- phate destroyed and of the glycerophosphate formed. The results show that whilst the sodium chloride formed and the trisodium phosphate destroyed are in molecular agreement throughout the amount of sodium glycerophosphate formed is always much less than that required by equation (I) the difference being very marked for the first ten hours. The author considers that the formation of sodium glycerophosphate takes place according t o equations (2) and (3) (2) Na8P0 + CET,Cl*CH(OH)*CH,*OH = 0 /\ Na,HPO + NaCl + CH,*CH*CH,*OH 7\ (3) C€€,*GH*CH,*OH + Na,HPO = P0,Ns,*r,H2*CH(OH)*C€~~*O€€ since he has shown thatl the glycide and disodium hydrogen phos- phate do react slowly to give sodium glycerophosphate about 80% of the glycide being transformed into glycerophosphate in about eight days.W. G. Electrolysis of the Alkali Salts of Aliphatic Sulphocarboxylic Acids.FR. FICHTER and THEODOR LICHTENHAHN (Ber. 1915 48 1949-1963).-The anodic oxidation of sulphoacetic acid and its potassium and ammonium salts of potassium sulphopropionate and ammonium sulphopropionate dissolved in the free acid of potassium methanesulphonate and of methanedisulphonic acid and its salts has been investigated. I n the case of sulphoacetic acid and its salts the chief products are sulphurid acid and carbon dioxide but carbon monoxide ethylenie formaldehyde sulphur dioxide and methane- and ethane-disulphonic acids may be detected the latter as their baxium salts. The normal product analogous t o the electro-syn- thesis of ethylene is ethanedisulphonic acid thus 2S03H*CI12*C02H + 0 = C2H4(S03H)2 + 2C0 + H20. Just after the commencement of the electrolysis however the neutral solution becomes alkaline and later on it accumulates neutral sulphates conditions which are favourable' to the Hofer and Moe'st reaction (A.1902 i 736) in which hydroxyl ions convert the fission product. of electrolysis into an alcohol. That is the residues *CK,*SO,H not only coalesce t o form ethanedisulph- onic acid but they give methanolsulphonic acid OH*C"H,-SO,H. This of course is speedily oxidised to the aldehyde CHO*S03H which will give sulphuric acid and formaldehyde on hydrolysis (and therefore also sulphur dioxide and carbon monoxide) or be oxidised t o sulphoformic acid CO,H*SO,H and finally t o sulphuric acid andORGANlC CHEMlSTRY. i. 115 carbon dioxide. The production of ethylem and methanedisulph- onic acid is attributed to anothelr reaction of the *CH,*SO,H residue thus 4*CH,*SO,H = ZCH,(SO,H) + C,H,.Just as the production of butane from a propionate falls very much behind the electrosynthesis of ethane the chief gaseous product being ehhylene so the main result of the electrolysis of a sulphopropionate is the formation of sulphuric acid ethylene and carbon dioxide thus SO,H*CH,.CH,*CO,H + 0 = H2S04 + C,H4 + CO,. Here again secondary reactions take place and carbon monoxide formaldehyde sulphur dioxide and acetic acid may be detected among the products. The electrolysis of potassium methanesulphonate leads to the pro- duction ol' carbon dioxide the sulphate and a little persulphate and also formaldehydesulphonic acid which becomes obvious on boiling the solution.No carbon monoxide o r hydrocarbon is formed. The result is an oxidat.ion unaccompanied by synthetic processes thus CH,*SO,H + 4 0 = CO + H,S04 + H20 and CI13.S0,H + 2 0 = CHO*SO,H + H20. Similarly methanedisulphonic acid or its salts is merely oxidised to sulpliurio acid and carbon dioxide just as it is by 30% hydrogen peroxide. I n the course of thel experiments i t was observed that barium metlhanedisulphotnate crystallises not only in the well-known form of very thin rhombic tablets but in very characteristic centi- metre-long transparent needles arranged in concentric groups. This form is obtained by crystallisation from dilute solutions a t a low temperature in the presence of a trace of acid (for example a drop of 2N-HCl). The needles belong t o the same system as the tablets.F o r the details of the current densities employed and the methods for identifying and isolating the products the original should be consulted. J. C. W. Trichloro-tert.-butyl Acetate (Acetylchloretone). T. B. ALDRICH (J. Amer. Chem. SOC. 1915 37 2720-2723).-When P-trichloropropan-P-ol CCl,*CMe,*OH is heated with a mixture of acetic anhydriae and sodium acetate it is converted into the corre- sponding acetate CCI,-CMe,*OAc b. p. 145-146O/246 mm. Hydro- lysis is effected only slowly with water o r dilute acids but concen- trated nitric acid causes rapid hydrolysis. The acetab has anzes- thetic properties similar to those of the parent alcohol but its toxicity towards guinea-pigs is slightly less. Fatty Acid Esters of Ethylene Glycol. R.F. RUTTAN and J. R. ROEBUCK (Trans. Roy. SOC. Canada 1915 9 1-ll).-The authors have prepared a number of mono- and di-acid esters from ethylene glycol by direct esterification a t high temperatures and with con- stant stirring. About 30 grams of the acid were mixed with an amount of glycol more than sufficient to convert the whole of the acid into mono-ester and the mixture was heated a t 185-187O in an open flask being constantly stirred by a platinum stirrer. The mixturel after fusion was freed from glycol by washing with hot D. F. T. f Si. 116 ABSTnhCTS OF CHEMICAL PAPERS. water and from free acid by iieutralisation with calcium hydroxide. The mono- and di-acid esters were separated by crystallisation from hot alcohol the di-acid ester separating out first.Ethylene ~list~earate C,H (C18H3,0,) crystallises in pearly plates in. p. 7 5 O 1.4385 0.8581; 100 grams of alcohol dissolve 0.010 grain a t Oo 0.028 gram at 25O 0.037 gram a t 2B0 and 0.112 gram a t 403 (compare Wiirtz APitk. Chim. phys. 1859 [iii] 55 436). The moji ost enm t e C,H,(OH) (C1,H3,02) crystallises in pearly plates m. p. 58*5O n;;5 1.4310 Dbl) 0.8780; 100 grams of alcohol dissolve 0.64 gram a t Oo 1.31 grams a t 7 * 4 O 2.10 grams a t 16O 4.17 grams a t 25O 10.61 grams a t 29O. 3 t h ylc. tz e d i p ? ni i ta t e C,H (C ,,H3,02) cry st allises in pearly plates in. p. 68*7O 9 2 g 7 1.4378 D77.9 0.8594; 100 grams of alcohol dissolve 0.018 gram a t Oo 0.087 gram a t 25O 0.109 gram a t 29O 0.31 gram a t 38O. The moizopnlmitnte C,H4(OH)(Cl,H,,0,) crystallises in pearly plates in.p. 51*5O n::s 1.4411 D60.5 0.8786; 100 grams of alcohol dissolve 1-62 grams a t Oo 5.76 grams a t 7*4O 10.67 grams a t 16O 24.08 grams a t 25O. Ethylene dimargarate C2H,(C17H3302)2 crystallises in needles or waxy scales in. p. 65*5O 122 1.4392 D67.1 0.8605; 100 grams of alcohol dissolve 0.024 gram a t Oo 0.101 gram a t 25O. The m0120- ?norprcite C,H,(Ol€)(C,,€13,02) crystallises in thin plates m. p. 5O*Zc ng 1.4440; 100 grams of alcohol dissolve 1-72 grams a t Oo. The esters with oleic acid were not satisfactorily separated as their solidification points seemed very near each other and t h a t of oleic acid itself. Ethylene chlorohydrin when heated in a sealed tube for twenty hours a t 105-115° with equivalent quantities of either stearic or palmitic acid gave the corresponding chloroethyl ester the action ceasing when 18-20% of the acid remained uncombined.Chloroethyl stearate C2H,C1*CI8H3,O2 crystallises in waxy scales m. p. 48-5O D49.5 0.9049 1.4433 ; 100 grams of alcohol dissolve 0.20 gram a t Oo 0.28 gram a t 7'4O 1.29 grams a t 16O 2-10 grams a t 25O 3.62 grams a t 29O. Chloroethyl palmitate C,H4C1-Cl,H,,O2 crystallises in pearly plates m. p. 41*5O w g 5 1.445 D46*I 0.9097; 100 grams of alcohol dissolve 0-48 gram a t Oo 1.16 grams a t 7'4O 3.8 grams a t 16O 8.87 grams a t 2 5 O 15.31 grams at 29O. Chloroetliyl stearate when heated with the calculated quantity of silver palmitate a t 140° for three t o four hours or with potassium palmitat'e for a much longer time gives ethylene stearopalmitate C2H,(C,8H3502)(CIFH3102) m.p. 65O n 2 1.4391 D7O.5 0.8584; 100 grams of alcohol dissolve 0.011 gram a t Oo 0.035 gram a t 25O 0.049 gram a t 29O 0.213 gram a t 39O. W. G. Catalytic Bleaching of Palm Oil. SOSALE GARALAPURY SASTRY (T. 1915 107 1828-1831. Compare Eng. Pat. 17784 of 1913).- A series of experiments is described on the bleaching of palm oil by blowing air or oxygen through it both air and oil being a t 80-90° in the preslence of the salts and oxides of manganese cobalt nickel iron and lead. Manganese borate and particularly cobalt borate,ORGANIC CHEMISTRY. i. 11'7 are found to be very efficient catalysts f o r this purpose f o r 60-70 grams of a crude oil were completely bleached in the presence of 0.01% of the latter by a current of air flowing a t the rate of abouf 17 litres per hour for lhree and a-half hours.The1 bleaching was permanent and oils treated in this way retain their characteristic perfume and soap-making qualities. KNOLL k Co. (D.R.-P. 284762; from J . SOC. Chem. Ind. 1915 34 1166).- Cobalt cliolate [C,,H,50,J,Co is prepared by the interaction of an alkali cholate with a cobalt salt or by other common methods. It readily swells in water but dissolves sparingly in water and alcohol and not a t all It has disinfecting properties when taken internally but therapeutic doses do riot injure the mucous membrane of the stomach. J. C. W. Preparation of a [Cobalt] Salt of Cholic Acid. in ether benzene o r chloroform. J. C. 117. Magnesium Citrate in Aqueous Solution. FRANCINE SWART and C.BLOMBERG ( J . Pharm. Chim. 1915 [vii] 12 387-391).- The authors do not agree with the existence of a heptahydrate of magnesium citrate as described by L6ger (A. 1915 i 496). They explain the slow separation of magnesium citrate tridecahydrate from aqueous solution as due t o the ionisation of the citrate giving rise to two complex ions (compare A. 1915 ii 737) which slowly recombine t o form the molecule which then crystallises as the tridecahydrate. They reaffirm the existence of the basic mag- nesium citrate Mg,CT*OH previously described by Blomberg (Phcwni. Tl~eebblcrd. 1915 September) and explain its formation by means of these complex ions. Magnesium Citrate in Aqueous Solution. E. LI~GER (J. Phnrm. Chim. 1915 [vii] 12 391-394).-A reply t o Swart and Blomberg (preceding abstract).W. G. W. G. Bromoacetglxylose and P-Triacetylmet hylxylosid e. J. K DALE ( J . Amer. Chem. SOC. 1915 37 2745-2747).-By treating xylose with a saturated solution of hydrobromic acid in acetic anhydride a t the ordinary temperature bronzot8.iacetyZx?/Zos~ crystals m. p. 10Zo [a]:" +212.2O (in chloroform) can be produced. This substance in acetic acid solution reacts with silver acetate giving 6-tetra-acetylxylose (compare Hudson and Johnson follow- ing abstract) and when treated in inethyl alcohol with silver nitrate yields 6-triacetyl?nethylxy~os~de thin plate-like crystals m. p. 115O fa]:' -60'5* which is converted by cold dilute sodium hydroxide solution into B-methylxyloside (Fisclier A. 1895 i 439). D. F. T. The Isomeric Tetra-acetates of Xylose.The Acetates of Melibiose Trehalose and Sucrose. C. S. HUDSON and J. M. JOHNSON ( J . ,4?ncr. Chem. Soc. 1915 37 2748-2753).-Tetra- acetylxylose m. p. 128O (corr.) (Stone A. 1894 i 104; Bader A 1896 i 336) when heated in acetic anhydride containing a littlei. 118 ABSTRACTS OF CHEMICAL PAPERS. zinc clilorid-e undesgoes chemical change as is clear from the occur- rence of a marked increase in the optical activity of the solution and there can be separated from the solution an isomeride m. p. 59O (corr.) ; an unstable alcoholate of this substance was isolated as an intermediate product in the process of separation. The1 optical activity of the new compound is [a]go +88*9O in chloroform +80*4O in benzene and +95*S0 in acetic acid whereas for the original compound m.p. 1 2 8 O the values for solutions of approxi- mately the same concentration (approx. 10%) were [ a ] f -25-l0 - 2 2 * 3 O and - 7 . 3 O respectively in the same three solvents; the former compound is therefore termed a-tet,ra-acetylxyIose as a prob- able derivative of the known dextrorotatory a-xylose whilst the less fusible hvorotatory compound is termed P-tetra-acetylxylose from its presumed relationship with the hypothetical P-xylose. On hydro- lysis of the a-tetra-acetyl derivative with alcoholic potassium hydr- oxide at Oo only ordinary xylose was obtained but acetylation of xylose with a mixture of acetic anhydride and commercial pyridine (compare Behrend A. 1907 i 481) gave a mixture of the a- and B-f orms of the tetra-acetyl compound.The tetra-acetylxylose ob- tained by Ryan and Ebrill (A. 1908 i 716) by the action of silver acetate on chloroacetoxylose in acetic acid is shown t o be the P-isomeride and an improved method is given for the preparation of chloroacetoxylose consisting in boiling xylose with acetyl chloride and a trace of zinc chloride until the sugar is completely dissolved. An acetic acid solution of hydrogen bromide rapidly converted both the a- and the P-tetra-acetyl compounds into one and the same bromoacetoxylose (compare Dale preceding abstract) which was convertled by methyl alcohol and silver nitrate into P-triacetyl- methylxylosidk. Melibiose octa-acetate m. p. 177.5O (corr.) [a] + 102.5O and + 101*9O in chloroform and acetic acid respectively when heated a t looo in acetic anhydride containing a little zinc chloride undergoes a marked increase in optical activity presumably due t o the forma- tion of an isomeride but the latter could only be isolated as a syrup.The new and more active isomeride will be the a-form whilst the original compound is t o be represented as the 8-isomeride. Trehalose octa-acetate m. p. 96-98O [ulto + 1 6 2 . 3 O in chloro- form and sucrose octa-acetate m. p. 69O [a]:' +59*6O in chloro- form showed no alteration in optical activity when dissolved in acetic anhydride with a little zinc chloride thus indicating the non- existence of isomerides as would inde'ed be expected from the lack of muta-rotation and the non-aldehydic character of these suqars. D. F. T. A Second Crystalline Lzevulose Pen ta-acetate (a-Lzevulose Penta-acetate).C. S. HUDSON and D. H. RRAUNS ( J . Amer. Chem SOC. 1915 37 2736-2745).-By the action of zinc chloride in acetic anhyAride solut\ion on lzvulose tetra-acetate the authors have obtained a d-lzevulose penta-acetate m. p. 70° [a!." +34*75O (in chloroform) and therefore quite distinct from the isomeric penta- acetate m. p. logo [a]go -120*9* recently described by the authorsORGANIC CHEMISTRY. i. 119 (A 1915 i 502). This new penta-acetate shows the same stability as that earlier described towards zinc chloride and therefore the method applicable to the establishment of equilibrium between aldose acetates fails in this case of a ketose derivative. The penta- acetatei ni. p. 1 0 8 O is obtained when lzvulose tetra-acetate is treated in the cold with sulphuric acid and acetic anhydride so that the same cyclic system must be present in both the penta-acetates which are therefore designated by the terms a- and P- f o r the more fusible and the less fusible isomerides respectively.a-Lzvulose penta-acetate can also be obtained directly from lzvulose by the action of zinc chloride in acetic anhydride solution and by the action of pyridiiie in the same solvent but the process described above is the most satisfactory. The best method for the production of laevulose tetra-acetate is with an acetic anhydride solution of zinc chloride and hvulose a t Oo stopping the reaction as soon as the last substance has passed into solution. A 30% yield of tetra-acetate can thus be obtained. ~ - L ~ v u l o s e penta-acetate when treated with an acetic acid solu- tion of hydrogen bromide is converted into laevulose tetra-acetate probably by way of the corresponding bromoacetyl compound.The a-peiita-acetate is unaffected by similar treatment 60 that it is probably correct t o regard the t'etra-acetate as a P-compound. As the original crystalline lzvulose was a P-compound and as the a- and P-penta-acetates do not give an equilibrium mixture i t is probable that in the production of the former from lzevulose a 113 olecular rearrangement occurs in one of the less acetylated deriv- atives but no experimental indication was forthcoming as to the stage of t.he acetylation at which rearrangement occurs. The authors have also prepared from lzevulose tetra-acetate a crystalline tetra-acetylmethyl-hvuloside which is to be described later.D. F. T. Action of Cyanides of the Alkali and the Alkaline Earth Metals on Sugars. E. RUPP and A. HOLZLE (Arch. Pharm. 1915 253 404-415. Compare A. 1914 i 142).-The preparation of a-glucoheptoic anhydride from dextrose is effected more con- veniently by barium cyanide than by potassium cyanide. The latter causes the formation of dark-coloured by-products but when its hydrolytic dissociation is diminished by the use for example of potassiurn ziacocyanide ths reaction product is obtained and remains nearly colourless. Zinc cyanide o r mercuric cyanide has no action on dextrose in aqueous solution. a-Glucoheptoic anhydride has recently come into use as a diabetic sugar under the name hediosite. Basic barium glucoheptoate OH-CH,*[CH*OH]5*CO*0.Ba.0H colourless crystalline precipitate is obtained by heating hediosite and barium hydroxide (1 rnol.) in saturated aqueous barium hydroxide at' 75O.The basic salt being sparingly soluble can be utilised to isolate the product of the reaction between dextrose and an alkali cyanide the yield of hediosite by this method being 30-33%. The velocity of reaction of a 10% dextrose solution and potassium 11.i. 120 ABSTRACTS OF CHEMICAL PAPERS. cyanide (1 mol.) has been followed polarimetrically the results being controlled by estimations of the ammonia evolved. About one-half of the sugar has reacted within two hours and the reaction ceases after three days. The estimation of the cyanide undecom- posed shows that the coiisumption of the cyanide increases rapidly with the concentration of the solution; the amount of potassium cyanide decomposed in a 10% dextrose solution in a few days is about the same as that decomposed in a 0.1% solution after one month.The consumption of the cyanidel is enormously accelerated catalytically by alkalis; a solution of dextrose and potassium cyanide when faintly acidified with sulphuric acid suffers in the course of weeks no greater loss of cyanide than does the same solution within a few hours after the addition of two drops of dilute sodium hydroxide or a few drops of aqueous ammonia. Mannose and potassium o r barium cyanide react in aqueous solu- tion with the evolution of ammonia and the formation of barium mannosecarboxylate from which the corresponding lactone is 0btaine.d by acidification.Laevulose and potassium or barium cyanide react hydrogen cyanide followed after several hours by ammonia being evolved ; the product obtained by evaporating the solution over sulphuric acid in a vacuum is probably potassium laevulomcarboxylatel but the free acid could not be isolated. The behaviour of galact,ose is quite similar t o that of lzevulose. I n the case of lactose hydrogen cyanide is evolved followed after several days by ammonia. The solution contains a dark-coloured viscous mass which was not further examined ; estimations of the undecomposed cyanide' after the lapse of- days show that the biosel reacts smoothly with 1 mol. of the cyanidel the more rapidly the greater is the coacentration of the solution but subsequently a second molecule of the cyanide is very slowly decomposed.These results are interpreted as indi- cating the formation of potassium lactosecarboxylate which is then hydrolysed to potassium glucoheptoate and galactose the latter being subsequently converted slowly into potassium galactosecarb- ox ylate. The behaviour of maltose is very similar t o that of lactose except that a second molecule of the cyanide scarcely enters int'o reaction. c. s. Preparation of Melibiose. C. S. HUDSON and T. S. HARDING (t7. Amer. Chem. SOC. 1915 37 2734-2736).-By a modification of the method of Bau and Loiseau (A. 1904 i 225 475) the authors have been able t o prepare melibiose from raffinose with a yield of 175-200 grams of pure1 crystalline pro'duct from 500 grams of the triose.Pure raffir-oset (500 grams) obtained by the process of Hudson and Harding (A. 1914 i 1166) was t,aken in approximately 10% aqueous solution together with baker's yeast (10 grams) acetic acid (one or two drops) and malt sprouts (I gram) the latter serving as a nitrogenous food; after thirty-six to forty-eight hours a t the ~ r d i n a r y temperature the optical activity had fallen t o approxi-ORGANIC CHEMISTRY. i. 121 mately that calculated for the resulting melibiose the kevulose having undergone further fermentation to carbon dioxide and alcohol. The solution was then filtered cleared with basic lead acetate solution decolorised by carbon and after evaporation t o a syrup cause'd to crystallise by the addition of alcohol and a nucleus of melibiose.D. F. T. Complex Metallic Ammines. 11. Additive Compounds Formed from trans-DichlorodietbylenediaminecobAltic Chloride. THOMAS SLATER PRICE and SIDNEY ALBERT BRAZIER (T. 1915 107 17 13-1 740).-The f crrmation of the additive compound between trans-dichlorodiethylenediaminecobaltic chloride and thiodiacetic acid (A. 1915 i 942) has led to the investigation of other dibasic acids including not only those containing sulphur but also acids of the oxalic acid series and certain unsaturated dibasic acids. It was found that all dibasic acids do not give rise to additive com- pounds; with one o r two exceptions the compounds formed are of two types which may be formulated as [Cl,Co en,]AH,H,A and [Cl,Coen,]AH where H,A is a dibasic acid. Acids which give compounds of the first type are malonic chloromalonic bromo- malonic glutaric acetonedicarboxylic thiodiacetic sulphonyldi- acetic and maleic acids whilst the following acids give compounds of tlie second type uxalic methylmalonic ethylmalonic dimethyl- malonic diethylmalonic dichloromalonic dibromomalonic succinic dibromosuccinic t'artaric meso-tartaric adipic dithiodiacetic dithiodipropionic fumaric citraconic mesaconic and itaconic acids.Thiodipropionic acid gives a compound of the type [Cl,Co ea,]Cl,H,A. A detailed consideration of the results hitherto obtained by Werner in connexion with analogous compounds together with the above reaults. leads the authors to the conclusion that the additive .-.GI compounds should be formulated as A<H--[--.C1 Co enJAH t l e hydrogens of t'he acid being connected withLthe chloriles of the complex by subsidiary valencies.An explanation of the fact that only certain dibasic acids give additive compounds is given in the light of the results hitherto obtained by Boeseken (A. 1913 i 1147) and Irvine and Steel (A. 1915 ii 669) it being shown that in all probability the acids giving rise t o compounds of the first type have their hydroxyl groups in the &position with respect t o each other malonic acid for example having the configuration ~ O * C H z * ~ o * the hydroxyl groups are then in a favourable posi- OH OH' tion for their hydrogen atoms to combine with the chlorine atoms of the dichloro-compound. Of the acids giving compounds of the second type it is shown that all of thelm with the exception of tlie substituted malonic acids and citraconic acid probably have their hydroxyl groups in the anti-position with respect to each other that is not in a favourable position for their hydrogen atoms to combine with the chlorine atoms of the dichloro-compound.The fact that cert.ain substituted malonic acids together with citraconic f "i. 122 ABSTRACTS OF' CHEMICAL PAPELIS. acid do not give additive compounds although their hydroxyl groups are probably in the cis-position with respect to each other is explained on the assumption that the substitution of hydrogen by radicles with much larger molecular volumes as for example methyl ethyl and the halogens influences the relative positions in space of the hydroxyl groups in such a manner that they are not favourably situated for forming an additive1 compound.I n order t o prepare the various compounds cold concentrated solutions of trans-dichlorodiethylenediaminecobaltic chloride and the acid were mixed the proportions taken being one molecular equivalent of thel chloride t o rather more than two molecular equi- valents of the acid. If no precipitate was formed sufficient sodium carbonate t o form the sodium hydrogen salt of the acid was added when precipitation rapidly took place. When the acid forms an additive compound i t is immateria.1 whether it be present in the reaction mixture as the free acid or the sodium hydrogen salt. All the compounds thus obtained were micro-crystalline. The' fresh aqueous solutions do not contain ionic chlorine but on keeping they slowly change in colour probably with the formation of chloro- aquo-compounds. trans - Dichlorodietlzyle?zediaminecobaltic hydrogen oxalat e YC,04H,2H20 where Y = [Cl2Co en2] forms emerald-green striated and elongated plates. I n one case under conditions which have to be investigated further the trans-dichloro-chloride and ammonium hydrogen oxalate gave crystals of oxalt'c acid-trans-dichlorodi- 4 t hylenedinniiiz eco baltic hydrogen oxalate YC,04E,C,H,0,. From the hydrogen oxalate oxalatodiethylenediaminecobaltic chloride [C,04C0 .en2]C1,4H20 is readily obtained by boiling the solution and subsequent concentration. Mnlonic nci~-trans-~t'ch?orodi- e t hylen ediaminecobaltic hydrogen malonat e forms dark emerald-green blunt prisms ; when the dichloro-chloride and the malonic acid were in the proportions of 2 l by weight instead of 3 :4 as in preparing the above compound mnlonic acid- trans-dichlor~~ietl7tyle~~cdicsmin ecobaltic chloride YCl,CH,(CO,H) was obtained.trans-Dir hlorodie thylenedinmin ecobaltic hydroge tz diethylmaZonat e YC02=CEt;,*C0,H crystallises as emerald-green square plates mixed with a few needles; the corresponding hydrogen dirnet hylmaloriate YCO,*CMe,*CO,H gives nodular aggregates of dark emerald-green crystals. The hydrogen ethyl- mnlonate YCO,*CHEt*CO,H and the h?/drogen methylmalonate YCO2*CHMe*C0,H each form emerald-green blunt-ended prisms. trans-Dichlorodieth ylen edinmineco bal tic hydrogen dibromomalon- Ute YC02-CBr,-C0,H consists of apple-grelen blunt-ended pris- matic crystals; the aqueous solution loses carbon dioxide on the water-bath and on evaporation dibromoacetic acid-trans-dichlorodi- at hylenediaminecobal tic (lib ro monceta te YCiH0,Br,,CHBr2* CO,H is ohtained in the form of milky green irregular plates.Bromomalonic acid-trans-cFichlorodieth ylenediamin eco baltic hydro- .c/e n bromomalond t e YCO,*CHBr*CO,H CHBr (CO,H) crystallises in emerald-green plates; the corresponding chloromalonate YC,O,H,,CH,( CO,H),,2H,O,ORGANIC CHEMISTRY. i. 123 YCOa*CHC1*C!O,H,CHCl(C0,H) also gives emerald-green crystals. Each of these compounds when thoroughly washed with alcohol loses a molecule of the halogenomalonic acid giving respectively trans-dichlorocliethylenediaminecobaltic hydrogen. bromomnlonate YCO,*CHBr*CO,H and the corresponding trans-hydrogen.chloro- nialonate YC0,-CHCl*CO,H. trans-Dicklorodiethylenediamine- cohaltic J L ~ ~ P O Y E I L dichloronzalonate YCO,*CCl,*CO,H crystallises as a conglomerate of light emerald-green plates; the aqueous solu- tion loses carbon dioxide on the water-bath and on evaporation emerald-green crystals of dichloroncetic acid-trans-dichlorodi- ethylen edia 771 ii~eco baltic dichloroaceta te YC,H0,C12 CHCl,*CO,H are obtained. Under similar conditions the additive compound with chloromalonic acid gives emerald-green flat prisms of chloroacetic n c id-tr ans-d i c h 1 or odi e t JL y 1 e 17 eclin nz i n e co b a 1 tic c h 1 or oa c e t a t e YC,H,O,Cl,CH,Cl*CO,H although the p i r e compound is best obtained from chloroacetic acid and the trans-dicliloro-chloride.trans - Dich lorodie th yletzedicrminecob alt ic Jbydrogen succimte Y C0,*[CH2],.C0,H,H,0 cryst,allises in dark emerald-green blunt- ended prisms. The hydrogcia dihromosucciaate YCO,*[CHBr],*CO,H gives malachite-green crystals of indefinite shape. The Jhydrogen tartra t e YCO,* [ CH-OH J2*C0,H H,O and J~ydrogen meso tartrate YCO,*[CH-OH],*CO,H crystallise as a felted mass of emerald-green needles and as an emerald-green conglomerate of very small plates ( 1) respectively. gives dark emerald-green square plates as also does the JLydrogen dith iodinceta te YCO,*CH,*S,*CH,* CO,H,H,O. ThO Ji ydrogcn di- t h io dip4 o pi0 11 n t e Y C 0 C H 11 e S C H Me - C 0 H H ,O gives pa 1 e emerald-green crystals whilst the hydrogen fumarate YCO,*CH:CH*CO,H gives irregular plates of the same colour.The hydrogen citrcrconiite h ydrogeia mesaconnte and hydrogen ifacouate YC5H504 form respectivelv emerald-green crystals pale green plate^ and emerald- green needles. Glutaric ncid-trans-clic~~lorodieth?/lP?iedi~mi7aPco~attic hydrogen glutarate YC0,-[$2H,]3*C0,H,[CH,1,(CO~H)2 gives dark emerald- green elongated plates. The following are also additive compounds Jrydrcqeiz thiodiacetnte YC0,*CH2*S*CH,*C0,H,S(CR,*C0,H) emerald-green plates ; Jbydrogen siilphon?lldincetn't~ very sinall emerald-green plates ; hydrogen maleate einera Id-green needles. d k m in eco hnl t ic h yzroqe n t h i d i n ce tn t e [Br,Co en,]CO,*CH,*S*CH,*CO,H,S( C'R,-CO,H) forms pea-green crystals whilst t hiodipro pionic ncict-trans-dichloro- d ~ e t h ~ l e n e d i a m i n e c ~ ~ a l t i c chloride YCI,S(CHMe*CO,H) crystai- lises in dark grass-green plates.The following cis-isomerides were also obtained cis-dichlorodi- The JLXidrogen adipate YCO,*[CH,],*CO,K YCO,*CH,*SO,*CH,*CO,H,SO,( CH,*CO,H) YC,H,OI ,C,H,O Thiodince t2 c ncid-trans-dibroi,iodie th ?$en e- f * 2i. 124 ABSTRACTS OF CHEMICAL PAPERS. ethyle,zedian~iizeco~altic oxdate Y2C204 violet crystals ; cis-hydro- gen succinate YC0,*(CH,)2*C0,H violet short bluntrended prisms ; and cis-udipate Y2(C0,),(CH2) violet prisms with blunt ends. A pure substance was not isolated from acetonedicarboxylic acid but the results indicated the formation of an additive compound. A solution of the additive compound formed with thiodiacetic acid when treated with potassium iodide gave a vivid green precipi- tate consisting of a conglomerate of very small tabular crystals of t r a ns-d ic h 1 or odi e t h y 1 e n edia min e co b n I f ic iodide YI.T . S. P . A New Oxidation Method. 111. Action of Aldebydes on Primary Hydroxyamines. I<. HESS and CL. UIBRIG (Ber. 1915 48 1974-1985. Compare A 1914 i 199).-The behaviour of liydroxylated primary amines towards formaldehyde acetaldehyde and benzaldehydel has been investigated. When diacetonalkamine is treated with formaldehyde in the cold i t first condenses according to the scheme NH,*CMe2*CH,*CHMe*OH + CH,O f OH*CH,*NH*CMe2*C€12*CHMe8-OH. A t about 50° however the product is an anhydride of the latter compound namely methylerLediacetonal?camine [P-methylene- nmin~o-~-r~zeth~/lpetztan-b-ol] CH,:N*CMes*CH,*CHMe*OH which is a very pale yellow oil b.p. 45-47O/23 mm. 150-155°/720 mm. and forms a picrate C,,H,,O,N long stout spikes m. p. 138-139O. I n the earlier paper this was mistaken f o r the isomeric diaceton- methylamine XHMe*CM%*CH,*COMe but it cannot be that for it is formed too easily and is too easily hydrolysed. A t higher tem- peratures further reactions take place. Thus when diacetonalk- amine was heated with 40% formaldehyde a t 142-145O in a sealed tube and the product was extracted with ether and then fraction- ated the following were isolated the above methylenediacetonalk- amine then d i m e tondimet h ylamine Ip-dirnethylamino-p-met hyl- p n t a n - & o n e ] NMe,*CMe,*CH,*COMe b. p. 59-61°/23 mm. a limpid mobile' highly refractive oil with a strong narcotic odour (picrate m.p. 183O) and finally methyldiacetonalkamine NHMe-CM%*CH,*CHMe*OH b. p. 73-75O/ 20 mm. The chief product obtained by heating diacetonalkamine with 40% acetaldehyde acidified with hydrochloric acid at) 115-120° was ethylene~iacetonalkamine r?-eth.ylenea?nino-P-m ethylpentan - 6 - 011 C,H,,ON a colourless mobile oil b. p. 42-47O/12 mm. with a powerful narcotic odour ( p i c m t e stout needles m. p. about 147O). Similarly benzaldehyde yields bemylidenediacetonalkamine [P-benz- ylidcn ect mi72 o-&met hylpen tan-8-01] CHPh:N*CMe2*CH,*CHMe*OH a yellow oil b. p. 94-95O/0*1 mm. 139-140°/19 mm. with a faint basic odour ( p i c m t e long prismatic needles m. p. 170-171°). The base is quickly transformed into the hydrochloride pink m.p. 199O when covered with concentrated hydrochloric acid and it is readily hydrolysed even in water. The urethane of diacetonalkamine [&xwbethoxyamino-j3-methyl- pen tnn-&ol] CO2Et-NH*CMe2-CH,-CHMe*OH was prepared as aORGANIC CHEMISTRY. i. 125 viscous oil b. p. 14Z0/23 mm. by the agency of ethyl chloroformate. When this is heated with an excess of 40% formaldehyde a t 145-1 50° it forms 0-carb e thoxy met hylamino-/3-methylpentan-6-one C02Et*NMe*CM~-CH2*COMe b. . p. 123-125O/ 14 mm. which readily yields formaldehyde again in the presence of water. If the urethane is mixed with alcohol and formaldehyde and heated a t ZOOo however it yields the melthylene cornpou?zd (OH*CHMe*CH,*CMe,*NH)2CH2 which crystallises in the triclinic system and has ni.p. 132O b. p. 165-170°/25 mm. Aminoethyl alcohol was shaken with propyl chlorof orinate and sodium carbonate solution and converted into ~ - c n r b o p r o p o x ~ a m ~ n o - ethyl alcohol C0,Pr.NH*CH,*CH2*OH a viscous oil b. p. 150-151°/13 mm. When this is heated with 40% formaldehyde a t 145O it yields carb opropoxymet h ylaminoacetaldehycle CO2Pr*NMe*CH,*CHOY a highly refractive limpid pleasant-smelling oil b. p. 103-105°/ 13 mm. which reduces ammoniacal silver oxide and forms a hydr- azone. /3-Amino-a-phenyletliyl alcohol obtained by reducing benzalde- hyde cyanohydrin by sodium amalgam was also converted into the ure tA a n e [ fl-carb e t hox?ya rn in. o-a-phe nyle t h y l alcohol] OH* CHPh.CH,*NH*CO,Et pearly leaflets m. p. 8G0 by the agency of ethyl chloroformate.When this is heated with excess of formaldehydel a t 140-145O it yields phenyl car6ethox?/methylami?~omet~~~l I* ,,e t one COPh*CH,*NMe*CO,Et b. p. 181-183O/16 mm. Behaviour of Amino-acids towards Neutral Salts in Aqueous Solution. P. PFEIFFER [with J. ~ U R G L E R and FR. ~ ~ I T T K A ] (Ber. 1915 48 1938-1943. Compare A. 1915 i 868).-In connexion with physiological processes it is important to determine whether the corcplex ‘‘ neutral-salt compounds ” of the amino-acids and poly- peptides with salts of the alkali and alkaline earth metals can exist as such i n equilibrium with their components and complex ions in aqueous solutions. This has been tested by determining tlie solu- bilities of various amino-acids in salt solutions by observing the influence of salts on the rotation of d- and Z-alanine in aqueous solution and by measuring the depression of tlie freezing point of w a k s containing glycine and various salts.I n all cases in which “ neutral-salt compounds ” are known t o exist in the solid state the solubility of the amino-acid in the particular salt solution is much increased. The1 rotation of alanine is raised as much as six times by certain sdts just as it is by mineral acids. The depression of the freezing point of water caused by glycine+a salt is less than the sum of the depressions caused by the separate solutes. It seems therefore t h a t the complex molecules do exist in aqueous solution. J. C. W. Preparation of Compounds of Urethanes and Diurethanes with Metallic Bromides.GEHE & Co. (U,R.-P. 284734; from J. C . W.i. 126 ABSTRACTS O F CHEMICAL PAPERS. J . SOC. C h m . Ind. 1915 34 1166).-Urethanes (4 mols.) are heated with calcium or strontium bromide (I mol.) in a suitable solvent for several hours. The products especially the double compound of calcium bromide with ethyl carbamate CaBr2,4NH,*CO,Et are powerful liypnotics and are useful in the treatment of nocturnal epilepsy; they have no deleterious action on the heart o r respira- tion. J. C. W. Preparation of Carbamide Nitrate from Cyanamide. OESTER- REICHISCHER VEREIN FUR CHEM. UND METALL. PRODUICTION (D.R.-P. 285259; from J . SOC. Chem. Z7zd. 1915 34 1166).-Carbamide nitrate is precipitated almost quantitatively when concentrated solutions of cyanamide and nitric acid are mixed a t below 20° thus CN-NH + HNO + H,O = CO(NH,),,HNO,.J. CT. W. Reaction of Nitroprusside with Thiocarbamide. L~VIO CAMBI ( d t t i R. Accad. Lincei 1915 [v] 24 ii 434-441. Compare A. 1913 i 606; 1914 i 967).-The author has investigated the reddish- violet salt obtained by Hofmann (A. 1900 i 591) by the action of sodium nitroprusside on thiocarbamide and regarded by him as having the formula [Fe(CN),NO*S*C(NH)*NH,INa,. That this formula is erroneous is shown by the analytical results which give 1 7 and not 1 8 for the ratio Fe N ; in correspondence with this fact is the author’s observation that the synthesis of the compound is accompanied by the liberation of nitrogen. It is known also that in presence of a weak acid alkali nitrites transform thiocarbamide into thiocyanic acid with quantitative evolution of nitrogen (com- pare Werner T.1912 101 2180; Coade and Werner T. 1913 103 l22l) NH,*CS*NH -+NH,*CS*OH -f HNCS. The assump tion is theref ore made that the nit“roso-group of the nitroprussids reacts not with the sulphur atom but with the amino-groups of the thiocarbamide KaOII 3Na2Fe(CN),N0 + CS(NH,),-+ Na,[Fe”(CN),NO-NH*CO*SH] + Na3[Fe(CN),,H,0] + N2 the first of these products representing Hofmann’s reddish-violet salt. The formation of the aquo-salt (compare Hofmann Zoc. cit.) in considerable proportion has indeed been observed and the accuracy of this representation of the reaction is indicated by the following results. The interaction of sodium nitroprusside and thiocarbamide in methyl-alcoholic solution in presence of excess of sodium alkyloxide yields an orange-yellow salt which undoubt- edly contains one thiocarbamide residue t o two atoms of iron and has probably the formula Na,[Fe”(CN),. ..NO*NH*CO*S*Fe”(CN),] ; in aqueous solution this’ compound decomposes with formation of Hofmann’s salt. Treatment of the latter with sodium hydroxide in aqueous methyl-alcoholic solution yields a deliquescent brownish- orange-yellow salt of the composition Na,[Fe(CN),NO*N*CO*S] ; this undergoes irnniediate hydrolysis t o the original salt in aqueousORGANIC CHEMISTRY. i. 127 solution whilst when kept for a long time in a vacuum in presence of water it undergoes partial decomposition with liberation of nitrogen dioxide. By silver or mercuric salts in the hot Hofmann’s salt is rapidly decomposed with liberation of nitrogen dioxide in the proportion l N 0 1Fe ; under similar conditions the salt obtained from thiocarbamide in methyl-alcoholic solution liberates nitrogen dioxide in the proportion 0*5NO:lFe in accordance with the formula given above.Reduction of Hofmann’s red salt by means of sodium amalgam gives a yellow salt Na,[Fe//(CN),*NH,*NH*CO*SH] in which the presence of the hydrazine residue NH,*NH* is demonstrated by the behaviour towards mercuric salts or oxide silver salts or Fehling’s solution whicli cause rapid decomposition with liberation of nitrogen even in the cold; bromine water also liberates nitrogen but yields no nitroprusaide whereas under similar conditions the red salt gives nitroprusside but no gas.Hofmann’s formula was based solely on the reaction of the red salt with ferric chloride which gives a green coloration o r precipi- tate but the author has observed similar behaviour with ferro- cyanides containing nitroso-ke$ones these being also intensely coloured. The possibility of the formula Na,[Fe///(CN),NO*NH*CO*S~ for the red salt is discussed; this salt does not however exhibit the characters of ferricyanides whilst the ferrous formula is in accord with its behaviour towards alkalis. T. H. P. The Hydraeide of Cyanoacetic Acid Oximinocyanoacetic Acid and Nitrocganoacetic Acid. AUGUST DARAPSKP and DIETRICH HILLERS ( J . pr. Chem. 1916 [ii] 92 297-341).-Methyl cyano- acetate (1 mol.) when heated in alcoholic solution with hydrazine hydrate (2 mols.) was converted into cyanoacetylliydrazide the hydrocJdoricle (crystals m.p. 145O) of which when treated in aqueous solution with sodium nitrite under a layer of ether was converted into cyanoucetylazide CN*CH,*CO-N a pale yellow explosive oil of extremely pungent odour ; this substance reacted with aniline in ethereal solution giving cyanoacetanilide and with boiling alcohol yielding cyaiao?izeth~luretl~ane CN-CH,*NH-CO,Et silky needles or slender prisms m. p. 1 4 5 O . When heated with diluted hydrochloric acid the urethane compound underwent dis- ruption giving carbon dioxide alcohol ammonia and glycine aminoacetonitrile probably being formed as an unisolatable inter- mediate product. The last reaction is of little importance as a method of preparing glycine but an analogous series of reactions with the alkyl derivatives of ethyl cyanoacetate may prove useful for the preparation of other amino-acids. It is of interest that the above method for the preparation of glycine from chloroacetic acid through cyanoacetic acid gives a product in which the amino-group and the carboxyl groups are held by different valencies from those occupied by the same groups in the product prepared by the action of ammonia on chloroacetic acid.These two modes for the prepara- tion of glycine can therefore serve as the basis of a proof of t h oi. 128 ABSTRACTS OF CHEMICAL PAPERS. equivalence of the four bonds of the carbon atom by applying them to ordinary chloroacetic acid and t o chloroacetic acid prepared by the stages CH2Ci40,H -+ CN*CH,*CO,H -+ C0,H*CH,*C02H + CO,H*CHCl*CO,H + CH,Cl*CO,H and CH,C1*C02H + CO,H*CH,*CO,H + CO,H*CH@l*CO,H -+ CO,H*CH(CO,H)*CO,H + CO,H*CCl(CO,H)*CO,H -+ CH,Cl*CO,H.Methyl oximinocyanoacetate (Conrad and Schulze A. 1909 i 21 1) reacted with an equimolecular proportion of liydrazine hydrate in alcoholic solution giving the hydmzine salt CN*C (:NO*N,H,)*CO,Me a yellow crystalline solid decomp. near looo after sintering a t 7 8 O . When the reagents were heated together in alcoholic solution on a water-bath the product was the ltydrazine salt yellow needles decomp. a t 1 3 5 O of oximinocyanoacetylhydrazine lustrous brown leaflets m. p. 1 6 6 O (decomp.) the latter being liberated from the salt by careful treatment in the cold with thel theoretical amount of hydrochlonc acid ; silver salt brown ; lead salt brown ; hydro- chloride yellow crystals decomp.a t 204O. If the hydrazine salt is treated in aqueous solution with benzaldehyde benzaldazine and oxim itmcynn oace t y l be n z?llidenekydruzitae CN*C(:NOH)*CO*NH-N:CHPh yellow needles decomp. a t 1 4 8 O are obtained the latter compound being also produced by the action of benzaldehyde on oximinocyano- acetylhydrazine itself. The hydrazine salt reacts in an analogous manlier with an excess of acetone giving bisdimethylazimethylene and oximinocyanoacet ylisopropylidene hydrazine CN*C( :NOH)*CO*NH*N:CMe coinpact yellow prismatic crystals m. p. 2 0 5 O . When the hydr- azine salt of oximinocyanoacetylhydrazine is treated in concen- trated aqueous solution under a layer of ether with sodium nitrite and dilute hydrochloric acid oxirninoc.yanoacetylazide CN*C(:NOH)-CO*N an explosive yellow crystalline solid of low m.p. is obtained which reacts with sodium hydroxide solution and aniline respec- tively giving sodium azoimide and oximinocyanoacetanilide (Dim- soth and Dienstbach A. 1909 i 62) and with Soiling alcohol yielding oximin ocyanomet Jtylure thane CN-C( :NOH)*NH* CO,Et colourless granular crystals m. p. 96-97O. Hydrolysis of the last product with hydrochloric acid gives rise to carbon dioxide alcohol ammonia hydroxylamine and oxalic acid the latter substances probably resulting from the decomposition of an intermediate amino-oximino acetonitrile NH,* C ( NOH) *CN. Jf e t h yl ? I i t rocyanoa ce fat e CX*CH(NO?) *CD2Me colourless silky needles (with lH?O) m.p. 76O was obtained as its potnssium salt CN*C(:NO,K)*CO,Me lustrous leaflets m. p. 2 6 4 - 2 6 G O (decomp.) by oxidation of methyl oximinocyanoacetate with potassium per- nianganate in aqueous solution; the free ester was liberated by converting it into the silver salt and decomposing with hydrogen sulphide. When treated in warm methyl-alcoholic solution with an equimoleoular proportion of hydrazine hydrate this ester gave aORGANIC CHEMISTRY. i. 129 yellow crystalline hydrazine salt m. p. 1 6 8 O but with longer heating and a sesquimolecular quantity of hydrazine hydrate the product was the hydrazine salt CN*C(N02*N2H,)*CO*NH*NH2 silky needles m. p. near 200° (decomp.) after sintering near 140° of nitrocyanoacetylhydrazine ; this hydrazine salt when treated with benzaldehyde yielded benzaldazine and the free nitrocyanoacetyl- liydrazine.By treating the potassium salt of methyl nitrocyano- acetate with hydrazine hydrate the analogous PO tassium salt CN*C(NO,K)*CO*NH*NH' long prisms was obtained. Nitrocyano- acetybhydrazide CN*CH(NO,)*CO*NH*NH obtained by the action of dilute hydrociiloric acid on the above hydrazine o r potassium derivative forms colourless needles (with 1H,O) and can be recrystallised rapidly from warm water without alteration but on boiling with water it is converted into the yellow anhydrous com- pound a similar dehydration being also effected in the hydrated saIt by heating a t 110-120O. The nitro-group renders nitrocyano- acetylhydrazide decidedly acidic in character and it is probably to this cause that the noteworthy stability towards acids and alkalis i3 due; even when boiled with sodium hydroxide solution o r dilute sulphuric acid for hours no scission of hydrazine occurs and even heating f o r six hours a t 120-130° with hydrochloric acid in a sealed tube only causes a partial hydrolysis. When treated with excess of hydrazine hydrate the hydrated form of nitrocyanoacetyl- hydrazide gives the above-described colourless hydrazine salt but the anhydrous compound yields a yellowish-red isomeride decomp.a t 200° after Pinbring a t 185-195O which when its red aqueous solution is acidified regenerates the anhydrous form of the free compound whereas under similar conditions the colourless hydr- azine salt yields the hydrated compound.The ammoizizcm salt also was obtained in an almost colourless form and in an orange-yellow form both crystaking in needles. Indications werel also obtained of the existence of a coloured modification of the potassium salt. This existence of two isomeric series of salts is regarded as analogous to the case of the nitroketones and dinitroparafins (Hantzsch A. 1907 i 500 555 ; Hantzsch and Voigt A. 1912 i 151 ; ii 508). By shaking with benzaldehyde in aqueous solution containing a little hydrochloric acid nitrocyanoacetylhydrazine can be converted into the benzylidene derivative# CN*CH(NO,)*CO*NH*N:CHPh a microcrystalline powder which carbonism without melting and is very readily resolved by warm water into benzaldehyde and nitro- cyanoacetylhydrazide.Sodium nitrite in aqueous solution reacts with nitrocyanoacetylhydrazide giving the sodiunz salt (yellow needles) of the ?zitroc?/anocccet?/lazidp CN*CH(NO,)*CO*N an almost colourless crystalline hygroscopic mass (with 1H,O) of low 111. p. which was obtained by cautious treatment of the salt with dilute sulpliuric acid. pale yellow granular crystals and when boiled with alcohol pro- duced a brown tarry mass which probably contained some of the expected urethane as treatment with boiling hydrochloric acid gave rise t o the formation of carboq dioxide ammonia and hydrogen The azide gave an aniline salt C,H803N,,H9O,i. 130 ABSTRACTS OF CHEMICAL PAPERS. cyanide ; in boiling aqueous solution also nitrocyanoacetylazide decomposes vigorously the products being similar t o the final pro- ducts from the treatment with hydrochloric acid with the addition of carbon monoxide.The above results iiidicate that with the intro'duction of the cyanoacetyl- oximinocyanoacetyl- and nitrocyanoacetyl-radicles into liydrazine this compound undergoes a gradual and regular weaken- iiig in basic character. D. F. T. Preparations of Esters of Hydrazinemonocarboxylic Acid. E. MERCK (D.R.-P. 285800; from J. SOC. Chem. Zizd. 1915 34 11 67) .-Reaction is brought about between equimolecular propor- tioiis of hydrazine hydrate and an ester of carbonic acid. J. C. W. Relations between the Constitution and the Physical Pro- perties of Isomeric and of Homologous Hydroaromatic Compounds. K. VON AUWERS (Annalen 191 5 4 10 287-336. Compare following abstract).-The author has collected from all trustworthy sources the magnitudes of the b.p.'s densities refrac- tive indices and exaltations of the specific refractions and disper- sions of cyclohetxane cyclohexene cyclohexanol and cyclohexanone and as far as possible of their mono- di- tri- tetra- and penta- methyl derivatives; in a few cases values f o r the methylene deriv- atives of cyclohexene and its methyl hoinologues are recorded. The data have been sifted and tables compiled containing values some of which are quite trustworthy others are the most probable and yet others am somewhat uncertain. Relations are then traced between these values and the constitutions of the various com- pounds. The most important of these are the following I n the case of isomeric compounds (I) the b.p. of saturated alcohols and ketones falls when the methyl group is in proximity to the hydroxyl or carbonyl group; the b. p. of unsaturated hydrocarbons rises with approximation of the methyl group t o the double linking. (2) The density in all four classes of compound increases with the pscking of the methyl groups in the molecule and with their proximity to the double linking the liydroxyl group o r the car- bony1 group. (3) Similar relations hold although less pronouncedly f o r the refractive indices. (4) The molecular refraction of isomeric substances of all four classes is greater the farther are the side- .chains from on0 another and from the double linking o r the oxygen- ated group. (5) The molecular dispersion is normal in all saturated and in endocyclic unsaturated compounds.The preceding relations only hold f o r mono- and di-methyl deriv- atives; in the case of more highlv methylated compounds generalisa- tions cannot be made owing to lack of trustworthy data. With regard t'o homologous compounds (1) I n cyclohexanes and cyclohexenes the introduction of methyl regularly causes an increase in the b. p. but in cyclohexanols and cyclohexanones such is fre- quently not the case. (2) As a rule the density of the oxygenated derivatives decreases as the number of methyl groups increases.ORGANIC CHEMISTRY. i. 131 (3) No regularities can be tsaced for the refractive indices of homo- logous compounds since here the constitutive influences are alto- gether predominant. It is noteworthy however that with few exceptions the value of )?go for all homologues of cyclohexene is the same about 1.445.c. 5. Simple Hydroaromatic Hydrocarbons Alcohols and Ketones K. VON AUWERS R. HINTERSEBER and WILHELBI TREPPMANN (A nnalen 1915 410 257-287).-Tlie compounds described in the paper are f o r the most part not new but have been prepared in a state of great purity and the magnitudes of various physical pro- perties hcve been measured in order to correlate these with t.he constitutions ; the saturated hydrocarbons and ket'ones are believed to be quite pure but the authors do not guarantee that the alcohols and unsaturated hydrocarbons are free from possible stereo- isomerides. The alcohols are hygroscopic and the observation has been made that the density continuously increases when these are submitted t o prolinged dryiiig a t a gentle heat in a current of hydrogen.Phosphoric oxide is recommended for convertihg secondary carbinols into unsaturated hydrocarbons and potassium hydrogen sulphate f o r tertiary carbinols. Saturated hydrocarbons are best obt'ained from secondary carbinols through the bromides. cycZoHexane has b. p. 80-0-80~2"/749 mm. D:1'2 0-7869 na1*42910 W~ 1.431 19 ?zP 1.43668 and 7 z y 1.441 16 st 10.85O. cycZoHexene has b. p. 83-83-5"/760 mm. I):"'6 0.8143 YZ 1*44653,1z 1.44981 nB 1.45620 and ny 1.46194 at 15.1". Methylenecyclohexane has b. p. 100~5-102~3'/756 inm. DY 0.8055 n 1.44934 nu 1.45222 ?zp 1.45958 and n 1.46568 a t 15.5'. 1 3 Diniethylcyclohexane prepared by Crossley and Renouf's method (l'.1905 87 1497) has b. p. 118-130' D,2180*7701 7 z a 1.42157 ?zD 1-42398 i z B 1.42940 and ~ ~ ~ 1 . 4 3 3 9 4 at 32.0'. 1 8-Dimethyl- Al-cycZoliexene has D:3'7 0.83 15,7t 1 *45906 n 1.46 1 i 8 '125 1.46908 and iz. 1 4'7517 at 13.5'. 1 3-Dimethyl-A3-cycZoliexene has b. p. 121-126°/760 min. 13g2'6 0.7998 1~~1.44863 n 1.44533 I L 1.45215 and uy 1.46795 at 22.4". 1 3-Dimethy1-4~-cycZohexeiie has b. p. 126-127*/746 mni. 0.797 PZ 1*44086,1z 1.64361 7l.B 1*45020 and ?iY 1.45587 at 21*lG. 1 4-Dimethyl-hl-c?ycZohexene has b. p. 124-126'1751 niin. 0-7985 I L 1-44112 7~~1.42372 izB 1.45056 and ny1.45636 at 22.0'. Ethylidenecyclohexae has b. p. 1 36.0-136-4°/7G6 niiii. D:' 0.8239 7~~1.46094 n,1-46389 ?zJ 1.47139 and i i Y 1.47773 a t 17.6". 1 3 5-Trimethylcyclohaxene b p.139-141"/766 mm. D:" 0.7941 w a 1.44102 7zD 1*4437S 128 1.45057 and iz 1.45638 at 24.7' reacts with hydrogen chloride and with hydrogen bromide in cooled glacial acetic acid to form 1 3 5-tI.inzethyLcyclohexyl chloride b. p. 68-69"/20 mm. Uy5 0.9217 ~ ~ ~ 1 . 4 5 1 8 2 12 1.45455 I Z ~ 1.46035 and IT 1.46555 a t 15*Z0 and the bromide lo. p. 95 -98"/23 Dim. Dil'l 1.1749 na1-47951 n,1*48380 9zp 1.48971 and ny 1.49532 at 11.1" ; neither of these derivatives could be satisfactorily converted into 1 3 5-trimethyl- cyclohexane.i. 132 ABSTRACTS OF CHEMICAL PAPERS. 1 3-Dinzethy1-5-?~zethylenecylohexa?ze C,H,Me,:CH prepared by heating 1 3-dimethylcyclohexylidene-5-acetic acid a t about 220' in a slow current of carbon dioxide has b. p. 135-136'/744 mm.D:4.60 7918 n 1.44334 n 1.44628 np 1*45313',and ny 1,45917 at 14.6" and yields 1 3-dimethylcycZohexan-5-one by oxidation with faintly alkaline 2% potassium permanganate. cycZoHexano1 has m. p. 23' Di7" 0.9373 nu 1.45902 n 1.46055 ?zp 1-46685 and ny 1.47146 a t 37.0". 1-Methylcyclohexanol has m. p. np 1.46428 and ny 1.46908 at 24.65'. I-MethylcycZohexan-2-01 has b. p. 167*4-167*6" D:"" 0.9333 n 1.46352 nD 1.46585 np 1.47180 and ny 1.47665 a t 13.4'. 1-Methyl- cyclohexan-3-01 has b. p. 76-78'/14 mm. D2'3 0.9182 nu 1.45217 72 1.45444 np 1-46031 and ny 1.46502 a t 24.3'. 1-Methylcyclo- hexan-4-01 has b. p. 74.7-75.3'/12 mm Dy5 0.9183 nu 1.45366 n D 1.45594 np 1.46160 and ny 1.46651 a t 32.5'. 1 3-Dimethylcyclohexan-3-01 has b. p. 79-81'/21 mm. DF'9 0.9028 1~~1.45177 nD 1.45414 np 1.45984 and ny 1-46463 a t 22.9'.1 4-Dimethylcyclohexan-4-01 has b. p. 70-72'/19 mm. (Sabatier and Mailhe and also Wallach have obtained this substance in the solid state) D~90*9060 nu 1.45317 n 1.45534 np 1.46141 and ny 1,46622 at 23.9'. 1 3-Dimethylcyclohexan-5-01 has m. p. 36-38' (other preparations remained liquid) DF'4 0.8810 nu 1.44440 n 1.44700 np 1.45238 and ny 1.45727 at 38.4'. 1 3 5-Trimethylcyclohexan-5-01 has b. p. 82-83'/19 mm. D:6'300.8880 n 1,45108 n 1.45371 np 1.45991 and ny 1.46422 a t 16.3". cycloPentanone has b. p. 23*2-23-6'/10 mm D:"3 0.9513 n 1.43587 n 1 43817 np 1.44390 and ny 1.44867 a t 17*33. cyclo- Hexanone has b. p. 156*6-156*8" Dy'3 0.9503 nu 1.45024 rt 1.45261 nS 1.45859 and n 1.463'70 a t 15.3'. cycLoHeptanone has Dy'9 0.9495 n 1.45801 n 1.46027 n p 1.46646 and ny 1.47149 at 21.9'.1-Methylcyclohexan-2-one has b. p. 167'/740 mm. 0.9300 n 1-44827 n 1-45049 np 1.45653,and ny 1.46135 a t 14.6'. 1-Methyl- cycZohexan-3-one has b. p. 60-60*2'/15 mm. D:'l5 04139 nu 1.44092 IZ 1.44313 np 1.44914 and nv 1.45394 a t 25-15'. 1-Met,hylcyclo- hexan-4-one has b. p. 55*8-56*4'/10.5 mm. 0.9119 n 1.44092 ~ ~ ~ 1 . 4 4 3 2 2 np 1.44918 and ?zy 1.45413 a t 24.4'. 1 3-Dimethylcyclo- hexan-5-one has b. p. 180' D:*'7 0.8962 1~~1.44270 n 1.44492 24-25' b. p. 56.5'/10 mm Dt4'" 0.9251 %,1.45631 n D 1.45874 np 1.45101 and ny 1.45579 at 14.7'. c. s. Thermal Reactions of Aromatic Hydrocarbons in the Vapour Phase. W. F. RITTMAN 0. BYRON and G. EGLOFF (J. Ind. 13mg. Chem. 1915 7 1019-1024. Compare this vol.i l).-The decomposition of aromatic hydrocarbons when heated in the vapour phase proceeds in the direction cymene + xylem -+ toluene + benzene -+ naphthalene + anthracene + tarry matter carbon and gas and scarcely appreciably in thel reverse direction. Any one hydrocarbon therefore gives rise t o any or all of the products following it in the above scheme according to conditions and not t o any of those preceding it. The paper is fully illustrated withORGANIC CHEMISTRY. i. 133 tables ahowing the quantitative results of the cracking experi- ments. G. 3'. M. Some Aromatic Fluoro-derivatives and the Nitration of p-Fluorochlorobeneene. FRED. SWARTS (Rec. ti-av. chzm. 1915 35 131-153).-A quantitative study of the nitration of pfluoro- chlorobenzene a number of fluoro-compounds being prepared and used f o r the identification of the products of nitration.The p-fluorochlorobenzeiie used was prepared from p-fluoroaniline by Gatterman's reaction. It had m. p. -26'9O; b. p. 130*15O/757.3 inin. (corr.) ; DO 1.2573; D11.2 1.2355 ; 72 '' 1.49432 ; 7~:'~ 1.50957 ; 9~:''~ 1.52085 ; nY2 1.49890 (compare Wallach and Heusler A. 1888 362). 6-I"l~~o~o-3-~7~1oro-l-nitrob en.ze12 e is prepared by diazotising 4-fluoro-3-nitroaniline in solution in concentrated hydrochloric acid. It crystallises from light petroleum in colourless prisms m. p. 10*2O b. p. 138.5/29 mm and is readily decomposed by aqueous alkali hydroxides giving the Corresponding salts of 4-chloro-2-nitrophenol. With sodium methoxide a t 25O the fluorine atom is replaced by the group *OMe and with alcoholic ammonia 4-chloro-2-nitroaniline is obtained.Attempts t o prepare 5-fl~oro-2-chloro-l-nitrobenzene by the action of phosphorus pentachloride on 4-fluoro-2-nitrophenol were not suc- cessful but i t was finally obtained from the corresponding fluoro- nitroaniline. pFluoroacetanilide when nitrated with acetyl nitrate in acetic acid solution a t Oo yielded 4-flzioro-2-?zitroacetanilide pale yellow prisms m. p. 71*5O which on hydrolysis with dilute hydro- chloric acid gave 4-fZ1coro-2-nit~oaniZ~~ze~ orange-coloured prismatic crystals m. p. 92-45O. This aniline when submitted t o Gatterman's reaction gave 5-fZzioro-2-chloro-l-nitrobe?~zene prisms in. p. 37.25O ; b. p. 238'5O. It is much more resistant to the action of alkalis than its isomeride being unacted on in the cold but when heated with sodium methoxide in a sealed tube at l l O o for thirty hours both the chlorine and tlie fluorine atoms were removed and the substance resinified.p-Fluorochlorobenzene was nitrated by slowly adding it t o con- centrated nitric acid cooled to -loo the temperature not being allowed t o rise above -7O the product being finally poured on to ice. The unchanged fluorochlorobenzene was distilied off under re- duced pressure and a small amount of 2-chloro-5-nitrophenol formed was removed by washing with a solution of sodium carbonate. The final nitrated mixture had a solidification point 23*75O and was analysed first by decomposition of the 6-fluoro-3-chloro-1-nitrobenz- ene with sodium metlioxide a t 25O and secondly by preparing the solidification-point curve of mixtures of the pure isomerides.The two methods agree in showing that in the nitration the NO group enters the ortho-position to the chlorine t o the extent of 62.25% and into the ortho-position to the fluorine to the extent of 27.75%. W. G. m-Difluorobenzene and its Nitration. FRED. SWARTS (Bee. trav. chim. 1915 35 154-165).-m-Difluorobenzene is readilyi. 134 ABSTRACTS OF CHEMICAL PAPERS. obtained by the diazotisatioii of rn-fluoroaniline in liydrofluoric acid solution followed by distillation. It has b. p. 82.8-82*85°/ 757.3 mm. 82*2O/742 mm. (cori-.) ; D15.5 1.1651 ; 17fij.j 1.43601 ; 144871 ; It was nitrated by slowly adding it t o coiicentrated nitric acid a t -4-Oo the product being poured on t o ice after one hour.When purified the product had m. p. 9 ' 5 2 O ; DI34 1.4577; 122 1.50998 ; T Z ~ ' 1.53220 and was mainly 2 4-diflu-oro-1-nitrobenz- ene with a trace of some other compound. A determination of the depression of the freezing point of pure 2 4-difluoro-1-nitrobenzene by the addition of fluorodinitrobenzene showed that the original nitration product contained a t the most 0.434% of 1 3-difluoro-2- nitrobenzene. 2 4-Difluoro-1-nitrobenzene is decoinposed by sodium methoxide giving 5-flr~oro-2-nitronnisole rn. p. 48.B0 b. p. 272O together with some 4-nitroresorcinol ni. p. 73O. When reduced with iron in the presence of sulphuric acid thel difluoronitrobenzene yielded 2 4-difluoronniliile m. p. - 7*5O b. p. 169*5O/ 753 mm. giving 2 4-difluoro~cetcsnil~~~ 111.p. 120'9O. When nitra.bd in the warm o r a t looo by nitric acid (D 1-52) and sulphuric acid m-difluorobenzene yielded quantitatively 4 6-6;- flzcoro-1 3-dinitrobeizzene colourless prisIyLs m. p. 74O. With sodium methoxide a t the ordinary temperature i t yielded the dimethyl ether of 4 6-dinitrcresorcinol m. p. 155*4O and with alcoholic ammonia in excess a t the ordinary temperature 4 6-dinitro-m- plienylenediamine m. p. 296O. Using cnly 2 mols. of ammonia the product was 3-fluoro-4 6-dinitrocniZine 111. p. 186*6O together with a small amount of 4 6-diiiitro-m-phenetid~~~ ni. p. 169O. Preparation of [Chlorine] Substituted Products of Toluene. L. CASSELLA & Co. (Eng. Pat. 16317 (1914); from J. Sac. Chem. Ind. 1915 34 1203).-Dry chlorine is passed over dry toluene in presence of anhydrous iron chloride a t 12-15O the mixture being stirred.When the trichlorotoluene which is thus formed crystal- lises out the temperature is raised t o 35O gradually increasing to 50° and treatment with chlorine is continued until the necessary increase in weight has occurred. On fractional distillation a yield of 90% of the theory of tetrachlorotoluene is obtained. Only traces of tile rentachloro-compound are produced as indicated by the slight precipit\ation on diluting a sample with an equal volume of carbon disulphide. Further chlorination of tetrachlorotoluene at 100-130° in violet or ultraviolet light gives tetrachlorobenzylidene chloride. G. F. M. Reactions in Energetic Solvents. I. The Direct Replace- ment of Sulpho-groups by Chlorine.HANS MEYER (MoTzatsh. 1915 36 719-722).-1n 1860 Carius observed that methane- and ethane-sulphonyl chlorides when heated at 150-1G0° with phoa phorus pentachloride underwent change according to the equation R*SO,Cl+ PCl = RC1+ SOCI + POCI,. The author has now dis- covered that thionyl chloride is especially favourable to the scission of sulphur dioxide from sulphonyl chlorides and lie believes that thionyl chloride was largely instrumental in producing the results obtained by Carius. 1'45628. W. G.ORGANIC CHEMISTRY. i. 135 At 160-180O in the presence of thionyl chloride aromatic sulphonic acids as also their chlorides and anhydrides are converted into the corresponding chloro-compounds with liberation of sulphur dioxide.Thus p-chlorobenzenesulphoiiic acid quantitatively yielded pdichlorobenzene and sodium benzenesulphonate gave chloro- benzene. With derivatives of the anthraquinone group the neces- sary temperature is higher and a t 200-220° the a- and P-sulphonic acids derived from anthraquinone were converted into the corre- sponding chloroanthraquinones. I n the absence of thionyl chloride whether other solvents such as tetrachloroethane are present or not the decomposition of the sulphonyl chlorides is only partial and frequently more complex in nature. D. F. T. Reactions in Energetic Solvents. 11. The Direct Replace- ment of Nitro-groups by Chlorine and a New Method of Chlorination. HAXS MEYER (Momtsh. 1915 86 723-730. Compare preceding abstract);-Other substituents in aromatic com- pounds besides tlie sulphonyl group can be replaced by chlorine under the influence of thionyl chloride the present publication only giving reaults on the replacement of the nitro-group. 4-Chloro- 3-nitrobenzenesulphonic acid pchloronitrobenzene 2 5-dichloro- nitrobenzene and nitrobenzene when heated with thionyl chloride a t temperatures between 140° and 180° lost their nitro-groups almost quantitatively with formation of 1 2 4-trichlorobenzene pdichloro- benzene 1 2 4-trichlorobenzene and chlorobenzene respectively.With m-nitrobenzenesulphonic acid the yield of m-dichlosobenzene was not so good direct chlorination occurring simultaneously to some extent so that the product also included a substance m. .p. 1G5-175C containing a high percentage of chlorine.A similar result was obtained with o-nitroanisole which gave a tri- chlorophenol in addition to o-chloroanisole. 1 5-Dinitroanthraquinone a t 180-200° was converted into 1 5-dichloroanthraquinone but with naphthalene compounds chlorination occurred very readily naphthalene itself a t 170-180° reacting with thionyl chloride giving 1 4-dichloronaphthalene. The presence of certain groups facilitates direct chlorination even of the benzene nucleus ; azobenzene reacts with thionyl chloride a t 180--2OOc giving 2 Z/-dichloroazobenzene together with its 4 4I-isomeride. A t somewhat higher temperatures namely 230-250° the suc- cessive substitution of t h e hydrogen atoms of a methyl radicle attached t o an aromatic nucleus may be effected ; thus toluene gave benzylidene dichloride and benzotrichloride whilst a-methylanthra- quinone yielded the monochloro- and dichloro-methyl derivatives. By the use of suitable solvents however the methyl group in such substances as tolueaesulphonic acids may be protected so that the action of the thionyl chloride is restricted to the replacement of the sulphonic group by chlorine. Sulphonatian of Benzene.’ 11.GERHARD MOIIRMANK (Aizitaleiz 1915 410 373-385).-The catalytic influence of sodium mercury D. F. T.i. 136 ABSTRACTS OF CHEMICAL PAPERS. and iron on the sulphonation of benzene has been described by Behrend and Mertelsmann (A. 1911 i 189). The author has examined the influence of members of the other groups of the periodic table namely aluminium lead arsenic selenium and manganese and also of cadmium and bismuth.Benzene vapour is passed into 97% sulphuric acid a t 235-245O containing the catalyst and the resulting m- and pbenzenedisulphonic acids (and in the case of lead the monosulphonic acid also) are converted through the sodium salts into the acid chlorides the crystals of which are separated mechanically. The results show that none of the substances approaches mercury in its catalytic effect. Manganese has scarcely any influence and cadmium has but little more. The other catalysts produce about the same effects with the exceptions of selenium which in the form of selenious acid causes carbonisation (although a t 160-170° i t has no sffect benzenelsulphonic acid only being produced) and of lead which in the form of lead sulphate brings about the forma- tion of 80.8% of the meta-disulphonic acid 9.7% of the para-acid N-Halogen Derivatives of the p-Halogen-substituted Benzene- sulphonamides.ROBERT REGINALD BAXTER and FREDERICK DANIEL CHATTAWAY (T. 1915 107 1814-1823).-The soluble sodium salts of various sulphonmonochloroamides have recently received con- siderable attention owing to their use in the treatment of infected wounds. Simple compounds of this nature were described some years ago (T. 1905 87 145) and a number of phalogen-substituted substances have now been prepared. The sulphondihalogenoamides are obtained by the action of the acids HOX on the amides and these give the sodium salts of the sulphonmonohalogenoamides when treated with sodium hydroxide. The sodium salts of the phalogenobenzenesulphonic acids which were required for the preparation of the sulphonyl chlorides were obtained by gradually adding the halogenobenzene to fuming sulphuric acid (10% SO,) a t below 60° and then pouring the cold solution into brine a t Oo.The salts were dried and separated from sodium chloride by solution in alcohol and then converted into the chlorides by grinding with phosphorus pentachloride. p-Chlorobenzenesulphondic?doroamide C,H,Cl*SO,*NCl crystal- lises in colourless rhombic prisms m. p. 83O and the dibromoamide in pale yellow six-sided rhombic prisms m. p. 102O (compare Kastle Keiser and Bradley A. 1896 i 555). Potassium pchloro- benzenesulphonchloroamide C,H,Cl*SO,K:NCl,H,O forms glisten- ing elongated prisms which lose water and then decompose violently a t about 160°; the sodium salt also crystallises with 1H,O and decomposes violently a t about 190°.p-Bromobenzenesulphondichloroamide (ibid.) gives potassium p-bromobe?zzerLesulphonchloroamide colourless needles with 1H,O which. explode a t 165O and the sodium salt 1H,O explosion p. 1 7 8 O . p-Bromo benze?aesulphondibromorrmide crystallises in pale yellow elongated rhombic prisms m. p. 132-133O (decomp.) and yields and 9.5% of the monosulphonic acid. c. s.ORGANIC CHEMISTRY. i. 137 the salts of pbromobenzenesulphonbromoamide ; potassium lR,O explosion p. 193O; sodium 1H,O expl. p. 211O. p-lodobeuzenesulphondic Jdoroamide crystallises in elongated rhombic prisms m. p. 147O and gives the salts of lpiodobeiizene sulFlionchloroamide; potassium 1H,O expl.p. 150O; sodium 1H,O expl. p. 185O. p-C Ji lorob enzeii esulpkonmet hylamide C,H,Cl*SO,*NHMe f orins shining whise plates m. p. 59O and yields the chloroa?iiicZe CGH,C1*SO,*NbkC1 six-sided rhombic prisms m. p. 66O and the bromonmide pale yellow rhombic prisms m. p. 99O. p-Chloro- b e w e nes dphonb en zylumide C,H,Cl-SO,*NH*CH,Ph crystallises in white needles m. p. 108-109° and forms the chloroamide rhombic prisms in. p. 1 2 4 O and bromoamide m. p. 1 1 2 O . The sulphonyl chlorides were also' condensed with various anilines and a large number of sulphovanilides and their corresponding chloroamides are described. C,H4C1* SO,*NPhCl forms six-sided rhombic prisms m. p. looo ; p-bromobe~zze~aeszcZphon- phe iL?/lchloroamide crystallises in elongated rhombic prisms m.p. 104O and the p-iodo-compound in colourless rhombs m. p. 139-140O. The p-chlorobenzenesulphonyl derivatives of substituted anilines are as follows -m-chloroanilide transparent rhombs m. p. 1 0 6 O ; -m-cJdoropJtenyZchloroamide C,H4C1*S0,~NCl*C,H,C1 rhombic prisms m. p. 90°; -p-chloronnilide needles m. p. 148O; -p-chloro- phenylchloroamide prisms m. p. 1 2 7 O ; -2 4-dichloroanilid~~ plates m. p. 108O; -2 4-dz'chloroph enylchloroamide prisms m. p. looo; p-bromounilide prisms m. p. 163O; -p-bromo- plenylchloroamide prisms m. p. 1 2 7 O ; -2 4-dihromoanilidr prisms in. p. 116O ; -2 4-dibromophe?zylchloroanzide prisms m. p. l l O o (decomp.); -p-iodoanilide prisms m. p. 173O; -p-iodo- pJ~eiz?/lchloroamide very unstable m. p. 70° (decomp.) ; -0-nitro- nnilide pale yellow prisms m.p. 114O (deoomp.) ; -0-nitrophenyl- cliloroarnide prisms m. p. 148O (decomp.) ; -m-nitroanilkZe pale yellow needles m. p. 124O ; -m-nitrophenylchloroamida almost colourless prisms m. p. 131O (decomp.) ; -p-nitroanilide yellow needles m. p. 159O (decomp.) ; -p-nitrophenylchloroamide prisms m. p. 1 4 3 O (decomp.); -0-toluidide colourless needles m. p. 1 1 1 O ; -o-tolylcl~loroa?nide prisms m. p. 1 2 7 O (decomp.) ; -p-toluididP prisms m. p. 8 8 O ; -p-tolylckloroamide prisms m. p. l l O o (decomp.) ; -p-tolylbromonmide pale yellow prisms m. p. 91O. The p-brornobenzenesulplion?/l derivatives are as follows -p-chloro- n?dide C,H,Br*SO,*NH*C,H,Cl prisms m. p. 138O ; -p-chloro- phenylchloronmide prisms m. p. 1 4 2 O ; -2 $-dichloroanilide prisms m.p. 134O ; -2 4-dichloro~hen~~Zchloronmine prisms m. p. 97O ; -p-,romoanilide prisms m. p. 141O ; -p-bromoph enylchloroamicTf> prisms m. p. 141O; -2 :4-dibromoanilide prisms m. p. 147O; -2 4-dibromophenylchloroamide prisms m. p. 1 1 7 O ; -p-iodonnilidp prisms m. p. 160° (decomp.) ; -p-iodophcn ylchloroamide very un- stable decomp. below 100° ; -o-nitron??ili& yellow needles m. p. 130O; -o-nitrophenylchloroam~de) prisms m p 160° (decomp.) ; p-C h loro b e nzencstilpJLonphen ylch lo roa mide,i. 138 ABSTRACTS OF CHEMICAL PAPERS. -m-nitroaidide yellow needles m. p. 140° ; -m-nitrophenylchloro- nmide long yellow prisms m. p. 140° (decomp.) ; -p-nitroanilide needles m. p. 183O ; -p-nitrophenylchloroamide prisms m. p. 1 6 4 O ; -0-toluidide prisms m.p. 119O ; -0-tolylchloroamide prisms m. p. 129O (decomp.) ; -p-toluididc prisms m. p. 99O ; -p-tolylchloroamide prisms m. p. 131O. The ypiodobenze?aes2ilphollyl derivatives are as follows -p-bromo- nnilide rliombic plates m. p. 1 7 4 O ; -p-bromopherLylchloroamide C,H,I*SO,*NCl*C,H,Br prisms m. p. 137O (decomp.) ; -p-iodo- clnzlzde glisbening plates m. p. 1 6 7 O (decomp.) ; -p-iodophenylchloro- nmide very unstable m. p. 142O (decomp.) ; -0-nitronizilide very pale yellow plates in. p. 137O ; -0-nitrophenylchloronmide very pale yellow prisms M. p. 167O ; -m-nitronnilide long yellow prisms m. p. 157O ; -m-?iit.1.opiiPnylc?~Zoroamide prisms m. p. 164O; -p-nitro- o d i d e glistening plates m. p. 154O; -o-toluidide long plates m. p. 161O ; -0-tolylchloroamide prisms m.p. 1 loo; -p-toluidide prisms in. p. 135O; -p-tolylchloroamide prisms m. p. 137O (decomp.). J. C. W. Nitrophenanthrenep. ADOLFO M E L ~ (diznl. E'is. Q i h L . 19 15 13 381-389).-A preliminary note describing the influence of the experimental conditions on the nitration of phenanthrene. A. J. W. A New Transformation of Acenaphthylene and Synthesis of Diacenaphthylidene a New Yellow Hydrocarbon. J. DOLIBSKI and K. DZIEWO~SKI (Ber. 1915 48 1917-1931).-The polymerisation of acenaphthylene under the influence of light and heat demonstrated the extreme lability of the substance (compare A. 1912 i 844; 1913 i 847; 1914 i 825). This is still further exemplified when the hydrocarbon is treated with traces of mineral acids for two' other so,lvmerides result.One of them is believed I d c==c-- to be diacenaphthylidene C,o€16<bH ~Ho>C!loH6 whilst the ' other is a complex subc,tance a t least Lpentameride. A solution of acenaphthylene in glacial acetic acid (50 grams to 120 grams) was mixed with 0.5 C.C. of concentrated hydrochloric acid and then warmed for an hour or two on the water-bath. The clear liquid gradually deposited a pale yellow heavy precipitate (40 grams) which was separated into the component polymerides by means of beazene the complex one being freely soluble. A better yield of the dimeride was obtained by treating the picrate of acenaphthylene with hydrochloric acid. 7 7-Diacenaphthylidene (diitapkthylenebuteii~~ C2iH16 was ob- tained in golde'n-yellow glistlening leaflets or tablets m.p. 2 7 7 O (corr.) which gave a greenish-blue solution in concentrated sulph- uric acid. Very dilute solutions in the aromatic hydrocarbons (for example a 0.00125% solution in benzene) exhibited a very intense violet-blue fluorescence which disappeared in bright sunlight owing to oxidation of the hydrocarbon. The dipicrate was obtained inORGANIC CHEMISTRY. i. 139 dark red needles m. p. 216-217O. The constitution of the hydro- carbon was ascertained by oxidation with sodium dichromate and acetic acid to naphthalic anhydride and by reduction with red phosphorus and hydriodic acid t o 7 7-diacenaphthyl (loc. c i t . ) . Bromine was not absorbed directly by the hydrocarbon but acted substitutively. On warming the' substance with a solution of bromine in carbon disulphide.it was transformed into 8 8-dibromo- diuceiwph t h ylide 11 e ?lo ' >(: C<yl ' ciliated orange-yellow C 11 13r c tl I h ' needles decomp. 203O which was oxidised to naphthalic anhydride. I n the cold however substitution in the naphthalene residues took place the product being aaf-dibroniodiaceiznphthylidene C,4H,,Br ciliated yellow needles m. p. 310° (decomp.) which was oxidised to a-bronionaphthalic anhydride. A fine suspension of the hydrocarbon in acetis acid was also treated with nitric acid (D 1.5) when aaf-di?zitrodiace?2nphthylide,ze C,,H,,O,N was obtained in dark red glistening needles which decomposed without melting a t above 360° and were oxidised t o a-nitronaphthalic anhydride. I n the polymerisation of acenaphthylene itself the chief product (70-80% yield) was the complex polymeride.This differs from the polyacenaphthyleiie obtained by thermo-polymerisation (loc. c i t . ) in m. p. and in being reiadily soluble in acetone and easily oxidised to naphthalic anhydride and it is theref ore designated allo-poly- ncenanhthwlene. It w2s obtained as an amorDhous. vellow sub- 1 d stance m. p. 185-190° approximating to the fkmula bG0H40. J. C. W. Some New Organic Compounds of Vanadium. A. T. MERTES and HERMAN FLECK ( J . Ind. E r ~ g . Chem. 1915 7 1037-1038).-When treated in the cold variously in carbon tetra- chloride o r benzene solution vanadium tetrachloride formed in- soluble additive compounds with certain organic bases. The following were isolated in an analytically pure condition With aniline a black powder of the composition 4NH,Ph,VC14 ; with dimethylaniline a green tar having the formula 4NMe,Ph,VC14 ; with phenylhydrazine a violet substance of constitution similar to the above ; with toluidine ammonia niethylamine and diphenyl- amine products were obtained approximating to the formulze 3CGH,Me*NH,,VCl4 4NH3,VC1,,4H,0 GNH,Me,VCl,,H,O and 3NHP1i,,2VCl4 respectively. A solution of vanadium tetrachloride in benzene deposited on keeping a purple compound with evolu- tion of hydrogen chloride.It varied in composition according to the length of time the solution was kept. Anthracene also formed a similar substitution product. Vanadium was estimated in the above compounds in the filtrate obtained from a lime fusion after precipitation of the chlorine with silver nitrate by precipitating as lead vanadate dissolving this in nitric acid and evaporat'ing with sulphuric acid to remove the lead reducing with sulphur dioxide and titrating the hot solution freed from excess of sulphurous acid with A7/ 20-permanganate.G . F. M.i. 140 ABSTRACTS OF CHEMICAL PAPERS. Monotropic Polymorphic Anilides. FREDERICK DANIEL CHATTAWAY and WILLIAM JAMES LAMBERT (T. 1915 107 1766--1773).-A close study of the behaviour of anilides when crystallising suggests that all anilides are capable of forming three very distinct types of crystals namely very slender hair-like crys- tals slender needles o r prisms and stout compact crystals. A large number of anilides can be made t o crystallise in two of these forms and some have been obtained in all three varieties.For example whea pbromoacetanilide and 2 4-dibromoacetanilide are allowed t o crystallise from hot alcoholic solutions they separate in long needles which slowly give place to the stable compact form. The rate of transformation varies with the solvent and the anilide used and increases rapidly with the temperature. Between Oo and the m. p. the compact form is stable and the solids therefore show no transition point within these limits. The view is held however that the transition point is much below the ordinary temperature but is unrecognisable because of the slow rate of the change. The point could be determined by measuring the solubilities of the two forms over a considerable range of temperature but this is a matter of extreme difficulty owing t o the rapidity of transform- ation in the warm solutions.Within the limits which have been f ouiid practicable the solubility curves for the two modifications ar0 parallel and therefore the two anilides are provisionally classed as monotropic. The development of the crystals is illustrated by photographs and the paEer also records careful determinations of the solu- bilities of p-chloro- 2 4-dicliloro- p-bromo- 2 4-dibromo- 4-chloro- 2-bromo- and 2-cliloro-4-bromo-acetanilides in alcohol a t from 5O t o 45O. J. C. W. Phenyl Esters of Oxalic Acid ROGER ADAMS and H. GILMAN ( J . Amer. Ch.ent. SOC. 1915 37 2716-2720).-Aryl oxalates can be prepared in almost quantitative yield by adding oxalyl chloride ( 5 grams) t o ice-cold pyridine (25 c.c.) crushing well the resuIting additive compound and gradually adding the phenol (2 mols.) dissolved in a few C.C.of pyridine. The mixture is kept a t Oo for two hours and is then poured into a mixture of concentrated hydrochloric acid and ice when the ester is precipitated. In addition t o the normal oxalates derived from pcresol a- and 8-naphthols and guaiacol the following esters were prepared o-Nitrophen~~Z oxalate C,O,(C,H,*NO,) yellow needles m. p. 185O ; o-nldehydopli euyl oxnlate C,O,(CGH,*CHO) plates m. p. 153-154O ; vnniZZ?yl oxnlate C20,[C,H3(0Me)*CHO] crystals ni. p. 203-204O ; p-ncet?/l-a-92nphth?/I oxalnte C20,(C,,H,Ac)2 leafy crystals m. p. 197O ; o-carbornethox,~pTten;yl oxalate C204(C,H,*C02Me) needles m. p. 158O. Quinol gave rise t o an ozalate C,O,(C,H,*OH) m.p. 2 1 2 O but if the reaction was allowed t o occur without cooling a mixture was obtained from which after treatment with acetic acid needles m. p. 226O could be isolated probably of the acetate of di-ph ydroxyp henyl ether C,,H,,04. D. F. T.ORGIANlC CBEMISTRY. i. 141 Preparation of 6-Nitro-3-aminophenol and its Methyl Ether. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 285638 ; from J . SOC. Chem. Ind. 1915 34 1135) .-When 4-nitro-1-acetyl- aminobenzene-3-sulplioiiic acid (nitroacetylsulphanilic acid) is heated at a high temperature under pressure with methyl-alcoholic alkali the acetyl group is saponified and the sulplionic acid group is replaced by liydroxyl o r methoxyl. m-Phenetidine and Some of its Derivativee. FRBDBRIC REVERDIN and J.LOKIETEK (BUZZ. Soc. chim. 1915 [iv] 17 406-409. Compare A. 1915 i 878).-~n-Phenetidine has been prepared by a new method and from it a number of derivatives have been obtained. Acetyl-m-aminophenol when heated for two hours in alcoholic solution with sodium hydroxide and ethyl bromide is readily ethylated giving ace to-m-phenetidide OEt*C,H,*NH*COMe greyish- white platsea m. p. 96-97O. Ethyl sulphab can also be used for the ethylation. This acetyl derivative is readily hydrolysed by heating on a water-bath with 35% hydrochloric acid giving the free base yielding a hydrochloride colousless leaflets and a picrate yellow needles m. p. 158O. The following acyl derivatives have been prepared by the usual metho,ds Formyl-m-ph eizetidide OEt*C,H,*NH*COH m.p. 52O ; benzo-m-phenetidide OEt*C,H,*"H*COPh long white needles m. p. 103O ; tolueTte-p-sulpho-m-phenetidide OEt~C,H,*NH*SO,~C,H,Me yellowish-white leaflets m. p. 157O ; o-nitro t oluene-p-sulpho-m-phenet idide OE t~C,H,~NH*SO,~C,H~Me*NO needles m. p. 8 8 O and 2' 4/-dzmtro-3-ethosy&phenylart~iiie OEt*C,H,*NH*C,H,(NO,) orangeyellow crystals m. p. 151O. m-Phenetidine has been diazotised and coupled with fl-naphthol giving a compound C,,H,,O,N red needles m. p. 107O y.ielding a sodium salt insoluble in cold water. Coupled with salicylic acid the diazo-salt gives a compound which dyes wool bright yellow; coupled with resorcinol a compound reddish-brown ; coupled with naphthionic acid an orange-red conzpzcizd ; and coupled with 1 4-naphtholsulphonic acid a red compozciid.Aromatic Telluretine Compounds. 111. (Conclusion). KARL LEDERER (Ber. 1915 48 1944-1949. Compare A. 1913 i 615 724 1182).-Some diary1 tellurides have been condensed with more halogeno-acids and esters and some triaryltelluronium picrates have been prepared. A mixture of diphenyl telluride and ethyl iodoacetate deposited when expoBed to light for a few days garnet-red crystals of diphenyl- telluronium iodide (from the free iodine) followed later by ethyl diph e n y 1 t ell ur e tin e iodide [iod odi ph e n y 1 t el l u r k c e t at el TePh,I* CH CO,E t m. p. l l O o (decomp.). A solution of diphenyl telluride in a-bromopropionic acid was warmed a t 60° for some time and then diluted with ether when J. C. W. W. G .i. 142 ABSTRACTS OF CHEMICAL PAPERS.dip?& e n y 1 t ellure tin e [a-b row odiiph eny l t elluri- propionic acid] TePh,Br-CHMe*C02H was precipitated as a white powder m. p. about 9S0. Similarly a-bromobutysic acid gave dz'ph4rLyl-a-butyryltelluTetine bromide [a-bronzodiphenyltelluri- trutyric acid] TePh2Br*CHEt*C02H m. p. 84-85O whilst ethyl a-bromobutyrate yielded the( corresponding ethyl ester an amorphous substance m. p. 142-143O and ethyl a-bromoiso- bu t$y r a t e formed b ro mide [a-bromodiphenyl t elluriiso~bu tyra t e] TePh2Br*CMe2* CO,Et m. p. about 1 3 0 O . A solution of di-ptolyl telluride in methyl bromoacetate gradually deposited the compound (C,H7)2TeBr-CH2*C02Me,CH2Br.C0,Me m. p. 6S0 from which the free methyl di-p-tolyltellztretine bromicle [ bromodi-ptolyZteZZu~~~cetute] was obtained by repeated crystallisa- tion from chloroform and ether in aggregates of small prisms m.p. 92-93O. The corresponding ethyl ester had in. p. 102-103°. Di-o-tolylmethyltelluronaum chloride (C,H,)2TelLleC1 was ob- tained by boiling the corresponding iodide with silver chloride and water. It crystallised from water in four-sided plates with 2H20 m. p. 93O and again at 14B0 and from chloroform with Triphenyltelluronium hydroxide TePh,*OH was obtained by boiling the iodide with silver oxide and water as an alkaline resin which formed a p'crate broad yellow needles m. p. 1 6 0 O . Tri-p-tolyltelluronium hydroxide a resin m. p. about l l O o also formed a picrate long prisms m. p. 194-195O whilst the resinous tri-octolybtellwroniecm hydroxide yielded a picrate long yellow prisms m.p. 1 8 2 O a chloride stout coiumns m. p. l'i5-176O and a bromide m. p. 197-198O. Z romide e t h y Z d i ph e n ?/l-a-is o b u t y r y 1 t el 1 ur e t in e iCHC13 1~1. p. 155-156'. J. C. W. Some New Oxidation Derivatives of Cholesterol. ST. ~IINOVICI and (MME.) TH. ZENOVICI-EREMIE (Bzill. Sci. Acad. Roumaine 1915 4 194-205. Compare Minovici and Vlahuta A. 1912 i 697).-The authors have oxidised cholesterol with hydrogen peroxide under varying conditions and have obtained five different compounds to which they have been unable to assign any definite constitution. When 10 grams of cholesterol were dissolved in 200 C.C. of glacial acetic acid on a water-bath and a mixture of 50 grams of hydrogen peroxide in 100 C.C. of sulphuric acid (20%) slowly added and the mixture slowly boiled for two hours a clear oily liquid was obtained which when separated and washed with water solidified t o white floccula.These when crystallised from acetone and water gave a compozcnd C2,H,,O4 acicular needles m. p. 1 6 0 O ; [a] + 41.47O. Submitted t o Salkowski's reaction for cholesterol the compound gave a colourless chloroform solution the acid being coloured orangeyellow. I n the Liebermann- Burchard reaction no play of colours was obtained but only a deep violet-red coloration. The compound did not give Lifschutz's reaction for oxycholesterol. The substance contains no hydroxyl phenolic o r ketonic group and is not an ozonide o r a peroxide.ORGANIC CHEhZISTRY. i. 143 It is very probably a lactone and contailis an acetyl group.It does not unite with bromine. When warmed with hydrobromic acid i t yields a compozcnd ClnHzsBr m. p. 130° and with hydrochloric acid a compound C,,H,,Cl m. p. 150O. The mother liquors from the compound C,,H,,O gave an oily substance which resinified on contact with air and after purification the compo?cnd was obtained as a yellow powder. The substance is slightly acid in character and is soluble in alkalis and gives a silver salt. It is probably a resin acid having the composition C,H,,O,. If in the original oxidation of the cholesterol an excess of hydrogen peroxide was used an amorphous compound was obtained which was not characterised. I f the original proportion of hydrogen peroxide was used but added in larger portions a t a time a compound was obtained in white lamellar crystals m.p. 200O. By slowly adding 20% sulphuric acid alone to a solution of cholesterol in gently boiling acetic acid on cooling a crystalline compound m. p. l l O o - l l l o was obtained. It was not cholesteryl acetate since it was not decomposed by boiling with alcohol or water. It differed from cholestanyl acetate in that with phosphorus pentachloride it gave a crystalline chloro-compound ni. p. 95-97O and with bromine in carbon disulphide a crystalline bromo- derivative m. p. 116-118°. W. G. Sitosterol and Stigmasterol. A. HEIDUSCHKA and H. W. GLOTH (Arch. Pharm. 1915 253 415-426).-After a brief sum- mary of the work of Burian Windaus Ritter Pickard and Yates and Jaeger on these two sterols the following new derivatives are described. Sitosteryl salicylnte C,7H,,0-CO*C,H,*OH has m.p. 147O and separates from ether and alcohol in colourless gelatinous flocks which ultimately become crystalline. Sitosteryl phenyl- cnrbamate C,,H,,O,N forms crystals m. p. 174O. By direct treat- ment with an excess of bromine sitosterol yields decabromosito- sterol C2,H%0Brl0 a brown powder m. p. about 185O and octabromositost erol C27H380BrS a yellow powder in. p. about 120° the former of which is almost insoluble in alcohol. Just as Windaus converted cholesterol by oxidising its dibromide with acidified permanganate and debrominating the product by zinc and acetic acid into cholestenone so has sitosterol been now con- verted into sitosteaone C27H440 crystals m. p. 82O which forms a semicarbazone crystals m.p. 254O (decomp.) sintering a t 243O. Stigmasterol forms a palmitate C,,H,90*CO*C,,H, silky crystals m. p. 99O stearate crystals m. p. lolo oleate colourless crystals m. p. 44O salicylate colourless needles in. p. 175O and cinnamate colourless crystals m. p. 155O. By the oxidation of stigmasterol tetrabromide and debromination of the product a crystalline substance m. p. 140° was obtained which did not exhibit the properties of a ketone. c . s. The Substituted Benzoylbenzoic Acids. ALICE HOFMANN (Moizatsh. 1915 36 805-824).-The author brings forwardi. 144 ABSTRACTS OF CHEMICAL PAPERS. further experimental proof of the fact that the presence of halogeii substituents in phthalic anhydride facilitates the Condensation of the latter with benzene derivatives.When 3 6-dichlorophthalic anhydride is heated with dicliloro- benzene and a little aluminium chloride a t 200° some hydrogen chloride is eliminated and there is also produced 3 6 2’ 5-tetrci- cldorobenzoylberzzoic acid needles m. p. 205-207O which on heating a t 140° with sulpliuric acid is converted into 1 4 5 8- tetrachloroanthraquinone (compare Schilling A. 1913 i 493). During this condensation the acid undergoes slight concurrent decomposition into dichlorobenzene and 3 6-dichlorophthalic acid the latter being observed as a sublimate of the anhydride. The tetrachlorobenzoylbenzoic acid was converted by thionyl chloride into the acid chloride which on treatment with methyl alcohol yielded the methyl ester needles m. p. 145-148O a second modifi- cation of this ester m.p. 1 7 2 O being obtained by the interaction of the acid and the alcohol in the presence of a little sulphuric acid ; the former modification (termed the pseudo-form) could be converted into the latter (the “normal” form) by boiling with methyl alcohol and a little sulphuric acid. Tetrachlorophthalic anhydride and chlorobenzene reacted at 140° in the presence of a little aluminium chloride producing pentachlorobenzoylbenzoic acid m. p. 165O which resembled the above tetrachloro- analogue in giving a non-crystalline “ pseudo ” methyl ester when the acid chloride was treated with the alcohol and an amorphous (‘normal” ester when esterified directly by methyl alcohol in the presence of sulphuric acid. When heated a t 140° with sulphuric acid pentachlorobenzoylbenzoic acid yielded peiitachloroanthraquinone. The condensation of tetrachlorophthalic anhydride and dichloro- benzene in the presence of aluminium chloride a t 220° gave hexa- chloro b enzoylb enzoic acid colourless crystals m.p. 238-239O which like the preceding acids could be converted through the chloride m. p. 181-184O into a ‘(pseudo” methyl ester m. p. 180-182° and by the usual process of esterification into an amorphous normal ” methyl ester. It also underwent intra- molecular condensation when heated with sulphuric acid yielding hexachloroanthraquinone pale yellow needles m. p. 298O. I n the usual manner tetrachlorophthalic anhydride and nitro- benzene condensed together giving tetrachloronitro b enzoyl b enzoic acid colourless crystals m.p. 242-245O the acid chloride (colour- less crystals) of which was converted by methyl alcohol into an amorphous methyl ester. By the addition of bromine to a heated mixture of phthalic acid and fuming sulphuric acid there was obtained tetrabromophthalic acid yellow crystals m. p. 268O which underwent condensation with benz_ene in the presence of aluminium chloride giving tetra- brornoben2oylbenzoic acid m. p. 230-232O; the methyl ester platelets m. p. 1O8-11lo when heated with sulphuric acid in the usual way apparently gives rise to a bromoanthraquinonesulphonic acid the tetrabromoanthraquinone presumably being less resistantORGANIC CHEMIS‘I’RY. i. 145 than 1 2 3 4-tetrachloroanthraquinone towards sulphuric acid ; the free acid however when carefully treated with sulphuric acid may be made to yield tetrabromoanthraquinone orange-red needles m.p. 200-202° (in a closed tube). With bromobenzene tetrabromophthalic anhydride undergoes condensation producing pentabromobenzoylbenzoic acid m. p. 228-230° which yields an oily “normal ” methyl ester and an amorphous ‘‘ pseudo” modification m. p. 178-183O and can also be made t o undergo further condensation to pentabromo- anthraquinone m. p. 230-240° the yield however being poor. Tetrabromophthalic anhydride and dibromobenzene interacted under the usual conditions producing hexabromobenzoylbenzoic acid m. p. 218-219O from which was obtained by heating with sulphuric acid a small quantity of hexa~bromoanthraquinone Ths condensation of tetrabromophthalic anhydride and dichloro- benzene gave tetrabromobenzoyldichloro benzoic acid m.p. 240- 245O. In a similar manner tetraiodophthalic anhydride and benzene gave tetraiodo b enaoylb enzoic acid microscopic yellow crystals m. p. 230-231O (sodium salt silver leaflets) from which it was found impossible to produce the corresponding tetraioclo- anthraquinone. D. F. T. Preparation of Sulphomethylbenzophenone - o - carboxylio [Sulphomethyl-o-benzoylbenzoic] Acids and Substitution Pro- ducts. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 285700; from J . SOC. Chem. Ind. 1915 34 1135).-The chlorides of benzoic acid or its substitution products are condensed with m-xylene the new substances are sulphonated and the resulting as-dimethylbenzophenonesulphonic acids having the sulphonic group in the xylene residue are oxidised.The o-carboxylic acids which are thus obtained may be condensed to anthraquinone deriv- atives by means of concentrated sulphuric acid. Preparation of Derivatives of 2-Hydroxy-3-naphthamide. FARBENFABRIKEN VORM. F. BAYER & Co. (D.R.-P. 284997; from J . SOC. Chem. Ind. 1915 34 1136).-The hydroxynaphthylamides of 2-hydroxy-3-naphthoic acid are obtained by condensing amino- naphthols with the haloids or with the acid itself in the presence of dehydrating agents. Whereas the anilide is only soluble in lime water and even so only t o a slight extent the new amides dissolve readily in warm dilute sodium carbonate. They are freely absorbed from such solutions by unmordanted cotton which then acquires very intense clear fast shades with diazo-solutions.J. C. W. 111. p. 280-285’. J. C. W. Preparation of Hydroxytriarylmethanecarboxylic Acids. FARBENFABRIKEN VORM. F. BAYER & Co. (D.R.-P. 286433; from J . SOC. Chem. Z d . 1915 34 1135).-A mixture of an aromatic o-hydroxycarboxylic acid (2 mols.) and an aromatic aldehyde (1 mol.) is treated with zinc chloride and phosphoryl chloride reaction being completed by warming a t 70°. The phosphoryl VOL. CX. i. Yi. 146 ABSTRACTS OF CHEMICAL PAPERS. chloride is recovered by distillation under reduced pressure. o-Chlorobenzaldehyde and o-creosotic acid yield chlorodihydroxy- climethyltriphenylmethanedicarboxylic acid. J. C. W. Phenylfumario Acid. G. KARL *~LMSTROM (Ber. 1915 48 2009-2010) .-A substance has been obtained in another connexioii which must be regarded as phenylfumaric acid but as it did not agree with Barisch's description (A.1880 43) the acid has been prepared by boiling phenylmaleic anhydride (Alexander A. 1890 1136) with 2N-sodium hydroxide. PA enylfumaric acid C,,H,O separates from benzene as a felted mass of needles m. p. 128-129O and from water in which i t is very soluble with 2H,O. It quickly reduces permanganate and is easily Converted into phenylmaleic anhydride by melting. J. C. W. Preparation of Compounds of Phenolphthalein and Alkali Carbonates. A. VON SZTANKAY and C. GEYER (D. R.-P. 286030; from J . SOC. Chem. Znd. 1915 34 1167).-Cmcentrated solutions of the alkali carbonates are treated with phenolphthalein either in solution or as a freshly prepared suspension in water a t the ordinary temperature.Compounds of the type 2C,,H,,0,,6Na2C0 are formed. They are strongly alkaline are stable only in aqueous solution and the therapeutic doses are much smaller than is the case with the known alkali salts of phenolphthalein. J. C. W. The Synthesis of Certain Substituted Syringic Acids. MARSTON TAYLOR BOGERT and EDWARD PLAUT (J. Anzer. Cheni. SOC. 1915 37 2723-2733).-A record of the earlier part of an investigation of derivatives of . syringic acid (4-hydroxy-3 5- dimethoxybenzoic acid). Methyl bromogallate trimethyl ether prepared by the action of bromine on methyl gallate trimethyl ether in acetic anhydride solu- tion was obtained for the first time in the solid state prisms m. p. 90° (corr.) b. p. 202O/16 mm. (compare Hamburg A.1899 i 364). Syringic acid was converted by the Fischer-Speier reaction into the methyl ester (Graebe and Martz A. 1903 i 262; Bogert and Isliam A. 1914 i 532) ethyl ester crystals m. p. 55'8O (corr.) and isoaniyl ester needles m. p. 1 0 1 O (corr.). On acetylatioii a t the ordinary temperature by acetic anhydride the methyl ester was converted into its acetyl derivative OAc*C,H2(0Me),*C02Me crystals ni. p. 129O (corr.) whilst bromination in cold acetic anhydride gave methyl 2-bsomosyriiigaf c OH*C6HBr(OMe),*CO,1e crystals m. p. 89O (corr.) which was also obtained by partial tiemethylation of methyl bromogallate trimethyl ether by heating with hydrobromic acid. Syringic acid in cold acetic acid solution is converted by nitric acid into 4 5-dinitropyrogaIlol-1 3-dimetliyl e t h e r pale yellow crystals m.p. 154O (corr.) the change being analogous to that undergone by trimethylgallie acid but in solution in acetic anhydride a t - 5 O methyl syringate undergoes nitration t o m ~ f I q ( ! 2-nitros?/s~npte OH*C,H(OMe),(NO,)*CO,Me paleORQANIC CHEMISTRY. i. 147 yellow crystals m. p. 68.3O (corr.) which can also be obtained by heating methyl nitrogallate trimethyl ether with hydrobromic acid. Ethyl 2-nitrosyi.inyccte almost colourless silky needles m. p. 7 4 O (corr.) was prepared in an analogous manner to the methyl ester. Tlie latter substance was reduced by tin and hydrochloric acid to i t i f thyl %amin osyringnt P OH*C,H (OMe)2(NH2)*C0,Me colour- less crystals in. p. l l O o (corr.) which gradually darkens in the air ; li,!~c?l.ociilr,ric~e needles m.p. 192O (corr.) ; diacetyl derivative large crystals m. p. 139'9O (corr.). By diazotisation in diluted sulphuric acid solution and subsequently heating a t looo the methyl ester was converted into 2 4-dz%yd~*ozy-3 5-~~iiietl~c),r.yhett r- oic ncid C,H(OH),(OMe),*CO,H pale yellow crystals m. p. 165O (tlecoinp.) ; dincetyl derivative crystals decomp. at 162O. I n a preliminary experiment in which the product from the thermal decomposition of the dihydroxyclimethoxy-acid was recrystallisetl from alcohol and subsequently treated with methyl sulphate and sodium hydroxide solution there was obtained a siibstcciicP glassy needles m. p. 89O (corr.) possibly apioiiol tetramethyl ether. D. F. T. Derivatives of Methylvanillin and a New Condensation Product.B. L. VANZETTI (Atti R. Accad. Limei 1915 [v] 24 ii 467-470. Compare Korner and Vanzetti A. 1912 i 352; Fritsch A. 1904 i 94).-Veratrylic acid [3 4 3' 4/-tetramethoxy- benzilic acid] cannot readily be obtained by transposition or oxida- tion of the corresponding ketonic compounds according to the schemes *CH(OH)*CO* + >C(OH)*CO,H and *CO*CO* -+ >C(OH)*CO,H although in other cases these changes are almost quantitative. Thus whilst benzoin is transformed directly into beiizilic acid by means of a current of air in presence of alkali iii the hot veratroin merely undergoes quantitative oxidation to veratril under these conditions. Veratrylic acid may be obtained moderately pure (m. p. about 68O) but by no means in quantita- tive yield by the prolonged action of alcoholic potassium hydroxide on verakril in the hot.Another starting point for preparing veratrylic acid is veratro- phenone (3 4 3/ 4/-tetramethoxybenzophenone) m. p. 144*5O which may be obtained by converting veratric acid into' veratroyl chloride m. p. 70-71° and treating the latter with veratrole (1 mol.) in presence of aluminium chloride. The further stages are represented by the scheme The various compounds obtained in this way which is not very coiivenieiit for preparing the acid are t o be described elsewhere. Fusion of veratril with potassium hydroxide also gives poor yields of veratrylic acid although high yields of benzilic and anisylic acids and somewhat lower ones of piperonylic acid are obtainable in this way.'The yield of veratrylic acid varies considerably with 9 2i. 148 ABSTRACTS OF CHEMICAL PAPERS. the temperature of the fusion and in some cases more complicated transformations occur the mass becoming dark coloured and resinous. Treatment of the resin with various solvents yields an orange-yellow compound m. p. 1 9 8 O and crystallisation of this from acetic acid gives shining brownish-red needles which a t 110- 1 20° are converted into the orange-yellow compound. With cold concentrated sulphuric acid the latter gives a greenish-blue colora- tion which changes in a few minutes to a red coloration; sub- sequent dilution either spontaneous or otherwise produces a reddish turbidity owing to precipitation of the compound in the form of powder. Except that the proportion of hydrogen is rather low the composition of this compound approximates closely to that of veratril.The transformation which the veratril undergoes i n the formation of this compound appears t o be analogous to the thermal decomposition of benzilic acid which is now under investigation. T. H. P. Preparation of Tetrachlorobenzalde byde and New Colouring Matters therefrom. 1,. CASSELLA & Co. (Eng. Pat. 1915 13970; from J. SOC. Chem. Ind. 1915 34 1243).-Tetrachloro- benzaldehyde is obtained as a white powder which crystallises from ether in colourless needles m. p. 97-98O by dissolving tetra- chlorobenzylidene chloride in six parts of concentrated sulphuric acid a t 90° and pouring into iced water. The above solution in sulphuric acid or tetrachlorobenzaldehyde itself condenses with o-hydroxycarboxylic acids such as o-cresotic acid to give leuco- compounds which on oxidation with sodium nitrite in sulphuric acid nitric acid nitro-compounds or fuming sulphuric acid yield valuable new dyes of the triphenylmethane series.These dyes surpass in intensity and fastness other known dyes of a similar character and are distinguished by their bright greenish-blue shade. G. F. M. Semicarbaeones. V. Semicarbazom s of Benzaldehy de and Some of its Substitution Products. JAMES ALEXANDER RUSSELL HENDERSON and ISIDOR MORRIS HEILBRON (T. 1915 107 1740- 1752. Compare T. 1912 101 1482; 1913 103 377 1504; 1914 105 2892).-The absorption spectra and the power t o form salts with dry hydrogen chloride of various semicarbazones have been investigated.Semicarbazones with hydroxy- or methoxy-groups in the nucleus are found t o absorb two molecular proportions of hydrogen chloride giving yellow to red salts. If the nucleus contains a strongly nega- tive substituent such as chlorine or nitroxyl the semicarbazone only absorbs one proportion of the gas forming a practically colourless salt. The acetylation or benzoylation of salicylaldehyde has no influence on the additive capacity of the semicarbazone but the pnitrobenzoyl derivative gives a semicarbazone which only absorbs 1 mol. of hydrogen chloride. No definite result could be obtained in the case of pdimethylaminobenzaldehydesemicarbazone which absorbed nearly 4HC1 and ptolualdehydesemicarbazone which combined with nearly 2HC1.ORG A N I C C HEM ISTR Y .149 Some semicarbazones were observed to form labile more coloured modifications which are probably the isomerides of the stable products finally obtained after repeated crystallisations. The absorption spectra were examined in solutions in alcohol alcoholic sodium ethoxide and concentrated sulphuric acid. With the exception of the p-dimethylamino- and p-nitro-compounds the semicarbazones show a band in N 1 10000-alcoholic solution a t about 1 / X 3500. The addition of sodium ethoxide t o the solutions of the Iiydroxy- but not methoxy-compounds displaces the band towards the red. Semicarbazones containing hydroxyl or methoxyl in the ortho-position show a band in concentrated sulphuric acid at about l/X2600 which is not exhibited by the others.p-Tolualdehydesemicarbazone gave a yellow Irydrochloride C,H ,ON,,l&HCl which rapidly decomposed in the air. Salicylaldehydesemicarbazone gave an unstable yellow &hydro- chloride and a straw-yellow fairly stable sulphate C,H,O,N,,H,SO decomp. 150O. o-Methoxybenzaldehydesemicarbaxone colourless needles m. p. 215O (decomp.) formed a dark orange fairly stable dihydrochtom'de. p-Hydroxybenzaldehydesemicarbazone when first formed contained a yellow admixture probably the labile iso- meride and it yielded an unstable yellow dihydrochloride and a yellow sulphate. pMethoxybenzaldeliydesemicarbazone was ob- tained in a labile form small transparent yellow prisms m. p. 168O very soluble in acetone and the usual colourless form ni. p. 2 0 9 O (decomp.). It gave an unstable orange-yellow CFihydro- chloride and a mustard-yellow stable sulylzate decomp.152O. Vanillinsemicarb'azone formed a very unstable orange-yellow dihydrochloride. Veratraldehydesemicarbazone yielded an un- stable orange di?bydrochloride decomp. 1 30°. Piperonalsemicarb- azolze dihydrochloride deep orange-red lost hydrogen chloride in the air. 2 - Hydroxy - m - methoxybenzaldehydesemicarbazotze CgH1103N3 colourless needles m. p. 225O (decomp.) gave an un- stable yellow &hydrochloride m. p. 1 5 8 O (decomp.). 2 3-Di- m e t hoxy b en za Zde h ydesemicar b n zo ne white needles m . p. 2 3 1 O (decomp.) yielded a dirty yellow dihydrocldoride. The chlorobenzaldehydesemicarbazones gave the following un- stable hy&oc?dorides ortko cream coloured decomp.203O * metu colourless decomp. 198O; para pale yellow decomp. 182;. The nitrobenzaldehydesemicarbazones yielded the following hydro- chlorides ortho cream coloured unstable decomp. 2 1 2 O ; I T M ~ C I cream coloured unstable decomp. 2 2 2 O ; p r a pink stable n o t decomposed a t 275O. o-Acetoxybe?zznldehydesenLicarbazone C,0H1103N3 a colourless granular powder m. p. 167O gave an unstable dark yellow &hydro- chloride. o - Benzoyloxyb e~zzaldei~ydesenzicar~azo~~e colourless needles rri. p. 195-196O (decornp.) formed a creani coloured unstable dihydrochloride. 2 - p - Nifroben~zoyloxybet~znldehyde CI4HgO,N was obtained by the action of the acyl chloride on salicylaldehyde in pyridine solution in the form of pale yellow leaflets m. p. 1 2 8 O which yielded the semicarbnzone NO,* CbH,*CO*O*C,H,*C'H N*NH*CO *NH2,i.150 ABSTRACTS OF CHEMICAL PAPERS. pale yellow needles in. p. 2 1 8 O (decomp.) ; hydrochloride colour- less and unstable. pDimethylaminobenzaldehydeseinicarbazone showed the same absorption band in alcohol as the p-hydroxy-compound did in alcoholic sodium ethoxide. When first formed i t was dark red but the recrystallised substance was white and the I/ ydrochlom'de 3-4HC1 was very unstable and greenish-blue. J. C. W. Constitution of the Salts of Phenol-aldehydes. 11. H. PAULY ( B e y . 1915 48 2010-2018. Compare A. 1915 i 689). -A continuation of the controversy with Hantzsch (A. 1915 i 55 1 1062). Hantzsch adheres t o his quinonoid isomerism theories to explain the coloured salts of phenol-aldehydes but Pauly main- tains that all the problems connected with the manifold activities of the carbonyl group are best explained by valence-electron formulation.The following salts are described The sodium salts of salicyl- aldehyde CiH,O,Na,C,H,O,,~H,O (Ettling 1840) and C,H,O,,C,H,O,Na (Hantzscli 1906) both of which are pure white; the sodizcm salt of isovanillin C",H,O3Na sulphur-yellow needles ; and tlie sodiu I ) / salt of bromoisovanillin C,H,O,BrNa a bright yellow crystalline precipitate. Hronioisoilnnillzii or probably 2-bromo-5-hydroxy-4- methoxybenzaldeliyde tlie product of the actioii of bromine d i s solved in acetic acid 011 isovanillin forms snow-white needles m. p. 208'. J. C. I%'. Isomerism of the Oximes. VII. 5-Bromovanillinoxime 5-Nitrovanillinoxime and 6-Nitropiperonaloxime.OSCAR LISLE BRADY and FREDERICK PERCY DCNN (T. 1915 107 1858-1862). -It has been found that certain negative substituents in the benzene ring seem t o favour the existence of two isomeric oximes. The effect of introducing such groups into1 vanillinoxime has there- fore been examined 'for tliis contains groups namely methoxyl and hydroxyl which inhibit the formation of a second isomeride. 5-Broino- and 5-nitro-vanillinoximes could only be obtained in the nn ti-form however which shows that the negative groups do not count,erbalance the effect exercised by the other groups. Unlike vanillinoxime piperonaloxime can readily be obtained in the syir- form m d therefore it was expected thatq tlie 6-nitro-derivative would also exist in the two forms.Strange t o say i t does not form a hydrochloride so the two distinct inodifications could not be cliaracterised. 5-Rrornoz'(/!)L17i,io,7.i/r/ P C,H80,NBr was obt'ained from the pro- duct of the direct bromination of vanillin in colourless needles 111. p. 179O. The position of the' bromine atom was proved by converting the oxime ultimately into 5-bromo-4-hydroxy-3- melthoxybeilzoic acid (Robertson T. 1908 93 792). The oxinie was first converted by boiling acetic anhydride into 5-brorno-4- ucetorry-3-?n e t h oxyb en Z O I I it rile C,,H,O,NBr colourless crystals in. p. llO-lllo and this was hydrolysed by boiling with diluteORGANIC CHEMISTRY. i. 151 sodium hydroxide f o r a few minutes to 5-byorno-4-hydroxy-3- ?t~efhoxybeizaoiait~ile needles m.p. 144O (sodium salt shining plates) and then on continuing the boiling t o t110 above acid. The oxime formed a diacetate C12H120,NBr a microcrystalline powder m. p. 1 2 2 O and a hydrochloride m. p. 175O (decomp.) from both of which the original oxime could be recovered. 5-Nitrovanillinoxiine as obtained from the aldehyde by means of hydroxylamine had m. p. 2 1 6 O (Vogl A. 1899 i 698 gave 111. p. 200-201°) and formed a red sodium salt. It was con- verted into a dincetate C,2H130,N2 a yellow crystalline powder in. p. 1 1 2 O and a nzoi~oacetate orange needles with 1H,O m. 11. 1 4 7 O the latter being obtained most conveniently by the action of acetyl chloride1 dissolved in pyridine. It also yielded a hydro- chloride iii. p. 2 0 4 O (decomp.) but all these derivatives gave the original oxiiiie when suitably treated.6-Nitropiperonaloxime was converted into the ncetnte C,,H,O,N yellow iiePYdles m. p. 1 4 2 O . J. C. W. Chlorination Experiments with Antimony Pentachloride KARL STEINER (Momtsh. 1915 36 825-829. Compare Eckert and Stleiner A. 1915 i 564 565).-An extension of tlhe earlier investigation. When -heated with antimony pentachloride benzopheiione gave Iiexachlmobenzene &s the main product together with a little ~7~rchlo?.obeiicopheno,7e CO(C,Cl,) colourless needles m. p. 318O and perchlorobenzoic acid. Benzil gave rise t o hexachlorobenzene with a little perchlorobenzoic acid. 1 2-Naphthaquinone yielded tetrachlorophthalic acid and perchloronaphthaquinone. Under similar treatment benzoic acid and benzoyl chloride yielded hexachlorobenzene together with a mixture of chlorinated beiizoic acid9 whilst phthalic acid gave a mixture of the same iia.turet.With benzoylbenzoic acid the chief products were per- chlorobenzoylbenzoic acid and 1 2 3 5 6 7 8-heptachloroanthra- quinoiie accompanied by small quantities of tetrachlorophthalic acid and hexachlorobenzene. By using a suitable solvent such as tetracliloroethane tlie action of the antimony pentachloride can be moderated and with a 10% solution of antliraquinone in this liquid the chief product is 1 4 5 8-tetrachloroanthraquinone. D. F. T. Indones. 11. Synthesis of 3-Phenvl-2-methylindone. R. DE FAZI ( A t t i R. Accad. Lincei 1915 [v] 24 ii 343-348. Com- pare A. 1915 i 1063).-Similarly t o 3-phenyl-2-ethylindone 3-phenyl-2-methylindone (compare Rupe Steiger and Fiedler A.1914 i 281) may be obtained by the action of cold concentrated sulphuric acid on ethyl 8-hydroxy-BB-diphenyl-a-methylpropionate (Rupe Steiger and Fisdler Zoc. c i t . ) :i 1.52 ABSTRACTS OF CHEMICAL PAPERS. The oxime of 3-phenyl-2-methylindone C16Hi30N forms shining yellowish-green prisms m. p. 199-200° and in the cold gives a blood-red coloration with concentrated sulphuric acid and a ruby- red coloration with concentrated nitric acid ; the semicarbazone forms orange-red indented leaflets m. p. 219-220° (Rup Steiger and Fiedler Zoc. cit. gave m. p. 200-201°) and gives intense blue and cherry-red colorations in the cold with concentrated sulphuric and nitric acids respect'ively ; the semioxamzone C,,Hl5O2N3 forms tufts of intensely yellow shining needles m.p. 203-205° and gives blue and cherry-red colorations in the cold with concentrated sulphuric and nitric acids respectively. The semicarbazone of 3-phenyl-2-ethylindone (compare A 1915 i 1064) Cl,H,,ON forms tufts of shining orange-yellow needles m. p. 198-199O and gives cherry-red and intense blue colora- tions in the cold with concentrated nitric and sulphuric acids respectively. T. H. P. Quinhydr-nes. WILHELN HIW:MUKD ( J . p i - . CIzcm. 19 15. [ii] 92 342-370. Compare A. 1909 i 109; 1911 i 654).-After a discussion ,Of the various constitutions proposed f o r t<he quin- hydrones the author decides in favour of the suggestion of Willstatter and Piccard (A 1908 i 475) who apply to these compounds a formula of the type the undulating lines indicating partial valencies.This view of the structure is considered to be in good accord with the tendency of the quinone constituent of some '' mixed " quinhydrones (that is quinhydrones in which the quinone and the phenol are1 not derived from the same parent hydrocarbon) t o remove hydroxylic hydrogen atoms from the accompanying phenol and so to effect oxidation t o the t'rue quinhydrone corresponding with the phenol. The following quinhydrone compounds are described the general method cf preparation being to mix a light petroleum solution of the quinone with an ethereal solution of the phenol and to allow the mixture t o crystallise. From thymoquinone and quinol the coni- pound 2~l,Hl,02,3C6H,0 red needles decomp.137O ; from thymoquinone and resorcinol an unstable red compound decomp. 43-45O the proportion of resorcinol being between unimolecular and sesquimolecular; from thymoquinone and catechol a red oily compound 2C,,H,,02 3c&H,O,. pXyloquinone with quinol and catechoil respectively gave red needles m. p. 153-156O and red msnoclinic crystals m. p. 87O; each of the molecular composition CsH80,,2C6H,02. m-Xyloquinone in a similar manner with quinol and catechol gave isomeric compounds of the same composition very deep red leaflets m. p. 12O-12lo and long red needles m. p. 44-45O respectively. Likewise o-xyloquinone with quinol and catechol gave similar compou?zds deep red needles with a green lustre m. p. 118O and red needles m. p. 60-62O respectively. Resorcinol formed no quinhydrone compounds with the xyloquinones.C,H,*O H 0 PU,~H,-O I€ *O*C,H Chlorobenzoquinone and quinol gave a c o v ~ p o ~ n d 2C,H,02a3C,H,( OH),,ORGANIC CHEMISTRY i. 153 bronze-coloured crystals m. p. 123-124O (compare Ling and Baker T. 1893 63 1314; Schmidlin A. 1911 i 727). ni- Dichloro- trichloro- and tetrachloro-benzoquinone when mixed with quinol oxidised this substance to ordinary benzoquinone- quinol quinhydrone. Benzoquinone with gentisic acid P-resor- cyclic acid and protocatechuic acid gave rise respectively to very deep red needles of no definite m. p. red prisms of no definite m. p. and deep red crystals m. p. 179-180° the products being isomerides of the composition C6H,0,,2C,H604. Benzoquinone with orcinol gave deep red prisms of a compound C6H40,,C,H802 hydrated orcinol also giving red crystals of a compound With gallic acid and ethyl gallate benzoquinone was converted into ordinary quinhydrone.The results show that although there is no simple law ruling the composition of the quinhydrones a considerable regularity exists in the influence exerted by various substituent groups. For the analysis of the above products the author made use of the titanium trichloride method (Knecht and Hibbert A. 1911 ii 76). C6H,O,,C7H,O,,H,O. D. F. T. The Action of the Three Isomeric Aminophenols on a-Naphthaquinone. EMIL GROSSMANN ( J . pr. Chem. 1915 [ii] 92 370-390).-The general method of procedure was to allow the naphthaquinone (2 mols.) to react with the aminophenol (1 mol.) in h o t alcoholic solution the resulting compound being formed by the condensation of one molecule of each the second molecule of naphthaquinone serving as the necessary oxidising agent.The condensation of paminophenol and naphthaquinone gave 2-p-hydroxyanilino-a-naphthaguinone C,,H,O,*NH*C,H,*OH red needles m. p. 225O which was reducible to a colourless compound. The formation of the condensation product was examined from a quantitative point of view and the mechanism was demonstrated to be as described above the second molecule of naphthaquinone being reduced to the corresponding quinol. The product gave cherry-red solutions in concentrated acids and blue solutions in alkalis ; it possessed only feeble acidic properties and the prepara- tion of the corresponding phenoxides miscarried with the possible exception of the potassium derivative in the attempt to produce which an unstable blue amorphous powder was obtained. Methyl- ation with methyl sulphate also failed t o give a satisfactory result the product consisting of a mixture of red needles and deep violet capillary needles.The methyl ether of 2-phydroxy- anilino-a-naphthaquinone C,,H50,*NH*C6H,*OMe was therefore prepared in the usual manner from naphthaquinone and p-anisidine in alcoholic solution containing a little acetic acid the product forming fiery red needles m. p. 158O; the corresponding e t h y l ether C,,H,0,*NH*c?6H4;OEt obtained from naphthaquinone and y- phenetidine consisted of deep red needles m. p. 264O; acetyl derivative C,,H,O,*NAc*C,H,~OEt a deep raspberry-red micro- crystalline powder m.p. 1 7 5 O . When treated in the cold with 9*i. 154( ABSTRACTS OF CHEMICAL PAPERS. acetic anhydride and concentrated sulphuric acid phydroxyanilino- a-naphthaquinone was converted into a diacetyl derivative CIoH50,*NAc*C6H4*OAc red prismatic needles m. p. 170° and with benzoyl chloride and pyridine i t gave a benzoyl derivative C,,H,O,*NH C,H4*OBz deep orange-red needles m. p. 210°. 2-m-l~ydroxya~aili~ao-a-~i a pli t h a gu ino 12 e was prepared in an analogous manner to its para-isomeride and was found t o form deep violet needles m. p. 242O soluble in potassium hydroxide t o an azure-blue solution and in sulphuric or hydrochloric acid to a cherry-red solution ; beizzoyl derivative deep red prismatic needles m. p. 208O. The methyl and ethyl ethers were obtained by effecting the condensation of naphthaquinone with nz-anisidine and ni- phenetidine the compounds forming long red needles m.p. 1 7 2 O and deep red needles m. p. 195O respectively. 2-o-Hydroxyanilino-a-napht?~n~i~inone prepared from naphtha- quicone and o-aminophenol is an almost black substance with very little tendency to crystallisation ; i t was obtained in brown flocks m. p. 175O and as a chocolate-brown microcrystalline powder m. p. 205O. The corresponding nzetlbyl and ethyl ethers obtained by effecting a similar condensation between naphthaquinone and o-anisidine and o-phenetidine formed deep red needles m. p. 146O and fiery red needles m. p. 152O respectively. Preparation of Chloroanthraquinones. AKTIEN GESELLSCIIAFT FCJR ANILIN-FABRIKATION (Eng.Pat. 1915 5182; from J . SOC. Chenz. Znd. 1915 34 1203).-Hydroxyl groups in anthraquinone derivatives are replaced by chlorine without affecting the ketonic groups or the hydrogen atoms of the nucleus by the action of the chlorine compounds of phosphorus. Thus for example 1- hydroxyanthraquinone when treated in nitrobenzene solution a t 150° with phosphorus pentachloride and boiled for three hours under a reflux gives after removing the nitrobenzene by steam tiistillation 1-chloroanthraquinone which is recrystallised from glacial acetic acid. Preparation of Anthraquinone Derivative8 [Mercaptans]. CHEMISCHE FABRIK GRIESHEIM-ELEKTRON (Eng. Pat. 8254 June 1915; from J . SOC. Chem. Znd. 1915 34 1136).-a-Hydroxy- or a-amino-derivatives of anthraquinone are heated with an alkaline sulphide with o r without added sulphur a t 140-150° when the hydrogen atom in the ortho-position with regard to the hydroxyl 0s amino-group is replaced by the thiol group.The products are valuable dyes or intermediate substances. Preparation of Dianthraquinone Oxides. AKTIEN GESELLSCHAFT FUR ANILIN-FABRIKATION (Eng. Pat. 24347 ; 1914 Dec. ; from J . SOC. Chem. Zna?. 1915 34 1135).-l-Nitroanthraquinone or its substituted products yield 1 1'-dianthraquinone oxide or its deriv- atives when heated with an acid-fixing substance such as an alkali carbonate' in a n indifferent solvent o€ t h e aromatic series. D. F. T. G. F. M. J. (2. W. J. C. W.ORGANIC CHEMISTRY. i. 155 Preparation of New Phenanthraquinone Dyes. E. R. WATSOP and K.C. MUKHERJEE (Eng. Pat 9311 June 1915; from J . Soc. C'henz. Incl. 1915 34 1136).-Bromo- or bromonitro-derivatives of phenanthraquinone are condensed with amines of the benzene or naphthalene series giving dyes which colour chrome-mordanted or unmordanted wool fast dark blue violet or greenish-blue shades. The fastness t o light is improved by sulphonation. Example bromo-2-nitrophenanthraquinone (100 parts) is boiled with aniline (1000) and copper powder (25) f o r two hours when the hot liquid is filtered into an excess of dilute hydrochloric acid the 2-nitroanilino- phenanthraquinone being precipitated. isoPulegolphosphonic Acid. FRAYCIS H. DODGE ( J . A n i c r . Chew. ~SOC. 1915 37 2756-2761).-A re-investigation of the compound originally termed citronellal-phosphoric acid and now designated isopulegolphosphonic acid which the author obtained earlier (A.7 1891 286) from citronella1 and phosphoric oxide in the presence of a little water.The substance is a monobasic acid m. p. 181-182O which crystallises in large monoclinic plates (a b c = 1-9828 1 1.9745 P=57*83O) ; potussizim salt C,,H,,P04K,3H,0 large plates ; socliiim salt plates; mngnesiiim salt plates; c d c i u t ~ i salt; silccr salt,. When cautiously heated the sodium salt decom- poses with formation of isopulegol. In spite of its monobasic character the acid is regarded as a phosphinic acid of the structure PRO(OH) the constitution of the radicle R being uncertain. The formation of this acid shows no promise of providing a reaction for the detection of citronella1 in essential oils.D. F. T. J. C. W. Constituents of Oil of Caesia. FRANCIS 1). DODGE and ALFRED E. SHERNDAL (J. Znd. Blzg. Chem. 1915 7 1055-1056).-The oil of Citinamonmm cassia contains at least 0.5% soluble in dilute alkali from which by acidification and steam distillation about 25% of its weight of salicylaldehyde was isolated. The' rest of the alkali soluble portion consisted of coumarin (60%) cinnamic acid (8-10%) and small amounts of benzoic and salicylic acids and an unidentified liquid volatilel acid. W. ADRIANI (Rec. trcrv. chim. 1915 37 180-210. Compare Fosse A. 1914 i 859).-An examination of the behaviour of xanthydrol towards substituted carbaniides and towards aromatic amines and their derivatives substituted in the nucleus or in the amino-group.Monosubstituted carbarnides give monoxanthyl derivatives with xanthydrol in alcoholic solution in the presence of acetic acid. The author has prepared xantl~ylmethylcarbanzide Cl5HI4O2N2 m. 11. about 230° phenylxanthylcarbamide m. p. 225O (compare Fosse loc. c i t . ) o-tolylxanthylcarbamide C,,H,,O,N m. p. 2 2 8 O p-tolyl- s.anthylcarb amide and /3-?mpht hylzant hylcnr bamide C,,~,,O,N,. Of the disubstituted carbamides the symmetrical derivatives do not form xanthyl compounds whilst the unsymmetric derivatives give monoxanthyl compounds such as diph eq7 y l m n thylcarbamidp G. F. M. Action of Xantbydrol with some Amides and Amines. p 2i. 156 ABSTRACTS OF CHEMICAL PAPERS. C,H,02N2 m. p. 179-180° and xanthyl-as-dimethylcarbamide C,,H,,0,N2 m.p. 225O have been prepared. s-Diphenylcarbamide and s-dimethylcarbamide were recovered unchanged. With aniline in the presence of a small amount of acetic acid in alcoholic solution xanthydrol gave dixant hytaniline C,,H,,O,N together with a small amount of xanthyla&ne ClSH150N m. p. 185'5-187O. The latter compound was also obtained by the action of xanthydrol on aniline hydrochloride under the usual conditions or by the action of xanthydrol on aniline in the presence of a large excess of acetic acid. The three toluidines gave dixanthyl derivatives. Thus dixanthyl- o-totuidine C133H2502N dixanthyl-m-toluidine and dixanthyl-p- t oluidine were prepared. Of the xylidines examined m-4-xylidine gave a dixmthyl C,,H,,O,N whilst m-2-xylidine only gave a ?nonoxanthyZ derivative m.p. 170.5O. The three nitroanilines all gave monoxanthyl derivatives rant hyl-o-nitroandine C,,H,,O,N xant hyl-m+,itroaniline and zanthyl-p-nitroadine being prepared. Neither 2 4-dinitroaniline nor picramide gave any xanthyl derivative. Of the anilines substituted in the amino-group methylaniline gave dixanthylme t hylaniline C33H2502N and dimethylaniline gave xanthyldimethylanilinel (compare Fosse loc. cit.). Diphenylamine yielded xanthyldiphenylamine CZ5Hl9ON and acetanilide gave a small amoant of xanthylaniline. From the naphthylamines there were obtained respectively di- xan th yl-a-napht hylamine C,Hz5O2N and dixanthyl-p-napht hyl- (I min e . As an example of aubstances in which the nitrogen is linked to a strongly negative group benzamide and methylnitroarnine were chosen.The former gave xunthylbenzamide C,,H,,O,N m. p. 218O and the latter gave xnnthylmethylnitroamine Cl,H,,0,N2 m. p. 1 1 7 ' 5 O . The behaviour of these compounds towards hydrochloric acid was then examined to see if xanthyl chloride was liberated as indicated .by an intense yellow coloration. Of the substances described above all gave a yellow coloration except xanthylaniline xanthylxylidine derived from m-2-xylidine xanthyldimethylanigne xanthyldiphenyl- amine and dixanthyl-a-naphthylamine. Dixanthylaniline gave the yellow coloration indicative of the formation of xanthyl chloride but a t the same time a precipitate of xanthylaniline m. p. 185*5-187O was obtained. These results indicate that in xanthylaniline xanthyldimethyl- aniline and xanthyldiphenylamine the xanthyl group and in di- xanthylaniline and dixanthylmethylaniline one of the xanthyl groups is attached to1 the benzene! ring and the other to the amino- nitrogen.I n the case of the monosubstituted carbamides and the asymmetric disubstituted carbamides the xanthyl group has entered the second amide group thus NHMe-CO*NH*C,,H,O and NM%*CO*NH*C,,H,O. I n the case of the derivatives from the three toluidines and m4-xylidine one of the xanthyl groups is attached t o the nitrogen atom and the other to the benzene ring.ORUANIC CHEMISTRY. i. 157 The evidence in the case of the three xanthylnitroanilines is not clear but the xanthyl group is possibly attached to the benzene ring. The two xanthyl groups in dixanthyl-a-naphthylamine are attached to carbon whilst in the l3-isomeride a t least one of the xanthyl groups is attached to nitrogen.I n xanthylbenzamide the xanthyl radicle is attached to nitrogen and this is probably true of xanthylmethylnitroamine since it gives the reaction for true nitroamines. Theise colour reactions with hydrochloric acid are confirmed by the green fluorescence test with sulphuric acid. The above-men- tioned exceptions do not give the green fluorescence characteristic of xanthydrol whilst all the others do. The author considers that the general constitution of these xanthydrol derivatives is better represented by formula I than by formula 11 bringing them into agreement with the accepted formula for xanthyl chloride. W. G. Process for Hydrogenating Unsaturated Substances.C. I!. BOEHRINGER & SOHNE (Eng. Pats. 1914 21583 and 21948; froin J . SOC. Chem. Znd. 1915 34 1225).-The unsaturated substance in aqueous or alcoholic solution or suspension is treated with hydrogen in presence of a suboxide of nickel copper iron or cobalt as catalyst. Details of the hydrogenation of quinine hydrochloride morphine cinnamylcocaine cinnamic acid and aminoacetonitrile are given. G. F. M. Preparation of a Derivative of Thebaine. $1. FREUND arid E. SPEYER (D.R.-P. 286431; from J . SOC. Chem. Ind. 1915 34 1168).-A new base C,,H,,O,N decomp. above 275O is obtained by treating thebaine in acid solution with hydrogen peroxide or potassium dichromate. J. C. W. Action of Grignard’s Reagent on Tertiary Pyrroles. K. HESS (Ber. 1915 48 1969-1974. Compare A.1914 i 725).-A reply to Oddo (A. 1914 i 1142). Hess and Wissing obtained some 2-acyl-1-methylpyrroles by treating 1-methylpyrrole with mag- nesium ethyl bromide and then with acyl chlorides. They assumed that magnesium 1-methyl-2-pyrryl bromide was first formed with t’he evolution of ethane. Odd0 pointed out that 1-methylpyrrole does not react with the Grignard reagent and assumed that Hess’s base contained free pyrrole. The author now states that his base was pure but that it certainly does notl give ethane unless water is present. It must combine with the magnesium ethyl bromide however otherwise this would react with the acyl chloride to give a carbinol which it does not. Moreovelr the additive compound which i t forms is unaffected by an acyl chloride until water is added when the 2-acyl-1 methylpyrrole and ethane are produced.i. 158 ABSTRACTS OF CEEMICAL PAPERS An arrangement is described by which it is possible to determine whether ethane is liberated even when such reactions are carried out in a hygroscopic liquid like ether and if so t o estimate it.J. C. W. Action of Derivatives of the Propane Series on Pgrrole. 11. KURT HESS and HEINRICH FINK (Ber. 1915 48 1986-2005. Compare A. 1913 i 1378).-The preparation of pyrroles substi- tuted by derivatives of propane opens up the possibility of synthesising certain bases of the pyrrolidine series such as hygrine cuskhygrine and tropine. A number of compounds of this nature have therefore been prepared. An ethereal solution of epichlorohydrin was treated with potassio- pyrrole when two products were obtained namely a-1-pgrryl- propylene by-oxide C',H,N*CK,*C fl-C'11 a limpid mobile oil \/' 0 with mustard-oil odour b.p. 93-94O/11 mm. and a dimeride of this a viscous odourless oil b. p. 195-200°/16 mm. The mechan- ism of the reaction is the same as in the action of epichlorohydrin on sodiomalonic esters and such compounds (Traube and Lehmann A 1899 i 417; 1901 i 501). The potassiopyrrole is first attached to the oxide ring and then potassium chloride is eliminated; thus C4H4NK + CH2-CH*CH2C1 = C,H,N*CET,*CH(C7K)*C~T2CI -+ \/ 0 C,H,N*CH2*CH-CH + KCI. \/ 0 This course would account for the production of the dimeride and is supported by the fact that monochlorohydrin and potassiopyrrole yield propylene oxide pyrrole and potassium chloride.Dichloroisopropyl acetate (acetyldichlorohydrin) also reacted with potassiopyrrolel to' form the above oxide and its dimeride. I n this caxe the hydrin se'enis to1 decompose into epichlosohydrin and acetyl chloride for the product also contains a new diucetylpyrrole C,H,O,N which remains behind as the potassium salt when the other substances are extracted with ether. The compound forms rectangular prisms m. p. 55* b. p. 105O/16 mm. The above a-1-pyrrylpropylene By-oxide was used in a number of reactions. Thus with an ethereal solutdon of magnesium ethyl bromide it reacted without any evolution of ethane to give y-bromo-a-l-~yrryZpro~?z-~-oT C,H,N*CH,*CH(OH)*CH,Br as a colourlees syrup h. p. 137-139°/14 mm. whilst in boiling benzene i t gave in addition a new pj/rryl alcohol probably C,H,N*CH,* CH (OH) CH,E t as a limpid oil with a faint odour b.p. 115-117°/14 mm. The bromohydrin was converted into the acetate y-bronzo-a-l-pyrryli~- propgZ acetate C4H4N*CR,=CH(OAc)*CR2Br by the1 action of magnesium ethyl bromide followed by acetyl chloride and byORGANIC CHEMISTRY. i. 159 similar meaiis into the p-tiifrobenzoate C,,H,,O,N,Br m. p. 79-80°. The acebate is an unstable aromatic syrup which gives a number of products when left with sodium methoxide of whicli only the chief has been isolated. This is probably y-nzethosy-a-l- pyrrylprolm n-B-ol C,H,N*CH,* CH (OH)*CH,* OMe which has h. p. 143O/12 mm. The propylene oxide readily combines with water when heated at looo in an atmosphere of nitrogen in a sealed tube t o forni a - l - ~ y r .~ y l p r o ~ ~ i e - ~ y - c l i o T as a limpid viscous oil b. p. 167-168O/ 15 mm. with a bitter taste. It also' absorbs hydrogen chloride in cold ethereal solution yielding y-c7Lloro-a-l-pyr~yl~ro~n-8-ol C,H,N*CH,*CH(OH)*CH,Cl b. p. 109-110°/ 12 mm. 122'5O/ 19 mm. This was methylated by means of methyl iodide and silver oxide the reaction requiring special care and y-chloro-8-methoxy- a-l-pjrrylpropise C,H,N*CH,-CH(OMe)*CH,Cl was obtained as a mobile fragrant oil b. p. 103~5-105°/20 mm. Attempts were inade to eliminate hydrogen chloride from this and potassiopyrrole was found t o be effective. This pives a mixture of Dvrrole. a bi- 2 . I cyclic co mpo mid probably of t1ie"f ormula 2>CH*OBIe c H y c H cH%H*N*CH a mobile oil with an intense not &pleasant odour b.p. 73-'74O/ 20 mm. and ~ - m e t h o ~ y - a y - d i - l - p y r r y l ~ r o ~ ~ ? ~ e (C,H,N*CH,),CH*OMe a very stable viscous oil b. p. 149*5-150*5°/20 mm. Methyl- alcoholic potassium hydroxide also effects the removal of hydrogen chloride giving the above bicyclic compound and also 8-nzethoxy- a-l-pyrrylpropun-y-ol C,H,N*CH2*CH (0 Me) CH,*OH b. p. 105-108°/26 mm. Dichlorohydrin was also methylated by carefully treating a solu- tion of it in methyl iodide with silver oxidel. The dichloroiso- propyl methyl ether CH(CH,C1)2*OMe thus obtained is a mobile highly refractive very volatile oil with a refreshing odour b. p. 47'5O/20 mm. 159-159.5O/740 mm. which reacts with potassio- pyrrole in benzene solution t o give the above1 bicyclic compound CH:C-CH C,H,,ON and an isomeride probably I >NH CH.OI\Ie of the formula (annexed) which is an unstable oil b.p. 104~5-106°/11 mm. s-Dichloroacetone wa5 boiled with acetic acid and excess of anhydrous potassium acetate and thus converted into chloroacetylnzethyl acetute CH,Cl*CO*CH,*OAc b. p. 112-114°/16 mm. JOHN GUNNING MOORE DUNLOP (tlic late) (T. 1915 107 1712-1713).-aa-Dimethylglutarimide has been relduced by means of sodium and boiling amyl alco.ho1 t o 3 3-cFirnefltylp~peridiize a strongly alkaline base with b. p. 1 3 7 O which forms a deliquescent JAydrochloride a fiydriodide m. p. 200° an aurichloride needles m. p. 182O and a benzoyl derivative needles m. p. 68-69O b. p. 204O/15 mm. It was desired t6 con- vert the base into 3 3-dimethyl-1 l-trimethylenepiperidinium CH C-CH,/ J.C. W. 3-genz-Dimethylpi~eridine.i. 160 ABSTRACTS OF CHEMICAL PAPERS. iodide in connexion with another research (compare T. 1912 101 1748) but this could not be realised. Preparation of a Carbonate of Sodium 2-Phenylquinoline- 4-carboxylate. CEIEMISCHE FABRIK AUF ACTIEN (VORM. E. SCHERING) (D.R.-P. 285499; from J . SOC. Chem. Ind. 1915 34 1167).-A compound C1,H,,O2NNa + C,,H,,O,N + H,CO which has more therapeutic value than 2-phenylquinoline-4-carboxylic acid or its sodium salt i6 obtained by the interaction of this acid and sodium carbonate or sodium hydrogen carbonate of the sodium salt and carbon dioxide or of 2-phenylquinoline-4-carboxylates and sodium hydrogen carbonate. J. C. W. Derivatives of o-Aminophenol and a-Amino-P-naphthol.E. VON MEYER ( J . I". Chem. 1915 [ii] 92 255-271).-An investiga- tion of the benzoxazolone compounds obtainable from o-amino- phenols and a-amino-P-naphthol by the action of carbonyl chloride. [With HUGO SAHLAND.]-~ 2-Dihydrobenzoxazolone (carbonyl- J. C. W. o-aminophenol) C,H,<-O->CO NH can be produced in better yield than that previously obtained (Schmitt and Hentschel ibid. 1888 [ii] 37 27) by allowing the action of the carbonyl chloride and o-aminophenol to occur in pyridine solution. With care o-hydroxyphenylcarbamic acid OII*C,H,*NH*CO,H m. p. 95O can be isolated as an intermediate product which a t looo passes into the oxazolone compound ; the silver salt undergoes a similar dehydr- ation a t l l O o .By treatment with phenylcarbimide and in alkaline solution with ethyl chloroformate dihydrobenzoxazolone is respec- tively converted into ethyl 1 2-dihydrobenzoxazolone-2-car6oxyZate *<U,H 4>N*Cil,Et. leaflets m. p. 78O and the corresponding nnilide O<!&%>N*CO*NHPh short needles m. p. 125O; a benzojyl derivative# O<-e 4>NBz crystlals m. p. 165O and a nitro-deriv- . -co- C H co- ative CO<~~>C,H;NO yellow needles rn. p. 242O were also prepared. Interaction with aniline produced a substance probably the and C,H4<O_>C:NP h insoluble in alkalis. Under similar conditions t o the preceding a-amino-P-naphthol was converted into 1 2dihydronaphthoxazolone (carbonylamino- naphthol) C,,H,<-O->CO prisms m. p. 206O which when heated with concentrated hydrochloric acid a t 150° undergoes fission into the origina.1 aminonaphthol and carbon dioxide.Treat'ment in alcohollic solution with methyl and ethyl iodide in the presence of potassium hydroxide produced respectively 2-met hyl-1 2-dihydro- naphthoxazolone C,,H,< >GO very pale red needles m. p. 184O and its 2-e thyl-analogue C,,H,<Y(~>CO needles M. p. NH NH NMe 0-ORGANIC CHEMISTRY. i. 161 141O. Acetylation and benzoylation yielded respectively 2-acetyl- 1 2-dih,yc%ro1zaphtlz~oxazolo?ze C,,H6<-O->Cd NAc pale red needles in. p. 121° and the corresponding 2-benzoyl compound colourless needles m. p. 256'. Treatment with aniline a t 250° effected fission of the heterocyclic ring with formation of P-hydroxy-a-naphthyz- taminoformanilide OH-C,,H,-NH*CO-NHPh needles m p.229' I n cold acetic acid solution chlorine converted the naphthoxazolone compound into a-chloro-1 2-dihydronaph thoxazolone c,oap<y>co uiifused atl 310° whereas in chloroform solution the product was an isomeric /3-chloro-compound pale yellow crystals of high m. p. ; longer treatment with chlorine in hot acetic acid solution gave rise t o dichloro-P-naphthaquinone. By heating with phosphorus penta- chloride and treating a hot acetic acid solution with chlorine a very pale reid dichloro-l 2-dihydronaphth oxcIzoloize KH C,,H,CI,<-()->C(' of high m. p. and a tetrachloroacetyl-l 2-dih~ydrona~hthoxnzolo~te a yellow crystalline solid m. p. 75O possibly of the structure ?Qb&->N-CO*CCI C HC1 were respectively obtained. Similarly by bromination in acetic acid solution a bromo-1 2-dihydronaphth- oxazolone C,,H,Br<-,>CO yellow neledles decomp.a t 250° NH and a dibromo-derivative C,,H,Br,<?E>CO yellow needles m. p. above 300° were obtained. Nitration in acetic acid solution by nitric acid or nitrous fumes in the latter case using a hot solution . yielded a nitro-1 2-dihycEronaphthoxazolone NO2*C1,Hs<-,>~ NH '0 needles decomp. near 270° m. p. above 300° whereas the action of sodium nitrite on a cold acetic acid solution gave 2-nitroso- 1 2-dihyd~onaphthoxazolone O<($~~>X*NO a yellowish-brown solid decomp. a t 170° m. p. 194O. [With PAUL RAS SFELD.]-M&~Y~ 4-amino-3-hydro~xybenzoate7 (" a-orthoform '7 is converted by formic acid into a formyl deriv- ative CHO*NH*C6H,(OH)*C0,Me colourless tetragonal leaflets m.p. 225O which a t 240' loses water with formation of methyl benzoxazole-5-carboxylate CO,Me*C,H,<~>CH yellow needles m. p. 99O. I n a similar manner the isomeric methyl 3-amino- 4-hydroxybnzoaf%e (" P-orthof orm ") is coavertible successively into itts formyl derivative silky neledles m. p. 222O and methyl benz- oxazole-4-carboxylate small needles m. p. 107O. The two methyl aminohydroxybenzoates can also be1 converted into their acetyl derivatives NHAc*C,H,(OH)*C'O,Me needles m. p. 18B0 and m. p. 204O respectively which can be dehydrated by zinc chloride a t looo and by acetic anhydride at 140-150° respectively givingi. 162 ABSTRACTS OF CHEMICAL PAPEHS. iit e t h y l 1-me thy1 b e1~zoxazole-5-carbozyla t e C0,Me*C6H,<~>CMa slender needles m.p. 103-104° and the isomeric methyl 1-methyl- be~iaoxazole-4-carbo~ylate silky needles m. p. 66O. Methyl 4-amino-3-liydroxybenzoate forms with ethyl oxalate ail trddztzve compound C22H,,0,,N needles m. p. 1 1 2 O which when tieated with excess of the ethyl oxalate is converted into methyl o,,,trT~ldi-(4-nn1 in o-3-h ydroxy b eir zoa t e ) C,O,[N H C,H (0 H) C O,Me] rods m. p. 298-300°; ammonium salt yellow powder; diacetyl derivative stellar groups of needles m. p. 171O; dibemoyl deriv- ative needles m. p. 231O. Methyl 3-amino-4-hydroxybenzoate gave 110 addit.ive compound with ethyl oxalate but on heating a mixture of the two substances met h y 1 o xaZyldi-( 3-amino-4-hydro xy b e nzoa t e) needles m.p. 312-313O was obtained which was also produced from a solution of the oxalat'e of the aminoester on prolonged boiling. When fused with phthalic anhydride methyl 4-amino-3-hydroxy- benzoate reacts giving a condensation product of the possible con- stitution (an- /\CO,Me nexed formula) I prisms. m. p. \/ 229O The same ester in dilute sodium hydroxide solution when treated with a toluene solution of carbonyl chloride gave leaflets m. p. 228O of 111 e thy1 1 2-dikydro b enzoxazolon e-5-curb oxyla t e co~"l".~'-o>cco-)c<~~:;;J 1 I-NH C6H4 \/ Y tlie alternative enolic constitution CO,M~*C,H,<;) >C*O H also being possible ; the compound gives a methyl derivative needles m. p. 16S0 and an acetyl derivative leaflets m. p. 170O. The interaction of me'thyl 3-amino-4-hydroxybenzoate and car- bony1 chloride has already been investigated (Einhorn and Ruppert A.1903 i 257). The action of carbon disulphide on this ester in alcoholic solution a t 160-170° gives methyl thio-1 2-dihydro- YH b enzo xaz ole-4-car b ox y la t e C0,Me 'C H3<~o->CS needles m. p. 228O which from its ability to dissolve in alkalis may have the tautomeric constitutio'n CO,Mo*C,I€,<~>C*S H. With the isomeric 4-amino-3-hydroxy-ester interaction with carbon disulphide occurs less smoothly. With nitrous acid methyl 4-amino-3-hydroxybeiizoate and its 3-ainino-4-liydroxy-isomeride are converted into dimonnhydrides N CO,Me*C,H,<O>N yellow solids decomp a t 70° and 1 1 7 O respec- tively with feeble explosion. Both products couple with phenols giving dyea D.F. T.ORGANIC CHEMISTRY. i. 16:j Preparation of Ether-like Derivatives of Barbituric Acid. CHEMISCHE WERKE VORM. H. BYK (D.R.-P. 285636; from J . Soc. C'hem. Znd. 1915 34 1167).-Alkylalkyloxyalkyl- or dialkyloxy- alkylmalonic acids or their derivatives are condensed with carbamide in the usual way giving products which are less toxic than diethyl- barbituric acid. Examples Ethyl malonate sodium ethoxide P-iododiethyl ether and carbamide yield ~ i - ~ - e t J i o s y e t J ~ y l i t i a l o i ~ ~ ~ ccrrbamide and ethyl malonate sodium ethoxide 8-iododiethyl ether ethyl iodide and carbamide yield ethyl-6-ethoxyeth ylmaloiiylca~b- uttiide and in turn from these' 5 5-cLi(B-ethozyeth?/l)bcirhitziric acid and 5-P thyl-5-P-e t Jz ox ye t 11 yl b a ~ b i t u ric a cid are formed.J. C. W. The Condensation of Aldehyde Diacetates and of Phenyl- hydrazones with 2-Thiohydantoin. BEN H. NICOLET ( J . ,41?ier. C'lzem. Soc. 1915 37 2753-2756).-It is already known that aromatic aldehydes cam be condensed with hydantoin 2-thiohydan- toin and substituted derivatives of the latter by boiling together with acetic acid and sodium acetate (Wheeler and Hoffmann A. 1911 i 498; Wheeler and Brautlecht A. 1911 i 500; Wheeler Nicolet and Johnson A. 1911 i 1031). The value of the condensa- tion lies in the possibility of reducing the products to benzyl- liydantoins which are readily hydrollysed to phenylalanines. The author now siiowe that the aldehyde in this condensation may be replaced by its diacetate or phenylhydrazone; the use of the latter derivative especially enables condensation products to be formed in cases where the corresponding aldehyde would be too volatile.Under the usual conditions of the condensation benzylidene diacetate and 2-thiohydantoin gave rise t o 2-thio-4-benzylidene- liydantoin and benzaldehydephenylhydrazone yielded the same pro- duct. With acetaldehydephenylhydrazone and 2-thiohydantoin the product was 2-thio-4-etIi ylidetzehydatztoiii YH.CO)C:CHMe a CS*NH yellowisli-brown crystalline powder m. p. rather indefinite a t 253O. D. F. T. 2 4 6-Triaminopyridine. HANS MEYER and ERICH RITTER VON BECK (J!onatsh. 1915 36 731-749. Compare Meyer and others A. 1912 i 514; 1913 i 530; 1914 i 438 439).-In an attempt to obtain 2 4 6-triaminopyridine citrazinic acid (2 6-dihydroxy- pyridine-4-carboxylic acid) was converted by the action of phos- phoryl chloride a t ZOOo into 2 6-dichloropyridine-4-carboxylic acid of which the1 nzPthyl ester C,H2NC1,-C0,Me needles m. p.8 2 O on treatment with hydrazine hydrate a t water-bath temper- ature readily gavel 2-c1iloi.0-6-hycEmzii~o~yri~i?~ e-4-carboxylh~ydrazide NH,*NH*C,H,NCl*CO*NH-NH needles m. p. 226O with redden- ing but the product obtained by working in alcoholic solution was 2 6-dicJztoropyridz'ize-4-cnr boxylhydrazide C,H,NC12*CO*NH*NH2 needles m. p. 1 8 4 O . This substance when treated in very dilute hydrochloric acid solution with sodium nitrite gave 2 6-dichloro-i. 164 ABSTRACTS OF CHEMICAL PAPERS ~ r i d i i z ~ - c a r b o x ~ l a z i d e C5H,NC12*CO*N3 a pungent feebly ex- plosive powder m.p. 89O which yielded ethyl 2 6-dichloro-4-pyridyl- carbamate C,H2NCl,*NH*C0,Et needles m. p. 132O when boiled with alcohol ; hydrolysis of this substance with aqueous alcoholic pot'assium hydroxide solution caused almost quantitative formation of 2 6-didhZoro-4-aminopyridine C,H,NCl,*NH colourless needles 111. p. 1 7 6 O . 2 6-Dichloropyridine-4-carboxylic acid was also heated a t 210° with a concentrated solution of ammonia and a little copper bronze when 2 6-diaminopyridine-4-carboxylic acid C,H2N(NH,),*C0,H was obtained as a .sparingly soluble powder the methyl e s h very pale yellow needles m. p. 1 7 3 O (&hydrochloride greenish-yellow needles m. p. 208O with decomp. ; dibenzoyl derivative needles m.p. 312O) of which slowly reacted with concenkrated ammonia solution at the1 ordinary temperaturel giving 2 E-diaminopyridine- 4-carboxyZamide C5H,N(NH2),*CO*NH2 leaflets m. p. 256O (decomp.) The methyl elster of the diaminopyridinecarboxylic acid failed t o react witlh hydrazine hydrate in boiling alcoholic solution but in the absence olf the alcohol the two1 substances interacted readily giving the hydrazide C,H,N(NH,),*CO*NH*NH colourless needles m. p. 260° (decomp.) in an open tnbe. It was not found possible to convert the hydrazide into the corresponding azoimide derivative probably ojn account of nitrous acid simultaneously affecting the amino-groups and endeavours to apply the corre- sponding dibnzoyldiamino-derivative to the reaction with nitrous acid were foiled by the1 failure to osbtain this substance from the action of methyl dibenzoyldiaminopyridinecarboxylate on hydrazine hydrate the product being the1 diaminopyridinecarboxyl- hydrazide itself.I n the absence of copper bronze the reaction pro- duct obtained from 2 6-dichloropyridine~4-carboxylic acid and corn- centrated ammonia solution a t 200° was 2-chloro-6-aminopyridine- 4-carboxylic acid needles of high m. p. (decomp.). The aim of the inveatigation wm successfully achieved by heating 2 6-dichloro-4-aminopyridine with ptoluenesulphonamide together with sodium carbsonate and a little copper bronze a t 180-190° and hydrolysing the1 resulting 4-amino-2 6-cFi-p-toZuenesulpho~yl- diaminopym'dine NH2*C5H2N(NH*S0,*C~H,Me)2 lustrous needles decsmp. above 360° with concentrated sulphuric acid when 2 4 6-triamino;ayridine C5H2N(NH,) was obtained as colourless needles m.p. 185O ; tIhe platinichloride reddish-yellow needles readily decomposes with liberation of platinum. F. KEHRMANN (Ber. 191 5 48 1931-1933).-The view that the green methylphenazonium periodide is a half-quinonoid compound is confirmed by its form- ation from the half-quinonoid iodide by the addition of iodine in alcoholic solution thus C,,H,,N,I,C,,H,,N,I + I + EtOH = (I,,H,,N,I,,EtOH (compare A. 1914 i 331). Oxidation of Uric Acid in Alkaline Solution. IiI. ROBERT BEHREND and RUDOLF ZIEGER (AnnaZe?z 1915 410 337-373. Compare Behrend A. 1904 i 950; Behrend and Schultz A D. F. T. [Methylphenazonium Iodides.] J. C. W.ORGANIC CHEMISTRY. i. 165 1909 i 272).-In tracing the course of the oxidation of uric acid in alkaline solution.Behrend (Zoc. cit.) assumes the intermediate ',N EVL;(OH~CO-T H. This must 'NH*C(OtI)*N H-CO formation of a substance CO be incorrect because Biltz's uric acid glycol (A. 1912 i 589) with which the preceding substance should be identical does not yield allantoin and uroxanic acid by hydrolysis but is converted into ammonia and syrupy products even by alkali carbonates in the cold. The suggation is now made that in its oxidation in alkaline solution uric acid is ruptured in the 1:6 position and an inter- NH*F(OH)*CO,H is produced. Attempts to synthesiss this substance from alloxanic acid and carbamide were unsuccessful. When an aqueous solution of alloxan tetrahydrate and a large excess of carbamide are heated to incipient boiling with 36% hydro- chloric acid carbamide alloxanate C4H40,N2,CO(NH2) is ob- tained together with a little alloxantin.The former crystallises from water in four-sided almost rectangular prisms decomp. 155-156O and is converted into carbamide nitrate by concentrated nitric acid and into normal or acid calcium alloxanate by calcium salts. Carbamidel alloxanate can also be obtained by warming uric acid glycol with 35% hydrochloric acid a t not more than 50°. When alloxan tetrahydrate is dissolved in warm water and the cooled solution after renoval of any alloxantin by filtration is treated with carbamide a substance C5HA06N4 colourless crystals decomp. 1 1 7 O or 133-134O is obtained which appears to be a saltc like compound of carbamide and alloxan monohydrate. It yields carbamide nitrate by treatment with nitric acid and is converted by 'heating alone or with glacial acetic acid into uric acid glycol; when boiled with acetic anhydride it yields an anhydride C5H606N4 microscopic nedles decomp.185-186O. Potassium ulloxan C4H,0,N2K pale red needles decomp. about 23Ci0 is obtained by dissolving alloxan tetrahydrate in warm water and treating the cooled filtered solution with 50% potassium hydr- oxide a t Oo. Methods are described f o r utilising this salt for the preparation of potassium alloxanate carbamide alloxanate and alloxanic acid. Methyl alloxanate C,H,O,N prisms decomp. 175-176O can only be obtained by warming alloxanic acid with thionyl chloride a t 40-50° and heating the resulting solid chloride with methyl alcohol.The aqueous solution of the ester reacts strongly acid towards litmus and decomposes hydrogen carbonates mediate substance Co<NH.C(OB)NH*CONR,' but is easily hydrolysed by 10% potassium hydroxide. c. s. Constitution and Colour. IV. Colour of Azo-compounds and their Salts. F. KEHRMANN (Ber. 1915 48 1933-1931. Compare A. 1908 i 699 993; 1913 i 1320).-Since azo-compounds contain two nitrogen atoms each of which may become the point of attachment of an acid by exerting it8 two additional valencies,i 166 ABSTRACTS OF CllEMlCAL PAI’ERS. they should give rise to two series of salts. This point has been tested by dissolving some azo-compounds in sulphuric acid of various strengths. Azobenzerie gives a very deep golden-yellow solution in con- ceiitrated sulphuric acid but a deep red in acid containing 25% SO which however soon becomes paler owing t o sulphonation.p-Aminoazobenzene gives a red solution in acid containing 25% SO a golden-yellow in the ordinary conceutrated acid and a bluish- red in ail acid of a certain dilution. Chrysoidin gives a golden- yellow solution in the concentrated acids and a bluish-red in diluted :wid. In the case of azobenzem i t is suggested that the two coloars are due to the mono-acid and the di-acid salts. The other cases are explained o n the assumption that salt formation a t the cliromo- pliolrei causes a deepening of colour whereas a t the amino-group i t iwially causes a lessening. J. C. W. A Decomposition of Cei fain o-Nitromandelic Acids.GERTRUDE MAUD ROBINSON and ROBERT ROBINSON (T. 1915 107 1753-1762).-Tn a previous communication (T. 1914 105 1466) i t was i2oted that 6-nitro-3 4-methylenedioxymandelic acid gave rise to a dark brown product when boiled with nitrobenzene. The nature of tbe decomposition has now been revealed in the first instance by a study of the action of heat on 6-nitro-3 4-dimethoxy- mandelic acid and i t is found that the chief products are azo- benzenedicarboxylic acids. The oxygen of the nitro-group oxidises the hydroxy-acid chain and the complete reaction may be repre- muted thus G -S i f r o -3 ; 4 -dime t Ib o x y tn a tad e I i c a c id NO,* CGH,( OMe),-CH(0H) *CO,H was prepared by the hydrogen cyanide synthesis from 6-nitrovertr- aldehyde in pale yellow needles m.p. 169-172O (decomp.). When this was heated in nitrobenzene a vigorous action took place and 4 ; 5 41 5/-tetrcrmethoxyrrxobeltze~ae-2 21-dicarboxylic acid was deposit,ed in crystals resembling haematite in colour and lustre. On triturating this with nitric acid (D 1-45) it yielded 2 2’-dinitro- 4 5 4’ 5’-tetramethoxyazobenzene [NO,*C,H,(OMe),],N which crystallised from nitrobenzene in brilliant red needles m. p. 315O (deconip.). An orange-coloured modification of the same compound identical in m. p. was obtained by the nitnration of azoveratrole by cold nitric acid (D 1.42) in acetic acid. Both forms dissolved in sulpliuric acid with intense blue colours but they were1 recovered in their original forms on dilution which precludes the idea of cis-trans-isomerism.Both f orm8 were also reduced by stannous chloride t o 4 5-diaminovaratrole which was isolated as 2 3-di- metlioxyphenanthraphenazine m. p. 259-261° by treatment with phenantliraquinone (compare Moureu 1896). [CO,H*C,H?(OMe),l,N,,ORaANlC ClIEMlS'l'HY. i. 16" Azoveratrole was obt.ained by a modification of Kauffmann and Kugel's method (A 1911 i 930) in glistening orange prisms m. p. 182O and not 1 6 3 O . When this was suspended in acetic acid and treated with fuming nitric acid it yielded apparently N 2 2'-tri- niti.0-4 5 4f 5f-tetranietholryhyclrcczobensene N0,*C,H,(OMe)2-NH*N(N0,).C,H,(OMe)2*N02 yellow needles m. p. 228O which was also1 converted into 2:3-di- methoxyplienanthraplienazine as above. The decomposition of 6-nitro-3 4-methylenedioxymandelic acid by heating in nitrobenzene solution differed somewhat from the above reaction in that nitrogen was also evolved.The chocolate- coloured product contained about 25% of other products besides the 4 5 4' 5/-dirnet?~ylerzetetrctozyazobenzer~e-2 2'-dicarboxylic acid LCH:02:C,H,(C02H)]2N2 but only this could be isolated. This was achieved through the soditim salt yellow leaflets and the acid was obtained in opaque masses of brick-red crystals m. p. 270° (decomp.). 'On nitration the carboxyl groups were replaced by nitroxyl giving 2 2'-dinitro-4 5 41 5f-dimet?~yletietetrooxynzrr- 71 Pnzene CI4HSOsN4 in crimson needles in. p. 305O (decomp.) which was reduced and then condensed with phenanthraquinone as above with the formation of 2 3 - r n e t h y l e n e d i o x y p l ~ e l z c t n t ~ ~ r a ~ ? ~ e r ~ ~ ( 6-Nitrohomopiperokyf chloride CH2:O2:CGH2(NO,)*CH2C1 was obtained by saturating an acetic acid solution of homopiperonyl alcohol with hydrogen chloride and then gradually adding nitric acid.It formed pale pink leaflets m. p. 86O and irritated the skin. When heated with nitrobenzene it changed into the above' 4 5 4' 5f-dimethylenetetraoxyazobenzene-2 2/-dicarboxylic acid whilst cold methyl-alcoholic potassium hydroxide converted it into 2 2'-di11itro-4 5 4' 5/-dimethylenetetraoxystdlbene brownish-red needles not molten a t 350O. The above a.zobenzene1 derivatives axe characterised by giving intense blue solutions in concentrated sulphuric acid even with the merest traces. J. C.W. [CH2:02:C,H2(NO,)12C,H2 The Preparation of Aliphatic Aminohydraeines. AUGUST DARAPSKY and HANS SPANNAGEL ( J . pr. Chem. 1915 [ii] 92 272-296).-A record of the results of a series of unsuccessful endeavours to prepare aliphatic aminohydrazines of the type NH2*CR*CR'*NH*NH2. The product of the interaction of dia~etylmo~noxime and hydr- azine varies with the solvent. I n aqueous solution a mixture of the former with hydrazine sulphate yielded the ketazine OHON CMe*CMe:N*N :CMe-CMe:N*OH (compare Forster and Day T. 1912 101 2240); dibenzoyl deriv- ative orange-red scales m. p. 215O. I n alcoholic solution using hydrazine hydrate t.he product is diacetylhydrazoxime m. p. 13S0 which has also been recently described (Eoc. cit.). OH*N:CMe*CMe:N*NH Thisi. 168 ABSTRACTS OF CEEMICAL PAPERS is unstable in aqueous solution readily undergoing conversion into the ket'azinel and hydrazine but is more stable in alcoholic solution and in this solvent reacts with aromatic aldehydes giving normal condensation products ; thus with salicylaldehyde o-hydroxybenzyl- idenediacetylhydrazoxime OH*N:CMe*CMe:N*N:CH*C6H4*OH yellolw needles m.p. 168O was obtained. An attempt t o confirm the structnre of this substance by an independent formation from diacetylmonoxime and o-hydroxybenzylidenehydrazine failed on account of the mfusal of these compounds to interact. Diacetyl- liydrazoxime gave a beizzoyl derivative ye'llow needles m. p. 201° and reacted with phenylthiocarbimide giving a thiosemicarbazone OH*N:CMe*CMe:N*NH*CS*NHPh flesh-red needles m.p. 201O. If a mixture of diacetylmonoxime and hydrazine hydrate in the absence of a solvent is boiled for several hours the oximino-group is replaced by the hydrazone group with the foxmation of diacetyl- diliydrazone NH,*N:CMe*CMe:N*NH m. p. 157O (dib enzylidenc derivative yellow needles m. p. 120° ; di-o-hydroxybeizzylidenc derivative yellow needles m. p. 245O) which in alcoholic solution in the presence of dilute hydrochloric acid undergoes change into dimethylaxiethane CMe<&i> N (compare Curtius and Thun A. 1891 1356). On account of t.he instability of diacetylhydrazoximel reduction t o the desired aminohydrazine could not be effechd and attention was therefore turned to the reduction of the more stable ketazine but without achieving the isolation of any reduction product.Benzilhydrazoxime (compare Forster and Day loc. cit.) was then submitted to reduction with so'dium amalgam in alcoholic solution but the product was meso-diphenylethylenediamine NH,*CHPh*CHPh*NH (Japp and Moir T. 1900 77 644). I n an attempt t o prepare benziIhydrazoxime by the action of hydroxylamine hydrochloride on benzilhydrazone a yellow substmce m. p. above 280° not show- ing the properties of an oxime was obtained. Aminoacetophcnone hydrochloride when treated in cold aqueous solution with hydrazine hydrate yielded diphenyldihydrocpyrazine the hydrazine hydrate merely acting as an alkali (compare Gabriel A. 1908 i 464) whilst with the heated reagents in the absencs of a solvent aminoacetophenoneaaine NH,*CH,*CPh:N*N:CPh*CH,*NH2 colourless needles m.p. 157O was obt'ained. When a solution of aminoacetophenone hydrochloride and hydrazine hydrochloride was neutralised with sodium hydroxide the effect on the first substance was merely that of an alkali the product being anhydrobisphen- acylamine (compare Gabriel loc. cit.). P-Bromopropylamine hydrobromide reacted with hydrazine hydrate in aqueous solution giving a basic viscous oil the com- position of which was represented approximately by the formula C3H,N ; tlhis gave an oily b enzoyl derivative. 8-Hydroxy- up-dlphenylethylamine was converted by phosphorus pentachloride into stilbene dichloride but the desired chlorodiphenylethylamine,ORGANIC CHEMISTRY. i. 169 NH,*CHPh*CHPhCl was prcduced by shaking a suspension of the hydrochloride of the hydroxydiphenylethylamine in acetyl chloride with phosphoxus pentachloride being obtained as an oil ; hydro- chloride m.p. 233O (decomp.) ; phtinichloride deep yellow needles m. p. 204O; nitrate tablets m. p. 185O; benzoyl derivative m. p. 195O. Chlorodiphenylethylamine in alcoholic solution is converted by hydrazine hydrate o r also by potassium hydroxide into di- >NTT colourless needles m. p. 83O ph enylet h yleneimine which does not reduce potassium permanganate and is reconverted even in ethereal solution by hydrogen chloxide into chlorodiphenyl- ethylamine hydrochloride. Benzo-€-chloron.liz?/lnmide when heated with excess of anhydrous Iiydrazine gave an oily product which when treated in aqueous solution with benzaldehyde instead of yielding the expected benzoylbenzylidenehydrazinoamylamine NHBz*[CH,],*NH*N:CHPh gave benzoylbenzylidenehydrazine NHBz*N:CHPh the chemical change having involved scission of the benzoyl radicle as benzoyl- liydrazine with concurrent conversion of the chloroamylamine into piperidine.D. F. T. $! H Ph c HPh Traneition Points of the Polymorphic Phthalylhydrazides. FREDERICK DANIEL CHATTAWAY and WILLIAM JAMES LAMBERT (T. 1915 107 1773-1 781) .-Phthalylphenylhydrazide and phthalyl- 13 henylnietliylhydrazide C,B,<CO>R*N co N P h and C,H,<::>N*N RlePh (T. 1911 99 2256 2261) are well-marked and readily obtainable examples of enantiomerides. The transition points f o r the two pairs have therefore been determined. This has been don0 in the first place by measuring the solubilities then in the cam of the second pair by observing the growth of the crystals of one form a t the expense of the other in acetone and finally by a dilatometric method.I n the case of phthalylphenylhydrazide the curve8 f o r the solubility in alcohol indicate a transition point a t about lUu; in chloroform a little above 9.4O; in ethyl acetate 9.2O; and in acetone 9.8O. The two forms are so much more soluble in the last three solvents and the transformation takes place so much faster that the transition points are more easily ascertained. The mean is about 9*5O. I n the case of phthalylphenylmethylhydrazide the solubility determination in alcohol indicates a transition point a t about 55O (by extrapolation) the second method gives 55-55*5O and the dilatometric method 55-55.2O.I n his theoretical deductions concerning the reversible trans- formation of polymorphic forms van't Hoff (1897-1898) showed that the ratio of the solubilities of the two forms must be constant for all solvents which only dissolve so little that the laws of dilute solutions are applicable. This conclusion has now been confirmedi. 170 ABSTRACTS OF CHEMICAL PAPERS. experimentally for the first time by the determination of the solu- bilities of these pairs of hydrazides. Aromatic-aliphatic Diaeoamino Compounds [ Arglazodicyano- diamides]. R. VON WALTHER and W. GRIESHANMER (J. pr. Chem. 1915 [ii] 92 209-255).-It has been discovered that not only does guanidine couple with simple diazonium salts producing stable compounds (investigation unpublished) but that' substances allied to guanidine namely dicyanodiamide cyanamide and dicyanodi- aniidine although less basic behave analogously towards diazo- compounds.Dicyanodiamide couples with an aromatic diazoxide in alkaline solution the solution when acidified depositing the diazoamino- compound. The first yield is polor but more can be obtained by making the filtrate alkaline and again acidifying; i t is suggested that tliis further formation of the diazoamino-compound may be due t o the dicyanodiamide in the alkaline solution existing in part as a disodium salt which a10110 is active towards the diazo-com- pound. The hydrogen atom of the *N,*NH* group in these diazo- amino-compounds is replaceable by metals and also by radicles but froin the fact that hydrolysis of the methyl derivative of p-toluene- azodicyanodiamide yields rnetliyltoluidine with a little pcresol i t is evident that in this case a t leastl alkylation does not entirely follow a single course.Benzeneazodicyanodiamide and its analogues are generally not very reactive. On hydrolysis in feebly acidic aqueous or alcoholic solution or suspension the former compound yields dicyanodiamide and tarry products without aniline thus indicating a structure C"*NH*C( :NH)*NH*N,Ph as opposed t o CN*NH*C ( NH) ON NHPh. 'hi strongly acidic solution or suspension the' products of hydrolysis are plienylguanylcarbamide and free nitrogen. The identity of the phenylguanylcarbamide was demonstrated by an independent syn- thesis by the hydrolysis of s-cyanophenylguanidine (Wheeler A.1903 i 751). I n explanation of tlie difference in behaviour of ~~enzeneazodicyanodianlide towards hydrolysis in feebly and strongly acidic solutions it is suggested t h a t in tlie former case the substance possesses its usual ( Z I I ti-configuration thus CS*NH*C(:N€l)*NH*N J. C. W. RPh + cN+wq:m)-sri + v2 + c!,~K,-T)TI whereas the stronger acid causes a conversion througIi the hydro- chloride into a syi)-configuratsioii CN*NH*C,:wR)*N t r y th sub- PhN" et ance 011 hydrolysis readily eliiiiiiiates nitrogen yielding phenyl- guanylcarbamide NH,*CO*NH*C( :NH)*NHPli. The isolation of an unstable hydrochloride leiids support to this idea but in 110 case have geometrical st.ereoisomerides been isolated. As is to be ex- pected the tendency to the addition of hydrogen chloride is less in the more acidic compounds of this class.In the description of theseORGANIC CHEMISTRY. i. 131 compounds the grouping NH:N*NH is termed triazen the first and third nitrogen atoms being designated by a and y (Wolff and Lindenhayn A. 1904 i 197). Beraeneazodicyanodiarnide (a-phen yltriaze ii-y-cyana niirioiniitLo- iiiethathe) CN*NH*C(:NH)*NH*N,Ph was prepared by mixing cold aqueous solutions of benzenediazonium chloride and dicyanodiamide and treating the diluted solution successively with solutions of sodium hydroxide and hydrochloric acid ; the product crystallises in prisms decomp. with slight explosion a t 123O. It! is decom- posed with mild explosion on contact with sulphuric acid. Boiling water causes decomposition into dicyanodiamide together with tarry matter in which a little phenol is present whilst hydrochloric acid of 15% concentration gives rise t o phenylguanylcarbamide.The following salts were prepa.red Sodium yellow needles ; ammoniurri prisms ; pyridine yellow ; siZuer explosive yellow powder; lead yellow ; cobalt bluish-red ; ferric yellow ; ferrous brown. By treating the sodium salt with an alco'holic solution of methyl iodide CN*NH*C( :NH)*N,*NMePh yellow needles decomp. a t 167-168O was obtained whilst with benzyl chloride and pnitrobenzyl chloride in a similar manner y-pheti yl- y-b e n z yl triazen-a-cyana rnidoirnin o met hati e CN-NH-C( :NH) *N,*NPli*CH,Pli I ieedles decomp. a t 165-1 66O and y-pl~eil.!jZ-y-p-)hitro7) eti syl triazetr -a- c.yaiw,~iit,oiniitivi7~et~ic[ti~ CN*NH*C(:NH)*N2*NPh*CH,.C,H4*N02 colourless needles decomp.at. 1 6 2 O were respectively obtained. p-ToZrcenenzodic!/anocFianzide (a-p-to7~~lt~iazei~-y-cyai1n??iii~o~niii~metfmne) CN-NH.C(:NH)-NH*N,-C,H,Me obtained by diazotising ptoluidine and proceeding as In the previous case forms yellow rhornbs decomp. a t 1 3 3 O ; sodium salt yellow needles; yotassiirw salt. The action of methyl sulpliate on the free compound in the presence of sodium hydroxide solution caused the format"ion of y-p- to7y7-y- I I I P th yl triaze?i-a-c!yana nt in o int in0 ?n et haw CN-NH*C( :NH)*N,*NMe*C,H,Me yellow needles decomp. a t 155-158O which on hydrolysis with dilute acid gave methyl-ptoluidine dicyanodiamide and a little p-cresol the formation of the latter proba,bly being due to t$eY presence of an isomeride.An alcoholic solution of benzyl chloride converted the sodium salt into y-p-tolyl-y-b eiiz.yltriazei~-a-cyaiianii~~~~- irnifto m e t 7m 12 e CN*NH*C (:NH) *N,*N( CH,Ph)* C6H4Me colourless needles decomp. a t 1 6 3 O whilst p-nitrobenzyl chloride under similar conditions produced y-p-toZ,Vl-y-p-nit rob e ? ~ z?/Ztl.iaze?~-a-c?/anamino- i mirhom e t han e CN0NH.C ( NH) ",ON( C,H,Me) *CH,*CGH4*N0 yellow needles deconip. at 1 5 8 O . An attempt to effect a rearrange- ment of ptolueneazodisyanodis.nide1 into the corresponding amino- azo-compound by warming with ptoluidine and aniline hydro- chloride evidently caused fission of the molecule the isolated pro- duct being aminoazo-ptoluene. o-Tolu en eazodicya n odia ??I ide (a-o- t oly 1 t riaz eqi - y-cyu I I a H I iriointin (1- methlane) CN*NH*C(:NH)*NH*N,*CsH4Me obtained in a similar nianner forms yellow needles decoinp.a.t 1 1 4 O ; sodizrnr salt yellow -ph e?) yl- y-m e t h y ltriaz en-a-cya 71 an2 in o iinino nz e t h a w ,i. 172 ABSTRACTS OF CHEMICAL PAPERS needles. y - o - Tolyl- y - methyltrimen - a - cyanaminoiminomethane CN*NH*C( :NH) N2*NMe*C6H4Me yellow leaflets decomp. a t 1 5 2 O and y-o-tolyl-y-b enzyltriazen-a-cyanaminoiminomethane CN*NH*C( :NH)*N,*N(C,H,Me)*CH,Ph pale yellow needles decomp. a t 160° were obtained similarly t o their para-isomerides. m-Tolueneazodicyan odiamide (a-m-t olyl triaz en- y-cyanaminoim ino- methane) yellow needles decomp. a t 1 1 5 O (potassium salt less soluble than the sodium salt) prepared in the usual manner was converted into y-m-tolyl-y-methyltriazen-a-cyu?i~minoiminonzetJ~a~~e yellow needles decomp. a t 1 4 8 O and y-m-tolyl-y-h enzyltriazen-a-cyan- ccminoirni7z.ometha7z e pale yellow needles and prisms decomp.at 1 5 3 O . ( a - p - c hlor o ph englt riu z o t i - y-cyanaminoiminomethane) CN-NH*C(:NH)*NH*N2-C6H,Cl yellow 1-liombs decomp. a t 140-160° (pJricFine salt yellow) was further converted into y-p-c hloroph eny l- y-me t h yl t riaz en-a-cyanamin oimiii o- niethnne CN*NH*C( :NH) *N2*NMe*C6H4c?l yellow needles decomp. a t 160° and into y-p-chlorophenyl-y-benzyltriazen-a-cyai2anziiioinii?io- methane CN-NH*C(:NH)*N,*N(C,H,Cl)*CH,Ph colourless needles m. p.. 170-175O. As with the benzeneazo-compound no very definite results were obtainable in reduction experiments with the pchlorobenzeneazo-compound and very little aminodicyanodiamide was pxoduced if any; a compound (or compounds) separated from the reduction product gave a p ' c m t e m.p. 190° and a pale yellow benzylidene derivative decornp. a t 1 7 0 O . ( a - p - bromopJ~enyltriuze,i- y-c yammimiminome t hane) CN*NH*C( :NH)*NH*N,*C,H,Br rhombs decomp. a t 160° (sodium salt; q,widine salt yellow) pre- pared in the general manner was convertible into y-p-bromophenyl- y-me t h y l triaaen-a-cyanaminoiminomethane CN0NH.C ( NH) *N,*NMe* C,H4Br yellow needles deoomp. a t 1 8 5 O and y-p-~~~~~~~~~~~~~~y-benzyltri- azen-a-cyanaminoiminome t hane CN =NH*C ( NH) *N,*N (C,H,Br) *CH2P h colourless needles decomp. a t 1 8 6 O . o-Curb oxyb enzeneazodicyanodiamide (a - o - curb o x y p k e i i y l tTiuze t i - y-cyanaminoiminomethane) CN*NH*C ( NH) *NH*N,*C,H,*CO,H prepared from diazotised anthranilic acid in the general manner is a yellow crystalline solid decomp.near 98O which is decomposed by boiling water intol salicylic acid dicyanodiamide and nitrogen ; sodium salt C,,H,,O,N,,Na ; silver salt C,,H,,O,N,,Ag an amorphous yellow solid. Attempts t o prepare a methyl o r benzyl derivative by way of the sodium salt were unsuccessful. I n an endeavour to convert benzeneazodicyanodiamide and its derivatives into the ethyl ester of the corresponding carboxylic acids by treatment with alcoholic hydrogen chloride i t was dis- covered t h a t nitrogen was eliminated with formation of an aryl- guanylcarbamide. There were thus prepared p-Chlorophenyl- gw.znyZcarbamide C,H,Cl*NH*C(:NH)*NH*CO.NH colourless rhomlx m.p. 1 2 5 O ; hydrochloride prisms m. p. 172-173O; platini- p-C hloro b en z enea zodicyanodia mide p-BromobenzeneazodicyamdiamideORGAKIC CHEMISTRY. i. 173 chloride yellow prisms; picrate m. p. 195O; silver salt colourless; t i ce t yl derivative C,H,Cl*NAc*C( :NH) *NH*CO *NH prisms m. p. 150-1 5 lo. Phe ?zylgziai~ylcarbnmide NHPh*C( :NH) -NH*CO*NH colourless hexagonal prisms m. p. 62-63O ; hydrochloride prisms 111. p. 174-175O; picrate m. p. 181-182O. p-Tolylgzianylcarbamidr C,H4Mel*NH*C(:NH)*NH*CU*NH2 rectangular leaflets m. p. 143O ; hydrochloride prisms m. p. 167-168O. o-Tolylgziu,zyTcarbamide octahedra m. p. 136O; hydrocldoride needles m. p. 73-74O.m-Toll/lguanylcarbamide hexagonal leaflets m. p. 97-98O ; hydro- chlorade prisms m. p. 183-184O. p-Bromophenylgzicrnylcarb- amide C,;H4Br-NH-C(;NH)-NH*CO*NH2 prisms m. p. 152O ; hydrochlorade leaflets m. p. near 170O. o-Carbozyyhenylyuanyl- cnrbamide CO,H*C,H,*NH-C( :NH)*NH*CO*NH prisms o r needles decomp. a t 275-280°; silver salt C9HH,03N,Ag,. An endeavour to extend the investigation of the effect of alcoholic hydrogen chloride to the methyl derivatives of the above compounds was prevented by the complexity of the reaction with these substances. I n the course of experiments attempting the synthesis of phenyl- guanylcarbamide by an independent method substances m. p. 155O 130° and above 280° were obtained from the interaction of silver cyanocarbamide and aniline hydrochloride under varying condi- tions.The interaction of phenylguanidine nitrate and potassium cyana,te under varying conditions yielded phenylgwznzdine car- bonate prisms m. p. 138O (decornp.) and a sparingly soluble sub- stance m. p. above 290° but failed to give the desired phenyl- guanylcarbamide which wa6 however successfully produced by heating cyanophenylguanidine CN-NH*C(:NH)*NHPh with dilute hydrochloric acid. diet h?llthiolphenylbi2Lret SMe*C( :NPh)*NH*CO*NH colourlelss needles m. p. 156O was obtained by a similar hydrolysis of s-cyanomethylthiolphenylisocarbamide SMe*C(:NPh)=NH.CN. The formation of phenylguanylcarbamide from benzeneazodi- cyanodiamide suggests that cyanophenylguanidine is an intermediate product and this substance can actually be isolated under suitable conditions.If benzeneazodicyanodiamide in ethereal suspension is treated with hydrogen chloride an unstable red substance is obtained which from its decomposition by warm water into cyano- phenylguanidine hydrogen chloride and nihrogen is in all prob- ability the hydrochloride of the syn-f orm of benzeneazodicyano- diamide. By a similar procedure all the benzeneazodicyanoldiamide derivatives described above with the exception of the o-carboxy- derivative which did n o t form a hydrochloride were made t o yield the corresponding cyano-arylguanidines. There were thus obtained s-cyano-p-tolylguanidine CN*NH=C( :NH)*NH*C,H,Me rectangular leaflets m. p. 207-208° ; s-cyano-m-tolylguanadane rectangular leaflets m. p. 193-194O ; s-cyano-p-chlorophenylguanidine CN*NH*C( :NH)*NH*C,H,Cl rectangular leaflets m.p. 197-198O ; s-cyano-p-bromophenylgzLcrrz- idine CN*NH*C(:NH)*NH.C,H,Rr rectangular leaflets m. p. nicyanodiamidine resembles dicyanodiamide in its ability t o 196-1 97'.i. 174 ABSTRACTS OF CHEMICAL. PAPERS. couple with diazo-compounds in alkaline solution the product obtained with an alkaline diazobenzene solution being b enzeneazo- rlicyanodirrnlidir,e (a - yhenyltriazen - y - carbnmidoiininoine fhnne) NH,*CO*NH*C( :NH)*NH-N,Ph yellow needles decomp. at. 176-177O which possesses feeble basic and still more feeble acidic properties; T/,yd~ochZoride yellow prisms decomp. near 92O ; picrate needles decomp. a t 70°. When treated with alcoholic hydrogen chloride solution this product behaves differently from its dicyano- diamidel analogue giving no cyanophenylcarbamide but only di- cyanodiamidinel and tarry matter.The coupling of cyanoamide in alkaline solution with a benzene diazo-oxide gives benzeneazocyanoamide which has already been described (Wolff and Lindenhayn Zoc. c i t . ) . The Refractive Indices of Solutions of Certain Proteine. IX. Edestin. CARL L. A. SCRWDT (J. Biol. Chem. 1915 23 487-493).-The solutions of edestin follow the law n - n1 = nc ; where i? is the observed index of the solution nl of the solvent c the percentage of protein and n a constant expressing a change in the refractive index due t o the addition of 1% of the protein. I n the case of edestin a=0*00174 +_0.00006. This remains constant even although the solvent produces hydrolysis.W. D. H. The Nature of Enzyme Action. IV. The Action of In- eoluble Enzymes. W. &I. BAYLISS (J. Physiol. 1915 50 85-94).- Urease Iipase emulsin invertase lactase papain peroxydase and catalase are active in media from which they can be filtered off by ordinary paper whilst the filtrates are inactive. Pepsin and trypsin are much inore active in suspensions than are the filtrates; these enzymes are capable of a small degree of colloidal solution i n such solutions. Enzymic activity is thus manifested a t the interface of contact between the solid enzyme phase and the liquid substrate phase. The catalysts concerned are not in true solution. The ‘Effect of Sodium Chloride on the Action of Invertase. H. A. FALES and J. M. NELSON ( J . Amer. Chern. SOC. 1915 37 2769-2786).-The concentration of hydrogen ion remains constant during the inversion of sucrose by invertase.The addition of sodium in the action may exert a twofold effect it caiises an increase in the coiicentration of the hydrogen ion if the concentra- tion of the hydrochloric acid present is greater than 0*0001 molar; and also effects a decrease in the activity of the invertase if com- parison is made between solutions of the same concentration with regard t o hydrogen ion. The latter effect varies according t o the concentration of the hydrogen ion and of the sodium chloride being least a t the optimum of the invertase action. The adjustment of the concentration of the hydrogen ion by the addition of mixtures of acids and salts (“buffers ”) as sometimes practised may intro- duce appreciable error unless it is restricted t o the neighbourhoocl of the optimum zone where the salt effect is a minimum. The addition of sodium chloride t o solutions of hydrochloric acid D. F. T. W. D. H.ORGbh’IC CHEMISTRY i. 175 cauaes an increase in the concentration of the hydrogen ion as measured by the E.M.F. method and by the hydrolysis of sucrose solutions. I n the region of enzyme activity i t is therefore necessary to measure the concentration of the hydrogen ion and i t is not permissible to calculate it from the concentration of the acid used. D. F. T. The Rstention of Activity by Urease and by Oxydase after Exposure to the Temperature of Liquid Air. JOSEPH Smum HEPBURN and CHARLES BLIZARD BAZZONI ( J . Franklin Ztist. 1915 180 603-605).-After exposure to the temperature of liquid air for 100 hours a solution of urease was found to have suffered but slight loss in its power of hydrolysing carbamide. The observed activity was 96.3% of that of the fresh solution. During the same period the activity of a solution which was kept a t ZOO in presence of 0.2% of tricresol was found to have fallen to 44.4%. Qualitative experiments show also that oxydase retains its power of reacting with Witte’s peptone after subjection to the temperature of liquid air for 33 hours. Preparation of 2-Chloro-4-dimetbylaminobenzene-l-arsinic Acid. C. F. BOEHRINGER S SOHNE (D.R.-P. 286546 ; from J . SOC. (:hem. Znd. 1915 34 1165).-m-Chlorodimethylaniline is treated with arsenic trichloride and the 2-chloro-4-dimethylaminobenzene- 1-arsenoxide so obtained is oxidised by means of hydrogen peroxide mercuric oxide or potassium permanganate. Compared with the non-halogenated compound 2-chloro-4-dimethylaminobenzene-2- arsinic acid is less toxic but has a greater therapeutic activity. J. C. W. H. M. D. Preparation of 4 4’- Dihydroxy-3 3’-diaminoarsenobenzene. fm ~TABLTSSEMENTS POULENC FR&RES (Eng. Pat. 1914 21421 ; from J . r C o ~ . Ch~nr. Incl 1915 34 1225).-3-Nitro-4-liydroxy- phenyl-1-arsinic acid is reduced by zinc and acetic acid a t 25-35’) and then in hydrochloric acid solution a t 50-60° in presence of a small quantity of sulphurous acid and is thereby converted into 3 3’-diamino-4 4/-dihydroxyarsenobenzene. The sulphurous acid appears to prevent the reduction being carried past the forinatioii of the arseno-compound. G. F. M. Preparation of a Bismethylhydrazinotetra-aminoarseno benzene. C. F. BOEHRINCER & SOHNE (D.R.-P. 285573; from J . Roc. C‘heni Z t i d . 1915 34 1165).-When 3 5-dinitro-4-methyl- nitroaminobenzene-1-arsinic acid is reduced by means of stannous chloride at 50° i t yields the hydrazine derizIafi?*e [ N H N Me C&,( NH&] ,As2 which has a pronounced trypanocidal action. J. c. w.