i. 65 Organic Chemist rg. Three Normal T e t r a t r i a c o n t a n e Saturated Hydrocarbons Triacontane and Hexatriacontane. ALBERT GASCARD (Conapt. rend. 19 12 154 1484-1487).-Pentadecyl alcohol (Simonini Abstr. 1892 1301) was converted into pentudecgZ iodide brilliant scales m. p. 24.5'. This was boiled with xylene and sodium for twelve hours when n-triacontane C30H62 was obtained as brilliant scales m. p. 65*2-65*5O isomeric if not identical with the hydro- carbons isolated from plants by Elobb (Abstr. 1910 ii l l O O ) and from the products of electrolysis of potassium palmitate by Petersen (Abstr. 1906 i 331). Heptadecyl stearate was prepared by heating silver stearate with iodine. The compound crystallises in silky lamellae m. p. 64*7O and on hydrolysis yields n-heptudecyl ulcohol pearly scales m.p. 54'. Heptudecyl iodide brilliant lamellze m. p 33&6O when treated with sodium gives n-tetratriacontane C34H70 occurring as very brilliant scales m. p. 73.2". Similarly octadecyl iodide m. p. 33.5' has been converted into n-hexat?-iacontccne C36H74 a substance cry s t a l k i n g in brilliant lttmellae m. p. 76'. w. 0. w. Catalytic Action. V. Friedel and Crafts' Reaction. JACOB B~ESEKEN (Rec. trccv. chim. 1911 30 381-391. Compare Abstr. 1910 i 152).-In continuation of the previous work it is shown that disaociable chlorides such as sulphuryl chloride pentachloroethane and chloral act as a mixture of the non-decomposed molecule in which the chlorine atoms are activated and of its products of decomposition. The first-named chloride has been tried with benzene toluene and anisole.With the two former the products of reaction are those of the condensation of the non-dissociated molecule as well as those of the products of dissociation. The latter are i n excess since the equilibrium SO,Cl Trr SO,+Cl is displaced to the right by the catalyst. In the case of anisole the reaction only yields the sub- stances formed from the products of dissociation probably owing to the fact t h a t the anisole is attacked so energetically by these products. With pentachloroethane i t is only t h e activated chlorine in the undecomposed molecule which attacks benzene although at the same time some of the pentachloroethane is decomposed into tetrachloro- ethylene and hydrogen chloride. Chloral and benzene give a very complex reaction a large number of substances being formed owing to the fact that the products of decomposition of the chloral can re-combine t o form other Substances.W. G. Autoxidation of Trichloroethylene. ERNST ERDMANN (J. pr. Chem. 1912 [ii] 85 78-89).-Trichloroethylene was prepared by VOL. CII. 1. fi. 66 ABSTRACTS OF CHEMICAL PAPERS the action of alcoholic potash on tetrachloroethane; i t has b. p. 85*8-86.0"/741.6 mm. m. p. - 8 3 O Dp 1.4649 D:" 1.4695. I n contact with air this liquid undergoes autoxidntion ; at elevated temperatures and increased pressure for example in an autoclave the reactions are complex a mixture of halogen compounds boiling between 100 and 240' being obtained due to polyrnerisations and secondary actions; at the ordinary pressure and below 60° the process is much simpler the final products being hydrogen chloride carbon monoxide carbonyl chloride and dichloroacetyl chloride the latter being the only liquid product.I n order to obtain measurable quantities of the products the experiment may have to extend over several weeks; the rate of reaction varies as the ratio of trichloroethylene to oxygen. With excess of oxygen after twenty-eight days the amount of oxygen removed is between 1 and 2 atoms for each molecule of trichloro- ethylene originally present thus indicating the simultaneous reactions CHCl:CCl + 0 = CHCl,*COCl and CHCl:CCI + 0 = CO + HCl + COCI,. On passing ozonised oxygen through trichloroethylene hydrogen chloride carbonyl chloride and carbon monoxide are formed but no dichloroacetyl chloride.By using a solution of trichloroeth ylene in hexahydrotoluene at -79" the increase in weight due to ozonide formation could be directly determined and indicated an addition of one molecule of ozoiie t o each molecule of trichloroethylene ; the ozonide which was too unstable and explosive to be examined in a pure C H Cl $XI state is therefore formulated I . The gases from an explosion 0-0:0 of the ozonide contained carbon monoxide carbonyl chloride hydrogen chloride and an oxide of chlorine ; the decomposition can be moderated by solution in chloroform or liexahydrotoluene but the product's are the same with the exclusion of the oxide of chlorine. I n decornpositioti in the presence of water hydrogen peroxide is formed. The spon- taneous decomposition of the ozonide in a dilute solution (for example excess of trichloroethylene) in the absence of water indicates that an atom of oxygen is first removed being chemically absorhed by the solvent and after removal of excess of trichloroethylene i n a vacuurn a pungent oil remains to which is attributed the formula it rapidly decomposes giving carbon monoxide hydrogen chloride and carbonyl chloride the first two of which can be regarded as the decom- position products of the intermediate formyl chloride.No indication of dichloroacetyl chloride was detected in any decomposition of the ozonide. The author therefore suggests an explanation of the sutoxidation of trichloroethylene described by the formulae ?HCl-$JCI 0-0 ; CHCl:CCl -+ CHCl*CCl -+ CHCl*CCI -+ CHCl,*COCl.\O/ \O/ .. 0 + O (1.) (11.) (111.) (IT. 1 The method of formation of the dichloroacetyl chloride is thus The nascent oxygen formed at (111) together with ordinary explained.ORGANIC CHEMISTRY i. 67 oxygen then attacks another molecule of t,richloroethylehe like a molecule of ozone giving tho ozonide which then decomposw a s described above. The possibility of autoxidation is not restricted t o unsymmetrical substituted ethylenes (compare Demola Abstr. 1878 847 ; Demole and Durr Abstr. 1878 846; Anschutz Abstr. 1880 98). The action of other oxidising agents on trichloroethylene was also investigated ; anhydrous ferric chloride attacks the substance in a sealed tube first at 8 5 O the former being reduced to the ferrous salt whilst the latter gives pentachloroethane ; a t higher temperatures the last substance loses a molecule of hydrogen chloride and the resultant tetrachloroethglene becomes further 'converted into hexachloroethane. D.F. T. The Distillation of Methyl Alcohol. GUSTAV BIRSTEIN H. DENNELER and ALFRED HEIDUSCRKA (Zeitsch. nngew. Chem. 1911 24 2429-2430).-Two series of experiments on the volatility of solutions of methyl alcohol have been carried out. In the first series in which the solutions were distilled under constant pressure it was shown that even dilute solutions of methyl alcohol yielded distillates comparatively rich in methyl alcohol. I n the second series in which the temperature was kept approximately constant and air drawn through the solution the concentration of alcohol in the distillate was found to be invariably slightly greater than in the original solution.The bearing of these results on the commercial preparation of formaldehyde is discussed. H. W. Action of Potassium Hydroxide on Primary Alcohols ; Preparation of the Corresponding Acids. MABCEL GUEHBET (Cornpt. rend. 1912 154 1487-1489 ; J. Phurm. Chim. 1912 [vii] 5 58-64).-Dumas and Stas (Ann. Chim. Phys. 1840 [2] 73 113) found that potassium hydroxide acts on methyl ethyl and amyl alcohols a t 200-230" transforming them into the corresponding acids with liberation of hydrogen. It is now shown that in the case of the lower alcohols dehydration also occurs with formation of ethylenic hydrocarbons. The higher alcohols however form only hydrogen and the potassium salt of the acid.This method of oxidation is very advantageons for alcohols above the C terms since i t is unnecessary to employ sealed tubes and the yield is practically theoretical. P-Methylpentanol gives a 95% yield of the corresponding acid which was characterised by conversion into its umide tn. p. 85O. B-Heptylhexoarnide CH; [ CH,],* CH(C7H15) *CH,-CO*NH has m. p. 108O. w. 0. w. Calcium Ethoxides. ROBERT DE FORCRAND (Compt. rend. 191 2 154 1441-1444. Compare Abstr. 1895 i 259; Doby Abstr. 1903 i 546 ; Chablay this vol. i 3).-Calcium ethoxide Ca(OEt),,ZEtOH when allowed to remain over concentrated sulphuric acid slowly loses alcohol. A specimen prepared in 1905 now approximates in com- f 2i. 68 ABSTRACTS OF CHEMICAL PAPERS. position to the formula 3Ca0 EtOH,2H20 or Ch(OEt),,5Ca0,5H,O.The suggestion is put forward that a process of catalytic decom- position occurs calcium oxide the active agent behaving as the thorium dioxide in Sabatier and Mailhe's experiments (Abstr. 1910 i 294). Calcium ethoxide is analogous to the hypothetical compound ThO(OEt) losing ethylene or ether like this substance but having greater stability a t the ordinary temperature. w 0. w. The Crystallographic Distinctions of Nitroglycerol. SIGURD NAUCKHOFF (Zeitsch. Scheiss. Spreoigstoflw. 191 1 6 124-125).-The paper contains sketches and measurements of two forms of nitro- glycerol crystals; they are of the bipyramidal class of the rhombic system but when obtained from supercooled nitroglycerol have a flattened tabular habit whilst those deposited from saturated ethereal solution are of rhombic character; their optical properties are also described.The author discusses the work of Kast (Atti V I Cong. Internax. chim. appZ. IlIb) and considers that the m. p. of nitroglycerol is - 12*5O instead of - 13.5' (Kast). F. M. G. M. Transformations of Thio- and Seleno-phosphoric Esters. P. PISTSCHIMUKA (J. p. Chcm. 1911 [ii] 84 746-760 ; from Mern. Inst. agr. forest. Now0 Alexandria 191 1 1-148).-Tloe esters of thiophosphoric acid should exist in two isomeric forms PO(0R);SR and PS(OR) but hitherto only the latter series have been prepared. It is found that the esters of this series combine with a large number of metallic salts yielding additive compounds which undergo decom- position either a t the ordinary temperature or when heated with the formation of derivat.ives of isothiophosphoric acid PO( OH),*SH ; thus the additive compounds of the alkyl esters with silver nitrate PS(OR)3,AgN0 readily lose one molecule of alkyl nitrate and form salts of the composition PO(OR),*SAg.The isomeric esters are obtained from these salts by the action of alkyl iodides. A similar transformation into derivatives of the isomeric acid is mused by alkalis alkyloxides alkyl halides and ammonia although the formation of intermediate additive products with these compounds could not be observed. The transformation is however not confined t o esters of monothiophosphoric acid but is common to all esters of the type PS(XK),*OR (where X = O or S) derivatives of PO(XH),*SH being produced.Esters of selenophosphoric acid PSe(OR) have also been prepared and converted into the isomeric forms by methods similar t o those employed in the case of the thiophosphates. The alkyl thiophosphates of the type PS(OR) were prepared by the method described pipeviously (Abstr. 1909 i 5) ; the ethyl ester has b. p. 106O/20 mm. D! 1.0944; the pvopyl ester b. p. 133-134O/ 20 mm D 1.0409 ; the isobutyl ester b. p. 155°/20 mm. Dt 0.9907 On treatment with nitric acid they yield esters of phosphoric acid and are converted by sodium into the corresponding alkyl phosphites. The compound PSCl,* SEt obtained by heating the acid chloride,ORGANIC CHEMISTRY. i. 69 PCl,*SEt with sulphur has b. p. 92.110 mm. Di 1.4453; i t reacts with sodium ethoxide yielding ethyl dithiopliosphate PS( OEt),*SEt b.p. 130°/20 mm. D 1,1340. Ethyl trithiophosphate obtained from the chloride PSCI,*OEt and sodium ethylmercaptide is a liquid b. p. 155'/20 mm. D,3 1.1716. The following additive compounds with mercuric chloride were prepared PS(OMe),,ZHgCI transparent needles melting a t 1 0 2 O and simultaneously losing methyl chloride forming the compound PO(OMe),*SHgCl,HgCl which passes a t 150' into the cornpound SHgCl*Pu(OMe)*OHgCI ; SHgC1.PO(OEt),,HgC12 forms stout trans- parent prisms m. p. 6 6 O which a t 85" yield the conapuund SHgCl*PO(OE t)-OHgCl; P S ( O P I - ~ ) ~ ~ H ~ C J ~ ; PS(OCH2Prfi),,2HgC1 ; PS(SEt),.0Et,2HgC12 white needles m. p. 81'; PS(SEt),,BNgCI m. p. 84'. All additive compounds of the type PS( XR),*OR,2HgC12 lose one molecule of alkyl chloride a t a relatively low temperature.The esters of thiophosphoric acid form with ferric chloride additive compounds of the general formula 3PS(OR),,2 FeCI which lose three molecules of alkyl chloride when heated ; the methyl compound forms large yellow prisms m. p. 125' ; the ethyl compound is crystalline ; the propyl and isobutyl compounds are oils. The ethyl esters of di- and tri-thiophosphoric acid yield with ferric chloride oily additive compounds having a similar composition. Compounds of the same type are formed with ferric bromide but only the methyl compound 3PS(OMe),,2FeBr3 m. p. 9 9 O is crystalline Ethyl thiophosphate combines with platinic chloride yielding the compound 3PS(OEt)3,2PtCl orange-yellow needles m. p. 103'. The crystalline compound of methyl thiophosphate and auric chloride has m.p. 110'. Silver nitrate dissolves in methyl thiophosphate yielding methyl nitrate and the silver salt PO(OMe),*SAg and in ethyl thiophosphate t o form the additive compound PS(OEt) AgNO which decomposes slowly a t the ordinary temperature into ethyl nitrate and the silver salt PO(OEt);SAg m. p. 8 2 O . Similar compounds are formed by the propyl and isobutyl esters. The phenyl ester reacts with silver nitrate yielding o-nitrophenol and the compound PO(OPh),*SAg. The behaviour of silver nitrite resembles that of the nitrate. Mercuric iodide combines with the alkyl thiophosphates PS(OR) t o form additive compounds which are derivatives of the isomeric ester PO(OR),*SR. Thus ethyl thiophosphate when heated with mercuric iodide a t 1 80" yields the cornpound PO(OEt),*SEt,2Hg12.Similar compounds are formed by the esters of di- and tri-thio- phosphoric acid. The interaction of alcoholic ammonia and ethyl thiophosphate yields ethylamine and the cornpound NH,*PO(OEt),. Sodium hydroxide sodium ethylmercaptide and sodium a1 kyl- oxides react with the d k y l thiophosphates to form sodium salts of the composition PO(0R);SNa. The action of sodium hydroxide and sodium alkyloxides on the esters of di- and tri-thiophospboric acids leads to the formation of a mercaptan or alkyl sulpbide togetheri. 70 ABSTRACTS OF CHEMICAL PAPERS. with sodium salts containing a smaller number of atoms in the molecule. Sodium ethylmercaptide on the other hand gives rise to the sodium salts SNa*PO(SEt)*OEt and PO(SEt),*SNa.The isomeric thiophosphoric esters of the type PO(OR),*SR are obtained by the action of alkyl iodide on the above-mentioned silver salts PO(OR),*SAg in alcoholic solution. The methyl ester has b. p. 107'/20 mm. D! 1.2685; the ethyl ester b. p. 122'/20 mm. D! 1,1245; the propyl ester b. p. 156'/20 mm. D! 1.0532; the isobutyl ester b. p. 170'/20 mm. D! 1.0102. The esters of selenophosphoric acid of the formula PSe(OR) are formed by the combination of gcmolecular" selenium and esters of phosphorous acid; the methyl ester is a liquid b. p. 95'/20 mm. DE 1.5387 ; the ethyl ester has b. p. 117'/20 mm. D 1.3189. The following additive compounds were prepared PSe(OMe),,HgCI ; PSe(OEt),,HgCI ; PSe(OMe),,HgI m. p. 66O and is simultaneously transformed into its isomeride PO( OBle),*SeMe,HgI ; PSe(OEt),,HgI large yellow prisms m.p. 32' which pass at 75' into the isomeride PO(OEt),*SeEt,HgI m. p. 95O and when warmed under diminished pressure lose ethyl iodide yielding the compound PO(OEt),*SeHgI. Ethyl selenophosphate and sodium ethyl mercaptide react to form the sodium salt PO(OEtj,*SeNa m. p. 196'; the corresponding lend salt is unstable and yields with ethyl iodide the ester PO(OEt),*SeEt a liquid b. p. 140°/20 mm. D 1.3593. Esters of the type PS(XR),*OR are transformed by prolonged heating with an excess of alkyl iodide into their isornerides. Thus ethyl thiophosphate PS(OEt) is converted by ethyl iodide into its isomeride PO(OEt),*SEt and by isobutyl iodide into the estey PO( OEt),*S*CH,Pr?.With respect to the mechanism of the above-mentioned transforma- tions the author considers that in all cases additive compounds containing either a quadrivalent or sexavalent sulphur or selenium atom are first produced and that these subsequently undergo tautomeric change and decomposition ; the action of sodium ethoxide on ethyl dithiophosphate is represented as follows PS(OEt),*SEt NaS*S(OEt):P(OEt),*SEt -+ NaS*S*P(OEt),*SEt -+ NaS*PO(OEt) + Et,S. F. B. Complex Compounds of Platinous Bromide with Organic Sulphides LEO A. TSCHUCIAEFF and (Mlle.) D. PRAENKEL (Compt. rend. 1912 154 33-35. Compare Abstr. 1910 i 354).-When an aqueous solution of potassium platinobromide is treated with ethylene- dithioglycol ether the compound [PtZC,H,(SEt),]PtBr separates as a grey microcrystalline precipitate m.p. 157". At looo this substance changes into a yellow isomeride having the same m. p. but a greater solubility in water and chloroform. The above constitution is assigned to the substance on the ground t h a t it unites with Reiset's bromide forming the salt [Pt4NH,]PtBr4 together with a yellow cornpound in. p. 157-158'. The latter has the constitution [C,H+(SF:t),],PtBr since it can also be prepared by mixing the grey salt with ethylenedi-ORGANIC CHEMISTRY. i. 71 thioglycol ether and potassium platinobrornide in equimolecular proportions Potassium platinobromide reacts with methyl sulphide giving an unstable grey compound [PtPMe,S]PtEr m. p. 160'. On crystal- lisation from chloroform this changes into Blomstrand's salt ( Me,S),PtBr,.Platinoiodides do not form derivatives with organic sulphides. w. 0. w. Intramolecular Rearrangements of Aliphatic Sulphoxides. THonrAs P. HILDITCH (Ber. 191 1,44 3583-3589).-By treatment with alcoholic hydrogen chloride or with boiling acetic anhydride diisoan?yI- sulphoxide is converted into isoamyl mercaptan and isovaleraldehyde ; by the former reagent thionyldiacetic acid is decomposed into thioglycollic and glyoxylic acids. SO( CMe,*CO,H) m. p. 186" is unchanged by alcoholic hydrogen chloride. a-T?~ionyldiisobzctyric acid An explanation of these decompositions is given which assumes the intermediate formation of thionium compounds. c. s. Complex Compounds of Platinum with Organic Selenides. I. E. FRITZMANN (Zeitech. anory. Chem. 1911 73 239-255).- The isomerism of the compounds of platinous chloride with organic sulphides has been discussed by Tschugaeff and Subbotin (Abstr.1910 i 354). The corresponding selenium compounds have not been examined with the exception of those derived from ethyl selenide (Petren Zeitsch. anorg. Chem. 1899 20 62). The isomerism observed is similar to that of the sulphur compounds. The a-componnds are more soluble than the P-compounds and are darker in colour. The former are to be regarded in accordance with Werner's views as &-modifications and the latter as trans- modifications. The y-compounds are less stable than those of sulphur. A 4% solution of potassium platinochloride (1 mol.) is shaken with the alkyl selenide (2 mols.) until decolorised. The a-compound is then chiefly obtained. I n order to prepare the P-compound 4 mols.of selenide are used and the mixture is digested at 70-75" in a closed vessel until all is dissolved. The cooled solution is evaporated in a vacuum over calcium chloride and solid paraffin or rubber and potassium chloride is then removed by washing. For analysis the compound is decomposed with sulphuric acid and heated in hydrogen t o remove selenium the residual platinum being weighed. Selenium is estimated by boiling with aqua regia in a quartz vessel evaporating and precipitating the slightly acid solution with a hot saturated solu- tion of hydrazine sulphate. The precipitated mixture of platinum and selenium is collected dried at loo" and weighed and the selenium is then removed by heating in hydrogen.Methyl selennide pZc&nous chloride PtC1,,2Me2Se has m. p. 163-1 63.5". The a-form is partly converted into the p-form by repeated crystallisa- ticm from chloroform arsd the reverse change is also observed. At ai. '72 ABSTRACTS OF CHEMICAL PAPERS. low temperature it is possible t o obtained the y-modification but it can only be isolated in the form of the green Magnus salt ( Pt,4Me2Se)C1 by t h e addition of a solution of Reiset's salt (Pt,4NH,)C12. Meth,yl selenide platinous bromide PtBr2,2Me2Se is red and has m. p. 171' (decornp.). Propyl selenide forms the compound PtC12,2Pr,Se m. p. 42.5-43'; only the a-modification has been obtained. n-Butyl selenide only yields an oily product. isoAmxl selenide yields a n a-compound PtCI2,2(C,H,,),Se m. p. 97 - 975O and rz P-compound m.p. 115-116'. The phenyl selenide a-compound has in. p. 180° and the fl-compound m. p. 178-1 79'. Piethyl trimethylene diselenide forms an a- and a P-compound 2PtCI2,2CH,(CH2*SeEt) both of which have m. p. 176-176.5". A y-modification has been recognised by conversion into the Magnus salt. C. H. D. Chemico-crystallographic Notes. L. WAGNER (Zeitsch. Xryst. Min. 191 1 50 47-56).-Phosphonium iodide PH,I ; tetragonal D 2.860. Tetramethylphosphonium iodide ; tetragonal a c = 1 0.7310 D 1.746. Calcium formate C:t(CHO,) ; orthorhombic (bipyramidal) [a b c = 0.7599 1 0.9363 (Plathan)] D 2.023. Strontium formate 8r(CH0,)2 ; orthorhombic (bisphenoidal) a b c = 0.7846 1 0.8292 D 2.693. Mixed crystals of calcium and strontium formate resemble those of either one or other of the simple salts but they also show an intermediate tetragonal form ; the two salts are therefore isotri- morphous.Strontium formate forms the hydrate Sr(CH0,),,2H2V D 2.259 ; but calcium formate forms no hydrate. Anhydrous oxalic acid; orthorhombic a b c = 0-8301 1 0.7678 D 1.900. Nitrobenzene; monoclinic (domatic?) a b c = 1.280 1 '3. ; p = 117'21' m. p. 3.8'. L. J. S. Direct Synthesis of the Glycerides. GIUSEPPE GIANOLI (Atti R. Accad. Lincei 1911 [v] 20 ii 653-654. Compare Abstr. 1911 i 349 ; Bellucci and Manzetti ibid. i 259).-Polemical. R. V. S. Formation of Cork. MAX VON SCHMIDT (J. pr. Chem. 19 11 [ii] 84 830-832).-A reply t o Zeisel's criticism (Abstr. 1911 i 768) of previous work of the author (Abstr. 1910 i 540).F. B. Derivatives of Tetrolaldehyde and its Acetal [ Diethoxy- butinene]. PAUL L. VIGUIER (Compt. rend. 1911 153 1231-1233. Compare Abstr. 1909 i 69 1).-On treating diethoxybutinene with aniline hydrochloride the hydrochloTide NHPh-CMe:CH*CH:NPh,HCI is obtained as yellow crystals decomposing at 160". No definite com- pound was obtained from aniline and phenylmethylpyrazole was the only definite product with phenylhydrazine. Urethane combines with the acetnl in presence of hydrogen chloride giving the compound CMeiC.CH(NH*CO,Et) slender needles m. p. 188-189". The acetal unites with alcohol in presence of scdiuur ethoxide formingORGANIC CHEMISTRY. i. 73 aay-triethoxy-A8-butyi?ene OEt*CMe:CH*CH(OEt) b. p. 190-1 95‘ under ordinary pressure 82-86”/15 mm.DZ1 0.908 !n,g 1.430. Exposure to air converts triethoxybutylene into /3-ethoxycrotonic acid. On hydrolysis i t appears to form acetoacetaldehyde but t b i s rapidly polymerises to triacetylbenzene. When treated with semi- carbazide hydrochloride i t yields a compound m. p. 127- 128’ w 0. w. 7 H CMe N-CO*NH,. CH-N> having the constitution Action of Monochlorocarbamide on Ketones. AUGUSTE R ~ H A L and A. DETCEUF (Compt. rend. 1911 153 1289-1231. Com- pare Ahstr. 191 1 i 957).-On allowing chlorocarbamide to act on the caIculated amount of an aliphatic ketone in aqueous solutions for three t o five days a n excellent yield of a monochloro-ketone is obtained. Symmetrical ketones give the halogen derivative in which the chlorine is next t o the carbonyl group whilst unsymmetrical ketones give two halogen derivatives the secondary one pre- dominating.On boiIing the semicarbazones of chloro-ketones with water hydrogen chloride is eliminated and a ketol formed; thus the semicarbazone of P-chloropropane-y-orre gives P-hydroxypropane-y-one. Chlorocarbamide and methyl hexyl ketone give a chloro-octanone m. p. - 25O b. p. 104-108”/20 mm. D 1.0034; the semicacrbaxone has m. p. 133”. Acetophenone forms only o-chloroacetophenone ; cyclic ketones also undergo chlorination. w. 0. w. Action of Dilute Nitric Acid on Starch and on Dextrin. WILLIAM OECHSNER DE CONINCK and ALBERT RAYNAUD (Rev. yen. Chim. pure appZ. 1910 14 169-l‘iO).-An investigation on the action of dilute nitric acid on dextrin and starch. The dilution of the nitric acid varied from 1 to 5 C.C.of acid (36OB8) in 50 C.C. water and the results indicated t h a t the amounts of dextrose formed during the same interval of time increased with the concentration of the acid but that this increase was less rapid with dextrin than with starch. With low concentrations more dextrin than starch underwent hydrolysis .but a t the highest concentration dextrin yielded 87.7% dextrose as compared with 90% from starch indicating that in the former oxidation had t o some extent interfered with saccharification. F. M. G. M. Modiflcations Undergone by Nitrated Celluloses and Powders Derived from them,under the Influence of Heat. R. FRIC (Compt. rend. 1912 154 31-32).-The changes produced in nitrated celluloses by heat can be followed by measuring the viscosity of a n acetone solution in the usual way.The effect of beating the solid a t 110’ is t o diminish the viscosity of the solution. w. 0. w. The ‘gCause’’ of the Beckmann Rearrangement. PIETER J . MONTAGNE (Cliem. VeekbZad 191 1 8 968-476. Compare Abstr. 1910 i 623).-In the author’s opinion the Eeckmann rearrangementi. 74 ABSTRACTS OF CHEMICAL PAPERS. is a simple exchange of position between the alkyl group attached to carbon and that attached to nitrogen. The assumption of the inter- mediate formation of an oxime-ester is a t variance with the experimental facts. A. J. W. New Compounds of the Choline Type. G. A. MENCIE (J. .BioZ. Chem. 191 1 10 399-406).-The chloride of a - methylchoZine NClMe,*CHMe*CH,*OH has been prepared as follows ally1 chloride was converted into the chlorohydrin and then into the corresponding acetate ; this by treatment with hydrochloric acid was converted into the acetate -chloride and saponified t o give the desired chlorohydrin CHMeCL*CH,*OH. On heating at 100' in a sealed tube with trimethylamine dissolved in alcohol the choline was obtained as a viscous yellow oil from which a hygroscopic colourless solid separated on cooling.The yellow platinichloride decomposes a t 254-255' ; the aurichloride is definitely crystalline it sinters above 180° m. p. 198-1 99 -5". By condensing monochloroacetone with magnesium alkyl halides the chlorohydrins of P-methylpropylene ap-glycol and P-methyl- butylene up-glycol are obtained. With trimethylamine these yield P-disubstituted cholines. P-Dimethylcholime cldoride NClMe,*CH,*CMe,-OH is obtained as a colourless hygroscopic solid.The platinichloride crystallises in yellow short individual prisms or foliated clusters which blacken at 240' decomp. 245'. P-Meth?lZ-P-eth?llcholine chloride NClMe,*CH,*CMeEt*OH forms a platinichloride which sinters a t 240° m. p. 242-243' (decomp. ). E. P. A. Stereoisomeric Cobalt Compounds. ALFRED WERNER (Annalen 1911 386 1-272).-The author's investigations on the stereo- isomeric cobalt compounds have now reached such a stage that stringent proofs have been obtained for the s tereochemical conceptions and methods which are free from objections have been devised for the determination of the configurations of the various isomerides. A summary of the methods used and of the results obtained is given in the present paper the greater part of the work consisting of hitherto unpublished investigations.The general results arrived at may be briefly summarised as follows The investigation of inorganic compounds containing the complex radicle CoA has shown that in all these compounds the six groups A are in direct connexion with the central cobalt atom. Any space formula used to represent these compounds must be such t h a t positions occupied by the groups A are all equivalent ; this follows from the fact that no stereoisomerides are known having the formula [Co i s ] . It has hitherto been impossible to prepare more I- _J than two stereoisomerides of the formula so that the groupsOKOANIC CHEMISTRY. i . 75 Aand B must occupy the corners of an octahedron the cobalt atom being in the centre ; the plane formula and prism formula would each give three possible isomerides.The groups B in the stereoisomerides [ c o 21 must consequently occupy the cis- and trans-positions. Investigation has shown that in all cases when t h e two groups B are replaced by a bivalent group giving three- four- five- or six-membered rings the same compound results no matter whether the cis- or trans- isomeride was used in the preparation. It appears therefore that there is only one position in the complex (the cis-position) favaurable t o the formation of such rings this being in accordance with the octahedral arrangement of the groups and in analogy with the forma- tion and non-formation of anhydrides from organic cis- and trans- isomerides.Use has been made of this result in the determination of the configuration of the various stereoisomerides but great caution is necessary in drawing conclusions owing to the ready transformation of one isomeride into the other Diaquo-salts H2° Co en X,.-The ois-isomerides have been characterised by their preparation from the carbonato-salts as also from the hexol- and diol-dicobaltic salts. The cis-compounds only are known in the tetrammine series whereas both cis- and trans-compounds of the ethylenediamine series have been prepared. The configuration of Ho Co en X is deduced from that of the the h~droxo-ccquo-salts diayuo-salts because of their formation from the latter by loss of a molecule of acid. Dihatogeno-salts [X Co en,]X,.-The two stereoisomeric dichloro- salts are known both in the tetrammine and diethylenediammine series. The cis-isomeride (violeo-salt) is the first product of the action of concentrated hydrochloric acid on the carbonato-salt ; it readily changes into the trans-isomeride (praseo-salt) under the influence of concentrated hydrochloric acid. The cis-dibromotetra- ammine salts are not known.Stereoisomeric hcdogeno-apuo-salts Co en,lX are not known ; in all cases +he cis-isomeride is [H,O 1 L a 2 0 I Both cis- and trans-isomerides are known. L A alone formed,' lfulogeno-isothiocyanato-salts rst co en,lX. - Stereoisomeric I- J chloro- and bromo-isothiocyanato-salts are known. Their configuration has to be decided chiefly by their colour (see later) since they so readily undergo transformation.The isothiocyanate group deepens the colour of the cobaltammines and it follows that the violet chloro-salts and indigo- blue bromo-salts are t h e trans-isomerides the cis-isomerides being red and bluish-red respectively. Similar results hold for the isothiocy anato-a puo-salts co en,]x the violet salts forming the trans- and the orange the cis-isomerides. The configuration of the I~~.ccZogeno-amnLin~d~t~yZ~n~~iu~?a~n~ salts [H,$ co en,& has been determined by oxidation of the corresponding halogeno-isothio-i. 76 ABSTRACTS OF CHEMICAL PAPERS cyanato-salts with hydrogen peroxide ; both the chloro- and bromo- salts have been prepared. The constitution of t h e apuo-ammine- diethglenediamine salts [:$ Co en,]X is determined by their transformation into the halogeno-ammine-salts by interaction with the halogen acids.The stereoisomeric diisothiocyanato-sai ts Co en,]X have already been described (Abstr. 1900 i S6) but the wrong configuration given t o them. The cis-isomerides are those which were formerly characterised as dithiocyanato-salts as may be deduced by their oxidation with hydrogen peroxide and subsequent evaporation with hydrochloric acid whereby the cis-chloro- ammine salts are formed. The trans-isomerides on oxidation with chlorine yield trans-diamminediethylenediaminecobaltic sal ts and were formerly characterised as diisothiocyanato-sal ts. The configuration of the diamminrzdiethylenediamine salts [:$ c o en,]^ was determined by their solubilities the cis- being more readily soluble than the trans-isomerides (compare below).The configuration previously ascribed to them (Abstr. 1907 i 290) is incorrect. Oxidation of the isoth ioc yanatoamminediethylenediamine salts [p; co en2]X2 with hydrogen peroxide giv’es rise to the diammine salts whereby the structure of the former salts is ascertained. The configuration of the nitroamminedieth&nedlamine salts [$3i co en,]^ follows from their formation from the isomeric aquo-ammine salts or from their transformation into the chloro-ammine salts. On oxidation of the isothiocyanatonitrodiethyZenediarnine salts [SCN Co en,]X with hydrogen peroxide nitroammine-salts are formed whereby the configuration of the former salts can be ascertained. Of the dinitro- diethylenediamine salts [(NO,) Co en,]X the croceo-salts are the trans- whilst the flavo-salts are the cis-isouerides.This is ascertained by their formation from the stereoisomeric diaquo-salts by the action of nitrous acid the dinitrito-salts first formed transforming into the dinitro-salts. The configuration of the chloronitro-salts [o, Co en2]X is ascertained by their transformation into the dinitro-salts by interaction with sodium nitrite. Influence of the Constitution of the Complex Radicle Co 4 on the Existence of Steveoisorneric Co6alt Ammonias.-The cis-compounds of the ammonia series are less readily produced than those of the diethylene- diamine series and transform much more readily into the trans- isomerides. cis-Dichloro-compounds of the trimethylenediamine series cannot be prepared all methods of preparation giving the green trans-isomerides. The nature of the halogen has an effect in that although cis- and trans-isomerides have been prepared in the dichloro- and di bromo-diethylenediamine series no cis-dibromo-compounds have been obtained in the ammonia series; in neither series eould iodo- O2N [ &IORGANIC CEEMISTRY.i. 77 compounds be obbained. The influence of the bivalent group Z in the salts [Z Go en,]X is shown by the fact that although sulphito- carbonato- oxalato- and malonato-salts have been prepared no com- pounds derived from succinic malic and tartaric acids have been obtaiaed. The formation of a seven-ring does not therefore take place which is in accordance with the results obtained with the alkyldiamines (compare Abstr.1907 ii 161). Ionisation 1somerides.-A full list of such compounds is given ; for example the cis- and trans-isomerides of the chloronitrothiocyanate nitroisothiocyanato-chloride and chloroisothiocyaiiato-nitrite in the diethylenediamine series. their Con- stitution and Conjguration.-The cis-isomerides are ge uerally more soluble than the trans-isomerides. There are exceptions as for example with the dinitrodiethylenediaminecobaltic iodides. It is pro- bable also that the solubility of the salt increases with the number of ionogenic radicles. Relation between the Colour of the Cobalt Ammonias and their Constitution and Configuration.-The chief influence on the colour is exerted by the radicles directly connected with the cobalt atom and is the only one considered here.No colourless cobalt compounds are known. The inflnence of the element directly attached t o the cobalt atom is shown by the series C N S 0 C1 Br I the elements being arranged in the order of their bathochromic action. This series can be extended as follows when the various radicles are taken into account CN CO; NO en NH NCS; SO,; OH O*NO 0-Acyl O H ; C1 Br I; thus the least-coloured compounds of cobalt are the pale yellow cyanocobaltammonias [Co(CN),]k,. Amines for example ethylenediamine propylenediamine hydroxylamine and pyridine have the same effect as ammonia. It is noteworthy that substitution in the trans-position has a much greater bathochromic effect than substitution i n the cis-position. Dareerences i n the Reactions of Stereoisomeric Cobalt A~nmnias.- Radicles which are in the cis-position with respect to each other are not so firmly combined as those in the tram-position and enter into reaction much more readily; for example by the action of hydro- chloric acid on cis-dinitrotetramminecobaltic salts both nitro-groups are replaced by chlorine with the formation of the trans-dichloro-salts whereas when the trans-dinitro-salts are heated with hydrochloric acid only one nitro-group is replaced the tvans-chloronitro-salts being formed.Differences of this kind have caused many difficulties in the determinations of the configuration of the stereoisomerides. These difficulties are especially marked in the case of the isothiocyanato-salts a full discussion of which compounds is given. Differences also occur in additive reactions ; for example the trans-chloroemurinediethylene- diamine salts readilv give the diammine salts when dissolved in liauid Relation between the L?olubiZiiy of the Cobalt Ammonias t ammonia [(I) ciCi en2]C12 + NH = [E Co en2 t6)H,N cis-compounds are unacted on even after keeping for hours dissolved - - in liquid ammonia.Intramolecular Reactions with the Cobult Ammonicm-The variousi. 78 ABSTRACTS OF CHEMICAL PAPERS. cases are summarised in which there occurs (a) Intramolecular reactions with expulsion of ammonia or water; for example the chlorides bromides and sulphates of chloro-aquo- and bromo-aquo-. diethylenecliaminecobaltic salts are stable whilst the nitrites on keeping change in accordance with the equation .-I roo Co en21N0 + H,O.( b ) Intramolecular reactions in which inter- ;hinge of thgacid-residues takes place; for example when a drop of water is added to the pure green tlrans-dichlorodiethylenediamine- cobaltic nitrite [CI Co en,]NO it immediately changes into the yellowish-red chloronitrodiethylenediamine chloride LO2 c o en,J CI. (c) Transformation of stereoisomerides into each other. Direct transformations have hitherto been observed in comparatively few cases and even then i t is probable that intermediate products are formed which have not so f a r been isolated. Additive Compounds of the Cobalt Ammonias.-A full discussion is given of cases such as the following By the addition of silver nitrate to a solution of the intensely-red coloured salt .I [[;; g c o en,]S2069 golden-yellow prisms of the composition I L:s Co en,lS,O,,AgNO,are obtained.this compound point to its having the constitution The change in colour observed Lnd the va&us reactions of [*qg Go e n 2 ] 3 2 6 that is it is a silver thiocyanatoamminediethylenedinminecobaltic salt. The study of such compounds is of great service in elucidating the mechanism of the various reactions of the cobalt ammonias. Spatial Change of Position during Reuctions of the Stereoisomeric Cobalt Ammonias.-(Compare Abstr. 191 1 i 494.) [With Jos. ~~~~~~~~.]-~arbonatodiethy~enediaminecoba~tic salts YX where Y=[CO,Coen,] are prepared from any dichloro- or dibromo-salt by the action of sodium or potassium carbonate. The mixture with water is boiled until the solution becomes an intense blue colour when the reaction is complete. The chloride YCl,H20 is thus obtained from 1 6-dichlorodiethylenediaminecobaltic chloride by interaction with sodium carbonate.The hot filtrate from undissolved salt deposits on cooling dark red flat columnar crystals which become anhydrous at 70-80°. It may also be obtained from a concentrated solution of the bromide by shaking with silver chloride. The bromide YBr,H,O is obtained from the chloride by precipitation with potassium bromide. On recrystallisation it deposits partly as hydrated and partly as anhydrous salt. The hydrated salt forms large dark red hexagonal efflorescent columns the anhydrous salt being brownish-red in colour. One gram of the salt dissolves in 30 C.C. of water at 50". The iodide YI is obtained similarly to the bromide and forms shining dark red flat prisms which are soluble in water to the extent of 1 gram in 70 C.C.of water at 80'. The nitrate YNO,,H,O,ORGANIC CHEMISTRY. i. 79 results from the interaction of the bromide and silver nitrate; it crystallises in dark bluish-red shining flat needles. Twenty C.C. of water dissolve 1 gram a t 60". The tlJiocyanate YSCN the dithionate Y,S,0G,2H,0 and the sulphccte Y2S0,,5H,O were also obtained by.reactions involving doubleidecomposition. They crystallise respectively in red hexagonal prisms or needles long dark red prisms and reddish-black flat prisms. [With R. H~~~~u~~.]-O~alatodiethylenediaminecoba~~~c salts [C,O Coen,]X have been known for some time (compare Abstr. 1899 ii S S O ) and an attempt has now been made t o introduce ammonia into the radicle to find out if a spatial transformation takes place.As a matter of fact ammonia does enter into the inner sphere but cis-diamminediethyknediamin,ecobaltic salts Y,(C,0,)X4 are alone formed where Y = [ Co \::3)2]. Four grams of the oxalato- diethylenediamine salt are heated with 15 C.C. of saturated ammonia solution for two hours in a bomb-tube at 1 1 0 O ; the contents of the tube are taken up with water the solution concentrated and potassium iodide added. The sparingly soluble oxalatodiethylene- diaminecobaltic iodide is first precipitated and from the mother liquor brown monoclir,ic columnar crystals of the iodide oxalate Y2(C20,)I are obtained. By interaction with silver chloride irregular light yellow crystalline aggregates of the chloride oxalate Y,(C,O,)Cl are obtained.I n contradistinction to the aqueous ammonia liquid ammonia has no action on the oxalato-chloride. Y = [C,H20 Co en,]. -Thehydrogen malonate Y C3H304 is obtained from carbonatodiethylene- diaminecobaltic bromide by first preparing the hydroxide by shaking the solution with freshly precipitated silver oxide. Malonic acid (2 mols.) is added to the filtrate from the silver bromide and on con- centrating carmine-red crystals of the desired salt are obtained. By double decomposition with potassium nitrate and ammonium thio- cyanate respectively red shining leaflets of the nitrate Y NO and thiocyanate YSCN are obtained. Attempts to prepare corresponding salts by using succinic malic or tartaric acids were unsuccessful.[With MARIE ~oKRows~~.]-~u~ph~tod~eth~y~ened~am~necobn~t~c salts YX where Y = [SO Co en2].-The chloride YCl,&H,O is obtained by boiling down a solution of sodium sulphite (10 grams) with trans- dichlorodiethylenediaminecobaltic chloride (1 0 grams free from hydrochloric acid) in 50 C.C. of water to half its bulk. After filtering dark brown crystals of indefinite shape are deposited. The same results are obtained if the cis-dichloro-chloride is used in the prepara- tion. The sulphito-group is co-ordinately connected with the cobalt in the cis-position since on heating with concentrated hydrochloric acid cis-dichlorodiethylenediaminecobaltic chloride is produced. Moreover the brown colour of the salt shows that the SO,-radicle is linked up with the cobalt by means of a sulphur valency thus The sulphate loses 5H,O at 100'.Mnlonatodiethylenediaminecobultic salts YX wherei. 80 ABSTRACTS OF CNEMlCAL PAPERS. since if i t were linked through two oxygen atoms it would be red in colour. On triturating the semihydrate with hydrochloric acid a reddish-brown solution is formed from which orange-brown shinirig scales of the trihydrate YC1,3H20 can be obtained. The solution gives characteristic precipitates with potassium iodide acetic acid and sodium nitrite and with chloroplatinic acid. On trituration with fuming hydrobromic acid and subsequent gentle warming green crystals of tvans-dibromodiethylenediaminecobaltic homide are obtained. Both hydrates can be dehydrated at 105'. By double decomposition with potassium thiocyanate brownit-h-yellow shining needles or scales of the thiocyanate YSCN,ZH,O are obtained.The pkatinichloride Y2PtC1,,4H,O forms brown star-shaped crystals ; the aurichloride YAuC1,,3H20 crystallises in thin yellowish-brown shining scales. [With K. R. LANGE.]-Di~quodietiyler~ed~a~~~ecobakt~c salts YX where Y = H2° Co en2].-The salts of the cis-series are all much more soluble than the tmns-isomerides. The latter are remarkable in that by precipitation of their aqueous solutions with potassium iodide the tyans-hydroxoaquo-iodide is formed and not the diaquo- iodide which shows that in aqueous solutions the diaquo-salts are hydrolysed in accordance with the equation L 2 O [(H20) Co en,]X [< Co en2 X,+HX. 1 A number of salts have been prepared in addition t o those previously described (compare Abstr.1907 i 188). The cis-nitrate Y(N0,)B,H20 was obtained from ci.s-d1aquodiethylenediaminecobaltic bromide by the action of concentrated nitric acid at a low temperature. It forms red glistening plates and can bs dehydrated over calcium chloride. The cis-subhate Y2(S04) was prepared from the bromide by inter- action with silver sulphate and crystallises in red glistening needles. Other cis-salts could not be obtained. New methods of preparation of the cis-bromide are as follows (1) 10 grams of carbonatodiethylenediaminecobaltic bromide are mixed with 18 C.C. of cold water and 5 C.C. of concentrated nitric acid added drop by drop. The solution is neutralised with potassium hydroxide half as much again of the hydroxide added and then precipitated with sodium bromide (23 grams).(2) The hydroxo- aquobromide is triturated with a little concentrated hydrobromic acid and then washed with alcohol and ether. The dry product is dissolved in cold water containing a little hydrobromic acid saturated (at 0') hydrobromic acid added and the solution allowed to crystallise in a freezing mixture. The trans-?bitrate Y(NO,) was prepared from the tmw-bromide by a method similar to that used for the cis-salt. It could also be obtained by interaction with silver nitrate. It forms brownish-red needles. The trans-sulphate Y2(S0,) was obtained from the bromide by interaction with sulphuric acid as brownish-red leaflets. The trans- dithionnate Y2(S2O,) and the trans-thiocyanate Y( SCN),,& H 20 crys- tallise respectively as slender brownish-red needles and as dark brown plates. The iodide could not be obtained for the reason already given.ORCtANLC CHEMIH'I'RY.i. 81 Au account is given of the transformatioil of the diaquodiethylenc- diaminecobaltic halogenides into dihalogeoodiethylenediaminecobaltic salts on keeping for some time or on heating a t 105-115'. A number of h ydroxoaquodieth ylenedimiineco baltic salts YX [H,O Co en2 have been previously described (Abstr. where Y = 1907 i 189). They have been further studied because the different stereoisomerides may be obtained from the same starting material under conditions of reaction which are only slightly different from each other; thus in the former paper the cis-bromide was prepared from cis-dichloro-chloride (violeo-chloride) but i t is now shown that when the latter compound is dissolved in concentrated aqueous ammonia and the solution triturated with solid sodium bromide the trans-bromide YBr is formed.The trans- thiocpnate is reddish-brown in colour. When dichlorovioleo-chloride (5 grams) is dissolved in concentrated ammonia (25 c.c.) by heating on a water-bath the-solution then kept in a vacuum over phosphoric oxide until the odour of ammonia has disappeared and then precipitated with sodium bromide a bluish-red precipitate of cis-chloroammiizediethylenediamis~ecobaltic bromide Ho 1 [.,".' Go en,]Br is formed. The production of this compound is not due to the inter- mediate formation of the diaquo-bromide since this salt when dissolved in concentrated ammonia gives rise to the hydroxoaquo-bromide only.The trans-bromide may also be prepared by carefully heating the trans-nitrate with dilute ammonia (1 1) until crystals begin to form on the side of the dish. [ bTith R. B o s s n ~ ~ ~ . ] - T h e formation of carbonatodiethylenedi- aminecobaltic salts from the stereoisomeric hydroxoaquo-salts has been studied. I n all cases one and the same series of carbonato-salts was formed it being impossible to prepare stereoisomerides. The carbonato-salts were prepared by the actiori of carbon dioxide either on alkaline solutions or on aqueous solutions of the hydroxoaquo- salts. Dichlorotetramminecobaltic salts YX where Y = [Cl Co(NH?)J.- The constitution of the silver and bismuth salts described previous1 y (Abstr.1897 ii 264) must be altered to Co(NH,),-/U12and [:: CO(NH,),ICI,. A new method of preparation of the cis-chloride is given. Carbonatotetramminecobalt chloride is shaken up with a saturated (at 0') solution of hydrogen chloride in absolute alcohol until the evolution of carbon dioxide ceases. The greyish-blue reaction product which is a mixture of the cis- and trans-dichloro-salts after being washed free from acid with alcohol and dried is ext,racted with a small quantity of ice-cold water the cis-isomeride going into solution. The filtrate is immediately precipitated with sodium dithionate in order to obtain the violeo-dithionate from which the chloride and other salts can be obtained in the manner previously described (Abstr. 1908 ii 42). There is always a considerable loss of violeo- VOL. c11.i. 9i. 82 ABSTRACTS OF CHEMICAL PAPERS. salt owing to its ready transformation in aqueous solution into chloroaquo-salt. The preparation by means of aqueous hydrochloric acid cooled with liquid air was by no means so satisfactory. DichZorocliethyZenedia??ainecobccEtic salts YX where Y = [C12 Co eo2]X. -A new method of preparation of the riormai trccns-chloride is t o precipitate an aqueous solution of the acid chloride with solid lithium chloride. The trans-nitrite YNO is obtained as small green crystals by precipitation of an aqueous solution of the chloride acidified with acetic acid with sodium nitrite. When sulphuric acid is used as the precipitant green crystals of the trans-hydroyen sulphate YHSO are obtained.The addition of silver nitrate to a solution of the chloride cooled with a freezing mixture gives a precipitate consisting of greenish-white glistening leaflets having the composition [ "g;; co en ]2(:$)2.H2Q New methods of preparation of cis-dichlorodietbylenediaminecobaltic salts from carbonatodiethylenediarninecobalt chloride are given ; they are similar to those already described for the corresponding tetrammirie salts except that the product of reaction is washed with cold water to free i t from impuritiee than which the cis-dichloro-salt is less soluble. A characteristic cis-sulphate Y2S0,,2H20 is described ; it crystallises in small reddish-violet needles. [With L. GERB S. LORIE and Jos. RAP] POKT.] -Dibromodiethylene- cliaminecobaltic salts YBr where Y = [Br Co en2.]-Only the trans- isomerides have hitherto been prepared (by Jorgensen) for which new methods of preparation are now given,as follows ( a ) a solution of cobalt bromide in 10% ethylenediamine is oxidised by leading air t.hrough it and then evaporated to dryness.The residue is then repeatedly treated with hydrobromic acid and evaporated until a uniform green salt remains which consists of the acid bromide. On treatment with a little water the trans-bromide is obtained. (6) Carbonatodiethylene- diaminecobalt bromide is heated on the water-bath with a solution of hydrobromic acid (D= 1.49) until the solution is green. On cooling the acid bromide separates from which the normal bromide is best obtained by heating at 110" until it no longer gives an acid solution.The trans-thiocyanate Y SCN is precipitated as a canary- green crystalline salt by the addition of potassium thiocyanate to a solution of the trccns-bromide. The methods for the preparation of the cis-bromide YBr are as follows (1) a solution of the trans-bromide is evaporated on the water-bat'h several times to a syrupy consistency. On keeping in a vacuum desiccator black crystals are then obtained which give a greyish-violet powder ; they consist chiefly of the cis-isomeride mixed with a little of the trans-isomeride. The latter can be extracted with a small quantity of water leaving the cis-form which can be purified by solution in water and precipitation with sodium bromide. (2) By fission of tetraethylenediaminedioldicobaltic bromide with concentrated hydrobromic acid into diaquo- bromideand therequireddibromo-bromide. The diaquo-salt is removed from the mixture by solution in absolute alcohol.(3) From carbonatodiethylenediaminecobaltic bromide by treatment with an alcoholic or aqueous solution of hydrogen bromideORGANIC CHEMISTRY. i. 83 by a method similar to that described for the correspouding dichloru- salts. The cis-bromide YBr forms scaly crystals possessing a colour. and glance similar to that of graphite. By double decomposition with the appropriate salts of the alkali metals the following compounds were prepared. The cis-iodide YI is similar in appearance t o the bromide ; the cis-nitrate YNO forms small gi eyish-viole t crystals as also does the cis-thiocyanate PSCN,H,O; the crystals of the cis- dithionute Y,S,O are somewhat lighter in colour than those of the other salts.Ch ZorobrorrLocliet?~.1/lenediu~i~~ecobctltic sul ts. Y X. where Y Y = rB c1 co enJX. L _I -Both the cis. and trans isomerides have been prepared ; the former are readily obtained pure the latter only with difficulty since they are generally mixed with trans-dibromo-salts. Two methods of pre- paration are given ( 1 ) Two grams of chloroayuodiethylenediamine- cobaltic bromide are covered with 2 C.C. of concentrated hydrobroulic acid and the mixture heated until complete solution takes place. On cooling a mixture of the green aod violet salt is obtained which is washed with alcohol and ether dried and then treated with a srriall quantity of water to dissolve out the green salt. The violet salt (cis-isomeride) is collected washed with water and alcohol and dried.The green filtrate gives precipitates kith metallic salts which give aualytical results corresponding with a mixture of dibromo- and chlorobromo-salts. (2) Chloroaquodiethylenediaminecobaltic bromide is heated for two hours a t l l O o whereby a ruixture of the cis- and tmns-chlorobromo-bromides is produced. This is separated as in (l) the trans-nitrate being precipitated from the green filtrate by ammonium nitrate. The trans-nitrate YNO forms small light green glistening leaflets. The trans-dithionate Y2S,0,. and trans-tJhiocyunute Y SCN are prepared from the green filtrate mentioned above by double decom- position with the appropriate alkali salts ; they form respectively glistening green flat crystals and a light green precipitate.The cis-bromide Y Br,H,O is a greyish-violet microcrystalline salt ; the cis-nitrate YNO forms dark violet needles and the cis-dithionate Y,S,O small violet leaflets. When the cis-bromide is gently warmed with concentrated hydro- bromic acid until a solution is formed i t is changed into trans- di bromodie t by I enediaminecobal tic bromide which is deposited on cooling in cauary-green crystals. [., c o en2 ~ . - - ~ n l y €IuZogenoaquodiethyZenediunainecobaltic sal ts the cis-isomerides have so far been obtained ; t h e cold aqueous solu- tions are fairly stable but on heating complicated changes take place. By the action of concentrated aqueous ammonia on the chloro- aquo- and bromoaquo-bromides hydroxochloro- and hydroxobromo- bromides are Obtained.1 cis-OhZoroaqzcodietrllylenediami?L~cobaZtic salts YX where Y = [H20 co en2 . Ii. 84 ABSTRACTS OF CHEMlCAL PAPERS. -The sulphude YS04,1$H,0 is prepared by heating 20 grams of trans- dichlorodiethglenediaminecobaltic chloride with 20 C.C. of water until a deep blue solution is obtained. After cooling and keeping for one hour ammonium sulphate (10 grams) is added ; on keeping for a further twelve hours bluish-red crystals of the sulphate are deposited mixed with some green crystals which can be removed by shaking with a little cold water. The sulphate dissolves in concentrated ammonia and the solution gives a bluish-red precipitate of chloro- amrninediethylenediamifiecobaltic bromide with concentrated hydro- bromic acid.The chloride YCI and the bromide YBr,,H,O are obtained from the sulphate by interaction,with the respective halogen acids. The former is microcrystalline and the latter forms small crystalline leaflets ; both are reddish-violet in colour. The bromide- nitrate YBrN03 prepared from the bromide and lithium nitrate is reddish-brown in colour. The mitrite Y(NO,) from the chloride and sodium nitrite gives dark violet micro-crystals. It is unstable changing to cis-chloronitrodiethylenediaminecobaltic nitrite. [With R. ~ ~ ~ ~ 1 1 ) ~ . ] - ~ ~ ~ - ~ r o n z 0 a q w 0 d i e t ~ ~ y ~ e n e d ~ a m ~ n e c o h salts YX where Y = LH$ Co en2].-The following methods are given for the preparation of the 6romide YEr2,H,0. (1) A solution of neutral 1 6-dichlorodiethylenediaminecobaltic chloride containing nitric acid is heated with a concentrated solution of silver nitrate until it assumes a Bordeaux-red colour.After collecting the silver bromide the filtrate is saturated with sodium bromide first filtering off any more silver bromide which may be formed. After a few hours the bromide has deposited as a violet microcrystalline powder. (2) A concentrated solution of the tyans-dibromo-bromide is heated a t 40" until it becomes violet in colour; after cooling it is saturated with sodium bromide. Any green crystals of praseo-bromide which are precipitated with the bromoaquo-bromide are removed by fractional solution in ice-cold water the praseo-bromide being the lesser soluble salt. (3) A solution of trans- di bromonitrate is treated similarly to t h e dibromo-bromide except that it is heated over the bare flame.(4) The carbonato- chloride or bromide is treated with concentrated hydrobromic acid (D i= 1.4). The bromoaquo-bromide is separated from the less soluble cis-dibromo-bromide which is formed at the same time by fractional solution. ( 5 ) cis-Diaquo-bromide is heated at 40' with j u s t enough water to give complete solution until a violet-coloured solution is obtained ; the bromoaquo-salt is then precipitated with sodium bromide. The bromide forms dark violet leaf-like crystals. By double decomposition with sodium nitrate and sodium nitrite respectively i t gives the nitrate Y(NO,),,H,(? and nitrite Y( NU,) as bluish-violet crystalline powders. it gives a yellowish-green tetranitrodiarnminecobalt compound.When triturated with Erdmann's salt H3)21 H49 Bydroxohalogeno-salts rHg Co A41 X.- I~y3roxochZorotetrccmmirne- L -I cobccltic drthiorbate [H Co (NHJ4] S206 is precipitatetlas a violet-blue 2ORGANIC CHEMISTRY. i. 85 salt when solid chloroaquotetramminecobal tic chloride is dissolved in a saturated solution of sodium dithionate in concentrated ammonia ammonium dithionate remaining in solution. The colour corresponds with that of the cis-dichlorotetrammine salts. The corresponding hydroxocr3Llorodiethylenetliccminecobalt~c bromide rH2 Co en Br is obtained as a brownish-violet crystalline paste when chloroaquo- diethylenediaminecobaltic bromide is treated with concentrated ammonia ; when heated with concentrated hydrogen chloride this salt gives a mixture containing a little 1 6-dichloro- with much 1 2- dichloro-diet h ylenediaminecobal t ic chloride. cis - Hyd~oxo bromodiethyl- eraediurninecobattic bromide ri Co en,]Br is similarly obtained as a brownish-violet salt from the bromoaquo-bromide and ammonia. When warmed with a little water addition takes place with the formation of the cis-hydroxoaquo-bromide ; similarly when triturated with concentrated hydrobromic acid the cis-diaquo-bromide is obtained .I Chloroisothiocyanc~todieth~llenediaminecobaltic salts Y X where Y = rScN c 1 Co en,l.-A few of the trans-isomerides which were howe& impure Gave been described previously (Abbtr. 1900 i 86). The trans-thiocyanate YSCN is obtained by precipitating a solution of 1 6-dichlorodiethylenediaminecobaltic chloride with potassium thio- cyanate. The precipitate consists of a mixture of about two-thirds of the trans- and one-third of the cis-isomeride.By appropriate treatment the pure trans-isomeride is obtained as sparingly soluble violet leaflets. When trituixted with hydrobromic acid it gives glistening bluish- violet crystals of the trans-bromide YBr,2H20. This salt may also be prepared from praseo-chloride (Abstr. 1907 i 291). With sodium dithionate it gives bluish-violet glistening crystals of the trans- dithionate Y2S206 and with perchloric acid violet leaflets of the trans-perchlorate YC10,. The perchlorate may also be obtained directly from the trans-dichlorothiocyanate and perchloric acid. The trans-isomerides dissolve readily in liquid ammonia giving red- dish-yellow solutions which deposit mixtures of the stereoisomeric iso- thiocyanatoammine salts.If the trans-perchlorate is boiled with sodium nitrite in concentrated aqueous solution until a reddish-brown colour is obtaiued the solution cooled and ammonium thiocyanate added an isomorphous mixture of the 1 6-chloroisothiocyanato- and 1 6-nitroisotgiocyanato-thiocyanates is precipitated. If the solution is boiled until brown in colour small quantities of the cis-nitroiso- thiocyanato-salt crystallise ou cooling. On heating a solution of tmns- chloroisothiocyanato-bromide with potassium thiocyanate and cooling needles of the trans-diisothiocyanato-thiocyanate separate and from the mother liquor small quantities of the cis-isomeride can be obtained; oxidation of the trans-salt with hydrogen peroxide gives the ty-ccns- diztmrnine salt.Or1 boiling a concentrated solution of the trans-chloroisothiocyanato- bromide (1 mol.) with silver nitrate (3 mols) filtelring from silver bromide and cooling light violet slender needles of an additive com-i. 86 AI<Sl'RAC'I'S O F CHEMICAL PAPERS. pound [hpSCN C1 Co en,](NO,) are obtained. On hoiling the aqueous solritiori of this salt silver chloride is slowly precipitated. cis-Chloroiso~hiocyanatodiethylenediaminecobaZt~c chloride YCI is obtained in the purification of the trans-thiocyanate in the form of bluish-red needles. It is purified by transformation into the per- chlorate and precipitation of the solution of this salt with concentrated hydrochloric acid.By double decomposition of a solution of the per- chlorate with the appropriate salts of the alkali metalcr the following compounds were obtained cis- Dithionate Y,S,OG,H,O brownish-red needles ; cis-nitrate YNO dark bluish-red needles ; cis-sulphate Y,SO violet-red powder. The cis-bromide Y Br,l-$H,O mas obtained from the chloride by interaction with hydrobromic acid. A method of preparation of the cis-chloride from cis-isothiocyanatonitro-chloride by interaction with hydrochloric acid is also given. The action of hydrogen peroxide liquid ammonia potassium thiocyanate sodium nitrite and silver nitrate on the cis-salts is fully described. Rro~zoisothioc~anatodieth ylencdiccminecoballic salts Y X where Y = LsEg Go en2].-Both series of isomerides are known but the cis- salts are difficult t o isolate since in aqueous solution they are readily trau sformed into aquo-sal ts.The trans-isomerides on oxidation wit b hydrogen peroxide under certain conditions give 1 6-bromoamine s;tlts and under other conditions 1 6-dibromo-salts. Hydrogen peroxide completely oxidises the thiocyannte residue of the cis- isouierides but if the aqueous solution is kept some time before hydrogen peroxide is added a salt of the aquo-series is formed which then gives rise t o the bromoamrnine salt. With ammonia both isomerides give a mixture of cis- and trans-isothiocyanatoammine- diet h ylenediami D ecobaltic salts. The trans-thiocyanate YSCN is prepared from 1 6-dibromo- diethylenediaminecobaltic bromide by precipitation with potassium thiocyanate.The green precipitate and mother liquor are heated until R deep red solution is obtained. On cooling and further addition of potassium thiocyanate green glistening needles of the required salt are obtained. Trituration with concentrated h ydrobromic acid gives dark blue prismatic crystals of the trans-bromide YBr 2H20 and pre- cipitation with perchloric acid the trans-perchlorate YCIO as dark blue almost black slender needles. The trans-dithionats Y2S,0 forms violet-blue leaflets. Three methods of preparation of the cis-bromide YBr are fully described namely from 1 6-dibromodiethylenediaminecobaltic bromide 1 2-aquoisothiocyanatodiethylenediaminecobaltic dithionate and 1 2-nitroisothiocyanatodiethylenediaminecobaltic sulphate. It forms garnet-red .glistening prismatic crystals and is used as a source or' preparation of the other salts by methods involving double decomposition. The cis-nitrate YNO is violet-brown in colour the cis-dithionccte Y,S,O brownish-red whilst the cis-sulphate Y,SO gives reddish-lilac silky thin leaflets.ORGANIC CHEMISTRY. i. 87 isoTliiocyanatoaquodiethylenediamin2ecobaltic salts Y X where L L -Both series of isomerides have been obtained whereas with all other acidoaquo-salts it has been possible to prepare one series only either the cis- or trans-. The salts of the cis-series are yellowish-red t o crimson in colour whilst those of the trans-series are violet; the former are obtained from the stereoisomeric chloroisothiocyanato-salts by the action of concentrated ammonia and the latter from the same salts by the action of potassium hydroxide.The cis-dithionate YS,O,,H,O is prepared by warming 1 6-chloro- isot hiocyao atodie t h y 1 ened iamineco bal tic bromide with concentrated ammonia until a red solution is formed. The cooled solution is then poured into absolute alcohol the precipitate dried on a porous plate dissolved in cold water and glacial acetic acid added to the solution until a precipitate begins to form. On further keeping orange-coloured needles of the dithionate separate. With potassium thiocyanate the solution gives R crimson precipitate of the cis-thiocyanate Y(SCN),. With hydrogen peroxide the dithionate gives a mixture of the cis- and trans-chloroammine salts ; with concentrated hydrochloric acid cis- chloroisothiocyanato-salts ; with nitrous acid cis-nitroisothiocyanato- O N diethglenediaminecobaltic dithionate SbN Co en,1,S2O6 in the form of L slender yellow needles ; with potassium thiozyanate cis-diisothio- cyanato-salts.With silver nitrate and perchloric acid an orange- coloured additive product LAgScN Co en,]gA:)2,2H2O is obtained. The trans-bromide YBr2,2H,0 is prepared as follows 1 6-chloro- isothiocyanatothiocyanate dissolves in potassium hydroxide to a red solution ; on cooling brownish-red leaflets of 1 6-hydroxoisothio- cyanccto-thiocyanat e [sEgCo en,]SCN,H,O separate. These are dis- solved in a little water excess of concentrated hydrobromic acid added and the solution kept over sulphuric acid in a desiccator. After a .few days dark red crystals of the required bromide separate.From this salt by the method of double decomposition the trans-thio- cyanate Y(SCN),,H,O is obtained as a violet precipitate the trans- nitrate Y(NO,),,H,O as bluish-red needles and the trans-nitrite Y(NO,) as dark violet-red crystals. On the addition of excess of silver nitrate to a well-cooled solution of the nitrate bright red H24 - needles of an additive product [Ag,$$ Co en,](NO,),,H,O are deposited. On oxidation with nitric acid or hydrogen peroxide and subsequent evaporation with concentrated hydrochloric acid the trans-aquoiso- thiocyanato-salts give only trans-chloroamrnine salts. When solid sodium nitrite is added to a concentrated solution of 1 6-isothiocyanatoaquo-nitrate acidified with a few drops of acetic acid a bright red precipitate of 1 6-nitritoisothiocyanatodiethyZ~ne- diaminecobdtic nitrite PNO,,H,O where Y = [tzi Co en,] is88 ABSTRACTS OF CHEMICAL PAPERS.produced ; with potassium thiocynnate the solution gives red needles of the 1 6-thiocyanate YSCN. ChloroamminediethyZenediaminecobcLEtic salts YX where Y = LH- Co en,].-The isomerides of this series are best distinguished by means of the dithionates ; the cis-dithionate forms thick crystals whilst the trans-dithionate crystallises in long glistening needles. Both series of salts are bluish-red in colour. The trans-salts react very quickly with liquid ammonia forming diammine salts whereas the cis-isomerides are scarcely acted on. Jorgensen has already prepared a number of the cis-isomerides. The best method of preparation f o r the cis-chloride YCI is the trituration of 1 6-dichlorodiethylenediaminecobaltic chloride with concentrated ammonia. The green salt first dissolves and then a red paste of the required chloride separates.The addition of solid sodium perchlorate t o a solution of the chloride precipitates long red prisms of the cis-chloride-perc72lorale YCl( (310,) ; on recry stallisation from concentrated hydrochloric acid it is transformed into the chloride. The cis-nitrite Y (NO,) forms brick-red crystals. The actions of sodium and silver nitrites of potassium thiocyanate and of liquid ammonia on the cis-chloride are fully described as also the changes which aqueous solutions of the cis-nitrite undergo on warming. To prepare the tram-chloride YCl,,€I,O 1 6-chloroisoLhiocyxnato- diethylenediaminecobaltic thiocyanate is oxidised with hydrogen peroxide in aqueous solution acidified with sulphuric acid. Precipita- tion with hydrochloric acid then gives a chloride-sulphate which is recrystallised from hydrochloric acid several times and the aqueous solution then precipitated with barium chloride to remove the sulphuric acid.It forms bright ruby-red prisms. It may also be prepared from 1 6-nitroammine salts by heating with concentrated hydrochloric acid and from 1 6-dichloro-salts by the action of a methyl-alcohol solution of ammonia. The trans-chloride-perchlorate YCI(ClO,) is prepared from 1 6-chloroisothiocyanatodiethylene- diaminecobaltic perchlorate by a method similar to that used for the chloride; it forms bright red glistening leaflets or flat needles.The trans -chloride hydrogen sulphate Y C1( H SO,) is obtained by repeated evaporation on the water-bath of 1 6-nitroamminedithionate with hydrochloric acid ; it crystallises in thick ruby-red plates. The trans-dithionate YS,O H20 crystallises as bright red slender needles when sodium dithionate is added to a solution of the chloride- perchlorate. The dichomate nitivate and nitvite have also been obtained. The actions of sodium and silver nitrites of potassium thiocyanate and of liquid ammonia on the trans-chloride-perchlorate a r e fully described as also the changes which aqueous solutions of the trans-nitrite undergo on keeping or on warming. Bromonrnminediethylenedi~n~inecobaltic salts YX where Y == Co en2].-Both series of isomerides have been prepared the cis-isomerides being the mom easily obtained.The determination of their configuration depends on the formation of the trans-isomerides from ‘trans-bromoisothiocjanato-sal ts by oxidation with hydrogen IORGANIC CHEMISTRY. i. 89 yaroxide. Both series are very similar i n colour. The cis-dithionate iorms short compact crystals whilst the trans-isomeride gives long slender needles ; also the former E a l t readily dissolves in concentrated hydrobromic acid with the formation of the bromide whereas the latter is unaltered. [With W. E. BoSs.1-The cis-bromide YBr2,2H,0 is obtained when moist 1 6-dibromodiethylenediaminecobaltic bromide is treated at a low temperature with ammonia (1 l) drop by drop until the green colour changes to a dark violet.At higher teu-peratures the diammine- salt is produced owing to the addition of a further molecule of ammonia. When recrystallised from water it forms bundles of reddish-violet glistening needles ; when precipitated from tbe aqueous solution by the addition of concentrated hydrobromic acid the anhydrous salt YBr is obtained as dark brownkh-red prisms or needles. It may also be prepared (1) by the action of ammonium bromide on tetrae thylenediamin ediaquotetrold icobal ticobn 1 tous sulphate and (2) by the action of hydrobromic acid on 1 2-nitroamminediethylene- diamiuecobaltic salts or on 1 2-aquoamminediethylenediaminecobaltic salts. By appropriate double decomposition the following salts were obtained cis-homide-nitrate YBr(N03) as reddish-violet crystals ; the cis-dithionate YS,O as reddish-violet thin leaflets ; the cis- pbatinochloride YPtCl as reddish-brown leaflets.The cis-nitmte Y(NO,) mas obtained from the bromide by trituration with concentrated nitric acid a s dark reddish-violet long rectangular columns. The trans-dithionate YS,O is obtained from 1 6-brornoisothio- cyanatodiethylenediaminecobaltic bromide by oxidation a t 50' with hydrogen peroxide in aqueons solution acidified with acetic acid and subsequent precipitation with sodium dithionate. It forms bluish rose-coloured slender needles. With ammonium iodide the solution gives reddish-brown glistening flat needles of the trans-iodide Y12,H,0. The trans-bromide Y Br,,H,O was prepared from 1 6-aquoamminediethylenediaminecobaltic bromide by evaporation with concentrated hydrobromic acid on the water-bath.It forms large dark reddish-violet prisms and serves as the hource of the trans-nitrate Y(NO,),,H,O and the trans-perchlortcte Y(CIO,) the latter crystallising in violet needles. AqzcoamminediethyEenediamineco6altic salts YX where Y = [g$ co en . I1 -Both series of isomerides have been prepared. They are obtained by the action of potassium hydroxide or of freshly precipitated silver oxide on the. stereoisomeric chloroammine- and bromoammine-diethy he- diaminecobaltic salts. I n every case partial transformation takes place so t h a t a mixture of t h e isomerides is produced. The product of action of the alkali is an hydroxoammine salt the aquoauimine salt being produced when the solution is acidified Potassium hydroxide produces a greater relative transformation than silver oxide ; more trans- isomeride seems t o be produced a t low than at ordinary temperatures. The mixture of the isomerides is separated by taking advantage of the fact that the tmns-aquoammine-bromide iA much less soluble in dilutei.90 ABSTRACTS OF CHEMICAL PAPERS. hydrobromic acid than the cis-isomeride. The isomerides can be dis- tinguished from each other (1) by transformation into the chloro- amminedithionate ( q . ~ . ) by warming with hydrochloric acid and subsequent precipitation with sodium dithionate ; (2) by warming the aqueous solution to which sodium nitrite and R little acetic acid has been added t o 60-70'. A yellow solution is produced which on the addition of sodium dithionate gives an insoluble precipitate if the cis-isomeride is present or a precipitate which can be recrystallised from water if the trarts-isomeride is present.The trans-bromide YBr,,H20 forms pale brick-red needles and is used as the source of other salts methods of double decomposition being employed. The trans-iodide YI,,H,O forms brownish-red flat prismatic crystaIs ; the trans-nityate Y( NO,) crystallises in fire-red glistening prisms ; the trans-platinichloride Y2(PtCl,),,2H,O gives small dark brownish-rcd crystals and the trans-platinochloride Y,( PtCl,)3,2H,0 forms slender light brown crystals. The cis-bromide YBr,,H,O forms clumps of small red crystals. The diisothiocyamatodaethylenediaminacobaltic salts YX where Y = [( SCN) Co en,] bave already been described (compare Brauniich Abstr.1900 i 86). Their true configuration has now been deter- mined as follows. By violent oxidation with concentrated nitric acid and subsequent evaporation with hydrochloric acid the trans-isomerides give mainly trans-chloroammine salts together with some trans- diammine salts ; oxidation with hydrogen peroxide gives only the latter salts. Under the same treatment the cis-isomerides give respectively t?*ans-dichloro-salts together with a little cis-chloro- ammine-salt and cis-chloroammine salt. On oxidation with chlorine the trans-isomerides give trans-diammine salts and the cis-isomerides trans-dichloro-sal t s. [With C. R1x.1-A new method of preparing the cis-salts is as follows 1 2-nitrosoisothiocyanntodiethylenediaminecobaltic thiocyan- ate is evaporated with hydrochloric acid whereby pure cis-diiso- thiocyanatodiethylenediaminecobaltic chloride YCl,$H,O is obtained.The solubilities at 25' of the various salts in grams per 50 C.C. of water containing acetic acid are as follows chloride 0.2766 ; bromide 0.1996 ; iodide (at 24') 0.465 ; nitrate 0.1968 ; thiocyanate 0.1860. Stereoisomeric dinmminediethylemdiamirnecobaltic salts YX where Y = [(NH5) Co en,] have already been described (Abstr. 1907 i 290) but the wrong configuration has been assigned to them; those which were formerly charncterised as cis-compounds are now found to be the trans-isomerides and vice-versa. The evidence for this is based on their relation with the diisothiocyanato- and isothiocyanato-ammine- salts which has already been indicated and on the resolution of the cis-compounds into the optically active isomerides.The trans-salts are sparingly soluble whilst the cis-salts are readily soluble. A new method of preparation is described by the oxidation of the isothio- cyanatoamminediethylenediaminecobaltic salts with hydrogen peroxide in the presence of halogen acid. [With R. SAMANEK.]-M~X~UWS of the two series of salts have also been obtained by the action of liquid ammonia on the following com- pounds 1 6-dichloro- 1 6-dibromo- and 1 2-dibromo-diethylene-ORGANIC CHEMISTRY. i. 91 diaminecobaltic salts; 1 6-chlorormmine- 1 6- and 1 2-brumo- ammine-diethylenediaminecobaltic salts. The separation of the isomerides can be brought about by taking advantage of the fact that the bromide of t h e trans-series is only sparingly soluble in hydrobromic acid whereas the cis-bromide is readily soluble ; or better still by precipitation of concentrated solutions of the salts with sodium dithionate whereby the trans-dithionate is obtained it being practically insoluble in water ; from the mother liquor the cis-periodide is precipitated by the addition of a solution of iodine in hydriodic acid and by trituration of this salt with sodium thiosulphate the cis-iodide is obbained. I n all reactions leading to the formation of diammine salts the cis-isomerides are formed in preponderating amount.If the action of ammonia on the 1 6-dichloro-salts is not sufficiently energetic some 1 2-chloroammine salt is formed.isol’f~iocyanatoamminedietl~ylened~iacmilzecobccItic salts YX where Y = [E? Co en2 .-The two series of isomerides have been obtained and are very important because of their genetic relations with other series in the determination of configurations etc. A mixture of both isomerides is always obtained in their preparation no matter whether 1 2-chloro- 1 2-bromo- or 1 6-chloro- 1 6-bromo-isothiocyanato- diethylenediaminecobaltic salts are used to obtain them by inter- action with liquid ammonia. The relative proportion of the isomerides produced is not independent of the nature of the ionogenic radicle in the salt used. The cis- and trans-thiocyanates Y(SCN) are obtained by dissolv- ing 1 6-chloroisothiocyanatodiethylenediaminecobaltic thiocyanate in liquid ammonia and allowing the solution to evaporate a t the ordinary temperature. The residue is dissolved in water containing acetic acid and on keeping the trans-thiocyanate is deposited as slender glisten- ing reddish-orange needles ; the cis- thiocyanate is precipitated from the mother liquors by the addition of much potassium thiocyanate in the form of reddish-brown crystalline crusts. By appropriate double decomposition the following salts were obtained cis-dithionate YS206 brilliau t orange-red leaflets ; cis-iodide Y I short columnar reddish- brown crjstals ; trans-iodide YI,,H,O small brick-red prisms.The trans-bronzide-dithionate Y,Br,(S20,),2H,0 was prepared by trituratiou of the thiocyanate with hydrobromic acid and subsequent precipitation with sodium dithionate ; it forms brownish-red -prismatic crystals.With silver nitrate the cis-dithionate gives glistening yellow crystals I of an additive product [AgSCN H P Co eni]sg whilst the trans-per- chlorate prepared from the thiocyanate and perchloric acid gives yellow needles of the additive product [ Ag2f$g c0 (No3)4’ A detailed account is given of the amion of oxidising agents and of Botassium thiocvanate on the cis- and trans-isomerides. Nitmtoan~,minediethylencdian2inecobaltic salts Y & where -7i. 92 ABSTRACTS OF CHEMICAL PAPERS. are oh tained by the evaporation ol the stereoisomeric aquoammine- diethylenediaminecobaltic nitrates with concentrated nitric acid. I n the preparation of the trans-isomeride from the 1 6-aquoammine salt some cis-isomeride is formed a t the same time but the two are readily separated by taking advantage of the fact t h a t the cis-dithionate is almost insoluble in water.Their configuration is determined by evaporation with concentrated hjdroctrloric acid whirh gives the corre- sponding chloroarnmice salts. Liquid ammonia gives a mixture of the stereoisomeric diammine salts. The cis-nitrate Y(NO,),. forms small glistening,'orsnge-red crystals ; the cis-dithionate. YS,O H,O is an orange-coloured powder. The trans-dithionate YS,O crystallises in orange-coloured needles. [With W. E. Bo~s].-NitroammirLacliethylelnedia~ainecoballic salts YX where Y = [%3? Co en,].-Both series of isomerides have been prepared and are distinguished from each other by the fact that the cis-salts are much moi e soluble than the trans-salts this difference being especially marked in the dithionates.The configuration is best decided by evaporation of the salt t o dryness with hydrochloric acid solution of the residue in water and precipitation with sodium dithionate of the chloroamminedieth y lenediaminecobal tic di thionat e the cis- and trans-isomerides of which are very characteristic. The cis-bromide YBr,? is obtained by adding an excess of a saturated solution of sodium nitrite t o a saturated (at 25') solution of 1 2-aquoamminediethylen~di~minecobaltic bromide acidifying with acetic acid and warming a t 40' until the solution becomes orange-yellow in colour. After keeping for twenty-four hours a precipitate consisting of a mixture of the bromide and nitrite is deposited ; i t is dissolved in water and the solution saturated st 3 5 O with potassium bromide.On cooling large dark yellow plates of the bromide are obtained. The following salts were obtained from the bromide for the most part by the usual methods of double decomposi- tion. The cis-chloride YCI forms orange-yellow prisms or else a microcrystalline precipitate ; the &iodide Y 12 crystallises in reddish-brown needles ; the cis-nitrate P(NO,) in flat tabular or needle-shaped crystals. The cis-dithionate YS,O forms small golden- yellow leaflets whilst the cis-sulphate YSO crystallises in long radiating light yellow prismatic needles. %he cis-bromide-nitrate YBr(NO,) is prepared by the gradual addition of concentrated nitric acid to a well-cooled solution of the nitrate; i t forms large glistening reddish-brown prisms.The following methods of preparation of the cis-isomerides are also described (1) B y the action of silver nitrite on 1 2-chloroammine- diethylenediauiinecobaltic chloride. (2) By the action of ammonia on 1 6-diuitrodiethylenediaminecobaltic salts. (3) By oxidation of 1 2-nitroisothiocyanatodiethylenediaminecobaltic salts. The trans-nitrate Y (NO,),,&H,O is prepared by dissolving 1 6-nitronitratodiethylenediaminecobaltic nitrate in liquid ammonia and allowing the solution to evaporate spontaneously. The residue is recrj stallised from water whereby 8 mixture of large dark brown plates and small light yellow crystals is obtained which areORGANIC CHEMISTRY. i. 93 mechanwally separated. The latter crystals consist of 1 6 diuitro- nitrate whilst the former asre the required trans-nitrate and after further recrystallisation are obtained a s flat rhombic tablets.By appropriate double decomposition the nitrate yielded the following salts the trans-iodide Y 12,H20 as brown glistening prismatic crystals ; the trans-bromide YBr as thick short columnar or tabular dark brown crystals ; the trans-tl~iocyccszate Y(SCN) as thick glistening bro wnish-yellow plates ; the trans-dithionate as long glistening fluted prisms. This latter salt was also obtained from a solution of the trans-chloride prepared by the interaction of 1 6 - chloronitrodiethyleneditlminecobaltic chloride and liquid ammonia. The solubilities of the various trans-salts expressed in grams of salt per 10 C.C.of water at 27" are nitrate 2.827 ; thiocyanate 1.458; bromide (at 26O) 0.6867 ; iodide 0,7707. Nitroisotl~iocyanatodiethylenediumis~ecobultic salts YX where Y = [,.!$ Co en,].-The salts of the tyans-series are more easily soluble than the cis-isornericles the sulphates showing the greatest difference in solubility. There is also a marked difference in the colour of the salts the cis-compounds being bro wnish-yellow whilst the trans- compounds are dark brown. Hydrogen peroxide partly oxidises the cis-salts to cis-nitroammine-salts and partly oxidises the thiocyanate group completely away ; the tyans-salts under similar conditions give only trans-nitroaquo-salts the thio- cyanate group being split off completely. On heating with concentrated hydrochloric acid the cis-isomerides give the cis-chloroisothiocyanwto- salts whereas the trans-isomerides are not affected by the Bame treat- ment.On oxidation with nitric acid and subsequent evii.poration with hydrochloric acid the cis-salts give 1 6-dichloro-salts whilst the truns-salts give 1 6-chloronitro-salts. [With C. Rrx.]-The cis-chloi-ide YCl,H,O is obtained by intra- molecular transt ormation from 1 2-chloronitrodiethyleuediamine- cobaltic thiocyanate a solution of which in water containing acetic acid is evaporated to half its volume. The red colour changes to brown and on cooling brownish-yello w needles of the cis-chloride deposit contain- ing 2H20 but 1H,O is lost in a desiccator over calcium chloride. The chloride serves for the preparation of the other salts for the most part by the method of double decomposition.The cis-bromide YBr forms light brown nodular crystals ; the cis-iodide YI crystallises in brown prism ; the cis-sulphccte Y2S0 forms yellow glistening scales ; the cis-nitrate YNO forms brown thick crystals ; and the cis-thio- cyanate YSCN crystallises in brown leaflets. The cis-sulphate may also be obtained by heating a solution of cis-chloroisothiocyanato- diethylenediaminecobaltic chloride with sodium nitrite and subsequent precipitation with ammonium sulphate. The cis-thiocyaoate is also prepared by heating a solution of the cis-chloronitro-chloride with potassium thiocyanate. [With N. Gos~~~cs.]-The trans-lhiocyanccte YSCN i b obtained as YS,O,,H,? The following Ieactions are different in tlie two series.i.94 ABSTRACTS OF CHEMICAL PAPERS. brown prismatic crystals lien potahsiurrl thiocyanate ib i t d d d to a solution of 1 6-chloronitrodiethylenediaminecobaltic nitrate. Methods are also described for its preparation by the action of potassium thio- cyanate on nitratonitrocliethylenediaminecobaltic thiocyanate and on 1 6 -nitroa mm ined iet h y lened iam inecobal tic nitrate. The trans- chloride YCl,H,O is obtained as reddish-brown tabular crystals by dissolving the thiocyanate in conceu trated hydrochloric acid and precipitation with alcohol; the other salts are prepared from i t by appropriate double decomposition. The trans-bromide YBr,H20 forms brown tabular crystals ; the trans-iodide YI crgstallises in glistening brown irregular leaflets ; the trans-nitrate YNO,,H,O forms brown plates as also does the trans-nitrite YNO,,H,O.With silver nitrate the trans-nitrate gives long yellow needles of an additive compound rAg\yg c o en2] (NO,),. L Din~trotetram~inecobaltic salts YX where Y = [(N0,)2Co(NH3)4].- [With L. COHN.]-B~ the addition of rubidium nitrate to a solution of the cis-nitrate (flavonitrate) a rubidium double nitrate Y NO,,RbNO is obtained as brown rhombic tabular crystals. It is analogous with the potassium double nitrate already prepared by Jiirgensen. Dinitrodiethy Zenediarnineco baltic salts YX where Y = [(O,”) Co en,]. -A number of the stereoibomerides have been described previously a8 dinitrito-salts (Abstr. 1901,i,511) ; thetruedinitrito-salts wereprepared later (Abstr. 1907 i 291).It has been found that the cis-nitrate is transformed into the tvans-nitrate when its aqueous solution is heated. The cis-thiocyanate YSCM is obtained from the cis-nitrate by precipi- tation with potassium thiocyanate ; i t forms glistening yellowish- brown tabular crystals. The trans-thiocyanute YSCN forms orange- yellow glistening thick crystals. The trans-hydrogen sulphate 3-H SO has been prepared from the iodide by interaction with silver oxide and subsequent neutralisation with sulphuric acid ; it forms glistening yellowish-red needles. Stereoisomeric chloro~zitrodieth~lenediaminecobaltic salts have already been describe$ (kbstr. 1961 i 512). It has since been found that the trans-salts can be exposed t o the action 6f concentrated hydrochloric acid for a long time without effect whilst the cis-salts rapidly give 1 2- and 1 6-dichloro-salts. trans - Nitronitrutodiethylenediaminecobaltic salts YX where Y = [gig Co en2].-Only the nitrate YNO has been obtained.It is prepared by the oxidation of 1 2-dinitrodiethylenediaminecobaltic nitrate with concentrated nitric acid and forms glistening chamois- coloured crystals. By precipitation of the aqueous solution with concentrated nitric acid an ucid nitrute YNO,,HNO is obtained. trans - Nitroaquodiethylenediaminecobaltic salts YY where Y = [22E Co en,].-The sulyiiate YSO is obtained as follows 2.8 grams of solid ammonium sulyhate are added to a solution of 4 gramsORGANIC CHEMISTRY. 1. 95 of 1 6-nitronitl.ato-diethylenrdiaminecobaltic uitr:tte i i i 10 c.c. of water and then alcohol added until no further precipitate forms.It crystallises in orange-coloured needles. No other salts could be obtained owing to their great solubility. DichZoroethyZenedian~inediccmlninecobaltic salts YX where Y = C I C ~ en (NHJ2]. -Both series of stereoisomerides have been obtained. The method of preparation is briefly as follows By warming trinitrotri- amminecobalt with ethylenediamine trinitroethylenediamineammine- cobalt is obtained en (NO,),Co(NH,) + en = (NO,),Co NH + 2NH,. 3 By heating with concentrated hydrochloric acid the latter salt is transformed in to dic hloroaquoe t hy lenediamineamm inecobal tic chloride [gb co en ]GI of which 1 gram is then dissolved in 25% ammonia (34 c.c.). After five minutes 3.5 C.C. of concentrated hydrochloric acid are added to the solution which is then heated until i t becomes greenish-blue in colour.On cooling green crystals of the trans- cldoride YCI,&H,O are deposited from which by the method of double decomposition the following salts were obtained generally as green precipitates trans-nitrate YNO ; trans-iodide Y I ; trans- bromide YBr ; trans-thiocycmate Y SCN ; trans-lqdroge~i sulphate YHSO,,H,O ; trans-dithionate Y,S,O,. The iodide is sensitive to light. The cis-isomerides were prepared from the trans-compounds as follows By heating a solution of the trans-chloride with potassium carbonate until the colour bad changed to red and then cooling garnet- red crystals of carbonatoetlbylenedianzinediamminecobuZtic chloride NH3 p 3 c 0 (BNnHS)JC” were obtained.By treating this compound with concentrated hydro- chloric acid in the cold a solution of the required cis-chloride was obtained from which on the addition of ammonium bromide the cis- bromide YBr was deposited as a bluish-violet precipitate. The cis-dithionate Y,S,O is a violet precipitate obtained from a solution of the bromide by the addition of sodium dithionate. [With G. L~~D~N~~~~.]-~~ac~doditrirnethy~enediaminecoba~t~c salts [X,Co (tn)2]X.-Only the 1 6-dinitro- and 1 6-dichloro-salts have so far been prepared. The 1 6-dichloro-salts are distinguished from the corresponding diethylenediamine salts by their ready hydration (formation of aquo-salts) in aqueous solution. The neutral green solution of a dichloroditrimethylenediamine salt rapidly becomes violet in colour ; the addition of concentrated hydrochloric acid restores the green colour.Carbonate-salts have been prepared from the 1 6-dichloro-salts but could not be made to furnish the stereoisomeric 1 2-dichloro- salts. trans-Dinitroditrimet~yZenedia~ineco~aZ~ic salts YX where Y = [(NO,) Co tn,].1. 96 ABSTRACTS OF CHEMICAL PAPERS. -The niirite Y NO is obtai ued by heating potassium cobaltinitrite with trime t>hylenediamine in ;tqueous solution. I t forms large thick yellowish- brown pleochroic rhornbic crystals. YBr,H,O and the iodide YI,2H20 are .obtained from the nitrite by interaction with potassium bromide and iodide respectively the former as brownish-yellow monoclinic crystals and the latter as yellow t o yellowish-green pleochroic rhonibic prisms.The chlovide PCl,H,O and nitrate YNO are best obtained from the iodide by interaction with silver chloride and nitrate respeotively ; the former gives light to dark brown pleochroic monoclinic c r j stals and the latter rhombic plates. 1 6-Dic?~lorodit~irnethylenediaminecoba2tie chloride [CI Co tnJC1 is obtained by heating the diriitronitrite with hydrochloric acid ; a green solution i s obtained which on cooling deposits green prismatic columnar crystals. The solution is turned red by sodium hydroxide and ammonia and gives characteristic precipitates with the bromide iodide thiocy anate permanganate ferrocyanide ferricyanide or nitrate of potassium and with sodium thiosulpbate. Hydrogen sulphide precipitates cobalt sulphide- Potassium platinichloride gives green crystals of the plati&hIoride [Cl Co tn,],PtC16.Carbonatoditrimetf~yEenediaminecobaEtic chlorzde [CO Co tn,]CI,H?O was obtained by heating a solution of the 1 6-dichloro-chloride with sodium carbonate until i t became bluish-red in colour. The addition of alcohol precipitated a white salt and the red solution remaining deposited the required chloride in red needle-shaped crystals. By interaction with hydrogen chloride no matter under what conditions t h e green 1 6-dichloro-chloride was always obtained. The bromide T. S . P. Optically-active C a m p o u n d s of Cobalt and Chromium. ALFHED WEHNEH. (Arch. Sci. Phys. Nut. 1911 [iv] 32 457-467).- A general account is given of results which have for the most part been already published (Abstr.1911 i 613 S38 960; this vol. i lo). I n addition the author mentions that optically-active com- pounds r of the tetraet?rylerLediurnin,e-p-ccmino~eroxodicobalt and tetra- ethylewdiarnine-p-umino-ol-dicobuZt series have been obtained. The rotations of the compounds of the first series are very large the nitrate of the first series having a specific rotation of 840° which corresponds with a molecular rotation of about 6000'. From a consideration of the results hitherto obtained i t follows t h a t the sign of the rotation is not connected with the configuration of the diethylenediaminecobaltic radicle. This is well shown by the fact t h a t I-tetraethylenediamine-p-aminoperoxodicobalt salts furnish d-tetra- ethylenediamine-p-amino-ol-dicobalt salts on reduction Also I- chl oroisothiocy ana todiet hylenediaminecobaltic salts and d-chloronitrodiethylenediaminecobaltic salts both give rise to d-nitro- isothiocyanatodiethylonediamineoobaltic salts by interaction with sodium nitrite and potassium thiocyauate respectively.ORGANIC CHEMISTRY.i. 97 An examination of the compounds hitherto prepared shows that it is not always the isomeride of the same sign of rotation which gives the least soluble salt with d-bromocamphorsulphonic acid. W Q D 1. IJ. I. Preparation of Acid Chlorides from Two or More Molecules of Carbamide Chloride by Elimination of' Hydrogen Chloride. VEREINIGTE CHININFABRIKEN ZIMMEE & Co. (D.R.-P. .238961).-\Vhen carbamide chloride is heated in the absence of moisture either with or without a solvent two or more molecules condense with evolution of hydrogen chloride. Allophanic chloride NH,*ClO*NH*COCl a fuming colourless readily decomposable powder which reacts energetically with water according to the equation NH,-CO*NH*COCl+ H,O = CO(NH,) + CO + HC1 was thus obtained a t 30° whilst a t about 100' three molecules combined yielding bitwetcccrboxyl chloride C,H,N,O,*COCl a colour- less non-fuming powder decomposed by water with elimination of hydrogen chloride and carbon dioxide C,H,O,N,*COCl + H,O = HCl+ CO + NH,*CO*NH*CO*NH,. ETIENNE BOISMENU (Compt.rend. 1912 154 1482-1484. Compare Abstr. 1911 i 957)- The action of a n aqueous solution of hypochlorous acid on amides at 0' gives rise t o monochloro- or dichloro-amides according to the proportion of amide and of water employed.The dichloro-derivatives are yellow liquids the stability of which diminishes as the molecular weight increases. On treatment with amides they yield monochloro- derivatives. Acetyldichloroumide OH,*CO*NCI has an odour of chlorine and' is insoluble in water. It decomposes above O' depositing crystals of acetyl- chloroamide. Propio?-iyZdichZoroccmic~e and formyldichloroamide have also been prepared. The latter is very explosive and must- be kept in well cooled vessels (compare Mauguin hbstr. 1909 i 892). I?. M. G. M. Hypochlorous [ Acid and] Amides. w. 0. w. Cobalt Thiocyanates and the Cause of the Colour Changes in Cobalt Salts. ARTHUR HANTZSCH and YUJI SHIBATA (Zeitsch. anorg. Chem. 1912 '73 309-321).-Cobaltous thiocyanate is largely bimolecular in urethane solution at 49" but almost completely uni- molecular in alcoholic solution at 78".The existence of complex ions in the alcoholic solution is shown by the method used by Donnan and Bassett (Trans. 1902,81,944). The absorption spectra show the blue cobalt band and a broad band in the ultra-violet with its maximum at l/h 3400 and minimum a t l / X 3850. The absorption is slightly increased at 55" and 80'. Beer's law is departed from at considerable dilutions. The colour of the blue solution is attributed to the presence of the complex salt Co(SCN),Co in confirmation of which it is noted that the compound Co(SCN,)Me is blue. The salt Co(SCN),K is blue but its spectrum in absolute alcohol is practically identical with that of cobalt thiocyanate indicating dissociation into i t s components.Amy1 alcohol gives a n almost identical solution whilst moist ether VOL. CII. i. hi. 98 ABSTRACTS OF CHEMICAL PAPERS contains the salt in an almost undissociated condition. The action of alcohols in prornoting dissociation is attributed to the formation of the known alcoholates of cobalt thioceynnate. The deconiposi tion is still more pronounced in aqueous soltition but is lessened by the addition of potassium thiocyanate. The blue colour of cobalt thiocyanate is changed to pink by the addition of mercuric chloride or zinc chloride. The colour of the salt CO(SCN)~,H~C~ is not altered by further addition of mercuric chloride. This salt has not been isolated but when the alcoholic solution is evaporated with a turther quantity of mercuric chloride pink crystals of a compound 2Co(SCN),,3HgCl2 are obtained. The change of colour in cobalt chloride solution is also due to the formation of a compound [COCI,,(H~C~,)~]CO and not as assumed by Donnan and Bassett to (HgC1,)Co.The molecular weight of cobalt thiocyanate in aqueous solution shows that it only dissociates into two ions except in very dilute solutions whilst the chloride and bromide yield three ions even in concentrated solutions. It is therefore considered to exist in solution as the compound CO@'~) SCN. The whole of the colour changes may be explained as changes of the co-ordinative unsaturated complex COX into the saturated complex COX,. [ (H20),1 C. H. D. Systems Formed by Antimony Chloride and Bromide with Monosubstituted Benzene Hydrocarbons. BORIS N.MENSCIIUT- KIN (J. Russ. Phys. Chern. Xoc. 1911 43 1275-1302. Compare Abstr. 1911 i 273).-The author has subjected to thermal analysis the systems formed by antimony chloride and bromide with toluene ethylbenzene propylbenzene (see Abstr. 191 1 i 532) and isoamyl- benzene. The results are given in the form both of curves and of tables. Rosenheim and Stellmann (Abstr. 1902 i 68) state that antimony trichloride forms with toluene a cornpound having a composition analogous to that of the benzene compound namely SSbCll13,C,H,Me ; but this compound is really 2SbC13,CGH5Me the solid phase corresponding with 3SbC1 C,H,Me being antimony trichloride itself. The melting points of the thirteen compounds formed by tlte eight systems examined are as follows SbXc&jH,Et .SbX,-C,H,Pr . . BSbCI C6H,R. SbCl,,C,H,R. BSbRr C,H,R. SbRr3,C,H,R. . . . . .. . 42.5" 15-16" 38-39" 9" (ciccomp. ) (decomp.) (decornp.) 33 > > 1 ) > -15 9 ) 39.0" - . ...... 37.0 ....... 9-10 1 *5 - (decomp. ) (decornp.) SbX3-C&'C,Hl1 . . . 7 '5' - 20'5 - It will be seen that increase of the magnitude of the benzene sub- stituent is accompanied by decrease in the stability of the compounds formed with antimony trichloride and tribromide. The transition (p) and eutectic (e) points and the corresponding0 RG A N I C C H EM IS TR 1'. i. 99 o,iitions (rnols. of hydrocarbon per 1~01. of antiiuouy chloride) aru given in the following table 2SLC)& U,H,R- SbCl,,C,H,t~. 2SbC1,CtiH&-SbU1,. SbC1:3,C,H5R-SLC1,.-- Temp. Coinposition. Temp Composition. Temp. Composltlon. SbC1,-C H Me .. 11" 1.8 ( p ) 40.0 0.46 (e) - SbCI,-C:HiEt ..... 35 0'62 (c) 36.8 0.47 (e) 33" 0 5 2 ( c ) SbC1,-C,H5Pr ...... - - 8.5 0.88 ( p ) 1 0.98 ( e ) - SbC1,-CGH5*C5HIl. -33 3.1 ( p ) -21.0 1.3 (;u) - 5 1.2 (P) The transition points for SbBr3,C,H,R-SbBr are as follows Tein p. Composition. - - Sbtlr,-C,,H,Me ........ SbBr,-C,H5*C5H1 ...... - 17 5.07 This continual fall in the transition temperature again indicates diminution of stability of these compounds as the magnitude of the hydrocarbon increases. T. H. P. Systems Formed by Antimony Trichloride and Tri- bromide with Disubstituted Benzene Hydrocarbons. BORIS N. MENSCHUTKIN (J. Rum. Phys. Chsm. Xoc. 1911 43 2305-1328). -The systems here described contain 0- rn- or p-xylene or p-cymene.The results of the thermal analyses are given as curves and tables. The replacement of a second hydrogen atom of benzene by an alkyl radicle (compare preceding abstract) produces no change in the character of the system the temperature diagrams being similar to those given by the systems containing monoeubstituted benzenes. Also here too antimony chloride gives compounds of the two types 2SbCl,,C,H4R2 and SbC13,CGH4R2 whilst the bromide as a rule yields only one compound SbBr3,C,H4R2. The compounds are of approxi- mately the same stability as those formed with toluene or ethylbenzene. The results obtained with the three xylenes show that isomerism exerts a marked influence on the physical properties of these compounds.The melting points of the hydrocarbons and of the various com- pounds they form are given below the numbers for methylbenzene being inserted for purposes of comparison .$ bBr,-C H5E t ......... 29" 1.17 SbBr,-C,H,Pr ......... - 5 3'1 SbCI,-p-C,H,hIe ...... S ~ C I - ~ ~ L - C ~ H ~ M ~ J . . . . . S bC I,-C6H 5E t SbBr,-;u-C6€I,Me,. ..... SbRr,-wz-C,H,Mc ... SbBr,-o-CtiH,Me2 ...... SbEr,-C,H,Et ......... SbCI,-o-CGH,Me ...... ......... SbCl,-p-C,H,&IePrS ... SbBr,-p-C,EI,RlePiS . . Hydro- carbon. 2SbX,CGH,R DX. 14" 7 0" 56" - 57 38 95 - 93 33.5 62 5 - 93 37 130 - 75 40 115 14 67.5 53.5 - - - 57 - 29 - 93 - - - - SbX3,C,H4R,. Diff. 56" 4 2" 7.5 64.5 19.5" 48 "5 39 132 5-6 80 (decoinp. ) (decomp. ) - - 13.5 70.5 24 53 33 126 10 85 '1'. H. P. h 2 (cleconip.) (clacoml). )n. 100 ABSTRACTS OF CHEMICAL PAPERS. Relations of Trisubstituted Benzene Hydrocarbons to Antimony Trichloride and Tribrornide. BORIS N. MENSCHUTKIN (J. Buss. Phys. Chem. SOC. 1911 43 1329-1341).-11he systems formed by antimony trichloride and tribromide with 1 3 5- and 1 2 4-trimethylbenzenes (mesitylene and $-cumene) have been examined. Mesitylene forms compounds of the two types 2SbS3,C6H3Me3 and SbX,,C,H,Me with both antimony chloride and bromide and the same is the case with $-cumene. The only other benzene hydrocarbon with which this has been found to occur is toluene. The melting points of these compounds are as follows 2SbX C,H,Me,. SbX,,C6H,Me,. SbC1,-1 3 5-C,H3Me ...... 75.5" 43" (decoinp.) SbCl,-l 2 4-C6H,Me ...... 56'0 - 4 to -5" SbIh-1 3 5-C6H,Me ......69-5 38-39 SbBr3-1 2 4-C6H,Me 36.0 (decomp.) 13 2 9 ...... The eutectic points and the corresponding compositions are as follows System ... (1) C,H,Me,-SbX,,C,H,Me,. (2) 25 bX,,C,H,Me,-SbX,. r A -.c A \ M. p. of Com- hydro- Coni- M. p. of Temp. positiou. carbon. Tcinp. position. SbX,. SbC1,-1 3 5-C,H3Me - 55.6" 126.2 - 54.4" 58.5" 0.15 73" SbBr,-1 3 5-O6H,Me3 - 55'2 147.0 - 54'4 69.0 0.42 94 SbCI,-l 2 4-C,H3Me - 60.0 8'25 -57'4 51.0 0.27 73 SbBr,-1 2 4-C6HiMe - 58.8 28'4 - 57.4 - - - (Tha composition is given in niols. of liydrocarboii per mol. of SbX,.) The transition points SbX,,C,H31\le,-2SbX3,C6H,~~e~ are as follows Temp. Composition. SbC1,-1 3 6-C6H,Rle .............. 38" 1 *8 SbC1,-1 2 4-C,H3Me ...............- 5 1 *83 ShEr,,-l 3 5-C6H,Zle,.,. ............ 29 3 '45 SbBr,-1 2 4-C6H,Me ............... 7 1.72 Increase of the number of hydrogen atoms of benzene replaced by alkyl radicles does not diminish but rather increases the capability of these hydrocarbons to form compounds with antimony trichloride and tribromide. T. H. P. Electrolytic Reduction of Nitrobenzene. RALPH CUTHBERT SNOWDON (J. Physical Chem. 1911 15 797-S4P).-The author endeavoured to develop an electrolytic method of reducing nitro- benzene which should not require the use of a porous cup or a platinum anode. Nitrobenzene was vigorously stirred with ferrous chloride solution a t looo in a long cell provided with iron electrodes. The amount of anode iron dissolved was largely in excess of the electrolytic equivalent and dissolution of iron also occurred at the cathode in increasing proportion as the current density was lowered.With high current densities (10 amp./dm2) cathode corrosion was very small and theORGANIC CHEMISTRY. i. 101 yield attained 95% of aniline on the total iron dissolved. Although sheet iron in ferrous chloride solution will not reduce nitrobenzene on boiling it was found that under the emulsifying influence of rapid stirring the iron electrodes dissolved equally without electrolytic aid and gave a 78% yield of aniline calculated on the iron dissolved so that the commercial reduction of nitrobenzene by massive iron might be rendered possible by suitable agitation to bring the substances into intimate contact. The presence of a dissolved ferrous salt is essential in the electrolytic as in the chemical reduction. Ferrous chloride is apparently without action on nitrobenzene so that its catalytic activity must be attributed to a depolarising influence on the iron. I n this respect ferrous chloride and acetate are more efficient than the sulphate and benzoate.Nitrobenzene is reduced a t 100" by alkaline sodium sulphide freshly precipitated ferrous hydroxide and sodium arsenite but not by alkaline potassium ferrocyanide. Sodium arsenite gives 60-90yA of azoxybenzene 5-14% of aniline and a trace of azobenzene. This is contrary to electrolytic experience where azobenzene is produced above and azoxybenzene below 90'. Alkaline sodium sul phide and ferrous hydroxide give aniline and small amounts of azobenzene. The yield appears to vary with the order in which the three components nitrobenzene sodium hydroxide and reducing agent are mixed.Aromatic Nitro-derivatives. ROBERTO CIUSA ( A t t i R. Accccd. Lince& 1911 [v] 20 ii 523-524. Compare Abstr. 1911 i 931).- The observation of Werner (hbstr. 1910 i 20) that trinitro- mesitylene gives yellow solutions in some organic solvents although i t is not dissociated in formic acid solution indicates that there is no connexion between the dissociability of the aromatic nitro-deriv- atives and 'their power t o form additive products. The author now finds that tetranitromethane also is not dissociated in formic acid solution although it can form additive products. Xsomorphous Mixtures the Systems Chloronitrobenzenea- Bromonitrobenzenes. ROBERT KREMANN (Zeitsch.Kryst. Min. 19 1 1 50 86; from J ~ h r b . k.k. geol. Keichs. 1908 58 659-672).-The time-cooling curves and the freezing curves of t h e three systems (ortho meta para) show that the crystallisation interval for mixtures of the ortbo-series is very small; that of the meta-series is also small but it is larger in ihe para-series. The fusion curves of the two last systems belong to Roozeboom'e type V. 1-Bromo-2 4 6-tri-iodo-3 5-dinitrobenzene and Some of its Derivatives. U. LORING JACKSON and HAROLD E. BIGELOW (Amer. Chem. J. 1911 46 549-574).-1t has been shown by Jackson and Robinson (Abstr. 1890 377) that 1 :3 :5-tribromo-4 6-dinitrobenzene is converted by ethyl sodiomalonate into ethyl 3-bromo-4 6-dinitro- phenylmalonate.It has now been found t h a t when 1-bromo-2 4 6-tri- iOd0-3 5-dinitrobenzene is treated with ethyl sodiomalonate a t the ordinary temperature 1 -bromo-2 6-di-iodo-3 5-dinitrobenzeno and ethyl ethanetetracarboxylate are produced whilst if the mixture is R. J. C. R. V. S. L. J. S.i. 1 0 2 ABSTRACTS OF CHEMICAL PAPERS. heated ethyl 2-bromo-3-iodo-4 6-dinitrophenylmalonate is obtained. This shows t h a t the explanation given previously (Jackson and Moore Abstr. 1890 497; Jackson Abstr. 1890 983) is not correct but t h a t it must be assumed t h a t ethyl sodiomalonate reacts in the enolic form and t h a t the iodine atom and the *C,BrT,(N0,)2 group are added a t the double bond with production of the compound C0,Et *CHI*C( OEt) (ONa) *C,I,Br( NO,),.On acidification tbe hydrogen of the *OH g ~ o u p might combine with the substituted phenyl group with formation of the compounds C,HBr12(N0,) and CHI(CO,Et) ; the latter would then react with the excess of ethyl sodiomalonate to produce ethyl ethanetetra- car box yl a te. 1 -Bromo-2 4 6-tri-iodobenzene C6H2Er13 130. p. 146O obtained by treating a mixture of 2 4 6-tri-iodoanilineY glacial acetic acid and hydrobromic acid with sodium nitrite crystallises in pale yellow needlec and when heated with fuming nitric acid is converted into 1-b7.orno-2 4 6-tri-iodo-3 5-dir~itrobenxene~ C,BrI,(NO,) m. p. 292' which forms white needles. When tri-iodoaniline containing dnrk- coloured impurities was employed the crude 1-bromo-2 4 6-tri-iodo- benzene yielded on nitration some 1 3-dibromo-2 :4 6-tri-iodo-5-nitro- benzene C,Br21,*N02 m.p. about 256' (decomp.) which crystallises in hexagonal prisms. 1-Bromo-2 6-di-iodo-3 5-dinitrobenxene C,HBr12(N02) m. p. 187' crystallises in straw-coloured needles. Ethyl 2-bronzo-3-iodo-4 6-di- nitrophenylrnalonate CGHBrI( NO,),*CH( CO,Et) m. p. 107" forms btout lemon-yellow crystals. A small quantity of another cot)ipound m. p about 250' (decomp.) was also isolated from the product of the reaction between ethyl sodiomalonate and 1-bromo-2 4 6-tri-iodo- 3 5-dinitrobenzene. By the action of sodium ethoxide on 1-bromo-2 4 6-tri-iodo-3 5-di- nitrobenzene 3-bromo-3 4 6-tri-iodo-5-uitr~ph~netoZe CGBr'T3( NO,).OEt m. p. 14S0 is obtained which crystallises in light pink needles and is reduced by zinc and acetic acid to m-aminophenol.3-Bromo-2 4 :6-tri- iodo-5-nitroccnisoZe C,BrJ3(N0,)*OMe m. p. 163' forms pale yellow needles. When 2-bromo-l 3 :5-tri-iodo-4 6-dinitrobenzene is heated with zinc and acetic acid 5-bromo-nz-phenylenediamine is produced hut on reduction with ferrous hydroxide i t is converted into 1-byorno- 2 4 6-tri-iodo-m-phenyZenediarnine C,Br.I,(NH2)2 m. p. 187' which forms stout greyish-white needles and yields a hydrochloride decomposing at 100'. Reduction experiments have been carried out with several other iodo-compounds. Zinc and acetic acid remove iodine from 1 3 5-tri- iodo-4 6-dinitrobenzene. 2 4 6-Tri-iodoaniline is not affected by tin and hydrochloric acid and only very slightly by zinc and acetic acid.1-Bromo-2 4 6-tri-iodobenzene is reduced by zinc and acetic acid with formation of p-iodobromobenzene. These experiments show t h a t iodine is more easily replaced by hydrogen than is bromine. Sodium ethoxide does not react with 2 4 6-tri-iodobenzene and only very slightly with 1-bromo-2 4 6-tri-iodobenzene. E. G.ORGANlC CHEMISTRY. i. 103 Preparation of Alkylamines by Catalysis. PAUL SAUATIER and ALPEIONSE MAILHE (Compt. rend. 1911 153 1204-1208. Compare Abstr. 1909 i 292; 1911 ii 627).-An extension of the general reaction already described to the preparation of new amines. isoPropyl alcohol is transformed into isopropylamine when its vapour mixed with ammonia is passed over thorium dioxide at 250' ; the yield is 20%. A t higher temperatures propylene is formed together with diisopropylamine.The reaction proceeds with difficulty in the case of diphenplcarbinol. A t 280' the corresponding amine is obtained but the chief product is tetraphenylethylene ; this substance is easily obtained a t 300' in absence of ammonia. cycloHexanol and also its 2- 3- and 4-methyl derivatives yield the primary and secondary amines at 290-320'. 4'-Methylcyclohexyl- arnino-4-rneth,ylcyclohexane (C,H,,Me),NH b. p. 275" (decomp.) forms a phenylcnybamide m. p. 181'. The following secondary amines were prepared by passing a mixture of cyclohexylamine and an alcohol over thorium dioxide a t 320'. Ethyl- aminocyclohexane CGH,,*NHEt. Propylaminocyclohexane b. p. 185' ; the phenylcai*bamide has m. p. 113'. iso Butylccminocyclohexan~ b.p. 193" ; the phenylcarbamide has TU. p. 90". i8oAmylaminocyclohexano b. p. 205' ; the phenylcarbamide has m. p. 129'. Benxylaminocyclo- hexane b. p. 195'/80 mm. the phenylcnrbamide has m. p. 121'. cycloHexyZamino-2-methylcyclohe~:ane b. p. 260' with slight decom- position ; the hydrochloride has m. p. 182' and the phenylcarbamide m. p. 140'; the 3-methyl derivative b. p. 270' (decomp.) forms a hydrochloride m. p. 197" and a phenylcnrbamide m. p. 191' whilst the 4-methyl derivative b. p. 2?0' gives a phenylcarbamide m. p. 108'. The yield of the latter was 20%; the lowest yield mas obtained in the Behaviour of Nitrosomonoarylcarbamides towards Primary Amines and 'Phenols. J. HAAGER (Monatsh 1911,32,1089-1102). -Nitrosomonoarylcarbamides condense in alcoholic solution with primary aromatic bases t o diazoamino-compounds which contain the aromatic nuclei of both components and to arylcarbamides which contain the nuclei of the bases.Accordingly the rest of the carbamic acid and not the nitroso-group is eliminated from the nitrosocarbamides. The change is the same when the mixture of the components is heated. Nitrosoarylcarbamides react also with alkaline and with alcoholic solutions or phenols and their derivatives with the formation of hydroxyazo-compounds and alkaline salts of cyanic acid which have been formed by the elimination of -CO*NH from the nitroso- car bamides. Nitrosophenylcarbamide reacts with aniline t o form diazoamino- benzene and phenylcarbamide ; with p-toluidine benzenediazoamino- toluene m.p. 85' and p-tolylcarbamide are obtained. Nitroso-p- tolyl- carbamide and aniline yield the same compounds. Nitrosocarbamide with phenol yields benzeneazophenol ; with resorcinol it gives benzoneazoresorcinol m. p. 161'. p-Nitrosotolyl- carbamide and resorcinal give rise to y-tolueneazoresorcinol m. p. 183-184'. E. F. A. case of methy~um~nocyclohexccne. w. 0. w.i. 104 ABSTRACTS OF CHEMICAJ PAF'EItS. The Action of Phosphorus Thiochloride on Alkaline Solutions of Phenols. WILHELM AUTENRIETH (BRT. 19 11 44 3754-3755).-The author draws attention to the fact that several of the substances prepared previously by himselF (Abstr. 1898 i 41 9) have since been described afresh with different nomenclature (Ephraim Abstr. 1911 i 284; this vol. i 26). Dinitrophenols. FRITZ ULLMANN and SHRIRANG 31.SANE (Ber. 1911 44 3730-3737. Compare Abstr. 1908 i 525; 1909 i 21 23).-0n warming 4-chloro-2 6-dinitrophenol with toluenesulphonyl chloi-irle and diethylaniline 1 4-dichloro-2 6-dinitrobenxene is obtained ; it forms colourless leaflets m. p. 105' (corr.). If however the diethyl- aniline is replaced by sodium carbonate solution the product is 4-chloro-2 6-dinitropilenyl . p-toluenesulphonate ; this crystallises in colourless needles m. p. 127'(corr.) ; the action of ammonia on a boil- ing xylene solution of this ester yields 4-chloro-2 6-dinitroaniline (compare Korner Abstr. 1876 i 230) ; similarly the action of aniline on an alcoholic solution of the ester produces orange-yellow needles of 4-chloro-2 6-dinitrodiphenylamisze m.p. 1 30° the same substance being obtained also from aniline and 1 4-dichloro-2 6-dinitrobenzene. The last-named substance also reacts with dimethyl- NO amine yielding 4-chloro- 2 g-dinitrodimethyl- aniline as orange-yellow crystals m. p. 111' (pro- I bably identical with that already described by "()-'-(/ Pinnow Abstr. 1899 i 203). By the action of the above-mentioned dichlorodinitrobenzene or chlorodinitrophcnyl p-toluenesulphonate on o-aminophenol there is obtained 3-chloro-5-nitrophenoxaxine (annexed formula) in violet needles m. p. about 192'. 1 2-Dichl0s~0-3 5-dinitrobenxeme is obtained from 6-chloro-2 4- dinitropbenol in R similar manner to the 1 4-dichloro-isomeride above; i t forms hexagonal pale yellow tablets m. p. 56'; in boiling alcoholic solution wit,h ammonia it yields yellow needles of 2-chloro- 4 6-dinitroaniline (m.p. 157') and with aniline brick-red crystals of 2-chloro-4 6-dinitrodip?hen$amine. Heated in alcoholic solution with o-nminophenol it yields 3 5-dinitrophenoxazine (compare Turpin Trans. 1891 59 722). 2-Chloro-3 5-dinitrotoluene m. p. 63' (cow.) is obtained by the action of to1 uenesulphoriyl chloride and diethylaniline on 3 5-dinitro- o-cresol; the lower m. p. previously obtained for this substance (Nietzki and Rehe Abstr. 1893 i 15) was due to impurity. I n the above process 3 5-dinitro-o-to191 p-toluenesulphonate (coloarless needles m. p. 167O) is obtained as a by-product. I f the above chlorodinitro- toluene is allowed to react with o-aminophenol 2 4-dinitro-6-methyl- 2'-hydroxydiphenylamine is obtained which crystallises in reddish- brown tablets m.p. 177" (corr.) and by treatment with dilute soda passes into 3-nit!1-0-5-metAylphenoxaxine (brown needles m. p. 205' with decomp.). The methyl esters of 3 5-dinitro-2-hydroxybenzoic acid and of 3 5-dinitro-4-hydroxybenzoic acid on treatment with toluenesulphonyl chloride and diethylaniline give the methyl eaters of 2-chloro-3 5- D. F. T. /\-NH-/\ORGANIC CHEMISTRY. i. 105 dinitrobenzoic acid (compare Purgotti Abstr. 1902 i 777) and 4-chloro-3 5-dinitrobenzoic acid (compare Ullmann Abstr. 1909 i 475) respectively. D. F. T. The Action of Metals on Fused Picric Acid. J. SAPOSHNIKOFF (Zeitsch. ges. Schiess. Sprengstoflwesen 191 1 6 183-185)- Kast's work is discussed (Abstr. 1911 i 852).The author heated one gram of various metals (in shavings or powder) with two grams of picric acid a t 125"; the amount of dissolved metal was estimated and found with the exception of tin to be in proportion to the equivalent weights of the metal. The respective weights dissolved by the picric acid were tin 0.00 ; aluminium 0.0488 ; iron 0.153 ; copper 0.1754 ; nickel 0.1862; zinc 0.2046 and lead 0.2798 gram. P. M. G. M. Electrolytic Reduction of Nitrated Phenyl Thiocyanates. FRITZ FICHTER and THEODOR BECK (Rer. 1911 44 3636-3648).- Muller has shown that the reduction of o-nitrophenyl p-nitrophenyl and 2 4-dinitrophenyl thiocyanates by alcoholic ammonium sulphide causes elimination of the thiocyano-group and the formation of nitrated diphenyl disulphides whilst tAeir reduction by stannous chloride yields thiazole derivatives (Zeit.Farb. Imd. 1906 5 357). The authors now show that different products are obtained by the electro- lytic reduction of these thiocyanates at lead or copper cathodes; the thiocyano-group is only attacked when lead cathodes are used. The reduction of pheny 1 thiocyanate in 2N-alcoholic sulphuric acid at a rotating lead cathode and with a current density of 0.02 ampere per sq. cm. (the anodic compartment contains a lead plate in 2N-sulphuric acid) yields hydrogen cyanide and 57.5% of phenyl mercaptan. Under similar conditions the reduction of o-nitrophenyl thiocyanate yields 1 -aminobenzthiazole which is probably produced by the secondary interaction of the o-aminophenyl mercaptan and hydrogen cyanide initially formed.With a copper cathode and a current density of 0.0 19 ampere per sq. cm. o-nitrophenylthiocyanate is reduced to the sulphate of 2-amino-5-hydroxyphenyl thiocpanate C7H,0N,S,H2S0,,H20 probably through the intermediate formation of a hydroxylamine derivative. 2- Amino-5-hydroxyphenyt thiocyanate NH,*C,H,(OH )*SCN m. p. 121" yields an N-acetyl derivative m. p. 206O (decomp.) (the methyl ether of which has m. p. 81°) a diacetyl derivative m. p. 183O and after diazotisation couples with P-naphthol to form an uzo- compound m. pa 130". p-Nitrophenyl thiocyanate is reduced to p-aminophenyl thiocyanate at a lead or copper cathode but in the latter case the intermediate pro- duct p-thiocyamoaxoxybenzsme ON,( C,H;SCN) m. p. 170-1 7 lo reddish-yellow leaflets can be isolated.The electrolytic reduction of 2 4-dinitrophenyl thiocyanate on account of its slight solubility and the consequent large volume of solution must be effected with large stationary cathodes of lead or copper foil ; also the solution (in alcoholic sulphuric acid) must be hot and a large current density 0.033-0.038 ampere per sq. cm. must bei. 106 ABS'1 RACTS OF CHEMlCAL PAPERS. employed. With r?. lead cathode the product is 1 4-diamino-5-hydroxy- the forma- tion of which is readily explicable in view of the course of the reduc- tion of the 0- and p-nitrophenyl thiocyanates. I n favour of this constitution is the fact tbat the sulphate yields a tliacetylamino- derivative m. p. 268' which is soluble in sodium hydroxide and forms 1 -amino-4-acet y lanzino-5-methoxybenztJLia xo le m.p. 2 5 7 - 2 5 go with methyl sulphate and sodium hydroxide. When reduced at a copper cathode and with a current density of 0*05-0.06 ampere per sq. cm. 2 4-dinitrophenyl thiocyanate yields at f i r p t the sulphate of 4-nitro- 2-umino - 5 - hydroxyphenyl thiocyanate 3C7H,03N3S,H,S04 (diucetyl derivative Cll*H90,NHS yellow microcrystalline powder) and finally the sulphate of 2 ; 4-dzamzno-5-hydroxypl~enyl thiocyanate (NN-diacetyl derivative m. p. 21 7" ; tyiacetyl derivative m. p. 156'). c. s henxthiazole sulphate NH,*C,H,(OH)<N>C*NH2,H2S0 S C,H,ON,S H2S04,H,0 New Halogen Compounds of the Normal Butane Series. JULIUS VON BRAUN and H. DEUTSCH (Ber. 1911 44 3699-3706. Compare Braun Abstr. 1911 i 6101.-Phenoxybutylene C,H,*OPh obtained on decomposition of phenoxybutyltrimethylammonium hydroxide OPh- [CH2];NMe,*0H yields with bromine phenyl-yi3- dihromobutyll ether OYh*C4H,Br2 which is converted by hydrogen bromide into a/3&tribi*omohutune CH,Br*CH,*CHBr-CH,Br.Mag- nesiurn removes two atoms of bromine forming magnesium butylene broviaide MgBr*[CH2J,*CH:CH2 and this is readily converted into Ay-pentenoic acid CH 2 C H CH,*CH,* C02H confirming the structural formula assigned t o the preceding compounds. Phenoxybutylene unites with hydrogen bromide to form phenyl y bromobutyl ether OPh*[CH,!,*CHMeBr. Phenoxybutylene is an oil b. p. 208-210°/760 mm. 94-(35'/ 16 mm. Phertyl y8-dibromobutyl ether is a colourless odourless oil b. p. 191-194°/13 mm. aB6-Tribrornobutane is a colourless liquid of pleasant odour b.p. 115-117'/10 mm. The magnesium compound interacts with a variety of substances so introducing the homoallyl complex CH,:CH*CH2=CH2 ; thus with benzaldehyde phenylbutenylcarbinoll 0 H*CHPh*[CH2],*CH:CH2 is obtained as a viscid colourless liquid of ethereal odour b. p. 125'/11 mm. Phenyl-y-bromobutyl ethey is a colourless odourless oil b. p. 130-1 3179 mm. After prolonged boiling with potassium cyanide t h e nitrile is obtained as a colourless odourless oil b. p. 156-157'1 10 mm. a d this when boiled for ten hours with alcoholic potassium hydroxide gives y-plt,enoxy-a-methylbutyric acid OPh CH,*CH,-C€€Me-CO H which separates in lustrous colourless crystals LTA. p. 79O. salt i s a colourless caseous precipitate. The silver E.F. A.ORGANIC CHEMISTRY. i. 107 Simple Method of Formation of Hydroxyhydrindones. KARL AUWERS (Ber. 1 9 11 44 3692-3699. Compare Abstr. 1910 i 629)-On heating p-tolyl a-bromopropionate with alummiurn chloride 7-hydroxy-4-methyl-l-hydrindone OH*C,H,Me<CO~>CH is obtained instead of o-bromopropionyl-p-cresol as expected. The structure of the hydrindone is established by the facts that it yields a semicarhazone and phenylhydrazone both soluble in alkali and contaiuing therefore a phenolic hydroxyl. The nucleus can be benzoylated and methylated and this methyl derivative still forms a semicarbazone. I n a similar manner the homologous isomeric methyl derivatives have been obtained from the p-tolyl a-bromobutyrate and a-bromoiso- butyrate. It is characteristic of these oxyhydrindones that their aqueous or alcoholic solutions are coloured deep blue by ferric chloride.It is probable in the above reaction that p-cresol vinyl ketone OH*C6H,Me*CO*CH:CH is formed as an intermediate product. The yield of hydroxyhydrindones is only about 50% of the possible ; coixmaranone derivatives are also formed. p- Z'oZyZ a-brornopropionate forms colourless lustrous needles m. p. 33" b. p. 145-150°/18 rnm. ' I - W ~ d r o z ~ - C m e t h y l - l -I,.ydyindone separates in flat colourless 1 ustrous needles m. p. 110-1 1 1". The semicarbaxone crystallises in colourless needles m. p. above 380' ; the pliengZhydraxom forms lustrouc almost colourless fatty needles m. p. 183". The benzylidene compound crys- tallises in faintly yellow-coloured needles m.p. 129". The benzoate is characterised by short calourless lustrous fatty needles m. p. J 24-125O and the methyl ether by stellate aggregates of slender colourless lustrous needles m. p. 112-1l3'. This methyl ether forms a semicarbaxone colourless needles m. p. 220-224° and a benzyzidene derivative colourless lustrous needles m. p. 185-1 86". p-ToZyZ a-bromoisobutyrate forms slender colourless needles m. p. 39-40" b. p. 152"/18 mm. 7-IZydroxy-2 4-dimethgl-1 -Iydrifidone OH*C,H,Me<~~~>CHMe crystallises in colourless needles m. p. 53" ; the benxoyZ derivative yields lustrous colourless needles m. p. 113-114" ; the semicaybaxone gives colourless glass-like crystals which gradually become citron- yellow on exposure; they become brown a t 220° m.p. 230-232'. CH This hydrindone does not form a benzylidene compound. separates in stunted colourless lustrous crystals m. p. 53-54". The senzicarbaxone forms stunted crystals m. p. 217" ; the benzylidene compound gives glass-like,. yellow flat needles m. p. 114". p-ToZyZ a-brontobutprate 1s an oil b. p. 160-163°/20 mm. E. F. A. Retene. 11. ALFRED HEIDUSCHKA and H. GRIMM (Arch. PJmrnz. 1912 250 33-45. Compare Abstr. 1910 i 397).-ltetenequinone reacts with organomagnesium haloids to form dihydroxydialkyl-i. 108 ABSTRACTS OF CHEMlCAL PAPERS. dihydroretenes and these mere isolated in a crystalline condition in the case of the phenyl benzyl p-tolyl naphthyl and methyl derivatives but could not be obtained pure in the case of o-tolyl m-xylyl bromocamphor ethyl or i-amyl derivatives.Experiments on the reduction and dehydration of dihydroxydiphenyldihydroretene are also recorded. Di~,yr€roxyd7pl~enyZdihZ/dro?.etenne CpnH,,O m. p. 172" obtained by condensing magnesium phenyl bromide with retenequinone in ether forms colourless crystals and is coloured red by sulphuric acid yellow by fuming nitric acid. Heated with acetyl chloride i t yields the corresponding anhydride C,,H,,< I >O m. p. 143-144" crys- tallising in clusters of needles and giving when heated with potassium hydroxide in alcohol in closed vessels an acid which probably corresponds with the product described by Acree (Abstr. 1905 i 216) as obtained from diphenylphenauthrone; its ethereal solution is coloured blue by ammoniacal copper oxide and then yields a copper derivative (C,,H,70,)2Cu m.p. 142' which at 125-140" slowly loses ammonia and turns green. When heated with zinc dust dihydroxydiphenyldihydroretene yields diphenyhetene m. p. N O ' crystallising in colourless needles from alcohol or acetone. Reduction with hydriodic acid and phosphorus gives rise to diphen?/lhezahydror~tene (which forms colourless crystals sinters at 8 2 O and melts completely a t 118')) and eventually t o Liebermnnn and Spiegel's retenedodecahydride. On bromination in carbon disulphide dihydroxydiphenyldihydro- retene gives a pale yellow finely granular powder which on distillation with zinc yielded diphenylretene. Chlorination produced a similar product containing 39.5% chlorine. Dihyclroxydi-p-tolyldihydroretene m. p. 203O obtained in a manner analogous to that described for the phenyl derivative forms glancing colourless leaflets.The anhydride m. p. 152-154O) occurs in colourless transparent small tablets. The products of bromination and chlorination resemble those of the lower homologue. Dihydroxy- dibenxyZdihydroretene m. p. 200-201° forms stellate clusters of small glancing needles. Dihydroxydinaphthyldi~ydroretene m. p. 2 17-218O was isolated with some difficulty by treating the crude product with warm toluene ; it yields an anhydride m. p. 188" which forms small glancing crystals from acetone or alcohol. Dihydroxydimet~yldihy~~o- retene IU. p. 166-167O was eventually obtained in poor yield as small colourless crystals giving a violet-brown coloration with sulphuric acid.On chlorination in carbon tetrachloride with iodine as carrier retene furnishes a viscid product which on precipitation from alcohol with water forms an amorphous colourless substance C18H14C19 [?I m. p. 98-100'. Influence of Sulphur and Sulphur-containing Groups on the Order of Substitution of Hydrogen Atoms in Benzene by Bromine. EUOUARD BOURGEOIS and A. A BRAHAM (Bec. trav. chim. 191 1 30 407-425. Compare Abstr. 1904 i 28).-Substances CPh CPh T. A. H.ORGANIC CHEMISTRY. i. 109 containing either of the groups -SH >KO -SO,H are completely transformed by bromine. The authors have studied the action of bromine on aromatic sulphides and disulphides sulphones and sulphonic acids. With bromine the sulphides give rise to dibromides of the type SRR’zBr which show no teridency to split up into the sulphide and free bromine but readily become transformed into substitution products.Phenylmethylsulphoniulin dibromide SMePhBr is obtained as a red crystalline substance m. p. 87-88’ when bromine acts on phenyl methyl sulphide in carbon tetrachloride solution below 0’. Above this temperature it gives off hydrogen bromide and is transformed into p-broi,io;uhe?~yl methyl sulphide m. p. 37-37-5O. This when oxidised by potassium permanganate in acetic acid solution yields the corre- sponding sulphone m. p. 102.5-103° which mlth phosphorus pentachloride gives p-chlorobromobenzene. The sulphide can also be obtained by the action of methyl iodide on the sodium salt of p-bromot hiophenol. Diphenylsulphonium dibromide SPh2Brs is obtained by a similar reaction to the above as a red crystalline precipitate which still more readily passes into the corresponding p-bromophenyl sulphide. Phenyl disulphide when dissolved in bromine yields p-dibromophenyl disulphide (compare Hubner and Alsberg Annulen 1870 156 328).Phenyl methyl sulphone is not attacked by bromine unless a catalyst such as ferric chloride is employed in which case there is produced p-bromophenylmethylsulphone identical with that obtained by the oxidation oE the corresponding sulphide with potassium permanganate (loc. cit.). I n all the above cases the bromine atom enters the para-position to the sulphur-containing group whilst in the case of the sulphonic acids the group -SO,H directs the bromine to the rrieta-position. W. G. Oxonium Compounds.GEORGE L. STADNIKOFF (J. Russ. Php. Chem. Soc. 1911 43 1244-1257).-According to Nef’s theory the first stage of the interaction of an alkyl halide with alcoholic alkali hydroxide consists of the dissociation of the alkyl halide into halogen hydracid which is neutralised by the alkali and the methylene residue R-CH which either combines with the alcohol forming a simple ether or undergoes isomeric change into an olefine. The fact that tert.-butyl iodide which is incapable of methylene dissociation gives no ether when treated with alcoholic alkali hydroxide is regarded as confirmation of Nef’s theory. The author finds that this evidence is fallacious since tertiary alkyl halides such as tert.-amyl bromide do give ethers under the above conditions although the yield is very small ; also te~t.-butyl iodide yields an appreciable amount of ether if treated with the alcoholic alkali in a sealed tube.Another observation which is not in agreement with Nef’s theory is that triphenylmethyl chloride reacts with alcohols giving ethers in theoretical yields. The most obvious method of explaining these reactions is t o assume that the alkyl halogen compound RX dissociates into ttlkyli. 110 ABSTRACTS OF CHEMICAL PAPERS. and halogen which then cotribirie with the alcotiol forming an oxoniuin compound R'H:O:KX. Tho latter may then decompose in two W L ~ giving (1) R'.O*R+I-IX or (2) K'H:O:HX+ an oiefine. Those reactions would herice he closely analogous t o those between alkyl halides and amines (see this vol. i 116). Owing t o the doubt which exists concerning the intermediate formation of oxonium compounds in such reactions as the above and i n the Grignard reaction the author has studied the following reactions.(1) The action of propyl iodide on triphenylmethF1 ethyl ether in presence of magnesium. E e r e the first stage of the reaction con- sists in the formation of the oxonium compound CPh,*OEt:PrI which then decomposes giving triphenylmethyl iodide and ethyl propyl ether. (2) With the same ether as in (1)) isobutyl iodide in presence of magnesium combines to form a n oxonium derivative which i H subsequently resolved into triphenylmethyl iodide and ethyl isobutyl ether. (3) Diphenylmethyl propyl ether and isobutyl iodide react in presence of magnesium giving the oxonium compound CHPh,*OPrI*C,H which decomposes in three ways giving (a) CHPh21 + C,H;OPr ; (bj C,H,T + CHPh,*OPr ; and ( c ) C,H,I +CHPh,-O-C,€I,(?).Diphenylmetibyl proppl ethey CHPh,*OPr prepared by the inter- action of diphenylbromorriethane and propyl alcohol in presence of potassium hydroxide is a colourless mobile liquid b p. 161°/11 mm. T. H. P. Some Chlorine Derivatives of Cholesterol. S'I'EPHAN MINOVNI and BELLA HAUSKNECHT (Biochem. Zeitsch. 19 12 38 46-52).- When cholesterol in alcoholic solution is treated with chlorine gas two substances are formed ; one C',,H7,O,Cl2 or C4,H7,OHCI2 is soluble in alcohol and contains water of crystallisation m. p. 125O and when anhydrous m. p. 130' ; the other C,GH,o,0,C12 m. p. 195' (precipitated from ethereal solution by alcohol) is insoluble in alcohol.The formation of the former substance can be explained on the assump- tion that two molecules of cholesterol combine t o form an ether from which by tha chlorinating and oxidising action of the chlorine two vinyl and two isobutyl groups are eliminated and replaced by hydroxyl and chlorine. By the action of hydrogen chloride and hydrogen peroxide a third chlorine derivative C,6H,70Cl was obtained ; it forms slender needles containing water of crystallisation m. p. 123'. S. B. S. Preparation of Arylpolymethylenechloro - compounds. EMANUEL MERCK ( D.R.-P. 23895 9). -When benzo-e-chloroam ylamide C6H,:CO*NH*[CH2],Cl is heated with aluminium chloride in benzene solution and the mixture subsequently treated with steam it yields benzo- ephenylam ylamide C,H CO -3 H [ CH,],.P h a yell0 w oil b. p. 273-275O115 mm. which on hydrolysis furnishes qdmylwtrql-ORGANIC CHEMISTRY i. 111 umine NH2*[CH2],Ph b. p. 131’/15 mm. picrdta m. p. 158-153O and platinichloride m. p. 220’. 4‘hZoroamylbefixene obtained by heating the foregoing benzophenyl- amylamide with phosphorus pentachloride has an unpleasant odour and b. p. 134’/18 mm. Benxo - 8 - pkenylbutyZarrLide glistening needles m. p. 83*5” is analogously prepared from benzochlorobutylamide with phosphorus pentachloride ; it furnishes 6-chlorobutyt?benxene C,H,*[CH2],Cl b. p. 122-1.23’/17 mm. F. M. G . M. Preparation of Derivatives of o-Thiolbenzoic Acid. BADISCHE ANILIN- & SODA-FABRIK (D.R.-P. 237773).-When dichloroethylene (1 mol.) reacts with an alcoholic solution of a thiolbenzoic acid (2 mols.) i t yields acetylbisthiolbenzoic acids (bismethinethiolbenzoic acids) of the general formula CO,R’*R*S*CH:C H:S*R*CO,R’ where R is a benzene or naphthalene residue and R a metal aryl or alkyl group.The preparation of acetylenebisthiolbenzoic acid is described. F. M. G. M. Products Formed by the Action of Heat on y-Sulphamido- benzoic Acid. W. B. STODDARD (Amer. Chew&. J. 1912 47 1-20) -Remsen and Muckenfuss (Abstr. 1896 i 481) found that when p-sulphamidobenxoic acid is heated at 220’ for eight hours there are formed p-sulphobenzoic acid ammonium hydrogen p-sulphobenzoate an ‘‘ infusible diamide of p-sulphobenzoic acid,’’ and “ iso-p-sulphamido- benzoic acid.” When the ‘‘ infusible diamide ” is heated with phosphorus penta- chloride at 194-197’ p-chlorobenzonitrile is produced.An attempt mas mado to remove one of the nitrogen atoms whilst leaving the other by heating the compound with hydrochloric acid but without success. It was also found t h a t the desired result could not be attained by ciiazotisation or by heating with sodium carbonate solution. When a current of steam was passed through a mixture of the diamide and magnesium hydroxide ammonia was liberated and a magnesium salt was obtained of an acid isomeric with p-sulphamidobenzoic acid but entirely different from ‘‘ iso-p-sulphamidobenzoic acid.” The corre- sponding potassium salt reacts readily with phosphorus pentachloride but the infusible diamide is not thereby regenerated. These facts indicate that the nitrogen atoms of the infusible diamide are both attached t o carbon and that the acid isomeric with p-sulphamido- benzoic acid is probably p-carbamido benzenesulphonic acid.When Remsen and Muckenf uss’ ‘‘ iso-p-sulphamidobenzoic acid ” is heated in a sealed tube with concentrated hydrochloric acid a t looo the infusible diamide is produced. If the acid is heated in a sealed tube with water a t 220° a small quantity of a substance is produced which crystallises in thin plates. Analyses of the barium and sodium salts of “ isop-sulphamidobenzoic acid ’’ have shown that this acid is not isomeric with p-sulphamidobenzoic acid but has the composition OF an anhydride of the latter C,H,<Co->NH. Determinations have so2i. 112 ABSTRACTS OF CHEMICAL PAPERS.been made of the electrical conductivity of solutions of both these acids. It is suggested that the action of heat on p-sulphamidobenzoic acid may be represented by the equation 4C02H-C,H,*S0,~NH2 = C,H4<S0,>(NH2)2 CO- + C0,H*C,H4*S0,H + E. G. Bornylene from P-Iodohydrobornylenecarboxylic [ P-Iodo- camphanecarboxylic] Acid Dibromobornylenecarboxylic [ap- Dibromocamphanecarboxylic) Acid and Dihydrobornylene- carboxylic [ortho-Camphanecarboxylic] Acid. JULIUS BREDT and W. HILBING (J. p r . Chem. 1911 [ii] 84 778-786. Compare Abstr. 19 10 i 498).-P-lodocam;olza~~,zec~s.6ozylic acid CH*C02H CSJ314<(5HI ' prepared by the action of hydrogen iodide on a glacial acetic acid solution of bornylenecarboxylic acid crystallises in needles m. p. 129-130'. It dissolves in hot aqueous sodium carbonate yielding a crystalline sodium salt together with the hydroxy-acid Cl1H,,O3 pre- viously described (Zoc.cit.). When heated with strong aqueous sodium hydroxide the sodium salt yields bornylene which has [.I - 23.68' in toluene and [a] - 23.94Oin benzene. A glacial acetic acid solu- tion of bornylene when heated at '70' with sulphuric acid yields a bornyl acetate b. p. 103-104'/14 mm. which on hydrolysis furnishes a borneol of m. D. 175-178'. I YBr*CO,H ap-Dibromocamphanecccrbox?/Eic mid C,EIl,<aHBr obtained by the addition of bromine to bornylenecarboxylic acid in carbon tetrachloride solution and purified by means of the sodium salt crystallises in needles m. p. 159-1609 ortho-Camphanecar boxylic acid (Zoc. cit.) prepared by reducing /3-iodo- camphanecarboxylic acid yields a chloride b.p. 114-115'/14 mm. and an amide m. p. 166-167" which is con- CH2*CH-CH*NH2 verted by the Hofmaun reaction into an I amine of the annexed formula. Improvements in 1 UMe2l the preparation of hornylenecarboxylic acid are CH~.&X~*CH also described. Ethyl bornyles~ecurboxylale obtained as a by- product in crystallising the anhydride from alcohol has b. p. 121-122°/16 mm. F. B. Electrolytic Reduction of Oamphononic Acid to cis-trams - Camphonolic Acid Camphonololactone. JULIUS BREDT [and in part with WILHELM LUND and AUGUST AMANN] (J. pr. Chem. 191 1 lii] 84 7S6-799).-When subjected to electrolytic reduction camphon- onic acid yields a mixture of two stereoisomeric camphonolic acids 2>CMe*C0,H OH*F)H-CMe CH2-CH,ORGANIC CHEMISTRY.i. 113 which may be separated by distillation whereby the cis-camphonolic acid is converted into the corresponding lactone whilst UH2*7H-0 the cis-trans-isomeride distils unchanged. I ?Me I cis-Canzpi6or~oZoZactorze (annexed formula) has m. p. CH,*CMe.CO 160-161' b. p. 239.2' [a] - 16.2' in alcohol. cis-Camphonolic acid is obtained by the addition of the calculated amount of cold dilute hydrochloric acid to its barium salt which is prepared by the action of barium hydroxide on the preceding lactone. It has [a] - 33.4" in alcohol aud a varying m. p. according to the rapidity of heating; when rapidly heated it has m. p. 197-198'. The isomeric cis-trans-ccc.lnphonolic acid has m. D. 249-250'. $!HBr* CMe CH,-C H 2 y-Bromocarn~Zion~nic acid 2>CMe*C02H obtained by the action of saturated aqueous hydrobromic acid on the cis-laclone has m.p. 146-147' and when treated with aqueous sodium carbonate 1s reconverted into the lactorre. Both cis-trans-camphononic acid and cis-camphonololactone are oxidised by concentrated nitric acid to camphoronic acid. Improvements in tile method of preparing camphononic acid (Lapworth and Lenton Trans. 1901 79 1287) are also described. F. B. Resolution of Mandelic Acid into its Active Gomponents by means of Phenylethylamine. LENNART Simwr (J. pr. Chem. 1911 [ii] 84 743-744).-The resolution of r-mandelic acid has been accomplished by crystallking the I-P-phenylethylamine salt from water the salt of the d-acid being the less soluble. The pure d-acid is obtained from the rnandelic acid recovered from the mother liquor by crystallisation with d-phenylethylamine. F.B. Atrolactic [a-Hydroxy-a-phenylpropionic] Acid. LENNART SMITH(J.~. Chem. 1911,[ii],8477Y1-743).-The first part of thispaper contains an account of a large number of experiments on the formation of acetophenonecyanohydrin and the hydrolysis of the latter compound to atrolactic acid. This is followed by a description of the resolution of tlhe acid into its optically active components and of its behaviour towards hydrochloric acid. I n the preparation of atrolactic acid by Spiegel's method (Abstr. 1881 277 ; compare Staudinger and Ruzicka Abstr. 1911 i 462) better yields are obtained by replacing the hydrochloric acid by glacial acetic acid. Atrolactic [a- hydroxy-a-phenylpropionic] acid crystallises with $H,O and the potassium sodium and mugnnesium salts with 2H,O; t h e strontium salt Sr(C,H90,),,4H20 and caclcium salt CaH2(CgH,0,) m.p. 216' (decomp.) are also described; the affinity constant K= 0.0341. The resolution of the acid into its optically active component is accomplished by crystallisation of its salt with I-/3-phenylethylamine the salt of the d-acid being the less soluhle (compare McRenzie and Clough VOL. CII. 1 2:i. 114 ABSTRACTS OF CHEMICAL PAPERS. Trans. 1910 9'7 1016). The pure 1-acid is obtained by crystallising the acid recovered from the mother liquors with d-phenylethylamine. The l-phen?/lethyZarrai?ze salts of both the d- and the I-acids were analysed. The barium BaX,,&H,O calcium CaX,,3$H,O and potassiuim KX,2H20 salts of the active acids are also described (X - C,H,O,).Hydratropic acid is readily obtained from atrolactic acid by heating it with concentrated hydrochloric acid for three-qurtrters of an hour on the water-bath and reducing the product with sodium amalgsm. When heated with concentrat,ed hydrochloric acid for four hours a t 130-1 35' atrolactic acid yields P-chloro-a-phenylpropionic acid together with a- and P-isoatropic acids. By heating tropic acid a t 170-180° it is converted into atropic acid which is accompaDied by small quantities of a- and P-isoatropic acids. From these experiments the conclusion is drawn that the action of hydrochloric acid on atrolactic acid yields successively atropic /3-chloro- a-phenylpropionic and isoatropic acids.F. B. a-Phenyl-a-ethylglycollic Acid. LENNART SMITH (J. pr. Clzem. 19 1 1 [lii] 84 744-745). - a-Phenyl-a-ethylglycollic [a-hydroxy- a-phenyl butyric] acid is best prepared by the addition of glacial acetic acid to a mixture of potassium cyanide and propiophenone and hydrolysis of the nitrile thus obtained by means of hydrogen chloride in ethereal sclution the resulting amide being finally hyclrolysed by aqueous sodium hydroxide. Jt crjstallises in needles m. p. 132' (corr.) (compare Grignard Abstr. 1903 i 32) and is resolved into its optically active components by crystallisation of the d-P-phenylethyl- a m i n e salt. Z-a-HpdPox y-a-phen ylbut yric acid has in aq rieous solution [a];* - 14'. F. B. Ethyl Anisoylacetates. AND& WAHL and C. SILBEEZWEJG (Bull.SOC. chim. 1912 [iv] 11 25-34. Compare Abstr. 1908 i 647 ; 1910 i 1163).-Ethyl rn- andp-methoxybenzoylacetates have been prepared by condensing ethyl acetate with ethyl m- and p-methoxy- benzoates in presence of sodium. The corresponding ortho-compound has already been prepared by Tahara (Abstr. 1892 844). Ethyl p-anisoylucetate OMe*C6H4*CO*CH,*C02Et is a pale yellow liquid b. p. 180-190°/10-12 mm. decomposing partly into p-anisoyldehydracetic acid. It yields a green copper salt (CI2HI,O4),Cu m. p. 2 loo and a nitroso-deri vative m. p. 11 3-1 14'. Ethyl m-methoxybenxoylacelate also decomposes very readily on tfis- tillation. I t yields a green copper salt m. p. 168-169O and a nitroso- derivative m. p. 94'. W. G. Preparation of Halogenated 2-Anthraquinonglaminobenzoic Acids.FRrrz ULLMANN (D.R.-P. 238106. Compare Abstr. 1906 i 426 953 ; 19 10 i 270).-4-Bromo-2-anthrapuinonylarninobenzoic acid Ci,H7O2*NH*C,H,Br.C0,H a violet powder which does not fuse a t 300' is obtained by heating l-chloroanthraquinone (24.2 parts) with 4-bromoan thranilic acid (22 parts) potassium acetate (20 parts) copper acetate (1 part) and copper powder (1 part) at 160' in amyl-alcoholic solution. F. M. G. M.ORGANIC CHEMISTRY. i. 113 Fagaramide a New Nitrogenous Substance from the Root- bark of Fagara xanthoxyloides. HERMANN THOMS and F. THUMEN (Ber. 1911,44,3717-3730).-The root-bark of Fagarcc zanthoxyloides contains a nitrogenous substance C,,H,,O,N crystallising from alcohol in well-formed crystals m. p. 119-120". Thirty grams were obtained from 40 kilos.of the drug. The compound termed fagaramide is identified as the isobutylainide of piperorzylcccrylic acid CH2:O2:CG)IT,*CH CH-CO*NH-CH,*CHMe,. On prolonged boiling with 50% alcoholic potassium hydroxide it is decomposed into isobutylamine and piperonylacryl ic acid. Pagaramide is prepared synthetically by condensing piperonyl- acrylic chloride and isobutylamine in ethereal solution. In a similar manner the isomerides are prepared namely the normal secondary and tertiary butylamides of piperonylacrylic acid. All four isomerides form chitracteristic crystalline dibromo-derivatives. Fagaramide reacts neutral and does not form salts; it belongs to the same group as piperine. All four isomerides have the same physiological action namely narcotic on cold-blooded animals but practically none 01 warm-blooded animals.Fugccramide is obtained by extraction with benzene. The dibronaicle C,,H,703NBr forms slender colourless needles m. p. 154-155'. i)n oxidation of fagaramide piperonal and piperonylic acid m. p. 230' (not 227.5-228') are obtained. Piperonylacrylic acid has m. p. 242" (not 2.38' or 232-234' as stated in the literature). isoButy1- amine hydrochloride bas in. p. 177-178' (not 160'). Piperonylacrylic chloride CB202:CGH,-CH:C1H*~OCl is conveniently prepared by the action of thionyl chloride on the acid. Piperonylacry I-n-butylarnide CH,0,:C,H3*CH:CII*CO*NH~[CH2]~l*CH forms very minute crystals m. p. 85-86'. in small colourless needles m. p. 134-135" (decornp.). CH20, C,H,* CH CH CO*NH*CHMeEt yields colourless needles m.p. 161-162'; the dibromide has m. p. 164-165" (decornp.). Piperonylacryl-tert. -6utylumide CH,O,:C,H,*CH CH*CO*NH* CMe forms strongly refractive pale yellow prisms which are colourless when powdered m. p. 138-139' ; the dibromide crystallises in slender colourless needles rn. p. 182-183" (decornp.). SIEGMUND GABRIEL and JAMES COLMAN (Bev. 191 I 44 3628-3636).-The analogous behaviour of ketones and sulphones in many reactions led the authors to hope that 7- and 6-aminosulphones might yield heterocyclic bases just as y- and 6-amino-ketones yield pyrrolines and tetrahydropyridines respectively. This expectation has not been fulfilled but the work has led to the production of the following substances. When warmed with phosphoriis pentachloride phthalyltaurine The dibromide separates Pzperonylacr?ll-sec.-butylalnide E.P. A. Aminosulphones and Allied Gompounde. i 2i. 116 ABSTRACTS OF CHEMICAL PAPERS. This substance is very stable to hoL water does not react with benzene and aluminium chloride but is converted into the methyl ester C,H4<CO>N*02H,*S0,Me co C6H4<Co>N* co C H,-CH,*SO Ph m. p. 103-104" by methyl-alcoholic sodium methoxide. Phenyl /3-phthcclimidoethyl sulphone m. p. 185-185.5" obtained from benzenesulphinic acid alcoholic sodium ethoxide and P-bromoethylphthalimide a t loo" yields by hydrolysis by acetic acid and hydrochloric acids a t 140° phenyl- P-nminoethylsulphone hydrochloride NH,*CH,*CH,*SO,Ph,HCl m. p. 155-155.5" glistening needles. Yhercyl-y-~ht?Lalirnidopropylsulphone m.p. 126' and phenyl-y-ccminopropylsulphone hydrochloride m. p. 222O are obtained by similar methods from y-iodopropylphthalimide. Phenyl mercaptan and P-bromoethylphthalimide react with boiling alcoholic potassium hydroxide tp form phcsnyl P-phthcclimidoethyl sulphide C6H4<CO>N-C H,*CH,*SPh m. p. 59-60" long needles by the hydrolysis of which plcenyl P-aminoethyl sulphidc hydrochloride NH,*CH,*CH,*SPh,HCl m. p. 160-161° is obtained. /3-Phthnlirnidoethyl mercaptan is converted by warm nitric acid D 1 '2 into ~ - p h t l c u l i ~ ~ ~ i c l o e t ~ ~ y ~ d ~ s u l p ~ ~ o ~ ~ c l e co (C,H,<g>N*CH,.CH ) + w. p. 155-156" which reacts in benzene with aluminium chloride on the water-bath to form after treating the product with hydro- chloric acid /3-pht~alimi~oet~~yl~~lp~Linic mid C,H4<Ez>N*CH,* CH,.S02H m. p. 149-1495' (decornp.) glistening white leaflets This acid which is also obtained by reducing the disulphoxide or phthalyltauryl chloride by zinc dust and 96% alcohol is decomposed by boiling 20% hjdrochloric acid yielding phthalic acid taurine and /I-phthalimido- Action of a-Hydroxyisobutyronitrile on the Nitrile Ester of Iminodi-phenylacetic Acid. GEORGE L. STADNIKOFF (J. Rues. Phys. Chem. Xoc. 1911 43 1235-1244).-1t has been previously suggested (Abstr. 1909 i 771 772; 1910 i 825) by the author that in the action of a-hydroxypropionitrile on the nitrile esters of propionyliminocycloheptanecarboxylic and iminodi-phenylacetic acids an intermediate unstable compound of the ammonium hydroxide type is formed this then undergoing decomposition into other hydroxy- nitriles and nitrile esters of imino-acids.Such intermediate forma- tion of ammonium hydroxide compounds is assumed also (1) in the formation of amines and amino- imino- and nitrilo-acids by the action of hydroxy-nitriles on either ammonia or its derivatives ; (2) in the interaction of alkyl halides or halogen derivatives of acids with ammonia or its organic derivatives and in a number of other reactions. ethyldisulphoxide. c. s.ORQAXIC CHEMISTRY. i. 117 Most of the reactions represented in this way are explained equally well by Nef’s ‘‘ methylene-dissociation ’’ ; thus the interaction of the nitrile ester of iminodi-phenylacetic acid and a-hydroxypropio- nitrile may be regarded as occurring in the following stages (I) the hydroxynitrile dissociates into rnethylene derivative arid water CH,*CH(OH)*CN = CH,*C(CN) + H,O ; (2) water and the nitrile ester give the ammonium hydroxide compound CN*CHPh*NH,(OR)*CHPh*CO,Et ; (3) the ethylidenecyanogen combines with the ammonium hydroxide compound giving the nitrile ester of a nitrilo-acid CK*CHPh*NH(OH)( CHMe*CN)-CHPh*CO,Et which then decomposes into derivatives of an imino-acid of lower molecular weight and mandelonitrile. I n order to arrive at4 a decision between these two explanations the author has investigated the action of a-hydroxyisobutyronitrile which is incapable of methylene dissociation on the nitrile ester of iminodi-phenylacetic acid.The result confirms the author’s view of these reactions the product of the reaction being anhydronitrilo- diisobutyricphenylacetic acid which is formed as follows CN*6HPh*NH*CHPh*CO2Et + OH.CMe,.CN = CN*CHPh*NH(OH)(CMe2*CN)*CHPh*C02Et = OH*CHPh.CN + UN*CMe,=NH*CHPh*CO,Et ; the latter + 0H*CMe,.CN = CN*CMe,*NH(OH)(CMe,*CN)*CHPh*CO,Et = H20 + CN*CMe2-N(CMe,*CN)*CHPh*C02Et.This nitrile ester then under- goes hydrolysis to the substituted triacetic acid which is subsequently transformed into the corresponding anhydride. AnAydronitriZodiisobutyricphen~lacetic acid C1,H,,O,N (see above) crystallises from aqueous alcohol in silky needles m. p. 180-181° (slowly heated in sealed capillary). As would be expected from the fact that iminodicarboxylic acids are rendered neutral to phenol- phthalein by one equivalent of alkali hydroxide two equivalents of the latter are sufficient to neutralise this anhydride.Photochemical Behaviour of Nitroterephthalaldehyde. HERMANN %IDA (J. pr. Chem. 1911 [ii] 84 827-83O).-The author finds that nitroterephthnlaldehyde is very sensitive to light. A cold xylene solution of the aldehyde on exposure to direct sunlight rapidly becomes turbid and deposits a yellow solid consisting of 2-nitroso- 4-aldehgdobenxoic acid CHO*C,H,(NO)*CO,H. The acid sl0wly chars at 250-300° but when placed in a bath a t 300’ instantly melts with decomposition It dissolves in alkalis and alkaline carbonates yield- ing yellowish-green solutions. Its solution in concentrated sulphuric acid develops with a trace of phenol an emerald-green coloration. Details of a lecture experiment illustrating the photochemical transformation of the aldehyde are given.Angeli-Rimini Reaction of the Aldehydes. ANGELO ANGELI ( A t t i R. Accad. Lincei 1911 [v] 20 ii 445-449. Compare Balbiano Abstr. 1911 i 987).-The author has prepared Wallach’s ketone OMe* C,H,*CH,*COMe and Balbiano’s product from anethole T. H. P. F. B.i. 118 ABSTRACTS OF CHEMICAL PAPERS. glycol and Gnds that they are identical and do not give the Angeli- Rimini reaction when i t is carried out as originally described. ' h e reaction however is given by these substances when an excess of alkali is employed. This explains Balbiano's resirlts. It is advisable to add the calculated quantity of alkali in small portions (compare Angeli and Castellana Abstr. 1909 i 392) and in the qualitative test it is better to use the sodium salt of Pilot,y's acid.Deoxybenzoin benzoin b e n d and dibenzyl ketone behave similarly giving the reaction only when an excess of alkali is employed. R. V. S. o-Hydroxyacetophenone 5-Chloro-o-hydroxyacetophenone and Certain Chlorochalkones and Chloroflavones. FRANZ Compare Abstr. 1901 i 213).-The authors describe the preparation of o-hydroxyacetophenone from 5-acetylamino-?-hydroxyacetophenone and of 5-w-dichZoro-2-1~7~drox~acetophenone (rn. p. 64") from o-chloro- 5-nrni~~o-2-hydroxyacetophenone. The corrsspondiug w-chloro-5-bromo- 2-h~droxyacstophenone has m. p. 68". 5-Chloro-2-bydroxyacetophenone condenses with benzaldehyde in the presence of sodium hydroxide t o form 5-chloro-Z-hycll.oxychalkone m. p. 10So which readily combines with bromine to form il dibl.omide of m. p.185'. H. W. GUIDO BARGELLTNI and LEDA RrNr (Gazzetta 191 1 41 ii 435-445).-Hydrochalkoues may be prepared conveniently by reducing chalkones with hydrogen in the presence of platinum-black. I n this way from an ethereal solution of 2-hydroxychalkone 2-hydroxydihydrochalkone was obtained ; the product is best purified by conversion into the semicurbaxone CI6Hl7O2N3 which forms white needles m. p. 174-175' (softening a t 170"). The reduction of 4-methoxychalkone with zinc dust and acetic acid yielded n substance (probably a diketonic condensation product) C32H.7004 which crystallises in colourless needles m. p. 224-225O. When 4-methoxychalkone in ethereal solution is reduced with bydrogen iu preseuce of platinum- black 4-methoxydihydrochaZkor~e C,6H1602 is obtained ; i t crystallises in colourless needles m.p. 59-60" (softeniog at 55O) arid it gives a yellow coloration with concentrated sulphuric acid. The semicarbaxone C17Hl,0,N3 forms colourless needles m. 1). 118-120". 3 4-Dimethyleneoxychalkone when reduced with zinc and acetic acid yields a substance C32H2S0 which crystallises in colourless needles and is solid a t 260'. When the reduction is effected with hydrogen in the presence of platinum-black 3 4-dinzethyEeneoxydi- hydrochalkone C16H1403 is produced ; it crystallises in colourless needles m. p. 39-40' (softening at 35O) and gives a red coloration with concentrated sulphuric acid. The semicarbaxone C17H1703N3 Preparation of Ben zoylaminoh ydroxy antbr aquinon es.FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (19. K-P. 238488).- When I 5-dibenzoyldiami~ortptbraquinones are oxidised with either KUNCKELL [with ALBERT FURSTENBERG] (Ber. 1911 44 3654-3666. Chalkone and Hydrochalkones. forms colourless needles m. €7. 153-154'. K. v. s,ORGANIC CHEMISTRY i. 119 manganese dioxide a persulphate or a perchlorate a by droxy-group is introduced into either position 4 or 8. 1 5-Dibenzoyldiamiooanthr:tquir1one (10 partsj dissolved in 100 parts of siilphuric acid (10% SO,) was slowly treated at 5-10" with manganese dioxide (3.5 parts) maintained below 15" with continual stirring during two hours and the 4-hydroxy-1 5-dibennxoyldiamiizo- nnthrayuinone subsequently isolated by known methods. 4-Chlo~o-8-hydroxy-1 5-dibenxoy Idiaminoanthraquinone was prepared in R similar manner with pot'assium persulphate from 4.chloro-1 :5- dibenzoyldiarninoanthraquinone whilst 2-chloro-1 5-dibenzoyldinmino- anthraquinone furnished 2-~7~lor0-4(8)-hydroxy-l 5-dibenzoyldiamino- anthmguinone.F. M. G. M. Preparation of Dianthraquinonyl- or Polyanthraquin onyl carbamides. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P 238550 238551 238552 and 238553. Compare Abstr. 1911 i 469 655 995).-The preparation of dianthraquinonylcarbamides has previously been described and the reaction has now been extended to the case of heteronuclear PP'-diaminoanthraqixinones. These compounds orange-yellow powders are obtained by the action of /3p'-anthraquinonyEenedicarboxyE chlorides (obtained from 2 6- or 2 7-diaminoanthraquinones with excess ef carbonyl chloride) on amino- or diamino-antlirayuinoncs. The second and third patent's state that PP'-dianthraquinonyl- carbamide can be readily prepared by heating P-aminoanthraquinone a t 170" with carbamide or ethyl urethane either with or without solvent until evolution of ammonia (and in the latter case alcohol) ceases.The foiirth patent deals with the employment of substituted iiryl- or diaryl-carbamides and describes p-tolyl-2-anthraqii.irionyl- carbamide yellow crystals obtained by the prolonged boiling of $2-toluidine with 2 2'-dianthraquinonylcarbamide. F. M. G. M. [Preparation of Anthracene Derivatives.] BADISCHE ANILIN- dz SODA-FABRIK (D.R.-P. 238980).-It is now found t h a t the compounds previously described (Abstr.1907 i 226) can be prepared from 1 1'-dianthraquinonyl-2 2'-dialdehyde by reduction with either an alkaline solution of sodium hyposulphite or with zinc in concentrated sulphuric acid solution. F. M. G. M. Decomposition of Alkylidenehydrazines Conversion of Ionone and +-Ionone into the Corresponding Hydrocarbons C,3H22. NICOLAI M. KIJNER (J. Russ. Phys. Chem. SOC. 1911 43 1398-1 402).-The decomposition of iononehydrazone in presence of potassium hydroxide is an exothermic reaction and gives rise t o a-ionane CHEt:CH=CH<CMeLC-$>CH CMe *CH which is a colourless liquid with a faint odour of turpentine b. p. 220-221°/747 mm. Dto 0.8530 n 1.4784. It readily oxidises in the air combines with 4 atoms of bromine and in acetic anhydride solution gives a raspberry-red coloratiolz with R drop of sulphuric acid.It shows the normal molecular refraction whereas the similar hydrocarbon correspondiog -i. 120 ABSTRACTS OF CHEMICAL PAPERS. with p-ionone should exhibit considerable exaltation owing t o the presence of conjugated double bonds. +-Io~mne C kiEt:CH*CH2*CMe:CH*CH2*CH:CMe ('t) obtained in a similar manner from +-ionone is a colourless faintly-smelling liquid b. p. 224-225'/751 mm. Di0 0.8151 73 1.4725; it rapidly turns yellow in contact with the air unites with 6 atoms of bromine and is converted into a-ionane when its acetic acid solution is boiled with a small quantity of sulphuric acid. The formula given above is of doubtful accuracy as the hydrocarbon does not exhibit optical exaltation. T. H. P. Crystalline Form and Optical Characters of Pinocampheol Methyl Xanthate.N. I. SURGUNOFF (Zeitsch. Rryst. Min. 1911 50 62-63; from Bull. SOC. Nat. Moscow 1907 543-551).-The crystals of pinocampheol methyl xanthate (Tschugaeff Abstr. 1908 i 93) are orthorhombic with a b c = 1.3747 1 0.9787. Constituents of Essential Oils. The Constitution of the Active Caryophyllenes ; Transformation of the Active Caryophyllenes into Monocyclic Derivatives. FRIEDRICH W. SEMMLER and ERWIN W. MAYER (Rer. 1911 44 3657-3679).-The authors have subjected caryophyllene to the action of ozone and studied the decomposition products of the ozonide so formed. They consider that crude caryophyllene is composed chiefly of three cnryo- phyllenes namely Deussen's inactive a-caryophyllene and two active caryophyllenes which they name terp-caryophy Ilene and lim-caryo- phyllene and to which they assign the respective provisional formulae L.J. S. CMe CH C'Me CH \ /\ \/ \ CH Me \ \ /,! \ \ CH Me Commercial caryophyllene when dissolved in ethyl chloride and subjected to the action of ozone yields a soluble ozonide C,,H,,O together with a small quantity of an insoluble ozonide which probably contains seven or eight atoms of oxygen. When the soluble ozonide is heated in glacial acetic acid solution it yields carbon dioxide and formaldehyde together with n mixtmre of acidic and neutral products. From the acidic products a keto-acid C,,H,,O a diketo-acid C,+H,,O and an acid C,H1,O were isolated. l'he keto-acid CllH1,03 is a pale yellow mobile oil of b. p. 183-187'/11*5 mm.D20 1.040 a +44' rt; 1.4677. Its siluev salt was analysed. The methyl ester has b. p. 139-142O/15.5 mu. D20 0.9913 n$ 1,4527 a? +42'. The samicarbazone has m. p. 183'. When oxidised with nitric acid the keto-acid yields dimethylsuccinic acid and dibasic caryophylkenic acid C9H1,0,. The latter forms a non- crystalline syrup of b. p. 215-218'/9 mm. 222-225'/13 mm. It isORGANIC CHEMISTRY. i. 121 remarkably stable towards nitric acid. The silver and copper salts were prepared. The methyl ester. has b. g . 127-131"/11 mm. D20 1.0456 n$ 1.4462 a + 44'. When boiled with acetic anhydride caryophyllenic acid yields an anhydride of b. p. 152-158'/10 mm. D20 1.1399 n$ 1.4755 a -25". Similar products were obtained when the keto-acid was oxidised by Iwomine in alkaline dolution.Oxidation with permanganate also gave caryophyllenic acid to which the formula CH ~~CMe(Co2H2>CMe \CIqCO,p) is assigned. The diketo-acid C,,K,,O is a viscous yellow oil of b. p. 239-2.32'/ 11.5 mm. D20 1.0830 nZ1.4804 az,O +41'. Its silver salt begins to darken at 130' and has m. 1). about 3145". Its methyZ ester has b. p. 184-188°/12 mm. DZo 1.047 a$ +38" n D 1.4680 With semi- clzrbazide hydrochloride i t gives no product of definite m. p. When oxidisod with nitric acid it. yields succinic acid and caryophyllenic acid. On kreatment with bromine in alkaline solution it yields caryophyllenic acid together witlh a mixture of acids of high boiling point. The acid CsH1402 has b. p. 120-128"/9 mm. DZo 0.9527 nD 1.4457 [a] + 17' and is monobasic.Its methyl ester has b. p. 64-6So/ 9 mm. D20 0.922 [a];' + 20' nD 1.4326. From the neutral portion (see above) a ketone CioH180 a probable keto-aldehyde C11Hls02 a diketone C1,HZoO2 and a deketo-aldehyde C,,H,,O were isolated. The ketone C,,H,,O is a mobile pale green liquid of b. p. 73-76"/ 11 *5 mm. It has DZo 0.8823 9b 1 *4387 - 7". Its semicarbaxone has m. p. 176'. When reduced by sodium :tmalgam i t yields an aZcohoZ Ci,H200 b. p. 87-89"/11*5 mm. D20 0.8707 7 ~ 1.4507 [a] - 6'. This on treatment with phosphorus pentachloride passes into the corresponding chloride (b. p. 70-73'/10 mm. D20 0*882) which when heated with quinoline yields the hydrocarbon CloH16. The latter has b. p. 50-54"/11*5 mm. D20 0.812 72 1.4410 a;' - 6'. When oxidised by bromine in alkaline solution the ketone yields carbon tetrabromide together with a nao~,obasic acid C,H,,P b.p. 131-133'/13.5 mm. D23 0.9773 12 1.4500 a - 7" the szlver salt of which had m. p. 219' after darkening at about 160". The methyl ester has b. p. 86-89'/15 mm. D23 0.9208 n 1.4360 a -5.5'. The amide has tn. p. 114". On oxidation with nitric acid the ketone yields an acid C,H,,02 b. p. 119-122"/12 inm. DZo 0.972 nz 1.4457 uz +7*5'. This yielded a methyl ester of b. p. 69-73"/15 mm. D20 0.9369 n$' 1.4307 a$ 3-22' and an umide rn. p. 115-116'. The formation of these compounds is represented by the scheme on p. 122. The diketone C,,H after treatment with permanganate to destroy any aldehyde present is a colourless mobile oil b. p. 137-142'/9 mm. DZo 0.9600 n 1.4677 uz +34".The b. p. mas unaltered by a second treatment with permanganate whilst the follow- ing values were found for the remaining constants D20 0.9598 nD 1.4622 uD + 39". On oxidation with nitric acid the diketone yields dimethylsuccinic acid and caryo- phyllenic acid. Oxidation with bromine in alkaline solutiorl leads to the same products. The dikuto-aZdzhyde Cl4H2,O3 is a viscous yellowish-green oil of I t s amide melts at 9 6 O . Its semicarbaxone had m p. 219O.i. 122 ARS'I'RACTS OF CHEMICAL PAPERS. b. p. lSl-l84O/13 mm. DZo 1.0280 nz 1.4774 a? -25". It does not yield a uniform semicarbazone. When oxidised with perman- ganate it yields the acid CI4Hz2O4 (see above). Nitricacid converts i t into succinic acid and caryophyllenic acid. CMe CH \ /\ \/ \ CH Me L terp.-Caryophyllene. HNOs CHMe ,f CHMe CHMe HC-CMe NaOH+Br HC-GMe HC-CMe \ \ \ cH,* CO Me CH;CO,H CO,H Ketone C,,H,,O. Acid C9H1,0,. Acid CsH,,O,. Deusseri's c:qwphyllene was converted into caryophyllene dihydro- chloride which on treatment with methyl-alcoholic potassium hydroxide yielded the previously-described '' recovered " dextrorotatory caryo- phyllene (Abstr. 1911 i 73). An attempt to transform this through the nitrosite into Deussen's la?vorotatory caryophenyllene was unsuccessful. Reduction of the blue nitrosite (Deussen Abstr. 1907 i 945) led to the formation of a substance C,,I-12?N which is probably an amine. It has in. p. 148-150"/13 mm. DZo 0.929'7 a2,0 + 1 3 O nz 1.5030. H. w. New Philippine Essential Oils. BENJAMIN T. BROOKS (PhiZippine J. Sci.1911 6 333-351. Compare Abstr. 1911 i 1000).-The essent,ial oil from the fl.owers of Michelia Zonpfolia contains linalool eugenol methyl ether and methylbutyric and acetic acids and a very small percentage of thymol. The leave.. of Toddalia asiatica (L.) (T. Acdeata Pem. Kurz) yield 0.08% of an essential oil which gave the following constants n3,0 1.4620 Di,O 0.9059. The oil is largely linalool but also contains a white crystalline camphor-like compound m. p. 96*5-97O which is very unstable. The lenves of Clausena anisum olens yield 1.20% of an essential oil with the following constants n? 1.5235 Dg8 0.963 ester number 3.6. It contains chavicol methyl ether to the extent of 93%. About 0.2% of an essential oil with 0.850 is obtainable from the leaves of LimnophiZn sp.Orange-peel oils were also examined the naranjita variety giving a much greater yield than the cajel. The two oils resemble oneORGANIC CHEMIS'I'ILY. i. 123 another very closely the former having constatits it 1.4700 [u] 90*85" ester number 8.0; the latter ng 1.4675 Di 0.8390 ester nnmter 8.5. The leaves of Citrus decumana yield 1.7% of an essential oil with constants n3,n 1.4644 D~~0*8700 [a] 22-90' ester number 10. It contains tlipenteue and linalool and a trace of an aldehyde. Tho oil from the leaves of Citrus hyatrix has the following constants 7tE 1.4850 IXi 0.9150 [a] - 10*50° ester number 50.2. W. G. The Essential Oil of Seseli bocconi. LUIGI FRANCESCONI and X. SERNAGIOTTO ( A t t i R. Accad. Lincei 191 1 [v] 20 ii 481-4S6).- The essential oil of this plant has been obtained by distilling it in steam By fractional distillation OF the oil a number of fractions mere isolated of which the more volatile consist of terpenes I-pinene and P-phellandrene having been identified.The oil also contains compounds with carbonyl groups (probably aldehydes) and ethers and alcohols are also present. R. V. S. Chemistry of Caoutchouc. 111. Theory of Vulcanisation. 11. DAVID SPENCE [with J H. SCOTT] (Zeitsch. Chem. Ind. Kot?t?oidp 1911 9 300-306. Compare Spence and Scott Abstr. 1911 i 657).-Further experiments have been made on the extrdction of sulphur from vulcanised caoutchouc by treatment for measured time intervals wit ti equal successive quantities of boiling acetone. These show that equilibrium between the adsorbed sulphur and that in the acetone solu- tion is rapidly attained aud this fact is regarded as favourable to the interpretation which has already been given to the exponential form of the extraction curves.From two series of observations made with the same mixture of para-caoutchouc and sulphur which had been subjected to the vulcnnisiug process for different periods of time it i t is found that the proportion of chemically combined sulphur increases with the period of vulcanisation and that the initial portions of the extraction curves corresponding with the removal of the free sulphur are also different in the two cases. When a non-vulcanised mixture of caoutchouc and sulphur is similarly extmctcd with boiling acetone the form of the extraction curve obtained is qliite different,.The removal of the sulphur from the unvulcani>od mixture is how- ever also a slow process by reason of the inclusion of the free huiphur in tbe jelly-like mass which the non-vulcanised caoutchouc forms in contact with the boiling acetone. An extraction experiment with ebonite. gave an extraction curve differing from those obtained with samples of vulcanised caoutchouc but in this case also there appears to be it considerable amount of sulphur which is present in the chemically combined form. H. M. D. Brazilian Copal. STANISLAUS MACHENBAUM (Arch. Pharrn. 19 12 250 6-12).-The copal was red to yellow in colour and was in small pieces showing a thin weathered layer. It sintered at 1 3 7 O melted completely at 160° and had the following percentage solubilities iui.124 ABSTRACTS OF CHEMICAL PAPERS. the solvents named alcohol 76 acetone 80 alcohol and ether 92 light petroleum 20. The copal gave the following constants acid numbers ( a ) direct 123.2 ( b ) indirect 128.5 ; sapouification numbers (a) cold 136.2 (6) hot 144.2. An ethereal extract of the resin was shaken with ammonium carbonate solution which (1) extracted two acids of which one brazil- copalic acid C24H4003 m. p. 170-175° yielded a lead salt insoluble in alcohol and (2) precipitated ,z mixture of two acids of which one m. p. 195-200° gave a lead salt insoluble in alcohol. Sodium carbonate solution then extracted from the ethereal solution two acids of which brazibopalolic acid Cz2€13s02 m. p. 95-10O0 gave an insoluble lead salt.The residual ethereal solution yielded nothing to potassium hydroxide solution but on steam distillation furnished a volatile oil boiling chiefly at E245-255° and a residue of a-6raxil- copaloresen as a brownish-yellow viscid mass. The portion of the copal insoluble in ether was dissolved in a mixture of alcohol and ether and extracted with potassium hydroxide solution which removed n mixture of resin acids. These were dissolved in alcohol precipitated as lead salts by lead acetate regenerated and separated into two portions by treatment with cold alcohol the soluble portion is a-brazilcopalinic acid C H 3o02 m. p. 180-1 S5O. The solution after extraction with potassium hydroxide contained P-brazilcopaloresen arid a little volatile oil. All the substances described are amorphous.The acids give phytosterol-like reactions and their acid numbers are recorded. T. A. H. Columbia Copal. STANISLAUS MACHENBAUM (Arch. Pharrn. 191 2 250 13-19).-'l'he copal was in large pieces and had a slight turpentine-like odour. It sintered at 120° melted completely at 155O and had the following percentage solubilities ether 56 alcohol 78 alcohol and ether 90 light petroleum 18. Its constants were as follows acid numbers ( a ) direct 105 ( b ) indirect 106.1 saponifica- tion numbers ( a ) cold 106.8 (b) hot 110.6. An ethereal extract of the resin was extracted with (1) ammonium carbonate solution and (2) sodium carbonate solution. I n each case a mixture of two resin acids was extracted and was separated into its components by solution in alcohol and precipitation by lead acetate.The acid giving an insoluble lead salt alone was examined in each case the other being viscid and intractable. As in the case of Brazilian copal (preceding abstract) ammonium carbonate precipitated two resin acids from the ethereal extract; of these the one giving an insoluble lead salt had m. p. 170-175O. That extracted by ammonium carbonate is cotumbia- copnlic acid C22H4003 m. p. 145-150O. The acid subsequently removed by sodium carbonate is columbiacopalolic c~cid (;122H4002 m. p. 90". The residual ethereal extract contained volatiIe oil boiling chiefly at 2 I 0-220° and brqwn viscid a-colwmbiacopalores~?~ The portion of the crude copal insoluble in ether was dissolved in a mixture of alcohol and ether and extracted with potassium hydroxide solution which removed a-cotunzbiacopalinic acid ClqH240 m.p. 180-1 85O soluble in cold alcohol and ~-colurnbiacopalznw acid C,Hz,03 xn. p.ORGANIC CHEMISTRY. i. 125 1 go’ soluble in hot alcohol. solution. and phytosterol-like reactions of the resin acids are recorded. ~-Co~urr~bic6copa~oresen reuaiued in the The acid numbers All the products mentioned are amorphous. T. A. H. So-called Chicle Gum. J. E. QUINTUS Bosz and N. H. COHEN (Arch. Phawn. 1912 250 52-62). -Tschirch and Schereschewski’s work on this material (Abstr. 1905 i 685) has been repeated and it is shown that their a-chiclalban is a-amyrin acetate their P-chiclalban is a mixture of esters of lupeol and /3-amyrin their y-chiclal ban con- tains as its principal constituent a substance C,GH,i,O C57H1,40 or C,,T3,,,0 m.p. 68’ which on admixture with Hesse’s p-cerotinone nielts a t 66-68’ and is possibly identical with that subst.ance (Abstr. 1893 i 57). Chiclafluavil is a mixture of all the substances mentioned above. On steam distillation chicle ‘‘ gum ” yielded a minute quantity of an alkaline distillate with an odour of amines and on hydrolysis by alkalis furnished acetic hexoic and cinnamic acids. The portion of the “gum” insoluble in acetone is brittle and has none of the properties of caoutchouc 90 that the properties of chicle ‘‘ gum,” which render it suitable for “chewing gum” manufacture do not depend on the presence of caoutchouc-like substances. T. A. H. Occurrence of Chitin. EDMUND 0. VON LIPPMANN (Ber. 1911 44 3716-3717).-A colourless thin tough skin foxming a light grey amorphous powder when dry which collected on the surface of some waste liquors in a sugar factory which had been set aside for several months is shown to be composed of chitin produced by bacterial action.E. F. A. Lutein from Yolk of Egg. RICHARD WILLSTATTER and HEIN- XICH H. ESCHER (Zeitsch. physiol. Chern. 1912 76 214-225).-The chemically indifferent yellow pigments of plants and animals are divided into the hydrocarbons of the carrotene group C40H56 soluble in light petroleum and the oxygen compounds of the xanthophyll group C40H5G02 soluble in alcohol (Willstiitter and Rlieg Abstr. 1907 i 865). Lycopene the colouring matter of tomatoes has been shown (Willstiitter and Escher Abstr. 1910 i 330) to belong to the carrotene group and it is now proved that lutein from the yolk of eggs is a xanthophyll isomeric with and closely related to that derived from chlorophyll.The methods of separating lutein from the phosphatides fats and cholesterol of the yolk are described the pure pigment crystal- ises slowly from carbon disulphide in well formed prisms or quickly in fire-red conglomerates of pointed microscopic needles m. p. 195-1 96’ (corr.). It crystallises from methyl alcohol in prisms with V-shaped indentations which arc amber-yellow with metallic lustre. Lutein forms an additive compound with iodine in ethereal solution ; the iodide is a dark violet powder consisting of microscopic pointed needles. It absorbs oxygen to the extent of 23% of its weight.i. 126 ABSTRACTS OF CHEMICAL PAPERS.I n alcoholic solution it. shows ahsorption bands in the blue and indigo- blue corresponding with thwe of xauthophyll froni leaves but differing from carrotene. E. F. A . [Preparation of Thionaphthen Derivatives.] KALLE & Co. (D.R.-I?. 239089. Compare Abstr. 1911 i 666 667 1009).-An account of the preparation of substances having the general formu1:t RS*C,H,(S*CH,.CO,H)*CO,H some of which have been previously described (Abstr. 1911 i 666). The following new compounds are mentioned 2-Carboxy-5 -methylthio~?'enylthiolacetic acid yello wish-white needles m. p. 220' (decomp.). 3-Keto-6-methyZth~ioZ-( I j-thionu~hthen-2-c~rbox?/lic acid :i colourl ess powder and 3-keto-6-nzeth?/ZthioZ-( 1 )-ti't,ionccphthen glistening needles m. p. 133-134'.F. M. G . 311. [Preparation of Thionaphthen Derivatives.] KALLE SS Co. (D.R.-P. 239092 j.-o-Nitro-m-xylidine was diazotised and converted by the action of potassium cyanide and copper sulphate into 2-nitro-m- zylonitrile needles m. p. 126'; this when heated a t 100° during twelve hours with 80% sulphuric acid yielded 6-nitro-2 4 -di.r,wtl'yl6enxoic acid yellow needles m. p. 180° and on reduction furnished the correspond- ing 6-amino-S 4-dimethylbenzoic acid :t yellow crystalline powder m. p. 126' (decomp.). The foregoing amino-acid when diazotised xanthogenated and treated with chloroacetic acid yielded 4-carboxy-m- xyZyZ-5-thioZacetic mid CO,H.C,H,n'le,*S.CH,.CO,H a microcrystallin e powder ru. p. 158-159' which on fusion with sodium hydroxide furnished keto-4 6 - d i r n e t ? ~ y l t ~ ~ i o n a p ~ ~ t ~ ~ e n c ~ c r ~ ( ~ ~ ~ ~ c acid red flakes arid was subsequently converted in to kelo-4 6 -clii,ietl~?llt?~ioi~(6p~~t~'en needles m.p. 93" which rapidly darkens on exposure to light. F. &I. G. ill. [Preparation of Anthraquinonethioxanthones.] FRITZ ULL- MANN (D.R.-P. 238983. Compare Abstr. 1911 i 1010).-Anthra- puinone-thioxanthorte orange-red leaflets m. p. 335' is prepared by healing anthraquinone-l-o-thiolbenzoic acid with phosphorus penta- chloride in nitrobenzene solution ; t b e anthraquiijone-thioxanthone m. p. 272O described previously (Abstr. 1910 i 270) has now been obtained by fusing anthraquinone-2-o-thiolbenzoic acid with p-toluene- sulphonyl chloride at 205O whilst anthraquinonyl-1 5-cli-o-thiol- benzoic acid and phosphorus pentachloride furnish an ccr~tl~raquinone- dithiozanthoue glistening orange needles which do not melt at 350".F. M. G. M. LPreparation of Thioindigo " Derivatives.] KALLE & Co. (D.R.-P. 239673).- When 3-oxy-( l)-thionaphthen-?-carboxylic acid arid its derivatives containing a free or substituted amino-group in the benzene nucleus are oxidised in either alkaline solutioii or neutral suspension they yield '; thioindigo " derivatives. " 6 6'-Diantinothioindigo " was obt;tined as a brown flocculent pre- cipitate by the oxidation of an aqueous alkaline solution of 6-amino-ORGANIC CHEMISTRY i. 127 3-oxy-(l)-thioiiaphtheu-2-carboxylic acid with air a t 70-80" ; cjthor MAX SIEGFIUED (Zeitsch. pluysio2. Cheni. 1912 '76 234-237).-The platinichloride of active lysine when dried over sulphuric acid has the composition C,H,,U,N,,PtH,CI,,EtOH and crystallises in needles more slender and darker than those of the platinichloride of inactive lysine which forms stouter paler yellow prisms having the composition C6H1,0,N,,PtH,Cl,.Racemic and active lysine may be sharply differentiated in this manner. oxidising agents can also be employed. F. ill. 0. nil. Lysine Platinichloride. E. F. A. Hzmopyrrole. RICHARD m T ~ ~ ~ ~ ~ B and ~ A S U H I K O ASAIIINA (Ber. 1911 44 3707-3710).-Haemopyrrole from haemjn or from chlorophyll has been shown to contain phyllopyrrole C,H,,N iso- haemopyrrole C,H&N and another base C,H,,N. The constitutions 2 3 4- and 2 4 3-dimethylethylpyrrole respectively were ascribed to the two latter compounds (Willstatter and Asahina this vol.i 41) but further investigation is necessary as neither of them proves to be identical with the 2 4-diruethyl-3-ethylpyrrole synthesised by Knorr and Hess (Abstr. 191 1 i 1019; compare also Fischer and Bartholomiius this vol. i 50). The synthesis of Knorr and Hess is confirmed; 2 4-dimethyl- 3-ethylpyrrole has b. p. 84"/10 mm. 197'/710 mm. Dfo 0.913. The styphnats forms four-sided prisms rn. p. 136' ; the cldoropicrute gives pri~ms m. p. 140O. On oxidation with nitrous acid methylethyl- maleiniinideoxime is obtained cryst$allising in prisms m. p. 215-21 6' (Knorr and Hess give 201'). The pyrrole base was reduced with hydrogen iodide and phosphorus a t 240° and finally with platinum and hydrogen.The pyrrolidine obtained has b. p. 145" and forms a plutirddoiide crystallising in pointed prisms m. p. 220° and an u-nu~hthylcarbamide crystnllising i n irregularly-defined rhombic plates m. p. 109-1 10'. It is essentially different from isohsmopyrrolidine. ~ I G I MARINO and v. SQUINTANI (Atti R. Accad. Lincei 1911 [v] 20 ii 666-670. Compare Marino Abstr. 1908 ii 833)- When absolutely dry recently sublimed selenious anhydride is mixed with an equimolecular quantity of a solution of pure piperidine in arihydrous benzene cooled with ice a colourless crystalline mass is deposited. The reaction is complete in eight or ten hours. The product after being washed with anhydrous benzene gives on analysis figures corresponding with the formula C5H,,N*Se0 but allowance has to be made for absorbed water owing to the extremely hygroscopic nature of the substance.The compound has m. p. 70-71' but traces of water may lower it t o 64-65'. It probably reacts with alcohol but the reaction product has not been isolated. E. F. A. Asymmetrio Selenites. The piperidine group is not involved in the reaction. R. V. S. Cyclic Ammonium Bases. JOHANNES GAUAMER (J. pr. Ci~en~. 1911 [ii] 84 817-820).-A reply to Decker and Kautman ( Abstr.,i. 128 ABSTRAOTS OF CHEMICAL PAPERS. 1911 i SO?') who erroneously attributed to the author the view that the cnrbinol bases have in all cases the structure of amino-aldehydes or ketones. F. B. Action of Methylamine and Aniline on Benzoyldehydracetic Acid. [Mutual Replacenient of Ammonia and Amines in Pyridone Derivatives.1 PAVEL I. PETRENKO-KRITSCHENKO and JOH. SCHOTTLE (Ber. 1911 44 3648-3654. Compare Abstr. 1911 i 102O).-The interaction of benzoyldehydracetic acid with methylamine and aniline has been studied whereby the methyl- and phenyl-lactams of benzoyldehydracetic acid have been obtained. These have m. p. 188" and 203" respectively. Unlike the lnctam described previously (Zoc. cit.) neither of these compounds yields a pyridonecwboxylic acid when warmed with alkali. The methyl-lactam on treatment with hydrochloric acid yielded 2 6-diphenyl-4-pyridone the plcctinichloricle of which m. p. 218-221° (clecomp.) was analysed. When similarly treated the phenyl-lactam yielded 2 6-diphenyl-1 4-pyridone. The methyl- and phenyl-lactams were also prepared by the action of alcoholic solutions of methylamine and aniline on the lactam. Con- versely the methyl-lactam when treated with alcoholic ammonia yields the lactam which was identified by conversion into 2 B-diphenyl- 4-pyridone-3-carboxylic acid and 2 6-diphenyl-4-pyridone ; on trent- ment with an alcoholic solution of aniline i t yields the phenyl-lactam.Similarly the anilino-group of the phenyl-lactam is replaceable under the action of ammonia or methylamine. H. W. The Condensation of Acetonedicarboxylic Ester with Aldehydes Ammonia and Amines. PAVEL I. PETRENKO- KRITSCHENKO (J. pr. Chem. 1912 [ii] 85 1-37).-A rksumQ of the results of already published investigations by the author and various co-workers (Abstr. 1906 i 452; 1907 i 708; 1908 i 564; 1909 i 605 959; 1910 i 188).D. F. T. Preparation of Derivatives and Homologues of Indole. GESELLSCHAFT FGR TEERVERWERTUNG (D.R.-P. 2381 38).-When aryl- hydrazones (or their keto- or aldehyde derivatives) are heated with zinc chloride they furnish indole derivatives. 2-Methylindole was obtained in 75% yield by heating acetonephenylhydrazone (1 part) in 3 parts of solvent naphtha with zinc chloride (1 part) at 150" during one hour extracting with water and subsequently fractionating in a vacunm. 3-Methylindole previously prepared by E. Fischer in 38% yield was produced in 80% yield from propionaldebydephenylhydrazone a t 200° whilst ethyl phenylhydrazonepyruvate furnished a 60% yield of 2-indolecarboxylic acid at 130". F. M. G. M. New S y n t h e s i s of Benzylidine-2- methylquinoline. VON ISMAILSKY (J.pr. Chem. 1912 [ii] 85 90-92).-1n the presence of sodium hydroxide solution o-aminobenzaldehyde slowly condenses with excess of styryl methyl ketone yielding benzylidene-2-methyl quinoline. The product agrees entirely with previous descriptionsORGANIC CHEMISTRY. i. 129 (Wallach and Wusten Abstr. 1883 1096 ; Jacobsen and Reimer Abstr. 1884 335 ; Doebner and Peters Abstr. 1890 1'76 ; Eibner Abstr. 1901 i 64). D. F. T. Condensation of para-Quinones w i t h Indolee and Pyrroles Containing Hydrogen in the 3-Position. RICHARD MOHLAU and ALFRED REDLICH Ber. 191 1 44 n60Fi-3618).-a-'Methylindole arid p-benzoquinone (2 mols.) react in boiling alchhol t o form 2-methyl- .inclyZ-3-bonxopuinone CH<Co.CH>C-C<C A 1 >NH dark violet CH-CO C Me bronze needles m.p. about 185' a n d quino1"in quantitative yield. That the reaction occurs directly a t the 3-hydrogen atom not a t the iruinic hydrogen atom is proved not only by the fact that the colourless buco-compound obtained by the action of hydrazine hydrate forms a diacetnta m. p. 132' (a triacotnte should be formed had the reaction occurred in position l) but also because 1 2-dirnethyl- indole and p-benzoquinone yield in a similar manner an almost quanti- tative amount of 1 2-dirnat~~y1ind~l-3-benzoqzcinone7 G16H1302N m. p. about 1 GO" violet-black needles. I n a similar manner 2-methylindole and toluquinone yield a corresponding substance Ci,H,802.N m. p. about 195' (decomp.) reddish-violet needles ; the colourless dzacetate of its leuco-compound has m.p. 146". 2-Phenylindole and p-benzo- quinone give about 40% of 2-phenylindyl-3-benzoquinone7 C H130,N m. p. about 205' blue needles ; 2 5-dimethylindole reacts wlth p-benzoquinoue and with toluquinone to form about 90% of 2 :5- dimethylindyl-3-benzoquinone Cl,H,,02N m. p. about 301" (decomp.) violet-black bronze needles and 3 5-dimethyZindyl-3-tol~quinon~~ C17H,,02N reddish-violet needles. As IS to be expected from the preceding pyrroles unsubstituted in positions 3 and 4 react with p-quinones (4 mols. two of which are utilised in oxidising the initially-formed leuco-compound) to form diqninonylpyrroles ; thus 2 5-dimethylpyrrole yields 3 4-diquinonyl- 2 3-dimeth,ylpyrrole9 black microcrystalline powder whilst 5-phenyl-2-methylpyrrole yields 3 4-diquii~onyl-5- phenyl-2-methylpyrrole C23H1504N brownish-black powder.Whilst with the preceding indoles and pyrroles only one nucleus enters the benzoquinone mole- CH,-CHMe 9. /- \ cule it is found that the more ' strongly basic 2-methyldihydro- indole reacts like the following bases with p-quinones in hhat CHMe*cH two nuclei enter the quinone molecule ; thus 2-methyldi- hydroindole yields a su6stance (annexed formula) m. p. 18'To9 brown needles ; met h ylaniline y ieldu bismethylccnilinoqucinone (NPhMe),C6H2O reddish-brown leaflets ; tetrahydroquinoline yields biststrahydroquino- Zinoquinone (C9NH1,),C,H202 m. p. 189O brown needles and 4-methyltetrahydroquinoline yields bis-6-methyltet~ahydroquinolino- CMe:~*C,H,O NH<CMe:C.C 6 4 2 \-/ 0 quinone !C,H,MeN) Z:,H,O m p.197". c. 5. VOL. CII. i. ki. 130 ABSTRACTS OF CHEMICAL PAPERS. Products of the Condensation of 9-Methylcarbazole and Phthalic Anhydride. FRANZ EHRENHEICH (Monatsh. 191 1 32 1103-1 11 4. Compare Scholl and Neovius Abstr. 191 1 i 567).- By the interaction of molecular proportions of 9-methylcarbazole and phthnlic anhydride the main product is 9-methylcarbazole-3-phthaloylic acid C H 4 ~ / U H * C 0 C,H,* CO,H together with small quantities of 9-methylcarbazole-3 6-diphthaloylic acid CO,H C,H4*CO* C,H,ywC,H,* CO*C,H,*CO,H. When twice as much phthalic anhydride is used the quantity of the latter is increased considerably. 9-Methylcarbazole is conveniently prepared by the action of methyl iodide or of methyl sulphate at the ordinary temperature on potassium carbazole.9- Methp Zcavbaxole- 3-pJhtha ZoyZic acid prepared by the interaction of the components in benzene solution with aluminium chloride crystal- lises in large well-formed rhombs m. p. 232'; i t shows a character- istic cherry-red coloration with Concentrated sulphuric acid changing t o green or. the addition of strong nitric acid. The methyl group is only very slowly and partly eliminated on boiling with hydrogen iodide and the attraction of alkyl to nitrogen is apparently increased by the phthaloyl group; indeed no trace of halogen alkyl is obtained on heating the diphthaloyl derivative with hydrogen iodide. The same methyl ester is obtained from the silver salt and methyl iodide or from the acid chloride and methyl alcohol; i t crystallises in monoclinic prisms m.p. 146". 9 - Methyl car baxole- 3 6 -diphthaZop Zic acid cry s tallises in slender needles m. p. 330O; the cherry-red coloration with sulphuric acid turns yellow on the addition of strong nitric acid. The dimethyl ester crystallises in large colourless prisms m. p. 196". 2 3 6 ; 'I-DiphthaZoyZ-9-metJ~ylcarbazoZe C H 4 < ~ ~ > C H 2 ~ / c H 2 < C O > C 6 1 r 4 ' co prepared by heating 9-methylcarbazole-3 6-diphthaloylic acid with sulphuric acid at 90' (compare Scholl and Neovius Zoc. cit.) crystal- lisea in reddish-yellow plates which have not melted at 400". With concentrated sulphuric acid a bluish-violet solution is obtained which becomes orange when strong nitric acid is added. E. F. A. Ester Acids of Thiocarboxylic Acids with Aliphatic Alcobol Acids.V. BROR HOLMBERG (J. pr. Chem. 1911 [ii] 84 634-636. Compare Abstr. 1910 i 361 834).-A detailed account of the action of amines towards the following acids xanthoacetic acid OEt*CS*S*CH,*CO,H ; ethyl dithiocarboglycollic acid SEt*CS*O*CH,*CO,H ; dithiocarbodiglycollic acid CO,H*CH,*S.CS-O*CH,*CO,H ; carbo- dithioglycollic acid CO(S*CH,*C0,H)2 and trithiocarbodiglycollic acid CS( S*CH,*CO,H),. The previously -observed formation of diphenylcarbamide by the action of aniline on xanthoacetic acid is considered by the author toORGANIC CHEMISTRY. i. 131 be due to the intermediate formation and decomposition of an additive compound with aniline according to the following scherrie CO H* C tI,*S*CS*OEt-+ C0,H.C H,*S.C(S*NH,Yh)(NHPh) QEt -+ CO,H*CH,*SH + EtOH + H,S + CO(NHPh),.Evidence in support of the author's view is furnished (1) hy the non-formation of diphenylcarbarnide in acid solution and in the absence of excess of aniline and (2) by the isolation of similar additive compounds of the thiocarbarnylglycollic acids with amines (see b+low). P-Phenylethylamine reacts with xsnthoacetic acid yielding an oily thiouret hane C fl MePh N H CS 0 Et . Ethyl dithiocarboglycollic acid forms with aniline in aqueous solution the ardine salt SEt=CS*O*CO,*NH,Ph m. p. 77.5-78" ; when heated with aniline in alcoholic solution diphenplcarbnmidd is produced. Dithiocarbodiglycollic acid reacts with ethylamine to form ethyl- thiocltrbamylthioglycollic acid and the anhydride of ethylthiocarbnmyl- glycollic acid mentioned below.With aniline in ethereal solution i t yields tile aniline salts C,H605Q0,2 NH,Ph lustrous pale yellow leaflets m. p. 97-97.5" and C,H,O,S,,NH,Ph m. p. 110-1 10.5". When heated with aniline in aqueous solution dithiocarbodi- glycollic acid gives rise to a mixture of substances the nature of which depends on the ratio of aniline t o acid and the temperature and duration of the reaction ; the following compoun Is were isolated from the product s-diphsnylthiocitrbamide phenylrhodanine trithiociwbo- d iglycollic acid g!ycollic acid t hiog I y co I lie acid p hen y 1 t hiocar ba m y 1- glycollic acid and its anhydride and phenylthiocarbamylglycollanilide. Trit hiocarbodiglycollic acid re'w t a with primary amines yielding thioglycollic acid and rhodanines (compare A bstr.1910 i 361); with P-phenylethylamine it forms 3-P-p?~enylethylrl~oda.nine s-cs>N CH MeP h bO*CH pale yellow tabular crystals m. p. 11 1-1 12'. Ethyltrithiocarb~glycollic acid and aniline in aqueous solution yield phenylrhodanine and ethyl trithiocarbonate. X-S,ibstituted derivatives of thiocarbamylglycollic acid are readily obtained by the intecaction of amines and ethyldithiocarboglycollic acid. EtiLylthiocarbamylg1;ycoZlic acid NHEt*CS*O*CH,*CO,H prepared from ethylamine in aqwous solution crystallises in stellar aggregates of smill white needles m. p. 97.5-98' ; the s o d i u ~ i ~ salt is amorphous; the barium salt (NEIEt%S-O*CH,*CO,),B~,3H2O forms colourless plates. It is oxidised by bromine to ethylcarba,nylyZ~collic ucid colourless prisms m.p. 85-86" and when warmed in aqueous sol 11 tio u forms a n anhydride (2 - thion-3 - ethyl - 4-oxozoliclone) bH,*CO '-">NE t which crystallises in colourless Iplstes m. p. 43-10*5". L)iethykhiocarb~myZ~lycolZic acid NEt,*CS*O*CH,*CO,H prepaid from diethylamine crystallises in flat colourless prisms m. p. 90.5 -9 lo VOL. CII. i. I?i. 132 ABSTRACTS OF CHEMXCAL PAPERS. and yields crystalline sodvum and barium salts; the eth$ ester is an oil. Phen y Zthiocarbumplyl yco Elic acid NHPh- CS 0 CYH,*CO €1 m. p. 11 1-1 12O obtained together with phenylrhodanine and diphenyl- carbamide by heating aniline with ethyldithiocarboglycollic acid in aqueous solution crystallises with one molecule of acetic acid in long colourless prisms which lose their acetic acid on exposiire to air ; the d i e c o l a salt and barium salt (NHPh*CS*O*CH2*CO,)Ba,3H,O were analysed.It readily loses water forming the anhydride (2-thion- 3-phenyl-4-oxaxolidone) I ">NPh which crystallises in stout irregular plates or short prisms m. p. 172-173' and dissolves in aqueous sodium carbonate to form the sodium salt of the original acid. When heated in neutral or alkaline solution it yields glycollic acid and diphenylcarbamide ; in aqueous ammonia phenylthio- carbamide is produced. Oxidation with potassium permanganate yields phenylcarbamylglycollic acid. Phemy Ethiocarbamy 29 Zycolluni Zide NHPh*CS-O*C H COO NHPh pre- pared by heating the acid with aniline i n aqueous solution forms lustrous white needles m. p. 133-134'. 2 - Thion - 3 - phenyl - 4 - oxazolidone is oxidised by bromine to 2 4-diketo-3-phenyloxazolidine.When dissolved in alcoholic sodium >C(SNa) *OEt ethoxide it forms a gelatinous sodium salt which is decomposed by acetic acid yielding 2-ethoxy-2-thiol-3- phen yl-4-oxaxolidor~ ~o*NPh>C(8H)*OEt. This crystallises in colour- less needles m. p. 73-73.5' and dissolves in alkalis forming salts of phenylthiocarbamylglycollic acid. The above-mentioned sodium com- pound reacts with ethyl iodide yielding a reddish-yellow oil probably >C(SEt)*OEt which on treatment with aqueous sodium QO*NPh CH,-0 hydroxide is converted into ethyl mercaptan and phenylcarbamyl- glycollic acid ; with ethyl chloroacetate it forms the compound YooNPh>C( OEt)-S*CH,-CO,Et which by dilute hydrochloric acid is hydrolgsed and converted into 2 4-diketo-3-phenylthiazolidine and by acetic acid is hydrolysed to phenylcarbamylglycollic acid and a substance crystallking in small flat prisms or white needles m.p. 171-172'. The latter substance is'probably diphenylisohydantoin eo*NPh>C:NPh. The interaction of chloroacetanilide and the sodium salt of 2-thiol-2-ethoxy-3-phenyl-4-oxazolidone yields a thiazolidone cornpound f;H2-S S-CH >C:NPh or & Npi>C:NPh which forms pale yellow CO*NPh crystals m. p. 174-175". The prolonged action of alcoholic sodium ethoxide on 2-thion- 3-phenyl-4-oxazolidone at the ordinary temperature gives rise to 0- CH,*CO $!O*NPh CH,-0 CH,-0 CH,--0 CH,-0ORGANIC CHEMISTRY. i. 133 sodium phenylthiocarbamylglycollate ; at 1 O O O xanthanilide is produced.Yiperidine combines with 2 - thiori - 3 - ethyl - 4 - oxazolidone in alcoholic solution to form 2-thiol-2-piperidyl-3-ethyZ-4-oxaxolidone ~o"Et>C(SH)*N:C~alo colourless prisms rn. p. 146-1 47' and CH,-0 with the corresponding phenyl derivative yielding Z-thioZ-2-piper- >C( SH) C5NHlo which forms iclyl-3-phen yl-4-oxaxolidme white needles m. p. 130-132O. 2-Thion-3-ethyl-4-oxazolidone condenses with benzaldehyde in the presence of sodium ethoxide yielding a-keto-py-diphenylbutyro- lactone (Erlenmeyer and Knight Abstr. 1894 i 592); the same compound accompanied by s-diphenylthiocarbamide is obtained by the condensation of 2-thion-3-phenyl-4-oxazolidone with benxaldehyde by sodium ethoxide. $!O*NPh CH,-0 2 - Fhion - 5 - belzzylidene - 3 - ethyl- 4 - oxazolidone rEt*Co>C CHPh cs-0 prepared by condensing 2-thion-3-ethyl-4-oxazolidone with benz- aldehyde in the presence of piperidine crystallises in colourless plates or short prisms m.p. 94-5-95'; when the condensation is effected by means of acetic anhydride a stereoisorneride crystaliising in long pale yellow prisms m. p. 137*5-138' is obtained. prepared by condensing 2-thion-3-phenyl-4-oxazolidone and benz- aldehyde by means of acetic anhydride forms slender golden-yellow needles m. p. 181.5-182O. 3-Phenylrhodanine reacts with piperidine in alcoholic solution yielding phenlyZpi(pe~idyZthioc~~.~a~~de NHPh-CS*C,NH,, thin white prisms m. p. 100-100~5' and with alcoholic sodium ethoxide t o form a sodium salt which on acidification with acetic acid yields yO*NPh CH,-S 4- ket 0-2-thiol-2-ethox y-3-phenyZthiaxolidine >C(SH)*OEt ; this L crystallises in colourless flat prismatic needles m.p. 61 -5-62'. in support of the thiazolidine formula assigned to the rhodanines. The formation of the latter compound furnishes additional evidence E. B. Nitro-derivatives and Nitro-hydrazones ROBERTO G~IUSA (Atti R. Accad. Lincei 1911 [v] 20 ii 578-583. Compare Hantzsch Abstr. 1910 i 475).-The author refers to the different coloured modifications of hydrazones of nitro-aromatic aldehydes whioh he has described and suggests that they are chromo-isomerides like the nitro- anilines of Hantzsch. According to him a nitrohydrazone of the formula NO,Ar*CH:N-NRPh can exist in the two forms P,NmAr*'H:N*~PhR (red) and O,N*Ar-CH:N -NPhR (yellow).Since %he hydrazones contain a -C:N- linking they can exist in 1 2i. 134 ABSTRACTS OF CHEMICAL PAPERS. s p - and anti-forms and it ie suggested that the red isomerides are the syn-forms because that configuration mould favour the origin of the internal additive product containing a secondary valence. R. V. S. ConBtitution of Buchner's so-called Pyrazolinecarboxylic Acids. CARL B~LOW (Ber. 1911 44 3710-3716).-By the inter- action OF phenylhydrazine and acraldehyde Fischer and Knoeve- nagel obtained phenylpyrazoline NPh<CH"*CH,. Subsequently N- FH L I N=QH pyrazoline NH< was obtained by Curtius and Wirsing by CHn*CH,' the interaction of hyiraziie and acraldehyde. This is very unstable towards oxidising agents but it can be distilled unchanged and is stable towards hydrochloric acid On the other hand the pyrazolinecarboxylic acids described by Buchner (Abstr.1893 i 430; 1894 i 348) obtained from aliphatic diazo-compounds and unsaturated mono- or di-carboxylic acids of the ethylene series are characterised by giving up all their nitrogen on heating or distillation and forming cyclopropanecarboxylic acids. When boiled with dilute mineral acids hydrazine is eliminated. Lastly they are readily converted into pyrazole derivatives. These facts are not in agreement with the relatively stable nature of heterocyclic five-membered rings and it is considered that Buchner's cids are more correctly formulated as mixed azines of glyoxylic and oxalacetic acid esters ; thus the product from ethyl diazoacetate and ethyl fumarttte has the formula CO,Me*CH N*N C( C0,Me) CH,* C0,Me.Azines such as benzylideneazine CHPh:N*N:CHPh give up the whole of their nitrogen on heating and the other properties of Buchner's acids are shown to be in accord with formulating them as mixed azines instead of as pyrazolinecarboxylic acids. E. F. A. Pyrimidines. LIV. Condensation of Carbamide and Guanidine with Esters of Allylmalonic and Some Alkyl- s u b s t i t u t e d Allylmalonic Acids. TREAT B. JOHNSON and ARTHUR J. HILL (Amer. Chem. J. 1911 40 537-549).-In an earlier paper (Abstr. 1911 i 502) it has been shown that ethyl allylmalonate reacts with thiocarbamide to form ethyl 2-amino-4-lceto-7-methyItetrshydro- hexathiazole-5-carboxylate instead of the expected allylthiobarbituric acid whilst ethyl benzylallylmalonate and diallylmalonate condense with thiocarbamide with production of acylthiocarbamides or their y-lactones.I n view of this abnormal behaviour experiments have been carried out to ascertain whether barbituric acid derivatives are formed by the condensation of ethyl allylmalonates with carbamide and guanidine. v 5- Allylmalonylcar bamide (allylbarbituric acid ) CO<~~:~~>CH~CH,-CH:CH m. p. 1 6 7 O obtained by the action of carbamide on ethyl malonate inOhGRNIC CHEM 1S'l'K.Y. i. 135 presence of sodium ethoxide crystallises in nearly colourless plates and is hydrolyscd by potassium hydroxide with formation of allpl- malonic acid. 5-AllylmaEonylyuan~dine NH C < s g ::>OH* CH,*CH:CH 2H20 m. p. 265-266" crystallises in pink prisms or hexagonal tablets.5 5 - DiallylmaZon?/lcnrbamide (dia?lyZbag*bituric acid) CO<~~:~~>C(CH2-CH:CH2)2 m. p. 173" obtained by the action of carbamide on ethyl diallyl- maloaate forms colourless rhombohedra1 crystals and on hydrolysis with potassium hydroxide yields diallylmalonic acid. 5 5-Diallyl- malonylyuanidine NH :C<zE gg>C( CH,*CH CH,) crystallises in colourless rhombohedral prisms does not melt below 300° and is hydrolysed by potassium hydroxide with formation of diallylmalonic acid. 5- Benx yl-5-allylmalon ylcarbamide (5- benxyl- 5 -all ylbarbituric ad) co<NH*CO NH*Co>C(CH2Ph)*CH2*CH:CH2 m. p. 19S0 prepared by the condensation of carbamide with ethyl benzylallylmalonate crystallises in prisms ; it can also be obtained by the action of ally1 iodide on silver benzylbarbiturate.The compound is not hydrolysed smoothly by potassium hydroxide. When gumidine is heated with ethyl benzyl- a1 ly 1 malon a t e in presence of sodium e thoxide benx ylally liminoma lonuric acid NH2*C(NH)*NH*CO*C(CH2Ph)(CH2*CH:CH2)*C02H or more probably NH:C<~&o~~~>C(CH2Ph)*CH2*CH:CH2 is produced which crystallises in needles does not melt below 300° and is immc- diately transformed by dilute bydrochloric acid into 5- benzyl-5-allyl- malonylguanidine hydrochloride. 5 -BenxyE5 - allylnialonylguanidine ,H*d<NH*CO NH.c-,>C(CH,Ph)*CH2*CH:CH can also be obtained by . the action of benzyl iodide on 5-allylmalonylguanidine ; it forms a fine cdourless powder and does not melt below 300". Attempts to obtain pure benzylallylmalonic acid by the hydrolysis of this compound with potassium hydroxide were not successful.Benzylallylmnlonic acid CH CH*CH,*C(CH,Ph)(CO,H) was obtained as a viscid uncrystallisable liquid by the hydrolysis of its ethyl ester with potassium hydroxide ; the silver salt was prepared. E. G. Preparation of 1 -p-Dimethylaminophenyl-2 3 4-trimethyl- 5-pyrazolone. FARBWERKE VORM. MEISTER LUCIUS & BRUNING (D.R.-P. 238256).-1 -p- A minophenyl-2 3 4- trimethy l-5-pyruxolone m. p. 225-22'io prepared by the reduction of 1-p-nitrophenyl- 2 3 4-trirnethyl-5-pyrazolone cryst,aIIises from water in colourless crystals containing 9H,O. When heated at 90-1 00" with methyl iodide it yields 1 -p-di~rlet~,?/Za?n~inop~e?~yl-~ 3 4-triinethyZ-~-pyraxololae which crystallises with 2H,O and has m.p. 140" (anhydrous). 1-p-Aminophenyl- The following compounds are also described :i. 136 ABSTRACTS OF CHEMICAL PAPERS. 3 4-dimet?~yl-,5-py1~azolone ti colourless crystalline powder m. p. 232O obtained by reducing the corresponding nitro-compound. 5-Elhoxy- 1-p-tcminophenyl-3 4-dimethylpyraxole m. p. 95-97O. 1-p-Acetylaccmilzo- phenyl-3 4-dimathyZ-5-pyi-axoZone a colourless crystalline powder m. p. 2 72-273". 5-Ethoxy- 1 -p-met ylaminophenyl-3 4-dirnethylpyruzole m. p. 130'. 5-Acetoxy- 1-p-acet~laminop~e?ayl-3 4-dimethylpyraxoEe m. p. 167-1 6 8". 1 - p-Meth ylaminophmyl- 3 4-cEirnothyl-5-pyraz010~ needles or leaflets (lH,O) m. p. 108-110'. 1 -p-Dimetl~?/Zaminophenyl- 3 4-dimethyl-5-pyruzolone LLI p.199-200". I-p-Acet?ilmethylamin~- phenyl-3 4-dimethyl-5-pyruxolone crystallises with 2H,9 m. p. 80" or 1 6 2" (anhydrous). 5- Ethoxy-l -p-methylaminophenyZ- 3 4-dzrneth ylpyraxoZe is an oil; its nitroso-derivative has m. p. 75". 1 -p-Acatylmethylaminophenyl-2 3 4-trimethyl-5-pyraxolone has m. p. 139-1 40". l-~-Methylai??ino~~enyl-2 ; 3 4-~rimsthyZ-5-;uyraxolone has m. p 168'. F. M. G. M. FARBWERKE VORM. MEISTER LUCJUS & BR~NING (D.R.-P. 238373).-1t is found that 4-&0- valerylamino-1 -phenyl-3-methyl-5 - pyrazolone and its derivatives can be methylated (methyl sulphate) without eliminating the isovaleryl group in position 4 ; the following compounds are described 4-iso- Vklerylumino-l -phenyt-2 3 -climst?iyl-5-pyrazoEone forms colourless crys- tals KU p.203". 4-iso74aleryZumino- 1 -phenyl-3-methyl-5-pyraxoZone forms colourless crystals m. p. 230". 4-iso ~ a z ~ ~ y l a l l ~ i ~ o - 5 - e t h o x y - l -pher&yl- 3 mthylpyrcmole has m. p. 115". 5-CT~Zoro-4-isovaZerylamino-1-p~n~l- 3-metlqlpyraxolee has m. p. 1 ZOO 4-isoVaZerylamino-5-isovaleryZoxy- l-;uhenyl-3-methylp~ruxoZe has m. p. 122-123". 4-a-Bromoisovaler~l- amino-1-phenyl-2 3-dintethyl- 5-pyraxolone forms colourless crystals m. p. 206". 4-a-BromoisoaccZeryZamino-5-a-bromoisouule~yZoxy-1-phenyl-3-~tAyl- pyrccxole colourless crystals m. p. 114-1 16" is obtained by treating an aqueous solution of 4-amino-l-phenyl-3-methyl-5-pyrazolone hydro- chloride with a-bromoisovaleryl bromide in the presence of sodium acetate. F. 31. G. M. [Preparation of Substituted Pyrazolones.1 Hydantoins.VIII. Action of Bromine on Tyrosinehydan- toin. TXEAT B. JOHNSON and CHARLES HOFFMAN (Amer. Chem. J. 1912 47 20-27).-It has been found by Wheeler Hoffman and Johnson (Abstr. 1911 i 923) that tyrosinehydantoin is converted by chlorine into the 3 5-dichloro-derivative and that the latter is hydro- lysed by barium hydroxide with formation of 3 5-dichlorotyrosine. It is now shown that iodine reacts in a similar manner with tyrosine- hydantoin with production of a nearly theoretical yield of 3 :5-di- iodotyrosinshydantoin. Witb bromine however tyrosinehydantoin behaves abnormally giving 3 5-dibromobenzylidenehydantoin as the chief product of the reaction and only a small quantity of 3 5- dibromotyrosinehydantoin. m. p. CO-y H NH-CO' 3 5-Di-iodotyrosinehydantoin OH*C,H,I,-CH,*CH< 235" (decornp.) crystallises in hexagonal plates.3 5-Dibronio- 4 -h yclroxybenzo ylhydantoic acid (3 5-dibmmotyrosine- hydantoic acid) NH,*CO~NH~C1~(C0,H)~CW,.C,H2Br.,.0H m. p.ORGANIC CHEMISTKY. i. 137 19l0 obtained by the action of potassium cyanate on 3 5-dibromo- tyrosine forms rhombohedra1 plates or square prisms and is hydrolysed bv concentrated hvdrochloric acid with formation of 3 5-di6romotvrosine- J .I CO-YH I m. p. 223-225O (decomp.) NHmCO' h yd an toin 0 H C,H Br,* C H2* C H< which crystnllises in prisms. 3 5-~~bronto-4-Ay~~oxybenzylideneh,~dccntoin CO-TH OH*U,H2Br,*CH:C<NH. co m. p. above 295" (decomp.) obtained by condensation of 3 5-dibromct- 4-hydroxy benzaldehyde with by dantoia forms small brownish-yellow needles yields a yellow ccmrnoniurn salt and is reduced by hydriodic acid with production of 3 5-dibromotyrosinehydantoin. 3 5-Dibromo- 4-hydroxybenzylidenehydantoin is also produced by the action of bromine on tgrosinehydantain and on 3 5-dibromotyrosinehydantain. The Reduction of Aromatic Aldazines.THEODOR CURTIUS (J. pr. Chem. 1912 [ii] 85 37-77. Compare Abstr. 1900 i 610). -The paper first gives a summarised account of the results of the investigations published hitherto by different workers on the products obtained by the reduction of benzaldazine (benzylidenehydrazine) and its substituted derivatives under various conditions. [With FRANZ SCHNEIDERS.] -Benzylhydrazine easily undergoes atmospheric oxidation giving a deposit of benzaldehydebenzyl- hydrazone (private communication from August Darapsky).Towards the esters of p- and y-ketonic acids benzylhydrazine behaves like phenylhydrazine. Warmed with benzoylacetic ester i t yields 3-phenyl-l-benxyl-5-pyraxolone a white crystalline powder m. p. 204-205'. Ferric chloride solution is without action on the substance (contrast the 1-benzy l-3 -methyl compound below). When treated in glacial acetic acid solution with sodium nitrite 4-oxirnino- 3-phenyl-1 -benzyl-5-pyrazolone is obtained ; it forms deep red needles m. p. 161-162'. On warming benzylhydrazine with ethyl hvulate l-benzyl-3-mebhyl- 6-p yridaxinone CH2< CH20co>N*CH,Ph CMe=N is obtained ; this crystal- lises from light petroleum in colourless prismatic crystals m. p. 56-57".When cautiously added to ethyl acetoacetate benzylhydrazine yields 1-benzyl-3-m,etl~yE-5-;r?yrcczolone a white crystalline solid m. p. L75-176O b. p. 192-194"/14 mm. ; the intermediate benzylhydr- azone of acetoacetic ester could not be isolated. The product is acid t o litmus and the copper cobalt nickel and silver salts are described ; the hydrochloride forms prismatic crystals m. p. 120'. l-Benzyl-3-methyl-5-pprazolone is exceedingly reactive. Ferric chloride solution in the cold gives a brown coloration and on boiling causes oxidation to the corresponding pyrazole-blue. Heated with phosphorus pentachloride it yields 4-dichloro- 1-benzyl- S-rnethyZ-5-pyrazolone which crystallises in leaves w. p. 59-61O ; the analogous 4-dibromo-compound forms small hard crystals with a tinge E.G.i. 138 ABS1'RACTS OF CHEMICAL PAPERS. of yellow (m. p. 81-83'); these two dibaIogen compounds am unlike the original substance indifferent t o both acid and alkali. 4-p-Tolueneaxo-1 -benxyl-3-methyl-5-pyrazolone obtained by the action of tolifenediazoniurn sulphate forms slender yellow needles m. p. 123-1 24'. 1 -Benx yl-4-6eraz ylidene - 3-methyl-5-pyrazolone ob taiiied by the action of benzaldehyde on benzylrnethylpyrazolone forms rcd crystals m. p. 11 1-1 12'. On heating benzylmethylpy I azulone with phenylhydra zine ammonia is cvolved and 4-bis-1-benzyl- 3-nieth yl-5-pyrazoZone SJ :CMe CMe:N obt'ained which forms white needle crystals melting above 330'; by oxidation with various oxidising agents it passes smoothly into CH,Ph*N-CO >CH*CH<C-J-r(T.CH,Ph' 7:CMe CMd? 1 -hen2 yl-3-meth ylp yraxole- bZue CH,Ph*N-CO >C:C<c()-N.CII,pb ; this crystallises in almost black needles m.p. 142-144' and is decomposed by strong acids and boiling alkali solutions. Careful oxidation of benzylmethylpyrazolone by pot,assium permanganate gives a white acid substance of indefinite m. p. which could not be further purified; the silver salt was obtained as a white precipitate m. p. 185-189' ; excess of permanganate causes oxidation to benzaldebyde and benzoic acid. On treating l-benzyl-3-metbyl-5-pyrazolone in dilute hydrochloric acid solution with sodium nitrite 4-oximino- 1 -benzpl- 3-methy 1-5 - pycczolone is obtained crystallising in yellow needles or prisms m. p 152-152.5'. By reduction with zinc dust in acetic acid solution the oximino-compound gives a solution of 4-amino-1-benxyl- 3-meth yl-5-pyrazoEone which was not isolable and attempts to isolate it as the benzylidene derivative merely caused oxidation to the corresponding rubazonic acid of 1 -benxyl-3-methyk5-pyrazolon~ :CMe CMe:N CH,Ph*N-CO >CH*N:C<Co-&.(7H2ph ; this more conveniently prepared by oxidation of the amino-compound with ferric chloride forms cinnabar-red crystals m.p. 160-161' ; its solutions in alkalis are violet-red. The ammonium salt of 4-oximino-l-benzyl-3-metbyl-5-pyrazolone forms a yellow powder (m. p. 175-176') ; with silver nitrate it yields fhe silver salt as a reddish-brown insoluble amorphous powder which decomposes completely a t 179'. On the other hand silver nitrate decomposes an acetic acid solution of the free oximino-compound nitrous fumes are evolved and finally microscopic needles of the silver salt of 4-nitro-1-benzyl-3-methyl- 5-pgrazolone are obtained which decompose at 245-246".4 - Nitro - 1 - benxy I - 3-naeth yL5-pyrazo Zone can be obtained from the silver salt or by oxidation of the oximino-compounds with nitric acid ; it forms colourless needles m. p. 144-145' (decomp.). The silver salt of t,hs nitro-compound gives with aniline a suhatcmee >(!:N(NHPh),*OAg which separates on couling i n y CR4e CH,Yh* N-UOORGANlC CHEMIS'l'KY. i. 139 yellow capillary crystals ; treatment with solvents removes aniline from the substance regenerating the original silver salt. 1-Benxyl-2 3-dimethyl-5-p~ruxolone (1 -benzylantipyrine) is obtained by methylating l-benzyl-3-metbyl-5-pyrazolone.It forms anhydrous hygroscopic crystals m. p. 84-S6' ; from moist solvente i t crystallises with &H,O and then has m. p. 102-103'. The picrata forms long yellow needles (from hot water.) m. p. 143-145'. 4-0ximino- i -benzyl-2 3-dimethylpyrccxolone is an unstable deep green viscous oil. If benzylantipyrine is oxidised with concentrated nitric acid 4 -nitro- 1- benzyl- 2 3-dimethylpyvazolone is obtained as colourloss prismatic crystals m. p. 161-162O. The physiological action of benzylantipyrine was investigated ; it appears to possess certain advantages over ordinary antipyrine. [With GUSTAV SPRENGER.] - p - Methylbenzylhydrazine (compare Abstr. 1900 i 612) is best prepared by reduction of p-metbyl- benzaldazine by sodium amalgam ; on dilution with water and cooling crystals of the p-methylbenzylhydrazone of p-tolualdehyde separate and can be decomposed by hydrochloric acid.The dihydro- chloride m. p. 150' (decomp.) the sulphate m. p . 178-179' and the oxalate m. p. 180° were obtained. Benzaldehydep-methy2benxylhydrazone forms large transparent tablet.G m. p. 88' ; the diacetyl derivative C6H4Me*CH2*N,HAc forms crystals m. p. 75' (indetinite). The stable nitroso-compound C,H4Me*CH2*N\NO)*NH2 crystallises from water in needles m. p. 78O and when warmed with dilute sulphuric acid yields p-methylbenzylazo- imide C,H,Me*CK,*N b. p. 94'/12 mm. (compare Curtius and Parap- sky Abstr. 1902 i 844). With ethyl acetoacetate p-methylbenzyl- hydrazine gives 1 - p - methylbenzyl-3-methyl-5-pyrazolone (compare Abstr.1900 i 61 2) ; its hydrochloride has m. p. 130'. By treat- ment with nitrous acid the above pyrazolone is converted into yellow 4-oximino-1 -p methyl benzyl-3-methyl-5-p yrazolone m. p. 1 54'. By methyl- ation the pyrazolone is converted into 1 -p-meth?~lbenxyl-2 3-dimethyl- 5pyraxolorie which forms prismatic crystals m. p. 78'. The sub- stance behaves analogously to antipyrine and benzylantipyrine towards nitrous acid and ferric chloride. I t s physiological effect has not yet been investigated. D. F. T. RALPH H. MCKEE (J. pr. C'hem. 1911 [ii] 84 821-826).-By the interaction of etbyl cyanoimidocarbonate and ethyl anthranilate Finger and Zeh (Abstr. 1910 i 382) obtained a compound which t)hey considered to be ethyl cyanoanilide - o-carbox y late. The author 11 as investigated the action of cyanogen bromide on ethyl anthranilate and finds t h a t the resulting compound which undoubtedly has the structure of ethyl cyanoanilide- o-carboxylate is different from Finger and Zeh's compound.The latter substance is considered to be ethvlbenzovleneisocarbamide Ethyl Cyanoanilide-o-carboxylate. .I >C*OEt or ~o*NH>C*@Et and this co--N C,H;N I3 C,H;N [2-ethc xyquinazolone] 1 view is supported by the- formation of the corresponding methyl com- pound by the interaction of methyl cyanoimidocarbonate and ethyl anthranilate. According to Finger and Zeh the products obtainedi. 140 ABSTRACTS OF CHEMICAL PAPERS. from both the methyl and ethyl cyanoimidocarbonates should be identical.Finger and Gunzler had already shown that it is a quinazo- line derivative (Abstr. 1911 i 237). Methyl cyartoimidocarbonate NH:C(CN)*OEt prepared by the action of hydrogen chloride on methyl alcohol and potassium cyanide is a colourless oil b. p. 115"/760 mm. having an odour of mice excre- ment. It reacts with ethyl anthranilate a t 80" in the presence of cuprous chloride yielding 2-methoxyquinaxoZorae I >C*OMe m. p. 231-232" (corr.) which is hydrolysed by hydrochloric acid to 2 4-diketodihydroquinazoline m. p. 3 5 7 O (corr.) ; Griess (Bey. 1869 2 416) gives 344O. Methyl cyanoanilide-o-carboxgiate CN*NH-C6H;C02Me obtained by the action of cyanogen bromide on methyl anthranilate in ethereal solution crystallises in needles m. p. 105' (corr.).When heated a t looo it polymerises t o tri-o-carbomethoxyphenylmelamine c27H240~N6 which has M. p. about 1 6 0 O . Ethyl cyanoanilide-o-carboxylate prepared from cyanogen bromide and ethyl anthranilate has m. p. 93-94O and polymerises to tri-o- carbethoxyphenylrnelanzine C3,,H3006N6 m. p. 1 90° with previous sintering. Methyl anthranilate forms a picrude N H2*CGH,*C02Me,C,H,07N3 crystallising in deep yellow microscopic needles m. p. 106O (corr.) ; the picrate of ethyl anthranilate has m. p. 1 16c (corr.). Preparation of Derivatives of Indophenols. LEOPOLD CASSELLA & Co. (D.R.-P. 23885'7). -1ndophenols prepared from carbazolecarb- oxylic acids and nitrosophenols co2R NH have previously been described ; .A/ \A - these substances on reduction I t 1 I NH-/ \OH furnish leuco-derivatives having \/- \/- \-/ the annexed general constitution which when slowly dropped into a hot solution of sodium polysulphide yield dark blue sulphur cotton dyes which are extremely fast to light washing or chlorine.Preparation of Anthraquinone Derivatives. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R.-P. 235981. Compare following abstract),- When acyl o-diaminoanthraquinones are treated with dehydrating reagents the following action takes place OO--N CGH4*NH F. B. F. M. G. M. = A<EC>CR + H,O where A is an anthraquinone residue (substituted or otherwise) R hydrogen alkyI or aryl and R' alkyl aryl or an ethoxy-group. 1 2-PhenyZanthraquirtoneiminnzoEe prepared from benzoyl-1 2- diaminoanthraquinone and 4-amino- 1 2 - phenylanthraquinonehin- azole obtained from benzoyl-1 2 4-triaminoanthraquinone by the action of sulphuric acid at 150° form yellow crystals and glistening metal1 ic need 1 es respectivoly.1 2-HydroxyanthraquinoneiminaxoZe (I) prepared by the action of carbonyl chloride on 1 2-diaminoanthraquinone crystallises from quinoline in needles.ORGANIC CEEMISTRY. i. 141 4 - Hpdrolcy- 2 - ethoxy- 1 -p-tol~lanthl.aquinolzeimincczole (II) yellow needles was obtained by the fusion (at 100') of p-toluidine with dinitro-P-amiooanthrnquinoneurethane ; it yields a sdphonic acid when heated with fuming sulphuric acid. 1 2-MsthyZanth~aquinn~~m~~uzoZe yellow needles obtained from 1 2-diaminoarithraquinone and acetic anhydride and the compound from the same base and formic acid are alco mentioned in the or i g i nal.NE-C*OH N(C,Ht )-C* OEt /VCO\/\-N I /\/ CO \/\--+ I I t I / I (OH \/\c(/\/ Preparation of Anthraquinone Derivatives. FARBENFABRIKEN VORM. FRIEDR. BAYER & Co. (D.R-P. 238982).-Condensation products of benzaldehyde and P-arninoanthraquinones have been described by Kaufler (Abstr. 1904 i 207) ; this condensation is now found to take place readily with o-diaminoanthraquinones and either aliphatic or aromatic aldehydes. The compounds prepared from 1 2 - diaminoanthraquinone and 1 2 4-triamimanthraquinone respectively with benzaldehyde are identical with those obtained from the benzoyl derivatives of these compounds when heated with sulphuric acid (compare preceding abstract) whilst 1 2diaminoanthraquinone with para-acetaldehyde in concentrated aulphuric acid at &lO0 yields the 1 2-methylanthra- qninoneiminazole also previously described.F. 31. G. M. [Preparation of Anthraquinoneacridone Derivatives.] 238978).-Anthraquinoneacridone can be conveniently nitrated with nitro-sulphuric acid at 0 - 5 O ; the nitrated product is yellow and does not fuse at 300'; when reduced with sodium sulphide at loOo i t furnishes aminoanthraquinoneacridone (not melted at 300'). Benzoylaminoanth4.u~u~noneacridorte separates in crystalline form when a nitrobenzene solution of aminoanthraquinoneacridone is boiled with benzoyl chloride ; the acetyl compound has also been prepared. The second patent states that the foregoing benzoylaminoanthra- quinoneacridone can be obtained by boiling a nitrobenzene solution of bromoanthraquinoneacridone with benzamide in the presence of copper and sodium carbonate during t wenty-four hours.AKTIEN-GESELLSCHAFT FUR ANrLIN-FABRIKATION (D.R.-P. 2389'77 and F. M. G. M. Nature of the Indanthren Fusion of 2-Aminoanthra- quinone 2-Hydroxylamino- and 2 2'-Azoxyanthraquinone. ROLAND SCHOLL and FRITZ EBERLE (Monactsh. 19 11 32 1035-1 042). -2-Hydroxylaminoanthraquinone obtained in small quantity by reduction of 2-nitroanthraquinone could not be converted into indanthren by fusion with an alkali hydroxide. I n alkaline solution hydroxy l r u n i n o a n t ~ a q ~ i ~ o n e ia very readily oxidised by atmospherici. 142 ABSTRACTS OF CHEMICAL PAPERS. oxygen to 2 2'-azoxyanthraquinone. This compound could not be reduced to the corresponding hydrazoanthraquinone 2-aminoan thra- quinone always resulting.The formation of indanthren from 2-aminoanthrnquinone is explained on the assumption that on fusion with an alkali hydroxide 2-aminodihydro-1 2'-dianthraquinonylamine is formed and that this loses hydrogen forming dihydroindanthren NH,*C,,H,( OH)2*NH*4,H102 C,,H,(0H),<~~>C14B~02' ~ydroxyla~~inoanthraquinone C,,H70,*N H*OH was obtained as an It dissolves in 2 2'-Azox~unthraquinon e ON,( C,H,<gg>C,H,)2 crys t allises in small light brown prisms and prismatic plates m. p. 342.5'. The solution in concentrated sulphuric acid is red. A solution in hot acetone gives a very characteristic cornflower-blue coloration on the addition of a few drops of sodium hydroxide. orange-red solid sintering at 140° m.p. 158-160". dilute sodium hjdroxide with an intense green coloration. E. F. A. [Preparation of Dimethylindanthren.] BADISCHE A NILIN & SODA- FA BRI K (D . R. -P. 2 3 89 7 9) .-3 3'- Dimet h ylind an thren a bluish- grey crystalline powder can be prepared by boiling an acetic acid solution of 2-amino-3-met hylanthraquinone (1 part) with lead peroxide (3 parts) during three hours or by boiling a naphthalene solution of 1 -bromo-2-amino-3-methylanthraquinone with copper oxide and anbydrous sodium acetate during four to five hours. A similar conyound can be obtained from Z-amino-6(7)-methylanthraquinone. F. M. G. M. Action of Semicarbazide on Hydroxamic Acids. HANS RUPE and F. FIEDLER (J. pr. Chem. 1911 [ii] 84 809-816).-It has been shown previously (Rupe and Kessler Abstr. 1910 i 93) that the action of semicarbazide hydrochloride on aliphatic oximino- ketones leads t o the replacement of the oximino-group by the semi- carbazide residue :N*NK*CO*NH,.A similar elimination of the oximino-group is found to take place with hydroxarnic acids resulting in the formation of semicarbazidts. The reaction is however not a general one. The replacement occurs readily with benzhydroxamic and acethydroxamic acids and with difficulty in the case of phenyl- acethydroxamic acid whilst with salicylhydroxamic and cinnam- hydroxamic acids no reaction takes place. Benzoylsemicarbazide obtained by heating benzhydroxamic acid with semicarbazide hydrochloride in aqueous solution has m. p. 215O and may also be prepared by the action of ethyl benzoate or benzoic anhydride on semicnrbazide.The high m. p. (225') given by Widmann and Cleve (Abstr. 1898 i 335) is due to the presence of hydrazo- dicai~boxylttrriide. The acetyl derivative C16Hl103N3 forms lustrous white leaflets m. p. 174O and is instantly hydrolysed by cold aqueous sodium bydroxide. . Cinnamoylsemicarbaxide C,,H,,O,N prepared by heating cinnamicORGANIC CHEMISTRY. i. 143 anhydride with semicar bazide crystallises in needles ; t be clcelpl derivative forms slender white needles LU. p. 177-178O. ~ ' ~ ~ e n ? / Z ~ 6 c e t ? / Z u e n ~ i c a r ~ u ~ ~ ~ ~ CYH1102N3 o btilined from the acid chloride or anhydride in a similar manner or by the interaction of phenyltiydroxamic acid aud semicarbuzide hydrochloride in aqueous solution crystallises in slender needles m. p.167-168'. Azines and Quinonediazides of the A n t h r a q u i n o n e Series. ROLAND SCHOLL FRITZ EBEHLE and M 7 ~ ~ ~ ~ ~ TRITSCR (Monatsh. 19 11 32 1043-1056). -( 1) Azines from Triuminoanthrccquinone.-On con- densiug 1 2 3-trinminoanthraquinone with o-dicarbonyl compounds azines of entirely different nature are to be expected according as the pytwine nucleus becomes attached in the angular 1 %position or the linear 2 3-position. The linear derivatives should possess the same properties as the azines from 2 3-diaminoanthraquinone (Scholl and Kacer Abstr. 1905 i 88) characterihed by their giving brown reduction products with alkaline sodium hyposulphite (Scholl and Edlbacher Abstr. 1911 i 756). Oxalic acid benz 1 1 2-naphthaquinone phenanthraquinone and isatin yield azines with triaminoanthraquiuone which all form insoluble brown products in alkaline sodium hyposulphite.The azines are accordingly regarded as linear (for nomenclature see Scholl Abstr. 1911 i 677). 1 2 3-Triaminoanthraquinone has m. p. 325" (decornp.). Bihydmxy-2 3-pyrazino-1-arninounti~ruguinone (annexed formula) produced on coudensation with oxalic acid sublimes in lustrous dark brown needles. /\/\/\/\OH It is not melted at 400'; in boiling with 1 I I 1 ]OH dilute sodium hydroxide it dissolves giving '\/\/\/\/ a red solution from which a red sodium salt separates on cooling. C,H4<CO>C,H(NH,)<N :&h' F. B. CO NK,N GO Diphen$-2 3-pyrazino-l -amirLoantl~~waquinono co KCPh prepared by condensation of triaminoanthraquinone and benzil crystallises in tiny red or brownish-red needles m.p. 241'; it sublimes without decomposition and gives a red coloration with concentrated sulphuric acid. 2 3( 1' 2'-)-Naphthanino-l(or 4-)-arninoanthraquinone is obtained as a dark brown amorphous compound m. p 266 -267O. 2 3( 9' IO'-)-Pllenanthruxiro- 1 -nmiroalnthrapuinone crystallises in well formed reddish-brown lustrous needles m. p. 361". 2 3-lndazino-1 (or 4-)-anzinoanthraquinone forms a dark brawn indefinitely crystalline powder m. p. above 400'. When heated with sodium hyposulphite and sodium hydroxide it forms a reddish-brown vat which dyes cotton yarn light brown. (2) QuiNoneuxides of the Anthraquinone Series. -The quinonediazides of the anthraquinone series in contrast to those of the benzene series cannot be coupled with naphthol or naphthylamine to azo- dyes.With resorcinol they couple only very slowly on prolonged heating.i. 144 ABSTRACTS OF CHEMICAL PAPERS. 2 6-nibror~~oant7~rnquinrme-l 5-bisdiazonium sulphate (I) produced on diazotisiug dibromodiaminoanthrayuinone separates in yellowish- red crystals m. p. 185-186O. When boiled with dilute sulphuric acid it is converted into ~6nth~apuinone-2 1 6 5-bisquinonediazide (11). CO N2*S04H co N2 Br CO N /\/\/\Br / \ / \ A 0 /\A& I l l I I I I ?/\/\/ OH CO Br Brl I I I \/\/\/ S04H-N2 CO (1.1 (11.) (111.) This crystallises in well-formed metallic-green lustrous crystals which explode at 156'. 4 6 8-~rib.rorno-5-hydroxyantl~raquinonc-2 1-qwinonediazide ( I I I ) prepared by diazotising 2 4 6 8-tetrabromo-1 5-diaminoanthra- quinone and boiling the crude diazo-product was obtained in a brown crystalline form from acetone which blackens and sinters above 360".E. F. A. [Preparation of ~-Azimino-compounds.] CHEMISCHE FABRPK GRIESHEIM-ELEKTRON (D.R.-P. 238353). When the azo-compounds obtained by the combination of /3 - diazoanthraquinones with /\/\'\ N' '\/\/\ p - naphthylamine are oxidised I I I- "-I I they yield +-azimino-compounds \/\/\/ \/\/ such as up-nayl~tl~ylene-~C/-azimino- ( a n n e x e d CO formula). The sulphonic derivatives are soluble in water and form valuable cotton dyes. co /3 - cbnthraquinonyl F. M. G. 31. Action of Hydrazoic Acid on Cyanogen. Formation of Cyanotetrazole. E.OLIVERI-MANDALA and T. PASSALACQUA (Gaxxetta 191 1 41 ii 430-435. Compare Oliveri-Mandal& Abstr. 1910 i 343; 1911 i 337 ; Oliveri-Mandalh and Coppola Abstr. 1910 i 593; Oliveri-Mandala and Alagna Abstr. 1911 i 243; Dimroth and Fester Abatr. 1910 i 645).-When cyanogen is passed in to a 40% aqueous solution of azoirnide cyanotetrazole [tetrazo&-5- ca~boxylonitrile] C'2HN5 is produced. The substance becomes slightly red at 70' and melts at 9 9 O forming a reddish-brown liquid. It yields ammonia quantitatively when boiled with potassium hydroxide solution. The silver salt C,N,Ag and the barium salt were prepared. When the silver salt of cyanotetrazole is treated with ethyl iodide 1 -ethyltetrazole- 5-carboxyllonitrib y(CN)*NEt>N is obtained; it is a colourless liquid b.p. 127"/46 mm. On distillation a t ordinary pressure it explodes at about 200". 1-E'thyltetraxoZe-6-carboxyZamide C,H70N is prepared by heating at 50-60" an alkaline solution of 1-ethyltetrszole-5-carboxy lonitrile with hydrogen peroxide solution ; (C2N5)2Ba,S&H20 N--NORGANIC CHEMISTRY. i. 145 i t crystallises in minute lustrous scales m. p. 125-126". I-EthpZ- tetrazole-5-cccrboxyl~c acid C,H,O,N is obtained by heating 1 -ethyl- tetrazole-5-carboxylonitrile with methyl-alcoholic potassium hydroxide and neutralising the potassium salt with sulphuric acid. The acid crystallises in acicular prisms m. p. 124-125'. In addition to the pohsium salt C,H,O,N,K the silver salt C,H,O,N,Ag was pre- pared. When 1 -ethyltetrazole-5-carboxylic acid is kept at 130-140' it loses carbon dioxide and 1-ethyltetrazole (identified as platini- chloride) is obtained identical with the N-ethyltetrazole formerly described.R. V S. Identity of the Guanine Pentoside from Molasses with Vernine. ERNST SCHULZE and GEORG TRIER (Zeitsch. physiol. Chem. 1912 76 145-147).-Vernine (guanine-d-ribose) for which the com- position C,,H,,O5N,,2H,O was recognised by Schulze and Castoro (Abstr. 1904 11 506) is identical with the guanosine obtained by Levene and Jacobs from nucleic acid and with the guaninepentoside isolated by Andrlik (Abstr. 1911 i 397) from molasses. I n 1.5% sulphuric acid it has [a]2,0 - 8.4". JS. F. A. The Fastness t o L i g h t of Hydroxyazo-compounds. Some Derivatives of a-Methoxy naphthalenes. N. WOROSHZOFF (ZeitscA.Farb.-Ind. 1911 10 169-173).-1t is found that the alkylation of the hydroxy-group in hy droxyazo-compounds increases the fastness to light of the colouring matters obtained therefrom and that methyl- ation can be conveniently carried out by shaking an alkaline solution of the compound with methyl sulphate. Sodium 1 - me thox y naphthalene- 4- su lphona te prepared by shaking a-naphthol-4-sulphonic acid with methyl sulphate in the presence of sodium hydroxide separates in glistening leaflets. 4-Xitro-l-rnethoxynaphthaZene yellow needles m. p. 8l0 is obtained by slowly adding an intimate mixture of the foregoing acid (10 parts) and anhydrous sodium carbonate (0.6 part) in small portions to a cooled solution of 1.5 grams of carbamide in 20 C.C. of nitric acid (D 1.4) ; on reduction with stannous chloride and hydrochloric acid it furnishes 4-msthoxy-a-naphthyZamine hydrochloride in colourless crystals ; the free bme is a dark oil ; its ucetyl derivative has m.p. 180-181". F. M. G. M. Salicylic Acid Azo-dyes. EUGEN~ GRANDMOUGIN (Ber. 191 1,44 3756).-8 claim for priority against Bulow (Abstr. 1911 i 338). D. F. T. Decomposition of Azines by Heat. I. and 11. PAUL PASCAL and LEON NOXMAND (Bull. Xoc. chim. 1911 [iv] 9 1029-1037 1059-1068).-Curtius and Jay (Abstr. 1889 393) showed that bnzaldazine decomposes when heated forming stilbene and Bouveault obtained di-ju-methylstilbene in a similar way from tolualdazine (Abstr. 1897 i 347 530) but failed t o generalise the reaction. In the first OF these gapers the authors show that in general the aromatic aldazines melt with very slight decomposition but when the tempera-i.146 ABSTRACTS OF CHEMICAL PAPERS. ture is raised above the melting point evolation of gizs commences and incrcastx with rise of temperature tho principal reaction being the production of nitrogen and the stilbene corresponding with the aldazine used. At the higher temperatures some ammonia and hydrogen are formed with as a solid product the corresponding phenanthrene due to loss of H atoms a t positions contiguous to the azine side-chain. The rate of decomposition was determined by measuring the gas evolved. By plotting temperatures as abscissse and volumes of ( I ) nitrogen and (2) ammonia disengaged as ordinates tw curves were obtained cutting one another on the temperature axis and thus giving the temperature of decompositioti which is sometimes 50" below that actually observed subjectively. \Vhen the evolution of gas ceases the contents of the tubes were distilled and give as a rule (1) a mixture of aldazine and t h e stilbene ; (2) green oils containing the phenanthrene ; (3) red oils and (4) a resinous or coke-like residue.I n the case of the '' red oils " from bonzaldazine the chief constituent is a substance m. p. 261° b. p. 460' crystallising in long needles and giving a yellow picrate m. p. 1 9 8 O ; it may heidentical with the product C,,K,,N obtained by Curtius from benzoin-hydrazine. The amounts of t h i s substance and its hornologues produced increase with rise in the molecular weight of the alduzine employed.Benzaldazine CHPh:N,:CHPh begins to decompose a t 275O furnish- ing stilbene phenanthrene and the product C,,H23N already referred to. Tolualdazine C,H,Me:N2:C6H,Me begins to decompose a t 3 14O forming di-p-methylstilbene ni. p. 18 1'. C H,Pr@*CH N, CH C6Y4Pr@ m. p. 113*6" forms yellow leaflets and begins to decompose a t 281° yielding cli-p-isopropylstilbene C,H4PrP*CH:CH*C6H4Pr@ m. p. 1 2 9 O which separates from alcohol in colourless scales and yields a dibromide m. p. 186-187O (approx. decomp.) crystallising in small brilliant colourless spangles. p-~ethyZbe?Lxaldaxine CKPh:K,:CH*C,H,Me m. p. 1 12' forms pale yellow crystals from alcohol and when heated gives p-methylstil bene m. p. 119.6'. Aldazines in which the benzene nucleus is replaced by naphthalene decompose only at high temperatures and the unsaturated product is difficult to free from tarry by-products.Furfuraldazine C40H4*CH:N2:CH*C,0H4 is decomposed by heat yielding furfuryl- stilbene m. p. 97.4". The aliphatic azines of low molecular weight distil easily and decompose only at a red heat The higher terms decompose slowly on distillation forming a fluorescent liquid with an odour of petroleum and of pyridine bases ; there is no evolution of nitrogen or ammonia. Di-p-cl~lorobenxnk~axine m. p. 2 1 lo forms yellow spangles from alcohol or boiling benzene ; it begins to decompose at 284' furnishing di-p-chlorostilbene m. p. 153*8' in silver-grey spangles which yields a dibrornide m. p. 195-197". Di-p-iminobenzaldaxine m. p. %5O obtained by the interaction of p-aminobenzaldehyde with hydrazine sulphate is a yellow powder ; it begins to decompose at 307' giving off a little nitrogen and much ammonia so that i t was impossible to isolate di-p-aminostilbene from the accompauying tarry by-products.Cuminaldazine,ORGANIC CHEMISTRY. i. 147 Di-o-methoxp benzaldazine begins to decompose at 270' and yields 80% of di-o-methoxystilbene m. p. 136' which separates from alcohol in colourless crystals and gives a dibromide m. p.. 190'; the corre- sponding meta-compound furnishes di-m-methoxystilbene m. p. 97*5' the dibromide of which m. p. 183*5-184.5' is colourless and crystal- line. Di-p-methoxybenzaldazine begins to decompose at 289' and yields di-p-methoxystilbene m. p. 213'. Bi-o-ethoxybenzaldazine m. p. 131.6" forms yellow crystals and commences t o decompose at 287' giving di-o-ethoxylstilbene m.p. 87*5' colourless crystals the dibromzde of which m. p. 218-219' forms pale yellow crystals. ~i-p-ethox?~benzcddazine m. p. 172*3' crystallises in pale yellow lamellz3 and begins t o decompose at 308' furnishing di-p-ethoxystilbene I ~ I p.' 208". Di-o-benxyZoxybenxaZdazine m. p. 157*7' yellow plates gives di- 0- benzyloxystilbene m. p. l l 7*6" in small brilliant colourless spangles whilst the corresponding. para-compound m. p. 209*3" pale yellow leaflets decomposes less easily forming a bulky '' coke " froni which no stilbene derivative has yet been isolated. T A. H. Decomposition of Azines by Heat. 111. PAUL PASCAL and L d o ~ NORMAND (Bull. SOC. chirn. 1912 [iv] 11 21-25. Compare preceding abstract).-The methoxynaphthaldaxine gives only a small yield of dimethoxynaphthylethylene at 362'.Vercctraldaxine gives but little 3 4 3' 4'-tetramethoxystilbene whilst the azine from piperon- aldehyde N,(:CH*C,H,:O,:CH,) does not yield a corresponding stilbene. The main conclusions arrived a t from results described in this and the preceding abstracts are as follows. Aromatic azines decompose at about 300" evolving nitrogen and ammonia and giving stilbene derivatives the yields being increased if the position ortho to the group *CH:N, is filled by any radicle. In the same homologous series the yield diminishes on ascending the series. If a substituent group such as amino- in the nucleus of the azine possesses a residual affinity the yield of stillnene compound is considerably lowered. Esterification in the case of several hydroxy- groups attached to each aromatic nucleus does not prevent decom- yosi tion. A study of the physical constants of the azines and stilbenes shows t h a t the iritroduction of one or more atoms of oxygen into the molecule produces a rise in the melting point. The reverse is the case if a hydroxyl group is replaced by a methoxy- or ethoxy-group. Finally the more symmetrical the molecule the higher is the melting point. W. G. The Existence of Sulphur Fixed as Sulphite in Wool. H. STRUNK and HANS PRIESS (Zeitsch. physiol. Chem. 1912 76 136-144).-Raikow (Abstr. 1905 i 725; 1907 i 666; compare Grandmougin Chem. Zeit. 1907 31 174) has stated that wool when kept for some time in contact with large quantities of concentrated phosphoric acid liberates small quantities of sulphurous acid. This is confirmed but the amount 0.0064 gram of sulphur dioxide from 300 grams of wool is too small for it to be assumed that part of thei. 148 ABSTRACTS OF CHEMICAL PAPERS. sulphur in the keratin molecule is united with oxygen as sulphite. Dry wool has a very pronounced affinity for hydrogen sulphide ; this is sufficient to explain the variations experienced in the amount of sulphur in wool. The hydrogen sulphide fixed by the wool is easily oxidised to sulphurous and sulphuric acids and it is probable that n small quantity of sulphurous acid may arise in the wool of the living animal in such manner. The Separation of Rennet and Pepsin. W. E. BURGE (Amer. J. Ph,ysioZ. 1912 29 330-334).-The passage of a direct current of 10 milliamperes for twenty-four hours through a solution containing both enzymes causes a complete destruction of peptic activity but leaves the rennet apparently unchanged. Activation of Sucrase [lnvertase] by Different Acids. GABRIEL BERTRAND M. KOSENBLATT and (Mme.) M. ROSENBLATT (Compt. rend. 1912,154,1515-1518).-The effect of the more commori organic and inorganic acids on the diastatic activity of sucrase has been determined under conditions more precisely defined than those of other observers. I n each case the optimum concentration of acid was determined. The results which are displayed in tabular form shorn that generally speaking the order of efficiency in which the acids stand as activating agents is the same as Ostwald’s order for their activity as catalysts in hydrolysis. Hydrochloric and nitric acids however are exceptions to the rule being less effective as activators than a s Action of Phospbatese. HANS EULER and STXTEN KULLBERG (Zeitsch. physiol. Chem. 1912 ’76 241. Compare Abstr. 1911 i 1051 ; this vol. i 61).-Reference is made to von Lebedeff’s work which does not agree with that of the authors; perhaps different kinds of yeast will explain the discrepancy ; no further experimental work is adduced. W. D. H. 4-Amino-3-hgdroxyphenylarsinic Acid and its Products of Reduction. LUDWIG BENDA (Ber. 19 11,44. 3578-3582. Compare this vol. i 61 -64) .-3-Nitro-4-aminophenylarsinic acid can be diazotised in the usual way yielding a solution of a diazonium salt which loses the *AsO(OH) group when boiled with dilute sulphuric acid. However by treatment with sodium acetate t o destroy the mineral acid the solution of the diazonium salt exchanges its nitro- for a hydroxyl group ; the solution of the resulting diazonium salt can be coupled with alkaline P-naphthol to form a red azo-dye which is reduced by sodium hyposulphite or by sodium hydroxide and aluminium yielding 1 -amino-2-napht hol and 4-amino-3 -h ydroxyphen ylarsinic acid NH,*C,H,( OH)*AsO<O H)2 the sodium salt C,H70,NAsNa,5H20 and silver salt of which are described. Under suitable conditions the red azo-dye is reduced by sodium hyposulphite yielding 4 4’ - diarnino - 3 3‘ - dihydroxyarsenobenxene As2[C,H,(NH,)*OH] the hydrochloride and sulphate of which are described c. s E. F. A. W. D. H. catalysts. w. 0. w.