77 Organic Chemistry. Density of Methane; Atomic Weight of Carbon. GEOBGES BAUME and F. LOUIS PERROT (Compt. rend. 1909 148 39-42).-The methane was prepared by the action of water on magnesium methyl iodide and after being passed through different reagents and then dried was purified by liquefaction and fractional distillation. The density determinations were carried out in tbree bulbs of different size in the usual way. As a mean of nine moderately concordant experiments the weight of a litre of the gas a t 0°/760 mm. is 0.7168 gram. From the results the atomic weight of carbon is calculated by the physico-chemical methods of Leduc D. Berthelot and Guye respectively; the mean value is C=12*004 (H=1*0077) in good agreement with the accepted value. G. S. Hydrocarbons C,H ; New Synthesis of Tetramethyl- methane [Dimethylpropane].ENOS FERRABIO and F. FAGETTI (Gazzetta 1908 38 ii 630-634).-Dimethylpropane may be prepared by the action of (1) methyl magnesium iodide on tert.-butyl iodide (15-20% yield) ; (2) tert.-butyl magnesium iodide on methyl iodide (15-20% yield) ; (3) methyl sulphate on tert.-butyl magnesium iodide (75% yield). The &t.-butyl alcohol required in the last of these syntheses may be obtained in 75% yield by the action of carbon dioxide on methyl magnesium iodide (compare Grignard Abstr. 1904 i 213). T. H. P. Synthesis of Ethylene from Carbon Monoxide and HydrQgen by Gontact with Nickel and Palladium. E. I. ORLOFF (J. Rust?. Phys. Chem. soc. 1908 40 1588-1590).-When a mixture of approximately equal volumes of carbon monoxide and hydrogen is passed over pieces of coke impregnated with reduced nickel and palladium and heated a t 95-lOO0 no formaldehyde is produced the gaseous mixture obtained consisting of carbon monoxide hydrogen and ethylene with a small proportion of air.In one experiment the gases contained 6.6% of ethylene and in another 8.3%. The first part of the reaction piobably consists in the reduction of the carbon monoxids to water and the methylene group CO + 2 8 = H,O + CH t g o methylene groups then combining to form ethylene. Attempts to absorb the ethylene in the mixture of gases formed by means of bromine or bromine water met with failure which the author accounts for by the great dilution of the ethylene with other gases. A concentrated solution of potassium mercuric iodide HgI,,BKI in sodium hydroxide constitutes a far more certain absorbent of ethylene than either bromine or bromine water.The formation of ethylene inbtead of methane which would bw espected from the results of Sabatier and Senderens and of Ipatieff is aot in accmd with the thermal chaagoe occurring during these VOL. XCVI. i. 918 ABSTRACTS OF CHEMICAL PAPBRS. reactions which would indicate the formation of methane rather than ethylene. When a mixture of carbon dioxide and hydpogm is passed over coke impregnated with nickel and palladium and heated at 95-looo the resultant gases do not contain either formaldehyde ethylene or methane. A t higher temperatures also no formation of formaldehyde is observable carbon dioxide and hydrogen yielding ethylene and methane ; this observation is not in accord with those of other investigators who state that only methane is formed by the reduction of carbon dioxide The carbon dioxide first undergoes rediiction in the presence of heated coke to carbon monoxide which is then reduced to ethylene and methane.T. H. I?. Preparation of Nitromethane. WILIXELM STEINKOPP (Ber. 1908 41 4457-4458).-A modification of the original Preibisch method (this Journ. 1874 462) which not only gives a much better yield of nitromethane but also avoids the evolution of hydrogen cyanide. A solution containing potassium chloroacetate ( = 200 grams of acid) and 300 grams of potassium nitrite in one litre of water is heated in a flask fitted t o a condenser until carbon dioxide begins to be evolved.Tne reaction then proceeds and the nitromethane distils in the steam. ’She yield is 49% of the theoretical. W. R. Ethylisoamylcarbinol and Methylisohexylcarbinol. ARMAND Compare Henry BUELENS (Bull. Acad. ?soy. Belg. 1908 921-929. Abstr. 1906 i 723).-E’tl~~ZisoanzyZca~binoZ CHMe2*CH2*CH2*CHEt*OH m. p. 61° b. p. 165-166” D 0.8084 n 1.42011 obtained by the action of magnesium isoamyl bromide on propaldehyde is IL liquid of pleasant odour and burning taste. The acetyl derirative ‘b. p. 184-185O D2O 0.8554 n 1.41602 is a colourless mobile pleasant-smelling liquid. Methylisohexylcarbinol CHMe,-CH,-CH,*CH2*CH~leeOH b. p. 171--172°/760 mm. D20 0-8128 n 1-42381 obtained by the interaction of magnesium isohexyl bromide with acetaldehyde is a liquid of agree- able odour and sharp taste.The ucetute b. p. 187-188O/768 mm. D20 0.8494 n 1-41 37 is a colourless mobile pleasant-smelling liquid. Methyl isol~xpl ketone b. p. 166’/770 mm. D20 0*8151 obtained by oxidising the alcohol with chromic acid is a colourless liquid and forms a sodium bisulphite compound. The methyl ethep CHRle,* CH2* CH2-CH,* CHMe* OMe b. p. 149-1 5 Oo/76O mm. D20 0-7945 obtained by the action of chloroethyl methyl ether MeCHCl-0 *Me on magno~iam isohexyl bromide i s a liquid of agreeable odour. /3-Jlethyll~eptaoze CHMe,*[CH,],*CH b. p. 1 ld0/760 mm. D2O 0.7134 m z 1.39807 was obtained by the action of metallic sodium on a mixture of propyl iodide and isoamyl iodide tho normal hexaiie and the decane simultaneously formed being eliminated by fractional distillation.It is a colourless very mobile pleasant-smelling liquid,ORGANIC CHEMISTRY. 79 The hohexgl alcohol b. p. 147-14S0 used in the research mas prepared by the action of trioxyrnethylene on magnesium isoamyl bromide in presence of zinc chloride. isoHezyZ bromide b.. p 146-147*/760 mm. D20 1.1683 n 1.44897 obtained by saturating the alcohol with hydrogen bromide and warming in a closed vessel is a colourlesq mobile liquid of slight not unpleasant odour. T. A. H. Direct Dehydration of Certain Tertiary Alcohols. LOUIS HENRY (Compt. rend. 1908 147 1260-1 262).-1n the production of fly-dimethyl-A"- bu tylene and Fi-dirne t h yl-As- but ylene by heating dimethyli8opropylcarbinol with acetic anhydride containing a small amount of sulphuric acid (Abstr.1907 i 374) it was originally considered that since only a very small proportion of sulphuric acid was present the acetic -anhydride acted as the dehydrating agent. Delacre however has shown (Abstr. 1907 i 459) that dimethyliso- propylcarbinol is transformed into its acetate by the action of acetic anhydride. Thus the sulphuric acid must be the active agent in the reaction which seems to be a curious instance of catalyeis. That the acetic anhjdride takes part in the reaction however is shown by the fact t h a t it is only iu the presence of a few drops of sulphuric acid that the decomposition of the acetate already formed takes place more easily and more ispidly than that of the alcohol as such. Contrary to the behaviour of dimethylisopropylcarbinol cyclopropyl- methylcarbinol (Abstr.1908 i 881) when heated with acetio anbydride containing a little sulphuric acid does not undergo dehydration but is completely transformed into its acetate. The con- clusion is drawn that the existence of a closed chain in the molecule confers stability on the alcohol. E. H. ~-DirnethylaJlylcarbinol. MAURICE VAN AERDE (Bull B a d . roy. Belg. 1908 929-939).-~-Chloro-/3-methyl-A~-amylene CUe, CH*CH,*CH,CI (Henry Abstr. 1907 i loti) yields a liquid dibromide D20 1.71 and is converted into the corresponding acetate (the dibronaide of this. has D20 1.551) by heating in c l o d tubes with potassium acetate and acetic acid and this on treatment with potassium carbonate yields yy-d.in~st?~:yZaZZylcarbinoZ CMe,:CH*CH,*CH,*OH b. p. 157-15S0/771 mm.D20 0.8615 n 1.44116 a colourless liquid with a slight terebinthinous odour and sharp acrid taste. On re-conversion into the acetate D20 0.9183 nD 1.4308 by the action of acetic anhydride the product obtained boiled a t 165-175O which would seem to indicate that the alcohol and chloride referred to above are mixtures in spite of their constant boiling points. Having regard to its method of foruation the hupposed chloride might consist of the two substances CMe,:CH*CH,*CH,Cl and C H 2:CMe*CH,.C d $C1 but it does not yield acetoiie on oxidation with chromic acid as t h e second suggested constituent should do. On adding acetic anhydride to the mixture resulting from the g z80 ABSTRACTS OF CHEMICAL PAPERS. action of magnesium methyl bromide on ethyl y-chlorobutyrate (Abstr.1907 i 106) adding water and extracting with ether a mixture of r-chloro-P-methylpentane-P-ol OH*CMe,*CH,*CH,.CH,Cl (Zoc. cit.) and dimethyltetramethylene oxide CMe,.y= wa8 o<CH,-CH,' Y * obtained in place of the expected chloroncetin T.A. H. Physico-chemical Properties of Ethylene Qlycol and of its Solutions in Water. F. SCHWERS (Bull. Acad. rog. Belg. 1908 814-854).-The author has determined the densities of ethylene glycol and of its mixtures with water at temperatures from 0-looo the specific heats of ethylene glycol and its mixtures with water and the heats developed when it is mixed with water in various proportions. From the results obtained which are given both in tabular and in graphic form the following conclusions are drawn (1) Ethylene glycol has D 1.12570 and its expansion by heat can be represented by the expression (2) A contraction in volume accompanied by a development of heat occurs when ethylene glycol is mixed with water in any proportion.At Oo the maximum contraction (1.545% of the initial volume) is observed with a concentration of 58% of glycol and 42% of water corresponding with the hydrate 2C,H,(OH)2,5H,0. The contraction decreases generally with increase in temperature but between 50' and 70° a slackening in the rate of this decrease is observed for all concentrations and is indicated by a flattening of the curves between these temperatures. This phenomenon which seems to be connected with the boiling points of the components of the mixture is also exhibited by mixtures of glycerol and water between 70° and 90°.Mixtures of the monohydric alcohols with water of certain concentra- tions undergo the same contraction a t all temperatures but a similar behaviour is not observed with aqueous solutions of the diols and triols. (3) The specific heat of ethylene glycol is 0.563 at 20' and 0.591 at 3.i0 whilst that of its aqueous solutions is always greater than that calculated additively from the specific heats of the glycol and of water (=l). (4) The heat developed by mixing glycol with water reaches a maximum for the concentration of 37% of glycol and 63% of water which corresponds with the hydrate C1H,(OH),,6H,0. It decreases with rise in temperature but the diminution is relatively small so that it is still positive a t the boiling point.The system ethylene glycol-water follows the thermodynamicrule that the difference between the calculated and observed specific heztts is equal to the coefficient of the heat of admixture. In all the above respects the properties of the diols are intermediate between those of the mono- and tri-hydric alcohols. Vt = Vo(l + 0.0005657t + 0*0000017074t2 + 0*00000000293t~). E. H. Expansion of Ethyl Ether and of Some Mixtures of the Ether and Ethyl Alcohol. WXLLY BEIN (Abhand. K b'ornabic?& rcngskom. 1908 7 reprint from author).-'l'he density a t 5 O loo,ORGANIC CHEMISTRY. 81 1 5 O 20° and 25* of the purest commercial ethyl ether (Kablbaum) Di5 = 0.7300 of a specimen of ordinary commercisl ether Dt6 = 0 7274 and of two mixtures obtained by mixing Kahlbaum’s ether with 5% and 10% of a commercial spirit containing 90% of alcohol by volume have been determined.The two latter specimens had Dis = 0.7280 and 0.7354 respectively. As the investigations were carried out mainly for revenue purposes no measurements were made with absolutely pure ethyl ether. The density determinations were made in a U-shaped dilatometer the upper parts of the two branches being long graduated capillary tubes; at the extreme ends the capillaries were so narrow that no appreciable error was caused by leaving them open. The density results are probably accurate to sonie units in the fifth decimal place and for convenience of reference they are also tabulated to 1 in 10,000. The mean expansion for lo ct = [( Vt/Yo) - l]t between 0’ and to is as follows allowance being made for the expansion of the glass Purest ether ..... . . . . . . . Ether of D = 0.7280 ... 0.001522 + 0.0000040t. 0.001480 + 0.0000042t. D = 0.7354. .. 0*001438 + 0*0000040t. The results are compared in detail with those obtained by previous observers. In an appendix the impurities which may be present in commercial ethyl ether and the methods of detecting and removing them are given. G. S. Alkylated Halohydrin and Vinyl Ethers. PAUL HORINGI (Bet-. 1908 41 4459-4460. Compare Abstr. 1908 i 497).- Polemical. A reply to Houben (Abstr. 1908 i 935). W. H. U. Action of Alkalis on Sodium Alkyl Thioaulphates. T. SLATER PRICE and DOUGLAS F. Twiss (Bev. 1908 41 4375-4378. Compare Trans. l908,93,1395).-The formation of disulphides by t h e action of alkalis on complex organic thiosulphates was observed originally 3y Bernthsen (Abstr.lbS9 775). The existence of Gut- mann’s thioethyl hydroperoxide (Abstr. 1908 i 497) is questioned. Fromm’s experiments (ibid 969) are also regarded as pointing to the non-existence of this compound. The authors’ previous view of the reaction between alkalis aud alkyl tbiosulphates is adhered to. J. J. S. Indirect Analysis by means of the Dilatometer. Lower Hydrate of Sodium Acetate. W. LASH MILLER (3. Physical C‘hem. 1908. 12 649-654).-When sodium acetate trihydrate is heated it partly melts at 58O with formation of a solution and separation of a new h a l t occurring in leaflets. The leaflets consist of a normal acetate of sodium but they cannot readily be separated from the solution for purposes of analysis. It is shown however on the basis of the phase rule that the com- position of the leaflets can be deduced by adding to a definite quantity82 ABSTRACTS OF CHEMICAL PAPERS.of the tribjdrate a known amoiint of the anhydrons acetnte and determining the proportion of trihydrate present in equilibrinm a t 58". The amount of trihydrate preseiit has been determined by dilntometer measurements. I n this way i t is shown t h a t the le~flets consist of the anhydrous salt a concluqion confirmcd by the direct experiments of Green (next abstract). G. S. The Melting Point of Hydrated Sodium Acetate. Solubility Curves. W. P. GREEN ( J . Physical Chem. 1908 12 655-660) - The leaflets separating when sodium acetate is heated to its apparent melting point at 5s' have been drained a t 9 5 O and shown by analysis and m.p. determination to be the anhydrous salt. The solubility of the anhydrous salt has heen determined from 0" t o 123" the boiling point of the saturated solution and t h a t of the trihydrate from its cryohydric point to 58'. The latter tempernture is a. transition point at which the reaction CH,-C02Na,3H,0= O*092CH3*C0,Na + solution (0 OS$CH,CO,Na + 3H,O) is in equi- librium. The lowest temperature a t which a clear solution can be obtained is 79" when the solution saturated with the anhydride has the same composition as the crystals of the trihydrate. G. S. Molecular Compounds of Magnesium Bromide and Iodide with Derivatives of Acetic and other Organio Acids. BORIS N. MENSCHUTKIN (Zeitsch.anorg. Chent. 1909 61 100-1 18. Corn- pare Abstr. 1907 i 19 395).-Magnesium iadide combines with methyl acetate forming the compound MgI,,6CH3*C02Me. Mixtures containing from 3.5% to 74.5% of the cornpound separate into two layers on melting. On the other hand the ethyl propyl and iso- butyl acetate compounds MgI,,GCH,*CO,Et MgI,,GCH,*CO,Pr~ and Mg1,,6CH,*C02*C,H9@ give regular freezing-point curves aud do not Eeparate into two liquid layers. Separation into two layers is brought about in the case of the ethyl acetate compound by the addition of a little water. Magnesiam bromide forms compounds containing 3 mols. of ester which however crystullise badly. Magnesium iodide and ethyl formate form a compound Mg12,6H*C0,Et which is less hygroscopic than the acetate compounds.The following compounds have been prepared but not further described M.gJJr2,2C,H,*C0,Et m. p. about 110"; RlgBr2,2C,H,.C0,*C4H9B m. p. about 130° ; Mg12,3C,H,*C0,Me m. p. 115-1 17" ; Mg12,3C,HS*C0,Etl m. p. 105". Ethyl mnlonate gives MgBr,,2CH,(COzEt)2 m. p 135' and Mg'l2,4CH,(CO,Et) m. p. about 115'. C. H. D. The Waxes of the Coniferze. A New Group of Natural Principles. J. ROUGAULT and LBON BOURDJER (Compb. rend. 1908 147 131 1-1 314).-By employing the method described by Bourquelot (J. Phurm. Chim. 1901 [vi] 14 481) the authors have isolated white,ORGANIC CHEMISTRY. 83 crystalline powders resembling certain known vegetable waxes in appearance from many of tho Conifers for example from Junipwue Sabina J. cornrntmi8 Picea excdsa Pinnus sytvestris and Thztyo occidsntaZis.Kawalier the only previous worker on these substances (J. p. Cl~m. 1F53 60 321 ; 1855 64 16) owing to the defective method used obtained erroncow results. The purified wax is not a simple substance that from J. Sabina having m. p. 73-78" and yield- ing on repeated recrystsllisation a series of substances having m. p.'s 65' to 84'. All the substances isolated however have the following properties they are acids with an acidity value varying from 25 t o 54 (indicating a molecular weight of 3OCO-1000 i f they are mono- basic acids) contain an alcohol group and are esters with saponification values of about 230. ,411 t heir snponificrrtion products are acids that is the waxes do not give any substances analogous t o glycerol or cetyl or melissyl alcobol.Thus the products of saponification are alccihol- acids and from the results obtained on acetylation seem to contain only a single alcohol and carbosyl group. So far only two of these acids have been isolated. The first has the compositioz CI6H3,O3 of a hydroxypalmitic acid i t has m. p. 9 5 O and is designated juniperic acid. The second sabinic acid m. p. 84O seems to be a hydroxylauric acid C12H2,0s. By connoting the results obtained the authors deduce the mheme R:CH( OH) [CR,],*CO* 0 CHR' [ CH21m-C0 O*CHR*[ CH,lp . . C0,H for the constitution of the waxes R R' R etc. and 72 mlp being either identical or different. The frequent appearance of juniperic acid suggests that they are generally identical. The name etholides is proposed for this group of natural substances whiuh probably differ by the number of acid-alcohol molecules associated in them rather than by differences in the acid-alcohol molecules themselves.They thus resemble the polypeptides more nearly than the polysaccharides. E. H. Eeteno XI. New Method of Formation of Carbon Suboxide. HERMAKN STAUDINGRB and ST. BEBEZA (Ber. 1908 41 4461-4465 Compare Staudinger and Ott Abstr. 1908 i 602).- In attempting to prepare malonic anhydride by acting on malonyl chloride in ether or ethyl acetato with silver lead or zinc oxide it was found that carbon suboxide was formed probably thus Carbon suboxide is also obtained when malonyl chloride is treated with either silver oxalah or malonate; however in none of these cases does the yield of aribon suboxide exceed 10%.Silver malonate inferacts with acid chlorides such as cinnamoyl chloride yielding gmdl quantities of carbon suboxide ; the latter must result from tihe decomposition of malonic anhydride or ft mixed anhydride ; consequantly malonic anhydride differs from its alkyl derivatives in that it yields carbon suboxide and not keten when it decomposes. Acetyl chloride forms with silver malonate a substance which is probably identical with that obtained by Diels and Lalin (Abstr. 1908 i 939) by acting on carbon suboxide with acetic a d . It is also probable that the analogous compound derived from carbon CH,(COCl) + Ag,O = C,O + %AgCl+ H,O.84 ABSTRACTS OF CHEMICAL PAPERS. suboxide and formic acid (loc. cit.) is a mixed anhydride of formic and malonic acid having the fmmula C&(CO*O*CHO) A compound having this constitution when heated would decompose yielding carbon monoxide carbon suboxide carbon dioxide acetic acid and formic acid.A 50-80% yield of carbon suboxide may be readily obtained by treating a solution of dibromomalonyl chloride in ether or ethyl acetate with zinc shavings. Dibrornomalonyl chlorzde CBr,( COCI) prepared by the action a€ phosphorus pentachloride on an ethereal solution of dibromomalonic acid is a colourless oil b. p. 75-7'i0/15 mm. which solidifies to a colourless crystalline mass a t the ordinary temperature. It reacts with aniline forming dibromoinalonanilide CBr,( CONHPh) compact crystals m. p. 143-144". Action of Zinc Dust at High Temperatures on Various Types of Aliphatic and Aromatic Acids. ALEXANDRE HEBERT (Bull.Soc. chim. 1909 [iv] 5 11-1 9).-A continuation of previous work (Abstr. 1901 i 251 ; 1003 i 396) on the products of the distillation of acids with zinc dust. The acids were mixed with from three t o four times their weight of zinc dust and heated at 350-400'. Succinic acid yielded carbon dioxide and inflammable gases composed principally of hydrogen water and liquid oletines. The residue in the flask contained some carbon and zinc Carbonate. Oxalic acid gave hydrogen carbon dioxide. carbon monoxide and water. Bonzoic acid furnished hydrogen carbon dioxide water benzene benzaldehyde some unchanged benzoic acid and a little naphthalene. The decom- position which ensued with cinnamic acid was very complicated. The gases evolved consisted of carbon dioxide hydrogen and some hydro- car bow.The liquid distillate included water benzene toluene xplene styrene diphenyl naphthalene and its homologues stilbene fluorene fluorauthrene homologues of anthracene and phenanthrene tolane and phenylmethanes ('l) with some tarry matters. The residue in the flask contained carbon and some zinc carbonate. Distillation of cinnamic acid with lime showed that styrene is not as is generally supposed practically the sole product of the reaction. The distillate resembled in composition that described above but contained more benzene and a little benzaldehyde. Phthalic acid gave carbon dioxide hydrogen gaseous hydrocarbons water benzene phthalic anhydride and tar. Action of Sulphuric Acid on Acetaldehyde and Paracet- aldehyde.Preparation of Grotonaldehyde. MABCEL DEL&PINE (Compt. rend. 1908 147 1316-1318 *).-The methed of preparing crotonaldehyde described previously (Abstr. 1902 i 133) has been improved by using pnracetaldehyde instead of acetaldehyde. Paracet- aldehyde (50 grams) is added in portions of 10-15 grams to ordinary concentrated d p h u r i c acid (250 c.c.) contained in a flask which is continually shaken and cooled by a stream of cold water. After fifteen minutes the product is diluted to 2 litres with water and * and Am. Chint. P7qs. 1909 [viii] 16 136-144. W. H. G. T. A. H.ORGANIC CHEMISTRY. 85 distilled. By rectification of the product 43% of the theoretical yield of crotonaldehyde is obtained. In tbe reaction tbere are also formed L cowound C,H,,O b.p. 92-98'/30 mm. which seems to be a bimolecular polymeride of crotonaldehyde and a considerable amount of resin. The new polymeride differs from those described by KekulB ( A r m a h 1872 163 105) Raper (Trans. 1907 91 1831) and Zeisel and Bit16 (Abetr. 1908 i 761) in t h a t it forms a gemicarbazone CgHl5O9N3 m. p. 191-194O and a stable o x i m m. p. 106O. The reains formed are fawn-coloured and on oxidation with nitric acid give oxalic acid and a yellow amorphous substance which dissolves in smmonia to an orange solution. E. H. Anodic Oxidation of Aldehydes. GEORGE W. HEIMROD and PHOEBUS A. LEVENE (Ber. 1908 41 4443-4448).-1t has already been shown that acetaldehyde is a good depolariser in acid solution (Dony-Hhault Abstr. 1900 ii 644) and in alkali solution (Baur Abstr.1902 i 77) and further Law (Trans. 1905 87 198) obtained quantities of carbon dioxide and monoxide as well as the corresponding fatty acid on electrolytic oxidation. Acetaldehyde in sodium sulphate or 0*85N-sulphuric acid solution at 4-5O with a current of 1 ampere using s spiral platinum electrode is oxidised almost quantitatively to acetic acid only small quantities of the oxides of carbon being liberated. I n 0-9N-sodium hydroxide solution however only 92% of the oxygen is absorbed by the aldehyde a large amount of carbon monoxide dioxide and oxygen being liberated in the anode gas. Formic acid is found i n the liquid and it is probable that acetic acid is only formed in small amount. Butaldehyde and isobutaldehyde in N-alkali solution give only small amounts of acid and a large volume of carbon dioxide; in the latter case acetone was found but formic acid could not be detected.W. R. Syntheses by means of Mixed Organo-metallic Zinc Derivatives @-Ketone Alcohols and &-Acyclic Uneaturated Ketones. EDMOND E. BLAISE and RI. MAIRE (Ann. Chim. Phyu. 1908 [viii] 15 556-576).-Mainly a resume of work already published (compare Abstr. 1907 i 749 ; 1908 i 79 248 318 596) ; the following compounds are described for the first time y-Hydroxy- y-ethylhcxnn-&one OH-C Et,*COEt b. p. 68'/11 mm. prepared by the action of magnesium ethyl iodide on ethyl semi-ortho-oxalate ; y-methyl- Ar-heyten-r-one CMeEt:CH*COEt b. p. 16Q0 forms a senzicurbazone m. p. 159' ; ethgl cacetoxy-sec.-butyZ htom [a-acetoxy-/3-ethylpsntan-y-m] OAc*CH,*CHEt*COEt b.p. 102'112 mm. ; y - r r a e t h y l m b n - b e CH,:CEt*COEt b. p. 137" ; p - acetoxy - y - ethylhexan- 8 - on.8 OAc*CHMe'CHEt=COEt b. p. l02"/ 12 mm. ; @-methyLA~-hexen-8-m CMe,:CH*COEt b. p. 145O forms a semicarbazooe m. p. 162'. Ethyl P-hydroxya-ethylisovalmate OH*CMe,*CEt*CO,Et b. p. 84O/ 9 mm.; the corresponding acid has m. p. 73'; ethyl PP-dimcthyl-a- ethytacrytate CMe,:CEt*Cc),Et b. p. 1 6 7 O obtained from the above ester by the action of phosphoric acid; the corresponding d has86 ABSTR&CTS OF CHEMICAL PAPERS. b. p. lOO"/lO nim. and the chloride b. p. 49'/13 mm. reacts with zinc ethyl to form P-methyl-y-ethyl-Ap-hexen-6 one CMe,:CEt*COEt b. p. 16P0 of which the semicarbaaone has m. p. 11Y. M. A. W.Formation of Hydrocellulosee by means of Sulphuric Acid. GEORG B~~TTNER and J. NEUMAN (Zeitsch. amgew. Chem. 1908 21 2609-2611. Compare Girard Abstr. 187'3 779 ; Bumke and Wolffenstein Abstr. 1899 852 ; Tauss Ding. Poly. J. 1889 286).- Arnyloid prepared by leaving cotton wool in contact with sulphuric acid (1.53) for several days then carefully precipitating and washing has the composition C 41-89! 42.00 and H 6.0 6.07%. An ideal hydrocellulose can be obtained by Ulzer's method (Wagnei's Jahresbe~*. 1905 192). The cotton is impregnated with 4% sulphuric acid pressed and kept a t the ordinary temperature for four days or until dry and then carefully heated at 7 5 O for eight hours. When touched the maw falls to a white powder and its suspensions in acid have a colloidal nature and do not clear wben kept.Analyses of the washed material dried at 100' gave C 43 S6 H 5.41% which agree with values required for the formula (C6H1005)6,HZ0. When this hydrocellulose is further treated with 50% sulphuric acid sometimes it does not undergo any further change sometimes it yields compounds of the types 3C,H,,O,,H,O and 2C6H,,0,,H,0. The hydrocelluloses are white powders with a gritty feel and are resistent t o acids and alkalis. With sulphuric acid and acetic anhydride they yield cellulose acetates which can be preoipitated by water. They are coloured blue by zinc chloriodide or a solution of iodine in potassium iodide solution and have reducing properties but are not turned black by the ovidising action of the atmosphere (compare Girard). J.J . S. Humin Substances in [Peat Wool ('( Quate de Tourbe"). L EOGER and E. VULQUIN (Compb. rend. 1908 147 1404-1406)- The humic acids extracted from peat wool by sodium hydroxide are derived from cellulose-like substances from which they differ in containing more carbon and nitrogen They contain neither pentosans nor hexosans; alcoholic hydroxyls still seem to be present for acetyl derivatives and thiocarbonates can be formed as in the case of celluloee. The benzene nucleus the grouping *CH,*CO and double linkings are also present. Example of Iaodimorphism. [Ethylamine Halides.] H. MAR AIS (Cmpt. ?*end 1909 148 45-47).-Ethyl:imine hydrochloride and the corresponding hydrobromide are monoclinic at the ordinary temperature. At 80° the hydrochloride changes t o a uniaxial modification which fuses at 10s'.A t 8 3 O the hydrobromide is also changed t o a uniaxial form which melts at 146". Puitlier i l l the superfused hydrobromide an anstable uniaxial f om1 appears which fuses at 118O but under ordinary conditions rapidly changes to the stable form. The monoclinic forms of the two compounds are miscible in all proportions tbe temperature of transformation remains betweea SOo G . B.ORGANIC CHEMISTRY. 57 and 83".. 'She forms obtained at higher temperatures are isodi- morphous the htable form of one being isomorphous with the unstable form of the other. Further as the composition approaches the point corresponding with 45% of the hydrobromide at loo' the unstable forms tend to become relatively stable. Valyl-leucine Anhydride.E. KRAUSE (Monatsh. 19OS 29 11 19-1 130).-The paper is mainly an account of unsuccessful ex- periments and of compounds already described-( Fischer A bstr. 1907 i 684). Vcilyl-leucine anhpdride m. p. 273-274O is formed by heating equal molecular quantities of valine and leucine ester8 at 180-190° or equal quantities of d i n e and leucine in an evacuated tube at 340'. Some Amides of Amino-acids. ERNST KOENIGS and BRUNO MYLO (L'er. 1908 41 4427-4443).-The amides of amino-monocarboxylic acids are not easily obtained in the pure state but i t is found that the ethyl esters are converted into the amides by liquid ammonia and as a rule they are unstable in the presence of water. When the ester of glycine is treated with three times its volume of liquid ammonia there is formed diketopiperazine glycylglycinarnide and glycinamide C2H,0N2 ; the latter compohnd cry stallises from chloroform in needles m.p. 65-67O (corr.). It is strongly alkaline and hygroscopic. The dina~htlulZe~sulp?~~ny~glycinumide from naphthalenesulphonyl chloride and amide crystallises in slender needles m. p. 201O (corr. decomp.) ; P-naphthalenesulphonamide is obtained on its hydrolyhis with N/lO-sodiurn hydroxide showing that the two naphthalenesulphonyl radicles are attached to the amido- nitrogen and not to the amino-group. Carbethoxyglycinamide (Fischer Abstr. 1903 i 609) may also be prepared from the amide by the action of ethyl chlorocarbonate in the presence of alkali and a 10% yield of bydnntoin is obtained from carbethoxyglycinamide by the action of N/Z-sodium bydroside during twenty-four hours at the ordinary temperature.d-AZaninamide C H ON crystallises from ohloroform in colourles~ slender prisms m. < $2' (corr,) [aID + 6' in 5.2% aqueous solution. The dl-alaninamide prepared by liquid ammonia agrees in all respects with that obtained by Franchimont and Friedmann in 1906. Carbethoxy-dl-alaninamide can be obtained in 86% yield from the amide (compare Fischer and Axhausen Abstr. 1905 i 689) and a-methyl bydantoin from the carbethoxycompound has m. pI 146.5' (corr.). p-Naprht~halene8u~p'phonyEdl-alani~amide C1,Hl,O,N,S has m. p. 220' (corr. decomp.). dl-a-Amino-n-butyramids C,H,oON crystallises in prisms II~. p 74-75' (corr.) and yields carbethoxy-dl-a-amino-n-butymmide which forms colourless needles m.p. 115-116O (corr.). u-EtrTryZ hydantoin C5H802N2 crystallises from chloroform in slender needles m. p. 11 8-1 20' (corr.) and p-nu~~trhalenesulphonyl-dl-amino~tyr~ am& Cl,H,,03N,S has m. p. 251O (corr. decomp.). dl-Yalinamide C,H,,ON only results after the ester and liquid G. S. c. s. C22HI SOP2S29 C7H1403N2,88 ABSTRACTS OF CHEMICAL PAPEHS ammonia have been in contact three mouths; it has m. p. 78-80° (corr.) and yields /3-nap/rthalenesulphonyZ-dl-ualinarnide C,,H,,O,N,S of m. p. 256-257O (aorr.) ; cnrbethoxy-dl-ualinamids,' C,H,,C),N slender needles m. p. 143-144' (corr.). dl-leucinumide C6Hl,0N2 has m. p. 106-107O (corr.) ; the P-nuphthabnesulphonyl derivative has m. p. 176-178' (corr.) ; cnrb- ethozy-dl-Zeucilzamide C,Hl,0,N2 m. p.1 OSO and 6-isobutylhydantoin (compare Pinner and Lifschutz Abstr. 1887 1055) is readily obtained from the preceding compound by shaking with sodium hydroxide. dl-~~enR/lalnninccmid~ C,H,,ON crystallises in prisms m. p. 138-1 40' (corr.) and yields the P-naphthalenesulphonyl compound of m. p. 164-166' (corr.) and the carbethoxy-dl-phenylataninamide C,,H,,0,N2 m. p. 141O (corr.). l-Y'yro~tznamride CgH,,O,N crystallises from alcohol in large flat prisms m. p. 153-154" [uE + 19.49' in water and its dicarbethoxy- derivative C,5H2006N2 forms needles m. p. 185' (corr.) ; the morio- carbethox y-1 -t yrosinamide OH*C,H,*CH,*CH( NH* C0,Et) *CO *NH has m. p. 155-157' (corr.). The dinaphthalaizesulphonyl compound C29H,,0,N2S has m. p. 204' (corr.). Carbethoxy-1-uspuragine C17H,205N2 crystallises from water and has m.p. 269-17 1' (COI r.) ; the p-nccphthaleneeul~~onyl-l-as~ragine C,,H,,O,N,S has m. p. 192-193' (corr,). C19H1803N2S'2~ W. R. Preparation of Glycocyamines or Guanino-acids. HENRIK RAMSAY (Ber. 1908 41 4385-4393. Compare Streckor Conzyt. rend. 1861 52 1212 ; Duvillier Abstr. 2880 895 ; 1887 850; Nencki and Sieber Abst r. 1879 70).-One of the simplest methods for the preparation of guanino-derivatives of fatty acids (glyco- cyamines) is warming tbe halogenated fatty acid with a large excess of guanidine (5-10 mols.) and a libtle water. With the simpler com- pounds up to bromoisohexoic acid a temperature of 60' for a few hours is su5cient. With the derivatives of higher fatty acids for example bromopalmitic acid or a-bromophenylacetic acid eight hours at loOD or ten hours at SOo are necessary.Guaninoacetic a-guanino- propionic a-guanino-n-butyric a-guaninoisovaleric a-guaninoisohexoic a-guaninopalmitic and a-guaninophenylacetic acids have been prepared by this method. a-Gunninopropionic acid (alacreatine) has m. p. 226' (corr.) when quickly heated whereas Baumann gives (Abstr. 1873 1024) m. p. lS0' ; the nit?-ate decomposes at 150" and the sulphate at 155-160°. a-Guanino-n-butyric acid (oxybutyrocyamine) crystallises from hot water in slender needles or rectangular prisms and has m. p. 243-245O (corr. decomp.). The nitrate decomposes at 162O and the sulphate at 165-168'. a-Guanino isovaleric acid (ox yvalerocyam in e) forms rectangular plates and has m. p. 842' (corr. decomp.).The nityate decomposes at 172-176' and the sdphute at 1T8-1S0°. a-Guaninoisohexoic acid (a-aminohexocyamine) crystallises in needles and decomposes at 242-243O (corr.). The nitrate decomposes at 177-180° and the szclphate a t 182-1S5O.ORGANIC CHEMISTRY. 89 a-Gzucninopalmitic acid CH,.[CH,Jl3.C(CH,N3).CO,H crystallises from methyl alcohol in octahedra has m. p. 173' (corr. decomp.) and dissolves in alkalis and in concentrated acids. crystallises in slender glistening needles and has m. p. 155-156' (corr. decomp.). The niti*ate (C,7H,,O,N,),,HNO The hydrochloride decomposes at 132-134O (corr.). Phenylguaninoscetic acid (glycol yl phen ylguanidine) CH,N,*CHPh-CO,H appears to be identical with the product obtained by Berger (Abstr. 1880 802) from phenylcyanamide and glgcine.decomposes at 220-226' and the hydrochlovide at 255-258' (corr.}. The nitrate (C,H,,O,N,) HNO,* J. J. S. Acetamide as a Solvent. BORIS N. MENSCHUTKIN (J. Russ. Phys. Chem. Xoc. 1908 40 1415-1434).-The author has determined the solubility curves of various salts in acetamide only salts being chosen for which the solu6ility curves in water have been worked out. The results show that acetamide closely resembles water both in the form of the solubility curves of salts in it and in other proper- ties for example the ionising power. It may indeed be expected that every salt which forms hydrates will give corresponding com- pounds with amides those formed with formamide and acetamide approximating in their properties most closely to those formed with water. No hydrate of potassium iodide is known yet Walker and John- eon (Trans.1905 87,1597) state that this salt forms with acetamide a stable cpmpound KI,GCOMe=NH m. p. 5 4 O . Besides th'e fact that compounds of such a type are usually formed by haloid salts of metals of the second and higher groups the low m. p. given argues against the existence of this compound. The author's investigation of the Byatem acetamide-potassium iodide characterises this system as one in which the components do not combine. The curve which has a form very closely recembling that of the water-potassium iodide curve con- sists of two branches (1) the curve OF lowering of the m. p. of acetamide by the addition of potassium iodide and (2) the curve of solubility of the iodide in acetamide.These two branches meet in a eutectic point about 53O the composition there corresponding approxi- mately with the formula KI,7*1COMe*NEC:,. Crystallisation from methyl alcohol of mixtures of potassium iodide and acetamide of the compositions KI,GCOMe*NH to KI,7COMe-NH2 yielded apparently homogeneous crystals which however the microscope showed were merely mixtures of crystals of potassium iodide and acetamide Hence the conclusion is drawn that Walker and Johnson's co,mpound KI,GCOMe-NH does not exist. The diagram for the system ncetamide-Podinm bromide indicates the existence of the compound NaBr,2COMe-NH2 which decomposes a+ 135-136O (compare Titherley Trans. 1901,79 413). Comparison of this diagram with that for the system water-sodium bromide Rhows that the three branches (1) curve of lowering of m.p. of scetamido OF wat,er by addition of mdiurn bromide (2) curve of solubility of90 ABSTRACTS OF CHEMICAL PMERS. NaBr,2H20 or NaBr,2COMe*NH2 and (3) curve of solubility of pure sodium bromide are practically identical in form in the two cases The diacetamide compound is less stable than the dihydrate a fact which may account for the noo-existence of a compound NaBr,SCOMe*NH corresponding with the pentahydrate. The curve representing the lowering of the m. p. of acetamide by sodium iodide ends in a eutectic point 41.5' corresponding -with NaI,5COMe*NH2 from which starts the curve of solubility ill acet- rtmide of the compound Na1,2COMe*NH2 which decomposes at 125O (compare Tithorley Trans. 1901 79 413). I n this case also no acetamide compound is formed corresponding with the pentahydrate.In the system acetamide-calcium chloride the eutectic point is very low namely 46' corresponding with CaC12,3COMe*NH,. Beyond this point comes the solubility curve of CaC12,6COMe*NH con- tinuing to the m. p. 64"; this compound crystallises from methyl alcohol in hygroscopic plates. At 64" begins the solubility curve of the compound CaC1,,3COMe*NH2 which crystallises in hygroscopic needles decomposing at l86" the solid phase beyond this temperature being probably CaCI,,COMe-NH,. Comparison of this diagram with that for the system water-calcium chloride shows that the solnbility curves for CaCl,,GCONe*NH and CaC12,6H20 are very similar ; with acetamide however no compounds are formed analogous to the a- and P-tetrahydrates and the dihydrate.Like the solubility curve of CaC12,3Me0H (compare Abstr. 1907 i 271) that of CaCl,,3COMe*NH2 also closely resembles that of CltC1,!2K,O. The triacetamide com- pound decomposes the trialcoholate with evolution of methyl alcohol the compounds CaC1,,3MeOH CaC1,,3COMe-NH2 and CaCl,,xH,O being in order of increasing stability. T. H. P. The Action of Chlorine on Garbamide whereby a Dichloro- carbamide is Produced. FHEDBRICK D. CHATTAWAY (Proc. Roy. Soc. 1908 A 81 381-3ss).-Diel~Zoroca;rbamicEe CO(NHCI) prepared by passing a very rapid stream of chlorine into a well- cooled solution of carbamide (%) grams) in water (40 c.c.) separates in thin colourless plst,es. The compound is endothermic and detonates when heated rapidly owing to the formation of nitrogen chloride; when heated cautiously it has m.p. about 83" (decomp.). It is readily hydrolysed by water and when kept in aqueous solution at the ordinary temperature cnrbon dioxide nitrogen nitrogen chloride and ammonium chloride are formed slowly. Acids and alkalis accelerate the hydrolysis and also alter the nature of the end products; thus in presence of dilute acids all the chlorine in the compound is liberated a s iiitrogen chloride but this compound is not formed when - hydrolysis takes place in alkaline solution. The addition of potassium hydroxide c:iuses violent evolution of nitrogen the reaction taking place qumtitatively in accordance with the following equation 3CH20N2C1 + 12KOH = 3K,CO + 2NH + ciKCl+ 2N2 + 6H,O.When carbamide is treated with excess of an alkaline hppobiomita,ORGANIC CHEMISTRY 91 it is probable that a dibromocarbamide is first formed; the manner in which this undergoes hydrolysis is supposed by the author t o furnish an explanation of the variable amount of nitrogen liberated during the decomposition. Dichlorocarbamide is an acidic substance and its aqueous solution reddens and then bleaches litmus; it shows all the reactions of a typical nitrogen chloride. w. 0. w. Dearnotropy and Merotropy. V. Gonstitution of Hydrogen Cyanide. ARTHUR MICHAEL and HAROLD HIBBERT (Annalen 1909 364 64-76).-1n continuation of previous work on the use of tertiary amines for distinguishing between enolic and ketonic deriv- atives (Michael and Smith Abstr. 1908 i 943) the authors have applied this method towards the elucidation of the constitution of hydrogen cyanide.When tertiary amines are brought into contact with anhydrous hydrogen cyanide at O" no salt is formed but only a very slight polymerisation takes place. The rapidity of the latter decreases according to the series triethyl- tripropyl- and triisoamyl-amine that is the capacity possessed by tertiary aminss of polymerising hydrogen cyanide changes in the same relation as their capacity of enolising desmotropic ketones. On the other hand primary and secondary amines unite with hydrogen cyanide forming unstable salts and polymerisation does not take place. This can only be explained by the assumption that hydrogen cyanide exhibits keto-merotropy and that primary and secondary amines can bring about merotropy in the substance whilst tertiary amines can not.The authors' experiments show that the dialkyl- are less dissociable than the trialkyl-ammonium cyanides that is by substituting a hydrogen atom i n NH,F,NC by a third alkyl radicle the affinity between hydrogen and nitrogen is lessened and hence mcondary amines can effect merotropy in hydrogen cyanide with the formation of salts whilst tertiary amines can not. The existence of trialkylammonium cyanide shows that if hydrogen cyanide were in the acidic form (HNC) salt formation with tertiary bases would be possible. The conclusion is drawn therefore that hydrogen cyanide possesses the nitrile constitution HCN. DipropgJ- and diisobuty2-ammonium cganides are white unstable salts; .the latter has m.p. 35". Diisoam$arnmoniitm cyanide is a white crystalline very unstable substance m. p. 68-70". Yiperido?kum cyunide is a white crystalline salt m. p. 47-48O; it is more stable than the other cyanides examined being decomposed only after twenty minutes on keeping i n a desiccator under diminished pressure. isoButyl- and isoamyl-ammonium cyanides remain on evaporation of their solutions in a vacuum partly as oils arid partly crystalline AL1.tJanzmoniuna cyanide is a viscid yellow oil. Aniline does not react with hydrogen cyanide. From the rise of temperature (15') observed on mixing 90% aqueous hydrocyanic acid and triettiylxmine at Oo the authors conclude that salt formation takes place. By treating the trialkylatnmonium chlorides with silver cyanide in methyl-alcoholic solution double salts are obtained.Thus trimethylammonium chloride92 ABSTRACTS OF CHEMICAL PAPERS. gives the salt NMe,HNC,AgNC a white crystalline substanm and triethylammonium chloride yields the salt NEt,HNC,AgNC in white felted needles. On adding hydrogen cyanide to an equimolecular mixture of triethylamine and water and evaporation of the solution in a vacuum an oil was obtained which gave the above double salt with silver cyanide and hence contained triethylammonium cyanide. Tripropylamine behaves similarly 'Dry ammonia combines i t &tautly with dry hydrogen cyanide or its ethereal solution to form am.nonium cyanide. J. C. C. Rewtion between Ferric SaJts and Thiocyanates. ARNALDO BBIONI (Gazxetta 1908 38 ii 638-640). -The author criticises Bongiovanni's views (Abstr.1908 i 770 859) on the interaction of a ferric salt and a thiocyanate. T. IT. P. Simple Preparation of Mercurio Oxycyanide Solution from its Components. ERWIN RUPP and F. LEHMANN (Chem Zentr. 1908 ii 1816; from Apoth. Zed. 1908 23 793-794. Compare Abstr. 1908 i 770).-The reaction indicated by the equation HgC1 + HgCy + 2KOH = HgCy,,HgO + 2KC1+ H,O is brought about by mixing aqueous solutions of molecular proportions of the com- ponents. For the preparation of a 1% solution the following details are given mercuric chloride 5 8 gram ; mercuric cyanide 5.4 grams dissolved in 800 grams of water a1 e add€ ;I slowly to potassium or sodium hydroxide 44.8 grams and water 1000 grams. This solution con- tains 0.25% sodium chloride or 0.32% potassium chloride.After keeping a bolution of mercuric oxycyanide prepued in this manner for three months the mercury mercuric cyanide and also the oxy-corn- ponent were estimated and the results were in good agreement wit4 kl gCy&W= J. V. E. Decomposition of Grtlcium Cyanamide. FELIX LOHLNIS and R. MOLL (Csntrr. Bakt. Par. 1908 ii 22 254-281. Compare Abstr. 1908 ii 230 and Kappen ibid. 414).-It is considered probable that in dissolving calcium cyanamide is converted into the compound Ca(NH*CN) which subbequently decomposes into calcium hydroxide and cyanamide. The latter when heated with lime or when subjected to the action of carbon dioxide yields fitst ammonium cyanate and then carbamide which is converted by bacteria into ammonium carbonate.h direct action of bacteria on cyanamide seems to be impossible. The bacteria flora found i n solutions of the substance consists of varieties which are able to resist the poisonous actiom of cyanamide and cyanates. Dicyanodiamide is not attacked by bacteria and there is no evidence that it exists in soils. N. H. J. M. Chemical Changes of Calcium Cyanamide in Manuring. HUBE~T RAPPEN (C'sntr. Bub. Par. 1908 ii 22,281-298. Cornpate Abstr. 1908 ii 728).-A criticism of Lohnis' results and oonclubions. When calcium cyanamide is digested for some time with distilledORGANIC CHEMISTRY. 93 water at 60° the filtered solution yields crystals of dicyanodiamide. The same change takes place a t the ordinary temperature when solutions are kept for L long time. In the case of concentrated solutions the sparingly soluble compound CN*N( Ca*OH)2,6H,0 and cyanamide are formed the latter changing gradually into dicyano- diamide under the influence of alkali.I n dilute solutions the calcium compound is not formed ; calcium hydroxide separates in crystals whilst the cyanamide all remains in solution and gradually polymerises. N. H. J. M. [Organo-mercury Compounds.] WALTER SCHRAUTE and WALTER SCHOELLER (Ber. 1908 41 4479-4480. Compare Abstr. 1908 i 617).-A reply to Biilmann (this vol. i 17). Action of Nitric Acid on Saturated Hydrocarbons. 11. S. S. NAMETKIN (J. Rust?. Phys. Chem. Soc. 1908 40 1570-1579. Compare Abstr. 1908 i 329).-Experiments on the action of nitric acid (D 1.2) on cycEohexnne show that the yield of nitro-products diminishes and that of acid oxidation products increases as the pro- portion of nitric acid used increases. Nitrocyclohexane C,H,,*N02 is a colourless liquid with a character- istic smell b.p. 109*5O/40 mm. 202'/742 mm. (decornp.) D! 1.0853 Dig 1.0680 nl,g1*4612. This nitro-derivative is not an intermediate product in the oxidation of cyclohexane t o ndipic acid as the latter is formed more readily from cyclohexane than from nitrocyclohexane. Such intermediate product is almost certainly unstable isonitrocycZohexane wbich immediately it is formed is transformed partly into the stable nitrocyclohexane and partly into aldehyde (or ketone according to the nature of the hydro- carbon) which undergoes further oxidation to the corresponding carboxylic acid. The process of formation of tertiary nitro-derivatives is essentially different from that of primary or secondary nitro-compounds the most striking difference lying in the mechanism of the formation of water in the two cases.In the first water is formed from the tertiary hydrogen and the hydroxyl group of the nitric acid R C:H + OHINO = R,C*NO + H20 whilst with primary or secondary hydrocarbons the oxygen atom only is taken from the nitric acid and the two hydrogen atoms from the hydrocarbon R 2 CiH--+-G;NO*OH ._._ 2 _.._____. = R2C:N02H + H20. ARNOLD F. HOLLEMAN (Rec. trau. chim. 1908 27 455-457).-This paper contains details for the preparation of 2-chloro-3-nitrotoluene from 3-nitro-o-boluidine by means of the Sandmeyer reaction. An 84% yield is obtained and the product has m.p. 215O (compare Wynne and Greeves Proc. Bromination of Toluene. 11. ARNOLD F. HOLLEMAN and J. J. POLAK with VAN DER LAAN and EUWES (Rec. trau. chim. 1908 27 435-454. Compare Abstr. 1906 i 154).-The authors continue W. H. G. ........_........ 3 L ...__.._ ~ _.__..__ T. H. P. Preparation of 2-Chloro-3-nitrotoluene. 1995 21 151). w. 0. w. VOL. XCVI. i. h94 ABSTRACTS OF CHEMICAL PAPERS. the studies on the bromination of toluene and in the present com- munication ciiscuss the influence of temperature and dilution and the action of catalysts on the ratio bromotoluenes benzyl bromide. Tables are given showing the percentages of benzyl bromide formed with various proportions of bromine and toluene at 25’ and 50°. The authors claim that their results are more accurate than those obtained by Bruner and Dluska (Bbstr.19OS i 146). On plotting in the form of a curve the values obtained by these authors in their experi- ments on the influence of temperature and comparing these with the data obtained by van der Laan certain discrepancies appear for which at present no explanation can be found. To explain the action of catalysts it has been supposed that these are capable of converting benzyl bromide into a mixture of bromo- toluenes no experimental evidence in support of this view could be obtained however since it was found that when benzyl bromide or chloride is boiled with toluene and ferric bromide the sole product is p-benzyltoluene. A similar experiment in which antimony tribromide was the catalyst resulted in the formation of a small quantity of a liquid containing 50.9% bromine (bromotoluene requires 46.78%).Bromine itself was found to be incapable of behaving as an au t ocatal ys t. Cohen Dawson and Crosland (Trans. 1905 87 1034) have recorded the production of chlorotoluene by the action of nascent chlorine generated by electrolysis on boiling toluene. The hypothesis put forward by Bruner and Dluska (Zoc. cit.) and by Bancroft (Abstr. 1908 ii 788) who suppose that the molecules of bromine attack the side-chain whilst the atoms bring about substitution in the benzene nucleus cannot however be sustained inasmuch as a repetition of Cohen’s experiments using toluorie and hydrogen bromide showed that benzyl bromide and bromotoluene were both formed but that the former underwent reduction by hydrogen produced in the electrolysis. The sugg6stion is made that the true explanation is to be found in the existence of compounds of the type HBrl that these attack the benzene nucleus whilst the molecules of bromine act only on the side-chain.This theory accounts satisfactorily for the influence of dilution for the increase in the amount of benzyl bromide a t higher temperatures and for the increase in the proportion of bromotoluenes brought about by substances such as acetic acid or nitrobenzene which act as solvents for hydrogen bromide. An explanation is also afforded of the specific action of the bromides of iron aluminium. and antimony wkch also promote substitution in the ring. w. 0. w. Properties of Diphenyleneiodonium Hydroxide and of some of its Derivatives.LUIGI MASCARELLI ( A t t i R. Accad. Lincei 1908 [v] 17 ii 580-583; Gaxxattcc 1908 38 ii 619-629. Compare Abstr. 1907 i 1021).-On treating diphenyleneiodonium iodide with moist silver oxide it yields the hydroxide ?6H4>I*OH which is a strong base and could not be isolated owing to the readi- ness with which it absorbs carbon dioxide from the air. I n aqueous (4%ORQANIC CHEMISTRY. 95 solution the hydroxide is reduced by sodium amalgam giving an almost quantitative yield of diphenyl C,,H,I*OH + 2H = C,,H + HI + H,O. This decorcposition indicates the slight stability of the heterocyclic ring containing carbon and iodine which is confirmed by the quantitative change of diphenyleneiodonium iodide into o o- di-iododiphenyl when it is heated for a short time at its melting point.Evidence has been obtained of the formation of a periodide P6HJ 2%- C6H4 DiphenyZeneiodonium bromide YGH4>I*Br separates from water as a white crystalline powder m. p. 245-250’ (decornp.). When heated a t its melting point it is converted into 2-bi*om0-2’-iododiphenyZ (?) m. p. 91*5O which is iinder investigation. T. H. P. Action of N-Amino-compounds on Dehydracetic Acid. CARL BULOW [with HANS FILCHNEB] (Ber. 1908,41 4161-4168)- Dehydracetic acid reacts with p-toluidine in alcoholic solution to form dehydracet ic-p- toluidide C H s < ~ ~ ~ ~ > C * C€€,*CMe N ‘C,H crystallising in colonrless needles m. p. 154’. Boiling with 10% sodium hydroxide resolves it into its components again. It reacts with phenylhydrazine p-toluidine being eliminated and de- hydracetic acid phenylhydrazone formed crystallising in golden- yellow plates m.p. 202O and identical with the compound obtained by the direct interaction of phenylhydrazine and dehy dracetic acid. It gives a characteristic blue coloration with concentrated sulphuric acid and a trace of ferric chloride and is resolved on boiling with 10% sodium hydroxide into its components. condenses with dehydracetic acid in a similar manner to p-toluidine. The condensation product Ethyl- 1 -amino-2 5 - dimethylpyrrole- 3 4 -dicarboxylate has m. p. 160’; it is of acid character and dissolves in &lute alkali whence it is precipitated by carbon dioxide. Dehydracetic acid formylhydraxona C,H,O,:NbNH*CHO crystallises in colourless needles m.p. 1 5 4 O and likewise possesses a faintly acid character. Dehydrucetic acid semicarbazone C,H,O,:N*NH*CO*NH crystallises in colourless needles m. p. 197-198O; it dissolves in weak alkali and is precipitated unchanged in crystalline form by weak acids. E. F. A. Chromophores without Double Linkings. HUGO KAUFFMANN and IMMANUEL FRITZ (Bey. 1908 41 4413-4422).-Ullmann and Loewenthal’s 2-iodo-1 4-dimethoxybenzene (Abstr. 1904 i 72ri) m. p. 2 3 O b. p. 157’/10 mm. is conveniently obtained in 90% yield by treating an alcoholic solution of quinol dimethyl ether with iodine and mercuric oxide. A small quantity of di-iodoqzcinol dimeth?/Z ether C,H,T,(OMe) m. p. 1 no is also obtained. Chloroiodoquinol dimethyl ether C6H2ClI(OMe)2 m. p. 115O in which the position of the chlorine h 296 ABSTRACTS OF CHEMICAL PAPERS.has not been ascertained is prepared by treating a chloroform solution of 2-iodo-1 4-dimethoxybenzene at 0' with chlorine digesting the red product with 10% sodium hydroxide and treating the resulting iodoso-compound with an acidified solution of potassium iodide ; it separates from alcohol in white needles C,H,Cl(OMe),* IC12 m. p. 45-50' (decomp.) is a brick-red crystalline powder? prepared by the action of chlorine on a chloroform solution of chloroiodoquinol dimethyl ether at 0'; by treatment with 10% sodium hydroxide it yields a white amorphous iodoso-compound C',H,Cl(OI\IIe),*IO m. p. 106' (decomp.). Dichloroiodoquinol dimethyl ether C6HC1,1(OMe) m. p. 81' is obtained when the preceding iododichloride is kept in a closed vessel for some days and separates from alcohol in white woolly crystals ; the iododichloride C,HCl,(OMe),*ICl m.p. 130° is a citron-yellow crystalline powder and the iodoso-compound m. p. 70' (decomp.) is a white amorphous substance. Trichloroiodoquinol dimethyl ether C,Cl,I(OMe) m. p. 135O crystallises in colourless needles and is prepared by leading chlorine into a chloroform solution of 2-iodo-1 4-dimethoxybenzene which is only slightly cooled so that the final temperature is about 30'. The iododichloride C,Cl,(OMe),*ICl m. p. 125-1 30' (decomp.) is a pale yellow crystalline powder and the iodoso-compound C,Cl,(OMe),*IO m. p. 120-125' prepared in the dark is white and amorphous. 1 4-Dimelhoxy~~heiz?/l di-iododichloride C,H,(ORle),(ICl,) m.p. 50-60° (decomp.) prepared by leading chlorine into a chloroform solution of di-iodoquinol dimethyl ether a t Oo is an orange crystalline powder which by keepinb for a few days in a closed vessel is converted into colourless dichlorodi-iodoquino2 dimethyl ether. The di-iocloso-com- Nitroquinol Dimethyl Ether. HUGO KAUFFMANN (Ber. 1908 41 4396-4412).-See this vol. ii 107. Fluorescence of Potassium Quinoldisulphonate. HUGO KAUFFMANN (Bey. 1908 41 4422-4423).-1~ reply to Hantzsch (Abstr. 1908 ii 446) the author states that the fluorescence of por;aasium~quinoldisulphonate so far from being slight is visible to the Derivatives of Ethyl Catechol. HERMANN PAULY and KARL NEUKAM (Ber. 1908 41 4151-4161. Compare Abstr. 1907 i 91 6).-The dibromide of 3 4-dihydroxystyrene (vinylcatechol) methyl- ene ether forms colourless matted needles m.p. 82' (compare Barger and Jowett Trans. 1905 87 967). When heated with bromine in carbon disulphide a tribromide m. p. 62" crystallising in colourless The iododichloride C,HCl,(OMe),~IO pound C,H,(OMe),( 10)2 is a yellow powder. c. s. naked eye in an ordinary test-tube. c'. s. needles is formed. The cyclic carbonate CO<O>C,H,*CH:CH 0 (Abstr. 1907 i 916) exists in two forms needles m. p. 195' (corr.) and needles m. p. 200' (corr.). CO<g>C,H,* CH Br*CH,Br The dibronzide,ORGANIC CHEMISTRY. 97 obtained by the action of bromine in carbon disulphide solution at - lo' crystallises in short obliquely-cut prisms m. p. 69-70'. Free vinylcatechol is best prepared by hydrolysis of the carbonate with aqueous pyridine. It is obtained as a deep yellow viscid oil which easily polymerises ; it dissolves in fuming hydrochloric acid with a rose-red coloration which disappears on dilution.The view formerly expressed that vinylcatechol exists in a quinonoid form is now held with all reserve. 3 ; 4-Dihydroxyphen yl-,B-chloro-a-ethanol methylene ether CH~<:>C,H,*CH(OH)*CH,CI prepared by the addition of hypochlorous acid to the styrene was ob- tained as a yellow oil which on purification by distillation in a vacuum formed a colourless odourless oil b. p. 157' (corr.)/9 mm. 163-164'1 13 mm. When kept the chlorine content increases and P-chloro- methylenedioxystyvene CH2<g>C6H3*CH:CHCl is formed with the elimination of water. This is also formed on slow distillation of the chlorohydrin; it is a transparent colourless oil with an anise or piperonaldehyde-like odour b.p. 1 38'/1 1 mm. 141-142'/13 mm. It forms an oily additive dibrornide. At the same time as the above chlorohydrin a substance containing an additional atom of chlorine is formed by the action of hypochlorous acid ; this crystallises in well- formed glistening colourless needles m. p. 197.5' (corr.). It shows no catechol reaction when heated with sodium carbonate. The corresponding chloroh3drin of the cyclic carbonate CO<E>C,H,* CK(0H) * CH2Cl prepared in a similar manner forms colourless crystals M. p. 95-96'. The bromohydrin prepared by the decomposition of the dibromide of vinylcatechol carbonate separates in small colourless prisms which melt at 100' to a red liquid and decompose to a greyish-violet dye m.slowly heated 96' or quickly heated 107'. These carbonate derivatives give yellowish-brown colorations with ferric chloride. The chlorohydrin of the catechol is obtained from the corresponding carbonate by heating with magnesium carbonate in acetone solution. The phenol is transferred t o warm benzene and quickly brought to crystallieation using special precautions to prevent the formation of dyes. It crystallises in thin colourless pointed plates m. p. lOa0 decomposing instantly into a greyish-violet dye. P-Methylamino-3 4-dihydroxyphenyl-a-ethanol methylene ether CH2<g>C6H,*CH( OHj*CH,*NHl\le prepared by double decomposition of the chlorohydrin with methyl- amine is a viscid colourless oil with a faint violet fluorescence b. p.170"/12-13 mm. It turns litmus blue and is perhaps identical with the methyIalkamine described by Barger and Jowett (Zoc. cit.). The picrate forms small yellow sandy crystals m. p 1 8 8 O (corr.) (Barger and Jowett give 178'). It unites with phenylcarbimide in alcoholic solution forming in the first place an easily soluble oil and sub- sequently a crystalline compound m. p. 155' probably a hydrothiazole.98 ABSTRACTS OF CHEMICAL PAPERS. The carbonate of the chlorohydrin forms an amorphous base with methylamine very similar to epinephrine (Abel Abstr. 1900 i 72). E. F. A. Resorcinolbenzein. MANS VON LIEBIG (J. p. Chern. 1908 [ii] '78 534-543. Compare Abstr. 1908 i 445; Kehrmann and Dengler Abstr.1908 i 1002 ; Doebner Abstr. 1883 861 ; Cohn Abstr. 1894 i 120).-Resorcinolbenzein is formed by fusing resorcinol with either benzil or benzoic anhydride. It is possible that in the latter case a reaction takes place similar to that which occurs in the synthesis of fluoresrein Ph*C:(C H *OH),:O P h C (C,H,* OH),:O H C6H:,(0H)212 -+ >06 >O + H E c,H,w),I Ph*C:O Ph*C:O Resorcinolbenzein forms a barium salt C76H42012Ba4 glistening bluish-red leaflets and a hydrochloride C7,H,,,O1,,4HC1 brownish- yellow leaflets. It is converted by an alcoholic solution of ammonia into anhydro~~esorcinolbenxein C7,H,,01,,EtOH (?) which crystallises in brownish-red leaflets with a blue shimmer. The latter compound and resorcinolbenzein when boiled with glacial acetic acid yield a substance C76H,,01,,Ac*OH obtained as brownish-red leaflets with a blue reflex.An alcoholic solution of potassium hydroxide converts resvrcinolbenzein into a substance CRSHSOOg almost colourless needles m. p. 147' and 2 4 2' 4'-tetrahydroxytritan-2 2'-ether Cl9Hl4O3 which crystallises with benzene of crystallisation in colourless leaflets or aggregates of prisms m. p. 170-171'. The latter substance is identical with Doebner's tetrahydroxytritan which however because it was crystallised from dilute spirit contained an additional H20. It yields an acetyl derivative C,gH120(OAc)2 m. p. 184" and a dimethyl derivative C,,H,,O(OMe) thin colourless leaflets m. p. 126". Resorcinolbenzein reacts with methyl sulphate forming a methyl derivative Cl~HiiO(OMe) colourless crystals m.p. 105O and with acetic anhydride yielding the ucetyl derivative CIgH,,O(OAc),,Et* OH colourless pointed prisms m. p. 147' ; when the acetylation is carried out in the presence of zinc dust the acatyl derivative C3,H2603(0Ac) is formed ; it crystallises in colourless glistening needles m. p. 1'79". W. H. G. The Structure of Guaiol. A. GANDURIN (Ber. 1908 41 4359-4363).-Guaiol (Wallach and Tuttle Abstr. 1894 i 538. Compare this vol. i 112) extracted from guaiacum-mood oil by means of ether crystallises from 70% alcohol in large colourless prisms [a]E - 26.64' ; it is triboluminescent. Dihydroguaiene prepared by the action of zinc dust on guaiol is a colourless almost odourless oil b. p. 122"/11 mm. [.IF5 - 2S.6S0 D 0.9089 D2p5 0.8914. ngz 1.49317.Guaiol methyl ether is a colourless almost odourless oil b. p. 141-143'/9 mm. [a] - 31*81' D 0.9513 Di5 0.9332 nZ5 1.48963. Guaiene prepared from guaiol through the xanthate (compare Wallach and Tuttle Zoc. cit.). is a colourless almost odourless oil b. p. 124'/11 mm.,ORGANIC CHEMISTRY. 99 [ C C ~ - 66.11° Di 0.9133 D',5 0.8954 ng 1.49468. The author draws the conclusion particularly from the mol. refraction of the above substances that guaicl is a tertiary dicyclic alcohol containing an ethylene linking. J. C. C. Triphenylcarbinols. Huao EAUFFMANN and IMMANUEL FRITZ (Ber. 1908 41 4423-4427. Compare Abstr. 1905 i 280 773).- 2-Iodo-1 4-dimethoxybenzene readily reacts with magnesium in dry ether and the reaction of the oily product with ethereal 2 5-dimeth- oxybenzophenone leads to the formation of 2 5 2' 5'-tetramethoxy- triphenylcavbinol OH*CPh[C,H,(OMe),] m.p. 1 ZOO which develops a dark green colour with concentrated sulphuric acid and is reduced by warm alcoholi. hydrogen chloride to 2 5 2' 5'-tetramethoxytripienyl- methane m. p. 74". The ethereal solution of the preceding organo- magnesium compound reacts with carbon dioxide yielding in the usual may a small amount of dimethylgentisic acid and as the main product Kauffmann and Grombach's 2 5 2' 5'-tetrsmethoxybenzophenone. The interaction of the latter and the organo-magnesium compound leads to the formation of 2 5 2' 5' 2'' 5"-hexamethoxytripJ~enyL carbiinol OH*C[C,LX,(OMe)2]3 m. p. 136" which gives an indigo-blue colorahion with Concentrated sulphuric acid a green coloration with concentrated hydrochloric acid and yields by reduction with alcoholic hydrogen chloride or with zinc and glacial acetic acid 2 5 2' 5' 2" 5"- hexamethoxytriphenylmethane m.p. 15 lo. c. s. Electrolytic Reduction of Benzoic and Salicylic Acids to the Corresponding Aldehydes. CARL METTLER (Bey. 1908 41 4148 -4150).-6enzoic acid i n presence of mineral acids is electro- lytically reduced to the corresponding alcohol (Abstr. 1905 i 436; 1906 i 851 ; 1907 i 315) and no trace of aldehyde is formed during the reaction. I n neutral or alkaline solution hydrogenated carboxy.lic acids are formed. On reduction however in presence of boric acid considerable quantities of aldehyde are formed (compare Weil Abstr. 1908 i 800). It is convenient to use an aqueous boric acid solution and sodium benzoate with a mercury cathode which gives rise to sodium amalgam on passing the current and this reduces the benzoic acid to aldehyde. It is necessary to ensure the continued presence of boric acid and to remove the aldehyde formed from further reducing action.To t b i s end benzene is added and the liquid stirred rapidly to keep it in a constant state of emulsion. Benzoic and salicylic acids and some of their derivatives can be reduced to aldehyde in this manner; the reaction t,akes place only with difficqlty in the case of the halogen benzoic acids and of hydroxynaphthoic acid. E. I?. A. Preparation of Benzoyl Cyanide. WILEELM WISLICENUS and ROBERT SCHAFER (Ber. 1908 41 4 169 -4l'il).-It has previously been shown (Abstr.1908 i 973; this vol. i 29) that the group :C(NO,)Br has a pronounced tendency t o eliminate bromine and nitric oxide and form the keto-group. Phenylacetonitrile is readily converted by meaas of ethyl nitrate and sodium ethoxide into the sodium100 ABSTRACTS OF CHEMICAL PAPERB. derivative of phenylisonitro-acetonitrile (Abstr. 1902 i 541) which Fliirscheim (Abstr. 1903 i 79) has converted into bromocyano- phenylnitromethane. Chlorine acts on the acetonitrile even more readily than bromine forming phenylchZoronitrocyanometham C,H,*CCl( NO,).CN a light yellow oil. This rapidly decomposes when warmed and affords almost the theoretical quantity of benzoyl cyanide crystallising in large plates m. p. 32-34'. Iodine is without action on phenyliso- nitro-ace toni trile.E. P. A. Z-Gampholic Acid. MARCEL GUERBET (Compt. rend. 1909 148 98-10t).-Z-Campholic acid can be prepared by the method described previously for the dextro-acid (Abstr. 190S i 661). When Lborneol identified with Z-camphol by Haller's method (Abstr. 1889 1206) is heated in sealed tubes with recently-fused potassium hydroxide it is oxidised thus C,H,<XE?OH + KOH = C,H1,<CH3 + H2. The resulting l-campholic acid forms colourless crystals m. p. 106-1 07' [a] - 49.1' (molecular solution in 95% alcohol). Its chemical properties are similar t o those of the d-acid (compare Guerbet Abstr. 1896 i 56). The ammonium salt readily dissociates evaporation of its aqueous solution leaving the acid. It cannot be esterified by the direct action of alcohol8 with or without the presence of hydrogen chloride. l-Campholic anhydride (C,,H,,O),O prepared by dehydrating the acid with acetic anhydride crystallihes from acetone in colourless square tablets m. p.57-58' which are not attacked by cold alcohol but give ethyl campholate on boiling with the latter. It is gradually hydrolysed by boiling aqueous potash. The chloride C,,H,,OCl obtained by treating the acid with a slight excess of phosphorus penta- chloride is a colourless liquid b. p. 222' (the same as the d-isomeride) which when heated with a trace of phosphoric oxide deconiposes into hydrogen chloride carbon monoxide and i-campholene C,H,,. Ethyl 1-campAoZate C,,H,,O,Et prepared by the action of alcohol on either the anhydride or the chloride is a colourless oily liquid b.p. 228'/765 mm. (corr.) having a strong odour of pears. It is not saponified by alkalis under ordinary conditions but is readily decomposed on heating with hydriodic acid. The sodium salt CloH170,Na,SH,0 crystallises in efflorescent nacreous lamellae whilst the copper salt (CloH,~02),Cu,0Et crystal- ises from ether in large green prisms containing ether of crystal- lisation. l-Cumpholamide obtained by the action of ammonia on an ethereal solution of the chloride forms eolourless needles m. p. 77-78" which are ditficultly hydrolysed by alkalis but readily by acids. Syntheses in the Camphor Group. I. isoLaurolene and isoLauronolic Acid (@-Campholytic Acid). GUSTAVE BLANC (Bull. SOC. chim. 1909 [iv] 5 24-3l).-A r6sum6 in greater detail of results already published (Abstr.1906 i 523) dealing with the syntheses of these two substances from a=-dimethyladiplc acid as a starting point. C0,K E. H.ORUANIC CHEMISTRY. 101 The product of the condensation of isolaurolene- with acetyl chloride in presence of aluminium chloride (Abstr. 1899 i 630 ; 1906 i 524) contains a substance which is probably tetrahydro-p- xylyl methyl ketone b. p. 210'. This is liquid and yields an oxim m. p. 106' crystallising in small prisms and sparingly soluble in light petroleum. The principal product of the condensation is the ketone I >C,H*COMe (Zoc. cit.) which yields a n o x h e m. p. 65" readily soluble in light petroleum and with care can be oxidised directly by sodium hypobromite to isolauronolic acid or the ketone may be reduced by sodium in alcohol to the secondary alcohol CMe2*CMe CH,-CH yMe,*CH Me CH,-CH >CH*CHMe*OH (loc.cit.) which on oxidation with chrGmic acid is converted into 3-acetyl-1 1 2-trimethylcyc3opentane b. p. 195O a mobile liquid with a faint odour; its semicarbazone m. p. 213' is sparingly soluble in alcolbl and the oxime m. p. 47O b. p. 137'/20 mm. forms large scales and is readily soluble in most organic solvents. This ketone is oxidised by nitric acid or better by sodium hypobromite solution to dihydroisolauronolic acid and this on bromination and treatment with potassium hydroxide in alcohol yields isolauronolic acid as described h e a d y (Abitr. 1906 i 524). T. A. H. Xylenolglycollic [Dimethylphenoxyacetic] Acids and their Derivatives. GIOVANNI JANDOLO (Rend.Accad. Sci. Pis. Mut. Napoli 1908 [iii] 14 149-155).-These acids may be obtained in good yield by melting the xylenols with chloroacetic acid and adding a quantity of sodium hydroxide solution (1.3) three times as great as that of the xylenol used. 2 ; 4-0imethyl~henoxyacetic acid (m-xylenolglycollic acid) C,H,Me,*O*CH,*CO,H crystallises from all the ordinary solvents in flat white needles m. p. 141'. I t s silver C,,H,,O,Ag and barium (C,,Hl,0,),Ba,2H,0 salts were prepared. The corresponding anilide C,H,Me2*O* CH,*CO*N HPh crystallises from alcohol in a silky mass of slender needles m. p. 104'. The anhydride ( C,,H,102),0 crystallises from alcohol in yellow needles m. p. 94-95'. a-2 4-Dimethy~phenox~ciizrzamic acid (m-xylenolcinnamic acid) C6H ,Me,*O C( CO,B) CHPh crys tallises from alcohol in transparent white prisms m.p. 1'71'. The barium and silver salts were prepared. 2 ; 5-Dirmethylphe~tox~acetic ucid (p-xylenolglycollic acid) C,H,Me,*O*CH:,*CO,H crystallises from water in transparent white needles m. p. 119'. The silver and barium ( + 2H,O) salts were prepared. The anilide C,H,Me,*O*CH,*CO*NHPh crystallises from alcohol in groups of white silky needles m. p. 90'. 3 ; 4-DimethyZphenoxyacetic acid (o-xylenolglycollic acid) C1,H,,O crysfiallises in sbining white scales m. p. 162". The silwer and102 ABSTRACTS OF CHEMICAL PAPERS. bavium ( 2H,O) salts were prepared. colourless rectangular monoclinic lamins m. p. 80'. The anilide CI6Hl1O2N forms a-3 4-Dimetl~ylphenoxycinna~ic acid (0-xylenolcinnarnic acid) -~ C17H1603 forms white prisms m.p. 180'. Attempts t^o prepare a-3 5-dimethyl phenoxycinnamic acid (p-xylenol- cinnamic acid) did not result in a pure product owing to the difficulty of crystallising it. T. H. P. Benzoylacrylic Acid. J. BOUGAULT (Ann. Chim. Phys. 1908 [viii] 15 491-515).-A detailed account of the preparation and properties of benzoylacrylic acid and its derivatives part of which has been already published (Abstr. 1908 i 179 269 422 537 791). Benzoylacrylic acid more conveniently prepared from /3- bromo- benzoylpropionic acid by the action of sodium acetate and acetic acid (Wolff Abstr. 1891 1185) combines with bromine to form the dibromo-derivative m. p. 148O (Pechmann Abstr. 1883 1074 gives 135'). When treated with ammonia benzoylacrylic acid yields the ammonium salt m.p. 197' of an amino-acid which probably has the constitution COPh*CH,*CH(NH,)*CO,H whilst with aniline it combines directly t o form an acid xn. p. 138' probably COPh*CH,-CH( NHPh)* CO,H which condenses with phenylhydrazine to form the acid C,,H,,O,N m. p. 151'. The compound obtained by Gabriel and Colman (Abstr. 1899 i 390) by the inheraction of hydrazine an'd benzoylacrylic acid is probably not the hydrdzoiie as described but 3-phenyZpyraxoline-5-carb- which yields the crystalline bromo- oxylic acid CO,H*CH< m p. 251'. The oxime and semi- derivative CO,H* C H< curbnzone of benzoylacrylic acid have m. p. 168' and 190' respectively. p-Methoxy- and methylenedioxy-benzoylacrylic acids (Abstr. 1908 i 269) can also be prepared by the action of sodium acetate and acetic acid on the broruo-derivative of p-methoxybenzoylpropionic acid and methylenedioxy benzoj lpropionic acid respectively.1'-Xethoxy- benzoylpropionic acid (anisoyipropionic acid) has m. p. 147' (Poppcnberg Abstr. 1902 i 60 gives 140-141') ; the bronzo- derivative OMe*CGK,*CO*CHBr*CH,*CO,H has m. p. 114' ; methyZeizedioxyberLzoylyro~~onic acid CH,O, C H;CO*CH,* CH,* CO,H m. p. 1 3 6 O yields a ~TOWO-derivative CH20,:C,H3*CO*CHBr*CH2-C0,H m. p. 147'. NH 'q CH,-C Ph' NH-N CHBr-8 Ph' M. A. W. The Colours of Indoneacetic Acids and their Carb- &zones. HANS STOBBE and OTTO HORN (Rer. 1908 41 4381-4384). -The colours of indoneacetic acid (this vol. i 31) 3-methyl-l- indone-2-acetic acid (Abbtr. 1904 i 503) and 3-phenyl-l-indone-2- acetic acid (ibid.1902 i 542) and of their semicarbazones have been examined and their ul tra-violet absorption spectra photographed.ORGANIC CHEMISTRY. 103 The substitution of methyl for hydrogen in either the acid or its semicarbazone has no effect on the colour whereas introduction of phenyl increases the depth of the colour the absorption limit of the phenylated acid being 34 wave-lengths nearer the red end of the spectrum. The relationships are much the same in the case of the semicarbazones (compare Abstr. 1906 i 960). All three semicarbazones are paler in colour than the corresponding acids. J. J. S. Mode of Oxidation of Phenyl Derivatives of Fatty Acids in the Animal Organism. 111. Synthesis of some Derivatives of Phenylpropionic Acid. HENRY D.DAKIN (J. BioZ. Chem. 1908 5 303-309. Compare Abstr. 1908 ii 720 964).-In the organism P-hydroxy-P-phenylpropionic acid is oxidised with much greater difficulty than P-phenylpropionic acid and is mostly excreted un- changed. I n order to test the hypothesis that combination with glycine it a necessary preliminary to combustion P-hydroxy-/3- phenylpropionylglycine OH°CHPh*CH,*CO*NH-CO,H was prepared. Cmnamoylglyciue CllH,,O,N obtained by the Schotten-Baumann reaction mas found to be identical with that previously obtained from urine (Zoc. cit.) and yielded successively ap-dibromo-6-phenylpropionyl- glycine C,,H110,NBr2 prisms m. p. 190-191' a-bromo-P-hydroxy-P- phenylpropionylglllcine C1 H,,O,N Br needles m. p. 87-88" and ~-hydroxy-~~henylp~o~ionyZglycine CIlI3,,O4N needles m.p. 146-1 47'. The last substance but one yields with warm concentrated hydro- chloric acid P-chloro-a-bronzo- P- phenylpropionylgZycine C,,H O,NClBr m. p. 203-204'. G. B. isoPhthalacene Group Structure of Phthalacene. 11. GIORGIO ERRERA (Gazzetta 1908 38 ii 588-598. Compare Abstr. 1908 i 183).-The author has investigated the structure of the acids obtained by the actionrof concentrated sulphuric acid on 3 B-diphenyl- toluene-2 2' 2"-tricarboxylic acid (Zoc. cit.). It is found that this action yields the following three isomeric monobasic acids which were separated by means of their ethyl esters (1) the original phthalacone- carboxylic acid which yields 3 5-diphenyltoluene-2 2' 2"-tricarboxylic acid when fused with potassium hydroxide ; (2) isophthalaconecarb- oxylic acid which when reduced with hydriodic acid and phosphorus yields (a) an isomeride of phthalacene to which the name iso- phthalacene is given and (P) isophthalacenecarboxylic acid ; (3) phthalacoiieisocarboxylic acid.The oxidation of isoph thalacene yields the oxide of isophthalacene and isophthalacone which are analogous with the corresponding oxidation products of phthalacene. crys- tallises from acetic acid in shining golden-yellow needles m. p. 316" and dissolves sparingly in alcohol o r befizene and readily in xylene. The corresponding acid C,,K,,O separates from xylene or acetic acid in minute irregular brownish-yellow cry.tals m. p. 370' (decornp.) and dissolves sparingly in the ordinary solvents. qO--$XCMe*8*FO C H,* C CH-C C A,* CO,E t' Ethyl ~so~htha~aconecarbox~~c6te,104 ABSTRACTS OF CHEMICAL PAPERS.is deposited from xylene in shining golden-yellow crystals m. p. isoPhthalacenecar6oxylic m i d crystal- lises from acetic acid in faintly yellow leaflets or needles m. p. 286-287' and dissolves sparingly in alcohol benzene or xylene. The ethyl rester C2,H2,02 separating from acetic acid as a dirty yellow crystalline powder m. p. 172-173O and the sodium salt C2,H,,02Na,4&H20 were DreDared. $?6H4*Q CH- CMe Q*QO CO-C~-=C*C,H,*CO,Et' Ethyl phthakaco~isocarboxytate 3 29-330'. QH2-Q CMe*s*QH C,H,* C:CH-C*C6H3*C02H' 1 . 1 . isoPhthakacene F!H2-?:CMe'g*?H2 crystallises from benzene in C,H,* C:CH-C* C6Hl faintlv vellow laminae m. D. 222'. . r w isoPhthalacene oxide ' CO'-YCM~*E*FH~ I acid in golden-yellow leaflets m.p. 216-218'. is0 Phthalacone ~o-F:cMe*Eo(?o crystallises from acetic C6H4*C:CH-C*CsH4' crystallises from aniline in C,H,*C:CH-C*C,H shining golden-yellow needles m. p. 355-356'. Hydrophthalic Acids ; Velocity of Addition of Bromine to the Tetrahydrophthalic Anhydrides. VI. GINO ABATI [with MAURO SOLIMENE] (Gaxxettcc 1908 38 ii 577-587. Compare Abstr. 1907 i 419 420).-The author has investigated the rate of addition of bromine (0.01 mol. solution) to each of the five tetrahydrophthalic anhydrides dissolved in chloroform (0.01 mol. solution) at 25'. Bauer (Abstr. 1905 i 729 ; 1907 i 307) finds that the accumula- tion of negative substituent groups at two carbon atoms connected by an ethylene linking diminishes or annuls the capacity of the compound to unite with bromine.This is in accord with the author's observation that the A1-tetrahydrophtbalic anhydride requires thirty-four days to complete the addition of bromine whilst with the cis-Abanhydride less than three days is required ; with the other anhydrides examined no such relation is observed. There appears to be a close connexion between the time occupied by the anhydride in absorbing bromine and the dissociation constant of the corresponding acid as is seen from the following table T. H. P. Time of Dissociation absorption of bromine. constant of acid. Al-Anhydride ............. 33-34 days 0-0590 A3-Anhvd ride .............. 25-26 0.0581 trans-A4-Anhydride ...... 20-21 0'0118-0 0130 A2-Anhydride ............... 24-15 0.0074 cis- A4-Anh ydrid e ...........2-3 9' 0.0062 The conclusion is drawn from these and other rewlts that the unsaturated carbon atoms constituting the ethylene linking are of such a nature that the influences tending to lower the capacity of the linking to take up a negative element tend to increase the capacity of additiou of a positive element and vice versa. T. H. P.ORGANIC CHEMISTRY. 105 Action of isoPhthalic and Terephthalic Acids on p-Amino- phenols. DOMENICO PUULIESE and GIAMBATTISTA SELVAGUI (Rend. Accad. Xci. Xiis. Mat. Napoli 2908 [iii] 14 141-146).-1n alcoholic solution isophthalic acid (1 mol.) and p-aminophenol or its ether8 (1 mol.) react giving the corresponding acid salt CO2H~C,H,*CO2H,NH2~CBH4*OR. With terephthalic acid however no reaction takes place probably owing to the slight solubility and feeble acid properties of the acid.When however isophthalic or terephthalic acid (1 mol.) and a p-aminophenol ether (1 or 2 mols.) are heated together in the absence of a solvent they react giving only the corresponding diamide I n some instances however further changes went on to such an extent even when the compounds were heated together in a stream of carbon dioxide that the diamide could not be separated in quantity sufficient for analysis. pAnisidine hydrogen isophthulute CO,H* C,H4*CO2*NH,*C,H4*O~e separates in shining white fragments and begins to turn brown without melting at above ZOO'. p-Phenetidine hydrogen isophthalate CO,H*C,H,* CO,*NH,*C,H,*OEt is deposited in tufts of white needles and decomposes at slightly above 100'. is0 Phthulodi-p-anisidide C,H,(CO*NH*C,H,*OMe) prepared by the interaction of isophthalic acid (1 mol.) and p-anisidine (2 mols.) crystallises from alcohol in slender neiitral white needles m.p. 268'. (rerepl,t?~aZodi-panisidide C,H,(CO*NH*C,H,*OMe) crystallises from alcohol in neutral nacreous scales m. p. 246-248'. Terephthulo~i- p-pheizetidicle C,H,( CO-NH-C,H,*OEt) prepared from terephthalic acid and p-phenetidine was obtained mixed with terephthalic acid which could not be removed by crystallisation. C,H,(CO,H) + 2NH,*C,H4*OR = C,H,(CO*N H*C,H,*OR) + 2H20. T. H. P. Phenylitaconic Acid. HANS STOBBE (Ber. 1908,41 4350-4357). -The author has made a further study of the reaction between ethyl succinate and benzaldehyde (Stobbe and Kloppel Abstr.1894 i 594) with the object of obtaining an increased yield of phenylitaconic acid (compare Hecht Abstr. 1903 i 700). The anhydride and the two mono-esters have also been investigated. [With OTTO Hoa~.]-Phenylitaconic acid is obtained in a 35% yield by adding slowly a mixture of ethyl succinate and benzaldehyde to finely-divided sodium ethoxide suspended in boiling ether and boil- ing the whole for three hours. The sodium salts of dibenzylidene- succinic phenylitaconic and phenylaticonic acids are separated by crystallisation and extraction with water. Phenylitaconic anhydride is readily obtained by treating the acid with cold acetyl chloride. The @ethyl ester GHPh:C( CH,*CO,H)*CO,Et ( Fittig and Leoni Abstr. 1890 894) crystallises in needles or tablets m.p. 72'. The bai-ium calcium and silver salts are described. [With PHOKION N~ori~.]-The a-ethyl ester (Fittig and Leoni loc. cit.) forms hairy woolly needles m. p. 76-79'. J. 0. C.106 ABSTRACTS OF CHEMICAL PAPERS. Iminodicarboxylio Acids. GEORGE STADNIKOFF (Ber. 1908 41 4364-4373 ; J . Buss. Phys. Chem. Soc. 1908 40 1638-1649).- The author finds that the rate of formation of derivatives of imino- acids decreases with increase of the molecular weight of the hydroxy- nitrile but has no relation to the molecular weight of the amino-ester. Both in the synthesis of the imino-acids previously described (Abstr. 1907 i 393 1015 1016) and in the interaction of hydroxypropio- nitrile and ethyl aminocycloheptanecarboxylate or phenylaminoacetic acid the reaction is at an end in five hours whilst the interaction of msndelonitrile and ethyl aminoacetate or phenylaminoacetate requires ten days for completion; it is however quicker in the sunlight than in t h e dark. C-Phenyliminodiacetic acid CO,H*CHPh*NH*CH,=CO,H prepared by condensing the hydrochloride of glycine ethyl ester with benzalde- hyde and potassium cyanide and hydrolysing the resulting nitrile hydrochlmide (m.p. 82O decomp.) crystallises in starry aggregates of small needles m. p. 220° (decomp.) ; the hpdrochloride forms leaflets m. p. 220' (decomp.); the copper salt (3H20) is described. The diethyl ester is a colourless oil with a faint odour b. p. 195-196'/17 mm.; the nitroso-derivative of the latter is a yellow viscid oil b. p. 220-221'/ 17 mm. The dzmethyl ester is a viscid oil b.p. 188-189'/17 mm. and yields a nitroso-derivative which is a viscid yellow oil b. p. 301-203'/16 mm. sym.-C-Phenyl-C-i,zetfiylinai~odiacetic acid CO H C H P h N H - C H &I e C 0 H prepared by the interaction of ethyl phenylaminoacetate hydrochloride acetaldehyde and potassium cyanide and hydr olysis of the resulting nitrile hydrochloride (m. p. 160-161° decomp.) crystsllises in starry aggregates of slender needles decomp. 210-21 3' ; the hydrochloride has m. p. 210-212' (decomp.) and the diethylester forms a viscid oil b. p. 182-183'/13 mm. By the condensation of ethyl phenylaminoacetate hydrochloiide benzaldehyde and potassium cyanide the hydrochloride of the nitrile ester CO Et*CHPh*NH*CHPh*CN,HCI is formed in slender needles m. p. 156-157O; with water it gives the nitrile ester a crystalline mass m.p. 43-45'. 011 boiling this with 20% hydrochloric acid it is decomposed into phenylaminoacetic acid benzsldehyde and hydrogen cyanide. J. C. C. Synthesis and Reactions of Ethyl Phloroglucinoldicarb- oxylate. Condensation of Esters containing Nitrogen and the Preparation of Sodium Cyanate. HERMANN LEUCHS and ARTHUR GESERICK (Ber. 1908,41 4171-4186).-The supposed ethyl phloroglucinoltricarboxylate synthesised by Baeyer by the sodium condensation of ethyl malonate mas shown by Moore (Trans. 1904 85,165) to be in reality ethyl phloroglucinoldicarboxylate. Willstatter (Bbstr. 1S99 i 576) isolated ethyl acetonetricarboxylate as an intermediate product and observed the formation of ethyl acetate which he attributed to the action of sodium ethoxide on ethyl malonate CH,(CO,Et) + EtOH = CH,*CO,Et + C0,Et2.He was unable to confirm the presence of ethyl carbonate but this theORUANIC CHEMISTRY. 107 authors have succeeded in doing. The Baeyer synthesis is explained thus two molecules of ethyl malonate unite to form ethyl acetone- tricarboxylate which in turn reacts with ethyl acetate. Ethyl malonate in cold ethereal solution is half converted into the sodium salt the ether distilled off and the residue heated at 130-140° any liquid which distils being collected. A yellow semi-solid mass is obtained which after purification yields colourless needles of ethyl phlnroglucinoldicarboxylate m. p. 107-108*5' (corr.). Ethyl carbonate was obtained in quan tity on fractionating the distilled liquid.Ethyl malonate dissolve? in light petroleum reacts with aluminium chloride forming colourless crystals of ethyl aluminomalonate m. p. 97-98' (Tistshenko gives 94-95' Abstr. 1900 i 270). This is decomposed by neither alkalis nor acids. By the action of nitric acid on ethyl phloroglucinoldicarboxylate three products are obtained. A very characteristic bluish-violet colora- tion is at first produced. &~'thyZ nitrop fLlorogZucinoEdicarboxylate N02*C6(OH),(C0,Et)2 crystallises in colourless six-sided plates or massive prisms m. p. 120-121' (corr.). It is conveniently prepared by heating equal weights of carbamide and the pbloroglucinol compound with concentrated nitric acid at 80'. EthyZ 5-nitro-2 4 6-trincetoxy- benzene-1 3-dicccrboxyZate forms colourless prismatic crystals m.p. 94-95'. NitrophZorogZucinoZ C,H,(OH),*NO prepared by heating the ester at 130-135' with potassium hydroxide crystallises in long sealing wax-red prisms which become yellowish-red on heating m. p. 186-1S7° (corr.). Ethyl ccminophlorogZzcci~toldicccrbox~Zate is obtained by reducing the nitro-compound with zinc and hydrogen chloride in the form of the hydrochloride crystallising in colourless needles m. p. 209' (corr. decomp.). The base separates in minute needles m. p. 96-97'. When left during several days in dilute methyl-alcoholic solution crystals separate and the alcohol assumes a deep red colour. The other products of the action of nitric acid on ethyl phloro- glucinoldicarboxylate are citron-yellow and dark red in colour ; they are isomeric and are formed from two molecules of ester united by an imino-group.The red substance C,H,O,N is regarded as a quinone derived from ethyl hexahydroxydiphenylaminetetracarboxylate ; it has m. p. 164-165O. By the action of acetic anbydride a mixture of substances is produced one of which has m. p. 138-152' and crystal- lises in orange-yellow needles. The quinone is reduced on prolonged boiling with alcohol or by means of sulphurous acid to a brown com- pound C,,H,,O,,N which on heating becomes bright red at 130' and dark brown again near the melting point 196-197' (corr.). The acetate crystallises in orange-yellow needles m. p. 175 -1 77'. The lactone from ethyl hexahydroxydiphenylaminetetracarboxylate crystallises in citron-yellow needles m.p. 220' (corr.) ; it forms a faintly yellow acetate m. p. 160-1 7 lo crystallising in needles. The condensation of ethyl sodio-N-carbethoxyglycine yields an ester CloHl,O,N crystallising in long needles m. p. 144- 145' (cow.). This hasan acid reactioninaqueoussolution,and may beethyldiketopiperazine- 1-carboxylate or ethyl aminocyclobutan-2 4-dione-1 3-dicarboxylate.108 ABSTRACTS OF CHEMICAL PAPERS. Attempts to condense sodium urethane showed that reaction takes place between several molecules but the intermolecular elimination of alcohol results in the quan titative formation of sodiiim cyanate. Similarly the action of sodium on urethane in boiling benzene results in the formation of sodium cyanate alone. This is a convenient method for preparing salts of cyanic acid.Sodium Benzaldehydesulphoxylate. A Correction. EMIL FROMM (Ber. 1908 41 4385. Compare Abstr. 1908 i 970).-When sodium benzaldehydesulphoxylate is heated with benzyl chloride and sodium hydroxide solution the product is not the unaltered sulph- oxylate as previously stated but sodium benzylsulphonate. J. BOUVEAULT and GUSTAV BLANC (Compt. rend. 1908 147 1314-1315).-From previous work the conclusion has been drawn (Abstr. 1908 i 134) that the amide formed by the action of sodamide on camphenilone E. F. A. J. J. S. Syntheses of Derivatives of Camphenilone. is isopropylcyc2opentan e- 3-carboxylarnide C H,* F HPrp NII,.C02*CH<(7*,.cH This conclusion is now verified by di;ect sinthesis. isoPropylcyclo- pentan-3-one is obtained by the decomposition of P-isopropyladipic anhydride and is shown t o beidentical with the ketone obtained from camphenilone by preparation of its semicarbazone and its dibenzyl- idene derivative. On reduction with sodium and boiling alcohol it gives a secondary alcohol identical with that obtained from 3-amino- 1-isopropylcyclopentane by the action of nitrous acid.This alcohol when heated a t 100’ with hvdrobromic acid is transformed into CH2* $JHPr@ CH;CH 3-bromo-1 -isopropyZcyclopentane CHBr< a heavy colour- I c 1 less liquid b. p. 82’/16 mm. The latter reacts with G rignard’s reagents giving magnesium derivatives which when saturated with dry carbon dioxide give 3-is0 propylcyclopen tanecar boxylic acid iden tical with that derived from camphenilone. The acid on treatment with phosphorus penta- chloride and then with gaseous ammonia readily furnishes the amide.E. H. A General Method of Preparing Mono- Di- and Tri-alkyl- acetophenones. ALBIN HALLER and ED. BAUER (Compt. rend. 1909 148 70-74).-1t has been shown previously (Abstr. 1908 i 987) that aromatic ketones of the type of benzophenone when heated with sodamide in benzene solution give either additive or decomposition products. The authors attempting to apply this reaction t o mixed fatty-aromatic ketones fiud that only those of the type in which R R’ and R are alkyl groups undergo the decomposition observed with diary1 ketones that is they break down into benzene and trislkylacetamides. 01 the ketones employed aaa-trimethylaceto- phenone COPh-CMe has been described by Nef (Abstr.1900 i 349) ; the others were prepared by alkylating acetophenone in the presence COP h- CRR’R”,ORGANIC CBEMISTTCY 109 of sodamide as in the method adopted with cyclic ketones (Haller Abstr. 1904 i 600 ; 1905 i 214 602) and by Claisen (Abstr 1905 i 256). aa-D imet hyl-a-eth$lacetophenone COPh* CMe,@t obtained by twice methylating propiopheaone or by ethylating phenyl isopropyl ketone is a mobile agreeably suielling liquid b. p. 112.5'/10 mm. ; the o~inrz forms needles m. p. 139' ; aa-dimethyl-a-p~*opylacetophenom COPh*CMe,Pra prepared by propylating phenyl isopropyl ketone is a liquid with z i penetrating odour b. p. 121-123°/10 mm. ; its oz:imet prepared by means of Crismer's reagent crystallises in needles m. p. 13%-133'; a-methyl-aa-d iethylacet ophenone COPh' CMeEt an nromdt ic smell i n g Iiquid b.p. 125-126c/l 1 mm. results on twice ethylating phenyl ethyl ketone ; the oxime has m. p. 12 1'1; aaa-triet~~?/laCeto~~~nan~ COPh-CEt obtained by successively ethylating acetophenone or by ethylating phenyl propyl ketone is an agreeably smelling liquid b. p. 146-1467' 16 mm. ; the ozirne prepared with Crismer's reagent forms needles m. p. 160-1 6 1' ; a-mathyl-cx-etrTryl-a-prop,uEcc~tophenone COPh*CMeEtPra prepared by successively methylating and propylating propiophenone is a liquid b. p. 135-136'/11 mm. which forms an oxime m p. 9 9- 1 0 Oo ; aa-d imet hyl- a- cclt y lace tophenone CO Ph* C Ale C,H a pleasant-smelling liquid b. p. 121"/11 mm. is formed by the actionof allyl iodide on phenyl isopropyl ketone; its oxime could not be obtained.By the action of propyl or allyl iodide on the additive product of sodamide and acetophenone not substituted ketones but condensation products of very high boiling point are formed ; the,higher homologues of acetophenone however undergo the normal reaction with these iodides. E. H Quinh ydrones. WILHELM Sr EGMUND (Xonatsh. 1 90 8 29 1087-1 109. Compare Urban Abstr. 1907 i 539).-By the addition of light petroleum to a benzene solution of p-benzoquinone and catechol a quinhydrone C1,Hl,O6 m. p. 90" (decomp.) DZo 1.359 is obtained which forms red needloa IS stable in boiling benzene and is decomposed by distillation with steam yielding p-benzoquinone and catechol t h e weight of the latter estimated as the lead derivative indicating that the quinnydrone contains 1 mol.C,H402 and 2 mols. Quinol and P-naphthaquinone do not react in water alcohol ether or benzene. In warm benzene p-benzoquinone and 1 2-dihydroxy- ]naphthalene yield in the molecular proportion 1 1 quinol and (/3-naphthaquinone ; in proportion 2 1 P-naphthsquinone and ordinary ,quinhydrone and in the proportion 1 2 quinol and R bluish-black ~substance C2,,H1204 m. p. 120° which seems to be identical with Stenhouse and Grove's dinaphthyldiquinhydrone (Trans. 1878 33 4 1 7). Xhe addition of light petroleum to a benzene solution of p-benzo- t quinone and 3 3-dihydroxynaphthalene produces tufts of blackish-red meedles of the mixed quinhydrone CI6Hl2O4' C,H*(W,. VOL. XCVL i. i110 ABSTRACTS OF CHEMICAL PAPERS. The formulae of the preceding quinhydrones are expressed in accord- Complete Synthesis of Camphor.GUSTAV KoMPPA (Ber. 1908,41 4470-4474).-The synthesis of camphor from a compound containing n smaller number of carbon atoms described by Wallach recently (Abstr. 1908 i 997) is not the first synthesis of camphor to be recorded since the author had previously synthesised racemic camphoric acid (Abstr. 1901 i 668; 1904 i l 4 l ) which he was subsequently able to convert into racemic camphor (Chem. Zeit. 1905 28 1202). It has since been found possible to obtain pure I-cam- phoric acid but not pure d-camphoric acid from the racemic acid by crystallisation of the quinine salts. Attempts are being made to resolve the racemic camphor into its components through the corre- sponding borneols.r-Cawpholide C,0H1602 prepared by the reduction of r-camphoric anhydride in alcoholic solution with sodium or better still by means of nickel and hydrogen crystallises in short thick needles m. p. 211°5-2120 (corr,). It combines with hydrogen bromide forming r-bromocampholic acid CloH170213r rhombic pldtes m. p. 178-179" and when heated with potassium cyanide at 230-240" yields r-cyanocampholic acid which is converted on hydrolysis into r-hornocamphoric acid C,H1&CO,B)2 obtained as feathery crystals m. p. 231-232' (corr.). The calcium salt C11H1,0,Ca,5H20 is a crystalline powder which when distilled with calcium hydroxide yields r-camphor m. p. 178-1 78.5' (corr.). Constituents of Ethereal Oils. Carvenene CI0Hl6 and Pure " Terpinene. FRIEDRICH W. SENMLER (Bey.1908 41 4474-4479).-Emphasis is laid ou the great differences in the physical properties of the (' pure " terpinenes obtained by various methods by the author (Abstr. 1907 i 714) Wallach (Abstr. 1907 i 64 ; 1908 i 813) and Harries and Majima (Abstr. 1908 i 733). I n order to throw some light therefore on the constitution of terpineine the author has prepared pure carvenene by reducing chloro- carvenene and finds that the hydrocarbon so obtained which must have the formula CPrB<C,2.CH2 CH-CH>CMe exhibits an exaltation of 1.5 units (compare Bruhl Abstr. 1908 ii 1002). It is thus definitely shown that two cyclic conjugate ethylene linkings produce a marked exaltation consequently the two terpenes A' 3- and -dihydro- cymene must differ considerably in their physical constants.The identity of carvenene with terpinene has not yet been definitely settled. The chlorocarvenene described by Klages and Kraith (Abstr. 1900 i 42) was impure. The pure substance has b. p. 95-98'/10 mm. -D$ 0.994 n 1.51700 and mol. ref. 51-90; that is it exhibits an exaltation of 1-71 units. It is readily reduced by sodium and alcohol to carvenene a colourless liquid b. p. 61-63'/10 mm. 179m5-180.50/735 mm. D 0.844 and n 1.49100 (compare Harries and Majima loc. cit.). The carvenene 60 prepared reacts slowly with nitrous acid yielding terpinene nitrosite. ance with Thiele'rs theory of partial valencies. c. s. W. H G. W. H. G .ORGANIC CHEMISTRY. 111 Aliphatic Terpenes and their Derivatives. 111. C . J ENKLAAR (Rec. trav. chim. 1908 27 422-434.Compare Ahgtr. 1908 i 664).-ln the present communication the author describes the preparation and properties of the ozonides of ocimene (van Romburgh Abstr. 1901 i 220) allo-ocimene and dihydro-ocimene. These ozonides are of somewhat variable composition the amount of oxygen depending on the time during which the hydrocarbons are exposed to ozone. Ocimeite ozonide C,,H,,O occurs as a pale yellow viscous oil. which explodes when heated or when brought into contact with concentrated sulphuric acid. When treated with water decomposition occurs with formation of acetone acetic acid malonic acid methyl- glyoxal and possibly malonaldehyde. allo-Ocimcne ozonide C,,H,,Og is an explosive oil rapidly decomposed by water with formation of acetone pyruvic acid and probably malonaldebyde. Dihydro-ocirnene ozonide under the same conditions gives acetone acetic acid lawulic acid and probably laevulinaldehyde and malon- aldehyde.An insoluble yellow resin was also obtained .in the decomposition of these ozonides by water ; further treatment with ozone converts this into an ozonide. A table is given showing the specific refractions for the a- and y-hydrogen lines and the D-sodium line and also the molecular refractions for the different rays of these three hydrocarbons. Tbe molecular dispersions between the a- and y-lines diverge considerably from the values calculated from Conrady's data. w. 0. w. Ethereal Oils. HEINRJCH HAENSEL (IImr~.prl)s HalJ-Yeurly Rep& October 1908. Compare Abstr. 1908 i 665).-dngeZica oil when free from terpene has D15 0.9508 aD - 3*16O acid number 0 ester number 87.3 after acetylation 168.1.Oil of Mugwort from t h e fresh plant Artemisia uulgcvm's (yield 0.0263%) is dark brown and smells strongly aromatic; D20 0.9279. The addition of 90% alcohol causes separation of small colourless plates which give a decided aldehyde reaction with ammoniacal silver solution. Birch-bark oil from Betula albcl has D20 0.9003 aD - 12-08' acid number 9.1 ester number 11 '4 after acetylatiou 36.5. The sesquiterpene isolated from this was colourless and nearly odourless ; it has b. p. 255-256'/744 mm. D20 0.8844 aD - 0.5' ; in glacial acetic acid it gives a cherry-red coloration with bromine and combines with 1 mol. hydrogen chloride when in absolute ethereal solution. The resulting dark-coloured hydrochloride D20 0,9753 when boiled with anhydrous sodiiim acetate and acetic acid yields a hydrocarbon b.p. 258-260"/747 mm. D2* 0.8898. Coriandlrr oil (Zoc. cit.) is for the most part d-linalool accompanied by small quantities of esters of this alcohol. Gym- gloesum oil prepared horn the leaves of Cynoglosmrn oflcimle (yield 0*107%) is dark brown with powerful camomile-like odour ; i t partly solidifies when cooled is solnble in all proportions of 90% alcohol and has D20 0.9412. Siberian pira needle oil from Bbies stbirica,has D20 0.9767 aD - 38.30° soluble 1 14.2 in 63% alcohol. Guaiacum-wood oil from BuZmia Sarm&mti,-Only about one- half of the guaiol contained in this oil is found by acetylation; it i 2112 ABSTRACTS OF CHEMICAL PAPERS.appears to be a ertiary alcohol in agreement with its behaviour towards phthalic anhydride. The guaiene obtained by warming the oil for an hour with three times its weight of anhydrous formic acid has b. p. 136-138°/14 mm. D20 0*9182 and is most probably a mixture of sesquiterpenev (compare Cl mdurin this vol. i 98). Oil of Lavender when free from teipene has D*'' 0.8898 an - 6-44' and is soluble 1 :Om95 in 80% alcohol. Oil of Lovrcye from Leoivticum oflcinale becomes slightly chaoged when kept ; it then contains myristic acid small quantities of an aldehyde possessing an odour resembling that of octaldehyde and also larger quantities of a brown resin which decomposes when warmed under reduced pressure Ginger-pass oil from Andropogon Schoenanthus is optically inactive has D20 0.8851 and dissolves in 3 5 parts of 60% alcohol.Italian Peppermint oil crude and purified has respectively D20 0.9035 and 0.9032 aD - 19.80' and - 18*10° ester number 11.2 and 9.1 after acetylation 154.4 and 145.9 content of esterified menthol 3% and 2*54% content of free menthol 45016% and 42.66%. Hungarian oil oJ~ Juniper.-D20 0.8672 aD - 1Z0 saponification value 5.9 after acetylation 20.9 and contains according to the phthalic anhydride test about 5% of a primary alcohol CloH,,O. The Italian oil bas D20 0.8658 aD - 9.82' saponification value 6-1 ; after acetyl- stion D20 0.8732 aD - 7-21' saponification value 21.3; after saponifica- tion and repeated acetylstion a reversal of optical rotation appears to take place. I n the higher boiling fractions phthalic anhydride indicates the presence of small quantities of a primary alcohol C,oH!,O ; the terpeue fractious do not contain nopinene.Olibanol from otl of Frankincense (Zoc. cit.) has b. p. 217'/20 mm. 333-3344751 mm. D20 0.9596 aD-71.50'; when warmed with an equal weight of molten zinc chloride a dark green oil is obtained b. p. 315-31S0/749 mm. D20 0.9400. Olibanol is only slightly oxidised by potassium permanganate in alkaline solution but in glacial acetic acid solution it is completely oxidised by chromic acid. J. V. E. Essential Oils. SCHIMMEL st Co. (Semi-Annual Report ATov. 1908 5-232. Compare Abstr. 1908 i 666).-A rBsum6 of informa- tion regarding essential oils accumulated during the period April t o November 1908. Much of the matter recorded has appeared in other journals and has been abstracted already.Cinnamon-bark oil.-Four samples from Mah6 Islands Seychelles had D15 0.9464-0.9670 [alD - 2'30' to - bolo' n 1*52843-1.53271 and contained from 35 to 35% of cinnamaldehyde and 6 to 15% '' phenols.') All the usual constituents of cinnamon-bark oil were present and in addition a small amount of camphor (compare Bull. Imp. Inst. 1908 6 111). Clove-leaf oil.-Clove leaves from the Seychelles yielded 4*55)! of oil (Zoc. cit.) ; this had D15 1.0489 [a) - 1°35' eugenol 87%. African Copaiba buham (oleo-resin) had D15 0.9919 [.ID - 2315' acid number 61.4 saponification number 68.5 and was not completely soluble in 98% alcohol. It contained 46.5% of volatile oil having DI5 0.9215 [a]D + 23'26' and acid number 2.2.Dalbergia cumingiann oil obtained to the extent of 0.5% from the wood had DZ6 0.891 [a] - 4'31' ester number 5 acetyl ester numberORGANIC CHEMISTRY 113 115. No aldehydes were present (Jaarboek Bept. Landb. Ncd. Id. 1906 45). DiZl herb oil from Spanish herb was greenish-blue had D15 0.9062 91 1.49185 and was dextrorotatory. It contained d-a-phellandrene terpinene carvone dillapiol (? dillisoapiol) and dipentene or limonene (P). Lemon &.-The chief constants of oils from different distriets in Sicily are recorded; they had D15 0*8569-0.8610 [ulg +56”50‘ to + 62’40’ left from 2.2 to 3.6% residue on evaporation and contained 4.3 to 7.1% citral. All these oils contained traces of pinene which is a natural constituent of lemon oil. Eucalyptus Rudderi leaves and twigs furnished 00309% of reddish-brown oil having D15 0.942 [a] - 8*5O and 9% 1.4898.The oil contained cineol and aromadendral but no pinene or phellandrene (Baker and Smith Proc. Linn. Xoc. N.S.W. 1906 31 ‘7 14). E Z C T O ~ U ~ Wormseed oil contains a-pinene terpinene terpineol and terpinenol and a sesquiterpene (b. p. 250’ approx.) (compare Schindel-Meioer Apoth. Zed. 1907 22 876). B’oeniculurn oficinale stalks and leaves grown in Java yielded an oil having DZG 0.950 [a]” +4’50’ b. p. 227-235” m. p. 12.8’. A second sample of oil had D15 0.9837 [a]D +b034‘ m. p. 16.2’. Both oils probably contain much aaethole (Janrboek Dept. Landb. Ned. Ind. 1906 45). Hyptis auaveolens oil from Java had [a] -1O56’ and saponification number 17. The yield was 1% and no aldehydes were present (Zoc.cit. p. 46). Andropogon cilrcctus oil is contained in largest quantity in the leave% and diminishes as the leaves age becoming at the same time richer in citral. The leaf sheaths contain a little oil and the thick roots 0.35 to 0.5%. A sample of “Cochin China lemon grass” oil produced in Barbados had D15 0.900 [u] - lo aldehydes 85.5 (neutral sulphite method). The ‘‘ acid sulphite ” and ‘‘ neutral sulphite ” processes for estimation of citral in lemon grass oil give results differing by from 2 to 5% so that the process of estimation should always be stated. Methylheptenol has been detected in Zinrtloe oil. Monarda dayma oil from the half-faded petals was pale yellow and had D15 0.8665 [ u ] ~ - 7’30’ ng 1.46892 and acid numbor 2.4 the yield was 0.32%.The dry leaves and stems furnisbed 0.096% of a lemon-yellow more soluble oil having D15 0.8855 [.ID -32‘38‘ n2,0 1.46898 and acid number 5.5. NutmegJEowers grown in Java yielded ’7.6% of oil having DZb 0.942 [a]% + 7’ and b. p. 155-285’. Fresh nutmegs furnished 3.8% of oil having D% 0.940 [u] + 10°20’ and b. p. 155-285’ (de Jong ‘‘ Teysmunnicl ’’ 1907 8). Condensed water from the distillatian of orris root oil contained acetaldehyde methyl alcohol diacetyl and furfuraldehyde. Pastinnca oil was found to coiitain heptoic and hexoic acids ( A p t h . Zeit. 1907 22 144). The physical constants of a number of Singapore and Java patchouli oils are recorded. ltaliun peppermint oiE distilled from plants grown trom Mitcham seed had 0.9090 [a]D - 21’12’ n 1-46248 and contained ‘‘ total ” menthol 50*5% and menthone 1702%.Java “peppermint ” oil had Dee 0-974 [a]? 12’28’ and ‘‘ total menthol ” 44.9% (Jaurboek Dept. h n d b . Ned. Ind. 1906 45) but doubt is expressed as to the validity of the above composition. Both oils had the odour of lavender.114 ABSTRACTS OF CHEMICAL PAPERS. Popbr bud oil.-Two samples had D15 0.8957 to 0.8991 5O16' to +5O45' acid number 2.8-6.4 and ester number 8.2-8.9. Acetylation experiments showed that the oil contained but little '* alcohols." East African sandalwood oil from Osyris ti3nu~oli.a 1- The yield from the wood was 4.86%. The oil had D15 0.9477 [aID- 42'50' ng 1.52191 ester number 11.1 acetyl ester number 72.8. The odour recalled those of vetiver and gurjun balsam oils.Thuja pZicatct.-The leaves and twigs yielded 0% to 1.4% of bright yellow oil which possessed a camphoraceous odour and had D25 0.9305 [a] - 6*9O acid number 0418 saponification number 5-7 and acetyl ester number 6-2. It contained pinene thujone fencbone and esters of borneol. Ylang-ybung oil from Madagascar had Dl5 0.9577 [a],,- 49'55' nz 1.51254 acid number 1.8 ester number 113.2 acetyl ester number 160.2. Samples from Mahd Island Seychelles had D15 0.924-0.958 and [aID - 18O46' to 45'27' (compare Bull. Imp. Inst. 1908 6 110). Arternisia arborescens yielded 0.62% of a dark blue oil possessing an odour like that of French wormwood oil and having D*5 0.9458 and acid number 9.8. " Mumuta " grass tubers (Andropogon sp.) from Samoa gave 1.05% of an oil with an odour like that of vetiver oil and having 1)15 0.9845 [a]D + 41°50' ng 1.5 1505 acid number 0-9 ester number 13.3 and acetyl ester number 65.2.From I' Nuanua " leaves (Nelitris sp.) from Samoa 0.63% of oil was obtained. This had an odour like that of ambergris and had DI6 0.9025 [aID+9O30' rnE 1.48490 acid number 2.2 and ester number 7.4 "Usi" leaves (Evodiu hortensis) from Samoa yielded 0.09% of a brown oil with a quinone-like odour and had D15 0.9450 [aID - loo and lzg 1.49685. '' Maali " resin from Samoa resembled elemi and gave 16.08% of a bright green solid oil with a faintly balsamic odour. It had m. p. 65-80° [.ID + 7'15' saponification number 3.3 and acetyl ester number 46.6. It contained m d y t ulcohot C15H260 m. p. 105O [a] + 1 8 * 3 3 O b. p. 260' (approx.) which crystallised from alcohol in silky needles often several inches in length and formed with resorcinol A complex condensation product m.p. 62O and with chromic anhydride a red additive product (C,,H,,O),,CrO,,. m. p. 1 1 1 O . On treatment with acetic anhydride or better formic acid maalyl alcohol is converted into a sesquite?*pone Cl,H2+ D15 0.9190 l a ] D + 12lo20' nD 1.52252 b. p. 270*5-271"/754 mm. which gives an indigo-blue coloration with sulphuric acid in acetic acid. No derivatives of the sesquiterpene could be prepared. The residue of the oil appears to consist of a solution of maalyl alcohol in a laevo- rotatory sesquiterpene. hlern%a indim(?) of Java yielded 0.28% of a bright brown oil having DZ6 0.949 [a] + 57'2' saponification number 99 acetyl ester number 228 (corresponding with 75.6% of thujyl alcohol).N o thujone could be detected (Jaarboek Bept. Landb. Ned. Id. 1906 44). Lantana odoratn from Jamaica gave 0.16% of lemon-yellow oil having an odour of hyssop and ambergris and having D15 0.9149 [aID - 1"36' w2,a 1,49630 ester number 4.7 acetyl ester number 51.0. Tagetes patula flowers from Mexico yielded 0.1% of a golden-yellow oil having D15 0-8856 [a]D - lio35' ng 1.49714 acid numDer 2.0 ester number 18.7 aoetyl Bster 4qmber 7493.ORGANIC CHEMISTRY. 11 5 The report concludes with a critical r6sumB of descriptions of essential oils in various pharmacopeias notes on recent chemical biological and physical research work on terpenes and their deriv- atives and a memoir on the history botany preparation and composition of Japanese peppermint oil by N.Inouye. T. A. H. Oxidation Products of Artemisin. ENRICO RIMINI (Atti R. Accad. Lincei 1908 [v] 17 ii 590-597).-The arteminic acid decribed by Horst (Abstr. 1902 i 387) as an oxidation product of artemisin is in reality a mixture of santonin and arternisin its formation being due to the use of impure artemisin. When artemisin is oxidised by alkaline permanganate (about 5 atoms of oxygen) in presence of ice it yields a ketonic acid C,,€€?,O in the form of a pale yellow syrup which reduces ammoniacal silver nitrate solution and Fehling's solution in the cold and yields iodoform with potassium hydroxide and iodine. The dipknyl- I~ydraxone of this acid C,,H2206(N213:Ph)2 forms chrome-yellow crystals m. p. 116-1 1 8 O (decomp.).If a large excess of permanganate is employed the oxidation of artemisin (1 mol.) yields oxalic acid (I mol.). T. H. P. Rhein. OTTO A. OESTERLE and ED. Trsza (Chena. Zentr. 1908 ii 1929-1930; from Schweiz Woch. Chem. Pharm. 1908 46 701-703. Compare Hesse Abstr. 1900 i 41).-When crystalhed about twenty times from pyridine and sublimed in a cathode ray vacuum this substance was obtained in small yellow needles or compact dark-coloured crystals m. p. 382-32 1.5' which gave on analysis 63.98 63 71% C and 2.88 2 81% H corresponding with C,,H,O the formul i suggested by Tschirch and Heuberger (Abstr. 1903 1 108). When acetylated in pyridine solution no higher acetyl derivative was obtained than the diacetate. When heated with propionic anhydride a pyridine solution of rhein yields a lemon-yellow crystalline propionate m.p. 223-224' ; analysis gave 68.21% C and 4.43% H. Benzoylation of rhein appears to result in the formation of at least two products which have not yet been separated. Methylation with methyl sulphate gives several metlqd ethers of which one insoluble in hot potassium hydroxide crystallices i n long pale yellow needles m. p. 2889 The conclusion is drawn that rhein is not a simple substance but a mixture. J. V. E. The Green Pigment of Bile. MAURTCE PIETTBE (Compt. rend. 1908 147 1492-1 495).-Bilirubin crystallises from benzyl chloride in long prisms often arranged in bundles ; it crystallises still better from a mixture of chloroform and carbon tetrachloride. The form- ation of biliverdin is not simply an oxidation f o r a green coloration is also produced when the halogens the halogen acids in glacial acetic acid trichloroacetic acid chloral bromal etc act on bilirubin.G. B.116 ABSTRACTS OF CHEMICAL PAPERS. Eetablishment of the Oxonium Theory. HERMAN DECKER and THEODOR VON FELLENBERG (Annulen 1909 364 1-44).-The salts of benzopyronium naphthapyronium and dibenzopyronium can only be regarded as compounds containing quadrivalent oxygen and the authors consider that the existence of quadrivalent basic oxygen is thereby established on as firm a basis as that of quinquevalent nitrogen quadrivalent sulphur and tervalent iodine The compounds regarded by Collie and Tickle Baeyer and Villiger Hewitt and Werner Fosse etc. as oxonium salts in spite of doubts which have been expressed as to this formulation are correctly so constituted and this also applies to Kehrmann's azoxonium compounds.The authors are in entire agreemenf with the views of Archibald and McIntosh (Trans 1904 85 919) on t h i s subject and they discufis at length the general resemblance between oxonium and ammonium compounds It is pointed out that the secondary valencies of oxygen are usually brought into play at a lower temperature than in the case of nitrogen ; thus oxonium compounds often decompose or even cannot exist at a temperature at which ammonium compounds are quite stable. I n this respect quadrivalent sulphur occupies a position intermediate between nitrogen and oxygen. The formation of a1 kylammonium salts as in the expression HI +- NH,Me ZZ NH,MeI NH + Me& whereby i the quaternary compound may decompose in two directions (to which phenomenon the term (' heterospasis " is applied) has its counterpart in the case of oxygen compounds and the formation of oxonium intermediate compounds with their possibility of hetero- spasis in many cases throws light on hitherto incompletely explained reactions.The syuthesis of benzopyronium derivatives is effected conveniently by condensing salicylaldehyde and its derivatives i n presence of sulphuric or hydrochloric acid with an aliphatic or aromatic aldehyde or ketone containing an acidic methylene group next to the carbinol group. Solutions of such oxonium salts in l0-15% hydrochloric acid are mostly yellow and on dilution or by partial neutralisation become colourless and deposit the corresponding colourless carbinol.Bonzo- pyronium ferrichloride is best prepared by shaking salicylaldehyde (2 mols.) and acetaldehyde (1 mol.) with 70% sulphuric acid and warming the mixture for three-quarters of an hour on the water-bath. After precipitating tar with hydrochloric acid solid ferric chloride is added. I n moist air it becomes black loses hydrogen chloride and coumarin is formed. 2-Methylbenzopyronium salts (Abstr. 1907 i 1064) are similarly prepared by the condensation of salicylaldehyde and acetone. The condensation of methyl ethyl ketone and salicyl- aldehyde in presence of sodium hydroxide lends to the formation of o-hydroxystyryl ethyl ketone OH*C,H,*CH:CH*COEt in small yellow crystals m. p. 101O (corr.) and a small amount of a compound C2.3H2203 in yellow leaflets m.p. 246-247" (corr.). Tho former on warming with fuming hydrochloric acid and adding ferric c h lor id e yield s 2 -e th ylbenaop yronium fewichlor ide C,,H ,OC1 FeC I in flesh-coloured crusts m. p. 68-70° (corr.) after sintering at 6 5 O . The salt becomes green on'exposure to light and decomposes under the influence of mcisture. When salicylaldehyde and methyl ethylORGANIC CHEMISTRY. 117 ketone are subjected to the action of hydrogen chloride and ferric Chloride added t o the purified product 2 3-dimethylbe~uopponium fmkhlorids C,,H,,OCl,FeCI,,. is formed in long yellow needles m. p. 117-118O (corr.) after sintering at 1129 On dissolving this in acetone and pouring into water the base probably dimetiiylbenzo- pyranol is precipitated.2-isoPropyZbsnmp yronium ferrichloridc C,2Hi,0Cl,FeCI prepared by condensing salicylaldehyde and valer- aldehyde in presence ol hydrogen chloride and subsequently adding ferric chloride forms long yellow needles m. p. 75-5-76.5O (con-.). 3-Itiethyl-2-ell~ylbeizzopyronium ferrhhloride Ci2H,,0C1 FeCl similarly prepned from salicylaldehyde and diethgl ketone forms golden leaflets m. p. 86.5-87.5' (corr.). With water it yields 3-rnethyt- 2-cthylbencopyrnnul Cl2Hl4O2 in small colourless needles m. p. 70-75" (corr. ). 'l'he condensation of salicylaldehyde and dipropyl ketone results in the production of a compound C2,H200 colourless glibtening leaflets m. p. 106-107° (corr.) and on adding ferric chloride t o the filtrate from this 3-eth y I- 2-prop ylbenxopyronium f eir-ichloride C14H,70CI,FeCI in yellow glistening leaflets m.p. 5 5 O which with water gives 3-ethyl-2 propylbenzopyrand in colourless needles m. p. 74-76O. 2-Phenylbenzopyronium ferrichloride is obtained in a 70% yield by condensing salicylaldehyde and acetophenone. 2 3-Dip?ien?/l- benzopyroniurn ferrichloride C2,H,,0Cl,FeCl similarly obtained froiri salicylaldehyde and deoxybenzoin crystallises i n long yellow needles m. p. 123-124' (corr.). With water this yields 2 3-diphnyZben:o- pymno7 C,,H,,O ic colourless needles m. p. 221-122' (corr.). On boiling this with methyl or ethyl alcohol the corresponding et?m is formed. 7-Hydroxy-2-phenylbenzopyronium chloride has the formiiln C,,HI,04Cl (Perkin Robinson and Turner Trans.1898 93 109Y give. C,,Hl,03C1). On heating at 140' in a current of bydrogen chloride the compound C,,Hl,02CI is formed. The picrate of t b e pyronium base turns brown at 19Uo and begins to sinter ; it is not cwnpletely melted a t 270° (Bulow and Sicherer Abstr. 1902 i 113 give m. p. 232-233'). The ferrichloride forms small yellow needles containing lC2H40 (from acetic acid) m. r. /\/'\ 165-163" (corr.) after previous sintering. I 11 I As a consequence of their work on benzopyronium OD\/\/ salts the authors consider that salts of phenacetein I 9 resacetein gallacetein quioacetein isobrasilein isohaema- tein fluorescein and coerulein are to be looked on as benzopyronium salts and suggest that the free bases contain the annexed chromogen. f2-P~en~lriaplithupyronium ferrichloride (annexed formuia) prepared by condensing /3-naphthaldehyde and acetophenone /\ and precipitating with ferric chloride forms small It I dark yellow needles m p.187.5" (corr.). On pour- \/\/'\ ing into water the colourless carbinol separates. I ' Ph 2 ; 3-Dip~enyZnaphtl,apyronium firrichloride \/\fl C?,H,@CJ,FeCJ3 9 similarly prepared from 6-naphthaldchyde and deoxy- cl FeCJs benzoin crystallises in small slender yellow needles rn. p. 205-206' (corr,); the carbinol base forms two picrcates that118 ABSTRACTS OF CHEMICAL PAPERS. with two mols. of picric 'acid forms dark-coloured crystals m. p. 118-1 ZOO and that with 1 mol. of picric acid gives smaller crystals m. p. 161O (decomp.) aftergintering at 145'. J. C. C. C heiroline the Alkaloid containing Sulphur obtained from wallflower Seeds.WILHELM SCHNEIDER(&W.,1908,41,4466-4470). -The formula assigned by Wagner to cheiroline (Abstr. 1908 i 202) is incorrect ; it should be C,H,,O,N,S,. Cheiroline is practically a neutral substance and is optically inactive ; it gives a white precipi- tate with mercuric chloride and when warmed with an alkaline solution of lead oxide yields lead sulphide and with an ammoniacal Rilver solution forms a mirror and silver sulphide. When the solution obtained by boiling the alkaloid (1 mol.) with dilute aqueous sodium hydroxide is acidified it evolves hydrogen sulphide (1 mol.) and carbon dioxide (about 1.4 mols.). The solution then contains a base,C,HIIO,NS which is obtained as an exceedingly deliquescent crystalline mass ; the hydrochloride C,H1,O,NS,HCl crystallises in almost colourless deliquescent prismatic needles m.p. 145-146'. The base when treated with sodium ethoxide and methyl iodide yields a quaternary methiodide C,H,,O,NIS obtained as glistening silky scales m. p. 183O; it is therefore probable that the base is a primary base. Since cheiroline readily parts with a carbon atom and a sulphur atom yielding a strong base it is probable that these atoms are connected to the two nitrogen atoms as in thiocarbamide. W. H. G. Ergot of Rye. ERNST VAHLEN (Archiu exp. Path. Pharm. 1908. 60 42-75).-The author controverts the statement of Barger and Dale (Abstr. 1908 i 204) that the crystalline product clavin previously isolated from ergot is a mixture of leucine and aspartic acid.H e shows that by means of cupric acetate or hydroxide it can be resolved into two constituents one of which gives an insoluble copper salt whereas the other gives a soluble salt. The latter is a weakly basic substance of the formula C,H,,O,N m. p. 258-260° and does not give precipitates with the ordinary alkaloidal reagents ; the former is Lleucine. For these reasons the formula C,,H240,N is assigned to clavin. Clavin leucine and the clavin base are all very similar to one another in their crystalline form solubility in solvents and capacity for subliming and the clavin is regarded as the leucine salt of the base. The author also criticises Dale's experiment on the physiological action and maintains in opposition to Dale that clavin has a specific action on the uterus.Experiments were also carried out t o determine the physiological action of the alkaloids ergotinine and hydroergotinine which were isolated and described by Kraft. The latter has been assumed to be identical with the so-called ergotoxine the water-sollible amorphous alkaloid isolated by Barger and Carr (Trans. 1907 91 337). It was found that more than 16 decigrams per kilo was the toxic dose of hydroergotinine for cats whereas according to Dale (Abstr. 1907 i 791 1-5 mg. of ergotoxine phosphate was a toxic dose for the sameORGANIC CmMLSTRY. 119 animals. For these reasons the chemical identity of hydroer otine and ergotoxine cannot be regarded as proved. It is suggestef that both might be contaminated with varying quantities of a highly toxic substance. Ergotinine is relatively non-toxic when compared with hydroergotinine. An' experiment was made with the crystalline secalaminosulphonic acid which was isolated by Kraft.It was found when injected into a frog to be physiologically inert. It is not therefore the active principle in the; preparations described as sclerotic and ergotic acide. S. B. S. apoMorphine Hydrochloride. DAVID B. DOTT (Pharm. J. 1908 [iv] 27 8Ol).-Experiments have been made which indicate that apomorphine hydrochloride has the composition represented by the tormula C,4H,,0,N2,2HCI,2H20 in which i t is assumed that apo- morphine is formed by the condensation of 2 mols. of moEphine with elimination of 1 mol. of water. E. G. Action of Acids on Di-iodo-a-methylsparteine. AMAND VALEUR (Cornpt.rend. 19OS 147 1318-1319. Compare Abstr. 1908 i lOO6).- When iodoisosparteine methiodide is heated with either dilute sulphuric hydrochloric or acetic acid and the solution cooled the product is invariably iodoiso8pa?*teins methiodide hydriodida C1,H2,N2Me 12,H I m. p. 1 9So which regenerates iodoisosparteine methiodide when treated with sodium carbonate. The reaction is probably to be explained by the eeparation of hydrogen iodide from part of the methiodide thus CH ___ CE[(CH,IJ+M~I = /CH(C,H,,N)*CH b H - CHZ /CH(C8HJ4N)eCH2\ HI + CH- CkI( .UH,) -NMel and the subsequent action of the liberated hydrogen iodide on the unchanged methiodide. This view is supported by the fact that tho mother liquors from the action of dilute acetic acid on the methiodide contain a small quantity of a substance containing approximately the proportion of iodine required by the above formula.Moreover when iodoisosparteine methiodide is heated in a sealed tube with diluta sodium hydroxide solution at 125-1 30° a-methylsparteine is formed probably according to the reaction C,,H,,N2MeI + 2NaOEl= CIgH2,N,Me + 2NaI + 0 + H,O the oxygen hberated serving to oxidae part of the a-methylsparteine produced. Relation between a-Methylsparteine and isosparteine. Reciprocal Transformation of these Bases. 11. isosparteine- methosulphste and Some Salts of this Base. 111. Action of Alkalis on i8oSpar teinemethoaulphate. Methylisosparteinium Hydroxide. AMAND VALEUR (BULL SOC. china. 1909 [iv] 5 31-37 37-40 40-42).-The first paper is theoretical and gives an inter- pretation of results recorded in 44e second qnd third papers and other \CH2- OH,/ E.H.120 ABSTRACTS OF CHEMICAL PAPERS. work (Abstr. 1908 i 1006) on the basis of the formula? previously assigned to sparteine a-methylsparteine and isosparteine (Abstr. 1905 i 659 717; 1908 i 206). Most of this work hag been published already (Zoc. cit. and 1908 i 736). isosparteine methosulphate (Zoc. cit.) dissolves in 1 *5 parts of water and the solution is slightly bitter neutral to litmus and does not reduce potassium permanganate. The anhydrous salt has m. p. 140-1 40.5O. isoSparteine methochloride hydrochloride m p. 192-193" (decomp.) [a] - 19*75" obtained by adding barium chloride to the solution of the methosulphate separates from alcohol on addition of acetone in transparent deliquescent crystals.isoSpar- tsine methobrowde hydrobromide m. p. 193' (decomp.) [aID - 15*3S0 similarly obtained is crybtalline and verv soluble in water. Its solution on addition of sodium hydroxide deposits an oil which goon crystallises and is probably isosparteine methobromide. isosparteine methiodide hydriodide (Abstr. 19OS i 44) has [a] - 11.80' and crystallises from alcohol with 1 H,O. Spa?-teine methosulphate Cl,H2,N,Me,HS0,,7 H,O [.ID - 24*54O obtained by the addition of the necessary quantity of sulphuric acid to a-methylsparteinium hydroxide crystallises from water on addition of alcohol and acetone. The solution is slightly acid to litmus and does not reduce permanganate. The transformution of isosparteine into a-methylsparteine described previously (AbGtr.1908 i 736) may be used for the recovery of a-methylsparteine from the mixture of bases obtained in methylating sparteine (Abstr. 1908 i 44). The mixture is treated with sulphuric acid whereby the u-methylsparteine is converted into isosparteine methosulphate the other bases remaining unchanged. The latter are washed out with ether and the residual methosulphate converted into a-methylisosparteinium hydroxide by the action of baryta and this into a-methylspsrteine. T. A. H. Stryohnos Alkaloids. 11. New Method for the Preparation of Sulphonic Acids. HERMANN LEUCHS and WILHELM SCHNEIDER (Ber. 1908 41 4393-4396. Compare Abstr. 1908 i 563).-It is extremely difficult to obtain strychninesulphonic acids by the direct action of sulphuric acid on the alkaloid but strychninesulphonic acid C,,H,,O,N,S is readily formed when sulphur dioxide is passed into warm water (60') in which finely-divided strychnine and manganese dioxide are suspended. The acid crystallises from hot water in colourless needles containing water of crystallisatiou which is given up at 105".The dried acid is extremely hygroscopic ?and has m. p. 350-360" (decomp.). It dissolves readily in dilute alkalis but not in 20% hydrochloric acid. The solution in sodium hydroxide has [u] - 233'. A hoG solution of the sodium salt deposits the free acid when cooled. EMILE BAUD (Compt. rend. 1909 148 96-98).-From determinations of the electro-capillary maxima of mixtures of water and pyridine Gouy (Abstr. 1906 ii 725) deduced the existence of a compound of these substances.To C,,H,,N,( CH$l) HC] J. J. S. Aqueous Solutions of Pyridine.ORGANIC CHEMISTRY. 121 tbe Fame end the author has studied the freezing temperatures con- tractions in volume refractive indices and heats of dissolution of similar mixtures. The curve obtained by plotting the solidification temperatures of mixtures of pyridine and water against their percentage composition consists rjensibly of four straight lines the first extending from 0 to 55% of pyridine representing the separation of ica ; the second from 55 to 77% of pyridine that of a hydrate ; the third from 77 to 83%*of pyridine of another hydrate whilst the fourth represents the separation of pure pyridine. The temperature reaches a minimum for 83% of pyridine (C,H,N + 0*9H20) which is accordingly the composition of a eutectic mixture.As the crystal- lisation curves of the hydrates intersect before the maximum tht3 composition of these hydrates cannot be deduced ; all that can be con- cluded is that one contains more than S*6H20 and the other mom than 1.3H20 per molecule of pyridine. The curve drawn with percentages of pyridine by weight as abscissae and the contractions in vtdume at' these mixtures as ortlinates exhibits a maximum for the mixture of the composition C,K,N,2H20. The index of refraction curve has a maximum also at the mixture of this composition. Tbe heat of dissolution of pure pyridine in a large excess of water diminishes with rise in temperature according t o the expression Q = 2.800 - 0904.4 (t - 19.5).Determination of the heats of dissolution of the mixtures of w'tter and pyridine permits of the calculation of the heats of formation of the latter. By calcdating the rebults with reference to the addition of increasing quantities of water t o a molecule of pyridine a smooth curve is obtained exhibiting a change of direction a t 2H,O and GH,O whilst calculation of the heats for the same volume of mixture gives a curve showing a maximum for C,H,N,2 W ,O. The conclusion is drawn that aqueous pyridine solutions contain a t l e ~ s t two hydrates C,H5N,2H,0 and C5€I,N,6H,0 dissociated at the ordinary temperature the more complex being the more dissociated. E. H. Alkaline Reduction of o-Nitrodiphenylmethane. PAUL CARRE (Compt. Tend. 1909 148 101-103*).-When o-nitrodiphenylmethane (Geigy and Kanigs Abstr.1885 1236) is reduced by gradually adding zinc dust to its boiling solution in alcoholic soda only 15-20% of o-llydrnzodiphenylmethane is formed the main product being o-aminodipheDylmetliane. o-~~d?.axodi~henylmet?~ane N,H,(C,H,-CH,Ph) crystallises in white lamella m. p. 148-149O. It i.; oxidised by mercuric oxide to o-azodiphenylmethane N,( C,H;CH,Ph) which exists in two forms. The a-modification crystallises from acetic acid in red needles m. p. 116-117" which on melting are transformed into the P-modification m. p. 124-125". The latter when recrystal- lised from acetic acid regenerates the a-compound whilst crystal- lisation of either from alcohol gives a mixture of the two forms. When o-hydrazodiphenylmethane is treated with dilute acids it under- goes the benzidine transformation giving 2 2'-dibenz&4 4'diamino- dipheizp? C,,H,(CH2Ph)2(NH,) which crystallises in long white * and Bull.SOC. chim. 1909 [iv] 5 119-121.122 ABSTRACTS OF CHEMICAL PAPERS. needleR m. p. 136q and forms a s u l p k t e C,6H24N,,H2S0 also crystallising in long white needles m. p 255" (decomp.) rapidly diesociated by boiling water and a hydrochloride C26H24N2 2 HCI,H,O crystallising in white needles m. p. 214' (decomp.) hydrolysed by water. o-Aminodiphenylmethane NH2*C,H,*CH2Ph prepared by Fischer and Schutte (Abstr. 1894 i ZOO) b u t not obtained by them in a crystalline form crystallises from ether in large light yellow prisms m. p. 5 2 O b. p. 19O-19lo/22 mm. 172-173O/12 mm. Its hydro- chZol*ide C,,H,,N,HCl crystallises in white needles m.p. 137' (decomp.) which are dissociated by boiliilg water. The amine when heated with phen y 1 t hiocar bi mide gives a-phen y l-fl-o-diphen ylmethane- thwcarbamide N HPh-CS*NH*C,H,*CH,Pb a white crystalline powder m. p. 138'. E. H. Reaction of Phenylhydraaine and a-Halogen Aryl Derivativee. GUIDO GOLDSCHMIEDT (G'cczxetta 1908 38 ii 634-638).-The results obtained by Ponzio and Valente (Abstr. 1908 i 458) had been published previously by Ofner (Abstr. 1904 i 818) and Flnschner (Abstr. '1905 i 936). FEANCESCO ANGELICO ( A tti R. Accad. Lincei 1908 [XI 17 ii 655-662).-Castellana and D'Angelo (Abstr. 1905 i 646) found that prolonged boiling of diazophenylindole with dilute sulphuric acid converts it into the corresponding azo-derivative. The author finds that diazotriphenylpyrrole does not undergo a similar transformation under the same conditions but that i t is con- verted into an isomeric compound which acts both as an acid and as a base dissolves readily in alcoholic potassium hydroxide solution giving a violet solution and separates in cinnabar-red scales ; with strong acids it gives insoluble blue salts.When treated with ethyl iodide in presence of sodium ethoxide it is converted into the ethyl derivative U,,HI,N,Et which crystallises from alcohol in shining indigo-blue needles m. p. 1 8 1 O . By the action of nitric acid on an acetic acid solution of the compound C,2H,5N3 the latter is converted into a diketone I which separates from alcohol in brownish-yellow crystals ni.p. 163O dissolves in concentrated sulphuric acid giving a blue solution and is converted by hydrazine into the correBponding axine C,2H14N4 crystallising from alcohol in golden-yellow needles m. p. 240° and subliming undecomposed. Reduction of the diketone bv means of zinc dust and acetic acid T. H. P. Transformations of Diazopyrroles. >NR yH:CH.s*N :N*y:CPh CH:CH*C-C:C'Ph CH:CH-E*N==T CH C H*C*CBz C Bz ' CH:CH R O N N*C:CPh CH:CH*C- yields the compound I ),:cph>O which crystallises from acetic acid in shining red needles m. p. 195' and is oxidiaed to the diketone by the action of nitric acid. T. H. P.ORGANIC CHEMISTRY. 123 Gonversion of Hydrazing Derivatives into Heterocyclic Compounds. XXV. N-Amino-osotriazoles. ROBERT STOLLE (J. p. Chem. 1908 [ii] '78 544-546.Compare Abstr. 1907 i 654).-The author now draws the conclusion that the compound obtained by the complete hydrolysis of 2 3-dibenzoyl-5 6-diphenyl- 2 3-dihydro-1 2 3 4-tetrazine which was thought previously to be 5 6-diphengl-2 3-dihydro-1 2 3 4-tetrazine (Abstr. 1905 i 97) is 1-amino-3 4-diphenyl-1 2 5-triazole 8ZiS>N*NH2 &ce when it is benzoylated it yields a compound isomeric with the dibenzoyl derivative j u s t mentioned but hiving m. p. 151"; this compound -is l-d&banxoylamino-3 4-diphnyl-1 2 6-t&axole is also formed when 2 3-dibenzoyl-5 6-diphenyl-2 3-dihydro- 1 2 3 4-tetrazine is heated at about 190° and by the benzoylation of the compound obtained by eliminating one of the benzoyl groups from the above dibenzoyltetrazine ; the latter compound must be therefore 1-benzoplamino-3 4-diphenyl-1 2 5-triazole It has also been shown that 2 3-dibenzoyl-5 6-dimethyl-2 3- dihydro-1 2 3 4-tetrazine when heated at about 150' passes into 1-dibenzoylarnino-3 4-dimethyl-1 2 5-triaxoZe YMeiN>N*NBz CJne.N m.p. 1 149 W. H. G. Addition of Hydrogen Chloride to Organic Bases and Aso-compounds. ANTONI KORCZY~SHI (Ber. 1908 41 4379 -438 I. Compare Abstr. 1908 i 977; Scholl and Escales ibid. 1898 i 18a).-Tbe absorption of hydrogen chloride by organic amines and azo-derivatives has been examined at various temperatures and in an apparatus similar to that used by Ley and Wiegner. The maximum number of molecules of hydrogen chloride absorbed is not a function of the strength of the base.At -75' aniline p-toluidine and 0- and m-nitroanilines form salts with 3HC1 and dibromo-p-toluidine End p-nitroaniline with 2HCl. At the ordinary temperature azo benzene p-hydroxyazo benzene p-me thoxyazobenzene and aminoazobenzene absorb 2HC1 and dimethylsminoazobenzene 3HC1. J. J. S. The Corntination of Iodine in Iodothyreoglobulin and aome Observations on Iodothyrin. ADOLF OSWALD (Arch. exp. Path. Pharm. Y.908 60 115-130).-The degradation of iodo- thyreoglobulin by pancreatin and barium hydroxide solution was studied. By means of the former a small amount of a substance was obtained which deposited from the digest and was goluble in alkalis but insoluble in acids ; it contained 3-4*5% iodine and was in many respects similar to Baumann's iodothyrin ; t h e greater part of the iodine found in the digest was not in combination with organic substances.By scission with barium hydroxide also only a small124 ABSTRACTS OF CHEMICAL PAPERS. amount of an organic iodine compound was obtained which was soluble in acids and was probably unchanged thyreoglobulin. S. €5. S. The Mono-amino-acids of Paramucin. FRITZ PREQL (Zeitsch. phpiol. Chern. 1908 58 229-232).-After acid hydrolysis paramucin yields glucosamine diamino-acids in traces leucine alanine proline phenyl-alanine as partic acid,.glutamic acid tyrosine and tryptophan. Quantitative data are not given. W. D. H. Hydrolysis of Glutokyrin. MAX SIEGFRIED and 0. PILZ (ZeitscA. plqsiol. Chem. 1908 58 215-228).-Glutokyrin P-sulphate was prepared from gelatin ; the phosphotungstic acid precipitate from it cwtains 80% of its nitrogen Arginine lysine and glutamic acid were found in the cleavage products after hydrolysis. Histidine and glycine were not obtained. W. D. H. Molecular Analysis of Proteins. ALEXANDRE ETARD and ANTONY VILA (Compt. rend.,. 1908 147 1323-1324. Compare Abstr. 1908 i 584).-The use of anhydrous methyl alcohol is advocated for separating and drying the mixtures of amino-acids formed in protein hydrolysis. A solution of barium hydroxide in anhydrous methyl alcohol is employed for precipitating the acidic substances thus obtained. G. B. The Influence of Acids Alkalis Neutral Salts and Carbo- hydrates on Trypsin. T. KUDO (Biochem. Zeitsch. 1909 15 473-500).-Tryptic digestion with ‘‘ pancreatin Rhenania ” proceeds best in a neutral medium. It is inhibited by alkalis and acids especially organic acids. Sodium carbonate has a very small destructive influence on the ferment acetic acid is indifferent other organic acids destroy it and mineral acids are rather more powerful in this direction. The destructive action is independent of their valency or concentration. Various salts have an inbibitory action but in most cases a slight one. Starch is also inhibitory but the sugars have little or no effect. W. D. H. The Adsorption of Diastase and Gatalase by Colloidal Protein and by Normal Lead’ Phosphate. AMOS W. PETERS (J. Biol. Chem. 1908 5 367-380).-A method of concentratioxi of enzymes is described in which the enzyme is adsorbed from solution by the addition of lead phosphate suspended in water or by peptone ,suspended in 50% acetone. Almost the whole of the enzyme is adsorbed and remains active in spite of the presence of the adsorbed precipitate from which it can only be separated to a slight extent by washing with water. The diastase employed mas obtained from germinating wheat from autolysed liver and from liquid bacterial cultures. The action of diastase is accelerated by the presence of lead phosphate but not for instance by that of zinc phosphate; the reason for the acceleration is unknown. G. U.