Komatsu, Shigeru

Nodzu, Ryuzaburo

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RIGHT:URL:CITATION:AUTHOR(S):ISSUE DATE:TITLE:Reaction between Aniline andChloracetic acid, INodzu, Ryuzaburo; Komatsu, ShigeruNodzu, Ryuzaburo ...[et al]. Reaction between Aniline and Chloracetic acid, I. Memoirs ofthe College of Science, Kyoto Imperial University 1922, 6(2): 73-761922-11-30http://hdl.handle.net/2433/256621Reaction between Aniline and Chloracetic acid, I. Ryuzaburo Nodzu aiul Shigern Komatsu. (Received June 7, 1922.) When 20 c.c. aniline ( 1•04 mo!.) and 20 grm: chloracetic acid ( I mol.) were mixed in a pressure bottle, white sublimate of chlor-acetanilide was observed to form immediately.1 The mixture was heated in a boiling water bath for one hour, and the reaction product treated with 250 c.c. water and was left to stand over night at ordinary temperature, and then filtered. The residue (I) suspended in 50 c.c. water, was digested with cone. ammonium carbonate solution on a water bath, cooled and filtered, the extraction being repeated once more to separate completely the acidic substance from the neutral reaction products. The combined filtrate, on acidifying with dilute hydrochloric acid, yielded a white• precipitate that amounted to I• 5 grm. The substance having been purified, by reprecipitation with hydrochloric acid from its ammonium salt solution, and by recrystallization from the 80 o/o alcohol solution, melted at 212° and gave on analysis the following results: I. 0•1449 grm. substance gave 0-3561 grm. CO2 and 0-0770 grm. H2O. II. 0•1498 grm. ,, ,, 12•4c.c. N2 at 15° and 764•6 m.m. Carbon Hydrogen Nitrogen Cale. for C1aH16N2O3 67-57 5-68 9-86 Found 67•02 5·95 9·78 1 P. Meyer, Ber. D. Chem. Ges., 8, n52 (1875). 74 Ryuzaburo Nodzu and Shigeru Komatsu. The physical and chemical properties of the substance so far as we studied agree with those of phenylimidodiacetic acid mono-anilide which was obtained together with phenylimidodiacetanilide by A. Hausdorfer1 from the reaction product of phenylimidodiacetic acid and aniline at 1700. The authors, however, expected that the substance was formed by the interaction of phenylglycine and chloracetanilide. For the purpose of testing this view, an equimolecular mixture of the two substances was heated in a sealed tube in a boiling water bath for one hour and phenylimidodiacetic acid mono anilide was isolated and thus our assump-tion has been realized. From the residue (II) insoluble in ammonium carbonate solution, a small quantity of diphenyldiketopiperazine and l gm. chloracetanilide were isolated, by extraction of the latter in the cold with 94 % alcohol leaving the former compound in the residue. Chloracetanilide thus obtained from the alcoholic solution, was purified by recrystalli-sation from hot aqueous solution, melted at 134- 0 and gave on analysis the following results : I. 0-1005 grm. substance gave 0-2108 grm. CO2 and 0-0479 grm. H 2O. II. 0-1523 grm. ,, ,, 0•1251 grm. AgCI. Carbon Hydrogen Chlorine 56-63 4-75 Found 57•22 5•20 The pure diphenyldiketopiperazine, obtained from the insoluble residue in 94% alcohol and purified by the recrystallization from hot alcoholic solution, melted at 263° and gave on analysis the following results: I. 0-1462 grm. substance gave 0•3844 grm. CO2 and 0-0708 grm. H 2O. II. 0-1462 grm. ,, ,, 13•4 c.c. N2 at 15° and 763•2 m.m. Cale. for C16H 14N2O3 Found Carbon Hydrogen Nitrogen 72-14 5•30 I0•52 71•7I 5•44 I0•8I The filtrate separated from the residue (I), indicates a strong acidic reaction, was neutralized with ammonia and concentrated under reduced pressure to its half volume. The concentrated solution being alkalined with ammonia the unchanged aniline was extracted with 30 c.c. ether and then acidified with dilute hydrochloric acid. The acid solution was 1 Ber. D. Chem. Ges., ZZ, 1795 (1889); 23, 1990 (1890). Reaction between Aniline and Chloracetic acid. I. 7 5 treated with 30 c.c. ether, the operation being repeated twice to expel completely phenylimidodiacetic acid, and again neutralized with ammonia water, and concentrated to 50 c.c. under reduced pressure. On standing the concentratnd solution, after it was acidified with dilute hydrochloric acid, for one day at ordinary temperature, phenylglycine crystallized out. The yield was 3 grm. It melted at 126-127°, and gave the following analytical results:-I. 0,2398 grm. substance gave 0•5592 grm. CO2 and 0•1310 gr. H2O. II. 0,1560 grm. ,, ,, 13•55 c.c. N2 at 15° and 757·8 mm. Cale. for CsH9NO2 Found Carbon 63•55 63•60 Hydrogen 6-oo 6•1 I Nitrogen 9•27 9•73 Distilling off the ether, from the ether extract, there remained 3 grm. phenylimidodiacetic acid1 which purified by crystallisation from the water solution, melted at 155 ° and gave on analysis the following results: I. 0•1838 grm. substance gave 0•387ogrm. CO2 and 0•0890 grm. H2O. II. 0-1686 grm. ,, ,, 9·9 c.c. N2 at 14° and 762•4 m.m. Carbon Hydrogen Nitrogen Cale. for CioH11NO4 57·39 5•30 6•71 Found 57•42 5•41 6•94 Of the reaction products between aniline and chloracetic acid at 100°, we have actually isolated chloracetanilide, diphenyldiketopiperazine, phenylimidodiacetic acid mono-anilide, phenylglycine and phenylimido-diacetic acid. The chemical reactions involving the synthesis of these substances will be classified in (a) the dehydration and (b) the dehydrochlorination as formulated below : ClCH2 COOH. NH2CsHs CGH5NH2+CICH2COOH/ =ClCH2 CONHC6Hs+H2O .......... (a) ~C6H;;NH2ClCH2COOH =C6H5NH2 CH2 COOH + HC!. ...... (b) Hydrochloric acid accelerates the reaction~ (a) and on the other hand aniline may produce a similar effect on the reaction ,(b). Even in the absence of any catalyst, when aniline comes into contact with 1 P. Meyer, Ber. D. Chem. Ges., 14, 1325 (1881); Hausdorfer, Loe. Cit. 2 H. Goldschmidt and C. Wachs, Zs. Physik. Chem., 24, 364 (1897J. 76 R. Nodzu & S. Komatsu, Reaction between Aniliue & Chloracetic acid, I. chloracetic acid in a sealed tube at 100°, and the reaction is started, one stimulates the other, they will proceed to their equilibrium states. The first reaction which takes place instantaneously after the reacting components are mixed would be easily decided to be (a) by the readiness of formation of the molecular compound. The presence of aniline which is capable forming an addition compound with hydro-chloric acid may naturally accelerate the formation of phenylglycine from aniline and chloracetic acid, of phenylimidodiacetic acid from phenylglycine and chloracetic acid. Consequently, chloracetanilide formed as an intermediated product, in the presence of an excess of aniline, without remaining in the reaction products would be entirely transformed into phenylglycineanilide &c. as will seen in A. Haus-dorfer's article. Furthermore, aniline plays the same part in the formation of diphenyldiketopiperazine from chloracetanilide and of phenylimidodi-acetic acid mono-anilide from chloracetanilide and phenylglycine, as caustic potash does in the formation of the former as observed by Abenius,1 and also by Prof. Kuhara and Chikashige.2 April, I922, Laboratory of Organic and Biochemistry. 1 Ber. D. Chem. Ges., 21, 1665 (1888). 2 Mem. Coll. Sci. Engin. Kyoto, 1, I ( 1903-8). 

Reaction between Aniline and Chloracetic acid, I

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Reaction between Aniline and Chloracetic acid, I

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