公开(公告)号：JPS6032766A

公开(公告)日：1985-02-19

申请号：JP13763483

申请日：1983-07-29

Applicant: TORAY INDUSTRIES

Inventor： FUJII SUNAO ,  IMAMURA SHINZOU ,  SATOU HARUYO

IPC: C07D205/08 ,  B01J23/00 ,  B01J23/44 ,  C07B61/00 ,  C07D207/16

Abstract: PURPOSE:To obtain a proline ester convertible to proline (amino acid) chemically or biochemically in high yield by one stage from a butyric acid derivative, by reacting a 2-cyanoethylglycine ester with hydrogen in the presence of a palladium catalyst. CONSTITUTION:A 2-cyanoethylglycine ester shown by the formula I (R is lower alkyl, etc., especially ethyl) is reacted with hydrogen in the presence of a palladium catalyst to give a proline ester shown by the formula II advantageously. The starting substance, for example, is obtained by subjecting acrylonitrile to Michael addition to a Schiff base of glycine ester and benzophenone, hydrolyzing the reaction product in the presence of an acid, and it may be in the form of a salt such as hydrochloride, etc.

公开(公告)号：JPS58955A

公开(公告)日：1983-01-06

申请号：JP9829481

申请日：1981-06-26

Applicant: TORAY INDUSTRIES

Inventor： SATOU HARUYO ,  IMAMURA SHINZOU

IPC: C07C255/28 ,  C07C67/00 ,  C07C253/00 ,  C07C255/61

Abstract: PURPOSE:To prepare the titled compound useful as an intermediate of amino acid, with simplified process, under mild conditions, in high yield, by reacting N-(diphenylmethylene)glycinonitrile with acrylamide. CONSTITUTION:The 4-cyano-4-(diphenylmethylene)aminobutyric acid amide of formula II can be prepared by reacting N-(diphenylmethylene)glycinonitrile of formulaIwith acrylamide in a solvent, preferably in a binary-phase solvent system containing a phase-transfer catalyst, in the presence of a base, at 0-80 deg.C, preferably at 0-40 deg.C. The compound of formula II can be converted to 4-amino- 4-cyanobutyric acid amide of formula III and benzophenone by hydrolyzing in the presence of an acid, and glutamic acid of formula IV can be obtained by heating the compound of formula III in the presence of an acid or base. The by-produced benzophenone is recycled and reused as a raw material of the compound of formulaI.

公开(公告)号：JPS57130972A

公开(公告)日：1982-08-13

申请号：JP1687081

申请日：1981-02-09

Applicant: TORAY INDUSTRIES

Inventor： SATOU HARUYO ,  IMAMURA SHINZOU ,  KURAMOTO HIROYOSHI

IPC: C07D209/18 ,  C07D209/20 ,  C07D403/06

Abstract: PURPOSE:To prepare tryptophan hydantoin, by hydrolyzing the compound obtained by the reaction of N-(diphenylmethylene)aminoacetonitrile with gramine in the presence of an alkyl sulfate, etc., and reacting the hydrolyzate with ammonium carbonate. CONSTITUTION:The objective compound of formula IV is prepared by (1) reacting the compound of formulaIwith gramine in the presence of an alkyl sulfate of formula R R SO4 (R and R are H or 1-4C alkyl, and are not H at the same time) or an alkyl halide of formula R X (R is 1-12C alkyl or aralkyl; X is Cl, Br or I), (2) hydrolyzing the resultant compound of formula II in the presence of an acid to afford the compound of formula III, and (3) reacting the product with ammonium carbonate. EFFECT:The objective compound can be prepared in high yield with simplified steps, and the by-products can be reused as a raw material for the preparation of starting raw material. USE:Intermediate of tryptophan.

公开(公告)号：JPS56166152A

公开(公告)日：1981-12-21

申请号：JP6888480

申请日：1980-05-26

Applicant: TORAY INDUSTRIES

Inventor： IMAMURA SHINZOU ,  SATOU HARUYO ,  OONO AKIRA

IPC: C07C209/28 ,  C07C67/00 ,  C07C209/00 ,  C07C211/09

Abstract: PURPOSE:To obtain the titled compound useful as a foaming catalyst of polyurethane in high yield with a small amount of formic acid to be used, by methylating hexamethylenediamine reductively with an acid containing a formaldehyde and at least formic acid in a specific proportion. CONSTITUTION:Hexamethylenediamine (HD) of formula I is reacted with an acid containing a formaldehyde and at least formic acid to give the titled compound (TM-HD) of formula III. In the reaction, the formaldehyde in an amount of 3.95- 4.20mol calculated as formaldehyde based on one mole HD, formic acid in an amount of (6.0-x) to (6.5-x)mol as the acid and y moles monobasic organic acid and/or z moles dibasic organic acid are used. Values of x, y and z are as follows: x is 0.5-2.0; y and z are positive numbers including 0; x=y+2z. The amount of raw chemicals, particularly the formic acid, can be reduced as compared with the conventional method, and TM-HD can be obtained with saved resources and energy.

公开(公告)号：JPS55145668A

公开(公告)日：1980-11-13

申请号：JP5402579

申请日：1979-05-04

Applicant: TORAY INDUSTRIES

Inventor： SATOU HARUYO ,  IMAMURA SHINZOU

IPC: C07D223/12

Abstract: PURPOSE:To prepare alpha-dimethylamino-epsilon-caprolactam, economically, in an industrial scale, by reacting alpha-amino-epsilon-caprolactam with an N-methylol compound and formic acid at a specific temperature. CONSTITUTION:alpha-Dimethylamino-epsilon-caprolactam is prepared by reacting alpha-amino- epsilon-caprolactam with an N-methylol compound and formic acid at 80-110 deg.C. The N- methylol compound, which is formaldehyde source, is pref. alpha-dimethylamino-N - methylol-epsilon-caprolactam, however, other methylol compounds having amide group, ureide group, etc., and capable of forming methylol compound in the presence of formaldehyde and formic acid, can also be used. The compound may be mixed with formaldehyde before the reaction.

公开(公告)号：JPS54106471A

公开(公告)日：1979-08-21

申请号：JP1147178

申请日：1978-02-06

Applicant: TORAY INDUSTRIES

Inventor： SHIBAHARA TERUROU ,  FURUYA MASAAKI ,  IMAMURA SHINZOU

IPC: C07D235/28

Abstract: PURPOSE:To obtain the title compound useful as an intermediate for medicines in high yield smoothly, by reacting a stable and easily available specific 2-aminocyclohexanone oxime or its salt with thiocyanic acid under specified conditions. CONSTITUTION:An 2-amino cyclohexanone oxime of formula I: (R is H, alkyl, allyl, or aralkyl group) or its salt is reacted with thiocyanic acid under neutral or acidic atmosphere (generally an acid, e.g. hydrochloric or sulfuric acid) in a solvent, e.g. water or (and) 1-8C alcohol at 40-180 deg.C, preferably 60-140 deg.C to give a 4, 5, 6, 7-tetrahydro-benzimidazoline-2-thione of formula II. The compound of formula I can be obtained by heating 2-chloro-1-nitroso-cyclohexane, prepared by reaction between cyclohexene and nitrosyl chloride, with liquid ammonia.

公开(公告)号：JPS5416598A

公开(公告)日：1979-02-07

申请号：JP8117277

申请日：1977-07-07

Applicant: TORAY INDUSTRIES

Inventor： IMAMURA SHINZOU ,  NAKADA MINORU ,  SAKAI ATSUSHI

IPC: C08G69/00 ,  C08G69/14 ,  C08G69/36

Abstract: PURPOSE:To prepare a polyamide molded article having improved dyeability with an acid dye, by copolymerizing a specific ?-caprolactam derivative.

公开(公告)号：JPS58150551A

公开(公告)日：1983-09-07

申请号：JP3294082

申请日：1982-03-02

Applicant: TORAY INDUSTRIES

Inventor： SATOU HARUYO ,  IMAMURA SHINZOU ,  OONO AKIRA

IPC: C07C227/04 ,  C07C67/00 ,  C07C227/00 ,  C07C227/06 ,  C07C229/22 ,  C07C241/00 ,  C07C251/24

Abstract: NEW MATERIAL:N-(Diphenylmethylene)serine expressed by formulaIand a salt thereof. USE:Useful as a synthetic intermediate for amino acids, and obtainable in high yield by easy operation. PROCESS:An alkyl ester of N-(diphenylmethylene)glycine expressed formula II (R is lower alkyl) is reacted with formaldehyde and/or paraformaldehyde preferably in a two-phase solvent system in the presence of a base, e.g. a carbonate, more preferably in the presence of a phase transfer catalyst, e.g. tetrabutylammonium hydrogensulfate or benzyltrimethylammonium hydroxide, at 0-80 deg.C, preferably 0-40 deg.C, under ordinary pressure for 5-120min to give the aimed compound expressed by formulaI.

公开(公告)号：JPS58116469A

公开(公告)日：1983-07-11

申请号：JP21381081

申请日：1981-12-28

Applicant: TORAY INDUSTRIES

Inventor： SATOU HARUYO ,  IMAMURA SHINZOU

IPC: C07D223/12

Abstract: NEW MATERIAL:The epsilon-caprolactam derivative of formulaI(R is H, lower alkyl or phenyl; phi is phenyl). EXAMPLE:alpha-Phenylmethyleneamino-epsilon-caprolactam. USE:Pharmaceuticals, agricultural chemicals, their intermediates, and intermediate of a dissolving agent (optically active alpha-mono-alkylamino-epsilon-caprolactam). PROCESS:The compound of formulaIcan be prepared by reacting alpha-amino-epsilon- caprolactam with the aromatic compound of formula II in the presence of a solvent such as benzene, toluene, etc. at 30-150 deg.C, preferably 50-110 deg.C. The compound of formulaI can be converted to a dissolving agent (alpha-monoalkylamino-epsilon-caprolactam) by alkylation followed by hydrolysis in the presence of an acid.

公开(公告)号：JPS58116468A

公开(公告)日：1983-07-11

申请号：JP21380981

申请日：1981-12-28

Applicant: TORAY INDUSTRIES

Inventor： SATOU HARUYO ,  IMAMURA SHINZOU

IPC: C07D223/12

Abstract: NEW MATERIAL:The optically active alpha-monoalkylamino-epsilon-caprolactam of formulaI (R is methyl, ethyl or propyl) and its salt. EXAMPLE:(-)-alpha-Monomethylamino-epsilon-caprolactam. USE:A basic resolving agent. It has excellent salt-forming property, crystallinity, stability and handleability, and is low cost. PROCESS:The compound of formulaIcan be prepared by (1) reacting alpha-amino- epsilon-caprolactam with benzaldehyde, (2) reacting the resultant alpha-phenylmethyleneamino-epsilon-caprolactam of formula II with an alkylation agent (e.g. methyl iodide, ethyl bromide, etc.), and (3) hydrolyzing the product in the presence of an acid such as hydrochloric acid, sulfuric acid, etc. The N -position of the alpha-amino-epsilon caprolactam can be selectively monoalkylated.