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：JPS54106472A

公开(公告)日：1979-08-21

申请号：JP1147278

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 which is an intermediate for medicines in simple procedures in high yield, by treating a specific compound, readily prepared through addition reaction between 2-amino-cyclohexanone oxime and a thioisocyanate, with an acidic substance. CONSTITUTION:A N-(2-hydroxyimino-cyclohexyl)-thiourea of formula I: (R is alkyl, allyl, or aralkyl group) is brought into contact with an acidic substance, e.g. hydrogen chloride, hydrogen bromide, sulfuric or benzenesulfonic acid, at 0- 150 deg.C, preferably 10-100 deg.C to give the objective compound of formula II. The thiourea of formula I is obtained by addition reaction of 2-amino-cyclohexanone oxime with a thiocyanate of formula IV according to the well-known method. Preferably, the amount of the acidic substance is 0.01 mole or more per mole of the compound of formula I.

公开(公告)号：JPS54106473A

公开(公告)日：1979-08-21

申请号：JP1147378

申请日：1978-02-06

Applicant: TORAY INDUSTRIES

Inventor： SHIBAHARA TERUROU ,  FURUYA MASAAKI ,  IMAMURA SHINZOU

IPC: C07D235/28

Abstract: NEW MATERIAL:A 4, 5, 6, 7-tetrahydro-benzimidazoline-2-thione of formula I: (R is H, alkyl, allyl, or aralkyl group; R is alkyl, allyl, or aralkyl group). EXAMPLE:1-Methyl-4, 5, 6, 7-tetrahydro-benzimidazoline-2-thione. USE:An intermediate for medicines, industrial rubbers or their intermediate, and rust inhibitors. PROCESS:One mole of an 2-amino-cyclohexanone oxime is reacted with 0.5-2 moles, preferably 0.8-1.2 moles of a thiocyanate of formula III in an inert solvent, e.g. benzene, and, without isolation, treated with an acidic substance to form the conpound of formula I.

公开(公告)号：JPS54103835A

公开(公告)日：1979-08-15

申请号：JP829878

申请日：1978-01-30

Applicant: TORAY INDUSTRIES

Inventor： SHIBAHARA TERUROU ,  FURUYA MASAAKI ,  IMAMURA SHINZOU

IPC: C23F11/16 ,  C07C67/00 ,  C07C325/00 ,  C07C335/14 ,  C23F11/00

Abstract: NEW MATERIAL:N-(2-Hydroxyimino-cyclohexyl)-thiourea derivatives of formula I (R is alkyl aryl, aralkyl). EXAMPLE:The compound of formula II. USE:Novel starting materials for medicines, agricultural chemicals, rubber additives, antirusting agents for metals. PREPARATION:In an example, the reaction of 2-amino-cyclohexanone oxime with a thioisocyanate of R-NCS in an inert solvent affords the objective compound of formula I. The 2-amino-cyclohexanone oxime is prepared by a method shown in the reaction equations.

公开(公告)号：JPS5476590A

公开(公告)日：1979-06-19

申请号：JP14077277

申请日：1977-11-25

Applicant: TORAY INDUSTRIES

Inventor： UEDA CHIAKI ,  SHIBAHARA TERUROU

IPC: C07D223/12

Abstract: PURPOSE:Specific amounts of formaldehyde and formic acid are made to act on alpha-amino-epsilon-caprolactam to convert selectively only the amino group to dimethyl derivative, thereby giving title compound under mild conditions in high yield. CONSTITUTION:To one mole of alpha-amino-epsilon-caprolactam are added no more than 8, preferably 2-5 moles of formaldehyde and no more than 12, preferably 2-7.5 moles of formic acid and the mixture is heated to 50-100 deg.C to form alpha-dimethylamino-epsilon-caprolactam. Formaldehyde can be used in the form of either an qqueous solution or an oligomer such as paraformaldehyde.

公开(公告)号：JPS54104457A

公开(公告)日：1979-08-16

申请号：JP1147578

申请日：1978-02-06

Applicant: TORAY INDUSTRIES

Inventor： SHIBAHARA TERUROU ,  SUGII KENJI ,  IMAMURA SHINZOU

IPC: C23G1/06 ,  C23G1/10

Abstract: PURPOSE:To provide the title inhibitor contg. N-(2-hydroxyimino-cyclohexyl)- thioureas as principal components and having a good corrosion inhibiting action independently of the kinds of metal and acid. CONSTITUTION:The inhibitor contains N-(2-hydroxyimino-cyclohexyl)-thioureas, as principal components, represented by the formula (where R is 1-8 C alkyl, phenyl or benzyl). These thioureas are obtd. e.g. by reacting 2-amino-cyclohexanone oxime with thiocyanates. The inhibitor is applicable to mild steel, Al and copper. It is added in an amt. of 0.001-0.5, pref. 0.002-0.2% to a pickling soln. of mineral acids such as hydrochloric and sulfuric acids, and org. acids such as acetic and citric acids. A known inhibitor may be added. The inhibitor of this invention shows a superior corrosion inhibiting effect independently of the kind of acid.

公开(公告)号：JPS54104456A

公开(公告)日：1979-08-16

申请号：JP1147478

申请日：1978-02-06

Applicant: TORAY INDUSTRIES

Inventor： SHIBAHARA TERUROU ,  SUGII KENJI ,  IMAMURA SHINZOU

IPC: C23G1/06 ,  C23G1/10

Abstract: PURPOSE:To provide the title inhibitor contg. 4, 5, 6, 7-tetrahydro-benzimidazoline- 2-thion derivatives as principal components and having a superior corrosion inhibiting effect independently of the kinds of metal and acid. CONSTITUTION:The inhibitor contains one or more kinds of 4, 5, 6, 7-tetrahydro- benzimidazoline-2-thion derivatives, as principal components, represented by the formula (where R is H or 1-8 C alkyl and R is 1-8 C alkyl, allyl or aralkyl). A known inhibitor may be added. The inhibitor of this invention shows a superior effect independently of the kind of acid and is applicable to mild steel, Al and copper. It is added to a pickling soln. in an amt. of 0.001-0.5, pref. 0.002-0.2%. 2-mercapto-4, 5, 6, 7-tetrahydro-benzimidazole derivatives are considered to be the same cpds. as the derivatives of the formula.

公开(公告)号：JPS54103870A

公开(公告)日：1979-08-15

申请号：JP1080578

申请日：1978-02-02

Applicant: TORAY INDUSTRIES

Inventor： SHIBAHARA TERUROU ,  FURUYA MASAAKI ,  IMAMURA SHINZOU

IPC: C07D235/28 ,  C08K5/34 ,  C08K5/36 ,  C23G1/06

Abstract: NEW MATERIAL:A 4,5,6,7-tetrahydrobenzimidazoline-2-thione derivative of formula I: (R is H, alkyl, allyl, or aralkyl group: R is alkyl, allyl, or aralkyl group). EXAMPLE:A compound of formula II. USE:Intermediate for medicines, chemicals for industrial rubbers, and their intermediates, and rust preventives. PROCESS:A 2-amino-cyclohexanone oxime or its derivative of formula III is reacted with a thiocyanate of formula IV, and the reaction product is treated with an acidic substance, e.g. bydrogen chloride to form the 4,5,6,7-tetrahydro-benzimidazoline- 2-thione derivative of formula I. The compound of formula II can be obtained by reacting cyclohexanone with NOCl and liquid SO2 to form a compound of formula V, which is reacted with a compound of the formula R NH2 in high yield industrially.