公开(公告)号：JPH0827148A

公开(公告)日：1996-01-30

申请号：JP16757694

申请日：1994-07-20

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  TSUCHIYA TORU ,  TAGUCHI YOICHI ,  OISHI AKIHIRO

IPC: G03C1/10 ,  A01N43/824 ,  C07D285/00 ,  C07D285/01 ,  C07D417/04 ,  C07D417/14

Abstract: PURPOSE:To readily obtain a dithiazolium salt in good yield and one pot under relatively mild conditions by reacting an N,N-di-substituted thiourea with isothiocyanate in the presence of a strong base and then acidifying and oxidizing the reactional product. CONSTITUTION:(A) An N,N-di-substituted thiourea of formula I (R and R are each an organic group) is reacted with (B) an isothiocyanate of the formula R -N=C=S (R is an organic group) in the presence of a strongly basic alkali metal (compound) such as sodium hydroxide and then, the reactional product solution is acidified and oxidized using an oxidizing agent, e.g. m- chloroperbenzoic acid or hydrogen hydroxide to provide the objective 1,2,4- dithiazolium salt of formula II (X is an acid radical).

公开(公告)号：JPH04364178A

公开(公告)日：1992-12-16

申请号：JP7234591

申请日：1991-03-12

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  YONEMOTO KATSUMI ,  TSUCHIYA TORU ,  TAGUCHI YOICHI ,  YASUMOTO MASAHIKO

IPC: B01J27/122 ,  B01J27/25 ,  C07B61/00 ,  C07D327/04

Abstract: PURPOSE:To obtain the subject compound which is synthetic intermediate of sulfur-containing organic compounds such as medicines, agricultural chemicals, etc., without using toxic carbonyl sulfide gas by treating a di-substituted dithiocarbamic acid phenacylethyl with a specific soft metal salt. CONSTITUTION:A compound expressed by formula I (R is di-substituted amino; Ar is phenyl which may have a substituent group) is reacted with a salt of soft metal such as silver, copper (I) or mercury (II) (preferably a silver salt), preferably in an organic solvent such as alcohols in the presence of a strong acid to provide the objective compound expressed by formula II (X is silver radical).

公开(公告)号：JPH01230574A

公开(公告)日：1989-09-14

申请号：JP5719788

申请日：1988-03-10

Applicant: AGENCY IND SCIENCE TECHN

Inventor： TAGUCHI YOICHI ,  SHIBUYA ISAO ,  SUHARA YASUO

IPC: C07D339/06

Abstract: PURPOSE:To obtain the subject compound useful as a raw material for a dye for the dyeing of paper or pulp, in one step and high yield without using deadly poisonous phosgene, etc., by using easily available epoxide and carbon disulfide as raw materials and reacting the components in the presence of a base under high pressure. CONSTITUTION:The objective compound of formula II can be produced by reacting an epoxide of formula I (R is alkyl or aryl; R is alkyl or H) with carbon disulfide in the presence of a base (e.g., triethylamine or pyridine) under high pressure. The reaction pressure is preferably as high as possible and is usually 500-9,000kg/cm . The reaction is carried out at room temperature -120 deg.C for usually 5-50hr. The reaction solvent is hexane, benzene, etc., and the compound of formula I is used in an amount nearly equimolar to the amount of the carbon disulfide.

公开(公告)号：JPH01225940A

公开(公告)日：1989-09-08

申请号：JP5307388

申请日：1988-03-07

Applicant: AGENCY IND SCIENCE TECHN ,  KONISHIROKU PHOTO IND ,  SANKYO CO

Inventor： YONEMOTO KATSUMI ,  SHIBUYA ISAO ,  SAKAMOTO HIDEKAZU ,  KANEKO YUTAKA

IPC: G03C1/34

Abstract: PURPOSE:To maintain stable photographic characteristics even after long-term preservation at an under a high temp. and high humidity by forming the fog restrainer of 1,4,2-dithiazolium salt compds. having a specific heteroarom. cation ring structure. CONSTITUTION:This fog restrainer is used by incorporating at least one selected from the 1,4,2-dithiazolium salt compds. having the heteroarom. cation ring structure into at least either of a silver halide emulsion layer and the hydrophilic colloid layer adjacent thereto. The purpose as the fog restrainer for photographs is attained if the 1,4,2-dithiazolium salts have the cation ring structure in this case. Generation of fogging is thereby suppressed during the long-term preservation or even if the photographic sensitive material is stored at a high temp. or at and under the high temp. and high humidity. The excellent photographic sensitive material which is free from degradation of the sensitivity and softening of the gradation is thus obtd.

公开(公告)号：JP2000095751A

公开(公告)日：2000-04-04

申请号：JP28339298

申请日：1998-09-18

Applicant: AGENCY IND SCIENCE TECHN ,  SHIMIZU MASAO ,  SHIBUYA ISAO

Inventor： SHIMIZU MASAO ,  SHIBUYA ISAO ,  GAMA YASUO

IPC: C07C313/24 ,  C07D275/04

Abstract: PROBLEM TO BE SOLVED: To obtain a new sulfenamide useful for profitably producing benzoisothiazolinone compounds by aminating the thiol group of a thiosalicylic acid ester compound without using a poisonous chlorine gas and a starting raw material which is difficult to obtain. SOLUTION: A compound of formula I [R1-R4 are each H or an inactive substituent (for example, an alkyl group); R5 is an inactive ingredient (for example, an aliphatic group)]. For example, a compound of formula II. The compound of formula I is obtained by aminating a thiosalicylic acid ester compound of formula III. The amination reaction is preferably carried out by reacting 1 equivalent of the thiosalicylic acid ester with 1.0-3 equivalents of the aminating agent (for example, hydroxyamine-O-sulfonic acid) in a reaction solvent (for example, water, a 1-6C aliphatic alcohol such as methanol, an ether compound such as diethyl ether or a nitrogen-containing organic solvent such as acetonitrile) at -30 to 50 deg.C.

公开(公告)号：JPH0899955A

公开(公告)日：1996-04-16

申请号：JP23730194

申请日：1994-09-30

Applicant: AGENCY IND SCIENCE TECHN

Inventor： TAGUCHI YOICHI ,  OISHI AKIHIRO ,  SHIBUYA ISAO ,  TSUCHIYA TORU

IPC: C07D201/02 ,  C07D205/08

Abstract: PURPOSE: To easily and efficiently obtain the subject derivative useful as a synthetic intermediate for β-amino acid derivatives or antibiotics having penicillin-simulated structure, by reaction between an isocyanate and a vinyl ether compound. CONSTITUTION: This β-lactam derivative of the formula is obtained by reacting (A) an isocyanate of formula, R NCO (R is a hydrocarbon) (e.g. methyl isocyanate, cyclopentyl isocyanate, phenyl isocyanate) with (B) a vinyl ether compound of formula, CH2 =CH-O-R (R is a hydrocarbon) (pref. methyl vinyl ether, ethyl vinyl ether, cyclopentyl vinyl ether etc.) under a pressure of pref. >=2000atm (more pref. 2000-12000atm) at 20-130 deg.C.

公开(公告)号：JPH06263744A

公开(公告)日：1994-09-20

申请号：JP7891193

申请日：1993-03-12

Applicant: AGENCY IND SCIENCE TECHN

Inventor： OISHI AKIHIRO ,  YASUMOTO MASAHIKO ,  GOTO MIDORI ,  TSUCHIYA TORU ,  SHIBUYA ISAO ,  TAGUCHI YOICHI

IPC: C07D239/95

Abstract: PURPOSE:To obtain the subject compound useful as a physiologically active substance, etc., from inexpensive raw materials direct and in high yield by reacting a phenyl isothiocyanate with an N,N-di-substituted cyanamide under high pressure. CONSTITUTION:A compound of formula I (R is alkyl, cycloalkyl, acryl, alkoxy, etc.; (n) is 0-4; with the proviso that at leas one ortho position based on isothiocyanate group of benzene ring has H) is reacted with a compound of formula II (R and R are alkyl, cycloalkyl, aryl, arylalkyl, alkoxy, etc.; R together R may form a ring) under 500-20,000 atmospheric pressure at 30-20 deg.C preferably in the absence of a solvent. Optionally, the reactional product is treated with an acid to give the objective compound of formula III (HX is inorganic acid or organic acid; (m) is 0 or 1).

公开(公告)号：JPH05310730A

公开(公告)日：1993-11-22

申请号：JP11396292

申请日：1992-04-07

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  YONEMOTO KATSUMI ,  YASUMOTO MASAHIKO ,  TAGUCHI YOICHI ,  TSUCHIYA TORU ,  MIZUNO MASAKI

IPC: B01J27/12 ,  B01J27/06 ,  B01J27/25 ,  B01J31/02 ,  B01J31/04 ,  B01J31/26 ,  C07B61/00 ,  C07D339/06

Abstract: PURPOSE:To easily and directly obtain a 2-(disubstituted methylens)-1,3-dithiol in an economically advantageous way from a 1,3-dithiol-2-thione compound. CONSTITUTION:The compound of formula II can advantageously be obtained by reaction of (A) a compound of formula I (R and R are each H or inert substituent, or may form a ring through mutual binding of their terminals) with (B) a compound of formula R -CH2-R (R and R are each electron- accepting group) in the presence of (C) a silver salt, e.g. an organic carboxylic acid silver salt such as silver benzoate or silver acetate, or an inorganic silver salt such as silver nitrate, silver tetrafluoroborate or silver perchlorate, esp. a fluorine-contg. organic carboxylic acid silver salt such as CF3COOAg and (D) a base, pref. a tertiary amine, pref. in an anhydrous solvent at 0-150 (pref. room temperature to 80) deg.C. The amounts of the components to be used are as follows: B=1-2mol, C=1-5mol (each per mol of A); D=2-10mol per mol of B.

公开(公告)号：JPH04210672A

公开(公告)日：1992-07-31

申请号：JP34105290

申请日：1990-11-30

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  YONEMOTO KATSUMI ,  TSUCHIYA TORU ,  YASUMOTO MASAHIKO ,  TAGUCHI YOICHI

IPC: C07C333/02 ,  C07C333/04 ,  C07C333/08

Abstract: NEW MATERIAL:An N-aroyl-S-(di-substituted carbamoyl)sulfenamide expressed by formula I (R is di-substituted amino; R is aryl). EXAMPLE:N-Benzoyl-S-(dimethylcarbamoyl) sulfenamide. USE:An anti-fogging agent in silver halide photograph. The compound expressed by formula I has complex forming ability also to various kind of metal ions other than silver and is useful also as a chelate agent and extracting reagent. PREPARATION:N-aroyl-S-substituted thiocarbonylsulfenamides expressed by formula II are reacted with metal salts (e.g. silver, copper (I), mercury or lead (II)) in the presence of an acid and water in a solvent (e.g. chloroform) at ambient temperature to heated temperature to provide the compound expressed by formula I.

公开(公告)号：JPH04169575A

公开(公告)日：1992-06-17

申请号：JP29300790

申请日：1990-10-30

Applicant: AGENCY IND SCIENCE TECHN

Inventor： TAGUCHI YOICHI ,  YASUMOTO MASAHIKO ,  TSUCHIYA TORU ,  YONEMOTO KATSUMI ,  SHIBUYA ISAO

IPC: C07D251/46

Abstract: PURPOSE:To easily obtain the subject compound useful as an intermediate for resin modifier, etc., in high yield by reacting an isothiocyanic acid ester in the presence of a base under high pressure, thereby converting the compound into a physiologically active compound. CONSTITUTION:The objective compound of formula can be produced by reacting an isothiocyanic acid ester of formula RNCS (R is alkyl or aryl) in a polar solvent (e.g. DMF) in the presence of a tert-amine catalyst (e.g. triethylamine) and a trace amount of water under a pressure of 1,000-12,000kg/cm at room temperature to 100 deg.C for 1-50hr, distilling out the solvent from the reaction mixture and carrying out vacuum distillation and purification of the product.