公开(公告)号：JPS63218682A

公开(公告)日：1988-09-12

申请号：JP5370287

申请日：1987-03-09

Applicant: AGENCY IND SCIENCE TECHN

Inventor： YONEMOTO KATSUMI ,  SHIBUYA ISAO

IPC: C07D327/04 ,  C07D285/00 ,  C07D291/06 ,  C07D339/06 ,  C07D521/00

Abstract: PURPOSE:To simply and inexpensively obtain a ring-expanded product by N atom useful as a synthetic intermediate for agricultural chemicals and medicine under mild conditions in high yield, by reacting a heterocyclic cationic compound with a sulfenamide derivative as a ring expanding reagent. CONSTITUTION:A heterocyclic cationic compound expressed by formula I (X and Y are hetero atoms; R is electron-donating group; Z is acid radical of inorganic strong acid; number of ring member of cation part is 5) such as 5- morpholine-3-phenyl-1,4,2-dithiazolium perchloric acid salt or mesoionic compound expressed by formula II (R is R ; R is inert substituent group; W is S or O) is reacted with a sulfenamide derivative expressed by formula III (R is N,N-disubstituted thiocarbamoylsulfenamide, heterocyclic group, aroyl or substituted imidoyl) such as dimethylthiocarbamoylsulphenamide in a solvent such as acetonitrile under mild conditions of room temperature and neutral for several ten minutes - several days to provide the aimed compound expressed by formula V (numbers of ring member are 6) having antiaromatic properties.

公开(公告)号：JPS63218673A

公开(公告)日：1988-09-12

申请号：JP5370187

申请日：1987-03-09

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  YANAGIYA KOSHIN ,  YASUMOTO MASAHIKO

IPC: C07D339/06 ,  B01J31/02 ,  C07B61/00 ,  C07D409/04

Abstract: PURPOSE:To obtain the titled compound which is an intermediate for synthetic compound such as medicine in one process and high yield without by-product, by using an acetylene compound, carbon disulfide and sulfur which are simple raw material and reacting the acetylene compound with the carbon disulfide and sulfur under high pressure in the presence of a base. CONSTITUTION:Acetylenes expressed by formula I (R and R are inert substituent groups or H), carbon disulfide and sulfur are used as raw material and the acetylenes are reacted with the carbon disulfide and sulfur under high pressure in the presence of a base, preferably triethylamine, pyridine, N,N- dimethylaniline, etc., preferably at room temperature - 100 deg.C normally for 5-50hr to provided the aimed compound expressed by formula II. Commercial products may be directly use as the carbon disulfide and sulfur which are the above-mentioned raw material and the carbon disulfide is preferably used in excess amount, since the carbon disulfide is a raw material for dissolving sulfur. Although higher pressure is preferred, the pressure is suitable normally in the range of 500-9,000kg/cm .

公开(公告)号：JPS62207268A

公开(公告)日：1987-09-11

申请号：JP4936686

申请日：1986-03-06

Applicant: AGENCY IND SCIENCE TECHN

Inventor： TAGUCHI YOICHI ,  YANAGIYA KOSHIN ,  SHIBUYA ISAO ,  SUHARA YASUO

IPC: C07D339/06

Abstract: PURPOSE:To obtain the titled compound useful as an intermediate for tetrathiafulvalene (electric charge transfer complex) or an intermediate substance for physiological active substance simply and in high yield, by reacting thiirane compound with carbon disulfide in the presence of a base at a high temperature. CONSTITUTION:A thiirane compound shown by formula I (R is alkyl or aryl; R and R are alkyl or H) is reacted with carbon disulfide in the presence of a base such as tertiary amine, e.g. triethylamine, pyridine, etc. at high pressure of 500-9,000kg/cm at room temperature -100 deg.C to give the aimed compound shown by formula II in high yield and efficiently. The compound shown by formula I can be readily synthesized from a corresponding epoxide and thiourea or potassium thiocyanate and carbon dioxide is inexpensively sold on the market.

公开(公告)号：JP2001058977A

公开(公告)日：2001-03-06

申请号：JP23299999

申请日：1999-08-19

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIMIZU MASAO ,  SHIBUYA ISAO ,  GAMA YASUO

IPC: C07C249/02 ,  C07C251/10 ,  C07C251/16

Abstract: PROBLEM TO BE SOLVED: To obtain a ketenimine in a high yield under a mild condition without causing the environmental pollution problem by reacting a thioamide compound with a haloiminium salt. SOLUTION: The objective compound of formula III (e.g. N- benzylphenylketenimine) is obtained by desulfhydrating reaction of a compound of formula I (R1 and R2 are each H, an alkyl or an aryl; R3 is an alkyl or an aryl with proviso that the case of R1, R2 and R3 of all an aryl is omitted), e.g. phenylacetic acid thioanilide with a compound of formula II (R4 and R5 are each a lower alkyl; X is a halogen; Y is a counter anion; n is 0 or 1), e.g. 2-chloro-1,3-dimethylimidazolinium chloride. The above reaction is preferably carried out in a reactive solvent (e.g. methylene chloride) in the presence of a base (e.g. triethylamine or the like).

公开(公告)号：JP2001019683A

公开(公告)日：2001-01-23

申请号：JP19549199

申请日：1999-07-09

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIMIZU MASAO ,  SHIBUYA ISAO ,  GAMA YASUO ,  SHIBAUE MOTONARI ,  TAKAGI TOSHIYUKI

IPC: C07D275/04

Abstract: PROBLEM TO BE SOLVED: To obtain in safety and good yield the subject derivative of 1,2- benzothiazolin-3-one having various bioactivities without using a toxic gas by heating a sulfenamide compound. SOLUTION: The objective derivative of formula II (e.g. 1,2-benzisothiazolin-3- one, etc., of formula III) is obtained by carrying out a cyclization reaction of a sulfenamide compound of formula I [R1-R4 are each H, an alkyl, an alkoxy, etc.; R5 is a (substituted)alkyl, a cycloalkyl, etc.], (e.g. methyl 2- sulfenamoylbenzoate, etc.). The reaction is preferably carried out in the presence of a solvent (e.g. toluene, etc.), at 50-150 deg.C, for 2-8 hours.

公开(公告)号：JPH0853373A

公开(公告)日：1996-02-27

申请号：JP19059794

申请日：1994-08-12

Applicant: AGENCY IND SCIENCE TECHN

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

IPC: C07D335/10 ,  B01J23/50 ,  B01J23/72 ,  B01J27/055 ,  B01J27/122 ,  B01J27/25 ,  B01J31/02 ,  C07B41/04 ,  C07B61/00 ,  C07C41/48 ,  C07D311/80 ,  C07D413/00

Abstract: PURPOSE:To easily obtain the subject compound suitable for protecting or modifying OH-group of a polyol originated from a natural product, etc., in high yield by reacting a polyalcohol with a thiocarbonyl compound in the presence of a base, and a silver salt or copper salt. CONSTITUTION:This compound is obtained by reacting (A) a polyalcohol such as ethylene glycol, glycerol or a polyol originated from a natural product (D) with a thiocarbonyl compound of the formula [R and R are each an aryl e.g. (nitro)phenyl, an alkyl, a pyridyl, etc.], etc., in the presence of (B) a base such as an organic tertiary amine (e.g. triethylamine) and a silver salt (e.g. silver trifluoroacetate, silver trifluoromethanesulfonate) or a copper salt [e.g. copper (II) trifluoroacetate or copper (II) trifluoromethanesulfonate]. Further, this reaction is carried out preferably in an organic solvent such as acetonitrile or THF.

公开(公告)号：JPH07242671A

公开(公告)日：1995-09-19

申请号：JP6550094

申请日：1994-03-08

Applicant: AGENCY IND SCIENCE TECHN

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

IPC: A01N43/90 ,  C07D491/04 ,  C07D491/048

Abstract: PURPOSE:To obtain a novel compound which is useful as a synthetic intermediate for beta-amino acid derivative, a sedative having a lactam structure, a herbicide having 2-substituted aminotetrahydrofuran structure and an antibiotic having penicillin-like structure. CONSTITUTION:This compound is expressed by the formula (R is an alkyl, a cycloalkyl or a halogen or an aryl substitutable), for example, 7-(p- chlorophenyl)-2-oxa-7-azabicyclo[3.2.0]heptan-6-one. The compound is obtained by reaction of an isocyanic ester of the formula, RNCO such as methyl isocyanate with 2,3-dihydrofuran, preferably using the dihydrofuran as a solvent, too. The reaction is preferably carried out at room temperature to 100 deg.C in a sealed tube or under 2,000 to 12,000 atmospheric pressure.

公开(公告)号：JPH07233096A

公开(公告)日：1995-09-05

申请号：JP4975494

申请日：1994-02-22

Applicant: AGENCY IND SCIENCE TECHN ,  KONISHIROKU PHOTO IND

Inventor： SHIBUYA ISAO ,  KATO EISAKU

IPC: C07D295/14 ,  B01J27/122 ,  B01J31/04 ,  C07B37/04 ,  C07B61/00 ,  C07C209/68 ,  C07C211/52 ,  C07C227/10 ,  C07C229/44 ,  C07C253/30 ,  C07C255/42 ,  C07D213/70 ,  C07D339/06

Abstract: PURPOSE:To easily obtain an olefin derivative useful as agrochemicals, etc., in high yield by reacting a specific thiocarbonyl compound with an active methylene compound in the presence of a base and a specific metal salt. CONSTITUTION:This olefin derivative of formula III, e.g. isoprothiolane of formula IV is produced by reacting (A) a compound of formula I (R and R each is H or a substituent such as an alkyl, an aryl and a heterocyclic group; R and R may together form a ring structure), e.g. ethylene trithiocarbonate with (B) a compound of formula II (X and Y each is H or a substituent and at least one of X and Y is an electron-attracting substituent such as CN, NO2, an alkoxycarbonyl and carbamoyl), e.g. diisopropyl malonate in the presence of (C) a silver salt such as silver trifluoroacetate or a copper salt such as cuprous acetate and (D) a base such as triethylamine.

公开(公告)号：JPH04182475A

公开(公告)日：1992-06-30

申请号：JP30925090

申请日：1990-11-15

Applicant: AGENCY IND SCIENCE TECHN

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

IPC: C07D285/34

Abstract: PURPOSE:To obtain a compound useful as an intermediate for medicine or agricultural chemical in one-stage reaction and good yield from an inexpensive raw material by reacting an N,N-disubstituted-cyanamide with carbonylsulfide under high pressure. CONSTITUTION:A N,N-di-substituted cyanamide expressed by formula I (R1 and R2 are alkyl or R1 and R2 may together form a ring) is reacted with carbonyl sulfide expressed by the formula S=C=O in a solvent such as toluene at 20-200 deg.C under pressure of 1000-12000 atom to provide the objective product expressed by formula II. The compound expressed by formula I and carbonyl sulfide are used at a molar ratio of 1:10 to 10:1. The compound expressed by formula II is used as an intermediate for drug for inflammatory disease and cardiopathy and useful as an intermediate for nematocide, insect pest control agent, etc.

公开(公告)号：JPH0476537A

公开(公告)日：1992-03-11

申请号：JP18943490

申请日：1990-07-19

Applicant: AGENCY IND SCIENCE TECHN ,  KONISHIROKU PHOTO IND

Inventor： SHIBUYA ISAO ,  YONEMOTO KATSUMI ,  HIRABAYASHI SHIGETO ,  KANEKO YUTAKA

IPC: G03C1/34

Abstract: PURPOSE:To maintain stable photographic characteristics in spite of long-time preservation at and under a high temp. and high humidity by incorporating a specific compd. into silver halide emulsion layers and the hydrophilic colloidal layers adjacent thereto. CONSTITUTION:The compd. expressed by formula is used. In the formula, R1 and R2 may be the same or different and respectively denote an alkyl group; R1 and R2 may form a hetero ring by making ring condensation together with a nitrogen atom; R3 denotes a hydrogen atom, halogen atom, alkoxy group, hydroxy group or dialkyl amino group. Then, the fogging is inhibited without generating the degradation in photographic characteristics, such as loss of sensitivity by the generation of the fogging and deterioration of gradation even under severe conditions.