公开(公告)号：JPH03258762A

公开(公告)日：1991-11-19

申请号：JP5578090

申请日：1990-03-07

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  YONEMOTO KATSUMI

IPC: C07D333/22 ,  C07C327/26 ,  C07D213/53 ,  C07D521/00

Abstract: NEW MATERIAL:A S-aroylthiooxime of formula I (Ar is aryl which may have a substituent; R is phenyl or heterocyclic group which may have a substituent at the p-position). EXAMPLE:S-Benzoylbenzthiooxime. USE:The compound exhibits a SHG activity and useful as a nonlinear optical material. Since the compound exhibits high reactivity and reacts with various kinds of reagents to give many derivatives, the compound is useful also for synthetic chemistry. PREPARATION:A S-aroylsulfenamide of formula II is reacted with an aldehyde of formula III in the presence of an acid catalyst in an organic solvent at 50-100 deg.C to provide the component of formula I. The compound of formula II is synthesized by dropping a hydroxylamine-O-sulfonic acid aqueous solution into the alkali aqueous solution of an aromatic thiocarboxylic acid at a temperature below room temperature.

公开(公告)号：JPS62106088A

公开(公告)日：1987-05-16

申请号：JP24344485

申请日：1985-10-30

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  NAKANISHI HIROSHI

IPC: H01B1/12 ,  A01N55/00 ,  C07C67/00 ,  C07C325/00 ,  C07C391/00 ,  C07D293/08 ,  G03G5/14

Abstract: NEW MATERIAL:A 2,4-bis(di-substituted amino)-6-substituted-1,3,5-selenadiazinium salt shown by the formula I [R -R are (substituted) alkyl, R and R , and R and R may be bonded to form ring; R is (substituted)di-substituted amino or aryl]. EXAMPLE:2-Dimethylamino-4-morpholino-6-phenyl-1,3,5-selenadiazinium tetrafluo roborate. USE:An intermediate for synthesizing cationic dye, electronic industrial material, selenium-containing and nitrogen-containing derivative. PREPARATION:A 1,3-bis(di-substituted amino)-1,3-dichloro-2-azopropenium chloride shown by formula II is reacted with a selenamide shown by formula III. The compound shown by the formula II can be obtained by reacting (dichloromethylene)dimethylammonium chloride shown by formula IV with a di-substituted dicyanamide (e.g., compound shown by formula V, etc.,) in a chlorine-containing solvent such as methylene chloride, etc.

公开(公告)号：JPS61205269A

公开(公告)日：1986-09-11

申请号：JP4705285

申请日：1985-03-08

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO

IPC: C07D293/02 ,  C07D293/04 ,  C07F11/00

Abstract: NEW MATERIAL:The compound of formula I(R -R are alkyl or aryl which may have inert substituent group; R and R or R and R may be bonded with each other at their terminals; X is inorganic strong acid radical). EXAMPLE:3-(1-Piperidino)-5-dimethylamino-1,2,4-diselenazolium perchlorate. USE:Intermediate for agricultural chemicals, cationic dyes, materials for electronic industry, and novel selenium-containing and nitrogen-containing derivatives. PREPARATION:The objective compound of formula I can be produced safety, in high yield, with extremely simple process, by treating the compound of formula II with sodium hydrogen selenide and then with a peroxide. The starting compound of formula II is obtained easily by treating an equimolar mixture of a disubstituted cyanamide and a disubstituted ammonium chloride in a chlorine-containing solvent such as methylene chloride.

公开(公告)号：JP2000095768A

公开(公告)日：2000-04-04

申请号：JP28339798

申请日：1998-09-18

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

Inventor： SHIMIZU MASAO ,  SHIBUYA ISAO ,  GAMA YASUO

IPC: C07D275/04

Abstract: PROBLEM TO BE SOLVED: To obtain in high yield the subject compound useful as an antimicrobial agent or the like using readily available starting materials without using toxic chlorine gas by intramolecularly cyclizing condensation of a specific sulfenamxde compound. SOLUTION: This compound of formula III (e.g. a compound of formula IV) is obtained by intramolecularly cyclizing condensation of a sulfenamide compound of formula I (R1 to R4 are each H or an inert substituent in the intramolecularly cyclizing condensation reaction of the sulfenamide compound; R5 is an inert substituent in the intramolecularly cyclizing condensation reaction of the sulfenamide compound) (e.g. a compound of formula II) pref. in the presence of a base such as an alkali metal hydroxide (e.g. potassium hydroxide) pref. in a solvent such as ethanol pref. at 0-100 deg.C normally for 30 min to 2 h.

公开(公告)号：JP2000072757A

公开(公告)日：2000-03-07

申请号：JP23786798

申请日：1998-08-25

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  GAMA YASUO ,  SHIMIZU MASAO ,  HONDA KAZUMASA

IPC: C07D251/20 ,  C07D251/46 ,  C07D405/04

Abstract: PROBLEM TO BE SOLVED: To efficiently obtain the subject compound useful as an intermediate for fine chemical products such as medicines and agrochemicals from easily available compounds as raw materials by a simple operation comprising reacting a thiocarbamoyl compound with silver cyanate. SOLUTION: This method for producing a 1,6-disubstituted-1,3,5-triazine-2,4(1 H,3H)-dione compound of formula II, for example, 1,6-diphenyl-1,3,5-triazine-2,4(1 H,3H)-dione, etc., comprises reacting (A) a thiocarbamoyl compound of formula I [Z is-R2,-NHR2, or-N(R2)2(R2 is an organic group); R1 is an organic group] with (B) silver cyanide. The component A is preferably thiobenzoyl anilide, etc., and the component B is preferably used in an amount of >=2 equivalents per mole of the component A. The reaction is preferably carried out in an organic solvent such as acetonitrile.

公开(公告)号：JPH10245365A

公开(公告)日：1998-09-14

申请号：JP4879797

申请日：1997-03-04

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  GAMA YASUO ,  SHIMIZU MASAO

IPC: C07D493/10 ,  C07C41/60 ,  C07C43/32 ,  C07C68/00 ,  C07C69/96

Abstract: PROBLEM TO BE SOLVED: To safely produce the subject compounds useful as an intermediate for agrochemical, medicines, etc., in high yield without using a special raw material by carrying out the desulfurizing reaction of a mono- and a dihydroxy compound and carbon disulfide in the presence of a base and a heavy metallic compound. SOLUTION: The desulfurizing reaction of (A) a monohydroxy compound represented by the formula R -OH (R is a monovalent hydrocarbon group, etc.) (e.g. ethanol) or (B) a dihydroxy compound represented by the formula HO-R -OH (R is a bivalent hydrocarbon group, etc.) (e.g. catechol) is carried out in the presence of a base (e.g. a tertianry amine such as triethylamine) and a heavy metallic compound (e.g. silver trifluoroacetate) to thereby afford the objective compound represented by formula I from the compound A or the objective compound represented by formula II from the compound B. A solvent (e.g. acetonitrile) is advantageously used for the desulfurizing reaction. The objective compound is useful as a synthetic intermediate for, e.g. guanidines, esters, carboxylic acid orthoesters, heterocyclic compounds etc., and used as an intermediate raw material for agrochemical, medicines and other organic chemicals.

公开(公告)号：JPH1045719A

公开(公告)日：1998-02-17

申请号：JP11051997

申请日：1997-04-28

Applicant: AGENCY IND SCIENCE TECHN

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

IPC: C07D223/08 ,  C07D225/02 ,  C09K3/00

Abstract: PROBLEM TO BE SOLVED: To easily obtain a new cyclic β-ketothioamide derivative having a chelating effect and a cyclic structure and useful as a separating agent or a recovering agent of a metal, a synthesis intermediate for various kinds of thioamide derivatives having substituted group at β-position, etc. SOLUTION: This cyclic β-ketothioamide derivative is represented by formula I (R is a hydrocarbon; A is a divalent hydrocarbon allowing O, S or N to intervene), e.g. N-methyl-3-oxo-ε-thiocaprolactam. The derivative of formula I is obtained by reacting a N-substituted lactam of formula II e.g. 1- methylpyrrolidin-2-one} with a bis(trialkylsilyl)thioketene of formula III (R , R and R are each an alkyl) and thereafter treating the reaction product with an alcohol.

公开(公告)号：JPH09295973A

公开(公告)日：1997-11-18

申请号：JP25572496

申请日：1996-09-27

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  GAMA YASUO ,  TSUCHIYA TORU ,  TAGUCHI YOICHI ,  OISHI AKIHIRO ,  GOTO MIDORI

IPC: C07D263/44 ,  A61K31/42 ,  A61K31/421 ,  A61K31/535 ,  A61K31/536 ,  A61K31/5377 ,  A61P31/04 ,  C07D265/06 ,  C07D265/10 ,  C07D265/12 ,  C07D265/26 ,  C07D498/04

Abstract: PROBLEM TO BE SOLVED: To obtain the subject two kinds of compounds each useful as an analgesic or germicide under mild conditions in high yield. SOLUTION: An α-hydroxycarboxylic compound of formula I (R and R are each H or an organic group; M is H or a salt-forming cation) is reacted with an organic isothiocyanate compound in the presence of a desulfurizing agent (e.g. silver trifluoroacetate) under basic conditions (e.g. in the presence of triethylamine), in a solvent if needed (e.g. in acetonitrile) at 0-200 deg.C to obtain the objective 2,4-diketoxazolidine compound of formula II. The other objective 2,4-diketometaoxazine compound of formula III (R and R are each H or an organic group) is obtained by reaction between a β-hydroxycarboxylic compound and an organic isothiocyanate compound under conditions similar to those mentioned above.

公开(公告)号：JPH09166842A

公开(公告)日：1997-06-24

申请号：JP34743195

申请日：1995-12-14

Applicant: AGENCY IND SCIENCE TECHN ,  KONISHIROKU PHOTO IND

Inventor： SHIBUYA ISAO ,  SUDA YOSHIHIKO ,  IKEDA TAKESHI ,  NOJIMA TAKAHIKO

IPC: G03C7/00 ,  G03C1/035 ,  G03C1/34

Abstract: PROBLEM TO BE SOLVED: To obtain a sensitive material less liable to variation in performance due to a humidity charge at the time of exposure and ensuring a stable finish by forming a photosensitive silver halide emulsion layer on a substrate and incorporating a specified compd. SOLUTION: This sensitive material has at least one photosensitive silver halide emulsion layer on the substrate and contains at least one kind of compd. represented by the formula, or contains silver halide particles having >=90mol%, preferably &i95mol% silver chloride content in at least one silver halide emulsion layer and contains at least one kind of compd. represented by the formula in the emulsion layer or other hydrophilic colloidal layer through which water permeates into the emulsion layer. In the formula, each of R1 and R2 is alkyl, aryl or a heterocyclic group. X is O or S and each of (m) and (n) is 0 or 1 bur both of them are not 0.

公开(公告)号：JPH08325269A

公开(公告)日：1996-12-10

申请号：JP12778395

申请日：1995-05-26

Applicant: AGENCY IND SCIENCE TECHN

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

IPC: B01J3/00 ,  C07D491/048 ,  C07D493/04

Abstract: PURPOSE: To simply and efficiently obtain a β-thioloctam derivative useful as a physiologically active substance such as a penicillin-like antibiotic and as its synthetic intermediate by reacting dihydrofuran with an isothiocyanic acid ester which are easily available materials. CONSTITUTION: (A) An isothiocyanic acid ester of the formula: R-NCS (R is an alkyl, an aryl) and (B) 2,3-dihydrofuran preferably in a large excessive amount are subjected to an addition-cyclization reaction preferably under >=2000 atmospheric pressure (especially 2000-10000 atmospheric pressure) at 0-200 deg.C (especially 20-150 deg.C) usually for 1-50hrs. The reaction solvent includes an aliphatic hydrocarbon solvent, an alicyclic hydrocarbon solvent and an aromatic hydrocarbon solvent.