公开(公告)号：JP2001019684A

公开(公告)日：2001-01-23

申请号：JP19513699

申请日：1999-07-08

Applicant: AGENCY IND SCIENCE TECHN

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

IPC: C07D275/04 ,  A61K31/428 ,  A61K31/431 ,  A61P31/04 ,  C07D417/12

Abstract: PROBLEM TO BE SOLVED: To obtain a derivative of 1,2-benzothiazolin-3-one having various bioactivities, producible in an industrially profitable method overcoming a defect of using toxic chlorine gas for preparation of a starting raw material. SOLUTION: This compound is expressed by formula I (R1 to R4 are each H or a substituent; Ar is an aromatic substituent), e.g. a compound expressed by formula II. The compound of formula I is obtained, for example, in a method, etc., reacting (A) a 1,2-benzisothiazoline-3-one compound of formula III having no substituent at the 2-position, and (B) a sulfenamide compound of the formula: Ar-S-NH2 having N-S bond which is relatively easy to cleave, in (C) a reaction solvent if necessary, preferably at 50-150 deg.C, more preferably at 80-120 deg.C, for 2-12 hours. Ethyl 2-sulfenamoylbenzoate, isopropyl 2-sulfenamoylbenzoate, ethyl 2-sulfenamoylpyridine-3-carboxylate, etc., are enumerated as the component B.

公开(公告)号：JP2000256296A

公开(公告)日：2000-09-19

申请号：JP5571299

申请日：1999-03-03

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIMIZU MASAO ,  SHIBUYA ISAO ,  GAMA YASUO

IPC: C07D311/82 ,  C07C249/02 ,  C07C251/16

Abstract: PROBLEM TO BE SOLVED: To produce the subject compound in high yield under mild conditions by reacting a specific thioamide compound with a dehydrosulfurizing agent comprising a specified haloiminium salt. SOLUTION: (A) A thioamide compound represented by formula I (Ar1 and Ar2 are each an aryl and Ar1 and Ar2 may each be bonded) is reacted with (B) a dehydrosulfurizing agent comprising a haloiminium salt represented by formula II (R1 and R2 are each a lower alkyl; X is a halogen; Y is a counteranion; and (n) is 0 or 1) in the presence of (C) a base (e.g. triethylamine) and (D), as necessary, in a reactional solvent, preferably at -30 to +100 deg.C, more preferably 0-60 deg.C for 30 min to 3 h to produce the objective compound (e.g. a compound represented by formula IV). 2-Chloro-1,3-dimethylimidazolinium chloride, 2-chloro-1,3-dimethyl-3,4,5,6-tetrahydropyrimidinium chloride, etc. are cited as the component B.

公开(公告)号：JP2000229950A

公开(公告)日：2000-08-22

申请号：JP3384399

申请日：1999-02-12

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  GAMA YASUO ,  SHIMIZU MASAO ,  OISHI AKIHIRO

IPC: C07D239/94 ,  B01J27/10 ,  C07B61/00 ,  C07D239/70 ,  C07D239/95

Abstract: PROBLEM TO BE SOLVED: To efficiently obtain in a simple operation the subject compound useful as an intermediate material for medicaments, agrochemicals, etc., by desulfurization reaction between an arylthiocarbamoyl compound and a disubstituted cyanamide compound in the presence of a metal salt. SOLUTION: This compound of formula II is obtained by desulfurization reaction between an N-arylthiocarbamoyl compound of formula I (R1 is an inert substituent; R2 is a hydrocarbon group; and (n) is 0-4) and an N,N- disubstituted cyanamide compound of the formula: NC-N-(R3)2 (R3 is a hydrocarbon group) in the presence of a metal salt (e.g. a silver salt of a strong acid such as perchloric acid, trifluoromethanesulfonic acid, trifluoroacetic acid or fluoroboric acid). The above reaction is carried out preferably as follows: >=2 equivalents, based on the compound of formula I, of the disubstituted cyanamide is dissolved in an organic solvent such as acetonitrile, dioxane, benzene, toluene or N,N-dimethylformamide followed by addition of >=2 equivalents of the metal salt, and the resulting system is agitated at room temperature and also, as necessary, heated.

公开(公告)号：JPH11209369A

公开(公告)日：1999-08-03

申请号：JP1031098

申请日：1998-01-22

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  GAMA YASUO ,  SHIMIZU MASAO

IPC: C07D319/08 ,  C07D493/10 ,  C07D495/10

Abstract: PROBLEM TO BE SOLVED: To obtain the subject compound in a high yield by subjecting a salicylic acid compound and an arylthioketone compound to a desulfurizing condensation reaction in the presence of a desulfurizing agent and a base. SOLUTION: This method for producing a 1,3-benzodioxan-4-one compound of formula III (for example, a compound of formula IV) comprises subjecting (A) a salicylic acid compound of formula I [R is H or a substituent; (n) is 1-4] and (B) (i) an arylthioketone compound of formula II (Ar and Ar are each an aryl) to a desulfurizing condensation reaction in the presence of (ii) a desulfurizing agent (for example, Cu) and (iii) a base (for example, an organic carboxylic acid alkali metal salt). In the reaction, the component Bii is preferably used in an amount of at least 1 equivalent per equivalent of the component Bi, and the component Biii is preferably used in an amount of at least 2 equivalents per equivalent of the component A.

公开(公告)号：JPH11209367A

公开(公告)日：1999-08-03

申请号：JP1033498

申请日：1998-01-22

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  GAMA YASUO ,  SHIMIZU MASAO

IPC: C07D317/34 ,  C07D317/72 ,  C07D493/10 ,  C07D495/10

Abstract: PROBLEM TO BE SOLVED: To obtain the subject compound in a high yield by subjecting an α-hydroxycarboxylic acid compound and an arylthioketone compound to a desulfurizing condensation reaction in the presence of a desulfurizing agent and a base. SOLUTION: This method for producing a 1,3-dioxolan-4-one compound of formula III (for example, a compound of formula IV) comprises subjecting (A) an α-hydroxycarboxylic acid compound of formula I [R and R are each H, a (substituted) alkyl or the like] and (B) (i) an arylthioketone compound of formula II (Ar and Ar are each an aryl) to a desulfurizing condensation reaction in the presence of (ii) a desulfurizing agent (for example, Ag) and (iii) a base (for example, a hydroxycarboxylic acid alkali metal salt). The component Bii is preferably used in an amount of at least 1 equivalent per equivalent of the component Bi, and the component Biii is preferably used in an amount of at least 2 equivalents per equivalent of the component A.

公开(公告)号：JPH0892203A

公开(公告)日：1996-04-09

申请号：JP23284694

申请日：1994-09-28

Applicant: AGENCY IND SCIENCE TECHN

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

IPC: C07D223/08 ,  C07C327/42 ,  C07C327/44 ,  C07D223/02 ,  C07D223/06 ,  C07D225/02

Abstract: PURPOSE: To provide a new β-ketothioamide derivative useful as a chelating reagent or an intermediate for organic synthesis and easily producible by a new reaction of an N,N-disubstituted amide with a bis(trialkylsilyl)thioketene. CONSTITUTION: This β-ketothioamide derivative is expressed by formula I (R and R are each a hydrocarbon group; R is H or a hydrocarbon group; R may be bonded with R or R to form a ring structure), e.g. N,N-dimethyl-3- oxothiobutyramide of formula II. The compound of formula I can be produced by reacting an N,N-disubstituted amide of formula III with a bis(trialkylsilyl) thioketene and treating the reaction product with an alcohol. The β- ketothioamide derivative can be produced by this production process with a simple procedure under mild reaction condition in high yield using an inexpensive raw material.

公开(公告)号：JPH0853485A

公开(公告)日：1996-02-27

申请号：JP19059994

申请日：1994-08-12

Applicant: AGENCY IND SCIENCE TECHN

Inventor： SHIBUYA ISAO ,  GAMA YASUO

IPC: C07H9/04 ,  C07B41/04

Abstract: PURPOSE:To selectively acetalize the specific sites of a saccharide in a good yield by reacting the saccharide with a bulky organic group-having thiocarbonyl compound in the presence of a base and a silver salt or a copper salt, while inhibiting side-reactions such as an isomerization reaction. CONSTITUTION:A saccharide (e.g. methyl-alpha-D-glycoside) is reacted with a highly bulky organic group-having thiocarbonyl compound [e.g. bis(dialkylaminophenyl) thioketone] of formula [R , R are (substituted)phenyl, isopropyl, t-butyl, pyridyl, thienyl, morpholino, dimethylamino, etc.] in the presence of a base (e.g. trifluoromethanesulfonic acid copper salt) in an organic solvent (e.g. dimethylformamide) to obtain the compound of formula II (A is the saccharide residue where the two hydroxyl groups at the 2,3-positions or at the 4,6-positions are removed) wherein the 2,3-positions or 4,6-positions of the saccharide are acetalized.

公开(公告)号：JPH0413658A

公开(公告)日：1992-01-17

申请号：JP11845790

申请日：1990-05-08

Applicant: AGENCY IND SCIENCE TECHN

Inventor： YONEMOTO KATSUMI ,  SHIBUYA ISAO

IPC: C07D295/20 ,  C07C313/28 ,  C07C313/32 ,  C07C313/34 ,  C07C327/28 ,  C07C327/52 ,  C07C333/20 ,  C07D213/81 ,  C07D333/40 ,  C07D405/12 ,  C07D409/12 ,  C07D417/12

Abstract: PURPOSE:To simply and rapidly produce various sulfenamide derivatives in good yield by treating an amide type compound with sodium hydride and then reacting the resultant compound with a disulfide derivative. CONSTITUTION:An amide type compound (e.g. 2-thiophenecarboxyamide) expressed by formula I (R is H, aryl, heterocyclic ring, alkyl, dialkylamino or alkoxy) is treated with sodium hydride and then reacted with a disulfide derivative (e.g. tetraethylthiuram disulfide) expressed by formula II (R is N,N- disubstituted thiocarbamoyl, aroyl, aryl or heterocyclic ring) to afford a sulfenamide derivative [e.g. N-(2-thenoyl)-S-diethylthiocarbamoylsulfenamide] expressed by formula III. Raw materials for the aforementioned method are readily available and reagents are inexpensive. The product has silver halide photographic inhibitory effects on fog.

公开(公告)号：JPH03109382A

公开(公告)日：1991-05-09

申请号：JP24860289

申请日：1989-09-25

Applicant: AGENCY IND SCIENCE TECHN

Inventor： TAGUCHI YOICHI ,  SHIBUYA ISAO

IPC: C07D251/34

Abstract: PURPOSE:To efficiently obtain the title compound useful as an improver for resins in high yield by reacting an isocyanic ester in the presence of a base under high pressure. CONSTITUTION:An isocyanic ester (e.g. phenyl isocyanate) shown by the formula NCO (R is alkyl or aryl) is reacted in the presence of a base (e.g. triethylamine) under high pressure (preferably 500-4,000kg/cm ) preferably at room temperature to 10 deg.C for 5-50 hours to give the objective compound shown by the formula.

公开(公告)号：JPH01230674A

公开(公告)日：1989-09-14

申请号：JP5912688

申请日：1988-03-11

Applicant: AGENCY IND SCIENCE TECHN

Inventor： TANAKA MOTOO ,  SEKIGUCHI TATSUO ,  KAWABATA KOJIRO ,  NAKAMURA TAKAYOSHI ,  TACHIBANA HIROAKI ,  MANDA EIICHIRO ,  YASUMOTO MASAHIKO ,  SHIBUYA ISAO

IPC: B41M5/26 ,  C09B23/00 ,  C09B57/00 ,  G03G5/06

Abstract: PURPOSE:To obtain a high-purity squarylium pigment suitable as, e.g., a recording material for optical discs is high yields, by condensing a specified colorant intermediate through dehydration with squaric acid in an organic solvent under a pressure higher than a specified value. CONSTITUTION:A colorant intermediate of the general formula R-H [wherein R is formula I, II, III or IV, R is C18H37, R is H, CH3 or Cl, R is CH3, R is H or CH3, R is H or Cl, X is C(CH3)2, Se or S, and Y is p- chlorobenzenesulfonic acid], e.g., (2,3,3-trimethyl-1-octadecyl-indolinium) p- chlorobenzenesulfonate, is condensed through dehydration with squaric acid in an organic solvent (e.g., methanol) under a high pressure >=1000kg/cm to obtain a squarylium colorant of formula V.