公开(公告)号：JP2002173458A

公开(公告)日：2002-06-21

申请号：JP2000369054

申请日：2000-12-04

Applicant: ASAHI GLASS CO LTD

Inventor： ASAI TOMOYUKI ,  NAKAJIMA YOSHIKO

IPC: C07C45/46 ,  C07C49/80 ,  C07F3/02

Abstract: PROBLEM TO BE SOLVED: To provide a workability-improved, industrially useful and efficient method for producing an acetophenone compound containing trifluoromethyl group. SOLUTION: This method for producing an acetophenone compound containing trifluoromethyl group such as 3,5-bis(trifluoromethyl)acetophenone comprises reacting a halogenobenzene containing trifluoromethyl group such as 3,5-bis(trifluoromethyl)bromobenzene with an alkylmagnesium halide such as ethylmagnesium bromide and reacting the thus obtained phenylmagnesium halide containing trifluoromethyl group such as 3,5-bis(trifluoromethyl) phenylmagnesium bromide with acetic anhydride.

公开(公告)号：JPH0967304A

公开(公告)日：1997-03-11

申请号：JP22343595

申请日：1995-08-31

Applicant: ASAHI GLASS CO LTD

Inventor： SHIMIZU TAMAKI ,  ASAI TOMOYUKI ,  KUMAI SEISAKU

IPC: C07C51/353 ,  C07C63/70 ,  C07C65/01 ,  C07C65/30 ,  C07C319/14 ,  C07C323/62

Abstract: PROBLEM TO BE SOLVED: To simply obtain the subject compound in high yield without protecting a carboxylic acid part by reacting a specific fluorobenzoic acid derivative with an electrophilic reagent, into which a specific prescribed group can be introduced, in the presence of a base, useful as a synthetic intermediate for a fluoroquinoline-based antimicrobial agent, etc. SOLUTION: (A) A compound of formula I (X is H or a halogen) is reacted with (B) an electrophilic reagent [e.g. a compound obtained by brominating and iodating one hydrogen of a (F, Cl-substituted) 1-10C aliphatic hydrocarbon], into which a group (R ) such as a 1-10C aliphatic hydrocarbon group, an alkylthio, an arylthio, a halogen, carboxyl, etc., can be introduced, in the presence of (C) a base such as a compound of the formula (R ) (R )NM (R and R are each a 1-10C organic group or R and R may form a ring; M is an alkali metal ion), etc., to give a compound of formula II.

公开(公告)号：JPH08325238A

公开(公告)日：1996-12-10

申请号：JP13217795

申请日：1995-05-30

Applicant: ASAHI GLASS CO LTD

Inventor： SHIMIZU TAMAKI ,  ASAI TOMOYUKI ,  KUMAI SEISAKU

IPC: C07D239/54 ,  B01J23/72 ,  B01J27/122 ,  C07B61/00

Abstract: PURPOSE: To easily obtain the subject compound useful as a synthetic intermediate for carcinostatic agent and antiviral agent from inexpensive raw materials in high yield by trifluoromethylating a halogenated uracil derivative having a specific structure. CONSTITUTION: The objective compound of formula II is produced by trifluoromethylating a 5-halogenated uracil derivative of formula I (R and R are each H, a 1-10C alkyl, benzyl, etc.; X is Cl, I or Br) with preferably 0.5-5 times mol (based on the compound of formula I) of 2,2- difluoro-2-(fluorosulfonyl)acetic acid methyl ester. Preferably, copper or copper iodide is used as a catalyst and DMF is used as a reaction solvent in the above reaction. The reaction is carried out at 50-150 deg.C for 3-10hr. N ,N -dibenzyl-5- trifluoromethyluracil of formula III is a new compound among the compounds of formula II. The compound of formula III can be produced e.g. from N ,N - dibenzyl-5-iodouracil.

公开(公告)号：JPH01113399A

公开(公告)日：1989-05-02

申请号：JP26943087

申请日：1987-10-27

Applicant: ASAHI GLASS CO LTD

Inventor： ASAI TOMOYUKI ,  SUGA ATSUO ,  MORISAWA YOSHITOMI ,  YASUDA ARATA ,  UCHIDA KEIICHI

IPC: C07H5/02 ,  C07H19/073 ,  C07H19/173

Abstract: NEW MATERIAL:A compound expressed by the formula [R1 are residue of nucleic acid bases which may have a protecting group, halogen or formula OX (X is H, protecting group or alkyl); R is protecting group of H or hydroxyl group]. EXAMPLE:2',3'-Deoxy-2'-fluorouridine. USE:An antiulcer agent or antiviral agent. PREPARATION:For example, 5'-O-tert.-butyldimethylsilyl-2'-deoxy-2'-fluorouridine dissolved in methylene chloride, etc., is reacted with 4-dimethylaminopyridine and phenylchlorothionocarbonate added to the above-mentioned solution to afford 5'-O-tert.-butyldimethylsilyl-2',3'-dideoxy-2'-fluorouridine, which is then reacted with tetrabutylammonium added to the above-mentioned fluorouridine derivative and the resultant reaction product is purified with a column chromatography to provide the compound expressed by the formula.

公开(公告)号：JPS6110551A

公开(公告)日：1986-01-18

申请号：JP12999384

申请日：1984-06-26

Applicant: Asahi Glass Co Ltd

Inventor： YASUDA ARATA ,  ASAI TOMOYUKI ,  KATOU MASAO ,  UCHIDA KEIICHI

IPC: C07D307/935 ,  C07C67/00 ,  C07C401/00 ,  C07C405/00 ,  C07F7/18

CPC classification number: Y02P20/55

Abstract: PURPOSE: To obtain the titled compound having OH groups protected with specific protective groups easily in high yield, by protecting OH of a specific prostaglandin, converting O of carbonyl into OH, protecting the OH with a specific protecting group.
CONSTITUTION: OH at the 7-position of a prostaglandin shown by the formula I [R
1 is 1W10C alkyl; R
2 is alkyl containing 3W7C cyclic group; R
3 and R
4 are protecting group except trimethylsilyl group; the formula II is substituent group in β orientation (the upper part of plane of molecule); dotted line (...) is substituent group in α orientation (the lower part of plane of molecule); wavy line (W) is substituent group in α or β orientation or substituent group of mixture of their isomers] is protected with trimethylsilyl group, O of the carbonyl group at the 9-position is converted into OH, the OH is then protected with a protecting group except trimethylsilyl, to give the aimed compound shown by the formula IV(R
5 =R
3 or R
4 ) useful as a precursor for a 7-fluoroprostaglandin I
2 shown by the formula III (R
6 and R
7 are protecting group of H).
COPYRIGHT: (C)1986,JPO&Japio

Abstract translation: 目的：通过保护特定前列腺素的OH，通过保护OH的特异性保护基得到具有高特异性保护基保护的OH基的标题化合物，将羰基O转化为OH，用特定保护基保护OH。 组成：式I [R 1]所示的前列腺素的7-位的OH为1-10C烷基; R 2是含有3-7C环烷基的烷基; R 3和R 4是除三甲基甲硅烷基之外的保护基; 式II是β取向的取代基（分子平面的上部）; 虚线（...）是α取向的取代基（分子平面的下部）; 波长线（ - ）是α或β取向的取代基或它们的异构体的混合物的取代基]用三甲基甲硅烷基保护，9位上的羰基的O转化为OH，然后用 除了三甲基甲硅烷基之外，得到用作式III表示的7-氟前列腺素I2的前体的式IV所示的目的化合物（R 5 = R 3或R 4））（R 6 >和R 7是H的保护基）。

公开(公告)号：JP2001039929A

公开(公告)日：2001-02-13

申请号：JP21565599

申请日：1999-07-29

Applicant: ASAHI GLASS CO LTD

Inventor： TANIGUCHI TOMOKO ,  ASAI TOMOYUKI

IPC: C07C201/06 ,  C07C205/12

Abstract: PROBLEM TO BE SOLVED: To simply obtain the subject compound useful as an intermediate for medicines and agrochemicals from readily preparable raw materials by a short process by treating aminochlorobenzotrifluoride with an oxidizing agent in a solvent. SOLUTION: An aminochlorobenzotrifluoride of formula I (e.g. 4-amino-3- chlorobenzotrifluoride of formula II, etc.), is treated with an oxidizing agent (e.g. a peroxide such as sodium perborate, sodium percarbonate, etc.), in a solvent (preferably water, a lower alcohol, a lower carboxylic acid or a nitrile, to be concrete, especially methanol, acetic acid, etc., may be cited) to give the objective compound of formula III (e.g. a compound of formula IV). The amount of the solvent used is preferably 3-30 times as much as parts by weight of the compound of formula I and the amount of the oxidizing agent is preferably 1-20 equivalents based on the compound of formula I.

公开(公告)号：JPH1171319A

公开(公告)日：1999-03-16

申请号：JP23490497

申请日：1997-08-29

Applicant: ASAHI GLASS CO LTD

Inventor： FUJIMA TOSHIHIKO ,  ASAI TOMOYUKI

IPC: B01J31/02 ,  C07B61/00 ,  C07C45/64 ,  C07C47/575

Abstract: PROBLEM TO BE SOLVED: To obtain the subject compound useful as an intermediate for pharmaceuticals and agrochemicals by reacting a hydroxybenzaldehyde compound with chlorodifluoromethane in the presence of water, an organic solvent, a base and a phase-transfer catalyst. SOLUTION: The objective compound expressed by the formula HCF2 O-Ph- CHO can be produced by reacting 1 mol of a hydroxybenzaldehyde compound of the formula HO-Ph-CHO (Ph is a 1-4C alkyl, a 1-4C alkoxy, F, unsubstituted phenylene, etc.), (e.g. p, m or o-hydroxybenzaldehyde) with 1.0-2.0 mol of chlorodifluoromethane in the presence of 50-600 ml of water, 200-1,200 ml, of an organic solvent (e.g. dichloromethane and ethylene glycol dimethyl ether), 2.0-4.0 mol of a base and 2-10 mol.% of a phase-transfer catalyst (preferably a quaternary ammonium salt or a quaternary phosphonium salt) preferably at -20 to +20 deg.C.

公开(公告)号：JPH08109143A

公开(公告)日：1996-04-30

申请号：JP18953795

申请日：1995-07-25

Applicant: ASAHI GLASS CO LTD

Inventor： ASAI TOMOYUKI ,  KUMAI SEISAKU

IPC: C07D263/10 ,  B01J23/34 ,  C07B37/04 ,  C07B49/00 ,  C07B61/00 ,  C07C1/32 ,  C07C15/14 ,  C07C17/263 ,  C07C22/08 ,  C07C25/18 ,  C07C41/30 ,  C07C43/205 ,  C07C43/225 ,  C07C67/343 ,  C07C69/76 ,  C07C69/94 ,  C07C255/50 ,  C07D257/04

Abstract: PURPOSE: To efficiently and readily obtain a biphenyl compound in high purity by reacting 2-chlorobenzonitrile, etc., with 4-methyl-phenyl magnesium bromide, etc., in the presence of metal manganese. CONSTITUTION: A compound of formula I (R is H, F, a 1-10C alkyl, a 1-10C alkoxyl, phenyl, etc.; X is Cl, Br or I) is reacted with a compound of formula II (R is H, F, a 1-10C alkyl, a 1-10C alkoxyl, cyano, etc.; Y is Cl, Br or I) in the presence of metal manganese in a solvent (e.g. THF) at the temperature from -100 deg.C to a reflux temperature of the solvent to provide the objective compound of formula III. The reaction is preferably carried out in the presence of chlorotrialkylsilanes. The compound of formula I is used in an amount of 1-1.5 equivalent based on 1 equivalent of the compound of formula II and the metal manganese is used in an amount of 0.01-10mol based on 1mol of the compound of formula II and the chlorotrialkylsilanes are used in an amount of 0.01-1 equivalent based on 1 equivalent of metal manganese. The compound of formula III is useful as an intermediate for medicines and agrochemicals, liquid crystals, heat-resistant polymers, liquid crystalline polymers, etc.

公开(公告)号：JPH06336449A

公开(公告)日：1994-12-06

申请号：JP14689593

申请日：1993-05-26

Applicant: ASAHI GLASS CO LTD

Inventor： FUJIMA TOSHIHIKO ,  ASAI TOMOYUKI ,  YASUDA ARATA

IPC: C07B61/00 ,  C07C17/00 ,  C07C17/23 ,  C07C25/13

Abstract: PURPOSE:To obtain the title compound which is useful as a synthetic intermediate of medicines and agrochemicals by dehydro-chlorinating reaction of a chlorinated m-difluorobenzene with a formate salt in the presence of a catalyst. CONSTITUTION:The objective m-difluorobenzene is obtained by dehydro- chlorinating reaction of a chlorinated m-difluorobenzene of the formula ((m) is 1 to 4) with a formate salt in the presence of a catalyst such as Pd on carbon in a solvent such as methanol at 20 to 150 deg.C under pressure of 0.5 to 100 atmospheric pressure for 0.5 to 24 hours. The formate salt is used in 1 to 10 equivalent amount per 1 equivalent amount of chlorine in the compound of the formula and the catalyst is used in an amount of 0.1 to 50 pts.wt. per 100 pts.wt. of the compound of the formula. The process can be operated under mild conditions without handling high-toxicity and unstable diazonium salt.

公开(公告)号：JPH059184A

公开(公告)日：1993-01-19

申请号：JP25455791

申请日：1991-09-06

Applicant: ASAHI GLASS CO LTD ,  DAINIPPON PHARMACEUTICAL CO

Inventor： ASAI TOMOYUKI ,  MORISAWA YOSHITOMI ,  YASUDA ARATA ,  YAMAMOTO HIROSHI ,  FUJITANI BUICHI ,  HOSOKI KAZU

IPC: A61K31/557 ,  A61K31/5575 ,  A61P7/02 ,  A61P9/00 ,  A61P9/08 ,  A61P9/10 ,  C07D307/935

Abstract: PURPOSE:To provide the subject new compound having strong platelet- coagulating action and antianginal action and low toxicity, and useful as a preventive and treating agent for circulatory diseases. CONSTITUTION:A prostaglandin I2 compound having a halogen atom on 7-site C atom of natural-type prostaglandin I2 and a cycloalkylene group on the alpha-chain, its ester and its salt expressed by formula I [R is (substituted) 1-10C alkyl, (substituted) 5- or 6-membered cycloalkyl, etc. ; R is H, 1-10C alkyl or cation; one of R and R is H and the other is F or Cl; (k), (l), (m) and (n) are 0-6; 0 is 1-10C alkyl, etc.; R and R are protecting group other than trimethylsilyl) into the compound of formula III and subjecting the product to fluorination, deprotection and, as necessary, hydrolysis, salt- forming, etc.