公开(公告)号：JPS6317858A

公开(公告)日：1988-01-25

申请号：JP16191186

申请日：1986-07-11

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  OBATA YOSHIKO ,  URATA HISAO

IPC: C07B61/00 ,  C07D203/08 ,  C07D301/02 ,  C07D303/08

Abstract: PURPOSE:To obtain a fluorine-containing cyclic compound useful as a raw material for fluorine-contained polymers simply and in a short process, by reacting a readily obtainable polyfluoroalkyl halide with an allyl compound in the presence of a palladium catalyst and a base. CONSTITUTION:A polyfluoroalkyl halide (e.g., perfluorooctyl iodide, etc.) shown by formula I (X is Br or I; R and R are H, halogen or polyfluorocarbon) is reacted with an allyl compound (e.g. allyl alcohol, etc.) shown by formula II (Q is O or -NR -; R -R are H, alkyl, alkenyl, aryl or aralyl) in the presence of both a palladium catalyst [e.g., Pd fine powder, dichloro(triphenylphosphine) palladium, etc.] and a base (especially preferably alkali metallic carbonate) to give a fluorine-containing cyclic compound (e.g., 3-perfluorooctyl-1,2- epoxypropane, etc.) shown by formula III.

公开(公告)号：JPS62174065A

公开(公告)日：1987-07-30

申请号：JP24176086

申请日：1986-10-11

Applicant: SAGAMI CHEM RES

Inventor： HIRAI KENJI ,  FUCHIGAMI TAKAMASA ,  MURATA ATSUKO ,  HIROSE HIROAKI ,  YOKOTA MASAHIRO ,  NAGATO SHOIN

IPC: C07D263/44 ,  A01N43/76

Abstract: NEW MATERIAL:A compound shown by formula I (R -R are H, halogen, NO2, alkykl, alkoxy, alkenyloxy, alkynyloxy or cycloalkyloxy wherein alkyl, alkoxy, alkenyloxy, alkynyloxy or cycloalkykloxy may be replaced, respectively; R and R are H, alkyl or aryl which may be replaced, respectively or R and R are bonded to form polymethylene chain). EXAMPLE:3-(4'-Chlorophenyl)-5-isopropylidene-1, 3-oxazolidine-2, 4-dione. USE:A herbicide. PREPARATION:A carbamic acid ester shown by formula II (R is alkyl) is treated with a base (e.g., tertiary amine or alkali metal alkoxide) to give a compound shown by formula I. The compound shown by formula II is obtained by reacting an aryl isocyanate shown by formula III (Y is isocyanato or chlorocarbamoyl) or carbamoyl chloride with a beta, gamma-unsaturated- alpha- hydroxycarboxylic acid ester shown by formula IV.

公开(公告)号：JPS61275247A

公开(公告)日：1986-12-05

申请号：JP11434985

申请日：1985-05-29

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  URATA HISAO ,  TANAKA MARIKO

IPC: C07C69/34 ,  B01J27/00 ,  B01J27/122 ,  B01J27/13 ,  C07B61/00 ,  C07C67/38 ,  C07C69/612 ,  C07C69/708 ,  C07C69/734

Abstract: PURPOSE:To produce the titled compound efficiently under mild conditions, by reacting a terminal olefin with an alcohol in te presence of a palladium catalyst and copper salt using a specific amount or more based on the terminal olefin, orthoester in CO atmosphere. CONSTITUTION:A terminal olefin, e.g. 1-dodecene, is reacted with an alcohol, e.g. ethanol, in the presence of a palladium catalyst, e.g. palladium chloride, and a copper salt, e.g. cupric chloride, using >=2 equivalents, particularly 2-4 equivalents orthoester, e.g. orthoformic acid ester in carbon monoxide atmosphere to give the aimed beta-alkoxycarboxylic acid ester, e.g. ethyl 3- ethoxytridecanoate. EFFECT:No investment in a equipment, e.g. pressurized device, is required. USE:Solvents, plasticizers, etc.

公开(公告)号：JPS61275246A

公开(公告)日：1986-12-05

申请号：JP11434885

申请日：1985-05-29

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  URATA HISAO ,  TANAKA MARIKO

IPC: C07B61/00 ,  B01J27/00 ,  B01J27/13 ,  C07C67/38

Abstract: PURPOSE:To produce the titled compound useful as a solvent, plasticizer, etc., by catalytically reacting an olefin with carbon monoxide, oxygen and alcohol in the presence of a palladium catalyst, copper salt and alkali metal halide under relatively mild conditions. CONSTITUTION:An olefin, e.g. 1-dodecene, is reacted with carbon monoxide, oxygen and an alcohol, e.g. methanol, in the presence of a palladium catalyst, e.g. fine powder of palladium, palladium halide, palladium acetate or palladium carbon, copper salt, e.g. copper acetate, copper chloride or copper iodide, and alkali metal halide, e.g. sodium chloride, lithium chloride or sodium iodide and, as desired, a compound of an iron family metal or cobalt family metal of Group VIII of the periodic table as a cocatalyst added thereto, e.g. iron carbonyl or cobalt carbonyl, to afford the aimed carboxylic acid ester, e.g. methyl 2-methyldodecanoate.

公开(公告)号：JPS61145167A

公开(公告)日：1986-07-02

申请号：JP26548284

申请日：1984-12-18

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  YAMANOUCHI AKIKO ,  SAKAI KUNIKAZU ,  YAMADA KAORU

IPC: C07D405/04 ,  A61K31/505 ,  A61P35/00 ,  C07D239/00 ,  C07D239/54 ,  C07D239/553 ,  C07D307/00

Abstract: NEW MATERIAL:The compound of formula I (R and R are alkyl, alkenyl, aralkyl or oxygen-containing heterocyclic group). EXAMPLE:1-Methyl-3-benzyl-5-fluoro-6-chlorouracil. USE:An antitumor agent having decreased toxicity of 5-fluorouracil with lowering its activity to suppress the proliferation of malignant tumor. PREPARATION:The compound of formula I can be produced economically without using hazardous fluorine agent, by (1) reacting the compound of formula II with phosphorus oxychloride in the absence of solvent, preferably in the presence of a tert-amine such as dimethyl-aniline, at room temperature-150 deg.C, or (2) reacting the compound of formula IV with the compound of formula V (X is halogen) in an aprotic solvent, preferably in the presence of an acid acceptor under cooling or at

公开(公告)号：JPS60179147A

公开(公告)日：1985-09-13

申请号：JP3251384

申请日：1984-02-24

Applicant: SAGAMI CHEM RES

Inventor： HIRAI KENJI ,  FUCHIGAMI TAKAMASA ,  HIROSE HIROAKI ,  OSHIMA IWAO

IPC: B01J27/06 ,  B01J27/128 ,  B01J27/138 ,  B01J31/02 ,  B01J31/22 ,  C07B61/00 ,  C07C67/333 ,  C07C69/732 ,  C07C69/738

Abstract: PURPOSE:To isomerize an ester of glycidic acid and 2-hydroxy-3-butenoic ester at comparatively low temp. with excellent yield by using a salt or a complex salt consisting of a specified metal, a ligand and Broensted acid conjugate base. CONSTITUTION:The titled catalyst consists of a salt or a complex salt show by formula (MLm) (Y)n [M is metals of groups I B, IIA, IIB or VIII, L is a ligand (for example, pi-allyl group, benzene), Y is Broensted acid conjugate base (fo example, nickel perchlorate), (m) is 1-4, (n) is 1-3]. An ester of glycidic acid and 2-hydroxy-3-butenoic ester are isomerized by said catalyst at comparatively low temp. with excellent yield without usage of many reagents for isomerization and a corrosive acid catalyst and arylpyruvic ester or the like can be obtained.

公开(公告)号：JPS60161947A

公开(公告)日：1985-08-23

申请号：JP1444584

申请日：1984-01-31

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  SUZUKI YASUYUKI

IPC: C07C57/52 ,  C07C51/00 ,  C07C51/353 ,  C07C51/363 ,  C07C67/00 ,  C07C67/307 ,  C07C67/343 ,  C07C69/65

Abstract: PURPOSE:To prepare the titled compound which is a raw material for polymers useful as molding agents and surface treatments in simple steps, by reacting an easily available alpha-trifluoromethylacrylic acid derivative with anonic species, e.g. a metal hydride, and treating the reaction product if desired with an acid. CONSTITUTION:An alpha-trifluoromethylacrylic acid derivative expressed by formula I (R is H, alkyl or alkali metal) is reacted with anionic species expressed by formula II (R' is H, alkyl, alkenyl, alkynyl, aryl or aralkyl) such as a metal hydride complex compound, metal hydride, Grignard reagent, organocopper reagent, e.g. ethylmagnesium bromide, to give a reaction product, which is if desired treated with an acid to afford the aimed beta,beta-difluoroacrylic acid derivative expressed by formula III (R is H or alkyl). The compound expressed by formula I , e.g. alpha-trifluoromethylacrylic acid, is easily obtained by reacting 2-bromo- 3,3,3-trifluoropropene with CO and water in the presence of a base, palladium and potassium iodide.

公开(公告)号：JPS6042411A

公开(公告)日：1985-03-06

申请号：JP14959283

申请日：1983-08-18

Applicant: CENTRAL GLASS CO LTD ,  SAGAMI CHEM RES

Inventor： KOISHI TOSHIO ,  TANAKA ISAO ,  YASUMURA TAKASHI ,  OSHIMA IWAO ,  FUCHIGAMI TAKAMASA

IPC: C08F16/00 ,  C08F16/16 ,  C08F20/00 ,  C08F20/02 ,  C08F20/10 ,  C08F20/22 ,  C08F216/18 ,  C08F220/22

Abstract: PURPOSE:To produce a fluorine-containing copolymer suitable for use as water repellents, oil repellents, resist materials, optical fiber clad materials, etc., by radical-copolymerizing an alpha-trifuoromethylacrylate with a vinyl ether. CONSTITUTION:A fluorine-containing copolymer having a monomer unit of formula III is produced by copolymerizing about 20-80mol% alpha-trifluoromethylacrylate (e.g., alpha-trifluoromethylacrylate, or 2,2,2-trifluoroethyl alpha-trifiloorumethlacrylate) with about 20-80mol% vinyl ether of formula II (wherein R' is a hydrocarbon-derived alkyl group), e.g., a vinyl ethyl (e.g., vinyl ethyl ether or vinyl 2-chloroethyl ether), in the presence of a radical polymerization initiator (e.g., diisopropyl peroxycarbonate or potassium persulfate).

公开(公告)号：JPS6042352A

公开(公告)日：1985-03-06

申请号：JP14959383

申请日：1983-08-18

Applicant: CENTRAL GLASS CO LTD ,  SAGAMI CHEM RES

Inventor： ISHIHARA AKIRA ,  YASUMURA TAKASHI ,  INOUE SHIYOUJI ,  OSHIMA IWAO ,  FUCHIGAMI TAKAMASA

IPC: C07C69/653 ,  C07C67/08

Abstract: PURPOSE:In preparing the titled substance useful as an industrially important fluorine polymer by reacting alpha-trifluoromethylacrylic acid with an alcohol, to improve the yield, by using fuming sulfuric acid as a dehydrating agent. CONSTITUTION:A fluorine-containing methacrylic acid shown by the formula I is reacted with an alcohol in the presence of fuming sulfuric acid preferably at

公开(公告)号：JPS59152335A

公开(公告)日：1984-08-31

申请号：JP2281383

申请日：1983-02-16

Applicant: Sagami Chem Res Center

Inventor： OSHIMA IWAO ,  FUCHIGAMI TAKAMASA

IPC: C07C17/263 ,  B01J31/00 ,  B01J31/20 ,  C07B61/00 ,  C07C17/00 ,  C07C17/26 ,  C07C21/02 ,  C07C21/04 ,  C07C21/14 ,  C07C21/17 ,  C07C21/18 ,  C07C22/08 ,  C07C67/00

CPC classification number: Y02P20/52

Abstract: PURPOSE: The reaction between halopolyfluoroalkane and allylsilane is carried out in the presence of a carbonyl complex of group VIII metal or under radical- generating conditions to permit the high-yield production of the titled substance which is used as a synthetic intermediate of fiber-treating agents.
CONSTITUTION: The reaction between a compound of formula I (R
1 , R
2 are H, halogen, 1W20C polyfluoroalkyl; X
1 is halogen; X
2 is Cl, Br, I; where at least one of R
1 , R
2 and X
1 is F or polyfluoroalkyl) and another compound of formula II(R
3 , R
4 are H, alkyl, aryl; R
5 WR
7 are H, alkyl, aryl) is conducted in the presence of a carbonyl complex of a metal of the group VIII in the periodic table or under radical-generating conditions. As the metal of the group VIII, is preferred iron or ruthenium and the process with the catalyst proceeds in high efficiency, when an amine is added to the system. The latter process is preferably under light irradiation or in the presence of a radical initiator.
COPYRIGHT: (C)1984,JPO&Japio

Abstract translation: 目的：卤代聚氟烷烃和烯丙基硅烷之间的反应是在VIII族金属的羰基络合物存在下或在自由基产生条件下进行的，可以高产量地制备作为纤维处理的合成中间体的标题物质 代理商。 构成：式I化合物（R 1，R 2）之间的反应是H，卤素，1-20C多氟烷基; X 1是卤素; X 2是Cl，Br，I;其中在 R 1，R 2和X 1中的至少一个是F或多氟烷基）和另一种式II化合物（R 3，R 4）是H，烷基，芳基; R 5 - R 7是H，烷基，芳基）在元素周期表中VIII族金属的羰基络合物或自由基产生条件下进行。 作为VIII族的金属，优选的是铁或钌，并且当向体系中加入胺时，具有催化剂的方法以高效率进行。 后一种方法优选在光照射下或在自由基引发剂的存在下进行。