公开(公告)号：JPS635040A

公开(公告)日：1988-01-11

申请号：JP14830086

申请日：1986-06-26

Applicant: SAGAMI CHEM RES

Inventor： FUCHIGAMI TAKAMASA ,  OISHI SHIGERO ,  HOSAKA SHIYURI

IPC: C07C25/18 ,  C07C17/00 ,  C07C41/00 ,  C07C43/225 ,  C07C67/00 ,  C07C201/00 ,  C07C205/12 ,  C07C231/00 ,  C07C231/12 ,  C07C233/15

Abstract: PURPOSE:To obtain the titled substance useful as an intermediate for the synthesis of an aromatic compound having a functional group such as halogen atom, amino group, etc., at a low cost, by using easily available aromatic compound and aromatic iodide as raw materials and reacting with a specific amount of concentrated sulfuric acid in the presence of an oxidization agent. CONSTITUTION:The objective compound of formula III can be produced by reacting (A) an aromatic iodide of formula I (R is alkyl, halogen, nitro, alkoxy or acylamino; m is 0 or 1-5; when m>=2, the R substituent groups are independently selected) with (B) an aromatic compound of formula II (R is alkyl, halogen, nitro, alkoxy or acylamino; n is 0 or 1-5; when n>=2, the R substituent groups are independently selected) and (C) 1-10 equivalent of concentrated sulfuric acid based on the component of formula I in the presence of (D) an oxidization agent such as potassium persulfate, preferably using a solvent containing acetic acid as a diluent at -20-+100 deg.C.

公开(公告)号：JPS62116541A

公开(公告)日：1987-05-28

申请号：JP25663485

申请日：1985-11-18

Applicant: Sagami Chem Res Center

Inventor： HIRAI KENJI ,  FUCHIGAMI TAKAMASA

IPC: C07C59/76 ,  B01J31/00 ,  B01J31/20 ,  C07B61/00 ,  C07C51/00 ,  C07C51/10 ,  C07C67/00

CPC classification number: Y02P20/52

Abstract: PURPOSE: The reaction of an arylmethyl halide with carbon monoxide is carried out in the coexistence of a nitrogen-containing compound, in the presence of a specific catalyst and compound, under moderate pressure of carbon monoxide for a short time to give the titled compound in high selectivity and yield.
CONSTITUTION: An arylmethyl halide of formula I (Ar is aryl; X is halogen) is allowed to react with carbon monoxide and water in an organic solvent such as a branched alcohol of 3W10 carbon atoms, in the presence of cobalt carbonyl, a nitrogen compound such as a quaternary ammonium compound such as triethylbenzylammonium chloride, tertiary amine or amide as catalysts, further in the presence of an inorganic base of alkaline earth metal, preferably at 35W70°C as the partial pressure of carbon monoxide is kept near normal pressure, to give the objective compound.
EFFECT: The process according to the present invention does not require pressure units and the reactions ends in a short time, thus it is very advantageous in efficiency, when it is produced on an industrial scale.
COPYRIGHT: (C)1987,JPO&Japio

Abstract translation: 目的：芳基甲基卤化物与一氧化碳的反应在含有化合物的情况下，在特定催化剂和化合物的存在下，在中等压力的一氧化碳下短时间内进行，得到标题化合物 高选择性和产率。 构成：在羰基钴存在下，使式I的芳基甲基卤（Ar是芳基; X是卤素）与一氧化碳和水在有机溶剂例如3-10个碳原子的支链醇中反应， 氮化合物如季铵化合物如三乙基苄基氯化铵，叔胺或酰胺作为催化剂，进一步在碱土金属的无机碱存在下，优选在35-70℃下保持一氧化碳的分压 接近正常压力，给出目标化合物。 效果：根据本发明的方法不需要压力单位，并且反应在短时间内结束，因此当其以工业规模生产时，其效率非常有利。

公开(公告)号：JPS61204150A

公开(公告)日：1986-09-10

申请号：JP4461185

申请日：1985-03-08

Applicant: SAGAMI CHEM RES

Inventor： HIRAI KENJI ,  FUCHIGAMI TAKAMASA

IPC: C07C59/56 ,  C07C51/00 ,  C07C51/353 ,  C07C57/58 ,  C07C59/64 ,  C07C67/00 ,  C07D213/55 ,  C07D213/63 ,  C07D213/64 ,  C07D213/76 ,  C07D215/14 ,  C07D215/20 ,  C07D217/00

Abstract: NEW MATERIAL:An alpha-halo-alpha-trifluoromethyl-beta-aryl-propionic acid shown by the formula (Ar is substituted or unsubstituted aromatic group; X is Cl, or Br). EXAMPLE:alpha-Chloro-alpha-trifluoromethyl-beta-phenylpropionic acid. USE:A raw material for synthesizing alpha-trifluoromethylphenylalanine useful as an antihypertensive, capable of synthesizing a compound as an antihypertensive economically and efficiently. PREPARATION:A diazonium salt shown by the formula II is reacted with alpha- trifluoromethylacrylic acid in the presence of a copper catalyst in a solvent such as water, acetone, etc. at -10-50 deg.C to give a compound shown by the formula I.

公开(公告)号：JPS6187644A

公开(公告)日：1986-05-06

申请号：JP20989384

申请日：1984-10-08

Applicant: Sagami Chem Res Center

Inventor： FUCHIGAMI TAKAMASA ,  URATA HISAO ,  TANAKA MARIKO ,  KONDO SEI

IPC: C07C69/675 ,  C07C69/732

Abstract: NEW MATERIAL:Compds. expressed by formula I [R is lower alkyl, R
1 is formula II (R
2 =R), formula III or formul IV (R
3 s are R or together form alkylene or polymethylene group)].
EXAMPLE: Methyl 5,5-dimethoxy-3,3-dimethylpentanoate.
USE: A raw material for 5-oxo-3,3-dimethylpentanoic esters useful as a starting material for insecticides such as permethrin.
PREPARATION: A 3,3-dimethyl-4-pentanoic ester expressed by formula V, and carboxylic acid expressed by the formula R
2 COOH such as acetic acid are reacted in the presence of oxygene and a Pd catalyst such as palladium acetate, at room temp. W 150°C, to form compds. expressed by formula I (R
1 is formulas II and III). The resultant products are reacted with an alcohol expressed by the formula R
3 OH such as methanol in the presence of an acetalizing catalyst such as p-toluenesulfonic acid at room temp. W 100°C to obtain the compd. expressed by formula I (R
1 is formula IV).
COPYRIGHT: (C)1986,JPO&Japio

Abstract translation: 新材料：Compds 由式I表示[R是低级烷基，R 1是式II（R 2 = R），式III或式IV（R 3是R或一起形成亚烷基或多亚甲基）]。 实施例：5,5-二甲氧基-3,3-二甲基戊酸甲酯。 用途：5-氧代-3,3-二甲基戊酸酯的原料，可用作杀虫剂如苄氯菊酯的起始原料。 制备：由式V表示的3,3-二甲基-4-戊酸酯和由式R 2 COOH如乙酸表示的羧酸在氧基和Pd催化剂如乙酸钯， 在室温 - 150摄氏度，形成compds。 由式I表示（R 1是式II和III）。 在室温下，在缩醛催化剂如对甲苯磺酸的存在下，使所得产物与式R 3 OH表示的醇如甲醇反应。 - 100℃以获得化合物 由式I表示（R 1是式IV）。

公开(公告)号：JPS60248713A

公开(公告)日：1985-12-09

申请号：JP10365784

申请日：1984-05-24

Applicant: CENTRAL GLASS CO LTD ,  SAGAMI CHEM RES

Inventor： KOISHI TOSHIO ,  ISHIHARA AKIRA ,  FUCHIGAMI TAKAMASA ,  OSHIMA IWAO

IPC: C08F20/00 ,  C06B23/00 ,  C08F20/22 ,  C08F212/00 ,  C08F212/04 ,  C08F220/22 ,  C08F220/24 ,  C08G18/40 ,  C08G18/48

Abstract: PURPOSE:To obtain a fluorine-contained copolymer useful as a water repellent or an oil repellent, or a resist material, etc. in high yield, by copolymerizing a specific fluorine-containing methacrylic acid ester with a styrenic monomer in the presence of a radical polymerization initiator. CONSTITUTION:(A) A fluorine-containing methacrylic acid ester shown by the formula I (R is alkyl group of hydrocarbon of fluorine) is copolymerized with (B) a styrenic monomer shown by the formula II (X is H, hydrocarbon alkyl, halogen, vinyl, amino, or hydroxyl group) in the presence of (C) a radical polymerization initiator, to give the aimed copolymer. A compound wherein R is CnH2n+1 (n is integer) or group shown by the formula III (m is 0-5 integer; Rf is 1-20C polyfluoroalkyl; R is lower alkyl, H, or Rf) is preferable as the component A.

公开(公告)号：JPS60190768A

公开(公告)日：1985-09-28

申请号：JP4377884

申请日：1984-03-09

Applicant: Sagami Chem Res Center

Inventor： FUCHIGAMI TAKAMASA ,  YAMANOUCHI AKIKO ,  SUZUKI YASUYUKI

IPC: C07D239/553 ,  C07D239/00 ,  C07D239/54 ,  C07D307/00 ,  C07D405/04

Abstract: PURPOSE: Readily available 5-fluoro-6-halouracil is used as a starting material to give the titled compound used as an antitumor agent only by reduction through simple and safe process.
CONSTITUTION: For example, a fluorobarbituric acid derivative is allowed to react with a halogenation agent such as phosphorus oxychloride to readily give 5-fluoro-6-halouracil derivative of furmula I (X is Cl, B, I; R
1 , R
2 are H, alkyl, aralkyo, aryl or oxygen-containing heterocyclic ring) such as 5-fluoro-6-chlorouracil. Then the product is reduced with hydrogen in the presence of a transition metal catalyst and a base to give 5-fluorouracil derivative of formula II such as 5-fluorouracil.
COPYRIGHT: (C)1985,JPO&Japio

Abstract translation: 目的：使用5-氟-6-氟尿嘧啶作为起始原料，仅通过简单安全的方法制备用作抗肿瘤剂的标题化合物。 构成：例如，使氟巴比妥酸衍生物与卤化剂如三氯氧化磷反应容易地得到糠醛I的5-氟-6-卤尿嘧啶衍生物（X是Cl，B，I; R 1，R 2是H，烷基，芳烷基，芳基或含氧杂环）如5-氟-6-氯尿嘧啶。 然后在过渡金属催化剂和碱的存在下用氢还原产物，得到式II的5-氟尿嘧啶衍生物如5-氟尿嘧啶。

公开(公告)号：JPS6019771A

公开(公告)日：1985-01-31

申请号：JP12617383

申请日：1983-07-13

Applicant: SAGAMI CHEM RES

Inventor： OSHIMA IWAO ,  FUCHIGAMI TAKAMASA ,  FUJITA MAKOTO

IPC: C07D239/22

Abstract: PURPOSE:To produce the titled compound useful as a synthetic raw material of a compound having carcinostatic and antiviral activities, easily in high yield, by using an alpha-perfluoroalkyl-acrylic acid and a urea derivative as raw materials, and reacting the compounds in the presence of a carboxylic acid anhydride. CONSTITUTION:The compound of formula IV is produced by reacting the alpha-perfluoroalkylacrylic acid of formula II (Rf is 1-10C perfluoroalkyl) with the urea derivative of formula III (R and R are H, alkyl, aralkyl or aryl, and at least one of R and R is H), e.g. methylurea, in the presence of a carboxylic acid anhydride of formula I (R is H, alkyl or aryl or two R's may together form alkylene or polymethylene group), preferably acetic anhydride, at room temperature -200 deg.C, preferably 60-150 deg.C. The compound of formula II is synthesized by reacting 1-halo-1-perfluoroalkylethylene with carbon monoxide and water.

公开(公告)号：JPS59137424A

公开(公告)日：1984-08-07

申请号：JP994083

申请日：1983-01-26

Applicant: Sagami Chem Res Center

Inventor： OSHIMA IWAO ,  FUCHIGAMI TAKAMASA

IPC: C07C41/00 ,  B01J31/20 ,  C07C27/00 ,  C07C67/00

Abstract: PURPOSE: To prepare the titled compound useful as an intermediate of surface agent, etc., economically, by reacting a 1W20C halopolyfluorocarbon with substituted or unsubstituted ethylene or acetylene in the presence of a VIII-group metal carbonyl complex.
CONSTITUTION: The objective compound of formula IV or formula V useful as an intermediate of a water-repellent, oil-repellent, textile sizing agent, etc. as well as the above-mentioned use, is prepared in a short time under mild reaction condition, by reacting (A) a 1W20C compound of formula I (X is Cl, Br, or I; R
1 and R
2 are H, halogen or poly-perfluorocarbon residue) with (B) the compound of formula II or III (R
3 WR
8 are group of R
1 or R
2 , or substituted or unsubstituted alkyl, vinyl, aromatic group, alkyloxy, acyloxy, NH
2 , amido, silyl, etc.) in the presence of (C) a carbonyl complex of the VIII-group metal of the periodic table (preferably Fe or Ru) preferably at room temperature W120°C.
COPYRIGHT: (C)1984,JPO&Japio

Abstract translation: 目的：为了制备可用作表面活性剂中间体等的标题化合物，经济上通过在VIII族金属羰基络合物的存在下使1-20C卤代多氟碳烷与取代或未取代的乙烯或乙炔反应。 构成：在温和的反应条件下，在短时间内制备用作防水，防油，纺织施胶剂等的中间体的式IV或式V的目的化合物，以及上述用途 （A）1-20C的式I化合物（X为Cl，Br或I; R 1和R 2为H，卤素或聚全氟化碳残基）与（B）化合物 式II或III（R 3 -R 8）是R 1或R 2的基团，或取代或未取代的烷基，乙烯基，芳基，烷氧基，酰氧基，NH 2，酰氨基，甲硅烷基等。 ）在（C）周期表的VIII族金属（优选Fe或Ru）的羰基络合物存在下，优选在室温-120℃下进行。

公开(公告)号：JPS57185233A

公开(公告)日：1982-11-15

申请号：JP6943481

申请日：1981-05-11

Applicant: SAGAMI CHEM RES

Inventor： OSHIMA IWAO ,  FUCHIGAMI TAKAMASA ,  YATABE MOMOKO

IPC: C07C43/313 ,  C07C41/00 ,  C07C67/00

Abstract: NEW MATERIAL:A 1,1-dialkoxy-2-trifluoromethylpropane expressed by formulaI (R is alkyl). EXAMPLE:1,1-Diethoxy-2-trifluoromethylpropane. USE:A starting material for various chemicals having CF3 group, e.g. 2-trifluoromethylpropanal, a stable equivalent to the trifluoromethylpropanal, and usable as a reagent for introducing the 2-trifluoromethylpropyl group. PROCESS:2-Trifluoromethylpropanal expressed by formula II is reacted with an orthoformic ester expressed by the formula HC(OR)3 in a solvent in the presence of ammonium chloride at room temperature -100 deg.C to give the compound expressed by formulaI.

公开(公告)号：JPS56164173A

公开(公告)日：1981-12-17

申请号：JP6593080

申请日：1980-05-20

Applicant: SAGAMI CHEM RES

Inventor： OSHIMA IWAO ,  FUCHIGAMI TAKAMASA

IPC: C07D263/42

Abstract: PURPOSE:To prepare the titled compound useful as an intermediate for an antimicrobial agent in simple steps, by reacting a readily available 2-perfluoroalkylpropanal with an N-acylglycine as raw materials in the presence of a base and acetic anhydride. CONSTITUTION:A 2-perfluoroalkylpropanal of formula I (Rf is perfluoroalkyl) is reacted with an N-acylglycine of formula II (R is substituted or unsubstituted alkyl or aromatic group) in the presence of a base, preferably lead acetate, and acetic anhydride, preferably in an ethereal solvent, e.g. tetrahydrofuran, at 50-150 deg.C to give an azlactone derivative of formula III, e.g. azlactone of alpha-benzoylamino- beta-(1-trifluoromethyl)ethylacrylic acid. The compound of formula I is obtained from a 1-perfluoroalkylethylene by the oxo reaction.