公开(公告)号：JPH03246288A

公开(公告)日：1991-11-01

申请号：JP1026190

申请日：1990-01-19

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  TAKAI TOSHIHIRO

IPC: B01J29/04 ,  B01J31/22 ,  C07B61/00 ,  C07D301/06

Abstract: PURPOSE:To selectively obtain the subject epoxy group-containing compound by reacting a specified compound containing an ethylenic double bond with an oxygen-containing gas using a specified nickel compound as a catalyst in the presence of a primary and/or secondary alcohol. CONSTITUTION:An ethylenic double bond-containing compound (e.g. 2- methyl-2-decene or cis-2-octene) of formula I (R -R are H, alkyl and aryl, provided that R and R , R and R may mutually bond and form ring) is reacted with an oxygen-containing gas using a nickel compound [e.g. bis(3- methylacetylacetonate)nickel] of formula II (R and R are lower alkyl and aryl; R is H, halogen, lower alkyl, aryl or arylalkyl, provided that R and R may mutually bond and form ring) as a catalyst in the presence of a primary and/or secondary alcohol, thus producing the objective compound of formula III.

公开(公告)号：JPH0352833A

公开(公告)日：1991-03-07

申请号：JP18819889

申请日：1989-07-20

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  ISAYAMA SHIGERU ,  INOKI SATORU ,  KATOU KOUJI ,  YAMADA TORU ,  TAKAI TOSHIHIRO

IPC: B01J31/22 ,  C07B61/00 ,  C07C27/00 ,  C07C29/04 ,  C07C31/20 ,  C07C33/26 ,  C07C67/29 ,  C07C69/76 ,  C07C69/80 ,  C07C69/82

Abstract: PURPOSE:To prepare a polyol especially useful as a raw material for polymers or a raw material for synthesizing other chemical compounds in a high conversion and in a high yield by reacting a polyene with an oxygen-containing gas in the presence of a specific cobalt complex catalyst and a secondary alcohol. CONSTITUTION:A polyene of formula I, II or III [R to R are H, lower alkyl or aryl; m, p, s and u are 0-6; m+p and s+u are 2-6, l>=1, n>=1; q>=0, t>=0 (when the position of formula II is ortho position, q and/or t are >=1); 0 =1, y>=1; X is O, CO, OCO, COO, etc.,] is reacted with an oxygen-containing gas in the presence of a catalyst of formula IV (R , R , R and R are H, lower alkyl, aryl or perfluoroalkyl; R and R are H, lower alkyl, halogen, etc., but cases of R =R =R =R =CF3 and R =R are excluded) in the presence of a secondary alcohol to provide a polyol advantageously.

公开(公告)号：JPH02209846A

公开(公告)日：1990-08-21

申请号：JP3076589

申请日：1989-02-09

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  ISAYAMA SHIGERU ,  KATOU KOUJI ,  INOKI SATORU ,  YAMADA TORU ,  TAKAI TOSHIHIRO

IPC: C07C69/716

Abstract: NEW MATERIAL:Compounds of the formula (R and R are lower alkyl) and salts thereof. EXAMPLE:Methyl 2-formylacetoacetate. USE:A ligand for transition metal complexes or chelate compounds. Useful for production of cobalt complexes having an excellent oxidation-reduction activity and the resultant cobalt complexes can be used as a catalyst in production of a hydroxyl group-containing compound or a ketone from an olefin. PREPARATION:For example, an alkyl 2-alkoxymethylene-beta-ketoacetate is decomposed using an alkali or an alkyl beta-ketoacetate is reacted with an alkyl orthoformate and acetic anhydride to synthesize an alpha-alkoxymethylene-beta- ketoacetic acid. The synthesized compound is decomposed using an alkali without isolation, thus obtaining the objective compound of the formula.

公开(公告)号：JPH02191290A

公开(公告)日：1990-07-27

申请号：JP928689

申请日：1989-01-18

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  ISAYAMA SHIGERU ,  KATOU KOUJI ,  INOKI SATORU ,  YAMADA TORU ,  TAKAI TOSHIHIRO

IPC: C07D295/18 ,  B01J31/22 ,  C07B61/00 ,  C07C29/04 ,  C07C31/02 ,  C07C31/13 ,  C07C33/18 ,  C07C235/72 ,  C07F15/06

Abstract: NEW MATERIAL:A complex shown by formula I (R and R are lower alkyl and/or aryl; R and R are H, lower alkyl, etc.; R , R , R and R are H, aryl, etc.). EXAMPLE:Bis(1-piperidinocarbamoyl-4,4-dimethyl-1,3-pentanedionato)cobalt (II). USE:A catalyst useful for efficiently obtaining a hydroxyl group-containing compound from an olefin-based compound. When the olefin-based compound contains functional group, the functional group will not decompose. PREPARATION:First, a dicarbonyl compound (salt) shown by formula II is dissolved or dispersed into an alcohol and an aqueous solution of NaOH is dripped into the solution while stirring. Then the solution is reacted with a cobalt compound such as cobalt chloride at pH8-12 at 0-50 deg.C.

公开(公告)号：JPH07188204A

公开(公告)日：1995-07-25

申请号：JP32735893

申请日：1993-12-24

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  HATA EIICHIRO ,  TAKAI TOSHIHIRO ,  YAMADA TORU

IPC: C07D309/30 ,  C07C51/31 ,  C07C59/125 ,  C07C62/08 ,  C07D313/04

Abstract: PURPOSE:To safely and simply produce the subject compound in high efficiency by oxidizing a cyclic ketone having an alkoxy group on a carbon at alpha-position in the presence of a metal compound and an aldehyde using a safe and inexpensive oxygen as an oxidizing agent. CONSTITUTION:A cyclic ketone having an alkoxy group on a carbon at alphaposition is reacted with oxygen in the presence of a compound of a metal such as nickel or cobalt and an aldehyde compound to afford the objective acetal lactone. The acetal lactone is further treated with an alcohol in the presence of an acid catalyst to give the objective acetal carboxylic acid. As the cyclic ketone, a ketone compound of formula I (R is an alkyl or a cycloalkyl; R to R each is H, a halogen, an alkyl, a cycloalkyl, an aryl, nitro, cyano, etc.) is preferably used. As the metal compound, a metal compound selected from complexes of nickel, cobalt, manganese, iron, copper and vanadium, respectively having 1,3-diketone compound as a ligand is preferably used. The compound of formula II and formula III (R and R each is an alkyl or a cycloalkyl) are obtained by this reaction.

公开(公告)号：JPH0649051A

公开(公告)日：1994-02-22

申请号：JP20376392

申请日：1992-07-30

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  TAKAI TOSHIHIRO ,  HATA EIICHIRO ,  YOROZU KIYOTAKA

IPC: B01J31/18 ,  B01J31/20 ,  B01J31/22 ,  C07B61/00 ,  C07D301/06 ,  C07D303/04 ,  C07D303/16

Abstract: PURPOSE:To efficiently obtain an epoxy group-containing compound at a low cost under mild conditions in a simple operation by reaction of a double bond- contg. compound with an oxygen gas-contg. gas in the presence of a complex compound and a ketone. CONSTITUTION:The objective compound of formula IV can be obtained by reaction of (A) a compound of formula R CH=CR R (R is H, alkyl or aryl; R and R are each H, alkyl, aryl, arylalkyl, etc.) with (B) an oxygen-contg. gas in the presence of (C) 0.005-30mol, per mol of the compound A, of a cobalt, manganese or iron complex compound of formula I, II (M is Co, Mn or Fe; R to R , R to R , and R to R are each lower alkyl, aryl, lower alkoxy, etc.; R and R are each lower alkyl, aryl, etc.; X and X are each O or N) and (D) 1-100mol, per mol of the compound A, of a ketone compound of formula III (R, R' and R'' are each alkyl or aryl) at 30-180 deg.C under an oxygen partial pressure of 0.1-10atm.

公开(公告)号：JPH054980A

公开(公告)日：1993-01-14

申请号：JP20097591

申请日：1991-08-09

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  YAMADA TORU ,  TAKAI TOSHIHIRO

IPC: B01J31/22 ,  C07B61/00 ,  C07D301/06 ,  C07D303/04 ,  C07D303/12

Abstract: PURPOSE:To obtain the subject compound useful as a synthetic intermediate, polymer raw material, etc., on an industrial scale at a low cost by reacting a specific compound containing double bond with an oxygen-containing gas in the presence of a specific nickel compound and isovaleraldehyde. CONSTITUTION:The objective compound of formula IV or V can be produced under mild reaction condition in high catalyst efficiency without using expensive oxidation agent such as peracid by reacting (A) a compound containing double bond and expressed by formula H C=CH(R1) (R1 is alkyl or aryl) or formula I [R2 and R3 are H, (substituted) alkyl or aryl; R4 is H, alkyl or aryl; 5 is alkyl or aryl] with (B) an oxygen-containing gas in the presence of (C) isovaleraldehyde and at least one kind of compound selected from nickel compounds of formula II or formula III (R7, R9, R10 and R12 are alkyl, aryl, alkoxy, etc.; R8 and R11 are H, lower alkyl, aryl, etc.; R7 and R8 or R11 and R12 may together form a ring).

公开(公告)号：JPH04342598A

公开(公告)日：1992-11-30

申请号：JP14501291

申请日：1991-06-17

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  YAMADA TORU ,  TAKAI TOSHIHIRO

IPC: B01J31/22 ,  C07B61/00 ,  C07D301/06 ,  C07F15/04

Abstract: PURPOSE:To profitably produce an epoxy group-containing compound by a novel method, by reacting a specific double bond-containing compound with an oxygen-containing gas in the presence of a novel nickel compound as a catalyst and in the presence of a primary or secondary alcohol. CONSTITUTION:A double bond-containing compound (e.g. 2-methyl-2-decene) of formula I [R -R are H, (substituted), alkyl, (substituted)aryl; R and R , and R and R may be combined with each other to form a ring, respectively] is allowed to react with an oxygen-containing gas in the presence of a nickel compound of formula II (R , R are lower alkyl, aryl; R is H, halogen, lower alkyl, aryl; R and R may combined with each other to form a ring) {e.g. bis[1,3-di(p-methoxyphenyl)-1,3-propanedionato] nickel} as a catalyst and in the presence of a primary alcohol and/or a secondary alcohol to produce an epoxy group-containing compound of material III (e.g. 2,2-dimethyl-3- heptyloxirane).

公开(公告)号：JPH04334342A

公开(公告)日：1992-11-20

申请号：JP10585891

申请日：1991-05-10

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  TAKAI TOSHIHIRO ,  YAMADA TORU

IPC: B01J31/22 ,  C07B61/00 ,  C07C45/34 ,  C07C47/19 ,  C07C47/192 ,  C07C49/17 ,  C07C49/245 ,  C07C49/255 ,  C07C49/577 ,  C07C67/00 ,  C07C69/675

Abstract: PURPOSE:To produce the subject compound such as alpha-hydroxyketones by carrying out new reaction of a double bond-containing compound using O2 in the coexistence of an aldehyde compound using a nickel compound or an iron compound and osmium tetroxide. CONSTITUTION:A double bond-containing compound (e.g. 3-methyl-2-butenyl benzoate) expressed by formula III (R and R are H, alkyl, etc.; R is H, alkyl, aryl, etc.; R and R or R and R may form a ring) is oxidized with inexpensive and readily handleable O2 in the presence of a nickel compound [e.g. bis(3- methyl-2,4-pentanedronato)nickel(II)] expressed by formula I (R and R are alkyl, aryl, etc.; R is H, alkyl, etc.; R and R are capable of forming a ring) or an iron compound expressed by formula II [e.g. tris(3-methyl-2,4- pentanedionato)iron] and osmium tetroxide and an aldehyde compound (acetaldehyde) expressed by the formula R CHO (R is alkyl, etc.) to afford the objective carbonyl group-containing compound expressed by formula IV. A nitrogen-containing heterocyclic compound such as pyridine is preferably further made to coexist in the reaction.

公开(公告)号：JPH03227952A

公开(公告)日：1991-10-08

申请号：JP2025590

申请日：1990-01-30

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  TAKAI TOSHIHIRO

IPC: B01J31/22 ,  B01J31/26 ,  C07B61/00 ,  C07C45/36 ,  C07C47/54 ,  C07C47/542 ,  C07C47/575

Abstract: PURPOSE:To produce the title compound by reacting a compound such as styrene or cis-beta-methylstyrene with an O2-containing gas using a compound selected from specific vanadium compounds as a catalyst in the absence of a primary or secondary alcohol. CONSTITUTION:Styrene, cis-beta-methylstyrene, cis-stilbene or a lower alkyl group and/or lower alkoxy group nuclear substitution substance thereof is oxidized with an O2-containing gas using at least one compound selected from vanadium compounds shown by formula I to formula VII as a catalyst preferably in the absence of a primary or secondary alcohol to give a carbonyl group-containing compound. By this method, the carbonyl group-containing compound can be obtained from styrene, cis-beta-methylstyrene or cis-stilbene as a starting raw material by the new reaction using the vanadium compound as a catalyst. The carbonyl groupcontaining compound is useful as a raw material for drugs and agricultural chemicals.