公开(公告)号：JPH02178248A

公开(公告)日：1990-07-11

申请号：JP33058188

申请日：1988-12-27

Applicant: MITSUI PETROCHEMICAL IND

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

IPC: B01J31/22 ,  C07B61/00 ,  C07C29/50 ,  C07C31/125 ,  C07C33/20 ,  C07C49/203 ,  C07C49/248 ,  C07C49/258 ,  C07C49/76 ,  C07C49/84 ,  C07C49/92 ,  C07C69/738 ,  C07F15/06

Abstract: NEW MATERIAL:A cobalt complex of a beta-dicarbonyl compound expressed by formula I (R , R , R and R each are independently H, lower alkyl or aryl; R and R each are independently lower alkyl, aryl, lower alkoxy or lower alkylamino). EXAMPLE:Bis(2-ethoxycarbonyl-1-phenyl-1,3-butanedionato)cobalt(II). USE:Useful as a catalyst for synthesizing hydroxyl group-containing compounds from olefinic compounds and capable of providing the hydroxyl group-containing compounds at a high conversion rate by bringing the olefinic hydrocarbon compounds into contact with an oxygen-containing gas in the coexistence of the compound expressed by formula I and a secondary alcohol. PREPARATION:For example, as shown in the reaction formulas, sodium hydroxide is dripped into a solution of a dicarbonyl compound corresponding to a ligand of an objective complex dispersed therein and a cobalt compound is then added thereto afford the compound expressed by formula I.

公开(公告)号：JPH02169539A

公开(公告)日：1990-06-29

申请号：JP32458188

申请日：1988-12-22

Applicant: MITSUI PETROCHEMICAL IND

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

IPC: B01J31/22 ,  C07B61/00 ,  C07C29/03 ,  C07C31/02 ,  C07C45/29 ,  C07C49/04 ,  C07C49/233 ,  C07C49/255 ,  C07C49/76 ,  C07C49/813 ,  C07C205/45

Abstract: NEW MATERIAL:A cobalt complex of a beta-dicarbonyl compound expressed by formula I [R and R are perfluoroalkyl; R and R are H; R and R are formula II to V (X is lower alkyl, aryl, alkoxy, F, NO2 or perfluoroalkyl; n is 1-5; m is 1-4; q is 0-4; p is 0-3)]. EXAMPLE:Bis[1,1,1-trifluoro-5-(4-methylphenyl)-2,4-pentadionato]cobalt (II). USE:A catalyst for converting olefinic hydrocarbon compounds into carbonyl group- and/or hydroxyl group-containing compounds at a high conversion rate without decomposition functional groups even if the raw material compounds have the functional groups. PREPARATION:An aqueous solution of sodium hydroxide is dripped into a solution of the corresponding dicarbonyl compound in an alcohol while stirring and a cobalt compound is then added to the above-mentioned solution to afford the compound expressed by formula I.

公开(公告)号：JPH02160734A

公开(公告)日：1990-06-20

申请号：JP31419888

申请日：1988-12-13

Applicant: MITSUI PETROCHEMICAL IND

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

IPC: B01J31/22 ,  C07B61/00 ,  C07C29/04 ,  C07C31/02 ,  C07C31/13 ,  C07C33/18

Abstract: PURPOSE:To obtain the objective secondary alcohol in high yield while suppressing the deterioration of catalyst by oxidizing olefins with oxygen in the presence of a cobalt complex catalyst while removing water produced by the reaction. CONSTITUTION:A compound of formula I (R -R are alkyl, aryl or arylalkyl or R is cycloalkyl and R -R are H; R -R may have substituents) is made to react in the presence of a secondary alcohol and a catalyst expressed by formula II (R , R , R and R are H, 1-10C alkyl, aryl having substituent such as lower alkyl, lower alkoxymethyl, CF3, etc.; R and R are H, lower alkyl, halogen, etc.; excluding the case that R =R =R =R =CF3 and R =R =H) while removing gas generated by the reaction. The objective compound of formula III (one of R and R is OH and the other is H) can be produced from the above raw material in high conversion while suppressing the deterioration of the catalyst.

公开(公告)号：JPH02121937A

公开(公告)日：1990-05-09

申请号：JP27244988

申请日：1988-10-28

Applicant: MITSUI PETROCHEMICAL IND

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

IPC: C07C29/04 ,  C07C31/10 ,  C07C31/12 ,  C07C31/125 ,  C07C33/20

Abstract: PURPOSE:To obtain alcohols in high conversion ratio and selectivity by reacting olefins with an oxygen-containing gas in the pressence of a cobalt complex catalyst and secondary alcohol. CONSTITUTION:A compound expressed by formula I (R is alkyl, aryl, cycloalkyl or arylalkyl; R to R are H, alkyl, aryl or arylalkyl) is reacted with an oxygen- containing gas in the presence of a Co complex catalyst, such as a catalyst expressed by formula II or III, and a secondary alcohol (e.g., isopropyl alcohol) at 60-130 deg.C under 0.2-10kg/cm pressure of oxygen to afford a compound expressed by formulas IV and/or V. During the reaction, stirring, bubbling, etc., are preferably carried out so as to provide sufficient contact of the oxygen- containing gas with the liquid phase. A hydrocarbon compound having OH and CO groups can be obtained by changing the reaction conditions or separating the reaction product.

公开(公告)号：JPH02111739A

公开(公告)日：1990-04-24

申请号：JP4941588

申请日：1988-03-02

Applicant: MITSUI PETROCHEMICAL IND

Inventor： TAKAI TOSHIHIRO ,  TANIGUCHI KATSUO

IPC: C07C67/08 ,  B01J31/10 ,  C07B61/00 ,  C07C45/00 ,  C07C45/54 ,  C07C49/83 ,  C07C67/00 ,  C07C69/78

Abstract: PURPOSE:To provide the subject compound in one step from starting raw materials and by simple operations in a high selectivity by employing a polysiloxane catalyst having a sulfonated phenyl group when a phenol is reacted with an aromatic carboxylic acid. CONSTITUTION:A phenol is reacted with an aromatic carboxylic acid in the presence of a polysiloxane catalyst having a sulfonated phenyl group usually at 100-400 deg.C, preferably 150-350 deg.C, to produce an ester compound, which is subjected to a Fries rearrangement reaction to provide a hydroxyaryl aryl ketone such as hydroxybezophenone useful as an intermediate for dyes, polymers, UV absorbents, synthetic resin stabilizers, color-producing agents, medicines, etc., in one step from the starting raw materials and in greatly high conversion and selectivity.

公开(公告)号：JPH01279850A

公开(公告)日：1989-11-10

申请号：JP10701688

申请日：1988-04-28

Applicant: MITSUI PETROCHEMICAL IND

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

IPC: C07C231/12 ,  B01J31/22 ,  C07B61/00 ,  C07C27/00 ,  C07C29/04 ,  C07C31/125 ,  C07C31/13 ,  C07C31/133 ,  C07C33/20 ,  C07C67/00 ,  C07C233/76

Abstract: PURPOSE:To obtain a hydrocarbon compound having OH group in high conversion and selectivity by reacting olefins with an oxygen-containing gas in the presence of a secondary alcohol using a Co complex as a catalyst. CONSTITUTION:The compound of formula III (either one of R and R is OH and the other is H) can be produced by reacting a compound of formula I (R is alkyl, aryl, cycloalkyl or arylalkyl; R -R are H, alkyl, aryl, etc.) with an oxygen-containing gas using a compound of formula II [R , R , R and R are H, lower alkyl, aryl or CF3; R and R are H, lower alkyl, COOR (R is H or alkyl) or CF3] as a catalyst in the presence of a secondary alcohol (e.g. isopropyl alcohol) under an oxygen pressure of 0.2-1.0kg/cm . The Co complex used as the catalyst can be synthesized e.g. from CoCl2 and a corresponding diketone having CF3 by desalting process.

公开(公告)号：JPH01224351A

公开(公告)日：1989-09-07

申请号：JP4941488

申请日：1988-03-02

Applicant: MITSUI PETROCHEMICAL IND

Inventor： KISO YOSHIHISA ,  TAKAI TOSHIHIRO ,  TANIGUCHI KATSUO

IPC: B01J31/06 ,  C07B61/00 ,  C07C67/08 ,  C07C69/773 ,  C07C69/78 ,  C07C69/80 ,  C07C69/82 ,  C07C69/94

Abstract: PURPOSE:To efficiently obtain compounds useful as an intermediate for dyes, high polymers, ultraviolet ray absorbers, etc., by reacting phenols with aromatic carboxylic acids in the presence of a polysiloxane catalyst having sulfonated phenyl groups. CONSTITUTION:Phenols expressed by the formula Ar-(OH)n (Ar is aromatic compound residue and benzene ring, naphthalene ring, etc.; n is 1-2) are reacted with aromatic carboxylic acids expressed by the formula Ar-(COOH)n in the presence of a polysiloxane catalyst having sulfonated phenyl groups at 100-400 deg.C temperature in a solvent, such as benzene, for 1-20hr to afford the aimed substances. The above-mentioned catalyst is obtained by sulfonating a polysiloxane having phenyl groups. The reaction is carried out by using the aromatic carboxylic acids in an amount of 1-1,000mol. based on 100mol. phenols and the catalyst in an amount of 0.1-100pts.wt. based on 100pts.wt. raw material compounds.

公开(公告)号：JPH01221343A

公开(公告)日：1989-09-04

申请号：JP4693788

申请日：1988-02-29

Applicant: MITSUI PETROCHEMICAL IND

Inventor： UEKI HIROMI ,  ISHIMARU ETSUJI ,  TAKAI TOSHIHIRO

IPC: C07C43/23 ,  C07C41/00 ,  C07C41/03 ,  C07C67/00 ,  C08G59/62 ,  C08G63/18 ,  C08G63/19 ,  C08G64/00

Abstract: NEW MATERIAL:The dihydric phenol compound of formula (n is 2-5). EXAMPLE:1,4-Bis-[2-hydroxy-3-[4-{2-hydroxy-3-(4-hydroxyphenoxy)-1- propanoxy}phenoxy]-1-propanoxy]benzene. USE:Useful for the production of epoxy resin, polycarbonate resin or various modified polyester resin, etc. The above resins such as epoxy resin produced by the use of the above compound have excellent heat-resistance, adhesivity and gas barrierness and is easily handleable. PREPARATION:The compound of formula can be produced e.g. by adding 4- benzyloxyphenol to hydroquinone diglycidyl ether and subjecting the resultant 1,4-bis-{2-hydroxy-3-(4-benzyloxyphenoxy)-1-propanoxy}benzene to catalytic hydrocracking.