公开(公告)号：JPH0366636A

公开(公告)日：1991-03-22

申请号：JP20189889

申请日：1989-08-03

Applicant: MITSUI PETROCHEMICAL IND

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

IPC: B01J31/22 ,  C07B61/00 ,  C07C29/50 ,  C07C35/36 ,  C07C41/26 ,  C07C43/23

Abstract: PURPOSE:To prepare the subject compound useful as an intermediate for medicines, agricultural chemicals, etc., in high conversion and yield in one process by reacting a dihydronaphthalene with an oxygen-containing gas in the presence of a secondary alcohol and a catalyst comprising a specific cobalt complex. CONSTITUTION:A compound of formula I or II (R to R8 are H, lower alkyl or alkoxy) is reacted with an oxygen-containing gas in the presence of a secondary alcohol and a catalyst of formula III (R , R , R and R are H, lower alkyl, aryl, arylalkyl, perfluoralkyl, CO2R or CONR R ; R to R are lower alkyl, aryl or arylalkyl; and R and R are further H, lower cycloalkyl or group of formula IV; but a case comprising R =R =R =R =CF3 and R =R =H is excluded) to provide the objective compound of formulae V, VI or VII in high conversion and yield yield without requiring a precisely anhydrous condition in are process.

公开(公告)号：JPH02129134A

公开(公告)日：1990-05-17

申请号：JP28344488

申请日：1988-11-09

Applicant: MITSUI PETROCHEMICAL IND

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

IPC: C07D209/46 ,  B01J31/22 ,  C07B61/00 ,  C07C27/12 ,  C07C35/08 ,  C07C45/34 ,  C07C49/403 ,  C07C67/31 ,  C07C67/313 ,  C07C69/757 ,  C07C253/30 ,  C07C255/46 ,  C07C255/47 ,  C07D317/20 ,  C07D317/26

Abstract: PURPOSE:To avoid hydrolysis of functional group of cyclohexenes and obtain the title compound in high conversion and yield by reacting cyclohexenes with an oxygen-containing gas in the presence of a secondary alcohol using a cobalt complex as a catalyst. CONSTITUTION:A compound expressed by formula II (R and R are H, alkyl, etc.; R to R are H, alkyl, CN, etc.) is subjected to oxidation and reduction reaction using a catalyst [e.g., bis(2,4-pentanedionate)cobalt(II)] expressed by formula I [R , R , R and R are alkyl, aryl, perfluoroalkyl, CO2R or CO2 NR R (R is alkyl or aryl; R and R are H, alkyl or aryl, etc.), except when R , R , R and R are CF3 and R and R are H] in the presence of a secondary alcohol to provide cyclohexanols and/or cyclohexanones. Also in cyclohexenes having a functional group such as CN or CO2CH3, functional group thereof is free from hydrolysis.

公开(公告)号：JPH01287047A

公开(公告)日：1989-11-17

申请号：JP11567188

申请日：1988-05-12

Applicant: MITSUI PETROCHEMICAL IND

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

IPC: B01J31/22 ,  B01J31/02 ,  C07B61/00 ,  C07C27/00 ,  C07C27/12 ,  C07C29/04 ,  C07C35/08 ,  C07C45/34 ,  C07C49/11 ,  C07C67/00

Abstract: PURPOSE:To obtain the title compound in high selectivity, in high yield and readily, by reacting a cyclohexene with an oxygen-containing gas by using a specific catalyst in the presence of a secondary alcohol. CONSTITUTION:A cyclohexene is reacted with an oxygen-containing gas by using a compound shown by the formula [R , R and R , R are H, lower alkyl, aryl or -CX2 (X is halogen); R and R are H, lower alkyl, -COOR (R is H or lower alkyl) or -CX3 or R -R may be the same or mutually different] as a catalyst in the presence of a secondary alcohol such as isopropyl alcohol, further preferably in the presence of an N-containing heterocyclic compound as a promoter preferably under 0.2-5.0kg/cm oxygen pressure at 50-150 deg.C to give the aimed compound. The amount of the catalyst used, for example, is preferably 5-20mol basacetylacetonatocobalt complex based on 1mol cylochexene.

公开(公告)号：JPH01257122A

公开(公告)日：1989-10-13

申请号：JP8374188

申请日：1988-04-05

Applicant: MITSUI PETROCHEMICAL IND

Inventor： KISO YOSHIHISA ,  TAKAI TOSHIHIRO ,  HAYASHI TETSUO ,  TAKAHATA KAZUNORI

IPC: B01J29/08 ,  C01B39/04 ,  C01B39/06 ,  C01B39/24

Abstract: PURPOSE:To increase the efficiency of Y type zeolite as a catalyst for a liq. phase dehydration reaction by dealuminizing the zeolite and fluorinating the surface of the zeolite so as to obtain a prescribed ratio of SiO2 to Al2O3 and a prescribed fluorine content. CONSTITUTION:Y type zeolite is dealuminized and the surface of the zeolite is fluorinated to obtain fluorinated dealuminized Y type zeolite having 5.5-20 molar ratio of SiO2/Al2O3, 0.1-30wt.% fluorine content and a crystal structure similar to that of Y type zeolite. Fluorinated dealuminized Y type zeolite having proton exchange ability has an X-ray diffraction pattern shown by table 1. The pattern is formed by diffraction analysis with CuKalpha rays and the relative intensity of a diffracted ray at 6.4+ or -0.2 is represented by 100.

公开(公告)号：JPH01224345A

公开(公告)日：1989-09-07

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 readily obtain the subject compounds which are an intermediate for dyes, etc., in high selectivity in one step, by reacting phenols with aromatic carboxylic acids in the presence of a specific polysiloxane catalyst and passing the resultant product through an ester compound. CONSTITUTION:Phenols are reacted with aromatic carboxylic acids in the presence of a polysiloxane catalyst having sulfonated phenyl groups as a catalyst in an amount within the range of 10-90mol. based on 100mol. phenols, normally at 100-400 deg.C, especially 150-350 deg.C to provide an ester compound, which is then subjected to the Fries rearrangement to afford the aimed compounds. The above-mentioned catalyst used is obtained by adding and reacting alcohols and dilute hydrochloric acid with a mixture of a phenyltrialkoxysilane with a tetraalkoxysilane, etc., and sulfonating the resultant polysiloxane having phenyl groups.

公开(公告)号：JPH08319269A

公开(公告)日：1996-12-03

申请号：JP12512395

申请日：1995-05-24

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MATSUI NARIKAZU ,  TAKAI TOSHIHIRO ,  MATSUOKA HIDETO ,  ISHIBASHI MASAYASU ,  KAGAYAMA AKISHI ,  KURODA HIROSHI ,  FUJITA TERUNORI

IPC: B01J31/22 ,  C07B61/00 ,  C07C407/00 ,  C07C409/08 ,  C07C409/10

Abstract: PURPOSE: To improve the initial selectivity of oxidizing reaction and produce the corresponding arylalkyl hydroperoxides at a high concentration in high selectivity by using a specifically treated transition metallic complex as a catalyst. CONSTITUTION: (A) A transition metallic complex is pretreated with oxygen or a peroxide (preferably alkyl hydroperoxides, etc.). (B) An arylalkyl- hydrocarbon of the formula [P and Q are each H or an alkyl; (n) is 1-3; Ar is an n-valent hydrocarbon] (e.g. cumene) is then oxidized with a gas containing oxygen in the presence of the resultant transition metallic complex as a catalyst and converted into arylalkyl hydroperoxides. Furthermore, the transition metal in the component (A) preferably has an ion of the transition metal, selected from the groups I, II, VI, VII and VIII of the periodic table (e.g. manganese) and coordinated with a ligand (preferably an aliphatic cyclic compound containing nitrogen, especially porphycenes, etc.) and the atom coordinated with the ion is preferably nitrogen, oxygen or sulfur.

公开(公告)号：JPH08311023A

公开(公告)日：1996-11-26

申请号：JP3356196

申请日：1996-02-21

Applicant: MITSUI PETROCHEMICAL IND

Inventor： FUJITA TERUNORI ,  MATSUI NARIKAZU ,  TAKAI TOSHIHIRO ,  MATSUOKA HIDETO ,  KAGAYAMA AKISHI ,  KURODA HIROSHI ,  ISHIBASHI MASAYASU ,  IWASAKI HIROSHI

IPC: C07D487/22 ,  B01J31/22 ,  C07B61/00 ,  C07C407/00 ,  C07C409/10 ,  C07D255/02 ,  C07D257/02 ,  C07D259/00 ,  C07D471/08

Abstract: PURPOSE: To obtain the subject compound at a high reaction rate, high conversion and high selectivity and in high concentration with suppressing decomposition of the product without by-product such as formic acid or acetic acid by using a specific catalyst and oxidizing an aryl alkyl hydrocarbon with an oxygen-containing gas. CONSTITUTION: (A) A compound of formula II (P and Q are each H or an alkyl; (x) is 1-3; Ar is an (x)-valued aromatic hydrocarbon group) is oxidized by (B) an oxygen-containing gas in the presence of (C) a transition metal complex catalyst containing a cyclic multifunctional amine compound having at least three N in a molecular chain generating a ring as a ligand e.g. a complex of formula I [A is a 1-6C alkylene, phenylene, naphthylene or pyridinediyl; R is H, an alkyl, (alkyl)aryl, etc.; M is a (+a) valued transition metal ion as a central metal ion; X is a (-b)-valued pair ion stable to oxidation; a and n are each 1-4; b>0; n=a/b; m is 0 or 1]}.

公开(公告)号：JPH0532648A

公开(公告)日：1993-02-09

申请号：JP20097491

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 ,  C07D303/16 ,  C07D303/17 ,  C07D303/22

Abstract: PURPOSE:To obtain an epoxy group-containing compound under a mild reaction condition industrially at a low cost in high catalytic efficiency without using an expensive peracid, etc. CONSTITUTION:One or more compounds shown by formula I (R is straight-chain or branched alkyl or aryl which may contain substituent group; R and R are H, substituted or nonsubstituted alkyl or aryl; R and R , R and R and R to R may be bonded to form ring, respectively) formula II and formula III (R , R , R and R are lower alkyl, aryl, alkoxy, halogenated alkyl, COOR or CONR R ; R to R are alkyl or aryl; R and R are H, halogen, lower alkyl, aryl or arylalkyl which may contain substituent group and further R and R , R and R , R and R are bonded to form ring, respectively) are reacted with an oxygen-containing gas in the presence of a compound shown by the formula R CHO (R is each group in R or cycloalkyl which may contain substituent group) to give the objective compound shown by formula IV advantageously.

公开(公告)号：JPH04273867A

公开(公告)日：1992-09-30

申请号：JP3430691

申请日：1991-02-28

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  INOKI SATORU ,  TAKAI TOSHIHIRO ,  YAMADA TORU

IPC: B01J31/22 ,  C07B61/00 ,  C07D301/06 ,  C07D303/38

Abstract: PURPOSE:To obtain the subject compounds useful, e.g. as an intermediate for synthesis of medical drugs and agricultural drugs by oxidizing an alpha,beta-unsaturated carbonyl compound using oxygen in the presence of specified vanadium compound and aldehyde. CONSTITUTION:A compound of formula I [R -R are H, alkyl, aryl or may be mutually bonded to form ring; R is formula II (R and R are H, alkyl, aryl or mutually bonded to form ring)] is reacted with an oxygen-containing gas in the presence of a vanadium compound of formula III or IV (R , R , R and R are lower alkyl, aryl, alkoxy, etc.; R and R are H, halogen, lower alkyl, aryl, etc.; R and R , R and R may be mutually bonded to form ring) and an aldehyde of formula R CHO (R is alkyl or aryl), as necessary, in a solvent (e.g. dichloroethane) at the ordinary pressure and at 0-100 deg.C, thus giving the objective compound of formula V.

公开(公告)号：JPH0477479A

公开(公告)日：1992-03-11

申请号：JP19202690

申请日：1990-07-20

Applicant: MITSUI PETROCHEMICAL IND

Inventor： MUKOYAMA MITSUAKI ,  TAKAI TOSHIHIRO ,  YAMADA TORU

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

Abstract: PURPOSE:To obtain the subject compound useful as a synthetic intermediate, etc., in high yield by reacting a double bond-containing compound with an oxygen-containing gas in the presence of alcohols using specific nickel compounds as a catalyst. CONSTITUTION:A double bond-containing compound expressed by formula I (R to R are H, alkyl or aryl) is reacted with an oxygen-containing gas in the presence of a primary alcohol or secondary alcohol, or both using at least one catalyst selected from nickel compounds expressed by formula II (R is lower alkyl or aryl; R is H or lower alkyl; R is lower alkyl) or formula III (R is lower alkyl or aryl ; R is H or lower alkyl ; R and R are lower alkyl) to afford an epoxy group-containing compound expressed by formula IV.