公开(公告)号：JP2000219652A

公开(公告)日：2000-08-08

申请号：JP2173699

申请日：1999-01-29

Applicant: DAICEL CHEM

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA

IPC: B01J31/04 ,  B01J31/20 ,  C07B61/00 ,  C07C51/23 ,  C07C51/255 ,  C07C53/122 ,  C07C53/124 ,  C07C53/126 ,  C07C63/06

Abstract: PROBLEM TO BE SOLVED: To efficiently obtain a carboxylic acid by oxidizing and cleaving a corresponding 1,2-diol with oxygen. SOLUTION: 1,2-Diol is reacted with oxygen in the presence of an imide compound of the formula (R1 and R2 are each the same or different and is a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group or an acyl group or R1 and R2 are mutually bonded to form a double bond or an aromatic or a nonaromatic ring; and X is an hydrogen atom or a hydroxyl group; one or two N-substituted cyclic imide groups shown in the formula may be formed in R1, R2 or the double bond or the aromatic or the nonaromatic ring formed by mutual bonding of R1 and R2). A corresponding carboxylic acid is formed by oxidatively cleaving the diol between two carbon atoms bonded to a hydroxyl group. A metal compound may be used as a cocatalyst.

公开(公告)号：JP2000212116A

公开(公告)日：2000-08-02

申请号：JP1647799

申请日：1999-01-26

Applicant: DAICEL CHEM

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA

IPC: B01J31/04 ,  B01J31/22 ,  C07B61/00 ,  C07C45/39 ,  C07C49/17 ,  C07C49/497

Abstract: PROBLEM TO BE SOLVED: To efficiently produce a corresponding hydroxyketone by oxidizing a secondary alcohol having plural hydroxy groups in the molecule by reacting the specific secondary alcohol with oxygen in the presence of a specified imide compound. SOLUTION: A secondary alcohol having plural hydroxy groups in the molecule, preferably 4-15C linear polyols or 4-15C cyclic polyols (including saccharides) is reacted with oxygen by using an imide compound of the formula (R1 and R2 are each H, a halogen, an alkyl, an aryl, a cycloalkyl, an acyl or the like; X is O or OH) as a catalyst, and a metallic compound as a cocatalyst to provide the objective ketone.

公开(公告)号：JPH11335304A

公开(公告)日：1999-12-07

申请号：JP35362098

申请日：1998-12-11

Applicant: DAICEL CHEM ,  ISHII YASUTAKA

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA ,  HIRAI NARIHISA

IPC: B01J27/128 ,  B01J31/02 ,  B01J31/04 ,  B01J31/20 ,  C07B41/06 ,  C07B61/00 ,  C07C1/207 ,  C07C1/24 ,  C07C13/28 ,  C07C13/615 ,  C07C27/04 ,  C07C29/136 ,  C07C35/22 ,  C07C45/33 ,  C07C45/45 ,  C07C45/46 ,  C07C47/34 ,  C07C49/323 ,  C07C49/345 ,  C07C49/453 ,  C07D303/04 ,  C07D303/14

Abstract: PROBLEM TO BE SOLVED: To obtain an acylating agent capable of simply and efficiently introducing an acyl group to a non-activated carbon atom, for example, even a carbon atom at the bridge head position of a polycyclic compound, by combining a specific dicarbonyl compound, oxygen, a metal compound, etc. SOLUTION: This acylating agent comprises (A) a 1,2-dicarbonyl compound or its hydroxy reduced product, preferably biacetyl, etc., (B) oxygen, and (C) (i) a metal compound, preferably a transition metal compound, concretely a cobalt compound, etc., and (ii) at least one compound selected from imide compounds of formula I (R and R are each H, a halogen, an alkyl, an aryl or the like; X is O or hydroxyl). The component A is preferably a compound of formula II (R and R are each a 1-4C alkyl, a cycloalkyl or the like; Z and Z are each O atom or hydroxyl).

公开(公告)号：JPH11246466A

公开(公告)日：1999-09-14

申请号：JP6945898

申请日：1998-03-04

Applicant: DAICEL CHEM ,  ISHII YASUTAKA

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA

IPC: B01J27/08 ,  B01J27/135 ,  C07B61/00 ,  C07C45/69 ,  C07C45/72 ,  C07C49/403

Abstract: PROBLEM TO BE SOLVED: To obtain the subject new compound useful as an intermediate raw material of monomer for functional polymers (e.g. acrylic resin for resist or polyester) or an intermediate for perfumes, medicines or agrochemicals by introducing an acyl group at 4 position. SOLUTION: This compound is represented by formula I (R to R are each H or a hydrocarbon group and R and R and R and R each may form a ring together with adjacent carbon atom), e.g. 2,3,5-trimethyl-4- propionylcyclohexane-1-one. The compound of formula I is obtained by bringing (A) a compound of formula II into contact with (B) a catalyst comprising a compound of the group 3 or 4 of the periodic table (e.g. a samarium compound or a zirconium compound) in an amount corresponding to 0.00001-1 mol based on 1 mol component A in the presence (or absence) of a solvent.

公开(公告)号：JPH11239730A

公开(公告)日：1999-09-07

申请号：JP316198

申请日：1998-01-09

Applicant: DAICEL CHEM ,  ISHII YASUTAKA

Inventor： NAKANO TATSUYA ,  SAKAGUCHI SATOSHI ,  ISHII YASUTAKA

IPC: B01J31/02 ,  C07B41/08 ,  C07B43/02 ,  C07C205/55 ,  C07C231/02 ,  C07C233/06 ,  C07C233/58 ,  C07C265/10 ,  C07C271/24

Abstract: PROBLEM TO BE SOLVED: To nitrate or carboxylate a substrate efficiently even in relatively mild conditions. SOLUTION: At least one functional group selected from a nitro group and a carboxyl group is introduced into a substrate by making the substrate contact at least one reagent selected from (i) a nitrogen oxide and (ii) a mixture of carbon monoxide and oxygen in the presence of an imide compound such as N-hydroxyphthalimide expressed by formula I (wherein R and R are each a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, and R and R are bonded together to form a double bond or an aromatic or a nonaromatic cycle; Y is O or OH; (n) is 1-3). The nitrogen oxide includes compounds such as N2 O3 , NO2 expressed by formula II NXOY, and the substrate includes compounds having a methine carbon atom such as adamantane, compounds having a methyl group or a methylene group at an adjacent position of an aromatic cycle.

公开(公告)号：JPH11228484A

公开(公告)日：1999-08-24

申请号：JP5444698

申请日：1998-02-18

Applicant: DAICEL CHEM ,  ISHII YASUTAKA

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA

IPC: B01J31/02 ,  C07B41/06 ,  C07B61/00 ,  C07C46/08 ,  C07C50/18

Abstract: PROBLEM TO BE SOLVED: To obtain the corresponding quinones in a good yield by oxidizing an aromatic hydrocarbon with molecular oxygen under mild conditions. SOLUTION: This method for producing quinones comprises oxidizing an aromatic hydrocarbon in the presence of a compound which can be oxidized by an imide compound and oxygen in a method for producing the corresponding quinones by oxidizing the aromatic hydrocarbon with molecular oxygen in the presence of the imide compound such as N-hydroxyphthalic imide. (a) A compound having carbon-hydrogen bond at a part which is adjacent to unsaturated bond (e.g. fluorene), (b) a compound, etc., having methine carbon atom can be used as the compound which can be oxidized by the imide compound and oxygen. According to the method, anthraquinone is produced in a good yield from anthracene.

公开(公告)号：JPH11180928A

公开(公告)日：1999-07-06

申请号：JP35339597

申请日：1997-12-22

Applicant: DAICEL CHEM ,  ISHII YASUTAKA

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA

IPC: B01J27/10 ,  B01J27/122 ,  B01J27/125 ,  B01J27/128 ,  B01J27/132 ,  B01J27/135 ,  B01J31/22 ,  C07B61/00 ,  C07C51/08 ,  C07C59/01 ,  C07C59/48 ,  C07C253/00 ,  C07C253/16 ,  C07C255/14 ,  C07C255/16

Abstract: PROBLEM TO BE SOLVED: To obtain the subject compound useful as a precursor of an α-hydroxy acid in good yield by a stable method by reacting an enol ester compound with a carbonyl compound and a cyanogenating agent in the presence of a metal catalyst. SOLUTION: An enol ester compound of formula I [R is a nonreactive atom or a nonreactive organic group; R to R are each hydrogen or a 1-5C alkyl] or an oxime ester compound of formula II (R and R are each a nonreactive atom or a nonreactive organic group and R and R may form a ring together with adjacent one or two carbons) is reacted with a carbonyl compound of formula III (R and R are each R or R ) and a cyanogenating agent (preferably hydrogen cyanide) to provide the objective compound of formula IV. Furthermore, the α-hydroxy acid is preferably obtained by hydrolyzing the compound of formula IV.

公开(公告)号：JPH11106377A

公开(公告)日：1999-04-20

申请号：JP21788497

申请日：1997-08-12

Applicant: DAICEL CHEM ,  ISHII YASUTAKA

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA

IPC: C07D295/02 ,  B01J31/02 ,  C07B41/08 ,  C07B61/00 ,  C07D209/48 ,  C07D213/79 ,  C07D265/32 ,  C07D307/48 ,  C07D307/68 ,  C07D333/40

Abstract: PROBLEM TO BE SOLVED: To efficiently produce the corresponding oxide from a heterocyclic compound by using an oxidation catalyst composed of a specific compound and a promoter. SOLUTION: A heterocyclic compound (e.g. 2,5-dimethylthiophene) is brought into contact with oxygen in the presence of an oxidation catalyst composed of an imide compound represented by the formula [R and R are each H, a halogen, an alkyl, an aryl or the like; X is O atom or hydroxyl; (n) is 1-3] (e.g. N-hydroxyophthalimide) and preferably a promoter (especially a transition metallic compound). The contact is preferably carried out in the presence of a protonic acid in a solvent such as acetic acid at 0-300 deg.C reactional temperature under atmospheric pressure or under an applied pressure for about 30 min to 48 hr.

公开(公告)号：JPH1149764A

公开(公告)日：1999-02-23

申请号：JP21202097

申请日：1997-08-06

Applicant: DAICEL CHEM ,  ISHII YASUTAKA

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA

IPC: C07D301/08 ,  B01J31/02 ,  C07B61/00 ,  C07D303/04

Abstract: PROBLEM TO BE SOLVED: To provide a method for producing the subject compound by reacting a compound having a non-aromatic, ethylenic double bond with oxygen in the presence of an oxidation catalyst to form the corresponding epoxy compound. SOLUTION: This epoxy compound is obtained by reacting a compound having a non-aromatic, ethylenic double bond, e.g. an alkene or cycloalkene compound, with oxygen in the presence of an oxidation catalyst composed of an imide compound shown by the formula [R and R are each H, a halogen, alkyl, aryl, cycloalkyl, hydroxyl, alkoxy, carboxyl, alkoxycarbonyl or acyl, wherein R and R are bound to each other to form a double bond or ring; X is O or hydroxyl; and (n) is 1 to 3]. The oxidation catalyst may be composed of a cocatalyst, e.g. a metallic compound containing a IV to VIII group element, together with the imide compound shown by the formula. The method gives an epoxy compound in high yield by a simple procedure, The epoxy compound can be obtained efficiently by the action of oxygen even under mild conditions.

公开(公告)号：JPH0977705A

公开(公告)日：1997-03-25

申请号：JP26225895

申请日：1995-09-13

Applicant: ISHII YASUTAKA ,  DAICEL CHEM

Inventor： ISHII YASUTAKA ,  NAKANO TATSUYA

IPC: C07D307/33 ,  C07B33/00 ,  C07B41/06 ,  C07B41/08 ,  C07C27/00 ,  C07C45/29 ,  C07C47/54 ,  C07C49/04 ,  C07C49/385 ,  C07C49/76 ,  C07C51/235 ,  C07C53/126 ,  C07C55/14 ,  C07C61/00 ,  C07C63/00 ,  C07C67/40 ,  C07C69/02 ,  C07C69/75

Abstract: PROBLEM TO BE SOLVED: To produce a corresponding carbonyl compound by oxidizing an alcohol with a halogen acid in high conversion and selectivity. SOLUTION: A primary or secondary alcohol is oxidized using an oxidizing agent comprising a halogen acid of the formula: M(XO3 )n (M is hydrogen atom or metal; X is a halogen atom; n is 1 or shows the valence of the metal M) or its salt (bromic acid, iodic acid or their alkali metal salt) and a reducing inorganic compound (sulfite, hydrogensulfite, thiosulfate or pyrosulfite) to give the corresponding carbonyl compound stoichiometrically. The oxidative esterification of a primary alcohol gives the corresponding ester and carboxylic acid, a secondary alcohol gives the corresponding ketone and an α,ω-diol gives the corresponding lactone or dicarboxylic acid.