Daicel Chemical Industries, Ltd.

Tomohide Ina

Hiroyuki Miura

Kazuyuki Matsuoka

Hitoshi Watanabe

Hidehiko Nakajima

Li Rui Pan

Keizo Inoue

Ikuo Takahashi

Noboru Kamei

Shinya Nagano

In the presence of (1) an oxidizing catalyst comprising an imide compound such as N-hydroxyphthalimide, or (2) an oxidizing catalyst comprising such imide compound and a transition metal element-containing compound as a co-oxidizing agent (e. g., oxides, halides, complexes, hetero polyacid salts) a hydrocaron, an alcohol, an aldehyde, or a ketone as a substrate is brought into contact with molecular oxygen for oxidation. In the above-described oxidation process, the water content of the oxidizing reaction system is 200 mol or lower relative to 1 mol of the imide compound. According to the present invention, a substrate is efficiently oxidized with molecular oxygen under mild conditions, and there can be obtained the object compound(s) of high quality.

Oxidation method

Process for preparing cycloalkanone

Process for producing t-butyl esters of bridged-ring polycarboxylic acids

In the presence of an oxidizing catalyst, a &bgr;-isophorone derivative of the following formula (1) is oxidized in a solvent substantially from acid components (organic carboxylic acids) to form a ketoisophorone derivative of the following formula (2). The amount of the acid component in the solvent is 0 to 4,000 ppm (weight basis). The oxidizing catalyst is a complex salt of a transition metal and an N,N&prime;-disalicylidenediamine. In the reaction, a cyclic base may further be employed as a co-catalyst. The solvent separated from the reaction mixture may be recycled to the oxidation reaction after removal of the acid component contained therein.

Process for the production of ketoisophorone derivatives and equipment therefor

Process for producing hydroquinone diester derivative

&bgr;-isophorone is formed by isomerizing &agr;-isophorone in the presence of an isomerizing catalyst (an aliphatic C polycarboxylic acid) in an isomerizing-reaction unit . The &bgr;-isophorone thus formed is oxidized with oxygen in an inert solvent in the presence of an oxidizing catalyst (a complex salt of a transition metal and an N,N&prime;-disalicylidenediamine) in an oxidizing-reaction unit , thereby forming ketoisophorone. After removing a low-boiling point component, which is an impurity (non-conjugated cyclic ketone), from the reaction mixture using a distilling unit , a high-boiling component (oxidizing catalyst) is separated in a distilling unit , and then ketoisophorone is separated from the solvent in the separation unit . Thereafter, the solvent containing 0 to 5,000 ppm (weight basis) of the impurities and substantially free from ketoisophorone is recycled to the oxidizing reaction through a recycling line . According to the present invention, the combination of the isomerizing reaction and the oxidizing reaction makes it possible to produce ketoisophorone from &agr;-isophorone while maintaining the activity of the oxydizing catalyst.

Process and apparatus for producing ketoisophorone

A carbonylation catalytic system comprises (A) a combination of (A1) a Group VIII metal source of Periodic Table of the Elements (e.g., palladium, palladium chloride) supported on a carrier, (A2) a ligand such as triphenylphosphine and (A3) an acid such as an alkylsulfonic acid, or (B) a combination of (B1) the Group VIII metal source except for palladium (e.g., a platinum compound), (B2) a ligand such as triphenylphosphine and (B3) an electron donative compound having an electron donability .DELTA..nu.D of not less than 2 (for instance, an amine such as a heterocyclic tertiary amine). The catalytic system (B) may further comprise (B4) an acid such as methanesulfonic acid. In the presence of the catalytic system (A) or (B), an acetylenic or olefinic unsaturated compound is allowed to react with carbon monoxide and a nucleophilic compound having an active hydrogen such as water, an alcohol and a carboxylic acid in a liquid phase to give an unsaturated or saturated carboxylic acid or an ester thereof with high transformation rate and selectivity.

Catalytic systems and methods for carbonylation

A carbonylation catalytic system comprises (A) a combination of (A1) a Group VIII metal source of Periodic Table of the Elements (e.g., palladium, palladium chloride) supported on a carrier, (A2) a ligand such as triphenylphosphine and (A3) an acid such as an alkyl-sulfonic acid, or (B) a combination of (B1) the Group VIII metal source except for palladium (e.g., a platinum compound), (B2) a ligand such as triphenylphosphine and (B3) an electron donative compound having an electron donability .DELTA..nu.D of not less than 2 (for instance, an amine such as a heterocyclic tertiary amine). The catalytic system (B) may further comprise (B4) an acid such as methanesulfonic acid. In the presence of the catalytic system (A) or (B), an acetylenic or olefinic unsaturated compound is allowed to react with carbon monoxide and a nucleophilic compound having an active hydrogen such as water, an alcohol and a carboxylic acid in a liquid phase to give an unsaturated or saturated carboxylic acid or an ester thereof with high transformation rate and selectivity.

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Himeji, Japan

Tomohide Ina