Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
1999-11-22
2001-05-08
Owens, Amelia (Department: 1612)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C549S273000, C549S295000, C549S518000, C560S129000
Reexamination Certificate
active
06229023
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a process for the co-oxidation of organic compounds, a process for the production of epoxy compounds, and a process for the production of esters or lactones. More particularly, it relates to a process of co-oxidizing an alkene, a cycloalkane or another compound having a non-aromatic ethylenic bond, or a ketone or an alcohol, by molecular oxygen in the coexistence of another organic compound to give a corresponding oxide, that is, an epoxy compound, or an ester or a lactone.
BACKGROUND ART
Chain or cyclic epoxy compounds, esters and lactones are important compounds as pharmaceuticals, perfumes, dyes, organic intermediates and materials for polymeric resins.
Epoxy compounds and esters or lactones are, even though they are different in reaction materials, common in that they are produced by oxidation reaction using perbenzoic acid, peracetic acid, trifluoroperacetic acid or another peracid. For example, an epoxy compound is produced by the reaction of an alkene, a cycloalkane or another compound having a non-aromatic ethylenic bond with the peracid. An ester or lactone is obtained by the reaction of a chain or cyclic ketone with the peracid, i.e., by a so-called Baeyer-Villiger rearrangement (oxidation). The peracid is, however, unstable and should be handled with extreme caution. In addition, an equivalent amount of a carboxylic acid is by-produced in the reaction using the peracid.
As a production process for epoxy compounds is known a process of allowing a hypohalogenous acid to act on an unsaturated compound to give a halohydrin, and treating the halohydrin with an alkali. This process is, however, unable to be applied to olefins each having a complicated structure. Furthermore, there is known a process of allowing a microorganism to act on an unsaturated compound in the presence of oxygen to give a corresponding epoxy compound. Such a process using a microorganism is, however, disadvantageous in productivity, because the concentration of a substrate cannot generally be increased.
Japanese Unexamined Patent Publication No. 9-327626 discloses a process of oxidizing an unsaturated chain hydrocarbon or an alkene, cyclohexanone or cyclohexanol by molecular oxygen in the presence of an imide compound. According to this literature, however, an unsaturated chain hydrocarbon or an alkene predominantly gives a ketone or an alcohol in which the adjacent position to a double bond is oxidized, and a corresponding epoxy compound is not obtained. Cyclohexanone or cyclohexanol predominantly gives a corresponding dicarboxylic acid, but no corresponding ester or lactone.
DISCLOSURE OF INVENTION
Accordingly, it is an object of the invention to provide a process which can oxidize alkenes, cycloalkenes and other compounds each having a non-aromatic ethylenic bond or chain or cyclic ketones, under mild conditions, by simple operations with efficiency.
Another object of the invention is to provide a process which can produce corresponding epoxy compounds from compounds each having a non-aromatic ethylenic bond, under mild conditions, by simple operations in high yield.
It is a further object of the invention to provide a process which can produce, under mild conditions, corresponding esters or lactones by the oxidation of ketones or their precursors, secondary alcohols, with facility and efficiency.
After intensive investigations to achieve the above objects, the present inventors found that an effective solution is the oxidation of a compound having a non-aromatic ethylenic bond or a ketone (or its alcohol) by molecular oxygen with the use of an imide compound having a specific structure as a catalyst and in the coexistence of a specific compound, or the oxidation of a secondary alcohol by molecular oxygen in the presence of an imide compound catalyst having a specific structure and subsequent treatment with an acid. By this configuration, an epoxidation reaction preferentially proceeds to give a corresponding epoxy compound in satisfactory yield when a compound having a non-aromatic ethylenic bond is used as a material, or a so-called Baeyer-Villiger type reaction proceeds to give a corresponding ester or lactone with efficiency when a ketone or a secondary alcohol is used as a material. The present invention has been accomplished based upon the above findings.
To be more specific, the invention provides a process for the co-oxidation of organic compounds, the process including the step of:
oxidizing (A) a compound selected from (A1) a compound having a non-aromatic ethylenic bond, and (A2) a ketone represented by the following formula (2):
(wherein each of R
a
and R
b
is, identical to or different from each other, an organic group having a carbon atom at a bonding size with the adjacent carbonyl carbon atom, where R
a
and R
b
may be combined to form a ring with the adjacent carbonyl carbon atom)
or an alcohol corresponding to the ketone, by molecular oxygen in the presence of an imide compound represented by the following formula (1):
(wherein each of R
1
and R
2
is, identical to or different from each other, 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, where R
1
and R
2
may be combined to form a double bond, or an aromatic or non-aromatic ring; X is an oxygen atom or a hydroxyl group; and one or two N-substituted cyclic imido groups indicated in the formula (1) may further be formed on the aforementioned R
1
, R
2
, or on the double bond or aromatic or non-aromatic ring formed together by R
1
and R
2
) and in the coexistence of (B) a compound being oxidizable by the imide compound and oxygen and being different from the compound (A).
R
1
and R
2
in the imide compound represented by the formula (1) may be combined to form an aromatic or non-aromatic 5- to 12-membered ring, and R
1
and R
2
may be combined to form a cycloalkane ring which may have a substituent, a cycloalkene ring which may have a substituent, a bridged carbocyclic ring which may have a substituent, or an aromatic ring which may have a substituent.
The compound (A1) having a non-aromatic ethylenic bond includes, but is not limited to, (A11) chain hydrocarbons each having an ethylenic bond and having 2 to 30 carbon atoms, (A12) compounds each having a 3- to 30-membered cycloalkene ring, (A13) unsaturated bridged cyclic hydrocarbons, and (A14) heterocyclic compounds each having a non-aromatic ethylenic bond as a constitutive element of its ring.
The ketone represented by the formula (2) includes, but is not limited to, cyclohexanones and other 3- to 20-membered cycloalkanones.
As the compound (B), use may be made of at least one compound selected from (a) primary or secondary alcohols, (b) compounds each having a carbon-hydrogen bond at the adjacent position to an unsaturated bond, (c) compounds each having a methine carbon atom, (d) cycloalkanes, (e) non-aromatic heterocyclic compounds each having a carbon-hydrogen bond at the adjacent position to a hetero atom, (f) conjugated compounds, (g) aromatic hydrocarbons, (h) thiols, (i) ethers, (j) sulfides, (k) aldehydes or thioaldehydes, and (l) amines.
In the process for the co-oxidation of organic compounds, the oxidation may be performed further in the presence of (C) at least one compound selected from the group consisting of (C1) compounds each having a carbonyl group combined with an electron attractive group, (C2) metallic compounds, and (C3) organic salts each composed of a polyatomic cation or a polyatomic anion and its counter ion, the polyatomic cation or anion containing a Group 15 or Group 16 element of the Periodic Table of Elements, the element having at least one organic group bonded thereto.
The invention provides, in another aspect, a process for the production of epoxy compounds, the process including the step of: oxidizing (A1) a compound having a non-aromatic ethylenic bond by molecular oxygen in the presence of the imide compound represented by the formula (1) to form
Ishii Yasutaka
Nakano Tatsuya
Daicel Chemical Industries Ltd.
Owens Amelia
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