Process for producing organic peroxides

Details Process for producing organic peroxides Process for producing organic peroxides

2003-05-13

2004-07-27

Dentz, Bernard (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

Reexamination Certificate

active

06768030

ABSTRACT:

This application is the national phase under 35 U.S.C. § 371 of PCT International Application No. PCT/JP01/09768 which has an International filing date of Nov. 8, 2001, which designated the United States of America.
TECHNICAL FIELD
The present invention relates to a process for producing bis(1-hydroxycycloalkyl) peroxides that are useful as, for example, raw materials for lactones and lactams.
BACKGROUND ART
Bis(1-hydroxycycloalkyl) peroxides are useful as, for example, raw materials for lactones and lactams. For example, By treating bis(1-hydroxycyclohexyl) peroxide with an acid, &egr;-caprolactone, which is important as a raw material for a polyester, can be produced in a good yield (U.S. Pat. No. 4,183,863). By allowing ammonia to act upon bis(1-hydroxycyclohexyl) peroxide, &egr;-caprolactam, which is useful as a raw material for a polyamide, can be obtained (Japanese Examined Patent Application Publication No. 46-25742).
Liebig Annalen der Chemie, vol. 565, pp. 7 (1949) discloses a process for producing a bis(1-hydroxycycloalkyl) peroxide by allowing cyclohexanone to react with hydrogen peroxide. This process, however, requires expensive hydrogen peroxide as a raw material and is not appropriate as an industrial process. PCT International Publication No. WO99/50204 mentions that, by allowing cyclohexanol to react with oxygen in the presence of cyclohexanone and N-hydroxyphthalimide and then allowing indium chloride to act upon the resulting mixture, bis(1-hydroxycyclohexyl) peroxide is produced in addition to &egr;-caprolactone. This process, however, requires relatively expensive cyclohexanol as a raw material, also requires cyclohexanone and is disadvantageous.
DISCLOSURE OF INVENTION
Accordingly, an object of the present invention is to provide a process for easily producing a bis(1-hydroxycycloalkyl) peroxide from an inexpensive raw material.
Another object of the present invention is to provide a process for directly producing a bis(1-hydroxycycloalkyl) peroxide from a cycloalkane and oxygen.
After intensive investigations to achieve the above objects, the present inventors have found that a bis(1-hydroxycycloalkyl) peroxide is directly produced from a cycloalkane and oxygen by using a specific catalyst. The present invention has been accomplished based on these findings.
Specifically, the present invention provides a process for producing an organic peroxide, the process including the step of allowing a cycloalkane to react with oxygen in the presence of a catalytic imide compound having an N-hydroxy (or N-oxo) cyclic imide skeleton to yield a corresponding bis(1-hydroxycycloalkyl) peroxide.
The catalytic imide compound includes, for example, a compound represented by following Formula (1):
wherein R
1
and R
2
are the same or different and are each 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, an aromatic or non-aromatic ring; X is an oxygen atom or a hydroxyl group; and one or two of N-substituted cyclic imido group indicated in the formula may be further formed on the R
1
, R
2
, or on the double bond or aromatic or non-aromatic ring formed by R
1
and R
2
. The cycloalkane includes, for example, cycloalkanes each having from 5 to 15 members.
BEST MODE FOR CARRYING OUT THE INVENTION
[Cycloalkanes]
Cycloalkanes for use as starting materials in the present, invention include, but are not limited to, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclononane, cyclodecane, cyclododecane, cyclotetradecane, cyclohexandecane, cyclooctadecane, cycloicosane, cyclodocosane, cyclotriacontane, and other cycloalkanes each having from about 3 to about 30 members. Among them, cyclopentane, cyclohexane, cyclooctane, cyclododecane, and other cycloalkanes each having from about 5 to about 15 members are preferred, of which cyclohexane and cyclododecane are typically preferred.
These cycloalkanes may have at least one substituent within a range not adversely affecting a reaction. Such substituents include, but are not limited to, halogen atoms, oxo group, hydroxyl group, mercapto group, substituted oxy groups (e.g., alkoxy groups, aryloxy groups and acyloxy groups), substituted thio groups, carboxyl group, substituted oxycarbonyl groups, substituted or unsubstituted carbamoyl groups, cyano group, nitro group, substituted or unsubstituted amino groups, alkyl groups (e.g., methyl, ethyl, isopropyl, t-butyl, hexylk octyl, decyl, and other C
1
-C
20
alkyl groups, of which C
1
-C
4
alkyl groups are preferred), alkenyl groups, alkynyl groups, cycloalkyl groups, cycloalkenyl groups, aryl groups (e.g., phenyl and naphthyl groups), aralkyl groups (e.g., benzyl group), and heterocyclic groups. Each of the cycloalkanes may have an aromatic or non-aromatic carbon ring or heterocyclic ring condensed to the cycloalkane ring within a range not adversely affecting the reaction.
[Oxygen]
As oxygen, either of molecular oxygen and nascent oxygen can be used. The molecular oxygen is not specifically limited and includes pure oxygen, oxygen diluted with an inert gas such as nitrogen, helium, argon or carbon dioxide, and air. Oxygen can be formed in the reaction system. The amount of oxygen is generally equal to or more than about 0.5 mole (for example, equal to or more than about 1 mole), preferably from about 1 to about 100 moles, and more preferably from about 2 to about 50 moles, relative to 1 mole of the substrate cycloalkane. Oxygen is often used in excess moles to the substrate.
[Catalytic Imide Compounds]
According to the present invention, an imide compound having an N-hydroxy (or N-oxo) cyclic imide skeleton is used as a catalyst. Such imide compounds include, for example, the compounds represented by Formula (1).
Of the substituents R
1
and R
2
in the imide compounds represented by Formula (1), the halogen atom includes iodine, bromine, chlorine and fluorine atoms. The alkyl group includes, but is not limited to, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, pentyl, hexyl, heptyl, octyl, decyl, and other straight- or branched-chain alkyl groups each having from about 1 to about 10 carbon atoms. Preferred alkyl groups are alkyl groups each having from about 1 to about 6 carbon atoms, of which lower alkyl groups each having from about 1 to about 4 carbon atoms are typically preferred.
The aryl group includes phenyl and naphthyl groups, for example. Illustrative cycloalkyl groups include cyclopentyl and cyclohexyl groups. Illustrative alkoxy groups are methoxy, ethoxy, propoxy, isopropoxy, butoxy, isobutoxy, t-butoxy, pentyloxy, hexyloxy, and other alkoxy groups each having from about 1 to about 10 carbon atoms, and preferably having from about 1 to about 6 carbon atoms. Among them, lower alkoxy groups each having from about 1 to about 4 carbon atoms are typically preferred.
Examples of the alkoxycarbonyl group include methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, isobutoxycarbonyl, t-butoxycarbonyl, pentyloxycarbonyl, hexyloxycarbonyl, and other alkoxycarbonyl groups each having from about 1 to about 10 carbon atoms in the alkoxy moiety. Preferred alkoxycarbonyl groups are alkoxycarbonyl groups each having from about 1 to about 6 carbon atoms in the alkoxy moiety, of which lower alkoxycarbonyl groups each having from about 1 to about 4 carbon atoms in the alkoxy moiety are typically preferred.
The acyl group includes, but is not limited to, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, and other acyl groups each having from about 1 to about 6 carbon atoms.
The substituents R
1
and R
2
may be identical to or different from each other. The substituents R
1
and R
2
in Formula (1) may be combined to form a double bond, or an aromatic or non-aromatic ring. The preferred aromatic or non-aromatic ring is a 5- to 12-membered ring, and especially

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