Process for producing organic compounds using nitrites

Details Process for producing organic compounds using nitrites Process for producing organic compounds using nitrites

2003-03-06

2004-07-27

Davis, Brian (Department: 1621)

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

Organic compounds

Amino nitrogen containing

C564S261000

Reexamination Certificate

active

06768023

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing organic compounds each having, for example, a nitrogen-containing group, an oxygen-containing group, or a carbon-carbon unsaturated bond-containing group using a nitrous ester and/or nitrite.
2. Description of the Related Art
Oximes and other organic compounds each having a nitrogen-containing group are useful as intermediate materials for monomers for the production of polymeric compounds or as intermediates in the synthesis of fine chemicals. For example, cycloalkanone oximes are very important as intermediate materials for polyamides. Such cycloalkanone oximes have been conventionally produced by, for example, a process of subjecting a cycloalkanone and hydroxylamine to dehydration condensation, a process of catalytically hydrogenating a nitrocycloalkenone in the presence of a palladium catalyst, or a process of subjecting a hydroxyaminocycloalkane to air oxidation in the presence of a divalent cobalt. However, these processes require relatively expensive material compounds.
Cyclohexanone oxime is commercially produced by a process in which cyclohexane is irradiated with radiation in the presence of nitrosyl chloride to thereby yield cyclohexanone oxime via nitrosocyclohexane. This process can directly convert cyclohexane into cyclohexanone oxime and can thereby reduce production costs. However, nitrosyl chloride used as a raw material is generally prepared by a reaction between nitrogen monoxide and chlorine, thus invites complicated facilities and decreased operability and imposes heavy loads on the environment.
As a possible solution to these problems, for example, Japanese Examined Patent Application Publication No. 02-13659 discloses a process of allowing a cycloalkane to come in contact with a nitrous ester in a gas phase at a temperature of 150° C. to 400° C. to thereby yield a cycloalkanone oxime. This process, however, requires severe reaction conditions and exhibits a low space-time yield.
SUMMARY OF THE INVENTION
Accordingly, an object of the present invention is to provide a process for easily producing a nitrogen-containing organic compound such as an oxime from low-cost materials under mild conditions.
Another object of the present invention is to provide a process for efficiently producing an organic compound having, for example, a nitrogen-containing group, an oxygen-containing group, or a carbon-carbon unsaturated bond-containing group using an ester or salt of nitrous acid.
Yet another object of the present invention is to provide a process for selectively producing a nitroso compound or a dimer thereof in a high yield.
Still another object of the present invention is to provide a process for selectively and efficiently producing an oxime.
After intensive investigations to achieve the objects, the present inventors have found organic compounds each having, for example, a nitrogen-containing group, an oxygen-containing group, or a carbon-carbon unsaturated bond-containing group can be produced in good yields by allowing a compound capable of generating a free radical to react with at least one of esters and salts of nitrous acid in the presence of a nitrogen-containing cyclic compound having a specific structure. The present invention has been accomplished based on these findings.
Specifically, the present invention provides a process for producing an organic compound, including allowing (A) a compound capable of generating a free radical to react with (B) at least one of esters and salts of nitrous acid in the presence of a nitrogen-containing cyclic compound constitutively having a skeleton represented by following Formula (i) in its ring:
wherein X is one of an oxygen atom and an —OR group, and wherein R is one of a hydrogen atom and a hydroxyl-protecting group.
By this procedure, oxime compounds and other nitrogen-containing organic compounds having a nitrogen-containing group combined with a radical generating site of the compound (A) capable of generating a free radical; oxygen-containing organic compounds having an oxygen-containing group combined with the radical generating site; and organic compounds having a carbon-carbon unsaturated bond-containing group and other products can be efficiently produced from easily available raw materials by easy and simple procedures under mild conditions.
Examples of the nitrogen-containing cyclic compound include cyclic imide compounds having a cyclic imide skeleton represented by following Formula (I):
wherein n is one of 0 and 1; X is one of an oxygen atom and an —OR group, and wherein R is one of a hydrogen atom and a hydroxyl-protecting group.
Examples of the nitrogen-containing cyclic compound also include compounds represented by following Formula (1):
wherein n is one of 0 and 1;
X is one of an oxygen atom and an —OR group,
wherein R is one of a hydrogen atom and a hydroxyl-protecting group;
R
1
, R
2
, R
3
, R
4
, R
5
, and R
6
are the same or different and are each one of hydrogen atom, halogen atoms, alkyl groups, aryl groups, cycloalkyl groups, hydroxyl group, alkoxy groups, carboxyl group, substituted oxycarbonyl groups, acyl groups, and acyloxy groups,
wherein at least two of R
1
, R
2
, R
3
, R
4
, R
5
, and R
6
may be combined to form a double bond, an aromatic ring, or a non-aromatic ring with a carbon atom or a carbon-carbon bond constituting the cyclic imide skeleton, and
wherein one or more of N-substituted cyclic imide group represented by following Formula (a):
wherein n and X have the same meanings as defined above, may be further formed on at least one of R
1
, R
2
, R
3
, R
4
, R
5
, and R
6
or at least one of the double bond, the aromatic ring and the non-aromatic ring formed by at least two of R
1
, R
2
, R
3
, R
4
, R
5
, and R
6
.
Examples of the compound (A) capable of generating a free radical include (A1) aromatic compounds and unsaturated compounds each having a methyl group or methylene group at the adjacent position to an aromatic ring or an unsaturated bond; (A2) non-aromatic cyclic compounds each constitutively having a methylene group in their ring; and (A3) compounds each having a methine carbon atom.
In the process, an oxime compound may be formed as a result of a reaction.
In the process, the nitrous ester or nitrite (B) may be added to reaction system intermittently in plural installments or continuously. By this procedure, a nitroso compound or its dimer, or an oxime compound in a further proceeded reaction can be selectively produced in a high yield. The process may further include allowing the compound (A) capable of generating a free radical to react with the at least one of esters and salts of nitrous acid (B) to thereby yield a nitroso compound or a dimer thereof. The process may also further include the steps of allowing the compound (A) capable of generating a free radical to react with the at least one of esters and salts of nitrous acid (B) to thereby yield a nitroso compound or a dimer thereof; and converting the formed nitroso compound or a dimer thereof into an oxime compound. Thus, an oxime compound can be selectively and efficiently produced.
Further objects, features and advantages of the present invention will become apparent from the following description of the preferred embodiments.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Nitrogen-Containing Cyclic Compounds
At least one nitrogen-containing cyclic compound constitutively having a skeleton represented by Formula (i) in its ring is used as a catalyst in the present invention.
In Formula (i), the bond between a nitrogen atom and X is a single or double bond. The nitrogen-containing cyclic compound may intramolecularly have a plurality of the skeleton represented by Formula (i). When X is an —OR group and R is a hydroxyl-protecting group, the nitrogen-containing cyclic compound may have a plurality of moieties combined through R, which moieties are derived from the skeleton represented by Formula (i) by removal of R.
Examples of the hydroxyl-protecting group represented by R in Formula (i)

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