Catalyst comprising nitrogen-containing heterocyclic...

Details Catalyst comprising nitrogen-containing heterocyclic... Catalyst comprising nitrogen-containing heterocyclic...

2000-09-01

2002-06-11

Lambkin, Deborah C. (Department: 1626)

Catalyst, solid sorbent, or support therefor: product or process

Catalyst or precursor therefor

Organic compound containing

C502S152000, C502S155000, C502S162000, C502S204000, C502S213000, C549S390000, C548S257000, C548S259000, C544S180000, C544S215000

Reexamination Certificate

active

06403521

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a catalyst which is useful for oxidation, nitration, carboxylation, and other reactions for introducing a group containing at least an oxygen atom into an organic substrate, and to a process for producing an organic compound using the catalyst.
2. Description of the Related Art
Oxidation reaction is one of the most basic reactions in organic chemical industries, and a variety of oxidation processes are known. For example, a process is known which includes the step of oxidizing a methyl group, or a methylene group or methine group corresponding to the benzyl position on an aromatic ring, an alcohol or a carbonyl compound with nitric acid to yield a corresponding carboxylic acid. However, this oxidation process using nitric acid invites by-production of nitrogen oxides and therefore requires expensive treating facilities of exhaust gas. In another known oxidation process, a substrate is oxidized with molecular oxygen in the presence of a metallic compound catalyst such as a cobalt catalyst. However, this process can be applied only within a narrow range and requires extreme conditions such as high temperatures and high pressures upon oxidation of some substrates.
On the other hand, a process using a mixed acid (a mixture of nitric acid and sulfuric acid) is in wide use as a process for the nitration of hydrocarbons. However, this process requires the use of highly concentrated strong acids in large amounts, and in addition, invites by-production of nitrogen oxides in large amounts as in the nitric acid oxidation process. The process in question therefore requires treating facilities for these substances.
As for carboxylation, few processes are known to introduce a carboxyl group directly into a hydrocarbon under mild conditions.
As is described, an oxygen-atom-containing group such as a hydroxyl group, a nitro group, or a carboxyl group cannot be generally significantly introduced into an organic substrate under mild conditions.
SUMMARY OF THE INVENTION
Accordingly, an object of the invention is to provide a catalyst which can introduce an oxygen-atom-containing group into an organic substrate under mild conditions, and to provide a process for producing an organic compound using the catalyst.
Another object of the invention is to provide a highly versatile catalyst which can be applied to a wide variety of reactions using oxygen-atom-containing reactants, and to provide a process for producing an organic compound using the catalyst.
A further object of the invention is to provide a catalyst which requires no exhaust gas treating facilities and can introduce an oxygen-atom-containing group into an organic substrate even by the use of the catalyst in a small amount, and to provide a process for producing an organic compound using the catalyst.
After intensive investigations to achieve the above objects, the present inventors found that when an organic substrate is allowed to react with an oxygen-atom-containing reactant such as oxygen in the presence of a nitrogen-containing heterocyclic compound having a specific structure, an oxygen-atom-containing group such as a hydroxyl group can be introduced into the organic substrate under mild conditions. The present invention has been accomplished based on these findings.
Specifically, the invention provides, in an aspect, a catalyst for a reaction using an oxygen-atom-containing reactant. This catalyst includes a nitrogen-containing heterocyclic compound shown 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, a haloalkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, an alkoxycarbonyl group, or an acyl group, and R
1
and R
2
may be combined to form a double bond or to form an aromatic or non-aromatic ring with the adjacent two carbon atoms, where one or two of heterocyclic ring containing three nitrogen atoms indicated in the formula may be further formed on the R
1
or R
2
, or on the double bond or aromatic or non-aromatic ring formed by R
1
and R
2
; X is an oxygen atom or a hydroxyl group; and Y is a single bond, a methylene group, or a carbonyl group.
In another aspect, the invention provides a process for producing an organic compound. This process includes the step of allowing an organic substrate to react with an oxygen-atom-containing reactant in the presence of the aforementioned catalyst to yield a product, to the product a group containing at least an oxygen atom is introduced.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[Nitrogen-containing Heterocyclic Compound]
Of the substituents R
1
and R
2
in the nitrogen-containing heterocyclic compound of the formula (1), the halogen atom includes, for example, iodine, bromine, chlorine, and fluorine atoms. Illustrative alkyl groups are methyl, ethyl, propyl, isopropyl, butyl, isobutyl, s-butyl, t-butyl, hexyl, decyl, and other straight- or branched-chain alkyl groups each having about 1 to 10 carbon atoms. Preferred alkyl groups are alkyl groups each having about 1 to 6 carbon atoms, of which lower alkyl groups each having about 1 to 4 carbon atoms are particularly preferred. The haloalkyl group includes, for example, trifluoromethyl group, and other haloalkyl groups each having about 1 to 4 carbon atoms.
The aryl group includes phenyl and naphthyl groups, for example. Illustrative cycloalkyl groups include cyclopentyl and cyclohexyl groups. Illustrative alkoxy groups are methoxy, ethoxy, isopropoxy, butoxy, t-butoxy, hexyloxy, and other alkoxy groups each having about 1 to 10 carbon atoms, and preferably having about 1 to 6 carbon atoms. Among them, lower alkoxy groups each having about 1 to 4 carbon atoms are especially preferred.
Illustrative alkoxycarbonyl groups include methoxycarbonyl, ethoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, t-butoxycarbonyl, hexyloxycarbonyl, and other alkoxycarbonyl groups each having about 1 to 10 carbon atoms in the alkoxy moiety. Preferred alkoxycarbonyl groups are alkoxycarbonyl groups each having about 1 to 6 carbon atoms in the alkoxy moiety, of which lower alkoxycarbonyl groups each having about 1 to 4 carbon atoms in the alkoxy moiety are particularly preferred. The acyl group includes, but is not limited to, formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, pivaloyl, benzoyl, and other acyl groups each having about 1 to 7 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 the formula (1) may be combined to form a double bond or to form an aromatic or non-aromatic ring with the adjacent two carbon atoms. Preferred aromatic or non-aromatic rings each have about 5 to 12 members, and preferably about 6 to 10 members. The ring may be any of carbocyclic rings and heterocyclic rings, and to these rings, another ring may be condensed. Such rings include, for example, non-aromatic alicyclic rings (e.g., cyclohexane ring, and other cycloalkane rings which may have a substituent; cyclohexene ring, and other cycloalkene rings which may have a substituent; and 5-norbornene ring, and other bridged hydrocarbon rings which may have a substituent), benzene ring, naphthalene ring, and other aromatic rings (including condensed rings) which may have a substituent, and pyridine ring and other aromatic heterocyclic rings which may have a substituent. The ring is composed of an aromatic ring (a carbocyclic ring or heterocyclic ring) in many cases. The ring may have a substituent. Such substituents include, but are not limited to, alkyl groups (e.g., C
1
-C
4
alkyl groups), haloalkyl groups (e.g., C
1
-C
4
haloalkyl groups), aryl groups, cycloalkyl groups, hydroxyl group, alkoxy groups(e.g., C
1
-C
4
alkoxy groups), carboxyl group, alkoxycarbonyl groups (e.g., C
1
-C
4
alkoxy-carbonyl groups), acyl groups (e.g., C
1
-C
7
acyl groups), nitro group, cyano group, sulfo group, substituted or unsubstituted amino gr

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