Organic compounds -- part of the class 532-570 series – Organic compounds – Sulfonic acids or salts thereof
Reexamination Certificate
2001-11-02
2004-03-16
Killos, Paul J. (Department: 1625)
Organic compounds -- part of the class 532-570 series
Organic compounds
Sulfonic acids or salts thereof
Reexamination Certificate
active
06706915
ABSTRACT:
TECHNICAL FIELD
The present invention relates to a process for producing organic sulfur acids or salts thereof which are useful, for example, as materials for pharmaceuticals, agrochemicals and dyes or as detergents.
BACKGROUND ART
A variety of processes are known for producing organic sulfur acids or salts thereof. For example, such processes for producing a sulfonic acid include a process of oxidizing a thiol or disulfide with an oxidizing agent, a process of allowing an aromatic hydrocarbon to react with anhydrous SO
3
-pyridine or chlorosulfuric acid by the use of a Friedel-Crafts reaction, and a process of synthetically obtaining a sulfonic acid by subjecting an unsaturated compound to free-radical addition. These processes, however, require extreme reaction conditions or inevitably produce large amounts of by-products. Separately, few processes for directly and efficiently sulfonating non-aromatic hydrocarbons have been known.
The Chemical Society of Japan, Spring Conference Proceedings (1999) reports on a sulfonation reaction of a hydrocarbon with sulfur dioxide and oxygen by catalysis of N-hydroxyphthalimide. This process can yield a corresponding sulfonic acid from a hydrocarbon such as adamantane through one step. However, demands have been made on a process for further efficiently producing sulfonic acids and other organic sulfur acids or salts thereof at a lower cost.
DISCLOSURE OF INVENTION
Accordingly, an object of the present invention is to provide a process for efficiently producing an organic sulfur acid or a salt thereof under mild conditions.
Another object of the present invention is to provide a process for directly and efficiently producing a corresponding sulfur acid or a salt thereof from a non-aromatic hydrocarbon.
After intensive investigations to achieve the above objects, the present inventors have found that, by using a metallic compound as a catalyst, a corresponding organic sulfur acid or a salt thereof can efficiently be obtained from an organic substrate and a sulfur oxide even in the absence of N-hydroxy and N-oxo cyclic imide compounds. The present invention has been accomplished based on these findings.
Specifically, the present invention provides a process for producing an organic sulfur acid or a salt thereof. The process includes the step of allowing an organic substrate to react with a sulfur oxide in the presence of a metallic compound catalyst and in the absence of N-hydroxy and N-oxo cyclic imide compounds to thereby yield a corresponding organic sulfur acid or a salt thereof. The sulfur oxide includes, for example, sulfur dioxide. Such organic substrates include, for example, (a) homocyclic or heterocyclic compounds each having a methylene group, (b) compounds each having a methine carbon atom, (c) compounds each having a methyl group or methylene group at the adjacent position to an unsaturated bond, (d) non-aromatic heterocyclic compounds each having a carbon-hydrogen bond at the adjacent position to a hetero atom, and (e) straight-chain alkanes.
The term “N-hydroxy and N-oxo cyclic imide compounds” specifically means compounds 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 or an aromatic or non-aromatic ring; X is an oxygen atom or a hydroxyl group, where one or two of N-substituted cyclic imido group indicated in the formula (1) may be further bonded to the aforementioned R
1
, R
2
or to the double bond or aromatic or non-aromatic ring formed together by R
1
and R
2
.
BEST MODE FOR CARRYING OUT THE INVENTION
[Organic Substrate]
The substrates for use in the invention are not specifically limited and include a wide variety of saturated or unsaturated compounds. Such compounds include, but are not limited to, hydrocarbons (aliphatic hydrocarbons, alicyclic hydrocarbons and aromatic hydrocarbons), heterocyclic compounds, alcohols, ethers, esters, ketones and aldehydes. Each of these substrates can be used alone or in combination.
Preferred substrates include, but are not limited to, (a) homocyclic or heterocyclic compounds each having a methylene group, (b) compounds each having a methine carbon atom, (c) compounds each having a methyl group or a methylene group at the adjacent position to an unsaturated bond, (d) non-aromatic heterocyclic compounds each having a carbon-hydrogen bond at the adjacent position to a hetero atom, and (e) straight-chain alkanes. In these compounds, a sulfur acid group such as a sulfonic acid group or sulfinic acid group is introduced into the methylene group, methine carbon atom, methyl group or methylene group, carbon atom at the adjacent position to the hetero atom, and carbon atom constituting the straight-chain alkane, respectively.
Of the compounds (a), homocyclic compounds (a1) having a methylene group include, but are not limited to, cycloalkanes (e.g., cyclopropane, cyclobutane, cyclopentane, cyclohexane, methylcyclohexane, 1,2-diethylcyclohexane, isopropylcyclohexane, cycloheptane, cyclooctane, methylcyclooctane, cyclononane, cyclodecane, cyclododecane, cyclotridecane, cyclotetradecane, cyclopentadecane, cyclohexadecane, cyclooctadecane, cyclononadecane, and other C
3
-C
30
cycloalkanes), cycloalkenes (e.g., cyclopropene, cyclobutene, cyclopentene, cyclohexene, 1-methyl-1-cyclohexene, cycloheptene, cyclooctene, cyclononene, cyclodecene, cyclododecene, and other C
3
-C
30
cycloalkenes), cycloalkadienes (e.g., cyclopentadiene, cyclohexadiene, cycloheptadiene, cyclooctadiene, cyclodecadiene, cyclododecadiene, and other C
5
-C
30
cycloalkadienes), cycloalkatrienes, cycloalkatetraenes, and condensed polycyclic aromatic hydrocarbons each having a 5- to 8-membered non-aromatic ring condensed therewith.
Of the compounds (a), heterocyclic compounds (a2) each having a methylene group include, for example, 5- or 6-membered cyclic compounds having a hetero atom selected from nitrogen, oxygen and sulfur atoms, or condensed heterocyclic compounds having an aromatic ring and a 5- or 6-membered ring having a hetero atom condensed to the aromatic ring. Examples of such heterocyclic compounds (a2) are dihydrofuran, tetrahydrofuran, pyran, dihydropyran, tetrahydropyran, piperidine, piperazine, pyrrolidine and xanthene. In the compounds (a), a sulfur acid group is introduced into the methylene group constituting a non-aromatic ring.
The compounds (b) each having a methine carbon atom (a methylidyne group) include, for example, (b1) chain hydrocarbons each having a tertiary carbon atom, (b2) bridged cyclic compounds and (b3) non-aromatic cyclic compounds each having a hydrocarbon group bonded to its ring.
The chain hydrocarbons (b1) each having a tertiary carbon atom include, but are not limited to, isobutane, isopentane, isohexane, 3-methylpentane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 2,3-dimethylpentane, 2,4-dimethylpentane, 2,3,4-trimethylpentane, 3-ethylpentane, 2,3-dimethylhexane, 2,4-dimethylhexane, 3,4-dimethylhexane, 2,5-dimethylhexane, 2-propylhexane, 2-methylheptane, 4-methylheptane, 2-ethylheptane, 3-ethylheptane, 2,6-dimethylheptane, 2-methyloctane, 3-methyloctane, 2,7-dimethyloctane, 2-methylnonane, and other aliphatic hydrocarbons each having from about 4 to about 20 (preferably from about 4 to about 10) carbon atoms. In the compounds (b1), a sulfur acid radical is introduced into the tertiary carbon atom.
The bridged cyclic compounds (b2) include, but are not limited to, decalin, bicyclo[2.2.0]hexane, bicyclo[2.2.2]octane, bicyclo[3.2.1]octane, bicyclo[4.3.2]undecane, thujone, carane, pinane, pinene, bornane, bornylene, norbornane, norbornene, camphor, camphoric acid, camphene, tricyclene, tricyclo[4.3.1.1
2,5
]undecane, tricyclo[5.2.1.0
3,8
]decane, exotricyclo[5.2.1.0
2,6
]decane, endotricyclo[5.2.1.0
2,6
&rsq
Ishii Yasutaka
Nakano Tatsuya
Daicel Chemical Industries Ltd.
Killos Paul J.
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