Organic compounds -- part of the class 532-570 series – Organic compounds – Heterocyclic carbon compounds containing a hetero ring...
Reexamination Certificate
2000-03-22
2001-03-13
McKane, Joseph K. (Department: 1626)
Organic compounds -- part of the class 532-570 series
Organic compounds
Heterocyclic carbon compounds containing a hetero ring...
C562S087000, C549S290000, C549S398000, C549S469000
Reexamination Certificate
active
06201131
ABSTRACT:
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for producing [2-(arylsulfonyl)ethenyl]benzene derivatives, which are useful as intermediates to pharmaceuticals, agricultural chemicals or the like.
2. Description of Related Art
It has been known that certain [2-(Arylsulfonyl)ethenyl]benzene derivatives have been produced from aryl vinyl sulfones (e.g., Japanese Patent Publication Kohyo No. H5-507288 (1993)). The aryl vinyl sulfones such as phenyl vinyl sulfones have been known as an irritant and have been isolated as a solid compound from a reaction mixture and charged into a reactor in a solid form. Such handling is inevitably accompanied by scattering of aryl vinyl sulfone dusts, laborious solid material handling and hence exposure of workers to the undesirable working environment in terms of safety and health (The Sigma-Aldrich Library of Chemical Safety Data, 2808 (1988) and Chemtech, Novvember, 34 (1996)).
SUMMARY OF THE INVENTION
An object of the invention is to provide a safer and more efficient process for producing [2-(arylsulfonyl)ethenyl]benzene derivatives, which process does not require the handling of solid aryl vinyl sulfones.
The present invention provides:
a process for producing [2-(arylsulfonyl)ethenyl]benzene derivatives of formula (3):
wherein R
1
and R
2
are the same or different, and each independently represent a hydrogen, fluorine, or chlorine atom, or a lower alkyl, lower alkoxy, nitro, cyano, amino, lower alkylamino, di(lower alkyl)amino, acyl, or alkoxycarbonyl group, and
R
3
and R
4
are the same or different and each idenpendently represent a hydrogen, fluorine, or chlorine atom, or a lower alkyl, lower alkoxy, nitro, cyano, amino, lower alkylamino, di(lower alkyl)amino, acyl, or alkoxycarbonyl group, and
two adjacent R
3
and R
4
may bond each other at their terminals to form a fused ring together with the benzene ring to which said R
3
and R
4
are bonded,
which comprises the steps of:
(a) reacting a 2-(arylsulfonyl)ethanol of formula (1):
wherein R
1
and R
2
are as the same as defined above, with an acid anhydride in the presence of a base, and
(b) subjecting the resulting reaction solution in step (a) to a reaction with an aromatic halide of formula (2):
wherein X represents a chlorine, bromine, or iodine atom, and
R
3
and R
4
are the same as defined above, in the presence of a palladium catalyst and a base.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
First, a description will be made to the step (a) as below.
Examples of the lower alkyl groups for R
1
and R
2
in 2-(arylsulfonyl)ethanol of the formula (1) include, for example, a straight or branched alkyl group having 1 to 6 carbon atoms, such as methyl, ethyl, propyl, butyl, pentyl, hexyl, isopropyl, isobutyl, sec-butyl, tert-butyl, isopentyl, neopentyl, and tert-pentyl groups.
Examples of the lower alkoxy group for R
1
and R
2
include, for example, a straight or branched alkoxy group having 1 to 6 carbon atoms, such as methoxy, ethoxy, propoxy, butoxy, pentoxy, hexoxy, isopropoxy, isobutoxy, sec-butoxy, tert-butoxy, isopentoxy, neopentoxy, and tert-pentoxy groups.
Examples of the lower alkylamino group for R
1
and R
2
include an amino group substituted with one lower alkyl group, wherein the lower alkyl group may be one of those as described above. Examples of such lower alkylamino group are methylamino, ethylamino, and tert-butylamino groups.
Examples of the di(lower alkyl)amino group include an amino group substituted with two lower alkyl groups, wherein the lower alkyl groups may be those as described above. Specific examples of such di(lower alkyl)amino group are dimethylamino, diethylamino, methylethylamino, and tert-butylmethylamino groups.
Examples of the acyl group may include, for example, aliphatic acyl groups having 2 to 8 carbon atoms, such as acetyl, propionyl, butyryl, isobutyryl, valeryl, isovaleryl, and trimethylacetyl groups, and aromatic acyl groups such as benzoyl group.
Examples of the alkoxycarbonyl group may include those groups consisting of a lower alkyl group as described above and a carbonyl group, such as methoxycarbonyl, ethoxycarbonyl, propoxycarbonyl, isopropoxycarbonyl, butoxycarbonyl, and tert-butoxycarbonyl groups.
Specific examples of such 2-(arylsulfonyl)ethanol of formula (1) include:
2-(phenylsulfonyl)ethanol, 2-(4-chlorophenylsulfonyl)ethanol,
2-(3,4-dichlorophenylsulfonyl)ethanol, 2-(4-fluorophenylsulfonyl)ethanol,
2-(4-methylphenylsulfonyl)ethanol, 2-(2,4-dimethylphenylsulfonyl)ethanol,
2-(4-ethylphenylsulfonyl)ethanol, 2-(4-isobutylphenylsulfonyl)ethanol,
2-(4tert-butylphenylsulfonyl)ethanol, 2-(4-methoxyphenylsulfonyl)ethanol,
2-(3, 4-dimethoxyphenylsulfonyl)ethanol,
2-(4-tert-butoxyphenylsulfonyl)ethanol, 2-(3-aminophenylsulfonyl)ethanol,
2-(3-methylaminophenylsulfonyl)ethanol,
2-(3-ethylaminophenylsulfonyl)ethanol,
2-(3-dimethylaminophenylsulfonyl)ethanol,
2-(3-diethylaminophenylsulfonyl)ethanol, 2-(3-nitrophenylsulfonyl)ethanol,
2-(4-cyanophenylsulfonyl)ethanol, 2-(3-acetylphenylsulfonyl)ethanol,
2-(4-benzoylphenylsulfonyl)ethanol,
2-(4-methoxycarbonylphenylsulfonyl)ethanol, and the like.
The 2-(arylsulfonyl)ethanols may readily be prepared, for example, by a process in which a thiophenol and ethylene oxide or 2-chloroethanol are reacted to obtain a sulfide, which is then oxidized (see, for example, Japanese Patent Publication Kokoku No. H4-17182 (1992); Bull. Korean Chem. Soc., 16, 670 (1995)). Alternatively, the substituent(s) on the aromatic ring may be introduced after the sulfone compound has been obtained.
The reaction of 2-(arylsulfonyl)ethanol of the formula (1) with an acid anhydride in the presence of a base, may be conducted by mixing the 2-(arylsulfonyl)ethanol of formula (1), the acid anhydride, and the base. The mixing method is not specifically restricted, and for example, may be such a method in which the acid anhydride and the base are added to the 2-(arylsulfonyl)ethanol of formula (1), or the 2-(arylsulfonyl)ethanol of formula (1) and the base are added to the acid anhydride. Said addition may be continuous or at one time.
The acid anhydrides include, for example, an acid anhydride of formula (4):
Q
2
O
wherein Q represents a hydrocarbylcarbonyl group which may be substituted (e.g., a carboxylic acid anhydride) or a hydrocarbylsulfonyl group which may be susbtituted (e.g., sulfonic anhydride).
Examples of the hydrocarbyl group herein include
an aliphatic group which may be substituted with a halogen atom (e.g., a (C1-C7)alkyl group, etc.), and
an aromatic group which may be substituted with an (C1-C4)alkyl group (e.g. a phenyl, or a tolyl group) or a halogen atom.
Specific examples of the carboxylic anhydrides include, for example, aliphatic carboxylic anhydrides such as acetic anhydride, propionic anhydride, and trifluoroacetic anhydride, and aromatic carboxylic anhydrides such as benzoic anhydride.
The sulfonic anhydrides include, for example, alkanesulfonic anhydrides such as methanesulfonic anhydride and trifluoromethanesulfonic anhydride, and aromatic sulfonic anhydrides such as p-toluenesulfonic anhydride.
The amount of acid anhydride is usually one mole or more per mol of 2-(arylsulfonyl)ethanol, and although the upper limit is not specifically limited, the amount is usually 3 moles or less, and preferably 2 moles or less, from an economic point of view.
The bases may include, for example, tertiary amines, pyridines, alkali metal carbonates, alkali metal bicarbonates, alkali metal carboxylates, alkali metal phosphates, and mixtures thereof. Among others tertiary amines are preferably used.
Examples of the tertiary amine include an amine substituted with three groups selected from a saturated(C1-C8) or unsaturated (C2-C8) aliphatic group which may be substituted with an aryl group (e.g. phenyl or naphthyl) and an aromatic group such as an aryl group as defined above. Specific examples of the tertiary aliphatic or aromatic amines such as trimethylamine, triethylamine, tripropylamine, triisopropylamine, tributylamine, tri
Kurihara Akio
Orita Akihiro
Otera Jyunzou
Birch & Stewart Kolasch & Birch, LLP
McKane Joseph K.
Murray Joseph
Sumitomo Chemical Company Limited
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