Method for producing arylvinylsulfone

There is provided a method for producing arylvinylsulfone of the formula: ##STR1## wherein, R.sup.1 and R.sup.2 denote each independently a hydrogen atom, a halogen atom, a lower alkyl group, a lower alkoxy group, PA1 a nitro group, an amino group, a lower alkylamino group and PA1 a lower di(alkylamino) group, which comprises reacting .beta.-haloethylarylsulfone of the formula: ##STR2## wherein, R.sup.1 and R.sup.2 are as defined above and X denotes a halogen atom, with an alkali metal carbonate or an alkali metal hydrogencarbonate in the presence of a catalytic amount of an amine or its inorganic acid salt or a quaternary ammonium salt.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
The present invention relates to a method for producing arylvinylsulfone. 
2. Description of the Related Art 
Vinylsolfone is widely used as an important functional group and has been 
prepared, for example, by reacting .beta.-chloroethylphenylsulfone with a 
stoichiometric amount of sodium hydroxide or triethylamine. U.S. Pat. No. 
2,554,576, DE 877607, J. Org. Chem., 58, 4506 (1993) and J. Chem. Soc., 
1754 (1949)! 
Alternatively, a readily available 2-phenylsulfonylethanol is mesylated and 
then the mesylate is reacted with triethylamine Bull. Korean Chem. Soc., 
16, 670 (1995)!. 
These processes were not always satisfactory, however, in that the yield of 
the desired product was not satisfactory when sodium hydroxide was used or 
a further tedious process was required to cope with a large amount of used 
triethylamine in wastewater, or the expensive mesyl chloride was required. 
Therefore, a further method to provide arylvinylsulfone has been desired. 
SUMMARY OF THE INVENTION 
The present inventors have found a novel process for producing 
arylvinylsulfone, which comprises reacting .beta.-haloethylarylsulfone 
with an alkali metal carbonate or an alkali metal hydrogencarbonate or a 
mixture thereof in the presence of a catalytic amount of an amine or its 
inorganic salt or a quaternary ammonium salt, and also found a process 
which comprises reacting a chlorinating agent with 2-arylsulfonylethanol 
to produce .beta.-haloethylarylsulfone, whereby reducing the burden of 
treating used triethylamine and producing the desired compound in good 
yield and economically. 
The present invention provides: 
a method for producing arylvinylsulfone of the formula: 
##STR3## 
wherein, R.sup.1 and R.sup.2 indicate each independently a hydrogen atom, 
a halogen atom, a lower alkyl group, a lower alkoxy group, a nitro group, 
an amino group, a lower alkylamino group and a lower di(alkyl)amino group, 
which comprises: reacting .beta.-haloethylarylsulfone of the formula: 
##STR4## 
wherein, R.sup.1 and R.sup.2 are as de-fined above and X denotes a halogen 
atom, with an alkali metal carbonate or an alkali metal hydrogencarbonate 
or a mixture thereof in the presence of a catalytic amount of an amine or 
its inoroganic acid salt or a quaternary ammonium salt; and 
a method for producing .beta.-haloethylarylsulfone of the formula II! as 
defined above, which comprises reacting 2-arylsulfonylethanol of the 
formula: 
##STR5## 
wherein, R.sup.1 and R.sup.2 are as defined above, with a chlorinating 
agent. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
First, a description will be made to the method for producing 
arylvinylsulfone of the formula I! as defined above, which comprises 
reacting .beta.-haloethylarylsulfone of the formula II! as defined above 
with an alkali metal carbonate or an alkali metal hydrogencarbonate or a 
mixture thereof in the presence of a catalytic amount of an amine or its 
inorganic acid salt or a quaternary ammonium salt. 
In the .beta.-haloethylarylsulfone of the formula II!, the halogen atom 
represented by R.sup.1 or R.sup.2 includes a fluorine, chlorine, bromine 
and iodine atom 
Examples of the lower alkyl group for R.sup.1 or R.sup.2 include a straight 
or branched chain alkyl group having 1 to 6 carbon atoms such as a methyl 
group, an ethyl group, a n-propyl group, a n-butyl group, a n-pentyl 
group, an i-propyl group, an i-butyl group, a sec-butyl group, a t-butyl 
group, a neopentyl group, a n-hexyl group and the like. 
Examples of the lower alkoxy group for R.sup.1 or R.sup.2 include a 
straight or branched chain alkoxy group having 1 to 6 carbon atoms such as 
a methoxy group, an ethoxy group, an n-propoxy group, an n-butoxy group, 
an n-pentoxy group, an i-propoxy group, an i-butoxy group, a sec-butoxy 
group, a t-butoxy group, an neopentoxy group, a n-hexyloxy group and the 
like. 
The lower alkylamino group for R.sup.1 and R.sup.2 includes an amino group 
substituted by one lower alkyl group, wherein the lower alkyl group here 
includes the alkyl groups as defined for R.sup.1 and R.sup.2 above. 
Examples of the lower alkylamino group include a methylamino group, an 
ethylamino group, a t-butylamino group and the like. 
The lower di(alkyl)amino group for R.sup.1 and R.sup.2 includes an amino 
group substituted by two lower alkyl groups, wherein the lower alkyl group 
is the same alkyl groups as described above. 
Examples of the lower di(alkyl)amino groups include a dimethylamino group, 
a methylethylamino group, a diethylamino group, a t-butylmethylamino group 
and the like. 
Examples of the halogen atom represented by X include a chlorine atom, 
bromine atom, iodine atom and the like. 
Specific examples of the .beta.-haloethylarylsulfone of the formula II! 
include (.beta.chloroethylsulfonyl)benzene, 
4-chloro-1-(.beta.-chloroethylsulfonyl)benzene, 
1-(.beta.-chloroethylsulfonyl)-3,4-dichlorobenzene, 
4-bromo-1-(.beta.-chloroethylsulfonyl)benzene, 
1-(.beta.-chloroethylsulfonyl)-4-fluorobenzene, 
1-(.beta.-chloroethylsulfonyl)-4-iodobenzene, 
1-(.beta.-chloroethylsulfonyl)-4-methylbenzene, 
1-(.beta.-chloroethylsulfonyl)-2,4-dimethylbenzene, 
1-(.beta.-chloroethylsulfonyl)-4-ethylbenze, 
1-(.beta.-chloroethylsulfonyl)-4-i-butylbenzene, 
1-(.beta.-chloroethylsulfonyl)-4-t-butylbenzene, 
1-(.beta.-chloroethylsulfonyl)-4-methoxybenzene, 
1-(.beta.-chloroethylsulfonyl)-3,4-dimethoxybenzene, 
1-(.beta.-chloroethylsulfonyl)-4-t-butoxybenzene, 
3-(.beta.-chloroethylsulfonyl)-aniline, 
3-(.beta.-chloroethylsulfonyl)-N-methylaniline 
3-(.beta.-chloroethylsulfonyl)-N-ethylaniline, 
3-(.beta.-chloroethylsulfonyl)-N,N-dimethylaniline, 
3-(.beta.-chloroethylsulfonyl)-N,N-diethylaniline, 
1-(.beta.-chloroethylsulfonyl)-3-nitrobenzene, and compounds having a 
.beta.-bromoethylsulfonyl group or a .beta.-iodoethylsulfonyl group in 
place of the .beta.-chloroethylsulfonyl group in the above-described 
compound. 
The alkali metal carbonate, for example, includes potassium carbonate, 
sodium carbonate and the like, and the alkali metal hydrogencarbonate, for 
example, includes potassium hydrogencarbonate, sodium hydrogencarbonate 
and the like. The alkali metal or alkali metal hydrogen carbonate may be 
used alone or in combination thereof, and among them, potassium carbonate 
is preferably used. 
The amount of the alkali metal carbonate or alkali metal hydrogencarbonate 
to be used is usually not less than 0.8 mol, preferably from 1 to 4 moles 
in terms of alkali metal per mol of .beta.-haloethylarylsulfone. 
Though the alkali metal carbonate or alkali metal hydrogencarbonate can be 
used in the form of powder, it is preferably used in the form of an 
aqueous solution, of which concentration can be appropriately set 
according to the alkali metal carbonate or alkali metal hydrogen carbonate 
employed. 
The amine or its inorganic acid salt or a quaternary ammonium salt may be 
used alone or in combination- thereof. 
The amine includes ammonia (e.g., aqueous ammonia), a heteroaryl amine, a 
primary, secondary or tertiary amine or its inorganic acid salt and is 
commercially available or may be obtained by a conventional method. The 
secondary or tertiary amine or its inorganic acid salt or a quaternary 
ammonium salt is preferably used in the present invention. 
Examples of the heteroaryl amine include pyridine, 2-picoline, 3-picoline, 
4-picoline and 2,4-dimethylpyridine. 
The primary amine includes an amine compound of the formula: QNH.sub.2, 
wherein 
Q represents: 
a saturated or unsaturated hydrocarbon group which may substituted, or 
an aryl group which may be substituted. 
The secondary amine includes an amine compound of the formula: QQ'NH, 
wherein 
Q and Q' are the same or different and each independently represent a 
saturated or unsaturated hydrocarbon group which may be substituted or an 
aryl group (e.g. phenyl or naphthyl) which may be substituted, or 
Q and Q' may together form an alkylene group or an alkenylene group, both 
of which may be substituted with at least one (C.sub.1 -C.sub.3)alkyl 
group and may contain a hetero atom (e.g., an oxygen atom). 
The tertiary amine includes an amine compound of a formula: QQ'Q"N, wherein 
Q and Q' are the same as define above and Q" independently has the same 
meaning as Q or Q". 
The saturated hydrocarbon group which may be substituted in Q, Q', Q" 
includes: 
a straight or branched chain (C.sub.1 -C.sub.20)alkyl group or a (C.sub.3 
-C.sub.8)cyclo alkyl group all of which may be substituted with a (C.sub.1 
-C.sub.8)alkoxy group or an aryl(e.g. phenyl, naphthyl) or a heteroaryl 
group (e.g. pyridine). 
The unsaturated hydrocarbon group which may be substituted in Q, Q', Q" 
includes: 
a straight or branched chain (C.sub.3 -C.sub.20)alkenyl group such as ally, 
methally and 2-butenyl. 
The aryl group (e.g. phenyl or naphthyl) which may be substituted in Q, Q', 
Q" includes an aryl group which may be substituted with at least one 
substituent selected from a group of an (C.sub.1 -C.sub.6)alkyl and an 
(C.sub.1 -C.sub.6)alkoxy. 
Examples of the primary amine include methylamine, ethylamine, 
n-propylamine, isopropylamine, butylamine(n-butylamine, isobutylamine, 
sec-butylamine, t-butylamine), cyclohexylamine, hexylamine, octylamine, 
2-ethylhexylamine, 3-(2-ethylhexyloxy)propylamine, 2-methoxyethylamine, 
3-ethoxypropylamine, benzylamine, aniline, 1-naphtylamine, 2-naphtylamine 
or the like. 
Examples of the secondary amine include dimethylamine, diethylamine, 
dipropylamine, diisopropylamine, dibutylamine, diisobutylamine, 
dicyclohexylamine di(methoxyethyl)amine, di-(allyl)amine or the like 
Examples of the secondary amine, formed by Q and Q', comprising an alkylene 
group or an alkenylene group, both of which may be substituted with at 
least one (C.sub.1 -C.sub.3)alkyl group and may contain a hetero atom 
(e.g., an oxygen atom) include: 
2-pipecoline, 3-pipecoline, 4-pipecoline, piperizine, pyrrolidine and 
morpholine. 
Examples of the tertiary amine include trimethylamine, triethylamine, 
tripropylamine, tributylamine, triisobutylamine, diisopropylethylamine, 
triallyamine, N,N-dimethylbenzylamine, 
N,N-dimethyl-N-1-naphthylmethylamine, N,N-diethylaniline, 
N-methylpiperidine, N-methylmorpholine and the like. 
Examples of the secondary or tertiary amine further include a polyamine of 
the formula: QQ'N--Y--NQ"Q'" or QNH--Y--NHQ' or QNH--Y--NQ'Q", wherein 
Q,Q' and Q" independently have the same meaning as defined above and Q'" 
independently has the same meaning as defined for Q, Q' or Q" above and Y 
represents an alkylene or alkenylene hydrocarbon group having 2 to 6 
carbon atoms. 
Specific examples of the polyamine include N,N'-dimethylethylenediamine, 
N,N',N"-trimethylethylenediamine, N,N-diethyl-N'-methylethylenediamine, 
N,N,N'-trimethyl-1,3-propanediamine, 
N,N,N',N'-tetramethyl-1,3-diaminopropane, 
N,N,N',N'-tetramethyl-1,6-hexamethylenediamine, 2-methylpiprerazine, 
2,5-dimethylpiperazine, 2,6-dimethylpiperazine, N-methylpiperazine, 
1,3-di(4-piperidyl)propane, 1,5-diazabicyclo4,3,0!non-5-ene, 
1,4-diazabicyclo2,2,2!octane and 1,8-diazabicyclo5,4,0!undec-7-ene and 
further include 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 
4-(N,N-dimethylamino)pyridine, 4-pyrrolidinopyridine, 
4-piperidinopyridine. 
Examples of the inorganic acid salt of the amine include a hydrochloride, 
hydrobromide, sulfate, hydrogensulfate of the corresponding amine as 
defined above. 
Specific examples of tertiary amine hydrocloride are trimethylamine 
hydrochloride, triethylamine hydrochloride and the like. 
Examples of the quaternary ammonium salt include triethylbenzylammonium 
chloride, tetramethylammonium chloride, tetramethylammonium bromide, 
tetraethylammonium chloride, tetraethylammonium bromide, 
tetrabutylammonium chloride, tetrabutylammoium bromide; and the like, 
respectively. 
The amount of the amine or its inorganic acid salt or quaternary ammonium 
salt may be catalytic and is usually from 0.005 to 0.5 mol, preferably 
from 0.01 to 0.3 mol per mol of .beta.-haloethylarylsulfone. 
The reaction is usually conducted in an inert solvent that does not 
adversely affect the reaction, and the examples of the solvent include a 
hydrophobic organic solvent selected from an ether solvent such as 
diethoxymethane, ethyl ether and the like, an aromatic solvent such as 
benzene, toluene, xylene, chlorobenzene, dichlorobenzene and the like, a 
halogenated hydrocarbon solvent such as dichloromethane, 
1,2-dichloroethane, chloroform, carbon tetrachloride, a mixed solvent 
thereof. In this reaction an aprotic polar organic solvent such as 
N,N-dimethylacetamide, N,N-dimethylformamide, dimethylsulfoxide or a mixed 
solvent thereof also may be used. 
The amount of the solvent is usually from 0.5 to 50 times by weight based 
on the weight of .beta.-haloethylarylsulfone. 
The reaction is conducted, for example, by mixing 
.beta.-haloethylarylsulfone, catalytic amount of the amine or its 
inorganic acid salt or quaternary ammonium salt and alkali metal carbonate 
or alkali metal hydrogen carbonate in a solvent. When the alkali metal 
carbonate or alkali metal hydrogencarbonate is used in a form of an 
aqueous solution, the reaction may be conducted in a two-phase system 
comprising a hydrophobic organic solvent and water. 
The reaction temperature is usually from 0 to 150.degree. C., and 
preferably from 10 to 100.degree. C. 
After completion of the reaction, water is usually added to the resulting 
reaction mixture, then the mixture is separated to give an aqueous phase 
and an organic phase of hydrophobic organic solvent containing the 
product, or extracted with a hydrophobic organic solvent when an aprotic 
polar solvent was used. 
When the alkali metal carbonate or alkali metal hydrogencarbonate is used 
in a form of an aqueous solution in the reaction, the separation may be 
conducted without adding water. 
After the separation, the resulted organic phase may be washed with water 
or an acidic aqueous solution such as diluted sulfuric acid, diluted 
hydrochloric acid and the like, if necessary. 
Then, desired arylvinylsulfone of the formula I! can be isolated from the 
resulting organic phase by a usual method, for example, by distilling off 
the solvent or cooling the solution 
Alternatively, desired arylvinylsulfone of the formula I! may be isolated 
from the organic phase by using a bad solvent. For example, the organic 
phase may be added to a bad solvent or a bad solvent may be added to the 
organic phase, and crystals of the desired product are allowed to form in 
the mixed organic solution on standing at an ambient temperature, or the 
resulting mixed solution may be successively cooled, for example, to a 
room temperature to -50.degree. C. to obtain the desired product, if 
necessary. 
Examples of the bad solvent include aliphatic hydrocarbon solvent such as 
hexane and heptane. 
The amount of the bad solvent is usually less than 100 times, preferably 
0.5 to 50 times by weight based on the weight content of the desired 
product in the organic phase, which can be determined by a conventional 
analysis of the organic phase prior to the crystallization procedure. 
The obtained arylvinylsulfone may be further purified by washing, 
recrystallization and the like, if necessary. 
The examples of thus obtained arylvinylsulfone include: phenylvinylsulfone, 
(4-chlorophenyl)vinylsulfone, (3,4-dichlorophenyl)vinylsulfone, 
(4-bromophenhyl)vinylsulfone, (4-fluorophenyl)vinylsulfone, 
(4-iodophenyl)vinylsulfone, (4-methylphenyl)vinylsulfone, 
(2,4-dimethylphenyl)vinylsulfone, (4-ethylphenyl)vinylsulfone, 
(4-i-butylphenyl)vinyl-sulfone, (4-t-butylphenyl)vinylsulfone, 
(4-methoxyphenyl)vinylsulfone, (3,4-dimethoxyphenyl)vinylsulfone, 
(4-t-butoxyphenyl)vinylsulfone, (3-aminophenyl)vinylsulfone, 
(3-methylaminophenol)vinylsulfone, (3-ethylaminophenyl)vinylsulfone, 
(3-dimethylaminophenyl)vinylsulfone, (3-diethylaminophenyl)vinylsulfone, 
(3-nitrophenyl)vinylsulfone and the like. 
Next a description will be made to the method for producing 
.beta.-haloethylarylsulfone of the formula II! as defined above, which 
comprises reacting 2-arylsulfonylethanol of the formula III! as defined 
above, with a chlorinating agent. 
Examples of 2-arylsulfonylethanol of the formula III! include 
2-(phenylsulfonyl)ethanol, 2-(4-chlorophenylsulfonyl )ethanol, 
2-(3,4-dichlorophenylsulfonyl)ethanol, 2-(4-bromophenylsulfonyl)ethanol, 
2-(4-fluorophenylsulfonyl)ethanol, 2-(4-iodophenylsulfonyl)ethanol, 
2-(4-methylphenylsulfonyl)ethanol, 2-(2,4-dimethylphenylsulfonyl)ethanol, 
2-(4-ethylphenylsulfonyl)ethanol, 2-(4-i-butylphenylsulfonyl)ethanol, 
2-(4-t-butylphenylsulfonyl)ethanol, 2-(4-methoxyphenylsulfonyl)ethanol, 
2-(3,4-dimethoxyphenylsulfonyl)ethanol, 
2-(4-t-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 
and the like. 
These 2-arylsulfonylethanols can be easily produced, for example, by 
reacting a thiophenol with ethylene oxide or 2-chloroethanol to obtain a 
sulfide compound and the resulted compound is oxidized for example, 
Japanese Patent Application Publication JP Hei 4-17182B, Bull. Korean 
Chem. Soc., 16, 670 (1995)!, and the like. In addition, the substituent on 
the aromatic ring may be optionally introduced by a conventional method 
after a sulfone group is introduced, if necessary. 
Examples of the chlorinating agent include thionyl chloride, phosphorus 
trichloride, phosphorus pentachloride, phosphorus oxychloride, and the 
like. Among them, thionyl chloride is preferred. The amount of the 
chlorinating agent is usually 1 mol, preferably 1 to 2 mols per mol of 
2-arylsulfonylethanol. 
The chlorinating reaction may be conducted either in a solvent or without 
using a solvent. When a solvent is employed in this reaction, the examples 
of the solvent that can be used include an inert aprotic organic solvent 
that does not adversely affect the reaction Such an inert solvent includes 
an ether solvent such as dimethoxyethane, ethyl ether and the like, an 
aromatic solvent such as benzene, toluene, xylene, chlorobenzene, 
dichlorobenzene and the like, a halogenated hydrocarbon solvent such as 
dichloromethane, 1,2-dichloroethane, chloroform, carbon tetrachloride and 
the like and a mixed solvent thereof. 
The amount of the solvent to be used is usually from 0.5 to 30 times by 
weight based on the weight of 2-arylsulfonylethanol. 
In the chlorinating reaction, an organic base may be added, if necessary, 
and the examples thereof include an amine such as pyridine, triethylamine 
and other amines as described above. Anhydrous organic bases other than 
aqueous solution are used in this reaction. 
The amount of the organic base to be used is usually not limited and is not 
less than 0.001 mol to 2 mols, preferably from 0.01 to 0.5 mol per mol of 
the chlorinating agent. 
The reaction is conducted, for example, by mixing 2-arylsulfonylethanol and 
a chlorinating agent, and when a solvent is used, 2-arylsulfonylethanol 
and a chlorinating agent may be mixed in a solvent. 
When an organic base is used, the base may be added together with 
2-arylsulfonylethanol and a chlorinating agent. The reaction temperature 
is usually from -30 to 150.degree. C., and preferably from -10 to 
100.degree. C. 
After completion of the reaction, the reaction mixture is usually subjected 
to a post-treatment such as dilution with water and/or extraction with an 
organic hydrophobic solvent or washed with water or aqueous alkali 
solution such as an aqueous sodium carbonate solution, an aqueous sodium 
hydrogencarbonate solution, aqueous potassium carbonate solution, aqueous 
potassium hydrogencarbonate solution and the like to remove an acidic 
substance resulted from the reaction prior to the next reaction to produce 
arylvinylsulfone of the formula I!, if necessary. Then 
.beta.-haloethylarylsulfone of the formula II! may be isolated by 
evaporation of the solvent used or further reacted to obtain 
arylvinylsulfone I! without isolating.

According to the method of the present invention, arylvinylsulfone can be 
produced by a simple treatment in a good yield from industrially readily 
available 2-arylsulfonylethanol. 
EXAMPLE 
The following examples further illustrate the present invention in detail 
but are not to be construed to limit the scope thereof. 
Example 1 
(.beta.-chloroethylsulfonyl)benzene (40.9 g, 200 mmol) was dissolved in 100 
g of toluene, to this solution were added 30.7 g of 49% aqueous potassium 
carbonate solution (potassium carbonate 109 mmol) and 1.01 g (10 mmol) of 
triethylamine, and the mixture was stirred for 3 hours at from 40 to 
45.degree. C. Then, the mixture was washed with 70 g of water once, with 
35 g of 5% aqueous sulfuric acid solution once and further with 35 g of 
water once, and the solvents were distilled off to obtain 33.1 g (yield 
98.4%) of phenylvinylsulfone. 
Example 2 
The same reaction was conducted as in Example 1 except that 55.6 g of 20% 
aqueous sodium carbonate solution (sodium carbonate 105 mmol) was used 
instead of 49% aqueous potassium carbonate solution, to obtain 30.6 g 
(yield 91.0%) of phenylvinylsulfone. 
Example 3 
1-(.beta.-chloroethylsulfonyl)-3-nitrobenzene (2.50 g, 10 mmol) was added 
to 20 g of toluene, to this solution were added 1.50 g of 49% aqueous 
potassium carbonate solution (potassium carbonate 5.3 mmol) and 50 mg (0.5 
mmol) of triethylamine, and the mixture was stirred for 2 hours at 
40.degree. C. Then, 10 g of water was added and the mixture was separated 
to an organic phase and aqueous phase. This aqueous phase was extracted by 
chloroform, and the resulted organic phase was combined with the previous 
organic phase, dried over magnesium sulfate, the solvents were distilled 
off, to obtain 2.00 g (yield 94.3%) of (3-nitrophenyl)vinylsulfone. 
Example 4 
(.beta.-chloroethylsulfonyl)benzene (4.09 g, 20 mmol) was added to 20 g of 
toluene, to this solution were added 3.00 g of 49% aqueous potassium 
carbonate solution (potassium carbonate 10.6 mmol) and 113 mg (1.0 mmol) 
or diisopropylethylamine, and the mixture was stirred for 4 hours at 
40.degree. C. Then, 10 g of water was added and the mixture was separated 
to an organic phase and aqueous phase. This aqueous phase was extracted by 
chloroform, and the resulted organic phase was combined with the previous 
organic phase, dried over magnesium sulfate, the solvents were distilled 
off, to obtain 2.76 g (yield 82.1%) of phenylvinylsulfone. 
Example 5 
The same procedure was conducted as in Example 4 except that 230 mg (1.0 
mmol) of triethylbenzylammonium chloride was used instead of 
diisopropylethylamine, to obtain 30.4 g (yield 90.4%) of 
phenylvinylsulfone. 
Example 6 
The same procedure was conducted as in Example 4 except that 290 mg (2.0 
mmol) of triisopropylamine was used instead of diisopropylethylamine, to 
obtain 33.3 g (yield 99.0%) of phenylvinylsulfone. 
Example 7 
The same procedure was conducted as in Example 4 except that 300 mg (3.0 
mmol) of diisopropylamine was used instead of diisopropylethylamine, to 
obtain 32.7 g (yield 97.2%) of phenylvinylsulfone. 
Example 8 
The same procedure was conducted as in Example 4 except that 610 mg (4.0 
mmol) of 1,8-diazabicyclo5.4.0!undec-7-ene was used instead of 
diisopropylethylamine, to obtain 30.4 g (yield 90.4%) of 
phenylvinylsulfone. 
Example 9 
2-(phenylsulfonyl)ethanol (143.8 g, purity 96.2%, 743 mmol) was added to 
71.9 g of toluene, and 30.0 g (38 mmol) of pyridine was added to the 
mixture. The resulting solution was heated to 60.degree. C., then 110.5 g 
(929 mmol) of thionyl chloride added over 5 hours at 60 to 70.degree. C., 
and the mixture was stirred for 2 hours at 70.degree. C. Then, the mixture 
was diluted with 143.9 g of toluene and cooled to 45.degree. C. Then 303.2 
g of 7% sodium bicarbonate solution and 193.4 g of toluene were added, 
washed separated. Obtained organic layer was mixed with 303.2 g of 7% 
sodium bicarbonate solution and stirred and separated. 5 g of the organic 
layer was sampled and subjected to HPLC analysis, which revealed that 
(.beta.-chloroethylsulfonyl)benzene was obtained in a yield of 98% and 
phenylvinylsulfone in a yield of 0.7%. (Internal Standard: methyl 
benzoate). 
3.7 g (36 mmol) of triethylamaine was added to the obtained organic 
solution and the resulting solution was heated to 60.degree. C., into 
which was added 202.6 g of 25% aqueous potassium carbonate over 3 hours 
and kept at 60.degree. C. for 5 hours. Then the solution was cooled to 
room temperature and separated. Separated organic layer was washed with 
57.9 g of 5% sulfuric acid twice and separated. Washed organic layer was 
further washed with 57.9 g of water and separated. 0.5 g of the organic 
layer was sampled and subjected to HPLC analysis, which revealed that 
phenylvinylsulfone was obtained in a yield of 100% (Internal Standard: 
methyl benzoate). Obtained solution was concentrated under reduced 
pressure to give 50% phenylvinylsulfone solution in toluene at 50.degree. 
C. which was then added dropwise to 186 g of hexane under an ambient 
temperature and then cooled to -10.degree. C. and kept at the same 
temperature for half an hour to yield crystals of phenylvinylsulfone, 
which was then collected by filtration. Collected crystral was washed with 
250 g of hexane and dried to give 121.5 g of phenylvinylsulfone as a white 
crystal. (Yield: 97.9%)