Method for production of sulfide group-containing thiol compound

A method for the production of a sulfide group-containing thiol compound which comprises causing alkylene sulfide to react with a thiol compound in the presence of at least one basic catalyst selected from the group consisting of basic ion-exchange resins, quaternary ammonium compounds and alkyl pyridinium compounds, thereby inducing the ring-opening addition of the alkylene sulfide to the thiol compound. Further, a method for the production of a sulfide group-containing mercaptocarboxylic ester which comprises causing an alkylene sulfide to react with a mercaptocarboxylic ester.

BACKGROUND OF THE INVENTION 
1. Field of the Invention 
This invention relates to a method for the production of a sulfide 
group-containing thiol compound. More particularly, this invention relates 
to a method for the production of a sulfide group-containing thiol 
compound by the ring-opening addition of alkylene sulfide to a thiol 
compound. 
The sulfide group-containing thiol compounds which are obtained by the 
method of this invention are useful compounds which find extensive utility 
such as in chelating agents, lubricant additives, additives for rubber, 
additives for refined petroleum oils, and polymerization chain transfer 
agents. 
2. Description of the Prior Art 
As means for producing a sulfide group-containing thiol compound by the 
ring-opening addition of alkylene sulfide to a thiol compound, a method 
which effects the reaction in the absence of a catalyst has been 
heretofore disclosed in DE-A-696, 774. Since this method requires a high 
temperature, however, U.S. Pat. No. 2,490,984 has proposed a method which 
uses boron trifluoride as a catalyst for the reaction and U.S. Pat. No. 
2,497,100 a method which uses sodium alkoxide by way of improvement. 
Methods which similarly use alkali metal alkoxides have been also proposed 
in J. Am. Chem. Soc. (1947), Vol. 69, page 2675-2677, J. Chem. Soc. 
(1948), page 1894-1895, and J. Chem. Soc. (1949), page 282-287. Though 
these catalysts are highly active, they are at a disadvantage in 
manifesting low selectivity for the products aimed at because they are 
liable, when taking part in a reaction using ethylene sulfide, to induce 
the polymerization of ethylene sulfide. 
A case of study using triethyl amine as a catalyst has been reported in 
Izv. Akad. Nauk, SSSR, Ser. Khim. (1975), No. 3, page 660-662. Then, U.S. 
Pat. No. 4,163,832 discloses a method which similarly uses either such 
amine compounds as trimethyl amine and triethyl amine or trimethyl 
phosphine. Further, J. Fluorine Chem. (1975), Vol. 6, page 145-159 
discloses a reaction of pentafluorothiophenol with ethylene sulfide by the 
use of pyridine. When amine compounds and pyridines are used as a 
catalyst, they indeed go to improve the selectivity for a relevant 
reaction. When the reaction involves a thiol compound with low reactivity 
or alkylene sulfide other than ethylene sulfide, however, this catalyst is 
at a disadvantage in lowering the reaction velocity. Moreover, since the 
thiol compound is weakly acidic, the basic amine catalyst which exists in 
the system poses the problem that it is not thoroughly separated and 
removed with ease even by the distillation. 
JP-B-07-5,585 has disclosed a method for effecting the reaction in a sodium 
hydroxide-benzene type aqueous solution with benzyl trimethyl ammonium 
chloride as a catalyst. This method, however, is deficient in yield and 
selectivity. The use of this quaternary ammonium compound as a catalyst is 
at a disadvantage in easily inducing the polymerization of alkylene 
sulfide due to the presence of water in a two-phase system and in not 
being applicable to a thiol compound containing an easily hydrolyzable 
ester group. 
As means for producing a sulfide group-containing mercaptocarboxylic ester, 
Chem. Pharm. Bull., 38(11), pp. 3035-3041 (1990) has disclosed a method 
for implementing the production by causing ethane-1,2-dithiol to react 
with chloroacetic ester in the presence of triethyl amine. This method, 
however, is deficient in economic usefulness because it gives rise to a 
by-product containing halogen. Japan Chemical Journal, Vol. 81, pp. 
328-331 (1960) teaches to obtain an ester by causing ethanol to react with 
the reaction product of .beta.-propiolactone with ethane-1,2-dithiol. This 
method forms by-products copiously and suffers a poor yield. Eur. Polym. 
J., 7, pp. 189-201 (1971) reports a method for polymerizing propylene 
sulfide by using mercaptopropionic acid as a chain transfer agent. The 
product obtained by this reaction is a polymer. This reaction has been 
incapable of obtaining such a low adduct as with the number of mols of 
added alkylene sulfide in the approximate range of 1 to 3. 
It is, therefore, an object of this invention to provide a novel method for 
the production of a sulfide-containing thiol compound. 
Another object of this invention is to provide a method for the production 
of a sulfide group-containing thiol compound by the use of a catalyst 
which can manifest high activity fit for various thiol compounds, avoid 
inducing the polymerization of alkylene sulfide, and promote the 
ring-opening addition reaction with high selectivity. 
Further object of this invention is to provide a novel method for the 
production of a sulfide group-containing mercaptocarboxylic ester. 
Furthermore object of this invention is to provide a method for the 
production of a sulfide group-containing mercaptocarboxylic ester by the 
use of a catalyst capable of proceeding the reaction by the ring-opening 
addition with high selectivity without inducing the polymerization of an 
alkylene sulfide. 
SUMMARY OF THE INVENTION 
These objects can be attained by the following items (1) to (17). 
(1) A method for the production of a sulfide group-containing thiol 
compound, characterized by causing alkylene sulfide represented by the 
general formula (2): 
##STR1## 
(wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4, which may be the same or 
different, each represents a hydrogen atom, an alkyl group of 1 to 10 
carbon atoms, or an aromatic group of 6 to 15 carbon atoms) to react with 
a thiol compound in the presence of at least one basic catalyst selected 
from the group consisting of basic ion-exchange resins, and quaternary 
ammonium compounds and alkyl pyridinium compounds both represented by the 
general formula (1): 
EQU A.sup.+ B.sup.- ( 1) 
(wherein A stands for quaternary ammonium or alkyl pyridinium, B for RCOO, 
ROCOO, RO, RS, or NCS, provided that R stand for a hydrogen atom, an alkyl 
group of 1 to 18 carbon atoms, or an aromatic group of 6 to 18 carbon 
atoms), thereby inducing the ring-opening addition of the alkylene sulfide 
to the thiol compound. 
(2) A method according to (1) mentioned above, wherein the basic 
ion-exchange resin is at least one ion-exchange resin selected from the 
group consisting of resins having a tertiary amino group, resins having a 
quaternary ammonium group, and resins having a pyridine ring severally as 
a functional group. 
(3) A method according to (1) mentioned above, wherein the quaternary 
ammonium compound is a compound represented by the general formula (3): 
##STR2## 
(wherein R.sup.5, R.sup.6, R.sup.7, and R.sup.8, which may be identical or 
different, each represents an alkyl group of 1 to 20 carbon atoms, an 
aromatic group of 6 to 20 carbon atoms, a benzyl group, or an allyl group 
and B has the same meaning as defined above). 
(4) A method according to (1) mentioned above, wherein the alkyl pyridinium 
compound is a compound represented by the general formula (4): 
##STR3## 
(wherein R.sup.9 stands for an alkyl group of 1 to 20 carbon atoms and B 
has the same meaning as defined above). 
(5) A method according to (3) or (4) mentioned above, wherein the reaction 
is carried out in a non-aqueous system. 
(6) A method according to (1) mentioned above, wherein the reaction is 
carried out by sequentially adding the alkylene sulfide into the reaction 
system. 
(7) A method according to any of (1) to (6) mentioned above, wherein the 
thiol compound is one member selected from the group consisting of 
polythiols, mercaptoalkanoic esters, allyl mercaptan, furfuryl mercaptan, 
and compounds represented by the general formula (5): 
EQU R.sup.10 SH (5) 
wherein R.sup.10 stands for a hydrogen atom, an alkyl group of 1 to 20 
carbon atoms, a hydroxyalkyl group of 2 to 20 carbon atoms, an aromatic 
group of 6 to 20 carbon atoms, or R.sup.11 CO-- (wherein R.sup.11 stands 
for an alkyl group of 1 to 20 carbon atoms or an aromatic group of 6 to 20 
carbon atoms)!. 
(8) A method according to any of (1) to (7) mentioned above, wherein the 
thiol compound is a compound represented by the general formula (5): 
EQU R.sup.10 SH (5) 
wherein R.sup.10 stands for a hydrogen atom, an alkyl group of 1 to 20 
carbon atoms, a hydroxyalkyl group of 2 to 20 carbon atoms, an aromatic 
group of 6 to 20 carbon atoms, or R.sup.11 CO-- (wherein R.sup.11 stands 
for an alkyl group of 1 to 20 carbon atoms or an aromatic group of 6 to 20 
carbon atoms)!. 
(9) A method according to any of (1) to (7) mentioned above, wherein the 
alkylene sulfide is ethylene sulfide or propylene sulfide and the thiol 
compound is one member selected from the group consisting of 
mercaptoalkanoic esters, mercaptoalkanols, aromatic thiols, aromatic 
thiocarboxylic acids, and alkane thiols. 
(10) A method according to (9) mentioned above, wherein the thiol compound 
is one member selected from the group consisting of mercaptoalkanoic 
esters and mercaptoalkanols. 
(11) A method according to (1) mentioned above, wherein the amount of the 
basic catalyst used is in the range of 0.01 to 10 parts by weight, based 
on 100 parts by weight of the reaction mixture. 
(12) A method according to (1) mentioned above, wherein the amount of the 
thiol compound is in the range of 1 to 10 mols per mol of the alkylene 
sulfide. 
(13) A method according to (1) mentioned above, wherein the reaction is 
carried out at a temperature in the range of 0.degree. to 200.degree. C. 
(14) A method for the production of a sulfide group-containing 
mercaptocarboxylic ester represented by the general formula (7): 
##STR4## 
(wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4, which maybe identical or 
different, each represents a hydrogen atom, an alkyl group of 1 to 10 
carbon atoms, or an aromatic group of 6 to 15 carbon atoms, R.sup.12 for a 
hydrocarbon group of 1 to 20 carbon atoms, and R.sup.13 for an alkylene 
group of 1 to 3 carbon atoms, and n is an integer in the range of 1 to 3), 
characterized by causing an alkylene sulfide represented by the general 
formula (2): 
##STR5## 
(wherein R.sup.1, R.sup.2, R.sup.3, and R.sup.4 have the same meanings as 
defined above) to react with a mercaptocarboxylic ester represented by the 
general formula (6): 
##STR6## 
(wherein R.sup.12 and R.sup.13 have the same meanings as defined above). 
(15) A method according to (14) mentioned above, wherein the reaction is 
carried out in the presence of a basic catalyst or a phosphine catalyst. 
(16) A method according to (14) or (15) mentioned above, wherein the amount 
of the mercaptocarboxylic ester is in the range of 1 to 10 mols per mol of 
the alkylene sulfide. 
(17) A method according to any of (14) to (16) mentioned above, wherein the 
reaction is carried out by the sequential addition of the alkylene sulfide 
into the reaction system. 
(18) A method according to any of (14) to (17) mentioned above, wherein the 
alkylene sulfide is ethylene sulfide or propylene sulfide and the 
mercaptocarboxylic ester is 3-mercaptopropionic ester or 2-mercaptoacetic 
ester. 
This invention allows a sulfide group-containing thiol compound to be 
produced with high activity and high selectivity by the ring-opening 
addition of alkylene sulfide to a thiol compound. Since the catalyst for 
this invention contains no halogens, it perfectly fits for the commercial 
production of the sulfide group-containing thiol compound without 
entraining such problems as corrosion of an equipment. Since the basic 
ion-exchange resin, when used as a catalyst, is in a solid state, the 
recovery and removal of the catalyst from the reaction mixture can be 
obtained very easily. Further, this invention allows a sulfide 
group-containing mercaptocarboxylic ester to be produced with a high yield 
from an alkylene sulfide and a mercaptocarboxylic ester as raw materials 
without substantially forming by-products which are subsequently 
discarded. 
DESCRIPTION OF THE PREFERRED EMBODIMENTS 
One characteristic of this invention is that a basic ion-exchange resin or 
a compound represented by the general formula (1): 
EQU A.sup.+ B.sup.- ( 1) 
is used as a catalyst in the reaction for producing a sulfide 
group-containing thiol compound by the ring-opening addition of alkylene 
sulfide to a thiol compound. In this general formula, A stands for 
quaternary ammonium or alkyl pyridinium and B stands for RCOO, ROCOO, RO, 
RS, or NCS, provided that R stand for a hydrogen atom, an alkyl group of 1 
to 18, preferably 1 to 8, carbon atoms, or an aromatic group of 6 to 18, 
preferably 6 to 10, carbon atoms. Most preferably B stands for RCOO or RO. 
The basic ion-exchange resins which are usable for the catalyst include 
ion-exchange resins having a tertiary amino group, ion-exchange resins 
having a quaternary ammonium group, and ion-exchange resins having a 
pyridine ring severally as a functional group, which can be easily 
obtained generally as commercial products. Among other basic ion-exchange 
resins cited above, weakly basic ion-exchange resins having a tertiary 
amino group as a functional group particularly excel in both activity and 
selectivity and find favorable acceptance. 
As respect such basic ion-exchange resins as are available in the market, 
the ion-exchange resins having a tertiary amino group include Amberlyst 
A-21, Amberlite IRA-93, Amberlite IRA-94, and Amberlite IRA-68 (produced 
by Rohm and Haas Company), Duolite A-368, Duolite A-561, and Duolite A-375 
(produced by Duolite International Corp.), Dowex MWA-1 (produced by The 
Dow Chemical Company), and Diaion WA30 (produced by Mitsubishi Chemical 
Co., Ltd.), for example. 
The ion-exchange resins having a quaternary ammonium group include 
Amberlite IRA-904, Amberlite IRA-938, Amberlite IRA-958, and Amberlite 
IRA-900 (produced by Rohm and Haas Company), Duolite A-161, Duolite A-165, 
and Duolite A-147 (produced by Duolite International Corp.), Dowex MSA-1 
and Dowex SBR (produced by The Dow Chemical Company), and Diaion SA10A and 
Diaion 06 (produced by Mitsubishi Chemical Co., Ltd.), for example. 
The ion-exchange resins having a pyridine ring include Sumichelate CR-2 
(produced by Sumitomo Chemical Co., Ltd.), for example. 
Among these compounds, compounds represented by the general formula (3): 
##STR7## 
are used advantageously as the quaternary ammonium compound. In this 
general formula, R.sup.5, R.sup.6, R.sup.7, and R.sup.8, which may be 
identical or different, each represents an alkyl group of 1 to 20, 
preferably 1 to 18, carbon atoms, an aromatic group of 6 to 20, preferably 
6 to 10, carbon atoms, a benzyl group, or an allyl group and B has the 
same meaning as defined above. Compounds represented by the general 
formula (4): 
##STR8## 
are advantageously used as the alkyl pyridinium compound. In this general 
formula, R.sup.9 represents an alkyl group of 1 to 20, preferably 1 to 18, 
and most preferably 1 to 16, carbon atoms and B has the same meaning as 
defined above. 
The typical quaternary ammonium compounds have a cation moiety which is 
selected among tetramethyl ammonium, tetraethyl ammonium, tetrapropyl 
ammonium, tetrabutyl ammonium, tetrahexyl ammonium, tetraoctyl ammonium, 
benzyltrimethyl ammonium, benzyltriethyl ammonium, phenyltrimethyl 
ammonium, phenyltriethyl ammonium, cetyl benzyldimethyl ammonium, and 
hexadecyl trimethyl ammonium, and an anion moiety which is selected among 
acetate, propionate, formate, benzoate, methyl carbonate, ethyl carbonate, 
propyl carbonate, butyl carbonate, phenyl carbonate, hydroxide, methoxide, 
ethoxide, propoxide, butoxide, phenoxide, hydrosulfide, methyl thiolate, 
ethyl thiolate, propyl thiolate, butyl thiolate, phenyl thiolate, and 
thiocyanate. 
The typical alkyl pyridinium compounds have a cation moiety which is 
selected among methyl pyridinium, ethyl pyridinium, propyl pyridinium, 
butyl pyridinium, octyl pyridinium, decyl pyridinium, lauryl pyridinium, 
cetyl pyridinium, and benzyl pyridinium, and an anion moiety which is 
selected among acetate, propionate, formate, benzoate, methyl carbonate, 
ethyl carbonate, propyl carbonate, butyl carbonate, phenyl carbonate, 
hydroxide, methoxide, ethoxide, propoxide, butoxide, phenoxide, 
hydrosulfide, methyl thiolate, ethyl thiolate, propyl thiolate, butyl 
thiolate, phenyl thiolate, and thiocyanate. 
Among these compounds, tetraalkyl ammonium acetates, benzyl trialkyl 
ammonium acetates, tetraalkyl ammonium hydroxides, and benzyl trialkyl 
ammonium hydroxides are particularly advantageous and are readily 
available as reagents and industrial products. 
These compounds are highly active as the catalyst and capable of fulfilling 
the role of a catalyst in a small amount. The fact that they exhibit high 
activity even in a non-aqueous system deserves a special notice. Thus, 
they not only permit the adoption of thiol compounds possessing such 
easily hydrolyzable functional groups as ester groups as a raw material 
but also allow easy implementation of the ring-opening addition of 
alkylene sulfide to a mercaptoalkanoic ester. Among other alkylene 
sulfides, ethylene sulfide possesses particularly high reactivity and 
tends to induce such secondary reactions as tolymerization. Owing to the 
use of the catalyst according to this invention, ethylene sulfide is 
prevented from inducing such secondary reactions and enabled to produce a 
sulfide group-containing thiol compound aimed at with high selectivity. 
Further even from the commercial point of view, the catalyst which 
contains no halogen is actually highly advantageous because it is free 
from such problems as corrosion of an equipment. 
Though the amount of this catalyst to be used in effecting the reaction is 
not particularly limited, it is generally in the range of 0.01 to 10 parts 
by weight, preferably 0.05 to 1 part by weight, based on 100 parts by 
weight of the reaction mixture. If this amount is less than 0.01 part by 
weight, the reaction velocity will be unduly low. Conversely, if this 
amount exceeds 10 parts by weight, the excess will go to impair the 
economy of the reaction, though it will have no adverse effect on the 
reaction itself. The method for using this catalyst varies with the form 
of the reaction. The catalyst may be added to the reaction mixture at the 
initial stage of the reaction or may be added sequentially thereto. The 
catalyst may be used in the form of a single compound or a mixture of two 
or more compounds. 
The manner of using the basic ion-exchange resin catalyst varies with the 
form of reaction. For the reaction which is performed batchwise, the 
catalyst may be added at the outset of the reaction or may be successively 
added. Since this catalyst is in a solid state, it can be very easily 
separated and recovered after the reaction by such means as decantation or 
filtration. In the reaction which is performed continuously, the catalyst 
may be retained in the form of a fixed bed in the reaction vessel and 
consequently enabled to permit continuous passage therethrough of the 
reaction mixture. 
The alkylene sulfide to be used in this invention is a compound represented 
by the general formula (2). 
##STR9## 
In this formula, R.sup.1, R.sup.2, R.sup.3, and R.sup.4, which may be the 
same or different, each represents a hydrogen atom, an alkyl group of 1 to 
10, preferably 1 to 6, carbon atoms, or an aromatic group of 6 to 15, 
preferably 6 to 10, carbon atoms. As typical examples of the alkylene 
sulfide, ethylene sulfide, propylene sulfide, isobutylene sulfide, and 
styrene sulfide may be cited. Among other alkylene sulfides cited above, 
ethylene sulfide and propylene sulfide prove particularly appropriate. 
As the thiol compound which may be used in this invention, polythiols, 
mercaptoalkanoic esters, allyl mercaptan, furfuryl mercaptan, and 
compounds represented by the general formula (5) as following: 
EQU R.sup.10 SH (5) 
may be cited. Among other thiol compounds cited above, mercaptoalkanoic 
esters and compounds represented by the general formula (5), more 
preferably, mercaptoalkanoic esters, mercaptoalkanols, aromatic thiols, 
aromatic thiocarboxylic acids, and alkane thiols, particularly 
mercaptoalkanoic esters and mercaptoalkanols may be preferably used. In 
this formula, R.sup.10 stands for a hydrogen atom, an alkyl group of 1 to 
20, preferably 1 to 12, carbon atoms, a hydroxyalkyl group of 2 to 20, 
preferably 2 to 8, carbon atoms, an aromatic group of 6 to 20, preferably 
6 to 12, carbon atoms, or R.sup.11 CO-- (wherein R.sup.11 stands for an 
alkyl group of 1 to 20, preferably 1 to 8, carbon atoms or an aromatic 
group of 6 to 20, preferably 6 to 12, carbon atoms). 
As typical examples of the thiol compound, alkane thiols such as methane 
thiol, ethane thiol, propane thiol, butane thiol, hexane thiol, and octane 
thiol, polythiols such as ethane dithiol, propane dithiol, butane dithiol, 
and bis(2-mercaptoethyl) sulfide, aromatic thiols such as thiophenol, 
1,2-benzene dithiol, 1,4-benzene dithiol, and 4-mercaptophenol, 
mercaptoalkanols such as 2-mercaptoethanol, 3-mercaptopropanol, 
1-methyl-2-mercaptoethanol, and thioglycerol, mercaptoalkanoic esters such 
as methyl ester, ethyl ester, propyl ester, butyl ester, hexyl ester, 
n-octyl ester, isooctyl ester, 2-ethylhexyl ester, lauryl ester, stearyl 
ester, ester of ethylene glycol, ester of glycerin, ester of trimethylol 
propane, ester of pentaerythritol, and ester of dipentaerythritol of 
3-mercaptopropionic acid, methyl ester, ethyl ester, propyl ester, butyl 
ester, hexyl ester, n-octyl ester, isooctyl ester, 2-ethylhexyl ester, 
lauryl ester, stearyl ester, ester of ethylene glycol, ester of glycerin, 
ester of trimethylol propane, ester of pentaerythritol, and ester of 
dipentaerythritol of 2-mercaptoproponic acid, methyl ester, ethyl ester, 
propyl ester, butyl ester, hexyl ester, n-octyl ester, isooctyl ester, 
2-ethylhexyl ester, lauryl ester, stearyl ester, ester of ethylene glycol, 
ester of glycerin, ester of trimethylol propane, ester of pentaerythritol, 
and ester of dipentaerythritol of thioglycolic acid, thiocarboxylic acids 
such as thioacetic acid, thiopropionic acid, thiobutyric acid, and 
thiobenzoic acid, and allyl mercaptan, benzyl mercaptan, furfuryl 
mercaptan, and hydrogen sulfide may be cited. 
In the ring-opening addition of alkylene sulfide to a thiol compound 
according to this invention, the number of mols of the alkylene sulfide to 
be added in the product can be controlled by the ratios of the raw 
materials to be charged. The production of an one mol adduct can be 
attained generally by using the thiol compound in an excess amount. To be 
specific, the thiol compound is used in an amount in the range of 1 to 10 
mols, preferably 1 to 5 mols, per mol of the alkylene sulfide. If the 
thiol compound is used in an excess amount, the excess will have no 
adverse effect on the reaction but will impair the productivity. When the 
thiol compound to be used has high reactivity such that the acid 
dissociation constant, pKa, is smaller than 8.0, the one mol adduct can be 
preferentially obtained even at a charging ratio (molar ratio) of 1:1. 
In the batchwise reaction, the selectivity for the one mol adduct is higher 
when the alkylene sulfide is successively added to the reaction system 
than when the raw materials are added collectively to the reaction system. 
When the alkylene sulfide is used in an excess amount, though the number 
of mols of addition is larger than 1, the product more often than not has 
a width of distribution. In this case, the amount of the alkylene sulfide 
to be used is generally in the range of 1 to 10 mols, preferably in the 
range of 1 to 3 mols, per mol of the thiol compound. If the alkylene 
sulfide is used in a still larger excess, the control of the number of 
mols of addition will become difficult. 
The reaction temperature in the method of this invention is generally in 
the range of 0.degree. to 200.degree. C., preferably in the range of 
10.degree. to 150.degree. C. The reaction contemplated by this invention 
proceeds amply even at or below room temperature because the basic 
ion-exchange resin as the catalyst to be used in this method is highly 
active. Though the reaction pressure is not particularly limited, it is 
generally in the range of 1 to 100 kg/cm.sup.2, preferably in the range of 
1 to 20 kg/cm.sup.2. For the purpose of preventing the thiol group from 
being oxidized with oxygen during the course of the reaction, it is 
appropriate to keep the interior of the reaction system under an ambience 
of an inert gas. As the inert gas, nitrogen, argon, or helium may be used. 
The method of this invention, when necessary, permits the use of a solvent. 
When the reaction elects to use a solvent, though the concentration of the 
reaction mixture is not particularly limited, it is generally in the range 
of 5 to 90% by weight, preferably in the range of 20 to 60% by weight. If 
this concentration is less than 5% by weight, the reaction velocity will 
be unduly low and, at the same time, the isolation of the product will 
prove uneconomical because the amount of the solvent to be separated and 
recovered is unduly large. Conversely, if this amount exceeds 90% by 
weight, the effect of diluting the reaction mixture with the solvent will 
not be manifested sufficiently. 
The solvent to be used in the method of this invention may be selected 
among solvents that are inert to the thiol compound and the alkylene 
sulfide. As typical examples of the solvent usable effectively herein, 
hydrocarbon type solvents such as hexane, cyclohexane, pentane, benzene, 
toluene, xylene, p-cymene, and mesitylene, ether type solvents such as 
diethyl ether, dibutyl ether, tetrahydrofuran, dioxane, 1,2-dimethoxy 
ethane, and diethylene glycol dimethyl ether, ketone type solvents such as 
acetone, methylethyl ketone, and methylisobutyl ketone, amide type 
solvents such as N,N-dimethyl formamide, N,N-dimethyl acetamide, 
formamide, and N-methylpyrrolidone, and acetonitrile, nitromethane, 
chlorobenzene, dimethyl sulfoxide, hexamethyl phosphoric triamide, and 
1,3-dimethyl-2-imidazolidinone may be cited. The removal of the heat of 
reaction can be more easily attained by performing the reaction under the 
reflux of the solvent. 
By performing the reaction as described above, a sulfide group-containing 
thiol compound represented by the following general formula (8): 
##STR10## 
(wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, and R.sup.10 have the same 
meanings as defined above and n is an integer in the range of 1 to 6, 
preferably in the range of 1 to 3), can be obtained. 
Another characteristic of this invention is that a sulfide group-containing 
mercaptocarboxylic ester can be obtained by causing a mercaptocarboxylic 
ester to react with an alkylene sulfide. To obtain a sulfide 
group-containing mercaptocarboxylic ester having the number of mols of 
added alkylene sulfide controlled in the range of 1 to 3, the amount of 
the mercaptopropionic ester to be used per mol of the alkylene sulfide 
advantageously is in the range of 1 to 10 mols. If the amount of the 
mercaptocarboxylic ester to be used is less than 1 mol per mol of the 
alkylene sulfide, the number of mols of the added alkylene sulfide will 
possibly increase and the reaction will form a compound close to a polymer 
from the physical point of view. Conversely, if this amount exceeds 10 
mols, the excess will go to lower the productivity, though a sulfide 
group-containing mercaptocarboxylic ester aimed at will be formed. 
The reactivity of the mercaptocarboxylic ester is variable with the kind of 
the ester to be used. Specifically, for the purpose of obtaining an 
one-mol adduct of alkylene sulfide, a 3-mercaptopropionic ester, for 
example, is appropriately used in an amount in the range of 3 to 7 mols 
and a 2-mercaptoacetic ester, a compound having higher reactivity, in an 
amount in the range of 1 to 2 mols, per mol of the alkylene sulfide. 
By causing the alkylene sulfide to be sequentially added into the reaction 
system, the possible increase in the number of mols of addition can be 
controlled more effectively. 
The mercaptocarboxylic ester which is used in an excess amount in this 
reaction can be easily separated and recovered as by distillation after 
the reaction and can be reused by the circulation. 
The alkylene sulfide to be used in this invention is a compound represented 
by the general formula (2): 
##STR11## 
In this general formula, R.sup.1, R.sup.2, R.sup.3, and R.sup.4 have the 
same meanings as defined above. As typical examples thereof, ethylene 
sulfide, propylene sulfide, isobutylene sulfide, and styrene sulfide may 
be cited Among other alkylene sulfides mentioned above, ethylene sulfide 
and propylene sulfide prove particularly appropriate. 
The mercaptocarboxylic ester to be used in this invention is a compound 
represented by the general formula (6): 
##STR12## 
In this general formula, R.sup.12 stands for a hydrocarbon group of 1 to 
20 carbon atoms and preferably an alkyl group of 1 to 15 carbon atoms, and 
R.sup.13 for an alkylene group of 1 to 3, preferably 1 to 2, carbon atoms. 
As typical examples of this mercaptocarboxylic ester, 3-mercaptopropionic 
esters such as methyl 3-mercaptopropionate, ethyl 3-mercaptopropionate, 
propyl 3-mercaptopropionate, butyl 3-mercaptopropionate, n-octyl 
3-mercaptopropionate, 2-ethylhexyl 3-mercaptopropionate, and n-dodecyl 
3-mercaptopropionate, 2-mercaptopropionic esters such as methyl 
2-mercaptopropionate, ethyl 2-mercaptopropionate, propyl 
2-mercaptopropionate, butyl 2-mercaptopropionate, n-octyl 
2-mercaptopropionate, 2-ethylhexyl 2-mercaptopropionate, and n-dodecyl 
2-mercaptopropionate, and 2-mercaptoacetic esters such as methyl 
2-mercaptoacetate, ethyl 2-mercaptoacetate, propyl 2-mercaptoacetate, 
butyl 2-mercaptoacetate, n-octyl 2-mercaptoacetate, 2-ethylhexyl 
2-mercaptoacetate, and n-dodecyl 2-mercaptopropionate may be cited. Among 
other mercaptocarboxylic esters enumerated above, 3-mercaptopropionic 
esters and 2-mercaptoacetic esters prove advantageous. 
In the method of this invention, the reaction can be proceeded smoothly in 
the presence of a basic catalyst or a phosphine catalyst. As concrete 
examples of the basic catalyst, alkali metal hydroxides such as sodium 
hydroxide, potassium hydroxide, and lithium hydroxide, alkaline earth 
metal hydroxides such as magnesium hydroxide, calcium hydroxide, and 
barium hydroxide, alkaline earth metal oxides such as magnesium oxide, 
calcium oxide, and barium oxide, alkali metal alkoxides such as sodium 
methoxide, sodium ethoxide, sodium isopropoxide, sodium butoxide, sodium 
phenoxide, potassium methoxide, potassium ethoxide, potassium 
isopropoxide, potassium butoxide, and potassium phenoxide, alkyl tertiary 
amines such as trimethyl amine, triethyl amine, triisopropyl amine, 
tributyl amine, and N-ethyldiisopropyl amine, alkylene polyamines such as 
N,N,N',N'-tetramethylethylene diamine, N,N,N',N'-tetramethyl-1,3-diamino 
propane, N,N,N',N'-tetramethyl-1,4-diamino butane, 
N,N,N',N'-tetramethyl-1,6-diamino hexane, and N,N,N',N',N'-pentamethyl 
diethylene triamine, amines such as N-methyl morpholine, 1,4-dimethyl 
piperazine, 2,4,6-tris(dimethylaminomethyl) phenol, 
1,4-diazabicyclo2.2.2!octane, and 1,8-diazabicyclo5.4.0!undecene, 
nitrogen-containing heterocyclic compounds such as pyridine, picoline, 
lutidine, quinoline, pyrazine, 4-dimethylamino pyridine, and 1-methyl 
imidazole, compounds selected among such tetraalkyl quaternary ammonium 
compounds as tetramethyl ammonium compounds, tetraethyl ammonium 
compounds, tetrapropyl ammonium compounds, tetrabutyl ammonium compounds, 
benzyl trimethyl ammonium compounds, benzyl triethyl ammonium compounds, 
and cetyl trimethyl ammonium compounds, which a pair anions are selected 
among carboxylates, alcoholates, thiolates, hydroxides, and hydrosulfides, 
compounds selected among such compounds selected among such alkyl 
pyridinium compounds as methyl pyridinium compounds, ethyl pyridinium 
compounds, propyl pyridinium compounds, butyl pyridinium compounds, cetyl 
pyridinium compounds, and benzyl pyridinium compounds, which pair anions 
are selected among carboxylates, alcoholates, thiolates, hydroxides, and 
hydrosulfides, and basic ion-exchange resins having a tertiary amino group 
or a quaternary ammonium group as a functional group may be cited. As 
concrete examples of the phosphine catalyst, trimethyl phosphine, triethyl 
phosphine, tripropyl phosphine, tributyl phosphine, and triphenyl 
phosphine may be cited. 
Though the amount of the basic catalyst or phosphine catalyst to be used is 
not particularly limited, it is generally in the range of 0.01 to 10 parts 
by weight, referably 0.05 to 1 part by weight, based on 100 parts by 
weight of the reaction mixture. If this amount is less than 0.01 part by 
weight, the reaction velocity will be unduly low. Conversely, if this 
amount exceeds 10 parts by weight, the excess will go to impair the 
economy of the reaction, though it will have no adverse effect on the 
reaction itself. 
The reaction temperature in the method of this invention is generally in 
the range of 0.degree. to 200.degree. C., preferably 10.degree. to 
150.degree. C. Though the reaction pressure is not particularly limited, 
it is generally in the range of 1 to 100 kg/cm.sup.2, preferably 1 to 20 
kg/cm.sup.2. For the purpose of precluding the otherwise possible 
oxidation of the mercapto group with oxygen during the course of reaction, 
it is advantageous to retain the interior of the reaction system under an 
ambience of an inert gas. As the inert gas, nitrogen, argon, helium, etc. 
may be used. 
The method of this invention, when necessary, may use a solvent. When a 
solvent is used, the concentration of the reaction mixture is not 
particularly limited, but is generally in the range of 5 to 90% by weight, 
preferably 20 to 60% by weight. If this concentration is less than 5% by 
weight, the reaction velocity will be unduly low and, at the same time, 
the isolation of the reaction product will necessitate the separation and 
recovery of a large amount of the solvent possibly to the extent of 
impairing the economy of the reaction. Conversely, if the amount exceeds 
90% by weight, the effect of diluting the reaction mixture with the 
solvent will not be manifested satisfactorily. 
Any solvents which are inert to the mercaptocarboxylic ester and the 
alkylene sulfide are invariably usable effectively in the method of this 
invention. As typical examples of the solvent, hydrocarbon type solvents 
such as hexane, cyclohexane, pentane, benzene, toluene, xylene, p-cymene, 
and mesitylene, ether type solvents such as diethyl ether, dibutyl ether, 
tetrahydrofuran, dioxane, 1,2-dimethoxy ethane, and diethylene glycol 
dimethyl ether, ketone type solvents such as acetone, methylethyl ketone, 
and methyl isobutyl ketone, amide type solvents such as N,N-dimethyl 
formamide, N,N-dimethyl acetamide, formamide, and N-methyl pyrrolidone, 
and acetonitrile, nitromethane, chlorobenzene, dimethyl sulfoxide, 
hexamethyl phosphoric triamide, and 1,3-dimethyl-2-imidazolidinone may be 
cited. When the alkylene sulfide is other than ethylene sulfide, such 
alcohols as methanol, ethanol, propanol, butanol, 2-methoxy ethanol, 
2-ethoxy ethanol, and 2-butoxy ethanol are further usable as the solvent. 
The heat of reaction can be removed more easily by carrying out the 
reaction under the reflux of the solvent. 
By carrying out the reaction as described above, the sulfide 
group-containing mercaptocarboxylic ester represented by the general 
formula (7): 
##STR13## 
(wherein R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.12, and R.sup.13 have 
the same meanings as defined above and n is an integer in the range of 1 
to 3, preferably 1 to 2) can be obtained. 
Now, this invention will be described more specifically below with 
reference to working examples and controls. It should be noted, however, 
that this invention is not limited by these examples.

EXAMPLE 1 
In a four-neck flask provided with a stirrer, a reflux condenser, a 
thermometer, and a dropping funnel, 24.0 g (200 m.mols) of methyl 
3-mercaptopropionate, 40 g of toluene, and 0.4 g of a basic ion-exchange 
resin (produced by Rohm and Haas Company and marketed under trademark 
designation of "Amberlyst A-21") were placed and kept at a temperature of 
50.degree. C. under a stream of nitrogen and 2.4 g (40 m.mols) of ethylene 
sulfide was added dropwise thereto over a period of 30 minutes. After the 
ensuant reaction was continued at the same temperature for two hours, the 
reaction product was extracted from the flask and analyzed by gas 
chromatography. Consequently, it was found to consist of one-mol adduct 
and two-mol adduct of ethylene sulfide at a ratio of 89:11 (area ratio of 
gas chromatograph). Thus, the total yield of the obtained ethylene sulfide 
adducts was found to be 98%, based on the weight of the ethylene sulfide. 
The results are shown in Table 1 and Table 2. 
EXAMPLE 2 
The results shown in Table 1 and Table 2 were obtained by following the 
procedure of Example 1 while using 24.0 g (200 m.mols) of ethyl 
2-mercaptoacetate and 12.0 g (200 m.mols) of ethylene sulfide as the raw 
materials for the reaction. 
EXAMPLE 3 
The results shown in Table 1 and Table 2 were obtained by following the 
procedure of Example 1 while using 15.6 g (200 m.mols) of 
2-mercaptoethanol and 2.4 g (40 m.mols) of ethylene sulfide as the raw 
materials for the reaction. 
EXAMPLE 4 
The results shown in Table 1 and Table 2 were obtained by following the 
procedure of Example 1 while using 27.6 g (200 m.mols) of thiobenzoic acid 
and 12.0 g (200 m.mols) of ethylene sulfide as the raw materials for the 
reaction. 
EXAMPLE 5 
The results shown in Table 1 and Table 2 were obtained by following the 
procedure of Example 1 while using 22.0 g (200 m.mols) of thiophenol and 
2.4 g (40 m.mols) of ethylene sulfide as the raw materials for the 
reaction. 
EXAMPLE 6 
The results shown in Table 1 and Table 2 were obtained by following the 
procedure of Example 1 while using 15.2 g (200 m.mols) of propanethiol 
and2.4 g (40 m.mols) of ethylene sulfide as the raw materials for the 
reaction. 
EXAMPLE 7 
The results shown in Table 1 and Table 2 were obtained by following the 
procedure of Example 1 while using 24.0 g (200 m.mols) of methyl 
3-mercapto propionate and 14.8 g (200 m.mols) of propylene sulfide as the 
raw materials for the reaction. 
EXAMPLE 8 
The results shown in Table 1 and Table 2 were obtained by following the 
procedure of Example 1 while using 0.4 g of a basic ion-exchange resin 
(produced by Rohm and Haas Company and marketed under trademark 
designation of "Amberlite IRA-904") as the catalyst instead. 
EXAMPLE 9 
In the same apparatus as used in Example 1, 13.8 g (100 m.mols) of 
thiobenzoic acid and 1.2 g of a catalyst (produced by Sumitomo Chemical 
Company and marketed under trademark designation of "Sumichelate CR-2") 
were placed and kept at a temperature of 60.degree. C. under a stream of 
nitrogen and 6.0 g (100 m.mols) of ethylene sulfide was added dropwise 
thereto over a period of 30 minutes. After the ensuant reaction was 
continued at the same temperature for six hours, the reaction product was 
extracted and analyzed by gas chromatography. The results shown in Table 1 
and Table 2 were obtained. 
Control 1 
The results shown in Table 1 and Table 2 were obtained by repeating the 
procedure of Example 1 while using 0.4 g of triethyl amine as the 
catalyst. 
TABLE 1 
__________________________________________________________________________ 
Molar ratio of raw materials 
Thiol Compound (A) 
Alkylene Sulfide (B) 
(A)/(B) Catalyst 
__________________________________________________________________________ 
Example 1 
Methyl 3-mercapto propionate 
ES 5/1 Amberlyst A-21 
Example 2 
Ethyl 2-mercaptoacetate 
ES 1/1 Amberlyst A-21 
Example 3 
2-Mercaptoethanol 
ES 5/1 Amberlyst A-21 
Example 4 
Thiobenzoic acid 
ES 1/1 Amberlyst A-21 
Example 5 
Thiophenol ES 5/1 Amberlyst A-21 
Example 6 
Propane thiol 
ES 5/1 Amberlyst A-21 
Example 7 
Methyl 3-mercapto propionate 
PS 1/1 Amberlyst A-21 
Example 8 
Methyl 3-mercapto propionate 
ES 5/1 Amberlite IRA-904 
Example 9 
Thiobenzoic acid 
ES 1/1 Sumichelate CR-2 
Control 1 
Methyl 3-mercapto propionate 
ES 5/1 Triethyl amine 
__________________________________________________________________________ 
Abbreviation: 
ES: Ethylene sulfide 
PS: Propylene sulfide 
Amberlyst A21: Ionexchange resin having a tertiary amino group as a 
functional group (produced by Rohm and Haas Company), and was used after 
washed with water and dried. 
Amerlite IRA904: Ionexchange resin having a quaternary amino group as a 
functional group (produced by Rohm and Haas Company), and was used after 
pretreatment with an aqueous sodium hydroxide solution, washed with water 
and dried. 
Sumichelate CR2: Ionexchange resin having a pyridine ring as a functional 
group (produced by Sumitomo Chemical Company), and was used after washed 
with water and dried. 
TABLE 2 
______________________________________ 
Total yield of 
Ratio of product 
product (%) 1 mol adduct 
2 mol adduct 
3 mol adduct 
______________________________________ 
Example 1 
98 89 11 Trace amount 
Example 2 
98 99 1 0 
Example 3 
97 93 7 Trace amount 
Example 4 
96 100 0 0 
Example 5 
99 97 3 0 
Example 6 
83 48 40 22 
Example 7 
73 88 12 0 
Example 8 
87 85 15 Trace amount 
Example 9 
82 97 3 0 
Control 1 
3 47 53 0 
______________________________________ 
EXAMPLE 10 
In a four-neck flask provided with a stirrer, a reflux condenser, a 
thermometer, and a dropping funnel, 60.1 g (0.5 mol) of methyl 
3-mercaptopropionate and 0.20 g of tetrabutyl ammonium acetate (produced 
by Aldrich) were placed and kept under a stream of nitrogen at a 
temperature of 50.degree. C. and 6.0 g (0.1 mol) of ethylene sulfide was 
added dropwise thereto over a period of 30 minutes. The ensuant reaction 
was further continued at the same temperature for three hours. Then, the 
reaction product was extracted from the flask and analyzed by gas 
chromatography. The product was found to consist of a 1-mol adduct and a 
2-mol adduct of ethylene sulfide at a ratio of 87:13 (area ratio of gas 
chromatograph). The total yield of the obtained ethylene sulfide adducts 
was 98%, based on the weight of the ethylene sulfide. The results are 
shown in Table 3 and Table 4. 
EXAMPLE 11 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 0.20 g of tetramethyl ammonium acetate 
(produced by Aldrich) as the catalyst instead. 
EXAMPLE 12 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 0.59 g of tetrabutyl ammonium benzoate 
(produced by Fluka) as the catalyst instead. 
EXAMPLE 13 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 0.20 g of tetrabutyl ammonium 
hydrosulfide (produced by Fluka) as the catalyst instead. 
EXAMPLE 14 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 0.20 g of tetrabutyl ammonium 
thiocyanate (produced by Tokyo Kasei Kogyo K. K.) as the catalyst instead. 
EXAMPLE 15 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 0.13 g of a methanol 40% benzyl 
trimethyl ammonium hydroxide solution (produced by Tokyo Kasei Kogyo K. 
K.) as the catalyst instead. 
EXAMPLE 16 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 0.53 g of a methanol 10% tetrabutyl 
ammonium hydroxide solution (produced by Tokyo Kasei Kogyo K. K.) as the 
catalyst instead. 
EXAMPLE 17 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 0.53 g of a methanol 10% tetramethyl 
ammonium hydroxide solution (produced by Tokyo Kasei Kogyo K. K.) as the 
catalyst instead. 
EXAMPLE 18 
In an agitation type autoclave, 9.0 g (0.1 mol) of dimethyl carbonate, 10.1 
g (0.1 mol) of triethyl amine, and 10.0 g of methanol as a solvent were 
placed and left reacting therein at a reaction temperature of 115.degree. 
C. under a reaction pressure of 5.0 kg/cm.sup.2 G for 12 hours. The 
resultant reaction solution was cooled, extracted from the autoclave, and 
distilled under a reduced pressure to remove the unaltered materials and 
the solvent and to obtain 9.8 g of solid triethylmethyl ammonium methyl 
carbonate (in accordance with the method of JP-B-08-19, 060, with 
necessary modifications). The results shown in Table 3 and Table 4 were 
obtained by following the procedure of Example 10 while using 0.20 g of 
triethylmethyl ammonium methyl carbonate obtained as described above as 
the catalyst instead. 
EXAMPLE 19 
A solution of 5.56 g (0.02 mol) of tetrabutyl ammonium chloride in 49.0 g 
of methanol was kept stirred and 1.08 g (0.02 mol) of sodium methoxide was 
gradually added thereto with stirred. The ensuant reaction was further 
continued at room temperature for 15 hours. Then, the reaction solution 
was filtered to obtain tetrabutyl ammonium methoxide. The results shown in 
Table 3 and Table 4 were obtained by following the procedure of Example 10 
while using 0.53 g of a methanol 10% tetrabutyl ammonium methoxide 
solution thus obtained as the catalyst instead. 
EXAMPLE 20 
To a solution of 7.16 g (0.02 mol) of cetyl pyridinium chloride monohydrate 
in 60.4 g of methanol, 1.08 g (0.02 mol) of sodium methoxide was added 
little by little as kept stirred. The ensuant reaction was further 
continued at room temperature for 15 hours. Then, the reaction solution 
was filtered to obtain cetyl pyridinium methoxide. The results shown in 
Table 3 and Table 4 were obtained by following the procedure of Example 10 
while using 0.53 g of a methanol 10% cetyl pyridinium methoxide solution 
as the catalyst instead. 
EXAMPLE 21 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 40.9 g (0.2 mol) of 2-ethylhexyl 
2-mercaptoacetate and 6.0 g (0.1 mol) of ethylene sulfide as the raw 
materials and 0.23 g of tetramethyl ammonium acetate as the catalyst 
instead. 
EXAMPLE 22 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 52.1 g (0.2 mol) of n-dodecyl 
2-mercaptoacetate and 6.0 g (0.1 mol) of ethylene sulfide as the raw 
materials and 0.35 g of tetrabutyl ammonium hydrosulfide as the catalyst 
instead. 
EXAMPLE 23 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 11.0 g (0.1 mol) of thiophenol and 7.4 
g (0.1 mol) of propylene sulfide as the raw materials and 0.06 g of 
tetrabutyl ammonium acetate as the catalyst instead. 
EXAMPLE 24 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 46.1 g (0.5 mol) of 
1-methyl-2-mercaptoethanol and 7.4 g (0.1 mol) of propylene sulfide as the 
raw materials and 0.05 g of tetrabutyl ammonium acetate as the catalyst 
instead. 
EXAMPLE 25 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 36.6 g (0.25 mol) of 1-octane thiol 
and 3.7 g (0.05 mol) of propylene sulfide as the raw materials and 0.12 g 
of tetrabutyl ammonium acetate as the catalyst instead. 
EXAMPLE 26 
The results shown in Table 3 and Table 4 were obtained by following the 
procedure of Example 10 while using 6.9 g (0.05 mol) of thiobenzoic acid 
and 3.7 g (0.05 mol) of propylene sulfide as the raw materials, 30 g of 
1,4-dioxane as the solvent, and 0.08 g of tetrabutyl ammonium acetate as 
the catalyst instead. 
TABLE 3 
__________________________________________________________________________ 
Thiol Compound Alkylene Sulfide 
Molar ratio of raw Amount of catalyst 
(A) (B) materials (A)/(B) 
Catalyst added (wt 
__________________________________________________________________________ 
%) 
Example 10 
Methyl 3- Ethylene sulfide 
5/1 Tetrabutyl ammonium acetate 
0.3 
mercaptopropionate 
Example 11 
Methyl 3- Ethylene sulfide 
5/1 Tetramethyl ammonium acetate 
0.3 
mercaptopropionate 
Example 12 
Methyl 3- Ethylene sulfide 
5/1 Tetrabutyl ammonium benzoate 
0.9 
mercaptopropionate 
Example 13 
Methyl 3- Ethylene sulfide 
5/1 Tetrabutyl ammonium hydrosulfide 
0.3 
mercaptopropionate 
Example 14 
Methyl 3- Ethylene sulfide 
5/1 Tetrabutyl ammonium thiocyanate 
0.3 
mercaptopropionate 
Example 15 
Methyl 3- Ethylene sulfide 
5/1 Benzyl trimethyl ammonium 
0.08oxide 
mercaptopropionate 
Example 16 
Methyl 3- Ethylene sulfide 
5/1 Tetrabutyl ammonium hydroxide 
0.08 
mercaptopropionate 
Example 17 
Methyl 3- Ethylene sulfide 
5/1 Tetramethyl ammonium hydroxide 
0.08 
mercaptopropionate 
Example 18 
Methyl 3- Ethylene sulfide 
5/1 Triethylmethyl ammonium methyl 
carbonate 0.3 
mercaptopropionate 
Example 19 
Methyl 3- Ethylene sulfide 
5/1 Tetrabutyl ammonium methoxide 
0.08 
mercaptopropionate 
Example 20 
Methyl 3- Ethylene sulfide 
5/1 Cetyl pyridinium methoxide 
0.08 
mercaptopropionate 
Example 21 
2-Ethylhexyl 
Ethylene sulfide 
2/1 Tetramethyl ammonium acetate 
0.5 
2-mercaptoacetate 
Example 22 
n-Dodecyl Ethylene sulfide 
2/1 Tetrabutyl ammonium hydrosulfide 
0.6 
2-mercaptoacetate 
Example 23 
Thiophenol 
Propylene sulfide 
1/1 Tetrabutyl ammonium acetate 
0.3 
Example 24 
1-Methyl-2- 
Propylene sulfide 
5/1 Tetrabutyl ammonium acetate 
0.1 
mercaptoethanol 
Example 25 
1-Octane thiol 
Propylene sulfide 
5/1 Tetrabutyl ammonium acetate 
0.3 
Example 26 
Thiobenzoic acid 
Propylene sulfide 
1/1 Tetrabutyl ammonium acetate 
0.2 
__________________________________________________________________________ 
Note) 
The amount of the catalyst added is represented as a concentration (% by 
weight) in the reaction mixture. 
The yield of the product is represented on the basis of the alkylene 
sulfide. 
TABLE 4 
______________________________________ 
Total yield of Ratio of product 
product (%) 1 mol adduct 
2 mol adduct 
3 mol adduct 
______________________________________ 
Example 10 
98 87 13 0 
Example 11 
94 86 14 Trace 
amount 
Example 12 
92 82 17 1 
Example 13 
96 80 19 1 
Example 14 
95 88 12 0 
Example 15 
98 86 14 0 
Example 16 
98 86 14 0 
Example 17 
97 87 13 0 
Example 18 
80 83 17 0 
Example 19 
95 85 15 Trace 
amount 
Example 20 
83 87 13 0 
Example 21 
96 99 1 0 
Example 22 
90 98 2 0 
Example 23 
92 99 1 0 
Example 24 
96 97 3 Trace 
amount 
Example 25 
79 74 22 4 
Example 26 
84 94 6 0 
______________________________________ 
Control 2 
The results shown in Table 5 and Table 6 were obtained by following the 
procedure of Example 10 while using 0.20 g of benzyl trimethyl ammonium 
chloride (produced by Wako Pure Chemical Industries Ltd.) as the catalyst 
instead. 
Control 3 
The results shown in Table 5 and Table 6 were obtained by following the 
procedure of Example 10 while using 0.20 g of tetrabutyl ammonium chloride 
(produced by Wako Pure Chemical Industries Ltd.) as the catalyst instead. 
Control 4 
The results shown in Table 5 and Table 6 were obtained by following the 
procedure of Example 10 while using 0.20 g of tetrabutyl ammonium bromide 
(produced by Wako Pure Chemical Industries Ltd.) as the catalyst instead. 
Control 5 
The results shown in Table 5 and Table 6 were obtained by following the 
procedure of Example 10 while using 0.20 g of tetrabutyl ammonium fluoride 
trihydrate (produced by Wako Pure Chemical Industries Ltd.) as the 
catalyst instead. In this reaction, a polymer of ethylene sulfide in the 
form of a white precipitate was partly formed. 
Control 6 
The results shown in Table 5 and Table 6 were obtained by following the 
procedure of Example 10 while using 0.20 g of tetrabutyl ammonium iodide 
(produced by Wako Pure Chemical Industries Ltd.) as the catalyst instead. 
TABLE 5 
__________________________________________________________________________ 
Thiol Compound 
Alkylene Sulfide 
Molar ratio of raw Amount of catalyst 
(A) (B) materials (A)/(B) 
Catalyst added (wt 
__________________________________________________________________________ 
%) 
Control 1 
Methyl 3- 
Ethylene sulfide 
5/1 Benzyl trimethyl ammonium 
0.3oride 
mercaptopropionate 
Control 2 
Methyl 3- 
Ethylene sulfide 
5/1 Tetrabutyl ammonium chloride 
0.3 
mercaptopropionate 
Control 3 
Methyl 3- 
Ethylene sulfide 
5/1 Tetrabutyl ammonium bromide 
0.3 
mercaptopropionate 
Control 4 
Methyl 3- 
Ethylene sulfide 
5/1 Tetrabutyl ammonium fluoride 
0.3 
mercaptopropionate 
Control 5 
Methyl 3- 
Ethylene sulfide 
5/1 Tetrabutyl ammonium iodide 
0.3 
mercaptopropionate 
__________________________________________________________________________ 
Note) 
The amount of the catalyst added is represented as a concentration (% by 
weight) in the reaction mixture. 
The yield of the product is represented on the basis of the standards of 
alkylene sulfide. 
TABLE 6 
______________________________________ 
Total yield of Ratio of product 
product (%) 1 mol adduct 
2 mol adduct 
3 mol adduct 
______________________________________ 
Control 2 
1 100 0 0 
Control 3 
2 100 0 0 
Control 4 
0 -- -- -- 
Control 5 
64 79 20 1 
Control 6 
1 100 0 0 
______________________________________ 
EXAMPLE 27 
In a four-neck flask provided with a stirrer, a reflux condenser, a 
thermometer, and a dropping funnel, 60.1 g (0.5 mol) of methyl 
3-mercaptopropionate and 0.20 g of tetrabutyl ammonium acetate (produced 
by Aldrich) were placed and kept under a stream of nitrogen at a 
temperature of 50.degree. C. and 6.0 g (0.1 mol) of ethylene sulfide was 
added dropwise thereto over a period of 30 minutes. The ensuing reaction 
was further continued at the same temperature for three hours. Then, the 
reaction product was extracted from the flask and analyzed by gas 
chromatography. It was consequently found to consist of an 1-mol adduct 
and a 2-mol adduct of ethylene sulfide at a ratio of 87:13 (area ratio of 
gas chromatograph). The total yield of the obtained ethylene sulfide 
adducts was 98%, based on the weight of the ethylene sulfide. The results 
are shown in Table 7 and Table 8. 
EXAMPLE 28 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.20 g of tetramethyl ammonium acetate 
(produced by Aldrich) as the catalyst instead. 
EXAMPLE 29 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.59 g of tetrabutyl ammonium benzoate 
(produced by Fluka) as the catalyst instead. 
EXAMPLE 30 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.20 g of tetrabutyl ammonium 
hydrosulfide (produced by Fluka) as the catalyst instead. 
EXAMPLE 31 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.13 g of a methanol 40% benzyl 
trimethyl ammonium hydroxide solution (produced by Tokyo Kasei Kogyo K. 
K.) as the catalyst instead. 
EXAMPLE 32 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.53 g of a methanol 10% tetrabutyl 
ammonium hydroxide solution (produced by Tokyo Kasei Kogyo K. K.) as the 
catalyst instead. 
EXAMPLE 33 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.53 g of a methanol 10% tetramethyl 
ammonium hydroxide solution (produced by Tokyo Kasei Kogyo K. K.) as the 
catalyst instead. 
EXAMPLE 34 
A solution of 5.56 g (0.02 mol) of tetrabutyl ammonium chloride in 49.0 g 
of methanol was kept stirred and 1.08 g (0.02 mol) of sodium methoxide was 
added gradually thereto. The ensuant reaction was further continued at 
room temperature for 15 hours. The resultant reaction solution was 
filtered. The results shown in Table 7 and Table 8 were obtained by 
following the procedure of Example 27 while using 0.53 g of a methanol 10% 
solution of tetrabutyl ammonium methoxide thus obtained as the catalyst. 
EXAMPLE 35 
A solution of 7.16 g (0.20 mol) of cetyl pyridinium chloride monohydrate in 
60.4 g of methanol was kept stirred and 1.08 g (0.02 mol) of sodium 
methoxide was added little by little thereto. The ensuant reaction was 
further continued at room temperature for 15 hours. The resultant reaction 
solution was filtered. The results shown in Table 7 and Table 8 were 
obtained by following the procedure of Example 27 while using 0.53 g of a 
methanol 10% solution of cetyl pyridinium methoxide thus obtained as the 
catalyst. 
EXAMPLE 36 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.13 g of sodium methoxide as the 
catalyst instead. 
EXAMPLE 37 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.02 g of potassium hydroxide as the 
catalyst instead. 
EXAMPLE 38 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.53 g of N,N,N',N'-tetramethyl 
ethylene diamine as the catalyst instead. 
EXAMPLE 39 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.53 g of 
2,4,6-tris(dimethylaminomethyl) phenol as the catalyst instead. 
EXAMPLE 40 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.53 g of N-methyl morpholine as the 
catalyst instead. 
EXAMPLE 41 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.53 g of 
1,4-diazabicyclo2.2.2!octane as the catalyst instead. 
EXAMPLE 42 
The results shown in Table 7 and Table 8 were obtained by following the 
procedure of Example 27 while using 0.53 g of 1-methyl imidazole as the 
catalyst instead. 
TABLE 7 
__________________________________________________________________________ 
Alkylene 
Molar ratio of Amount of 
Mercaptocarboxylic ester 
Sulfide 
raw materials catalyst added 
(A) (B) (A)/(B) 
Catalyst (wt %) 
__________________________________________________________________________ 
Example 27 
Methyl 3-mercaptopropionate 
ES 5/1 Tetrabutyl ammonium acetate 
0.3 
Example 28 
Methyl 3-mercaptopropionate 
ES 5/1 Tetramethyl ammonium acetate 
0.3 
Example 29 
Methyl 3-mercaptopropionate 
ES 5/1 Tetrabutyl ammonium benzoate 
0.9 
Example 30 
Methyl 3-mercaptopropionate 
ES 5/1 Tetrabutyl ammonium hydrosulfide 
0.3 
Example 31 
Methyl 3-mercaptopropionate 
ES 5/1 Benzyl trimethyl ammonium 
0.08oxide 
Example 32 
Methyl 3-mercaptopropionate 
ES 5/1 Tetrabutyl ammonium hydroxide 
0.08 
Example 33 
Methyl 3-mercaptopropionate 
ES 5/1 Tetramethyl ammonium hydroxide 
0.08 
Example 34 
Methyl 3-mercaptopropionate 
ES 5/1 Tetrabutyl ammonium hydroxide 
0.08 
Example 35 
Methyl 3-mercaptopropionate 
ES 5/1 Cetyl pyridinium methoxide 
0.08 
Example 36 
Methyl 3-mercaptopropionate 
ES 5/1 Sodium methoxide 0.2 
Example 37 
Methyl 3-mercaptopropionate 
ES 5/1 Potassium hydroxide 
0.3 
Example 38 
Methyl 3-mercaptopropionate 
ES 5/1 N,N,N',N'-Tetramethyl ethylenediamine 
0.8 
Example 39 
Methyl 3-mercaptopropionate 
ES 5/1 2,4,6-Tris(dimethylaminomethyl)phenol 
0.8 
Example 40 
Methyl 3-mercaptopropionate 
ES 5/1 N-Methyl morpholine 
0.8 
Example 41 
Methyl 3-mercaptopropionate 
ES 5/1 1,4-Diazabicyclo2.2.2!octane 
0.8 
Example 42 
Methyl 3-mercaptopropionate 
ES 5/1 1-Methyl imidazole 
0.8 
__________________________________________________________________________ 
Note) 
The amount of the catalyst added is represented as a concentration (% by 
weight) in the reaction mixture. 
The yield of the product is represented on the basis of the alkylene 
sulfide. 
Abbreviation) 
ES: Ethylene sulfide; 
PS: Propylene sulfide; 
Amberlyst A21: Ionexchange resin having a tertiary amino group as a 
functional group (produced by Rohm and Haas Company) was used after washe 
with water and dried. 
Amberlite IRA904: Ionexchange resin having a quaternary ammonium group as 
a functional group (produced by Rohm and Haas Company) was used after 
pretreated with an aqueous sodium hydroxide solution, washed with water 
and dried. 
TABLE 8 
______________________________________ 
Total yield of Ratio of product 
product (%) 1 mol adduct 
2 mol adduct 
3 mol adduct 
______________________________________ 
Example 27 
98 87 13 0 
Example 28 
94 86 14 Trace 
amount 
Example 29 
92 82 17 1 
Example 30 
96 80 19 1 
Example 31 
98 86 14 0 
Example 32 
98 86 14 0 
Example 33 
97 87 13 0 
Example 34 
95 85 15 Trace 
amount 
Example 35 
83 87 13 0 
Example 36 
93 91 9 0 
Example 37 
96 91 9 0 
Example 38 
94 90 10 0 
Example 39 
88 93 7 0 
Example 40 
72 90 10 0 
Example 41 
91 91 9 0 
Example 42 
89 88 12 0 
______________________________________ 
EXAMPLE 43 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 0.53 g of 4-dimethyl amino pyridine as 
the catalyst instead. 
EXAMPLE 44 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 6.6 g of pyridine as the catalyst 
instead. 
EXAMPLE 45 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 6.6 g of 3-picoline as the catalyst 
instead. 
EXAMPLE 46 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 0.20 g of tri-n-butyl phosphine as the 
catalyst instead. 
EXAMPLE 47 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 0.20 g of triphenyl phosphine as the 
catalyst instead. 
EXAMPLE 48 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 21.2 g (0.2 mol) of methyl 
2-mercaptoacetate and 6.0 g (0.1 mol) of ethylene sulfide as the raw 
materials and 0.41 g of 2,4,6-tris (dimethylaminomethyl) phenol as the 
catalyst instead. 
EXAMPLE 49 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 21.2 g (0.2 mol) of methyl 
2-mercaptoacetate and 6.0 g (0.1 mol) of ethylene sulfide as the raw 
materials and 0.16 g of calcium hydroxide as the catalyst instead. 
EXAMPLE 50 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 21.2 g (0.2 mol) of methyl 
2-mercaptoacetate and 6.0 g (0.1 mol) of ethylene sulfide as the raw 
materials and 0.16 g of calcium oxide as the catalyst instead. 
EXAMPLE 51 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 20.4 g (0.1 mol) of 2-ethylhexyl 
2-mercaptoacetate and 7.4 g (0.1 mol) of propylene sulfide as the raw 
materials, 40 g of tetrahydrofuran as the solvent, and 2.0 g of magnesium 
oxide as the catalyst instead. 
EXAMPLE 52 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 40.9 g (0.2 mol) of 2-ethylhexyl 
2-mercaptoacetate and 6.0 g (0.1 mol) of ethylene sulfide as the raw 
materials and 0.23 g of tetramethyl ammonium acetate as the catalyst 
instead. 
EXAMPLE 53 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 52.1 g (0.2 mol) of n-dodecyl 
2-mercaptoacetate and 6.0 g (0.1 mol) of ethylene sulfide as the raw 
materials and 0.35 g of tetrabutyl ammonium hydrosulfide as the catalyst 
instead. 
EXAMPLE 54 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 10.6 g (0.1 mol) of methyl 
2-mercaptoacetate and 6.0 g (0.1 mol) of ethylene sulfide as the raw 
materials, 30 g of 1,4-dioxane as the solvent, and 0.47 g of triethyl 
amine as the catalyst instead and changing the reaction time to 10 hours. 
EXAMPLE 55 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 27 while using 10.6 g (0.1 mol) of methyl 
2-mercaptoacetate and 7.4 g (0.1 mol) of propylene sulfide as the raw 
materials, 60 g of methanol as the solvent, and 0.15 g of sodium hydroxide 
as the catalyst instead and changing the reaction time to 5 hours. 
EXAMPLE 56 
In the same apparatus as used in Example 27, 24.0 g (0.2 mol) of methyl 
3-mercaptopropionate, 40 g of toluene, and 0.4 g of a basic ion-exchange 
resin (produced by Rohm and Haas Company and marketed under trademark 
designation of "Amberlyst A-21") were placed and kept under a stream of 
nitrogen at a temperature of 50.degree. C. and 2.4 g (0.04 mol) of 
ethylene sulfide was added dropwise thereto over a period of 30 minutes. 
The ensuant reaction was further continued at the same temperature for two 
hours. Then, the reaction product was extracted from the apparatus and 
analyzed by gas chromatography. The results by the analysis were shown in 
Table 9 and Table 10. 
EXAMPLE 57 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 56 while using 24.0 g (0.2 mol) of ethyl 
2-mercaptoacetate and 12.0 g (0.2 mol) of ethylene sulfide as the raw 
materials instead. 
EXAMPLE 58 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 56 while using 24.0 g (0.2 mol) of methyl 
3-mercaptopropionate and 14.8 g (0.2 mol) of propylene sulfide as the raw 
materials instead. 
EXAMPLE 59 
The results shown in Table 9 and Table 10 were obtained by following the 
procedure of Example 56 while using 0.4 g of a basic ion-exchange resin 
(produced by Rohm and Haas Company and marketed under trademark 
designation of "Amberlite IRA-904") as the catalyst instead. 
TABLE 9 
__________________________________________________________________________ 
Alkylene 
Molar ratio of Amount of 
Mercaptocarboxylic ester 
Sulfide 
raw materials catalyst added 
(A) (B) (A)/(B) 
Catalyst (wt %) 
__________________________________________________________________________ 
Example 43 
Methyl 3-mercaptopropionate 
ES 5/1 4-Dimethyl amino pyridine 
0.8 
Example 44 
Methyl 3-mercaptopropionate 
ES 5/1 Pyridine 10 
Example 45 
Methyl 3-mercaptopropionate 
ES 5/1 3-Picoline 10 
Example 46 
Methyl 3-mercaptopropionate 
ES 5/1 Tri-n-butyl phosphine 
0.3 
Example 47 
Methyl 3-mercaptopropionate 
ES 5/1 Triphenyl phosphine 
0.3 
Example 48 
Methyl 2-mercaptoacetate 
ES 2/1 2,4,6-Tris(dimethylaminomethyl)phenol 
1.5 
Example 49 
Methyl 2-mercaptoacetate 
ES 2/1 Calcium hydroxide 
0.6 
Example 50 
Methyl 2-mercaptoacetate 
ES 2/1 Calcium oxide 0.6 
Example 51 
2-Ethylhexyl 2-mercaptoacetate 
PS 1/1 Magnesium oxide 2.9 
Example 52 
2-Ethylhexyl 2-mercaptoacetate 
ES 2/1 Tetramethyl ammonium acetate 
0.5 
Example 53 
n-Dodecyl 2-mercaptoacetate 
ES 2/1 Tetrabutyl ammonium hydrosulfide 
0.6 
Example 54 
Methyl 2-mercaptoacetate 
ES 1/1 Triethyl amine 1.0 
Example 55 
Methyl 2-mercaptoacetate 
PS 1/1 Sodium hydroxide 0.2 
Example 56 
Methyl 3-mercaptopropionate 
ES 5/1 Amberlyst A-21 0.6 
Example 57 
Ethyl 2-mercaptoacetate 
ES 1/1 Amberlyst A-21 0.5 
Example 58 
Methyl 3-mercaptopropionate 
PS 1/1 Amberlyst A-21 0.5 
Example 59 
Methyl 3-mercaptopropionate 
ES 5/1 Amberlite IRA-904 
0.6 
__________________________________________________________________________ 
Note) 
The amount of the catalyst added is represented as a concentration (% by 
weight) in the reaction mixture. 
The yield of the product is represented on the basis of the alkylene 
sulfide. 
Abbreviation) 
ES: Ethylene sulfide; 
PS: Propylene sulfide; 
Amberlyst A21: Ionexchange resin having a tertiary amino group as a 
functional group (produced by Rohm and Haas Company) was used after washe 
with water and dried. 
Amberlite IRA904: Ionexchange resin having a quaternary ammonium group as 
a functional group (produced by Rohm and Haas Company) was used after 
pretreated with an aqueous sodium hydroxide solution, washed with water 
and dried. 
TABLE 10 
______________________________________ 
Total yield of Ratio of product 
product (%) 1 mol adduct 
2 mol adduct 
3 mol adduct 
______________________________________ 
Example 43 
91 87 13 Trace 
amount 
Example 44 
98 87 13 0 
Example 45 
96 86 14 Trace 
amount 
Example 46 
85 87 13 0 
Example 47 
94 88 11 1 
Example 48 
85 99 1 0 
Example 49 
94 97 3 0 
Example 50 
80 97 3 0 
Example 51 
72 89 11 0 
Example 52 
96 99 1 0 
Example 53 
90 98 2 0 
Example 54 
91 88 7 5 
Example 55 
93 95 5 0 
Example 56 
98 89 11 Trace 
amount 
Example 57 
98 99 1 0 
Example 58 
73 88 12 0 
Example 59 
87 85 15 Trace 
amount 
______________________________________ 
The entire disclosure of Japanese Patent Application Nos. 08-186372i 
08-186373 and 08-186374 filed on Jul. 16, 1996 including specification, 
claims and summary are incorporated herein by reference in its entirety.