3-(2-Thiophenesulfonyl)-2-halopropanenitriles of the formula ##STR1## wherein R is H, C.sub.1-4 alkyl, Br or Cl and X is Br or Cl. The compounds have antimicrobial utility.

DESCRIPTION OF THE PRIOR ART 
U.S. Pat. No. 3,238,094 discloses phenylsulfonyl haloalkanenitriles wherein 
the phenyl group may be substituted and the haloalkanenitriles are 
halopropionitriles, halo being chloro or bromo. The compounds are said to 
be bactericidal and fungicidal. U.S. Pat. No. 3,903,298 discloses 
compounds of the formula RSO.sub.3 CH.sub.2 CN where R is said to be 
phenyl, substituted phenyl, thienyl or substituted thienyl. The sole 
thienyl compound actually disclosed is cyanomethyl 2-thiophenesulfonate. 
The compounds are said to inhibit plant pathogenic bacteria and fungi. 
SUMMARY OF THE INVENTION 
This invention concerns 3-(2-thiophenesulfonyl)-2-halopropanenitriles 
represented by the formula 
##STR2## 
wherein R is H, C.sub.1-4 alkyl, Br or Cl and X is Br or Cl. The compounds 
have antimicrobial utility. The compounds are adducts of a 
thiophenesulfonyl halide and acrylonitrile. 
The compounds are prepared by reacting a 2-thiophenesulfonyl chloride or 
bromide with acrylonitrile in the presence of acetonitrile, anhydrous 
cupric chloride or bromide and a tri-(lower alkyl) amine hydrochloride or 
hydrobromide, advantageously by freezing the mixture, evacuating the 
vessel containing the mixture and heating the sealed mixture in an oil 
bath at about 115.degree. C. until reaction is substantially complete, 
usually within about 24 hours. After cooling, the seal of the reaction 
container is broken and the contents transferred to a vessel, the 
volatiles are removed in vacuo and a residual heavy oil product is 
recovered. It is mixed with a small amount of lower alkanol, 
advantageously methanol, and the resulting solution is cooled to give 
crude product. The crude product is recrystallized from absolute ethanol 
to give purified product as small plates. In the reaction, a substantial 
excess of acrylonitrile is used, usually about 2 molar proportions per 
molar proportion of the 2-thiophenesulfonyl halide. The primary reactant 
may be either a 2-thiophenesulfonyl chloride or bromide. When the chloride 
is used, then a tri-(lower alkyl) amine hydrochloride and cupric chloride 
are used in the reaction mixture, and when the sulfonyl bromide is used as 
primary reactant, then a tri-(lower alkyl) amine hydrobromide and cupric 
bromide are used in the reaction mixture. 
The compounds have antimicrobial utility. In conventional in vitro agar 
Petri dish dilution tests for determining antimicrobial activity, the 
compounds of the Examples had minimum inhibitory concentrations (MIC) 
against the indicated organisms in parts per million (ppm) as follows: 
TABLE I 
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Compound 
of MIC, ppm 
Example 
Sa* 
Ec Ca Tm An Be Aa Cp Pp St Ps 10 
CI Tr 42 
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1 100 
100 
10 10 100 
100 
100 
10 10 100 
100 
100 
100 
2(a) 50 -- 50 50 50 
10 50 
50 50 50 500 
50 
50 
2(b) 5 50 
500 
50 500 
5 100 
100 
500 
5 500 
100 
500 
2(c) 5 500 
50 50 500 
5 500 
50 50 50 500 
50 
500 
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*Sa = S. aureus 
Ec = E. coli 
Ca = C albicans 
Tm = T. mentagrophytes 
An = A. niger 
Bs = B. subtilis 
Aa = A. aerogenes 
Cp = C. pelliculosa 
Pp = P. pullulans 
St = S. typhosa 
Ps 10 = Pseudomonas Sp. Strain 10 
CI = Ceratocystis IPS 
Tr 42 = Trichoderm Sp. Madison P42 
-- = not tested

DESCRIPTION OF SOME PREFERRED EMBODIMENTS 
The following additional description and examples further describe the 
invention and the manner and process of making and using it to enable the 
art skilled to make and use the same and set forth the best mode 
contemplated by the inventor of carrying out the invention. 
EXAMPLE 1--3-(2-Thiophenesulfonyl)-2-chloropropane nitrile 
In a Fisher-Porter pressure reactor were placed 18.26 g (0.10 mol) of 
2-thiophenesulfonyl chloride, 10.60 g (0.20 mol) of acrylonitrile, 2 g of 
acetonitrile, 0.130 g (1.0 mmol) of cupric chloride, and 0.210 g (1.5 
mmol) of triethylamine hydrochloride. The contents of the tube were frozen 
in a solid carbon dioxide bath, then evacuated to a pressure of 2 mm Hg 
and sealed. The tube was then heated in an oil bath at 115.degree. C. for 
24 hours. The tube was allowed to cool, and the contents were transferred 
to a single-neck, round-bottom flask. The volatiles were removed in vacuo, 
leaving a heavy oil. A small amount of methanol was added thereto, and the 
resulting solution was cooled to give 10.55 g of crude product. The crude 
product was recrystallized from absolute ethanol to give 4.13 g of the 
title compound as small plates, mp 80.degree.-82.degree. C. A 4.00 g 
second crop, mp 78.degree.-80.degree. C., was also obtained. 
Anal. Calculated for C.sub.7 H.sub.6 ClNO.sub.2 S.sub.2 : C, 35.67; H, 
2.56; N, 5.94; S, 27.21. Found: C, 35.70; H, 2.64; N, 6.13; S, 27.40. 
EXAMPLE 2--3-(5-Lower alkyl-2-thiophenesulfonyl)-2-chloropropanenitrile 
The procedure of Example 1 was repeated, substituting (a) 5-methyl-, (b) 
5-ethyl- and (c) 5-n-butyl-substituted-2-thiophenensulfonyl chloride in 
place of 2-thiophenesulfonyl chloride to obtain the corresponding homologs 
of Example 1. Their physical properties are summarized in the following 
Table: 
TABLE II 
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Compound Analysis 
of Calculated Found 
Example 
M.p., .degree.C. 
C H N Cl C H N Cl 
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2(a) 84 38.5 
3.2 
5.62 
14.25 
38.3 
3.26 
5.50 
13.9 
2(b) 142-144 
-- 3.82 
5.30 
-- -- 4.13 
5.22 
-- 
2(c) 133 -- 4.84 
4.80 
12.10 
-- 5.09 
4.71 
12.01 
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-- = not determined 
Preparation of Starting Materials 
The 2-thiophenesulfonyl chlorides are prepared by the method disclosed in 
Chemical Abstracts 56:456f, German Pat. No. 1,088,509. The corresponding 
sulfonyl bromides are prepared by adding to a solution of methanol and 
hydrazine a 2-thiophenesulfonyl chloride at a reaction temperature between 
about 7.degree. and about 15.degree. C. to form the corresponding 
thiophenesulfonyl hydrazine, allowing the reaction mixture to warm to room 
temperature, removing the methanol in vacuo, recovering a mixture of a 
heavy oil and a solid, treating the mixture with water whereby the solid 
is dissolved and the oil is separated. Thereafter, the mixture of oil and 
water is mixed in a flask containing chloroform and a magnetic stirrer, 
crushed ice is added thereto and to the resulting slurry is added bromine 
to form the sulfonyl bromide, the bromine being added at such a rate that 
the reaction temperature remains below 10.degree. C. After the addition of 
bromine is complete and the bromine color has dissipated, the layers are 
separated, the chloroform layer is dried over magnesium sulfate, and the 
chloroform removed in vacuo to leave a yellow oil which crystallizes on 
addition of hexane. The solid is filtered and dried to give the 
corresponding sulfonyl bromide in crystalline form.