Triazolyl-mercaptides and their use as microbicides

Triazoyl mercaptides of the formula (I) ##STR1## in which M is an alkaline metal cation, an equivalent of an alkaline earth cation, an equivalent of a copper zinc, iron or nickel cation or an ammonium cation and PA0 R.sup.1 is various radicals, a process for the production of the novel substances and their use to combat undesired micro-organisms.

Preparation and use of the substances according to the invention can be 
seen from the examples which follow. 
PREATION EXAMPLES 
Example 1 
##STR645## 
At room temperature, a solution of 50 g (0.146 mol) of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1- 
yl)-propan-2-ol in 730 ml of absolute ethanol is admixed dropwise with 
stirring with a solution of 5.84 g (0.146 mol) of sodium hydroxide in 365 
ml of absolute ethanol. After the addition has ended, the reaction mixture 
is concentrated under reduced pressure. The residue that remains is washed 
with n-hexane and dried. In this manner, 52.8 g (98% of theory) of the 
sodium salt of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1- 
yl)-propan-2-ol are obtained in the form of a solid substance of melting 
point 268-270.degree. C. 
Example 2 
##STR646## 
At room temperature, a solution of 1.72 g (5 mmol) of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1- 
yl)-propan-2-ol in 20 ml of absolute methanol is admixed dropwise with 
stirring with a solution of 0.5 g (2.5 mmol) of copper(II) acetate in 5 ml 
of water. After the addition has ended, the reaction mixture is heated 
with stirring at 50.degree. C. for 2 hours. The reaction mixture is 
subsequently concentrated under reduced pressure. The residue that remains 
is dried under high vacuum. In this manner, 1.9 g (100% of theory) of the 
copper salt of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1- 
yl)-propan-2-ol are obtained in the form of a solid substance of melting 
point 107-109.degree. C. 
Example 3 
##STR647## 
At room temperature, a solution of 1.72 g (5 mmol) of 
2-(1-chlorocyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1-y 
l)-propan-2-ol in 20 ml of dichloromethane is admixed dropwise with 
stirring with 0.5 g (5 mmol) of triethylamine. After the addition has 
ended, the reaction mixture is initially stirred for a further hour at 
20.degree. C. and then concentrated under reduced pressure. The residue 
that remains is dried under high vacuum. In this manner, 2.2 g (99% of 
theory) of the triethylammonium salt of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,5-triazol-1- 
yl)-propan-2-ol are obtained in the form of an oil. 
.sup.1 H NMR spectrum (200 MHz; CDCl.sub.3 ; TMS): .delta.=0.6-0.9 (m, 4H); 
1.3 (t, 9H); 3.2 (q, 6H); 3.35 (AB, 2H); 4.65 (AB, 2H); 5.9 (s, OH); 
7.1-7.65 (m, 4H); 7.6 (s, 1H); 11.7 (NH) ppm. 
The compounds listed in the Examples below are also prepared by the method 
given in Example 3. 
Example 4 
##STR648## 
Oil 
.sup.1 H NMR spectrum (200 MHz; CDCl.sub.3, TMS): .delta.=0.6-1.0 (m, 4H); 
0.95 (t, 9H); 1.3-1.7 (m, 12H), 3.0 (m, 6H); 3.15 (d, 1H); 3.55 (d, 1H); 
4.55 (d, 1H); 4.75 (d, 1H); 6.05 (OH); 7.1-7.65 (m, 4H); 7.55 (s, 1H); 
11.6 (NH) ppm. 
Example 5 
##STR649## 
Melting point: 86.degree. C. 
Example 6 
##STR650## 
Oil 
.sup.1 H NMR spectrum (400 MHz; CDCl.sub.3, TMS): .delta.=0.7-0.9 (m, 4H); 
0.9 (t, 9H); 1.25 (m, 30H); 1.5 (m, 3H); 2.8 (t, 2H); 3.2 (d, 1H); 3.5 (d, 
.sub.1 H); 4.5 (d, .sub.1 H); 4.75 (d, .sub.1 H); 6.2 (OH); 7.5-7.55 (m, 
4H); 7.65 (s, 1H) ppm. 
Example 7 
##STR651## 
Melting point: 132-135.degree. C. 
Example 8 
##STR652## 
At room temperature, 1.72 g (5 mmol) of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1- 
yl)-propan-2-ol and 0.91 g (5 mmol) of tetramethylammonium hydroxide in the 
form of the pentahydrate are dissolved with stirring in 30 ml of 
dichloromethane. The reaction mixture is subsequently concentrated under 
reduced pressure. The residue that remains is dried under high vacuum. In 
this manner, 2.1 g (100% of theory) of the tetramethylammonium salt of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1- 
yl)-propan-2-ol are obtained in the form of a solid substance of melting 
point 155.degree. C. 
Preparation of starting materials: 
Example 9 
##STR653## 
Variant .alpha.: 
At -20.degree. C., a mixture of 3.12 g (10 mmol) of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(1,2,4-triazol-1-yl)-propan- 
2-ol and 45 ml of absolute tetrahydrofuran is admixed with 8.4 ml (21 mmol) 
of n-butyllithium in hexane and stirred at 0.degree. C. for 30 minutes. 
The reaction mixture is then cooled to -70.degree. C., admixed with 0.32 g 
(10 mmol) of sulphur powder and stirred at -70.degree. C. for 30 minutes. 
The mixture is warmed to -10.degree. C., admixed with ice-water and 
adjusted to pH 5 by addition of dilute sulphuric acid. The mixture is 
extracted repeatedly with ethyl acetate and the combined organic phases 
are dried over sodium sulphate and concentrated under reduced pressure. In 
this manner, 3.2 g (93% of theory) of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1- 
yl)-propan-2-ol are obtained in the form of a solid substance which, after 
recrystallization, melts at 138-139.degree. C. 
Variant .beta.: 
A mixture of 3.12 g (10 mmol) of 
2-(1-chloro-cyclopropyl)-1-(2-chloro-phenyl)-3-(1,2,4-triazol-1-yl)-propan 
-2-ol, 0.96 g (30 mmol) of sulphur powder and 20 ml of absolute 
N-methyl-pyrrolidone is heated with stirring at 200.degree. C. for 44 
hours. The reaction mixture is subsequently concentrated under reduced 
pressure (0.2 mbar). The resulting crude product (3.1 g) is recrystallized 
from toluene. In this manner, 0.7 g (20% of theory) of 
2-(1-chloro-cyclopropyl)-1-(2-chlorophenyl)-3-(5-mercapto-1,2,4-triazol-1- 
yl)-propan-2-ol is obtained in the form of a solid substance of melting 
point 138-139.degree. C. 
Example 10 
##STR654## 
At -70.degree. C., a mixture of 1.41 g (5 mmol) of 
1,2-dichloro-4,4-dimethyl-5-fluoro-3-hydroxy-3-[(1,2,4-triazol-1-yl)-methy 
l]-1-pentene and 25 ml of absolute tetrahydrofuran is admixed with 4 ml (10 
mmol) of n-butyl-lithium in hexane and stirred at -70.degree. C. for one 
hour. The reaction mixture is then admixed with 0.19 g (6 mmol) of sulphur 
powder and stirred at -70.degree. C. for 4 hours. The mixture is 
subsequently hydrolyzed by adding 1 ml of methanol and 1 ml of acetic acid 
at -70.degree. C. The reaction mixture is initially diluted with ethyl 
acetate and then extracted repeatedly with saturated aqueous ammonium 
chloride solution. The organic phase is dried over sodium sulphate and 
concentrated under reduced pressure. The resulting crude product (1.7 g) 
is purified by silica gel chromatography using a mixture of petroleum 
ether and ethyl acetate=1:1 as eluent. In this manner, 0.5 g (32% of 
theory) of 
1,2-dichloro-4,4-dimethyl-5-fluoro-3-hydroxy-3-[(5-mercapto-1,2,4-triazol- 
1-yl)-methyl]-1-pentene is obtained in the form of a solid substance of 
melting point 162-164.degree. C. 
The compounds listed in Table 13 below are also prepared by the methods 
given in Examples 9 and 10. 
TABLE 13 
__________________________________________________________________________ 
(II-b) 
#STR655## 
- 
Ex. 
Comp. Physical 
No. No. R.sup.2 R.sup.3 constant 
__________________________________________________________________________ 
11 (II-3) --CCl.dbd.CHCl --C(CH.sub.3).sub.3 mp. 168- 
169.degree. C. 
- 12 (II-4) 
#STR656## 
GC/MS (Cl):376 (M + H.sup.+) 
- 13 (II-5) 
#STR658## 
mp. 163- 164.degree. C. 
- 14 (II-6) 
--C(CH.sub.3).sub.3 mp. 
127.degree. C. 
- 15 (II-7) 
#STR661## 
Oil 662## 
- 16 (II-8) 
#STR663## 
GC/MS (Cl):340 (M + H.sup.+) 
- 17 (II-9) 
#STR665## 
GC/MS (Cl):424 (M + H.sup.+) 
- 18 (II-10) 
#STR667## 
mp. 168.degree. C. 
- 19 (II-11) 
#STR669## 
GC/MS (Cl):314 (M + H.sup.+) 
- 20 (II-12) 
#STR671## 
GC/MS (Cl):346 (M + H.sup.+) 
- 21 (II-13) 
#STR673## 
mp. 115- 118.degree. C. 
- 22 (II-14) 
--C(CH.sub.3).sub.3 GC/MS 
(Cl):340 (M + H.sup.+) 
- 23 (II-15) 
#STR676## 
GC/MS (Cl):334 (M + H.sup.+) 
- 24 (II-16) 
--C.sub.4 H.sub.9 -n *) 
__________________________________________________________________________ 
*)The compound is characterized by the following signals in the .sup.1 H 
NMR spectrum (400 MHz, CDCl.sub.3 /TMS): 
.delta. = 0.8(t, 3H); 0.85(m, 2H); 1.25(m, 2H); 1.8(m, 1H); 2.55(m, 1H); 
4.6(OH); 4.9(AB, 2H); 7.2(dd, 1H); 7.35(d, 1H); 7.7(s, 1H); 7.75(d, 1H); 
12.3(5H) ppm. 
Example 25 
##STR679## 
At -70.degree. C., a mixture of 1.3 g (4 mmol) of 
3-(2-chloro-phenyl)-2-(4-fluoro-phenyl)-2-(1,2,4-triazol-1-yl-methyl)-oxir 
ane (Z form) and 25 ml of absolute tetrahydrofuran is admixed with 2.0 ml 
(5 mmol) of n-butyl-lithium in hexane and stirred at -70.degree. C. for 1 
hour. The reaction mixture is then admixed with 0.16 g (5 mmol) of sulphur 
powder and stirred at -70.degree. C. for 4 hours. At -70.degree. C., 1 ml 
of methanol and 1 ml of acetic acid are subsequently added simultaneously, 
dropwise and with stirring. The resulting mixture is diluted with 
dichloromethane and extracted repeatedly with saturated aqueous ammonium 
chloride solution. The organic phase is dried over sodium sulphate and 
then concentrated under reduced pressure. The resulting crude product (1.9 
g), which, according to GC contains 51.0% of the desired product in 
addition to 20.7% of starting material, is recrystallized from toluene. In 
this manner, 0.8 g (55% of theory) of 
3-(2-chlorophenyl)-2-(4-fluoro-phenyl)-2-(5-mercapto-1,2,4-triazol-1-yl-me 
thyl)oxirane (Z form) is obtained as a solid substance of melting point 179 
to 180.degree. C. 
.sup.1 H NMR spectrum (200 MHz; CDCl.sub.3, TMS): .delta.=3.7 (d, J=15 Hz, 
1H); 4.1 (s, 1H); 5.15 (d, J=15 Hz, 1H); 6.95-7.6 (m, 8H); 7.65 (s, 1H); 
11.0 (SH) ppm. 
GC/MS (ci): 362 (M+H.sup.+) 
Example 26 
##STR680## 
At -20.degree. C., a mixture of 1.6 g (5 mmol) of 
5-(4-chlorobenzyl)-2,2-dimethyl-1-(1,2,4-triazol-1-yl-methyl)-cyclopentan- 
1-ol (Z form) and 30 ml of absolute tetrahydrofuran is admixed with 4 ml 
(10 mmol) of n-butyl-lithium in hexane and stirred at 0.degree. C. for 
another 30 minutes. The reaction mixture is subsequently cooled to 
-70.degree. C., admixed with stirring with 0.19 g (6 mmol) of sulphur 
powder and then stirred at -70.degree. C. for 1 hour and then at 0.degree. 
C. for 2 hours. The resulting mixture is diluted with ethyl acetate and 
extracted repeatedly with saturated aqueous ammonium chloride solution. 
The organic phase is dried over sodium sulphate and then concentrated 
under reduced pressure. The resulting crude product (2.0 g) is 
recrystallized from toluene. In this manner, 1.1 g (63% of theory) of 
5-(4-chloro-benzyl)-2,2-dimethyl-1-(5-mercapto-1,2,4-triazol-1-yl-methyl)- 
cyclopentan-1-ol (Z form) are obtained as a solid substance of melting 
point 179 to 180.degree. C. 
GC/MS (ci): 352 (M+H.sup.+) 
Example 27 
##STR681## 
At -20.degree. C., a mixture of 1.59 g (5 mmol) of 
2-(4-chloro-benzylidene)-5,5-dimethyl-1-(1,2,4-triazol-1-yl-methyl)-cyclop 
entan-1-ol and 30 ml of absolute tetrahydrofuran is admixed with 4.4 ml (11 
mmol) of n-butyl-lithium in hexane and stirred at 0.degree. C. for another 
30 minutes. The reaction mixture is subsequently cooled to -70.degree. C., 
admixed with stirring with 0.19 g (6 mmol) of sulphur powder and then 
stirred at -70.degree. C. for 1 hour and then at 0.degree. C. for 2 hours. 
The resulting mixture is diluted with ethyl acetate and extracted 
repeatedly with saturated aqueous ammonium chloride solution. The organic 
phase is dried over sodium sulphate and then concentrated under reduced 
pressure. The resulting crude product (1.9 g) is chromatographed over 
silica gel using ethyl acetate. In this manner, 0.8 g (46% of theory) of 
2-(4-chloro-benzylidene)-5,5-dimethyl-1-(5-mercapto-1,2,4-triazol-1-yl-met 
hyl)-cyclopentan-1-ol is obtained. 
.sup.1 H NMR spectrum (200 MHz; CDCl.sub.3, TMS): .delta.=0.9 (s,3H); 1.15 
(s,3H); 1.6-1.95 (m,2H); 2.4-3.0 (m,2H); 4.25 (d,1H); 4.55 (d,1H); 5.9 
(m,1H); 7.1-7.3 (m,4H); 7.6 (s,1H) ppm 
Example 28 
##STR682## 
At 0.degree. C., a mixture of 1.58 g (5 mmol) of 
bis-(4-fluoro-phenyl)-methyl-(1,2,4-triazol-1-yl-methyl)-silane and 30 ml 
of absolute tetrahydrofuran is admixed with 2 ml (5 mmol) of 
n-butyl-lithium in hexane and stirred at 0.degree. C. for 1 hour. The 
reaction mixture is subsequently cooled to -70.degree. C., admixed with 
stirring with 0.16 g (5 mmol) of sulphur powder and then stirred at 
-70.degree. C. for 1 hour and then at 0.degree. C. for 2 hours. The 
resulting mixture is diluted with ethyl acetate and extracted repeatedly 
with saturated aqueous ammonium chloride solution. The organic phase is 
dried over sodium sulphate and then concentrated under reduced pressure. 
The resulting crude product (1.8 g) is purified by silica gel 
chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as 
eluent. In this manner, 0.6 g (35% of theory) of 
bis-(4-fluoro-phenyl)-methyl-(5-mercapto-1,2,4-triazol-1-yl-methyl)-silane 
is obtained. 
.sup.1 H NMR spectrum (200 MHz; CDCl.sub.3, TMS): .delta.=0.7 (s, 3H); 4.2 
(s, 2H); 7.05 (m, 4H); 7.55 (m, 5H); 13.1 (s, 1H) ppm 
GC/MS(EI): 347 (M.sup.+, 20%) 
Example 29 
##STR683## 
At -20.degree. C., a mixture of 1.53 g (5 mmol) of 
2-(2,4-difluoro-phenyl)-1,3-bis-(1,2,4-triazol-1-yl)-propan-2-ol and 30 ml 
of absolute tetrahydrofuran is admixed with 4.4 ml (11 mmol) of 
n-butyl-lithium in hexane and stirred at 0.degree. C. for another 30 
minutes. The reaction mixture is subsequently cooled to -70.degree. C., 
admixed with stirring with 0.19 g (6 mmol) of sulphur powder and then 
stirred at -70.degree. C. for 1 hour and then at 0.degree. C. for 2 hours. 
The resulting mixture is diluted with ethyl acetate and extracted 
repeatedly with saturated aqueous ammonium chloride solution. The organic 
phase is dried over sodium sulphate and then concentrated under reduced 
pressure. The resulting crude product (2.3 g) is purified by silica gel 
chromatography using a mixture of ethyl acetate and ethanol=9:1 as eluent. 
In this manner, 1.0 g (59% of theory) of 
2-(2,4-difluoro-phenyl)-1-(5-mercapto-1,2,4-triazol-1-yl)-3-(1,2,4-triazol 
-1-yl)-propan-2-ol is obtained in the form of a solid substance of melting 
point 187.degree. C. 
GC/MS(ci): 339 (M+H.sup.+) 
Example 30 
##STR684## 
At -20.degree. C., a mixture of 1.72 g (5 mmol) of 
2,2-dimethyl-3-hydroxy-4-(1,2,4-triazol-1-yl)-1-(4-trifluoromethoxy-phenyl 
)-pentane and 30 ml of absolute tetrahydrofuran is admixed with 4.4 ml (11 
mmol) of n-butyl-lithium in hexane and stirred at 0.degree. C. for another 
30 minutes. The reaction mixture is subsequently cooled to -70.degree. C., 
admixed with stirring with 0.19 g (6 mmol) of sulphur powder and then 
stirred at -70.degree. C. for 1 hour and then at 0.degree. C. for 2 hours. 
The resulting mixture is diluted with ethyl acetate and extracted 
repeatedly with saturated aqueous ammonium chloride solution. The organic 
phase is dried over sodium sulphate and then concentrated under reduced 
pressure. The resulting crude product (2.2 g) is purified by silica gel 
chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as 
eluent. In this manner, 1.4 g (75% of theory) of 
2,2-dimethyl-3-hydroxy-4-(5-mercapto-1,2,4-triazol-1-yl)-1-(4-trifluoromet 
hoxy-phenyl)-pentane are obtained in the form of a solid substance of 
melting point 125 to 126.degree. C. 
GC/MS(ci): 376 (M+H.sup.+) 
Example 31 
##STR685## 
At -20.degree. C., a mixture of 1.48 g (5 mmol) of 
1-(4-chloro-phenoxy)-1-(1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2-ol and 30 
ml of absolute tetrahydrofuran is admixed with 4 ml (10 mmol) of 
n-butyl-lithium in hexane and stirred at -20.degree. C. for another 30 
minutes. At -20.degree. C., the reaction mixture is subsequently admixed 
with stirring with 0.19 g (6 mmol) of sulphur powder and then stirred at 
-20.degree. C. for 1 hour and then at 0.degree. C. for 2 hours. The 
resulting mixture is diluted with ethyl acetate and extracted repeatedly 
with saturated aqueous ammonium chloride solution. The organic phase is 
dried over sodium sulphate and then concentrated under reduced pressure. 
The resulting crude product (1.9 g) is purified by silica gel 
chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as 
eluent. In this manner, 0.7 g (43% of theory) of 
1-(4-chlorophenoxy)-1-(5-mercapto-1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2 
-ol is obtained in the form of a solid substance of melting point 193 to 
194.degree. C. 
MS(ci): 328 (M +H.sup.+) 
Example 32 
##STR686## 
A mixture of 2.0 g (5 mmol) of 
2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-2-(1,2,4-triazol-1-yl-methyl)-4-m 
ethyl-1,3-dioxolane, 0.32 g (10 mmol) of sulphur powder and 10 ml of 
absolute N-methylpyrrolidone is heated with stirring at 200.degree. C. for 
22 hours. The reaction mixture is subsequently concentrated under reduced 
pressure (0.2 mbar). The residue that remains is admixed with ethyl 
acetate, and the resulting mixture is extracted repeatedly with saturated 
aqueous ammonium chloride solution. The organic phase is dried over sodium 
sulphate and then concentrated under reduced pressure. The resulting crude 
product (1.8 g) is purified by silica gel chromatography using a mixture 
of petroleum ether and ethyl acetate=1:1 as eluent. In this manner, 0.9 g 
(41% of theory) of 
2-[2-chloro-4-(4-chloro-phenoxy)-phenyl]-2-[(5-mercapto-1,2,4-triazol-1-yl 
)-methyl]4-methyl-1,3-dioxolane is obtained in the form of an isomer 
mixture. 
MS(ci): 438 (M +H.sup.+, 100%) 
Example 33 
##STR687## 
Under an atmosphere of nitrogen and with stirring, a mixture of 1.42 g (5 
mmol) of 2-(2,4-dichloro-phenyl)-1-(1,2,4-triazol-1-yl)-pentane, 0.32 g 
(10 mmol) of sulphur powder and 10 ml of absolute N-methyl-pyrrolidone is 
heated at 200.degree. C. for 3 hours. The reaction mixture is subsequently 
concentrated under reduced pressure. The residue that remains is admixed 
with ethyl acetate and the resulting mixture is extracted repeatedly with 
saturated aqueous ammonium chloride solution. The organic phase is dried 
over sodium sulphate and then concentrated under reduced pressure. The 
resulting crude product (2.1 g) is purified by silica gel chromatography 
using a mixture of petroleum ether and ethyl acetate=1:1 as eluent. In 
this manner, 1.5 g (95% of theory) of 
2-(2,4-dichloro-phenyl)-1-(5-mercapto-1,2,4-triazol-1-yl)-pentane are 
obtained in the form of a solid substance of melting point 103.degree. C. 
Example 34 
##STR688## 
Under an atmosphere of nitrogen and with stirring, a mixture of 2.93 g (10 
mmol) of 
1-(4-chloro-phenoxy)-1-(1,2,4--triazol-1-yl)-3,3-dimethyl-butan--2-one, 
0.64 g (20 mmol) of sulphur powder and 10 ml of absolute 
N-methylpyrrolidone is heated at 200.degree. C. for 8 hours. The reaction 
mixture is subsequently concentrated under reduced pressure, and the 
residue that remains is dissolved in dichloromethane. The resulting 
mixture is extracted repeatedly with saturated aqueous ammonium chloride 
solution. 
The organic phase is dried over sodium sulphate and then concentrated under 
reduced pressure. The resulting crude product (2.7 g) is purified by 
silica gel chromatography using a mixture of petroleum ether and ethyl 
acetate=1:1 as eluent. In this manner, 2.0 g (62% of theory) of 
1-(4-chlorophenoxy)-1-(5-mercapto-1,2,4-triazol-1-yl)-3,3-dimethyl-butan-2 
-one are obtained in the form of a solid substance of melting point 134 to 
136.degree. C. 
Example 35 
##STR689## 
Under an atmosphere of nitrogen and with stirring, a mixture of 1.68 g (5 
mmol) of 
4-(4-chloro-phenyl)-2-cyano-2-phenyl-1-(1,2,4-triazol-1-yl)-butane, 0.32 g 
(10 mmol) of sulphur powder and 10 ml of absolute N-methylpyrrolidone is 
heated at 200.degree. C. for 47 hours. The reaction mixture is 
subsequently concentrated under reduced pressure, and the residue that 
remains is dissolved in ethyl acetate. The resulting mixture is extracted 
repeatedly with saturated aqueous ammonium chloride solution. The organic 
phase is dried over sodium sulphate and then concentrated under reduced 
pressure. The resulting crude product (1.9 g) is purified by silica gel 
chromatography using a mixture of petroleum ether and ethyl acetate=1:1 as 
eluent. In this manner, 0.7 g (38% of theory) of 
4-(4-chloro-phenyl)-2-cyano-2-phenyl-1-(5-mercapto-1,2,4-triazol-1-yl)-but 
ane is obtained in the form of an oil. 
.sup.1 H NMR spectrum (400 MHz; CDCl.sub.3, TMS): .delta.=2.4 (m, 3H); 2.75 
(m, 1H); 4.5 (AB, 2H); 7.0 (d, 2H); 7.2 (d, 2H); 7.4 (m, 3H); 7.55 (m, 
2H); 7.8 (s, 1H); 11.7 (1H) ppm. 
Example A 
Erysiphe test (barley)/curative 
Solvent: 10 parts by weight of N-methyl-pyrrolidone 
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for curative activity, young plants are dusted with spores of 
Erysiphe graminis f.sp. hordei. 48 hours after the inoculation, the plants 
are sprayed with the active compound preparation at the stated application 
rate. 
The plants are placed in a greenhouse at a temperature of approximately 
20.degree. C. and a relative atmospheric humidity of approximately 80% to 
promote the development of mildew pustules. 
Evaluation is carried out 7 days after the inoculation. 0% means an 
efficacy which corresponds to that of the control, whereas an efficacy of 
100% means that no infection is observed. 
Active compounds, active compound application rates and test results are 
shown in the table below. 
TABLE A 
__________________________________________________________________________ 
Erysiphe test (barley)/curative 
Active compound 
application 
Active compound rate in g/ha Efficacy in % 
__________________________________________________________________________ 
according to the invention 
##STR690## 250 100 
- 
##STR69 250 100 
__________________________________________________________________________ 
Example B 
Erysiphe test (barley)/protective 
Solvent: 10 parts by weight of N-methyl-pyrrolidone 
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for protective activity, young plants are sprayed with the active 
compound preparation at the stated application rate. 
After the spray coating has dried on, the plants are dusted with spores of 
Erysiphe graminis f.sp. hordei. 
The plants are placed in a greenhouse at a temperature of approximately 
20.degree. C. and a relative atmospheric humidity of approximately 80% to 
promote the development of mildew pustules. 
Evaluation is carried out 7 days after the inoculation. 0% means an 
efficacy which corresponds to that of the control, whereas an efficacy of 
100% means that no infection is observed. 
Active compounds, active compound application rates and test results are 
shown in the table below. 
TABLE B 
__________________________________________________________________________ 
Erysiphe test (barley)/protective 
Active compound 
application 
Active compound rate in g/ha Efficacy in % 
__________________________________________________________________________ 
according to the invention 
##STR692## 250 100 
- 
##STR69 250 100 
__________________________________________________________________________ 
Example C 
Erysiphe test (wheat)/curative 
Solvent: 10 parts by weight of N-methyl-pyrrolidone 
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. To test for curative activity, young plants are dusted with 
spores of Erysiphe graminis f.sp. tritici. 48 hours after the inoculation, 
the plants are sprayed with the active compound preparation at the stated 
application rate. 
The plants are placed in a greenhouse at a temperature of approximately 
20.degree. C. and a relative atmospheric humidity of approximately 80% to 
promote the development of mildew pustules. 
Evaluation is carried out 7 days after the inoculation. 0% means an 
efficacy which corresponds to that of the control, whereas an efficacy of 
100% means that no infection is observed. 
Active compounds, active compound application rates and test results are 
shown in the table below. 
TABLE C 
__________________________________________________________________________ 
Erysiphe test (wheat)/curative 
Active compound 
application 
Active compound rate in g/ha Efficacy in % 
__________________________________________________________________________ 
According to the invention 
##STR694## 250 100 
- 
##STR69 250 100 
__________________________________________________________________________ 
Example D 
Erysiphe test (wheat)/protective 
Solvent: 10 parts by weight of N-methyl-pyrrolidone 
Emulsifier: 0.6 part by weight of alkylaryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for protective activity, young plants are sprayed with the active 
compound preparation at the stated application rate. 
After the spray coating has dried on, the plants are dusted with spores of 
Erysiphe graminis f.sp. tritici. 
The plants are placed in a greenhouse at a temperature of approximately 
20.degree. C. and a relative atmospheric humidity of approximately 80% to 
promote the development of mildew pustules. 
Evaluation is carried out 7 days after the inoculation. 0% means an 
efficacy which corresponds to that of the control, whereas an efficacy of 
100% means that no infection is observed. 
Active compounds, active compound application rates and test results are 
shown in the table below. 
TABLE D 
__________________________________________________________________________ 
Erysiphe test (wheat)/protective 
Active compound 
application 
Active compound rate in g/ha Efficacy in % 
__________________________________________________________________________ 
According to the invention 
##STR696## 250 100 
- 
##STR69 250 100 
__________________________________________________________________________ 
Example E 
Sphaerotheca test (cucumber)/protective 
Solvent: 47 parts by weight of acetone 
Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for protective activity, young plants are sprayed with the active 
compound preparation at the stated application rate. After the spray 
coating has dried on, the plants are dusted with conidia of the fungus 
Sphaerotheca fuliginea. 
The plants are subsequently placed in a greenhouse at 23 to 24.degree. C. 
and a relative atmospheric humidity of approximately 75%. 
Evaluation is carried out 10 days after the inoculation. 0% means an 
efficacy which corresponds to that of the control, whereas an efficacy of 
100% means that no infection is observed. 
Active compounds, active compound application rates and test results are 
shown in the table below. 
TABLE E 
______________________________________ 
Sphaerotheca test (cucumber)/protective 
Active 
compound 
application Efficacy 
Active compound rate in g/ha in % 
______________________________________ 
According to the invention 
##STR698## 10 100 
______________________________________ 
Example F 
Botrytis test (beans)/protective 
Solvent: 47 parts by weight of acetone 
Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for protective activity, young plants are sprayed with the active 
compound preparation at the stated application rate. After the spray 
coating has dried on, 2 small pieces of agar overgrown with Botrytis 
cinerea are placed onto each leaf. The inoculated plants are placed in a 
dark humid chamber at 20.degree. C. 
3 days after the inoculation, the size of the infected areas on the leaves 
is determined and expressed in %. 0% means an efficacy which corresponds 
to that of the control, whereas an efficacy of 100% means that no 
infection is observed. 
Active compounds, active compound application rates and test results are 
shown in the table below. 
TABLE F 
______________________________________ 
Botrytis test (beans)/protective 
Active 
compound 
application Efficacy 
Active compound rate in g/ha in % 
______________________________________ 
According to the invention 
##STR699## 500 98 
______________________________________ 
Example G 
Podosphaera test (apple)/protective 
Solvent: 47 parts by weight of acetone 
Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for protective activity, young plants are sprayed with the active 
compound preparation at the stated application rate. After the spray 
coating has dried on, the plants are inoculated with an aqueous spore 
suspension of the causative organism of apple mildew Podosphaera 
leucotricha. The plants are placed in a greenhouse at approximately 
23.degree. C. and a relative atmospheric humidity of approximately 70%. 
Evaluation is carried out 10 days after the inoculation. 0% means an 
efficacy which corresponds to that of the control, whereas an efficacy of 
100% means that no infection is observed. 
Active compounds, active compound application rates and test results are 
shown in the table below. 
TABLE G 
______________________________________ 
Podosphaera test (apple)/protective 
Active 
compound Effi- 
application cacy 
Active compound rate in g/ha in % 
______________________________________ 
According to the invention 
##STR700## 50 100 
- 
##STR701# 50 100 
- 
50 1002## 
______________________________________ 
Example H 
Venturia test (apple)/protective 
Solvent: 47 parts by weight of acetone 
Emulsifier: 3 parts by weight of alkyl-aryl polyglycol ether 
To produce a suitable preparation of active compound, 1 part by weight of 
active compound is mixed with the stated amounts of solvent and 
emulsifier, and the concentrate is diluted with water to the desired 
concentration. 
To test for protective activity, young plants are sprayed with the active 
compound preparation at the stated application rate. After the spray 
coating has dried on, the plants are inoculated with an aqueous conidia 
suspension of the causative organism of apple scab Venturia inaequalis and 
then remain in an incubation cabin at approximately 20.degree. C. and 100% 
relative atmospheric humidity for 1 day. 
The plants are then placed in a greenhouse at approximately 21.degree. C. 
and a relative atmospheric humidity of approximately 90%. 
Evaluation is carried out 12 days after the inoculation. 0% means an 
efficacy which corresponds to that of the control, whereas an efficacy of 
100% means that no infection is observed. 
Active compounds, active compound application rates and test results are 
shown in the table below. 
TABLE H 
__________________________________________________________________________ 
Venturia test (apple)/protective 
Active 
compound 
application 
Active compound rate in g/ha Efficacy in % 
__________________________________________________________________________ 
According to the invention 
##STR703## 50 100 
- 
##STR 50 100 
- 
50 100 ## 
- 
50 1006## 
__________________________________________________________________________