Thiazolylidene-oxo-propionitriles, insecticidal composition containing these compounds

A thiazolylidene-oxo-propionitriles of the formula ##STR1## in which R.sub.1, R.sub.2 and R.sub.3 have the meaning defined in the specification. The compounds are valuable as insecticides of a superior activity against specific groups of insects.

BACKGROUND OF THE INVENTION 
The invention relates to thiazolylidene-oxo-propionitriles, insecticidal 
compositions containing these compounds and process for making same. 
Thiazolyl cinnamic acid nitriles with insecticidal activity have been 
disclosed in German published application No. 2,703,542. The action of 
these compounds, however, is not always adequate. 
Likewise, compositions of a different chemical structure, but having 
similar activity are, for instance, phosphoric acid esters (West German 
Patent No. 814,152), chlorinated hydrocarbons (West German Patent No. 
1,015,797), carbamates (U.S. Pat. No. 2,903,478) and pyrethroids (Belgian 
Patent No. 857,859). These agents have usually a broad range of activity. 
The object of the present invention is rather the development of an 
insecticide which has a narrow spectrum of activity and can be used 
successfully for controlling specific insects. 
ESSENCE OF THE INVENTION 
This object is met by an insecticidal agent which contains one or more 
compounds of the formula 
##STR2## 
In this formula R.sub.1 is hydrogen, halogen, C.sub.1 -C.sub.6 -alkyl, 
C.sub.3 -C.sub.6 -cycloalkyl, thienyl, pyridyl or an aromatic hydrocarbon 
residue substituted in one or several positions by the same or different 
radicals from the group constituted by C.sub.1 -C.sub.4 -alkyl, C.sub.1 
-C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, halogeno, trifluoromethyl, 
nitro and cyano. 
R.sub.2 is hydrogen, halogen, C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.6 
-cycloalkyl, thienyl, pyridyl, phenyl, or an aromatic hydrocarbon residue 
which is substituted in one or several positions by the same or different 
radicals selected from the group consisting of C.sub.1 -C.sub.4 -alkyl, 
C.sub.1 -C.sub.4 -alkoxy, C.sub.1 -C.sub.4 -alkylthio, halogeno, 
trifluoromethyl, nitro and cyano. 
R.sub.3 is an aromatic hydrocarbon residue which may also be substituted in 
one or several positions by the same or different radicals from the group 
consisting of C.sub.1 -C.sub.4 -alkyl, halogeno-C.sub.1 -C.sub.4 -alkyl, 
C.sub.1 -C.sub.4 -alkoxy, halogen, trifluoromethyl, nitro and cyano. 
The compounds of the invention have a surprising insecticidal activity 
which partly is superior to the agents of analogous chemical constitution 
and they are highly effective against very specific insects. 
A superior activity is found in the compounds of the invention, 
particularly against pests of the genera Coleopterans, Lepidopterans, 
Dipterans and Rhynchotens which are economically of great significance. 
The compounds of the invention display their superior activity at 
concentrations of about 0.005 to 5.0%, preferably between 0.01 and 0.5%. 
The compounds of the invention can either be used by themselves or 
intermixed with each other or with other insecticidal agents. If desired, 
other plant protection agents or pesticides such as acaricides or 
fungicides may be added depending on the specific objective. 
An increase of the intensity of activity and speed of activity can, for 
instance, be accomplished by additives such as organic solvents, wetting 
agents, and oils. Such additives therefore may permit a lowering of the 
dosage of the primary effective agent. 
The compounds or their mixtures are preferably used in the form of 
compositions such as powders, spraying agents, granulates, solutions, 
emulsions or suspensions. Liquid and/or solid carrier materials or 
diluents may be added and, if desired, wetting agents, adhesion promoting 
agents, emulsifier and/or dispersants, may also be added. 
Suitable liquid carriers are, for instance, water, aliphatic and aromatic 
hydrocarbons and furthermore cyclohexanone, isophorone, dimethylsulfoxide, 
dimethylformamide, and mineral oil fractions. 
As solid carrier materials there may be used mineral earths, for instance 
tonsil, silicagel, talc, kaolin, attaclay, limestone, silicic acid and 
plant products such as flours. 
There may also be added surface active agents such as 
calciumlignosulfonate, polyoxyethylene-alkylphenylether, naphthalene 
sulfonic acids and their salts, phenolsulfonic acids and their salts, 
formaldehyde condensation products, fettyl alcoholsulfates, as well as 
substituted benzosulfonic acids and their salts. 
The proportion of the active agent or agents in the different compositions 
can be varied within a broad range. The compositions may for instance 
contain about 5 to 95% by weight of active agent, about 95 to 5% by weight 
of liquid or carrier materials and, if desired, up to 20% by weight of 
surface active agents may be added upon a corresponding reduction of the 
carrier materials. 
The application of the agents can be effected in conventional form, for 
instance with water as the carrier material in spray amounts of between 
100 to 3000 l/ha (hectare=about 2.54 acres). 
The application can be effected in the so-called low volume and ultra low 
volume procedure and also in the form of so-called microgranulates. 
The making of these compositions can be effected in conventional form, for 
instance, by mixing or grinding processes. If desired, individual 
components can also be mixed only shortly prior to their use as this is 
for instance done in actual practice in the so-called tank mixing 
procedure. 
Among the compounds of the invention, those are particularly outstanding 
with regard to their insecticidal action in which in the above equation 
R.sub.1 is methylphenyl, halogenophenyl, tert.-butyl or thienyl, 
R.sub.2 is hydrogen, and 
R.sub.3 is phenyl substituted in one or two positions by the same or 
different radicals from the group consisting of methyl, fluoro, chloro, 
bromo, iodo, trifluoromethyl, nitro or methoxy. 
The compounds of the invention can be made, for instance, by a process in 
which thiazolyl acetonitriles of the formula 
##STR3## 
or their alkali salts are reacted with acid halides of the formula 
EQU R.sub.3 --CO--X 
in which case the reaction may take place in an inert solvent upon addition 
of an organic base. R.sub.1, R.sub.2 and R.sub.3 in these equations have 
the same significance as in the above broad formula of the final 
compounds. X is halogen and preferably chlorine. 
The reaction preferably is carried out by heating a mixture of the reaction 
components to between 120.degree. and 160.degree. C. or a solution thereof 
in an inert solvent such as xylene to about 140.degree. C. upon addition 
of catalytic amounts of an organic base, for instance, pyridine or 
4-dimethylaminopyridine. If the alkali salts of the thiazolyl 
acetonitriles are used, the reaction preferably is carried out at a 
temperature of -10.degree. C. to +40.degree. C. in dimethylformamide, 
tetrahydrofuran or ether.

The following examples will further illustrate the making of the compounds: 
EXAMPLE 1 
3-(2-chloro-6-fluorophenyl)-2-(4-tert.-butyl-2,3-dihydrothiazol-2-ylidene)- 
3-oxopropionitrile 
155 g (1.55 mol) of cyanothioacetamide dissolved in 17.1 of ethanol and 
40.degree. C. were reacted in a rapid operation with 280 g (1.55 mol) 
bromopinacoline and are subjected to boiling under reflux for 1 hour. 
After concentration in a vacuum the residue was treated with an aqueous 
sodium carbonate solution and extracted with methylene chloride. The 
organic phase was dried on magnesium sulfate, concentrated and distilled 
in a high vacuum. 
The yield was 178 g=63% of the theoretical value of 
4-tert.-butyl-2-cyanomethylthiazole. 
bp.sub.2 : 101.degree.-118.degree. C. 
9.0 g (0.05 mol) of the just obtained thiazol and 0.5 g of 
4-dimethylaminopyridine were suspended in 20 ml xylene. After adding 9.7 g 
(0.05 mol) of 2-chloro-6-fluorobenzoylchloride the mass was subjected to 
boiling under reflux for 20 minutes. The solvent was distilled off in a 
vacuum and the residue was heated with 20 ml ethanol for 5 minutes. After 
further concentration in a vacuum recrystallization was effected from 
ethanol. 
The yield was 5.1 g=30% of the theoretical value of 
3-(2-chloro-6-fluorophenyl)-2-(4-tert.-butyl-2,3-dihydrothiazole-2-ylidene 
)-3-oxopropionitrile. 
mp: 198.degree.-199.degree. C. 
EXAMPLE 2 
3-(2-chlorophenyl)-2-[4-(2-methylphenyl)-2,3-dihydrothiazole-2-ylidene]-3-o 
xopropionitrile 
A solution of 94 g (0.94 mol) of cyanothioacetamide in 1 l ethanol was 
slowly reacted at 40.degree. C. upon stirring with 50.6 g (0.94 mol) of 
sodium ethylate. After 10 minutes 200 g (0.94 mol) of 
2-methyl-.omega.-bromoacetophenone were added dropwise and the mass was 
then subjected to boiling upon reflux for 20 minutes. 
The solution was concentrated in a vacuum and stirred into 4 l of water. 
The aqueous phase was extracted several times with ethylene chloride. The 
combined organic phases were dried on magnesium sulfate and concentrated 
in a vacuum. The oily residue was distilled in a high vacuum. 
The yield was 76 g=38% of the theoretical value of 
2-cyanomethyl-4-(2-methylphenyl)-thiazole. 
bp.sub.0.1 : 159.degree.-162.degree. C. 
10.7 g (0.05 mol) of the just obtained thiazole were suspended in 20 ml 
xylene and reacted with 0.5 g of 4-dimethyl-aminopyridine. After adding 
8.8 g (0.05 mol) of 2-chlorobenzoyl chloride, the mass was boiled for 20 
minutes upon reflux. The solvent was then removed in a vacuum and the mass 
was boiled with 20 ml methanol and again concentrated. The residue was 
recrystallized from acetonitrile. 
The yield was 9.5 g=54% of the theoretical value of 
3-(2-chlorophenyl)-2-(4-(2-methylphenyl)-2,3-dihydrothiazole-2-ylidene)-3- 
oxopropionitrile. 
mp.: 168.degree. C. 
In an analogous manner the following compounds were made: 
______________________________________ 
Compound Physical constants 
______________________________________ 
3-(2-methylphenyl)-2-(5-methyl- 
4-phenyl-2,3-dihydrothiazole-2- 
ylidene)-3-oxopropionitril 
m.p.: 108-100.degree. C. 
3-(2-fluorophenyl)-3-oxo-2-(4- 
tert.-butyl-2,3-dihydrothia- 
zole-2-ylidene)-propionitrile 
m.p.: 176-177.degree. C. 
3-(2-chlorophenyl)-3-oxo-2-(4- 
tert.-butyl-2,3-dihydrothia- 
zole-2-ylidene)-propionitrile 
m.p.: 217-219.degree. C. 
2-(4-tert.-butyl-2,3-dihydro- 
thiazole-2-ylidene)-3-(2-tri- 
fluoromethylphenyl)-3-oxopro- 
pionitrile m.p.: 195-196.degree. C. 
3-(2-chlorophenyl)-3-oxo-2-[4- 
(2-thienyl)-2,3-dihydrothia- 
zole-2-ylidene]-propionitrile 
m.p.: 162-163.degree. C. 
3-(2-bromophenyl)-3-oxo-2-[4- 
(2-thienyl)-2,3-dihydrothia- 
zole-2-ylidene]-propionitrile 
m.p.: 147-148.degree. C. 
3-(2-fluorophenyl)-2-[4-(2- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
pionitrile m.p.: 163-164.degree. C. 
3-(2-chloro-6-fluorophenyl)-2- 
[4-(2-methylphenyl)-2,3-di- 
hydrothiazole-2-ylidene]-3-oxo- 
propionitrile m.p.: 191-192.degree. C. 
3-(2-bromophenyl)-2-[4-(2- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
pionitrile m.p.: 167-168.degree. C. 
3-(2-methoxyphenyl)-2-[4-(2- 
methylphenyl)-2,2-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
pionitrile m.p.: 149-151.degree. C. 
3-(2-iodophenyl)-2-[4-(2-me- 
thylphenyl)-2,3-dihydrothiazole- 
2-ylidene]-3-oxopropionitrile 
m.p.: 165-166.degree. C. 
3-(2-chlorophenyl)-2-[4-(3- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
pionitrile m.p.: 157-158.degree. C. 
2-[4-(2-chlorophenyl)-2,3-di- 
hydrothiazole-2-ylidene]-3-oxo- 
3-phenylpropionitrile m.p.: 170-170.5.degree. C. 
3-(2-chlorophenyl)-2-[4-(2- 
chlorophenyl)-2,3-dihydrothiazole- 
2-ylidene]-3-oxopropionitrile 
m.p.: 170-171.degree. C. 
3-(2-chlorophenyl)-2-[4-(2- 
fluorophenyl)-2,3-dihydrothia- 
zole-2-ylidene]-3-xoxpropionitrile 
m.p.: 164-170.degree. C. 
2-(5-bromo-4-phenyl-2,3-dihydro- 
thiazole-2-ylidene)-3-(2-chloro- 
phenyl)-3-oxopropionitrile 
m.p.: 143.degree. C. 
(decomposition) 
3-(2-chlorophenyl)-3-oxo-2-[4-(2- 
pyridyl)-2,3-dihydrothiazole-2- 
ylidene]-propionitrile 
m.p.: 200-201.degree. C. 
______________________________________ 
The compounds of the invention are usually practically insoluble in water 
and gasoline. They are moderately soluble in methanol, acetone and acetic 
acid ester and have a good solubility in dimethylformamide. They are 
crystalline bodies. 
The following examples will further illustrate the application and activity 
of the compounds of the invention: 
USE AND ACTIVITIES 
EXAMPLE 3 
The compounds of the inventions were used in this Example as aqueous 
suspensions in the concentration indicated in the Table below. 
These active agents in the form of 4 mg of a spray/cm.sup.2 were sprayed on 
cauliflower leaves disposed in polystyrene Petri dishes. After drying of 
the deposits 10 juvenile caterpillars of the cabbage moth (Plutella 
maculipennis), were placed into each Petri dish, and the Petri dishes were 
closed for 2 days to leave the caterpillars with the feed indicated. 
In the Table below the criteria for the activity was the mortality of the 
caterpillars stated in percentage after 2 days. 
______________________________________ 
Concentration of 
Mortality 
Compound active agents in % 
in % 
______________________________________ 
3-(2-methylphenyl)-2-(5- 
methyl-4-phenyl-2,3-di- 
hydrothiazole-2-ylidene)- 
0.1 100 
3-oxopropionitrile 
3-(2-fluorophenyl)-3-oxo- 
2-(4-tert.-butyl-2,3-di- 
hydrothiazole-2-ylidene)- 
0.1 100 
propionitrile 
3-(2-chlorophenyl)-3-oxo-2- 
(4-tert.-butyl-2,3-dihydro- 
thiazole-2-ylidene)-propioni- 
0.1 100 
trile 
3-(2-chloro-6-fluorophenyl)- 
2-(4-tert.-butyl-2,3-di- 
hydrotiazole-2-ylidene)-3- 
0.1 100 
oxopropionitrile 
2-(4-tert.-butyl-2,3-dihydro- 
thiazole-2-ylidene)-3-(2-tri- 
fluoromethylphenyl)-3-oxopro- 
0.1 100 
pionitrile 
3-(2-chlorophenyl)-3-oxo-2-[4- 
(2-thienyl)-2,3-dihydrothia- 
0.1 100 
zole-2-ylidene]-propionitrile 
3-(2-bromophenyl)-3-oxo-2-[4- 
(2-thienyl)-2,3-dihydrothia- 
0.1 100 
zole-2-ylidene]-propionitrile 
3-(2-chlorophenyl)-2-[4-(2- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
0.1 100 
pionitrile 
3-(2-fluorophenyl)-2-[4-(2- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
0.1 100 
pionitrile 
3-(2-chloro-6-fluorophenyl) 
2-[4-(2-methylphenyl)-2,3- 
dihydrothiazole-2-ylidene]-3- 
0.1 100 
oxopropionitrile 
3-(2-bromophenyl)-2-[4-(2- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
0.1 100 
3-(2-methoxyphenyl)-2-[4-(2- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxo- 
0.1 100 
propionitrile 
3-(2-iodophenyl)-2-[4-(2- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
0.1 100 
pionitrile 
3-(2-chlorophenyl)-2-[4-(3- 
methylphenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
0.1 100 
pionitrile 
2-[4-(2-chlorophenyl)-2,3-di- 
hydrothiazole-2-ylidene]-3- 
0.1 100 
oxo-3-phenylpropionitrile 
3-(2-chlorophenyl)-2-[4-(2- 
chlorophenyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxopro- 
0.1 100 
pionitrile 
3-(2-chlorophenyl)-2-[4-(2- 
fluorophenyl)-2,3-dihydrothia- 
0.1 100 
zole-2-ylidene]-3-oxopropionitrile 
2-(5-bromo-4-phenyl-2,3-di- 
hydrothiazole-2-ylidene)-3- 
(2-chlorophenyl)-3-oxopropio- 
0.1 100 
nitrile 
3-(2-chlorophenyl)-3-oxo-2-[4- 
(2-pyridyl)-2,3-dihydrothiazole- 
0.1 100 
2-ylidene]-propionitrile 
______________________________________ 
EXAMPLE 4 
The compounds of the invention were used in this example as aqueous 
suspensions in the concentration indicated in the Table below. The 
comparison compounds were likewise diluted with water so as to form 
suspensions or emulsions in the concentrations indicated. 
These active agents were then sprayed in dosages of 4 mg spray amounts 
cm.sup.2 into the lids and bottoms of polystyrene Petri dishes. To these 
spray deposits there were then exposed 25 adult Mediterranean fruit flies 
(Ceratitis capitata) per dish for 48 hours. The test was carried out in 
the laboratory with the Petri dishes closed and under conditions of a 
long-day illumination. 
The criterium for the activity was the mortality of the flies expressed in 
percentages after 48 hours. The data appear from the following Table. 
______________________________________ 
Concentration 
Mortality 
of active agent 
in % 
in % after 48 h 
______________________________________ 
Compound 
2-(4-tert.-butyl-2,3-di- 
hydrothiazole-2-ylidene)- 
3-(2-trifluoromethylphenyl)- 
0.0025 90 
3-oxopropionitrile 
3-(2-chloro-6-fluorophenyl)- 
2-[4-(2-methylphenyl)-2,3- 
dihydrothiazole-2-ylidene]- 
0.0025 98 
3-oxopropionitrile 
3-(2-iodophenyl)-2-[4-(2- 
methyl henyl)-2,3-dihydro- 
thiazole-2-ylidene]-3-oxo- 
0.0025 95 
propionitrile 
3-(2-chlorophenyl)-2-[4-(2- 
chlorophenyl)-2,3-dihydrothia- 
zole-2-ylidene]-3-oxopropioni- 
0.0025 93 
trile 
COMISON COMPOUNDS 
2'-chloro-3-hydroxy-2-(4- 
phenyl-2-thiazolyl)-cinnamic 
acid nitrile 0.0025 73 
(West German Patent OS 27 03 542) 
2-(4-chlorophenyl)-isovaleric acid 
(.alpha.-cyano-3-phenoxybenzyl)-ester 
(Belgian Patent PS 857-859) 
0.0025 65 
6,7,8,9,10,10-hexachloro-1,5,5a, 
6,9,9a-hexahydro-6,9-methano- 
2,4,3-benzodioxathiepine-3-oxyd 
(West German Patent 1,015,797) 
0.0025 68 
______________________________________ 
EXAMPLE 5 
The compounds of the invention were used as aqueous suspensions in the 
concentrations indicated below. The comparison compounds were likewise 
diluted with water and used as suspensions or emulsions in the indicated 
concentrations. 
These active agents were then sprayed in amounts of 4 mg of spray 
amounts/cm.sup.2 on cauliflower leaves disposed in polystyrene Petri 
dishes. After drying of the spray deposits there were placed ten juvenile 
caterpillars of the cabbage moth (Plutella maculipennis) into each dish 
and the caterpillars were then left for 2 days in the closed Petri dishes 
with the indicated feed. 
The criterium for the activity was the mortality of the caterpillar 
expressed in percentages after 2 days. The data are compiled in the 
following Table. 
______________________________________ 
Concentration of 
Mortality 
active agent in % 
in % 
______________________________________ 
Compound 
3-(2-chloro-6-fluorophenyl)- 
2-(4-tert.-butyl-2,3-di- 
0.01 100 
hydrothiazole-2-ylidene)-3- 
0.005 65 
oxopropionitrile 
3-(2-chloro-6-fluorophenyl)- 
2-4-(2-methylphenyl)-2,3- 
0.01 90 
dihydrothiazole-2-ylidene- 
0.005 90 
COMISON COMPOUNDS 
2'-bromo-3-hydroxy-2-(4-phenyl- 
2-thiazolyl)-cinnamic acid 
0.01 90 
nitrile 0.005 50 
(German published application 
27 03 542) 
1-naphthyl-methylcarbamate 
0.01 50 
(U.S. Pat. 2,903,478) 
0.005 10 
0,0-dimethyl-0-(p-nitro- 
phenyl)-thiono-phosphoric 
0.01 70 
acid ester 0.005 50 
(German Patent 814,152 
______________________________________ 
Without further analysis, the foregoing will so fully reveal the gist of 
the present invention that others can, by applying current knowledge, 
readily adapt it for various applications without omitting features that, 
from the standpoint of prior art, fairly constitute essential 
characteristics of the generic or specific aspects of this invention.