Novel carbamic acid ester derivatives, pesticidal compositions containing them and a process for their preparation

The present invention relates to pesticides containing carbamic acid ester derivatives of the formula (I), ##STR1## to pesticide compositions containing these compounds and to a process for their preparation. In the general formula PA0 R.sup.1 is alkyl of from one to four carbon atoms; PA0 R.sup.2 represents alkyl of from one to four carbon atoms or (when X is alkyl of from one to twelve carbon atoms) alkyl of from one to twelve carbon atoms; PA0 R.sup.3 is H, methyl or ethyl; PA0 R.sup.4 and R.sup.5 are, independently from each other, H or halogen atoms; PA0 n=0, 1 or 2; PA0 X represents alkyl of from one to twelve carbon atoms or an 4-aryloxyphenoxyalkyl group of formula (II). ##STR2## The pesticide of the invention can be used for controlling insects and mites.

The present invention relates to N-sulfenyl-carbamic acid esters, 
N-sulfinyl-carbamic acid esters and N-sulfonyl-carbamic acid esters of the 
formula (I), 
##STR3## 
to processes for their preparation, to their use in pest control, 
especially as insecticides and acaricides, and pesticidal compositions. 
The compounds having the general formula (I), 
wherein 
R.sup.1 is alkyl of from one to four carbon atoms; 
R.sup.2 represents alkyl of from one to four carbon atoms or (when X is 
alkyl of from one to twelve carbon atoms) alkyl of from one to twelve 
carbon atoms; 
R.sup.3 is H, methyl or ethyl; 
R.sup.4 and R.sup.5 are, independently from each other, H or halogen, 
preferably Cl, Br or F atoms; 
n=0, 1 or 2; 
X represents alkyl of from one to twelve carbon atoms or an 
4-aryloxyphenoxyalkyl group of formula (II), 
##STR4## 
where R.sup.3, R.sup.4 and R.sup.5 are as above. 
If X stands for the group of formula (II), then R.sup.3, R.sup.4 and 
R.sup.5 correspond to the groups R.sup.3, R.sup.4, and R.sup.5 in formula 
(I). 
If X represents alkyl of from one to twelve carbon atoms, it is preferably 
alkyl of from one to eight carbon atoms. Examples of such groups are 
methyl, ethyl, n-propyl, isopropyl, n-butyl, n-octyl and the like. 
If R.sup.2 represents alkyl of from one to twelve carbon atoms, examples of 
such groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, n-octyl, 
n-dodecyl and the like. 
The alkyl groups defined above may have straight or branched chain. 
U.S. Pat. No. 4,215,139 and European Pat. No. 4334 disclose insecticidal 
compositions containing 2-phenoxyethylcarbamates of formula (A), 
##STR5## 
wherein, inter alia, A is substituted phenyl, Z is oxygen, sulfur atom or 
methylene group, W is oxygen or sulfur, R is alkyl of from one to six 
carbon atoms, and Q is oxygen atom, sulfur atom, sulfonyl, carbonyl or 
methylene group. 
Published European patent application No. 138,037 describes pesticidal 
carbamates of formula (B), 
##STR6## 
wherein R.sup.6 is H or methyl, W is oxygen or sulfur, and R.sup.7 is 
alkyl group. 
U.S. Pat. No. 4,413,010 discloses insecticidal carbamates of formula (C), 
##STR7## 
wherein A is substituted phenyl, Z is oxygen, sulfur atom or methylene 
group, R.sup.8 is H or methyl, R.sup.9 is H or alkyl group containing one 
to four carbon atoms, Y is oxygen or sulfur and R.sup.10 is alkyl 
containing one to four carbon atoms. 
Published German patent application (DOS) No. 3,334,983 discloses 
insecticidal N-aryl-sulfenyl-carbamate derivatives of formula (D), 
##STR8## 
wherein A is substituted phenyl, R.sup.11 is alkyl or alkoxy group 
containing one to six carbon atoms, R.sup.12 and R.sup.13 are H, halogen 
nitro, trifluoromethyl or lower alkyl. 
The present invention is directed to develop novel pesticidal agents which 
are more efficient than the presently used ones and are not harmful to 
non-target organisms, especially vertebrates. 
Now we have found that pesticidal compositions containing compounds 
described by the general formula (I) as the active ingredient influence 
the hormonal regulating system of the morphogenesis of insects and mites 
and inhibit metamorphosis causing death or abnormalities at later 
developmental stages. The presently used insecticides exert their killing 
effect by acting on the nervous system. 
We have also found that compounds of formula (I) are active at very low 
doses, have longer duration of activity but they are not persistent in the 
field. They are also selective and non-toxic to vertebrates. 
The invention is also directed to processes for the preparation of the 
compounds of formula (I). 
The compounds of formula (I) can be prepared by methods (a) or (b) as shown 
on Schemes [A] and [B]. 
##STR9## 
(a) Carbamate derivatives of formula (I), where X stands for a group (II), 
R.sup.1, R.sup.2, R.sup.3, R.sup.4, R.sup.5 and n are as defined above, 
are prepared by reacting a carbamic acid derivative of formula (III) with 
a sulfur compound of the general formula S(O).sub.n Y.sub.2, wherein Y is 
halogen, preferably Cl or Br and n is 0, 1 or 2. 
The reaction is carried out in an inert, aprotic organic solvent, 
preferably diethyl ether, tetrahydrofuran, acetone, halogenated 
hydrocarbons or pyridine, or a mixture of these solvents. The use of an 
acid acceptor is advantageous. Sulfur dichloride, sulfur monochloride, 
thionyl chloride and sulfuryl chloride can be used as sulfur compound. The 
reaction temperature can range from -10.degree. C. to the boiling point of 
the solvent. As acid acceptor, the usual inorganic or organic bases can be 
used. These are alkali metal carbonates (e.g. K.sub.2 CO.sub.3), alkali 
metal hydrides (e.g. NaH), or tertiary amines containing one or two 
nitrogen atoms, such as triethylamine, pyridine, 4-dimethylaminopyridine, 
1,4-diazabicyclo[2.2.2]octane or a mixture thereof. Pyridine can also be 
used as solvent. The molar ratio of carbamate (III), the sulfur compound 
and the acid acceptor is preferably 2:1-1.2:1.9-50. The reaction product 
is separated from the reaction mixture by known procedures, e.g. by 
extraction. 
(b) For the preparation of compounds (I), where X is an alkyl group 
containing one to twelve carbon atoms and the other substituents have the 
same meaning as reported earlier, the carbamate of formula (III) is 
reacted with a carbamate derivative of formula (IV), where Y and n are as 
above. The reaction is carried out in an inert solvent and in the presence 
of an acid acceptor as described in Method (a), at a temperature ranging 
from -10.degree. C. to the boiling point of the solvent. 
The molar ratio of compounds (III), (IV) and the acid acceptor is 
preferably 1:1-2:0.9-20. 
Compounds of formula (IV) can be preferably prepared "in situ", immediately 
before the reaction described above, from the corresponding carbamic acid 
ester and a sulfur compound of formula S(O).sub.n Y.sub.2, where n is as 
defined above. 
The reaction product is isolated by known procedures, for example by 
extraction. 
The starting materials for the preparation of compounds of formula (I) are 
known or can be prepared by known methods. For example, 
2-(4-phenoxyphenoxy)ethylcarbamic acid esters of formula (III) can be 
prepared as described in U.S. Pat. No. 4,215,139 or European Pat. No. 
4334. N-chlorosulfinylcarbamic acid esters of formula (IV) can be prepared 
as described by Fahmy et al. (J. Agric. Food Chem. 26, 550 /1978/). 
Compounds of formula (I) where n is 1 or 2 can be prepared by the oxidation 
of compounds of formula (I) where n is 0. The oxidation is accomplished by 
known methods using oxidizing agents, for example 1-5 molar 
equivalents--depending on the desired product--of organic peracids. The 
reaction is carried out in an inert organic solvent.

The invention is illustrated by the following non-limiting Examples. The 
structure of the compounds was proven by their elemental analyses, IR and 
NMR spectra. 
EXAMPLE 1 
Ethyl N,N'-sulfenyl-bis[2-(4-phenoxyphenoxy)-ethylcarbamate] 
(Compound No. 1) 
To an ice-cooled solution of 3.2 g (0.01 mole) of ethyl 
2-(4-phenoxyphenoxy)-ethylcarbamate, 0.9 ml of dry pyridine and 0.36 g of 
4-dimethylaminopyridine in 20 ml of dry dichloromethane 0.35 ml (0.0055 
mole) of sulfur dichloride is added, and the solution is stirred at 
ambient temperature for 18 hours. The mixture is diluted with 30 ml of 
chloroform, washed with 20 ml each of 5% hydrochloric acid solution, 
saturated sodium hydroxide carbonate solution and water, dried, and 
concentrated in vacuo. The residue is purified by column chromatography to 
give 0.77 g of a light yellowish viscous oil. The compound is 
characterized by the physical constants shown in Table 1. 
The following compounds were prepared in an analogous manner: 
Isopropyl N,N'-sulfenyl-bis(2-/4-phenoxyphenoxy/-ethylcarbamate) (Compound 
No. 2) (oil); 
Propyl N,N'-sulfenyl-bis[2-(4-/3-fluorophenoxy/-phenoxy)-ethylcarbamate] 
(Compound No. 3) (oil); 
(.+-.) Ethyl 
N,N'-sulfenyl-bis[2-(4-/2,4-dichlorophenoxy/-phenoxy)-propylcarbamate] 
(Compound No. 4) (oil); 
Ethyl N,N'-sulfenyl-bis[2-(4-/4-chlorophenoxy/-phenoxy)-ethylcarbamate] 
(Compound No. 5) (oil); 
Ethyl N,N'-sulfenyl-bis[2-(4-/3,5-dichlorophenoxy/-phenoxy)-ethylcarbamate] 
(Compound No. 6) (oil). 
EXAMPLE 2 
Ethyl N,N'-sulfinyl-bis(2-/4-phenoxyphenoxy/-ethylcarbamate) (Compound No. 
7) 
To an ice-cooled solution of 2.0 g (0.0066 mole) of ethyl 
2-(4-phenoxyphenoxy)-ethylcarbamate, 1.1 ml (0.008 mole) of triethylamine 
in 6 ml of dry tetrahydrofurane 0.25 ml (0.0034 mole) of thionyl chloride 
is added and the solution is stirred at 30.degree. C. for 18 hours. 10 ml 
of benzene and 10 ml of hexane are added, the mixture is washed with 10 ml 
each of dilute hydrochloric acid, saturated sodium hydrogen carbonate 
solution and water, dried, and concentrated in vacuo. The residue is 
purified by column chromatography to give 0.68 g of a light viscous oil. 
The physical characteristics of the compounds are given in Table 1. 
The following compounds were prepared in an analogous manner: 
Isopropyl N,N'-sulfinyl-bis[2-(4-phenoxyphenoxy)-ethylcarbamate] (Compound 
No. 8) (oil); 
(.+-.) Ethyl 
N,N'-sulfinyl-bis[2-(4-/2,4-dichlorophenoxy/-phenoxy)-propylcarbamate] 
(Compound No. 9) (oil); 
Ethyl N,N'-sulfinyl-bis[2-(4-/4-chlorophenoxy/-phenoxy)-ethylcarbamate] 
(Compound No. 13) (oil). 
EXAMPLE 3 
[N-/(Ethoxycarbonyl-isopropylamino)sulfenyl]-2-(4-phenoxyphenoxy)-ethylcarb 
amic acid ethyl ester (Compound No. 10) 
To an ice-cooled solution of 2.0 g (0.0066 mole) of 
2-(4-phenoxyphenoxy)ethylcarbamate and 5 ml of dry pyridine 1.3 g (0.0067 
mole) of ethyl N-(chlorosulfenyl)-isopropylcarbamate is added and the 
solution is stirred at ambient temperature for 18 hours. The reaction 
mixture is diluted with 20 ml of diethyl ether and 20 ml of hexane, the 
precipitate is filtered, the filtrate is washed successively with 20 ml 
each of dilute hydrochloric acid, saturated sodium hydrogen carbonate 
solution and water, dried, and concentrated in vacuo. The residue is 
purified by column chromatography to give 1.8 g of a light viscous oil. 
The physical characteristics of the compounds are given in Table 1. 
The following compounds were prepared in a analogous manner: 
[N-(n-Octyloxycarbonyl-methylamino)sulfenyl]-2-(4-phenoxyphenoxy)-ethylcarb 
amic acid ethyl ester (Compound No. 11) (oil); 
[N-(n-Dodecyloxycarbonyl-butylamino)sulfenyl]-2-(4-phenoxyphenoxy)-ethylcar 
bamic acid ethyl ester (Compound No. 12) (oil). 
TABLE 1 
______________________________________ 
Physical constants of compounds of formula (I) 
Com- S content N content Cl content 
pound calc. found calc. 
found calc. found IR 
No. % % % cm 
______________________________________ 
1 5.07 5.19 4.43 4.33 1711 
(C = O) 
2 4.60 5.03 4.02 3.82 1715 
(C = O) 
3 4.50 4.61 3.93 3.87 1710 
(C = O) 
4 4.02 4.15 3.51 3.45 8.88 8.93 1715 
(C = O) 
5 4.57 4.80 3.99 3.90 10.11 10.00 1715 
(C = O) 
6 4.02 4.16 3.51 3.46 8.88 8.94 1715 
(C = O) 
7 4.94 5.02 4.32 4.28 1717 
(C = O) 
1298 
(S = O) 
8 4.74 4.80 4.14 4.11 1710 
(C = O) 
9 4.07 4.21 3.56 3.18 18.03 17.62 1719 
(C = O) 
1297 
(S = O) 
10 6.93 6.68 6.06 5.78 1709 
(C = O) 
13 4.47 4.60 3.90 3.86 9.88 9.75 1715 
(C = O) 
1296 
(S = O) 
______________________________________ 
The carbamate derivatives of general formula (I) have pesticidal activity; 
thus they can be used as active ingredients of insecticidal and acaricidal 
compositions. 
The biological activity of the compounds has been tested in laboratory as 
well as in the field. 
EXAMPLE 4 
Laboratory experiments with Pieris brassicae 
The morphogenetic activity of the compounds was tested on 24-hour old last 
instar caterpillars of the large cabbage white, Pieris brassicae, 
collected from a constant laboratory culture. The compounds to be assayed 
were topically applied to the dorsal surface of thorax using doses ranging 
from 0.01 to 0.1 .mu.g/specimen in 2 .mu.l of acetone solution, each dosis 
to 25 to 50 larvae. The treated groups of 12 to 15 caterpillars were kept 
in plastic cups of 0.5 liter at 25.degree. C. and 18 hours/day exposure to 
light, continuously fed with fresh cabbage leaves. The percentages of 
morphogenetically affected forms--or larvae incapable of living--as well 
as normal pupae were estimated after the the moult or pupation of insects. 
The results arre shown in Table 2. 
TABLE 2 
______________________________________ 
Morphogenetically 
Compound Dosis suffered caterpillars 
No. mg/caterpillar 
% 
______________________________________ 
1 0.1 100 
0.01 100 
7 0.1 100 
0.01 90 
10 0.1 100 
0.01 89 
______________________________________ 
EXAMPLE 5 
Field test on fall webworm (Hyphantria cunea) 
The following composition in the form of a wettable powder was prepared 
from a compound of formula (I) as an active ingredient, where R.sup.1 
=R.sup.2 is ethyl, R.sup.3 is H, and X is 2-(4-phenoxyphenyl)-ethyl, n=0 
(Compound No. 1): 
active ingredient--50% 
kaolin--40% 
sodium lignosulfonate 
sodium lauryl sulfate 
All percentages refer to mass based on the total mass of the composition. 
From this concentrate, suspensions containing 0.01, 0.001 and 0.0001% by 
volume of the active ingredient were prepared by appropriate dilution with 
water. These suspensions were sprayed onto branches of plum (Prunus) tree 
in special isolator. These branches had been previously infested with 
50--50 last instar (L.sub.7 -stage) larvae of the fall webworm, Hyphantria 
cunea. An assessment was made after 20 days. The results showed that all 
treatments caused a complete or substantial (up to 90%) reduction of 
viable pupae, as compared to an untreated control experiment where no 
morphogenetical abnormalities could be observed and 100% of the larvae 
emerged as moth. 
EXAMPLE 6 
Laboratory experiments with Quadraspidiotus perniciosus 
8 ml of an acetonic solution of 5 millimoles of the compounds of formula 
(I) (see Table 3) was sprayed onto a fruit of Cucurbita ficifolia. Then 
the fruit was infected with 50-60 larvae of the San Jose scale 
(Quadraspidiotus perniciosus) reared on non-treated Cucurbita ficifolia. 
The experiment was conducted at 28.degree. C. An evaluation was made three 
months after the treatment and the efficacy of the treatment was expressed 
in percentages using the Henderson-Tilton formula. The results are shown 
in Table 3. 
TABLE 3 
______________________________________ 
Compound 
Efficacy 
No. % 
______________________________________ 
Control 0 
1 100 
5 78 
7 100 
10 100 
11 100 
12 100 
13 0 
______________________________________ 
For application, the compounds of formula (I) can be processed into the 
form of dust, emulsion concentrates, granulates, water-dispersible 
concentrates, solutions, using usual auxiliary materials. 
The content of the active ingredient in the composition is between 0.0001 
and 95% by mass, preferably 0.01 to 80% by mass. 
The composition can contain, as auxiliary materials, solid or liquid 
carriers, diluting or excipient materials as well as surface active 
agents. The solid or liquid auxiliary materials can be natural or 
artificial origin, and are known in common practice and described in the 
literature. 
The surface active agents can be ionic or non-ionic dispersing agents, 
emulsifier or wetting agents, etc. 
Depending on the application, the composition can contain other commonly 
used auxiliary materials, antioxidants, stabilizers, odorant substances, 
etc. 
The pesticidal composition of the invention can be used in agriculture 
against insects and mites and also in other, especially sanitary, areas 
where the presence of insects and mites is harmful. 
The insecticidal properties of the compounds of the invention can be 
improved by so-called synergizing agents which enhance their activity. 
Examples of synergists are piperonyl butoxide, propargyl ether derivatives 
and S,S,S-tributyl-trithiophosphate. 
The following examples illustrate the composition of an emulsion 
concentrate: 
______________________________________ 
(A) active ingredient 
40 parts by weight 
N--methyl-pyrrolidone 
50 parts by weight 
polyethylene glycol 
10 parts by weight 
(B) active ingredient 
25 parts by weight 
xylene 55 parts by weight 
dimethyl sulfoxide 
10 parts by weight 
triethanolamine 5 parts by weight 
cationic tenside 
5 parts by weight 
______________________________________