CLIAMS:We claim:
1. Novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides having insecticidal activity and the following formula VI:

Formula VI
wherein R and R1 each is H, CH3 or C1 – C4 alkyl group and X is a halogen atom.

2. Novel pyrazole-5-carboxamides as claimed in claim 1, which is 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide.

3. A process for the preparation of novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides having insecticidal activity and the following formula VI:

Formula VI
wherein R and R1 each is H, CH3 or C1 – C4 alkyl group and X is a halogen atom which comprises chlorinating a compound of the following formula VII:

Formula VII
wherein R, R1 and X are as defined above with a chlorinating agent in the presence of an organic solvent under reflux temperature of the solvent and condensing the resulting compound of the following formula VIII:

Formula VIII
wherein R, R1 and X are as defined above with a compound of the following formula IX:

Formula IX
in the presence of a base and a solvent at - 10 to 120°C.

4. The process as claimed in claim 3, wherein the chlorination of compound of formula VII is carried out in an aromatic hydrocarbon selected from benzene, toluene and xylene.
5. The process as claimed in claim 3, wherein the chlorination of compound of formula VII is carried out in a halogenated hydrocarbon selected from dichloromethane, dichloroethane and chloroform.

6. The process as claimed in claim 3, wherein the chlorination of compound of formula VII is carried out in an organic solvent which includes another solvent selected from dimethyl formamide, dimethylacetamide and polyethylene glycol (PE), preferably polyethylene glycol-200 (PEG 200) or polyethylene glycol-400 (PEG 400).

7. The process as claimed in claim 3, wherein the chlorination of the compound of formula VII is carried out with a chlorinating agent selected from chloride, sulfuryl chloride, thionyl chloride and phosphorous oxy chloride.

8. The process as claimed in claim 3, wherein the condensation of the compound of formula VIII is carried out in the presence of a solvent selected from dioxane, actonitrile, dimethyl sulfoxide, N- methylpyrrolidone,N,N-Dimethyl formamide, tetrahydrofuran, acetonitrile, water, aromatic hydrocarbon selected from benzene, xylene and toluene, halogenated hydrocarbon selected from dichloromethane, dichloroethane, chloroform, mono chlorobenzene, dichlorobenzene, chloroxylene and aliphatic esters selected from ethyl acetate, methyl acetate and diethyl acetate.

9. The process as claimed in claim 3, wherein the condensation of the compound of formula VIII is carried out at -10 to 1000 C.

10. The process as claimed in claim 3, wherein the condensation of compound of the formula VIII is carried out with a base consisting of inert aliphatic amine selected from triethyl amine and pyridine or metal hydroxide or carbonate.

11. The process as claimed in claim 3, for the preparation of 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide.

12. An insecticidal composition comprising novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides of the following formula VI:

Formula VI

wherein R and R1 each is H, CH3 or C1 – C4 alkyl group and X is a halogen atom, in combination with conventional insecticidal and agricultural adjuvants and chemicals.

13. The insecticidal composition as claimed in claim 12, which includes one or more compatible conventional insecticides.

14. The insecticidal composition as claimed in claim 12, which comprises 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide.

15. A method of controlling insects by applying an insecticidally effective amount of novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides or insecticidal composition comprising the same.

16. The method of controlling insects as claimed in claim 15, by applying an insecticidally effective amount of 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide or insecticidal composition comprising the same.
,TagSPECI:FORM 2
THE PATENTS ACT, 1970
(39 OF 1970)
As amended by the Patents (Amendment) Act, 2005
&
THE PATENTS RULES, 2003
As amended by the Patents (Amendment) Rules, 2014
COMPLETE SPECIFICATION
(See section 10 and rule 13)

TITLE OF THE INVENTION
Novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides having insecticidal activity and process for the synthesis thereof

APPLICANTS

Godrej Agrovet Limited, Pirojshanagar, Eastern Express Highway, Vikhroli (East), Mumbai 400079, Maharashtra, India, an Indian Company

INVENTORS
Sahu Pramod Kumar, Tomar Ajeet Singh, Waghmare Samson, Godrej Nadir Burjor and Dogra Rakesh, all of Godrej Agrovet Limited, Pirojshanagar, Eastern Express Highway, Vikhroli (East), Mumbai 400079, Maharashtra, India, all Indian Nationals

PREAMBLE TO THE DESCRIPTION
The following specification particularly describes this invention and the manner in which it is to be performed:
FIELD OF THE INVENTION
This invention relates to novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides having insecticidal activity and process for the synthesis thereof.

This invention also relates to insecticidal composition comprising the novel thiadiazole–pyrazole carboxamides and method of controlling insects with the novel compounds or with the insecticidal composition thereof.

BACKGROUND OF THE INVENTION
Amongst the various classes of insecticides, pyrazoles and pyrroles insecticides are known to be safer and ecofriendly as compared to organo phosphorous and organo carbamates insecticides. Okada et al teach pyrazole amides, insecticide or miticide containing the pyrazole amides and method of controlling insects and mites with the pyrazole amides. The pyrazole amides are of the following Formula I:

Formula I
wherein R1 represents C1 -C4 alkyl group; R2 represents hydrogen atom, C1 -C4 alkyl group, cyclopropyl group, C1 -C4 alkoxy group or C2 -C4 alkylcarbonyl group; X represents hydrogen atom, halogen atom, C1 -C4 alkyl group, C1 -C4 alkoxy group, C1 -C3 haloalkoxy group, C2 -C4 alkylcarbonyloxy group or hydroxy group; R2 and X may combine together to form the group shown in the following Formula II or III

Formula II Formula III
in which R9 represents hydrogen atom or C1 -C3 alkyl group; one of R3, R4 and R5 is hydrogen atom and the others represent independently hydrogen atom, halogen atom, C1 -C4 alkyl group, C1 -C4 haloalkyl group, C3 -C6 cycloalkyl group, C1 -C4 alkoxy group, C1 -C4 haloalkoxy group, amino group, C1 -C4 alkylamino group, C2 -C6 dialkylamino group, C2 -C5 alkoxycarbonylamino group, C1 -C4 alkylthio group, C1 -C4alkylsulfinyl group, C1 -C4 alkylsulfonyl group, C2 -C5 alkoxycarbonyl group, C2 -C5 alkylcarbonyl group, nitro group, cyano group, hydroxymethyl group, C2 -C4alkoxyalkyl group and C3 -C6 alkoxyalkoxyalkyl group; R3 and R4 may combine together to form the group shown in the following formula IV or V:

Formula IV Formula V
in which R10 and R11 represent independently hydrogen atom or C1 -C4 alkyl group; one of R6 and R7 represents hydrogen atom and the other represents hydrogen atom, C1 -C4 alkyl group, C1 -C4 alkoxy group or halogen atom; Y represents oxygen atom, sulfur atom, sulfinyl group, sulfonyl group or carbonyl group; B represents --CH-- or nitrogen atom; R8 represents hydrogen atom or methyl group and Z represents oxygen atom or sulfur atom, with the proviso that all of R3, R4 and R5 are not hydrogen atoms when Y is oxygen and B is --CH--. (US 5039693).

N-(substituted or not-substituted aralkyl)-1-(substituted phenyl)-4-(substituted thio, substituted sulfoxy or substituted sulfonyl)-5-pyrazolecarboxamides are also reported. (Japanese Patent Application Laid-Open (KOKAI) No. 63-258859). These compounds are distinguished by a substituted thio group, substituted sulfoxy group or substituted sulfonyl group at the 4-position of the pyrazole ring. It is also reported that N-(substituted or not-substituted benzyl)-3-methyl-4-nitro-5-pyrazolecarboxamide has medicinal activity (Synthesis, 727 (1981); Farmaco, Ed Sci, 38, 369 (1984) and J Med Chem, 27 986 (1984).

The role and importance of insecticides in agriculture and horticulture needs no elaboration. However, because of the continuous and repeated use of conventional insecticides for the past many years, some of the insects have developed resistance to some of the conventional insecticides and it has been difficult to control certain insects by some of the conventional insecticides. A typical example is the case of insects having resistance to organophosphorous, carbamates and synthetic pyrethroids compounds. Some of the organophosphorous and carbamates compounds also exhibit high toxicity and disturb the ecological system due to their high residual effect which is quite alarming and dangerous. There is thus need for new insecticidal compounds which are effective against a wide range of insects, pests and mites and which are more effective and safer and ecofriendly and which have different modes of action. To address such need, extensive research and development activities are being carried out by us in the field of agrochemicals. As a result, we have developed certain new insecticidal compounds and process for the synthesis thereof, insecticidal composition containing them and method of controlling insects therewith.

DESCRIPTION OF THE INVENTION
According to the invention there is provided novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides having insecticidal activity and the following Formula VI:

Formula VI
wherein R and R1 each is H, CH3 or C1 – C4 alkyl group and X is a halogen atom.

According to the invention there is also provided a process for the preparation of novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides having insecticidal activity and the following Formula VI:

Formula VI
wherein R and R1 each is H, CH3 or C1 – C4 alkyl group and X is a halogen atom which comprises chlorinating a compound of the following Formula VII:

Formula VII
wherein R, R1 and X are as defined above with a chlorinating agent in the presence of an organic solvent under reflux temperature of the solvent and condensing the resulting compound of the following Formula VIII:

Formula VIII
wherein R, R1 and X are as defined above with a compound of the following Formula IX:

Formula IX

in the presence of base and a solvent at - 10 to 120°C.

Halogen atom as referred in the specification includes chlorine, bromine or iodine. The organic solvent for carrying out chlorination of compound of formula VII is preferably an aromatic hydrocarbon selected from benzene, toluene and xylene or preferably a halogenated hydrocarbon selected from dichloromethane, dichloroethane and chloroform. The organic solvent for carrying out the chlorination of the compound of formula VII optionally includes another solvent selected from dimethyl formamide, dimethylacetamide and polyethylene glycol (PE), preferably polyethylene glycol-200 (PEG 200) or polyethylene glycol-400 (PEG 400). The chlorinating agent for carrying out the chlorination of the compound of formula VII is selected from chloride, sulfuryl chloride, thionyl chloride and phosphorous oxy chloride.

The condensation of the compound of formula VIII is preferably carried out in the presence of a solvent selected from dioxane, actonitrile, dimethyl sulfoxide, N- methylpyrrolidone,N,N-Dimethyl formamide, tetrahydrofuran, acetonitrile, water, aromatic hydrocarbon selected from benzene, xylene and toluene, halogenated hydrocarbon selected from dichloromethane, dichloroethane, chloroform, mono chlorobenzene, dichlorobenzene, chloroxylene and aliphatic esters selected from ethyl acetate, methyl acetate and diethyl acetate. The condensation of the compound of formula VIII is preferably carried out at -10 to 100°C. The base for carrying out the condensation of compound of the formula VIII is preferably inert aliphatic amine selected from triethyl amine and pyridine or metal hydroxide or carbonate.

According to the invention there is also provided an insecticidal composition comprising novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides of the formula VI, in combination with conventional insecticidal and agricultural adjuvants and chemicals. The insecticidal composition may include one or more compatible conventional insecticides.

According to the invention there is also provided a method of controlling insects by applying an insecticidally effective amount of novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides of the formula VI or insecticidal composition comprising the same.

The composition of the invention may be in any applicable form including emulsifiable concentrates, suspension concentrates, emulsions, micro emulsions, wettable powders, granules, fine powders or dust or aerosols formulated with compatible adjuvants and agricultural chemicals being conventionally used in the art of insecticides. The concentration of the active ingredient in the insecticidal composition may vary from 0.2 to 20% by weight, preferably, from 1-10% by weight for dust, from 1-90% by weight, preferably, 10-80% by weight for wettable powder, from 1-90% by weight, preferably, 10-40% by weight for emulsifiable concentrate. As an insecticidal or miticidal agent for treatment of plants and crops, the active ingredient is used usually within a range of concentration from 5 to 1000 ppm, preferably, from 10 to 500 ppm. In seed treatment, the active ingredient may be used from 2 to 200 g/100 kg of the seed.

To the best of our knowledge and information, pyrazole carboxamides containing a thiadiazole moiety at 5- position (condensation position) of the pyrazole ring are not reported or suggested or hinted in the prior art literature. Therefore, we believe that the compounds of the formula VI are novel. We have found that pyrazole carboxamides containing a thiadiazole at 5 position of the pyazole ring posses extremely potent insecticidal activities against a wide range of insect-pest-mites in various agricultural crops. Therefore, the novel compounds of the formula VI have valuable agricultural applications and usage for controlling a wide range of insects- pests-mites in agricultural crops. Being pyrazole insecticides, the compounds of the invention are also safer and ecofriendly as compared to certain organophosphorous and organo carbamates insecticides.

The following experimental examples illustrative of the invention but not limitative of the scope thereof.

Preparation Example 1
A mixture of of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid (5.0 gm) and thionyl chloride (20 gm) in methane dichloride (150 ml) was refluxed for 12 hrs. After distilling off the thionyl chloride, the residue was dissolved in xylene (50 ml) to form a solution of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid chloride.

5-Amino-1,2,3-thiadiazole (5.0 gm) and triethyl amine (10.0 gm) with dichloro methane (100 ml) was cooled to -10 0C . The above solution of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid chloride in xylene was dropped to the above mixture at -10 0C to 35 0C. After completion of dropping, the mixture was stirred for 10 hrs and excess solvent was distilled out under reduced pressure. Water was added to the residue and extracted with ethyl acetate.

Organic layer was separated from the aqueous layer, washed with ice cold water and distilled under reduce pressure. Residue (crude product) was solvent crystallized using isopropyl alcohol to obtain 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]1Hpyrazole-5-carboxamide (4.45 gm) having the following characteristics :
MP - 176- 178 0C.
IR (KBr) cm-1 : 3256, 3023, 1660,1409, 1292, 1119, 1031, 881.
NMR H1 ( CDCl3): delta ppm 1.26(t,3H), 2.67- 2.72(m,2H), 3.08(m, 1H), 4.22(s,3H) ,8.7 (s,1H), 10(s,1H).

Preparation Example 2
A mixture of of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid (5.0 gm) and thionyl chloride (20 gm) in toluene (75 ml) was refluxed for 8 hrs. After distilling off the thionyl chloride, a solution of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid chloride was obtained as residue.

5-Amino-1,2,3-thiadiazole (5.0 gm) and pyridine (10.0 gm) with dichloro ethane (100 ml) was cooled to 0 0C . The above solution of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid chloride in toluene was dropped to the above mixture at 0 0C to 45 0C. After completion of dropping, the mixture was stirred for 10 hrs and excess solvent was distilled out under reduced pressure. Water was added to the residue and extracted with ethyl acetate.

Organic layer was separated from the aqueous layer, washed with ice cold water and distilled under reduce pressure. Residue (crude product) was solvent crystallized using isopropyl alcohol to obtain 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]1Hpyrazole-5-carboxamide (4.0 gm) having the following characteristics :
MP - 176- 178 0C.
IR (KBr) cm-1 : 3256, 3023, 1660,1409, 1292, 1119, 1031, 881.
NMR H1 ( CDCl3): delta ppm 1.26(t,3H), 2.67- 2.72(m,2H), 3.08(m, 1H), 4.22(s,3H) ,8.7 (s,1H), 10(s,1H).

Preparation Example 3
A mixture of of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid (5.0 gm) and thionyl chloride (20 gm) in chloro benzene (80 ml) was refluxed for 12 hrs. After distilling off the thionyl chloride, a solution of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid chloride was obtained as residue.
5-Amino-1,2,3-thiadiazole (5.0 gm) and pyridine (10.0 gm) with dichloro methane (150 ml) was cooled to 0 0C . The above solution of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid chloride in toluene was dropped to the above mixture at 0 0C to 45 0C. After completion of dropping, the mixture was stirred for 10 hrs and excess solvent was distilled out under reduced pressure. Water was added to the residue and extracted with chloroform 150 ml.
Organic layer was separated from the aqueous layer, washed with ice cold water and distilled under reduce pressure. Residue (crude product) was solvent crystallized using isopropyl alcohol to obtain 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]1Hpyrazole-5-carboxamide (3.75gm) having the following characteristics :
MP - 176- 178 0C.
IR (KBr) cm-1 : 3256, 3023, 1660,1409, 1292, 1119, 1031, 881.
NMR H1 ( CDCl3): delta ppm 1.26(t,3H), 2.67- 2.72(m,2H), 3.08(m, 1H), 4.22(s,3H) ,8.7 (s,1H), 10(s,1H).

Preparation Example 4
A mixture of of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid (5.0 gm) and sulfuryl chloride (20 gm) in toluene (75 ml) was refluxed for10 hrs. After distilling off the thionyl chloride, a solution of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid chloride was obtained as residue.
5-Amino-1,2,3-thiadiazole (5.0 gm) and triethylamine (10.0 gm) with dichloro ethane (100 ml) was cooled to 0 0C . The above solution of N-methyl-3-ethyl-4-chloro pyrazole-5-carboxylic acid chloride in toluene was dropped to the above mixture at 0 0C to 45 0C. After completion of dropping, the mixture was stirred for 10 hrs and excess solvent was distilled out under reduced pressure. Water was added to the residue and extracted with ethyl acetate.

Organic layer was separated from the aqueous layer, washed with ice cold water and distilled under reduce pressure. Residue (crude product) was solvent crystallized using isopropyl alcohol to obtain 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]1Hpyrazole-5-carboxamide (3.9gm) having the following characteristics :
MP - 176- 178 0C.
IR (KBr) cm-1 : 3256, 3023, 1660,1409, 1292, 1119, 1031, 881.
NMR H1 ( CDCl3): delta ppm 1.26(t,3H), 2.67- 2.72(m,2H), 3.08(m, 1H), 4.22(s,3H) ,8.7 (s,1H), 10(s,1H).

Formulation Example 1A
Five parts by weight of 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide of Examples 1 to 4 were mixed in 90 parts by weight of isopropyl alcohol, followed by addition of 2.5 parts by weight of NANSA (a mixture of anionic surfactant and non-ionic surfactant) of Huntsman International (India) Pvt Ltd to obtain an emulsifiable concentrate having the active ingredient content at 5 percent by weight.

Test Example 1 A
Slices of cabbage leaves (5x5 cm) were immersed for one minute in water diluted solutions of the Formulation of Example 1A, air-dried and placed in plastic vials ( 7 cm diameter). Five larvae of third instar of Plutella xylostella were released in each vials. Two days after releasing the larvae, the number of dead larvae were counted to determine the mortality (%).Mortality (%) = (number of dead larvae/ number of treated larvae) x 100. Test was repeated thrice for each concentration of the formulation. The rest results were as shown in the following Table 1:

Table 1
Formulation Concentration
(ppm) Mortality (%)
Plutella xylostella
50 60
100 92
200 100
500 100

Test Example 2A
Germinated seedlings of rice plant were set in a cylindrical glass jar (4 cm diameter, 18 cm length) and five larvae of fourth instar of Nilaparvata lugens were released to the seedlings in the jar. Formulation of Example 1A diluted with water was scattered over the seedlings (0.5 ml) using potter tower. One day after treatment ( 24 hours after treatment) , the number of dead larvae was counted to determine the mortality(%). Mortality (%) = (number of dead larvae/ number of treated larvae) x 100. Test was repeated four times for each concentration of the formulation. The rest results were as shown in the following Table 2:

Table 2

Formulation Concentration
(ppm) Mortality (%)
Nilpaarvata lugens
50 55
100 90
200 100
500 100

Test Example 3A
Cotton with fully expanded cotyledon leaves were trimmed to one cotyledon per plant and infested with cotton aphid (wingless adult and nymph) one day prior to application of Formulation of Example 1A. Each plant was examined before application of Formulation of Example 1A to ensure proper infestation (30-50 aphids per plant). Formulation of Example 1A diluted with water was applied on the cotton cotyledon leaves until runoff to both sides of the cotton cotyledon leaves. Five plants (5 replications) were used for each concentration. Reference plants (untreated) were sprayed with only water. Treated plants were kept in room for 3 days at approximately at 230C and 40% humidity. Three days later insecticidal activity of the treated plants was measured by corrected % control using Abbott?s correction formula. Corrected % control = 100* (x-y)/x, where x = No. of live aphids on untreated (water spray) plants, y = No. of live aphids on treated plants. The results were as shown in the following Table 3:

Table 3
Formulation Concentration
(ppm) % control of Aphis gossypii on Cotton
50 75.0
100 95.0
200 100.0
500 100.0
Control (water spray) 0.0

We claim:
1. Novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides having insecticidal activity and the following formula VI:

Formula VI
wherein R and R1 each is H, CH3 or C1 – C4 alkyl group and X is a halogen atom.

2. Novel pyrazole-5-carboxamides as claimed in claim 1, which is 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide.

3. A process for the preparation of novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides having insecticidal activity and the following formula VI:

Formula VI
wherein R and R1 each is H, CH3 or C1 – C4 alkyl group and X is a halogen atom which comprises chlorinating a compound of the following formula VII:

Formula VII
wherein R, R1 and X are as defined above with a chlorinating agent in the presence of an organic solvent under reflux temperature of the solvent and condensing the resulting compound of the following formula VIII:

Formula VIII
wherein R, R1 and X are as defined above with a compound of the following formula IX:

Formula IX
in the presence of a base and a solvent at - 10 to 120°C.

4. The process as claimed in claim 3, wherein the chlorination of compound of formula VII is carried out in an aromatic hydrocarbon selected from benzene, toluene and xylene.
5. The process as claimed in claim 3, wherein the chlorination of compound of formula VII is carried out in a halogenated hydrocarbon selected from dichloromethane, dichloroethane and chloroform.

6. The process as claimed in claim 3, wherein the chlorination of compound of formula VII is carried out in an organic solvent which includes another solvent selected from dimethyl formamide, dimethylacetamide and polyethylene glycol (PE), preferably polyethylene glycol-200 (PEG 200) or polyethylene glycol-400 (PEG 400).

7. The process as claimed in claim 3, wherein the chlorination of the compound of formula VII is carried out with a chlorinating agent selected from chloride, sulfuryl chloride, thionyl chloride and phosphorous oxy chloride.

8. The process as claimed in claim 3, wherein the condensation of the compound of formula VIII is carried out in the presence of a solvent selected from dioxane, actonitrile, dimethyl sulfoxide, N- methylpyrrolidone,N,N-Dimethyl formamide, tetrahydrofuran, acetonitrile, water, aromatic hydrocarbon selected from benzene, xylene and toluene, halogenated hydrocarbon selected from dichloromethane, dichloroethane, chloroform, mono chlorobenzene, dichlorobenzene, chloroxylene and aliphatic esters selected from ethyl acetate, methyl acetate and diethyl acetate.

9. The process as claimed in claim 3, wherein the condensation of the compound of formula VIII is carried out at -10 to 1000 C.

10. The process as claimed in claim 3, wherein the condensation of compound of the formula VIII is carried out with a base consisting of inert aliphatic amine selected from triethyl amine and pyridine or metal hydroxide or carbonate.

11. The process as claimed in claim 3, for the preparation of 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide.

12. An insecticidal composition comprising novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides of the following formula VI:

Formula VI

wherein R and R1 each is H, CH3 or C1 – C4 alkyl group and X is a halogen atom, in combination with conventional insecticidal and agricultural adjuvants and chemicals.

13. The insecticidal composition as claimed in claim 12, which includes one or more compatible conventional insecticides.

14. The insecticidal composition as claimed in claim 12, which comprises 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide.

15. A method of controlling insects by applying an insecticidally effective amount of novel 4- Halo-3-alkyl-1-alkyl-N-(1,2,3-thiadiazole)1H pyrazole-5-carboxamides or insecticidal composition comprising the same.

16. The method of controlling insects as claimed in claim 15, by applying an insecticidally effective amount of 4-chloro-3-ethyl-1-methyl-N-[1,2,3-thiadiazole]-1H- pyrazole-5-carboxamide or insecticidal composition comprising the same.
Dated this 18 September 2014

(Jose M A)
of Khaitan & Co
Agent for the Applicants
Reg No IN/PA-44