FORM 2
THE PATENTS ACT, 1970
COMPLETE SPECIFICATION
[SEE SECTION 10]
NOVEL NEO - NICOTINOID COMPOUND USEFUL AS A BROAD
SPECTRUM INSECTICIDE, AN INSECTICIDAL COMPOSITION
CONTAINING THE NOVEL COMPOUND AND A PROCESS FOR THE
PREPARATION OF THE NOVEL COMPOUND AND ITS
COMPOSITION S.
RALLIS INDIA LIMITED, AN INDIAN COMPANY REGISTERED UNDER THE INDIAN COMPANY'S ACT, 1956 HAVING ITS REGISTERED OFFICE AT "RALLI HOUSE" 21, D. S. MARG, FORT, MUMBAI -400 001. MAHARASHTRA , INDIA
The following specification particularly describes and ascertains the nature of this invention and the manner in which it is to be performed.


FIELD OF INVENTION
This invention relates to novel neo-nicotinoid compound and its derivatives useful as an insecticide. This invention, particularly, relates to novel 2-chloro-5-pyridylmethyl and its derivatives having the general formula I given below

Where: X = halogens and R = Chloro Thiazole Group
The invention also relates to insecticidal compositions containing the compound of the formula I as defined above and its derivatives, which are useful as a broad-spectrum contact and systemic insecticide for the control of sucking insects namely aphids, thrips, hoppers, whiteflies, scales and mealy bugs.
This invention particularly relates to the novel compound, N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine having the formula II.

The derivatives of the general formula I are those where R represents groups such as 6-Chloro-3-methyl pyridyl, methyl, ethyl and the like .
This compounds of the formula I as defined above and its derivatives of the present invention are ideal for controlling certain insect pests, which are of economic importance from the point of crop losses. For e.g., aphids, thrips, leaf hoppers, plant hoppers, whiteflies etc. from the order homoptera on various crops.
This invention also relates to a process for the preparation of the compounds of the general formula I as defined above and its derivatives and a process for the preparation of Insecticidal compositions containing the compounds of the formula I and its derivatives.
PRIOR ART
The existing systemic and contact insecticide Acetamiprid is effective for the control of sucking insects like aphids, thrips, whiteflies etc., which are a major menace on cotton, vegetables, oil seeds plantation crops etc. However, this insecticide is not much effective against hard to kill pests like mealy bugs, scales and planthogens which infest the above said crops regularly.
Method of preparing 2-Chloro-5-chloromethyl thiazole is described in US Patent No 4748243, which comprises of chlorination of allyl isothiocyanate by chlorine gas in chloroform at 60 °C or by chlorination of allyl thiocyanate by sulfuryl chloride at reflux temperatures. The method of preparing N-(2-Chloro-5-pyridylmethyl)-2-nitrimino-4,5-dihydroimidazolidine are described in Indian Patent No 181755 involves the preparation of Nitriminoimidazolidine starting from methyl thiocyanate and methyl mercaptan to form 2,2-bis thio methyl formimidine which is nitrated using nitric acid and sulfuric acid

to get 2,2-bis thiomethyl formimidine nitrate which on condensation with ethylene diamine gives the desired product and 2-chloro-5-chloromethylpyridine is prepared from 6-chloro nicotinic acid . Nitriminoimidazolidine and 2-Chloro-5-chloromethylpyridine thus prepared are condensed in Acetonitrile at 80 °C in presence of potassium carbonate to get N-(2-Chloro-5-pyridylmethyl)-2-nitrimino-4,5-dihydroimidazolidine.
OBJECTIVES OF THE INVENTION
The main objective of the present invention is to provide novel insecticides of the formula I as defined above and its derivatives which are useful to combat hard to kill pests like whiteflies, mealy bugs, scales, brown plant hoppers including aphids, hoppers, thrips etc.
Another objective of the present invention is to brovide novel broad-spectrum superior systemic and contact insecticide of the formula I as defined above and its derivatives.
Still another objective of the present invention is to provide a novel broad-spectrum superior systemic and contact insecticide namely 2-chloro-5-methylpyridylmethyl and its derivatives having the general formula I defined above.
Yet another objective of the present invention is to provide a novel broad-spectrum superior systemic and contact insecticide namely N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine having the formula II given above.
Yet another objective of the present invention is to provide a insecticidal composition containing 2-chloro-5-pyridylmethyl and its derivatives having the

general formula I given above particularly the novel compound N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine having the formula II given above useful as a broad-spectrum superior systemic and contact insecticide.
Still another objective of the present invention is to provide a process for preparing the broad-spectrum superior systemic and contact insecticide namely 2-chloro-5-pyridylmethyl and its derivatives having the general formula I defined above, particularly the novel compound N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine having the formula II given above.
Yet another objective of the present invention is to provide a process for the preparation of a broad-spectrum superior systemic and contact insecticide composition containing 2-chloro-5-pyridylmethyl and its derivatives having the general formula I given above particularly the novel compound N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine having the formula II given above.
DESCRIPTION OF THE INVENTION

Accordingly the present invention provides novel insecticides of the formula I as defined above and its derivatives which are useful to combat hard to kill pests like whiteflies, mealy bugs, scales, brown plant hoppers including aphids, hoppers, thrips etc.

According to another embodiment of the present invention there is provided novel insecticides of the formula II as defined above and its derivatives which are useful to combat hard to kill pests like whiteflies, mealy bugs, scales, brown plant hoppers including aphids, hoppers, thrips etc.
According to another feature of the present invention there is provided a process for the preparation of novel insecticides of the formula I as defined above and its derivatives which comprises condensing the compound of the formula III with a thiazole of the formula IV in the presence of a base and if desired ,converting the resulting compounds into its derivatives by conventional methods .

Where R= Halogens Where Y= Ethyl or Methyl Groups
III IV
According to another feature of the present invention there is provided a process for the preparation of the novel N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine having the formula II given above which comprises condensing N-(2-chloro-5-pyridylmethyl)-2-nitrimino-4,5-dihydroimidazolidine of the formula III A with 2-chloro-5-chloromethylthiazole of the formula IV A in the presence of a base and if desired, converting the resulting compounds into its derivatives by conventional methods


The condensation reaction may be effected in the presence of a non-aqueous solvent or mixture of solvents. The solvent, which can be used, may be selected from N, N-Dimethyl formamide, Dimethyl sulfoxide, Acetonitrile, Acetone, Methyl isobutyl ketone, Diethyl ketone etc. More preferably N, N-Dimethyl formamide and Acetonitrile and the like. The amount of solvent, which may be employed, may be in the range of 0-25 times molar equivalent of 2-chloro-5-chloro methyl thiazole employed.
When no solvent is used the reaction mixture will be in the form of a melt. The product in this case is isolated by dissolving in a solvent like acetone, acetonitrile and then evaporating the solvent.
The base such as a hydroxide, carbonate or bicarbonate or any organic bases like tertiary amines may be used.
The process may be carried out at a temperature in the range of 25-80 °C, typically in the range of 25-50 °C.
The derivatives of the compounds of the formula I & II may be prepared by condensing the resulting compound of the formula I with chlorothiazole or with ethyl or methyl derivative of thiazole under suitable conditions.
According to another feature of the invention there is provided a broad-spectrum insecticide composition comprising the compound of the formula I as defined above its derivatives and a carrier normally employed in such composition
According to another feature of the invention there is provided a broad spectrum insecticide composition comprising the compound of the formula II as defined above its derivatives and a carrier normally employed in such composition

The amount of the active compound present in the composition may range between 1% to 95% by weight of the active substance with 5% to 99% of the carrier and other ingredients which are appropriately reduced or increased.
Preferably the active ingredient may range between 5% and 75% more preferably may be between 20% and 75%.
The necessary formulation auxiliaries such as inert materials, surfactants, solvents and other additives, employed in the composition are all known and have been described. For example, in Watkins, "Handbook of Insecticide Dust Diluents and Garriers", 2nd Ed., Dartand Books, Caldwell N. J.; H. v. Olphen, "Introduction to Clay Colloid Chemistry", 2nd Ed., J. Wiley & Sons, N.Y.; Marsden, "Solvents Guide", 2nd Ed., Interscience, N.Y. 1950; McCutcheon's, "Detergents and Emulsifiers Annual", MC Publ. Corp., Ridgewood N.J.; Sisley and Wood, "Encyclopedia of Surface Active Agents", Chem. Publ. Co. Inc., N.Y. 1964; Schonfeldt, "Grenzflachenaktive Athylenoxidaddukte", [Surface-active ethylene oxide adducts] Wiss. Verlagsgesell., Stuttgart 1967; Winnacker-Kuchler, "Chemische Technologie", Volume 7, C. Hauser Verlag Munich, 4th Edition 1986.
Based on these formulations, it is also possible to prepare combinations with other pesticidally active materials, fertilizers and/ or growth regulators, for example in the form of a ready-mix formulation or a tank mix. Wettable powders are preparations which are uniformly dispersible in water which, besides the active substance, also comprise wetters, for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkylsulfonates or alkylphenolsulfonates and dispersants, for example sodium lignosulfonate or sodium 2,2,-dinaphthylrnethane-6,6'-disulfonate, in addition to the diluent or inert material.

Besides, the above mentioned active substance formulations comprise, if appropriate, the tackifiers, wetters, dispersants, emulsifiers, penetrants, solvents, fillers or carriers which are conventional in each case.
According to another embodiment of the present invention there is provided a process for the preparation of a broad spectrum insecticide composition which comprises mixing thoroughly the active ingredient of the compound of the formula I and its derivatives with inert material and / or adjuvants.
According to another embodiment of the present invention there is provided a process for the preparation of a broad-spectrum insecticide composition, which comprises mixing thoroughly the active ingredient of the compound of the formula II and its derivatives with inert material and / or adjuvants.
According to an embodiment of the present invention there is provided a process for the preparation of a broad spectrum insecticide composition which comprises mixing thoroughly 1 to 95% by weight of the active substance with 5% - 99% of inert material and/ or adjuvants. Preferably the active compound may range between 5% and 75% more preferably may be between 20% and 75%.
The mixing may be effected in an experiment called ribbon blender, subsequently the mixture is pulverized. This is done at ambient temperatures.
The composition may be in the form of Wettable powders (WP), Emulsifiable concentrates (EC), Aqueous solutions (SL), Emulsions, Sprayable solutions, Oil-or Water based dispersions (SC), Dusts, Seed dressing products, Granules in the form of Microgranules, Spray granules, Coated granules and Absorption granules, water Dispersible granules (WG). The composition may be converted into above said various forms by conventional means and specialized techniques. In the case of SC the mixture has to be passed through a dynomill. In

the case of WG one has to employ a fluidized bed drier or spray granulation methods. In the case of EW; specialized emulsifier has to be used depending on the biological and/ or chemical-physical parameters, which prevail.
Emulsifiable concentrates are prepared by dissolving the active substance in an organic solvent, for example butanol, cyclohexanone, dimethylformamide, xylene or else higher-boiling aromatics or hydrocarbons, with addition of one or more emulsifiers. As emulsifiers, the following can be used. For example: calcium alkylarylsulfonates such as calcium dodecylbenzenesulfonate, or nonionic emulsifiers such as fatty acid polyglycol esters, alkylaryl polyglycol ethers, fatty alcohol polyglycol ethers, propylene oxide/ ethylene oxide condensates, alkyl polyethers, sorbitan fatty acid esters, polyoxyethylene sorbitan fatty acid esters or polyoxyethylene sorbitol esters.
Dusts are obtained, for example, by grinding the active substance with finely divided solid materials, for example talc or natural clays, such as kaolin, bentonite, pyrophyllite or diatomaceous earth. Granules can be prepared either by atomizing the active substance onto adsorptive, granulated inert material or by applying active substance concentrates onto the surface of carrier materials such as sand or kaolinites, or of granulated inert material, by means of adhesives. For example polyvinyl alcohol or sodium polyacrylate, or else mineral oils. Suitable active substances can also be granulated in the manner, which is customary for the preparation of fertilizer granules, if desired as a mixture with fertilizers.
The active substance concentration in wettable powders is, for example, approximately 10 to 90% by weight, the remainder to 100% by weight is composed of customary formulation auxiliaries. In the case of emulsifiable concentrates, the active substance concentration may be approximately 5% to 80% by weight. Formulations in the form of dusts usually comprise 5% to 20%

by weight of active substance, sprayable solutions approximately 2% to 20% by weight. In the case of granules, the active substance content depends partly on whether the active compound is in liquid or solid form and on which granulation auxiliaries, fillers and the like are being used.
For use, the concentrates, which are present in commercially available form, are, if desired, diluted in the customary manner, for example in the case of wettable powders, emulsifiable concentrates, dispersions and in some cases also microgranules using water. Preparations in the form of dusts and granules and sprayable solutions are usually not diluted any further with other inert substances prior to use.
The application rate required varies with the external conditions such as, inter alia, temperature and humidity. It may vary within wide limits, for example between 0.002and 0.5 kg/ ha or more of active substance, but it is preferably between 0.01 and 0.5 kg/ha.
The composition may contain 20gms and 50gms a.i. of the active ingredient/ hectare with high volume sprayer by using an average of 500 Liters of water per hectare.
The invention is described in detail in the examples given below, which are given only by way of illustration and therefore should not be construed to limit the scope of the invention
EXAMPLE 1
Process for the Preparation of novel N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine of the formula II.

N-(2-chloro-5-pyridylmethy[)-2-Nitrimino-4/5-dihydro imidazolidine (0.1 mole) is reacted with 2-chloro-5-chloromethyl thiazoie (0.1 mole) in N,N-Dimethyl formamide (40ml) in presence of potassium carbonate (0.1 mole) at 50 °C for 4 hours. The reaction is followed by gas chromatography and once the starting materials have been converted the solvent is distilled off under reduced pressure and the residue is recrystallised from methanol to obtain N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine YIELD : 33.28 grams (86%).
EXAMPLE 2
Process for the Preparation of N-(2-Chloro-5-pyridylmethyl)-Ny-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine of the formula II.
2-chloro-5-(l\l-ethylenediamino methyl) pyridine (0.1 mole) is reacted with 2-chloro-5-chloromethyl thiazoie (0.1 mole) in presence of N,N-Dimethyl formamide (40ml) at 25 °C for 8 hours. The resulting product is treated with nitroguanidine (0.1 mole) in the presence of potassium carbonate (0.1 mole) for 6 hours. On removing the solvent under reduced pressure crude product is obtained, which is purified by recrystallising from methanol to obtain N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine.YIELD : 27.1 grams (70%).
EXAMPLE 3 - FORMULATION - DUST
A dust is obtained by mixing 10 parts by weight of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine prepared by the process described in Example 1 and 90 parts by weight of talc as inert material and pulverized the mixture in a hammer mill. The dust so obtained is found to have good insecticidal properties.

EXAMPLE 4 - A WETTABLE POWDER
A wettable powder, which is readily dispersible in water, is obtained by mixing 25 parts by weight of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine prepared by the process described in Example 1 65 parts by weight of kaolin-containing quartz as inert material. 9 parts by weight of potassium lignosulfonate and 1 part by weight of sodium oleoylmethyl taurinate as wetter and dispersant and grinding the mixture in a pinned-disk mill. The resulting powder is found to have good insecticidal effect.
EXAMPLE 5 - DISPERSION
A dispersion concentrate, which is readily dispersible in water, is prepared by mixing 40 parts by weight of N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine prepared by the process described in Example 2 with 7 parts by weight of a sulfosuccinic monoester. 2 parts by weight of a sodium lignosulfonate and 51 parts by weight of water and grinding the mixture in a ball mill to a fineness of below 5 microns. The resulting powder is found to have good insecticidal effect
EXAMPLE 6 - AN EMULSIFIABLE CONCENTRATE
An emulsifiable concentrate can be prepared from 15 parts by weight of N-(2-Chloro-5-pyridylmethyl)-N1-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine prepared by the process described in Example 2 75 parts by weight of cyclohexanone as solvent and 10 parts by weight of oxyethylated nonylphenol (10 EO) as emulsifier. The emulsifiable concentrate is found to have good insecticidal properties.

EXAMPLE 7-GRANULES
Granules are prepared by mixing 5 parts by weight of N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine prepared by the process described in Example 2 and 7 parts by weight of an inert liquid like Diethylene glycol or any other suitable solvent. This mixture is sprayed on to the surface of 88 parts by weight of Bentonite Granules, mixed and then dried.
BIOLOGICAL EXAMPLES EXAMPLE 8 5% Granules Effect on the Rice Brown Plant hoppers:
Order: Homoptera
Family: Delphacidae
Insect: Nilaprvatha Lugens Stal
The field experiment was conducted at Gangavathi (Karnataka) in order to evaluate the efficacy of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (5% G) obtained by the process described in the example 7 against Rice brown plant hoppers.
It was tested @ 50 & 75 gal/ ha in comparison with the known Carbofuran 3 G @ 750 gal/ ha and @ phorate 10G( Known ) @ 1000 gai/ ha. The experiment was laid out in the field with plots measuring 25 Sq.m. as per randomized block design with four replications. Soil application of test doses of insecticides were applied twice at 20 days interval with sand. Total number of hoppers (both nymphs and adults) were counted in 10 randomly selected hills in each plot before, 7 & 14 days after each application. Results shows that N-(2-Chloro-5-

pyridylmethyl)-N'-(2-chloro-5-thia2olylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (5% G) at 50 gai/ ha (3.10 to 6.20 hoppers per hill) we comparable with Carbofuran 3G @ 750 gai/ ha (5.16 to 8.23 hoppers per h and superior to phorate 10 G @ 1000 gai/ ha (8.20 to 15.18 hoppers per hi Where as, untreated check recorded 81.70 to 108.41 hoppers per hill.
Tablel : Effect of N-(2-Chloro-5-pyridylmethyl)-N"-(2-chloro-5-thiazolylmethyl)-2-nitrimino 4,5-dihydroimidazolidine (5% G) against Rice brown plant hopper, Nilaparvata lugens

Treatments Dose
(ga.i./ha) Mean no. ofBPH/hill

Before Spray 7 days after I spray 14 days after I spray 7 days after II spray 14 days after II spray
N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (5%G) 50 75.81 3.10 6.20 4.61 5.01
N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (5%G) 70 61.80 2.21 3.19 3.81 4.16
Carbofuran 3G(Known) 750 73.45 7.20 7.26 5.16 8.23
Phorate lOG(Known) 1000 80.65 8.21 14.41 8.20 15.18
Control - 71.80 81.70 94.73 93.86 108.41
Sem ± CD at 5% 1.21 3.63 0.91 2.73 0.83 2.49 0.75 2.25
The above results indicate that N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (5% G) at 50 gai/ ha (3.10 to 6.20 hoppers per hill) were comparable with Carbofuran 3G @ 750 gai/ ha (5.16 to 8.23 hoppers per hill) and superior to phorate 10 G @ 1000 gai/ ha

(8.20 to 15.18 hoppers per hill). Where as, untreated check recorded 81.70 to 108.41 hoppers per hill.
EXAMPLE 9
75% Wettable Seed dresser
Effect on the Okra (Bhendi) Sucking pests:
Order: Homoptera Family: Aphididae Insect: Aphis gassypii G
Order: Homoptera
Insect: Amrasca biguttula biguttula Ishida
Order: Thysanoptera Family: Thripidae Insect: Thrips tabaci Lind
The experiment was conducted in the field for the efficacy of N-(2-Chloro-5-pyridylmethyl)-N^(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (75% WS) against Okra sucking pests. N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitnmino-4,5-
dihydroimidazolidine (75% WS) prepared by the Example 4 was tested at 5 & 7.5 g/ kg seed in comparison with known ImidacloPrid 70% WS at 5 & 7.5 g/ kg of seed, known Thiamethoxam 70% WS at 4.8 g/ kg seed and known carbosulfan 25% DS at 50 g/ kg seed. The chemicals wee treated with seeds prior to sowing. Observations were recorded on number of seeds germinated in each plot 25 days after sowing.

Observations were also made on total number of Aphids, Thrips and Jassids from 3 leaves in each plot in 10 randomly selected plants in each plot 30 & 45 days after sowing. It is evident from the results that N-(2-Chloro-5-pyridylmethyl)-N%-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (75% WS) at 5 & 7.5 g/ kg seed was on par with Imidacloprid 70% WS, Thiamethoxam 70% WS and superior to Carbosulfan 25% DS.
Table2 : Effect of N-(2-Chloro-5-pyridylmethyl)-N-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (75%WS) against sucking pests of Okra

Treatment Dose
(9/kg
weed) Mean percent germination (25 DAS) Mean no. of insects/leaf

Aphids Thrips Jassids

30 DAS 45 DAS 30 DAS 45 DAS 30 DAS 45
DAS
N-(2-Chloro-5-
pyridylmethyl)-^-^-
chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(75%WS) [Example 4] 5.0 80.28 2.1 2.9 2.9 3.5 2.0 2.9
N-(2-Chloro-5-
pyridylmethyl)-N,-(2-
chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(75%WS) [Example 4] 7.5 82.61 2.0 2.7 2.8 3.1 2.3 2.8
Imidacloprid 70WS Known 5.0 79.91 1.9 2.0 2.6 3.1 1.9 2.1
Imidacloprid 70WS Known 7.5 83.40 1.7 2.4 2.1 2.9 1.6 2.3
Thiamethoxam 70WS Known 4.8 82.33 2.0 2.3 2,4 3.6 2.0 2.5

Carbosulfan 25DS Known 50 83.41 6.3 8.1 4.5 5.8 3.1 5.6
Control (Untreated check) 83.90 , 35.6 58.6 13.6 24.3 8.1 12.8
SEm± CD at 5% - - 0.30 0.90 0.48 1.44 0.40 1.21 0.60 1.82 0.51 1.53 0.75 2.25
DAS: Days After Sowing
It is clear from the results that N-(2-Chioro-5-pyridylmethyl)-N*-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dthydroimidazolicline was on par with Imidacloprid, Thiamethoxam and superior to Carbosulfan .
EXAMPLE 10
75% Wettable Seed dresser Effect on the Cotton Sucking Pests:
Order: Homoptera Family: Aphididae Insect: Aphis gassypii G
Order: Homoptera
Family: Cicadellidae
Insect: Amrasca biguttula biguttula Ishida
Order: Thysanoptera Family: Thripidae Insect: Thrips tabaci Lind
The experiment was conducted in the field to evaluate the efficacy of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-

nitrimino-4,5-dihydroimidazolidine (75% WS) prepared according to the Example 4 against Cotton sucking pests viz Aphids, Jassids and Thrips. N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine (75% WS) was tested at 5 & 7.5 g/ kg seed in comparison imidacloprid, thiamethaxam and carbosulphan. The experiment was laid out in a randomized block design with three replications. The seeds were treated with chemicals prior to sowing. Observations were made on number of seeds germinated in each plot 25 days after sowing. Observations were also made on total number of Aphids, Thrips and Jassids from six leaves per plant in 10 randomly selected plants in each plot 30 & 45 days after sowing. Results reveal that N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (75% WS) @ 5 & 7.5 g/ kg of seed was comparable with the known Imidacloprid 70% WS at 5g & 7.5 g/ kg seed & known Thiamethoxam 70% WS @ 4.8 g/ kg seed and superior to commonly used insecticide known carbosulfan 25 DS @ 50 g/ kg seed, in checking the population of sucking pests.
Table3: Effect of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (75%WS) against Cotton sucking pests

Treatment Dose
(9/kg
seed) Mean
percent of germination (25 DAS) Mean no. of insects / leaf

Aphids Thrips Jassids

30 DAS 45 DAS 30 DAS 45 DAS 30 DAS 45 DAS
N-(2-Chloro-5-
pyridylmethyl)-N' -(2-
chloro-5-thiazo!ylmethyl)-
2-nitrimino-4,5-
dihydroimidazolidine
(75%WS) 5 75.63 3.0 4.8 2.1 3.9 2.9 4.8

N-(2-Chloro-5-
pyridylmethyl)-N'-(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4,5-
dihydroimidazolidine
(75%WS) 7.5 74.81 2.9 4.3 2.3 3.7 3.1 4.4
Imidacloprid 70WS
Known 5.0 76.90 2.6 3.1 2.0 3.4 2.6 4.3
Imidacloprid 70WS
Known 7.5 73.43 1.9 3.0 1.9 3.0 2.8 3.9
Thiamethoxam 70WS Known 4.8 77.41 2.3 3.3 2.4 3.6 3.0 4.2
Carbosulfan 25DS Known 50 75.83 12.8 16.1 6.8 10.4 6.8 9.9
Control (Untreated check) -- 75.90 35.3 58.4 28.8 35.6 15.8 21.6
SEm± CD at 5% - 0.96 2.88 0.41 1.23 0.35 1.05 0.30 0.90 0.43 1.29
DAS : Days After Sowing
Results reveal that N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine was comparable with the known Imidacloprid & known Thiamethoxam seed and superior to commonly used insecticide known carbosulfan.
EXAMPLE 11
0.2% Dust
Effect on the Rice Brown Plant hopper:
Order: Homoptera Family: Delphacidae

Insect: Nilaparvatha lugens Stal
The field trial with a randomized block design with three replications was conducted during Kharif 2000 with N-(2-Chloro-5-pyridylmethyl)-N^-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (0.2 % Dust) prepared by the process of Example 3 at 50 and 75 gai/ ha against Rice brown plant hopper, Nilaparvatha lugens Stal. This was compared with known Fenveralate 0.4% Dust at 100 gai/ ha and known Endosulfan 4% Dust at 1000 gai/ ha. Observations were made on total number of hoppers in 10 randomly selected hills in each plot before, 2, 7 and 14 days after first application and 7 and 14 days after second application. Results show that N-(2-Chloro-5-pyridylmethyl)-N1 -(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (0.2% Dust) @ 50 & 75 gai/ ha is superior to commonly used insecticides, Fenveralate 0.4% Dust @ 25 kg/ ha and Endosulfan 4% Dust at 25 kg/ ha.
Table4: Effect of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (0.2%Dust) against Rice brown plant hopper, Nilaparvata lugens

Treatments Dose
(g
a.i./ha) Mean no. of BPH/hill

Before spray 48 firs after I spray 7 days after I spray 14 days after I spray 7 days after II spray 14 days after II spray
N-(2-Chloro-5-
pyridylmethyl)-l\T-
(2-chloro-5-
thiazo{yfmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(0.2%Dust) 20 45.60 7.81 3.31 5.33 3.84 4.71

N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(0.2%Dust) 50 38.41 5.42 1.40 2.81 8.64 4.88
Fenvalerate 0.4% Dust [Known] 100 51.48 10.30 7.21 8.10 8.18 7.26
Endosulfan 4% Dust [Known] 1000 40.61 11.41 7.10 8.38 5.86 6.77
Control (Untreated check) 43.80 45.66 51.88 61.41 70.88 90.88
SEm± CD at 5% 1.21 3.63 0.45 1,35 0.53 1.59 0.60 1.80 0.58 1.74
Results show that N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroirnidazolidine is superior to commonly used insecticides, Fenveralate and Endosulfan 4% Dust.
EXAMPLE 12
20% Wettable Powder, Soluble Liquid, Suspension Concentration, Wettable Granules Effect on the Brinjal (EggPlant) jassids:
Order: Homoptera
Family: Cicadellidae
Insect: Amrasca biguttula biguttula Ishida
The field experiments was conducted during Rabi 2000 at Kolar (Karnataka) in a plot size of 50 Sq.rn in order to evaluate the efficacy of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-

dihydroimidazolidine (20% EC , WP, SL and WG) prepared according to Example 4 against brinjal jasslds. Each formulation was tested at 20 & 50 gai/ ha in comparison with known Imidacloprid 20 SL @ 20 gai/ ha and known Acetamiprid 20 SP at 20 gai/ ha and commonly used insecticide, Acephate 75% SP @ 500 gai/ ha. First application was made on 02-03-2001 and subsequent was at 15 days after first application by using high volume Knapsack sprayer. All the stages of jassids were counted on 6 randomly selected leaves per plant in 10 randomly selected plants in each plot before, 7 & 15 days after each spray. Results indicate that all the formulations of N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine at all the doses were found to be effective in checking the jassids population and were on par with Imidacloprid 20 SL @ 20 gai/ ha and Acetamiprid 20 SP @ 20 gai/ ha and superior to Acephate 75 SP.
Table 5 : Effect of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2- nitrimino-4,5-dihydroimidazolidine against Brinjal (egg plant) jassids, Amrasca biguttula biguttula

Treatment Dose
(g
a.i./ha) Mean number of jassids / 6 leaves

Before spray 7 days after I spray 15 days after I spray 7 days after II spray 15 days after II spray
N-(2-Chloro-5-
pyridy/metfiy/)-N' -(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4,5-
dihydroimidazolidine
(20%WP) 20 27.6 2.8 5.6 1.1 1.9

N-(2-Chloro-5-
pyridylmethyl)-N' -(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4,5-
dihydroimidazolidine
(20%WP) 50 25.8 2.1 5.9 0.9 1.3
N-(2-Chioro-5-
pyridylm ethyl )-N* -(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4,5-
dihydroimidazolidine
(20%SL) 20 27.1 3.0 5.3 1.3 1.4
N-(2-Chloro-5-
pyridylmethyl)-N' -(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4/5-
dihydroimidazolidine
(20%SL) 50 25.6 2.6 5.1 0.8 1.7
N-(2-Chloro-5-
pyridylmethyl)-N,-(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4/5-
dihydroimidazolidine
(20%WG) 20 27.9 2.8 6.0 0.9 1.2
N-(2-Chloro-5-
pyridylmethyl)-N * -(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4,5-
dihydroimidazolidine
(20%WG) 50 26.3 2.2 5.8 0.7 1.4

N-(2-Chloro-5-
pyridylmethyl)-N,-(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4,5-
dihydroimidazolidine
(20%SC) 20 27.5 3.1 5.9 1.0 1.8
N-(2-Chloro-5-
pyridylmethyl)-N"-(2-
chloro-5-thiazolylmethyl)-
2-nitrimino-4,5-
dihydroimidazolidine
(20%SC) 50 25.1 2.3 53 0.8 1.1
I m idacio prid [ Known] 20 26.9 2.1 4.3 0.9 1.8
Acetamiprid 20%SP[known] 20 25.8 2.0 4.6 1.0 1.6
Acetphate 75%SP[known] 600 26.1 6.4 10.1 4.3 8.7
Control (Untreated check) - 27.1 33.8 39.6 56.3 50.6
SEm± CD at 5% - - 0.43 1.29 0.85 2.55 0.40 1.20 0.53
1.59
Results indicate that all the formulations of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine at all the doses were found to be effective in checking the jassids population and were on par with Imidacloprid and Acetamiprid and superior to Acephate 75 SP.

EXAMPLE 13
20% Wettable Powder, Soluble Liquid, Suspension Concentration,
Wettable Granule
Effect on the Tobacco Aphid:
Order: Homoptera
Family: Aphididae
Insect: Myzus persicae Sulzer
The field experiment was conducted at Mysore (Karnataka) to evaluate the effect of N-(2-Chloro-5-pyridylmethyl)-N-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5 dihydroimidazolidine (20% SC, SL, WP & WG) prepared according to Example 4 against tobacco aphids during peak incidence. All the formulations of N-(2-Chloro-5-pyridylmethyl)-N^-(2-chloro-5-thiazolylmethy[)-2-nitrimino-4,5-dihydroimidazolidine were tested at 20 & 50 gai/ ha and were compared with known Imidacloprid 20 SL @ 20 gai/ ha, known Acetamiprid 20 SP @ 20 gai/ ha and known Acephate 75 SP @ 600 gai/ ha. The experiment was laid out as per randomized block design with 3 replications. Two applications were made at fortnightly intervals during peak aphid populations. Total spray volume was 400L/ ha with high volume Knapsack sprayer. Observations were made on total number of aphids from 3 (eaves in each pfant in 10 randomly selected plants in each plot before, 2, 7 & 14 days after each application. Results indicate that 20 & 50 gai/ ha of all the formulations of N-(2-Chloro-5-pyridylmethyl)-l\f -(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine are comparable with Imidacloprid 20 SL and Acetamiprid 20 SP and superior to Acephate 75 SP in checking the population of ahpids.

Table 6 : Effect of N-(2-Chloro-5-pyridylmethyl)-N' -(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine against Tobacco aphid, Myzus persicae

Treatment Dose (g -i./ha) Mean number of aphids / 3 leaves

Before spray 1 48 hrs after I spray 7 days after I spray 14 days after I spray 7 days after II spray 14 days after II spray
N-(2-Chloro-5- 20 148.6 5.7 33 12.8 1.8 6.4
pyridylmethyl)-N'-(2-
chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidin^
(20%SC)
N-(2-ChJoro-5- 50 150.2 5,1 4.2 12.2 2.1 5.9
pyridylmethyl)-N'-(2-
chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%SC)
N-(2-Chloro-5- 20 138.3 6.1 3.6 13.0 1.6 6.2
pyridylmethyl)-N' -Q.
chloro-5-
methyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%SL)

N-(2-Chloro-5-
pyridylmethyl)-N' -{2-
ch)oro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%SL) 50 141.8 5.8 3.1 11.9 2.2 6.0
N-(2-Chloro-5-
pyridylmethyl)-N ' -(2-
chloro-5-
thi'azolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WP) 20 150.7 6.3 3.8 12.5 2.1 5.6
N-(2-Chloro-5-
py ridy Imethy 1) - N' -(2-
chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WP) 50 138.8 5.4 3.5 13.2 1.7 5.8
N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-
dihydroimidazolidine (20%WG) 20 135.5 5.9 4.2 11.6 2.6 5.2
N-(2-Chloro-5-
pyridylmethyl)-N'-(2-
chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WG) 50 140.6 5.4 3.9 12.4 2.7 6.1

Imidacloprid 20SL [Known ] 20 148.7 4.4 2.2 11.3 1.3 4.2
Acetamiprid 20SP [Known] 20 150.6 4.9 2.8 12.0 1.4 4.8
Acephate 75SP [known ] 600 140.4 9.6 5.7 18.7 6.4 11.6
Control (Untreated check) 136.8 159.7 248.7 216.8 311.7 418.7
SEm + CD at 5% - - 0.94 2.92 0.71 2.13 0.80 2.40 0.65
1.95 0.91 2.73
Results indicate N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine are comparable with Imidacloprid and Acetamiprid and superior to Acephate
EXAMPLE 14
20% Wettable Powder, Soluble Liquid, Suspension Concentration, Wettable Granule Effect on the Chilli Aphid:
Order: Homoptera
Family: Aphididae
Insect: Myzus persicae Sulzer
The field experiment was conducted to evaluate the efficacy of four formulations of M-(2-Chloro-5-pyridylmethyl)-Ns-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine (20%) prepared by Example 4 against aphids on chilli variety Bydagi. It was compared with known Imidacloprid 20 SL @ 20 gai/ ha, known Acetamiprid 20 SP @ 20 gai/ ha and known Monocrotophas 36 SL @ 350 gai/ ha during peak incidence of aphids. Each formulations of N-(2-Chloro-5-

pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine was tested @ 20 & 50 gai/ ha. The experiment was laid out as per randomized block design with 3 replications. Insecticides were applied with a Knapsack sprayer using 450L spray liquid/ ha at 15 days intervals. Total number of aphids were counted in 3 leaves per plant in 10 randomly selected plants in each plot before, 48 hours, 7 & 15 days after each spray. Observations reveal that application of all the formulations of N-(2-Chforo-5-pyridylmethyl)-N' -(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine at 20 & 50 gai/ ha are significantly superior to Imidacloprid 20 SL, Acetamiprid 20 SP and including commonly used insecticide Monocrotophos 36 SL.
Table 7: Effect of N-(2-Chloro-5-pyridylmethyl)-N-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine against Chilli aphid, Myzus persicae

Treatment Dose
(g a.i./ha) Mean number of aphids / 6 leaves

Before spray 48 hrs after I spray 7 days after I spray 15 days after I spray 7 days after II spray 15 days after II spray
N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WP) 20 128.66 18.17 2.74 7.33 2.98 8.64
N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WP) 50 103.33 3.19 0.00 4.19 2.16 5.19

N-(2-Chloro-5-
pyridylmethyl)-N,-
(2-chloro-5-
thiazolyl methyl )-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WG) 50 . 123.96 5.48 0.68 3.81 2.24 4.96
Acetamiprid 20%SP [Known] 20 134.31 19.42 4.18 7.86 5.28 11.63
Imidacloprid 20%SL [Known] 20 124.85 21.38 12.59 10.48 7.49 16.19
Monocrotophos 36%SL[Known] 350 131.73 49.84 53.79 92.87 31.82 58.37
Control (Untreated check) - 127.48 143.29 138.72 164.53 183.94 190.81
SEm ± CD at 5% _ ; - 0.88 2.66 0.71 2.14 0.42 1.27 0.76 2.27
Observations show that application of all the formulations of N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine are significantly superior to Imidacloprid and Acetamiprid and including commonly used insecticide Monocrotophos.
EXAMPLE 15
20% Wettable Powder, Soluble Liquid, Suspension Concentration, Wettable Granule Effect on the Rice Brown plant hopper:
Order: Homoptera
Family: Delphacidae
Insect: Nilaparvatha lugens Stal
The field experiment was conducted at Warangal (Andhra Pardesh) to evaluate the bio-effcacy of Four formulations, viz SL, SC, WP & WG of N-(2-Chloro-5-

pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (20%) prepared by the Example 4 against brown plant hopper on rice. Each formulations were tested at 20 & 50 gai/ ha in comparison with known Imidacloprid 20 SL @ 20 gai/ ha and commonly used insecticides, known Acephate 75 SP @ 600 gai/ ha and known Chlorpyriphos 20 EC @ 300 gai/ ha. The trial was laid out in field with plots of 25 Sq.m area as per randomized block design with 3 replications. Total spray volume was 500ml/ ha with high volume sprayer. All the stages of hoppers were counted in 10 randomly selected hills per plot before, 2, 7,& 14 days after each spray. Results indicate that all the formulations of N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyI)-2-nitrimino-4,5-dihydroimidazolidine (20%) were significantly superior to commonly used insecticides, Acephate 75 SP and Chlorpyriphos 20 EC in controlling the brown plant hoppers. But it was on par with Imidacloprid 20 SL @ 20gai/ ha.
Table 8 : Effect of N-(2-Chloro-5-pyridylmethyl)-N' -(2-chloro-5-thiazoly1methyl)-2- nitrimino-4,5-dihydroimidazolidine against Rice brown plant hopper, Nilaparvata lugens

Treatment Dose (ga.l./ha) Mean number of brown plant hoppers/hill

Before spray 48 hrs after I spray 7 days after I spray 14 days after I spray 7 days after II spray 14 days after II spray
N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
thiazo/y/methyf)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WP) 20 84.73 6.89 6.18 7.64 3.16 5.96

N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chioro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WP) 50 78.48 3.52 1.32 2.96 0.84 3.67
N-(2-Chloro-5-pyridylrnethyi)-N' -
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%5L) 20 57.62 5.96 5.39 6.63 3.94 6.49
N-(2-Chloro-5-
pyridyl>TtethYi)-N'-
(2-ch)oro-5-
thiazQ(ylmethy()-2-
nitrimirto-4,5-
dihydroimidazoiidine
(20%SL) 50 63.13 2.87 2.16 3.27 1.23 2.82
N-(2-Chloro-5-pyridylmethyO-N' -
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroirrudazolidine
(20%SC) 20 46.24 5.23 4.37 5.66 2.87 4.69
N-(2-Chloro-5-
pyridylmethyl)-f\f-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%SC) 50 52.87 2.67 1.97 2.19 1.32 1.93

N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WG) 20 59.84 6.18 5.26 6.28 3.78 5.28
N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WG) 50 66.71 3.13 2.34 2.74 2.14 2.19
Imidacloprid 20SL Known 20 89.34 5.63 6.24 4.38 3.21 4.68
Acephate 75%SP Known 600 48.74 19.74 14.38 17.46 7.48 18.74
Chlorpyriphos 20%EC Known 300 51.86 24.86 23.14 37.43 23.74 32.82
Control (Untreated check) - 73.96 76.90 79.64 86.39 94.62 113.74
Sem + CD at 5% - - 0.71 2.17 1.02 3.08 0.83 2.49 0.55 1.69 0.78 2.37
Results indicate that all the formulations of N-(2-Chloro-5-pyridylmethyl)-Nv-(Z-chloro-S-thiazolylmethyO^-nitrimino^^-dihydroimidazolidine were significantly superior to commonly used insecticides, Acephate and Chlorpyriphos in controlling the brown plant hoppers. But it was on par with Imidacloprid.
EXAMPLE 16
20% Wettable Powder, Soluble Liquid, Suspension Concentration,
Wettable Granule
Effect on the Cotton aphid:

Order: Homoptera Family: Aphididae Insect: Ahpis gossypii G.
The field experiment was conducted on cotton to evaluate the efficacy of WP, SL, SC and WG formulations of N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (20%) prepared by the Example 4 against cotton aphids. This experiment was conducted at Bellary (Karnataka) on Cotton variety Savitha as per randomized block design with 12 treatments and 3 replications.(This is a standard ststistical design used for field experiments). The plot size was 25 Sq.m. The compositions were sprayed twice at an interval of 15 days with high volume Knapsack sprayer by using 500 Litres of spray volume per hectare during peak incidence. Total number of aphids were counted in 3 leaves per plant in 10 randomly selected plants per plot before, 7 & 14 days after application. The results indicate that all the formulations (20%WG/ 20 %Wp, 20%SI, 20 % SC) of N-(2-Chloro-5-pyhdylmethyl)-N^-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (20%) at all the doses (20 g a.i/ha and 50g a.i/ha) found to be significantly effective in checking the populations of aphids (0.4 to 4.8 aphids per 3 leaves) and was comparable to known Imidacloprid 20 SL @ 20 gai/ ha (2.4 to 5.8 aphids per 3 leaves), known Acetamiprid 20 SP @ 20 gai/ ha (3.1 to 4.6 aphids per 3 leaves) and superior to known Dimethoate 30 EC @ 350 gai/ ha (26.7 to 91.9 aphids per 3 leaves). Whereas untreated check (control) recorded 124.8 to 164.3 aphids per 3 leaves.
Table 9 : Effect of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine against Cotton aphid, Aphis gossypii

Treatment Dose
(g a.i./ha) Mean number of aphids / 3 leaves

Before spray 7 days after I spray 14 days after I spray 7 days after II spray 14 days after II spray
N-(2-Chloro-5-pyridylrnethyl)-
l\f-(2-chloro-5-
thiazolylmethyl)-2-nitrirnino-
4,5-dihydroimidazolidine
(20%WP) 20 95.3 3.1 4.8 1.76 4.3
N-(2-Chloro-5-pyridylmethyl)-
N'-(2-chloro-5-
thiazolylmethyl)-2-nitrirnino-
4,5-dihydroimidazolidine
(20%WP) 50 116.8 2.3 1.6 0.62 2.1
N-(2-Chloro-5-pyridylmethyl)-
N'-(2-chloro-5-
thiazolylmethyl)-2-nitrirnino-
4,5-dihydroimidazolidine
(20%SL) 20 98.7 2.8 3.7 2.2 3.4
N-(2-Chloro-5-pyridylmethyl)-
N'-(2-chloro-5-
thiazolylmethyl)-2-nitrimino-
4,5-dihydroimidazolidine
(20%SL) 50 106.9 1.9 1.4 0.8 1.3
N-(2-Chloro-5-pyridylmethyl)-
N'-(2-ch!oro-5-
thiazolylmethyl)-2-nitrimino-
4,5-dihydroimidazolidine
(20%SC) 20 94.2 3.3 3.2 1.9 2.7
N-(2-Chloro-5-pyridylmethyl)-
N1-(2-chloro-5-
thiazolylmethyl)-2-nitrimino-
4,5-dihydroimidazolidine
(20%SC) 50 124.3 2.1 1.6 0.4 0.8

N-(2-Chloro-5-pyridylmethyl)-l\f-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (20%WG) 20 92.1 2.9 3.3 2.0 2.6
N-(2-Chloro-5-pyridylmethyl)-
N'-(2-chloro-5-
thiazolylmethyl)-2-nitrimino-
4,5-dihydroimidazolidine
(20%WG) 50 99,9 1.7 2.1 0.6 0.8
Dimethoate 30%EC Known 350 103.0 42.8 91.9 26.7 61.4
Imidacloprid 20%SL known 20 127.1 4.6 4.7 2.4 5.8
Acetamiprid 20%SP Known 20 108.4 3.9 4.2 3.1 4.6
Control (Untreated check) - 113.7 124.8 142.3 164.3 159.8
Sem + CD at 5% - NS 1.03 3.09 0.98 2.94 0.89 2.67 0.96 2.88
The results indicate that N-(2-Chloro-5-pyridylmethyl)-N*-(2-chloro-5-thiazolylmethy))-2-nitrimino-4r5-dihydroimidazolidine (20%) at all the doses ( 20g a.i/ha and 50g a.i/ha) found to be significantly effective in checking the populations of aphids and was comparable to known Imidacloprid, known Acetamiprid and superior to known Dimethoate.
EXAMPLE 17 75% Wettable Seedresser Effect on the Sorghum Shoot fly:
Order: Diptera
Family: Muscidae
Insect: Atherigona varia Soccata Rend
N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4/5-dihydroimidazolidine (75% WS) seed dresser was prepared and

tested against Sorghum shootfly, Atherigona variasoccata Rond under field
conditions. This formulation was evaluated at 5 and 7.5 g/ kg seed in comparison
with known Imidacloprid 70 WS @ 5 and 7.5 g/ kg seed, known Truamethoxam
70 WS @ 4.8 g/ kg seed and known Carbosulfan 25 DS @ 50 g/ kg seed.
Observations were made on number of seeds germinated 25 days after sowing.
Observations were also recorded on number of damaged shoots and healthy
shoots in each plot 30 and 45 days after sowing. Observations reveal that all the
chemical treatments were found significantly superior in checking the shootfly
incidence. However, N-(2-Chloro-5-pyridylmethyl)-Nv-(2-chloro-5-
thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine @ 5 and 7.5 g/ Kg seed is superior to Carbosulfan 25 DS @ 50 g/ kg seed.
Table 10 : Effect of N-(2-Chloro-5-pyridylmethyl)-N-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine (75%WS) against Sorghum shootfly, Atherigona variasoccata

Treatment Dose
(g/kg seed) Mean per cent germination (25 DAS) Mean percent shootfly infestation

30 DAS 45 DAS
N-(2-Chloro-5-pyridylmethyl)-N' -(2-chloro-5-thiazoly[methyl)-2-nitrimino-4,5-dihydroimidazolidine (75%WS) 5 78.12 3.41 5.58
N-(2-Chloro-5-pyridylmethyl)-N' -(2-chloro-5-thiazolylmethyl)-2-nitrimino-
4,5-dihydroimidazolidine (75%WS) 7.5 79.63 3f94 5.06
Imidacloprid 70WS Known 5 80.30 2.73 4.78
Imidacloprid 70WS Known 7.5 78.44 2.62 4.90
Thiamthoxam 70WS Known 4.8 76.84 2.81 4.80
Carbosulfan 25DS Known 5.0 77.38 2.34 4.30
Control (Untreated check) - 78.44 25.63 35.78
Sem ± CD at 5% - - 0.80 2.40 0.61 1.83
DAS - Days after sowing

Observations reveal that all the chemical treatments were significantly superior in checking the shootfly incidence However, N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5_ dihydroimidazolidine is superior to carbosulfan.
EXAMPLE 18
20% Wettable Powder, Soluble Liquid, Suspension Concentration,
Wettable Granule
Effect on the Mongo Hoppers:
Order: Homoptera
Family: Cicadellidae
Insect: Amritodus atkinsoni L
The field experiment was conducted to test the efficiency of four formulations of
N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolyimethyl)-2-nitrimino-4,5-dihydroimidazolidine (20%) prepared as per the example 4 and was tested against Mango hoppers. All the formulations were tested @ 0.2 to 0.4 ml per litre of water in comparison with the standards, known imidacloprid 20 SL @ 0.2 ml per litre of water and known Acetamiprid 20 SP @ 0.2 g per litre of water and commonly used insecticide Endosulfan 35 EC (cp 2.5ml per litre of water. Insecticides were sprayed twice at 15 days interval with the help of Foot sprayer by using 4 litre spray volume per tree on 6 years aid Mango trees. In each tree, ten inflorescences were tagged and all the stages of hoppers were counted in each tagged inflorescence before, 48 hours, 7 any 14 days after each spray. Results reveal that all the formulations of N-(2-choloro-5,pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimiuazoidine (2o%) at 0.2 ml or 0.2 g/L was the most effective treatment compared to other treatments in controlling mango hoppers and it was statistically on par with imidacloprid 20 SL @ 0.2 ml per litre of water and Acetamiprid 20 SP @ 0.2 g per litre of water and

superior to commonly used insecticide, known Endosulfan 35 E @ 2.5ml per lil of water.
Table 11 : Effect of N-(2-Chloro-5-pyridylmethyl)-N'-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine against Mango hoppers, Amritodusatkinsoni

Treatment Dose
(ml/g/L) Mean number of hoppers / inflorescence

Before spray 48 hrs after I Spray 7 days after I spray 14 days after I spray 7 days after II spray 14 days after II spray
N-(2-Chloro-5-
pyridylmethyl)-l\r-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WP) 0.2 28.71 0.98 0.84 1.17 2.27 2.13
M-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
thiazoly!methyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WP) 0.4 30.64 0.71 0.12 0.98 0.84 0.94
N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%SL) 0.2 24.82 1.06 0.69 1.52 1.98 2.47

N-(2-Chloro-5-
pyridylmethyI)-N'-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%SL) 0.4 21.53 0,52 1 0.00 1 0.81 0.74 1 0.93 1
N-(2-Chloro-5-
pyridylmethyl)-N'-
(2-chloro-5-
th\axolylmetUvl>2-
nitrimino-4,5-
dihydroimidazolidine
(20%SC) 0.2 23.65 0.97 0.68 1.37 2.03 3.16
N-(2-Chloro-5-
pyridylmetbyO-rsT-
(2-chloro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
t20%SC) 0.4 27.81 0.64 0.00 0.16 0.46 0.84
N-(2-Chloro-5-
pyridylrnethyl)-N" -
(2-chloro-5-
thiazolylmethyI)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WG) 0.2 24.26 0.81 0.49 0.68 1.63 1.93
N-(2-Chloro-5-
pyridylrnethyl)-N"-
(2-ch)oro-5-
thiazolylmethyl)-2-
nitrimino-4,5-
dihydroimidazolidine
(20%WG) 0.4 26.84 0.48 0.00 0.00 0.25 0.88

Imidacloprid 20%SL Known 0.2 23.46 3.92 2.46 4.62 1.64 3.72
Acetamiprid 20%SP Known 0.2 27.84 4.84 3.01 3.94 2.38 4.28
Endosulfan 35%EC Known 2.5 23.81 10.26 8.19 12.19 9.86 11.86
Control (Untreated check) 26,97 29.43 41.85 47.52 53.95 59.24
Sem + CD" at 5% - - 0.74 2.23 0.40 1.21 0.43 1.39 0.45
1.31 0.62 1.86
Results reveal that all the formulations of N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thia2olylmethyl)-2-nitrimino-4,5-dihydroimidazolidine was the most effective treatment compared to other treatments in controlling mango hoppers and it was statistically on par with Imidacloprid and Acetamiprid r and superior to commonly used insecticide, known Endosulfan.
ADVANTAGES of the present invention
1. The efficacy of the composition is superior to conventional insecticides and on
par with certain insecticides such as Imidacloprid20%SL, Acetamiprid 20% SP.
2. The composition is relatively safer to insect parasitoid, predators and
honeybees.
3. The composition has got phytotonic effect on cotton, rice, vegetables etc.
4. The composition does not have any phytotoxicity effect on crop plants.
5. The composition is highly compatible with commonly used insecticides and fungicides.
WE CLAIM
1. A Novel 2-chloro-5-pyridylmethyl and its derivatives having the general

formula I.

Where: X = Halogens and R = Chloro Thiazole Group and its derivatives useful as broad-spectrum insecticide.
2. A Novel N-(2-Chloro-5-pyridylmethyl)-N*-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine having the formula II.

and its derivatives useful as a broad spectrum insecticide
3. A Process for the preparation novel compounds of the formula 1 as defined in claiml and its derivatives which is useful as a broad spectrum insecticide which comprises condensing a compound of the formula III with a thiazole of the formula IV


in the presence of a base and if desired ,converting the resulting compounds into its derivatives by conventional methods .
4. A Process for the preparation of N-(2-Chloro-5-pyridylmethyl)-Nv-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine of the formula II which is useful as a broad spectrum insecticide and its derivatives which comprises condensing N-(2-chloro-5-pyridylmethyI)-2-nitrimino-4,5-dihydroimidazolidine of the formula IIIA with 2-chloro-5-chloromethylthiazole of the formula IVA.

and if desired, converting the resulting compounds into its derivatives by conventional methods.
5. A Process as claimed in claims 3 & 4 wherein the condensation is effected
in the presence of a non-aqueous solvent or mixture thereof.
6. A Process as claimed in claim 5 wherein the solvents such as N,N-Dimethyl formamide, Dimethyl sulfoxide, acetonitrile, acetone, methyl isobutyl ketone, diethyl ketone etc. More preferably, N, N-Dimethyl formamide and acetonitrile and the like is sued in the condensation reaction.
7. A Process as claimed in claim 5 & 6 wherein the amount of solvent which is employed is in the range of 0-25 times molar equivalent of thiazole employed .
8. A Process as claimed in claims 3 to 7 wherein the condensation is effected

in the presence of a base such as hydroxide, carbonate or bicarbonate or any organic bases like tertiary amines.
9. A Process as claimed in claims 3 to 8 wherein the condensation is effected
at a temperature in the range of 25-80 °C, preferably in the range of 25-50 °C.
10. A Broad spectrum insecticide composition comprising the compound of
the formula I as defined in claim 1 and a carrier normally employed in such
composition.
11. A Broad spectrum insecticide composition as claimed in claim 10 wherein
the compound of the formula I employed is N-(2-Chloro-5-pyridylmethyl)-N,-(2-
chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine of the formula II.
12. A Broad spectrum insecticide composition as claimed in claims 10 & 11 wherein the amount of the active compound present in the composition ranges between 1 to 95% by weight of the active substance with 5% - 99% of inert materials and/ or adjuvants. Preferably the active ingredient may be in the range between 5% and 75% more preferably may be between 20% and 75%.
13. A Broad spectrum insecticide composition as claimed in claims 10 to 12 wherein the auxiliaries such as inert materials, surfactants, solvents and other additives, employed in the composition is / are those which is / are normally used in such compositions.
14. A Broad spectrum insecticide composition as claimed in claims 10 to 13 wherein the composition is in the form of a ready-mix formulation or a tank mix, Wettable powders which are uniformly dispersible.

15. A Broad spectrum insecticide composition as claimed in claims 10 to 14 wherein the composition also contains wetters, for example polyoxyethylated alkylphenols, polyoxyethylated fatty alcohols, alkylsulfonates or alkylphenolsulfonates and dispersants , for example ,sodium lignosulfonate or sodium 2,2'-dinaphthylrnethane-6,6'-disulfonate, in addition to the diluent or inert material.
16. A broad spectrum insecticide composition as claimed in claims 10 to 15 wherein the composition also contains other pesticidally active materials, fertilizers and/or growth regulators, besides the active substance and the inert agents.
17. A process for the preparation of a broad spectrum insecticide composition which comprises mixing thoroughly the compound of the formula I as active substance with inert material and adjuvants.
18. A process for the preparation of a broad spectrum insecticide composition as claimed in claim 17 wherein the compound used is N-(2-Chloro-5-pyridylmethyl)-N,-(2-chloro-5-thiazolylmethyl)-2-nitrimino-4,5-dihydroimidazolidine of the formula II
19. A process for the preparation of a broad spectrum insecticide composition as claimed in claims 17 & 18 wherein the amount of the active ingredient used ranges between l to 95% by weight of the active substance with 5% - 99% of inert material and/ or adjuvants. Preferably the active ingredient may be in the range between 5% and 75% more preferably may be between 20% and 75%.
20. Novel compound of the formula I as defined above and its derivatives
substantially as herein described with reference to the Examples 1 & 2.

21. Novel 2-chloro-5-pyridylmethyl and its derivatives having the general
formula II substantially as herein described with reference to the examples 1 &
2.
22. Novel broad spectrum insecticide composition containing Novel 2-chloro-5-
pyridylmethyl and its derivatives having the formula II substantially as herein
described with reference to the Examples 3 to 9.
23. A process for the preparation of broad spectrum insecticide containing Novel 2-chloro-5-pridylmethyl and its derivatives having the formula II substantially as herein described with reference to the Examples 3 to 18.