FORM 2
THE PATENT ACT, 1970
(39 OF 1970)
COMPLETE SPECIFICATION
(See Section 10; rule 13)
Tiltle : PROCESS OF MANUFACTURE OF METOFLUTHRIN TECHNICAL
Applicant: SHOGUN ORGANICS LIMITED, 502 B, Kotia Nirman, Link Road, Andheri (W), Mumbai- 400 053. Maharashtra, India, An Indian Company.
The following specification particularly describes the nature of the invention and the manner in which it is to be performed.

Description
The process design is used to manufacture a pyrethroid ester insecticide. Its is effective to kill or repel mosquitoes and other insects. This pyrethroid insecticide is based on a Chrysanthemic Acid derivative binder and a tetrafluorobenzyl that exhibits good insecticidal activity. This is suitable against home insects and pests. At appropriate low dosage in product applications along with other carriers and solvents , this chemical can help to effective in repelling mosquitoes and other insects.
The ester is based on Chrysanthemic Acid 2,2-dimethyl -3-{2-methylprop-1 -enyl) Cyclopropanecarboxylate which is then reacted with a flurobenzyl in prescribed conditions with a catalyst. Compounds with these ingredients have shown to have insecticidal properties .
For consumer use , formulations are used with this chemical , in different ways. This active compound Metofluthrin or along with other materials are made into conventional solutions and formulations. Some formulations mix the active compound with volatile solvents , liquefied gases , or are used in mosquito repellent spiral coils.
Need for low cost active components are more on the rise. The current product and process help to achieve higher yield by efficient process factors and use of new catalyst to achieve higher yield and purity. Thereby giving a new low cost, effective , and pure technical material. For these specific input reactants addition of a new catalyst , in place of organic solvent , can increase purity and yield .

Process
A1 Acid io Acid Chloride :

(1 R,3R)-2,2-dimethyl -3-(2-methylprop-1-eny!) Cyciopropanecarboxylate
Charge Chrysanthemic Acid 90% trans 75 gms and n-Heptane 105 ml in vessel. Charge high purity Thionyl Chloride 63.6 gms in separate vessel. Charge 215 ml n-Heptane in main reactor. Heat the contents to 65° C. Begin addition of Thionyl Chloride with and mix of Chrysanthemic Acid and n-Heptane alternatively. Gradually over a 2 hour time period. Once entire quantity is added maintain reflux for 140 minutes. Control temperature at 65° C. Cool the mixture to 40° C . Then heat up to 70° C. Repeat and continue till Acid is reacted. Then transfer to distillation. Heat the contents and maintain temperature at 95 C under vaccum 670 mmHG. Run distillation for 3 to 4 hours only. Purity of 98.6% trans chrysanthemic acid chloride output 82.7 gms
B1 Reaction of the Specifically prepared Acid Chloride with 2.3,5,6-tetrafluoro-4- methoxvmethvlbenzvl ;

Optimum use of temperature control , mixing of reactants and the addition parameters and reaction time have contributed to higher yields and better purity. Vaccum reactions save time and thereby reduce cost of energy and utilities used . Ideal balance of Vaccum and temperature was also observed in this synthesis process.

Add 51 gms 2,3,5,6-tetrafluoro-4-methoxymethylben2y| and 320 ml Toluene in presence of 1.5 gms catalyst in main reactor. Temperature controlled between 8°C to 12°C. Stirring for 15 mins. Add Caustic Soda and Water. Add the specifically prepared Acid Chloride under vacuum. Temp should be maintained at 12 C. Alternate addition of Caustic soda and 64 gms Chrysanthemic Acid Chloride spread over 90 minutes. After addition of caustic solution , complete addition of acid chloride. Maintain the reaction and mass for 120 to 140 minutes. Neutralize the mass and control Ph by adding Hydrochloric acid and water . Then separate and extract the organics layer. Transfer mass for distillation. Heat the mass appropriately upto 130° C under vaccum of 700 mmHg
This gives total 94.4 gms Metofluthrin with a purity of 98.9%

Example 1 :
A]
A 500 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser. Charged Chrysanthemic Acid 80 gms in glass addition flask. Charged 68 gms ThionyJ Chloride in another adding flask. Charged n-Heptane 300 ml in main glass flask. Started heating n-Heptane to 60° C. Started adding slowly Thionyl chloride and chrysanthemic Acid in main flask alternatively. Started stirring and heating the flask to get mixture reflux. Maintained refluxing for 140 minutes with temperature 65° C. Checked the presence of chrysanthemic acid. Obtained 85 .3 gms Chrysanthemic Acid chloride with 97.2% purity
B]
A 1000 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser and two adding glass flask. Charged 80 gms of 97.2% purity Chrysanthemic Acid Chloride in a adding glass flask. Then charged Caustic Soda solution 10% in water in another glass adding flask. Charged 65 gms of 2,3,5,6- tetrafluoro-4-methoxymethylbenzyl Alcohol in a main glass flask with catalyst 2.8 gms and Toluene 340 ml. Started adding slowly the Chrysanthemic Acid Chloride and Caustic solution 10% in main glass flask to reaction with 2,3,5,6-tetrafluoro-4-methoxymethyl benzyl Alcohol with stirring. Temparature maintained between 20° to 25° C. Adding completed in 21/2 hr time. On the completion of the reaction, the reaction mixture was washed three times with 10% of HCL and water. Added 200 ml water to get pH neutral After washing is completed sent the reacted mixture for distillation with the temp 135° C and Vacuum 670 mmHg. Obtained 114.2 gms of Metofluthrin with purity 96.8%
Example 2 :
A]
A 500 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser. Charged 75 gms Chrysanthemic Acid in glass addition flask. Charged 65 gms Thionyl Chloride in another adding flask. Charged 300 ml n-Heptane in main glass flask. Started heating n-Heptane to 60° C. Started adding slowly Thionyl chloride and chrysanthemic Acid in main flask alternatively. Started stirring and heating the flask to get mixture reflux. Maintained refluxing for 2 Hrs with temperature 70° C. Checked the presence of Chrysanthemic acid. Obtained 82 5 gms Chrysanthemic Acid chloride with 97.5 purity
B]
A 1000 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser and two adding glass flask. Charged 67 gms Chrysanthemic Acid Chloride in a adding glass flask. Then charged 33 ml Pyridine in main glass flask.
Charged 55 gms 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl Alcohol in a main glass flask with Toluene 240 ml. Started adding slowly the Chrysanthemic Acid Chloride in main glass flask to reaction with 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl Alcohol with stirring. Temparature maintained between 25° to 30° C. Adding completed in 21/2 hrs time. On the completion of the reaction, the reaction mixture was washed two times with 30% and 10% of HCL and water and one time with 2.5% NaOH solution. Added 220 ml water for further wash to get pH neutral After washing is completed sent the reacted mixture for distillation with the temp 1400 C and Vacuum 670 mmHg. Obtained 98.3 gms Metofluthrin with purity 96.6%
Example 3 :
A]
A 500 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser Charged 75 gms Chrysanthemic Acid and 310 ml n-Heptane in glass flask. Charged 63.6 gms Thionyl Chloride in adding flask. Started adding slowly Thionyl chloride in main flask. Started heating the flask to get mixture reflux. Maintained refluxing for 2 hrs with temperature 70° C. Checked the presence of chrysanthemic acid. Obtained 82.1 gms Chrysanthemic Acid chloride with 97.2% purity
B]
A 1000 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser and two adding glass flask. Charged 65 gms Chrysanthemic Acid Chloride in a adding glass flask. Then charged 35 ml Pyridine in main glass flask. Charged 55 gms 2,3,5,6-tetrafluoro-4-methoxymethyIbenzyl Alcohol in a main glass flask with Toluene 240 ml. Started adding slowly the Chrysanthemic Acid Chloride in main glass flask to reaction with 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl Alcohol with stirring. Temparature maintained between 20° to 25° C Adding completed in 2Vi hrs time. On the completion of the reaction, the reaction mixture was washed two times with 30% and 10% of HCL and water and one time with 2.5% NaOH solution. Added 220 ml water for further wash to get pH neutral. After washing is completed sent the reacted mixture for distillation with the temp 135° C and Vacuum 700 mmHg. Obtained 97.5 gms Metofluthrin with purity 97%
Example 4:
A]
A 500 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser. Charged 75 gms Chrysanthemic Acid in glass addition flask. Charged 63.6 gms Thionyl Chloride in another adding flask. Charged 320 ml n-Heptane in main glass flask. Started heating n-Heptane to 60° C. Started adding slowly Thionyl chloride and chrysanthemic Acid in main flask alternatively. Started stirring and heating the flask
to get mixture reflux. Maintained refluxing for 2 hrs with temperature 70° C. Checked the presence of chrysanthemic acid. Obtained 82.5 gms Chrysanthemic Acid chloride with 98.5% purity
B]
A 1000 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser and two adding glass flask. Charged 65 gms Chrysanthemic Acid Chloride in a adding glass flask. Then charged Caustic Soda solution 15% in water in another glass adding flask. Charged 51 gms of 2,3,5,6-tetrafluoro-4- methoxymethylbenzyl Alcohol in a main glass flask with catalyst 1.6 gms and Toluene 300 ml. Started adding slowly the Chrysanthemic Acid Chloride and Caustic solution 15% in main glass flask to reaction with 2,3,5,6-tetrafluoro-4-methoxymethylbenzyl Alcohol with stirring. Temparature maintained between 15° to 20° C. Adding completed in 2 hr time. On the completion of the reaction, the reaction mixture was washed two times with 30% of HCL and water. Added 200 ml water to get pH neutral. After washing is completed sent the reacted mixture for distillation with the temp 125° C and Vacuum 700 mmHg. Obtained 91.5 gms of purity 97 .8%
Example S :
A]
A 500 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser. Charged 75 gms Chrysanthemic Acid in glass addition flask. Charged 63.6 gms Thionyl Chloride in another adding flask. Charged 320 ml n-Heptane in main glass flask. Started heating n-Heptane to 65° C Started adding slowly Thionyl chloride and chrysanthemic Acid in main flask alternatively. Started stirring and heating the flask to get mixture reflux. Maintained refluxing for 2 hrs with temperature 70° C. Checked the presence of chrysanthemic acid. Obtained 82 7 gms Chrysanthemic Acid chloride with 98.6% purity
B]
A 1000 ml volume four necked glass flask equipped with a stirrer, a thermometer and a reflux condenser and two adding glass flask Charged 64 gms Chrysanthemic Acid Chloride in a adding glass flask. Then charged Caustic Soda solution 15% in water in another glass adding flask. Charged 51 gms of 2,3,5,6-tetrafluoro-4- methoxymethylbenzyl Alcohol in a main glass flask with catalyst 1.5 gms and Toluene 320 ml. Started adding slowly the Chrysanthemic Acid Chloride and Caustic solution 15% in main glass flask to reaction with 2,3,5,6-tetrafluoro-4-methoxy methyl benzyl Alcohol with stirring. Temparature maintained between 8° to 12° C. Adding completed in VA hr time. On the completion of the reaction, the reaction mixture was washed two times with 30% of HCL and water. Added 200 ml water to get pH neutral. After washing is completed sent the reacted mixture for distillation with the temp 130° C and Vacuum 700 mmHg. Obtained 94.4 gms of purity 98 .9%

Claims
We claim , process of manufacture of Metofluthrin Technical comprising following steps:
1. Chrysanthemic Acid 75 gms and n-Heptane 105 ml, high purity Thionyl Chloride 63.6 gms input
2. Temperature of 65°C and 140 minutes reaction
3. Cooling to 40° C . Then heating to 70° C
4. Distill at 95°C under vaccum 670 mmHG
5. Purity of 98.6% chrysanthemic acid chloride output 82.7 grams
6. Reaction of 51 gms of 2,3,5t6-tetrafluoro-4-methoxymethylbenzyl, 320 ml Toluene in presence of catalyst, with 64 gms Chrysanthemic Acid Chloride
7. Temperature controlled between 8°C to 12°C
8. Gradual adding time of 90 minutes of reactants
9. Reaction of 120 to 140 minutes.
10. Distillation upto 130° C and vaccum of 700 mmHg
11. Output 94.4 gms Metofluthrin purity of 98.9%
12. Use of derivative nucleophilic catalyst in range of 0.1 grams to 3 grams , in place of conventional heterocyclic organic solvents to give better yield and better reactivity