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WO2023148565A1 - Procédé de préparation de chlorhydrate de cartap - Google Patents

Procédé de préparation de chlorhydrate de cartap Download PDF

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Publication number
WO2023148565A1
WO2023148565A1 PCT/IB2023/050304 IB2023050304W WO2023148565A1 WO 2023148565 A1 WO2023148565 A1 WO 2023148565A1 IB 2023050304 W IB2023050304 W IB 2023050304W WO 2023148565 A1 WO2023148565 A1 WO 2023148565A1
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Prior art keywords
alcohol
dithiocyanato
propane
dimethylamino
predetermined temperature
Prior art date
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PCT/IB2023/050304
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English (en)
Inventor
Diwakar K Shenoy
Laxminarayan S Shet
Yatin S SAMANGADKAR
Vinay V Kalasapur
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Gharda Chemicals Ltd
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Gharda Chemicals Ltd
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Priority to AU2023215819A priority Critical patent/AU2023215819A1/en
Publication of WO2023148565A1 publication Critical patent/WO2023148565A1/fr
Anticipated expiration legal-status Critical
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C333/00—Derivatives of thiocarbamic acids, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
    • C07C333/02—Monothiocarbamic acids; Derivatives thereof
    • C07C333/04—Monothiocarbamic acids; Derivatives thereof having nitrogen atoms of thiocarbamic groups bound to hydrogen atoms or to acyclic carbon atoms

Definitions

  • the present disclosure relates to a process for the preparation of cartap hydrochloride.
  • Cartap is a thiocarbamate insecticide, having the chemical formula C7H16CIN3O2S2 [CAS No. 15263-53-3]. It is commonly used in the hydrochloride form (Cartap hydrochloride: C7H15N3O2S3HCI).
  • the chemical name of Cartap hydrochloride (I) is S-(3- carbamoylsulfanyl-2-(dimethylamino) propyl) carbamothioate hydrochloride.
  • Cartap hydrochloride is a nereistoxin analog that effectively eliminates insects through its contact, systemic and stomach action. It is essentially a contact insecticide and is highly effective against both chewing and sucking pests, resulting in paralysis. Cartap hydrochloride is categorized as an effective, relatively low-toxic, and low-residue insecticide. Cartap hydrochloride is preferred because of its broad-spectrum activity.
  • Another object of the present disclosure is to provide a process for the preparation of cartap hydrochloride.
  • Another object of the present disclosure is to provide a process for the preparation of cartap hydrochloride with a comparatively better yield and purity.
  • Yet another object of the present disclosure is to provide a process for the preparation of cartap hydrochloride using reagents which can be handled easily on a large scale.
  • Still another object of the present disclosure is to provide a process for the preparation of cartap hydrochloride by avoiding the use of dry HC1 gas.
  • Still another object of the present disclosure is to provide a simple and cost-efficient process for the preparation of cartap hydrochloride.
  • the present disclosure relates to a process for the preparation of cartap hydrochloride.
  • the process comprises reacting a compound selected from l,3-dithiocyanato-2- (dimethylamino) propane and its hydrochloride salt with a predetermined amount of first alcohol in a fluid medium and optionally by using an inorganic acid at a first predetermined temperature to obtain a first reaction mixture.
  • the first reaction mixture is cooled to a second predetermined temperature followed by slowly adding a predetermined amount of thionyl chloride for a first predetermined time period to obtain a second reaction mixture.
  • the second reaction mixture is heated to a third predetermined temperature for simultaneous removal of water and by-products to obtain a reaction mass.
  • the reaction mass is cooled to a fourth predetermined temperature followed by adding a second alcohol and refluxed for a second predetermined time period to obtain a slurry.
  • the slurry is cooled to a fifth predetermined temperature followed by filtration to obtain a wet cake and a first filtrate.
  • the wet cake is washed with at least one third alcohol followed by drying to obtain the cartap hydrochloride and a second filtrate.
  • Embodiments are provided so as to thoroughly and fully convey the scope of the present disclosure to the person skilled in the art. Numerous details are set forth, relating to specific components, and methods, to provide a complete understanding of embodiments of the present disclosure. It will be apparent to the person skilled in the art that the details provided in the embodiments should not be construed to limit the scope of the present disclosure. In some embodiments, well-known processes, well-known apparatus structures, and well-known techniques are not described in detail. The terminology used, in the present disclosure, is only for the purpose of explaining a particular embodiment and such terminology shall not be considered to limit the scope of the present disclosure.
  • first, second, third, etc. should not be construed to limit the scope of the present disclosure as the aforementioned terms may be only used to distinguish one element, component, region, layer or section from another component, region, layer or section. Terms such as first, second, third etc., when used herein do not imply a specific sequence or order unless clearly suggested by the present disclosure.
  • Cartap hydrochloride is a nereistoxin analog that effectively eliminates insects through its contact, systemic and stomach action. It is essentially a contact insecticide and is highly effective against both chewing and sucking pests, resulting in paralysis. Cartap hydrochloride is categorized as an effective, relatively low-toxic, and low-residue insecticide. Cartap hydrochloride is preferred because of its broad-spectrum activity. Conventional processes for the preparation of cartap hydrochloride are associated with disadvantages such as low yield, use of dry HC1 gas for carrying out the hydrolysis of thiocyanate intermediate compound. The use of dry HC1 gas on a large scale is associated with drawbacks such as increased production costs and handling issues. Further, hydrogen chloride (HC1) gas has a suffocating odour and is harmful to the respiratory tract of the person carrying out the reaction.
  • HC1 hydrogen chloride
  • the present disclosure provides an improved process for the preparation of cartap hydrochloride.
  • the process of the present disclosure is simple, environment friendly, economical, resulting in improved yields and higher purity.
  • the process of the present disclosure discloses a process for the preparation of cartap hydrochloride(I):
  • Molar mass: 237.3 the process comprising the following steps: a. reacting a compound selected from l,3-dithiocyanato-2- (dimethylamino)propane and its hydrochloride salt with a predetermined amount of first alcohol in a fluid medium and optionally by using an inorganic acid at a first predetermined temperature to obtain a first reaction mixture; b. cooling the first reaction mixture to a second predetermined temperature followed by slowly adding a predetermined amount of thionyl chloride for a first predetermined time period to obtain a second reaction mixture; c. heating the second reaction mixture to a third predetermined temperature for simultaneously removing water and by-products to obtain a reaction mass; d.
  • a first step the compound selected from l,3-dithiocyanato-2-(dimethylamino) propane and its hydrochloride salt is reacted with a predetermined amount of first alcohol in at least one fluid medium and optionally by using an inorganic acid at a first predetermined temperature to obtain a first reaction mixture.
  • the l,3-dithiocyanato-2- (dimethylamino) propane contains l,2-dithiocyanato-3-(dimethylamino)propane in an amount in the range of 0 to 10%.
  • l,3-dithiocyanato-2-(dimethylamino) propane is employed.
  • 1, 3-dithiocyanato-2-(dimethylamino) propane is a mixture of 1, 3-dithiocyanato-2-(dimethylamino) propane (90% w/w) and 1, 2- dithiocyanato-3 -(dimethylamino) propane (10% w/w) is employed.
  • the l,3-dithiocyanato-2- (dimethylamino) propane hydrochloride salt contains l,2-dithiocyanato-3- (dimethylamino)propane hydrochloride salt in an amount in the range of 0 to 10%.
  • l,3-dithiocyanato-2- (dimethylamino) propane hydrochloride salt is employed.
  • 1, 3-dithiocyanato-2-(dimethylamino) propane hydrochloride salt is a mixture of 1, 3-dithiocyanato-2-(dimethylamino) propane hydrochloride salt (90% w/w) and 1, 2- dithiocyanato-3 -(dimethylamino) propane hydrochloride salt (10% w/w) is employed.
  • the first alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, t- butanol, pentanol and isopentanol.
  • the first alcohol is methanol.
  • the fluid medium is selected from the group consisting of toluene, dichloroethane, xylene, chlorobenzene, and bromobenzene.
  • the fluid medium is toluene.
  • the fluid medium is dichloroethane.
  • the inorganic acid is aqueous HC1.
  • the concentration of inorganic acid is in the range of 25% w/w to 30% w/w HC1. In an exemplary embodiment of the present disclosure, the concentration of inorganic acid is 30% w/w HC1.
  • the first predetermined temperature is in the range of 25 °C to 40°C, preferably in the range of 30°C to 35 °C. In an exemplary embodiment of the present disclosure, the first predetermined temperature is 32°C.
  • the mole ratio of the compound selected from l,3-dithiocyanato-2-(dimethylamino) propane and its hydrochloride salt to the first alcohol is in the range of 1:4 to 1:10. In an exemplary embodiment of the present disclosure, the mole ratio is 1:4.94. In another exemplary embodiment of the present disclosure, the mole ratio is 1:6.18. In yet another exemplary embodiment of the present disclosure, the mole ratio is 1:8.65.
  • the first predetermined time period is in the range of 1 hour to 5 hours. In an exemplary embodiment of the present disclosure, the first predetermined time period is 4 hours.
  • the first reaction mixture is cooled to a second predetermined temperature followed by slowly adding a predetermined amount of thionyl chloride for a first predetermined time period to obtain a second reaction mixture.
  • the second predetermined temperature is in the range of 0.0°C to 25°C. In an exemplary embodiment of the present disclosure, the second predetermined temperature is below 25.0°C.
  • the second predetermined time period is in the range of 30 minutes to 120 minutes. In an exemplary embodiment of the present disclosure, the second predetermined time period is 60 minutes.
  • the mole ratio of the compound selected from 1, 3-dithiocyanato-2-(dimethylamino) propane and its hydrochloride salt to the thionyl chloride is in the range of 1: 1 to 1:5. In an exemplary embodiment of the present disclosure, the mole ratio is 1: 1.76. In another exemplary embodiment of the present disclosure, the mole ratio is 1:2. In still another exemplary embodiment of the present disclosure, the mole ratio is 1:2.5. In yet another exemplary embodiment of the present disclosure, the mole ratio is 1:4.
  • the second reaction mixture is heated to a third predetermined temperature for simultaneously removing water and by-products to obtain a reaction mass.
  • the third predetermined temperature is in the range of 70°C to 110°C. In an exemplary embodiment, the third predetermined temperature is 104°C. In another exemplary embodiment of the present disclosure, the third predetermined temperature is 82°C.
  • reaction mass is cooled to a fourth predetermined temperature followed by the addition of at least one second alcohol and refluxed for a second predetermined time period to obtain a slurry.
  • the fourth predetermined temperature is in the range of 50°C to 80°C. In an exemplary embodiment of the present disclosure, the fourth predetermined temperature is 65°C.
  • the second alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, t- butanol, pentanol and isopentanol.
  • the second alcohol is methanol.
  • the slurry is cooled to a fifth predetermined temperature followed by filtration to obtain a wet cake and a first filtrate.
  • the fifth predetermined temperature is in the range of 15°C to 25°C. In an exemplary embodiment of the present disclosure, the fifth predetermined temperature is 20°C.
  • the wet cake is washed with at least one third alcohol followed by drying to obtain the cartap hydrochloride (crop I) and a second filtrate.
  • the third alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, t- butanol, pentanol and isopentanol.
  • the third alcohol is methanol.
  • the alcohol and the fluid medium recovered are methanol and toluene. In another exemplary embodiment of the present disclosure, the alcohol and the fluid medium recovered are methanol and dichloroethane.
  • the fourth alcohol is selected from the group consisting of methanol, ethanol, propanol, isopropanol, n-butanol, t- butanol, pentanol and isopentanol.
  • the fourth alcohol is methanol.
  • the sixth predetermined temperature is in the range of 20°C to 35°C. In an exemplary embodiment of the present disclosure, the sixth predetermined temperature is 30°C.
  • the process of the present disclosure is simple, avoids the use of dry HC1 gas for preparing Cartap hydrochloride. The preparation of dry HC1 gas in the laboratory requires a specialized experimental setup. Further, it is very difficult to handle dry hydrochloric acid gas on a large scale. Hydrogen chloride (HC1) gas has a suffocating odour and is harmful to the respiratory tract of the person carrying out the reaction. The process of the present disclosure is safe and environment friendly.
  • the yield of the cartap hydrochloride obtained by the process of the present disclosure is in the range of 82% to 90%, comparatively higher in respect of the conventional processes.
  • the purity of the cartap hydrochloride obtained by the process of the present disclosure is >99.0 %.
  • the alcohol, toluene, and dichloroethane employed in the process of the present disclosure are separated, recovered, and recycled from the reaction process. Hence, the process of the present disclosure is economic and environment friendly.
  • the by-products such as sulphur-dioxide and methyl chloride formed during the process of the present disclosure are also scrubbed & compressed out. Therefore, the process of the present disclosure is environment friendly and suitable for industrial applications.
  • the purity of crop-I of cartap hydrochloride in accordance with the present disclosure is above 99%.
  • the yield of crop-I of cartap hydrochloride in accordance with the present disclosure is in the range of 75% to 90%.
  • the purity of crop-II of cartap hydrochloride as per the process of the present disclosure is above 87% to 90%.
  • the yield of crop-II of cartap hydrochloride as per the process of the present disclosure is in the range of 5 wt% tolO wt% which will be recycled in the process.
  • the reactor was equipped with an overhead stirrer, Dean and Stark system, thermometer, and glass condenser. 300 ml of toluene, 200 ml of methanol, and 100 ml of 30 % w/w HC1 were charged into a reactor and heated to 32°C, followed by adding 237.5 gm of (98.0 % purity) 1, 3-dithiocyanato-2-(dimethylamino) propane hydrochloride salt to obtain a first reaction mixture. The first reaction mixture was cooled to 15°C, maintaining the temperature below 25°C, 238.0 gm of thionyl chloride was slowly added over a period of 4 hours to obtain a second reaction mixture.
  • the so obtained second reaction mixture was equilibrated for 1 hour, and the temperature was raised up to 104°C (azeotropic reflux) with simultaneous removal of water and by-products to obtain a reaction mass.
  • the azeotropic distillation was continued till there was no more water separation at Dean and stark apparatus.
  • the addition of thionyl chloride and the rise in the temperature leads to the evolution of gases i.e., SO2 and methyl chloride.
  • SO2 generated was scrubbed with water, and the methyl chloride was passed through the brine cooled condenser and collected as a liquid.
  • the reaction mass was cooled to 65 °C followed by the addition of 1000 ml of methanol and refluxed for 1.0 hour to obtain a slurry.
  • the first filtrate and the second filtrate were mixed to obtain a filtrate mixture.
  • the methanol and toluene were recovered from the mixture of the first filtrate and the second filtrate by distillation till the precipitation of bottom mass to obtain a resultant mixture.
  • the so obtained resultant mixture was mixed with 100 ml of methanol and cooled to 30°C followed by filtration to obtain cartap hydrochloride (crop II).
  • the cartap hydrochloride (crop II) can be recycled in the next batch.
  • the reactor was equipped with an overhead stirrer, Dean and Stark system, thermometer, and glass condenser.
  • 350 ml of toluene, 200 ml of methanol, and 100 ml of 30 % w/w HC1 were charged into a reactor and heated to 32°C, followed by adding 237.5 gm of (98.0 % purity) 1, 3-dithiocyanato-2-(dimethylamino) propane hydrochloride salt and 13.7 grams of crop-II cartap hydrochloride (obtained in example 1) to obtain a first reaction mixture.
  • the first reaction mixture was cooled to 15°C, maintaining the temperature below 25°C added 238.0 gm of thionyl chloride slowly over a period of 4 hours to obtain a second reaction mixture.
  • the so obtained second reaction mixture was equilibrated for 1 hour, and the temperature was raised up to 104°C (azeotropic reflux) with simultaneous removal of water and by-products to obtain a reaction mass.
  • the azeotropic distillation was continued till there was no more water separation at Dean and stark apparatus.
  • the addition of thionyl chloride and the rise in the temperature leads to the evolution of gases i.e., SO2 and methyl chloride.
  • the SO2 generated was scrubbed with water, and the methyl chloride was passed through the brine cooled condenser and collected as a liquid.
  • the reaction mass was cooled to 65 °C followed by the addition of 1000 ml of methanol and refluxed for 1 hour to obtain a slurry.
  • the slurry was cooled to 20°C followed by filtration to obtain a wet cake and a first filtrate.
  • the so obtained wet cake was washed with 200 ml of methanol and dried to obtain the cartap hydrochloride and a second filtrate.
  • the purity of Cartap hydrochloride was >99.0 % and the yield was 246.0 gram (90.0 m%) gram (Crop I).
  • the first filtrate and the second filtrate were mixed to obtain a filtrate mixture.
  • the methanol and toluene were recovered from the mixture of first filtrate and second filtrate by distillation till the precipitation of bottom mass to obtain a resultant mixture.
  • the so obtained resultant mixture was mixed with 100 ml of methanol and cooled to 30 °C followed by filtration to obtain cartap hydrochloride (crop II).
  • the cartap hydrochloride (crop II) can be recycled in the next batch.
  • the reactor was equipped with an overhead stirrer, Dean and Stark system, thermometer, and glass condenser. 300 ml of toluene, 200 ml of methanol, and 100 ml of 30 % w/w HC1 were charged into a reactor and heated to 32°C, -followed by the addition of 237.5 gram of 90:10 ratios of l,3-dithiocyanato-2-(dimethylamino) propane hydrochloride salt:l,2- dithiocyanato-3-(dimethylamino)propane hydrochloride salt to obtain a first reaction mixture.
  • the first reaction mixture was cooled to 15 °C, maintaining the temperature below 25 °C and 238.0 gm of thionyl chloride was slowly added over a period of 4 hours to obtain a second reaction mixture.
  • the so obtained second reaction mixture was equilibrated for 1 hour, and the temperature was raised up to 104 °C (azeotropic reflux) with simultaneous removal of water and by-products to obtain a reaction mass.
  • the azeotropic distillation was continued till there was no more water separation at Dean and stark apparatus.
  • the addition of thionyl chloride and the rise in the temperature leads to the evolution of gases i.e., SO2 and methyl chloride.
  • the SO2 generated was scrubbed with water, and the methyl chloride was passed through the brine cooled condenser and collected as a liquid.
  • the reaction mass was cooled to 65 °C followed by the addition of 1000 ml of methanol and refluxed for 1 hour to obtain a slurry.
  • the so obtained slurry was cooled to 20°C followed by filtration to obtain a wet cake and a first filtrate.
  • the so obtained wet cake was washed with 200 ml of methanol and dried to obtain the cartap hydrochloride and a second filtrate.
  • the purity of cartap hydrochloride was >99.0 % and the yield was 205.0 gram (75.0 m%) (Crop I).
  • the first filtrate and the second filtrate were mixed to obtain a filtrate mixture.
  • the methanol and toluene were recovered from the mixture of first filtrate and second filtrate by distillation till the precipitation of bottom mass to obtain a resultant mixture.
  • the so obtained resultant mixture was mixed with 100 ml of methanol and cooled to 30°C followed by filtration to obtain cartap hydrochloride (crop II).
  • the cartap hydrochloride (crop II) can be recycled in the next batch.
  • the reactor was equipped with an overhead stirrer, Dean and Stark system, thermometer, and glass condenser. 750 ml of dichloroethane, 250 ml of methanol, and 100 ml of 30 % w/w HC1 were charged into a reactor and heated to 32°C, followed by the addition of 237.5 gram of (98.0 % purity) l,3-dithiocyanato-2-(dimethylamino) propane hydrochloride salt to obtain a first reaction mixture. The first reaction mixture was cooled to 15 °C, maintaining the temperature below 25 °C and 238.0 gm of thionyl chloride was slowly added over a period of 4 hours to obtain a second reaction mixture.
  • the so obtained second reaction mixture was equilibrated for 1 hour, and the temperature was raised up to 82 °C (azeotropic reflux) with simultaneous removal of water and by-products to obtain a reaction mass.
  • the azeotropic distillation was continued till there was no more water separation at Dean and stark apparatus.
  • the addition of thionyl chloride and the rise in the temperature leads to the evolution of gases i.e., SO2 and methyl chloride.
  • SO2 generated was scrubbed with water, and the methyl chloride was passed through brine cooled condenser and collected as a liquid.
  • the reaction mass was cooled to 65 °C followed by the addition of 1000 ml of methanol and refluxed for 1 hour to obtain a slurry.
  • the first filtrate and the second filtrate were mixed to obtain a filtrate mixture.
  • the methanol and dichloroethane were recovered from the filtrate mixture of the first filtrate and the second filtrate by using distillation till the precipitation of bottom mass to obtain a resultant mixture.
  • the so obtained resultant mixture was mixed with 100 ml of methanol and cooled to 30 °C followed by filtration to obtain cartap hydrochloride (crop II).
  • the cartap hydrochloride (crop II) can be recycled in the next batch.
  • the reactor was equipped with an overhead stirrer, Dean and Stark system, thermometer, and glass condenser. 750 ml of dichloroethane and 350 ml of methanol were charged into the reactor and heated to 32°C, followed by the addition of 237.5 gram of (98.0 % purity) 1, 3-dithiocyanato-2-(dimethylamino) propane hydrochloride salt to obtain a first reaction mixture. The first reaction mixture was cooled to 15 °C, maintaining a temperature below 25°C and 476.0 gm of thionyl chloride was slowly added over a period of 4 hours to obtain a second reaction mixture.
  • the so obtained second reaction mixture was equilibrated for 1 hour, and the temperature was raised up to 82°C (azeotropic reflux) with simultaneous removal of water and by-products to obtain a reaction mass.
  • the azeotropic distillation was continued till there was no more water separation at Dean and stark apparatus.
  • the addition of thionyl chloride and the rise in the temperature leads to the evolution of gases i.e. SO2 and methyl chloride.
  • SO2 generated was scrubbed with water, and the methyl chloride was passed through the brine cooled condenser and collected as a liquid.
  • the reaction mass was cooled to 65 °C followed by the addition of 1000 ml of methanol and refluxed for 1 hour to obtain a slurry.
  • the first filtrate and the second filtrate were mixed to obtain a filtrate mixture.
  • the methanol and dichloroethane were recovered from the mixture of the first filtrate and the second filtrate by distillation till the precipitation of bottom mass to obtain a resultant mixture.
  • the so obtained resultant mixture was mixed with 100 ml of methanol and cooled to 30 °C followed by filtration to obtain cartap hydrochloride (crop II).
  • the cartap hydrochloride (crop II) can be recycled in the next batch.
  • the reactor was equipped with an overhead stirrer, Dean and Stark system, thermometer, and glass condenser. 750 ml of dichloroethane, 250 ml of methanol, and 50ml water were charged into the reactor and heated to 32°C, followed by the addition of 237.5 gram of (98.0 % purity) l,3-dithiocyanato-2-(dimethylamino) propane hydrochloride salt to obtain a first reaction mixture. The first reaction mixture was cooled to 15°C, maintaining a temperature below 25 °C and 476.0 gm of thionyl chloride was slowly added over a period of 4 hours to obtain a second reaction mixture.
  • the so obtained second reaction mixture was equilibrated for 1 hour, and the temperature was raised to 82°C (azeotropic reflux) with simultaneous removal of water and by-products to obtain a reaction mass.
  • the azeotropic distillation was continued till there was no more water separation at Dean and stark apparatus.
  • the addition of thionyl chloride and the rise in the temperature leads to the evolution of gases i.e. SO2 and methyl chloride.
  • SO2 generated was scrubbed with water, and the methyl chloride was passed through the brine cooled condenser and collected as a liquid.
  • the reaction mass was cooled to 65 °C followed by the addition of 1000 ml of methanol and refluxed for 1 hour to obtain a slurry.
  • the slurry was cooled to 20°C followed by filtration to obtain a wet cake and first filtrate.
  • the so obtained wet cake was washed with 200 ml of methanol and dried to obtain the cartap hydrochloride and second filtrate.
  • the purity of Cartap hydrochloride was >99.0 % and the yield was 230.0 gram (84.0 m%).
  • the first filtrate and the second filtrate were mixed to obtain a filtrate mixture.
  • the methanol and dichloroethane were recovered from the mixture of the first filtrate and the second filtrate by distillation till the precipitation of bottom mass to obtain a resultant mixture.
  • the so obtained resultant mixture was mixed with 100 ml of methanol and cooled to 30°C followed by filtration to obtain cartap hydrochloride (crop II).
  • the cartap hydrochloride (crop II) can be which was recycled in the next batch.
  • the purity of cartap hydrochloride (crop-II) was 89% and the yield was 19.0 gram (7.0 m%).
  • the reactor was equipped with an overhead stirrer, Dean and Stark system, thermometer, and glass condenser.
  • 300 ml of toluene, 200 ml of methanol, and 100 ml of 30 % w/w HC1 were charged into a reactor and heated to 32°C, followed by adding 201 gm of (98.0 % purity) 1, 3-dithiocyanato-2- (dimethylamino) propane to obtain a first reaction mixture.
  • the first reaction mixture was cooled to 15°C, maintaining the temperature below 25°C, 297.5 gm of thionyl chloride was slowly added over a period of 4 hours to obtain a second reaction mixture.
  • the so obtained second reaction mixture was equilibrated for 1 hour, and the temperature was raised up to 104°C (azeotropic reflux) with simultaneous removal of water and by-products to obtain a reaction mass.
  • the azeotropic distillation was continued till there was no more water separation at Dean and stark apparatus.
  • the addition of thionyl chloride and the rise in the temperature leads to the evolution of gases i.e., SO2 and methyl chloride.
  • SO2 generated was scrubbed with water, and the methyl chloride was passed through the brine cooled condenser and collected as a liquid.
  • the reaction mass was cooled to 65 °C followed by the addition of 1000 ml of methanol and refluxed for 1.0 hour to obtain a slurry.
  • the first filtrate and the second filtrate were mixed to obtain a filtrate mixture.
  • the methanol and toluene were recovered from the mixture of the first filtrate and the second filtrate by distillation till the precipitation of bottom mass to obtain a resultant mixture.
  • the so obtained resultant mixture was mixed with 100 ml of methanol and cooled to 30°C followed by filtration to obtain cartap hydrochloride (crop II).
  • the cartap hydrochloride (crop II) can be recycled in the next batch.
  • the reactor was equipped with an overhead stirrer, Dean and Stark system, thermometer, and glass condenser.
  • 300 ml of toluene, 200 ml of methanol, and 100 ml of 30 % w/w HC1 were charged into a reactor and heated to 32°C, followed by adding 201 gm of gram of 90:10 ratios of l,3-Dithiocyanato-2-(dimethylamino) propane: 1,2-Dithiocy anato-3- (dimethylamino)propane to obtain a first reaction mixture.
  • the first reaction mixture was cooled to 15°C, maintaining the temperature below 25°C added 297.5 gm of thionyl chloride slowly over a period of 4 hours to obtain a second reaction mixture.
  • the so obtained second reaction mixture was equilibrated for 1 hour, and the temperature was raised up to 104 °C (azeotropic reflux) with simultaneous removal of water and byproducts to obtain a reaction mass.
  • the azeotropic distillation was continued till there was no more water separation at Dean and stark apparatus.
  • the addition of thionyl chloride and the rise in the temperature leads to the evolution of gases i.e., SO2 and methyl chloride.
  • the SO2 generated was scrubbed with water, and the methyl chloride was passed through the brine cooled condenser and collected as a liquid.
  • the reaction mass was cooled to 65 °C followed by the addition of 1000 ml of methanol and refluxed for 1 hour to obtain a slurry.
  • the slurry was cooled to 20°C followed by filtration to obtain a wet cake and a first filtrate.
  • the so obtained wet cake was washed with 200 ml of methanol and dried to obtain the cartap hydrochloride and a second filtrate.
  • the purity of Cartap hydrochloride was >99.0 % and the yield was 205.0 gram (75.0 m%) gram (Crop I).
  • the first filtrate and the second filtrate were mixed to obtain a filtrate mixture.
  • the methanol and toluene were recovered from the mixture of first filtrate and second filtrate by distillation till the precipitation of bottom mass to obtain a resultant mixture.
  • the so obtained resultant mixture was mixed with 100 ml of methanol and cooled to 30 °C followed by filtration to obtain cartap hydrochloride (crop II).
  • the cartap hydrochloride (crop II) can be recycled in the next batch.
  • the process of the present disclosure doesn’t use dry HC1, thus avoiding expensive infrastructure requirements for performing the reaction. Further, the optimized process conditions ensure the obtained product with high purity (>99%) irrespective of the raw material quality (90:10 reactant isomer ratio).

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  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

La présente divulgation concerne un procédé de préparation de chlorhydrate de cartap. Le procédé selon la présente divulgation est mis en œuvre en présence d'un milieu fluide qui peut être facilement séparé, récupéré et recyclé. Le procédé est simple, efficace, respectueux de l'environnement, et fournit du chlorhydrate de cartap avec une pureté comparativement élevée et un rendement élevé. Le procédé selon la présente divulgation est économique et utilise des réactifs qui peuvent être manipulés facilement à grande échelle.
PCT/IB2023/050304 2022-02-01 2023-01-13 Procédé de préparation de chlorhydrate de cartap Ceased WO2023148565A1 (fr)

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AU2023215819A AU2023215819A1 (en) 2022-02-01 2023-01-13 A process for the preparation of cartap hydrochloride

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118993965A (zh) * 2024-10-24 2024-11-22 湖南工程学院 一种提高杀虫单产品收率和纯度的方法

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018181672A1 (fr) * 2017-03-30 2018-10-04 住友化学株式会社 Chlorhydrate de 1,3-dicarbamoylthio-2-(n,n-diméthylamino)propane stable et son procédé de production

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2018181672A1 (fr) * 2017-03-30 2018-10-04 住友化学株式会社 Chlorhydrate de 1,3-dicarbamoylthio-2-(n,n-diméthylamino)propane stable et son procédé de production

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN118993965A (zh) * 2024-10-24 2024-11-22 湖南工程学院 一种提高杀虫单产品收率和纯度的方法

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