Manufacturing Method For and Insecticidal Compositions Comprising Thiocyclam Hydrochloride

Abstract

A method for manufacturing an insecticidal compound and insecticidal compositions comprising the insecticidal compound and methods of use are presented herein. The manufacturing method presented herein allows for a high purity grade of thiocyclam hydrochloride to be synthesized. The insecticidal compositions comprising the thiocyclam hydrochloride can be used for prevention of crop destruction by insects. The use of thiocyclam hydrochloride in insecticidal compositions as described herein can achieve greater efficacy than previously known insecticides, by eliminating the insect pests more reliably and efficiently.

1 . A method of manufacturing N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride comprising the steps of:
 a) providing a mixture of thiosulfuric acid S,S′-[2-(dimethylamino)trimethylene] ester monosodium salt and sodium hydroxide;   b) adding an aqueous saline solution to the mixture of thiosulfuric acid S,S′-[2-(dimethylamino)trimethylene] ester monosodium salt and sodium hydroxide, wherein the aqueous saline solution is added over the course of at least 3 hours;   c) separating the phases of the mixture;   d) collecting the solids from the mixture using filtration;   c) washing the solids with organic solvent; and   f) drying the solids,   wherein the dried solids are N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride.   
     
     
         2 . The method according to  claim 1 , wherein the organic solvent comprises methyl-t-butyl ether, toluene, isopropanol or mixtures thereof. 
     
     
         3 . The method according to  claim 1 , wherein the aqueous saline solution comprises sodium chloride. 
     
     
         4 . The method according to  claim 1 , wherein the temperature during step b) is between −10 to −25° C. 
     
     
         5 . The method according to  claim 4 , wherein the temperature during step b) is between −15 to −20° C. 
     
     
         6 . The method according to  claim 1 , wherein 2M ethereal hydrochloric acid is added to the mixture after step c) and before step d). 
     
     
         7 . The method according to  claim 1 , wherein 2M hydrochloric acid in isopropanol is added to the mixture after step c) and before step d). 
     
     
         8 . The method according to  claim 1 , wherein the aqueous saline solution comprises sodium sulfide. 
     
     
         9 . The method according to  claim 1 , wherein the purity of the N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride is greater than 90%. 
     
     
         10 . The method according to  claim 9 , wherein the purity of the N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride is greater than 95%. 
     
     
         11 . The method according to  claim 1 , wherein the % yield of N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride is greater than 30%. 
     
     
         12 . The method according to  claim 11 , wherein the % yield of N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride is greater than 60%. 
     
     
         13 . An insecticidal composition wherein the composition comprises:
 a) N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride and/or solvate thereof;   b) one or more auxiliary component; and   c) optionally, a safener.   
     
     
         14 . An insecticidal composition according to  claim 13 , wherein the composition comprises from about 1-10 parts by weight N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride. 
     
     
         15 . An insecticidal composition according to  claim 14 , wherein the composition comprises about 1 part by weight N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride. 
     
     
         16 . The insecticidal composition according to  claim 13 , wherein the safener is selected from the group isoxadifen-ethyl, 1,8-dicarboxylic anhydride, mefenpyr-diethyl, fenchlorazole-ethyl, cloquintocet-mexyl, and combinations of the foregoing. 
     
     
         17 . The insecticidal composition according to  claim 16 , wherein the safener comprises isoxadifen-ethyl. 
     
     
         18 . The insecticidal composition according to  claim 16 , wherein relative to 1 part by weight of the N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride, the safener comprises about 0.1 to 10 parts by weight. 
     
     
         19 . The insecticidal composition according to  claim 13  that comprises an auxiliary selected from the group consisting of an emulsifier, a thickener, a surfactant, an inert solid carrier, an organic suspending medium, or combinations of the foregoing. 
     
     
         20 . The insecticidal composition according to  claim 19 , wherein the auxiliary is an emulsifier selected from the group consisting of a fatty alcohol-polyoxyethylene ether, dehydrated sorbitol polyoxyethylene ether, dibenzyl phenol polyoxyethylene ether, polyoxyethylene dehydrated sorbitol ether monooleate, styryl phenol polyoxyethylene ether, fatty amine polyoxyethylene ether, and combinations of one or more of the foregoing. 
     
     
         21 . The insecticidal composition according to  claim 19 , wherein the auxiliary is a thickener selected from the group consisting of polyvinylpyrrolidone, xanthan gum, aluminium-magnesium silicate, polyvinyl alcohol and polyvinyl acetate, and combinations of one or more of the foregoing. 
     
     
         22 . The insecticidal composition according to  claim 19 , wherein the auxiallry is a surfactant selected from the group consisting of sodium methylene bis-naphthalene sulfonate, sodium lignin sulfonate, calcium lignosulphonate, calcium dodecyl benzene sulfonate, sodium succinate, diisobutyl naphthalene sulfonic acid sodium salt (nekal BX), sodium laurylsulfate, and combinations of one or more of the foregoing. 
     
     
         23 . The insecticidal composition according to  claim 19 , wherein the auxiallry is an inert solid carrier selected from the group consisting of clay, silica, diatomaceous earth, kaolin, attapulgite, moat-morillonite, bentonite, talcum powder, white carbon black, calcium carbonate, and combinations of one or more of the foregoing. 
     
     
         24 . The insecticidal composition according to  claim 19 , wherein the auxiliary is an organic suspending medium selected from the group consisting of soybean oil, rapeseed oil, corn oil, sunflower oil, cottonseed oil, linseed oil, coconut oil, palm oil, peanut oil, olive oil, castor oil, transesterification products thereof, and combinations of one or more of the foregoing. 
     
     
         25 . The insecticidal composition according to  claim 13 , wherein a ratio of the part by weight of the N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride to the parts by weight of the one or more auxiliary is 1: (0.2-15). 
     
     
         26 . The insecticidal composition of  claim 13 , wherein the composition is in the form of a solution, emulsifiable concentrate, wettable powder, suspension, powder, dust, paste, soluble powder, granules, suspo-emulsion concentrate, oil spray, aerosol, natural and synthetic materials impregnated with the composition, or as capsules in polymeric substances. 
     
     
         27 . The insecticidal composition of  claim 26 , wherein the composition is in the form of an emulsifiable concentrate, wettable powder, granules, dust, oil spray, or aerosol. 
     
     
         28 . A method for prevention of insects for a crop using a insecticidal composition comprising;
 a) N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride and/or a solvate thereof;   b) one or more auxiliary compounds; and   c) optionally, a safener; and   wherein an insecticidally effective amount of the insecticidal composition is applied to a crop.   
     
     
         29 . The method according to  claim 28 , wherein the crop comprises at least one of radish and bean. 
     
     
         30 . The method according to  claim 28 , wherein the insects comprise at least one of codling moths, soybean loopers, aphids, and white flies. 
     
     
         31 . The method according to  claim 28 , wherein the insecticidal composition comprises:
 i) about 1 part by weight N,N-dimethyl-1,2,3-trithian-5-ylamine hydrochloride and/or a solvate thereof;   ii) about 0.01-90 parts by weight of one or more auxilliary; and   iii) optionally, about 0.1-10 parts by weight safener.   
     
     
         32 . The method according to  claim 28 , wherein an application rate of the insecticidal composition is in a range from 0.0225 g/m 2  to 0.7500 g/m 2 . 
     
     
         33 . The method according to  claim 28 , wherein the insecticidal composition is in the form of a solution, emulsifiable concentrate, wettable powder, suspension, powder, dust, paste, soluble powder, granules, suspo-emulsion concentrate, oil spray, aerosol, natural and synthetic materials impregnated with the composition, or as capsules in polymeric substances. 
     
     
         34 . The method according to  claim 28 , wherein the composition is in the form of an emulsifiable concentrate, wettable powder, granules, dust, oil spray, or aerosol.