- Synthesis, characterization and crystal structure of n-(3-((2-chlorothiazol-5-yl)methyl)-5-methyl-1,3,5-oxadiazinan-4-ylidene)nitramide
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N-(3-[(2-chlorothiazol-5-yl)methyl]-5-methyl-1,3,5-oxadiazinan-4-ylidene)nitramide (I), i.e., thiamethoxam, it is a broad-spectrum insecticide that effectively controls insects, being a second generation neonicotinoid compound belonging to the chemical subclass the thianicotinyls. It was prepared from 5-(chloromethyl)-2-(phenylthio)thiazole (1) via chlorination by Cl2/HCl system and then condensation by K2CO3/CsI. The product was characterized by NMR and LC-MS. The crystal structure of compound I was investigated using X-ray diffraction and SHELXTL-97 software. The result indicated that compound I crystallized in the monoclinic system, space group P 21/n with a = 6.488(13), b = 28.786 (6), c = 6.804(14) ?, V=1225.1 (5) ?3; Z4.
- He, Jian-Ling,Cheng, Wei-Hua
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Read Online
- Synthesis method of 2-chloro-5-chloromethylthiazole by photocatalytic chlorination
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The invention relates to the technical field of synthesis of 2-chloro-5-chloromethylthiazole, and provides a synthesis method of 2-chloro-5-chloromethylthiazole by photocatalytic chlorination, which comprises the following steps: S1. adding 2-chloropropenyl thioisocyanate, sulfonyl chloride and acetonitrile into a tower reactor, and stirring to dissolve; S2, adding a catalyst, irradiating with ultraviolet light, and starting chlorination reaction; S3, carrying out reduced pressure distillation to remove the solvent acetonitrile; S4, dissolving distilled residues in dichloromethane, respectively washing with a NaHCO3 solution and water to be neutral, and carrying out reduced pressure distillation to obtain a 2-chloro-5-chloro methylthiazole product. Through the technical scheme, the problems of poor product quality and low yield in the prior art are solved.
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Paragraph 0023-0032
(2021/04/17)
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- Continuous production process of 2-chloro-5-chloromethylthiazole
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The invention provides a continuous production process of 2-chloro-5-chloromethylthiazole, which comprises the following steps of providing an organic solvent, and mixing a raw material 2-chloro-3-isothiocyano-1-propylene into the organic solvent to form a mixed solution, providing a continuous chlorination device, introducing chlorine into the device, and carrying out chlorination reaction, providing a rectification device, and sequentially carrying out solvent distillation removal, light component distillation removal and heavy component removal rectification in a vacuum state to obtain a 2-chloro-5-chloromethylthiazole product. The chlorination reaction is carried out in a continuous feeding and continuous overflowing manner; and the rectification device adopts the operation conditions of continuous feeding and continuous vacuum rectification. According to the process, the content of 2-chloro-5-chloromethylthiazole is increased to 99% or above, the content of by-products is reduced by 0.5% or below, the yield is increased to 91% or above, continuous production is safe and controllable, the generation amount of by-products and wastes is small, the product quality is stable, and green, environment-friendly and safe industrial production is achieved.
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Paragraph 0049-0072
(2021/10/27)
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- Tower reactor preparation 2 chloro -5 chloro - methylthiazole
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The invention relates to the technical field 2 chlorine -5 chlorine - methylthiazole preparation, in particular to a tower reactor for preparing 2 chloro -5 chloro - methylthiazole, which comprises the following steps: S1. The sodium thiocyanate and the catalyst tetrabutylammonium bromide are added into the tower reactor, and then are metered into 2, 3 - dichloropropene and toluene respectively, stirred and heated to reflux. S2, followed by addition of tetrabutylammonium bromide, and isomerization reaction was performed after the temperature increase, and after completion of the reaction, negative pressure distillation was performed to obtain 2 - chloroallyl isothiocyanate. To the method, pollution to the environment can be reduced, hydrogen chloride gas generated in the reaction process can be reused, and the problem that the color of the product 2 chlorine -5 chlorine - methyl thiazole is too deep can be solved.
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Paragraph 0021; 0024-0026; 0029-0031; 0034-0035; 0038; ...
(2021/11/10)
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- Synthesis process of 2-chloro-5-chloromethylthiazole
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The invention discloses a synthesis process of 2-chloro-5-chloromethylthiazole, and relates to the technical field of synthesis of 2-chloro-5-chloromethylthiazole. The method comprises the following steps: adding excessive sodium thiocyanate, water and a catalyst C2 into a reactor, slowly adding 2, 3-dichloropropene under the conditions of ultrasonic shearing and stirring, stopping ultrasonic treatment after the addition is completed, keeping stirring, slowly heating the mixed solution to reflux, and keeping the temperature until the reaction is complete; stopping stirring after the reaction is completed, carrying out primary standing layering, separating and transferring a primary organic layer into a distillation kettle after complete layering, stirring the residual solution, carrying out ultrasonic uniform mixing, carrying out secondary standing layering, separating and transferring a secondary organic layer into the distillation kettle after complete layering, and carrying out reduced pressure distillation to obtain an intermediate product; and adding the intermediate product and trichloromethane into a reactor, stirring at normal temperature, slowly dropwise adding sufficient sulfuryl chloride, and stirring at 45-55 DEG C until the reaction is complete after dropwise adding. The method is simple in process, low in raw material cost and high in product yield.
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Paragraph 0032-0039
(2021/07/17)
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- Clean and environment-friendly production process of 2-chloro-5-chloromethylthiazole
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The invention relates to a clean and environment-friendly production process of 2-chloro-5-chloromethylthiazole, which comprises the following steps: dissolving sodium thiocyanate in water, dropwiselyadding 2, 3-dichloropropene, carrying out heat preservation reaction after the dropwisely adding is completed, washing the obtained material with water, layering, and distilling to obtain an intermediate product 2-chloropropenyl isothiocyanate; dissolving the intermediate product in dichloroethane, dropwise adding sulfonyl chloride for the first time at the temperature of 30-60 DEG C, carrying out heat preservation reaction after dropwise adding is finished, degassing, desolventizing and cooling the obtained material, dropwise adding sulfonyl chloride for the second time, carrying out heat preservation reaction after dropwise adding for the second time, adding a stabilizer into the obtained material, and distilling to obtain 2-chloro-5-chloromethylthiazole. According to the invention, a pure byproduct sodium chloride is obtained, and the problem of high ammonia-nitrogen wastewater is solved. Due to the fact that the sulfonyl chloride is appropriate in use amount and is added in two times, by-products of sulfur dioxide and hydrogen chloride gas are reduced, the problem of environmental pollution is solved, and the production process is mild in reaction condition, small in toxicity,high in yield and purity and environmentally friendly.
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Paragraph 0016; 0022-0024
(2020/10/30)
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- Continuous synthesis method of 2-chloro-5-chloromethylthiazole
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The invention discloses a continuous synthesis method of 2-chloro-5-chloromethylthiazole. The continuous synthesis method comprises the following steps: step 1, adding a diluting solvent into a chlorination reaction device; step 2, gradually spraying a 2-chloro-3-isothiocyano-1-propylene solution into the chlorination reaction device, meanwhile, gradually introducing chlorine, carrying out a reaction, controlling the reaction temperature to range from 18 DEG C to 40 DEG C, then carrying out heat preservation till the reaction is completed, and thus obtaining a reaction material; and step 3, desolventizing, removing light components, and rectifying to obtain the 2-chloro-5-chloromethylthiazole product. Continuous reaction is adopted in the invention, compared with an existing process, the product quality and the product yield are greatly improved by controlling the addition of chlorine; the mass content of the 2-chloro-5-chloromethylthiazole is increased from 98.5% to 99.0% or above inthe process; by-products are reduced from 1.0% to 0.2% or below, the chlorination reaction yield is greatly increased to 92% compared with 75% of the existing process, the quality of the continuous feeding reaction process is stable, the total concentration of materials participating in the reaction is low, the production process is safe and controllable, and thus the green, environment-friendly and safe industrial production process is achieved.
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Paragraph 0029-0044
(2020/11/01)
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- Thiamethoxam and uses thereof
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A crystalline form of 3-(2-chloro-1,3-thiazol-5-ylmethyl)-5-methyl 1,3,5-oxadiazinan-yledene (nitro)amine (thiamethoxam) is provided. The crystalline form exhibits an X-ray powder diffraction pattern having characteristic peaks (expressed in degrees 2?? +/- 0.2?° ??) at one or more of the following positions: 6.09, 15.37, 17.83, 18.43, 20.86, 22.01, 26.95 and 27.84, and an Infrared (IR) spectrum having characteristic peaks at about 2933.62, 2161.78 and 1593.88 cm-1. A method of preparing the crystalline form comprises crystallizing 3-(2-chloro-1,3-thiazol-5-ylmethyl)-5-methyl-1,3,5-oxadiazinan -4-yledene (nitro)amine (thiamethoxam) from a solvent system comprising a solvent selected from an alcohol, a glycol, an ether, a ketone, an ester, an amide, a nitrile, an aliphatic or aromatic hydrocarbon, or mixtures thereof; and isolating the resulting crystals. The exemplified solvents are methanol, ethanol, 1-propanol, ethylene glycol, toluene and xylene.
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Paragraph 0081-0084
(2020/02/17)
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- Thiamethoxam production method and extractant
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The invention provides a thiamethoxam production method and an extractant, belongs to the technical field of pesticides, particularly provides an extractant taking ethylene glycol salicylate as a complexing agent, and also provides a composite extractant. The extractant comprises a complexing agent and a diluent, and the complexing agent comprises the ethylene glycol salicylate and P204, wherein the extraction ratio of ethylene glycol salicylate to P204 is 1:1.5 to 1:2. The ethylene glycol salicylate used as the complexing agent and -N- of thiamethoxam have strong ion association to generate an ion extract with the same structure, so that the distribution ratio is increased; and when the extractant and the P204 are used for composite extraction, hydrogen bond association of the strong electron withdrawing group nitro -NO2 of thiamethoxam and -OH of P204 can be promoted, and when the extraction ratio of ethylene glycol salicylate to the P204 extractant is 1:(1.5-2), the distribution ratio can be synergistically increased, and the extraction rate is increased.
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Paragraph 0088-0090; 0093
(2020/05/01)
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- Preparation method of 2-chloro-5-chloromethylthiazole
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The invention discloses a preparation method of 2-chloro-5-chloromethylthiazole. The preparation method comprises the following steps: S1, adding 1-isothiocyanato-2-chloro-2-propylene to an organic solvent, and carrying out a chlorination reaction at a temperature of 5-20 DEG C; S2, recovering the organic solvent, and exporting gaseous hydrogen chloride; and S3, performing heating and reduced pressure distillation after the recovery of the organic solvent in order to obtain the pure product 2-chloro-5-chloromethylthiazole. The preparation method of the 2-chloro-5-chloromethylthiazole in the embodiment of the invention has the advantages of avoiding of the use of a large amount of hydrochloric acid in the refining process, simplification of reaction steps, mild reaction conditions, no threewastes and high yield, and is in line with the development direction of green chemistry.
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Paragraph 0047-0058
(2019/02/13)
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- PROCESS FOR THE PREPARATION OF THIAMETHOXAM
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There is disclosed the use of a solvent system comprising a C1 to C4 alcohol, a substituted benzene derivative bearing two or more C1 to C4 alkyl substituents, or a mixture thereof in the preparation of a crystalline form of 3-(2-chloro-1, 3-thiazol-5-yl methyl)-5-methyl-1, 3, 5-oxadiazinan-4-yledene (nitro) amine (thiamethoxam). Crystalline thiamethoxam prepared in this way exhibits a significantly improved stability, in particular a resistance to photolysis, compared with crystalline thiamethoxam prepared using other solvents.
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Page/Page column 17
(2019/05/22)
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- A synthetic method of 2-chloro-5-chloromethyl thiazole
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A synthetic method of 2-chloro-5-chloromethyl thiazole is provided. The method includes adding 2,3-dichloropropene and sodium thiocyanate into an organic solvent, reacting the mixture, processing thereaction solution to obtain colorless liquid that is 2-chloroallyl isothiocyanate; then dissolving the 2-chloroallyl isothiocyanate into an organic solvent, adding hydrochloric acid and performing electrolysis to obtain the 2-chloro-5-chloromethyl thiazole. No chlorine is directly used in the synthetic process, while the 2-chloro-5-chloromethyl thiazole is synthesized through electrochemical chlorination, thus avoiding harm caused by chlorine, increasing the synthesis efficiency and saving the water resource and energy. In addition, the electrolytic reaction has high selectivity and the purityof the synthesized 2-chloro-5-chloromethyl thiazole is high. The method is suitable for synthesizing the 2-chloro-5-chloromethyl thiazole and further used for synthesizing thiamethoxam as an insecticide.
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Paragraph 0016-0018
(2019/06/07)
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- Synthesis method of chloromethyl thiazole
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The invention discloses a synthesis method of chloromethyl thiazole, and 1-isothiocyano-2-chlorine-2-propylene and chlorine are taken as the raw materials to react to obtain chloromethyl thiazole. Theprocess is simple, the reaction route is short, the cost is low, the yield is high, the molar yield is up to 99% (compared with dichloropropene), the process design is reasonable, the process is safeand controllable, no wastewater process is used, and the cost for treating wastewater is reduced.
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Paragraph 0051; 0052; 0053; 0054
(2018/09/21)
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- Method for preparing 2-chloro-5-chloromethylthiazole
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The invention discloses a method for preparing 2-chloro-5-chloromethylthiazole. The method comprises the following steps: in a micro-reactor and under a solvent-free condition, a chlorination reactionof chlorine and 1-isothiocyano-2-chloro-2-propylene is performed under the action of a composite initiator, and 2-chloro-5-chloromethylthiazole is prepared and obtained. The method has the advantagesof being free of solvent, low in cost, gentle in reaction condition, high in reaction speed, relatively small in the amount of three wastes, simple in process, relatively high in target product yield, relatively high in purity, and the like.
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Paragraph 0031-0043
(2018/06/15)
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- Synthesis method of thiamethoxam
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The invention relates to the field of compound synthesis, in particular to a synthesis method of an agricultural insecticide thiamethoxam. According to the preparation method of the thiamethoxam provided by the invention, through selecting appropriate reaction raw materials, a new synthetic route is designed, and an intermediate 2-chlorine-5-chloromethyl-thiazole can be prepared at room temperature, so that a cooling device is not needed, the energy is saved, and the reaction yield can be improved.
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Paragraph 0027; 0029; 0033; 0037
(2018/07/07)
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- Synthesis method of 2-chloro-5-chloromethylthiazole
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The invention relates to a preparation method of a key intermediate 2-chloro-5-chloromethylthiazole of thiamethoxam. According to the preparation method, the defects of the prior art, are overcome, the intermediate 2-chloro-5-chloromethylthiazole can be prepared at the room temperature through selecting appropriate reaction raw materials, no cooling equipment is needed, the energy is saved, and the reaction yield can be improved.
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Paragraph 0024; 0026; 0032
(2018/07/30)
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- A 2-chloro-5-chloromethyl-thiazole high-temperature decomposition method (by machine translation)
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The invention discloses a 2-chloro-5-chloromethyl-thiazole high-temperature decomposition method, relates to 2-chloro-5-chloromethyl-thiazole rectification technology field. In 2-chloro-5-chloromethyl-thiazole crude adding epoxy soybean oil, and then pressure reducing rectification, the first fraction cut, to distill share 2-chloro-5-chloromethyl-thiazole product; for the adding amount of epoxy soybean oil 2-chloro-5-chloromethyl-thiazole in crude product of 2-chloro-5-chloromethyl-thiazole quality 5-20%. The method of the invention lies in avoiding the main advantages of the 2-chloro-5-chloromethyl-thiazole high-temperature decomposition, the high content of 2-chloro-5-chloromethyl-thiazole finished product, is greatly improved in high-temperature rectification process of the 2-chloro-5-chloromethyl-thiazole yield and quality of the finished product, the production cost is reduced, improving the economic benefit. (by machine translation)
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Paragraph 0013; 0014; 0015; 0016; 0017
(2016/10/08)
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- Green synthesis method for high-quality 2-chloro-5-chloromethylthiazole
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The invention discloses a green synthesis method for high-quality 2-chloro-5-chloromethylthiazole. The method comprises the following steps that a, 1-isothiocyano-2-chloro-2-propylene is added to an organic solvent, and chlorine is introduced; b, after chlorine is introduced, stirring is conducted for 1-2 hours at the same temperature, then hydrogen chloride is introduced into the system, and the temperature is dropped to 2-15 DEG C and kept for 2-8 hours; c, the product obtained in step b is filtered, solid and liquid are separated, and a 2-chloro-5-chloromethylthiazole hydrochloride filter cake is obtained; d, a proper quantity of solvent is added to the obtained 2-chloro-5-chloromethylthiazole hydrochloride filter cake, the temperature is raised to 20-50 DEG C, degassing is conducted for 2-6 hours, and hydrogen chloride is absorbed through a three-level falling film absorption tower. By means of the method, reaction steps are simplified, hydrogen chloride generated in the whole process is absorbed through the falling film absorption tower, a clean byproduct hydrochloric acid is obtained, a large amount of wastewater brought by operation such as washing and alkali washing is avoided, and the idea of green production is met.
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Paragraph 0045; 0046
(2016/11/21)
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- Method for preparing 2-chloro-5-chloromethylthiazole by jet loop reactor
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The invention discloses a method for preparing 2-chloro-5-chloromethylthiazole by a jet loop reactor, and relates to the technical field of synthesis of the 2-chloro-5-chloromethylthiazole. The jet loop reactor comprises an ejector, wherein the ejector is arranged at the upper part of the reaction kettle; a lower outlet of the reaction kettle is communicated with an inlet of a circulating pump; an outlet of the circulating pump is communicated with the inlet of a heat exchanger; the outlet of the heat exchanger is communicated with the top inlet of the ejector; an air inlet pipe is arranged on the side surface of the ejector; 1-isothiocyano-2-chlorine-2-propylene is dissolved into an inert organic solvent to prepare a liquid-phase material; the liquid-phase material is added to the reaction kettle, and enters from the top inlet of the ejector after passing through the circulating pump and the heat exchanger; chlorine enters the ejector through the air inlet pipe and is mixed with the liquid-phase material; the mixed material passes through the reaction kettle, the circulating pump and the heat exchanger and then returns to the top inlet of the ejector; circular reaction is carried out until the chlorine is introduced; a 2-chloro-5-chloromethylthiazole product is obtained after post-treatment. The method disclosed by the invention is high in yield, few in solid wastes and high in production efficiency; the reaction temperature is easy to control.
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Paragraph 0024; 0025; 0026
(2017/01/19)
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- METHOD OF PRODUCING THIAMETHOXAM
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A process for the preparation of thiamethoxam: is provided, which process comprises reacting 3-methyl-N-nitro- 1,3,5,oxadiazinan-4-imine: with 2-chloro-5-chloromethyl thiazole: in the presence of a solvent system comprising dimethylformamide (DMF), a phase transfer catalyst and a base.
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Page/Page column 12; 13
(2015/12/18)
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- METHOD FOR PRODUCING THIAZOLE COMPOUND
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Disclosed is a simple and advantageous method for producing a thiazole compound, which method is suitable for commercial-scale implementation. In this method, a thiazole compound is produced by a reaction between 2-halogeno-allylisothiocyanate and sulfuryl chloride generating a large amount of heat, while suppressing decrease in the yield of the thiazole compound. Specifically disclosed is a method for producing 2-chloro-5-chloromethylthiazole represented by the formula (1): This method is characterized in that sulfuryl chloride is added to and reacted with 2-halogeno-allylisothiocyanate represented by the formula (2): wherein Hal represents chlorine or bromine, while blowing a gas inactive to the reaction into the reaction liquid.
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Page/Page column 4
(2008/12/08)
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- ION CHANNEL MODULATORS
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The present teachings provide carboxylic amide compounds that can modulate the activity of ion channels in a mammal. The present teachings also provide processes for producing said compounds and their pharmaceutically acceptable salts, hydrates and esters, and methods of treating a pathological condition or disorder, or alleviating a symptom thereof, using said compounds including their pharmaceutically acceptable salts, hydrates and esters. The compounds can be useful in modulating ion channel activity including treating a variety of conditions associated with the abnormal modulation of one or more voltage-gated calcium channels.
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Page/Page column 149
(2008/12/06)
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- ION CHANNEL MODULATORS
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The present teachings provide compounds of Formula (I): and pharmaceutically acceptable salts, hydrates, and esters thereof, wherein Ar, R1, R2, R3, p, and X are defined herein. The present teachings also provide processes for producing said compounds and their pharmaceutically acceptable salts, hydrates and esters, and methods of treating a pathological condition or disorder, or alleviating a symptom thereof, using said compounds including their pharmaceutically acceptable salts, hydrates and esters. The compounds can be useful in modulating ion channel activity including treating a variety of conditions associated with the abnormal modulation of one or more voltage-gated calcium channels.
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Page/Page column 85; 106; 110
(2008/12/06)
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- ION CHANNEL MODULATORS
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The present teachings provide compounds of Formula (I) and pharmaceutically acceptable salts, hydrates, and esters thereof, wherein Ar, R1, R1', R2, R3, R4 R4', and p are defined herein. The present teachings also provide processes for producing said compounds and their pharmaceutically acceptable salts, hydrates and esters, and methods of treating a pathological condition or disorder, or alleviating a symptom thereof, using said compounds including their pharmaceutically acceptable salts, hydrates and esters. The compounds can be useful in modulating ion channel activity including treating a variety of conditions associated with the abnormal modulation of one or more voltage-gated calcium channels.
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Page/Page column 54; 80
(2008/12/06)
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- CARBOXAMIDE DERIVATIVES AS ION CHANNEL MODULATORS
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The present teachings provide compounds of Formula (I) wherein Ar, R1, R2, R3, X, p and n are defined herein. The present teachings also provide processes for producing said compounds and methods of treating a pathological condition or disorder, or alleviating a symptom thereof, using said compounds. The compounds can be useful in modulating ion channel activity including treating a variety of conditions associated with the abnormal modulation of one or more voltage-gated calcium channels.
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Page/Page column 82; 112
(2008/12/06)
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- PROCESS FOR PURIFICATION OF 2-CHLORO-5-CHLOROMETHYL -1,3-THIAZOLE
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The present invention provides a process for purifying 2-chloro-5-chloromethyl-1,3-thiazole represented by the formula (I): by distillation of a crude product thereof, comprising treating the crude product with a lower alcohol before the distillation. The present purification process is a new one for purifying 2-chloro-5-chloromethyl-1,3-thiazole, suitable for industrial practice.
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Page/Page column 4-5
(2008/06/13)
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- SPIRO-OXINDOLE COMPOUNDS AND THEIR USES AS THERAPEUTIC AGENTS
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This invention is directed to spiro-oxindole compounds of formula (I): wherein k, j, Q, R1, R2a, R2b, R2c, R2d, R3a, R3b, R3c, and R3d are as defined herein, as a stereoisomer, enantiomer, tautomer thereof or mixtures thereof; or a pharmaceutically acceptable salt, solvate or prodrug thereof, which are useful for the treatment and/or prevention of sodium channel-mediated diseases or conditions, such as pain. Pharmaceutical compositions comprising the compounds and methods of preparing and using the compounds are also disclosed.
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Page/Page column 291
(2010/11/24)
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- Synthesis and Herbicidal Activity of 2-Cyano-3-(2-chlorothiazol-5-yl)methylaminoacrylates
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A series of 2-cyano-3-(2-chlorothiazol-5-yl)methylaminoacrylates were synthesized as herbicidal inhibitors of PSII electron transport. All of these compounds exhibited good herbicidal activities. In particular, (Z)-ethoxyethyl 2-cyano-3-isopropyl-3-(2-chlorothiazol-5-yl)methylaminoacrylate showed excellent herbicidal activities even at a dose of 75 g/ha. A suitable group at the 3-position of acrylate was essential for high herbicidal activity. 2-Cyanoacrylates containing a 2-chloro-5-thiazolyl group are a novel class of herbicides and display herbicidal activities comparable to existing analogues bearing chloropyridyl or chlorophenyl.
- Wang, Qingmin,Li, Heng,Li, Yonghong,Huang, Runqiu
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p. 1918 - 1922
(2007/10/03)
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- PROCESS FOR THE PREPARATION OF 2-CHLORO-5-CHLOROMETHYL-THIAZOLE
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The invention relates to a process for the preparation of 2-chloro-5-chloromethyl-thiazole, which is employed as intermediate in the preparation of compounds having a pesticidal action, which process comprises reacting a compound of formula (II), in free form or in salt form, (III), (IV), (V) or (VI) with a chlorinating agent, where R and M+ are as defined in claim 1; to the compounds of the formulae (III) and (IV), which are used in this process as intermediates; and to the use of, and a process for the preparation of, the compounds of formulae (III) and (IV).
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- Process for the manufacture of thiazole derivatives with pesticidal activity
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A process for the preparation of a compound of the formula (I) in which Q, Y, Z, R1, R2 are as defined in claim 1; in which a) a compound of the formula (II), in which X is a leaving group, is reacted with a halogenating agent to give a compound of the formula (III), in which W is a halogen atom; and b) the resulting compound of the formula (III) is reacted with a compound of the formula (IV), in which R1, R2, Y, Z and Q are as defined in claim 1; wherein the preparation of the compound of the formula (III) according to process stage a) involves a purification step in which the reaction mass which has formed is treated with water in the acidic pH range; a process for the preparation of a compound of the formula (III) according to the abovementioned process a), and the use of the compounds of the formulae (II), (III) and (IV) in a process as detailed above are described.
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- Catalytic process for the preparation of thiazole derivatives
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There are described a process for the preparation of a compound of formula in free form or in salt form, wherein Q is CH or N; Y is NO2 or CN; Z is CHR3, O, NR3 or S; R1 and R2 are, for example, C1-C8 alkyl or together form an alkylene bridge; R3 is H or C1-C1-2 alkyl which is unsubstituted or substituted by R4; and R4 is unsubstituted or substituted aryl or heteroaryl; wherein a) a compound of formula (II), wherein X is a leaving group, is reacted with a chlorinating agent to form a compound of formula (III), in free form or in salt form; and b) the compound of formula (III) thereby obtained is reacted with a compound of formula wherein R1, R2, Y, Z and Q are as defined for compound (I); in which process the chlorination according to process step a) is performed using a chlorinating agent in the presence of catalytic amounts of SO2; a process for the preparation of a compound of formula (III) according to process a) hereinbefore; and the use of the compouds of formulae (II), (III) and (IV) in a process as described hereinbefore.
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- Method for producing 2-chloro-5-chloromethyl-1,3-thiazole
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A process for the preparation of 2-chloro-5-chloromethyl-1,3-thiazole, in which allyl isothiocyanate of formula CH2═CH—CH2-NCS is reacted at from ?40° C. to +30° C., in a solvent that is inert under the reaction conditions, with from 1 to 2 mol of a chlorinating agent per mol of allyl isothiocyanate; to the reaction mixture so obtained there is added, at a reaction temperature of from 0° C. to the boiling temperature of the solvent used, from 1 to 5 mol of oxidising agent per mol of allyl isothiocyanate, and then 2-chloro-5-chloromethyl-1,3-thiazole is isolated from the reaction mixture and is optionally converted by crystallisation into high-purity 2-chloro-5-chloromethyl-1,3-thiazole.
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- Process for preparing 2-chloro-5-chloromethylthiazole
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A novel process for preparing 2-chloro-5-chloromethylthiazole is provided which is suitable for industrial application. The process for preparing 2-chloro-5-chloromethylthiazole involves allowing 2-halogenoallyl isothiocyanate to react with chlorinating agent in the presence of an aromatic hydrocarbon which may have one or more substituents.
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- Process for preparing a 2-chloro-5-chloromethyl-thiazole compound
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The invention relates to a process for preparing a compound of formula (I) in which A is chlorine or 3-methyl-4-nitroimino-perhydro-1,3,5-oxadiazin-5-yl; to intermediates used in this process; to the use of these intermediates; and to a process for the preparation of these intermediates. The compounds of formula (I) are valuable intermediates in the process of preparing pesticidal, especially insecticidal or acaricidal, formulations.
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- Process for preparing 2-chloro-5-chloromethylthiazole
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The invention relates to a novel process for preparing 2-chloro-5-chloromethylthiazole by reacting 2-halogenoallyl isothiocyanates with a chlorinating agent.
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- Process for the preparation of thiazole derivatives
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A process for the preparation of a compound of formula (I), wherein X is a leaving group; which process comprises, a) for the preparation of a compound of formula (I) wherein X is —OS(═O)2A and A is as defined in the specification, reacting a compound of formula (II) with a sulfonylating agent; or, b) for the preparation of a compound of formula (I) wherein X is iodine, reacting a compound of formula (III) with an iodinating agent, preferably sodium iodide; or, c) for the preparation of a compound of formula (I) whrein X is bromine, reacting a compound of formula (IV) with a brominating agent; or, d) for the preparation of a compound (I) wherein X is chlorine or bromine, reacting a compound (V), wherein R and X are as defined in the specification, with a chlorinating agent, a compound of formula (Ib), the use thereof and a process for the preparation of a compound of formula (II) and a compound of formula (A) are described.
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- Synthetic approaches towards CGA 293'343: A novel broad-spectrum insecticide
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Synthetic approaches towards CGA 293'343 (ISO draft common name: thiamethoxam), a novel broad-spectrum insecticide from the class neonicotinoids, are described. 2-Chloro-5-chloromethylthiazole, an important synthetic intermediate, was prepared from five different precursors. Alternatively, CGA 293'343 was prepared via the intermediate 2-benzylmercapto-5-chloromethylthiazole, the synthesis of which is also described.
- Goebel, Thomas,Gsell, Laurenz,Hueter, Ottmar F.,Maienfisch, Peter,Naef, Rudolf,O'Sullivan, Anthony C.,Pitterna, Thomas,Rapold, Thomas,Seifert, Gottfried,Senn, Marcel,Szczepanski, Henry,Wadsworth, David J.
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p. 355 - 357
(2007/10/03)
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- Process for the preparation of 2-chloro-5-chloromethyl-1,3-thiazole
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According to the present invention, provided are (1) a process for the preparation of 2-chloro-5-chloromethyl-1,3-thiazole, by reacting 3-chloro-1-isothiocyanato-1-propene with a chlorinating agent, (2) a process for the preparation of 3-chloro-1-isocyanato-1-propene, by rearranging 3-chloro-1-thiocyanato-2-propene in the presence of a salt of one or more than one metal selected from the group consisting of metals belonging to Group 2A, Group 7A, Group 8 and Group 1B of the long-form periodic table, and (3) a process for the preparation of 3-chloro-1-thiocyanato-2-propene, by reacting 1,3-dichloropropene and a thiocyanate salt (a) in the presence of water, (b) in the presence of an organic solvent which is water-soluble and has a boiling point of 150° C. or lower, or (c) in an organic solvent in the presence of a phase transfer catalyst.
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- Method for substitution of an amino group of a primary amine by a chlorine atom and a synthetic method by application thereof
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This invention relates to methods for substitution of an amino group of a heterocyclic primary amine by a chlorine atom and synthesis of 2-chloro-5-methylthiazole and its derivatives by application thereof. Typically, a heterocyclic primary amine and sodium nitrite are caused to react in the presence of hydrochloric acid, followed by heating the formed diazonium base at 30°-100° C. in the presence of an equimolar or more of hydrochloric acid to substitute the amino group by the chlorine atom. Further, 2-amino-5-methylthiazole and sodium nitrite are caused to react in the presence of hydrochloric acid, followed by heating the formed diazonium base at 30°-100° C. in the presence of an equimolar or over of hydrochloric acid to give 2-chloro-5-methylthiazole. Then, the resultant 2-chloro-5-methylthiazole is caused to react with a chlorinating agent to give 2-chloro-5-chloro-methylthiazole.
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- Preparation of substituted thiazoles
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A process for the preparation of a substituted thiazole comprises reacting an isothiocyanate compound of the general formula in which Hal is a chlorine or bromine atom and R1 and R2 is each a hydrogen atom or an alkyl group containing 1 to 3 carbon atoms, in solution with a chlorinating or brominating agent. The compound 2-chloro-5-(chloromethyl) thiazole, which is an important intermediate in the manufacture of agrochemical and pharmaceutical products, may very advantageously be prepared by this method.
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- Process for the preparation of 2-chloro-5-chloromethylthiazole
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The invention relates to a novel process for the preparation of 2-chloro-5-chloromethylthiazole by reacting 5-methylene-l,3-thiazolidine-2-thiones with a chlorinating agent.
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- Process for the preparation of chlorothiazole derivatives
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Novel processes for preparing 2-chlorothiazoles, useful as an intermediate for insecticides, from allyl isothiocyanate derivatives having the formula [II]: STR1 wherein X represents a leaving group, are simple and convenient reaction procedures under mild conditions without need of a large excess of a chlorinating agent. Further, processes for preparing 5-(aminomethyl)-2-chlorothiazole or salts thereof from the compound [II] achieve higher yields by simple, convenient and inexpensive procedures.
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- Preparation of 2-chloro-5-chloromethylthiazole
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A process for the preparation of 2-chloro-5-chloromethyl-thiazole of the formula: STR1 comprising reacting allyl isothiocyanate of the formula with about 2 to 20 times its molar amount of chlorine at a temperature from above 0° to 150° C.
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