CN104016941A - Preparation method of 2-chlorine-5-chloromethylthiazole - Google Patents
Preparation method of 2-chlorine-5-chloromethylthiazole Download PDFInfo
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- CN104016941A CN104016941A CN201410098099.3A CN201410098099A CN104016941A CN 104016941 A CN104016941 A CN 104016941A CN 201410098099 A CN201410098099 A CN 201410098099A CN 104016941 A CN104016941 A CN 104016941A
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- chlorine
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- thiocyanate
- chloromethyl thiazoles
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D277/00—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings
- C07D277/02—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings
- C07D277/20—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members
- C07D277/32—Heterocyclic compounds containing 1,3-thiazole or hydrogenated 1,3-thiazole rings not condensed with other rings having two or three double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention discloses a preparation method of 2-chlorine-5-chloromethylthiazole. The method is characterized by comprising the following preparation steps of 1) dissolving thiocyanate into water and adding a phase transfer catalyst and 2,3-chloropropene at the temperature of 20-70 DEG C; 2) controlling reaction temperature to be between 80 and 150 DEG C and reacting for 4-10 hours, standing and layering, performing reduced pressure distillation on an oil layer to obtain 2-chlorine-3-isothiocyanic acid propylene; 3) dissolving the 2-chlorine-3-isothiocyanic acid propylene obtained in the step 2) into a solvent, adding a chloride agent at the temperature of 0-70 DEG C and reacting for 4-12 hours, condensing a reaction system, adding hydrochloric acid and removing impurities; 5) performing reduced pressure distillation and purification on the product obtained in the step 4) to obtain 2-chlorine-5-chloromethylthiazole. The preparation method is easily available in raw materials, less in reaction steps, simple to operate, and high in yield of products and quality of the obtained products, so that industrial production of 2-chlorine-5-chloromethylthiazole can be realized.
Description
Technical field
The present invention relates to a kind of preparation method of 2 chlorine 5 5-chloromethyl thiazoles.
Background technology
Anabasine insecticide be after organic phosphates, amino formate and pyrethroid insecticides the 4th generation sterilant.Because it has the features such as low toxicity, target is unique, application method is various, make them become an insecticides in agriculture production with extensive use, caused pesticide research persons' extensive concern.
Clothianidin is the important kind in anabasine insecticide, it has broad-spectrum insecticidal activity, active similar to Provado, using method is flexible, both having can be used for cauline leaf processes, also can be used for soil seed and process, can effectively prevent and treat Hemiptera, Coleoptera and some lepidoptera pest, be applicable to paddy rice, fruit tree, cotton, tealeaves, turf and ornamental plant etc.Clothianidin is lived chemical weapons field/Baeyer by Japan and is developed jointly, and December calendar year 2001, in Japan, obtains registration.
Diacloden is the anabasine insecticide of 1991 Nian You Novartis Co.,Ltd exploitation, its mechanism of action is similar to Provado, alternative inhibition insect central nervous system nicotinic acid nAChR ligands, and then the normal conduction of blocking-up insect central nervous system, dead while causing insect to occur paralysis machine.Not only have tag, stomach toxicity, systemic activity, and there is higher activity, better security, wider insecticidal spectrum and the feature such as speed of action is fast, the lasting period is long, be the better kind that replaces those are high to mammalian toxicity, have residual and environmental problem organophosphorus, carbamate, organochlorine insecticides.To Coleoptera, Diptera, lepidopteran, especially homoptera pest has high reactivity, can effectively prevent and treat the insect that the insects such as various aphids, leafhopper, plant hopper, aleyrodid, chafer larva, colorado potato bug, nematode, ground beetle, leaf miner and knot broad variety chemical pesticide produce resistance.With Provado, acetamiprid, Ti304 without cross resistance.Both can be used for cauline leaf processing, seed treatment, also can be used for soil treatment.Suitable crop is rice class crop, beet, rape, potato, cotton, Kidney bean, fruit tree, peanut, Sunflower Receptacle, soybean, tobacco and citrus etc.Under recommended dose, use to crop safety, without poisoning.
2-chloro-5-chloromethyl thiazole is the important intermediate of synthetic anabasine insecticide Diacloden and clothianidin.Therefore,, for advancing agriculture development, be necessary research and disclose a kind of method that applicable suitability for industrialized production is prepared 2-chloro-5-chloromethyl thiazole.
Summary of the invention
The object of the invention is to for above-mentioned defect of the prior art, a kind of preparation method of improved 2 chlorine 5 5-chloromethyl thiazoles is provided, this preparation method's raw material is easy to get, reactions steps is few, simple to operate, product yield is high, and the product 2 chlorine 5 5-chloromethyl thiazole quality betters that obtain, thereby can realize suitability for industrialized production.
For achieving the above object, the present invention has adopted following technical scheme: a kind of 2 chlorine 5 chloromethyl thiophenes
The preparation method of azoles, is characterized in that its preparation process is as follows:
1) thiocyanate-is soluble in water, in temperature, be, under the condition of 20～70 ℃, to add phase-transfer catalyst and 2,3 dichloropropylenes;
2) temperature of reaction is controlled under the reaction conditions of 80～150 ℃, reacts 4～10 hours; After stratification, oil reservoir underpressure distillation is obtained to 2 chlorine 3 isothiocyanic acid propylene;
3) by step 2) 2 chlorine 3 isothiocyanic acid propylene of gained are dissolved in solvent, are, under the reaction conditions of 0～70 ℃, to add chlorination reagent in temperature range, and the reaction times is 4～12 hours;
4) concentration response system, adds hydrochloric acid, removes impurity; And,
5) by step 4) the product underpressure distillation purifying of gained obtains 2 chlorine 5 5-chloromethyl thiazoles.
In addition, the present invention also provides following attached technical scheme:
The preparation method's of described 2 chlorine 5 5-chloromethyl thiazoles operational path is as follows:
Described step 1) in, thiocyanate-is Sodium Thiocyanate 99, potassium sulfocyanate or ammonium thiocyanate.
Described step 1) in, phase-transfer catalyst is tetrabutyl ammonium fluoride, Tetrabutyl amonium bromide, tetrabutylammonium iodide or 16 crown ethers.
Described step 3) the certain solvent in, this solvent is toluene, dimethylbenzene, tetrahydrofuran (THF), acetone, methylene dichloride, 1,2 ethylene dichloride, chloroform, normal hexane, normal heptane, sherwood oil, ethyl acetate or acetonitrile.
Described step 3) chlorination reagent in is chlorine or SULPHURYL CHLORIDE.
Than prior art, advantage of the present invention is: it has disclosed a kind of preparation method of 2 chlorine 5 5-chloromethyl thiazoles, this preparation method is with 2,3 dichloropropylenes are raw material, with thiocyanate-together with phase-transfer catalyst, give certain temperature of reaction and reaction times, after underpressure distillation, obtain 2 chlorine 3 isothiocyanic acid propylene (II), recycle resulting 2 chlorine 3 isothiocyanic acid propylene and react with chlorination reagent, after concentrated, removal of impurities, underpressure distillation purifying, obtain highly purified 2 chlorine 5 5-chloromethyl thiazoles successively.Therefore, this preparation method has embodied raw material and has been easy to get, and reactions steps is few, simple to operate, and product yield is high, and the advantages such as superior product quality that obtain, and makes 2 chlorine 5 5-chloromethyl thiazoles can realize suitability for industrialized production.
Embodiment
Below in conjunction with preferred embodiment, technical solution of the present invention is further non-limitingly described in detail.
Prepare a kind of 2 chlorine 5 5-chloromethyl thiazoles, its operational path is roughly as follows:
Add 0.6 kg water in reaction flask after, stir, then add 0.162 kilogram of thiocyanate----Sodium Thiocyanate 99, and 0.0018 kilogram of phase-transfer catalyst---Tetrabutyl amonium bromide, stir 0.5 hour, after solution clarification, then add 0.2 kilogram of 2,3 dichloropropylene.After being slowly warming up between 90～95 ℃, reflux standing 0.5 hour, separate 0.24 kilogram, oil reservoir below, and transfer them in matrass.By the oil reservoir underpressure distillation that heats up, distillation temperature is that 67～72 ℃, distillation pressure are 0.01MPa, finally collects 0.2 kilogram of product 2 chlorine 3 isothiocyanic acid propylene, and yield is 83%.Marker method GC purity 97.2%.
In another reaction flask, add 0.1 kilogram of 2 chlorine 3 isothiocyanic acid propylene obtained above, then add 0.3 kilogram of solvent---toluene, stir, and control temperature between 25～30 ℃, be added dropwise to 0.1108 kilogram of chlorination reagent---SULPHURYL CHLORIDE.After adding, above-mentioned mixing solutions is arranged in the environment of 25～30 ℃ to insulation reaction 2～4 hours, after insulation reaction finishes, adds concentration to be 0.5 kilogram of 36% hydrochloric acid, then standing, separate organic phase, and reclaim solvent.It is 8～9 that water is adjusted to pH value with ammoniacal liquor, then uses dichloromethane extraction, extracts three times, and each extraction quantity is 300 milliliters.After organic phase is concentrated, underpressure distillation, distillation temperature is between 90～110 ℃, and distillation pressure is 0.01MPa, finally collects 0.106 kilogram of high purity product 2 chlorine 5 5-chloromethyl thiazole, and yield is 85%.Marker method GC purity 98.5%.
In the present invention, thiocyanate-, except Sodium Thiocyanate 99, can also be potassium sulfocyanate or ammonium thiocyanate etc.Phase-transfer catalyst, except Tetrabutyl amonium bromide, can also be to be tetrabutyl ammonium fluoride, tetrabutylammonium iodide or 16 crown ethers etc.Solvent, except toluene, can also be dimethylbenzene, tetrahydrofuran (THF), acetone, methylene dichloride, 1,2 ethylene dichloride, chloroform, normal hexane, normal heptane, sherwood oil, ethyl acetate or acetonitrile etc.Chlorination reagent, except SULPHURYL CHLORIDE, can also be chlorine.
The preparation method of 2 disclosed chlorine 5 5-chloromethyl thiazoles, with 2,3 dichloropropylenes are raw material, with MSCN together with phase-transfer catalyst, give certain temperature of reaction and reaction times, after underpressure distillation, obtain 2 chlorine 3 isothiocyanic acid propylene, recycle resulting 2 chlorine 3 isothiocyanic acid propylene and react with chlorination reagent, after concentrated, removal of impurities, underpressure distillation purifying, obtain highly purified 2 chlorine 5 5-chloromethyl thiazoles successively.Therefore, this preparation method has embodied raw material and has been easy to get, and reactions steps is few, simple to operate, and product yield is high, and the advantages such as superior product quality that obtain, and makes 2 chlorine 5 5-chloromethyl thiazoles can realize suitability for industrialized production.
It is pointed out that above-mentioned preferred embodiment is only explanation technical conceive of the present invention and feature, its object is to allow person skilled in the art can understand content of the present invention and implement according to this, can not limit the scope of the invention with this.All equivalences that spirit is done according to the present invention change or modify, within all should being encompassed in protection scope of the present invention.
Claims (6)
1. a preparation method for 2 chlorine 5 5-chloromethyl thiazoles, is characterized in that its preparation process is as follows:
1) thiocyanate-is soluble in water, in temperature, be, under the condition of 20～70 ℃, to add phase-transfer catalyst and 2,3 dichloropropylenes;
2) temperature of reaction is controlled under the reaction conditions of 80～150 ℃, reacts 4～10 hours; After stratification, oil reservoir underpressure distillation is obtained to 2 chlorine 3 isothiocyanic acid propylene;
3) by step 2) 2 chlorine 3 isothiocyanic acid propylene of gained are dissolved in solvent, are, under the reaction conditions of 0～70 ℃, to add chlorination reagent in temperature range, and the reaction times is 4～12 hours;
4) concentration response system, adds hydrochloric acid, removes impurity; And,
5) by step 4) the product underpressure distillation purifying of gained obtains 2 chlorine 5 5-chloromethyl thiazoles.
2. the preparation method of 2 chlorine 5 5-chloromethyl thiazoles according to claim 1, is characterized in that its operational path is as follows:
3. the preparation method of 2 chlorine 5 5-chloromethyl thiazoles according to claim 1, is characterized in that: described step 1), thiocyanate-is Sodium Thiocyanate 99, potassium sulfocyanate or ammonium thiocyanate.
4. the preparation method of 2 chlorine 5 5-chloromethyl thiazoles according to claim 1, is characterized in that: described step 1), phase-transfer catalyst is tetrabutyl ammonium fluoride, Tetrabutyl amonium bromide, tetrabutylammonium iodide or 16 crown ethers.
5. the preparation method of 2 chlorine 5 5-chloromethyl thiazoles according to claim 1, it is characterized in that: the solvent described step 3) is toluene, dimethylbenzene, tetrahydrofuran (THF), acetone, methylene dichloride, 1,2 ethylene dichloride, chloroform, normal hexane, normal heptane, sherwood oil, ethyl acetate or acetonitrile.
6. the preparation method of 2 chlorine 5 5-chloromethyl thiazoles according to claim 1, is characterized in that: the chlorination reagent described step 3) is chlorine or SULPHURYL CHLORIDE.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438304A (en) * | 2018-12-12 | 2019-03-08 | 湖南海利常德农药化工有限公司 | A kind of preparation method of 2- Chloroallyl isothiocyanates |
| CN111777568A (en) * | 2020-08-05 | 2020-10-16 | 河北硕俊生物科技有限公司 | Clean and environment-friendly production process of 2-chloro-5-chloromethyl thiazole |
| CN113121465A (en) * | 2021-05-28 | 2021-07-16 | 安徽海顺化工有限公司 | Synthesis process of 2-chloro-5-chloromethyl thiazole |
| CN113603527A (en) * | 2021-08-05 | 2021-11-05 | 安徽省司尔特肥业股份有限公司 | High-yield and high-efficiency special fertilizer for cotton and preparation method thereof |
| CN113620902A (en) * | 2021-09-23 | 2021-11-09 | 邯郸市瑞田农药有限公司 | Preparation of 2-chloro-5-chloro-methylthiazole by tower reactor |
| CN116102517A (en) * | 2022-11-14 | 2023-05-12 | 郑州大学 | Synthesis method of 2-chloro-5-chloromethylthiazole |
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Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109438304A (en) * | 2018-12-12 | 2019-03-08 | 湖南海利常德农药化工有限公司 | A kind of preparation method of 2- Chloroallyl isothiocyanates |
| CN111777568A (en) * | 2020-08-05 | 2020-10-16 | 河北硕俊生物科技有限公司 | Clean and environment-friendly production process of 2-chloro-5-chloromethyl thiazole |
| CN113121465A (en) * | 2021-05-28 | 2021-07-16 | 安徽海顺化工有限公司 | Synthesis process of 2-chloro-5-chloromethyl thiazole |
| CN113603527A (en) * | 2021-08-05 | 2021-11-05 | 安徽省司尔特肥业股份有限公司 | High-yield and high-efficiency special fertilizer for cotton and preparation method thereof |
| CN113620902A (en) * | 2021-09-23 | 2021-11-09 | 邯郸市瑞田农药有限公司 | Preparation of 2-chloro-5-chloro-methylthiazole by tower reactor |
| CN113620902B (en) * | 2021-09-23 | 2023-08-18 | 邯郸市瑞田农药有限公司 | Preparation of 2-chloro-5-chloro-methylthiazole in tower reactor |
| CN116102517A (en) * | 2022-11-14 | 2023-05-12 | 郑州大学 | Synthesis method of 2-chloro-5-chloromethylthiazole |
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Application publication date: 20140903 |