CN106749086A - A kind of preparation method of the 5-chloromethyl thiazole of 2 chlorine of pesticide intermediate 5 - Google Patents
A kind of preparation method of the 5-chloromethyl thiazole of 2 chlorine of pesticide intermediate 5 Download PDFInfo
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- CN106749086A CN106749086A CN201611222381.3A CN201611222381A CN106749086A CN 106749086 A CN106749086 A CN 106749086A CN 201611222381 A CN201611222381 A CN 201611222381A CN 106749086 A CN106749086 A CN 106749086A
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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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- Organic Chemistry (AREA)
- Thiazole And Isothizaole Compounds (AREA)
Abstract
The invention discloses a kind of preparation method of the 5-chloromethyl thiazole of 2 chlorine of pesticide intermediate 5, it is related to technical field of biochemical industry, it is reaction raw materials with 5 hydroxymethylthiazoles, acetonitrile is reaction dissolvent, N chlorosuccinimides are chlorination reagent, iodine is catalyst, and the 5-chloromethyl thiazole of 2 chlorine 5 is obtained through chlorination reaction.The present invention with 5 hydroxymethylthiazoles be raw material, the 5-chloromethyl thiazole of 2 chlorine 5 is prepared using one kettle way, two one-step chlorination reactions are carried out under the synergy of chlorination reagent N chlorosuccinimides and catalyst iodine, the 5-chloromethyl thiazole yield of 2 chlorine of obtained product 5 and purity are higher, yield reaches 93.8%, and purity reaches 99.2%.
Description
Technical field：
The present invention relates to technical field of biochemical industry, and in particular to a kind of pesticide intermediate 2- chloro-5-chloromethyl thiazoles
Preparation method.
Background technology：
2- chloro-5-chloromethyl thiazoles are the key intermediates of synthesizing efficient insecticide imidaclothiz.Imidaclothiz is a kind of new one
It is strong systemic insecticide for chlorination nicotinic insecticide, is the acting body of nicotinic acetylcholine esterase acceptor, is suck for preventing and treating
Suction mouthpart insect, such as aphid, Ye Chan, plant hopper, thrips, aleyrodid and its resistant strain, while obvious to rice-stem borer virulence
Higher than like product, the crops such as paddy rice, wheat, tea tree, fruit tree, vegetables are widely used in.
Synthetic method report about 2- chloro-5-chloromethyl thiazoles is a lot, mainly including following several：(1) with the different sulphur of 1-
Cyanic acid base -2- propylene is raw material, and chloroform is solvent, and being passed through chlorine carries out chlorination reaction；(2) with the chloro- 1- of 1- isothiocyanic acid base -3-
Propylene is raw material, and chloroform is solvent, and chlorosulfuric acid is added dropwise or chlorine is passed through carries out chlorination reaction；(3) with 1- isothiocyanic acid bases -2-
Chloro-2-propene is raw material, and acetonitrile is solvent, and chlorosulfuric acid is added dropwise at low temperature or chlorine is passed through carries out chlorination reaction；(4) with propylene
Aldehyde is raw material, is obtained 2- amino -5-Hydroxymethylthiazole with hydrogen peroxide and thiocarbamide reaction in the basic conditions, then to carry out diazotising anti-
Hydrolyzed in substantial amounts of hydrochloric acid after answering, heated, yield 30%, purity 95%.
Above-mentioned route is analyzed, route (1) needs a large amount of excessive chlorine, and side reaction is more, and crude product purity is 41.4%, letter
Purity after simple distillation is also only 47.8%, and yield 50.4% need to can just obtain sterling by rectifying；Raw material 1- in route (2)
The suitable inverse proportion of the chloro- 1- propylene of isothiocyanic acid base -3- influences very big on reaction yield, when suitable inverse ratio is 2:Yield 69.2% when 3,
Purity 93.8%, when suitable inverse ratio is 4:Yield 45.3%, purity 92.6% when 1 are higher to reaction condition requirement；Route (3)
Product purity reaches 90%, and yield reaches 85%, but the toxicity of chlorosulfuric acid and chlorine is larger；Route (4) is related to diazo-reaction,
Reaction condition is harsh, and yield is relatively low.
The content of the invention：
The technical problems to be solved by the invention are to provide a kind of gentle reaction condition, small toxicity and yield and purity are high
Pesticide intermediate 2- chloro-5-chloromethyl thiazoles preparation method.
The technical problems to be solved by the invention are realized using following technical scheme：
A kind of preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazoles, with 5-Hydroxymethylthiazole as reaction raw materials, second
Nitrile is reaction dissolvent, and N- chlorosuccinimides are chlorination reagent, and iodine is catalyst, and the chloro- 5- chloromethanes of 2- are obtained through chlorination reaction
Base thiazole.
A kind of preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazoles, specific preparation process is：By 5- methylol thiophenes
Azoles is dissolved in acetonitrile, and N- chlorosuccinimides are added at 0 DEG C, and reaction is warmed to room temperature naturally after adding, and treats 5- hydroxyl first
The iodine of catalytic amount is added after the reaction completely of base thiazole, and is heated to back flow reaction, reaction concentrates out solvent after terminating, then will be surplus
Excess is down to 0 DEG C, and adds 2- chloro-5-chloromethyl thiazole crystal seeds, insulated and stirred crystallization, suction filtration, filter cake washing, most afterwards through vacuum
2- chloro-5-chloromethyl thiazoles are obtained after drying.
The molar ratio of the 5-Hydroxymethylthiazole and N- chlorosuccinimides is 1:2-3.
The room temperature reaction time is 1-3h.
The reflux time is 2-4h.
The beneficial effects of the invention are as follows：The present invention prepares the chloro- 5- chlorine of 2- with 5-Hydroxymethylthiazole as raw material using one kettle way
Methylthiazol, carries out two one-step chlorination reactions, instead under the synergy of chlorination reagent N- chlorosuccinimides and catalyst iodine
Mild condition is answered, reaction reagent toxicity used is relatively small, and the obtained chloro- methylthiazol yields of the chloro- 5- of product 2- and purity
Higher, yield reaches 93.8%, and purity reaches 99.2%, so as to go to prepare as intermediate beneficial to 2- chloro-5-chloromethyl thiazoles
Efficient pesticides imidaclothiz.
Specific embodiment：
In order that technological means, creation characteristic, reached purpose and effect that the present invention is realized are easy to understand, tie below
Specific embodiment is closed, the present invention is expanded on further.
Embodiment 1
0.1mol 5-Hydroxymethylthiazoles are dissolved in acetonitrile, add 0.2mol N- chloros succinyl sub- at 0 DEG C
Amine, is warmed to room temperature reaction 1h naturally after adding, add the iodine of catalytic amount, and is heated to back flow reaction 3h, and reaction terminates rear dense
Contracted solvent, and residue then is down into 0 DEG C, and adds 2- chloro-5-chloromethyl thiazole crystal seeds, insulated and stirred crystallization, suction filtration, filter
Cake is washed, last vacuum dried rear prepared 2- chloro-5-chloromethyl thiazoles, yield 91.4%, purity 98.5%.
Embodiment 2
0.1mol 5-Hydroxymethylthiazoles are dissolved in acetonitrile, add 0.25mol N- chloros succinyl sub- at 0 DEG C
Amine, is warmed to room temperature reaction 2h naturally after adding, add the iodine of catalytic amount, and is heated to back flow reaction 3h, and reaction terminates rear dense
Contracted solvent, and residue then is down into 0 DEG C, and adds 2- chloro-5-chloromethyl thiazole crystal seeds, insulated and stirred crystallization, suction filtration, filter
Cake is washed, last vacuum dried rear prepared 2- chloro-5-chloromethyl thiazoles, yield 93.4%, purity 99.2%.
Embodiment 3
0.1mol 5-Hydroxymethylthiazoles are dissolved in acetonitrile, add 0.3mol N- chloros succinyl sub- at 0 DEG C
Amine, is warmed to room temperature reaction 2h naturally after adding, add the iodine of catalytic amount, and is heated to back flow reaction 4h, and reaction terminates rear dense
Contracted solvent, and residue then is down into 0 DEG C, and adds 2- chloro-5-chloromethyl thiazole crystal seeds, insulated and stirred crystallization, suction filtration, filter
Cake is washed, last vacuum dried rear prepared 2- chloro-5-chloromethyl thiazoles, yield 93.8%, purity 99.2%.
General principle of the invention and principal character and advantages of the present invention has been shown and described above.The technology of the industry
Personnel it should be appreciated that the present invention is not limited to the above embodiments, simply explanation described in above-described embodiment and specification this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and modifications of the present invention are possible, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appending claims and its
Equivalent thereof.
Claims (5)
1. a kind of preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazoles, it is characterised in that：It is anti-with 5-Hydroxymethylthiazole
Raw material is answered, acetonitrile is reaction dissolvent, and N- chlorosuccinimides are chlorination reagent, and iodine is catalyst, and 2- is obtained through chlorination reaction
Chloro-5-chloromethyl thiazole.
2. a kind of preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazoles, it is characterised in that specific preparation process is：Will
5-Hydroxymethylthiazole is dissolved in acetonitrile, and N- chlorosuccinimides are added at 0 DEG C, is warmed to room temperature naturally after adding anti-
Should, after the iodine of addition catalytic amount after 5-Hydroxymethylthiazole reaction completely, and back flow reaction being heated to, reaction concentrates out molten after terminating
Agent, is then down to 0 DEG C, and add 2- chloro-5-chloromethyl thiazole crystal seeds, insulated and stirred crystallization, suction filtration, filter cake water by residue
Wash, last vacuum dried rear prepared 2- chloro-5-chloromethyl thiazoles.
3. the preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazoles according to claim 1 and 2, it is characterised in that：
The molar ratio of the 5-Hydroxymethylthiazole and N- chlorosuccinimides is 1:2-3.
4. the preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazoles according to claim 2, it is characterised in that：Institute
The room temperature reaction time is stated for 1-3h.
5. the preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazoles according to claim 2, it is characterised in that：Institute
Reflux time is stated for 2-4h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201611222381.3A CN106749086B (en) | 2016-12-27 | 2016-12-27 | A kind of preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazole |
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| CN201611222381.3A CN106749086B (en) | 2016-12-27 | 2016-12-27 | A kind of preparation method of pesticide intermediate 2- chloro-5-chloromethyl thiazole |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0260560A1 (en) * | 1986-09-17 | 1988-03-23 | Bayer Ag | Process for the preparation of 2-chlor-5-chlormethyl thiazole |
| CN1368966A (en) * | 1999-08-10 | 2002-09-11 | 辛根塔参与股份公司 | Process for preparation of thiazole derivatives |
| CN105732570A (en) * | 2014-12-12 | 2016-07-06 | 沈阳中化农药化工研发有限公司 | Cyclohexenone compound containing five-membered heterocycle and application thereof |
-
2016
- 2016-12-27 CN CN201611222381.3A patent/CN106749086B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0260560A1 (en) * | 1986-09-17 | 1988-03-23 | Bayer Ag | Process for the preparation of 2-chlor-5-chlormethyl thiazole |
| CN1368966A (en) * | 1999-08-10 | 2002-09-11 | 辛根塔参与股份公司 | Process for preparation of thiazole derivatives |
| CN105732570A (en) * | 2014-12-12 | 2016-07-06 | 沈阳中化农药化工研发有限公司 | Cyclohexenone compound containing five-membered heterocycle and application thereof |
Non-Patent Citations (2)
| Title |
|---|
| 徐家业 等，: "《有机合成化学及近代技术》", 31 December 1997, 西北工业大学出版社 * |
| 苏企洵: "《有机化学反应历程》", 31 December 1965, 高等教育出版社 * |
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