CN108164522A - The synthetic method of Diacloden - Google Patents
The synthetic method of Diacloden Download PDFInfo
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- CN108164522A CN108164522A CN201810150380.5A CN201810150380A CN108164522A CN 108164522 A CN108164522 A CN 108164522A CN 201810150380 A CN201810150380 A CN 201810150380A CN 108164522 A CN108164522 A CN 108164522A
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- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D417/00—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00
- C07D417/02—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings
- C07D417/06—Heterocyclic compounds containing two or more hetero rings, at least one ring having nitrogen and sulfur atoms as the only ring hetero atoms, not provided for by group C07D415/00 containing two hetero rings linked by a carbon chain containing only aliphatic carbon atoms
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Abstract
The present invention relates to compound synthesis field, more particularly to the synthetic method of agricultural insecticide Diacloden.Diacloden preparation method provided by the invention by the synthetic route for selecting suitable reaction raw materials design new, can prepare 2 chlorine of intermediate, 5 5-chloromethyl thiazole at room temperature, energy saving without cooling system, and can improve the yield of reaction.
Description
Technical field
The present invention relates to compound synthesis field, more particularly to the synthetic method of agricultural insecticide Diacloden.
Background technology
Diacloden (Thiamethoxam) is the second generation anabasine insecticide developed by Novartis Co., Ltd of Switzerland in 1991,
Chemical name is 3- (the chloro- thiazole -5- methyl of 2-) -5- methyl -4-N- nitro-imine base -1,3,5- oxadiazines.Diacloden structure
Formula is as follows：
The mechanism of action of Diacloden is similar to imidacloprid, and alternative inhibits insect nerve system nicotinic acetylcholine esterase
Receptor, and then the normal conduction of insect CNS is blocked, pest is caused to occur benumbing and dead.Diacloden and imidacloprid
Compared to active higher, safety is stronger, insecticidal spectrum is wider, speed of action faster, the lasting period it is longer, have and tag, is stomach toxicity, interior
Activity is inhaled, is to replace those are high to mammalian toxicity, have residual and environmental problem organophosphor, carbamates, organic
The preferable kind of chlorine insecticides.
Diacloden can effectively prevent the pests such as Lepidoptera, coleoptera, Thysanoptera, especially have to homoptera pest very high
Activity can effectively prevent various aphids, leafhopper, plant hopper, aleyrodid, chafer larva, colorado potato bug, flea beetle, nematode, ground
The pests such as beetle, leaf miner and the pest that resistance is generated to multiple types chemical pesticide.With imidacloprid, Acetamiprid, Nitenpyram
Etc. no interactions resistance.Cauline leaf process, seed treatment are can be not only used for, can also carry out soil treatment.Suitable for crop is rice class crop, sweet tea
Dish, rape, potato, cotton, Kidney bean, fruit tree, peanut, sunflower, soybean, tobacco and citrus etc..Under recommended dose, to making
Object safety, no poisoning.
Diacloden sterling is white powder, and 139.1 DEG C of fusing point is stablized at 20 DEG C, and solubility (25 DEG C) is in water
4100mg/L, is soluble in organic solvent, and vapour pressure is 6.6 × 10-9Pa (25 DEG C), KowLogP=-0.13 (25 DEG C).The medicament
To rat acute toxicity LD50For 1563mg/kg；Rat acute percutaneous toxicity LD50＞ 2000mg/kg；Rat acute sucks
Toxicity LC50(4h) is 3720mg/m3；It is non-stimulated to lagophthalmos eyeball and skin.It is to quail acute toxicity LD50It is wild for 1552mg/kg
Duck LC50＞ 5200 × 10-6；Rainbow trout LC50(96h) ＞ 100mg/L；Earthworm EC50(14d) ＞ 1000mg/L soil；Water flea EC50
(96h) ＞ 100mg/L；Honeybee LC50For every 0.024 μ g of bee active ingredient；There is moderate toxicity to sugared shrimp, be one to people and animals and ring
The foolproof insecticide in border.
In the prior art, Diacloden can through 2- chloro-5-chloromethyl thiazoles and 3- methyl -4- nitroiminoperhydros -
1,3,5- oxadiazines is obtained by condensation reaction.Wherein, intermediate 2- chloro-5-chloromethyl thiazoles are at low ambient temperatures, by 2-
Amino -5- methylthiazols carry out diazotising, chlorination reaction obtains.This needs cooling system, and consumes mass energy.This is anti-
Answer route yield relatively low.Therefore, it is necessary to overcome the above problem, energy consumption is reduced, improves the yield of reaction route.
Invention content
Technical problem
The technical problem to be solved by the present invention is to overcome the deficiencies in the prior art, by selecting suitable reaction raw materials, energy
It is enough to prepare intermediate 2- chloro-5-chloromethyl thiazoles at room temperature, it is energy saving without cooling system, and reaction can be improved
Yield.
Technical solution
Diacloden synthetic route of the present invention is as follows：
(1) the chloro- 5- methylthiazols of 2- are prepared：In the presence of t- fourth sulphur nitriles, by 2- amino -5- methylthiazols and anhydrous chlorination
Copper (II) reaction is post-treated to obtain the chloro- 5- methylthiazols of 2-；
(2) 2- chloro-5-chloromethyl thiazoles are prepared：The chloro- 5- methylthiazols of 2- are reacted with appropriate N- chlorosuccinimides,
2- chloro-5-chloromethyl thiazoles are prepared；
(3) Diacloden is synthesized：By 3- methyl -4- nitroiminoperhydro -1,3,5- oxadiazines and the chloro- 5- chloromethyls of 2-
Thiazole obtains Diacloden through condensation reaction.
Specific preparation method is as follows：
(1) the chloro- 5- methylthiazols of 2- are prepared：It is passed through nitrogen in a kettle, then adds in dry anhydrous cupric chloride
(II), it is being vigorously stirred and under nitrogen protection, the drying acetonitrile solution of t- fourth sulphur nitriles (t-Bu-S-N=O) is added in into reaction kettle
In, then 2- amino -5- methylthiazols are added portionwise, 20% hydrochloric acid solution is added in after reaction, vacuum distillation removes solvent, adds in
Appropriate chloroform with saturated common salt water washing, and is dried with anhydrous magnesium sulfate, and vacuum distillation removes solvent, obtains the chloro- 5- methyl of 2-
Thiazole；
(2) 2- chloro-5-chloromethyl thiazoles are prepared：The chloro- 5- methylthiazols of 2- are dissolved in chloroform, add in appropriate N- chloros fourth two
Acid imide.After heating up and reacting under light illumination, suitable quantity of water is added in into reactor to remove succimide.After organic layer precipitation
Obtain 2- chloro-5-chloromethyl thiazoles；
(3) Diacloden is synthesized：It puts into 3- methyl -4- nitroiminoperhydros -1,3,5- successively into reaction bulb and dislikes two
Piperazine and dimethyl carbonate, 2- chloro-5-chloromethyl thiazoles, are slowly added to tetramethylammonium hydroxide, potassium carbonate and dimethyl carbonate
Mixture, be 6.5 with the pH value of hydrochloric acid conditioning solution, stratification, concentration of organic layers cools down and filters after reaction
It is dry, obtain white powder product, as Diacloden.
In step (1), the molar ratio of t- fourth sulphur nitriles and 2- amino -5- methylthiazols is 1:10-10:1, preferably 1:5-5:
1, more preferable 3:2；Reaction can be carried out at 0 DEG C to 60 DEG C, preferably carried out at 10 DEG C to 40 DEG C, more preferably at 25 DEG C into
Row；2- amino -5- methylthiazols are slowly added in 30-60min, are preferably slowly added in 35-50min, are more preferably existed
It is slowly added in 40min.
In step (2), the molar ratio of the chloro- 5- methylthiazols of 2- and N- chlorosuccinimides is 1:10-10:1, preferably
1:5-5:1, more preferable 1:1；Reaction can carry out at 30 DEG C to 70 DEG C, preferably be carried out at 45 DEG C to 60 DEG C, more preferably 50
It is carried out at DEG C.
In step (3), 2- chloro-5-chloromethyl thiazoles and 3- methyl -4- nitroiminoperhydros -1,3,5- oxadiazines
Molar ratio be 1:10-10:1, preferably 1:5-5:1, more preferable 1:1.15；Reaction can carry out at 50 DEG C to 80 DEG C, and preferably 60
DEG C to carrying out at 70 DEG C, more preferably carried out at 67 DEG C；The mixture of tetramethylammonium hydroxide, potassium carbonate and dimethyl carbonate
Feed time is 30-70min, preferably 40-60min, more preferable 50min.
Advantageous effect
Equipment cost can be reduced by using the Diacloden preparation method of the present invention, it is energy saving, and improve thiophene worm
The yield of piperazine.
Embodiment
It can be obtained by following embodiment and the present invention is best understood from, the embodiment is used to illustrate, but not
It should be interpreted that and limit the scope of the invention.The scope of the present invention is provided by claim, and is also included and be equal to claim
Meaning and scope in all modifications.
Embodiment 1：
(1) the chloro- 5- methylthiazols of 2- are prepared：T- fourth sulphur nitrile 72g (0.6mol) are dissolved in dry acetonitrile (1.5L) to be configured to
Solution.It is passed through nitrogen in a kettle, then adds in dry anhydrous cupric chloride (II) 65g (0.48mol), is being vigorously stirred simultaneously
Under nitrogen protection, the t- fourth sulphur nitriles solution of preparation is added in reaction kettle, 25 DEG C are then kept, within the time of 40min or so
2- amino -5- methylthiazols (45.6g, 0.40mol) are added portionwise.Reaction mixture reacts 2h at 25 DEG C, then adds in
20% hydrochloric acid solution.Vacuum distillation removes solvent, adds in 300ml chloroforms, with saturated common salt water washing 100mL × 3, and uses nothing
Water magnesium sulfate is dried, and vacuum distillation removes solvent, obtains the chloro- 5- methylthiazols of 49.7g2-, yield 93%；
(2) 2- chloro-5-chloromethyl thiazoles are prepared：The chloro- 5- methylthiazols of 49.7g (0.372mol) 2- are dissolved in 100ml chlorine
It is imitative, add in equimolar N- chlorosuccinimides.After being warming up to 50 DEG C and reacting 5h under light illumination, added in into reactor
150ml water is to remove succimide.40.65g 2- chloro-5-chloromethyl thiazoles, yield 65% are obtained after organic layer precipitation；
(3) Diacloden is synthesized：It is complete to put into 44.53g (0.278mol) 3- methyl -4- nitroiminos successively into reaction bulb
- 1,3,5- oxadiazines and 148.8g dimethyl carbonates, 40.65g (0.242mol) 2- chloro-5-chloromethyl thiazoles are hydrogenated, is slowly added
Enter the mixture of 1g tetramethylammonium hydroxide, 58g potassium carbonate and 130g dimethyl carbonates, after reaction, add in 150ml
Water is 6.5 with the pH value of hydrochloric acid conditioning solution, and organic layer is concentrated under reduced pressure in stratification, and cool down crystallization, and filtration drying obtains
57.89g white powder products, as Diacloden, yield 82%.
Embodiment 2：
(1) the chloro- 5- methylthiazols of 2- are prepared：T- fourth sulphur nitrile 96g (0.8mol) are dissolved in dry acetonitrile (2.0L) to be configured to
Solution.It is passed through nitrogen in a kettle, then adds in dry anhydrous cupric chloride (II) 81.6g (0.60mol), is being vigorously stirred
And under nitrogen protection, the t- fourth sulphur nitriles solution of preparation is added in reaction kettle, 25 DEG C are then kept, in the time of 40min or so
2- amino -5- methylthiazols (45.6g, 0.40mol) are inside added portionwise.Reaction mixture reacts 2h at 25 DEG C, then adds in
20% hydrochloric acid solution.Vacuum distillation removes solvent, adds in 350ml chloroforms, with saturated common salt water washing 150mL × 3, and uses nothing
Water magnesium sulfate is dried, and vacuum distillation removes solvent, obtains the chloro- 5- methylthiazols of 49.3g2-, yield 92%；
(2) 2- chloro-5-chloromethyl thiazoles are prepared：The chloro- 5- methylthiazols of 49.3g (0.368mol) 2- are dissolved in 100ml chlorine
It is imitative, add in equimolar N- chlorosuccinimides.After being warming up to 50 DEG C and reacting 5h under light illumination, added in into reactor
150ml water is to remove succimide.39.89g 2- chloro-5-chloromethyl thiazoles, yield 64% are obtained after organic layer precipitation；
(3) Diacloden is synthesized：It is complete to put into 56.64g (0.354mol) 3- methyl -4- nitroiminos successively into reaction bulb
- 1,3,5- oxadiazines and 148.8g dimethyl carbonates, 39.89g (0.236mol) 2- chloro-5-chloromethyl thiazoles are hydrogenated, is slowly added
Enter the mixture of 1g tetramethylammonium hydroxide, 58g potassium carbonate and 130g dimethyl carbonates, after reaction, add in 150ml
Water is 6.5 with the pH value of hydrochloric acid conditioning solution, and organic layer is concentrated under reduced pressure in stratification, and cool down crystallization, and filtration drying obtains
55.07g white powder products, as Diacloden, yield 80%.
Embodiment 3：
(1) the chloro- 5- methylthiazols of 2- are prepared：T- fourth sulphur nitrile 120g (1.0mol) are dissolved in dry acetonitrile (3.0L) to be configured to
Solution.It is passed through nitrogen in a kettle, then adds in dry anhydrous cupric chloride (II) 130.56g (0.96mol), is acutely stirring
Mix and under nitrogen protection, the t- fourth sulphur nitriles solution of preparation added in reaction kettle, then keep 25 DEG C, 50min or so when
It is interior that 2- amino -5- methylthiazols (114g, 1.0mol) are added portionwise.Reaction mixture reacts 3h at 25 DEG C, then adds in
20% hydrochloric acid solution.Vacuum distillation removes solvent, adds in 450ml chloroforms, with saturated common salt water washing 200mL × 3, and uses nothing
Water magnesium sulfate is dried, and vacuum distillation removes solvent, obtains the chloro- 5- methylthiazols of 120.6g2-, yield 90%；
(2) 2- chloro-5-chloromethyl thiazoles are prepared：The chloro- 5- methylthiazols of 120.6g (0.90mol) 2- are dissolved in 200ml chlorine
It is imitative, add in equimolar N- chlorosuccinimides.After being warming up to 50 DEG C and reacting 6h under light illumination, added in into reactor
300ml water is to remove succimide.95.82g 2- chloro-5-chloromethyl thiazoles, yield 63% are obtained after organic layer precipitation；
(3) Diacloden is synthesized：It is complete to put into 92.16g (0.576mol) 3- methyl -4- nitroiminos successively into reaction bulb
- 1,3,5- oxadiazines and 354.1g dimethyl carbonates, 95.82g (0.576mol) 2- chloro-5-chloromethyl thiazoles are hydrogenated, is slowly added
Enter the mixture of 2.38g tetramethylammonium hydroxide, 138g potassium carbonate and 309.4g dimethyl carbonates, after reaction, add in
400ml water is 6.5 with the pH value of hydrochloric acid conditioning solution, and organic layer is concentrated under reduced pressure in stratification, and cool down crystallization, filtration drying,
Obtain 131.06g white powder products, as Diacloden, yield 78%.
Claims (9)
1. a kind of preparation method of Diacloden, it is characterised in that the described method comprises the following steps：
(1) the chloro- 5- methylthiazols of 2- are prepared：In the presence of t- fourth sulphur nitriles, by 2- amino -5- methylthiazols and anhydrous cupric chloride
(II) it reacts post-treated and obtains the chloro- 5- methylthiazols of 2-；
(2) 2- chloro-5-chloromethyl thiazoles are prepared：The chloro- 5- methylthiazols of 2- with appropriate N- chlorosuccinimides are reacted, are prepared
Obtain 2- chloro-5-chloromethyl thiazoles；
(3) Diacloden is synthesized：By 3- methyl -4- nitroiminoperhydro -1,3,5- oxadiazines and 2- chloro-5-chloromethyl thiazoles
Diacloden is obtained through condensation reaction.
2. the preparation method of Diacloden according to claim 1, it is characterised in that in step (1), t- fourth sulphur nitriles and 2-
The molar ratio of amino -5- methylthiazols is 1:10-10:1, reaction can carry out at 0 DEG C to 60 DEG C, 2- amino -5- methylthiazols
It is slowly added in 30-60min.
3. the preparation method of Diacloden according to claim 1, it is characterised in that the chloro- 5- methyl thiazoliums of 2- in step (2)
The molar ratio of azoles and N- chlorosuccinimides is 1:10-10:1, preferably 1:5-5:1, most preferably 1:1；Reaction is at 30 DEG C to 70
It carries out at DEG C, is preferably carried out at 45 DEG C to 60 DEG C, most preferably carried out at 50 DEG C.
4. the preparation method of Diacloden according to claim 1, it is characterised in that the chloro- 5- chloromethyls of 2- in step (3)
The molar ratio of thiazole and 3- methyl -4- nitroiminoperhydro -1,3,5- oxadiazines is 1:10-10:1, reaction can be at 50 DEG C
It is carried out to 80 DEG C, the mixture feed time of tetramethylammonium hydroxide, potassium carbonate and dimethyl carbonate is 30-70min.
5. the preparation method of Diacloden according to claim 2, it is characterised in that in step (1), t- fourth sulphur nitriles and 2-
The molar ratio of amino -5- methylthiazols is 1:5-5:1, reaction can carry out at 10 DEG C to 40 DEG C, and 2- amino -5- methylthiazols exist
It is slowly added in 35-50min.
6. the preparation method of Diacloden according to claim 4, it is characterised in that the chloro- 5- chloromethyls of 2- in step (3)
The molar ratio of thiazole and 3- methyl -4- nitroiminoperhydro -1,3,5- oxadiazines is 1:5-5:1, reaction can be at 60 DEG C extremely
It is carried out at 70 DEG C, the mixture feed time of tetramethylammonium hydroxide, potassium carbonate and dimethyl carbonate is 40-60min.
7. the preparation method of Diacloden according to claim 5, it is characterised in that in step (1), t- fourth sulphur nitriles and 2-
The molar ratio of amino -5- methylthiazols is 3:2, it reacts and is carried out at 25 DEG C；2- amino -5- methylthiazols are slow in 40min
It adds in.
8. the preparation method of Diacloden according to claim 6, it is characterised in that in step (3), the chloro- 5- chloromethyls of 2-
The molar ratio of thiazole and 3- methyl -4- nitroiminoperhydro -1,3,5- oxadiazines is 1:1.15, react at 67 DEG C into
Row, the mixture feed time of tetramethylammonium hydroxide, potassium carbonate and dimethyl carbonate is 50min.
9. according to the preparation method of claim 1-8 any one of them Diaclodens, it is characterised in that the method includes following
Step：
(1) the chloro- 5- methylthiazols of 2- are prepared：It is passed through nitrogen in a kettle, then adds in dry anhydrous cupric chloride (II),
It is vigorously stirred and under nitrogen protection, the drying acetonitrile solution of t- fourth sulphur nitriles (t-Bu-S-N=O) is added in reaction kettle, then in batches
2- amino -5- methylthiazols are added in, 20% hydrochloric acid solution is added in after reaction, vacuum distillation removes solvent, adds in appropriate chloroform,
It with saturated common salt water washing, and is dried with anhydrous magnesium sulfate, vacuum distillation removes solvent, obtains the chloro- 5- methylthiazols of 2-；
(2) 2- chloro-5-chloromethyl thiazoles are prepared：The chloro- 5- methylthiazols of 2- are dissolved in chloroform, it is sub- to add in appropriate N- chloros succinyl
Amine.After heating up and reacting under light illumination, suitable quantity of water is added in into reactor to remove succimide.It is obtained after organic layer precipitation
2- chloro-5-chloromethyl thiazoles；
(3) Diacloden is synthesized：Put into successively into reaction bulb 3- methyl -4- nitroiminoperhydro -1,3,5- oxadiazines and
Dimethyl carbonate, 2- chloro-5-chloromethyl thiazoles are slowly added to the mixed of tetramethylammonium hydroxide, potassium carbonate and dimethyl carbonate
Object is closed, is 6.5 with the pH value of hydrochloric acid conditioning solution after reaction, stratification, concentration of organic layers, cool down simultaneously filtration drying,
Obtain white powder product, as Diacloden.
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092783A (en) * | 2019-06-04 | 2019-08-06 | 湖南化工研究院有限公司 | A kind of preparation method of Diacloden |
| CN111036158A (en) * | 2019-12-28 | 2020-04-21 | 邯郸市瑞田农药有限公司 | 2 chlorine-5 chloromethyl thiazole synthesis reaction system |
| CN115385904A (en) * | 2022-09-15 | 2022-11-25 | 内蒙古同创高科化学有限公司 | Green synthesis method of thiamethoxam |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106029658A (en) * | 2014-05-28 | 2016-10-12 | 龙灯农业化工国际有限公司 | Method of producing thiamethoxam |
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- 2018-02-13 CN CN201810150380.5A patent/CN108164522B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106029658A (en) * | 2014-05-28 | 2016-10-12 | 龙灯农业化工国际有限公司 | Method of producing thiamethoxam |
Non-Patent Citations (2)
| Title |
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| HAIBO YU ET AL.: "Synthesis and Insecticidal Activity of N-Substituted (1,3-Thiazole)alkyl Sulfoximine Derivatives", 《J. AGRIC. FOOD CHEM.》 * |
| SHIGERU OAE ET AL.: "Direct Conversion of Arylamines to Halides By Deamination with Thionitrite or Related Compounds and Anhydrous Coppe(II) Halides", 《BULL. CHEM. SOC.》 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110092783A (en) * | 2019-06-04 | 2019-08-06 | 湖南化工研究院有限公司 | A kind of preparation method of Diacloden |
| CN110092783B (en) * | 2019-06-04 | 2020-11-20 | 湖南化工研究院有限公司 | Preparation method of thiamethoxam |
| CN111036158A (en) * | 2019-12-28 | 2020-04-21 | 邯郸市瑞田农药有限公司 | 2 chlorine-5 chloromethyl thiazole synthesis reaction system |
| CN115385904A (en) * | 2022-09-15 | 2022-11-25 | 内蒙古同创高科化学有限公司 | Green synthesis method of thiamethoxam |
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