CN106478494B - The production method of the chloro- 4- methanesulfonylpyridine of 2,3,5,6- tetra- - Google Patents
The production method of the chloro- 4- methanesulfonylpyridine of 2,3,5,6- tetra- Download PDFInfo
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- CN106478494B CN106478494B CN201610844428.3A CN201610844428A CN106478494B CN 106478494 B CN106478494 B CN 106478494B CN 201610844428 A CN201610844428 A CN 201610844428A CN 106478494 B CN106478494 B CN 106478494B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D213/00—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members
- C07D213/02—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members
- C07D213/04—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom
- C07D213/60—Heterocyclic compounds containing six-membered rings, not condensed with other rings, with one nitrogen atom as the only ring hetero atom and three or more double bonds between ring members or between ring members and non-ring members having three double bonds between ring members or between ring members and non-ring members having no bond between the ring nitrogen atom and a non-ring member or having only hydrogen or carbon atoms directly attached to the ring nitrogen atom 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
- C07D213/62—Oxygen or sulfur atoms
- C07D213/70—Sulfur atoms
- C07D213/71—Sulfur atoms to which a second hetero atom is attached
Abstract
The invention discloses a kind of production method of 2,3,5,6- tetra- chloro- 4- methanesulfonylpyridines, it is related to replacing and aoxidizing the optimal conditions of two-step reaction.Method of the present invention is using penta chloropyridine as raw material; catalyst is added; it is dissolved in solvent and substitution reaction one-step method generation 2 occurs under room temperature with sodium methyl mercaptide aqueous solution; 3,5,6- tetra- chloro- 4- first mercaptopyridines; 2; 3,5,6- tetra- chloro- 4- first mercaptopyridines are dissolved in methylene chloride; oxidant Oxidation at room temperature is added and generates target product 2; 3,5,6- tetra- chloro- 4- methanesulfonylpyridines; reaction terminates through simple purification step; product purity can reach 99%, and the total recovery of two-step reaction reaches 90% or more, have very strong directiveness to industrialized production.
Description
Technical field
The present invention relates to a kind of industrialized preparing process of 2,3,5,6- tetra- chloro- 4- methanesulfonylpyridines, belong to chemical industry conjunction
At technical field.
Background technique
Pyridine and benzene belong to bioisostere.Although the two in many chemical aspects be it is similar, the two is dredged
Aqueous difference is larger.Therefore, substituting noval chemical compound obtained from phenyl ring as pyridine often has higher bioactivity, lower
Toxicity, higher absorbability or selectivity.And there is brilliant Environmental compatibility to beneficial organism.Pyridine farm chemical mainly relates to
And fungicide, insecticide and herbicide etc..The pesticide of nearly all classification all contains pyridine structure, at present in the world
The pesticide containing pyridine ring of commercialization has more than 70 kinds, and in China, the pesticide active ingredient containing pyridine ring of registration shares more than 50 kinds, wherein
Including the market-ripes such as diquat dibromide, paraquat, chlopyrifos, imidacloprid, nicosulfuron, production capacity and the biggish mainstream pesticide product of yield
Kind.China development and production have bright market prospects pyridine downstream pesticide, as fluazinam, fluorine humulone, fluazifop,
Acetamiprid, Nitenpyram and diflufenican etc..
Producting and exporting country of the China as the maximum pesticide original medicine in the whole world is looked forward in 2, more than 600 family's pesticide producings according to statistics
More than 400 family, industry (including hygienic insecticide manufacturing enterprise) Zhong You raw medicine manufacturing enterprise.Currently, the compound containing pyridine ring structure
Have become the innovation direction of novel agrochemical former medicine manufacturing enterprise.
Just because of pyridine ring has such unique effect in pesticide molecule design, the very big of organic chemist is caused
Interest.Scientist is in the ascendant to the research of this kind of compound, and constantly has new Pesticidal products to come out.2,3,5,6- tetra- is chloro-
4- methanesulfonylpyridine is a newcomer in this kind of pesticide, and have the characteristics that pyridine farm chemical: dissolubility is low in water
And have appropriate dissolubility in organic solvent, it is particularly applicable in the infringement for preventing mould to crops.It also in ink, make
There is relatively broad application in the fields such as paper, weaving and polymeric material.
Traditional 2,3,5,6- tetra- chloro- 4- methanesulfonylpyridine production technologies are to utilize severe toxicity using penta chloropyridine as raw material
Reagent vulcanized sodium carries out nucleophilic substitution to it, the sodium mercaptides intermediate of generation again with the methyl such as iodomethane or dimethyl suflfate
Change reagent to react to obtain the chloro- 4- first mercaptopyridine of intermediate 2,3,5,6- tetra-.Finally use hydrogen peroxide, the concentrated sulfuric acid or chlorine oxidation
Final products are obtained, these existing techniques are low there are reaction yield and used vulcanized sodium, iodomethane or dimethyl suflfate etc.
Poisonous reagent not only generates a large amount of three wastes while making severe operational environment, belongs to superseded outmoded technique.
Summary of the invention
For in the chloro- 4- methanesulfonylpyridine production technology of original 2,3,5,6- tetra- not be used only vulcanized sodium, iodomethane
Or the toxic articles raw material such as dimethyl suflfate, but also hydrogen peroxide is used, the Strong oxdiatives such as the concentrated sulfuric acid or chlorine and strong reagents.It is raw
Production process have the characteristics that it is explosive, generate a large amount of spent acid, exhaust gas and cumbersome.The purpose of the present invention is to provide a kind of easily behaviour
The process route of work effectively improves goal response yield, reduces environmental pollution.The present invention uses sodium methyl mercaptide aqueous solution (20%
Mass concentration) 2,3,5,6- tetra- chloro- 4- first mercaptopyridine of one-step synthesis method, then it is oxidized to by m-chloro-benzoic acid peroxide
Sulfone, and reaction condition is optimized, effectively increase the purity and yield of target product.
To achieve the above objectives, the technical solution adopted by the present invention is that:
A kind of production method of 2,3,5,6- tetra- chloro- 4- methanesulfonylpyridines, this method are added using penta chloropyridine as raw material
Catalyst is dissolved in solvent and substitution reaction one-step method generation 2,3,5,6- tetra- occurs under room temperature with sodium methyl mercaptide aqueous solution
Chloro- 4- first mercaptopyridine, 2,3,5,6- tetra- chloro- 4- first mercaptopyridines are dissolved in methylene chloride, and it is raw that oxidant Oxidation at room temperature is added
At the chloro- 4- methanesulfonylpyridine of target product 2,3,5,6- tetra-, structural formula are as follows:
Described 2, the production method of 3,5,6- tetra- chloro- 4- methanesulfonylpyridines, the oxidant select m-chloro peroxide
Change benzoic acid.
Described 2, the production method of 3,5,6- tetra- chloro- 4- methanesulfonylpyridines, the oxidant m-chloro benzoyl peroxide
Formic acid total amount is the 2.0-2.3 molar equivalent of 2,3,5,6- tetra- chloro- 4- first mercaptopyridines, is divided into the addition of three batches, and reaction is opened
One third is added when the beginning, then at interval of 15 minutes addition one thirds.
Described 2, the production method of 3,5,6- tetra- chloro- 4- methanesulfonylpyridines, the solvent are hydrophilic solvent.
Described 2, the production method of 3,5,6- tetra- chloro- 4- methanesulfonylpyridines, the solvent are tetrahydrofuran, N, N-
One of dimethylformamide, ethyl alcohol or methanol, penta chloropyridine and solvent quality ratio are 1:3~1:15.
Described 2, the production method of 3,5,6- tetra- chloro- 4- methanesulfonylpyridines, the catalyst using sodium iodide or
The mass ratio of potassium iodide, catalyst and penta chloropyridine is 1:2000~1:500.
Specific embodiment
Embodiment one:
Penta chloropyridine (10g, 40.2mmol) is dissolved in tetrahydrofuran (THF) (50mL), and ice bath is cooling, in one hour slowly
20% sodium methyl mercaptide aqueous solution (16.9g, 48.2mmol) is added dropwise.Reaction solution reacts at room temperature five hours.GC has detected raw material
End of reaction.Tetrahydrofuran is recovered under reduced pressure, is added ethyl acetate (80mL), is washed with (2 × 30mL), organic phase is through anhydrous slufuric acid
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10g, 95%) are concentrated under reduced pressure to obtain in sodium after drying, filtering.
Penta chloropyridine (10g, 40.2mmol) and NaI (60mg, 0.4mmol) are dissolved in tetrahydrofuran (THF) (50mL), ice
20% sodium methyl mercaptide aqueous solution (16.9g, 48.2mmol) is slowly added dropwise in water-bath cooling in one hour.Reaction solution room temperature reaction
Three hours.GC detects raw material end of reaction.Tetrahydrofuran is recovered under reduced pressure, is added ethyl acetate (80mL), with (2 × 30mL)
Washing, organic phase is dried over anhydrous sodium sulfate, be concentrated under reduced pressure after filtering 2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10g,
95%).
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10g, 38.0mmol) are dissolved in methylene chloride DCM) in (80mL), ice water
Bath cooling, in three times every batch of every 15 minutes addition m-chloro-benzoic acid peroxides (14.4g, 83.6mmol).Reaction solution room temperature is anti-
It answers three hours.GC detects raw material end of reaction.Reaction solution is first washed with (2 × 20mL) saturated sodium carbonate solution, then with (2 ×
20mL) to wash, organic phase is dried over anhydrous sodium sulfate, and crude product is concentrated under reduced pressure to obtain after filtering, and ethyl alcohol (5mL) mashing is added in crude product,
Filtration drying obtains (10.8g, 96%) 2,3,5,6- tetra- chloro- 4- methanesulfonylpyridine.
Embodiment two:
Penta chloropyridine (10g, 40.2mmol) is dissolved in n,N-Dimethylformamide (DMF) (50mL), and ice-water bath is cooling, and one
20% sodium methyl mercaptide aqueous solution (16.9g, 48.2mmol) is slowly added dropwise in hour.Reaction solution reacts at room temperature five hours.GC inspection
Survey raw material end of reaction.DMF is recovered under reduced pressure, is added ethyl acetate (40mL), is washed with (2 × 20mL), organic phase is through nothing
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10.1g, 95.2%) are concentrated under reduced pressure to obtain in aqueous sodium persulfate after drying, filtering.
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10g, 38.0mmol) are dissolved in DCM (80mL), and ice-water bath is cooling,
Every batch of was every 15 minutes addition m-chloro-benzoic acid peroxides (14.4g, 83.6mmol) in three times.Reaction solution reacts at room temperature two hours.
GC detects raw material end of reaction.Reaction solution is first washed with (2 × 20mL) saturated sodium carbonate solution, then is washed with (2 × 20mL),
Organic phase is dried over anhydrous sodium sulfate, and DCM residue 5mL is concentrated under reduced pressure into after filtering, filters (10.5g, 94%) 2,3,5,6-
Four chloro- 4- methanesulfonylpyridines.
Embodiment three:
Penta chloropyridine (10g, 40.2mmol) is dissolved in DMF (50mL), and ice-water bath is cooling, is slowly added to 98% solid first
Sodium mercaptides (3.45g, 48.2mmol).Reaction solution reacts at room temperature three hours.GC detects raw material end of reaction.It is recovered under reduced pressure
DMF, solid are beaten with water (5mL), dry 2,3,5,6- tetra- chloro- 4- first mercaptopyridines (9.7g, 92%) after filtering.
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10g, 38.0mmol) are dissolved in dichloroethanes (DCE) (80mL), ice water
Bath cooling, in three times every batch of every 15 minutes addition m-chloro-benzoic acid peroxides (14.4g, 83.6mmol).Reaction solution room temperature is anti-
It answers two hours.GC detects raw material end of reaction.Reaction solution is first washed with (2 × 20mL) saturated sodium carbonate solution, then with (2 ×
20mL) to wash, organic phase is dried over anhydrous sodium sulfate, and crude product is concentrated under reduced pressure to obtain after filtering, and ethyl alcohol (5mL) mashing is added in crude product,
Filtration drying obtains (10.6g, 95%) 2,3,5,6- tetra- chloro- 4- methanesulfonylpyridine.
Example IV:
Penta chloropyridine (10g, 40.2mmol) is dissolved in ethyl alcohol (50mL), and ice bath is cooling, is slowly added dropwise 20% in one hour
Sodium methyl mercaptide aqueous solution (16.9g, 48.2mmol).Reaction solution reacts at room temperature five hours.GC detects raw material end of reaction.
It is concentrated under reduced pressure and removes ethyl alcohol, the solid particulate filters of precipitation simultaneously clean filter cake with water (5mL), and it is chloro- to obtain 2,3,5,6- tetra- after dry
4- first mercaptopyridine (10.1g, 96%).
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10g, 38.0mmol) are dissolved in DCM (80mL), and ice-water bath is cooling,
Every batch of was every 15 minutes addition m-chloro-benzoic acid peroxides (14.4g, 83.6mmol) in three times.Reaction solution reacts at room temperature two hours.
GC detects raw material end of reaction.Reaction solution first uses (15mL) 5%NaOH aqueous cleaning, then is washed with (2 × 20mL), has
Machine is mutually dried over anhydrous sodium sulfate, and crude product is concentrated under reduced pressure to obtain after filtering, and ethyl alcohol (5mL) mashing is added in crude product, and filtration drying obtains
(10.6g, 95%) 2,3,5,6- tetra- chloro- 4- methanesulfonylpyridine.
Embodiment five:
Penta chloropyridine (10g, 40.2mmol) and NaI (60mg, 0.4mmol) are dissolved in methanol (50mL), and ice-water bath is cooling,
20% sodium methyl mercaptide aqueous solution (16.9g, 48.2mmol) is slowly added dropwise in one hour.Reaction solution reacts at room temperature three hours.GC
Detect raw material end of reaction.It being concentrated under reduced pressure and removes methanol, the solid particulate filters of precipitation simultaneously clean filter cake with water (5mL),
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10.1g, 96%) are obtained after drying.
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10g, 38.0mmol) are dissolved in DCM (80mL), and ice-water bath is cooling,
Every batch of was every 15 minutes addition m-chloro-benzoic acid peroxides (14.4g, 83.6mmol) in three times.Reaction solution reacts at room temperature two hours.
GC detects raw material end of reaction.Reaction solution first uses (15mL) 5%NaOH aqueous cleaning, then is washed with (2 × 20mL), has
Machine is mutually dried over anhydrous sodium sulfate, and crude product is concentrated under reduced pressure to obtain after filtering, and methanol (5mL) mashing is added in crude product, and filtration drying obtains
(10.6g, 95%) 2,3,5,6- tetra- chloro- 4- methanesulfonylpyridine.
Embodiment six:
Penta chloropyridine (10g, 40.2mmol) and NaI (60mg, 0.4mmol) are dissolved in methanol (38mL), and ice-water bath is cooling,
20% sodium methyl mercaptide aqueous solution (16.9g, 48.2mmol) is slowly added dropwise in one hour.Reaction solution reacts at room temperature three hours.Subtract
Pressure concentration removes methanol, and the solid particulate filters of precipitation simultaneously clean filter cake with water (5mL), obtain 2,3,5,6- tetra- chloro- 4- after dry
First mercaptopyridine (9.3g, 88%).
Penta chloropyridine (10g, 40.2mmol) and NaI (60mg, 0.4mmol) are dissolved in methanol (190mL), and ice-water bath is cold
But, 20% sodium methyl mercaptide aqueous solution (16.9g, 48.2mmol) is slowly added dropwise in one hour.Reaction solution reacts at room temperature three hours.
It is concentrated under reduced pressure and removes methanol, the solid particulate filters of precipitation simultaneously clean filter cake with water (5mL), and it is chloro- to obtain 2,3,5,6- tetra- after dry
4- first mercaptopyridine (9.6g, 91%).
2,3,5,6- tetra- chloro- 4- first mercaptopyridines (10g, 38.0mmol) are dissolved in DCM (80mL), and ice-water bath is cooling, and one
M-chloro-benzoic acid peroxide (14.4g, 83.6mmol) is added in secondary property.Reaction solution reacts at room temperature two hours.GC has detected raw material
End of reaction.Reaction solution first uses (15mL) 5%NaOH aqueous cleaning, then is washed with (2 × 20mL), and organic phase is through anhydrous slufuric acid
Crude product is concentrated under reduced pressure to obtain in sodium after drying, filtering, methanol (5mL) mashing is added in crude product, and filtration drying obtains (9.6g, 86%) 2,3,5,
The chloro- 4- methanesulfonylpyridine of 6- tetra-.
Table 1: comparison of the different substitution reaction conditions to target product yield
Table 1 the result shows that, the molar equivalent of sodium methyl mercaptide is the most suitable when being 1.2.As the NaI that 0.01 molar equivalent is added
When catalyst, it can significantly shorten the reaction time.Tetra- kinds of solvents of THF, DMF, MeOH and EtOH are suitable for this reaction, wherein industrializing
Use MeOH the most suitable for solvent in production.
Table 2: comparison of the different oxidizing conditions to target product yield
| Serial number | M-CPBA (equivalent) | Solvent | Temperature (DEG C) | Time (h) | Yield (%) |
| 1 | 2.0 | DCM | 0-20 | 3 | 78.3 |
| 2 | 2.1 | DCM | 0-20 | 3 | 86.5 |
| 3 | 2.2 | DCM | 0-20 | 3 | 96.0 |
| 4 | 2.3 | DCM | 0-20 | 3 | 96.0 |
| 5 | 2.2 | DCM | 0-20 | 2 | 81.2 |
| 6 | 2.2 | DCE | 0-20 | 3 | 95.0 |
Table 2 the result shows that, the molar equivalent of m-CPBA is the most suitable when being 2.2.DCM and the various solvents of DCE two are suitable for
This reaction, wherein uses DCM for sweetening agent economical rationality in industrialized production.
Claims (4)
1. the production method of the chloro- 4- methanesulfonylpyridine of one kind 2,3,5,6- tetra-, it is characterised in that: using penta chloropyridine as raw material,
Catalyst is added, is dissolved in solvents tetrahydrofurane and the generation of substitution reaction one-step method occurs under room temperature with sodium methyl mercaptide aqueous solution
2,3,5,6- tetra- chloro- 4- first mercaptopyridines, 2,3,5,6- tetra- chloro- 4- first mercaptopyridines are dissolved in methylene chloride, and oxidant is added
M-chloro-benzoic acid peroxide, Oxidation at room temperature generate the chloro- 4- methanesulfonylpyridine of target product 2,3,5,6- tetra-, reaction equation are as follows:
2. the production method of according to claim 12,3,5,6- tetra- chloro- 4- methanesulfonylpyridines, it is characterised in that: institute
The oxidant m-chloro-benzoic acid peroxide total amount stated is the 2.0-2.3 molar equivalent of 2,3,5,6- tetra- chloro- 4- first mercaptopyridines,
It is divided into the addition of three batches, one third is added when starting in reaction, then at interval of 15 minutes addition one thirds.
3. the production method of according to claim 1 or 22,3,5,6- tetra- chloro- 4- methanesulfonylpyridines, it is characterised in that:
The penta chloropyridine and solvent quality ratio is 1:3~1:15.
4. the production method of according to claim 12,3,5,6- tetra- chloro- 4- methanesulfonylpyridines, it is characterised in that: institute
The catalyst stated uses sodium iodide or potassium iodide, and the mass ratio of catalyst and penta chloropyridine is 1:2000~1:500.
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