CN109053553A - The synthetic method of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines - Google Patents
The synthetic method of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines Download PDFInfo
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- CN109053553A CN109053553A CN201811203019.0A CN201811203019A CN109053553A CN 109053553 A CN109053553 A CN 109053553A CN 201811203019 A CN201811203019 A CN 201811203019A CN 109053553 A CN109053553 A CN 109053553A
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- 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
- C07D213/24—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 substituted hydrocarbon radicals attached to ring carbon atoms
- C07D213/28—Radicals substituted by singly-bound oxygen or sulphur atoms
- C07D213/32—Sulfur atoms
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Abstract
The invention discloses a kind of synthetic methods of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines, belong to pesticide pharmaceutical field, it is characterized in that, by the halogenated -2- trifluoromethyl pyridine of 5- and methyl ethyl sulfide, reaction obtains 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines under the effect of the catalyst.The reaction process are as follows: 1) under the conditions of protecting gas; methyl ethyl sulfide, solvent A, catalyst and acid binding agent are mixed; it is warming up to 110~135 DEG C; control pressure is 2~3 atmospheric pressure; the mixture of 5- halogenated -2- trifluoromethyl pyridine and solvent B is added dropwise, 30~45min of control is dripped off, and control reaction temperature is 140~155 DEG C; reaction pressure is 4~7 atmospheric pressure, and the reaction was continued, and 10~15h terminates；2) system is cooling, it is filtered to remove insoluble matter and obtains filtrate, filtrate is added in the saturated salt solution of about 2~3 times of volumes, stratification, after organic phase washing, after desiccant dryness, it is few to be concentrated to get 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridine steps of the present invention, yield is higher, and disposal of pollutants is less.
Description
Technical field
The invention belongs to pesticide pharmaceutical fields, and in particular to a kind of insecticide sulfoxaflor intermediate 3- [1- (first sulphur
Base) ethyl] -6 (trifluoromethyl) pyridines synthetic method.
Background technique
Sulfoxaflor (sulfoxaflor) is that The Dow Agrosciences, LLC. (Dow AgroSciences) develops the 1st
Novel Sulfoximine class agricultural insecticide, on November 2nd, 2010 hold in world pesticide research meeting in London, should
Company is announced.Sulfoxaflor insecticidal spectrum and neonicotinoid insecticide are different, and the thorn of resistance is generated to anabasine
Absorption insect also has compared with high preventive effect effect, it may be said that is a new pesticide control in terms of resistance management, by resistance to insecticides
Action Committee (Insecticide Resistance Action Committee, IRAC) regards as completely new Group 4C class
Unique member in insecticide.The molecular formula of sulfoxaflor is C10H10F3N3OS, chemical structural formula are as follows:
Sulfoxaflor is sulfimide insecticides, and sulfimide acts on the nervous system of insect, that is, acts on gallbladder
Alkali is played insecticidal function by internal unique binding site.It can absorb and enter in plant through leaf, stem, root.Flonicamid
Nitrile has efficient, broad spectrum of activity, and usage amount is low and the residual period is long.Suitable for prevention and treatment cotton account for stinkbug, aphid, aleyrodid, plant hopper and
Coccid etc..The suction juice class that resistance is generated to nicotinoids, pyrethroids class, organophosphate and carbamate pesticide can be effectively prevented
Pest.It is low to non-target arthropod toxicity, it is integrated pest control preferred agents.
3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines are the important intermediates for being synthetically prepared sulfoxaflor,
Structural formula is as follows:
In the prior art, the method for synthesizing 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines mainly has: 1. with 3-
(dimethylamino) acrylonitrile is raw material, reacts to obtain target compound by 6 steps.This method synthetic route is long, low yield, operation
Complexity, and " Grignard Reagent " is used in reaction.2. using n-butanal as Material synthesis target compound.This method experimental implementation
Complexity will also use the chloride of noble metal zirconium.3. using Beta-methyl methacrylaldehyde as Material synthesis target compound.This method exists
The longer disadvantage of reaction step.
Summary of the invention
The purpose of the present invention is to provide a kind of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] -6 (three
Methyl fluoride) pyridine synthetic method, the synthetic method reaction step is short, and yield is higher.
To achieve the above object, the present invention adopts the following technical scheme:
The synthetic method of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines,
It is characterized in that, by the halogenated -2- trifluoromethyl pyridine of 5- and methyl ethyl sulfide, reaction obtains 3- [1- under the effect of the catalyst
(methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines.
The reaction process are as follows:
1) under the conditions of protecting gas, methyl ethyl sulfide, solvent A, catalyst and acid binding agent are mixed, it is warming up to 110~
135 DEG C, control pressure is 2~3 atmospheric pressure, and the mixture of 5- halogenated -2- trifluoromethyl pyridine and solvent B, control 30 is added dropwise
~45min is dripped off, and control reaction temperature is 140~155 DEG C, and reaction pressure is 4~7 atmospheric pressure, and the reaction was continued, and 10~15h is tied
Beam；
2) system is cooling, it is filtered to remove insoluble matter and obtains filtrate, the saturation that filtrate is added to about 2~3 times of volumes is eaten
In salt water, stratification after desiccant dryness, is concentrated to get 3- [1- (methyl mercapto) ethyl] -6 (trifluoros after organic phase washing
Methyl) pyridine.
Halogenated -2- the trifluoromethyl pyridine of 5- be the chloro- 2- trifluoromethyl pyridine of 5-, the bromo- 2- trifluoromethyl pyridine of 5- or
The iodo- 2- trifluoromethyl pyridine of person 5-.
The catalyst is solid base catalyst.
The solid base catalyst the preparation method comprises the following steps: by calcium oxide, zinc oxide and aluminium oxide according to the mass ratio of the material 1:
(0.8~0.96): (1.12~1.25) are ground after mixing, and take 500~800 mesh particles, and 12~17h is roasted at 750~800 DEG C
Obtain solid base catalyst.
In step 1), protection gas is nitrogen or argon gas.
Solvent A is toluene, dimethylbenzene or nitrobenzene.
Acid binding agent is triethylamine or diethylamine.
Solvent B is benzene or toluene.
The molar ratio of the halogenated -2- trifluoromethyl pyridine of 5-, methyl ethyl sulfide and acid binding agent is 1:(1.6~2.2):
The amount ratio of (1.4~1.7), methyl ethyl sulfide and solvent A be 1g:(8~12) ml, the halogenated -2- trifluoromethyl pyridine of 5- with
The amount ratio of solvent B is 1g:(4~7ml), the mass ratio of the halogenated -2- trifluoromethyl pyridine of 5- and catalyst be 1:(0.25~
0.36)。
In step 2), desiccant is dead plaster or anhydrous calcium chloride.
The present invention uses solid catalyst, belongs to strong alkali catalyst, selects specific granular size, is conducive to carry out table
Face reaction.First by methyl second class thioether under conditions of solid alkali, high temperature and pressurization, in solid base Surface Creation following two
Kind carbanion transition state, two kinds of carbanions can be mutually converted by the rearrangement of methyl, as follows:
Then, nucleophilic substitution is carried out on the surface of catalyst with the halogenated -2- trifluoromethyl pyridine of 5-.In system condition
Under, the halogen in the stronger transition state b carbanion of nucleophilicity (alkalinity is stronger) halogenated -2- trifluoromethyl pyridine of attack 5- is former
Son carries out nucleophilic substitution, and halogen atom is taken off to form hydrogen halides, and carbanion is connected to the pyridine where original halogen atom
Position on ring generates target product.On the one hand hydrogen halides avoids the evolution of hydrogen halides from being formed in conjunction with the acid binding agent in system
Pollution；On the other hand, constantly the hydrogen halides molecule absorption of generation is disposed, is also beneficial to the further progress of reaction, improved
Reaction yield.
Compared with the existing technology, advantages of the present invention has:
1, step is short, and side reaction is few, and reaction yield is higher；
2, non-pollutant discharge.
Specific embodiment
Combined with specific embodiments below, the present invention is further illustrated.
Embodiment 1
The synthetic method of 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines, comprising the following steps:
1) under protection of argon gas, methyl ethyl sulfide, nitrobenzene, catalyst and triethylamine are mixed, are warming up to 125 DEG C,
Control pressure is 2.5 atmospheric pressure, and the mixture of 5- bromo- the 2- trifluoromethyl pyridine and toluene of 1mol is added dropwise, and controls 40min drop
Complete, control reaction temperature is 149 DEG C, and reaction pressure is 6 atmospheric pressure, and the reaction was continued, and 14h terminates.
Wherein, catalyst is solid base, preparation process are as follows: by calcium oxide, zinc oxide and aluminium oxide according to the mass ratio of the material
1:0.91:1.18 is ground after mixing, and takes 800 mesh particles, and 17h is roasted at 800 DEG C and obtains catalyst.
The molar ratio of the bromo- 2- trifluoromethyl pyridine of 5-, methyl ethyl sulfide and triethylamine is 1:1.9:1.55, Methylethyl
The amount ratio of thioether and nitrobenzene is 1g:10ml, and the amount ratio of the bromo- 2- trifluoromethyl pyridine of 5- and toluene is 1g:6.5ml, 5-
The mass ratio of bromo- 2- trifluoromethyl pyridine and catalyst is 1:0.28.
2) system is cooling, it is filtered to remove insoluble matter and obtains filtrate, filtrate is added to the saturated common salt of about 2.5 times of volumes
In water, stratification, after organic phase washing, with anhydrous calcium chloride it is dry after, be concentrated to get product, molar yield 97.6%,
HPLC purity 97.2%
Embodiment 2
The synthetic method of 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines, comprising the following steps:
1) under nitrogen protection, methyl ethyl sulfide, toluene, catalyst and ethylenediamine are mixed, are warming up to 110 DEG C, control
Pressing pressure is 2 atmospheric pressure, and the mixture of 5- chloro- the 2- trifluoromethyl pyridine and benzene of 1mol is added dropwise, and control 30min is dripped off, controlled
Reaction temperature processed is 140 DEG C, and reaction pressure is 4 atmospheric pressure, and the reaction was continued, and 10h terminates.
Wherein, catalyst is solid base, preparation process are as follows: by calcium oxide, zinc oxide and aluminium oxide according to the mass ratio of the material
1:0.8:1.12 is ground after mixing, and takes 500 mesh particles, and 12h is roasted at 750 DEG C and obtains catalyst.
The molar ratio of the chloro- 2- trifluoromethyl pyridine of 5-, methyl ethyl sulfide and ethylenediamine is 1:1.6:1.4, Methylethyl
The amount ratio of thioether and toluene is 1g:8ml, and the amount ratio of the chloro- 2- trifluoromethyl pyridine of 5- and benzene is 1g:4ml, the chloro- 2- tri- of 5-
The mass ratio of Fluoromethylpyridin and catalyst is 1:0.25.
2) system is cooling, it is filtered to remove insoluble matter and obtains filtrate, filtrate is added to the saturated salt solution of about 2 times of volumes
In, stratification after organic phase washing, after dead plaster drying, is concentrated to get product, molar yield 96.2%, HPLC
Purity 96.1%
Embodiment 3
The synthetic method of 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines, comprising the following steps:
1) under protection of argon gas, methyl ethyl sulfide, dimethylbenzene, catalyst and triethylamine are mixed, are warming up to 135 DEG C,
Control pressure is 3 atmospheric pressure, and the mixture of 5- iodo- the 2- trifluoromethyl pyridine and toluene of 1mol is added dropwise, and controls 45min drop
Complete, control reaction temperature is 155 DEG C, and reaction pressure is 7 atmospheric pressure, and the reaction was continued, and 15h terminates.
Wherein, catalyst is solid base, preparation process are as follows: by calcium oxide, zinc oxide and aluminium oxide according to the mass ratio of the material
1:0.96:1.25 is ground after mixing, and takes 650 mesh particles, and 15h is roasted at 780 DEG C and obtains catalyst.
The molar ratio of the iodo- 2- trifluoromethyl pyridine of 5-, methyl ethyl sulfide and triethylamine is 1:2.2:1.7, Methylethyl
The amount ratio of thioether and dimethylbenzene is 1g:12ml, and the amount ratio of the iodo- 2- trifluoromethyl pyridine of 5- and toluene is 1g:7ml, 5-
The mass ratio of iodo- 2- trifluoromethyl pyridine and triethylamine is 1:0.36.
2) system is cooling, it is filtered to remove insoluble matter and obtains filtrate, filtrate is added to the saturated salt solution of about 3 times of volumes
In, stratification after organic phase washing, after anhydrous calcium chloride drying, is concentrated to get product, molar yield 97.1%, HPLC
Purity 96.6%
Embodiment 4
Reaction temperature before the mixture that the bromo- 2- trifluoromethyl pyridine of 5- and toluene is added dropwise is set as 100 DEG C, reaction pressure
It is set as 1 atmospheric pressure, for example each substance of other conditions and dosage, reaction condition are constant, molar yield 45.1%, HPLC purity
62.3%.
Embodiment 5
Reaction temperature before the mixture that the bromo- 2- trifluoromethyl pyridine of 5- and toluene is added dropwise is set as 145 DEG C, reaction pressure
4 atmospheric pressure are set as, for example each substance of other conditions and dosage, reaction condition are constant, molar yield 59.6%, HPLC purity
71.6%.
Embodiment 6
Reaction temperature after the mixture that the bromo- 2- trifluoromethyl pyridine of 5- and toluene is added dropwise is set as 130 DEG C, reaction pressure
4 atmospheric pressure are set as, for example each substance of other conditions and dosage, reaction condition are constant, molar yield 20.6%, HPLC purity
55.1%.
Embodiment 8
Reaction temperature after the mixture that the bromo- 2- trifluoromethyl pyridine of 5- and toluene is added dropwise is set as 160 DEG C, reaction pressure
8 atmospheric pressure are set as, for example each substance of other conditions and dosage, reaction condition are constant, molar yield 44.6%, HPLC purity
77.9%.
8 atlas analysis of embodiment
MS (m/z), 221 (M+), molecular ion peak, mass spectral analysis, molecular weight of product is consistent with object.
1H-NMR (DMSO): chemical shift δ: 1.64 (d, 3H), 1.97 (d, 3H), 4.01 (q, 1H), 7.71 (d, 1H),
7.94 (dd, 1H), 8.70 (d, 1H), nmr analysis, product structure are consistent with object.
Claims (10)
- The synthetic method of insecticide sulfoxaflor intermediate 3- 1. [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines,It is characterized in that, reaction obtains under the effect of the catalyst by the halogenated -2- trifluoromethyl pyridine of 5- and methyl ethyl sulfide 3- [1- (methyl mercapto) ethyl] -6 (trifluoromethyl) pyridines.
- 2. -6 (trifluoromethyls) of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 1 The synthetic method of pyridine, which is characterized in that the reaction process are as follows:1) under the conditions of protecting gas, methyl ethyl sulfide, solvent A, catalyst and acid binding agent is mixed, are warming up to 110~135 DEG C, control pressure be 2~3 atmospheric pressure, be added dropwise 5- halogenated -2- trifluoromethyl pyridine and solvent B mixture, control 30~ 45min is dripped off, and control reaction temperature is 140~155 DEG C, and reaction pressure is 4~7 atmospheric pressure, and the reaction was continued, and 10~15h is tied Beam；2) system is cooling, it is filtered to remove insoluble matter and obtains filtrate, filtrate is added to the saturated salt solution of about 2~3 times of volumes In, stratification after desiccant dryness, is concentrated to get 3- [1- (methyl mercapto) ethyl] -6 (fluoroforms after organic phase washing Base) pyridine.
- 3. -6 (trifluoromethyls) of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 1 The synthetic method of pyridine, which is characterized in that the halogenated -2- trifluoromethyl pyridine of 5- is the chloro- 2- trifluoromethyl pyridine of 5-, 5- Bromo- 2- trifluoromethyl pyridine or the iodo- 2- trifluoromethyl pyridine of 5-.
- 4. -6 (trifluoromethyls) of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 1 The synthetic method of pyridine, feature exist, and the catalyst is solid base catalyst.
- 5. -6 (trifluoromethyls) of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 4 The synthetic method of pyridine, which is characterized in that the solid base catalyst the preparation method comprises the following steps: by calcium oxide, zinc oxide and oxidation Aluminium is according to the mass ratio of the material 1:(0.8~0.96): (1.12~1.25) are ground after mixing, and take 500~800 mesh particles, 750~ 12~17h is roasted at 800 DEG C obtains solid base catalyst.
- 6. -6 (trifluoromethyls) of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 1 The synthetic method of pyridine, which is characterized in that in step 1), protection gas is nitrogen or argon gas.
- 7. -6 (trifluoromethyls) of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 1 The synthetic method of pyridine, which is characterized in that in step 1), solvent A is toluene, dimethylbenzene or nitrobenzene.
- 8. -6 (trifluoromethyls) of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 1 The synthetic method of pyridine, which is characterized in that in step 1), acid binding agent is triethylamine or diethylamine.
- 9. -6 (trifluoromethyls) of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 1 The synthetic method of pyridine, which is characterized in that in step 1), solvent B is benzene or toluene.
- 10. -6 (fluoroforms of insecticide sulfoxaflor intermediate 3- [1- (methyl mercapto) ethyl] according to claim 1 Base) pyridine synthetic method, which is characterized in that in step 1), the halogenated -2- trifluoromethyl pyridine of 5-, methyl ethyl sulfide and tie up The molar ratio of sour agent is 1:(1.6~2.2): the amount ratio of (1.4~1.7), methyl ethyl sulfide and solvent A is 1g:(8~12) The amount ratio of the halogenated -2- trifluoromethyl pyridine of ml, 5- and solvent B are 1g:(4~7ml), the halogenated -2- trifluoromethyl pyridine of 5- with The mass ratio of catalyst is 1:(0.25~0.36).
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665982A (en) * | 2019-01-22 | 2019-04-23 | 深圳市第二人民医院 | The synthetic method of Nefiracetam intermediate 2-Pyrrolidone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103874413A (en) * | 2011-08-17 | 2014-06-18 | 陶氏益农公司 | 5-fluoro-4-imino-3-(substituted)-3,4-dihydropyrimidin-2-(1H)-ketone derivatives |
| CN104378985A (en) * | 2012-04-18 | 2015-02-25 | 陶氏益农公司 | N-substituted(6-haloalkylpyridin-3-yl)alkyl sulfoximines as a seed treatment to control coleopteran insects |
| CN105151684A (en) * | 2015-08-31 | 2015-12-16 | 邝嘉豪 | Stone conveyer |
-
2018
- 2018-10-16 CN CN201811203019.0A patent/CN109053553A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103874413A (en) * | 2011-08-17 | 2014-06-18 | 陶氏益农公司 | 5-fluoro-4-imino-3-(substituted)-3,4-dihydropyrimidin-2-(1H)-ketone derivatives |
| CN104378985A (en) * | 2012-04-18 | 2015-02-25 | 陶氏益农公司 | N-substituted(6-haloalkylpyridin-3-yl)alkyl sulfoximines as a seed treatment to control coleopteran insects |
| CN105151684A (en) * | 2015-08-31 | 2015-12-16 | 邝嘉豪 | Stone conveyer |
Non-Patent Citations (1)
| Title |
|---|
| OLEKSANDR S. KANISHCHEV AND WILLIAM R. DOLBIER, JR.: "Ni/Ir-Catalyzed Photoredox Decarboxylative Coupling of S-Substituted Thiolactic Acids with Heteroaryl Bromides:Short Synthesis of Sulfoxaflor and Its SF5 Analog", 《CHEM. EUR. J.》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109665982A (en) * | 2019-01-22 | 2019-04-23 | 深圳市第二人民医院 | The synthetic method of Nefiracetam intermediate 2-Pyrrolidone |
| CN109665982B (en) * | 2019-01-22 | 2022-07-08 | 深圳市第二人民医院 | Synthetic method of nefiracetam intermediate 2-pyrrolidone |
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