CN109180529A - A kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide - Google Patents
A kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide Download PDFInfo
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- CN109180529A CN109180529A CN201811241186.4A CN201811241186A CN109180529A CN 109180529 A CN109180529 A CN 109180529A CN 201811241186 A CN201811241186 A CN 201811241186A CN 109180529 A CN109180529 A CN 109180529A
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- cyano benzyl
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/0277—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature
- B01J31/0278—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre
- B01J31/0281—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member
- B01J31/0284—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides comprising ionic liquids, as components in catalyst systems or catalysts per se, the ionic liquid compounds being used in the molten state at the respective reaction temperature containing nitrogen as cationic centre the nitrogen being a ring member of an aromatic ring, e.g. pyridinium
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- Chemical Kinetics & Catalysis (AREA)
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of synthetic methods of pesticide intermediate 4- cyano benzyl cyanide, Cymag, 4- cyano benzyl chloride, acetonitrile, anhydrous potassium fluoride, bis- (chlorine sulphonyl) imines, 1- butyl 3- methylimidazole bromide are primary raw material, synthesis technology of the invention is under the effect of homogeneous ionic-liquid catalyst, 4- cyano benzyl chloride and Cymag occur nucleophilic substitution and generate 4- cyano benzyl cyanide compared to conventional precious metal catalyst, recycling not only reduces reaction cost, and the higher yield of product is maintained, simplify subsequent process for separating and purifying.
Description
Technical field
The present invention relates to a kind of synthetic methods of intermediate 4- cyano benzyl cyanide, belong to chemical industry synthesis field.
Background technique
4- cyano benzyl cyanide (4- (cyanomethyl) benzonitrile) CAS:876-31-3 is synthetic pesticide cyanogen fluorine
The important intermediate of worm hydrazone etc..In recent years, the primary synthetic methods of report have: benzene acetonitrile and acetonitrile reaction generate 4- cyano benzene second
Nitrile, while 2- cyano benzyl cyanide and 3- cyano benzyl cyanide can be generated, it is not readily separated；The derivatives reaction of fragrant halogen and isoxazole generates
4- cyano benzyl cyanide, reaction need expensive palladium catalyst；Benzyl halogen and cyanating reagent occur nucleophilic substitution and generate 4- cyano
Benzene acetonitrile, the method yield is higher, but by-product is complicated, more difficult to later period separating-purifying；Therefore developing one kind can
It improves product yield and product separates easy technique and has great importance.
Summary of the invention
The purpose of the present invention is to provide a kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide, this method is optimizing
Under the conditions of can be catalyzed 4- cyano benzyl chloride and Cymag nucleophilic substitution, product yield with higher occurs；
A kind of synthetic method of intermediate 4- cyano benzyl cyanide, method includes the following steps:
Step 1, in three-necked flask of the 250ml equipped with blender, thermometer and condenser, water, Cymag and ionic liquid is added
Body catalyst [bmim] [FSI] is warming up to 95 DEG C while opening stirring；
4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, and solution colour is gradually become by colorless and transparent during charging
It is transparent for Chinese red, it maintains the reflux for, the reaction was continued after charging 1h；
Step 3, reaction stop and cooling, divides and mother liquor water phase is gone to obtain Chinese red SOLID ORGANIC phase, add water washing three times, isolated mother
Liquid water phase and cleaning solution carry out harmless treatment with excessive ferrous sulfate；
Step 4 filters gained organic phase up to off-white powder, is recrystallized with dehydrated alcohol, obtains sterling 4- cyano benzene second
Nitrile.
The ionic-liquid catalyst [bmim] [FSI] the preparation method is as follows:
Step 1, in 250ml three-necked flask, acetonitrile 50ml, anhydrous potassium fluoride 11g is added in magnetic agitation, drips under water-bath cooling
Add bis- (chlorine sulphonyl) imines 7.0g, during dropwise addition, reaction temperature is no more than 20 DEG C；
50 DEG C of reaction 15h after step 2, completion of dropwise addition remove solvent using Rotary Evaporators after reaction, obtain solid production
Object；
Tetrahydrofuran 200ml is added in step 3 in above-mentioned solid, then extracts double fluorine sulfimide potassium in three times, after filtering,
The concentration of gained filtrate, is added dehydrated alcohol, and bis- (fluorine sulphonyl) imines potassium solids are precipitated；
22g ionic liquid 1- butyl 3- methylimidazole bromide is first slowly heated to 80 DEG C by step 4, then by above-mentioned bis- (fluorine sulphurs
Acyl) quality such as imines potassium are slowly added into ionic liquid, stir under a nitrogen atmosphere for 24 hours；
Step 5 dissolves above-mentioned gained mixture with ethyl acetate solvent, and precipitating KBr is separated by filtration, filtrate is taken to be evaporated
Obtain ionic-liquid catalyst [bmim] [FSI].
The utility model has the advantages that the present invention provides a kind of synthetic methods of pesticide intermediate 4- cyano benzyl cyanide, in homogeneous ion
Under liquid catalyst [bmim] [FSI] effect, 4- cyano benzyl chloride and Cymag occur nucleophilic substitution and generate 4- cyano benzene second
Nitrile.Homogeneous catalyst [bmim] [FSI] can preferably promote reaction to carry out from the point of view of reaction result, this is because catalyst is first
First CN is exchanged with Cymag in water phase-Then anion is transferred in organic phase in the form of ion pair, i.e., oil-soluble to urge
Agent cation is CN-Anion is brought into organic phase, CN-Solvation degree of the anion in organic phase greatly reduces, because
And reactivity is very high, can react with 4- cyano benzyl chloride rapidly.Then, catalyst cation association halide anion returns to water
Phase, repeatedly, so that rapid reaction carries out.Compared to conventional precious metal catalyst, recycling not only reduce reaction at
This, and the higher yield of product is maintained, simplify subsequent process for separating and purifying.
Specific embodiment
Embodiment 1
A kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide, method includes the following steps:
Step 1,250ml equipped with blender, thermometer and condenser three-necked flask in, be added 50ml water, 39g Cymag and
30g ionic-liquid catalyst [bmim] [FSI] is warming up to 95 DEG C while opening stirring；
33g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；
Step 3, reaction stop and cooling, divides and mother liquor water phase is gone to obtain Chinese red SOLID ORGANIC phase, add water washing three times, isolated mother
Liquid water phase and cleaning solution carry out harmless treatment with excessive ferrous sulfate；
Step 4 filters gained organic phase up to off-white powder, is recrystallized with dehydrated alcohol, obtains sterling 4- cyano benzene second
Nitrile.
The ionic-liquid catalyst [bmim] [FSI] the preparation method is as follows:
Step 1, in 250ml three-necked flask, acetonitrile 50ml, anhydrous potassium fluoride 11g is added in magnetic agitation, drips under water-bath cooling
Add bis- (chlorine sulphonyl) imines 7.0g, during dropwise addition, reaction temperature is no more than 20 DEG C；
50 DEG C of reaction 15h after step 2, completion of dropwise addition remove solvent using Rotary Evaporators after reaction, obtain solid production
Object；
Tetrahydrofuran 200ml is added in step 3 in above-mentioned solid, then extracts double fluorine sulfimide potassium in three times, after filtering,
The concentration of gained filtrate, is added dehydrated alcohol, and bis- (fluorine sulphonyl) imines potassium solids are precipitated；
22g ionic liquid 1- butyl 3- methylimidazole bromide is first slowly heated to 80 DEG C by step 4, then by above-mentioned bis- (fluorine sulphurs
Acyl) quality such as imines potassium are slowly added into ionic liquid, stir under a nitrogen atmosphere for 24 hours；
Step 5 dissolves above-mentioned gained mixture with ethyl acetate solvent, and precipitating KBr is separated by filtration, filtrate is taken to be evaporated
Obtain ionic-liquid catalyst [bmim] [FSI].
Embodiment 2
30g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Embodiment 3
27g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Embodiment 4
24g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Embodiment 5
21g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Embodiment 6
18g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Embodiment 7
15g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Embodiment 8
33g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Embodiment 9
36g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Embodiment 10
39g 4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, during charging solution colour by it is colorless and transparent by
It is transparent to fade to Chinese red, maintains the reflux for, the reaction was continued after charging 1h；Remaining step is the same as embodiment 1.
Reference examples 1
It is with 1 difference of embodiment: in the synthesis step 1 of intermediate, uses equivalent ionic liquid [bmim] Br as catalysis
Agent, remaining step are identical with embodiment 1.
Reference examples 2
Be with 1 difference of embodiment: in the synthesis step 1 of intermediate, not adding ionic-liquid catalyst, remaining step with
Embodiment 1 is identical.
Reference examples 3
It is with 1 difference of embodiment: in the synthesis step 1 of catalyst, replaces acetonitrile, remaining step and reality with the acetone of equivalent
It is identical to apply example 1.
Reference examples 4
It is with 1 difference of embodiment: in the synthesis step 1 of catalyst, replaces acetonitrile, remaining step and reality with the ethyl alcohol of equivalent
It is identical to apply example 1.
Reference examples 5
Be with 1 difference of embodiment: in the synthesis step 1 of catalyst, anhydrous potassium fluoride, bis- (chlorine sulphonyl) imines mass ratioes are
1:1, remaining step are identical with embodiment 1.
Reference examples 6
Be with 1 difference of embodiment: in the synthesis step 1 of catalyst, anhydrous potassium fluoride, bis- (chlorine sulphonyl) imines mass ratioes are
7:11, remaining step are identical with embodiment 1.
Reference examples 7
It is with 1 difference of embodiment: in the synthesis step 4 of catalyst, bis- (fluorine sulphonyl) imines potassium, 1- butyl 3- methylimidazole
Bromide mass ratio 1:2；Remaining step is identical with embodiment 1.
Reference examples 8
It is with 1 difference of embodiment: in the synthesis step 4 of catalyst, bis- (fluorine sulphonyl) imines potassium, 1- butyl 3- methylimidazole
Bromide mass ratio 2:1；Remaining step is identical with embodiment 1.
It is as shown in the table for reaction result under embodiment and reference examples different condition
The experimental results showed that catalyst has good catalytic effect to the nucleophilic substitution of 4- cyano benzyl chloride and Cymag,
In one timing of reaction condition, intermediate yield is higher, and catalytic performance is better, otherwise poorer；4- cyano benzyl chloride, NaCN quality ratio
When for 11:13, other ingredients are fixed, and synthetic effect is best, with embodiment 1 the difference lies in that embodiment 2 to embodiment 10 is distinguished
Change primary raw material 4- cyano benzyl chloride, the dosage of Cymag and proportion, in spite of certain effect, but is not so good as 1 high income of embodiment；
Reference examples 1 to reference examples 2 do not add ionic-liquid catalyst and are replaced with equivalent [bmim] Br, other steps are identical,
Cause product yield to be substantially reduced, illustrates that bis- (fluorine sulphonyl) imines potassium effectively improve the catalytic performance of catalyst；Reference examples 3 to
Reference examples 4 use the acetone of equivalent and ethyl alcohol to replace acetonitrile as solvent, and effect is still bad, illustrates that acetonitrile solvent is more suitable for being catalyzed
The synthesis of agent；Reference examples 5 to 6 anhydrous potassium fluoride of reference examples, bis- (chlorine sulphonyl) imines mass ratioes changes, and product yield is still
It is not high, illustrate that the proportion of the two affects the synthetic effect of bis- (fluorine sulphonyl) imines potassium；Reference examples 7 are to bis- (the fluorine sulphurs of reference examples 8
Acyl) imines potassium, 1- butyl 3- methylimidazole bromide mass ratio change, the not rebalancing of the zwitterion proportion in catalyst,
Reaction effect is obviously deteriorated, and illustrates that ionic liquid can play preferable catalytic effect in the system of charge balance；Therefore it uses
Catalyst of the invention has excellent catalytic effect to the synthetic reaction of intermediate 4- cyano benzyl cyanide.
Claims (3)
1. a kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide, which is characterized in that its with Cymag, 4- cyano benzyl chloride,
Acetonitrile, anhydrous potassium fluoride, bis- (chlorine sulphonyl) imines, 1- butyl 3- methylimidazole bromide are main Material synthesis.
2. a kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide according to claim 1, it is characterised in that
Method includes the following steps:
Step 1, in three-necked flask of the 250ml equipped with blender, thermometer and condenser, water, Cymag and ionic liquid is added
Body catalyst [bmim] [FSI] is warming up to 95 DEG C while opening stirring；
4- cyano benzyl chloride is slowly added portionwise in step 2 in 60min, and solution colour is gradually become by colorless and transparent during charging
It is transparent for Chinese red, it maintains the reflux for, the reaction was continued after charging 1h；
Step 3, reaction stop and cooling, divides and mother liquor water phase is gone to obtain Chinese red SOLID ORGANIC phase, add water washing three times, isolated mother
Liquid water phase and cleaning solution carry out harmless treatment with excessive ferrous sulfate；
Step 4 filters gained organic phase up to off-white powder, is recrystallized with dehydrated alcohol, obtains sterling 4- cyano benzene second
Nitrile.
3. a kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide according to claim 2, it is characterised in that
The ionic-liquid catalyst [bmim] [FSI] the preparation method is as follows:
Step 1, in 250ml three-necked flask, acetonitrile 50ml, anhydrous potassium fluoride 11g is added in magnetic agitation, drips under water-bath cooling
Add bis- (chlorine sulphonyl) imines 7.0g, during dropwise addition, reaction temperature is no more than 20 DEG C；
50 DEG C of reaction 15h after step 2, completion of dropwise addition remove solvent using Rotary Evaporators after reaction, obtain solid production
Object；
Tetrahydrofuran 200ml is added in step 3 in above-mentioned solid, then extracts double fluorine sulfimide potassium in three times, after filtering,
The concentration of gained filtrate, is added dehydrated alcohol, and bis- (fluorine sulphonyl) imines potassium solids are precipitated；
22g ionic liquid 1- butyl 3- methylimidazole bromide is first slowly heated to 80 DEG C by step 4, then by above-mentioned bis- (fluorine sulphurs
Acyl) quality such as imines potassium are slowly added into ionic liquid, stir under a nitrogen atmosphere for 24 hours；
Step 5 dissolves above-mentioned gained mixture with ethyl acetate solvent, and precipitating KBr is separated by filtration, filtrate is taken to be evaporated
Obtain ionic-liquid catalyst [bmim] [FSI].
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| Application Number | Priority Date | Filing Date | Title |
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| CN201811241186.4A CN109180529A (en) | 2018-10-24 | 2018-10-24 | A kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide |
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| CN201811241186.4A CN109180529A (en) | 2018-10-24 | 2018-10-24 | A kind of synthetic method of pesticide intermediate 4- cyano benzyl cyanide |
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Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381918A (en) * | 2011-08-31 | 2012-03-21 | 河南科技大学 | Method for synthesizing benzyl cyanide compound by using benzyl chloride compound |
| CN102766073A (en) * | 2012-08-02 | 2012-11-07 | 黄河三角洲京博化工研究院有限公司 | Method for synchronizing m-benzenyl trifluoride di-cyan acetonphenone |
| CN108530355A (en) * | 2018-06-08 | 2018-09-14 | 福州华博立乐新材料科技有限公司 | A kind of synthetic method of 3- [2- (the chloro- 2- quinolyls of 7-) vinyl] benzaldehyde |
-
2018
- 2018-10-24 CN CN201811241186.4A patent/CN109180529A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102381918A (en) * | 2011-08-31 | 2012-03-21 | 河南科技大学 | Method for synthesizing benzyl cyanide compound by using benzyl chloride compound |
| CN102766073A (en) * | 2012-08-02 | 2012-11-07 | 黄河三角洲京博化工研究院有限公司 | Method for synchronizing m-benzenyl trifluoride di-cyan acetonphenone |
| CN108530355A (en) * | 2018-06-08 | 2018-09-14 | 福州华博立乐新材料科技有限公司 | A kind of synthetic method of 3- [2- (the chloro- 2- quinolyls of 7-) vinyl] benzaldehyde |
Non-Patent Citations (3)
| Title |
|---|
| WHEELER, CHRISTY 等: "Ionic liquids as catalytic green solvents for nucleophilic displacement reactions", 《CHEMICAL COMMUNICATIONS》 * |
| 何逸波: "含氟离子液体催化剂的制备及其用于Friedel-Crafts烷基化反应的研究", 《中国博士学位论文全文数据库 工程科技I辑》 * |
| 王璇 等: "4-氰基苄氯氰化物的合成和晶体结构研究", 《化学试剂》 * |
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