CN117185956A - Synthesis of benzoyl cyanide by composite phase transfer catalyst catalysis method - Google Patents

Synthesis of benzoyl cyanide by composite phase transfer catalyst catalysis method Download PDF

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CN117185956A
CN117185956A CN202311158692.8A CN202311158692A CN117185956A CN 117185956 A CN117185956 A CN 117185956A CN 202311158692 A CN202311158692 A CN 202311158692A CN 117185956 A CN117185956 A CN 117185956A
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phase transfer
transfer catalyst
cyanide
benzoyl
composite phase
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王学铭
王鹏飞
石利平
马立香
郭博杰
张艳敏
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Handan Ruitian Pesticide Co ltd
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Handan Ruitian Pesticide Co ltd
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Abstract

The invention relates to the technical field of pesticide preparations, and provides a composite phase transfer catalyst catalytic method for synthesizing benzoyl cyanide, which comprises the following steps: s1, adding sodium cyanide and cuprous cyanide into dimethylbenzene, and carrying out azeotropic dehydration to obtain an azeotrope; s2, acetonitrile is added into the azeotrope, dehydration is carried out, and then a phase transfer catalyst and benzoyl chloride are added for reaction, thus obtaining the benzoyl cyanide. By adopting the technical scheme, the reaction condition for synthesizing the benzoyl cyanide by using the sodium cyanide and the benzoyl chloride is harsh, and the reaction yield is low.

Description

Synthesis of benzoyl cyanide by composite phase transfer catalyst catalysis method
Technical Field
The invention relates to the technical field of pesticide preparations, in particular to a method for synthesizing benzoyl cyanide by a composite phase transfer catalyst catalysis method.
Background
Benzoyl cyanide is an important fine chemical intermediate, is widely applied to the synthesis of pesticides and medicines, has a plurality of synthesis methods, and is commonly used in the prior art at present by a reaction method of benzoyl chloride, benzoic anhydride and sodium cyanide, a dimethylamine catalytic hydrocyanic acid reaction method and a reaction method of sodium cyanide and benzoyl chloride, but the reaction methods have the problems of higher reaction temperature and long reaction time, and further lower synthesis yield of benzoyl cyanide. In the new technology of synthesizing the patent document CN 109651192A-benzoyl cyanide, a reaction method of sodium cyanide and benzoyl chloride is adopted, and a reaction catalyst and a phase transfer catalyst are added at the same time, wherein the used phase transfer catalysts are all commonly known phase catalysts, and the defect of low catalytic efficiency and low synthesis yield of the benzoyl cyanide exists. Therefore, it is extremely important to use a method for producing benzoyl cyanide under mild reaction conditions and in high yield.
Disclosure of Invention
The invention provides a composite phase transfer catalyst catalytic method for synthesizing benzoyl cyanide, which solves the problems of harsh reaction conditions and low reaction yield of synthesizing benzoyl cyanide by sodium cyanide and benzoyl chloride in the related technology.
The technical scheme of the invention is as follows:
the invention provides a composite phase transfer catalyst catalytic method for synthesizing benzoyl cyanide, which comprises the following steps:
s1, adding sodium cyanide and cuprous cyanide into dimethylbenzene, and carrying out azeotropic dehydration to obtain an azeotrope;
s2, acetonitrile is added into the azeotrope, dehydration is carried out, and then a phase transfer catalyst and benzoyl chloride are added for reaction, thus obtaining the benzoyl cyanide.
As a further technical scheme, the molar ratio of the sodium cyanide to the benzoyl chloride is 1:1-1:1.5.
As a further technical scheme, the addition mass of the cuprous cyanide is 0.5% -1.5% of the mass of the benzoyl chloride, and the addition mass of the phase transfer catalyst is 0.2% -0.5% of the mass of the benzoyl chloride.
As a further technical scheme, the volume-mass ratio of the dimethylbenzene to the benzoyl chloride is 1:1-2:1 in terms of g/mL.
As a further technical scheme, the water content of the dimethylbenzene is less than or equal to 250PPm.
As a further technical scheme, the mass ratio of acetonitrile to benzoyl chloride is 1:0.05-1:0.1.
As a further technical scheme, the water content of the acetonitrile is less than or equal to 500PPm.
As a further technical scheme, the phase transfer catalyst is triethylbenzyl ammonium chloride and/or triethylhydrogen ammonium chloride.
As a further technical scheme, the phase transfer catalyst is a mixture of triethylbenzyl ammonium chloride and triethylhydrogen ammonium chloride in a mass ratio of 2:1-3:1.
As a further technical scheme, the reaction temperature is 90-130 ℃, and the reaction time is 3-5 h.
As a further technical scheme, the phase transfer catalyst is modified by porous ceramsite.
As a further technical scheme, the mass of the porous ceramsite is 0.5% -1% of the mass of the phase transfer catalyst.
As a further technical scheme, the modification method comprises the following steps: adding porous ceramsite into the aqueous solution of the phase transfer catalyst, uniformly mixing, and drying to obtain the modified phase transfer catalyst.
As a further technical scheme, the porous ceramsite is prepared by the following method: adding the porous ceramsite into water, adding ammonium carbonate to prepare slurry, soaking the organic foam template into the slurry, drying and sintering to obtain the porous ceramsite.
As a further technical scheme, the addition mass of the ammonium carbonate is 15% -25% of the mass of the porous ceramsite.
As a further technical scheme, the dipping temperature is 80-100 ℃, and the dipping time is 10-15 h.
The working principle and the beneficial effects of the invention are as follows:
1. in the invention, dimethylbenzene is used as a first solvent, sodium cyanide and cuprous cyanide are added for azeotropic dehydration to obtain an azeotrope, acetonitrile is added into the azeotrope, and then a composite phase transfer catalyst is added to promote the reaction of sodium cyanide, cuprous cyanide and benzoyl chloride, so that the efficiency of catalytic reaction is improved, and the composite phase transfer catalyst is added to simultaneously reduce the reaction temperature, shorten the reaction time and reduce the generation of reaction byproducts, thereby obtaining the benzoyl cyanide with high yield.
2. In the invention, the strong polar acetonitrile solvent is added into the azeotrope, thereby accelerating the reaction rate, shortening the reaction time and improving the yield of benzoyl cyanide.
3. In the invention, the dimethylbenzene reaction solvent is dehydrated, so that the generation of reaction byproducts can be effectively reduced, benzoyl chloride is prevented from being decomposed easily when meeting water, and the composite phase transfer catalyst is promoted to transfer anions in a reaction substrate sodium cyanide and cuprous cyanide from an aqueous phase to an organic phase to react with benzoyl chloride, thereby improving the yield and purity of benzoyl cyanide.
4. In the invention, triethylbenzyl ammonium chloride and triethylammonium chloride are used as composite phase transfer catalysts, so that the catalytic reaction efficiency is improved, the reaction time is shortened, the reaction temperature and the generation of reaction byproducts are reduced, and the yield of the product benzoyl cyanide is further improved.
5. According to the invention, the porous ceramsite is used for modifying the composite phase transfer catalyst, so that not only can the activity of the composite phase transfer catalyst be improved, but also the reaction rate is improved, and the yield of the product benzoyl cyanide is further improved.
6. According to the invention, the porous ceramsite is modified by the organic foam template and the pore-forming agent ammonium carbonate, so that the pores of the porous ceramsite can be enlarged, the impregnation effect of the composite phase transfer catalyst on the porous ceramsite is further promoted, the activity of the composite phase transfer catalyst is improved, and the yield of the product benzoyl cyanide is further improved.
Detailed Description
The technical solutions of the embodiments of the present invention will be clearly and completely described below in conjunction with the embodiments of the present invention, and it is apparent that the described embodiments are only some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by one of ordinary skill in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
S1, adding 1014L of dimethylbenzene into an MT-1 reaction kettle, stirring, adding 353.5kg of sodium cyanide and 5.1kg of cuprous cyanide, heating to 150 ℃ for reflux, and performing azeotropic dehydration until the water content of the dimethylbenzene is less than or equal to 250PPm to obtain an azeotrope;
s2, cooling the azeotrope to 90 ℃, adding 51kg of acetonitrile, dehydrating until the water content of the acetonitrile is less than or equal to 500PPm, heating to 95 ℃, adding 2kg of triethylbenzyl ammonium chloride, dropwise adding 1014kg of benzoyl chloride within 1-1.5 h, heating to 90 ℃, preserving heat for 5h, sampling and detecting that the benzoyl chloride conversion rate in the filtrate is 99.8%, namely that the benzoyl chloride is less than 0.2%, finishing the reaction, cooling to 40 ℃ after the reaction is finished, centrifuging, filtering, using 30% of dimethylbenzene washing agent for secondary filtering residues, collecting filtrate, evaporating and concentrating the filtrate to obtain 971kg of benzoyl cyanide, detecting that the purity of the benzoyl cyanide is 99.3% by using a high performance liquid chromatograph, and the yield of the benzoyl cyanide is 95.3%.
Example 2
S1, adding 2028L of dimethylbenzene into an MT-1 reaction kettle, stirring, adding 235.7kg of sodium cyanide and 15.2kg of cuprous cyanide, heating to 150 ℃ for reflux, and performing azeotropic dehydration until the water content of the dimethylbenzene is less than or equal to 250PPm to obtain an azeotrope;
s2, cooling the azeotrope to 90 ℃, adding 101kg of acetonitrile, dehydrating until the water content of the acetonitrile is less than or equal to 500PPm, heating to 95 ℃, adding 3kg of triethylammonium chloride, dropwise adding 1014kg of benzoyl chloride within 1-1.5 h, heating to 130 ℃, preserving heat for 3h, sampling and detecting that the benzoyl chloride conversion rate in the filtrate is 99.8%, namely that the benzoyl chloride residue is less than 0.2%, namely that the reaction is completed, cooling to 40 ℃ after the reaction is completed, centrifuging, filtering, using 30% of xylene detergent for secondary filtering residues, collecting filtrate, evaporating and concentrating the filtrate to obtain 976kg of benzoyl cyanide, detecting that the purity of the benzoyl cyanide is 99.2% by using a high performance liquid chromatograph, and the yield of the benzoyl cyanide is 95.7%.
Example 3
This example differs from example 1 only in that in step S2 triethylbenzyl ammonium chloride is replaced by tetrabutylammonium bromide. 969kg of benzoyl cyanide was finally obtained, and the purity of benzoyl cyanide was 99.1% as measured by high performance liquid chromatography, and the yield of benzoyl cyanide was 94.9%.
Example 4
This example differs from example 1 only in that 1kg of triethylammonium chloride was also added in step S2, and the remainder was the same as in example 1. 993kg of benzoyl cyanide was finally obtained, and the purity of benzoyl cyanide was 99.1% as measured by high performance liquid chromatography, and the yield of benzoyl cyanide was 97.2%.
Example 5
This example differs from example 1 only in that 0.8kg of triethylammonium hydroxide was also added in step S2, and the remainder was the same as in example 1. 995kg of benzoyl cyanide was finally obtained, and the purity of benzoyl cyanide was 99.3% as measured by high performance liquid chromatography, and the yield of benzoyl cyanide was 97.6%.
Example 6
This example differs from example 1 only in that 0.7kg of triethylammonium hydroxide was also added in step S2, and the remainder was the same as in example 1. 996kg of benzoyl cyanide was finally obtained, and the purity of benzoyl cyanide was 99.3% as measured by high performance liquid chromatography, and the yield of benzoyl cyanide was 97.7%.
Example 7
The present example differs from example 5 only in that in step S2, the composite phase transfer catalyst of triethylbenzyl ammonium chloride and triethylammonium chloride is modified with porous ceramic particles.
The preparation method of the porous ceramsite comprises the following steps: adding 100g of porous ceramsite into 200mL of water, adding 15g of ammonium carbonate to prepare slurry, immersing 100g of organic foam template into the slurry, heating to 80 ℃, immersing for 15h, drying and sintering at 500 ℃ to obtain porous ceramsite,
the modification method of the composite phase transfer catalyst comprises the following steps: 100g of phase transfer catalyst is added into 200mL of water, 50g of porous ceramsite is added, and the mixture is uniformly mixed and dried to obtain the modified phase transfer catalyst. 1014kg of benzoyl cyanide was finally obtained, and the purity of benzoyl cyanide was 99.1% and the yield of benzoyl cyanide was 99.3% as measured by high performance liquid chromatography.
Example 8
The present example differs from example 5 only in that in step S2, the composite phase transfer catalyst of triethylbenzyl ammonium chloride and triethylammonium chloride is modified with porous ceramic particles.
The preparation method of the porous ceramsite comprises the following steps: adding 100g of porous ceramsite into 200mL of water, adding 25g of ammonium carbonate to prepare slurry, immersing 100g of organic foam template into the slurry, heating to 100 ℃, immersing for 10h, drying and sintering at 500 ℃ to obtain porous ceramsite,
the modification method of the composite phase transfer catalyst comprises the following steps: 100g of phase transfer catalyst is added into 200mL of water, 100g of porous ceramsite is added, and the mixture is uniformly mixed and dried to obtain the modified phase transfer catalyst. Finally 1015kg of benzoyl cyanide is obtained, the purity of the benzoyl cyanide is 99.3% by high performance liquid chromatograph, and the yield of the benzoyl cyanide is 99.6%.
Example 9
This example differs from example 5 only in that triethylammonium chloride was replaced with polyethylene glycol, and the remainder was the same as example 5. 948kg of benzoyl cyanide was finally obtained, and the purity of benzoyl cyanide was 99.4% as measured by high performance liquid chromatography, and the yield of benzoyl cyanide was 93.1%.
Comparative example 1
The comparative example differs from example 1 only in that azeotropic dehydration is not performed in step S1. 943g of benzoyl cyanide was obtained, and the purity of benzoyl cyanide was 89.2% and the yield of benzoyl cyanide was 83.1% by high performance liquid chromatography.
Comparative example 2
The present comparative example differs from example 1 only in that acetonitrile was not added in step S2. 904kg of benzoyl cyanide was finally obtained, and the purity of benzoyl cyanide was 99.3% and the yield of benzoyl cyanide was 88.7% as measured by high performance liquid chromatography.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, alternatives, and improvements that fall within the spirit and scope of the invention.

Claims (10)

1. The method for synthesizing benzoyl cyanide by using the composite phase transfer catalyst is characterized by comprising the following steps of:
s1, adding sodium cyanide and cuprous cyanide into dimethylbenzene, and carrying out azeotropic dehydration to obtain an azeotrope;
s2, acetonitrile is added into the azeotrope, dehydration is carried out, and then a phase transfer catalyst and benzoyl chloride are added for reaction, thus obtaining the benzoyl cyanide.
2. The composite phase transfer catalyst catalytic synthesis of benzoyl cyanide according to claim 1, wherein the molar ratio of the sodium cyanide to the benzoyl chloride is 1:1-1:1.5.
3. The composite phase transfer catalyst catalytic synthesis method of benzoyl cyanide according to claim 1, wherein the addition mass of cuprous cyanide is 0.5% -1.5% of benzoyl chloride, and the addition mass of the phase transfer catalyst is 0.2% -0.5% of benzoyl chloride.
4. The method for synthesizing benzoyl cyanide by using the composite phase transfer catalyst according to claim 1, wherein the volume-mass ratio of the xylene to the benzoyl chloride is 1:1-2:1 in terms of g/mL.
5. The method for synthesizing benzoyl cyanide by using the composite phase transfer catalyst according to claim 1, wherein the mass ratio of acetonitrile to benzoyl chloride is 1:0.05-1:0.1.
6. The method for synthesizing benzoyl cyanide by using the composite phase transfer catalyst according to claim 1, wherein the phase transfer catalyst is triethylbenzyl ammonium chloride and/or triethylhydrogen ammonium chloride;
preferably, the phase transfer catalyst is a mixture of triethylbenzyl ammonium chloride and triethylhydrogen ammonium chloride in a mass ratio of 2:1-3:1.
7. The method for synthesizing benzoyl cyanide by using the composite phase transfer catalyst according to claim 1, wherein the reaction temperature is 90-130 ℃, and the reaction time is 3-5 hours.
8. The method for synthesizing benzoyl cyanide by using the composite phase transfer catalyst according to claim 1, wherein the phase transfer catalyst is modified by porous ceramsite;
preferably, the addition mass of the porous ceramsite is 0.5% -1% of the mass of the phase transfer catalyst.
9. The method for synthesizing benzoyl cyanide by using the composite phase transfer catalyst according to claim 8, wherein the modification method is as follows: adding porous ceramsite into the aqueous solution of the phase transfer catalyst, uniformly mixing, and drying to obtain the modified phase transfer catalyst.
10. The composite phase transfer catalyst catalytic synthesis of benzoyl cyanide according to claim 9, wherein the porous ceramsite is prepared by the following method: adding porous ceramsite into water, adding ammonium carbonate to prepare slurry, soaking an organic foam template into the slurry, drying and sintering to obtain porous ceramsite;
preferably, the adding mass of the ammonium carbonate is 15% -25% of the mass of the porous ceramsite;
preferably, the dipping temperature is 80-100 ℃, and the dipping time is 10-15 h.
CN202311158692.8A 2023-09-08 2023-09-08 Synthesis of benzoyl cyanide by composite phase transfer catalyst catalysis method Pending CN117185956A (en)

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