CN106083647A - One-step method prepares the synthesis technique of salicylonitrile - Google Patents
One-step method prepares the synthesis technique of salicylonitrile Download PDFInfo
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- CN106083647A CN106083647A CN201610384298.XA CN201610384298A CN106083647A CN 106083647 A CN106083647 A CN 106083647A CN 201610384298 A CN201610384298 A CN 201610384298A CN 106083647 A CN106083647 A CN 106083647A
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- salicylonitrile
- organic layer
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- salicylamide
- phosgene
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/20—Preparation of carboxylic acid nitriles by dehydration of carboxylic acid amides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/32—Separation; Purification; Stabilisation; Use of additives
- C07C253/34—Separation; Purification
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention provides one-step method to prepare the synthesis technique of salicylonitrile, main technological steps is as follows: the salicylamide of 1 weight portion is dissolved in the solvent chlorobenzene of 2 weight portions by (1), after being sufficiently stirred for, control temperature, continue to be passed through phosgene to react, monitor reaction process by high performance liquid chromatography, when the content of question response thing salicylamide is less than 1%, stop being passed through phosgene；(2) mixture after reaction being terminated is transferred to scrubbing tower, first alkali cleaning, then wash, after stratification, decompression distillation obtains grease, in grease, add petroleum ether, stratification after stirring fully, extract with concentrated sulphuric acid, after separating organic layer, being diluted organic layer with the dilute hydrochloric acid of 60%, finally carry out recrystallization with the petroleum ether of heat, the crystalline product drying after recrystallization obtains target product salicylonitrile after processing.The present invention by simply repeatedly extracting, distill, efficiently separating of target product and other impurity can be realized, thus improve product purity.
Description
Technical field
The present invention relates to pesticide synthesis field, be specifically related to one-step method and prepare the synthesis technique of salicylonitrile.
Background technology
Salicylonitrile, has another name called salicylonitrile, is a kind of gray powdery solid, and great penetrating odor is on a small quantity
People can be allowed to breathe be affected, abnormal smells from the patient is pained.Salicylonitrile is commonly used for the intermediate of organic synthesis bunitrolol, antibacterial Fluoxastrobin
Intermediate.Synthesis about salicylonitrile reports seldom mainly have two categories below to react:
First kind reaction is that salicylide first generates Saldox. with hydroxylamine hydrochloride, then is dehydrated by acetic anhydride or thionyl chloride
Obtain salicylonitrile；
Equations of The Second Kind reaction is that salicylamide is dehydrated in the presence of phosgene or thionyl chloride or phosphorus oxychloride, prepares salicylonitrile；
First kind reaction is the more salicylonitrile preparation method of domestic application, it can obtain high-load be used as measure
The sensitive analysis reagent of Pt, Cu, Zn etc. and the intermediate Saldox. for synthetic drug bunitrolol etc..But the method is grasped
Make loaded down with trivial details, the cost of raw material is more expensive, the total recovery of salicylonitrile is low, produce substantial amounts of three industrial wastes, be unfavorable for industrialized production.The
Two class methods are amides compound nitrile glycosylation reactions, and this type of reactions steps is simple, quantity of three wastes is few, and post processing is complicated, and solvent disappears
Consumption is big, and the total recovery of salicylonitrile is about 80%.
Summary of the invention
For problems of the prior art, the present invention provides one-step method to prepare the synthesis technique of salicylonitrile.
The present invention can be achieved through the following technical solutions:
One-step method prepares the synthesis technique of salicylonitrile, and main technological steps is as follows:
(1) salicylamide of 1 weight portion is dissolved in the solvent chlorobenzene of 2 weight portions, after being sufficiently stirred for, slowly improves anti-
Answer temperature, and control temperature at 90-100 DEG C, continue to be passed through phosgene and carry out phosgenation reaction, anti-with high performance liquid chromatography monitoring
Answer process, when the content of question response thing salicylamide is less than 1%, stops being passed through of phosgene immediately, be filled with nitrogen simultaneously and catch up with
Gas, the exit of gas arranges capture tank and processes tail gas；
(2) mixture after reaction being terminated is transferred to scrubbing tower, adds diluted sodium hydroxide solution and carries out alkali cleaning, then water
Washing, after stratification, taking-up organic layer carries out decompression distillation and obtains grease, adds petroleum ether, then stir in grease
Mix, stratification after stirring fully, extract with concentrated sulphuric acid, after separating organic layer, then with 60% dilute hydrochloric acid to organic layer
Being diluted, constantly separate out crystal, finally carry out recrystallization with the petroleum ether of heat in dilution, the crystallization after recrystallization is produced
Product drying obtains target product salicylonitrile after processing.
Further, the upper outlet of the capture tank described in step (1) is provided with alkali liquor absorption system, lower part outlet and
The import of scrubbing tower is connected.
The invention have the benefit that 1) replace the xylene solvent in traditional handicraft as solvent with chlorobenzene, permissible
Accelerate the dissolving of raw material salicylamide, be conducive to the carrying out of reaction simultaneously；2) by arranging capture tank, can effectively absorb anti-
The hydrogen chloride gas produced in should and phosgene；3) use high performance liquid chromatography detection course of reaction, target product can be improved
The productivity of salicylonitrile, reduces the generation of by-product simultaneously；4) after reaction terminates, by simply repeatedly extracting, distilling, Ji Keshi
Existing target product efficiently separates with other impurity, thus improves product purity.
Detailed description of the invention:
By embodiment, the detailed description of the invention of the present invention is made an explanation below.
Embodiment
One-step method prepares the synthesis technique of salicylonitrile, and main technological steps is as follows: (1) is by molten for the salicylamide of 1 weight portion
Solution is in the solvent chlorobenzene of 2 weight portions, after being sufficiently stirred for, slowly improves reaction temperature, and controls temperature at 100 DEG C, continues logical
Enter phosgene and carry out phosgenation reaction, monitor reaction process by high performance liquid chromatography, the product of target product salicylonitrile can be improved
Rate, reduces the generation of by-product simultaneously, when the content of question response thing salicylamide is less than 1%, stops being passed through of phosgene immediately, with
Time be filled with nitrogen and carry out catching up with gas, the exit of gas arranges capture tank and processes tail gas, and the upper outlet of capture tank is provided with alkali liquor
Absorption system, can effectively absorb the hydrogen chloride gas and the import phase of phosgene, lower part outlet and scrubbing tower produced in reaction
Even；(2) mixture after reaction being terminated is transferred to scrubbing tower, adds diluted sodium hydroxide solution and carries out alkali cleaning, then wash, stands
After layering, taking-up organic layer carries out decompression distillation and obtains grease, adds petroleum ether, then be stirred in grease, stirring
Stratification after fully, extracts with concentrated sulphuric acid, after separating organic layer, then carries out dilute with the dilute hydrochloric acid of 60% to organic layer
Releasing, constantly separate out crystal, finally carry out recrystallization with the petroleum ether of heat in dilution, the crystalline product after recrystallization is through dry
Target product salicylonitrile is obtained after dry process.By simply repeatedly extracting, distilling, target product and other impurity can be realized
Efficiently separate, thus improve product purity.
The foregoing is only highly preferred embodiment of the present invention, not in order to limit the present invention, all essences in the present invention
Any amendment, equivalent and the improvement etc. made within god and principle, should be included within the scope of the present invention.
Claims (2)
1. one-step method prepares the synthesis technique of salicylonitrile, it is characterised in that main technological steps is as follows:
(1) salicylamide of 1 weight portion is dissolved in the solvent chlorobenzene of 2 weight portions, after being sufficiently stirred for, slowly improves reaction temperature
Degree, and control temperature at 90-100 DEG C, continues to be passed through phosgene and carries out phosgenation reaction, with high performance liquid chromatography monitoring react into
Journey, when the content of question response thing salicylamide is less than 1%, stops being passed through of phosgene immediately, is filled with nitrogen simultaneously and carries out catching up with gas, gas
The exit of body arranges capture tank and processes tail gas；
(2) mixture after reaction being terminated is transferred to scrubbing tower, adds diluted sodium hydroxide solution and carries out alkali cleaning, then washes, quiet
After putting layering, taking-up organic layer carries out decompression distillation and obtains grease, adds petroleum ether, then is stirred, stir in grease
Stratification after mixing fully, extracts with concentrated sulphuric acid, after separating organic layer, then carries out dilute with the dilute hydrochloric acid of 60% to organic layer
Releasing, constantly separate out crystal, finally carry out recrystallization with the petroleum ether of heat in dilution, the crystalline product after recrystallization is through dry
Target product salicylonitrile is obtained after dry process.
One-step method the most according to claim 1 prepares the synthesis technique of salicylonitrile, it is characterised in that described in step 1
The upper outlet of capture tank is provided with the import of alkali liquor absorption system, lower part outlet and scrubbing tower and is connected.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610384298.XA CN106083647A (en) | 2016-05-28 | 2016-05-28 | One-step method prepares the synthesis technique of salicylonitrile |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610384298.XA CN106083647A (en) | 2016-05-28 | 2016-05-28 | One-step method prepares the synthesis technique of salicylonitrile |
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| Publication Number | Publication Date |
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| CN106083647A true CN106083647A (en) | 2016-11-09 |
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| CN201610384298.XA Pending CN106083647A (en) | 2016-05-28 | 2016-05-28 | One-step method prepares the synthesis technique of salicylonitrile |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098830A (en) * | 2017-04-13 | 2017-08-29 | 安徽广信农化股份有限公司 | A kind of refined process of salicylonitrile |
| CN115636763A (en) * | 2021-07-20 | 2023-01-24 | 联化科技股份有限公司 | Continuous preparation process of 4-carbamoylbenzoyl chloride and process for preparing 4-cyanobenzoyl chloride by using same |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739518A (en) * | 2013-12-26 | 2014-04-23 | 安徽广信农化股份有限公司 | Synthesis process for 2-hydroxybenzonitrile |
| CN105152972A (en) * | 2015-09-28 | 2015-12-16 | 湖南国发精细化工科技有限公司 | Method for synthesizing o-hydoxybenzonitrile |
-
2016
- 2016-05-28 CN CN201610384298.XA patent/CN106083647A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103739518A (en) * | 2013-12-26 | 2014-04-23 | 安徽广信农化股份有限公司 | Synthesis process for 2-hydroxybenzonitrile |
| CN105152972A (en) * | 2015-09-28 | 2015-12-16 | 湖南国发精细化工科技有限公司 | Method for synthesizing o-hydoxybenzonitrile |
Non-Patent Citations (1)
| Title |
|---|
| 何伟明等: "光气法合成邻羟基苯甲腈研究", 《上海化工》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107098830A (en) * | 2017-04-13 | 2017-08-29 | 安徽广信农化股份有限公司 | A kind of refined process of salicylonitrile |
| CN115636763A (en) * | 2021-07-20 | 2023-01-24 | 联化科技股份有限公司 | Continuous preparation process of 4-carbamoylbenzoyl chloride and process for preparing 4-cyanobenzoyl chloride by using same |
| CN115636763B (en) * | 2021-07-20 | 2024-03-08 | 联化科技股份有限公司 | Continuous preparation process of 4-carbamoyl benzoyl chloride and process for preparing 4-cyano benzoyl chloride by using same |
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Application publication date: 20161109 |
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