CN105152972A - Method for synthesizing o-hydoxybenzonitrile - Google Patents
Method for synthesizing o-hydoxybenzonitrile Download PDFInfo
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- CN105152972A CN105152972A CN201510625127.7A CN201510625127A CN105152972A CN 105152972 A CN105152972 A CN 105152972A CN 201510625127 A CN201510625127 A CN 201510625127A CN 105152972 A CN105152972 A CN 105152972A
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Abstract
The invention provides a method for synthesizing o-hydoxybenzonitrile. The method comprises the following steps that salicylamide and a solvent are mixed and stirred, phosgene is introduced at the temperature of 80 DEG C to 110 DEG C for reacting, and mixed liquid and mixed gas are obtained; nitrogen is introduced, and the mixed gas is completely exhausted; under the vacuum condition of 8 mmHg to 16 mmHg, the mixed liquid is rectified, and o-hydoxybenzonitrile is obtained. According to the method for synthesizing o-hydoxybenzonitrile, through the differences between the boiling points of o-hydoxybenzonitrile and the solvent and other impurities, the mixed liquid is rectified under the vacuum condition of 8 mmHg to 16 mmHg, o-hydoxybenzonitrile is obtained, the process steps are simple, solvent consumption is low, and the yield of o-hydoxybenzonitrile is above 87%.
Description
Technical field
The present invention relates to the field of chemical synthesis, particularly relate to salicylonitrile synthetic method.
Background technology
Salicylonitrile is one of important intermediate of synthesizing fungicide Azoxystrobin, and its synthesis mainly contains following two class methods:
The first kind: salicylic aldehyde and azanol hydrochloric acid generate salicylaldoxime, then obtain salicylonitrile by aceticanhydride or sulfur oxychloride dehydration;
Equations of The Second Kind: salicylic amide and phosgene or sulfur oxychloride or phosphorus trioxide exist lower dehydration, obtain salicylonitrile.
First kind method is that report synthesizes at most the method for salicylonitrile both at home and abroad, its maximum feature is the intermediate salicylaldoxime utilizing this method can obtain high-content, it can as the sensitive analysis reagent of mensuration Pt, Cu, Zn, Ni and Pb and for the synthesis of medical bunitrolol etc., but this class methods processing step is many, complex operation, raw materials cost is expensive, total recovery is low, only 55% ~ 58%, quantity of three wastes is large, is not suitable for suitability for industrialized production.
Equations of The Second Kind method is the classics reaction of amides itrile group, the feature of this type of reaction is that reactions steps is simple, quantity of three wastes is few, and need by loaded down with trivial details aftertreatment, recrystallization just can obtain the salicylonitrile of 98% mass content, solvent-oil ratio is large, and total recovery is about 80%.
Summary of the invention
Based on this, provide that a kind of processing step is simple, solvent-oil ratio is little and the salicylonitrile synthetic method that total recovery is high.
A kind of salicylonitrile synthetic method, comprises the following steps:
Salicylic amide and solvent are stirred, at 80 DEG C ~ 110 DEG C, passes into phosgene reaction, obtain mixed solution and mixed gas;
Pass into nitrogen, described mixed gas is caught up with to the greatest extent; And
Under the vacuum condition of 8mmHg ~ 16mmHg, described mixed solution is carried out rectifying, obtains salicylonitrile.
Wherein in an embodiment, the mass ratio of described salicylic amide and solvent is 1:1.6 ~ 2.2.
Wherein in an embodiment, described solvent is the toluene of more than 90% mass content.
Wherein in an embodiment, described in pass into phosgene reaction step be specially:
Pass into phosgene, monitor extent of reaction by liquid phase analysis, until salicylic amide reaction remains to less than 2%, stop passing into phosgene.
Wherein in an embodiment, described described mixed solution is carried out rectifying, the step obtaining salicylonitrile is specially:
Described mixed solution is carried out rectifying, collects the cut of 0 DEG C ~ 140 DEG C and the cut of 145 DEG C ~ 155 DEG C;
Cut into slices after the cut condensation of described 145 DEG C ~ 155 DEG C, obtain salicylonitrile.
Wherein in an embodiment, described described mixed solution is carried out rectifying, after collecting the step of the cut of 0 DEG C ~ 140 DEG C and the cut of 145 DEG C ~ 155 DEG C, further comprising the steps of:
By the cut recovery of described 0 DEG C ~ 140 DEG C.
Wherein in an embodiment, described salicylonitrile is the salicylonitrile of 97% ~ 98% mass content.
Above-mentioned salicylonitrile synthetic method, utilizes salicylonitrile and solvent and other impurity boiling point differences, by under the vacuum condition of 8mmHg ~ 16mmHg, mixed solution is carried out the method for rectifying, obtain salicylonitrile, processing step is simple, solvent-oil ratio is little, and salicylonitrile yield is more than 87%.
Embodiment
For enabling above-mentioned purpose of the present invention, feature and advantage become apparent more, are described in detail below to the specific embodiment of the present invention.Set forth a lot of detail in the following description so that fully understand the present invention.But the present invention can be much different from alternate manner described here to implement, those skilled in the art can when without prejudice to doing similar improvement when intension of the present invention, therefore the present invention is by the restriction of following public specific embodiment.
A kind of salicylonitrile synthetic method, comprises the following steps:
Step S110, salicylic amide and solvent to be stirred, at 80 DEG C ~ 110 DEG C, pass into phosgene reaction, obtain mixed solution and mixed gas.
Wherein, the mass ratio of salicylic amide and solvent is 1:1.6 ~ 2.2.Solvent is the toluene of more than 90% mass content.
In the present embodiment, salicylic amide and solvent mix and blend in Cupric sulfate dissolution kettle.
Wherein, the step passing into phosgene reaction is specially: pass into phosgene, monitors extent of reaction by liquid phase analysis, until salicylic amide reaction remains to less than 2%, stops passing into phosgene.
Be appreciated that in mixed solution containing toluene and salicylonitrile.Containing phosgene and hydrogenchloride in mixed gas.
Step S120, pass into nitrogen, above-mentioned mixed gas is caught up with to the greatest extent.
Be appreciated that in other embodiments, other rare gas elementes can also be passed into, as long as above-mentioned mixed gas can be caught up with to the greatest extent.
Step S130, under the vacuum condition of 8mmHg ~ 16mmHg, above-mentioned mixed solution is carried out rectifying, obtains salicylonitrile.
Wherein, above-mentioned mixed solution is carried out rectifying, the step obtaining salicylonitrile is specially:
Above-mentioned mixed solution is carried out rectifying, collects the cut of 0 DEG C ~ 140 DEG C and the cut of 145 DEG C ~ 155 DEG C;
Cut into slices after the cut condensation of above-mentioned 145 DEG C ~ 155 DEG C, obtain salicylonitrile.
In the present embodiment, above-mentioned mixed solution is carried out rectifying, after collecting the step of the cut of 0 DEG C ~ 140 DEG C and the cut of 145 DEG C ~ 155 DEG C, further comprising the steps of:
By the cut recovery of above-mentioned 0 DEG C ~ 140 DEG C.
Wherein, the cut of 0 DEG C ~ 140 DEG C is toluene.The cut of 145 DEG C ~ 155 DEG C is salicylonitrile.
In the present embodiment, by the vacuum condition of lobe pump control 8mmHg ~ 16mmHg.Preferably, by the vacuum condition of lobe pump control 14mmHg.
Above-mentioned salicylonitrile synthetic method, utilize salicylonitrile and solvent and other impurity boiling point differences, by under the vacuum condition of 8mmHg ~ 16mmHg, mixed solution is carried out the method for rectifying, obtain salicylonitrile, processing step is simple, and solvent-oil ratio is little, salicylonitrile yield is more than 87%, and salicylonitrile is the salicylonitrile of 97% ~ 98% mass content.
In addition, toluene can recovery, reduces cost, decreases environmental pollution.
It is below specific embodiment.
Embodiment 1
By 0.8 ton of salicylic amide and 2000L toluene mix and blend, at 90 DEG C ~ 100 DEG C, pass into phosgene, monitor extent of reaction by liquid phase analysis, react 10 ~ 12 hours, until salicylic amide reaction remains to less than 2%, stop passing into phosgene, obtain mixed solution and mixed gas.
Pass into nitrogen, caught up with by mixed gas to the greatest extent, then open high vacuum lobe pump, the vacuum condition of control 14mmHg, collected the cut of 0 DEG C ~ 140 DEG C by rectifying tower, this cut is toluene, recovery.Regather the cut of 145 DEG C ~ 155 DEG C, obtained the salicylonitrile of 98% content by microtome, yield is 90%.
Embodiment 2
By 0.8 ton of salicylic amide and 1600L toluene mix and blend, at 90 DEG C ~ 100 DEG C, pass into phosgene, monitor extent of reaction by liquid phase analysis, react 10 ~ 12 hours, until salicylic amide reaction remains to less than 2%, stop passing into phosgene, obtain mixed solution and mixed gas.
Pass into nitrogen, caught up with by mixed gas to the greatest extent, then open high vacuum lobe pump, the vacuum condition of control 14mmHg, collected the cut of 0 DEG C ~ 140 DEG C by rectifying tower, this cut is toluene, recovery.Regather the cut of 145 DEG C ~ 155 DEG C, obtained the salicylonitrile of 98% content by microtome, yield is 88%.
Embodiment 3
By 0.8 ton of salicylic amide and 2000L toluene mix and blend, at 90 DEG C ~ 100 DEG C, pass into phosgene, monitor extent of reaction by liquid phase analysis, react 10 ~ 12 hours, until salicylic amide reaction remains to less than 2%, stop passing into phosgene, obtain mixed solution and mixed gas.
Pass into nitrogen, caught up with by mixed gas to the greatest extent, then open high vacuum lobe pump, the vacuum condition of control 8mmHg, collected the cut of 0 DEG C ~ 140 DEG C by rectifying tower, this cut is toluene, recovery.Regather the cut of 145 DEG C ~ 155 DEG C, obtained the salicylonitrile of 97% content by microtome, yield is 92%.
Embodiment 4
By 0.8 ton of salicylic amide and 2000L toluene mix and blend, at 100 DEG C ~ 110 DEG C, pass into phosgene, monitor extent of reaction by liquid phase analysis, react 10 ~ 12 hours, until salicylic amide reaction remains to less than 2%, stop passing into phosgene, obtain mixed solution and mixed gas.
Pass into nitrogen, caught up with by mixed gas to the greatest extent, then open high vacuum lobe pump, the vacuum condition of control 16mmHg, collected the cut of 0 DEG C ~ 140 DEG C by rectifying tower, this cut is toluene, recovery.Regather the cut of 145 DEG C ~ 155 DEG C, obtained the salicylonitrile of 97% content by microtome, yield is 87%.
Embodiment 5
By 0.8 ton of salicylic amide and 2000L toluene mix and blend, at 80 DEG C ~ 90 DEG C, pass into phosgene, monitor extent of reaction by liquid phase analysis, react 10 ~ 12 hours, until salicylic amide reaction remains to less than 2%, stop passing into phosgene, obtain mixed solution and mixed gas.
Pass into nitrogen, caught up with by mixed gas to the greatest extent, then open high vacuum lobe pump, the vacuum condition of control 14mmHg, collected the cut of 0 DEG C ~ 140 DEG C by rectifying tower, this cut is toluene, recovery.Regather the cut of 145 DEG C ~ 155 DEG C, obtained the salicylonitrile of 97% content by microtome, yield is 87%.
The above embodiment only have expressed several embodiment of the present invention, and it describes comparatively concrete and detailed, but therefore can not be interpreted as the restriction to the scope of the claims of the present invention.It should be pointed out that for the person of ordinary skill of the art, without departing from the inventive concept of the premise, can also make some distortion and improvement, these all belong to protection scope of the present invention.Therefore, the protection domain of patent of the present invention should be as the criterion with claims.
Claims (7)
1. a salicylonitrile synthetic method, is characterized in that, comprises the following steps:
Salicylic amide and solvent are stirred, at 80 DEG C ~ 110 DEG C, passes into phosgene reaction, obtain mixed solution and mixed gas;
Pass into nitrogen, described mixed gas is caught up with to the greatest extent; And
Under the vacuum condition of 8mmHg ~ 16mmHg, described mixed solution is carried out rectifying, obtains salicylonitrile.
2. salicylonitrile synthetic method according to claim 1, is characterized in that, the mass ratio of described salicylic amide and solvent is 1:1.6 ~ 2.2.
3. salicylonitrile synthetic method according to claim 1, is characterized in that, described solvent is the toluene of more than 90% mass content.
4. salicylonitrile synthetic method according to claim 1, is characterized in that, described in pass into phosgene reaction step be specially:
Pass into phosgene, monitor extent of reaction by liquid phase analysis, until salicylic amide reaction remains to less than 2%, stop passing into phosgene.
5. salicylonitrile synthetic method according to claim 1, is characterized in that, described described mixed solution is carried out rectifying, and the step obtaining salicylonitrile is specially:
Described mixed solution is carried out rectifying, collects the cut of 0 DEG C ~ 140 DEG C and the cut of 145 DEG C ~ 155 DEG C;
Cut into slices after the cut condensation of described 145 DEG C ~ 155 DEG C, obtain salicylonitrile.
6. salicylonitrile synthetic method according to claim 5, is characterized in that, described described mixed solution is carried out rectifying, further comprising the steps of after collecting the step of the cut of 0 DEG C ~ 140 DEG C and the cut of 145 DEG C ~ 155 DEG C:
By the cut recovery of described 0 DEG C ~ 140 DEG C.
7. the salicylonitrile synthetic method according to any one of claim 1 ~ 6, is characterized in that, described salicylonitrile is the salicylonitrile of 97% ~ 98% mass content.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008261A (en) * | 2016-05-28 | 2016-10-12 | 安徽广信农化股份有限公司 | Synthesis process of salicylic nitrile used as pesticide intermediate |
| CN106083647A (en) * | 2016-05-28 | 2016-11-09 | 安徽广信农化股份有限公司 | One-step method prepares the synthesis technique of salicylonitrile |
| CN106083655A (en) * | 2016-05-28 | 2016-11-09 | 安徽广信农化股份有限公司 | A kind of novel method for synthesizing of salicylonitrile |
| CN106083648A (en) * | 2016-05-28 | 2016-11-09 | 安徽广信农化股份有限公司 | A kind of synthetic method of high yield salicylonitrile |
| CN106496066A (en) * | 2016-09-27 | 2017-03-15 | 江苏嘉隆化工有限公司 | A kind of preparation method of salicylonitrile |
| CN113717077A (en) * | 2021-09-22 | 2021-11-30 | 重庆长风化学工业有限公司 | Salicylic nitrile impurity and preparation method thereof |
| CN115636769A (en) * | 2021-07-20 | 2023-01-24 | 联化科技股份有限公司 | Preparation process of 4-carbamoylbenzoyl chloride and process for preparing 4-cyanobenzoyl chloride by using same |
| 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 |
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2015
- 2015-09-28 CN CN201510625127.7A patent/CN105152972A/en active Pending
Non-Patent Citations (1)
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| 陈强等: "水杨醛一步法合成邻羟基苯甲腈", 《农药研究与应用》 * |
Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106008261A (en) * | 2016-05-28 | 2016-10-12 | 安徽广信农化股份有限公司 | Synthesis process of salicylic nitrile used as pesticide intermediate |
| CN106083647A (en) * | 2016-05-28 | 2016-11-09 | 安徽广信农化股份有限公司 | One-step method prepares the synthesis technique of salicylonitrile |
| CN106083655A (en) * | 2016-05-28 | 2016-11-09 | 安徽广信农化股份有限公司 | A kind of novel method for synthesizing of salicylonitrile |
| CN106083648A (en) * | 2016-05-28 | 2016-11-09 | 安徽广信农化股份有限公司 | A kind of synthetic method of high yield salicylonitrile |
| CN106496066A (en) * | 2016-09-27 | 2017-03-15 | 江苏嘉隆化工有限公司 | A kind of preparation method of salicylonitrile |
| CN115636769A (en) * | 2021-07-20 | 2023-01-24 | 联化科技股份有限公司 | Preparation process of 4-carbamoylbenzoyl chloride and process for preparing 4-cyanobenzoyl chloride by using same |
| 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 |
| CN115636769B (en) * | 2021-07-20 | 2024-04-16 | 联化科技股份有限公司 | Preparation process of 4-carbamoyl benzoyl chloride and process for preparing 4-cyano benzoyl chloride by using same |
| CN113717077A (en) * | 2021-09-22 | 2021-11-30 | 重庆长风化学工业有限公司 | Salicylic nitrile impurity and preparation method thereof |
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Application publication date: 20151216 |