CN112239415A - Synthetic method of alpha-cyanobenzene sodium hydroxamate - Google Patents
Synthetic method of alpha-cyanobenzene sodium hydroxamate Download PDFInfo
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- CN112239415A CN112239415A CN202011110564.2A CN202011110564A CN112239415A CN 112239415 A CN112239415 A CN 112239415A CN 202011110564 A CN202011110564 A CN 202011110564A CN 112239415 A CN112239415 A CN 112239415A
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- C07C253/00—Preparation of carboxylic acid nitriles
- C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
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Abstract
The invention relates to a synthetic method of alpha-cyanobenzene sodium oxime, which comprises the following two steps: the method comprises the following steps: reacting an alcohol (alcohol: sodium nitrite: acid =1:1-3.5: 1-5) solution and a sodium nitrite (alcohol: sodium nitrite: acid =1:1-3.5: 1-5) solution under an acidic condition (alcohol: sodium nitrite: acid =1:1-3.5: 1-5) to prepare nitrite; step two: reacting the prepared nitrite with benzyl cyanide (benzyl cyanide: nitrite: alkali =1: 1-3: 1-3) to prepare nitrile benzaldehyde oxime sodium. The advantages are that: the cost is reduced, the operation is convenient, the safety coefficient is high, and the method is suitable for industrial production.
Description
Technical Field
The invention relates to a method for synthesizing alpha-cyanobenzene sodium oxime, which has the advantages of low cost, convenient operation and high safety factor and is suitable for industrial production.
Background
Nitrile benzophenone sodium oxime is an important medical intermediate, and one important application is the synthesis of pesticide phoxim. The production process of phoxim initiated polymerization has been reported at present, and is characterized by that under the acidic condition methanol and sodium nitrite are reacted to produce methyl nitrite gas, then reacted with benzyl cyanide and alkali liquor to produce alpha-cyano-benzene methyl oxime sodium. The method is also a route generally adopted in domestic production at present, but the route is high in risk, and firstly, methyl nitrite gas generated is easy to explode and is high in risk. Secondly, the acid adjustment and isomerization are needed after the generation of the sodium oxime, and the alkali adjustment is needed again after the acid adjustment, so that the wastewater amount is large and is 40 times of the raw material amount, and the operation is very complicated.
In addition, as for a reported production method of phoxim, sodium oxime needs to be refined and then undergoes the next reaction, compared with the method which can directly undergo the next reaction without refining, the method has the advantages of higher cost which is about 20 percent higher than that of the sodium oxime, and is not suitable for large-scale production.
Disclosure of Invention
The design purpose is as follows: avoids the defects in the background technology, designs a synthetic method of alpha-cyanobenzene sodium oxime, which has the advantages of low cost, convenient operation and high safety factor and is suitable for industrial production.
The design scheme is as follows: in order to achieve the above design objectives. The invention provides the following technical scheme:
the synthesis process of alpha-cyano sodium benzoate includes the following two steps:
the method comprises the following steps: reacting alcohol and sodium nitrite solution under an acidic condition to prepare nitrite;
step two: reacting the prepared nitrite with phenylacetonitrile to prepare nitrile benzaldehyde oxime sodium.
According to the further technical scheme, in the first step, sodium nitrite and water are added into a three-neck flask to be dissolved, then alcohol is added, acid is slowly added while stirring, the mixture reacts for 30min-1h at the temperature of-5 ℃, after TLC detection reaction is completed, liquid is separated, and drying agent is dried to obtain benzyl nitrite.
The further technical scheme is that the alcohol in the first step is benzyl alcohol, cyclohexanol and n-hexyl alcohol
In a further technical scheme, the acid in the step one is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid or p-toluenesulfonic acid.
The further technical scheme is that in the step one, petroleum ether in TLC chromatographic solution: ethyl acetate is (1-5): 1.
according to a further technical scheme, in the step one, the drying agent is anhydrous magnesium sulfate, anhydrous sodium carbonate, calcium hydride and calcium carbide.
According to a further technical scheme, the mol ratio of the alcohol, the sodium nitrite, the water and the acid in the step one is as follows: 1: (2-4): (4-10): (1-5).
According to a further technical scheme, in the second step, benzonitrile and a solvent A are mixed, then alkali is added, benzyl nitrite obtained in the first step is dripped, heating is carried out for 2-4h, a mixture containing yellow solids is obtained, and the yellow solids, namely alpha-cyanobenzohydroxamate sodium, are obtained through suction filtration.
In a further technical scheme, the solvent A is benzyl alcohol, cyclohexanol, n-hexanol and dichloromethane.
In a further technical scheme, the alkali is sodium hydroxide, sodium carbonate or sodium ethoxide.
In the first step of the invention, TLC is needed to determine the end point of the reaction, and the reaction time is controlled to be 0.5-1h, because if the time is too long, the by-products are increased, benzyl nitrite in the water phase can be extracted by ethyl acetate after liquid separation, and otherwise, part of the benzyl nitrite is lost. In the second step, the reaction time is controlled to be 2-4h, and if the reaction time is insufficient (less than 2.5 h), the yield is lower than 80%.
The benzyl nitrite generated by the method and other methods for generating methyl nitrite have great advantages. For example: the boiling point of benzyl nitrite is much higher than that of methyl nitrite, the safety coefficient is high, and the operation is convenient; the benzyl nitrite reacts with the benzonitrile without refining, so the cost is lower; the present invention is the best method from the viewpoints of cost and safety.
The invention relates to a method for synthesizing alpha-benzohydroxamate sodium, which uses benzyl alcohol and sodium nitrite as raw materials, adds acid and reacts at low temperature to generate benzyl nitrite. Then, benzonitrile is used for obtaining the alpha-benzohydroxamic sodium under the alkalinity, the products are all in the required cis form, the operation is safe and simple, and the method is suitable for industrial production.
Drawings
FIG. 1 is a schematic representation of the infrared profile of phoxim.
FIG. 2 is a schematic nuclear magnetic curve of phoxim.
FIG. 3 is a schematic representation of oxime infrared curves.
FIG. 4 is a nuclear magnetic representation of oxime.
Detailed Description
FIGS. 1-4 show typical nuclear magnetic and infrared spectra of alpha-cyanobenzenestrobin sodium prepared according to the invention, and the nuclear magnetic and infrared spectra of phoxim prepared from the alpha-cyanobenzenestrobin sodium.
Example 1: the synthesis process of alpha-cyanobenzene sodium hydroxamate includes the following two steps:
synthesis of benzyl nitrite
Adding 14g (0.2 mol) of sodium nitrite and 42g of water (2.33 mol) into a 100ml beaker, dissolving, pouring into a 250ml three-neck flask, adding 22g (0.2 mol) of benzyl alcohol, cooling the mixture to about 0 ℃, slowly adding 36g (1 mol) of 36% concentrated hydrochloric acid dropwise, controlling the reaction temperature below 5 ℃, reacting for 30-40min, detecting whether the reaction is complete by TLC, separating liquid, taking upper layer yellow transparent liquid, and obtaining the yield of 73.1%.
Synthesis of alpha-cyanobenzene sodium hydroxamate
In a 250ml three-necked flask were placed 22g (0.2 mol) of benzyl alcohol, 9.5g (0.08 mol) of benzyl cyanide, and 8g (0.2 mol) of sodium hydroxide in this order. After the addition, 14g (0.1 mol) of benzyl nitrite is gradually dripped into the mixed system, the reaction temperature is controlled to be 70-80 ℃ for 2-3 h, TLC is used for detecting whether the reaction is complete, after the reaction is finished, suction filtration is carried out, and dichloromethane is used for washing a filter cake to obtain yellow solid alpha-cyanobenzene oxime sodium, wherein the yield is 80.2%.
Example 2: the synthesis process of alpha-cyanobenzene sodium hydroxamate includes the following two steps: synthesis of cyclohexane methyl nitrite
Adding 14g (0.2 mol) of sodium nitrite and 42g of water (2.33 mol) into a 100ml beaker, dissolving, pouring into a 250ml three-neck flask, adding 20g (0.2 mol) of cyclohexanol, cooling the mixture to about 0 ℃, slowly dripping 36g (1 mol) of 36% concentrated hydrochloric acid, controlling the reaction temperature below 5 ℃, reacting for 30-40min, separating, taking the upper layer of yellow transparent liquid, and obtaining the yield of 85%.
Synthesis of alpha-cyanobenzene sodium hydroxamate
Into a 250ml three-necked flask were charged 20g (0.2 mol) of cyclohexanol, 9.5g (0.16 mol) of benzonitrile and an aqueous solution of sodium hydroxide in this order. After the addition, 14g (0.1 mol) of cyclohexane methyl nitrite is gradually dropped into the mixed system, the reaction temperature is controlled to be 70-80 ℃ for 2-3 h, TLC is used for detecting whether the reaction is complete, and after the reaction is finished, suction filtration is carried out to obtain yellow solid alpha-cyanobenzene oxime sodium, wherein the yield is 80.2%.
Example 3: the synthesis process of alpha-cyanobenzene sodium hydroxamate includes the following two steps:
synthesis of n-hexane nitrite
Adding 14g (0.2 mol) of sodium nitrite and 42g of water (2.33 mol) into a 100ml beaker, pouring the mixture into a 250ml three-neck flask after dissolving, adding 20.4g (0.2 mol) of n-hexanol, cooling the mixture to about 0 ℃, slowly dripping 36g (1 mol) of 36% concentrated hydrochloric acid, controlling the reaction temperature below 5 ℃, reacting for 30-40min, separating the liquid, taking the upper layer of yellow transparent liquid, and obtaining the yield of 80.3%.
Synthesis of alpha-cyanobenzene sodium hydroxamate
Into a 250ml three-necked flask were charged 20g (0.2 mol) of cyclohexanol, 9.5g (0.16 mol) of benzonitrile and an aqueous solution of sodium hydroxide in this order. After the addition, 14g (0.1 mol) of cyclohexane benzyl nitrite is gradually dropped into the mixed system, the reaction temperature is controlled to be 30-40 ℃ for 2-3 h, TLC is used for detecting whether the reaction is complete, and after the reaction is finished, suction filtration is carried out to obtain yellow solid alpha-cyanobenzene oxime sodium, wherein the yield is 80.2%.
It is to be understood that: although the above embodiments have described the design idea of the present invention in more detail, these descriptions are only simple descriptions of the design idea of the present invention, and are not limitations of the design idea of the present invention, and any combination, addition, or modification without departing from the design idea of the present invention falls within the scope of the present invention.
Claims (10)
1. A synthetic method of alpha-cyanobenzene sodium hydroxamate is characterized in that: the method comprises the following two steps:
the method comprises the following steps: reacting alcohol and sodium nitrite solution under an acidic condition to prepare nitrite;
step two: reacting the prepared nitrite with benzonitrile to obtain nitrile benzaldehyde oxime sodium.
2. The method of synthesizing α -cyanobenzenestrobime according to claim 1, wherein: the method comprises the following steps: reacting an alcohol (alcohol: sodium nitrite: acid =1:1-3.5: 1-5) solution and a sodium nitrite (alcohol: sodium nitrite: acid =1:1-3.5: 1-5) solution under an acidic condition (alcohol: sodium nitrite: acid =1:1-3.5: 1-5) to prepare nitrite;
step two: reacting the prepared nitrite with benzyl cyanide (benzyl cyanide: nitrite: alkali =1: 1-3: 1-3) to prepare nitrile benzaldehyde oxime sodium.
3. The method of synthesizing α -cyanobenzenestrobime according to claim 2, wherein: in the first step, sodium nitrite (alcohol: sodium nitrite: acid =1:1-3.5: 1-5) and water (sodium nitrite: water =1: 2-4) are added into a three-neck flask, after dissolution, alcohol (alcohol: sodium nitrite: acid =1:1-3.5: 1-5) is added, acid (6-18 mol/L) is slowly added while stirring, the mixture is reacted for 30min-1h at-5 ℃ to 5 ℃, after TLC detection reaction is completed, liquid is separated, and drying agent is dried to obtain nitrite.
4. The method for synthesizing α -cyanobenzenestrobime according to claim 2 or 3, wherein: the alcohol in the first step is benzyl alcohol, cyclohexanol and n-hexyl alcohol.
5. The method for synthesizing α -cyanobenzenestrobime according to claim 2 or 3, wherein: the acid in the first step is hydrochloric acid, sulfuric acid, phosphoric acid, nitric acid and p-toluenesulfonic acid.
6. The method for synthesizing α -cyanobenzenestrobime according to claim 2 or 3, wherein: in the first step, the drying agent is anhydrous magnesium sulfate, anhydrous sodium carbonate, calcium hydride and calcium carbide.
7. The method for synthesizing α -cyanobenzenestrobime according to claim 2 or 3, wherein: the mol ratio of the alcohol, the sodium nitrite, the water and the acid in the first step is as follows: 1: (1-3.5): (2-4): (1-5).
8. The method of synthesizing α -cyanobenzymidine sodium according to claim 2, wherein: in the second step, benzyl cyanide and a solvent A (alcohol: solvent A =1: 0.5-2) are mixed, then alkali (the mol ratio of benzyl cyanide to nitrite to alkali is 1: 1-3: 1-3) is added, the nitrite obtained in the first step is dripped, the mixture containing yellow solid is obtained after heating for 2-4h, and the yellow solid obtained by suction filtration is alpha-cyano benzene oxime sodium.
9. The method of claim 8, wherein the synthesis of sodium α -cyanobenzenesulfonate comprises: the solvent A is benzyl alcohol, cyclohexanol, n-hexanol and dichloromethane; the alkali is sodium hydroxide, sodium carbonate or sodium ethoxide.
10. The method for synthesizing alpha-cyanobenzenestrobime sodium according to claims 2 and 8, wherein the molar ratio of phenylacetonitrile, nitrite and alkali in the second step is: 1:(1-3): (1-3).
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260555A (en) * | 1979-11-07 | 1981-04-07 | Ciba-Geigy Corporation | Process for the manufacture of cyanooximinonitriles |
| CN1081680A (en) * | 1992-07-27 | 1994-02-09 | 连云港市第二农药厂 | Improve the method for phoxim crude content |
| CN1115319A (en) * | 1994-07-19 | 1996-01-24 | 石家庄化工厂胜芳分厂 | Phoxim production technique by initiating polymerizing |
| CN1353107A (en) * | 2000-11-07 | 2002-06-12 | 王爱彬 | Refined alpha-cyanobenzaldoxine and its preparing process |
-
2020
- 2020-10-16 CN CN202011110564.2A patent/CN112239415B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4260555A (en) * | 1979-11-07 | 1981-04-07 | Ciba-Geigy Corporation | Process for the manufacture of cyanooximinonitriles |
| CN1081680A (en) * | 1992-07-27 | 1994-02-09 | 连云港市第二农药厂 | Improve the method for phoxim crude content |
| CN1115319A (en) * | 1994-07-19 | 1996-01-24 | 石家庄化工厂胜芳分厂 | Phoxim production technique by initiating polymerizing |
| CN1353107A (en) * | 2000-11-07 | 2002-06-12 | 王爱彬 | Refined alpha-cyanobenzaldoxine and its preparing process |
Non-Patent Citations (1)
| Title |
|---|
| 天津农药厂: "新农药-辛硫磷", 《化学通报》 * |
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