CN115536549B - Preparation method of 5-hexenenitrile - Google Patents

Preparation method of 5-hexenenitrile Download PDF

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Publication number
CN115536549B
CN115536549B CN202211241666.7A CN202211241666A CN115536549B CN 115536549 B CN115536549 B CN 115536549B CN 202211241666 A CN202211241666 A CN 202211241666A CN 115536549 B CN115536549 B CN 115536549B
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hexenenitrile
mmol
powder
preparation
reaction
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CN115536549A (en
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张奉志
杨修东
李崇富
徐欣
陈善任
郭鹏
杜家亮
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Zaozhuang Runan Pharmaceutical New Material Co ltd
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Zaozhuang Runan Pharmaceutical New Material Co ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/30—Preparation of carboxylic acid nitriles by reactions not involving the formation of cyano groups
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/128—Halogens; Compounds thereof with iron group metals or platinum group metals
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/132—Halogens; Compounds thereof with chromium, molybdenum, tungsten or polonium
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/06—Halogens; Compounds thereof
    • B01J27/138—Halogens; Compounds thereof with alkaline earth metals, magnesium, beryllium, zinc, cadmium or mercury

Abstract

The application relates to a preparation method of 5-hexenenitrile, which comprises the following steps: under inert atmosphere, inorganic salt, metal powder, allyl bromide and acrylonitrile are added into a solvent in proportion to react to prepare the 5-hexenenitrile. The preparation method of the 5-hexenenitrile has the advantages of mild reaction conditions, safe and simple operation, simple post-treatment, better yield and suitability for industrial production.

Description

Preparation method of 5-hexenenitrile
Technical Field
The application relates to the technical field of hexenenitrile synthesis, in particular to a preparation method of 5-hexenenitrile.
Background
5-hexenenitrile, the name being 5-cyano-1-pentene or 5-hexanenitrile, of formula C 6 H 9 N is a fine chemical, is commonly used as a medical intermediate or a material intermediate, is an important raw material for producing corresponding epoxynitrile, corresponding unsaturated acid and ester thereof, and has wide application in chemical industry or medical industry.
At present, regarding the preparation of 5-hexenenitrile, there are mainly the following methods:
(1) Sodium cyanide (Synlett, 2018, 29,6, 785-792) or potassium cyanide (Australian Journal of Chemistry,1993, 46,8, 1213-1228) is used as a raw material, and substitution reaction is carried out on the sodium cyanide or the potassium cyanide and 5-bromo-1-pentene to obtain 5-hexenenitrile; the preparation method has the defects of high raw material toxicity, high price and the like, and is difficult to carry out industrial production.
(2) Thoma et al (Tetrahedron Letters,1989, 30, 22, 2907-2910) prepared 5-hexenenitrile by free radical addition starting from bromopropyl bromide and acrylonitrile; the preparation method needs illumination, has higher requirements on equipment, and is not suitable for large-scale production because the catalyst is expensive.
Disclosure of Invention
Based on the defects in the prior art, the application aims to provide a preparation method of 5-hexenenitrile, which has the advantages of mild reaction conditions, safe and simple operation, simple post-treatment, better yield and suitability for industrial production.
Therefore, the application provides the following technical scheme.
The application provides a preparation method of 5-hexenenitrile, which comprises the following steps:
under inert atmosphere, inorganic salt, metal powder, allyl bromide and acrylonitrile are added into a solvent in proportion to react to prepare the 5-hexenenitrile.
Preferably, the solvent is at least one selected from tetrahydrofuran, dichloromethane, toluene, N-dimethylacetamide and ethanol.
Preferably, the inorganic salt is a metal chloride.
Preferably, the inorganic salt is selected from FeCl 3 、CrCl 3 、CuCl 2 At least one of them.
Preferably, the metal powder is selected from at least one of Fe powder, mn powder, zn powder and Mg powder.
Preferably, the molar ratio of the inorganic salt to the metal powder is from 1:1 to 3:1, preferably 2:1.
Preferably, the molar ratio of allyl bromide to the metal powder is from 1:1 to 1:2.
Preferably, the molar ratio of the allyl bromide to the acrylonitrile is 1:2 to 1:5.
Preferably, the reaction temperature is 25-80 ℃.
Preferably, the inert atmosphere is a nitrogen atmosphere.
The application has the following technical effects:
according to the preparation method of the 5-hexenenitrile, provided by the application, the addition reaction of allyl bromide and acrylonitrile is promoted by adding the inorganic salt and the metal powder, no illumination is needed, and the preparation method has the advantages of mild reaction conditions, safe and simple operation and simple post-treatment, simultaneously keeps a better yield, and is suitable for industrial production.
Detailed Description
In order to make the technical scheme and the beneficial effects of the application more obvious and understandable, the following detailed description is given by way of example. The present application will be further understood by the following description of embodiments, but the specific embodiments given by the applicant should not be considered as limiting the technical solution of the present application, and any modification of the definition of components or technical features and/or the form of the whole structure without substantial change should be considered as the protection scope defined by the technical solution of the present application. Unless defined otherwise, technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
The present application will be further described with reference to the following specific embodiments, and it should be noted that, on the premise of no conflict, new embodiments may be formed by any combination of the embodiments or technical features described below.
The application provides a preparation method of 5-hexenenitrile, which comprises the following steps:
under inert atmosphere, inorganic salt, metal powder, allyl bromide and acrylonitrile are added into a solvent in proportion to carry out free radical addition reaction, and the 5-hexenenitrile is prepared. Wherein, the addition reaction formula of allyl bromide and acrylonitrile is:
in the embodiment, the addition reaction of allyl bromide and acrylonitrile is promoted by adding inorganic salt and metal powder without illumination, so that the method has the advantages of mild reaction conditions, safe and simple operation and simple post-treatment, simultaneously keeps better yield, and is suitable for industrial production.
In one embodiment, the solvent is at least one selected from tetrahydrofuran, dichloromethane, toluene, N-dimethylacetamide, and ethanol. Preferably, the solvent is tetrahydrofuran or N, N-dimethylacetamide, and the dissolution effect is better.
In one embodiment, the inorganic salt is a metal chloride.
Further, the inorganic salt is selected from FeCl 3 、CrCl 3 、CuCl 2 At least one of them. Preferably, the inorganic salt is CrCl 3 ，CrCl 3 The catalyst is matched with metal powder, so that the free radical addition reaction is promoted, the formation of byproducts is reduced, and the yield of 5-hexenenitrile is further improved.
In one embodiment, the metal powder is selected from at least one of Fe powder, mn powder, zn powder, mg powder. Preferably, the metal powder is Mn powder, and the Mn powder is matched with inorganic salt, so that the free radical addition reaction is promoted, the formation of byproducts is reduced, and the yield of 5-hexenenitrile is improved. Further, in the preparation method of the application, the inorganic salt is CrCl 3 The metal powder is Mn powder.
In one embodiment, the molar ratio of the inorganic salt to the metal powder is 1:1-3:1 to form a good reaction promoting effect.
In one embodiment, the molar ratio of the allyl bromide to the metal powder is from 1:1 to 1:2.
In one embodiment, the molar ratio of the allyl bromide to the acrylonitrile is from 1:2 to 1:5.
In one embodiment, under inert atmosphere, inorganic salt, metal powder, allyl bromide and acrylonitrile are added into solvent in proportion, and free radical addition reaction is carried out at a certain reaction temperature to prepare 5-hexenenitrile. The reaction temperature is 25-80 ℃.
In one embodiment, the inert atmosphere is a nitrogen atmosphere.
The process of the present application is illustrated by the following specific examples, it being understood that these examples are illustrative of the basic principles, main features and advantages of the present application, and the present application is not limited by the scope of the following examples; the implementation conditions employed in the examples may be further adjusted according to specific requirements, and the implementation conditions not specified are generally those in routine experiments.
In the following examples 1 H NMR representation method: t=triplet, m=multiplet.
Example 1
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) To tetrahydrofuran was added 16.2g (100 mmol) of FeCl 3 2.7g (50 mmol) Mn powder, 6.0g (50 mmol) allyl bromide and 5.3g (100 mmol) acrylonitrile, and heating to 25 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue obtained was distilled under reduced pressure to give 3.4g of 5-hexenenitrile with a yield of 71%; wherein, the liquid crystal display device comprises a liquid crystal display device,
1 H NMR(CDCl 3 ，400MHz)δ1.72-1.81(m，2H)；2.12-2.32(m，2H)；2.35(t，2H,J＝7.6Hz)；5.04-5.15(m，2H)；5.66-5.82(m，1H)。
example 2
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 31.7g (200 mmol) of CrCl are added to tetrahydrofuran 3 5.4g (100 mmol) Mn powder, 12.0g (100 mmol) allyl bromide and 10.6g (200 mmol) acrylonitrile, and heating to 25 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 7.2g of 5-hexenenitrile in a yield of 76%.
Example 3
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 31.7g (200 mmol) of CrCl are added to tetrahydrofuran 3 6.5g (100 mmol) Zn powder, 12.0g (100 mmol) allyl bromide and 10.6g (200 mmol) acrylonitrile, and heating to 25 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 5.3g of 5-hexenenitrile in a yield of 56%.
Example 4
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 15.8g (100 mmol) of CrCl are added to tetrahydrofuran 3 5.4g (100 mmol) Mn powder, 12.0g (100 mmol) allyl bromide and 10.6g (200 mmol) acrylonitrile, and heating to 25 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 4.6g of 5-hexenenitrile in a yield of 49%.
Example 5
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) To tetrahydrofuran was added 47.4g (300 mmol) of CrCl 3 5.4g (100 mmol) Mn powder, 12.0g (100 mmol) allyl bromide and 10.6g (200 mmol) acrylonitrile, and heating to 25 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) A saturated ammonium chloride solution was added to the reaction flask, and extracted with methyl tert-butyl ether. The combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 7.1g of 5-hexenenitrile in 75% yield.
Example 6
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 31.7g (200 mmol) of CrCl are added to tetrahydrofuran 3 5.4g (100 mmol) Mn powder, 12.0g (100 mmol) allyl bromide and 26.5g (500 mmol) acrylonitrile, and heating to 25 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 7.7g of 5-hexenenitrile as a product in a yield of 81%.
Example 7
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 63.4g (400 mmol) of CrCl are added to tetrahydrofuran 3 10.8g (200 mmol) Mn powder, 12.0g (100 mmol) allyl bromide and 26.5g (500 mmol) acrylonitrile, and heating to 25 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 7.9g of 5-hexenenitrile in 83% yield.
Example 8
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 31.7g (200 mmol) of CrCl are added to tetrahydrofuran 3 5.4g (100 mmol) Mn powder, 12.0g (100 mmol) allyl bromide and 26.5g (500 mmol) acrylonitrile, and heating to 55 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 8.2g of 5-hexenenitrile in 86% yield.
Example 9
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 31.7g (200 mmol) of CrCl are added to tetrahydrofuran 3 5.4g (100 mmol) Mn powder, 12.0g (100 mmol) allyl bromide and 26.5g (500 mmol) acrylonitrile, and heating to 80 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 7.5g of 5-hexenenitrile in 79% yield.
Example 10
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 26.9g (200 mmol) of CuCl are added to tetrahydrofuran 2 5.6g (100 mmol) Fe powder, 12.0g (100 mmol) allyl bromide and 26.5g (500 mmol) of acrylonitrile, and heating to 80 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 5.8g of 5-hexenenitrile in 61% yield.
Example 11
The preparation method of the 5-hexenenitrile in the embodiment comprises the following steps:
(1) Under the protection of nitrogen, tetrahydrofuran is added into a reaction bottle and cooled to 0 ℃;
(2) 26.9g (200 mmol) of CuCl are added to tetrahydrofuran 2 2.4g (100 mmol) of Mg powder, 12.0g (100 mmol) of allyl bromide and 26.5g (500 mmol) of acrylonitrile, and raising the temperature to 80 ℃; preserving heat and reacting for 12 hours, and finishing the reaction;
(3) Adding saturated ammonium chloride solution into a reaction bottle, and extracting with methyl tertiary butyl ether; the combined organic phases were dried over anhydrous sodium sulfate, filtered and concentrated, and the residue was distilled under reduced pressure to give 4.1g of 5-hexenenitrile in 43% yield.
According to the preparation method of the 5-hexenenitrile, provided by the application, the addition reaction of allyl bromide and acrylonitrile is promoted by adding the inorganic salt and the metal powder, no illumination is needed, and the preparation method has the advantages of mild reaction conditions, safe and simple operation and simple post-treatment, can obtain a better yield, and is suitable for industrial production.
It should be understood that the above examples are illustrative and are not intended to encompass all possible implementations encompassed by the claims. Various modifications and changes may be made in the above embodiments without departing from the scope of the disclosure. Likewise, the individual features of the above embodiments can also be combined arbitrarily to form further embodiments of the application which may not be explicitly described. Therefore, the above examples merely represent several embodiments of the present application and do not limit the scope of protection of the patent of the present application.

Claims (8)

1. A process for the preparation of 5-hexenenitrile, characterized in that it comprises the following steps:
under inert atmosphere, adding inorganic salt, metal powder, allyl bromide and acrylonitrile into a solvent in proportion, and reacting to obtain 5-hexenenitrile;
the inorganic salt is selected from FeCl 3 、CrCl 3 、CuCl 2 At least one of (a) and (b);
the metal powder is selected from at least one of Fe powder, mn powder, zn powder and Mg powder.
2. The method according to claim 1, wherein the solvent is at least one selected from tetrahydrofuran, dichloromethane, toluene, N-dimethylacetamide and ethanol.
3. The method of claim 1, wherein the molar ratio of the inorganic salt to the metal powder is 1:1 to 3:1.
4. A method of preparing according to claim 3, wherein the molar ratio of the inorganic salt to the metal powder is 2:1.
5. The method of claim 1, wherein the molar ratio of allyl bromide to the metal powder is from 1:1 to 1:2.
6. The method of claim 1, wherein the molar ratio of allyl bromide to acrylonitrile is from 1:2 to 1:5.
7. The process according to claim 1, wherein the reaction temperature is 25 to 80 ℃.
8. The method of claim 1, wherein the inert atmosphere is a nitrogen atmosphere.
CN202211241666.7A 2022-10-11 2022-10-11 Preparation method of 5-hexenenitrile Active CN115536549B (en)

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Citations (4)

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Publication number Priority date Publication date Assignee Title
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Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101033200A (en) * 2001-05-09 2007-09-12 住友化学工业株式会社 Malononitrile compounds and their use as pesticides
CN101143874A (en) * 2007-11-05 2008-03-19 杭州师范大学 Method for preparing allylchlorosilane containing different substituents
CN101519355A (en) * 2009-03-17 2009-09-02 西北师范大学 Method for preparing methyl dihydrojasmonate
CN105642127A (en) * 2016-01-13 2016-06-08 厦门理工学院 Preparation method of anthraquinone functionalized polyvinylidene fluoride ultrafiltration membrane

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