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CN110804000A - Preparation method of dicyano norbornane - Google Patents

Preparation method of dicyano norbornane Download PDF

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CN110804000A
CN110804000A CN201911099206.3A CN201911099206A CN110804000A CN 110804000 A CN110804000 A CN 110804000A CN 201911099206 A CN201911099206 A CN 201911099206A CN 110804000 A CN110804000 A CN 110804000A
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formula
compound
tetrabutylammonium
cyanide
catalyst
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CN110804000B (en
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任永平
梁万根
张超
崔卫华
费潇瑶
孙志利
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Yifeng New Material Co.,Ltd.
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Shandong Efirm Biochemistry and Environmental Protection Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/14—Preparation of carboxylic acid nitriles by reaction of cyanides with halogen-containing compounds with replacement of halogen atoms by cyano groups
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C17/00—Preparation of halogenated hydrocarbons
    • C07C17/093—Preparation of halogenated hydrocarbons by replacement by halogens
    • C07C17/10—Preparation of halogenated hydrocarbons by replacement by halogens of hydrogen atoms
    • 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
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2602/00—Systems containing two condensed rings
    • C07C2602/36—Systems containing two condensed rings the rings having more than two atoms in common
    • C07C2602/42—Systems containing two condensed rings the rings having more than two atoms in common the bicyclo ring system containing seven carbon atoms

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Abstract

The invention provides a preparation method of dicyano norbornane, which comprises the steps of reacting a compound with a structure shown in a formula (Y) with a cyaniding reagent under the condition of a catalyst to obtain dicyano norbornane; wherein the catalyst is selected from one or more of tetrabutylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, 15-Crown-5 and sodium iodide; furthermore, the method provided by the invention has the advantages of simple preparation process, high purity of the obtained product and high yield.

Description

Preparation method of dicyano norbornane
Technical Field
The invention relates to the field of synthesis, and particularly relates to a preparation method of dicyano norbornane.
Background
At present, dicyanonorbornane is an important chemical reagent, the method for preparing dicyanonornane is obtained by a hydrogen cyanide method of cyanonorbornene or norbornadiene, and the specific disclosed preparation process comprises the following steps:
1) U.S. patent specification 2666780 provides a process using a cobalt carbonyl catalyst and triphenylphosphine as a catalyst system.
2) JP-A-3-95151 and U.S. Pat. No. 3328443 disclose a method in which a zero-valent nickel complex catalyst and a Lewis acid are used as a catalyst system.
However, both of the above-disclosed methods require the use of an expensive catalyst, and the cyanation agent used is hydrogen cyanide, which is extremely toxic and has a low boiling point and an explosion limit of 5.6% to 12.8% in air, and thus is very dangerous. Further, the above-mentioned method for separating a complex, which includes a purification step, has problems of low yield and complicated operation.
Disclosure of Invention
In view of the above, the technical problem to be solved by the present invention is to provide a method for preparing dicyanonorbornane, which has a simple preparation process, and the obtained product has high purity and high yield.
The invention provides a preparation method of dicyano norbornane, which comprises the following steps:
reacting a compound with a structure shown in a formula (Y) with a cyaniding reagent under the condition of a catalyst to obtain dicyano norbornane;
wherein the catalyst is one or more of tetrabutylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, 15-Crown-5 and sodium iodide.
Figure BDA0002267697430000011
Wherein, R is3、R4Independently selected from halogen or cyano.
According to the invention, said R3、R4Independently selected from chloro, ao, iodo or cyano.
According to the invention, the cyanating agent is sodium cyanide, zinc cyanide, silver cyanide, potassium cyanide, calcium cyanide, potassium ferrocyanide (K)4[Fe(CN)6]) One or more of acetone cyanohydrin and trimethyl cyanosilane.
According to the invention, the solvent for the reaction is one or more of dimethyl sulfoxide, N-dimethylformamide, acetonitrile, diethyl ether, methyl acetone, dichlorobenzene, toluene, o-xylene, m-xylene and hexamethyl phosphoric triamide.
According to the invention, the molar ratio of the compound with the structure of the formula (Y) to the catalyst is 1 to (0.1-1).
According to the invention, the molar ratio of the compound with the structure of the formula (Y) to the cyaniding reagent is 1 to (2-5).
According to the invention, the mass ratio of the compound with the structure of the formula (Y) to the solvent is 1: 10-25.
According to the invention, the reaction temperature is 80-180 ℃.
According to the invention, the compound with the structure of the formula (Y) is prepared according to the following method:
mixing and reacting a compound shown in a formula (X) and hydrogen halide to obtain a compound shown in a formula (Y);
Figure BDA0002267697430000021
wherein, R is1、R2Independently selected from hydrogen or cyano.
According to the invention, the temperature of the mixed reaction of the compound represented by the formula (X) and the hydrogen halide is 70-120 ℃.
Compared with the prior art, the invention provides a preparation method of dicyano norbornane, which comprises the steps of reacting a compound with a structure shown in a formula (Y) with a cyaniding reagent under the condition of a catalyst to obtain dicyano norbornane; wherein the catalyst is selected from one or more of tetrabutylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, 15-Crown-5 and sodium iodide; furthermore, the method provided by the invention has the advantages of simple preparation process, high purity of the obtained product and high yield.
Drawings
FIG. 1 is a hydrogen spectrum of dicyanonorbornane provided in example 1.
Detailed Description
The invention provides a preparation method of dicyano norbornane, which comprises the following steps:
reacting a compound with a structure shown in a formula (Y) with a cyaniding reagent under the condition of a catalyst to obtain dicyano norbornane;
wherein the catalyst is one or more of tetrabutylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, 15-Crown-5 and sodium iodide.
Figure BDA0002267697430000031
Wherein, R is3、R4Independently selected from halogen or cyano.
According to the invention, the compound with the structure of formula (Y) reacts with a cyaniding reagent under the condition of a catalyst to obtain dicyano norbornane; in the compound with the structure of the formula (Y), R3 and R4Independently selected from chlorine, bromine, iodine or cyano, more preferably independently selected from chlorine, bromine or cyano; the cyaniding agent is preferably sodium cyanide, zinc cyanide, silver cyanide, potassium cyanide, calcium cyanide, potassium ferrocyanide (K)4[Fe(CN)6]) One or more of acetone cyanohydrin and trimethyl cyanosilane, preferably one or more of sodium cyanide, potassium cyanide and zinc cyanide; the catalyst for the reaction is preferably tetrabutylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, 15-Crown-5 or sodium iodide; the solvent for the reaction is preferably one or more of dimethyl sulfoxide, N-dimethylformamide, acetonitrile, diethyl ether, methyl acetone, dichlorobenzene, toluene, o-xylene, m-xylene and hexamethylphosphoric triamide; the molar ratio of the compound with the structure shown in the formula (Y) to the catalyst is preferably 1 to (0.1-1), more preferably 1 to (0.3-0.8), and more preferably 1 to (0.5-0.6); the molar ratio of the compound with the structure of the formula (Y) to the cyaniding reagent is preferably 1 to (2-5), more preferably 1 to (3-4), and the mass ratio of the compound with the structure of the formula (Y) to the solvent is preferablyIs 1 to (10-25), more preferably 1 to (13-20), and most preferably 1 to (15-18). The reaction temperature is preferably 80-180 ℃, and more preferably 120-150 ℃; the reaction time is preferably 5-10 hours, and more preferably 6-8 hours.
In the invention, the compound with the structure of formula (Y) is preferably prepared according to the following method:
mixing a compound shown in a formula (X) and hydrogen halide for reaction to obtain a compound shown in a formula (Y); wherein the hydrogen halide is preferably hydrogen chloride or hydrogen bromide; the mass ratio of the compound represented by the formula (X) to the hydrogen chloride is preferably 1: 2-5, and more preferably 1: 2-3; the reaction time is 6-12 h, preferably 7-10 h; the reaction temperature is 70-120 ℃, and preferably 70-90 ℃. In the invention, the compound shown in the formula (X) and the reaction liquid obtained by mixing and reacting the compound shown in the formula (X) and the hydrogen halide are extracted by using an organic solvent to obtain the compound shown in the formula (Y), wherein the solvent for extraction is one or more of ethyl acetate, dichloromethane, petroleum ether and acetonitrile, and dichloromethane or ethyl acetate is more preferable.
Figure BDA0002267697430000041
Wherein, R is1And R2 is independently selected from hydrogen or cyano.
The preparation method of dicyano norbornane provided by the invention comprises the steps of reacting a compound with a structure shown in a formula (Y) with a cyaniding reagent under the condition of a catalyst to obtain dicyano norbornane; wherein the catalyst is selected from one or more of tetrabutylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, 15-Crown-5 and sodium iodide; furthermore, the method provided by the invention has the advantages of simple preparation process, high purity of the obtained product and high yield.
The following will clearly and completely describe the technical solutions of the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.
Example 1
1.1916g of cyanonorbornene (bicyclo [2.2.1] -5-heptene-2-carbonitrile) was weighed into a 50ml single-neck flask, 3.0g of 40% hydroaminonic acid was added thereto, the mixture was reacted in an oil bath at T ═ 80 ℃ for 10 hours, and after the reaction was completed, the system was extracted with ethyl hexanoate to obtain 1.91g of cyanonorbornane containing-Br, and the above steps were repeated to obtain a total of 3.81g of cyanonorbornane containing-Br; the yield thereof is shown in Table 1.
2.00g of cyanonorbornane containing-Br obtained in the above-mentioned step was weighed into a 50ml single-neck flask, 1.48g of tetrabutylammonium iodide, 1.22g of sodium cyanide and 24.0g of dimethyl sulfoxide were added thereto, and then the reaction was carried out in an oil bath at T130 ℃ for 8 hours, followed by filtration of the system and removal of the solvent by rotary evaporation to obtain 1.36g of dicyanonorbornane, the yield and purity of which are shown in Table 1.
The structure of the obtained dicyanonorbornane was identified and the results are shown in fig. 1, fig. 1 being a hydrogen spectrum of the dicyanonorbornane provided in example 1.
Example 2
92.14g of norbornadiene (2, 5-norbornadiene) is weighed into a 500ml single-neck flask, 276.42g of 35% hydrochloric acid is added into the flask, the mixture is reacted for 9 hours in an oil bath at the temperature of 90 ℃ T, and after the reaction is finished, the system is extracted by ethyl caproate to obtain 153.51g of norbornane containing-C1; the yield thereof is shown in Table 1.
The above steps were repeated to obtain 307.01g of norbornane containing-Cl; 165.06g of norbornane containing-Cl obtained in the above step was weighed into a 5000ml single-neck flask, 52.29g of tetrabutylammonium fluoride, 140.92g of zinc cyanide and 1650g of toluene were added thereto, and then the mixture was reacted in an oil bath at 140 ℃ T for 8 hours, followed by filtration of the system and removal of the solvent by rotary evaporation to obtain 135.96g of dicyanonorbornane. The yield and purity are shown in table 1.
Example 3
119.16g of cyanonorbornene (bicyclo [2.2.1] -5-heptene-2-carbonitrile) was weighed into a 1000ml single-neck flask, 357.48g of 35% hydrochloric acid was added thereto, and the mixture was reacted in an oil bath at T ═ 80 ℃ for 8 hours, and after the completion of the reaction, the system was extracted with dichloromethane to give 146.28g of cyanonorbornane containing-Cl. The above steps were repeated to give 292.56g of cyanonorbornane containing-C1; the yield thereof is shown in Table 1.
155.62g of cyanonorbornane containing-C1 obtained in the above step was weighed into a 5000ml single-neck flask, 65.36g of tetrabutylammonium fluoride, 146.78g of zinc cyanide and 1980.72g of N, N-dimethylformamide were added thereto, and then the mixture was reacted in an oil bath at 120 ℃ T for 9 hours, followed by filtration of the system and removal of the solvent by rotary evaporation to obtain 137.34g of dicyanonorbornane. The yield and purity are shown in table 1.
Comparative example 1
A50 ml glass round bottom flask equipped with a stirrer, a thermometer, a nitrogen inlet and a condenser was charged with 1.07g (4.5mmol) of nickel chloride hexahydrate, 0.60g (9.2mmol) of zinc, 8.90g (28.7mmol) of triphenyl phosphite containing 0.2 wt% of triphenyl phosphate purified by a known method and 26.5g (22.2mmol) of cyanonorbornene, and nitrogen substitution in the gas phase portion was reliably performed to obtain a tetrakis (triphenyl phosphite) nickel catalyst. Then, 307.0g (2.58mol) of cyanonorbornene, 90.0g of toluene and the catalyst synthesis solution obtained above were charged in a 1L glass-made flat-bottomed separable flask equipped with a stirrer, a thermometer, a nitrogen inlet, a hydrogen cyanide inlet and a condenser, and after nitrogen substitution in the gas phase portion was sufficiently performed at room temperature, the temperature was raised to 60 ℃. Then, 69.13g (2.66mol) of liquid hydrogen cyanide was supplied over 3.5 hours, and a cyanato hydrogenation reaction was carried out to obtain 480.7g of crude dicyanonorbornane.
480.7g of the crude dicyanonorbornane was bubbled through the crude dicyanonorbornane at a flow rate of 500ml/min of nitrogen for 1 hour to degas it, and then insoluble matter was filtered. To the filtrate, 1.9g of 40% sulfuric acid was added, and the mixture was heated at 60 ℃ for 3 hours to decompose the catalyst, and further, 5.5g of 25% sodium hydroxide was added, and the mixture was heated at 40 ℃ for 2 hours to neutralize the resultant, 449.0g of toluene was added to extract dicyanonorbornane to obtain a dicyanonornane toluene solution, and then toluene was distilled off to obtain 447.6g of 85% dicyanonornane.
The results of the conditions of the examples and comparative examples are summarized in table 1:
TABLE 1
Figure BDA0002267697430000061
The data in the examples, the comparative examples and the tables show that the method has simple and convenient operation steps, easily obtained and cheap catalyst, and higher purity of the obtained product.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.

Claims (10)

1. A process for the preparation of dicyanonorbornane comprising:
reacting a compound with a structure shown in a formula (Y) with a cyaniding reagent under the condition of a catalyst to obtain dicyano norbornane;
wherein the catalyst is one or more of tetrabutylammonium iodide, tetrabutylammonium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, tetrabutylammonium hydroxide, 15-Crown-5 and sodium iodide;
Figure FDA0002267697420000011
wherein, R is3、R4Independently selected from halogen or cyano.
2. The method of claim 1, wherein R is3、R4Independently selected from chlorine, bromine, iodine or cyano.
3. The method according to claim 1, wherein the cyaniding agent is one or more selected from the group consisting of sodium cyanide, zinc cyanide, silver cyanide, potassium cyanide, calcium cyanide, potassium ferrocyanide, acetone cyanohydrin, and trimethylsilyl cyanide.
4. The method according to claim 1, wherein the solvent for the reaction is one or more selected from the group consisting of dimethyl sulfoxide, N-dimethylformamide, acetonitrile, diethyl ether, methyl acetone, dichlorobenzene, toluene, o-xylene, m-xylene, and hexamethylphosphoric triamide.
5. The preparation method of claim 1, wherein the molar ratio of the compound with the structure of formula (Y) to the catalyst is 1: 0.1-1.
6. The preparation method according to claim 1, wherein the molar ratio of the compound with the structure of formula (Y) to the cyanating reagent is 1: 2-5.
7. The preparation method of claim 1, wherein the mass ratio of the compound with the structure of formula (Y) to the solvent is 1: 10-25.
8. The method according to claim 1, wherein the reaction temperature is 80 to 180 ℃.
9. The method according to claim 1, wherein the compound having the structure of formula (Y) is prepared by the following method:
mixing and reacting a compound shown in a formula (X) and hydrogen halide to obtain a compound shown in a formula (Y);
Figure FDA0002267697420000021
wherein, R is1、R2Independently selected from hydrogen or cyano.
10. The method according to claim 9, wherein the temperature of the mixed reaction of the compound represented by the formula (X) and the hydrogen halide is 70 to 120 ℃.
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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021093585A1 (en) * 2019-11-11 2021-05-20 山东益丰生化环保股份有限公司 Method for preparing dicyanonorbornane

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04282347A (en) * 1991-03-11 1992-10-07 Mitsui Toatsu Chem Inc Method for producing norbornane diaminomethyls
JPH06184082A (en) * 1992-12-24 1994-07-05 Mitsui Toatsu Chem Inc Production of norcamphane dicarbonitrile
JP2002069043A (en) * 2000-08-25 2002-03-08 Mitsui Chemicals Inc 2,5(6)-bisaminomethyl-bicyclo[2.2.1]heptane slight in discoloratoin with time
JP2003055328A (en) * 2001-08-09 2003-02-26 Mitsui Chemicals Inc Method for producing dicyanonorbornanes
JP2003055327A (en) * 2001-08-09 2003-02-26 Mitsui Chemicals Inc Method for producing dicyanonorbornanes
CN101443308A (en) * 2006-06-30 2009-05-27 三井化学株式会社 Process for producing dicyanonorbornane and zerovalent-nickel complex catalyst
JP2017014156A (en) * 2015-07-02 2017-01-19 国立研究開発法人産業技術総合研究所 Manufacturing method of nitryl compound

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP3356901B2 (en) * 1994-12-27 2002-12-16 三井化学株式会社 Guanamines, their production method, derivatives and uses
US5631332A (en) * 1995-01-17 1997-05-20 Mitsui Toatsu Chemicals, Inc. Curing agents for epoxy resins comprising bis(aminomethyl)bicyclo[2.2.1]heptane adducts
JPH09235352A (en) * 1995-12-27 1997-09-09 Mitsui Toatsu Chem Inc Curing agent for resin
CN110804000B (en) * 2019-11-11 2020-09-22 山东益丰生化环保股份有限公司 Preparation method of dicyano norbornane

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH04282347A (en) * 1991-03-11 1992-10-07 Mitsui Toatsu Chem Inc Method for producing norbornane diaminomethyls
JPH06184082A (en) * 1992-12-24 1994-07-05 Mitsui Toatsu Chem Inc Production of norcamphane dicarbonitrile
JP2002069043A (en) * 2000-08-25 2002-03-08 Mitsui Chemicals Inc 2,5(6)-bisaminomethyl-bicyclo[2.2.1]heptane slight in discoloratoin with time
JP2003055328A (en) * 2001-08-09 2003-02-26 Mitsui Chemicals Inc Method for producing dicyanonorbornanes
JP2003055327A (en) * 2001-08-09 2003-02-26 Mitsui Chemicals Inc Method for producing dicyanonorbornanes
CN101443308A (en) * 2006-06-30 2009-05-27 三井化学株式会社 Process for producing dicyanonorbornane and zerovalent-nickel complex catalyst
JP2017014156A (en) * 2015-07-02 2017-01-19 国立研究開発法人産業技術総合研究所 Manufacturing method of nitryl compound

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
刘少华等: "有机合成中的氰化反应", 《精细与专用化学品》 *
赵宙兴等: "有机氰化取代反应研究进展", 《青海大学学报》 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021093585A1 (en) * 2019-11-11 2021-05-20 山东益丰生化环保股份有限公司 Method for preparing dicyanonorbornane

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