CN111517986B - Novel method for preparing aliphatic tri-nitrile and aliphatic tri-nitrile prepared by novel method - Google Patents
Novel method for preparing aliphatic tri-nitrile and aliphatic tri-nitrile prepared by novel method Download PDFInfo
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Abstract
The application belongs to the technical field of organic synthesis, and particularly relates to a novel method for preparing aliphatic tri-nitrile and the aliphatic tri-nitrile prepared by the novel method. The present application provides a novel process for the preparation of aliphatic trisnitriles, comprising the steps of: removal of COOC from Compound II b H c X d Obtaining aliphatic tri-nitrile; the structural formula of the compound II is as follows:
Description
Technical Field
The application belongs to the technical field of organic synthesis, and particularly relates to a novel method for preparing aliphatic tri-nitrile and the aliphatic tri-nitrile prepared by the novel method.
Background
Aliphatic tri-nitrile is an important industrial raw material, for example, 1,3, 6-hexane tri-nitrile is currently used as an electrolyte additive, has obvious effect of improving the high voltage stability of a battery, and reduces the decomposition of the traditional organic carbonate solvent under high voltage. In the earliest stage, 1,3, 6-hexanetrinitrile is a byproduct of preparing adiponitrile by electrolyzing acrylonitrile, and has low yield and needs multiple distillation and separation.
The cyclization of adiponitrile under an equivalent strong base to form 2-amino-1-cyclopentene-1-carbonitrile (journal of the chemical 1909,700) is known to be less selective, and so few researchers have proposed the synthesis of hexanetrinitrile by reacting 2-amino-1-cyclopentene-1-carbonitrile with acrylonitrile, and the soviet chemistry J (journal of applied chemistry of the USSR,1972, 2683-2684) has proposed the synthesis with elemental sodium as a base, the safety hazard making it difficult to mass-produce it. In 2001, german bayer corporation in DE1003288 patent, weak bases were used for ring opening, but the first step intermediate was still expensive potassium tert-butoxide. Patent CN105037203 of Santa Classification of China proposes that 1, 6-dichloro-2-butene is reacted with NaCN to synthesize 1, 6-dinitrile-2-butene, which is added with hydrochloric acid to obtain chloro and then reacted with NaCN to obtain the product.
In view of the above, the current methods for synthesizing aliphatic tri-nitriles have more or less drawbacks and problems.
Disclosure of Invention
In order to solve the above technical problems, a first aspect of the present application provides a novel method for preparing aliphatic tri-nitrile, the method comprising the steps of: removal of COOC from Compound II b H c X d Obtaining aliphatic tri-nitrile;
the structural formula of the compound II is as follows:wherein a is an integer of 3-12, b is not less than 1, c is not less than 1, d is not less than 0, e is 2, and X is a heteroatom.
As a preferable technical scheme, a is an integer of 3-12, b is 1-8,c more than or equal to 3, d is 0, and e is 2.
As a preferred embodiment, the compound II is used for COOC removal b H c X d The method of (2) is selected from one of the following: (1) COOC removal under acidic conditions b H c X d The method comprises the steps of carrying out a first treatment on the surface of the (2) COOC removal under alkaline conditions b H c X d The method comprises the steps of carrying out a first treatment on the surface of the (3) hydrolysis followed by decarboxylation by heating; (4) COOC removal by DMSO and catalyst b H c X d The method comprises the steps of carrying out a first treatment on the surface of the (5) High-temperature heating COOC removal b H c X d 。
As a preferred technical scheme, the preparation raw materials of the compound II include: compound III and acrylonitrile; the structural formula of the compound III isWherein a is an integer of 3-12, b is not less than 1, c is not less than 1, d is not less than 0, and X is a heteroatom.
As a preferred technical scheme, the preparation method of the compound II comprises the following steps: the compound III and acrylonitrile are reacted in a first inorganic base and/or a first organic strong base system.
As a preferable technical scheme, the reaction temperature is 0-150 ℃; the mol ratio of the compound III to the acrylonitrile is 0.1-10:1, a step of; the addition amount of the first inorganic base or the first organic strong base is 0.01-2.0 mol equivalent of the compound III.
As a preferred technical scheme, the preparation raw materials of the compound III include: compound IV and compound V; the structural formula of the compound V isThe structural formula of the compound IV is +.>Wherein a is an integer of 3-12, b is more than or equal to 1, c is more than or equal to 1, d is more than or equal to 0, X is a heteroatom, and Y is selected from one of halogen, alkylsulfonyl, alkylarylsulfonyl, haloalkylsulfonyl and haloalkylphenylsulfonyl.
As a preferred technical scheme, the preparation method of the compound III comprises: the compound IV and the compound V are reacted in a second inorganic base and/or a second organic strong base system.
As a preferable technical scheme, the reaction temperature is 50-250 ℃; the molar ratio of the compound IV to the compound V is 0.1-100:1, a step of; the addition amount of the second inorganic base or the second organic strong base is 0.1-10.0 molar equivalents of the compound IV.
The second aspect of the application provides the high-purity aliphatic tri-nitrile prepared by the method.
The beneficial effects are that: the method is simple to operate and answer, raw materials are easy to obtain, and the method is environment-friendly and has great implementation value and social and economic benefits; overcomes the safety problem of preparing aliphatic tri-nitrile under the condition of sodium in the traditional process, and has high yield and high product purity.
Detailed Description
In order to solve the above problems, the present application provides a novel process for preparing aliphatic tri-nitriles, comprising the steps of: removal of COOC from Compound II b H c X d Obtaining aliphatic tri-nitrile;
the structural formula of the aliphatic tri-nitrile is as follows:
the structural formula of the compound II is as follows:wherein a is an integer of 3-12, b is not less than 1, c is not less than 1, d is not less than 0, e is 2, and X is a heteroatom.
Preferably, a is an integer of 3 to 12, b is 1 to 8,c.gtoreq.3, d is 0 and e is 2.
More preferably, a is an integer from 3 to 8, b is 2, c is 5,d is 0, e is 2; further preferably, a is an integer from 3 to 6, b is 2, c is 5,d is 0, and e is 2.
In the present application, the "heteroatom" means an element other than carbon and hydrogen atoms, such as chlorine, bromine, iodine, fluorine, sulfur, nitrogen, phosphorus, and the like.
In some embodiments, the aliphatic tri-nitrile is selected from one of 1,3, 7-heptanetrinitrile, 1,3, 6-hexanetrinitrile, 1,3, 8-octanetrianitrile, 1,3, 9-nonanetrinitrile, 1,3,10-decane tri-nitrile.
In some embodiments, the compound II is selected from one of ethyl 2, 5-dicyano-2-cyanoethyl-pentanoate, ethyl 2, 6-dicyano-2-cyanoethyl-hexanoate, methyl 2, 5-dicyano-2-cyanoethyl-pentanoate, methyl 2, 6-dicyano-2-cyanoethyl-hexanoate, propyl 2, 5-dicyano-2-cyanoethyl-pentanoate, propyl 2, 6-dicyano-2-cyanoethyl-hexanoate, butyl 2, 5-dicyano-2-cyanoethyl-pentanoate, butyl 2, 6-dicyano-2-cyanoethyl-hexanoate.
Preparation of aliphatic dinitriles from Compound II
Preferably, the compound II removes COOC b H c X d The method of (2) is selected from one of the following: (1) COOC removal under acidic conditions b H c X d The method comprises the steps of carrying out a first treatment on the surface of the (2) COOC removal under alkaline conditions b H c X d The method comprises the steps of carrying out a first treatment on the surface of the (3) hydrolysis followed by decarboxylation by heating; (4) COOC removal by DMSO and catalyst b H c X d The method comprises the steps of carrying out a first treatment on the surface of the (5) High-temperature heating COOC removal b H c X d 。
When COOC is removed under acidic conditions b H c X d When the acid is selected from at least one of sulfuric acid, hydrochloric acid, nitric acid and C2-C5 carboxylic acid, the removal temperature is 25-250 ℃, and the addition amount of the acid is 0.1-10.0 molar equivalents of the compound II; preferably, the removal temperature is 50-150 ℃, and the addition amount of the acid is 0.1-5.0 molar equivalents of the compound II; on the premise of not affecting the purpose of the application, water, alcohols, ethers, esters, nitriles and other solvents can be added for removal reaction. The solvent includes at least one of water, methanol, ethanol, isopropanol, butanol, acetonitrile, butyronitrile, diethyl ether, butyl ether, methylethyl ether, methylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol methylbutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1, 4-dioxane, benzene, toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, dichloroethane, trichloromethane, trichloroethane, tetrachloroethane, trichloropropane, tetrachloroethylene, ethyl acetate, butyl acetate, isopropyl acetate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone. The addition amount of the solvent is 0.1-20 times of the mass of the compound II.
In one embodiment, the acid is sulfuric acid, the solvent is methylene chloride, the removal temperature is 80-120 ℃, the addition amount of the acid is 0.1-2 times of the mass of the compound II, and the addition amount of the solvent is 2 times of the mass of the compound II.
When COOC is removed under alkaline conditions b H c X d In this case, the base is not particularly limited,can form alkaline conditions without affecting the purpose of the application; preferably, the base is MZ, wherein M is one of sodium, potassium, iron, calcium, lithium, barium, copper, lead, palladium; z is one of hydroxide, carbonate, bicarbonate, phosphate and biphosphate, and the alkali can be a combination of 2 or more than 2 alkali; the removal temperature is 25-250 ℃, and the addition amount of the alkali is 0.1-10.0 molar equivalents of the compound II; preferably, the removal temperature is 50-200 ℃, and the amount of the base added is 0.1-5 molar equivalents of the compound II.
On the premise of not affecting the purpose of the application, water, alcohols, ethers, esters, nitriles and other solvents can be added for removal reaction. The solvent includes at least one of water, methanol, ethanol, isopropanol, butanol, acetonitrile, butyronitrile, diethyl ether, butyl ether, methylethyl ether, methylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol methylbutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1, 4-dioxane, benzene, toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, dichloroethane, trichloromethane, trichloroethane, tetrachloroethane, trichloropropane, tetrachloroethylene, ethyl acetate, butyl acetate, isopropyl acetate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone. The addition amount of the solvent is 1-20 times of the mass of the compound II.
In one embodiment, the base is potassium hydroxide, the solvent is dichloromethane and water, and the base is added in an amount of 0.1 to 2 molar equivalents of compound II; the addition amount of the solvent is 1-10 times of the mass of the compound II.
When the hydrolysis is performed first and then the decarboxylation is performed by heating, the hydrolysis is performed by adding a base, which is not particularly limited, and can form an alkaline condition without affecting the object of the present application; preferably, the base is MN, wherein M is one of sodium, potassium, iron, calcium, lithium, barium, copper, lead, palladium; n is one of hydroxyl, carbonate, bicarbonate, phosphate and biphosphate, and the alkali can be a mixture of various alkalis; the hydrolysis temperature is 25-250 ℃, and the addition amount of the alkali is 0.1-10.0 molar equivalents of the compound II; on the premise of not affecting the purpose of the application, solvents such as water, alcohols, ethers, esters, nitriles and the like can be added for hydrolysis reaction; the addition amount of the solvent is 1 to 50.0 times of the mass of the compound II; after the hydrolysis is completed, the high-temperature heating decarboxylation is carried out, and the heating temperature is 100-250 ℃.
In one embodiment, in the step of hydrolyzing by adding a base, the base is potassium hydroxide and the solvent is dichloromethane and methanol; after the hydrolysis is completed, the high-temperature heating decarboxylation is carried out, and the heating temperature is 160-210 ℃.
When COOC is removed under the conditions of DMSO and a catalyst b H c X d When the catalyst is metal halide, the metal is one of sodium, potassium, iron, calcium, lithium, barium, copper, lead and palladium; the removal temperature is 100-250 ℃, and the addition amount of the catalyst is 0.1-10.0 molar equivalents of the compound II.
In one embodiment, the catalyst is sodium chloride, the removal temperature is 140-180 ℃, and the catalyst is added in an amount of 0.1-1 molar equivalent of the compound II.
The term "DMSO" refers to dimethyl sulfoxide.
When heating at high temperature to remove COOC b H c X d When the temperature is 150-300 ℃; preferably, the heating temperature is 200 to 250 ℃.
Preparation of Compound II from Compound III
The preparation raw materials of the compound II comprise: compound III and acrylonitrile; the structural formula of the compound III isWherein a is an integer of 3-12, b is not less than 1, c is not less than 1, d is not less than 0, and X is a heteroatom.
Preferably, a is an integer of 3 to 12, b is 1 to 8,c.gtoreq.3, and d is 0.
More preferably, a is an integer from 3 to 8, b is 2, c is 5,d and 0; further preferably, a is an integer of 3 to 6, b is 2, c is 5,d and 0.
The preparation method of the compound II comprises the following steps: reacting a compound III with acrylonitrile in a first inorganic base and/or a first organic strong base system; wherein the reaction temperature is 0-150 ℃; the mol ratio of the compound III to the acrylonitrile is 0.1-10:1, a step of; the addition amount of the first inorganic base or the first organic strong base is 0.01-2.0 mol equivalent of the compound III. Preferably, the reaction temperature is 20-100 ℃; preferably, the molar ratio of the compound III to the acrylonitrile is 0.1-2:1.
the first organic strong base comprises at least one of 1, 8-diazabicyclo undec-7-ene (DBU for short), 1, 3-tetramethyl guanidine and N-methylmorpholine; the cation of the first inorganic base comprises one of sodium, potassium, iron, calcium, lithium, barium, copper, lead and palladium, and the anion comprises one of hydroxide, carbonate, bicarbonate, hydrogen, methoxy, ethoxy, tert-butoxy, diisopropyl, amino, n-butyl, tert-butyl and isobutyl. Preferably, the first inorganic base includes one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide, and sodium hydride.
Water and/or an organic solvent including at least one of methanol, ethanol, isopropanol, butanol, acetonitrile, butyronitrile, diethyl ether, butyl ether, methylethyl ether, methylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1, 4-dioxane, benzene, toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, dichloroethane, trichloromethane, trichloroethane, tetrachloroethane, trichloropropane, tetrachloroethylene, ethyl acetate, butyl acetate, isopropyl acetate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone may also be added without affecting the object of the present application. The addition amount of the solvent is 1-10 times of the total mass of the compound III and the acrylonitrile.
Preparation of Compound III from Compound IV
The preparation raw materials of the compound III comprise: compound IV and compound V; the structural formula of the compound V isThe structural formula of the compound IV is +.>Wherein a is an integer of 3-12, b is more than or equal to 1, c is more than or equal to 1, d is more than or equal to 0, X is a heteroatom, and Y is selected from one of halogen, alkylsulfonyl, alkylarylsulfonyl, haloalkylsulfonyl and haloalkylphenylsulfonyl.
Preferably, a is an integer of 3-12, b is 1-8,c ≡4, d is 0, and Y is selected from one of halogen, alkylsulfonyl, alkylaryl sulfonyl, haloalkylsulfonyl and haloalkylphenyl sulfonyl.
More preferably, a is an integer from 3 to 8, b is 2, c is 5,d and 0; further preferably, a is an integer of 3 to 6, b is 2, c is 5,d, and Y is selected from one of Cl, alkylaryl sulfonyl, fluoroalkyl phenylsulfonyl.
The preparation method of the compound III comprises the following steps: reacting the compound IV with the compound V in a second inorganic base and/or a second organic strong base system; wherein the reaction temperature is 50-250 ℃; the molar ratio of the compound IV to the compound V is 0.1-100:1, a step of; the addition amount of the second inorganic base or the second organic strong base is 0.1-10.0 molar equivalents of the compound IV.
Preferably, the reaction temperature is 50-200 ℃; the molar ratio of the compound IV to the compound V is 0.1-10:1, a step of; the addition amount of the second inorganic base or the second organic strong base is 0.1-5.0 mol equivalent of the compound IV.
The second organic strong base comprises at least one of 1, 8-diazabicyclo undec-7-ene (DBU for short), 1, 3-tetramethyl guanidine and N-methylmorpholine; the cation of the second inorganic base comprises one of sodium, potassium, iron, calcium, lithium, barium, copper, lead and palladium, and the anion comprises one of hydroxide, carbonate, bicarbonate, hydrogen, methoxy, ethoxy, tert-butoxy, diisopropyl, amino, n-butyl, tert-butyl and isobutyl. Preferably, the second inorganic base includes one of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium methoxide, sodium tert-butoxide, and sodium hydride.
Water and/or an organic solvent including at least one of methanol, ethanol, isopropanol, butanol, acetonitrile, butyronitrile, diethyl ether, butyl ether, methylethyl ether, methylbutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, ethylene glycol dibutyl ether, ethylene glycol methyl butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, tetrahydrofuran, 1, 4-dioxane, benzene, toluene, chlorobenzene, dichlorobenzene, trichlorobenzene, dichloromethane, dichloroethane, trichloromethane, trichloroethane, tetrachloroethane, trichloropropane, tetrachloroethylene, ethyl acetate, butyl acetate, isopropyl acetate, dimethyl carbonate, methyl ethyl carbonate, diethyl carbonate, ethylene carbonate, propylene carbonate, N-dimethylformamide, N-dimethylacetamide, hexamethylphosphoramide, N-methylpyrrolidone may also be added without affecting the object of the present application. The addition amount of the solvent is 1-20 times of the total mass of the compound V and the compound IV.
The second aspect of the present application provides a high purity aliphatic tri-nitrile obtained by the preparation method.
The present application will be specifically described below by way of examples. It is noted herein that the following examples are given solely for the purpose of further illustration and are not to be construed as limitations on the scope of the application, as will be apparent to those skilled in the art in light of the foregoing disclosure.
In addition, the raw materials used are commercially available unless otherwise indicated.
Examples
Example 1
Preparation of ethyl 2, 5-dicyano-2-cyanoethyl-pentanoate (Compound II)
(1) Preparation of ethyl 2, 5-dicyanovalerate (compound III): 113 g of ethyl cyanoacetate, 104 g of 4-chlorobutyronitrile, 160 g of potassium carbonate, 500 g of N, N-dimethylformamide are reacted for 6 hours at 150-160 ℃, concentrated, 500 g of dichloromethane are added, 500 g of water is washed, layering, filtrate concentration and distillation are carried out, 160 g of ethyl 2, 5-dicyanovalerate is obtained, and the yield is 88.9%.
HNMR data: (cdcl 3,400 mhz): 1.31 (t, j=8.00 hz, 3H), 1.87 (m, 2H), 2.10 (m, 2H), 2.45 (t, j=8.00 hz, 2H), 3.57 (t, j= 8.00,1H), 4.27 (q, j=8.00 hz, 2H).
(2) Preparation of ethyl 2, 5-dicyano-2-cyanoethyl-pentanoate (compound II): 160 g of ethyl 2, 5-dicyanovalerate is put into 480 g of toluene, 5 g of sodium methoxide is added, 47 g of acrylonitrile is added dropwise at the temperature of 60 ℃, the temperature is kept for 1 hour after the dripping, hydrochloric acid is added for quenching reaction, and the mixture is concentrated in a layering way, so that 200 g of ethyl 2, 5-dicyano-2-cyanoethyl-valerate is obtained, and the yield is 96.6%;
HNMR data: (cdcl 3,400 mhz): 1.35 (t, j=8.00 hz, 3H), 1.72 (m, 1H), 1.93 (m, 2H), 2.15 (m, 2H), 2.36 (m, 1H), 2.45 (t, j=8.00 hz, 2H), 2.50 (m, 1H), 2.59 (m, 1H), 4.32 (q, j= 8.00,2H).
Example 2
Preparation of ethyl 2, 5-dicyano-2-cyanoethyl-pentanoate (Compound II)
(1) Preparation of ethyl 2, 5-dicyanovalerate (compound III): 113 g of ethyl cyanoacetate, 500 g of N-methylpyrrolidone, 100 g of sodium tert-butoxide are added at a temperature of 40 ℃, after the addition is completed, 250 g of N-butyronitrile p-toluenesulfonate (CAS number 107289-42-9) is added at a temperature of 40 ℃ for reaction for 2 hours at a temperature of 110-120 ℃, the mixture is concentrated, 500 g of dichloromethane is added, 500 g of water is washed, layering is carried out, the filtrate is concentrated, 165 g of ethyl 2, 5-dicyanovalerate is obtained by distillation, and the yield is 91.7%.
HNMR data: (cdcl 3,400 mhz) 1.31 (t, j=8.00 hz, 3H), 1.87 (m, 2H), 2.10 (m, 2H), 2.45 (t, j=8.00 hz, 2H), 3.57 (t, j= 8.00,1H), 4.27 (q, j=8.00 hz, 2H).
(2) Preparation of ethyl 2, 5-dicyano-2-cyanoethyl-pentanoate (compound II): 165 g of ethyl 2, 5-dicyanovalerate is put into 480 g of 1, 2-dichloroethane, 5 g of sodium hydroxide is added, 49 g of acrylonitrile is added dropwise at the temperature of 60 ℃, the temperature is kept for 1 hour after the completion of the dripping, hydrochloric acid is added for quenching reaction, the mixture is concentrated in layers, 210 g of ethyl 2, 5-dicyano-2-cyanoethyl-valerate is obtained, the yield is 98.3%,
HNMR data: (cdcl 3,400 mhz) 1.35 (t, j=8.00 hz, 3H), 1.72 (m, 1H), 1.93 (m, 2H), 2.15 (m, 2H), 2.36 (m, 1H), 2.45 (t, j=8.00 hz, 2H), 2.50 (m, 1H), 2.59 (m, 1H), 4.32 (q, j= 8.00,2H).
Example 3
Preparation of ethyl 2, 5-dicyano-2-cyanoethyl-pentanoate (Compound II)
(1) Preparation of ethyl 2, 5-dicyanovalerate (compound III): 40 g of 60% sodium hydride (60% sodium hydride means 60% sodium hydride and 40% mineral oil) is added into 500 g of tetrahydrofuran, then 113 g of ethyl cyanoacetate is added dropwise at the temperature of 40 ℃, the mixture is stirred for 1 hour at room temperature after the dripping is finished, then 220 g of nitrile triflate is added dropwise at the temperature of 40 ℃, the mixture is refluxed for 2 hours after the dripping is finished, the mixture is concentrated under reduced pressure, 500 g of dichloromethane and 500 g of water are added, the mixture is layered, the filtrate is concentrated and distilled to obtain 158 g of ethyl 2, 5-dicyanovalerate, and the yield is 87.8%.
HNMR data: (cdcl 3,400 mhz) 1.31 (t, j=8.00 hz, 3H), 1.87 (m, 2H), 2.10 (m, 2H), 2.45 (t, j=8.00 hz, 2H), 3.57 (t, j= 8.00,1H), 4.27 (q, j=8.00 hz, 2H).
(2) Preparation of ethyl 2, 5-dicyano-2-cyanoethyl-pentanoate (compound II): 158 g of ethyl 2, 5-dicyanovalerate is put into 480 g of methylene dichloride, 5 g of DBU is added, 47 g of acrylonitrile is added dropwise at the temperature of 60 ℃, the temperature is kept for 1 hour after the dripping, hydrochloric acid is added for quenching reaction, the mixture is concentrated in layers, 201 g of ethyl 2, 5-dicyano-2-cyanoethyl-valerate is obtained, the yield is 98.3%,
HNMR data: (cdcl 3,400 mhz) 1.35 (t, j=8.00 hz, 3H), 1.72 (m, 1H), 1.93 (m, 2H), 2.15 (m, 2H), 2.36 (m, 1H), 2.45 (t, j=8.00 hz, 2H), 2.50 (m, 1H), 2.59 (m, 1H), 4.32 (q, j= 8.00,2H).
Example 4
Preparation of 1,3, 6-hexanetrinitrile
50 g of ethyl 2, 5-dicyano-2-cyanoethyl-valerate prepared in example 1 was taken, 100 g of DMSO was added, 8 g of water was added, naCl2.5 g was added, the temperature was raised to 160℃until no more gas overflowed, after removal of DMSO and water by concentration under reduced pressure, distillation was continued to obtain 1mM Hg, fraction 32.0 g at 195-196℃was obtained, yield 92.8% and GC purity was 99.5%.
Example 5
Preparation of 1,3, 6-hexanetrinitrile
50 g of ethyl 2, 5-dicyano-2-cyanoethyl-valerate prepared in example 1 was taken, 100 g of 10wt% sulfuric acid was added and refluxed at 100℃for 5 hours, after the gas was no longer overflowed, 100 g of methylene chloride was added, the layers were separated, the organic phase was concentrated under reduced pressure, and distillation was continued to obtain a product of 0.5mmHg, 30.1 g of a fraction at 183-184℃was obtained, the yield was 87.2%, and the GC purity was 99.2%.
Example 6
Preparation of 1,3, 6-hexanetrinitrile
50 g of ethyl 2, 5-dicyano-2-cyanoethyl-valerate prepared in example 1 was taken, 100 g of water, 12 g of potassium hydroxide were added, the temperature was raised to reflux for 5 hours, after the gas was no longer overflowed, 100 g of methylene chloride was added, the layers were separated, the organic phase was concentrated under reduced pressure, and distillation was continued to obtain a product of 0.5mmHg, fraction 29.0 g at 184 to 186℃with a yield of 84.1% and GC purity of 99.4%.
Example 7
Preparation of 1,3, 6-hexanetrinitrile
50 g of ethyl 2, 5-dicyano-2-cyanoethyl-valerate prepared in example 1 was taken and placed in a flask, heated to 230℃and gas started to emerge, after no more gas was evolved, distillation gave the product 0.5mmHg, 32.0 g of a fraction at 185-186℃with a yield of 92.8% and a GC purity of 99.4%.
Example 8
Preparation of 1,3, 6-hexanetrinitrile
50 g of ethyl 2, 5-dicyano-2-cyanoethyl-valerate prepared in example 1 is taken, 100 g of methanol and 12 g of potassium hydroxide are added, stirring is carried out for 1 hour at room temperature, 300 g of methylene dichloride is added, hydrochloric acid is added to ensure that the pH value is=5-6, the layers are separated, the organic phase is concentrated under reduced pressure, 46 g of obtained residual liquid is heated to 190 ℃, gas is emitted from the beginning, and after the gas is not emitted any more, the distillation is continued to obtain 0.5mmHg of product, 30.8 g of fraction at 186-187 ℃ is obtained, the yield is 89.3%, and the GC purity is 99.4%.
Example 9
Preparation of ethyl 2, 6-dicyano-2-cyanoethyl-hexanoate (Compound II)
(1) Ethyl 2, 6-dicyanohexanoate (preparation of compound III): 113 g of ethyl cyanoacetate, 118 g of 5-chlorovaleronitrile, 166 g of potassium carbonate, 500 g of N, N-dimethylacetamide and 166-168 ℃ are subjected to reflux reaction for 5 hours, concentrated, 600 g of ethyl acetate is added, 600 g of water is washed, layering and filtrate concentration are carried out, 176 g of ethyl 2, 6-dicyanohexanoate is obtained by distillation, and the yield is 90.6%.
HNMR data: (cdcl 3,400 mhz) 1.27 (t, j=8.00 hz, 3H), 1.64 (m, 4H), 1.93 (m, 2H), 2.35 (t, j=8.00 hz, 2H), 3.51 (t, j= 8.00,1H), 4.21 (q, j=8.00 hz, 1H).
(2) Preparation of ethyl 2, 6-dicyano-2-cyanoethyl-hexanoate (compound II): 176 g of ethyl 2, 6-dicyanohexanoate is put into 480 g of methylene dichloride, 5 g of sodium tert-butoxide is added, 53 g of acrylonitrile is added dropwise at the temperature of 60 ℃, the temperature is kept for 1 hour after the dripping, hydrochloric acid is added for quenching reaction, the mixture is concentrated in layers, 217 g of ethyl 2, 6-dicyano-2-cyanoethyl-hexanoate is obtained, the yield is 96.9%,
HNMR data: (cdcl 3,400 mhz) 1.32 (t, j=8.00 hz, 3H), 1.49 (m, 1H), 1.68 (m, 3H), 1.82 (m, 1H), 1.97 (m, 1H), 2.13 (m, 1H), 2.36 (m, 3H), 2.46 (m, 1H), 2.57 (m, 1H), 4.30 (q, j= 8.00,2H).
Example 10
Preparation of 1,3, 7-heptanetrinitrile
50 g of ethyl 2, 6-dicyano-2-cyanoethyl-hexanoate prepared in example 9 is taken, 100 g of DMSO is added, 8 g of water is added, naCl2.5 g is added, the temperature is raised to 165 ℃, after gas is no longer overflowed, after the DMSO and the water are removed by decompression concentration, distillation is continued to obtain 1mM Hg of product, 31 g of fraction at 200-202 ℃, the yield is 87.5%, the GC purity is 99.5%,
HNMR data: (cdcl 3,400 mhz) 1.32 (m, 6H), 1.94 (m, 2H), 2.36 (t, j=8.00 hz, 2H), 2.53 (m, 2H), 2.72 (m, 1H).
Example 11
Preparation of 1,3, 7-heptanetrinitrile
50 g of ethyl 2, 6-dicyano-2-cyanoethyl-hexanoate prepared in example 9 is taken, 100 g of 10wt% sulfuric acid is added, reflux is carried out at 102 ℃ for 4 hours, after no more gas overflows, 100 g of methylene dichloride is added, the layers are separated, the organic phase is concentrated under reduced pressure, and distillation is continued to obtain 1mmHg of the product, 32.5 g of fraction at 200-202 ℃ is obtained, the yield is 91.7%, the GC purity is 99.5%,
HNMR data: (cdcl 3,400 mhz) 1.32 (m, 6H), 1.94 (m, 2H), 2.36 (t, j=8.00 hz, 2H), 2.53 (m, 2H), 2.72 (m, 1H).
Comparative example
(1) Preparation of ethyl 2, 5-dicyano-2-cyanopropyl-valerate (compound II): 160 g of ethyl 2, 5-dicyanovalerate is put into 480 g of toluene, 5 g of sodium methoxide is added, 104 g of 4-chlorobutyronitrile is added, reflux reaction is carried out for 6 hours at 150-160 ℃, concentration is carried out, 500 g of methylene dichloride is added, 500 g of water washing is carried out, layering and filtrate concentration are carried out, and 2, 5-dicyano-2-cyanopropyl-ethyl valerate is obtained by distillation, the yield is 12%, and the purity is 76%.
The above description is only a preferred embodiment of the present application, and is not intended to limit the application in any way, and any person skilled in the art may make modifications or alterations to the disclosed technical content to equivalent embodiments without departing from the technical content of the present application, and any simple modification, equivalent changes and alterations to the above embodiments according to the technical substance of the present application still fall within the scope of the technical solution of the present application.
Claims (1)
1. A process for preparing an aliphatic tri-nitrile, comprising the steps of: removal of COOC from Compound II b H c X d Obtaining aliphatic tri-nitrile;
the structural formula of the compound II is as follows:wherein a is an integer from 3 to 8, b is 2, c is 5,d is 0, e is 2, and X is a heteroatom;
the preparation raw materials of the compound II comprise: compound III and acrylonitrile; the structural formula of the compound III isWherein a is an integer from 3 to 8, b is 2, c is 5,d is 0, and X is a heteroatom; the preparation method of the compound II comprises the following steps: the compound III and acrylonitrile react in a first inorganic base and/or a first organic alkali system; the reaction temperature is 0-150 ℃, and the mol ratio of the compound III to the acrylonitrile is 0.1-10:1, a step of; the addition amount of the first inorganic base or the first organic strong base is 0.01-2.0 mol equivalent of the compound III;
the compound II removes COOC b H c X d The method of (2) is selected from one of the following: (1) COOC removal under acidic conditions b H c X d The method comprises the steps of carrying out a first treatment on the surface of the Wherein the acid is at least one of sulfuric acid, hydrochloric acid, nitric acid and C2-C5 carboxylic acid, the removal temperature is 50-150 ℃, and the addition amount of the acid is 0.1-10.0 molar equivalents of the compound II; (2) COOC removal under alkaline conditions b H c X d The method comprises the steps of carrying out a first treatment on the surface of the The removal temperature is 50-200 ℃, and the addition amount of the alkali is 0.1-5 molar equivalents of the compound II; (3) hydrolysis followed by decarboxylation by heating; hydrolyzing by adding alkali, wherein the hydrolysis temperature is 25-250 ℃, and the addition amount of the alkali is 0.1-10.0 molar equivalents of the compound II; (4) COOC removal by DMSO and catalyst b H c X d The method comprises the steps of carrying out a first treatment on the surface of the The catalyst is metal halide, the removal temperature is 100-250 ℃, and the addition amount of the catalyst is 0.1-10.0 molar equivalents of the compound II; (5) High-temperature heating COOC removal b H c X d The method comprises the steps of carrying out a first treatment on the surface of the The heating temperature is 200-250 ℃;
the preparation raw materials of the compound III comprise: compound IV and compound V; the structural formula of the compound V isThe structural formula of the compound IV is +.>Wherein a is an integer of 3-8, b is 2, c is 5,d, X is a heteroatom, and Y is selected from one of halogen, alkylsulfonyl, alkylaryl sulfonyl, haloalkylsulfonyl and haloalkylphenylsulfonyl;
the preparation method of the compound III comprises the following steps: the compound IV and the compound V react in a second inorganic base and/or a second organic alkali system; wherein the reaction temperature is 50-250 ℃; the molar ratio of the compound IV to the compound V is 0.1-100:1, a step of; the addition amount of the second inorganic base or the second organic strong base is 0.1-10.0 molar equivalents of the compound IV.
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