CN110003047B - Method for preparing nitrile by reacting acetone cyanohydrin with alkyl halide - Google Patents
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Abstract
The invention provides a method for preparing nitrile by reacting acetone cyanohydrin with alkyl halide. The invention uses acetone cyanohydrin as a cyaniding reagent, and solves the problems of long reaction time, low yield, strict reaction conditions and the like of the existing preparation method which uses virulent sodium cyanide, potassium cyanide or expensive trimethyl silicon cyanide as a cyanogen source. The method comprises the following steps: dissolving acetone cyanohydrin in a mixed solvent composed of an aprotic high boiling point dipolar solvent and an aprotic low boiling point solvent, adding a catalyst lithium hydroxide, stirring for one hour at 25-50 ℃, adding alkyl halide, continuing to react for 2-3 hours, adding saturated saline solution, washing twice, separating an organic layer, drying, and evaporating the solvent to obtain the nitrile compound. The method for preparing the nitrile compound has the advantages of low reaction toxicity, simple process, easy operation, low production cost and yield of more than 95 percent.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and relates to a method for preparing nitrile by reacting acetone cyanohydrin with alkyl halide.
Background
Nitrile is a cyano-containing organic substance, is an important chemical raw material, and has important application in the fields of medicines, new materials and the like, wherein a representative compound such as adiponitrile is a raw material for preparing nylon 66, and phenylacetonitrile is an intermediate for producing various medicines and pesticides; acrylonitrile can be copolymerized with other monomers to produce synthetic rubbers and engineering plastics, etc.
Many methods are available for preparing nitriles, but the most common method is to prepare nitriles by nucleophilic substitution reaction of aliphatic halohydrocarbons with metal cyanides. The method has the limitations that (1) metal cyanide is virulent sodium cyanide and potassium cyanide, so that the problems of serious environmental pollution, personal safety and the like are caused; (2) sodium cyanide/potassium cyanide belong to inorganic salts, are almost insoluble in organic solvents, and need to be added with phase transfer catalysts such as tetrabutylammonium bromide, hexadecyltrimethylammonium, 18-crown 6 ether and the like, so that the production cost is increased; (3) when the reactant is tertiary alkyl halide, the reaction is mainly to eliminate the product, resulting in lower yield of the substituted product; (4) when the reactant is alkyl halide with weak reaction activity, such as alkyl chloride or alkyl bromide, potassium iodide or sodium iodide is needed to be added as a cocatalyst. In order to overcome the defects of the reaction, trimethyl silylcyanide is mostly used as a cyaniding reagent in the laboratory at present, but the material is expensive, the atom utilization rate is low, and the reaction is required to be carried out under strict anhydrous and oxygen-free conditions, so that the industrial production requirement cannot be met.
The acetone cyanohydrin is relatively safe and replaces virulent cyaniding reagents such as hydrocyanic acid (the death causing amount of human beings is 0.57mg/kg), sodium cyanide, potassium cyanide (the LD50 of the acetone cyanohydrin is 52mg/kg, and the LD50 of the sodium cyanide is 6mg/kg), and the like, so that the problems of environmental pollution, personal safety and the like caused by the use of the acetone cyanohydrin are avoided; the acetone cyanohydrin is a byproduct in acrylonitrile production, is low in price, replaces expensive cyaniding reagent with the acetone cyanohydrin, greatly reduces the production cost, and has more practical value. The existing method for preparing cyanide by nucleophilic substitution reaction of alkyl halide by using acetone cyanohydrin as a cyanogen source is few, and the catalyst used in the existing report is the unusual strong organic base tetramethyl guanidine or the water-repellent and inflammable lithium hydride.
Disclosure of Invention
The invention aims to solve the problems that virulent sodium cyanide and potassium cyanide catalysts or expensive trimethyl silicon cyanide with poor atom economy is used as a cyanide source, the reaction time is long, the yield is low, the reaction conditions are strict and the like in the conventional method for preparing nitrile by using alkyl halide. Provides a new method for preparing nitrile by utilizing nucleophilic substitution reaction of alkyl halide and acetone cyanohydrin.
The invention relates to a method for preparing nitrile by utilizing nucleophilic substitution reaction of acetone cyanohydrin and alkyl halide, which comprises the following steps:
dissolving acetone cyanohydrin in mixed solvent composed of aprotic high boiling point dipolar solvent and aprotic low boiling point solvent, adding lithium hydroxide as catalyst, stirring at 25-50 deg.C for one hour, adding alkyl halide, and monitoring by TLCAfter the materials disappeared, washing with water, extracting with ethyl acetate, washing ethyl acetate layer with water and saturated brine, and washing with anhydrous Na2SO4After drying, the nitrile is obtained by filtration and concentration.
Further the cyanating reagent is acetone cyanohydrin.
Further the molar ratio of acetone cyanohydrin to alkyl halide is 1.1-1.5: 1.
The catalyst is further lithium hydroxide monohydrate, and the molar ratio of the lithium hydroxide monohydrate to the alkyl halide is 1.1-1.5: 1.
Further said alkyl halides are primary and secondary alkyl halides.
Further said alkyl halides are alkyl chlorides, bromides and iodides, wherein the alkyl halides can be, but are not limited to, the following compounds: benzyl chloride, n-butyl chloride, sec-butyl chloride, 1, 4-dichlorobutane, 1-chlorooctane, ethyl 3-chloropropionate, 1-chloro-2-phenylethane, 3-chloropropionitrile, 1, 2-dichloroethane and chlorododecane; n-butyl bromide, sec-butyl bromide, 1, 4-dibromobutane, 1-bromo-3-phenylpropane, 3-bromopropionitrile, benzyl bromide, methyl 3-bromo-propionate, 1-bromoethylbenzene, methyl 4-bromobutyrate, n-octane bromide, octadecylene bromide, diphenylmethane bromide, 2-bromopentane, ethyl 7-bromoheptanoate, and 1, 2-dibromoethane; n-butyl iodide, n-octane iodide and tetradecane iodide.
Further the reaction temperature is 25-50 deg.C, preferably 50 deg.C.
The reaction solvent is a mixed solvent consisting of an aprotic high-boiling point dipolar solvent and an aprotic low-boiling point solvent, wherein the aprotic high-boiling point dipolar solvent is 1, 3-dimethyl imidazolidinone, N-methyl pyrrolidone and hexamethylphosphoric triamide; the low boiling point solvent is dichloromethane, chloroform, acetone, acetonitrile, tetrahydrofuran or diethyl ether.
Further, the ratio of the mixed solvent is such that the volume ratio of the aprotic high-boiling dipolar solvent to the aprotic low-boiling solvent is 1:2 to 1:7, preferably 1: 3.
The reaction principle of the invention is as follows: the acetone cyanohydrin can generate nucleophilic substitution reaction with alkyl halide to prepare nitrile under the catalysis of lithium hydroxide monohydrate.
The invention has the beneficial effects that:
the invention uses acetone cyanohydrin as a cyanogen source to replace highly toxic sodium cyanide and potassium cyanide; replaces expensive cyaniding reagents such as trimethyl cyanogen silane.
The method has the advantages of mild reaction conditions, short reaction time and high reaction yield of over 95 percent.
The invention uses low-price lithium hydroxide monohydrate as the catalyst, and has simple process and lower production cost.
Drawings
FIG. 1 is the NMR spectrum of phenylacetonitrile in example one;
FIG. 2 is the NMR carbon spectrum of phenylacetonitrile in example one;
FIG. 3 is an IR spectrum of phenylacetonitrile according to example I.
FIG. 4 is a nuclear magnetic resonance hydrogen spectrum of succinonitrile of example C;
FIG. 5 is a NMR carbon spectrum of succinonitrile of example C;
FIG. 6 is an IR spectrum of succinonitrile of example ten.
Detailed Description
The technical solution of the present invention is not limited to the following specific embodiments, but includes any combination of the specific embodiments.
The first embodiment is as follows: the method for preparing the nitrile by reacting acetone cyanohydrin with alkyl halide comprises the following specific steps:
dissolving acetone cyanohydrin in mixed solvent composed of aprotic high boiling point dipolar solvent and aprotic low boiling point solvent, adding lithium hydroxide as catalyst, stirring at 25-50 deg.C for one hour, adding alkyl halide, TLC monitoring for disappearance of raw material, washing with water, extracting with ethyl acetate, washing ethyl acetate layer with water and saturated sodium chloride respectively, and washing with anhydrous Na2SO4After drying, the nitrile is obtained by filtration and concentration.
The second embodiment is as follows: the first difference between the present embodiment and the specific embodiment is: the reaction solvent is a mixed solvent consisting of 1, 3-dimethyl imidazolidinone and tetrahydrofuran. The rest is the same as the first embodiment.
The third concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the reaction solvent is a mixed solvent consisting of 1, 3-dimethyl imidazolidinone and dichloromethane. The rest is the same as the first embodiment.
The fourth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the reaction solvent is a mixed solvent consisting of N-methyl pyrrolidone and acetone: the rest is the same as the first embodiment.
The fifth concrete implementation mode: the first difference between the present embodiment and the specific embodiment is: the volume ratio of the mixed solvent consisting of 1, 3-dimethyl imidazolidinone and tetrahydrofuran is 1: 2. the rest is the same as the first embodiment.
The sixth specific implementation mode is as follows: the first difference between the present embodiment and the specific embodiment is: the volume ratio of the mixed solvent consisting of 1, 3-dimethyl imidazolidinone and tetrahydrofuran is 1: 5. the rest is the same as the first embodiment.
The seventh embodiment: the first difference between the present embodiment and the specific embodiment is: the volume ratio of the mixed solvent consisting of 1, 3-dimethyl imidazolidinone and tetrahydrofuran is 1: 7. the rest is the same as the first embodiment.
The specific implementation mode is eight: the first difference between the present embodiment and the specific embodiment is: the molar ratio of the catalyst lithium hydroxide monohydrate to the alkyl halide was 1.3: 1. The rest is the same as the first embodiment.
The specific implementation method nine: the first difference between the present embodiment and the specific embodiment is: the molar ratio of the catalyst lithium hydroxide monohydrate to the alkyl halide was 1.5: 1. The rest is the same as the first embodiment.
The detailed implementation mode is ten: the first difference between the present embodiment and the specific embodiment is: the molar ratio of acetone cyanohydrin to alkyl halide was 1.2: 1. The rest is the same as the first embodiment.
The concrete implementation mode eleven: the first difference between the present embodiment and the specific embodiment is: the molar ratio of acetone cyanohydrin to alkyl halide is 1.5: 1. The rest is the same as the first embodiment.
The specific implementation mode twelve: the first difference between the present embodiment and the specific embodiment is: the reaction temperature was 50 ℃. The rest is the same as the first embodiment.
The specific implementation mode is thirteen: the present embodiment differs from the first to twelfth embodiments in that: the alkyl halide is benzyl chloride, n-butyl chloride, sec-butyl chloride, 1, 4-dichlorobutane, 1-chlorooctane, 3-chloropropionic acid ethyl ester, 1-chloro-2-phenylethane, 3-chloropropionitrile, 1, 2-dichloroethane, chlorododecane; n-butyl bromide, sec-butyl bromide, 1, 4-dibromobutane, 1-bromo-3-phenylpropane, 3-bromopropionitrile, benzyl bromide, methyl 3-bromo-propionate, 1-bromoethylbenzene, methyl 4-bromobutyrate, n-octane bromide, octadecylene bromide, diphenylmethane bromide, 2-bromopentane, ethyl 7-bromoheptanoate, and 1, 2-dibromoethane; n-butyl iodide, n-octane iodide and tetradecane iodide. The rest of the description is the same as the first to twelfth embodiments.
The following examples are given to illustrate the present invention, and the following examples are carried out on the premise of the technical solution of the present invention, and give detailed embodiments and specific procedures, but the scope of the present invention is not limited to the following examples.
Example 1:
the method for preparing nitrile by reacting acetone cyanohydrin with alkyl halide is characterized by comprising the following steps:
dissolving 1.5mol of acetone cyanohydrin in a mixed solvent composed of 1, 3-dimethyl imidazolidinone and tetrahydrofuran (volume ratio is 1:3), adding 1.5mol of catalyst lithium hydroxide monohydrate, stirring at 50 ℃ for one hour, adding 1mol of benzyl bromide, monitoring by TLC (thin layer chromatography) for disappearance of raw materials, adding water for washing, extracting with ethyl acetate, washing the ethyl acetate layer with water and saturated saline respectively, and washing with anhydrous Na2SO4Drying, filtering and concentrating to obtain the benzyl cyanide product. The reaction time was 2.5h, and the yield was 97%.
Nuclear magnetic resonance hydrogen spectrum (300 MH) of phenylacetonitrileZ，CDCl3In ppm) as shown in FIG. 1: 7.39-7.32(m,5H),3.75(s, 2H).
Nuclear magnetic resonance carbon spectrum of phenylacetonitrile(75MHZ，CDCl3In ppm) as shown in FIG. 2: 129.9,128.9,127.8,127.7,117.8,23.3
Infrared Spectrum of benzyl cyanide (KBr coating method, unit: cm)-1) As shown in fig. 3: 3068,3034,2251,1603,1497,1454,1417,1078,1030,740
The structure of the synthesized compound is correct by combining the hydrogen spectrum, the carbon spectrum and the infrared spectrum of the compound.
Example 2: all experimental conditions and workup procedures in this example were the same as in example 1 except that benzyl bromide was changed to benzyl chloride, the reaction time was 4.5h and the yield was 95.6%.
Example 3: in this example, all the experimental conditions and the treatment method were the same as in example 1 except that the mixed solvent of 1, 3-dimethylimidazolidinone and tetrahydrofuran was changed to the mixed solvent of 1, 3-dimethylimidazolidinone and methylene chloride, the reaction time was 5.5 hours, and the yield was 95.7%.
Example 4: in this example, all experimental conditions and treatment methods were the same as in example 1 except that the mixed solvent of 1, 3-dimethylimidazolidinone and tetrahydrofuran was changed to a mixed solvent of N-methylpyrrolidone and acetone, the reaction time was 3.5 hours, and the yield was 96.3%.
Example 5: all experimental conditions and treatment methods of this example were the same as those of example 1 except that the mixed solvent of 1, 3-dimethylimidazolidinone and tetrahydrofuran was changed to a mixed solvent of hexamethylphosphoric triamide and diethyl ether, the reaction time was 5 hours, and the yield was 95.2%.
Example 6: in this example, all experimental conditions and treatment methods were the same as in example 1 except that the volume ratio of the mixed solvent of 1, 3-dimethylimidazolidinone and tetrahydrofuran was changed to 1:5 from 1:3, the reaction time was 3.5 hours, and the yield was 96.7%.
Example 7: all experimental conditions and workup procedures in this example were the same as in example 1 except that the molar ratio of lithium hydroxide monohydrate to benzyl bromide catalyst was changed to 1.5:1 to 1.3:1, the reaction time was 4.5h and the yield was 96.2%.
Example 8: all experimental conditions and workup procedures in this example were the same as in example 1 except that the molar ratio of acetone cyanohydrin to benzyl bromide was changed to 1.2:1 at 1.5:1, the reaction time was 4h and the yield was 95.9%.
Example 9: all experimental conditions and treatment procedures in this example were the same as in example 1 except that the temperature was changed from 50 ℃ to 25 ℃ and the reaction time was 5 hours, giving a yield of 95.3%.
Example 10: all experimental conditions and workup procedures in this example were the same as in example 1 except that benzyl bromide was changed to 3-chloropropionitrile, the reaction time was 3.5h and the yield was 98%. Nuclear magnetic resonance hydrogen spectrum (300 MH) of product butanedinitrileZ，CDCl3In ppm) as shown in FIG. 4: 2.76(s, 4H); nuclear magnetic resonance carbon spectrum (75 MH) of succinonitrileZ，CDCl3Unit ppm) is shown in fig. 5: 116.2, 14.7; infrared Spectrum of succinonitrile (KBr coating method, unit: cm)-1) As shown in fig. 6: 3465,2989,2955,2254,1427,1003,964,822,762,605.
Example 11: all experimental conditions and workup procedures in this example were the same as in example 1 except that benzyl bromide was changed to 1-chloro-2-phenylethane, the reaction time was 2.5h and the yield was 97.9%. Nuclear magnetic resonance hydrogen spectrum data (300 MH) of phenylpropionitrile productZ，CDCl3Unit ppm): 7.36-7.24(m,5H),2.97(t, J ═ 7.36Hz,2H),2.63(t, J ═ 7.40Hz, 2H); NMR carbon spectrum data of benzonitrile (75 MH)Z，CDCl3Unit ppm): 138.1,128.9,128.2,127.2,119.1,31.5, 19.3; infrared spectrum data of benzonitrile (KBr coating method, unit: cm)-1)：3087,3069,3030,2868,2246,1604,1496,1454,1425,1079,1340,749。
Example 12: all experimental conditions and workup procedures in this example were the same as in example 1 except that the benzyl bromide was changed to ethyl 3-chloropropionate, the reaction time was 3.5h and the yield was 95.9%. NMR hydrogen spectrum data (300MHz, CDCl3, unit ppm) of ethyl 3-cyanopropionate product: 4.19(q, J ═ 7.09Hz,2H), 2.65(s, 4H), 1.27(t, J ═ 7.13Hz, 3H); NMR carbon Spectroscopy data for Ethyl 3-Cyanopropionate (75 MH)Z，CDCl3Unit ppm): 170.0,118.5,61.5,30.0,14.1, 12.6; infrared spectroscopic data of ethyl 3-cyanopropionate (KBr coating method, unit: cm)-1)：2927,2854,2251,1736,1691,1422,1377,1199,1114,1018,854,617。
Example 13: all experimental conditions and procedures of this example were the same as in example 1 except that benzyl bromide was changed to chlorooctadecane, the reaction time was 4.5h, and the yield was 95.1%. NMR Hydrogen Spectroscopy data for product N-nonadecylnitrile (300MHz, CDCl3, units ppm): 2.33(t, J ═ 7.03,2H), 1.68-1.63(m2H),1.49-1.44(m,2H),1.26(s,28H),0.88(t, J ═ 5.54Hz, 3H); NMR carbon Spectroscopy data for N-nonadecylnitrile (75 MH)Z，CDCl3Unit ppm): 119.9,32.0,29.7,29.6,29.4,28.8,28.7,25.4, 22.7,17.2, 14.2; infrared spectroscopic data of N-nonadecylanecarbonitrile (KBr coating method, unit: cm)-1)：3064,3032,2987,2938,2877,2242,1958,1896,1669,1385,752,570。
Example 14: all experimental conditions and workup procedures in this example were the same as in example 1 except that benzyl bromide was changed to diphenylmethane bromide, the reaction time was 4.5h, and the yield was 95.2%. Nuclear magnetic resonance hydrogen spectrum data (300 MH) of diphenylacetonitrile productZ，CDCl3Unit ppm): 7.35(m,10H),5.14(s, 1H); nuclear magnetic resonance carbon spectrum data of diphenylacetonitrile (75 MH)Z，CDCl3Unit ppm): 135.9,129.2,128.3,127.8, 42.8; infrared Spectrum data of diphenylacetonitrile (KBr pellet method, unit: cm)-1)3027,2933,2852,2243,1658,1597,1492,1118,1079,744,697,540。
Example 15: all experimental conditions and workup procedures in this example were the same as in example 1 except that benzyl bromide was changed to 1-bromo-3-phenylpropane, the reaction time was 3 hours, and the yield was 96%. Nuclear magnetic resonance hydrogen spectrum data (300 MH) of product 4-phenylbutyronitrileZ，CDCl3Unit ppm): 7.36-7.17(m,5H),2.80-2.75(t, J ═ 7.40Hz,2H),2.34-2.29(t, J ═ 7.09Hz,2H),2.00-1.95(m, 2H); 4-Phenylbutyronitrile NMR carbon spectrum data (75 MH)Z，CDCl3Unit ppm): 139.7,128.6,128.4,126.5,119.5,34.3,26.9, 16.3; 4-Phenylbutyronitrile infrared spectrum data (KBr coating method, unit: cm)-1)：3085,3069,3029,2928,2867,2246,1603,1497,1455,1425,1082,1030,748,701。
Example 16: all experimental conditions and treatment methods and examples of this exampleThe same as in example 1, except that the benzyl bromide was changed to ethyl 7-bromoheptanoate, the reaction time was 4h, and the yield was 96.8%. Preparation of product ethyl 7-cyanoheptanoate: nuclear magnetic resonance hydrogen spectroscopy data (300 MH)Z，CDCl3Unit ppm): 4.15-4.11(q, J ═ 7.02Hz,2H),2.34-2.27(t, J ═ 11.72Hz,4H),1.66-1.61(m,4H),1.47-1.40(t, J ═ 5.39Hz 2H),1.38-1.35(m,2H),1.27-1.22(t, J ═ 7.04Hz, 3H); nuclear magnetic resonance carbon spectrum data (75 MH) of ethyl 7-cyanoheptanoateZ，CDCl3Unit ppm): 173.4,119.6,132.4,60.1,34.0,28.2,28.1,25.0,24.4,16.9, 14.1; infrared spectroscopic data of ethyl 7-cyanoheptanoate (KBr film coating method, unit: cm)-1)：2936,2863,2245,1732,1464,1373,1252,1187,1096,1033。
Example 17: all experimental conditions and workup procedures in this example were the same as in example 1 except that benzyl bromide was changed to 1, 4-dibromobutane, the reaction time was 3 hours, and the yield was 97.9%. Nuclear magnetic resonance hydrogen spectrum (300 MH) of adiponitrile productZ，CDCl3Unit ppm): 2.44-2.41(m, 4H); 1.83-1.81(m, 4H); nuclear magnetic resonance carbon Spectroscopy (75 MH) of adiponitrileZ，CDCl3Unit ppm): 118.72, 24.21, 16.59; infrared Spectrum of adiponitrile (KBr coating method, Unit: cm)-1)：2949,2881,2249,1697,1462,1427,1335,898,766。
Example 18: all experimental conditions and procedures of this example were the same as in example 13 except that 1, 4-dibromobutane was changed to 1, 4-dichlorobutane, the reaction time was 4.5 hours, and the yield was 95.3%.
Example 19: all experimental conditions and workup procedures in this example were the same as in example 1 except that benzyl bromide was changed to methyl 3-bromopropionate and the reaction time was 3.5h, the yield was 98.2%. Nuclear magnetic resonance hydrogen spectrum (300 MH) of product methyl 3-cyanopropionateZ，CDCl3Unit ppm): 3.73(s, 3H), 2.70-2.61(m, 4H); nuclear magnetic resonance carbon Spectroscopy (75 MH) of methyl 3-cyanopropionateZ，CDCl3Unit ppm): 170.4,118.4,52.3,29.8, 13.0; infrared Spectrum of methyl 3-cyanopropionate (KBr coating method, Unit: cm)-1)：3328,2959,2251,1667,1576,1506,1387,1279,1181,950,883,682。
Example 20: in this embodimentExperimental conditions and treatment were the same as in example 1 except that benzyl bromide was changed to n-butyl iodide, the reaction time was 3.5 hours, and the yield was 95.5%. Nuclear magnetic resonance hydrogen spectrum data (300 MH) of product valeronitrileZ，CDCl3Unit ppm): 2.34(t, J ═ 7.02Hz,2H), 1.67-1.59(m, 2H),1.52-1.44(m,2H),0.92(t, J ═ 7.20Hz, 3H); carbon nuclear magnetic resonance data (75 MH) of valeronitrileZ，CDCl3Unit ppm): 119.8,27.4,21.8,16.8, 13.2; infrared spectrum data of valeronitrile (KBr film coating method, unit: cm)-1)：2992,2941,2243,1460,1382,1190,1141,976,876,696,596,475。
Example 21: all experimental conditions and treatment procedures of this example were the same as in example 1 except that benzyl bromide was changed to iodo-n-octane, the reaction time was 3.5h, and the yield was 97.2%. NMR data on nonanenitrile product (300 MH)Z，CDCl3Unit ppm): 2.35-2.30(t, J ═ 7.06Hz,2H),1.69-1.60(m,2H),1.43-1.41(m,2H),1.30-1.27(m,8H),0.87-0.85(t, J ═ 6.62Hz, 3H); nuclear magnetic resonance carbon spectrum data (75 MH) of nonanenitrile productZ，CDCl3Unit ppm): 119.9,31.7,29.0,28.7,22.6,17.1, 14.1; infrared spectrum data (KBr film coating method, unit: cm) of nonanenitrile product-1)：2927,2856,2246,1466,1427,1377,723。
Example 22: all experimental conditions and treatment procedures in this example were the same as in example 1 except that benzyl bromide was changed to iodotetradecane, the reaction time was 3 hours, and the yield was 96.6%. Nuclear magnetic resonance hydrogen spectrum data (300 MH) of pentadecanenitrile productZ，CDCl3Unit ppm): 2.33(t, J ═ 7.09Hz,2H), 1.68-1.63(m, 2H),1.44-1.41(m,2H),1.25(s,20H),0.88(t, J ═ 6.17Hz, 3H); nuclear magnetic resonance carbon spectrum data of pentadecanenitrile (75 MH)Z，CDCl3Unit ppm): 119.8,31.9,29.7,29.6,29.5,29.4,29.3,28.7,25.4,22.7,17.1, 14.1; infrared spectrum data of pentadecanenitrile (KBr coating method, unit: cm)-1)：2926,2854,2247,1686,1466,1427,1378,1297,722。
The structure of the synthesized compounds is correct as shown by the product structure data of examples 10-22.
Claims (7)
1. A method for preparing nitrile by reacting acetone cyanohydrin with alkyl halide is characterized by comprising the following steps: dissolving acetone cyanohydrin in mixed solvent composed of aprotic high boiling point dipolar solvent and aprotic low boiling point solvent, adding catalyst lithium hydroxide monohydrate, stirring at 25-50 deg.C for one hour, adding alkyl halide, TLC monitoring for disappearance of raw material, washing with water, extracting with ethyl acetate, washing ethyl acetate layer with water and saturated saline solution, washing with anhydrous Na2SO4After drying, the nitrile is obtained by filtration and concentration.
2. The synthesis process according to claim 1, wherein the molar ratio of acetone cyanohydrin to alkyl halide is 1.1 to 1.5: 1.
3. The synthesis process according to claim 1, wherein the molar ratio of the lithium hydroxide monohydrate to the alkyl halide is from 1.1 to 1.5: 1.
4. The method of synthesis as claimed in claim 1, characterized in that the alkyl halide is a primary alkyl halide or a secondary alkyl halide.
5. The synthesis process according to claim 1 or 4, characterized in that the alkyl halide is an alkyl chloride, alkyl bromide or alkyl iodide, wherein the alkyl chloride is selected from: benzyl chloride, n-butyl chloride, sec-butyl chloride, 1, 4-dichlorobutane, 1-chlorooctane, ethyl 3-chloropropionate, 1-chloro-2-phenylethane, 3-chloropropionitrile, 1, 2-dichloroethane and chlorododecane; the alkyl bromide is selected from: n-butyl bromide, sec-butyl bromide, 1, 4-dibromobutane, 1-bromo-3-phenylpropane, 3-bromopropionitrile, benzyl bromide, methyl 3-bromo-propionate, 1-bromoethylbenzene, methyl 4-bromobutyrate, n-octane bromide, octadecylene bromide, diphenylmethane bromide, 2-bromopentane, ethyl 7-bromoheptanoate, and 1, 2-dibromoethane; the alkyl iodide is selected from: n-butyl iodide, n-octane iodide and tetradecane iodide.
6. The synthesis method according to claim 1, wherein the reaction solvent is a mixed solvent of an aprotic dipolar solvent with a high boiling point and an aprotic dipolar solvent with a low boiling point, wherein the aprotic dipolar solvent with a high boiling point is selected from the group consisting of 1, 3-dimethylimidazolidinone, N-methylpyrrolidone, hexamethylphosphoric triamide; the low boiling point solvent is selected from dichloromethane, chloroform, acetone, acetonitrile, tetrahydrofuran, and diethyl ether.
7. The synthesis method according to claim 1 or 6, wherein the ratio of the mixed solvent is 1:2 to 1:7 by volume of the aprotic high-boiling dipolar solvent to the aprotic low-boiling solvent.
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| CN114456086B (en) * | 2021-12-28 | 2024-10-01 | 哈尔滨理工大学 | Synthesis method of beta-cyano ketone |
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