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Preparation method of cyano tertiary amine

A technology based on tertiary amines and alkyl groups, applied in the field of preparation of cyano tertiary amines, can solve the problems of high toxicity of cyanogen halide, limited wide application, lack of versatility, low yield and the like

Active Publication Date: 2020-11-27
HENAN CHEM IND RES INST +1
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  • Abstract
  • Description
  • Claims
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AI Technical Summary

Problems solved by technology

[0003] Tertiary cyanoamine was first synthesized by Vliet in 1924 through the alkylation reaction of calcium cyanamide (Journal of the American Chemical Society, 1924,46(5):1305-1308). The process is simple, but due to the The low yield limits the wide application of this process
Sun Chenghui (Synlett, 2017, 28 (19): 2675-2679) and Birkinshaw (Journal of the Chemical Society, Perkin Transactions 1, 1984, (0): 147-153) and others used cyanogen bromide as the cyanide reagent to prepare cyanide tertiary amines, the high toxicity of cyanogen halides greatly limits the wide application of this process in the synthesis of tertiary cyanoamines
Andrzej et al. (Synthesis, 1978:882-883) take cyanamide and halogenated hydrocarbon as raw materials, adopt phase transfer catalyst to prepare cyano tertiary amine, this method can not synthesize the different cyano tertiary amine of substituting group, the high toxicity of cyanamide This limits the wide application of the process
[0004] In view of the problems of low yield, high toxicity of raw materials, and lack of versatility in the existing process, it is of great theoretical and practical significance to develop a green cyano-tertiary amine synthesis process with high yield, low toxicity of raw materials, and versatility.

Method used

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  • Preparation method of cyano tertiary amine
  • Preparation method of cyano tertiary amine
  • Preparation method of cyano tertiary amine

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0067]

[0068] Add 16.5 grams (0.1mol) of 2-bromo-1,3,4-thiadiazole, 60.72 grams (0.6mol) of diisopropylamine, 0.15 grams of copper powder and 1.64 grams of cuprous bromide to 250 ml In a round-bottomed flask, heat and reflux for 2 hours, after naturally cooling to room temperature, suction filtration, the filtrate is removed unreacted diisopropylamine by a rotary evaporator, and 10.66 grams of a light yellow liquid is obtained by distillation under reduced pressure, with a yield of 84.5%. ; IR (KBr tablet, cm -1 ):2976.16, 2933.73, 2877.79, 2196.92, 1523.76, 1463.97, 1386.82, 1371.39, 1334.74, 1242.16, 1184.29, 1130.29, 1101.35, 1053.13, 893.04; 1 H NMR (400MHz, CDCl 3 )δ (ppm): 3.17-3.23 (m, 2H), 1.25-1.27 (d, 12H, J=6.8Hz); 13 C NMR (100MHz, CDCl 3 )δ (ppm): 114.56, 50.62, 21.08. MS(m / z) / (M + ):126[M + ](55), 111(25), 69(100).

Embodiment 2

[0070]

[0071] 16.5 grams (0.1mol) of 2-bromo-1,3,4-thiadiazole, 77.52 grams (0.6mol) of di-n-butylamine, 0.15 grams of copper powder and 1.64 grams of cuprous bromide were added to 250 In a round-bottomed flask of 1 ml, heat and reflux for 2 hours, after naturally cooling to room temperature, suction filtration, the filtrate removes unreacted di-n-butylamine through a rotary evaporator, and obtains 13.26 grams of a light yellow liquid through vacuum distillation. The yield is 85.9%; 1 H NMR (400MHz, CDCl 3 )δ(ppm):2.96-3.00(t,4H),1.59-1.63(m,4H),1.36-1.44(m,4H),0.93-0.95(t,6H); 13 C NMR (100MHz, CDCl 3 )δ (ppm): 110.5, 51.20, 29.67, 19.68, 13.63. MS(m / z) / (M + ):154[M + ](20), 125(10), 111(35), 84(10), 69(100), 56(60), 44(25).

Embodiment 3

[0073]

[0074] 16.5 grams (0.1mol) of 2-bromo-1,3,4-thiadiazole, 17.03 grams (0.2mol) of piperidine, 0.15 grams of copper powder, 1.64 grams of cuprous bromide and 100 milliliters of toluene Join in the round-bottomed flask of 250 milliliters, heat and reflux for 2 hours, after naturally cooling to room temperature, suction filtration, filtrate removes toluene and unreacted piperidine through rotary evaporator, obtains 6.82 grams of light yellow liquid through decompression distillation, The yield is 61.9%; 1 H NMR (400MHz, CDCl 3 )δ (ppm): 3.16-3.19 (t, 4H), 1.62-1.68 (m, 4H), 1.54-1.60 (m, 2H); 13 C NMR (100MHz, CDCl 3 )δ (ppm): 118.27, 49.83, 24.23, 22.64. MS(m / z) / (M + ):110[M + ](75), 82(10), 69(45), 56(45), 42(100), 28(20).

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Abstract

The invention relates to the technical field of organic synthesis methods, in particular to a preparation method of N, N-disubstituted cyanamide. According to the invention, secondary amine and 2-bromo-1, 3, 4-thiadiazole, 2, 5-dibromo-1, 3, 4-thiadiazole or 2-bromo-5-methyl-1, 3, 4-thiadiazole are used as raw materials to prepare N, N-disubstituted cyano tertiary amine under the catalysis of a metal salt; the synthetic process is simple, the yield is high, the toxicity of the raw materials is extremely low, the reaction temperature is low, the reaction time is sort, the aftertreatment is simple, and the preparation process is a green preparation process with universality. The method for preparing N, N-disubstituted cyanamide solves the problems of low yield, high toxicity of raw materials, no universality, difficulty in asymmetric disubstituted synthesis and the like in the existing preparation process, and has industrial large-scale application prospects.

Description

technical field [0001] The invention relates to the field of organic synthesis, in particular to a preparation method of cyano tertiary amine. Background technique [0002] The cyano group has strong electron-withdrawing characteristics and strong polarity, and can be easily converted into various functional groups, such as hydrolyzed into carboxylic acid or amide, converted into amine by reduction reaction, and can also be prepared by ring-forming reaction Many nitrogen-containing heterocyclic compounds. Tertiary cyanoamines are an important class of organic compounds containing cyano groups. They are products in which hydrogen on secondary amines is replaced by cyano groups. Has a wide range of applications. [0003] Tertiary cyanoamine was first synthesized by Vliet in 1924 through the alkylation reaction of calcium cyanamide (Journal of the American Chemical Society, 1924,46(5):1305-1308). The process is simple, but due to the The low yield limits the wide application...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C261/04C07D295/215C07D215/08C07D209/86C07D209/08C07D207/325C07D213/75
CPCC07C261/04C07D295/215C07D215/08C07D209/86C07D209/08C07D207/325C07D213/75Y02P20/584
Inventor 霍二福程伟琴鲁鹏冯明杨帅王延花王毅楠
Owner HENAN CHEM IND RES INST
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