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Method for one-step synthesis of cyan tertiary amine compound from allylic tertiary amine compound

A technology of tertiary amine compounds and cyano group, which is applied in the field of synthesizing cyano tertiary amine compounds, can solve the problems of expensive deallylation catalyst, control many by-products, and high synthesis cost, and achieve low price and high raw material Easy to obtain, less synthetic steps

Active Publication Date: 2017-07-11
BEIJING INSTITUTE OF TECHNOLOGYGY
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

Due to the high synthesis cost in the above method, expensive deallylation catalyst is needed, the operation is complicated, the selectivity is not easy to control, and there are many by-products.

Method used

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  • Method for one-step synthesis of cyan tertiary amine compound from allylic tertiary amine compound
  • Method for one-step synthesis of cyan tertiary amine compound from allylic tertiary amine compound
  • Method for one-step synthesis of cyan tertiary amine compound from allylic tertiary amine compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0030] Add 5ml of anhydrous DMF to a 25ml reaction flask, then add 12mmol of cyanogen bromide to dissolve it, then add 4mmol of 1-allylpiperidine (structural formula such as 1a) dropwise under argon protection, and seal the reaction environment , magnetically stirred at 25°C. After 16 hours, the reaction solution was separated by column chromatography, the mobile phase ratio was 10:90 by volume of ethyl acetate and petroleum ether, and the product was obtained after the mobile phase was removed by rotary evaporation.

[0031] The test results are as follows:

[0032] IR(KBr):2945,2857,2210,1451cm -1

[0033] 1 H NMR (CDCl 3 , 400MHz): δ1.46-1.47(2H),1.53-1.54(4H),3.06-3.07(4H).

[0034] 13 C NMR (CDCl 3 , 100MHz): δ118.6, 50.1, 24.5, 23.0.

[0035] HRMS(ESI+)calculated for[C6H10N2Na] + (M+Na) + :m / z133.073677,found133.073619.

[0036] The product is 1-cyanopiperidine with the structural formula as 1b, and the yield is 75%.

[0037]

Embodiment 2

[0039] Add 4ml of anhydrous chloroform to a 25ml reaction flask, then add 8mmol of cyanogen bromide to dissolve it, then add 4mmol of 1-allylpyrrolidine (structural formula as 2a) dropwise under the protection of inert gas argon, and seal it Reaction environment, magnetic stirring at 15°C. After 20 hours, the reaction solution was separated by column chromatography, the mobile phase ratio was ethyl acetate to petroleum ether volume ratio 12:88, and the product was obtained after the mobile phase was removed by rotary evaporation.

[0040] The test results are as follows:

[0041] IR(KBr):2985,2885,2220,1635,1488,1352,1027,909cm -1 .

[0042] 1 H NMR (CDCl 3 , 400MHz): δ1.87(4H),3.36(4H).

[0043] 13 C NMR (CDCl 3 , 100MHz): δ117.8, 50.5, 25.6.

[0044] HRMS(ESI+)calculated for[C5H8N2Na] + (M+Na) + :m / z119.058023,found119.057969.

[0045] The product is 1-cyanopyrrolidine, the structural formula is as 2b, and the yield is 70%.

[0046]

Embodiment 3

[0048] Add 4.5ml of anhydrous 1,4-dioxane to a 25ml reaction flask, then add 10mmol of cyanogen bromide to dissolve it, and then add 4mmol of 1-allyl mol dropwise under the protection of inert gas argon. Phenol (structural formula such as 3a), closed reaction environment, magnetic stirring at 17°C. After 24 hours, the reaction solution was separated by column chromatography, the mobile phase ratio was ethyl acetate to petroleum ether volume ratio 37:63, and the mobile phase was removed by rotary evaporation to obtain the product.

[0049] The test results are as follows:

[0050] IR(KBr):2973,2926,2862,2219,1454,1377,1114,1002,850cm -1 .

[0051] 1 H NMR (CDCl 3 , 400MHz): δ3.15(4H),3.64(4H).

[0052] 13 C NMR (CDCl 3 , 100MHz): δ117.2, 65.5, 48.7.

[0053] HRMS(ESI+)calculated for[C5H9N2O] + (M+H) + :m / z 113.070997,found113.070939.

[0054] The product is 1-cyanomorpholine, the structural formula is as 3b, and the yield is 73%.

[0055]

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Abstract

The invention relates to a method for one-step synthesis of a cyan tertiary amine compound from an allylic tertiary amine compound, and belongs to the technical field of organic synthesis methods. The method concretely comprises the following steps: adding cyanogen bromide into an anhydrous organic solvent in a closed reaction environment, dropwise adding the allylic tertiary amine compound into the above obtained solution under the protection of an inert gas to obtain a solution with the allylic tertiary amine compound concentration of 0.8-1 mol / L, carrying out a reaction at room temperature for 16-24 h, and carrying out column chromatographic separation and purification to obtain the corresponding cyan tertiary amine compound. The method has the advantages of avoiding of an expensive deallylation catalyst, few synthesis steps, easily available raw materials, low price, mild reaction conditions, simplicity in operation, and easiness in technological and industrial production, and allows the yield to be 50-80%.

Description

[0001] Technical field: [0002] The invention relates to a method for synthesizing cyano tertiary amine compounds in one step from allyl tertiary amine compounds, in particular to a one-step method of nucleophilic substitution reaction using allyl tertiary amine compounds and cyanogen bromide at room temperature A method for synthesizing cyano tertiary amine compounds. It belongs to the technical field of organic synthesis methods. [0003] Background technique: [0004] The cyano group is a carbon-nitrogen triple bond with strong polarity and electron-withdrawing properties. As a group often cited in clinically used drugs, the cyano group has the following characteristics: (1) The volume of the cyano group is only 1 / 3 of that of the methyl group. 8; (2) The cyano group is a good hydrogen bond acceptor; (3) The cyano group is a biological isostere of functional groups such as carbonyl and halogen. The introduction of the cyano group into the small molecule of the drug can cha...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D295/14C07C261/04
Inventor 孙成辉梁鸿刚庞思平
Owner BEIJING INSTITUTE OF TECHNOLOGYGY