Method for preparing C2-position alkynyl compound by catalyzing thiamine type compound desulfuration through cuprous halides

A compound and thiamine technology, which is applied in the field of cuprous halide catalyzing the desulfurization of thiamine compounds to prepare C2-position alkynyl compounds, can solve the problems of cumbersome experimental steps, harsh conditions, environmental pollution, etc. Simple, high-yield effects

Inactive Publication Date: 2016-07-06
HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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Problems solved by technology

However, these methods generally use expensive cuprous thiophene as a desulfurization reagent, and the reaction cannot occur when using cuprous halide and other cuprous salts, and the conditions are harsh, the experimental steps are cumbersome, the yield is low, and the pollution to the environment bigger

Method used

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  • Method for preparing C2-position alkynyl compound by catalyzing thiamine type compound desulfuration through cuprous halides

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0023] 28 mg (0.2 mmol) of 2-mercapto-5-pyrimidinecarbaldehyde, 33 mg (0.4 mmol) of 3,3-dimethyl-1-butyne and 1.5 mg (2%) of palladium triphenylphosphine acetate, 102 mg ( 1mmol) triethylamine, 2ml N,N-dimethylformamide were added to the Schlenk tube under nitrogen atmosphere, and copper salt (0.6mmol) (cuprous iodide, cuprous chloride, cuprous bromide , cuprous oxide, copper acetate monohydrate), at 110 o The reaction was stirred at C for 1 hour. Through GC detection and analysis, when cuprous iodide is used as a desulfurizing agent, the yield of the coupling reaction can reach 60% yield.

Embodiment 2

[0025] 28 mg (0.2 mmol) of 2-mercapto-5-pyrimidinecarbaldehyde, 33 mg (0.4 mmol) of 3,3-dimethyl-1-butyne and 1.5 mg (2%) of palladium triphenylphosphine acetate, 114 mg ( 0.6mmol) cuprous iodide and 1.0mmol base (triethylamine, sodium carbonate, pyridine, sodium acetate, N,N-diisopropylethylamine, 1,8-diazabicycloundec-7- Alkenes) were added to the Schlenk tube under nitrogen atmosphere, under N 2 Add 2.0ml of N,N-dimethylformamide under the environment, at 110 o The reaction was stirred at C for 12 hours. Through GC detection and analysis, under the catalysis of 5 times the equivalent of sodium carbonate, the coupling reaction can reach a yield of 92%.

Embodiment 3

[0027] 28 mg (0.2 mmol) of 2-mercapto-5-pyrimidinecarbaldehyde, 33 mg (0.4 mmol) of 3,3-dimethyl-1-butyne and 1.5 mg (2%) of palladium triphenylphosphine acetate, 114 mg ( Add 0.6mmol) cuprous iodide, 106mg sodium carbonate into the Schlenk tube under nitrogen atmosphere, add 2.0ml solvent (N,N-dimethylformamide, toluene, tetrahydrofuran, acetonitrile, 1,4-di Oxyhexane), at 110 o The reaction was stirred at C for 1 hour. Through GC detection and analysis, under the condition of N,N-dimethylformamide as solvent, the coupling reaction can reach a yield of 92%.

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Abstract

The invention provides a method for efficiently synthesizing derivatives which contain different substitution functional groups and have C2-position alkynyl substituted.According to the method, Pd(OAc)2(PPh3)2 / CuI is used as a catalyst, Na2CO3 is added as alkaline, compounds containing thiamine and terminal alkyne are used as oligomer, and organic solvent is added to the reaction system.The method has the advantages that the catalyst is low in price and easy to obtain; the reaction condition is mild, safe and reliable; the highest yield of target products reaches 92%.The method overcomes the defects that in traditional desulfuration reaction, cuprous thiophene needs to be used as a desulfurizing agent and cuprous halides can not react; the operation process is simple, and good industrial application prospects are achieved.

Description

technical field [0001] The invention relates to the applied catalytic synthesis field of desulfurization coupling, in particular to a preparation method for preparing thiamine C2 alkynyl derivatives by catalyzing the desulfurization of sulfur-containing amine compounds with cuprous halide. 【Background technique】 [0002] The derivatives substituted at the C2 position of thiamine are an important class of organic compounds, which have important pharmacological activity, optical activity and biological activity, making them widely used in biology, medicine and asymmetric catalytic synthesis. [0003] 2-(3,3-Dimethyl-1-butynyl)-5-pyrimidinecarbaldehyde is another typical raw material for autocatalytic reactions, which is of great significance in revealing the origin of life. And the thiamine compounds with C2 alkyne substitution are also an important class of synthetic intermediates. Although many organic molecules with biological activity contain structural units substituted...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B37/00C07D239/26C07D277/64C07D405/04
CPCC07B37/00C07D239/26C07D277/64C07D405/04
Inventor 杨涛杨赞周从山李姣
Owner HUNAN INSTITUTE OF SCIENCE AND TECHNOLOGY
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