Synthesis method of 2-(4-cyano) pyridyl (3-cyano) thioanisole

A technology of anisole sulfide and a synthesis method, applied in the direction of organic chemistry and the like, can solve the problems of transition metal residue, low total yield, long reaction period, etc., and achieves easy operation, high reaction efficiency, and low requirements for reaction conditions. Effect

Inactive Publication Date: 2017-09-12
WENZHOU UNIVERSITY
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AI Technical Summary

Problems solved by technology

In a word, these methods all need multi-step reaction, the reaction cycle is long, the efficiency is low and the total yield is not high.
Simultaneously, these methods also all will inevitably use a large excess of alkali, which will also produce a large amount of waste in the post-reaction treatment process; in addition, 2-(4-cyano)pyridyl(3-chloro)benzene The synthesis of methyl sulfide (I) needs to adopt the alkyl halide compound with high toxicity and poor stability as alkylating reagent; The synthesis requires the use of transition metal catalysts, and there may be problems with transition metal residues
Therefore, these methods still have many shortcomings, which need to be improved urgently.

Method used

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  • Synthesis method of 2-(4-cyano) pyridyl (3-cyano) thioanisole
  • Synthesis method of 2-(4-cyano) pyridyl (3-cyano) thioanisole
  • Synthesis method of 2-(4-cyano) pyridyl (3-cyano) thioanisole

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Experimental program
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Effect test

Embodiment 1

[0023] Preparation of 2-(4-cyano)pyridyl(3-chloro)sulfide anisole (I)(0.50mmol) from 2-chloro-4-cyanopyridine, thiourea and 3-chlorobenzyl alcohol

[0024]

[0025] 2-Chloro-4-cyanopyridine (82.8mg, 0.60mmol, 1.2equiv.), thiourea (45.6mg, 0.60mmol, 1.2equiv.), 3-chlorobenzyl alcohol (71.0mg, 0.50mmol,) and water (9.0mg, 0.50mmol) were directly sealed under air, and then heated to 140°C for 24h under solvent-free conditions. After the completion of the reaction monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 70% (91.0 mg). 1 H NMR (400MHz, CDCl 3 )δ8.59(d,J=5.0Hz,1H),7.39(s,1H),7.37(s,1H),7.28–7.13(m,4H),4.41(s,2H); 13 C NMR (100MHz, CDCl 3 ) δ 160.4, 150.1, 139.4, 134.3, 129.8, 129.1, 127.6, 127.1, 123.7, 120.4, 116.2, 33.6.

Embodiment 2

[0027] Preparation of 2-(4-cyano)pyridyl(3-chloro)sulfide anisole (I)(10.0mmol) from 2-chloro-4-cyanopyridine, thiourea and 3-chlorobenzyl alcohol

[0028]

[0029] In the tubular reactor, 2-chloro-4-cyanopyridine (1.656g, 12.0mmol, 1.2equiv.), thiourea (0.912g, 12mmol, 1.2equiv.) and 3-chlorobenzyl alcohol (1.420g, 10mmol ,), sealed directly in the air, and then heated to 140°C for 24h under solvent-free conditions. After the completion of the reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 65% (1.692g). 1 H NMR (400MHz, CDCl 3 )δ8.59(d,J=5.0Hz,1H),7.39(s,1H),7.37(s,1H),7.28–7.13(m,4H),4.41(s,2H); 13 C NMR (100MHz, CDCl 3 ) δ 160.4, 150.1, 139.4, 134.3, 129.8, 129.1, 127.6, 127.1, 123.7, 120.4, 116.2, 33.6.

Embodiment 3

[0031] Preparation of 4-(2-formamido)pyridyl(3-bromo)sulfide anisole(II)(10.0mmol) from 4-chloropyridine-2-carboxamide, thiourea and 3-bromobenzyl alcohol

[0032]

[0033] 4-chloropyridine-2-carboxamide (1.872g, 12.0mmol, 1.2equiv.), thiourea (0.912g, 12mmol, 1.2equiv.) and 3-bromobenzyl alcohol (1.860g, 10mmol,), sealed directly in the air, and then heated to 140°C for 24h under solvent-free conditions. After the completion of the reaction was monitored by TLC, the product was separated and purified by column chromatography, and the separation yield was 33% (1.054g). 1 H NMR (400MHz, CDCl 3 )δ8.33(d,J=5.0Hz,1H),8.08(d,J=1.5Hz,1H),7.86(brs,1H),7.57(s,1H),7.42(d,J=8.0Hz, 1H), 7.34(d, J=8.0Hz, 1H), 7.27–7.16(m, 3H), 5.76(s, 1H), 4.24(s, 2H). 13 C NMR (100MHz, CDCl 3 ) δ 166.2, 150.8, 149.1, 147.7, 137.4, 131.8, 131.0, 130.4, 127.5, 123.1, 122.8, 119.1, 35.1.

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Abstract

The invention provides a synthesis method of 2-(4-cyano) pyridyl (3-cyano) thioanisole. The invention also provides a synthesis method of 4-(2-formamido) pyridyl (3-bromo) thioanisole. According to the technical scheme, 2-chloro-4-cyanopyridine / 4-chloropyridine-2-formamide, micromolecular sulfur compounds and 3-chloro / bromobenzyl alcohol are used for directly synthesizing 2-(4-cyano) pyridyl (3-cyano) thioanisole (I) and 4-(2-formamido) pyridyl (3-bromo) thioanisole (II) under the condition of no additional catalysts. The method has the advantages that the reaction conditions are simple; inert gas protection is not needed; solvents are not needed; the operation is easy. By the method, the 20-time amplification production can be conveniently realized; the product gram grade preparation is performed, so that certain study and industrial application prospects are realized.

Description

technical field [0001] The invention belongs to the field of chemical synthesis, in particular to 2-(4-cyano)pyridyl (3-chloro)anisole sulfide and 4-(2-formamido)pyridyl (3-bromo)anisole sulfide Ether synthesis method. The method is directly prepared by 2-chloro-4-cyanopyridine / 4-chloropyridine-2-carboxamide, small molecule sulfur-containing compound and 3-chloro / bromobenzyl alcohol without any external catalyst. green approach. Background technique [0002] 2-(4-cyano)pyridyl(3-chloro)sulfide anisole (I) and 4-(2-formamido)pyridyl(3-bromo)sulfide anisole (II) have been shown to exhibit showed good anti-tuberculosis activity. Therefore, their synthesis has attracted the attention of more and more organic chemists. [0003] In the known synthetic method, 2-(4-cyano) pyridyl (3-chloro) sulfide anisole (I) can pass through 2-chloro 4-cyanopyridine, thiourea and 3-chlorobenzyl chloride in excess Under the action of sodium methoxide, it is prepared by multi-step reaction, an...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D213/84
CPCC07D213/84
Inventor 徐清马献涛苏陈良
Owner WENZHOU UNIVERSITY
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