Synthesis method of N2-beta-sulfanyl triazole derivative

A technology of sulfanyl triazoles and synthetic methods, applied in organic chemistry methods, organic chemistry, etc., can solve the problems of reduced aromaticity of quinone structure, limited application range of derivatives, difficulty in realization, etc., and achieve universality of reaction Strong, easy to operate, no effect of transition metal participation

Active Publication Date: 2021-12-07
ZHOUKOU NORMAL UNIV
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  • Abstract
  • Description
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Problems solved by technology

However, the control of N-selectivity of triazoles, especially N 2 - Selectivity is a very challenging task, mainly because there is a dynamic equilibrium between N1 and N2 isomers, and N1 isomers are more stable, so the current functionalization of triazoles is generally obtained in N1 Moderate selectivity at the N2 position and no selectivity at the N2 position
In addition, compared with non-benzotriazoles, due to the reduced aromaticity of the quinone structure, the N of benzotriazoles 2 - Selectivity is more difficult to achieve
[0003] At present, most of the research work mainly focuses on the N of triazoles 1 - selective functionalization, while N 2 - Selective functionalization is yet to be developed, which greatly limits the range of applications of such derivatives

Method used

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  • Synthesis method of N2-beta-sulfanyl triazole derivative
  • Synthesis method of N2-beta-sulfanyl triazole derivative
  • Synthesis method of N2-beta-sulfanyl triazole derivative

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preparation example Construction

[0018] N 2 When the sulfur source benzene sulphenyl chloride in a solvent Ⅰ, the tetrahydrothiophene absence of a catalyst or catalyst role, or in the presence of a base: -β- synthetic methods sulfanyl triazole derivatives, comprising the steps of absence of a base, a triazole, a sulfur source, an olefin, a reaction at 50-80 ℃ 12-36 h, was concentrated in vacuo and the title compound obtained by column chromatography; triazole is a benzotriazole, a benzotriazole derivative thereof, 1,2,3-triazole or 1,2,3-triazole derivative.

[0019] N 2 The structure of the -β-thioalkyl triazole derivative is as shown in formula I and II:

[0020]

[0021] Rage I and II 1 Hydrogen, methyl, n-butyl, halogen, nitro, carboxy, phenyl, phenyl, methylene, nitro-substituted phenyl group or halogen substituted phenyl; 2 For phenyl, acetyloxy phenyl, chloromethylphenyl, halogenated phenyl, phenyl substituted phenyl, methyl substituted phenyl, tert-butyl substituted phenyl, methoxy substituted phenyl , ...

Embodiment 1

[0037] Chloroform as a solvent, 0.05 mmol tetrahydrothiophene (THT) as catalyst, 0.25 mmol N, N, N ', N'- tetramethyl-propanediamine (TMPDA) is an alkali, 0.5 mmol benzotriazole, 1.0 mmol PhSCl and 1.5 mmol of styrene was reacted at 70 ℃ 36 h, after column chromatography and concentrated to give the title compound can be A, a yield of 86%, N 2 - selectivity 88%.

[0038] 1 H NMR (400 MHz, CDCl 3 ) Δ 7.85 (dd, J = 6.6, 3.1 Hz, 2H), 7.44 (dd, J = 7.7, 1.5 Hz, 2H), 7.39 - 7.15 (m, 11H), 6.04 (dd,J = 9.6, 5.5 Hz, 1H), 4.25 (dd, J = 14.1, 9.6 Hz, 1H), 3.78 (dd, J = 14.1, 5.5 Hz, 1H); 13 C NMR (100MHz, CDCl 3 ) Δ 144.2, 137.6, 134.3, 131.3, 129.0, 128.8, 128.1, 127.2, 127.1,126.3, 118.2, 70.1, 40.0.

Embodiment 2

[0040] The specific synthetic steps of Reference Example 1, the triazole is a benzotriazole, an olefin of 4-acetoxystyrene.

[0041] B Yield 66%, N 2 - selectivity was 84%.

[0042] 1 H NMR (400 MHz, CDCl 3 ) Δ 7.84 (dd, J = 6.6, 3.1 Hz, 2H), 7.47 (d, J = 8.6 Hz, 2H), 7.36 (dd, J = 6.7, 3.0 Hz, 4H), 7.28 - 7.22 (m, 2H), 7.20 (t, J = 7.2 Hz, 1H), 7.04 (d, J = 8.6 Hz, 2H), 6.03 (dd, J = 9.6, 5.4 Hz, 1H), 4.23 (dd, J = 14.2, 9.7 Hz, 1H), 3.75 (dd, J = 14.2, 5.4 Hz, 1H), 2.25 (s, 3H). 13 CNMR (100 MHz, CDCl 3 ) Δ 169.1, 150.9, 144.2, 135.1, 134.1, 131.3, 129.1,128.5, 127.3, 126.5, 122.0, 118.2, 69.5, 40.1, 21.0.

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Abstract

The invention provides a synthesis method of a N2-beta-sulfanyl triazole derivative, which comprises the steps that in a solvent I, under the action of tetrahydrothiophene as a catalyst or no catalyst, and under the condition of alkali or no alkali, triazole, a sulfur source and olefin react for 12-36 hours at the temperature of 50-80 DEG C, and a target compound is obtained after concentration and column chromatography, wherein the triazole is benzotriazole, a benzotriazole derivative, 1, 2, 3-triazole or a 1, 2, 3-triazole derivative, and the sulfur source is benzene sulfenyl chloride. The method has the advantages of simple and mild reaction conditions, no transition metal participation, wide substrate adaptability range, high yield and high N2-selectivity.

Description

Technical field [0001] The present invention belongs to the technical field of chemical synthesis, specifically relates to N 2 sulfanyl -β- synthesis of triazole derivatives. Background technique [0002] Triazole heterocyclic ring is an important structural element, widely present in many drugs, functional materials and organic ligands, and are also widely used in synthetic chemistry. Where N 2 - alkyl substituted triazole having a broad spectrum of biological activity, it is used as antianxiety drugs, anticancer drugs, antiviral and antibacterial agents. Although there have been reported by cyclization can build a triazole ring, but directly to the commercialization of triazole N 2 - selective functionalization strategy advantage. However, N- triazole selectively control, in particular N 2 - selective, is a very challenging task, mainly because of the presence of dynamic equilibrium between the N1 and N2 isomers, and the N1 isomer is more stable, so the current triazole functio...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D249/18C07D409/06C07D249/06C07D249/04C07D401/06
CPCC07D249/18C07D409/06C07D249/06C07D249/04C07D401/06C07B2200/07
Inventor 张辉朱莉莉刘广路杨志广
Owner ZHOUKOU NORMAL UNIV
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