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A kind of thioamide derivative and preparation method thereof

A technology for thioamides and derivatives, applied in the field of thioamide derivatives and their preparation, can solve the problems of high production cost, benzaldehyde pollution, environmental pollution and the like, and achieves the advantages of reduced process cost, simple operation and easy availability of raw materials. Effect

Inactive Publication Date: 2019-07-09
ZHEJIANG UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0005] (1) Obtained by coupling aniline with benzaldehyde and sulfur under the action of potassium carbonate (H.Xu, H.Deng, Z.Li, H.Xiang, X.Zhou, Eur.J.Org.Chem.2013,7054 .), the main problem that this method exists is that benzaldehyde easily pollutes the environment in the reaction raw material
(2) Benzaldehyde, secondary amine and sulfur generate under the effect of microwave (O.I.Zubruyev, N.Stiasni, C.O.Kappe, J.Comb.Chem.2003,5,145.), this method needs microwave to promote the carrying out of reaction, industrialization Production increases production costs with potential impact of ionizing radiation on the environment
(5) Benzylamine is directly generated from 2-phenylethylamine and sulfur at 110-130°C (T.B.Nguyen, L. Ermolenko, A.Al-Mourabit, Org.Lett.2012, 14, 4274.); this method is simple to operate , easy, but only suitable for benzylamine, the scope of application is too narrow
(6) It can also be synthesized by coupling phenylacetylene with amine and sulfur under the action of pyridine (T.B.M.Q.Tran, L.Ermolenko, A.Al-Mourabit, Org.Lett.2014, 16, 310.), but in this method The raw material alkyne is expensive and the production cost is high
[0006] There are many deficiencies in the above methods: the reagents used in the reaction are highly toxic or corrosive, the raw materials are not easy to obtain, the reaction process is demanding, the production cost is high, and the environment is polluted.

Method used

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  • A kind of thioamide derivative and preparation method thereof
  • A kind of thioamide derivative and preparation method thereof
  • A kind of thioamide derivative and preparation method thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0041] In a dry 25 mL Schlenk reaction tube, 37 mg of 4-methoxyaniline, 71 mg of 4-methylstyrene, 38.4 mg of sulfur, 35 mg of potassium fluoride and 1.5 mL of dimethylsulfoxide were added. Under nitrogen protection, stir at 100°C for 24 hours. After the reaction was completed, it was cooled to room temperature, filtered to remove insoluble matter, washed with water, extracted with ethyl acetate, and directly passed through a silica gel column (the volume ratio of ethyl acetate to petroleum ether was 1:50-1:3) to obtain 73.2 mg of the product, with a yield of 95%, the reaction process is as follows:

[0042]

[0043] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0044] 1 H NMR (400MHz, CDCl 3 ):δ2.40(s,3H),2.83(s,3H),6.95(d,J=9.2Hz, 2H),7.22(d,J=8.0Hz,2H),7.60(d,J=8.8Hz ,2H),7.77(d,J=8.0Hz,2H),8.95(br,1H). 13 C NMR (100MHz, CDCl 3 ): δ198.23, 158.20, 141.90, 140.06, 132.12, 129.26, 126.75, 125.77, 114.18, 55.51, 21.42. ...

Embodiment 2

[0046] In a dry 25 mL Schlenk reaction tube, 37 mg of 4-methoxyaniline, 71 mg of 4-methylstyrene, 38.4 mg of sulfur, 35 mg of potassium fluoride and 1.5 mL of dimethylsulfoxide were added. Stir at 60°C for 24 hours under nitrogen protection. After the reaction, cool to room temperature, remove insoluble matter by filtration, wash with water, extract with ethyl acetate, and directly pass through a silica gel column (the volume ratio of ethyl acetate to petroleum ether is 1:50-1:3) to obtain 9.3 mg of product, the yield 12%, the reaction process is shown in the following formula:

[0047]

[0048] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0049] 1 H NMR (400MHz, CDCl 3 ):δ2.40(s,3H),2.83(s,3H),6.95(d,J=9.2Hz, 2H),7.22(d,J=8.0Hz,2H),7.60(d,J=8.8Hz ,2H),7.77(d,J=8.0Hz,2H),8.95(br,1H). 13 C NMR (100MHz, CDCl 3 ): δ198.23, 158.20, 141.90, 140.06, 132.12, 129.26, 126.75, 125.77, 114.18, 55.51, 21.42.

Embodiment 3

[0051] In a dry 25 mL Schlenk reaction tube, 37 mg of 4-methoxyaniline, 71 mg of 4-methylstyrene, 38.4 mg of sulfur, 35 mg of potassium fluoride and 1.5 mL of dimethylsulfoxide were added. Under nitrogen protection, stir at 120°C for 24 hours. After the reaction was completed, it was cooled to room temperature, filtered to remove insoluble matter, washed with water, extracted with ethyl acetate, and directly passed through a silica gel column (the volume ratio of ethyl acetate to petroleum ether was 1:50-1:3) to obtain 42.4 mg of the product. The yield was 55%, the reaction process is shown in the following formula:

[0052]

[0053] Carry out nuclear magnetic resonance analysis to the product that present embodiment prepares:

[0054] 1 H NMR (400MHz, CDCl 3 ):δ2.40(s,3H),2.83(s,3H),6.95(d,J=9.2Hz, 2H),7.22(d,J=8.0Hz,2H),7.60(d,J=8.8Hz ,2H),7.77(d,J=8.0Hz,2H),8.95(br,1H). 13 C NMR (100MHz, CDCl 3 ): δ198.23, 158.20, 141.90, 140.06, 132.12, 129.26, 126.75, 125.77, 114...

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Abstract

The invention discloses a thioamide derivative. The structural formula of the thioamide derivative is represented by the formula (I) or the formula (II). The invention also provides a preparation method of the thioamide derivative. According to the preparation method, alkali metal salts are taken as the alkalis, amines are directly coupled with alkenes and sulfur, and by selecting the alkali, twodifferent thioamide derivatives represented by the formula (I) and the formula (II) can be prepared from same raw materials. The provided preparation method has the advantages that the raw materials are cheap and easily available, the synthesis method is simple, and the cost is largely reduced. The provided thioamide derivatives can be used in fields such as bioactive molecules, drug synthesis, and the like, and has a wide application range.

Description

technical field [0001] The invention belongs to the field of organic synthesis, and in particular relates to a thioamide derivative and a preparation method thereof. Background technique [0002] Compounds containing thioamide structures are widely found in biologically active molecules and some drugs, such as sulfamide drugs clinically used to treat hyperthyroidism include Thyroxine (CMZ), pyridine methylthiourea, methamazole (MMI) and methimazole (MMI) Pyridinethiourea (PTU). [0003] In addition, in organic synthesis, thioamide is an important synthon, and many organic compounds such as amides, sulfur-containing heterocycles (such as thiophene, thiadiazole, thiazole and thiazoline) amidines can be used as raw materials through thioamide Therefore, chemists are also making continuous efforts to explore new structures based on thioamides and their new synthetic methods. [0004] At present, the methods for synthesizing thioamide derivatives with organic amines as raw mate...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07C327/48C07C327/44
CPCC07C327/44C07C327/48
Inventor 陈万芝张平顺
Owner ZHEJIANG UNIV