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Method of preparing sulfo-carbamate compound based on photocatalysis

A carbamate and compound technology, which is applied in the field of preparation of thiocarbamate compounds based on photocatalysis, can solve the problems of human injury, cumbersome operation, and high energy consumption, and avoid the use of metal reagents and reaction energy. Clean, process safe and reliable results

Inactive Publication Date: 2018-12-07
QINGDAO UNIV OF SCI & TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

[0014] There are obvious shortcomings in most of the above synthetic methods: most of methods 1-3 use toxic phosgene to prepare raw materials, phosgene pollutes the environment and causes great harm to the human body; method 4 uses carbon monoxide poisonous gas as a reaction raw material, which also pollutes the environment , endanger human health. In addition, this type of reaction also needs to add metal catalyst or equivalent alkali accelerator, which consumes a lot of energy and has many by-products; method 5 needs to prepare thiosulfonate raw materials with thiophenol and sulfinate in advance, The operation is cumbersome, the cost is high, and the reaction produces an equivalent amount of waste sulfinate, which makes the post-processing reaction difficult

Method used

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  • Method of preparing sulfo-carbamate compound based on photocatalysis
  • Method of preparing sulfo-carbamate compound based on photocatalysis
  • Method of preparing sulfo-carbamate compound based on photocatalysis

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0040]

[0041] At room temperature, in a 15 mL reaction tube, add p-methylthiophenol (0.2 mmol), ethyl isocyanoacetate (0.5 mmol), photocatalyst Rose Bengal (0.004 mmol), ethyl acetate 0.5 mL and water 0.5 mL, mix well, and then under the irradiation of 3w blue LED light, stir and react in the air for 3h. After the completion of the reaction as detected by TLC, ethyl acetate was added for extraction 3 times, and the extract was concentrated under reduced pressure in a vacuum (0.08Mpa) to no solvent to obtain a crude product, which was then purified with petroleum ether and ethyl acetate at a volume ratio of 5:1. Washing with a mixed eluent, followed by flash column chromatography on a silica gel column, the thiocarbamate product of this example was obtained as 42.0 mg of a yellow oil, with a yield of 83%.

[0042] 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.39 (d, J = 8.0 Hz, 2H), 7.16 (d, J =8.0 Hz, 2H), 5.82 (s, 1H), 4.11 (q, J = 7.2 Hz, 2H), 3.94 (d, J = 5.1 Hz,2H), ...

Embodiment 2

[0044]

[0045] At room temperature, add m-methylthiophenol (0.2 mmol), ethyl isocyanoacetate (0.5 mmol), photocatalyst water-soluble eosin (0.004 mmol), ethyl acetate 0.5 mL and water 0.5 mL in sequence in a 15 mL reaction tube , mixed evenly, and then stirred and reacted in the air for 3 hours under the irradiation of a 3w blue LED light. After the completion of the reaction as detected by TLC, ethyl acetate was added for extraction 3 times, and the extract was concentrated under reduced pressure in a vacuum (0.08Mpa) to no solvent to obtain a crude product, which was then purified with petroleum ether and ethyl acetate at a volume ratio of 5:1. Washing with a mixed eluent, followed by flash column chromatography on a silica gel column, the thiocarbamate product of this example was obtained as 38.4 mg of a yellow oil, with a yield of 76%.

[0046] 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.41 (s, 1H), 7.39 (d, J = 7.9 Hz, 1H), 7.32 (d, J = 7.6 Hz, 1H), 7.25 (d, J = 7...

Embodiment 3

[0048]

[0049] At room temperature, add 23.6 μL (0.2 mmol) of o-methylthiophenol, 55 μL (0.5 mmol) of ethyl isocyanoacetate, photocatalyst Rose Bengal (0.004 mmol), 0.5 mL of isocyanide and 0.5 mL of water, mix well, and then under the irradiation of 3w blue LED light, stir and react in the air for 3h. After the completion of the reaction as detected by TLC, ethyl acetate was added for extraction 3 times, and the extract was concentrated under reduced pressure in a vacuum (0.08Mpa) to no solvent to obtain a crude product, which was then purified with petroleum ether and ethyl acetate at a volume ratio of 5:1. Washing with a mixed eluent, followed by flash column chromatography on a silica gel column, the thiocarbamate product of this example was obtained as 44.3 mg of a yellow oil, with a yield of 88%.

[0050] 1 H NMR (CDCl 3 , 500 MHz, ppm): δ 7.58 (d, J = 7.7 Hz, 1H), 7.38-7.34 (m,2H), 7.26-7.23 (m, 1H), 5.89 (s, 1H), 4.18 (q, J = 7.2 Hz, 2H), 4.00 (d, J =5.2 H...

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Abstract

The invention relates to a method for preparing a sulfo-carbamate compound based on photocatalysis and particularly relates to a method for preparing the sulfo-carbamate compound based on photocatalysis. A reaction formula in the method is formula (shown in the description), wherein R1 represents optionally substituted aryl, naphthyl, heteroaryl and C1-C10 alkyl; R2 represents optionally substituted aryl, naphthyl, heteroaryl or optionally substituted aryl C1-C10 alkyl. According to the method, the substituted sulfo-carbamate compound is synthesized by virtue of visible light catalysis, the reaction energy source is clean, and the conditions are mild; the raw materials are easily available, the use of toxic phosgene and carbon monoxide is avoided, the reaction operation is simple, and theprocess is safe and reliable; and by utilizing a nonmetal photocatalyst, the use of a metal reagent is avoided, and water is taken as a cosolvent, so that the method is environment-friendly.

Description

technical field [0001] The invention relates to a method for synthesizing a thiocarbamate compound, in particular to a method for preparing a thiocarbamate compound based on photocatalysis. Background technique [0002] Thiocarbamate compounds have a very wide application value in medicinal chemistry, natural product chemistry and related interdisciplinary fields including agronomy and material science. They often exist in a variety of pharmaceutical molecules, used as antiviral agents, anesthetics, insecticides, herbicides and fungicides, etc. ( Tetrahedron , 1999, 55 , 7957; J. Fluorine Chem.1999, 99 , 17; Bioorg. Med. Chem. Lett . 2002, 12 , 767; J. Agric. Food Chem. 1979, 27 , 709; Synthesis 1981, 622). [0003] The method of existing synthetic thiocarbamate compound mainly comprises: [0004] (1) Use phosgene to react with amine to obtain amino acid chloride, and then react with nucleophilic substitution of thiophenol or thiol ( J. Am. Chem. Soc, 1951, 7...

Claims

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Application Information

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IPC IPC(8): C07C333/04C07C333/06C07C333/08
CPCC07C333/04C07C333/06C07C333/08C07C2601/14
Inventor 魏伟鲍鹏丽吕玉芬杨道山王桦
Owner QINGDAO UNIV OF SCI & TECH
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