Preparation method of thiocarbamate compound

A technology of thiocarbamate and carbamate, applied in organic chemistry methods, chemical instruments and methods, organic chemistry, etc., can solve problems such as unfavorable actual production, complex and cumbersome operation, instability and easy oxidation, and achieve Avoid the use of metal reagents, process safety, and the effects of avoiding the use of toxic phosgene and carbon monoxide

Active Publication Date: 2019-03-22
QUFU NORMAL UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

However, the above two types of methods also have obvious shortcomings: method (1) needs to use metal catalysts and oxidants to mediate the reaction of thiophenol and sulfinate in advance to prepare thiosulfonate raw materials, the operation is complicated and cumbersome, the cost is large, and the reaction produces The equivalent waste sulfinate ester is difficult to deal with after the reaction; method (2) directly uses unstable, easily oxidized and smelly thiophenols or mercaptans, without using actual production

Method used

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  • Preparation method of thiocarbamate compound
  • Preparation method of thiocarbamate compound
  • Preparation method of thiocarbamate compound

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028]

[0029] At room temperature, sodium benzenesulfinate (0.2mmol), ethyl isocyanoacetate (0.4mmol), water (0.6mmol), acetonitrile (1.5mL), molecular iodine (0.02mmol), and dimethyl phosphite (0.4mmol), mix well, then in 100 o After heating and stirring under the condition of C for 6 hours, after the reaction was detected by TLC, 2 mL of water was added, and then extracted with ethyl acetate (4 mL) for 3 times, and the extract was concentrated under reduced pressure at 0.08 Mpa to solvent-free to obtain the crude product. Then wash with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 5:1, and perform flash column chromatography on a silica gel column to obtain 83% thiocarbamate, 39.7 mg of a white solid.

[0030] 1 H NMR (500 MHz, CDCl 3 ): δ 7.61 – 7.59 (m, 2H), 7.47 – 7.42 (m, 3H),6.00 (s, 1H), 4.21 (q, J = 7.2 Hz, 2H), 4.04 (d, J = 5.1 Hz, 2H), 1.28 (t, J = 7.2 Hz, 3H); 13 C NMR (125 MHz, CDCl 3 ): δ 169.3, 166.9, 135.6, 130.0...

Embodiment 2

[0032]

[0033] At room temperature, sodium benzenesulfinate (0.2mmol), ethyl isocyanoacetate (0.4mmol), water (0.6mmol), ethyl acetate (1.5mL), molecular iodine (0.02mmol ), and diethyl phosphite (0.4mmol), mix well, then in 100 oAfter heating and stirring for 6 hours under the condition of C, after the reaction was detected by TLC, 2 mL of water was added, and then extracted 3 times with ethyl acetate (4 mL). Then wash with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 5:1, and perform flash column chromatography on a silica gel column to obtain 75% thiocarbamate, 35.9 mg of a white solid.

Embodiment 3

[0035]

[0036] At room temperature, sodium benzenesulfinate (0.2mmol), ethyl isocyanoacetate (0.4mmol), water (0.6mmol), ethyl acetate (1.5mL), molecular iodine (0.02mmol ), and diisopropyl phosphite (0.4mmol), mix well, and then in 100 o After heating and stirring for 6 hours under the condition of C, after the reaction was detected by TLC, 2 mL of water was added, and then extracted 3 times with ethyl acetate (4 mL). Then wash with a mixed eluent of petroleum ether and ethyl acetate with a volume ratio of 5:1, and perform flash column chromatography on a silica gel column to obtain 60% thiocarbamate, 28.7 mg of a white solid.

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Abstract

The invention belongs to the field of synthesis of a compound, relates to a preparation method of a thiocarbamate compound, in particular to a method for synthesizing thiocarbamate through reacting ofcatalyzing three components of sodium sulfinate, isonitrile and water by iodine. The method comprises the following steps: adding the sodium sulfinate, the isonitrile and the water into ethyl acetate, then adding a molecular iodine catalyst and a phosphite reducing agent, heating, stirring and reacting for 6 to 10 hours under a condition that the temperature is 80 to 100 DEG C, and extracting, separating and purifying after finishing the reaction, thus obtaining the thiocarbamate. According to the method disclosed by the invention, the isonitrile is adopted as a carbon source, so that poisonous photogene and carbon monoxide are prevented from being used; odorless sodium sulfinate is adopted as a sulfur source, so that odorous thiophenol or thiol is prevented from being used; non-metalliciodine is adopted for catalyzing, so that a metal reagent is prevented from being used; the reaction has the advantages that the operation is simple and convenient, the technology is safe, environmentfriendliness is realized, and the like.

Description

technical field [0001] The invention belongs to the field of compound synthesis, and relates to a preparation method of a thiocarbamate compound, in particular to a method for synthesizing a thiocarbamate by iodine-catalyzed three-component reaction of sodium sulfinate, isonitrile and water. Background technique [0002] Thiocarbamate is an important class of organic compounds, which have a wide range of applications in medicinal chemistry, biochemistry and pesticides. In medicinal chemistry, it can be used as anesthetic, fungicide and antiviral agent; in biology, it can be used as biological regulator and enzyme inhibitor; in pesticide, it can be used as insecticide and herbicide. In addition, in synthetic chemistry, thiocarbamate is also an important class of synthons that participate in a variety of reactions, so its synthesis method has been attracting attention. [0003] The synthetic method of traditional thiocarbamate compound mainly comprises the hydrolysis alcoholy...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C331/06C07C333/04C07D333/34C07B45/00
CPCC07B45/00C07C331/06C07C333/04C07C2601/14C07D333/34
Inventor 魏伟鲍鹏丽吕玉芬王桦
Owner QUFU NORMAL UNIV
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