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Method for catalyzing addition reaction of phenyl isocyanate or phenyl isothiocyanate with thiol

A technology of phenyl isothiocyanate and phenyl isocyanate, which is applied in the field of catalyzing the addition reaction of phenyl isocyanate or phenyl isothiocyanate and mercaptan, and can solve the problem of limited catalyst metal types and catalyst dosage Large size, poor substrate universality, etc., to achieve the effect of wide application range of substrates, mild reaction temperature and mild reaction conditions

Active Publication Date: 2018-09-14
SUZHOU UNIV
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0008] Although the above catalytic systems can catalyze the intermolecular addition reaction of phenyl isocyanate or phenyl isothiocyanate and mercaptan to obtain thiocarbamate compounds, there are many problems in these systems, such as: The raw materials are poisonous, the amount of catalyst used is large, the types of catalyst metals are limited, the reaction conditions are harsh, and the universality of the substrate is poor, etc.

Method used

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  • Method for catalyzing addition reaction of phenyl isocyanate or phenyl isothiocyanate with thiol
  • Method for catalyzing addition reaction of phenyl isocyanate or phenyl isothiocyanate with thiol
  • Method for catalyzing addition reaction of phenyl isocyanate or phenyl isothiocyanate with thiol

Examples

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Effect test

Embodiment 1

[0038] Example 1: 10mol% La[N(SiMe 3 ) 2 ] 3 Catalyzes the intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 30 °C:

[0039] Anhydrous and oxygen-free, under the protection of argon, add 0.0620g (1.00×10 -4 Mole)La[N(SiMe 3 ) 2 ] 3 , then add 117.39μL (1.00×10 -3 mol) benzylthiol was stirred at room temperature for 15 min under an argon atmosphere, and 108.69 μL (1.00×10 -3 mol) phenyl isocyanate, stirred and reacted in a constant temperature bath at 30°C. After 24 hours, the protective argon gas was removed to quench the reaction, and the NMR yield was 83% according to the NMR analysis. The NMR data: 1 H NMR (400MHz, CDCl 3 ): δ7.39-7.13(m,9H,ArH),7.02(dd,J 1 =19.4,J 2 =12.0Hz, 2H, ArH, NH), 4.15(s, 2H, CH 2 )ppm. As can be seen from Comparative Example 1 and Example 1, La[N(SiMe 3 ) 2 ] 3 When used as a catalyst, its final yield is greatly improved compared with the yield without rare earth catalyst.

Embodiment 2

[0040] Example 2: 10mol% of Sm[N(SiMe 3 ) 2 ] 3 Catalyzes the intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 30 °C:

[0041] Under anhydrous, oxygen-free and argon protection, add 0.0625g (1.00×10 -4 Mole)Sm[N(SiMe 3 ) 2 ] 3 , then add 117.39μL (1.00×10 -3 mol) benzylthiol was stirred at room temperature for 15 min under an argon atmosphere, and 108.69 μL (1.00×10 -3 mol) phenyl isocyanate, stirred and reacted in a constant temperature bath at 30°C. After 24 hours, the protective argon gas was removed and the reaction was quenched by air exposure. The NMR yield was 79% according to NMR analysis.

Embodiment 3

[0042] Example 3: 10mol% Yb[N(SiMe 3 ) 2 ] 3 Catalyzes the intermolecular addition reaction of phenyl isocyanate and benzyl mercaptan at 30 °C:

[0043] Anhydrous and oxygen-free, under the protection of argon, add 0.0655g (1.00×10 -4 Mole)Yb[N(SiMe 3 ) 2 ] 3 , then add 117.39μL (1.00×10 -3 mol) benzylthiol was stirred at room temperature for 15 min under an argon atmosphere, and 108.69 μL (1.00×10 -3 mol) phenyl isocyanate, stirred and reacted in a constant temperature bath at 30°C. After 24 hours, the protective argon gas was removed to vent the reaction to quench the reaction, and the NMR yield was 75% according to NMR analysis.

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Abstract

The invention relates to a method for catalyzing addition reaction of phenyl isocyanate or phenyl isothiocyanate with thiol. The method for catalyzing the addition reaction of the phenyl isocyanate orthe phenyl isothiocyanate with the thiol includes the steps of allowing the phenyl isocyanate or phenyl isothiocyanate shown in a formula (1) and the thiol shown in a formula (2) to react at the temperature of 10-75 DEG C under the catalysis of a catalyst of rare earth amination and obtaining a thiocarbamate compound shown in a formula (3). The reaction route is as follows, wherein R1 and R3 areindependently selected from C1-C6 alkyl, halogen, C1-C6 alkoxy, nitro or trifluoromethyl; X is an oxygen atom or a sulfur atom; R2 is substituted benzyl, furanmethyl, cyclohexyl or trityl; a substituent group on the substituted benzyl is a C1-C6 alkyl, a halogen or a C1-C6 alkoxy; the molecular formula of the rare earth amination is RE[N(SiMe3)2]3; Re is a rare earth metal element. The method forcatalyzing the addition reaction of the phenyl isocyanate or the phenyl isothiocyanate with the thiol has the advantages that raw materials are simple and easy to get; operation is easy; reaction conditions are mild; yield is high; substrates have a wide range of applications.

Description

technical field [0001] The invention relates to the field of organic chemistry, in particular to a method for catalyzing the addition reaction of phenyl isocyanate or phenyl isothiocyanate and mercaptan. Background technique [0002] Thiocarbamic acid-S-ester compounds have an important role in medicine as bactericides and antiviral toxins; in biology, these compounds can be used as biological regulators and enzyme inhibitors; in agriculture, they can be used These compounds are used to kill insects and weeds. Therefore, the synthesis of thiocarbamic acid-S-ester compounds has great significance in various aspects. At present, the methods for synthesizing this compound mainly include: (1) carbonylation reaction of amine with carbon monoxide and sulfur, and then hydrocarbylation reaction with alkyl halide to generate target product; (2) molecular weight of thiocarbonyl compound (3) Oxidative coupling reaction of amines with carbon monoxide and aryl thiol compounds; (4) Sele...

Claims

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Application Information

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IPC IPC(8): C07C333/08C07D307/38C07C333/24
CPCC07C333/08C07C333/24C07C2601/14C07D307/38
Inventor 陆澄容陆语欣赵蓓胡黎娟
Owner SUZHOU UNIV
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