阅读说明：本技术 一类芳基硫醚类化合物及其制备方法 (Aryl thioether compounds and preparation method thereof ) 是由 陈铁桥 徐添豪 刘龙 黄添增 唐智 李春娅 于 2021-10-08 设计创作，主要内容包括：本发明揭示了一类芳基硫醚化合物及其合成法,该方法以芳基羧酸和硫醇(酚)为主要原料,在镍催化剂、膦配体及添加剂的作用下,芳基羧酸和硫醇(酚)为原料在有机溶剂中反应,反应结束后经过后处理得到相应的芳基硫醚。本方法具有成本较低,产率高,操作简便、无污染等优点,具有潜在的工业应用前景。该方法为芳基硫醚类化合物的制备提供了一条廉价、绿色的途径。(The invention discloses an aryl thioether compound and a synthesis method thereof, wherein aryl carboxylic acid and mercaptan (phenol) are used as main raw materials, the aryl carboxylic acid and the mercaptan (phenol) are used as the raw materials to react in an organic solvent under the action of a nickel catalyst, a phosphine ligand and an additive, and after the reaction is finished, the corresponding aryl thioether is obtained through post-treatment. The method has the advantages of low cost, high yield, simple and convenient operation, no pollution and the like, and has potential industrial application prospect. The method provides a cheap and green way for preparing aryl thioether compounds.)

1. An aryl thioether compound and a synthetic method thereof, wherein the structural formula of the aryl thioether compound 3 is as follows:

wherein Ar is 1-naphthyl, 2-naphthyl, independent or unsubstituted aryl; r is substituted or unsubstituted phenyl, alkyl; wherein the substituents on the phenyl group include C₂-C₄Methyl group of (2)₄Tert-butyl, methoxy, trifluoromethyl, nitrile, phenyl; the alkyl is 2-naphthyl ethyl; alkenyl is cinnamyl; the synthesis method of the compound 3 is characterized in that aryl carboxylic acid 1 and mercaptan (phenol) 2 are used as raw materials to react in an organic solvent under the action of a catalyst, a ligand and an acid anhydride, and after the reaction is finished, the corresponding aryl thioether 3 is obtained through post-treatment.

2. The synthesis of claim 1, wherein the aryl carboxylic acid 1 and thiol (phenol) 2 starting materials have the following structural formulas:

wherein Ar is 1-naphthyl, 2-naphthyl, independent or unsubstituted aryl; r is substituted or unsubstituted phenyl, alkyl; wherein, the substituent on the phenyl group comprises methyl, tert-butyl, methoxyl, trifluoromethyl, nitrile group and phenyl; the alkyl is 2-naphthyl ethyl; alkenyl is cinnamyl.

3. The synthesis method according to claim 1, wherein the zero-valent nickel is a catalyst, the bidentate phosphine ligand is a ligand, the acid anhydride is an additive, the organic solvent is a reaction solvent, the reaction time is 14 h, and the reaction temperature is 140%^oC。

[ technical field ] A method for producing a semiconductor device

The invention belongs to the field of catalytic organic synthesis, and particularly relates to an aryl thioether compound and a preparation method thereof.

[ background of the invention ]

Organosulfur compounds are an important class of bio-organic compounds that can be found in pharmaceuticals, natural products, and agrochemicals. Aryl sulfide, sulfoxide and sulfone molecules are of great interest in modern pharmaceutical and agrochemical science. Thilidazine is a classical neurological drug used to treat schizophrenia in adults and children. Ametryn is a triazine herbicide with selective absorption and transmission effects. Isoxaflutole is an isoxazole-containing compound, a Herbicide (HPPD) that acts as an inhibitor of p-hydroxyphenylpyruvate dioxygenase. In view of the importance of these compounds, it is of great interest to develop a new process for the preparation of aryl sulfides. Transition metal catalyzed cross-coupling reactions of C-S bonds between aryl (pseudo) halides thiols are the most classical and most important method for the synthesis of aryl sulfides. However, aryl halides are relatively toxic and expensive.

In order to synthesize the aromatic thioether more efficiently and environmentally, a novel method for synthesizing the aromatic thioether compound is developed, namely, aryl carboxylic acid and mercaptan (phenol) are used as raw materials, and the aryl thioether compound is synthesized through decarbonylation coupling to obtain some novel aryl thioether compounds. At present, the published documents and patent applications of aryl thioether compound synthesis by decarbonylation coupling are not available at home and abroad.

[ summary of the invention ]

The invention aims to react aryl carboxylic acid and mercaptan (phenol) which are used as raw materials in an organic solvent under the action of a catalyst, a ligand and an additive, and obtain corresponding aryl thioether after the reaction is finished and post-treatment is carried out. The method has the advantages of low cost, high yield, simple and convenient operation, no pollution and the like, and has certain feasibility for realizing the industrial production. In order to achieve the above purpose, the invention provides the following technical scheme:

an aryl alkyne compound and a synthesis method thereof, wherein the structural formula of an aryl thioether compound 3 is as follows:

wherein Ar is 1-naphthyl, 2-naphthyl, independent or unsubstituted aryl. R is substituted or unsubstituted phenyl or alkyl. Wherein, the substituent on the phenyl group comprises methyl, tert-butyl, methoxyl, trifluoromethyl, nitrile group and phenyl; the alkyl is 2-naphthyl ethyl; alkenyl is cinnamyl. The synthesis method of the compound 3 is characterized in that aryl carboxylic acid 1 and mercaptan (phenol) 2 are used as raw materials to react in an organic solvent under the action of a catalyst, a ligand and an acid anhydride, and after the reaction is finished, the corresponding aryl thioether 3 is obtained through post-treatment.

In the above synthesis method, the structural formulas of the raw materials, i.e., aryl carboxylic acid 1 and thiol (phenol) 2, are as follows:

ar is 1-naphthyl, 2-naphthyl, independent or unsubstituted aryl. R is substituted or unsubstituted phenyl or alkyl. Wherein the substituents on the phenyl group include C₂-C₄Methyl group of (2)₄Tert-butyl, methoxy, trifluoromethyl, nitrile, phenyl; the alkyl is 2-naphthyl ethyl; alkenyl is cinnamyl.

In the synthesis method, aryl carboxylic acid and mercaptan (phenol) are used as raw materials to react in an organic solvent under the action of a catalyst, a ligand and an additive, and after the reaction is finished, the corresponding aryl thioether is obtained through post-treatment.

The synthesis method of the aryl alkyne compound provided by the invention opens up a new low-cost 'green' approach, and has the advantages that: the yield of the target product is high, the reaction condition is mild, and the reaction operation is simple and convenient.