阅读说明：本技术 一种异硫氰酸苯酯衍生物的制备方法 (Preparation method of phenyl isothiocyanate derivative ) 是由 不公告发明人 于 2019-11-26 设计创作，主要内容包括：本发明涉及一种异硫氰酸苯酯衍生物的制备方法。异硫氰酸苯酯衍生物通过以下制备方法制得：将硫代氯甲酸苯酯衍生物与苯胺衍生物溶于有机溶剂中,以碘化亚铜、固体碱作为催化剂,加热反应后经提纯得到。本发明所公开的异硫氰酸苯酯衍生物的制备方法原料经济易得；一步法反应所得到的目标产物产率在65-85％左右,相比于传统的硫代氯甲酸苯酯法产率有了极大地提升。所公开的制备方法有力地推进了异硫氰酸苯酯及其衍生物的生产效率,具有广阔的工业化前景。(The invention relates to a preparation method of a phenyl isothiocyanate derivative. The phenyl isothiocyanate derivative is prepared by the following preparation method: dissolving a phenyl thiocarboformate derivative and an aniline derivative in an organic solvent, heating to react by using cuprous iodide and solid alkali as catalysts, and purifying to obtain the compound. The raw materials of the preparation method of the phenyl isothiocyanate derivative disclosed by the invention are economical and easy to obtain; the yield of the target product obtained by the one-step reaction is about 65-85%, and is greatly improved compared with the yield of the traditional phenyl thiocarbamate method. The preparation method disclosed powerfully promotes the production efficiency of phenyl isothiocyanate and derivatives thereof, and has wide industrial prospect.)

1. A preparation method of phenyl isothiocyanate derivatives is characterized in that the phenyl isothiocyanate derivatives are prepared by the following preparation method: dissolving a phenyl thiocarboformate derivative and an aniline derivative in an organic solvent, heating to react by using cuprous iodide and solid alkali as catalysts, and purifying to obtain the compound.

2. The method according to claim 1, wherein the phenylthiocarbonate derivative structure is a structure in which one or more substituents selected from halogen, hydroxyl, carboxyl, cyano, phenyl, nitro, amino, alkenyl, alkynyl or alkyl groups are present at the ortho-, meta-or para-positions of the benzene ring of phenylthiocarbonate.

3. The method for producing a phenyl isothiocyanate derivative according to claim 1, wherein the aniline derivative has a structure in which a substituent selected from the group consisting of halogen, hydroxyl, carboxyl, cyano, phenyl, nitro, amino, alkenyl, alkynyl and alkyl is absent from the ortho-, meta-or para-position of aniline.

4. The process for producing a phenyl isothiocyanate derivative according to claim 2 or 3, wherein the alkyl group is a C1-C10 alkyl group.

5. The method of claim 4, wherein the alkyl group is absent or one or more branches are present, and the branches are C1-C3 alkyl groups.

6. The method for producing a phenyl isothiocyanate derivative according to claim 1, wherein the mass of the cuprous iodide is 0.1 to 1% by mass of phenyl thiocarbonate.

7. The method for producing a phenyl isothiocyanate derivative according to claim 1, wherein the mass of the solid base is 0.5 to 2 wt% of the mass of phenyl thiocarbonate.

8. The process for producing a phenyl isothiocyanate derivative according to claim 1, wherein the solid base is selected from the group consisting of sodium hydroxide, potassium hydroxide, magnesium hydroxide, copper hydroxide, barium hydroxide, copper hydroxide and aluminum hydroxide.

9. The method for producing a phenyl isothiocyanate derivative according to claim 1, wherein the heating temperature is 100-120 ℃.

10. The method for producing a phenyl isothiocyanate derivative according to claim 1, wherein the organic solvent is selected from the group consisting of dichloromethane, chloroform, tetrahydrofuran, toluene, chlorobenzene, methyl methacrylate, and dimethyl sulfoxide.

Technical Field

The invention belongs to the field of organic synthesis, and particularly relates to a preparation method of a phenyl isothiocyanate derivative.

Background

Isothiocyanate and its derivative are important organic synthesis intermediates, can participate in various organic reactions, are used for synthesizing various compounds containing nitrogen and sulfur, especially for constructing heterocyclic skeleton. Phenyl isothiocyanate and derivatives thereof are popular in academia and business as important branch structures of isothiocyanate and are widely applied to preparation of industrial products such as medicines, pesticides, dyes and the like. The enormous market demand encourages efficient, simple and economical methods for the preparation of phenylisothiocyanate and its derivatives.

Methods for preparing phenyl isothiocyanates and their derivatives have been previously reported. The current mainstream preparation method is a preparation way using primary amine as a raw material, and the preparation method is relatively simple. The first generation method is a phosgene synthesis method, and because raw materials are difficult to obtain and a byproduct thiourea generated in the reaction is more and is eliminated by people; the second generation method is a carbon disulfide method, and the main idea is that carbon disulfide reacts with a desulfurizer under the catalysis of alkali, and the defects are harsh conditions and complicated post-treatment; the third generation method is phenyl thiocarbonate method, which is relatively environment-friendly and can generate products with primary amine one-step method. The reaction steps are convenient and environmentally friendly, so the method is the most common method.

However, the phenylthiocarbonate method has drawbacks mainly in that the yield of phenylisothiocyanate or a derivative thereof produced by the one-step method is too low. The method is mainly characterized in that in the process of preparing phenyl isothiocyanate or a derivative thereof by a one-step method, in addition to obtaining a target product, two byproducts of phenyl thio (N-phenyl) carbamate and diphenylthiourea are obtained simultaneously, and the sum of the two byproducts can reach about 50-80% of the final product. This greatly reduces the yield of the objective product, and wastes a large amount of reaction substrates and energy required for the reaction, making it difficult to ensure the economy and efficiency of industrialization.

Therefore, it is highly desirable to find a new phenyl thiocarbonate method for preparing phenyl isothiocyanate and its derivatives, which overcomes the above-mentioned drawbacks.

Disclosure of Invention

The invention discloses a preparation method of a phenyl isothiocyanate derivative. The preparation method adopts a phenyl thiocarbonate method, but overcomes the inherent defects of the reaction, and greatly improves the yield of phenyl isothiocyanate and derivatives thereof, thereby strongly promoting the industrial development of the phenyl thiocarbonate method.

The technical scheme of the invention is realized by the following technical means.

A method for producing a phenyl isothiocyanate derivative, which is produced by the following production method: dissolving a phenyl thiocarboformate derivative and an aniline derivative in an organic solvent, heating to react by using cuprous iodide and solid alkali as catalysts, and purifying to obtain the compound.

Further, the structure of the phenyl thiocarbamate derivative is a structure in which one or more substituents are present at the ortho-position, the meta-position or the para-position of a benzene ring of the phenyl thiocarbamate, and the substituents are selected from halogen, hydroxyl, carboxyl, cyano, phenyl, nitro, amino, alkenyl, alkynyl or alkyl.

Further, the aniline derivative has a structure in which a substituent selected from halogen, hydroxyl, carboxyl, cyano, phenyl, nitro, amino, alkenyl, alkynyl or alkyl is absent or present at the ortho, meta or para positions of aniline.

Further, the alkyl group is selected from C1-C10 alkyl groups.

Further, the alkyl group is absent, or one or more branches are present, the branches being C1-C3 alkyl groups.

Further, the mass of the cuprous iodide is 0.1 to 1 wt% of the mass of phenyl thiocarbonate.

Further, the mass of the solid base is 0.5 to 2 wt% of the mass of phenyl thiocarbonate.

Further, the solid base is selected from sodium hydroxide, potassium hydroxide, magnesium hydroxide, copper hydroxide, barium hydroxide, copper hydroxide or aluminum hydroxide.

Further, the heating temperature is 100-120 ℃.

Further, the organic solvent is selected from dichloromethane, chloroform, tetrahydrofuran, toluene, chlorobenzene, methyl methacrylate or dimethyl sulfoxide.

The invention has the following beneficial effects: the preparation method of the phenyl isothiocyanate derivative disclosed by the invention adopts a phenyl thiocarbonate method for preparation. The substrate adopts a phenyl thiocarbonate derivative and an aniline derivative, and the raw materials are economical and easy to obtain; the yield of the target product obtained by the one-step reaction is about 65-85%, and is greatly improved compared with the yield of the traditional phenyl thiocarbamate method. The preparation method disclosed powerfully promotes the production efficiency of phenyl isothiocyanate and derivatives thereof, and has wide industrial prospect.

Detailed Description