Synthetic method for 2-substituted-1,4-naphthoquinone derivatives

Abstract

The invention discloses a synthetic method for 2-substituted-1,4-naphthoquinone derivatives. The method comprises the following steps: with 2-alkynylacetophenone compounds as shown in a formula I which is described in the specification as a raw material and dimethyl sulfoxide as an oxidizing agent and a solvent, carrying out a reaction at 80 to 140 DEG C under stirring and the action of a copper catalyst for 2 to 10 h; and subjecting a reaction solution obtained after completion of the reaction to post-treatment so as to obtain the 2-substituted-1,4-naphthoquinone derivatives as shown in a formula II which is described in the specification, wherein the copper catalyst is a mixture of bis(copper trifluoromethanesulfonate) and an inorganic cuprous salt, and the inorganic cuprous salt is one selected from a group consisting of cuprous iodide, cuprous chloride, cuprous bromide and cuprous cyanide. The method has the advantages that the raw materials are variable; the number of the prepared derivatives is great; the catalyst is cheap and easily available; cost is substantially reduced; no pollution is produced; no extra oxidizing agent is needed; dimethyl sulfoxide both functions as the oxygen source and the solvent, so cost is saved; and the method has the characteristics of high reaction yield, good substrate applicability, simple operation, etc.

Description

[0001] (1) Technical field [0002] The invention belongs to the technical field of organic compound synthesis, and in particular relates to a synthesis method of 2-substituted-1,4-naphthoquinone derivatives. [0003] (2) Background technology [0004] Naphthoquinones are a class of small molecular compounds that widely exist in nature. Due to their diverse biological activities, they are widely used in various fields such as medicine, pesticides and dyes. Naphthoquinone is an important raw material in fine chemicals, a polymerization regulator for synthetic rubber and resin, and an important substance for the synthesis of new paper cooking aids. At the same time, naphthoquinone compounds have good anti-corrosion, bactericidal and anti-ultraviolet functions, and are used in dye intermediates. Many naphthoquinone compounds also have unique antitumor effects, such as shikonin, juglone, lancidone, vitamin K3, salvicine, etc. A large number of naphthoquinone derivatives are some p...

AI Technical Summary

Problems solved by technology

At present, the existing method for synthesizing aryl naphthoquinones has the following shortcomings: (1) generally use some transition metal catalysts that are relatively expensive and polluted, and cannot be recycled, (see Kamal M Dawood. et al. Tetrahedron, 2007, 63(39): 9642-9645; Yuta Fujiwara. et al. J.Am.Chem.Soc., 2011, 133(10): 3292-3295;

(2) low reaction selectivity, poor universality and low yield (referring to people such as Pravin Patil.J.Org.Chem., 2014,79,2331-2336; Teresa Molina et al. Org. Lett., 2009, 21(11)) etc.

(3) The reaction time is long, the post-treatment is complicated, and the pollution is serious (referring to people such as Yuta Fujiwara. J.Am.Chem.Soc., 2011, 133 (10): 3292-3295) etc.

(4) The source of raw materials and the oxidant used in the reaction process are all expensive, heavily polluting and toxic reagents, greatly increasing the cost and wasting resources

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