Preparation methods of dracorhodin and salt and intermediates thereof and intermediate compounds

Abstract

The invention relates preparation methods of dracorhodin and salt and intermediates thereof and intermediate compounds. Synthesis of multifunctional group-substituted benzene ring core structures, that is, the intermediate compounds V, VI and VII is achieved by taking phloroglucinol trimethyl ether as a starting raw material, combining a formylation reaction, a Huang-Minlon reduction method, a methyl ether demethylation reaction, the reaction that benzyl is introduced onto phenolic hydroxyl through benzyl halogen, the reaction that methyl is introduced onto phenolic hydroxyl by taking dimethyl carbonate as a methylation reagent, a debenzylation reaction, a demethylation reaction and the like, utilizing the intramolecular hydrogen bond effect of formyl and phenolic hydroxyl on benzene rings and controlling the proper reaction conditions through proper combinations of the reactions and a protection-deprotection strategy. According to the method, dracorhodin and the salt thereof are synthesized by adopting the raw material which is low in cost, easy to obtain and low in toxicity, the process route is short, the cost is low, the chemical selectivity of all the steps is high, the total yield reaches up to about 10%, the process reproducibility is good, industrialization can be achieved, and the green and economical properties are achieved.

Description

technical field

[0001] The invention belongs to the technical field of the preparation of hematoxylin, and in particular relates to the preparation method of hematoxylin and its salts, intermediates and these intermediate compounds. Background technique

[0002] Dermatogenin is one of the chemical components of the traditional Chinese medicine Dracaena, which was first extracted from Drosophila and then synthesized.

[0003] The document "The Pigments of Dragon's Blood Resin" PART Ⅱ "ADysthesis of Dracorhodin" (Robertson and Whalley, J.Chem.Soc., April 1950, pages 1882-1884) discloses a synthetic method of hematogenin, which first synthesizes 2,6- Methyl dihydroxy-4-methoxy-3-methylbenzoate (as starting material), and then further synthesized 4,6-dihydroxy-2-methoxy-3-methylbenzene formaldehyde, and condense 4,6-dihydroxy-2-methoxy-3-methylbenzaldehyde with benzophenone to generate hematine hydrochloride, etc. The document "Synthesis of Hematogenin" (Gao Wenfang et al., Ch...

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