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

A kind of compound, the technology of dracoidin, which is applied in the field of drexin preparation, can solve the problems of low total yield, poor selectivity, poor process reproducibility, etc.

Active Publication Date: 2016-05-25
INNOCHEM BEIJING TECH CO LTD
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

However, the selectivity of some steps in the above process, such as reactions such as methylation, is poor, resulting in a low overall yield; and the process has poor reproducibility and a small reaction scale, which cannot be applied on a large scale in industry

Method used

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

Examples

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Effect test

preparation example Construction

[0121] As shown in the above reaction process (a), the preparation method of hematogenin provided by the present invention comprises the following steps:

[0122] 1) Vilsmeier formylation of compound SM and formylation reagent to produce compound I,

[0123]

[0124] 2) In solvent B, make compound I, 50-85wt% hydrazine hydrate and sodium hydroxide or potassium hydroxide undergo Huang Minglong reduction reaction, so that the aldehyde group of compound I is reduced to methyl, and compound II is obtained.

[0125]

[0126] 3) Vilsmeier formylation of compound II and formylation reagent to produce compound III,

[0127]

[0128] 4) In solvent D, under the protection of nitrogen, use a demethylation reagent to crack the methoxy group on the benzene ring of compound III to remove the methyl group to obtain compound IV,

[0129]

[0130] 5) Substituting the phenolic hydroxyl group of compound IV with benzyl halide in solvent E and in the presence of base E to obtain comp...

Embodiment 1

[0143] This example is used to illustrate the preparation method of hematine hydrochloride / perchlorate.

[0144] Step 1): preparation of compound Ⅰ (2,4,6-trimethoxybenzaldehyde)

[0145]

[0146] specific method:

[0147] Mix 100g of compound SM (phloroglucinol trimethyl ether) and 500ml of DMF, cool the temperature in an ice-salt bath to below 0°C, add 201g (2.2eq) of phosphorus oxychloride dropwise, control the temperature below 0°C, and finish adding at below 0°C Insulation reaction for 1h, TLC tracking reaction completed; the reaction solution was poured into ice water, adjusted to weakly alkaline (pH 8-10) with potassium carbonate solution, crystallized overnight, suction filtered to obtain a white solid, and dried to obtain 101g of the product (compound Ⅰ), its hydrogen nuclear magnetic resonance (HNMR) spectrum is shown in figure 1 .

[0148] Compound Ⅰ proton magnetic spectrum (see figure 1 ) chemical shift data are: (CDCl3, 300M), 3.871-3.879, MeO, 9H; 6.071, ...

Embodiment 2

[0184] This example is used to illustrate the preparation method of heserodin perchlorate.

[0185] As shown in the following reaction formula, the perchlorate (compound Ⅸ) of hematine can be prepared from the hydrochloride (compound Ⅷ) according to the existing method.

[0186]

[0187] Therefore, in this embodiment, hematine hydrochloride can be prepared first by referring to steps 1)-8) of the embodiment, and then hematine perchlorate can be prepared according to the following step 9), the specific method is as follows:

[0188] specific method:

[0189] 5 g of compound VIII was dissolved in 60 ml of methanol, 80 ml of methanol solution of 2 ml of perchloric acid was added dropwise, and the reaction was stirred for 2 h. Precipitate orange-red crystals, filter, and recrystallize the solid with methanol to obtain 5g of compound IX pure product, its hydrogen nuclear magnetic resonance (HNMR) spectrum is shown in Figure 4 .

[0190] Compound Ⅸ proton magnetic spectrum (s...

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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...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07D311/60
CPCC07D311/60
Inventor 陈从喜田永建梁秋严鲍晓伟
Owner INNOCHEM BEIJING TECH CO LTD
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