A kind of preparation method of 24-epibrassin intermediate (22e, 24r)-3α, 5-ring-5α-ergosta-7,22-dien-6-one

A technology for intermediates and surface Brassica, applied in the field of preparation of plant growth regulators, can solve the problems of low total yield, high operator requirements, environmental pollution, etc., and achieves the effects of fast reaction rate and simple post-processing

Active Publication Date: 2021-03-19
郑州郑氏化工产品有限公司
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  • Abstract
  • Description
  • Claims
  • Application Information

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Problems solved by technology

Due to the long steps and low overall yield, the preparation of intermediate 3 adopts the chromium trioxide / pyridine oxidation system, which will produce a large amount of waste liquid and solid waste containing heavy metal ions, which seriously pollutes the environment;
[0005] (2) McMorris et al. improved the synthetic method of 24-epibrassinolin in 1993 (McMorris T.C., Patil, J.Org.Chem.1993,58,2338.), and shortened the synthetic steps to seven steps, but Still using the chromium trioxide / pyridine oxidation system to prepare intermediate 3, resulting in a large amount of waste liquid and solid waste containing heavy metal ions, which seriously pollutes the environment;
Osmium tetroxide is a volatile and highly toxic solid powder, which is expensive, high in cost, and requires high requirements for operators
And when using potassium bromide + TBAOX or TBAB + Oxone combination, the reaction conversion is very slow

Method used

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  • A kind of preparation method of 24-epibrassin intermediate (22e, 24r)-3α, 5-ring-5α-ergosta-7,22-dien-6-one
  • A kind of preparation method of 24-epibrassin intermediate (22e, 24r)-3α, 5-ring-5α-ergosta-7,22-dien-6-one
  • A kind of preparation method of 24-epibrassin intermediate (22e, 24r)-3α, 5-ring-5α-ergosta-7,22-dien-6-one

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0045] A preparation method of 24-epibrassin intermediate (22E, 24R)-3α, 5-ring-5α-ergosta-7,22-dien-6-one, comprising the following steps:

[0046] 1) Add 100.0 g of ergosterol, 800.0 g of acetone and 4.3 g of tetrabutylammonium bisulfate to the reaction flask, stir for 0.5 h, cool down to -5~5°C with ice-cold brine, add 29.0 g of methanesulfonyl chloride, and Add 25.5g of triethylamine dropwise at 5-5°C for 0.5h. After the dropwise addition, continue the reaction at -5-5°C for 4h. After the reaction, intermediate 1 is obtained. Filter the reaction solution to obtain a white solid and pale yellow filtrate containing intermediate 1;

[0047] 2) Add 200 g of water and 32.8 g of potassium bicarbonate to the light yellow filtrate containing intermediate 1 obtained in step 1), stir and heat up to 50° C. and keep the temperature for 5 hours. After the reaction, stop stirring under heat preservation, and separate the phases. The lower aqueous phase was separated, and the upper orga...

Embodiment 2

[0053] A preparation method of 24-epibrassin intermediate (22E, 24R)-3α, 5-ring-5α-ergosta-7,22-dien-6-one, comprising the following steps:

[0054] 1) Add 100.0 g of ergosterol, 900.0 g of acetone and 8.6 g of tetrabutylammonium bisulfate to the reaction flask, stir for 0.5 h, cool down to -5~5°C with ice-cold brine, add 58.0 g of methanesulfonyl chloride, and Add 51.0g of triethylamine dropwise at 5~5°C for 0.5h. After the dropwise addition, continue the reaction at -5~5°C for 3h. After the reaction, Intermediate 1 is obtained. Filter the reaction solution to obtain a white solid and pale yellow filtrate containing intermediate 1;

[0055] 2) Add 150 g of water and 50.0 g of potassium bicarbonate to the light yellow filtrate containing intermediate 1 obtained in step 1), stir and heat up to 55° C. and keep the temperature for 3 hours. After the reaction, stop stirring under heat preservation, and separate the phases. The lower aqueous phase was separated, and the upper orga...

Embodiment 3

[0060] A preparation method of 24-epibrassin intermediate (22E, 24R)-3α, 5-ring-5α-ergosta-7,22-dien-6-one, comprising the following steps:

[0061] 1) Add 100.0 g of ergosterol, 1000.0 g of acetone and 43.0 g of tetrabutylammonium bisulfate to the reaction flask, stir for 0.5 h, cool down to -5~5°C with ice-cold brine, add 87.0 g of methanesulfonyl chloride, and 76.5g of triethylamine was added dropwise at 5-5°C for 0.5h. After the dropwise addition, the reaction was continued at -5-5°C for 2h. After the reaction, Intermediate 1 was obtained. The reaction solution was filtered to obtain a white solid and pale yellow filtrate containing intermediate 1;

[0062] 2) Add 100 g of water and 75.0 g of potassium bicarbonate to the light yellow filtrate containing intermediate 1 obtained in step 1), stir and heat up to 60° C. and keep the temperature for 2 hours. After the reaction, stop stirring under heat preservation, and separate the phases. The lower aqueous phase was separated...

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Abstract

The invention discloses a preparation method of a 24-epibrassinolide intermediate, and belongs to the field of chemical synthesis, and the preparation method comprises the following steps: 1) taking ergosterol as an initial raw material, carrying out methanesulfonylation under the catalysis of tetrabutylammonium hydrogen sulfate to obtain a first-step product, namely an intermediate 1, filtering afirst-step reaction solution, and directly carrying out a next-step reaction on a filtrate; 2) adding water and potassium bicarbonate into the filtrate obtained in the step 1), carrying out heating reaction, and carrying out split-phase water removal, concentration, cooling and filtration to obtain an intermediate 2; 3) reacting the intermediate 2 with benzyl halide in the presence of an acid-binding agent to generate an etherification product; 4) reacting the etherification product with tetrabutylammonium bromide and tetrabutylammonium hydrogen persulfate to obtain an intermediate 3; compared with a traditional CrO3 / pyridine oxidation method, the method has the advantages that the use of an oxidizing agent containing heavy metal chromium and having serious pollution to the environment isavoided, the reaction conditions are mild, the yield is high, the post-treatment is simple, the next step of reaction can be performed without refining, and the method is suitable for industrial production.

Description

technical field [0001] The invention belongs to the technical field of preparation of plant growth regulators, in particular to a 24-epibrassin intermediate (22E, 24R)-3α, 5-ring-5α-ergosta-7,22-diene-6- Method for the preparation of ketones. Background technique [0002] 24-epibrassinolide is a broad-spectrum and high-efficiency plant growth regulator. It was discovered by American agricultural scientists in 1970 and named brassinosteroid, also known as 24-epibrassinolide. 24-epibrassinolide is different from other plant growth regulators in its one-way targeting in promoting crop yield and quality. Not only has the physiological function of auxin and cytokinin, but also has the functions of improving photosynthesis, regulating nutrient distribution, promoting the transport of carbohydrates from stems and leaves to grains, improving the resistance of crops to external adverse factors, and promoting the growth of weak parts of plants, etc. function, therefore, it has extre...

Claims

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Application Information

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Patent Type & Authority Patents(China)
IPC IPC(8): C07J9/00C07J53/00C07J31/00
CPCC07J9/00C07J31/006C07J53/004
Inventor 郑先福闻东亮许伟长
Owner 郑州郑氏化工产品有限公司
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