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Method for preparing high-purity hinokitiol and coordination complex thereof

A high-purity technology for hinokitiol, which is applied in the field of preparation of high-purity hinokitiol and its complexes, can solve the problems of difficult to eliminate isomer by-products, cannot be industrially produced, and takes a long time to generate, and achieves excellent inhibitory effect and savings Production cost, effect of reducing the use of organic reagents

Inactive Publication Date: 2018-09-28
SHANDONG NORMAL UNIV
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Problems solved by technology

The existing synthetic routes mainly include: (1) synthesis from methoxy cycloheptatriene through isopropyl cycloheptatrienone and aminoisopropyl cycloheptatrienone; (2) synthesis from carvone through epoxidation , acetalization and other six-step reaction synthesis; (3) from isopropyl cyclohexanone or isopropyl cyclohexenone through conversion into hydroxynitrile, two steps to make isopropyl cycloheptanone, and then through oxidation, bromination (4) bromotropin reacts with an organic substance, and then synthesizes by catalytic hydrogenation; (5) generates cyclopentadienyl potassium from cyclopentadiene and potassium hydroxide, and then 1-isopropyl cyclopentadiene is obtained with isopropyl bromide; the reaction product of dichloroacetyl chloride and triethylamine is added to 1-isopropyl cyclopentadiene to obtain 1-isopropyl cyclopentadiene ene ketene adduct; 1-isopropylcyclopentadiene ketene adduct undergoes ring expansion reaction to synthesize hinokitiol; but the first four routes are more complicated, some have lower yields, some have lower purity, and some It is raw material that is difficult to obtain, can't industrial production in fact; The fifth route raw material is simple and easy to get, easy to operate, is suitable for industrialized large-scale production, but in this route, cyclopentadiene potassium is produced by cyclopentadiene and potassium hydroxide , and then in the process of preparing 1-isopropyl cyclopentadiene with isopropyl bromide, it will be accompanied by isomers 2-isopropyl cyclopentadiene and 5-isopropyl cyclopentadiene, which need to be used The method of standing for a long time is to convert the isomers into 1-isopropyl cyclopentadiene, which results in a longer generation time, and it is difficult to completely eliminate the isomer by-products in the large-scale production process, so this route Need to improve and optimize

Method used

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  • Method for preparing high-purity hinokitiol and coordination complex thereof
  • Method for preparing high-purity hinokitiol and coordination complex thereof

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preparation example Construction

[0023] In order to overcome the defects in the synthesis of hinokitiol described in the background technology, one of the purposes of the present invention provides a method for preparing high-purity hinokitiol, comprising the following steps:

[0024] (1) Add cyclopentadiene to water at a temperature of 0-5°C, react with sodium hydroxide, N-chlorosuccinimide, and ether, filter the reaction solution with suction, add hydrochloric acid to the reaction solution, and adjust the pH The value is 6 to 7. After decompressing to distill off the ether, the reaction solution is extracted with ethyl acetate and concentrated to obtain 1-chlorocyclopentadiene;

[0025] (2) Add 1-chlorocyclopentadiene to water, keep the solution temperature at 0°C, and react with dichloroacetyl chloride, barium hydroxide, and chloroform to obtain 1-chlorocyclopentadiene-4,4-dichlorocyclobutane 5-keto;

[0026] (3) Add 1-chlorocyclopentadiene 4,4-dichlorocyclobutane 5-one to a mixed solvent of acetic acid, ...

Embodiment 1

[0041]Add 66g (1mol) of cyclopentadiene into 330mL of water, set the reaction temperature to 0-5°C, slowly add 150g of sodium hydroxide solution with a concentration of 40% dropwise, stir for 30min after the dropwise addition, rise to room temperature, and divide Add 140g of N-chlorosuccinimide in four batches, 35g in each batch. After adding the last batch of NCS, keep stirring at 40°C for 30 minutes. TLC monitors the complete reaction of the raw materials. After cooling down to 10°C, pour into the reaction solution Add 460g of diethyl ether, a white solid precipitates, filter the reaction solution with suction, add a certain amount of hydrochloric acid to the reaction solution, adjust the pH to 6-7, then distill the ether under reduced pressure, the diethyl ether can be reused, and extract the reaction solution with ethyl acetate , 96 g of 1-chlorocyclopentadiene was obtained after concentration, and the yield was 96%.

Embodiment 2

[0043] Add 66g (1mol) of cyclopentadiene into 330mL of water, set the reaction temperature to 0-5°C, slowly add 100g of sodium hydroxide solution with a concentration of 40% dropwise, stir for 30min after the dropwise addition, rise to room temperature, and divide Add 140g of N-chlorosuccinimide in four batches, 35g in each batch. After adding the last batch of NCS, keep stirring at 40°C for 30 minutes. TLC monitors the complete reaction of the raw materials. After cooling down to 10°C, pour into the reaction solution Add 460g of diethyl ether, a white solid precipitates, filter the reaction solution with suction, add a certain amount of hydrochloric acid to the reaction solution, adjust the pH to 6-7, then distill the ether under reduced pressure, the diethyl ether can be reused, and extract the reaction solution with ethyl acetate After concentration, 74 g of 1-chlorocyclopentadiene was obtained, and the yield was 74%.

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Abstract

The invention belongs to the technical field of synthesis of pharmaceutical intermediates, and relates to a method for preparing high-purity hinokitiol and a coordination complex thereof. The method comprises the steps that 1-perchlorocyclopentadiene is generated by using cyclopentadiene, sodium hydroxide and NCS and reacts with dichloracetyl chloride, barium hydroxide is added, dilute sulphuric acid and chloroform are added after the reaction, and 1-chloro cyclopentadiene 4,4-dichloro cyclobutyl5-ketone is obtained through a final reaction; 1-chloro cyclopentadiene 4,4-dichloro cyclobutyl5-ketone is mixed with a mixed solution of acetic acid, acetone and water, then barium hydroxide is added, and 2-hydroxyl-4-chloro-2,4,6-cycloheptatrien-1-ketone is obtained through a final reaction; 2-hydroxyl-4-chloro-2,4,6-cycloheptatrien-1-ketone is added to THF, potassium phosphate and isopropylboronic acid are added, and the mixture after the reaction is added to a mixed solution of methanol, HCl / 1 and 4-dioxane to obtain hinokitiol at last. The method has the advantages that the process is simple, the cost is low, and the product purity is high.

Description

technical field [0001] The invention belongs to the technical field of synthesis of pharmaceutical intermediates, and in particular relates to a preparation method of high-purity hinokitiol and its complexes. Background technique [0002] The chemical name of hinokitiol is 2-hydroxy-4-(1-methylethyl)-2,4,6-cycloheptatrien-1-one, and the molecular formula is C 10 h 12 o 2 , with a molecular weight of 164.2. It is a natural compound of monoterpene with a tropolone skeleton extracted from the trunk of Taiwan cypress by the Japanese scientist Anderson in 1948. Repelling effect, it is a high-safety plant ingredient that can be used as an antibacterial and insect repellant. Hinokitiol is the main component of Taiwanese cypress essential oil. It has a wide range of biological activities and strong bactericidal ability. The minimum inhibitory concentration for general bacteria is 10-100ppm. Bacteria, prevent pests from invading the human body, and inhibit human pathogenic bacte...

Claims

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Application Information

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IPC IPC(8): C07C45/77C07C45/68C07C49/717A01N35/06A01P1/00
CPCA01N35/06C07C17/10C07C45/455C07C45/61C07C45/68C07C45/77C07C49/717C07C2601/10C07C2601/18C07C2602/20C07C49/627C07C23/08
Inventor 孙彬
Owner SHANDONG NORMAL UNIV
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