Process for synthesizing of hydroquinone derivatives with heptadecatrienyl side chain

Patent metadata

Field	Value
Publication number	US-11078144-B2
Application number	US-201916662308-A
Country	US
Kind code	B2
Filing date	Oct 24, 2019
Priority date	Oct 24, 2019
Publication date	Aug 3, 2021
Grant date	Aug 3, 2021

Abstract

Disclosed herein is a process for chemically synthesizing of hydroquinone derivatives, especially for hydroquinone derivatives with heptadecatrienyl side chain, which is synthesized via a Wittig reaction of 2-(10′-oxononyl)-1,4-diacetoxyl benzene and (3E, 5Z)-3,5-heptadien-1-triphenylphosphonium iodide and then deacetylation. In addition, the product is solid powder.

First claim

What is claimed is:

1. A method of preparing a hydroquinone derivative with heptadecatrienyl side chain, comprising:
(a) activating 1,4-dimethoxybenzene with n-butyl lithium in tetrahydrofuran, and then reacting with 1,10-dibromodecane at room temperature to obtain a compound of formula (1)

(b) reacting the compound of formula (1) with boron tribromide to obtain a compound of formula (2)

(c) reacting the compound of formula (2) with acetic anhydride in pyridine to obtain a compound of formula (3)

(d) reacting the compound of formula (3) with sodium iodide to obtain a compound of formula (4)

(e) treating the compound of formula (4) with sodium bicarbonate in dimethyl sulfoxide and benzene, and extracting with 0.1N HCl and saturated sodium chloride to obtain a compound of formula (5)

(f) subjecting the compound of formula (5) and heptadien-1-triphenylphosphonium iodide to a Wittig reaction and then a deacetylation reaction to obtain a hydroquinone derivative with heptadecatrienyl side chain, which is a compound of formula (11)

(g) reacting the compound of formula (11) with sodium methoxide in methanol at room temperature to obtain a compound of formula (12)

wherein the compound of formula (11) is reacted with the sodium methoxide in methanol at least 20 hours, then extracted with benzene, and organic layers are combined and evaporated to dryness under reduced pressure, then purified by a silica gel column to obtain the compound of formula (12).

2. The method according to claim 1 , wherein the step (a) is carried out by activating 1,4-dimethoxybenzene with n-butyl lithium in tetrahydrofuran at −78° C. for 1 h and stirring at room temperature for 1 h, and then reacting with 1,10-dibromodecane at room temperature to obtain the compound of formula (1), then the compound of formula (1) is reacted with boron tribromide to demethylate to the compound of formula (2),
and finally, the compound of formula (2) is reacted with acetic anhydride in pyridine at 110° C., 5 h to obtain the compound of formula (3).

3. The method according to claim 1 , wherein the step (e) is carried out by the compound of formula (4) treated with sodium bicarbonate in dimethyl sulfoxide and benzene at 90° C. reflux for 4 h, and extracted with 0.1N HCl and saturated sodium chloride, after water removal with saturated sodium sulfate, obtaining the compound of formula (5).

Assignees

• Iner Aec Executive Yuan

Inventors

• Lin Kun-Liang
• Wang Ping-Yen
• Wang Mei-Hui

Classifications

• C07C41/30

  by increasing the number of carbon atoms, e.g. by oligomerisation · CPC title

• C07C67/08

  by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds · CPC title

• C07C37/0555 Primary

  being esterified hydroxy groups · CPC title

• C07C67/287

  by introduction of halogen; by substitution of halogen atoms by other halogen atoms · CPC title

• C07C67/40

  by oxidation of primary alcohols · CPC title