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Ether bond breaking method of phenyl alkyl ether

A technology of phenyl alkyl ether and ether bond, which is applied in the field of intermediate synthesis of pharmaceuticals and chemical raw materials, can solve the problems of poor stability of carbodiimide, physical injury of operators, poor storage stability, etc., and achieve stable properties and applicable Wide range and low air pollution effect

Active Publication Date: 2017-12-15
JINGCHU UNIV OF TECH
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0004] CN106278825A discloses a method for breaking ether bonds with aluminum triiodide-pyridine, which removes the methyl group of eugenol with a near quantitative yield, but because pyridine affects the aluminum triiodide by complexing with aluminum triiodide Oxophilicity, resulting in this method can only be used for o-hydroxy phenyl alkyl ethers, but not for the ether bond cleavage of ordinary phenyl alkyl ethers without ortho-hydroxyl groups
[0005] CN106866377A discloses the method of aluminum triiodide-carbodiimide breaking ether bond, basically solves the ether bond breaking problem of all kinds of common phenyl alkyl ethers, yet the by-product of carbodiimide becomes Impurities that need to be removed, and carbodiimides are generally less stable
[0006] Pyridine smells very heavy, pollutes the air, and does certain harm to the operator's body
Carbodiimide is generally more expensive and has poor storage stability
In addition, by-products of pyridine and carbodiimide production are organic and can become organic pollutants if not handled properly

Method used

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  • Ether bond breaking method of phenyl alkyl ether
  • Ether bond breaking method of phenyl alkyl ether
  • Ether bond breaking method of phenyl alkyl ether

Examples

Experimental program
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Effect test

Embodiment 1

[0030] Embodiment 1 (eugenol demethylation)

[0031]

[0032] Add aluminum triiodide (2.242g, 5.5mmol), acetonitrile (40ml), potassium tert-butoxide (1.237g, 11.0mmol) and eugenol (0.819g, 5.0mmol) to a 100ml eggplant-shaped flask, heat to 80 ℃, stop stirring after 18 hours of reaction, cool to room temperature, add 2mol / L dilute hydrochloric acid (10ml) into the eggplant-shaped bottle to acidify, extract with ethyl acetate (50ml×3), combine the organic phases, and first use thiosulfuric acid Wash with saturated sodium aqueous solution (10ml), then with saturated brine (10ml), dry over anhydrous magnesium sulfate, filter, and the filtrate is evaporated to dryness with a rotary evaporator, and the residue is subjected to flash column chromatography (eluent is ethyl acetate / Petroleum ether=1:4, volume ratio) purification to obtain 0.733g 4-allyl catechol crude product, take the 4-allyl catechol crude product (0.709g) and sublimate under reduced pressure with an oil pump to o...

Embodiment 2

[0035] Embodiment 2 (eugenol demethylation)

[0036]

[0037] CuO (5.966g) was used to replace potassium tert-butoxide, and the other conditions were consistent with Example 1 to obtain 4-allyl catechol (yield 88%).

Embodiment 3

[0038] Embodiment 3 (eugenol demethylation)

[0039]

[0040] CaO (4.200g) was used to replace CuO, and the remaining conditions were consistent with Example 2 to obtain 4-allyl catechol (yield 95%).

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Abstract

The invention discloses an ether bond breaking method of phenyl alkyl ether. The ether bond breaking method comprises the following step: in an organic solvent, in the presence of aluminum triiodide and an inorganic acid scavenger, performing an ether bond breaking reaction on the phenyl alkyl ether from -20 DEG C to the refluxing temperature to produce phenol and derivatives thereof. The ether bond breaking method is mild in condition, easy to operate and high in yield, and is suitable for a wide range of phenyl alkyl ether.

Description

technical field [0001] The invention relates to the technical field of intermediate synthesis of medicines and chemical raw materials, in particular to a method for breaking ether bonds of phenyl alkyl ethers. Background technique [0002] Dealkylation of phenyl alkyl ethers by cleavage of ether bonds is a common functional group transformation for the preparation of phenols. Ether bond cleavage can be realized with Bronsted acid or Lewis acid, commonly used Bronsted acid has HBr and HI etc., commonly used Lewis acid has boron tribromide, aluminum trichloride and aluminum triiodide etc. (Synthesis 1983,15,249-282; Tetrahedron 2005, 61, 7833-7863; Organic Preparations and Procedures International 1996, 28, 371-409). When the substrate contains both acid-sensitive functional groups and active hydrogen, demethylation by these methods will be more difficult, such as eugenol demethylation by these methods can only obtain moderately low yields (Journal of Agricultural and FoodChe...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07B41/02C07C37/055C07C39/19C07C39/08C07C45/64C07C47/565C07C49/825C07C201/12C07C205/44C07C205/22C07C231/12C07C233/18C07C253/30C07C255/53
CPCC07B41/02C07C37/055C07C45/64C07C201/12C07C231/12C07C253/30C07C39/19C07C39/08C07C47/565C07C49/825C07C205/44C07C205/22C07C233/18C07C255/53
Inventor 田娟易翠翠姚明桑大永
Owner JINGCHU UNIV OF TECH
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