Method for synthesizing 3-aryl allyl group ether

A kind of technology of aryl allyl ether and synthesis method, which is applied in ether preparation, organic chemistry, etc., can solve the problems of non-recyclable metal, harm to human body and environment, instability of allyl tin, etc., and achieve moderate activity and low price Inexpensive, easy to operate and convenient effect

Inactive Publication Date: 2008-03-05
HANGZHOU NORMAL UNIVERSITY
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Problems solved by technology

When allyl bromide is used as the allylation reagent, an equivalent amount of metal is required as a reducing agent such as: iron, magnesium, zinc, copper, manganese, aluminum, indium, samarium, etc., but the metal cannot be recycled, and allyl bromide Bromine has certain toxicity and is harmful to the human body and the environment; allyl tin itself is relatively unstable and has certain toxicity, and requires equivalent metal catalysts such as: titanium tetrachloride, aluminum trichloride , tin tetrachloride; no matter from an economic point of view or from an environmental point of view, it is more unfavorable to use allyl bromide or allyl tin as an allylation reagent, so allyl silane is allyl Reagent of choice for alkylation
But allyl chlorosilane is relatively active, and its participation in the reaction needs to be carried out under anhydrous conditions, and the scope of substrates is also greatly limited; allyl alkylsilane often requires complicated reaction conditions as an allylation reagent, such as Requires equivalent Lewis acid catalyst (titanium tetrachloride, aluminum trichloride, boron trifluoride ether, etc.), anhydrous low temperature and other conditions, using acetal two-step synthesis

Method used

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  • Method for synthesizing 3-aryl allyl group ether
  • Method for synthesizing 3-aryl allyl group ether

Examples

Experimental program
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Effect test

Embodiment 1

[0017] Ferric chloride catalyzes the reaction of benzaldehyde with allyltriethoxysilane to prepare 3-phenylallyl ethyl ether.

[0018] Put a 10ml glass bottle with a rubber stopper on the 85-2 type constant temperature magnetic stirrer, add 2ml of nitromethane, 0.106g (1mmol) benzaldehyde, 0.224g (1.1mmol) allyltriethoxysilane, quickly Weigh 0.0162g (0.1mmol) of ferric trichloride into the reaction bottle, and cover with a rubber stopper. Then stir at room temperature for 3 hours to react. Then extracted three times with 1:1 petroleum ether / diethyl ether (15ml×3), combined the organic phases, dried over anhydrous sodium sulfate, and evaporated the solvent under reduced pressure to obtain 1.67g of oily liquid product with a yield of 95%. m / z176(M + )135(100)107(79)79(63) 1 H NMR (400MHz, CDCl 3 ) 7.30 (m 5H) 5.77 (m 1H) 5.34 (m 2H) 4.26 (t J = 8.0Hz 1H) 3.36 (m 2H) 2.57 (m 1H) 2.40 (m 1H) 1.18 (t J = 8.0Hz 3H) 13 C NMR (100MHz, CDCl 3 ) 142.26 134.84 128.12 127.28 126.48 ...

Embodiment 2

[0020] Ferric chloride catalyzes the reaction of o-chlorobenzaldehyde and allyl triethoxysilane to prepare 3-(1-chlorophenyl) allyl ethyl ether.

[0021] Put a 10ml glass bottle with a rubber stopper on the 85-2 type constant temperature magnetic stirrer, add 2ml of nitromethane, 0.141g (1mmol) o-chlorobenzaldehyde, 0.224g (1.1mmol) allyltriethoxysilane , quickly weighed 0.0162g (0.1mmol) ferric chloride into the reaction bottle, and covered with a rubber stopper. Then it was stirred for 3 hours at normal temperature. Then it was extracted three times with 1:1 petroleum ether / diethyl ether (15mlx3), the organic phases were combined, dried over anhydrous sodium sulfate, and the solvent was evaporated under reduced pressure to obtain 0.202 g of an oily liquid product with a yield of 96%. m / z210(M + )171(28)169(84)141(100)113(30) 1 H NMR (400MHz, CDCl 3 )7.49(m 1H)7.30(m 2H)7.20(m 1H)5.87(m 1H)5.05(m 2H)3.87(m 1H)3.38(m 2H)2.46(m 2H)1.19(t J=8.0Hz 3H) 13 C NMR (100MHz, CDCl ...

Embodiment 3

[0023] Indium trichloride catalyzes the reaction of p-bromobenzaldehyde with allyl triethoxysilane to prepare 3-(3-bromophenyl) allyl ethyl ether.

[0024] Put a 10ml glass bottle with a rubber stopper on the 85-2 type constant temperature magnetic stirrer, add 2ml of dichloromethane, 0.185g (1mmol) p-bromobenzaldehyde, 0.224g (1.1mmol) allyltriethoxysilane , quickly weighed 0.0221g (0.1mmol) indium trichloride, 0.163g (1.5mmol) trimethylchlorosilane and added to the bottle. Then it was stirred for 3 hours at normal temperature. Then extracted three times with 1:1 petroleum ether / diethyl ether (15mlx3), combined the organic phases, dried over anhydrous sodium sulfate, and evaporated the solvent under reduced pressure to obtain 0.225g of oily liquid product with a yield of 96%. m / z255(M + )215(92)213(100)187(75)185(89)157(32)77(62) 1 H NMR (400MHz, CDCl 3 ) 7.46 (d J = 8.0Hz 2H) 7.18 (d J = 8.0Hz 2H) 5.74 (m 1H) 5.02 (m 2H) 4.23 (t J = 6.0Hz 1H) 3.34 (m 2H) 2.54 (m 1H) 2.35...

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Abstract

The present invention relates to synthesis of organic material, and is especially process of synthesizing 3-arylallyl ether. Inside solvent of nitromethane, dichloromethane, ethyl cyanide, trichloromethane, toluene or tetrahydrofuran, and in the presence of catalyst of ferric chloride, indium chloride, zinc dichloride, copper bromide, ferric perchlorate or magnesium perchlorate, aromatic aldehyde and allylalkoxyl silane are reacted to produce 3-arylallyl ether. Adding trimethylchlorosilane into indium chloride catalyst can result in even high catalytic effect. The present invention has the advantages of simple operation, high safety, environment friendship, etc. and the synthesized organic intermediate has wide application.

Description

technical field [0001] The invention relates to a method for synthesizing organic matter, in particular to a method for synthesizing 3-aryl allyl ether. technical background [0002] 3-Aryl allyl ethers are an important class of organic compounds, which are mainly obtained from the reaction of acetals or aldehydes with allylating reagents under the catalysis of Lewis acids. In recent years, there are generally three types of allylation reagents for the synthesis of 3-aryl allyl ethers: allyl bromide, allyl tin, and allyl silane. When allyl bromide is used as the allylation reagent, an equivalent amount of metal is required as a reducing agent such as: iron, magnesium, zinc, copper, manganese, aluminum, indium, samarium, etc., but the metal cannot be recycled, and allyl bromide Bromine has certain toxicity and is harmful to the human body and the environment; allyl tin itself is relatively unstable and has certain toxicity, and requires equivalent metal catalysts such as: ti...

Claims

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Application Information

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IPC IPC(8): C07C43/166C07C43/176C07C41/01
Inventor 徐利文杨明松张飞豹邱化玉蒋剑雄来国桥
Owner HANGZHOU NORMAL UNIVERSITY
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