Alpha-amino acetophenone photoinitiator preparation method

A technology of aminoacetophenone and photoinitiator, which is applied in the direction of organic chemistry, can solve the problems of unsuitable control of reaction temperature, increase of environmental pressure, and high cost of raw materials, so as to reduce the chance of cross-contamination, reduce the number of separations, and increase the reaction time. Effect

Active Publication Date: 2016-03-09
SHANDONG JIURI CHEM TECH CO LTD
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  • Abstract
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  • Claims
  • Application Information

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Problems solved by technology

[0009] From the perspective of these two preparation processes, there are many steps, the operation is complicated and cumbersome, and each step of the reaction needs to replace different types of solvents.
The disadvantages of the second preparation process are:
[0010] 1) After replacing fluorobenzene with chlorobenzene, the morpholinyl group is introduced through a high-pressure reaction. Although the cost is reduced, the equipment requirements are relatively high;
[0011] 2) At the same time, the use of high temperature and high pressure to feed or introduce catalyst cuprous chloride must go through complex operations such as activated carbon decolorization and thermal liquid separation, especially now that the restrictions on heavy metals are becoming more and more strict. The introduction of copper ions is not only not environmentally friendly but also It also affects the appearance of the product;
[0012] 3) Using glacial acetic acid as a solvent during bromination consumes a large amount of bromine. After the reaction is completed, a large amount of sodium hydroxide is used to neutralize glacial acetic acid, resulting in a large amount of high-salt wastewater. This method is uneconomical and environmentally friendly;
[0013] 4) In the experimental step of replacing bromine with dimethylamine, solid potassium carbonate is used as an acid-binding agent, butanone is used as a solvent, and dimethylamine gas is used for substitution reaction. The raw material bromide is dissolved in butanone as a liquid, and potas

Method used

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Examples

Experimental program
Comparison scheme
Effect test

Example Embodiment

[0044] Example 1: Preparation of 1-p-fluorophenyl-1-butanone

[0045] In a 500ml four-neck flask, dissolve n-butyryl chloride (55.5g, 0.52mol) in dichloroethane (250ml), stir well, cool to about 0°C, and dissolve fluorobenzene (52.1, 0.57mol) 100ml of dichloroethane was added dropwise to the n-butyryl chloride solution. After the dripping was completed, the reaction was kept warm and the reaction was monitored by TLC or gas chromatography. After the reaction was completed, poured into the iced dilute hydrochloric acid solution, stirred for 1 hour, and allowed to stand. The phases were washed with water and saturated sodium carbonate solution respectively, and the solvent was removed. Finally, 77.8g of product was obtained by distillation under reduced pressure (conditions for collecting fractions: 102~105℃ / 9mmHg), with a yield of 90% and a purity of 99.0%. 1 HNMR(DMSO-d 6 ): d8.03(q,2H,J=9.0Hzand5.6Hz),7.31(t,2H,J=8.9Hz),2.97(t,2H,J=7.0Hz),1.65-1.55(m,2H) ,0.91(t,3H,J=7.3Hz).

Example Embodiment

[0046] Example 2: Preparation of 2-bromo-1-p-fluorophenyl-1-butanone

[0047] Take the 1-p-fluorophenyl-1-butanone (66.5g, 0.40mol) prepared according to the method of Example 1 and dissolve it in 140ml of toluene, stir it evenly, and add 6.7g of concentrated sulfuric acid dropwise to the end within 0.5h , Warm to room temperature, add bromine (51.1g, 0.32mol) dissolved in 70ml of toluene into the reaction system dropwise, after 1h drip, keep the reaction warm, and monitor the reaction by TLC or liquid chromatography. After the reaction is complete, add 67ml of Stir for 0.5h with water, stand still for layering, separate the water phase, and then extract with 70ml of toluene, combine the toluene phases, wash with saturated sodium carbonate solution, the resulting organic phase is 2-bromo-1-p-fluorophenyl-1-butan The toluene solution of ketones has a liquid content of 96.8%, and the next step is to react without purification.

Example Embodiment

[0048] Example 3: Preparation of 2-dimethylamino-1-p-fluorophenyl-1-butanone

[0049] The toluene solution of 2-bromo-1-p-fluorophenyl-1-butanone prepared in Example 2 was added to a 1L four-neck flask, and 90g of 40% dimethylamine aqueous solution (36g, 0.8mol) and sodium carbonate were added. (21.2g, 0.2mol), the reaction is stirred at room temperature, and the reaction is monitored by TLC or liquid chromatography. After the reaction is complete, stand still for layering, separate the organic phase, and then wash with water to obtain 2-dimethylamino-1-p-fluorophenyl- The toluene solution of 1-butanone has a liquid content of 96.5% and does not need to be purified to continue the next step.

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Abstract

The present invention relates to an alpha-amino acetophenone photoinitiator preparation method, particularly to a preparation method of 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone and 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)butanone. According to the present invention, 1-p-fluorophenyl-1-butanone is adopted as the raw material, and only the safe and cheap solvent is used in the whole method to conveniently prepare 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butanone and 2-(4-methylbenzyl)-2-dimethylamino-1-(4-morpholinophenyl)butanone; and the method has characteristics of cheap and readily available raw materials, high yield, no requirement of intermediate purification, and continuous reaction without solvent replacement, and is the preparation method with characteristics of low cost, environmental protection and easy operation and suitable for industrialization.

Description

technical field [0001] The present invention relates to a kind of preparation method of α-aminoacetophenone photoinitiator, be specifically related to 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl) butanone and 2-(4 The preparation method of -methylbenzyl)-2-dimethylamino-1-(4-morpholine phenyl) butanone is to use 1-p-fluorophenyl-1-butanone as the raw material, and the whole method only uses safe and cheap solvent, convenient preparation of 2-benzyl-2-dimethylamino-1-(4-morpholine phenyl) butanone and 2-(4-methylbenzyl)-2-dimethylamino-1- (4-morpholinephenyl) butanone. The raw materials of the method are cheap and easy to obtain, the yield is high, and the intermediates can be continuously reacted without purification and replacement of solvents, and are cheap, environmentally friendly, easy to operate and suitable for industrialization. Background technique [0002] α-amino ketone derivatives are a class of important photoinitiators, in which 2-benzyl-2-dimethylamino-1...

Claims

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Application Information

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IPC IPC(8): C07D295/135
Inventor 张齐罗想武瑞王涛刘川伟李伊庆李洪洲李可吕振波赵国锋
Owner SHANDONG JIURI CHEM TECH CO LTD
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