CN103242261A - Synthetic method of alpha-amino aromatic ketone compound - Google Patents
Synthetic method of alpha-amino aromatic ketone compound Download PDFInfo
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Abstract
The invention relates to a synthetic method of an alpha-amino aromatic ketone compound. The reaction method comprises step one, reacting benzene or substituted benzene and 2-bromo-isobutyl chloride with a water-insoluble solvent in the presence of a catalyst in the absence of water to generate an intermediate product 2-bromo-2-methyl-1-benzene or substituted propiophenone; and step two, reacting the intermediate product with a compound having a secondary amine structure under an action of an organic solvent and the catalyst, and performing aftertreatment of hydrolysis, extraction and the like to obtain the alpha-amino aromatic ketone compound of which the final yield is up to more than 80 percent and the purity is more than 97 percent. The synthetic method of the alpha-amino aromatic ketone compound is high in yield and product purity, low in environmental pollution and low in cost, and an industrial production requirement of alpha-amino aromatic ketone photoinitiator can be met, so that the possibility is provided for the industrial production of the product.
Description
Technical field
The present invention relates to the synthetic method of a kind of ultraviolet initiator-alpha-amino group arone compounds.
Background technology
Alpha-amino group arone photoinitiator is because wherein have amido, and it is water-soluble relatively good.Because can being combined with inorganic salt, amido forms salt simultaneously, so the property transformed of amine light trigger is very strong.From the light trigger 369 of initial exploitation to light trigger 379,907, N-1414, Polymeric 910, the trend of the oriented macromolecular photoinitiator development of the development of amine light trigger.Because its synthetic difficulty is bigger, particularly light trigger 907, and study on the synthesis both domestic and external is few.
(1) external synthesis technique
(WO2006034966) such as the Pretot Roger of Ciba-Geigy company is starting raw material with the thioanisole, after friedel-crafts reaction, halogenating reaction, epoxidation reaction, obtains light trigger 907 with the morpholine reaction.This technology has following deficiency: reactions steps is many, complex procedures, the difficult suitability for industrialized production that realizes; Except meeting generates the alpha-chloro reaction product, also can generate polysubstituted by product in the chlorination, be unfavorable for the purification of product; Produce a large amount of waste water, contaminate environment in the subsequent disposal of each step reaction.
(JP10114736) such as the flat husbands of Tanaka is starting raw material with the chlorobenzene, by reacting with isobutyryl chloride, obtain 2-methyl isophthalic acid-(4-chloro-phenyl-)-1-acetone, afterwards under the effect of phase-transfer catalyst, obtain 2-methyl isophthalic acid-(4-methylthio group) phenyl-1-acetone with the thiomethyl alcohol gas reaction, obtain light trigger 907 with chlorine and morpholine reaction again, total recovery has reached 87.9 ﹪.But shortcoming is the reaction process complexity, and by product is more, and target product needs repeatedly recrystallization just can obtain satisfactory product.
(2) domestic synthesis technique
Liu Bijian etc. (CN101633647) improve the operational path of Ciba-Geigy company exploitation.Adopt isobutyryl chloride to substitute isobutyric anhydride, bromine substitutes chlorine and carries out halogenating reaction, obtains product, overall yield of reaction 86 ﹪ through epoxidation and amine replacement ring-opening reaction.But shortcoming is the reaction process complexity; The reaction raw materials bromine belongs to hazardous substance, is not suitable for long-distance transport; Epoxidation reaction condition needs definitely anhydrous, makes that the reaction yield fluctuation is bigger, difficult quality guarantee.
Luo Bikui etc. (CN1354175) are raw material with the thioanisole, and Louis's acid as catalyst by paying gram, halo, amine replacement three-step reaction, obtains light trigger 907, purity 99.4 ﹪, yield 92.7 ﹪ through crystallization, filtration, drying.But shortcoming is to use noxious solvent oil of mirbane and bromine, makes production operation danger increase.
Zhao Wen superfine (CN101659644) is raw material with 2-methyl-2-(4-morpholinyl)-1-(4-chloro-phenyl-)-1-acetone, carries out thioetherification reaction with the sodium methyl mercaptide aqueous solution under the effect of quaternary amine phase-transfer catalyst, obtains light trigger 907.This method weak point is: reaction raw materials 2-methyl-2-(4-morpholinyl)-1-(4-chloro-phenyl-)-1-acetone is expensive; Raw material and product separation difficulty, subsequent operations step complexity.
Summary of the invention
The objective of the invention is at above-mentioned present situation, aim to provide a kind of demand that can satisfy alpha-amino group arone photoinitiator suitability for industrialized production, the yield of product and purity height, the synthetic method of a kind of alpha-amino group arone compounds that environmental pollution is little, cost is low.
Purpose implementation of the present invention is, a kind of novel synthesis of Alpha-hydroxy arone compounds, and reaction is carried out in two steps:
The first step, benzene or substituted benzene, 2-bromo isobutyryl chloride, water-insoluble solvent is reacted under catalyzer aluminum trichloride (anhydrous) and anhydrous condition, generates intermediate product 2-bromo-2-methyl isophthalic acid-benzene or substituted benzene acetone,
Described benzene or substituted benzene refer to benzene, thioanisole, toluene or chlorobenzene,
Described water-insoluble solvent refers to benzene, 1,2-ethylene dichloride, toluene or chlorobenzene,
The mol ratio of 2-bromo isobutyryl chloride and catalyzer aluminum trichloride (anhydrous) is 1:1～1.2;
In second step, intermediate product is under organic solvent, the effect of catalyzer aluminum trichloride (anhydrous), and the compound reaction with containing the secondary amine structure gets alpha-amino group arone class compounds through aftertreatments such as hydrolysis, chloroform extractions, and the ultimate yield of its product reaches more than 80 ﹪,
The described compound that contains the secondary amine structure refers to morpholine, diethylamine or piperidines,
Described organic solvent refers to 60-90 ℃ of sherwood oil, toluene or benzene,
The mol ratio of intermediate product and catalyzer aluminum trichloride (anhydrous) is 1:0.1～1;
Concrete reaction formula is:
In the formula: R
1Be H, SCH
3, CH
3Or Cl,
R
2Be morpholine, diethylamine or piperidines,
The present invention is raw materials used cheap and easy to get, the reaction conditions gentleness, and by product is few, and the ultimate yield of product reaches more than 80 ﹪; Can satisfy the suitability for industrialized production demand of alpha-amino group arone photoinitiator, the yield of product and purity height, environmental pollution is little, cost is low, has good industrial prospect, for the suitability for industrialized production of product provides possibility.
Embodiment
Reaction of the present invention is carried out in two steps:
The first step, benzene or substituted benzene, 2-bromo isobutyryl chloride, water-insoluble solvent are reacted under catalyzer and anhydrous condition, generate intermediate product 2-bromo-2-methyl isophthalic acid-benzene or substituted benzene acetone.
In the four-hole boiling flask that thermometer, drying tube, mechanical stirring, constant pressure funnel are housed, add benzene or substituted benzene, catalyzer aluminum trichloride (anhydrous), water-insoluble solvent, after stirring, drip 2-bromine isobutyryl chloride 0～5 ℃ of temperature of reaction, dropwise back room temperature reaction 9h; After reaction finishes, obtain water with the extraction of 10 ﹪ aqueous hydrochloric acids; Tell organic phase with organic solvent subsequently; Regulate organic phase to pH=7 with saturated sodium bicarbonate solution washing, the underpressure distillation of gained organic phase obtains intermediate product 2-bromo-2-methyl isophthalic acid-benzene or substituted benzene acetone to-0.096mpa;
Described water-insoluble solvent is 60-90 ℃ of sherwood oil, ethylene dichloride or toluene,
The described organic solvent of telling organic phase is 60-90 ℃ of sherwood oil, ethylene dichloride or toluene.
In second step, intermediate product is under organic solvent, catalyst action, and the compound reaction with containing the secondary amine structure gets the alpha-amino group arone compounds through last handling processes such as hydrolysis, extraction, recrystallizations, and the ultimate yield of its product reaches more than 80 ﹪.
Add organic solvent, intermediate product, catalyzer aluminum trichloride (anhydrous) in the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring, constant pressure funnel are housed, contain the compound of secondary amine structure, 30～55 ℃ of stirring reaction 5～16h; After reaction finished, distillation removed the intact raw material of unreacted; With 10% aqueous hydrochloric acid conditioned reaction liquid pH=2, add organic solvent extraction, leave standstill and tell water, with saturated sodium carbonate solution water transfer phase pH=10, separate out faint yellow solid; The solid of separating out with trichloromethane dissolving is told organic phase again, be distilled to-0.096mpa obtains thick product; Use the mixed solvent recrystallization of ethanol and water subsequently, obtain alpha-amino group arone compounds product, the volume ratio 2:1 of ethanol and water;
Described organic solvent is 60-90 ℃ of sherwood oil, toluene or benzene,
The compound that contains the secondary amine structure is morpholine, diethylamine or piperidines.
With specific embodiment in detail the present invention is described in detail below:
Synthesizing of embodiment 1,2-methyl-2-(4-morpholinyl)-1-phenyl-acetone
In the four-hole boiling flask that thermometer, drying tube, induction stirring, constant pressure funnel are housed, add 300ml benzene, 80g(0.6mol) aluminum chloride, after stirring, drip 93g (0.5mol) α-bromine isobutyryl chloride for 0～5 ℃ in temperature of reaction, dropwise back room temperature reaction 9h.After reaction finishes, obtain water with the extraction of 1000ml 10 ﹪ aqueous hydrochloric acids, use the extraction of 2 * 100ml benzene to tell organic phase subsequently.Regulate organic phase to pH=7 with 2 * 100ml saturated sodium bicarbonate solution washing, the underpressure distillation of gained organic phase obtains intermediate product 2-methyl-2-bromo-1-Propiophenone to-0.096mpa.
In the four-hole boiling flask that thermometer, constant pressure funnel are housed, add 60-90 ℃ of sherwood oil of 300ml, 104g(1.2mol) morpholine, 6.7g(0.05mol) aluminum chloride.Dropping 113.5g(0.5mol under stirring) 2-methyl-2-bromo-1-Propiophenone is in reaction system.Dropwise 30 ℃ of reaction 5h.Sherwood oil and morpholine etc. are removed in distillation.Drip 10% aqueous hydrochloric acid conditioned reaction liquid pH=2 subsequently, add 100ml60-90 ℃ of petroleum ether and stirring and leave standstill extraction and obtain water.Add saturated sodium carbonate solution water transfer phase pH=10, separate out faint yellow solid.The solid of using 2 * 100ml trichloromethane dissolving to separate out is again told organic phase, and underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-(4-morpholinyl)-1-phenyl-acetone product 107.2 grams, content 96.3%, yield 88.6%.
Synthesizing of embodiment 2,2-methyl-2-(diethylin)-1-phenyl-acetone
The synthetic method of intermediate product 2-methyl-2-bromo-1-Propiophenone is with embodiment 1.
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring, dropping funnel are housed, add 0.2mol 2-methyl-2-bromo-1-Propiophenone, 300ml toluene, 2.7g(0.02mol) aluminum chloride.Stir and drip 60ml(0.6mol down) diethylamine.Dropwise back 55 ℃ of reaction 16h.After reaction finished, toluene and diethylamine etc. were removed in distillation, drip 10% aqueous hydrochloric acid conditioned reaction liquid pH=2 subsequently, and adding 100ml toluene stirs to leave standstill tells water.With saturated sodium carbonate solution water transfer phase pH=10.Use 2 * 100ml chloroform extraction to tell organic phase again, underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water gets 2-methyl-2-(diethylin)-1-phenyl-acetone product 35.9 grams, product purity 98.8%, yield 80.9%.
Synthesizing of embodiment 3,2-methyl-2-piperidyl-1-phenyl-acetone
The synthetic method of intermediate product 2-methyl-2-bromo-1-Propiophenone is with embodiment 1.
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring, dropping funnel are housed, add 0.2mol 2-methyl-2-bromo-1-Propiophenone, 400ml benzene, 27g(0.2mol) aluminum chloride.Stir and drip 30ml(0.3mol down) piperidines.Dropwise back 40 ℃ of reaction 6h.After reaction finished, benzene and piperidines etc. were removed in distillation, drip 10% aqueous hydrochloric acid conditioned reaction liquid pH=2 subsequently, and adding 100ml benzene stirs to leave standstill tells water.With saturated sodium carbonate solution water transfer phase pH=10, use 2 * 100ml chloroform extraction to tell organic phase again, underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water gets 2-methyl-2-piperidyl-1-phenyl-acetone product 38.9 grams, and product purity is 98.3%, yield 82.9%.
Synthesizing of embodiment 4,2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-acetone (907)
In the four-hole boiling flask that thermometer, mechanical stirring, tail gas absorption tube and constant pressure funnel are housed, in ice bath, add 100g(0.8mol) the aminomethyl phenyl thioether, 500ml 1, the 2-ethylene dichloride, 21.4g(0.16mol) aluminum trichloride (anhydrous), drip 30g(0.16mol) 2-bromo isobutyryl chloride.Dropwise back normal-temperature reaction 9h.After reaction finishes, obtain water with the extraction of 1000ml 10 ﹪ aqueous hydrochloric acids.Add 2 * 100ml 1 subsequently, organic phase is told in the extraction of 2-ethylene dichloride.Regulate organic phase to PH=7 with saturated sodium bicarbonate solution.The underpressure distillation of gained organic phase obtains intermediate product 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-bromo-1-acetone to-0.096mpa.
With 137g (0.5mol) 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-bromo-1-acetone, 300ml60-90 ℃ sherwood oil, 131g(1.5mol) morpholine joins in the four-hole boiling flask that thermometer, constant pressure funnel and reflux condensing tube are housed, stirs.Taking by weighing 6.7g(0.05mol again) aluminum chloride is added in the reaction system.30 ℃ of reaction 5h.After reaction finished, sherwood oil and morpholine etc. were removed in distillation.With 10 ﹪ aqueous hydrochloric acid conditioned reaction liquid pH=2,60-90 ℃ of petroleum ether and stirring of adding 100ml leaves standstill tells water.Add saturated aqueous sodium carbonate and regulate water pH=10, have faint yellow solid to separate out.Use 2 * 100ml chloroform extraction to tell organic phase again, underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water obtains 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-(4-morpholinyl)-1-product acetone 129.6g, yield 91 ﹪, product purity 98 ﹪.
Example 5,2-methyl-2-(4-diethylin)-1-[4-(methyl sulfo-) phenyl]-1-acetone synthetic
Synthesizing with embodiment 4 of intermediate product 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-bromo-1-acetone.
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring, dropping funnel are housed, add 0.2mol 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-bromo-1-acetone, 300ml toluene, 27g(0.2mol) aluminum chloride, mix, drip 60ml(0.6mol again) diethylamine.Dropwise back 55 ℃ of reaction 16h, toluene, diethylamine etc. are removed in distillation.Add 10% aqueous hydrochloric acid conditioned reaction liquid pH=2.Adding 100ml toluene stirs to leave standstill tells water, with saturated sodium carbonate solution water transfer phase pH=10.Use 2 * 100ml chloroform extraction to tell organic phase again, underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-(4-diethylin)-1-[4-(methyl sulfo-) phenyl]-1-product acetone 43.3g, product purity is 99.2%, yield 80.9 ﹪.
Example 6,2-methyl-2-(4-piperidyl)-1-[4-(methyl sulfo-) phenyl]-1-acetone synthetic
Synthesizing with embodiment 4 of intermediate product 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-bromo-1-acetone.
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring and constant voltage addition funnel are housed, add 0.2mol 2-methyl isophthalic acid-[4-(methyl sulfo-) phenyl]-2-bromo-1-acetone, 400ml benzene, 27g(0.2mol) aluminum chloride, stirring makes and mixes.Drip 30ml(0.3mol again) piperidines, drip and finish back 40 ℃ of reaction 12h.Benzene and piperidines etc. are removed in distillation.Drip 10% aqueous hydrochloric acid conditioned reaction liquid pH=2, stir to leave standstill with 100ml benzene and tell water, with saturated sodium carbonate solution water transfer phase pH=10.Tell organic phase with 2 * 100ml chloroform extraction.Underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-(4-piperidyl)-1-[4-(methyl sulfo-) phenyl]-1-product acetone 47.3g, product purity 98.3%, yield 83.9%.
Synthesizing of example 7,2-methyl-2-(4-morpholinyl)-1-(4-aminomethyl phenyl)-1-acetone
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring and constant pressure funnel are housed, add 500ml toluene, 147g(1.1mol) aluminum chloride, after waiting to stir, drip 186g (1mol) 2-bromine isobutyryl chloride down in reaction flask 0～5 ℃ of temperature of reaction.Dropwise back room temperature reaction 9h.Reaction solution is added the 1000ml 10 ﹪ hydrochloric acid ice aqueous solution, stir to leave standstill and tell water, use the extraction of 2 * 100ml toluene to tell organic phase again, regulate organic phase pH=7 with saturated sodium bicarbonate solution, tell organic phase.Underpressure distillation obtains intermediate product 2-methyl-2-bromo-1-(4-aminomethyl phenyl)-1-acetone to-0.096mpa.
In the four-hole boiling flask that thermometer, mechanical stirring, constant pressure funnel and reflux condensing tube are housed, add 137g (0.5mol) 2-methyl-2-bromo-1-(4-aminomethyl phenyl)-1-acetone, 300ml 60-90 ℃ sherwood oil, 131g(1.5mol) morpholine, 6.7g(0.05mol) aluminum chloride, 30 ℃ of reaction 5h.Reaction finishes the back distillation and removes sherwood oil and morpholine etc.With 10 ﹪ aqueous hydrochloric acid conditioned reaction liquid pH=2, leave standstill with a 100ml 60-90 ℃ petroleum ether and stirring and to tell water, add saturated aqueous sodium carbonate subsequently and regulate pH=10, there is faint yellow solid to separate out.Use 2 * 100ml chloroform extraction to tell organic phase again.Underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-(4-morpholinyl)-1-(4-aminomethyl phenyl)-1-product acetone 114.3g, yield 90.2 ﹪, product purity 97.5 ﹪.
Synthesizing of example 8,2-methyl-2-(diethylin)-1-(4-aminomethyl phenyl)-1-acetone
Intermediate product 2-methyl-2-bromo-1-(4-aminomethyl phenyl)-1-acetone synthetic method is with embodiment 7.
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring and dropping funnel are housed, add 0.2mol 2-methyl-2-bromo-1-(4-aminomethyl phenyl)-1-acetone, 300ml toluene, 2.7g(0.02mol) aluminum chloride, 60ml(0.6mol) diethylamine, 55 ℃ of reaction 16h.After reaction finished, toluene and diethylamine etc. were removed in distillation.Drip 10% aqueous hydrochloric acid conditioned reaction liquid pH=2, add the extraction of 100ml toluene and tell water.With saturated sodium carbonate solution water transfer phase pH=10.Use 2 * 100ml chloroform extraction to tell organic phase again, underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-(diethylin)-1-(4-aminomethyl phenyl)-1-product acetone 37.3g, product purity 97.9%, yield 78.3%.
Synthesizing of example 9,2-methyl-2-piperidyl-1-(4-aminomethyl phenyl)-1-acetone
Intermediate product 2-methyl-2-bromo-1-(4-aminomethyl phenyl)-1-acetone synthetic method is with embodiment 7.
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring and dropping funnel are housed, add 0.2mol 2-methyl-2-bromo-1-(4-aminomethyl phenyl)-1-acetone, 400ml benzene, 2.7g(0.02mol) aluminum chloride, 30ml(0.3mol) piperidines, 40 ℃ of reaction 2h.After reaction finished, benzene and piperidines etc. were removed in distillation.In reaction solution, drip 10% aqueous hydrochloric acid adjusting pH=2.Tell water with the extraction of 2 * 100ml benzene, with saturated sodium carbonate solution water transfer phase pH=10.Use 2 * 100ml chloroform extraction to tell organic phase again.Underpressure distillation obtains thick product to-0.096mpa, uses the mixed solvent recrystallization of ethanol and water subsequently, and the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-piperidyl-1-(4-aminomethyl phenyl)-1-product acetone 37.5 and restrains product purity 98.1%, yield 75.1%.
Synthesizing of example 10,2-methyl-2-(4-morpholinyl)-1-(4-chloro-phenyl-)-1-acetone
In the four-hole boiling flask that thermometer, drying tube, mechanical stirring and constant pressure funnel are housed, add 300ml chlorobenzene, 133g(1mol) aluminum chloride.Stir, drip 186g (1mol) 2-bromine isobutyryl chloride down 0～5 ℃ of temperature of reaction, dropwise under the room temperature of back and react 9h.Adding 1000ml 10 ﹪ aqueous hydrochloric acids stirred to leave standstill and tell water after reaction finished, and told organic phase with 100ml * 2 chlorobenzenes extraction.Add saturated sodium hydrogen carbonate solution and regulate organic phase pH=7, tell organic phase.Use 2 * 100ml water washing organic phase again.Underpressure distillation obtains intermediate product 2-methyl-2-bromo-1-(4-chloro-phenyl-)-1-acetone to-0.096mpa.
In the four-hole boiling flask that thermometer, constant pressure funnel and reflux condensing tube are housed, add 137g (0.5mol) 2-methyl-2-bromo-1-(4-chloro-phenyl-)-1-acetone, 300ml60-90 ℃ sherwood oil, 131g(1.5mol) morpholine, 6.7g(0.05mol) aluminum chloride, 30 ℃ of reaction 5h, reaction finishes the back distillation and removes sherwood oil and morpholine etc.Add 10 ﹪ aqueous hydrochloric acid conditioned reaction liquid pH=2, tell water with a 100ml 60-90 ℃ petroleum ether extraction.Add saturated aqueous sodium carbonate and regulate water pH=10, use 2 * 100ml chloroform extraction to tell organic phase again, underpressure distillation obtains thick product to-0.096mpa.Mixed solvent with ethanol and water carries out recrystallization subsequently, and the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-(4-morpholinyl)-1-(4-chloro-phenyl-)-1-product acetone 124.2g, yield 88.9 ﹪, product purity 95.8 ﹪.
Synthesizing of example 11,2-methyl-2-(diethylin)-1-(4-chloro-phenyl-)-1-acetone
Synthesizing with embodiment 10 of intermediate product 2-methyl-2-bromo-1-(4-chloro-phenyl-)-1-acetone.
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring and dropping funnel are housed, add 0.2mol 2-methyl-2-bromo-1-(4-chloro-phenyl-)-1-acetone, 300ml toluene, 2.7g(0.02mol) aluminum chloride, 60ml(0.6mol) diethylamine, 55 ℃ of reaction 16h.After reaction finished, toluene and diethylamine etc. were removed in distillation.In reaction solution, drip 10% hydrochloric acid adjusting pH=2.Add the extraction of 100ml toluene subsequently and tell water, with saturated sodium carbonate solution water transfer phase pH=10.Tell organic phase with 2 * 100ml chloroform extraction, underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-(diethylin)-1-(4-chloro-phenyl-)-1-product acetone 42.1 grams, and product purity is 98.7%, yield 81.9%.
The preparation of example 12,2-methyl-2-piperidyl-1-(4-chloro-phenyl-)-1-acetone
Synthesizing with embodiment 10 of intermediate product 2-methyl-2-bromo-1-(4-chloro-phenyl-)-1-acetone.
In the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring and dropping funnel are housed, add 0.2mol 2-methyl-2-bromo-1-(4-chloro-phenyl-)-1-acetone, 400ml benzene, 2.7g(0.02mol) aluminum chloride, 30ml(0.3mol) piperidines, 40 ℃ of reaction 8h.After reaction finished, benzene and piperidines etc. were removed in distillation.In reaction solution, drip 10% aqueous hydrochloric acid adjusting pH=2.Leave standstill with 2 * 100ml benzene extraction and to tell water, and with saturated sodium carbonate solution water transfer phase pH=10.Use 2 * 100ml chloroform extraction to leave standstill again and tell organic phase.Underpressure distillation obtains thick product to-0.096mpa.Use the mixed solvent recrystallization of ethanol and water subsequently, the volume ratio 2:1 of ethanol and water obtains 2-methyl-2-piperidyl-1-(4-chloro-phenyl-)-1-product acetone 39.2 grams, product purity 97.6%, yield 71.9%.
Claims (3)
1. the synthetic method of an alpha-amino group arone compounds is characterized in that reaction carries out in two steps:
The first step, benzene or substituted benzene, 2-bromo isobutyryl chloride, water-insoluble solvent is reacted under catalyzer aluminum trichloride (anhydrous) and anhydrous condition, generates intermediate product 2-bromo-2-methyl isophthalic acid-benzene or substituted benzene acetone,
Described benzene or substituted benzene refer to benzene, thioanisole, toluene or chlorobenzene,
Described water-insoluble solvent refers to benzene, 1,2-ethylene dichloride, toluene or chlorobenzene,
The mol ratio of 2-bromo isobutyryl chloride and catalyzer aluminum trichloride (anhydrous) is 1:1～1.2;
In second step, intermediate product is under organic solvent, the effect of catalyzer aluminum trichloride (anhydrous), and the compound reaction with containing the secondary amine structure gets alpha-amino group arone class compounds through aftertreatments such as hydrolysis, chloroform extractions, and the ultimate yield of its product reaches more than 80 ﹪,
The described compound that contains the secondary amine structure refers to morpholine, diethylamine or piperidines,
Described organic solvent refers to 60-90 ℃ of sherwood oil, toluene or benzene,
The mol ratio of intermediate product and catalyzer aluminum trichloride (anhydrous) is 1:0.1～1;
Concrete reaction formula is:
In the formula: R
1Be H, SCH
3, CH
3Or Cl,
R
2Be morpholine, diethylamine or piperidines.
2. the synthetic method of a kind of alpha-amino group arone compounds according to claim 1, it is characterized in that in the four-hole boiling flask that thermometer, drying tube, mechanical stirring, constant pressure funnel are housed, adding benzene or substituted benzene, catalyzer aluminum trichloride (anhydrous), water-insoluble solvent, after stirring, drip 2-bromine isobutyryl chloride 0～5 ℃ of temperature of reaction, dropwise back room temperature reaction 9h; After reaction finishes, obtain water with the extraction of 10 ﹪ aqueous hydrochloric acids; Tell organic phase with organic solvent subsequently; Regulate organic phase to pH=7 with saturated sodium bicarbonate solution washing, the underpressure distillation of gained organic phase obtains intermediate product 2-bromo-2-methyl isophthalic acid-benzene or substituted benzene acetone to-0.096mpa;
Described water-insoluble solvent is 60-90 ℃ of sherwood oil, ethylene dichloride or toluene,
The described organic solvent of telling organic phase is 60-90 ℃ of sherwood oil, ethylene dichloride or toluene.
3. the synthetic method of a kind of alpha-amino group arone compounds according to claim 1, it is characterized in that the compound that in the four-hole boiling flask that thermometer, reflux condensing tube, mechanical stirring, constant pressure funnel are housed, adds organic solvent, intermediate product, catalyzer aluminum trichloride (anhydrous), contain the secondary amine structure, 30～55 ℃ of stirring reaction 5～16h; After reaction finished, distillation removed the intact raw material of unreacted; With 10% aqueous hydrochloric acid conditioned reaction liquid pH=2, add organic solvent extraction, leave standstill and tell water, with saturated sodium carbonate solution water transfer phase pH=10, separate out faint yellow solid; The solid of separating out with trichloromethane dissolving is told organic phase again, be distilled to-0.096mpa obtains thick product; Use the mixed solvent recrystallization of ethanol and water subsequently, obtain alpha-amino group arone compounds product, the volume ratio 2:1 of ethanol and water;
Described organic solvent is 60-90 ℃ of sherwood oil, toluene or benzene,
The compound that contains the secondary amine structure is morpholine, diethylamine or piperidines.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327220B (en) * | 2014-10-17 | 2017-06-13 | 武汉理工大学 | A kind of preparation method of polyacrylic acid based water reducer |
| CN106947057A (en) * | 2016-01-07 | 2017-07-14 | 北京英力科技发展有限公司 | A kind of Photocurable composition and its purposes as varnish and colored paint |
| CN114426525A (en) * | 2021-12-29 | 2022-05-03 | 天津久日新材料股份有限公司 | White solid photoinitiator and preparation method and application thereof |
| CN115894197A (en) * | 2022-12-06 | 2023-04-04 | 湖南久日新材料有限公司 | Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354175A (en) * | 2000-11-21 | 2002-06-19 | 北京英力高科技术发展有限公司 | Preparation method of carbonyl alpha-substitution nitrogenous compound |
-
2013
- 2013-05-21 CN CN2013101898652A patent/CN103242261A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1354175A (en) * | 2000-11-21 | 2002-06-19 | 北京英力高科技术发展有限公司 | Preparation method of carbonyl alpha-substitution nitrogenous compound |
Non-Patent Citations (1)
| Title |
|---|
| 程乾: "2-羟基芳酮类光引发剂的合成与性能研究", 《中国优秀硕士学位论文全文数据库》, 15 December 2012 (2012-12-15) * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104327220B (en) * | 2014-10-17 | 2017-06-13 | 武汉理工大学 | A kind of preparation method of polyacrylic acid based water reducer |
| CN106947057A (en) * | 2016-01-07 | 2017-07-14 | 北京英力科技发展有限公司 | A kind of Photocurable composition and its purposes as varnish and colored paint |
| CN106947057B (en) * | 2016-01-07 | 2019-08-27 | 北京英力科技发展有限公司 | A kind of Photocurable composition and its purposes as varnish and colored paint |
| CN114426525A (en) * | 2021-12-29 | 2022-05-03 | 天津久日新材料股份有限公司 | White solid photoinitiator and preparation method and application thereof |
| CN114426525B (en) * | 2021-12-29 | 2024-03-29 | 天津久日新材料股份有限公司 | White solid photoinitiator and preparation method and application thereof |
| CN115894197A (en) * | 2022-12-06 | 2023-04-04 | 湖南久日新材料有限公司 | Alkaline hydrolysis method for preparing alpha-hydroxyisobutyrophenone |
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