CN102786405B - Preparation method for 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-acetone - Google Patents
Preparation method for 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-acetone Download PDFInfo
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- CN102786405B CN102786405B CN201210311169.XA CN201210311169A CN102786405B CN 102786405 B CN102786405 B CN 102786405B CN 201210311169 A CN201210311169 A CN 201210311169A CN 102786405 B CN102786405 B CN 102786405B
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Abstract
The invention relates to a preparation method for 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-acetone. The preparation method comprises the steps of uniformly agitating 2-(4-isobutyryl phenoxy) ethyl acetate, a certain amount of solvent, sodium hydroxide with concentration of 10 to 50%, and phase transfer catalyst with concentration of 1%; controlling the temperature to 25 to 50 DEG C; dropping 0.6 to 1.2 equivalent weight of bromine; carrying out one-pot reaction to obtain corase product of the 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-acetone; and then crystallizing and drying to obtain the finished product of the 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-acetone. The preparation method is carried out through the one-pot reaction, and has the advantages of simple operation, less emission of three wastes, short production period, and low cost of production.
Description
Technical field
The present invention relates to a kind of Chemicals preparation field, particularly a kind of 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl] preparation method of-2-methyl isophthalic acid-acetone.
Background technology
2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl]-2-methyl isophthalic acid-acetone is that a kind of unique FDA certification system allows available light initiator, compared with other commercial ultraviolet initiators, has extremely low volatility and smell.Containing hydroxyl in its structure, it can be made to be grafted on resin by reaction, thus reduce the extractibility of system medium ultraviolet light trigger.Therefore, 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl]-2-methyl isophthalic acid-acetone is specially adapted to water-based system and needs the field of low smell, as the ink in food product pack.
Current alpha-hydroxyacetone compounds mainly contains following four kinds of preparation methods:
Method 1: at Bull.Soc.Chim.France; in 1957 (3): 1047-1052, Elphimoff-FelkiN and M.Verrier acetone and HCN generate cyanalcohol; hydroxyl is protected with dihydropyrane; react with phenyl-magnesium-bromide, hydrolysis obtains Alpha-hydroxy-Alpha-Methyl-1-phenyl-acetone again.But the method hydroxyl dihydropyrane is protected, and yield only has about 30%, is not suitable for industrial production.
Method 2: at J.Am.Chem.Soc., in 1982 (104): 4151, Creary X. and Geiger C.C. acetone and trimethyl silicane prussiate and potassium cyanide react and generate acetone cyanohydrin trimethylsilane in acetonitrile, then react with phenyl lithium, are hydrolyzed and obtain product.The method need be reacted at-78 DEG C, consumes energy high, and raw material organolithium is expensive, is difficult to buy, total reaction yield about 40%.So yield low cost is high, condition is harsher, therefore is difficult to industrialization.
Method 3: " synthesis of photoinitiator 2-hydroxy-2-methyl-1-phenyl-acetone " (Hu Yingxi, Liu Xia, Li Yanyun, Deng, chemistry world .2001, (4): 203-209) disclose with phenyl aldehyde, magnesium, 2-N-PROPYLE BROMIDE, bromine etc. for main raw material, through four-step reaction synthesizing ultraviolet initiator Alpha-hydroxy-Alpha-Methyl-1-phenyl-acetone.Although the method raw material is easy to get, technique is simple, and use potassium bichromate, environmental pollution is heavier.
Method 4: " water-soluble photoinitiator 2-hydroxyl-1-[4-(2-hydroxyethyl) phenyl]-2-methyl isophthalic acid-acetone " (grandson's a large bell; Lu Weijie; Deng; Shandong chemical industry .2003; (3): 5-9) disclose with ethylene glycol phenyl ether acetate and isobutyryl chloride as raw material, under Louis acid catalysis, friedel-crafts acylation reaction occurs; product carries out bromination in solvent Glacial acetic acid; add ethanol after brominated product precipitation and aqueous sodium hydroxide solution is hydrolyzed, purified crystals obtains product 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl]-2-methyl isophthalic acid-acetone.The shortcoming of this technique is that bromination reaction adopts Glacial acetic acid as solvent, and large to equipment corrosion, reaction is slow, needs more than 10 hours.Hydrolytic process will utilize a large amount of ethanol as solvent, and aftertreatment is cumbersome, and cost is higher.
Summary of the invention
The object of the invention is the deficiency overcoming prior art existence, a kind of (one kettle way) simple to operate, obvious energy conservation, easily industrialization, lower-cost 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl be provided]-2-methyl isophthalic acid-acetone preparation method.
The preparation technology's main flow that the present invention relates to is as follows:
Technical problem to be solved by this invention is realized by following technical scheme.The present invention is a kind of 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl] preparation method of-2-methyl isophthalic acid-acetone, the step that it comprises:
1) 2-(4-isobutyryl phenoxy group) ethyl acetate, a certain amount of solvent, phase-transfer catalyst and certain density sodium hydroxide solution are joined in reaction flask, bromine is instilled under stirring temperature control, react complete separatory, aqueous phase enters sewage disposal, organic phase retains, organic phase is acidified to neutrality, low pressure precipitation;
2) precipitation is complete, adds solvent crystallization and obtains detecting qualified wet product, obtain qualified product 50-60 DEG C of low pressure drying.
The present invention is a kind of 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl] preparation method of-2-methyl isophthalic acid-acetone, its feature is as follows:
(1) described reaction adopts one kettle way to complete;
(2) reaction solvent described in is the mixing of one or more in ethylene dichloride, chloroform or chlorobenzene;
(3) concentration of the sodium hydroxide described in is 10%-50%;
(4) temperature of reaction described in is 25-50 DEG C, preferred 25-35 DEG C;
(5) described reaction bromine amount ranges 0.6-1.2 equivalent, preferred 0.8-1.1 equivalent;
(6) phase-transfer catalyst of described use be Tetrabutyl amonium bromide, a kind of in tetrabutylammonium chloride, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate or benzyl trimethyl ammonium chloride or their mixing, usage quantity is the 0.01%-10% of raw material weight, preferred 1%-2%.
Compared with prior art, the preparation method that the present invention relates to is more reasonable, and production process one kettle way completes, and simplifies plant operations, decreases three waste discharge, shortens the production cycle, reduces production cost.
Embodiment
The present invention will be described further by following embodiment.
The reagent that the present invention uses is commercially available prod.
Below further describe concrete technical scheme of the present invention, so that those skilled in the art understand the present invention further, and do not form the restriction to its right.
Embodiment 1:
The sodium hydroxide solution of 200g 2-(4-isobutyryl phenoxy group) ethyl acetate, 2g Tetrabutyl amonium bromide, 400ml ethylene dichloride and 150g 50% is joined in the four-hole bottle of 1000ml; temperature control 35-45 DEG C; stir lower dropping 128g bromine (being dissolved in 200ml ethylene dichloride); GC follows the tracks of reaction; after raw material disappears, terminate reaction.Discard the alkali lye of lower floor, organic phase is acidified to neutrality, with 600ml mixed solvent (sherwood oil: acetone=3: 1) recrystallization drying obtains product, GC content 99.4%, product yield 89.5% after low pressure precipitation.
Embodiment 2:
The sodium hydroxide solution of 200g 2-(4-isobutyryl phenoxy group) ethyl acetate, 2g benzyltriethylammoinium chloride, 400ml chloroform and 150g 30% is joined in the four-hole bottle of 1000ml; temperature control 30-35 DEG C; stir lower dropping 141g bromine (being dissolved in 200ml chloroform); GC follows the tracks of reaction; after raw material disappears, terminate reaction.Discard the alkali lye of lower floor, organic phase is acidified to neutrality, with 600ml mixed solvent (isopropyl ether: ethyl acetate and acetone=3: 1) recrystallization drying obtains product, GC content 99.0%, product yield 75.0% after low pressure precipitation.
Embodiment 3:
The sodium hydroxide solution of 200g 2-(4-isobutyryl phenoxy group) ethyl acetate, 2g Tetrabutyl amonium bromide, 400ml chlorobenzene and 150g30% is joined in the four-hole bottle of 1000ml; temperature control 25-30 DEG C; then 153g bromine (being dissolved in 200ml chlorobenzene) is dripped; GC follows the tracks of reaction; after raw material disappears, terminate reaction.Discard the alkali lye of lower floor, organic phase is acidified to neutrality, with 600ml mixed solvent (methyl tertiary butyl ether: acetone=3: 1) recrystallization drying obtains product, GC content 99.3%, product yield 85.1% after low pressure precipitation.
Embodiment 4:
The sodium hydroxide solution of 200g 2-(4-isobutyryl phenoxy group) ethyl acetate, 2g Tetrabutyl amonium bromide, 200ml chlorobenzene, 200mil ethylene dichloride and 150g 30% is joined in the four-hole bottle of 1000ml; temperature control 25-30 DEG C; then 153g bromine (being dissolved in 200ml ethylene dichloride) is dripped; GC follows the tracks of reaction; after raw material disappears, terminate reaction.Discard the alkali lye of lower floor, organic phase is acidified to neutrality, with 600ml mixed solvent (sherwood oil: ethyl acetate=3: 1) recrystallization drying obtains product, GC content 99.4%, product yield 88.0% after low pressure precipitation.
Claims (11)
1. 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl] preparation method of-2-methyl isophthalic acid-acetone; it is characterized in that the step that it comprises: 2-(4-isobutyryl phenoxy group) ethyl acetate carries out bromo hydrolysis one pot reaction in the basic conditions, reaction scheme:
2. 2-hydroxyl-1-[4-(2-hydroxy ethoxy) phenyl] preparation method of-2-methyl isophthalic acid-acetone, it is characterized in that the step that it comprises:
1) 2-(4-isobutyryl phenoxy group) ethyl acetate, a certain amount of solvent, phase-transfer catalyst and certain density sodium hydroxide solution are joined in reaction flask, bromine is instilled under stirring temperature control, react complete separatory, aqueous phase enters sewage disposal, organic phase retains, organic phase is acidified to neutrality, low pressure precipitation;
2) precipitation is complete, adds solvent crystallization and obtains detecting qualified wet product, obtain qualified product 50-60 DEG C of low pressure drying.
3. preparation method according to claim 2, is characterized in that step 1) solvent be selected from a kind of in ethylene dichloride, chloroform or chlorobenzene or their mixing.
4. preparation method according to claim 2, is characterized in that step 1) the concentration of sodium hydroxide be selected from 10%-50%.
5. preparation method according to claim 2, is characterized in that step 1) temperature control scope be selected from 15-50 DEG C.
6. preparation method according to claim 2, is characterized in that step 1) bromine amount ranges 0.6-1.2 equivalent.
7. preparation method according to claim 2, it is characterized in that step 1) phase-transfer catalyst that uses is selected from one or more mixing in Tetrabutyl amonium bromide, tetrabutylammonium chloride, benzyltriethylammoinium chloride, 4-butyl ammonium hydrogen sulfate, benzyl trimethyl ammonium chloride, and usage quantity is the 0.01%-10% of raw material weight.
8. preparation method according to claim 2, is characterized in that step 2) solvent that uses is selected from a kind of in sherwood oil, methyl tertiary butyl ether, isopropyl ether, ethyl acetate, acetone and ethanol or their mixing.
9. the preparation method according to claim 2 or 5, is characterized in that step 1) best temperature control scope 25-35 DEG C.
10. the preparation method according to claim 2 or 6, is characterized in that step 1) bromine optimum amount scope 0.8-1.1 equivalent.
11. preparation methods according to claim 2 or 7, is characterized in that step 1) use the amount ranges of phase-transfer catalyst to be selected from 1%-2%.
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