CN104844430B - A kind of preparation method of light trigger 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone - Google Patents

A kind of preparation method of light trigger 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone Download PDF

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CN104844430B
CN104844430B CN201510276467.3A CN201510276467A CN104844430B CN 104844430 B CN104844430 B CN 104844430B CN 201510276467 A CN201510276467 A CN 201510276467A CN 104844430 B CN104844430 B CN 104844430B
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phenyl
methyl
propyl group
hydroxy
group ketone
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CN104844430A (en
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李德江
刘义稳
谢益碧
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Hubei Weidehe Innovative Material Technology Co ltd
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China Three Gorges University CTGU
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
    • C07C45/67—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton
    • C07C45/68—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by isomerisation; by change of size of the carbon skeleton by increase in the number of carbon atoms

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

The present invention relates to light trigger 4’The preparation method of methylol 2 hydroxyl 2 methyl 1 phenyl 1 propyl group ketone, with aluminum chloride as catalyst, methylene chloride as solvent, 2 hydroxyl 2 methyl 1 phenyl 1 propyl group ketone generate 4 with polyformaldehyde reaction/Chloromethyl 2 hydroxyl 2 methyl 1 phenyl 1 propyl group ketone, control temperature 90 100 DEG C, 4’Chloromethyl 2 hydroxyl 2 methyl 1 phenyl 1 propyl group ketone reacts with water and obtains 4’Methylol 2 hydroxyl 2 methyl 1 phenyl 1 propyl group ketone, liquid phase purity reaches 99.21%.This preparation method, simple to operate, technique is advanced, solvent recoverable, it is easy to industrialized production.

Description

A kind of preparation method of light trigger 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
Technical field
The invention belongs to light trigger field, be specifically related to a kind of light trigger 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-third The preparation method of base ketone.
Technical background
Light trigger be absorb radiation energy after through chemical change produce can cause monomer carry out the free radical of polyreaction, cation, Anion or the material of ion Bai Youji isoreactivity intermediate.In recent years due to research, the development and application of novel photoinitiator, Its range of application is rapidly spread to multiple field, such as in electron trade, light trigger be widely used in chip manufacturing, Photoresist, photoresist, plasma panel etc..4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone and 2-hydroxyl -2-methyl isophthalic acid-phenyl-1-propyl group ketone is compared, and has the advantage that (1) UV Absorption efficiency is high, quantum yield is high；(2) Light-initiated efficiency is high, and the reactive intermediate reactivity of generation is high；(3) resin compatible is good, nontoxic odorlessness, after photodissociation not Produce poisonous fragment；(4) non-volatile, the mobility solidifying backward product surface is low.Therefore, 4 '--methylol-2-hydroxyl-2- Methyl isophthalic acid-phenyl-1-propyl group ketone has broad application prospects, but 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone is complete Synthesis there is presently no report.
Summary of the invention
The task of the present invention is to provide that a kind of technique is simple, yield is high, low cost, pollution are little, good product quality, be suitable for industry 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone preparation method that metaplasia is produced.For solving above-mentioned technical problem, the present invention By the following technical solutions:
A: Lewis acid be dissolved in organic solvent, adds 2-hydroxyl 2-methyl isophthalic acid-phenyl-1-propyl group ketone, and temperature control is to 20-50 DEG C After, add paraformaldehyde.Under conditions of temperature 20-50 DEG C, react 15-16 hour, after having reacted, be cooled to room temperature, Joining in aqueous hydrochloric acid solution, layering, organic facies water successively, saturated sodium-chloride wash, and separate organic layer, and decompression steams organic Solvent, obtains 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone, and reaction equation is as follows:
B: by soluble in water for 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone, in temperature 80-110 DEG C, reacts 15-17 Hour, after reaction terminates, to adjust the aobvious neutrality of pH with sodium carbonate liquor, add extractant, stratification, organic liquor decompression is steamed Obtaining 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone after evaporating collection extractant, reaction equation is as follows:
Beneficial effects of the present invention is as follows:
1, provide with 2-hydroxyl 2-methyl isophthalic acid-phenyl-1-propyl group ketone, paraformaldehyde, hydrochloric acid for Material synthesis 4 '-methylol-2- The complete preparation method of hydroxy-2-methyl-1-phenyl-1-propyl group ketone.
2, this production method, simple to operate, and technique is advanced, solvent recoverable, it is easy to industrialized production.
3, the 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone prepared by this preparation method, liquid phase purity is high, up to 99.21%,
Detailed description of the invention
Below in conjunction with embodiment, the invention will be further described, but the scope of protection of present invention is not limited to the model of embodiment statement Enclose.
Embodiment 1:
A kind of preparation method of 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone, the method comprises the steps of:
The preparation of 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
In enamel reaction still, put into 2000L dichloroethane solution, start stirring, at room temperature add powder aluminum chloride 2028Kg (15244mol), after adding, control temperature in the kettle, at 30-35 DEG C, drips 2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone 500 Kilogram (3049mol), adds paraformaldehyde 650 kilograms, reacts 15-16 hour at 30-35 DEG C.After having reacted, by above-mentioned instead Liquid is answered slowly to be added drop-wise to equipped with in the hydrochloric acid of the 10% of 1000Kg, static layering.Aqueous phase, through evaporation, concentration, sucking filtration, prepares AlCl3·6H2O.Organic facies steams dichloroethanes, obtains 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone, yield 85.6%.
The preparation of 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
Prepared 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone is added drop-wise to equipped with 1000Kg H2The enamel of O is anti- Answer in still, react 13-15 hour at 90-100 DEG C.After having reacted, adjust pH value to be neutrality with sodium bicarbonate solid, add 600Kg butyl acetate, stirs 0.5-1.0 hour, static separates organic facies.After organic liquid normal pressure steams butyl acetate, decompression Steam light yellow liquid, obtain target compound 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone, yield 93.5%.
1H NMR(CDCl3, 400MHz) δ: 7.86 (d, J=7.3,2H, Ar-H), 7.15 (d, J=7.4,2H, Ar-H), 5.2 (s, 1H, OH),4.3(s,1H,OH),1.59(s,6H,2CH3)。
Embodiment 2:
The preparation of 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
The amount of aluminum chloride increases to 2433Kg (18294mol), and other is with example one, 4 '-chloromethyl-2-hydroxy-2-methyl -1-phenyl-1-propyl group ketone yield 91.2%.
The preparation of 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
Changing extractant butyl acetate into isobutyl acetate, other is with example one, 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1- Propyl group ketone yield 90.2%.
Embodiment 3:
The preparation of 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
The amount of aluminum chloride increases to 2839Kg (21343mol), and other is with example one, 4 '-chloromethyl-2-hydroxy-2-methyl -1-phenyl-1-propyl group ketone yield 89.6%.
The preparation of 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
Changing extractant butyl acetate into pentyl acetate, other is with example one, 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-third Base ketone yield 89.5%.
Embodiment 4:
The preparation of 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
The amount of aluminum chloride increases to 3244Kg (24392mol), and other is with example one, 4 '-chloromethyl-2-hydroxy-2-methyl -1-phenyl-1-propyl group ketone yield 84.5%.

Claims (1)

1. one kind 4 ’ The preparation method of-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone, the method comprises the steps of:
4 ’ The preparation of-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
2000 L dichloroethane solutions are put in enamel reaction still, start stirring, at room temperature add powder aluminum chloride 2028Kg, 15244mol, after adding, control temperature in the kettle, at 30-35 DEG C, drips 2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone 500 kilograms, 3049mol, add paraformaldehyde 650 kilograms, react 15-16 hour at 30-35 DEG C, after having reacted, above-mentioned reactant liquor is slowly added drop-wise in the hydrochloric acid of 10% equipped with 1000 Kg, static layering, aqueous phase, through evaporation, concentration, sucking filtration, prepares AlCl3•6H2O, organic facies steams dichloroethanes, obtains 4 '-chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone, yield 85.6%；
4 ’ The preparation of-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone
By prepared 4 ’ -chloromethyl-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone is added drop-wise to equipped with 1000 Kg H2In the enamel reaction still of O, react 13-15 hour at 90-100 DEG C, after having reacted, adjust pH value to be neutrality with sodium bicarbonate solid, add 600 Kg butyl acetates, stir 0.5-1.0 hour, static separate organic facies, after this organic facies normal pressure steams butyl acetate, decompression steams light yellow liquid, obtains target compound 4 ’ -methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone, yield 93.5%.
CN201510276467.3A 2015-05-27 2015-05-27 A kind of preparation method of light trigger 4 '-methylol-2-hydroxy-2-methyl-1-phenyl-1-propyl group ketone Expired - Fee Related CN104844430B (en)

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1942424A (en) * 2004-04-19 2007-04-04 西巴特殊化学品控股有限公司 Novel photoinitiators
CN101928233A (en) * 2009-10-23 2010-12-29 湖北迅达药业股份有限公司 Cholromethylation method of benzoic acid derivative
CN102060684A (en) * 2010-11-12 2011-05-18 深圳市有为化学技术有限公司 Para-position or meta-position functional group aromatic ketone compounds, preparation method and photopolymerization initiator thereof

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1942424A (en) * 2004-04-19 2007-04-04 西巴特殊化学品控股有限公司 Novel photoinitiators
CN101928233A (en) * 2009-10-23 2010-12-29 湖北迅达药业股份有限公司 Cholromethylation method of benzoic acid derivative
CN102060684A (en) * 2010-11-12 2011-05-18 深圳市有为化学技术有限公司 Para-position or meta-position functional group aromatic ketone compounds, preparation method and photopolymerization initiator thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
烷基苯氯甲基化反应;谢光勇等;《中南民族大学学报(自然科学版)》;20090331;第28卷(第1期);8-11 *

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