CN102249832A - Novel synthesis method of alpha-hydroxyl arone compound - Google Patents
Novel synthesis method of alpha-hydroxyl arone compound Download PDFInfo
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Abstract
The invention relates to a novel synthesis method of an alpha-hydroxyl arone compound. The method comprises the following two steps: step 1, carrying out a reaction on substituted or non-substituted arene and alpha-substituted acrylyl halogen as well as anhydrous hydrogen halide under the environments of a catalyst and no water and a non-aqueous solvent in an hermetic system under the pressurizing condition so as to generate an alpha-halo-alpha-substituted-1-substituted or non-substituted arene acetone intermediate product; and step 2, carrying out one-phase or two-phase hydrolysis reaction on the intermediate product in the presence of an organic solvent and a phase transfer catalyst under the basic environment, carrying out post-treatments such as extraction with an extractant and the like so as to obtain alpha-hydroxyl alpha-substituted-1-ubstituted or non-substituted arene acetone. In the method, acylation reaction and addition reaction are combined to be carried out in one step; an organic solvent-water system, the phase transfer catalyst and the basic environment are adopted, thereby achieving one-phase or two phase hydrolysis reaction; and the quality of the product is good, the total yield of the product can reach above 60%, and the content of the alpha-hydroxyl arone compound reaches 98%. The synthesis method has the advantages of less environment pollution and low cost.
Description
Technical field
The present invention relates to the synthetic method of a kind of ultraviolet initiator-Alpha-hydroxy arone compounds.
Background technology
Photocuring technology has obtained vigorous growth in recent years as a kind of eco-friendly green technology.Light trigger is the major ingredient of photocuring system, and sensitivity plays a decisive role to curing system for it.
But in actual applications,, be difficult to coating,, generally need to add reactive monomer, during spraying, also need add a small amount of solvent and regulate viscosity in order to satisfy the requirement of complete processing because the viscosity of prepolymer in the UV curing system or resin is bigger.Activity diluting monomer and solvent may be harmful to environment and HUMAN HEALTH, many reactive monomers are difficult to complete reaction in the UV solidification process, residue has permeability, may influence the hygienic safety index and the long-term behaviour of solidifying product, so an important development direction of UV curing technology is to replace activity diluting monomer with water, to eliminate problems such as its caused pollution and stimulation.
From the eighties, Europe, the United States, day etc., developed country carried out the research and development of water-based UV curing system in succession, obtained at aspects such as screen printing ink, resist, tackiness agent, wood coating, flexible printing plates and to develop rapidly, more existing products emerge.
Gorgeous good solid (Irgacure) 2959 that vapour Ba-Jia Ji company produces is exactly a kind of relatively water-soluble light trigger of success, belongs to the Alpha-hydroxy arone compounds.It has the efficiency of initiation height, Heat stability is good, anti-xanthochromia, advantages such as free from extraneous odour.This photoinitiator is particularly useful for emulsion-type or latex type photopolymerization system and water-soluble photo-polymerization system, thereby can be widely used in various fields, as paint, coating, light-sensitive emulsion, printing-ink, tackiness agent, plastics, leather, papermaking and electronic product etc.
The synthetic method of existing alpha-hydroxyacetone compounds mainly contains following several:
Method one: Elphimoff-Felkin and M Verrier generate cyanalcohol with acetone and HCN, protect hydroxyl with dihydropyrane, and with the phenyl-magnesium-bromide reaction, hydrolysis obtains Alpha-hydroxy-Alpha-Methyl-1-phenyl-acetone again.
The hydroxyl of this method is protected with dihydropyrane, and this protection itself has caused different products, and need reflux under acidic conditions and slough tetrahydropyrans, and backflow with this understanding can take place to eliminate reaction, and yield is low, has only about 30%.Be not suitable for industrial production.
Method two: Creary X and Geiger C C use acetone and trimethyl silicane prussiate and potassium cyanide to react in acetonitrile and generate acetone cyanohydrin three silicomethanes, obtain product with phenyl lithium reaction, hydrolysis again.
This reaction needs-78 ℃ of reactions down, and power consumption is high, moreover the organolithium costliness, is difficult on the market buy, and yield is also not too high, and is about 40%, because of yield is low, and the cost height, severe reaction conditions is so be difficult to industrialization.
Method three: the Hu Yingxi of Beijing Institute of Petrochemical Technology etc. are main raw material with phenyl aldehyde, magnesium, 2-N-PROPYLE BROMIDE, bromine etc., have synthesized ultraviolet initiator Alpha-hydroxy-Alpha-Methyl-1-phenyl-acetone through four-step reaction.
This raw materials technology is easy to get, and technology is simple, by product is few, and aftertreatment is simple, and cost is low, and total recovery is higher than 80%, and constant product quality, realizes industrialization easily.
Method five: the old Oxone that uses in groups of Lanzhou University
And trifluoro-acetic anhydride (TFAA) makes oxygenant, in the presence of the iodobenzene of catalytic amount, the 'alpha '-hydroxylation of ketone studied, and successfully synthesized 16 alpha-hydroxyacetone compounds.
This method raw material is simple and easy to, the reaction conditions gentleness, and productive rate is higher.But only limit to theoretical investigation, do not have further industrialized developing research.
Method six: the Sun Yong of test center of Shandong Normal University etc. are with ethylene glycol phenyl ether, and isobutyryl chloride is synthetic a kind of water-soluble light trigger 1-[4-(2-hydroxy ethoxy) phenyl of raw material]-the new synthetic route of Alpha-hydroxy-Alpha-Methyl-1-acetone (Irgacure 2959).
Because of this method does not have concrete technological process, can't estimate.
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 suitability for industrialized production to 2-hydroxyl arone photoinitiator, the yield of product and purity height, the novel synthesis of a kind of Alpha-hydroxy arone compounds that environmental pollution is little, cost is low.
Purpose implementation of the present invention is, a kind of novel synthesis of 2-hydroxyl arone compounds, and reaction is carried out in two steps:
The first step, replace or non-substituted arene, alpha-substitution acryloyl halide and anhydrous hydrogen halide under the environment of catalyzer and anhydrous, water-insoluble solvent, in enclosed system, under pressurized conditions, react, generating alpha-halogen-alpha-substitution-1-replaces or non-substituted arene acetone intermediate product
Described anhydrous hydrogen halide environment is meant and contains F, Cl, and Br, the environment of I hydride,
Described catalyzer is meant the sodium of the halogen, vitriol, nitrate, acetate, oxalate or the oxygen acid that contain two or more element among Fe, Sn, V, Zr, W, Pd, Al, Ti, Zn, Sb, Cr, Mn, Bi or the Mo or the product that sylvite forms through co-precipitation, filtration, oven dry, roasting, pulverizing;
Described anhydrous, water-insoluble solvent is meant that the catalyzer raw material has the F that contains of certain solubility, Cl, Br, I, S, the aliphatic saturated hydrocarbon of O, saturated alicyclic hydrocarbon, aromatic hydrocarbon, heterogeneous ring compound to replacing or non-substituted arene, alpha-substitution acryloyl halide, anhydrous hydrogen halide;
The pressure of compressive reaction is the 0.01-10 normal atmosphere;
In second step, intermediate product is realized a phase or a two-phase hydrolysis reaction under organic solvent, phase-transfer catalyst and alkaline environment, through last handling processes such as extraction agent extractions, obtain Alpha-hydroxy-alpha-substitution-1-and replace or non-substituted arene acetone,
Described organic solvent is meant all has the water-soluble or water-insoluble organism of certain solubility to middle product and final product, as contains aliphatic saturated hydrocarbon, saturated alicyclic hydrocarbon, aromatic hydrocarbon or the heterogeneous ring compound of F, Cl, Br, I, S or O,
Described extraction agent is meant all has the water-insoluble organism of certain solubility to middle product and final product, as contains aliphatic saturated hydrocarbon, saturated alicyclic hydrocarbon, aromatic hydrocarbon or the heterogeneous ring compound of F, Cl, Br, I, S or O,
Described alkaline environment is meant and contains Na, K, and Ca, the oxyhydroxide of Mg, carbonate, acetate, oxalate, and sodium methylate or potassium, sodium tert-butoxide or potassium compound,
Described phase-transfer catalyst is meant and contains N, the salt of P, crown ether, and acyclic polyether or PEG class,
Concrete reaction formula is:
In the formula: R
1Be H, aliphatic saturated hydrocarbon, saturated alicyclic hydrocarbon, aromatic hydrocarbon, heterogeneous ring compound,
X is F, Cl, Br or I,
R
2Be H, aliphatic saturated hydrocarbon, saturated alicyclic hydrocarbon, aromatic hydrocarbon, heterogeneous ring compound.
The present invention with acylation reaction, addition be incorporated in one the step carry out; Adopt organic solvent-aqueous systems, phase-transfer catalyst, alkaline environment, realize a phase or a two-phase hydrolysis reaction, good product quality, total yield of products can reach more than 60%, and the content of Alpha-hydroxy arone compounds can reach 98%, and environmental pollution is little, and cost is low.
Description of drawings
Fig. 1 is a technological process block-diagram of the present invention,
Fig. 2 is old technological process block-diagram.
Embodiment
Reaction of the present invention is carried out in two steps:
The first step, replace or non-substituted arene, alpha-substitution acryloyl halide and anhydrous hydrogen halide under the environment of catalyzer and anhydrous, water-insoluble solvent, in enclosed system, under pressurized conditions, react, generate alpha-halogen-alpha-substitution-1-and replace or non-substituted arene acetone intermediate product.
Replace or non-substituted arene, alpha-substitution acryloyl halide and anhydrous hydrogen halide are at catalyzer and anhydrous, under the environment of water-insoluble solvent, in enclosed system, be warming up to reflux temperature, stir 1h, reaction mixture darkens, leave standstill cool to room temperature, pour hydrolysis in trash ice-concentrated hydrochloric acid solution of 2: 1 of volume ratio into, use the reaction solvent extracting and demixing, the organic phase of extraction is washed up to neutrality with saturated sodium carbonate solution successively, water washing, and normal pressure steams solvent after the organic phase drying, fraction is collected in underpressure distillation again, gets alpha-halogen-alpha-substitution-1-and replaces or non-substituted arene acetone intermediate product.
In second step, intermediate product is realized a phase or a two-phase hydrolysis reaction under organic solvent, phase-transfer catalyst and alkaline environment, through last handling processes such as extraction agent extractions, obtains Alpha-hydroxy-alpha-substitution-1-and replaces or non-substituted arene acetone.
Intermediate product is under organic solvent, phase-transfer catalyst and alkaline environment, stirring is warmed up to little boiling, after realizing a phase or two-phase hydrolysis reaction, normal pressure steams organic solvent, reduce to room temperature, add water decomposition, use the water-insoluble organic substance extraction that middle product and final product is all had certain solubility, tell organic phase, be washed to neutrality.Normal pressure steams solvent after the organic phase drying, and underpressure distillation collection fraction or recrystallization obtain Alpha-hydroxy-alpha-substitution-1-replacement or non-substituted arene acetone again.
With specific embodiment in detail the present invention is described in detail below:
Embodiment 1: Alpha-hydroxy-Alpha-Methyl Propiophenone (D-173) synthetic
The aluminum trichloride (anhydrous) of 19g (0.14mol) is dropped in the 170ml dry-out benzene, be cooled to 0-5 ℃ with ice-water-bath, stir the alpha-methacryloylchloride that drips 10.7g (0.1mol) down, feed excessive anhydrous hydrogen chloride simultaneously and reach 0.1Mpa, closed reactor up to pressure.After dripping, be warming up to 80 ℃ of stirring 1h that reflux again, reaction mixture darkens.Leave standstill cool to room temperature, pour reaction mixture in 500g trash ice-concentrated hydrochloric acid solution (volume ratio 2: 1) hydrolysis, the layering extraction.Organic phase is extremely neutral with saturated sodium carbonate solution washing successively, washes with water again.Normal pressure steams solvent after the organic phase drying, and 125-130 ℃/8.4KPa fraction, i.e. α-chloro-Alpha-Methyl Propiophenone are collected in underpressure distillation again.
In the there-necked flask of electronic stirring is housed, add α-chloro-Alpha-Methyl Propiophenone of 18.5g (0.1mol), and dilute with 100ml methyl alcohol, add the sodium methylate of 5.4g (0.1mol), drop into 1.5g consisting of phase-transferring agent PEG-400.Stirring is warmed up to little boiling, and liquid chromatography is followed the tracks of to react to raw material and disappeared.Normal pressure steams methyl alcohol, reduces to room temperature.Add the 100ml water decomposition, 100ml 1, and organic phase is told in the extraction of 2-ethylene dichloride, is washed to neutrality.112-115 ℃/0.667kPa fraction is collected in the organic phase underpressure distillation, is product Alpha-hydroxy-Alpha-Methyl Propiophenone (D-173).
Embodiment 2: Alpha-hydroxy-Alpha-Methyl Propiophenone (D-173) synthetic
The potassium titanate of 0.6mol put into fill the 0.5mol dry-out benzene, 200ml 1, in the 500ml four-hole bottle of 2-ethylene dichloride, be cooled to 0-5 ℃ with ice-water-bath, stir the 2-methacrylic chloride that drips 0.5mol down, feed excessive anhydrous hydrogen chloride to pressure simultaneously and reach 0.04Mpa, closed reactor.After dripping, be warming up to 80 ℃ of stirring 1h that reflux again, reaction mixture darkens.Leave standstill cool to room temperature, pour reaction mixture in 1500g trash ice-concentrated hydrochloric acid solution (volume ratio 2: 1) hydrolysis, with 200ml 1, the extraction of 2-ethylene dichloride, layering.Organic phase is extremely neutral with saturated sodium carbonate solution washing successively, washes with water again.Normal pressure steams solvent after the organic phase drying, and 135-140 ℃/10KPa fraction, i.e. α-chloro-Alpha-Methyl Propiophenone are collected in underpressure distillation again.
In the there-necked flask of electronic stirring is housed, add α-chloro-Alpha-Methyl Propiophenone of 18.5g (0.1mol), and dilute with the 100ml chlorobenzene, add the yellow soda ash of 0.3mol, 100ml water drops into 1.5g consisting of phase-transferring agent zephiran chloride front three amine salt.Stirring is warmed up to little boiling, and liquid chromatography is followed the tracks of to react to raw material and disappeared.Add 100ml water again, stir, leave standstill and tell organic layer.Organic layer is washed to neutrality with 20ml.112-115 ℃/0.667kPa fraction is collected in underpressure distillation, is product Alpha-hydroxy-Alpha-Methyl Propiophenone (D-173).
Embodiment 3: Alpha-hydroxy-Alpha-Methyl Propiophenone (D-173) synthetic
The anhydrous butter of antimony of 0.6mol put into fill the 0.5mol dry-out benzene, in the 500ml four-hole bottle of 200mol CCl4, be cooled to room temperature with ice-water-bath, stir the alpha-methacryloylchloride that drips 0.5mol down, feed excessive anhydrous hydrogen chloride to pressure simultaneously and reach 0.01Mpa, closed reactor.After dripping, be warming up to 80 ℃ of stirring 1h that reflux again, reaction mixture darkens.Leave standstill cool to room temperature, pour reaction mixture into hydrolysis in 1500g trash ice-concentrated hydrochloric acid solution (volume ratio 2: 1), standing demix.Water with 100mol CCl4 extraction, merges organic layer again.Organic phase is extremely neutral with saturated sodium carbonate solution washing successively, washes with water again.Normal pressure steams solvent after the organic phase drying, and 135-140 ℃/10KPa fraction, i.e. α-chloro-Alpha-Methyl Propiophenone are collected in underpressure distillation again.
In the there-necked flask of electronic stirring is housed, α-chloro-Alpha-Methyl the Propiophenone that adds 18.5g (0.1mol), and with the dilution of 100ml chlorobenzene, the calcium oxide of adding 0.2mol, the 30ml aqueous solution drops into 0.5g consisting of phase-transferring agent 4-(dimethylamino)-N-(2-ethyl) hexyl pyridine () salt.Stirring is warmed up to little boiling, and liquid chromatography is followed the tracks of to react to raw material and disappeared.Tell organic phase, alkali cleaning, be washed to neutrality.112-115 ℃/0.667kPa fraction is collected in the organic phase underpressure distillation, is product Alpha-hydroxy-Alpha-Methyl Propiophenone (D-173).
Embodiment 4:1-[4-(2-hydroxy ethoxy) phenyl]-Alpha-hydroxy-Alpha-Methyl-1-acetone (Irgacure2959) synthetic
In the 250ml there-necked flask of being furnished with agitator, add 200ml dithiocarbonic anhydride, the ethylene glycol phenyl ether acetate of 18g (0.098mol) drying adds 14.1g (0.105mol) aluminum trichloride (anhydrous) again.Under high degree of agitation, add 14.5g (0.0985mol) alpha-methacryloylchloride through constant pressure funnel, feed excessive anhydrous hydrogen chloride to pressure simultaneously and reach 0.05Mpa, tube sealing reaction.After dripping, after the stirring at room, be warming up to 50 ℃ of backflows again, till reaction mixture darkens.After being chilled to room temperature, under agitation, slowly pour hydrolysis in 1000g trash ice-concentrated hydrochloric acid solution (volume ratio 2: 1) into, leave standstill after 1 hour and divide oil-yielding stratum.With the washing of 10% sodium hydroxide solution, water washing is to neutral successively for organic layer.The oil reservoir air distillation reclaims 1, behind the 2-ethylene dichloride, and the residuum underpressure distillation, the cut of 188-194 ℃/8.4KPa of collection is 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] acetic ester.
In the there-necked flask of electronic stirring is housed, add 100g (0.35mol) 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] acetic ester, add 500ml 1, the 2-ethylene dichloride, add 210g 10% (0.525mol) aqueous sodium hydroxide solution again, 5g Tetrabutyl amonium bromide consisting of phase-transferring agent.Stirring is warmed up to little boiling, and liquid chromatography is followed the tracks of reaction, to 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] till acetic ester reacted.Leave standstill, tell organic phase.Water is used 100ml 1 again, the extraction of 2-ethylene dichloride.Merge organic phase, be washed to neutrality.The air distillation of organic layer elder generation goes out partial solvent, is refrigerated to-5 ℃ of crystallizations again.With 1: 3 recrystallizing methanol of weight ratio, promptly get Irgacure 2959.
Embodiment 5:1-[4-(2-hydroxy ethoxy) phenyl]-Alpha-hydroxy-Alpha-Methyl-1-acetone (Irgacure2959) synthetic
In the 250ml there-necked flask of being furnished with agitator, add 200ml 1, the 2-ethylene dichloride, the ethylene glycol phenyl ether acetate of 18g (0.098mol) drying adds the 0.125mol iron trichloride again.Under high degree of agitation, add 14.5g (0.0985mol) 2-methacrylic chloride through constant pressure funnel, feed excessive anhydrous hydrogen chloride to pressure simultaneously and reach 0.03Mpa, tube sealing reaction.After dripping, after the stirring at room, be warming up to 80 ℃ of backflows again, till reaction mixture darkens.After being chilled to room temperature, under agitation, slowly pour hydrolysis in 1000g trash ice-concentrated hydrochloric acid solution (volume ratio 2: 1) into, leave standstill after 1 hour and divide oil-yielding stratum, oil reservoir uses 10% sodium hydroxide solution and water washing to neutral successively.The organic layer air distillation reclaims 1, behind the 2-ethylene dichloride.The residuum underpressure distillation, the cut of 188-194 ℃/8.4KPa of collection is 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] acetic ester.
In the there-necked flask of electronic stirring is housed, add 100g (0.35mol) 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] acetic ester, add the 100ml trimethyl carbinol, add 0.7mol potassium hydroxide again, 1g benzyltriethylammoinium chloride consisting of phase-transferring agent.Stirring is warmed up to little boiling, and liquid chromatography is followed the tracks of reaction, to 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] till acetic ester reacted.Normal pressure steams the trimethyl carbinol, reduces to room temperature.Add the 100ml water decomposition, 100ml 1, and organic phase is told in the extraction of 2-ethylene dichloride, is washed to neutrality.Elder generation's air distillation goes out partial solvent, is refrigerated to-5 ℃ of crystallizations again.With 1: 3 recrystallizing methanol of weight ratio, be Irgacure 2959.
Embodiment 6:1-[4-(2-hydroxy ethoxy) phenyl]-Alpha-hydroxy-Alpha-Methyl-1-acetone (Irgacure2959) synthetic
In the 250ml there-necked flask of being furnished with agitator, add 200ml 1, the 2-ethylene dichloride, 18g (0.098mol) ethylene glycol phenyl ether acetate adds the anhydrous butter of antimony of 0.105mol again.Under high degree of agitation, add 14.5g (0.0985mol) alpha-methacryloylchloride through constant pressure funnel, feed excessive anhydrous hydrogen chloride to pressure simultaneously and reach 0.01Mpa, tube sealing reaction.After dripping, after the stirring at room, suitably be warming up to backflow again, till reaction mixture darkens.After being chilled to room temperature, under agitation, slowly pour hydrolysis in 1000g trash ice-concentrated hydrochloric acid solution (volume ratio 2: 1) into, leave standstill after 1 hour and divide oil-yielding stratum.Organic layer uses 10% sodium hydroxide solution and water washing to neutral successively.The organic layer air distillation reclaims 1, behind the 2-ethylene dichloride, and the residuum underpressure distillation, the cut of 188-194 ℃/8.4KPa of collection is 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] acetic ester.
In the there-necked flask of electronic stirring is housed, add 100g (0.35mol) 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] acetic ester, add the 500ml tetracol phenixin, add the 0.75mol potassium oxalate again, 100ml water, 1g hexaoxacyclooctadecane-6-6 consisting of phase-transferring agent.Stirring is warmed up to little boiling, and liquid chromatography is followed the tracks of reaction, to 2-[4-(α-chloro-Alpha-Methyl propyl group phenoxy group)] till acetic ester reacted.Tell organic phase, be washed to neutrality.The air distillation of organic phase elder generation goes out partial solvent, is refrigerated to-5 ℃ of crystallizations again.With 1: 3 recrystallizing methanol of weight ratio, be Irgacure 2959.
Claims (3)
1. the novel synthesis of an Alpha-hydroxy arone compounds is characterized in that reaction carries out in two steps:
The first step, replace or non-substituted arene, alpha-substitution acryloyl halide and anhydrous hydrogen halide under the environment of catalyzer and anhydrous, water-insoluble solvent, in enclosed system, under pressurized conditions, react, generating alpha-halogen-alpha-substitution-1-replaces or non-substituted arene acetone intermediate product
Described anhydrous hydrogen halide environment is meant and contains F, Cl, and Br, the environment of I hydride,
Described catalyzer is meant the sodium of the halogen, vitriol, nitrate, acetate, oxalate or the oxygen acid that contain two or more element among Fe, Sn, V, Zr, W, Pd, Al, Ti, Zn, Sb, Cr, Mn, Bi or the Mo or the product that sylvite forms through co-precipitation, filtration, oven dry, roasting, pulverizing;
Described anhydrous, water-insoluble solvent is meant that the catalyzer raw material has the F that contains of certain solubility, Cl, Br, I, S, the aliphatic saturated hydrocarbon of O, saturated alicyclic hydrocarbon, aromatic hydrocarbon, heterogeneous ring compound to replacing or non-substituted arene, alpha-substitution acryloyl halide, anhydrous hydrogen halide;
The pressure of compressive reaction is the 0.01-10 normal atmosphere;
In second step, intermediate product is realized a phase or a two-phase hydrolysis reaction under organic solvent, phase-transfer catalyst and alkaline environment, through extraction agent extraction last handling process, obtain Alpha-hydroxy-alpha-substitution-1-and replace or non-substituted arene acetone,
Described organic solvent is meant all has the water-soluble or water-insoluble organism of certain solubility to middle product and final product, as contains aliphatic saturated hydrocarbon, saturated alicyclic hydrocarbon, aromatic hydrocarbon or the heterogeneous ring compound of F, Cl, Br, I, S or O,
Described extraction agent is meant all has the water-insoluble organism of certain solubility to middle product and final product, as contains aliphatic saturated hydrocarbon, saturated alicyclic hydrocarbon, aromatic hydrocarbon or the heterogeneous ring compound of F, Cl, Br, I, S or O,
Described alkaline environment is meant and contains Na, K, and Ca, the oxyhydroxide of Mg, carbonate, acetate, oxalate, and sodium methylate or potassium, sodium tert-butoxide or potassium compound,
Described phase-transfer catalyst is meant and contains N, the salt of P, crown ether, and acyclic polyether or PEG class,
Concrete reaction formula is:
In the formula: R
1Be H, aliphatic saturated hydrocarbon, saturated alicyclic hydrocarbon, aromatic hydrocarbon, heterogeneous ring compound,
X is F, Cl, Br or I,
R
2Be H, aliphatic saturated hydrocarbon, saturated alicyclic hydrocarbon, aromatic hydrocarbon, heterogeneous ring compound.
2. the novel synthesis of a kind of Alpha-hydroxy arone compounds according to claim 1, it is characterized in that replacing or non-substituted arene, alpha-substitution acryloyl halide and anhydrous hydrogen halide are at catalyzer and anhydrous, under the environment of water-insoluble solvent, in enclosed system, be warming up to reflux temperature, stir 1h, reaction mixture darkens, leave standstill cool to room temperature, pour hydrolysis in trash ice-concentrated hydrochloric acid solution of 2: 1 of volume ratio into, use the reaction solvent extracting and demixing, the organic phase of extraction is washed up to neutrality with saturated sodium carbonate solution successively, water washing, normal pressure steams solvent after the organic phase drying, and fraction is collected in underpressure distillation again, gets alpha-halogen-alpha-substitution-1-and replaces or non-substituted arene acetone intermediate product.
3. the novel synthesis of a kind of Alpha-hydroxy arone compounds according to claim 1, it is characterized in that intermediate product is at organic solvent, under phase-transfer catalyst and the alkaline environment, stirring is warmed up to little boiling, after realizing a phase or two-phase hydrolysis reaction, normal pressure steams organic solvent, reduce to room temperature, add water decomposition, with the water-insoluble organic substance extraction that middle product and final product is all had certain solubility, tell organic phase, be washed to neutrality, normal pressure steams solvent after the organic phase drying, and underpressure distillation collection fraction or recrystallization obtain Alpha-hydroxy-alpha-substitution-1-replacement or non-substituted arene acetone again.
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| CN106518638A (en) * | 2016-11-02 | 2017-03-22 | 怀化金鑫新材料有限公司 | New synthesis technology for photoinitiator1173 |
| CN114315575A (en) * | 2021-12-29 | 2022-04-12 | 湖南久日新材料有限公司 | Preparation method and application of photoinitiator intermediate |
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| CN102786405A (en) * | 2012-08-29 | 2012-11-21 | 天津久日化学股份有限公司 | Preparation method for 2-hydroxy-1-[4-(2-hydroxyethoxy) phenyl]-2-methyl-1-acetone |
| CN103613492A (en) * | 2013-12-10 | 2014-03-05 | 岳阳市国发植物用药工程技术研究中心有限公司 | Synthesis method of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
| CN103613492B (en) * | 2013-12-10 | 2015-04-15 | 岳阳市国发植物用药工程技术研究中心有限公司 | Synthesis method of photoinitiator 2-hydroxy-2-methyl-1-phenyl-1-propyl ketone |
| CN106518638A (en) * | 2016-11-02 | 2017-03-22 | 怀化金鑫新材料有限公司 | New synthesis technology for photoinitiator1173 |
| CN114315575A (en) * | 2021-12-29 | 2022-04-12 | 湖南久日新材料有限公司 | Preparation method and application of photoinitiator intermediate |
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