CN103588729A - Synthetic method of 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one - Google Patents
Synthetic method of 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one Download PDFInfo
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- CN103588729A CN103588729A CN201310644086.7A CN201310644086A CN103588729A CN 103588729 A CN103588729 A CN 103588729A CN 201310644086 A CN201310644086 A CN 201310644086A CN 103588729 A CN103588729 A CN 103588729A
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- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/04—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms
- C07D295/10—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms
- C07D295/104—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms with substituted hydrocarbon radicals attached to ring nitrogen atoms substituted by doubly bound oxygen or sulphur atoms with the ring nitrogen atoms and the doubly bound oxygen or sulfur atoms attached to the same carbon chain, which is not interrupted by carbocyclic rings
Abstract
The invention discloses a synthetic method of 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one which is efficient free radical photoinitiator. The synthetic method of the 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one specifically comprises the steps that biphenyl serves as a raw material, an acylation reaction and a chlorination reaction are carried out on the biphenyl, and finally the biphenyl reacts with morpholine. According to the three reactions, intermediates do not need to be processed through purification, solvent dose not need to be replaced, continuous reactions can be carried out, the total yield is high, and the technology is friendly to the environment. The synthetic method of the 1-(biphenyl-4-yl)-2-methyl-2-morpholinopropan-1-one is low in cost, friendly to the environment, easy to operate and applicable to industrialization.
Description
Technical field
The present invention relates to a kind of efficient free radical photo-initiation 1-(xenyl-4-yl) synthetic method of-2-methyl-2-morpholinyl propane-1-ketone; being specifically related to 1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone take biphenyl as raw material; through acylations, chloro; finally react with morpholine; this three-step reaction intermediate does not need to purify, do not need to change solvent can successive reaction, and the synthetic method of a cheapness, environmental protection, easy to operate, suitability for industrialized is provided.
Background technology
1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone is a kind of new ultra-violet alpha-aminoacetophenone photoinitiator, there is efficient radical polymerization initiating activity, can use separately, also can with ITX or traditional hydroxyketone and the composite use of diphenyl ketone type light trigger.
Shenzhen promising chemical technology Development Co., Ltd applies for a patent CN101724099 and has disclosed a series of 1-(of comprising xenyl-4-yls) the derivative amido ketone compounds with light-initiated activity of the xenyl of-2-methyl-2-morpholinyl propane-1-ketone, and provide 1-(xenyl-4-yl) synthetic method of-2-methyl-2-morpholinyl propane-1-ketone, the isobutyryl chloride obtaining and biphenyl generate aryl ketones intermediate at aluminum chloride generation acylation reaction, intermediate reacts with bromine and generates α-bromoketone class intermediate, finally obtain target product with morpholine generation substitution reaction again.
The defect of this technique:
1, the large usage quantity of aluminum chloride (1.5eq.), causes product cost high, and the waste acid water of generation is more, not environmental protection;
2, bromine has been used in reaction, and price is higher, consumption large (1.1eq.), and atom utilization is low, uneconomical;
3, the corrodibility of bromine own is strong, high to equipment requirements, not easy to operate, poor stability, not environmental protection;
4, α-bromoketone class intermediate reacts morpholine and makes reactant and do again acid binding agent with morpholine, and consumption large (2.1eq.), is difficult for reclaiming, and produces a large amount of waste water;
5, α-bromoketone class intermediate reacts with morpholine, the time long (24h), only have medium yield (81%), and be difficult for being purified to more than 99%, and length, cost remain high to cause the whole explained hereafter cycle.
Therefore, from economic angle or environmental, being all not suitable for industrialization generates.
Chen Ting applies for a patent CN102924630 and finds 1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone is the effective substitute of Irgacure 907.Irgacure 907 is very important light trigger in UV uv radiation curing field, but in the structure of this compound, in aromatic nucleus system, contain first sulfydryl, inevitably cause occurring xanthochromia, remaining unpleasant odor and produce the carcinogenic problems such as volatile organic compounds in Light Curing, in a lot of places, having limited its use.And 1-(xenyl-4-yl) in-2-methyl-2-morpholinyl propane-1-ketone structure containing element sulphur, it is applied in and has not only embodied excellent yellowing resistance containing time in unsaturated allyl compound system UV radical photopolymerization solidification process as one of light trigger or photoinitiator composite, eliminate sulfur-bearing adverse residue smell completely, and significantly reduced all kinds of harmful volatile organic compoundss release.Meanwhile, under same or analogous application conditions, this compound has represented the light-initiated activity equal or higher with Irgacure 907 in the Financial cost competition of advantage.The product that can substitute in the market Irgacure 907 is very limited, people are more and more higher to the requirement of environment simultaneously, 1-(xenyl-4-yl that performance is more excellent)-2-methyl-2-morpholinyl propane-1-ketone can be more and more important in photocuring field, therefore develops the more friendly synthetic 1-(xenyl-4-yl of more economical environment) to obtain operational path be very necessary to-2-methyl-2-morpholinyl propane-1-ketone and be badly in need of.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of 1-(xenyl-4-yl) synthesis technique of-2-methyl-2-morpholinyl propane-1-ketone.This synthesis technique can overcome in existing method and has the problems such as cost is high, toxicity is large, waste water is many, difficult industrial implementation, is that a kind of cost is low, environmental friendliness, yield are high, easily operation, have that industrial production is worth synthetic method.
The present invention synthesizes 1-(xenyl-4-yl) technical process of-2-methyl-2-morpholinyl propane-1-ketone is as follows:
Technical problem to be solved by this invention is to realize by following concrete technical scheme.The present invention is a kind of 1-(xenyl-4-yl) synthesis technique of-2-methyl-2-morpholinyl propane-1-ketone, concrete steps are as follows:
1), friedel-crafts acylation: solvent and catalyzer are joined in reaction flask; be cooled to 10 ℃ and add below biphenyl in batches; at 5 ℃ of following isobutyryl chlorides that drip; biphenyl, aluminum chloride, isobutyryl chloride amount of substance ratio are selected from 1:1.0～1.2:1.0～1.2; the consumption of solvent is selected from 3.0～6.0 times of biphenyl quality; 30min drips complete, is then warming up to 5～20 ℃, reacts 3～5 hours.TLC or GC follow the tracks of reaction, after reacting completely, reaction solution are poured in 3～4% dilute hydrochloric acid and are carried out acidolysis, and aqueous phase discarded, washing organic phase, obtains 1-(xenyl-4-yl) the solution GC content of-2-methylpropane-1-ketone is more than 99%;
2), chlorination reaction: by 1) the synthetic 1-(xenyl-4-yl obtaining)-2-methylpropane-1-ketone solution directly puts in chlorination bottle, is warming up to 90～120 ℃, passes into chlorine, reacts 4～8 hours, TLC or LC follow the tracks of reaction.After reaction finishes, be down to room temperature, add respectively appropriate water, saturated sodium bicarbonate agitator treating, divide the phase of anhydrating, obtain 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, content is more than 98%;
3), substitution reaction: by 2) the synthetic 1-(xenyl-4-yl obtaining)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, morpholine, alkaline aqueous solution mixes, and is heated to certain temperature, insulation reaction 3～6 hours, TLC or LC follow the tracks of reaction.After reaction finishes, cooling, separates water and organic phase, organic phase distillating recovering solvent, and recovered solvent can directly overlap and use next batch reaction through pre-treatment.The residue obtaining after organic phase distillating recovering solvent is 1-(xenyl-4-yl) crude product of-2-methyl-2-morpholinyl propane-1-ketone, add appropriate methanol crystallization, filter, dryly obtain white 1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone, purity is more than 99%, three-step reaction total recovery 90% and more than, gained filtrate can be applied mechanically to next batch crystallization for continuous 1～2 time, and then Distillation recovery is applied mechanically.
1-(xenyl-4-yl provided by the invention) synthetic method of-2-methyl-2-morpholinyl propane-1-ketone, it is characterized in that step 1), 2), 3) solvent that jointly uses is selected from methylene dichloride, trichloromethane, ethylene dichloride, chlorobenzene, normal hexane, sherwood oil, preferably methylene dichloride, ethylene dichloride, chlorobenzene or their mixing.
1-(xenyl-4-yl provided by the invention) synthetic method of-2-methyl-2-morpholinyl propane-1-ketone, is characterized in that the catalyzer that step 1) is used is selected from aluminum chloride, iron trichloride, zinc chloride, titanium chloride, preferably aluminum chloride and iron trichloride.
1-(xenyl-4-yl provided by the invention) synthetic method of-2-methyl-2-morpholinyl propane-1-ketone, is characterized in that the amount of step 3) morpholine used is selected from 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone with the amount of morpholine materials than 1:1.0～1.2.
1-(xenyl-4-yl provided by the invention) synthetic method of-2-methyl-2-morpholinyl propane-1-ketone, is characterized in that the temperature of reaction of step 3) is selected from 40～80 ℃.
1-(xenyl-4-yl provided by the invention) synthetic method of-2-methyl-2-morpholinyl propane-1-ketone, is characterized in that step 3) alkali used is selected from mineral alkali or their mixing such as sodium bicarbonate, sodium carbonate, saleratus, salt of wormwood, calcium hydroxide, sodium hydroxide, potassium hydroxide; While using salt of wormwood, sodium carbonate or calcium hydroxide, its consumption is 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone than the amount of alkaloid substance than 1:0.5～0.6; While using saleratus, sodium bicarbonate, sodium hydroxide or potassium hydroxide, its consumption is 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone than the amount of alkaloid substance than 1:1.0～1.2.
The inventor finds in research process, and during step 3) reaction, excess Temperature and morpholine concentration are crossed and is mostly unfavorable for reaction, and by product increases.Test of many times finds can not only guarantee when 60 ℃ of left and right that speed of response can also reduce side reaction simultaneously, it is 1-(xenyl-4-yl that the theory of morpholine needs minimum)-the amount of substances such as 2-methyl-2 cbloropropane isopropyl chloride-1-ketone, but in reaction process, produce gradually hydrogenchloride, the hydrogenchloride producing can preferentially consume again morpholine (the 1-(xenyl-4-yl producing with reaction)-2-methyl-2-morpholinyl propane-1-ketone and compare, the alkalescence of morpholine and locus factor all can be preferentially and hcl reaction), when ruing out of morpholine reaction, carry out maybe can not proceeding very slowly, therefore if needing morpholine amount when other acid binding agent is not used in this step reaction is at least 1-(xenyl-4-yl) 2 times of-2-methyl-2 cbloropropane isopropyl chloride-1-ketone amount of substance, there is so the hydrogenchloride that the morpholine of 1 times of amount can be produced in reaction process to consume, in this case, while just starting to react, the high tendency that produces by product that has of concentration of morpholine, considering the present invention selects inorganic base aqueous solution to do acid binding agent, reduce the consumption of morpholine, due to the water-soluble and organic solvent of morpholine energy itself, although be therefore two phase reaction, do not need with phase-transfer catalyst, just can guarantee speed of response in addition, simultaneously due to the water-soluble characteristic of morpholine, some morpholine can be distributed in the aqueous solution, morpholine is reduced in the concentration of organic phase, avoid the situation of the excessive concentration of morpholine when just starting to react.
1-(xenyl-4-yl provided by the invention)-2-methyl-2-morpholinyl propane-1-ketone synthesis technique not only avoids using price, raw material that corrodibility is strong, can also obtain surpassing the product yield (three step total recoverys 90% and more than, the total recovery of document two-step reaction just has 88.1%) of document simultaneously.Synthesis technique three-step reaction provided by the invention shares a solvent simultaneously, saved distillation procedure, not only simplified technique, reduced the loss of solvent simultaneously, saved cost, convenient unified the depositing of recovered solvent, has reduced the chance of solvent crossed contamination, and recovered solvent can be applied mechanically through simple pre-treatment (such as sedimentation).
1-(xenyl-4-yl provided by the invention)-2-methyl-2-morpholinyl propane-1-ketone synthesis technique advantage is:
1) having used chlorine cheap, that be easy to get is halogenating agent;
2) three-step reaction has only been used a solvent, and has saved distillation procedure, not only reduces equipment investment and working cost, has reduced the loss of solvent simultaneously, has saved cost;
3) reduced the consumption of morpholine, used inorganic base aqueous solution to do acid binding agent, speed of response is fast, and yield is high;
4) shortened the reaction times, can reduce the production cycle, enhanced productivity;
5) simple to operate, be easy to industrializing implementation.
Embodiment
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 1:1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone is synthetic
1) in the reactor of 1000 milliliters, add 450 grams of isopropylformic acids, be warming up to 45 ℃, then add 320 grams of phosphorus trichlorides, 55 ℃ are incubated 6 hours, and GC follows the tracks of reaction, after raw material isopropylformic acid disappears, finish reaction.Divide the mineral acid that falls down layer, obtain 541.8 grams of isobutyryl chlorides, GC content 99.4%, product yield approximately 99.6%.
2) in the reaction flask of 1000 milliliters, add 376 grams of anhydrous ethylene dichloride, be cooled to 10 ℃, add 90 grams of aluminum trichloride (anhydrous)s, biphenyl 100g, continue to be cooled to 5 ℃, add 76 grams of the acyl chlorides that step 1) makes, 5 ℃ of insulations 5 hours, GC follows the tracks of reaction, after raw material biphenyl disappears, finishes reaction.Above-mentioned reaction solution is poured in the dilute hydrochloric acid of 240 gram 3%, stirred after 1 hour, separatory obtains 1-(xenyl-4-yl)-2-methylpropane-1-ketone solution, GC content 99.3%.
3) in 250 milliliters of reaction flasks, add step 2) 1-(xenyl-4-yl of making)-2-methylpropane-1-ketone solution, be warming up to 90 ℃, then pass into chlorine, GC follows the tracks of reaction, 1-(xenyl-4-yl) after-2-methylpropane-1-ketone disappears, finish reaction.Cooling adds 133 ml waters to stir separatory after 30 minutes, in organic phase, adds 75ml saturated sodium carbonate solution, stirs separatory after 30 minutes, collects organic phase and obtains 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution.
4) toward the synthetic 1-(xenyl-4-yl of step 3)) add 62.2 grams of morpholines and 114g saturated sodium carbonate solution in-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, be heated to 60 ℃ of reactions, GC follows the tracks of reaction, after reaction finishes, standing, separate water, organic phase is with after isopyknic washing, after decompression and solvent recovery, obtain 1-(xenyl-4-yl) 192.6 grams of the crude products of-2-methyl-2-morpholinyl propane-1-ketone, recovered solvent can directly overlap and use next batch reaction through sedimentation, in above-mentioned crude product, add dehydrated alcohol recrystallization, suction filtration, dry, obtain 182.5 grams of white powder solids, yield 91%, purity 99.4%, the filtrate obtaining can be overlapped and be used next batch crude product crystallization 1～2 time.
Embodiment 2:1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone is synthetic
1) in the reaction flask of 1000 milliliters, add 376 grams of anhydrous chlorobenzenes, be cooled to 10 ℃, add 90 grams of aluminum trichloride (anhydrous)s, biphenyl 100g, continue to be cooled to 5 ℃, add 76 grams of the acyl chlorides that embodiment 1 makes, 5 ℃ of insulations 5 hours, GC follows the tracks of reaction, after raw material biphenyl disappears, finishes reaction.Above-mentioned reaction solution is poured in the dilute hydrochloric acid of 240 gram 3%, stirred after 1 hour, separatory obtains 2-methyl isophthalic acid-xenyl-1-acetone soln, GC content 99.5%.
2) the 1-(xenyl-4-yl that adds step 1) to make in 250 milliliters of reaction flasks)-2-methylpropane-1-ketone solution, is warming up to 90 ℃, then passes into chlorine, and GC follows the tracks of reaction, 1-(xenyl-4-yl) after-2-methylpropane-1-ketone disappears, finish reaction.Cooling adds 133 ml waters to stir separatory after 30 minutes, in organic phase, adds 75ml saturated sodium carbonate solution, stirs separatory after 30 minutes, collects organic phase and obtains 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution.
3) toward step 2) synthetic 1-(xenyl-4-yl) add 62.2 grams of morpholines and 114g saturated sodium carbonate solution in-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, be heated to 60 ℃ of reactions, GC follows the tracks of reaction, after reaction finishes, standing, separate water, organic phase is with after isopyknic washing, after decompression and solvent recovery, obtain 1-(xenyl-4-yl) 193.2 grams of the crude products of-2-methyl-2-morpholinyl propane-1-ketone, recovered solvent can directly overlap and use next batch reaction through sedimentation, in above-mentioned crude product, add dehydrated alcohol recrystallization, suction filtration, dry, obtain 181.5 grams of white powder solids, yield 90.5%, content 99.3%, the filtrate obtaining can be overlapped and be used next batch crude product crystallization 1～2 time.
Embodiment 3:1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone is synthetic
1) in the reaction flask of 1000 milliliters, add 376 grams of anhydrous ethylene dichloride, be cooled to 8 ℃, add 95 grams of aluminum trichloride (anhydrous)s, biphenyl 100g, continue to be cooled to 3 ℃, add 76 grams of the acyl chlorides that embodiment 1 makes, 14 ℃ of insulations 4 hours, GC follows the tracks of reaction, after raw material biphenyl disappears, finishes reaction.Above-mentioned reaction solution is poured in the dilute hydrochloric acid of 220 gram 3.5%, stirred after 1 hour, separatory, organic phase is 1-(xenyl-4-yl) and-2-methylpropane-1-ketone solution, GC content 99.0%.
2) in the reaction flask of 250 milliliters, add 1) 1-(xenyl-4-yl of making)-2-methylpropane-1-ketone solution, be warming up to 90 ℃, then pass into chlorine, GC follows the tracks of reaction, until 1-(xenyl-4-yl) after-2-methylpropane-1-ketone disappears, finish reaction.Cooling adds 133 ml waters to stir separatory after 30 minutes, in organic phase, adds 75ml saturated sodium carbonate solution, stirs separatory after 30 minutes, collects organic phase and obtains 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution.
3) toward step 2) synthetic 1-(xenyl-4-yl) add 197.3 grams of morpholines in-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, be heated to 60 ℃ of reactions, GC follows the tracks of reaction, finish after reaction, unreacted morpholine and solvent are reclaimed in water pump underpressure distillation, be cooled to below 80 ℃, add 200 toluene and 200 ml waters, wash the hydrochloride of the morpholine of reaction generation off, stir separatory after 30 minutes, after organic phase vacuum distillation recovered solvent, obtain 1-(xenyl-4-yl) 190 grams of the crude products of-2-methyl-2-morpholinyl propane-1-ketone, in above-mentioned crude product, add dehydrated alcohol, stir lower heating for dissolving recrystallization, suction filtration, dry, obtain 170.5 grams of buff powder solids, GC content 98.6%, use again new dehydrated alcohol secondary crystal, suction filtration, dry, obtain 156.5 grams of white powder solids, GC content 99.3%, three-step reaction total recovery 79%.
Embodiment 4:1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone is synthetic
1) in the reaction flask of 1000 milliliters, add 376 grams of anhydrous chlorobenzenes, be cooled to 6 ℃, add 104 grams of aluminum trichloride (anhydrous)s, biphenyl 100g, continue to be cooled to 0 ℃, add 76 grams of the acyl chlorides that embodiment 1 makes, 20 ℃ of insulations 3 hours, GC follows the tracks of reaction, after raw material biphenyl disappears, finishes reaction.Above-mentioned reaction solution is poured in the dilute hydrochloric acid of 200 gram 4%, stirred after 1 hour, separatory, organic phase is 1-(xenyl-4-yl) and-2-methylpropane-1-ketone solution, GC content 99.2%.
2) the 1-(xenyl-4-yl that adds step 1) to make in the reaction flask of 250 milliliters)-2-methylpropane-1-ketone solution, is warming up to 90 ℃, then passes into chlorine, and GC follows the tracks of reaction, after 2-methyl isophthalic acid-xenyl-1-acetone disappears, finishes reaction.Cooling adds 133 ml waters to stir separatory after 30 minutes, in organic phase, adds 75ml saturated sodium carbonate solution, stirs separatory after 30 minutes, collects organic phase and obtains 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution.
3) toward step 2) synthetic 1-(xenyl-4-yl) add 62.2 grams of morpholines and 114g saturated sodium carbonate solution in-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, be heated to 120 ℃ of reactions, GC follows the tracks of reaction, after reaction finishes, standing, separate water, organic phase is with after isopyknic washing, decompression and solvent recovery, obtain 1-(xenyl-4-yl) 191 grams of the crude products of-2-methyl-2-morpholinyl propane-1-ketone, in above-mentioned crude product, add dehydrated alcohol recrystallization, suction filtration, dry, obtain 172.5 grams of buff powder solids, GC content 98.7%, use again new dehydrated alcohol secondary crystal, suction filtration, dry, obtain 162.5 grams of white powder solids, GC content 99.1%, three-step reaction total recovery 81%.
Claims (7)
1. a 1-(xenyl-4-yl) synthetic method for-2-methyl-2-morpholinyl propane-1-ketone, is characterized in that the step that it comprises:
1), friedel-crafts acylation: solvent and catalyzer are joined in reactor; be cooled to 10 ℃ and add below biphenyl in batches; at 5 ℃ of following isobutyryl chlorides that drip; biphenyl, aluminum chloride, isobutyryl chloride amount of substance ratio are selected from 1:1.0～1.2:1.0～1.2; the consumption of solvent is selected from 3.0～6.0 times of biphenyl quality; 30min drips complete, is then warming up to 5～20 ℃, reacts 3～5 hours.TLC or GC follow the tracks of reaction, after reacting completely, reaction solution are poured in the dilute hydrochloric acid of 3-4% and are carried out acidolysis, and aqueous phase discarded, washing organic phase, obtains 1-(xenyl-4-yl) solution of-2-methylpropane-1-ketone;
2), chlorination reaction: by 1) the synthetic 1-(xenyl-4-yl obtaining)-2-methylpropane-1-ketone solution directly puts in chlorination tank, heating, passes into chlorine, reacts 4～8 hours, TLC or liquid chromatography are followed the tracks of reaction.After reaction finishes, be down to room temperature, add respectively appropriate water, saturated sodium bicarbonate agitator treating, divide the phase of anhydrating, obtain 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution;
3), substitution reaction: by 2) the synthetic 1-(xenyl-4-yl obtaining)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, morpholine, alkaline aqueous solution mixes, and is heated to certain temperature, insulation reaction 3～6 hours, TLC or LC follow the tracks of reaction.After reaction finishes, cooling, separate water and organic phase, organic phase distillating recovering solvent, the residue obtaining is 1-(xenyl-4-yl) crude product of-2-methyl-2-morpholinyl propane-1-ketone, add appropriate methanol crystallization, filter, dryly obtain white 1-(xenyl-4-yl)-2-methyl-2-morpholinyl propane-1-ketone.
2. synthetic method according to claim 1, is characterized in that step 1), 2), 3) solvent that jointly uses is selected from methylene dichloride, trichloromethane, ethylene dichloride, chlorobenzene, normal hexane, sherwood oil or their mixing.
3. synthetic method according to claim 1, is characterized in that the catalyzer that step 1) is used is selected from aluminum chloride, iron trichloride, zinc chloride, titanium chloride.
4. synthetic method according to claim 1, is characterized in that step 2) temperature of reaction that passes into chlorine is selected from 90～120 ℃.
5. synthetic method according to claim 1, is characterized in that the consumption of step 3) morpholine is selected from 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone with the amount of morpholine materials than 1:1.0～1.2.
6. synthetic method according to claim 1, is characterized in that the temperature of reaction of step 3) is selected from 40～80 ℃.
7. synthetic method according to claim 1, is characterized in that step 3) basic cpd used is selected from sodium bicarbonate, sodium carbonate, saleratus, salt of wormwood, sodium hydroxide, potassium hydroxide or their mixing; While using salt of wormwood, sodium carbonate, its consumption is 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone than basic cpd amount of substance than 1:0.5～0.6; While using saleratus, sodium bicarbonate, sodium hydroxide or potassium hydroxide, its consumption is 1-(xenyl-4-yl)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone than basic cpd amount of substance than 1:1.0～1.2.
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| CN105384707A (en) * | 2014-09-03 | 2016-03-09 | 山东久日化学科技有限公司 | Alpha-amino acetophenone photoinitiator preparation method |
| CN109456173A (en) * | 2018-12-24 | 2019-03-12 | 交城县兆晨煤焦有限公司 | A kind of preparation method of acyl chlorides |
| CN112552259A (en) * | 2020-12-28 | 2021-03-26 | 湖南久日新材料有限公司 | Preparation method of 2-methyl-1- (4-substituted phenyl) -2-morpholinyl-1-acetone |
| 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 |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105384707A (en) * | 2014-09-03 | 2016-03-09 | 山东久日化学科技有限公司 | Alpha-amino acetophenone photoinitiator preparation method |
| CN105384707B (en) * | 2014-09-03 | 2018-04-17 | 山东久日化学科技有限公司 | A kind of preparation method of α amino acetophenones light trigger |
| CN109456173A (en) * | 2018-12-24 | 2019-03-12 | 交城县兆晨煤焦有限公司 | A kind of preparation method of acyl chlorides |
| CN112552259A (en) * | 2020-12-28 | 2021-03-26 | 湖南久日新材料有限公司 | Preparation method of 2-methyl-1- (4-substituted phenyl) -2-morpholinyl-1-acetone |
| 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 |
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| CN103588729B (en) | 2016-06-29 |
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