CN103588729B - 1-(xenyl-4-base) synthetic method of-2-methyl-2-morpholinopropane-1-ketone - Google Patents
1-(xenyl-4-base) synthetic method of-2-methyl-2-morpholinopropane-1-ketone Download PDFInfo
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- C07—ORGANIC CHEMISTRY
- 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
A kind of efficiently free radical photo-initiation 1-(xenyl-4-base of disclosure) synthetic method of-2-methyl-2-morpholinopropane-1-ketone; concrete 1-(xenyl-4-base) synthetic method of-2-methyl-2-morpholinopropane-1-ketone is with biphenyl for raw material; through acyl group, chlorination; finally reacting with morpholine, this three-step reaction intermediate does not need to purify, do not need to change solvent successive reaction, total recovery height, process environments close friend.1-(xenyl-4-base disclosed by the invention) synthetic method of-2-methyl-2-morpholinopropane-1-ketone is that one cheap, environmental protection, easily operation, synthetic method suitable for industrialized.
Description
Technical field
The present invention relates to a kind of efficiently free radical photo-initiation 1-(xenyl-4-base) synthetic method of-2-methyl-2-morpholinopropane-1-ketone; it being specifically related to 1-(xenyl-4-base)-2-methyl-2-morpholinopropane-1-ketone is with biphenyl for raw material; through acyl group, chloro; finally react with morpholine; this three-step reaction intermediate does not need to purify, not needing to change solvent can successive reaction, it is provided that one cheap, environmental protection, easily operation, synthetic method suitable for industrialized.
Background technology
1-(xenyl-4-base)-2-methyl-2-morpholinopropane-1-ketone is a kind of new ultra-violet alpha-aminoacetophenone photoinitiator, there is efficient radical polymerization initiating activity, can be used alone, it is also possible to ITX or tradition hydroxy-ketone and the composite use of diphenyl ketone type light trigger.
Shenzhen promising chemical technology Development Co., Ltd applies for a patent CN101724099 and discloses a series of 1-(of including xenyl-4-base) the derivative amido ketone compounds with space charge force of the xenyl of-2-methyl-2-morpholinopropane-1-ketone, and provide 1-(xenyl-4-base) synthetic method of-2-methyl-2-morpholinopropane-1-ketone, the isobutyryl chloride obtained generates aryl ketones intermediate with biphenyl at aluminum chloride generation acylation reaction, intermediate and bromine react generation α-bromoketone class intermediate, finally obtain target product with morpholine generation substitution reaction again.
The defect of this technique:
1, the large usage quantity (1.5eq.) of aluminum chloride, causes that product cost is high, and the waste acid water of generation is more, not environmentally；
2, reaction employs bromine, and price is higher, and consumption big (1.1eq.), atom utilization is low, uneconomical；
3, the corrosivity of bromine own is strong, and equipment requirements is high, not easily operates, poor stability, not environmentally；
4, not only α-bromoketone class intermediate and morpholine react morpholine and make reactant but also do acid binding agent, consumption big (2.1eq.), are not easily recycled, produce a large amount of waste water；
5, α-bromoketone class intermediate reacts with morpholine, and time length (24h), only moderate yield (81%) are not easily purified to more than 99%, and causes that the whole explained hereafter cycle is longer, cost high.
Therefore, no matter economically or environmental is unsuitable for industrialization and generates.
Chen Ting applies for a patent CN102924630 and finds 1-(xenyl-4-base)-2-methyl-2-morpholinopropane-1-ketone is the effective succedaneum of Irgacure907.Irgacure907 is very important light trigger in UV uv radiation curing field, but containing first sulfydryl in aromatic ring system in the structure of this compound, inevitably lead to occur xanthochromia, remaining bad smell in Light Curing and produce the problems such as carcinogenic volatile organic compounds, limiting its use in a lot of places.And 1-(xenyl-4-base) in-2-methyl-2-morpholinopropane-1-ketone structure without element sulphur, it is applied in containing the yellowing resistance not only embodying excellence time in unsaturated allyl compound system UV radical photopolymerization solidification process as one of light trigger or photoinitiator composite, completely eliminate sulfur-bearing adverse residue abnormal smells from the patient, and significantly reduce the release of all kinds of noxious volatile organic compound.Meanwhile, under same or analogous application conditions, this compound is competed in the Financial cost of advantage and is presented the space charge force equal or higher with Irgacure907.The product that can substitute Irgacure907 in the market is extremely limited, people are more and more higher to the requirement of environment simultaneously, 1-(xenyl-4-the base that performance is more excellent)-2-methyl-2-morpholinopropane-1-ketone in curing field can more and more important, therefore develop the synthesis 1-(xenyl-4-base that more economical environment is more friendly)-2-methyl-2-morpholinopropane-1-ketone obtain process route be very necessary and urgent need.
Summary of the invention
The technical problem to be solved in the present invention is to provide a kind of 1-(xenyl-4-base) synthesis technique of-2-methyl-2-morpholinopropane-1-ketone.This synthesis technique can overcome existing method exists cost height, the problem such as toxicity is big, waste water is many, difficult industrial implementation, be that a kind of cost is low, environmental friendliness, yield high, easily operate, there is what commercial production was worth synthetic method.
The present invention synthesizes 1-(xenyl-4-base) technological process of-2-methyl-2-morpholinopropane-1-ketone is as follows:
The technical problem to be solved is to be realized by technical scheme in detail below.The present invention is a kind of 1-(xenyl-4-base) synthesis technique of-2-methyl-2-morpholinopropane-1-ketone, specifically comprise the following steps that
1), friedel-crafts acylation: solvent and catalyst are joined in reaction bulb; it is cooled to less than 10 DEG C and is dividedly in some parts biphenyl; isobutyryl chloride is dripped below 5 DEG C; 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, then heats to 5～20 DEG C, reacts 3～5 hours.TLC or GC follows the tracks of reaction, after reacting completely, is poured into by reactant liquor and carries out acidolysis in the dilute hydrochloric acid of 3～4%, aqueous phase discarded, washes organic facies, obtains 1-(xenyl-4-base) the solution G/C content more than 99% of-2-methylpropane-1-ketone；
2), chlorination reaction: by 1) the 1-(xenyl-4-base that is synthetically derived)-2-methylpropane-1-ketone solution is directly thrown in chlorination bottle, is warming up to 90～120 DEG C, passes into chlorine, react 4～8 hours, TLC or LC follows the tracks of reaction.Reaction is down to room temperature after terminating, and is separately added into appropriate water, saturated sodium bicarbonate agitator treating, phase of point anhydrating, and obtains 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, content more than 98%；
3), substitution reaction: by 2) the 1-(xenyl-4-base that is synthetically derived)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution, morpholine, alkaline aqueous solution mixing, be heated to uniform temperature, insulation reaction 3～6 hours, TLC or LC follows the tracks of reaction.After reaction terminates, cooling, separate aqueous phase and organic facies, organic facies distillating recovering solvent, recovered solvent can directly overlap through pretreatment uses next group reaction.The residue obtained after organic facies distillating recovering solvent is 1-(xenyl-4-base) crude product of-2-methyl-2-morpholinopropane-1-ketone, add proper amount of methanol crystallization, filter, dry the 1-(xenyl-4-base obtaining white)-2-methyl-2-morpholinopropane-1-ketone, purity more than 99%, three-step reaction total recovery 90% and more than, gained filtrate can be applied to next group crystallization continuous 1～2 time, then redistillation recovery.
1-(xenyl-4-base provided by the invention) synthetic method of-2-methyl-2-morpholinopropane-1-ketone, it is characterized in that step 1), 2), 3) solvent that is used in conjunction with is selected from dichloromethane, chloroform, dichloroethanes, chlorobenzene, normal hexane, petroleum ether, it is preferable that dichloromethane, dichloroethanes, chlorobenzene or their mixing.
1-(xenyl-4-base provided by the invention) synthetic method of-2-methyl-2-morpholinopropane-1-ketone, it is characterised in that the catalyst that step 1) uses is selected from aluminum chloride, ferric chloride, zinc chloride, titanium chloride, it is preferable that aluminum chloride and ferric chloride.
1-(xenyl-4-base provided by the invention) synthetic method of-2-methyl-2-morpholinopropane-1-ketone, it is characterised in that the amount of morpholine used by step 3) is selected from 1-(xenyl-4-base) amount of-2-methyl-2 cbloropropane isopropyl chloride-1-ketone and morpholine materials is than 1:1.0～1.2.
1-(xenyl-4-base provided by the invention) synthetic method of-2-methyl-2-morpholinopropane-1-ketone, it is characterised in that the reaction temperature of step 3) is selected from 40～80 DEG C.
1-(xenyl-4-base provided by the invention) synthetic method of-2-methyl-2-morpholinopropane-1-ketone, it is characterised in that the alkali used by step 3) is selected from inorganic base or their mixing such as sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, calcium hydroxide, sodium hydroxide, potassium hydroxide；Use potassium carbonate, sodium carbonate or during calcium hydroxide, its consumption be 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone than the amount of alkaloid substance than 1:0.5～0.6；Use potassium bicarbonate, sodium bicarbonate, sodium hydroxide or during potassium hydroxide, its consumption be 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone than the amount of alkaloid substance than 1:1.0～1.2.
The present inventor finds in research process, and during step 3) reaction, too high the mistake with morpholine concentration of temperature is mostly unfavorable for reaction, and by-product increases.Test of many times finds to ensure that when about 60 DEG C response speed can also reduce side reaction simultaneously；The theoretical demand of morpholine is minimum for 1-(xenyl-4-base) amount of substance such as-2-methyl-2 cbloropropane isopropyl chloride-1-ketone, but in course of reaction, produce hydrogen chloride gradually, the hydrogen chloride produced can preferentially consume again compared with morpholine (with the 1-(xenyl-4-base that reaction produces)-2-methyl-2-morpholinopropane-1-ketone, the alkalescence of morpholine and locus factor all can preferentially and hcl reaction), carry out maybe can not proceeding very slowly when ruing out of morpholine reaction, if therefore this step reaction do not use need morpholine amount to be at least 1-(xenyl-4-base during other acid binding agent) 2 times of-2-methyl-2 cbloropropane isopropyl chloride-1-ketone amount of substance, the morpholine so having 1 times amount can be consumed by the hydrogen chloride produced in course of reaction, in this case, when just starting to react, the concentration height of morpholine has the tendency producing by-product, considering the present invention selects inorganic base aqueous solution to do acid binding agent, reduce the consumption of morpholine, water and organic solvent can be dissolved in due to morpholine itself, thus while be two phase reaction, need not additionally with phase transfer catalyst it is ensured that response speed, simultaneously because morpholine is dissolved in the characteristic of water, some morpholine can be distributed in aqueous solution, morpholine is made to reduce in the concentration of organic facies, avoid the situation of the excessive concentration of morpholine when just starting to react.
1-(xenyl-4-base provided by the invention)-2-methyl-2-morpholinopropane-1-ketone synthesis technique not only avoids using price, raw material that corrosivity is strong, can also obtain exceeding 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, eliminate distillation procedure, not only simplify technique, decrease the loss of solvent simultaneously, save cost, the convenient unification of recovered solvent is deposited, and decreases the chance of solvent cross-contamination, and recovered solvent can be applied mechanically through simple pretreatment (such as sedimentation).
1-(xenyl-4-base provided by the invention)-2-methyl-2-morpholinopropane-1-ketone synthesis technique advantage is in that:
1) employing chlorine cheap, that be easy to get is halogenating agent；
2) three-step reaction only employs a solvent, and eliminates distillation procedure, not only reduces equipment investment and operating cost, decreases the loss of solvent simultaneously, saved cost；
3) decreasing the consumption of morpholine, use inorganic base aqueous solution to do acid binding agent, response speed is fast, and yield is high；
4) shorten the response time, it is possible to reduce the production cycle, improve production efficiency；
5) simple to operate, it is easy to industrializing implementation.
Detailed description of the invention
The concrete technical scheme of the present invention described further below, in order to those skilled in the art are further understood that the present invention, and do not constitute the restriction to its right.
Embodiment 1:1-(xenyl-4-base) synthesis of-2-methyl-2-morpholinopropane-1-ketone
1) adding 450 grams of isopropylformic acid .s in the reactor of 1000 milliliters, be warming up to 45 DEG C, be subsequently adding Phosphorous chloride. 320 grams, 55 DEG C are incubated 6 hours, and GC follows the tracks of reaction, after raw material isopropylformic acid. disappears, terminate reaction.Divide the mineral acid falling down layer, obtain isobutyryl chloride 541.8 grams, G/C content 99.4%, product yield about 99.6%.
2) reaction bulb of 1000 milliliters adds 376 grams of anhydrous dichloroethanes, be cooled to 10 DEG C, add aluminum trichloride (anhydrous) 90 grams, biphenyl 100g, continuing to be cooled to 5 DEG C, add the acyl chlorides 76 grams that step 1) prepares, 5 DEG C are incubated 5 hours, GC follows the tracks of reaction, after raw material biphenyl disappears, terminates reaction.Being poured into by above-mentioned reactant liquor in the dilute hydrochloric acid of 240 gram 3%, after stirring 1 hour, separatory obtains 1-(xenyl-4-base)-2-methylpropane-1-ketone solution, G/C content 99.3%.
3) 250 milliliters of reaction bulbs add step 2) the 1-(xenyl-4-base for preparing)-2-methylpropane-1-ketone solution, be warming up to 90 DEG C, then pass to chlorine, GC follows the tracks of reaction, 1-(xenyl-4-base) after-2-methylpropane-1-ketone disappears, end is reacted.Cooling adds separatory after 133 milliliters of water stir 30 minutes, adds 75ml saturated sodium carbonate solution, separatory after stirring 30 minutes in organic facies, collects organic facies and namely obtains 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution.
4) toward the 1-(xenyl-4-base of step 3) synthesis)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution adds morpholine 62.2 grams and 114g saturated sodium carbonate solution, heat to 60 DEG C of reactions, GC follows the tracks of reaction, after reaction terminates, stand, separate aqueous phase, organic facies is with after isopyknic washing, after decompression and solvent recovery, obtain 1-(xenyl-4-base) crude product 192.6 grams of-2-methyl-2-morpholinopropane-1-ketone, recovered solvent can directly overlap through sedimentation uses next group reaction, dehydrated alcohol recrystallization is added in above-mentioned crude product, sucking filtration, dry, obtain white powder solid 182.5 grams, yield 91%, purity 99.4%, the filtrate obtained can be overlapped and be used next group crude crystalline 1～2 time.
Embodiment 2:1-(xenyl-4-base) synthesis of-2-methyl-2-morpholinopropane-1-ketone
1) reaction bulb of 1000 milliliters adds 376 grams of anhydrous chlorobenzene, be cooled to 10 DEG C, add aluminum trichloride (anhydrous) 90 grams, biphenyl 100g, continuing to be cooled to 5 DEG C, add the acyl chlorides 76 grams that embodiment 1 prepares, 5 DEG C are incubated 5 hours, GC follows the tracks of reaction, after raw material biphenyl disappears, terminates reaction.Being poured into by above-mentioned reactant liquor in the dilute hydrochloric acid of 240 gram 3%, after stirring 1 hour, separatory obtains 2-methyl isophthalic acid-xenyl-1-acetone soln, G/C content 99.5%.
2) 250 milliliters of reaction bulbs add the 1-(xenyl-4-base that step 1) prepares)-2-methylpropane-1-ketone solution, be warming up to 90 DEG C, then pass to chlorine, GC follows the tracks of reaction, 1-(xenyl-4-base) after-2-methylpropane-1-ketone disappears, end is reacted.Cooling adds separatory after 133 milliliters of water stir 30 minutes, adds 75ml saturated sodium carbonate solution, separatory after stirring 30 minutes in organic facies, collects organic facies and namely obtains 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution.
3) toward step 2) the 1-(xenyl-4-base that synthesizes)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution adds morpholine 62.2 grams and 114g saturated sodium carbonate solution, heat to 60 DEG C of reactions, GC follows the tracks of reaction, after reaction terminates, stand, separate aqueous phase, organic facies is with after isopyknic washing, after decompression and solvent recovery, obtain 1-(xenyl-4-base) crude product 193.2 grams of-2-methyl-2-morpholinopropane-1-ketone, recovered solvent can directly overlap through sedimentation uses next group reaction, dehydrated alcohol recrystallization is added in above-mentioned crude product, sucking filtration, dry, obtain white powder solid 181.5 grams, yield 90.5%, content 99.3%, the filtrate obtained can be overlapped and be used next group crude crystalline 1～2 time.
Embodiment 3:1-(xenyl-4-base) synthesis of-2-methyl-2-morpholinopropane-1-ketone
1) reaction bulb of 1000 milliliters adds 376 grams of anhydrous dichloroethanes, be cooled to 8 DEG C, add aluminum trichloride (anhydrous) 95 grams, biphenyl 100g, continuing to be cooled to 3 DEG C, add the acyl chlorides 76 grams that embodiment 1 prepares, 14 DEG C are incubated 4 hours, GC follows the tracks of reaction, after raw material biphenyl disappears, terminates reaction.Above-mentioned reactant liquor is poured in the dilute hydrochloric acid of 220 gram 3.5%, after stirring 1 hour, separatory, organic facies is 1-(xenyl-4-base) and-2-methylpropane-1-ketone solution, G/C content 99.0%.
2) reaction bulb of 250 milliliters adds 1) the 1-(xenyl-4-base for preparing)-2-methylpropane-1-ketone solution, be warming up to 90 DEG C, then pass to chlorine, GC follows the tracks of reaction, until 1-(xenyl-4-base) after-2-methylpropane-1-ketone disappears, end is reacted.Cooling adds separatory after 133 milliliters of water stir 30 minutes, adds 75ml saturated sodium carbonate solution, separatory after stirring 30 minutes in organic facies, collects organic facies and namely obtains 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution.
3) toward step 2) the 1-(xenyl-4-base that synthesizes)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution adds morpholine 197.3 grams, heat to 60 DEG C of reactions, GC follows the tracks of reaction, after terminating reaction, the water pump decompression unreacted morpholine of Distillation recovery and solvent, it is cooled to less than 80 DEG C, add 200 toluene and 200 milliliters of water, wash the hydrochlorate of the morpholine that reaction produces off, separatory after stirring 30 minutes, 1-(xenyl-4-base is obtained after organic facies vacuum distillation recovered solvent) crude product 190 grams of-2-methyl-2-morpholinopropane-1-ketone, dehydrated alcohol is added in above-mentioned crude product, the lower heating for dissolving recrystallization of stirring, sucking filtration, dry, obtain buff powder solid 170.5 grams, G/C content 98.6%, again with new dehydrated alcohol secondary crystallization, sucking filtration, dry, obtain white powder solid 156.5 grams, G/C content 99.3%, three-step reaction total recovery 79%.
Embodiment 4:1-(xenyl-4-base) synthesis of-2-methyl-2-morpholinopropane-1-ketone
1) reaction bulb of 1000 milliliters adds 376 grams of anhydrous chlorobenzene, be cooled to 6 DEG C, add aluminum trichloride (anhydrous) 104 grams, biphenyl 100g, continuing to be cooled to 0 DEG C, add the acyl chlorides 76 grams that embodiment 1 prepares, 20 DEG C are incubated 3 hours, GC follows the tracks of reaction, after raw material biphenyl disappears, terminates reaction.Above-mentioned reactant liquor is poured in the dilute hydrochloric acid of 200 gram 4%, after stirring 1 hour, separatory, organic facies is 1-(xenyl-4-base) and-2-methylpropane-1-ketone solution, G/C content 99.2%.
2) reaction bulb of 250 milliliters adds the 1-(xenyl-4-base that step 1) prepares)-2-methylpropane-1-ketone solution, it is warming up to 90 DEG C, then passes to chlorine, GC follows the tracks of reaction, after 2-methyl isophthalic acid-xenyl-1-acetone disappears, terminates reaction.Cooling adds separatory after 133 milliliters of water stir 30 minutes, adds 75ml saturated sodium carbonate solution, separatory after stirring 30 minutes in organic facies, collects organic facies and namely obtains 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution.
3) toward step 2) the 1-(xenyl-4-base that synthesizes)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution adds morpholine 62.2 grams and 114g saturated sodium carbonate solution, heat to 120 DEG C of reactions, GC follows the tracks of reaction, after reaction terminates, stand, separate aqueous phase, organic facies is with after isopyknic washing, decompression and solvent recovery, obtain 1-(xenyl-4-base) crude product 191 grams of-2-methyl-2-morpholinopropane-1-ketone, dehydrated alcohol recrystallization is added in above-mentioned crude product, sucking filtration, dry, obtain buff powder solid 172.5 grams, G/C content 98.7%, again with new dehydrated alcohol secondary crystallization, sucking filtration, dry, obtain white powder solid 162.5 grams, G/C content 99.1%, three-step reaction total recovery 81%.
Claims (3)
1. the synthetic method of 1-(xenyl-4-base)-2-methyl-2-morpholinopropane-1-ketone, it is characterised in that the step that it includes:
1), friedel-crafts acylation: solvent and catalyst are joined in reactor; it is cooled to less than 10 DEG C and is dividedly in some parts biphenyl; isobutyryl chloride is dripped below 5 DEG C; biphenyl, catalyst, 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, then heats to 5～20 DEG C, reacts 3～5 hours；TLC or GC follows the tracks of reaction, after reacting completely, is poured into by reactant liquor and carries out acidolysis in the dilute hydrochloric acid of 3-4%, aqueous phase discarded, washes organic facies, obtains the solution of 1-(xenyl-4-base)-2-methylpropane-1-ketone；
2), chlorination reaction: by 1) 1-(xenyl-4-the base)-2-methylpropane-1-ketone solution that is synthetically derived is directly thrown in chlorination tank, heating, pass into chlorine, reacting 4～8 hours, TLC or liquid chromatograph follow the tracks of reaction, after reaction terminates, it is down to room temperature, it is separately added into appropriate water, saturated sodium bicarbonate solution agitator treating, phase of point anhydrating, obtain 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution；
3), substitution reaction: by 2) 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone solution of being synthetically derived, morpholine, alkaline aqueous solution mixes, it is heated to uniform temperature, insulation reaction 3～6 hours, TLC or LC follows the tracks of reaction, after reaction terminates, cooling, separate aqueous phase and organic facies, organic facies distillating recovering solvent, the residue obtained is the crude product of 1-(xenyl-4-base)-2-methyl-2-morpholinopropane-1-ketone, add ethanol in proper amount crystallization, filter, dry 1-(xenyl-4-the base)-2-methyl-2-morpholinopropane-1-ketone obtaining white；
Wherein step 1), 2), 3) be used in conjunction with step 1) in affiliated solvent, solvent is selected from dichloromethane, chloroform, dichloroethanes, chlorobenzene, normal hexane, petroleum ether or their mixing；
Step 2) pass into the reaction temperature of chlorine selected from 90～120 DEG C；
Step 3) consumption of morpholine selected from the amount of 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone and morpholine materials than 1:1.0～1.2；
Step 3) heating-up temperature is selected from 40～80 DEG C.
2. synthetic method according to claim 1, it is characterised in that step 1) catalyst that uses is selected from aluminum chloride, ferric chloride, zinc chloride, titanium chloride.
3. synthetic method according to claim 1, it is characterised in that step 3) used by alkali compounds selected from sodium bicarbonate, sodium carbonate, potassium bicarbonate, potassium carbonate, sodium hydroxide, potassium hydroxide or their mixing；Use potassium carbonate, sodium carbonate time, its consumption be 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone than alkali compounds amount of substance than 1:0.5～0.6；Use potassium bicarbonate, sodium bicarbonate, sodium hydroxide or during potassium hydroxide, its consumption be 1-(xenyl-4-base)-2-methyl-2 cbloropropane isopropyl chloride-1-ketone than alkali compounds amount of substance than 1:1.0～1.2.
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| CN101724099A (en) * | 2009-12-18 | 2010-06-09 | 深圳市东方信维科技有限公司 | Aromatic ketone compound and photoinitiator with same |
| CN102924630A (en) * | 2011-08-09 | 2013-02-13 | 陈婷 | UV light curing application system containing amino ketone compound 1-([1,1'-biphenyl]-4-yl)-2-methyl-2-morpholinopropan-1-one |
| CN103288873A (en) * | 2012-03-02 | 2013-09-11 | 深圳市有为化学技术有限公司 | Sulfonyl or quinonyl functionalized acylphosphine oxide compound |
-
2013
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Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5190940A (en) * | 1990-09-14 | 1993-03-02 | American Home Products Corporation | Cholesterol ester hydrolase inhibitors |
| CN101724099A (en) * | 2009-12-18 | 2010-06-09 | 深圳市东方信维科技有限公司 | Aromatic ketone compound and photoinitiator with same |
| CN102924630A (en) * | 2011-08-09 | 2013-02-13 | 陈婷 | UV light curing application system containing amino ketone compound 1-([1,1'-biphenyl]-4-yl)-2-methyl-2-morpholinopropan-1-one |
| CN103288873A (en) * | 2012-03-02 | 2013-09-11 | 深圳市有为化学技术有限公司 | Sulfonyl or quinonyl functionalized acylphosphine oxide compound |
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