CN104610197B - A kind of method based on acid anhydrides synthesizing propylene morpholide - Google Patents
A kind of method based on acid anhydrides synthesizing propylene morpholide Download PDFInfo
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- CN104610197B CN104610197B CN201510051599.6A CN201510051599A CN104610197B CN 104610197 B CN104610197 B CN 104610197B CN 201510051599 A CN201510051599 A CN 201510051599A CN 104610197 B CN104610197 B CN 104610197B
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- acid
- trichloroacetic
- anhydride
- morpholine
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- 238000000034 method Methods 0.000 title claims abstract description 25
- 230000002194 synthesizing effect Effects 0.000 title claims abstract description 8
- 150000008065 acid anhydrides Chemical class 0.000 title abstract description 3
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 title abstract 3
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 title abstract 3
- XLPJNCYCZORXHG-UHFFFAOYSA-N 1-morpholin-4-ylprop-2-en-1-one Chemical compound C=CC(=O)N1CCOCC1 XLPJNCYCZORXHG-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000006243 chemical reaction Methods 0.000 claims abstract description 39
- YNAVUWVOSKDBBP-UHFFFAOYSA-N Morpholine Chemical compound C1COCCN1 YNAVUWVOSKDBBP-UHFFFAOYSA-N 0.000 claims abstract description 38
- ZAIRDSNFTQCIHS-UHFFFAOYSA-N (2,2,2-trichloroacetyl) prop-2-enoate Chemical compound ClC(C(=O)OC(C=C)=O)(Cl)Cl ZAIRDSNFTQCIHS-UHFFFAOYSA-N 0.000 claims abstract description 23
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims abstract description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims abstract description 16
- YNJBWRMUSHSURL-UHFFFAOYSA-N trichloroacetic acid Chemical compound OC(=O)C(Cl)(Cl)Cl YNJBWRMUSHSURL-UHFFFAOYSA-N 0.000 claims abstract description 14
- WFDIJRYMOXRFFG-UHFFFAOYSA-N Acetic anhydride Chemical compound CC(=O)OC(C)=O WFDIJRYMOXRFFG-UHFFFAOYSA-N 0.000 claims description 39
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 239000003112 inhibitor Substances 0.000 claims description 27
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 15
- 239000012043 crude product Substances 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 14
- NWVVVBRKAWDGAB-UHFFFAOYSA-N hydroquinone methyl ether Natural products COC1=CC=C(O)C=C1 NWVVVBRKAWDGAB-UHFFFAOYSA-N 0.000 claims description 12
- CNHDIAIOKMXOLK-UHFFFAOYSA-N toluquinol Chemical compound CC1=CC(O)=CC=C1O CNHDIAIOKMXOLK-UHFFFAOYSA-N 0.000 claims description 12
- QIGBRXMKCJKVMJ-UHFFFAOYSA-N Hydroquinone Chemical compound OC1=CC=C(O)C=C1 QIGBRXMKCJKVMJ-UHFFFAOYSA-N 0.000 claims description 10
- 239000002253 acid Substances 0.000 claims description 10
- 150000008064 anhydrides Chemical class 0.000 claims description 10
- SJRJJKPEHAURKC-UHFFFAOYSA-N N-Methylmorpholine Chemical compound CN1CCOCC1 SJRJJKPEHAURKC-UHFFFAOYSA-N 0.000 claims description 9
- 230000015572 biosynthetic process Effects 0.000 claims description 9
- 238000003786 synthesis reaction Methods 0.000 claims description 9
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 9
- 239000011230 binding agent Substances 0.000 claims description 8
- 239000012467 final product Substances 0.000 claims description 8
- 230000035484 reaction time Effects 0.000 claims description 8
- JIGUICYYOYEXFS-UHFFFAOYSA-N 3-tert-butylbenzene-1,2-diol Chemical compound CC(C)(C)C1=CC=CC(O)=C1O JIGUICYYOYEXFS-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 6
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- 229910021591 Copper(I) chloride Inorganic materials 0.000 claims description 5
- OXBLHERUFWYNTN-UHFFFAOYSA-M copper(I) chloride Chemical compound [Cu]Cl OXBLHERUFWYNTN-UHFFFAOYSA-M 0.000 claims description 5
- 229940045803 cuprous chloride Drugs 0.000 claims description 5
- AZQWKYJCGOJGHM-UHFFFAOYSA-N 1,4-benzoquinone Chemical compound O=C1C=CC(=O)C=C1 AZQWKYJCGOJGHM-UHFFFAOYSA-N 0.000 claims description 4
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 claims description 4
- BGNXCDMCOKJUMV-UHFFFAOYSA-N Tert-Butylhydroquinone Chemical compound CC(C)(C)C1=CC(O)=CC=C1O BGNXCDMCOKJUMV-UHFFFAOYSA-N 0.000 claims description 4
- LQNUZADURLCDLV-UHFFFAOYSA-N nitrobenzene Chemical compound [O-][N+](=O)C1=CC=CC=C1 LQNUZADURLCDLV-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- CDBYLPFSWZWCQE-UHFFFAOYSA-L sodium carbonate Substances [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 4
- 239000011259 mixed solution Substances 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 claims description 3
- 150000003512 tertiary amines Chemical class 0.000 claims description 3
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 3
- WJFKNYWRSNBZNX-UHFFFAOYSA-N 10H-phenothiazine Chemical compound C1=CC=C2NC3=CC=CC=C3SC2=C1 WJFKNYWRSNBZNX-UHFFFAOYSA-N 0.000 claims description 2
- 229940044119 2-tert-butylhydroquinone Drugs 0.000 claims description 2
- HPNMFZURTQLUMO-UHFFFAOYSA-N diethylamine Chemical compound CCNCC HPNMFZURTQLUMO-UHFFFAOYSA-N 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- 229950000688 phenothiazine Drugs 0.000 claims description 2
- OXNIZHLAWKMVMX-UHFFFAOYSA-N picric acid Chemical compound OC1=C([N+]([O-])=O)C=C([N+]([O-])=O)C=C1[N+]([O-])=O OXNIZHLAWKMVMX-UHFFFAOYSA-N 0.000 claims description 2
- 238000002360 preparation method Methods 0.000 claims description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 claims description 2
- 235000017557 sodium bicarbonate Nutrition 0.000 claims description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 7
- 239000000178 monomer Substances 0.000 abstract description 3
- 239000000047 product Substances 0.000 description 12
- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 7
- 238000001914 filtration Methods 0.000 description 6
- 239000002904 solvent Substances 0.000 description 6
- 239000000203 mixture Substances 0.000 description 5
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 4
- 239000012752 auxiliary agent Substances 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 2
- WQDUMFSSJAZKTM-UHFFFAOYSA-N Sodium methoxide Chemical compound [Na+].[O-]C WQDUMFSSJAZKTM-UHFFFAOYSA-N 0.000 description 2
- 238000007098 aminolysis reaction Methods 0.000 description 2
- 238000004523 catalytic cracking Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- 239000002516 radical scavenger Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 238000004227 thermal cracking Methods 0.000 description 2
- MLAKIIPISRSRGQ-UHFFFAOYSA-N 3-methoxy-1-morpholin-4-ylpropan-1-one Chemical compound COCCC(=O)N1CCOCC1 MLAKIIPISRSRGQ-UHFFFAOYSA-N 0.000 description 1
- XHRSBADJCZDQSU-UHFFFAOYSA-N ClC(C(=O)OC(C(Cl)(Cl)Cl)=O)(Cl)Cl.C(C=C)(=O)O Chemical compound ClC(C(=O)OC(C(Cl)(Cl)Cl)=O)(Cl)Cl.C(C=C)(=O)O XHRSBADJCZDQSU-UHFFFAOYSA-N 0.000 description 1
- 108010010803 Gelatin Proteins 0.000 description 1
- HWXVVGGGYFSZJT-UHFFFAOYSA-N N1(CCOCC1)CCC(=O)N1CCOCC1.C(CC)(=O)N1CCOCC1 Chemical class N1(CCOCC1)CCC(=O)N1CCOCC1.C(CC)(=O)N1CCOCC1 HWXVVGGGYFSZJT-UHFFFAOYSA-N 0.000 description 1
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 description 1
- 239000003377 acid catalyst Substances 0.000 description 1
- 238000005917 acylation reaction Methods 0.000 description 1
- 238000007259 addition reaction Methods 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 125000000217 alkyl group Chemical group 0.000 description 1
- CREMABGTGYGIQB-UHFFFAOYSA-N carbon carbon Chemical compound C.C CREMABGTGYGIQB-UHFFFAOYSA-N 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 150000001732 carboxylic acid derivatives Chemical class 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 239000012024 dehydrating agents Substances 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 229940079593 drug Drugs 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical group 0.000 description 1
- 229920000159 gelatin Polymers 0.000 description 1
- 239000008273 gelatin Substances 0.000 description 1
- 235000019322 gelatine Nutrition 0.000 description 1
- 235000011852 gelatine desserts Nutrition 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000003607 modifier Substances 0.000 description 1
- FAIAAWCVCHQXDN-UHFFFAOYSA-N phosphorus trichloride Chemical compound ClP(Cl)Cl FAIAAWCVCHQXDN-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000011435 rock Substances 0.000 description 1
- 150000003334 secondary amides Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical group 0.000 description 1
- 238000007086 side reaction Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- -1 sodium alkoxide Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000013268 sustained release Methods 0.000 description 1
- 239000012730 sustained-release form Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 239000000057 synthetic resin Substances 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- 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
- C07D295/16—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 acylated on ring nitrogen atoms
- C07D295/18—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 acylated on ring nitrogen atoms by radicals derived from carboxylic acids, or sulfur or nitrogen analogues thereof
- C07D295/182—Radicals derived from carboxylic acids
- C07D295/185—Radicals derived from carboxylic acids from aliphatic carboxylic acids
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a kind of method based on acid anhydrides synthesizing propylene morpholide.The present invention acrylic acid Trichloroacetic anhydride and morpholine react generation acryloylmorpholine monomer, and acrylic acid Trichloroacetic anhydride used is reacted by acrylic acid and trichloroacetic acid and prepares.The method of synthesizing propylene morpholide of the present invention, process route is simple, reacts easily controllable；Reaction condition is gentle, improves purity and the yield of product；Selected low in raw material price, product structure are stable, low cost, have the prospect of industrial applications.
Description
Technical Field
The invention relates to a synthesis method of acryloyl morpholine, in particular to a method for synthesizing acryloyl morpholine based on anhydride, belonging to the field of compound synthesis.
Background
Acryloylmorpholine (ACMO) is a water-soluble compound with carbon-carbon unsaturated double bonds, is colorless or light yellow transparent liquid, and has the structural formula:
because the acryloyl morpholine is nontoxic and has good biocompatibility, the homopolymer thereof is often used as a drug sustained release agent, a cosmetic propping agent and the like, and in recent years, the acryloyl morpholine replaces toxic acrylamide in the field of water purification treatment to be used as a water treatment agent. The acryloyl morpholine is also an excellent auxiliary agent and modifier of synthetic resin, is used as a reaction diluent of ultraviolet curing resin, is easy to generate copolymerization reaction with substances such as acrylic acid, acrylamide, gelatin and the like, can obviously improve the viscoelasticity, shear resistance and other properties of products, and is widely applied to the fields of oil field auxiliary agents, printing ink auxiliary agents, papermaking auxiliary agents, adhesives and the like.
Chinese patent CN101293880B discloses a method for preparing acryloyl morpholine by acylation reaction of acryloyl chloride, wherein phosphorus trichloride reacts with acrylic acid to generate acryloyl chloride, the acryloyl chloride is solvated and then reacts with morpholine to generate crude acryloyl morpholine, and then the reaction solution is rectified under vacuum condition to obtain high-purity acryloyl morpholine.
Japanese patent JP11100375A (JP19970279395) discloses a method for synthesizing acryloyl morpholine by thermal cracking, wherein alkyl substituted propionyl morpholine (4-morpholinyl propionyl morpholine) is used as raw material, acid catalyst is added, and vacuum thermal cracking is carried out at 390 ℃ to generate acryloyl morpholine. The method has simple process route, but the product is easy to polymerize, the yield is low, generally 29 percent, and the raw materials are expensive and have high production cost.
Song rock et al, in the article "synthetic research on N-acryloylmorpholine", disclose that acryloylmorpholine is prepared from morpholine and methyl acrylate as main raw materials by the processes of double bond protection, catalytic aminolysis, catalytic cracking and the like: firstly, methyl acrylate and methanol are subjected to addition reaction under the catalysis of sodium alkoxide (sodium methoxide) to obtain 3-methoxy methyl propionate; then under the action of an ester exchange catalyst, carrying out catalytic aminolysis reaction with morpholine to obtain 3-methoxypropionyl morpholine; finally, the acryloyl morpholine is obtained through catalytic cracking. The whole reaction process has a long process route and is not easy to control.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for synthesizing acryloyl morpholine based on acid anhydride. Acrylic acid trichloroacetic anhydride reacts with morpholine to generate acryloyl morpholine monomer. The preparation steps are as follows:
(1) reacting trichloroacetic anhydride acrylate with the secondary amine group in morpholine to produce a secondary amide.
Dissolving acrylic trichloroacetic anhydride in an organic solvent, dropwise adding a mixed solution of morpholine and an acid-binding agent, and reacting for 1-4 hours at 0-5 ℃ to obtain a crude product of acryloyl morpholine. The reaction formula is as follows:
wherein,
the acid-binding agent comprises but is not limited to one or more of triethylamine, diethylamine, pyridine, N-methylmorpholine, tripropylamine, trioctyl tertiary amine, sodium bicarbonate and sodium carbonate. The preferred acid scavenger is triethylamine.
The organic solvent includes, but is not limited to, one or more of ethyl acetate, acetone, and toluene.
The mol ratio of acrylic acid trichloroacetic anhydride to morpholine is as follows: 1:1 to 1: 1.5. Preferably, the molar ratio of acrylic acid trichloroacetic anhydride to morpholine is: 1:1.1.
The molar ratio of the acid-binding agent to the acrylic trichloroacetic anhydride is 1: 0.9-1: 1.1. Preferably, the molar ratio of the acid scavenger to the acrylic trichloroacetic anhydride is 1:1.
Preferably, the reaction temperature is 2-4 ℃, and the reaction time is 1.5-3 hours.
Preferably, the reaction temperature is 3 ℃ and the reaction time is 2 hours.
(2) Polymerization inhibitor is used in the rectification process to prevent monomer polymerization reaction so as to increase yield. And (2) adding the crude acryloyl morpholine obtained in the step (1) into a reduced-pressure rectifying tower filled with a polymerization inhibitor for rectification, and collecting fractions at 140-160 ℃ to obtain the final product acryloyl morpholine.
The polymerization inhibitor is one or a combination of more of hydroquinone, p-benzoquinone, phenothiazine, methyl hydroquinone, nitrobenzene, picric acid, p-hydroxyanisole, tert-butyl catechol, 2-tert-butyl hydroquinone, 4-methoxyphenol, cuprous chloride and ferric trichloride. Preferably, the polymerization inhibitor is formed by combining hydroquinone, tert-butyl catechol and cuprous chloride according to the proportion of 10:10: 1.
The acrylic acid trichloroacetic anhydride used in the invention can be prepared by reacting acrylic acid with trichloroacetic acid. Using acetic anhydride as a dehydrating agent, and reacting two molecules of carboxylic acid to remove one molecule of water to generate the anhydride. Mixing acrylic acid and trichloroacetic acid, adding phosphorus pentoxide and a polymerization inhibitor, dropwise adding acetic anhydride, and reacting for 3-6 hours at the temperature of 95-100 ℃. And (3) after the reaction is finished, carrying out reduced pressure distillation to remove front fraction, namely the acrylic trichloroacetic anhydride. The reaction formula is as follows:
wherein,
the molar ratio of the acrylic acid to the acetic anhydride to the trichloroacetic acid is 1:1: 0.5-1: 1.1:2, and the molar ratio of the acrylic acid to the acetic anhydride to the trichloroacetic acid is 1:1: 1.
Preferably, the reaction temperature is 96-98 ℃, and the reaction time is 4-5.5 hours.
Preferably, the reaction temperature is 97 ℃ and the reaction time is 5 hours.
Compared with the prior art, the invention has the following advantages:
(1) the reaction condition is mild, the polymerization of double bonds is reduced in the reaction process, the side reaction is reduced, the stability of the product quality is ensured, the conversion rate of the raw materials is higher, the purity is more than 98 percent, the yield is higher than 75 percent, and the purity and the yield are both greatly improved.
(2) The process route is simple, the operation is simple and convenient, and the reaction is easy to control. The reaction can be carried out stably by directly controlling the molar ratio of the raw materials and the reaction temperature, and the target product can be directly obtained without producing an intermediate.
(3) Environment-friendly, nontoxic and does not produce gas pollutants.
(4) The raw materials are low in price and cost, the product structure is stable, and the method has an industrial application prospect.
Detailed Description
The technical solution of the present invention will be further specifically described below by way of specific examples. It is to be understood that the following examples are given by way of illustration only and are not to be construed as limiting the scope of the present invention, and that various changes and modifications apparent to those skilled in the art in light of the teachings herein are deemed to be within the scope of the present invention.
Example 1:
(1) 72g of acrylic acid and 164g of trichloroacetic acid were added to a four-necked flask, 5g of phosphorus pentoxide and 2.6 g of a polymerization inhibitor were added, and 110g of acetic anhydride was dropwise added to the mixture and reacted at 97 ℃ for 5 hours.
(2) After the reaction is finished, reduced pressure distillation is carried out, and front fractions are removed to obtain 165g of product, namely acrylic trichloroacetic anhydride.
(3) Adding 165g of anhydride into a solvent, cooling to 0 ℃, dropwise adding 72g of morpholine, adding 76.5g of triethylamine, maintaining the reaction temperature at 3 ℃, and reacting for 2 hours after dropwise adding to obtain a crude product of acryloyl morpholine.
(4) And filtering the crude product of the acryloyl morpholine, adding a polymerization inhibitor, carrying out reduced pressure distillation, and collecting fractions at 140-160 ℃ to obtain 96g of a product, namely the final product of the acryloyl morpholine. The polymerization inhibitor is prepared by combining hydroquinone, tert-butyl catechol and cuprous chloride according to the proportion of 10:10: 1.
The yield was 89.95% and the purity 98.7%.
Example 2:
(1) adding 900g of acrylic acid and 1025g of trichloroacetic acid into a reaction kettle, mixing, adding 50g of phosphorus pentoxide and 26 g of polymerization inhibitor, dripping 1100g of acetic anhydride into the mixed solution, and reacting for 3 hours at 100 ℃.
(2) After the completion of the reaction, distillation was carried out under reduced pressure to remove the front fraction, whereby 2071g of acrylic acid trichloroacetic anhydride was obtained.
(3) Adding 2071g of anhydride into a solvent, dropwise adding 826.5g of morpholine, adding 682.5g of pyridine, maintaining the reaction temperature at 5 ℃, and reacting for 1 hour after the dropwise addition is finished to obtain a crude product of acryloyl morpholine.
(4) And filtering the crude product of the acryloyl morpholine, adding a polymerization inhibitor, carrying out reduced pressure distillation, and collecting fractions at 140-160 ℃ to obtain 1193g of a product, namely the final product of the acryloyl morpholine. The polymerization inhibitor is tert-butyl catechol.
The yield was 79.06% and the purity was 98.8%.
Example 3:
(1) 135g of acrylic acid and 615g of trichloroacetic acid were mixed in a four-necked flask, 10g of phosphorus pentoxide and 5.2 g of a polymerization inhibitor were added, and 200g of acetic anhydride was dropwise added to the mixture to react at 97 ℃ for 5 hours.
(2) After the completion of the reaction, distillation was carried out under reduced pressure to remove the front fraction, whereby 311g of acrylic acid trichloroacetic anhydride was obtained.
(3) Adding 311g of anhydride into a solvent, cooling to 0 ℃, dropwise adding 186g of morpholine, adding 158.5g of N-methylmorpholine, maintaining the reaction temperature at 0 ℃, and reacting for 4 hours after dropwise addition to obtain a crude product of acryloyl morpholine.
(4) And filtering the crude product of the acryloyl morpholine, adding a polymerization inhibitor, carrying out reduced pressure distillation, and collecting fractions at 140-160 ℃ to obtain 181g of a product, namely the final product of the acryloyl morpholine. The polymerization inhibitor is methyl hydroquinone.
The yield was 82.98% and the purity was 99.1%.
Example 4:
(1) in a four-necked flask, 20g of acrylic acid was charged and mixed with 71.1g of trichloroacetic acid, 1.5g of phosphorus pentoxide and 3.8 g of a polymerization inhibitor were added, and 30g of acetic anhydride was dropwise added to the mixture and reacted at 95 ℃ for 3 hours.
(2) After completion of the reaction, distillation was carried out under reduced pressure to remove the front fraction, whereby 56.52g of acrylic acid trichloroacetic anhydride was obtained.
(3) 56.52g of anhydride is added into a solvent, the temperature is reduced to 0 ℃, 25.83g of morpholine is added dropwise, 35.5g of tripropylamine is added, the reaction temperature is maintained at 3 ℃, and the crude product of acryloyl morpholine is obtained after the reaction is finished for 3 hours.
(4) And filtering the crude product of the acryloyl morpholine, adding a polymerization inhibitor, carrying out reduced pressure distillation, and collecting fractions at 140-160 ℃ to obtain 34.06g of a product, namely the final product of the acryloyl morpholine. The polymerization inhibitor is methyl hydroquinone.
The yield was 83.17% and the purity 98.6%.
Example 5:
(1) in a four-necked flask, 45g of acrylic acid was charged and mixed with 127.25g of trichloroacetic acid, 1.4 g of a polymerization inhibitor was added, 3g of phosphorus pentoxide was added, and 65g of acetic anhydride was dropwise added to the mixture and reacted at 96 ℃ for 4.5 hours.
(2) After completion of the reaction, distillation was carried out under reduced pressure to remove the front fraction, whereby 126.43g of acrylic acid trichloroacetic anhydride was obtained.
(3) Adding 126.43g of anhydride into a solvent, cooling to 0 ℃, dropwise adding 65.68g of morpholine, adding 198.63g of trioctyl tertiary amine, maintaining the reaction temperature at 4 ℃, and reacting for 2.5 hours after dropwise adding to obtain a crude product of acryloyl morpholine.
(4) And filtering the crude product of the acryloyl morpholine, adding a polymerization inhibitor, carrying out reduced pressure distillation, and collecting fractions at 140-160 ℃ to obtain 74.77g of a product, namely the final product of the acryloyl morpholine. The polymerization inhibitor is methyl hydroquinone.
The yield was 81.44%, and the purity was 98.9%.
Example 6:
(1) 56g of acrylic acid and 205.11g of trichloroacetic acid were put into a four-necked flask, 1.6 g of a polymerization inhibitor was added, 4g of phosphorus pentoxide was added, and 80g of acetic anhydride was dropwise added to the mixture and reacted at 97 ℃ for 4 hours.
(2) After completion of the reaction, distillation was carried out under reduced pressure to remove the front fraction, whereby 158.99g of acrylic acid trichloroacetic anhydride was obtained.
(3) Adding 158.99g of anhydride into a solvent, cooling to 0 ℃, dropwise adding 73.17g of morpholine, adding 58.07g of sodium bicarbonate, maintaining the reaction temperature at 3 ℃, and reacting for 3.5 hours after dropwise adding to obtain a crude product of acryloyl morpholine.
(4) And filtering the crude product of the acryloyl morpholine, adding a polymerization inhibitor, carrying out reduced pressure distillation, and collecting fractions at 140-160 ℃ to obtain 89.96g of a product, namely the final product of the acryloyl morpholine. The polymerization inhibitor is methyl hydroquinone.
The yield was 87.48% and the purity was 99.2%.
Claims (9)
1. A method for synthesizing acryloyl morpholine based on anhydride comprises the following steps:
(1) dissolving acrylic trichloroacetic anhydride in an organic solvent, dropwise adding a mixed solution of morpholine and an acid-binding agent, and reacting for 1-4 hours at 0-5 ℃ to obtain a crude product acryloyl morpholine; the reaction formula is as follows:
wherein,
the acid-binding agent is selected from one or more of triethylamine, diethylamine, pyridine, N-methylmorpholine, tripropylamine, trioctyl tertiary amine, sodium bicarbonate and sodium carbonate;
the organic solvent is selected from one or more of ethyl acetate, acetone and toluene;
the mol ratio of the acrylic acid trichloroacetic anhydride to the morpholine to the acid-binding agent is as follows: 1:1: 0.9-1: 1.5: 1.1.
(2) Adding the crude product acryloyl morpholine obtained in the step (1) into a reduced-pressure rectifying tower filled with a polymerization inhibitor for rectification, and collecting fractions at 140-160 ℃ to obtain a final product acryloyl morpholine;
the polymerization inhibitor is one or a combination of more of hydroquinone, p-benzoquinone, phenothiazine, methyl hydroquinone, nitrobenzene, picric acid, p-hydroxyanisole, tert-butyl catechol, 2-tert-butyl hydroquinone, 4-methoxyphenol, cuprous chloride and ferric trichloride;
the preparation method of acrylic acid trichloroacetic anhydride in the step (1) comprises the following steps: mixing acrylic acid and trichloroacetic acid, adding phosphorus pentoxide and a polymerization inhibitor, dropwise adding acetic anhydride, and reacting for 3-6 hours at the temperature of 95-100 ℃; after the reaction is finished, carrying out reduced pressure distillation to remove front fraction, namely acrylic trichloroacetic anhydride; the reaction formula is as follows:
wherein,
the molar ratio of the acrylic acid to the acetic anhydride to the trichloroacetic acid is 1:1: 0.5-1: 1.1: 2.
2. The process for the synthesis of acryloylmorpholine according to claim 1, characterized in that: the acid-binding agent is triethylamine.
3. The process for the synthesis of acryloylmorpholine according to claim 1, characterized in that: the mol ratio of the acrylic acid trichloroacetic anhydride to the morpholine to the acid-binding agent is as follows: 1:1.1:1.
4. The process for the synthesis of acryloylmorpholine according to claim 1, characterized in that: the reaction temperature in the reaction process of the acrylic trichloroacetic anhydride and the morpholine is 2-4 ℃, and the reaction time is 1.5-3 hours.
5. The process for the synthesis of acryloylmorpholine according to claim 4, characterized in that: the reaction temperature was 3 ℃ and the reaction time was 2 hours.
6. The process for the synthesis of acryloylmorpholine according to claim 1, characterized in that: the polymerization inhibitor is formed by combining hydroquinone, tert-butyl catechol and cuprous chloride according to the mass ratio of 10:10: 1.
7. The process for the synthesis of acryloylmorpholine according to claim 1, characterized in that: the molar ratio of the acrylic acid to the acetic anhydride to the trichloroacetic acid is 1:1: 1.
8. The process for the synthesis of acryloylmorpholine according to claim 1, characterized in that: the reaction temperature for preparing the acrylic trichloroacetic anhydride is 96-98 ℃, and the reaction time is 4-5.5 hours.
9. The process for the synthesis of acryloylmorpholine according to claim 8, characterized in that: the reaction temperature was 97 ℃ and the reaction time was 5 hours.
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