CN108084023A - A kind of preparation method of 1- chloroethenes yl acetate - Google Patents
A kind of preparation method of 1- chloroethenes yl acetate Download PDFInfo
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- CN108084023A CN108084023A CN201711275614.0A CN201711275614A CN108084023A CN 108084023 A CN108084023 A CN 108084023A CN 201711275614 A CN201711275614 A CN 201711275614A CN 108084023 A CN108084023 A CN 108084023A
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- chloroethenes
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- 238000002360 preparation method Methods 0.000 title claims abstract description 13
- -1 1- chloroethenes yl acetate Chemical class 0.000 title claims description 18
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims abstract description 20
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 18
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910000041 hydrogen chloride Inorganic materials 0.000 claims abstract description 18
- 238000006243 chemical reaction Methods 0.000 claims abstract description 14
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000007259 addition reaction Methods 0.000 claims abstract description 9
- 239000003054 catalyst Substances 0.000 claims abstract description 7
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 18
- 239000012452 mother liquor Substances 0.000 claims description 18
- 239000002904 solvent Substances 0.000 claims description 13
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 12
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 10
- 150000001242 acetic acid derivatives Chemical class 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 7
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 6
- AFVFQIVMOAPDHO-UHFFFAOYSA-N Methanesulfonic acid Chemical compound CS(O)(=O)=O AFVFQIVMOAPDHO-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
- 238000001035 drying Methods 0.000 claims description 6
- KBIWNQVZKHSHTI-UHFFFAOYSA-N 4-n,4-n-dimethylbenzene-1,4-diamine;oxalic acid Chemical compound OC(=O)C(O)=O.CN(C)C1=CC=C(N)C=C1 KBIWNQVZKHSHTI-UHFFFAOYSA-N 0.000 claims description 4
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Natural products OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 4
- 239000003795 chemical substances by application Substances 0.000 claims description 4
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 4
- 229940098779 methanesulfonic acid Drugs 0.000 claims description 3
- 238000010790 dilution Methods 0.000 claims description 2
- 239000012895 dilution Substances 0.000 claims description 2
- 239000012046 mixed solvent Substances 0.000 claims description 2
- 125000001478 1-chloroethyl group Chemical group [H]C([H])([H])C([H])(Cl)* 0.000 claims 1
- 239000002253 acid Substances 0.000 claims 1
- 150000002148 esters Chemical class 0.000 claims 1
- UCTLHLZWKJIXJI-LXIBVNSESA-N [(3s,8r,9s,10r,13s,14s)-17-chloro-16-formyl-10,13-dimethyl-2,3,4,7,8,9,11,12,14,15-decahydro-1h-cyclopenta[a]phenanthren-3-yl] acetate Chemical compound C([C@@H]12)C[C@]3(C)C(Cl)=C(C=O)C[C@H]3[C@@H]1CC=C1[C@]2(C)CC[C@H](OC(=O)C)C1 UCTLHLZWKJIXJI-LXIBVNSESA-N 0.000 abstract description 11
- 238000000034 method Methods 0.000 abstract description 7
- 230000000694 effects Effects 0.000 abstract description 3
- 238000012805 post-processing Methods 0.000 abstract description 2
- 239000000284 extract Substances 0.000 abstract 1
- 239000000463 material Substances 0.000 abstract 1
- 238000000197 pyrolysis Methods 0.000 abstract 1
- 239000000376 reactant Substances 0.000 abstract 1
- 238000010189 synthetic method Methods 0.000 abstract 1
- 238000005292 vacuum distillation Methods 0.000 abstract 1
- 238000003756 stirring Methods 0.000 description 10
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 239000007787 solid Substances 0.000 description 5
- 238000005406 washing Methods 0.000 description 5
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 4
- IAZDPXIOMUYVGZ-WFGJKAKNSA-N Dimethyl sulfoxide Chemical compound [2H]C([2H])([2H])S(=O)C([2H])([2H])[2H] IAZDPXIOMUYVGZ-WFGJKAKNSA-N 0.000 description 4
- ALIVXCSEERJYHU-UHFFFAOYSA-N Flurbiprofen axetil Chemical compound FC1=CC(C(C)C(=O)OC(OC(C)=O)C)=CC=C1C1=CC=CC=C1 ALIVXCSEERJYHU-UHFFFAOYSA-N 0.000 description 4
- 229950005941 flurbiprofen axetil Drugs 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- VEUUMBGHMNQHGO-UHFFFAOYSA-N ethyl chloroacetate Chemical class CCOC(=O)CCl VEUUMBGHMNQHGO-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- IKHGUXGNUITLKF-UHFFFAOYSA-N Acetaldehyde Chemical compound CC=O IKHGUXGNUITLKF-UHFFFAOYSA-N 0.000 description 2
- 238000005481 NMR spectroscopy Methods 0.000 description 2
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- SHZIWNPUGXLXDT-UHFFFAOYSA-N ethyl hexanoate Chemical compound CCCCCC(=O)OCC SHZIWNPUGXLXDT-UHFFFAOYSA-N 0.000 description 2
- 125000001544 thienyl group Chemical group 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 description 1
- CGKKDGMMKSOGLM-UHFFFAOYSA-N CC(OC(C)=O)Cl Chemical compound CC(OC(C)=O)Cl CGKKDGMMKSOGLM-UHFFFAOYSA-N 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000001460 carbon-13 nuclear magnetic resonance spectrum Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000002330 electrospray ionisation mass spectrometry Methods 0.000 description 1
- 230000032050 esterification Effects 0.000 description 1
- 238000005886 esterification reaction Methods 0.000 description 1
- SYTBZMRGLBWNTM-UHFFFAOYSA-N flurbiprofen Chemical compound FC1=CC(C(C(O)=O)C)=CC=C1C1=CC=CC=C1 SYTBZMRGLBWNTM-UHFFFAOYSA-N 0.000 description 1
- 229960002390 flurbiprofen Drugs 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000002085 irritant Substances 0.000 description 1
- 231100000021 irritant Toxicity 0.000 description 1
- 239000011968 lewis acid catalyst Substances 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 239000000041 non-steroidal anti-inflammatory agent Substances 0.000 description 1
- 229940021182 non-steroidal anti-inflammatory drug Drugs 0.000 description 1
- 150000007524 organic acids Chemical class 0.000 description 1
- SQYNKIJPMDEDEG-UHFFFAOYSA-N paraldehyde Chemical compound CC1OC(C)OC(C)O1 SQYNKIJPMDEDEG-UHFFFAOYSA-N 0.000 description 1
- 229960003868 paraldehyde Drugs 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 230000004936 stimulating effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/28—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group
- C07C67/287—Preparation of carboxylic acid esters by modifying the hydroxylic moiety of the ester, such modification not being an introduction of an ester group by introduction of halogen; by substitution of halogen atoms by other halogen atoms
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/48—Separation; Purification; Stabilisation; Use of additives
- C07C67/52—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C67/54—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
Abstract
The invention discloses a kind of preparation methods of 1 chloroethene yl acetate, comprise the following steps:In certain temperature range, addition reaction occurs under the effect of the catalyst for vinyl acetate and hydrogen chloride, and reactant is washed, and extracts, dry, and vacuum distillation obtains 1 chloroethene yl acetate.The 1 chloroethene yl acetate purity prepared by this method is more than 90%, and yield is more than 60%.The advantage of the invention is that：The synthetic method cost of material is low, and reaction yield is high, and post processing is easy, there is industrial application value.
Description
Technical field
The invention belongs to field of medicine and chemical technology, more particularly to a kind of preparation method of 1- chloroethenes yl acetate.
Background technology
Flurbiprofen axetil (Flurbiprofen axetil) is a kind of non_steroidal anti_inflammatory drug, at present flurbiprofen axetil
Synthetic route be all to be given birth to by Flurbiprofen and 1- ethyl chloroacetates or 1- bromoacetates by a step esterification mostly
Into as shown in Equation 1：
Important starting material of the 1- ethyl chloroacetates as synthesis flurbiprofen axetil, preparation method is actually rare, such as China
Chloroacetic chloride and para-acetaldehyde are condensed generation 1- ethyl chloroacetates, such as formula 2 by patent CN103012144B under the effect of the catalyst
Shown, this method needs to add in lewis acid catalysts and the low-temp reactions such as zinc chloride.
Or using chloroacetic chloride and acetaldehyde synthesized under the catalysis of zinc chloride 1- chloroethenes yl acetate (Synlett, 2006,10,
1485~1490, if formula 3 is shown, this method, which uses two kinds of chloroacetic chloride and acetaldehyde, to be had compared with strong and stimulating and unstable raw material, unsuitable
For industrialized production.
1- (thiophenyl) ethylhexoate also generates 1- chloroethenes yl acetate (Acta Chemica under the action of sulfonic acid chloride
Scandinavica, 1989,43 (1), 74~77), if formula 4 is shown, 1- (thiophenyl) ethylhexoate is expensive in this method
It is difficult to obtain.
The content of the invention
The object of the present invention is to provide a kind of method for preparing 1- chloroethene yl acetates, this method avoid using chloroacetic chloride,
The irritant and unstable raw material such as acetaldehyde, reaction condition is mild, while raw material is cheap and easy to get, and easy to operate, is prepared into
The 1- chloroethene yl acetate purity ＞ 90% arrived is suitble to industrialized production；Organic acid is added in the present invention simultaneously to be catalyzed, is made
The carbonium ion that carbon-carbon double bond is formed during addition reaction is more stablized, so as to promote the quickening of reaction rate, further
Improve reaction yield.
The technical scheme is that：
A kind of preparation method of 1- chloroethenes yl acetate, comprises the steps of：
(a) under the conditions of 5~45 DEG C, the catalyst of 2~50mol is added in into the vinyl acetate of 100mol, and 9~
The 27 interior hydrogen chloride for being passed through 80~300mol when small carry out addition reaction, obtain reaction solution；
(b) after the solvent dilution of 150~300mol is added in into reaction solution, washed, extracted with water, it is organic relevant
It is dry；
(c) dried organic phase under 5~40 DEG C, -0.04Mpa~-0.07MPa pressure conditions is concentrated under reduced pressure, steamed
Except solvent, mother liquor is obtained；
(d) mother liquor is continued to be evaporated under reduced pressure under 30~50 DEG C, -0.07 to -0.10MPa pressure condition, obtains 1- chloroethenes
Yl acetate.
In certain temperature range, under the effect of the catalyst, addition reaction occurs for vinyl acetate and hydrogen chloride, obtains
1- chloroethenes yl acetate (as shown in Equation 5).Reaction condition is mild, and post-processing operation is simple, suitable for industrialized production.
Solvent therein is evaporated off in step (c), and step (d) carries out product distilation, and the distillation of two steps is to temperature and very
The requirement of reciprocal of duty cycle is different, and two steps are distilled compared with a step way of distillation, can clearly receive the condition of product, meanwhile, it can be more thorough
The separating solvent with product of bottom, improves the purity of product.
Catalyst is selected from step (a)：One kind in ethanedioic acid, acetic acid, septichen, methanesulfonic acid.
Solvent is selected from step (b)：One kind in ethyl acetate, dichloromethane, chloroform, n-hexane, toluene or
More than one mixed solvent.
The step (a) is the catalysis for adding in 5~10mol into 100mol vinyl acetates under the conditions of 10~30 DEG C
Agent, and when 10~18 is small, the interior hydrogen chloride for being passed through 100~200mol carries out addition reaction, obtains reaction solution.
The step (a) is the acetic acid for adding in 5mol into 100mol vinyl acetates under the conditions of 10~30 DEG C, and 11
~14 interior hydrogen chloride for being passed through 150mol when small carry out addition reaction, obtain reaction solution.
The step (c) be by dried organic phase under 25~35 DEG C, -0.06Mpa~-0.07MPa pressure conditions
It is concentrated under reduced pressure, solvent is evaporated off, obtain mother liquor.
The step (d) is to continue to be evaporated under reduced pressure under 35~48 DEG C, -0.08 to -0.10MPa pressure condition by mother liquor,
Obtain 1- chloroethene yl acetates.
The invention has the advantages and positive effects that：The synthetic route of a new 1- chloroethene yl acetate is explored,
The route process conditions are mild, and easy to operate, raw material is cheap and easy to get, the 1- chloroethene yl acetate purity ＞ 90% being prepared,
Yield is 60.3-65.3%.
Description of the drawings
Fig. 1 is the gas chromatogram of the 1- chloroethene yl acetates prepared in the embodiment of the present invention 1.
Fig. 2 is the ultraviolet spectrogram of the 1- chloroethene yl acetates prepared in the embodiment of the present invention 1.
Fig. 3 is the infrared spectrogram of the 1- chloroethene yl acetates prepared in the embodiment of the present invention 1.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of the 1- chloroethene yl acetates prepared in the embodiment of the present invention 1.
Fig. 5 is the carbon-13 nmr spectra figure of the 1- chloroethene yl acetates prepared in the embodiment of the present invention 1.
Fig. 6 is the mass spectrogram of the 1- chloroethene yl acetates prepared in the embodiment of the present invention 1.
Specific embodiment
Embodiment 1,
Vinyl acetate 86.09g (1.0mol) and ethanedioic acid 2.70g (0.03mol) are weighed, is added sequentially to 500ml tri-
In mouth bottle, stirring controls 25~35 DEG C of temperature in bottle, interior when 12 is small to be passed through hydrogen chloride 43.8g (1.2mol).
After being passed through hydrogen chloride, chloroform 179.07g (1.5mol) is added in, separatory funnel is transferred to after stirring evenly
In.100g water is added in into separatory funnel, organic phase is collected in washing, liquid separation.Anhydrous sodium sulfate is added in after repeating the operation 3 times
When drying 5 is small.
It filters and removes solid, mother liquor transfer is concentrated under reduced pressure by control vacuum degree -0.06MPa~-0.07MPa, 20 DEG C
After~30 DEG C are evaporated off solvent, mother liquor continues to be evaporated under reduced pressure, and controls vacuum degree -0.07~-0.09Mpa, receives top temperature 40 DEG C~50
DEG C fraction, obtains 1- chloroethene yl acetate 80.03g, purity 97.8%, yield 65.3%.GC purity：97.804%；
ESI-MS, m/z：79.1[C2H4ClO-],87.1[C4H7O2 -]；IR(cm-1):2992,939,1769,1442,1211,673；1H-
NMR(DMSO-d6):δ 6.55 (m, 1H), 2.51 (s, 3H), 1.74 (d, J=8.4,3H)13C-NMR(DMSO-d6):δ 20.90,
31.01,81.89,168.56.
Embodiment 2,
Vinyl acetate 86.09g (1.0mol) and acetic acid 3.00g (0.05mol) are weighed, is added sequentially to tri- mouthfuls of 500ml
In bottle, stirring controls 15~25 DEG C of temperature in bottle, interior when 20 is small to be passed through hydrogen chloride 54.75g (1.5mol).
After being passed through hydrogen chloride, dichloromethane 254.79g (3.0mol) is added in, separatory funnel is transferred to after stirring evenly
In.100g water is added in into separatory funnel, organic phase is collected in washing, liquid separation.Anhydrous sodium sulfate is added in after repeating the operation 3 times
When drying 5 is small.
It filters and removes solid, mother liquor transfer is concentrated under reduced pressure by control vacuum degree -0.05MPa~-0.06MPa, 30 DEG C
After~40 DEG C are evaporated off solvent, mother liquor continues to be evaporated under reduced pressure, and controls vacuum degree -0.08~-0.10Mpa, receives 35~45 DEG C of top temperature
Fraction obtains 1- chloroethene yl acetate 78.06g, purity 95.2%, yield 63.7%.
Embodiment 3,
Vinyl acetate 86.09g (1.0mol) and acetic acid 1.80g (0.03mol) are weighed, is added sequentially to tri- mouthfuls of 500ml
In bottle, stirring controls 5 DEG C~15 DEG C of temperature in bottle, interior when 9 is small to be passed through hydrogen chloride 32.85g (0.9mol).
After being passed through hydrogen chloride, ethyl acetate 220.28g (2.5mol) is added in, separatory funnel is transferred to after stirring evenly
In.100g water is added in into separatory funnel, organic phase is collected in washing, liquid separation.Anhydrous sodium sulfate is added in after repeating the operation 3 times
When drying 5 is small.
It filters and removes solid, mother liquor transfer is concentrated under reduced pressure by control vacuum degree -0.04MPa~-0.06MPa, 30 DEG C
After~40 DEG C are evaporated off solvent, mother liquor continues to be evaporated under reduced pressure, and controls vacuum degree -0.08~-0.10Mpa, receives top temperature 40 DEG C~50
DEG C fraction, obtains 1- chloroethene yl acetate 73.90g, purity 91.6%, yield 60.3%.
Embodiment 4,
Vinyl acetate 86.09g (1.0mol) and ethanedioic acid 1.80g (0.02mol) are weighed, is added sequentially to 500ml tri-
In mouth bottle, stirring controls 15 DEG C~20 DEG C of temperature in bottle, interior when 24 is small to be passed through hydrogen chloride 91.25g (2.5mol).
After being passed through hydrogen chloride, dichloromethane 169.86g (2.0mol) is added in, separatory funnel is transferred to after stirring evenly
In.100g water is added in into separatory funnel, organic phase is collected in washing, liquid separation.Anhydrous sodium sulfate is added in after repeating the operation 3 times
When drying 5 is small.
It filters and removes solid, mother liquor transfer is concentrated under reduced pressure by control vacuum degree -0.06MPa~-0.07MPa, 25 DEG C
After~35 DEG C are evaporated off solvent, mother liquor continues to be evaporated under reduced pressure, and controls vacuum degree -0.07~-0.09Mpa, receives top temperature 35 DEG C~48
DEG C fraction, obtains 1- chloroethene yl acetate 75.37g, purity 90.8%, yield 61.5%.
Embodiment 5,
Vinyl acetate 86.09g (1.0mol) and methanesulfonic acid 4.81g (0.05) are weighed, is added sequentially to 500ml there-necked flasks
In, stirring controls 10 DEG C~25 DEG C of temperature in bottle, interior when 24 is small to be passed through hydrogen chloride 73.00g (2.0).
After being passed through hydrogen chloride, ethyl acetate 220.28g (2.5mol) is added in, separatory funnel is transferred to after stirring evenly
In.100g water is added in into separatory funnel, organic phase is collected in washing, liquid separation.Anhydrous sodium sulfate is added in after repeating the operation 3 times
When drying 5 is small.
It filters and removes solid, mother liquor transfer is concentrated under reduced pressure by control vacuum degree -0.05MPa~-0.06MPa, 30 DEG C
After~40 DEG C are evaporated off solvent, mother liquor continues to be evaporated under reduced pressure, and controls vacuum degree -0.08~-0.10Mpa, receives top temperature 30 DEG C~45
DEG C fraction, obtains 1- chloroethene yl acetate 78.55g, purity 93.6%, yield 64.1%.
The embodiment of the present invention is described in detail above, but the content is only presently preferred embodiments of the present invention,
It should not be construed as limiting the practical range of the present invention.Any changes and modifications in accordance with the scope of the present application,
It should all still belong within the patent covering scope of the present invention.
Claims (7)
1. a kind of preparation method of 1- chloroethenes yl acetate, it is characterised in that：It comprises the steps of：
(a) under the conditions of 5~45 DEG C, the catalyst of 2~50mol is added in into the vinyl acetate of 100mol, and it is small 9~27
When it is interior be passed through 80~300mol hydrogen chloride carry out addition reaction, obtain reaction solution；
(b) after the solvent dilution of 150~300mol is added in into reaction solution, washed, extracted with water, organic phase drying；
(c) dried organic phase under 5~40 DEG C, -0.04Mpa~-0.07MPa pressure conditions is concentrated under reduced pressure, be evaporated off molten
Agent obtains mother liquor；
(d) mother liquor is continued to be evaporated under reduced pressure under 30~50 DEG C, -0.07~-0.10MPa pressure conditions, obtains 1- chloroethyl second
Acid esters.
2. a kind of preparation method of 1- chloroethenes yl acetate according to claim 1, it is characterised in that：It is urged in step (a)
Agent is selected from：One kind in ethanedioic acid, acetic acid, septichen, methanesulfonic acid.
3. a kind of preparation method of 1- chloroethenes yl acetate according to claim 1, it is characterised in that：It is molten in step (b)
Agent is selected from：One or more than one kinds of mixed solvents in ethyl acetate, dichloromethane, chloroform, n-hexane, toluene.
4. a kind of preparation method of 1- chloroethenes yl acetate according to claims 1 to 3 any one, it is characterised in that：
The step (a) is the catalyst for adding in 5~10mol into the vinyl acetate of 100mol under the conditions of 10~30 DEG C, and
9~27 interior hydrogen chloride for being passed through 100~200mol when small carry out addition reaction, obtain reaction solution.
5. a kind of preparation method of 1- chloroethenes yl acetate according to claim 4, it is characterised in that：The step (a)
For under the conditions of 10~30 DEG C, the acetic acid of 5mol is added in into the vinyl acetate of 100mol, and interior when 11~14 is small is passed through
The hydrogen chloride of 150mol carries out addition reaction, obtains reaction solution.
6. a kind of preparation method of 1- chloroethenes yl acetate according to claim 5, it is characterised in that：The step (c)
For dried organic phase is concentrated under reduced pressure under 25~35 DEG C, -0.06Mpa~-0.07MPa pressure conditions, solvent is evaporated off, obtains
Obtain mother liquor.
7. a kind of preparation method of 1- chloroethenes yl acetate according to claim 6, it is characterised in that：The step (d)
To continue to be evaporated under reduced pressure mother liquor under 35~48 DEG C, -0.08~-0.10MPa pressure conditions, 1- chloroethene yl acetates are obtained.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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