CN103073421A - High-efficiency simple synthetic method for delta-chlorobutyl ester - Google Patents
High-efficiency simple synthetic method for delta-chlorobutyl ester Download PDFInfo
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- CN103073421A CN103073421A CN 201110326576 CN201110326576A CN103073421A CN 103073421 A CN103073421 A CN 103073421A CN 201110326576 CN201110326576 CN 201110326576 CN 201110326576 A CN201110326576 A CN 201110326576A CN 103073421 A CN103073421 A CN 103073421A
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- chloride
- tetrahydrofuran
- acyl chlorides
- thf
- synthetic method
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- 238000010189 synthetic method Methods 0.000 title claims 9
- 150000002148 esters Chemical class 0.000 title abstract description 6
- 229920005556 chlorobutyl Polymers 0.000 title abstract 3
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims abstract description 82
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 claims abstract description 41
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 claims abstract description 26
- 150000001263 acyl chlorides Chemical class 0.000 claims abstract description 23
- 238000006243 chemical reaction Methods 0.000 claims abstract description 16
- 235000005074 zinc chloride Nutrition 0.000 claims abstract description 13
- 239000011592 zinc chloride Substances 0.000 claims abstract description 13
- 238000002360 preparation method Methods 0.000 claims abstract description 12
- 230000035484 reaction time Effects 0.000 claims abstract description 11
- 238000004821 distillation Methods 0.000 claims abstract description 10
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 6
- 239000002994 raw material Substances 0.000 claims abstract description 6
- 239000002904 solvent Substances 0.000 claims abstract description 5
- -1 δ-chloro butyl Chemical group 0.000 claims description 21
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- YYROPELSRYBVMQ-UHFFFAOYSA-N 4-toluenesulfonyl chloride Chemical compound CC1=CC=C(S(Cl)(=O)=O)C=C1 YYROPELSRYBVMQ-UHFFFAOYSA-N 0.000 claims description 4
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 4
- 235000014113 dietary fatty acids Nutrition 0.000 claims description 4
- 229930195729 fatty acid Natural products 0.000 claims description 4
- 239000000194 fatty acid Substances 0.000 claims description 4
- 150000004665 fatty acids Chemical class 0.000 claims description 4
- LSNNMFCWUKXFEE-UHFFFAOYSA-M Bisulfite Chemical compound OS([O-])=O LSNNMFCWUKXFEE-UHFFFAOYSA-M 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- 150000002632 lipids Chemical class 0.000 claims description 2
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims 3
- ICGLOTCMOYCOTB-UHFFFAOYSA-N [Cl].[Zn] Chemical compound [Cl].[Zn] ICGLOTCMOYCOTB-UHFFFAOYSA-N 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 claims 1
- 239000012442 inert solvent Substances 0.000 claims 1
- 239000004615 ingredient Substances 0.000 claims 1
- 239000000203 mixture Substances 0.000 claims 1
- 239000000376 reactant Substances 0.000 claims 1
- YBBRCQOCSYXUOC-UHFFFAOYSA-N sulfuryl dichloride Chemical compound ClS(Cl)(=O)=O YBBRCQOCSYXUOC-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 18
- 239000003054 catalyst Substances 0.000 abstract description 3
- 238000007796 conventional method Methods 0.000 abstract 1
- 238000004519 manufacturing process Methods 0.000 abstract 1
- 238000000746 purification Methods 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- 238000009413 insulation Methods 0.000 description 5
- 238000003756 stirring Methods 0.000 description 5
- ZCYVEMRRCGMTRW-UHFFFAOYSA-N 7553-56-2 Chemical compound [I] ZCYVEMRRCGMTRW-UHFFFAOYSA-N 0.000 description 3
- 239000011630 iodine Substances 0.000 description 3
- 229910052740 iodine Inorganic materials 0.000 description 3
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- FOCAUTSVDIKZOP-UHFFFAOYSA-N chloroacetic acid Chemical compound OC(=O)CCl FOCAUTSVDIKZOP-UHFFFAOYSA-N 0.000 description 2
- 230000007812 deficiency Effects 0.000 description 2
- MTZQAGJQAFMTAQ-UHFFFAOYSA-N ethyl benzoate Chemical compound CCOC(=O)C1=CC=CC=C1 MTZQAGJQAFMTAQ-UHFFFAOYSA-N 0.000 description 2
- KLRHPHDUDFIRKB-UHFFFAOYSA-M indium(i) bromide Chemical compound [Br-].[In+] KLRHPHDUDFIRKB-UHFFFAOYSA-M 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 239000012074 organic phase Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- RKIDDEGICSMIJA-UHFFFAOYSA-N 4-chlorobenzoyl chloride Chemical compound ClC(=O)C1=CC=C(Cl)C=C1 RKIDDEGICSMIJA-UHFFFAOYSA-N 0.000 description 1
- VGCXGMAHQTYDJK-UHFFFAOYSA-N Chloroacetyl chloride Chemical compound ClCC(Cl)=O VGCXGMAHQTYDJK-UHFFFAOYSA-N 0.000 description 1
- 239000002841 Lewis acid Substances 0.000 description 1
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 1
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 1
- WETWJCDKMRHUPV-UHFFFAOYSA-N acetyl chloride Chemical compound CC(Cl)=O WETWJCDKMRHUPV-UHFFFAOYSA-N 0.000 description 1
- 239000012346 acetyl chloride Substances 0.000 description 1
- PASDCCFISLVPSO-UHFFFAOYSA-N benzoyl chloride Chemical compound ClC(=O)C1=CC=CC=C1 PASDCCFISLVPSO-UHFFFAOYSA-N 0.000 description 1
- 229910052797 bismuth Inorganic materials 0.000 description 1
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000005336 cracking Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 230000026030 halogenation Effects 0.000 description 1
- 238000005658 halogenation reaction Methods 0.000 description 1
- PNDPGZBMCMUPRI-UHFFFAOYSA-N iodine Chemical compound II PNDPGZBMCMUPRI-UHFFFAOYSA-N 0.000 description 1
- 229910052746 lanthanum Inorganic materials 0.000 description 1
- FZLIPJUXYLNCLC-UHFFFAOYSA-N lanthanum atom Chemical compound [La] FZLIPJUXYLNCLC-UHFFFAOYSA-N 0.000 description 1
- 150000007517 lewis acids Chemical class 0.000 description 1
- 229930014626 natural product Natural products 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- PODWXQQNRWNDGD-UHFFFAOYSA-L sodium thiosulfate pentahydrate Chemical compound O.O.O.O.O.[Na+].[Na+].[O-]S([S-])(=O)=O PODWXQQNRWNDGD-UHFFFAOYSA-L 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a preparation method for delta-chlorobutyl ester. A key point of the invention is as follows: tetrahydrofuran is used as a raw material to react with acyl chloride under catalysis of zinc chloride so as to rapidly and mildly synthesize delta-chlorobutyl ester with high yield and high purity. According to the invention, reduced pressure distillation and purification are directly carried out under the condition of no separation; unfavorable factors of low yield, long reaction time, excess usage amount of raw materials, need for expensive catalysts, severe reaction conditions and the like in conventional methods are avoided; the method is characterized by no use of a solvent or use of a small amount of the solvent, a small catalyst usage amount, a low price, mild reaction conditions and high yield; the whole process of preparation is simple and safe and costs little, and the method is applicable to industrial mass production.
Description
Technical field:
The invention belongs to field of fine chemical, relate to the preparation method of δ-chloro butyl ester.
Technical background:
δ-chloro butyl ester is widely used in the synthetic natural product that contains 4 carbon atom chains, medicine etc., is an important intermediate of synthesizing a lot of compounds.People notice for a long time at Lewis acid such as ZnCl
2, BCl
3, the lower tetrahydrofuran (THF)s of effect such as halogenation bismuth, organic lanthanum title complex and iodine can the cracking open loop.But the method for having reported has many deficiencies, low such as productive rate, cost is high or reagent is difficult to obtain, and the reaction times that certain methods need to be grown, harsh reaction conditions, needs to use solvent and reaction under the condition that refluxes, harmful catalyzer and the very loaded down with trivial details method of environment for use.Therefore the novel method of seeking preparation δ-chloro butyl ester is of great practical significance.(JACS 1939, and 2667-2669) open loop under zinc chloride catalysis generates the method for a series of δ-chloro butyl ester to the report tetrahydrofuran (THF) with different acyl chlorides, but the method productive rate is low, and reacting reflux time is long, and need are with excessive acyl chlorides for Jone Cloke etc.Pasha M.A. etc. (Ultrasonics sonochemistry, 2006,175-179) doing catalyzer high yield under ul-trasonic irradiation with zinc powder has obtained δ-chloro butyl ester, but uses zinc powder and ultrasonic wave to be unfavorable for industrial production.(the synthetic communication such as Pasha M.A., 2007,927-932) do the catalyzer tetrahydrofuran (THF) with iodine and acyl chlorides has generated δ-chloro butyl ester in the room temperature high yield, but it is more expensive to react used iodine, tetrahydrofuran (THF) is greatly excessive, has not only wasted expensive tetrahydrofuran (THF), also will remove iodine with Sulfothiorine simultaneously, aftertreatment is loaded down with trivial details, is not suitable for industrial production.Yadav J.S., Suresh V. philosophy with InBr (Journal of molecular Catalysis A:chemical, 2007,266-269), Bi (NO
3)
3(Canadian Journal of chemistry, 2007,1037-1040), La (NO
3)
3(synthetic communication2008,92-99) etc. makees catalyzer, and acyl chlorides successfully generates δ-chloro butyl ester with the tetrahydrofuran (THF) open loop, but these catalyzer are relatively expensive.Field etc. (JACS 1995,77,1206-7) reported the method for preparing 4-chlorobutyl p-toluenesulfonic esters, but the method productive rate low (34%), temperature is high, and long reaction time reacts too violent, dangerous property during beginning.
Summary of the invention:
In order to overcome the deficiency of above-mentioned technique, the object of the present invention is to provide the preparation method of a kind of δ-chloro butyl ester, compare with existing method, equipment requirements of the present invention is simple, easy to operate, the reaction process environmental protection, starting material are inexpensive, and easily control has good industrial prospect.
For achieving the above object, technical scheme of the present invention is:
The preparation method of a kind of δ-chloro butyl ester may further comprise the steps:
1) take tetrahydrofuran (THF) as raw material, under zinc chloride catalysis with acyl chloride reaction fast gentle, obtain δ-chloro butyl ester to high yield.
2) react rear direct underpressure distillation and got highly purified δ-chloro butyl ester
Preferably:
Described step 1) mol ratio of tetrahydrofuran (THF) and acyl chlorides is 1～1.1: 1 in; It is 0 ℃～30 ℃ for the fatty acid chloride temperature of reaction; For the aromatic acid temperature of reaction generally at 25 ℃～50 ℃; For Tosyl chloride, temperature is at 60 ℃～80 ℃; The consumption of zinc chloride and the mol ratio of tetrahydrofuran (THF) are 10%～0.1%.Here acyl chlorides can any acyl chlorides comprises the acyl chlorides of lipid acid, aromatic acid and sulfonic acid.Reaction times is short, and for fatty acid chloride, the reaction times is less than 1 hour, to the aromatic acid acyl chloride reaction time at 1-2 hour, for its reaction times of yellow acyl chlorides at 3-5 hour.
Route involved in the present invention is as follows:
Embodiment
Key point of the present invention is take tetrahydrofuran (THF) as raw material, under zinc chloride catalysis with acyl chloride reaction fast, gentleness, high yield, obtain δ-chloro butyl ester to high purity.Direct underpressure distillation purifying in unseparated situation.Existing methodical low-yield, long reaction time, the large excessive or unfavorable factors such as catalyzer that need to be more expensive or severe reaction conditions of raw material have been avoided.Characteristics of the present invention are not use or use a small amount of solvent, and catalyst levels is few, cheap, and the gentle productive rate of reaction conditions is high.Simultaneously simple, the safety of whole process, low cost are fit to that industry is large produces.The following examples can more specifically be understood the present invention, but in fact illustrate rather than limit the scope of the invention.
The preparation of embodiment 1:4-butylene-chlorohydrin ethyl ester
Add Zinc Chloride Anhydrous 1 gram in 250 milliliters of there-necked flasks, Acetyl Chloride 98Min. 78.5 grams stir lower tetrahydrofuran (THF) 72 grams that drip, ice bath cools off to maintain the temperature at below 30 degree, drips off rear insulation 1 hour, and the water pump underpressure distillation gets 4-butylene-chlorohydrin ethyl ester 145 grams, productive rate 96%, purity 99.5%.
The preparation of embodiment 2:4-butylene-chlorohydrin chloracetate
Add Zinc Chloride Anhydrous 1 gram in 250 milliliters of there-necked flasks, chloro-acetyl chloride 113 grams stir lower room temperature and drip tetrahydrofuran (THF) 72 grams, drip in the process and to keep being stabilized in 40 and spend, drip off rear insulation 1 hour, underpressure distillation gets 4-butylene-chlorohydrin chloracetate 166.6 grams, productive rate 90%, purity 99.2%.
The preparation of embodiment 3:4-butylene-chlorohydrin benzoic ether
Add Zinc Chloride Anhydrous 1 gram in 250 milliliters of there-necked flasks, Benzoyl chloride 141 grams stir lower room temperature and drip tetrahydrofuran (THF) 72 grams, drip in the process and to keep being stabilized in below 40 degree, drip off rear insulation 2 hours, underpressure distillation gets 4-butylene-chlorohydrin benzoic ether 200 grams, productive rate 94%, purity 99.35%.
The preparation of embodiment 4:4-butylene-chlorohydrin Chlorodracylic acid ester
Add Zinc Chloride Anhydrous 1 gram in 250 milliliters of there-necked flasks, parachlorobenzoyl chloride 175 grams, stir lower room temperature and drip tetrahydrofuran (THF) 72 grams, drip in the process and to keep being stabilized in 40 and spend, drip off rear insulation 2 hours, underpressure distillation gets 4-butylene-chlorohydrin Chlorodracylic acid ester 230 grams, productive rate 93%, purity 99.6%
The preparation of embodiment 5:4-butylene-chlorohydrin p-toluenesulfonic esters
Add Zinc Chloride Anhydrous 4 grams in 250 milliliters of there-necked flasks, to yellow acyl chlorides 76 grams of toluene, toluene 20ML, be heated with stirring to 80 degree, drip 37.5 gram tetrahydrofuran (THF)s, drip off rear insulation 2 hours, reaction solution is poured in the frozen water, adding toluene makes organic phase be inverted to the upper strata, branch vibration layer, organic phase is washed till neutrality with sodium hydrogen carbonate solution respectively, again with the saturated common salt washing, behind the anhydrous magnesium sulfate drying, toluene is reclaimed in underpressure distillation, the oil pump underpressure distillation gets 4-butylene-chlorohydrin p-toluenesulfonic esters 77 grams, productive rate 73%, purity 98% again
Claims (9)
1. the preparation method of δ-chloro butyl ester take tetrahydrofuran (THF) as raw material, obtains δ-chloro butyl ester with acyl chloride reaction under zinc chloride catalysis, has reacted rear direct underpressure distillation and has got highly purified δ-chloro butyl ester.
2. synthetic method according to claim 1 is characterized in that: tetrahydrofuran (THF) is produced δ-chloro butyl ester with acyl chlorides effect open loop under the condition that the anhydrous chlorine zinc of catalytic amount exists.
3. synthetic method according to claim 2, it is characterized in that: the mol ratio of tetrahydrofuran (THF) and acyl chlorides is 1～1.5: 1～1.2; Preferably 1～1.05: 1～1.05.
4. synthetic method according to claim 2 is characterized in that the consumption of zinc chloride and the mol ratio of tetrahydrofuran (THF) are 10%～0.1%.Here acyl chlorides can any acyl chlorides comprises the acyl chlorides of lipid acid, aromatic acid and sulfonic acid.
5. synthetic method according to claim 2 is characterized in that: be 0 ℃～30 ℃ for the fatty acid chloride temperature of reaction; For the aromatic acid temperature of reaction generally at 25 ℃～50 ℃; For Tosyl chloride, temperature is at 60 ℃～80 ℃.
6. synthetic method according to claim 2 is characterized in that:, or react in a small amount of inert solvent as can be solvent-free to the yellow acyl chloride reaction of toluene for SULPHURYL CHLORIDE, such as benzene, toluene etc.
7. according to claim 2,6 described synthetic methods, it is characterized in that: the mole-volume ratio of employed yellow acyl chlorides and quantity of solvent is 1 (mole): 0～200 (ml) is 0-200ml/mole, preferably: 20-100ml/mol, more preferably 20-50ml/mol.
8. synthetic method according to claim 2 is characterized in that for fatty acid chloride, and the reaction times is less than 1 hour, to the aromatic acid acyl chloride reaction time at 1-2 hour, for its reaction times of yellow acyl chlorides at 3-5 hour.
9. according to claim 1,2 described synthetic methods, it is characterized in that: the order of addition(of ingredients) of reactant is that tetrahydrofuran (THF) is added drop-wise in the mixture of acyl chlorides and zinc chloride.
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622407A (en) * | 2016-02-05 | 2016-06-01 | 中国海洋石油总公司 | Preparation method of acrylic acid-3-chloropropyl ester |
| CN105646213A (en) * | 2016-02-15 | 2016-06-08 | 南通市东昌化工有限公司 | Preparation method of acrylic acid-4-chlorobutyl ester compounds |
| CN109776484A (en) * | 2017-11-14 | 2019-05-21 | 石家庄圣泰化工有限公司 | The synthetic method of 1,4- butane sultones |
| CN111410600A (en) * | 2020-01-21 | 2020-07-14 | 安徽省诚联医药科技有限公司 | Preparation method of p-phenylbutoxy benzoic acid |
| CN112062677A (en) * | 2020-08-21 | 2020-12-11 | 温州国仕邦高分子材料有限公司 | Methacrylic acid-4-hydroxybutyl ester and preparation method thereof |
-
2011
- 2011-10-25 CN CN 201110326576 patent/CN103073421A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105622407A (en) * | 2016-02-05 | 2016-06-01 | 中国海洋石油总公司 | Preparation method of acrylic acid-3-chloropropyl ester |
| CN105646213A (en) * | 2016-02-15 | 2016-06-08 | 南通市东昌化工有限公司 | Preparation method of acrylic acid-4-chlorobutyl ester compounds |
| CN109776484A (en) * | 2017-11-14 | 2019-05-21 | 石家庄圣泰化工有限公司 | The synthetic method of 1,4- butane sultones |
| CN109776484B (en) * | 2017-11-14 | 2023-05-09 | 河北圣泰材料股份有限公司 | Synthesis method of 1, 4-butane sultone |
| CN111410600A (en) * | 2020-01-21 | 2020-07-14 | 安徽省诚联医药科技有限公司 | Preparation method of p-phenylbutoxy benzoic acid |
| CN112062677A (en) * | 2020-08-21 | 2020-12-11 | 温州国仕邦高分子材料有限公司 | Methacrylic acid-4-hydroxybutyl ester and preparation method thereof |
| CN112062677B (en) * | 2020-08-21 | 2022-12-23 | 温州国仕邦高分子材料有限公司 | Methacrylic acid-4-hydroxybutyl ester and preparation method thereof |
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Application publication date: 20130501 |