CN104119227A - Method for performing esterification reaction on carboxylic acid and ethylene oxide compound - Google Patents
Method for performing esterification reaction on carboxylic acid and ethylene oxide compound Download PDFInfo
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- CN104119227A CN104119227A CN201310152071.9A CN201310152071A CN104119227A CN 104119227 A CN104119227 A CN 104119227A CN 201310152071 A CN201310152071 A CN 201310152071A CN 104119227 A CN104119227 A CN 104119227A
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- acid
- ethylene oxide
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/24—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran
- C07C67/26—Preparation of carboxylic acid esters by reacting carboxylic acids or derivatives thereof with a carbon-to-oxygen ether bond, e.g. acetal, tetrahydrofuran with an oxirane ring
Abstract
The invention belongs to the field of chemical synthesis, relates to a method for performing esterification reaction on an ethylene oxide compound and a carboxylic acid, and concretely relates to a method for performing solvent-free esterification reaction on a carboxylic acid and ethylene oxide in a double-activating synergetic catalysis way. The method employs ferric trichloride and pyridine as catalysts, and performs synergetic catalysis on the carboxylic acid and the ethylene oxide compound at a reaction temperature of 20-100 DEG C. The method is capable of well catalyzing esterification reaction on saturated carboxylic acids and the ethylene oxide compound to synthesize beta-hydroxy esters, is high in catalysis efficiency, and generates relatively less byproducts. The method has wide application prospect in industrialized production.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to the method that oxirane compound reacts with carboxylic esterification.Be specifically related to a kind of method of dual-active concerted catalysis carboxylic acid and oxyethane esterification under condition of no solvent, especially
A kind of method that iron trichloride reacts with carboxylic esterification with pyridine concerted catalysis oxirane compound.
Background technology
Beta-hydroxy esters is important intermediate conventional in organic synthesis, the most popular method of at present synthetic beta-hydroxy esters is to utilize carboxylic acid to carry out selective opening reaction to oxyethane, the catalyzer adopting in reaction comprises the organic weak bases such as the Lewis acid such as iron trichloride, chromium trichloride, DMA, triethylamine, hexafluoro-2-propyl alcohol, tributylphosphine or ionic liquid etc.
But known method often needs higher temperature of reaction, longer reaction times at present, and generally all need in the poisonous and harmful organic solvents such as tetrahydrofuran (THF), methyl alcohol, acetonitrile, methylene dichloride or benzene, react.All be starved of in synthetic and industrial production in actual laboratory a kind of can be with the efficient synthesis technique of high conversion, high regio-selective synthesis beta-hydroxy esters under condition of no solvent.
Summary of the invention
The object of the invention is to overcome the defect of prior art, the novel method that provides a kind of oxirane compound to react with carboxylic esterification, the novel method that is specifically related to dual-active concerted catalysis carboxylic acid and oxyethane esterification under condition of no solvent, relates in particular to a kind of method that iron trichloride reacts with carboxylic esterification with pyridine concerted catalysis oxirane compound.
The present invention adopts iron trichloride and pyridine as two deactivated catalysts, improve while using iron trichloride and can not transform completely, the low problem of catalytic efficiency while using pyridine, can not only be efficiently, catalysis carboxylic acid and oxirane compound esterification rapidly, and the esterification products making has good regioselectivity.
In the method for carboxylic acid provided by the invention and oxirane compound esterification, adopt iron trichloride and pyridine to make catalyzer, at 20-100 DEG C of temperature of reaction, concerted catalysis carboxylic acid reacts with oxirane compound.Preferably 40-80 DEG C of temperature of reaction in the present invention.
In the present invention, the consumption in reacting is respectively 0.05-3 mol% to catalyzer iron trichloride with pyridine, and catalyzer preferable amount is iron trichloride 0.25-1.5 mol%, pyridine 0.25-1.5 mol%.
In the present invention, carboxylic acid can be selected from various carboxylic acids, and especially saturated monoprotic acid, as acetic acid, propionic acid, butyric acid, 2 Methylpropionic acid, 2 Ethylbutanoic acid etc.
In the present invention, oxirane compound can be selected from oxyethane and substituted epoxy ethane, as 2-methyl oxirane, 2-chloromethyloxirane, 2-brooethyl oxyethane, 2-allyloxy methyl oxirane, 2-phenyl ethylene oxide, 2-decyl oxyethane, 2,2-dimethyl ethylene oxide etc.
In the inventive method, reaction adopts condition of no solvent.
The esterification of iron trichloride provided by the invention and pyridine dual-active concerted catalysis oxirane compound and carboxylic acid, FeCl in reaction process
3form coordinate bond as Lewis acid and the Sauerstoffatom of oxyethane, activation oxirane ring, makes it be subject to nucleophilic reagent attack, thereby reaches the object that catalyzed reaction is carried out; And pyridine is with form and the carboxylic acid generation salification of weak base, the Sauerstoffatom on activated carboxyl, increases its nucleophilicity, improves reaction efficiency.Iron trichloride and pyridine co-catalysis have good catalytic activity, have very strong katalysis between 20-100 DEG C, wherein best with the temperature of reaction of 40-80 DEG C.
Method of the present invention is catalysis carboxylic acid and the synthetic beta-hydroxy esters of reacting of oxyethane well, and catalytic efficiency is high, obviously be better than the catalytic effect of alone iron trichloride or alone pyridine, and less generation by product.The method is with a wide range of applications in suitability for industrialized production.
Embodiment
Embodiment 1: synthesis of acetic acid-(3-chlorine-2-hydroxyl) propyl ester
Method 1(iron trichloride/pyridine concerted catalysis method): iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in acetic acid (50mmol), at 0 DEG C, 2-chloromethyloxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-chloromethyloxirane transformation efficiency is 99%, and acetic acid-(3-chlorine-2-hydroxyl) propyl ester is analyzed yield 88.2% through GC marker method.
Method 2(ferric trichloride catalytic method): iron trichloride (1.0mol%) is dissolved in acetic acid (50mmol), at 0 DEG C, 2-chloromethyloxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 60 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-chloromethyloxirane transformation efficiency is 80%, and acetic acid-(3-chlorine-2-hydroxyl) propyl ester is analyzed yield 71.6% through GC marker method.
Method 3(pyridine catalysis method): pyridine (1.0mol%) is dissolved in acetic acid (50mmol), at 0 DEG C, 2-chloromethyloxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 60 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-chloromethyloxirane transformation efficiency is 60%, and acetic acid-(3-chlorine-2-hydroxyl) propyl ester is analyzed yield 53.1% through GC marker method.
Embodiment 2: propionic acid synthesized-(3-chlorine-2-hydroxyl) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in propionic acid (50mmol), at 0 DEG C, 2-chloromethyloxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-chloromethyloxirane transformation efficiency is 100%, and propionic acid-(3-chlorine-2-hydroxyl) propyl ester is analyzed yield 88.2% through GC marker method.
Embodiment 3: synthetic butyric acid-(3-chlorine-2-hydroxyl) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in butyric acid (50mmol), at 0 DEG C, 2-chloromethyloxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-chloromethyloxirane transformation efficiency is 100%, and butyric acid-(3-chlorine-2-hydroxyl) propyl ester is analyzed yield 80.4% through GC marker method.
Embodiment 4: synthetic isopropylformic acid-(3-chlorine-2-hydroxyl) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in isopropylformic acid (50mmol), at 0 DEG C, 2-chloromethyloxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-chloromethyloxirane transformation efficiency is 100%, and isopropylformic acid-(3-chlorine-2-hydroxyl) propyl ester is analyzed yield 82.5% through GC marker method.
Embodiment 5: synthetic 2 Ethylbutanoic acid-(3-chlorine-2-hydroxyl) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in 2 Ethylbutanoic acid (50mmol), at 0 DEG C, 2-chloromethyloxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-chloromethyloxirane transformation efficiency is 100%, and 2 Ethylbutanoic acid-(3-chlorine-2-hydroxyl) propyl ester is analyzed yield 96.0% through GC marker method.
Embodiment 6: synthetic 2 Ethylbutanoic acid-(2-hydroxyl) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in 2 Ethylbutanoic acid (50mmol), at 0 DEG C, 2-methyl oxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-methyl oxirane transformation efficiency is 100%, and 2 Ethylbutanoic acid-(2-hydroxyl) propyl ester is analyzed yield 83.3% through GC marker method.
Embodiment 7: synthetic 2 Ethylbutanoic acid-(the bromo-2-hydroxyl of 3-) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in 2 Ethylbutanoic acid (50mmol), at 0 DEG C, 2-brooethyl oxyethane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-brooethyl oxyethane transformation efficiency is 100%, and 2 Ethylbutanoic acid-(the bromo-2-hydroxyl of 3-) propyl ester is analyzed yield 94.3% through GC marker method.
Embodiment 8: synthetic 2 Ethylbutanoic acid-(2-hydroxy-2-methyl) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in 2 Ethylbutanoic acid (50mmol), at 0 DEG C, by 2,2-dimethyl ethylene oxide (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2,2-dimethyl ethylene oxide transformation efficiency is 100%, and 2 Ethylbutanoic acid-(2-hydroxy-2-methyl) propyl ester is analyzed yield 100% through GC marker method.
Embodiment 9: synthetic 2 Ethylbutanoic acid-(2-phenyl-2-methyl) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in 2 Ethylbutanoic acid (50mmol), at 0 DEG C, 2-phenyl ethylene oxide (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-phenyl ethylene oxide transformation efficiency is 100%, and 2 Ethylbutanoic acid-(2-phenyl-2-methyl) propyl ester is analyzed yield 100% through GC marker method.
Embodiment 10: synthetic 2 Ethylbutanoic acid-(2-hydroxyl) dodecyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in 2 Ethylbutanoic acid (50mmol), at 0 DEG C, 2-decyl oxyethane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-decyl oxyethane transformation efficiency is 100%, and 2 Ethylbutanoic acid-(2-hydroxyl) dodecyl ester is analyzed yield 100% through GC marker method.
Embodiment 11: synthetic 2 Ethylbutanoic acid-(3-allyloxy-2-hydroxyl) propyl ester
Iron trichloride (1.0mol%) and pyridine (0.5mol%) are dissolved in 2 Ethylbutanoic acid (50mmol), at 0 DEG C, 2-allyloxy methyl oxirane (52.5mmol) is slowly added drop-wise in above-mentioned solution, after at room temperature stirring 10min, be warming up to 50 DEG C of reaction 12h, GC and 1H NMR monitoring are carried out in sampling.2-allyloxy methyl oxirane transformation efficiency is 100%, and 2 Ethylbutanoic acid-(3-allyloxy-2-hydroxyl) propyl ester is analyzed yield 100% through GC marker method.
Claims (7)
1. a method for carboxylic acid and oxirane compound esterification, is characterized in that, adopting iron trichloride and pyridine is catalyzer, concerted catalysis carboxylic acid and oxirane compound esterification at 20-100 DEG C of temperature of reaction.
2. by the method for claim 1, it is characterized in that, the consumption in reacting is respectively 0.05-3 mol% to described catalyzer iron trichloride with pyridine.
3. by the method for claim 1, it is characterized in that, described temperature of reaction is 40-80 DEG C.
4. by the method for claim 1, it is characterized in that, described carboxylic acid is selected from saturated monoprotic acid.
5. by the method for claim 4, it is characterized in that, described saturated monoprotic acid is selected from acetic acid, propionic acid, butyric acid, 2 Methylpropionic acid or 2 Ethylbutanoic acid.
6. by the method for claim 1, it is characterized in that, described oxirane compound is selected from 2-methyl oxirane, 2-chloromethyloxirane, 2-brooethyl oxyethane, 2-allyloxy methyl oxirane, 2-phenyl ethylene oxide, 2-decyl oxyethane or 2,2-dimethyl ethylene oxide.
7. by the arbitrary method described in claim 1 to 6, it is characterized in that, described reaction adopts condition of no solvent.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047038A (en) * | 2018-01-09 | 2018-05-18 | 浙江瑞通光电材料有限公司 | A kind of preparation method of the chloro- propyl ester compounds of acetic acid 2- hydroxyls -3- |
| CN114105799A (en) * | 2022-01-25 | 2022-03-01 | 中山大学附属第七医院(深圳) | Amino lipid and preparation method and application thereof |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1468836A (en) * | 2002-06-11 | 2004-01-21 | ��ʽ�����ձ���ý | Process for producing(methyl) propenoic acid hydroxyalkyl ester |
| CN1993312A (en) * | 2004-08-06 | 2007-07-04 | 株式会社日本触媒 | Processes for producing hydroxyalkyl (meth)acrylate |
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2013
- 2013-04-27 CN CN201310152071.9A patent/CN104119227A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1468836A (en) * | 2002-06-11 | 2004-01-21 | ��ʽ�����ձ���ý | Process for producing(methyl) propenoic acid hydroxyalkyl ester |
| CN1993312A (en) * | 2004-08-06 | 2007-07-04 | 株式会社日本触媒 | Processes for producing hydroxyalkyl (meth)acrylate |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108047038A (en) * | 2018-01-09 | 2018-05-18 | 浙江瑞通光电材料有限公司 | A kind of preparation method of the chloro- propyl ester compounds of acetic acid 2- hydroxyls -3- |
| CN114105799A (en) * | 2022-01-25 | 2022-03-01 | 中山大学附属第七医院(深圳) | Amino lipid and preparation method and application thereof |
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Application publication date: 20141029 |