CN102718655A - Preparation process of DL-2-hydroxy-3-butenoic acid ester - Google Patents
Preparation process of DL-2-hydroxy-3-butenoic acid ester Download PDFInfo
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- CN102718655A CN102718655A CN2012102312352A CN201210231235A CN102718655A CN 102718655 A CN102718655 A CN 102718655A CN 2012102312352 A CN2012102312352 A CN 2012102312352A CN 201210231235 A CN201210231235 A CN 201210231235A CN 102718655 A CN102718655 A CN 102718655A
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Abstract
The invention discloses a preparation process of a DL-2-hydroxy-3-butenoic acid ester represented by a general formula (I). In the general formula (I), R represents methyl, ethyl or n-propyl. The preparation process includes that cheap acrolein and hydrocyanic acid are used as initial raw materials, alcohol ROH is used as a solvent, the mixture is catalyzed by inorganic ammonia salts or organic amine and then subjected to cyaniding reaction to obtain 2-hydroxy-3-butenenitrile, concentrated sulfuric acid is added into the obtained reaction fluid or hydrogen chloride is accessed to the obtained reaction fluid to adjust PH value of solution to 1-6, the solid-liquid separation is performed, under the catalysis of the concentrated sulfuric acid or the hydrogen chloride, the obtained fluid and the alcohol ROH are subjected to hydrolyzing and esterification to achieve one-step preparation of the DL-2-hydroxy-3-butenoic acid ester, and the obtained reactant is subjected to simple purification to obtain highly purified DL-2-hydroxy-3-butenoic acid ester products. The preparation process has the advantages of being short in synthetic route and simple and convenient to operate, and the products are easy to separate, high in purity and yield, low in producing cost and good in application prospect.
Description
Technical field
The invention belongs to chemical field, relate to the preparation technology of one type of chemical.
Background technology
DL-2-hydroxyl-3-crotonate is one type of chemical reagent, fine chemicals, medicine intermediate and material intermediate; Wherein DL-2-hydroxyl-3-M Cr (CAS numbers 5837-73-0) only has imported product (purity>96.0%) to sell at home; But about 2700 yuan of the price of 5 gram products costs an arm and a leg.Do not see at present the preparation technology of this compounds of bibliographical information.
Summary of the invention
In view of this, the object of the present invention is to provide the preparation technology of a kind of DL-2-hydroxyl-3-crotonate, easy and simple to handle, product is easy to separate, purity is high, yield is high, and production cost is low.
For achieving the above object, the present invention provides following technical scheme:
DL-2-hydroxyl-3-crotonate shown in the general formula I, R is methyl, ethyl or n-propyl in the formula:
Its preparation technology comprises the steps:
A.2-hydroxyl-3-crotononitrile is synthetic: propenal and prussic acid are carried out cyanogenation in alcohol roh, under inorganic ammonium salt or the organic amine catalysis, and generation 2-hydroxyl-3-crotononitrile, the gained reaction solution is subsequent use;
Synthesizing of b.DL-2-hydroxyl-3-crotonate: in step a gained reaction solution, add the vitriol oil or feed hydrogen chloride gas with regulator solution pH to 1 ~ 6, solid-liquid separation, gained liquid and alcohol roh are hydrolyzed under the vitriol oil or hydrogen chloride gas catalysis, esterification; Generate DL-2-hydroxyl-3-crotonate; The cooling of gained reaction solution, solid-liquid separation, gained liquid feeds ammonia with regulator solution pH to 6 ~ 10; Solid-liquid separation is collected liquid;
The purifying of c.DL-2-hydroxyl-3-crotonate: the liquid that step b is collected is in 80 ~ 160 ℃ of underpressure distillation of temperature; Collect cut, the gained cut is used organic solvent extraction, organic extract liquid with water washing after; Reclaim organic solvent, promptly get DL-2-hydroxyl-3-crotonate product; Perhaps, the gained cut reclaims alcohol roh, promptly gets DL-2-hydroxyl-3-crotonate product.
Described in step a, b and the c in the alcohol roh definition of R identical with the definition of R in the general formula I.
Preferably, step a carries out cyanogenation temperature-40 ℃ ~ 20 ℃; Step b be hydrolyzed 40 ~ 100 ℃ of temperature, esterification.
Preferably, inorganic ammonium salt described in the step a is volatile salt, bicarbonate of ammonia or ammonium chloride, and said organic amine is triethylamine or tetraethylammonium bromide; Organic solvent described in the step c is methylene dichloride, ETHYLE ACETATE or ether.
Preferably, the weight ratio that feeds intake of propenal described in the step a and prussic acid is 1:0.5 ~ 2, and the consumption of said inorganic ammonium salt or organic amine is 1 ~ 20% of a propenal weight; The consumption of alcohol described in the step b is 1 ~ 5 times of propenal weight, and the consumption of the said catalyzer vitriol oil or hydrogen chloride gas is 2 ~ 4 times of propenal weight.
Preferred, R is that the preparation technology of the DL-2-hydroxyl-3-crotonate of methyl comprises the steps:
A.2-hydroxyl-3-crotononitrile is synthetic: propenal and prussic acid in methyl alcohol, under the triethylamine catalysis, ℃ are carried out cyanogenation in temperature-20, and generation 2-hydroxyl-3-crotononitrile, the gained reaction solution is subsequent use; The weight ratio that feeds intake of said propenal and prussic acid is 1:0.8, and the consumption of said triethylamine is 7% of a propenal weight;
Synthesizing of b.DL-2-hydroxyl-3-crotonate: in step a gained reaction solution, add the vitriol oil with regulator solution pH to 4, solid-liquid separation, gained liquid and methyl alcohol are under sulphuric acid catalysis; In 60 ℃ of temperature be hydrolyzed, esterification, generate DL-2-hydroxyl-3-crotonate, the cooling of gained reaction solution; Solid-liquid separation; Gained liquid feeds ammonia with regulator solution pH to 8, and solid-liquid separation is collected liquid; The consumption of said methyl alcohol is 1.68 times of propenal weight, and the consumption of the said catalyzer vitriol oil is 3 times of propenal weight;
The purifying of c.DL-2-hydroxyl-3-crotonate: the liquid that step b is collected is collected cut in 120 ℃ of underpressure distillation of temperature, and the gained cut reclaims methyl alcohol for 50 ℃ in temperature, promptly gets DL-2-hydroxyl-3-crotonate product.
Preferred, R is that the preparation technology of the DL-2-hydroxyl-3-crotonate of ethyl comprises the steps:
A.2-hydroxyl-3-crotononitrile is synthetic: propenal and prussic acid in ethanol, under the tetraethylammonium bromide catalysis, ℃ are carried out cyanogenation in temperature-20, and generation 2-hydroxyl-3-crotononitrile, the gained reaction solution is subsequent use; The weight ratio that feeds intake of said propenal and prussic acid is 1:0.8, and the consumption of said tetraethylammonium bromide is 20% of a propenal weight;
Synthesizing of b.DL-2-hydroxyl-3-crotonate: in step a gained reaction solution, add the vitriol oil with regulator solution pH to 5, solid-liquid separation, gained liquid and ethanol are under sulphuric acid catalysis; In 60 ℃ of temperature be hydrolyzed, esterification, generate DL-2-hydroxyl-3-crotonate, the cooling of gained reaction solution; Solid-liquid separation; Gained liquid feeds ammonia with regulator solution pH to 9, and solid-liquid separation is collected liquid; Said consumption of ethanol is 2.5 times of propenal weight, and the consumption of the said catalyzer vitriol oil is 3 times of propenal weight;
The purifying of c.DL-2-hydroxyl-3-crotonate: the liquid that step b is collected is collected cut in 140 ℃ of underpressure distillation of temperature, and the gained cut reclaims ethanol in 60 ℃ of underpressure distillation of temperature, promptly gets DL-2-hydroxyl-3-crotonate product.
Preferred, R is that the preparation technology of the DL-2-hydroxyl-3-crotonate of n-propyl comprises the steps:
A.2-hydroxyl-3-crotononitrile is synthetic: propenal and prussic acid in n-propyl alcohol, under the ammonium chloride catalysis, ℃ are carried out cyanogenation in temperature-20, and generation 2-hydroxyl-3-crotononitrile, the gained reaction solution is subsequent use; The weight ratio that feeds intake of said propenal and prussic acid is 1:0.9, and the consumption of said ammonium chloride is 20% of a propenal weight;
Synthesizing of b.DL-2-hydroxyl-3-crotonate: in step a gained reaction solution, add the vitriol oil with regulator solution pH to 5, solid-liquid separation, gained liquid and n-propyl alcohol are under sulphuric acid catalysis; In 60 ℃ of temperature be hydrolyzed, esterification, generate DL-2-hydroxyl-3-crotonate, the cooling of gained reaction solution; Solid-liquid separation; Gained liquid feeds ammonia with regulator solution pH to 8, and solid-liquid separation is collected liquid; The consumption of said n-propyl alcohol is 2.8 times of propenal weight, and the consumption of the said catalyzer vitriol oil is 3 times of propenal weight;
The purifying of c.DL-2-hydroxyl-3-crotonate: the liquid that step b is collected is collected cut in 160 ℃ of underpressure distillation of temperature, and the gained cut reclaims n-propyl alcohol in 100 ℃ of underpressure distillation of temperature, promptly gets DL-2-hydroxyl-3-crotonate product.
Beneficial effect of the present invention is: the present invention is a starting raw material with the propenal and the prussic acid of cheapness; With the alcohol roh is solvent; Under inorganic ammonium salt or organic amine catalysis, make 2-hydroxyl-3-crotononitrile through the cyaniding addition reaction; The latter need not from reaction solution, to separate, can be directly under the vitriol oil or hydrogen chloride gas catalysis with the alcohol roh effect, make DL-2-hydroxyl-3-crotonate through hydrolysis, one step of esterification; The gained reactant can obtain highly purified DL-2-hydroxyl-3-crotonate product after simple purification.Advantages such as it is short that technology of the present invention has synthetic route, easy and simple to handle, and product is easy to separate, purity is high, yield is high, and production cost is low, application prospect is good.
Embodiment
In order to make the object of the invention, technical scheme and advantage clearer, will carry out detailed description to the preferred embodiments of the present invention below.Should be appreciated that preferred embodiment has been merely explanation the present invention, rather than in order to limit protection scope of the present invention.
The preparation of embodiment 1, DL-2-hydroxyl-3-M Cr
A.2-hydroxyl-3-crotononitrile is synthetic
In the 500ml flask, add 70g methyl alcohol and 7g volatile salt, stir, be cooled to-20 ℃; Add 80g prussic acid; Stir, slowly drip the 100g propenal again, the control drop rate makes reacting liquid temperature remain on-20 ℃ in the dropping process; After dropwising ,-20 ℃ of insulation reaction to reactions finish;
Synthesizing of b.DL-2-hydroxyl-3-M Cr
In step a gained reaction solution, add the vitriol oil, regulator solution pH to 4, suction filtration will be filtrated and 168g methyl alcohol adds in the 1000ml flask; Drip the 300g vitriol oil down in agitation condition again, the control drop rate makes reacting liquid temperature remain on 40 ℃ in the dropping process, after dropwising, and 40 ℃ of insulation reaction; Finish until the reaction of 2-hydroxyl-3-crotononitrile, reaction solution is cooled to suction filtration after the room temperature, in filtrating, feed ammonia; Regulator solution pH to 8, suction filtration is collected filtrating;
The purifying of c.DL-2-hydroxyl-3-M Cr
The filtrating that step b is collected is collected cut in 120 ℃ of vacuum rotary steams, and the gained cut divides three extractions with the 200ml methylene dichloride; Merge organic phase; With three washings of 80g moisture, revolve to steam in 80 ℃ again and remove methylene dichloride, promptly make DL-2-hydroxyl-3-M Cr product; Purity is 96.2%, and yield is 83.2%.
The preparation of embodiment 2, DL-2-hydroxyl-3-M Cr
A.2-hydroxyl-3-crotononitrile is synthetic
In the 500ml flask, add 50g methyl alcohol and 1g bicarbonate of ammonia, stir, be cooled to-40 ℃; Add 50g prussic acid; Stir, slowly drip the 100g propenal again, the control drop rate makes reacting liquid temperature remain on-40 ℃ in the dropping process; After dropwising ,-40 ℃ of insulation reaction to reactions finish;
Synthesizing of b.DL-2-hydroxyl-3-M Cr
In step a gained reaction solution, feed hydrogen chloride gas; Regulator solution pH to 6, suction filtration will be filtrated and 500g methyl alcohol adds in the 1000ml flask; Feed the 200g hydrogen chloride gas down in agitation condition again, the control Ventilation Rate makes reacting liquid temperature remain on 100 ℃ in the venting process; After ventilation finished, 100 ℃ of insulation reaction finished until the reaction of 2-hydroxyl-3-crotononitrile, and reaction solution is cooled to suction filtration after the room temperature, in filtrating, fed ammonia, regulator solution pH to 6, and suction filtration is collected filtrating;
The purifying of c.DL-2-hydroxyl-3-M Cr
The filtrating that step b is collected is collected cut in 150 ℃ of vacuum rotary steams, and the gained cut divides three extractions with the 80ml methylene dichloride; Merge organic phase; With three washings of 50g moisture, revolve to steam in 50 ℃ again and remove methylene dichloride, promptly make DL-2-hydroxyl-3-M Cr product; Purity is 95.3%, and yield is 85.0%.
The preparation of embodiment 3, DL-2-hydroxyl-3-M Cr
A.2-hydroxyl-3-crotononitrile is synthetic
In the 1000ml flask, add 400g methyl alcohol and 20g volatile salt, stir, be cooled to 20 ℃; Add 200g prussic acid; Stir, slowly drip the 100g propenal again, the control drop rate makes reacting liquid temperature remain on 20 ℃ in the dropping process; After dropwising, 20 ℃ of insulation reaction to reactions finish;
Synthesizing of b.DL-2-hydroxyl-3-M Cr
In step a gained reaction solution, feed hydrogen chloride gas; Regulator solution pH to 1, suction filtration will be filtrated and 100g methyl alcohol adds in the 2000ml flask; Feed the 400g hydrogen chloride gas down in agitation condition again, the control Ventilation Rate makes reacting liquid temperature remain on 80 ℃ in the venting process; After ventilation finished, 80 ℃ of insulation reaction finished until the reaction of 2-hydroxyl-3-crotononitrile, and reaction solution is cooled to suction filtration after the room temperature, in filtrating, fed ammonia, regulator solution pH to 10, and suction filtration is collected filtrating;
The purifying of c.DL-2-hydroxyl-3-M Cr
The filtrating that step b is collected is collected cut in 80 ℃ of vacuum rotary steams, and the gained cut divides three extractions with the 380ml ether; Merge organic phase; With three washings of 200g moisture, revolve to steam in 90 ℃ again and remove ether, promptly make DL-2-hydroxyl-3-M Cr product; Purity is 96.8%, and yield is 76.1%.
The preparation of embodiment 4, DL-2-hydroxyl-3-M Cr
A.2-hydroxyl-3-crotononitrile is synthetic
In the 500ml flask, add 70g methyl alcohol and 7g triethylamine, stir, be cooled to-20 ℃; Add 80g prussic acid; Stir, slowly drip the 100g propenal again, the control drop rate makes reacting liquid temperature remain on-20 ℃ in the dropping process; After dropwising ,-20 ℃ of insulation reaction to reactions finish;
Synthesizing of b.DL-2-hydroxyl-3-M Cr
In step a gained reaction solution, add the vitriol oil, regulator solution pH to 4, suction filtration will be filtrated and 168g methyl alcohol adds in the 1000ml flask; Drip the 300g vitriol oil down in agitation condition again, the control drop rate makes reacting liquid temperature remain on 60 ℃ in the dropping process, after dropwising, and 60 ℃ of insulation reaction; Finish until the reaction of 2-hydroxyl-3-crotononitrile, reaction solution is cooled to suction filtration after the room temperature, in filtrating, feed ammonia; Regulator solution pH to 8, suction filtration is collected filtrating;
The purifying of c.DL-2-hydroxyl-3-M Cr
The filtrating that step b is collected is collected cut in 120 ℃ of vacuum rotary steams, and the gained cut is removed methyl alcohol in 50 ℃ of vacuum rotary steams, makes DL-2-hydroxyl-3-M Cr product, and purity is 96.8%, and yield is 88.0%.
The preparation of embodiment 5, DL-2-hydroxyl-3-butenoic acid ethyl
A.2-hydroxyl-3-crotononitrile is synthetic
In the 500ml flask, add 90g ethanol and 20g tetraethylammonium bromide, stir, be cooled to-20 ℃; Add 80g prussic acid; Stir, slowly drip the 100g propenal again, the control drop rate makes reacting liquid temperature remain on-20 ℃ in the dropping process; After dropwising ,-20 ℃ of insulation reaction to reactions finish;
Synthesizing of b.DL-2-hydroxyl-3-butenoic acid ethyl
In step a gained reaction solution, add the vitriol oil, regulator solution pH to 5, suction filtration will be filtrated and 250g ethanol adds in the 1000ml flask; Drip the 300g vitriol oil down in agitation condition again, the control drop rate makes reacting liquid temperature remain on 60 ℃ in the dropping process, after dropwising, and 60 ℃ of insulation reaction; Finish until the reaction of 2-hydroxyl-3-crotononitrile, reaction solution is cooled to suction filtration after the room temperature, in filtrating, feed ammonia; Regulator solution pH to 9, suction filtration is collected filtrating;
The purifying of c.DL-2-hydroxyl-3-butenoic acid ethyl
The filtrating that step b is collected is collected cut in 140 ℃ of vacuum rotary steams, and the gained cut is removed ethanol in 60 ℃ of vacuum rotary steams, makes DL-2-hydroxyl-3-butenoic acid ethyl product, and purity is 93.7%, and yield is 78.4%.
The preparation of embodiment 6, DL-2-hydroxyl-3-butenoic acid propyl ester
A.2-hydroxyl-3-crotononitrile is synthetic
In the 500ml flask, add 150g n-propyl alcohol and 20g ammonium chloride, stir, be cooled to-20 ℃; Add 90g prussic acid; Stir, slowly drip the 100g propenal again, the control drop rate makes reacting liquid temperature remain on-20 ℃ in the dropping process; After dropwising ,-20 ℃ of insulation reaction to reactions finish;
Synthesizing of b.DL-2-hydroxyl-3-butenoic acid propyl ester
In step a gained reaction solution, add the vitriol oil, regulator solution pH to 5, suction filtration will be filtrated and the 280g n-propyl alcohol adds in the 1000ml flask; Drip the 300g vitriol oil down in agitation condition again, the control drop rate makes reacting liquid temperature remain on 60 ℃ in the dropping process, after dropwising, and 60 ℃ of insulation reaction; Finish until the reaction of 2-hydroxyl-3-crotononitrile, reaction solution is cooled to suction filtration after the room temperature, in filtrating, feed ammonia; Regulator solution pH to 8, suction filtration is collected filtrating;
The purifying of c.DL-2-hydroxyl-3-butenoic acid propyl ester
The filtrating that step b is collected is collected cut in 160 ℃ of vacuum rotary steams, and the gained cut is removed n-propyl alcohol in 100 ℃ of vacuum rotary steams, makes DL-2-hydroxyl-3-butenoic acid propyl ester product, and purity is 94.8%, and yield is 76.6%.
Claims (7)
1. the preparation technology of the hydroxyl of the DL-2-shown in the general formula I-3-crotonate, R is methyl, ethyl or n-propyl in the formula,
It is characterized in that said preparation technology comprises the steps:
A.2-hydroxyl-3-crotononitrile is synthetic: propenal and prussic acid are carried out cyanogenation in alcohol roh, under inorganic ammonium salt or the organic amine catalysis, and generation 2-hydroxyl-3-crotononitrile, the gained reaction solution is subsequent use;
Synthesizing of b.DL-2-hydroxyl-3-crotonate: in step a gained reaction solution, add the vitriol oil or feed hydrogen chloride gas with regulator solution pH to 1 ~ 6, solid-liquid separation, gained liquid and alcohol roh are hydrolyzed under the vitriol oil or hydrogen chloride gas catalysis, esterification; Generate DL-2-hydroxyl-3-crotonate; The cooling of gained reaction solution, solid-liquid separation, gained liquid feeds ammonia with regulator solution pH to 6 ~ 10; Solid-liquid separation is collected liquid;
The purifying of c.DL-2-hydroxyl-3-crotonate: the liquid that step b is collected is in 80 ~ 160 ℃ of underpressure distillation of temperature; Collect cut, the gained cut is used organic solvent extraction, organic extract liquid with water washing after; Reclaim organic solvent, promptly get DL-2-hydroxyl-3-crotonate product; Perhaps, the gained cut reclaims alcohol roh, promptly gets DL-2-hydroxyl-3-crotonate product;
Described in step a, b and the c in the alcohol roh definition of R identical with the definition of R in the general formula I.
2. the preparation technology of DL-2-hydroxyl according to claim 1-3-crotonate is characterized in that, step a carries out cyanogenation temperature-40 ℃ ~ 20 ℃; Step b be hydrolyzed 40 ~ 100 ℃ of temperature, esterification.
3. the preparation technology of DL-2-hydroxyl according to claim 2-3-crotonate is characterized in that inorganic ammonium salt described in the step a is volatile salt, bicarbonate of ammonia or ammonium chloride, and said organic amine is triethylamine or tetraethylammonium bromide; Organic solvent described in the step c is methylene dichloride, ETHYLE ACETATE or ether.
4. the preparation technology of DL-2-hydroxyl according to claim 3-3-crotonate is characterized in that, the weight ratio that feeds intake of propenal described in the step a and prussic acid is 1:0.5 ~ 2, and the consumption of said inorganic ammonium salt or organic amine is 1 ~ 20% of a propenal weight; The consumption of alcohol roh described in the step b is 1 ~ 5 times of propenal weight, and the consumption of the said catalyzer vitriol oil or hydrogen chloride gas is 2 ~ 4 times of propenal weight.
5. the preparation technology of DL-2-hydroxyl according to claim 4-3-crotonate is characterized in that, R is that the preparation technology of the DL-2-hydroxyl-3-crotonate of methyl comprises the steps:
A.2-hydroxyl-3-crotononitrile is synthetic: propenal and prussic acid in methyl alcohol, under the triethylamine catalysis, ℃ are carried out cyanogenation in temperature-20, and generation 2-hydroxyl-3-crotononitrile, the gained reaction solution is subsequent use; The weight ratio that feeds intake of said propenal and prussic acid is 1:0.8, and the consumption of said triethylamine is 7% of a propenal weight;
Synthesizing of b.DL-2-hydroxyl-3-crotonate: in step a gained reaction solution, add the vitriol oil with regulator solution pH to 4, solid-liquid separation, gained liquid and methyl alcohol are under sulphuric acid catalysis; In 60 ℃ of temperature be hydrolyzed, esterification, generate DL-2-hydroxyl-3-crotonate, the cooling of gained reaction solution; Solid-liquid separation; Gained liquid feeds ammonia with regulator solution pH to 8, and solid-liquid separation is collected liquid; The consumption of said methyl alcohol is 1.68 times of propenal weight, and the consumption of the said catalyzer vitriol oil is 3 times of propenal weight;
The purifying of c.DL-2-hydroxyl-3-crotonate: the liquid that step b is collected is collected cut in 120 ℃ of underpressure distillation of temperature, and the gained cut reclaims methyl alcohol in 50 ℃ of underpressure distillation of temperature, promptly gets DL-2-hydroxyl-3-crotonate product.
6. the preparation technology of DL-2-hydroxyl according to claim 4-3-crotonate is characterized in that, R is that the preparation technology of the DL-2-hydroxyl-3-crotonate of ethyl comprises the steps:
A.2-hydroxyl-3-crotononitrile is synthetic: propenal and prussic acid in ethanol, under the tetraethylammonium bromide catalysis, ℃ are carried out cyanogenation in temperature-20, and generation 2-hydroxyl-3-crotononitrile, the gained reaction solution is subsequent use; The weight ratio that feeds intake of said propenal and prussic acid is 1:0.8, and the consumption of said tetraethylammonium bromide is 20% of a propenal weight;
Synthesizing of b.DL-2-hydroxyl-3-crotonate: in step a gained reaction solution, add the vitriol oil with regulator solution pH to 5, solid-liquid separation, gained liquid and ethanol are under sulphuric acid catalysis; In 60 ℃ of temperature be hydrolyzed, esterification, generate DL-2-hydroxyl-3-crotonate, the cooling of gained reaction solution; Solid-liquid separation; Gained liquid feeds ammonia with regulator solution pH to 9, and solid-liquid separation is collected liquid; Said consumption of ethanol is 2.5 times of propenal weight, and the consumption of the said catalyzer vitriol oil is 3 times of propenal weight;
The purifying of c.DL-2-hydroxyl-3-crotonate: the liquid that step b is collected is collected cut in 140 ℃ of underpressure distillation of temperature, and the gained cut reclaims ethanol in 60 ℃ of underpressure distillation of temperature, promptly gets DL-2-hydroxyl-3-crotonate product.
7. the preparation technology of DL-2-hydroxyl according to claim 4-3-crotonate is characterized in that, R is that the preparation technology of the DL-2-hydroxyl-3-crotonate of n-propyl comprises the steps:
A.2-hydroxyl-3-crotononitrile is synthetic: propenal and prussic acid in n-propyl alcohol, under the ammonium chloride catalysis, ℃ are carried out cyanogenation in temperature-20, and generation 2-hydroxyl-3-crotononitrile, the gained reaction solution is subsequent use; The weight ratio that feeds intake of said propenal and prussic acid is 1:0.9, and the consumption of said ammonium chloride is 20% of a propenal weight;
Synthesizing of b.DL-2-hydroxyl-3-crotonate: in step a gained reaction solution, add the vitriol oil with regulator solution pH to 5, solid-liquid separation, gained liquid and n-propyl alcohol are under sulphuric acid catalysis; In 60 ℃ of temperature be hydrolyzed, esterification, generate DL-2-hydroxyl-3-crotonate, the cooling of gained reaction solution; Solid-liquid separation; Gained liquid feeds ammonia with regulator solution pH to 8, and solid-liquid separation is collected liquid; The consumption of said n-propyl alcohol is 2.8 times of propenal weight, and the consumption of the said catalyzer vitriol oil is 3 times of propenal weight;
The purifying of c.DL-2-hydroxyl-3-crotonate: the liquid that step b is collected is collected cut in 160 ℃ of underpressure distillation of temperature, and the gained cut reclaims n-propyl alcohol in 100 ℃ of underpressure distillation of temperature, promptly gets DL-2-hydroxyl-3-crotonate product.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106748786A (en) * | 2015-11-24 | 2017-05-31 | 北京利源新赛化工有限公司 | A kind of synthetic method of 3-butenoic acid ester |
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| US20110282075A1 (en) * | 2010-05-14 | 2011-11-17 | Albert-Ludwigs-Universitat Freiburg | Method for preparing vittatalactone |
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| US20110282075A1 (en) * | 2010-05-14 | 2011-11-17 | Albert-Ludwigs-Universitat Freiburg | Method for preparing vittatalactone |
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| CN106748786A (en) * | 2015-11-24 | 2017-05-31 | 北京利源新赛化工有限公司 | A kind of synthetic method of 3-butenoic acid ester |
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