CN106187950A - A kind of control method of the reaction end that DL epoxychloropropane is prepared by chemical resolution dextrorotation epoxychloropropane - Google Patents
A kind of control method of the reaction end that DL epoxychloropropane is prepared by chemical resolution dextrorotation epoxychloropropane Download PDFInfo
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- CN106187950A CN106187950A CN201610503746.3A CN201610503746A CN106187950A CN 106187950 A CN106187950 A CN 106187950A CN 201610503746 A CN201610503746 A CN 201610503746A CN 106187950 A CN106187950 A CN 106187950A
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- epoxychloropropane
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B57/00—Separation of optically-active compounds
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/32—Separation; Purification
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/08—Compounds containing oxirane rings with hydrocarbon radicals, substituted by halogen atoms, nitro radicals or nitroso radicals
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
- C07B2200/00—Indexing scheme relating to specific properties of organic compounds
- C07B2200/07—Optical isomers
Abstract
The invention belongs to the control method of a kind of reaction end that DL epoxychloropropane is prepared dextrorotation epoxychloropropane in the control field of reaction end by chemical resolution.In the presence of a catalyst, DL epoxychloropropane and glacial acetic acid carry out priming reaction under conditions of being passed through air, obtain reactant liquor；Control reacting liquid temperature at 20 25 DEG C, it is slowly added dropwise water to be hydrolyzed reaction, water completion of dropwise addition for the first time carries out insulation reaction, after be slowly added dropwise second time water, then in 20 25 DEG C of insulation reaction, when hydrolysis carry out to the 38th little time, under 20 DEG C of constant temperatures detect reactant liquor rate of specific gravity, every detection in 30 minutes once, when proportion reaches 1.095 1.100g/cm3In the range of be reaction end；The method has the advantages such as easy to detect, quick, low cost, testing result are reliable.
Description
Technical field
The invention belongs to the control field of reaction end, particularly relate to one and DL epoxychloropropane is torn open by chemistry
Divide the control method of the reaction end of preparation dextrorotation epoxychloropropane.
Background technology
The preparation of dextrorotation epoxychloropropane be with DL epoxychloropropane (also known as racemation epoxy chloropropane), water, acetic acid,
Catalyst is that raw material is prepared by resolution reaction, and the response time in production process is fixing 44 hour, but industry metaplasia
Inevitably because the factors such as small environment cause response speed to change in product, cause at resolution reaction at 44 hours
Extent of reaction generation deviation during terminal, in the same response time, often obtains different knots because of small such environmental effects
Really.The reaction of DL epoxychloropropane has exceeded the needs (being commonly called as reacting) of the degree of fractionation, the dextrorotation epoxy now obtained
Chloropropane specific optical rotation is up to standard, but yield index has been substantially reduced；Reaction mass is not reaching to the needs of fractionation degree and (is commonly called as anti-
Should have not been cooked or heated long enough), the product specific optical rotation quality of formation is less than the required standard of+33 °, and the process that needs to do over again forms substantial amounts of material and damages
Lose.Therefore, in actual production, grasp the degree of reaction mass in time, terminate its reaction and carry out next step operation, make reaction substance
Amount reaches optimal, is to determine product dextrorotation epoxychloropropane specific optical rotation quality and the key of yield index.
The most domestic more than 20 manufacturers use chemical resolution method to produce dextrorotation epoxychloropropane, although aborning
Take gas phase process detection endpoint technique, however it is necessary that the tracing detection of the several sample of every batch, waste time and energy, work efficiency
Lowly, often because the continuation that result in again reaction Check-Out Time of 1 hour simultaneously when sample survey is qualified, product yield declines
Problem yet suffers from；Also because the characteristic of feed liquid causes the severe attrition of gas phase instrument, even damage.Though vapor detection method
The most ripe, but apparatus expensive complex operation, it is not suitable with the production needs of tracking and monitoring.Therefore, a kind of reliable, warp is developed
The control method of the reaction end that Ji is suitable for industrialized great production easily is new problem the most urgently to be resolved hurrily.
Summary of the invention
It is an object of the invention to provide one and DL epoxychloropropane is prepared dextrorotation epoxy chloropropionate by chemical resolution
The control method of the reaction end of alkane, the method has the advantages such as easy to detect, quick, low cost, testing result are reliable.
For achieving the above object, the present invention adopts the following technical scheme that DL epoxychloropropane is torn open by one by chemistry
Divide the control method of the reaction end of preparation dextrorotation epoxychloropropane, said method comprising the steps of:
(1) in the presence of a catalyst, DL epoxychloropropane and glacial acetic acid carry out activation instead under conditions of being passed through air
Should, obtain reactant liquor；
(2) controlling reacting liquid temperature at 20-25 DEG C, be slowly added dropwise water and be hydrolyzed reaction, water completion of dropwise addition for the first time is entered
Row insulation reaction, after be slowly added dropwise second time water, then in 20-25 DEG C of insulation reaction, when hydrolysis carry out to the 38th little time
Start, under 20 DEG C of constant temperatures, detect reactant liquor rate of specific gravity, every detection in 30 minutes once, when proportion reaches 1.095-
1.100g/cm3In the range of be reaction end；
In step (1), described catalyst is chirality (R, R)-Salen-Co III catalyst；Described DL epoxy chloropropionate
Alkane is 220:1-1.5 with the weight ratio of glacial acetic acid, and preferred weight ratio is 220:1.25；Described DL epoxychloropropane and catalyst
Weight ratio be 220:5-7, preferred weight ratio is 220:5.94；The temperature of described priming reaction is 10-15 DEG C, and described activation is anti-
The time answered is 5-7 hour, and the preferably response time is 6 hours；In step (2), the time of dropping of described first time water is 1 little
Time interior；The time that described first time water completion of dropwise addition carries out insulation reaction is 1.5-2.5 hour, and the preferably time of insulation reaction is
2 hours；Described DL epoxychloropropane is 220:5-10 with the weight ratio of water for the first time, and preferred weight ratio is 220:6；Described mixed
Rotation epoxychloropropane is 220:20-30 with the weight ratio of second time water, and preferred weight ratio is 220:26；Complete in described step (2)
Also including step (3) after one-tenth, carry out the distillation reaction liquid that reduces pressure immediately, the mixed liquor collecting dextrorotation epoxychloropropane and water is placed in appearance
Standing in device, then separate the dextrorotation epoxychloropropane of lower floor, sample examination product optical rotation >=+33 ° are and reach product matter
Amount required standard；In step (3), described mixed liquor be placed in container stand time be 20-60 minute, preferably stand time
Between be 30 minutes.
The present invention is characterized by and a kind of by chemical resolution prepared by DL epoxychloropropane dextrorotation epoxychloropropane
The control method of reaction end, its principle is that (1) application DL epoxychloropropane occurs selective hydrolysis under catalyst action
Reaction, along with the increase of by-product 3-chlorine-1,2-propylene glycol growing amount causes reactant liquor rate of specific gravity to promote change the most therewith, it is anti-
The rate of specific gravity answering solution is also gradually increased, and when rate of specific gravity reaches required standard, reaction mass reaches optimal degree needs, this
Time immediately carry out decompression distillation, it is thus achieved that quality high-quality, the dextrorotation epoxychloropropane product of stable yield；(2) present invention can in time,
Intuitively and accurately judge that DL epoxychloropropane splits the control of preparation dextrorotation epichlorohydrin reaction terminal, in order to enter in time
The operation of row subsequent processing, makes the extent of reaction reach optimal, it is thus achieved that the dextrorotation epoxychloropropane that Functionality, quality and appealing design, yield index are stable produces
Product；(3) of the present invention is a kind of physical method, and this mensuration control method need not special expensive equipment, is not subject to
The soda acid degree of reactant liquor limits and the impact of testing conditions, is not limited by the time, the shadow of the most examined personnel specialty
Ring, can simple and fast, convenience, intuitively, accurately and reliably reflect the optimal state residing for resolution reaction, it is to avoid subjectivity is recognized
For 44 little the reaction times judge produced errors, provide reliably for the industrialized production of product, economy easily
Detection method.
A kind of controlling party of the reaction end that DL epoxychloropropane is prepared by chemical resolution dextrorotation epoxychloropropane
Method compared with prior art, has the advantages such as easy to detect, quick, low cost, testing result are reliable, is suitable for the big life of industrialization
Produce, will be widely used in control of reaction end point field.
Detailed description of the invention
Below in conjunction with embodiment, the present invention is described further, and embodiment contributes to being more fully understood that the present invention, but
The present invention is not limited only to following embodiment.
Embodiment one
1,220g DL epoxychloropropane is added in 500ml three-necked bottle, be subsequently adding 1.25g glacial acetic acid and 5.94g hands
Property (R, R)-Salen-Co III catalyst, is passed through air-activated reaction 6 hours in 10-15 DEG C, obtains reactant liquor.
2, control reacting liquid temperature at 20-25 DEG C, in 1 hour, be slowly added dropwise 6g water be hydrolyzed reaction, for the first time water
Completion of dropwise addition insulation reaction 2 hours, is then slowly added dropwise second time water 26g, in 20-25 DEG C of insulation reaction, when hydrolysis enters
Walk to the 38th hour start, under 20 DEG C of constant temperatures detect reactant liquor rate of specific gravity, every 30 minutes detection once, when react into
Walk to the 40th little constantly, reactant liquor rate of specific gravity is 1.095g/cm3, reach the control of reaction end point scope of the present invention.
3, carrying out the distillation reaction liquid that reduces pressure immediately, the mixed liquor collecting dextrorotation epoxychloropropane and water is placed in 250ml separatory
Standing 30 minutes in funnel, then separate lower floor DL epoxychloropropane 99g, yield index 45.00%, sample examination product revolves
Luminosity is+33.50 °, is the definite quality standard reaching product optical rotation >=+33 °.
Embodiment two
1,220g DL epoxychloropropane is added in 500ml three-necked bottle, be subsequently adding 1.25g glacial acetic acid and 5.94g hands
Property (R, R)-Salen-Co III catalyst, is passed through air-activated reaction 6 hours in 10-15 DEG C, obtains reactant liquor.
2, control reacting liquid temperature at 20-25 DEG C, in 1 hour, be slowly added dropwise 6g water be hydrolyzed reaction, for the first time water
Completion of dropwise addition insulation reaction 2 hours, is then slowly added dropwise second time water 26g, in 20-25 DEG C of insulation reaction, when hydrolysis enters
Walk to the 38th hour start, under 20 DEG C of constant temperatures detect reactant liquor rate of specific gravity, every 30 minutes detection once, when react into
Walk to the 40.5th little constantly, reactant liquor rate of specific gravity is 1.096g/cm3, reach the control of reaction end point scope of the present invention.
3, carrying out the distillation reaction liquid that reduces pressure immediately, the mixed liquor collecting dextrorotation epoxychloropropane and water is placed in 250ml separatory
Standing 30 minutes in funnel, then separate lower floor DL epoxychloropropane 98.70g, yield index 44.86%, sample examination produces
Product optical rotation is+33.65 °, is the definite quality standard reaching product optical rotation >=+33 °.
Embodiment three
1,220g DL epoxychloropropane is added in 500ml three-necked bottle, be subsequently adding 1.25g glacial acetic acid and 5.94g hands
Property (R, R)-Salen-Co III catalyst, is passed through air-activated reaction 6 hours in 10-15 DEG C, obtains reactant liquor.
2, control reacting liquid temperature at 20-25 DEG C, in 1 hour, be slowly added dropwise 6g water be hydrolyzed reaction, for the first time water
Completion of dropwise addition insulation reaction 2 hours, is then slowly added dropwise second time water 26g, in 20-25 DEG C of insulation reaction, when hydrolysis enters
Walk to the 38th hour start, under 20 DEG C of constant temperatures detect reactant liquor rate of specific gravity, every 30 minutes detection once, when react into
Walk to the 41st little constantly, reactant liquor rate of specific gravity is 1.097g/cm3, reach the control of reaction end point scope of the present invention.
3, carrying out the distillation reaction liquid that reduces pressure immediately, the mixed liquor collecting dextrorotation epoxychloropropane and water is placed in 250ml separatory
Standing 30 minutes in funnel, then separate lower floor DL epoxychloropropane 98.50g, yield index 44.77%, sample examination produces
Product optical rotation is+33.73 °, is the definite quality standard reaching product optical rotation >=+33 °.
Embodiment four
1,220g DL epoxychloropropane is added in 500ml three-necked bottle, be subsequently adding 1.25g glacial acetic acid and 5.94g hands
Property (R, R)-Salen-Co III catalyst, is passed through air-activated reaction 6 hours in 10-15 DEG C, obtains reactant liquor.
2, control reacting liquid temperature at 20-25 DEG C, in 1 hour, be slowly added dropwise 6g water be hydrolyzed reaction, for the first time water
Completion of dropwise addition insulation reaction 2 hours, is then slowly added dropwise second time water 26g, in 20-25 DEG C of insulation reaction, when hydrolysis enters
Walk to the 38th hour start, under 20 DEG C of constant temperatures detect reactant liquor rate of specific gravity, every 30 minutes detection once, when react into
Walk to the 40th little constantly, reactant liquor rate of specific gravity is 1.099g/cm3, reach the control of reaction end point scope of the present invention.
3, carrying out the distillation reaction liquid that reduces pressure immediately, the mixed liquor collecting dextrorotation epoxychloropropane and water is placed in 250ml separatory
Standing 30 minutes in funnel, then separate lower floor DL epoxychloropropane 98.10g, yield index 44.59%, sample examination produces
Product optical rotation is+33.96 °, is the definite quality standard reaching product optical rotation >=+33 °.
Embodiment five
1,220g DL epoxychloropropane is added in 500ml three-necked bottle, be subsequently adding 1.25g glacial acetic acid and 5.94g hands
Property (R, R)-Salen-Co III catalyst, is passed through air-activated reaction 6 hours in 10-15 DEG C, obtains reactant liquor.
2, control reacting liquid temperature at 20-25 DEG C, in 1 hour, be slowly added dropwise 6g water be hydrolyzed reaction, for the first time water
Completion of dropwise addition insulation reaction 2 hours, is then slowly added dropwise second time water 26g, in 20-25 DEG C of insulation reaction, when hydrolysis enters
Walk to the 38th hour start, under 20 DEG C of constant temperatures detect reactant liquor rate of specific gravity, every 30 minutes detection once, when react into
Walk to the 41.5th little constantly, reactant liquor rate of specific gravity is 1.100g/cm3, reach the control of reaction end point scope of the present invention.
3, carrying out the distillation reaction liquid that reduces pressure immediately, the mixed liquor collecting dextrorotation epoxychloropropane and water is placed in 250ml separatory
Standing 30 minutes in funnel, then separate lower floor DL epoxychloropropane 97.90g, yield index 44.50%, sample examination produces
Product optical rotation is+34.06 °, is the definite quality standard reaching product optical rotation >=+33 °.
Claims (6)
1. DL epoxychloropropane is prepared by chemical resolution a control method for the reaction end of dextrorotation epoxychloropropane,
It is characterized in that, said method comprising the steps of:
(1) in the presence of a catalyst, DL epoxychloropropane and glacial acetic acid carry out priming reaction under conditions of being passed through air,
To reactant liquor；
(2) controlling reacting liquid temperature at 20-25 DEG C, be slowly added dropwise water and be hydrolyzed reaction, water completion of dropwise addition for the first time is protected
Temperature reaction, after be slowly added dropwise second time water, then in 20-25 DEG C of insulation reaction, when hydrolysis carry out to the 38th little time,
Reactant liquor rate of specific gravity is detected, every detection in 30 minutes once, when proportion reaches 1.095-1.100g/ under 20 DEG C of constant temperatures
cm3In the range of be reaction end.
The most according to claim 1 a kind of DL epoxychloropropane is prepared dextrorotation epoxychloropropane by chemical resolution
The control method of reaction end, it is characterised in that in step (1), described catalyst is chirality (R, R)-Salen-Co III
Catalyst；Described DL epoxychloropropane is 220:1-1.5 with the weight ratio of glacial acetic acid, and preferred weight ratio is 220:1.25；Institute
The weight ratio stating DL epoxychloropropane and catalyst is 220:5-7, and preferred weight ratio is 220:5.94；Described priming reaction
Temperature is 10-15 DEG C, and the time of described priming reaction is 5-7 hour, and the preferably response time is 6 hours.
The most according to claim 1 a kind of DL epoxychloropropane is prepared dextrorotation epoxychloropropane by chemical resolution
The control method of reaction end, it is characterised in that in step (2), the time of dropping of described first time water is 1 hour in；Institute
State for the first time water completion of dropwise addition carrying out time of insulation reaction is 1.5-2.5 hour, and the preferably time of insulation reaction is 2 hours.
The most according to claim 1 a kind of DL epoxychloropropane is prepared dextrorotation epoxychloropropane by chemical resolution
The control method of reaction end, it is characterised in that described DL epoxychloropropane is 220:5-10 with the weight ratio of water for the first time,
Preferred weight ratio is 220:6；Described DL epoxychloropropane is 220:20-30 with the weight ratio of second time water, preferred weight ratio
For 220:26.
The most according to claim 1 a kind of DL epoxychloropropane is prepared dextrorotation epoxychloropropane by chemical resolution
The control method of reaction end, it is characterised in that also include step (3) after described step (2) completes, carries out decompression immediately and steams
Evaporating reactant liquor, the mixed liquor collecting dextrorotation epoxychloropropane and water is placed in container standing, then separates the dextrorotation epoxy of lower floor
Chloropropane, sample examination product optical rotation >=+33 ° are and reach product quality required standard.
The most according to claim 5 a kind of DL epoxychloropropane is prepared dextrorotation epoxychloropropane by chemical resolution
The control method of reaction end, it is characterised in that in step (3), described mixed liquor be placed in container stand time be 20-
60 minutes, the time preferably stood was 30 minutes.
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| CN201610503746.3A CN106187950A (en) | 2016-06-30 | 2016-06-30 | A kind of control method of the reaction end that DL epoxychloropropane is prepared by chemical resolution dextrorotation epoxychloropropane |
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| CN201610503746.3A CN106187950A (en) | 2016-06-30 | 2016-06-30 | A kind of control method of the reaction end that DL epoxychloropropane is prepared by chemical resolution dextrorotation epoxychloropropane |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115710240A (en) * | 2022-11-01 | 2023-02-24 | 宁夏坤正生物科技有限公司 | Novel catalysis method for L-carnitine raw material S-epichlorohydrin |
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2016
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| JPH08256791A (en) * | 1995-03-17 | 1996-10-08 | Japan Energy Corp | Production of optically active epihalohydrin |
| CN1649861A (en) * | 2002-08-27 | 2005-08-03 | 罗迪亚药业公司 | Kinetics resolution method |
| CN104607250A (en) * | 2015-02-02 | 2015-05-13 | 舒兰市金马化工有限公司 | Polyhedral oligomeric silsesquioxane dendritic macromolecule catalyst and application thereof |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115710240A (en) * | 2022-11-01 | 2023-02-24 | 宁夏坤正生物科技有限公司 | Novel catalysis method for L-carnitine raw material S-epichlorohydrin |
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