CN1275926C - Alpha-nalogenated propanoic acid with optical activity and its intermediate preparing method - Google Patents
Alpha-nalogenated propanoic acid with optical activity and its intermediate preparing method Download PDFInfo
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Abstract
The present invention relates to a method for preparing alpha-halogenating propionic acid with optical activity and an intermediate body of alpha-halogenating propionic acid amine salt. The method begins with a racemic [DL]-alpha-halogenating propionic acid diamine salt, and alpha-halogenating propionic acid or [D]-alpha-halogenating propionic acid is disassembled and prepared by a preferable crystallization method. The method comprising the following steps that a given amount of racemic [DL]-alpha-halogenating propionic acid diamine salt is dissolved in water solution or mixed liquor of water and organic solvent which is codissolved with the water; the solution temperature is controlled between-15 DEG C and 65 DEG C, excessive [L]-alpha-halogenating propionic acid diamine salt or [D]-alpha-halogenating propionic acid diamine salt with optical activity is added, and thus, the alpha-halogenating propionic acid amine salt with the same optical activity is prepared after certain time; the prepared alpha-halogenating propionic acid amine salt with optical activity is refined to prepare alpha-halogenating propionic acid with optical activity. The method enables the product optical purity to achieve more than 95%, the cost of the technical line is low, and the product is easy to produce in industrialization.
Description
One, technical field
(simple and convenient process for preparing of α-halopropionic) especially splits with the preferential crystallization method and obtains alpha-halogen propionic acid amine salt, and re-refining obtains the method for optically active alpha-halogen propionic acid to the present invention relates to a kind of optically active alpha-halogen propionic acid.
Two, background technology
Having optically active alpha-halogen propionic acid is the important intermediate of making plant protection product and medicine, and people are seeking the method for this optically active alpha-halogen propionic acid of a kind of reasonable preparation always for many years.
By JP57/094295, JP62/205797, JP61/111699, EP-A196625 is known, can be by the enzyme enantioselectivity racemic alpha-halogen propionic ester that dissociates, obtain optically active alpha-halogen propionic acid, but the productive rate of this method maximum only is 50%, and the enantiomeric purity of the alpha-chloro propionic ester that generates is not high.
U.S. Pat 898972 provides the racemic modification dissociative method of being carried out the alpha-chloro propionic ester by the lipase of column candiyeast.
Racemize alpha-halogen propionic acid can pass through enzyme process selectivity dehalogenation, the D-enantiomorph changes into optical activity lactic acid and optical activity L-halopropanoic acid remains unchanged and separated, also there is the lower defective (biocatalysis of productive rate in this method, D.A.Abramovicz CZ compiles van Nostrand R.New York (1990), common microcosmic biology periodical, 128,1755 (1982)).
European patent EP 257716 discloses a kind of continuation method, D wherein, the alpha-brominated methyl propionate of L-uses as racemic modification, and in two-phase system, lipase by column column candiyeast changes into L-(-)-alpha-brominated methyl propionate, but, in this method, be regardless of dried up hydrolysis products.
S.K.Dahod and P.Sinta-Mangano are in biotechnology, biotechnology, 30 (8), in 995 (1987), described the lipase-catalyzed hydrolysis of L-alpha-chloro methyl propionate in the presence of tetracol phenixin, the shortcoming of this method is, except that using the chlorating solvent, at enantiomeric purity only is 95% time, 30% the low-yield of only having an appointment.
EP-A511526, JP5130881 disclose a kind of in by water and the two-phase system formed with organic solvent with the immiscible ester of water basically, the enzyme solution of racemize α-Lv Bingsuan ester.But this method is very complicated, because organic phase must many times separate, contact with lytic enzyme and circulate, because transform not exclusively, although the reaction times is quite long, also can not get pure enantiomorph product, is not suitable for applicable industry production.
As seen from the above, the method for splitting of racemize alpha-halogen propionic acid mainly is an enzyme process, and this technology investment is big, cost is high, industrialization difficulty height.
The additive method of preparation tool optical activity alpha-halopropanoic acid, by EP-A401104, JP6I/057534, JP02/104560 knows, can prepare optical activity alpha-halopropanoic acid ester by the halogenation of optical activity lactate, the refining then optical activity alpha-halopropanoic acid that obtains.But the method that is to use optical activity lactic acid to prepare optical activity alpha-halopropanoic acid can only obtain a kind of optical activity alpha-halopropanoic acid of configuration.
DE19951001452 in addition; US5763659; EP0804405; CN1168130 and CN1069630B; JP105122717, WO9622272 relate to a kind of method for preparing optically active alpha-halogen propionic acid, wherein corresponding optically active alpha-halogen alkyl propionates under heating up, in the acyl group shift reaction with a kind of carboxylic acid reaction; generate optically active alpha-halogen propionic acid and alkyl carboxylates, optically active alpha-halogen propionic acid that will generate is then separated from reaction mixture.Though this method can make the alpha-halogen propionic acid of high-optical-purity, productive rate is also higher, severe reaction conditions, step complexity.
On the contrary, preferential crystallization method (English name is the preferential crystallizationprocedure) does not need expensive resolution reagent, the advantage of this optical resolution is as long as a spot of crystal seed just can be finished the fractionation to racemic mixture, yet the preferential crystallization method to racemize alpha-halogen propionic acid splits, and report is not arranged so far.
According to the Shandong chemical industry, 2000,29 3 phases of volume, the 18-20 page or leaf, the optical resolution report of racemic mixture: the preferential crystallization method is a kind of not only suitable prepared in laboratory but also a suitable industrial reasonable method in the optical resolution, and in general, each operation is 10%～30% to the racemic modification supersaturation rate of splitting out partly in the solution before splitting in the preferential crystallization method resolution cycle, to the racemic modification of adding, the rate of splitting out is about 100%.
Three, summary of the invention
The objective of the invention is to overcome deficiency on the prior art, a kind of short-cut method for preparing the alpha-halogen propionic acid of high-optical-purity is provided.The present invention adopts following technical scheme for this reason:
A kind of preparation has the method for optically active alpha-halogen propionic acid, begin by racemic [DL]-alpha-halogen propionic acid two amine salt, split the method that the preferential crystallization method prepares [L]-alpha-halogen propionic acid or [D]-alpha-halogen propionic acid by compound, described method comprises following sequential steps:
A) preparation racemize [DL]-alpha-halogen propionic acid two amine salt, general formula is as follows:
Wherein R1 and R2 respectively are C1-C8 alkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl, one or more halogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxyl group, C1-C4 acyloxy or C1-C4 esterifying carboxyl group inert substituents of being selected from can also be arranged as required, perhaps they are interconnected to form a ring that 4-7 ring atom arranged, and R1 and R2 also can be hydrogen; R3 and R4 respectively are C1-C8 alkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl, one or more halogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxyl group, C1-C4 acyloxy or C1-C4 esterifying carboxyl group inert substituents of being selected from can also be arranged as required, perhaps they are interconnected to form a ring that 4-7 ring atom arranged, and R3 and R4 also can be hydrogen;
N is the integer of 1-6;
X is a halogen, and halogen atom is fluorine or chlorine or bromine or iodine;
Above-mentioned Ia and Ib the aqueous solution or water and with the mixed solution of the codissolved organic solvent of water in dissolve; In solution, the mass percent concentration of racemize alpha-halogen propionic acid amine salt is controlled at 2%-100%, and the temperature of solution is controlled at-15 ℃-65 ℃;
B) broadcast into L or D crystal seed, gather in the crops solid behind the certain hour, obtain optical activity alpha-halopropanoic acid amine salt;
Broadcast the step of L or D crystal seed and also can carry out in a), during preparation racemize alpha-halogen propionic acid amine salt, make L-alpha-halogen propionic acid or D-alpha-halogen propionic acid excessive, effect also is equal to;
C) optical activity alpha-halopropanoic acid amine salt warp that obtains is made optical activity alpha-halopropanoic acid.
Described preparation has the method for optically active alpha-halogen propionic acid, and step c) is with optical activity alpha-halopropanoic acid amine salt acidifying; The acid that will obtain with extraction agent extracts from alpha-halogen propionic acid amine salt solution again, and removes extraction agent, obtains optical activity alpha-halopropanoic acid.The acid that described acidifying is adopted is inorganic acid aqueous solution, and the acid that will obtain with extraction agent extracts from alpha-halogen propionic acid amine salt inorganic acid aqueous solution again; Mineral acid described here is preferentially selected hydrochloric acid or sulfuric acid for use.
Described extraction agent can be an one of the following: 1. benzene and derivative thereof; 2. ketone; 3. ether; 4. halogenated alkane; 5. ester.
Concrete used extraction agent can be the arbitrary combination of one of the following or following reagent: 1. 2. 3. 4. 5. ethyl acetate of tetracol phenixin of ether of acetone of toluene.
Preparation has the method for optically active alpha-chloro propionic acid: begun by racemic [DL]-alpha-chloro propionic acid two amine salt, split preparation [L]-alpha-chloro propionic acid or [D]-alpha-chloro propionic acid by the preferential crystallization method.Preferred [the DL]-alpha-chloro propionic acid ethylenediamine salt of used racemic [DL]-alpha-chloro propionic acid two amine salt, promptly the n among general formula I a and the Ib is 2, and X is Cl, and R1, R2, R3, R4 are hydrogen.
It is 2 that used racemic [DL]-alpha-chloro propionic acid two amine salt also can be selected the n among general formula I a and the Ib for use, and X is Cl, and R1, R2, R3, R4 are independent separately to be-CH
2CH
3Or-CH
3
Described and the codissolved organic solvent of water refer to non-hydroxyl solvent, or alcohol, can be one of following formulas: 1. 2. 3. 4. DMF solvent of ethanol of methyl alcohol of tetrahydrofuran (THF)
Described preparation has the method for optically active alpha-halogen propionic acid, and the solution temperature optimum control in the described step a) is at 15 ℃-45 ℃.
A kind of preparation has the method for the intermediate alpha-halogen propionic acid amine salt of optically active alpha-halogen propionic acid, begin by racemic [DL]-alpha-halogen propionic acid two amine salt, split the method for preparing [L]-alpha-halogen propionic acid amine salt or [D]-alpha-halogen propionic acid amine salt by the preferential crystallization method, described method comprises following sequential steps:
A) preparation racemize [DL]-alpha-halogen propionic acid two amine salt, general formula is as follows:
Wherein R1 and R2 respectively are C1-C8 alkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl, one or more halogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxyl group, C1-C4 acyloxy or C1-C4 esterifying carboxyl group inert substituents of being selected from can also be arranged as required, perhaps they are interconnected to form a ring that 4-7 ring atom arranged, and R1 and R2 also can be hydrogen; R3 and R4 respectively are hydrogen, C1-C8 alkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl, one or more halogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxyl group, C1-C4 acyloxy or C1-C4 esterifying carboxyl group inert substituents of being selected from can also be arranged as required, perhaps they are interconnected to form a ring that 4-7 ring atom arranged, and R3 and R4 also can be hydrogen;
N is the integer of 1-6;
X is a halogen, and halogen atom is fluorine or chlorine or bromine or iodine;
Above-mentioned Ia and Ib the aqueous solution or water and with the mixed solution of the codissolved organic solvent of water in dissolve; In solution, the mass percent concentration of racemize alpha-halogen propionic acid amine salt is controlled at 2%-100%, and the temperature of solution is controlled at-15 ℃-65 ℃;
B) broadcast into L or D crystal seed, gather in the crops solid behind the certain hour, obtain optical activity alpha-halopropanoic acid amine salt
The present invention has the following advantages with respect to existing:
(1) can obtain the alpha-halogen propionic acid of the high-optical-purity of two kinds of optical configuration, optical purity of products reaches more than 95%, even can reach more than 99%, and total recovery can reach more than 85%.
(2) this technological line cost is low, is easy to industrializing implementation production.
Four, embodiment
Embodiment 1
In the 1000ml beaker, add the 500ml purified water, the adding of 150g alpha-chloro propionic acid ethylenediamine salt is wherein stirred evenly, heating for dissolving between 60 ℃ and 30 ℃ of temperature, is broadcast into optically pure D-alpha-chloro propionic acid ethylenediamine salt an amount of first, cool, separate out D-alpha-chloro propionic acid ethylenediamine salt crystal, filter, vacuum drying weigh 24g.
Embodiment 2
In the 1000ml beaker, the mother liquor that obtains among the embodiment 1 is all added, adding 20g racemize alpha-chloro propionic acid ethylenediamine salt again stirs evenly, heating for dissolving, between 60 ℃ and 30 ℃, broadcast into optically pure L-alpha-chloro propionic acid ethylenediamine salt an amount of, cool, obtain L-alpha-chloro propionic acid ethylenediamine salt 20g.
Embodiment 3
In the 1000ml beaker, the mixed solution that adds 500ml first alcohol and water (1: 2), the adding of 60g alpha-chloro propionic acid ethylenediamine salt is wherein stirred evenly, heating for dissolving, between 30 ℃ and 0 ℃, broadcast into optically pure D-alpha-chloro propionic acid ethylenediamine salt an amount of, cool, get D-alpha-chloro propionic acid ethylenediamine salt.
Embodiment 4
In the 1000ml beaker, the mixed solution that adds 300ml water and tetrahydrofuran (THF) (4: 1), add 30g alpha-chloro propionic acid ethylenediamine salt again, heating for dissolving, between 15 ℃ of temperature and-15 ℃, broadcast an amount of into optically pure D-alpha-chloro propionic acid ethylenediamine salt, cool, obtain D-alpha-chloro propionic acid ethylenediamine salt.
Embodiment 5
In the 50ml beaker, add 50% aqueous hydrochloric acid of 20ml, add D-alpha-chloro propionic acid ethylenediamine salt again, after the dissolving, pour separating funnel into fully; Add the extraction of 200ml toluene again.Get toluene layer, remove solvent toluene, obtain pure alpha-chloro propionic acid, through measuring, be D-alpha-chloro propionic acid, optical purity is 99% (optically-active light-intensity method), and yield is 90%.
Embodiment 6
In the 50ml beaker, add 50% aqueous sulfuric acid of 20ml, add the L-alpha-chloro propionic acid ethylenediamine salt of 20g optical purity 98% again, after the dissolving, pour separating funnel into fully; Add the 200ml carbon tetrachloride extraction again.Get carbon tetrachloride layer, remove solvent, obtain pure alpha-chloro propionic acid, through measuring, be L-alpha-chloro propionic acid, optical purity is 99% (optically-active light-intensity method), and yield is 90%.
Embodiment
In the 1000ml beaker, add 500ml water, add 120g alpha-fluoro propionic acid ethylenediamine salt again, heating for dissolving is broadcast into optically pure D-alpha-fluoro propionic acid ethylenediamine salt between 60 ℃ and 30 ℃ of temperature, cools, and obtains D-alpha-fluoro propionic acid ethylenediamine salt.
Embodiment 8
In the 1000ml beaker, add 500ml water and ethanol (5: 1), add the alpha-brominated propionic acid ethylenediamine salt of 120g again, heating for dissolving, between 60 ℃ and 30 ℃ of temperature, broadcast alpha-brominated propionic acid ethylenediamine salt, cool, obtain the alpha-brominated propionic acid ethylenediamine salt of D-into optically pure D-.
Embodiment 9
In the 1000ml beaker, add 500ml water, add 120g alpha-chloro propionic acid propylene diamine salt (1 again, the 3-propylene diamine), heating for dissolving is broadcast into optically pure D-alpha-chloro propionic acid propylene diamine salt between 60 ℃ and 30 ℃ of temperature, cool, obtain D-alpha-chloro propionic acid propylene diamine salt.
Embodiment 10
In the 1000ml beaker, add 500ml water, add 120g alpha-chloro propionic acid butanediamine salt (1 again, the 4-butanediamine), heating for dissolving is broadcast into optically pure D-alpha-chloro propionic acid butanediamine salt between 60 ℃ and 30 ℃ of temperature, cool, obtain D-alpha-chloro propionic acid butanediamine salt.
Embodiment 11
In the 1000ml beaker, add the mixed solution of 300ml water and DMF (3: 1), with the racemic N of 50g, N, N ', N '-Tetramethyl Ethylene Diamine dichloro-propionic salt adding wherein stirs evenly, heating for dissolving is broadcast into optically pure D-α-N, N between 60 ℃ and 30 ℃ of temperature, N ', N '-Tetramethyl Ethylene Diamine dichloro-propionic salt is an amount of, cools, obtain D-α-N, N, N ', N '-Tetramethyl Ethylene Diamine salt dichloro-propionic salt.
Claims (11)
1. one kind prepares the method with optically active alpha-halogen propionic acid, it is characterized in that beginning by racemic [DL]-alpha-halogen propionic acid two amine salt, split the method for preparing [L]-alpha-halogen propionic acid or [D]-alpha-halogen propionic acid by the preferential crystallization method, described method comprises following sequential steps:
A) racemize [DL]-alpha-halogen propionic acid two amine salt, general formula is as follows:
Wherein R1 and R2 respectively are C1-C8 alkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl, one or more halogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxyl group, C1-C4 acyloxy or C1-C4 esterifying carboxyl group inert substituents of being selected from can also be arranged as required, perhaps they are interconnected to form a ring that 4-7 ring atom arranged, and R1 and R2 also can be hydrogen; R3 and R4 respectively are C1-C8 alkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl, one or more halogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxyl group, C1-C4 acyloxy or C1-C4 esterifying carboxyl group inert substituents of being selected from can also be arranged as required, perhaps they are interconnected to form a ring that 4-7 ring atom arranged, and R3 and R4 also can be hydrogen;
N is the integer of 1-6;
X is a halogen, and halogen atom is fluorine or chlorine or bromine or iodine;
Above-mentioned Ia and Ib the aqueous solution or water and with the mixed solution of the codissolved organic solvent of water in dissolve; In solution, the mass percent concentration of racemize alpha-halogen propionic acid amine salt is controlled at 2%-100%, and the temperature of solution is controlled at-15 ℃-65 ℃;
B) broadcast into L or D crystal seed, gather in the crops solid behind the certain hour, obtain optical activity alpha-halopropanoic acid amine salt;
C) with the optical activity alpha-halopropanoic acid amine salt acidifying that obtains; The acid that will obtain with extraction agent extracts from alpha-halogen propionic acid amine salt solution again, and removes extraction agent, obtains optical activity alpha-halopropanoic acid.
2. preparation as claimed in claim 1 has the method for optically active alpha-halogen propionic acid, it is characterized in that the acid that described acidifying is adopted is inorganic acid aqueous solution, and the acid that will obtain with extraction agent extracts from alpha-halogen propionic acid amine salt inorganic acid aqueous solution again.
3. preparation as claimed in claim 2 has the method for optically active alpha-halogen propionic acid, it is characterized in that described mineral acid can be hydrochloric acid or sulfuric acid.
4. described preparation has the method for optically active alpha-halogen propionic acid as one of claim 1-3, it is characterized in that described extraction agent can be an one of the following:
1. 2. 3. 4. 5. ester of halogenated alkane of ether of ketone of benzene and derivative thereof.
5. described preparation has the method for optically active alpha-halogen propionic acid as one of claim 1-3, it is characterized in that described extraction agent can be the arbitrary combination of one of the following or following reagent:
1. 2. 3. 4. 5. ethyl acetate of tetracol phenixin of ether of acetone of toluene.
6. preparation as claimed in claim 1 has the method for optically active alpha-halogen propionic acid, it is characterized in that being begun by racemic [DL]-alpha-chloro propionic acid two amine salt, splits preparation [L]-alpha-chloro propionic acid or [D]-alpha-chloro propionic acid by the preferential crystallization method.
7. preparation as claimed in claim 6 has the method for optically active alpha-halogen propionic acid, it is characterized in that described racemic [DL]-alpha-chloro propionic acid two amine salt are [DL]-alpha-chloro propionic acid ethylenediamine salt; N among general formula I a and the Ib is 2, and X is Cl, and R1, R2, R3, R4 respectively are-H.
8. preparation as claimed in claim 1 has the method for optically active alpha-halogen propionic acid, it is characterized in that described and the codissolved organic solvent of water are non-hydroxyl solvent, or alcohol.
9. preparation as claimed in claim 8 has the method for optically active alpha-halogen propionic acid, it is characterized in that described and the codissolved organic solvent of water are one of following formula:
1. 2. 3. 4. DMF solvent of ethanol of methyl alcohol of tetrahydrofuran (THF).
10. preparation as claimed in claim 1 has the method for optically active alpha-halogen propionic acid, it is characterized in that the solution temperature in the described step (a) is controlled at 15 ℃-45 ℃.
11. one kind prepares the intermediate with optically active alpha-halogen propionic acid as claimed in claim 1 and has optical activity alpha-halopropanoic acid amine salt method, it is characterized in that beginning by racemic [DL]-alpha-halogen propionic acid two amine salt, split the method for preparing [L]-alpha-halogen propionic acid amine salt or [D]-alpha-halogen propionic acid amine salt by the preferential crystallization method, described method comprises following sequential steps:
(a) racemize [DL]-alpha-halogen propionic acid two amine salt, general formula is as follows:
Wherein R1 and R2 respectively are C1-C8 alkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl, one or more halogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxyl group, C1-C4 acyloxy or C1-C4 esterifying carboxyl group inert substituents of being selected from can also be arranged as required, perhaps they are interconnected to form a ring that 4-7 ring atom arranged, and R1 and R2 can be hydrogen; R3 and R4 respectively are C1-C8 alkyl, C3-C8 cycloalkyl or C3-C8 cycloalkyl, C1-C8 alkyl, one or more halogen, hydroxyl, C1-C4 alkyl, C1-C4 alkoxyl group, C1-C4 acyloxy or C1-C4 esterifying carboxyl group inert substituents of being selected from can also be arranged as required, perhaps they are interconnected to form a ring that 4-7 ring atom arranged, and R3 and R4 can be hydrogen;
N is the integer of 1-6;
X is a halogen, and halogen atom is fluorine or chlorine or bromine or iodine;
Above-mentioned Ia and Ib the aqueous solution or water and with the mixed solution of the codissolved organic solvent of water in dissolve; In solution, the mass percent concentration of racemize alpha-halogen propionic acid amine salt is controlled at 2%-100%, and the temperature of solution is controlled at-15 ℃-65 ℃;
B) broadcast into L or D crystal seed, gather in the crops solid behind the certain hour, obtain optical activity alpha-halopropanoic acid amine salt.
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Application publication date: 20050216 Assignee: Jining Senli Biological Technology Co., Ltd. Assignor: Zhou Wei Contract record no.: 2014370000123 Denomination of invention: Alpha-nalogenated propanoic acid with optical activity and its intermediate preparing method Granted publication date: 20060920 License type: Exclusive License Record date: 20140716 |
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