CN117567323A - Preparation method of (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate - Google Patents
Preparation method of (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate Download PDFInfo
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- CN117567323A CN117567323A CN202311411531.5A CN202311411531A CN117567323A CN 117567323 A CN117567323 A CN 117567323A CN 202311411531 A CN202311411531 A CN 202311411531A CN 117567323 A CN117567323 A CN 117567323A
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- C07—ORGANIC CHEMISTRY
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- C07C269/00—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups
- C07C269/04—Preparation of derivatives of carbamic acid, i.e. compounds containing any of the groups, the nitrogen atom not being part of nitro or nitroso groups from amines with formation of carbamate groups
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- C07C227/00—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton
- C07C227/14—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof
- C07C227/18—Preparation of compounds containing amino and carboxyl groups bound to the same carbon skeleton from compounds containing already amino and carboxyl groups or derivatives thereof by reactions involving amino or carboxyl groups, e.g. hydrolysis of esters or amides, by formation of halides, salts or esters
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Abstract
The invention discloses a preparation method of (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate, which comprises the steps of taking L-homoserine as an initiator, and sequentially carrying out steps of haloacylation, amino protection and the like to obtain a final product of (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate. Compared with the prior art, the preparation method of the invention can improve the stability of the intermediate, prolong the shelf life of the intermediate, obviously improve the properties of intermediate products and is beneficial to industrial production.
Description
Technical Field
The invention belongs to the technical field of organic synthesis, and particularly relates to a preparation method for preparing (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate from L-homoserine.
Background
Glufosinate is a high-efficiency low-toxicity biocidal herbicide developed successfully in the 80 s by the Hurst company, is easy to degrade, and belongs to a biological friendly phosphorus-containing herbicide. The quick-acting property of the herbicide is between paraquat and glyphosate, and the herbicide is a nonselective contact herbicide. The glufosinate has long lasting period and broad weed killing spectrum, does not damage the root system of crops in the process, has good safety and quick acting property, and has better preventing and killing effect on some resistant weeds.
Glufosinate is a chiral compound with two optical isomers, L-glufosinate and D-glufosinate. Wherein, the weeding activity of the L-glufosinate is twice that of the racemic DL-glufosinate, and the glufosinate preparation sold in the market at present is generally the racemic DL-glufosinate.
L-glufosinate is also known as arginate-glufosinate, and has the chemical name of 4- [ hydroxy (methyl) phosphono group]L-homoalanine with the formula shown below and the molecular formula of C 5 H 12 NO 4 P, molecular weight 181.1; the glufosinate-ammonium is easy to dissolve in water, is not easy to dissolve in organic solvents, and is stable to light; melting point of 214-216 ℃, CAS number 35597-44-5. The glufosinate-ammonium is an effective body for truly exerting the weeding activity, and has the advantages that the dosage is only 1/2 of that of the traditional glufosinate-ammonium, the environmental pollution is small, and the application cost is low.
CN106083922a discloses a route for the synthesis of arginate, wherein (S) -4-chloro-2- ((ethoxycarbonyl) amino) ethyl butyrate is prepared by adding ethyl (S) - (2-oxotetrahydrofuran-3-yl) carbamate and thionyl chloride, phosgene, triphosgene, trimethylhalosilane to an alcohol.
However, the addition of Lewis acids (e.g., zinc chloride, zinc bromide, boron trifluoride etherate) is required when thionyl chloride and trimethylhalosilane are employed; when phosgene or triphosgene is used, nucleophilic reagents (such as pyridine, triethylamine, N-dimethylformamide, etc.) need to be added.
CN110386882a discloses a method for preparing (S) -4-chloro-2- ((ethoxycarbonyl) amino) ethyl butyrate, which uses (S) - (2-oxo-tetrahydrofuran-3-yl) ethyl carbamate, thionyl chloride and ethanol as raw materials, and separates and purifies the raw materials after reacting at a certain temperature to prepare (S) -4-chloro-2- ((ethoxycarbonyl) amino) ethyl butyrate, wherein the synthesis process is as follows.
However, the ethyl (S) -4-chloro-2- ((ethoxycarbonyl) amino) butyrate prepared under this condition has an impurity in which the protecting group is detached, namely ethyl (S) -4-chloro-2-amino butyrate.
CN114163471a discloses a method of long chain homoserine derivatives, which can be used for the production of L-glufosinate. Wherein when n=1, the raw material homoserine undergoes haloacylation to obtain (S) -4-chloro-2-aminobutyric acid. The halogenating reagent adopted by the method is dihalosulfoxide, phosgene, triphosgene, oxalyl halide and the like, however, the reaction time is long and the reaction time is required to be 8-24 hours.
Disclosure of Invention
In the pesticide preparation process, the purity and the shelf life of the intermediate are also important standards, and the (S) -4-chloro-2-aminobutyric acid ethyl ester intermediate prepared by the haloacylation reaction of L-homoserine in the prior art has poor properties, does not influence the next reaction, but can undergo a large amount of deterioration after long-time storage.
In order to solve the problems, the technical scheme of the invention is to provide a preparation method of (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate, which comprises the following steps:
l-homoserine, ethanol and halogenated reagent are used as raw materials, and the (S) -4-chloro-2-aminobutyric acid ethyl ester can be obtained through reaction at a certain temperature. And (S) -4-chloro-2-aminobutyric acid ethyl ester reacts with an amino protective reagent to obtain (S) -4-chloro-2- ((ethoxycarbonyl) amino) ethyl butyrate.
By adopting the technical scheme, L-homoserine and a chloro reagent react to generate (S) -4-chloro-2-aminobutyric acid ethyl ester, after ethanol is removed, impurities are removed and purified through washing with solvents such as petroleum ether or toluene, then the mixture is neutralized under strong alkali, carbonate is utilized to keep alkaline environment, hydrogen chloride generated by the reaction of (S) -4-chloro-2-aminobutyric acid ethyl ester and methyl chloroformate is removed, and finally the product (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate is obtained through extraction separation for synthesis of L-glufosinate.
The chlorination reaction can be carried out by stirring L-homoserine and a chlorinating agent at a low temperature for a few hours, then heating and reacting for a period of time, and removing ethanol. And in the second step, water is added into a solid product of the chlorination reaction for dissolution, then an acid binding agent is added, the pH is regulated to be alkaline, methyl chloroformate is stirred and dropwise added at a low temperature, after the dropwise addition is finished, the reaction is carried out for a plurality of times, an extractant is added for extraction, an organic phase is combined, the extractant is removed, and the (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate hydrochloride is obtained, wherein the pure product of the target product is colorless transparent liquid.
The process for preparing ethyl (S) -4-chloro-2- ((methoxycarbonyl) amino) butyrate, which is characterized in that the two-step reaction is carried out continuously in one pot.
In general, compared with the prior art, the technical scheme of the invention has the following advantages:
1. after washing treatment of the (S) -4-chloro-2-aminobutyric acid ethyl ester hydrochloride prepared by petroleum ether, toluene, cyclohexane and the like, the property of the intermediate is obviously improved, the purity is slightly improved, but the shelf life is greatly prolonged.
2. The purity of the (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate prepared by the purified (S) -4-chloro-2-amino ethyl butyrate hydrochloride is obviously improved, the properties are also obviously improved, and the color is changed from brown to colorless or light yellow.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention. In addition, the technical features of the embodiments of the present invention described below may be combined with each other as long as they do not collide with each other.
The preparation method of the (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate is mainly realized by the following steps:
l-homoserine, solvent and ethanol are added into a reaction bottle equipped with mechanical stirring, a chloro reagent (which is dissolved in the solvent if triphosgene is selected) is slowly added at low temperature, and the reaction is stirred for 0.5 hour under the temperature condition. After completion, the temperature is raised to continue the reaction for a while. And detecting that the reaction raw materials are consumed by thin-layer chromatography or high performance liquid chromatography, and the reaction reaches the end point. The ethanol was removed and the ethyl (S) -4-chloro-2-aminobutyrate hydrochloride solid was washed with petroleum ether. Adding water for dissolution, then adding an acid binding agent and an amino protecting agent in sequence, adding an extracting agent after the detection reaction is finished, and standing and separating liquid after uniform stirring. The organic phase was concentrated without reduced pressure to give a colorless transparent oily liquid or a pale yellow transparent oily liquid.
The following are examples:
example 1
50g (0.42 mol) of L-homoserine and 350mL (2.1 mol) of ethanol solution (6 mol/L) of hydrogen chloride are added into a 500mL three-neck flask, stirred and mixed, the temperature is raised to 60 ℃, the reaction is kept for 5 hours, the solvent is evaporated after the detection reaction is finished, 100mL of petroleum ether is added for washing and evaporation to dryness, 83.8g (namely (S) -4-chloro-2-aminobutyric acid ethyl ester) of white crystal is obtained, and the yield is 99.3% and the purity is 97.9%. After 60 days of the solid, the assay purity was 97.7%, which remained essentially unchanged.
To the obtained white solid, 200mL of water was added, and the mixture was stirred and dissolved, 63.6g (0.6 mol) of sodium carbonate was added, 71.4g (0.76 mol) of methyl chloroformate was slowly added, the temperature was kept below 5℃and after the dropwise addition was completed, stirring was continued for 1 hour, and the mixture was warmed to room temperature and reacted further for 2 hours, and after the completion of the detection reaction, 100mL of methylene chloride was added, stirred, left to stand for delamination, and the aqueous phase was extracted with 100mL of methylene chloride, and the organic phase was combined and distilled under reduced pressure to obtain 92.3g of colorless oil with a yield of 98.3% and a purity of 99.5%.
Comparative example 1
50g (0.42 mol) of L-homoserine, 350mL (2.1 mol) of ethanol solution (6 mol/L) of hydrogen chloride, stirring and mixing, heating to 60 ℃, preserving heat and reacting for 5 hours, detecting the reaction, and evaporating the solvent to dryness to obtain 84.2g (namely (S) -4-chloro-2-aminobutyric acid ethyl ester) of brown solid, wherein the yield is 99.7%, and the purity is 95.1%. After the solid was left for 60 days, the purity was checked to decrease to 72.4%.
Comparative example 2
50g (0.42 mol) of L-homoserine, 350mL (2.1 mol) of ethanol solution (6 mol/L) of hydrogen chloride, stirring and mixing, heating to 60 ℃, preserving heat and reacting for 5 hours, detecting the reaction, and evaporating the solvent to dryness to obtain 84.2g (namely (S) -4-chloro-2-aminobutyric acid ethyl ester) of brown solid, wherein the yield is 99.7%, and the purity is 95.1%.
To the brown solid obtained, 200mL of water was added, and the mixture was stirred and dissolved, 63.6g (0.6 mol) of sodium carbonate was added, 71.4g (0.76 mol) of methyl chloroformate was slowly added, the temperature was kept below 5℃and after the addition was completed, stirring was continued for 1 hour, the mixture was warmed to room temperature and reacted further for 2 hours, 100mL of methylene chloride was added after the detection reaction was completed, stirring was carried out, the mixture was allowed to stand for delamination, and the aqueous phase was extracted with 100mL of methylene chloride, and the organic phase was combined and distilled under reduced pressure to obtain 92.3g of brown oily substance with a yield of 98.3% and a purity of 95.3%.
Example 2
50g (0.42 mol) of L-homoserine, 120mL of absolute ethyl alcohol and stirring and mixing are added into a 500mL three-neck flask, 200mL of 1, 2-dichloroethane solution of triphosgene (99.7 g,0.34 mol) is slowly added dropwise, the temperature is controlled below 20 ℃, the temperature is raised to 60 ℃, the reaction is kept for 5 hours, after detection, 100mL of toluene is added for washing and drying after the completion of the detection, and white solid (namely (S) -4-chloro-2-aminobutyric acid ethyl ester) is obtained with the yield of 98.5% and the purity of 98.7%. After 60 days of the solid, the assay purity was 98.2%, which remained essentially unchanged.
To the obtained white solid, 200mL of water was added, and the mixture was stirred and dissolved, 100.8g (1.2 mol) of sodium hydrogencarbonate was added, 71.4g (0.76 mol) of methyl chloroformate was slowly added, the temperature was kept below 5℃and after the addition was completed, stirring was continued for 1 hour, and the mixture was warmed to room temperature and reacted for 2 hours, and after the completion of the detection reaction, 100mL of methylene chloride was added, stirred, and allowed to stand for delamination, and the aqueous phase was extracted with 100mL of 1, 2-dichloroethane, and the organic phases were combined and distilled under reduced pressure to give 93.1g of an oil with a yield of 99.2% and a purity of 98.0%.
Example 3
50g (0.42 mol) of L-homoserine and 350mL (2.1 mol) of ethanol solution (6 mol/L) of hydrogen chloride are added into a 500mL three-neck flask, stirred and mixed, the temperature is raised to 60 ℃, the reaction is kept for 5 hours, the solvent is evaporated after the detection reaction is finished, 100mL of toluene is added for washing and evaporation, and white solid (namely (S) -4-chloro-2-aminobutyric acid ethyl ester) is obtained, wherein the yield is 99.2% and the purity is 99.2%. After 60 days of the solid, the assay purity was 98.6%, which remained essentially unchanged.
To the obtained white solid, 200mL of water was added, and the mixture was stirred and dissolved, 63.6g (0.6 mol) of sodium carbonate was added, 71.4g (0.76 mol) of methyl chloroformate was slowly added, the temperature was kept below 5℃and after the dropwise addition was completed, stirring was continued for 1 hour, and the mixture was warmed to room temperature and reacted further for 2 hours, and after the completion of the detection reaction, 100mL of methylene chloride was added, stirred, left to stand for delamination, and the aqueous phase was extracted with 100mL of methylene chloride, and the organic phase was combined and distilled under reduced pressure to obtain 92.3g of colorless oil with a yield of 99.4% and a purity of 98.5%.
Comparative example 3
50g (0.42 mol) of L-homoserine and 350mL (2.1 mol) of ethanol solution (6 mol/L) of hydrogen chloride are added into a 500mL three-neck flask, stirred and mixed, the temperature is raised to 60 ℃, the reaction is kept for 5 hours, the reaction is detected, the solvent is evaporated to dryness after the reaction is finished, 84.2g (namely (S) -4-chloro-2-aminobutyric acid ethyl ester) of brown solid is obtained, the yield is 99.7%, and the purity is 95.3%. After the solid was left for 60 days, the purity was checked to be reduced to 74.3%.
To the brown solid obtained, 200mL of water was added, and the mixture was stirred and dissolved, 63.6g (0.6 mol) of sodium carbonate was added, 71.4g (0.76 mol) of methyl chloroformate was slowly added, the temperature was kept below 5℃and after the addition was completed, stirring was continued for 1 hour, the mixture was warmed to room temperature and reacted further for 2 hours, 100mL of methylene chloride was added after the detection reaction was completed, stirring was carried out, the mixture was allowed to stand for delamination, and the aqueous phase was extracted with 100mL of methylene chloride, and the organic phase was combined and distilled under reduced pressure to obtain 92.3g of brown oily substance with a yield of 97.4% and a purity of 95.5%.
Example 4
50g (0.42 mol) of L-homoserine, 200mL of absolute ethyl alcohol and stirring and mixing are added into a 500mL three-neck flask, 124.9g (1.05 mol) of thionyl chloride is slowly added dropwise, the temperature is controlled below 40 ℃, the temperature is raised to 60 ℃, the temperature is kept for 5 hours for reaction, the reaction is detected, the solvent is evaporated to dryness, 100mL of petroleum ether is added for washing, and the mixture is evaporated to dryness, so that white solid (namely (S) -4-chloro-2-aminobutyric acid ethyl ester) is obtained.
To the obtained white solid, 200mL of water was added, and the mixture was stirred and dissolved, 40g (1.0 mol) of sodium hydroxide was added, 71.4g (0.76 mol) of methyl chloroformate was slowly added, the temperature was kept below 5℃and after the completion of the dropwise addition, stirring was continued for 1 hour, and the mixture was warmed to room temperature and reacted for 2 hours, and after the completion of the detection reaction, 100mL of ethyl acetate was added, stirred, allowed to stand and layer, the aqueous phase was extracted with 100mL of ethyl acetate, and the organic phase was combined and distilled under reduced pressure to give 93.2g of a pale yellow oily substance with a yield of 99.3%.
Example 5
50g (0.42 mol) of L-homoserine and 350mL (2.1 mol) of ethanol solution (6 mol/L) of hydrogen chloride are added into a 500mL three-neck flask, stirred and mixed, the temperature is raised to 60 ℃, the reaction is kept for 5 hours, the solvent is evaporated to dryness after the detection, 100mL of cyclohexane is added for washing, and the mixture is evaporated to dryness to obtain white solid (namely (S) -4-chloro-2-aminobutyric acid ethyl ester).
To the obtained white solid, 200mL of water was added, and the mixture was stirred and dissolved, 121.4g (1.2 mol) of triethylamine was added, 71.4g (0.76 mol) of methyl chloroformate was slowly added, the temperature was kept below 5℃and after the dropwise addition, stirring was continued for 1 hour, and the mixture was warmed to room temperature and reacted further for 2 hours, and after the detection reaction was completed, 100mL of ethyl acetate was added, stirred, left to stand for delamination, and the aqueous phase was extracted with 100mL of ethyl acetate, and the organic phase was combined and distilled under reduced pressure to give 93.3g of a pale yellow oily substance with a yield of 99.4%.
In addition to the specific types of inorganic strong base, carbonate weak base and water used in the above embodiments, other inorganic strong base, carbonate weak base, organic base, water and organic solvent mixed systems may be used as the reaction solvent.
Unless otherwise specified, the various reaction starting materials (e.g., L-homoserine, sodium bicarbonate, triethylamine) in the present invention are commercially available, and the purity is preferably of analytical grade.
It will be readily appreciated by those skilled in the art that the foregoing description is merely a preferred embodiment of the invention and is not intended to limit the invention, but any modifications, equivalents, improvements or alternatives falling within the spirit and principles of the invention are intended to be included within the scope of the invention.
Claims (8)
1. The preparation method of the (S) -4-chloro-2- ((methoxycarbonyl) amino) ethyl butyrate is characterized by comprising the following steps:
the first step, L-homoserine, ethanol and halogenated reagent are taken as raw materials, and the raw materials react at a certain temperature to obtain (S) -4-chloro-2-aminobutyric acid ethyl ester;
secondly, reacting the (S) -4-chloro-2-aminobutyric acid ethyl ester with an amino protecting reagent to obtain the (S) -4-chloro-2- ((ethoxycarbonyl) amino) butyrate, wherein the reaction formula is as follows:
2. the process according to claim 1, wherein the solvent used in the first step is one or more of ethanol, methylene chloride, ethylene dichloride and tetrahydrofuran.
3. The preparation method of claim 1, wherein the chlorinating agent is one or more of thionyl chloride, hydrogen chloride, phosphorus trichloride, triphosgene and oxalyl chloride, and the molar ratio of the chlorinating agent to L-homoserine is 2-4: 1, the chlorination reaction temperature is 50-80 ℃ and the reaction time is 1-3 hours.
4. The process according to claim 1, wherein the crude product obtained after the chlorination reaction is washed with petroleum ether, toluene and cyclohexane to obtain ethyl (S) -4-chloro-2-aminobutyrate.
5. The preparation method according to claim 1, wherein the acid-binding agent used in the first reaction is one or more of inorganic base and organic base such as sodium bicarbonate, sodium carbonate, sodium hydroxide, potassium carbonate, potassium hydroxide, lithium hydroxide or triethylamine.
6. The method of claim 1, wherein the molar ratio of the acid-binding agent to L-homoserine is from 0.5 to 5:1.
7. the method of claim 1, wherein the amino protecting agent is methyl chloroformate and the molar ratio of the amino protecting agent to the ethyl (S) -4-chloro-2-aminobutyrate is 1.0 to 4.5:1.
8. the process according to claim 1, wherein the reaction temperature is 0 to 30℃and the reaction time is 1 to 3 hours.
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