CN103483212A - Synthesis method for O-tert-Butyl-L-threonine tert-butyl ester acetate salt - Google Patents
Synthesis method for O-tert-Butyl-L-threonine tert-butyl ester acetate salt Download PDFInfo
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Abstract
The invention discloses a synthesis method for O-tert-Butyl-L-threonine tert-butyl ester acetate salt. The synthesis method is characterized by taking 1,4-dioxane, L-threonine and isobutene as raw materials, and taking a series solid superacid composite system based on SO4<2-> as a catalyst, as well as being performed in a room-temperature phase. The synthesis method has the advantages of being moderate in reaction conditions, easy to control, few in side reactions, high in product purity; refining for the product is performed by normal-pressure and reduced-pressure vacuum distillation, thus simplifying operation and greatly decreasing energy consumption. The solid product can be obtained by directly using liquid-phase O-tert-Butyl-L-threonine tert-butyl ester acetate salt as the raw material, further dripping the mixture of glacial acetic acid and cyclohexane, and performing cooling crystallization. The operation is simple, convenient and efficient, and the use of an organic volatile solvent is avoided.
Description
Technical field
The invention belongs to technical field of organic chemistry, relate to that to take based on solid super-strong acid series composite solid alkali systems be catalyzer, 1.4 dioxane, L-threonine, iso-butylene is starting raw material, adopt room temperature reaction, air distillation and azeotropic underpressure distillation prepare the solid phase O-tertiary butyl-L-Thr tert-butyl ester acetate.
Background technology
The O-tertiary butyl-L-Thr tert-butyl ester acetate is as the intermediate of important bio-pharmaceuticals.
The synthetic method of the O-tertiary butyl-L-Thr tert-butyl ester can be divided into single stage method and the large class of two step method two according to the difference of reaction raw materials:
Wherein single stage method is with the vitriol oil, 1.4 dioxane, and L-threonine, iso-butylene is that starting raw material is raw material, and single step reaction synthesizes the O-tertiary butyl-L-Thr tert-butyl ester, and reaction formula is as follows:
Two step method is with the trimethyl carbinol, and oxalic acid is starting raw material, and first reaction obtains iso-butylene liquid, and iso-butylene liquid reacts with L-threonine and obtains the O-tertiary butyl-L-Thr tert-butyl ester again, and its reaction formula is as follows:
The method of single step reaction is with the vitriol oil, 1.4 dioxane, and L-threonine, iso-butylene is that starting raw material is raw material, single step reaction synthesizes the O-tertiary butyl-L-Thr tert-butyl ester; Two step reactions are first with the trimethyl carbinol, oxalic acid is starting raw material, first reaction obtains iso-butylene liquid, and liquid iso-butylene reacts with L-threonine and obtains the O-tertiary butyl-L-Thr tert-butyl ester, after the iso-butylene liquid reactions first generated in two step reactions, the L-threonine reaction generates crude product, therefore the by product existed in reaction is more, and reactions steps is loaded down with trivial details, to technologic strict, therefore, single stage method is the current synthetic method generally adopted.From adopting the method preparation of two step method reaction, the by product of reaction is many, poor stability.In single stage method, iso-butylene is constantly passed into to the bottom of reaction solution, utilize special reactor to be reacted, this method is easy and simple to handle, be easy to control, by product is few, but iso-butylene boiling point low (6 ℃), require at airtight pressure vessel: as the tetrafluoroethylene reactor of special function.One step forwarding method have the reaction conditions gentleness, easy to operate, be easy to industrialized advantage.
In single stage method, the building-up reactions of the O-tertiary butyl-L-Thr tert-butyl ester mechanism is that hydroxyl on 3 in L-threonine is replaced and generates the O-tertiary butyl-L-threonine by the tertiary butyl, then continues reaction and generates the O-tertiary butyl-L-Thr tert-butyl ester; Reaction process is as follows:
Simultaneous reactions is attended by addition following side reaction and occurs:
Under the environment that 1) product mixes at 1.4 dioxane and the vitriol oil, portion of product rests on the O-tertiary butyl-L-threonine;
2) the amino acid tert-butyl ester is easily decomposed by acid under certain environment,
Characteristics for this reaction system, development as catalyst system, not only can effectively promote steadily carrying out smoothly of reaction based on solid super-strong acid, reduces the generation of side reaction, and catalyzer itself also have inexpensive, be easy to get, be convenient to the advantage that reclaims and recycle.
Summary of the invention
The object of the invention is to based on solid super-strong acid as catalyst system, effectively promote to reduce the generation of side reaction by steadily carrying out smoothly of reaction; Thereby provide the synthetic method of a kind of O-tertiary butyl-L-Thr tert-butyl ester acetate.
Technical scheme of the present invention:
The synthetic method of a kind of O-tertiary butyl-L-Thr tert-butyl ester acetate, it take 1.4 dioxane, L-threonine and iso-butylene as raw material, based on SO
4 2serial solid super-strong acid compound system be catalyzer, carry out the synthetic method of the O-tertiary butyl-L-Thr tert-butyl ester acetate in the room temperature stage.
Follow these steps to carry out:
A, reaction mass 1.4 dioxane are added in reactor fully and add catalyzer after stirring and dissolving, wherein, catalyzer: the mass ratio of 1.4 dioxane=10-35:100, then add L-threonine, wherein 1.4 dioxane: the mass ratio of L-threonine=10-25:1;
Preferably: the catalyzer add-on is catalyzer: the mass ratio of 1.4 dioxane=20-35:100.
Described catalyzer is: CrSO
4/ ZrO
2series (the pH value 8-9 of its aqueous solution of 10%), and SO
4 2/ MOO
3-TiO
2type; SO
4 2/ TiO
2/ La
3the rare earth solid acid; SO
4 2/ ZrO
2a kind of in/MCM-41 tetra-species complexs systems.
B, temperature of reaction kettle remain on 10 ~ 25 ℃ and start to pass into iso-butylene, iso-butylene wherein: the mass ratio of L-threonine=4-10:1, keeping temperature of reaction is 5-13 10 ℃ of-25 ℃ of values of the pH to system, after system becomes homogeneous phase, reactor is remained on to room temperature, continue to react the pH value 7-9 to system, reaction finishes;
Preferably: 1.4 dioxane: L-threonine: iso-butylene mass ratio=10-20:1:4-7.
After c, reaction finish, filtering separation obtains liquid phase crude product and catalyzer, and crude product proceeds to lower one-step refining, and catalyzer can be recycled 5-10 times, and 2-5 times catalyzer is used without processing direct circulation, and while using for 6-10 times, catalyzer will carry out manipulation of regeneration.
Described synthetic method divides three steps to carry out, and at first, at 1.4 dioxane and L-threonine, is being less than under 25 ℃ and is reacting 3-7 hours; Secondly, after the reaction of system finishes, at pressure, be under 0.05MPa, temperature passes into iso-butylene at 17 ~ 25 ℃, ventilation continuously in first 12 hours, latter 48 hours, be interrupted ventilation, react 60 hours with interior end, finally, after system is static, the pH value is down to 7-8, removes by filter catalyzer and obtains crude product.
The process for purification of d, described crude product is: crude product is extracted, crude product divides 3 times and adds, carry out the washing stage, crude product in water washing process each time: the mass ratio=1:5 of water-10, then utilize hexanaphthene to be extracted, then carry out air distillation and underpressure distillation two portions, the air distillation temperature is at 80-100 ℃, vacuum distillation temperature, at 45-85 ℃, makes system remain the system boiling state in vacuum distillation process.
At first utilize hexanaphthene and distilled water to carry out respectively thick product centrifugal, after extraction, carry out atmospheric distillation and underpressure distillation two portions, underpressure distillation is that vacuum tightness is at-0.075 arrive-0.09MPa, 45-80 ℃ of distillation temperatures, make the O-tertiary butyl-L-Thr tert-butyl ester after underpressure distillation.
The solid preparation method of e, the described O-tertiary butyl-L-Thr tert-butyl ester acetate: directly take after making with extra care the liquid phase O-tertiary butyl-the L-Thr tert-butyl ester is raw material, add by hexanaphthene and Glacial acetic acid mixing solutions and dripped, the mass ratio of hexanaphthene and Glacial acetic acid=1-5:1 in mixing solutions wherein, the O-tertiary butyl-L-Thr tert-butyl ester: the mass ratio of hexanaphthene and Glacial acetic acid mixed solution=5-10:1, crystallisation by cooling obtains the water content mass percent lower than 5% solid product.
The regeneration of f, described catalyzer: catalyzer is washed successively, and each deionized water consumption is 2-8 times of volumes of catalyzer, after washing 1-5 times, with chloroform, wash again, each chloroform: catalyst quality ratio=2-4:1, wash 1-5 times, finally in 90-120 ℃ of lower vacuum-dryings 8-18 hours.
The present invention is based on SO
4 2serial solid super-strong acid compound system be catalyzer, the synthetic method of the O-tertiary butyl-L-Thr tert-butyl ester acetate is carried out respectively in reaction in the room temperature stage, in synthetic method the pH value of reaction system be easy to regulate and control, the reaction conditions gentleness.Adopted underpressure distillation to crude product is refining, not only shortened the operating time, also facilitated actual behaviour's body.Make this synthetic method have that the reaction times is short, selectivity is high, productive rate is high, product purity is high, energy consumption is low, catalyzer can be recycled, without the characteristics of using the volatile organic solvent.
To refining employing normal pressure and the reduced vacuum distillation of product, not only simplified operation, also greatly reduce energy consumption.Can be directly with the liquid phase O-tertiary butyl-L-threonine tert-butyl ester raw material, drip the mixture of glacial acetic acid and hexanaphthene through a step, the solid product obtained after crystallisation by cooling, simple to operation, convenient, efficiently, and avoided use volatile organic solvent.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail; it is important to point out; following embodiment is only for the present invention is described further; can not be interpreted as limiting the scope of the invention; affiliated art skilled staff is according to the foregoing invention content; the present invention is made to some nonessential improvement and adjustment is specifically implemented, should still belong to protection scope of the present invention.
embodiment 1
The solid O-tertiary butyl-L-Thr tert-butyl ester acetate is synthetic:
Add successively 1.4 dioxane 1kg in reaction flask, add acidity of catalyst SO
4 20.29kg, constantly add L-threonine 0.07kg, open and stir after L-threonine dissolves fully, keep the pH value of system 8.Maintain the temperature at 15 ℃ and start to pass into isobutene gas, ventilation continuously in first 12 hours, latter 48 hours, being interrupted ventilation (maintaining the temperature at 10 ℃-25 ℃) system became the homogeneous phase end, and the usage quantity of iso-butylene is 0.42kg.Remove by filter catalyzer and obtain crude product, crude product adds hexanaphthene to be extracted, deionized water (divide and add for the 4 times) extraction that then adds 4 times of volumes, normal pressure and the underpressure distillation of carrying out thick product obtain the O-tertiary butyl-L-Thr tert-butyl ester liquid, then drip the mixture (hexanaphthene in mixing solutions wherein: the mass ratio=2.1:1 of Glacial acetic acid of glacial acetic acid and hexanaphthene; The O-tertiary butyl-L-Thr tert-butyl ester: the mass ratio=5.35:1 of hexanaphthene and Glacial acetic acid mixed solution), crystallisation by cooling obtains the solid O-tertiary butyl-L-Thr tert-butyl ester acetate 37.5g, purity 95.5.
embodiment 2
The solid O-tertiary butyl-L-Thr tert-butyl ester acetate is synthetic:
Add successively 1.4 dioxane 1kg in reaction flask, add acidity of catalyst SO
4 2/ TiO
2/ La
3rare earth solid acid 0.28kg, constantly add L-threonine 0.09kg, opens and stir after L-threonine dissolves fully, keeps the pH value of system 8.Maintain the temperature at 15 ℃ and start to pass into isobutene gas, ventilation continuously in first 12 hours, latter 48 hours, being interrupted ventilation (maintaining the temperature at 10 ℃-25 ℃) system became the homogeneous phase end, and the usage quantity of iso-butylene is 0.45kg.Remove by filter catalyzer and obtain crude product, crude product adds hexanaphthene to be extracted, deionized water (divide and add for the 6 times) extraction that then adds 6 times of volumes, normal pressure and the underpressure distillation of carrying out thick product obtain the O-tertiary butyl-L-Thr tert-butyl ester liquid, then drip the mixture (hexanaphthene in mixing solutions wherein: the mass ratio=2.1:1 of Glacial acetic acid of glacial acetic acid and hexanaphthene; The O-tertiary butyl-L-Thr tert-butyl ester: the mass ratio=5.35:1 of hexanaphthene and Glacial acetic acid mixed solution), crystallisation by cooling obtains the solid O-tertiary butyl-L-Thr tert-butyl ester acetate 40.10g, purity 96.5.
embodiment 3
The solid O-tertiary butyl-L-Thr tert-butyl ester acetate is synthetic:
Add successively 1.4 dioxane 1kg in reaction flask, add acidity of catalyst CrSO
4/ ZrO
2series 0.26kg, constantly add L-threonine 0.09kg, opens and stir after L-threonine dissolves fully, keeps the pH value of system 8.Maintain the temperature at 15 ℃ and start to pass into isobutene gas, ventilation continuously in first 12 hours, latter 48 hours, being interrupted ventilation (maintaining the temperature at 10 ℃-25 ℃) system became the homogeneous phase end, and the usage quantity of iso-butylene is 0.45kg.Remove by filter catalyzer and obtain crude product, crude product adds hexanaphthene to be extracted, deionized water (divide and add for the 6 times) extraction that then adds 6 times of volumes, normal pressure and the underpressure distillation of carrying out thick product obtain the O-tertiary butyl-L-Thr tert-butyl ester liquid, drip again the mixture (hexanaphthene in mixing solutions wherein: the mass ratio=2.1:1 of Glacial acetic acid of glacial acetic acid and hexanaphthene, the O-tertiary butyl-L-Thr tert-butyl ester: the mass ratio=5.35:1 of hexanaphthene and Glacial acetic acid mixed solution), crystallisation by cooling obtains the solid O-tertiary butyl-L-Thr tert-butyl ester acetate 41.5g, purity 97.8.
embodiment 4
The solid O-tertiary butyl-L-Thr tert-butyl ester acetate is synthetic:
Add successively 1.4 dioxane 1kg in reaction flask, add acidity of catalyst SO
4 2/ MOO
3-TiO
2type 0.26kg, constantly add L-threonine 0.09kg, opens and stir after L-threonine dissolves fully, keeps the pH value of system 8.Maintain the temperature at 15 ℃ and start to pass into isobutene gas, ventilation continuously in first 12 hours, latter 48 hours, being interrupted ventilation (maintaining the temperature at 10 ℃-25 ℃) system became the homogeneous phase end, and the usage quantity of iso-butylene is 0.45kg.Remove by filter catalyzer and obtain crude product, crude product adds hexanaphthene to be extracted, deionized water (divide and add for the 6 times) extraction that then adds 6 times of volumes, normal pressure and the underpressure distillation of carrying out thick product obtain the O-tertiary butyl-L-Thr tert-butyl ester liquid, drip again the mixture (hexanaphthene in mixing solutions wherein: the mass ratio=2.1:1 of Glacial acetic acid of glacial acetic acid and hexanaphthene, the O-tertiary butyl-L-Thr tert-butyl ester: the mass ratio=5.35:1 of hexanaphthene and Glacial acetic acid mixed solution), crystallisation by cooling obtains the solid O-tertiary butyl-L-Thr tert-butyl ester acetate 41.8g, purity 97.6.
embodiment 5
The solid O-tertiary butyl-L-Thr tert-butyl ester acetate is synthetic:
Add successively 1.4 dioxane 1kg in reaction flask, add acidity of catalyst SO
4 2/ ZrO
2/ MCM-41 type 0.26kg, constantly add L-threonine 0.09kg, opens and stir after L-threonine dissolves fully, keeps the pH value of system 8.Maintain the temperature at 15 ℃ and start to pass into isobutene gas, ventilation continuously in first 12 hours, latter 48 hours, being interrupted ventilation (maintaining the temperature at 10 ℃-25 ℃) system became the homogeneous phase end, and the usage quantity of iso-butylene is 0.45kg.Remove by filter catalyzer and obtain crude product, crude product adds hexanaphthene to be extracted, deionized water (divide and add for the 6 times) extraction that then adds 6 times of volumes, normal pressure and the underpressure distillation of carrying out thick product obtain the O-tertiary butyl-L-Thr tert-butyl ester liquid, then drip the mixture (hexanaphthene in mixing solutions wherein: the mass ratio=2.1:1 of Glacial acetic acid of glacial acetic acid and hexanaphthene; The O-tertiary butyl-L-Thr tert-butyl ester: the mass ratio=5.35:1 of hexanaphthene and Glacial acetic acid mixed solution), crystallisation by cooling obtains the solid O-tertiary butyl-L-Thr tert-butyl ester acetate 41.0g, purity 98.0.
embodiment 6
Recycling for the first time of catalyzer:
The catalyzer that filtration obtains, without further processing, is directly used, and reaction conditions is with embodiment 1.Obtain solid contents: the solid O-tertiary butyl-L-Thr tert-butyl ester acetate 41.5g, purity 97.3.
embodiment 7
Recycle for the 5th time of catalyzer:
The catalyzer that filtration obtains, without further processing, is directly used, and reaction conditions is with embodiment 1.Obtain solid contents: the solid O-tertiary butyl-L-Thr tert-butyl ester acetate 37.5g, purity 96.5.
embodiment 8
The regeneration of catalyzer:
Catalyst recirculation is used and to be regenerated in the 6th o'clock, and the catalyzer that filtration is obtained first joins 35 ml deionized waters, fully washs, after repeating this operation 1-5 times.Again catalyzer is joined in 40 ml anhydrous chloroforms to fully washing, after repeating this operation 1-5 times, finally catalyzer is completed to regeneration in 8-18 hours in 105 ℃ of lower vacuum-dryings.
Claims (10)
1. the synthetic method of the O-tertiary butyl-L-Thr tert-butyl ester acetate, is characterized in that it take 1.4 dioxane, L-threonine and iso-butylene as raw material, based on SO
4 2serial solid super-strong acid compound system be catalyzer, carry out the synthetic method of the O-tertiary butyl-L-Thr tert-butyl ester acetate in the room temperature stage.
2. the synthetic method of the O-tertiary butyl-L-Thr tert-butyl ester acetate is characterized in that following these steps to carrying out:
A, reaction mass 1.4 dioxane are added in reactor fully and add catalyzer after stirring and dissolving, wherein, catalyzer: the mass ratio of 1.4 dioxane=10-35:100, then add L-threonine, wherein 1.4 dioxane: the mass ratio of L-threonine=10-25:1;
B, temperature of reaction kettle remain on 10 ~ 25 ℃ and start to pass into iso-butylene, iso-butylene wherein: the mass ratio of L-threonine=4-10:1, keeping temperature of reaction is 5-13 10 ℃ ~ 25 ℃ values of the pH to system, after system becomes homogeneous phase, reactor is remained on to room temperature, continue to react the pH value 7-9 to system, reaction finishes;
After c, reaction finish, filtering separation obtains liquid phase crude product and catalyzer, and crude product proceeds to lower one-step refining, and catalyst recirculation is used 5-10 times, and 2-5 times catalyzer is used without processing direct circulation, and while using for 6-10 times, catalyzer will carry out manipulation of regeneration.
3. the synthetic method of the O-tertiary butyl according to claim 2-L-Thr tert-butyl ester acetate, the process for purification that it is characterized in that described crude product is: crude product is extracted, crude product divides 3 times and adds, carry out the washing stage, crude product in water washing process each time: the mass ratio=1:5 of water-10, then utilize hexanaphthene to be extracted, carry out again air distillation and underpressure distillation, the air distillation temperature is at 80 ~ 100 ℃, vacuum distillation temperature, at 45 ~ 85 ℃, makes system remain the system boiling state during underpressure distillation.
4. according to the synthetic method of the described O-tertiary butyl of claim 2 or 3-L-Thr tert-butyl ester acetate, the process for purification that it is characterized in that described crude product is: at first utilize hexanaphthene and distilled water to carry out respectively thick product centrifugal, after extraction, carry out atmospheric distillation and underpressure distillation two portions, underpressure distillation is that vacuum tightness is at-0.075 arrive-0.09MPa, 45 ~ 80 ℃ of distillation temperatures, make the O-tertiary butyl-L-Thr tert-butyl ester after underpressure distillation.
5. the synthetic method of the O-tertiary butyl according to claim 2-L-Thr tert-butyl ester acetate, the solid preparation method who it is characterized in that the described O-tertiary butyl-L-Thr tert-butyl ester acetate: directly take after making with extra care the liquid phase O-tertiary butyl-the L-Thr tert-butyl ester is raw material, add by hexanaphthene and Glacial acetic acid mixing solutions and dripped, the mass ratio of hexanaphthene and Glacial acetic acid=1-5:1 in mixing solutions wherein, the O-tertiary butyl-L-Thr tert-butyl ester: the mass ratio of hexanaphthene and Glacial acetic acid mixed solution=5-10:1, crystallisation by cooling obtains the water content mass percent lower than 5% solid product.
6. the synthetic method of the O-tertiary butyl according to claim 2-L-Thr tert-butyl ester acetate, is characterized in that described catalyzer is: CrSO
4/ ZrO
2series, and SO
4 2/ MOO
3-TiO
2type; SO
4 2/ TiO
2/ La
3the rare earth solid acid; SO
4 2/ ZrO
2a kind of in/MCM-41 tetra-species complexs systems.
7. the synthetic method of the O-tertiary butyl according to claim 2-L-Thr tert-butyl ester acetate, is characterized in that the catalyzer add-on is catalyzer: the mass ratio of 1.4 dioxane=20-35:100.
8. the synthetic method of the O-tertiary butyl according to claim 2-L-Thr tert-butyl ester acetate, it is characterized in that synthetic with 1.4 dioxane, L-threonine, iso-butylene is starting raw material, 1.4 dioxane: L-threonine: iso-butylene mass ratio=10-20:1:4-7.
9. the synthetic method of the O-tertiary butyl according to claim 2-L-Thr tert-butyl ester acetate, is characterized in that described synthetic method divides three steps to carry out, and at first, at 1.4 dioxane and L-threonine, is being less than under 25 ℃ and reacting 3-7 hours; Secondly, after the reaction of system finishes, at pressure, be under 0.05MPa, temperature passes into iso-butylene at 17 ~ 25 ℃, ventilation continuously in first 12 hours, latter 48 hours, be interrupted ventilation, react 60 hours with interior end, finally, after system is static, the pH value is down to 7-8, removes by filter catalyzer and obtains crude product.
10. the synthetic method of the O-tertiary butyl according to claim 2-L-Thr tert-butyl ester acetate, it is characterized in that the regeneration to described catalyzer: catalyzer is washed successively, each deionized water consumption is 2-8 times of volumes of catalyzer, after washing 1-5 times, with chloroform, wash again, each chloroform: catalyst quality ratio=2-4:1, wash 1-5 times, finally in 90-120 ℃ of lower vacuum-dryings 8-18 hours.
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| CN106478439A (en) * | 2016-10-08 | 2017-03-08 | 珠海市海瑞德生物科技有限公司 | A kind of preparation method of O tert-butyl group L threonine tert-butyl ester |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1041757A (en) * | 1988-10-12 | 1990-05-02 | 吉林大学 | The single stage method of tert-butyl threonine is synthetic |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1041757A (en) * | 1988-10-12 | 1990-05-02 | 吉林大学 | The single stage method of tert-butyl threonine is synthetic |
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| 李群 等: "《绿色化学原理与绿色产品设计》", 31 August 2008 * |
Cited By (2)
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| CN106478439A (en) * | 2016-10-08 | 2017-03-08 | 珠海市海瑞德生物科技有限公司 | A kind of preparation method of O tert-butyl group L threonine tert-butyl ester |
| CN106478439B (en) * | 2016-10-08 | 2018-09-18 | 珠海市海瑞德生物科技有限公司 | A kind of preparation method of O- tertiary butyls-L-threonine tert-butyl ester |
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