CN101100428B - Method for catalytically synthesizing chiral L- or D-diethyl tartrate by using boric acid - Google Patents
Method for catalytically synthesizing chiral L- or D-diethyl tartrate by using boric acid Download PDFInfo
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- CN101100428B CN101100428B CN2007100119237A CN200710011923A CN101100428B CN 101100428 B CN101100428 B CN 101100428B CN 2007100119237 A CN2007100119237 A CN 2007100119237A CN 200710011923 A CN200710011923 A CN 200710011923A CN 101100428 B CN101100428 B CN 101100428B
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Abstract
Synthesis of chiral L-or D-ethyl tartrate by boric acid catalyzing is carried out by mixing chiral L-or D-ethyl tartrate with needed alcohol proportionally, taking carbon tetrachloride as solvent and boric acid as catalyst, oil bathing while heating, controlling temperature, reflux-reacting, washing, drying, reducing pressure while distilling and purifying to obtain final product. It's economical, has better quality and no secondary environmental pollution; it saves energy and decreases discharge.
Description
Technical field
The present invention relates to a kind of method of utilizing boric acid catalysis synthesis of chiral L-or D-diethyl tartrate, particularly relate to a kind of production technology of employing nontoxic, non-corrosive boric acid catalyst catalytically synthesizing chiral (L-or D-) diethyl tartrate.Chirality (L-or D-) diethyl tartrate is widely used in the extraction of stereoselectivity chirality and splits enantiomer of drugs, and it is the raw material that synthesizes important chirality building block chiral alcohol, also can be used as chiral catalyst and is used for asymmetric synthesis.
Background technology
In recent years, along with the development of chemical industry, people how emphasis have been turned to that more effective simulating nature, the synthetic occurring in nature of highly selective exist those have the material of new sp act.One of them very important and dynamic field are exactly the synthetic of chiral material.Chirality is synthetic to have a wide range of applications, but some specific conditions of its reaction needed.In general, reaction system will have the chirality factor, as chiral reactant, chiral reagent, chiral solvent and chiral catalyst etc.Along with the further investigation of chirality synthetic, the preparation of optical activity or chipal compounds occupies more and more important position in medical and agricultural, industry.
The importance of chirality also shows economic aspect.Since nineteen ninety-two, chiral drug market increases always fast, surpasses 1,000 hundred million dollars for the first time in 1999, and the single enantiomer sales amount of medicine reaches 1,150 hundred million dollars, increases by 16% than 1998, accounts for 32% of 3,600 hundred million dollars of world's drug markets.Reached 1,460 hundred million dollars in 2003.In best-selling preceding 100,300, the 500 kind of medicine in the world, the single enantiomer medicine meets or exceeds 50%.Expect 2010, in the chemosynthesis new drug of whole world listing, have 70% to be the single enantiomer medicine approximately.
Chirality (L-or D-) diethyl tartrate is important chirality edge compound, on three-dimensional arrangement, has the optical activity feature, thereby has the function of stereoselectivity and chiral recognition; From structure of functional groups, contain functional groups such as alkyl, hydroxyl and ester, have polarization, induce and multiple molecule such as hydrogen bond between action function.Rely between the multiple molecule reactive force to be used for the extraction of stereoselectivity chirality and split enantiomer of drugs; Rely on the function of stereoselectivity and chiral recognition, it is the raw material of important chirality building block chiral alcohol, also can be used as chiral catalyst and is used for asymmetric synthesis.Chirality (L-or D-) diethyl tartrate is used more and more widely in medical and agricultural, industry.
Summary of the invention
The object of the present invention is to provide a kind of method of utilizing boric acid catalysis synthesis of chiral (L-or D-) diethyl tartrate; the product of producing with this method; quality height, added value height; catalyzer boric acid and solvent tetracol phenixin can reclaim utilization again in technological process simultaneously; this method reaction process zero release can produce environment protection and double benefit economically.
The objective of the invention is to be achieved through the following technical solutions:
Utilize the method for boric acid catalysis synthesis of chiral L-or D-diethyl tartrate, utilize the acid alcohol mechanisms of esterification reaction, at first with chirality L-or D-tartrate and required alcohol mixing, blending ratio is according to the kind difference of synthetic chirality tartrate, and its mol ratio is different; With the tetracol phenixin is solvent, boric acid catalyst, and the oil bath heating, controlled temperature after the back flow reaction, obtains chirality L-or D-diethyl tartrate by washing, drying, underpressure distillation purge process.
The described method of utilizing boric acid catalysis synthesis of chiral L-or D-diethyl tartrate, it adopts nontoxic, non-corrosive boric acid catalyst.
The described method of utilizing boric acid catalysis synthesis of chiral L-or D-diethyl tartrate, it adopts tetracol phenixin to make solvent.
The described method of utilizing boric acid catalysis synthesis of chiral L-or D-diethyl tartrate, its this method catalyzer boric acid and solvent tetracol phenixin in technological process can reclaim again and utilize.
Advantage of the present invention and effect are:
1. present method has proposed chirality (L-or D-) the diethyl tartrate production method of a kind of not only economy but also environmental protection; the quality product height; the added value height; catalyzer boric acid and solvent tetracol phenixin can reclaim utilization again in technological process simultaneously, can bring environment protection and economic benefit bumper harvests to enterprise.
2. employing boric acid catalyst, nontoxic, do not have corrosion, facility investment is reduced, production cost reduces, and whole technology zero release, does not cause secondary pollution, can reach the purpose of energy-saving and emission-reduction.
Description of drawings
Accompanying drawing of the present invention is a technological process block-diagram.
Embodiment
The present invention is described in detail with reference to the accompanying drawings.
1. ultimate principle of the present invention
Utilize the acid alcohol mechanisms of esterification reaction, at first a certain amount of chirality (L-or D-) tartrate and required a kind of alcohol (as ethanol etc.) are mixed that (blending ratio is different according to the kind of synthetic chirality tartrate, its mol ratio is different), with the tetracol phenixin is solvent, boric acid catalyst, oil bath heating, control certain temperature, behind the back flow reaction certain hour, obtain chirality (L-or D-) diethyl tartrate by purge processes such as washing, drying, underpressure distillation.
Concrete chemical equation is as follows:
2. general planning of the present invention
The first step is that a certain amount of chirality (L-or D-) tartrate and required a kind of alcohol (as ethanol etc.) are mixed (blending ratio is different according to the kind of synthetic chirality tartrate, and its mol ratio is different);
Second step was that the adding tetracol phenixin is a solvent, boric acid catalyst;
The 3rd step was the oil bath heating, control certain temperature, back flow reaction certain hour;
The 4th step was that product is washed;
The 5th step was that dry continuation of washed product dewatered;
The 6th step was product to be carried out underpressure distillation obtain chirality (L-or D-) diethyl tartrate.
3. technological method of the present invention
The present invention adopts reflux to distill the esterification dewatering process according to the acid alcohol mechanisms of esterification reaction, and technology is simple, is easy to industrialization.The unconverted tartrate of vinasse is reclaimed, will separate raffinate and concentrate or recycle several times, after boric acid reached capacity, crystallization was reclaimed boric acid and is directly returned technology, and technology does not have discharging, the reaction process zero release.
4. specific embodiment of the present invention
The tartrate of weighing 30g (0.1mol) adds in the there-necked flask, and then measures 58.6ml dehydrated alcohol and 30ml tetracol phenixin and add in the there-necked flask and mix; Taking by weighing 0.5g boric acid adds in the flask; Begin heating, the temperature of control magnetic stirring apparatus is 70 ℃; Add boric acid 0.5g per then half an hour, continue to divide water to be back to (water is on the upper strata in the water trap, and tetracol phenixin is in lower floor) till the no longer water outlet.Then the magnetic agitation actuator temperature is upgraded to 80 ℃, ethanol and tetracol phenixin are steamed, reaction finishes when waiting to no longer include overhead product.Measure water and other product volume.
Pour material in the there-necked flask into graduated cylinder and add isopyknic toluene, slowly pour in the separating funnel, leave standstill after the concussion, after the two-phase static layering, carry out extracting and separating, separatory reclaims toluene, obtains thick product.
Crude product is poured in the Ke Shi matrass, installed reliever, carry out underpressure distillation.Adopt heat collecting type magnetic stirring apparatus (oil bath), the rising gradually of the temperature of oil bath in this process.Probably carried out 1～2 hour, and when no longer including overhead product, stopped underpressure distillation.After cooling, pour overhead product in graduated cylinder reading, and product poured in the Erlenmeyer flask preserve.
Optimum reaction condition, reaction acid-alcohol ratio 5: 1,70 ℃ of temperature of reaction, in 8～9 hours reaction times, catalyst levels is 1/15 of a tartrate quality, the tetracol phenixin volume is half of dehydrated alcohol volume; Esterification yield 96.68%, yield 90%.
Claims (1)
1. utilize the method for boric acid catalysis synthesis of chiral L-or D-diethyl tartrate, it is characterized in that utilizing the acid alcohol mechanisms of esterification reaction, at first with chirality L-or D-tartrate and required alcohol mixing, blending ratio is according to the kind difference of synthetic chirality tartrate, and its mol ratio is different; With the tetracol phenixin is solvent, boric acid catalyst, and the oil bath heating, controlled temperature after the back flow reaction, obtains chirality L-or D-diethyl tartrate by washing, drying, underpressure distillation purge process, and catalyzer boric acid and solvent tetracol phenixin reclaim again and utilize.
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| Application Number | Priority Date | Filing Date | Title |
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| CN2007100119237A CN101100428B (en) | 2007-06-29 | 2007-06-29 | Method for catalytically synthesizing chiral L- or D-diethyl tartrate by using boric acid |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2007100119237A CN101100428B (en) | 2007-06-29 | 2007-06-29 | Method for catalytically synthesizing chiral L- or D-diethyl tartrate by using boric acid |
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| Publication Number | Publication Date |
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| CN101100428A CN101100428A (en) | 2008-01-09 |
| CN101100428B true CN101100428B (en) | 2010-04-14 |
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| CN104003883B (en) * | 2013-02-26 | 2016-08-17 | 东丽精细化工株式会社 | The manufacture method of high-purity dialkyl tartrate |
| CN104926658A (en) * | 2015-04-30 | 2015-09-23 | 东莞波顿香料有限公司 | Preparation technology for catalytically synthetizing L-(+)-diethyl tartrate by using strong acid cation exchange resin as catalyst |
| CN112876363B (en) * | 2021-03-04 | 2022-05-13 | 盘锦洪鼎化工有限公司 | Preparation method of pentaerythritol tetraisooctanoate |
| CN114805064B (en) * | 2022-04-24 | 2023-08-29 | 广西壮族自治区林业科学研究院 | Method for synthesizing alpha-hydroxy carboxylic ester |
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Non-Patent Citations (3)
| Title |
|---|
| 王春芳等.硼酸催化合成水杨酸异丙酯的研究.河北化工 第4期.2001,(第4期),第22-23页. * |
| 陈国斌等.手性选择体 L-酒石酸正己酯的合成,.合成化学Vol.12 第3期.2004,Vol.12(第3期),第207-209页. |
| 陈国斌等.手性选择体 L-酒石酸正己酯的合成,.合成化学Vol.12 第3期.2004,Vol.12(第3期),第207-209页. * |
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