CN107337603A - The preparation method of L (+) ethyl tartrate - Google Patents
The preparation method of L (+) ethyl tartrate Download PDFInfo
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- CN107337603A CN107337603A CN201710528523.7A CN201710528523A CN107337603A CN 107337603 A CN107337603 A CN 107337603A CN 201710528523 A CN201710528523 A CN 201710528523A CN 107337603 A CN107337603 A CN 107337603A
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- ethyl tartrate
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/14—Preparation of carboxylic acid esters from carboxylic acid halides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/58—Preparation of carboxylic acid halides
- C07C51/60—Preparation of carboxylic acid halides by conversion of carboxylic acids or their anhydrides or esters, lactones, salts into halides with the same carboxylic acid part
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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
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- Oil, Petroleum & Natural Gas (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of preparation method of L (+) ethyl tartrate, belong to organic chemical synthesis technical field.Described preparation method is that L (+) tartaric acid, anhydrous ethanol solvent are added in reaction vessel, thionyl chloride is added dropwise under the conditions of 0~30 DEG C, time for adding is 1~3h, is added dropwise, and is warming up to 30~60 DEG C of reactions, 1~5h of insulation reaction, after reaction terminates, it is evaporated under reduced pressure and removes alcohol solvent, obtain L (+) ethyl tartrate crude product, then catalyst is added in crude product to be reacted, L (+) ethyl tartrate product is obtained after filtering.The preparation method of the present invention is using thionyl chloride as acylating agent; reaction conversion ratio is significantly improved; molar yield reaches more than 95%; solvent is used as using alcohols (ethanol); recoverable, industrial residu is not produced, crude product through catalyst after catalytic reaction is carried out; the byproduct of reaction in crude product is eliminated, product purity can reach more than 99.0%.
Description
Technical field
The present invention relates to a kind of preparation method of L- (+)-ethyl tartrate, belong to organic chemical synthesis technical field.
Background technology
In chipal compounds, different enantiomers often shows different property, continuous with chiral synthesis
Further investigation, the preparation of enantiomeric compounds have large effect in agricultural, industrial trade, especially in medicine synthesis neck
Domain, often drug effect is different for different enantiomers, or even the enantiomer having has side effect.L- (+)-ethyl tartrate is a kind of nothing
Color or pale yellow oily liquid, there is the function of stereoselectivity and chiral Recognition, it is mainly used in the chiral extraction of medicine point
Field is synthesized from asymmetry catalysis, structural formula is as follows：
At present, synthetic method conventional L- (+)-ethyl tartrate be under sulphuric acid catalysis by L- (+)-tartaric acid and
Ethanol synthesis, synthesized in the environment of carbon tetrachloride is as dehydrating agent, because concentrated sulfuric acid acidity is stronger, bring the same of environmental hazard
When, and side reaction is also easy to produce, product yield is relatively low, is not suitable for industrialized production.
CN101100428A discloses a kind of method using boric acid catalysis synthesis of chiral L- or D- ethyl tartrate, text
Middle proposition replaces sulphuric acid catalysis to obtain product with boric acid, but introduces toluene in extract and separate, cost is added, by right
Crude product is evaporated under reduced pressure collection distillate and obtains product, and distillation energy consumption is higher, and bottoms are difficult to handle, and industrialization difficulty is big.
CN104926658A discloses a kind of using storng-acid cation exchange resin as catalyst synthesis L- (+)-wine
The preparation technology of stone diethyl phthalate, caused pickling waste waters is more in preparation process, and recovery catalyst needs activated, dried
Dry, cost is higher, and product is distillated by the way that crude product is evaporated under reduced pressure into collection under 120 DEG C of temperature, vacuum 66.7Pa
Thing obtains, and for molar yield 70% or so, distillation energy consumption is higher, vacuum to equipment requirement compared with it is high, industrialization difficulty is big, and steam
Residue is evaporated to be difficult to handle.
Therefore, for above mentioned problem present in existing process, it is necessary to carry out further optimizing research.
The content of the invention
It is an object of the invention to provide a kind of preparation method of L- (+)-ethyl tartrate, solve in existing process and deposit
High energy consumption, product yield is low, it is high that equipment is required in itself, industrialization difficulty is big the problem of, have simple to operate, equipment will
Ask low, do not produce the characteristics of industrial residu.
The preparation method of L- (+)-ethyl tartrate of the present invention, comprises the following steps：
(1) L- (+)-tartaric acid, anhydrous ethanol solvent are added in reaction vessel, chlorine is added dropwise under the conditions of 0~30 DEG C
Change sulfoxide, time for adding is 1~3h, is added dropwise, and is warming up to 30~60 DEG C of reactions, 1~5h of insulation reaction, reacts after terminating,
It is evaporated under reduced pressure and removes alcohol solvent, obtains L- (+)-ethyl tartrate crude product；Reaction equation is as follows：
(2) add catalyst in the L- (+) obtained into step (1)-ethyl tartrate crude product to be reacted, after filtering
Obtain L- (+)-ethyl tartrate product.
Wherein it is preferred to technical scheme is as follows：
The volumetric usage (mL) of absolute ethyl alcohol is 3~10 times of L- (+)-tartaric acid quality dosage (g) in step (1).
The ratio between mole dosage of L- (+)-tartaric acid and thionyl chloride is 1 in step (1):2~8.
The ratio between mole dosage of L- (+)-tartaric acid and catalyst is 1:0.15~0.5.
Catalyst is any one in sodium acid carbonate, saleratus, ammonium hydrogen carbonate, sodium carbonate, potassium carbonate in step (2)
It is or a variety of.
The catalytic reaction time is 1~3h in step (2).
Catalytic reaction temperature is 20~50 DEG C in step (2).
Beneficial effects of the present invention are as follows：
(1) preparation method of the invention is significantly improved using thionyl chloride as acylating agent, reaction conversion ratio, mole
Yield reaches more than 95%；Using alcohols (ethanol) as solvent, recoverable, industrial residu is not produced；
(2) L- (+)-ethyl tartrate crude product eliminates the reaction in crude product after catalytic reaction is carried out through catalyst
Accessory substance, product purity can reach more than 99.0%；
(3) preparation technology of the invention avoids high temperature in traditional handicraft, high vacuum distillation demand, the requirement to equipment
Reduce, security is improved, and is produced in technical process without bottoms, clean environment firendly, it is easier to industrialized production.
Embodiment
The present invention is described further with reference to embodiments.
Embodiment 1
The preparation method of L- (+)-ethyl tartrate, comprises the following steps：
(1) L- (+)-tartaric acid 30g is put into tri- mouthfuls of glass flasks of 500mL, then measures absolute ethyl alcohol 100mL additions
Into three-necked flask, stirring is opened, thionyl chloride 47.8g, time 1.5h is added dropwise at 0~10 DEG C in temperature in control, and process is added dropwise
In have heat release, be warming up to 60 DEG C after being added dropwise to complete, react 1h, be then evaporated under reduced pressure, remove ethanol, obtain L- (+)-tartaric acid two
Ethyl ester；
(2) sodium acid carbonate 2.5g is added into L- (+)-ethyl tartrate crude product, is warming up to 20 DEG C, stirring reaction 3h,
Filter off and remove solid, obtain colourless or pale yellow oily liquid L- (+)-ethyl tartrate 39.2g, molar yield is
95.2%, after testing, product purity 99.3%.
Embodiment 2
The preparation method of L- (+)-ethyl tartrate, comprises the following steps：
(1) L- (+)-tartaric acid 30g is put into tri- mouthfuls of glass flasks of 500mL, then measures absolute ethyl alcohol 150mL additions
Into three-necked flask, stirring is opened, thionyl chloride 95.4g, time 1.5h is added dropwise at 0~30 DEG C in temperature in control, and process is added dropwise
In have heat release, be warming up to 50 DEG C after being added dropwise to complete, react 2h, be then evaporated under reduced pressure, remove ethanol, obtain L- (+)-tartaric acid two
Ethyl ester；
(2) saleratus 3.3g is added into L- (+)-ethyl tartrate crude product, is warming up to 20 DEG C, stirring reaction 3h,
Filter off and remove solid, obtain colourless or pale yellow oily liquid L- (+)-ethyl tartrate 39.6g, molar yield is
96.2%, after testing, product purity 99.4%.
Embodiment 3
The preparation method of L- (+)-ethyl tartrate, comprises the following steps：
(1) L- (+)-tartaric acid 30g is put into tri- mouthfuls of glass flasks of 500mL, then measures absolute ethyl alcohol 250mL additions
Into three-necked flask, stirring is opened, temperature is added dropwise thionyl chloride 135.4g, time 2.0h, be added dropwise at 10~20 DEG C in control
There is heat release in journey, 50 DEG C are warming up to after being added dropwise to complete, react 2h, be then evaporated under reduced pressure, remove ethanol, obtain L- (+)-tartaric acid
Diethylester crude product；
(2) potassium carbonate 12.5g is added into L- (+)-ethyl tartrate crude product, is warming up to 40 DEG C, stirring reaction 2h, mistake
Elimination removes solid, obtains colourless or pale yellow oily liquid L- (+)-ethyl tartrate 39.6g, molar yield 96.2%,
After testing, product purity 99.5%.
Embodiment 4
The preparation method of L- (+)-ethyl tartrate, comprises the following steps：
(1) L- (+)-tartaric acid 50g is put into tri- mouthfuls of glass flasks of 500mL, then measures absolute ethyl alcohol 150mL additions
Into three-necked flask, stirring is opened, temperature is added dropwise thionyl chloride 187.8g, time 2.5h, be added dropwise at 0~10 DEG C in control
There is heat release in journey, 30 DEG C are warming up to after being added dropwise to complete, react 5h, be then evaporated under reduced pressure, remove ethanol, obtain L- (+)-tartaric acid
Diethylester crude product；
(2) sodium carbonate 9.6g is added into L- (+)-ethyl tartrate crude product, is warming up to 50 DEG C, stirring reaction 1h, mistake
Elimination removes solid, obtains colourless or pale yellow oily liquid L- (+)-ethyl tartrate 39.4g, molar yield 95.5%,
After testing, product purity 99.2%.
Claims (7)
- A kind of 1. preparation method of L- (+)-ethyl tartrate, it is characterised in that：Comprise the following steps：(1) L- (+)-tartaric acid, absolute ethyl alcohol are added in reaction vessel, thionyl chloride is added dropwise under the conditions of 0~30 DEG C, dripped It is 1~3h between added-time, is added dropwise, is warming up to 30~60 DEG C of reactions, 1~5h of insulation reaction, after reaction terminates, vacuum distillation removes Ethanol is removed, obtains L- (+)-ethyl tartrate crude product；(2) catalyst is added in the L- (+) obtained into step (1)-ethyl tartrate crude product to be reacted, obtained after filtering L- (+)-ethyl tartrate product.
- 2. the preparation method of L- (+)-ethyl tartrate according to claim 1, it is characterised in that：Nothing in step (1) The volumetric usage (mL) of water-ethanol is 3~10 times of L- (+)-tartaric acid quality dosage (g).
- 3. the preparation method of L- (+)-ethyl tartrate according to claim 1, it is characterised in that：L- in step (1) The ratio between mole dosage of (+)-tartaric acid and thionyl chloride is 1:2~8.
- 4. the preparation method of L- (+)-ethyl tartrate according to claim 1, it is characterised in that：L- (+)-tartaric acid It is 1 with the ratio between the mole dosage of catalyst:0.15~0.5.
- 5. the preparation method of L- (+)-ethyl tartrate according to claim 1, it is characterised in that：Step is urged in (2) Agent is any one or more in sodium acid carbonate, saleratus, ammonium hydrogen carbonate, sodium carbonate, potassium carbonate.
- 6. the preparation method of L- (+)-ethyl tartrate according to claim 1, it is characterised in that：Step is urged in (2) The change reaction time is 1~3h.
- 7. the preparation method of L- (+)-ethyl tartrate according to claim 1, it is characterised in that：Step is urged in (2) It is 20~50 DEG C to change reaction temperature.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
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| CN201710528523.7A CN107337603A (en) | 2017-07-01 | 2017-07-01 | The preparation method of L (+) ethyl tartrate |
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| CN201710528523.7A CN107337603A (en) | 2017-07-01 | 2017-07-01 | The preparation method of L (+) ethyl tartrate |
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| CN107337603A true CN107337603A (en) | 2017-11-10 |
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Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003883A (en) * | 2013-02-26 | 2014-08-27 | 东丽精细化工株式会社 | Method for manufacturing high purity tartaric acid dialkyl esters |
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- 2017-07-01 CN CN201710528523.7A patent/CN107337603A/en active Pending
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104003883A (en) * | 2013-02-26 | 2014-08-27 | 东丽精细化工株式会社 | Method for manufacturing high purity tartaric acid dialkyl esters |
Non-Patent Citations (1)
| Title |
|---|
| 姜艳等: "新型C2轴对称吡啶羧酸酯手性多齿配体的合成", 《合成化学》 * |
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