CN104292074A - R-1-(2,4-dimethyl phenyl) ethanol and synthetic method of R-1-(2,4-dimethyl phenyl) ethanol ester - Google Patents
R-1-(2,4-dimethyl phenyl) ethanol and synthetic method of R-1-(2,4-dimethyl phenyl) ethanol ester Download PDFInfo
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- CN104292074A CN104292074A CN201410527164.XA CN201410527164A CN104292074A CN 104292074 A CN104292074 A CN 104292074A CN 201410527164 A CN201410527164 A CN 201410527164A CN 104292074 A CN104292074 A CN 104292074A
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- -1 R-1-(2,4-dimethyl phenyl) ethanol ester Chemical class 0.000 title claims abstract description 28
- 238000010189 synthetic method Methods 0.000 title claims abstract 7
- DNHQUGRUHBFDFT-SECBINFHSA-N (1r)-1-(2,4-dimethylphenyl)ethanol Chemical compound C[C@@H](O)C1=CC=C(C)C=C1C DNHQUGRUHBFDFT-SECBINFHSA-N 0.000 title abstract 3
- 229940090668 parachlorophenol Drugs 0.000 claims abstract description 18
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 claims abstract description 14
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000003054 catalyst Substances 0.000 claims abstract description 9
- 230000006340 racemization Effects 0.000 claims abstract description 7
- 239000011347 resin Substances 0.000 claims abstract description 7
- 229920005989 resin Polymers 0.000 claims abstract description 7
- 239000004367 Lipase Substances 0.000 claims abstract description 5
- 102000004882 Lipase Human genes 0.000 claims abstract description 5
- 108090001060 Lipase Proteins 0.000 claims abstract description 5
- 235000019421 lipase Nutrition 0.000 claims abstract description 5
- 230000007062 hydrolysis Effects 0.000 claims abstract description 3
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 79
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 21
- 150000002148 esters Chemical class 0.000 claims description 12
- WXNZTHHGJRFXKQ-UHFFFAOYSA-N 4-chlorophenol Chemical compound OC1=CC=C(Cl)C=C1 WXNZTHHGJRFXKQ-UHFFFAOYSA-N 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 6
- 230000003287 optical effect Effects 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
- 238000003786 synthesis reaction Methods 0.000 claims description 4
- 229960000549 4-dimethylaminophenol Drugs 0.000 claims description 3
- QOSSAOTZNIDXMA-UHFFFAOYSA-N Dicylcohexylcarbodiimide Chemical compound C1CCCCC1N=C=NC1CCCCC1 QOSSAOTZNIDXMA-UHFFFAOYSA-N 0.000 claims description 3
- 239000012141 concentrate Substances 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- 239000000284 extract Substances 0.000 claims description 3
- 238000001914 filtration Methods 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 238000010992 reflux Methods 0.000 claims description 3
- 238000004440 column chromatography Methods 0.000 claims description 2
- 238000001514 detection method Methods 0.000 claims description 2
- 150000007524 organic acids Chemical class 0.000 claims description 2
- 238000003825 pressing Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims description 2
- 239000003513 alkali Substances 0.000 claims 1
- 238000009776 industrial production Methods 0.000 abstract description 2
- 239000002994 raw material Substances 0.000 abstract description 2
- ODIGIKRIUKFKHP-UHFFFAOYSA-N (n-propan-2-yloxycarbonylanilino) acetate Chemical compound CC(C)OC(=O)N(OC(C)=O)C1=CC=CC=C1 ODIGIKRIUKFKHP-UHFFFAOYSA-N 0.000 abstract 1
- DNHQUGRUHBFDFT-UHFFFAOYSA-N 1-(2,4-dimethylphenyl)ethanol Chemical compound CC(O)C1=CC=C(C)C=C1C DNHQUGRUHBFDFT-UHFFFAOYSA-N 0.000 abstract 1
- 239000002253 acid Substances 0.000 abstract 1
- 238000002360 preparation method Methods 0.000 description 7
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- 239000003814 drug Substances 0.000 description 5
- NQPDZGIKBAWPEJ-UHFFFAOYSA-N valeric acid Chemical compound CCCCC(O)=O NQPDZGIKBAWPEJ-UHFFFAOYSA-N 0.000 description 5
- 150000002168 ethanoic acid esters Chemical class 0.000 description 4
- 229940070710 valerate Drugs 0.000 description 3
- 229940079593 drug Drugs 0.000 description 2
- 235000019439 ethyl acetate Nutrition 0.000 description 2
- FKRCODPIKNYEAC-UHFFFAOYSA-N ethyl propionate Chemical compound CCOC(=O)CC FKRCODPIKNYEAC-UHFFFAOYSA-N 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- KJTLSVCANCCWHF-UHFFFAOYSA-N Ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 201000010099 disease Diseases 0.000 description 1
- 208000037265 diseases, disorders, signs and symptoms Diseases 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 238000010931 ester hydrolysis Methods 0.000 description 1
- 239000012847 fine chemical Substances 0.000 description 1
- 238000005194 fractionation Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- 229910052707 ruthenium Inorganic materials 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940005605 valeric acid Drugs 0.000 description 1
- 239000000273 veterinary drug Substances 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C67/00—Preparation of carboxylic acid esters
- C07C67/08—Preparation of carboxylic acid esters by reacting carboxylic acids or symmetrical anhydrides with the hydroxy or O-metal group of organic compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/095—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of esters of organic acids
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P41/00—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture
- C12P41/003—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions
- C12P41/004—Processes using enzymes or microorganisms to separate optical isomers from a racemic mixture by ester formation, lactone formation or the inverse reactions by esterification of alcohol- or thiol groups in the enantiomers or the inverse reaction
-
- C—CHEMISTRY; METALLURGY
- C12—BIOCHEMISTRY; BEER; SPIRITS; WINE; VINEGAR; MICROBIOLOGY; ENZYMOLOGY; MUTATION OR GENETIC ENGINEERING
- C12P—FERMENTATION OR ENZYME-USING PROCESSES TO SYNTHESISE A DESIRED CHEMICAL COMPOUND OR COMPOSITION OR TO SEPARATE OPTICAL ISOMERS FROM A RACEMIC MIXTURE
- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/62—Carboxylic acid esters
-
- 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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- Engineering & Computer Science (AREA)
- Wood Science & Technology (AREA)
- Microbiology (AREA)
- General Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Biotechnology (AREA)
- Health & Medical Sciences (AREA)
- Biochemistry (AREA)
- Bioinformatics & Cheminformatics (AREA)
- General Engineering & Computer Science (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The invention relates to R-1-(2,4-dimethyl phenyl) ethanol and a synthetic method of R-1-(2,4-dimethyl phenyl) ethanol ester. The synthetic method comprises the following steps: carrying out dynamic kinetic resolution by taking the 1-(2,4-dimethyl phenyl) ethanol as a raw material, lipase as a biological resolution catalyst, acid resin as a racemization catalyst and parachlorophenol ester as an acylate donor to obtain the R-1-(2,4-dimethyl phenyl) ethanol ester; and carrying out LiOH hydrolysis to obtain the R-1-(2,4-dimethyl phenyl) ethanol. The synthetic method disclosed by the invention has the advantages of moderation condition, environment friendliness, good product yield and high selectivity, and the process has extremely high application value in industrial production because the used racemization catalyst is low in cost and easy to obtain and the like.
Description
Technical field
The present invention relates to the preparation method of a kind of optical homochiral alcohol and ester, especially the Dynamic Kinetic Resolution preparation method of R-1-(2,4-3,5-dimethylphenyl) ethanol and ester thereof.
Background technology
Chiral drug is significant in the control of numerous disease, after medicine circle " reaction stops event ", the study on the synthesis of chiral drug in human body medicine, agricultural chemicals, veterinary drug more and more by national governments, enterprise pay attention to.Chiral alcohol and chiral ester are the chipal compounds that wherein a class is important, can be applied to the synthesis of medicine and fine chemicals as important chiral intermediate and raw material.
R-1-(2, the 4-3,5-dimethylphenyl) ethanol of current report and ester thereof are mainly obtained by biological resolution raceme alcohol, and biological resolution method can be divided into kinetic resolution and Dynamic Kinetic Resolution again.The theoretical yield that general dynamics splits only has 50%, and the method for Dynamic Kinetic Resolution can obtain optically pure chiral alcohol compound with the productive rate of 100% in theory, but R-1-(2 is prepared in the fractionation of the Dynamic Kinetic of existing report, 4-3,5-dimethylphenyl) reaction of ethanol ester generally will use rhodium, and the noble metal catalysts such as ruthenium are as the racemization catalyst in Dynamic Kinetic Resolution process.Greatly improve the cost of reaction, the production of industry words is realized to technique there is great restriction.
Summary of the invention
The present invention, on the basis being lipase kinetic resolution, introduces acidic resins as racemization catalyst, carries out Dynamic Kinetic Resolution 1-(2,4-3,5-dimethylphenyl) ethanol and prepare R-1-(2,4-3,5-dimethylphenyl) ethanol ester.Gained R-1-(2,4-3,5-dimethylphenyl) ethanol ester can obtain R-1-(2,4-3,5-dimethylphenyl) ethanol by hydrolysis again.In the process splitting preparation R-1-(2,4-3,5-dimethylphenyl) ethanol ester, adopt acidic resins as racemization catalyst, both the problem that product yield is low had been overcome, in turn ensure that the cheap and easy to get of catalyzer, can reuse, be easy to realize suitability for industrialized production.
Concrete operation step is as follows:
1) ratio in 1:1-1.2:1-1.2:0.01-0.05 in methylene dichloride adds organic acid successively, para-chlorophenol, DCC, DMAP, and stirring at normal temperature is reacted, and after some plate detection reaction terminates, filters, concentrated, crossing post, to obtain pure para-chlorophenol ester stand-by as acry radical donor.2) in toluene solvant, 1-(2 is added in the ratio of 1:1-1.5,4-3,5-dimethylphenyl) para-chlorophenol ester after ethanol and purifying, then the ratio of pressing 1-(2,4-3,5-dimethylphenyl) ethanol massfraction 5%-20% adds the acidic resins after lipase CRL and process.System is put in the shaking table of 35-70 DEG C and reacts.After reaction certain hour, 1-(2,4-3,5-dimethylphenyl) ethanol completely dissolve can be detected, be converted into R-1-(2,4-3,5-dimethylphenyl) ethanol ester completely, and the optical purity of product is greater than 99%.Reacted product carries out filtering, concentrate, cross column chromatography can obtain pure R-1-(2,4-3,5-dimethylphenyl) ethanol ester.3) in step 2, the pure R-1-of gained (2,4-3,5-dimethylphenyl) ethanol ester joins the alcohol of 10 times of volumes and LiOH(concentration is 1mol/L) be hydrolyzed in mixing solutions, the volume ratio of alcohol and LiOH is 1:1.After reflux certain hour, the completely dissolve of R-1-(2,4-3,5-dimethylphenyl) ethanol ester can be detected, be converted into R-1-(2,4-3,5-dimethylphenyl) ethanol.Final system methylene dichloride repeatedly extracts, after separatory, combined dichloromethane, carry out drying, concentrated after, obtain R-1-(2,4-3,5-dimethylphenyl) ethanol.
The present invention is used to prepare R-1-(2,4-3,5-dimethylphenyl) ethanol and ester thereof not only mild condition, environmental friendliness, product yield is good, selectivity is higher, and racemization catalyst used is cheap and easy to get, this makes this technique have high using value in the industrial production.
Specific implementation method
1) preparation of acry radical donor para-chlorophenol ester
The methylene dichloride of 500ml is added in the round-bottomed flask of 1000ml.Add 128g (1mol) para-chlorophenol more successively, the positive valeric acid of 72g (1.2mol), 247.5g (1.2mol) DCC, 2.44g(0.02mol) DMAP.Stirred at ambient temperature 10 hours, some plate detects para-chlorophenol and disappears, then react end.Solution carries out filtering, concentrating, and then crosses post and can obtain pure para-chlorophenol acetic ester 162.5g, yield 95.6%.
Other para-chlorophenol propionic esters, para-chlorophenol butanic acid ester, the positive valerate of para-chlorophenol etc. also can example preparation according to this.
2) Dynamic Kinetic Resolution prepares R-1-(2,4-3,5-dimethylphenyl) ethanol ester
In the triangular flask of 500ml, add 250ml toluene, then add 68g (0.5mol) 1-(2,4-3,5-dimethylphenyl) ethanol successively, 93.5g (1.1mol) para-chlorophenol acetic ester, 3g CRL, 6g acidic resins CD550.Add complete, Erlenmeyer flask sealing is put into 45 degree of constant-temperature tables and is reacted.After 12 hours, reaction terminates, and 1-(2,4-3,5-dimethylphenyl) ethanol is converted into R-1-(2,4-3,5-dimethylphenyl) alcohol, acetic acid ester completely, and detecting its ee value is 99.8%.After end, solution is filtered, concentrated, cross post pure R-1-(2,4-3,5-dimethylphenyl) alcohol, acetic acid ester 89.6g, yield 93.2%.
Other are with para-chlorophenol propionic ester, and para-chlorophenol butanic acid ester, the positive valerate of para-chlorophenol etc. is prepared R-1-(2,4-3,5-dimethylphenyl) ethanol ester for acry radical donor and can example be carried out according to this.
3) R-1-(2,4-3,5-dimethylphenyl) ethanol Ester hydrolysis prepares R-1-(2,4-3,5-dimethylphenyl) ethanol
1000ml methyl alcohol is first added and LiOH(concentration is 1mol/L in 2000ml round-bottomed flask) mixing solutions of 1:1 preparation by volume, then add 96.06gR-1-(2,4-3,5-dimethylphenyl) alcohol, acetic acid ester reflux and react.Point plate detects the completely dissolve of R-1-(2,4-3,5-dimethylphenyl) alcohol, acetic acid ester, then react end.System carries out underpressure distillation removing methyl alcohol, after cooling, adds 200ml methylene dichloride and extracts, after separatory, dichloromethane solution carried out drying, concentrate to obtain R-1-(2,4-3,5-dimethylphenyl) ethanol 69.1g, yield 92.1%, and ee value is 99.4%.
Other are hydrolyzed R-1-(2,4-3,5-dimethylphenyl) ethanol propionic ester, R-1-(2,4-3,5-dimethylphenyl) ethanol butanic acid ester, R-1-(2,4-3,5-dimethylphenyl) preparation such as ethanol positive valerate R-1-(2,4-3,5-dimethylphenyl) ethanol can example carry out according to this.
Claims (3)
1.R-1-(2,4-3,5-dimethylphenyl) synthetic method of ethanol and ester thereof, it is characterized in that its step is as follows: the ratio 1) in 1:1-1.2:1-1.2:0.01-0.05 in methylene dichloride adds organic acid successively, para-chlorophenol, DCC, DMAP, stirring at normal temperature is reacted, after some plate detection reaction terminates, filter, concentrated, crossing post, to obtain pure para-chlorophenol ester stand-by as acry radical donor; 2) in toluene solvant, 1-(2 is added in the ratio of 1:1-1.5,4-3,5-dimethylphenyl) para-chlorophenol ester after ethanol and purifying, then the ratio of pressing 1-(2,4-3,5-dimethylphenyl) ethanol massfraction 5%-20% adds the acidic resins after lipase CRL and process; System is put in the shaking table of 35-70 DEG C and reacts; After reaction certain hour, the synthesis completely dissolve of 1-(2,4-3,5-dimethylphenyl) ethanol and ester thereof can be detected, be converted into R-1-(2,4-3,5-dimethylphenyl) ethanol ester completely, and the optical purity of product is greater than 99%; Reacted product carries out filtering, concentrate, cross column chromatography can obtain pure R-1-(2,4-3,5-dimethylphenyl) ethanol ester; 3) in step 2, the pure R-1-of gained (2,4-3,5-dimethylphenyl) ethanol ester joins the alcohol of 10 times of volumes and LiOH(concentration is 1mol/L) be hydrolyzed in mixing solutions, the volume ratio of alcohol and LiOH is 1:1; After reflux certain hour, the completely dissolve of R-1-(2,4-3,5-dimethylphenyl) ethanol ester can be detected, be converted into R-1-(2,4-3,5-dimethylphenyl) ethanol; Final system methylene dichloride repeatedly extracts, after separatory, combined dichloromethane, carry out drying, concentrated after, obtain R-1-(2,4-3,5-dimethylphenyl) ethanol.
2. according to claim 1, optical purity R-1-(2,4-3,5-dimethylphenyl) synthetic method of ethanol and ester thereof, it is characterized in that step 2) described in biological resolution catalyzer have lipase CRL, racemization catalyst is acidic resins CD550 or CD8604.
3. according to claim 1, the synthetic method of optical purity R-1-(2,4-3,5-dimethylphenyl) ethanol and ester thereof, is characterized in that hydrolysis R-1-phenylglycollic ester used in step 3) alkali used is LiOH solution.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201410527164.XA CN104292074A (en) | 2014-10-09 | 2014-10-09 | R-1-(2,4-dimethyl phenyl) ethanol and synthetic method of R-1-(2,4-dimethyl phenyl) ethanol ester |
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| CN201410527164.XA CN104292074A (en) | 2014-10-09 | 2014-10-09 | R-1-(2,4-dimethyl phenyl) ethanol and synthetic method of R-1-(2,4-dimethyl phenyl) ethanol ester |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503729A (en) * | 2008-12-08 | 2009-08-12 | 浙江大学 | Enzymatic resolution method of dl 1-phenylethanol compounds |
| CN102127584A (en) * | 2010-12-27 | 2011-07-20 | 浙江大学 | Dynamic kinetic method for resolving secondary alcohol |
-
2014
- 2014-10-09 CN CN201410527164.XA patent/CN104292074A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101503729A (en) * | 2008-12-08 | 2009-08-12 | 浙江大学 | Enzymatic resolution method of dl 1-phenylethanol compounds |
| CN102127584A (en) * | 2010-12-27 | 2011-07-20 | 浙江大学 | Dynamic kinetic method for resolving secondary alcohol |
Non-Patent Citations (2)
| Title |
|---|
| 戴晓庭等: "酰基供体结构对褶皱念珠菌脂肪酶（CRL）催化芳香仲醇动力学拆分立体选择性的影响", 《生物加工过程》 * |
| 程咏梅等: "脂肪酶-酸性树脂耦合催化1-苯乙醇的动态动力学拆分", 《有机化学》 * |
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