CN106893746A - Biological catalysis synthesize the method for 3- cyclopentene -1,1- dioctyl phthalate - Google Patents
Biological catalysis synthesize the method for 3- cyclopentene -1,1- dioctyl phthalate Download PDFInfo
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- CN106893746A CN106893746A CN201510947506.8A CN201510947506A CN106893746A CN 106893746 A CN106893746 A CN 106893746A CN 201510947506 A CN201510947506 A CN 201510947506A CN 106893746 A CN106893746 A CN 106893746A
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- cyclopentene
- dioctyl phthalate
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- C12P7/00—Preparation of oxygen-containing organic compounds
- C12P7/40—Preparation of oxygen-containing organic compounds containing a carboxyl group including Peroxycarboxylic acids
- C12P7/44—Polycarboxylic acids
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Abstract
The invention discloses a kind of biological catalysis synthesis 3- cyclopentene -1, the method of 1- dioctyl phthalate, using 3- cyclopentene -1,1- dicarboxylates or 3- cyclopentene -1,1- dicarboxylic acid dimethyl esters are initiation material, through Perhydrolase catalyzing hydrolysis 3- cyclopentene -1,1- dicarboxylates or 3- cyclopentene -1, the ester group in 1- dicarboxylic acid dimethyl ester structures are carboxyl.The present invention uses biological enzyme, reflects mild condition, low cost；Without materials such as highly basic, strong acid in production process, to equipment and operator's not damaged.
Description
Technical field
The invention belongs to biological technical field, relate more specifically to a kind of biological catalysis synthesis 3- cyclopentene -1,1- bis-
The method of formic acid.
Background technology
3- cyclopentene -1,1- dioctyl phthalate is the intermediate for synthesizing 3- cyclopentene -1- formic acid and its derivative, and the latter mainly uses
In common important drugs such as the production sweet, prostaglandins of homocyclic nucleus.
Synthesis 3- cyclopentene -1,1- dioctyl phthalate heats hydrolysis 3- cyclopentene -1,1- diformazans under being mainly basic conditions at present
Diethyl phthalate or 3- cyclopentene -1,1- dicarboxylic acid dimethyl esters, the method need a large amount of highly basic, and react a large amount of acid of end needs
Solution is neutralized, and this process produces a large amount of high salts, high-COD waste water, and the requirement of current green production is no longer adapted to.
The content of the invention
1st, the purpose of the present invention.
The present invention in order to solve the infringement that is caused to equipment and operator during prior art generating mode and
Caused material waste in production process, and a kind of biological catalysis synthesis 3- cyclopentene -1 for proposing, the method for 1- dioctyl phthalate.
2nd, the technical solution adopted in the present invention.
Biological catalysis synthesis 3- cyclopentene -1, the method for 1- dioctyl phthalate, using 3- cyclopentene -1,1- dicarboxylates
Or 3- cyclopentene -1,1- dicarboxylic acid dimethyl esters are initiation material, through Perhydrolase catalyzing hydrolysis 3- cyclopentene -1,1- dioctyl phthalate two
Ethyl ester or 3- cyclopentene -1, the ester group in 1- dicarboxylic acid dimethyl ester structures is carboxyl, and its synthetic route is as follows：
。
Further in specific embodiment, extraction and the solvent to product recrystallization are ethyl acetate, dichloromethane, first
Benzene.
Further in specific embodiment, extraction and the solvent to product recrystallization are ethyl acetate.
Further in specific embodiment, described hydrolase is the thick enzyme powder of lipase including coming from Pseudomonas fluorescens
Lipase A and from rice black wool mould lipase B.
Further in specific embodiment, described hydrolase uses Pseudomonas fluorecens lipase A.
Further in specific embodiment, the ratio of hydrolase used and unclassified stores is 1:100~20:100.
Further in specific embodiment, the ratio of hydrolase used and unclassified stores is 10:100.
Further in specific embodiment, reaction dissolvent is water.
3rd, beneficial effects of the present invention.
（1）The present invention uses biological enzyme, reflects mild condition, low cost；
（2）Without materials such as highly basic, strong acid in production process of the present invention, to equipment and operator's not damaged.
Specific embodiment
In order that the auditor of Patent Office especially the public can be more clearly understood from technical spirit of the invention and having
Beneficial effect, applicant will elaborate by way of example below, but the description to embodiment is not to this hair
The limitation of bright scheme, any only formal rather than substantial equivalent transformation according to done by present inventive concept all should
It is considered as technical scheme category.
The present invention is 10% in hydrolysis enzyme-to-substrate mass ratio, and water is solvent, pH=7~9, and temperature is under conditions of 45 DEG C,
Catalyzing hydrolysis 3- cyclopentene -1,1- dicarboxylates or 3- cyclopentene -1,1- dicarboxylic acid dimethyl esters are 3- cyclopentene -1,1- two
Formic acid, its synthetic route is as follows：
。
The present invention be directed to 3- cyclopentene -1,1- dioctyl phthalate, there is provided the synthesis technique of a set of environmental protection, there should be technique
Simply, it is to avoid vigorous reaction condition, the advantages of " three wastes " less.
Embodiment 1
50 grams of 3- cyclopentene -1,1- dicarboxylates are added in 1000mL round-bottomed flasks, 500mL sodium phosphate buffers is poured into molten
Liquid（PH=8, concentration are 100mM）, 5 grams of lipase As are added, appropriate stir speed (S.S.) is set, temperature is adjusted to 45 DEG C or so, with 10%
Sodium hydroxide solution maintenance reaction system pH=7~9.
Reaction 18 hours, is cooled to room temperature, regulation pH=3 or so, filters off lipase A, adds 500mL ethyl acetate, stirring
30 minutes, stratification separated organic layer, then extracted once with 500mL ethyl acetate, it is ensured that extraction is complete.
Concentration and recovery ethyl acetate 800mL, room temperature is cooled to simultaneously by the ethyl acetate solution of 3- cyclopentene -1,1- dioctyl phthalate
2 hours are stood, 3- cyclopentene -1,1- dicarboxylic acid crystals are separated out, 33.84 grams of the white solid such as filtering, liquid phase purity is 98%, is received
Rate is 92%.1H NMR (d-DMSO, ppm):δ2.89 (S,4H),5.59 (S,1H),12.75 (s,2H).
Embodiment 2
50 grams of 3- cyclopentene -1,1- dicarboxylates are added in 1000mL round-bottomed flasks, 500mL sodium phosphate buffers is poured into molten
Liquid（PH=8, concentration are 100mM）, 5 grams of lipase Bs are added, appropriate stir speed (S.S.) is set, temperature is adjusted to 45 DEG C or so, with 10%
Sodium hydroxide solution maintenance reaction system pH=7~9.
Reaction 18 hours, is cooled to room temperature, regulation pH=3 or so, filters off lipase B, adds 500mL ethyl acetate, stirring
30 minutes, stratification separated organic layer, then extracted once with 500mL ethyl acetate, it is ensured that extraction is complete.
Concentration and recovery ethyl acetate 800mL, room temperature is cooled to simultaneously by the ethyl acetate solution of 3- cyclopentene -1,1- dioctyl phthalate
2 hours are stood, 3- cyclopentene -1,1- dicarboxylic acid crystals are separated out, 26.60 grams of the white solid such as filtering, liquid phase purity is 98%, is received
Rate is 72%.1H NMR (d-DMSO, ppm):δ2.89 (S,4H),5.59 (S,1H),12.75 (s,2H).
Embodiment 3
50 grams of 3- cyclopentene -1,1- dicarboxylic acid dimethyl esters are added in 1000mL round-bottomed flasks, 500mL sodium phosphate buffers is poured into molten
Liquid（PH=8, concentration are 100mM）, 5 grams of lipase As are added, appropriate stir speed (S.S.) is set, temperature is adjusted to 45 DEG C or so, with 10%
Sodium hydroxide solution maintenance reaction system pH=7~9.
Reaction 18 hours, is cooled to room temperature, regulation pH=3 or so, filters off lipase A, adds 500mL ethyl acetate, stirring
30 minutes, stratification separated organic layer, then extracted once with 500mL ethyl acetate, it is ensured that extraction is complete.
Concentration and recovery ethyl acetate 800mL, room temperature is cooled to simultaneously by the ethyl acetate solution of 3- cyclopentene -1,1- dioctyl phthalate
2 hours are stood, 3- cyclopentene -1,1- dicarboxylic acid crystals are separated out, 38.58 grams of the white solid such as filtering, liquid phase purity is 98%, is received
Rate is 91%.1H NMR (d-DMSO, ppm):δ2.89 (S,4H),5.59 (S,1H),12.75 (s,2H).
Embodiment 4
50 grams of 3- cyclopentene -1,1- dicarboxylic acid dimethyl esters are added in 1000mL round-bottomed flasks, 500mL sodium phosphate buffers is poured into molten
Liquid（PH=8, concentration are 100mM）, 5 grams of lipase Bs are added, appropriate stir speed (S.S.) is set, temperature is adjusted to 45 DEG C or so, with 10%
Sodium hydroxide solution maintenance reaction system pH=7~9.
Reaction 18 hours, is cooled to room temperature, regulation pH=3 or so, filters off lipase B, adds 500mL ethyl acetate, stirring
30 minutes, stratification separated organic layer, then extracted once with 500mL ethyl acetate, it is ensured that extraction is complete.
Concentration and recovery ethyl acetate 800mL, room temperature is cooled to simultaneously by the ethyl acetate solution of 3- cyclopentene -1,1- dioctyl phthalate
2 hours are stood, 3- cyclopentene -1,1- dicarboxylic acid crystals are separated out, 27.56 grams of the white solid such as filtering, liquid phase purity is 98%, is received
Rate is 65%.1H NMR (d-DMSO, ppm):δ2.89 (S,4H),5.59 (S,1H),12.75 (s,2H).
Claims (8)
1. a kind of biological catalysis synthesize 3- cyclopentene -1, the method for 1- dioctyl phthalate, it is characterised in that using 3- cyclopentene -1,1-
Dicarboxylate or 3- cyclopentene -1,1- dicarboxylic acid dimethyl esters be initiation material, through Perhydrolase catalyzing hydrolysis 3- cyclopentene -
1,1- dicarboxylate or 3- cyclopentene -1, the ester group in 1- dicarboxylic acid dimethyl ester structures is carboxyl, and its synthetic route is as follows：
。
2. biological catalysis according to claim 1 synthesize 3- cyclopentene -1, the method for 1- dioctyl phthalate, it is characterised in that：
Extraction and the solvent to product recrystallization are ethyl acetate, dichloromethane, toluene.
3. biological catalysis according to claim 2 synthesize 3- cyclopentene -1, the method for 1- dioctyl phthalate, it is characterised in that：
Extraction and the solvent to product recrystallization are ethyl acetate.
4. biological catalysis according to claim 1 synthesize 3- cyclopentene -1, the method for 1- dioctyl phthalate, it is characterised in that：
Described hydrolase is that the thick enzyme powder of lipase is included from Pseudomonas fluorecens lipase A and from rice black wool mould lipase B.
5. biological catalysis according to claim 4 synthesize 3- cyclopentene -1, the method for 1- dioctyl phthalate, it is characterised in that：
Described hydrolase uses Pseudomonas fluorecens lipase A.
6. biological catalysis according to claim 1 synthesize 3- cyclopentene -1, the method for 1- dioctyl phthalate, it is characterised in that：
The ratio of hydrolase used and unclassified stores is 1:100~20:100.
7. biological catalysis according to claim 6 synthesize 3- cyclopentene -1, the method for 1- dioctyl phthalate, it is characterised in that：
The ratio of hydrolase used and unclassified stores is 10:100.
8. biological catalysis according to claim 1 synthesize 3- cyclopentene -1, the method for 1- dioctyl phthalate, it is characterised in that：
Reaction dissolvent is water.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510947506.8A CN106893746A (en) | 2015-12-17 | 2015-12-17 | Biological catalysis synthesize the method for 3- cyclopentene -1,1- dioctyl phthalate |
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| CN201510947506.8A CN106893746A (en) | 2015-12-17 | 2015-12-17 | Biological catalysis synthesize the method for 3- cyclopentene -1,1- dioctyl phthalate |
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003820A (en) * | 2006-01-18 | 2007-07-25 | 佳和桂科技股份有限公司 | Processes for the preparations of optically active cyclopentenones and cyclopentenones prepared therefrom |
| JP2015024980A (en) * | 2013-07-29 | 2015-02-05 | 国立大学法人 筑波大学 | Polyethylene glycol having polyfunctional group as terminal group |
-
2015
- 2015-12-17 CN CN201510947506.8A patent/CN106893746A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101003820A (en) * | 2006-01-18 | 2007-07-25 | 佳和桂科技股份有限公司 | Processes for the preparations of optically active cyclopentenones and cyclopentenones prepared therefrom |
| JP2015024980A (en) * | 2013-07-29 | 2015-02-05 | 国立大学法人 筑波大学 | Polyethylene glycol having polyfunctional group as terminal group |
Non-Patent Citations (5)
| Title |
|---|
| GEORGE H. SCHMID ET AL.: "An Improved Synthesis of 3-Cyclopentene-1-Carboxylic Acid from l,4-Dichlorobutene-2", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| JEAN-PIERRE DEPRBS ET AL.: "Improved Selectivity in the Preparation of Some 1,l-Difunctionalized 3-Cyclopentenes. High-Yield Synthesis of 3-Cyclopentenecarboxylic Acid", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| K. C. MURDOCK AND ROBERT B. ANGIER: "A New Route to 1-Substituted 3-Cyclopentenes", 《THE JOURNAL OF ORGANIC CHEMISTRY》 * |
| WILLIAM A. NUGENT ET AL.: "Practical Catalyst for Cyclic Metathesis. Synthesis of Functional and/or Enantiopure Cycloalkenes", 《JOURNAL OF THE AMERICAN CHEMICAL SOCIETY》 * |
| 张宏等: "3- 环戊烯 -1- 甲酸的合成研究", 《化工中间体》 * |
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Application publication date: 20170627 |
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