CN106380373A - Germacrone alcoholization and biological resolution method - Google Patents

Germacrone alcoholization and biological resolution method Download PDF

Info

Publication number
CN106380373A
CN106380373A CN201610802069.5A CN201610802069A CN106380373A CN 106380373 A CN106380373 A CN 106380373A CN 201610802069 A CN201610802069 A CN 201610802069A CN 106380373 A CN106380373 A CN 106380373A
Authority
CN
China
Prior art keywords
alcohol
alkene
diethyl
compound
dimethyleyelohexane
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
CN201610802069.5A
Other languages
Chinese (zh)
Inventor
王际菊
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Individual
Original Assignee
Individual
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Individual filed Critical Individual
Priority to CN201610802069.5A priority Critical patent/CN106380373A/en
Publication of CN106380373A publication Critical patent/CN106380373A/en
Pending legal-status Critical Current

Links

Classifications

    • 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
    • C07C29/132—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group
    • C07C29/136—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH
    • C07C29/143—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of ketones
    • 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
    • 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
    • C07C29/74—Separation; Purification; Use of additives, e.g. for stabilisation
    • C07C29/88—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound
    • C07C29/92—Separation; Purification; Use of additives, e.g. for stabilisation by treatment giving rise to a chemical modification of at least one compound by a consecutive conversion and reconstruction
    • 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
    • C12P41/005—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 carboxylic acid 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

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Wood Science & Technology (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Zoology (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Microbiology (AREA)
  • Biotechnology (AREA)
  • Biochemistry (AREA)
  • Bioinformatics & Cheminformatics (AREA)
  • General Engineering & Computer Science (AREA)
  • General Health & Medical Sciences (AREA)
  • Genetics & Genomics (AREA)
  • Analytical Chemistry (AREA)
  • Steroid Compounds (AREA)
  • Preparation Of Compounds By Using Micro-Organisms (AREA)
  • Cosmetics (AREA)

Abstract

The invention discloses a germacrone alcoholization and biological resolution method. The method comprises the following steps: by taking germacrone extracted from cedar branches and leaves as a raw material, carrying out reduction with sodium borohydride to obtain a compound II, carrying out enzymatic kinetic resolution reaction on the compound II to obtain a compound III and a compound IV, or carrying out dynamic kinetic resolution to obtain a compound III of which the yield is more than 90%, and hydrolyzing the compound III to obtain a compound V. According to the invention, a latent chiral ketone group in germacrone is further changed to a chiral hydroxyl center so as to carry out further resolution. The method disclosed by the invention has the characteristics of simple operation, high product yield, good optical purity and the like.

Description

Germacrone alcoholization and biological resolution
Technical field
The present invention relates to a kind of reduction alcoholization of prochiral ketone and the biological resolution method of alcohol, more particularly, to germacrone Reduce preparation 3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol for raw material, be further carried out enzymatic dynamically moving Mechanics method for splitting.
Background technology
Germacrone has a kind of warm sweet sample fragrance, with the musical tone that dry flower is fragrant. and the interpolation of 2-3% can produce purple sieve The effect of blue ketone. when adding to 10%, it can be in harmonious proportion the fragrance of a flower and Radix Aucklandiae element. it is particularly well-suited to the fragrance of a flower of sweet perfume-fragrant and sweet class Formula.It or a kind of latent chiral assimilation compound simultaneously, can reduce alcoholization further, be changed into a kind of handss having chiral centre Property alcoholic compound.
But have not yet to see and be related to the synthesis of 3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol phase pass Report, also fails to see and is related to its two kinds of optical isomer R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol with And the synthesis of S -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol and the report of fractionation.
Content of the invention
In order to study to germacrone further, the present invention, with germacrone as raw material, its prochiral ketone group is carried out Further reaction obtains chiral hydroxyl group neutrality, further splits, obtains a kind of new compound of 3 chiral centres.Specifically Realize process as follows：
1）Under condition of ice bath, with alcohol as solvent, add raw material germacrone, sodium borohydride by a certain percentage, then keep low temperature bar Reacted under part, obtained compound ii, i.e. 3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol；
2）In organic solvent toluene, with step 1) gained compound ii as raw material, by a certain percentage add acry radical donor, fat Enzyme, carries out kinetic resolution reaction at a certain temperature, obtains compound III, i.e. R -3,6- diethyl -2,5- diformazan basic ring The acyl compounds of hex- 2- alkene -1- alcohol；And compounds Ⅳ, i.e. S -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- Alcohol；After reaction terminates, filter, concentrate, crossing column purification respectively to pure compound III and compounds Ⅳ；
3）In organic solvent toluene, with step 1) gained compound ii, add acry radical donor, Digestive Enzyme by a certain percentage, disappear Rotation catalyst carries out Dynamic Kinetic Resolution reaction at a certain temperature, compound ii can be fully converted to compound III, The i.e. acyl compounds of R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol；
4）By step 2）Or step 3）The acyl compounds of gained R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol It is added in the oxolane prepared by a certain percentage and the mixed solution of Lithium hydrate, be stirred overnight at room temperature reaction, detection inspection Measured reaction progress, after reaction terminates, crosses column purification and can obtain sterling R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol, The optical purity of final products can reach more than 99%；
Step 2）And step 3）Described in acry radical donor be parachlorophenol acetass, its addition rubs for starting compound II 1.0 ~ 1.5 times of that amount；Step 2）And step 3）Described in Digestive Enzyme be porcine pancreatic lipase, its addition be raw material chemical combination The 1% ~ 10% of thing II mass number；Step 3）Described in racemization catalyst be acidic resins D006, its addition be raw material chemical combination The 5% ~ 20% of thing II mass.
The present invention reduces to obtain -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- with germacrone for raw material is hydrogenated Alcohol；Alcohol obtains R -3 through Dynamic Kinetic Resolution again, 6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acyl compounds, then Be hydrolyzed final R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol；Or respectively obtain through kinetic resolution R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acyl compounds and S -3,6- diethyl -2,5- dimethyl Hexamethylene -2- alkene -1- alcohol, separates R -3 obtaining, 6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acyl compounds warp again Hydrolysis operation, you can obtain R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol.This method possesses simple to operate, product The features such as high income, optical purity are good, has great guidance and using value in the preparation research of Cuculus polioephalus ketone derivatives.
Specific embodiment
Embodiment 1
1）Under the conditions of 0 DEG C, add 250ml absolute methanol, 18g germacrone in single-necked flask, after stirring 15min, add 12g Sodium borohydride, after the completion of feeding intake, uses balloon sealed flask, keeps 0 DEG C of conditioned response 3h, and TLC detection Cuculus polioephalus reactive ketone completely, stops Only react；Go out sodium borohydride to no longer there being bubble to emerge with dilute hydrochloric acid solution, is extracted with 100ml dichloromethane after methanol is evaporated off Three times, combined dichloromethane, drying, -3,6- diethyl -2 can be obtained after concentration, 5- dimethyleyelohexane -2- alkene -1- alcohol 17.8g, Yield is 98.0%.
2）In constant-temperature table, with 200ml indigo plant lid bottle as reaction vessel, add 60ml toluene, 3, the 6- diethyl of 9.1g Base -2,5- dimethyleyelohexane -2- alkene -1- alcohol, 11g parachlorophenol acetass, 0.6g porcine pancreatic lipase PPL, 1.5g acidic resins D006, feeds intake and finishes, and is warming up to 45 DEG C and is reacted, and after 12 hours, detects -3,6- diethyl -2,5- dimethyleyelohexane -2- Alkene -1- alcohol disappears, and is converted into R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acetyl compound；Will be reacted Solution cooling, filtration, concentration, obtain crude product.
3）By step 2）Middle gained crude product is added in 150ml oxolane, and adds Lithium hydrate 7g, is stirred at room temperature Carry out reacting 24 hours, point plate detection R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acetyl compound point disappears When stopped reaction；After adding 150ml water, reactant liquor is concentrated, is boiled off oxolane, then with dichloromethane to surplus solution Carry out extracting, divide liquid, drying, be concentrated to give the crude product containing R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol.
4）By step 3）Gained contains the crude product volume of R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol Than for 10:1 petroleum ether and the mixed solution of ethyl acetate carry out silica gel column chromatography.R -3,6- diethyl -2,5- finally can be obtained Dimethyleyelohexane -2- alkene -1- alcohol 8.2g, yield 90.9%, after testing, and final products R -3,6- diethyl -2,5- diformazan basic ring The ee value of hex- 2- alkene -1- alcohol is 99.3%.
5）In constant-temperature table, with 200ml indigo plant lid bottle as reaction vessel, add 60ml toluene, 3, the 6- diethyl of 9.11g Base -2,5- dimethyleyelohexane -2- alkene -1- alcohol, 11g parachlorophenol acetass, 0.5g porcine pancreatic lipase PPL, feed intake and finish, heat up Reacted to 40 DEG C, after 6 hours, detected 3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol conversion reaches 50%；Stop Only react, reacted solution is cooled down, filter, concentrate, cross post, respectively obtain S -3,6- diethyl -2,5- diformazan basic ring Hex- 2- alkene -1- alcohol 4.37g, yield is 97.2%, product ee value 99.8%；Obtain R-3,6- diethyl -2,5- dimethyleyelohexane -2- Alkene -1- alcohol acetyl compounds 5.48g, yield is 97.8%.
6）By step 5）Middle gained R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acetyl compounds 5.48g is added in 150ml oxolane, and adds Lithium hydrate 7g, is stirred at room temperature and carries out reacting 24 hours, point plate detection R Stopped reaction when -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acetyl compound point disappears；Add 150ml water Afterwards, reactant liquor is concentrated, is boiled off oxolane, then with dichloromethane, surplus solution is carried out extracting, point liquid, drying, dense Contract, cross column purification, obtain R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol 4.4g, this walks yield 96.9%, product Ee value is 99.6%.
Embodiment 2
1）Under the conditions of 0 DEG C, add 1000ml absolute methanol, 180g germacrone in single-necked flask, after stirring 20min, add 150g sodium borohydride, after the completion of feeding intake, uses balloon sealed flask, keeps 0 DEG C of conditioned response 4h, and TLC detection Cuculus polioephalus reactive ketone is complete Entirely, stopped reaction；Dilute hydrochloric acid solution goes out sodium borohydride to no longer there being bubble to emerge, and uses 300ml acetic acid second after methanol is evaporated off Ester extracts three times, combined ethyl acetate, drying, can obtain -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol after concentration 178.9g, yield is 98.3%.
2）In constant-temperature table, with 1000ml indigo plant lid bottle as reaction vessel, add 700ml toluene, 3, the 6- diethyl of 91g Base -2,5- dimethyleyelohexane -2- alkene -1- alcohol, 110g parachlorophenol acetass, 9g porcine pancreatic lipase PPL, 18g acidic resins D006, feeds intake and finishes, and is warming up to 40 DEG C and is reacted, and after 12 hours, detects -3,6- diethyl -2,5- dimethyleyelohexane -2- Alkene -1- alcohol disappears, and is converted into R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acetyl compound；Will be reacted Solution cooling, filtration, concentration, obtain crude product.
3）By step 2）Middle gained crude product is added in 600ml oxolane, and adds Lithium hydrate 80g, and room temperature is stirred Mix and carry out reacting 24 hours, point plate detection R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acetyl compound point disappears Stopped reaction during mistake；After adding 300ml water, reactant liquor is concentrated, is boiled off oxolane, more molten to residue with dichloromethane Liquid carries out extracting, divides liquid, drying, is concentrated to give the crude product containing R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol.
4）By step 3）Gained contains the crude product volume of R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol Than for 10:1 petroleum ether and the mixed solution of ethyl acetate carry out silica gel column chromatography.R -3,6- diethyl -2,5- finally can be obtained Dimethyleyelohexane -2- alkene -1- alcohol 86.8g, yield 95.4%, after testing, and final products R -3,6- diethyl -2,5- diformazan basic ring The ee value of hex- 2- alkene -1- alcohol is 99.2%.
5）In constant-temperature table, with 1000ml indigo plant lid bottle as reaction vessel, add 700ml toluene, 3, the 6- diethyl of 91g Base -2,5- dimethyleyelohexane -2- alkene -1- alcohol, 110g parachlorophenol acetass, 9g porcine pancreatic lipase PPL, feed intake and finish, heat up Reacted to 45 DEG C, after 6 hours, detected 3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol conversion reaches 50%；Stop Only react, reacted solution is cooled down, filter, concentrate, cross post, respectively obtain S -3,6- diethyl -2,5- diformazan basic ring Hex- 2- alkene -1- alcohol 44.77g, yield is 98.4%, product ee value 99.9%；R -3,6- diethyl -2,5- dimethyleyelohexane - 2- alkene -1- alcohol acetyl compounds 54.94g, yield is 98.1%.
6）By step 5）Middle gained R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acetyl compounds 54.94g is added in 600ml oxolane, and adds Lithium hydrate 70g, is stirred at room temperature and carries out reacting 24 hours, point plate detection Stopped reaction when R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol acetyl compound point disappears；Add 300ml water Afterwards, reactant liquor is concentrated, is boiled off oxolane, then with dichloromethane, surplus solution is carried out extracting, point liquid, drying, dense Contract, cross column purification, obtain R -3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol 53.78g, this walks yield 97.9%, produce Product ee value is 99.6%.

Claims (4)

1. a kind of germacrone alcoholization and biological resolution method are it is characterised in that comprise the following steps：
1) under condition of ice bath, with alcohol as solvent, add raw material germacrone, sodium borohydride by a certain percentage, then keep low temperature bar Reacted under part, obtained compound ii, i.e. 3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol；
2) in organic solvent toluene, with step 1) gained compound ii as raw material, by a certain percentage add acry radical donor, fat Enzyme, carries out kinetic resolution reaction at a certain temperature, obtains compound III, i.e. R-3,6- diethyl -2, and 5- dimethyleyelohexane - The acyl compounds of 2- alkene -1- alcohol；And compounds Ⅳ, i.e. S-3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol；Instead After should terminating, filter, concentrate, crossing column purification respectively to pure compound III and compounds Ⅳ；
3) in organic solvent toluene, with step 1) gained compound ii, add acry radical donor, Digestive Enzyme by a certain percentage, disappear Rotation catalyst carries out Dynamic Kinetic Resolution reaction at a certain temperature, compound ii can be fully converted to compound III, The i.e. acyl compounds of R-3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol；
4) by step 2) or step 3) acyl compounds of gained R-3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol add Enter in the mixed solution of the oxolane prepared by a certain percentage and Lithium hydrate, be stirred overnight at room temperature reaction, detection detection Extent of reaction, after reaction terminates, crosses column purification and can obtain sterling R-3,6- diethyl -2,5- dimethyleyelohexane -2- alkene -1- alcohol, The optical purity of finished product can reach more than 99%, and product yield is preferable；According to above step, equation of the present invention As follows：
2. according to claim 1 a kind of alcoholization of germacrone and biological resolution method it is characterised in that：Step 2) and step Acry radical donor described in rapid 3) is parachlorophenol acetass, and its addition is the 1.0～1.5 of starting compound II mole Times.
3. according to claim 1 a kind of alcoholization of germacrone and biological resolution method it is characterised in that：Step 2) and step Digestive Enzyme described in rapid 3) is porcine pancreatic lipase, and its addition is the 1%～10% of starting compound II mass number.
4. according to claim 1 a kind of alcoholization of germacrone and biological resolution method it is characterised in that：Step 3) described in Racemization catalyst be acidic resins D006, its addition be starting compound II mass 5%～20%.
CN201610802069.5A 2016-09-04 2016-09-04 Germacrone alcoholization and biological resolution method Pending CN106380373A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201610802069.5A CN106380373A (en) 2016-09-04 2016-09-04 Germacrone alcoholization and biological resolution method

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201610802069.5A CN106380373A (en) 2016-09-04 2016-09-04 Germacrone alcoholization and biological resolution method

Publications (1)

Publication Number Publication Date
CN106380373A true CN106380373A (en) 2017-02-08

Family

ID=57937995

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201610802069.5A Pending CN106380373A (en) 2016-09-04 2016-09-04 Germacrone alcoholization and biological resolution method

Country Status (1)

Country Link
CN (1) CN106380373A (en)

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102605034A (en) * 2012-02-21 2012-07-25 重庆惠健生物科技有限公司 Biological enzyme resolution method for preparing optically pure (S)-5-(4-fluorophenyl)-5-hydroxypentanoate
CN104262093A (en) * 2014-10-09 2015-01-07 王同俊 R-1-(3-methylphenyl)ethanol and synthesis of ester thereof

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN102605034A (en) * 2012-02-21 2012-07-25 重庆惠健生物科技有限公司 Biological enzyme resolution method for preparing optically pure (S)-5-(4-fluorophenyl)-5-hydroxypentanoate
CN104262093A (en) * 2014-10-09 2015-01-07 王同俊 R-1-(3-methylphenyl)ethanol and synthesis of ester thereof

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
R. SREEKUMAR等: "Regioselective Reduction of Epoxides and Conjugated Carbonyl Compounds Using Zeolite Supported Zinc Borohydride", 《TETRAHEDRON LETTERS》 *

Similar Documents

Publication Publication Date Title
BR112015023334B1 (en) process for producing (r)-3-hydroxybutyl (r)-3-hydroxybutyrate
CN103898037B (en) A kind of coproduction geraniol and the genetic engineering bacterium and its construction method of nerol and application
CN106520896B (en) A kind of method that the conversion of microorganism one-step fermentation prepares Dexamethasone Intermediate
Zhang et al. Enantioselective biomimetic cyclization of 2′-hydroxychalcones to flavanones
CN101108928A (en) Powder paint solidifying agent and method of manufacturing used long chain carbon polyanhydride
CN105051022B (en) Method and intermediate for preparing pregabalin
CN106380373A (en) Germacrone alcoholization and biological resolution method
CN105732373B (en) The method that one kind prepares the phenylbutyrate of (R) 2 hydroxyl 4
CN110438101A (en) A kind of isoflavones O- transmethylase GmIOMT3 and encoding gene and application
CN103724217B (en) A kind of method of asymmetric synthesis of D-Tyrosine
CN114105769A (en) Method for catalytically synthesizing n-propyl cinnamate based on choline chloride eutectic solvent
CN103554005A (en) Novel simple synthesis method of L-5-hydroxytryptophan
CN102010345B (en) Method for preparing D-phenylalanine through dynamic kinetic resolution
CN113717132A (en) Key intermediate of antiepileptic drug and preparation method thereof
CN106467454A (en) Germacrone reduction and fractionation
Sharma et al. Enantio-reversal in Candida rugosa lipase-catalyzed esterification of 3-hydroxybutyric acid
CN1594585A (en) Process for enzymatic synthesis of ethyl lactate in solvent phase
CN111892483B (en) Method for resolving D, L-menthol
CN109879925A (en) A kind of preparation method of phytosterin ester
KR101093415B1 (en) Synthesis of bis-eugenol from eugenol with suspension cell of Kalopanax pictus Nakai
CN106119307B (en) Preparation method of alpha-ketoglutaric acid
CN106349013A (en) +-Nootkatone derivative
CN106397118A (en) Synthesis and resolution methods of chiral alcohol
CN105348280B (en) Green preparation method for 3-alkenyl indolizine derivative
CN106478588A (en) A kind of chiral 1 piperonyl 2 propanol and its isomery preparation

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
WD01 Invention patent application deemed withdrawn after publication

Application publication date: 20170208

WD01 Invention patent application deemed withdrawn after publication