CN105087697A - Method for roducing (S)-ethoxyl phenyl methanesulfonate by use of cells - Google Patents
Method for roducing (S)-ethoxyl phenyl methanesulfonate by use of cells Download PDFInfo
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- 238000000034 method Methods 0.000 title claims abstract description 11
- WXVUCMFEGJUVTN-UHFFFAOYSA-N phenyl methanesulfonate Chemical compound CS(=O)(=O)OC1=CC=CC=C1 WXVUCMFEGJUVTN-UHFFFAOYSA-N 0.000 title 1
- 238000006243 chemical reaction Methods 0.000 claims abstract description 41
- 241000235056 Pichia norvegensis Species 0.000 claims abstract description 21
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 36
- -1 (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester Chemical class 0.000 claims description 24
- 239000000243 solution Substances 0.000 claims description 20
- 230000002210 biocatalytic effect Effects 0.000 claims description 18
- 210000005253 yeast cell Anatomy 0.000 claims description 18
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 17
- 239000008103 glucose Substances 0.000 claims description 17
- 238000009423 ventilation Methods 0.000 claims description 17
- 210000004027 cell Anatomy 0.000 claims description 14
- 235000015097 nutrients Nutrition 0.000 claims description 13
- 238000002360 preparation method Methods 0.000 claims description 13
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 12
- 239000000843 powder Substances 0.000 claims description 12
- 239000000758 substrate Substances 0.000 claims description 11
- OWEGMIWEEQEYGQ-UHFFFAOYSA-N 100676-05-9 Natural products OC1C(O)C(O)C(CO)OC1OCC1C(O)C(O)C(O)C(OC2C(OC(O)C(O)C2O)CO)O1 OWEGMIWEEQEYGQ-UHFFFAOYSA-N 0.000 claims description 7
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 7
- GUBGYTABKSRVRQ-PICCSMPSSA-N Maltose Natural products O[C@@H]1[C@@H](O)[C@H](O)[C@@H](CO)O[C@@H]1O[C@@H]1[C@@H](CO)OC(O)[C@H](O)[C@H]1O GUBGYTABKSRVRQ-PICCSMPSSA-N 0.000 claims description 7
- SRBFZHDQGSBBOR-LECHCGJUSA-N alpha-D-xylose Chemical compound O[C@@H]1CO[C@H](O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-LECHCGJUSA-N 0.000 claims description 7
- 230000035484 reaction time Effects 0.000 claims description 7
- 229960003487 xylose Drugs 0.000 claims description 7
- 240000008042 Zea mays Species 0.000 claims description 6
- 235000005824 Zea mays ssp. parviglumis Nutrition 0.000 claims description 6
- 235000002017 Zea mays subsp mays Nutrition 0.000 claims description 6
- 239000000872 buffer Substances 0.000 claims description 6
- 208000012839 conversion disease Diseases 0.000 claims description 6
- 235000005822 corn Nutrition 0.000 claims description 6
- LOKCTEFSRHRXRJ-UHFFFAOYSA-I dipotassium trisodium dihydrogen phosphate hydrogen phosphate dichloride Chemical compound P(=O)(O)(O)[O-].[K+].P(=O)(O)([O-])[O-].[Na+].[Na+].[Cl-].[K+].[Cl-].[Na+] LOKCTEFSRHRXRJ-UHFFFAOYSA-I 0.000 claims description 6
- 238000001914 filtration Methods 0.000 claims description 6
- 235000011187 glycerol Nutrition 0.000 claims description 6
- 239000002953 phosphate buffered saline Substances 0.000 claims description 6
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 claims description 6
- 229920000053 polysorbate 80 Polymers 0.000 claims description 6
- 238000004519 manufacturing process Methods 0.000 abstract description 4
- 238000007796 conventional method Methods 0.000 abstract 1
- NIXKBAZVOQAHGC-UHFFFAOYSA-M phenylmethanesulfonate Chemical compound [O-]S(=O)(=O)CC1=CC=CC=C1 NIXKBAZVOQAHGC-UHFFFAOYSA-M 0.000 abstract 1
- 239000008055 phosphate buffer solution Substances 0.000 abstract 1
- 238000006555 catalytic reaction Methods 0.000 description 7
- 239000005515 coenzyme Substances 0.000 description 7
- 239000002609 medium Substances 0.000 description 7
- 229920001817 Agar Polymers 0.000 description 6
- 239000008272 agar Substances 0.000 description 6
- 239000007787 solid Substances 0.000 description 6
- 239000001888 Peptone Substances 0.000 description 5
- 108010080698 Peptones Proteins 0.000 description 5
- 229940041514 candida albicans extract Drugs 0.000 description 5
- 239000001963 growth medium Substances 0.000 description 5
- 235000019319 peptone Nutrition 0.000 description 5
- 238000011218 seed culture Methods 0.000 description 5
- 239000012138 yeast extract Substances 0.000 description 5
- 230000000694 effects Effects 0.000 description 4
- 238000002474 experimental method Methods 0.000 description 4
- 238000012807 shake-flask culturing Methods 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000003786 synthesis reaction Methods 0.000 description 3
- 101000925662 Enterobacteria phage PRD1 Endolysin Proteins 0.000 description 2
- 101710157860 Oxydoreductase Proteins 0.000 description 2
- 239000003905 agrochemical Substances 0.000 description 2
- 230000001580 bacterial effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000001419 dependent effect Effects 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000012847 fine chemical Substances 0.000 description 2
- 238000005457 optimization Methods 0.000 description 2
- 241000024287 Areas Species 0.000 description 1
- 239000002028 Biomass Substances 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 239000013543 active substance Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 238000011914 asymmetric synthesis Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 230000005389 magnetism Effects 0.000 description 1
- 239000013028 medium composition Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000001737 promoting effect Effects 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000012429 reaction media Substances 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 230000008929 regeneration Effects 0.000 description 1
- 238000011069 regeneration method Methods 0.000 description 1
- 238000012216 screening Methods 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
A method for producing (S)-4-(1-ethoxyl)phenyl methanesulfonate by biocatalysis of candida norvegensis cells comprises the steps of adding a phosphate buffer solution into a reaction tank and using the candida norvegensis cells for biocatalysis reaction. The method is high in product yield and enantiomeric excess, and solves the problem of difficult production of a conventional method.
Description
Technical field
The invention belongs to technology of pharmaceutical engineering field, be related specifically to the technology that candida norvegensis cell biocatalysis prepares chiral medicinal intermediate (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester.
Background technology
Chirality (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester is the important intermediate of synthesis of chiral medicine, fine chemicals, agricultural chemicals product and other exotic materialss.Biocatalysis asymmetric reaction has environmental friendliness, mild condition, selectivity advantages of higher, prepares the first approach of chipal compounds as green high-efficient, is applied to the chipal compounds producing some high added values more and more.Biocatalysis is prepared chirality (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester and is had good application prospect.
Biocatalysis has the outstanding advantages such as catalytic efficiency is high, selectivity strong, mild condition, environmental friendliness, is the important method substituting and expand traditional organic chemical synthesis in process of sustainable development.Wherein chiral separation and asymmetric synthesis are the Application Areass of biocatalysis most magnetism.As in six large fermentoids of biological catalyst, lytic enzyme catalytic kinetics resolution of racemates can obtain quiral products, in industrial biocatalytic, play key player always.In recent years, oxydo-reductase application industrially obtained and increased rapidly.At present, the ratio adopting the industry of lytic enzyme Kinetic Resolution, biological reducing method and biological oxidation process to prepare optical activity chirality compound is 4:2:1.
Biological reducing method is for Kinetic Resolution, and maximum advantage is that theoretical yield can reach 100%, and Atom economy is good.But bioreduction needs the participation of coenzyme or cofactor, limit its application to a certain extent.Due to the dependent cause of coenzyme, in bioreduction, many Bian intact cells are as catalyzer, realize the purification procedures eliminating enzyme in body while coenzyme cyclic regeneration.
(S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester is the important chiral building block of synthesis of chiral medicine, fine chemicals, agricultural chemicals product.Existing method ubiquity low conversion rate, long reaction time, needs add expensive coenzyme, high in cost of production major defect, are difficult to carry out suitability for industrialized production.The present invention will adopt biomass cells catalysis preparation (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester to fall.
Summary of the invention
The present invention adopts candida norvegensis cell catalysis to prepare (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester, and reaction formula is as follows:
To Propiophenone methanesulfonates (1) through candida norvegensis catalyzed reaction, obtain product (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester (2).Have multiple-microorganism can catalysis this reaction, through great many of experiments screening, finally determine adopt candida norvegensis as catalyzer because the effect of its catalyzed reaction is best, reaction yield, enantiomeric excess rate (ee%) are all very high.
Many candida norvegensis can carry out this reaction of biocatalysis, but its effect is different, differs greatly, and through experiment, the present invention selects candida norvegensis bacterial strain to be ATCC60365, its catalyzed reaction best results.
Because most oxydo-reductase is coenzyme NAD (P) H dependent form, and the coenzyme amount contained by cell itself may be less, therefore, when carrying out redox reaction, for promoting regenerating coenzyme, improving reaction efficiency, in reaction system, also adding cosubstrate form transformation system.Conventional cosubstrate kind is more, and the cosubstrate needed for different cell is different, and effect difference is very large, adopts several cosubstrate to combine, can obtain better effects, need carry out great many of experiments and could determine best cosubstrate.The cosubstrate that the present invention determines through great many of experiments is: wood sugar 20-24g/L, maltose 12-15g/L, Virahol 8-10%V/V (volumetric concentration).
Because substrate solubility is lower, so, add tensio-active agent to increase the solubleness of substrate.
developing medium:
1, seed culture medium composition is: yeast extract 10g/L, glucose 20g/L, peptone 20g/L, pH nature; The agar powder of 15g/L is added during preparation solid medium;
2, nutrient solution composition: glucose 25-30g/L, glycerine 25-30g/L, corn plumule powder 30-40g/L, KH2PO49-11g/L, MgSO4.7H2O0.3-0.4g/L, pH value is 6.0.
2, solid medium composition: add the agar powder of 2% in liquid medium within.
1 yeast cell preparation.Candida norvegensis through inclined-plane, shaking flask, seed tank culture obtain seed liquor; Fermentor tank adds nutrient solution, fermentor tank adds nutrient solution, 121 DEG C of autoclavings 30 minutes, be cooled to 30-31 DEG C, candida norvegensis seed liquor is seeded to fermentor tank, inoculative proportion is 6-6.5%, ventilation ratio is 0.6-0.8V/(V minute), cultivate 47-50 hour, obtain wet yeast cell, as biocatalytic reaction catalyzer with filtering centrifuge is centrifugal for 30-31 DEG C.
Biocatalytic Conversion.Add phosphate buffered saline buffer in bottom ventilation stirred tank, pH is 6.4, adds substrate to Propiophenone methanesulfonates, makes concentration of substrate be 80-90g/L.Other compositions: glucose 26-30g/L, tween 80 6-8g/L, wood sugar 20-24g/L, maltose 12-15g/L, Virahol 8-10%V/V (volumetric concentration), 121 DEG C of autoclavings 30 minutes; When being cooled to 30-31 DEG C, add wet yeast cell and make concentration be 89-92g/L, ventilation ratio is 0.11-0.13V/(V minute), namely per minute air flow is 0.11-0.13 times of reaction solution volume, carries out biocatalytic reaction, and the reaction times is 69-72 hour; After reaction terminates, leach cell, be extracted with ethyl acetate reaction solution, steam ethyl acetate, obtain product (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester, reaction conversion ratio 98-99%, product yield 96-97%, enantiomeric excess rate 98.5-99%.
The present invention carries out the work and comprises bacterial strain selection, catalytic reaction condition optimization (temperature of reaction, air flow, pH), reaction medium selection and concentration optimization, comprises concentration of substrate, malt extract content, cosubstrate combination, kinds of surfactants and concentration etc.
embodiment 1
Seed culture medium composition is: yeast extract 10g/L, glucose 20g/L, peptone 20g/L, pH nature; The agar powder of 15g/L is added during preparation solid medium.
Nutrient solution composition is: glucose 25-30g/L, glycerine 25-30g/L, corn plumule powder 30-40g/L, KH2PO49-11g/L, MgSO4.7H2O0.3-0.4g/L, and pH value is 6.0.
Wet yeast cell preparation process is as follows: candida norvegensis ATCC60365 through inclined-plane, shake-flask culture, obtain seed liquor.1L fermentor tank adds nutrient solution, 121 DEG C of autoclavings 30 minutes, be cooled to 30 DEG C, candida norvegensis seed liquor is seeded to fermentor tank, inoculative proportion is 6%, and ventilation ratio is 0.6-0.8V/(V minute), cultivate 47 hours for 30 DEG C, wet yeast cell is obtained, as biocatalytic reaction catalyzer with filtering centrifuge is centrifugal.
Biocatalytic Conversion: add phosphate buffered saline buffer in 0.5L bottom ventilation stirred reactor, pH is 6.4, add substrate to Propiophenone methanesulfonates, concentration is made to be 80g/L, glucose 26g/L, tween 80 8g/L, wood sugar 20g/L, maltose 15g/L, Virahol 8%V/V (volumetric concentration), 121 DEG C of autoclavings 30 minutes; When being cooled to 30 DEG C, add wet yeast cell and make concentration be 89g/L, ventilation ratio is 0.11V/(V minute), carry out biocatalytic reaction, the reaction times is 69 hours; After reaction terminates, leach cell, be extracted with ethyl acetate reaction solution, steam ethyl acetate, obtain product (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester, reaction conversion ratio 99%, product yield 97%, enantiomeric excess rate 98.5%.
embodiment 2
Seed culture medium composition is: yeast extract 10g/L, glucose 20g/L, peptone 20g/L, pH nature; The agar powder of 15g/L is added during preparation solid medium.
Nutrient solution composition is: glucose 25-30g/L, glycerine 25-30g/L, corn plumule powder 30-40g/L, KH2PO49-11g/L, MgSO4.7H2O0.3-0.4g/L, and pH value is 6.0.
Wet yeast cell preparation process is as follows: candida norvegensis ATCC60365 through inclined-plane, shake-flask culture, obtain seed liquor.5L fermentor tank adds nutrient solution, 121 DEG C of autoclavings 30 minutes, be cooled to 31 DEG C, candida norvegensis seed liquor is seeded to fermentor tank, inoculative proportion is 6.5%, and ventilation ratio is 0.6-0.8V/(V minute), cultivate 50 hours for 31 DEG C, wet yeast cell is obtained, as biocatalytic reaction catalyzer with filtering centrifuge is centrifugal.
Biocatalytic Conversion: add phosphate buffered saline buffer in 5L bottom ventilation stirred reactor, pH is 6.4, add substrate to Propiophenone methanesulfonates, concentration is made to be 90g/L, glucose 30g/L, tween 80 6g/L, wood sugar 24g/L, maltose 12g/L, Virahol 10%V/V (volumetric concentration), 121 DEG C of autoclavings 30 minutes; When being cooled to 31 DEG C, add wet yeast cell and make concentration be 92g/L, ventilation ratio is 0.12V/(V minute), carry out biocatalytic reaction, the reaction times is 72 hours; After reaction terminates, leach cell, be extracted with ethyl acetate reaction solution, steam ethyl acetate, obtain product (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester, reaction conversion ratio 98%, product yield 96%, enantiomeric excess rate 99%.
embodiment 3
Seed culture medium composition is: yeast extract 10g/L, glucose 20g/L, peptone 20g/L, pH nature; The agar powder of 15g/L is added during preparation solid medium.
Nutrient solution composition is: glucose 25-30g/L, glycerine 25-30g/L, corn plumule powder 30-40g/L, KH2PO49-11g/L, MgSO4.7H2O0.3-0.4g/L, and pH value is 6.0.
Wet yeast cell preparation process is as follows: candida norvegensis ATCC60365 through inclined-plane, shake-flask culture, obtain seed liquor.10L fermentor tank adds nutrient solution, 121 DEG C of autoclavings 30 minutes, be cooled to 30 DEG C, candida norvegensis seed liquor is seeded to fermentor tank, inoculative proportion is 6.3%, and ventilation ratio is 0.6-0.8V/(V minute), cultivate 48 hours for 30 DEG C, wet yeast cell is obtained, as biocatalytic reaction catalyzer with filtering centrifuge is centrifugal.
Biocatalytic Conversion: add phosphate buffered saline buffer in 10L bottom ventilation stirred reactor, pH is 6.4, add substrate to Propiophenone methanesulfonates, concentration is made to be 84g/L, glucose 28g/L, tween 80 7g/L, wood sugar 22g/L, maltose 13g/L, Virahol 9%V/V (volumetric concentration), 121 DEG C of autoclavings 30 minutes; When being cooled to 30 DEG C, add wet yeast cell and make concentration be 90g/L, ventilation ratio is 0.13V/(V minute), carry out biocatalytic reaction, the reaction times is 70 hours; After reaction terminates, leach cell, be extracted with ethyl acetate reaction solution, steam ethyl acetate, obtain product (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester, reaction conversion ratio 98.5%, product yield 96.5%, enantiomeric excess rate 99%.
embodiment 4
Seed culture medium composition is: yeast extract 10g/L, glucose 20g/L, peptone 20g/L, pH nature; The agar powder of 15g/L is added during preparation solid medium.
Nutrient solution composition is: glucose 25-30g/L, glycerine 25-30g/L, corn plumule powder 30-40g/L, KH2PO49-11g/L, MgSO4.7H2O0.3-0.4g/L, and pH value is 6.0.
Wet yeast cell preparation process is as follows: candida norvegensis ATCC60365 through inclined-plane, shake-flask culture, obtain seed liquor.10L fermentor tank adds nutrient solution, 121 DEG C of autoclavings 30 minutes, be cooled to 31 DEG C, candida norvegensis seed liquor is seeded to fermentor tank, inoculative proportion is 6.5%, and ventilation ratio is 0.6-0.8V/(V minute), cultivate 49 hours for 31 DEG C, wet yeast cell is obtained, as biocatalytic reaction catalyzer with filtering centrifuge is centrifugal.
Biocatalytic Conversion: add phosphate buffered saline buffer in 20L bottom ventilation stirred reactor, pH is 6.4, add substrate to Propiophenone methanesulfonates, concentration is made to be 86g/L, glucose 29g/L, tween 80 8g/L, wood sugar 23g/L, maltose 14g/L, Virahol 9%V/V (volumetric concentration), 121 DEG C of autoclavings 30 minutes; When being cooled to 31 DEG C, add wet yeast cell and make concentration be 91g/L, ventilation ratio is 0.13V/(V minute), carry out biocatalytic reaction, the reaction times is 71 hours; After reaction terminates, leach cell, be extracted with ethyl acetate reaction solution, steam ethyl acetate, obtain product (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester, reaction conversion ratio 99%, product yield 96.5%, enantiomeric excess rate 99%.
Claims (2)
1. the method for candida norvegensis cell biocatalysis preparation (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester, it is characterized in that adding phosphate buffered saline buffer in retort, pH is 6.4, add substrate to Propiophenone methanesulfonates, substrate is made to be 80-90g/L to Propiophenone methanesulfonates addition, glucose 26-30g/L, tween 80 6-8g/L, wood sugar 20-24g/L, maltose 12-15g/L, Virahol 8-10%V/V, 121 DEG C of autoclavings 30 minutes; When being cooled to 30-31 DEG C, add wet yeast cell and make concentration be 89-92g/L, ventilation ratio is 0.11-0.13V/(V minute), carry out biocatalytic reaction, the reaction times is 69-72 hour; After reaction terminates, leach cell, be extracted with ethyl acetate reaction solution, steam ethyl acetate, obtain product (S)-4-(1-hydroxyethyl) benzene methanesulfonic acid ester, reaction conversion ratio 98-99%, product yield 96-97%, enantiomeric excess rate 98.5-99%.
2. method according to claim 1, is characterized in that wet yeast cell preparation process is as follows: candida norvegensis ATCC60365, and through inclined-plane, shaking flask, seed tank culture obtain seed liquor; Fermentor tank adds nutrient solution, 121 DEG C of autoclavings 30 minutes, be cooled to 30-31 DEG C, candida norvegensis seed liquor is seeded to fermentor tank, inoculative proportion is 6-6.5%, and ventilation ratio is 0.6-0.8V/(V minute), cultivate 47-50 hour for 30-31 DEG C, wet yeast cell is obtained, as biocatalytic reaction catalyzer with filtering centrifuge is centrifugal; In fermentor tank, nutrient solution composition is: glucose 25-30g/L, glycerine 25-30g/L, corn plumule powder 30-40g/L, KH2PO49-11g/L, MgSO4.7H2O0.3-0.4g/L, and pH value is 6.0.
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Application publication date: 20151125 |