CN101967497A - Preparation of 2-(6'-methoxy-2'-naphthyl) allyl alcohol by laccase method - Google Patents
Preparation of 2-(6'-methoxy-2'-naphthyl) allyl alcohol by laccase method Download PDFInfo
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- CN101967497A CN101967497A CN 201010229704 CN201010229704A CN101967497A CN 101967497 A CN101967497 A CN 101967497A CN 201010229704 CN201010229704 CN 201010229704 CN 201010229704 A CN201010229704 A CN 201010229704A CN 101967497 A CN101967497 A CN 101967497A
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- Prior art keywords
- naphthyl
- methoxyl group
- reaction
- propylene
- laccase
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- XXROGKLTLUQVRX-UHFFFAOYSA-N allyl alcohol Chemical compound OCC=C XXROGKLTLUQVRX-UHFFFAOYSA-N 0.000 title claims abstract description 41
- 108010029541 Laccase Proteins 0.000 title claims abstract description 28
- 238000002360 preparation method Methods 0.000 title claims abstract description 11
- 238000000034 method Methods 0.000 title abstract description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 26
- 238000006243 chemical reaction Methods 0.000 claims abstract description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 22
- QQONPFPTGQHPMA-UHFFFAOYSA-N propylene Natural products CC=C QQONPFPTGQHPMA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 125000004805 propylene group Chemical group [H]C([H])([H])C([H])([*:1])C([H])([H])[*:2] 0.000 claims abstract description 19
- 239000012429 reaction media Substances 0.000 claims abstract description 16
- 239000007864 aqueous solution Substances 0.000 claims abstract description 9
- 238000004440 column chromatography Methods 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 8
- 239000007853 buffer solution Substances 0.000 claims abstract description 4
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims abstract 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims abstract 2
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 21
- 238000000605 extraction Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 238000010790 dilution Methods 0.000 claims description 10
- 239000012895 dilution Substances 0.000 claims description 10
- 239000012141 concentrate Substances 0.000 claims description 8
- 230000003647 oxidation Effects 0.000 claims description 5
- 238000007254 oxidation reaction Methods 0.000 claims description 5
- CFMZSMGAMPBRBE-UHFFFAOYSA-N 2-hydroxyisoindole-1,3-dione Chemical compound C1=CC=C2C(=O)N(O)C(=O)C2=C1 CFMZSMGAMPBRBE-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- ZPEIMTDSQAKGNT-UHFFFAOYSA-N chlorpromazine Chemical compound C1=C(Cl)C=C2N(CCCN(C)C)C3=CC=CC=C3SC2=C1 ZPEIMTDSQAKGNT-UHFFFAOYSA-N 0.000 claims description 4
- 229960001076 chlorpromazine Drugs 0.000 claims description 4
- NPZTUJOABDZTLV-UHFFFAOYSA-N hydroxybenzotriazole Substances O=C1C=CC=C2NNN=C12 NPZTUJOABDZTLV-UHFFFAOYSA-N 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 3
- OHDRQQURAXLVGJ-HLVWOLMTSA-N azane;(2e)-3-ethyl-2-[(e)-(3-ethyl-6-sulfo-1,3-benzothiazol-2-ylidene)hydrazinylidene]-1,3-benzothiazole-6-sulfonic acid Chemical compound [NH4+].[NH4+].S/1C2=CC(S([O-])(=O)=O)=CC=C2N(CC)C\1=N/N=C1/SC2=CC(S([O-])(=O)=O)=CC=C2N1CC OHDRQQURAXLVGJ-HLVWOLMTSA-N 0.000 claims description 3
- 239000000872 buffer Substances 0.000 claims description 3
- 150000001875 compounds Chemical class 0.000 claims description 3
- QKUSRAKPUWQSJS-UHFFFAOYSA-N diazanium 3-ethyl-2H-1,3-benzothiazole-6-sulfonate Chemical class [NH4+].[NH4+].[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1.[O-]S(=O)(=O)C1=CC=C2N(CC)CSC2=C1 QKUSRAKPUWQSJS-UHFFFAOYSA-N 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 244000248349 Citrus limon Species 0.000 claims description 2
- 235000005979 Citrus limon Nutrition 0.000 claims description 2
- 229910019142 PO4 Inorganic materials 0.000 claims description 2
- 239000002253 acid Substances 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 230000000694 effects Effects 0.000 claims description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-K phosphate Chemical compound [O-]P([O-])([O-])=O NBIIXXVUZAFLBC-UHFFFAOYSA-K 0.000 claims description 2
- 239000010452 phosphate Substances 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- YEDUAINPPJYDJZ-UHFFFAOYSA-N 2-hydroxybenzothiazole Chemical compound C1=CC=C2SC(O)=NC2=C1 YEDUAINPPJYDJZ-UHFFFAOYSA-N 0.000 claims 1
- 159000000021 acetate salts Chemical class 0.000 claims 1
- 125000000746 allylic group Chemical group 0.000 claims 1
- 230000008878 coupling Effects 0.000 claims 1
- 238000010168 coupling process Methods 0.000 claims 1
- 238000005859 coupling reaction Methods 0.000 claims 1
- 238000001035 drying Methods 0.000 abstract description 7
- 238000010010 raising Methods 0.000 abstract description 7
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 abstract 1
- 238000007865 diluting Methods 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- 230000001590 oxidative effect Effects 0.000 abstract 1
- 238000000926 separation method Methods 0.000 abstract 1
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 18
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- -1 allyl group naphthalene compound Chemical class 0.000 description 5
- UFWIBTONFRDIAS-UHFFFAOYSA-N naphthalene-acid Natural products C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 5
- 239000008055 phosphate buffer solution Substances 0.000 description 5
- 108010054320 Lignin peroxidase Proteins 0.000 description 3
- 108010059896 Manganese peroxidase Proteins 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 2
- 108090000790 Enzymes Proteins 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 2
- 241000233866 Fungi Species 0.000 description 2
- CMWTZPSULFXXJA-UHFFFAOYSA-N Naproxen Natural products C1=C(C(C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 239000008351 acetate buffer Substances 0.000 description 2
- 230000001760 anti-analgesic effect Effects 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 238000006356 dehydrogenation reaction Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 238000009776 industrial production Methods 0.000 description 2
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- CMWTZPSULFXXJA-VIFPVBQESA-N naproxen Chemical compound C1=C([C@H](C)C(O)=O)C=CC2=CC(OC)=CC=C21 CMWTZPSULFXXJA-VIFPVBQESA-N 0.000 description 2
- 229960002009 naproxen Drugs 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 102000004169 proteins and genes Human genes 0.000 description 2
- 108090000623 proteins and genes Proteins 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000000758 substrate Substances 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- 238000001644 13C nuclear magnetic resonance spectroscopy Methods 0.000 description 1
- 238000005160 1H NMR spectroscopy Methods 0.000 description 1
- 241000003910 Baronia <angiosperm> Species 0.000 description 1
- 108010031396 Catechol oxidase Proteins 0.000 description 1
- 102000030523 Catechol oxidase Human genes 0.000 description 1
- 241000196324 Embryophyta Species 0.000 description 1
- 238000007341 Heck reaction Methods 0.000 description 1
- 241000238631 Hexapoda Species 0.000 description 1
- 241000864407 Panus conchatus Species 0.000 description 1
- 102000003992 Peroxidases Human genes 0.000 description 1
- 244000044283 Toxicodendron succedaneum Species 0.000 description 1
- 241000222355 Trametes versicolor Species 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000003110 anti-inflammatory effect Effects 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000004043 dyeing Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 239000002608 ionic liquid Substances 0.000 description 1
- 239000010985 leather Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000000050 nutritive effect Effects 0.000 description 1
- 150000007530 organic bases Chemical class 0.000 description 1
- 239000003973 paint Substances 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 108040007629 peroxidase activity proteins Proteins 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 description 1
- 238000004076 pulp bleaching Methods 0.000 description 1
- 229930000044 secondary metabolite Natural products 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 230000003637 steroidlike Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 238000004065 wastewater treatment Methods 0.000 description 1
Landscapes
- Preparation Of Compounds By Using Micro-Organisms (AREA)
Abstract
The invention discloses a laccase method for preparing 2-(6'-methoxy-2'-naphthyl) allyl alcohol. 2-(6'-methoxy-2'-naphthyl) propylene is taken as a raw material, a buffer solution and reaction medium combined system is utilized, and under the action of laccase, methyl at the allyl position is oxidized into a hydroxyl target by taking air as an oxidant. The method comprises the following steps of: dissolving the 2-(6'-methoxy-2'-naphthyl) propylene in ethanol, diluting by using buffer solution with the pH value of 4.5, raising the temperature to 45 DEG C, and adding a reaction medium and aqueous solution of the lacase; and introducing a slight amount of air into a reaction system, continuously stirring for 20 to 30 hours, after the reaction is finished, extracting by using methylbenzene, drying and concentrating the extracting solution, and performing column chromatography and separation to obtain the 2-(6'-methoxy-2'-naphthyl) allyl alcohol product. The preparation method is simple, is easy to operate, can prepare the product on a large scale and lightly pollutes environment.
Description
(1) technical field
The present invention relates to a kind of laccase legal system be equipped with 2-(6 '-methoxyl group-2 '-naphthyl) technology of vinyl carbinol.
(2) background technology
2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol is the Chinese medicine intermediate of preparation non-steroidal anti-inflammatory, analgesic and analgesic Naproxen Base (Naproxen), has wide demand market at home and abroad.The synthetic method of this compound has only two kinds at present.In the synthetic route of U.S. Pat 5286902 reports, set out, in the high-temperature tubular reactor, behind dehydrogenation catalyst dehydrogenation generation allyl group naphthalene compound, make through the tin anhydride oxidation by 2-methoxyl group-6-isopropyl naphthalene.With this synthetic method complicated operation, severe reaction conditions, used tin anhydride oxygenant toxicity is big, and the raw material sources difficulty of Synthetic 2-methoxyl group-6-isopropyl naphthalene, and synthetic route is longer, and yield is low, is difficult to carry out large-scale industrial production.Pei Wen etc. utilize the Heck reaction, have studied under palladium metal or the nickel catalysis, in ionic liquid, alkali and phosphine part reaction system, by naphthalene halide and vinyl carbinol reaction, have synthesized 2-and have replaced the naphthalene allyl alcohol compound.But in suitability for industrialized production, the chemical synthesis process process is owing to need to relate to problem of environmental pollution with the reaction medium, organic bases and the catalyzer that reclaim use.Therefore, development environment close friend's biosynthesis technology is the important content of Green Chemistry research, and utilizes the research of synthetic this compounds of biotechnology not appear in the newspapers as yet.
Laccase (Laccase) is the cupric polyphenoloxidase of a class degradable xylogen.As far back as 1883, Japanese scholar Yoshida found a kind of protein from lacquer tree (Rhus vernicifern), and it can make paint solidify rapidly.Bertrand was with this protein called after laccase in 1894.The distribution of laccase is very extensive, and except plant, it also is distributed in insect, bacterium and the higher fungi.Owing to originated, the restriction of aspect such as culture condition, when actual industrial production laccase all based on higher fungi, as Corilus versicolor Quel. (Coriolus versicolor), conchoidal leather ear bacterium (Panus conchatus).Except that decomposing xylogen, but laccase also catalyzed oxidation a large amount of with first similar phenolic compound of body structure of xylogen and aromatic amine, especially under the synergy of redox mediator, the substrate scope of laccase effect can further enlarge.Compare with other peroxidase, laccase has bigger actual application value.At first, lignin peroxidase (LiP) and manganese peroxidase (MnP) are the strict secondary metabolites that produces under limit carbon, limit nitrogen condition, and in the Industrial Wastewater Treatment process, a large amount of existence of carbon, nitrogenous source nutritive substance have limited the secretion of cell to enzyme.Secondly, because lignin peroxidase and manganese peroxidase when degradable organic pollutant, need a large amount of H
2O
2As auxiliary, this has limited its application in actual production.And laccase can not have H
2O
2Existence under, directly to the substrate catalyzed oxidation.Laccase has obtained extensive studies and application in the analysis of association with pulp bleaching, yarn fabric dyeing and finishing, organic pollutant processing, biosensor, trace substance, the fields such as improvement of food quality in recent years.The particularly important is laccase and under the assistance of some small molecules redox mediators, have stronger catalyzed oxidation ability, help developing the new application of this enzyme.Therefore, laccase-redox mediator system more and more receives concern both domestic and external as a kind of system with very big potential using value.
Summary of the invention
The object of the invention is to provide a kind of preparation technology simple, excellent catalytic effect, utilize laccase biosynthesis technology highly selective prepare 2-(6 '-methoxyl group-2 '-naphthyl) method of vinyl carbinol.
The technical solution used in the present invention is:
A kind of 2-(6 '-methoxyl group-2 '-naphthyl) preparation method of vinyl carbinol, it is characterized in that may further comprise the steps:
(1) with load weighted 2-(6 '-methoxyl group-2 '-naphthyl) propylene is dissolved in a certain amount of ethanol, every mmole 2-(6 '-methoxyl group-2 '-naphthyl) propylene, 1～10 milliliter of ethanol consumption;
(2) with the pH value be the propylene ethanolic soln of 4.5 buffered soln dilution step (1), every mmole 2-(6 '-methoxyl group-2 '-naphthyl) propylene, 1～10 milliliter of buffered soln consumption;
(3) step (2) dilution back solution is warmed up to 40-50 ℃;
(4) aqueous solution of reaction medium and laccase is joined step (3) and heats up in the solution of back, guarantee every mmole 2-(6 '-methoxyl group-2 '-naphthyl) propylene, the reaction medium consumption is 1～10 milliliter, laccase consumption 100～300IU;
(5) in reaction system, feed faint air and continuous the stirring 20～30 hours;
(6) after reaction finishes, with toluene 10-15ml extraction three times;
(7) combining extraction liquid and dry concentrates;
(8) at last with column chromatography separate 2-(6 '-methoxyl group-2 '-naphthyl) the vinyl carbinol product,
Reaction formula is as follows:
Described 2-(6 '-methoxyl group-2 '-naphthyl) preparation method of vinyl carbinol, it is characterized in that:
Described buffer solution system is selected from a kind of in citric acid/phosphoric acid buffer liquid system, the acetic acid/acetate buffer solution system, is preferably lemon acid/phosphate buffered liquid system;
Described reaction medium is selected from 2,2 '-Lian nitrogen-two (3-ethyl-benzothiazole-6-sulfonic acid) di-ammonium salts ABTS, I-hydroxybenzotriazole HOBT, 2,2,6, a kind of in 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO), chlorpromazine (CPZ), N-hydroxyphthalimide and 1-Nitroso-2-naphthol-3,6 sodium disulfonate (NNDS);
Described temperature of reaction is 40～50 ℃, is preferably 45 ℃;
The described reaction times is 20～30 hours, is preferably 24 hours.
Preparation method of the present invention, preparation technology is simple, and is easy to operate, but scale preparation, environmental pollution is little.
Embodiment
The present invention is described further below in conjunction with specific embodiment, but protection scope of the present invention is not limited in this:
Embodiment 1:
With 2-(6 '-methoxyl group-2 '-naphthyl) propylene 0.2 gram (1 mmole) is dissolved in 5 milliliters of ethanol, with 5 milliliters of dilutions of citric acid/phosphate buffer solution, 45 ℃ of heat temperature raisings, add 5 milliliters of reaction medium N-hydroxyphthalimides, the aqueous solution of laccase 150IU, in reaction system, feed faint air and continuous the stirring 24 hours, after reaction finishes, with 10 milliliters of extractions of toluene 3 times, the extraction liquid drying, concentrate, with column chromatography [V (ethyl acetate)/V (normal hexane)=1/2] separate 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol product 0.12 restrains yield 57%.132～133 ℃ of fusing points;
1H NMR (CDCl
3, 400MHz) δ: 1.76 (s, 1H), 3.91 (s, 3H), 4.63 (s, 2H), 5.41 (s, 1H), 5.58 (s, 1H), 7.11～7.16 (m, 2H), 7.57～7.59 (m, 1H), 7.70～7.74 (m, 2H), 7.82 (m, 1H);
13C NMR (CDCl
3, 400MHz) δ: 60.1,65.9,106.4,113.1,119.7,125.3,125.5,127.6,129.5,130.4,134.9,139.1,147.8,158.6; IR (KBr) v:3050,1590,1450,1390cm
-1MS (70eV) m/z (%): 214 (M
+).
Embodiment 2:
With 2-(6 '-methoxyl group-2 '-naphthyl) propylene 0.2 gram (1 mmole) is dissolved in 5 milliliters of ethanol, with 5 milliliters of dilutions of acetic acid/acetate buffer solution, 45 ℃ of heat temperature raisings, add reaction medium I-hydroxybenzotriazole (HOBT) 5 milliliters, the aqueous solution of laccase 150IU, in reaction system, feed faint air and continuous the stirring 24 hours, after reaction finishes, with 10 milliliters of extractions of toluene 3 times, the extraction liquid drying, concentrate, with column chromatography [V (ethyl acetate)/V (normal hexane)=1/2] separate 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol product 0.12 restrains yield 57%.
Embodiment 3:
With 2-(6 '-methoxyl group-2 '-naphthyl) propylene 0.2 gram (1 mmole) is dissolved in 10 milliliters of ethanol, with 10 milliliters of dilutions of citric acid/phosphate buffer solution, 40 ℃ of heat temperature raisings, add 1 milliliter of reaction medium N-hydroxyphthalimide, the aqueous solution of laccase 100IU, in reaction system, feed faint air and continuous the stirring 24 hours, after reaction finishes, with 10 milliliters of extractions of toluene 3 times, the extraction liquid drying, concentrate, with column chromatography [V (ethyl acetate)/V (normal hexane)=1/2] separate 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol product 0.1 restrains yield 48%.
Embodiment 4:
With 2-(6 '-methoxyl group-2 '-naphthyl) propylene 0.2 gram (1 mmole) is dissolved in 5 milliliters of ethanol, with 5 milliliters of dilutions of citric acid/phosphate buffer solution, 50 ℃ of heat temperature raisings, add reaction medium 2,5 milliliters of 2 '-Lian nitrogen-two (3-ethyl-benzothiazole-6-sulfonic acid) di-ammonium salts (ABTS), the aqueous solution of laccase 300IU, in reaction system, feed faint air and continuous the stirring 20 hours, after reaction finishes, with 10 milliliters of extractions of toluene 3 times, the extraction liquid drying concentrates, with column chromatography [V (ethyl acetate)/V (normal hexane)=1/2] separate 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol product 0.09 gram, yield 45%.
Embodiment 5:
With 2-(6 '-methoxyl group-2 '-naphthyl) propylene 0.2 gram (1 mmole) is dissolved in 5 milliliters of ethanol, with 5 milliliters of dilutions of citric acid/phosphate buffer solution, 45 ℃ of heat temperature raisings, add reaction medium 2,2,6,5 milliliters in 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO), the aqueous solution of laccase 150IU feeds faint air and continuous the stirring 24 hours in reaction system, after reaction finishes, with 10 milliliters of extractions of toluene 3 times, the extraction liquid drying concentrates, with column chromatography [V (ethyl acetate)/V (normal hexane)=1/2] separate 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol product 0.1 gram, yield 48%.
Embodiment 6:
With 2-(6 '-methoxyl group-2 '-naphthyl) propylene 0.2 gram (1 mmole) is dissolved in 5 milliliters of ethanol, with 5 milliliters of dilutions of citric acid/phosphate buffer solution, 45 ℃ of heat temperature raisings, add reaction medium 1-Nitroso-2-naphthol-3,5 milliliters of 6 sodium disulfonates (NNDS), the aqueous solution of laccase 150IU, in reaction system, feed faint air and continuous the stirring 30 hours, after reaction finishes, with 10 milliliters of extractions of toluene 3 times, the extraction liquid drying concentrates, with column chromatography [V (ethyl acetate)/V (normal hexane)=1/2] separate 2-(6 '-methoxyl group-2 '-naphthyl) vinyl carbinol product 0.12 gram, yield 57%.
Claims (2)
- A 2-(6 '-methoxyl group-2 '-naphthyl) preparation method of vinyl carbinol, it is characterized in that: with 2-(6 '-methoxyl group-2 '-naphthyl) propylene is raw material, utilize buffered soln and reaction medium coupling system, under the effect of laccase, with the air be oxygenant to make the methyl oxidation of allylic be the hydroxyl target compound, concrete steps are as follows:(1) with load weighted 2-(6 '-methoxyl group-2 '-naphthyl) propylene is dissolved in a certain amount of ethanol, every mmole 2-(6 '-methoxyl group-2 '-naphthyl) propylene, 1～10 milliliter of ethanol consumption;(2) with the pH value be 4.5 the described propylene ethanolic soln of buffered soln dilution step (1), every mmole 2-(6 '-methoxyl group-2 '-naphthyl) propylene, 1～10 milliliter of buffered soln consumption;(3) step (2) dilution back solution is warmed up to 40-50 ℃;(4) aqueous solution of reaction medium and laccase is joined step (3) and heats up in the solution of back, guarantee every mmole 2-(6 '-methoxyl group-2 '-naphthyl) propylene, the reaction medium consumption is 1～10 milliliter, laccase consumption 100～300IU;(5) in reaction system, feed faint air and continuous the stirring 20～30 hours;(6) after reaction finishes, with toluene 10-15ml extraction three times;(7) combining extraction liquid and dry concentrates;(8) at last with column chromatography separate 2-(6 '-methoxyl group-2 '-naphthyl) the vinyl carbinol product,Reaction formula is as follows:
- 2-2. according to claim 1 (6 '-methoxyl group-2 '-naphthyl) preparation method of vinyl carbinol, it is characterized in that:Described buffer solution system is selected from a kind of in citric acid/phosphoric acid buffer liquid system, the acetate salt buffer liquid system, is preferably lemon acid/phosphate buffered liquid system;Described reaction medium is selected from 2,2 '-Lian nitrogen-two (3-ethyl-benzothiazole-6-sulfonic acid) di-ammonium salts ABTS, I-hydroxybenzotriazole HOBT, 2,2,6, a kind of in 6-tetramethyl piperidine-nitrogen-oxide compound (TEMPO), chlorpromazine (CPZ), N-hydroxyphthalimide and 1-Nitroso-2-naphthol-3,6 sodium disulfonate (NNDS);Described temperature of reaction is 40～50 ℃, is preferably 45 ℃;The described reaction times is 20～30 hours, is preferably 24 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN 201010229704 CN101967497B (en) | 2010-07-15 | 2010-07-15 | Preparation of 2-(6'-methoxy-2'-naphthyl) allyl alcohol by laccase method |
Applications Claiming Priority (1)
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726504A (en) * | 2015-03-27 | 2015-06-24 | 南京理工大学 | Method for laccase catalytic synthesis of 5,5'-dehydrodiacetovanillone |
| CN110845018A (en) * | 2019-11-07 | 2020-02-28 | 桂林理工大学 | Method for improving degradation rate of laccase for degrading diethylstilbestrol |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101161617A (en) * | 2007-11-15 | 2008-04-16 | 浙江工业大学 | A method for preparing 2-(6'-methoxy group-2'-naphthyl) propenol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101161617A (en) * | 2007-11-15 | 2008-04-16 | 浙江工业大学 | A method for preparing 2-(6'-methoxy group-2'-naphthyl) propenol |
Non-Patent Citations (3)
| Title |
|---|
| 《Tetrahedron Letters》 19980813 Elke Fritz-Langhals 等 Synthesis of aromatic aldehydes by laccase-mediator assisted oxidation 5955-5956 1-2 第39卷, 第33期 * |
| 《Tetrahedron》 20060605 Isabel W. C. E. Arends 等 Comparison of TEMPO and its derivatives as mediators in laccase catalysed oxidation of alcohols 6659-6665 1-2 第62卷, 第28期 * |
| 《有机化学》 20081031 姜标 等 用于生物氧化的蓝色漆酶 1715-1723 1-2 第28卷, 第10期 * |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104726504A (en) * | 2015-03-27 | 2015-06-24 | 南京理工大学 | Method for laccase catalytic synthesis of 5,5'-dehydrodiacetovanillone |
| CN104726504B (en) * | 2015-03-27 | 2018-08-10 | 南京理工大学 | The Laccase Catalyzed synthetic method of 5,5 '-dehydrogenation, two Acetovanillone |
| CN110845018A (en) * | 2019-11-07 | 2020-02-28 | 桂林理工大学 | Method for improving degradation rate of laccase for degrading diethylstilbestrol |
| CN110845018B (en) * | 2019-11-07 | 2021-12-07 | 桂林理工大学 | Method for improving degradation rate of laccase for degrading diethylstilbestrol |
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Denomination of invention: Preparation of 2- (6 '- methoxy-2' - naphthyl) allyl alcohol by laccase method Granted publication date: 20121205 Pledgee: Agricultural Bank of China Limited Dongzhi County Branch Pledgor: Chizhou Fangda Technology Co.,Ltd.|Chen Fang Registration number: Y2024980002081 |
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