CN101768608B - Method utilizing one-pot method to synthesize Wieland-Michelle ketone compound - Google Patents
Method utilizing one-pot method to synthesize Wieland-Michelle ketone compound Download PDFInfo
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- CN101768608B CN101768608B CN2009101556875A CN200910155687A CN101768608B CN 101768608 B CN101768608 B CN 101768608B CN 2009101556875 A CN2009101556875 A CN 2009101556875A CN 200910155687 A CN200910155687 A CN 200910155687A CN 101768608 B CN101768608 B CN 101768608B
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- 238000000034 method Methods 0.000 title claims abstract description 25
- -1 ketone compound Chemical class 0.000 title claims abstract description 17
- 238000005580 one pot reaction Methods 0.000 title abstract 2
- 238000006243 chemical reaction Methods 0.000 claims abstract description 23
- 108090000790 Enzymes Proteins 0.000 claims abstract description 18
- 102000004190 Enzymes Human genes 0.000 claims abstract description 18
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 12
- 125000005594 diketone group Chemical group 0.000 claims abstract description 11
- 239000000758 substrate Substances 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 8
- 241000282894 Sus scrofa domesticus Species 0.000 claims description 8
- 210000000496 pancreas Anatomy 0.000 claims description 8
- 229910002027 silica gel Inorganic materials 0.000 claims description 8
- 239000000741 silica gel Substances 0.000 claims description 8
- 229960001866 silicon dioxide Drugs 0.000 claims description 8
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 6
- 210000002784 stomach Anatomy 0.000 claims description 5
- 108010019077 beta-Amylase Proteins 0.000 claims description 4
- 239000000126 substance Substances 0.000 claims description 4
- 235000007340 Hordeum vulgare Nutrition 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 239000000706 filtrate Substances 0.000 claims description 2
- 240000005979 Hordeum vulgare Species 0.000 claims 1
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 description 15
- 229940088598 enzyme Drugs 0.000 description 14
- 150000001875 compounds Chemical class 0.000 description 13
- 238000010025 steaming Methods 0.000 description 12
- 150000002576 ketones Chemical class 0.000 description 10
- 238000005160 1H NMR spectroscopy Methods 0.000 description 6
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonia chloride Chemical class [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 6
- 239000007795 chemical reaction product Substances 0.000 description 6
- 239000000047 product Substances 0.000 description 6
- 238000011084 recovery Methods 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- 230000015572 biosynthetic process Effects 0.000 description 4
- 229930014626 natural product Natural products 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 108010059892 Cellulase Proteins 0.000 description 3
- 229940106157 cellulase Drugs 0.000 description 3
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 2
- 241000209219 Hordeum Species 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000035484 reaction time Effects 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- XDCHRHIXCMMJNQ-UHFFFAOYSA-N CC(C(CN1)=O)C1=O Chemical compound CC(C(CN1)=O)C1=O XDCHRHIXCMMJNQ-UHFFFAOYSA-N 0.000 description 1
- JECHAQVVHAMRKP-UHFFFAOYSA-N CC(CC1)(C(CN2)=O)C2=CC1=O Chemical compound CC(CC1)(C(CN2)=O)C2=CC1=O JECHAQVVHAMRKP-UHFFFAOYSA-N 0.000 description 1
- PDSNLYSELAIEBU-UHFFFAOYSA-N Longifolene Chemical compound C1CCC(C)(C)C2C3CCC2C1(C)C3=C PDSNLYSELAIEBU-UHFFFAOYSA-N 0.000 description 1
- ZPUKHRHPJKNORC-UHFFFAOYSA-N Longifolene Natural products CC1(C)CCCC2(C)C3CCC1(C3)C2=C ZPUKHRHPJKNORC-UHFFFAOYSA-N 0.000 description 1
- 241001465754 Metazoa Species 0.000 description 1
- NTIZESTWPVYFNL-UHFFFAOYSA-N Methyl isobutyl ketone Chemical compound CC(C)CC(C)=O NTIZESTWPVYFNL-UHFFFAOYSA-N 0.000 description 1
- 238000006845 Michael addition reaction Methods 0.000 description 1
- 229930012538 Paclitaxel Natural products 0.000 description 1
- ONIBWKKTOPOVIA-UHFFFAOYSA-N Proline Natural products OC(=O)C1CCCN1 ONIBWKKTOPOVIA-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000005575 aldol reaction Methods 0.000 description 1
- 230000001093 anti-cancer Effects 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000005842 biochemical reaction Methods 0.000 description 1
- 230000003115 biocidal effect Effects 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 229930004069 diterpene Natural products 0.000 description 1
- 150000004141 diterpene derivatives Chemical class 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 235000021050 feed intake Nutrition 0.000 description 1
- 230000004957 immunoregulator effect Effects 0.000 description 1
- 230000004060 metabolic process Effects 0.000 description 1
- 239000006225 natural substrate Substances 0.000 description 1
- 230000004770 neurodegeneration Effects 0.000 description 1
- TVMXDCGIABBOFY-UHFFFAOYSA-N octane Chemical compound CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 1
- 229960001592 paclitaxel Drugs 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 229930004725 sesquiterpene Natural products 0.000 description 1
- 150000004354 sesquiterpene derivatives Chemical class 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000010189 synthetic method Methods 0.000 description 1
- 239000003760 tallow Substances 0.000 description 1
- RCINICONZNJXQF-MZXODVADSA-N taxol Chemical compound O([C@@H]1[C@@]2(C[C@@H](C(C)=C(C2(C)C)[C@H](C([C@]2(C)[C@@H](O)C[C@H]3OC[C@]3([C@H]21)OC(C)=O)=O)OC(=O)C)OC(=O)[C@H](O)[C@@H](NC(=O)C=1C=CC=CC=1)C=1C=CC=CC=1)O)C(=O)C1=CC=CC=C1 RCINICONZNJXQF-MZXODVADSA-N 0.000 description 1
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- Preparation Of Compounds By Using Micro-Organisms (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention provides a method utilizing a one-pot method to synthesize a Wieland-Michelle ketone compound. The method includes the following steps: diketone and methyl vinyl ketone shown in a formula (I) are adopted as a reaction substrate and are reacted in an organic solvent under the catalytic action of enzyme so as to obtain the Wieland-Michelle ketone compound shown in the formula (I). The method in the invention mainly has the following benefits: by adopting the above method, the Wieland-Michelle ketone compound can be synthesized in one step; moreover, the method is simple, the efficiency is high, and the product yield is high.
Description
(1) technical field
The present invention relates to the method for the synthetic Wei Lande of a kind of one kettle way-Mi Xieer ketone compounds.
(2) background technology
Enzyme is a kind of protein that catalytic activity is arranged, and is a kind of biological catalyst that viable cell produces in the organism.Under can be in the body very gentle condition, the various biochemical reactions of catalysis promote the metabolism of organism expeditiously.Has high efficiency, specificity, characteristics such as reaction conditions gentleness.The eighties, scientist finds that enzyme also has the activity of height in organic solvent, this has expanded the application of enzyme in organic synthesis greatly.In recent years, " the confusion catalysis of enzyme " becomes a new focus of biocatalysis research field again, it be meant enzyme except can catalysis its natural substrate, ability that can also other reaction of catalysis.Such as discovering that lypase can catalysis Michael addition and aldol reaction.
Wei Lande-Mi Xieer ketone is the basic raw material of sterid synthetic.Natural product has in complete synthesis and surpasses in 50 compound and need use it as starting raw material in modern times.Sesquiterpene particularly, diterpene, and the synthesis material of natural product such as SUV, often have as starting raw material synthetic natural product with it anticancer, antibiotic, opposing neurodegeneration and immunoregulatory effect.Begin from Wei Lande-Mi Xieer ketone exactly such as the taxol of Dan Nixie Paderewski is complete synthesis; Longifolene in the section is complete synthesis also to be to do raw material with Wei Lande-Mi Xieer ketone.Therefore, we say that Wei Lande-Mi Xieer ketone is a kind of very important midbody with natural product of extensive effect.Efficient with a kind of approximate natural synthetic method, synthesize to environmental protection this material and still on meaning, all seem very important technically.
(3) summary of the invention
The object of the invention provides a kind of method that one kettle way synthesizes Wei Lande-Mi Xieer ketone compounds under the catalysis of enzyme.
The technical scheme that the present invention adopts is:
A kind of one kettle way synthesizes the method for Wei Lande-Mi Xieer ketone compounds; Said method comprises: with diketone shown in the formula (I) and methylene acetone is reaction substrate; Under the katalysis of enzyme, in organic solvent, react, make the Wei Lande shown in the formula (II)-Mi Xieer ketone compounds;
In formula (I), the formula (II), n is 1 or 2; N is 2 o'clock, and product is Wei Lande-Mi Xieer ketone;
Said organic solvent is one of following: 1. normal hexane, 2. pyridine, 3. octane, 4. isopropyl acetone, 5. tetracol phenixin, 6. methylene dichloride, 7. N, dinethylformamide, 8. 1,4-dioxane, 9. DMSO, the 10. alcohol of C1～C6;
Said enzyme is one of following: 1. glycase, 2. stomach en-, 3. cellulase, 4. animal tallow enzyme.Enzyme dosage is advisable with catalytic amount, also can be excessive slightly.
Wei Lande-Mi Xieer the ketone compounds of tradition described in the method for making makes as follows: by two kinds of substrates shown in the formula (I), under the catalysis of acid, first synthetic mesophase product b obtains product d with proline(Pro) catalysis after doing certain processing then again.It is complicated that technology shows slightly, and have certain contaminative.
The inventive method is: next step generates title product under the catalysis of enzyme, and reaction equation is shown below:
Diketone shown in the said formula (I) and methylene acetone consumption are so that diketone fully reacts is advisable, and normally methylene acetone is excessive slightly, and the ratio of diketone shown in the said formula (I) and methylene acetone amount of substance is preferably 1: 1～and 1.5, most preferably be 1: 1.5.
Said reaction can be carried out to the solvent boiling point TR at 0 ℃, preferably carries out 3～48 hours reaction times at 20～70 ℃.Most preferably under 70 ℃, carry out reaction times 36h.
It is one of following that said enzyme is preferably: 1. from the AMS of Pancreas Sus domestica, 2. from the stomach en-of Pancreas Sus domestica, 3. from the beta-amylase of barley.
Said organic solvent is preferably the alcohol of C1～C6, most preferably is ethanol.
Preferably, said method is following: enzyme is dissolved in the organic solvent, adds methylene acetone; Bathed altogether 0.5～1 hour in 35～38 ℃, add the diketone shown in the formula (I) then, 60～70 ℃ of shaking tables reaction 30～36h; After reaction finishes, filter, getting filtrates to revolve to boil off desolventizes; Silicagel column separates, and obtains said Wei Lande-Mi Xieer ketone compounds; The feed intake ratio of amount of substance of diketone shown in the formula (I) and methylene acetone is 1: 1.5.
Beneficial effect of the present invention is mainly reflected in: adopt the inventive method, but the said Wei Lande of one-step synthesis-Mi Xieer ketone compounds, because enzyme is insoluble to organic solvent, separation is simple, and method is simply efficient, and product yield is high.
(4) embodiment
Below in conjunction with specific embodiment the present invention is described further, but protection scope of the present invention is not limited in this:
Embodiment 1: the AMS catalysis generation Wei Lande-Mi Xieer reactive ketone formula from Pancreas Sus domestica is following:
In the 25mL flask, add new dimethyl-hydroresorcinol (5.0mmol), the glycase 25mg (available from the lark prestige) of steaming, put into 5ml ethanol; Under 37 ℃, bathe half a hour altogether, add the new methylene acetone (7.5mmol) that steams then, put into 70 ℃ of following shaking tables, 160 commentaries on classics/min; Reaction 36h adds the saturated ammonium chloride termination reaction, filters; After revolving steaming, separate end product, get faint yellow oily compound after the processing with silicagel column.Total recovery about 95%.
Compound characterizes: IR (cm
-1): 2960 (C-H), 1685 (C=O), 1620 (C=C);
1H NMR (CDCl
3): 5.85 (s, 1H), 2.86 (m, 2H), 2.50 (m, 4H), 2.25 (m, 3H), 1.70 (m, 1H), 1.45 (s, 3H), 1.33 (s, 3H) .MS (70eV): m/z (%)=178 (M
+).
Embodiment 2: the AMS catalysis from Pancreas Sus domestica generates product 7a-methyl-2,3,5,6,7,7a-six hydrogen-1H-indenes-1,5-diketone
Similar with embodiment 1, in the 25mL flask, add new dimethyl-hydroresorcinol (5.0mmol), the glycase 25mg of steaming, put into the 5ml normal hexane; Under 37 ℃, bathe half a hour altogether, add the new methylene acetone (5.0mmol) that steams then, put into 60 ℃ of following shaking tables, 160 commentaries on classics/min; Reaction 36h adds the saturated ammonium chloride termination reaction, filters; After revolving steaming, separate end product, get faint yellow oily compound after the processing with silicagel column.Total recovery about 90%.
Compound characterizes:
1H-NMR(CDCl3，δ，ppm)：5.98(s，1H)，2.96(m，1H)，2.80(m，2H)，2.50(m，2H)，2.10(m，2H)，1.91(m，1H)，1.33(s，3H)IR(cm
-1)：2957，1680，1610.MS(70eV)：m/z(％)＝164(M
+).
Embodiment 3: the stomach en-catalysis generation Wei Lande-Mi Xieer reactive ketone that comes from Pancreas Sus domestica is following:
In the 25mL flask, add new dimethyl-hydroresorcinol (5.0mmol), stomach en-(available from the lark prestige) 25mg of steaming, put into 5mlDMSO; Under 37 ℃, bathe half a hour altogether, add the new methylene acetone (5.0mmol) that steams then, put into 70 ℃ of following shaking tables, 160 commentaries on classics/min; Reaction 36h adds the saturated ammonium chloride termination reaction, filters; After revolving steaming, separate end product, get faint yellow oily compound after the processing with silicagel column.Total recovery about 93%.
Compound characterizes: IR (cm
-1): 2960 (C-H), 1685 (C=O), 1620 (C=C);
1H NMR (CDCl
3): 5.85 (s, 1H), 2.86 (m, 2H), 2.50 (m, 4H), 2.25 (m, 3H), 1.70 (m, 1H), 1.45 (s, 3H), 1.33 (s, 3H) .MS (70eV): m/z (%)=178 (M
+).
Embodiment 4: lypase L0057 (available from the lark prestige) catalysis that comes from Pancreas Sus domestica generates Wei Lande-Mi Xieer ketone
React as follows:
In the 25mL flask, add new dimethyl-hydroresorcinol (5.0mmol), the lypase L005730mg (available from the lark prestige) of steaming, put into 5ml ethanol; Under 37 ℃, bathe half a hour altogether, add the new methylene acetone (5.0mmol) that steams then, put into 70 ℃ of following shaking tables, 160 commentaries on classics/min; Reaction 18h adds the saturated ammonium chloride termination reaction, filters; After revolving steaming, separate end product, get faint yellow oily compound after the processing with silicagel column.Total recovery about 97%.
Compound characterizes: IR (cm
-1): 2960 (C-H), 1685 (C=O), 1620 (C=C);
1H NMR (CDCl
3): 5.85 (s, 1H), 2.86 (m, 2H), 2.50 (m, 4H), 2.25 (m, 3H), 1.70 (m, 1H), 1.45 (s, 3H), 1.33 (s, 3H) .MS (70eV): m/z (%)=178 (M
+).
Embodiment 5: the cellulase catalysis that comes from viride generates Wei Lande-Mi Xieer ketone: react as follows:
In the 25mL flask, add new dimethyl-hydroresorcinol (5.0mmol), the cellulase 25mg (available from the lark prestige) of steaming, put into 5ml ethanol; Under 37 ℃, bathe half a hour altogether, add the new methylene acetone (5.0mmol) that steams then, put into 70 ℃ of following shaking tables, 160 commentaries on classics/min; Reaction 36h adds the saturated ammonium chloride termination reaction, filters; After revolving steaming, separate end product, get faint yellow oily compound after the processing with silicagel column.Total recovery about 85%.
Compound characterizes: IR (cm
-1): 2960 (C-H), 1685 (C=O), 1620 (C=C);
1H NMR (CDCl
3): 5.85 (s, 1H), 2.86 (m, 2H), 2.50 (m, 4H), 2.25 (m, 3H), 1.70 (m, 1H), 1.45 (s, 3H), 1.33 (s, 3H) .MS (70eV): m/z (%)=178 (M
+).
Embodiment 6: the beta-amylase catalysis generation Wei Lande-Mi Xieer reactive ketone that comes from barley is following:
In the 25mL flask, add new dimethyl-hydroresorcinol (5.0mmol), the beta-amylase 25mg (available from the lark prestige) of steaming, put into 5mlDMSO; Under 37 ℃, bathe half a hour altogether, add the new methylene acetone (5.0mmol) that steams then, put into 70 ℃ of following shaking tables, 160 commentaries on classics/min; Reaction 36h adds the saturated ammonium chloride termination reaction, filters; After revolving steaming, separate end product, get faint yellow oily compound after the processing with silicagel column.Total recovery about 90%.
Compound characterizes: IR (cm
-1): 2960 (C-H), 1685 (C=O), 1620 (C=C);
1H NMR (CDCl
3): 5.85 (s, 1H), 2.86 (m, 2H), 2.50 (m, 4H), 2.25 (m, 3H), 1.70 (m, 1H), 1.45 (s, 3H), 1.33 (s, 3H) .MS (70eV): m/z (%)=178 (M
+).
Claims (5)
1. the method for the synthetic Wei Lande of an one kettle way-Mi Xieer ketone compounds; Said method comprises: with diketone shown in the formula (I) and methylene acetone is reaction substrate; Under the katalysis of enzyme; In organic solvent, reacted 3～48 hours, make the Wei Lande shown in the formula (II)-Mi Xieer ketone compounds at 20～70 ℃;
In formula (I), the formula (II), n is 1 or 2;
Said organic solvent is one of following: 1. normal hexane, 9. DMSO, the 10. alcohol of C1～C6;
Said enzyme is one of following: 1. from the AMS of Pancreas Sus domestica, 2. from the stomach en-of Pancreas Sus domestica, 3. from the beta-amylase of barley.
2. the method for claim 1, the ratio that it is characterized in that diketone shown in the said formula (I) and methylene acetone amount of substance is 1: 1～1.5.
3. the method for claim 1 is characterized in that said organic solvent is the alcohol of C1～C6.
4. method as claimed in claim 3 is characterized in that said organic solvent is an ethanol.
5. the method for claim 1 is characterized in that said method is following: enzyme is dissolved in the organic solvent, adds methylene acetone; Bathed altogether 0.5～1 hour in 35～38 ℃, add the diketone shown in the formula (I) then, 60～70 ℃ of shaking tables reaction 30～36h; After reaction finishes, filter, getting filtrates to revolve to boil off desolventizes; Silicagel column separates, and obtains said Wei Lande-Mi Xieer ketone compounds; Diketone shown in the formula (I) is 1: 1.5 with the ratio of methylene acetone amount of substance.
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2009
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Patent Citations (4)
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|---|---|---|---|---|
| WO2003061651A1 (en) * | 2002-01-22 | 2003-07-31 | The Regents Of The University Of California | Non-steroidal ligands for the glucocorticoid receptor, compositions and uses thereof |
| WO2003086294A2 (en) * | 2002-04-11 | 2003-10-23 | Merck & Co., Inc. | 1h-benzo[f]indazol-5-yl derivatives as selective glucocorticoid receptor modulators |
| CN101557857A (en) * | 2006-12-13 | 2009-10-14 | 吉万奥丹股份有限公司 | Cylohexenyl butenones and fragrance compositions comprising them |
| CN101343220A (en) * | 2008-08-22 | 2009-01-14 | 西安瑞联近代电子材料有限责任公司 | Preparation method for 3-methyl-4-phenyl-2-butanone |
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