CN102557880B - Method for synthesizing p-menthane-3,9-diol - Google Patents
Method for synthesizing p-menthane-3,9-diol Download PDFInfo
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- CN102557880B CN102557880B CN201110428885.1A CN201110428885A CN102557880B CN 102557880 B CN102557880 B CN 102557880B CN 201110428885 A CN201110428885 A CN 201110428885A CN 102557880 B CN102557880 B CN 102557880B
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- isopulegol
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Abstract
The invention discloses a method for synthesizing p-menthane-3,9-diol[2-(1-methyl-2-hydroxyl)ethyl-5-methylcyclohexan-1-ol]. The method comprises the following steps of: performing epoxidation reaction on isopulegol serving as a raw material to obtain 8,9-epoxy isopulegol, and performing selective reduction on the 8,9-epoxy isopulegol by a raney nickel catalytic hydrogenation method to obtain p-menthane-3,9-diol. The invention has the advantages that: the synthesis process is simple, reaction conditions are mild, and the method is easy and convenient to operate, environment-friendly and suitable for industrially producing the p-menthane-3,9-diol on a large scale.
Description
Technical field
The invention belongs to organic chemical synthesis technical field, be specifically related to a kind of take isopulegol as raw material synthetic to menthane-3, the method for 9-glycol [2-(1-methyl-2-hydroxyl) ethyl-5-methyl cyclohexane-1-alcohol].
Background technology
To menthane-3,9-glycol has special fragrance and cool feeling, and it can be used as intermediate useful in organic synthesis, prepares dihydro peppermint lactone as can be used for.
From isopulegol, synthesize menthane-3, the synthetic method of 9-glycol is divided two kinds: (1) take isopulegol as raw material, by after 3 hydroxyl protections, by hydroboration-oxidizing reaction, deprotection, makes to menthane-3 9-glycol; (2) take isopulegol as raw material, available superoxide epoxidation synthesizes 8,9-epoxy isopulegol (Waddell T.G., Ross P.A.J.Org.Chem., 1987,52:4802-4804; Schulte-Elte, K H., Ohloff, G., Helv.Chim.Acta, 1961,50 (21): 153-165.), with highly basic catalysis such as diisopropylamine lithiums, make it tautomerize to 2-(1-methylol) vinyl-5-methyl cyclohexane-1-alcohol again, rear catalytic hydrogenation carbon-carbon double bond makes menthane-3,9-glycol.
The shortcoming of first method is: technique is loaded down with trivial details, cost is higher: hydroboration requires by sodium borohydride, to produce diborane with the complex compound scene of reacting of boron trifluoride diethyl etherate under anhydrous and oxygen-free condition, requirement of shelter to equipment and personnel is high, expensive (the Casanovas of reagent, J., Namba, A M., et al., J.Org.Chem.2001,66,3775-3782; Schmid, G., Hofheinz, W., J.Am.Chem.Soc., 1983,105:624-625); 3 alcoholic extract hydroxyl groups need protection and deprotection.The shortcoming of second method is: by under isopulegol epoxidation, anhydrous condition with quadrol lithium catalysis methyl oxirane ring tautomerize to vinyl carbinol, catalytic hydrogenation carbon-carbon double bond obtains target product again, need altogether three-step reaction comparatively loaded down with trivial details, following (the schemel) (Schulte-Elte of reaction formula, K H., Ohloff, G., Helv.Chim.Acta, 1961,50 (21): 153-165).
Summary of the invention
Prior art before technical scheme of the present invention does not have to propose to how efficient, easy preparation to menthane-3,9-glycol [2-(1-methyl-2-hydroxyl) ethyl-5-methyl cyclohexane-1-alcohol], those skilled in the art does not still have corresponding terms of settlement.And object of the present invention is also to provide a kind of synthetic to menthane-3, the method for 9-glycol, the method synthesis technique is simple, productive rate is high, selectivity is good, be applicable to large-scale commercial production to menthane-3,9-glycol.
For reaching above-mentioned purpose, technical scheme of the present invention is: take isopulegol as starting raw material, first through superoxide epoxidation reaction, make 8,9-epoxy isopulegol, again under 10atm to 100atm hydrogen pressure through raney ni catalysis hydrogenation 8,9-epoxy isopulegol shares two-step reaction and makes menthane-3,9-glycol [2-(1-methyl-2-hydroxyl) ethyl-5-methyl cyclohexane-1-alcohol].
Method of the present invention specifically comprises following two steps:
Step 1: epoxidation: with superoxide, as metachloroperbenzoic acid, Peracetic Acid or hydrogen peroxide etc. are oxidized to 8 by isopulegol, 9-epoxy isopulegol.Reaction formula following (scheme2):
Step 2: selective hydration: 8,9-epoxy isopulegol is produced menthane-3 with selective hydration under raney ni catalysis under heating and pressurizing condition, 9-glycol, reaction formula following (scheme3):
The consumption of catalyzer Raney's nickel is between the 5%-50% of 8,9-epoxy isopulegol quality, and 25-35% is better catalytic amount, and 30% is best.Raney ni catalysis hydrogenation 8,9-epoxy isopulegol is synthetic to menthane-3, adds the hydrogen of dividing potential drop 10atm-100atm during 9-glycol.
The reaction medium of catalyzer Raney's nickel is small molecular alcohol: a kind of as in methyl alcohol, ethanol, Virahol, butanols etc., or a kind of in the mixed solvent of methyl alcohol+water, ethanol+water, Virahol+water, the mixed solvent of particular methanol+water, ethanol+water or Virahol+water.
Provided by the present inventionly by selective hydration, prepare menthane-3, the method for 9-glycol is very simplified on operating procedure, and original comparatively loaded down with trivial details three-step reaction can be simplified to two steps reactions can complete; And to menthane-3, the yield of 9-glycol is greater than 60%.Therefore, technique of the present invention has that synthesis technique is simple, productive rate is higher, selectivity good, catalyst activity is high, reclaim good effect and the features such as simple, be applicable to large-scale commercial production to menthane-3,9-glycol, efficiently solves the problem of high cost in the original preparation process of target product or complex process.
In sum, method of the present invention can make preparation technology more simplify, and the yield of product can significantly improve, and the industrial applications prospect of target product is had to great contribution, efficiently solves long-term puzzlement those skilled in the art's technical barrier.
Embodiment
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
The present invention be take isopulegol as raw material, and synthetic 8, the 9-epoxy isopulegol concrete operations of available superoxide epoxidation can be referring to document: Waddell T.G., Ross P.A.J.Org.Chem., 1987,52:4802-4804; Schulte-Elte, K H., Ohloff, G., Helv.Chim.Acta, 1961,50 (21): 153-165.
Embodiment 1
In 100mL autoclave, add 1.0g (5.9mmol) 8,9-epoxy isopulegol and 2mL methyl alcohol, add Raney's nickel 0.3g, passes into the hydrogen of 48atm.At 60 ℃, stirring reaction is 5 hours, and reaction is finished, and carefully reaction solution is inclined to.Filter, concentrated rear pillar chromatographic separation, to menthane-3, the yield of 9-glycol is 64%.To menthane-3, the spectral data of 9-glycol is:
1h NMR: δ 0.81-1.06 (m, 2H), 0.92 (d, J=6.8Hz, 3H), 0.96 (d, J=7.2Hz, 3H), 1.16-1.28 (m, 1H), 1.31-1.45 (m, 2H), 1.54-1.65 (m, 2H), 1.84 (s, 1H), 1.94-1.97 (m, 1H), 3.43 (dt, J=4.4, J=10.2,1H), 3.55-3.65 (m, 2H), 3.95 (s, br, 2H) .MS m/z (100%): 172 (m
+, 2), 81 (100).
Embodiment 2
In 100mL autoclave, add 1.0g (5.9mmol) 8,9-epoxy isopulegol and 3mL ethanol, add Raney's nickel 0.3g, passes into the hydrogen of 48atm.At 60 ℃, stirring reaction is 5 hours, and reaction is finished, and carefully reaction solution is inclined to.Filter, concentrated rear pillar chromatographic separation, to menthane-3, the yield of 9-glycol is 66%.To menthane-3, the spectral data of 9-glycol is with embodiment 1.
Embodiment 3
In 100mL autoclave, add 1.0g (5.9mmol) 8, the mixed solvent of 9-epoxy isopulegol and 4mL methyl alcohol and water (volume ratio is 1/1), adds Raney's nickel 0.3g, passes into the hydrogen of 80atm.At 150 ℃, stirring reaction is 3 hours, and reaction is finished, and aftertreatment is with embodiment 1, and to menthane-3, the yield of 9-glycol is 73%.To menthane-3, the spectral data of 9-glycol is with embodiment 1.
Embodiment 4
In 100mL autoclave, add 1.0 gram 8, the mixed solvent of 9-epoxy isopulegol and 4mL ethanol and water (volume ratio is 1/1), adds Raney's nickel 0.3g, passes into the hydrogen of 80atm.At 150 ℃, stirring reaction is 3 hours, and reaction is finished, and aftertreatment is with embodiment 1, and to menthane-3, the yield of 9-glycol is 79%.To menthane-3, the spectral data of 9-glycol is with embodiment 1.
Embodiment 5
In 100mL autoclave, add 0.7 gram 8, the mixed solvent of 9-epoxy isopulegol and 4mL Virahol and water (volume ratio 1/1), adds Raney's nickel 0.3g, passes into the hydrogen of 80atm.At 150 ℃, stirring reaction is 3 hours, and reaction is finished, and aftertreatment is with embodiment 1, and to menthane-3, the yield of 9-glycol is 66%.To menthane-3, the spectral data of 9-glycol is with embodiment 1.
Claims (5)
1. one kind to menthane-3, and the synthetic method of 9-glycol [2-(1-methyl-2-hydroxyl) ethyl-5-methyl cyclohexane-1-alcohol], take isopulegol as raw material, by superoxide epoxidation reaction, obtains 8,9-epoxy isopulegol; It is characterized in that, then under 10atm to 100atm hydrogen pressure through raney ni catalysis hydrogenation 8,9-epoxy isopulegol reaction makes menthane-3,9-glycol; The add-on of described Raney's nickel is the 25-35% of 8,9-epoxy isopulegol mass percent.
2. according to claim 1 to menthane-3, the synthetic method of 9-glycol [2-(1-methyl-2-hydroxyl) ethyl-5-methyl cyclohexane-1-alcohol], is characterized in that, the add-on of described Raney's nickel is 30% of 8,9-epoxy isopulegol mass percent.
According to described in claim 1-2 any one to menthane-3, the synthetic method of 9-glycol [2-(1-methyl-2-hydroxyl) ethyl-5-methyl cyclohexane-1-alcohol], it is characterized in that, the reaction medium of described Raney's nickel is a kind of in organic solvent methyl alcohol, ethanol, Virahol, butanols, or the mixed solvent of described organic solvent and water.
4. according to claim 3 to menthane-3, the synthetic method of 9-glycol [2-(1-methyl-2-hydroxyl) ethyl-5-methyl cyclohexane-1-alcohol], it is characterized in that, the reaction medium of described Raney's nickel is a kind of in the mixed solvent of methyl alcohol+water, ethanol+water, Virahol+water.
5. according to claim 1 to menthane-3, the synthetic method of 9-glycol [2-(1-methyl-2-hydroxyl) ethyl-5-methyl cyclohexane-1-alcohol], described superoxide is metachloroperbenzoic acid, Peracetic Acid or hydrogen peroxide.
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Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3975449A (en) * | 1974-08-05 | 1976-08-17 | Chevron Research Company | Hydrogenation of epoxides to primary alcohols |
| CN101333151A (en) * | 2007-06-27 | 2008-12-31 | 上海继凯科技发展有限公司 | Method for synthesizing 1,2,4-butanetriol |
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Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3975449A (en) * | 1974-08-05 | 1976-08-17 | Chevron Research Company | Hydrogenation of epoxides to primary alcohols |
| CN101333151A (en) * | 2007-06-27 | 2008-12-31 | 上海继凯科技发展有限公司 | Method for synthesizing 1,2,4-butanetriol |
Non-Patent Citations (2)
| Title |
|---|
| Jean-Marc Gaudin.Synthesis and Organoleptic properties of p-Menthane lactones.《Tetrahedron》.2000,第56卷第4769-4776页. |
| Synthesis and Organoleptic properties of p-Menthane lactones;Jean-Marc Gaudin;《Tetrahedron》;20001231;第56卷;第4769-4776页 * |
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