CN104909992A - Method for preparing (1R,2S,5R)-2-isopropyl-5-methyl cyclohexanol from 2S-trans-5-methyl-2-(1-methylethyl)cyclohexanone - Google Patents
Method for preparing (1R,2S,5R)-2-isopropyl-5-methyl cyclohexanol from 2S-trans-5-methyl-2-(1-methylethyl)cyclohexanone Download PDFInfo
- Publication number
- CN104909992A CN104909992A CN201510297766.5A CN201510297766A CN104909992A CN 104909992 A CN104909992 A CN 104909992A CN 201510297766 A CN201510297766 A CN 201510297766A CN 104909992 A CN104909992 A CN 104909992A
- Authority
- CN
- China
- Prior art keywords
- methyl
- methylethyl
- trans
- cyclohexanol
- pimelinketone
- 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
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
- C07C29/145—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 with hydrogen or hydrogen-containing gases
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention belongs to the technical field of chemical industry, and relates to a method for preparing (1R,2S,5R)-2-isopropyl-5-methyl cyclohexanol from 2S-trans-5-methyl-2-(1-methylethyl)cyclohexanone. The 2S-trans-5-methyl-2-(1-methylethyl)cyclohexanone is subjected to catalytic hydrogenation in an organic solvent by using a specific catalyst to obtain the (1R,2S,5R)-2-isopropyl-5-methyl cyclohexanol at higher yield and stereoselectivity. The method has favorable industrialization prospects.
Description
Technical field
The invention belongs to chemical industry synthesis field, be specifically related to the method for the trans-5-methyl of one 2S--2-(1-methylethyl) pimelinketone preparation (1R, 2S, 5R)-2-sec.-propyl-5-methyl-cyclohexanol.
Background technology
Containing the abundant trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone in natural labiate oil, how trans-for relatively inexpensive 2S-5-methyl-2-(1-methylethyl) pimelinketone is converted into the higher (1R of value, 2S, 5R)-2-sec.-propyl-5-methyl-cyclohexanol is a more popular research topic always.The hydrogen reduction of bibliographical information calcium is had to obtain 97% yield (Tsuhako, Akiko et al, Tetrahedron Letters, 48 (52), 9120-9123; , but calcium hydrogen too vivaciously operates dangerous 2007).There is bibliographical information to obtain product with hydrogen reducing under the catalysis of copper, but lack stereoselectivity (Ravasio, Nicoletta et al, Tetrahedron Letters, 43 (21), 3943-3945; 2002).So a kind of high yield and highly-solid selectively must be found and the method for reducing of convenient operation, to carry out suitability for industrialized production.General high with transition metal-catalyzed yield, and catalyst levels is little, after chiral ligand, substantially can obtain very high stereoselectivity.After known transition metal and part are screened, we have found a kind of suitable catalyzer, shown in I, be (1R in the trans-5-methyl of catalysis S--2-(1-methylethyl) pimelinketone hydrogenation, 2S, in the reaction of 5R)-2-sec.-propyl-5-methyl-cyclohexanol, there is higher yield and stereoselectivity, have good industrial applications to be worth.
Summary of the invention
The invention provides the trans-5-methyl of one 2S--2-(1-methylethyl) pimelinketone preparation (1R, 2S, 5R) method of-2-sec.-propyl-5-methyl-cyclohexanol, the inventive method yield is high, stereoselectivity is high, simple to operate, be applicable to suitability for industrialized production.
The technical solution used in the present invention is as follows:
The trans-5-methyl of one 2S--2-(1-methylethyl) pimelinketone preparation (1R, 2S, 5R) the method for-2-sec.-propyl-5-methyl-cyclohexanol, it is characterized in that with the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone for raw material, (1R is obtained in organic solvent with special catalyst hydrogenation, 2S, 5R)-2-sec.-propyl-5-methyl-cyclohexanol, this chemical equation is as follows:
The structural formula of described special catalyst is such as formula shown in I:
Wherein X is the one in halogen Cl, Br, I, and the structure of Ar is as shown in II:
Described prepares (1R with the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone, 2S, 5R) the method for-2-sec.-propyl-5-methyl-cyclohexanol, is characterized in that described organic solvent is one or several mixing in methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF), toluene, methylene dichloride, chloroform.
Described prepares (1R with the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone, 2S, 5R) the method for-2-sec.-propyl-5-methyl-cyclohexanol, it is characterized in that described temperature of reaction is 30 DEG C-150 DEG C, hydrogen pressure is 10bars-100bars.
Described prepares (1R with the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone, 2S, 5R) the method for-2-sec.-propyl-5-methyl-cyclohexanol, is characterized in that the mol ratio of the trans-5-methyl of described 2S--2-(1-methylethyl) pimelinketone and special catalyst is 50-5000:1.
The method of the trans-5-methyl of 2S-disclosed in this invention-2-(1-methylethyl) pimelinketone preparation (1R, 2S, 5R)-2-sec.-propyl-5-methyl-cyclohexanol, its yield and stereoselectivity high, simple to operate, be applicable to suitability for industrialized production.
Embodiment
Contribute to understanding the present invention by following examples, but be not limited to content of the present invention.
Embodiment 1:
In the reaction flask of a 200ml, part (S)-(-)-5,5 '-bis-diphenylphosphine-4 is added, the luxuriant 0.94g of 4 '-two-1,3-Ben Bing bis-Evil, [RuCl under the protection of nitrogen
2(C
6h
6)]
2for 0.33g, ethanol 150ml, benzene 20ml.Stir 1h at 55-60 degree, filter, done by filtrate reduced in volume, obtain 1.27g catalyzer, wherein halogen X is chlorine.
Embodiment 2:
The catalyzer 1.27g prepared by above-described embodiment 1 is added in a 500ml autoclave, add the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone 90g, methyl alcohol 150ml, replace into hydrogen, airtight, be heated with stirring to 100 degree, pressure is risen to 80bars, reaction 15h, system no longer inhales hydrogen, stopped reaction.Steamed by reaction solution and desolventize, decompression steams product (1R, 2S, 5R)-2-sec.-propyl-5-methyl-cyclohexanol, obtains 89.5g, yield 98.2%, ee value 98.5%.
Embodiment 3:
In the reaction flask of a 200ml, part (S)-(-)-5,5 '-bis-diphenylphosphine-4 is added, the luxuriant 0.94g of 4 '-two-1,3-Ben Bing bis-Evil, [RuBr under the protection of nitrogen
2(C
6h
6)]
2for 0.45g, methyl alcohol 52ml, benzene 36ml.Stir 1h at 55-60 degree, filter, done by filtrate reduced in volume, obtain 1.35g catalyzer, wherein halogen X is bromine.
Embodiment 4:
The catalyzer 1.35g prepared by above-described embodiment 3 is added in a 500ml autoclave, add the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone 90g, methyl alcohol 150ml, replace into hydrogen, airtight, be heated with stirring to 100 degree, pressure is risen to 80bars, reaction 14h, system no longer inhales hydrogen, stopped reaction.Steamed by reaction solution and desolventize, decompression steams product (1R, 2S, 5R)-2-sec.-propyl-5-methyl-cyclohexanol, obtains 89.8g, yield 98.5%, ee value 98.8%.
Embodiment 5:
In the reaction flask of a 200ml, part (S)-(-)-5,5 '-bis-diphenylphosphine-4 is added, the luxuriant 0.94g of 4 '-two-1,3-Ben Bing bis-Evil, [RuI under the protection of nitrogen
2(C
6h
6)]
2for 0.59g, ethanol 20ml, methylene dichloride 40ml, benzene 10ml.Stir 3h at 55-60 degree, filter, done by filtrate reduced in volume, obtain 1.38g catalyzer, wherein halogen X is iodine.
Embodiment 6:
The catalyzer 1.38g prepared by above-described embodiment 5 is added in a 500ml autoclave, add the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone 90g, methyl alcohol 150ml, replace into hydrogen, airtight, be heated with stirring to 100 degree, pressure is risen to 80bars, reaction 13h, system no longer inhales hydrogen, stopped reaction.Steamed by reaction solution and desolventize, decompression steams product (1R, 2S, 5R)-2-sec.-propyl-5-methyl-cyclohexanol, obtains 90.1g, yield 98.8%, ee value 99.1%.
Claims (4)
1. prepare (1R with the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone for one kind, 2S, 5R) the method for-2-sec.-propyl-5-methyl-cyclohexanol, it is characterized in that with the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone for raw material, (1R is obtained in organic solvent with special catalyst hydrogenation, 2S, 5R)-2-sec.-propyl-5-methyl-cyclohexanol, this chemical equation is as follows:
The structural formula of described special catalyst is such as formula shown in I:
Wherein X is the one in halogen Cl, Br, I, and the structure of Ar is as shown in II:
2. use the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone to prepare (1R as claimed in claim 1,2S, 5R) the method for-2-sec.-propyl-5-methyl-cyclohexanol, is characterized in that described organic solvent is one or several mixing in methyl alcohol, ethanol, Virahol, tetrahydrofuran (THF), toluene, methylene dichloride, chloroform.
3. use the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone to prepare (1R as claimed in claim 1,2S, 5R) the method for-2-sec.-propyl-5-methyl-cyclohexanol, it is characterized in that described temperature of reaction is 30 DEG C-150 DEG C, hydrogen pressure is 10bars-100bars.
4. use the trans-5-methyl of 2S--2-(1-methylethyl) pimelinketone to prepare (1R as claimed in claim 1,2S, 5R) the method for-2-sec.-propyl-5-methyl-cyclohexanol, is characterized in that: the mol ratio of the trans-5-methyl of described 2S--2-(1-methylethyl) pimelinketone and special catalyst is 50-5000:1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510297766.5A CN104909992A (en) | 2015-06-03 | 2015-06-03 | Method for preparing (1R,2S,5R)-2-isopropyl-5-methyl cyclohexanol from 2S-trans-5-methyl-2-(1-methylethyl)cyclohexanone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201510297766.5A CN104909992A (en) | 2015-06-03 | 2015-06-03 | Method for preparing (1R,2S,5R)-2-isopropyl-5-methyl cyclohexanol from 2S-trans-5-methyl-2-(1-methylethyl)cyclohexanone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN104909992A true CN104909992A (en) | 2015-09-16 |
Family
ID=54079500
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201510297766.5A Pending CN104909992A (en) | 2015-06-03 | 2015-06-03 | Method for preparing (1R,2S,5R)-2-isopropyl-5-methyl cyclohexanol from 2S-trans-5-methyl-2-(1-methylethyl)cyclohexanone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN104909992A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0850945A1 (en) * | 1996-12-26 | 1998-07-01 | Takasago International Corporation | Chiral diphosphine compound, intermediate for preparing the same, transition metal complex having the same diphosphine compound as ligand and asymmetric hydrogenation catalyst |
| EP1153908A2 (en) * | 2000-05-10 | 2001-11-14 | Takasago International Corporation | Method for producing 1-menthol |
| CN1558908A (en) * | 2001-09-28 | 2004-12-29 | Synkem | Novel diphosphines, their complexes with transisition metals and their use in asymmetric synthesis |
| CN102010297A (en) * | 2010-11-23 | 2011-04-13 | 广东省食品工业研究所 | Method for chiral synthesis of levorotatory menthol |
-
2015
- 2015-06-03 CN CN201510297766.5A patent/CN104909992A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0850945A1 (en) * | 1996-12-26 | 1998-07-01 | Takasago International Corporation | Chiral diphosphine compound, intermediate for preparing the same, transition metal complex having the same diphosphine compound as ligand and asymmetric hydrogenation catalyst |
| EP1153908A2 (en) * | 2000-05-10 | 2001-11-14 | Takasago International Corporation | Method for producing 1-menthol |
| CN1558908A (en) * | 2001-09-28 | 2004-12-29 | Synkem | Novel diphosphines, their complexes with transisition metals and their use in asymmetric synthesis |
| CN102010297A (en) * | 2010-11-23 | 2011-04-13 | 广东省食品工业研究所 | Method for chiral synthesis of levorotatory menthol |
Non-Patent Citations (1)
| Title |
|---|
| 郑昌戈等: "l-薄荷醇的合成研究进展", 《化工进展》 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| JP5147309B2 (en) | Process for producing 2,5-furandicarboxylic acid | |
| CN107721833B (en) | Method for preparing menthone | |
| CN107253937B (en) | A kind of synthetic method of gamma-valerolactone | |
| CN106694046B (en) | A kind of preparation method of modified class zeolite imidazole skeleton material and its application in carbon dioxide hydrogenation reaction | |
| CN105330523A (en) | Method for preparing cyclopentanone by taking biomass resource as raw material | |
| CN111960948B (en) | Synthesis process of tetrabutylammonium bromide | |
| CN107935816B (en) | Method for preparing cyclohexanol by catalytic hydrogenation and deoxidation of guaiacol | |
| CN106866360A (en) | A kind of method that 5 hydroxymethyl furfural catalyzed conversion prepares 1,6-HD | |
| CN104923299A (en) | Ruthenium catalysts used for catalyzing acetophenone for producing alpha-phenylethanol, and preparation method thereof | |
| CN108409802B (en) | Preparation process of (S) -1-ferrocene ethyl dimethylamine | |
| CN107954821B (en) | Method for preparing polyaromatic substituted naphthalene derivative by cyclization reaction of ruthenium-catalyzed dibenzyl ketone and internal alkyne and application | |
| Shi et al. | Synthesis Cu (I)–CN-based MOF with in-situ generated cyanogroup by cleavage of acetonitrile: Highly efficient for catalytic cyclization of propargylic alcohols with CO2 | |
| CN104447261A (en) | Method for preparing cyclopentanol and cyclopentanone by using cyclopentane | |
| WO2018048175A1 (en) | Method for preparing 1,3-cyclohexanedimethanol | |
| CN106622219B (en) | Catalyst for preparing tetrahydrofurfuryl alcohol by furfuralcohol liquid phase hydrogenation, preparation method and application thereof | |
| CN106946668B (en) | Method for preparing cyclohexanone by phenol hydrogenation | |
| CN101058532A (en) | Method of preparing chiral primary alcohol and secondary alcohol with chirality center at ortho position of hydroxyl group | |
| CN103224591B (en) | Bimetallic catalytic hydrogenation method of nitrile rubber | |
| CN110624604B (en) | Modified palladium-carbon catalyst, preparation method and application thereof | |
| CN109622031B (en) | Preparation method of 2-hydroxy phosphono zirconium acetate and application thereof in furfuryl alcohol synthesis | |
| CN105111044A (en) | Method for synthesizing isopentenol from butenol | |
| CN106732725A (en) | The preparation and its application of the carbon-based transition-metal catalyst of MgO-Supported N doping | |
| CN104387233B (en) | A kind of method of synthesizing tricyclic decane dimethanol | |
| CN104909992A (en) | Method for preparing (1R,2S,5R)-2-isopropyl-5-methyl cyclohexanol from 2S-trans-5-methyl-2-(1-methylethyl)cyclohexanone | |
| CN108311158B (en) | Catalyst, preparation method thereof and application thereof in reduction of vanillin |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| RJ01 | Rejection of invention patent application after publication |
Application publication date: 20150916 |
|
| RJ01 | Rejection of invention patent application after publication |