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Efficient and economic asymmetric synthesis of nootkatone, tetrahydronootkatone, their precursors and derivatives

A technology of tetrahydronootkatone and dihydronootkatone, which is applied in the preparation of organic compounds, organic chemistry, organic chemical methods, etc., can solve the problems of lengthy synthesis steps, hindering commercial application, high cost, etc.

Inactive Publication Date: 2008-05-21
BOARD OF SUPERVISORS OF LOUISIANA STATE UNIV & AGRI & MECHANICAL COLLEGE
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

[0016] Existing methods for the synthesis of nootkatone suffer from one or more of the following disadvantages: lengthy synthetic steps; relatively expensive starting materials for the synthesis; low yields; racemic mixtures in the synthesis; The starting material is not on the GRAS list (generally recognized as safe)
However, the high cost of nootkatone and its related compounds has hindered their commercial application in other fields, such as repellants or poisons for termites or other pests

Method used

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  • Efficient and economic asymmetric synthesis of nootkatone, tetrahydronootkatone, their precursors and derivatives
  • Efficient and economic asymmetric synthesis of nootkatone, tetrahydronootkatone, their precursors and derivatives
  • Efficient and economic asymmetric synthesis of nootkatone, tetrahydronootkatone, their precursors and derivatives

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0028]6,6-Dimethyl-bicyclo[3.3.1]heptan-2-one, nopinone (compound 2): finely ground KMnO4 (2.8 g, 17.8 mmol), acidic alumina (Brockmann Activity 1, 11.2 g, 0.1098 mol) and water (2.79 g, 0.1552 mol) were mixed for 5 minutes to give a homogeneous mixture. Commercially available (-)-β-pinene (0.5 g, 0.582 ml, 3.67 mmol) was dissolved in dichloromethane (DCM) (100 mL), and the solution was placed in a round bottom flask. To the above solution was added the permanganate / alumina mixture in small portions over 10 minutes while continuing to stir. The reaction was allowed to proceed at room temperature and the progress of the reaction was monitored by TLC (90:10 / Hexane:EtOAc). After reaction of essentially all starting material was complete, the crude mixture was filtered through a fritted glass funnel and the residue was washed with DCM (2 x 50 mL). Excess solvent was removed by rotary evaporator to give a yellow oil, which was further purified by column chromatography (90:10 / hexa...

Embodiment 2

[0030] (1R,5R)-6,6-Dimethyl-3-(E)-ethylidenebicyclo[3.3.1]heptan-2-one (Compound 3): Place a magnetic stirring bar on a device equipped with a constant pressure Addition funnel and 2 inlet valves in a clean, dry three necked jacketed round bottom flask. The flask was then purged with argon. Compound 2 (1 g, 1.0194 ml, 7.24 mmol) and KOH (0.4872 g, 8.7 mmol) were dissolved in ethanol (17.2 mL) in a flask under argon. The resulting solution was cooled to 5°C. Still under argon, a solution of acetaldehyde (0.609 mL, 0.4781 g, 10.9 mmol) in EtOH (4.3 mL) was added to the flask over 30 minutes. The mixture was reacted at 5°C for 15 hours. An additional 4 parts of acetaldehyde (0.609 mL) in EtOH (4.3 mL) was added to the reaction mixture at 15 hour intervals, maintained at 5 °C. Stirring was continued for 6 hours after addition of the last portion of acetaldehyde and EtOH. A solution of p-toluenesulfonic anhydride (1.927 g, 10.1 mmol) in EtOH (5 mL) was then added to the mixtur...

Embodiment 3

[0033] 3-Ethylidene-6,6-dimethyl-2-(2-methyl-allyl)-bicyclo[3.1.1]heptan-2-ol (compound 4a): at 60°C, 30 A solution of methallyl chloride (0.692 g, 7.64 mmol) in freshly distilled tetrahydrofuran (THF) (2.5 mL) was added to flame-dried Mg metal (0.28 g, 11.5 mmol) within minutes. THF (2.5mL) suspension. The resulting Grignard solution darkened during an additional 20 minutes at reflux. The mixture was then cooled to -42°C (dry ice / chlorobenzene bath), and a solution of enone compound 3 (0.4182 g, 2.6 mmol) in THF (2.5 mL) was added dropwise. After 5 minutes the cooling bath was removed and the reaction was stirred for 1.5 hours while allowing to warm to room temperature. The mixture was then poured into ice-cold 0.1N HCl (50 mL) and extracted with ether. The combined organic fractions were washed with water and brine, Na 2 SO 4 Dry, filter and concentrate. Column chromatography (90:10 / Hexane:EtOAc) afforded compound 4a (0.52 g, 92% yield) as a colorless liquid. 1 HNMR: ...

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Abstract

An inexpensive, stereoselective synthesis for nootkatone, tetrahydronootkatone, and their derivatives is disclosed. The starting materials used in the synthesis are inexpensive. The principal starting material, (-)-beta-Pinene, is on the GRAS list (generally recognized as safe).

Description

[0001] Anne M. Sauer, William E. Crowe, Roger A. Laine, Gregg [0002] Henderson [0003] File No.02A10W Sauer [0004] Express Mail No.EV854030824 [0005] The research part of the present invention enjoys the U.S. government funding, the license number is 58-6435-8-084, and is funded by the U.S. Department of Agriculture, Agricultural Research Service. The US Government has certain rights in this invention. [0006] This application claims the benefit of US Patent Application Serial No. 11 / 106,338, filed April 14, 2005, under certain treaties and agreements applicable in various countries. In the United States, this application is a continuation-in-part of US Patent Application Serial No. 11 / 106,338, filed April 14, 2005. technical field [0007] The present invention relates to the synthesis of nootkatone and its derivatives and precursors. Background technique [0008] The IUPAC name of nootkatone is 4,4a,5,6,...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/00C07C35/00
CPCC07C49/653C07C45/28C07C45/66C07C45/65C07C49/693C07C45/74C07C49/433C07C29/44C07B2200/07C07C2602/42C07C35/28
Inventor A·M·索尔W·E·克洛维R·A·雷内G·汉德森
Owner BOARD OF SUPERVISORS OF LOUISIANA STATE UNIV & AGRI & MECHANICAL COLLEGE
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