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Optically active 3-methylcyclopentadecanone and method for producing intermediate thereof

一种甲基环十五烷酮、光学活性的技术，应用在光学活性3-甲基环十五烷酮及其中间体的制备领域，能够解决不能避免生成等问题

Inactive Publication Date: 2008-04-23
TAKASAGO INTERNATIONAL CORPORATION
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  • Summary
  • Abstract
  • Description
  • Claims
  • Application Information

AI Technical Summary

Problems solved by technology

In addition, many studies have been made on the method of optically separating the racemic form (for example, refer to Patent Document 1), but this method cannot avoid the formation of the (S)-form.

Method used

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  • Optically active 3-methylcyclopentadecanone and method for producing intermediate thereof
  • Optically active 3-methylcyclopentadecanone and method for producing intermediate thereof
  • Optically active 3-methylcyclopentadecanone and method for producing intermediate thereof

Examples

Experimental program
Comparison scheme
Effect test

Embodiment 1

[0154] O,O'-(R)-(1,1'-binaphthyl-2,2'-diyl)-N-benzyl-N-(R)-(1-phenethyl)idene represented by the following chemical formula Synthesis of Phosphoramide (L-1)

[0155] [Chemical 12]

[0156]

[0157] Under nitrogen flow, in a 50 mL three-necked flask with a thermometer and a dropping funnel, add 20 mL of THF, 1.05 g (5.0 mmol) of (R)-(+)-N-benzyl-N-(1-phenethyl)amine The solution was cooled to -50°C, and 3.2 mL (5.0 mmol) of n-butyllithium (1.58 mol / L hexane solution) was added dropwise. After stirring at -50°C for 1 hour, 6.8 g (50 mmol) of phosphorus trichloride was added, the temperature was gradually raised to room temperature, and the mixture was stirred for 2 hours. Then, the solvent and phosphorus trichloride were removed under reduced pressure, and 20 mL of toluene was added to the residue. The toluene solution was cooled to -20°C, and 1.43 g (5.0 mmol) of (R)-(+)-1,1'-bi(2-naphthol), 2.53 g (25 mmol) of triethylamine, and 10 mL of toluene were added dropwise. mix...

Embodiment 2

[0163] Synthesis of (R)-3-methyl-1-cyclopentadecenyl propionate represented by the following formula

[0164] [Chemical 13]

[0165]

[0166]Under nitrogen flow, into a 30 mL reaction flask with a thermometer, add 21.0 mg (0.04 mmol) of the optically active ligand O, O'-(R)-(1,1'-binaphthyl-2, obtained in Example 1, 2'-Diyl)-N-benzyl-N-(R)-(1-phenethyl)phosphoramidite, 7.2 mg (0.02 mmol) Cu(OTf) 2 and 7 mL of toluene, stirred at room temperature for 30 minutes. To this solution was added 1.4 mL (2.8 mmol) of a dimethylzinc toluene solution (2.0 mol / L), followed by stirring for 30 minutes. Then, the solution was cooled to -20°C, and 0.29 g (2.2 mmol) of propionic anhydride and 0.44 g (2.0 mmol) of 2-(E)-cyclopentadecenone were added dropwise. After completion of the dropwise addition, the mixture was stirred for 2 hours. Then, a 5% sulfuric acid aqueous solution was added to stop the reaction and separate liquids. The obtained organic layer was washed with water, and th...

Embodiment 3

[0174] Synthesis of (R)-Muskone represented by the following formula

[0175] [Chemical 14]

[0176]

[0177] To a 30 mL eggplant-shaped flask, 0.53 g (1.8 mmol) of (R)-3-methyl-1-cyclopentadecenyl propionate obtained in Example 2 and 20 g of toluene were added, and the mixture was stirred. After adding dropwise 0.39 g (2.0 mmol) of a 28% sodium methoxide-methanol solution at 20°C, the mixture was stirred for 1 hour. Then, after adding a 5% sulfuric acid aqueous solution to the reaction solution, the solution was separated, the organic layer was washed with water, and the solvent was removed under reduced pressure to obtain 0.60 g of a crude product. The crude product was purified by silica gel column chromatography to obtain (R)-muskone in a yield of 97%. The optical purity was determined by high performance liquid chromatography and the result was 86.1% ee.

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PUM

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Abstract

The invention relates to a preparation method of optically active 3-methylcyclopentadecane-1-one, which is characterized in that in the presence of a copper catalyst, an enolate anion capture agent and a specific optically active phosphoramidite, the methyl 1, 4-conjugated addition reaction of methyl group to 2-cyclopentadecen-1-one by chemical organometallic compound to obtain optically active 3-methyl-1-cyclopentadecene derivative, and then The obtained 3-methyl-1-cyclopentacene derivative was subjected to solvolysis.

Description

technical field [0001] The invention relates to a preparation method of optically active 3-methylcyclopentadecanone and an intermediate thereof. In addition, the present invention also relates to a novel optically active ligand for preparing optically active 3-methylcyclopentadecanone and its intermediates. Background technique [0002] In recent years, people's tendency to yearn for nature has been increasing, and fragrances are also concentrated on fragrances with high preference that can characteristically reflect the natural environment. [0003] Musk is dried from musk gland secretions of male musk deer, and has been a very valuable spice and crude drug since ancient times. Those with strong musk aroma are the best products, and now those containing more than 2% musk ketones are listed as top grades. Musk deer are deer species that inhabit the Himalayas to mainland China. Imports and exports are now prohibited under the Washington Treaty. Therefore, only natural mus...

Claims

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Application Information

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Patent Type & Authority Applications(China)
IPC IPC(8): C07C45/51C07C69/02C07C49/385C07B53/00C07C67/00C07F9/6574
CPCC07C2101/18C07B2200/07C07C45/54C07C67/00C07F9/657154C07C45/513C07B53/00C07C2601/18C07C49/385C07C69/013C07C69/24C07C45/51
Inventor 田中茂石田贤哉松田洋幸
Owner TAKASAGO INTERNATIONAL CORPORATION
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