CN103449972A - 3,3-dimethyl-5-(2,2,3-trimethyl-cyclopentyl-3-vinyl)-pent-4-en-2-ol and preparation method thereof - Google Patents
3,3-dimethyl-5-(2,2,3-trimethyl-cyclopentyl-3-vinyl)-pent-4-en-2-ol and preparation method thereof Download PDFInfo
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- CN103449972A CN103449972A CN2012101745722A CN201210174572A CN103449972A CN 103449972 A CN103449972 A CN 103449972A CN 2012101745722 A CN2012101745722 A CN 2012101745722A CN 201210174572 A CN201210174572 A CN 201210174572A CN 103449972 A CN103449972 A CN 103449972A
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Abstract
The invention relates to 3,3-dimethyl-5-(2,2,3-trimethyl-cyclopentyl-3-vinyl)-pent-4-en-2-ol and a new method for preparing the same.
Description
The field of invention
The present invention relates to 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol and prepare its novel method.
Background of invention
Need to prepare the novel method of perfume molecules in fragrance industry always.Art-recognizedly to the actual consideration such as synthetic, may hinder the use of perfume molecules in commercial applications.Sometimes whether the synthetic of unpredictable appointment perfume molecules can carry out by commercial size.Therefore, the fragrance industry unremitting effort is with the novel and economic method of research and development preparation perfume molecules.
Summary of the invention
The present invention relates to be expressed from the next 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol:
More specifically, the present invention relates to prepare the novel method of 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol.
Can be expressly understood these embodiments of the present invention and other embodiment by reading following specification sheets.
Embodiment
3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol is commercially available spices.The wooden aromatic of this compound and the fragrance of a flower are adjusted and are widely used in current perfumed product.But the synthetic method of report need to be through long-time reaction, process complexity and expensive (for example, referring to United States Patent (USP) the 4th, 610, No. 813) before.Therefore, the invention provides novelty, convenience and economic improving one's methods.
According to the present invention, can prepare 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol according to following reaction scheme, in an embodiment described reaction scheme is described in detail.Reagent all can commercially availablely be buied.
It should be appreciated by those skilled in the art that compound of the present invention has mulitiple chiral centers, thereby many isomer of claimed compound are provided.Compound as herein described comprises the isomeric mixtures of these compounds, and can by technical point well known by persons skilled in the art from these isomerss.For example, suitable technology comprises distillation and chromatography, as is called the high performance liquid chromatography, particularly silica gel column chromatography of HPLC, and gas-chromatography (GC) trapping.But the commercially available prod major part provides with isomer mixture.
As described in above reaction scheme, of the present invention 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol can, by commercially available campholenic aldehyde (campholenic aldehyde) and methylethylketone (MEK) by aldol condensation and methylation reaction, then be gone back original preparation.
Specific implementations of the present invention below is provided.Other distortion of the present invention will be apparent for a person skilled in the art.Within should be appreciated that these distortion are included in the scope of the invention.Unless otherwise indicated, all percentage ratio used herein is all weight percentage, and g is interpreted as gram, and mol is interpreted as mole.In an embodiment, IFF means international flavouring agent and (the International Flavors & of spices company limited of New York, United States New York; Fragrances Inc., New York, NY, USA).
example I
The preparation of 3-methyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-3-alkene-2-ketone: in reaction flask, add MEK (396g, 5.5mol), potassium hydroxide (KOH) (14g, 0.25mol) and methyl alcohol (CH
3oH) (442g, 13.8mol), the simultaneous reactions temperature remains higher than 0 ℃, the highlyest is about 50 ℃ (for example, about 25-30 ℃).Under agitation, added campholenic aldehyde (152g, 1mol) in reaction mixture in 4 hours.Then will react again aging 5 hours.Analyze monitoring reaction course and react by GC and whether complete.Then use acetic acid termination reaction mixture, water cleans once.Separate and retain organic layer, and it is added in boric acid and toluene.Temperature of reaction stably is increased to approximately 145 ℃, thereby removes water from reaction.With sodium bicarbonate (NaHCO
3) (10%) cleaning reaction mixture, until the pH of water slightly is alkalescence.Further distillation organic layer, obtain 3-methyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-3-alkene-2-ketone (165g, 0.8mol, productive rate approximately 80%).
example II
3,3-dimethyl-5-(2,2, the preparation of 3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-ketone: under about room temperature condition, add 3-methyl-5-(2 in reaction flask, 2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-3-alkene-2-ketone (synthetic in above-described embodiment 1) (206g, 1mol), sodium hydroxide (NaOH) (140g, 3.5mol), toluene (115g, 1.25mol) and phase-transfer catalyst aliquat 336 (aliquat 336) (22.1g, 0.05mol).Under agitation, added again methyl chloride gas (CH in reaction mixture in 8 hours
3cl) (65.7g, 1.3mol).By reaction mixture aging 2 hours again, then water cleaned three times, obtains crude product 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-ketone (165g, 0.75mol, productive rate approximately 75%).
Other suitable phase-transfer catalyst includes but not limited to, for example, and tetrabutylammonium, tetrabutylammonium iodide, cetrimonium bromide and octadecyl trimethyl ammonium bromide.
eXAMPLE III
The preparation of 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol: under atmospheric pressure, in reaction flask by tri sec-butoxy aluminum (Al (sec-BuO)
3) and sec-butyl alcohol be heated to reflux.Added 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-ketone (synthetic in above-described embodiment II) in 4 hours.Then under the vacuum condition that is 150mmHg at pressure, by distillation, remove unreacted sec-butyl alcohol.Under about 85 ℃ of conditions, with sodium borohydride (NaBH
4) to 3 of remained unreacted, 3-dimethyl-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-ketone is further processed.Separate, retain organic layer, and clean until pH slightly is acidity with acetic acid.The crude product that further distillation obtains, obtain 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-ketone (200g, 0.9mol, productive rate approximately 90%).
Claims (10)
1. a method for preparing 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol, it comprises the following steps:
(i) by the reaction of methylethylketone and campholenic aldehyde, to obtain 3-methyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-3-alkene-2-ketone;
(ii) the 3-methyl-5-(2 under the condition existed at phase-transfer catalyst, step (i) obtained, 2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-3-alkene-2-ketone reacts with methyl chloride, to obtain 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle, penta-3-thiazolinyl)-penta-4-alkene-2-ketone; With
(iii) step (ii) is obtained 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-ketone reduction, thus obtain 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-alcohol.
2. the method for claim 1, is characterized in that, described step (i) is carried out under 0-50 ℃ of temperature condition.
3. method as claimed in claim 2, is characterized in that, described temperature is 25-30 ℃.
4. the method for claim 1, is characterized in that, described phase-transfer catalyst is selected from aliquat 336, tetrabutylammonium, tetrabutylammonium iodide, cetrimonium bromide and octadecyl trimethyl ammonium bromide.
5. the method for claim 1, is characterized in that, described step (iii) is carried out under the existence of sec-butyl alcohol and tri sec-butoxy aluminum.
6. method as claimed in claim 5, it comprises further the additional step by 3,3-dimethyl-5-(2,2,3-trimethylammonium-encircle penta-3-thiazolinyl)-penta-4-alkene-2-ketone reacts with sodium borohydride.
7. method as claimed in claim 6, is characterized in that, described additional step carries out under the temperature condition of 85 ℃.
8. the method for claim 1, is characterized in that, described method also comprises the step of cleaning and purifying.
9. method as claimed in claim 8, is characterized in that, described cleaning step comprises with acetic acid and cleaning.
10. method as claimed in claim 8, is characterized in that, described purification step comprises distillation.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590500A (en) * | 2019-09-29 | 2019-12-20 | 格林生物科技股份有限公司 | Preparation of 3-methyl-5- (2,2, 3-trimethyl-3-cyclopenten-1-yl) pent-4-en-2-ol |
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| CN1569811A (en) * | 2004-04-22 | 2005-01-26 | 宁夏大学 | Process for synthesizing dibutyl carbonate |
| CN101723804A (en) * | 2008-10-14 | 2010-06-09 | 上海香料研究所 | Method for synthesizing polysantalol |
| US20110275840A1 (en) * | 2009-01-09 | 2011-11-10 | Mitsubishi Gas Chemical Company, Inc. | Glycol compound having dioxane structure and method for producing the same |
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2012
- 2012-05-30 CN CN2012101745722A patent/CN103449972A/en active Pending
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| CN1097004A (en) * | 1993-12-21 | 1995-01-04 | 衡阳三化实业股份有限公司 | The preparation method and the equipment thereof of single, double, three tetramethylolmethane |
| CN1569811A (en) * | 2004-04-22 | 2005-01-26 | 宁夏大学 | Process for synthesizing dibutyl carbonate |
| CN101723804A (en) * | 2008-10-14 | 2010-06-09 | 上海香料研究所 | Method for synthesizing polysantalol |
| US20110275840A1 (en) * | 2009-01-09 | 2011-11-10 | Mitsubishi Gas Chemical Company, Inc. | Glycol compound having dioxane structure and method for producing the same |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110590500A (en) * | 2019-09-29 | 2019-12-20 | 格林生物科技股份有限公司 | Preparation of 3-methyl-5- (2,2, 3-trimethyl-3-cyclopenten-1-yl) pent-4-en-2-ol |
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