CN102260153A - Method for synthesizing 4-oxo-beta-damascone - Google Patents
Method for synthesizing 4-oxo-beta-damascone Download PDFInfo
- Publication number
- CN102260153A CN102260153A CN2011101454281A CN201110145428A CN102260153A CN 102260153 A CN102260153 A CN 102260153A CN 2011101454281 A CN2011101454281 A CN 2011101454281A CN 201110145428 A CN201110145428 A CN 201110145428A CN 102260153 A CN102260153 A CN 102260153A
- Authority
- CN
- China
- Prior art keywords
- beta
- synthetic method
- oxo
- copper compound
- organic solvent
- 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
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for synthesizing 4-oxo-beta-damascone. In the method, beta-damascone is reacted with a metal copper compound and tert-butyl hydroperoxide at temperature of lower than 80DEG C in an organic solvent, and the corresponding 4-oxo-beta-damascone is synthesized by one step. The method is easy to implement and ensures high yield; and the produced 4-oxo-beta-damascone is widely applied to food additives, cosmetics, medicines, cigarettes and the like, and has high application value.
Description
Technical field:
The present invention relates to a kind of synthetic method of producing corresponding 4-oxo-beta-trans-Damascenone by dorinone.
Technical background:
4-oxo-beta-trans-Damascenone is a white crystal, has graceful fragrant and sweet and fruital, is soluble in alcohol, the acetone equal solvent.He is a kind of very important tobacco aromatics using and organic synthesis intermediate, is usually used in preparation and the preparation of heterogeneous ring compound and the synthetic intermediate of tobacco aromatics using Megastigmatrienone etc. of essence.It adds in the cigarette on a small quantity, just can play the effect of exquisiteness, soft cigarette smoke.At present, the synthetic report of relevant 4-oxo-beta-trans-Damascenone is considerably less both at home and abroad, but its purposes and effect in the essence and flavoring agent industry is obvious day by day.
Existing synthetic method has dichloro dioxy base vanadium oxide oxidation style, chromic acid tert-butyl oxidation style, chloro chromic acid pyridine (PCC) oxidation style, methods such as sodium chlorate oxidation style and molecular oxygen catalysis oxidation style, these method operational requirement height, yield is low, aftertreatment is inconvenient and environmental pollution is serious.
Therefore, it is extremely important to seek a kind of synthetic method of simple 4-oxo-beta-trans-Damascenone.We use the synthetic method in this patent, have successfully synthesized 4-oxo-beta-trans-Damascenone.
This method is simple, and is efficient, safety, and environmental protection, product is easy to purifying, its industrial strong operability.
Formula I 4-oxo-beta-trans-Damascenone
Summary of the invention
Purpose of the present invention aims to provide a kind of simple to operation, and reactions steps is few, and the reaction conditions gentleness is with low cost, environmental friendliness, and speed of response is fast, the preparation method of 4-oxo-beta-trans-Damascenone that productive rate is high.
Technical scheme of the present invention is: raw material dorinone and catalyst metal copper compound and oxygenant tertbutyl peroxide are no more than 80 ℃ of reactions down, one-step synthesis 4-oxo-beta-trans-Damascenone in organic solvent.
The concrete preparation method of the present invention is:
The reaction raw materials dorinone that will take by weighing under magnetic agitation joins in the organic solvent, and to wherein adding the catalyst metal copper compound, drip tertbutyl peroxide again, control reaction temperature is not higher than 80 ℃, after the reaction, rotating filter is removed the catalyst metal copper compound, and decompression steams the organic solvent and the reduzate trimethyl carbinol, through extracted with diethyl ether, mass percent concentration is 15～25% Na
2SO
3Clear water washing again behind the solution washing, anhydrous Na
2SO
4Drying promptly gets corresponding 4-oxo-beta-trans-Damascenone through separating behind the rotary evaporation.
4-oxo-beta-the trans-Damascenone that obtains by above method is after column chromatography is handled, and product purity is not less than 98%.
Organic solvent in the present invention's reaction is meant the organic solvent of big (polarity scope 4-10) of traditional polarity, as acetonitrile, and acetate, acetone, ethanol, the methyl ethyl diketone or the trimethyl carbinol etc.;
Metallic copper compound of the present invention is CuCl
2, Cu (NO
3)
2, Cu (Ac)
2, divalence or monovalence copper compounds such as CuI.
Optimal reaction temperature of the present invention is 30-60 ℃.
The preferable reaction times of the present invention is 2-8 hour, the peak optimization reaction time be 2-6 hour.
Dorinone in the described reaction: metallic copper compound: the preferable ratio range of tertbutyl peroxide is 1mol: (0.01～0.1mol): (1～8mol).
The advantage of technology of the present invention is: simple to operation, reactions steps is a step, and technology greatly can simplify the operation.And temperature of reaction is no more than 80 ℃ (optimal reaction temperature is 30-60 ℃), the reaction conditions gentleness, and speed of response is fast, just can react completely in 2-8 hour, and former technology is generally more than 10 hours; Raw materials cost is low; The metallic copper compound with alcohol immersion after, airing or oven dry again reclaimed easily, can reuse; By product is few, the productive rate height; Need not use the oxygenant of pollution, and the product after the oxygenant decomposition itself is also pollution-free, belongs to environmentally friendly.
Embodiment:
Following examples are intended to illustrate the present invention rather than limitation of the invention further.
Embodiment 1
Synthetic 4-oxo-beta-trans-Damascenone
Dorinone 19.2g, CuCl
22H
2O 6.80g, the 30ml acetonitrile, 60 ℃ drip 140g mass percent 65% tertbutyl peroxide solution (following examples are together) reaction down.3.0h after, sampling is carried out GC-MS and is detected, and raw material all transforms fully, stopped reaction.Show that from the GC-MS detected result chromatographic peak area ratio of 4-oxo-beta-trans-Damascenone is 68%.Remove catalyzer, rotary evaporation is with solvent and trimethyl carbinol evaporate to dryness, 2*20ml extracted with diethyl ether, 20% Na
2SO
3Solution 40ml washing, clear water 2*50ml washing, anhydrous Na
2SO
4Drying, rotary evaporation, sherwood oil: ethyl acetate=4: 1 is an eluent, column chromatography is separated and is obtained 11.54g (yield: 4-oxo-beta-trans-Damascenone 56%).
Isolated 4-oxo-beta-trans-Damascenone is the white crystals body, 48 ℃～50 ℃ of fusing points.Analyze through GC-MS, its molecular ion peak is 206 (molecular ion peak M
+, abundance 31%), 206 (M
+, 31), 191 (30), 163 (12), 150 (10), 138 (29), 121 (12), 109 (8), 91 (7%), 79 (9), 69 (100), 55 (7).
1H NMR δ: 1.196 (s, 6H), 1.623 (s, 3H), 1.912-1.934 (t, J=6.9Hz, 2H), 1.963-1.991 (q, J
1=6.9Hz, J
2=J
3=1.5Hz, 3H), 6.161-6.230 (m, 1H), 6.690-6.812 (m, 1H);
13C NMR δ: 198.843,197.828,160.814,148.037,132.810,129.393,37.973,34.647,34.204,27.232,18.657,13.037; Meet with literature value.Ultimate analysis: by molecular formula C
13H
18O
2Calculated value, C 75.25%, and H 9.66%.Measured value: C 75.68%, H 9.81%.
Embodiment 2
Synthetic 4-oxo-beta-trans-Damascenone
Dorinone 19.2g, CuCl
22H
2O 6.8g, 30ml ethanol, 60 ℃ down with 140g tertbutyl peroxide (65%) reaction, sampling is through the GC-MS detection behind the 5h, the chromatographic peak peak area of 4-oxo-beta-trans-Damascenone reaches 58%.
Embodiment 3
Synthetic 4-oxo-beta-trans-Damascenone
Dorinone 19.2g, Cu (Ac)
28.0g, 30ml ethanol, with 140g tertbutyl peroxide (65%) reaction, sampling detects through GC-MS behind the 5h under the room temperature, and 4-oxo-beta-trans-Damascenone integral area has only 28%.
Embodiment 4
Synthetic 4-oxo-beta-trans-Damascenone
Dorinone 19.2g, CuCl
22H
2O 6.8g, 30ml acetone, under the room temperature with the 140g tertbutyl peroxide (the 65%th, what unit?) reaction, sampling detects through GC-MS behind the 3h, and 4-oxo-beta-trans-Damascenone integral area has only 56%.
Claims (8)
1. the synthetic method of a 4-oxo-beta-trans-Damascenone, it is characterized in that: raw material dorinone and catalyst metal copper compound and oxygenant tertbutyl peroxide are no more than 80 ℃ of reactions down, the corresponding 4-oxo-beta-trans-Damascenone of one-step synthesis in organic solvent.
2. synthetic method according to claim 1 is characterized in that: the metallic copper compound is divalence or monovalence copper compound.
3. synthetic method according to claim 2 is characterized in that: the metallic copper compound is CuCl
2, Cu (NO
3)
2, Cu (Ac)
2, CuSO
4Or CuI.
4. synthetic method according to claim 1 is characterized in that: control reaction temperature is at 30-60 ℃.
5. according to the synthetic method in the claim 1, described organic solvent is that polarity is 4-10.
6. according to the synthetic method in the claim 1, described organic solvent is acetonitrile, acetate, acetone, ethanol, methyl ethyl diketone or the trimethyl carbinol.
7. according to the synthetic method described in the claim 1, it is characterized in that: the reaction times is 2-8 hour.
8. according to the synthetic method of claim 1-7 described in each, it is characterized in that the reaction raw materials dorinone that will take by weighing joins in the organic solvent under magnetic agitation, and to wherein adding the catalyst metal copper compound, drip tertbutyl peroxide again, control reaction temperature, rotating filter are removed the catalyst metal copper compound, and decompression steams the organic solvent and the reduzate trimethyl carbinol, through extracted with diethyl ether, mass percent concentration is 15～25% Na
2SO
3Clear water washing again behind the solution washing, anhydrous Na
2SO
4Drying promptly gets 4-oxo-beta-trans-Damascenone through separating behind the rotary evaporation.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101454281A CN102260153A (en) | 2011-05-31 | 2011-05-31 | Method for synthesizing 4-oxo-beta-damascone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2011101454281A CN102260153A (en) | 2011-05-31 | 2011-05-31 | Method for synthesizing 4-oxo-beta-damascone |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN102260153A true CN102260153A (en) | 2011-11-30 |
Family
ID=45007023
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2011101454281A Pending CN102260153A (en) | 2011-05-31 | 2011-05-31 | Method for synthesizing 4-oxo-beta-damascone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102260153A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630289A (en) * | 2015-01-12 | 2015-05-20 | 安徽华业香料股份有限公司 | Synthesis method of (S)-(-)-alpha-damascenone |
| CN112375064A (en) * | 2020-11-10 | 2021-02-19 | 湖北吉和昌化工科技有限公司 | Vinyl sulfate synthesis process |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817842A (en) * | 2005-12-30 | 2006-08-16 | 贵州黄果树烟草集团公司 | Synthesis of ketone-substituted alpha-ionone, ketone-substituted beta-ionone, ether and ester derivative by one-step method |
| CN101143810A (en) * | 2007-10-11 | 2008-03-19 | 湖南中烟工业公司 | Allylic oxidation method for cyclohexene derivative |
| CN101624336A (en) * | 2009-08-07 | 2010-01-13 | 湖南中烟工业有限责任公司 | Oxo-alpha, beta-lonone preparation method |
-
2011
- 2011-05-31 CN CN2011101454281A patent/CN102260153A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1817842A (en) * | 2005-12-30 | 2006-08-16 | 贵州黄果树烟草集团公司 | Synthesis of ketone-substituted alpha-ionone, ketone-substituted beta-ionone, ether and ester derivative by one-step method |
| CN101143810A (en) * | 2007-10-11 | 2008-03-19 | 湖南中烟工业公司 | Allylic oxidation method for cyclohexene derivative |
| CN101624336A (en) * | 2009-08-07 | 2010-01-13 | 湖南中烟工业有限责任公司 | Oxo-alpha, beta-lonone preparation method |
Non-Patent Citations (2)
| Title |
|---|
| 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 20101115 尹大锋 alpha，beta-不饱和酮与不饱和羧酸类香料的合成及其在卷烟中的应用 第B024-99页 1-8 , 第11期 * |
| 尹大锋: "α，β-不饱和酮与不饱和羧酸类香料的合成及其在卷烟中的应用", 《中国优秀硕士学位论文全文数据库工程科技Ⅰ辑》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104630289A (en) * | 2015-01-12 | 2015-05-20 | 安徽华业香料股份有限公司 | Synthesis method of (S)-(-)-alpha-damascenone |
| CN112375064A (en) * | 2020-11-10 | 2021-02-19 | 湖北吉和昌化工科技有限公司 | Vinyl sulfate synthesis process |
| CN112375064B (en) * | 2020-11-10 | 2022-07-05 | 湖北吉和昌化工科技有限公司 | Vinyl sulfate synthesis process |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105153110A (en) | Synthesis method for chiral intermediate of atorvastatin calcium | |
| CN101143810B (en) | Allylic oxidation method for cyclohexene derivative | |
| CN101845017A (en) | Preparation method of atracurium besilate intermediates | |
| CN103694204B (en) | 1,2,4-trisubstituent furan compound and preparation method thereof | |
| CN102260153A (en) | Method for synthesizing 4-oxo-beta-damascone | |
| CN101624336A (en) | Oxo-alpha, beta-lonone preparation method | |
| CN101805249B (en) | Method for synthesizing oxo-alpha-ionone or oxo-beta-ionone | |
| Furuhata et al. | Nature of thioxyallyl intermediate in the decomposition of allene episulfide and pyrazoline-4-thione | |
| CN106588698B (en) | A kind of preparation method of the third ammonium aldehyde of N-Boc biphenyl | |
| Bartoli et al. | The Role of the α‐Stereogenic Center in the Control of Stereoselection in the Reduction of α‐Alkyl‐β‐hydroxy Ketones: A Highly Diastereoselective Protocol for the Synthesis of 1, 2‐syn‐2‐Alkyl‐1, 3‐diols | |
| CN114293210A (en) | Method for continuously electrosynthesis of benzopyran-4-ketone by using micro-reaction device | |
| CN108440460B (en) | Preparation method of perillene and analogues thereof | |
| CN102372745A (en) | Preparation method of hydroformylation catalyst precursor | |
| CN110128303B (en) | Method for synthesizing musk extract (2R,5R) -Musclide-A1 | |
| CN112441997B (en) | Method for synthesizing alpha- (2-tetrahydrofuryl) -acetophenone compound | |
| CN109833908A (en) | A kind of chirality high price iodine catalyst and its preparation method and application | |
| CN103224484A (en) | Preparation method of 2-((4R, 6S)-6-chloromethyl-2-alkyl-1,3-dioxane -4-yl)acetic acid | |
| CN109776610A (en) | Chiral P based on phenyl ethylamine skeleton, N, N ligand class compound and preparation method and application | |
| Kephart et al. | Synthesis of oxetane-3-carboxaldehyde and methyl oxetane-3-carboxylate via homologation of oxetane-3-one | |
| CN113651720B (en) | Substituted alkenyl thiocyanate compound and preparation method thereof | |
| CN102775268B (en) | Preparation method of 1-methyl-1-phenyl-3-phenylpropadiene compounds | |
| CN103880705B (en) | Dioxime ionone as well as preparation method and application thereof | |
| CN113372209B (en) | Synthesis method of megastigmatrienone | |
| Kashin et al. | Addition of stannylated carboxylic acid derivatives to the carbonyl group of aldehydes | |
| CN102329203A (en) | One-step synthetic method of 4-oxo-beta-damascenone |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C02 | Deemed withdrawal of patent application after publication (patent law 2001) | ||
| WD01 | Invention patent application deemed withdrawn after publication |
Application publication date: 20111130 |