CN101624336A - Oxo-alpha, beta-lonone preparation method - Google Patents
Oxo-alpha, beta-lonone preparation method Download PDFInfo
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- CN101624336A CN101624336A CN200910044044A CN200910044044A CN101624336A CN 101624336 A CN101624336 A CN 101624336A CN 200910044044 A CN200910044044 A CN 200910044044A CN 200910044044 A CN200910044044 A CN 200910044044A CN 101624336 A CN101624336 A CN 101624336A
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- beta
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Abstract
The invention discloses a oxo-alpha, beta-lonone oxidation method, belonging to the fine chemical engineering technical field and the method comprises the following steps: adopting alpha, beta-lonone, copper compound and hydroxyl-hydrogen peroxide to react in organic solvent below 80 DEG C for several hours and synthesizing corresponding oxo-alpha, beta-lonone through one step. The invention has simple operation and high yield; the prepared oxo-alpha, beta-lonone can be widely used in food additives, cosmetics, medicines, cigarettes and the like and has very high application value.
Description
Technical field:
The invention belongs to the fine chemical technology field, relate to a kind ofly by α, alpha, beta-lonone is produced corresponding oxo α, the novel method of alpha, beta-lonone.
Background technology:
Oxo α, alpha, beta-lonone comprises 4-oxo-beta-jononeionone (I) and 3-oxo-α-Zi Luolantong (II), they are a kind of very important tobacco aromatics using and organic synthesis intermediate, are usually used in preparation and the preparation of heterogeneous ring compound and the synthetic intermediate of tobacco aromatics using Megastigmatrienone etc. of essence.
4-oxo-beta-jononeionone is a kind of good tobacco aromatics using, it joins in the cigarette, can play exquisiteness, the effect of soft cigarette smoke, be that intermediate synthetic carotenoid compounds is applied to medicine and material science with it simultaneously, obtained in recent years paying close attention to widely.3-oxo-α-Zi Luolantong is mainly used in food, makeup and fragrance industry, also is the key intermediate of synthetic carotenoid compounds, the important source material of especially synthetic green nourishing spices such as glucoside derivative.
At present, synthesizing oxo α, the method for alpha, beta-lonone has often, and that has reported has sodium chlorate oxidation style, biological oxidation process, molecular oxygen oxidation method, a chromic salts oxidation style etc.But the productive rate of these synthetic method gained is unsatisfactory.Or building-up process is tediously long, complex process; Or use some valuable metals and its title complex; Or use the disagreeableness reagent of environment, as chromium trioxide, chromium trioxide-pyridine, chromic acid tert-butyl, dichromic acid pyridine, pyridinium chlorochromate etc.These method cost height, product is difficult to purifying, has limited mass production.
Therefore, seek a kind of simple, efficient, safety, environmental protection, low consumed α, alpha, beta-lonone method for oxidation are the common recognitions in the fragrance industry.
Summary of the invention:
It is simple that purpose of the present invention aims to provide a kind of reactions steps, easy to operate, with low cost, environmental friendliness, and speed of response is fast, the oxo α that productive rate is high, the preparation method of alpha, beta-lonone.
Technical scheme of the present invention is: with reaction raw materials α, alpha, beta-lonone and metallic copper compound and alkyl hydrogen peroxide are in organic solvent, and 10-80 ℃ is reacted the corresponding oxo α of one-step synthesis, alpha, beta-lonone down.
Organic solvent in the described reaction is meant the organic solvent that traditional polarity is bigger, as acetonitrile, and acetate,
Acetone, ethanol, the methyl ethyl diketone or the trimethyl carbinol etc.;
Described metallic copper compound is CuCl
2, Cu (NO
3)
2, Cu (Ac)
2, CuI or CuSO
4Etc. divalence or monovalence copper compound.
Described alkyl hydrogen peroxide preferred tertiary butylhydroperoxide.
The preferred temperature of reaction of the present invention is at 10-70 ℃, and optimal reaction temperature is 10-60 ℃.
Optimum reacting time of the present invention is 2-10 hour.
α in the described reaction, alpha, beta-lonone: metallic copper compound: the proportioning of tertbutyl peroxide is 1mol: (0.01～1mol): (1～20mol).
The concrete embodiment of the present invention is:
The reaction raw materials α that under magnetic agitation, will take by weighing, alpha, beta-lonone joins in the organic solvent, to wherein adding the metallic copper compound, drip the alkyl hydrogen peroxide again, control reaction temperature 10-80 ℃, after reaction for some time, remove catalyzer, steam organic solvent and reduzate under the decompression, through organic extractant extraction, Na
2SO
3Clear water washing again behind the solution washing, anhydrous Na
2SO
4Drying promptly gets corresponding oxo α, alpha, beta-lonone through separating behind the rotary evaporation.After simple process, product purity is not less than 98%.
The contriver has found the metallic copper compound through repeatedly testing, and this catalysts can effectively promote the smooth of entire reaction, efficiently carries out.Advantage of the present invention is that also reaction process is simple, and reactions steps is a step, and technology greatly simplifies the operation.In reaction process of the present invention, required raw materials cost is low, and mantoquita reclaims 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-jononeionone
Alpha, beta-lonone 19.2g, CuCl
2.2H
2O 6.80g, the 30ml acetonitrile, 60 ℃ drip 140g tertbutyl peroxide (65%) 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-jononeionone is 68%, 5, the chromatographic peak area of 6-epoxy-bata-ionone is 27%.Remove by filter catalyzer through leaving standstill, rotary evaporation is with solvent and trimethyl carbinol evaporate to dryness, 2*20ml extracted with diethyl ether, 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-jononeionone 56%).
Isolated 4-oxo-beta-jononeionone is the colourless crystallization body, 50 ℃～52 ℃ of fusing points.Analyze through GC-MS, its molecular ion peak is 206 (the sub-peak M of molecule
+, abundance 72%), 163 (M
+-CH
3CO, 100%), 149 (M
+-C
2H
5CO, 20%), 135 (M
+-C
4H
7O, 25%), 121 (M
+-C
5H
9O, 47%); IR/v:1667cm
-1NMR
1H (CDCl
3, 300MHz): 1.010 (s, 3H), 1.082 (s, 3H), 1.898-1.903 (s, 3H), 2.123-2.184 (d, J=17.1Hz, 1H), 2.287 (s, 3H), 2.337-2.395 (d, J=16.8Hz, 1H), 2.699-2.731 (d, J=9.6Hz, 1H), and 5.984-5.993 (m, 1H), 6.161-6.216 (q, J=15.6Hz, 1H), 6.632-6.716 (q, J
1=15.6Hz, J
2=9.6Hz, 1H).
13C (CDCl
3): 198.247,197.485,159.106,143.528,133.680,126.852,55.366,47.264,36.630,27.842,27.514,27.270,23.440.
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-jononeionone
Alpha, beta-lonone 19.2g, CuCl
2.2H
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-jononeionone reaches 58%.
Embodiment 3:
Synthetic 4-oxo-beta-jononeionone
Alpha, beta-lonone 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-jononeionone integral area has only 28%.
Embodiment 4:
Synthetic 3-oxo-α-Zi Luolantong
α-Zi Luolantong 19.2g, CuCl
2.2H
2O 6.80g, the 20ml acetonitrile, 60 ℃ drip 140g tertbutyl peroxide (65%) reaction down, and behind the 5.0h, 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-jononeionone is 18.3%, the chromatographic peak area of 3-oxo-α-Zi Luolantong is 81.0%.Remove by filter catalyzer through leaving standstill, rotary evaporation is with solvent and trimethyl carbinol evaporate to dryness, 2*20ml ethyl acetate extraction, Na
2SO
3Solution 40ml washing, clear water 2*40ml washing, anhydrous Na
2SO
4Drying, rotary evaporation, sherwood oil: ethyl acetate=4: 1 is an eluent, column chromatography is separated and is obtained 14.8g (yield: 3-oxo-α-Zi Luolantong 71.8%).
Isolated 3-oxo-α-Zi Luolantong is faint yellow xln, 71 ℃～72 ℃ of fusing points.Analyze through GC-MS, its molecular ion peak is 206 (molecular ion peak M
+, abundance 1%), 191 (1%), 163 (1%), 150 (23%), 135 (6%), 121 (3%), 108 (100%), 91 (5%), 77 (10%), 65 (2%); NMR
1H (CDCl
3, 300MHz): 1.199 (s, 6H), 1.802 (s, 3H), 1.897-1.925 (t, J=6.9Hz, 2H), 2.364 (s, 3H), 2.539-2.565 (t, J=6.9Hz, 2H), 6.165-6.220 (d, J=16.5Hz, 1H), 7.218-7.277 (q, J
1=16.5Hz, J
2=J3=7.2Hz, 1H).
13C (CDCl
3): 198.514,197.393,157.694,140.271,133.451,131.254,37.164,35.432,34.067,27.865,27.193,13.332. and literature value meet.Ultimate analysis: by molecular formula C
13H
18O
2Calculated value, C 75.25%, and H 9.65%.Measured value: C 75.71%, H 9.79%.
Embodiment 5:
Synthetic 3-oxo-α-Zi Luolantong
α-Zi Luolantong 19.2g, CuCl
2.2H
2O 6.80g, 30ml ethanol, 60 ℃ drip 140g tertbutyl peroxide (65%) reaction down, and behind the 5.0h, sampling is carried out GC-MS and is detected, and raw material transforms fully substantially, stopped reaction.Show that from the GC-MS detected result chromatographic peak area ratio of 4-oxo-beta-jononeionone is 27.6%, the chromatographic peak area of 3-oxo-α-Zi Luolantong is 70.6%
Embodiment 6:
Synthetic 3-oxo-α-Zi Luolantong
α-Zi Luolantong 19.2g, Cu (NO
3)
2.3H
2O 9.6g, 30ml ethanol, 40 ℃ drip 140g tertbutyl peroxide (65%) reaction down, and behind the 5.0h, sampling is carried out GC-MS and is detected, and raw material transforms fully substantially, stopped reaction.Show that from the GC-MS detected result chromatographic peak area ratio of 4-oxo-beta-jononeionone is 12.6%, the chromatographic peak area of 3-oxo-α-Zi Luolantong is 23.8%.
Claims (7)
1 one kinds of oxo α, the preparation method of alpha, beta-lonone is characterized in that: with reaction raw materials α, alpha, beta-lonone and metallic copper compound and alkyl hydrogen peroxide are in organic solvent, in 10-80 ℃ of reaction down, the corresponding oxo α of one-step synthesis, alpha, beta-lonone.
2 preparation methods according to claim 1, described metallic copper compound is CuCl
2, Cu (NO
3)
2, Cu (Ac)
2, CuSO
4Or CuI.
3 preparation methods according to claim 1, the alkyl hydrogen peroxide is a tertbutyl peroxide
4 preparation methods according to claim 1 is characterized in that: control reaction temperature is at 10-70 ℃.
5 according to the preparation method described in the claim 1, and organic solvent is acetonitrile, acetate, acetone, ethanol, methyl ethyl diketone or the trimethyl carbinol.
6 according to the preparation method described in the claim 1,, the reaction times is 2-10 hour.
7, according to the preparation method described in the claim 1, in the described reaction, α, alpha, beta-lonone: metallic copper compound: tertbutyl peroxide is 1mol: (0.01～1mol): (1～20mol).
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805249A (en) * | 2010-04-07 | 2010-08-18 | 湖南中烟工业有限责任公司 | Method for synthesizing oxo-alpha-ionone or oxo-beta-ionone |
| CN102260153A (en) * | 2011-05-31 | 2011-11-30 | 湖南中烟工业有限责任公司 | Method for synthesizing 4-oxo-beta-damascone |
| CN110183321A (en) * | 2019-04-25 | 2019-08-30 | 安徽中烟工业有限责任公司 | A method of efficiently preparing keto-ionone |
| CN113684096A (en) * | 2021-09-18 | 2021-11-23 | 浙江中烟工业有限责任公司 | Sweet-baked tobacco essence and preparation method and application thereof |
-
2009
- 2009-08-07 CN CN200910044044A patent/CN101624336A/en active Pending
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101805249A (en) * | 2010-04-07 | 2010-08-18 | 湖南中烟工业有限责任公司 | Method for synthesizing oxo-alpha-ionone or oxo-beta-ionone |
| CN101805249B (en) * | 2010-04-07 | 2012-12-19 | 湖南中烟工业有限责任公司 | Method for synthesizing oxo-alpha-ionone or oxo-beta-ionone |
| CN102260153A (en) * | 2011-05-31 | 2011-11-30 | 湖南中烟工业有限责任公司 | Method for synthesizing 4-oxo-beta-damascone |
| CN110183321A (en) * | 2019-04-25 | 2019-08-30 | 安徽中烟工业有限责任公司 | A method of efficiently preparing keto-ionone |
| CN110183321B (en) * | 2019-04-25 | 2022-05-10 | 安徽中烟工业有限责任公司 | Method for efficiently preparing oxoionone |
| CN113684096A (en) * | 2021-09-18 | 2021-11-23 | 浙江中烟工业有限责任公司 | Sweet-baked tobacco essence and preparation method and application thereof |
| CN113684096B (en) * | 2021-09-18 | 2023-10-20 | 浙江中烟工业有限责任公司 | Essence for roasted sweet and fragrant cigarettes and preparation method and application thereof |
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Open date: 20100113 |