CN103641701B - A kind of synthetic method of 4-oxo-beta-ionone - Google Patents
A kind of synthetic method of 4-oxo-beta-ionone Download PDFInfo
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- CN103641701B CN103641701B CN201310552553.3A CN201310552553A CN103641701B CN 103641701 B CN103641701 B CN 103641701B CN 201310552553 A CN201310552553 A CN 201310552553A CN 103641701 B CN103641701 B CN 103641701B
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- beta
- lonone
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- ionone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention relates to a kind of synthetic method of 4-oxo-beta-ionone, be specially and add C5H6Br2N2O2 in alpha, beta-lonone, react under alkali and solvent exist.The productive rate of the inventive method synthesis 4-oxo-beta-ionone can reach 85%, and the inventive method is easy, reaction conditions is gentle, yield is high, easy realization batch production.
Description
Technical field
The present invention relates to a kind of synthetic method of spices, specifically, relate to a kind of synthetic method of 4-oxo-beta-ionone.
Background technology
4-oxo-beta-ionone is one important in the degraded product spices of a series of carotenoid in tobacco, and in smoking property of cigarette, the soft fine and smooth flue gas of energy, improves cigarette sensory quality.
Direct oxidation alpha, beta-lonone is prepared 4-oxo-beta-ionone and is summed up and mainly contains chromic salts oxidation style, halate oxidation style, biological oxidation process, electrolytic oxidation, transition metal-catalyzed molecular oxidation method, N-bromo-succinimide (NBS) oxidation style etc.The shortcoming that wherein chromic salts oxidation style is maximum is that chromic salts consumption is large, easily causes serious environmental pollution.And halate oxidation rule condition is wayward, reaction yield fluctuation is larger.Biological oxidation process is difficult to realize batch production, and electrolytic oxidation by product is more, and yield is low, and energy consumption is large.
At present, transition metal-catalyzed molecular oxygen oxidation method receives many concerns, but molecular oxygen oxidation method also can because of catalyzer be difficult to removing or reactions steps long, there is the weakness such as certain danger and be difficult to realize batch production in reaction, if (JP:56161370, the 1981-12-11.) reports such as Oonoshi are by the esterification of alpha, beta-lonone enol, molecular oxygen catalysis oxidation again, hydrolysis obtains 4-oxo-beta-ionone, and the reactions steps of the method is long, and total productive rate is lower.
Patent CN101244992A discloses N-bromo-succinimide can prepare 4-oxo-beta-ionone by oxidation step alpha, beta-lonone, the method exist oxygenant NBS more unstable, comparatively large and that environmental pollution is slightly large shortcoming is stimulated to human body.
Summary of the invention
In order to solve the problems of the technologies described above, the invention provides a kind of easy, reaction conditions is gentle, yield is high, easily carry out producing in batches the method for 4-oxo-beta-ionone.
Technical scheme provided by the invention adds to make oxygenant to the C5H6Br2N2O2 of environment low toxicity in alpha, beta-lonone, reacts under alkali and solvent exist, synthesis 4-oxo-beta-ionone.
The oxygenant C5H6Br2N2O2 that the present invention relates to (complete by name: DBDMH, or be 1, bromo-2, the 4-imidazolinediones of 3-bis-, 1,3-dibromo-5,5-dimethylhydantoin, is abbreviated as DBDMH), its chemical structure is as follows:
Compared with N-bromo-succinimide in patent CN101244992A, C5H6Br2N2O2 has that active bromine content is high, excellent storage stability, use economic dispatch advantage, and to environment low toxicity.
The chemical structural formula of the raw material beta-ionone that the present invention relates to and product 4-oxo-beta-ionone (English called after 2-cyclohexen-1-one, 2,4,4-trimethyl-3-[3-oxo-1-butenyl]-) is as follows:
Alpha, beta-lonone 4-oxo-beta-ionone
According to the difference of naming method, the title that 4-oxo-beta-ionone also has other different, as ketone generation-alpha, beta-lonone, 3-oxo-beta-ionone etc.But there is the material of as above constitutional features shown in chemical structural formula, no matter be what title, all belong to 4-oxo-beta-ionone of the present invention.
In the present invention, C5H6Br2N2O2 charging capacity is defined as 0.5 ~ 1.5 times of the mol ratio of raw material beta-ionone, when the amount of C5H6Br2N2O2 is lower than this proportional range, the then low conversion rate of alpha, beta-lonone, containing more 3 in product, 4-dehydrogenation-alpha, beta-lonone by product, affects the yield of target product 4-oxo-beta-ionone.On the other hand, the amount of C5H6Br2N2O2 is greater than this proportional range, then product is complicated, color burn, containing more bromo oxidation products, affects the yield of target product equally.C5H6Br2N2O2 charging capacity is preferably 0.9 ~ 1.1 times of the mol ratio of raw material beta-ionone.
In the inventive method, added alkali, comprises mineral alkali and organic bases.Described mineral alkali is the oxyhydroxide of metal, or the carbonate of metal, or the supercarbonate of metal, be preferably sodium hydroxide, potassium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, calcium hydroxide, calcium carbonate, Calcium hydrogen carbonate, organic bases is preferably pyridine etc.The usage quantity of alkali is 1.0 ~ 3.0 times of alpha, beta-lonone mol ratio, and preferred usage quantity is 1.5 ~ 1.8 times.
Reaction solvent can be water, and also can be the mixture of water and organic solvent, organic solvent comprises acetone, methyl alcohol, ethanol, tetrahydrofuran (THF), methylene dichloride, trichloromethane, hexanaphthene, normal hexane etc.
The heat release of the reaction that the present invention relates to own, under room temperature, (20 ~ 30 DEG C) reaction just can be carried out, and reaction preference is fine.
The method take alpha, beta-lonone as raw material, adds C5H6Br2N2O2, alkali and solvent wherein, stirs under room temperature or heating state, reaction 4h ~ 8h, " treat different things alike " and synthesize 4-oxo-beta-ionone, under optimum condition, the productive rate of 4-oxo-beta-ionone can reach 85%.With the inventive method synthesis 4-oxo-beta-ionone, easy, reaction conditions is gentle, yield is high, easy realizations is produced in batches.
Embodiment
Following examples for illustration of the present invention, but are not used for limiting the scope of the invention.Without departing from the spirit and substance of the case in the present invention, the amendment do the inventive method, step or condition or replacement, all belong to scope of the present invention.
If do not specialize, the conventional means that technique means used in embodiment is well known to those skilled in the art.
Embodiment 1
1.92g alpha, beta-lonone, 0.6g sodium hydroxide (being equivalent to 1.5 times of alpha, beta-lonone mol ratio), 20mL water, 3.3g C5H6Br2N2O2 (being equivalent to 1.1 times of alpha, beta-lonone mol ratio), stirring at room temperature, reaction 5h, reaction is finished, pillar layer separation is purified to obtain 4-oxo-beta-ionone 1.75g, and productive rate is 85%.GC-MS analyzes in crude product in addition a little 3,4-dehydrogenations-alpha, beta-lonone.Isolated 4-oxo-beta-ionone is light yellow crystal, and fusing point is 50 DEG C ~ 52 DEG C.Analyze through GC-MS, its molecular ion peak is 206 (molecular ion peak M
+, abundance 72%), fragment peak has 163(100%), 149(20%), 135(25%), 121(47%);
1h-MNR (CD
3cl, 400MHz) δ: 1.20 (s, 6H), 1.80 (d; J=0.9Hz, 3H), 1.88 ~ 1.93 (m; 2H), 2.36 (s, 3H); 2.52 ~ 2.57 (m, 2H), 6.19 (d; J=16.5Hz, 1H), 7.25 (dd; J=16.5Hz, J=0.9Hz, 1H);
13c-MNR δ: 13.3,27.2,27.9,34.1,35.4,37.2,131.3,133.5,140.3,157.7,197.4,198.5. conforms to literature value.
Embodiment 2
Repeat embodiment 1 according to described same steps, the amount of C5H6Br2N2O2 is reduced to 0.5 times that 1.5g(is equivalent to alpha, beta-lonone mol ratio), after reaction 6h, reaction is finished, and pillar layer separation is purified to obtain 4-oxo-beta-ionone 0.76g, and productive rate is 37%.Analyze through GC-MS, result is the same.
Embodiment 3
Repeat embodiment 1 according to described same steps, the amount of C5H6Br2N2O2 is increased to 1.5 times that 4.5g(is equivalent to alpha, beta-lonone mol ratio), after reaction 4h, reaction is finished, and pillar layer separation is purified to obtain 4-oxo-beta-ionone 1.28g, and productive rate is 62%.Analyze through GC-MS, result is the same.
Embodiment 4
1.92g alpha, beta-lonone, 0.8g potassium hydroxide (being equivalent to 1.5 times of alpha, beta-lonone mol ratio), 20mL water, 3.3g C5H6Br2N2O2 (being equivalent to 1.1 times of alpha, beta-lonone amount of substance), stirring at room temperature, reaction 5h, reaction is finished, pillar layer separation is purified to obtain 4-oxo-beta-ionone 1.48g, and productive rate is 72%.Analyze through GC-MS, result is the same.
Embodiment 5
1.92g alpha, beta-lonone, 1.1g sodium carbonate (being equivalent to 1.0 times of alpha, beta-lonone mol ratio), 20mL water, 3.3g C5H6Br2N2O2 (being equivalent to 1.1 times of alpha, beta-lonone mol ratio), stirring at room temperature, reaction 6h, reaction is finished, pillar layer separation is purified to obtain 4-oxo-beta-ionone 1.36g, and productive rate is 66%.Analyze through GC-MS, result is the same.
Embodiment 6
1.92g alpha, beta-lonone, 2.4g pyridine (being equivalent to 3.0 times of alpha, beta-lonone mol ratio), 20mL water and acetone, 5mL tetrahydrofuran (THF), 3.3g C5H6Br2N2O2 (being equivalent to 1.1 times of alpha, beta-lonone amount of substance), stirring at room temperature, reaction 6h, reaction is finished, and pillar layer separation is purified to obtain 4-oxo-beta-ionone 0.56g, and productive rate is 27%.Analyze through GC-MS, result is the same.
Although above the present invention is described in detail with a general description of the specific embodiments, on basis of the present invention, can make some modifications or improvements it, this will be apparent to those skilled in the art.Therefore, these modifications or improvements without departing from theon the basis of the spirit of the present invention, all belong to the scope of protection of present invention.
Claims (7)
1. the synthetic method of a 4-oxo-beta-ionone, it is characterized in that, C5H6Br2N2O2 is added in alpha, beta-lonone, react under alkali and solvent exist, the charging capacity of described C5H6Br2N2O2 is 0.5 ~ 1.5 times of alpha, beta-lonone mol ratio, and the usage quantity of described alkali is 1.0 ~ 3.0 times of alpha, beta-lonone mol ratio.
2. synthetic method according to claim 1, is characterized in that, the charging capacity of described C5H6Br2N2O2 is 0.9 ~ 1.1 times of alpha, beta-lonone mol ratio.
3. synthetic method according to claim 1, is characterized in that, described alkali is mineral alkali or organic bases, and wherein said mineral alkali is the supercarbonate of the oxyhydroxide of metal, the carbonate of metal or metal.
4. synthetic method according to claim 3, it is characterized in that, described mineral alkali is selected from one or more in sodium hydroxide, potassium hydroxide, lithium hydroxide, hydrated barta, sodium carbonate, salt of wormwood, sodium bicarbonate, saleratus, calcium hydroxide, calcium carbonate, Calcium hydrogen carbonate, and described organic bases is pyridine.
5. synthetic method according to claim 1, is characterized in that, the usage quantity of described alkali is 1.5 ~ 1.8 times of alpha, beta-lonone mol ratio.
6. synthetic method according to claim 1, is characterized in that, described solvent is the mixture of water or water and organic solvent.
7. synthetic method according to claim 1, is characterized in that, temperature of reaction is room temperature.
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| CN201310552553.3A CN103641701B (en) | 2013-11-08 | 2013-11-08 | A kind of synthetic method of 4-oxo-beta-ionone |
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| CN201310552553.3A CN103641701B (en) | 2013-11-08 | 2013-11-08 | A kind of synthetic method of 4-oxo-beta-ionone |
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| CN103641701A CN103641701A (en) | 2014-03-19 |
| CN103641701B true CN103641701B (en) | 2015-09-23 |
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| US7429674B2 (en) * | 2004-04-14 | 2008-09-30 | Merck & Co. Inc.. | Process for preparing fluoroleucine alkyl esters |
| CN101244992B (en) * | 2007-02-15 | 2011-11-23 | 湖南中烟工业有限责任公司 | Simple synthesizing method for 4-oxo-beta-jonone |
| CN102503927B (en) * | 2011-11-21 | 2013-07-24 | 湖南大学 | Method for preparing helional from 4-(2-methylallyl)-1,2-dihydroxybenzene |
| CN102826979B (en) * | 2012-07-04 | 2014-12-24 | 华东师范大学 | Method for selectively oxidizing benzyl alcohols into benzaldehyde and methyl benzoate compounds through using 1,3-dibromo-5,5-dimethylhydantoin (DBDMH) |
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