CN102249880B - Method for synthesizing oxo-irisone by oxidizing irisone - Google Patents
Method for synthesizing oxo-irisone by oxidizing irisone Download PDFInfo
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- CN102249880B CN102249880B CN 201110123283 CN201110123283A CN102249880B CN 102249880 B CN102249880 B CN 102249880B CN 201110123283 CN201110123283 CN 201110123283 CN 201110123283 A CN201110123283 A CN 201110123283A CN 102249880 B CN102249880 B CN 102249880B
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Abstract
The invention relates to a synthesizing method of oxo-irisone. According to the method for synthesizing the oxo-irisone, provided by the invention, the irisone is oxidized by a reaction system containing N-hydroxyl-phthalimide (NHPI) to carry out a catalytic oxidization to synthesize the oxo-irisone. By oxidizing the irisone through the method, other oxidants which cause pollution are not used so that the method is environment-friendly; and the source of the used oxygen gas or air is abundant and cheap so that the cost is low.
Description
Technical field
The oxo jononeionone that the present invention relates to comprises 3-oxo-α-Zi Luolantong [2-Cyclohexen-1-one, 3,5,5-trimethyl-4-(3-oxo-1-butenyl)-] (formula I) and 4-oxo-beta-jononeionone [2-cyclohexen-1-one, 2,4,4-trimethyl-3-[3-oxo-1-butenyl]-] synthetic method of (formula II)
Background technology
According to the difference of naming method, 4-oxo-beta-jononeionone and 3-oxo-α-Zi Luolantong also have other different title, as being called as ketone generation-α (or β)-jononeionone, 3-oxo-α (or the β)-jononeionone etc. that is otherwise known as sometimes sometimes.But what title no matter have suc as formula (I) and the material of constitutional features (II), be, all belongs to 3-oxo-α-Zi Luolantong of the present invention and 4-oxo-beta-jononeionone.
4-oxo-beta-jononeionone is a kind of important tobacco aromatics using, joins in the cigarette, can play the effect of exquisiteness, soft cigarette smoke.Be that the synthetic carotenoid compounds of intermediate 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, can be used as food flavouring or spices in the foods and cosmetics preparation, also be the key intermediate of synthetic carotenoid compounds, the important source material of especially synthetic green nourishing spices such as glucoside derivative.
The oxo jononeionone can be obtained by allylic oxidation by jononeionone, and traditional method such as the end of the forties in last century, Oppenauer etc. have synthesized 4-oxo-beta-jononeionone with the chromic acid tert-butyl oxidation.Existing method is concluded and is mainly contained chromic salts oxidation style, sodium chlorate oxidation style, biological oxidation process, electrolytic oxidation etc.Wherein the shortcoming of chromic salts oxidation style maximum is that consumption is big, easily causes serious environmental to pollute.And sodium chlorate oxidation rule condition is wayward, the large usage quantity of oxygenant.And biological oxidation process is difficult to realize producing in batches, and the electrolytic oxidation by product is more, and yield is low, and energy consumption is big.From the angle of environmental protection, the molecular oxygen method should be the most promising also be the method for being praised highly most.But the key of molecular oxygen oxidation method is how selecting catalyst comes activate molecular oxygen, and itself and raw material jononeionone are reacted.Report such as Oonoshi is with the esterification of alpha, beta-lonone enol, and molecular oxygen catalysis oxidation again, hydrolysis obtain 4-oxo-beta-jononeionone, and this method has also been utilized the molecular oxygen catalysis oxidation style.But the reactions steps of this method is long, and total productive rate is lower.
Summary of the invention
The method that the purpose of this invention is to provide a kind of synthesizing oxo-jonone by oxidizing jonone, it is many to overcome existing method by product, shortcomings such as the low or easy contaminate environment of yield.
The method of synthesizing oxo jononeionone provided by the invention is, to contain the reaction system jonone by oxidizing of N-hydroxyl-phthalic imidine (NHPI), catalyzed oxidation synthesizing oxo jononeionone.
In above-mentioned reaction system, as the NHPI of catalyzer, increase the selectivity that its consumption can obviously improve the oxo jononeionone, reduce the amount of NHPI, therefore the selectivity of oxo jononeionone reduces, the usage quantity of NHPI be preferably raw material amount 1%～100%.
In above-mentioned reaction system, be oxygenant with oxygen or air preferably.
In above-mentioned reaction system, preferable reaction temperature is 40～150 ℃
Further preferable reaction temperature is 60～90 ℃.
Further, according to embodiments of the invention, preferably in reaction system, add methyl ethyl diketone transition metal complex, for example acetylacetone cobalt or vanadium acetylacetonate.The adding of this complex compound can fast reaction speed.
The present invention selects to contain the reaction system jonone by oxidizing of NHPI, be oxygenant with oxygen or air, catalyzed oxidation synthesizing oxo jononeionone, the raw material jononeionone can almost completely transform, the chromatographic peak peak area ratio of oxo jononeionone can reach 75% in the reaction product, selectivity is good, has removed the shortcoming of polystep reaction complex steps from, is particularly suitable for producing in batches.Use this method jonone by oxidizing need not use other oxygenant of pollution, environmental friendliness; And the oxygen that uses or air source are abundant, inexpensive, and cost is low.
Embodiment
Embodiment 1
In having the 150mL three-necked bottle of prolong, add 5g alpha, beta-lonone and 55mL acetone, N-hydroxyl-phthalyl Asia (NHPI) 4.25g (consumption be alpha, beta-lonone amount of substance 100%), the inferior cobalt 0.38g of methyl ethyl diketone, 80 ℃ down by the bubbler aerating oxygen, reaction 6h, GC-MS detects the raw material alpha, beta-lonone and all transforms stopped reaction.The chromatographic peak peak area ratio that GC-MS detects 5,6-epoxy-bata-ionone is 23%; 4-oxo-beta-jononeionone chromatographic peak peak area ratio be 75%.
Isolated 4-oxo-beta-jononeionone is light yellow crystal, and fusing point is 50 ℃～52 ℃.Analyze through GC-MS, its molecular ion peak is 206 (molecular ion peak M
+, 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:1663cm
-1 1H-MNR (CD
3Cl, 400MHz): 1.14 (s, 6H, 2H
3C-C (4)), 1.80～1.83 (m, 2H, 2H-C (5)), (2.49 m, 2H, 2H-C (6)), 1.68 (s, 3H, 3H-C (2)), 7.26～7.30 (m, J=16,1H, 1H-C (1 ')), 6.11～6.15 (m, J=16,1H, 1H-C (2 ')), 2.32 (s, 3H, 3H-C (4 ')), conform to literature value.Ultimate analysis: by molecular formula C
13H
18O
2Calculated value: C 75.25%, H 9.66%.Measured value: C75.69%, H 9.80%.
Embodiment 2
Repeat embodiment 1 according to described same steps as, but N-hydroxyphthalimide (NHPI) 4.25g amount reduces to 0.11g, consumption is 2.5% of alpha, beta-lonone amount of substance, promotor is vanadium acetylacetonate (0.15 gram), behind the bearing reaction 12h, the chromatographic peak peak area ratio of 5,6-epoxy-bata-ionone is that the chromatographic peak peak area ratio of 80%, 4-oxo-beta-jononeionone is 8%.
Embodiment 3
Repeat embodiment 1 according to described same steps as, but temperature of reaction is 50 ℃, N-hydroxyphthalimide consumption is 30% of alpha, beta-lonone amount of substance.Behind the bearing reaction 10h, 4-oxo-beta-jononeionone chromatographic peak peak area ratio is 65%.
Embodiment 4
Repeat embodiment 1 according to described same steps as, but replace oxygen to make oxygenant with air, behind the bearing reaction 12h, feedstock conversion is complete.GC-MS detect 4-oxo-beta-jononeionone chromatographic peak peak area ratio be 70%.
Embodiment 5
Repeat embodiment 1 according to described same steps as, but replace oxygen to make oxygenant with air, temperature of reaction is 130 ℃, behind the bearing reaction 12h, GC-MS detect 4-oxo-beta-jononeionone chromatographic peak peak area ratio be 75%.
Embodiment 6
Repeat embodiment 1 according to described same steps as, but do not add the inferior cobalt of promotor methyl ethyl diketone, behind the bearing reaction 6h, the chromatographic peak peak area ratio that the raw material alpha, beta-lonone only transforms 10%, 4-oxo-beta-jononeionone is 5%.
Embodiment 7
Repeat embodiment 1 according to described same steps as, but raw material replaces alpha, beta-lonone with α-Zi Luolantong, behind the bearing reaction 6h, the chromatographic peak peak area ratio of 3-oxo-α-Zi Luolantong is 75%.Isolating 3-oxo-α-Zi Luolantong is light yellow crystal, and fusing point is 71～72 ℃.Analyze through GC-MS, its molecular ion peak is 206 (molecular ion peak M
+, 0.9%), 150 (21%), 135 (5%), 121 (2%), 108 (100%), 91 (6%), 77 (15%);
1H-MNR (CD
3Cl, 400MHz): 1.07 (s, 6H, 2H
3C-C (5)), 2.13～2.41 (m, 2H, 2H-C (6)), 5.99 (s, 1H, 1H-C (2)), 1.92 (s, 3H, 1H
3C-C (3)), 6.71 (dd, J=16Hz, 1H, 1H-C (1 ')), 6.19 (d, J=16Hz, 1H, 1H-C (2 ')), 2.31 (s, 3H, 3H-C (4 ')), 2.74 (d, J=9.0Hz, 1H, 1H-C (4)) conform to literature value.Ultimate analysis: by molecular formula C
13H
18O
2Calculated value, C 75.25%, and H 9.66%.Measured value: C75.71%, H 9.79%.
Claims (1)
1. the method for a synthesizing oxo-jonone by oxidizing jonone, described oxo jononeionone is 4-oxo-beta-jononeionone and 3-oxo-α-Zi Luolantong; Concrete grammar is selected from any one in following several scheme:
Scheme 1: in having the 150mL three-necked bottle of prolong, add 5g alpha, beta-lonone and 55mL acetone, N-hydroxyl-phthalic imidine: 4.25g, the inferior cobalt 0.38g of methyl ethyl diketone, 80 ℃ down by the bubbler aerating oxygen, reaction 6h, GC-MS detects the raw material alpha, beta-lonone and all transforms stopped reaction;
Scheme 2: carry out according to scheme 1 described same steps as, but temperature of reaction is 50 ℃ that N-hydroxyphthalimide consumption is 30% of alpha, beta-lonone amount of substance, reaction 10h;
Scheme 3: carry out according to scheme 1 described same steps as, but replace oxygen to make oxygenant with air, reaction 12h;
Scheme 4: carry out according to scheme 1 described same steps as, but replace oxygen to make oxygenant with air, temperature of reaction is 130 ℃, reaction 12h;
Scheme 5: carry out according to scheme 1 described same steps as, but raw material replaces alpha, beta-lonone with α-Zi Luolantong reaction 6h.
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| CN 201110123283 CN102249880B (en) | 2007-02-15 | 2007-02-15 | Method for synthesizing oxo-irisone by oxidizing irisone |
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| CN102249880B true CN102249880B (en) | 2013-07-03 |
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| 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 |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4393243A (en) * | 1981-03-17 | 1983-07-12 | Hoffmann-La Roche Inc. | Carotenoid intermediate by an oxidation process |
-
2007
- 2007-02-15 CN CN 201110123283 patent/CN102249880B/en active Active
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4393243A (en) * | 1981-03-17 | 1983-07-12 | Hoffmann-La Roche Inc. | Carotenoid intermediate by an oxidation process |
Non-Patent Citations (2)
| Title |
|---|
| N-羟基邻苯二甲酰亚胺(NHPI)用于有机氧化反应的研究进展;梁舰等;《化学研究与应用》;20041031;第16卷(第5期);第597-600页 * |
| 梁舰等.N-羟基邻苯二甲酰亚胺(NHPI)用于有机氧化反应的研究进展.《化学研究与应用》.2004,第16卷(第5期), |
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