CN100513400C - Use of hydroxyl cupric phosphate in synthesizing 5,6-epoxy-bata-ionone and method of synthesizing 5,6-epoxy-bata-ionone - Google Patents
Use of hydroxyl cupric phosphate in synthesizing 5,6-epoxy-bata-ionone and method of synthesizing 5,6-epoxy-bata-ionone Download PDFInfo
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- CN100513400C CN100513400C CNB2006100322369A CN200610032236A CN100513400C CN 100513400 C CN100513400 C CN 100513400C CN B2006100322369 A CNB2006100322369 A CN B2006100322369A CN 200610032236 A CN200610032236 A CN 200610032236A CN 100513400 C CN100513400 C CN 100513400C
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Abstract
The invention discloses a synthesizing method and application of 5, 6-epoxy-beta-ionone based on cupric phosphate hydroxyl as catalyst, which is characterized by the following: adopting the molar rate of raw material and catalyst at 0.01-50%; heating to 40-150 deg.c; oxidizing beta-ionone through oxygen or air to obtain the product.
Description
Technical field
The present invention relates to hydroxyl cupric phosphate and synthesizing 5, the application in the 6-epoxy-bata-ionone, and synthesize 5, the method for 6-epoxy-bata-ionone.
Background technology
5, the systematic naming method of 6-epoxy-bata-ionone is: " 3-buten-2-one, 4-{2,2,6-trimethyl-7-oxabicyclo (4.1.0) hept-1-yl}-".This compound is the important spices of a class, in particular as tobacco aromatics using, various cigarette is had significant perfuming effect.Along with smoking and health problem are subject to people's attention day by day, fall that smoke that Jiao causes is thin must to need synthetic tobacco aromatics using to remedy.The epoxidation Reaction of Alkenes method is a lot, molecular oxygen is because oxidation products is a water, pollution-free and economy is easy to get and is described as " green oxygen source ", contains chromium cpd and oxymuriate or hypochlorite oxidizing reaction relatively with general, and molecular oxygen or atmospheric oxidation have environment-friendly advantage clearly.Which kind of catalyst activation molecular oxygen is the key of molecular oxygen oxidation be to adopt, and makes it to interact with alkene.Conclusion is got up, and the oxide catalyst of alkene is divided into homogeneous catalytic reaction system and heterogeneous catalytic reaction system.The former comprises some metalloporphyrin classes, metal phthalocyanine class, Schiff bases, picolinamide Base Metal title complex etc., and heterogeneous catalyst comprises polymer carrier loading type, inorganic carrier catalyst catalyzer, heteropolyacid salt type catalyzer etc.These catalyzer otherwise be difficult to the preparation, the cost height as the metalloporphyrin class, or exists selectivity not high, by product is many, perhaps reclaims problems such as difficulty.
Summary of the invention
The objective of the invention is to hydroxyl cupric phosphate is applied to as catalyzer synthetic 5, in the 6-epoxy-bata-ionone, can make synthetic method have environmental protection, reaction is efficient, convenience operation.
Another object of the present invention is to provide a kind of and synthesize 5,6-epoxy-bata-ionone method.
The objective of the invention is to realize by following manner:
The present invention is used for hydroxyl cupric phosphate to synthesize 5, the 6-epoxy-bata-ionone as catalyzer first.
The present invention is used for the oxidizing reaction of catalysis alpha, beta-lonone with hydroxyl cupric phosphate, and reacted hydroxyl cupric phosphate can reclaim use again after filtering, cleaning.Hydroxyl cupric phosphate wherein also is named as the copper based phosphates, or alkali formula cupric phosphate, and chemical formula is Cu
2(OH) PO
4By the special Application of Catalyst of the present invention, make and synthesize 5,6-epoxy-bata-ionone method has environmental protection, efficient, convenience operation.
The catalyzer that uses among the present invention can obtain hydroxyl phosphoric acid ketone by the following method, certainly also can be according to other synthetic method preparation.Can also with the hydroxyl cupric phosphate of natural generation catalyzer.
With CuAc
2, H
3PO
4With quadrol be raw material synthetic Cu under hydrothermal condition
2(OH) PO
4, the synthesis material mol ratio is: 1.0H
2NCH
2CH
2NH
2: 2.9H
3PO
4: 1.0CuAc
2: 25H
2O. with CuAc
2Water-soluble, add phosphoric acid, stir 30min, after the solution clarification, add quadrol, stir 1h, the reactor of packing into obtains blackish green crystal Cu at 150 ℃ of crystallization 3d
2(OH) PO
4
The present invention is synthetic 5, and 6-epoxy-bata-ionone method is: will be equivalent to the alpha, beta-lonone mol ratio and be 0.01%～50% hydroxyl cupric phosphate and join in the alpha, beta-lonone, be under 40～150 ℃ in Heating temperature, aerating oxygen or air.The GC-MS detection reaction is carried out degree, and is complete up to feedstock conversion.Filter, and clean recyclable catalyzer.
The employed oxygenant of oxidation alpha, beta-lonone is oxygen or air among the present invention.The Heating temperature scope of catalyzed oxidation is 40～150 ℃, and wherein preferred Heating temperature is 60～90 ℃.Reaction temperature is spent low, and then speed of response is slow.But temperature of reaction is too high, and by product is many, and product selectivity reduces.Catalyzer hydroxyl cupric phosphate better catalytic activity, the catalytic amount of 1.7% (with respect to the amount of raw material) just has reasonable catalytic effect.Though the increase of catalytic amount can increase the speed of oxidizing reaction, from cost consideration, the preferred amount ranges of catalyzer is for being equivalent to alpha, beta-lonone amount of substance 0.5%～10%.
The catalytic oxidation raw material is an alpha, beta-lonone, and structural formula is seen formula 1.
Formula 1
Catalytic oxidation product 5,6-epoxy-bata-ionone structural formula is seen formula 2.
Formula 2
Embodiment
Illustrate catalyzed oxidation below and synthesize 5, the method for 6-epoxy-bata-ionone.
Embodiment 1
In having the 150mL three-necked bottle of prolong, add alpha, beta-lonone 30g, add the 40mL organic solvent again, hydroxyl cupric phosphate 0.66g (be equivalent to raw material amount 1.77%), 80 ℃ down by the bubbler aerating oxygen, reaction 7h, GC-MS detects the raw material alpha, beta-lonone and all transforms stopped reaction.Filter, and clean, reclaim catalyzer.GC-MS detects and finds 5, and 6-epoxy-bata-ionone chromatographic peak peak area per-cent reaches 90%.Mass-spectrometric data and standard spectrum storehouse matching degree are up to 90%, and main mass-spectrometric data is that m/z is 123 (100%), and 135 (15%), 208 (M
+, 0.14%).
Embodiment 2
Repeat embodiment 1 according to described same steps as, but the amount of hydroxyl cupric phosphate increase to 3.73g (be equivalent to raw material amount 10%), feedstock conversion is complete behind the bearing reaction 5h, and 5,6-epoxy-bata-ionone chromatographic peak peak area per-cent reaches 92%.
Embodiment 3
Repeat embodiment 1 according to described same steps as, but the amount of hydroxyl cupric phosphate increase to 16.8g (be equivalent to raw material amount 45%), feedstock conversion is complete behind the bearing reaction 3h, and 5,6-epoxy-bata-ionone chromatographic peak peak area per-cent reaches 89%.
Embodiment 4
Repeat embodiment 1 according to described same steps as, but reacting Heating temperature is 60 ℃, feedstock conversion is complete behind the bearing reaction 12h, and 5,6-epoxy-bata-ionone chromatographic peak peak area per-cent reaches 90%.
Embodiment 5
Repeat embodiment 1 according to described same steps as, but oxygenant replaces oxygen with pressurized air, feedstock conversion is complete behind the bearing reaction 8h, and 5,6-epoxy-bata-ionone chromatographic peak peak area per-cent reaches 83%.
Embodiment 6
Repeat embodiment 1 according to described same steps as, but the reaction Heating temperature is 140 ℃, reaction 4h feedstock conversion is complete, and 5,6-epoxy-bata-ionone chromatographic peak peak area per-cent reaches 70%, but color atlas shows complexity of product.
Claims (4)
1, the application of hydroxyl cupric phosphate is characterized in that: hydroxyl cupric phosphate as catalyzer, is used for alpha, beta-lonone and oxygen or air catalytic oxidation preparation 5, the reaction of 6-epoxy-bata-ionone.
2, synthetic 5, the method of 6-epoxy-bata-ionone, it is characterized in that: the consumption of hydroxyl phosphoric acid ketone is 0.01%～50% of an alpha, beta-lonone amount of substance in the reaction system, under 40～150 ℃ of Heating temperatures, with oxygen or atmospheric oxidation alpha, beta-lonone, synthesize 5, the 6-epoxy-bata-ionone.
3, according to claim 2 synthetic 5, the method for 6-epoxy-bata-ionone is characterized in that: the consumption of hydroxyl cupric phosphate is equivalent to 0.5%～10% of alpha, beta-lonone amount of substance.
4, according to claim 2 synthetic 5, the method for 6-epoxy-bata-ionone is characterized in that: the reaction Heating temperature is 60～90 ℃.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100322369A CN100513400C (en) | 2006-09-13 | 2006-09-13 | Use of hydroxyl cupric phosphate in synthesizing 5,6-epoxy-bata-ionone and method of synthesizing 5,6-epoxy-bata-ionone |
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2006100322369A CN100513400C (en) | 2006-09-13 | 2006-09-13 | Use of hydroxyl cupric phosphate in synthesizing 5,6-epoxy-bata-ionone and method of synthesizing 5,6-epoxy-bata-ionone |
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| Publication Number | Publication Date |
|---|---|
| CN1923824A CN1923824A (en) | 2007-03-07 |
| CN100513400C true CN100513400C (en) | 2009-07-15 |
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| CNB2006100322369A Active CN100513400C (en) | 2006-09-13 | 2006-09-13 | Use of hydroxyl cupric phosphate in synthesizing 5,6-epoxy-bata-ionone and method of synthesizing 5,6-epoxy-bata-ionone |
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Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103551172B (en) * | 2013-11-01 | 2015-05-20 | 长沙理工大学 | Amorphous copper catalyst and application thereof |
| CN113880788A (en) * | 2021-10-13 | 2022-01-04 | 上海应用技术大学 | Preparation method of 5, 6-epoxy-beta-ionone |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048201A (en) * | 1976-03-01 | 1977-09-13 | International Flavors & Fragrances Inc. | Novel enol esters |
| US4098827A (en) * | 1977-01-17 | 1978-07-04 | Hoffmann-La Roche Inc. | 1-(2,6,6-Trimethyl-3-hydroxy-1-cyclohexen-1-yl)-3-methyl-penta-1,4-diene[or 1-yn-4-EN]-3-ols |
| CN1099742A (en) * | 1993-06-11 | 1995-03-08 | 霍夫曼-拉罗奇有限公司 | Manufacture of beta-ionone |
| CN1129209A (en) * | 1995-10-05 | 1996-08-21 | 复旦大学 | Process for production of beta-jonone |
-
2006
- 2006-09-13 CN CNB2006100322369A patent/CN100513400C/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4048201A (en) * | 1976-03-01 | 1977-09-13 | International Flavors & Fragrances Inc. | Novel enol esters |
| US4098827A (en) * | 1977-01-17 | 1978-07-04 | Hoffmann-La Roche Inc. | 1-(2,6,6-Trimethyl-3-hydroxy-1-cyclohexen-1-yl)-3-methyl-penta-1,4-diene[or 1-yn-4-EN]-3-ols |
| CN1099742A (en) * | 1993-06-11 | 1995-03-08 | 霍夫曼-拉罗奇有限公司 | Manufacture of beta-ionone |
| CN1129209A (en) * | 1995-10-05 | 1996-08-21 | 复旦大学 | Process for production of beta-jonone |
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| CN1923824A (en) | 2007-03-07 |
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