CN110183321B - Method for efficiently preparing oxoionone - Google Patents
Method for efficiently preparing oxoionone Download PDFInfo
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- CN110183321B CN110183321B CN201910336822.XA CN201910336822A CN110183321B CN 110183321 B CN110183321 B CN 110183321B CN 201910336822 A CN201910336822 A CN 201910336822A CN 110183321 B CN110183321 B CN 110183321B
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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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Abstract
The invention discloses a method for efficiently preparing oxo-ionone, which takes manganese dioxide as a catalyst to obtain the oxo-ionone by catalytic oxidation at allylic position of the ionone. The method can synthesize the oxo-ionone with high yield, and has the advantages of simple operation, low cost and environmental protection.
Description
Technical Field
The invention relates to an organic synthesis method, in particular to a method for efficiently preparing oxo-ionone.
Background
The ionone has three isomers of alpha, beta and gamma, and the structural formula is as follows:
in natural products, the alpha-ionone and the beta-ionone exist in a mixture, and the gamma-ionone does not exist. In taste and sense, the alpha and beta ionones are rich in the sense of fruit flavor of the elecampane, slightly bitter, and flower and tree fragrance at the tail fragrance. Compared with the prior art, the sweet note of the alpha-ionone is more sufficient, and the beta-ionone is richer in certain cream fragrance and fruit fragrance. The ionone can be used in small amount in essence with wine taste and tobacco taste, and the ionone with lower purity can be used in soap. Beta-ionones can also be used as intermediates for vitamin a. The derivative of ionone is C of carotenoid widely existing in various flowers, plants and tobacco13Degradation products. In 1972, E.Demole et al discovered major components, columella trienones (I) and (IV) in burley, Turkey and Greece tobacco leaves, and subsequently, Swedish chemists discovered the similarly structured compounds 3-oxo-alpha-ionol (II) and 4-oxo-beta-ionol (III) having the following structural formulae:
the above compounds are widely used in tobacco, but since these compounds are unstable and easily polymerized, carbonate derivatives of these compounds are produced by BASF corporation and used in tobacco products. They are relatively stable in nature, have no flavor in unlit smoke, and decompose to generate the above substances upon ignition, thereby producing good flavor, and playing roles of decoration, rounding and synergy. The 3-oxo-alpha-ionol (II) and the 4-oxo-beta-ionol (III) are not only aroma components in tobacco leaves, but also important organic synthesis intermediates, and are widely applied to the industries of food, cosmetics and spices. The ionone derivatives I and II can be derived from alpha-ionone and the compounds III and IV can be derived from beta-ionone derivatives, the most critical of which is the carbonylation of the above allylic position, i.e. the oxidation of the allylic position.
There are many methods for oxidizing the allylic position, and conventional methods mainly include chromium salt oxidation, selenium dioxide oxidation, t-butanol peroxide oxidation, chlorate oxidation, molecular oxygen oxidation, electrolytic oxidation, and the like. The biggest defect of the chromium salt oxidation method is that the consumption of chromium salt is large, waste water and waste residue are generated, and serious environmental pollution is caused; selenium dioxide has great toxicity, and the compound used as a catalyst can cause environmental pollution; the reaction conditions of the chlorate oxidation method are harsh and difficult to control, and the dosage is large; the electrolytic oxidation method has many byproducts, low yield and high energy consumption, and is not beneficial to production. From the viewpoint of green chemistry, the molecular oxidation process is a relatively good oxidation process, but the key to the molecular oxidation process is how to select a catalyst that activates molecular oxygen. In 1981, Oonoshi et al, Japan reported in JP56161370 that 4-oxo- β -ionol was produced by molecular oxygen oxidation, which had a long reaction step and a low total yield. Yanhuawu et al (patent No. ZL201110123283) invent that N-hydroxyphthalimide (NHPI) reaction system is used for oxidizing the allylic position of ionone to synthesize 3-oxo-alpha-ionone and 4-oxo-beta-ionone, the catalyst uses NHPI, cobalt acetylacetonate, vanadium acetylacetonate and cobaltous acetylacetonate, and the reagents are relatively expensive and have high cost, so that the application of the catalyst is limited.
Manganese dioxide is a very stable transition metal oxide and is generally classified into Natural Manganese Dioxide (NMD), Electrolytic Manganese Dioxide (EMD), Chemical Manganese Dioxide (CMD), Activated Manganese Dioxide (AMD), and the like. The crystal lattice structure of manganese dioxide is also relatively complex, 5 crystal forms of alpha, beta, gamma, delta, epsilon and the like and more than 30 paracrystals exist, and the crystal forms can be mutually transformed under certain conditions. The types and contents of crystal forms contained in NMD, EMD, CMD and AMD are greatly different, and the crystal forms contained in NMD produced in different areas are different. Traditionally, NMD is mostly beta and delta type, EMD is gamma type, AMD mainly contains alpha and gamma type, and CMD has different crystal forms according to different synthesis conditions, so that the crystal form is strictly the key factor for determining the reaction activity of manganese dioxide. The reaction of catalytic oxidation of allylic position by active manganese dioxide has also been reported (such as development of fine petrochemical engineering, 2007,8(9), 46-48; advanced chemical engineering, 2000,14(5), 448-452; chemical world, 2000(Z1), 20-21; Zhejiang chemical, 1999,30(2), 31-33; fine chemical, 1997,14(4),45-46, etc.), but the substrates of the reaction are the oxidation of benzyl hydrogen, which has great limitation and low reaction yield.
Disclosure of Invention
Aiming at the defects of the prior art, the invention provides a method for efficiently preparing oxo-ionone, overcomes the defects of the traditional method, and realizes the allylic oxidation reaction of ionone with low cost and environmental friendliness.
The invention relates to a method for efficiently preparing oxo-ionone, which takes manganese dioxide as a catalyst to obtain the oxo-ionone by catalytic oxidation at the allylic position of the ionone.
The catalyst is alpha, gamma or delta type manganese dioxide, preferably gamma type manganese dioxide.
The solvent of the reaction system is N, N-Dimethylformamide (DMF), dimethyl sulfoxide (DMSO) or N-methylpyrrolidone (NMP), preferably DMF.
The temperature of the catalytic reaction is 80-140 ℃, and preferably 120 ℃; the reaction time is 1-6h, preferably 4 h.
The amount of the catalyst used is 1 to 6 times, preferably 4 times, the molar amount of ionone.
The ionone is alpha ionone or beta ionone.
The reaction route of the invention is as follows:
the invention selects gamma-type manganese dioxide as an oxidant, and catalyzes and oxidizes the allylic position of ionone in DMF as a solvent, thereby efficiently obtaining oxoionone. The method has no pollution, environment friendliness and low cost.
Detailed Description
The general procedure is as follows: adding 0.1mol of ionone, 20mL of solvent and a proper amount of manganese dioxide into a three-neck flask with a condensing tube, stirring and reacting for a certain time at a proper temperature, stopping the reaction, and performing column chromatography separation (petroleum ether/ethyl acetate: 6/1, v/v) to obtain the target product.
The example parameters are shown in the following table:
1) self-made manganese dioxide;
2) 3-oxo-alpha-ionone (1),1H-NMR(CDCl3,400MHz)δ:6.83(m,1H),6.13(m,1H),5.80(m,1H),2.56(m,1H),2.41(m,2H),2.25(s,3H),2.09(s,3H),0.98(s,6H);
4-oxo-beta-ionone (2),1H-NMR(CDCl3,400MHz)δ7.40(m,1H),6.33(m,1H),3.16(m,2H),2.34(s,3H),1.97(s,3H),1.32(m,2H),1.24(s,6H);
3) isolated yield.
As can be seen from the table, when the solvent was DMF, the reaction temperature was 120 ℃, the reaction time was 4 hours, the catalyst was gamma-type manganese dioxide, and the amount of the catalyst was 4 times or more (molar ratio) of the substrate, the reaction yield was good, about 90%.
Claims (3)
1. A process for the preparation of oxoionones characterized by: gamma-type manganese dioxide is used as a catalyst, and oxo-ionone is obtained by catalytic oxidation at the allylic position of ionone;
the reaction solvent is N, N-dimethylformamide;
the temperature of the catalytic reaction is 120 ℃, and the reaction time is 4 hours;
the dosage of the catalyst is 4 to 6 times of the molar weight of the ionone.
2. The method of claim 1, wherein:
the amount of the catalyst is 4 times of the molar amount of the ionone.
3. The method of claim 1, wherein:
the ionone is alpha ionone or beta ionone.
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Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB919454A (en) * | 1959-10-07 | 1963-02-27 | Derek Harold Richard Barton | Ionone epoxide and the preparation of substituted ionones therefrom |
WO2000039133A1 (en) * | 1998-12-28 | 2000-07-06 | Loyola University Of Chicago | C-15 phosphonate reagent for preparing canthaxanthin |
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 |
CN102249880A (en) * | 2007-02-15 | 2011-11-23 | 湖南中烟工业有限责任公司 | Method for synthesizing oxo-irisone by oxidizing irisone |
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2019
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Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB919454A (en) * | 1959-10-07 | 1963-02-27 | Derek Harold Richard Barton | Ionone epoxide and the preparation of substituted ionones therefrom |
WO2000039133A1 (en) * | 1998-12-28 | 2000-07-06 | Loyola University Of Chicago | C-15 phosphonate reagent for preparing canthaxanthin |
CN102249880A (en) * | 2007-02-15 | 2011-11-23 | 湖南中烟工业有限责任公司 | Method for synthesizing oxo-irisone by oxidizing irisone |
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 (3)
Title |
---|
MnO2/TBHP: A Versatile and User-Friendly Combination of Reagents for the Oxidation of Allylic and Benzylic Methylene Functional Groups;Stefano Serra;《Eur. J. Org. Chem.》;20151231;第6472-6474页,Scheme1及表1Entry5-6 * |
二氧化锰氧化间甲酚制取间经基苯甲醛;刘俊峰;《浙江化工》;19990630;第30卷(第2期);第31页 * |
对氯苯甲醛的合成及应用;吴卫等;《精细石油化工进展》;20080315;第8卷(第9期);第47页左栏1.3.1节 * |
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Application publication date: 20190830 Assignee: Anhui jiaotianxiang Biotechnology Co.,Ltd. Assignor: CHINA TOBACCO ANHUI INDUSTRIAL Co.,Ltd. Contract record no.: X2023980036634 Denomination of invention: An efficient method for preparing oxyionone Granted publication date: 20220510 License type: Exclusive License Record date: 20230620 |