CN104447263B - Method for realizing one-step synthesis of carvone through catalytic oxidation - Google Patents
Method for realizing one-step synthesis of carvone through catalytic oxidation Download PDFInfo
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- CN104447263B CN104447263B CN201410615640.3A CN201410615640A CN104447263B CN 104447263 B CN104447263 B CN 104447263B CN 201410615640 A CN201410615640 A CN 201410615640A CN 104447263 B CN104447263 B CN 104447263B
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- metal
- carvone
- limonenes
- carvol
- vanadium
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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
Abstract
The invention discloses a one-step synthesis method of carvone through catalytic oxidation, belonging to the field of catalytic oxidation and organic synthesis. According to the method, limonene serving as a raw material is oxidized by tert-butyl hydroperoxide in the presence of a metal modified vanadium phosphorus oxide catalyst, thus obtaining the carvone product in one step. Under the optimized reaction condition, the limonene conversion rate is higher than 80 percent, the yield of carvone is 30 percent, the total effective yield of carvone/carveol/epoxidated limonene can be 60 percent, and the results are superior to reported values. According to the carvone preparation method disclosed by the invention, the problems such as low conversion rate, low selectivity and severe pollution existing in the conventional methods are solved.
Description
Technical field
The present invention relates to a kind of preparation method of carvol, particularly a kind of Cuiization Yangization limonene prepares the side of carvol
Method, belongs to technical field of organic synthesis.
Background technology
Carvol is called spearmint oil, 1- Caraway ketone, and systematic naming method is 2,3- dimethyl -5- isopropenyls-cyclohexanone,
English name Carvone.Carvol is the main component of spearmint oil, and its content is about 50% ~ 60%, it have it is strong, pure and fresh,
Saturating, straightforward spearmint gas, are widely used in the industries such as toothpaste, candy, beverage, perfumed soap.The carvol yield of natural extraction is little,
High cost, complex process, and also many factors such as climate, geography affect.It is natural with the development of carvol application industry
Extracting carvol far can not meet the demand in market, thus artificial synthesized carvol is developed rapidly.
Technique Shi of carvol is industrially produced at present with limonene as raw material, Jing nitroso chlorinations, dehydrochlorination, hydrolysis three
Step synthesis carvol.
Although the technique yield is higher, low cost, substantial amounts of a- terpinols and hydroxyl Sheep's-parsley can be generated during being somebody's turn to do
Ketone, and the acetoxime containing carcinogenic possibility and a large amount of sulfate effluents in industrial wastewater, environmental pollution is serious.In
State's patent CN1092402A discloses a kind of improved method of the technique so that yield is improved, and solvent is easily recycled, more conducively
Adopt in industrial production, but it can not be fully solved serious this problem of environmental pollution.
United States Patent (USP) US6,500,989 methods for disclosing another kind of production carvol, are urging in selective poisoning
Agent hydrogenates carvoxime under conditions of existing, and the method reaction equation is as follows：
With carvoxime as raw material, the formation for making hydroxyl carvol and a- terpinols is minimized the method.The but party
Method product is complex, it is difficult to purify, and catalyst cost is also very high.Patent CN101613263A is then proposed with brand-new or activation
Manganese dioxide is heated to reflux aoxidizing carvoxime, pollution less, low cost and step it is simple, but product separate need to by reduce pressure into
OK, condition requires higher.
Additionally, the method for also preparing carvol as the step oxidation of raw material one with limonene, such as Wang Shi are sent out with cobalt salt as catalysis
The step oxidation of agent one prepares carvol, Jean-Francois Bartol etc. with homemade new catalyst Fe (TDCPN5P) Cl and
Single oxygen donor PhIO is in CH2Cl2Cuiization Yangization limonene in-MeCN solvents, J. Bussi groups with hydrotalcite loaded palladium catalyst,
Molecular oxygen is oxidant Jin Hang limonene Selective Oxidations etc..But these methods are all present, and conversion ratio is low, selective low, pollution
Serious the problems such as.
The content of the invention
The present invention is directed to deficiency of the prior art, it is proposed that a kind of method of catalysis oxidation one-step synthesis carvol, should
Method is simple to operation, high income, pollute it is low.
Synthetic method of the present invention is as follows：With limonene as raw material, in organic solvent, in metal-modified vanadium phosphorus oxygen（M-VPO）Urge
In the presence of agent, by TBHP（TBHP）There is following reaction in oxidation：
Finally give carvol product.
The catalyst that the catalytic oxidation of limonene is adopted in Ben Faming is metal-modified vanadium-phosphor oxide catalyst（M-VPO）.
In described catalyst, phosphorus is 0.5~2 with the mol ratio of vanadium：1, preferably 0.8~1.2：1；In metal-modified vanadium-phosphor oxide catalyst
Metallic element is silver, zirconium or bismuth, and metallic element molar content is the 0.01 ~ 0.2 of V atoms：1, preferably 0.05~0.1：1.
Described catalyst is prepared using following methods, V2O5In by proportioning add metal component precursor, in isobutanol
Flow back 12 h at 120 DEG C, then by P/V proportionings, adds H3PO4, at 110 DEG C continue flow back 6 h, resulting sediment wash to
Neutrality, is dried, and described metal-modified vanadium-phosphor oxide catalyst is prepared after roasting.
Preferably, the mol ratio 1 of Yuan Liao limonenes and oxidant TBHP：2~5；The mass ratio 20 of raw material and catalyst ~
100：1.
Described organic solvent is the low boiling point solvents such as methyl alcohol, acetonitrile, dichloroethanes, tetrahydrofuran, in solvent refluxing bar
React under part, the reaction time is 8~36 h, and stir speed (S.S.) is 650r/min.
Additionally, the consumption of solvent meets appropriate needed for conventional organic reaction, solvent usage amount Yi limonene in the present invention
Volume be standard, be its 90 ~ 110 times.
Beneficial effects of the present invention：
In the present invention, original material limonene in the pericarp of such as orange peel content compared with horn of plenty, China's oranges and tangerines aboundresources, from
Isolate that limonenes source is wide, price is low in its skin oil, be preferable raw material.
The oxidant TBHP of the present invention is modal organic peroxide, stable in properties, using safety,
It is easily controllable.The reduzate of TBHP is the tert-butyl alcohol and water, and non-corrosiveness is low for equipment requirements, and effect on environment very little.
Up to 88.9%, the selectivity of carvol is up to 30.0% for the high conversion rate of present invention , limonenes in the presencing of catalyst.Should
Catalyst also shows preferable reusability.
More than summary, it is an advantage of the current invention that various chemical raw materials needed for reaction are all cheap and easy to get, reaction condition is gentle,
Reaction time is short, high conversion rate, and selective good, simple to operate, effect on environment is little.
Specific embodiment
Embodiment 1
Weigh 2.5 g V2O5, by n (Ag)/n (V)=0.1 the metal component precursor AgNO of amount of calculation is added3, it is placed in 40
In mL isobutanols, flow back 12 h at 120 DEG C, then by the proportioning of n (P)/n (V)=1, adds H3PO4, continue back at 110 DEG C
Flow 6 h, gained sediment deionized water filtration washing to neutrality, the h of air drying 12 at 110 DEG C, then in atmosphere
400 DEG C of h of roasting 4 are obtained cyan Ag-VPO catalyst.
Above-mentioned catalyst 0.02g, acetonitrile 5mL , limonenes 0.5mL and tert-butyl hydroperoxide are added in 100mL round-bottomed flasks
Hydrogen 2mL, 82 DEG C of heating of constant temperature oil bath, the r/min of magnetic agitation 650, condensation 10 h of lower backflow.Sample after reaction, Jing gas-chromatographies
The conversion ratio of analysis , limonenes is 84.3%, and the selectivity of carvol is 25.2%, and carveol/Huan Yangization limonene is selectively 30%.
Embodiment 2
Catalyst preparation, the synthetic method of carvol and feeding quantity, reaction condition etc. are substantially same as Example 1, no
It is 0.75mL that same is the Yuan Liao limonenes amount for adding, and the conversion ratio of Ci Shi limonenes is 68.3%, and the selectivity of carvol is 22.8%.
Embodiment 3
Weigh 2.5g V2O5, by n (Zr)/n (V)=0.1 the metal component precursor ZrOCl of amount of calculation is added2·8H2O,
In being placed in 40 mL isobutanols, flow back 12 h at 120 DEG C, then by the proportioning of n (P)/n (V)=1, adds H3PO4, at 110 DEG C
It is lower to continue 6 h that flow back, gained sediment deionized water filtration washing to neutrality, the h of air drying 12 at 110 DEG C；Then
In atmosphere 400 DEG C of h of roasting 4 are obtained cyan Zr-VPO catalyst.
As catalyst, catalysis oxidation synthesis carvol, reaction condition takes Zr-VPO with preparation with embodiment 1 after reaction
Sample, the conversion ratio of Jing gas chromatographic analysis , limonenes is 88.9%, and the selectivity of carvol is 30.0%, carveol/Huan Yangization limonenes
Selective is 31.5%.
Comparative example 4
Weigh 2.5 g V2O5In being placed in 40 mL isobutanols, by the proportioning of n (P)/n (V)=1, H is added3PO4,
Flow back 6 h at 110 DEG C, gained sediment deionized water filtration washing to neutrality, the h of air drying 12 at 110 DEG C；So
Afterwards in atmosphere 400 DEG C of h of roasting 4 are obtained vpo catalyst.
As catalyst, catalysis oxidation synthesis carvol, reaction condition equivalent integers 1 take VPO with preparation after reaction
Sample, Jing gas phase colour analysis, the conversion ratio of Ci Shi limonenes is 84.8%, and the selectivity of carvol is 14.6%.
Embodiment 5
Method for preparing catalyst is substantially same as Example 1, except for the difference that press in catalyst preparation n (Bi)/n (V)=
0.05 amount of calculation adds metal component precursor Bi (NO3)3·5H2O。
Bi-VPO with preparation is as catalyst, and the catalytic oxidation of catalysis oxidation synthesis carvol , limonenes is complete with enforcement 1
Exactly the same, the conversion ratio of Ci Shi limonenes is 86.3%, and the selectivity of carvol is 22.3%, carveol/Huan Yangization limonene selectivity
For 21.3%.
Comparative example 6
Catalyst preparation is same as Example 3.
Zr-VPO with preparation is as catalyst, and the catalytic oxidation of catalysis oxidation synthesis carvol , limonenes is basic with real
Example 1 is applied, except for the difference that solvent is water, and the conversion ratio of Ci Shi limonenes is 87.3%, and the selectivity of carvol is 13.6%, Huan Yangization Limonene
Alkene is selectively 17.7%.
Claims (5)
1. a kind of method of catalysis oxidation one-step synthesis carvol, it is characterised in that：In organic solvent, Jiang Yuan Liao limonenes, oxidation
Agent TBHP and metal-modified vanadium-phosphor oxide catalyst mix, and the oxidation of , limonenes is reacted under reflux temperature and generates carvol；
The Yuan Liao limonenes are 1 with the mol ratio of TBHP：2 ~ 5, Yuan Liao limonenes are 20 ~ 200 with the mass ratio of catalyst：
1；Metallic element is silver, zirconium or bismuth in the metal-modified vanadium-phosphor oxide catalyst, and metallic element is with the mol ratio of v element
0.01~0.2：1, phosphorus is 0.5 ~ 2 with the mol ratio of vanadium：1；The metal-modified vanadium-phosphor oxide catalyst is prepared using following methods,
V2O5In add metal component precursor by proportioning, 120 DEG C in the isobutanol at flow back 12 h, then by P/V proportionings, add H3PO4,
Continue 6 h that flow back at 110 DEG C, resulting sediment is washed to neutrality, is dried, prepare after roasting described metal-modified
Vanadium-phosphor oxide catalyst.
2. method according to claim 1, it is characterised in that metallic element and v element in the metal-modified vanadium phosphorus oxygen
Mol ratio be 0.05~0.1：1.
3. method according to claim 1, it is characterised in that phosphorus is with the mol ratio of vanadium in the metal-modified vanadium phosphorus oxygen
0.8~1.2：1.
4. method according to claim 1, it is characterised in that described organic solvent be methyl alcohol, acetonitrile, dichloroethanes or
Tetrahydrofuran.
5. method according to claim 1, it is characterised in that described method 8 ~ 36h of back flow reaction in atmospheric conditions.
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| CN201410615640.3A CN104447263B (en) | 2014-11-05 | 2014-11-05 | Method for realizing one-step synthesis of carvone through catalytic oxidation |
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| CN201410615640.3A CN104447263B (en) | 2014-11-05 | 2014-11-05 | Method for realizing one-step synthesis of carvone through catalytic oxidation |
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| CN104447263B true CN104447263B (en) | 2017-05-17 |
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| CN108067223B (en) * | 2016-11-15 | 2020-11-24 | 中国科学院大连化学物理研究所 | Catalyst for preparing carvone by catalyzing and oxidizing carvol molecular oxygen and preparation method thereof |
| CN111729669B (en) * | 2020-06-28 | 2022-10-18 | 云南中烟工业有限责任公司 | Metal-loaded cerium-zirconium solid solution material, preparation method thereof and application of metal-loaded cerium-zirconium solid solution material in catalytic synthesis of carvone |
| CN111701608B (en) * | 2020-07-09 | 2021-08-31 | 中国科学院过程工程研究所 | Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143810B (en) * | 2007-10-11 | 2010-06-09 | 湖南中烟工业有限责任公司 | Allylic oxidation method for cyclohexene derivative |
| CN101891602A (en) * | 2010-07-21 | 2010-11-24 | 浙江新化化工股份有限公司 | Method for synthesizing carvone |
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- 2014-11-05 CN CN201410615640.3A patent/CN104447263B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101143810B (en) * | 2007-10-11 | 2010-06-09 | 湖南中烟工业有限责任公司 | Allylic oxidation method for cyclohexene derivative |
| CN101891602A (en) * | 2010-07-21 | 2010-11-24 | 浙江新化化工股份有限公司 | Method for synthesizing carvone |
Non-Patent Citations (2)
| Title |
|---|
| Limonene oxidation over V2O5/TiO2 catalysts;P. Oliveira，et al.;《Catalysis Today》;20060822;第118卷;第307–314页 * |
| Vanadium phosphorus oxide modified by silver doping: A highly effective catalyst for allylic oxidation of cycloolefins;Junhua Liu，et al.;《Catalysis Communications》;20110828;第15卷;第103-107页 * |
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