CN104447263A - 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 PDF

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Publication number
CN104447263A
CN104447263A CN201410615640.3A CN201410615640A CN104447263A CN 104447263 A CN104447263 A CN 104447263A CN 201410615640 A CN201410615640 A CN 201410615640A CN 104447263 A CN104447263 A CN 104447263A
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limonene
karvon
carvone
vanadium
mol ratio
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CN201410615640.3A
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CN104447263B (en
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刘俊华
张谨
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Nanjing Normal University
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Nanjing Normal University
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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
    • 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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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

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

A kind of method of catalyzed oxidation one-step synthesis Karvon
Technical field
The present invention relates to a kind of preparation method of Karvon, particularly a kind of Cuiization Yangization limonene prepares the method for Karvon, belongs to technical field of organic synthesis.
Background technology
Karvon is again Oleum Menthae Rotundifoliae, 1-Caraway ketone, and systematic naming method is 2,3-dimethyl-5-pseudoallyl-pimelinketone, English name Carvone.Karvon is spearmint main body of oil, and its content is about 50% ~ 60%, and it has strong, pure and fresh, saturating, straightforward spearmint gas, is widely used in the industries such as toothpaste, candy, beverage, perfumed soap.The Karvon output of natural extract is little, cost is high, complex process, and the impact of the many factors such as climate, geography.Along with the development of Karvon application industry, natural extract Karvon can not meet the demand in market far away, and thus synthetic Karvon is developed rapidly.
The technique Shi of current industrial production Karvon take limonene as raw material, through nitroso-group chlorination, dehydrochlorination, hydrolysis three step synthesis Karvon.
Although this technique productive rate is higher, cost is low, can generate a large amount of a-terpinol and hydroxyl Karvon in this process, and in trade effluent, contain the acetoxime of carcinogenic possibility and a large amount of vitriol effluent, environmental pollution is serious.Chinese patent CN1092402A discloses improving one's methods of this technique a kind of, and yield is improved, and solvent is easy to reclaim, and is more conducive to adopt in industrial production, but it can not solve environmental pollution this problem serious completely.
US Patent No. 6,500,989 disclose another kind of method of producing Karvon, and be hydrogenation carvoxime under selective fouled catalyst existent condition, the method reaction equation is as follows:
The method is raw material with carvoxime, the formation of hydroxyl Karvon and a-terpinol is down to minimum.But the method product is comparatively complicated, is difficult to purifying, and catalyzer cost is also very high.Patent CN101613263A then proposes the Manganse Dioxide reflux oxidation carvoxime with brand-new or activation, and pollute less, cost is low and step simple, but product separation need be undertaken by decompression, conditional request is higher.
In addition, also having is the method that raw material oxidation step prepares Karvon Yi limonene, is that catalyzer oxidation step prepares Karvon as Wang Shi to send out etc. with cobalt salt, the homemade new catalyst Fe (TDCPN such as Jean-Francois Bartol 5p) Cl and single oxygen donor PhIO is at CH 2cl 2cuiization Yangization limonene in-MeCN solvent, J. Bussi group with hydrotalcite loaded palladium catalyst, molecular oxygen for Hang limonene Selective Oxidation of oxygenant Jin etc.But all there is the problems such as low conversion rate, selectivity be low, seriously polluted in these methods.
Summary of the invention
The present invention is directed to deficiency of the prior art, propose a kind of method of catalyzed oxidation one-step synthesis Karvon, the method is simple to operation, yield is high, it is low to pollute.
Synthetic method of the present invention following: is raw material Yi limonene, in organic solvent, under metal-modified vanadium phosphorus oxygen (M-VPO) catalyzer exists, by tertbutyl peroxide (TBHP) oxidation, following reaction occurs:
Finally obtain Karvon product.
The catalyzer that the catalytic oxidation of Zhong limonene of the present invention adopts is metal-modified vanadium-phosphor oxide catalyst (M-VPO).In described catalyzer, the mol ratio of phosphorus and vanadium is 0.5 ~ 2:1, 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 0.01 ~ 0.2:1 of V atom, preferably 0.05 ~ 0.1:1.
Described catalyzer adopts following methods preparation, V 2o 5in add metal component precursor by proportioning, reflux at 120 DEG C 12 h in isopropylcarbinol, then press P/V proportioning, adds H 3pO 4, continue backflow 6 h at 110 DEG C, the throw out obtained washing is to neutral, dry, prepares described metal-modified vanadium-phosphor oxide catalyst after roasting.
As preferably, mol ratio 1:2 ~ 5 of Yuan Liao limonene and oxygenant TBHP; Mass ratio 20 ~ the 100:1 of raw material and catalyzer.
Described organic solvent is the low boiling point solvents such as methyl alcohol, acetonitrile, ethylene dichloride, tetrahydrofuran (THF), and react under solvent refluxing condition, the reaction times is 8 ~ 36 h, and stir speed (S.S.) is 650r/min.
In addition, the consumption of solvent meets needed for conventional organic reaction appropriate, and in the present invention, the volume of solvent usage quantity Yi limonene is standard, is its 90 ~ 110 times.
Beneficial effect of the present invention:
In the present invention, former material limonene is content comparatively horn of plenty in the pericarp of such as orange skin, China's oranges and tangerines aboundresources, and the limonene isolated from its skin oil source is wide, price is low, is desirable raw material.
Oxygenant tertbutyl peroxide of the present invention is modal organo-peroxide, stable in properties, use safety, is easy to control.The reduzate of TBHP is the trimethyl carbinol and water, and non-corrosiveness is low for equipment requirements, and very little to environmental influence.
The transformation efficiency of the present invention's ， limonene in the presence of catalyzer is up to 88.9%, and the selectivity of Karvon reaches 30.0%.This catalyzer also shows good reusability.
More than summary, the invention has the advantages that the required various chemical feedstocks of reaction is all cheap and easy to get, reaction conditions is gentle, and the reaction times is short, and transformation efficiency is high, and selectivity is good, simple to operate, little to environmental influence.
Embodiment
Embodiment 1
Take 2.5 g V 2o 5, the metal component precursor AgNO of calculated amount is added by n (Ag)/n (V)=0.1 3, be placed in 40 mL isopropylcarbinols, reflux at 120 DEG C 12 h, then press the proportioning of n (P)/n (V)=1, adds H 3pO 4, at 110 DEG C, continue backflow 6 h, gained throw out is with deionized water filtration washing to neutral, and air drying 12 h at 110 DEG C, then 400 DEG C of roasting 4 h can obtain cyan Ag-VPO catalyzer in atmosphere.
In 100mL round-bottomed flask, add above-mentioned catalyzer 0.02g, acetonitrile 5mL, limonene 0.5mL and tertbutyl peroxide 2mL, constant temperature oil bath 82 DEG C heating, magnetic agitation 650 r/min, reflux under condensation 10 h.Sampling after reaction, the transformation efficiency through gas chromatographic analysis ， limonene is 84.3%, and the selectivity of Karvon is 25.2%, and carveol/Huan Yangization limonene selectivity is 30%.
Embodiment 2
The synthetic method of catalyst preparing, Karvon and feeding quantity, reaction conditions etc. are basic identical with embodiment 1, and the transformation efficiency being 0.75mL, Ci Shi limonene unlike the Yuan Liao limonene amount added is 68.3%, and the selectivity of Karvon is 22.8%.
Embodiment 3
Take 2.5g V 2o 5, the metal component precursor ZrOCl of calculated amount is added by n (Zr)/n (V)=0.1 28H 2o, is placed in 40 mL isopropylcarbinols, and reflux at 120 DEG C 12 h, then presses the proportioning of n (P)/n (V)=1, adds H 3pO 4, at 110 DEG C, continue backflow 6 h, gained throw out is extremely neutral with deionized water filtration washing, air drying 12 h at 110 DEG C; Then 400 DEG C of roasting 4 h can obtain cyan Zr-VPO catalyzer in atmosphere.
With the Zr-VPO of preparation for catalyzer, catalyzed oxidation synthesis Karvon, reaction conditions is with embodiment 1, sampling after reaction, the transformation efficiency through gas chromatographic analysis ， limonene is 88.9%, the selectivity of Karvon is 30.0%, and carveol/Huan Yangization limonene selectivity is 31.5%.
Comparative example 4
Take 2.5 g V 2o 5be placed in 40 mL isopropylcarbinols, by the proportioning of n (P)/n (V)=1, add H 3pO 4, reflux 6 h at 110 DEG C, and gained throw out is extremely neutral with deionized water filtration washing, air drying 12 h at 110 DEG C; Then 400 DEG C of roasting 4 h can obtain vpo catalyst in atmosphere.
With the VPO of preparation for catalyzer, catalyzed oxidation synthesis Karvon, reaction conditions equivalent integers 1, sampling after reaction, through gas phase chromatographic analysis, the transformation efficiency of Ci Shi limonene is 84.8%, and the selectivity of Karvon is 14.6%.
Embodiment 5
Method for preparing catalyst is basic identical with embodiment 1, adds metal component precursor Bi (NO unlike in catalyst preparing by n (Bi)/n (V)=0.05 calculated amount 3) 35H 2o.
With the Bi-VPO of preparation for catalyzer, the catalytic oxidation of catalyzed oxidation synthesis Karvon ， limonene is identical with enforcement 1, and the transformation efficiency of Ci Shi limonene is 86.3%, and the selectivity of Karvon is 22.3%, and carveol/Huan Yangization limonene selectivity is 21.3%.
Comparative example 6
Catalyst preparing is identical with embodiment 3.
With the Zr-VPO of preparation for catalyzer, the catalytic oxidation of catalyzed oxidation synthesis Karvon ， limonene is substantially with embodiment 1, the transformation efficiency being water Ci Shi limonene unlike solvent is 87.3%, and the selectivity of Karvon is 13.6%, Huan Yangization limonene selectivity is 17.7%.

Claims (8)

1. the method for a catalyzed oxidation one-step synthesis Karvon, it is characterized in that: in organic solvent, Yuan Liao limonene, oxygenant tertbutyl peroxide and metal-modified vanadium-phosphor oxide catalyst are mixed, react the oxidation of limonene under reflux temperature and generate Karvon, in described metal-modified vanadium-phosphor oxide catalyst, metallic element is silver, zirconium or bismuth, and the mol ratio of metallic element and v element is 0.01 ~ 0.2:1, and the mol ratio of phosphorus and vanadium is 0.5 ~ 2:1.
2. method according to claim 1, is characterized in that, described metal-modified vanadium-phosphor oxide catalyst adopts following methods preparation, V 2o 5in add metal component precursor by proportioning, reflux at 120 DEG C 12 h in isopropylcarbinol, then press P/V proportioning, adds H 3pO 4, continue backflow 6 h at 110 DEG C, the throw out obtained washing is to neutral, dry, prepares described metal-modified vanadium-phosphor oxide catalyst after roasting.
3. method according to claim 1 and 2, is characterized in that, in described metal-modified vanadium phosphorus oxygen, the mol ratio of metallic element and v element is 0.05 ~ 0.1:1.
4. method according to claim 1 and 2, is characterized in that, in described metal-modified vanadium phosphorus oxygen, the mol ratio of phosphorus and vanadium is 0.8 ~ 1.2:1.
5. method according to claim 1 and 2, is characterized in that, the mol ratio of described Yuan Liao limonene and tertbutyl peroxide is 1:2 ~ 5.
6. method according to claim 1 and 2, is characterized in that, the mass ratio of described Yuan Liao limonene and catalyzer is 20 ~ 200:1.
7. method according to claim 1 and 2, is characterized in that, described organic solvent is methyl alcohol, acetonitrile, ethylene dichloride or tetrahydrofuran (THF).
8. method according to claim 1 and 2, is characterized in that, described method is back flow reaction 8 ~ 36h in atmospheric conditions.
CN201410615640.3A 2014-11-05 2014-11-05 Method for realizing one-step synthesis of carvone through catalytic oxidation Expired - Fee Related CN104447263B (en)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
CN108067223A (en) * 2016-11-15 2018-05-25 中国科学院大连化学物理研究所 A kind of catalyst that carvol processed is aoxidized for carveol molecular oxygen catalysis and preparation method thereof
CN111701608A (en) * 2020-07-09 2020-09-25 中国科学院过程工程研究所 Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite
CN111729669A (en) * 2020-06-28 2020-10-02 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

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Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN108067223A (en) * 2016-11-15 2018-05-25 中国科学院大连化学物理研究所 A kind of catalyst that carvol processed is aoxidized for carveol molecular oxygen catalysis and preparation method thereof
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
CN111729669A (en) * 2020-06-28 2020-10-02 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
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
CN111701608A (en) * 2020-07-09 2020-09-25 中国科学院过程工程研究所 Method for preparing vanadium-phosphorus-oxygen catalyst with assistance of hydrotalcite
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

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