CN106928037B - Preparation method of carvone - Google Patents
Preparation method of carvone Download PDFInfo
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- CN106928037B CN106928037B CN201511028776.5A CN201511028776A CN106928037B CN 106928037 B CN106928037 B CN 106928037B CN 201511028776 A CN201511028776 A CN 201511028776A CN 106928037 B CN106928037 B CN 106928037B
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- 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
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
- C07C29/09—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis
- C07C29/10—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes
- C07C29/103—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers
- C07C29/106—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrolysis of ethers, including cyclic ethers, e.g. oxiranes of cyclic ethers of oxiranes
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- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
- C07D301/19—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds with organic hydroperoxides
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Abstract
The invention relates to a method for preparing carvone, which uses α -pinene which is easy to obtain as a raw material, and prepares the carvone through three steps of epoxidation-isomerization-oxidation reaction, wherein the epoxidation-isomerization reaction can be continuously carried out, and after the epoxidation reaction is finished, a ligand, a free radical initiator and a transition metal additive are added to carry out isomerization reaction to generate carvol, so that the carvone is prepared through oxidation reaction.
Description
Technical Field
The invention relates to a preparation method of carvone, belonging to the field of fine organic synthesis.
Background
Carvone is an aliphatic compound containing six-membered ring and has molecular formula C10H14O, named as Carvone in British, is a common spice, wherein D-Carvone has strong, fresh and refreshing spearmint fragrance, is widely applied to industries such as toothpaste, candies, beverages, perfumed soaps and the like, can also be used as a high-efficiency solvent, has annual output of more than 2000 tons, and belongs to bulk chemicals.
Sources of carvone can be divided into natural and synthetic sources, wherein the natural carvone is low in yield, high in cost, complex in process, easy to be influenced by other factors such as climate and the like, and far from meeting the market demand, so that the synthetic carvone is produced at the same time.
At present, the process for industrially producing carvone takes limonene as a raw material and is prepared by three steps of reactions, namely nitroso chlorination, dehydrochlorination and hydrolysis, wherein the reaction equation is as follows:
the said technological process has poor selectivity, great side reactions, great amount of terpineol produced, difficult separation, great amount of waste water produced, nitroso compound, carcinogenic acetone oxime and inorganic salt, high toxicity and difficult biochemical treatment. In addition, the nitrosyl chloride used is a highly toxic substance, and threatens the life safety of operators.
In view of the above disadvantages, the skilled person has developed numerous alternatives. Patent WO1999012880a1 discloses a Wacker type oxidation reaction, which uses palladium salt as a catalyst, copper salt as a cocatalyst, molecular oxygen as an oxidant, and then adds an inorganic salt and an organic acid, under the preferable reaction conditions, limonene can be directly oxidized into carvone, wherein the conversion rate of limonene is 99.5%, the selectivity of carvone is only 61%, and other byproducts include carvone, carvone acetate and the like. Chinese patent CN104447263 discloses that in the presence of a metal modified vanadium phosphorus oxide catalyst, limonene is oxidized into carvone in one step by using tert-butyl hydroperoxide, under the preferable reaction conditions, the conversion rate of limonene is 80%, the yield of carvone is 30%, and the total effective yield of carvone \ carvol \ epoxidized limonene is only 60%.
Chinese patent CN101891602 discloses a two-step process for preparing carvone, starting from limonene oxide, using one or two of zinc octoate and 2-aminophenol as catalysts to prepare carvol first, and after rectification separation, the carvol is oxidized into carvone under the above-mentioned catalytic system. Under the preferable reaction conditions, the conversion rate of epoxy limonene and the selectivity of carveol are respectively about 85%, in the carveol oxidation step, the conversion rate is 91%, the selectivity is 89%, and the total yield of the two-step reaction is 58%.
The two-step reaction equation in the above patent based on epoxy limonene is as follows:
the raw material limonene oxide for preparing carveol by a two-step method is generally prepared by limonene epoxidation, and due to the fact that limonene contains two double bonds in a molecule, three products A (limonene oxide), B, C are generated, limonene and three products A, B, C are respectively shown as follows:
wherein the properties of A and B are very close, the separation is difficult by the conventional rectification means, in order to improve the selectivity of the target product A, the limonene must be greatly excessive, but the generation of the product B cannot be avoided, thereby increasing the complexity of operation and separation. Meanwhile, peroxyacetic acid is generally used as an oxidant in the epoxidation reaction, and is very unstable and easy to decompose and explode under heating, and the reaction product acetic acid has strong corrosivity, which bring adverse effects to production equipment.
α -pinene (structure shown as formula D) is extracted from turpentine oil, and has wide application in essence and perfume industry, the yield of pinene in our country is 6-7 ten thousand tons according to the first position of the world, and about ten thousand tons are exported every year, since only one double bond is present in α -pinene molecule, adverse effect caused by two double bonds of limonene can be avoided during epoxidation reaction, and the product oxidation α -pinene selectivity can reach more than 98%.
Zeolite molecular sieves from different sources are researched by Nomuran Zhengren and Stadium, etc. as catalysts to catalyze and oxidize the isomerization reaction of α -pinene, the obtained main product is campholenic aldehyde, carveol is used as one of the byproducts, the selectivity is less than 10%, and the method has no practical value.
The method has the advantages that the one-step oxidation of limonene into carvone has the defects of low raw material conversion rate, low yield of carvone products and poor product selectivity, the two-step preparation method of carvone by using limonene oxide as a raw material has the defects of complex raw material preparation process, large equipment investment, high operation risk and the like, the total yield of carvone products is not high, and the selectivity of byproduct carvone is extremely low by using α -pinene as a raw material through catalytic oxidation and isomerization reactions, so that the carvone cannot be fully utilized to prepare carvone.
Therefore, it is necessary to develop a new method for preparing carvone to solve various disadvantages in the prior art.
Disclosure of Invention
The invention aims to provide a method for preparing carvone, which can conveniently and quickly prepare the carvone by three steps of epoxidation-isomerization-oxidation from α -pinene.
In order to achieve the above purpose, the invention adopts the following technical scheme:
a preparation method of carvone comprises the following steps:
(1) α -pinene is reacted in the presence of catalyst and peroxide to produce oxidized- α -pinene;
(2) under the action of bidentate ligand, free radical initiator and transition metal additive, the oxidation- α -pinene is subjected to isomerization reaction to generate carveol;
(3) carrying out oxidation reaction on carveol to prepare carvone.
The reaction process is as follows:
the α -pinene is subjected to epoxidation reaction under the action of a catalyst and peroxide to generate oxidized α -pinene, the catalyst is a molybdenum catalyst, and comprises but is not limited to molybdenum trioxide, molybdenum acetylacetonate, ethylene glycol molybdate, propylene glycol molybdate, molybdenum stearate, molybdenum naphthenate, molybdenum hexanoate and molybdenum nonanoate, preferably one or more of molybdenum stearate, molybdenum acetylacetonate and molybdenum naphthenate, and the molar ratio of α -pinene to the catalyst is 100:1-10000:1, preferably 500:1-5000: 1.
The peroxide in the step (1) of the invention has a formula of ROOH, wherein a substituent R is an alkyl or aryl group containing 3 to 20 carbon atoms, the peroxide is preferably one or more of tert-butyl hydroperoxide (TBHP), ethylbenzene hydroperoxide (EBHP) and Cumene Hydroperoxide (CHP), and the molar ratio of α -pinene to the peroxide is 0.5:1-10:1, preferably 1.1:1-1.2: 1.
In the invention, the epoxidation reaction conditions in the step (1) are as follows: the reaction temperature is 20-200 ℃, and the preferable reaction temperature is 60-120 ℃; the reaction time is 1 to 12 hours, preferably 2 to 5 hours.
Because α -pinene molecule has only one double bond, by controlling the catalyst dosage, the reaction raw material proportion and the reaction condition, the selectivity of α -pinene epoxidation reaction product in the step (1) can reach more than 98 percent, the substrate conversion rate is more than 99 percent, and the product oxidation α -pinene does not need to be separated, the step (2) adds bidentate ligand, free radical initiator and transition metal additive into the oxidation α -pinene obtained by the reaction in the step (1) to cause the isomerization reaction, and the epoxidation in the step (1) and the ring opening reaction in the step (2) are continuously carried out.
After the reaction in the step (1) is finished, the generated oxidized- α -pinene is not required to be separated, and the ligand, the free radical initiator and the metal additive in the step (2) are directly added to carry out the isomerization reaction of the oxidized- α -pinene.
The bidentate ligand described in step (2) of the present invention has the following structure:
wherein Ar is phenyl, 2-naphthyl, 2-pyridyl, 2-quinolyl, 2-pyrazinyl, 2-pyrimidinyl, 2-furyl or 2-thienyl, preferably phenyl, 2-naphthyl, 2-pyridyl or 2-pyrimidinyl; n is an integer of 1 to 3, preferably 1 or 2; x is hydroxyl, amino or mercapto, preferably hydroxyl or amino.
In the present invention, the bidentate ligand preferably includes, but is not limited to
(2-pyridylmethylamine),
(2-phenylethanol),
(2-naphthylmethylamine),
(2- (2-pyridyl) -ethanol) and
one or more of (2-aminomethyl pyrimidine).
In the present invention, the molar ratio of α -pinene to the bidentate ligand is 100:1 to 10000:1, preferably 500:1 to 5000: 1.
In step (2) of the present invention, the radical initiator includes, but is not limited to, one or more of azobisisobutyronitrile, azobisisoheptonitrile, perbenzoic acid, m-chloroperoxybenzoic acid, liquid bromine, benzoyl peroxide and dimethyl azobisisobutyrate, preferably one or more of azobisisoheptonitrile, benzoyl peroxide, azobisisobutyronitrile and dimethyl azobisisobutyrate.
In the invention, the molar ratio of α -pinene to the free radical initiator is 100:1-10000:1, preferably 500:1-5000: 1.
In order to improve the conversion rate of the epoxy α -pinene and the selectivity of carveol, a transition metal additive is also required to be added in the step (2), wherein the transition metal additive is a niobium additive, preferably one or more of niobium oxide, niobium hydroxide, niobium dioxide, niobium pentachloride and lithium niobate, and more preferably one or more of niobium hydroxide, niobium oxide and lithium niobate.
In the invention, the molar ratio of the dosage of the transition metal additive to the free radical initiator is 0.1: 1-10:1, preferably 0.5:1 to 5: 1.
The reaction conditions of the α -pinene oxidation isomerization in the step (2) of the invention are that the reaction temperature is 40-150 ℃, the preferable reaction temperature is 80-120 ℃, the reaction time is 1-24 hours, and the most preferable reaction time is 3-6 hours.
In the step (2), the bidentate ligand, the free radical initiator and the transition metal additive exist simultaneously, so that the four-membered ring and the epoxy are opened simultaneously, the carveol is generated by isomerization, the selectivity of the product carveol is more than 95%, and the substrate conversion rate is more than 98%.
The carvone product obtained in the step (2) is separated and purified, and then is subjected to oxidation reaction in the step (3) to prepare carvone.
The oxidant used in step (3) of the present invention is one or more of conventional oxidants including, but not limited to, NaClO, Jones reagent, tetramethylpiperidine nitroxide, N-methylmorphine-N-oxide, pyridine-N-oxide, etc., and the molar ratio of oxidant to carveol is 2:1-1:1, preferably 1.5:1-1.2:1, and the reaction temperature is-10 ℃ to 50 ℃, preferably 0 ℃ to 25 ℃ in order to reduce side reactions and increase selectivity of carvone.
In the step (3), the carveol is converted into the carvone, and the selectivity is greater than 98%.
The invention starts from α -pinene, and obtains carvone with total yield of 85%, α -pinene conversion rate of 95% and total product selectivity of 90% after three-step reaction.
The invention has the beneficial effects that:
bidentate ligand, free radical initiator and transition metal additive are simultaneously introduced in the isomerization reaction of oxidized α -pinene, so that the method realizes the isomerization preparation of carveol by oxidized α -pinene, the single step conversion rate is more than 98 percent, the selectivity is more than 95 percent, the defects of low product yield, poor selectivity and the like caused by using limonene as a raw material are avoided, the problems of difficult product separation, generation of a large amount of industrial wastewater which is difficult to treat and the like in the prior production technology are solved, the raw material α -pinene is cheap and easy to obtain, the preparation process is simple, the requirement on equipment is not high, and the method is suitable for industrial production.
Drawings
FIG. 1 is the nuclear magnetic hydrogen spectrum of the product carveol.
Fig. 2 is a nuclear magnetic carbon spectrum of carveol.
Examples
The preparation process provided by the present invention is further illustrated in detail by the following examples, but the present invention is not limited thereto.
Gas phase analysis conditions: the instrument model is as follows: shimadzu 2010Plus, injection port temperature: 300 ℃; the split ratio is as follows: 30: 1; a chromatographic column: DB-5(30m 0.25mm 0.25 μm); temperature rising procedure: keeping the temperature at 50 ℃ for 2 minutes, heating to 80 ℃ at 5 ℃/min, keeping the temperature for 0min, heating to 300 ℃ at 15 ℃/min, and keeping the temperature for 10 min; FID detector temperature: at 300 ℃.
Nuclear magnetic analysis instrument model: BRUKER Ultrashield 400Plus.
The deuterated reagent is deuterated methanol with the purity of 97 wt%;
α -pinene, purchased from Chinese medicine reagent, with purity of 97.5 wt%;
t-butyl hydroperoxide (TBHP), Cumene Hydroperoxide (CHP), ethylbenzene peroxide (EBHP) were obtained from the avadin reagent;
niobium oxide, niobium hydroxide, lithium niobate were purchased from the alatin reagent, purity: 99.9 wt%;
benzoyl peroxide, azobisisobutyronitrile, purchased from alatin reagent, purity: 99 wt%; azobisisoheptonitrile, dimethyl azobisisobutyrate, purchased from TCI, purity: 98 wt%;
the acetylacetonato molybdenum, the naphthenic acid molybdenum and the stearic acid molybdenum are purchased from Chinese medicine reagents, and the purity is as follows: 99 wt%;
2-picolylamine, 2-phenylethanol, purchased from alatin reagent, purity: 99 wt%; 2-Naphthylmethylamine, 2-aminomethyl pyrimidine, 2- (2-pyridyl) -ethanol from Seika reagent, purity: 98 wt%.
Example 1
73.4 g of α -pinene (purity 97.5 wt%) and 100 g of a tert-butanol solution containing 47.3 wt% of tert-butyl hydroperoxide (TBHP) and 171 mg of molybdenum acetylacetonate were charged into a flask, the flask was replaced with nitrogen gas 3 times, the reaction was carried out at 90 ℃ for 2 hours, the conversion of α -pinene was 99.9% and the selectivity of oxy- α -pinene was 98.6% as determined by gas phase internal standard method and 1H NMR, 16.9 mg of 2-naphthylmethylamine, 257 mg of benzoyl peroxide and 698.7 mg of niobium oxide were further charged into the reaction flask, the reaction was carried out at 120 ℃ for 6 hours, the conversion of oxy- α -pinene was 99.5% and the selectivity of carveol was 97.3%, crude carveol was obtained by distillation under reduced pressure, and pure carveol (purity 97.5 g) was obtained by distillation, and the yield of carveol was 93.5% from α -pinene.
Performing qualitative analysis on the obtained carveol by using nuclear magnetism, and referring to FIGS. 1 and 2, respectively, the nuclear magnetic hydrogen spectrum and the carbon spectrum of the obtained carveol are shown.
Adding 74.5g of carvone (purity 97%) and 10 ml of acetic acid into a reaction bottle, keeping the reaction liquid at 0 ℃, dissolving 60 g of NaClO into 50 ml of water, adding the NaClO into the reaction liquid through a metering pump, continuing to react for 3 hours after 30 minutes, measuring the conversion rate of the carvone to be 99.6% through gas phase, and obtaining 70.1 g of carvone pure product through rectification, wherein the selectivity of the product is 98.5%, and the yield is 98.1%.
Example 2
73.4 g of α -pinene (purity of 97.5 wt%), 153 g of ethylbenzene solution containing 43 wt% of ethylbenzene peroxide and 890 mg of molybdenum naphthenate are added into a flask, the flask is replaced by nitrogen for 3 times, the reaction is carried out for 0.5 hour at 100 ℃, the conversion rate of α -pinene is 99.7% and the selectivity of α -pinene is 98.0% as measured by a gas phase internal standard method and 1HNMR, 20.8 mg of 2-picolylamine, 1.285 g of benzoyl peroxide and 93.6 mg of niobium hydroxide are added into a reaction bottle, the reaction is carried out for 15 hours at 40 ℃, the conversion rate of oxidized- α -pinene is 98.3% and the selectivity of carveol is 95.1%, a crude carveol product is obtained by reduced pressure distillation, and a pure carveol product (purity of 97 wt%) is obtained by rectification, 72.1 g is obtained, and the yield of carveol is 90.5% from α -pinene.
74.5g of carvone (purity 97%) and 50 ml of acetone are added into a reaction bottle, 252 ml of Jones reagent (2.5mol/L) is added into the reaction liquid through a metering pump at 25 ℃, the addition is finished for 1 hour, the reaction is continued for 2 hours, the conversion rate of the carvone is 99.2% through gas phase determination, the selectivity of the product is 99.8%, 71.5 g of carvone pure product is obtained through rectification, and the yield is 99%.
Example 3
28.3 g of α -pinene (purity 97.5%), 50g of a cumene solution containing 51.3 wt% of Cumene Hydroperoxide (CHP) and 132 mg of molybdenum stearate were added to the flask, the flask was replaced with nitrogen gas 3 times, the reaction was carried out at 80 ℃ for 4 hours, the conversion of α -pinene was 99.9% and the selectivity of α -pinene was 98.5% as determined by gas phase internal standard method and 1H NMR, 2.3 mg of 2-aminomethylpyrimidine, 6.7 mg of azobisisobutyronitrile and 6 mg of lithium niobate were added to the reaction flask, the reaction was carried out at 80 ℃ for 4.5 hours, the conversion of α -pinene was 98.7% and the selectivity of carveol was 96.5%, crude carveol was obtained by distillation under reduced pressure and then distilled to obtain pure carveol (purity 97 wt%) 29.0g, and the yield of carveol was 92.0% from α -pinene.
Adding 30.8 g of carvone and 30 ml of ethanol into a reaction bottle, adding 20.6 g of tetramethylpiperidine nitroxide (TEMPO) into the reaction bottle in batches at 15 ℃, finishing the addition within 0.5 hour, continuing the reaction for 1 hour, determining the conversion rate of the carvone to be 99.1% through gas phase determination, ensuring the selectivity of the product to be 99%, and rectifying to obtain 29.8 g of carvone pure product with the yield of 98.2%.
Example 4
141.5 g of α -pinene (purity 97.5%), 150 g of cumene solution containing 52.8 wt% Cumene Hydroperoxide (CHP) and 182 mg molybdenum stearate were added to the flask, the flask was replaced with nitrogen gas for 3 times, the reaction was carried out at 90 ℃ for 2 hours, the conversion of α -pinene was 99.8% as determined by gas phase internal standard method and 1H NMR, the selectivity of α -pinene was 98.8%, 249 mg of 2-phenylethanol, 25.6 mg azobisiso-heptonitrile and 9 mg of niobium hydroxide were added to the reaction flask, the reaction was carried out at 100 ℃ for 3 hours, the conversion of α -pinene was 99.2% as determined by gas phase internal standard method and the selectivity of carveol was 95.8%, crude carveol was obtained by vacuum distillation, and pure carveol (97 wt%) 152g was obtained by rectification, from α -pinene, the yield of carveol was 91.5%.
152g of carvone and 200 ml of ethanol are added into a reaction bottle, 142 g of N-methylmorphine-N-oxide (NMO) is added into the reaction bottle in batches at 50 ℃, the reaction is continued for 4 hours after 1 hour, the conversion rate of the carvone is 99.4 percent through gas phase measurement, the selectivity of the product is 99 percent, the pure carvone product is 149.6 g through rectification, and the yield is 98.5 percent.
Example 5
71.5 g of α -pinene (purity 97.5%), 150 g of ethylbenzene solution containing 60 wt% of ethylbenzene hydroperoxide (EBHP) and 34 mg of molybdenum acetylacetonate were added into a flask, the flask was replaced with nitrogen gas for 3 times, the reaction was carried out at 110 ℃ for 1.5 hours, the conversion of α -pinene was 99.6% and the selectivity of α -pinene was 99.5% as determined by gas phase internal standard method and 1H NMR, 660 mg of 2- (2-pyridyl) -ethanol, 44.8 mg of dimethyl azodiisobutyrate and 254 mg of niobium oxide were added into a reaction flask, the reaction was carried out at 150 ℃ for 1 hour, the conversion of α -pinene was 99% and the selectivity of carveol was 97.2%, crude carveol was obtained by vacuum distillation and pure carveol (purity 97 wt%) was obtained by rectification, 73.4 g was obtained, and the yield of carveol was 92% from α -pinene.
Adding 73.4 g of carvone and 50 ml of methanol into a reaction bottle, adding 67.4 g of pyridine-N-oxide into the reaction bottle in batches at-5 ℃, finishing the addition for 30min, continuing the reaction for 2 hours, determining the conversion rate of the carvone to be 99.1% through gas phase determination, ensuring the selectivity of the product to be 98.6%, and rectifying to obtain 70.8 g of carvone pure product with the yield of 97.7%.
Comparative example 1
73.4 g of α -pinene (purity 97.5%), 100 g of a tert-butanol solution containing 43.0 wt% of tert-butyl hydroperoxide (TBHP) and 445 mg of molybdenum naphthenate were charged into a flask, the flask was replaced with nitrogen gas 3 times, the reaction was carried out at 100 ℃ for 0.5 hour, the conversion of THBP was 99.7% as determined by gas phase internal standard method and 1H NMR, the selectivity of α -pinene was 98.0%, 127 mg of benzoyl peroxide and 112 mg of niobium hydroxide were further charged into the reaction flask, the reaction was carried out at 130 ℃ for 6 hours, the conversion of α -pinene oxide was 8.4% as determined by gas phase internal standard method, and the selectivity of carveol was 16.2%, and no separation was carried out.
Comparative example 2
73.4 g of α -pinene (purity 97.5%), 100 g of a tert-butanol solution containing 43.0 wt% of tert-butyl hydroperoxide (TBHP) and 445 mg of molybdenum naphthenate were charged into a flask, the flask was replaced with nitrogen gas 3 times, the reaction was carried out at 100 ℃ for 0.5 hour, the conversion of THBP was 99.7% and the selectivity of α -pinene was 98.0% as determined by gas phase internal standard method and 1H NMR, 127 mg of benzoyl peroxide was further charged into the reaction flask, the reaction was carried out at 130 ℃ for 6 hours, the conversion of α -pinene was 29.6% and the selectivity of carveol was 25.1% as determined by gas phase internal standard method, and no separation was carried out.
Comparative example 3
73.4 g of α -pinene (purity 97.5%), 100 g of a tert-butanol solution containing 43 wt% of tert-butyl hydroperoxide (TBHP) and 445 mg of molybdenum naphthenate were charged into a flask, the flask was replaced with nitrogen gas for 3 times, the reaction was carried out at 100 ℃ for 0.5 hour, the conversion of THBP was 99.7% and the selectivity of α -pinene was 98.0% as determined by gas phase internal standard method and 1H NMR, 112 mg of niobium hydroxide was further charged into the reaction flask, the reaction was carried out at 130 ℃ for 6 hours, the conversion of α -pinene oxide was 59.6% and the selectivity of carveol was 55.1% as determined by gas phase internal standard method, and no separation was carried out.
Claims (17)
1. A preparation method of carvone comprises the following steps:
(1) α -pinene is reacted in the presence of catalyst and peroxide to produce oxidized- α -pinene;
(2) under the action of bidentate ligand, free radical initiator and transition metal additive, the oxidation- α -pinene is subjected to isomerization reaction to generate carveol;
the bidentate ligand has the following structure:
wherein Ar is phenyl, 2-naphthyl, 2-pyridyl or 2-pyrimidinyl; n is an integer of 1 to 3; x is hydroxyl or amino;
the transition metal additive is selected from one or more of niobium hydroxide, niobium oxide and lithium niobate;
(3) carrying out oxidation reaction on carveol to prepare carvone.
2. The method of claim 1, wherein the molar ratio of α -pinene to the bidentate ligand is from 100:1 to 10000: 1.
3. The method of claim 2, wherein the molar ratio of α -pinene to the bidentate ligand is from 500:1 to 5000: 1.
4. The method of claim 1, wherein: in the structural formula of the bidentate ligand in the step (2), n is 1 or 2.
5. The method of claim 4, wherein: the bidentate ligand in the step (2) is
One or more of (a).
6. The method according to claim 1 or 2, wherein the radical initiator in the step (2) is one or more selected from the group consisting of azobisisobutyronitrile, azobisisoheptonitrile, perbenzoic acid, m-chloroperoxybenzoic acid, liquid bromine, benzoyl peroxide and dimethyl azobisisobutyrate, and the molar ratio of α -pinene to the radical initiator is 100:1 to 10000: 1.
7. The method according to claim 6, wherein the radical initiator in the step (2) is one or more selected from the group consisting of azobisisoheptonitrile, benzoyl peroxide, azobisisobutyronitrile and dimethyl azobisisobutyrate, and the molar ratio of α -pinene to the radical initiator is 500:1 to 5000: 1.
8. The method according to any one of claims 1-5, wherein: the molar ratio of the transition metal additive to the free radical initiator is 0.1: 1-10: 1.
9. the method of claim 8, wherein: the molar ratio of the transition metal additive to the free radical initiator is 0.5:1 to 5: 1.
10. The method according to any one of claims 1-5, wherein: the isomerization reaction conditions in the step (2) are as follows: the reaction temperature range is 40-150 ℃; the reaction time is 1-24 hours.
11. The method of claim 10, wherein: the isomerization reaction conditions in the step (2) are as follows: the reaction temperature range is 80-120 ℃; the reaction time is 3-6 hours.
12. The method according to claim 1, wherein the catalyst in the step (1) is a molybdenum-based catalyst, and the molar ratio of α -pinene to the catalyst is 100:1-10000: 1.
13. The method of claim 12, wherein the catalyst in step (1) is one or more of molybdenum trioxide, molybdenum acetylacetonate, ethylene glycol molybdate, propylene glycol molybdate, molybdenum stearate, molybdenum naphthenate, molybdenum hexanoate and molybdenum nonanoate, and the molar ratio of α -pinene to the catalyst is 500:1 to 5000: 1.
14. The method of claim 13, wherein: in the step (1), the catalyst is one or more of molybdenum stearate, molybdenum acetylacetonate and molybdenum naphthenate.
15. The method according to claim 1 or 12, wherein the peroxide in step (1) is an organic hydrogen peroxide of the formula ROOH, wherein the substituent R is an alkyl or aryl group containing 3 to 20 carbon atoms, and the molar ratio of α -pinene to peroxide is in the range of 0.5:1 to 10: 1.
16. The method as claimed in claim 15, wherein the peroxide in step (1) is one or more selected from tert-butyl hydroperoxide, ethylbenzene hydroperoxide and cumene hydroperoxide, and the molar ratio of α -pinene to peroxide is in the range of 1.1:1-1.2: 1.
17. The method according to any one of claims 1 to 5, wherein the oxidized- α -pinene formed after the completion of step (1) is subjected to the isomerization of oxidized- α -pinene by directly adding the ligand, the radical initiator and the metal additive described in step (2) without separation.
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| US3560571A (en) * | 1967-05-29 | 1971-02-02 | Procter & Gamble | Novel photochemical reaction of 4-caranone and novel reaction products resulting therefrom |
| CN101891602A (en) * | 2010-07-21 | 2010-11-24 | 浙江新化化工股份有限公司 | Method for synthesizing carvone |
| CN102471297A (en) * | 2009-07-24 | 2012-05-23 | 荒川化学工业株式会社 | Method for manufacturing an epoxy compound and method for epoxidizing a carbon-carbon double bond |
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| US3560571A (en) * | 1967-05-29 | 1971-02-02 | Procter & Gamble | Novel photochemical reaction of 4-caranone and novel reaction products resulting therefrom |
| CN102471297A (en) * | 2009-07-24 | 2012-05-23 | 荒川化学工业株式会社 | Method for manufacturing an epoxy compound and method for epoxidizing a carbon-carbon double bond |
| 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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