CN107721833B - Method for preparing menthone - Google Patents
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- CN107721833B CN107721833B CN201710972703.4A CN201710972703A CN107721833B CN 107721833 B CN107721833 B CN 107721833B CN 201710972703 A CN201710972703 A CN 201710972703A CN 107721833 B CN107721833 B CN 107721833B
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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
- C07C45/002—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by dehydrogenation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/22—Organic complexes
- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2291—Olefins
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
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- C—CHEMISTRY; METALLURGY
- 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
- C07C29/17—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds
- C07C29/172—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by hydrogenation of carbon-to-carbon double or triple bonds with the obtention of a fully saturated alcohol
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/70—Oxidation reactions, e.g. epoxidation, (di)hydroxylation, dehydrogenation and analogues
- B01J2231/76—Dehydrogenation
- B01J2231/763—Dehydrogenation of -CH-XH (X= O, NH/N, S) to -C=X or -CX triple bond species
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/821—Ruthenium
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/824—Palladium
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Abstract
The invention discloses a method for preparing menthone, which uses a palladium-ruthenium catalyst to carry out heterogeneous catalysis under mild conditions to prepare the menthone from isopulegol. The palladium-ruthenium catalyst can efficiently catalyze the conversion of the isopulegol to the menthone under mild conditions due to the special spatial configuration of the cluster-shaped compound.
Description
Technical Field
The invention belongs to the field of menthone preparation, and particularly relates to a method for preparing menthone by isopulegol heterogeneous catalysis.
Background
Menthone, also known as menthone, has the cooling characteristic aroma of natural mint. Menthone exists in the form of two stereoisomers: menthone and isomenthone, each of which exists in the form of two enantiomers, are mainly used for preparing mint-type essences, and thus the synthesis of menthone has been receiving attention.
Patent US3124614 reports that menthone can be obtained by hydrogenation of thymol under the action of Pd catalyst, but raw material thymol is not easily available, reaction conditions are severe, and requirements for equipment are high.
Patent CN106061933A reports a method for preparing menthone by contacting isopulegol in gas phase with activated oxidized copper catalyst, in the method, the copper catalyst needs to be pre-activated, the pre-activation method is complicated, the activation effect has a large influence on the reaction yield, and the method is not suitable for large-scale industrial production.
Patent CN 104603095A uses a metal complex containing a phosphine ligand as a catalyst. The process can achieve a menthone yield of more than 85%, but cannot achieve high revolution per revolution (TON), has short catalyst life, and is not suitable for industrial synthesis of menthone in consideration of high cost of the catalyst.
Patent CN106068160A describes a ruthenium-phenol catalyst for transfer hydrogenation reaction and the catalyst has excellent performance in transfer hydrogenation reaction, and the catalyst is used for preparing menthone from isopulegol, and has higher conversion rate and selectivity. However, the process has a limited increase in the number of revolutions per minute (TON), the catalyst life is still short, and a large amount of phenol derivative is used, which has adverse effects on the post-treatment and the environment.
Therefore, a method which is simple in process, mild in reaction conditions, economical, efficient, environment-friendly and easy to realize industrialization is urgently needed to realize the preparation of menthone.
Disclosure of Invention
The invention aims to provide a method for preparing menthone, so that a plurality of problems in the existing menthone preparation process are solved.
If not otherwise specified, the term "menthone" refers to any of the possible stereoisomers, including:
if not otherwise specified, the term "isopulegol" refers to any of the possible stereoisomers, including:
in order to achieve the purpose of the invention, the technical scheme adopted by the invention is as follows:
a process for the preparation of menthone from isopulegol: the isopulegol is contacted with a palladium-ruthenium catalyst to carry out heterogeneous catalytic reaction, and the menthone is prepared with high yield.
Wherein the isopulegol is one or more of various possible stereoisomers of isopulegol.
In the present invention, the palladium-ruthenium catalyst is prepared by supporting a palladium metal precursor and a ruthenium metal precursor on aluminum hydroxide by a coprecipitation method generally known in the art.
The palladium metal precursor is selected from one or more of palladium acetate, (tricyclohexylphosphine) palladium dichloride, bis (tributylphosphine palladium), tetratriphenylphosphine palladium and bis (dibenzylidene acetone) palladium, and is preferably Pd [ (t-Bu)3P]2、Pd(PPh3)4And bis (dibenzylideneacetone) palladium, more preferably Pd (PPh)3)4。
The amount of the palladium metal precursor is 0.1 mol% to 2 mol%, preferably 0.1 mol% to 0.5 mol%, based on the molar amount of the palladium element in the palladium metal precursor.
The ruthenium metal precursor is selected from RuCl3·3H2O、Ru(COD)Cl2、[Ru(COD)](BF4)2、[Ru(COD)](ClO4)2、[Ru(COD)](PF6)2One or more of dichloro (p-methyl isopropylphenyl) ruthenium dimer, preferably [ Ru (COD)](ClO4)2And/or twoChloro (p-methylisopropylphenyl) ruthenium dimer, more preferably dichloro (p-methylisopropylphenyl) ruthenium dimer.
In the catalyst, the molar ratio of palladium element in a palladium metal precursor to ruthenium element in a ruthenium metal precursor is 1: 2-4.
In the catalyst, the mass fraction of the carrier aluminum hydroxide is 80-87 wt% based on the total mass of the catalyst.
In the present invention, the preparation of menthone from isopulegol requires two steps:
a) adding a palladium-ruthenium catalyst into a reaction kettle, introducing hydrogen to replace reaction gas, conveying isopulegol into the kettle, fully stirring, and carrying out hydrogenation reaction at the reaction temperature of 10-40 ℃, preferably 20-30 ℃, maintaining the reaction gauge pressure of 0-1.0 MPaG, preferably 0.1-0.5 MPaG, and the reaction time of 6-24 h, preferably 8-12 h.
b) And after the hydrogenation reaction is finished, introducing nitrogen to replace a gas environment, then introducing compressed air to replace reaction gas, and carrying out oxidation reaction, wherein the reaction gauge pressure is maintained to be 0-0.05 MPaG, the reaction temperature is 50-150 ℃, preferably 80-120 ℃, and the reaction time is 3-12 hours, preferably 4-8 hours.
The composition of the compressed air is preferably 78% nitrogen, 21% oxygen, 0.939% rare gas, and 0.061% other gas by volume.
The palladium-ruthenium catalyst has higher catalytic activity in both aqueous phase and organic phase solvents, has recoverability, and has no attenuation in catalytic performance after being recovered and applied for at least 10 times.
In the invention, the chemical selectivity of the final product of the heterogeneous catalytic reaction is 85-99%, the conversion rate can reach 90-99.9%, and the conversion number (TON) of the catalyst can reach 60000-90000.
The catalyst has the advantages that palladium and ruthenium metal precursors form a cluster compound with special space conformation, and can be specifically complexed with a substrate due to space limitation, and metal atoms of palladium and ruthenium are specifically combined with double bonds and oxygen on isopulegol under high hydrogen partial pressure, so that hydrogen anions can more easily attack the double bonds to generate menthol; the alcoholic hydroxyl hydrogen is easier under low hydrogen partial pressureAnd (3) the menthone is desorbed to generate the menthone, and after the menthone is generated, the adsorption force of the menthone and metal cluster atoms is weakened, so that the menthone is easier to desorb, and a chemical cycle similar to enzyme catalysis is formed. In particular Pd (PPh)3)4The cocooning compound structure formed by dichloro (p-methyl isopropylphenyl) ruthenium (II) dimer is the most excellent and has the best catalytic effect.
The method has the advantages that: under the action of a heterogeneous catalyst prepared from the specifically screened palladium and ruthenium ligands and under mild reaction conditions, the menthone can be prepared from isopulegol with high yield and high cycle number, and the method has remarkable operability and economy; and in addition, other solvents are not involved in the system, so that the introduction of other impurities is reduced, and the method has good environmental friendliness. Finally, the heterogeneous catalyst has the advantages of easy recovery, high catalytic activity and the like.
Detailed Description
The following examples serve to illustrate the invention without any limiting nature:
an analytical instrument:
gas chromatograph: agilent 7890, chromatographic column INNO-WAX, inlet temperature: 300 ℃; the split ratio is 50: 1; carrier gas flow: 30 ml/min; temperature rising procedure: 80-230 ℃,3 ℃/min, detector temperature: 280 ℃.
Raw materials and reagents:
dichloro (p-methylisopropylphenyl) ruthenium (II) dimer, 99 wt%, jiangsu xinuoke catalyst ltd;
[Ru(COD)](ClO4)299 wt%, Jiangsu Xinnoco catalyst Co., Ltd;
Pd(PPh3)499 wt%, Jiangsu Xinnoco catalyst Co., Ltd;
Pd[(t-Bu)3P]299 wt%, Jiangsu Xinnoco catalyst Co., Ltd;
bis (dibenzylideneacetone) palladium, 99 wt%, Jiangsu Xinnoco catalyst, Inc.;
aluminum sec-butoxide, 98 wt%, welengi technologies ltd;
tetraethyleneglycol, 98 wt%, carbofuran technologies ltd;
98 wt% of 1-butanol, Allantin reagent Co., Ltd;
98 wt% acetone, Aladdin reagent, Inc.;
99.9 wt% isopulegol, alatin reagent, inc;
example 1:
pd (PPh)3)4(260mg, 0.225mmol), dichloro (p-methylisopropylphenyl) ruthenium (II) dimer (275.57mg, 0.450mmol), tetraethylethylene glycol (418mg, 2.20mmol), aluminum sec-butoxide (9.50g, 38.5mmol), 1-butanol (3ml, 32.7mmol) were added to a 50ml round bottom flask with a condenser and stirred at 120 ℃ for 10h to make a suspension. 2ml of pure water was added dropwise, the reaction mixture was stirred at 120 ℃ for 30min, the solid catalyst was sieved out, washed with acetone and then dried at room temperature in air to give a powdered catalyst.
Example 2:
bis (dibenzylideneacetone) palladium (258.75mg, 0.450mmol), dichloro (p-methylisopropylphenyl) ruthenium (II) dimer (275.57mg, 0.450mmol), tetraethyleneglycol (418mg, 2.20mmol), aluminum sec-butoxide (9.50g, 38.5mmol), 1-butanol (3ml, 32.7mmol) were added to a 50ml round bottom flask with a condenser and stirred at 120 ℃ for 10h to make a suspension. 2ml of pure water was added dropwise, the reaction mixture was stirred at 120 ℃ for 30min, the solid catalyst was sieved out, washed with acetone and then dried at room temperature in air to give a powdered catalyst.
Example 3:
pd [ (t-Bu)3P]2(260mg，0.225mmol)，[Ru(COD)](ClO4)2(275.51mg, 0.675mmol), tetraethyl glycol (418mg, 2.20mmol), aluminum sec-butoxide (9.50g, 38.5mmol), 1-butanol (3ml, 32.7mmol) were added to a 50ml round bottom flask with a condenser and stirred at 120 ℃ for 10h to make a suspension. 2ml of pure water was added dropwise, the reaction mixture was stirred at 120 ℃ for 30min, the solid catalyst was sieved out, washed with acetone and then dried at room temperature in air to give a powdered catalyst.
Example 4:
the palladium-ruthenium catalyst prepared in example 1 was placed in its entirety in a dry 500ml autoclave. The gas displacement was accomplished by 5 repetitions of this step using 99% pure hydrogen to punch to 0.5MPaG and venting to atmospheric pressure. 6.94g of isopulegol is conveyed into a kettle by using a constant flow pump, the temperature is maintained at 20 ℃, the pressure of the reaction kettle is kept at 0.1MPaG, the stirring is started, the uniform stirring is ensured, and the reaction lasts for 8 hours.
And after the hydrogenation reaction is finished, filling nitrogen to 3MPaG, relieving the pressure to normal pressure, repeating the operation for 4 times, then using compressed air to ram to 0.5MPaG, relieving the pressure to normal pressure, and repeating the step for 5 times to finish gas replacement. Heating to 80 ℃, keeping the pressure of the reaction kettle at 0.05MPaG, starting stirring, ensuring uniform stirring, and reacting for 8 hours.
After the reaction was completed, the solution after the reaction was subjected to gas phase detection using a gas chromatograph. The conversion of isopulegol was 98% and the selectivity of the reaction was 97.5%.
Example 5:
the palladium-ruthenium catalyst prepared in example 2 was placed in its entirety in a dry 500ml autoclave. And (3) stamping to 0.5MPa by using 99% purity hydrogen, decompressing to normal pressure, and repeating the step for 5 times to complete gas replacement. 69.41g of isopulegol is conveyed into a kettle by using a constant flow pump, the temperature is maintained at 25 ℃, the pressure of the reaction kettle is kept at 0.3MPa, stirring is started, the uniform stirring is ensured, and the reaction lasts for 10 hours.
And after the hydrogenation reaction is finished, filling nitrogen to 3MPa, relieving the pressure to the normal pressure, repeatedly performing the operations for 4 times, then using compressed air to press the mixture to 0.5MPa, relieving the pressure to the normal pressure, and repeating the step for 5 times to finish gas replacement. Heating to 100 ℃, keeping the pressure of the reaction kettle at 0.03MPa, starting stirring, ensuring uniform stirring, and reacting for 6 hours.
After the reaction was completed, the solution after the reaction was subjected to gas phase detection using a gas chromatograph. The conversion of isopulegol was 98.8%, and the selectivity of the reaction was 98.1%.
Example 6:
the palladium-ruthenium catalyst prepared in example 1 was placed in its entirety in a dry 500ml autoclave. And (3) stamping to 0.1MPa by using 99% purity hydrogen, decompressing to normal pressure, and repeating the step for 5 times to complete gas replacement. 11.57g of isopulegol is conveyed into a kettle by using a constant flow pump, the temperature is maintained at 30 ℃, the pressure of the reaction kettle is kept at 0.5MPa, stirring is started, the uniform stirring is ensured, and the reaction lasts for 12 hours.
And after the hydrogenation reaction is finished, filling nitrogen to 3MPa, relieving the pressure to the normal pressure, repeatedly performing the operations for 4 times, then using compressed air to press the mixture to 0.5MPa, relieving the pressure to the normal pressure, and repeating the step for 5 times to finish gas replacement. Heating to 100 ℃, keeping the pressure of the reaction kettle at 0.01MPa, starting stirring, ensuring uniform stirring, and reacting for 8 hours.
After the reaction was completed, the solution after the reaction was subjected to gas phase detection using a gas chromatograph. The conversion of isopulegol was 99.5%, and the selectivity of the reaction was 99.7%.
Example 7:
the palladium-ruthenium catalyst prepared in example 3 was placed in its entirety in a dry 500ml autoclave. And (3) stamping to 0.1MPa by using 99% purity hydrogen, decompressing to normal pressure, and repeating the step for 5 times to complete gas replacement. And (3) conveying 11.57g of isopulegol into the kettle by using a constant flow pump, maintaining the temperature at 25 ℃, keeping the pressure of the reaction kettle at 0.3MPa, starting stirring, ensuring uniform stirring, and reacting for 10 hours.
And after the hydrogenation reaction is finished, filling nitrogen to 3MPa, relieving the pressure to the normal pressure, repeatedly performing the operations for 4 times, then using compressed air to press the mixture to 0.5MPa, relieving the pressure to the normal pressure, and repeating the step for 5 times to finish gas replacement. Heating to 100 ℃, keeping the pressure of the reaction kettle at 0.01MPa, starting stirring, ensuring uniform stirring, and reacting for 10 hours.
After the reaction was completed, the solution after the reaction was subjected to gas phase detection using a gas chromatograph. The conversion of isopulegol was 95.5% and the selectivity of the reaction was 94.3%.
Comparative example 1:
X540T 1/8(150g, 30-40% copper oxide, 10-25% aluminum oxide, 0-25% magnesium oxide and 30-40% copper aluminum oxide) was charged to a gas phase reactor and the catalyst was made to contain H2Gas stream (20-40NL/h) at a temperature of 180 ℃.
The evaporator and the reactor were subsequently operated at atmospheric pressure with a nitrogen flow (20NL/h) at a temperature of 170 ℃.
Isopulegol (water content 3.7% by weight, 15g/h) is continuously introduced into the evaporator. The product mixture was condensed at the reactor outlet, after a test time of 5 hours, the reactor and the evaporator were cooled under a nitrogen stream (20NL/h), and the composition was analyzed by gas chromatography. The conversion of isopulegol is 100% and the selectivity of the reaction is 76%.
Claims (11)
1. The method for preparing menthone is characterized in that isopulegol is contacted with a palladium-ruthenium catalyst to carry out heterogeneous catalytic reaction, and the reaction steps for generating the menthone are as follows: adding a palladium-ruthenium catalyst into a reaction kettle, introducing hydrogen, conveying isopulegol into the kettle to perform hydrogenation reaction, and introducing compressed air after the hydrogenation reaction is finished to perform oxidation reaction;
the palladium-ruthenium catalyst is prepared by supporting a palladium metal precursor and a ruthenium metal precursor on aluminum hydroxide;
the palladium metal precursor is selected from Pd (OAc)2、(PCy3)PdCl2、Pd[(t-Bu)3P]2、Pd(PPh3)4One or more of bis (dibenzylideneacetone) palladium;
the ruthenium metal precursor is selected from RuCl3·3H2O、Ru(COD)Cl2、[Ru(COD)](BF4)2、[Ru(COD)](ClO4)2、[Ru(COD)](PF6)2One or more of dichloro (p-methyl isopropylphenyl) ruthenium dimer;
the molar ratio of palladium element in the palladium metal precursor to ruthenium element in the ruthenium metal precursor is 1: 2-4;
calculated by the molar weight of palladium element in the palladium metal precursor, the dosage of the palladium metal precursor is 0.1-2 mol% of isopulegol.
2. The method of claim 1, wherein the palladium metal precursor is selected from the group consisting of Pd [ (t-Bu)3P]2，Pd(PPh3)4Bis (dibenzylidene)Acetone) palladium.
3. The method of claim 2, wherein the palladium metal precursor is Pd (PPh)3)4。
4. The method of claim 1, wherein the palladium metal precursor is used in an amount of 0.1 to 0.5 mol% based on the molar amount of palladium in the palladium metal precursor.
5. The method of claim 1, wherein the ruthenium metal precursor is selected from the group consisting of [ Ru (COD) ]](ClO4)2And \ or dichloro (p-methylisopropylphenyl) ruthenium dimer.
6. The method of claim 5, wherein the ruthenium metal precursor is dichloro (p-methylisopropylphenyl) ruthenium dimer.
7. The method according to claim 1, wherein the mass fraction of the supported aluminum hydroxide in the catalyst is 80 to 87 wt% based on the total mass of the catalyst.
8. The method according to claim 1, wherein the temperature of the hydrogenation reaction is 10 to 40 ℃; the reaction time is 6-24 h; the reaction gauge pressure is 0-1 MPaG.
9. The method according to claim 1, wherein the temperature of the hydrogenation reaction is 20 to 30 ℃; the reaction time is 8-12 h; the reaction gauge pressure is 0.1-0.5 MPaG.
10. The method according to any one of claims 1 or 8, wherein the temperature of the oxidation reaction is 50 to 150 ℃; the reaction time is 3-12 h; the reaction gauge pressure is 0-0.05 MPaG.
11. The method according to any one of claims 1 or 8, wherein the temperature of the oxidation reaction is 80 to 120 ℃; the reaction time is 4-8 h; the reaction gauge pressure is 0-0.05 MPaG.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN108503520B (en) * | 2018-05-22 | 2021-08-10 | 江城 | Process for synthesizing menthone by reactive distillation |
| CN109293487B (en) * | 2018-10-10 | 2021-09-07 | 万华化学集团股份有限公司 | Method for preparing menthone |
| CN109456157B (en) * | 2018-12-10 | 2021-09-07 | 万华化学集团股份有限公司 | Method for preparing L-menthone from R-citronellal |
| CN109704943B (en) * | 2018-12-25 | 2022-07-12 | 万华化学集团股份有限公司 | Method for preparing optically pure L-menthone and catalyst used in method |
| CN109704944B (en) * | 2018-12-25 | 2022-01-07 | 万华化学集团股份有限公司 | Method for preparing menthone from citronellal and catalyst system used in method |
| CN110903173B (en) * | 2019-12-04 | 2022-09-16 | 万华化学集团股份有限公司 | Method for preparing L-menthone from R-citronellal |
| CN110922316B (en) * | 2019-12-04 | 2022-11-08 | 万华化学集团股份有限公司 | Method for preparing L-menthone from R-citronellal |
| CN115872845B (en) * | 2022-12-08 | 2024-04-09 | 万华化学集团股份有限公司 | Preparation method of menthone |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2703375A1 (en) * | 2012-08-31 | 2014-03-05 | LANXESS Deutschland GmbH | Method for manufacturing menthol |
| CN104603095A (en) * | 2012-09-10 | 2015-05-06 | 巴斯夫欧洲公司 | Method for producing menthone from isopulegol |
| CN106068160A (en) * | 2014-03-05 | 2016-11-02 | 巴斯夫欧洲公司 | Ruthenium phenol catalyst for transfer hydrogenation |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP2703375A1 (en) * | 2012-08-31 | 2014-03-05 | LANXESS Deutschland GmbH | Method for manufacturing menthol |
| CN104603095A (en) * | 2012-09-10 | 2015-05-06 | 巴斯夫欧洲公司 | Method for producing menthone from isopulegol |
| CN106068160A (en) * | 2014-03-05 | 2016-11-02 | 巴斯夫欧洲公司 | Ruthenium phenol catalyst for transfer hydrogenation |
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