CN114085133B - Synthesis method of 4-hydroxy-2,2,6-trimethylcyclohexanone - Google Patents
Synthesis method of 4-hydroxy-2,2,6-trimethylcyclohexanone Download PDFInfo
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- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
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- C07C45/64—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by introduction of functional groups containing oxygen only in singly bound form
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Abstract
The invention provides a synthesis method of 4-hydroxy-2,2,6-trimethylcyclohexanone, which comprises the following steps: (1) The method comprises the following steps of (1) selectively hydrogenating tea scented ketone under the action of a Lindlar catalyst to obtain 2,2,6-trimethyl-1,4-cyclohexanedione, (2) selectively hydrogenating 2,2,6-trimethyl-1,4-cyclohexanedione to obtain 4-hydroxy-2,2,6-trimethylcyclohexanone, and in the step (2), chiral rhodium is adopted as a hydrogenation catalyst. The invention provides a novel method for synthesizing a damascenone intermediate 4-hydroxy-2,2,6-trimethylcyclohexanone, which has the advantages of simple operation, easy obtainment of starting raw material, high yield and high selectivity of 4-hydroxy-2,2,6-trimethylcyclohexanone.
Description
Technical Field
The invention relates to the field of organic synthesis, in particular to a method for synthesizing 4-hydroxy-2,2,6-trimethylcyclohexanone.
Background
Damascenone has elegant rose fragrance, is an important raw material of essence for daily use, and can be used as edible spice. There are many methods for synthesizing damascenone, and the synthesis of damascenone from 4-hydroxy-2,2,6-trimethylcyclohexanone is one of the methods.
Patents US4250332 and US3927107 report that 4-hydroxy-2,2,6-trimethylcyclohexanone undergoes alkynylation and rearrangement to form damascenone, and the hydroxyketone produced in the reaction can be further dehydrated to damascenone by phosphorus oxychloride. The reaction scheme is schematically as follows:
the method for synthesizing damascenone from 4-hydroxy-2,2,6-trimethylcyclohexanone is simplified, the need of using metal hydride or Grignard reagent in other routes is avoided, and the method is favorable for reducing cost and realizing safe production. However, the raw material 4-hydroxy-2,2,6-trimethylcyclohexanone is not easy to synthesize and has limited sources.
The tea scented ketone is also named as 4-oxo-isophorone, the source is wide, the tea scented ketone is used for preparing 4-hydroxy-2,2,6-trimethylcyclohexanone, and then the advantages of the synthetic damascenone are obvious, but the tea scented ketone is used for preparing 4-hydroxy-2,2,6-trimethylcyclohexanone, the selective reduction of ketone carbonyl is involved, and the synthetic difficulty is high.
Disclosure of Invention
The invention aims to provide a synthesis method of 4-hydroxy-2,2,6-trimethylcyclohexanone, which takes the tea ketone as a starting material to prepare the 4-hydroxy-2,2,6-trimethylcyclohexanone through selective hydrogenation, and the prepared 4-hydroxy-2,2,6-trimethylcyclohexanone has high yield and high selectivity. The 4-hydroxy-2,2,6-trimethylcyclohexanone prepared by the method can be used as a damascenone synthesis intermediate to synthesize damascenone through ethynylation and Meyer-Schueter rearrangement, and has the advantages of mild reaction route and low cost.
In order to solve the problems, the invention provides a method for synthesizing 4-hydroxy-2,2,6-trimethylcyclohexanone, which comprises the following steps:
(1) The tea-scented ketone is selectively hydrogenated under the action of Lindlar catalyst to obtain 2,2,6-trimethyl-1,4-cyclohexanedione,
(2) 5363 and selectively hydrogenating and reducing 4-carbon-oxygen double bond to prepare 4-hydroxy-2,2,6-trimethylcyclohexanone by using 2,2,6-trimethyl-1,4-cyclohexanedione, wherein chiral rhodium is adopted as a hydrogenation catalyst in the step (2).
In the invention, the Pd content in the Lindlar catalyst in the step (1) is 1-20%, and the dosage of the Pd content is 0.5-10%, preferably 1-5% of the mass of the raw material, namely the tea scented ketone; a kettle type or fixed bed reactor can be selected, the reaction temperature is 40-90 ℃, the reaction pressure (gauge pressure) is 0.2-6.0 MPa, and the reaction time is 0.5-24 h. The conversion rate of the step (1) can reach more than 97%, and the selectivity can reach more than 98%.
In the present invention, the step (1) may be diluted with a solvent or without a solvent, wherein the solvent is selected from one or more of inert aliphatic alkane, aromatic hydrocarbon, ether and alcohol which do not react with the raw material, such as one or more of n-heptane, toluene and ethanol; the amount of the solvent is 0.1 to 3.0 times, preferably 0.2 to 1.0 times the mass of the raw material 2,2,6-trimethylcyclohexenone. In the step (1), the reaction liquid and the catalyst can be separated by adopting a filtration mode, and the 2,2,6-trimethyl-1,4-cyclohexanedione can be purified by adopting a distillation or rectification mode after the catalyst is separated.
In the invention, the chiral rhodium catalyst in the step (2) further comprises a diphosphine ligand, the chiral rhodium catalyst is prepared by coordinating the diphosphine ligand with a rhodium metal compound, and the diphosphine ligand is a diphosphine ligand with steric hindrance, such as: XANTPHOS, BINAP, meO-BIPHEP, preferably XANTPHOS.
In the present invention, the rhodium metal compound is selected from RhCl 3 、Rh(CO) 2 acac、Rh 4 (CO) 12 Or Rh 6 (CO) 16 Further preferably Rh (CO) 2 acac。
Preferably, the molar ratio of the diphosphine ligand to the rhodium metal compound is 8:1-1:1.
The structures of XANTPHOS, BINAP and MeO-BIPHEP are as follows:
in the invention, the preparation process of the chiral rhodium catalyst comprises the following steps: under inert atmosphere, dissolving diphosphine ligand in solvent, stirring, dripping rhodium metal compound solution, reacting to obtain catalyst solution or extracting solvent under reduced pressure to obtain catalyst. The reaction time is 1-6h, and the reaction temperature is 10-60 ℃.
In the invention, the dosage of the chiral rhodium catalyst (calculated by the molar amount of the metal rhodium) is 2,2,6-trimethyl-1,4-cyclohexanedione 0.01-0.5%, preferably 0.01-0.1%, preferably, the reaction temperature of the step (2) is 0-60 ℃, the reaction pressure is 0.2-6.0 MPa, and the reaction time is 0.5-24 h. The conversion rate of the carbon-oxygen double bond selective hydrogenation step can reach more than 97%, and the selectivity can reach more than 93%.
In the invention, an organic base is further added in the step (2) as an auxiliary agent, and the organic base is an organic base with steric hindrance, such as: diisopropylethylamine (DIPEA), 1,8-diazabicycloundec-7-ene (DBU). The dosage of the organic base is 2,2,6-trimethyl-1,4-cyclohexanedione 0.01-0.5%, preferably 0.02-0.3%.
In the present invention, the step (2) may be diluted with a solvent or without a solvent, and the solvent is selected from one or more of inert aliphatic alkane, aromatic hydrocarbon, ether and alcohol which do not react with the raw material, such as one or more of n-heptane, toluene and ethanol; the amount of the solvent is 0.1 to 3.0 times, preferably 0.2 to 1.0 times the mass of the raw material 2,2,6-trimethylcyclohexenone. In the step (2), the reaction liquid and the catalyst can be separated by adopting a filtering mode, and the 4-hydroxy-2,2,6-trimethylcyclohexanone can be purified by adopting a distillation or rectification mode after the catalyst is separated.
The reaction scheme is as follows:
the difficulty of the invention lies in that the carbon-oxygen double bond at the 4 th position in 2,2,6-trimethyl-1,4-cyclohexanedione needs to be selectively reduced, because the chemical properties of the carbon-oxygen double bond at the 1 st position and the carbon-oxygen double bond at the 4 th position are similar, the difference exists only in the aspect of steric hindrance, the model selection reduction difficulty is large, the scheme adopts diphosphine ligand with steric hindrance and adds organic base auxiliary agent, the target product can be obtained with high selectivity, and the yield of the target product is improved.
The invention provides a novel method for synthesizing a damascenone intermediate 4-hydroxy-2,2,6-trimethylcyclohexanone, and the operation is simple.
The initial raw material of the invention, namely the tea aroma ketone, is easy to obtain, and the 4-hydroxy-2,2,6-trimethylcyclohexanone has high yield and high selectivity.
The 4-hydroxy-2,2,6-trimethylcyclohexanone prepared by the method can be used for synthesizing damascenone, the problem that raw materials in a damascenone synthesis route are limited is solved, the damascenone synthesis route using the intermediate is simple and convenient, no complex operation is needed, the synthesis difficulty is reduced, and the total yield of the damascenone is improved.
Detailed Description
The present invention will be described in more detail with reference to examples, but the present invention is not limited to the examples.
The gas chromatography test conditions of the present invention are as follows:
the instrument model is as follows: agilent GC; a chromatographic column: agilent Cyclodex-B (30 m. Times.0.25 mm. Times.0.25 μm); column temperature: the initial temperature is 40 ℃, the temperature is increased to 100 ℃ at the speed of 5 ℃/min, then the temperature is increased to 200 ℃ at the speed of 10 ℃/min, and the temperature is kept for 15min; sample inlet temperature: 280 ℃; FID detector temperature: 300 ℃; split-flow sample injection, wherein the split-flow ratio is 60; sample introduction amount: 2.0 mu L; h 2 Flow rate: 40mL/min; air flow rate: 400mL/min.
Example 1:
(1) Firstly, adding tea ketone 1521.2g, 5% palladium-calcium carbonate catalyst 15.2g and ethanol 1500g into an autoclave, sealing the autoclave, replacing for 3 times by nitrogen, then pressing the nitrogen to 3.0MPa to confirm that the tightness of the autoclave is good, then evacuating the nitrogen, replacing for 6 times by hydrogen with 2.0MPa, starting a stirring paddle, keeping the hydrogen pressure at 2.0MPa, and keeping the internal temperature of the autoclave at 60 ℃ for reaction for 3 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: 2,2,6-trimethyl-1,4-cyclohexanedione 99.72%, theacetone 0.05%, others 0.23%. The reaction solution was filtered and ethanol was removed by distillation under reduced pressure at 90 ℃ and 100hPa to give 2,2,6-trimethyl-1,4-cyclohexanedione crude 1543.3g.
(2) Under inert atmosphere, 0.5mmol Rh (CO) 2 acac was dissolved in 5mL of anhydrous ethanol, 2mmol of XANTPHOS was dissolved in 10mL of anhydrous ethanol, and Rh (CO) was added dropwise to the XANTPHOS solution at 20 deg.C 2 and (3) adding the acac ethanol solution, keeping the temperature and continuing stirring for 2 hours after the dropwise addition is finished. The solvent was removed under reduced pressure of 100Pa to obtain a catalyst.
(3) Adding 100g of ethanol, 0.4g of DBU and 154.2g of 2,2,6-trimethyl-1,4-cyclohexanedione prepared in the step (1) into the prepared catalyst in an anhydrous and oxygen-free atmosphere, replacing 6 times by using 0.5MPa hydrogen, starting a stirring paddle, keeping the hydrogen pressure at 0.5MPa, and keeping the internal temperature of a reaction kettle at 20 ℃ for reacting for 6 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction liquid, wherein the reaction liquid comprises the following components: 4-hydroxy-2,2,6-trimethylcyclohexanone 95.12%,2,2,6-trimethyl-1,4-cyclohexanedione 0.95%,2,2,6-trimethyl-1,4-cyclohexanediol 3.56%, others 0.37%.2,2,6-trimethyl-1,4-cyclohexanedione conversion was 99.05% with a selectivity of 96.30% for 4-hydroxy-2,2,6-trimethylcyclohexanone.
Example 2:
(1) Firstly, adding tea ketone 1521.2g, 10% palladium-calcium carbonate catalyst 8.0g and ethanol 800g into an autoclave, sealing the autoclave, replacing for 3 times by nitrogen, then pressing the nitrogen to 6.0MPa to confirm that the tightness of the autoclave is good, then evacuating the nitrogen, replacing for 6 times by hydrogen with 5.0MPa, starting a stirring paddle, keeping the hydrogen pressure at 5.0MPa, and keeping the internal temperature of the autoclave at 70 ℃ for reaction for 5 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: 2,2,6-trimethyl-1,4-cyclohexanedione 99.82%, tea scented ketone 0.02%, others 0.16%. The reaction solution was filtered and ethanol was removed by distillation under reduced pressure at 90 ℃ and 100hPa to give 2,2,6-trimethyl-1,4-cyclohexanedione crude 1543.5g.
(2) Under inert atmosphere, 0.025mmol Rh was first introduced 4 (CO) 12 Dissolving in 5mL of anhydrous ethanol, dissolving 0.08mmol of BINAP in 10mL of anhydrous ethanol, and adding Rh to the solution of BINAP at 20 deg.C 4 (CO) 12 And (3) keeping the temperature and continuing stirring for 2 hours after the dropwise addition is finished in the ethanol solution. The solvent was removed under reduced pressure of 100Pa to obtain a catalyst.
(3) Under the anhydrous and oxygen-free atmosphere, 200g of ethanol, 0.7g of DBU and 154.2g of 2,2,6-trimethyl-1,4-cyclohexanedione prepared in the step (1) are added into the prepared catalyst, 5MPa hydrogen is used for replacement for 6 times, a stirring paddle is started, the hydrogen pressure is kept at 5MPa, and the internal temperature of a reaction kettle is kept at 60 ℃ for reaction for 6 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: 4-hydroxy-2,2,6-trimethylcyclohexanone 93.34%,2,2,6-trimethyl-1,4-cyclohexanedione 1.32%,2,2,6-trimethyl-1,4-cyclohexanediol 4.91%, others 0.43%.2,2,6-trimethyl-1,4-cyclohexanedione conversion 98.68%, 4-hydroxy-2,2,6-trimethylcyclohexanone selectivity 94.76%.
Example 3:
(1) Firstly, adding tea ketone 1521.2g, 10% palladium-calcium carbonate catalyst 80g and ethanol 1000g into an autoclave, sealing the autoclave, replacing the autoclave with nitrogen for 3 times, then pressing the autoclave to 2.0MPa to confirm that the sealing property of the autoclave is good, then evacuating the nitrogen, replacing the autoclave with 1.0MPa hydrogen for 6 times, starting a stirring paddle, keeping the hydrogen pressure at 1.0MPa, and keeping the internal temperature of the autoclave at 80 ℃ for reaction for 12 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: 2,2,6-trimethyl-1,4-cyclohexanedione 99.43%, theacetone 0.01%, others 0.56%. The reaction solution was filtered and distilled under reduced pressure at 90 ℃ and 100hPa to remove ethanol, yielding 2,2,6-trimethyl-1,4-cyclohexanedione crude 1543.6g.
(2) Under inert atmosphere, 0.15mmol Rh was first introduced 6 (CO) 16 Dissolving in 5mL of anhydrous ethanol, dissolving 1.2mmol of MeO-BIPHEP in 10mL of anhydrous ethanol, and adding Rh to the MeO-BIPHEP solution dropwise at 20 deg.C 6 (CO) 16 And (3) keeping the temperature and continuing stirring for 2 hours after the dropwise addition is finished in the ethanol solution. The solvent was removed under reduced pressure of 100Pa to obtain a catalyst.
(3) 50g of ethanol, 0.02g of DIPEA and 2,2,6-trimethyl-1,4-cyclohexanedione 154.2g are added into the prepared catalyst in an anhydrous and oxygen-free atmosphere, 1MPa hydrogen is used for replacement for 6 times, a stirring paddle is started, the hydrogen pressure is kept at 1MPa, and the internal temperature of a reaction kettle is kept at 40 ℃ for reaction for 6 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: 4-hydroxy-2,2,6-trimethylcyclohexanone 90.75%,2,2,6-trimethyl-1,4-cyclohexanedione 4.59%,2,2,6-trimethyl-1,4-cyclohexanediol 4.03%, others 0.63%.2,2,6-trimethyl-1,4-cyclohexanedione conversion 95.38%, 4-hydroxy-2,2,6-trimethylcyclohexanone selectivity 95.69%.
Example 4:
(1) Under inert atmosphere, 0.5mmol Rh (CO) 2 acac was dissolved in 5mL of anhydrous ethanol, 2mmol of XANTPHOS was dissolved in 10mL of anhydrous ethanol, and the solution of XANTPHOS was added dropwise to Rh (CO) at 20 deg.C 2 and (3) adding the acac ethanol solution, keeping the temperature and continuing stirring for 2 hours after the dropwise addition is finished. The solvent was removed under reduced pressure of 100Pa to obtain a catalyst.
(2) 100g of ethanol and 154.2g of 2,2,6-trimethyl-1,4-cyclohexanedione prepared in the step (1) of example 1 were added to the prepared catalyst in an anhydrous and oxygen-free atmosphere, and the mixture was replaced with 0.5MPa hydrogen for 6 times, and the stirring paddle was turned on to maintain a hydrogen pressure of 0.5MPa, and the internal temperature of the reactor was maintained at 20 ℃ for 6 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: 4-hydroxy-2,2,6-trimethylcyclohexanone 54.73%,2,2,6-trimethyl-1,4-cyclohexanedione 40.82%,2,2,6-trimethyl-1,4-cyclohexanediol 3.92%, others 0.53%.2,2,6-trimethyl-1,4-cyclohexanedione conversion 59.07%, 4-hydroxy-2,2,6-trimethylcyclohexanone selectivity 92.92%.
Comparative example 1
Under inert atmosphere, 0.5mmol Rh (CO) 2 acac was dissolved in 5mL of absolute ethanol, 2mmol of DPPE (1,2-bis (diphenylphosphino) ethane) was dissolved in 10mL of absolute ethanol, and the DPPE solution was added dropwise to Rh (CO) at 20 ℃ 2 and (3) adding the acac ethanol solution, keeping the temperature and continuing stirring for 2 hours after the dropwise addition is finished. The solvent was removed under reduced pressure of 100Pa to obtain a catalyst.
100g of ethanol and 154.2g of 2,2,6-trimethyl-1,4-cyclohexanedione prepared in example 1 were added to the prepared catalyst in an anhydrous and oxygen-free atmosphere, and hydrogen gas at 0.5MPa was used for 6 times of replacement, and the stirring paddle was turned on to maintain the hydrogen pressure at 0.5MPa, and the internal temperature of the reaction kettle was maintained at 20 ℃ for 6 hours. Stopping stirring, emptying gas, and then carrying out GC analysis on the reaction solution, wherein the reaction solution comprises the following components: 4-hydroxy-2,2,6-trimethylcyclohexanone 21.93%,2,2,6-trimethyl-1,4-cyclohexanedione 0.79%,2,2,6-trimethyl-1,4-cyclohexanediol 76.86%, others 0.42%.2,2,6-trimethyl-1,4-cyclohexanedione conversion was 99.21% with 4-hydroxy-2,2,6-trimethylcyclohexanone selectivity 22.17%.
Claims (23)
1. A synthetic method of 4-hydroxy-2,2,6-trimethylcyclohexanone is characterized by comprising the following steps:
(1) The tea-scented ketone is selectively hydrogenated under the action of Lindlar catalyst to obtain 2,2,6-trimethyl-1,4-cyclohexanedione,
(2) 5363, preparing 4-hydroxy-2,2,6-trimethylcyclohexanone from 2,2,6-trimethyl-1,4-cyclohexanedione through selective hydrogenation, wherein chiral rhodium is adopted as a hydrogenation catalyst in the step (2);
the chiral rhodium catalyst in the step (2) further comprises a diphosphine ligand, the chiral rhodium catalyst is prepared by coordination of the diphosphine ligand and a rhodium metal compound, and the diphosphine ligand is a diphosphine ligand with steric hindrance and is selected from the following groups: XANTPHOS, BINAP, meO-BIPHEP;
and (3) adding an organic base as an auxiliary agent in the step (2), wherein the organic base is an organic base with steric hindrance.
2. The method as claimed in claim 1, wherein in the step (1), the content of Pd in the Lindlar catalyst is 1-20%, and the dosage of Pd is 0.5-10% of the mass of the raw material, namely the tea scented ketone; the reaction temperature is 40-90 ℃, the reaction pressure is 0.2-6.0 MPa, and the reaction time is 0.5-24 h.
3. The method as claimed in claim 2, wherein the amount of the Lindlar catalyst used in the step (1) is 1 to 5% by mass of the raw material, the theanone.
4. The method according to claim 1 or 2, wherein the step (1) is diluted with or without a solvent, and the solvent is selected from one or more of inert aliphatic alkane, aromatic hydrocarbon, ether and alcohol which do not react with the raw material.
5. The method according to claim 4, wherein in the step (1), the solvent is selected from one or more of n-heptane, toluene and ethanol.
6. The method of claim 4, wherein in step (1), the amount of the solvent used is 0.1 to 3.0 times the mass of the raw material 2,2,6-trimethylcyclohexenone.
7. The method of claim 6, wherein the solvent is used in an amount of 0.2 to 1.0 times the mass of the raw material 2,2,6-trimethylcyclohexenone.
8. The method of claim 1, wherein the bisphosphine ligand is XANTPHOS.
9. The process of claim 1 wherein the rhodium metal compound is selected from RhCl 3 、Rh(CO) 2 acac、Rh 4 (CO) 12 Or Rh 6 (CO) 16 One or more of (a).
10. The method of claim 9, wherein the rhodium metal compound is Rh (CO) 2 acac。
11. The process of claim 1 wherein the molar ratio of rhodium metal compound to rhodium metal compound is 8:1 to 1:1.
12. The method of claim 1, wherein the chiral rhodium catalyst is prepared by: under inert atmosphere, dissolving diphosphine ligand in solvent, stirring, dripping rhodium metal compound solution, reacting to obtain catalyst solution or extracting solvent under reduced pressure to obtain catalyst.
13. The process of claim 12, wherein the coordination reaction is carried out for a reaction time of 1 to 6 hours and at a reaction temperature of 10 to 60 ℃.
14. The method according to claim 1, wherein the chiral rhodium catalyst is used in an amount of 0.01 to 0.5% by mole based on the metal rhodium, based on 2,2,6-trimethyl-1,4-cyclohexanedione.
15. The method of claim 14, wherein the chiral rhodium catalyst is used in an amount of 0.01 to 0.1% by mole based on the metal rhodium, based on 2,2,6-trimethyl-1,4-cyclohexanedione.
16. The method according to claim 1, wherein the reaction temperature of the step (2) is 0-60 ℃, the reaction pressure is 0.2-6.0 MPa, and the reaction time is 0.5-24 h.
17. The method of claim 1, wherein the organic base is selected from diisopropylethylamine, 1,8-diazabicycloundec-7-ene.
18. The method of claim 17, wherein the organic base is present in an amount of 0.01 to 0.5% by mass of 2,2,6-trimethyl-1,4-cyclohexanedione.
19. The process of claim 18, wherein the amount of organic base used is 0.02 to 0.3% by mass of 2,2,6-trimethyl-1,4-cyclohexanedione.
20. The method according to claim 1, wherein the step (2) is diluted with or without a solvent, and the solvent is selected from one or more of inert aliphatic alkane, aromatic hydrocarbon, ether and alcohol which do not react with the raw material.
21. The method according to claim 20, wherein in the step (2), the solvent is selected from one or more of n-heptane, toluene and ethanol.
22. The process of claim 20 wherein the solvent is used in an amount of 0.1 to 3.0 times the mass of the feedstock 2,2,6-trimethylcyclohexenone.
23. The method of claim 22, wherein in step (2), the amount of solvent used is 0.2 to 1.0 times the mass of the raw material 2,2,6-trimethylcyclohexenone.
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| US4026949A (en) * | 1974-08-21 | 1977-05-31 | Hoffmann-La Roche Inc. | Optically active cyclohexane derivatives |
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