CN108329198A - A kind of preparation method of tetrahydrochysene irisone - Google Patents
A kind of preparation method of tetrahydrochysene irisone Download PDFInfo
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- CN108329198A CN108329198A CN201810332792.0A CN201810332792A CN108329198A CN 108329198 A CN108329198 A CN 108329198A CN 201810332792 A CN201810332792 A CN 201810332792A CN 108329198 A CN108329198 A CN 108329198A
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- irisone
- tetrahydrochysene
- autoclave
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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
- C07C45/61—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
- C07C45/62—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 hydrogenation of carbon-to-carbon double or triple bonds
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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
- C07C45/78—Separation; Purification; Stabilisation; Use of additives
- C07C45/81—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation
- C07C45/82—Separation; Purification; Stabilisation; Use of additives by change in the physical state, e.g. crystallisation by distillation
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- Crystallography & Structural Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The invention discloses a kind of preparation methods of tetrahydrochysene irisone, irisone and Raney's nickel catalyst are put into autoclave, solvent and stabilizer is added, it is passed through hydrogen, control the reaction temperature of the Hydrogen Vapor Pressure and material in autoclave at reaction conditions, pressure-maintaining and heat-preservation reaction is carried out, and is constantly sampled analysis, the reaction condition of subsequent reactions is adjusted according to the changes of contents of raw material irisone, intermediate product dihydroionone；When dihydroionone content is less than or equal to 2% in autoclave, stop hydrogenation and heated material into autoclave, with hydrogen in nitrogen displacement autoclave, stops reaction；After material cooling, supernatant is carried out, is filtered, discharging obtains tetrahydrochysene irisone.This method can solve the problems, such as that hydrogenation reaction temperature is high, Hydrogen Vapor Pressure is high, green low power consuming and safety, meanwhile, there is yield height, the high advantage of product purity.
Description
Technical field
The present invention relates to a kind of preparation method of terpenoid more particularly to a kind of preparation sides of tetrahydrochysene irisone
Method.
Background technology
Tetrahydrochysene irisone, also known as 6,10- dimethyl -9- hendecene -2- ketone, molecular formula C13H24O, molecular weight are
196.33, it is a kind of artificial synthesized organic compound.Tetrahydrochysene irisone has root of Aucklandia lappa Decne, the fragrance of a flower and fruity note, like purple sieve
Lan Xiang, rose fragrant and the fruit-like flavour with sweet tea, the slightly fragrance of apple and peach, for essence.Tetrahydrochysene irisone can be by purple
Rowland ketone is hydrogenated in the presence of pallamine and is prepared, and can also use linalool, aceticanhydride and sodium ethoxide reaction, then hydrogenated,
Or it is acted on through acyl chlorides by geraniol and is made.Tetrahydrochysene irisone is made by the hydrogenated catalysis of raw material of irisone mostly,
Currently, temporarily without pertinent literature report and industrialized production.
Invention content
The purpose of the present invention is to provide a kind of preparation methods of tetrahydrochysene irisone.This method can solve existing plus hydrogen
The problem that reaction temperature is high, Hydrogen Vapor Pressure is high, green low power consuming and safety, meanwhile, have that yield is high, high excellent of product purity
Point.
Above-mentioned purpose of the present invention is achieved through the following technical solutions：A kind of preparation method of tetrahydrochysene irisone, including
Following steps：
(1) irisone and Raney's nickel catalyst are added in autoclave, solvent and stabilizer is added, is passed through nitrogen
Displaced air, then it is passed through hydrogen displacement nitrogen, the Hydrogen Vapor Pressure in autoclave is controlled within the scope of 0.5~1MPa, it will be high
The reaction temperature of pressure material in reactor is maintained at 40~50 DEG C, carries out pressure-maintaining and heat-preservation reaction, is constantly taken in reaction process
Sample is analyzed, so as to according to the changes of contents of raw material irisone, intermediate product dihydroionone and product tetrahydrochysene irisone
Adjust the reaction condition of subsequent reactions；
(2) when the irisone content in autoclave≤3%, Hydrogen Vapor Pressure is adjusted to 1.0~1.5MPa, is adjusted
Reaction temperature carries out pressure-maintaining and heat-preservation reaction to 50~60 DEG C；
(3) when the intermediate product dihydroionone content in autoclave≤2%, stop into autoclave
Hydrogen is added, and stops heating material in autoclave, with hydrogen in nitrogen displacement autoclave, terminates reaction；
(4) after the cooling of the material of autoclave, supernatant filters, discharging, obtains the mixed of tetrahydrochysene irisone and solvent
Close object；
(5) mixture of the tetrahydrochysene irisone and solvent is added in distillation still, is distilled to recover solvent, obtain tetrahydrochysene
Irisone.
It is initial to carry out air-distillation recycling design in the step (5), and monitor kettle internal solvent content；When in distillation still
Solvent content≤10% when, adjust pressure in kettle and adjust temperature in the kettle to 100~110 DEG C, continue to distill to 20~30kPa
Recycling design；When the solvent content in distillation still≤3%, adjusts pressure in kettle and adjust temperature in the kettle to 110 to 3~10kPa
~120 DEG C；When the solvent content in distillation still≤0.5%, material in distillation still heat in stopping, and reduction temperature in the kettle is to normal
Temperature is filtered, discharging obtains tetrahydrochysene irisone with air in nitrogen displacement kettle.
The irisone is synthesis or natural, content >=95%.
The irisone, Raney's nickel catalyst, solvent and stabilizer mass ratio be 1:0.01~0.03:1.6~
2.2:0.002~0.005.
The preferred model RTH3110Ni of Raney's nickel catalyst.
The solvent is ethyl alcohol, and the stabilizer is triethanolamine.
In the step (4), the Raney's nickel catalyst obtained after filtering is repeatedly applied in the reaction of next batch.
In the step (5), the solvent of distillation recovery is repeatedly applied in the reaction of next batch.
The present invention has the following advantages：
1. the present inventor is by research for many years to terpene component structure and hydropyrolysis experiment is repeated, to the catalytic reaction
The factors such as screening, reaction pressure and the temperature of agent make continuous change, and analyze its reason, finally found that in the reaction, reaction
Temperature and hydrogenation pressure have a very big impact the yield of tetrahydrochysene irisone.If fixing a reaction temperature and plus hydrogen pressure
Power, then its yield is extremely difficult to peak, and the reaction later stage is extremely difficult to reaction end.The present invention tracks high pressure by analysis
The process reacted in reaction kettle makes reaction towards four according to the corresponding adjusting control reaction temperature of reaction depth and hydrogenation pressure
The high direction of hydrogen irisone yield mildly carries out in an orderly manner, to achieve the purpose that improve tetrahydrochysene irisone yield and purity.
2. the Raney's nickel catalyst of different model has different catalytic effects, the preferred model RTH3110Ni's of the present invention
Organic solvent ethyl alcohol is added as hydrogenation catalyst in Raney's nickel catalyst, can solve existing hydrogenation reaction temperature height, hydrogen
The high problem of pressure reduces the energy consumption of reaction, reaction milder, safety.
3. reacting the Raney's nickel catalyst being obtained by filtration later and solvent being reusable.
4. since intermediate product dihydroionone continues to be easy to generate during adding hydrogen to generation tetrahydrochysene irisone
Other by-products influence the selectivity and yield of tetrahydrochysene irisone, and the present inventor studies by-product by analysis, passes through addition
Micro stabilizer inhibits the generation of by-product, so that reaction is carried out towards the direction for generating tetrahydrochysene irisone, by continuous
Stabilizer is screened, it is found that triethanolamine is best as the reaction effect of stabilizer.
Specific implementation mode
Invention is further described in detail With reference to embodiment, but does not constitute any limit to the present invention
System.
Embodiment 1
(1) irisone and 1.2g Raney's nickel catalysts that 40g contents are 97.1% are added in autoclave, are added
88g ethyl alcohol and 0.2g triethanolamines, the i.e. mass ratio of irisone, Raney's nickel catalyst, solvent and stabilizer are 1:0.03:
2.2:0.005.Three times, then three times with hydrogen displacement with air in nitrogen displacement autoclave, it is finally passed through hydrogen again, controls
Hydrogen Vapor Pressure in autoclave processed is to 0.5MPa.The reaction temperature of material in autoclave is maintained at 40 DEG C, is carried out
Pressure-maintaining and heat-preservation reacts.Reaction starts sampling analysis in 2 hours, so as to according to raw material irisone, intermediate product dihydroionone
The reaction condition of subsequent reactions is adjusted with the changes of contents of product tetrahydrochysene irisone.
(2) when the irisone content in autoclave≤3%, Hydrogen Vapor Pressure is adjusted to 1.0MPa, adjusts reaction
Temperature carries out pressure-maintaining and heat-preservation reaction to 50 DEG C.
(3) when the intermediate product dihydroionone content in autoclave≤2%, stop into autoclave
Hydrogen is added, and stops heating material in autoclave, with hydrogen in nitrogen displacement autoclave, terminates reaction.
(4) after the cooling of the material of autoclave, supernatant filters, discharging, obtains the mixed of tetrahydrochysene irisone and solvent
Close object.The Raney's nickel catalyst obtained after filtering is repeatedly applied in the reaction of next batch.
(5) mixture of the tetrahydrochysene irisone and solvent is added in distillation still, air-distillation recycling design.Work as steaming
When evaporating solvent content in kettle≤10%, opens vacuum pump and be evaporated under reduced pressure, adjust pressure in kettle and adjusted in kettle to 20kPa
Temperature is to 100 DEG C；When the solvent content in distillation still≤3%, adjusts pressure in kettle and adjust temperature in the kettle to 110 to 4kPa
℃。
(6) when the solvent content in distillation still≤0.5%, material in distillation still heat in stopping, reduction temperature in the kettle
It is filtered, discharging obtains tetrahydrochysene irisone with air in nitrogen displacement kettle to room temperature.The solvent of distillation recovery is repeatedly applied to
In the reaction of next batch.
(7) product analysis is carried out to tetrahydrochysene irisone obtained：Tetrahydrochysene irisone content is 88.6%, irisone
It is 0, conversion ratio 100%, tetrahydrochysene irisone is selectively 91.25%.
Embodiment 2
(1) irisone and 2g Raney's nickel catalysts that 100g contents are 96.8% are added in autoclave, are added
190g ethyl alcohol and 0.35g triethanolamines, the i.e. mass ratio of irisone, Raney's nickel catalyst, solvent and stabilizer are 1:0.02:
1.9:0.0035.Three times, then three times with hydrogen displacement with air in nitrogen displacement autoclave, it is finally passed through hydrogen again,
The Hydrogen Vapor Pressure in autoclave is controlled to 0.7MPa.The reaction temperature of material in autoclave is maintained at 45 DEG C, into
Row pressure-maintaining and heat-preservation reacts.Reaction starts sampling analysis in 2 hours, so as to according to raw material irisone, intermediate product dihydro violet
The changes of contents of ketone and product tetrahydrochysene irisone adjusts the reaction condition of subsequent reactions.
(2) when the irisone content in autoclave≤3%, Hydrogen Vapor Pressure is adjusted to 1.2MPa, adjusts reaction
Temperature carries out pressure-maintaining and heat-preservation reaction to 55 DEG C.
(3) when the intermediate product dihydroionone content in autoclave≤2%, stop into autoclave
Hydrogen is added, and stops heating material in autoclave, with hydrogen in nitrogen displacement autoclave, terminates reaction.
(4) after the cooling of the material of autoclave, supernatant filters, discharging, obtains the mixed of tetrahydrochysene irisone and solvent
Close object.The Raney's nickel catalyst obtained after filtering is repeatedly applied in the reaction of next batch.
(5) mixture of the tetrahydrochysene irisone and solvent is added in distillation still, air-distillation recycling design.Work as steaming
When evaporating solvent content in kettle≤10%, opens vacuum pump and be evaporated under reduced pressure, adjust pressure in kettle and adjusted in kettle to 25kPa
Temperature is to 105 DEG C；When the solvent content in distillation still≤3%, adjusts pressure in kettle and adjust temperature in the kettle to 115 to 8kPa
℃。
(6) when the solvent content in distillation still≤0.5%, material in distillation still heat in stopping, reduction temperature in the kettle
It is filtered, discharging obtains tetrahydrochysene irisone with air in nitrogen displacement kettle to room temperature.The solvent of distillation recovery is repeatedly applied to
In the reaction of next batch.
(7) product analysis is carried out to tetrahydrochysene irisone obtained：Tetrahydrochysene irisone content is 88.2%, irisone
It is 0, conversion ratio 100%, tetrahydrochysene irisone is selectively 91.12%.
Embodiment 3
(1) irisone and 4g Raney's nickel catalysts that 400g contents are 96.2% are added in autoclave, are added
640g ethyl alcohol and 0.8g triethanolamines, the i.e. mass ratio of irisone, Raney's nickel catalyst, solvent and stabilizer are 1:0.01:
1.66:0.002.Three times, then three times with hydrogen displacement with air in nitrogen displacement autoclave, it is finally passed through hydrogen again,
The Hydrogen Vapor Pressure in autoclave is controlled to 1MPa.The reaction temperature of material in autoclave is maintained at 50 DEG C, is carried out
Pressure-maintaining and heat-preservation reacts.Reaction starts sampling analysis in 2 hours, so as to according to raw material irisone, intermediate product dihydroionone
The reaction condition of subsequent reactions is adjusted with the changes of contents of product tetrahydrochysene irisone.
(2) when the irisone content in autoclave≤3%, Hydrogen Vapor Pressure is adjusted to 1.5MPa, adjusts reaction
Temperature carries out pressure-maintaining and heat-preservation reaction to 60 DEG C.
(3) when the intermediate product dihydroionone content in autoclave≤2%, stop into autoclave
Hydrogen is added, and stops heating material in autoclave, with hydrogen in nitrogen displacement autoclave, terminates reaction.
(4) after the cooling of the material of autoclave, supernatant filters, discharging, obtains the mixed of tetrahydrochysene irisone and solvent
Close object.The Raney's nickel catalyst obtained after filtering is repeatedly applied in the reaction of next batch.
(5) mixture of the tetrahydrochysene irisone and solvent is added in distillation still, air-distillation recycling design.Work as steaming
When evaporating solvent content in kettle≤10%, opens vacuum pump and be evaporated under reduced pressure, adjust pressure in kettle and adjusted in kettle to 30kPa
Temperature is to 110 DEG C；When the solvent content in distillation still≤3%, adjusts pressure in kettle and adjust temperature in the kettle to 120 to 10kPa
℃。
(6) when the solvent content in distillation still≤0.5%, material in distillation still heat in stopping, reduction temperature in the kettle
It is filtered, discharging obtains tetrahydrochysene irisone with air in nitrogen displacement kettle to room temperature.The solvent of distillation recovery is repeatedly applied to
In the reaction of next batch.
(7) product analysis is carried out to tetrahydrochysene irisone obtained：Tetrahydrochysene irisone content is 87.4%, irisone
It is 0, conversion ratio 100%, tetrahydrochysene irisone is selectively 90.85%.
Claims (9)
1. a kind of preparation method of tetrahydrochysene irisone, which is characterized in that include the following steps：
(1) irisone and Raney's nickel catalyst are added in autoclave, solvent and stabilizer is added, be passed through nitrogen displacement
Air, then it is passed through hydrogen displacement nitrogen, the Hydrogen Vapor Pressure in autoclave is controlled within the scope of 0.5~1MPa, high pressure is anti-
It answers the reaction temperature of material in kettle to be maintained at 40~50 DEG C, carries out pressure-maintaining and heat-preservation reaction, be constantly sampled in reaction process point
Analysis, to be adjusted according to the changes of contents of raw material irisone, intermediate product dihydroionone and product tetrahydrochysene irisone
The reaction condition of subsequent reactions；
(2) when the irisone content in autoclave≤3%, Hydrogen Vapor Pressure is adjusted to 1.0~1.5MPa, adjusts reaction
Temperature carries out pressure-maintaining and heat-preservation reaction to 50~60 DEG C；
(3) when the intermediate product dihydroionone content in autoclave≤2%, stop being added into autoclave
Hydrogen, and stop heating material in autoclave, with hydrogen in nitrogen displacement autoclave, terminate reaction；
(4) after the cooling of the material of autoclave, supernatant filters, and discharging obtains the mixing of tetrahydrochysene irisone and solvent
Object；
(5) mixture of the tetrahydrochysene irisone and solvent is added in distillation still, is distilled to recover solvent, obtain tetrahydrochysene purple sieve
Blue ketone.
2. the preparation method of tetrahydrochysene irisone according to claim 1, which is characterized in that in the step (5), initially
Air-distillation recycling design is carried out, and monitors kettle internal solvent content；
When the solvent content in distillation still≤10%, adjust in kettle pressure to 20~30kPa, adjust temperature in the kettle to 100~
110 DEG C, continue to be distilled to recover solvent；
When the solvent content in distillation still≤3%, adjusts pressure in kettle and adjust temperature in the kettle to 110~120 to 3~10kPa
℃；
When the solvent content in distillation still≤0.5%, material in distillation still heat in stopping, reduction temperature in the kettle to room temperature,
With air in nitrogen displacement kettle, filter, discharging obtains tetrahydrochysene irisone.
3. the preparation method of tetrahydrochysene irisone according to claim 1, which is characterized in that the irisone is synthesis
Or natural, content >=95%.
4. a kind of preparation method of tetrahydrochysene irisone according to claim 1 or 2 or 3, which is characterized in that purple sieve
Blue ketone, Raney's nickel catalyst, solvent and stabilizer mass ratio be 1:0.01~0.03:1.6~2.2:0.002~0.005.
5. the preparation method of tetrahydrochysene irisone according to claim 1, which is characterized in that the Raney's nickel catalyst
Model RTH3110Ni.
6. the preparation method of tetrahydrochysene irisone according to claim 1, which is characterized in that the solvent is ethyl alcohol.
7. the preparation method of tetrahydrochysene irisone according to claim 1, which is characterized in that the stabilizer is three ethyl alcohol
Amine.
8. the preparation method of tetrahydrochysene irisone according to claim 1, which is characterized in that in the step (4), filtering
The Raney's nickel catalyst obtained afterwards is repeatedly applied in the reaction of next batch.
9. the preparation method of tetrahydrochysene irisone according to claim 1, which is characterized in that in the step (5), distillation
Recovered solvent is repeatedly applied in the reaction of next batch.
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| CN201810332792.0A CN108329198B (en) | 2018-04-13 | 2018-04-13 | Preparation method of tetrahydro ionone |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111871429A (en) * | 2020-08-28 | 2020-11-03 | 万华化学集团股份有限公司 | Raney catalyst and preparation method thereof, and method for preparing gamma-ketene from alpha, gamma-dienone |
| CN113773170A (en) * | 2021-09-15 | 2021-12-10 | 苏州敬业医药化工有限公司 | Preparation method of 4-methyl-2-pentanol |
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| CN1212902A (en) * | 1998-09-14 | 1999-04-07 | 中国科学院广州化学研究所 | Method preparation of compound catalyst with selective preparation of dihydro-beta-irisone |
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2018
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN1212902A (en) * | 1998-09-14 | 1999-04-07 | 中国科学院广州化学研究所 | Method preparation of compound catalyst with selective preparation of dihydro-beta-irisone |
Non-Patent Citations (2)
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| LAKSHMI KANTAM M∗等: "Layered double hydroxides supported nano palladium: An efficient catalyst for the chemoselective hydrogenation of olefinic bonds", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111871429A (en) * | 2020-08-28 | 2020-11-03 | 万华化学集团股份有限公司 | Raney catalyst and preparation method thereof, and method for preparing gamma-ketene from alpha, gamma-dienone |
| CN111871429B (en) * | 2020-08-28 | 2022-07-12 | 万华化学集团股份有限公司 | Raney catalyst and preparation method thereof, and method for preparing gamma-ketene from alpha, gamma-dienone |
| CN113773170A (en) * | 2021-09-15 | 2021-12-10 | 苏州敬业医药化工有限公司 | Preparation method of 4-methyl-2-pentanol |
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