CN106674244A - Preparation method of cineole - Google Patents
Preparation method of cineole Download PDFInfo
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- CN106674244A CN106674244A CN201611154731.7A CN201611154731A CN106674244A CN 106674244 A CN106674244 A CN 106674244A CN 201611154731 A CN201611154731 A CN 201611154731A CN 106674244 A CN106674244 A CN 106674244A
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- cineole
- catalyst
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D493/00—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system
- C07D493/02—Heterocyclic compounds containing oxygen atoms as the only ring hetero atoms in the condensed system in which the condensed system contains two hetero rings
- C07D493/08—Bridged systems
Abstract
The invention relates to a preparation method of cineole. The preparation method employs terpineol as a raw material, solid acid is used for catalysis, optimization selection is as follows: cineole with high purity is synthesized and separated in a condition at normal pressure with heating. The invention develops a cineole synthesis process which is a green synthesis process with low industrial pollution, low cost and high added values.
Description
【Technical field】
The present invention relates to food, daily use chemicals perfume material technical field.More particularly it relates to the synthetically prepared side of Cineole
Method.
【Background technology】
1, 8-Cineole is referred on Cineole ordinary meaning, is a kind of important fine chemical product.Mainly as fragrance applications
In commodity, food additives industry, have functions that sterilization is applied to field of medicaments as well as it.Eucalyptus in the market
The main application form of foline is divided into two kinds of eucalyptus oils and Cineole, and the sales volume of wherein eucalyptus oil is 4 times of Cineole, and price is true
It is 0.5 times of Cineole price.It is natural products mainly due to the main source of eucalyptus oil, it is widely present in blue gum, eucalyptus
Branch, the Ye Zhong of Ye Shu, cinnamomum camphora tree, camphor tree etc., is re-refined by the processing of the methods such as natural extraction, steam distillation and is obtained.The day
So contain a large amount of molecular structures, property, boiling point, the impurity of dissolving similar temperament in eucalyptus oil, be difficult to using conventional separation method
Isolated high-purity, in high yield Cineole.
With Cineole, in the international market demand is continuously increased, natural folium eucalypti（Oil）Plain price, supply fluctuation are larger,
Therefore the synthesis Cineole of stable supply super quality and competitive price is extremely urgent.The synthesis Cineole technique of maturation is there is no both at home and abroad, only
Minority report is dehydrated again synthesis Cineole using australene by sulfuric acid isomerization.But this method wastewater flow rate is big, produce great
Industrial pollution.A kind of green synthesis process of present invention exploitation, reduces industrial pollution, reduces cost, by pine tar cheap and easy to get
Alcohol, synthesizes the higher Cineole of added value under conditions of solid acid catalyst.
【The content of the invention】
[technical problem to be solved]
It is an object of the invention to provide a kind of preparation method of Cineole.
Technical scheme]
The present invention is achieved through the following technical solutions.
The present invention relates to a kind of preparation method of Cineole.
The step of the method, is as follows：
Terpinol, solvent, catalyst are added in a reactor by weight 1:0~20：
0.01~0.1, atmospheric agitation is well mixed.Then 0.5h~24h is reacted in a heated condition, is refiltered.Filter cake is with molten
Agent drip washing is reused afterwards several times, and filtrate is incorporated in vacuum pressure and steams for 0.06KPa~0.1Kpa, 25 °~45 ° concentrations of temperature
Institute's solubilizer.Remaining crude product obtains high-purity Cineole after rectifying column rectifying.
Another kind of preferred embodiment of the invention, reaction temperature be 80 °~250 ° under the conditions of carry out.
Another kind of preferred embodiment of the invention, the agitating mode of the reaction is normal pressure mechanical agitation, and rotating speed is
150~250 rev/min.
Another kind of preferred embodiment of the invention, reaction used catalyst is acidic catalyst, including solid is strong
Acid catalyst and solid super acid catalyst.
Another kind of preferred embodiment of the invention, reaction dissolvent selects methyl alcohol, ethanol, isopropanol, ethylene glycol.
Another kind of preferred embodiment of the invention, the reactor is assembling agitator, condenser, heating coil
Round-bottomed flask, stainless steel reactor or enamel reactor.
Another kind of preferred embodiment of the invention, the drip washing solvent used by filter cake be reaction dissolvent, terpinol with
Solvent is according to 1：10~80 weight ratios, mix at room temperature 30~60min drip washing again, and drip washing number of times is 3-6 time；In decompression 0.06
~ 0.1KPa, under the conditions of 25 DEG C~35 DEG C of temperature suction filtration is carried out.
Another kind of preferred embodiment of the invention, filtrate is well mixed after drip washing, in the 0.06 ~ 0.1KPa that reduces pressure,
Concentrated under the conditions of 25 DEG C~45 DEG C of temperature.
Another kind of preferred embodiment of the invention, concentrate is refined by rectifying column；Rectifying column is from diameter
3mm-8mm glass spring fillers, in the 3 ~ 6KPa that reduces pressure, under the conditions of 55 DEG C~105 DEG C of temperature rectification under vacuum are carried out.
The present invention is described in more detail below.
The present invention relates to a kind of preparation method of Cineole.Cineole has following chemical formula：
The step of preparation method, is as follows：
Terpinol, solvent, catalyst are added in a reactor by weight 1:0~20：
0.01~0.1, atmospheric agitation is well mixed.Then 0.5h~24h is reacted in a heated condition, is refiltered.Filter cake is with molten
Agent drip washing is reused afterwards several times, and filtrate is incorporated in vacuum pressure and steams for 0.06KPa~0.1Kpa, 25 °~45 ° concentrations of temperature
Institute's solubilizer.Remaining crude product obtains high-purity Cineole after rectifying column rectifying.
In the present invention, when the consumption of terpinol, solvent is in the scope, if the consumption of solvent is more than 20, receive
Rate is reduced, and product is reduced；Therefore, the consumption of solvent be for 0 ~ 20 it is rational, preferably 5~15, more preferably 8~12.
Similarly, when the consumption of terpinol and catalyst is in the scope, if the consumption of catalyst is less than 0.01,
The conversion of pine tar raw polyol is incomplete；If the consumption of catalyst is more than 0.1, increase cost, do not meet economy；Therefore, it is catalyzed
The consumption of agent be for 0.01~0.1 it is rational, preferably 0.03~0.08, more preferably 0.036~0.068.
Preferably, the reaction is heated to reflux 5h~16h under conditions of 80~200 DEG C of temperature, it is highly preferred that the reaction exists
5.5h~14.5h is heated to reflux under conditions of 88~190 DEG C of temperature.
The Main Function being heated to reflux in this step is to promote reaction to complete in 0.5h ~ 24h.The time being heated to reflux
For 0.5~4h, preferably 5~16h, more preferably 5.5~14.5h.
Drip washing solvent used by described filter cake is reaction dissolvent, and terpinol is with solvent according to 1：1~8 weight ratio, in room
The lower mixing 30~60min drip washing again of temperature, drip washing number of times is 3-6 time；In the 0.06 ~ 0.1KPa that reduces pressure, 25 DEG C~35 DEG C conditions of temperature
Under carry out suction filtration.
Preferably terpinol and solvent are according to 1：25~60 weight ratios, mix at room temperature 35~45min drip washing again, drench
It is 3-6 time to wash number of times；In the 0.07 ~ 0.098KPa that reduces pressure, under the conditions of 22 DEG C~34 DEG C of temperature suction filtration is carried out.
More preferably terpinol and solvent are according to 1：35~45 weight ratios, mix at room temperature 36~43min drip washing again,
Drip washing number of times is 4-5 time；In the 0.075 ~ 0.095KPa that reduces pressure, under the conditions of 28 DEG C~30 DEG C of temperature suction filtration is carried out.
In the present invention, concentrate is refined by rectifying column；Rectifying column is 3mm-8mm glass spring fillers from diameter,
In the 3 ~ 6KPa that reduces pressure, under the conditions of 55 DEG C~105 DEG C of temperature rectification under vacuum is carried out.
Preferably concentrate is refined by rectifying column；Rectifying column is 4mm-6mm glass spring fillers from diameter,
3.5~6.5KPa of decompression, carries out rectification under vacuum under the conditions of temperature 60 C~100 DEG C.
Preferably concentrate is refined by rectifying column；Rectifying column is 4.5mm-5.5mm glass spring fillers from diameter,
In the 3.3~5.5KPa that reduces pressure, under the conditions of 65 DEG C~95 DEG C of temperature rectification under vacuum is carried out.
Determine that the product that rectifying is obtained is 1, 8-Cineole, pure using nuclear magnetic resonance and the detection of gas phase mass spectrometric analysis method
Degree reaches more than 95%.
NMR：Bruck-400M NMRs, tetramethylsilane is internal standard, and deuterochloroform is solvent.
Gaseous-mass spectrography instrument：Agilent GC-MS 6890-5973 type gas phase combined instruments.Mass Spectrometry Conditions：Ion
Source be EI sources, ionization energy 70eV, 230 DEG C of ion source temperature, mass scan range be 50-550amu (M/Z).
Nuclear magnetic resonance（Hydrogen is composed）It is as follows with MASS SPECTRAL DATA ANALYSIS:
1H NMR (400M, CDCl3) δ 1.40~1.56（m,8H）,1.35(s,3H), 1.29(s,6H).
MS( M/Z): 154,96,81.
[beneficial effect]
The invention has the beneficial effects as follows preparing high-purity Cineole by green synthesis process, the product belongs to natural perfume material model
Farmland, future market has a extensive future.The technology energy consumption is low, without industrial pollution and equipment investment is few, low production cost, additional
Value is high, is conducive to promoting the further application and development of Cineole, meets domestic and international market growth requirement direction.
【Specific embodiment】
The present invention will be clarified in more detail below by embodiment.
Embodiment 1：The preparation of Cineole
The implementation steps of the embodiment are as follows：
Pine is sequentially added in an assembling agitator, condenser, the round-bottomed flask of heating bath chuck
Oleyl alcohol, ethanol, catalyst RND1# are by weight 1: 20：0.1, atmospheric agitation is well mixed.Then in a heated condition
Reaction 20h, refilters.Filter cake terpinol is with ethanol by weight 1:10,30min is mixed at room temperature, decompression 0.075 ~
0.095KPa, under the conditions of 28 DEG C~30 DEG C of temperature suction filtration is carried out.After the above-mentioned drip washing of repetition operates 2 times；Filtrate is incorporated in vacuum pressure
Power is 0.09Kpa, temperature 45 C concentration steams ethanol.By rectifying column rectifying, rectifying column is 6mm glass from diameter to remaining crude product
Glass spring filler, in decompression 6KPa, carries out obtaining the Cineole of purity 95.6% after rectification under vacuum under the conditions of 105 DEG C of temperature.
Embodiment 2：The preparation of Cineole
The implementation steps of the embodiment are as follows：
Pine is sequentially added in an assembling agitator, condenser, the round-bottomed flask of heating bath chuck
Oleyl alcohol, ethanol, catalyst RND2# are by weight 1: 20：0.1, atmospheric agitation is well mixed.Then 95 ° of bars are being heated to
16h is reacted under part, is refiltered.Filter cake terpinol is with ethanol by weight 1:5,40min is mixed at room temperature, in decompression
0.07KPa, under the conditions of 30 DEG C of temperature suction filtration is carried out.After the above-mentioned drip washing of repetition operates 3 times；Filtrate is incorporated in vacuum pressure
0.09Kpa, temperature 45 C concentration steam ethanol.By rectifying column rectifying, rectifying column is 6mm glass bullets from diameter to remaining crude product
Spring filler, in decompression 5.5KPa, carries out obtaining the Cineole of purity 98.4% after rectification under vacuum under the conditions of 95 DEG C of temperature.
Embodiment 3：The preparation of Cineole
The implementation steps of the embodiment are as follows：
Pine is sequentially added in an assembling agitator, condenser, the round-bottomed flask of heating bath chuck
Oleyl alcohol, ethanol, catalyst RND2# are by weight 1: 5：0.05, atmospheric agitation is well mixed.Then 95 ° of conditions are being heated
Lower reaction 16h, refilters.Filter cake terpinol and ethanol mass ratio 1：3,35min is mixed at room temperature, in decompression 0.01KPa,
Suction filtration is carried out under the conditions of 30 DEG C of temperature.After the above-mentioned drip washing of repetition operates 4 times；Filtrate is incorporated in vacuum pressure for 0.08Kpa, temperature
45 DEG C of concentrations steam ethanol.By rectifying column rectifying, rectifying column is 6mm glass spring fillers from diameter to remaining crude product, is being subtracted
Pressure 3KPa, carries out obtaining the Cineole of purity 98.0% after rectification under vacuum under the conditions of 92 DEG C of temperature.
Embodiment 4：The preparation of Cineole
The implementation steps of the embodiment are as follows：
Pine is sequentially added in an assembling agitator, condenser, the round-bottomed flask of heating bath chuck
Oleyl alcohol, ethylene glycol, catalyst RND1# are by weight 1: 10：0.05, atmospheric agitation is well mixed.Then in heating 180
3h is reacted under the conditions of DEG C, is refiltered.The filter cake ethylene glycol of 5 times of weight ratios, mixes at room temperature 40min, in decompression 0.1KPa,
Suction filtration is carried out under the conditions of 35 DEG C of temperature.After the above-mentioned drip washing of repetition operates 2 times；Filtrate is incorporated in vacuum pressure for 0.1Kpa, temperature
45 DEG C of concentrations steam a small amount of alcohol.By rectifying column rectifying, rectifying column is 6mm glass spring fillers from diameter to remaining crude product,
Decompression 6KPa, carries out obtaining the Cineole of purity 86.3% after rectification under vacuum subsection receiing cut under the conditions of 105 DEG C of temperature.
Embodiment 5：The preparation of Cineole
The implementation steps of the embodiment are as follows：
Sequentially add in an assembling agitator, condenser, the enamel reaction still of heating bath chuck
Terpinol, isopropanol, catalyst RND3# are by weight 1: 2：0.015, atmospheric agitation is well mixed.Then in heating 85
6h is reacted under the conditions of DEG C, is refiltered.Filter cake terpinol and isopropanol in mass ratio 1:10 drip washing, mix at room temperature 40min,
In decompression 0.1KPa, under the conditions of 35 DEG C of temperature suction filtration is carried out.After the above-mentioned drip washing of repetition operates 4 times；Filtrate is incorporated in vacuum pressure
Isopropanol is steamed for 0.085Kpa, temperature 60 C concentration.By rectifying column rectifying, rectifying column is 4mm from diameter to remaining crude product
Glass spring filler, in decompression 3KPa, carries out obtaining purity after rectification under vacuum subsection receiing cut under the conditions of 92 DEG C of temperature
95.8% Cineole.
Embodiment 6：The preparation of Cineole
The implementation steps of the embodiment are as follows：
Terpinol, ethanol are sequentially added in an assembling agitator, condenser, the stainless steel steel reactor of heating bath chuck, urge
Agent RND2# is by weight 1: 0：0.01, atmospheric agitation is well mixed.Then 8h is reacted under the conditions of heating 85 °, is refiltered.
Filter cake terpinol and ethanol mass ratio 1：5,40min is mixed at room temperature, in 0. 1KPa that reduces pressure, enter under the conditions of 23 DEG C of temperature
Row suction filtration.After the above-mentioned drip washing of repetition operates 4 times；Filtrate is incorporated in vacuum pressure and steams second for 0.08Kpa, temperature 45 C concentration
Alcohol.By rectifying column rectifying, rectifying column is 6mm glass spring fillers from diameter to remaining crude product, in decompression 3KPa, temperature 92
Carry out obtaining the Cineole of purity 98.8% after rectification under vacuum under the conditions of DEG C.
Embodiment 7：The preparation of Cineole
The implementation steps of the embodiment are as follows：
Terpinol, methyl alcohol are sequentially added in an assembling agitator, condenser, the stainless steel steel reactor of heating bath chuck, urge
Agent RND3# is by weight 1: 0：0.028, atmospheric agitation is well mixed.Then 4h is reacted under the conditions of heating 105 °, after
Filter.Filter cake terpinol compares 1 with methanol quality：5,20min is mixed at room temperature, in decompression 0.06KPa, under the conditions of 23 DEG C of temperature
Carry out suction filtration.After the above-mentioned drip washing of repetition operates 4 times；Filtrate is incorporated in vacuum pressure and steams first for 0.06Kpa, 30 DEG C of concentrations of temperature
Alcohol.By rectifying column rectifying, rectifying column is 4mm glass spring fillers from diameter to remaining crude product, in decompression 3KPa, temperature 92
Carry out obtaining the Cineole of purity 96.8% after rectification under vacuum under the conditions of DEG C.
Claims (10)
1. a kind of preparation method of Cineole
A kind of preparation method of Cineole, its feature is as follows in the preparation method step：
Terpinol, solvent, catalyst are added in a reactor by weight 1:0~20：
0.01~0.1, atmospheric agitation is well mixed；Then 0.5h~24h is reacted in a heated condition, is refiltered；Filter cake is with molten
Agent drip washing is reused afterwards several times, and filtrate is incorporated in vacuum pressure and steams for 0.06KPa~0.1Kpa, 25 °~45 ° concentrations of temperature
Institute's solubilizer；Remaining crude product obtains high-purity Cineole after rectifying column rectifying.
2. method according to claim 1, it is characterised in that terpinol, solvent, catalyst are by weight 1:0~20：
0.01~0.1 is reacted.
3. method according to claim 1, it is characterised in that reaction temperature is 80 °~250 °.
4. method according to claim 1, it is characterised in that the agitating mode of reaction is normal pressure mechanical agitation, and rotating speed is 150
~250 rev/min.
5. method according to claim 1, it is characterised in that catalyst is self-control acidic catalyst, including catalyst RND1#,
Catalyst RND2#, catalyst RND3#.
6. method according to claim 1, it is characterised in that solvent is oil-dissolving solvent, including methyl alcohol, ethanol, isopropanol,
Ethylene glycol.
7. method according to claim 1, it is characterised in that the reactor is assembling agitator, condenser, heating coil
Round-bottomed flask, stainless steel reactor or enamel reactor.
8. method according to claim 1, it is characterised in that in the 0.06 ~ 0.1KPa that reduces pressure, under the conditions of 25 DEG C~35 DEG C of temperature
Carry out suction filtration.
9. method according to claim 1, it is characterised in that in the 0.06 ~ 0.1KPa that reduces pressure, 25 DEG C~45 DEG C conditions of temperature
Under concentrated.
10. method according to claim 1, it is characterised in that rectifying column is 4mm-8mm glass spring fillers from diameter,
In the 3 ~ 6KPa that reduces pressure, under the conditions of 55 DEG C~105 DEG C of temperature rectification under vacuum is carried out.
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537573A (en) * | 2017-09-23 | 2018-01-05 | 江苏正大清江制药有限公司 | The method of the Cineole of high selectivity 1,8 |
| CN108558902A (en) * | 2018-05-25 | 2018-09-21 | 云南悦馨香料科技有限公司 | The method that terpinol synthesizes 1,8- Cineoles |
| CN108864126A (en) * | 2018-06-05 | 2018-11-23 | 云南国润香料制造有限公司 | A kind of method of eucalyptus oil series classification rectifying |
| CN110639615A (en) * | 2019-09-05 | 2020-01-03 | 广西民族师范学院 | Preparation method and application of immobilized phosphotungstic acid catalyst |
| CN111647002A (en) * | 2020-05-22 | 2020-09-11 | 成都市明典世家生物科技有限公司 | Method for preparing high-purity 1, 8-cineole by using alkane diol mixed green solvent |
| CN114230575A (en) * | 2021-12-07 | 2022-03-25 | 南昌工程学院 | Method for synthesizing 1, 8-cineole by catalyzing alpha-terpineol in solvent-free system |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270023A1 (en) * | 1986-12-03 | 1988-06-08 | Union Camp Corporation | Improved method of preparing cineoles |
| EP0300117A2 (en) * | 1987-07-24 | 1989-01-25 | Union Camp Corporation | Method of preparing cineoles |
| CN103467475A (en) * | 2013-09-23 | 2013-12-25 | 长汀劲美生物科技有限公司 | Purification method for 1, 8-cineole |
| CN103785468A (en) * | 2014-02-25 | 2014-05-14 | 厦门大学 | Preparation method for solid heteropolyacid catalyst for synthesizing 1,8-cineole |
-
2016
- 2016-12-14 CN CN201611154731.7A patent/CN106674244A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270023A1 (en) * | 1986-12-03 | 1988-06-08 | Union Camp Corporation | Improved method of preparing cineoles |
| EP0300117A2 (en) * | 1987-07-24 | 1989-01-25 | Union Camp Corporation | Method of preparing cineoles |
| CN103467475A (en) * | 2013-09-23 | 2013-12-25 | 长汀劲美生物科技有限公司 | Purification method for 1, 8-cineole |
| CN103785468A (en) * | 2014-02-25 | 2014-05-14 | 厦门大学 | Preparation method for solid heteropolyacid catalyst for synthesizing 1,8-cineole |
Non-Patent Citations (3)
| Title |
|---|
| ENIO J. LEAO LANA ET AL.: ""Synthesis of 1,8-cineole and 1,4-cineole by isomerization of α-terpineol catalyzed by heteropoly acid"", 《JOURNAL OF MOLECULAR CATALYSIS A: CHEMICAL》 * |
| 张健生 等: ""助剂辅助真空间歇精馏分离1,8-桉叶素"", 《化工进展》 * |
| 张广求 等: ""桉叶素精制工艺初步研究"", 《云南民族大学学报: 自然科学版》 * |
Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107537573A (en) * | 2017-09-23 | 2018-01-05 | 江苏正大清江制药有限公司 | The method of the Cineole of high selectivity 1,8 |
| CN108558902A (en) * | 2018-05-25 | 2018-09-21 | 云南悦馨香料科技有限公司 | The method that terpinol synthesizes 1,8- Cineoles |
| CN108864126A (en) * | 2018-06-05 | 2018-11-23 | 云南国润香料制造有限公司 | A kind of method of eucalyptus oil series classification rectifying |
| CN108864126B (en) * | 2018-06-05 | 2021-06-04 | 云南国润香料制造有限公司 | Method for continuously and hierarchically rectifying eucalyptus oil |
| CN110639615A (en) * | 2019-09-05 | 2020-01-03 | 广西民族师范学院 | Preparation method and application of immobilized phosphotungstic acid catalyst |
| CN111647002A (en) * | 2020-05-22 | 2020-09-11 | 成都市明典世家生物科技有限公司 | Method for preparing high-purity 1, 8-cineole by using alkane diol mixed green solvent |
| CN111647002B (en) * | 2020-05-22 | 2023-02-24 | 成都市明典世家生物科技有限公司 | Method for preparing high-purity 1,8-cineole by using alkanediol mixed green solvent |
| CN114230575A (en) * | 2021-12-07 | 2022-03-25 | 南昌工程学院 | Method for synthesizing 1, 8-cineole by catalyzing alpha-terpineol in solvent-free system |
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