CN106366090A - Method of synthesizing 1,8-cineole from alpha-terpilenol - Google Patents
Method of synthesizing 1,8-cineole from alpha-terpilenol Download PDFInfo
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- CN106366090A CN106366090A CN201610725260.4A CN201610725260A CN106366090A CN 106366090 A CN106366090 A CN 106366090A CN 201610725260 A CN201610725260 A CN 201610725260A CN 106366090 A CN106366090 A CN 106366090A
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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
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P20/00—Technologies relating to chemical industry
- Y02P20/50—Improvements relating to the production of bulk chemicals
- Y02P20/584—Recycling of catalysts
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method of synthesizing 1,8-cineole from alpha-terpilenol. The method is characterized in that one of trichloroacetic acid, dichloroacetic acid, chloroacetic acid or trifluoroacetic acid is employed in the process of synthesizing the 1,8-cineole from the raw material alpha-terpilenol. The method can reach 99% maximumly in conversion rate of the alpha-terpilenol. The selectivity of the product 1,8-cineole can reach 51% maximumly. The water solution of a catalyst can be recycled, thereby greatly increasing the utilization rate of the raw material. The method has simple process, is convenient to operate and has low production cost.
Description
Technical field
The present invention relates to 1, 8-Cineole synthesis field, synthesize the side of 1, 8-Cineole particularly to a kind of alpha-terpineol
Method.
Background technology
1, 8-Cineole also known as eudesmol, cineole, 1, 8-Cineole, Ou Kanabutuo, chemical name: 1,3,
3- trimethyl -2- oxabicyclo [2.2.2.] octane (cas no 470-82-6), has the camphoraceous abnormal smells from the patient of class, refrigerant, fragrant
Pungent, it is widely used in pharmaceutical products, cough drop, in artificial mint, also have more wide in gargarism, toothpaste, air sanitizer
General application.
At present, the 1, 8-Cineole on market is mainly and passes through water from myrtle Eucalyptus globulus Labill and canella Radix Cinnamomi porrecti
Steam distillation extracts and obtains, and its key step includes: the branch and leaf of Eucalyptus globulus Labill and Radix Cinnamomi porrecti obtain Eucalyptus Globulus oil and perfume (or spice) by steam distillation
Camphor oil, then it is refining to obtain the 1, 8-Cineole finished product of high-load further by the method such as rectification and freezing and crystallizing.Due to Eucalyptus globulus Labill
Oil and Radix Cinnamomi porrecti oil ingredient are complicated, in addition to the higher 1, 8-Cineole of content, also limonene, pinene and other terpin alkenes thing
Matter.These materials and 1, 8-Cineole have similar physicochemical properties it is very difficult to be separated with 1, 8-Cineole, lead
Cause to be difficult in commercial production obtain highly purified 1,8- cineole.Meanwhile, Eucalyptus Globulus oil and Radix Cinnamomi porrecti these natural plant essential oils of oil
Raw material sources are also very limited so that the quality of 1, 8-Cineole product and yield all far can not meet the demand in market.
Therefore, to obtain 1, 8-Cineole using other raw materials and to synthesize 1, 8-Cineole especially with chemical method and to seem abnormal heavy
Will.
Researchers theoretically demonstrate the feasibility to synthesize 1, 8-Cineole with alpha-terpineol for raw material first,
In follow-up research, it is catalyst that people use various liquid acid or solid acid, is successfully realized and is urged for raw material with alpha-terpineol
It is combined to 1,8- cineole.Such as mitchell et al. to synthesize 1, 8-Cineole with phosphoric acid and oxalic acid for catalyst, mole
Rate reaches as high as 15%；Elena et al. phosphotungstic acid load on silica, react in organic solvent, also successfully with α-
Terpineol is Material synthesis 1,8- cineole；With Bismuth triflate as catalyst, benzene is solvent to lambert et al., with relatively
High yield is prepared into 1,8- cineole from alpha-terpineol.The research that China synthesizes 1, 8-Cineole with regard to chemical method is less, literary composition
Offering report Wang Hong great waves et al. using silicon dioxide carried phosphotungstic acid is catalyst, catalysis alpha-terpineol synthesis 1, 8-Cineole.
Though the above method successfully can synthesize 1, 8-Cineole, but still there are various shortcomings, such as 1, 8-Cineole
Reaction yield is low, preparation process of silicon dioxide carried phosphotungstic acid catalyst is complicated, catalyst high cost and usage amount is big, reaction
During need the problems such as lead to the loaded down with trivial details post processing of technique complicated and relatively costly using various organic solvents.
Content of the invention
It is an object of the invention to provide one kind does not use organic solvent, pollution-free, easy and simple to handle, reaction is gentle and reacts
The synthetic method of the 1,8- cineole of selectivity and high conversion rate.
For achieving the above object, technical scheme proposed by the present invention is: the method that alpha-terpineol synthesizes 1, 8-Cineole, its
It is characterised by, using trichloroacetic acid, dichloroacetic acid, monoxone or trifluoro during raw material alpha-terpineol synthesis 1, 8-Cineole
One of acetic acid.
Further, the method that alpha-terpineol of the present invention synthesizes 1, 8-Cineole, comprises the steps:
Step 1: raw material alpha-terpineol and water and catalyst are added in reaction bulb；
Step 2: heating stirring reaction；
Step 3: reaction terminates rear reactant liquor standing, layering, upper oil phase vacuum distillation after alkali cleaning, that is, obtain highly purified
1,8- cineole product.
Further, in step 1, raw material alpha-terpineol gas chromatogram content is 40%-98%, and water is tap water.
Further, in step 1, the mass ratio of raw material alpha-terpineol and water is 1:0.5～1:1, raw material alpha-terpineol and
The mass ratio of catalyst is 1:0.05～1:0.1.
Further, in step 2, the reaction temperature after heating is 25 DEG C～50 DEG C, and the stirring reaction time is 2 h～8h.
The method that 1, 8-Cineole is synthesized using technique scheme, alpha-terpineol of the present invention, raw material alpha-terpineol
Conversion ratio highest can reach 99%, the selectivity of product 1, 8-Cineole also may be up to 51%, and the aqueous solution of catalyst
Can recycle, be a kind of synthetic method of green.The present invention synthesizes 1,8- cineole method phase with existing alpha-terpineol
Than having an advantage following outstanding:
1) aqueous catalyst solution can recycle, and reduces production cost, it is to avoid environmental pollution；
2) selectivity of catalyst is good, may be up to 51% to the selectivity of 1, 8-Cineole；
3) simple to the content requirement of raw material alpha-terpineol, widen the source of raw oil；
4) process is simple, is easy to operate.
Specific embodiment
With reference to specific embodiment, the present invention will be further described.
Embodiment 1
30g raw oil (containing alpha-terpineol 40%), 15g tap water and 1.5g monoxone are added in reaction bulb；Stir at 50 DEG C
Reaction 8h；Reactant liquor contains alpha-terpineol 0.4% through gas chromatographic detection, and 1, 8-Cineole content is 20.1%.
Embodiment 2
The trichloroacetic acid of 15g raw oil (containing alpha-terpineol 40%), 12g tap water and 1.5g is added in reaction bulb；At 25 DEG C
Heated and stirred reacts 2h；Reactant liquor contains alpha-terpineol 8%, 1, 8-Cineole 14.4% through gas chromatographic detection.
Embodiment 3
The trifluoroacetic acid of 30g raw oil (containing alpha-terpineol 70.1%), 30g tap water and 2.5g is added in reaction bulb；45℃
Lower heated and stirred reacts 5h；Reactant liquor contains alpha-terpineol 6.5%, 1, 8-Cineole 30.2% through gas chromatographic detection.
Embodiment 4
The dichloroacetic acid of 30g raw oil (containing alpha-terpineol 85.2%), 15g tap water and 3g is added in reaction bulb；At 50 DEG C
Heated and stirred reacts 8h；Reactant liquor contains alpha-terpineol 0.4%, 1, 8-Cineole 43.3% through gas chromatographic detection.
Embodiment 5
The trichloroacetic acid of 30g raw oil (containing alpha-terpineol 98%), 30g tap water and 2.5g is added in reaction bulb；At 50 DEG C
Heated and stirred reacts 6h；Reactant liquor contains alpha-terpineol 0.5%, 1, 8-Cineole 49.7% through gas chromatographic detection.
Embodiment 6
The trifluoroacetic acid of 30g raw oil (containing alpha-terpineol 58.4%), 15g tap water and 3g is added in reaction bulb；At 40 DEG C
Heated and stirred reacts 4h；Reactant liquor contains alpha-terpineol 1.1%, 1, 8-Cineole 28.0% through gas chromatographic detection.
Embodiment 7
The monoxone of 30g raw oil (containing alpha-terpineol 90%), 20g tap water and 2g is added in reaction bulb；Heat at 35 DEG C
Stirring reaction 8h；Reactant liquor contains alpha-terpineol 0.9%, 1, 8-Cineole 44.5% through gas chromatographic detection.
Embodiment 8
The trichloroacetic acid of 30g raw oil (containing alpha-terpineol 50%), 15g tap water and 1.5g is added in reaction bulb；At 50 DEG C
Heated and stirred reacts 7h；Reactant liquor contains alpha-terpineol 1.2%, 1, 8-Cineole 24.5% through gas chromatographic detection.
Embodiment 9
The trifluoroacetic acid of 15g raw oil (containing alpha-terpineol 98%), 12g tap water and 1g is added in reaction bulb；Add at 40 DEG C
5h is reacted in thermal agitation；Reactant liquor contains alpha-terpineol 1.6%, 1, 8-Cineole 47.8% through gas chromatographic detection.
Embodiment 10
The dichloroacetic acid of 30g raw oil (containing alpha-terpineol 80%), 25g tap water and 2.4g is added in reaction bulb；At 50 DEG C
Heated and stirred reacts 6h；Reactant liquor is through gas chromatographic detection content containing alpha-terpineol 1.8%, 1, 8-Cineole 38.4%.
Although specifically show and describe the present invention in conjunction with preferred embodiment, those skilled in the art should be bright
In vain, in the spirit and scope of the present invention being limited without departing from appended claims, in the form and details to this
Bright make a variety of changes, be protection scope of the present invention.
Claims (5)
1. alpha-terpineol synthesizes the method for 1, 8-Cineole it is characterised in that synthesizing 1, 8-Cineole mistake in raw material alpha-terpineol
One of trichloroacetic acid, dichloroacetic acid, monoxone or trifluoroacetic acid is adopted in journey.
2. alpha-terpineol according to claim 1 synthesizes the method for 1, 8-Cineole it is characterised in that also including walking as follows
Rapid:
Step 1: raw material alpha-terpineol and water and catalyst are added in reaction bulb；
Step 2: heating stirring reaction；
Step 3: reaction terminates rear reactant liquor standing, layering, upper oil phase vacuum distillation after alkali cleaning, that is, obtain highly purified
1,8- cineole product.
3. alpha-terpineol according to claim 1 synthesizes the method for 1, 8-Cineole it is characterised in that in step 1, raw material
Alpha-terpineol gas chromatogram content is 40%-98%, and water is tap water.
4. alpha-terpineol according to claim 1 synthesizes the method for 1, 8-Cineole it is characterised in that in step 1, raw material
The mass ratio of alpha-terpineol and water is 1:0.5～1:1, and the mass ratio of raw material alpha-terpineol and catalyst is 1:0.05～1:0.1.
5. alpha-terpineol according to claim 1 synthesizes the method for 1, 8-Cineole it is characterised in that in step 2, heating
Reaction temperature afterwards is 25 DEG C～50 DEG C, and the stirring reaction time is 2h～8h.
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| Application Number | Priority Date | Filing Date | Title |
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| CN201610725260.4A CN106366090A (en) | 2016-08-26 | 2016-08-26 | Method of synthesizing 1,8-cineole from alpha-terpilenol |
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| CN201610725260.4A CN106366090A (en) | 2016-08-26 | 2016-08-26 | Method of synthesizing 1,8-cineole from alpha-terpilenol |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113980030A (en) * | 2021-08-09 | 2022-01-28 | 江西农业大学 | Method for high-selectivity catalytic synthesis of1,8-cineole |
| 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 (5)
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|---|---|---|---|---|
| EP0270023A1 (en) * | 1986-12-03 | 1988-06-08 | Union Camp Corporation | Improved method of preparing cineoles |
| GB2354771A (en) * | 1999-10-01 | 2001-04-04 | Mcbride Ltd Robert | Bactericide combinations in detergents |
| CN102627528A (en) * | 2012-03-16 | 2012-08-08 | 云南森美达生物科技有限公司 | Method for synthesis of terpineol by supersonic wave assistance |
| 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
- 2016-08-26 CN CN201610725260.4A patent/CN106366090A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| EP0270023A1 (en) * | 1986-12-03 | 1988-06-08 | Union Camp Corporation | Improved method of preparing cineoles |
| GB2354771A (en) * | 1999-10-01 | 2001-04-04 | Mcbride Ltd Robert | Bactericide combinations in detergents |
| CN102627528A (en) * | 2012-03-16 | 2012-08-08 | 云南森美达生物科技有限公司 | Method for synthesis of terpineol by supersonic wave assistance |
| 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)
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| J. EINHORN等: "Ultrasound in Organic Synthesis. 18.Selective Oxymercuration via Sonochemically in Situ Generated Mercury Salts", 《J. ORG. CHEM》 * |
| LAURA FARINA，等: "Terpene compounds as possible precursors of 1，8-cineole in red grapes and wines", 《JOURNAL OF AGRICULTURAL AND FOOD CHEMISTRY》 * |
| NORA COMELLI等: "Hydration of α-pinene catalyzed by acid clays", 《CENT. EUR. J. CHEM.》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN113980030A (en) * | 2021-08-09 | 2022-01-28 | 江西农业大学 | Method for high-selectivity catalytic synthesis of1,8-cineole |
| 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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