CN107537573A - The method of the Cineole of high selectivity 1,8 - Google Patents
The method of the Cineole of high selectivity 1,8 Download PDFInfo
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- CN107537573A CN107537573A CN201710869981.7A CN201710869981A CN107537573A CN 107537573 A CN107537573 A CN 107537573A CN 201710869981 A CN201710869981 A CN 201710869981A CN 107537573 A CN107537573 A CN 107537573A
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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
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Abstract
The invention provides a kind of high selectivity Formula（Ⅰ）The method of the oxabicyclo of 1,3,3 trimethyl 2 [2,2,2] octane, method selectivity is high, and conversion ratio is good, the recyclable recycling of catalyst, safety and environmental protection, and easy to operate, is adapted to industrialized production.
Description
Technical field
The present invention relates to high selectivity Formula（Ⅰ）1,3,3- trimethyl -2- oxabicyclos [2,2,2] octane
The method of [being hereafter sometimes referred to as 1,8- Cineoles].
Background technology
1,8- Cineoles（1,8-Cineole）, chemical name 1,3,3- trimethyl -2- oxabicyclos [2,2,2] octane, is one
Kind monoterpenes compound, is colourless transparent liquid, there is camphor breath and refrigerant herbal medicine taste, is the main component of eucalyptus oil, main
It is present in myrtle blue gum and canella camphor tree, there is wind-expelling pain-stopping.It is as a kind of important
Fine chemical product, it is widely used in the field of industrial production such as medicine, essence and flavoring agent.
Most domestic prepares 1, 8-Cineole using natural extraction process at present, but natural plant resource is limited, 1.8-
Cineole yield is difficult to meet the market demand, and impurity component is more in the eucalyptus oil extracted, mainly has：Limonene, australene, β-
Firpene, laurene, phellandrene, γ-terpinenes, to P-cymene, terpinol etc., their boiling points are closer to, it is difficult to pass through day
So extraction, the method for crystal refining obtain the 1, 8-Cineole of high-purity.
Some external periodicals（Fariña L,Boido E,Carrau F,et al.Terpene compounds as
possible precursors of 1,8-cineolo in red grapes and wines[J].Journal of
agricultural and food chemistry,2005,53(5):1633-1636）Report by limonene, terpinol system
The method of standby 1, 8-Cineole, but yield and selectivity are relatively low.
Patent CN103785468A reports the synthetic method of 1, 8-Cineole, and it is solid that it first prepares phosphotungstic acid/silica
Body heteropolyacid catalyst, then 1, 8-Cineole is prepared by the catalyst alpha-terpineol.It reacts the α-pine tar that can obtain 70%
Alcohol conversion and close to 35% 1,8- Cineoles selectivity.But above-mentioned patent preparation method, when preparing heteropolyacid catalyst, institute
The amount of etoh solvent and water is especially big, and catalyst drying post processing is relatively complicated, considerably increases production cost, it is difficult to
Amplification production；The quantity of solvent of catalytic reaction is also larger, and the yield for reacting overall is relatively low, and less than 35%, impurity is more, mainly has：α-
Thujene, 1,4- Cineoles, 2- this cause produce finished product be significantly larger than the value of 1,8- Cineoles in itself.
Changing the preparation method of phosphotungstic acid/carrier solids heteropolyacid catalyst, adjustment is catalyzed the condition of alpha-terpineol reaction,
The use of solvent is greatly reduced, and simplifies the processing method of catalyst, while the conversion ratio of alpha-terpineol is reached
100%, the selectivity of 1, 8-Cineole reaches 61%.
The content of the invention
Goal of the invention：For synthesis 1, 8-Cineole poor selectivity at present, the problem of yield is low, and production cost is high, there is provided
High selectivity, the crucial catalyst that high-conversion rate catalysis prepares 1, 8-Cineole obtain preparation method.
Another object of the present invention is to provide to prepare the conditions of 1,8- Cineoles by affiliated catalyst.
In order to reach as above purpose, the present invention adopts the following technical scheme that：
The preparation method of crucial phosphate-tungstic acid/carrier solids heteropoly acid of high selectivity 1, 8-Cineole, it is prepared
Step is as follows：
1）Carrier high-temperature roasting；
2）Carrier after roasting is added in the heteropoly acid aqueous solution, heating stirring absorption, then filter to obtain solid filter cake；
3）By filtration cakes torrefaction, phosphotungstic acid/carrier solids heteropolyacid catalyst is obtained.
Step 1）Carrier is selected from diatomite or silica, and temperature selects 500 DEG C of -550 DEG C of roasting 8-10h.
Step 2）Phosphotungstic acid aqueous solution concentration is 0.4-0.6g/ml, and the carrier of roasting compares carrier according to quality：Phosphotungstic acid=
3：1~4:1 ratio is added in phosphotungstic acid aqueous solution, 80~100 DEG C of heating-up temperature, stirring and adsorbing time 8-10h.
Step 3）150~200 DEG C of dry cake temperature, 8~10h of drying time
It is as follows using the solid heteropoly acid catalysis alpha-terpineol synthesis 1, 8-Cineole of above-mentioned preparation, synthetic method：
1）Alpha-terpineol is added in reaction bulb, stirring solvent is added and is uniformly dissolved, adds and is urged by prepared by claim 1
Agent, heating stirring reaction；
2）Vapor detection, alpha-terpineol fundamental reaction stop reacting completely, filter recovery catalyst, and collect filtrate；
3）Filtrate decompression is distilled to recover solvent, concentrate is obtained and is evaporated under reduced pressure to obtain 1, 8-Cineole crude product again.
Synthetic method step 1）Solvent selects normal heptane, n-hexane, hexamethylene etc., and solvent is according to volume（Solvent）：Quality
（Alpha-terpineol）=10:1~15:1 ratio adds, and catalyst is according to mass ratio, catalyst：Alpha-terpineol=0.6:1~1:1
Ratio adds,
40-70 DEG C of heating-up temperature, react 6-12h.
Synthetic method step 3）Reduced vacuum degree 0.001MPa, 90-100 DEG C of temperature.
Using the present invention of as above technical scheme, had the advantages that relative to existing technology：
1）The method for preparing solid acid catalysts is simple, and cost is relatively low, and the catalyst recoverable, environmental pollution
It is small.
2）Phosphotungstic acid/carrier solids heteropolyacid catalyst catalytic activity is high, and reaction temperature is moderate, and post processing is simple, is easy to
Production operation.
3）Phosphotungstic acid/carrier solids heteropolyacid catalyst catalysis alpha-terpineol synthesis 1, 8-Cineole, the selectivity of reaction
And conversion ratio, mainly have with the preparation condition of catalyst, the rate of charge of catalyst and reaction substrate, reaction temperature and reaction time
Close.The present invention uses phosphotungstic acid/carrier solids heteropolyacid catalyst catalysis alpha-terpineol synthesis 1, 8-Cineole, most high available
100% conversion ratio and 61% 1,8- Cineoles selectivity.
Brief description of the drawings：
Fig. 1 is the reaction solution vapor detection collection of illustrative plates of embodiment 1
Fig. 2 is the reaction solution vapor detection collection of illustrative plates of embodiment 2
Fig. 3 is the reaction solution vapor detection collection of illustrative plates of embodiment 3
Fig. 4 is the reaction solution vapor detection collection of illustrative plates of embodiment 4
Fig. 5 is the reaction solution vapor detection collection of illustrative plates of embodiment 5
Fig. 6 is the reaction solution vapor detection collection of illustrative plates of embodiment 6
Fig. 7 is the reaction solution vapor detection collection of illustrative plates of embodiment 7
Fig. 8 is the reaction solution vapor detection collection of illustrative plates of embodiment 8
Form is described in further details to present disclosure again by the following examples, but not the present invention should not be interpreted as with regard to this
Following examples are only limitted in above-mentioned subject area.Under the premise of the above-mentioned technology of the present invention is not departed from, according to the common skill in this area
The modification of corresponding replacement or change that art knowledge and customary means are made, is included in the present invention.
Embodiment 1
1. being calcined carrier, diatomite and silica are calcined 8-10h under 500-550 DEG C of environment, cooling is stand-by.2. prepare
0.4g/ml Salkowski's solution 40ml, the diatomite added after 48g roastings, heat up 90~100 DEG C, stirring and adsorbing 8h, are cooled to often
Temperature, suction filtration, the dry 8~10h of 200 DEG C of filter cake to obtain phosphotungstic acid/diatomite solid acid catalysts 47.1g to dry.3. reacting
50g alpha-terpineols are added in bottle, 500ml normal heptanes stirring 5min is added, is uniformly dissolved, adds consolidating for the above-mentioned preparations of 30g
Body heteropoly acid, it is warming up to 60~65 DEG C of stirring reactions, vapor detection reaction, pine tar alcohol conversion 89.1%, 1, 8-Cineole selection
Property 32.2%（See accompanying drawing 1）.
Vapor detection condition is as follows：
Chromatographic column：PEG 20000 or the similar post of polarity, carrier gas：Nitrogen, flow velocity：1ml/min, detector：FID, sample introduction
Amount：1 μ l, split ratio：1：50,220 DEG C of detector temperature,
Column temperature：60 DEG C of initial temperature, 5min is kept, then rise to 200 DEG C with 5 DEG C/min speed, keep 5min.
Embodiment 2
1. being calcined carrier, diatomite and silica are calcined 8-10h under 500-550 DEG C of environment, cooling is stand-by.2. prepare
0.4g/ml Salkowski's solution 40ml, the diatomite added after 48g roastings, heat up 90~100 DEG C, stirring and adsorbing 8h, are cooled to often
Temperature, suction filtration, the dry 8~10h of 200 DEG C of filter cake to obtain phosphotungstic acid/diatomite solid acid catalysts 47.2g to dry.3. reacting
50g alpha-terpineols are added in bottle, 500ml normal heptanes stirring 5min is added, is uniformly dissolved, adds consolidating for the above-mentioned preparations of 30g
Body heteropoly acid, it is warming up to 55~60 DEG C of stirring reactions, vapor detection reaction, pine tar alcohol conversion 79.0%, 1, 8-Cineole selection
Property 31.8%（See accompanying drawing 2）.
Embodiment 3
1. being calcined carrier, diatomite and silica are calcined 8-10h under 500-550 DEG C of environment, cooling is stand-by.2. prepare
0.5g/ml Salkowski's solution 40ml, the diatomite added after 60g roastings, heat up 90~100 DEG C, stirring and adsorbing 8h, are cooled to often
Temperature, suction filtration, the dry 8~10h of 200 DEG C of filter cake to obtain phosphotungstic acid/diatomite solid acid catalysts 60.1g to dry.3. reacting
50g alpha-terpineols are added in bottle, 500ml normal heptanes stirring 5min is added, is uniformly dissolved, adds consolidating for the above-mentioned preparations of 30g
Body heteropoly acid, it is warming up to 55~60 DEG C of stirring reactions, vapor detection reaction, pine tar alcohol conversion 85.1%, 1, 8-Cineole selection
Property 39.8%（See accompanying drawing 3）.
Embodiment 4
1. being calcined carrier, diatomite and silica are calcined 8-10h under 500-550 DEG C of environment, cooling is stand-by.2. prepare
0.5g/ml Salkowski's solution 40ml, the diatomite added after 60g roastings, heat up 90~100 DEG C, stirring and adsorbing 8h, are cooled to often
Temperature, suction filtration, the dry 8~10h of 200 DEG C of filter cake to obtain phosphotungstic acid/diatomite solid acid catalysts 59.8g to dry.3. reacting
50g alpha-terpineols are added in bottle, 500ml normal heptanes stirring 5min is added, is uniformly dissolved, adds consolidating for the above-mentioned preparations of 35g
Body heteropoly acid, it is warming up to 60~65 DEG C of stirring reactions, vapor detection reaction, pine tar alcohol conversion 92.4%, 1, 8-Cineole selection
Property 41.9%（See accompanying drawing 4）.
Embodiment 5
1. being calcined carrier, diatomite and silica are calcined 8-10h under 500-550 DEG C of environment, cooling is stand-by.2. prepare
0.5g/ml Salkowski's solution 40ml, the diatomite added after 60g roastings, heat up 90~100 DEG C, stirring and adsorbing 8h, are cooled to often
Temperature, suction filtration, the dry 8~10h of 200 DEG C of filter cake to obtain phosphotungstic acid/diatomite solid acid catalysts 60.0g to dry.3. reacting
50g alpha-terpineols are added in bottle, 500ml normal heptanes stirring 5min is added, is uniformly dissolved, adds consolidating for the above-mentioned preparations of 40g
Body heteropoly acid, it is warming up to 60~65 DEG C of stirring reactions, vapor detection reaction, pine tar alcohol conversion 100%, 1, 8-Cineole selection
Property 53.7%（See accompanying drawing 5）.
Embodiment 6
1. being calcined carrier, diatomite and silica are calcined 8-10h under 500-550 DEG C of environment, cooling is stand-by.2. prepare
0.5g/ml Salkowski's solution 40ml, the diatomite added after 60g roastings, heat up 90~100 DEG C, stirring and adsorbing 8h, are cooled to often
Temperature, suction filtration, the dry 8~10h of 200 DEG C of filter cake to obtain phosphotungstic acid/diatomite solid acid catalysts 60.0g to dry.3. reacting
50g alpha-terpineols are added in bottle, 500ml normal heptanes stirring 5min is added, is uniformly dissolved, adds consolidating for the above-mentioned preparations of 40g
Body heteropoly acid, it is warming up to 55~60 DEG C of stirring reactions, vapor detection reaction, pine tar alcohol conversion 100%, 1, 8-Cineole selection
Property 60.3%（See accompanying drawing 6）.
Embodiment 7
1. being calcined carrier, diatomite and silica are calcined 8-10h under 500-550 DEG C of environment, cooling is stand-by.2. prepare
0.6g/ml Salkowski's solution 40ml, the diatomite added after 60g roastings, heat up 90~100 DEG C, stirring and adsorbing 8h, are cooled to often
Temperature, suction filtration, the dry 8~10h of 200 DEG C of filter cake to obtain phosphotungstic acid/diatomite solid acid catalysts 60.1g to dry.3. reacting
50g alpha-terpineols are added in bottle, 500ml normal heptanes stirring 5min is added, is uniformly dissolved, adds consolidating for the above-mentioned preparations of 40g
Body heteropoly acid, it is warming up to 55~60 DEG C of stirring reactions, vapor detection reaction, pine tar alcohol conversion 100%, 1, 8-Cineole selection
Property 59.8%（See accompanying drawing 7）.
Embodiment 8
1. being calcined carrier, diatomite and silica are calcined 8-10h under 500-550 DEG C of environment, cooling is stand-by.2. prepare
0.6g/ml Salkowski's solution 40ml, the silica added after 60g roastings, heat up 90~100 DEG C, stirring and adsorbing 8h, are cooled to
Normal temperature, suction filtration, the dry 8~10h of 200 DEG C of filter cake to obtain phosphotungstic acid/silica solid heteropolyacid catalyst 60.1g to dry.3.
50g alpha-terpineols are added in reaction bulb, 500ml normal heptanes stirring 5min is added, is uniformly dissolved, adds the above-mentioned preparations of 40g
Solid heteropoly acid, be warming up to 55~60 DEG C of stirring reactions, vapor detection reaction, pine tar alcohol conversion 100%, 1, 8-Cineole
Selectivity 58.6%（See accompanying drawing 8）.
The present invention has advantages below compared with prior art：
1. the present invention is with phosphotungstic acid/diatomite（Or silica）Solid heteropoly acid is catalyst, carries out catalytic reaction, selectivity
Height, conversion ratio is good, the recyclable recycling of catalyst, safety and environmental protection, and easy to operate, is adapted to industrialized production.
2. gained target product crude product purity of the invention is higher, amount of impurities is few, is easy to later crystallization to purify, and prepares high-purity
The 1,8- Cineoles of degree.
Claims (10)
1. a kind of preparation method of crucial phosphate-tungstic acid/carrier solids heteropoly acid of high selectivity 1, 8-Cineole,
Its preparation process is as follows：
1）Carrier high-temperature roasting；
2）Carrier after roasting is added in the heteropoly acid aqueous solution, heating stirring absorption, then filter to obtain solid filter cake；
3）By filtration cakes torrefaction, phosphotungstic acid/carrier solids heteropolyacid catalyst is obtained.
2. carrier described in claim 1 is selected from diatomite or silica.
3. the preparation method of phosphotungstic acid/carrier solids heteropoly acid described in claim 1, it is characterised in that step 1）Diatomite or
Silica needs 500 DEG C of roasting 8h-10h.
4. the preparation method of phosphotungstic acid/carrier solids heteropoly acid described in claim 1, it is characterised in that step 2）Phosphotungstic acid water
Solution solubility is 0.4-0.6g/ml.
5. the preparation method of phosphotungstic acid/diatomite solid heteropoly acid described in claim 1, it is characterised in that step 2）Will roasting
Carrier afterwards is according to mass ratio, carrier：Phosphotungstic acid=3：1~4:1 ratio is added in phosphotungstic acid aqueous solution.
6. the preparation method of phosphotungstic acid/carrier solids heteropoly acid described in claim 1, it is characterised in that step 2）Heating-up temperature
90~100 DEG C, stirring and adsorbing time 8-10h.
7. the preparation method of phosphotungstic acid/carrier solids heteropoly acid described in claim 1, it is characterised in that step 3）Dry cake
150~200 DEG C of temperature, 8~10h of drying time.
8. the catalyst alpha-terpineol synthesis 1, 8-Cineole for requiring to prepare using right 1, synthetic method are as follows：
1）Alpha-terpineol is added in reaction bulb, stirring solvent is added and is uniformly dissolved, adds and is urged by prepared by claim 1
Agent, heating stirring reaction；
2）Vapor detection, alpha-terpineol fundamental reaction stop reacting completely, filter recovery catalyst, and collect filtrate；
3）Filtrate decompression is distilled to recover solvent, concentrate is obtained and is evaporated under reduced pressure to obtain 1, 8-Cineole crude product again.
9. the synthetic method described in claim 8, it is characterised in that solvent selects normal heptane, n-hexane, hexamethylene etc., and solvent is pressed
According to volume（Solvent）：Quality（Alpha-terpineol）=10:1~15:1 ratio adds.
10. the synthetic method described in claim 8, it is characterised in that by catalyst according to mass ratio, catalyst：Alpha-terpineol=
0.6:1~1:1 ratio adds, 40-70 DEG C of heating-up temperature, reacts 6-12h, reduced vacuum degree -0.1MPa, temperature 90-100
℃。
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| CN201710869981.7A CN107537573A (en) | 2017-09-23 | 2017-09-23 | The method of the Cineole of high selectivity 1,8 |
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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 |
| CN109810118A (en) * | 2019-01-07 | 2019-05-28 | 厦门大学 | A kind of method of alpha-terpineol synthesis 1,8- 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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| CN1729053A (en) * | 2002-12-20 | 2006-02-01 | 昭和电工株式会社 | Heteropolyacid and/or its salt supported catalyst, production process of the catalyst and production process of compound using the catalyst |
| CN103785468A (en) * | 2014-02-25 | 2014-05-14 | 厦门大学 | Preparation method for solid heteropolyacid catalyst for synthesizing 1,8-cineole |
| CN103936562A (en) * | 2014-05-14 | 2014-07-23 | 湖南大学 | Method for preparing bisphenol F |
| CN106674244A (en) * | 2016-12-14 | 2017-05-17 | 盐城市春竹香料有限公司 | Preparation method of cineole |
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2017
- 2017-09-23 CN CN201710869981.7A patent/CN107537573A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1729053A (en) * | 2002-12-20 | 2006-02-01 | 昭和电工株式会社 | Heteropolyacid and/or its salt supported catalyst, production process of the catalyst and production process of compound using the catalyst |
| CN103785468A (en) * | 2014-02-25 | 2014-05-14 | 厦门大学 | Preparation method for solid heteropolyacid catalyst for synthesizing 1,8-cineole |
| CN103936562A (en) * | 2014-05-14 | 2014-07-23 | 湖南大学 | Method for preparing bisphenol F |
| CN106674244A (en) * | 2016-12-14 | 2017-05-17 | 盐城市春竹香料有限公司 | Preparation method of cineole |
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| Title |
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| ENIO J. LEÃO 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》 * |
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 |
| CN109810118A (en) * | 2019-01-07 | 2019-05-28 | 厦门大学 | A kind of method of alpha-terpineol synthesis 1,8- 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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