CN108358872A - A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature - Google Patents
A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature Download PDFInfo
- Publication number
- CN108358872A CN108358872A CN201810233053.6A CN201810233053A CN108358872A CN 108358872 A CN108358872 A CN 108358872A CN 201810233053 A CN201810233053 A CN 201810233053A CN 108358872 A CN108358872 A CN 108358872A
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- CN
- China
- Prior art keywords
- ammonium tungstate
- limonene
- tetrahydrofuran
- room temperature
- olefinic oxide
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- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D301/00—Preparation of oxiranes
- C07D301/02—Synthesis of the oxirane ring
- C07D301/03—Synthesis of the oxirane ring by oxidation of unsaturated compounds, or of mixtures of unsaturated and saturated compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D303/00—Compounds containing three-membered rings having one oxygen atom as the only ring hetero atom
- C07D303/02—Compounds containing oxirane rings
- C07D303/04—Compounds containing oxirane rings containing only hydrogen and carbon atoms in addition to the ring oxygen atoms
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The present invention discloses a kind of method utilizing ammonium tungstate synthesis lemon olefinic oxide at room temperature, including at ambient temperature, after ammonium tungstate is mixed with tetrahydrofuran by a certain percentage, limonene and tetrahydrofuran mixed liquor being added dropwise.Stirring, after completion of dropwise addition, 1,2 limonene epoxides are made in distillation.This method is easy to operate, and target product yield is high, and the reagent of high-purity is provided for subsequent chemical synthesis and polymerization reaction experiment.
Description
Technical field
The present invention relates to a kind of methods for utilizing ammonium tungstate to synthesize lemon olefinic oxide at room temperature, especially with tetrahydrofuran
For solvent, using ammonium tungstate as major catalyst, under the conditions of 20-40 DEG C, the method for synthesizing 1,2- limonene epoxides, belonging to
Close object preparation field.
Background technology
Limonene is most important in addition to firpene in natural essential oil and is distributed widest monoterpene, it be present in 300 kinds with
On essential oil in, wherein in lemon oil, orange oil, bergamot oil, caraway seed oil and dill oil etc. content be up to 90% with
On, limonene can in large quantities from citrus peel, pulp steam distillation in obtain, and these pericarps, pulp be production fruit
The remaining unemployed waste residue of institute after juice and pressed oil.
Limonene can synthesize many compounds through deep processing, and especially limonene alternative epoxy compound is at 1,2- rings
Oxygen limonene, and this epoxides is one of the intermediate that purposes is extremely wide in organic synthesis, can be opened with a variety of nucleopilic reagents
Ring reaction obtains a series of compounds.
Currently, in limonene epoxy compound at 1,2- limonene epoxides (in structure such as following formula shown in compound a) this mistake
Cheng Zhong mostly uses epoxidation reagent and is catalyzed, but by-product 8 would generally be generated in reaction process, 9- limonene epoxides and
Dual oxide limonene epoxide.
In recent years, in many epoxidation reagents, m-chloro-benzoic acid peroxide is selected because it is catalyzed 1,2- limonene epoxides
Selecting property is preferably widely used, but in the catalytic process, reaction would generally discharge a large amount of reaction heat, to cause 1,2- rings
Oxygen limonene yield declines, and therefore, which must carry out at 0 DEG C or less, this is but also seek a kind of easier 1,2- rings
Oxygen limonene synthetic method becomes the problem of urgent need to resolve.
Invention content
The purpose of the present invention is to provide a kind of method for utilizing ammonium tungstate to synthesize lemon olefinic oxide at room temperature, the present invention
Purpose be achieved through the following technical solutions, steps are as follows：Under room temperature at 20-40 DEG C, by ammonium tungstate by certain ratio
Example mix with tetrahydrofuran after, be added dropwise to limonene and tetrahydrofuran mixed liquor, stirring, after completion of dropwise addition, be not necessarily into
The processing of one step, distillation, you can obtain target product --- 1,2- limonene epoxide.
A concentration of 0.01-0.1g/ml of the ammonium tungstate in tetrahydrofuran solution, the limonene are mixed with tetrahydrofuran
The volume ratio for closing liquid is 1：10-1：25.
The advantages and positive effects of the present invention are：
1, it under the conditions of room temperature (20-40 DEG C), by adjusting solvents tetrahydrofurane addition, is catalyzed and synthesized using ammonium tungstate
1,2- limonene epoxide, substantially reduces synthesis cost.
2, this invention simplifies last handling processes, directly select distillation mode and prepare 1,2- limonene epoxides, shorten conjunction
At the time.
Specific implementation mode
With reference to embodiment, the present invention is further described, and following embodiments are illustrative, are not restrictive,
Protection scope of the present invention cannot be limited with following embodiments.
Embodiment 1
It under the conditions of 20-25 DEG C, weighs 2g ammonium tungstates (purity 75%) and is dissolved in 60ml tetrahydrofurans, stir；It has waited for
After fully dissolved, be added dropwise to 80ml limonenes tetrahydrofuran solution (the ratio between its addition volume be limonene：Tetrahydrofuran
It is 1：20), control rate of addition is added dropwise in 3 hours, stirs；After completion of dropwise addition, without being further processed, distillation,
1,2- limonene epoxides can be obtained, yield is about 96%.
Embodiment 2
It under the conditions of 25-30 DEG C, weighs 2g ammonium tungstates (purity 75%) and is dissolved in 30ml tetrahydrofurans, stir；It has waited for
After fully dissolved, be added dropwise to 80ml limonenes tetrahydrofuran solution (the ratio between its addition volume be limonene：Tetrahydrofuran
It is 1：20), control rate of addition is added dropwise in 5 hours；Stirring, after completion of dropwise addition, without being further processed, distillation,
1,2- limonene epoxides can be obtained, yield is about 92%.
Embodiment 3
It under the conditions of 30-35 DEG C, weighs 5g ammonium tungstates (purity 75%) and is dissolved in 60ml tetrahydrofurans, stir；It has waited for
After fully dissolved, be added dropwise to 80ml limonenes tetrahydrofuran solution (the ratio between its addition volume be limonene：Tetrahydrofuran
It is 1：20), control rate of addition is added dropwise in 2 hours；Stirring, after completion of dropwise addition, without being further processed, distillation,
1,2- limonene epoxides can be obtained, yield is about 89%.
Embodiment 4
It under the conditions of 35-40 DEG C, weighs 2g ammonium tungstates (purity 75%) and is dissolved in 60ml tetrahydrofurans, stir；It has waited for
After fully dissolved, be added dropwise to 80ml limonenes tetrahydrofuran solution (the ratio between its addition volume be limonene：Tetrahydrofuran
It is 1：10), control rate of addition is added dropwise in 6 hours；Stirring, after completion of dropwise addition, without being further processed, distillation,
1,2- limonene epoxides can be obtained, yield is about 95%.
Claims (4)
1. a kind of method utilizing ammonium tungstate synthesis lemon olefinic oxide at room temperature, it is characterised in that：Under the conditions of 20-40 DEG C,
It after ammonium tungstate is mixed with tetrahydrofuran by a certain percentage, is added dropwise in the mixed liquor of limonene and tetrahydrofuran, stirs,
After completion of dropwise addition, distillation, you can obtain target product --- 1,2- limonene epoxide.
2. the method for utilizing ammonium tungstate synthesis lemon olefinic oxide at room temperature according to claim 1, it is characterised in that：It is described
A concentration of 0.01-0.1g/ml of the ammonium tungstate in tetrahydrofuran.
3. the method for utilizing ammonium tungstate synthesis lemon olefinic oxide at room temperature according to claim 1, it is characterised in that：It is described
The volume ratio of limonene and tetrahydrofuran is 1：10-1：25.
4. the method for utilizing ammonium tungstate synthesis lemon olefinic oxide at room temperature according to claim 1, it is characterised in that：Control
The time for adding of ammonium tungstate and tetrahydrofuran mixed solution is 2-6 hours.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810233053.6A CN108358872A (en) | 2018-03-21 | 2018-03-21 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810233053.6A CN108358872A (en) | 2018-03-21 | 2018-03-21 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN108358872A true CN108358872A (en) | 2018-08-03 |
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|---|---|---|---|
| CN201810233053.6A Pending CN108358872A (en) | 2018-03-21 | 2018-03-21 | A method of utilize ammonium tungstate to synthesize lemon olefinic oxide at room temperature |
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101829559A (en) * | 2009-03-13 | 2010-09-15 | 复旦大学 | Preparation method and application of WO3/ZrO2 solid super acidic catalyst |
| CN101959872A (en) * | 2008-02-28 | 2011-01-26 | 昭和电工株式会社 | The manufacture method of epoxy compounds |
| JP2013032340A (en) * | 2011-07-01 | 2013-02-14 | Jnc Corp | Quaternary ammonium salt, oxidation catalyst obtained from the same, and method for producing epoxy derivative using the catalyst |
| CN102993129A (en) * | 2012-11-23 | 2013-03-27 | 南昌大学 | Method for preparing 1,2-epoxyoctane |
| CN104725336A (en) * | 2015-03-31 | 2015-06-24 | 天津市职业大学 | Method for preparing 1,2-limonene epoxide at room temperature |
| CN105017179A (en) * | 2015-06-08 | 2015-11-04 | 华中农业大学 | Catalytic synthesis method for limonene-1,2-epoxide |
| WO2016184953A1 (en) * | 2015-05-21 | 2016-11-24 | Symrise Ag | Oxidation of limonene |
-
2018
- 2018-03-21 CN CN201810233053.6A patent/CN108358872A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101959872A (en) * | 2008-02-28 | 2011-01-26 | 昭和电工株式会社 | The manufacture method of epoxy compounds |
| CN101829559A (en) * | 2009-03-13 | 2010-09-15 | 复旦大学 | Preparation method and application of WO3/ZrO2 solid super acidic catalyst |
| JP2013032340A (en) * | 2011-07-01 | 2013-02-14 | Jnc Corp | Quaternary ammonium salt, oxidation catalyst obtained from the same, and method for producing epoxy derivative using the catalyst |
| CN102993129A (en) * | 2012-11-23 | 2013-03-27 | 南昌大学 | Method for preparing 1,2-epoxyoctane |
| CN104725336A (en) * | 2015-03-31 | 2015-06-24 | 天津市职业大学 | Method for preparing 1,2-limonene epoxide at room temperature |
| WO2016184953A1 (en) * | 2015-05-21 | 2016-11-24 | Symrise Ag | Oxidation of limonene |
| CN105017179A (en) * | 2015-06-08 | 2015-11-04 | 华中农业大学 | Catalytic synthesis method for limonene-1,2-epoxide |
Non-Patent Citations (4)
| Title |
|---|
| ELŻBIETA KACZMARCZYK: ""Kinetic study of the phase-transfer catalytic epoxidation of 1,4-bis(allyloxy)butane"", 《JOURNAL OF COLLOID AND INTERFACE SCIENCE》 * |
| HONG-CHANGSHI: ""Epoxidation of α,β-unsaturated acids catalyzed by tungstate (VI) or molybdate (VI) in aqueous solvents: a specific direct oxygen transfer mechanism"", 《TETRAHEDRON》 * |
| KENNETH S. KIRSHENBAUM AND K. BARRY SHARPLESS: ""Improved procedure for the tungstate-catalyzed epoxidation of α,β-unsaturated acids"", 《J. ORG. CHEM.》 * |
| 吴春华: ""杂多酸负载介孔分子筛催化α-蒎烯的环氧化反应"", 《西南林业大学学报》 * |
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Application publication date: 20180803 |
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