CN1821195A - Method for synthesizing verbenol and verbenone with alpha-pinene - Google Patents
Method for synthesizing verbenol and verbenone with alpha-pinene Download PDFInfo
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- CN1821195A CN1821195A CN 200610010776 CN200610010776A CN1821195A CN 1821195 A CN1821195 A CN 1821195A CN 200610010776 CN200610010776 CN 200610010776 CN 200610010776 A CN200610010776 A CN 200610010776A CN 1821195 A CN1821195 A CN 1821195A
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Abstract
The present invention relates to the synthesis of oxygen containing derivatives of alpha-pinene, and is especially process of synthesizing verbenol and verbenone with alpha-pinene. The process has cationic surfactant ammonium cetyl trimethyl halide as template and ethyl silicate as silicon source, cobalt nitrate as dopping precursor to prepare mesoporous M-MCM-41 molecular sieve under alkaline condition; and oxidizes alpha-pinene selectively at normal pressure with the mesoporous M-MCM-41 molecular sieve as catalyst and oxygen as oxygen source to synthesize verbenol and verbenone. The present invention has alpha-pinene converting rate up to 97.17 % and total selectivity up to 65 %, obviously higher than that of available technology.
Description
Affiliated technical field
The invention belongs to the synthetic method of the containing oxygen derivative of α-Pai Xi, particularly relate to the method for mesopore molecular sieve of utilizing as synthetic verbenol of catalyzer and verbenone.
Background technology
Verbenol (4,6,6-trimethylammonium dicyclo [3.1.1]-3-heptene-2-alcohol), verbenone (4,6,6-trimethylammonium dicyclo [3.1.1]-3-hepten-2-one) are the containing oxygen derivatives of α-Pai Xi, in the middle of organic synthesis and chemical industry important use are arranged.For example, in recent years, utilize verbenol and verbenone to prevent and treat the dried insect of post-Song bark beetle of serious harm Pinus seeds as pheromone at the western loose bark beetle (Dedroctonusbreviscomis) of North America, dendroctonus frontalis (D.frontalis), the red wing bark beetle of dragon spruce (D.pseudotsugae) and pinus yunnanensis vertical pit cutting pin small moth (Tomicus piniperda), can avoid the chemical pesticide pollution on the environment, and obtain positive effect.
Be oxidized in alcohol, the reactive ketone at traditional alkene, α-Pai Xi oxidizing reaction custom catalysts is as Manganse Dioxide (MnO
2), chromium trioxide (CrO
3) all have certain catalytic oxidation performance (the Han Guang pasture, Zhao Shuwei, Li Shuwen, etc. organic preparation chemistry handbook (in) [M]. Beijing: petrochemical industry press, 1977.).
Verbenol (4,6,6-trimethylammonium dicyclo [3.1.1]-3-heptene-2-alcohol), verbenone (4,6,6-trimethylammonium dicyclo [3.1.1]-3-hepten-2-one) be the containing oxygen derivative of α-Pai Xi, report is arranged during they synthetic, usually the catalyzer that adopts is loose ester acid cobalt, productive rate is respectively 13.6% and 35.6%, overall selectivity be 35% (the high bamboo grove Zhou Nan of Yin Caixia etc. the synthetic and biological activity determination of loose bark beetle pheromone α-Pai Xi containing oxygen derivative. Yunnan University's journal (natural science edition) 2001,23 (2): 132～134).The transformation efficiency of α-Pai Xi is not high, and total selectivity is also undesirable.Therefore, develop a kind of synthetic verbenol of high conversion highly selective and the very big challenge that verbenone remains the present technique field.
MCM-41 is that (Am.Chem.Soc 1992.114 for people such as Kresge, 10834) the hole silicon controlled rectifier hydrochlorate of a kind of organic formwork assembling of invention, it forms the characteristics of vesica easily by surfactant molecule, template as mesopore molecular sieve, form micella or micell in the aqueous solution, tetraethoxysilance hydrolysis dissolving generates SiO
4 4-Form inorganic wall round micella or micell, be sintered into six side's phase structures again, have the mesoporous nano duct of one-dimensional linear and homogeneous.Because mesoporous limitation of size, add that inner duct can carry out chemically modified by ion-exchange, MCM-41 can carry out selectivity molecular diffusion and the absorption in the hole, its high-specific surface area and relative good thermostability and good selectivity and permeability, demonstrate good prospects for application at catalysis, absorption, separation field, especially the mesopore orbit of mesoporous material homogeneous is well suited for the reaction that organic macromolecule participates in or generates, and can realize that bulky molecular catalysis transforms.
Summary of the invention
The objective of the invention is to develop a kind of synthetic verbenol of high conversion highly selective and the method for verbenone.
The present invention realizes above-mentioned purpose by the following method:
It is characterized in that α-Pai Xi, transitional metal ion Co, the adulterated MCM-41 catalyzer of Mn, Ni are added container successively, separate, collect verbenol and verbenone after aerating oxygen between 60～80 ℃, question response finish.
Described α-Pai Xi is 1: 0.02～0.08 with transitional metal ion Co, the adulterated MCM-41 catalyst quality ratio of Mn, Ni.
Transitional metal ion Co, the adulterated MCM-41 catalyzer of Mn, Ni, be to utilize cats product cetyl trimethyl ammonium halide to be template, tetraethoxy is the silicon source, and the strong acid salt of Co, Mn, Ni is the doping precursor, and alkaline condition is the mesoporous M-MCM-41 molecular sieve of preparation down.
The temperature of reaction of synthetic verbenol of described α-Pai Xi and verbenone is 60-80 ℃, and the reaction times is 3～11h.
Particularly, when catalyzer was the Co doping MCM-41, temperature was 75-80 ℃, and the reaction times is 6-9h.
The present invention is with an amount of transition metal ion, Co, Mn, Ni are entrained in catalyzed oxidation α-Pai Xi reaction in the mesoporous material, be proved to be gating catalytic oxidation is had good performance, the transformation efficiency of α-Pai Xi reaches 97.17%, the selectivity of verbenol and verbenone can reach more than 65%, has fairly obviously than traditional method and improves.For this reason, the present invention has great importance and application prospect in this technical field.
Embodiment
In the there-necked flask that water distilling apparatus, thermometer, magnetic stirring apparatus are housed, add Simao, 10g Yunnan high-quality turps (α-Pai Xi contains 92.6%) and 0.1-0.8g M-MCM-41 catalyzer, stir, and with the flow velocity aerating oxygen of 1000-1200mL/min, temperature of reaction is controlled at 60～80 ℃ of desired values, and cooling back filtration catalizer gets faint yellow liquid phase crude product.Analyze verbenol and verbenone and unconverted α-Pai Xi peak area and some other by products as can be known through GC-MS.Experiment parameter and result such as following table:
Temperature, time and catalyzer and reaction experiment be table as a result
| Numbering | Catalyzer | Temperature ℃ | Time (h) | Catalyzer (g) | Product content % | Selectivity | |||
| 1 | 2 | 1 | 2 | Always | |||||
| 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 | Ni-MCM-41 Co-MCM-41 Co-MCM-41 Co-MCM-41 Mn-MCM-41 Mn-MCM-41 Co-MCM-41 Co-MCM-41 Co-MCM-41 Co-MCM-41 Ni-MCM-41 Mn-MCM-41 Co-MCM-41 Co-MCM 41 Co-MCM-41 Mn-MCM-41 do not have | 60 60 60 60 60 70 70 70 70 70 75 80 80 80 80 80 70-75 | 3 5 7 9 11 2 4 6 9 10 11 3 5 7 9 11 7 | 0.1 0.2 0.2 0.8 0.2 0.2 0.2 0.2 0.2 0.3 0.4 0.2 0.2 0.2 0.3 0.2 0 | 16.70 22.80 20.83 20.72 20.05 7.63 26.12 25.60 26.61 20.15 12.06 22.96 24.69 19.08 13.52 2.57 0 | 16.98 16.24 14.25 20.62 18.17 - 27.15 21.57 24.73 24.00 37.82 18.29 19.61 39.25 40.45 47.20 0 | 18.63 25.43 23.23 23.11 26.83 8.55 29.14 28.60 29.68 22.48 13.45 25.61 27.54 21.28 15.08 2.87 0 | 18.94 18.11 15.90 23.00 20.27 - 30.28 24.06 27.59 26.77 42.19 20.40 21.87 43.78 45.12 52.65 0 | 37.57 43.54 39.13 46.11 47.10 - 59.42 52.66 57.27 49.35 55.65 46.01 49.41 65.06 60.20 55.52 0 |
Last table is 1 verbenol in product content % and selectivity hurdle, and 2 is verbenone, and M-MCM-41 represents Co, Ni, Mn mesopore molecular sieve respectively in catalyst column.
Claims (4)
1, the method for synthetic verbenol of a kind of α-Pai Xi and verbenone, it is characterized in that α-Pai Xi, transitional metal ion Co, the adulterated MCM-41 catalyzer of Mn, Ni are added container successively, after finishing, aerating oxygen between 60～80 ℃, question response separate, collect verbenol and verbenone.
2, the method for synthetic verbenol of α-Pai Xi according to claim 1 and verbenone is characterized in that α-Pai Xi and transitional metal ion Co, the adulterated MCM-41 catalyst quality ratio of Mn, Ni are 1: 0.02～0.08.
3, the method for synthetic verbenol of α-Pai Xi according to claim 1 and verbenone is characterized in that temperature of reaction is 60-80 ℃, and the reaction times is 3～11h.
4, the method for synthetic verbenol of α-Pai Xi according to claim 1 and verbenone is characterized in that when catalyzer is the Co doping MCM-41 temperature is 75-80 ℃, and the reaction times is 6-9h.
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| Application Number | Priority Date | Filing Date | Title |
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| CNB2006100107767A CN100408529C (en) | 2006-03-24 | 2006-03-24 | Method for synthesizing verbenol and verbenone with alpha-pinene |
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| CNB2006100107767A CN100408529C (en) | 2006-03-24 | 2006-03-24 | Method for synthesizing verbenol and verbenone with alpha-pinene |
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| CN1821195A true CN1821195A (en) | 2006-08-23 |
| CN100408529C CN100408529C (en) | 2008-08-06 |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863750A (en) * | 2010-06-08 | 2010-10-20 | 中国科学院长春应用化学研究所 | Synthesis method of oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol |
| CN101985415A (en) * | 2010-11-11 | 2011-03-16 | 江南大学 | Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature |
| CN110156566A (en) * | 2019-06-18 | 2019-08-23 | 中国林业科学研究院森林生态环境与保护研究所 | Synthesize the trans- verbenol of (-)-and its enantiomer (+)-trans- verbenol green, simple preparation method |
-
2006
- 2006-03-24 CN CNB2006100107767A patent/CN100408529C/en not_active Expired - Fee Related
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101863750A (en) * | 2010-06-08 | 2010-10-20 | 中国科学院长春应用化学研究所 | Synthesis method of oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol |
| CN101863750B (en) * | 2010-06-08 | 2014-01-08 | 中国科学院长春应用化学研究所 | Synthesis method of oxygen-containing derivative bark beetle pheromone verbena ketene of alpha-pinene and verbenol |
| CN101985415A (en) * | 2010-11-11 | 2011-03-16 | 江南大学 | Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature |
| CN101985415B (en) * | 2010-11-11 | 2013-01-02 | 江南大学 | Preparation method of verbenol and verbenone through air oxidation of a-pinene at room temperature |
| CN110156566A (en) * | 2019-06-18 | 2019-08-23 | 中国林业科学研究院森林生态环境与保护研究所 | Synthesize the trans- verbenol of (-)-and its enantiomer (+)-trans- verbenol green, simple preparation method |
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| CN100408529C (en) | 2008-08-06 |
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Owner name: YUNNAN YUXI YUNXI ESSENCE PERFUME CO., LTD. Free format text: FORMER OWNER: YUNNAN UNIVERSITY Effective date: 20091204 |
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Effective date of registration: 20091204 Address after: Yuxi Hongta Yunnan Gao Cang Industrial Zone Patentee after: Yunan Province Yuxi City Yunxi Essence & Spicery Co., Ltd. Address before: Yunnan Province, Kunming City Lake Road No. 2 Patentee before: Yunnan University |
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