CN103922912A - Novel method of preparing isolongifolenone - Google Patents
Novel method of preparing isolongifolenone Download PDFInfo
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- CN103922912A CN103922912A CN201410179304.9A CN201410179304A CN103922912A CN 103922912 A CN103922912 A CN 103922912A CN 201410179304 A CN201410179304 A CN 201410179304A CN 103922912 A CN103922912 A CN 103922912A
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- isolongifolenone
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/28—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of CHx-moieties
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2603/00—Systems containing at least three condensed rings
- C07C2603/93—Spiro compounds
- C07C2603/95—Spiro compounds containing "not free" spiro atoms
- C07C2603/96—Spiro compounds containing "not free" spiro atoms containing at least one ring with less than six members
- C07C2603/97—Spiro compounds containing "not free" spiro atoms containing at least one ring with less than six members containing five-membered rings
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Abstract
The invention discloses a novel method of preparing isolongifolenone. The method comprises the following steps: by taking isolongifolene (an isomerized product of longifolene) as a raw material, copper power as a catalyst, tertiary butanol as a solvent and tert-butyl hydroperoxide as an oxidizing agent, oxidizing the longifolene in one step to obtain isolongifolenone; at the end of reaction, filtering out the copper powder; evaporating out tertiary butanol at normal pressure; and then carrying out reduced pressure distillation and collecting an isolongifolenone fraction. The novel method disclosed by the invention is simple in operating process, strong in oxidizing selectivity and good in catalytic effect. The catalyst and the solvent can be repeatedly used, and the catalyst is low in price and abundant. The novel method overcomes the deficiencies of existing preparation methods,such as expensive catalysts, complex process and poor reaction selectivity.
Description
Technical field
The invention belongs to organic compound technical field, be specifically related to a kind of novel method of preparing different rare ketone that comes into leaves.
Background technology
Isolongifolenone is a kind of spices that has very much using value, has strong fragrant and sweet, the banksia rose, and with amber aroma and slight camphor fragrance breath.Industrial, Isolongifolenone is a kind of important sesquiterpenoids, and Isolongifolenone and derivative thereof have been used in space sprays, makeup, washing composition, reodorant, fabric, cellulosic and paper product.In addition, Isolongifolenone and derivative thereof have been found effectively to suppress the activity of TYR enzyme, are considered to clinically effectively tyrosinase inhibitor, are used for the treatment of some due to the calm skin blackspot causing of melanism.In addition, saturated Isolongifolenone has been used as the estrogenic part of preparation chirality, for prevention and treatment mammary cancer, and the hormonal surrogate of hormone in climacteric.In recent years the research for Isolongifolenone has had again new development, and experiment finds that it has good expulsion mosquito effect, and effect is better than conventional Metadelphene at present, and safety non-toxic, as novel wormer, has considerable market outlook.
The method of the synthetic Isolongifolenone of bibliographical information Isolongifolene has following several diverse ways.Liu Zhen etc. are with the air oxidation process of organic cobalt salt or the catalysis of manganese salt, at 30 ~ 120 ℃, and blowing air oxidizing reaction 12 ~ 60h, Isolongifolenone productive rate can reach 80%.But higher to equipment requirements, and the reaction times is longer.Homemade polydimethylsiloxane/the polysulfones of employing (PDMS/PSF) composite membranes such as military French are prepared oxygen-rich air, and oxidation Isolongifolene is prepared Isolongifolenone.But Isolongifolenone yield is only 59.8%, and the need of production specific equipment oxygen enricher of oxygen enrichment, its price comparison is expensive, and cost of use is also higher, causes the production cost of Isolongifolenone also higher.Zhang Aijuns etc. be take tertbutyl peroxide as oxygenant, and Chromium hexacarbonyl is catalyzer, the 2 ~ 4h that refluxes in acetonitrile-benzene mixed solvent, and the transformation efficiency of Isolongifolene can reach 100%, and the yield of Isolongifolenone is greater than 82%.But catalyzer six cobalt-carbonyls easily distil and are bonded at and are attached to the condensation mouth of pipe in reaction process, reuse difficulty.And catalyzer price is high, the solvent acetonitrile of use and benzene are all toxic, unfriendly to environment.CHEN Weiqiangs etc. are usingd cobaltous acetate as catalyzer, with air oxidant oxidation Isolongifolene, make Isolongifolenone, but the reaction times are oversize, reach 48 h, and yield are also on the low side.For this reason, exploring new synthetic route and synthetic method is one of research direction of synthetic Isolongifolenone.
Summary of the invention
Goal of the invention: for the deficiencies in the prior art, the object of this invention is to provide a kind of novel method of preparing Isolongifolenone, to make it have simple, with low cost, the good product quality of preparation and yield advantages of higher.
Technical scheme: in order to realize foregoing invention object, the technical solution used in the present invention is as follows:
A novel method of preparing Isolongifolenone, take different come into leaves rare as raw material, with copper powder make catalyzer, take the trimethyl carbinol as solvent, take tertbutyl peroxide as oxygenant, Isolongifolene oxidation step is obtained to Isolongifolenone.
The described novel method of preparing Isolongifolenone, is specially: different rare, copper powder and the t-butanol solvent of coming into leaves added respectively in reactor, be heated to while stirring reflux state, drip the t-butanol solution of tertbutyl peroxide, drip off rear continuation reaction.Reaction solution reclaims after catalyzer after filtration, under normal pressure, steams the trimethyl carbinol.Last underpressure distillation, collects different rare ketone cut that comes into leaves, then through freezing and crystallizing, obtains pale yellow crystals Isolongifolenone.
Concrete reaction scheme is:
A kind of novel method of preparing Isolongifolenone, in the four-hole boiling flask that thermometer, agitator, reflux exchanger and constant voltage feed hopper are housed, add Isolongifolene, catalysts and solvents, heated and stirred is to backflow, utilize constant voltage feed hopper slowly to drip tertbutyl peroxide, carry out oxidizing reaction 6-12 h.After reaction finishes, reclaim after filtration catalyzer, filtrate is under normal pressure after distillating recovering solvent, carry out rectification under vacuum, the cut of collecting 172 ~ 190 ℃/7300KPa is Isolongifolenone cut again, then through freezing and crystallizing, obtain pale yellow crystals Isolongifolenone, purity is 98.57%, and fusing point is 47.5 ℃, specific rotatory power
.EI-MS（m/z）：218（M
+，50），175（100），147（60），119（30），91（37），91（37），55（11）。
Beneficial effect: compared with prior art, advantage of the present invention comprises: the present invention adopts solid Cu catalyzer and the trimethyl carbinol to make solvent, have that catalyst recovery is easy and catalytic efficiency is high, solvent is nontoxic and the rate of recovery is high, has overcome and has adopted the high Cr (CO) of price
6catalyzer and poisonous CH
3cN/C
6h
6solvent system; Compare with air oxidation process, yield and the reaction preference of product significantly improve.
Embodiment
Below in conjunction with specific embodiment, the present invention is described further.
Embodiment 1
In being furnished with the 50mL there-necked flask of magnetic stirring apparatus, thermometer and prolong, add respectively 5.10g different come into leaves rare, 0.15g copper powder, 5.1g the trimethyl carbinol, be heated with stirring to backflow, with constant pressure funnel, drip 10.4g tertbutyl peroxide, under reflux state, react 12h.By GC, follow the tracks of detection, transformation efficiency 100%, selectivity 93.39%.Reaction solution reclaims after catalyzer after filtration, under normal pressure, steams the trimethyl carbinol; Last underpressure distillation, collects different rare ketone cut that comes into leaves, then through freezing and crystallizing, obtains pale yellow crystals Isolongifolenone.
Embodiment 2
To being furnished with in the 250mL there-necked flask of magnetic agitation, thermometer and prolong, add respectively 20.4g different come into leaves rare, 0.62g copper powder, the 100g trimethyl carbinol, be heated with stirring to backflow, with constant pressure funnel, drip 10.4g tertbutyl peroxide, under reflux state, react 12h.By GC, follow the tracks of detection, transformation efficiency 100%, selectivity 92.99%.Reaction solution reclaims after catalyzer after filtration, under normal pressure, steams the trimethyl carbinol; Last underpressure distillation, collects different rare ketone cut that comes into leaves, then through freezing and crystallizing, obtains pale yellow crystals Isolongifolenone.
Comparative example 1
In being furnished with the 250mL there-necked flask of agitator, thermometer, reflux condensing tube and air airway, add 20.4g Isolongifolene, 0.45g catalyst acetic acid cobalt, 100mL benzene, pass into through the dried air of the vitriol oil, air flow quantity is 200mL/min, under 60 ℃ of conditions, reacts 12h.By GC, following the tracks of detection transformation efficiency is 22.9%, selectivity 56.3%.Reaction solution cooled and filtered is removed catalyzer, vacuum distillation recovered solvent, and raffinate uses 5% sodium bicarbonate aqueous solution (50mL * 3) and water (50mL * 3) washing to neutral successively, and dry rear underpressure distillation, collects Isolongifolenone cut.
Comparative example 2
In being furnished with the 250mL there-necked flask of agitator, thermometer, reflux condensing tube, add 20.4g Isolongifolene, 11g Chromium hexacarbonyl, 150mL acetonitrile, refluxes the reaction mixture of gained slowly, dropwise drips 41.6g tertbutyl peroxide, reaction 3.5h.By GC, detected transformation efficiency 100%, selectivity 93%.Reaction mixture is cooled to room temperature, by a sinter funnel, filters.After cold benzene for the throw out of Chromium hexacarbonyl (30 * 4mL) washing, reclaim.Filtrate and benzene washings are merged, with hexanaphthene (50mL) dilution, then water (30 * 5 milliliters) and salt water washing, then use anhydrous Na
2s0
4be dried.Remove again solvent under reduced pressure, collect different rare ketone cut that comes into leaves, then through freezing and crystallizing, obtain pale yellow crystals Isolongifolenone.
Comparative example 3
In being furnished with the 250mL there-necked flask of agitator, thermometer, reflux condensing tube, add 20.4g Isolongifolene, 0.41g CuO is catalyzer, the 100g trimethyl carbinol, be heated with stirring to backflow, with constant pressure funnel, drip 10.4g tertbutyl peroxide, under reflux state, react 12h.By GC, follow the tracks of detection, transformation efficiency 90.0%, selectivity 83.3%.Reaction solution reclaims after catalyzer after filtration, under normal pressure, steams the trimethyl carbinol; Last underpressure distillation, collects different rare ketone cut that comes into leaves.
Comparative example 4
In being furnished with the 250mL there-necked flask of agitator, thermometer, reflux condensing tube, add 20.4g Isolongifolene, 0.62g CuSO
4for catalyzer, 100g acetonitrile, is heated with stirring to backflow, with constant pressure funnel, drips 10.4g tertbutyl peroxide, under reflux state, reacts 13h.By GC, follow the tracks of detection, transformation efficiency 2.4%, selectivity 41.7%.Reaction solution reclaims after catalyzer after filtration, under normal pressure, steams the trimethyl carbinol; Last underpressure distillation, collects different rare ketone cut that comes into leaves.
Comparative example 5
To being furnished with in the 250mL there-necked flask of magnetic agitation, thermometer and prolong, add respectively 20.4g different come into leaves rare, 0.62g copper powder, the 100g trimethyl carbinol, is heated with stirring to backflow, with the low liquid funnel of constant voltage, drips 4.25g(75mmol, 60%) hydrogen peroxide reacts 12h under reflux state.By GC, follow the tracks of detection, transformation efficiency 25.7%, selectivity 60.0%.Reaction solution reclaims after catalyzer after filtration, under normal pressure, steams the trimethyl carbinol; Last underpressure distillation, collects different rare ketone cut that comes into leaves.
Claims (4)
1. a novel method of preparing Isolongifolenone, is characterized in that: take different come into leaves rare as raw material, with copper powder make catalyzer, take the trimethyl carbinol as solvent, take tertbutyl peroxide as oxygenant, Isolongifolene oxidation step is obtained to Isolongifolenone.
2. the novel method of preparing Isolongifolenone according to claim 1, it is characterized in that: different rare, copper powder and the t-butanol solvent of coming into leaves added respectively in reactor, be heated to while stirring reflux state, the t-butanol solution that adds tertbutyl peroxide by constant voltage dropping liquid drip, drips off rear continuation reaction; Reaction solution reclaims after catalyzer after filtration, under normal pressure, steams the trimethyl carbinol; Last underpressure distillation, collects different rare ketone cut that comes into leaves, then through freezing and crystallizing, obtains pale yellow crystals Isolongifolenone.
3. the novel method of preparing Isolongifolenone according to claim 1 and 2, is characterized in that: the reaction times is 6-12h.
4. the novel method of preparing Isolongifolenone according to claim 2, is characterized in that: collecting Isolongifolenone cut is the cut of 172 ~ 190 ℃/7300KPa.
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| CN201410179304.9A CN103922912B (en) | 2014-04-30 | 2014-04-30 | A kind of method preparing different rare ketone that comes into leaves |
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| CN201410179304.9A CN103922912B (en) | 2014-04-30 | 2014-04-30 | A kind of method preparing different rare ketone that comes into leaves |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187722A (en) * | 2016-06-27 | 2016-12-07 | 广西梧松林化集团有限公司 | The production method of Isolongifolenone |
| CN113511963A (en) * | 2021-04-20 | 2021-10-19 | 金溪华香香料有限公司 | Efficient green environment-friendly isolongifolanone synthesis method |
Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101801901A (en) * | 2007-07-13 | 2010-08-11 | 美国农业部 | Use Isolongifolene ketone and/or the arthropodan method of Isolongifolene keto analog repellent |
-
2014
- 2014-04-30 CN CN201410179304.9A patent/CN103922912B/en not_active Expired - Fee Related
Patent Citations (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101801901A (en) * | 2007-07-13 | 2010-08-11 | 美国农业部 | Use Isolongifolene ketone and/or the arthropodan method of Isolongifolene keto analog repellent |
Non-Patent Citations (1)
| Title |
|---|
| 刘震等: "异长叶烯的空气催化氧化反应", 《林产化学与工业》, vol. 17, no. 2, 30 June 1997 (1997-06-30), pages 1 - 6 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106187722A (en) * | 2016-06-27 | 2016-12-07 | 广西梧松林化集团有限公司 | The production method of Isolongifolenone |
| CN113511963A (en) * | 2021-04-20 | 2021-10-19 | 金溪华香香料有限公司 | Efficient green environment-friendly isolongifolanone synthesis method |
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