CN103524333B - The preparation method of 2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid - Google Patents
The preparation method of 2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid Download PDFInfo
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- CN103524333B CN103524333B CN201310463751.2A CN201310463751A CN103524333B CN 103524333 B CN103524333 B CN 103524333B CN 201310463751 A CN201310463751 A CN 201310463751A CN 103524333 B CN103524333 B CN 103524333B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/34—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with ozone; by hydrolysis of ozonides
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/16—Systems containing only non-condensed rings with a six-membered ring the ring being unsaturated
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Abstract
The present invention relates to the synthesis field of organic intermediate, disclose a kind of preparation method of 2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid.The inventive method for raw material with 4-oxo-beta-ionone, adds alcohol and water and stirs, and logical ozone carries out ozonization, temperature of reaction controls at-80 ~-20 DEG C, react rear logical nitrogen purge ozone, reclaimed alcohol, add hexanaphthene recrystallization and obtain target product.The advantages such as present invention process route is simple and direct, selectivity good, yield is high, speed of response is fast, aftertreatment is simple meet the trend of current green chemical industry, have industrial value.
Description
Technical field
The present invention relates to the synthesis of important organic intermediate, specifically a kind of preparation method of 2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid.
Background technology
2,6,6-trimethylammonium-3-oxo-cyclohex-1-zinecarboxylic acid is the important intermediate of a class novel plant hormone witchweed element and derivative thereof.Its synthesis mainly contains four kinds of methods.(1) with β-cyclocitral for raw material finally prepares target product (J.Am.Chem.Soc., 1976,98:3661-3668) by Jones reagent oxidation through oxidation, bromination, hydrolysis.(2) with α-cyclocitral for raw material is through the open loop again of benzoyl hydroperoxide epoxidation, finally prepare target product (J.Am.Chem.Soc., 1976,98:3661-3668) by Jones reagent oxidation again.(3) α-ionone is that raw material finally prepares target product (J.Org.Chem., 1985,50 (5): 628-632) by Jones reagent oxidation through benzoyl hydroperoxide epoxidation, ozone oxidation, open loop.(4) being raw material with 1,5,5-trimethylammonium-6-methylenecyclohex alkene finally prepares target product (Tetrahedron.1998,54:2753-2762) through Jones reagent oxidation again through bromination, TMANO oxidation.These method stepss are all long, yield is lower and all will use the larger Jones reagent of expensive pollution, are all difficult to realize industrialization.
Summary of the invention
Problem to be solved by this invention is the defect overcoming the existence of above-mentioned prior art, provides the preparation method of 2,6, the 6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acids that a kind of synthetic route is simple and direct, yield is high, cost is low.
In order to solve the problems of the technologies described above, the present invention is solved by following technical proposals:
The present invention adopts following technical scheme: with 4-oxo-beta-ionone for raw material obtains target product 2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid through ozone oxidation in alcohol-water solution, synthetic route is as follows:
Particularly, the inventive method for raw material with 4-oxo-beta-ionone, adds alcohol and water and stirs, logical ozone carries out ozonization, and temperature of reaction controls at-80 ~-20 DEG C, has reacted rear logical nitrogen purge ozone, reclaim alcohol, add hexanaphthene recrystallization and obtain target product.This operational path is simple and direct, selectivity good, yield is high, speed of response is fast, and aftertreatment is simple, is applicable to large-scale industrial production.
As preferably, described alcohol adopts methyl alcohol, ethanol or Virahol.Methyl alcohol, ethanol or Virahol are comparatively cheap, are conducive to reducing costs.
As preferably, the mole dosage of the described water added be the 1.0-3.0 of 4-oxo-beta-ionone mole dosage doubly.
As preferably, described recovery alcohol process adopts normal pressure or water pump reclaim under reduced pressure.
Above-mentioned reaction raw materials 4-oxo-beta-ionone is provided by Zhejiang Medicine Co, also can according to document preparations such as [fragrance flavor and cosmetic, 2010, (3), 3-5] and US4209450.
The present invention, owing to have employed above technical scheme, has significant technique effect:
The present invention with 4-oxo-beta-ionone for raw material obtains target product 2 through ozone oxidation in alcohol-water solution, 6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid, the advantages such as this operational path is simple and direct, selectivity good, yield is high, speed of response is fast, aftertreatment is simple meet the trend of current green chemical industry, have industrial value.
Embodiment
Below in conjunction with specific embodiment, the present invention is described in further detail:
The instrument and equipment used in following examples: ozonizer, GF-G-3-010G(Qingdao Guolin Industry Co., Ltd.); Nuclear magnetic resonance analyser, mark in AVANCEDMX II I 400M(TMS, Bruker company); Liquid chromatography, Agilent company of the AgilentHPLC1200(U.S.).
Embodiment 1
61.8 grams of 4-oxo-beta-ionones (0.3mol) and 200 ml methanol and 3.6 grams of water are joined in 500mL four-hole bottle, mechanical stirring is at-80 DEG C, ozonization is carried out after regulating oxygen flow, gas-chromatography follows the tracks of reaction, within about 2 hours, raw material disappears, and reaction terminates to stop ozonize.Ozone in reaction flask is caught up with by logical nitrogen, after normal pressure reclaims dry methyl alcohol, adds 250 milliliters of hexanaphthene recrystallizations and obtains faint yellow solid 50.2 grams, liquid content 98.1%, yield 90.2%.Above-mentioned operational path is simple and direct, selectivity good, yield is high, speed of response is fast, aftertreatment is simple, has industrial value.
Product structure confirms:
1HNMR(δppm,400MHz,CDCl
3):1.315(s,6H,2CH
3),1.829(s,3H,CH
3),1.938(t,J=6.8Hz,2H,CH
2),2.584(t,J=6.8Hz,2H,CH
2).
13CNMR(δppm,100MHz,CDCl
3):16.91,27.86,34.51,36.14,37.84,142.59,150.15,170.24,197.42
Embodiment 2
61.8 grams of 4-oxo-beta-ionones (0.3mol) and 200 milliliters of ethanol and 5.4 grams of water are joined in 500mL four-hole bottle, mechanical stirring is at-40 DEG C, ozonization is carried out after regulating oxygen flow, gas-chromatography follows the tracks of reaction, within about 1.5 hours, raw material disappears, and reaction terminates to stop ozonize.Ozone in reaction flask is caught up with by logical nitrogen, after the dry ethanol of water pump reclaim under reduced pressure, adds 250 milliliters of hexanaphthene recrystallizations and obtains faint yellow solid 48.5 grams, liquid content 98.6%, yield 87.6%.Product nuclear magnetic spectrogram is identical with embodiment 1.
Embodiment 3
61.8 grams of 4-oxo-beta-ionones (0.3mol) and 200 milliliters of Virahols and 1.8 grams of water are joined in 500mL four-hole bottle, mechanical stirring is at-20 DEG C, ozonization is carried out after regulating oxygen flow, gas-chromatography follows the tracks of reaction, within about 1.5 hours, raw material disappears, and reaction terminates to stop ozonize.Ozone in reaction flask is caught up with by logical nitrogen, after the dry Virahol of water pump reclaim under reduced pressure, adds 250 milliliters of hexanaphthene recrystallizations and obtains faint yellow solid 48.1 grams, liquid content 97.3%, yield 85.7%.Product nuclear magnetic spectrogram is identical with embodiment 1.
In a word, the foregoing is only preferred embodiment of the present invention, all equalizations done according to the present patent application the scope of the claims change and modify, and all should belong to the covering scope of patent of the present invention.
Claims (2)
- The preparation method of 1.2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid, it is characterized in that, method is as follows:With 4-oxo-beta-ionone for raw material, add alcohol and water and stir, logical ozone carries out ozonization, and temperature of reaction controls at-80 DEG C, and reaction 2h, has reacted rear logical nitrogen purge ozone, reclaims alcohol, adds hexanaphthene recrystallization and obtain target product; Described alcohol adopts methyl alcohol, ethanol or Virahol; The mole dosage of the described water added is 1.0-3.0 times of 4-oxo-beta-ionone mole dosage.
- 2. the preparation method of 2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acids according to claim 1, is characterized in that: described recovery alcohol process adopts water pump normal pressure or reclaim under reduced pressure.
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| CN201310463751.2A CN103524333B (en) | 2013-10-08 | 2013-10-08 | The preparation method of 2,6,6-trimethylammonium-3-oxo-1-cyclohexenecarboxylic acid |
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| β-环柠檬醛的合成;和承尧 等;《云南化工》;20040229;第31卷(第1期);第1-5页 * |
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