CN102225885A - Method for increasing optical purity of alpha-terpineol - Google Patents
Method for increasing optical purity of alpha-terpineol Download PDFInfo
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Abstract
The invention discloses a method for increasing optical activity of alpha-terpineol, which uses a racemate of alpha-terpineol or alpha-terpineol with low optical activity as a raw material, and cheap chiral dehydroabietylamine as a resolving agent, and performs resolution by an inclusion resolution method to obtain both laevorotary alpha-terpineol and a certain amount of dextral alpha-terpineol. The resolving agent of dehydroabietylamine used in the invention can be obtained by separating and purifying rosin oil, and is cheap and easily available; the resolution process has simple operations, and all the resolving agent, the solvent and the eluent can be recycled and reused; the method has low cost, no pollution, and is applicable to industrial production; because of the reproducibility and the low toxicity of terpineol, the product of the invention can be widely used as a green synergist for common agricultural emulsifiable or aqua pesticides, herbicides, and bactericides.
Description
Technical field
The present invention relates to a kind of method for splitting of chiral material.More specifically say so and alpha-terpineol is split as the method for left-handed alpha-terpineol and dextrorotation alpha-terpineol.
Background technology
Terpineol 350 claims terpinol again, it is a kind of monocyclic monoterpene alcohol compound, be the colourless extremely slightly liquid or the transparent crystallization of viscosity of little yellow, have α-, β-, γ-three kind of isomer, wherein alpha-terpineol is the most common at nature, it is the monoterpene alcohol that contains a chiral carbon atom in the molecule, and its left and right body that revolves can extract from different plants essential oils respectively.The optical activity of alpha-terpineol determines it to have different effects, and on as spices, levo form is cooler, and dextrorotatory form is clear partially, on medicinal very big difference is arranged also, and the parasitic energy of dextrorotatory form alpha-terpineol trapping force rate levo form is much better than.And commercially available commodity Terpineol 350 is a kind of racemic modification Terpineol 350 based on alpha-terpineol mostly, and quality is only decided with the content of alpha-terpineol, does not make full use of its optically-active characteristic.Though the synthetic report of optical activity alpha-terpineol is arranged in recent years, discloses a kind of method of utilizing mordenite as the synthetic dextrorotation alpha-terpineol of catalyzer one step catalysis as [ZL 90104026] such as Xiao Shude; It is catalyzer that Huang Kelin etc. [ZL03178548.4] disclose a kind of spent ion exchange resin, in the method for the synthetic left-handed alpha-terpineol of fixed bed previous step catalysis, and find that left-handed alpha-terpineol has the activity stronger than the raceme alpha-terpineol at aspects such as agricultural insecticidal, sterilization, health degerming, mosquito repellings.But the optical purity of the alpha-terpineol that synthetic method obtained of above-mentioned disclosed optical activity alpha-terpineol is all not high, therefore, in order to give full play to the activity of left-handed alpha-terpineol, be necessary to adopt a kind of simple method to obtain the alpha-terpineol of high optical activity at aspects such as agricultural insecticidal, sterilization, health degerming, mosquito repellings.
Dehydroabietylamine is the major ingredient of the converted products nilox resin of natural rosin, can from nilox resin, extract, because it has optical activity, and stable in properties, and the source is abundant, extraction is easy, successfully is used for the fractionation of multiple racemize material.[US 2585436] such as nineteen fifty-two Cannon L C successfully apply to dehydroabietylamine the production of microbiotic penicillin; 1976 [US 3969397] such as Kalser A report is used for the production of the many fragrant plants of L; 1985 [US 4559178A] such as Buzby Jr George C report is used for splitting 3-thiobenzoyl-2 Methylpropionic acid; Fritz in 1987. report such as lining good fortune [CN 85106365A] is used for splitting D (+) vitamin H key intermediate 1,3-dibenzyl six hydrogen-1H-furo (3,4-d) imidazoles-2,4-diketone; Report such as nineteen ninety B Kohl [EP 386654] is used for splitting optical activity medicine intermediate 2-(ω-phenoxyalkyl) epoxy carboxylic acid.1994 [US 5280122A] such as Chiu Charles K report is used for splitting 2-benzyl-4-piperidone Succinic Acid.Calendar year 2001 woods Guoqiang etc. [CN 01113303] reported and has been used for splitting preparation optically pure 2-fluoro-Alpha-Methyl-[1, the 1-phenylbenzene]-4-acetate, and this method is not only easy, and productive rate height, cost are low, and split fully, are suitable for suitability for industrialized production.2007 [Tetrahedron Asymmetry, 2007,18 (9): 1038-1041] such as Bolchi C have reported that being used for splitting 2-replaces-1,4-benzo dioxane; Cypress one intelligent grade [journal of Zhejiang university (engineering version) 2008,42 (4): 702-706] report was used for splitting 6-fluoro-3,4-dihydro-2H-1-chromene-2-formic acid in 2008.Yellow spring in 2010 [fine chemistry industry 2010, Vol27, N01:57-59] report such as woods is used for splitting 1,1 '-union-2-naphthol.But up to the present, also less than report about alpha-terpineol fractionation aspect.
Summary of the invention
The object of the present invention is to provide a kind of simple to operate, optically active novel method of raising alpha-terpineol that cost is low, specifically be meant and adopt the inclusion Split Method raceme or the low alpha-terpineol of optical activity to be split as the method for left-handed alpha-terpineol and dextrorotation alpha-terpineol.
Technical scheme of the present invention is:
At first respectively a certain amount of raceme or the low alpha-terpineol of optical activity are dissolved in the solvent, wait to dissolve complete back and add resolving agent, reflux 1～3 hour, temperature of reaction is not less than the boiling point of solvent for use, room temperature left standstill 24～48 hours, filtered, and obtained filtrate A and filter residue B.
Underpressure distillation filtrate A reclaims solvent, and is remaining for being mixed with the faint yellow crystallisate C of thick liquid, thick liquid for not with resolving agent bonded alpha-terpineol, the complexing inclusion complex that faint yellow crystallisate C is left-handed alpha-terpineol and dehydroabietylamine.The solvent that underpressure distillation is collected can be collected recycling.
The faint yellow crystallisate C that obtains is dissolved in the eluent, and stirring at normal temperature 0.5～1.5 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor then is respectively the left-handed alpha-terpineol of resolved product that the present invention obtains.
Filter residue B is with identical solvent wash, and obtaining sediment D is the complexing inclusion complex of dextrorotation alpha-terpineol and dehydroabietylamine.
The sediment D that obtains is dissolved in the eluent, and stirring at normal temperature 0.5～1.5 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor then is respectively the fractionation by product dextrorotation alpha-terpineol that the present invention obtains.
The specific rotatory power of the left-handed alpha-terpineol of resolved product [α]
D 20Value is-40 °～-70 °, and the e.e value is 38～65%, and yield is 65～72% (in the theoretical values of left-handed alpha-terpineol); The specific rotatory power of dextrorotation alpha-terpineol [α]
D 20Value is+45 °～+ 75 °, and the e.e value is 41～70%, yield 45～55% (in the theoretical value of dextrorotation alpha-terpineol).
Merge the upper strata eluent layer that phase-splitting obtains, eluent is reclaimed in underpressure distillation, obtains xanchromatic resolving agent dehydroabietylamine crystal, dehydroabietylamine crystal recrystallization 1～2 time in corresponding eluent.The eluent that underpressure distillation is collected and the resolving agent dehydroabietylamine of recovery can be reused and not influence result of use.
Described resolving agent is the optical purity dehydroabietylamine, its specific rotatory power [α]
D 20=+56.1 °, the e.e value is 95～98%, and the mol ratio of dehydroabietylamine and raw material alpha-terpineol or left-handed alpha-terpineol is 0.7～1.1: 1;
Described solvent is C
1-4The low-carbon (LC) alcohols, a kind of or their mixture as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol etc., the consumption of solvent is 3～8 times of raw material alpha-terpineol volume.
Described eluent is a kind of of tetracol phenixin, toluene, dimethylbenzene, hexanaphthene and normal hexane or their mixture, and the consumption of eluent is to treat 2～8 times of eluate weight.
Advantage of the present invention:
The present invention is a resolving agent with chirality dehydroabietylamine cheap and easy to get, by the inclusion Split Method, once raceme or the low alpha-terpineol of optical activity is split as specific rotatory power [α]
D 20Value is-40 °～-70 °, and the e.e value is 38～65% left-handed alpha-terpineol and specific rotatory power [α]
D 20Value is+45 °～+ 75 °, and the e.e value is 41～70% dextrorotatory form alpha-terpineol.Do not influence result of use because used solvent, eluent, resolving agent are all reusable, have easy and simple to handle, aftertreatment is simple, cost is low, " three wastes " less, be fit to the advantage of suitability for industrialized production, again because the recyclability and the hypotoxicity of Terpineol 350, so product of the present invention can be used as the green synergistic agent of common agricultural missible oil class or aqua insecticides, weedicide, degerming agent and can be extensive use of.
Embodiment
In order to understand the present invention better, further set forth below in conjunction with embodiment, but these embodiment should not be construed as any limitation of the invention.
Embodiment 1
Taking by weighing the alpha-terpineol total content is 98%, specific rotatory power [α]
D 20=-23.6 °, the e.e value is that 22% the optically active left-handed alpha-terpineol 31.4g (0.2mol) that has is dissolved in the 105ml dehydrated alcohol, wait to dissolve complete back and add 39.9g (0.14mol) chirality dehydroabietylamine, 82 ℃ of left and right sides heating reflux reactions 1 hour, room temperature left standstill 24 hours, filter to get filtrate A and deposit B are with a small amount of absolute ethanol washing precipitation.
The deposit B that obtains after the washing is dissolved in the 50ml toluene eluent, and stirring at normal temperature 0.5 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 8.45g, is the dextrorotatory form alpha-terpineol, its [α]
D 20=+74.1 °, the e.e value is 68.9%, is 48.5% based on the yield of dextrorotation alpha-terpineol theoretical value.
The filtrate A vacuum distillation recovered solvent dehydrated alcohol that above-mentioned filtration obtains, add 90ml toluene eluent, stirring at normal temperature 0.5 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 20.29g, is the levo form alpha-terpineol, its [α]
D 20=-65.1 °, the e.e value is 61.3%, is 66.2% based on the yield of left-handed alpha-terpineol theoretical value.
Merge the upper strata eluent layer that above-mentioned twice phase-splitting collected, underpressure distillation obtains xanchromatic resolving agent dehydroabietylamine crystal after reclaiming eluent toluene, with toluene the dehydroabietylamine crystal is carried out 1 recrystallization again after, wait until repeated use.
Embodiment 2
Taking by weighing the alpha-terpineol total content and be 90% raceme alpha-terpineol 34.2g (0.2mol) is dissolved in the 280m1 n-propyl alcohol, wait to dissolve complete back and add 62.7g (0.22mol) chirality dehydroabietylamine, 100 ℃ of left and right sides heating reflux reactions 2 hours, room temperature left standstill 36 hours, filter to get filtrate A and deposit B are with a small amount of n-propyl alcohol washing precipitation.
Deposit B after the washing is dissolved in the 200ml toluene eluent, and stirring at normal temperature 1 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 10.2g, is the dextrorotatory form alpha-terpineol, its [α]
D 20=+47.9 °, the e.e value is 44.4%, is 49.2% based on the yield of dextrorotation alpha-terpineol theoretical value.
The filtrate A vacuum distillation recovered solvent n-propyl alcohol that above-mentioned filtration obtains, adding 360ml toluene and tetracol phenixin volume ratio are 1: 1 eluent, stirring at normal temperature 1 hour, leave standstill phase-splitting, the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 13.38g, be the levo form alpha-terpineol, its [α]
D 20=-45.9 °, the e.e value is 42.3%, is 61.8% based on the yield of left-handed alpha-terpineol theoretical value.
Merge the upper strata eluent layer that above-mentioned twice phase-splitting collected, after eluent is reclaimed in underpressure distillation, obtaining xanchromatic resolving agent dehydroabietylamine crystal, is after 1: 1 eluent carries out 1 recrystallization to the dehydroabietylamine crystal, to wait until repeated use with toluene and tetracol phenixin volume ratio again.
Embodiment 3
Taking by weighing the alpha-terpineol total content is 98%, [α]
D 20=-30.2 °, the e.e value is that 28% the optically active left-handed alpha-terpineol 31.4g (0.2mol) that has is dissolved in the 180ml Virahol, wait to dissolve complete back and add 45.6g (0.16mol) chirality dehydroabietylamine, 85 ℃ of left and right sides heating reflux reactions 1.5 hours, room temperature left standstill 36 hours, filter to get filtrate A and deposit B are with a small amount of washed with isopropyl alcohol precipitation.
Deposit B after the washing is dissolved in the 100ml tetracol phenixin eluent, and stirring at normal temperature 1 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 7.92g, has been to revolve the body alpha-terpineol its [α]
D 20=+73.6 °, the e.e value is 68.5%, is 50.3% based on the yield of dextrorotation alpha-terpineol theoretical value.
The filtrate A vacuum distillation recovered solvent Virahol that above-mentioned filtration obtains, add 180ml tetracol phenixin eluent, stirring at normal temperature 1 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 21.73g, is the levo form alpha-terpineol, its [α]
D 20=-65.9 °, the e.e value is 62.7%, is 70.2% based on the yield of left-handed alpha-terpineol theoretical value.
Merge the eluent layer that above-mentioned twice phase-splitting collected, underpressure distillation obtains xanchromatic resolving agent dehydroabietylamine crystal after reclaiming the eluent tetracol phenixin, with tetracol phenixin the dehydroabietylamine crystal is carried out 1 recrystallization again after, wait until repeated use.
Embodiment 4
Taking by weighing the alpha-terpineol total content is 98%, [α]
D 20=-33.1 °, the e.e value is that 30% the optically active left-handed alpha-terpineol 31.4g (0.2mol) that has is dissolved in the 210ml methyl alcohol, wait to dissolve complete back and add 45.6g (0.16mol) chirality dehydroabietylamine, 78 ℃ of left and right sides heating reflux reactions 2 hours, room temperature left standstill 36 hours, filter to get filtrate A and deposit B are used the small amount of methanol washing precipitation.
The deposit B that washing is good is dissolved in the 80ml dimethylbenzene eluent, and stirring at normal temperature 1.5 hours leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 8.18g, is the dextrorotatory form alpha-terpineol, its [α]
D 20=+72.7 °, the e.e value is 67.1%, is 52.4% based on the yield of dextrorotation alpha-terpineol theoretical value.
The filtrate A vacuum distillation recovered solvent methyl alcohol that above-mentioned filtration obtains, add 150ml dimethylbenzene eluent, stirring at normal temperature 1.5 hours leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 22.34g, is the levo form alpha-terpineol, its [α]
D 20=-66.0 °, the e.e value is 62.9%, is 71.3% based on the yield of left-handed alpha-terpineol theoretical value.
Merge the eluent layer that above-mentioned twice phase-splitting collected, underpressure distillation obtains xanchromatic resolving agent dehydroabietylamine crystal after reclaiming eluent dimethylbenzene, with dimethylbenzene the dehydroabietylamine crystal is carried out 1 recrystallization again after, wait until repeated use.
Embodiment 5
Taking by weighing the alpha-terpineol total content is 98%, [α]
D 20=-33.1 ° of e.e values are that 30% the optically active left-handed alpha-terpineol 31.4g (0.2mol) that has is dissolved in the 180ml propyl carbinol, wait to dissolve complete back and add 45.6g (0.16mol) chirality dehydroabietylamine, 120 ℃ of left and right sides heating reflux reactions 2 hours, room temperature left standstill 36 hours, filter to get filtrate A and deposit B are with a small amount of propyl carbinol washing precipitation.
The deposit B that washing is good is dissolved in the 100ml hexanaphthene eluent, and stirring at normal temperature 1 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 8.27g, is the dextrorotatory form alpha-terpineol, its [α]
D 20=+72.9 °, the e.e value is 67.9%, is 53.6% based on the yield of dextrorotation alpha-terpineol theoretical value.
The filtrate A vacuum distillation recovered solvent propyl carbinol that above-mentioned filtration obtains, add 225ml hexanaphthene eluent, stirring at normal temperature 1 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 22.26g, is the levo form alpha-terpineol, its [α]
D 20=-67.8 °, the e.e value is 63.5%, is 71.7% based on the yield of left-handed alpha-terpineol theoretical value.
Merge the eluent layer that above-mentioned twice phase-splitting collected, underpressure distillation obtains xanchromatic resolving agent dehydroabietylamine crystal after reclaiming the eluent hexanaphthene, with hexanaphthene the dehydroabietylamine crystal is carried out 1 recrystallization again after, wait until repeated use.
Embodiment 6
Taking by weighing the alpha-terpineol total content is 98%, [α]
D 20=-37.6 ° of e.e values are that 32% the optically active left-handed alpha-terpineol 31.4g (0.2mol) that has is dissolved in the 250ml isopropylcarbinol, wait to dissolve complete back and add 57.0g (0.2mol) chirality dehydroabietylamine, 110 ℃ of left and right sides heating reflux reactions 3 hours, room temperature left standstill 36 hours, filter to get filtrate A and deposit B are with a small amount of isopropylcarbinol washing precipitation.
The deposit B that washing is good is dissolved in the 180ml normal hexane eluent, and stirring at normal temperature 1.5 hours leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 8.30g, is the dextrorotatory form alpha-terpineol, its [α]
D 20=+71.8 °, the e.e value is 66.9%, is 54.6% based on the yield of dextrorotation alpha-terpineol theoretical value.
The filtrate A underpressure distillation that above-mentioned filtration is obtained removes the isopropylcarbinol that desolvates, and adds 300ml normal hexane eluent, and stirring at normal temperature 1.5 hours leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 22.09g, is the levo form alpha-terpineol, its [α]
D 20=-69.2 °, the e.e value is 64.7%, is 71.4% based on the yield of left-handed alpha-terpineol theoretical value.
Merge the eluent layer that above-mentioned twice phase-splitting collected, underpressure distillation obtains xanchromatic resolving agent dehydroabietylamine crystal after reclaiming the eluent normal hexane, with normal hexane the dehydroabietylamine crystal is carried out 1 recrystallization again after, stay to be equipped with and reuse.
Embodiment 7
Taking by weighing the alpha-terpineol total content is 98%, [α]
D 20=-30.2 °, the e.e value is that 28% the optically active left-handed alpha-terpineol 31.4g (0.2mol) that has is dissolved in the Virahol that 200ml reclaims from embodiment 3, wait to dissolve the chirality dehydroabietylamine that complete back adds 45.6g (0.16mol) embodiment 2 and embodiment 3 recovery, 85 ℃ of left and right sides heating reflux reactions 1.5 hours, room temperature left standstill 48 hours, filter to get filtrate A and deposit B are with a small amount of washed with isopropyl alcohol precipitation.
The good precipitation of washing is dissolved in the tetracol phenixin eluent that 100ml reclaims from embodiment 3, and stirring at normal temperature 1.5 hours leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 8.14g, is the dextrorotatory form alpha-terpineol, its [α]
D 20=+72.7 °, the e.e value is 67.7%, is 51.1% based on the yield of dextrorotation alpha-terpineol theoretical value.
Filtrate A vacuum distillation recovered solvent Virahol above-mentioned filtration obtains adds the tetracol phenixin eluent that 150ml reclaims, stirring at normal temperature 1.5 hours, leave standstill phase-splitting, the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 22.19g, be the levo form alpha-terpineol, its [α]
D 20=-64.3 °, the e.e value is 61.9%, is 70.8% based on the yield of left-handed alpha-terpineol theoretical value.
Merge the eluent layer that above-mentioned twice phase-splitting collected, underpressure distillation obtains xanchromatic resolving agent dehydroabietylamine crystal after reclaiming the eluent tetracol phenixin, with tetracol phenixin the dehydroabietylamine crystal is carried out 2 recrystallizations again after, wait until repeated use.
Embodiment 8
Taking by weighing the alpha-terpineol total content and be 90% raceme alpha-terpineol 34.2g (0.2mol), to be dissolved in 220ml n-propyl alcohol and dehydrated alcohol volume ratio be in 3: 1 the mixed solvent, wait to dissolve complete back and add 62.7g (0.22mol) chirality dehydroabietylamine, 90 ℃ of left and right sides heating reflux reactions 2 hours, room temperature left standstill 36 hours, filter to get filtrate A and deposit B are 3: 1 mixed solvent washing precipitation with a small amount of n-propyl alcohol dehydrated alcohol volume ratio.
The deposit B that washing is good is dissolved in the 120ml toluene eluent, and stirring at normal temperature 1 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 11.2g, is the dextrorotatory form alpha-terpineol, its [α]
D 20=+73.0 °, the e.e value is 68.4%, is 49.8% based on the yield of dextrorotation alpha-terpineol theoretical value.
Mixed solvent is reclaimed in the filtrate A underpressure distillation that above-mentioned filtration obtains, and adding 150ml toluene and tetracol phenixin volume ratio are 1: 1 eluent, stirring at normal temperature 1 hour, leave standstill phase-splitting, the upper strata is the eluent layer, and lower floor obtains weak yellow liquid 15.4g, be the levo form alpha-terpineol, its [α]
D 20=-65.5 °, the e.e value is 62.7%, is 61.6% based on the yield of left-handed alpha-terpineol theoretical value.
Merge the upper strata eluent layer that above-mentioned twice phase-splitting collected, after eluent is reclaimed in underpressure distillation, obtaining xanchromatic resolving agent dehydroabietylamine crystal, is after 1: 1 eluent carries out 1 recrystallization to the dehydroabietylamine crystal, to wait until repeated use with toluene and tetracol phenixin volume ratio again.
Claims (5)
1. one kind is improved the optically active method of alpha-terpineol, it is characterized in that: adopt the inclusion Split Method, raceme or the low alpha-terpineol of optical activity are split as the method for left-handed alpha-terpineol and dextrorotation alpha-terpineol, its process comprises the following steps:
(1) raw material raceme or the low alpha-terpineol of optical activity are dissolved in the solvent, wait to dissolve complete back and add resolving agent, reflux 1～3 hour, temperature of reaction is not less than the boiling point of solvent for use, room temperature left standstill 24～48 hours then, filtered, and obtained filtrate A and filter residue B respectively;
(2) underpressure distillation filtrate A reclaims solvent, obtains having the faint yellow crystallisate C of thick liquid;
(3) faint yellow crystallisate C is dissolved in the eluent, stirring at normal temperature 0.5～1.5 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor then is respectively and splits the left-handed alpha-terpineol of product;
(4) filter residue B obtains sediment D with identical solvent wash;
(5) sediment D is dissolved in the eluent, stirring at normal temperature 0.5～1.5 hour leaves standstill phase-splitting, and the upper strata is the eluent layer, and lower floor then is respectively and splits byproduct dextrorotation alpha-terpineol;
Described resolving agent is the optical purity dehydroabietylamine, its specific rotatory power [α]
D 20=+56.1 °, the e.e value is 95～98%, and the mol ratio of dehydroabietylamine and raw material alpha-terpineol is 0.7～1.1: 1;
Described solvent is C
1-4Low-carbon alcohol, consumption is 3～8 times of raw material alpha-terpineol volume;
Described eluent is a kind of of tetracol phenixin, toluene, dimethylbenzene, hexanaphthene and normal hexane or their mixture, and consumption is to treat 2～8 times of eluate weight.
2. the optically active method of raising alpha-terpineol according to claim 1 is characterized in that: low-carbon alcohol comprises a kind of or their mixture such as methyl alcohol, ethanol, n-propyl alcohol, Virahol, propyl carbinol, isopropylcarbinol.
3. the optically active method of raising alpha-terpineol according to claim 1 is characterized in that: the specific rotatory power [α] of the left-handed alpha-terpineol of fractionation product that obtains
D 20Value is-40 °～-70 °, and the e.e value is 38～65%, and yield is 65～72%; The specific rotatory power of dextrorotation alpha-terpineol [α]
D 20Value is+45 °～+ 75 °, and the e.e value is 41～70%, and yield is 45～55%.
4. the optically active method of raising alpha-terpineol according to claim 1 is characterized in that: used resolving agent dehydroabietylamine, and reusable after recrystallization is purified.
5. the optically active method of raising alpha-terpineol according to claim 1 is characterized in that: used solvent, eluent can be reused after recovery is collected in underpressure distillation.
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| CN104193588A (en) * | 2014-08-07 | 2014-12-10 | 广西众昌树脂有限公司 | Method for preparing high-purity dextro alpha-terpilenol |
| CN104193589A (en) * | 2014-08-07 | 2014-12-10 | 广西众昌树脂有限公司 | Preparation method of high-purity L-alpha terpilenol |
| CN114751831A (en) * | 2022-03-25 | 2022-07-15 | 广西大学 | Dehydroabietylamine chloride salt and preparation method and application thereof |
| CN114751833A (en) * | 2022-03-25 | 2022-07-15 | 广西大学 | Dehydroabietylamine chiral ionic liquid and preparation method and application thereof |
| CN115568479A (en) * | 2022-11-03 | 2023-01-06 | 江西正邦作物保护股份有限公司 | Compound herbicide composition containing xaflufen-ethyl and preparation method thereof |
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| CN1056866A (en) * | 1990-05-29 | 1991-12-11 | 中国科学院广州化学研究所 | The novel method of one-step synthesis optical activity alpha-terpineol |
| CN1482113A (en) * | 2003-07-16 | 2004-03-17 | 广西壮族自治区化工研究院 | Process for preparing levogyrate alpha-terpineol |
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2011
- 2011-04-13 CN CN 201110091311 patent/CN102225885B/en active Active
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1056866A (en) * | 1990-05-29 | 1991-12-11 | 中国科学院广州化学研究所 | The novel method of one-step synthesis optical activity alpha-terpineol |
| CN1482113A (en) * | 2003-07-16 | 2004-03-17 | 广西壮族自治区化工研究院 | Process for preparing levogyrate alpha-terpineol |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN104193588A (en) * | 2014-08-07 | 2014-12-10 | 广西众昌树脂有限公司 | Method for preparing high-purity dextro alpha-terpilenol |
| CN104193589A (en) * | 2014-08-07 | 2014-12-10 | 广西众昌树脂有限公司 | Preparation method of high-purity L-alpha terpilenol |
| CN114751831A (en) * | 2022-03-25 | 2022-07-15 | 广西大学 | Dehydroabietylamine chloride salt and preparation method and application thereof |
| CN114751833A (en) * | 2022-03-25 | 2022-07-15 | 广西大学 | Dehydroabietylamine chiral ionic liquid and preparation method and application thereof |
| CN114751831B (en) * | 2022-03-25 | 2023-10-31 | 广西大学 | Dehydroabietylamine chloride and preparation method and application thereof |
| CN114751833B (en) * | 2022-03-25 | 2023-10-31 | 广西大学 | Dehydroabietylamine chiral ionic liquid and preparation method and application thereof |
| CN115568479A (en) * | 2022-11-03 | 2023-01-06 | 江西正邦作物保护股份有限公司 | Compound herbicide composition containing xaflufen-ethyl and preparation method thereof |
| CN115568479B (en) * | 2022-11-03 | 2023-11-14 | 江西正邦作物保护股份有限公司 | Composite herbicide composition containing fenpyrad and preparation method thereof |
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