CN1482113A - Process for preparing levogyrate alpha-terpineol - Google Patents
Process for preparing levogyrate alpha-terpineol Download PDFInfo
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- CN1482113A CN1482113A CNA031785484A CN03178548A CN1482113A CN 1482113 A CN1482113 A CN 1482113A CN A031785484 A CNA031785484 A CN A031785484A CN 03178548 A CN03178548 A CN 03178548A CN 1482113 A CN1482113 A CN 1482113A
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Abstract
The present invention provides one-step levo-alpha-terpineol synthesizing process, in which turpentine oil with alpha-pinene as main component is used as the material, low-carbon alcohol or ketone as solvent and modified strong acid styrene cationic exchange resin as catalyst and the catalytic hydration is completed in a fixed bed reactor. It has catalyst/alpha-pinene weight ratio of 1 to 1-10, alpha-pinene/water molar ratio of 1 to 1.1-2, water/solvent molar ratio of 1 to 0.1-0.9, reaction temperature of 70-100 deg.c, reaction period of 5-13 hr, alpha-pinene converting rate over 95 % and levo-alpha-terpineol yield over 65 %.
Description
Technical field
The present invention relates to a kind of preparation method of left-handed alpha-terpineol.More particularly, relating to a kind of is catalyzer with the modified cation-exchange resin, the method for the left-handed alpha-oil alcohol of fixed bed one-step synthesis.
Background technology
Terpineol 350 (terpineol) also claim Chinese parasol tree oil, terpinol, is a kind of monocyclic monoterpene alcohol compound, molecular formula C
10H
18O, molecular weight 154.24, have α-, β-, γ-three kind of isomer, wherein alpha-terpineol is the most common at occurring in nature, has found that alpha-terpineol is present in the leaf of 200 various plants, flower, the grass blade.That alpha-terpineol has is left-handed, dextrorotation and three kinds of optically active forms of racemization, the dextrorotation Terpineol 350 is present in the plants essential oils such as cypress, Elettaria cardamomum (L.) Maton, star anise, flores aurantii, L-terpineol is present in the plants essential oils such as Lavandula hybrida, Punetree, limette, basyleaves, and the racemization Terpineol 350 is present in Oleum Pelargonii Graveolentis, cajeput oil, ucuhuba oil, sweet marjoram oil, the pamorusa oil.Yet directly extracting Terpineol 350 from plants essential oil does not have economic worth, generally is to produce the commodity Terpineol 350 by chemosynthesis.The commodity Terpineol 350 is a kind of racemic mixture based on alpha-terpineol, is colourless viscous liquid, and the fragrance with Syringa oblata Lindl. is one of main synthetic perfume kind.
Two-step process is adopted in conventional at present Terpineol 350 production, these sources of law make Terpineol 350 from the Terpine hydrate dehydration that Tilden found in 1878, promptly use 25～35% vitriolization turps, make α-Pai Xi wherein be transformed into a Terpine hydrate intermediate, again the intermediate dehydration is made thick Terpineol 350, after rectification under vacuum obtains elaboration, product is the raceme Terpineol 350, is characterized in that product fragrance is pure.Technical process is long, energy consumption is high, equipment corrosion is serious, labour intensity is big, spent acid is seriously polluted, the more high shortcoming of production cost but also exist.Therefore, carried out the research of one-step technology both at home and abroad, the solid acid catalyst of employing synthesizes Terpineol 350, and the catalyzer of selecting for use has zeolite, ion exchange resin, layered solid acid etc.(the Japan such as Kikuchi of Japan, Kokai 78 34748) disclose Zeo-karb and α-Pai Xi and in the presence of organic solvent, stirred 20 hours thick Terpineol 350s of one-step synthesis in 62 ℃, though this method is fairly simple, but it is oversize that reaction lasts, the Terpineol 350 of catalyst breakage severity and gained also is a raceme, and the yield of alpha-terpineol is 50.1%.Domestic Hu Meikang [chemistry world .1987, (6) .249～251], Lin Zhongxiang etc. [Guangdong chemical industry .1992. (1) .43～44], [Journal of Natural Science of Hunan Normal University .1997 such as Li Qianhe, 20 (1) .36～39], [the journal .2000 of Zhongnan Forestry Inst. such as Zhang Zhiliu, 20 (2) .32～35], [forest product industry .2000 such as Yang Yan, 27 (2) .25～26] delivered the research of the synthetic Terpineol 350 of relevant catalyzing cation exchange resin respectively, though in the reaction times, aspects such as product yield make a modest advance than Japanese Patent, but the yield of alpha-terpineol not high (about 55%), product is still the Terpineol 350 of racemization.People such as Xiao Shude [ZL 90104026.6] disclose one-step synthesis and have had the method for optical activity alpha-terpineol, employing exchanges and calcines the mordenite of alternate treatment as catalyzer through acid, with the halogenated alkyl quaternary ammonium salt is cocatalyst, in the presence of alcohols, ethers, ketones solvent, the hydration of catalysis α-Pai Xi, single stage method prepares alpha-terpineol, and the product of gained is the dextrorotation Terpineol 350.
Summary of the invention
Have optically active left-handed alpha-terpineol, show good effect at aspects such as desinsection, sterilization, mosquito repellents, and its perviousness is strong, and medicine is had certain synergism, have a extensive future at aspects such as agricultural chemicals, medicine, daily-use chemical industries.The object of the invention is to provide a kind of method of directly producing left-handed alpha-terpineol, and not only raw material is easy to get, and technical process is short, and is easy and simple to handle, and the product yield height.
The invention provides a kind of is raw material with turps, is catalyzer with the modification strongly acidic styrene type cation exchange resin, by one step of fixed-bed reactor hydration reaction, obtains the method for left-handed alpha-terpineol again by rectifying.Technical scheme is as follows:
With 001 * 7 or the hydrogen type strong acid styrene type cation exchange resin of D001 be raw material, handle under special conditions through liquor ferri trichloridi, Cupric Chloride Solution, titanium tetrachloride solution, zirconium nitrate solution, make modification strongly acidic styrene type cation exchange resin catalyzer at last, this solid acid catalyst is packed in the tubular fixed-bed reactor, catalysis α-Pai Xi hydration reaction, the left-handed alpha-terpineol of one-step synthesis.
Concrete is, the hydrogen type strong acid styrene type cation exchange resin is handled with 0.1～1.5% liquor ferri trichloridi, the volume ratio of ion exchange resin and solution is 1: 3, in 50～55 ℃ temperature and-0.05～-vacuum tightness of 0.06MPa under, soaked re-treatment 2～3 times 8～12 hours.With identical method, respectively ion exchange resin is handled with 0.1～1.5% Cupric Chloride Solution, 0.1～1.5% titanium tetrachloride solution, 0.1～1.5% zirconium nitrate solution successively again, be washed till no chlorion with deionized water then, in 100～120 ℃ temperature ,-0.06～-dry under the vacuum tightness of 0.095MPa, make modification hydrogen type strong acid styrene type cation exchange resin catalyzer.
Described modification hydrogen type strong acid styrene type cation exchange resin catalyzer is packed in the tubular fixed-bed reactor of diameter 20～300mm, length 300～2000mm.To put into vaporizer in proportion based on turps, water, alcohols or the ketones solvent of α-Pai Xi, and evaporate the steam of mixing solutions, and flow in the tubular fixed-bed reactor through condensation, and carry out the hydration reaction of α-Pai Xi, one-step synthesis goes out left-handed alpha-terpineol.The weight ratio of described modification strongly acidic styrene type cation exchange resin catalyzer and α-Pai Xi is 1: 1～10, the mol ratio of α-Pai Xi and water is 1: 1.1～2, the mol ratio of water and solvent is 1: 0.1～0.9, temperature of reaction is 70～100 ℃, be preferably 85～95 ℃, reaction times is 5～13 hours, is preferably 8～12 hours.After reaction finished, reaction solution reclaimed solvent by simple distillation, obtained left-handed alpha-terpineol through the rectification under vacuum intercepting again.Recovered solvent is reusable.Modification strongly acidic styrene type cation exchange resin catalyzer is difficult for inactivation, but life-time service.The spectral analysis data of product is consistent with the alpha-terpineol structure, and the rotational analysis data are left-handed.
Preparation method provided by the invention, because the strongly acidic styrene type cation exchange resin solid acid catalyst is active high through modification, and fixed bed temperature height, solvent load are few, the α-Pai Xi transformation efficiency is more than 95%, and left-handed alpha-terpineol yield is more than 65%.
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
Preparation of catalysts
Hydrogen D001 large hole strong acid styrene system cation exchange resin is put into 1.2% liquor ferri trichloridi, the volume ratio of ion exchange resin and solution is 1: 3, in 50～55 ℃ temperature and-0.05～-vacuum tightness of 0.06MPa under, soaked 8 hours, the elimination liquor ferri trichloridi is pressed the similarity condition re-treatment 2～3 times again.With identical method, respectively ion exchange resin is handled with 1.3% Cupric Chloride Solution, 0.2% titanium tetrachloride solution, 0.5% zirconium nitrate solution successively again, be washed till no chlorion with deionized water then, in 110～120 ℃ temperature ,-0.09～-dry under the vacuum tightness of 0.095MPa, prepare modification D001 hydrogen type strong acid styrene type cation exchange resin catalyzer.
Embodiment 2
Preparation of catalysts
Hydrogen 001 * 7 strongly acidic styrene type cation exchange resin is put into 0.5% liquor ferri trichloridi, the volume ratio of ion exchange resin and solution is 1: 3, in 50～55 ℃ temperature and-0.05～-vacuum tightness of 0.06MPa under, soaked 11 hours, the elimination liquor ferri trichloridi is pressed the similarity condition re-treatment 2～3 times again.With identical method, respectively ion exchange resin is handled with 0.3% Cupric Chloride Solution, 0.1% titanium tetrachloride solution, 0.2% zirconium nitrate solution successively again, be washed till no chlorion with deionized water then, in 100 ℃ temperature ,-0.09～-dry under the vacuum tightness of 0.095MPa, prepare modification 001 * 7 hydrogen type strong acid styrene type cation exchange resin catalyzer.
Embodiment 3
Synthesizing of left-handed alpha-terpineol
It is in the tubular fixed-bed reactor of 20mm, length 600mm that the modification D001 hydrogen type strong acid styrene type cation exchange resin catalyzer 280 of preparation among the embodiment 1 is restrained the diameter of packing into.In being housed, 1000 milliliters of three-necked flasks of reflux exchanger, thermometer add 300 gram α
25 D=-12.5 ° turps (contains firpene 91% approximately, 2 moles), 54 gram water (3 moles) and 60 gram 99% n-propyl alcohols (1 mole), heating makes firpene, water and n-propyl alcohol evaporation and control steam output, enter in the tubular fixed-bed reactor after condenser condenses and react, refluxing then enters three-necked flask, continuously circulation, keep the fixed bed reaction actuator temperature about 90 ℃, reacted 9 hours.Reaction finishes, and removes n-propyl alcohol by simple distillation, and the cut of 130～140 ℃/40mmHg of rectification under vacuum collection gets the left-handed alpha-terpineol of 243 grams again, and product yield is 75%; α
25 D=-23.2 °.
Embodiment 4
Synthesizing of left-handed alpha-terpineol
It is in the tubular fixed-bed reactor of 40mm, length 1000mm that the modification D001 hydrogen type strong acid styrene type cation exchange resin catalyzer 1600 of preparation among the embodiment 1 is restrained the diameter of packing into.In being housed, 50 liters of evaporating kettles of reflux exchanger, thermometer add 15000 gram α
25 D=-12.5 ° turps (contains firpene 91% approximately, 100.4 mole), 2300 gram water (127.8 moles) and 3030 gram 99% n-propyl alcohols (50 moles), heating makes firpene, water and n-propyl alcohol evaporation and control steam output, enter in the tubular fixed-bed reactor after condenser condenses and react, refluxing then enters evaporating kettle, continuously circulation, keep the fixed bed reaction actuator temperature about 93 ℃, reacted 11 hours.Reaction finishes, and removes n-propyl alcohol by simple distillation, and the cut of 130～140 ℃/40mmHg is collected in rectification under vacuum again, gets the left-handed alpha-terpineol of 11718 grams, and product yield is 72%; α
25 D=-23.6 °.
Embodiment 5
Synthesizing of left-handed alpha-terpineol
It is in the tubular fixed-bed reactor of 20mm, length 600mm that modification 001 * 7 hydrogen type strong acid styrene type cation exchange resin catalyzer 350 of preparation among the embodiment 2 is restrained the diameter of packing into.In being housed, 1000 milliliters of three-necked flasks of reflux exchanger, thermometer add 300 gram α
25 D=-12.5 ° turps (contains firpene 91% approximately, 2 moles), 65 gram water (3.6 moles) and 48 gram 95% ethanol (1 mole), heating makes firpene, water and ethanol evaporation and controls steam output, enter in the tubular fixed-bed reactor after condenser condenses and react, refluxing then enters three-necked flask, continuously circulation, keep the fixed bed reaction actuator temperature about 85 ℃, reacted 10 hours.Reaction finishes, and removes ethanol by simple distillation, and the cut of 130～140 ℃/40mmHg of rectification under vacuum collection gets 213 gram alpha-terpineols again, and product yield is 66%; α
25 D=-21.6 °.
Embodiment 6
Synthesizing of left-handed alpha-terpineol
It is in the tubular fixed-bed reactor of 40mm, length 1000mm that modification 001 * 7 hydrogen type strong acid styrene type cation exchange resin catalyzer 1800 of preparation among the embodiment two is restrained the diameter of packing into.In being housed, 50 liters of evaporating kettles of reflux exchanger, thermometer add 15000 gram α
25 D=-12.5 ° turps (contains firpene 91% approximately, 100.4 mole), 3240 gram water (180 moles) and 3870 gram 95% ethanol (80 moles), heating makes firpene, water and ethanol evaporation and controls steam output, enter in the tubular fixed-bed reactor after condenser condenses and react, refluxing then enters evaporating kettle, continuously circulation, keep the fixed bed reaction actuator temperature about 86 ℃, reacted 12 hours.Reaction finishes, and removes ethanol by simple distillation, and the cut of 130～140 ℃/40mmHg is collected in rectification under vacuum again, gets the left-handed alpha-terpineol of 10580 grams, and product yield is 65%; α
25 D=-21.1 °.
Claims (6)
1, a kind of preparation method of left-handed alpha-terpineol, based on the turps that contains α-Pai Xi is raw material, low-carbon alcohol or ketone are solvent, the hydrogen type strong acid styrene type cation exchange resin is a catalyzer, produce left-handed alpha-terpineol by fixed-bed reactor single stage method hydration reaction, it is characterized in that described Zeo-karb is successively through the strongly acidic styrene type cation exchange resin of liquor ferri trichloridi, Cupric Chloride Solution, titanium tetrachloride solution, zirconium nitrate solution modification; Described hydration reaction condition is: the weight ratio of modification strongly acidic styrene type cation exchange resin catalyzer and α-Pai Xi is 1: 1～10, the mol ratio of α-Pai Xi and water is 1: 1.1～2, the mol ratio of water and solvent is 1: 0.1～0.9, the temperature of reaction of fixed bed is 70～100 ℃, and the reaction times is 5～13 hours.
2, preparation method as claimed in claim 1, it is characterized in that described modification strongly acidic styrene type cation exchange resin is that the hydrogen type strong acid styrene type cation exchange resin is handled with 0.1～1.5% liquor ferri trichloridi, the volume ratio of ion exchange resin and solution is 1: 3, in 50～55 ℃ temperature and-0.05～-vacuum tightness of 0.06MPa under, soaked re-treatment 2～3 times 8～12 hours; With identical method, respectively ion exchange resin is handled with 0.1～1.5% Cupric Chloride Solution, 0.1～1.5% titanium tetrachloride solution, 0.1～1.5% zirconium nitrate solution successively again, be washed till no chlorion with deionized water then, in 100～120 ℃ temperature ,-0.06～-dry under the vacuum tightness of 0.095MPa, make modification hydrogen type strong acid styrene type cation exchange resin catalyzer.
3, preparation method as claimed in claim 1 or 2 is characterized in that described fixed bed reaction temperature is 85～95 ℃, and the reaction times is 8～12 hours.
4, preparation method as claimed in claim 1 or 2 is characterized in that described hydrogen type strong acid styrene type cation exchange resin is 001 * 7 or D001.
5, preparation method as claimed in claim 1 or 2 is characterized in that described fixed-bed reactor are the tubular fixed-bed reactor of diameter 20～300mm, length 300～2000mm.
6, preparation method as claimed in claim 1 or 2 is characterized in that described solvent is any one in n-propyl alcohol, ethanol, the acetone.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN100402485C (en) * | 2006-04-19 | 2008-07-16 | 广西壮族自治区化工研究院 | Method for reaction rectification coupling continuous preparation of and series acetate |
| CN100567241C (en) * | 2008-01-30 | 2009-12-09 | 中国科学院广州化学研究所 | A kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone |
| CN102225886A (en) * | 2011-04-13 | 2011-10-26 | 广西壮族自治区化工研究院 | Method for preparing alpha-terpineol with high optical purity |
| CN102225885A (en) * | 2011-04-13 | 2011-10-26 | 广西壮族自治区化工研究院 | Method for increasing optical purity of alpha-terpineol |
| CN102229524A (en) * | 2011-04-19 | 2011-11-02 | 广西壮族自治区化工研究院 | Reaction device for synthesizing levo terpineol |
| CN103044202A (en) * | 2013-01-08 | 2013-04-17 | 江苏宏邦化工科技有限公司 | Preparation method of 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 |
| 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 |
| CN109721468A (en) * | 2018-12-21 | 2019-05-07 | 怀集县长林化工有限责任公司 | A kind of australene bisabolene isomer prepares the preparation method of terpineol |
| CN116102400A (en) * | 2023-02-13 | 2023-05-12 | 中国林业科学研究院林产化学工业研究所 | Preparation method of L-4-terpineol |
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| CN101926354A (en) * | 2010-08-16 | 2010-12-29 | 广西壮族自治区化工研究院 | Bactericide composite containing flusilazole and levo alpha-terpineol and production method thereof |
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- 2003-07-16 CN CNB031785484A patent/CN100357240C/en not_active Expired - Lifetime
Cited By (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100402485C (en) * | 2006-04-19 | 2008-07-16 | 广西壮族自治区化工研究院 | Method for reaction rectification coupling continuous preparation of and series acetate |
| CN100567241C (en) * | 2008-01-30 | 2009-12-09 | 中国科学院广州化学研究所 | A kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone |
| CN102225886A (en) * | 2011-04-13 | 2011-10-26 | 广西壮族自治区化工研究院 | Method for preparing alpha-terpineol with high optical purity |
| CN102225885A (en) * | 2011-04-13 | 2011-10-26 | 广西壮族自治区化工研究院 | Method for increasing optical purity of alpha-terpineol |
| CN102225885B (en) * | 2011-04-13 | 2013-08-28 | 广西壮族自治区化工研究院 | Method for increasing optical purity of alpha-terpineol |
| CN102225886B (en) * | 2011-04-13 | 2013-09-25 | 广西壮族自治区化工研究院 | Method for preparing alpha-terpineol with high optical purity |
| CN102229524A (en) * | 2011-04-19 | 2011-11-02 | 广西壮族自治区化工研究院 | Reaction device for synthesizing levo terpineol |
| CN103044202A (en) * | 2013-01-08 | 2013-04-17 | 江苏宏邦化工科技有限公司 | Preparation method of 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 |
| 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 |
| CN109721468A (en) * | 2018-12-21 | 2019-05-07 | 怀集县长林化工有限责任公司 | A kind of australene bisabolene isomer prepares the preparation method of terpineol |
| CN116102400A (en) * | 2023-02-13 | 2023-05-12 | 中国林业科学研究院林产化学工业研究所 | Preparation method of L-4-terpineol |
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