CN100567241C - A kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone - Google Patents
A kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone Download PDFInfo
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- CN100567241C CN100567241C CNB2008100261453A CN200810026145A CN100567241C CN 100567241 C CN100567241 C CN 100567241C CN B2008100261453 A CNB2008100261453 A CN B2008100261453A CN 200810026145 A CN200810026145 A CN 200810026145A CN 100567241 C CN100567241 C CN 100567241C
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Abstract
The invention discloses a kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone, comprise the steps: α-Pai Xi is dissolved in the trimethyl carbinol aqueous solution and be cooled to-10～18 ℃, keep the temperature of system to finish reaction in 23～25 hours after adding potassium permanganate-10～18 ℃ of reactions, keep temperature of reaction system to float in the adition process at 0～4 ℃, with reacting liquid filtering, filtrate reclaimed to leave standstill behind the trimethyl carbinol be divided into oil reservoir and water layer, get oil reservoir, underpressure distillation, collect 110～115 ℃ of cuts, add organic solvent in-10～-18 ℃ place down recrystallizations obtain purifying (1S, 2S, 5S)-2-hydroxyl-3-pinone.The trimethyl carbinol in the preparation process of the present invention in the used solvent tertiary butanol aqueous solution has good returnability, and rate of recovery height can recycle in industrial production, meets the needs that industrial production reduces cost.
Description
Technical field
The invention belongs to the preparation field of chemical intermediate, particularly a kind of (1S, 2S, 5S)-2-hydroxyl-3-pinone ((1S, 2S, preparation method 5S)-2-Hydroxy-3-pinanone).
Background technology
China's turps output occupies first place in the world, but isolated α-Pai Xi is that added value of product is low based on material outlet always from turps.
People such as Takayuki Suga are at Journal of Organic Chemistry, 30 (2), 669-670, report is said the oxidation products (1S of α-Pai Xi in 1965,2S, 5S)-and 2-hydroxyl-3-pinone (structural formula is suc as formula (a)) can generate the compound isothymol (Carvacrol) with anti-food source property spoilage organism and pathogenic activity through dehydration reaction, and this method has excellent industrial application foreground.
Formula (a)
People such as Takayuki Suga are at Journal of Organic Chemistry, 30 (2), 669-670, in 1965, people such as Carlson R.G. are at Journal of Organic Chemistry, 36,2319-2324, in 1971, Kuwata T. is at Journal of American Chemistry Society, 59, the 2509-2511, (1S that is reported in 1937,2S, 5S)-and the 2-hydroxyl-preparation method of 3-pinone all takes the method for potassium permanganate oxidation α-Pai Xi in the homogeneous system, and solvent for use is high density aqueous acetone solution (massfraction is 90%), and only 56.48 ℃ of acetone boiling points, with water azeotropic not, reclaim and require height, the rate of recovery is low, considers to be unfavorable for industrialization from the production cost aspect.
Summary of the invention
The objective of the invention is to overcome the shortcoming of prior art, provide a kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone, this method is keeping under the constant prerequisite of product yield, has solvent recuperation and requires advantages such as low, that solvent recovering rate is high and preparation cost is low.
Purpose of the present invention is achieved through the following technical solutions: a kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone, adjust the temperature to-10～18 ℃ after comprising the steps: to be dissolved in α-Pai Xi in 8～15 quality trimethyl carbinol aqueous solution doubly, add potassium permanganate, keep temperature of reaction system to float at 0～4 ℃ in the adition process, the ratio of the potassium permanganate that is added and the amount of substance of α-Pai Xi is 1.3: 1～2: 1; Keep the temperature of system-10～18 ℃ of reactions 23～25 hours after adding potassium permanganate, finish reaction, with reacting liquid filtering, filtrate reclaimed to leave standstill behind the trimethyl carbinol be divided into oil reservoir and water layer, get oil reservoir, in 1.8～2.2kPa underpressure distillation, collect 110～115 ℃ of cuts, add 3～5 quality organic solvent doubly in-10～-18 ℃ place down recrystallizations obtain purifying (1S, 2S, 5S)-2-hydroxyl-3-pinone.
The massfraction of the described trimethyl carbinol aqueous solution is 30～60%, and the massfraction of the preferred tertiary butanols aqueous solution is 40～50%.
Described organic solvent is sherwood oil, ether, normal hexane, ethyl acetate, ethanol or ethylene glycol monomethyl ether etc.
It is to come controlled temperature to change by controlling each feeding quantity that the present invention adds in the potassium permanganate process, adjust the temperature to-5～10 ℃ after preferably α-Pai Xi being dissolved in the trimethyl carbinol aqueous solution, adjust the temperature to-5～5 ℃ after most preferably α-Pai Xi being dissolved in the trimethyl carbinol aqueous solution.
Describedly filtrate is reclaimed the trimethyl carbinol steam to reclaim the trimethyl carbinol to the azeotrope outflow of not having the trimethyl carbinol and water for filtrate decompression is revolved.
The conventional filtration method is adopted in described filtration, the filter cake that will filter the back gained for the yield that improves product use with as behind the identical trimethyl carbinol solution washing of the trimethyl carbinol concentration of aqueous solution of solvent, with washing lotion and filtrate merging.
Be to improve the yield of product, the present invention can reclaim filtrate the water layer organic solvent extraction organic phase that standing demix obtains behind the trimethyl carbinol, and with organic phase and oil reservoir merging and remove organic solvent, described organic solvent is sherwood oil, ether etc.
The present invention compared with prior art has following advantage and beneficial effect:
Existing (5S)-preparation method of 2-hydroxyl-3-pinone all adopts the solvent of aqueous acetone solution as homogeneous reaction system, and the acetone boiling point is low for 1S, 2S, high volatility, and it is big to reclaim loss, as the production cost height of industrial application.The trimethyl carbinol in the preparation process of the present invention in the used solvent tertiary butanol aqueous solution has good returnability, and rate of recovery height can recycle in industrial production, meets the needs that industrial production reduces cost.The present invention makees solvent with the trimethyl carbinol aqueous solution and can keep product yield constant substantially.
Description of drawings
Fig. 1 be the present invention preparation-obtained (1S, 2S, 5S)-2-hydroxyl-3-pinone
1The H-NMR spectrogram.
Fig. 2 be the present invention preparation-obtained (1S, 2S, 5S)-2-hydroxyl-3-pinone
13The C-NMR spectrogram.
Fig. 3 be the present invention preparation-obtained (1S, 2S, 5S)-infrared spectrogram of 2-hydroxyl-3-pinone.
Embodiment
The present invention is described in further detail below in conjunction with embodiment and accompanying drawing, but the working of an invention mode is not limited thereto.
Embodiment 1
Taking by weighing α-Pai Xi 13.6g (0.1mol) joins in the 500mL there-necked flask that is connected to mechanical stirring and thermometer, adding the 200g massfraction is 50% trimethyl carbinol aqueous solution, stirring is cooled to 0 ℃ after making the α-Pai Xi dissolving, add potassium permanganate 26.8g (0.17mol) when treating homo(io)thermism, keep temperature of reaction system to float in the adition process and be no more than 4 ℃, add the back that finishes and keep system temperature to finish reaction at 0 ℃ of reaction 24h.With reacting liquid filtering, the filter cake massfraction is 50% trimethyl carbinol aqueous solution 20g washing 3 times, washing lotion and filtrate are incorporated in 80 ℃ of following vacuum rotary steams recovery trimethyl carbinols to the azeotrope outflow of not having the trimethyl carbinol and water, leave standstill and be divided into oil reservoir and water layer, isolate oil reservoir, twice of extracted with diethyl ether of water layer, with water, saturated sodium bicarbonate washing back are steamed in the normal temperature backspin and removed ether successively after ether layer and the oil reservoir merging, then in the 1.8kPa underpressure distillation, collect 110～115 ℃ of cuts, add 3 quality sherwood oil doubly and get the 10.9g white crystals in-10 ℃ of placement recrystallizations, by
1The H-NMR spectrum,
13C-NMR spectrum and ir data identify its be (1S, 2S, 5S)-2-hydroxyl-3-pinone, yield 65%.Its
1H-NMR (CDCl
3Solvent 400MHz) is composed spectrogram as shown in Figure 1, its
13C-NMR (CDCl
3Solvent 400MHz) is composed spectrogram as shown in Figure 2, and its infrared spectra (directly filming) spectrogram as shown in Figure 3.
Present embodiment reclaims the trimethyl carbinol and water azeotrope 123.8g, and t butanol content is 80%, and the trimethyl carbinol rate of recovery is 90%.
Embodiment 2
Taking by weighing α-Pai Xi 13.6g (0.1mol) joins in the 500mL there-necked flask that is connected to mechanical stirring and thermometer, adding the 200g massfraction is 40% trimethyl carbinol aqueous solution (being made by the 100g trimethyl carbinol water azeotrope and the 100g water that reclaim among the embodiment 1), after stirring makes the α-Pai Xi dissolving, be cooled to-5 ℃, add potassium permanganate 31.6g (0.2mol) when treating homo(io)thermism, keep temperature of reaction system to float in the adition process and be no more than 4 ℃, add the back that finishes and keep system temperature to finish reaction at-5 ℃ of reaction 25h.With reacting liquid filtering, the filter cake massfraction is 40% trimethyl carbinol aqueous solution 20g washing 3 times, washing lotion and filtrate are incorporated in 80 ℃ of following vacuum rotary steams recovery trimethyl carbinols to the azeotrope outflow of not having the trimethyl carbinol and water, leave standstill and be divided into oil reservoir and water layer, isolate oil reservoir, water layer is with using twice of petroleum ether extraction, water successively after petroleum ether layer and oil reservoir merged, saturated sodium bicarbonate washing back is steamed in the normal temperature backspin and is removed sherwood oil, then in the 2kPa underpressure distillation, collect 110～115 ℃ of cuts, add 4 quality ether doubly and get 9.6g (1S, 2S in-15 ℃ of placement recrystallizations, 5S)-and 2-hydroxyl-3-pinone, yield is 57.1%.
Present embodiment reclaims the trimethyl carbinol and water azeotrope 94.4g, t butanol content 78%, the trimethyl carbinol rate of recovery 92%.
Embodiment 3
Taking by weighing α-Pai Xi 13.6g (0.1mol) joins in the 500mL there-necked flask that is connected to mechanical stirring and thermometer, adding the 200g massfraction is 30% trimethyl carbinol aqueous solution (being made by the trimethyl carbinol water azeotrope and the water that reclaim among the embodiment 2), after stirring makes the α-Pai Xi dissolving, be cooled to 18 ℃, add potassium permanganate 20.5g (0.13mol) when treating homo(io)thermism, keep temperature of reaction system to float in the adition process and be no more than 4 ℃, add the back that finishes and keep system temperature to finish reaction at 18 ℃ of reaction 23h.With reacting liquid filtering, the filter cake massfraction is 30% trimethyl carbinol aqueous solution 20g washing 3 times, washing lotion and filtrate are incorporated in 40 ℃ of following vacuum rotary steams recovery trimethyl carbinols to the dripless outflow, leave standstill and be divided into oil reservoir and water layer, isolate oil reservoir, twice of extracted with diethyl ether of water layer, water successively after ether layer and oil reservoir merged, saturated sodium bicarbonate washing back is steamed in the normal temperature backspin and is removed ether, then in the 2kPa underpressure distillation, collect 110～115 ℃ of cuts, add 5 quality normal hexane doubly and get 10.0g (1S, 2S in-18 ℃ of placement recrystallizations, 5S-2-hydroxyl-3-pinone, yield are 59.5%.
Present embodiment reclaims the trimethyl carbinol and water azeotrope 67.4g, and t butanol content 81%, the trimethyl carbinol rate of recovery are 91%.
Embodiment 4
Taking by weighing α-Pai Xi 13.6g (0.1mol) joins in the 500mL there-necked flask that is connected to mechanical stirring and thermometer, adding the 136g massfraction is 60% trimethyl carbinol aqueous solution, after stirring makes the α-Pai Xi dissolving, be cooled to 5 ℃, add potassium permanganate 25.3g (0.16mol) when treating homo(io)thermism, keep temperature of reaction system to float in the adition process and be no more than 4 ℃, add the back that finishes and keep system temperature to finish reaction at 5 ℃ of reaction 23h.With reacting liquid filtering, the filter cake massfraction is 60% trimethyl carbinol aqueous solution 20g washing 3 times, washing lotion and filtrate are incorporated in 40 ℃ of following vacuum rotary steams recovery trimethyl carbinols to the dripless outflow, leave standstill and be divided into oil reservoir and water layer, isolate oil reservoir, twice of extracted with diethyl ether of water layer, water successively after ether layer and oil reservoir merged, saturated sodium bicarbonate washing back is steamed in the normal temperature backspin and is removed ether, then in the 2.2kPa underpressure distillation, collect 110～115 ℃ of cuts, add 3 quality ethyl acetate doubly and get 10.1g (1S, 2S in-18 ℃ of placement recrystallizations, 5S)-and 2-hydroxyl-3-pinone, yield is 60.2%.
Present embodiment reclaims the trimethyl carbinol and water azeotrope 91.8g, and t butanol content 79%, the trimethyl carbinol rate of recovery are 93%.
Embodiment 5
Taking by weighing α-Pai Xi 13.6g (0.1mol) joins in the 500mL there-necked flask that is connected to mechanical stirring and thermometer, adding the 110g massfraction is 40% trimethyl carbinol aqueous solution (being made by the trimethyl carbinol water azeotrope and the water that reclaim among the embodiment 4), after stirring makes the α-Pai Xi dissolving, be cooled to 10 ℃, add potassium permanganate 28.4g (0.18mol) when treating homo(io)thermism, keep temperature of reaction system to float in the adition process and be no more than 4 ℃, add the back that finishes and keep system temperature to finish reaction at 10 ℃ of reaction 23h.With reacting liquid filtering, the filter cake massfraction is 40% trimethyl carbinol aqueous solution 20g washing 3 times, washing lotion and filtrate are incorporated in 40 ℃ of following vacuum rotary steams recovery trimethyl carbinols to the dripless outflow, leave standstill and be divided into oil reservoir and water layer, isolate oil reservoir, twice of extracted with diethyl ether of water layer, water successively after ether layer and oil reservoir merged, saturated sodium bicarbonate washing back is steamed in the normal temperature backspin and is removed ether, then in the 2kPa underpressure distillation, collect 110～115 ℃ of cuts, add 3 quality ethanol doubly and get 10.3g (1S, 2S in-18 ℃ of placement recrystallizations, 5S)-and 2-hydroxyl-3-pinone, yield is 61.5%.
Present embodiment reclaims the trimethyl carbinol and water azeotrope 57.7g, and t butanol content 82%, the trimethyl carbinol rate of recovery are 91%.
Embodiment 6
Taking by weighing α-Pai Xi 13.6g (0.1mol) joins in the 500mL there-necked flask that is connected to mechanical stirring and thermometer, adding the 110g massfraction is 40% trimethyl carbinol aqueous solution, after stirring makes the α-Pai Xi dissolving, be cooled to-10 ℃, add potassium permanganate 28.4g (0.18mol) when treating homo(io)thermism, keep temperature of reaction system to float in the adition process and be no more than 4 ℃, add the back that finishes and keep system temperature to finish reaction at-10 ℃ of reaction 23h.With reacting liquid filtering, get filtrate and reclaim the trimethyl carbinol to the dripless outflow in 40 ℃ of following vacuum rotary steams, leave standstill and be divided into oil reservoir and water layer, isolate oil reservoir,, collect 110～115 ℃ of cuts in the 2kPa underpressure distillation, add 3 quality ethanol doubly and get 10g (1S in-18 ℃ of placement recrystallizations, 2S, 5S)-2-hydroxyl-3-pinone, yield is 59.5%.
Present embodiment reclaims the trimethyl carbinol and water azeotrope 48.3g, and t butanol content 82%, the trimethyl carbinol rate of recovery are 90%.
The comparative example
Taking by weighing α-Pai Xi 13.6g (0.1mol) joins in the 500mL there-necked flask that is connected to mechanical stirring and thermometer, adding 200g massfraction is 90% aqueous acetone solution, after stirring makes the α-Pai Xi dissolving, be cooled to 0 ℃, add potassium permanganate 26.8g (0.17mol) when treating homo(io)thermism, keep temperature of reaction system to float in the adition process and be no more than 4 ℃, add the back that finishes and keep system temperature to finish reaction at 0 ℃ of reaction 24h.With reacting liquid filtering, the filter cake massfraction is 90% aqueous acetone solution 20g washing 3 times, washing lotion and filtrate are incorporated in 56 ℃ of vacuum rotary steams reclaim acetone after do not have acetone and flow out, leave standstill and be divided into oil reservoir and water layer, isolate oil reservoir, twice of extracted with diethyl ether of water layer, water successively after ether layer and oil reservoir merged, saturated sodium bicarbonate washing back is steamed in the normal temperature backspin and is removed ether, then in the 2kPa underpressure distillation, collect 110～115 ℃ of cuts, add 3 quality ethylene glycol monomethyl ether doubly and get 10.4g (1S, 2S in-18 ℃ of placement recrystallizations, 5S)-and 2-hydroxyl-3-pinone, yield 62%.
Present embodiment reclaims acetone 141.4g, acetone content 98%, the acetone rate of recovery 70%.For guaranteeing to reach the acetone rate of recovery of maximum possible, present embodiment has adopted increase condensation area, 10 ℃ of control methods such as cryogenic condensation water when vacuum rotary steam reclaims acetone.From embodiment 1～6 and comparative example's result as can be seen, the inventive method can reduce production costs keeping having the high advantage of solvent recovering rate under the constant substantially prerequisite of product yield.
The foregoing description is a preferred implementation of the present invention; but embodiments of the present invention are not restricted to the described embodiments; other any do not deviate from change, the modification done under spirit of the present invention and the principle, substitutes, combination, simplify; all should be the substitute mode of equivalence, be included within protection scope of the present invention.
Claims (9)
1, a kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone, adjust the temperature to-10～18 ℃ after comprising the steps: to be dissolved in α-Pai Xi in 8～15 quality trimethyl carbinol aqueous solution doubly, add potassium permanganate, keep temperature of reaction system to float at 0～4 ℃ in the adition process, the ratio of the potassium permanganate that is added and the amount of substance of α-Pai Xi is 1.3: 1～2: 1; Keep the temperature of system-10～18 ℃ of reactions 23～25 hours after adding potassium permanganate, finish reaction, with reacting liquid filtering, filtrate reclaimed to leave standstill behind the trimethyl carbinol be divided into oil reservoir and water layer, get oil reservoir, in 1.8～2.2kPa underpressure distillation, collect 110～115 ℃ of cuts, add 3～5 quality organic solvent doubly in-10～-18 ℃ place down recrystallizations obtain purifying (1S, 2S, 5S)-2-hydroxyl-3-pinone.
It is 2, according to claim 1 that (5S)-preparation method of 2-hydroxyl-3-pinone, it is characterized in that: the massfraction of the described trimethyl carbinol aqueous solution is 30～60% for 1S, 2S.
It is 3, according to claim 1 that (5S)-preparation method of 2-hydroxyl-3-pinone, it is characterized in that: the massfraction of the described trimethyl carbinol aqueous solution is 40～50% for 1S, 2S.
It is 4, according to claim 1 that (5S)-preparation method of 2-hydroxyl-3-pinone, it is characterized in that: described organic solvent is sherwood oil, ether, normal hexane, ethyl acetate, ethanol or ethylene glycol monomethyl ether for 1S, 2S.
It is 5, according to claim 1 that (1S, 2S 5S)-preparation method of 2-hydroxyl-3-pinone, is characterized in that: describedly adjust the temperature to-5～10 ℃ after being dissolved in α-Pai Xi in the trimethyl carbinol aqueous solution.
It is 6, according to claim 1 that (1S, 2S 5S)-preparation method of 2-hydroxyl-3-pinone, is characterized in that: describedly adjust the temperature to-5～5 ℃ after being dissolved in α-Pai Xi in the trimethyl carbinol aqueous solution.
It is 7, according to claim 1 that (1S, 2S 5S)-preparation method of 2-hydroxyl-3-pinone, is characterized in that: describedly filtrate is reclaimed the trimethyl carbinol reclaim the trimethyl carbinol to the azeotrope outflow of not having the trimethyl carbinol and water for filtrate decompression being revolved steam.
8, (1S according to claim 1,2S, 5S)-preparation method of 2-hydroxyl-3-pinone, it is characterized in that: the filter cake of described filtration gained use with as behind the identical trimethyl carbinol solution washing of the trimethyl carbinol concentration of aqueous solution of solvent, washing lotion and filtrate are merged.
9, (1S according to claim 1,2S, 5S)-preparation method of 2-hydroxyl-3-pinone, it is characterized in that: described water layer organic solvent extraction organic phase, organic phase and oil reservoir are merged and remove organic solvent, described organic solvent is sherwood oil or ether.
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| 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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| 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 |
Non-Patent Citations (2)
| Title |
|---|
| The synthesis and Stereochemistry of the FourIsomeric Pinane-2,3-diols. ROBERT G. CARLSON, et al.J. Org. Chem.,Vol.36 No.16. 1971 * |
| 均相体系中β-蒎烯氧化制备诺蒎酸. 马世营等.林产化学与工业，第27卷第2期. 2007 * |
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