CN101229996A - Method for preparing (1S,2S,5S)-2-hydroxy-3-pinone - Google Patents
Method for preparing (1S,2S,5S)-2-hydroxy-3-pinone Download PDFInfo
- Publication number
- CN101229996A CN101229996A CNA2008100261453A CN200810026145A CN101229996A CN 101229996 A CN101229996 A CN 101229996A CN A2008100261453 A CNA2008100261453 A CN A2008100261453A CN 200810026145 A CN200810026145 A CN 200810026145A CN 101229996 A CN101229996 A CN 101229996A
- Authority
- CN
- China
- Prior art keywords
- pinone
- trimethyl carbinol
- hydroxyl
- preparation
- aqueous solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Landscapes
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
Abstract
The invention discloses a method for manufacturing (1S, 2S, 5S)-2-hydroxy-3-pinone, which comprises the following steps: Alpha-pinene is dissolved in aqueous solution of tertbutyl alcohol and the temperature is reduced to minus 10 to 18 DEG C; after potassium permanganate is added into the solution to carry out reaction under the temperature which is kept between minus 10 to 18 DEG C and reaction is finished after 23 to 25 hours; the temperature of the reaction system is kept between 0 to 4 DEG C in the process of adding the potassium permanganate; the reaction liquid is filtered and after the tertbutyl alcohol of filter liquid is recycled, the filter liquid is put in quiescence to be divided into an oil layer and a water layer; the oil layer is fetched and decompressed as well as distilled to collect distillation cut of 110 to 115 DEG C; organic solvent is added in the distillation cut under minus 10 to minus 18 DEG C and recrystallization is put into the mixture to get rarefied (1S, 2S, 5S)-2-hydroxy-3-pinone. The tertbutyl alcohol in the aqueous solution of the solvent tertbutyl alcohol which is used in the manufacturing process of the invention has good recoverability and high coefficient of recovery, and can be recycled in the industrial production and is suitable for the requirement of reducing cost in the industrial production.
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)-and 2-hydroxyl-3-pinone, yield is 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. (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.
2. according to claim 1 (1S, 2S, 5S)-and the preparation method of 2-hydroxyl-3-pinone, it is characterized in that: the massfraction of the described trimethyl carbinol aqueous solution is 30～60%.
3. according to claim 1 (1S, 2S, 5S)-and the preparation method of 2-hydroxyl-3-pinone, it is characterized in that: the massfraction of the described trimethyl carbinol aqueous solution is 40～50%.
4. according to claim 1 (1S, 2S, 5S)-and the 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.
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. according to claim 1 (1S, 2S 5S)-preparation method of 2-hydroxyl-3-pinone, is characterized in that: described water layer organic solvent extraction organic phase, and organic phase and oil reservoir are merged and remove organic solvent, described organic solvent is sherwood oil or ether.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100261453A CN100567241C (en) | 2008-01-30 | 2008-01-30 | A kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CNB2008100261453A CN100567241C (en) | 2008-01-30 | 2008-01-30 | A kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101229996A true CN101229996A (en) | 2008-07-30 |
| CN100567241C CN100567241C (en) | 2009-12-09 |
Family
ID=39896871
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CNB2008100261453A Expired - Fee Related CN100567241C (en) | 2008-01-30 | 2008-01-30 | A kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN100567241C (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481317B (en) * | 2009-02-04 | 2011-11-09 | 南京林业大学 | L-N-substituted-3-pinane, synthesis and use thereof |
| CN101665421B (en) * | 2009-09-18 | 2012-09-05 | 南京林业大学 | Synthetic method of camphorquinone |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100357240C (en) * | 2003-07-16 | 2007-12-26 | 广西壮族自治区化工研究院 | Process for preparing levogyrate alpha-terpineol |
-
2008
- 2008-01-30 CN CNB2008100261453A patent/CN100567241C/en not_active Expired - Fee Related
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101481317B (en) * | 2009-02-04 | 2011-11-09 | 南京林业大学 | L-N-substituted-3-pinane, synthesis and use thereof |
| CN101665421B (en) * | 2009-09-18 | 2012-09-05 | 南京林业大学 | Synthetic method of camphorquinone |
Also Published As
| Publication number | Publication date |
|---|---|
| CN100567241C (en) | 2009-12-09 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110878007B (en) | Refining method of non-petroleum ethylene glycol | |
| CN113072434B (en) | Method for preparing cyclopropyl methyl ketone by one-step method | |
| CN110372512A (en) | A kind of process for separating and purifying of dimethyl carbonate | |
| CN106187841B (en) | A kind of industrialized process for preparing of clethodim | |
| CN100567241C (en) | A kind of (1S, 2S, 5S)-preparation method of 2-hydroxyl-3-pinone | |
| CN103467244A (en) | Technology using benzene to prepare cyclohexanol | |
| CN110818542A (en) | Purification method of 1, 2-cyclohexanedione | |
| CN105294491B (en) | A kind of preparation method of cyanoacetic acid and its derivative | |
| EP2589584B1 (en) | Method for preparing chlorohydrins and method for preparing epichlorohydrin using chlorohydrins prepared thereby | |
| EP2592063B1 (en) | Method for preparing chlorohydrins composition and method for preparing epichlorohydrin using chlorohydrins composition prepared thereby | |
| EP2589586B1 (en) | Method for preparing chlorohydrins composition and method for preparing epichlorohydrin using chlorohydrins composition prepared thereby | |
| CN102311307A (en) | Method for preparing octacosanol and triacontanol from rice bran wax | |
| EP2594549B1 (en) | Method for preparing a composition of chlorohydrins | |
| CN102558117A (en) | Method for preparing 5-nitro-2-furoate from abandoned biomass | |
| CN104591989B (en) | The preparation method of 5 [(4 chlorphenyl) methyl] 2,2 cyclopentanone dimethyls | |
| CN108976183A (en) | A method of by preparation by furfural gas phase hydrogenation for gamma-valerolactone | |
| CN112225653B (en) | Green synthesis method of natural benzaldehyde | |
| CN100448828C (en) | Method of raising solanesol content in crude product effectively | |
| CN102070620B (en) | Preparation method of antibacterial ester | |
| CN106957235B (en) | A kind of preparation method of tamoxifen | |
| EP2589585B1 (en) | Method for preparing chlorohydrins and method for preparing epichlorohydrin using chlorohydrins prepared thereby | |
| CN106518633B (en) | The production method of high-purity triethylene glycol | |
| CN110642683A (en) | Synthesis method of cement grinding aid component using dichloroisopropyl ether as raw material | |
| CN111018701B (en) | Method for preparing decanediol dicarboxylate and derivatives thereof | |
| EP2589583B1 (en) | Method for preparing chlorohydrins and method for preparing epichlorohydrin using chlorohydrins prepared thereby |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20091209 Termination date: 20130130 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |