CN101412706A - Novel method for preparing 1,3-dihydroxy acetone from glycerol - Google Patents
Novel method for preparing 1,3-dihydroxy acetone from glycerol Download PDFInfo
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- CN101412706A CN101412706A CNA2008101623108A CN200810162310A CN101412706A CN 101412706 A CN101412706 A CN 101412706A CN A2008101623108 A CNA2008101623108 A CN A2008101623108A CN 200810162310 A CN200810162310 A CN 200810162310A CN 101412706 A CN101412706 A CN 101412706A
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Abstract
The invention discloses a new method for preparing 1, 3-dihydroxyacetone from glycerol, which comprises the following steps: (1) acetalation reaction, which is to perform acetalation reaction of the glycerol and benzaldehyde in the presence of a water-carrying agent and under the action of an acid catalyst A so as to obtain glycerol benzaldehyde acetal ester having a structure as shown in the formula (I); (2) oxidation reaction, which is to oxidize the glycerol benzaldehyde acetal ester in an organic solvent and under the action of an oxidizer so as to obtain 5-carbonyl-2-phenyl -1, 3-dioxane having a structure as shown in the formula (II); and (3) hydrolysis reaction, which is to hydrolyze the obtained 5-carbonyl-2-phenyl -1, 3-dioxane in the presence of an acid catalyst B so as to prepare a 1, 3-dihydroxyacetone dimer having a structure as shown in the formula (III). The synthetic route of the method uses the glycerin as a raw material, thus both the selectivity and the yield are higher than that by a method of direct oxidation, the target product is simple and convenient to separate, and the product purity can reach 99 percent; and compared with the prior art, the synthetic route of the method has stronger market competitiveness.
Description
(1) technical field
The present invention relates to a kind of 1, the preparation method of 3-otan.
(2) background technology
In recent years along with grease chemical article expanding production continuously of biofuel particularly, seriously drug on the market to cause its by-product glycerin, price glides significantly, is the problem that exploitation that raw material carries out derived product can well solve the glycerine surplus with glycerine, can reduce the production cost of biofuel again.1, (DHA dihydroxyacetone), is a kind of important medicine intermediate, industrial chemicals and foodstuff additive, the composition of makeup sun-screening agent to the 3-otan.Also can be used as a kind of Anti-virus agent,, can kill 51%～100% ewcastle disease virus as in the egg embryo culture; The anti-corrosive fresh-keeping that also can be used for fruits and vegetables, fishery products, meat product; Still have many other purposes among positive research and development.
At present, 1, the industrialized process for preparing of 3-otan comparative maturity mainly is enzyme method for making (J.Ferment Technol, 1979,57 (3): 227), promptly with glycerine dehydrogenation enzyme glycerine is oxidized to 1,3-otan.But the existence of mushroom has limited the concentration range of glycerine, makes the yield of enzyme method for making be difficult to improve, and because the more influence of by product makes whole aftertreatment technology become numerous and diverse, time consumption and energy consumption, production cost is high.Because DHA is of many uses, market capacity is big, and excessive as biological diesel oil byproduct glycerin, and the research high yield, to purify be that the novel method of feedstock production DHA has great importance easily with glycerine.
Be existing a lot of patents of otan and bibliographical information abroad, but mainly be that direct catalytic oxidation prepares otan with the chemical synthesis glycerine converting.Because glycerine is polyol, adopt the direct oxidation route, the transformation efficiency of glycerine and the productive rate of otan are all lower.The result of study that Kimura.etal announces shows, during the glycerine oxidation, in the Pt catalyzer, add Bi, can greatly improve selectivity to secondary alcohol, when catalyzer is 1%Bi-5%Pt/C, in one batch reaction productive rate of otan be 20% (Appl.Catal.A, 1993,96:217).When catalyzer is 0.6%Bi-3%Pt when loading on the gac, transformation efficiency is 40% in a mixed bed reaction, the productive rate of DHA be 30% (German Patent, DE4228487).Under acidic conditions, and add a certain amount of auxiliary agent, use the Pt catalyzer, the transformation efficiency of glycerine reaches as high as 70%, but the maximum yield that transformation of glycerol forms otan for only 37% (Catalysis Today, 2000,57:127).This is up to now, and the glycerine oxidation prepares the highest data of otan productive rate.The direct catalyzed oxidation glycerine method of domestic report, catalyzer is 9%Pt-5%Bi/C, 55 ℃ of temperature of reaction, 50 hours reaction times, the selectivity of DHA has only 40.2%, and the transformation efficiency of glycerine is 81.6%, but the productive rate of DHA only is 32.8% (Hainan Normal University's journal (natural science edition), 2007,20 (3)).The direct oxidation of glycerine as can be seen only depends on and improves the shortcoming that catalyzer is difficult to change long reaction time, poor selectivity.
(3) summary of the invention
It is feedstock production 1 with glycerine that the technical problem to be solved in the present invention is to provide a kind of, the method for 3-otan, this preparation method's transformation efficiency height, selectivity are good, product separate purify simple.
For solving the problems of the technologies described above, the present invention adopts following technical scheme:
A kind of 1, the preparation method of 3-otan, described preparation method is as follows: (1) acetalation: in the presence of the band aqua, acetalation takes place and obtains structure suc as formula the glycerine phenyl aldehyde acetal ether shown in (I) in glycerine and phenyl aldehyde under acid catalyst A effect; (2) oxidizing reaction: the glycerine phenyl aldehyde acetal ether of gained under the oxygenant effect the oxidized structure that obtains suc as formula the 5-carbonyl-2-phenyl-1 shown in (II), 3-dioxane; (3) hydrolysis reaction: the hydrolysis in the presence of acid catalyst B of gained 5-carbonyl-2-phenyl-1,3-dioxane makes structure suc as formula 1 shown in (III), 3-otan dimer.
Reaction equation is as follows:
Each reactions steps to above-mentioned preparation method is elaborated below.
The described acetalation of step of the present invention (1) specifically can be carried out according to following steps: glycerine, phenyl aldehyde, acid catalyst A and band aqua are joined in the reaction vessel, be warming up to 100～130 ℃ of reactions 1～6 hour under stirring, after reaction finished, aldolization liquid obtained structure suc as formula the glycerine phenyl aldehyde acetal ether shown in (I) through separation and purification; The amount of substance ratio that feeds intake of described glycerine, phenyl aldehyde is 1:1.0～1.5, and the consumption of described acid catalyst A is 1～10% of a glycerine weight.
Further, the acid catalyst A that uses in the described acetalation can be liquid acid or solid acid, be preferably the vitriol oil, p-methyl benzenesulfonic acid or strongly acidic cation-exchange, described strongly acidic cation-exchange can be selected strongly acidic cation-exchanges such as CD550, D072.
The band aqua that uses in the described acetalation is preferably benzene or toluene, more preferably benzene.The volumetric usage of described band aqua is 3～5 times of glycerine volume.
Separation purification method described in the described acetalation can carry out according to following: described aldolization liquid through washing, dry, reclaim the band aqua after in the mixing solutions of benzene and sherwood oil in-9.0～-25.0 ℃ of crystallizations, obtain glycerine phenyl aldehyde acetal ether.
In the above-mentioned purification procedures, washing, dry, reclaim the band aqua, crystallization is routine operation, preferably, above-mentioned separation purification method is recommended to carry out according to following steps: aldolization liquid is used successively 10% NaOH solution washing, deionized water wash, use the Anhydrous potassium carbonate drying again, the band aqua is reclaimed in underpressure distillation, the mixing solutions (volume ratio 1:1) that adds benzene and sherwood oil, be refrigerated to-9.0～-25.0 ℃, after 3～4 hours, suction filtration is with cold benzene and the mixing solutions of sherwood oil (volume ratio 1:1) washing, obtain primary products, obtain purity near 100% glycerine phenyl aldehyde acetal ether through recrystallization again.The crystalline mother solution that band aqua that recovery obtains and crystallization obtain can be reused for aldolization, and recycle improves utilization ratio of raw materials, reduces cost.
The described oxidizing reaction of step of the present invention (2) is specifically carried out according to following steps: glycerine phenyl aldehyde acetal ether is joined in the organic solvent that contains oxygenant, under room temperature, reacted 0.5～10 hour, after reaction finishes, oxidation afterreaction liquid obtains structure suc as formula the 5-carbonyl-2-phenyl-1 shown in (II), 3-dioxane by separation and purification.
Further, the oxygenant that uses in the above-mentioned oxidizing reaction can be other metal oxide oxygenants such as potassium permanganate, comprises Collins reagent (chromium trioxide two pyridines), PCC reagent (chromium trioxide pyridine hydrochloride), DCC reagent (Dimethylammonium chloride chromium trioxide); Oxygenant also can be air or oxygen, and should add catalyzer in the system this moment, and feeds the air or the oxygen of capacity, and catalyzer can be TEMPO (2,2,6,6-tetramethyl piperidine-1-oxyradical), NaNO
2And FeCl
3, TEMPO, NaNO
2And FeCl
3Mole dosage be respectively 0.1～10%, 0.3～10% and 0.3～10% of glycerine phenyl aldehyde acetal ether molar weight.Described oxygenant is preferably Collins reagent, PCC reagent or DCC reagent, and its consumption is 2～5 times of glycerine phenyl aldehyde acetal ether weight.
Collins reagent used in the present invention, PCC reagent and DCC reagent can be prepared as follows:
(1) Collins reagent (chromium trioxide two pyridines)
Under the ice bath cooling, chromium trioxide is slowly joined in the excessive pyridine, controlled temperature (is being noted: definitely pyridine can not be added in the chromium trioxide below 20 ℃, otherwise can cause danger because of very exothermic), under constantly stirring, can produce yellow pyridine chromic oxide precipitation, continue to stir, yellow mercury oxide just gradates the crystallization of laking particle.Filtration is also used petroleum ether, gets Collins reagent after the drying.
(2) PCC reagent (chromium trioxide pyridine hydrochloride)
In 6mol/L hydrochloric acid, add chromium trioxide (adding while stirring) fast, after the 5min, homogeneous phase solution is chilled to 0 ℃, obtain reddish-brown liquid, normal pressure removes by filter insolubles, in 10min, pyridine is added then, adding along with pyridine, there is yellow solid to separate out gradually, drips pyridine, be chilled to 0 ℃ again, obtain the safran solid, filter to collect product with sand core funnel, product be placed in the vacuum drier behind the dry 1h, be placed on again in the moisture eliminator that Vanadium Pentoxide in FLAKES is housed behind the Air drying 48h PCC reagent.
(3) DCC reagent (Dimethylammonium chloride chromium trioxide)
In filling the beaker of deionized water, add chromium trioxide.After waiting to dissolve, stir the Dimethylammonium chloride that adds equimolar amount down again.Heating in water bath is incubated 10～15 minutes again to the solids dissolving.Cooling back decompress filter with the frozen water washing once, gets DCC reagent after the oven dry.
Further again, the organic solvent that uses in the above-mentioned oxidizing reaction preferably uses methylene dichloride, trichloromethane, hexanaphthene or N, dinethylformamide.The quality consumption of described organic solvent is 10～30 times of glycerine phenyl aldehyde acetal ether weight.
Separation purification method described in the described oxidizing reaction carries out according to following: oxidation afterreaction liquid is after organic solvent is reclaimed in washing, drying, distillation, and recrystallization obtains 5-carbonyl-2-phenyl-1,3-dioxane.
In the above-mentioned purification procedures, washing, drying, distillation, recrystallization are routine operation, preferably, above-mentioned separation and purification is recommended to carry out according to following steps: with oxidation afterreaction liquid, use the saturated common salt water washing, use anhydrous magnesium sulfate drying again, organic solvent is reclaimed in air distillation, surplus materials ether recrystallization obtains highly purified 5-carbonyl-2-phenyl-1, the 3-dioxane.
The described hydrolysis reaction of step of the present invention (3) specifically carries out according to following steps: with 5-carbonyl-2-phenyl-1,3-dioxane, acid catalyst B and deionized water join in the reaction vessel respectively, be warming up to 50～90 ℃ under stirring, reacted 2～10 hours, after reaction is finished, obtain 1 by separation and purification, 3-otan dimer; The consumption of described acid catalyst B is 5-carbonyl-2-phenyl-1,1～4 times of 3-dioxane weight.
Further, the acid catalyst B that uses in the described hydrolysis reaction can select catalyzer commonly used in the general hydrolysis reaction, as p-methyl benzenesulfonic acid, sulfuric acid, hydrochloric acid, the present invention recommends to use solid acid catalyst, the preferred CD550 strongly acidic cation-exchange of described solid acid catalyst, D072 strongly acidic cation-exchange or D061 strongly acidic cation-exchange.
The consumption that adds entry in the said hydrolyzed reaction is 5-carbonyl-2-phenyl-1,10～30 times of 3-dioxane weight.
Separation purification method described in the described hydrolysis reaction adopts present technique field method commonly used, such as when using solid acid catalyst, can carry out separation and purification as follows and obtain product: after hydrolysis reaction is finished, the solids removed by filtration acid catalyst, filtrate adds propyl carbinol with a small amount of normal hexane washing back and removes moisture by being lower than 40 ℃ of vacuum component distillations under the condition, at room temperature the stirred crystallization thing is after about 16～20 hours, filter and the flushing crystal with 0 ℃ acetone, and be lower than under 40 ℃ the condition dry, obtain 1,3-otan dimer.The solid acid catalyst that filtration obtains can be reused.
Available thin-layer chromatography method detects 5-carbonyl-2-phenyl-1 among the present invention, the hydrolysis situation of 3-dioxane, hydrolysis reaction detected the hydrolysis situation every 1 hour, use the silica-gel plate thin-layer chromatography, solvent systems is hexanaphthene: ethyl acetate=1:1,5-carbonyl-2-phenyl-1, the migration ratio R of 3-dioxane
f=0.67.
In addition, the present invention is marked with A, B respectively with the acid catalyst of using in acetalation and the hydrolysis reaction, its objective is to be used to distinguish different step, does not represent that they cannot be catalyzer of the same race.
Compared with prior art, beneficial effect of the present invention is:
1, synthetic route of the present invention is raw material with glycerine, and all than the method height of direct oxidation, target product separates easy for selectivity and yield, and product purity can reach 99%;
2, use solid acid catalyst in the hydrolysis reaction of the present invention, easily separate with product, it is easy to purify, and technology is simple, and solid acid catalyst can reuse, and also can use continuously.
Therefore, than prior art, of the present invention by glycerine preparation 1, the route of 3-otan has the bigger market competitiveness.
(4) description of drawings:
Fig. 1 is 1,3-otan dimer proton nmr spectra, and chloroform-d (D, 99.8%)+TMS 0.03% (v/v) is a solvent.
(5) specific embodiments
With specific embodiment technical scheme of the present invention is described further below, but protection scope of the present invention is not limited thereto:
Embodiment one
Step (1): in the 250ml round-bottomed flask of prolong, water trap is housed, add p-methyl benzenesulfonic acid 0.6g, glycerine 58.0g, phenyl aldehyde 61.0g, benzene 100ml, heated and stirred, condensing reflux.Temperature of reaction is controlled at 130 ℃, 2 hours reaction times.Reaction solution after washing, Anhydrous potassium carbonate drying, underpressure distillation (recovery benzene) in-10 ℃ benzene and the mixing solutions of sherwood oil (volume ratio 1:1) crystallization obtain glycerine phenyl aldehyde acetal ether 12.4g, its productive rate is 12.3%.Benzene that reclaims and acetal crystalline mother solution keep stand-by.
Step (2): the 1mol chromium trioxide is slowly joined in the 2mol pyridine, and control reaction temperature can produce yellow pyridine chromic oxide precipitation below 40 ℃ under constantly stirring, continue to stir, and yellow mercury oxide just gradates the crystallization of laking particle.Filtration is also used petroleum ether, gets Collins reagent (chromium trioxide two pyridines) after the drying.In the there-necked flask of prolong is housed, add 250ml methylene dichloride and 60.0gCollins reagent successively, add 12.4g glycerine phenyl aldehyde acetal ether again.Reaction after 1.5 hours goes out the upper solution decant under the room temperature, with the bottoms washed with dichloromethane, merges decant liquid and washings, and behind saturated common salt water washing, anhydrous magnesium sulfate drying, methylene dichloride is reclaimed in air distillation.Distillation back solid ether recrystallization, and get 10.1g5-carbonyl-2-phenyl-1 after the vacuum-drying at room temperature, 3-dioxane, productive rate are 81.5%.
Step (3): the CD550 strongly acidic cation-exchange was immersed in after with deionized water wash in the deionized water after 24 hours, take out dry standby.In being housed, the there-necked flask of prolong adds 10.1g5-carbonyl-2-phenyl-1,3-dioxane and 100ml deionized water, heated and stirred to 80 ℃ adds the 30.0gCD550 strongly acidic cation-exchange after waiting to dissolve again, utilizes thin-layer chromatography to follow the tracks of the detection reaction terminal point.After reaction was finished, decompress filter was removed catalyzer, and filtrate is washed with normal hexane, adds propyl carbinol then, and 40 ℃ of following vacuum component distillations are removed moisture.Stirred crystallization thing at room temperature filters and the flushing crystal with 0 ℃ acetone, and is being lower than under 40 ℃ the condition dryly, obtains 1,3-otan dimer 4.9g, productive rate 97.0%.The chemical structure of product is through the HNMR analysis confirmation, and the phosphorus molybdenum acid solution colour developing is positive reaction.
Embodiment two
Step (1): in the 250ml round-bottomed flask of prolong, water trap is housed, add 98% sulfuric acid 1ml, glycerine 58g, phenyl aldehyde 61g (phenyl aldehyde excessive about 6%) and acetal crystalline mother solution 100ml, heated and stirred, condensing reflux, 130 ℃ of temperature of reaction, 6 hours reaction times.The reaction finish after, reaction solution after washing, Anhydrous potassium carbonate drying, underpressure distillation (recovery benzene) in-10 ℃ benzene and the mixing solutions of sherwood oil (1:1) crystallization obtain glycerine phenyl aldehyde acetal ether 21.6g, its productive rate is 21.4%.Benzene that reclaims and crystalline mother solution keep stand-by.
Step (2): in 6mol/L hydrochloric acid (containing 1.1molHCl), add 100g chromium trioxide (adding while stirring) fast, after the 5min, homogeneous phase solution is chilled to 0 ℃, obtain reddish-brown liquid, normal pressure removes by filter insolubles, in 10min, the 79.1g pyridine is added then,, have yellow solid to separate out gradually along with the adding of pyridine, drip pyridine, again be chilled to 0 ℃, obtain the safran solid, filter with sand core funnel and collect product, product is placed in the vacuum drier behind the dry 1h, be placed on Air drying 48h in the moisture eliminator that Vanadium Pentoxide in FLAKES is housed again, obtain constant weight product 180g, be i.e. PCC reagent (chromium trioxide pyridine hydrochloride).In the there-necked flask of prolong is housed, add 250ml methylene dichloride and 45.0gPCC reagent successively, add 21.6g glycerine phenyl aldehyde acetal ether again.Reaction after 4 hours goes out the upper solution decant under the room temperature, with the bottoms washed with dichloromethane, merges decant liquid and washings, and behind saturated common salt water washing, anhydrous magnesium sulfate drying, methylene dichloride is reclaimed in air distillation; To distill back solid ether recrystallization, and get 5-carbonyl-2-phenyl-1 after the vacuum-drying at room temperature, 3-dioxane, productive rate are 85.2%.
Step (3): the D072 strongly acidic cation-exchange was immersed in after with deionized water wash in the deionized water after 24 hours, take out dry standby.In being housed, the there-necked flask of prolong adds 18.4g5-carbonyl-2-phenyl-1,3-dioxane and 100ml deionized water, heated and stirred to 90 ℃ adds the 40.0gD072 strongly acidic cation-exchange after waiting to dissolve again, utilizes thin-layer chromatography to follow the tracks of the detection reaction terminal point.After reaction was finished, decompress filter was removed catalyzer, and filtrate is washed with normal hexane, adds propyl carbinol then, and 40 ℃ of following vacuum component distillations are removed moisture.At room temperature the stirred crystallization thing is about 24 hours, filters and the flushing crystal with 0 ℃ acetone, and is being lower than under 40 ℃ the condition dryly, obtains 1,3-otan dimer, productive rate 97.8%.The chemical structure of product is through the HNMR analysis confirmation, and the phosphorus molybdenum acid solution colour developing is positive reaction.
Embodiment three
Step (1): in the 250ml round-bottomed flask of prolong, water trap is housed, add D072 strongly acidic cation-exchange 6g, glycerine 58.0g, phenyl aldehyde 61.0g (phenyl aldehyde excessive about 6%), benzene 100ml, heated and stirred, condensing reflux, water and entrainer benzene azeotropic that reaction produces steam.Temperature of reaction is controlled at 110 ℃, 6 hours reaction times.After reaction was finished, reaction solution obtained glycerine phenyl aldehyde acetal ether 18.0g in-10 ℃ benzene and the mixing solutions of sherwood oil (1:1) after washing, Anhydrous potassium carbonate drying, underpressure distillation (recovery benzene), and its productive rate is 17.9%.Benzene that reclaims and acetal crystalline mother solution keep stand-by.
Step (2): heavily add 50g (0.5mol) chromium trioxide at the beaker that fills 20mL water.After waiting to dissolve, add 40.8g (0.5mol) Dimethylammonium chloride again under stirring.Heating in water bath is incubated 10～15 minutes again to the solids dissolving.Cooling back decompress filter with the frozen water washing once, gets 70g orange crystal, i.e. DCC reagent (Dimethylammonium chloride chromium trioxide) after the oven dry.In the there-necked flask of prolong is housed, add 250ml methylene dichloride and 45.0gDCC reagent successively, add 18.0g glycerine phenyl aldehyde acetal ether again.Reaction after 6 hours goes out the upper solution decant under the room temperature, with the bottoms washed with dichloromethane, merges decant liquid and washings, and behind saturated common salt water washing, anhydrous magnesium sulfate drying, methylene dichloride is reclaimed in air distillation; , will distill back solid ether recrystallization, and get 15.3g5-carbonyl-2-phenyl-1 after the vacuum-drying at room temperature, 3-dioxane, productive rate are 85.0%.
Step (3): the D061 strongly acidic cation-exchange was immersed in after with deionized water wash in the deionized water after 24 hours, take out dry standby.In being housed, the there-necked flask of prolong adds 15.3g5-carbonyl-2-phenyl-1,3-dioxane and 100ml deionized water, heated and stirred to 80 ℃ adds 35.0g D061 strongly acidic cation-exchange again after waiting to dissolve, utilize thin-layer chromatography to follow the tracks of the detection reaction terminal point.After reaction was finished, decompress filter was removed catalyzer, and filtrate is washed with normal hexane, adds propyl carbinol then, and 40 ℃ of following vacuum component distillations are removed moisture.At room temperature the stirred crystallization thing is about 24 hours, filters and the flushing crystal with 0 ℃ acetone, and is being lower than under 40 ℃ the condition dryly, obtains 1,3-otan dimer 7.5g, productive rate 98.0%.The chemical structure of product is through the HNMR analysis confirmation, and the phosphorus molybdenum acid solution colour developing is positive reaction.
Embodiment four
Step (1): in the 250ml round-bottomed flask of prolong, water trap is housed, add p-methyl benzenesulfonic acid 0.6g, glycerine 58.0g, phenyl aldehyde 61.0g, benzene 100ml, heated and stirred, condensing reflux.Temperature of reaction is controlled at 130 ℃, 2 hours reaction times.Reaction solution after washing, Anhydrous potassium carbonate drying, underpressure distillation (recovery benzene) in-10 ℃ benzene and the mixing solutions of sherwood oil (1:1) crystallization obtain glycerine phenyl aldehyde acetal ether 18.0g, its productive rate is 17.8%.Benzene that reclaims and acetal crystalline mother solution keep stand-by.
Step (2): in the there-necked flask that prolong, bubbler and thermometer are housed, add the N of 250ml successively, dinethylformamide, 3.5mmolNaNO
2, 3.5mmolFeCl
35H
2O, 1.4mmolTEMPO (2,2,6,6-tetramethyl piperidine-1-oxyradical) add 17.8g glycerine phenyl aldehyde acetal ether again.Under room temperature and magnetic agitation condition, the air that feeds the purification of capacity is an oxygenant, regulates spinner-type flowmeter to 2000ml/min, carries out blistering reaction, and 6～8h afterreaction finishes.Reaction solution is behind washing, anhydrous magnesium sulfate drying, and N, dinethylformamide are reclaimed in underpressure distillation.Distillation back solid ether recrystallization, and get 12.5g5-carbonyl-2-phenyl-1 after the vacuum-drying at room temperature, 3-dioxane, productive rate are 70%.
Step (3): the CD550 strongly acidic cation-exchange was immersed in after with deionized water wash in the deionized water after 24 hours, take out dry standby.In being housed, the there-necked flask of prolong adds 12.5g5-carbonyl-2-phenyl-1,3-dioxane and 100ml deionized water, heated and stirred to 80 ℃ adds the CD550 strongly acidic cation-exchange of 35.0g again after waiting to dissolve, utilize thin-layer chromatography to follow the tracks of the detection reaction terminal point.After reaction was finished, decompress filter was removed catalyzer, and filtrate is washed with normal hexane, adds propyl carbinol then, and 40 ℃ of following vacuum component distillations are removed moisture.Stirred crystallization thing at room temperature filters and the flushing crystal with 0 ℃ acetone, and is being lower than under 40 ℃ the condition dryly, obtains 1,3-otan dimer 6.2g, productive rate 98.5%.The chemical structure of product is through the HNMR analysis confirmation, and the phosphorus molybdenum acid solution colour developing is positive reaction.
Embodiment five
Step (1): in the 250ml round-bottomed flask of prolong, water trap is housed, add p-methyl benzenesulfonic acid 0.6g, glycerine 58.0g, phenyl aldehyde 61.0g, benzene 100ml, heated and stirred, condensing reflux.Temperature of reaction is controlled at 130 ℃, 2 hours reaction times.Reaction solution after washing, dry, underpressure distillation (recovery benzene) in-10 ℃ benzene and the mixing solutions of sherwood oil (1:1) crystallization obtain glycerine phenyl aldehyde acetal ether 20.0g, its productive rate is 19.8%.
Step (2): in the there-necked flask that prolong, bubbler and thermometer are housed, add 250mlN successively, dinethylformamide, 3.6mmolNaNO
2, 3.6mmolFeCl
35H
2O, 1.5mmolTEMPO (2,2,6,6-tetramethyl piperidine-1-oxyradical) add 19.8g glycerine phenyl aldehyde acetal ether again.Under room temperature and magnetic agitation condition, be oxygenant with the pure oxygen, regulate spinner-type flowmeter to 500ml/min, carry out blistering reaction, 6～8h afterreaction finishes.Reaction solution is behind washing, anhydrous magnesium sulfate drying, and N, dinethylformamide are reclaimed in underpressure distillation.Distillation back solid ether recrystallization, and get 14.8g5-carbonyl-2-phenyl-1 after the vacuum-drying at room temperature, 3-dioxane, productive rate are 75%.
Step (3): the CD550 strongly acidic cation-exchange was immersed in after with deionized water wash in the deionized water after 24 hours, take out dry standby.In being housed, the there-necked flask of prolong adds 14.8g5-carbonyl-2-phenyl-1,3-dioxane and 100ml deionized water, heated and stirred to 60 ℃ adds the CD550 strongly acidic cation-exchange of 40.0g again after waiting to dissolve, utilize thin-layer chromatography to follow the tracks of the detection reaction terminal point.After reaction was finished, decompress filter was removed catalyzer, and filtrate is washed with normal hexane, adds propyl carbinol then, and 40 ℃ of following vacuum component distillations are removed moisture.Stirred crystallization thing at room temperature filters and the flushing crystal with 0 ℃ acetone, and is being lower than under 40 ℃ the condition dryly, obtains 1,3-otan dimer 7.3g, productive rate 98.0%.The chemical structure of product is through the HNMR analysis confirmation, and the phosphorus molybdenum acid solution colour developing is positive reaction.
Claims (10)
1, a kind of 1, the preparation method of 3-otan, it is characterized in that described preparation method is: (1) acetalation: in the presence of the band aqua, acetalation takes place and obtains structure suc as formula the glycerine phenyl aldehyde acetal ether shown in (I) in glycerine and phenyl aldehyde under acid catalyst A effect; (2) oxidizing reaction: described glycerine phenyl aldehyde acetal ether in organic solvent under the oxygenant effect the oxidized structure that obtains suc as formula the 5-carbonyl-2-phenyl-1 shown in (II), 3-dioxane; (3) hydrolysis reaction: described 5-carbonyl-2-phenyl-1, the hydrolysis in the presence of acid catalyst B of 3-dioxane makes structure suc as formula 1 shown in (III), 3-otan dimer;
2, as claimed in claim 11, the preparation method of 3-otan, it is characterized in that described step (1) acetalation specifically carries out according to following steps: glycerine, phenyl aldehyde, acid catalyst A and band aqua are joined in the reaction vessel, be warming up to 100～130 ℃ of reactions 1～6 hour under stirring, after reaction finished, aldolization liquid obtained structure suc as formula the glycerine phenyl aldehyde acetal ether shown in (I) through separation and purification; The amount of substance ratio that feeds intake of described glycerine, phenyl aldehyde is 1:1.0～1.5, and the consumption of described acid catalyst A is 1～10% of a glycerine weight.
3, as claimed in claim 11, the preparation method of 3-otan, it is characterized in that described step (2) oxidizing reaction specifically carries out according to following steps: glycerine phenyl aldehyde acetal ether is joined in the organic solvent that contains oxygenant, under room temperature, reacted 0.5～10 hour, after reaction finishes, oxidation afterreaction liquid obtains structure suc as formula the 5-carbonyl-2-phenyl-1 shown in (II), 3-dioxane by separation and purification.
4, as claimed in claim 11, the preparation method of 3-otan, it is characterized in that described step (3) hydrolysis reaction specifically carries out according to following steps: with 5-carbonyl-2-phenyl-1,3-dioxane, acid catalyst B and deionized water join in the reaction vessel respectively, be warming up to 50～90 ℃ under stirring, reacted 2～10 hours, after reaction is finished, obtain 1 by separation and purification, 3-otan dimer; The consumption of described acid catalyst B is 5-carbonyl-2-phenyl-1,1～4 times of 3-dioxane weight.
5, described 1 as one of claim 1～4, the preparation method of 3-otan is characterized in that the acid catalyst A that uses in described step (1) acetalation is sulfuric acid, p-methyl benzenesulfonic acid or strongly acidic cation-exchange.
6, described 1 as one of claim 1～4, the preparation method of 3-otan is characterized in that the band aqua that uses in described step (1) acetalation is benzene or toluene.
7, described 1 as one of claim 1～4, the preparation method of 3-otan is characterized in that the oxygenant that uses in described step (2) oxidizing reaction air or oxygen as capacity, also add catalyzer 2 in the reaction system this moment, 2,6,6-tetramethyl piperidine-1-oxyradical, NaNO
2And FeCl
3, added 2,2,6,6-tetramethyl piperidine-1-oxyradical, NaNO
2And FeCl
3Mole dosage be respectively 0.1～10%, 0.3～10% and 0.3～10% of glycerine phenyl aldehyde acetal ether molar weight.
8, described 1 as one of claim 1～4, the preparation method of 3-otan is characterized in that the oxygenant that uses in described step (2) oxidizing reaction is chromium trioxide two pyridines, chromium trioxide pyridine hydrochloride or hydrochloric acid dimethylammonium chromium trioxide; The consumption of described oxygenant is 2～5 times of glycerine phenyl aldehyde acetal ether (I) weight.
9, described 1 as one of claim 1～4, the preparation method of 3-otan is characterized in that the organic solvent that uses in described step (2) oxidizing reaction is methylene dichloride, trichloromethane, hexanaphthene or N, dinethylformamide.
10, as one of claim 1～4 described 1, the preparation method of 3-otan, it is characterized in that the acid catalyst B that uses in described step (3) hydrolysis reaction is solid acid catalyst, described solid acid catalyst is selected from the CD550 strongly acidic cation-exchange, D072 strongly acidic cation-exchange or D061 strongly acidic cation-exchange.
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