CN101412706B - 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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- CN101412706B CN101412706B CN2008101623108A CN200810162310A CN101412706B CN 101412706 B CN101412706 B CN 101412706B CN 2008101623108 A CN2008101623108 A CN 2008101623108A CN 200810162310 A CN200810162310 A CN 200810162310A CN 101412706 B CN101412706 B CN 101412706B
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- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 title claims abstract description 132
- 238000000034 method Methods 0.000 title abstract description 22
- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 title abstract description 10
- 238000006243 chemical reaction Methods 0.000 claims abstract description 68
- 235000011187 glycerol Nutrition 0.000 claims abstract description 63
- DHKHKXVYLBGOIT-UHFFFAOYSA-N acetaldehyde Diethyl Acetal Natural products CCOC(C)OCC DHKHKXVYLBGOIT-UHFFFAOYSA-N 0.000 claims abstract description 31
- 239000003377 acid catalyst Substances 0.000 claims abstract description 20
- -1 glycerol benzaldehyde acetal ester Chemical class 0.000 claims abstract description 17
- 238000006460 hydrolysis reaction Methods 0.000 claims abstract description 16
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 13
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 239000003960 organic solvent Substances 0.000 claims abstract description 9
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 75
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 66
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 125000002777 acetyl group Chemical class [H]C([H])([H])C(*)=O 0.000 claims description 29
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 25
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 25
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 25
- 230000002378 acidificating effect Effects 0.000 claims description 22
- 238000005341 cation exchange Methods 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 19
- 229910021641 deionized water Inorganic materials 0.000 claims description 19
- 238000000746 purification Methods 0.000 claims description 16
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 claims description 14
- 239000007788 liquid Substances 0.000 claims description 14
- 238000002360 preparation method Methods 0.000 claims description 14
- 229940117975 chromium trioxide Drugs 0.000 claims description 12
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical group [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 claims description 12
- 238000000926 separation method Methods 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 230000001590 oxidative effect Effects 0.000 claims description 10
- 239000011973 solid acid Substances 0.000 claims description 9
- 239000003054 catalyst Substances 0.000 claims description 8
- 239000000126 substance Substances 0.000 claims description 8
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 6
- JOXIMZWYDAKGHI-UHFFFAOYSA-N toluene-4-sulfonic acid Chemical compound CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 6
- HERWQQFSESWGRK-UHFFFAOYSA-N chromium(6+) oxygen(2-) pyridin-1-ium chloride Chemical compound Cl.N1=CC=CC=C1.[O-2].[O-2].[O-2].[Cr+6] HERWQQFSESWGRK-UHFFFAOYSA-N 0.000 claims description 5
- 150000003222 pyridines Chemical class 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 4
- 230000000694 effects Effects 0.000 claims description 4
- 230000007062 hydrolysis Effects 0.000 claims description 4
- 229910052760 oxygen Inorganic materials 0.000 claims description 4
- 239000001301 oxygen Substances 0.000 claims description 4
- 238000010792 warming Methods 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 2
- 229960001701 chloroform Drugs 0.000 claims description 2
- 239000002994 raw material Substances 0.000 abstract description 4
- IIRSIUDKSUUCNC-UHFFFAOYSA-N C(=O)=C1COC(OC1)C1=CC=CC=C1 Chemical compound C(=O)=C1COC(OC1)C1=CC=CC=C1 IIRSIUDKSUUCNC-UHFFFAOYSA-N 0.000 abstract description 3
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 abstract 2
- 239000003795 chemical substances by application Substances 0.000 abstract 1
- 239000007800 oxidant agent Substances 0.000 abstract 1
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 abstract 1
- CXEMWUYNUIKMNF-UHFFFAOYSA-N tert-butyl 4-chlorosulfonylpiperazine-1-carboxylate Chemical compound CC(C)(C)OC(=O)N1CCN(S(Cl)(=O)=O)CC1 CXEMWUYNUIKMNF-UHFFFAOYSA-N 0.000 abstract 1
- 238000005406 washing Methods 0.000 description 28
- 239000000243 solution Substances 0.000 description 26
- 238000004821 distillation Methods 0.000 description 23
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 22
- 239000000047 product Substances 0.000 description 18
- 239000003153 chemical reaction reagent Substances 0.000 description 15
- 238000002425 crystallisation Methods 0.000 description 15
- 230000008025 crystallization Effects 0.000 description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 12
- 238000001035 drying Methods 0.000 description 12
- 239000007787 solid Substances 0.000 description 12
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 11
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 description 10
- 238000001953 recrystallisation Methods 0.000 description 9
- 238000002156 mixing Methods 0.000 description 8
- 239000013078 crystal Substances 0.000 description 7
- 230000035484 reaction time Effects 0.000 description 7
- 238000011084 recovery Methods 0.000 description 7
- 238000004809 thin layer chromatography Methods 0.000 description 7
- 239000012027 Collins reagent Substances 0.000 description 6
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 6
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 238000011010 flushing procedure Methods 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000010413 mother solution Substances 0.000 description 6
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 6
- NPRDHMWYZHSAHR-UHFFFAOYSA-N pyridine;trioxochromium Chemical compound O=[Cr](=O)=O.C1=CC=NC=C1.C1=CC=NC=C1 NPRDHMWYZHSAHR-UHFFFAOYSA-N 0.000 description 6
- 238000004458 analytical method Methods 0.000 description 5
- 238000012790 confirmation Methods 0.000 description 5
- 238000001514 detection method Methods 0.000 description 5
- AMWVZPDSWLOFKA-UHFFFAOYSA-N phosphanylidynemolybdenum Chemical compound [Mo]#P AMWVZPDSWLOFKA-UHFFFAOYSA-N 0.000 description 5
- 229910000027 potassium carbonate Inorganic materials 0.000 description 5
- 238000010992 reflux Methods 0.000 description 5
- 230000009466 transformation Effects 0.000 description 5
- 238000001291 vacuum drying Methods 0.000 description 5
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical class [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 4
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000001914 filtration Methods 0.000 description 4
- 102000004190 Enzymes Human genes 0.000 description 3
- 108090000790 Enzymes Proteins 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical group O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 239000006227 byproduct Substances 0.000 description 3
- HNRCYODWHIIIFY-UHFFFAOYSA-N chromium(6+) N-methylmethanamine oxygen(2-) hydrochloride Chemical compound [O-2].[O-2].[O-2].[Cr+6].CNC.Cl HNRCYODWHIIIFY-UHFFFAOYSA-N 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 244000124209 Crocus sativus Species 0.000 description 2
- 238000013019 agitation Methods 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000002551 biofuel Substances 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- IQDGSYLLQPDQDV-UHFFFAOYSA-N dimethylazanium;chloride Chemical compound Cl.CNC IQDGSYLLQPDQDV-UHFFFAOYSA-N 0.000 description 2
- 239000003814 drug Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910000474 mercury oxide Inorganic materials 0.000 description 2
- UKWHYYKOEPRTIC-UHFFFAOYSA-N mercury(ii) oxide Chemical compound [Hg]=O UKWHYYKOEPRTIC-UHFFFAOYSA-N 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 239000003208 petroleum Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- 235000001674 Agaricus brunnescens Nutrition 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 1
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- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 238000006356 dehydrogenation reaction Methods 0.000 description 1
- 239000002283 diesel fuel Substances 0.000 description 1
- 229940120503 dihydroxyacetone Drugs 0.000 description 1
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- 239000000203 mixture Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical group 0.000 description 1
- 239000012286 potassium permanganate Substances 0.000 description 1
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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-dioxanehaving 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 that the exploitation that raw material carries out derived product can well solve the superfluous problem of glycerine 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.
The external chemical synthesis glycerine converting of using is existing a lot of patents of otan and bibliographical information, but mainly is that direct catalytic oxidation prepares otan.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 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, be 40% a mixed bed conversion rate, 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 is merely 32.8% (Hainan Normal University's journal (natural science edition); 2007,20 (3)).Can find out the direct oxidation of glycerine, only depend on and improve 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 that the present invention will solve is to provide a kind of, the method for 3-otan, and it is simple that this preparing method's transformation efficiency is high, selectivity is good, product separates purification.
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, said preparation method is following: (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 following:
Each reactions step in the face of above-mentioned preparation method is elaborated down.
The said 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 said glycerine, phenyl aldehyde is 1:1.0～1.5, and the consumption of said acid catalyst A is 1～10% of a glycerine weight.
Further; The acid catalyst A that uses in the said acetalation can be liquid acid or solid acid; Be preferably the vitriol oil, p-methyl benzenesulfonic acid or strongly acidic cation-exchange, said strongly acidic cation-exchange can be selected strongly acidic cation-exchanges such as CD550, D072.
The band aqua that uses in the said acetalation is preferably benzene or toluene, more preferably benzene.The volumetric usage of said band aqua is 3～5 times of glycerine volume.
Separation purification method described in the said acetalation can be according to carrying out as follows: said 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, drying, recovery band aqua, crystallization are routine operation, preferably; Above-mentioned separation purification method is recommended to carry out according to following steps: aldolization liquid is used 10% NaOH solution washing, deionized water wash successively, use Anhydrous potassium carbonate dry again, the band aqua is reclaimed in underpressure distillation; The mixing solutions (volume ratio 1:1) that adds benzene and sherwood oil is refrigerated to-9.0～-25.0 ℃, after 3～4 hours; Suction filtration; With the washing of cold benzene and the mixing solutions of sherwood oil (volume ratio 1:1), 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 said 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 through separation and purification.
Further; The oxygenant that uses in the above-mentioned oxidizing reaction can be other MOX 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.Said 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 prepare according to following method:
(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 can not pyridine be added in the chromium trioxide, otherwise can cause danger because of very exothermic) below 20 ℃, under constantly stirring, can produce yellow pyridine chromic oxide deposition; 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; Along with the adding of pyridine, there is yellow solid to separate out gradually, 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 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.Be incubated 10～15 minutes again after the dissolving of heating in water bath to solids.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 said organic solvent is 10～30 times of glycerine phenyl aldehyde acetal ether weight.
Separation purification method described in the said oxidizing reaction is according to carrying out as follows: 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 is used the ether recrystallization, obtains highly purified 5-carbonyl-2-phenyl-1, the 3-dioxane.
The said 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 accomplished; Obtain 1 through separation and purification, 3-otan dimer; The consumption of said 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 said hydrolysis reaction can select catalyzer commonly used in the general hydrolysis reaction; Like 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 said 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 said hydrolysis reaction adopts present technique field method commonly used; Such as when using solid acid catalyst, can carry out separation and purification according to following method and obtain product: after hydrolysis reaction is accomplished, the solids removed by filtration acid catalyst; Filtrating adds propyl carbinol with a small amount of normal hexane washing back and removes moisture through 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 whenever detected the hydrolysis situation at a distance from 1 hour, used the silica-gel plate thin-layer chromatography, and solvent systems is hexanaphthene: ETHYLE 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 the method than direct oxidation is high with yield for selectivity, and title product separates easy, and product purity can reach 99%;
2, use solid acid catalyst in the hydrolysis reaction of the present invention, be prone to 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:
Figure one is 1,3-otan dimer proton nmr spectra, and chloroform-d (D, 99.8%)+TMS0.03% (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 is dry through washing, Anhydrous potassium carbonate, after the 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 for use.
Step (2): the 1mol chromium trioxide is slowly joined in the 2mol pyridine, and control reaction temperature can produce yellow pyridine chromic oxide deposition 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, and bottoms is used 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 is used the ether recrystallization, and gets 10.1g 5-carbonyl-2-phenyl-1 after the vacuum-drying at room temperature, and 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 subsequent use., the there-necked flask of prolong adds 10.1g 5-carbonyl-2-phenyl-1 in being housed; 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 accomplished, decompress filter was removed catalyzer, and filtrating adds propyl carbinol then with the normal hexane washing, 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.After reaction was accomplished, reaction solution was dry through washing, Anhydrous potassium carbonate, after the 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 for use.
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, along with the adding of pyridine; There is yellow solid to separate out gradually, drips pyridine, be chilled to 0 ℃ again; Obtain the safran solid, filter to collect product, product is placed in the vacuum drier behind the dry 1h with sand core funnel; 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, and bottoms is used 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 the back solid and use the 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 subsequent use., the there-necked flask of prolong adds 18.4g5-carbonyl-2-phenyl-1 in being housed; 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 accomplished, decompress filter was removed catalyzer, and filtrating adds propyl carbinol then with the normal hexane washing, 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 accomplished, 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 for use.
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.Be incubated 10～15 minutes again after the dissolving of heating in water bath to solids.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, and bottoms is used 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 the back solid and use the 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 subsequent use., the there-necked flask of prolong adds 15.3g5-carbonyl-2-phenyl-1 in being housed; 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 accomplished, decompress filter was removed catalyzer, and filtrating adds propyl carbinol then with the normal hexane washing, 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 is dry through washing, Anhydrous potassium carbonate, after the 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 for use.
Step (2): in the there-necked flask that prolong, bubbler and TM 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 is used the ether recrystallization, and gets 12.5g5-carbonyl-2-phenyl-1 after the vacuum-drying at room temperature, and 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 subsequent use., the there-necked flask of prolong adds 12.5g5-carbonyl-2-phenyl-1 in being housed; 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 accomplished, decompress filter was removed catalyzer, and filtrating adds propyl carbinol then with the normal hexane washing, 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 TM 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 is used the ether recrystallization, and gets 14.8g 5-carbonyl-2-phenyl-1 after the vacuum-drying at room temperature, and 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 subsequent use., the there-necked flask of prolong adds 14.8g5-carbonyl-2-phenyl-1 in being housed; 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 accomplished, decompress filter was removed catalyzer, and filtrating adds propyl carbinol then with the normal hexane washing, 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 (7)
1. the preparation method of a 3-otan; It is characterized in that said 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; Described acid catalyst A is sulfuric acid, p-methyl benzenesulfonic acid or strongly acidic cation-exchange; Described band aqua is benzene or toluene; (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; Described oxygenant is the air or oxygen of capacity, and also add catalyzer 2,2,6,6-tetramethyl piperidine-1-oxyradical, NaNO in the reaction system this moment
2And FeCl
3Perhaps described oxygenant is chromium trioxide two pyridines, chromium trioxide pyridine hydrochloride or hydrochloric acid dimethylammonium chromium trioxide; (3) hydrolysis reaction: said 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; Described acid catalyst B is a solid acid catalyst, and said solid acid catalyst is selected from the CD550 strongly acidic cation-exchange, D072 strongly acidic cation-exchange or D061 strongly acidic cation-exchange;
2. as claimed in claim 11; The preparation method of 3-otan; It is characterized in that said 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 said glycerine, phenyl aldehyde is 1:1.0～1.5, and the consumption of said 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 said 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 through separation and purification.
4. as claimed in claim 11, the preparation method of 3-otan is characterized in that said 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 accomplished; Obtain 1 through separation and purification, 3-otan dimer; The consumption of said acid catalyst B is 5-carbonyl-2-phenyl-1,1～4 times of 3-dioxane weight.
5. described 1 like one of claim 1～4, the preparation method of 3-otan, the oxygenant that it is characterized in that using in said step (2) oxidizing reaction is the air or oxygen of 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.
6. described 1 like one of claim 1～4, the preparation method of 3-otan is characterized in that the oxygenant that uses in said step (2) oxidizing reaction is chromium trioxide two pyridines, chromium trioxide pyridine hydrochloride or hydrochloric acid dimethylammonium chromium trioxide; The consumption of said oxygenant is 2～5 times of glycerine phenyl aldehyde acetal ether (I) weight.
7. described 1 like one of claim 1～4, the preparation method of 3-otan is characterized in that the organic solvent that uses in said step (2) oxidizing reaction is methylene dichloride, trichloromethane, hexanaphthene or N, dinethylformamide.
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| JP6405443B2 (en) * | 2016-12-27 | 2018-10-17 | 花王株式会社 | Process for producing 1,3-dioxane-5-ones |
| US10829482B2 (en) | 2016-12-27 | 2020-11-10 | Kao Corporation | Method for producing glyceric acid ester |
| CN109415334B (en) * | 2016-12-27 | 2023-12-08 | 花王株式会社 | Process for producing 1, 3-dioxane-5-ones |
| CN109641866B (en) | 2016-12-27 | 2022-02-25 | 花王株式会社 | Process for producing glycerate |
| CN109553516A (en) * | 2017-09-26 | 2019-04-02 | 美拉德化工(大连)有限公司 | A kind of method of glycerol indirect oxidation synthesis C3H6O3 |
| CN109485629B (en) * | 2018-11-21 | 2020-11-06 | 浙江工业大学 | Production process of anhydrous acetone glycidol |
| CN109574981B (en) * | 2019-01-15 | 2020-06-23 | 上海芜玮环境科技有限公司 | Method for preparing glycerol benzaldehyde |
| CN109705084A (en) * | 2019-01-15 | 2019-05-03 | 浙江昊唐实业有限公司 | A kind of method of industrialized production glycerin shrinkage benzaldehyde |
| CN112174927B (en) * | 2020-11-05 | 2021-07-20 | 金睿睿 | Preparation method of glycerol formal |
| CN114213230B (en) * | 2021-11-17 | 2024-03-01 | 山东师范大学 | Method for preparing 1, 3-dihydroxyacetone |
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| Deutsch, J等."Investigations on heterogeneously catalysed condensations of glycerol to cyclic acetals".《Journal of catalysis》.2007,第425卷(第2期),428-435. * |
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