CN114213230A - Method for preparing 1, 3-dihydroxyacetone - Google Patents
Method for preparing 1, 3-dihydroxyacetone Download PDFInfo
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- CN114213230A CN114213230A CN202111362699.2A CN202111362699A CN114213230A CN 114213230 A CN114213230 A CN 114213230A CN 202111362699 A CN202111362699 A CN 202111362699A CN 114213230 A CN114213230 A CN 114213230A
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- dihydroxyacetone
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- glycerol
- benzaldehyde
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- RXKJFZQQPQGTFL-UHFFFAOYSA-N dihydroxyacetone Chemical compound OCC(=O)CO RXKJFZQQPQGTFL-UHFFFAOYSA-N 0.000 title claims abstract description 65
- 238000000034 method Methods 0.000 title claims abstract description 32
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims abstract description 101
- HUMNYLRZRPPJDN-UHFFFAOYSA-N benzaldehyde Chemical compound O=CC1=CC=CC=C1 HUMNYLRZRPPJDN-UHFFFAOYSA-N 0.000 claims abstract description 60
- 238000006243 chemical reaction Methods 0.000 claims abstract description 60
- 239000003054 catalyst Substances 0.000 claims abstract description 34
- -1 dihydroxyacetone benzaldehydes Chemical class 0.000 claims abstract description 30
- QNGNSVIICDLXHT-UHFFFAOYSA-N para-ethylbenzaldehyde Natural products CCC1=CC=C(C=O)C=C1 QNGNSVIICDLXHT-UHFFFAOYSA-N 0.000 claims abstract description 30
- 238000007327 hydrogenolysis reaction Methods 0.000 claims abstract description 18
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 18
- FRVUAWIBHDBFBZ-UHFFFAOYSA-N benzaldehyde propane-1,2,3-triol Chemical class OCC(O)CO.O=CC1=CC=CC=C1 FRVUAWIBHDBFBZ-UHFFFAOYSA-N 0.000 claims abstract description 13
- 238000000926 separation method Methods 0.000 claims abstract description 9
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 7
- 230000009471 action Effects 0.000 claims abstract description 4
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 claims description 39
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 36
- 229940074076 glycerol formal Drugs 0.000 claims description 35
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 34
- 239000003960 organic solvent Substances 0.000 claims description 33
- 239000002904 solvent Substances 0.000 claims description 32
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical group CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 claims description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 27
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 26
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 24
- 238000003756 stirring Methods 0.000 claims description 24
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 18
- 239000000203 mixture Substances 0.000 claims description 17
- 239000005457 ice water Substances 0.000 claims description 16
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical group OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 15
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002390 rotary evaporation Methods 0.000 claims description 13
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 claims description 12
- 229940120503 dihydroxyacetone Drugs 0.000 claims description 12
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 12
- 239000012074 organic phase Substances 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000012295 chemical reaction liquid Substances 0.000 claims description 10
- 230000008569 process Effects 0.000 claims description 10
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 claims description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 239000001257 hydrogen Substances 0.000 claims description 8
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- JOXIMZWYDAKGHI-UHFFFAOYSA-N p-toluenesulfonic acid Substances CC1=CC=C(S(O)(=O)=O)C=C1 JOXIMZWYDAKGHI-UHFFFAOYSA-N 0.000 claims description 8
- 239000003377 acid catalyst Substances 0.000 claims description 7
- 238000001035 drying Methods 0.000 claims description 7
- 238000000605 extraction Methods 0.000 claims description 7
- 238000001914 filtration Methods 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 230000003647 oxidation Effects 0.000 claims description 7
- 238000002425 crystallisation Methods 0.000 claims description 6
- 230000008025 crystallization Effects 0.000 claims description 6
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 claims description 5
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 5
- 239000003513 alkali Substances 0.000 claims description 5
- 229960001701 chloroform Drugs 0.000 claims description 5
- 239000003208 petroleum Substances 0.000 claims description 5
- 239000000126 substance Substances 0.000 claims description 5
- 239000012670 alkaline solution Substances 0.000 claims description 3
- UOCLXMDMGBRAIB-UHFFFAOYSA-N 1,1,1-trichloroethane Chemical compound CC(Cl)(Cl)Cl UOCLXMDMGBRAIB-UHFFFAOYSA-N 0.000 claims description 2
- SCYULBFZEHDVBN-UHFFFAOYSA-N 1,1-Dichloroethane Chemical compound CC(Cl)Cl SCYULBFZEHDVBN-UHFFFAOYSA-N 0.000 claims description 2
- 230000002378 acidificating effect Effects 0.000 claims description 2
- 238000010533 azeotropic distillation Methods 0.000 claims description 2
- 238000006482 condensation reaction Methods 0.000 claims description 2
- 150000002576 ketones Chemical class 0.000 claims description 2
- 125000005489 p-toluenesulfonic acid group Chemical group 0.000 claims description 2
- 239000000843 powder Substances 0.000 claims description 2
- 238000001953 recrystallisation Methods 0.000 claims description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 claims description 2
- RKBCYCFRFCNLTO-UHFFFAOYSA-N triisopropylamine Chemical compound CC(C)N(C(C)C)C(C)C RKBCYCFRFCNLTO-UHFFFAOYSA-N 0.000 claims description 2
- YFTHZRPMJXBUME-UHFFFAOYSA-N tripropylamine Chemical compound CCCN(CCC)CCC YFTHZRPMJXBUME-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 6
- 238000000746 purification Methods 0.000 abstract description 5
- 239000002994 raw material Substances 0.000 abstract description 3
- 230000002194 synthesizing effect Effects 0.000 abstract 1
- 235000011187 glycerol Nutrition 0.000 description 25
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 14
- 239000007787 solid Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 6
- 229910019093 NaOCl Inorganic materials 0.000 description 5
- 239000007864 aqueous solution Substances 0.000 description 5
- 238000003760 magnetic stirring Methods 0.000 description 5
- 239000012452 mother liquor Substances 0.000 description 5
- SUKJFIGYRHOWBL-UHFFFAOYSA-N sodium hypochlorite Chemical compound [Na+].Cl[O-] SUKJFIGYRHOWBL-UHFFFAOYSA-N 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical class [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 4
- HEDRZPFGACZZDS-MICDWDOJSA-N Trichloro(2H)methane Chemical compound [2H]C(Cl)(Cl)Cl HEDRZPFGACZZDS-MICDWDOJSA-N 0.000 description 4
- 229940117975 chromium trioxide Drugs 0.000 description 4
- WGLPBDUCMAPZCE-UHFFFAOYSA-N chromium trioxide Inorganic materials O=[Cr](=O)=O WGLPBDUCMAPZCE-UHFFFAOYSA-N 0.000 description 4
- GAMDZJFZMJECOS-UHFFFAOYSA-N chromium(6+);oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Cr+6] GAMDZJFZMJECOS-UHFFFAOYSA-N 0.000 description 4
- MNQZXJOMYWMBOU-UHFFFAOYSA-N glyceraldehyde Chemical compound OCC(O)C=O MNQZXJOMYWMBOU-UHFFFAOYSA-N 0.000 description 4
- 238000004064 recycling Methods 0.000 description 4
- JHJLBTNAGRQEKS-UHFFFAOYSA-M sodium bromide Chemical compound [Na+].[Br-] JHJLBTNAGRQEKS-UHFFFAOYSA-M 0.000 description 4
- 239000002351 wastewater Substances 0.000 description 4
- 238000005160 1H NMR spectroscopy Methods 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 230000003301 hydrolyzing effect Effects 0.000 description 3
- GDOPTJXRTPNYNR-UHFFFAOYSA-N methyl-cyclopentane Natural products CC1CCCC1 GDOPTJXRTPNYNR-UHFFFAOYSA-N 0.000 description 3
- 239000012046 mixed solvent Substances 0.000 description 3
- 238000010992 reflux Methods 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000000967 suction filtration Methods 0.000 description 3
- 239000002253 acid Substances 0.000 description 2
- 230000008014 freezing Effects 0.000 description 2
- 238000007710 freezing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000010413 mother solution Substances 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- ROFVEXUMMXZLPA-UHFFFAOYSA-N Bipyridyl Chemical compound N1=CC=CC=C1C1=CC=CC=N1 ROFVEXUMMXZLPA-UHFFFAOYSA-N 0.000 description 1
- 239000012027 Collins reagent Substances 0.000 description 1
- 238000005903 acid hydrolysis reaction Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- SLUNEGLMXGHOLY-UHFFFAOYSA-N benzene;hexane Chemical compound CCCCCC.C1=CC=CC=C1 SLUNEGLMXGHOLY-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 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 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018044 dehydration Effects 0.000 description 1
- 238000006297 dehydration reaction Methods 0.000 description 1
- 238000010511 deprotection reaction Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 239000007800 oxidant agent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 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 1
- 238000011084 recovery Methods 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
- C07C45/61—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups
- C07C45/65—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by reactions not involving the formation of >C = O groups by splitting-off hydrogen atoms or functional groups; by hydrogenolysis of functional groups
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D319/00—Heterocyclic compounds containing six-membered rings having two oxygen atoms as the only ring hetero atoms
- C07D319/04—1,3-Dioxanes; Hydrogenated 1,3-dioxanes
- C07D319/06—1,3-Dioxanes; Hydrogenated 1,3-dioxanes not condensed with other rings
Abstract
The invention belongs to the technical field of chemical synthesis, and relates to a method for preparing 1, 3-dihydroxyacetone, wherein glycerol and benzaldehyde react to generate glycerol benzaldehydes, the glycerol benzaldehydes are subjected to oxidation reaction to obtain dihydroxyacetone benzaldehydes, and the dihydroxyacetone benzaldehydes are subjected to hydrogenolysis reaction under the action of a catalyst to obtain the 1, 3-dihydroxyacetone. Compared with the prior art, the method for synthesizing the 1, 3-dihydroxyacetone has the advantages of cheap and easily obtained raw materials, simple and convenient operation, mild reaction conditions, high yield and easy separation and purification of products.
Description
Technical Field
The invention belongs to the technical field of chemical synthesis, and relates to a method for preparing 1, 3-dihydroxyacetone.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
According to the research of the inventor, in the process of preparing 1, 3-Dihydroxyacetone (DHA) by a glycerol indirect oxidation method, glycerol generally reacts with benzaldehyde to generate glycerol benzaldehydes, then PCC (chromium trioxide pyridine hydrochloride), Collins reagent (chromium trioxide bipyridine) or TEMPO/NaBr/NaOCl are oxidized to prepare the dihydroxyacetone benzaldehydes, and then the dihydroxyacetone is subjected to acidic hydrolysis and then subjected to post-treatment such as dehydration, separation and purification to prepare the 1, 3-dihydroxyacetone. The inventor researches and discovers that the method has main problems including: chromium trioxide is used as an oxidant, so that the generated waste water is not easy to treat, and the environment is seriously polluted; by using a TEMPO/NaBr/NaOCl method, the TEMPO price is high, the NaOCl aqueous solution dosage is large, and the salt-containing organic wastewater is difficult to treat; 1, 3-dihydroxyacetone generated by hydrolyzing dihydroxyacetone benzaldehyde by hydrochloric acid is dissolved in an acid-containing aqueous solution, and extraction and purification are difficult.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide the method for preparing the 1, 3-dihydroxyacetone, which has the advantages of mild reaction conditions, high yield, simple and convenient operation and easy separation and purification of DHA.
In order to achieve the purpose, the technical scheme of the invention is as follows:
a method for preparing 1, 3-dihydroxyacetone comprises the steps of reacting glycerol with benzaldehyde to generate glycerol formal, carrying out oxidation reaction on the glycerol formal to obtain dihydroxyacetone formal, and carrying out hydrogenolysis reaction on the dihydroxyacetone formal under the action of a catalyst to obtain the 1, 3-dihydroxyacetone.
In order to solve the problem of difficult extraction in the preparation of 1, 3-dihydroxyacetone by hydrolyzing dihydroxyacetone benzaldehyde through hydrochloric acid, the preparation method adopts a hydrogenolysis method to avoid adding water into a reaction system, so that the extraction is simpler. However, in general, in the hydrogenolysis process, the catalyst can activate not only ether bond but also ketone carbonyl group, so that the ketone carbonyl group is easily reduced to form hydroxyl group in the hydrogenolysis process, so that 1, 3-dihydroxyacetone cannot be obtained, and in order to avoid the reduction of the ketone carbonyl group in the hydrogenolysis process, the ketone carbonyl group is protected, then hydrogenolysis is carried out, and then deprotection is carried out, so that the reaction route is increased, and the yield is reduced due to the increase of the route, so that the dihydroxyacetone benzaldehyde is not treated by the hydrogenolysis method by the person skilled in the art.
However, the present invention has been found through experiments unexpectedly that, in the dihydroxyacetone benzaldehyde of the present invention, after hydrogenolysis reaction is performed by a catalyst, not only can the ketocarbonyl group not be reduced, but also the yield of the 1, 3-dihydroxyacetone is high.
In order to solve the problem that chromium trioxide pollutes the environment or NaOCl aqueous solution generates a large amount of wastewater which is difficult to treat in the oxidation reaction process, dimethyl sulfoxide (DMSO) and phosphorus pentoxide are used for oxidation in the oxidation reaction. When the oxidation system is used for oxidation, an alkaline substance such as triethylamine needs to be added, and hydrochloric acid needs to be added dropwise for removing the triethylamine. However, the inventors have found that the addition of hydrochloric acid results in a decrease in the yield of dihydroxyacetone benzaldehydes. Thus, further, the oxidation reaction is followed by extraction, and the extracted organic phase is then washed with aqueous alkaline solution. The method can greatly improve the yield of the dihydroxyacetone benzaldehyde.
In addition, the synthesis of the glycerol formal generally adopts a glycerol excess mode for reaction, however, the glycerol excess affects the product separation and purification, and the post-treatment process is extremely complex. The research shows that the reaction in the mode of excess benzaldehyde can simplify the post-treatment process of generating glycerin formal, and in order to solve the problem, the molar quantity of benzaldehyde is more than that of glycerin in the reaction of glycerin and benzaldehyde to generate glycerin formal.
The invention has the beneficial effects that:
1. the invention takes the glycerol and the benzaldehyde as raw materials to synthesize the glycerol formal under the reaction condition, the raw materials are cheap and easy to obtain, the operation is simple and convenient, and the yield is high.
2. The invention prepares the 1, 3-dihydroxyacetone by the hydrogenolysis reaction of the dihydroxyacetone benzaldehyde, the reaction condition is mild, the yield is high, and the product is easy to separate and purify.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of exemplary embodiments according to the invention. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The chemical structural formula of the glycerol formal is shown in the specification
The chemical structural formula of the dihydroxyacetone benzaldehyde is shown in the specification
In view of the problem that 1, 3-dihydroxyacetone generated by hydrolyzing dihydroxyacetone benzaldehyde by hydrochloric acid is difficult to extract and purify when dissolved in an acid-containing aqueous solution, the invention provides a method for preparing 1, 3-dihydroxyacetone.
In a typical embodiment of the present invention, a method for preparing 1, 3-dihydroxyacetone is provided, wherein glycerol reacts with benzaldehyde to generate glycerol formal, the glycerol formal undergoes an oxidation reaction to obtain dihydroxyacetone formal, and the dihydroxyacetone formal undergoes a hydrogenolysis reaction under the action of a catalyst to obtain 1, 3-dihydroxyacetone.
After the hydrogenolysis reaction is carried out by the catalyst, the method not only can ensure that the ketocarbonyl group is not reduced, but also has higher yield of the obtained 1, 3-dihydroxyacetone.
In some examples of this embodiment, the oxidation is carried out using dimethyl sulfoxide and phosphorus pentoxide. Can solve the problem that chromium trioxide environmental pollution or NaOCl aqueous solution is used to generate a large amount of wastewater in the oxidation reaction process.
In one or more embodiments, the oxidation reaction is followed by extraction, and the extracted organic phase is then washed with aqueous alkaline solution. Can solve the problem of the yield reduction of the dihydroxyacetone benzaldehyde caused by dripping hydrochloric acid.
In some examples of this embodiment, the glycerol is reacted with benzaldehyde to form glycerol formal, the molar amount of benzaldehyde being greater than the molar amount of glycerol. Can simplify the post-treatment process of the glycerol formal.
In some examples of this embodiment, the reaction of glycerol with benzaldehyde to produce glycerol formal is: the glycerol and the benzaldehyde are subjected to condensation reaction in an organic solvent under an acidic condition, water generated by the reaction is subjected to azeotropic distillation with the organic solvent, is timely separated from a reaction system through an oil-water separator, and is cooled to room temperature and then is placed at low temperature to obtain the glycerol benzaldehyde.
Specifically, benzaldehyde, glycerol, an acid catalyst and an organic solvent are added into a reaction bottle with an oil-water separator, stirring is carried out, the temperature is increased to 55-90 ℃, azeotropic water separation is carried out, the reaction is carried out for 3-8 hours, no water is separated, the reaction is finished, the reaction liquid is cooled to room temperature, and then the glycerol formal is separated out after the reaction is placed at the low temperature (-10 to-25 ℃).
More specifically, the mass ratio of the substances of the reaction glycerol and the benzaldehyde is 1: 1.0-1.1, wherein the amount of the acid catalyst is 1-3% of the weight of the glycerol.
More specifically, the acid catalyst is p-toluenesulfonic acid.
More specifically, the organic solvent used in the synthesis reaction of glycerol formal is benzene, toluene, cyclohexane, hexane, petroleum ether or a mixture of solvent 1 and solvent 2, wherein solvent 1 is benzene or toluene, solvent 2 is cyclohexane, hexane or petroleum ether, and preferably a mixture of solvent 1 and solvent 2. The volume ratio of the solvent 1 to the solvent 2 is preferably 1: 1. The volume consumption of the organic solvent is 2-5 times of the volume of the glycerol.
The separation method of the glycerol formal in the synthesis reaction of the glycerol formal refers to low-temperature crystallization of reaction liquid containing an acid catalyst and a mixed organic solvent, and preferably crystallization at-10 to-25.0 ℃.
The crystallization mother liquor after the separation of the glycerol formal is added with benzaldehyde and glycerol for the synthesis reaction of the glycerol formal again for recycling, so that the yield of the glycerol formal can be greatly improved.
In some examples of this embodiment, glycerol formal is added to a system containing a solvent, phosphorus pentoxide, and dimethyl sulfoxide under inert atmosphere and ice-water bath conditions, the mixture is reacted at room temperature with stirring, then organic amine is added under ice-water bath conditions, the mixture is reacted with stirring at room temperature, organic solvent is added, organic phase is separated, alkali washing, water washing and drying are carried out, and the solvent is removed by rotary evaporation to obtain dihydroxyacetone formal.
Specifically, in N2Under the conditions of protection and ice-water bath, dripping glycerol formal into an organic solvent containing phosphorus pentoxide and dimethyl sulfoxide, stirring, and reacting at room temperature for 3-6 hours; and then adding organic amine under the condition of ice-water bath, and stirring and reacting for 5-10 hours at room temperature. After the reaction is finished, adding an organic solvent, separating out an organic phase, carrying out alkali washing, water washing and drying, and removing the solvent by rotary evaporation to obtain the dihydroxyacetone benzaldehyde.
More specifically, the organic solvent in the oxidation reaction is dichloromethane, trichloromethane, dichloroethane, trichloroethane, preferably dichloromethane; the mass consumption of the organic solvent is 10-30 times of the weight of the glycerol formal.
More specifically, the phosphorus pentoxide is a dry phosphorus pentoxide powder. The mass consumption of the phosphorus pentoxide is 1-3 times of the weight of the glycerol benzaldehyde.
More specifically, the dimethyl sulfoxide is dried dimethyl sulfoxide. The mass amount of the dimethyl sulfoxide is 1-3 times of the weight of the glycerol formal.
More specifically, the organic amine is triethylamine, tripropylamine, triisopropylamine or tributylamine, preferably triethylamine. The mass consumption of the organic amine is 2-4 times of the weight of the glycerol benzaldehyde.
More specifically, the separation method of the dihydroxyacetone benzaldehyde is that organic solvent is added after the reaction is finished, organic phase is separated out, alkali washing, water washing and drying are carried out, the solvent is removed by rotary evaporation, and residue is recrystallized by ether to obtain the dihydroxyacetone benzaldehyde.
In some examples of this embodiment, dihydroxyacetone benzaldehyde is added to an organic solvent and a Pd/C catalyst, stirred at room temperature, hydrogen is introduced to carry out hydrogenolysis reaction, the catalyst is filtered off after the reaction is finished, the solvent is removed by rotary evaporation, and the residue is recrystallized to obtain 1, 3-dihydroxyacetone.
Specifically, adding dihydroxyacetone benzaldehyde, an organic solvent and a Pd/C catalyst into a reaction bottle, vacuumizing and introducing nitrogen for three times, then introducing hydrogen for hydrogenolysis reaction, stirring and reacting at room temperature for 10-72 hours, filtering out the catalyst after the reaction is finished, removing the solvent by rotary evaporation, and recrystallizing the residue to obtain the 1, 3-dihydroxyacetone.
More specifically, the catalyst is a 5% Pd/C or 10% Pd/C catalyst, preferably a 10% Pd/C catalyst; the mass amount of the catalyst is 5-20% of the weight of the dihydroxyacetone benzaldehyde; the Pd/C catalyst obtained by filtration and recovery can be reused.
More specifically, the organic solvent is methanol, ethanol, ethyl acetate; the dosage of the organic solvent is 5-20 times of the weight of the glycerol ketone benzaldehyde.
More specifically, the organic solvent used for recrystallization in the reaction is methanol or ethanol; the crystallization temperature in the organic solvent is preferably 0 to-10.0 ℃.
The route of the invention is as follows:
in order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
In a stirring and dropping funnel and a thermometer92.2g of glycerol, 1.0g of p-toluenesulfonic acid and 300mL (1:1) of a mixed solvent of toluene and petroleum ether are added into a four-neck flask, a condenser, an oil-water separator and the four-neck flask, stirring is carried out, 112.0g of benzaldehyde is slowly dropped into a reaction liquid by using a constant-pressure dropping funnel under the protection of nitrogen, heating reflux is carried out to separate water, the azeotropic temperature is started to be about 70 ℃, the reaction is carried out for about 6 hours, the water in the water separator is not increased any more, the reaction is stopped, the reaction liquid is cooled to room temperature, the reaction liquid is placed in a refrigerator to be frozen (-15 ℃), white crystals are separated out, and suction filtration is carried out to obtain 48.3g of white solid glycerol benzaldehyde, wherein the yield is 26.8%.1HNMR(400MHz,CDCl3),δ(ppm):2.45(d,1H,OH),3.65(m,1H),4.16-4.22(m,4H),5.57(s,1H),7.38-7.52(m,5H)。
And (5) recycling the mother liquor. To the mother solution was added 46.1g (0.5mol) of glycerin and 56.0g (0.53mol) of benzaldehyde, and the reaction was repeated to obtain 86.7g of white glycerin formal as a solid with a yield of 96.3%.
Example 2
92.2g of glycerol, 1.2g of p-toluenesulfonic acid and 300mL (1:1) of a benzene-hexane mixed solvent are added into a four-neck flask provided with a stirring device, a dropping funnel, a thermometer, a condenser, an oil-water separator and a nitrogen protection device, stirring is carried out, 112.0g of benzaldehyde is slowly dropped into a reaction liquid by using a constant-pressure dropping funnel under the protection of nitrogen, heating reflux is carried out to separate water, the azeotropic temperature is about 75 ℃, the reaction is about 5 hours, the water in the separator is not increased any more, the reaction liquid is stopped, cooled to the room temperature, a refrigerator is placed for freezing (-15 ℃), white crystals are separated out, and suction filtration is carried out to obtain 45.5g of white solid glycerol benzaldehyde, wherein the yield is 25.3%.
And (5) recycling the mother liquor. 46.1g of glycerol and 56.0g of benzaldehyde are added into the crystallization mother liquor, and the reaction operation is repeated to obtain 86.1g of white solid glycerol formal with the yield of 95.6 percent.
Example 3
92.2g of glycerol, 1.0g of p-toluenesulfonic acid and 300mL (1:1) of a toluene and cyclohexane mixed solvent are added into a four-neck flask provided with a stirring device, a dropping funnel, a thermometer, a condenser, an oil-water separator and a nitrogen protection device, stirring is carried out, 115.0g of benzaldehyde is slowly dropped into a reaction liquid by using a constant-pressure dropping funnel under the protection of nitrogen, heating reflux is carried out to separate water, the azeotropic temperature is about 80 ℃, the reaction is about 4 hours, the water in the separator is not increased any more, the reaction liquid is stopped, cooled to the room temperature, a refrigerator is placed for freezing (-15 ℃), white crystals are separated out, and suction filtration is carried out to obtain 41.6g of white solid glycerol benzaldehyde, wherein the yield is 23.1%.
And (5) recycling the mother liquor. To the mother solution was added 46.1g of glycerin and 56.0g of benzaldehyde, and the reaction was repeated to obtain 82.3g of white glycerin formal as a solid with a yield of 91.5%.
Example 4
200mL of dichloromethane and 28.5g of phosphorus pentoxide are added into a four-neck flask provided with a stirring device, a dropping funnel, a thermometer and a condenser, the mixture is cooled in an ice-water bath, 16.7mL of dimethyl sulfoxide is dropwise added, 18g of glycerol formal dissolved in dichloromethane is dropwise added, the mixture is stirred at room temperature for 4 hours, then 58mL of triethylamine is slowly dropwise added under the ice-water bath, the mixture is stirred at room temperature for 6 hours after the dropwise addition, the reaction is stopped, 200mL of dichloromethane is added, an organic phase is separated, saturated sodium carbonate solution and water are respectively used for washing, anhydrous sodium sulfate is used for drying, the filtration is carried out, the solvent is removed by rotary evaporation, the residue is recrystallized by ether, 16.1g of dihydroxyacetone formal is obtained, and the yield is 90.4%.1HNMR(400MHz,CDCl3),δ(ppm):4.40(s,2H)，4.45(s,2H)，5.84(s,1H)，
7.38-7.57(m,5H)。
Example 5
Adding 200mL of dichloromethane and 35.5g of phosphorus pentoxide into a four-neck flask provided with a stirring device, a dropping funnel, a thermometer and a condenser, cooling in an ice-water bath, dropwise adding 20mL of dimethyl sulfoxide, dropwise adding 18g of glycerol benzaldehyde dissolved in dichloromethane, stirring at room temperature for 4 hours, then slowly dropwise adding 70mL of triethylamine in the ice-water bath, stirring at room temperature for reaction for 6 hours after dropwise adding, stopping the reaction, adding 200mL of dichloromethane, separating an organic phase, washing with a saturated sodium carbonate solution and water respectively, drying with anhydrous sodium sulfate, filtering, removing the solvent by rotary evaporation, and recrystallizing the residue with diethyl ether to obtain 16.2g of dihydroxyacetone benzaldehyde, wherein the yield is 91.0%.
Example 6
200mL of trichloromethane and 28.5g of phosphorus pentoxide are added into a four-neck flask provided with a stirring device, a dropping funnel, a thermometer and a condenser, the mixture is cooled in an ice-water bath, 16 mL and 7mL of dimethyl sulfoxide are added dropwise, 18g of glycerol formal dissolved in trichloromethane is added dropwise, the mixture is stirred at room temperature for 4 hours, then 58mL of triethylamine is slowly added dropwise in the ice-water bath, the mixture is stirred and reacted at room temperature for 6 hours after the dropwise addition, the reaction is stopped, 200mL of trichloromethane is added, an organic phase is separated out, the mixture is respectively washed by saturated sodium carbonate solution and water, anhydrous sodium sulfate is dried, the solvent is removed by filtration and rotary evaporation, the residue is recrystallized by ether, 15.4g of dihydroxyacetone formal is obtained, and the yield is 86.5%.
Example 7
200mL of dichloromethane and 28.5g of phosphorus pentoxide are added into a four-neck flask provided with a stirring device, a dropping funnel, a thermometer and a condenser, the mixture is cooled in an ice-water bath, 16.7mL of dimethyl sulfoxide is dropwise added, 18g of glycerol formal dissolved in dichloromethane is dropwise added, the mixture is stirred at room temperature for 4 hours, then 58mL of triethylamine is slowly dropwise added under the ice-water bath, the mixture is stirred at room temperature for reaction for 6 hours, 10% hydrochloric acid is dropwise added until the mixture is neutral, the reaction is stopped, 200mL of dichloromethane is added, an organic phase is separated out, the mixture is respectively washed by saturated sodium carbonate solution and water, anhydrous sodium sulfate is dried, the solvent is filtered and removed by rotary evaporation, and the residue is recrystallized by diethyl ether to obtain 5.6g of dihydroxyacetone formal, and the yield is 15.6%.
Example 8
In a 100mL three-neck flask, 3.60g dihydroxyacetone benzaldehyde and 30mL ethanol are added, 0.5g of 10% Pd/C catalyst is added under magnetic stirring, the reaction system is vacuumized and filled with N2Three times, then introducing hydrogen and reacting for 60 hours. After the reaction, the catalyst was filtered off, the solvent was evaporated off, and the resulting product was recrystallized from ethanol to give 1.68g of 1, 3-dihydroxyacetone as a white powdery solid with a yield of 93.6%.1H NMR(400MHz,D2O)，δ(ppm)：4.24(s,4H),3.40-3.49(t,2H)。
Example 9
In a 100mL three-neck flask, 3.60g dihydroxyacetone benzaldehyde and 30mL methanol were added, 0.7g 10% Pd/C catalyst was added under magnetic stirring, the reaction system was evacuated and N was charged2Three times, then introducing hydrogen, and reacting for 60 hours. Filtering out the catalyst after the reaction is finished, evaporating the solvent in a rotary manner, and recrystallizing by using ethanol to obtain1.65g of 1, 3-dihydroxyacetone was obtained as a white powdery solid in a yield of 91.5%.
Example 10
In a 100mL three-necked flask, 3.60g of dihydroxyacetone benzaldehyde and 30mL of ethyl acetate were added, 0.6g of 10% Pd/C catalyst was added under magnetic stirring, and the reaction system was evacuated and charged with N2Three times, then hydrogen was introduced, and the reaction was carried out for 72 hours. After the reaction, the catalyst was filtered off, the solvent was evaporated off, and the resulting product was recrystallized from ethanol to give 1.65g of 1, 3-dihydroxyacetone as a white powdery solid with a yield of 91.5%.
Example 11
In a 100mL three-neck flask, 3.60g dihydroxyacetone benzaldehyde and 30mL ethanol are added, 0.7g of 5% Pd/C catalyst is added under magnetic stirring, the reaction system is vacuumized and filled with N2Three times, then hydrogen was introduced, and the reaction was carried out for 72 hours. After the reaction, the catalyst was filtered off, the solvent was evaporated off, and the resulting product was recrystallized from ethanol to give 1.5g of 1, 3-dihydroxyacetone as a white powdery solid with a yield of 83.5%.
Example 12
In a 100mL three-necked flask, 3.60g of dihydroxyacetone benzaldehyde and 30mL of ethanol were added, the 10% Pd/C catalyst recovered in example 8 was added under magnetic stirring, and the reaction system was evacuated and N was charged2Three times, then hydrogen was introduced, and the reaction was carried out for 72 hours. After the reaction, the catalyst was filtered off, the solvent was evaporated off, and the resulting product was recrystallized from ethanol to give 1.67g of 1, 3-dihydroxyacetone as a white powdery solid with a yield of 92.7%.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. A method for preparing 1, 3-dihydroxyacetone is characterized in that glycerol reacts with benzaldehyde to generate glycerol formal, the glycerol formal undergoes an oxidation reaction to obtain dihydroxyacetone formal, and the dihydroxyacetone formal undergoes a hydrogenolysis reaction under the action of a catalyst to obtain the 1, 3-dihydroxyacetone.
2. The process for preparing 1, 3-dihydroxyacetone according to claim 1, wherein the oxidation is carried out using dimethyl sulfoxide and phosphorus pentoxide.
3. The process for preparing 1, 3-dihydroxyacetone according to claim 2, wherein the oxidation is followed by extraction and the organic phase of the extraction is then washed with aqueous alkaline solution.
4. The method of claim 1, 3-dihydroxyacetone production according to claim 1, wherein the molar amount of benzaldehyde is greater than the molar amount of glycerol in the reaction of glycerol with benzaldehyde to produce glycerol formal.
5. The method of claim 1, 3-dihydroxyacetone production process of claim 1, wherein the step of reacting glycerol with benzaldehyde to produce glycerol formal comprises: the glycerol and the benzaldehyde are subjected to condensation reaction in an organic solvent under an acidic condition, water generated by the reaction is subjected to azeotropic distillation with the organic solvent, is timely separated from a reaction system through an oil-water separator, and is cooled to room temperature and then is placed at low temperature to obtain the glycerol benzaldehyde.
6. The method for preparing 1, 3-dihydroxyacetone according to claim 1, wherein benzaldehyde, glycerol, acid catalyst and organic solvent are added into a reaction bottle with an oil-water separator, stirred, heated to 55-90 ℃, subjected to azeotropic water separation, reacted for 3-8 hours, no more water is separated, the reaction is finished, the reaction liquid is cooled to room temperature, and then placed at low temperature to separate out glycerol formal;
preferably, the mass ratio of the substances of the reaction glycerol and the benzaldehyde is 1: 1.0-1.1, wherein the dosage of the acid catalyst is 1-3% of the weight of the glycerol;
preferably, the acid catalyst is p-toluenesulfonic acid;
preferably, the organic solvent used in the synthesis reaction of glycerol formal is benzene, toluene, cyclohexane, hexane, petroleum ether or a mixture of solvent 1 and solvent 2, wherein solvent 1 is benzene or toluene, and solvent 2 is cyclohexane, hexane or petroleum ether.
7. The process for producing 1, 3-dihydroxyacetone according to claim 1, wherein the reaction is carried out by adding glycerol formal to a system comprising a solvent, phosphorus pentoxide and dimethyl sulfoxide in an inert atmosphere in an ice-water bath, reacting at room temperature while stirring, adding organic amine in an ice-water bath, reacting while stirring at room temperature, adding an organic solvent, separating an organic phase, washing with alkali, washing with water, drying, and removing the solvent by rotary evaporation to obtain dihydroxyacetone formal.
8. The process for preparing 1, 3-dihydroxyacetone according to claim 7, wherein N is2Under the conditions of protection and ice-water bath, dripping glycerol formal into an organic solvent containing phosphorus pentoxide and dimethyl sulfoxide, stirring, and reacting at room temperature for 3-6 hours; then, under the ice-water bath condition, adding organic amine, and stirring and reacting for 5-10 hours at room temperature;
preferably, the organic solvent in the oxidation reaction is dichloromethane, trichloromethane, dichloroethane, trichloroethane, preferably dichloromethane; the mass consumption of the organic solvent is 10-30 times of the weight of the glycerol formal;
preferably, the phosphorus pentoxide is a dry phosphorus pentoxide powder. The mass consumption of the phosphorus pentoxide is 1-3 times of the weight of the glycerol benzaldehyde;
preferably, the dimethyl sulfoxide is dried dimethyl sulfoxide. The mass amount of the dimethyl sulfoxide is 1-3 times of the weight of the glycerol formal;
preferably, the organic amine is triethylamine, tripropylamine, triisopropylamine or tributylamine, preferably triethylamine; the mass consumption of the organic amine is 2-4 times of the weight of the glycerol benzaldehyde;
preferably, the dihydroxyacetone benzaldehyde is separated by adding an organic solvent after the reaction is finished, separating an organic phase, performing alkali washing, water washing and drying, removing the solvent by rotary evaporation, and recrystallizing the residue with diethyl ether to obtain the dihydroxyacetone benzaldehyde.
9. The method of claim 1, 3-dihydroxyacetone production according to claim 1, wherein the dihydroxyacetone benzaldehyde is subjected to hydrogenolysis reaction by adding an organic solvent and a Pd/C catalyst under stirring at room temperature while introducing hydrogen gas, the catalyst is filtered off after the completion of the hydrogenolysis reaction, the solvent is removed by rotary evaporation, and the residue is recrystallized to obtain 1, 3-dihydroxyacetone.
10. The method of claim 9, wherein the 1, 3-dihydroxyacetone is prepared by charging dihydroxyacetone benzaldehyde, organic solvent and Pd/C catalyst into a reaction flask, evacuating, introducing nitrogen three times, introducing hydrogen to carry out hydrogenolysis reaction, stirring at room temperature for 10-72 hours, filtering off the catalyst after the reaction, removing the solvent by rotary evaporation, and recrystallizing the residue to obtain 1, 3-dihydroxyacetone;
preferably, the catalyst is a 5% Pd/C or 10% Pd/C catalyst, preferably a 10% Pd/C catalyst; the mass amount of the catalyst is 5-20% of the weight of the dihydroxyacetone benzaldehyde;
preferably, the organic solvent is methanol, ethanol, ethyl acetate; the dosage of the organic solvent is 5-20 times of the weight of the glycerol ketone benzaldehyde;
preferably, the organic solvent used for recrystallization in the reaction is methanol or ethanol; the crystallization temperature in the organic solvent is preferably 0 to-10.0 ℃.
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