CN107141208B - Preparation method of 1, 3-dihydroxyacetone - Google Patents
Preparation method of 1, 3-dihydroxyacetone Download PDFInfo
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- CN107141208B CN107141208B CN201710535199.1A CN201710535199A CN107141208B CN 107141208 B CN107141208 B CN 107141208B CN 201710535199 A CN201710535199 A CN 201710535199A CN 107141208 B CN107141208 B CN 107141208B
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- 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
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- C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
- C07C45/29—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation of hydroxy groups
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Abstract
The invention relates to the technical field of organic synthesis, and discloses a preparation method of 1, 3-dihydroxyacetone, which comprises the following steps: (1) in the presence of a catalyst, glycerol and a halogenated reagent are subjected to contact reaction to prepare 1, 3-dichloro-2-propanol; (2) carrying out oxidative dehydrogenation reaction on the 1, 3-dichloro-2-propanol to obtain an intermediate product 1, 3-dichloro-2-propanone; (3) 1, 3-dichloro-2-propanone and alkaline substance are contacted in a water-containing medium for hydrolysis reaction to obtain 1, 3-dihydroxyacetone, wherein the temperature of the hydrolysis reaction is 25-60 ℃. The preparation method of 1, 3-dihydroxyacetone provided by the invention has the advantages that the conversion rate of glycerol and the yield of 1, 3-dihydroxyacetone are high, zirconium oxide is used as a catalyst, the efficiency is high, the cost is low, and the like, and the preparation method has an industrial application prospect.
Description
Technical Field
The invention relates to the technical field of organic synthesis, in particular to a preparation method of 1, 3-dihydroxyacetone.
Background
1, 3-Dihydroxyacetone (DHA) is the simplest ketose, and is easily soluble in organic solvents such as water, ethanol, acetone, and diethyl ether. DHA is an important chemical raw material and is widely applied to the industries of fine chemical engineering, food, cosmetics, water purification and the like; meanwhile, DHA is also an important organic synthesis intermediate, and can be used for preparing various chiral compounds by aldol condensation, reducing to prepare secondary alcohol with optical activity, preparing saccharide compounds by Diels-Alder addition, or further reacting for the addition reaction, carrying out insertion reaction with carbene, and reacting with 2, 2-dialkoxy cyclopropane derivative to prepare lactone.
Currently, 1, 3-dihydroxyacetone is mainly prepared by a microbial fermentation method and a direct catalytic oxidation method of glycerol. The microbial fermentation method is a method for producing DHA by fermenting and converting glycerol with Acetobacter. Because the strain has strict requirements on survival conditions, the strain is easy to lose activity in the storage and transportation process; while the accumulation of substrates and products at high concentrations around the bacterial cells prolongs the fermentation period (300-400 hours) and reduces the yield. Therefore, the cost of the microbial fermentation process is high. The direct catalytic oxidation method of glycerol is a method for converting glycerol into dihydroxyacetone through a one-step reaction under the combined action of a catalyst and an oxidant. Hiroshi Kimura et al, in Pt/C, Pt-Bi/C and Pt-Bi-Ce/C catalysts, convert up to 70% of glycerol, but have a very low DHA selectivity (appl. Catal., A,1993,96, 217-228.). CN 102432445A discloses a method for preparing DHA by selectively oxidizing glycerol with hydrogen peroxide, but the selectivity of DHA in the method is still low and only reaches 24.2-85.7%.
By combining the analysis, the existing DHA preparation process still has room for improvement, and the effective utilization rate of glycerol needs to be further improved and the production cost of DHA needs to be reduced.
Disclosure of Invention
The invention aims to provide a preparation method of 1, 3-dihydroxyacetone aiming at the defects of the prior art, and the preparation method has the advantages of short synthesis period, high efficiency and low cost.
In order to achieve the above object, the present invention provides a method for preparing 1, 3-dihydroxyacetone, comprising the steps of:
(1) in the presence of a catalyst, glycerol and a halogenated reagent are subjected to contact reaction to prepare 1, 3-dichloro-2-propanol;
(2) carrying out oxidative dehydrogenation reaction on the 1, 3-dichloro-2-propanol to obtain an intermediate product 1, 3-dichloro-2-propanone;
(3) 1, 3-dichloro-2-propanone and alkaline substance are contacted in a water-containing medium for hydrolysis reaction to obtain 1, 3-dihydroxyacetone, wherein the temperature of the hydrolysis reaction is 25-60 ℃.
According to the technical scheme, the invention provides a preparation method of 1, 3-dihydroxyacetone, which is characterized in that glycerol is used as a raw material, and the glycerol is subjected to catalytic halogenation, oxidative dehydrogenation and hydrolysis reaction to prepare the 1, 3-dihydroxyacetone. The conversion rate of the glycerol and the yield of the 1, 3-dihydroxyacetone are both high, and the method adopts the zirconium oxide as the catalyst, so that the efficiency is high, the cost is low, and the method has an industrial application prospect.
Additional features and advantages of the invention will be set forth in the detailed description which follows.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain the principles of the invention and not to limit the invention. In the drawings:
FIG. 1 is a mass spectrum of glycerol in the present invention;
FIG. 2 shows NMR of glycerol in the present invention13C spectrum;
FIG. 3 is NMR of 1, 3-dichloro-2-propanol in example 113C spectrum;
FIG. 4 is a mass spectrum of 1, 3-dichloro-2-propanol from example 1;
FIG. 5 is the NMR of 1, 3-dichloroacetone in example 113C spectrum;
FIG. 6 is a mass spectrum of 1, 3-dichloroacetone in example 1;
FIG. 7 is NMR of 1, 3-dihydroxyacetone in example 113And (4) C spectrum.
Detailed Description
The following describes in detail specific embodiments of the present invention. It should be understood that the detailed description and specific examples, while indicating the present invention, are given by way of illustration and explanation only, not limitation.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value, and such ranges or values should be understood to encompass values close to those ranges or values. For ranges of values, between the endpoints of each of the ranges and the individual points, and between the individual points may be combined with each other to give one or more new ranges of values, and these ranges of values should be considered as specifically disclosed herein.
The invention provides a preparation method of 1, 3-dihydroxyacetone, which comprises the following steps:
(1) in the presence of a catalyst, glycerol and a halogenated reagent are subjected to contact reaction to prepare 1, 3-dichloro-2-propanol;
(2) carrying out oxidative dehydrogenation reaction on the 1, 3-dichloro-2-propanol to obtain an intermediate product 1, 3-dichloro-2-propanone;
(3) 1, 3-dichloro-2-propanone and alkaline substance are contacted in a water-containing medium for hydrolysis reaction to obtain 1, 3-dihydroxyacetone, wherein the temperature of the hydrolysis reaction is 25-60 ℃.
According to the invention, in step (1), specifically, the contact reaction is: the preparation method comprises the steps of uniformly mixing glycerol and a catalyst in an organic solvent according to a proportion to form a mixed system, dropwise adding a halogenated reagent into the mixed system, and reacting for 1-10 hours at 50-120 ℃.
According to the present invention, the organic solvent used in the present invention is an organic solvent that is miscible with glycerin, and may be at least one of alcohol, ether, ketone, amine, and the like, and is preferably C1～C5Alcohol of (1), C2～C5And more specifically, may be at least one of methanol, ethanol, isopropanol, N-butanol, acetone, N-methylpyrrolidone, diethyl ether, methyl tert-butyl ether, vinyl ether, acetamide, dimethylene sulfone, and o-cresol.
According to the invention, in the step (1), the halogenated reagent is slowly mixed with glycerol in a dropwise adding manner, so that the halogenated reagent is prevented from being added into a mixed system at one time, the concentration of the halogenated reagent in the mixed system can be effectively reduced, the yield of byproducts is reduced, the conversion rate of the halogenated reagent is improved, the content of free halogen in a reaction system is reduced, and the harm of the free halogen to the environment is reduced, preferably, the dropwise adding rate of the halogenated reagent is 6-12 mL/min.
According to the invention, in the step (1), in order to improve the conversion rate of the glycerol in the halogenation reaction and reduce the yield of byproducts, the ratio of the glycerol to the halogenated hydrocarbon should be reasonably controlled, and the molar ratio of the glycerol to the halogenating agent is preferably 1.0 (1.0-3.0).
According to the invention, the content of the catalyst is one of important factors influencing the catalytic reaction efficiency, in the step (1), in order to improve the catalytic reaction efficiency, the catalytic effect of the catalyst is optimal, and further preferably, the mass ratio of the glycerol to the catalyst is 1 (0.01-0.8).
According to the invention, further, in the step (1), the catalyst is a zirconium oxide catalyst loaded with sulfuric acid, and the catalyst is a solid-loaded super acidic catalytic material, and has the characteristics of high catalytic activity, good selectivity, no environmental pollution, no corrosion to equipment, reusability and relatively low cost.
According to the present invention, further, in the step (1), the halogenating agent is at least one of hydrogen halide, phosphorus halide and thionyl chloride, such as at least one of hydrogen chloride, hydrogen bromide, phosphorus trichloride, phosphorus pentachloride and thionyl chloride, and in order to enable the halogenating agent to be better mixed with glycerol in an organic solvent, the halogenating agent is further in a liquid state, such as hydrochloric acid, hydrobromic acid, phosphorus trichloride, an aqueous solution of phosphorus pentachloride and an ethanol solution of thionyl chloride.
According to the invention, in the step (2), the oxidative dehydrogenation method comprises the steps of dissolving 1, 3-dichloro-2-propanol, sodium bromide and sodium dichloroisocyanurate in an organic solvent to obtain a mixed solution, adding a pH buffering agent into the mixed solution, adjusting the pH of the solution to 8.0-9.5, and dropwise adding sodium hypochlorite into the mixed solution under the condition of stirring.
According to the present invention, in the step (2), since the oxidative dehydrogenation of 1, 3-dichloro-2-propanol releases a large amount of heat, further, the oxidative dehydrogenation is performed in an ice water bath in order to reduce the system heat.
According to the invention, further, in the step (2), the temperature of the oxidative dehydrogenation reaction is 0-28 ℃ and the time is 30-180 min.
According to the invention, in the oxidative dehydrogenation reaction of the 1, 3-dichloro-2-propanol, the influence of the pH value of the system on the reaction is large. When the system is acidic, chlorine gas is generated, thereby reducing the selectivity of the desired product. Therefore, the pH value of the solution is adjusted by adding an alkaline buffer, and further, the buffer is one of sodium bicarbonate and sodium carbonate buffer, boric acid-borax buffer, glycine-sodium hydroxide buffer and borax-sodium hydroxide buffer.
According to the invention, the boiling point of the product 1, 3-dihydroxyacetone is 70-75 ℃. Therefore, in the step (3), the 1, 3-dihydroxyacetone can be purified by adopting a distillation method, and further, the distillation temperature is 70-80 ℃.
The present invention will be described in detail below by way of examples.
Nuclear magnetic resonance of materials of the invention13The C spectrum was obtained by testing a UNITYLINOVA 500MHz NMR spectrometer (5mm double resonance probe, phi 4mm ZrO2 rotor) manufactured by Varian corporation, USA; the MASs spectrum was obtained by GC-MAS test type Agilent 5977A.
In the invention, glycerin, sodium bromide, sodium dichloroisocyanurate, sodium hypochlorite, sodium bicarbonate and sodium carbonate, sodium hydroxide, phosphorus trichloride, phosphorus pentachloride and thionyl chloride are purchased from national medicine group chemical reagent limited. Wherein the nuclear magnetic resonance of glycerol13The spectrum C is shown in figure 1, the high-resolution mass spectrum is shown in figure 2,13peaks at chemical shifts 63.0 and 72.4 in a C NMR spectrum are respectively assigned to end carbon and middle carbon, and a peak with a mass-to-charge ratio of 61 in a mass spectrum is a standard peak.
The conversion of glycerol in the present invention is calculated by the following formula:
glycerol conversion (%) ═ m1-m2)/m1×100％
Production of 1, 3-dihydroxyacetoneThe ratio (%) < mPractice of/mTheory of the invention×100％
Wherein: m is1M is the amount of glycerol added2The residual amount of the glycerol after the reaction in the step (1) is finished;
mtheory of the inventionIs the theoretical amount of 1, 3-dihydroxyacetone produced, mPractice ofIs the actual amount of 1, 3-dihydroxyacetone produced.
Example 1
Uniformly mixing 0.2mol of glycerol and 1g of catalyst in 100mL of acetone to form a mixed system (the catalyst is zirconium oxide loaded with sulfuric acid, the mass of the sulfuric acid is 8% of that of the zirconium oxide), then dropwise adding 40mL of hydrochloric acid with the mass fraction of 35% into the mixed system at the speed of 9mL/min, then reacting for 2h at 80 ℃, and obtaining a mixed product after the reaction is finished;
filtering the mixed product, collecting the filter residue (the main component of the filter residue is catalyst), extracting the filtrate with 100mL water for 3 times, collecting the lower solution, and distilling the lower solution under reduced pressure to obtain 25.8g (0.2mol) of 1, 3-dichloro-2-propanol, which is subjected to nuclear magnetic resonance13The spectrum C is shown in figure 3, the high resolution mass spectrum is shown in figure 4,13peaks at chemical shifts of 45.8 and 71 in the C NMR spectrum are respectively assigned to end carbon and middle carbon, and a peak with a mass-to-charge ratio of 79 in the mass spectrum is a standard peak.
Putting 100mL of water into an ice water bath, then adding 0.2mol of 1, 3-dichloro-2-propanol, 0.3mol of sodium bromide and 0.4mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, adding sodium bicarbonate and sodium carbonate buffer solution into the mixed solution, adjusting the pH of the solution to 9.0, dropwise adding 70mL of 5M sodium hypochlorite solution into the mixed solution under the condition of stirring, reacting for 30min, washing and drying the product to obtain 23.24g (0.183mol) of 1, 3-dichloro-2 acetone, and carrying out nuclear magnetic resonance on the 1, 3-dichloro-2-acetone13The spectrum C is shown in figure 5, the high-resolution mass spectrum is shown in figure 6,13peaks at chemical shifts 46.3 and 195 in the C NMR spectrum are respectively assigned to end carbon and middle carbon, and a peak with a mass-to-charge ratio of 77 in the mass spectrum is a standard peak.
0.183mol of 1, 3-dichloro-2-propanone was added to 100mL of 6M sodium hydroxide solution, and the mixture was hydrolyzed at 50 ℃ for 1 hour under stirring, after the reaction was completed, the system was transferred to a distillation flask and distilled at 78 ℃ to obtain 15.35g (0.171mol) of 1, 3-dihydroxyacetone, whose mass spectrum is shown in FIG. 7, in which the peak having a mass-to-charge ratio of 145 was the standard peak.
Example 2
Uniformly mixing 0.2mol of glycerol and 1.2g of catalyst in 100 mLN-methyl pyrrolidone to form a mixed system (the catalyst is zirconium oxide loaded with sulfuric acid, and the mass of the sulfuric acid is 10% of that of the zirconium oxide), then dropwise adding 26mL of hydrobromic acid with the mass fraction of 40% into the mixed system at the speed of 6mL/min, then reacting for 5 hours at 60 ℃, and obtaining a mixed product after the reaction is finished;
filtering the mixed product, collecting filter residues, extracting the filtrate for 3 times by using 100mL of water, taking the lower-layer solution, and carrying out reduced pressure distillation on the lower-layer solution to obtain 23.64g (0.183mol) of 1, 3-dichloro-2-propanol;
putting 100mL of water into an ice water bath, then adding 0.18mol of 1, 3-dichloro-2-propanol, 0.18mol of sodium bromide and 0.27mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, adding a glycine-sodium hydroxide buffer solution into the mixed solution, adjusting the pH of the solution to 9.5, dropwise adding 100mL of a 5M sodium hypochlorite solution into the mixed solution under the condition of stirring, reacting for 30min, washing and drying a product to obtain 20.1g (0.158mol) of 1, 3-dichloro-2 acetone;
0.158mol of 1, 3-dichloro-2-propanone was added to 100mL of 6M sodium hydroxide solution, and hydrolysis reaction was carried out at 30 ℃ for 1.5h with continuous stirring, after the reaction was completed, the system was transferred to a distillation flask and distilled at 75 ℃ to obtain 13.1g (0.145mol) of 1, 3-dihydroxyacetone.
Example 3
Uniformly mixing 0.2mol of glycerol and 0.5g of catalyst in 100mL of toluene to form a mixed system (the catalyst is zirconium oxide loaded with sulfuric acid, and the mass of the sulfuric acid is 3% of that of the zirconium oxide), dropwise adding 45mL of phosphorus trichloride into the mixed system at the speed of 9mL/min, reacting at 50 ℃ for 10 hours, and obtaining a mixed product after the reaction is finished;
filtering the mixed product, collecting filter residues, extracting the filtrate for 3 times by using 100mL of water, taking the lower layer solution, and carrying out reduced pressure distillation on the lower layer solution to obtain 24.4g (0.189mol) of 1, 3-dichloro-2-propanol;
putting 100mL of water into a water bath kettle, adjusting the temperature of the water bath kettle to 10 ℃, then adding 0.18mol of 1, 3-dichloro-2-propanol, 0.36mol of sodium bromide and 0.54mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, adding a borax-sodium hydroxide buffer solution into the mixed solution, adjusting the pH of the solution to 8.7, dropwise adding 30mL of a sodium hypochlorite solution of 6M into the mixed solution under the condition of stirring, reacting for 30min, washing and drying a product to obtain 17.27g (0.136mol) of 1, 3-dichloro-2 acetone;
0.136mol of 1, 3-dichloro-2-propanone was added to 100mL of a 6M solution of sodium carbonate, hydrolysis was carried out at 25 ℃ for 15min with continuous stirring, and after the reaction was completed, the system was transferred to a distillation flask and distilled at 78 ℃ to obtain 11.4g (0.127mol) of 1, 3-dihydroxyacetone.
Example 4
Uniformly mixing 0.2mol of glycerol and 0.8g of catalyst in 100mL of methyl tert-butyl ether to form a mixed system (the catalyst is zirconium oxide loaded with sulfuric acid, and the mass of the sulfuric acid is 5% of that of the zirconium oxide), then dropwise adding 40mL of hydrochloric acid with the mass fraction of 30.2% into the mixed system at the speed of 10mL/min, then reacting for 3h at 80 ℃, and obtaining a mixed product after the reaction is finished;
filtering the mixed product, collecting filter residues, extracting the filtrate for 3 times by using 100mL of water, taking the lower-layer solution, and carrying out reduced pressure distillation on the lower-layer solution to obtain 22g (0.17mol) of 1, 3-dichloro-2-propanol;
putting 100mL of water into a water bath kettle, adjusting the temperature of the water bath kettle to be 18 ℃, then adding 0.17mol of 1, 3-dichloro-2-propanol, 0.36mol of sodium bromide and 0.45mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, adding a boric acid-borax buffer solution into the mixed solution, adjusting the pH of the solution to be 8.5, dropwise adding 50mL of 6M sodium hypochlorite into the mixed solution under the condition of stirring, reacting for 30min, washing and drying a reaction product to obtain 19.56g (0.154mol) of 1, 3-dichloro-2 acetone;
0.165mol of 1, 3-dichloro-2-propanone was added to 100mL of 6M sodium hydroxide solution, hydrolysis was carried out at 40 ℃ for 1.5h with continuous stirring, and after the reaction was completed, the system was transferred to a distillation flask and distilled at 80 ℃ to obtain 12.28g (0.136mol) of 1, 3-dihydroxyacetone.
Example 5
Uniformly mixing 0.2mol of glycerol and 0.3g of catalyst in a mixed solvent of 200mL of isopropanol and 100mL of n-butanol to form a mixed system (the catalyst is zirconium oxide loaded with sulfuric acid, the mass of the sulfuric acid is 15% of that of the zirconium oxide), dropwise adding 65mL of 60% dichloromethylsulfonylbenzene ethanol solution into the mixed system at the speed of 12mL/min, reacting at 120 ℃ for 1h, and obtaining a mixed product after the reaction is finished;
filtering the mixed product, collecting filter residues, extracting the filtrate for 3 times by using 100mL of water, taking the lower-layer solution, and carrying out reduced pressure distillation on the lower-layer solution to obtain 19.37g (0.15mol) of 1, 3-dichloro-2-propanol;
putting 100mL of water into a water bath kettle, adjusting the temperature of the water bath kettle to 28 ℃, then adding 0.15mol of 1, 3-dichloro-2-propanol, 0.075mol of sodium bromide and 0.15mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, adding sodium bicarbonate and sodium carbonate buffer solution into the mixed solution, adjusting the pH of the solution to 9.0, dropwise adding 30mL of 4M sodium hypochlorite solution into the mixed solution under the condition of stirring, reacting for 30min, washing and drying the product to obtain 17.65g (0.139mol) of 1, 3-dichloro-2 acetone;
0.139mol of 1, 3-dichloro-2-propanone was added to 100mL of 4M sodium hydroxide solution, hydrolysis was carried out at 60 ℃ for 30min with continuous stirring, and after the reaction was completed, the system was transferred to a distillation flask and distilled under reduced pressure at 70 ℃ to obtain 9.77g (0.108mol) of 1, 3-dihydroxyacetone.
Example 6
The procedure of example 1 was followed, except that the catalyst was zirconia and the catalytic reaction time was 12 hours, as follows:
uniformly mixing 0.2mol of glycerol and 1g of zirconia in 100mL of acetone to form a mixed system, dropwise adding 40mL of hydrochloric acid with the mass fraction of 35% into the mixed system at the speed of 9mL/min, and reacting at 80 ℃ for 24 hours to obtain a mixed product after the reaction is finished;
filtering the mixed product, collecting filter residues, extracting the filtrate for 3 times by using 100mL of water, taking the lower-layer solution, and carrying out reduced pressure distillation on the lower-layer solution to obtain 15.2g (0.118mol) of 1, 3-dichloro-2-propanol;
putting 100mL of water into an ice water bath, then adding 0.118mol of 1, 3-dichloro-2-propanol, 0.045mol of sodium bromide and 0.06mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, adding a sodium bicarbonate buffer solution and a sodium carbonate buffer solution into the mixed solution, adjusting the pH of the solution to 9.0, dropwise adding 10mL of a 5M sodium hypochlorite solution into the mixed solution under the condition of stirring, reacting for 30min, washing and drying a product to obtain 10.3g (0.08mol) of 1, 3-dichloro-2 acetone;
0.125mol of 1, 3-dichloro-2-propanone was added to 10mL of 6M sodium hydroxide solution, hydrolysis was carried out at 50 ℃ for 1h with continuous stirring, and after the reaction was completed, the system was transferred to a distillation flask and distilled at 78 ℃ to obtain 4.6g (0.05mol) of 1, 3-dihydroxyacetone.
Example 7
The procedure of example 1 was followed except that the pH of the solution was not adjusted using a buffer solution, and the specific procedure was as follows:
uniformly mixing 0.2mol of glycerol and 1g of catalyst in 100mL of acetone to form a mixed system (the catalyst is zirconium oxide loaded with sulfuric acid, the mass of the sulfuric acid is 8% of that of the zirconium oxide), then dropwise adding 40mL of hydrochloric acid with the mass fraction of 35% into the mixed system at the speed of 9mL/min, then reacting for 2h at 80 ℃, and obtaining a mixed product after the reaction is finished;
filtering the mixed product, collecting filter residues, extracting the filtrate for 3 times by using 100mL of water, taking the lower-layer solution, and carrying out reduced pressure distillation on the lower-layer solution to obtain 25.2g (0.195mol) of 1, 3-dichloro-2-propanol;
putting 100mL of water into an ice water bath, then adding 0.195mol of 1, 3-dichloro-2-propanol, 0.3mol of sodium bromide and 0.4mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, dropwise adding 70mL of 5M sodium hypochlorite solution into the mixed solution under the condition of stirring, reacting for 30min, and washing and drying a product to obtain 10.8g (0.085mol) of 1, 3-dichloro-2-propanone;
0.085mol of 1, 3-dichloro-2-propanone was added to 100mL of 6M sodium hydroxide solution and hydrolyzed at 50 ℃ for 1h with constant stirring, after the reaction was completed, the system was transferred to a distillation flask and distilled at 78 ℃ to obtain 6.81g (0.076mol) of 1, 3-dihydroxyacetone.
Comparative example 1
The method for preparing 1, 3-dihydroxyacetone in Chinese patent CN 102432445A comprises the following steps:
2.42kgCu (NO)3)2·3H2O、5.82kgNi(NO3)2·6H2O and 3.75kgAl (NO)3)3·9H2Preparing 40L solution from O by using deionized water; mixing 1.06kgNa2CO3Preparing 40L solution with deionized water, mixing the two solutions, stirring vigorously at 60 deg.C for 0.5 hr, and adding NaOH to control pH of the mixture to 10.0. Filtering or centrifuging the obtained colloid for dewatering, washing with water to neutrality, oven drying at 100 deg.C, and placing at 500 deg.C under N2Calcining for 2 hours in the atmosphere, putting the obtained sample into a glycerol aqueous solution with the mass percentage concentration of 40%, controlling the pH value at 10.0, stirring for 24 hours at the temperature of 80 ℃, filtering or centrifugally dewatering the obtained colloid, and drying at the temperature of 100 ℃ to obtain the required catalyst. Taking 5L of glycerol aqueous solution with the mass percentage concentration of 40%, adding the prepared catalyst with the mass percentage concentration of 20% of glycerol, heating to 50 ℃, then dropwise adding hydrogen peroxide with the mass percentage concentration of 3.0%, reacting for 24h, and then centrifugally separating the catalyst and reaction liquid to obtain the 1, 3-dichloro-2-acetone.
Comparative example 2
The procedure of example 1 was followed except that the temperature of the hydrolysis reaction in step (3) was 20 ℃ and the specific procedure was as follows:
uniformly mixing 0.2mol of glycerol and 1g of catalyst in 100mL of acetone to form a mixed system (the catalyst is zirconium oxide loaded with sulfuric acid, the mass of the sulfuric acid is 8% of that of the zirconium oxide), then dropwise adding 40mL of hydrochloric acid with the mass fraction of 35% into the mixed system at the speed of 9mL/min, then reacting for 2h at 80 ℃, and obtaining a mixed product after the reaction is finished;
filtering the mixed product, collecting filter residues, extracting the filtrate for 3 times by using 100mL of water, taking the lower-layer solution, and carrying out reduced pressure distillation on the lower-layer solution to obtain 24.6g (0.191mol) of 1, 3-dichloro-2-propanol;
putting 100mL of water in an ice water bath, then adding 0.191mol of 1, 3-dichloro-2-propanol, 0.3mol of sodium bromide and 0.4mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, adding a sodium bicarbonate buffer solution and a sodium carbonate buffer solution into the mixed solution, adjusting the pH of the solution to 9.0, dropwise adding 70mL of a 5M sodium hypochlorite solution into the mixed solution under the condition of stirring, reacting for 30min, washing and drying a product to obtain 23.49g (0.185mol) of 1, 3-dichloro-2 acetone;
0.185mol of 1, 3-dichloro-2-propanone was added to 100mL of 6M sodium hydroxide solution, and hydrolyzed at 20 ℃ for 1h with constant stirring, and after the reaction was completed, the system was transferred to a distillation flask and distilled at 78 ℃ to obtain 1.62g (0.018mol) of 1, 3-dihydroxyacetone.
Comparative example 3
Uniformly mixing 0.2mol of glycerol and 1g of catalyst in 100mL of acetone to form a mixed system (the catalyst is zirconium oxide loaded with sulfuric acid, the mass of the sulfuric acid is 8% of that of the zirconium oxide), then dropwise adding 40mL of hydrochloric acid with the mass fraction of 35% into the mixed system at the speed of 9mL/min, then reacting for 2h at 80 ℃, and obtaining a mixed product after the reaction is finished;
filtering the mixed product, collecting filter residues, extracting the filtrate for 3 times by using 100mL of water, taking the lower-layer solution, and carrying out reduced pressure distillation on the lower-layer solution to obtain 25.3g (0.196mol) of 1, 3-dichloro-2-propanol;
putting 100mL of water into an ice-water bath, then adding 0.196mol of 1, 3-dichloro-2-propanol, 0.3mol of sodium bromide and 0.4mol of sodium dichloroisocyanurate into the water, fully mixing to obtain a mixed solution, adding sodium bicarbonate and sodium carbonate buffer solution into the mixed solution, adjusting the pH of the solution to 9.0, dropwise adding 70mL of 5M sodium hypochlorite solution into the mixed solution under the condition of stirring, reacting for 30min, washing and drying the product to obtain 23.9g (0.188mol) of 1, 3-dichloro-2 acetone;
1, 3-dichloro-2-propanone (0.188mol) was added to 100mL of 6M sodium hydroxide solution, and the mixture was hydrolyzed at 80 ℃ for 20min with continuous stirring, and after the reaction was completed, the system was transferred to a distillation flask and distilled at 78 ℃ to obtain 3.15g (0.035mol) of 1, 3-dihydroxyacetone.
1, 3-dihydroxyacetone was prepared by the methods in examples 1-7 and comparative examples 1-3, wherein the data for glycerol conversion, 1, 3-dihydroxyacetone yield, and the entire reaction cycle are compiled in Table 1.
TABLE 1
| Example numbering | Glycerol conversion/% | 1, 3-dihydroxyacetone yield% | Reaction period |
| Example 1 | 100 | 85.3 | About 6h |
| Example 2 | 91.6 | 72.9 | About 10h |
| Example 3 | 94.6 | 63.4 | About 12h |
| Example 4 | 85.3 | 68.8 | About 6h |
| Example 5 | 75.1 | 54.3 | About 4h |
| Example 6 | 58.9 | 25 | About 28h |
| Example 7 | 97.5 | 37.8 | About 6h |
| Comparative example 1 | - | - | 55h |
| Comparative example 2 | 95.5 | 9 | About 6h |
| Comparative example 3 | 98 | 17.5 | About 6h |
The experimental structure shows that: the conversion rate of the glycerol is high, the yield of the final product 1, 3-dihydroxyacetone is also high and reaches 54.3-85.3%, the preparation method is short in period, the zirconium oxide with low price is used as the catalyst, the expensive catalyst is not needed, the production cost is reduced, and the method has wide application prospects in industrial production of the 1, 3-dihydroxyacetone.
The preferred embodiments of the present invention have been described in detail, however, the present invention is not limited to the specific details of the above embodiments, and various simple modifications may be made to the technical solution of the present invention within the technical idea of the present invention, and these simple modifications are within the protective scope of the present invention. It should be noted that the various features described in the above embodiments may be combined in any suitable manner without departing from the scope of the invention. The invention is not described in detail in order to avoid unnecessary repetition.
In addition, any combination of the various embodiments of the present invention is also possible, and the same should be considered as the disclosure of the present invention as long as it does not depart from the spirit of the present invention.
Claims (9)
1. A preparation method of 1, 3-dihydroxyacetone is characterized by comprising the following steps:
(1) in the presence of a catalyst, glycerol and a halogenated reagent are subjected to contact reaction to prepare 1, 3-dichloro-2-propanol;
(2) dissolving 1, 3-dichloro-2-propanol, sodium bromide and sodium dichloroisocyanurate in an organic solvent to obtain a mixed solution, adding a pH buffering agent into the mixed solution, adjusting the pH of the solution to 8.0-9.5, and dropwise adding sodium hypochlorite into the mixed solution under the stirring condition to obtain an intermediate product 1, 3-dichloro-2-propanone;
(3) 1, 3-dichloro-2-propanone and alkaline substance are contacted in a water-containing medium for hydrolysis reaction to obtain 1, 3-dihydroxyacetone, wherein the temperature of the hydrolysis reaction is 25-60 ℃.
2. The production method according to claim 1, wherein, in step (1), the contact reaction is: the preparation method comprises the steps of uniformly mixing glycerol and a catalyst in an organic solvent according to a proportion to form a mixed system, dropwise adding a halogenated reagent into the mixed system, and reacting for 1-10 hours at 50-120 ℃.
3. The production method according to claim 1 or 2, wherein the molar ratio of the glycerin to the halogenating agent is 1 (1-3).
4. The production method according to claim 3, wherein the mass ratio of the glycerin to the catalyst is 1 (0.01 to 0.8).
5. The production method according to claim 1, wherein, in step (1), the catalyst is a sulfuric acid-supported zirconia catalyst.
6. The production method according to claim 1 or 5, wherein, in step (1), the halogenating agent is at least one of hydrogen chloride, phosphorus trichloride, phosphorus pentachloride and thionyl chloride.
7. The preparation method according to claim 2, wherein, in the step (1), the organic solvent is at least one of ethanol, isopropanol, N-butanol, acetone, N-methylpyrrolidone, diethyl ether, methyl tert-butyl ether, vinyl ether, toluene and benzene.
8. The production method according to claim 1, wherein in the step (2), the oxidative dehydrogenation is carried out at a temperature of 0 to 28 ℃ for 30 to 180 min.
9. The method of claim 8, wherein the buffer is one of a sodium bicarbonate and sodium carbonate buffer, a boric acid-borax buffer, a glycine-sodium hydroxide buffer, and a borax-sodium hydroxide buffer.
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| "Preparation of dihydroxyacetone"，WaldmannE.et al.，Monatshefte fuer Chemie，第82卷，第861-867页;WaldmannE.et al.;《Monatshefte fuer Chemie》;19511231;第82卷;第861-867页 * |
| "甘油合成1,3-丙二醇"，陈国辉等，精细化工，第28卷第4期，第406-409页;陈国辉等;《精细化工》;20110430;第28卷(第4期);第406-409页 * |
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