CN107382712B - Preparation method of 1, 10-sebacic acid - Google Patents
Preparation method of 1, 10-sebacic acid Download PDFInfo
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Abstract
The invention discloses a preparation method of 1, 10-sebacic acid, which comprises the following steps: hydrolyzing and ring-opening the substance A in an acid environment to obtain 4, 7-diketone-1, 10-sebacic acid; hydrogenating and deoxidizing the 4, 7-diketone-1, 10-sebacic acid, hydrogen, trifluoromethanesulfonate and a hydrogenation catalyst to obtain the 1, 10-sebacic acid. The method has the advantages of good atomic economy, high product yield, high product purity, small environmental pollution, simple process route, convenient operation, cheap and easily-obtained raw materials and suitability for industrial large-scale production.
Description
Technical Field
The invention relates to the technical field of chemical substance preparation, in particular to a preparation method of 1, 10-sebacic acid.
Background
The 1, 10-decanedioic acid has wide application, is mainly used for preparing esters of the decanedioic acid, and has wide application of the esters, such as dibutyl sebacate, dioctyl sebacate and diisooctyl sebacate. The esters can be used as plasticizers for plastics and cold-resistant rubber; can also be used for preparing polyamide, polyurethane, alkyd resin, synthetic lubricating oil, lubricating oil additive, spice, paint, cosmetics, etc.; can also be used as raw materials for producing nylon 10, nylon 9,10, nylon 8,10, nylon 6,10 and nylon 9 and high-temperature-resistant lubricating oil diethylhexyl ester; and also as raw materials for plasticizers, softeners and solvents for alkyd resins (used as surface coatings, plasticized cellulose nitrate coatings and urea resin varnishes) and polyurethane rubbers, cellulose resins, vinyl resins and synthetic rubbers.
1, 10-sebacic acid was obtained by dry distillation of castor oil with alkali at the earliest and a synthesis method was developed subsequently. At present, a new route for preparing 1, 10-sebacic acid by fermenting petroleum normal paraffin is being developed. Another production method of 1, 10-sebacic acid is the electrolytic oxidation of adipic acid developed by Asahi chemical industry Co., Japan, but the above method uses a limited source of raw materials or a non-renewable petroleum resource.
Disclosure of Invention
Based on the technical problems in the background art, the invention provides the preparation method of the 1, 10-sebacic acid, and the preparation method has the advantages of cheap and easily-obtained raw materials, good atomic economy, high product yield, high product purity, small environmental pollution, simple process route, convenient operation and suitability for industrial large-scale production.
The invention provides a preparation method of 1, 10-sebacic acid, which comprises the following steps: hydrolyzing and ring-opening the substance A in an acid environment to obtain 4, 7-diketone-1, 10-sebacic acid; the 4, 7-diketone-1, 10-sebacic acid is hydrogenated and deoxidized with hydrogen, trifluoromethanesulfonate and a hydrogenation catalyst to obtain the 1, 10-sebacic acid, wherein a chemical structural formula of a substance A is as follows:
wherein R is a hydrogen atom or an alkyl group.
Preferably, R is a hydrogen atom or an alkyl group having less than 5 carbon atoms.
Preferably, the pH of the acidic environment is less than 1.
Preferably, the triflate is a metal triflate having a valence of +3 to + 6.
Preferably, the molar ratio of the 4, 7-diketone-1, 10-sebacic acid to the triflate is 10-100: 1.
the above-mentioned trifluoromethanesulfonate comprises W (OTf)6、Hf(OTf)4、Al(OTf)3、Ta(OTf)5、Nb(OTf)5、Zr(OTf)4And (c) an equivalent metal salt of trifluoromethanesulfonic acid having a valence of +3 to + 6.
Preferably, the hydrogenation catalyst is a catalyst comprising a group VIII transition metal element.
Preferably, the molar ratio of the metal element in the group VIII transition metal element-containing catalyst to the 4, 7-diketone-1, 10-sebacic acid is 1: 10-1000.
The hydrogenation catalyst refers to a catalyst used when a compound is added with hydrogen, such as: group VIII transition metals, metal oxides containing group VIII transition metal elements, metal complexes, and the like; the support for the metal complex is typically alumina or activated carbon; the specific hydrogenation catalyst comprises: palladium on carbon, platinum on carbon, and the like.
Preferably, the reaction solvent for hydrodeoxygenation is a carboxylic acid.
Preferably, the reaction solvent for hydrodeoxygenation is acetic acid.
Preferably, the acidic environment is maintained with an acidic substance.
Preferably, the acidic substance is a strong inorganic acid.
The inorganic strong acid includes conventional inorganic strong acids such as hydrochloric acid and sulfuric acid.
Preferably, the hydrogen pressure is 3 to 100 atm.
Preferably, the hydrogen pressure is 3 to 50 atm.
Preferably, the reaction temperature for hydrodeoxygenation is 120-.
Preferably, the reaction temperature for hydrodeoxygenation is 160-.
Preferably, the reaction time for hydrodeoxygenation is between 1 and 24 h.
Preferably, the specific steps of hydrolytic ring opening are: and (3) uniformly mixing the methanol and the substance A, adjusting the pH to be less than 1, refluxing, and spin-drying to obtain a solid, namely the 4, 7-diketone-1, 10-sebacic acid.
Preferably, the pH is adjusted to less than 1 with an aqueous acidic material solution during hydrolytic ring opening.
Preferably, the mass fraction of the aqueous acidic substance solution is 20 to 50 wt%.
Preferably, the reflux is carried out for 10-24h during the hydrolytic ring opening process.
Preferably, in the hydrolytic ring opening process, after spin-drying, the 4, 7-diketone-1, 10-sebacic acid is obtained through purification.
Preferably, the specific steps of purification are: dissolving the solid in an alkaline aqueous solution, adding activated carbon for decolorization, filtering to obtain filtrate, adjusting the pH to be less than 1, and crystallizing to obtain the 4, 7-diketone-1, 10-sebacic acid.
Preferably, the hydrodeoxygenation comprises the following specific steps: uniformly mixing 4, 7-diketone-1, 10-sebacic acid, a hydrogenation catalyst, trifluoromethanesulfonate and a reaction solvent, stirring and heating in a hydrogen atmosphere, and keeping the temperature and stirring to obtain the 1, 10-sebacic acid.
Preferably, in the hydrodeoxygenation process, after heat preservation and stirring, the 1, 10-sebacic acid is obtained through purification.
Preferably, the specific steps of purification are: filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; the solid was decolorized to give 1, 10-decanedioic acid.
Preferably, the specific steps of decoloring are as follows: dissolving the solid in sodium hydroxide aqueous solution, adding active carbon for decoloring, filtering to obtain filtrate, regulating the pH value to be less than 2 by using hydrochloric acid, filtering to obtain filter cake, and drying to obtain the 1, 10-sebacic acid.
Preferably, furfural and a substance B are subjected to catalytic condensation by a basic substance to obtain a substance A, wherein the chemical structural formula of the substance B is as follows:
wherein, the substance B is the same as R in the substance A.
The furfural and the substance B are subjected to catalytic condensation by alkaline substances to obtain a substance A, which is a conventional aldol condensation reaction, and the synthetic route is as follows:
the preparation method of the aldol condensation reaction is quite complete, and the preparation can be carried out according to the conventional method in the field by a person skilled in the art, and can also be carried out according to the following definition:
preferably, when R is a hydrogen atom, the basic substance is a basic substance containing a metal element.
The alkaline substance containing metal element includes sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium ethoxide, potassium tert-butoxide, etc.
Preferably, the molar ratio of basic substance to substance B is greater than 1 when R is a hydrogen atom.
Preferably, when R is an alkyl group, the basic substance is an organic base.
Preferably, when R is an alkyl group, the basic substance is an organic base, wherein the organic base contains at least one of a primary amine group, a secondary amine group, and a tertiary amine group.
The organic base includes pyrrole, triethylamine, morpholine, pyridine and other conventional organic bases.
Preferably, when R is hydrogen atom, after condensation, acidification is required to obtain the substance A.
Preferably, when R is a hydrogen atom, the condensation comprises the following specific steps: and uniformly mixing the alkaline substance and the substance B solution, heating to reflux, dropwise adding the furfural solution, refluxing for 1-24h, and acidifying to obtain a substance A.
Preferably, when R is a hydrogen atom, the solvent of the solution of substance B is water during the condensation.
Preferably, when R is a hydrogen atom, the solvent of the furfural solution is methanol during the condensation.
Preferably, when R is a hydrogen atom, acidification is performed with an acidic aqueous solution during condensation.
Preferably, the acidic aqueous solution is 5-10 wt% hydrochloric acid aqueous solution.
Preferably, when R is hydrogen, the substance A is obtained by acidification and purification during condensation.
Preferably, the specific steps of purification are: filtering to obtain a filter cake, washing with ice water, and recrystallizing with hot water to obtain a substance A.
Preferably, when R is a hydrogen atom, the molar ratio of the substance B to the furfural in the condensation process is 5: 1-3.
Preferably, when R is alkyl, the specific steps of condensation are: and uniformly mixing the alkaline substance, the substance B and the furfural, and stirring at room temperature for 1-24h to obtain a substance A.
Preferably, when R is alkyl, the condensation is followed by stirring at room temperature and purification to give substance A.
Preferably, the specific steps of purification are: filtering to obtain filtrate, and concentrating to obtain concentrate; the concentrate was dissolved in ethyl acetate, eluted with a silica gel column and spin dried to give material a.
Preferably, when R is alkyl, the molar ratio of the basic substance, substance B, and furfural in the condensation process is 1: 1-10: 1-10.
In the hydrolytic ring-opening process, the dosage of the methanol is not specified, and the dosage is determined according to specific operation; the reflux temperature is not specified, and the reflux state is maintained.
In the hydrodeoxygenation process, the amount of the reaction solvent is not specified, and is determined according to the specific operation.
In the condensation process when R is a hydrogen atom, the concentration of the substance A solution and the concentration of the furfural solution are not specified, and the concentrations are determined according to specific operations; the reflux temperature is not specified, and the reflux state is maintained.
In the processes of hydrodeoxygenation, condensation and hydrolytic ring opening, the completion of the reaction can be monitored by the aid of thin-layer chromatography.
The synthetic route of the invention is as follows:
the inventor of the invention has intensively studied and found that the substance A (delta-furfuryl levulinic acid or ester thereof) is hydrolyzed and opened in an acid environment to obtain 4, 7-diketone-1, 10-sebacic acid, and ketone carbonyl in the 4, 7-diketone-1, 10-sebacic acid is hydrogenated and converted into secondary alcohol hydroxyl, and then the secondary alcohol hydroxyl is easily reacted with carboxylic acid to obtain secondary alcohol ester under the promotion of triflate; the secondary alcohol ester can remove hydroxyl by hydrogenolysis under the promotion of the triflate, so that the 4, 7-diketone-1, 10-sebacic acid is selectively subjected to hydrodeoxygenation under a hydrogenation catalyst and triflate co-catalysis system to obtain 1, 10-sebacic acid; the method has the advantages of good atomic economy, high product yield, high product purity, small environmental pollution, simple process route, convenient operation, suitability for industrial large-scale production, wide application field of the product 1, 10-sebacic acid, good market prospect and high added value of the product, and has potential industrial application prospect; and furfural and a substance B (levulinic acid or ester thereof) are selected as raw materials to prepare the substance A, the furfural can be obtained by hydrolysis of hemicellulose, the substance B can be obtained by hydrolysis or alcoholysis of cellulose, the source is wide, the substance B is a renewable biomass resource, and the method is cheap and easy to obtain, simple to operate, capable of reducing the production cost and suitable for industrial production.
Drawings
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1, 10-sebacic acid prepared by the present invention.
FIG. 2 is a nuclear magnetic carbon spectrum of 1, 10-sebacic acid prepared according to the present invention.
FIG. 3 is a nuclear magnetic hydrogen spectrum of 4, 7-diketone-1, 10-sebacic acid prepared by the present invention.
FIG. 4 is the nuclear magnetic carbon spectrum of 4, 7-diketone-1, 10-sebacic acid prepared by the invention.
Detailed Description
The technical solution of the present invention will be described in detail below with reference to specific examples.
Example 1
A preparation method of 1, 10-sebacic acid comprises the following steps: hydrolyzing and ring-opening the substance A in an acid environment to obtain 4, 7-diketone-1, 10-sebacic acid; hydrogenating and deoxidizing 4, 7-diketone-1, 10-sebacic acid, hydrogen, trifluoromethanesulfonate and hydrogenation catalyst to obtain 1, 10-sebacic acid
Example 2
A preparation method of 1, 10-sebacic acid comprises the following steps: uniformly mixing methanol and delta-furfuryl methyl levulinate, adjusting the pH to be less than 1 by using a hydrochloric acid aqueous solution with the mass fraction of 37 wt%, refluxing for 17h, and spin-drying to obtain a solid; dissolving the solid in sodium hydroxide aqueous solution, adding activated carbon, heating for decoloring, filtering to obtain filtrate, regulating the pH to be less than 1 by using hydrochloric acid, and crystallizing to obtain 4, 7-diketone-1, 10-sebacic acid;
mixing 4, 7-diketone-1, 10-decanedioic acid, palladium carbon, Al (OTf)3Mixing with acetic acid, and regulating hydrogen pressure in hydrogen atmosphereStirring at 80atm, heating to 140 deg.C, stirring for 20 hr, filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; dissolving the solid in sodium hydroxide water solution, adding active carbon for decolorization, filtering to obtain filtrate, adjusting pH to less than 2 with hydrochloric acid, filtering to obtain filter cake, and oven drying to obtain 1, 10-sebacic acid, wherein 4, 7-diketone-1, 10-sebacic acid, W (OTf)6In a molar ratio of 55: 1, the molar ratio of palladium element in palladium carbon to 4, 7-diketone-1, 10-sebacic acid is 1: 500.
example 3
A preparation method of 1, 10-sebacic acid comprises the following steps:
uniformly mixing sodium hydroxide and a levulinic acid aqueous solution, heating until reflux is achieved, dropwise adding a furfural methanol solution, refluxing for 1h, acidifying by using a hydrochloric acid aqueous solution with the mass fraction of 5 wt%, filtering to obtain a filter cake, washing by using ice water, and recrystallizing by using hot water to obtain the delta-furfuryl levulinic acid, wherein the molar ratio of levulinic acid to furfural is 5: 3, the molar ratio of sodium hydroxide to levulinic acid is 1.05: 1;
uniformly mixing methanol and delta-furfuryl levulinic acid, adjusting the pH to be less than 1 by using a hydrochloric acid aqueous solution with the mass fraction of 20 wt%, refluxing for 10 hours, and spin-drying to obtain a solid; dissolving the solid in 10 wt% sodium hydroxide aqueous solution, adding activated carbon, heating for decolorization, filtering to obtain filtrate, adjusting pH to less than 1 with hydrochloric acid, and crystallizing to obtain 4, 7-diketone-1, 10-sebacic acid;
mixing 4, 7-diketone-1, 10-decanedioic acid, platinum carbon, Zr (OTf)4Mixing with acetic acid, adjusting hydrogen pressure to 100atm in hydrogen atmosphere, stirring and heating to 120 deg.C, stirring for 24 hr, filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; dissolving the solid in sodium hydroxide aqueous solution, adding active carbon for decolorization, filtering to obtain filtrate, regulating pH to be less than 2 with hydrochloric acid, filtering to obtain filter cake, and drying to obtain 1, 10-sebacic acid, wherein 4, 7-diketone-1, 10-sebacic acid, Zr (OTf)4In a molar ratio of 100: 1, the molar ratio of the platinum element in the platinum carbon to the 4, 7-diketone-1, 10-sebacic acid is 1: 10.
example 4
A preparation method of 1, 10-sebacic acid comprises the following steps:
uniformly mixing sodium ethoxide and a levulinic acid aqueous solution, heating to reflux, dropwise adding a furfural methanol solution, refluxing for 24 hours, acidifying by using a hydrochloric acid aqueous solution with the mass fraction of 10 wt%, filtering to obtain a filter cake, washing by using ice water, and recrystallizing by using hot water to obtain the delta-furfuryl levulinic acid, wherein the molar ratio of the levulinic acid to the furfural is 5: 1, the molar ratio of sodium ethoxide to levulinic acid is 1.05: 1;
uniformly mixing methanol and delta-furfuryl levulinic acid, adjusting the pH to be less than 1 by using a sulfuric acid aqueous solution with the mass fraction of 50 wt%, refluxing for 24 hours, and spin-drying to obtain a solid; dissolving the solid in 10 wt% sodium hydroxide aqueous solution, adding activated carbon, heating for decolorization, filtering to obtain filtrate, adjusting pH to less than 1 with hydrochloric acid, and cooling for crystallization to obtain 4, 7-diketone-1, 10-sebacic acid;
mixing 4, 7-diketone-1, 10-decanedioic acid, palladium carbon, Hf (OTf)4Mixing with acetic acid, adjusting hydrogen pressure to 3atm in hydrogen atmosphere, stirring at 600r/min for 30min, heating to 250 deg.C, stirring for 1h, filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; dissolving the solid in sodium hydroxide water solution, adding active carbon for decolorization, filtering to obtain filtrate, adjusting pH to less than 2 with hydrochloric acid, filtering to obtain filter cake, and oven drying to obtain 1, 10-sebacic acid, wherein 4, 7-diketone-1, 10-sebacic acid, Hf (OTf)4In a molar ratio of 10: 1, the molar ratio of palladium element in palladium carbon to 4, 7-diketone-1, 10-sebacic acid is 1: 1000.
example 5
A preparation method of 1, 10-sebacic acid comprises the following steps:
mixing triethylamine, ethyl levulinate and furfural uniformly, stirring at room temperature for 1h, filtering to obtain filtrate, and concentrating to obtain a concentrate; dissolving the concentrate with ethyl acetate, eluting with a silica gel column, and spin-drying to obtain delta-furfuryl ethyl levulinate, wherein the molar ratio of triethylamine to ethyl levulinate to furfural is 1: 1: 1;
uniformly mixing methanol and delta-furfuryl ethyl levulinate, adjusting the pH to be less than 1 by using a hydrochloric acid aqueous solution with the mass fraction of 30 wt%, refluxing for 12h, and spin-drying to obtain a solid; dissolving the solid in 10 wt% sodium hydroxide aqueous solution, adding activated carbon, heating for decolorization, filtering to obtain filtrate, adjusting pH to less than 1 with hydrochloric acid, cooling to 0 ℃, and crystallizing for 10h to obtain 4, 7-diketone-1, 10-sebacic acid;
mixing 4, 7-diketone-1, 10-decanedioic acid, platinum carbon, Ta (OTf)5Mixing with acetic acid, regulating hydrogen pressure to 10atm in hydrogen atmosphere, stirring at 700r/min for 30min, heating to 200 deg.C, stirring for 12 hr, filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; dissolving the solid in sodium hydroxide aqueous solution, adding active carbon for decolorization, filtering to obtain filtrate, regulating pH to be less than 2 with hydrochloric acid, filtering to obtain filter cake, and drying to obtain 1, 10-sebacic acid, wherein 4, 7-diketone-1, 10-sebacic acid, Ta (OTf)5In a molar ratio of 80: 1, the molar ratio of the platinum element in the platinum carbon to the 4, 7-diketone-1, 10-sebacic acid is 1: 700.
example 6
A preparation method of 1, 10-sebacic acid comprises the following steps:
uniformly mixing pyridine, butyl levulinate and furfural, stirring at room temperature for 24 hours, filtering to obtain filtrate, and concentrating to obtain a concentrate; dissolving the concentrate with ethyl acetate, eluting with a silica gel column, and spin-drying to obtain delta-furfuryl butyl levulinate, wherein the molar ratio of pyridine to butyl levulinate to furfural is 1: 10: 10;
uniformly mixing methanol and delta-furfuryl butyl levulinate, adjusting the pH to be less than 1 by using a sulfuric acid aqueous solution with the mass fraction of 35 wt%, refluxing for 20h, and spin-drying to obtain a solid; dissolving the solid in 10 wt% sodium hydroxide aqueous solution, adding activated carbon, heating for decolorization, filtering to obtain filtrate, adjusting pH to less than 1 with hydrochloric acid, cooling to 0 ℃, and crystallizing for 10h to obtain 4, 7-diketone-1, 10-sebacic acid;
mixing 4, 7-diketone-1, 10-decanedioic acid, palladium carbon, Nb (OTf)5Mixing with acetic acid, regulating hydrogen pressure to 60atm in hydrogen atmosphere, stirring at 650r/min for 30min, heating to 220 deg.C, stirring for 8 hr, filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; dissolving the solid in sodium hydroxide aqueous solution, adding active carbon for decolorization, filtering to obtain filtrate, adjusting pH to less than 2 with hydrochloric acid, filtering to obtain filter cake, and oven drying to obtain 1, 10-sebacic acid, wherein 4, 7-diketone-1, 10-sebacic acid, Nb (OTf)5In a molar ratio of 40: 1, the molar ratio of palladium element in palladium carbon to 4, 7-diketone-1, 10-sebacic acid is 1: 100.
example 7
A preparation method of 1, 10-sebacic acid comprises the following steps:
uniformly mixing pyrrole, methyl levulinate and furfural, stirring at room temperature for 8 hours, filtering to obtain filtrate, and concentrating to obtain a concentrate; dissolving the concentrate with ethyl acetate, eluting with silica gel column, and spin-drying to obtain delta-furfuryl methyl levulinate, wherein the molar ratio of pyrrole to methyl levulinate to furfural is 1: 8: 8;
uniformly mixing methanol and delta-furfuryl methyl levulinate, adjusting the pH to be less than 1 by using a sulfuric acid aqueous solution with the mass fraction of 40 wt%, refluxing for 15h, and spin-drying to obtain a solid; dissolving the solid in a 10 wt% sodium hydroxide aqueous solution, adding activated carbon, heating for decoloration, filtering to obtain a filtrate, adjusting the pH to be less than 1 by using hydrochloric acid, cooling to 0 ℃, and crystallizing for 10 hours to obtain 4, 7-diketone-1, 10-sebacic acid, wherein the molar ratio of delta-furfuryl methyl levulinate to sulfuric acid is 1: 2.8, the molar volume (mol/l) ratio of methyl δ -furfuryl levulinate to methanol was 1: 1;
4, 7-diketone-1, 10-decanedioic acid, palladium carbon with palladium content of 5 wt%, Hf (OTf)3Mixing with acetic acid, introducing hydrogen to replace four times of gas, charging hydrogen at room temperature until the hydrogen pressure is 50atm, stirring at 800r/min for 30min, heating to 160 deg.C, stirring for 15h, cooling, relieving pressure, filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; dissolving the solid in 10 wt% sodium hydroxide aqueous solution, adding active carbon, heating for decolorizing for 30min, filtering to obtain filtrate, adjusting pH to less than 2 with hydrochloric acid, filtering to obtain filter cake, and oven drying to obtain 1, 10-sebacic acid, wherein 4, 7-diketone-1, 10-sebacic acid, Al (OTf)3In a molar ratio of 50: 3, the molar ratio of the palladium element in the palladium-carbon to the 4, 7-diketone-1, 10-sebacic acid is 1: the molar volume (mol/l) ratio of 50, 4, 7-diketone-1, 10-sebacic acid and acetic acid is 1: 15.
example 8
A preparation method of 1, 10-sebacic acid comprises the following steps:
adding sodium carbonate into a levulinic acid aqueous solution with the concentration of 1.55mol/l in batches, uniformly mixing, heating until reflux is achieved, dropwise adding a furfural methanol solution with the concentration of 5.81mol/l, refluxing for 1h, acidifying with a hydrochloric acid aqueous solution with the mass fraction of 7.5 wt%, filtering to obtain a filter cake, washing with ice water, and recrystallizing with hot water to obtain the delta-furfuryl levulinic acid, wherein the molar ratio of levulinic acid to furfural is 1: 0.6, the molar ratio of sodium carbonate to levulinic acid is 1.46: 1;
uniformly mixing methanol and delta-furfuryl levulinic acid, adjusting the pH to be less than 1 by using a hydrochloric acid aqueous solution with the mass fraction of 37 wt%, refluxing for 15h, and spin-drying to obtain a solid; dissolving the solid in a 10 wt% sodium hydroxide aqueous solution, adding activated carbon, heating for decoloration, filtering to obtain a filtrate, adjusting the pH to be less than 1 by using hydrochloric acid, cooling to 0 ℃, and crystallizing for 10 hours to obtain 4, 7-diketone-1, 10-sebacic acid, wherein the molar ratio of delta-furfuryl levulinic acid to hydrochloric acid is 1: 7.2, the molar volume (mol/l) ratio of δ -furfuryl levulinic acid and methanol is 3: 4;
4, 7-diketone-1, 10-decanedioic acid, palladium carbon with 10 wt% palladium content, W (OTf)6Mixing with acetic acid, introducing hydrogen to replace four times of gas, charging hydrogen at room temperature to hydrogen pressure of 30atm, stirring at 500r/min for 30min, heating to 180 deg.C, stirring for 10 hr, cooling, relieving pressure, filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; dissolving the solid in 10 wt% sodium hydroxide aqueous solution, adding active carbon, heating for decolorizing for 30min, filtering to obtain filtrate, adjusting pH to less than 2 with hydrochloric acid, filtering to obtain filter cake, and oven drying to obtain 1, 10-sebacic acid, wherein 4, 7-diketone-1, 10-sebacic acid, W (OTf)6In a molar ratio of 50: 3, the molar ratio of the palladium element in the palladium-carbon to the 4, 7-diketone-1, 10-sebacic acid is 1: the molar volume (mol/l) ratio of 50, 4, 7-diketone-1, 10-sebacic acid and acetic acid is 1: 10.
nuclear magnetic analyses were performed on the 4, 7-dione-1, 10-sebacic acid and 1, 10-sebacic acid obtained in example 8, and the results were shown in FIGS. 1 to 4.
FIG. 1 is a nuclear magnetic hydrogen spectrum of 1, 10-sebacic acid prepared according to the present invention, and the result is1H NMR(400MHz,DMSO):δ＝11.98(s,2H),2.18(t,J＝7.4Hz,4H),1.55-1.40(m,4H),1.25(s,8H)；
FIG. 2 shows the nuclear magnetic carbon spectrum of 1, 10-decanedioic acid prepared according to the invention, the result being13C NMR(101MHz,DMSO):δ＝174.97,34.12,29.03(d,J＝11.7Hz),24.94；
FIG. 3 is a nuclear magnetic hydrogen spectrum of 4, 7-diketone-1, 10-sebacic acid prepared by the invention, and the result is1H-NMR(400MHz,DMSO):δ＝12.10(s,2H),2.66(dd,J＝11.4,4.6Hz,8H),2.38(t,J＝6.5Hz,4H)；
FIG. 4 shows the nuclear magnetic carbon spectrum of 4, 7-diketone-1, 10-sebacic acid prepared according to the invention, and the result is13C-NMR(101MHz,DMSO):δ＝208.30,174.17,37.04,36.06,28.12；
The detection results show that the prepared 4, 7-diketone-1, 10-sebacic acid and 1, 10-sebacic acid are obtained.
The yields of examples 7 and 8 were counted, and the purities of δ -furfuryl levulinic acid, δ -furfuryl methyl levulinate, 4, 7-dione-1, 10-sebacic acid, and 1, 10-sebacic acid were measured, and the results were as follows:
as can be seen from the above table, the yield of the invention is high, and the purity of the prepared 1, 10-sebacic acid is good.
The above description is only for the preferred embodiment of the present invention, but the scope of the present invention is not limited thereto, and any person skilled in the art should be considered to be within the technical scope of the present invention, and the technical solutions and the inventive concepts thereof according to the present invention should be equivalent or changed within the scope of the present invention.
Claims (15)
1. A preparation method of 1, 10-sebacic acid is characterized by comprising the following steps: hydrolyzing and ring-opening the substance A in an acid environment to obtain 4, 7-diketone-1, 10-sebacic acid; the 4, 7-diketone-1, 10-sebacic acid is hydrogenated and deoxidized with hydrogen, trifluoromethanesulfonate and a hydrogenation catalyst to obtain the 1, 10-sebacic acid, wherein a chemical structural formula of a substance A is as follows:
wherein R is a hydrogen atom or an alkyl group;
the hydrogen pressure is 3-30 atm;
the reaction temperature of hydrodeoxygenation is 120-180 ℃;
the reaction solvent for hydrodeoxygenation is a carboxylic acid.
2. The method for preparing 1, 10-sebacic acid according to claim 1, characterized in that R is hydrogen or alkyl with a number of carbon atoms less than 5; the pH of the acidic environment is less than 1.
3. The method for producing 1, 10-sebacic acid according to claim 1, characterised in that the triflate is a metal triflate having a valence of +3 to + 6.
4. The process for producing 1, 10-sebacic acid according to claim 1, characterised in that the hydrogenation catalyst is a catalyst containing a group VIII transition metal element.
5. The method of claim 1, 10-decanedioic acid production according to claim 1, wherein the hydrodeoxygenation reaction solvent is acetic acid.
6. The method of claim 1, 10-decanedioic acid production wherein an acidic environment is maintained with an acidic substance; the acidic substance is strong inorganic acid.
7. The method for producing 1, 10-sebacic acid according to claim 1, ch a racterized i n that the hydrogen pressure is 3-10 atm; the reaction temperature of hydrodeoxygenation is 160-180 ℃; the reaction time of hydrodeoxygenation is 1-24 h.
8. The method for preparing 1, 10-sebacic acid according to claim 1, characterized in that the hydrolytic ring opening comprises the following steps: and (3) uniformly mixing the methanol and the substance A, adjusting the pH to be less than 1, refluxing, and spin-drying to obtain a solid, namely the 4, 7-diketone-1, 10-sebacic acid.
9. The method for preparing 1, 10-sebacic acid according to claim 8, characterized in that, during the hydrolytic ring-opening, the pH is adjusted to less than 1 with an aqueous solution of an acidic substance; refluxing for 10-24h in the hydrolytic ring-opening process; in the hydrolytic ring-opening process, after spin-drying, the 4, 7-diketone-1, 10-sebacic acid is obtained by purification.
10. The method for preparing 1, 10-sebacic acid according to claim 9, characterized by the specific steps of purification: dissolving the solid in an alkaline aqueous solution, adding activated carbon for decolorization, filtering to obtain filtrate, adjusting the pH to be less than 1, and crystallizing to obtain the 4, 7-diketone-1, 10-sebacic acid.
11. The method for preparing 1, 10-sebacic acid according to claim 1, characterized in that the hydrodeoxygenation comprises the following steps: uniformly mixing 4, 7-diketone-1, 10-sebacic acid, a hydrogenation catalyst, trifluoromethanesulfonate and a reaction solvent, stirring and heating in a hydrogen atmosphere, and keeping the temperature and stirring to obtain the 1, 10-sebacic acid.
12. The method of claim 11, wherein the 1, 10-decanedioic acid is obtained by further purifying the mixture after stirring while maintaining the temperature during the hydrodeoxygenation process.
13. The method for preparing 1, 10-sebacic acid according to claim 12, characterized by the specific steps of purification: filtering to obtain filtrate, and distilling under reduced pressure to obtain solid; the solid was decolorized to give 1, 10-decanedioic acid.
14. The method for preparing 1, 10-sebacic acid according to claim 13, characterized by the specific steps of decolorizing: dissolving the solid in sodium hydroxide aqueous solution, adding active carbon for decoloring, filtering to obtain filtrate, regulating the pH value to be less than 2 by using hydrochloric acid, filtering to obtain filter cake, and drying to obtain the 1, 10-sebacic acid.
15. The method for preparing 1, 10-sebacic acid according to claim 1, wherein furfural and substance B are catalytically condensed with an alkaline substance to obtain substance a, wherein substance B has the following chemical structural formula:
wherein, the substance B is the same as R in the substance A.
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| CN109694313B (en) * | 2018-12-06 | 2020-08-25 | 中国科学技术大学 | Method for preparing medium-chain aliphatic carboxylic acid |
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| CN111187161B (en) * | 2020-01-20 | 2021-10-01 | 中国科学技术大学 | Preparation method of dihydrocapsaicin and dihydrocapsaicin ester |
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