CN102452920B - Method for preparing corresponding hydroxy acid by catalytically oxidizing cyclic ketone - Google Patents
Method for preparing corresponding hydroxy acid by catalytically oxidizing cyclic ketone Download PDFInfo
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Abstract
The invention discloses a method for preparing a corresponding hydroxy acid by catalytically oxidizing cyclic ketone. The method is characterized by comprising the following steps of: undergoing a reaction at the temperature of 76-99 DEG C under the pressure of 0.1-3.0 MPa in the presence of a catalyst in the molar ratio of 1:(0-80):(0.2-20) of the cyclic ketone to a solvent to hydrogen peroxide; recovering to obtain the corresponding hydroxyl acid, wherein the catalyst is a titanium-silicon molecular sieve; and the mass ratio of the catalyst to the cyclic ketone is 1:(5-100). Compared with the prior art, the method has the advantage that: the defects of complex production process, corrosion of equipment, potential safety hazard, severe environmental pollution and the like existing in the conventional oxidizing method are overcome.
Description
Technical field
The invention relates to a kind of environmental friendliness and prepare the method for alcohol acid, more specifically say that about a kind of hydrogen peroxide be the method that oxidizer catalytic oxidizing cyclic ketone is prepared corresponding alcohol acid.
Background technology
Alcohol acid is important industrial chemicals.Taking 6 hydroxycaproic acid as example, it has a wide range of applications in organic synthesis and polymeric material field, for example, preparation 6-aldehyde radical caproic acid, 6-caprolactone, hexanodioic acid etc., its derivative 6 hydroxycaproic acid ethyl ester etc. is conventional organic chemical industry's intermediate.US Patent No. P2008306153 has introduced a kind of at CH
2cl
2in solvent, taking PCC (pyridinium chlorochromate Pyridinium Chlorochromate) as oxygenant is under 37 DEG C of conditions, 6 hydroxycaproic acid is oxidized to 6-aldehyde radical caproic acid.
At present, mainly prepare 6 hydroxycaproic acid taking pimelinketone, caprolactone and hexanodioic acid as raw material in the world.Wherein, pimelinketone is due to the advantage such as relative low price, raw material sources be extensive, and causes people's concern.(Inorganica Chimica Acta, 349, the 195-202 such as LENARDA Maurizio; 2003) using HBEA type molecular sieve H β is catalyzer, and the oxidizing reaction of having carried out pimelinketone obtains 6 hydroxycaproic acid.Document (Polish Journal of Chemistry, 78 (5), 687-697; 2004) reported under several catalyst actions, taking water and propyl carbinol as solvent, the reaction that hydrogen peroxide oxidation pimelinketone is 6 hydroxycaproic acid.Document (Angewandte Chemie, International Edition, 41 (23), 4481-4484; 2002) in, introduced at water and (CF
3)
2in CHOH solution, with p-MeC
6h
4sO
3h is catalyzer, and at 55 DEG C, pimelinketone is 6 hydroxycaproic acid by hydrogen peroxide oxidation.But catalyzer used is homogeneous catalyst, there is not easily separated, environmentally hazardous drawback and cannot drop into suitability for industrialized production.
Document (Organic & Biomolecular Chemistry, 7 (4), 725-732; 2009) reported a kind of method of being prepared 6 hydroxycaproic acid by caprolactone, the first step is in 0 DEG C of water and dioxane solvent, and caprolactone first reacts with NaOH 2.5 hours, is raised to subsequently room temperature and reacts with HCl and obtain 6 hydroxycaproic acid.Document (Journal of the American Chemical Society, 130 (5), 1718-1726; 2008) introduced equally a kind of pimelinketone through reacting with highly basic (NaOH) and strong acid (HCl) process that makes 6 hydroxycaproic acid.Document (Applied and Environmental Microbiology, 65 (5), 2232-2234; 1999) introduced and a kind ofly approached in neutral water surrounding at 30 DEG C, enzyme catalysis caprolactone is hydrolyzed to the reaction of 6 hydroxycaproic acid.Be reactant owing to having adopted strong acid and highly basic in above-mentioned the whole bag of tricks, serious to equipment corrosion, produce a large amount of wastes, environment exerted an influence, therefore do not meet the green and chemical principle of Sustainable development.
CN1211969A discloses a kind of by hexanodioic acid, adipate monoester or di adipate or contain hexanodioic acid or its ester prepares 1 as the starting material shortening of main ingredient, the method of 6-hexylene glycol and 6 hydroxycaproic acid or its ester, wherein, distillation hydrogenation products is recycled to hydrogenation step to remove the tower kettle product obtaining after hexylene glycol and hydroxycaproic acid or its ester, and tower kettle product mainly contains the oligomer ester of 6 hydroxycaproic acid; The mixture that makes starting material and recycle stream at 100-300 DEG C and 10-300 bar, in liquid phase, react on described hydrogenation catalyst, and in reactor, the carboxyl of hydrogenation and the molar ratio of hydrogen is 1: 5-1: 100.
Summary of the invention
The object of the invention is the deficiency existing in alcohol acid method for preparing in prior art, provide a kind of clean and effective, eco-friendly cyclic ketones catalyzed oxidation to prepare the method for corresponding alcohol acid.
Cyclic ketones catalyzed oxidation provided by the invention is prepared the method for corresponding alcohol acid, it is characterized in that according to cyclic ketones: solvent: hydrogen peroxide=1: (0～80): mole proportioning of (0.2～20), temperature is 76～99 DEG C, gauge pressure is the condition of 0～3.0MPa, under a kind of catalyzer exists, react and reclaim the alcohol acid obtaining, described catalyzer is HTS, and the mass ratio of catalyzer and cyclic ketones is 1: 5～300.
In method provided by the invention, said cyclic ketones is selected from monocycle ketone, many cyclic ketones and the cyclic ketones with side chain R, and R is alkyl functional group.For example, cyclic ketones is pimelinketone, cyclopentanone or methylcyclohexanone etc.
In method provided by the invention, said catalyzer is HTS, can be selected from one or more the mixture in TS-1, TS-2, Ti-BETA, Ti-MCM-22, Ti-MCM-41 and Ti-MCM-48, preferred HTS is TS-1, in US Patent No. P4410501, announce first the synthetic method of titanium-silicon molecular sieve TS-1.As preferred embodiment, in the present invention, HTS used is a kind of TS-1 HTS of unique hollow structure, in the Chinese patent of ZL99126289.1, disclose above-mentioned unique hollow structure TS-1 HTS and preparation method thereof, it has the HTS of MFI crystalline structure, crystal grain is hollow structure, and the radical length of the cavity part of this hollow crystal grain is 5～300 nanometers; This sieve sample is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is at least 70 milligrams/grams, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, has hysteresis loop.The said TS-1 HTS with hollow structure, have and have larger mesoporous volume, more than being generally 0.16mL/g, and conventional TS-1 HTS, mesoporous volume is generally in 0.084mL/g left and right, and contriver is surprised to find that, uses it in the reaction of the corresponding alcohol acid of cyclic ketones oxidation preparation, under same reaction conditions, can effectively improve the selectivity of transformation efficiency and the alcohol acid of cyclic ketones.
In method provided by the invention, taking hydrogen peroxide as oxygenant, hydrogen peroxide, because its reduzate is only water, environmental friendliness, is Green Oxidant.High density hydrogen peroxide is because its character is unstable, in production, accumulating, use procedure, there is potential safety hazard, and cost is higher, normally the form of the aqueous hydrogen peroxide solution taking mass concentration as 10～60% adds in reaction system, the aqueous hydrogen peroxide solution of such as technical grade has 27.5%, 30% and 35% etc., and conventionally selecting massfraction is 30% hydrogen peroxide.Inventor's discovery, lower concentration hydrogen peroxide has more efficient catalytic oxidation activity under appropriate reaction condition.In proportioning raw materials, said hydrogen peroxide is in hydrogen peroxide.
In the method that present method provides, said solvent is selected inertia organism and/or water.Said inertia organism is the compound close with boiling point of reactant or the compound that polarity is large, specific inductivity is high.Wherein, the said compound close with boiling point of reactant such as can be, lower than 6 fat of carbon atom alcohol, ketone, acid, ester, methyl alcohol, ethanol, the trimethyl carbinol, acetone, acetic acid, dioxane or ethyl acetate etc.; The inert organic solvents that said polarity is large, specific inductivity is high is acetonitrile, chloroform or tetramethylene sulfone etc. such as.
Contriver is surprised to find that, in the reaction system that particularly, low temperature lower at hydrogen peroxide concentration and catalyst concn are lower, under ethanol or ethyl acetate exist as solvent, the selectivity of corresponding alcohol acid is higher.For example, in the time adopting ethanol or ethyl acetate to be solvent, particularly cyclic ketones: mole proportioning of hydrogen peroxide is 1: the mass ratio of (0.2～10) and catalyzer and cyclic ketones is 1: 5～100, temperature is the lower time of condition that 80～95 DEG C, pressure are 0.1～0.5MPa, with other organism such as acetonitrile, methyl alcohol make solvent, the selectivity of corresponding alcohol acid is improved largely, therefore, in method provided by the invention, said solvent is ethanol or ethyl acetate more preferably, with the mol ratio proportioning of cyclic ketones be (0.5～10): 1.
Method provided by the invention can adopt periodical operation or continuous operating method.For example, while adopting intermittent mode to carry out, cyclic ketones, solvent, catalyzer are encased in after reactor, once add or add continuously hydrogen peroxide; Adopt continuous mode while carrying out, adopt fixed bed or slurry bed reactor, will catalyzer, add continuously cyclic ketones, hydrogen peroxide after solvent making beating, continuous separated product simultaneously.Method provided by the invention can also adopt closed still reaction, adds rear reaction by catalyzer, solvent, cyclic ketones, hydrogen peroxide simultaneously.
The process of the alcohol acid that in the present invention, said recovery obtains is familiar with by those skilled in the art, adopt conventional separation means, comprise distillation, crystallization and extraction etc., from mixture of reaction products, separate and obtain corresponding alcohol acid, for example, in this research, can first adopt Crystallization Separation under relatively-high temperature to go out the by product di-carboxylic acid of this reaction, under relative low temperature, recrystallize separates and obtains corresponding monocarboxylic acid.
Cyclic ketones catalyzed oxidation provided by the invention is prepared the method for corresponding alcohol acid, has following feature:
1. overcome conventional oxidation method complex manufacturing, equipment corrosion, had potential safety hazard and the drawback such as environmental pollution is serious.
2. taking hydrogen peroxide as oxygenant, under relatively mild reaction conditions, can obtain higher cyclic ketones transformation efficiency and corresponding alcohol acid yield, especially there is good activity stability.
3., in the reaction system that particularly, low temperature lower at hydrogen peroxide concentration and catalyst concn are lower, under ethanol or ethyl acetate exist as solvent, the selectivity of corresponding alcohol acid is higher.
Embodiment
Below by embodiment, the present invention is further described, but content not thereby limiting the invention.
In each of the embodiments described below, reagent used is commercially available chemically pure reagent.
In comparative example and embodiment, after reaction, the concentration of each material is used vapor-phase chromatography to carry out quantitative analysis.The 6890 type gas chromatographs that Agilent company used produces; Analysis chromatographic column used is FFAP post.
In embodiment, the transformation efficiency of cyclic ketones, alcohol acid selectivity are respectively to calculate according to the following equation:
Embodiment 1
(Hunan is built feldspathization company and is produced to take 3.45 grams of hollow HTS, trade mark HTS, it is the HTS of MFI structure through X-ray diffraction analysis, between the adsorption isothermal line of the nitrogen absorption under low temperature of this molecular sieve and desorption isotherm, have hysteresis loop, crystal grain is that the radical length of hollow crystal grain and cavity part is 15～180 nanometers; This sieve sample is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is 78 milligrams/gram, lower same) be loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 16.82 grams of cyclopentanone, 7.2 grams of water and 23ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 1 again.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 82 DEG C of left and right, reacts after 6 hours, and the transformation efficiency of cyclopentanone is 42.68%, and the selectivity that generates 5-hydroxypentanoic acid is 63.01%.
Embodiment 2
Take 4.88 grams of hollow HTS and be loaded in 100ml three-necked flask, then add successively the hydrogen peroxide that magnetic stir bar, 16.83 grams of cyclopentanone, 6.4 grams of methyl alcohol and 46ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 2.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 83 DEG C of left and right, reacts after 8 hours, and the transformation efficiency of cyclopentanone is 75.61%, and the selectivity that generates 5-hydroxypentanoic acid is 67.98%.
Embodiment 3
Take 2.65 grams of hollow HTS and be loaded in 100ml three-necked flask, then add successively the hydrogen peroxide that magnetic stir bar, 16.83 grams of cyclopentanone, 14.8 grams of trimethyl carbinols and 23ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 1.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 79 DEG C of left and right, reacts after 2 hours, and the transformation efficiency of cyclopentanone is 38.57%, and the selectivity that generates 5-hydroxypentanoic acid is 72.35%.
Embodiment 4
Taking 3.98 grams of hollow HTS is loaded in 100ml three-necked flask, add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of pimelinketone, 5.3 grams of acetone, 7.4 grams of trimethyl carbinols and 23ml concentration are 30%, now the mol ratio of pimelinketone and hydrogen peroxide is 1: 1 again.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 90 DEG C of left and right, reacts after 6 hours, and the transformation efficiency of pimelinketone is 50.28%, and the selectivity that generates 6 hydroxycaproic acid is 73.01%.
Embodiment 5
Take 4.42 grams of hollow HTS and be loaded in 100ml three-necked flask, then add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of pimelinketone, 23.9 grams of water and 11.5ml concentration are 30%, now the mol ratio of pimelinketone and hydrogen peroxide is 2: 1.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction was controlled at about 84 DEG C reactions after 6 hours, and the transformation efficiency of pimelinketone is 21.32%, and the selectivity that generates 6 hydroxycaproic acid is 57.62%.
Embodiment 6
Taking 3.76 grams of hollow HTS is loaded on 100ml and is with in manometric closed reactor, add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of pimelinketone, 18 grams of acetonitriles and 23ml concentration are 30%, now the mol ratio of pimelinketone and hydrogen peroxide is 1: 1 again.Three-necked flask is put on the temperature control magnetic stirring apparatus with oil bath pan, starts magnetic stirring apparatus and heating unit, start reaction.Temperature of reaction is controlled at 95 DEG C of left and right, and autogenous pressure is 0.65MPa left and right, reacts after 6 hours, and the transformation efficiency of pimelinketone is 79.62%, and the selectivity that generates 6 hydroxycaproic acid is 63.39%.
Embodiment 7
Take 4.23 grams of conventional titanium-silicon molecular sieve TS-1s (Zeolites, 1992, Vol.12,943rd～950 pages).Catalyzer is loaded in 100ml three-necked flask, then adds successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of pimelinketone, 3.6 grams of water and 23ml concentration are 30%, and now the mol ratio of pimelinketone and hydrogen peroxide is 1: 1.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 87 DEG C of left and right, reacts after 3 hours, and the transformation efficiency of pimelinketone is 43.79%, and the selectivity that generates 6 hydroxycaproic acid is 52.88%.
Embodiment 8
Taking 3.76 grams of hollow HTS is loaded on 100ml and is with in manometric closed reactor, add successively the hydrogen peroxide that magnetic stir bar, 19.63 grams of pimelinketone, 30 grams of ethanol and 23ml concentration are 30%, now the mol ratio of pimelinketone and hydrogen peroxide is 1: 1 again.Three-necked flask is put on the temperature control magnetic stirring apparatus with oil bath pan, starts magnetic stirring apparatus and heating unit, start reaction.Temperature of reaction is controlled at 115 DEG C of left and right, and autogenous pressure is 0.65MPa left and right, reacts after 1 hour, and the transformation efficiency of pimelinketone is 49.62%, and the selectivity that generates 6 hydroxycaproic acid is 97.39%.
Embodiment 9
Take 4.88 grams of hollow HTS and be loaded in 100ml three-necked flask, then add successively the hydrogen peroxide that magnetic stir bar, 16.83 grams of cyclopentanone, 32 grams of ethyl acetate and 46ml concentration are 30%, now the mol ratio of cyclopentanone and hydrogen peroxide is 1: 2.Three-necked flask is put on temperature control magnetic stirring apparatus, refluxes with condensing tube condensation in three-necked flask top, starts magnetic stirring apparatus and heating unit, starts reaction.Temperature of reaction is controlled at 86 DEG C of left and right, reacts after 8 hours, and the transformation efficiency of cyclopentanone is 94.23%, and the selectivity that generates 5-hydroxypentanoic acid is 98.67%.
Claims (4)
1. a catalytic oxidation of cyclic ketone is prepared the method for corresponding alcohol acid, it is characterized in that according to cyclic ketones: solvent: hydrogen peroxide=1: (0.5～10): mole proportioning of (0.2～10), be 1: 5～100 at the mass ratio of catalyzer and cyclic ketones, temperature is under 80～95 DEG C, the pressure condition that is 0.1～0.5MPa, react and reclaim the alcohol acid obtaining, said solvent is selected from ethanol or ethyl acetate, described catalyzer is titanium-silicon molecular sieve TS-1, its crystal grain is hollow structure, and the radical length of the cavity part of crystal grain is 5～300 nanometers; This sieve sample is at 25 DEG C, P/P
0=0.10, the benzene adsorptive capacity recording under the adsorption time condition of 1 hour is at least 70 milligrams/grams, between the adsorption isothermal line of nitrogen absorption under low temperature and desorption isotherm, has hysteresis loop.
2. according to the process of claim 1 wherein, described cyclic ketones is selected from monocycle ketone, many cyclic ketones and the cyclic ketones with side chain R, and R is alkyl functional group.
3. according to the process of claim 1 wherein, described cyclic ketones is pimelinketone, cyclopentanone or methylcyclohexanone.
4. according to the method for claim 1, described hydrogen peroxide is that mass concentration is 10～60% aqueous hydrogen peroxide solution.
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| CN109836561A (en) * | 2019-01-30 | 2019-06-04 | 青岛科技大学 | A kind of synthetic method of 6 hydroxycaproic acid oligomer and its resulting oligomer |
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| CN106964400B (en) * | 2016-01-14 | 2019-09-24 | 中国石油化工股份有限公司 | The method of the forming method and preformed catalyst and its application and oxidizing cyclohexanone of Titanium Sieve Molecular Sieve |
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| US6344586B1 (en) * | 1998-07-30 | 2002-02-05 | Sumitomo Chemical Company, Limited | Process for producing adipic acid |
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| US6344586B1 (en) * | 1998-07-30 | 2002-02-05 | Sumitomo Chemical Company, Limited | Process for producing adipic acid |
| CN1301599A (en) * | 1999-12-24 | 2001-07-04 | 中国石油化工集团公司 | Titanium-silicon molecular sieve and its preparing method |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN109836561A (en) * | 2019-01-30 | 2019-06-04 | 青岛科技大学 | A kind of synthetic method of 6 hydroxycaproic acid oligomer and its resulting oligomer |
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