CN103086878A - Preparation method of cyclohexyl compound by aromatic compound catalytic hydrogenation - Google Patents
Preparation method of cyclohexyl compound by aromatic compound catalytic hydrogenation Download PDFInfo
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Abstract
The invention discloses a preparation method of a cyclohexyl compound by aromatic compound catalytic hydrogenation. The method comprises the following steps of: adding an aromatic compound, a solvent and a nitrogen doped mesoporous carbon loaded nanometer metal catalyst into a hydrogenation reaction container, wherein the hydrogen pressure in the reaction container is 0.1Mpa-10Mpa, the reaction temperature is 30-250 DEG C, and the cyclohexyl compound can be obtained after the catalytic hydrogenation is finished. The nitrogen doped mesoporous carbon loaded nanometer metal catalyst which is high in catalytic activity is used in the method disclosed by the invention, the selectivity of the cyclohexyl compound is more than 97%, and in addition, according to the preparation method, the reaction condition is easily controlled, and the posttreatment is simple, so that the preparation method is suitable for industrialized production.
Description
Technical field
The present invention relates to the shortening technical field, specifically relate to a kind of method that aromatic compound shortening prepares the cyclohexyl compound.
Background technology
Aromatic compound such as phenylformic acid, benzoic ether, the cyclohexyl compounds of phthalic ester benzene ring hydrogenation preparation correspondence is significant.For example hexahydrobenzoic acid is a kind of important chemical intermediate, can be used for the synthetic of light curing agent 184, simultaneously be also the solubilizing agent of efficient ultraviolet light polymerization initiator and non-flavescence light trigger, vulcanized rubber, also be used for the synthetic of medicine anti-pregnant 392 and treatment schistosomicide new drug praziquantel, its derivative such as heptanaphthenic acid methyl esters, trans-4-sec.-propyl heptanaphthenic acid etc. are all many Chemicals and the synthetic important intermediate of medicine.Trans-4-sec.-propyl heptanaphthenic acid is to ask body in a kind of important medicine, and Na Gelie splits for the production of Glucovance; The hexamethylene formic ether class is for the synthesis of many medicine and Chemicals that contain cyclohexyl structure.
The method of synthesizing cyclohexyl formic acid and derivative thereof mainly contains at present: sodium reduction process, and the cyclohexene method, hydrolysis method, oxidation reduction process, these methods all relate to the shortening process, and the process more complicated.Can a step obtain hexahydrobenzoic acid by benzoic direct benzene ring hydrogenation.Introduced a kind of in fixed-bed reactor in patent documentation CN1406666, take aluminum oxide as carrier, group vib or VIII family metal are the method that the catalyst to catalyzing hydrogenating phenylformic acid obtains hexahydrobenzoic acid, and the method selectivity is high, but condition is harsh, and activity is not high.Introduced a kind of hydrogen storage metal alloy NiLa that utilizes in Japanese documentation JP06056702
5The benzoic method of hydrogenation.Document (J.Amer.Chem.Soc.1945,67,272-276) introduced the benzoic method of a kind of platinum oxide shortening in acetic acid.Document (Catal.Lett.2007,119,16-20) introduced a kind of in water the carbon nanofiber take load P d obtain the method for hexahydrobenzoic acid as the catalyst to catalyzing hydrogenating phenylformic acid.Document (Chem.Eur.J.2009,15,6953-6963) introduced a kind of take activated carbon supported ruthenium as catalyzer in water the benzoic method of shortening.The problems such as all there is severe reaction conditions in above-mentioned method, and reactive behavior is not high.
Phthalic ester is that a kind of fluidizer commonly used is a very important Organic chemical products of class, at industrial main softening agent and tenderizer as rubber-plastics materials such as polyvinyl chloride, also extensively make an addition in daily high molecular plastics and rubber goods, as toy for children, packaging material for food, medical material, family expenses and automobile-used finishing material.It not the covalent linkage Chemical bond between phthalic ester and high molecular polymer, but physical bond, therefore As time goes on, can slowly overflow from material, polluted air, soil, water source and even food, phthalic ester can build up in human body and can resolve into corresponding meta-bolites and then be detrimental to health.Therefore its toxicity is mainly manifested in phenyl ring residual in its molecule, and present research direction concentrates on wherein benzene ring hydrogenation is generated the hexanaphthene side chain.This reaction at present report is less, and document (Catal.Commun.2011,16,30-34) reported with metal oxide supported Ni shortening and dioctyl phthalate (DOP) has been converted into hexanaphthene 1,2-dioctyl phthalate dioctyl ester.Document (the Shandong chemical industry, 2012,41,31-33) reported that nickel-base catalyst shortening dioctyl phthalate (DOP) in fixed-bed reactor generates 1,2-cyclohexyl dioctyl phthalate dioctyl ester.Above-mentioned preparation method's selectivity is general.
Summary of the invention
The invention provides a kind of method that aromatic compound shortening prepares the cyclohexyl compound, the method adopts the metallic catalyst of the mesoporous carbon-loaded of nitrogen doping, catalytic activity is high, has improved the selectivity of cyclohexyl compound, and reaction process and aftertreatment simple.
A kind of aromatic compound shortening prepares the method for cyclohexyl compound, comprise: the metallic catalyst of the mesoporous carbon-loaded of aromatic compound, solvent and nitrogen doping is placed in the hydrogenation reaction container, in reaction vessel, hydrogen pressure is 0.1Mpa～10MPa, temperature of reaction is 30～250 ℃, shortening is completed, and obtains the cyclohexyl compound.
Aforesaid method can be used for the shortening of multiple benzene ring compound, and by the test detected result as can be known, when described aromatic compound was phenylformic acid, benzoic ether or phthalic ester, the catalytic activity of catalyzer was very high, and the selectivity of cyclohexyl compound is higher.Described cyclohexyl compound is corresponding hexahydrobenzoic acid, hexahydrobenzoic acid ester or 1,2-cyclohexyl dicarboxylic acid esters.
The meso-porous carbon material of used catalyst solid support material nitrogen of the present invention doping can be with nitrogenous ionic liquid and other nitrogenous organic molecule such as amino acid molecular, take silicon sol, SBA-15, MCM-41 etc. as template, prepare by hydrothermal method, be prior art.In the meso-porous carbon material of nitrogen doping, the mass percentage content of nitrogen is 0.1～80%, and test shows, in the meso-porous carbon material of nitrogen doping, the best in quality degree of nitrogen is 1～30%.In the metallic catalyst of the mesoporous carbon-loaded of nitrogen doping, nano metal can be selected one or several the combination in Pd, Au, Ag, Pt, Ru, Rh, Ni, Cu, Fe, Co, Cr, W, Mo, Ti, Ta etc.The mass percentage content of nano metal is generally 0.1%～50%, and test shows, the best in quality degree of nano metal is 0.1%～30%.
The solvent that uses in the present invention is generally product solvability organic solvent preferably, to promote that catalytic hydrogenation reaction carries out fast to positive dirction.Described organic solvent is generally selected one or more in ethanol, Virahol, methylene dichloride, trichloromethane, Isosorbide-5-Nitrae-dioxane, normal hexane, hexanaphthene, dimethyl sulfoxide (DMSO), dimethyl formamide, benzene, toluene, pyridine, ethyl acetate.Perhaps, for reducing the pollution to environment, described solvent also can be selected water.Because product polarity is lower, not dissolve each other with water, when selecting water as solvent, aftertreatment is more simple, and has avoided the corrosion of solvent to hydrogenation unit, is suitable for suitability for industrialized production.
In above-mentioned preparation method, the mass ratio of the metallic catalyst of the mesoporous carbon-loaded of the raw material aromatic compound of use and nitrogen doping is between 300: 1 to 1: 1, and optimum proportion is between 50: 1 to 1: 1.Optimal reaction temperature is 50～150 ℃, and too high temperature of reaction is unfavorable for the control of reacting, and too low temperature of reaction can significantly widen the reaction times, increases reaction cost.Optimum response pressure is at 0.1MPa～3MPa, and hypertonia has increased the risk level of hydrogenation reaction.
The catalyzer that uses in the present invention is the metallic catalyst of the mesoporous carbon-loaded of nitrogen doping, and after reaction finished, adopting simple filter method was recyclable catalyzer, reduces the use cost of catalyzer.The filtrate that filtration obtains is directly concentrated can obtain the cyclohexyl compound.
Compare with traditional method, beneficial effect of the present invention is embodied in:
(1) the present invention adopts the metallic catalyst of the mesoporous carbon-loaded of nitrogen doping, and catalytic activity is high, and the selectivity of cyclohexyl compound is all more than 97%, and easy control of reaction conditions, and aftertreatment is simple, is suitable for suitability for industrialized production.
(2) utilize method of the present invention fast the benzene ring hydrogenation in the fluidizer phthalic ester to be become cyclohexyl, may be to people's harm to reduce fluidizer; Simultaneously, utilize method of the present invention phenylformic acid and benzoic ether conversion can be obtained useful product.
The metallic catalyst of the mesoporous carbon-loaded of the nitrogen doping of (3) adopting in the present invention has following advantage: (a) good thermostability; (b) good chemical stability, water, ethanol, methylene dichloride, trichloromethane, toluene, benzene, etc. highly stable in organic solvent; (c) higher catalytic activity and selectivity; (d) easily separate; (e) recovery repeatedly.
Embodiment
Embodiment 1
The preparation method of the gold/mesoporous carbon catalyst of supported palladium: 10g glucosamine hydrochloride and 5g silicon sol are mixed, add 40g water, 180 ℃ of hydro-thermals 24 hours, then filter, filter residue washes in rear nitrogen atmosphere 800 ℃ of calcinings 2 hours with water, then remove silicon-dioxide with hydrofluoric acid, obtain nitrogenous meso-porous carbon material; Take the nitrogenous mesoporous carbon material of 0.1g, add in 10mL water ultrasonicly, then add the PdCl of 5mg according to charge capacity
2Solution, ultrasonic and add the NaBH of 5mg
4Reduction is filtered fully, washing, and drying obtains the gold/mesoporous carbon catalyst (in the meso-porous carbon material of nitrogen doping, the weight percent content of N is 10%, and in catalyzer, the mass percentage content of Pd is 3%) of supported palladium.
With the 100mg phenylformic acid, 5mL water, the metal Pd catalyzer of the mesoporous carbon-loaded of 25mg nitrogen doping joins in the 50mL reactor, with the air in the hydrogen exchange reactor three times, airtight after, the pressure of hydrogen is 0.5MPa, in 90 ℃ of heating in water bath, magnetic agitation was reacted 30 hours.Adopt the method for filtering that catalyzer is separated with reaction solution, the reaction solution gas chromatographic detection, mark in doing with toluene, detecting and obtaining benzoic transformation efficiency is 100%, the selectivity of hexahydrobenzoic acid is greater than 99%.
Embodiment 2-3
Other conditions are with embodiment 1, and difference is that respectively result is as shown in table 1 take methyl benzoate and dioctyl phthalate (DOP) as reactant, and wherein the product that obtains of embodiment 2 is the hexahydrobenzoic acid ester; The product that embodiment 3 obtains is 1,2-cyclohexyl dicarboxylic acid esters.
Table 1
Embodiment 4～19
Be similar to the preparation method of embodiment 1, respectively with the nanometer Pd of the mesoporous carbon-loaded of nitrogen doping, Au, Ag, Pt, Rh, Ru etc. make catalyzer, with the different mass ratio of phenylformic acid with catalyzer, react under differing temps, and result is as shown in table 2.Other NM reaction conditions is with embodiment 1.
Table 2
By embodiment 2～19 reaction results as can be known, when utilizing method para Toluic Acid of the present invention, benzoic ether or phthalic ester to carry out shortening, the transformation efficiency of raw material is higher, and all about more than 90%, the selectivity of reaction product is higher, all more than 97%.
Claims (10)
1. an aromatic compound shortening prepares the method for cyclohexyl compound, it is characterized in that, comprise: the metallic catalyst of the mesoporous carbon-loaded of aromatic compound, solvent and nitrogen doping is placed in the hydrogenation reaction container, in reaction vessel, hydrogen pressure is 0.1Mpa～10MPa, temperature of reaction is 30～250 ℃, shortening is completed, and obtains the cyclohexyl compound.
2. aromatic compound shortening according to claim 1 prepares the method for cyclohexyl compound, it is characterized in that, described aromatic compound is phenylformic acid, benzoic ether or phthalic ester, described cyclohexyl compound is corresponding hexahydrobenzoic acid, hexahydrobenzoic acid ester or 1,2-cyclohexyl dicarboxylic acid esters.
3. aromatic compound shortening according to claim 1 prepares the method for cyclohexyl compound, it is characterized in that, in the meso-porous carbon material of described nitrogen doping, the mass percentage content of nitrogen is 0.1～80%.
4. according to claim 1 or 3 described aromatic compound shortenings prepare the method for cyclohexyl compound, it is characterized in that, in the metallic catalyst of the mesoporous carbon-loaded of described nitrogen doping, nano metal is one or several the combination in Pd, Au, Ag, Pt, Ru, Rh, Ni, Cu, Fe, Co, Cr, W, Mo, Ti and Ta.
5. aromatic compound shortening according to claim 4 prepares the method for cyclohexyl compound, it is characterized in that, in the metallic catalyst of the mesoporous carbon-loaded of described doping, the mass percentage content of nano metal is 0.1%～50%.
6. aromatic compound shortening according to claim 1 prepares the method for cyclohexyl compound, it is characterized in that, described solvent is a kind of in ethanol, Virahol, methylene dichloride, trichloromethane, Isosorbide-5-Nitrae-dioxane, normal hexane, hexanaphthene, dimethyl sulfoxide (DMSO), dimethyl formamide, benzene, toluene, pyridine and ethyl acetate.
7. aromatic compound shortening according to claim 1 prepares the method for cyclohexyl compound, it is characterized in that, described solvent is water.
8. aromatic compound shortening according to claim 1 prepares the method for cyclohexyl compound, it is characterized in that, the mass ratio of the metallic catalyst of the mesoporous carbon-loaded of described aromatic compound and doping is 300～1: 1.
9. aromatic compound shortening according to claim 1 prepares the method for cyclohexyl compound, it is characterized in that, described temperature of reaction is 50～150 ℃.
10. aromatic compound shortening according to claim 1 prepares the method for cyclohexyl compound, it is characterized in that, in described reaction vessel, hydrogen pressure is 0.1～3MPa.
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| CN114643066A (en) * | 2020-12-18 | 2022-06-21 | 湖南长岭石化科技开发有限公司 | Hydrogenation catalyst, preparation method and application thereof, and preparation method of cyclohexanecarboxylic acid |
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| CN114433164A (en) * | 2022-01-26 | 2022-05-06 | 西安凯立新材料股份有限公司 | Method for preparing cyclohexanecarboxylic acid by hydrogenation of benzoic acid under catalysis of fixed bed |
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