CN101045213A - Solid carried ion liquid-nanometer metal particle catalyst, and its preparing method, and application in synthesis of arylamine - Google Patents
Solid carried ion liquid-nanometer metal particle catalyst, and its preparing method, and application in synthesis of arylamine Download PDFInfo
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- CN101045213A CN101045213A CN 200710017803 CN200710017803A CN101045213A CN 101045213 A CN101045213 A CN 101045213A CN 200710017803 CN200710017803 CN 200710017803 CN 200710017803 A CN200710017803 A CN 200710017803A CN 101045213 A CN101045213 A CN 101045213A
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Abstract
A catalyst carrying ionic liquid and metallic nanoparticles for preparing high-quality arylamine by hydrocatalyzing aromatic nitro compound is prepared through preparing immobilized ionic liquid by bonding the ionic liquid onto carrier, binding it with the active component containing transition metal or precursor, and reductive exchange. Its advantages are low reaction temp, long service life and no waste generation.
Description
Technical field:
The present invention relates to a kind of solid carried ion liquid-nanometer metal particle catalyst and preparation method thereof and the application in the synthetic arylamine of hydrogenation under the aromatic nitro compound temperate condition, more particularly, be a kind of method of producing high-quality arylamine by immobilized ionic liquid stabilized nano metallic catalyst and preparation method thereof and this catalyst aromatic nitro compound hydrogenation of use.
Background technology:
Arylamine is important Organic Ingredients of a class and intermediate, is widely used in fields such as chemical industry, medicine, dyestuff, agricultural chemicals, can be used to prepare agricultural chemicals, dyestuff, medicine and polyurethane high molecule material etc.Catalytic hydrogenation is simple, a clean and economic method that nitro compound is reduced to corresponding arylamine, also is the main method in the present industrial production.The world produces per year in more than 430 ten thousand tons of aniline, just accounts for 85% with catalytic hydrogenation process production.Existing catalytic hydrogenation process comprises two kinds of vapor phase method and liquid phase methods.The shortcoming of vapor phase method mainly is to need higher reaction temperatures, excessive hydrogen, higher pressure and special reactor etc.Simultaneously, because reaction heat is difficult for removing, cause to be difficult to avoid because of caused side reaction of hot-spot and catalysqt deactivation.For example, with metals such as the palladium of alumina load, lead is hydrogenation catalyst, 1-30bar and 200-400 ℃, in the gas phase fixed bed, carry out hydrogenation reaction (US P5,877,350), be catalyst perhaps with ceramic supported palladium, vanadium, lead, rhenium etc., at hydrogen pressure 0.5-5bar, temperature 180-500 ℃, the mol ratio of hydrogen and nitryl group is 3-30: under 1 the condition, react in the gas phase fixed bed (CN1252787A).The advantage of liquid phase method is not need high temperature, accessory substance is few, equipment capacity is big, but have catalyst to cost an arm and a leg, shortcomings such as service life is undesirable, equipment operation and maintenance cost height, and the disadvantage of liquid-phase hydrogenatin is to use volatile, harmful, dangerous in a large number organic solvent, cause environmental pollution, solvent recovery complexity, product must separate easily with catalyst and solvent, cost is raise greatly (as J.Chem.Tech.Biotechnol, 1987,37,233-245; Transition Met.Chem., 1991,16,293-295; The clear 54-130526 of the public Reported of Gong Open Te Xu, 1979; And the Pd-Pt/C catalyst of Dupont process using is involved).
Catalyst is the core of catalytic hydrogenation technical development.Discovered in recent years, metallic catalyst comprises the catalytic performance that shows excellence in the aromatic nitro compound liquid phase catalytic hydrogenation in many reactions.For example: Ru/SnO
2The catalytic hydrogenation of composite nano-catalyst catalysis parachloronitrobenzene in 4.0Mpa, 333K and methyl alcohol, the reaction 2.5-5h, the selectivity of parachloroanilinum up to more than 99.9% (J.Catal.2004,222,493-498); The nm of gold of silica gel load, silver catalyst are reacted 2.5-5h in 4.0Mpa, 140 ℃ and ethanolic solution, can make multiple aromatic nitro compound highly selective be converted into corresponding arylamine (CN1775351A; J.Catal., 2006,242,227-230).But because the thermodynamic phase of nano metal particles, autohemagglutination and make catalyst activity reduction easily, shorten service life.Simultaneously, hitherto reported is the aromatic nitro compound liquid phase catalytic hydrogenation that catalyst carries out with the nano metal particles, still can not break away from an organic solvent and problem such as the environmental pollution that brings and cost rising.
Ionic liquid is the stabilized nanoscale metallic effectively, and at alkene (J.Am.Chem.Soc.2002,124,4228-4229; Inorg.Chem.2003,42,4738-4742) and aromatic hydrocarbons (Chem.-Eur.J.2003,9,3263-3269; Chem.-Eur.J.2004,10, obtained result preferably in catalytic hydrogenation 3734-3740).But, ionic liquid expensive and poisonous (Green Chem.2005,1,9-14; Green Chem.2006,8,238-240), even in use a small amount of the loss also can be brought the remarkable rising and the environmental pollution of cost, thereby the Green Chemistry that has reduced it is worth.Ionic liquid is immobilized on carrier by the covalent bonding mode, and ionic liquid can be avoided ion liquid loss in conjunction with firmly being difficult for by wash-out, and make catalyst system and catalyzing more stable, thereby keep high activity, long-life (as alkylated reaction: Green Chemistry, 2002,4,88-93; Suzuki coupling reaction: J.Catal., 2006,242,357-364; Oxidation reaction: Chem.-Eur.J.2006,12,5220-5224; The epoxidation of alkene: J.Am.Chem.Soc.2005,127,530-531).But solid-loaded ionic-liquid and ionic liquid itself are applied to the catalytic hydrogenation of aromatic nitro compound does not see bibliographical information so far.
Simultaneously, the inventor considers that what reported all is individual layer with the immobilized ionic liquid of covalent bond, be that a glyoxaline cation is only arranged on each side chain, can only form one deck at carrier surface and be right after carrier surface, film with two dimensional surface character, rather than the such solid of similar free ion liquid, the liquid phase of three dimensions character, thereby the even phasic property that still lacks ionic liquid to a certain extent and had, mobile, limited the further raising of catalytic activity, for this reason, the present invention further adopts solid carried multilaminar ion liquid (Chinese patent 200710017755.2) to combine with nano transition metal and forms catalyst, the load capacity of transition metal is higher in this catalyst, disperse better, consumption is little, active high, the life-span is long, and can be at normal temperature and pressure and solvent-free or be under the condition of solvent with the pure water, catalyze aromatic nitro compound hydrogenation is produced high-quality arylamine, the problems such as environmental pollution of having broken away from an organic solvent and having brought.
Innovation part of the present invention is immobilized ionic liquid is combined the new catalyst of formation one class with nano transition metal, and is applied to the catalytic hydrogenation reaction of aromatic nitro compound.
Summary of the invention:
The objective of the invention is to solve the aromatic nitro compound hydrogenation and produce aforesaid shortcoming in the existing catalyst of arylamine and the current technology, it is solid-loaded ionic-liquid catalyst of active component and preparation method thereof that a kind of transition metal nanoparticles is provided, with use this catalyst normal temperature and pressure and solvent-free or with the condition of pure water as solvent under, catalyze aromatic nitro compound hydrogenation is produced the method for high-quality arylamine.
The present invention addresses the above problem the technical scheme that is proposed: transition metal nanoparticles is dispersed on the immobilized single or multiple lift ionic liquid of insoluble carrier (perhaps being called " ionic liquid brush "), forms a class solid carried ion liquid-nanometer metal particle catalyst.Solid carried ion liquid-nanometer metal particle catalyst provided by the invention mainly is made up of carrier, connection base, single or multiple lift ionic liquid cation, transition metal simple substance and ionic liquid anion five parts, it is characterized in that this catalyst has structural formula as shown in Equation 1:
Wherein:
Carrier is the indissoluble inoganic solids oxide that contains hydroxyl on the surface, is selected from silica, diatomite, aluminium oxide, aluminosilicate, zeolite, titanium oxide, zirconia, preferably silica, diatomite, zeolite;
M is any positive integer between the 0-10, and n is any positive integer between the 1-10, and preferred m and n are 1 or 2;
Q, Q
1, Q
2For connecting base, be selected from (CH
2)
x, (CH
2)
aC
6H
4(CH
2)
b, (CH
2)
aC
6H
4O (CH
2)
y, (CH
2)
xO (CH
2)
y, (CH
2)
xS (CH
2)
y, (CH
2)
xOC
6H
4O (CH
2)
yDeng group, they can be mutually the same also can be different, wherein x and y are respectively any positive integer of 2-18, a and b are respectively any positive integer of 0-18; (CH preferably
2)
x, (CH
2)
aC
6H
4(CH
2)
b, (CH
2)
aC
6H
4O (CH
2)
y, (CH
2)
xO (CH
2)
y, they can be mutually the same also can be different, wherein x and y are respectively any positive integer of 2-10, a, b are respectively any positive integer of 0-10;
L is a substituting group, is selected from the alkoxyl of C1-4, preferably methoxy or ethoxy;
R is a terminal groups, be selected from C1-20 alkyl, cycloalkyl, aralkyl, contain the alkyl of aerobic or sulfur heteroatom etc.; The preferably alkyl of C1-10, cycloalkyl, aralkyl;
Substituent R on the imidazole ring
1-R
9Can be hydrogen atom, also can be alkyl, cycloalkyl, aralkyl of C1-20 etc., and they can be the same or different, hydrogen atom preferably, and methyl, ethyl, propyl group, butyl, phenyl, benzyl, they can be the same or different;
Anion Y
Q-For univalent anion or multivalent anions, be selected from halide ion, or IIIA, IVA, the polyhalide anion of VA family element, their oxyacid radical ion or complex anion, or the organic acid ion of C1-8; Q is anion Y
Q-Charge number, take from any positive integer between the 1-10; Fluorine preferably, chlorine, bromine, iodine, fluoboric acid root, fluorophosphoric acid root, trifluoracetic acid root, TFMS root, tetrafluoroborate, hexafluoro-phosphate radical, methanesulfonate, trifluoromethane sulfonic acid root, benzene sulfonic acid root, p-methyl benzenesulfonic acid root etc.;
What M represented is transition metals such as IB and/or VIII family metal, be selected from a kind of in platinum, palladium, ruthenium, rhodium, iridium, nickel, cobalt, gold, silver, the copper etc. or/and the mixture of several transition metals, preferred platinum, palladium, ruthenium, rhodium or wherein a kind of or/and several mixtures.
In the said catalyst, the amount of bond ion liquid is the 0.1-20% of vehicle weight, preferred 1-10%; The amount of transition metal is the 0.1-20% of vehicle weight, preferred 0.5-5%.
Solid carried ion liquid-nanometer metal particle catalyst provided by the invention, its preparation method are characterised in that and comprise the following step:
1) solid carried multilaminar ion liquid is that raw material reacts with the salt that contains transition metals such as IB and/or VIII family metal;
2) salt that will contain transition metal with reducing agent is reduced to the nano metal particles of simple substance form;
3) handle with containing suitable anionic salt compounds; But this step is not necessary;
Here said solid-loaded ionic-liquid has the structural formula of formula 2 representatives:
Carrier wherein, m, n, Q, Q
1, Q
2, L, R, R
1-R
9, Y
Q-Deng identical with claim 1 or a kind of corresponding every definition of 2 described formulas.
The salt of said transition metal is halide, nitrate, sulfate, the acetate of elements such as platinum, palladium, ruthenium, rhodium, iridium, nickel, cobalt, gold, silver, copper, the salt that their polyhalide anion and alkali metal ion form, or they are with the salt of the complex anion of the part formation that also contains phosphorus, nitrogen, oxygen or element sulphur except that carbon containing and hydrogen etc.; Preferably halide, nitrate, sulfate, the acetate of elements such as platinum, palladium, ruthenium, rhodium, iridium, nickel, cobalt, gold, silver, copper, the salt that their polyhalide anion and alkali metal ion form;
Said reducing agent is a metal hydride, hypophosphorous acid, formaldehyde, hydrazine and hydrazine hydrate, hydrogen, low-carbon alcohols such as methyl alcohol, ethanol, isopropyl alcohol etc.; Sodium borohydride preferably, formaldehyde, hydrazine and hydrazine hydrate, hydrogen, low-carbon alcohols such as methyl alcohol, ethanol, isopropyl alcohol etc.;
The said general formula that contains suitable anionic salt is Z
q P+Y
p Q-, anion Y wherein
Q-Meaning and the Y of formula 1 or formula 2
Q-Identical, cation Z
P+Be cation, ammonium ion or its organic derivative of alkali metal, alkaline-earth metal, IIIA, IVA family element, p is cationic charge number; Sodium tetrafluoroborate preferably, sodium hexafluoro phosphate, sodium trifluoroacetate, TFMS sodium, potassium tetrafluoroborate, Potassium Hexafluorophosphate, trifluoracetic acid potassium, TFMS potassium etc.;
The preparation method of solid carried ion liquid-nanometer metal particle catalyst provided by the invention, the condition that it is characterized in that respectively going on foot in the synthetic reaction is:
1) the weight of material ratio is: weight=8 of metallic element: 1-1: 1 in the salt of the weight of the solid-loaded ionic-liquid of formula 2 representative/contain transition metal; Reaction condition is an inert atmosphere, can be nitrogen, argon gas etc.; Reaction medium is alcohols or nitrile solvents; Temperature is that room temperature arrives between the boiling temperature of solvent for use; Reaction time 6-96 hour;
2) molar ratio of material is: the catalyst precarsor that reducing agent/step 1 obtains=5: 1-1: 1; Reaction medium is an alcohols solvent; Temperature 20-80 ℃; Reaction time 1-10 hour;
3) molar ratio of material by: the anion number of salt compounds and anion electrically charged long-pending/cation number=5 of solid-loaded ionic-liquid: 1-1: 1; Reaction medium selects the mixed solvent of water, acetonitrile, acetone, ethanol or above-mentioned solvent; Temperature 10-80 ℃; Reaction time 6-96h.
The preparation method of solid carried ion liquid-nanometer metal particle catalyst provided by the invention is characterized in that respectively going on foot that optimum condition is in the synthetic reaction:
1) the weight of material ratio is: weight=6 of metallic element: 1-2: 1 in the salt of the weight of the solid-loaded ionic-liquid of formula 2 representative/contain transition metal; Reaction condition is an inert atmosphere, can be nitrogen or argon gas; Reaction medium is ethanol or acetonitrile; The boiling temperature of 60 ℃-solvent for use of reaction temperature; Reaction time 48-72 hour;
2) molar ratio of material is: the catalyst precarsor that reducing agent/step 1 obtains=4: 1-2: 1; Reaction medium is an ethanol; Reaction temperature 20-30 ℃; Reaction time 2-4 hour;
3) molar ratio of material by: the anion number of salt compounds and anion electrically charged long-pending/cation number=3 of solid-loaded ionic-liquid: 1-1.2: 1; Reaction medium is water, acetonitrile or acetone; Temperature 15-30 ℃; Reaction time 48-72h.
The stable transition metal nanoparticles catalyst of solid carried multilaminar ion liquid provided by the invention is used for the purposes of organic reaction; can be used for but be not limited to following reaction: the aromatic nitro compound catalytic hydrogenation is produced corresponding arylamine, or the reaction that simple substance transition metal particle such as the catalytic hydrogenation of other unsaturated bond and hydroformylation, Heck reaction, Suzuki coupling reaction can catalysis.
The aromatic nitro compound that is applicable to the inventive method can also have one or more substituting groups on the aromatic ring of these compounds for the single nitro of benzene aromatic hydrocarbon or single nitro or many nitro compounds of many nitro compounds or heterocyclic compound, comprises C
1-C
20Alkyl, cycloalkyl, aralkyl, aryl, contain heteroatomic alkyl such as aerobic, nitrogen or sulphur, alcoxyl, hydroxyl, carboxyl, ester group, sulfonic group, amido, amide groups etc., they can be the same or different.
Catalyst of the present invention is produced in the course of reaction of corresponding arylamine at the aromatic nitro compound catalytic hydrogenation, and the mol ratio of reaction substrate and catalytic active center metal is 1-10000, preferably 250-5000.
In the above-mentioned catalytic hydrogenation reaction process of the present invention, the catalytic reaction temperature is 0-100 ℃, and the rising temperature does not have adverse effect to the activity of catalytic reaction, but has increased energy consumption, takes all factors into consideration preferable reaction temperature 20-50 ℃.
In the above-mentioned catalytic hydrogenation reaction process of the present invention, catalytic reaction pressure preferred atmosphere is pressed, and this can make catalytic reaction carry out under very gentle condition, but this is not essential, and reaction can more can carried out under partial vacuum again under the high pressure.
In the above-mentioned catalytic hydrogenation reaction process of the present invention, the reaction time is 0.5-48h, and the preferred reaction time is 0.5-3h, and the concrete reaction time is determined according to whole transform actual consuming time next of reactant.
Above-mentioned catalytic hydrogenation reaction process of the present invention is preferably carried out under condition of no solvent or under the water as solvent condition, but this is not essential, also can carry out in organic solvent system, organic solvent/water homogeneous system or organic solvent/water two-phase system.Actual conditions is according to decisions such as state under reaction temperature of reaction raw materials and product, solubility, and for example, raw material and product are liquid can select solvent-free system under reaction temperature; Be that solid-state and water-fast raw material and product can be selected aqueous systems under reaction temperature, organic solvent/water homogeneous system, or organic solvent/water two-phase system.
In the above-mentioned catalytic hydrogenation reaction process of the present invention, for the situation of carrying out in organic solvent system, organic solvent can be one-component or multicomponent, and wherein, multi-component organic solvent can be immiscible, also can be miscible.These organic solvents are selected from: various hydro carbons can be linear paraffin, branched paraffin or cycloalkane; Aromatic hydrocarbon solvent can be benzene, toluene, ethylbenzene or other single replacements or polysubstituted alkylbenzene; Halogenated hydrocarbon solvent can be a halogenated alkane, or halogenated aryl hydrocarbon; Esters solvent can be aromatic esters, fatty acid ester, or trialkylphosphate; Alcohols solvent can be methyl alcohol, ethanol, the tert-butyl alcohol or ethylene glycol; Lower aliphatic ether, cyclic ethers, polyether or ring-type polyether can be ether, methyl tertiary butyl ether(MTBE), dioxane; Rudimentary aliphatic nitrile can be an acetonitrile; Lower aliphatic carboxylic acid amide etc., the perhaps mixture of two or more solvents in them.
In the above-mentioned catalytic hydrogenation reaction process of the present invention, for the situation of carrying out in organic solvent/water homogeneous system, organic solvent is selected from: alcohols solvent can be methyl alcohol, ethanol, the tert-butyl alcohol; And a series of solvents that dissolve each other with water such as acetonitrile, acetone, DMF, DMSO, dioxane, the preferred alcohols kind solvent can be methyl alcohol, ethanol, the tert-butyl alcohol, acetonitrile, dioxane etc.
In the above-mentioned catalytic hydrogenation reaction process of the present invention, for the situation of carrying out in organic solvent/water two-phase system, organic solvent is selected from: various hydro carbons can be linear paraffin, branched paraffin or cycloalkane; Aromatic hydrocarbon solvent can be benzene, toluene, ethylbenzene or other single replacements or polysubstituted alkylbenzene; Halogenated hydrocarbon solvent can be a halogenated alkane, or halogenated aryl hydrocarbon; Esters solvent can be aromatic esters, fatty acid ester, or trialkylphosphate; Lower aliphatic ether, cyclic ethers, polyether or ring-type polyether can be a series of and not miscible organic solvents of water such as ether, methyl tertiary butyl ether(MTBE), preferred carrene/aqueous systems.
After above-mentioned catalytic hydrogenation reaction of the present invention finishes, look concrete condition, catalyst can obtain reclaiming and recycling by simple filtration, washing, also can wash directly to recycle.
After above-mentioned catalytic hydrogenation reaction of the present invention finished, the separation of product can be carried out according to selected dicyandiamide solution.For the situation of solvent-free system or water as solvent, can pass through standing demix, tell aqueous solvent or/and the water that generates in the reaction and product is separated distills the pure product that obtain then as required; Also can extract, reclaim organic solvent by appropriate organic solvent is separated product.For with organic solvent that can be miscible with water, as methyl alcohol or ethanol, as the situation of solvent, product can separate by existing process purifies.For select organic solvent/water two-phase system or with the situation of the immiscible organic solvent of water as solvent, can pass through standing demix, tell aqueous solvent or/and the water that generates in the reaction through the recovery solvent, is separated product then.
Catalyst provided by the invention can be widely used in all kinds of hydrogenation reactions, and especially being suitable for the aromatic nitro compound is that raw material is produced arylamine, compares with existing technologies to have following positive effect:
1. catalyst of the present invention is with ionic liquid, the multiple advantages of nano transition metal and inorganic carrier is got up, a kind of new way of heterogeneousization of nano transition metal catalyst is provided, simultaneously, combine firmly difficult by wash-out with carrier by the immobilized single or multiple lift ionic liquid of covalent bonding mode, can avoid ion liquid loss, solve problems such as expensive and environmental pollution.
2. catalyst of the present invention can by change terminal substituting group be connected the base and ion liquid anion a suitable hydrophilic, hydrophobic environment is provided, help aromatic nitro compound " the dissolving in " in immobilized ionic liquid and " discharge " of product arylamine or water byproduct, thereby can normal temperature and pressure and solvent-free or with under the condition of pure water as solvent, catalytic hydrogenation is produced high-quality arylamine.The catalyst activity height, selectivity is good, and can make the aromatic nitro compound Quantitative yield is corresponding arylamine, and course of reaction cleans, do not have accessory substance and generation of waste materials.
3. catalyst of the present invention has the characteristic of three-phase, can not add phase transfer catalyst, under condition of no solvent or under the water as solvent condition, carry out, but this is not essential, also can in organic solvent system, organic solvent/water homogeneous system or organic solvent/water two-phase system, carry out, avoid the follow-up complex separations process of using phase transfer catalyst and other additive to bring.
4. catalyst of the present invention has the side chain of hedge shape can the stable catalytic activity center, prolongs the service life of catalyst, after catalytic hydrogenation reaction finishes, through simple filtering, washing, can recycling, cycle-index surpasses 15 times, does not still find any loss of activity.
Description of drawings
Fig. 1 is the transmission electron microscope photo of catalyst C of the present invention.
Fig. 2 is the XRD spectra of catalyst C of the present invention.
Fig. 3 is that catalyst C of the present invention is at the aniline yield rate of preceding 15 circulations of the solvent-free catalytic hydrogenation of nitrobenzene and the graph of a relation of cycle-index.
Fig. 4 is that catalyst C of the present invention is at 15 later transmission electron microscope photos of circulation of the solvent-free catalytic hydrogenation of nitrobenzene.
The specific embodiment
Next illustrate in greater detail the present invention by following embodiment, but protection scope of the present invention is not subjected to the restriction of these embodiment, wherein all percentage all is mass ratio.All relate among the embodiment of catalytic hydrogenation, and the product arylamine all passes through gas-chromatography, fusing point/boiling point, infrared spectrum, nuclear magnetic resonance and standard sample contrast, obtains structural identification and quantitative assay.
Synthetic (end is an octyl group, and palladium quality percentage composition is 2.0%) of the palladium nanocatalyst that immobilized two-layer ionic liquid is stable:
Immobilized pair of imidazoles (formula 2, carrier=silica of 1g octaneization; M=1, n=0; Q=(CH
2)
3, Q
1=(CH
2)
4L=OCH
2CH
3R=C
8H
17, R
1-R
6=H), being suspended in the 10mL acetonitrile solution of 0.033g palladium bichloride (0.19mmol), backflow 48h under nitrogen protection filters, and uses deionized water, absolute ethanol washing successively, 60 ℃ of vacuum drying, note is made immobilized catalyst precarsor A
0
To be dissolved with 0.021g NaBH
43mL ethanol solution (0.57mmol) slowly is added drop-wise to and is suspended with 1.0g A
0The 10mL absolute ethyl alcohol in, the mixture color deepens finally to become black gradually, after reacting completely.Filter, use deionized water and absolute ethanol washing successively, 60 ℃ of vacuum drying, the gained solid is suspended in 0.1mol/L KPF
6(0.18g, in 10mL acetone soln 0.001mol), stirring at room 48h filters, with deionized water, absolute ethanol washing, till wash solution does not contain chloride (chlorion), 60 ℃ of vacuum drying, the catalyst A that obtains.
CHN analyzes (N:2.946; C:12.62; H:2.552) corresponding to the every gram carrier of the double-deck imidazole ion liquid of 1.05mmol.
The EDXA energy spectrometer analysis shows that wherein the weight supported quantity of palladium is 2.0%.
Embodiment 2-7
According to the method for embodiment 1, change terminal substituting group octyl group and be other alkane, it is as follows that change material variety or ratio obtain a series of catalyst:
2) immobilized pair of imidazoles (formula 2, carrier=silica of 1g octaneization; M=1, n=0; Q=(CH
2)
3, Q
1=(CH
2)
4L=OCH
2CH
3R=C
8H
17, R
1-R
6=H), 0.025g palladium bichloride (0.14mmol), 0.015g NaBH
4(0.42mmol); Obtain catalyst B (Pdwt%=1.5).
3) immobilized pair of imidazoles (formula 2, carrier=silica of 1g octaneization; M=1, n=0; Q=(CH
2)
3, Q
1=(CH
2)
4L=OCH
2CH
3R=C
8H
17, R
1-R
6=H), 0.017g palladium bichloride (0.09mmol), 0.011g NaBH
4(0.27mmol); Obtain catalyst C (Pd wt%=1.0).
4) butylated immobilized pair of imidazoles (formula 2, carrier=silica of 1g; M=1, n=0; Q=(CH
2)
3, Q
1=(CH
2)
4L=OCH
2CH
3R=C
4H
9, R
1-R
6=H), 0.017g palladium bichloride (0.09mmol), 0.011g NaBH
4(0.27mol); Obtain catalyst D (Pd wt%=1.0).
5) immobilized pair of imidazoles (formula 2, carrier=silica of 1g dodecylization; M=1, n=0; Q=(CH
2)
3, Q
1=(CH
2)
4L=OCH
2CH
3R=C
12H
25, R
1-R
6=H), 0.017g palladium bichloride (0.09mmol), 0.011g NaBH
4(0.27mol); Obtain catalyst E (Pd wt%=1.0).
6) immobilized pair of imidazoles (formula 2, carrier=silica of 1g octaneization; M=1, n=0; Q=(CH
2)
3, Q
1=(CH
2)
4L=OCH
2CH
3R=C
8H
17, R
1-R
6=H), 0.023g potassium chloroplatinate (0.05mmol), 0.006g NaBH
4(0.15mmol); Obtain catalyst F (Pt wt%=1.0).
7) immobilized single imidazoles (formula 2, the carrier=silica of 1g octaneization; M=0, n=1; Q=(CH
2)
3, L=OCH
2CH
3R=C
8H
17, R
7-R
9=H), 0.017g palladium bichloride (0.09mmol), 0.011g NaBH
4(0.27mmol); Obtain catalyst G (Pdwt%=1.0).
Embodiment 8 (Comparative Examples)
Synthesizing of the direct loaded palladium catalyst of silica gel:
1g directly is suspended in the 10mL deionized water solution of 0.017g palladium bichloride (0.09mmol) according to the silica gel of conventional method activation, stirring at room 24h, all the other building-up processes are carried out according to embodiment 1, and the mass loading amount that finally obtains palladium is 1.0% catalyst H.
The application of catalyst A in catalytic hydrogenation reaction:
In being connected with the catalytic hydrogenation device of vavuum pump, hydrogen gas tank, equilibration flask, eudiometer, add 50mg catalyst A (Pdwt%=2.0,9.4 * 10
-6Mol), sealing.With the air in the hydrogen exchange reaction system 3 times, again eudiometer is filled hydrogen to certain volume.Under 30 ℃, 1atm and electromagnetic agitation, earlier with the saturated 1h of hydrogen, when the volume for the treatment of hydrogen no longer changes, to hydrogenation reaction bottle injection 4.1g nitrobenzene (mol ratio of nitrobenzene and palladium is 3500: 1).The variable quantity of record hydrogen volume, and use the gas chromatographic detection product, determine the reaction deadline thus, and calculate the conversion ratio and the selectivity that generates aniline of nitrobenzene, the results are shown in Table 1.
Embodiment 10-30
According to the catalytic hydrogenation reaction process of embodiment 7, change kind, the consumption of catalyst, reaction substrate, solvent etc., its catalytic hydrogenation effect is as follows:
10) 50mg catalyst B (Pd wt%=1.5,7.1 * 10
-6Mol), 3.0g nitrobenzene (0.025mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm.
11) 50mg catalyst C (Pdwt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm.
12) 50mg catalyst D (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm.
13) 50mg catalyst E (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm.
14) 50mg catalyst F (Pt wt%=1.0,2.6 * 10
-6Mol), 1.1g nitrobenzene (0.009mol), the mol ratio that makes nitrobenzene and platinum is 3500: 1,30 ℃, 1atm.
15) 50mg catalyst G (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm.
16) (Comparative Examples) 50mg catalyst H (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm.
17) (Comparative Examples) 10mg catalyst P d/C (Pd wt%=5.0,4.7 * 10
-6Mol, the commercial purchase), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm.
18) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.9g nitrobenzene (0.024mol), the mol ratio that makes nitrobenzene and palladium is 5000: 1,30 ℃, 1atm.
19) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 3.5g nitrobenzene (0.028mol), the mol ratio that makes nitrobenzene and palladium is 6000: 1,30 ℃, 1atm.
20) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,50 ℃, 1atm.
21) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,70 ℃, 1atm.
22) (Comparative Examples) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm, 3mL water.
23) (Comparative Examples) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm, 3mL absolute ethyl alcohol.
24) (Comparative Examples) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.0g nitrobenzene (0.016mol), the mol ratio that makes nitrobenzene and palladium is 3500: 1,30 ℃, 1atm, 3mL95% ethanol.
The catalytic hydrogenation reaction of embodiment 9-24 the results are shown in Table 1.
25) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), a certain amount of aromatic nitro compound, the mol ratio that makes aromatic nitro compound and palladium is 3500: 1,30 ℃, 1atm, 10mL water.
26) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.26g para-nitrotoluene (0.016mol), the mol ratio that makes para-nitrotoluene and palladium is 3500: 1,30 ℃, 1atm, 10mL carrene/water (1: 1).
27) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.26g para-nitrotoluene (0.016mol), the mol ratio that makes para-nitrotoluene and palladium is 3500: 1,30 ℃, 1atm, 10mL ethyl acetate/water (1: 1).
28) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), 2.26g para-nitrotoluene (0.016mol), the mol ratio that makes para-nitrotoluene and palladium is 3500: 1,30 ℃, 1atm, 10mL toluene (1: 1).
29) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), a certain amount of nitrotoleune (adjacent,, to), the mol ratio that makes nitrotoleune and palladium is 3500: 1,30 ℃, 1atm, 10mL carrene/water (1: 1).
30) 50mg catalyst C (Pd wt%=1.0,4.7 * 10
-6Mol), a certain amount of nitrophenol (adjacent,, to), the mol ratio that makes nitrophenol and palladium is 3500: 1,30 ℃, 1atm, 10mL carrene/water (1: 1).
The catalytic hydrogenation reaction of embodiment 25-30 the results are shown in Table 2.
Embodiment 31
According to the catalytic hydrogenation reaction process of embodiment 9, catalyst C recycles effect in nitrobenzene solvent-free reaction system:
After reaction finishes under embodiment 11 desired reaction conditions, pass through simple filtering, tell product aniline, catalyst is directly put in the catalytic hydrogenation process of next round, so reuse, whole recycle for 15 times the results are shown in Figure of description 3, the 15 times the results are shown in Table 1, the conversion ratio of the nitrobenzene that at every turn circulates can both reach 100%.Catalyst C and the transmission electron microscope photo that recycles after 15 times thereof are seen Figure of description 1 and accompanying drawing 4, and the particle diameter of nano metal particles only has a small amount of autohemagglutination before and after the reaction, so kept the high activity and the long-life of catalyst.
The catalytic hydrogenation effect of nitrobenzene relatively under the table 1 differential responses condition
| Catalyst | Nitrobenzene and activated centre palladium mol ratio (mol/mol) | Solvent (mL) | Temperature (℃) | Reaction time (h) [1] | Productive rate (%) | TOF [2] |
| A B C D E F [3] C C C C C [4] C C C G [5] H [6] Pd [7] | 3500 3500 3500 3500 3500 3500 5000 6000 3500 3500 3500 3500 3500 3500 3500 3500 3500 | -----------absolute ethyl alcohol 95% ethanol deionized water--- | 30 30 30 30 30 30 30 30 50 70 30 30 30 30 30 30 30 | 9.5 8.5 8.5 11.5 13.0 10.5 15.0 20.0 8.0 8.0 9.0 7.0 7.5 11.5 12.0 11.0 11.0 | 100 100 100 100 100 100 100 100 100 100 100 100 100 100 65 75 75 | 368 411 411 304 269 333 333 300 438 438 388 500 467 304 292 318 318 |
[1] reaction time is that the conversion ratio of nitrobenzene reaches 100% o'clock used time.
[2] unit of TOF value is: mole aniline generates/(the mole activated centre per hour).
[3] used activity of such catalysts component is a platinum.
[4] catalytic hydrogenation of nitrobenzene is reused 15 times situation.
[5] palladium with the direct load of silica gel is a catalyst.
[6] with the stable palladium catalyst of the monolayer ionic liquid of supported on silica-gel.
[7] be catalyst with commercial Pd/C.
The catalytic hydrogenation result of other aromatic nitro compound under the table 2 differential responses condition
[1]
[1] reaction condition: 5 μ molPd, 17.5mmol aromatic nitro compound, substrate/Pd mole ratio=3500, T=303K, P=1atm.
[2] reaction time is that the conversion ratio of nitrobenzene reaches 100% o'clock used time.
[3] unit of TOF value is: the mole arylamine generates/(the mole activated centre per hour).
[4] productive rate of dechlorination accessory substance.
Claims (10)
1. solid carried ion liquid-nanometer metal particle catalyst is characterized in that this catalyst has structural formula as shown in Equation 1:
Wherein:
Carrier is the indissoluble inoganic solids oxide that contains hydroxyl on the surface, is selected from silica, diatomite, aluminium oxide, aluminosilicate, zeolite, titanium oxide, zirconia;
M is any positive integer between the 0-10, and n is any positive integer between the 1-10;
Q, Q
1, Q
2For connecting base, be selected from (CH
2)
x, (CH
2)
aC
6H
4(CH
2)
b, (CH
2)
aC
6H
4O (CH
2)
y, (CH
2)
xO (CH
2)
y, (CH
2)
xS (CH
2)
y, (CH
2)
xOC
6H
4O (CH
2)
yDeng group, they can be mutually the same also can be different, wherein x and y are respectively any positive integer of 2-18, a and b are respectively any positive integer of 0-18;
L is a substituting group, is selected from the alkoxyl of C1-4;
R is a terminal groups, be selected from C1-20 alkyl, cycloalkyl, aralkyl, contain the alkyl of aerobic or sulfur heteroatom etc.;
Substituent R on the imidazole ring
1-R
9Can be hydrogen atom, also can be alkyl, cycloalkyl, aralkyl of C1-20 etc., and they can be the same or different;
Anion Y
Q-For univalent anion or multivalent anions, be selected from halide ion, or IIIA, IVA, the polyhalide anion of VA family element, their oxyacid radical ion or complex anion, or the organic acid ion of C1-8; Q is anion Y
Q-Charge number, take from any positive integer between the 1-10;
M is transition metals such as IB and/or VIII family metal, is selected from a kind of or/and the mixture of several transition metals in platinum, palladium, ruthenium, rhodium, iridium, nickel, cobalt, gold, silver, the copper etc.;
2. solid carried ion liquid-nanometer metal particle catalyst according to claim 1 is characterized in that a preferred class is in the formula 1:
Carrier is silica, diatomite, zeolite;
M and n are 1 or 2;
Q, Q
1, Q
2Be (CH
2)
x, (CH
2)
aC
6H
4(CH
2)
b, (CH
2)
aC
6H
4O (CH
2)
y, (CH
2)
xO (CH
2)
y, they can be mutually the same also can be different, wherein x and y are respectively any positive integer of 2-10, a and b are respectively any positive integer of 0-10;
L is a methoxy or ethoxy;
R is C1-10 alkyl, cycloalkyl, aralkyl;
Substituent R on the imidazole ring
1-R
9Can be hydrogen atom, methyl, ethyl, propyl group, butyl, phenyl, benzyl, they can be the same or different;
Anion Y
Q-Be fluorine, chlorine, bromine, iodine, fluoboric acid root, fluorophosphoric acid root, trifluoracetic acid root, TFMS root, tetrafluoroborate, hexafluoro-phosphate radical, methanesulfonate, trifluoromethane sulfonic acid root, benzene sulfonic acid root, p-methyl benzenesulfonic acid root etc.;
M is platinum, palladium, ruthenium, rhodium or wherein a kind of or/and several mixtures.
3. according to claim 1 and 2 described solid carried ion liquid-nanometer metal particle catalysts, wherein the amount of bond ion liquid is the 0.1-20% of vehicle weight, preferred 1-10%; The amount of transition metal is the 0.1-20% of vehicle weight, preferred 0.5-5%.
4. solid carried ion liquid-nanometer metal particle catalyst according to claim 1, its preparation method are characterised in that and comprise following steps:
1) solid-loaded ionic-liquid with formula 2 representatives is that raw material reacts with the salt that contains transition metals such as IB and/or VIII family metal;
2) salt that will contain transition metal with reducing agent is reduced to the nano metal particles of simple substance form;
3) handle with containing suitable anionic salt; But this step is not necessary;
Here said solid-loaded ionic-liquid has the structural formula of formula 2 representatives:
Formula 2
Carrier wherein, m, n, Q, Q
1, Q
2, L, R, R
1-R
9, Y
Q-Deng identical with claim 1 or a kind of corresponding every definition of 2 described formulas;
The salt of said transition metal is halide, nitrate, sulfate, the acetate of elements such as platinum, palladium, ruthenium, rhodium, iridium, nickel, cobalt, gold, silver, copper, the salt that their polyhalide anion and alkali metal ion form, or they are with the salt of the complex anion of the part formation that also contains phosphorus, nitrogen, oxygen or element sulphur except that carbon containing and hydrogen etc.; Preferably halide, nitrate, sulfate, the acetate of elements such as platinum, palladium, ruthenium, rhodium, iridium, nickel, cobalt, gold, silver, copper, the salt that their polyhalide anion and alkali metal ion form;
Said reducing agent is a metal hydride, hypophosphorous acid, formaldehyde, hydrazine and hydrazine hydrate, hydrogen, low-carbon alcohols such as methyl alcohol, ethanol, isopropyl alcohol etc.; Sodium borohydride preferably, formaldehyde, hydrazine and hydrazine hydrate, hydrogen, low-carbon alcohols such as methyl alcohol, ethanol, isopropyl alcohol etc.;
The said general formula that contains suitable anionic salt is Z
q P+Y
p Q-, anion Y wherein
Q-Meaning and the Y of formula 1 or formula 2
Q-Identical, cation Z
P+Be cation, ammonium ion or its organic derivative of alkali metal, alkaline-earth metal, IIIA, IVA family element, p is cationic charge number; Sodium tetrafluoroborate preferably, sodium hexafluoro phosphate, sodium trifluoroacetate, TFMS sodium, potassium tetrafluoroborate, Potassium Hexafluorophosphate, trifluoracetic acid potassium, TFMS potassium etc.;
5. the preparation method of solid carried ion liquid-nanometer metal particle catalyst according to claim 4, the condition that it is characterized in that respectively going on foot in the synthetic reaction is:
1) the weight of material ratio is: weight=8 of metallic element: 1-1: 1 in the salt of the weight of the solid-loaded ionic-liquid of formula 2 representative/contain transition metal; Reaction condition is an inert atmosphere, can be nitrogen, argon gas etc.; Reaction medium is alcohols or nitrile solvents; Temperature is that room temperature arrives between the boiling temperature of solvent for use; Reaction time 6-96 hour;
2) molar ratio of material is: the catalyst precarsor that reducing agent/step 1 obtains=5: 1-1: 1; Reaction medium is an alcohols solvent; Temperature 20-80 ℃; Reaction time 1-10 hour;
3) molar ratio of material by: the anion number of salt compounds and anion electrically charged long-pending/cation number=5 of solid-loaded ionic-liquid: 1-1: 1; Reaction medium selects the mixed solvent of water, acetonitrile, acetone, ethanol or above-mentioned solvent; Temperature 10-80 ℃; Reaction time 6-96h.
6. according to the preparation method of claim 4 and 5 described solid carried ion liquid-nanometer metal particle catalysts, it is characterized in that respectively going on foot that optimum condition is in the synthetic reaction:
1) the weight of material ratio is: weight=6 of metallic element: 1-2: 1 in the salt of the weight of the solid-loaded ionic-liquid of formula 2 representative/contain transition metal; Reaction condition is an inert atmosphere, can be nitrogen or argon gas; Reaction medium is ethanol or acetonitrile; The boiling temperature of 60 ℃-solvent for use of reaction temperature; Reaction time 48-72 hour;
2) molar ratio of material is: the catalyst precarsor that reducing agent/step 1 obtains=4: 1-2: 1; Reaction medium is an ethanol; Reaction temperature 20-30 ℃; Reaction time 2-4 hour;
3) molar ratio of material by: the anion number of salt compounds and anion electrically charged long-pending/cation number=3 of solid-loaded ionic-liquid: 1-1.2: 1; Reaction medium is water, acetonitrile or acetone; Temperature 15-30 ℃; Reaction time 48-72h.
7. solid carried ion liquid-nanometer metal particle catalyst according to claim 1 is used for the purposes of organic reaction; can be used for but be not limited to following reaction: the aromatic nitro compound catalytic hydrogenation is produced corresponding arylamine, or the reaction that simple substance transition metal particle such as the catalytic hydrogenation of other unsaturated bond and hydroformylation, Heck reaction, Suzuki coupling reaction can catalysis.
8. catalyst according to claim 7 is used, the aromatic nitro compound that is applicable to the inventive method can be the single nitro of benzene aromatic hydrocarbon or single nitro or many nitro compounds of many nitro compounds or heterocyclic compound, can also have one or more substituting groups on the aromatic ring of these compounds, comprise C
1-C
20Alkyl, cycloalkyl, aralkyl, aryl, contain heteroatomic alkyl such as aerobic, nitrogen or sulphur, alcoxyl, hydroxyl, carboxyl, ester group, sulfonic group, amido, amide groups etc., they can be the same or different.
9. use according to claim 7 or claim 8 described catalyst, it is characterized in that:
In the catalytic hydrogenation reaction of aromatic nitro compound, reaction temperature is 20-60 ℃, preferably 20-30 ℃;
The reaction pressure preferred atmosphere is pressed, and this is not essential, either can or high pressure but also can under partial vacuum, carry out;
Reaction time is 0.5-48h, the time that substrate transforms fully in the preferred concrete reaction;
The mol ratio of substrate and active component is 1-10000, preferably 250-5000.
10. use according to the described catalyst of claim 7 to 10, the catalytic hydrogenation reaction process is preferably carried out under condition of no solvent or under the water as solvent condition, but this is not essential, can carry out in organic solvent system, organic solvent/water homogeneous system or organic solvent/water two-phase system yet.
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