CN103214392A - Synthetic method of N-benzylideneaniline compound - Google Patents
Synthetic method of N-benzylideneaniline compound Download PDFInfo
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- CN103214392A CN103214392A CN2013101332457A CN201310133245A CN103214392A CN 103214392 A CN103214392 A CN 103214392A CN 2013101332457 A CN2013101332457 A CN 2013101332457A CN 201310133245 A CN201310133245 A CN 201310133245A CN 103214392 A CN103214392 A CN 103214392A
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Abstract
The invention discloses a synthetic method of an N-benzylideneaniline compound. The method comprises the following steps of: adding inorganic base under the effect of a supported noble metal catalyst in a solvent-free condition or a reaction solvent based on a nitrobenzene compound as shown in a formula I and benzyl alcohol; and under nitrogen atmosphere, stirring for reaction at 50-240 DEG C for 1-30 hours; and post-treating the reaction liquid to prepare the N-benzylideneaniline compound. The supported noble metal catalyst comprises a carrier and active components attached to the carrier. The active components are noble metals which are palladium, ruthenium, gold, silver, iridium, platinum or rhodium. The noble metal catalyst prepared by the invention is high in activity and stability, and good in selectivity. The conversion ratio of the nitrobenzene compound is 100%, the selectivity of the N-benzylideneaniline compound is greater than 95%, and the environment is not polluted by preparation of the catalyst.
Description
(1) technical field
The present invention relates to a kind of method by nitrobenzene compounds and the synthetic benzylideneaniline compounds of phenylcarbinol one kettle way, particularly under the loaded noble metal catalyst effect, nitrobenzene compounds and phenylcarbinol one kettle way synthesize the method for benzylideneaniline compounds in alkaline condition.
(2) background technology
Benzylideneaniline compounds (benzylidene aniline compounds) is the important organic synthesis intermediate of a class, and medical aspect is mainly used in medicine, syncillin class antibiotic medicine and the parasiticide class medicine etc. of synthetic anxiety, calming soporific.In pesticide producing, be mainly used in and produce acetamide-group herbicides and organic phosphorous insecticide.Aspect food and feed additive, can be applicable to the production of amino acids.
The prior synthesizing method of benzylideneaniline compounds is amino benzenes compounds and the direct condensation of phenyl aldehyde.Though this method is very easy, but exceed much than nitrobenzene compounds and phenylcarbinol as the amino benzenes compounds and the phenyl aldehyde price of raw material, and the amino benzenes compounds instability, toxicity is bigger.There is the investigator to replace phenyl aldehyde, generates the benzylideneaniline compounds with the amino benzenes compounds condensation with phenylcarbinol.Prepare the palladium catalyst of a series of different carriers loads as Kwon etc., be used for aniline and phenylcarbinol condensation reaction, in 20 hours reaction times, when catalyzer was 5.0%Pd/C, the benzylideneaniline productive rate had only 19%, and catalyzer is 3.5%Pd/Al
2O
3The time, the benzylideneaniline productive rate is 42%(Kwon M, Kim S, Park S, et al.One-Pot Synthesis of Imines and Secondary Amines by Pd-Catalyzed Coupling of Benzyl Alcohols and Primary Amines.J.Org.Chem., 2009,74 (7): 2877-2879).This method yield is very low.Also have aniline is substituted with oil of mirbane, with the phenyl aldehyde catalytic hydrogenation reaction.As report such as Santos with Au/TiO
2Be used for oil of mirbane and phenyl aldehyde catalytic hydrogenation reaction, the oil of mirbane transformation efficiency is 94%, the benzylideneaniline selectivity is 93%(Santos L L, Sern P, Corma A.Chemoselective Synthesis of Substituted Imines, Secondary Amines, and β-Amino Carbonyl Compounds from Nitroaromatics through Cascade Reactions on Gold Catalysts.Chem.Eur., 2009,15 (33): 8196-8203).This method target product yield is higher, but needs in the reaction process to add hydrogen as hydrogen source.In recent years, Tang etc. have reported the research of oil of mirbane and the reaction of phenylcarbinol one kettle way, with Au/TiO
2Be catalyzer, reacted 14 hours, oil of mirbane transformation efficiency 100%, the reaction highly selective has generated Phenhenzamine---further reduzate (the Tang C H of benzylideneaniline, He L, Liu Y M, et al.Direct One-Pot Reductive N-Alkylation of Nitroarenes by using Alcohols with Supported Gold Catalysts.Chem.Eur.J.2011,17:7172-7177).This method is simple than aforesaid method, and cost is low, and does not need hydrogen in the reaction process, operational safety.But the benzylideneaniline compounds further reduces easily and generates the Phenhenzamine compounds.
(3) summary of the invention
The synthetic method of the benzylideneaniline compounds that the purpose of this invention is to provide that a kind of technology is simple, cost is low, safety, environmental friendliness, transformation efficiency and selectivity is high.
The technical solution used in the present invention is as follows:
The synthetic method of the benzylideneaniline compounds shown in a kind of formula II, described method is: with the nitrobenzene compounds shown in the formula I and phenylcarbinol under condition of no solvent or in the reaction solvent, under the effect of loaded noble metal catalyst, add mineral alkali, under the nitrogen atmosphere, stirring reaction under 50～240 ℃ of temperature reacted after 1～30 hour, and the reaction solution aftertreatment prepares the benzylideneaniline compounds shown in the formula II; Nitrobenzene compounds shown in the described formula I is 1:2～30 with the ratio of the amount of substance of phenylcarbinol, preferred 1:5～30, more preferably 1:7～13; Described reaction solvent is toluene, methyl alcohol, ethanol, acetonitrile, acetone or water, is preferably toluene;
Among described formula I or the formula II, R
1, R
2, R
3, R
4, R
5Independent separately is hydrogen, halogen, methyl, ethyl, methoxyl group, oxyethyl group, formyl radical or vinyl, and described halogen is fluorine, chlorine, bromine or iodine;
Further, preferred R
1, R
2, R
3, R
4, R
5All be hydrogen, or preferred R
1～R
5In a substituting group be methyl or halogen, all the other substituting groups are hydrogen; Or preferred R
1～R
5In two substituting groups be halogen, all the other substituting groups are hydrogen.More preferably formula I is oil of mirbane, Ortho Nitro Toluene or 3, the 5-dichloronitrobenzene.
Described loaded noble metal catalyst comprises carrier and the active ingredient that is carried on the carrier, and described carrier is SiO
2, Al
2O
3, gac, porous carbon materials, TiO
2, ZrO
2Or molecular sieve, be preferably SiO
2Or porous carbon materials; Described active ingredient is a precious metal, and described precious metal is palladium, ruthenium, gold and silver, iridium, platinum or rhodium, is preferably palladium or ruthenium.The charge capacity of described precious metal counts 0.5～10.0% with the quality of carrier, and preferred 2～5%;
Described loaded noble metal catalyst can also comprise carrier and be carried on active ingredient and promotor on the carrier, and described promotor is one or more the combination in alkalimetal oxide, alkaline earth metal oxide, rare earth oxide, the base metal; Described base metal is nickel, copper, cobalt or molybdenum, and described alkalimetal oxide is preferably sodium oxide, potassium oxide, and described alkaline earth metal oxide is preferably calcium oxide, barium oxide or magnesium oxide; Described rare earth oxide is preferably cerium oxide, lanthanum trioxide or Samarium trioxide; Described promotor is lanthanum trioxide more preferably; The charge capacity of described promotor counts 0～20% with the quality of carrier, and is preferred 0～5%, and 0 representative wherein is infinitely close to 0 but be not 0.
Further, loaded noble metal catalyst of the present invention preferably is made up of carrier and the active ingredient that is carried on the carrier, and described active ingredient is a precious metal, and the charge capacity of described precious metal counts 0.5～10.0% with the quality of carrier, and preferred 2～5%.
Or described loaded noble metal catalyst is made up of carrier and the active ingredient and the promotor that are carried on the carrier, described active ingredient is a precious metal, the charge capacity of precious metal counts 0.5～10.0% with the quality of carrier, and described promotor is one or more the combination in alkalimetal oxide, alkaline earth metal oxide, rare earth oxide, the base metal; Described base metal is nickel, copper, cobalt or molybdenum, and described alkalimetal oxide is preferably sodium oxide, potassium oxide, and described alkaline earth metal oxide is preferably calcium oxide, barium oxide or magnesium oxide; Described rare earth oxide is preferably cerium oxide, lanthanum trioxide or Samarium trioxide; The charge capacity of described promotor counts 0～20% with the quality of carrier, and 0 representative wherein is infinitely close to 0 but be not 0.
Mineral alkali of the present invention is preferably sodium bicarbonate, yellow soda ash, salt of wormwood, potassium hydroxide, sodium hydroxide or ammoniacal liquor, preferred potassium hydroxide or sodium hydroxide, most preferably potassium hydroxide.
The present invention's reaction can be carried out under condition of no solvent or in the reaction solvent, and condition of no solvent does not promptly add under the reaction solvent condition.
The mass ratio of the nitrobenzene compounds shown in described mineral alkali and the formula I is generally 0.05～2:1, preferred 0.1～0.3:1.
The mass ratio of the nitrobenzene compounds shown in described loaded noble metal catalyst and the formula I is 0.01～0.3:1, preferred 0.1～0.3:1.
The mass ratio of nitrobenzene compounds shown in the described formula I and reaction solvent is 1:5～35, preferred 1:15～25.
Described reaction solution post-treating method is: after reaction finishes, and reacting liquid filtering, the aqueous ethanolic solution recrystallization with volumetric concentration 20%～70% behind the filtrate steaming removal solvent makes the benzylideneaniline compounds shown in the formula II.
The temperature of the present invention's reaction is preferably 160～180 ℃.
Preferred 16～26 hours of the time of described reaction, more preferably 16～22 hours.
Concrete, preferred the method for the invention is carried out according to the following steps: the ratio according to nitrobenzene compounds and phenylcarbinol amount of substance is 1:5～30, the mass ratio of nitrobenzene compounds and reaction solvent is 1:5～35, the quality of mineral alkali is 0.05～2.0 times of nitrobenzene compounds quality, the consumption of loaded noble metal catalyst is 0.01～0.3 times of nitrobenzene compounds quality, with nitrobenzene compounds, phenylcarbinol, reaction solvent, mineral alkali adds reactor, air in the logical nitrogen replacement reactor also keeps nitrogen atmosphere, intensification remains on 50～240 ℃, stirring reaction 1～30 hour, reaction finishes afterreaction liquid filters, and the aqueous ethanolic solution recrystallization with volumetric concentration 70% behind the filtrate steaming removal solvent makes the benzylideneaniline compounds shown in the formula II.
Loaded noble metal catalyst of the present invention can be made by pickling process, and is concrete:
(1) loaded noble metal catalyst by carrier when being carried on active ingredient on the carrier and forming, the preparation method is: the charge capacity according to precious metal counts 0.5～10.0% with the carrier quality, the theoretical amount of the solubility precious metal salt of the amount of substances such as precious metal element of calculating and load, take by weighing the water-soluble precious metal steeping fluid that is made into of solubility precious metal salt of theoretical amount, described solubility precious metal salt is generally precious metal nitrate, precious metal chloride, precious metal acetate or precious metal vitriol, carrier is immersed in the precious metal steeping fluid fully, flooded 2～8 hours down in 15～35 ℃ (preferred 20～30 ℃), add excessive reductive agent then, described reductive agent is generally 2～8:1 with the ratio of the amount of substance of precious metal, preferred 4～6:1, described reductive agent is generally sodium borohydride, POTASSIUM BOROHYDRIDE, Trisodium Citrate, hydrazine hydrate or polyvalent alcohol, again in stirring at room 2～8 hours, suction filtration, filter cake washs no acid group negatively charged ion to the filtrate with redistilled water, in 60～150 ℃ of vacuum-dryings 2～12 hours, make described loaded noble metal catalyst at last.
(2) loaded noble metal catalyst by carrier when being carried on active ingredient on the carrier and promotor and forming, the preparation method is: the charge capacity according to promotor counts 0～20% with the quality of carrier, the theoretical amount of the soluble metallic salt of the amount of substances such as metallic element in calculating and the promotor, take by weighing the water-soluble auxiliary agent steeping fluid that is made into of soluble metallic salt of theoretical amount, carrier is immersed in the auxiliary agent steeping fluid fully, flooded 2～8 hours down in 15～350 ℃ (preferred 20～30 ℃), then with whole auxiliary agent steeping fluids and carrier 80～150 ℃ of dryings 2～12 hours, in 400～800 ℃ of following roastings 2～8 hours, get the catalyst intermediate that load has promotor again;
Charge capacity according to precious metal counts 0.5～10.0% with the carrier quality, the theoretical amount of the solubility precious metal salt of the amount of substances such as precious metal element of calculating and load, take by weighing the water-soluble precious metal steeping fluid that is made into of solubility precious metal salt of theoretical amount, described solubility precious metal salt is generally precious metal nitrate, precious metal chloride, precious metal acetate or precious metal vitriol, there is the catalyst intermediate of promotor to be immersed in fully in the precious metal steeping fluid load, flooded 2～8 hours down in 15～35 ℃ (preferred 20～30 ℃), add excessive reductive agent then, described reductive agent is generally 2～8:1 with the ratio of the amount of substance of precious metal, preferred 4～6:1, described reductive agent is generally sodium borohydride, POTASSIUM BOROHYDRIDE, Trisodium Citrate, hydrazine hydrate or polyvalent alcohol, again in stirring at room 2～8 hours, suction filtration, filter cake washs no acid group negatively charged ion to the filtrate with redistilled water, in 60～150 ℃ of vacuum-dryings 2～12 hours, make described loaded noble metal catalyst at last.
The immersion process for preparing loaded catalyst is to well known to a person skilled in the art method.
Loaded noble metal catalyst of the present invention also available hydrogen reduction makes:
(i) loaded noble metal catalyst by carrier when being carried on active ingredient on the carrier and forming, the preparation method is: the charge capacity according to precious metal counts 0.5～10.0% with the carrier quality, the theoretical amount of the solubility precious metal salt of the amount of substances such as precious metal element of calculating and load, take by weighing the water-soluble precious metal steeping fluid that is made into of solubility precious metal salt of theoretical amount, described solubility precious metal salt is generally precious metal nitrate, precious metal chloride, precious metal acetate or precious metal vitriol, carrier is immersed in the precious metal steeping fluid fully, flooded 2～8 hours down in 15～35 ℃ (preferred 20～30 ℃), 80～150 ℃ of dryings 2～12 hours, again in 400～800 ℃ of following roastings 2～8 hours, last 300～700 ℃ feed reducing gas reduction 1～10 hour down, make described loaded noble metal catalyst; Described reducing gas is the gas mixture of hydrogen or hydrogen and nitrogen.
(ii) loaded noble metal catalyst by carrier when being carried on active ingredient on the carrier and promotor and forming, the preparation method is: the charge capacity according to promotor counts 0～20% with the quality of carrier, the theoretical amount of the soluble metallic salt of the amount of substances such as metallic element in calculating and the promotor, take by weighing the water-soluble auxiliary agent steeping fluid that is made into of soluble metallic salt of theoretical amount, carrier is immersed in the auxiliary agent steeping fluid fully, flooded 2～8 hours down in 15～350 ℃ (preferred 20～30 ℃), then with whole auxiliary agent steeping fluids and carrier 80～150 ℃ of dryings 2～12 hours, in 400～800 ℃ of following roastings 2～8 hours, get the catalyst intermediate that load has promotor again;
Charge capacity according to precious metal counts 0.5～10.0% with the carrier quality, the theoretical amount of the solubility precious metal salt of the amount of substances such as precious metal element of calculating and load, take by weighing the water-soluble precious metal steeping fluid that is made into of solubility precious metal salt of theoretical amount, described solubility precious metal salt is generally precious metal nitrate, precious metal chloride, precious metal acetate or precious metal vitriol, there is the catalyst intermediate of promotor to be immersed in fully in the precious metal steeping fluid load, flooded 2～8 hours down in 15～35 ℃ (preferred 20～30 ℃), 80～150 ℃ of dryings 2～12 hours, again in 400～800 ℃ of following roastings 2～8 hours, last 300～700 ℃ feed reducing gas reduction 1～10 hour down, make described loaded noble metal catalyst; Described reducing gas is the gas mixture of hydrogen or hydrogen and nitrogen.
The present invention compared with prior art, its beneficial effect is embodied in:
1. prepared noble metal catalyst is active and stability is high, and selectivity is good; The transformation efficiency of nitrobenzene compounds is 100%, and the selectivity of benzylideneaniline compounds can be greater than 95%; Preparation of catalysts is free from environmental pollution, and the recyclable utilization of catalyzer.
2. reaction is a starting raw material with nitrobenzene compounds and phenylcarbinol, and reaction do not need to provide in addition hydrogen source, and technology is simple, cost is low, safe, environmentally friendly.
(4) embodiment:
Below with specific embodiment technical scheme of the present invention is described, but protection scope of the present invention is not limited thereto:
Embodiment 1:
1) preparation of porous carbon carrier, 9.4g phenol under 50 ℃ of attitudes, adds the 10mL0.5mol/L sodium hydroxide solution, stirs 10～15 minutes, drip 4.1g37% formaldehyde solution, the mol ratio of phenol, formaldehyde and sodium hydroxide is 2:1:0.1, and temperature rises to 85～95 ℃, stirs reaction down 1 hour, temperature is reduced to room temperature, with 0.5mol/L hydrochloric acid soln adjust pH neutrality, remove moisture through underpressure distillation again, brown liquid 11g, add dehydrated alcohol and be mixed with 20% resol ethanol solution.8g F127 is dissolved in the 32g dehydrated alcohol; with the mass ratio of dehydrated alcohol be 1:4; mix with above-mentioned 20% resol ethanol solution, room temperature left standstill 4～6 hours, and underpressure distillation eliminates ethanol; thermopolymerization 24 hours under 100～120 ℃ of temperature then; obtain polymkeric substance, at last in tube type resistance furnace, under the nitrogen protection; 400 ℃ kept 1 hour, and 800 ℃ keep calcining in 0.5 hour to obtain porous carbon materials 3g.
2) load active component, setting the palladium charge capacity is 2.0%, the mass concentration that 1g step 1) gained porous carbon carrier is added 2mL Pd is the H of 0.010g/mL
2PdCl
6In the solution, stirred 2 hours, add borane reducing agent sodium hydride 0.029g then in the room temperature lower magnetic force, again in 3 hours suction filtrations of stirring at room, filter cake is washed till no acid group negatively charged ion in the filtrate with redistilled water, and last 80 ℃ of vacuum-dryings 3 hours make the palladium charge capacity and be 2.0% load type palladium catalyst 1g.
3) the above-mentioned catalyzer of 0.24 gram is added 100 milliliters of reactors, again 1.20 gram oil of mirbane, 8.5 gram phenylcarbinols, 0.25 gram potassium hydroxide solid, 30 milliliters of toluene are added reactor, air in the logical nitrogen replacement reactor also keeps nitrogen atmosphere, 160 ℃ of temperature of reaction, 18 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 96.7%.Reacting liquid filtering, filtrate revolve and steam to remove the back of desolvating and make benzylideneaniline 1.64g with the aqueous ethanolic solution recrystallization of specific volume 70%.
Embodiment 2:
Catalyst preparation process is with embodiment 1, and difference is that the palladium catalyst charge capacity is 5.0%, and the mass concentration that is about to 1g porous carbon carrier adding 5mL Pd is the H of 0.010g/mL
2PdCl
6In the solution, stirred 2 hours in the room temperature lower magnetic force, add borane reducing agent sodium hydride 0.073g then, subsequent step is identical, makes the palladium charge capacity and be 5% load type palladium catalyst.0.36 gram catalyzer is added 100 milliliters of reactors, and other reaction conditions is with embodiment 1, and in 16 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 85.0%.
Embodiment 3:
Catalyst preparation process is with embodiment 1, and difference is that palladium catalyst content is 3.0%, and the mass concentration that is about to 1g porous carbon carrier adding 3mL Pd is the H of 0.010g/mL
2PdCl
6In the solution, stirred 2 hours in the room temperature lower magnetic force, add borane reducing agent sodium hydride 0.044g then, subsequent step is identical, makes the palladium charge capacity and be 3% load type palladium catalyst.0.36 gram catalyzer is added 100 milliliters of reactors, and other reaction conditions is with embodiment 1, and in 18 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 97.8%.
Embodiment 4:
Catalyst preparation process is with embodiment 1, difference is 0.36 gram catalyzer is added 100 milliliters of autoclaves, and other reaction conditions is with embodiment 1,18 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 98.0%.
Embodiment 5:
Catalyst preparation process is with embodiment 1, and difference is that temperature of reaction is 180 ℃, and other reaction conditions is with embodiment 1, and in 18 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 88.9%.
Embodiment 6:
Catalyst preparation process is with embodiment 1, difference is 0.125 gram potassium hydroxide solid is added 100 milliliters of reactors, and other reaction conditions is with embodiment 1,18 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 94.1%.
Embodiment 7:
Catalyst preparation process is with embodiment 1, and difference is metal Ru is loaded on the porous carbon materials, and ruthenium content is 5.0%, and the mass concentration that is about to 1g porous carbon carrier adding 5mL Ru is the RuCl of 0.010g/mL
3In the solution, stirred 2 hours in the room temperature lower magnetic force, add borane reducing agent sodium hydride 0.075g then, subsequent step is identical, makes the ruthenium charge capacity and be 5% load ruthenium catalyst Ru/C.0.36 gram Ru/C catalyzer is added 100 milliliters of reactors, and other reaction conditions is with embodiment 1, and in 22 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 94.1%.
Embodiment 8:
Catalyst preparation process is with embodiment 1.0.24 gram palladium catalyst is added 100 milliliters of reactors, again with 1.89 grams 3,5-dichloronitrobenzene, 8.5 gram phenylcarbinols, 0.25 gram potassium hydroxide solid, 30 milliliters of toluene add reactor, 160 ℃ of temperature of reaction, nitrogen atmosphere, 18 hours reaction times, gas chromatographic detection gets 3, the transformation efficiency of 5-dichloronitrobenzene is 100%, N-benzylidene 3, and the selectivity of 5-dichlorphenamide bulk powder is 96.0%.
Embodiment 9:
Catalyst preparation process is with embodiment 1.0.24 gram palladium catalyst is added 100 milliliters of reactors, again 1.35 gram Ortho Nitro Toluenes, 8.5 gram phenylcarbinols, 0.25 gram potassium hydroxide solid, 30 milliliters of toluene are added reactor, 160 ℃ of temperature of reaction, nitrogen atmosphere, 18 hours reaction times, the transformation efficiency that gas chromatographic detection gets Ortho Nitro Toluene is 100%, and the selectivity of N-benzylidene Ortho Toluidine is 86.8%.
Embodiment 10:
Preparation Pd/SiO
2Catalyzer: with 1g SiO
2The mass concentration that carrier adds 6mL Pd is the H of 0.005g/mL
2PdCl
6In the solution, dipping is 6 hours under room temperature, 110 ℃ of dryings 12 hours, and again in 500 ℃ of following roastings 4 hours, last 300 ℃ fed hydrogen reducings 4 hours down, made the Pd charge capacity and be 3% Pd/SiO
2Catalyzer.
The above-mentioned palladium catalyst of 0.36 gram is added 100 milliliters of reactors, and other reaction conditions is with embodiment 1, and in 18 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 93.6%.
Embodiment 11:
Catalyst preparation process is with embodiment 10, and difference is precious metal palladium is loaded on the SiO that the auxiliary agent lanthanum trioxide is modified
2On.The Preparation of catalysts process is as follows: the charge capacity according to the auxiliary agent lanthanum trioxide counts 5.0% with the quality of carrier, takes by weighing the La (NO of 0.133g
3)
36H
2O is dissolved in the 5mL water, gets in the lanthanum nitrate aqueous solution, with 1g SiO
2Carrier is immersed in the lanthanum nitrate aqueous solution fully, in 20 ℃ of following dippings 5 hours, 110 ℃ of dryings 12 hours, again in 500 ℃ of following roastings 4 hours, obtains the catalyst intermediate La of lanthanum oxide-carrying then
2O
3-SiO
2Setting the palladium charge capacity is 3.0%, with 1g La
2O
3-SiO
2The mass concentration that adds 6mL Pd is the H of 0.005g/mL
2PdCl
6In the solution, dipping is 6 hours under room temperature, 110 ℃ of dryings 12 hours, and again in 500 ℃ of following roastings 4 hours, last 300 ℃ fed hydrogen reducings 4 hours down, made the Pd charge capacity and be 3% Pd/La
2O
3-SiO
2Catalyzer.
The above-mentioned palladium catalyst of 0.36 gram is added 100 milliliters of reactors, and other reaction conditions is with embodiment 1, and in 16 hours reaction times, the transformation efficiency that gas chromatographic detection gets oil of mirbane is 100%, and the selectivity of benzylideneaniline is 95.8%.
Claims (10)
1. the synthetic method of the benzylideneaniline compounds shown in the formula II, it is characterized in that described method is: with the nitrobenzene compounds shown in the formula I and phenylcarbinol under condition of no solvent or in the reaction solvent, under the effect of loaded noble metal catalyst, add mineral alkali, under the nitrogen atmosphere, stirring reaction under 50～240 ℃ of temperature reacted after 1～30 hour, and the reaction solution aftertreatment prepares the benzylideneaniline compounds shown in the formula II; Nitrobenzene compounds shown in the described formula I is 1:2～30 with the ratio of the amount of substance of phenylcarbinol; Described reaction solvent is toluene, methyl alcohol, ethanol, acetonitrile, acetone or water;
Among described formula I or the formula II, R
1, R
2, R
3, R
4, R
5Independent separately is hydrogen, halogen, methyl, ethyl, methoxyl group, oxyethyl group, formyl radical or vinyl, and described halogen is fluorine, chlorine, bromine or iodine;
Described loaded noble metal catalyst comprises carrier and the active ingredient that is carried on the carrier, and described carrier is SiO
2, Al
2O
3, gac, porous carbon materials, TiO
2, ZrO
2Or molecular sieve; Described active ingredient is a precious metal, and described precious metal is palladium, ruthenium, gold and silver, iridium, platinum or rhodium; The charge capacity of described precious metal counts 0.5～10.0% with the quality of carrier.
2. the method for claim 1, it is characterized in that described loaded noble metal catalyst comprises carrier and is carried on active ingredient and promotor on the carrier, described promotor is one or more the combination in alkalimetal oxide, alkaline earth metal oxide, rare earth oxide, the base metal; The charge capacity of described promotor counts 0～20% with the quality of carrier, and 0 representative wherein is infinitely close to 0 but be not 0.
3. method as claimed in claim 2 is characterized in that described base metal is nickel, copper, cobalt or molybdenum, and described basic metal is oxidized to sodium oxide, potassium oxide, and described alkaline earth metal oxide is calcium oxide, barium oxide or magnesium oxide; Described rare earth oxide is cerium oxide, lanthanum trioxide or Samarium trioxide.
4. method as claimed in claim 1 or 2 is characterized in that described precious metal is palladium or ruthenium.
5. method as claimed in claim 1 or 2 is characterized in that described mineral alkali is sodium bicarbonate, yellow soda ash, salt of wormwood, potassium hydroxide, sodium hydroxide or ammoniacal liquor.
6. method as claimed in claim 1 or 2, the mass ratio that it is characterized in that the nitrobenzene compounds shown in described mineral alkali and the formula I is 0.05～2:1.
7. method as claimed in claim 1 or 2, the mass ratio that it is characterized in that the nitrobenzene compounds shown in described loaded noble metal catalyst and the formula I is 0.01～0.3:1.
8. method as claimed in claim 1 or 2, the mass ratio that it is characterized in that nitrobenzene compounds shown in the described formula I and reaction solvent is 1:5～35.
9. the method for claim 1, it is characterized in that described reaction solution post-treating method is: after reaction finishes, reacting liquid filtering, the aqueous ethanolic solution recrystallization with volumetric concentration 20%～70% behind the filtrate steaming removal solvent makes the benzylideneaniline compounds shown in the formula II.
10. method as claimed in claim 1 or 2, it is characterized in that described method is: the ratio according to nitrobenzene compounds and phenylcarbinol amount of substance is 1:5～30, the mass ratio of nitrobenzene compounds and reaction solvent is 1:5～35, the quality of mineral alkali is 0.05～2.0 times of nitrobenzene compounds quality, the consumption of loaded noble metal catalyst is 0.01～0.3 times of nitrobenzene compounds quality, with nitrobenzene compounds, phenylcarbinol, reaction solvent, mineral alkali adds reactor, air in the logical nitrogen replacement reactor also keeps nitrogen atmosphere, intensification remains on 50～240 ℃, stirring reaction 1～30 hour, reaction finishes afterreaction liquid filters, and the aqueous ethanolic solution recrystallization with volumetric concentration 70% behind the filtrate steaming removal solvent makes the benzylideneaniline compounds shown in the formula II.
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| WO2015013957A1 (en) * | 2013-08-01 | 2015-02-05 | 中国科学技术大学 | Method for preparing nitrogen-containing aromatic compound through catalytic pyrolysis from organic materials |
| CN105195140A (en) * | 2015-09-17 | 2015-12-30 | 浙江工业大学 | Palladium/alkali metal compound supported catalyst and preparation method and application thereof |
| CN106608847A (en) * | 2015-10-21 | 2017-05-03 | 中国科学院大连化学物理研究所 | Preparation method for imine |
| CN107029759A (en) * | 2016-02-01 | 2017-08-11 | 苏州大学 | Application of the ruthenium trichloride in catalysis nitrobenzene compounds and alcohol compound reaction prepare imines |
| CN108689786A (en) * | 2018-05-08 | 2018-10-23 | 中国科学院青岛生物能源与过程研究所 | A method of borrowing hydrogen reduction coupling synthesizing imine and aminated compounds |
| CN113145152A (en) * | 2021-02-01 | 2021-07-23 | 重庆工商大学 | Visible light catalysis one-pot multidirectional chemoselectivity N-alkylation method |
| CN114453020A (en) * | 2021-12-30 | 2022-05-10 | 浙江微通催化新材料有限公司 | Carbon-supported Pd-Ru-ILs catalyst, and preparation method and application thereof |
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| US9975859B2 (en) | 2013-08-01 | 2018-05-22 | University Of Science And Technology Of China | Method for preparing nitrogen-containing aromatic compound by catalytic pyrolysis of organic material |
| CN104520271A (en) * | 2013-08-01 | 2015-04-15 | 中国科学技术大学 | Method for preparing nitrogen-containing aromatic compound through catalytic pyrolysis from organic material |
| CN104520271B (en) * | 2013-08-01 | 2017-03-22 | 中国科学技术大学 | Method for preparing nitrogen-containing aromatic compound through catalytic pyrolysis from organic material |
| WO2015013957A1 (en) * | 2013-08-01 | 2015-02-05 | 中国科学技术大学 | Method for preparing nitrogen-containing aromatic compound through catalytic pyrolysis from organic materials |
| CN105195140A (en) * | 2015-09-17 | 2015-12-30 | 浙江工业大学 | Palladium/alkali metal compound supported catalyst and preparation method and application thereof |
| CN106608847A (en) * | 2015-10-21 | 2017-05-03 | 中国科学院大连化学物理研究所 | Preparation method for imine |
| CN106608847B (en) * | 2015-10-21 | 2019-09-06 | 中国科学院大连化学物理研究所 | A method of preparing imines |
| CN107029759A (en) * | 2016-02-01 | 2017-08-11 | 苏州大学 | Application of the ruthenium trichloride in catalysis nitrobenzene compounds and alcohol compound reaction prepare imines |
| CN107029759B (en) * | 2016-02-01 | 2019-11-26 | 苏州大学 | Ruthenium trichloride reacts the application prepared in imines with alcohol compound in catalysis nitrobenzene compounds |
| CN108689786A (en) * | 2018-05-08 | 2018-10-23 | 中国科学院青岛生物能源与过程研究所 | A method of borrowing hydrogen reduction coupling synthesizing imine and aminated compounds |
| CN108689786B (en) * | 2018-05-08 | 2021-08-27 | 中国科学院青岛生物能源与过程研究所 | Method for synthesizing imine and amine compounds by hydrogen reduction coupling |
| CN113145152A (en) * | 2021-02-01 | 2021-07-23 | 重庆工商大学 | Visible light catalysis one-pot multidirectional chemoselectivity N-alkylation method |
| CN113145152B (en) * | 2021-02-01 | 2022-05-27 | 重庆工商大学 | Visible light catalysis one-pot multidirectional chemoselectivity N-alkylation method |
| CN114453020A (en) * | 2021-12-30 | 2022-05-10 | 浙江微通催化新材料有限公司 | Carbon-supported Pd-Ru-ILs catalyst, and preparation method and application thereof |
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