CN103539596A - Method for catalyzing transfer of hydrogen controllable reduction nitro-compound in formic acid or formate - Google Patents
Method for catalyzing transfer of hydrogen controllable reduction nitro-compound in formic acid or formate Download PDFInfo
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Abstract
The invention relates to a method for catalyzing the transfer of a hydrogen controllable reduction nitro-compound in formic acid or formate. Carbon nitride supported nano palladium or polymer semiconductor supported nano metal is used as a catalyst, the formic acid or formate is used as a hydrogen source, the reaction temperature is 0-15 DEG C, and the transfer of hydrogen in the formic acid or formate to a substrate nitro is efficiently catalyzed so as to selectively generate corresponding amine. Compared with the prior art, the method disclosed by the invention has the advantages that the reaction conditions are mild, the substrate conversion rate and product selectivity are high, the catalyst is easy to recover with good circularity, the system is environment-friendly and low in energy consumption, and the method has a vitally important value in industrial application.
Description
Technical field
The invention belongs to technology of fine chemicals, be specifically related to a kind of method that the controlled reduction unsaturated compounds of hydrogen in formic acid or formate is shifted in carbonitride loaded with nano palladium catalysis.Further for compound selectives such as carbonitride loaded nanometer palladium catalyst catalysis nitros, generate the method for corresponding amine.
Background technology
It is very important catalyzed reaction that selective catalysis nitro-compound hydrogenation generates amine, at chemical industry and pharmaceutical industry, is widely used.Amine is widely used in the fine chemical products such as synthetic drugs, dyestuff, polymkeric substance, sterilant, spices and tensio-active agent, biomass fuel.Direct-reduction nitro-compound is its conventional preparation means.Liquid and gas hydrogenation is industrial two kinds of production methods that generally adopt, and liquid-phase hydrogenatin makes its scope of application more extensive owing to not existing to the restriction of substrate boiling point, is particularly useful for small-scale fine chemicals as the production of the fine chemicals such as amine.
The method that realizes this hydrogenation process mainly comprises with (1) photo catalytic reduction, electrical catalyze reduction, take Sodium Sulphide, hydrazine hydrate, Selenium Sulfide, metal hydride is reductive agent reduction, these method reaction conditionss are gentle, technique is simple, but has the defect that conversion rate is low or reductive agent is expensive; (2) with the reductive agent of stoichiometric ratio as metallic reducings such as iron, zinc, aluminium, copper, the method productive rate is high, technique is simple, but the high product sepn process of by product is complicated, serious to environmental disruption; (3) take hydrogen as hydrogen source, precious metal or nickel-base catalyst catalytic substrate hydrogenation, the method scale is suitable for industrial application, however the commercial run based on hydrogen shortening has high energy consumption, expensive, the defect that selectivity is on the low side.Meanwhile, the decomposition transfer process of hydrogen needs high temperature, and speed is lower, and meanwhile, hydrogen has brought extra cost as the storage and transport process of industrial raw material for producing.
Another substituting catalytic hydrogenation process is to make nitro-compound hydrogenation by extracting and shift hydrogen atom from hydrogen donor molecule, compares traditional catalytic hydrogenation process and has obvious advantage.The method selects homogeneous phase or different-phase catalyst and hydrogen donor to form reaction system, under gentle reaction conditions, nitro-compound efficient selective is generated to amine.In optional hydrogen donor (hydrazine hydrate, alcohols, formic acid and formate etc.), the advantage such as biomass formic acid has low toxicity, good stability, cheap, output is large, is that very safe sustainability hydrogen source is used in a kind of accumulating.
In research in recent years, contain ruthenium, rhodium, palladium, copper, cobalt, the homogeneous catalyst of the metal centers such as molybdenum and iron (12875 pages of 133 phases of J.Am.Chem.Soc.2011) has shown very high activity in hydrogen transference shortening nitro-compound, its catalytic activity is directly related with specific organic ligand, yet it is less to take the example that formic acid is hydrogen source.And orgnometallic catalyst is very responsive to air and humidity, during reaction, must carry out noble gas protection, this has limited the prospect of its large-scale industrial application.Different-phase catalyst has the features such as reusability is good and receives publicity as the catalyzer of the nanoparticles such as nickel-base catalyst or gold-supported, platinum, palladium, as Raney's nickel is used to the hydrogen transference of catalysis formic acid to nitro-compound, but the method exists catalyzer soluble, the defects (2889 pages of 30 phases of Syn.Commun.2000) such as formic acid consumption is large, and reaction yield is low.Palladium-carbon catalyst is used to the hydrogen transference of catalysis formic acid to nitro-compound (709 pages of Ind.J.Chem.2000), but the method reaches 30% to 50% in the weight ratio of reaction time catalizer and substrate, and formic acid is greatly excessive, the easy inactivation of catalyzer.Titanium dichloride load golden nanometer particle catalyzer (281 pages of 353 phases of Adv.Synth.Catal.2011) is also used to catalysis formic acid nitro compound reducing, but this catalyzer transformation efficiency is very low, can not reach the requirement of Industrial Catalysis far away.Therefore, present stage is badly in need of a kind of efficient, the different-phase catalyst of catalysis formic acid (or formate) hydrogen transference.
We have proposed the new carbonitride loaded nanometer palladium catalyst of a class, further expand as polymer semiconductor's loaded with nano metal catalyst, can the hydrogen transference of efficient catalytic formic acid to amine corresponding to the single-minded generation of substrate nitro.Polymer semiconductor as substrate can divide three classes, carbonitride, doping carbon and conjugated polymer.Wherein carbonitride has with low costly as substrate, and preparation process is simple, is easy to from advantages such as reaction system separation.Carbonitride can regulate the electronic structure of metal nanoparticle simultaneously, and its surface amino groups has stabilization to noble metal active center; The dispersiveness of carbonitride in solvent is better, high to the affinity of organic substrates, and these are all that it improves the major reason of catalyst activity as substrate.Doping carbon material is the emerging carbon material of a class, when having carbon material advantage, also by introducing hetero-atoms, has regulated its electronic structure, has increased avtive spot, thereby has had the catalytic property different from carbon material, has broad application prospects.Conjugated polymer wide material sources, structural unit is abundant, and chemical property differs greatly, and can select suitable conjugated polymer to regulate reactive behavior as catalyst substrate for different catalyzed reactions, is a focus of studying at present.Present method is by selecting different catalyst substrate and metal catalytic center combination, realized gentle reaction conditions, high substrate conversion speed and selectivity of product, have that catalyzer is easy to reclaim, cyclicity is good simultaneously, the advantages such as system environment-friendly and green and less energy-consumption, have extremely important potential industrial application value.
Summary of the invention
Object of the present invention is exactly to provide a kind of method that solves the controlled reduction unsaturated organic compound of carbonitride loaded with nano Ba Huo polymer semiconductor loaded with nano metal catalysis of problem existing in original shortening commercial run in order to overcome the defect of above-mentioned prior art existence.
Object of the present invention can be achieved through the following technical solutions:
The method of the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis, take formic acid or formate as hydrogen source, at 0 ℃, at 150 ℃, in solvent, efficient catalytic formic acid or formate hydrogen transference to substrate nitro selectivity are generated to corresponding amine, specifically adopt following steps:
Take formic acid or formate as hydrogen source, control temperature of reaction is 0-150 ℃, in solvent, mix with nitro substrate, the mol ratio of controlling formic acid or formate and nitro substrate is 0.01:1-2000:1, the carbonitride loaded with nano Ba Huo polymer semiconductor loaded with nano metal of take is catalyzer, and the hydrogen transference of formic acid or formate to controlled reduction in nitro substrate is converted into corresponding aminated compounds.
Described formate is chemistry or the biological substance that contains formate, includes but not limited to lithium formate, sodium formiate, potassium formiate, ammonium formate, triethylammonium formate or formic acid triethanolamine salt.
Organic molecule or polymkeric substance that described nitro substrate contains nitro functions, include but not limited to fragrance, heterocycle or condensed ring nitro-compound.
As preferred embodiment, aromatic nitro compound is oil of mirbane or substituted aroma oil of mirbane, and heterocycle nitro-compound is nitrogen heterocyclic nitro-compound.
As the embodiment being more preferably; the substituting group of substituted aroma oil of mirbane pushes away electronics or electron-withdrawing group for one or more; described electron donating group is alkyl, alkoxyl group, amino methyl or hydroxyl, and described electron-withdrawing group is fluorine, acyl group, ketone group, nitro, carboxyl or the ester group being directly connected with aromatic ring.
The preferred 1:1-7:1 of mol ratio of described formic acid or formate and nitro substrate.
Described solvent includes but not limited to water, nitrogen nitrogen dimethylformamide, ethanol, acetonitrile, ethyl acetate or tetrahydrofuran (THF).
The preferred 10-50 ℃ of described temperature of reaction.
Palladium particle size in described carbonitride loaded nanometer palladium catalyst is 1-50nm, carrier is carbonitride, the weight ratio of palladium and carbonitride is 0.001:99.999-40:60, the metal adopting in described polymer semiconductor's loaded with nano metal catalyst is one or more in gold and silver, iridium, nickel, ruthenium, platinum or rhodium, metal particle size is 1-50nm, its carrier is nitrogen-doped graphene, polyacetylene, polyacrylonitrile, polyparaphenylene's acetylene, polyparaphenylene's second is rare or Polythiophene in one or more; The weight ratio of metal and carrier is 0.001:99.999-40:60.
As preferred embodiment, the preferred 8:92 of the weight ratio of palladium and carbonitride in carbonitride loaded nanometer palladium catalyst, the preferred 8:92 of weight ratio of metal and carrier in polymer semiconductor's loaded with nano metal catalyst.
Compared with prior art, the present invention using formic acid or formate with low cost as hydrogen donor, security is good, the gentle speed of reaction of reaction conditions is high, selectivity of product is high, and catalyzer easily reclaims, and cyclicity is good, environmental friendliness, energy consumption is low, has high industrial applications prospect.The more important thing is, the present invention is applicable to the catalystic converter system in any gas atmosphere, it is air atmosphere, high catalytic conversion and selectivity all can be provided in the systems such as inert gas atmosphere, the hydroformylation step that exists the formic acid of activation to deviate from due to palladium surface is transferred to nitro-compound, do not need through polystep reaction and various partial hydrogenation product, simultaneously, the direct electronic structure that can regulate palladium particle that contacts of carrier and palladium particle, carbonitride loaded nanometer palladium catalyst obtains high conversion rate and selectivity thus.
Accompanying drawing explanation
Fig. 1 is the X-ray diffraction spectrogram of carbonitride supported palladium nanoparticle powder;
Fig. 2 is the transmission electron microscope photo of carbonitride supported palladium nanoparticle.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
Semiconducting nitride carbon is dispersed in deionized water, floods for some time after adding the acid of appropriate chlorine palladium or chlorine palladium acid sodium solution.With sodium hydroxide solution, regulate and disperseed, after the chlorine palladium acid of semiconducting nitride carbon or the pH of chlorine palladium acid sodium solution, add reductive agent to reduce and wash, dry.
The chemical constitution of the carbonitride loaded nanometer palladium catalyst that the present invention prepares by aforesaid method is: palladium-carbonitride catalyzer that palladium massfraction is 0.1-40%.Fig. 1 is the carbonitride loaded nanometer palladium catalyst powder x-ray diffraction spectrogram of embodiment 1, has illustrated that a large amount of palladium metal (111) and (200) crystal face exist; Fig. 2 is the carbonitride loaded nanometer palladium catalyst catalyzer transmission electron microscope photo of embodiment 1, and the Pd nano particle of carbonitride institute load is less than 5nm as seen from the figure, and distribution of sizes is homogeneous relatively.The stable existence of nano level metal palladium particle is the major reason of carbonitride supported palladium nanoparticle high reaction activity.
Embodiment 2:
Respectively by nitrogen-doped graphene, polyacetylene, polyacrylonitrile, polyparaphenylene's acetylene, polyparaphenylene's second is rare and the polymer semiconductor such as Polythiophene is dispersed in deionized water, floods for some time after adding the acid of appropriate chlorine palladium or chlorine palladium acid sodium solution.With sodium hydroxide solution, regulate and disperseed, after the chlorine palladium acid of polymer semiconductor or the pH of chlorine palladium acid sodium solution, add sodium borohydride solution to reduce and wash, dry.
The chemical constitution of polymer semiconductor's nano Pd catalyst that the present invention prepares by aforesaid method is: polymer semiconductor's nano Pd catalyst that palladium massfraction is 0.001:99.999 to 40:60.
Embodiment 3:
Polymer semiconductor described in example 2 is dispersed in deionized water, floods for some time after adding respectively the appropriate solution containing gold and silver, iridium, nickel, ruthenium, platinum or rhodium.With sodium hydroxide solution, regulate after the pH of the solution containing gold and silver, iridium, nickel, ruthenium, platinum or rhodium that has disperseed semiconducting nitride carbon, add reductive agent to reduce and wash, dry.The chemical constitution of polymer semiconductor's loaded with nano metal catalyst that the present invention prepares by aforesaid method is: the catalyzer that the gold and silver of polymer semiconductor's load, iridium, nickel, ruthenium, platinum or rhodium massfraction are 0.001:99.999 to 40:60.
Embodiment 4:
By 0.5mmol oil of mirbane, 10mg8% palladium-carbonitride catalyzer adds 3.75mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 5:
By 0.5mmol oil of mirbane, 10mg8% palladium-carbonitride catalyzer adds respectively ultrasonic 30s in 5mL ethanol, acetonitrile, add pure formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 95% afterwards, and aniline selectivity is greater than 99%.
Embodiment 6:
By 0.5mmol oil of mirbane, 10mg8% palladium-carbonitride catalyzer adds respectively 5mL deionized water for ultrasonic 30s, add pure formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 7:
By 0.5mmol oil of mirbane, 10mg8% palladium-carbonitride catalyzer adds respectively 5mL deionized water for ultrasonic 30s, add 0.2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 8:
By 0.5mmol oil of mirbane, 10mg8% palladium-carbonitride catalyzer adds respectively 5mL deionized water for ultrasonic 30s, add 8M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 9:
By 0.5mmol oil of mirbane, 10mg8% palladium-carbonitride catalyzer adds 3.75mL deionized water for ultrasonic 30s, add 2M aqueous sodium formate solution to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 10:
By 2.5mmol oil of mirbane, 50mg8% palladium-carbonitride catalyzer adds respectively 25mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 11:
By 5mmol oil of mirbane, 100mg8% palladium-carbonitride catalyzer adds respectively 25mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 12:
By 0.5mmol oil of mirbane, 10mg0.1% palladium-carbonitride catalyzer adds respectively 5mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 13:
By 0.5mmol oil of mirbane, 10mg40% palladium-carbonitride catalyzer adds respectively 5mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 14:
By 0.5mmol ortho-methylnitrobenzene, meta-methylnitrobenzene, to methyl nitro, p-fluoronitrobenzene, to hydroxyl oil of mirbane, to methoxy nitrobenzene, 6-nitroquinoline, 2, 6-dimethyl nitrobenzene, nitro-naphthalene, 1, 3-dinitrobenzene, amino-3 methyl oil of mirbane of 2-, p-nitroacetophenone, methyl p-hydroxybenzoate, benzene, respectively add 3.75mL deionized water for ultrasonic 30s with 10mg8% palladium-carbonitride catalyzer respectively, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 93% afterwards, amine selectivity is greater than 99%.
Embodiment 15:
The catalyst recovery that repetition embodiment 4 is reacted after 1 time, add 0.5mmol oil of mirbane, 3.75mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 16:
The catalyst recovery that repetition embodiment 4 is reacted after 8 times, add 0.5mmol oil of mirbane, 3.75mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 17:
By 0.5mmol oil of mirbane, 10mg8% gold-carbonitride catalyzer adds respectively 25mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Embodiment 18:
By 0.5mmol oil of mirbane, 10mg8% palladium-Polythiophene catalyzer adds respectively 25mL deionized water for ultrasonic 30s, add 2M aqueous formic acid to start reaction, reaction finishes with gas-chromatography (fid detector) analytical results, to obtain result transformation efficiency and be greater than 99% afterwards, and aniline selectivity is greater than 99%.
Claims (10)
1. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis, it is characterized in that, the method adopts following steps: take formic acid or formate as hydrogen source, control temperature of reaction is 0-150 ℃, in solvent, mix with nitro substrate, the mol ratio of controlling formic acid or formate and nitro substrate is 0.01:1-2000:1, the carbonitride loaded with nano Ba Huo polymer semiconductor loaded with nano metal of take is catalyzer, and the hydrogen transference of formic acid or formate to controlled reduction in nitro substrate is converted into corresponding aminated compounds.
2. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis according to claim 1, it is characterized in that, described formate is chemistry or the biological substance that contains formate, includes but not limited to lithium formate, sodium formiate, potassium formiate, ammonium formate, triethylammonium formate or formic acid triethanolamine salt.
3. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis according to claim 1, it is characterized in that, organic molecule or polymkeric substance that described nitro substrate contains nitro functions, include but not limited to fragrance, heterocycle or condensed ring nitro-compound.
4. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis according to claim 3, it is characterized in that, aromatic nitro compound is oil of mirbane or substituted aroma oil of mirbane, and heterocycle nitro-compound is nitrogen heterocyclic nitro-compound.
5. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis according to claim 4; it is characterized in that; the substituting group of described substituted aroma oil of mirbane pushes away electronics or electron-withdrawing group for one or more; described electron donating group is alkyl, alkoxyl group, amino methyl or hydroxyl, and described electron-withdrawing group is fluorine, acyl group, ketone group, nitro, carboxyl or the ester group being directly connected with aromatic ring.
6. according to the catalysis described in any one in claim 1-5, shift the method for the controlled nitro compound reducing of hydrogen in formic acid or formate, it is characterized in that the preferred 1:1-7:1 of mol ratio of described formic acid or formate and nitro substrate.
7. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis according to claim 1, it is characterized in that, described solvent includes but not limited to water, nitrogen nitrogen dimethylformamide, ethanol, acetonitrile, ethyl acetate or tetrahydrofuran (THF).
8. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis according to claim 1, it is characterized in that the preferred 10-50 ℃ of described temperature of reaction.
9. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis according to claim 1, it is characterized in that,
Palladium particle size in described carbonitride loaded nanometer palladium catalyst is 1-50nm, and carrier is carbonitride, and the weight ratio of palladium and carbonitride is 0.001:99.999-40:60,
The metal adopting in described polymer semiconductor's loaded with nano metal catalyst is one or more in gold and silver, iridium, nickel, ruthenium, platinum or rhodium, metal particle size is 1-50nm, its carrier is nitrogen-doped graphene, polyacetylene, polyacrylonitrile, polyparaphenylene's acetylene, polyparaphenylene's second is rare or Polythiophene in one or more; The weight ratio of metal and carrier is 0.001:99.999-40:60.
10. the method for the controlled nitro compound reducing of hydrogen in formic acid or formate is shifted in catalysis according to claim 9, it is characterized in that,
The preferred 8:92 of weight ratio of palladium and carbonitride in described carbonitride loaded nanometer palladium catalyst,
The preferred 8:92 of weight ratio of metal and carrier in described polymer semiconductor's loaded with nano metal catalyst.
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| CN112920055B (en) * | 2021-02-01 | 2022-08-05 | 重庆工商大学 | Visible light catalytic one-pot hydrogenation and amidation method for nitroarene and carboxylic acid |
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| CN115364886B (en) * | 2022-06-20 | 2023-07-28 | 山东大学 | Plasma photocatalytic material and application thereof in carbon dioxide cycloaddition reaction |
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