- Palladium on Polydopamine: Its True Potential in Catalytic Transfer Hydrogenations and Heck Coupling Reactions
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The application of Pd–polydopamine and magnetic Fe3O4@Pd–polydopamine catalysts in catalytic transfer hydrogenation reactions and the Heck arylation is reported. The reduction of a wide range of aromatic nitro-compounds bearing both electron-donating and -withdrawing substituents to the corresponding anilines could be efficiently performed, although the reduction of carbonyl compounds was found to be less general. In the latter case, only aromatic ketones could be reduced to the corresponding alcohols, whereas aldehyde substrates were unaffected, which may be owing to their reaction with the catalyst support leading to catalyst deactivation. By using magnetic Fe3O4@Pd–polydopamine system, facilitated catalyst recovery and reuse for five consecutive cycles without considerable loss of activity in nitro-group reduction. The efficiency of the catalyst in Heck reactions was comparable to that in transfer hydrogenation, however, no catalytic activity was observed upon reuse in this case, likely as a result of metal leaching. We also explored tandem Heck reaction/catalytic transfer hydrogenation sequences, however, the two reactions showed limited compatibility under the applied conditions.
- Kunfi, Attila,Szabó, Vivien,Mastalir, ágnes,Bucsi, Imre,Mohai, Miklós,Németh, Péter,Bertóti, Imre,London, Gábor
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- Metal-free Reduction of Nitro Aromatics to Amines with B 2 (OH) 4 /H 2 O
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A metal-free reduction of nitro aromatics mediated by diboronic acid with water as both the hydrogen donor and solvent under mild conditions has been developed. A series of aromatic amines were obtained with good functional group tolerance and in good yields.
- Chen, Danyi,Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Liu, Qixing,Zhang, Kaili,Uozumi, Yasuhiro
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- Water as a hydrogen source in palladium-catalyzed reduction and reductive amination of nitroarenes mediated by diboronic acid
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An unprecedented palladium-catalyzed chemoselective reduction and reductive amination of nitroarenes with water as a hydrogen source mediated by diboronic acid have been discovered. A series of aryl amines containing various reducible functional groups were obtained in good to excellent yields.
- Zhou, Yanmei,Zhou, Haifeng,Liu, Sensheng,Pi, Danwei,Shen, Guanshuo
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- Transition-metal-free access to primary anilines from boronic acids and a common +NH2 equivalent
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Diversely substituted anilines are prepared by treatment of functionalized arylboronic acids with a common, inexpensive source of electrophilic nitrogen (H2N-OSO3H, HSA) under basic aqueous conditions. Electron-rich substrates are found to be the most reactive by this method. However, even moderately electron-poor substrates are well tolerated under the room temperature conditions. Sterically hindered substrates appear to be equally effective compared to unhindered ones. Highly electron-deficient substrates afford product in very low yields at room temperature, but moderate to good yields are obtained at refluxing temperatures. Our method is also amenable to electrophilic amination of several common boronic acid derivatives (e.g., pinacol esters). We demonstrate that it can be combined with metal-halogen exchange reactions or a variety of directed ortho metalation protocols in a "one-pot" sequence for the synthesis of aromatic amines with unique substitution patterns. DFT studies, in combination with experimental results, suggest that the reaction occurs via base-mediated activation of HSA, followed by 1,2 aryl B-N migration. This mode of activation appears to be critical for the success of the reaction and allows, for the first time, a general, electrophilic amination of boronic acids at ambient temperature.
- Voth, Samantha,Hollett, Joshua W.,Mccubbin, J. Adam
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- Methoxy aniline compound and synthesis method thereof
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The invention mainly relates to a preparation method of anisidine. According to the technical scheme, under the promotion of the photocatalyst and blue light, in the argon atmosphere, nitro compounds and methanol generate methoxyaniline, wherein products and additional products with stable molecular structures and excellent chemical properties are prepared, wherein a photocatalyst and a blue light source are used in the method, and a new path is provided for synthesis of methoxyaniline compounds. The method has the characteristics of mild reaction conditions, simple reaction system, less reaction equipment, simplicity and convenience in experimental operation and the like. The methoxyaniline derivative and the synthetic method thereof can be applied to a plurality of industrial production fields of dyes, pesticides, medicines, rubber additives and the like. The method is particularly suitable for scientific research, development and utilization of efficient and selective synthesis of methoxyaniline compounds by a one-pot method.
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Paragraph 0027; 0030-0032; 0041-0042
(2021/05/19)
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- Method for reducing aromatic nitro into arylamine
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The invention relates to a method for reducing aromatic nitro to arylamine. The method comprises the following steps: (1) taking an aromatic nitro compound as a raw material, water as a hydrogen source, a palladium compound, cheap and easy to obtain, as a catalyst and tetrahydroxydiboron as an additive to reduce nitro to obtain a product; (2) taking the aromatic nitro compound as the raw material, a copper salt, cheap and easy to obtain, as the catalyst, the tetrahydroxydiboron as the additive to reduce the nitro to obtain a product; and (3) taking the aromatic nitro compound as the raw material, water as the hydrogen source, and the tetrahydroxydiboron as the additive, without needing a metal catalyst, to reduce the nitro to obtain a product. A preparation method for the arylamine, which is provided by the invention, is mild in reaction condition, low in costs, environment-friendly, high in yield, and suitable for industrial production.
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Paragraph 0113-0116
(2020/07/15)
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- Synthesis method of aminobenzoate compound (by machine translation)
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The synthesis method comprises the following steps: carrying out a hydrogenation reduction reaction of a nitroanisole compound with a carbon-coated nickel containing alkaline earth metal in a hydrogen atmosphere; wherein the shell layer is a graphitized carbon layer containing alkaline earth metal, nitrogen and oxygen. To the method, the alkaline earth metal-containing carbon-coated nano composite material is used as a catalyst, the carbon material and the nickel nanoparticles cooperate to play a good catalytic effect, and the alkaline earth metal of the shell layer further synergistically improves the catalytic performance of the material. (by machine translation)
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Paragraph 0094-0098; 0137-0139
(2020/08/09)
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- Synthesis method of amino-anisole compound
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The invention provides a synthesis method of an amino-anisole compound. The synthesis method comprises the following steps: taking a carbon-coated nickel nano composite material containing alkali metals as a catalyst, and catalyzing a hydrogenation reduction reaction of a nitro-anisole compound in a hydrogen atmosphere; wherein the nano composite material contains a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer containing alkali metals, nitrogen and oxygen, and the inner core is nickel nano particles. According to the method, the nanocomposite material is used as a catalyst; a carbon material and the nickel nano particles generate a synergistic effect and a good catalytic effect, the alkali metals of the shell layer further synergistically improve the catalytic performance of the nano composite material, and the catalyst is used for hydrogenation reduction of nitro-anisole compounds to synthesize amino-anisole compounds, and has excellent activity, selectivity and safety.
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Paragraph 0147-0149
(2020/08/09)
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- Synthesis method of amino-anisole compound
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The invention provides a synthesis method of an amino-anisole compound. The synthesis method comprises the following steps: taking a carbon-coated nickel nano composite material containing alkali metals as a catalyst, and catalyzing a hydrogenation reduction reaction of a nitro-anisole compound in a hydrogen atmosphere; wherein the nano composite material contains a core-shell structure with a shell layer and an inner core, the shell layer is a graphitized carbon layer containing alkali metals and oxygen, and the inner core is nickel nano particles. According to the method, the nano compositematerial is used as a catalyst; a carbon material and the nickel nano particles generate a synergistic effect and a good catalytic effect, the alkali metals of the shell layer further synergisticallyimprove the catalytic performance of the nano composite material, and the catalyst is used for hydrogenation reduction of nitro-anisole compounds to synthesize amino-anisole compounds, and has excellent activity, selectivity and safety.
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Paragraph 0057; 0154-0156
(2020/08/09)
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- Direct synthesis of anilines and nitrosobenzenes from phenols
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A one-pot synthesis of anilines and nitrosobenzenes from phenols has been developed using an ipso-oxidative aromatic substitution (iSOAr) process. The products are obtained in good yields under mild and metal-free conditions. The leaving group effect on reactions that proceed through mixed quionone monoketals has also been investigated and a predictive model has been established.
- St Amant,Frazier,Newmeyer,Fruehauf,Read De Alaniz
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p. 5520 - 5524
(2016/07/06)
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- Assembly of Primary (Hetero)Arylamines via CuI/Oxalic Diamide-Catalyzed Coupling of Aryl Chlorides and Ammonia
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A general and practical catalytic system for aryl amination of aryl chlorides with aqueous or gaseous ammonia has been developed, with CuI as the catalyst and bisaryl oxalic diamides as the ligands. The reaction proceeds at 105-120°C to provide a diverse set of primary (hetero)aryl amines in high yields with various functional groups.
- Fan, Mengyang,Zhou, Wei,Jiang, Yongwen,Ma, Dawei
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supporting information
p. 5934 - 5937
(2015/12/11)
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- Palladium-catalyzed amination of aryl chlorides and bromides with ammonium salts
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We report the palladium-catalyzed coupling of aryl halides with ammonia and gaseous amines as their ammonium salts. The coupling of aryl chlorides and ortho-substituted aryl bromides with ammonium sulfate forms anilines with higher selectivity for the primary arylamine over the diarylamine than couplings with ammonia in dioxane. The resting state for the reactions of aryl chlorides is different from the resting state for the reactions of aryl bromides, and this change in resting states is proposed to account for a difference in selectivities for reactions of the two haloarenes.
- Green, Rebecca A.,Hartwig, John F.
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supporting information
p. 4388 - 4391
(2015/01/08)
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- BRIDGED BICYCLIC COMPOUNDS FOR THE TREATMENT OF BACTERIAL INFECTIONS
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Novel bridged bicyclic compounds are disclosed herein, along with their pharmaceutically acceptable salts, hydrates and prodrugs. Also disclosed are compositions comprising such compounds, methods of preparing such compounds and methods of using such compounds as antibacterial agents. The disclosed compounds, their pharmaceutically acceptable salts, hydrates and prodrugs, as well as compositions comprising such compounds, salts, hydrates and prodrugs, are useful for treating bacterial infections and associated diseases and conditions.
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Page/Page column 279
(2013/03/26)
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- NOVEL CATALYSTS
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The present invention provides novel compounds and ligands that are useful in transition metal catalyzed cross-coupling reactions. For example, the compounds and ligands of the present invention are useful in palladium or gold catalyzed cross-coupling reactions.
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Page/Page column 61-62
(2012/06/01)
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- A P,N-Ligand for palladium-catalyzed ammonia arylation: Coupling of deactivated aryl chlorides, chemoselective arylations, and room temperature reactions
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(Figure Presented) Amazing ammonia: A new air-stable P,N-ligand (Mor-DalPhos) is reported that enables the palladium-catalyzed crosscoupling of ammonia to a variety of aryl chloride and aryl tosylate substrates with high chemoselectivity and, for the first time, at room temperature (see scheme; Ad = adamantyl, Ts=para-toluenesulfonyl).
- Lundgren, Rylan J.,Peters, Brendan D.,Alsabeh, Pamela G.,Stradiotto, Mark
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supporting information; experimental part
p. 4071 - 4074
(2010/07/05)
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- CuI/4-hydro-L-proline as a more effective catalytic system for coupling of aryl bromides with N-boc hydrazine and aqueous ammonia
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(Chemical Equation Presented) CuI/4-hydroxy-L-proline-catalyzed coupling of aryl bromides and N-Boc hydrazine takes place in DMSO at 80°C to give N-aryl hydrazides. When aryl iodides are employed, this reaction completes at 50°C and no ligand is required. Under the catalysis of CuI/4-hydroxy-L- proline, the coupling reaction of aqueous ammonia with aryl bromides proceeds smoothly at 50°C to afford primary arylamines. In this case K 2CO3 is found as a better base than Cs2CO 3. These processes allow assembly of N-aryl hydrazides and primary arylamines that bear a wide range of functional groups including hydroxyl, amine, trifluoromethyl, ester, nitro, and ketone.
- Jiang, Liqin,Lu, Xu,Zhang, Hui,Jiang, Yongwen,Ma, Dawei
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experimental part
p. 4542 - 4546
(2009/09/25)
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- Method for preparing aromatic secondary amino compound
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Disclosed are (1) a method for preparing an aromatic secondary amino compound which comprises reacting an N-cyclohexylideneamino compound in the presence of a hydrogen moving catalyst and a hydrogen acceptor by the use of a sulfur-free polar solvent and/or a cocatalyst, and (2) a method for preparing an aromatic secondary amino compound which comprises reacting cyclohexanone or a nucleus-substituted cyclohexanone, an amine and a nitro compound corresponding to the amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst, a cocatalyst being added or not added. In a further aspect, a method is provided for the preparation of aminodiphenylamine by reacting phenylenediamine and cyclohexanone in the presence of a hydrogen transfer catalyst in a sulfur-free polar solvent while using nitroaniline as a hydrogen acceptor.
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- Method for preparing aromatic secondary amino compound
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Disclosed are (1) a method for preparing an aromatic secondary amino compound which comprises reacting an N-cyclohexylideneamino compound in the presence of a hydrogen moving catalyst and a hydrogen acceptor by the use of a sulfur-free polar solvent and/or a cocatalyst, and (2) a method for preparing an aromatic secondary amino compound which comprises reacting cyclohexanone or a nucleus-substituted cyclohexanone, an amine and a nitro compound corresponding to the amine in a sulfur-free polar solvent in the presence of a hydrogen moving catalyst, a cocatalyst being added or not added.
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- Collisionally induced dissociation in the study of A-ring hydroxylated vitamin D type compounds
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Colllslonally Induced dissociation (CID) is often used to determine the structure of ions based on comparison with the CID spectra of known ions. The latter are generated from Judiciously selected compounds taking into account basic principles of Ion chemistry. We report here on the use of this approach toward determination of the site of A-ring hydroxylation of vitamin D. Although not Intrinsically an aromatic compound, vitamin D gives rise in its mass spectrum to an aromatic methytstyryl cation at mlz 118. A-ring hydroxylated metabolites of vitamin D would thus Incorporate the extra OH group on the ion at mlz 118, shifting it to mlz 134. The position of substitution of the extra OH group on a metabolite could then be ascertained by comparing the CID spectrum of its mlz 134 fragment to those of the four possible (hydroxymethyl)styryl cations generated from synthesized authentic compounds. Because of their propensity to polymerize, these cations were generated in situ via the McLafferty rearrangement of the corresponding (hydroxyphenyl)ethanols. For optimum differentiation of Isomeric Ions, preparation of permethylated derivatives of vitamin D was necessary. The validity of the hypothesis was verified using 1,25-dihydroxy-vitamin D3 as a test compound. This method provides a viable approach for the characterization of A-ring hydroxylated metabolites of vitamin D as well as for related aromatic compounds.
- Young, David C.,Vouros, Paul,Holick, Michael F.,Higuchi, Tetsuo
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p. 837 - 842
(2007/10/02)
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- Antibacterial water-soluble cutting fluids resistant to yeast-like fungi
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A bactericide is added to conventional water-soluble cutting fluids to suppress deterioration by micro-organisms. Such fluids are however accompanied by the drawbacks that the bactericide has a narrow antibacterial spectrum and moreover its effects last a short time. It is the object of the present invention to offers water--soluble cutting fluids which remain resistant to a wide variety of microorganisms for a long time. The present invention therefore offers water-soluble cutting fluids to which has been added a specific amine selected from amines known to date.
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- ONE-POT CHEMOSELECTIVE REDUCTIVE ALKYLATION OF NITROARENES: A NEW GENERAL METHOD OF SYNTHESIS OF ALKYLANILINES.
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A New facile and general synthesis of alkylanilines by one-pot reductive alkylation of nitroarenes is reported.This method is based on the "in situ" reduction by hydrides (LiAlH4 or NaBH4) in the presence of catalytic amounts of Pd/C, of nitronate adducts arising from the conjugate addition of Grignard reagents to mononitroarenes.LiAlH4 showed to be a more efficient but less selective reducing agent than NaBH4.The reaction can be successfully applied to mono, homo and hetero bicyclic systems and allows to introduce a large variety of alkyl chains without isomerisation phenomena.
- Bartoli, Giuseppe,Bosco, Marcella,Pozzo, Renato Dal,Petrini, Marino
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p. 4221 - 4226
(2007/10/02)
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- Process for producing 4-alkoxyanilines
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4-Alkoxyanilines are obtained industrially advantageously by catalytically hydrogenating a nitrobenzene in the presence of a noble metal catalyst in a mixed solvent containing a lower aliphatic alcohol, sulfuric acid, and water or a lower aliphatic carboxylic acid or both to induce hydrogenation and a Bamberger-type rearrangement reaction. The mixed solvent contains at least 10 moles, preferably 30 to 60 moles, of the lower aliphatic alcohol per mole of the nitrobenzene, 1 to 10 moles, preferably 2 to 7 moles, of sulfuric acid per mole of the nitrobenzene, and 2 to 30% by weight, preferably 3 to 10% by weight, of water, the lower aliphatic carboxylic acid or both.
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