- One-pot reductive amination of carboxylic acids: a sustainable method for primary amine synthesis
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The reductive amination of carboxylic acids is a very green, efficient and sustainable method for the production of (bio-based) amines. However, with current technology, this reaction requires two to three reaction steps. Here, we report the first (heterogeneous) catalytic system for the one-pot reductive amination of carboxylic acids to amines, with solely H2 and NH3 as the reactants. This reaction can be performed with relatively cheap ruthenium-tungsten bimetallic catalysts in the green and benign solvent cyclopentyl methyl ether (CPME). Selectivities of up to 99% for the primary amine could be achieved at high conversions. Additionally, the catalyst is recyclable and tolerant for common impurities such as water and cations (e.g. sodium carboxylate).
- Coeck, Robin,De Vos, Dirk E.
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supporting information
p. 5105 - 5114
(2020/08/25)
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- Direct ortho-Selective Amination of 2-Naphthol and Its Analogues with Hydrazines
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Described herein is a regioselective ortho-amination of 2-naphthol and its analogues with substituted hydrazines. It provides a direct methodology for the synthesis of N-arylaminated naphthol derivatives without the formation of related 1,1′-biaryl-2,2′-diamine or carbazole byproducts. Specifically, using N,N-disubstituted hydrazine precursors, N-unsubstituted ortho-aminated derivatives and related secondary amines can be formed in ethylene glycol in moderate to excellent yields. Variation of substrates to N,N′-diarylhydrazines and N-methyl-N,N′-diarylhydrazines led to N-aryl-1-amino-2-naphthol compounds. It is noted that biologically interesting indazole motifs can be facilely created by the reaction of N,N′-dialkylhydrazines with 2-naphthols. These ortho-amination reactions have the advantage of one-pot operation without the use of transition metal catalysts.
- Jia, Lei,Tang, Qiang,Luo, Meiming,Zeng, Xiaoming
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p. 5082 - 5091
(2018/05/15)
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- Continuous Production of Dialkylamines by Selective Hydrogenation of Nitriles on a Nickel-Zeolite Catalyst
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Hydrogenation of aliphatic nitriles in the presence of nickel supported by NaX zeolite was studied. The data obtained were used to develop a continuous method for obtaining dialkylamines with the yield of the target product of up to 98%.
- Popov, Yu. V.,Mokhov,Latyshova,Panov,Pletneva, M. Yu.
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p. 1778 - 1782
(2018/03/21)
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- Colloid and nanosized catalysts in organic synthesis: XVI.1 Continuous hydrogenation of carbonitriles catalyzed by nickel nanoparticles applied on a support
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Conversion of the starting nitriles and selectivity of the products formation during continuous hydrogenation of various nitriles catalyzed by Ni0/Ceokar-2 have been studied as functions of temperature. Performing the process at temperature 120–260°С has led to the formation of a mixture of products containing di- and trialkylamines as well as the corresponding imines and enamines.
- Popov, Yu. V.,Mokhov,Latyshova,Nebykov,Panov,Pletneva, M. Yu.
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p. 2276 - 2281
(2017/11/24)
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- Colloid and nanosized catalysts in organic synthesis: XVII. Reductive amination of carbonitriles in the presence of supported nickel nanoparticles
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Reductive amination of carbonitriles catalyzed by nickel nanoparticles applied onto a solid support in a plug flow reactor in the gas phase or the gas–liquid–solid catalyst system occurs at atmospheric pressure of hydrogen affording the nonsymmetrical secondary or tertiary amines. The effect of the support type on the target product yield and conversion of the substrate has been studied.
- Popov, Yu. V.,Mokhov,Latyshova,Panov,Shirkhanyan
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p. 2546 - 2551
(2017/12/26)
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- Colloid and nanosized catalysts in organic synthesis: XII. Hydrogenation of carbonitriles catalyzed by nickel nanoparticles
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Hydrogenation of carbonitriles catalyzed by nickel nanoparticles in isopropanol proceeds under atmospheric pressure of hydrogen within 6-15 h to yield mainly secondary amines. Hydrogenation of α-aminonitriles results in reductive decyanation. β-Aminonitriles undergo hydrogenolysis at the nitrogen-carbon bond.
- Mokhov,Popov,Shcherbakova
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p. 273 - 280
(2016/04/20)
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- Reduction of hydrazines to amines with low-valent titanium reagent
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The N,N bond cleavage in hydrazines to amines via low-valent titanium reagent prepared in situ by treatment of TiCl4 with Mg powder in THF or CH2Cl2-Et2O is described. The reaction proceeds smoothly under mild conditions to afford amines in good to excellent yields with diverse functional group tolerance such as chloride, methoxyl, benzyloxyl, ester, acyl, as well as C,C double bonds and benzyl-nitrogen bonds. ARKAT-USA, Inc.
- Ren, Fang,Zhang, Yan,Hu, Lan,Luo, Meiming
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p. 165 - 173
(2013/06/27)
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- Catalytic hydrogenation of amides to amines under mild conditions
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Under (not so much) pressure: A general method for the hydrogenation of tertiary and secondary amides to amines with excellent selectivity using a bimetallic Pd-Re catalyst has been developed. The reaction proceeds under low pressure and comparatively low temperature. This method provides organic chemists with a simple and reliable tool for the synthesis of amines. Copyright
- Stein, Mario,Breit, Bernhard
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supporting information
p. 2231 - 2234
(2013/03/28)
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- An efficient synthesis of tertiary amines from nitriles in aprotic solvents
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Tertiary amines are utilized extensively as non-nucleophilic proton scavengers for a number of organic transformations. Herein we report the efficient syntheses of tertiary alkyl amines from their corresponding alkyl nitriles in the presence of a heterogeneous palladium catalyst and a source of dihydrogen in aprotic solvents. The reaction is atom economic, the conditions are mild, and the isolated yields are virtually quantitative. The degree of amine alkylation shows some solvent dependency; in polar protic solvents such as ethanol or methanol, the reaction affords a mixture of products with the secondary alkyl amine as the major product.
- Shares, Jonathan,Yehl, Jenna,Kowalsick, Amanda,Byers, Philip,Haaf, Michael P.
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scheme or table
p. 4426 - 4428
(2012/09/25)
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- Reduction of hydrazines to amines with aqueous solution of titanium(iii) trichloride
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N-N bond cleavage in hydrazines is widely used in the preparation of amines and thus occupies a significant place in organic synthesis. In this paper, we report a new method for the reductive cleavage of N-N bonds in hydrazines by commercially available and cheap aqueous titanium(iii) trichloride. The reaction proceeds smoothly under a broad pH range from acidic to neutral and basic conditions to afford amines in good yields. This method is compatible with substrates containing functionalities such as C-C double bonds, benzyl-nitrogen bonds, benzyloxy and acyl groups. The Royal Society of Chemistry 2011.
- Zhang, Yan,Tang, Qiang,Luo, Meiming
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supporting information; experimental part
p. 4977 - 4982
(2011/08/05)
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- Formation of secondary or tertiary aliphatic amines in aqueous media
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Secondary and tertiary amines can be easily obtained from primary and secondary amines, respectively, in completely aqueous media, in the presence of a bicatalytic system formed of cheap commercial aluminum (Al) powder and 5% rhodium (Rh) or ruthenium (Ru) deposed on charcoal.
- Marieta Simion, Alina,Arimura, Takashi,Miyazawa, Akira,Simion, Cristian,Surya Prakash,Olah, George A.,Tashiro, Masashi
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scheme or table
p. 2859 - 2865
(2009/12/03)
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- A new method for N-N bond cleavage of N,N-disubstituted hydrazines to secondary amines and direct ortho amination of naphthol and its analogues
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An unexpected reaction of N,N-disubstituted hydrazine with naphthol and its analogues under simply thermal conditions has been disclosed. 2-Naphthol reacted with various N,N-disubstituted hydrazines under argon to afford 1-amino-2-naphthol and the corresponding secondary amines in excellent yields. Ortho amination of 2-naphthols, hydroxyquinoline, and naphthalenamine occurred when they reacted with N-methyl-N-phenylhydrazine. Copyright
- Tang, Qiang,Zhang, Chao,Luo, Meiming
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p. 5840 - 5841
(2008/09/19)
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- Reaction of primary amines with Pt/C catalyst in water under microwave irradiation: A convenient synthesis of secondary amines from primary amines
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Upon microwave irradiation in water, Pt/C converts primary amines into secondary amines in good yield via retro-reductive and reductive amination.
- Miyazawa, Akira,Saitou, Kaori,Tanaka, Kan,G?dda, Thomas M.,Tashiro, Masashi,Prakash, G. K. Surya,Olah, George A.
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p. 1437 - 1439
(2007/10/03)
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- Microwave-assisted direct transformation of amines to ketones using water as an oxygen source
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Retro-reductive animations, direct transformations of amines to ketones, were catalyzed by Pd/C in water under microwave irradiation. The Royal Society of Chemistry 2005.
- Miyazawa, Akira,Tanaka, Kan,Sakakura, Toshiyasu,Tashiro, Masashi,Tashiro, Hideki,Surya Prakash,Olah, George A.
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p. 2104 - 2106
(2007/10/03)
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- Preparation of amines
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A process for preparing an amine by catalytic reaction of an olefin with ammonia or a primary or secondary amine by contacting a mixture of the reactants in a reactor at 200° to 400° C. and an elevated pressure up to 700 bar in the presence of a catalyst consisting essentially of an X-ray amorphous (non-crystalline) mesoporous catalyst, some of which may have a microporous non-crystalline content. The catalyst has the composition where Q is at least one of the trivalent elements aluminum, boron, chromium, iron or gallium, and M is at least one of the tetravalent elements silicon, titanium or germanium. The molar ratio of a:b is from 0.5:1 to 1000:1 and the molar ratio of c:b is from 0 to 2:1. As prepared and used in the process, this non-crystalline catalyst has a specific BET surface area of from 200 to 1000 m2 /g.
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- Convenient preparations of imines and symmetrical secondary amines possessing primary or secondary alkyl groups
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Hindered alkyl aldehydes react with benzotriazole and ammonia in dry ethanol or methanol to yield the corresponding bis[1-(benzotriazol-1-yl)alkyl]amines 2. The reaction of aryl aldehydes, however, yields 1-(benzotriazol-1-yl)-N-alkylidenealkylamines 3. The reactions of adducts 2 and 3 with lithium aluminum hydride furnishes dialkyl- and dibenzylamine derivatives 4. Although the reactions of 2 and 3 with organometallic reagents are not as general, in several cases the reactions of amines 2 with Grignard reagents yield 1-alkyl or aryl substituted N-alkylidenealkylamines 5. Similar reactions of amines 2 with phenyl lithium afford 1,1'-diphenyldialkylamines 7.
- Katritzky,Zhao,Hitchings
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p. 703 - 708
(2007/10/02)
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- RELATIONSHIPS OF TRANSAMINATION OF SUBSTITUTED UREAS. V. THERMODYNAMICS OF TRANSAMINATION OF DIARYLUREAS BY DIALKYLAMINES
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The equilibrium constant of the transamination of N,N'-diarylureas by dialkylamines in o-dichlorobenzene in the range of 120-158 deg C depends significantly on the nature of both reagents.The enthalpy of activation and the entropy of dissociation of diarylureas are proportional to the thermal effect of the transamination of these ureas by diisobutylamine.The same relationships is observed between the enthalpy of activation of the bimolecular reaction of N,N'-diphenylurea with dialkylamines and the enthalpy of the process.The established relationships between the enthalpies of activation and the enthalpy of equilibrium are explained satisfactorily in terms of the Hammond-Thornton model.
- Chimishkyan, A. L.,Gulyaev, N. D.,Leonova, T. V.
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- Denitrosation of Nitrosamines to Secondary Aliphatic Amines with Chlorosulphonyl Isocyanate
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A novel method for the denitrosation of nitrosamines with chlorosulphonyl isocyanates is described.
- Dhar, Durga N.,Bag, Amal K.
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- Antimicrobial composition and method containing N-(3,5-dihalophenyl)-imide compounds
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Novel N-(3,5-dihalophenyl)imide compounds, which exhibit a strong antimicrobial activity against microorganisms including phytopathogenic fungi, parasites of industrial products and pathogenic microorganisms, represented by the formula, STR1 wherein X and X' each represent halogens and A represents a substituted ethylene such as chloroethylene, C1 - C4 alkylthioethylene, C1 - C2 alkyl-ethylene or 1,2-di-C1 - C2 -alkyl-ethylene, a cyclopropylene such as 1,3-dimethylcyclopropylene, trimethylene, a cyclohexylene-1,2-, cyclohexenylene-1,2-, cyclohexadienylene-1,2- or o-phenylene. The N-(3,5-dihalophenyl)imide compounds can be obtained by any of methods which produce imide compounds or reaction of an N-(3,5-dihalophenyl)maleimide compound with a mercaptan, a hydrogen halide, phosphorus chloride or thionylchloride.
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