- Method for promoting acylation of amine or alcohol by carbon dioxide
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The invention relates to a method for promoting acylation of amine or alcohol by carbon dioxide, which comprises the following steps of: mixing an amine compound, carboxylate or thiocarboxylate compound and a reaction solvent under the action of carbon dioxide, and reacting to obtain an amide compound, or under the action of carbon dioxide, mixing the alcohol compound, the thiocarboxylate compound and the reaction solvent [gamma]-valerolactone, and reacting to obtain the ester compound. According to the invention, under the promotion action of carbon dioxide, carboxylate or thiocarboxylate is used as an acylation reagent, and amine and alcohol are converted into amide and ester compounds in the absence of a transition metal catalyst, so that acylation reagents such as acyl chloride or anhydride with irritation and corrosivity are avoided; and the method has the advantages of simple operation, mild reaction conditions, high tolerance of substrate functional groups, strong applicability and high yield, and provides an efficient, reliable and economical preparation method for synthesis of amide and ester compounds.
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Paragraph 0033-0034
(2021/05/29)
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- Nickel-Catalyzed Hydrodeoxygenation of Aryl Sulfamates with Alcohols as Mild Reducing Agents
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The nickel-catalyzed hydrodeoxygenation of aryl sulfamates has been developed with alcohols as mild reductants. A variety of functional groups and heterocycles were tolerated in this reaction system to give the desired products in high yields. In addition, the gram-scale process and stepwise cine-substitution were also achieved with high efficiency.
- Matsuo, Kasumi,Kuriyama, Masami,Yamamoto, Kosuke,Demizu, Yosuke,Nishida, Koyo,Onomura, Osamu
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p. 4449 - 4460
(2021/08/25)
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- Meta Selective C-H Borylation of Sterically Biased and Unbiased Substrates Directed by Electrostatic Interaction
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An electrostatically directed meta borylation of sterically biased and unbiased substrates is described. The borylation follows an electrostatic interaction between the partially positive and negative charges between the ligand and substrate. With this strategy, it has been demonstrated that a wide number of challenging substrates, especially 4-substituted substrates, can selectively be borylated at the meta position. Moreover, unsubstituted substrates also displayed excellent meta selectivity. The reaction employs a bench-stable ligand and proceeds at a milder temperature, precluding the need to synthesize a bulky and sophisticated ligand/template.
- Chaturvedi, Jagriti,Haldar, Chabush,Bisht, Ranjana,Pandey, Gajanan,Chattopadhyay, Buddhadeb
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p. 7604 - 7611
(2021/05/26)
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- N-Alkylation of N-trimethylsilyl derivatives of lactams, amides, and imides with alkyl sulfonates
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The reaction of N-trimethylsilyl derivatives of amides and imides with alkyl sulfonates on heating affords the corresponding N-alkyl derivatives and trimethylsilyl sulfonates.
- Baukov, Yu. I.,Kramarova, E. P.,Negrebetsky, Vad. V.,Shagina, A. D.,Shipov, A. G.,Tarasenko, D. V.
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p. 398 - 400
(2020/04/15)
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- Amide Bond Formation Catalyzed by Recyclable Copper Nanoparticles Supported on Zeolite Y under Mild Conditions
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A series of catalysts based on supported copper nanoparticles have been prepared and tested in the amide bond formation from tertiary amines and acid anhydrides, in the presence of tert-butyl hydroperoxide as an oxidant. Copper nanoparticles on zeolite Y (CuNPs/ZY) was found to be the most efficient catalyst for the synthesis of amides, working in acetonitrile as solvent, under ligand- and base-free conditions in air. The products were obtained in good to excellent yields and in short reaction times. The CuNPs/ZY system also exhibited higher catalytic activity than some commercially available copper and iron sources and it was reused in ten reaction cycles without any further pre-treatment. This methodology has been successfully scaled-up to a gram scale with no detriment to the yield.
- Moglie, Yanina,Buxaderas, Eduardo,Mancini, Agustina,Alonso, Francisco,Radivoy, Gabriel
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p. 1487 - 1494
(2019/02/16)
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- N-Ethynylation of Anilides Decreases the Double-Bond Character of Amide Bond while Retaining trans-Conformation and Planarity
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Activated amide bonds have been attracting intense attention; however, most of the studied moieties have twisted amide character. To add a new strategy to activate amide bonds while maintaining its planarity, we envisioned the introduction of an alkynyl group on the amide nitrogen to disrupt amide resonance by nN→Csp conjugation. In this context, the conformations and properties of N-ethynyl-substituted aromatic amides were investigated by DFT calculations, crystallography, and NMR spectroscopic analysis. In contrast to the cis conformational preference of N-ethyl- and vinyl-substituted acetanilides, N-ethynyl-substituted acetanilide favors the trans conformation in the crystal and in solution. It also has a decreased double bond character of the C(O)?N bond, without twisting of the amide. N-Ethynyl-substituted acetanilides undergo selective C(O)?N bond or N?C(sp) bond cleavage reactions and have potential applications as activated amides for coupling reactions or easily cleavable tethers.
- Yamasaki, Ryu,Morita, Kento,Iizumi, Hiromi,Ito, Ai,Fukuda, Kazuo,Okamoto, Iwao
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supporting information
p. 10118 - 10122
(2019/07/05)
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- Method for preparing N-aryl tertiary amide with substituted Meldrum's acid as acylating agent in water phase
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The invention discloses a method for preparing N-aryl tertiary in a water phase. According to the method, water is used as the solvent, and substituted Meldrum's acid and N-aryl secondary amine react at 80-100 DEG C for 1-10 h to obtain the N-aryl tertiary. The molar ratio of substituted Meldrum's acid to N-aryl secondary amine is 1:10-10:1. The reaction concentration of substituted Meldrum's acid or N-aryl secondary amine is 0.5-4 mol/L. The method overcomes the defect that in the prior art, acyl chloride, anhydride, dehydration coupling reagent, organic solvent, phase transfer catalyst or metal catalyst needs to be adopted, and has the advantages that by using substituted Meldrum's acid as an acylating agent, pre-activating of carboxylic acid or using of a dehydration coupling reagent is avoided; due to the fact that substituted Meldrum's acid is easy to prepare, using of certain carboxylic acid and activated derivatives which are hard to get or expensive is avoided; water is used as the solvent, so that using of toxic organic solvent is avoided; no acid, alkali or metal catalyst is adopted, so that influences of acid and alkali on sensitive groups and equipment and metal ion residues in products are avoided. The synthesis method can play an important role in industrial production of N-aryl tertiary, especially N-aryl tertiary of complex carboxylic acid.
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Paragraph 0014; 0034
(2017/04/22)
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- Electrophilic Amination with Nitroarenes
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An exceptionally general electrophilic amination, which directly transforms commercially available nitroarenes into alkylated aromatic aminoboranes with zinc organyl compounds was developed. The reaction starts with a two-step partial reduction of the nitro group to a nitrenoid, which is used in situ as the electrophilic amination reagent. To facilitate isolation, the resulting air- and moisture-sensitive aminoboranes were reacted with a range of electrophiles. The method not only represents a direct transformation of nitro compounds into electrophilic amination reagents but also provides an elegant alternative to dehydrocoupling methods for the generation of aminoboranes.
- Rauser, Marian,Ascheberg, Christoph,Niggemann, Meike
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supporting information
p. 11570 - 11574
(2017/09/11)
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- N-Acyl-N-(4-chlorophenyl)-4-nitrobenzenesulfonamides: Highly selective and efficient reagents for acylation of amines in water
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A variety of N-acyl-N-(4-chlorophenyl)-4-nitrobenzenesulfonamides (1a-e) were synthesized in one pot from 4-chloroaniline under solvent-free conditions and have been developed as chemoselective N-acylation reagents. Selective protection of primary amines in the presence of secondary amines, acylation of aliphatic amines in the presence of aryl amines, and monofunctionalization of primary-secondary diamines as well as selective N-acylation of amino alcohols using these reagents are described. All of the acylation reactions were carried out in water as a green solvent. High stability and easy preparation of these acylating reagents are other advantages of this method.
- Ebrahimi, Sara,Saiadi, Safoura,Dakhilpour, Simin,Mirsattari, Seyed Nezamoddin,Massah, Ahmad Reza
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- Orthogonal Discrimination among Functional Groups in Ullmann-Type C-O and C-N Couplings
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The copper-catalyzed arylation of nucleophiles has been established as an efficient methodology for the formation of C-C and C-heteroatom bonds. Considering the advances during the last two decades, the ligand choice plays a key role in such transformations and can strongly influence the catalytic efficiency. The applicability of these Ullmann-type coupling reactions regarding the orthogonal selectivity of different functional groups constitutes a challenging subject for current synthetic strategies. Herein, we report a useful toolkit of Cu-based catalysts for the chemoselective arylation of a wide-range of nucleophiles in competitive reactions using aryl iodides and bromides. We show in this work that the arylation of all kinds of amides can be orthogonal to that of amines (aliphatic or aromatic) and phenol derivatives. This high chemoselectivity can be governed by the use of different ligands, yielding the desired coupling products under mild conditions. The selectivity trends are maintained for electronically biased iodobenzene and bromobenzene electrophiles. Radical clock experiments discard the occurrence of radical-based mechanisms.
- Rovira, Mireia,Soler, Marta,Güell, Imma,Wang, Ming-Zheng,Gómez, Laura,Ribas, Xavi
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supporting information
p. 7315 - 7325
(2016/09/09)
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- Iron-catalyzed Cα-H oxidation of tertiary, aliphatic amines to amides under mild conditions
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De novo syntheses of amides often generate stoichiometric amounts of waste. Thus, recent progress in the field has focused on precious metal catalyzed, oxidative protocols to generate such functionalities. However, simple tertiary alkyl amines cannot be used as starting materials in these protocols. The research described herein enables the oxidative synthesis of amides from simple, noncyclic tertiary alkyl amines under synthetically useful, mild conditions through a biologically inspired approach: Fe-catalyzed Cα-H functionalization. Mechanistic investigations provide insight into reaction intermediates and allow the development of a mild Cα-H cyanation method using the same catalyst system. The protocol was further applied to oxidize the drug Lidocaine, demonstrating the potential utility of the developed chemistry for metabolite synthesis. Let′s iron it out! The title reaction enables the oxidative synthesis of amides directly from tertiary, noncyclic alkyl amines under synthetically useful, mild conditions through a biologically inspired approach employing oxidative iron catalysis. Mechanistic studies suggest that hemiaminals are likely intermediates in this reaction and that the catalytic system can be employed for other Cα-H oxidations of amines.
- Legacy, Christopher J.,Wang, Anqi,O'Day, Brian J.,Emmert, Marion H.
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supporting information
p. 14907 - 14910
(2016/02/05)
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- The copper-catalyzed aerobic oxidative amidation of tertiary amines
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A general and efficient method for the synthesis of tertiary amides has been developed via the copper-catalyzed aerobic oxidative amidation of tertiary amines. Due to the use of the O2 oxidant, various functional groups were well tolerated under the present conditions. Extensive substrates studies demonstrated its potential as a practical approach for the synthesis of tertiary amides.
- Cheng, Hui-Cheng,Hou, Wen-Jun,Li, Zeng-Wen,Liu, Ming-Yu,Guan, Bing-Tao
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supporting information
p. 17596 - 17599
(2015/12/08)
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- Iron-catalyzed aerobic oxidative amidation of tertiary amines with carboxylic acids
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An oxidative amidation of tertiary amines with carboxylic acids has been developed in the presence of FeCl3·6H2O as catalyst and oxygen as oxidant. A variety of tertiary amides were obtained in good to excellent yields from inexpensive and readily available reagents. The possible reaction pathways were investigated.
- Ma, Lina,Li, Yuanming,Li, Zhiping
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p. 1310 - 1315
(2015/03/18)
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- Electrochemical reduction of 2-chloro-N-phenylacetamides at carbon and silver cathodes in dimethylformamide
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Cyclic voltammetry and controlled-potential (bulk) electrolysis have been employed to investigate the direct electrochemical reduction of 2-chloro-N-methyl-N-phenylacetamide (1a), 2-chloro-N-ethyl-N-phenylacetamide (1b), and 2-chloro-N-phenylacetamide (1c) at carbon and silver cathodes, as well as the catalytic reduction of these compounds by electrogenerated nickel(I) salen, in dimethylformamide (DMF) containing 0.050 M tetramethylammonium tetrafluoroborate (TMABF4). Cyclic voltammograms for reduction of 1a and 1b show a single irreversible cathodic peak for cleavage of the carbon-chlorine bond, but two irreversible cathodic peaks are observed in cyclic voltammograms for reduction of 1c. Controlled-potential reduction of 1a and 1b gives mixtures of dechlorinated amide and N-alkyl-N-phenylaniline, whereas bulk electrolyses of 1c afford N-phenylacetamide in almost quantitative yield. In addition, bulk electrolyses of 1a and 1b result in the formation of very small amounts of dimeric species that arise from coupling of the radical intermediate formed by one-electron cleavage of the carbon-chlorine bond. On the basis of the coulometric n values and product distributions, together with computations based on density functional theory, we propose mechanistic pictures for the reduction of 1a and 1b that involve radical intermediates, whereas reduction of 1c involves carbanion intermediates.
- Pasciak, Erick M.,Sengupta, Arkajyoti,Mubarak, Mohammad S.,Raghavachari, Krishnan,Peters, Dennis G.
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p. 159 - 166
(2014/04/03)
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- Catalysed anti-Markovnikov oxidation of terminal aryl alkenes to aldehydes and transformation of methyl aryl tertiary amines to formamides with H2O2 as a terminal oxidant
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Anti-Markovnikov oxidation of terminal aryl alkenes to aldehydes and transformation of N-methyl aryl tertiary amines to formamides with H2O2 as a terminal oxidant under mild conditions have been achieved with moderate to good product yields using [FeIII(TF4DMAP)OTf] as catalyst. This journal is
- Du, Yi-Dan,Tse, Chun-Wai,Xu, Zhen-Jiang,Liu, Yungen,Che, Chi-Ming
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supporting information
p. 12669 - 12672
(2015/05/20)
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- Ligand-free Ullmann-type C-heteroatom couplings under practical conditions
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A new practical ligand-free protocol for copper-catalyzed C-heteroatom cross-coupling reactions (Ullmann-type) is described. The use of dimethyl sulfoxide (DMSO) as the solvent overcomes the need to use organic auxiliary ligands; thus, DMSO is revealed as a nontoxic and superior solvent for Ullmann-type coupling reactions. This method allows the arylation of a wide range of amides, alcohols, and amines under practical conditions with bromobenzene and iodobenzene derivatives and will likely find direct application in current organic synthesis. The competitive reactivity among different functional groups is reported and rationalized, and the possibility to achieve selective arylation reactions is demonstrated. Copyright
- Gueell, Imma,Ribas, Xavi
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p. 3188 - 3195
(2014/06/09)
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- Amide bond formation through iron-catalyzed oxidative amidation of tertiary amines with anhydrides
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A general and efficient method for amide bond synthesis has been developed. The method allows for synthesis of tertiary amides from readily available tertiary amines and anhydrides in the presence of FeCl2 as catalyst and tert-butyl hydroperoxide in water (T-Hydro) as oxidant. Mechanistic studies indicated that the in situ-generated α-amino peroxide of tertiary amine and iminium ion act as key intermediates in this oxidative transformation.
- Li, Yuanming,Ma, Lina,Jia, Fan,Li, Zhiping
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p. 5638 - 5646
(2013/07/26)
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- Synthetic studies connected with the preparation of N-[3-(3- cyanopyrazolo[1,5-a]pyrimidin-5-yl)phenyl]-N-ethylacetamide, a zaleplon regioisomer
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N-[3-(3-Cyanopyrazolo[1,5-a]pyrimidin-5-yl)phenyl]-N-ethyl-acetamide, a principal impurity of zaleplon, is prepared by Suzuki-Miyaura cross coupling reaction of the corresponding boronic acid and/or boronates with 5-chloropyrazolo[1,5-a]pyrimidin-3-carbonitrile (7). Various methods of preparation of both components are described, as well as approaches based on the final modification of the 5-(3-aminophenyl)-pyrazolo[1,5-a]pyrimidine-3- carbonitrile moiety prepared by Suzuki-Miyaura cross coupling. All the prepared compounds were unambiguouesly identified by NMR techniques. Spectral characteristics (IR, UV, MS) of these compounds are also given.
- Radl, Stanislav,Blahovcova, Michaela,Tkadlecova, Marcela,Havlicek, Jaroslav
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experimental part
p. 1359 - 1376
(2010/10/20)
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- Acyl iodides in organic synthesis: XI. Unusual N-C bond cleavage in tertiary amines
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Acyl iodides reacted with excess primary and secondary amines in a way similar to acyl chlorides, yielding the corresponding carboxylic acid amide and initial amine hydroiodide. Reactions of tertiary amines with acyl iodides were accompanied by cleavage of the N-C bond with formation of the corresponding N,N-di(hydrocarbyl)carboxamide and alkyl iodide. In the presence of excess tertiary amine the latter was converted into quaternary tetra(hydrocarbyl) ammonium iodide.
- Voronkov,Tsyrendorzhieva,Rakhlin
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experimental part
p. 481 - 484
(2009/04/11)
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- A new synthesis of N-phenyl lactams
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The synthesis of N-phenyl lactams by phase transfer oxidation of N,N- (polymethylene) anilines with potassium permanganate is reported.
- Markgraf, J. Hodge,Stickney, Carolyn A.
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p. 109 - 110
(2007/10/03)
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- A new phase transfer catalyst (PTC) for N-alkylation reactions
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Hexamethylene tetramine bromide HMTA+ Br- - a new phase transfer catalyst is reported for N-Alkylation reactions of industrially important anilides.
- Bisarya,Rao
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p. 3305 - 3313
(2007/10/02)
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- EFFECT OF THE STRUCTURE OF THE AMINE ON THE RATE OF BASE-CATALYZED ACYLATION OF ALKYL AROMATIC AMINES BY BENZOYL CHLORIDE AND 2,4-DINITROPHENYL ACETATE
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The kinetics of the noncatalytic and base-catalyzed aminolysis of benzoyl chloride (with pyridine as catalyst) and 2,4-dinitrophenyl acetate (with pyridine, ε-caprolactam and pyridine N-oxide as catalysts) by alkyl aromatic amines PhNHR were studied in benzene at 25 deg C.The obtained rate constants are described satisfactorily by the modified Taft equation, which takes account of the steric and inductive effects of the structure of the amine.The results are discussed in terms of base and nucleophilic mechanisms of catalysis.
- Oleinik, N. M.,Sadovskii, Yu. S.,Litvinenko, L. M.,Radchenko, N. D.,Korzhilova, L. I.
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p. 1144 - 1152
(2007/10/02)
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- AN ANOMALOUS DEALKYLATION-ACYLATION OF N,N-DIALKYLANILINES
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N,N-Dialkylaniline undergoes a thermal N-dealkylation and acylation in the presence of 2-acetoxypyridines.
- Newkome, George R.,Yuanjiao, Xia
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p. 981 - 982
(2007/10/02)
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- Catalytic and Non-catalytic Addition of Aromatic Amines to Terminal Acetylenes in the Presence of Mercury(II) Chloride and Acetate
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The addition of aromatic amines to terminal acetylenes in the presence of catalytic amounts of mercury(II) chloride gives imines, enamines, and 1,2,3,4-tetrahydroquinoline derivatives; mercury(II) acetate shows considerably less catalytic activity and may be used for the non-catalytic preparation of imines, enamines, N,N'-disubstituted acetamidines, and N,N-disubstituted acetamides.
- Barluenga, Jose,Aznar, Fernando,Liz, Ramon,Rodes, Rosa
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p. 2732 - 2737
(2007/10/02)
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