- Hypervalent iodine mediated oxidative radical amination of heteroarenes under metal-free conditions
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A metal-free, PhI(OCOCF3)2-mediated C[sbnd]N bond forming reaction was developed between quinolines and nitrogen source, affording a facile route for the construction of 2-aminoquinolines via a nitrogen-centered radical process. This reaction represents a significant addition to the limited number of existing transition metal-catalyzed processes for the C-2 amination of quinolines and will find practical application in the synthesis of nitrogen-functionalized quinolines.
- Zhao, Feng,Sun, Ting,Sun, Hefeng,Xi, Gaolei,Sun, Kai
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Read Online
- Site-Selective Deoxygenative Amination of Azine N-Oxides with Carbodiimides under Catalyst-, Activator-, Base-, and Solvent-Free Conditions
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An operationally simple method for synthesizing 2-amino azines via [3+2] dipolar cycloaddition of azine N-oxide with carbodiimide has been demonstrated. The reaction can proceed smoothly under simple heating conditions without any transition metal catalyst, activator, base, and solvent. This transformation demonstrates a broad substrate scope and produces CO2 as the only co-product. The applicability of this method is highlighted by the late-stage modification of bioactive molecules, including quinine, (±)-α-tocopherol, and tryptamine modified quinoline.
- Sarmah, Bikash Kumar,Konwar, Monuranjan,Das, Animesh
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p. 10762 - 10772
(2021/07/31)
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- Solvent-Dependent Cyclization of 2-Alkynylanilines and ClCF2COONa for the Divergent Assembly of N-(Quinolin-2-yl)amides and Quinolin-2(1 H)-ones
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Herein, we present an expedient Cu-catalyzed [5 + 1] cyclization of 2-alkynylanilines and ClCF2COONa to divergent construction of N-(quinolin-2-yl)amides and quinolin-2(1H)-ones by regulating the reaction solvents. Notably, nitrile acts as a solvent and performs the Ritter reactions. ClCF2COONa is used as a C1 synthon in this transformation, which also represents the first example for utilization of ClCF2COONa as an efficient desiliconization reagent. The current protocol involves in situ generation of isocyanide, copper-activated alkyne, Ritter reaction and protonation.
- Wang, Ya,Zhou, Yao,Ma, Xingxing,Song, Qiuling
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p. 5599 - 5604
(2021/08/01)
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- Catalyst-free synthesis of substituted pyridin-2-yl, quinolin-2-yl, and isoquinolin-1-yl carbamates from the corresponding hetaryl ureas and alcohols
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A novel catalyst-free synthesis ofN-pyridin-2-yl,N-quinolin-2-yl, andN-isoquinolin-1-yl carbamates utilizes easily accessibleN-hetaryl ureas and alcohols. The proposed environmentally friendly technique is suitable for the good-to-high yielding synthesis of a wide range ofN-pyridin-2-yl orN-quinolin-2-yl substituted carbamates featuring electron-donating and electron-withdrawing groups in the azine rings and containing various primary, secondary, and even tertiary alkyl substituents at the oxygen atom (48-94%; 31 examples). The DFT calculation and experimental study showed that the reaction proceeds through the intermediate formation of hetaryl isocyanates. The method can be applied to obtainN-isoquinolin-1-yl carbamates, although in lower yields, and ethyl benzo[h]quinolin-2-yl carbamate has also been successfully synthesized (68%).
- Baykov, Sergey V.,Boyarskaya, Irina A.,Boyarskiy, Vadim P.,Geyl, Kirill K.,Kasatkina, Svetlana O.
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p. 6059 - 6065
(2021/07/21)
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- Developing Inhibitors of the p47phox-p22phox Protein-Protein Interaction by Fragment-Based Drug Discovery
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Nicotinamide adenine dinucleotide phosphate oxidase isoform 2 is an enzyme complex, which generates reactive oxygen species and contributes to oxidative stress. The p47phox-p22phox interaction is critical for the activation of the catalytical NOX2 domain, and p47phox is a potential target for therapeutic intervention. By screening 2500 fragments using fluorescence polarization and a thermal shift assay and validation by surface plasmon resonance, we found eight hits toward the tandem SH3 domain of p47phox (p47phoxSH3A-B) with KD values of 400-600 μM. Structural studies revealed that fragments 1 and 2 bound two separate binding sites in the elongated conformation of p47phoxSH3A-B and these competed with p22phox for binding to p47phoxSH3A-B. Chemical optimization led to a dimeric compound with the ability to potently inhibit the p47phoxSH3A-B-p22phox interaction (Ki of 20 μM). Thereby, we reveal a new way of targeting p47phox and present the first report of drug-like molecules with the ability to bind p47phox and inhibit its interaction with p22phox.
- Solbak, Sara Marie ?ie,Zang, Jie,Narayanan, Dilip,H?j, Lars Jakobsen,Bucciarelli, Saskia,Softley, Charlotte,Meier, Sebastian,Langkilde, Annette Eva,Gotfredsen, Charlotte Held,Sattler, Michael,Bach, Anders
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p. 1156 - 1177
(2020/03/10)
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- Reaction of Pyridine-N-Oxides with Tertiary sp2-N-Nucleophiles: An Efficient Synthesis of Precursors for N-(Pyrid-2-yl)-Substituted N-Heterocyclic Carbenes
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N-(Pyrid-2-yl)-substituted azolium and pyridinium salts, precursors for hybrid NHC-containing ligands, were obtained with excellent regioselectivity, employing a deoxygenative CH-functionalization of pyridine-N-oxides with substituted imidazoles, thiazoles, and pyridine. Unlike the traditional SNAr-based methods, this approach provides high yields for substrates bearing substituents of different electronic nature. The utility of azolium and pyridinium salts thus prepared was also highlighted by the synthesis of pyridyl-substituted imidazolyl-2-thione, benzodiazepine as well as 2-aminopyridines.
- Bugaenko, Dmitry I.,Karchava, Alexander V.,Yurovskaya, Marina A.
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p. 5777 - 5782
(2020/12/01)
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- Copper and L-(?)-quebrachitol catalyzed hydroxylation and amination of aryl halides under air
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L-(?)-Quebrachitol, a natural product obtained from waste water of the rubber industry, was utilized as an efficient ligand for the copper-catalyzed hydroxylation and amination of aryl halides to selectively give phenols and aryl amines in water or 95percent ethanol. In addition, the hydroxylation of 2-chloro-4-hydroxybenzoic acid was validated on a 100-g scale under air.
- Bao, Xuefei,Chen, Guoliang,Dong, Jinhua,Du, Fangyu,Li, Hui,Liang, Xinjie,Wu, Ying,Zhang, Yongsheng
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supporting information
(2020/08/03)
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- Metal-free Deoxygenative 2-Amidation of Quinoline N-oxides with Nitriles via a Radical Activation Pathway
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A metal-, base- and reductant-free approach for the efficient synthesis of various N-acylated 2-aminoquinolines was reported. In this work, readily available nitriles are used as the amide source, and methyl carbazate as both the radical activating reagent and oxygen source. This is the first report on the ester-radical-activated highly regioselective addition of nitriles to quinolone N-oxides. This procedure is expected to complement the current methods for functionalization of N-oxides via an electrophilic activation mechanism. (Figure presented.).
- Xie, Long-Yong,Peng, Sha,Liu, Fang,Yi, Jin-Yu,Wang, Ming,Tang, Zilong,Xu, Xinhua,He, Wei-Min
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supporting information
p. 4259 - 4264
(2018/10/15)
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- Nickel-Catalyzed Amination of Aryl Carbamates with Ammonia
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Aryl carbamates were employed in the nickel-catalyzed monoarylation of ammonia. The applied, well-defined single-component nickel(II) precatalyst contains a Josiphos ligand, is air-stable, and operates without any ancillary reductant. This catalyst system
- Schranck, Johannes,Furer, Patrick,Hartmann, Veronika,Tlili, Anis
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supporting information
p. 3496 - 3500
(2017/07/04)
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- One-pot synthesis of primary amines from carboxylic acids through rearrangement of in situ generated hydroxamic acid derivatives
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A one-pot synthesis of primary amines from carboxylic acids through a Lossen rearrangement of hydroxamic acid derivatives, which were in situ generated by the reaction of carboxylic acids with O-trimethylsilylhydroxylamine (NH2OTMS) and carbonyl diimidazole (CDI, 1.5 equiv) in dimethyl sulfoxide at room temperature, has been achieved. This one-pot method could be applied to various carboxylic acids such as aromatic, heteroaromatic, aliphatic, and optically active substrates.
- Hoshino, Yujiro,Ohtsuka, Naoya,Okada, Takuya,Honda, Kiyoshi
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p. 5304 - 5307
(2016/11/16)
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- A base-mediated self-propagative Lossen rearrangement of hydroxamic acids for the efficient and facile synthesis of aromatic and aliphatic primary amines
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A variety of aromatic and aliphatic hydroxamic acids were converted to the corresponding primary amines via base-mediated rearrangement. This rearrangement could proceed with less than 1 equiv. of K2CO3 in polar solvents under thermal conditions with no external reagents. This rearrangement has several features including no external activating agents needed for promoting the rearrangement, less than one equivalent of a base is sufficient for the reaction, and a clean reaction in which only carbon dioxide is produced as a by-product. A self-propagating mechanism via an isocyanate intermediate is proposed and elementary reaction steps, namely, chain propagation reactions are supported by experiments.
- Ohtsuka, Naoya,Okuno, Moriaki,Hoshino, Yujiro,Honda, Kiyoshi
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p. 9046 - 9054
(2016/10/05)
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- A fluorescence chemosensor based on imidazo[1,2-a]quinoline for Al3+ and Zn2+ in respective solutions
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A new chemosensor, N′-[(2-hydroxyphenyl)methylidene]imidazo[1,2-a]quinoline-2-carbohydrazide (L2), was developed, which could detect Al3+ in DMSO/H2O HEPES buffer and Zn2+ in EtOH/H2O HEPES buffer. The chemosensor exhibits high selectivity and sensitivity for sensing Al3+ and Zn2+ with a fluorescence "turn-on" mode.
- Sun, Junhua,Liu, Zheng,Wang, Ying,Xiao, Shihua,Pei, Meishan,Zhao, Xiuxian,Zhang, Guangyou
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p. 100873 - 100878
(2015/12/05)
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- In situ generation of ammonia for the copper-catalyzed synthesis of primary aminoquinolines
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The synthesis of primary aminoquinolines from iodoquinolines was carried out in the presence of copper(i) iodide and formamide as the solvent and source of ammonia generated in situ. The reaction proceeded under mild conditions within a few hours and was applicable to various iodoquinolines.
- Aillerie, Alexandre,Pellegrini, Sylvain,Bousquet, Till,Pélinski, Lydie
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p. 1389 - 1391
(2014/05/06)
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- Mild and highly selective palladium-catalyzed monoarylation of ammonia enabled by the use of bulky biarylphosphine ligands and palladacycle precatalysts
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A method for the Pd-catalyzed arylation of ammonia with a wide range of aryl and heteroaryl halides, including challenging five-membered heterocyclic substrates, is described. Excellent selectivity for monoarylation of ammonia to primary arylamines was achieved under mild conditions or at rt by the use of bulky biarylphosphine ligands (L6, L7, and L4) as well as their corresponding aminobiphenyl palladacycle precatalysts (3a, 3b, and 3c). As this process requires neither the use of a glovebox nor high pressures of ammonia, it should be widely applicable.
- Cheung, Chi Wai,Surry, David S.,Buchwald, Stephen L.
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supporting information
p. 3734 - 3737
(2013/08/23)
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- Ligandless copper-catalyzed coupling of heteroaryl bromides with gaseous ammonia
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A range of different N- and S-containing heterocyclic bromides can be efficiently coupled with gaseous ammonia in the presence of copper(II) acetylacetonate [Cu(acac)2] as catalyst and in the absence of additional ligands. Unstable aminothiophenes and aminobenzothiophenes can be further reacted in situ to afford functionalized derivatives. Copyright
- Fantasia, Serena,Windisch, Johannes,Scalone, Michelangelo
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supporting information
p. 627 - 631
(2013/04/11)
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- One-pot synthesis of 2-aminoquinoline-based alkaloids from acetonitrile
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α-Diaminoboryl carbanions, readily prepared from acetonitrile, stereoselectively convert 2-nitrobenzaldehydes into nitrophenyl (Z)-acrylonitriles. Subsequent reductive cyclization leads to a series of 2-aminoquinoline derivatives. The entire procedure is practically operated in a single flask.
- Tomioka, Takashi,Takahashi, Yusuke,Maejima, Toshihide
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p. 5113 - 5118
(2012/08/07)
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- A general and efficient 2-amination of pyridines and quinolines
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(Chemical Equation Presented) Pyridine N-oxides were converted to 2-aminopyridines in a one-pot fashion using Ts2O-t-BuNH2 followed by in situ deprotection with TFA. The amination proceeded in high yields, excellent 2-/4-selectivity, and with good functional group compatibility. 2-Amino (iso)quinolines were also obtained in the same manner. Combined with the simple oxidation of pyridines to pyridine N-oxides, this method provides a general and efficient way for amination of 2-unsubstituted pyridines.
- Yin, Jingjun,Xiang, Bangping,Huffman, Mark A.,Raab, Conrad E.,Davies, Ian W.
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p. 4554 - 4557
(2008/02/04)
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- N-(aryl/heteroaryl) amino acid derivatives pharmaceutical compositions comprising same and methods for inhibiting β-amyloid peptide release and/or its synthesis by use of such compounds
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Disclosed are compounds which inhibit β-amyloid peptide release and/or its synthesis, and, accordingly, have utility in treating Alzheimer's disease. Also disclosed are pharmaceutical compositions comprising a compound which inhibits β-amyloid peptide release and/or its synthesis as well as methods for treating Alzheimer's disease both prophylactically and therapeutically with such pharmaceutical compositions.
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- Allyl amines as ammonia equivalents in the preparation of anilines and heteroarylamines
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A series of anilines and heteroarylamines were synthesized in moderate to excellent yields by palladium catalyzed cross coupling reaction of aryl or heteroaryl halides with allyl- or N,N-diallylamine followed by deallylation.
- Jaime-Figueroa, Saul,Liu, Yanzhou,Muchowski, Joseph M.,Putman, David G.
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p. 1313 - 1316
(2007/10/03)
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- Chichibabin aminations of pyridine bases
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Improved Chichibabin aminations of pyridine bases are described which are conducted under a pressurized gas phase containing ammonia and in the presence of a selected additive which increases the reaction rate, and also in preferred processes favorably alters the isomer ratios and product yields from the aminations while benefiting product workup and recovery as well.
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- Compatibility of Various Carbanion Nucleophiles with Heteroaromatic Nucleophilic Substitution by the SRN1 Mechanism
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Carbanions generated from 2,4,4-trimethyl-2-oxazoline (1a), 2-benzyl-4,4-dimethyl-2-oxazoline (1b), 2,4-dimethylthiazole (13a), 2-benzyl-4-methylthiazole (13b), N,N-dimethylacetamide (17a), tert-butyl acetate (17b), ethyl phenylacetate (17c), N-methyl-N-phenyl-2-butenamide (22), tert-butyl 3-butenoate (25), and dimethyl methylphosphonate (29a) by means of KNH2 in liquid NH3 all reacted with 2-bromopyridine (2) via photoassisted reactions that exhibited characteristics of the SRN1 mechanism. Similar results were obtained in reactions of these carbanions with other substrates, including 2-chloroquinoline (6), iodobenzene (9), bromobenzene (10), and bromomesitylene (11).
- Wong, Jim-Wah,Natalie Jr., Kenneth J.,Nwokogu, Godson C.,Pisipati, Jyothi S.,Flaherty, Patrick T.,Greenwood, Thomas D.,Wolfe, James F.
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p. 6152 - 6159
(2007/10/03)
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- A short and versatile synthesis of 3-substituted 2-aminoquinolines
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A short and versatile synthesis of a series of 3-substituted 2-aminoquinolines was accomplished in good yields starting from 2-nitrobenzaldehyde. Organic phosphonates were used as key synthetic intermediates and in some cases amino acids as readily available starting materials. The final two key steps of the sequence involving a reduction and ring closure that led to the 2-aminoquinoline skeleton were carried out in a 'one pot' procedure using SnCL22H2O.
- Compagnone, Reinaldo S.,Suarez, Alirica I.,Zambrano, Jorge L.,Pina, Ivette C.,Dominguez, Jose N.
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p. 1631 - 1641
(2007/10/03)
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- The Chemistry of 5-Oxodihydroisoxazoles. XIV. Synthesis of 2-(1-Aryltetrazol-5-yl)propanoic Acids
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A number of N-arylisoxazol-5(2H)-ones (aryl = phenyl, isoquinolin-1-yl, quinolin-2-yl, 2-phenylquinazolin-4-yl and benzothiazol-2-yl) have been reacted with lithium azide to give 2-(1-aryltetrazol-5-yl)acetic esters, which have been C-methylated and hydrolysed.The resulting 2-(1-aryltetrazol-5-yl)propanoic acid had low antiinflammatory activity, as judged by inhibition of synthesis of prostaglandin PGE2 or tumor necrosis factor α.
- Caiazza, Daniela,Prager, Rolf H.,Schafer, Karl
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p. 1861 - 1872
(2007/10/03)
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- A simple new synthetic method for the preparation of 2-aminoquinolines
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2-Chloroquinolines (1a - j) heated in acetamide at 200° in the presence of potassium carbonate give 2-aminoquinolines (2a - j) in good yields.
- Korodi
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p. 1841 - 1846
(2007/10/02)
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- Quinoline amides
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Compounds of the formula: (wherein Ra represents an optionally substituted alkyl, alkenyl, alkynyl, cycloalkyl, cycloalkylalkyl, aryl, aralkyl or heteroaryl group; Rb and Rc, which may be the same or different, each represents hydrogen or an optionally substituted alkyl, cyclo- alkyl, cycloalkylalkyl, alkenyl, alkynyl, phenyl or benzyl group, or Rb and Rc together with the nitrogen atom therebetween represent a saturated nitrogen containing heterocyclic ring; and Rd represents a hydrogen atom or an alkyl or alkanoyl group) and the salts thereof are useful as agents for binding to benzodiazepine receptors, and especially possess anxiolytic activity.
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- Electrolytic reduction of pyridine-2-carboxaldehyde-2-quinolylhydrazone at pyrolytic graphite electrode
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The electrochemical reduction of pyridine-2-carboxaldehyde-2-quinolylhydrazone at pyrolytic graphite electrode has been studied in the phosphate buffers of pH range 3.0-10.8.The products of reduction have been characterized.On the basis of linear and cyclic sweep voltammetry, coulometry, spectral studies and product identification, a redox mechanism has been suggested.
- Mathur, Navin C.,Goyal, R. N.,Malik, W. U.
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p. 765 - 769
(2007/10/02)
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- 151. Azidinium-Salze. 24. Mitteilung. Thermolyse heterocyclischer Azidinium-tetrafluoroborate
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The thermolysis of some azidinium salts was investigated.It led to a large variety of products which were isolated or identified by GC/MS.Reaction mechanisms are discussed to explain the product formation.
- Huys-Francotte, Martine,Balli, Heinz
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p. 1679 - 1684
(2007/10/02)
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- Migration to electron-deficient nitrogen. A one pot synthesis of aromatic and Heteroaromatic amines from carboxylic acids
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Treatment of a range of aroyl and heteroaroyl chlorides with hydroxylamine-O-sulphonic acid in dry toluene, under reflux, gives good yields of the corresponding arylamine.
- Wallace,Barker,Wood
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p. 1143 - 1144
(2007/10/02)
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- Anxiolytic 4-aminoquinoline-3-carboxamides
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The present invention comprises certain amide derivatives of 4,8-disubstituted quinoline-3-carboxylic acids of formula I; pharmaceutically acceptable salts of the compounds of formula I; pharmaceutical compositions containing a compound of formula I, or a pharmaceutically acceptable salt thereof, for use in the treatment of anxiety; and processes for the manufacture of the compounds of formula I, as well as intermediates for use in such manufacture.
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- BASIC MEDIA BEHAVIOR OF N- ETHYL CARBAMATES (Y=SMe, SOMe, SO2Me, H, Br, CN)
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From the results obtained in the hydrolysis reaction of the carbamate group of some thioderivatives compounds whose common structure is (2-EtOOCNH-C6H4)-CHOH-CH2Y a mechanism is suggested to explain the products, as well as the relationship between the relative configuration of diastereoisomeric sulfoxides (Y=SOMe) with the reaction rate and with the stereochemical outcome.Other interesting and unexpected products are yielded when the hydrolysis reaction of other carbamates (Y=H, Br, CN) is carried out.In the present cases, the carbamate function seems to behave as a very versatile group capable of readily undergoing conversions to several kinds of heterocycles.
- Ruano, Jose Luis Garcia,Pedregal, Concepcion,Rodriguez, Jesus H.
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p. 203 - 214
(2007/10/02)
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- Etude de la metallation des pivalamido-2, -3 et -4 quinoleines
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The three isomeric 2-, 3- and 4-pivalamidoquinolines react with lithiating reagents to give either metalation or nucleophilic addition products.Metalation occurs best with the 2-substituted isomer.Surprisingly the 4-pivalamidoquinoline is lithiated at C(8).A new directing group derived from the amine, the ureido substituent, directs the lithiation at C(2) of the 3-aminoquinoline derivative.
- Godard, Alain,Jacquelin, Jean-Marie,Queguiner, Guy
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p. 273 - 286
(2007/10/02)
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- 192. Azidinium-Salze 23.Mitteilung Photolyse heterocyclischer Azidinium-Salze
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The photochemistry of some azidinium salts was investigated.Their photolysis led to a large variety of products whichh were isolated and identified.Reaction mechanisms involving singlet and triplet nitrene intermediates are discussed to explain the product formation.
- Balli, Heinz,Huys-Francotte, Martine,Schmidlin, Fred
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p. 2045 - 2057
(2007/10/02)
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- Polarographic Behaviour of 2,2'-Dipyridyl-2-pyridylhydrazone (DPPH) and Pyridine-2-aldehyde-2-quinolylhydrazone (PAQH) at the Droping Mercury Electrode
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The polarographic behaviour of 2,2'-dipyridyl-2-pyridylhydrazone (DPPH) and pyridine-2-aldehyde-2-quinolylhydrazone (PAQH) at dme were studied in aqueous Britton-Robinson buffers containing 50percent ethanol.The polograms consist of one irreversible wave in the acidic and alkaline medium.Two electrods are consumed in the splitting of the N-N bond.The effect of pH on the limiting current and E as well as the reduction mechanism are discussed and compared with similar compounds.The values of the kinetic parameters for the electrode reaction at different pH values are also computed from the polarographic results. - Keywords: Electrochemistry; Reduction mechanism; Kinetic parameters
- Zuhri, Ali Z. Abu,Shalabi, Jamal S.
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p. 1335 - 1344
(2007/10/02)
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- DISSYMMETRY OF CERTAIN SUBSTITUTED DIPYRIDOTETRAAZAPENTALENES
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In a two-step synthesis from staring amines, a series of compounds has been prepared in which steric crowding (1b,c,d,f) was introduced into the "bay region" of pyridoimidazoimidazopyridine (1a).This forces the tetracyclic ring system into non-planarity.Two hexa-heterohelicenes 2a and b were prepared that incorporate the 1,3,4,6-tetraazapentalene ring system and provide molecular crowding in the "bay region" due to the terminal rings, which similarly distort the hexacyclic ring system from planarity.Single crystal X-ray structure determinations revealed that the compounds (1b,c,d,f,2a and b) exist as enantiomeric pairs in the crystalline state.
- Pereira, David E.,Clauson, Gary L.,Leonard, Nelson J.
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p. 4931 - 4946
(2007/10/02)
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- On the Chichibabin Amination of Quinoline and some Nitroquinolines
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Quinoline is aminated into 2-aminoquinoline (55-60percent) when treated with potassium amide/liquid ammonia/potassium permanganate at -65 deg C.When the amination is carried out by allowing the solution of quinoline in potassium amide/liquid ammonia to raise from -60 deg C to +15 deg C before addition of potassium permanganate, the main product is 4-aminoquinoline.Using as reagent liquid ammonia/potassium permanganate (thus without the presence of potassium amide) 3-nitroquinoline is exclusively aminated at -40 deg C into 4-amino-3-nitroquinoline.Using the same conditions, from 4-nitroquinoline 3-amino-4-nitroquinoline is obtained.The mechanism of these amination reactions is discussed.
- Tondyz, Hanna,Plas, Henk C. van der,Wozniak, Marian
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p. 353 - 355
(2007/10/02)
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- Photostimulated Reactions of 2-Bromopyridine and 2-Chloroquinoline with Nitrile-Stabilized Carbanions and Certain Other Nucleophiles
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Potassiophenylacetonitrile (2) reacts with 2-bromopyridine (1) and 2-chloroquinoline (4) via the SRN1 mechanism when the reactants are exposed to near-UV light in liquid NH3.Potassioacetonitrile (6) reacts similarly with 1 and 4 upon photostimulation; however, the photo-SRN1 reaction with 1 is accompanied by SNAr2 amination which becomes the major reaction in the dark or in the presence of di-tert-butyl nitroxide.Substrate 4 undergoes competing SNAr2 amination with amide ion to form 2-aminoquinoline (10) and SN(ANRORC) reactions with both amide ion and carban ion 6 to form 3-methylquinazoline (11) and 2-methyl-3-cyanoquinoline (12), respectively.Formation of 12 becomes the major pathway in reactions between 4 and 6 carried out in the dark. 4-Picolylpotassium (14) reacts with 1, 4, and 4-bromopyridinium chloride (16) under photostimulation to form the appropriate dihetarylmethanes, along with the corresponding amino heterocycles.Amination of 1, 4, and 16 predominates when these reactions are carried out in the dark.Ammonium thiophenoxide (20) undergoes a slow photo-SRN1 reaction with 1 but fails to produce the expected 2-quinolyl phenyl sulfide with 4 after 2 h of irradiation.Potassium salts of acetylene, phenylacetylene, and phthalimide do not react with 1 or 4 after 2 h of exposure to near-UV light.
- Moon, Marcus P.,Komin, Andrew P.,Wolfe, James F.,Morris, Gene F.
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p. 2392 - 2399
(2007/10/02)
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- An Unusual Reaction of Dimethyl Acetylenedicarboxylate with s-Triazolopyridine and Its Quinoline Analogue
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1,2,4-Triazolopyridine (I) reacts with dimethyl acetylenedicarboxylate in the presence of 5percent palladium-carbon catalyst to give 3-(1,2,4-triazolopyridin-3-yl)propynal (VI), this being the first example of DMAD serving directly as source of -- unit.A similar reaction with 1,2,4,triazoloquinoline (III), however, yields 2-aminoquinoline.Plausible mechanisms in both the cases are discussed.
- Ram, P. Sai,Reddy, P. S. N.,Srinivasan, V. R.
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- A SIMPLE METHOD FOR THE PREPARATION OF SOME AMINO N-HETEROAROMATICS
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The heating of some halogenated pyrazines, pyridines, and quinolines with benzamide in the presence of potassium carbonate gave the corresponding amino derivatives.The similar reaction using acetamide afforded acetamido derivatives, together with amines in some cases.
- Watanabe, Tokuhiro,Kikuchi, Etsuko,Tamura, Wataru,Akita, Yasuo,Tsutsui, Mayumi,Ohta, Akihiro
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p. 287 - 290
(2007/10/02)
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