- Designing Metallogelators Derived from NSAID-based Zn(II) Coordination Complexes for Drug-Delivery Applications
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A crystal engineering approach has been invoked to design a new series of eight Zn(II) coordination complexes derived from various non-steroidal anti-inflammatory drugs (NSAIDs), namely diclofenac (DIC), ibuprofen (IBU), naproxen (NAP), flufenamic acid (FLU) and meclofenamic acid (MEC), and two co-ligands, namely N-phenyl-3-pyridylamide (3-Py) and N-phenyl-4-pyridylamide (4-Py), and Zn(NO3)2 as potential supramolecular gelators. Half of the coordination complexes thus synthesized were able to form aqueous gels (MG-3-PyMEC, MG-3-PyDIC, MG-4-PyNAP and MG-4-PyMEC). Single-crystal structures of all eight complexes revealed that they possessed a gelation-inducing 1D hydrogen-bonded network including amide…amide synthon in some cases, which supported strongly the design principles based on which these complexes were synthesized. Interestingly, one such metallogelator complex, namely 3-PyMEC, showed an intriguing anticancer property against a human breast cancer cell line (MDA-MB-231), as revealed by both MTT and cell migration assays.
- Mondal, Swapneswar,Dastidar, Parthasarathi
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Read Online
- Direct Synthesis of N,N-Disubstituted Formamides by Oxidation of Imines Using an HFIP/UHP System
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The straightforward synthesis of N,N-disubstituted formamides using a combination of 1,1,1,3,3,3-hexafluoroispropanol (HFIP) and H2O2 is described. The unique features of HFIP allowed the utilization of a green oxidant such as H2O2, and the products, arising from an oxidation-rearrangement sequence, were obtained in good to high yields under smooth reaction conditions.
- Llopis, Natalia,Gisbert, Patricia,Baeza, Alejandro
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- An efficient and mild oxidative amidation of aldehydes using B(C6F5)3 as a catalyst and biological evaluation of the products as potential antimicrobial agents
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A mild and efficient protocol for oxidative amidation of diverse aldehydes with amines was developed using 3 mol% tris(pentafluorophenyl)borane and tert-butyl hydroperoxide to generate the corresponding amides in good to excellent yields. This method has significant advantages such as short reaction time, low toxicity, low catalyst loading, and being environmentally friendly and an operationally simple procedure. Acid labile protecting groups such as acyl and Boc displayed tolerance under the present catalytic system. Applicability in large scale synthesis of amides is an added advantage of the protocol. Moreover, direct amidation of aldehydes using substituted N-benzylanilines for the synthesis of corresponding amides was devised using the present catalytic system. Compounds 3n and 3o displayed promising antimicrobial activity against Staphylococcus aureus (Gram positive) with MIC ranging from 0.4-0.7 μg mL?1 and against Escherichia coli (Gram negative) with MIC 0.7-1.2 μg mL?1 with reference to the standard drug Ciprofloxacin.
- Guggilapu, Sravanthi Devi,Chari, Alpina Ramnath,Nagarsenkar, Atulya,Sigalapalli, Dilep Kumar,Babu, Bathini Nagendra
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Read Online
- Method for preparing amide compound by photocatalysis of organic amine
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The invention relates to the technical field of organic synthesis, in particular to a method for preparing amide compounds through photocatalysis of organic amine. The preparation method comprises the following steps: mixing tetrahalomethane with a solvent, sequentially adding an amine compound, a catalyst and organic carboxylic acid, performing stirring and reacting under an oxygen-containing atmosphere and an illumination condition, and performing separating and purifying to obtain the amide compound with a structure shown in formulas V-VII. According to the method, the reaction is carried out in the air atmosphere under the illumination condition at room temperature and normal pressure, the reaction condition is mild, the raw material source is wide, the cost is low, the byproduct generated after the reaction is the halogen simple substance, the added value is high, a large amount of waste is avoided, and the method has higher atom economy and environmental friendliness and is beneficial to large-scale production.
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Paragraph 0044-0045
(2021/06/06)
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- Manganese Catalyzed Direct Amidation of Esters with Amines
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The transition metal catalyzed amide bond forming reaction of esters with amines has been developed as an advanced approach for overcoming the shortcomings of traditional methods. The broad scope of substrates in transition metal catalyzed amidations remains a challenge. Here, a manganese(I)-catalyzed method for the direct synthesis of amides from a various number of esters and amines is reported with unprecedented substrate scope using a low catalyst loading. A wide range of aromatic, aliphatic, and heterocyclic esters, even in fatty acid esters, reacted with a diverse range of primary aryl amines, primary alkyl amines, and secondary alkyl amines to form amides. It is noteworthy that this approach provides the first example of the transition metal catalyzed amide bond forming reaction from fatty acid esters and amines. The acid-base mechanism for the manganese(I)-catalyzed direct amidation of esters with amines was elucidated by DFT calculations.
- Fu, Zhengqiang,Wang, Xinghua,Tao, Sheng,Bu, Qingqing,Wei, Donghui,Liu, Ning
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p. 2339 - 2358
(2021/02/03)
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- Activated charcoal supported copper nanoparticles: A readily available and inexpensive heterogeneous catalyst for the N-arylation of primary amides and lactams with aryl iodides
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A novel heterogeneous copper catalyst has been developed by supporting copper nanoparticles on activated charcoal via in situ reducing copper(II) with aqueous hydrazine as reductant. The characterization of Cu/C catalyst showed that the Cu0 nano-particles were formed on the surface of charcoal. This catalyst displayed good catalytic activities toward the N-arylation of primary amides and lactams with aryl iodides.
- Zhao, Rong,Dong, Wenwen,Teng, Jiangge,Wang, Zhiwei,Wang, Yunzhong,Yang, Jianguo,Jia, Qiang,Chu, Changhu
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supporting information
(2020/12/21)
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- Amine-boranes as Dual-Purpose Reagents for Direct Amidation of Carboxylic Acids
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Amine-boranes serve as dual-purpose reagents for direct amidation, activating aliphatic and aromatic carboxylic acids and, subsequently, delivering amines to provide the corresponding amides in up to 99% yields. Delivery of gaseous or low-boiling amines as their borane complexes provides a major advantage over existing methodologies. Utilizing amine-boranes containing borane incompatible functionalities allows for the preparation of functionalized amides. An intermolecular mechanism proceeding through a triacyloxyborane-amine complex is proposed.
- Choudhary, Shivani,Hamann, Henry J.,Ramachandran, P. Veeraraghavan
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- Dual targeting of cholinesterase and amyloid beta with pyridinium/isoquinolium derivatives
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With the surge in the cases of Alzheimer's disease (AD) over the years, several targets have been explored to curb the disease. Cholinesterases, namely acetylcholinesterase (AChE) and butyrylcholinesterase (BuChE), remain to be the available targets that are amendable to currently approved treatments. In this study, a series of novel compounds based on tramiprosate, a highly specific amyloid beta (Aβ) inhibitor, was designed to inhibit AChE, BuChE, and Aβ aggregation. In particular, the addition of a pyridinium/isoquinolinium ring to the tramiprosate moiety (to give compounds 3a–j) led to an increase in the binding affinity for the catalytic active site of cholinesterase, which was hampered by the presence of sulfonic acid. Exclusion of the sulfonic acid moiety led to a novel but effective class of cholinesterase inhibitors (9a–w). in vitro Aβ aggregation inhibition assay indicated that compounds 3a–j, 9e–f, 9i–l, 9q, 9r, 9u–w, and 12 could inhibit over 10% Aβ aggregation at 1 mM concentration. Cholinesterase inhibition assay suggested that compounds 9g, 9h, 9o, and 9q–t exhibit over 70% inhibition on both AChE and BuChE at a concentration of 100 μM. Amongst the designed molecules, compound 9r (ca 18% at 1 mM) showed comparable inhibitory effect on the inhibition of Aβ aggregation with tramiprosate (ca 20% at 1 mM), along with impressive cholinesterase inhibitory potential (AChE IC50 = 13 μM and BuChE IC50 = 12 μM), acceptable toxicity and ability to pass through blood brain barrier, which could be used to ameliorate the phenotypes of AD in preclinical models.
- Chakravarty, Harapriya,Ju, Yaojun,Chen, Wen-Hua,Tam, Kin Y.
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p. 242 - 255
(2019/12/27)
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- 3,6-Di(pyridin-2-yl)-1,2,4,5-tetrazine (pytz) catalysed metal-free amide bond formation from thioacids and amines at room temperature
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A 3,6-di(pyridin-2-yl)-1,2,4,5-tetrazine (pytz) catalysed efficient, mild and metal-free method has been developed for direct amide bond synthesis from simple thioacids and amines as starting materials. This methodology is useful for aromatic, aliphatic, and heteroaromatic thioacids as well as primary, secondary, heterocyclic, and even functionalized amines. A wide substrates scope, operationally mild conditions, and acylation of amines without affecting other functional groups such as alcohols, esters, carbodithioates, among others make this strategy very attractive and practical.
- Samanta, Suvendu,Ray, Shounak,Bhaduri, Samanka Narayan,Samanta, Partha Kumar,Biswas, Papu
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supporting information
(2020/08/10)
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- Compound containing bipyrazole ring, intermediate thereof and application thereof
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The invention discloses a compound containing a bipyrazole ring, and an intermediate and application thereof. The invention provides the compound containing a bipyrazole ring, as shown in a formula Iwhich is described in the specification. The compound can be used as a ligand, is high in selectivity, and is suitable for the application range of amide in C-N coupling and the C-C coupling reactionof arylboronic acid and aryl chloride, especially coupling with aryl chloride.
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Paragraph 0275-0277
(2020/05/14)
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- Preparation method of compound containing bipyrazole ring and intermediate thereof
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The invention discloses a preparation method of a compound containing a bipyrazole ring and an intermediate of the compound. The preparation method of a bipyrazole ring-containing compound as shown ina formula I comprises the following steps: (1) adding alkali into a mixture of a bipyrazole ring compound as shown in a formula I-1 and a solvent for replacement reaction to obtain a mixed system; and (2) adding an organic phosphorus compound shown as a formula I-2 into the mixed system in the step (1), and carrying out a phosphonation reaction shown in the specification, so as to obtain the bipyrazole ring-containing compound shown as the formula I, wherein R1 and R2 are independently a C1-C6 alkyl group, a C3-C8 cycloalkyl group and a phenyl group, R3 is a C1-C6 alkyl group, and X is halogen. The prepared compound containing a bipyrazole ring can be used as a ligand, and is suitable for the application range of amide in C-N coupling and the C-C coupling reaction of arylboronic acid andaryl chloride.
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Paragraph 0275-0277
(2020/05/14)
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- Synthesis of amides from acid chlorides and amines in the bio-based solvent Cyrene
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Cyrene as a bio-alternative dipolar aprotic solvent: a waste minimizing and molar efficient protocol for the synthesis of amides from acid chlorides and primary amines in the bio-available solvent Cyrene is disclosed. This protocol removed the use of toxic solvents, such as dimethylformamide and dichloromethane. A simple aqueous work-up procedure for the removal of the high boiling solvent Cyrene resulted in up to a 55-fold increase in molar efficiency (Mol E.%) versus standard operating procedures. In order to rapidly compare the molar efficiency of this process against other methodologies an Excel based Mol. E% calculator was developed that automates many of the calculations. An investigation into the hydration of Cyrene found that it readily hydrates to form a geminal diol in the presence of water and that this process is exothermic.
- Bousfield, Thomas W.,Pearce, Katharine P. R.,Nyamini, Simbarashe B.,Angelis-Dimakis, Athanasios,Camp, Jason E.
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supporting information
p. 3675 - 3681
(2019/07/09)
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- Clickable coupling of carboxylic acids and amines at room temperature mediated by SO2F2: A significant breakthrough for the construction of amides and peptide linkages
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The construction of amide bonds and peptide linkages is one of the most fundamental transformations in all life processes and organic synthesis. The synthesis of structurally ubiquitous amide motifs is essential in the assembly of numerous important molecules such as peptides, proteins, alkaloids, pharmaceutical agents, polymers, ligands and agrochemicals. A method of SO2F2-mediated direct clickable coupling of carboxylic acids with amines was developed for the synthesis of a broad scope of amides in a simple, mild, highly efficient, robust and practical manner (>110 examples, >90% yields in most cases). The direct click reactions of acids and amines on a gram scale are also demonstrated using an extremely easy work-up and purification process of washing with 1 M aqueous HCl to provide the desired amides in greater than 99% purity and excellent yields.
- Wang, Shi-Meng,Zhao, Chuang,Zhang, Xu,Qin, Hua-Li
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p. 4087 - 4101
(2019/04/30)
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- Aminocarbonylation of N -Containing Heterocycles with Aromatic Amines Using Mo(CO) 6
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We describe herein the palladium-catalyzed aminocarbonylation of nitrogen-containing heterocycles with aniline derivatives using molybdenum hexacarbonyl as a CO solid source, expanding the scope of the limited examples. This method is compatible with a variety of substitutions on the aniline moiety. The simple reaction conditions include easily available Pd(dppf)Cl 2 catalyst, DBU as base in DMF at 120 °C for 3 hours in sealed tube thereby leading to the isolation of 21 compounds with yields ranging from 18 to 82%. We also show that double aminocarbonylation reactions are possible in satisfactory yields regarding both coupling partners.
- Mamone, Marius,Aziz, Jessy,Le Bescont, Julie,Piguel, Sandrine
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p. 1521 - 1526
(2018/01/27)
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- Towards a sustainable synthesis of amides: chemoselective palladium-catalysed aminocarbonylation of aryl iodides in deep eutectic solvents
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A palladium-catalysed aminocarbonylation of (hetero)aryl iodides has, for the first time, been accomplished in deep eutectic solvents as environmentally benign and recyclable media, under mild conditions. The reactions proceeded with a good substrate scope, and a variety of amides have been synthesized in yields up to 98%.
- Messa, Francesco,Perrone, Serena,Capua, Martina,Tolomeo, Francesco,Troisi, Luigino,Capriati, Vito,Salomone, Antonio
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supporting information
p. 8100 - 8103
(2018/07/29)
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- Synthesis of nanomagnetic supported thiourea–copper(I) catalyst and its application in the synthesis of triazoles and benzamides
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A novel nanomagnetic supported thiourea–copper(I) complex and inorganic–organic Takemoto-like hybrid nanomagnetic catalyst was designed, and synthesized. The prepared naomagnetic catalyst was characterized using Fourier transform infrared spectroscopy, X-ray diffraction, energy-dispersive X-ray analysis, transmission and scanning electron microscopies, thermogravimetry, nitrogen adsorption/desorption, zeta potential and vibrating sample magnetometry. Furthermore, the fabricated dual-role inorganic–organic hybrid catalyst shows a striking and robust catalytic activity for the synthesis of triazoles and benzamides through click and coupling reactions, respectively, under mild and eco-friendly reaction conditions.
- Mohammadi, Leila,Zolfigol, Mohammad Ali,Khazaei, Ardeshir,Yarie, Meysam,Ansari, Samira,Azizian, Saeid,Khosravi, Maryam
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- A Cross-Coupling Approach to Amide Bond Formation from Esters
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A palladium-catalyzed cross-coupling between aryl esters and anilines is reported, enabling access to diverse amides. The reaction takes place via activation of the C-O bond by oxidative addition with a Pd-NHC complex, which enables the use of relatively non-nucleophilic anilines that otherwise require stoichiometric activation with strong bases in order to react. High yields of aromatic, aliphatic, and heterocyclic products are obtained. A range of activated esters are evaluated in the presence and absence of catalyst, demonstrating that the catalytic methodology substantially increases the types of electrophiles that can be utilized for amide bond formation in the absence of harsh bases.
- Ben Halima, Taoufik,Vandavasi, Jaya Kishore,Shkoor, Mohanad,Newman, Stephen G.
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p. 2176 - 2180
(2017/08/09)
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- Copper-Catalyzed Coupling Reaction of (Hetero)Aryl Chlorides and Amides
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Cu2O/N,N′-bis(thiophen-2-ylmethyl)oxalamide is established to be an effective catalyst system for Goldberg amidation with inferior reactive (hetero)aryl chlorides, which have not been efficiently documented by Cu-catalysis to date. The reaction is well liberalized toward a variety of functionalized (hetero)aryl chlorides and a wide range of aromatic and aliphatic primary amides in good to excellent yields. Furthermore, the arylation of lactams and oxazolidinones is achieved. The present catalytic system also accomplished an intramolecular cross-coupling product.
- De, Subhadip,Yin, Junli,Ma, Dawei
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supporting information
p. 4864 - 4867
(2017/09/23)
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- Synthesis method of nicotinoyl aniline salt
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The invention discloses a synthesis method of nicotinoyl aniline salt. The synthesis method comprises the following steps: (1) adding nicotinic acid and aniline into a reactor according to the weight ratio of 1:(0.6-2.5), heating to 170-190DEG C, performing reflux reaction for 2-7h, heating to 190-210DEG C, and preserving heat and reacting for 0.5-1.5h; (2) transferring the liquid obtained in the step (1) to another water container and evenly stirring, cooling to 50-70DEG C, adding hydrochloric acid or sulfuric acid, and stirring for 10-50min, to obtain nicotinoyl aniline salt liquid; and (3) adding inorganic salt to the liquid obtained in the step (2), cooling to the temperature lower than 20DEG C, and performing suction filtration, to obtain rough nicotinoyl aniline salt. The synthesis method has the beneficial effects that the synthesis method is simple to operate, the reaction conditions are easily controlled, and the synthesis method is suitable for large-scale production and popularization; the purity of the synthesized nicotinoyl aniline salt is high, and the effects are excellent; and the cost is lowered, green and environment-friendly production is achieved, the environment pollution caused by organic solvents can be greatly decreased, and the treatment cost of three wastes can be lowered.
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Paragraph 0029; 0030
(2017/01/17)
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- Amine Activation: Synthesis of N-(Hetero)arylamides from Isothioureas and Carboxylic Acids
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A novel method for N-(hetero)arylamide synthesis based on rarely explored amine activation, rather than classical acid activation, is reported. The activated amines are easily prepared using a three-component reaction with commercial reagents. The new method shows a broad scope including challenging amides not (efficiently) accessible via classical protocols.
- Zhu, Yan-Ping,Sergeyev, Sergey,Franck, Philippe,Orru, Romano V. A.,Maes, Bert U. W.
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supporting information
p. 4602 - 4605
(2016/09/28)
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- Green alternative solvents for the copper-catalysed arylation of phenols and amides
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Investigation of the use of green organic solvents for the Cu-catalysed arylation of phenols and amides is reported. Alkyl acetates proved to be efficient solvents in the catalytic processes, and therefore excellent alternatives to the typical non-green solvents used for Cu-catalysed arylation reactions. Solvents such as isosorbide dimethyl ether (DMI) and diethyl carbonate also appear to be viable possibilities for the arylation of phenols. Finally, a novel copper catalysed acyl transfer process is reported.
- Sambiagio, Carlo,Munday, Rachel H.,John Blacker,Marsden, Stephen P.,McGowan, Patrick C.
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p. 70025 - 70032
(2016/08/06)
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- Palladium-Catalyzed Synthesis of Aryl Amides through Silanoate-Mediated Hydrolysis of Nitriles
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A procedure for the formation of aryl amides through the palladium-catalyzed coupling of nitriles and aryl bromides, via the formation of intermediary silanoate derived imidate species is reported. Optimization was undertaken and examples of the process are described that furnish the products in up to 86% isolated yield.
- McPherson, Christopher G.,Livingstone, Keith,Jamieson, Craig,Simpson, Iain
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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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- Efficient conversion of acids and esters to amides and transamidation of primary amides using OSU-6
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OSU-6, an MCM-41 type hexagonal mesoporous silica with strong Bronsted acid properties, has been used to promote the high-yield conversion of carboxylic acids and esters to carboxamides as well as transamidations of primary amides in a one-pot solventless approach. A metal-free heterogeneous catalyst that promotes all of these processes has not been previously reported. OSU-6 enables these transformations to proceed in shorter times and at lower temperatures for a broad range of substrates. An added benefit is that the catalyst can be recycled and reused multiple times without significant loss of activity.
- Nammalwar, Baskar,Muddala, Nagendra Prasad,Watts, Field M.,Bunce, Richard A.
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p. 9101 - 9111
(2015/11/09)
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- Imidazolium salt-supported Mukaiyama reagent: An efficient condensation reagent for amide bond formation
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A novel imidazolium salt-supported Mukaiyama reagent (2-chloropyridinium salt) has been developed and explored as an efficient coupling agent for amide bond formation. The use of an ionic liquid-supported reagent enabled isolation of the amide products by simple extraction with organic solvents in high purity and avoiding column chromatography purification. This journal is
- Pandey, Khima,Muthyala, Manoj Kumar,Choudhary, Sunita,Kumar, Anil
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p. 13797 - 13804
(2015/02/19)
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- Pyridyl-decorated self-folding heptaamide cavitands as ligands in the rhodium-catalyzed hydrogenation of norbornadiene
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The different binding geometries exhibited in solution by the Rh I cationic complexes of three regioisomeric self-folding heptaamide cavitands, each decorated with one pyridyl group at the upper rim, are taken into account to explain the diverse distributions of products obtained when these complexes are employed as catalysts for the hydrogenation of norbornadiene. Copyright
- Korom, Sasa,Ballester, Pablo
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p. 4276 - 4282
(2014/07/21)
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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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- Mesoporous niobium oxide spheres as an effective catalyst for the transamidation of primary amides with amines
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Mesoporous niobium oxide spheres (MNOS), conveniently prepared by a novel antisolvent precipitation approach, have been shown to be an effective catalyst for the transamidation of primary amides with amines. This novel transamidation can be efficiently carried out under solvent-free conditions and is applicable to a wide range of primary amides and amines to provide N-alkyl amides in good to excellent yields. The catalyst is highly stable and reusable. The application of this transamidation reaction has been demonstrated in the synthesis of antidepressant drug moclobemide and other druglike compounds.
- Ghosh, Subhash Chandra,Li, Cheng Chao,Zeng, Hua Chun,Ngiam, Joyce S. Y.,Seayad, Abdul M.,Chen, Anqi
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p. 475 - 484
(2014/05/20)
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- Benzoic acid-catalyzed transamidation reactions of carboxamides, phthalimide, ureas and thioamide with amines
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An efficient and simple method for the transamidation of carboxamides, phthalimide, ureas and thioamide with amines catalyzed by commercially available benzoic acid under metal-free conditions is described. Furthermore, to the best of our knowledge, this is the first report about the transamidation of an aromatic thioamide with amines.
- Wu, Ji-Wei,Wu, Ya-Dong,Dai, Jian-Jun,Xu, Hua-Jian
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supporting information
p. 2429 - 2436
(2014/09/30)
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- Copper-catalyzed regioselective synthesis of N-aryl amides from aldoximes and aryl halides
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Ligand-assisted copper-catalyzed reaction of aldoximes with aryl halides is described for the regioselective synthesis of N-aryl amides. This protocol is simple and compatible with a wide range of functional groups attached to the aryl ring of the halides as well as aldoximes. Copyright
- Panda, Niranjan,Mothkuri, Raghavender,Nayak, Dinesh Kumar
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supporting information
p. 1602 - 1605
(2014/03/21)
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- Copper-Catalyzed Regioselective Synthesis of N-Aryl Amides from Aldoximes and Aryl Halides
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Ligand-assisted copper-catalyzed reaction of aldoximes with aryl halides is described for the regioselective synthesis of N-aryl amides. This protocol is simple and compatible with a wide range of functional groups attached to the aryl ring of the halides as well as aldoximes.
- Panda, Niranjan,Mothkuri, Raghavender,Nayak, Dinesh Kumar
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supporting information
p. 1602 - 1605
(2015/10/05)
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- BippyPhos: A single ligand with unprecedented scope in the Buchwald-Hartwig amination of (hetero)aryl chlorides
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Over the past two decades, considerable attention has been given to the development of new ligands for the palladium-catalyzed arylation of amines and related NH-containing substrates (i.e., Buchwald-Hartwig amination). The generation of structurally diverse ligands, by research groups in both academia and industry, has facilitated the accommodation of sterically and electronically divergent substrates including ammonia, hydrazine, amines, amides, and NH heterocycles. Despite these achievements, problems with catalyst generality persist and access to multiple ligands is necessary to accommodate all of these NH-containing substrates. In our quest to address this significant limitation we identified the BippyPhos/[Pd(cinnamyl)Cl]2 catalyst system as being capable of catalyzing the amination of a variety of functionalized (hetero)aryl chlorides, as well as bromides and tosylates, at moderate to low catalyst loadings. The successful transformations described herein include primary and secondary amines, NH heterocycles, amides, ammonia and hydrazine, thus demonstrating the largest scope in the NH-containing coupling partner reported for a single Pd/ligand catalyst system. We also established BippyPhos/ [Pd(cinnamyl)Cl]2 as exhibiting the broadest demonstrated substrate scope for metal-catalyzed cross-coupling of (hetero)aryl chlorides with NH indoles. Furthermore, the remarkable ability of BippyPhos/[Pd(cinnamyl)Cl] 2 to catalyze both the selective monoarylation of ammonia and the N-arylation of indoles was exploited in the development of a new one-pot, two-step synthesis of N-aryl heterocycles from ammonia, ortho- alkynylhalo(hetero)arenes and (hetero) aryl halides through tandem N-arylation/hydroamination reactions. Although the scope in the NH-containing coupling partner is broad, BippyPhos/[Pd(cinnamyl)Cl]2 also displays a marked selectivity profile that was exploited in the chemoselective monoarylation of substrates featuring two chemically distinct NH-containing moieties.
- Crawford, Sarah M.,Lavery, Christopher B.,Stradiotto, Mark
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supporting information
p. 16760 - 16771
(2014/01/06)
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- Highly efficient aminocarbonylation of iodoarenes at atmospheric pressure catalyzed by a robust acenaphthoimidazolyidene allylic palladium complex
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A robust allylic palladium-NHC complex was developed and exhibited extremely high catalytic activity toward aminocarbonylation of various (hetero)aryl iodides under atmospheric carbon monoxide pressure, in which a broad range of secondary and primary amines were well tolerated. In addition, the concise synthesis of an anticancer drug tamibarotene was accomplished even in a gram scale, further highlighting the practical applicability of the protocol.
- Fang, Weiwei,Deng, Qinyue,Xu, Mizhi,Tu, Tao
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supporting information
p. 3678 - 3681
(2013/08/23)
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- Palladium-catalyzed amidation of aryl halides using 2-dialkylphosphino- 2′-alkoxyl-1,1′-binaphthyl as ligands
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Palladium-catalyzed intermolecular C-N bond-forming reactions between aryl halides and amides are described using 2-dialkylphosphino-2′-alkoxyl-1, 1′-binaphthyl, which is both bulky and electron-rich, as the ligand. A variety of amides, including aliphatic and aromatic primary amides, lactams, and carbamates, were viable substrates for the amidation, which exhibited good functional group compatibility. By tuning the substituents at the 2,2′-position of 1,1′-binaphthyl of the ligand, the palladium-catalyzed amidation of bulky aryl halides was realized and this coupling reaction was used to synthesize 2-amino-2′-methoxy-1,1′- binaphthyl in high yield.
- Ma, Fangfang,Xie, Xiaomin,Zhang, Lei,Peng, Zhiyong,Ding, Lina,Fu, Lei,Zhang, Zhaoguo
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experimental part
p. 5279 - 5285
(2012/08/07)
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- Pd0/PR3-catalyzed arylation of nicotinic and isonicotinic acid derivatives
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(Chemical Eqation Presented) Good for your health: Intermolecular C-H functionalization of pyridine rings at the 3- and 4-positions is described using a Pd0/PR3/ArBr catalytic system. This reaction provides a powerful method for the preparation of structurally diverse nicotinic and isonicotinic acids that are of great importance in drug discovery.
- Wasa, Masayuki,Worrell, Brady T.,Yu, Jin-Quan
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experimental part
p. 1275 - 1277
(2010/05/02)
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- Iron-catalyzed N-arylations of amides
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A method was proposed for iron-catalyzed N-arylation of primary amides and its applicability to the synthesis of N-heterocycles by intramolecular ring closures. The method used a catalyst system of 10 mol % of FeCl3 and 20 mol % of N,N'-dimethylethylenediamine (DMEDA). The study found that secondary amides of N-methylbenzamide and N-benzylbenzamide produce N-arylated products in trace amounts. The method developed an iron-based catalyst system for efficient N-arylations of primary amides with aryl iodides. The study used a sealable tube equipped with a magnetic stir bar charged with amide, or K 3PO4, or K2CO3, or FeCl3. The study used NMR spectroscopic analysis to determine the identity and purity of the products. The method observed that different substituted aryl iodides made a positive impact on the reaction.
- Correa, Arkaitz,Elmore, Simon,Bolm, Carsten
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experimental part
p. 3527 - 3529
(2009/04/11)
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- Single-crystal to single-crystal phase transitions of bis(N- phenylisonicotinamide)silver(I) nitrate reveal cooperativity properties in porous molecular materials
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Two single-crystal to single-crystal phase transitions in trans-[Ag(NPI)2](NO3)·2CH3OH (1a), (NPI = N-phenylisonicotinamide) were characterized with X-ray crystallography; the first transition is reversible and arises from a desolvation transition induced by vacuum and generated 1b; the second transition was induced by heat at 140°C and generated 1c. The Royal Society of Chemistry.
- Mukherjee, Partha S.,Lopez, Nazario,Arif, Atta M.,Cervantes-Lee, Francisco,Noveron, Juan C.
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p. 1433 - 1435
(2008/02/04)
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- Palladium-catalyzed aminocarbonylation of aryl chlorides at atmospheric pressure: The dual role of sodium phenoxide
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(Chemical Equation Presented) No pressure, no worries: A general, functional-group-tolerant, mild system for the Pd-catalyzed carbonylation of aryl chlorides to the corresponding amides has been developed. The catalyst operates at 1 atm CO using an inexpensive, air-stable, and commercially available ligand (see scheme, Cy = cyclohexyl). Sodium phenoxide is a critical additive in this transformation; its role has been studied using in situ IR spectroscopy.
- Martinelli, Joseph R.,Clark, Thomas P.,Watson, Donald A.,Munday, Rachel H.,Buchwald, Stephen L.
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p. 8460 - 8463
(2008/09/18)
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- Homogeneous catalytic aminocarbonylation of nitrogen-containing iodo-heteroaromatics. Synthesis of N-substituted nicotinamide related compounds
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Various primary and secondary amines, including amino acid methyl esters, were used as nucleophiles in palladium-catalysed aminocarbonylation of 2-iodopyridine, 3-iodopyridine and iodopyrazine. N-Substituted nicotinamides and 3-pyridyl-glyoxylamides (2-oxo-carboxamide type derivatives) of potential biological importance can be obtained from 3-iodopyridine as a result of simple and double carbon monoxide insertions, respectively. The latter examples can be obtained in synthetically acceptable yields by using elevated carbon monoxide pressure. On the contrary, N-alkyl/aryl-carboxamides were obtained exclusively in the whole pressure range by using 2-iodopyridine and iodopyrazine.
- Takács, Attila,Jakab, Balázs,Petz, Andrea,Kollár, László
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p. 10372 - 10378
(2008/02/13)
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- A β-keto ester as a novel, efficient, and versatile ligand for copper(I)-catalyzed C-N, C-O, and C-S coupling reactions
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(Formula Presented) Employing ethyl 2-oxocyclohexanecarboxylate as a novel, efficient, and versatile ligand, the copper-catalyzed coupling reactions of various N/O/S nucleophilic reagents with aryl halides could be successfully carried out under mild conditions. A variety of products including N-arylamides, N-arylimidazoles, aryl ethers, and aryl thioethers were synthesized in good to excellent yields.
- Lv, Xin,Bao, Weiliang
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p. 3863 - 3867
(2008/02/02)
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- Formation of acrylanilides, acrylamides, and amides directly from carboxylic acids using thionyl chloride in dimethylacetamide in the absence of bases
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A general one-pot procedure is described that rapidly converts acrylic acid to anilides upon sequential treatment of the acid in dimethylacetamide (DMAC) with thionyl chloride and stoichiometric amounts of anilines in 88-98% yields, with DMAC offering rate and stability advantages over the use of DMF. The use of DMAC was extended to other organic acids in forming anilides. Benzylamine amides can also be formed using stoichiometric amounts of benzylamine and brought to completion by warming in the absence of additional base. In addition, it was shown that tert-butylamides can be easily formed with the addition of excess tert-butylamine at 20 °C.
- Cvetovich, Raymond J.,DiMichele, Lisa
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p. 944 - 946
(2012/12/23)
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- N-arylamides from selenium-catalyzed reactions of nitroaromatics and amides in the presence of carbon monoxide and mixed organic bases
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N-Arylamides were exclusively obtained in moderate to good yields from selenium-catalyzed reactions of nitroaromatics with amides in the presence of CO and mixed organic bases Et3N and DBU.
- Chen, Jinzhu,Ling, Gang,Yu, Zhengkun,Wu, Sizhong,Zhao, Xiaodan,Wu, Xiaowei,Lu, Shiwei
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p. 1267 - 1270
(2007/10/03)
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- Improved synthesis of N-substituted 2,3-pyridine-dicarboximides with microwave irradiation
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The microwave-induced synthesis of N-substituted 2,3- pyridinedicarboximides (1) by means of two different approaches is presented. One involves direct N-alkylation of quinolinimide (2) (Method A) and the other, dehydrative condensation of quinolinic anhydride (4) and amines (Method B). Reactions resulted highly accelerated, with improved yields in relation to those obtained by conventional heating. The scope and limitations of each method and its variants are discussed.
- Blanco, Maria M.,Levin, Gustavo J.,Schapira, Celia B.,Perillo, Isabel A.
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p. 1881 - 1890
(2007/10/03)
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- α-nitrogen activating effect in the room temperature copper-promoted N-arylation of heteroarylcarboxamides with phenyl siloxane or p-toluylboronic acid
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Heteroarylcarboxamides containing α-nitrogens undergo copper-promoted N-phenylation with hypervalent phenyl trimethylsiloxane at room temperature, in the absence of base and in air. Arylboronic acid can substitute for phenyl trimethylsiloxane as the organ
- Lam, Patrick Y.S.,Deudon, Sophie,Hauptman, Elisabeth,Clark, Charles G.
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p. 2427 - 2429
(2007/10/03)
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- Synthesis of 2-pyridinylbenzoxazole: Mechanism for the intramolecular photosubstitution of the haloarene with the carbonyl oxygen of the amide bond in basic medium
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2-Pyridinylbenzoxazole derivatives have been synthesized by the intramolecular photosubstitution reaction of N-(2- halophenyl)pyridinecarboxamide (1 and 2) with its amide bond in basic medium. In neutral medium both intramolecular photosubstitution and photoreduction reactions occurred. In the photosubstitution reaction a singlet state of the o-haloarene is involved, whereas in the photoreduction a triplet state of the o-haloarene is involved; oxygen inhibited the photoreduction but not the photosubstitution. The relative rate studies showed that a base accelerates the photosubstitution reaction but decelerates the photoreduction. o- Iodoarenecarboxamide is more reactive than o-bromoarenecarboxamide, which in turn is more reacitive than o-chloroarenecarboxamide. UV-vis absorption change in the presence of a base showed that an imidol and/or imidolate anion is involved in the reaction. Several transient species, such as charge- transfer excited states and a cyclohexadienyl anion radical, have been identified from the photolysis of 1 and 2 in basic medium by laser flash photolysis. In neutral medium dibromide anion radical and a phenyl radical were identified in addition to the above intermediates. On the basis of the photokinetic and laser flash photolysis studies, an intramolecular photosubstitution of N-(o-halophenyl)pyridinecarboxamide with its amide bond occurs via an intramolecular S(N)(ET)Ar* mechanism to afford 2- pyridinylbenzoxazole derivative, and the photoreduction proceeds via a free radical mechanism to give N-phenylpyridinecarboxamide.
- Park, Yong-Tae,Jung, Chang-Hee,Kim, Kwang-Wook,Kim, Ho Sik
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p. 8546 - 8556
(2007/10/03)
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- AN UNUSUAL SYNTHESIS OF NICOTINAMIDES
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Reaction of 2,3-pyridinedicarboxylic anhydride (1) with a substituted aniline (2) in acetic acid gave rise to a mixture of two products.These two products were identified as the cyclic imide (4) and nicotinamide (5).A mechanistic scheme consistent with empirical observations is proposed.
- Harrington, Philip M.
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p. 683 - 687
(2007/10/02)
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- POLAROGRAPHIC REDUCTION OF 1-BENZYL-N-(p-X-PHENYL)-3-AMINOCARBONYLPYRIDINIUM SALTS
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The substitution effect of different groups X (N(CH2CH3)2, OH, OCH3, CH3, NHCOCH3, H, Cl, COOCH2CH3 and NO2) on the polarographic behaviour of 3-(N-p-X-phenylaminocarbonyl)pyridines (I),1-benzyl-N-(p-X-phenyl)-3-aminocarbonylpyridinium cations (II) and their respective 1,4-dihydroderivatives (III) has been investigated in anhydrous solution of dimethylformamide with 0.1 mol 1-1 (n-C4H9)4N+PF6- as supporting electrolyte.The half-wave potentials of the reduction wave of I and II, which correspond to the uptake of a single electron (wave B) and to the formation of a primary radical, obey a Hammett correlation in a similar way as it is in the case of 1-benzyl- and 1-phenyl-3-amino-carbonylopyridinium cations substituted at carbon 4 on the benzene nucleus.The slope q?,R in the Hammett plot equals 0.192 V (I) and 0.104 V (II) for anhydrous DMF and compares thus with this slope obtained with the 1-benzyl- and 1-phenyl derivatives in our previous communications.
- Krechl, Jiri,Beranova, Sarka,Volkeova, Vera,Volke, Jiri,Kuthan, Josef
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p. 2008 - 2018
(2007/10/02)
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- The Use of a Nicotinoyl Group as a Protective Group for Hydroxyl and Amino Functions
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The effective use of a nicotinoyl group as an easily introducible and cleavable protective group for hydroxyl and amino groups is described.Deprotection by alkaline hydrolysis is performed after activation by quarternization of pyridine moiety with methyl iodide.
- Ushida, Satoshi
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