- Thermodynamic Properties of Organic Compounds. 3. Sublimation Enthalpy and Heat Capacities of 2,4,6-Trimethylbenzonitrile N-Oxide
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Experimental heat capacities (6-319 K) and enthalpy of sublimation, ΔsubH deg m(313.5K) = 87.52 +/- 0.53 kJ mol-1, are reported for 2,4,6-trimethylbenzonitrile N-oxide.Heat capacity data show a reversible solid-phase trans
- Acree, William E.,Sevruk, Viktor M.,Kozyro, Alexander A.,Krasulin, Alexander P.,Kabo, Gennady J.,Frenkel, Michael L.
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Read Online
- N,O-Nucleosides from Ene Reaction of (Nitrosocarbonyl)mesitylene with Crotyl Alcohol: Selectivity, Scope, and Limitations
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The (nitrosocarbonyl)mesitylene intermediate undergoes an ene reaction with crotyl alcohol, affording two regioisomeric adducts in fair yields. The sterically demanding (nitrosocarbonyl)mesitylene slightly shifts the C2/Markovnikov orientation towards a C
- Carosso, Serena,Memeo, Misal Giuseppe,Bovio, Bruna,Valletta, Elena,Macchi, Beatrice,Quadrelli, Paolo
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- Arylation of nitromethane with sterically hindered aryl halides
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Efficient conditions for Pd-catalyzed cross-coupling of sterically hindered aryl halides with nitromethane were developed to give corresponding aryl nitromethanes. The opportunity to carry out the reaction of polynitromethylation under these conditions wa
- Ageshina, A. A.,Asachenko, A. F.,Lysenko, A. N.,Minaeva, L. I.,Nechaev, M. S.,Rasskazova, M. A.,Rzhevskiy, S. A.,Topchiy, M. A.
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- Regioselective [3+2] cycloaddition of nitrile oxides to 1Н-pyrrole-2,3-diones: synthesis of spiro[pyrroledioxazoles]
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[Figure not available: see fulltext.] 1,3-Dipolar cycloaddition of 1H-pyrrole-2,3-diones to nitrile oxides generated in situ from N-hydroxybenzimidoyl chlorides by the action of triethylamine proceeds regioselectively with the formation of 1,4,2-dioxazole
- Dmitriev, Maksim V.,Maslivets, Andrey N.,Moroz, Anna А.
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- Palladium-Catalyzed (3+3) Annulation of Allenylethylene Carbonates with Nitrile Oxides
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In this paper, we designed and synthesized a new type of cyclic carbonates, allenylethylene carbonates (AECs). With AECs as reactive precursors, we developed palladium-catalyzed (3+3) annulation of AECs with nitrile oxides. Various AECs worked well in this reaction under mild reaction conditions. A variety of 5,6-dihydro-1,4,2-dioxazine derivatives with allenyl quaternary stereocenters can be accessed in a facile manner in high yields (≤98%).
- Pan, Ting,Gao, Xing,Yang, Sen,Wang, Lan,Hu, Yimin,Liu, Min,Wang, Wei,Wu, Yongjun,Zheng, Bing,Guo, Hongchao
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p. 5750 - 5754
(2021/08/16)
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- In Situ Generation of Nitrile Oxides from NaCl-Oxone Oxidation of Various Aldoximes and Their 1,3-Dipolar Cycloaddition
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Reported is a new green protocol for the efficient in situ generation of nitrile oxides through NaCl/Oxone oxidation of aldoximes and their dipolar cycloaddition. The key feature is the use of a green chemistry approach to address the substrate scope of aldoximes: broad scope (aliphatic, aromatic, and alkenyl aldoximes) without production of organic byproducts derived from oxidant and/or catalyst. Importantly, NaCl/Oxone-promoted three-component cycloaddition of aldehyde, hydroxylamine hydrochloride, and alkene was demonstrated to be competent (63-81%).
- Zhao, Guodong,Liang, Lixin,Wen, Chi Ho Ethan,Tong, Rongbiao
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supporting information
p. 315 - 319
(2019/01/08)
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- Macromolecular surface design: Photopatterning of functional stable nitrile oxides
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The efficient trapping of photogenerated thioaldehydes with functional shelf-stable nitrile oxides in a 1,3-dipolar cycloaddition is a novel and versatile photochemical strategy for polymer end-group functionalization and surface modification under mild a
- Altintas, Ozcan,Glassner, Mathias,Rodriguez-Emmenegger, Cesar,Welle, Alexander,Trouillet, Vanessa,Barner-Kowollik, Christopher
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supporting information
p. 5777 - 5783
(2015/05/20)
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- Electroorganic synthesis of nitriles via a halogen-free domino oxidation-reduction sequence
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A direct electroorganic sequence yielding nitriles from oximes in undivided cells is reported. Despite the fact that intermediate nitrile oxides might be formed, the method is viable to prepare benzonitriles without substituents ortho to the aldoxime moiety. This constant current method is easy to perform for a broad scope of substrates and employs common electrodes, such as graphite and lead.
- Hartmer, Marius F.,Waldvogel, Siegfried R.
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supporting information
p. 16346 - 16348
(2015/11/16)
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- N, O -nucleosides from ene reactions of nitrosocarbonyl intermediates with the 3-methyl-2-buten-1-ol
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Nitrosocarbonyl intermediates undergo ene reactions with allylic alcohols, affording regioisomeric adducts in fair yields. Nitrosocarbonyl benzene reacts with 3-methyl-2-buten-1-ol and follows a Markovnikov orientation and abstracts preferentially the twi
- Quadrelli, Paolo,Mella, Mariella,Carosso, Serena,Bovio, Bruna
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p. 516 - 526
(2013/03/14)
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- From the ene reaction of nitrosocarbonyl intermediates with 3-methylbut-2-En-1-Ol, a new class of purine N,O-nucleoside analogues
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Sterically encumbered nitrosocarbonyl derivatives of mesitylene or anthracene undergo ene reactions with 3-methylbut-2-en-1-ol to give the corresponding the 5-hydroxyisoxazolidine adducts in fair yields. According to the proposed mechanism, these heterocy
- Quadrelli, Paolo,Mella, Mariella,Carosso, Serena,Bovio, Bruna
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p. 1414 - 1420
(2013/07/04)
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- A comparative study of the effect of water and organic solvents on 1,3-dipolar cycloaddition reactions of mesitonitrile oxide with c-sulfonyl- and sulfanyl-dithioformates
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1,3-Dipolar cycloadditions of the C-sulfonylated- and sulfanylated- dithioformates with mesitonitrile oxide occurred smoothly in organic and aqueous media to afford 1,4,2-oxathiazoles in good yields. The structures of these cycloadducts have been establis
- El-Sayed, Ibrahim,Ali, Omar M.,Hawata, Mohamed A.,Hegazey, Sally Abou
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scheme or table
p. 1979 - 1985
(2010/11/18)
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- Amine-promoted cyclocondensation of highly substituted aromatic nitrile oxides with diketones
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Base-promoted cyclocondensation of hindered nitrile oxides and cyclic diketones affords highly functionalized, sterically-encumbered isoxazole products in good yield. The mild reaction conditions (NEt3, EtOH) are tolerant to a wide variety of f
- Bode, Jeffrey W.,Hachisu, Yoshifumi,Matsuura, Tomoo,Suzuki, Keisuke
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p. 3555 - 3558
(2007/10/03)
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- Regioselective synthesis and side-chain metallation and elaboration of 3-aryl-5-alkylisoxazoles
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A number of 3-aryl-5-alkylisoxazoles have been synthesized in high yields by reacting arylnitrile oxides with free enolate ions regioselectively obtained by metallation of various alkyl methyl ketones with LDA in THF at -78°C followed by dehydration. Inve
- Di Nunno, Leonardo,Scilimati, Antonio,Vitale, Paola
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p. 2659 - 2665
(2007/10/03)
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- Sugar-based ethenyl ethers: Stereoselective dipolar cycloadditions of nitrile oxides
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Selected sugar-based ethenyl ethers have been employed in 1,3-dipolar cycloaddition with nitrile oxides. In the D-fructo series, high diastereoselectivity was observed as compared with the 3-epimeric D-psico series.
- Desroses, Matthieu,Chery, Florence,Tatibouet, Arnaud,De Lucchi, Ottorino,Rollin, Patrick
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p. 2535 - 2539
(2007/10/03)
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- Cycloadditions of nitrile oxides to α,β-unsaturated aldehydes. Frontier orbital interactions and secondary orbital interactions at work in determining regiochemistry
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The regiochemistry of the cycloadditions of nitrile oxides to crotonaldehyde and cinnamaldehyde has been determined and is dictated by frontier orbital interactions and secondary orbital interactions as well. In cycloadditions to α,β-unsaturated compounds the directive effect of the frontier orbital interactions can be diverted by steric drifts and secondary orbital interactions. (C) 2000 Elsevier Science Ltd.
- Toma, Lucio,Quadrelli, Paolo,Perrini, Giancarlo,Gandolfi, Remo,Di Valentin, Cristiana,Corsaro, Antonino,Caramella, Pierluigi
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p. 4299 - 4309
(2007/10/03)
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- Generation of nitrile oxides from oxime derivatives by the oxidation with ammonium hexanitratocerate(IV)
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Aromatic and aliphatic nitrile oxides are generated by the oxidation of α-hydroxyimino carboxylic acid with ammonium hexanitratocerate(IV). They react with olefinic and acetylenic dipolarophiles to give the corresponding cycloaddition products in good yield. The oxidation of α-oxo aldoximes also affords α-oxo carbonitrile oxides.
- Arai, Noriyoshi,Iwakoshi, Mitsuhiko,Tanabe, Katsuhiko,Narasaka, Koichi
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p. 2277 - 2285
(2007/10/03)
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- Enthalpies of combustion of 2,4,6-trimethylbenzonitrile, 2,4,6-trimethylbenzonitrile N-oxide, 2,6-dimethylbenzonitrile, 2,4,6-trimethoxybenzonitrile, and 2,4,6-trimethoxybenzonitrile N-oxide: the dissociation ethalpies of the (N-O) bonds
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The standard (pdeg = 0.1 MPa) molar enthalpies of combustion at 298.15 K were measured by static-bomb calorimetry and the standard molar enthalpies of sublimation at 298.15 K were measured by microcalorimetry for the following aromatic nitriles and aromatic nitrile N-oxides: .From the standard molar enthalpies of formation of the gaseous compounds, the molar dissociation enthalpies of the (N-O) bonds were derived: D(N-O)/(kJ*mol-1): trimethylbenzonitrile N-oxide, (222.2 +/- 4.6); trimethoxybenzonitrile N-oxide, (232.8 +/- 3.8).
- Acree, W. E.,Tucker, Sheryl A.,Zvaigzne, Anita I.,Meng-Yan, Yang,Pilcher, G.,Ribeiro da Silva, Maria D. M. C.
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- A Convenient Synthesis of Nitrile Oxides from Aldoximes by 1-Chlorobenzotriazole
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Nitrile oxides can be conveniently prepared from aldoximes utilizing 1-chlorobenzotriazole in dichloromethane.The reaction and work-up procedures are simple and the isolated yields high.
- Kim, Jae Nyoung,Ryu, Eung K.
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p. 1373 - 1377
(2007/10/02)
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- 1,3-Dipolar Cycloaddition of Nitrile Oxides to N-Vinylcarbazole: Regioselective Formation of 5-(9-Carbazolyl)-Δ2-Isoxazolines
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Aryl substituted nitrile oxides undergo 3 + 2 cycloaddition to N-vinylcarbazole to afford only one regioisomer, i.e., 3-aryl sustituted 5-(9-carbazolyl)-Δ2-isoxazolines III in good yield.
- Rao, K. Rama,Nageswar, Y. V. D.,Sattur, P. B.
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p. 255 - 256
(2007/10/02)
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- ESR STUDIES OF SOME IMINOXYL RADICALS CONTAINING 13C, PHOSPHORUS AND SULPHUR SUBSTITUENTS
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Some new aryliminoxyl radicals with a 13C, a 31P or a sulphur atom bonded to the azomethine carbon have been generated and studied by ESR spectroscopy.The influence of substitution on the relative stabilities of the syn and anti isomeric forms of these radicals are discussed.It is shown that a relation exists between the phosphorus splittings in these iminoxyls and the a(31P) of similarly substituted phosphonyl and thiophosphonyl radicals.
- Alberti, Angelo,Pedulli, Gian Franco
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p. 131 - 134
(2007/10/02)
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- Aqeous and Nonaqueous Polarographic Studies of Substituted 2,6-Dimethylbenzonitrile N-Oxides1)
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Aqueous and nonaqueous polarographic properties of 4-substituted 2,6-dimethylbenzonitrile N-oxides (stable nitrile N-oxides) have been studied and compared with those of the substituted pyridine N-oxides and benzylidenemethylamine N-oxides (nitrones) investigated previously by us.The first reduction wave in both the aqueous and N,N-dimethylformamide (DMF) solvent systems is due to the deoxygenation reaction of the nitrile N-oxide group except when certain substituents are present (see text).This conclusion has also been verified by controlled potential electrolysis in aqueous solution and by cyclic voltammetry in DMF solvent.A plot of the Hammett ? constants of the substituents against E1/2 values was linear with a positive slope for both the aqueous and DMF solvent systems.The slope is smaller than in the case of pyridine N-oxides and nitrones, this being reasonably attributable to the triple bond nature of the CNO group.Half-wave reduction potentials of the nitrile N-oxides are positively shifted compared with those of pyridine N-oxides, particularly in an aqueous solvent.Molecular orbital calculations were applied to interpret the substituent effect on the reduction potentials of the N-oxides. Keywords --- aqueous polarography; nonaqueous polarography; substituent effect on half-wave potential; cyclic voltammetry; controlled potential electrolysis; PPP-SCFMO; CNDO/2; LUMO energy; 4-substituted 2,6-dimethylbenzonitrile N-oxide
- Kubota, Tanekazu,Hiramatsu, Sadaaki,Kano, Kenji,Uno, Bunji,Miyazaki, Hiroshi
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p. 3830 - 3839
(2007/10/02)
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- STEREOCHEMISTRY OF IMINOXY RADICALS
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Iminoxy radicals of general structure Ar-C(X)=N-O, where X=H, CH2OH, n-Bu, t-Bu, SiEt3, SiPh3, GePh3, SnMe3, SnBu3, SnPh3, SMe, SBu, SPh, Cl and Br, have been photolytically generated from the parent oximino compounds or from aromatic nitrile N-oxides in an aprotic solvent.Two configurational isomers, interconvertible in solution, have been detected by electron spin resonance spectroscopy for the majority of these radicals.The preferred geometry of iminoxyls derived from ortho-unsubstituted benzaldoximes is that which places the aryl ring and the oxygen atom on the same side of the C=N double bond (anti).Substitution of the azomethine proton leads to a stabilization of the syn configuration, the effect being larger the greater the atomic number of the leading atom of the substituent group.The relative stability of the syn isomer is also increased by substitution of the aromatic ortho protons.INDO calculations have been carried out on several model systems in order to rationalize the experimental results.The effects responsible for the configurational preference of the different terms of this series of radicals are discussed in terms of a perturbation molecular orbital (PMO) approach.
- Alberti, Angelo,Barbaro, Gaetano,Battaglia, Arturo,Guerra, Maurizio,Bernardi, Fernando,et al.
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p. 742 - 750
(2007/10/02)
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