1122-61-8Relevant articles and documents
C-Nitration of pyridine by the kyodai-nitration modified by the Bakke procedure. A simple route to 3-nitropyridine and mechanistic aspect of its formation
Suzuki, Hitomi,Iwaya, Masao,Mori, Tadashi
, p. 5647 - 5650 (1997)
N-Nitropyridinium nitrate was generated in situ from pyridine, nitrogen dioxide and ozone in an inert organic solvent and subsequently treated with aqueous sodium hydrogen sulfite to afford 3-nitropyridine in good yield, together with sodium pyridine-4-sulfonate as a water-soluble by-product.
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Cazianis,Eaton
, p. 2463,2464, 2465, 2467 (1974)
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A computational approach to tuning the photochemistry of platinum(IV) anticancer agents
Tai, Hui-Chung,Zhao, Yao,Farrer, Nicola J.,Anastasi, Anna E.,Clarkson, Guy,Sadler, Peter J.,Deeth, Robert J.
, p. 10630 - 10642,13 (2012)
Diazido PtIV complexes are inert stable prodrugs that can be photoactivated to produce PtII species with promising anticancer activity. Our studies of the photochemistry of PtIV complexes, [Pt(X)2(Y)2(Z)2]0/-1 (X=N-ligands (NH3, pyridine, etc.)/S(CH3)2/H-, Y=(pseudo)halogen (N3-, I-), Z=OR-, R=H, Ac) by time-dependent density functional theory (TDDFT) show close agreement with spectroscopic data. Broad exploration of cis/trans geometries, trans influences, the nature of the OR- and (pseudo)halogen ligands, electron-withdrawing/donating/delocalising substituents on the N-ligands, and intramolecular H bonds shows that: 1) the design of platinum(IV) complexes with intense bands shifted towards longer wavelengths (from 289 to ～330 nm) can be achieved by introducing intramolecular H bonds involving the OH ligands and 2-hydroxyquinoline or by iodido ligands; 2) mesomeric electron-withdrawing substituents on pyridine result in low-energy absorption with significant intensity in the visible region; and 3) the distinct makeup of the molecular orbitals involved in the electronic transitions for cis/trans-{Pt(N 3)2} isomers results in different photoproducts. In general, the comparison of the optimised geometries shows that PtIV complexes with longer Pt-L bonds are more likely to undergo photoreduction with longer-wavelength light. The novel complex trans,trans,trans-[Pt(N 3)2(OH)2(NH3)(4-nitropyridine)] with predicted absorption in the visible region has been synthesised. The experimental UV/Vis spectrum in aqueous solution correlates well with the intense band in the computed spectrum, whereas the overlay in the low-energy region can be improved by a solvent model. This combined computational and experimental study shows that TDDFT can be used to tune the coordination environment for optimising photoactive PtIV compounds as anticancer agents. Computer-aided design: Platinum(IV) complexes are inert stable prodrugs that can be photoactivated to produce species with promising anticancer activity. Here a combined computational and experimental study was carried out to show that TDDFT can aid the design of the coordination environment of Pt IV complexes to allow optimisation of the photoactivity of these PtIV anticancer agents (see figure). Copyright
Kinetics and mechanistic study on deoxygenation of pyridine oxide catalyzed by {MeReVO(pdt)} 2 dimer
Ibdah, Abdellatif,Alduwikat, Salwa
supporting information, p. 9 - 20 (2017/05/19)
The oxorhenium(V) dimer {MeReO(pdt)}2 (where pdt?=?1,2-propanedithiolate) catalyze the oxygen atom transfer (OAT) reaction from the pyridine oxide to triphenylarsine (Ph3As). The rate law is given by ν?=?k[Re-dimer][PyNO] and zero order dependence on Ph3As. The value of k at 25?°C in CHCl3 is 139?±?3?L?mol?1?s?1. The activation parameters are ΔH??=?12.2?±?1.0?kcal?mol?1 and ΔS??=??7.9?±?3.24?cal?K?1?mol?1. According to the proposed mechanism, the rate determining step is the oxidation of ReVO to ReVIIO2 and the pyridine release. The triphenylarsine enters the catalytic cycle after the rate determining step. The reaction constant ρ?=??1.4 obtained from Hammett correlation with σ for different substituted pyridine N-oxide. The computational study indicates that the oxidation of ReV to ReVII and release of the pyridine step is insensitive to the nature of the substituent on the pyridine with the average estimated activation barrier ≈11.5?kcal/mol from six different substituted pyridine oxide. It is proposed that electron donor substituent enrich the equilibrium of the first step of the proposed mechanism which is the coordination of the pyridine oxide with one rhenium atom to form I1 (Scheme 2). The electron donor substituent on the pyridine increase the concentration of I1 which will increase the rate of the reaction as the ν?=?k2[I1].
Catalytic deoxygenation of pyridine N-oxides with N-fused porphyrin rhenium complexes
Toganoh, Motoki,Fujino, Keitaro,Ikeda, Shinya,Furuta, Hiroyuki
, p. 1488 - 1491 (2008/09/18)
Deoxygenation reactions of pyridine N-oxide derivatives catalyzed by N-fused porphyrin rhenium(VII) trioxo complexes are developed, affording the corresponding pyridine derivatives in quantitative yields with excellent turnover numbers up to 340,000.
