14335-33-2Relevant articles and documents
Rotational spectra and structures of the C6H6-HCN dimer and Ar3-HCN tetramer
Gutowsky, H. S.,Arunan, E.,Emilsson, T.,Tschopp, S. L.,Dykstra, C. E.
, p. 3917 - 3927 (1995)
A comparative study has been made of the rotational properties of C6H6-HCN and Ar3-HCN, observed with the Balle/Flygare pulsed beam, Fourier transform microwave spectrometer.C6H6-HCN is found to be a prolate symmetric top and Ar3-HCN an oblate one, both with the H in the middle.The rotational constants B0, DJ, and DJK of the parent species are 1219.9108(4) MHz, 1.12(3) kHz, and 18.32(8) kHz for C6H6-HCN,and 886.4878(1) MHz, 10.374(2) kHz, and 173.16(1) kHz for Ar3-HCN.Rotational constants are reported for the isotopic species C6H6-H13CN, -HC15N, and 13CC5H6-HC15N, and for Ar3-HC15N and -DCN.Analysis of the 14N hyperfine interaction χ finds its projection on the figure axis to be -4.223(4) MHz in C6H6-HCN and -1.143(2) in Ar3-HCN.They correspond to average projection angles θ between the HCN and figure axes of 15.2 deg and 45.3 deg, respectively.A pseudodiatomic analysis of the rotational constants gives the c.m. to c.m. distance to be 3.96 Angstroem in C6H6-HCN and 3.47 Angstroem in Ar3-HCN.While the rotational properties of C6H6-HCN are normal those of Ar3-HCN display a long list of abnormalities .They include a J-dependent χ(14N) similar to that of Ar-HCN; a very large projection angle θ, large centrifugal distortion including higher-order terms in HJ and HJK; splitting of the K=3 transitions into J-dependent doublets; and the ready observation of an excited vibrational state.These behavior differences are related qualitatively to the interaction surfaces for the two clusters, calculated with the molecular mechanics for clusters (MMC) model, and discussed.The potential minimum for C6H6-HCN is smooth, circular, steep except for a flat bottom, and deep (1762 cm-1).That for Ar3-HCN is tricuspid, with large gullies, and shallow (507 cm-1).In addition to the dispersion forces, the dominant interaction forming C6H6-HCN is between the benzene quadrupole moment and the HCN dipole moment, a strong 4-2 potential.That in Ar3-HCN is polarization of the spherical Ar by the HCN dipole and quadrupole moments, a weak 0-2,4 potential.
83Kr nuclear quadrupole coupling, microwave spectrum, and structure of KrHCN
Campbell, E. J.,Buxton, L. W.,Legon, A. C.
, p. 3483 - 3493 (1983)
Rotational spectra have been observed for ten isotopic species of KrHCN using the pulsed Fabry-Perot Fourier transorm technique.The 83Kr nuclear quadrupole coupling constant has been measured in 83KrHC14N, 83KrHC15N, and 83KrDC14N.Values of the rotational constants B0, centrifugal distortion constants DJ and H, 14N and 83Kr nuclear quadrupole coupling constants are: . aCalculated using DJ=47.401 kHz, H=69.4 Hz. bCalculated using DJ=40.350 kHz, H=54.3 Hz. cCalculated using DJ=26.973 kHz, H=27.2 Hz.These constants are consistent with a linear or near-linear configuration, with a Kr-HCN center-off-mass separation of 4.54 Angstroem, and the Kr atom located 27 deg off the HCN figure axis on average, where the vertex of this angle is placed on the HCN center-off-mass.KrHCN exhibits unusually large centrifugal distortion in comparison to previously studied Kr-hydrogen halide systems.We find that the measured 83Kr nuclear quadrupole coupling constants in 83KrHC14N and 83KrDC14N are consistent with a long range polarization model previously used to explain values of χKr in KrH(D)Cl and KrH(D)F.
Williams, D.,Plyler, E. K.
, p. 319 - 321 (1937)
Synthesis and biological evaluation of deuterated sofosbuvir analogs as HCV NS5B inhibitors with enhanced pharmacokinetic properties
Ao, Wangwei,Ma, Xueqin,Lin, Youping,Wang, Xiaojing,Song, Wei,Wang, Qinglin,Zhang, Xiquan,Xu, Hongjiang,Zhang, Yinsheng
, p. 215 - 229 (2019/05/07)
A series of deuterated sofosbuvir analogs were designed and prepared with the aim of improving their pharmacokinetic properties. The devised synthetic routes allow for site-selective deuterium incorporation with high levels of isotopic purity. As expected, the deuterated analogs (37-44) are as efficacious as sofosbuvir when tested in vitro inhibition of viral replication (replicon) assays. Compared with sofosbuvir, deuterated analog 40 displays improved in vivo pharmacokinetics profiles in rats and dogs in terms of the metabolite and the prodrug. The Cmax and area under the curve (AUC) of 40 in dogs were increased by 3.4- and 2.7-fold, respectively. Due to the enhanced pharmacokinetic properties and the great synthetic advantage of an inexpensive deuterium source (D2O) for 40, it was chosen for further investigation.
Oxidation of lower oxyacids of phosphorus by tetraethylammonium chlorochromate: A kinetic and mechanistic study
Vadera, Khushboo,Sharma,Agarwal,Sharma, Pradeep K.
, p. 302 - 306 (2011/01/10)
Oxidation of lower oxyacids of phosphorus by tetraethylammonium chlorochromate in dimethyl sulphoxide leads to the formation of corresponding oxyacids with phosphorus in a higher oxidation state. The reaction exhibits 1:1 stoichiometry. The reaction is first order each with respect to chlorochromate and the oxyacids. The reaction does not induce polymerization of acrylonitrile. The oxidation of deuterated phosphinic and phosphorous acids exhibits a substantial primary kinetic isotope effect. The oxidation has been studied in nineteen different organic solvents. The effect of solvent indicates that the solvent polarity plays a major role in the process. It has been shown that the pentacoordinated tautomer of the phosphorus oxyacid is the reactive reductant and the tricoordinated form of phosphorus oxyacids does not participate in the oxidation process. A mechanism involving transfer of a hydride ion in the rate determining step has been proposed.
