91597-65-8Relevant academic research and scientific papers
Solute-solvent interactions and chiral induction in liquid crystals
Celebre, Giorgio,De Luca, Giuseppina,Maiorino, Michela,Iemma, Francesca,Ferrarini, Alberta,Pieraccini, Silvia,Spada, Gian Piero
, p. 11736 - 11744 (2007/10/03)
The induction of a cholesteric phase by doping an achiral nematic liquid crystal with an enantiopure solute is a phenomenon that, as in all general supramolecular phenomena of chiral amplification, depends in a subtle way on intermolecular interactions. T
Large-scale preparation of [13C]methyl phenyl sulfide from [13C]methanol by a one-step process
Martinez, Rodolfo A.,Alvarez, Marc A.,Velarde, Stephen P.,Silks, Louis A. Pete,Stotter, Philip L.,Schmidt, Juergen G.,Unkefer, Clifford J.
, p. 851 - 854 (2013/09/06)
We have developed a large-scale "one-pot" procedure for the conversion of commercially available [13C]- or [2H3,13C]-methanol to [13C]- or [2H3,13C]methyl phenyl sulfide. [13C]methyl phenyl sulfide is a potentially versatile, chemically stable, and nonvolatile labeling precursor. In addition, we report an efficient method for the oxidation of [13C]methyl phenyl sulfide to [13C]methyl phenyl sulfone. Finally, we have used [13C]methyl phenyl sulfide to produce 13C-labeled methyl iodide, containing exactly one or two deuterons.
Design, synthesis, and in vitro inhibitory activity toward human leukocyte elastase, cathepsin G, and proteinase 3 of saccharin-derived sulfones and congeners
Groutas, William C.,Epp, Jeffrey B.,Venkataraman, Radhika,Kuang, Rongze,Truong, Tien My,McClenahan, Jerry J.,Prakash, Om
, p. 1393 - 1400 (2007/10/03)
The inhibitory activity toward human leukocyte elastase (HLE), cathepsin G (Cat G), and proteinase 3 (PR 3) of a series of saccharin derivatives having a sulfinate leaving group was investigated. The results of this study revealed that (a) inhibitory acti
Mechanisms of long-range 13C,13C spin-spin coupling in thioanisole and its derivatives. Conformational applications
Schaefer, Ted,Penner, Glenn H.
, p. 1229 - 1238 (2007/10/02)
The 13C nuclear magnetic resonance chemical shifts and the long-range 13C,13C spin-spin coupling constants are reported for 23 thioanisole derivatives enriched in 13C at the methyl position.For para and meta substituted thioanisole derivatives, nJ(C,C) (n being the formal number of bonds intervening between the coupled nuclei) can be related to functions of the angle by which the thiomethyl group twists out of the aromatic plane.For n = 3, 4, 5 the ensuing relationships yield estimates of the twofold barriers to rotation about the C(1)-S bond.The barrier is lower in ethyl phenyl sulfide than in thioanisole derivatives.Complications arise for ortho substituted thioanisole derivatives but estimates of the torsional motion about the C(1)-S bond can be obtained from the observed nJ(C,C).Among the complications is the expected fact that 3J(C,C), which is shown to be larger in the cis than the trans orientation of the intervening bonds ("anti-Karplus" behaviour), is perturbed by the substituent attached to the coupled nucleus.It is confirmed that in 2-hydroxythioanisole the thiomethyl group is oriented effectively perpendicular to the benzene plane, attributable to a stereospecific hydrogen bond between the hydroxyl group and the 3p lone-pair on the sulfur atom.In acetone-d6 solution, an equilibrium exists between this conformation and one in which an intermolecular hydrogen bond exists with solvent molecules.In the latter, the thiomethyl group prefers a coplanar orientation.In 2-aminothioanisole, the thiomethyl group twists out of the plane by about 60 deg so as to optimize the N-H...3p interaction.This twist angle is changed very little in acetone-d6 solution because the second N-H bond can hydrogen bond to the solvent molecules without disrupting the intramolecular N-H...3p interaction.Is is also shown that the chemical shift of the 13C nucleus in the methyl group is a good conformational indicator in meta and para substituted thioanisoles.Therefore it can be used as such for molecules in which nJ(C,C) is difficult to find, in 1,4-dithiomethylbenzene, for example.
Motion about the Csp2-S bond in thioanisole and some derivatives by the J method
Schaefer, Ted,Baleja, James D.
, p. 1376 - 1381 (2007/10/02)
Conformations about the Csp2-S bond in thioanisole and eight of its derivatives in solution are investigated by means of long-range spin-spin coupling constants over six bonds between the sidechain (13)C nucleus and the para ring proton or (19)F nucleus.According to geometry optimized STO 3G MO calculations the internal barrier to rotation is predominantly twofold in the gas phase in thioanisole and is 6.2 kJ/mol.In benzene solution the coupling constant yields 5.5(4) kJ/mol.Para fluorine and methyl substituents reduce the magnitude of the internal barrier, but meta methyl or chlorine substituents cause significant increases.In the presence of two ortho fluorine substituents the conformation of lowest energy has the C-S bond in a plane perpendicular to the aromatic plane, but the barrier may now contain a fourfold component.Addition of further fluorine substituents in the meta or para positions causes characteristic changes in conformational preferences of the thiomethyl group.
