Search results for "SoMe"
showing 10 items of 5114 documents
Development of MR active contrast agents via Parahydrogen Induced Polarization
2009
Parahydrogen Induced Polarization provides dramatic MR signal enhancement that can be exploited for molecular imaging. This method allows amongst others for Magnetic Resonance Imaging of 13C and 15N, which is usually constrained by the low MR sensitivity of these nuclei. By combining hydrogenation of barbiturates with parahydrogen under special experimental conditions (PASADENA under pressure) with a polarization transfer sequence we demonstrate the transfer of the initial 1H polarization to 13C. The polarization transfer yields a signal increase for 13C of more than 1000. Hence, the role of certain target compounds such as anesthetics like the barbituric acid derivatives could be investiga…
Photochemical isomerization of aryl hydrazones of 1,2,4-oxadiazole derivatives into the corresponding triazoles
2012
The photochemical version of the Boulton-Katritzky reaction has been studied, examining the behaviour of the arylhydrazones of 3-benzoyl-5-X-1,2,4-oxadiazoles. The effect of several modifications of the substrates structure (the E and/or Z structures of arylhydrazones, the possible presence of substituents in the arylhydrazono moiety, and the nature of substituents at C-5 of the 1,2,4-oxadiazole ring) on the course of the photochemical rearrangement has been examined.
Competing Ring-Photoisomerization Pathways in the 1,2,4-Oxadiazole Series. An Unprecedented Ring-Degenerate Photoisomerization
2002
The irradiation of some 5-alkyl-3-amino-1,2,4-oxadiazoles at lambda = 254 nm in methanol in the presence of triethylamine (TEA) gave ring-photoisomerization both into 2-alkyl-5-amino-1,3,4-oxadiazoles and, unprecedently, into the ring-degenerate 3-alkyl-5-amino-1,2,4-oxadiazoles. The competing ring contraction-ring expansion route and the internal cyclization-isomerization mechanism explain the results.
ISomerization of xylene: MINDO/3 study of the cyclization of benzenium cation into bicyclo[3.1.0]hexenyl cation
1989
Abstract A MINDO/3 study of thermal electrocyclic closing of the benzenium cation to form a bicyclo[3.1.0]hexenyl cation is presented. The calculated mechanism discusses the possibility of cyclization of xylenium cations on a silica catalyst or in superacid media. The structure and energy of the transition state, the enthalpies of isomerization and barriers of activation were calculated for the following processes: isomerization of 2,6-dimethylbenzenium cation into 2,6-dimethylbicyclo[3.1.0]hexenyl cation, isomerization of 2,4-dimethylbenzenium cation into 2,4-dimethylbicyclo[3.1.0]-hexenyl cation, and isomerization of benzenium cation into bicyclo[3.1.0]-hexenyl cation. Equilibrium and kin…
Synthesis and Conformational Analysis of Tetrahydroisoquinoline-Fused 1,3,2-Oxazaphospholidines and 1,2,3-Oxathiazolidines
2008
The cyclizations of tetrahydroisoquinoline 1,2-amino alcohols with phenylphosphonic dichloride, bis(2-chloroethyl)phosphoramidic dichloride, thionyl chloride and sulfuryl chloride were utilized to synthesize 1,5,6,10b-tetrahydro-1,3,2-oxazaphospholo[4,3-a]isoquinolines (2, 3), 1,5,10,10a-tetrahydro-1,3,2-oxazaphospholo[3,4-b]isoquinolines (8, 9), 1,5,6,10b-tetrahydro-1,2,3-oxathiazolo[4,3-a]isoquinolines (4–6) anda 1,5,10,10a-tetrahydro-1,2,3-oxathiazolo[3,4-b]isoquinoline (11), which are the first representatives of these ring systems. NMR spectroscopic analysis revealed the existence of conformational equilibria that are fast on the NMR timescale. Theoretical DFT calculations pointed to t…
Corrigendum to “Light-induced, site-selective isomerization of glyoxylic acid in solid xenon” [Chem. Phys. Lett. 616–617 (2014) 91–97]
2015
Synthesis and structural characterization of cis- and trans-fused 4a,5,6,7,8,8a-hexahydro-2H,4H-1,3-benzodithiines and their 2-methyl and 2,2-dimethy…
2002
Both cis- and trans-fused 4a,5,6,7,8,8a-hexahydro-2H,4H-1,3-benzodithiine together with their 2-methyl and 2,2-dimethyl derivatives were prepared as racemates from the appropriate dithiols obtained via multistep syntheses. The products were characterized by 1 H and 13 C NMR, mass spectrometry, and for two of the cis-fused compounds by X-ray diffraction. 1 H, 1 H vicinal coupling constants indicated that all compounds attain chair-chair conformations as their predominant conformations. All three trans-fused isomers exist in totally biased chair-chair conformations and are essentially conformationally locked, whereas the cis-fused compounds are conformationally mobile and can potentially atta…
The Chemistry of the [1,2,3]Triazolo[1,5-a]pyridines: An Update
2010
Publisher Summary This chapter discusses the recent advancement in the chemistry of [1,2,3] triazolo[1,5-a]pyridines. It describes new discoveries in the physical properties and theoretical chemistry, focusing on synthesis of [1,2,3]triazolo[1,5-a]pyridine system, synthesis of novel aryltriazolopyridines, chiral ligands from [1,2,3]triazolo[1,5-a]pyridines, pyridylcarbene formation from triazolopyridines, ring-chain isomerization on [1,2,3]triazolo[1,5-a]pyridines, and novel pyridylcarbonylpyridines. All triazolopyridines have interesting ligand properties to form polynuclear complexes with different metal ions. X-ray single-crystal studies, magnetic, photo-magnetic, and colorimetric measur…
Ab Initio Study of Stereo- and Regioselectivity in the Diels−Alder Reaction between 2-Phenylcyclopentadiene and α-(Methylthio)acrylonitrile
1997
Ab initio molecular orbital calculations have been used to investigate the Diels−Alder reaction between 2-phenylcyclopentadiene and α-(methylthio)acrylonitrile. Geometry optimizations were performed with the RHF/3-21G, RHF/3-21G*, and RHF/6-31G* calculations while the correlation energy has been calculated at MP2 and MP3 levels. Four asynchronous transition structures corresponding to the formation of different stereoisomers and regioisomers associated with the four reaction channels have been located. The observed endo/exo stereoselectivity and para/meta regioselectivity are correctly described at all levels of calculation, and the calculated activation energies reflect accurately the rela…
Generation of hexahydroazulenes
2009
(Z)-Cyclodec-1-en-6-yne (3) generates three conjugated hexahydroazulenes 3→1k→1c, 1l under FVP conditions, whereas flash vacuum pyrolysis (FVP) of cyclodecyne (2) leads to 1,2,9-decatriene (9). We attribute the different thermal behavior of 2 (ring opening) and 3 (ring closure) to different transannular interactions. Altogether 22 constitutional isomers of hexahydroazulene should exist; three new isomers (1k, 1l, and 1m) are presented here, ten were described earlier, but the reinvestigation of the dehydration route of bicyclic alcohol 11 showed that one of the ten structures has to be revised.