Oxidative fluorination in the Ph2SO–XeF2–Cl− system and fluorine exchange in the Ph2S(O)F2–Ph2S(O)F+ system

1996 ◽  
Vol 74 (11) ◽  
pp. 2002-2007 ◽  
Author(s):  
Xiaobo Ou ◽  
Alexander F. Janzen
Keyword(s):  
Nmr Spectroscopy ◽  
Ab Initio ◽  
Key Words ◽  
Exchange Process ◽  
Chloride Ion ◽  
Fluoride Ion ◽  
Molecular Orbital Calculations ◽  
Xenon Difluoride ◽  
Mild Conditions ◽  
C Nmr

Oxidative fluorination of diphenyl sulfoxide with xenon difluoride occurs under mild conditions in the presence of chloride ion to give Ph2S(O)F2 in quantitative yield. Chloride ion appears to react with xenon difluoride to generate fluoride ion, and a mechanism of oxidative fluorination is proposed that involves anionic Ph2S(O)F− and radical Ph2S(O)F• intermediates. Addition of cationic Ph2S(O)F+ to Ph2S(O)F2 initiates rapid fluorine exchange, presumably via a symmetrical fluorine-bridged intermediate, and this exchange process was monitored by 13C and 19F NMR spectroscopy. In the presence of chloride ion, Ph2S(O)Cl2 is formed and can be identified by 13C NMR and by its hydrolysis to Ph2SO2. Mechanisms are proposed for these reactions, and ab initio molecular orbital calculations (GAUSSIAN92) were carried out of the postulated intermediates. Key words: preparation of Ph2S(O)F2, Ph2S(O)F+, and Ph2S(O)Cl2; oxidative fluorination in the Ph2SO–XeF2–Cl− system; fluorine exchange in the Ph2S(O)F2–Ph2S(O)F+ system.

An unusual reaction of a bridged triterpenoid α-diketone with acetic anhydride

1991 ◽  
Vol 56 (12) ◽  
pp. 2917-2935 ◽  
Author(s):  
Eva Klinotová ◽  
Václav Křeček ◽  
Jiří Klinot ◽  
Miloš Buděšínský ◽  
Jaroslav Podlaha ◽  
...  
Keyword(s):  
Acetic Acid ◽  
Nmr Spectroscopy ◽  
Acetic Anhydride ◽  
Spectral Methods ◽  
X Ray Diffraction ◽  
X Ray ◽  
Mild Conditions ◽  
Condensation Products ◽  
Unsaturated Lactones ◽  
C Nmr

3β-Acetoxy-21,22-dioxo-18α,19βH-ursan-28,20β-olide (IIIa) reacts with acetic anhydride in pyridine under very mild conditions affording β-lactone IVa and γ-lactones Va and VIIa as condensation products. On reaction with pyridine, lactones Va and VIIa undergo elimination of acetic acid to give unsaturated lactones VIIIa and IXa, respectively. Similarly, the condensation of 20β,28-epoxy-21,22-dioxo-18α,19βH-ursan-3β-yl acetate (IIIb) with acetic anhydride leads to β-lactone IVb and γ-lactone Vb; the latter on heating with pyridine affords unsaturated lactone VIIIb and 21-methylene-22-ketone Xb. The structure of the obtained compounds was derived using spectral methods, particularly 1H and 13C NMR spectroscopy; structure of lactone IVa was confirmed by X-ray diffraction.

Preparation, 1H and 13C NMR, and ab initio/IGLO study of mono-O-protonated deltic acid and theoretical investigation of di-, tri-, and tetra-O-protonated deltic acids

1999 ◽  
Vol 77 (5-6) ◽  
pp. 525-529 ◽  
Author(s):  
GK Surya Prakash ◽  
Golam Rasul ◽  
George A Olah ◽  
Ronghua Liu ◽  
Thomas T Tidwell
Keyword(s):  
Nmr Spectroscopy ◽  
Ab Initio ◽  
Theoretical Investigation ◽  
13C Nmr ◽  
Chemical Shifts ◽  
1H And 13C Nmr ◽  
Nmr Chemical Shifts ◽  
Molar Solution ◽  
Protonated Species ◽  
C Nmr

The hitherto elusive mono-O-protonated deltic acid C3O3H3+ was prepared by protolysis of di-tert-butoxy deltate in FSO3H-SO2ClF and in FSO3H:SbF5 (Magic Acid; 1:1 molar solution) in SO2ClF as solvent at -78°C and was characterized by 1H and 13C NMR spectroscopy. The structure and NMR chemical shifts were also calculated by the ab initio/IGLO method. No NMR evidence was found for persistent di-O-protonated deltic acid under these conditions, although a limited equilibrium with the mono-O-protonated species can be involved. Di-, tri-, and tetra-O-protonated deltic acids were also studied by ab initio/IGLO method.Key words: protonated deltic acid, aromaticity, superacids, NMR spectroscopy, ab initio and IGLO calculations.

Ligand scrambling reactions of cyano(thione)gold(I) complexes and determination of their equilibrium constants

2002 ◽  
Vol 80 (10) ◽  
pp. 1279-1284 ◽  
Author(s):  
Saeed Ahmad ◽  
Anvarhusein A Isab ◽  
Herman P Perzanowski
Keyword(s):  
Ionic Strength ◽  
Nmr Spectroscopy ◽  
Key Words ◽  
Equilibrium Constants ◽  
Solvent Polarity ◽  
Approach To Equilibrium ◽  
Initial Concentration ◽  
C Nmr

Ligand scrambling reactions in cyano(thione)gold(I) complexes ([>C=S-Au-CN]) to form [Au(>C=S)2]+ and [Au(CN)2]– species have been investigated for a series of thiones in DMSO using 13C and 15N NMR spectroscopy. Rapid approach to equilibrium occurred and resulted in distinct signals for the [>C=S-Au-CN] and [Au(CN)2]– complexes, both in 13C and 15N NMR. Equilibrium constants (Keq) were determined for scrambling of all the complexes by integrating the CN resonances in the 13C NMR recorded at 298 K. The influence of various factors (initial concentration, ionic strength, temperature, and solvent polarity) on the Keq value was examined for a representative complex (ImtAuCN (Imt = Imidazolidine-2-thione)).Key words: cyanogold(I) complexes, thiones, ligand scrambling, NMR, Keq.

scholarly journals Fluoride-mediated rearrangement of phenylfluorosilanes

2018 ◽  
Vol 96 (6) ◽  
pp. 587-590 ◽  
Author(s):  
Natalie L. Dean ◽  
J. Scott McIndoe
Keyword(s):  
Nmr Spectroscopy ◽  
Real Time ◽  
Exchange Process ◽  
Cross Coupling ◽  
Mass Spectrometric ◽  
Mass Spectrometric Analysis ◽  
Spectrometric Analysis ◽  
Fluoride Ion ◽  
Rapid Formation

Combining Ph3SiF and fluoride ion under conditions used for the Hiyama coupling causes rapid formation of the expected [Ph3SiF2]−; however, real-time electrospray mass spectrometric analysis reveals that phenyl-fluoride exchange occurs concomitantly, also producing substantial quantities of [PhnSiF5–n]− (n = 0–2). The exchange process is verified using 19F NMR spectroscopy. This observation may have implications for Hiyama reaction protocols, which use transmetallation from triaryldifluorosilicates as a key step in cross-coupling.

scholarly journals Binding Cellulose and Chitosan via Intermolecular Inclusion Interaction: Synthesis and Characterisation of Gel

2015 ◽  
Vol 2015 ◽  
pp. 1-6 ◽  
Author(s):  
Jiufang Duan ◽  
Chunrui Han ◽  
Liujun Liu ◽  
Jianxin Jiang ◽  
Jianzhang Li ◽  
...  
Keyword(s):  
Nmr Spectroscopy ◽  
Lithium Chloride ◽  
Room Temperature ◽  
Self Healing ◽  
Mild Conditions ◽  
Inclusion Interaction ◽  
Ferrocenecarboxylic Acid ◽  
Novel Method ◽  
Chitosan Gel ◽  
C Nmr

A novel cellulose-chitosan gel was successfully prepared in three steps: (1) ferrocene- (Fc-) cellulose with degrees of substitution (DS) of 0.5 wt% was synthesised by ferrocenecarboxylic acid and cellulose within dimethylacetamide/lithium chloride (DMAc/LiCl); (2) theβ-cyclodextrin (β-CD) groups were introduced onto the chitosan chains by reacting chitosan with epichlorohydrin in dimethyl sulphoxide and a DS of 0.35 wt%; (3) thus, the cellulose-chitosan gel was obtained via an intermolecular inclusion interaction of Fc-cellulose andβ-CD-chitosan in DMA/LiCl, that is, by an intermolecular inclusion interaction, between the Fc groups of cellulose and theβ-CD groups on the chitosan backbone at room temperature. The successful synthesis of Fc-cellulose andβ-CD-chitosan was characterised by13C-NMR spectroscopy. The gel based onβ-CD-chitosan and Fc-cellulose was formed under mild conditions which can engender autonomous healing between cut surfaces after 24 hours: the gel cannot self-heal while the cut surfaces were coated with a solution of a competitive guest (adamantane acid). The cellulose-chitosan complex made by this method underwent self-healing. Therefore, this study provided a novel method of expanding the application of chitosan by binding it with another polymer.

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