O-Methylation of a sulfone with methyl fluoride – antimony pentafluoride – sulfur dioxide. Preparation and properties of tetrahydro-1-methoxythiophenium 1-oxide hexafluoroantimonate

1984 ◽  
Vol 62 (1) ◽  
pp. 69-73 ◽  
Author(s):  
Magdy Malak Abdel-Malik ◽  
Philip Arthur Woodworth Dean ◽  
James Frederick King
Keyword(s):  
Sulfur Dioxide ◽  
Antimony Pentafluoride ◽  
Liquid Sulfur ◽  
Methyl Fluoride ◽  
Methyl Group ◽  
Spectroscopic Evidence ◽  
Group A

Reaction of sulfolane (tetrahydrothiophene 1,1-dioxide) (1) with methyl fluoride – antimony pentafluoride in liquid sulfur dioxide gives crystalline tetrahydro-1-methoxythiophenium 1-oxide hexafluoroantimonate (2), thereby providing the first characterized example of an alkoxysulfoxonium salt. This salt (2) is also formed, but more slowly, by reaction of methyl fluoride with the crystalline 1:1 complex of sulfolane and antimony pentafluoride. Reaction of 2 with nucleophiles leads to transfer of the methyl group, a facile process even with such weak nucleophiles as nitrobenzene and phenyl N,N-dimethylsulfamate. Spectroscopic evidence has been obtained for O-methylation of other sulfones, either by reaction with MeF•SbF5•SO2, or via the sulfone•SbF5 complex and methyl fluoride, or by transmethylation with 2.

scholarly journals Eightfold Electrophilic Methylation of Octacyanotungstate [W(CN)8]4−/3−: Preparation of Homoleptic, Eight-coordinate Methylisocyanide Complexes [W(CNMe)8]4+/5+

2021 ◽  
Author(s):  
Malte Sellin ◽  
Susanne Margot Rupf ◽  
Ulrich Abram ◽  
Moritz Malischewski
Keyword(s):  
Sulfur Dioxide ◽  
Single Crystal ◽  
Epr Spectroscopy ◽  
X Ray Diffraction ◽  
Liquid Sulfur ◽  
Methyl Fluoride ◽  
X Ray ◽  
First Time ◽  
Ir And Raman ◽  
Methyl Triflate

Homoleptic eight-fold coordinated methylisocyanide complexes of W(IV) and W(V) have been prepared for the first time. The reaction of [NBu4]4[W(CN)8] with methyl triflate MeOTf gives [W(CNMe)8][OTf]4. The even stronger methylating mixture of methyl fluoride MeF and arsenic pentafluoride AsF5 in liquid sulfur dioxide SO2 is able to fully alkylate both [NBu4]4[W(CN)8] and [NBu4]3[W(CN)8]. The paramagnetic octakis(methylisocyanide)- tungsten(V) [W(CNMe)8][AsF6]5 is thermally highly unstable above −30 °C. All compounds have been characterized via single-crystal X-ray diffraction, IR and Raman, as well as NMR or EPR spectroscopy<br>

scholarly journals Eightfold Electrophilic Methylation of Octacyanotungstate [W(CN)8]4−/3−: Preparation of Homoleptic, Eight-coordinate Methylisocyanide Complexes [W(CNMe)8]4+/5+

2021 ◽  
Author(s):  
Malte Sellin ◽  
Susanne Margot Rupf ◽  
Ulrich Abram ◽  
Moritz Malischewski
Keyword(s):  
Sulfur Dioxide ◽  
Single Crystal ◽  
Epr Spectroscopy ◽  
X Ray Diffraction ◽  
Liquid Sulfur ◽  
Methyl Fluoride ◽  
X Ray ◽  
First Time ◽  
Ir And Raman ◽  
Methyl Triflate

Homoleptic eight-fold coordinated methylisocyanide complexes of W(IV) and W(V) have been prepared for the first time. The reaction of [NBu4]4[W(CN)8] with methyl triflate MeOTf gives [W(CNMe)8][OTf]4. The even stronger methylating mixture of methyl fluoride MeF and arsenic pentafluoride AsF5 in liquid sulfur dioxide SO2 is able to fully alkylate both [NBu4]4[W(CN)8] and [NBu4]3[W(CN)8]. The paramagnetic octakis(methylisocyanide)- tungsten(V) [W(CNMe)8][AsF6]5 is thermally highly unstable above −30 °C. All compounds have been characterized via single-crystal X-ray diffraction, IR and Raman, as well as NMR or EPR spectroscopy<br>

The Preparation and Properties of Complexes of Antimony and Bismuth Trifluorides with Strong Fluoride Acceptors

1973 ◽  
Vol 51 (5) ◽  
pp. 667-673 ◽  
Author(s):  
T. Birchall ◽  
P. A. W. Dean ◽  
B. Della Valle ◽  
R. J. Gillespie
Keyword(s):  
Raman Spectrum ◽  
Sulfur Dioxide ◽  
Raman Spectra ◽  
Mössbauer Spectra ◽  
Type A ◽  
Antimony Pentafluoride ◽  
Type B ◽  
Liquid Sulfur ◽  
Mossbauer Spectra

The reactions of antimony and bismuth trifluorides with the pentafluorides of antimony and arsenic in liquid sulfur dioxide yield the adducts SbF3•SbF5 (type A), SbF3•AsF5, BiF3•3SbF5, and BiF3•AsF5; no adducts of the trifluorides with BF3 were isolated. Antimony metal reacts with excess of antimony pentafluoride and arsenic pentafluoride in liquid sulfur dioxide giving a second form of SbF3•SbF5 (type B) and the same form of SbF3•AsF5 as produced from SbF3, respectively. BiF3•3SbF5 can be formulated as Bi(SbF6)3, but its Raman spectrum indicates the presence of extensive cation–anion fluorine-bridging. Their Raman spectra suggest that BiF3•AsF5, SbF3•AsF5, and SbF3•SbF5 (type B) have similar structures, possibly containing polymeric fluorine-bridged cations, but that SbF3•SbF5 (type A) has a different structure probably like that of AsF3•SbF5. The 121Sb Mössbauer spectra of the SbF3 adducts support the assignment of similar structures to SbF3•AsF5 and SbF3•SbF5 (type B), and the suggestion that SbF3•AsF5 and both forms of SbF3•SbF5 contain antimony (III) fluoro-cations. 19F n.m.r. shows that SbF3 has appreciable solubility in SO2 solutions of SbF5 and indicates the possible formation of "fluxional" SbF2–SbnF5n+1 molecules in SbF3–SbF5 solutions.

ChemInform Abstract: Indium-Triflate-Catalyzed Ritter Reaction in Liquid Sulfur Dioxide.

ChemInform ◽  
2016 ◽  
Vol 47 (29) ◽  
Author(s):  
Daniels Posevins ◽  
Krista Suta ◽  
Maris Turks
Keyword(s):  
Sulfur Dioxide ◽  
Ritter Reaction ◽  
Liquid Sulfur ◽  
Indium Triflate

The biosynthesis of ephedrine

1989 ◽  
Vol 67 (6) ◽  
pp. 998-1009 ◽  
Author(s):  
Gunnar Grue-Sørensen ◽  
Ian D. Spenser
Keyword(s):  
Carbon Atom ◽  
Benzoic Acid ◽  
Pyruvic Acid ◽  
Nmr Spectra ◽  
Carbon Skeleton ◽  
Resonance Spectroscopy ◽  
Methyl Group ◽  
Acid Incorporation ◽  
Group A ◽  
C Nmr

It is shown by 13C nuclear magnetic resonance spectroscopy that the labelled C2 fragment of [2,3-13C2]pyruvic acid is transferred intact into the C-methyl group and the adjacent carbon atom of the Ephedra alkaloids, norephedrine, ephedrine, norpseudoephedrine, and pseudoephedrine, in growing plants of Ephedragerardiana. This finding serves to identify pyruvate as the elusive precursor of the aliphatic C2 terminus of the skeleton of the alkaloids. In earlier experiments with C-labelled substrates, label from [3-14C]pyruvic acid was incorporated mainly, but not exclusively, into the C-methyl group of ephedrine, and label from [2-14C]pyruvate was incorporated similarly into the carbon atom adjacent to the C-methyl group. A C6–C1 unit related to benzaldehyde or benzoic acid has long been known to generate the benzylic fragment of the carbon skeleton of the Ephedra alkaloids. It is likely that the carbon skeleton of ephedrine is generated from pyruvate and either benzaldehyde or benzoic acid, by a reaction analogous to the formation of acetoin or diacetyl from pyruvate and acetaldehyde or acetic acid, respectively. Keywords: biosynthesis of ephedrine, Ephedra alkaloids, 13C NMR spectra, ephedrine, biosynthesis of pyruvic acid, incorporation into ephedrine13C NMR spectra.

Mikrowellenspektrum und Struktur von Fluortribromsilan und Methyltribromsilan

1968 ◽  
Vol 23 (11) ◽  
pp. 1819-1821 ◽  
Author(s):  
M. Mitzlaff ◽  
R. Holm ◽  
H. Hartmann
Keyword(s):  
Least Squares ◽  
Internal Rotation ◽  
Kcal Mole ◽  
Rotational Constants ◽  
Methyl Group ◽  
Microwave Spectra ◽  
Group A

The microwave spectra of SiFBr3 and CH3SiBr have been investigated in the region from 30 to 40 GHz. Assuming reasonable values for dSi-F, dSi-C and the methyl group a least squares analysis of the rotational constants yieldsdSi-Br ≮Br—Si—BrSiFBr3 (2,171 ± 0,001) A (111,36 ± 0,15)°,CH3SiBr3 (2,175±0,001) A (111,09±0,15)°.A barrier to internal rotation of about 1 kcal/mole is estimated by the intensity method.

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