Article abstract of DOI:10.1080/10426509608046422

Carbamates containing an N,N-disulfonylamino moiety (RSO₂)₂N - are reported for the first time. The compounds (MeSO₂)₂N - C(O) - OR, where R = ClCH₂, MeCHCI, ClCH₂CH₂, BrCH₂CH₂, Cl₃CCH₂ or Ph, were obtained in good yields by treating the corresponding chloroformates with Me₃SiN(SO₂Me)₂ in CH₂Cl₂ at room temperature in the presence of a catalytic amount of pyridine. Under the same conditions, methyl chloroformate afforded a mixture of (MeSO₂)₂N - Me and (MeSO₂)₂N - C(O) - OMe (1a), whereas benzyl chloroformate was quantitatively decarboxylated to give (MeSO₂)₂N - Bz and higher alkyl chloroformates (R = Et, ⁿBu, ⁱBu) were found to be unreactive. Metathesis of (MeSO₂)₂NAg with chloroformates in MeCN solution at room temperature is an extremely sluggish process and generally unsuitable for synthetic purposes; however, the carbamate (MeSO₂)₂N - C(O) - OCCl₃ (1c), which could not be obtained via the Me₃SiCl elimination reaction, was isolated in moderate yield by the silver salt method. The crystal structures of 1a (monoclinic, space group P2_t/c, two independent molecules) and 1a (monoclinic, P2_t/c) were determined by low-temperature X-ray diffraction. The most important result is the weakened S₂N - C(O) bond as indicated by the N - C bond lengths 144.3 and 144.6 pm in 1a and 141.3 pm in 1c. In both compounds, the nitrogen and carbon atoms of the carbamoyl groups have a trigonal-planar environment; the trigonal planes are tilted at interplanar angles of 62.0 and 49.5° in 1a and 48.1° in 1c.

Full text of DOI:10.1080/10426509608046422

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Phosphorus, Sulfur, and Silicon and the
Related Elements
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POLYSULFONYLAMINE: TEIL LXXIV.1 N-
(ORGANYLOXYCARBONYL)-DIMESYLAMINE
(N,N-DIMESYLCARBAMATE):
ERSTSYNTHESE UND AUSGEWÄHLTE
FESTKÖRPERSTRUKTUREN
Jörg Dalluhn a , Hans-Heinrich Pröhl a , Dagmar Henschel a , Armand
Blaschette a & Peter G. Jones a
a Institut für Anorganische und Analytische Chemie, Technische
Universität , Postfach 3329, 38023, Braunschweig, Deutschland
Published online: 04 Oct 2006.
To cite this article: Jörg Dalluhn , Hans-Heinrich Pröhl , Dagmar Henschel , Armand Blaschette &
Peter G. Jones (1996) POLYSULFONYLAMINE: TEIL LXXIV.1 N-(ORGANYLOXYCARBONYL)-DIMESYLAMINE
(N,N-DIMESYLCARBAMATE): ERSTSYNTHESE UND AUSGEWÄHLTE FESTKÖRPERSTRUKTUREN, Phosphorus,
Sulfur, and Silicon and the Related Elements, 114:1-4, 149-160, DOI: 10.1080/10426509608046422
To link to this article: http://dx.doi.org/10.1080/10426509608046422
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