Polysulfonylamine, CXXXVIII [1]. 1,1-Di(organosulfonyl)-3,3-diorganylharnstoffe: Synthese von acht Vertretern und Kristallstruktur des Prototyps (MeSO

Polysulfonylamine, CXXXVIII [1].

1,1-Di(organosulfonyl)-3,3-diorganylharnstoffe:Synthese von acht Vertretern und Kristallstruktur des Prototyps (MeSO

)

NÐC(O)ÐNMe

Polysulfonylamines, CXXXVIII [1].

1,1-Di(organosulfonyl)-3,3-diorganylureas: Synthesis of Eight Representatives and Crystal Structure of the Prototype (MeSO

)

NÐC(O)ÐNMe

Jörg Dalluhn, Hans-Heinrich Pröhl, Armand Blaschette und Peter G. Jones

Sonderdruckanforderungen an Prof. Dr. A. Blaschette oder Prof. Dr. P. G. Jones.

Fax: +49 (0) 5 31 3 91 53 87. E-mail: p.jones@tu-bs.de.

Herrn Professor Dr. H. P. Fritz gewidmet

Z. Naturforsch.56 b, 680Ð688 (2001); eingegangen am 14. März 2001 Sulfonylureas, Amide Single Bond, Rotational Barrier

Eight compounds of the type (RSO₂)₂NÐC(O)ÐNR2⬘, where R = Me or 4-tolyl and R⬘= Me, Et,ⁱPr or Ph, were obtained in good yields by treating the corresponding carbamoyl chlorides R⬘2NC(O)Cl with silver salts AgN(SO2R)2in acetonitrile solution. The pronounced sensitivity of the compounds towards atmospheric moisture is indicative of a high degree of electrophilic activation at the carbonyl centre; bulk hydrolysis rapidly leads to carbon dioxide and the corresponding ammonium salt R⬘2NH⁺₂^-N(SO₂R)₂. In t he¹H and¹³C NMR solution spectra, the R2⬘N groups of the ureas give rise to distinct R⬘resonances at room temperature, reflecting unusually high barriers to rotation about the C(O)ÐNR2⬘bonds. For (MeSO2)2NÐ C(O)ÐNMe₂(1a) and the analogous ditosyl compound, the¹H NMR signals of the dimethyl- amino group were found to coalesce at 107∞C and 93∞C, respectively, which corresponds to a rotational barrier of∆G_C^#⬇80 kJ mol^Ð1. In the crystal of1a(triclinic, space groupP1¯,Z= 2; X-ray diffraction atÐ75∞C), the molecule possesses an essentially planar Me₂NÐC(O)Ð N moiety (except H atoms), whereas the CÐNS₂grouping is pyramidalized to such an extent that N lies 27.8(2) pm out of the plane defined by the carbonyl C atom and the two sulfonyl S atoms [SÐNÐS 120.52(11)∞, CÐNÐS 115.73(14) and 115.06(14)∞]. The mostremarkable features of the molecular structure are the exceedingly long C(O)ÐNS₂bond [148.6(3) pm]

and the concomitantly short CÐO and C(O)ÐNC₂ bonds [121.4(3) and 132.2(3) pm]. The crystal packing of1ais governed by a three-dimensional network of nine intermolecular CÐ H · · · O hydrogen bonds originating from the activated MeÐS and MeÐN donor groups (H · · · O 230Ð266 pm, CÐH · · · O 123Ð173∞).