81293-02-9Relevant academic research and scientific papers
POLYSULFONYLAMINE: TEIL LXXI. EIN MOLEKUEL MIT EINER LANGEN Si(sp3)-O-BINDUNG: SYNTHESE, STRUKTUR UND REAKTIVITAET VON N,N-DIMESYLAMIDOSCHWEFELSAEURETRIMETHYLSILYLESTER
Hiemisch, Oliver,Blaschette, Armand,Jones, Peter G.
, p. 161 - 172 (2007/10/03)
The title compound (MeSO2)2N-SO2-O-SiMe3 (2; m.p. 57 deg C) is obtained by treating (MeSO2)2N-SiMe3 (3) with one equivalent of sulfur trioxide in CH2Cl2 at -20 deg C.The crystal structure of 2 (triclinic, space group P) was established by low-temperature X-ray diffraction.The most interesting feature of the molecular structure is the geometry of the S-O-Si sequence, displaying a very long Si(sp3)-O bond, a short S(sp3)-O bond and a large angle at oxygen (mean values for two independent molecules: Si-O 174.1, S-O 151.1 pm, S-O-Si 134.3 deg).The coordination at nitrogen is trigonal-planar (S-N-S 118.5-121.0 deg, S-N 170.5-173.1 pm). 2 is instantaneously hydrolyzed by excess water to form (MeSO2)2NH, sulfuric acid and (Me3Si)2O.In vacuo at 60 deg C, molten 2 will readily dissociate into its precursors 3 and SO3.It is shown that 2 may react either as an SO3 donor or as a sulfosilylating reagent.Reaction with Lewis bases such as Me3N, pyridine or R2PCl (R = tBu, Ph) proceeds with the formation of the corresponding complexes B*SO3; thermolysis of the isolable phosphane complexes affords the respective phosphane oxides R2(Cl)PO.Sulfosilylation of phenol, cyclohexene or 2,3-dimethyl-2-butene with 2 in CH2Cl2 gives the trimethylsilyl esters of 4-hydroxybenzenesulfonic, cyclohexene-3-sulfonic, or 2,3-dimethyl-1-butene-3-sulfonic acids, respectively.Key words: Trimethylsilyl N,N-dimesylamidosulfonate, synthesis, X-ray structure, long Si(sp3)-O bond, SO3 transfer, sulfosilylation.
Sulfosilylation of Aromatic Hydrocarbons by Trimethylsilyl Chlorosulfonate
Hofmann, Karin,Simchen, Gerhard
, p. 282 - 297 (2007/10/02)
Aromatic hydrocarbons 2 ,6 ,8 ,9 ,13 ,16 ,18 ,19 ,22 react with trimethylsilyl chlorosulfonate (1) to give trimethylsilyl arenesulfonates 5, 7, 11, 12, 15, 23 or sulfonic acids 17, 20, 21.If trimethylsilyl sulfonates are obtained, working up of the sulfonation mixtures is possible by distillation.By hydrohalogenolysis of trimethylsilyl sulfonates 5 at 0-5 deg C anhydrous sulfonic acids 3 result.The pathways to diphenylsulfone (25a) in the reaction of benzene (2a) with 1 were investigated.In this connection we succeeded in synthesizing benzenepyrosulfonic acid (28) and trimethylsilyl benzenepyrosulfonate (29).
