5347-82-0Relevant articles and documents
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.
Polysulfonylamines, XV. Synthesis of N,N,N',N'-Tetramesyl Dicarboxylic Diamides. Cyclization of N,N,N',N'-Tetramesyl Succinic Diamide to υ-Dimesylamino-Δβ,γ-butenolide
Blaschette, Armand,Linoh, Karin,Koch, Dietrich
, p. 465 - 474 (2007/10/02)
N,N,N',N'-Tetramesyl dicarboxylic diamides Ms2NC(O)-Q-C(O)NMs2 were prepared by reacting AgNMs2 (1) with the appropriate dicarboxylic dichlorides in acetonitrile at room temperature (2a, 2c - 2e) or at 0 deg C (2b), respectively.Under similar conditions, malonic dichloride undergoes an elimination, forming AgCl, HNMs2 and probably polymeric C3O2.At 20 deg C in CH3CN, the succinic acid derivative 2b eliminates one mole of HNMs2 and, by ring closure, yields γ-dimesylamino-Δβ,γ-butenolide (4a), the first example of a stable γ-amino-Δβ,γ-butenolide.Treatment of 4a with aqueous NaOH results in the formation of NaNMs2 and sodium succinate.Crystalline 4a is thermally stable at 100 deg C; no signs of an isomerization 4a -> γ-dimesylamino-Δβ,γ-butenolide could be detected.Unlike the structurally related α-angelicalactone (4c), whose bromination affords the saturated dibromolactone 9 as a mixture of cis- and trans-isomers. 4a adds bromine (20 deg C, CHCl3) under ring cleavage to form BrC(O)CH2CHBrC(O)NMs2 (7).The new compounds 2, 4a and 7 as well as the stereoisomers of 9 were characterized by spectroscopic (1H and 13C NMR, MS, IR) and analytical methods.In order to obtain reference values for the chemical shifts of 7, the following new compounds were prepared: CH3(CH2)2C(O)NMs2 (10c, from 1 and butyryl chloride); CH3CH2CHBrC(O)NMs2 (12c, from 1 and 2-bromobutyryl bromide); C2H5OC(O)CH2CHBrC(O)NMs2 (13, from 7 with ethanol and from 4a by simultaneous reaction with bromine and ethanol). - Keywords: N,N,N',N'-Tetramesyl Dicarboxylic Diamides, Silver Dimesylamide, Dicarboxylic Dichlorides, γ-Dimesylamino-Δβ,γ-butenolide, α-Angelicalactone
Polysulfonylamines, XII. N-Acyl Dimesylamines (Carboxylic Acid N,N-Dimesylamides)
Blaschette, Armand,Safari, Firouz,Linoh, Karin,Koch, Dietrich
, p. 1495 - 1500 (2007/10/02)
N-Acyl dimesylamines RC(O)N(SO2CH3)2 (3) have been prepared by reacting solid KN(SO2CH3)2 with neat liquid RC(O)Cl at 70-90 deg C or solutions of AgN(SO2CH3)2 in methyl cyanide with RC(O)Cl at room temperature .Addition of chlorine or bromine to 3 (R = CH2=CH) affords the corresponding compounds 3 with R = CH2Cl-CHCl and CH2Br-CHBr, respectively.By hydrolysis of 3 (R = CCl3), CCl3C(O)NHSO2CH3 (5) is obtained.The new compounds 3 and 5 are characterized by spectroscopic (NMR, MS) and analytical methods. - Keywords: N-Acyl Dimesylamines, Potassium and Silver Dimesylaminides, Acyl Chlorides
Hydrolysis of Di- and Trimesylhydroxylamines and their Methylated Derivatives
Brink, Klaus,Mattes, Rainer
, p. 351 - 354 (2007/10/02)
The mesylhydroxylamines (CH3SO2)2NOH, (CH3SO2)2NOCH3, CH3SO2N(H)OSO2CH3, CH3SO2N(CH3)OSO2CH3 (1-4) and (CH3SO2)2NOSO2CH3 (5) were treated with basic, neutral, and acidic aqueous solutions.The reaction products were identified.Possible decomposition mechanisms were discussed.
