Polysulfonylamine, XV [1] Synthese von N,N,N′,N′-Tetramesyl-dicarbonsäurediamiden. Cyclisierung von N,N,N′,N′-Tetramesyl-bernsteinsäurediamid zu γ-DimesyIamino-Δβγ-butenolid / Polysulfonylamines, XV [1]. Synthesis of N,N,N′,N′-Tetramesyl Dicarboxylic Diamides. Cyclization of N,N,N′,N′-Tetramesyl Succinic Diamide to γ-Dimesylamino-Δβγ-butenolide

Abstract

N, N, N′, N′ -Tetramesyl dicarboxylic diamides Ms2NC(O)-Q-C(O)NMs2 [Q = (CH2)n with n = 0 (2a), 2 (2b), 3 (2c), 4 (2d); Q = o-phenylene (2e)] were prepared by reacting AgNMs2 (1) with the appropriate dicarboxylic dichlorides in acetonitrile at room temperature (2a, 2 c-2e) or at 0 °C (2b), respectively. Under similar conditions, malonic dichloride undergoes an elimination, forming AgCl, HNMs2 and probably polymeric C3O2. At 20 °C in CH3CN, the succinic acid derivative 2b eliminates one mole of HNMs2 and, by ring closure, yields γ-dimesylamino-Δβγ- butenolide (4a), the first example of a stable γ-amino-Δβγ-butenolide. Treatment of 4a with aqueous NaOH results in the formation of NaNMs2 and sodium succinate. Crystalline 4a is thermally stable at 100 °C; no signs of an isomerization 4a → γ-dimesylamino-Δαγ-butenolide could be detected. Unlike the structurally related α-angelicalactone (4c), whose bromination affords the saturated dibromolactone 9 as a mixture of cis- and mws-isom ers, 4a adds bromine (20 °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 butvryl chloride); CH3CH2CHBrC(O)NMs2 (12c, from 1 and 2-bromobutyryl bromide); C2H5OC(O)CH 2CHBrC(O)NMs2 (13, from 7 with ethanol and from 4a by simultaneous reaction with bromine and ethanol).