98572-17-9Relevant academic research and scientific papers
Reaction of Tosylamide Monosodium Salt with Bis(halomethyl) Compounds: An Easy Entry to Symmetrical N-Tosyl Aza Macrocycles
Bottino, Francesco,Grazia, Michele Di,Finocchiaro, Paolo,Fronczek, Frank R.,Mamo, Antonino,Pappalardo, Sebastiano
, p. 3521 - 3529 (2007/10/02)
A one-step, general procedure for a variety of N-tosyl aza macrocycles (including aza-crown ethers, pyridino- and bipyridino-aza-crown analogues, and azacyclophanes), by reaction of appropriate bis(halomethyl) precursors with tosylamide monosodium salt (TsNHNa) in N,N-dimethylformamide, is described.In polymethyl-substituted 2,11-diazacyclophane systems, the methyl substituents play an important role in inducing stereospecific ring closures.Thus, coupling of 1,4-bis(chloromethyl)-2,5-dimethylbenzene (15b) with TsNHNa produced only one of the two possible diastereomeric dimers, to which chiral structure 16db was assigned by means of the chiral Eu(dcm)3 shift reagent.This stereochemical assignment was confirmed by a single-crystal X-ray study on 16d.Detosylation of N-tosyl aza macrocycles to the free polyamino macrocycles by reductive (Na-NH3) or hydrolytic (90percent H2SO4) methods, followed by N-methylation (CH2O-HCO2H), was also accomplished in excellent yield.The 1H NMR spectra of 2,11-diazacyclophanes and 2,11-diaza(2,6)pyridinophanes are discussed in terms of conformation and conformational mobility.
FORMATION OF COMPLEXES BETWEEN AZA DERIVATIVES OF CROWN ETHERS AND PRIMARY ALKYLAMMONIUM SALTS. PART 8. 12-CROWN-4, 15-CROWN5, 21-CROWN-7, AND 24-CROWN-8 DERIVATIVES
Johnson, Martin R.,Jones, Nigel F.,Sutherland, Ian O.
, p. 1637 - 1644 (2007/10/02)
The monoaza-crown ethers (3), (4), and (5) and the diaza-crown ethers (6), (7), (10), and (11) form complexes with primary alkylammonium thiocyanates in organic solvents.The diaza-15-crown-5 system (11) forms well defined 1:1 complexes with the cis-, cis-stereochemistry shown in (16) but the diaza-24-crown-8-derivative (7) forms a 2:1 complex (G:H ratio) with benzylammonium thiocyanate having the cis,cis,trans,trans-stereochemistry (17a).The diaza-24-crown-6 derivative (10) forms weak 1:1 complexes which apparently adopt the double nesting conformation (18).
A VERSATILE ONE-POT SYNTHESIS OF SYMMETRICAL N-TOSYLAZAMACROCYCLES
Pappalardo, Sebastiano,Bottino, Francesco,Grazia, Michele Di,Finocchiaro, Paolo,Mamo, Antonino
, p. 1881 - 1884 (2007/10/02)
A variety of title compounds (azacrown ethers, pyridino-azacrown analogues and azacyclophanes) have been synthesized in moderate to good yield by coupling appropriate bis(halomethyl) or bis(tosylate ester) precursors with tosylamide monosodium salt.A revised mechanism is proposed.
