Aminolysis of N-Acyl Derivatives of Bicyclic Oxalactams

Abstract

ABSTRACT:The aminolysis of N-acyllactams with n-butylamine was carried out in N,Ndimethylformamide at 25°C. The amine reacted with both of exo-and endocyclic carbonyl groups in the N-benzoyl derivatives of bicyclic oxalactams, such as 8-oxa-6-azabicyclo[3.2. l]octan-7-one (1) and the 4(e)-bromo-substituted analogue. In contrast, only the exocyclic carbonyl group in the monocyclic N-benzoyllactams, N-benzoyl-2-pyrrolidone and N-benzoyl-s-caprolactam, reacted under the same conditions. These results reflect high reactivity of the bicyclic oxalactams in the base-catalyzed ring-opening polymerization. The present aminolysis was kinetically analyzed in order to estimate the reactivity of N-acyllactams more quantitatively.

Proton transfer-controlled anionic polymerization of methyl-substituted ?-lactams with potassiumt-butoxide and subsequent coupling reaction with saccharides

“…10 The N-benzoyl derivatives of 1 and 2 were also prepared by the same methods as described in previous articles. 18,20 Commercially available potassium t-butoxide was used without purification. It was divided in ampoules equipped with breakable seals in a dry box filled with dry nitrogen and kept in vacuo until use.…”

Preparation of monodisperse hydrophilic polyamide by anionic polymerization of bicyclic oxalactam

“…The time-conversion curves in Figure 1 indicate that the polymerization activated with NiBzBOL was slightly faster than that with BzBOL, consistent with a previous observation that the aminolysis of NiBzBOL with n-butylamine is faster than that of BzBOL by a factor of about 30. 19 In both runs the conversion was found to reach to about 84% in 20 min and the residual monomer concentration was determined to be 0.36 mol/L. In fact the unreacted monomer and Me,SO were detected by 'H-NMR spectroscopy in the residue after removing volatile components from the recovered solution.…”

Synthesis of novel block copolymers containing polyamide4 segments and control of their biodegradability

“…After the evaporation of the solvent, the crude product was recrystallized from a n ‐hexane‐benzene mixed solvent: yield, 2.6 g(17%); mp, 173°C. N ‐Benzoyl‐2‐pyrrolidone,24, 25 N ‐benzoyl‐8‐oxa‐6‐azabicyclo[3.2.1]octan‐7‐one,24 and N,N ′‐terephthaloylbis(ε‐caprolactam)16, 26 were prepared from the corresponding lactams and acid chlorides by a similar method. Tolylene‐2,4‐diisocyanate was distilled in vacuo , after being kept in a sealed flask for a week.…”