One-Pot Synthesis of Novel Molecular Clips and Macrocyclic Polyamines Derived from Bis(ethoxycarbonyl)glycoluril

Abstract

A new class of molecular clips and two novel macrocyclic polyamines were synthesized in one-pot procedures from aliphatic­ amines, formaldehyde, and rigid bis(ethoxy­carbonyl)glycoluril. Apart from characterization of all reaction products by ¹H NMR, ¹³C NMR, mass, and IR spectroscopy, a clip molecule and two macrocyclic cycloadducts were also studied by X-ray crystallography.

Key words

amines - polyamines - macrocycles - molecular clips - glycoluril

References

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21

Crystal structure data for compound 4h: CCDC 298975. C₃₀H₃₆N₆O₈, chemical formula weight: 608.65, monoclinic space group P2(1)/c, a = 16.1053 (15), b = 12.2053 (12), c = 15.5855 (15) Å; α = 90.00°, β = 104.955 (2)°, γ = 90.00°, U = 2959.9 (5) ų, T = 292 (2) K, Z = 4, D _C = 1.366 Mg/M³, µ = 0.101 mm^-1, λ = 0.71073 Å, F(000) 1288, crystal size 0.20 × 0.20 × 0.06 mm³, 5809 independent reflections [R(int) = 0.0528], reflections collected 22523, refinement method: full-matrix least-squares on F ², goodness-of-fit on F ² 1.043, final R indices [I > 2σ(I)], R1 = 0.0695, wR2 = 0.1534, largest diff. peak and hole 0.335 Å^-3 and -0.199e Å^-3.

22

Crystal structure data for macrocycle 5: CCDC 298974. C₄₄H₅₂N₁₂O₁₂, chemical formula weight: 940.98, monoclinic space group P2(1)/c, a = 11.1357 (15), b = 21.172 (3), c = 13.9437 (18) Å; α = 90.00°, β = 105.731 (2)°, γ = 90.00°, U = 3164.3 (7) ų, T = 292 (2) K, Z = 2, D _C = 1.489 Mg/M³, µ = 0.591 mm^-1, λ = 0.71073 Å, F(000) 1456, crystal size 0.30 × 0.30 × 0.30 mm³, 5564 independent reflections [ R(int) = 0.4432], reflections collected 19152, refinement method: full-matrix least-squares on F ², goodness-of-fit on F ² 0.971, final R indices [I > 2σ(I)], R1 = 0.1031, wR2 = 0.2710, largest diff. peak and hole 0.636 Å^-3 and -0.630 e×Å^-3.

23

Crystal structure data for macrocycle 6: CCDC 298973. C₄₄H₅₂N₁₂O₁₂, chemical formula weight: 940.98, monoclinic space group P2 (1)/c, a = 19.950 (8), b = 7.791 (3), c = 14.556 (6) Å; α = 90.00°, β = 102.217 (8)°, γ = 90.00°, U = 2211.3 (16) ų, T = 292 (2) K, Z = 2, D _C = 1.413 Mg/M³, µ = 0.105 mm^-1, λ = 0.71073 Å, F(000) 992, crystal size 0.20 × 0.10 × 0.06 mm³, 4329 independent reflections [R(int) = 0.1582], reflections collected 16027, refinement method: full-matrix least-squares on F ²: goodness-of-fit on F ² 0.913, final R indices [I > 2σ(I)], R1 = 0.0652, wR2 = 0.1379, largest diff. peak and hole 0.293 Å^-3 and -0.278 e×Å^-3.