Synthesis of Saturated Imidazolidin[1,5-a]- and Thiazolidin[3,4-a]perhydroquinoxalin-4-one and Imidazolidin[1,5-a]piperazin-4-one Derivatives. Ring Contraction of Perhydroquinoxalin-4-one to Perhydrobenzimidazolin-2-one

Barbara Zaleska; Robert Socha; Marcin Karelus; Jacek Grochowski; Paweł Serda

doi:10.1055/s-2004-829185

PAPER

Synthesis of Saturated Imidazolidin[1,5-a]- and Thiazolidin[3,4-a]perhydroquinoxalin-4-one and Imidazolidin[1,5-a]piperazin-4-one Derivatives. Ring Contraction of Perhydroquinoxalin-4-one to Perhydrobenzimidazolin-2-one

Barbara Zaleska*^a, Robert Socha^a, Marcin Karelus^a, Jacek Grochowski^b, Paweł Serda^b
^a Department of Organic Chemistry, Jagiellonian University, ul. Ingardena 3, 30-060 Kraków, Poland
Fax: +48(12)6340515; e-Mail: zaleska@chemia.uj.edu.pl;
^b Regional Laboratory of Physicochemical Analysis and Structural Research, ul. Ingardena 3, 30-060 Kraków, Poland

Abstract

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Abstract

Saturated fused systems such as imidazolidin[1,5-a]- and thiazolidin[3,4-a]perhydroquinoxalin-4-one as well as imidazolidin[1,5-a]piperazin-4-one derivatives were prepared by cyclocondensation reactions of appropriate perhydroquinoxalin-3-one and piperazin-3-one derivatives with diiodomethane and thiophosgene. An unusual ring contraction of perhydroquinoxalin-3-one derivatives to perhydrobenzimidazolidin-2-one derivatives by reaction with 1,2-dibromoethane was proved using crystal structure analysis with synchrotron and laboratory radiation sources.

Key words

imidazolidin[1,5-a]perhydroquinoxaline - thiazolidin[3,4-a]perhydroquinoxaline - imidazolidin[1,5-a]piperazine - fused saturated hetorocycles

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References

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Compound 8 with formula C₁₈H₂₃N₃OS crystallizes in the monoclinic system, space group P2₁/n, with unit cell parameters a = 1086.70(2), b = 722.07(1), c = 2201.27 (3) pm, β = 91.748(1)º, V = 1.72647(5) × 10⁹ pm³, Z = 4. A total of 14964 reflections were collected and merged to give 3957 independent reflections (R(int) = 0.0274) on a single-crystal sample (size 0.35 × 0.2 × 0.15 mm) using a KappaCCD diffractometer and MoKα radiation. The structure was solved by direct methods and refined by the full-matrix least squares method on F² using the SHELX97 program system. All hydrogen atoms were located on a difference Fourier map of electron density. Final R indices for I>2σ(I) were equal to R1 = 0.0441, wR2 = 0.1105, and R1 = 0.0604, w R2 = 0.1210 for all data. The final difference Fourier map of electron density was featureless with the largest peak and hole at 2.38 × 10^-7 and -3.29 × 10^-7 e.pm^-3, respectively. The structural data have been deposited at the Cambridge Crystallographic Data Centre under the reference number CCDC 239169.