Download PDF
Synthesis 2004(13): 2169-2172  
DOI: 10.1055/s-2004-829185
PAPER
© Georg Thieme Verlag Stuttgart · New York

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 Sochaa, Marcin Karelusa, Jacek Grochowskib, Paweł Serdab
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
Further Information

Publication History

Received 26 April 2004
Publication Date:
30 July 2004 (online)

   Permissions and Reprints All articles of this category
Preview

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

    References

  • 1 Hansen HC, and Watjen F. inventors; S. African ZA  8904430.  ; Chem. Abstr. 1990, 113, 212016
  • 2 Hansen HC. inventors; PCT Int. Appl. WO  9200298.  ; Chem. Abstr. 1992, 116, 174168
  • 3 Tenbrink RE, Jacobsen EJ, and Gammill RB. inventors; PCT Int. Appl. WO  9222552.  ; Chem. Abstr. 1993, 119, 72624
  • 4 Watjen F, and Hansen HC. inventors; Eur. Pat. Appl. EP  368652.  ; Chem. Abstr. 1990, 113, 172052
  • 5 Hansen HC, and Watjen F. inventors; Eur. Pat. Appl. EP  347094.  ; Chem. Abstr. 1990, 113, 115337
  • 6 Watjen F, and Hansen HC. inventors; PCT Int. Appl. WO  9107407.  ; Chem.Abstr. 1991, 115, 114549
  • 7 Tenbrink RE, Jacobsen EJ, and Gammill RB. inventors; US Patent  5541324.  ; Chem. Abstr. 1996, 125, 195687
  • 8 Jacobsen EJ. Stelzer LS. Tenbrink RE. Belonga L. Carter DB. Im HK. Im WB. Sethy VH. Tang AH. VonVoigtländer PF. Petke JD. Zhong W.-Z. Mickelson JW. J. Med. Chem.  1999,  42:  1123 
    CrossrefSearch in Google Scholar
  • 9 Jacobsen EJ. Stelzer LS. Belonga KL. Carter B. Im WB. Sethy VH. Tang AH. VonVoigtländer PF. Petke JD. J. Med. Chem.  1996,  39:  3820 
    CrossrefPubMedSearch in Google Scholar
  • 10 Lee TDY, and Brown RE. inventors; Eur. Pat. Appl. EP  70518.  ; Chem. Abstr. 1983, 99, 22496
  • 11 Davey DD. inventors; Eur. Pat. Appl. EP  400583.  ; Chem. Abstr. 1991, 114, 185550
  • 12 Lee TD, and Brown RE. inventors; US Patent  4440929.  ; Chem. Abstr. 1984, 101, 7202
  • 13 Ager IR. Barnes AC. Danswan GW. Hairsine PW. Kay DP. Kennewell PD. Matharu SS. Miller P. Robson P. Rowlands DA. Tully WR. Westwood R. J. Med. Chem.  1988,  31:  1098 
    CrossrefPubMedSearch in Google Scholar
  • 14 Taguchi M, Kondo H, and Sakamoto F. inventors; Jpn. Kokai Tokkyo Koho JP  04120081.  ; Chem. Abstr. 1992, 117, 212523
  • 15 Zaleska B. Bazanek T. Socha R. Karelus M. Grochowski J. Serda P. J. Org. Chem.  2002,  67:  4526 
    CrossrefPubMedSearch in Google Scholar
  • 16 Zaleska B. Karelus M. Synlett  2002,  1831 
    Thieme Connect
  • 17 Zaleska B. Socha R. Karelus M. Szneler E. Grochowski J. Serda P. J. Org. Chem.  2003,  68:  2334 
    CrossrefPubMedSearch in Google Scholar
18

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.