Synthesis 2010(7): 1209-1216  
DOI: 10.1055/s-0029-1218670
PAPER
© Georg Thieme Verlag Stuttgart ˙ New York

Reactions of 2-Methyl- and 1,2-Dimethyl-1,4,5,6-tetrahydropyrimidine with Aroyl Chlorides: Diverse Reactivities of Cyclic Ketene N,N′-Acetals Generated in situ

Guozhong Yea, Sabornie Chatterjeea, Aihua Zhoub, Bobby Lloyd Barkera, Chunlong Chenc, Yingquan Songa, Charles U. Pittman Jr.*a
a Department of Chemistry, Mississippi State University, Mississippi State, MS 39762, USA
b Pharmacy School, University of Wisconsin-Madison, WI 53706, USA
c Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA
Fax: +1(662)3257611; e-Mail: cpittman@chemistry.msstate.edu;
Further Information

Publication History

Received 6 November 2009
Publication Date:
05 February 2010 (eFirst)

Abstract

2-Methyl-1,4,5,6-tetrahydropyrimidine reacted with two equivalents of aroyl chloride in tetrahydrofuran-triethylamine to give N,N′-diaroyl cyclic ketene N,N-acetals that are inert to excess aroyl chlorides. No carbon-carbon bond was formed in these reactions. Conversely, 1,2-dimethyl-1,4,5,6-tetrahydropyrimidine reacted with three equivalents of aroyl chloride under the same conditions to give N-aroyl N′-methyl β,β-dioxo cyclic ketene N,N′-acetals, with formation of two carbon-carbon bonds. Various reactions of cyclic amidines with aroyl chlorides were observed and are discussed in terms of the effects of the ring size and substituents on the reactivities of the cyclic ketene N,N′-acetals generated in situ.

    References

  • For examples, see:
  • 1a Grainger RS. Welsh EJ. Angew. Chem. Int. Ed.  2007,  46:  5377 
  • 1b Wang SLB. Liu X. Ruiz MC. Gopalsamuthiram V. Wulff WD. Eur. J. Org. Chem.  2006,  5219 
  • 1c Martins MAP. Cunico W. Brondani S. Peres RL. Zimmermann N. Rosa FA. Fiss GF. Zanatta N. Bonacorso HG. Synthesis  2006,  1485 
  • 1d Hamasaki A. Ducray R. Boger DL. J. Org. Chem.  2006,  71:  185 
  • 1e Rustullet A. Alibés R. de March P. Figueredo M. Font J. Org. Lett.  2007,  9:  2827 
  • 1f Gompper R. Elser W. Tetrahedron Lett.  1964,  29:  1971 
  • 1g Ziegler T. Layh M. Effenberger F. Chem. Ber.  1987,  120:  1347 
  • 1h Neidlein R. Klotz UJ. Chem. Ber.  1985,  118:  3217 
  • 1i Gillard M. T’Kint C. Sonveaux E. Ghosez L. J. Am. Chem. Soc.  1979,  101:  5837 
  • 1j Sauer J. Heldmann DK. Hetzenegger J. Krauthan J. Sichert H. Schuster J. Eur. J. Org. Chem.  1998,  2885 
  • 2a Beyerstedt F. McElvain SM. J. Am. Chem. Soc.  1936,  58:  529 
  • 2b Barnes HM. Kundiger D. McElvain SM. J. Am. Chem. Soc.  1940,  62:  1281 
  • 2c McElvain SM. Tate BE. J. Am. Chem. Soc.  1945,  67:  202 
  • 2d McElvain SM. Chem. Rev.  1949,  45:  453 
  • 3a Meyers AI. Nazarendo N. J. Am. Chem. Soc.  1972,  94:  3243 
  • 3b Zhou A. Pittman CU., Jr. Tetrahedron Lett.  2004,  45:  8899 
  • 3c Quast H. Ach M. Balthasar J. Hergenröther T. Regnat D. Lehmann J. Banert K. Helv. Chim. Acta.  2005,  88:  1589 
  • 3d Roberts RM. Corse J. Boschan R. Seymour D. Winstein S. J. Am. Chem. Soc.  1958,  80:  1247 
  • 3e Gruseck U. Heuschmann M. Chem. Ber.  1987,  120:  2053 
  • For examples, see:
  • 4a Cao L. Wu Z. Zhu PC. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.)  1999,  39:  406 
  • 4b Cao L. Wu Z. Pittman CU. J. Polym. Sci., Part A: Polym. Chem.  1999,  37:  2841 
  • 4c Cao L. Pittman CU. J. Polym. Sci., Part A: Polym. Chem.  1999,  37:  2823 
  • 4d Wu Z. Cao L. Pittman CU. Recent Res. Dev. Polym. Sci.  1998,  2:  467 
  • 4e Wu Z. Cao L. Pittman CU. J. Polym. Sci., Part A: Polym. Chem.  1998,  36:  861 
  • 4f Zhu PC. Pittman CU. J. Polym. Sci., Part A: Polym. Chem.  1996,  34:  169 
  • 4g Wu Z. Cao L. Zhu PC. Polym. Prepr. (Am. Chem. Soc., Div. Polym. Chem.)  1997,  38:  121 
  • 4h Pittman CU. Wu Z. Zhu PC. J. Polym. Sci., Part A: Polym. Chem.  1997,  35:  485 
  • 4i Zhu PC. Pittman CU. J. Polym. Sci., Part A: Polym. Chem.  1996,  34:  73 
  • 4j Liu Y. Pittman CU. J. Polym. Sci., Part A: Polym. Chem.  1997,  35:  3655 
  • 5a Zhou A. Pittman CU. Tetrahedron Lett.  2005,  46:  3801 
  • 5b Zhu PC. Lin J. Pittman CU. J. Org. Chem.  1995,  60:  5729 
  • 5c Wu Z. Stanley RR. Pittman CU. J. Org. Chem.  1999,  64, 8386 
  • 5d Cao L. PhD Thesis   Mississippi State University; USA: 1999. 
  • 5e Li H. MS Thesis   Mississippi State University; USA: 2005. 
  • 5f Ye G. PhD Thesis   Mississippi State University; USA: 2008. 
  • 6a Gruseck U. Heuschmann M. Tetrahedron Lett.  1987,  28:  6027 
  • 6b Gruseck U. Heuschmann M. Chem. Ber.  1987,  120:  2065 
  • 6c Ye G. Henry WP. Chen C. Zhou A. Pittman CU. Tetrahedron Lett.  2009,  50, 2135 
  • 6d Zhou A. Cao L. Li H. Liu Z. Pittman CU. Synlett  2006,  201 
  • 6e Zhou A. Cao L. Li H. Liu Z. Cho H. Henry WP. Pittman CU. Tetrahedron.  2006,  62:  4188 
  • 6f Diaz-Ortiz A. Diez-Barra E. de la Hoz A. Prieto P. Moreno A. Langa F. Prange T. Neuman A. J. Org. Chem.  1995,  60:  4160 
  • 7a Tohda Y. Kawashima T. Ariga M. Akiyama R. Shudoh H. Mori Y. Bull. Chem. Soc. Jpn.  1984,  57:  2329 
  • 7b Zhou A. Pittman CU. Synthesis  2006,  37 
  • 7c Zhou A. Pittman CU. Tetrahedron Lett.  2005,  46:  2045 
  • 8 Ye G. Zhou A. Henry WP. Song Y. Chatterjee S. Beard DJ. Pittman CU. J. Org. Chem.  2008,  73:  5170 
  • 9 Ye G. Chen C. Chatterjee S. Collier WE. Zhou A. Song Y. Beard DJ. Pittman CU. Synthesis  2010,  141 
  • For examples, see:
  • 10a Sandström J. Sjöstrand U. Wennerbeck I. J. Am. Chem. Soc.  1977,  99:  4526 
  • 10b Adhikesavalu D. Venkatesan K. Acta Crystallog., Sect. C  1983,  39:  1044 
  • 10c Kleinpeter E. Schulenburg A. Tetrahedron Lett.  2005,  46:  5995