Tandem Reactions of 2-Methylimidazoline
and 1,2-Dimethylimidazoline with Various Benzoyl Chlorides

Guozhong Ye; Chunlong Chen; Sabornie Chatterjee; Willard E. Collier; Aihua Zhou; Yingquan Song; Debbie J. Beard; Charles U. Jr. Pittman

doi:10.1055/s-0029-1217048

PAPER

Tandem Reactions of 2-Methylimidazoline and 1,2-Dimethylimidazoline with Various Benzoyl Chlorides

Guozhong Ye*^a, Chunlong Chen^b, Sabornie Chatterjee^a, Willard E. Collier^a, Aihua Zhou^c, Yingquan Song^a, Debbie J. Beard^a, Charles U. Jr. Pittman *^a
^a Department of Chemistry, Mississippi State University, Starkville, MS 39762, USA
Fax: +1(662)3257611; e-Mail: cpittman@chemistry.msstate.edu; e-Mail: gye001@gmail.com;
^b Department of Chemistry, University of Pittsburgh, Pittsburgh, PA 15260, USA
^c Pharmacy School, University of Wisconsin-Madison, Madison, WI 53706, USA

Abstract

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Abstract

The reactions of 2-methylimidazoline with excess benzoyl chlorides under mild conditions generated N,N′-diacyl-β-keto cyclic ketene-N,N′-acetals. Conversely, the corresponding reactions of 1,2-dimethylimidazoline under the same conditions stereoselectively formed the ring-opened (Z)-vinyl benzoates. The latter reactions feature the formation of carbon-carbon bonds, carbon-nitrogen bonds, and carbon-oxygen bonds in one sequential cascade.

Key words

acyl ketene-N,N′-acetal - carbon-carbon bond formation - 2-methylimidazoline - 1,2-dimethylimidazoline

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References

<A NAME="RM04409SS-1">1</A> McElvain SM. Tate BE. J. Am. Chem. Soc. 1945, 67: 202

<A NAME="RM04409SS-2">2</A> Gruseck U. Heuschmann M. Chem. Ber. 1987, 120: 2053

<A NAME="RM04409SS-3">3</A> Clemens DH. Bell AJ. O’Brien JL. J. Org. Chem. 1964, 29: 2932

<A NAME="RM04409SS-4">4</A> Baganz H. Domaschke L. Chem. Ber. 1962, 95: 2095

<A NAME="RM04409SS-5">5</A> Bredereck H. Effenberger F. Beyerlin HP. Chem. Ber. 1964, 97: 3081

<A NAME="RM04409SS-6">6</A> Weingarten H. White WA. J. Org. Chem. 1966, 31: 2874

<A NAME="RM04409SS-7">7</A> Hasek RH. Gott PG. Martin JC. J. Org. Chem. 1964, 29: 2513

<A NAME="RM04409SS-8">8</A> Hall JH. Wojciechowska M. J. Org. Chem. 1978, 43: 4869

<A NAME="RM04409SS-9">9</A> Armati A. De Ruggieri P. Rossi E. Stradi R. Synthesis 1986, 573

<A NAME="RM04409SS-10">10</A> Rossi E. Pini E. Tetrahedron 1996, 52: 7939

<A NAME="RM04409SS-11">11</A> Neidlein R. Klotz UJ. Chem. Ber. 1985, 118: 3217

<A NAME="RM04409SS-12">12</A> Schoeni JP. Fleury JP. Tetrahedron 1975, 31: 671

<A NAME="RM04409SS-13">13</A> Nakayama J. Akimoto K. Sugihara Y. Tetrahedron Lett. 1998, 39: 5587

<A NAME="RM04409SS-14">14</A> Marcelis ATM. Van der Plas HC. Tetrahedron 1989, 45: 2693

<A NAME="RM04409SS-15">15</A> Gruseck U. Heuschmann M. Chem. Ber. 1987, 120: 2065

<A NAME="RM04409SS-16">16</A> Heuschmann M. Chem. Ber. 1988, 121: 39

<A NAME="RM04409SS-17">17</A> Sauer J. Heldmann DK. Hetzenegger J. Krauthan J. Sichert H. Schuster J. Eur. J. Org. Chem. 1998, 12: 2885

<A NAME="RM04409SS-18">18</A> Mueller K. Sauer J. Tetrahedron Lett. 1984, 25: 2541

<A NAME="RM04409SS-19">19</A> Fioravanti S. Loreto MA. Pellacani L. Tardella PA. Heterocycles 1987, 25: 433

<A NAME="RM04409SS-20">20</A> Rajagopalan P. Talaty CN. Tetrahedron Lett. 1966, 38: 4537

<A NAME="RM04409SS-21">21</A> Gotthardt H. Flosbach C. Chem. Ber. 1988, 121: 951

<A NAME="RM04409SS-22">22</A> Gotthardt H. Blum J. Chem. Ber. 1987, 120: 109

<A NAME="RM04409SS-23A">23a</A> Aspinall SR. J. Org. Chem. 1941, 6: 895

<A NAME="RM04409SS-23B">23b</A> Bergman J. Goonewardena H. Sjoeberg B. Heterocycles 1982, 19: 297

<A NAME="RM04409SS-24">24</A> Zhou A. Pittman CU. Tetrahedron Lett. 2004, 45: 8899

<A NAME="RM04409SS-25">25</A> Zhou A. Pittman CU. Synthesis 2006, 37

<A NAME="RM04409SS-26">26</A> Zhou A. Pittman CU. Tetrahedron Lett. 2005, 46: 2045

<A NAME="RM04409SS-27">27</A> Ye G. Zhou A. Henry WP. Song Y. Chatterjee S. Beard DJ. Pittman CU. J. Org. Chem. 2008, 73: 5170

<A NAME="RM04409SS-28A">28a</A> Tieman CH, Kollmeyer WD, and Roman SA. inventors; US 4002765. ; Chem. Abstr. 1977, 86, 134904

<A NAME="RM04409SS-28B">28b</A> Nutt DJ. French N. Handley S. Hudson A. Husband S. Jackson H. Jordan S. Lalies MD. Lewis J. Lione L. Mallard N. Prat J. Ann. N. Y. Acad. Sci. 1995, 763: 125

<A NAME="RM04409SS-28C">28c</A> Jonas J.-C. Garcia-Barrado M.-J. Angel I. Henquin J.-Cl. Eur. J. Pharmacol. 1994, 264: 81

<A NAME="RM04409SS-28D">28d</A> Venn RM. Bradshaw CJ. Spencer R. Brealey D. Caudwell E. Naughton C. Vedio A. Singer M. Feneck R. Treacher D. Willatts SM. Grounds RM. Anaesthesia 1999, 54: 1136

<A NAME="RM04409SS-28E">28e</A> Buerkle H. Yaksh T. Br. J. Anaesth. 1998, 81: 208

<A NAME="RM04409SS-28F">28f</A> Lemke KA. Can. Vet. J. 2004, 45: 475

<A NAME="RM04409SS-28G">28g</A> Emanuel B. Kompatscher P. Meyer VE. Plast. Reconstr. Surg. 2001, 108: 637

<A NAME="RM04409SS-28H">28h</A> Pigini M. Bousquet P. Brasili L. Carrieri A. Cavagna R. Dontenwill M. Gentili F. Giannella M. Leonetti F. Piergentili A. Quaglia W. Carotti A. Bioorg. Med. Chem. 1998, 6: 2245

<A NAME="RM04409SS-28I">28i</A> Van Zwieten PA. J. Hypertens. 1997, 15: 117

<A NAME="RM04409SS-28J">28j</A> LeBrigand L. Virsolvy A. Peyrollier K. Manechez D. Godfroid JJ. Guardiola Lemaitre B. Bataille D. Br. J. Pharmacol. 1997, 122: 786

<A NAME="RM04409SS-28K">28k</A> Molderings GJ. Donecker K. Burian M. Simon WA. Schroeder DW. Göthert M. J. Pharmacol. Exp. Ther. 1998, 285: 170

X-ray crystallographic description of 12a: Crystal dimensions (mm): 0.38 × 0.35 × 0.22. C₂₆H_25.5N₂O_4.25; Mr = 433.98. Triclinic; space group P1; a = 8.571(2) Å, b = 10.140(2) Å, c = 14.383(3) Å; α = 103.687(3)˚, β = 106.909(3)˚, γ = 96.759(4)˚; V = 1138.5(4) Å^³; Z = 2; D(calcd) = 1.266 g/cm^³; µ (mm^-¹) = 0.086; F(000) = 459; Reflections collected/unique = 8421/4000; refinement method: full-matrix least-squares on F ^²; final R indices [I > 2s (I)]. R1 = 0.0468, wR2 = 0.1099, R indices (all data) R1 = 0.1093, wR2 = 0.1370; goodness of fit on F^² = 1.000. Crystals were grown by slow evaporization of pentane into a CHCl₃-EtOAc solution of 12a. CCDC number for compound 12a is CCDC 683239. This data can be obtained free of charge from the Cambridge Crystallographic Data Centre via ww.ccdc.cam.ac.uk/datarequest/cif.

SMART Version 5.625, SAINT+Version 6.22, 2001. Bruker Analytical X-ray Systems, Inc., Madison, Wisconsin, USA.

G. M. Sheldrick; SHELXTL Version 6.1, 2000; Bruker Analytical X-ray Systems, Inc., Madison, Wisconsin, USA.

Cyclic amidinium salts readily undergo ring-opening hydrolysis in the presence of water, see:

<A NAME="RM04409SS-32A">32a</A> DeWolfe RH. Cheng MWL. J. Org. Chem. 1969, 34: 2595

<A NAME="RM04409SS-32B">32b</A> DeWolfe RH. J. Am. Chem. Soc. 1960, 82: 1585

<A NAME="RM04409SS-32C">32c</A> Perrin CL. Thoburn JD. J. Am. Chem. Soc. 1993, 115: 3140

<A NAME="RM04409SS-33">33</A> Forsberg JH. Spaziano VT. Balasubramanian TM. Liu GK. Kinsley SA. Duckworth CA. Poteruca JJ. Brown PS. Miller JL. J. Org. Chem. 1987, 52: 1017