Abstract
A simple and convenient synthesis for functionalised bi-2(1H )-pyrazinones 9 , 11a -h starting from 3,5-dichloro-2(1H )-pyrazinones 7 , 10a -h is described. The pyrazinone is homo-coupled by means of a Suzuki-type reaction of an in situ generated boronate. The reactions were carried out under conventional heating as well as under microwave irradiation and dramatic improvements in the rates and yields have been observed under the latter conditions.
Key words
bis-heterocycle - pyrazinone - Suzuki chemistry - bis(pinacolato)diboron
References 1 Currently on a leave of absence from Helwan University, Cairo, Egypt.
2a
Sleiman H.
Baxter P.
Lehn JM.
Rissanen K.
J. Chem. Soc., Chem. Commun.
1995,
715
2b
Ziessel R.
Youinou MT.
Angew. Chem., Int. Ed. Engl.
1993,
32:
877
2c
Harding MM.
Koert U.
Lehn JM.
Marquisrigault A.
Piguet C.
Siegel J.
Helv. Chim. Acta
1991,
74:
594
2d
Hasenknopf B.
Lehn JM.
Kneisel BO.
Baum G.
Fenske D.
Angew. Chem., Int. Ed. Engl.
1996,
35:
1838
2e
Baxter PNW.
Lehn JM.
Fischer J.
Youinou MT.
Angew. Chem., Int. Ed. Engl.
1994,
33:
2284
2f
Baxter PNW.
Hanan GS.
Lehn JM.
Chem. Commun.
1996,
2019
3a
Lehn JM.
Regnouf De Vains JB.
Helv. Chim. Acta
1992,
75:
1221
3b
Papet AL.
Marsura A.
Synthesis
1993,
478
3c
Papet AL.
Marsura A.
Ghermani NE.
Lecomte C.
Friant P.
Rivail JL.
New J. Chem.
1993,
17:
181
3d
Bodar-Houillon F.
Humbert T.
Marsura A.
Devains JBR.
Dusausoy O.
Bouhmaida N.
Ghermani NE.
Dusausoy Y.
Inorg. Chem.
1995,
34:
5205
4
Bodar-Houillon F.
Marsura A.
New J. Chem.
1996,
20:
1041
5 The product most closely resembling these structures is [2,2′-biquinoxaline]-3,3′(4H ,4′H )-dione reported in: Hünig S.
Pütter H.
Chem. Ber.
1977,
110:
2532
6
Vekemans J.
Pollers-Wieërs C.
Hoornaert G.
J. Heterocycl. Chem.
1983,
20:
919
7a
Azzam R.
De Borggraeve W.
Compernolle F.
Hoornaert GJ.
Tetrahedron Lett.
2004,
45:
1885
7b
Kaval N.
Bisztray K.
Dehaen W.
Kappe CO.
Van der Eycken E.
Mol. Diversity
2003,
7:
125
8 We tried to suppress the homodimerisation by slowly adding a solution of pyrazinone 10b (1 mmol in 10 mL of dioxane) via an infusion pump (over a time period of 3 h) to a stirred suspension of [B(Pin)]2 (1 mmol), K2 CO3 (1 mmol) and tetrakis (3 mol%) in 10 mL of dioxane at 80 °C. However, even using slow addition, the formation of the bipyrazinones could not be prevented.
9 Comparable methodology for the synthesis of symmetrical biaryls was reported in: Nising CF.
Schmid UK.
Nieger M.
Bräse S.
J. Org. Chem.
2004,
69:
6830
10a
Van der Eycken E.
Appukkuttan P.
De Borggraeve W.
Dehaen W.
Dallinger D.
Kappe CO.
J. Org. Chem.
2002,
67:
7904
10b
Kaval N.
Van der Eycken J.
Caroen J.
Dehaen W.
Strohmeier GA.
Kappe CO.
Van der Eycken E.
J. Comb. Chem.
2003,
5:
560
11 EM-Discover, CEM Corporation P.O. Box 200 Matthews, NC 28106.
12 Also in the microwave experiments, formation of minor amounts of protodeboronation product (<10%) could not be avoided.