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Molecules 2001, 6, M205

4-Hydroxy-methylen-4'-methyl-2,2'-bipyridine

Michael Kercher and Burkhard König*

Institut für Organische Chemie, Universität Regensburg, D-93040 Regensburg, Germany. Fax (+49) 941 943 171; E-mail: [email protected]

Received: 16 November 2000 / Accepted: 15 December 2000 / Published: 25 March 2001

A key intermediate in the synthesis of extended bipyridine ligands [1] is 4-hydroxymethylene-4-methyl-2,2-bipyridine (3), because the hydroxy group is readily converted into a variety of other chemical moieties, such as leaving or carbonyl groups. Two syntheses [2] for the preparation of 3 have been reported, both yielding 3 in two steps from 1 in 34% yield. We report here a more convenient one pot procedure giving an improved higher yield.

To a solution of one equivalent of 4,4-dimethyl-2,2-bipyridene (1) in dry THF were added at -78°C 1.02 equivalents of freshly prepared LDA in THF to form the deeply red anion. After stirring for 30 minutes one equivalent of 2-phenylsulfonyl-3-phenyloxaziridine 2 [3] in THF was slowly added whereby the solution turned yellow. The mixture was allowed to warm up to room temperature, quenched with aqueous sat. NH₄Cl, washed with brine and the organic phase was evaporated to dryness. Column chromatography of the crude product on silica (CH₂Cl₂/CH₃OH/NH₃; 100/5/0.5) yielded 52 % of 4-hydroxymethylene-4-methyl-2,2-bipyridine 3. All spectroscopic data are identical to reported values in the literature.[2a].

¹H NMR (300 MHz, CDCl₃): d = 2.34 (s, 3H, CH₃), 4.66 (s, 2H, CH₂), 5.25 (br s, 1H OH), 7.05-7.18 (m, 2H), 8.07-8.19 (m, 2H), 8.39-8.46 (m, 2H).

¹³C NMR (75 MHz, CDCl₃) d = 21.4 (CH₃), 63.1 (CH₂), 119.0 (CH), 121.4 (CH), 122.6 (CH), 125.0 (CH), 148.7 (C quart), 148.9 (CH), 149.2 (CH), 152.2 (C quart), 155.9 (C quart), 156.0 (C quart).

IR (KBr): 3200, 1596, 1456, 819.

References

1. Lehn, J.-M.; Rigault, A.; Siegel, J.; Harrowfield, J.; Chevier, B.; Moras, D. Proc. Natl. Acad. Sci. U.S.A.1987, 84, 2565.

2. a) Ciana, L. D.; Hamachi, I.; Meyer, T. J. J. Org. Chem. 1989, 54, 1731-1735; b) Chin, T.; Gao, Z.; Lelouche, I.; Shin, Y.-G.; Purandare, A.; Knapp, S.; Isied, S. S. J. Am. Chem. Soc. 1997, 119, 12849-12858; c) Polin, J.; Schmohel, E.; Balzani, V. Synthesis 1998, 3, 321-324; d) Veriot, G.; Dutasta, J.-P.; Matouzenko, G.; Collet, A. Tetrahedron1995,51, 389-400; e) Furue, M.; Kuroda, N.; Nozakura, S.-I. Chem. Lett. 1986, 1209-1212; f) Furue, M.; Yoshidzumi, T.; Kinoshita, S.; Kushida, T.; Nozakura, S.-I.; Kamachi, M. Bull. Chem. Soc. Jpn.1991, 64, 1632-1640.

3. This reagent was synthesized within few hours from commercially available N-benzylidenebenzenesulfonamide according to a known procedure by Davis, F. A.; Chattopadhyay, S.; Towson, J. C.; Lal, S.; Reddy, T J. Org. Chem. 1988, 53, 2087-2089.

Sample availability: available form the authors and MDPI .

1.	Lehn, J.-M.; Rigault, A.; Siegel, J.; Harrowfield, J.; Chevier, B.; Moras, D. Proc. Natl. Acad. Sci. U.S.A.1987, 84, 2565.
2.	a) Ciana, L. D.; Hamachi, I.; Meyer, T. J. J. Org. Chem. 1989, 54, 1731-1735; b) Chin, T.; Gao, Z.; Lelouche, I.; Shin, Y.-G.; Purandare, A.; Knapp, S.; Isied, S. S. J. Am. Chem. Soc. 1997, 119, 12849-12858; c) Polin, J.; Schmohel, E.; Balzani, V. Synthesis 1998, 3, 321-324; d) Veriot, G.; Dutasta, J.-P.; Matouzenko, G.; Collet, A. Tetrahedron1995,51, 389-400; e) Furue, M.; Kuroda, N.; Nozakura, S.-I. Chem. Lett. 1986, 1209-1212; f) Furue, M.; Yoshidzumi, T.; Kinoshita, S.; Kushida, T.; Nozakura, S.-I.; Kamachi, M. Bull. Chem. Soc. Jpn.1991, 64, 1632-1640.
3.	This reagent was synthesized within few hours from commercially available N-benzylidenebenzenesulfonamide according to a known procedure by Davis, F. A.; Chattopadhyay, S.; Towson, J. C.; Lal, S.; Reddy, T J. Org. Chem. 1988, 53, 2087-2089.