4-Hydroxy-methylen-4'-methyl-2,2'-bipyridine
Institut für Organische Chemie, Universität Regensburg, D-93040 Regensburg, Germany
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Molecules 2001, 6(3), M205; https://doi.org/10.3390/M205
Submission received: 16 November 2000
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Accepted: 15 December 2000
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Published: 25 March 2001
(This article belongs to the Section Molbank Section of Molecules, 1997-2001)
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
- Lehn, J.-M.; Rigault, A.; Siegel, J.; Harrowfield, J.; Chevier, B.; Moras, D. Proc. Natl. Acad. Sci. U.S.A. 1987, 84, 2565. [Google Scholar] [CrossRef] [PubMed]
- 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.
- 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.
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Kercher, M.; König, B. 4-Hydroxy-methylen-4'-methyl-2,2'-bipyridine. Molecules 2001, 6, M205. https://doi.org/10.3390/M205
AMA Style
Kercher M, König B. 4-Hydroxy-methylen-4'-methyl-2,2'-bipyridine. Molecules. 2001; 6(3):M205. https://doi.org/10.3390/M205
Chicago/Turabian StyleKercher, Michael, and Burkhard König. 2001. "4-Hydroxy-methylen-4'-methyl-2,2'-bipyridine" Molecules 6, no. 3: M205. https://doi.org/10.3390/M205
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