tert-Butanol → 1-Propanone, 1,1'-(2,6-pyridinediyl)bis[2,2-dimethyl-

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Reaction Conditions

Reaction Steps

tBuOH (10.0 ml, 105 mmol) was dissolved in THF (50 ml) and cooled to 0° C. nBuLi, 1.6M in hexane, (66 ml, 106 mmol) was added over 30 minutes. The resulting light pale yellow solution was stirred at 0° C. for one hour. This ButOLi solution was then added over 30 minutes into the suspension of CuI (I) (20.0 g, 105 mmol) in THF (100 ml) which was cooled to 0° C. The resulting orange-brown suspension was stirred at room temperature for 45 minutes and then cooled to -78° C. tBuLi, 1.7M in pentane, (62 ml, 105 mmol) was added over 50 minutes and stirred at same temperature for another one hour, giving orange-gray suspension. 2,6-pyridinedicarboxylic acid dichloride (8.2 g, 40.2 mmol) in THF (80 ml) was added over 40 minutes, leading to a dark red-brown solution. The stirring was continued for another one hour at -78° C., then MeOH (40 ml) was added over 5 minutes. The mixture was stirred for about 20 minutes and then warmed up to room temperature, whereupon it became black. Saturated NH4Cl--H2O (400 ml) was added. The organic solution was separated off The aqueous layer was extracted with ether (4×50 ml). The combined organic solutions were dried overnight over Na2SO4. After filtered, the solvents were removed under reduced pressure. The crude product was subjected to chromatography on silica gel column, eluted with hexane/AcOEt (16:1). Yield: 8.1 g (82%). 1H-NMR (CDCl3): dH=8.05-7.85(m, 3 H, aromatic) and 1.47 (s, 18 H, CH3). 13C-NMR (CDCl3): dC=205.46 (C=O), 153.44 (C2,6), 137.69 (C4), 125.87 (C3,5), 43.75 (C(CH3)3), 27.16 (C(CH3)3).

Provenance & Evidence