2,6-lutidine from acetone

Parker and Eberson [17] demonstrated that the oxidation of 9,10-dibromoanthracene in the presence of a nucleophile (e.g. 3,5-lutidine) results in the replacement of a bromine by the nucleophile. In a series of papers [18], various polyfluoroaromatic amines were oxidized at platinum in an acetone-water mixture for example, octafluoroacridone was synthesized from 2-aminononafluorobenzophenone (Scheme 2). 

A 1-1. three-necked flask is fitted with a dry ice-acetone condenser, a glass stirrer, and a glass stopper (Note 1). Potassium amide is prepared in 400 ml. of liquid ammonia from 8.0 g. (0.20 g.-atom) of potassium metal (Note 2). The glass stopper is replaced with an addition funnel containing 32.1 g. (0.300 mole) (Note 3) of 2,(>-hitidine dissolved in about 20 ml. of anhydrous ether. The lutidine solution is added to the amide... 

Figure 7.6 Response of rates of elimination of HX (log kE) and substitution (log ks) of cyclohexyl X, induced by NBu4C1 in acetone containing lutidine at 75°C, to change of leaving group X. From P. Beltrame, G. Biale, D. J. Lloyd, A. J. Parker, M. Ruane, and S. Winstein, J. Amer. Chem. Soc., 94, 2228 (1972). Reprinted by permission of the American Chemical Society.

With bridgehead substituted bicyclo[4,2.0]alkanes, each pair of cis- or /ran.v-fused systems gives essentially the same ratio of products. Thus, solvolysis of cis- and m 5-l-(3,5-dinitrophenyl-methoxy)bicyclo[4.2.0]octane in 80% aqueous acetone buffered with 2,6-lutidine at 140°C and 100°C, respectively, gave the same mixture of spiro[2.5]octan-4-ol 14 and bicyclo[4.2.0]octan-l-ol 13 obtained from spirocyclopropylmethyl cation derivatives, suggesting one or more common intermediates. ... 

Scheme 26.2 Synthesis of subset of DOS library from compound 2 (a) cyclopenta-diene, RhjfOAc) (1 mol%), CHjClj (b) m-CPBA, CHjCI (c) OSO4 (2.5mol%), NMO, acetone-HjO (9 1) (d) aldehyde/ketone, CSA (10mol%), 3 A molecular sieves, CHjClj,- (e) SOCI2, CH2CI2 (f) 2,6-lutidine, NMO, OSO4 (2.5mol%), Phl(OAc)2, acetone-HjO (10 1), then dimethylamine, NaBH(OAc)3, CHjClj ...

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