Pyridine, double bond equivalency

The //NMR spectrum contains five signals with integral levels in the ratios 1 1 1 1 3 four lie in the shift range appropriate for aromaties or heteroaromaties and the fifth is evidently a methyl group. The large shift values (up to Sh = 9.18, aromaties) and typical coupling constants (8 and 5 Hz) indicate a pyridine ring, which accounts for four out of the total five double-bond equivalents. 

A monosubstituted pyridine ring and a methyl group add up to CgJT N. The atoms C and O which are missing from the empirical formula and a double-bond equivalent indicate a carbonyl group. The only structure compatible with the presence of these fragments is 3-acetylpyridine. 

In pyridine, as in 2-propanol, the selectivity of reduction favors the A" -3-ketone over the 17- and 20-ketones.Kupfer suggests that resonance interactions between the double bond and the 3-ketone are smaller in pyridine and in 2-propanol than in methanol. However, by slow addition (1 hour) of one equivalent of NaBH4 in pyridine to a solution of androst-4-ene-3,17-dione i n methanol, testosterone has been obtained in good yield (72 %). Similarly,... 

When two equivalents of pyridine were added to the nmr sample and the probe heated to 80° C, the enol formate 61 decreased and phenyl cyclopropyl ketone 58 appeared at a rate approximately ten times faster than in the previous buffered system. The observation of intermediate 61 and the kinetic results, together with the observed induction periods, are consistent with the idea that some and perhaps all of the rearranged product ketone in the solvolysis of this system arises via double-bond participation in 61 rather than triple-bond participation and a vinyl cation (80). 

Aresta (54) has investigated the platinum complexes formed with o-allylphenol and o-allylthiophenol. The phenolic ligand reacts with the PtCl4 ion (in a suitable acetate buffer) to form the chelate complex shown in Fig. 40. The coordinated double bonds of this compound are successively replaced by two equivalents of pyridine. 

The reaction of sulphides with (dichloroiodo)benzene can lead to several kinds of products depending on the substrate and the reaction conditions [19]. Sulphides of great structural diversity (aliphatic, aromatic, heterocyclic) were oxidized efficiently by (dichloroiodo)benzene (one equivalent) in aqueous pyridine. The reaction was almost instantaneous and not noticeably sensitive to steric or electronic effects. Ethylenic double bonds were not attacked under these conditions however, in vinylic sulphides containing an electron-withdrawing group (COOH or RSO) ft- to the sulphur atom the oxidation was accompanied by nucleophilic attack to the double bond resulting in a mixture of products. The method is suitable for the preparation of I80-labelled sulphoxides using small quantities of H2,80. 

The addition of two hydroxylic groups to the double bonds of unsaturated ketones is carried out by the same methods used for hydroxylations of alkenes (equations 71-83). As an example, hydroxylation of the double bond in 3p-hydroxyandrost-5-en-17-one is accomplished by treatment with one equivalent of osmium tetroxide in pyridine and subsequent reductive cleavage of the osmate ester with sodium bisulfite in aqueous pyridine (equation 442) [950. ... 

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