Sodium picolyls , reactions with

The 3-pyridyl Grignard reagent has been alkenylated by reaction with allyl halides and the 2-picolyl Grignard reagent homologated with alkyl halides and to-diethoxyalkyl halidesi . Of much greater importance has been the use of picolyl lithium, potassium and sodium compounds in reactions with alkyl and aralkyl halides. 

The picolylsulfone 5 is obtained by a reaction involving the conversion of a sulfonate sodium salt 2 into a sulfmate sodium salt 4 and reaction of the latter with 2-picolyl chloride (refs 6,7 eqn. 1). 

When a mixture of aniline hydrochloride and 2-chloromethylpyridlne is heated at 135 to 140 for 2 hours and then made alkaline with sodium carbonate, A -(2-picolyl)aniline (IX-22S) results. If the reaction temperature is raised to 225 to 230°, rearrangement occurs and 4-(2-picolyl)aniline (IX-226) is obtained instead. ... 

The reactions of pyridyl and picolyl metallic derivatives with organic reagents are of great synthetic value. Since the courses taken are, more often than not, normal, no attempt will be made to do more than substantially exemplify these uses and to note some of the infrequent irregularities. It can be said that almost always the yields realized in reactions using the Grignard reagents are inferior to those obtained with lithium, potassium or sodium compounds. 

The side-chain ethylation and propylation of picolines with olefins under pressure, in the presence of sodium, has been carried out a, 6O8, These reactions are evidently nucleophilic attacks by the picolyl anions upon the olefins. With increasing substitution of the side chain only the more acidic... 

Pyridyl lithium gives a small yield of the Michael addition product with benzalacetophenone , as does 4-picolyl sodium with methyl vinyl ketone i2 . In contrast, 2-picolyl sodium forms the carbinol, perhaps because of initial reaction at the nitrogen atom... 

In coordination chemistry, architectures containing the triazole heterocycle have been developed as monodentate and polydentate nitrogen ligands. Special attention has been given to (2-pyridyl)- and more flexible (2-picolyl)-l,2,3-triazoles. Thus, a hbrary of selected 1,4-disubstituted 1,2,3-triazoles differently functionahzed with pyridine, pyrimidine, and pyrazine have been synthesized by the reaction of aryl, heteroaryl, and heteroarylmethyl azides with alkynes. Three different copper(l) sources, that is, CuSO /sodium ascorbate, CuBrlPPhglg, and (CuOTf)2 CgHg, were used to promote the reactions [89]. 

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