Methyl-pyridines side-chain acidity

Only a few examples of the use of this reaction to synthesize pyridine side-chain acids were found. 4-Pyridyl propyl ketone was converted to the methyl ester of 4-pyridylbutyric acid. ... 

Several methyl esters were synthesized by the treatment of pyridine acetic adds with diazomethane. A variety of C-21 steroidal alco-hols " and the following alcohols have been employed in esterification reactions with pyridine side-chain acids. ... 

Indolizines, formation from pyridine acetates, 355-357 formation from pyridine side-chain carboxylic acids, 355-357, 481-488 5-methyl, synthesis, 352 N-(2- (3-Indolyl)ethyl]-2-halo (or ethoxy) pyridinium bromide, hydrolysis, 787 ring closure by fusion, 787... 

Radiation Induced Reactions. Graft polymers have been prepared from poly(vinyl alcohol) by the irradiation of the polymer-monomer system and some other methods. The grafted side chains reported include acrylamide, acrylic acid, acrylonitrile, ethyl acrylate, ethylene, ethyl methacrylate, methyl methacrylate, styrene, vinyl acetate, vinyl chloride, vinyl pyridine and vinyl pyrrolidone (13). Poly(vinyl alcohols) with grafted methyl methacrylate and sometimes methyl acrylate have been studied as membranes for hemodialysis (14). Graft polymers consisting of 50% poly(vinyl alcohol), 25% poly(vinyl acetate) and 25% grafted ethylene oxide units can be used to prepare capsule cases for drugs which do not require any additional plasticizers (15). 

The structure and numbering system for pyridine are given in Section 11.21, where we are also told that pyridine is aromatic. Oxidation of 3-methylpyridine is analogous to oxidation of toluene. The methyl side chain is oxidized to a carboxylic acid. 

Silylation with silyl chlorides or silyl triflates is performed in the presence of auxiliary bases, e.g. pyridine, TEA, imidazole, etc., in solvents such as CH2CI2, CHQ3, DMF, or As milder reagents A-methyl-G-(trimethylsilyl)acetamide and preferably A,C)-bis(trimethylsilyl)acetamide (BTMSA, 136) (Scheme 72) are used for such purposes. Since the acetamide that results from this reaction is difficult to remove from the reaction medium, cyanotrimethylsilanet or l-(trimethylsilyl)imidazole (137).t l may be used as alternatives. For quantitative silylation of amino acids containing additional side-chain functionalities, excess silylating agent is required. 

Large rate accelerations have been observed in the metal ion-promoted hydrolysis of some lactams and these reactions are considered in Section 61.4.10. Other investigations have dealt with divalent metal ion-catalyzed hydrolysis of p-nitrophenyl picolinate in the presence of imidazoles and pyridines having hydroxyl groups in their side chains, the zinc(II)-facilitated hydrolysis of esters of 2-hydroxy acids and the metal ion-promoted hydrolysis of methyl 2-( JV-acetylhydrazono) propanoate. ... 

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