Poly alkyl halide treatment

Direct alkylation of hydrazine itself with halides and sulfates usually gives mixtures of mono- and poly-alkylated hydrazines. It is possible to get useful yields of the monoalkylhydrazine by using an excess of hydrazine. Several specific procedures leading to monoalkylhydrazines are based on selective alkylation of hydrazine derivatives with protecting groups attached. So, easily prepared acetone N-(diethoxyphosphoryl)hydrazone (75) can be used. Phase-transfer catalyzed N-alkylation of (75), followed by deprotection with p-toluenesulfonic acid provides monoalkylhydrazine sulfonates (76 Scheme 17). Similarly, N-alkyl-N-arylhydrazines have been prepared by phase-transfer catalyzed N-alkylation of arylhydrazones (Scheme 18). An efficient, one-pot method for the synthesis of a variety of polysilyl-ated hydrazines employs hexamethyldisilane (equation 30). Polysilylated hydrazines were found to react with aldehydes or ketones to give hydrazones under anhydrous conditions. By treatment with triphenylphosphine and diethyl azodicarboxylate primary and secondary alcohols can be converted to hy-dr ine derivatives (equation 31). ... 

Polymeric amines can be proton acceptors, acyl transfer agents, or ligands for metal ions. The 2- and 4-isomers of poly(vinylpyridine) (11) and (12) and the weakly basic ion exchange resins, p-dimethylaminomethylated PS (2) and poly(2-dimethylaminoethyl acrylate), are commercial. The ion exchange resins are catalysts for aldol condensations, Knoevenagel condensations, Perkin reactions, cyanohydrin formation and redistributions of chlorosilanes. " The poly(vinylpyridine)s have been used in stoichiometric amounts for preparation of esters from acid chlorides and alcohols, and for preparation of trimethylsilyl ethers and trimethylsilylamines from chlorotrimethylsilane and alcohols or amines. Polymer-suppored DBU (l,8-diazabicyclo[5.4.0]undec-7-ene) (52) in stoichiometric amounts promotes dehydrohalogenation of alkyl bromides and esterification of carboxylic acids with alkyl halides. The protonated tertiary amine resins are converted to free base form by treatment with aqueous sodium hydroxide. 

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