Oxidatively Assisted Alkylations of Sodium Nitrocyanamide and Sodium Azide.

摘要

Chloroperbenzoic acid (HCPBA) oxidatively assisted reactions at 25 deg C between straight chain primary alkyl iodides and sodium nitrocyanamide to give corresponding alkyl nitrocyanamides (M-alkylation) and H-alkoxy-N'-cyanodiazene H-oxides (O-alkylation). Each alkyl nitrocyanamide thermolysed to an alkyl isocycanate. In the absence of of oxidative assistance sodium nitrocyanamide suspended in an inert solvent (25 deg C to 110 deg C) did not convert straight chain primary alkyl halides. Simple secondary and tertiary alkyl iodides and isobutyl iodide in the presence of MCPBA and sodium nitrocyanamide were converted to intractable mixtures that did not contain detectable amounts of alkyl nitrocyanamides, isocyanates, or H-alkoxy-H'-cyanodiazine H-oxides. This differential reactivity between the various types of alkyl iodides was supported by a similar conversion of straight chain primary alkyl iodides to corresponding azides and other alkyl iodides to intractable mixtures on treatment with sodium azide under conditions that brought about no reaction in the absence of oxidative assistance by MCPBA. Alkyl iodides were unreactive to sodium cyanate in the presence or absence of peroxides. Keywords: Alkylation, Chemical reactions, Oxidation, Sodium nitrocyanamide, Sodium, Azide, MCPBA, Reprints. (jg)