Reaction of Cyanogen with Organic Compounds. XII. Glycols and Glycol Monoethers¹

The Chemistry of Imidates.

“…Glycols have received less attention, but Pinner (253) was able to prepare an imidate from ethylene glycol and hydrogen cyanide. 1,2-and 1,3-propanediols as well as 2,3-butanediol react with cyanogen to give symmetrical oxaldiimidate dihydrochlorides (349), An early literature reference to the attempted preparation of an imidate by this method is to be found in the work of Beckurts and Otto (25), but credit for the elucidation of the nature of this reaction and for detailed study of these compounds must be reserved for Pinner (252,268).…”

Imidates

“…(1) is still widely used and consists of condensing a nitrile with an alcohol under anhydrous conditions at 0°C in the presence of hydrogen chloride or bromide [ l a , b ] . Solvents such as ether [28], dioxane [29], dimethyl cellosolve [30], chloroform [22g], benzene [31] and nitrobenzene [22g] are sometimes employed as diluents and as an aid to crystallization of the imidate salt. The use of excess alcohol may cause ortho ester formation.…”

“…Glycols [36] and diols [30] are also effective in the Pinner synthesis (Eqs. 18,19), as well as mercaptans (Eq.…”

“…56°C (2.5 Torr.). The IR (neat) c m " T h e silver salts of amides [85a-c] and anilides [86a-d] react with ethyl iodide to give imidates [56][57][58]. In the case of the amide, using methyl iodide in place of ethyl iodide gives a mixture of iV-substituted imidate and the iV,iV-disubstituted amide ( E q .…”

Transformation of 2-alkoxyimidate-1,10-phenanthroline metal (Mn2+, Co2+ and Ni2+) chlorides from bis(2-cyano-1,10-phenanthroline) metal chlorides: Syntheses, characterizations and their catalytic behavior toward ethylene oligomerization

“…The addition reaction of alcohols to nitriles was discovered by Nef in 1895 [1], in which the reaction of cyanogen with an aqueous ethanol solution of potassium cyanide gave ethyl 1-cyanoformimidate and diethyl oxalimidate. Such reaction was extended to other alcohols [2], and could be catalyzed by alkoxide in the presence of electron-withdrawing groups in the nitrile [3]. The resultant imidate products were found useful in organic synthesis [4,5], for example, the phenanthroline derivatives bearing chiral 2-oxazolinyl groups were prepared by the condensation reaction of 2-cyano-1,10-phenanthroline with the suitable optically active baminoalcohol [4,6].…”