A Study of the Pi Complexes of Tetracyanoethylene with Phenols, Aromatic Hydrocarbons, and Aryl Ethers.

Abstract

The 7r complexes of tefracyanoethylene (TCNE) are useful for determining many pure organic molecules, analogous to the broad utility of metal-EDTA chelates in inorganic analysis. TCNE, like EDTA, is a fairly gen-

Study of the Pi Complexes of 2,4,7-Trinitrofluorenone with Phenols, Aromatic Hydrocarbons, and Aromatic Amines.

“…Similar differences in reactivity have been noted with TONE (16) where the colors of TONE complexes disappear with heating on paper but not in solution. Evidently the chemistry of the complexes on paper is different than that in solution.…”

“…It is also apparent that TNF is a more selective acid when the base is large enough to overlap the nitro groups as well as the ring system of TNF. Some of the TCNE detection limits in Table II have already been calculated from Equation 2 (16). Using Equation 2, a K of 73 and an e of 103 for pyrene-TNF, a detection limit (A = 0.10) of 2.3 X 10_W was calculated for pyrene.…”

“…Obviously, large amounts of benzene, halogenated aromatics, and nitroaromatics can be tolerated in the determination of stronger jr bases such as durene (16) or pyrene.…”

“…Acid-Catalyzed Acetylation. The substitution of an electron-withdrawing group like the acetyl group on a phenol or aromatic amine markedly reduces the basicity of these compounds (16). This is accomplished by uncatalyzed acetylation of amines or acid-catalyzed acetylation of amines, phenols, and mercaptans.…”

“…TCNE and TNF both form 1 : 1 complexes with x bases. The formation constant, or stability constant, expression for analytical situations where the x acid is at concentrations appreciably higher than the aromatic x loase is (16):…”