Bieber, Theodore I.

Vanadyl etioporphyrin I has C4 symmetry and is chiral. Hence,
it should be resolvable. Attempts were made to resolve it into its
enantiomers by chromatography using optically active ads or bents since
it has no functional groups which can be used to form isolable
diastereomers. Numerous optically active ads or bents were tried in the
pure state and adsorbed on silica gel. In most cases the Rf values were
either close to zero or close to one, making resolution impossible. Only
in the case of lactose on silica gel and using benzene as the solvent was
the Rf value such (approx. 0. 52) that resolution seemed, at least, possible.
However, no optically active fraction could be obtained on column
chromatography. Since oxygen exchange between the vanadyl group of vanadyl
etioporphyrin I and water might occur and cause rapid interconversion
of the enantiomers (hence racemization), thereby vitiating resolution
attempts, the possibility of such oxygen exchange was investigated under
a variety of conditions by means of H2 O^18 . The I. R. method was used to
detect any such exchange (VO^18 vs. VO^16). It was found that vanadyl etioporphyrin
I fails to undergo any measurable exchange under all the conditions
tried, although the vanadyl ion of vanadyl sulfate does undergo
exchange.

Dihaloacetonitriles (DHANs) are shown to be produced
by the chlorination of natural water, thus joining the
ranks of the trihalomethanes (THMs) likewise produced by
chlorination. Certain amino acids such as aspartic acid,
tryptophan, and tyrosine are implicated as precursor substances
for the DHANs and also to some extent for the THMs.
The degradation of DHANs by hydrolysis and by thiosulfate
was studied. Various methods of analysis are evaluated with
respect to their ability to determine DHANs and THMs. The
dilemma faced by water plants in dealing with the dual
problem of DHANs and THMs is discussed. The role of hydrolysis
in the formation of THMs has also been evaluated.

The acid-catalyzed N-alkylation of an amide by an alcohol or an alkene
occurs successfully if the intermediate carbenium ion is highly stabilized
and therefore readily formed. This is because carbenium ion formation
must compete successfully with protonation and consequent deactivation
of the amide. The carbenium ion will N-alkylate the amide unless steric
requirements preclude such attack. In boiling glacial acetic acid acetamide is N-alkylated readily by ferrocenylmethanol, a-hydroxyethylferrocene and vinylferrocene but slowly by triphenylmethanol. Triphenylnmethylation is accelerated by a small amount of sulfuric acid. Reaction
of acetamide with diphenylmethanol in boiling glacial acetic acid yields
N-diphenylmethylacetamide in the presence of sulfuric acid, diphenylmethyl acetate in the ascence of sulfuric acid. Under both these conditions
the reaction of acetamide with benzyl alcohol fails, benzyl acetate
being the sole product. Nicotinamide is triphenylmethylated and ferrocenylmethylated only on the amide nitrogen, not on the pyridine nitrogen.
N-methylacetamide, a secondary amide, can be N-ferrocenylmethylated.