Synthesis of 2-methyl-4-selenoquinazolone, 2-phenylbenzoselenazole, and its derivatives: Dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Faculty of Pure Science of Columbia UniversityChen, Yü-Gwan
Science
Synthesis of 2-methyl-4-selenoquinazolone, 2-phenylbenzoselenazole, and its derivatives: Dissertation submitted in partial fulfillment of the requirements for the degree of Doctor of Philosophy in the Faculty of Pure Science of Columbia University
Chen, Yü-Gwan
Organic compounds -- Synthesis; Selenium; Thesis (Ph. D.)
It would be most natural to conclude that the chromophore :CS is more
powerful than :CO, and that :CSe is most powerful of all, as shown in
our study of quinazoline compounds. It would equally follow that :S is
a more powerful color-forming radical in a cyclic compound than that of
:O; and :NH than that of :S; and :Se again most powerful of the whole
series.
Lesser and Weiss(41) in their research on selenoindigo stated that the
selenium dyestuff, on account of its greater molecular weight than
sulphur, shows a deeper blue. This hypothesis meets a difficulty in the
case of coumorandione, thionaphthenequinone and isatin series, where
the -NH- radical has an atomic weight of 15, and -S- 32, and showed the
reversed order of color. This seems to be the case in the selenophene
series also. Therefore this theory is not without exceptions.
The diselenides present a very interesting study also. Methyl
disulphide is colorless, but methyldiselenide(42) is a reddish
yellow liquid. Methyl disulphide only becomes yellow when it is
treated with chlorine, and in such cases (CH₃)₂S₂Cl₂ is formed(43),
in yellow rhombic crystals. Ethyldisulphide is colorless: ethyl-
disulphidedichloride is a faint yellow oil(44). But the corresponding
ethyldiselenide is a red liquid(45). Phenyl disulphide is colorless,
and phenyldisulphide dibromide is of mother-of-pearl appearance, and
practically colorless(46), while phenyl diselenide forms pure yellow
needles(47), and phenyldiselenide dibromide orange red ones.
While phenyldisulphide is colorless, when an auxochrome group is
added, such as NH₂, the compound is colored. This is the case with
o-diaminodiphenyldisulphide(48) which is yellow both in solution and
in crystalline form. In other words, an auxochrome in addition to the
chromophore group transforms a colorless chromogen into a colored one.
Therefore groups like -S.S- and -Se.Se- are chromophores in the same
sense as -N:N-. This is in agreement with the chromophore ideas of Hugo
Kaufmann. The -Se.Se- is a more powerful chromophore than -S.S-.
This brings one directly to the inquiry as to why 2-phenylbenzo-
selenazole, which contains a :Se radical, should be colorless; and that
even 6-nitro-2-phenylselenazole, with the addition of a chromophore
NO₂, should be only faintly colored. The benzothiazoles, their isomers
and derivatives are mostly colorless, and similar causes are probably
responsible in the case of the phenylbenzoselenazole, for its lack of
color. But when this selenazole is combined with another chromophore,
for example an azomethine grouping, the result is a more positively
colored compound (in this case benzalaminoselenazole), the crystals
being yellow. The corresponding thiazole derivative is light colored.
Public-domain text, read in full here on John Shaqi.
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