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 — John Shaqi
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.)
(d) 10 grams of anthranilic nitrile, twenty grams of acetic anhydride,
and twenty-five grams of sodium selenide were mixed in a sealed
tube and heated together for three hours and a half at 110°-115°. The
condensation product was crystalline when the tube was cooled to room
temperature. The contents of the tube were extracted with dilute alkali
as before, filtered, precipitated by carbon dioxide, and recrystallized
from dilute alcohol. The yield was not over twenty per cent.
(e) An attempt was made to make o-aminobenzoselenamide, and from the
latter, by treatment with acetic anhydride, to form the quinazoline,
but the yield of the amide was too small to carry the reaction further.
The substance prepared by the above methods crystallizes from dilute
alcohol in needles or prisms of dark brown color. It melts at 213.5°
(corr.). It dissolves readily in hot alcohol but on concentration
sometimes forms a sticky mass with a peculiar but not unpleasant odor.
It dissolves readily in alkalis and is slightly soluble in hot benzene
and chloroform, but insoluble in hot water. Crystals purified from (a)
were analyzed and gave the following results:
Calculated for Found
C₉H₈N₂Se I II
Carbon 48.38% 48.45% 48.62%
Hydrogen 3.61 3.82 3.52
Nitrogen 12.55 12.51 12.66
Selenium 35.46 35.60 35.42
The crystals on standing in the presence of air and light decomposed
with separation of finely divided selenium and methyl quinazolone.
Analysis of Selenium Organic Compounds
In the quantitative determination of selenium in quinazoline
the method adapted by Becker and Meyer was found to be quite
satisfactory(56). Other methods are listed in the bibliography(57).
In the ultimate analysis of carbon and hydrogen, the ordinary absolute
method was followed with the use of copper oxide, lead chromate,
and lead peroxide in the tube. In the determination of nitrogen
the ordinary absolute method was also followed excepting that a
considerable quantity of specially prepared lead chromate powder was
mixed with the sample in a number six porcelain boat. This was found to
be desirable when the dinitroselenazole was burned. Selenium dioxide,
which is a solid, seems to be formed in the tube and carried away by
the current of carbon dioxide with some difficulty. In such a case the
analysis usually took four hours after the combustion had actually
started. In the carbon and hydrogen determination selenium dioxide was
easily absorbed in the presence of oxygen gas.
Preparation of 2-Phenylbenzoselenazole
The first method employed was a modification of the method described
by Fromm and Martin(58). Method (b) is an adaptation of the method for
preparing benzothiazoles.
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