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.)
Twenty-five grams of the selenazole were dissolved in 150 grams of
concentrated sulphuric acid, keeping the temperature below the room
temperature until complete solution took place. It was then cooled
on a freezing mixture and a mixture of sulphuric and nitric acids
(previously prepared and cooled by mixing 9.5 grams of nitric and
fifteen grams of sulphuric acids) slowly dropped into it in the course
of half an hour, using mechanical stirring for four hours. The solution
was then poured into two liters of water (ice water), filtered, dried,
and recrystallized from acetic acid, and alcohol with the help of
animal charcoal. The yield was 95 per cent.
This nitro compound crystallizes in flattened needles of a light
yellow color. It melts at 202.4°C. (corr.). It is very insoluble in
water; but soluble in hot acetic acid, acetic anhydride, nitrobenzene,
nitrotoluene, toluene, benzene, alcohol, and difficultly soluble when
cold. The crystals were analyzed and gave the following results,
Calculated for Found
C₁₃H₈N₂O₂Se I II
Nitrogen 9.24% 9.36% 9.48%
Monoamino Derivative
The conversion of mononitro compound to 6-amino-2-phenylbenzoselenazole
was accomplished by the action of tin and hydrochloric acid as follows:
30.3 grams of nitro compound were mixed with 42 grams of twenty mesh
tin in a liter flask, immersing the latter in cold water. 175 cc.
of conc. HCl were slowly added to the flask. In some cases it was
necessary to apply initial heating but when once the reaction started
it took place rapidly. After the effervescence had abated, the flask
was heated over a free flame, under a return condenser, for two hours.
The solution usually turned to a pasty mass, due to the formation of a
tin double salt. The mixture was dissolved in a large volume of water
and heated on a water-bath, the precipitate filtered out, washed, and
preserved. The clear filtrate was treated with concentrated alkali, in
excess, the separated amine collected, washed with water, dried and
recrystallized from alcohol, using bone-black. The precipitate set
aside was treated with strong alkali, the insoluble residue washed,
recrystallized, and added to the main product. The yield was 75 per
cent.
This amine crystallizes from alcohol in fine yellowish needles,
melting at 201.2°-202.3°C (corr.). It is insoluble in water and ether,
difficultly soluble in the hot; and fairly soluble in aniline. A pure
sample was analyzed and gave the following results:
Calculated for Found
C₁₃H₁₀N₂Se I II
Nitrogen 10.25% 10.34% 10.42%
Carbon 57.18 57.17 57.00
Hydrogen 3.69 3.79 3.85
Decomposition of Monoamino Derivative
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