436
RTISHCHEV, SELITRENNIKOV
Photolysis of nitroquinoxalines II IV. Nitro
(3H and 2H, 6-OC2H5, J 7.5 Hz), 9.25 and 9.31 (2H,
2-H and 3-H, AB, J 3 Hz), 8.12 and 8.20 (2H, 7-H
and 8-H, AB, J 9 Hz).
compound, 0.20 g, was dissolved in 8.4 ml of conc.
H2SO4, water and ethanol (150 ml each) were added,
and the mixture was stirred until the precipitate that
formed dissolved completely. The solution was ir-
radiated until the new absorption band no longer grew
ACKNOWLEDGMENTS
(
250 265 nm). The protoreaction progress was
The work was financially supported by the Mi-
nistry of Education of the Russian Federation in the
framework of the Scientific Research of High School
in Chemistry and Chemical Products Program,
General and Technical Chemistry Section.
a
followed by the absorption spectra of samples of the
reaction mixture, duluted 100 times with 0.2 N H2SO4.
The photolysate was neutralized with a solution of
12 g of NaOH in 50 ml of water and 0.5 g of
NaHCO3 and treated with chloroform (5 30 ml). The
extract was washed with water (5 30 ml) and dried
with Na2SO4. The solvent was removed in a water-jet-
pump vacuum, and the residue was dried in a dessica-
tor over P2O5. The dried residues were treated by
procedures specific for each compound.
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5-Hydroxy-6-methylquinoxaline (X). A brown
tarry dry residue, 0.17 g, resulting from the photolysis
of nitro compound II was sublimed in a vacuum to
obtain 0.11 g (65%) of the reaction product as yellow
crystals, mp 80 91 C. Recrystallization of a 0.10-g
portion of the product from 5 ml of 50% aqueous
ethanol gave 0.04 g of compound X as colorless
needles, mp 91 93 C [1]. The melting point did not
change after vacuum sublimation, Rf 0.65 0.75.
3. Chapman, O.L., Heckert, D.C., Reasoner, J.W., and
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6-Chloro-5-hydroxyquinoxaline (XI). A greenish-
brown dry residue, 0.16 g, resulting from the pho-
tolysis of nitro compound III, was sublimed in a
vacuum to obtain 0.11 g (64%) of the reaction product
as green crystals, mp 129 137 C. Crystallization from
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1
135 137 C, Rf 0.55 0.65. IR spectrum, , cm :
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3075 s., br. (assoc. OH). 1HNMR spectrum [CF3COO
CDCl3, 1:1 (v/v), external reference TMS), , ppm:
9.37 and 9.48 (2H, 2-H and 3-H, AB, J 3 Hz), 8.03
and 8.26 (2H, 7-H and 8-H, AB, J 9 Hz). Found, %:
C 53.11; H 2.80; N 15.65. C8H5ClN2O. Calculated,
%: C 53.19; H 2.77; N 15.51.
1980, no. 1, p. 95.
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Teranishi, H., J. Phys. Chem., 1980, vol. 84, no. 16,
p. 2074.
6-Ethoxy-5-hydroxyquinoxaline (XII). A
greenish brown tarry dry residue, 0.16 g, resulting
from the photolysis of nitro compound IV, that had
crystallized in part within several days, was sublimed
in a vacuum to obtain 0.08 g (46%) of the reaction
product as a yellow semicrystalline material which
melted completely at 94 C and got orange when
handled in air. Repeated vacuum sublimation gave
compound XII as yellow crystals, mp 100 106 C, Rf
13. Physical Methods in Heterocyclic Chemistry, Kat-
ritzky, A. R., Ed., New York: Academic, 1963.
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panion, New York: Wiley, 1972.
1
1
0.5 0.6. IR spectrum, , cm : 3320 s (assoc.OH). H
NMR spectrum [CF3COOH CDCl3 (1:1 (v/v),
xternal reference TMS), , ppm: 1.63 t and 4.55 q
17. Grabowska, A., Herbich, J., Kirkor-Kaminska, E., and
Pakula, B., J. Mol. Spectrosc., 1972, vol. 42, no. 2,
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RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 74 No. 3 2004