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TABATSKAYA, BEREGOVAYA
1
Table 1. 1H (CDCl3, , ppm) and 19F NMR ( F, ppm), IR ( , cm ), and UV ( max, nm) spectra of anthraquinones
VII, XI, XII, XIV, and XVIII XX and benzanthrones IX, X, and XIII
Comp.
no.
1H NMR spectrum
IR, UV, and 19F NMR spectra
VII
6.35 s [CH(CN)2], 7.97 m (2H, 6-H, 7-H), 8.15 8.26 m (2H, 5-H, IR: 1360 and 1540 (NO2), 2200 w (CN),
8-H), 8.18 d and 8.31 d (2-H and 3-H, J = 8.5 Hz) 1675 s (CO)
7.78 m (2H, 9-H, 10-H), 7.83 d, 8.13 d (4-H, 5-H, J = 8.5 Hz), IR: 1630 s (CO); 2220 s (CN); 3240,
IX
X
8.44 d.d and 9.03 d.d (8-H, 11-H, J = 8.0, 2.0 Hz)
3350, 3400 (NH2)
UV (DMF): 380
IR: 1625 (CO); 2220 s (CN); 3230, 3350
(NH2)
UV: 534
XI
6.96 s (CHCN), 7.83 m (2H, 6-H, 7-H), 7.86 d. 8.43 d (2-H, 3-H, 19F NMR: 2.04 (2F), 11.00, 23.22 (2F)
J = 8.5 Hz), 8.19 m (2H, 5-H, 8-H)
XII
XIII
6.85 s (CHCN), 7.78 m (2H, 6-H, 7-H), 7.90 d and 8.14 d (2-H, 19F NMR: 1.67 (2F), 10.37 and 23.02
3-H, J = 8.5 Hz), 8.07 8.23 m (2H, 5-H, 8-H)
(2F)
7.08 d and 7.61 d (4-H, 5-H, J = 9.0 Hz), 7.49 d.d and 8.37 d.d 19F NMR: 2.77 and 3.66 (2F each),
(7-H, 11-H, J = 7.5, 2.0 Hz), 7.30 7.40 m (2H, 9-H, 10-H)
10.45 and 11.49 (1F each), 24.74 and
25.10 (2F each)
XIV
7.41d and 7.66 d (2-H, 3-H, J = 8.5 Hz), 7.83 m (2H, 6-H, 7-H), 19F NMR: 0.82 (2F), 13.16 and 22.46
8.12 d and 8.29 d (5-H, 8-H, J = 8.0 Hz), 12.92 s (OH)
(2F, each)
XVIII 1.35 t (3H, CH3), 4.32 q (2H, CH2), 5.94 br.s (CHCN), 7.87 m (2H,
6-H, 7-H), 7.68 d and 7.80 d (2-H, 3-H, J = 8.5 Hz), 8.21 d.d and
8.42 d.d (5-H, 8-H, J = 7.5, 2.0 Hz)
XIX
1.46 s [18H, 3 ,5 -(t-Bu)2], 5.38 s (OH), 7.08 s (2H, 2 -H, 6 -H),
7.66 d and 7.73 d (2-H, 3-H, J = 8.5 Hz), 7.78 m (2H, 6-H, 7-H),
8.08 m and 8.20 m (5-H, 8-H)
XX
1.45 s [18H, 3 ,5 -(t-Bu)2], 5.30 s (OH), 7.05 s (2H, 2 -H, 6 -H),
7.50 d and 7.70 d (2-H, 3-H, J = 8.5 Hz), 7.82 m (2H, 6-H, 7-H),
7.99 m and 8.21 m (5-H, 8-H)
of 7:10. Apart from the products of nucleophilic
substitution by pentafluorophenylacetonitrile anion,
the mixture contained 10 15 mol% of 1-hydroxy-4-
nitroanthraquinone (XVI). The formation of hydroxy
derivatives may be explained by participation of the
released nitrite ion and hydroxide ion of the base
catalyst. Under similar conditions anthraquinone II
is converted into product XI as a result of exclusive
replacement of the fluorine atom.
Mixtures containing both chlorine and nitro group
substitution products were also obtained by reactions
of anthraquinone I with the anion derived from
2,6-di-tert-butylphenol (VI). In this case, the replace-
ment of chlorine was the predominant reaction path-
way: the ratio of 4-nitro- and 4-chloroanthraquinones
XIX and XX in the reaction mixtures was (5 6):1.
The reaction was always accompanied by formation
of hydroxynitroanthraquinone XVI (12 15 mol %).
The reaction of chloronitroanthraquinone I with
ethyl cyanoacetate (V) in the presence of alkali metal
hydroxide or potassium carbonate both at room tem-
perature and at 45 C yields approximately equal
amounts of products XVII and XVIII as a result of
replacement of the chlorine atom and nitro group,
respectively. 1-[(Cyano)ethoxycarbonylmethyl]-4-
nitroanthraquinone (XVII) was obtained previously as
the sole product of the reaction of fluoronitroanthra-
quinone II with the same nucleophile [4].
The reaction of fluoronitroanthraquinone II with
an equimolar amount of phenol VI in the presence of
potassium hydroxide at 20 45 C afforded a mixture
1
of products, in which we identified by H NMR spec-
troscopy compounds XIX and XVI and also initial
reagent VI. No denitration product was detected, for
ion peak with m/z 430 was not found in the mass
1
spectrum and the H NMR spectrum lacked signals
from OH proton and 2-H and 6-H of hydroxyphenyl
fragment, belonging to a compound other than XIX.
RUSSIAN JOURNAL OF ORGANIC CHEMISTRY Vol. 37 No. 3 2001