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Russ.Chem.Bull., Int.Ed., Vol. 51, No. 1, January, 2002
Keshtov et al.
Table 2. Spectral characteristics of compounds 1—6
Comꢀ
pound
NMR (CDCl3), δ (J/Hz)
IR,
ν/cm–1
1H
13C
19F
1
7.01—7.07 (m, 2 H); 7.11—7.17 (m, 2 H);
7.50—7.54 (m, 2 H); 7.60 (d, 2 H, J = 8);
193.95 (CO); 165.36 (CF); 162.78 (CF); 136.79,
133.68, 132.39, 131.29, 129.69, 127.39, 118.84,
–105.33, 2220 (C≡C);
–109.52 1645
(C=O);
7.74 (d, 2 H, J = 8); 7.79—7.84 (m, 2 H)
7.13—7.21 (m, 4 H); 7.80—7.85 (m, 4 H);
7.99—8.04 (m, 2 H); 8.07 (d, 2 H, J = 8)
118.80, 115.64, 115.38, 91.37 (C≡C); 88.26 (C≡C)
193.88 (СО); 192.85 (СО); 191.75 (СО); 167.47
(СF); 164.90 (СF); 142.58, 135.01, 132.72, 132.62, –103.92 1652 (СО);
1217 (C—F)
–100.19, 1662 (СО);
2
129.84, 129.70, 129.01, 128.99, 116.37, 115.64
194.42 (СО); 166.47 (CF); 164.28 (CF); 163.94
(CF); 161.80 (CF); 151.90, 151.75, 142.67,
141.09, 140.89, 137.27, 134.42, 134.39, 133.28,
133.26, 132.47, 132.38, 131.67, 131.58, 130.39,
130.14, 129.69, 129.63, 129.01, 128.94
194.24 (СО); 166.77 (СF); 165.04 (СF); 164.96
(CF); 164.23 (CF); 162.54 (CF); 162.45 (CF);
154.85, 154.79, 154.26, 154.19, 148.23, 148.05,
143.54, 143.29, 141.74, 141.68, 140.08, 139.81,
138.33, 138.24, 133.67, 133.60, 133.56, 133.33,
132.49, 132.03, 131.92, 131.83, 130.78, 130.71,
129.83, 129.80, 129.73
1210 (СF)
–105.12, 1650 (CO);
–111.23 1224 (CF)
3a
3b
6.99—7.04 (m, 2 H); 7.10—7.14 (m, 2 H);
7.48—7.52 (m, 2 H); 7.63 (d, 2 H);
7.74 (d, 2 H); 7.76—7.82 (m, 4 H);
8.13—8.16 (m, 2 H)
9.08—9.06 (m, 1 H); 8.57—8.54 (m, 1 H);
8.33—8.30 (m, 1 H); 7.88—7.80 (m, 4 H);
7.72—7.69 (m, 2 H); 7.62—7.57 (m, 2 H);
7.20—7.67 (m, 4 H)
–104.87,
–109.42,
–109.70
3c
8.085—8.04 (m, 1 H); 7.95 (s, 1 H);
7.85—7.74 (m, 2 H); 7.75 (d, 2 H,
J = 8.4); 7.63 (d, 3 H, J = 8.4);
7.52—7.49 (m, 2 H); 7.15 (t, 2 H,
J = 8.4); 7.03 (t, 2 H, J = 8.4);
2.62 (s, 3 H)
164.62 (СО); 166.64, 164.39, 164.35, 164.11,
161.91, 161.87, 151.93, 151.75, 151.17, 150.98,
143.03, 141.35, 141.22, 141.15, 140.92, 139.77,
139.58, 137.34, 137.29, 134.74, 133.49, 132.89,
132.64, 132.48, 131.74, 131.72, 131.66, 131.64,
129.78, 129.73, 128.66, 128.59, 127.94, 127.88,
21.85 (Me); 21.82 (Me)
–105.07,
–111.39
4
12.90 (s, 1 H); 8.50 (s, 1 H);
8.13—7.13 (m, 15 H)
193.59, 193.52, 165.85, 165.71, 163.35, 163.20,
162.58, 160.76, 160.76, 160.15, 144.69, 144.24,
139.10, 138.15, 136.80, 136.09, 135.59, 133.53,
133.46, 132.34, 132.25, 132.16, 132.09, 131.17,
130.83, 130.70, 130.09, 129.90, 129.79, 129.50,
129.42, 129.34, 127.70, 127.32, 126.95, 126.47,
124.61, 124.46, 115.80, 115.64, 115.58, 115.53,
115.43, 115.31, 115.24, 115.02, 94.90 (Сl)
–105.63,
–106.01,
–112.16,
–114.18
5
6
7.85—7.79 (m, 2 H); 7.78 (d, 2 H, J = 8.4); 193.96 (СО); 166.84 (CF); 105.76 (CF); 114.30
7.67 (d, 2 H, J = 8.4); 7.59—7.56 (m, 2 H); (CF); 163.23 (CF); 154.30, 153.82, 139.39,
–104.18,
–106.29
7.17 (t, 2 H, J = 8.4);
7.09 (t, 2 H, J = 8.4)
138.57, 132.85, 132.80, 132.75, 131.65, 131.60,
130.62, 130.00, 129.50, 115.99, 116.04, 116.24,
116.29, 112.78
12.81 (s, 1 H); 8.17—7.29 (m, 17 H)
193.62 (СО); 165.75 (СF); 163.50 (CF); 163.25
(CF); 161.02 (CF); 139.02, 136.60, 132.07,
131.88, 130.26, 129.23, 129.13, 128.18, 127.36,
126.71, 125.63, 124.66, 118.49, 116.77,
116.21, 115.80
–105.97,
–112.18
4,4´ꢀdifluorobenzophenone, and nonactivated fluoroꢀ
benzene provides information on the reactivities of DFAC
and also allows the prediction of the relative reactivities in
the series of quinoxalines 3a—c (see Table 3). Since posiꢀ
tions 4 and 4´ in DFAC are nonequivalent, the chemical
shifts of two fluorophenyl groups of DFAC are different.
The chemical shifts δF of the fluorophenyl group at posiꢀ
tion 4 of DFAC and 4,4´ꢀdifluorobenzophenone have
close values (from –103.92 to –105.63), whereas the sigꢀ
nals of the fluorophenyl group at position 4´ are in the δF
range from –100.19 to –112.18. The signals for the F
atom at position 4´ in compound 2 (αꢀdiketone) and in
compound 5 containing the dicyanopyrazine ring are obꢀ
served at δF –100.19 and –106.29, respectively, whereas
the corresponding signals in the spectra of compounds 4
and 6 bearing the imidazole ring are observed at δF –112.16
and –112.18, respectively, which are comparable with
that observed for fluorobenzene.