J Fluoresc (2010) 20:415–420
419
Table 2 The molecular electronic properties (HOMO-LUMO energy, GAP) of the spiro-oxazino-quinolines (6, 8 and 10) and 2-aminoquinoline-
3-carobonitrile (4)
Comp.
R
R1
R2
Heat of formation (K Cal.)
Ionization potential (eV)
HOMO (eV)
LUMO (eV)
GAP (eV)
4
–
79.30
5.53
9.015
8.80
8.80
8.72
8.79
8.83
8.79
−9.015
−8.80
−8.80
−8.725
−8.793
−8.834
−8.794
−1.223
−0.903
−0.904
−0.881
−0.889
−0.937
−0.979
7.792
7.897
7.896
7.844
7.904
7.897
7.815
6a
6b
6c
6d
8
H
H
CH3
H
–
H
H
H
CH3
H
0.132
1.69
H
CH3
–
H
1.017
10.43
39.38
–
10
–
–
–
GAP = ELUMO-EHOMO
(20), 142(10), 127(30), 113(15). Anal. Calcd. For
C16H17N3O (267.33): C, 71.97; H, 6.41; N, 15.73. Found
C, 72.19; H, 6.63; N, 15.51.
3170 m, 3077 m, 2950 m, 1680 s, 1620 s, 1560 m,
1489 m, 818 m, 768 m cm−1 1H NMR (300 MHz,
DMSO-d6) δ: 0.82 (d, 3H, CH3), 1.20 (t, 2H, CH2), 1.55–
1.90 (t, 7H, 3×CH2 and CH), 7.70 (bs, 1H, NH), 8.50 (bs,
1H, NH), 7.20 (t, 1H, ArH), 7.5–7.6 (dd, 2H, ArH), 7.90
(d, 1H, ArH), 8.60 (s, 1H, ArH). Anal. Calcd. For
C17H19N3O (281.35): C, 72.66; H, 6.81; N, 14.95. Found
C, 72.52; H, 6.58; N, 14.68.
4-Methylspiro[1,3]oxazino[4,5-b]quinoline-2,
1′-cyclohexan]-4(1H)-imine (6b)
Yield: 2.15 g (65%), recrystallized from ethyl acetate to
afford pale yellow crystal; mp 242–244 °C. IR (KBr):
3248 m, 3168 m, 2949 m, 2927 m, 1672 s, 1622 s, 1577 m,
Spiro[1,3]oxazino[4,5-b]quinoline-2,1′-cyclopentan]-4
(1H)-imine (8)
1
1390 m, 806 m, 766 m cm−1. H NMR (300 MHz,CDCl3)
δ: 0.91 (d, 3H, CH3), 1.30 (q, 2H, CH2), 1.60 (q, 1H, CH),
1.80 (t, 4H, 2×CH2), 2.20(t, 2H, CH2), 3.80 (bs, 1H, NH),
6.90 (bs, 1H, NH), 7.20–7.60 (m, 4H, ArH), 8.60 (s, 1H,
ArH). 13C NMR (75 MHz, CDCl3) δ: 22, 38, 68, 112, 124,
126, 130, 132, 136, 140, 148, 154, 162. Anal. Calcd. For
C17H19N3O (281.35): C, 72.66; H, 6.81; N, 14.95. Found
C, 72.43; H, 6.52; N, 14.71.
Yield: 1.79 g (60%), recrystallized from ethanol to afford
yellow crystal; mp 236–238 °C IR (KBr): 3174 m, 3057 m,
2939 m, 1685 s, 1618 s, 1568 m, 1502 m, 1429 m, 810 m,
1
760 m cm−1. H NMR (300 MHz, CDCl3) δ: 1.85 (q, 4H,
2×CH2), 2.01 (q, 4H, 2×CH2), 5.80 (bs, 1H, NH), 6.70 (bs,
1H, NH), 7.20–7.80 (m, 4H, ArH), 8.60(s, 1H, ArH). MS
(70 eV) m/z (%): 253 (90) [M+1], 241(50), 236(90), 202
(40), 169(20), 127(20). Anal. Calcd. For C15H15N3O
(253.3): C, 71.21; H, 5.97; N, 16.60. Found C, 71.41; H,
6.18; N, 16.88.
2-Methylspiro[1,3]oxazino[4,5-b]quinoline-2,
1′-cyclohexan]-4(1H)-imine(6c)
Yield: 2.20 g (68%), recrystallized from ethanol to afford pale
yellow crystal; mp 235–238 °C. IR (KBr): 3186 m, 3051 m,
3′,4′-Dihydro-2′H-spiro[1,3]oxazino[4,5-b]quinoline-2,
1′-naphthalen]-4(1H)-imine (10)
1
2929 m, 1666 s, 1620 s, 1578 m, 1502 s, 1433 s cm−1. H
NMR (300 MHz, DMSO-d6) δ: 0.9 (d, 3H, CH3), 1.22 (q,
1H, CH), 1.50 (t, 2H, CH2), 1.60 (t, 2H, CH2), 1.72 (t, 2H,
CH2), 1.94 (t, 2H, CH2), 8.35 (bs, 1H, NH), 8.40 (bs, 1H,
NH), 7.20–7.80 (m, 4H, ArH), 8.60 (s, 1H, ArH). MS
(70 eV) m/z (%): 282 (50) [M+1], 265(10), 241 (40), 169
(20), 127(10). Anal. Clacd. For C17H19N3O (281.35): C,
72.66; H, 6.81; N, 14.95. Found C, 72.44; H, 6.78; N, 14.68.
Yield: 2.60 g (70%), recrystallized from ethanol to
afford pale yellow crystal; mp 266–268 °C. IR (KBr):
3178 m, 3024 m, 2935 m, 1654 s, 1618 s, 1573 m,
1504 m, 1433 m, 1390 m, 1346 m, 818 m, 755 m cm−1.
1H NMR (300 MHz, DMSO) δ: 2.04 (t, 2H, CH2), 2.60 (t,
2H, CH2), 2.80 (t, 2H, CH2), 7.10–7.30 (m, 4H, ArH),
7.40–7.80 (m, 4H, ArH), 8.20 (bs, 1H, NH), 8.60 (s, 1H,
ArH), 8.80 (bs, 1H, NH). 13C NMR (75 MHz, DMSO) δ:
18, 28, 68, 111, 122, 123, 125, 126, 127, 128, 129, 131,
136, 139, 149, 154, 160. Anal. Calcd. For C20H17N3O
(315.37): C, 76.26; H, 5.43; N, 13.33. Found C, 75.92; H,
5.21; N, 13.20.
3-Methylspiro[1,3]oxazino[4,5-b]quinoline-2,
1′-cyclohexan]-4(1H)-imine(6d)
Yield: 1.90 g (60%), recrystallized from ethanol to
afford yellow crystal; mp 228–230 °C. IR (KBr):