M. Bobin et al. / Tetrahedron 63 (2007) 11048–11054
11053
m/z 238 (100), 203 (20), 176 (13). IR (KBr): 2225 cmꢀ1
4.8. 2,4-Dichloroacridine-9-carbonitrile (3f)
(CN). Anal. Calcd for C14H7N2Cl: C, 70.45; H, 2.96; N,
11.74; Cl, 14.85. Found: C, 70.44; H, 3.00; N, 11.79; Cl,
14.67. HRMS (EI) calculated for C14H7N235Cl: 238.0298.
Found: 238.0302.
Yield 130 mg, 24% (procedure C). Yellow crystals, mp 196–
1
198 ꢁC (hexane). H NMR (500 MHz, CDCl3) d 8.42 (d,
J¼8.8 Hz, 1H), 8.36 (d, J¼8.8 Hz, 1H), 8.28 (d, J¼2.1 Hz,
1H), 7.97 (d, J¼2.1 Hz, 1H), 7.95 (ddd, J¼8.8, 6.7,
1.2 Hz, 1H), 7.84 (ddd, J¼8.8, 6.7, 1.2 Hz, 1H). 13C NMR
(125 MHz, CDCl3) d 148.4, 142.9, 136.1, 134.6, 131.8,
131.7, 131.1, 130.6, 126.9, 126.7, 125.0, 122.8, 115.2,
114.4. MS (EI) m/z 272 (100), 237 (13), 202 (26), 175
(10). IR (KBr): 2226 cmꢀ1 (CN). HRMS (EI) calculated
for C14H6N235Cl2: 271.9908. Found: 271.9901.
4.4. Acridine-9-carbonitrile (3b)
Yield 81 mg, 20% (procedure A). Yellow crystals, mp
186 ꢁC (ethanol), lit.18 mp 181–182 ꢁC. 1H NMR
(500 MHz, CDCl3) d 8.35–8.37 (m, 2H), 8.29–8.32 (m,
2H), 7.88 (ddd, J¼8.8, 6.6, 1.4 Hz, 2H), 7.77 (ddd, J¼8.6,
6.6, 1.2 Hz, 2H). 13C NMR (125 MHz, CDCl3) d 148.3,
131.0, 130.4, 129.1, 126.1, 125.2, 115.4, 115.0. MS (EI)
m/z 204 (100), 177 (15). IR (KBr): 2227 cmꢀ1 (CN).
HRMS (EI) calculated for C14H8N2: 204.0687. Found:
204.0688.
4.9. 1,2-Dichloroacridine-9-carbonitrile (3g)
Yield 393 mg, 54% (procedure C). Yellow crystals, mp 254–
256 ꢁC (ethanol). 1H NMR (500 MHz, CDCl3) d 8.58 (ddd,
J¼8.6, 1.3, 0.7 Hz, 1H), 8.30 (m, 1H), 8.20 (d, J¼9.3 Hz,
1H), 7.95 (ddd, J¼8.6, 6.6, 1.3 Hz, 1H), 7.88 (d,
J¼9.3 Hz, 1H), 7.86 (ddd, J¼8.6, 6.6, 1.3 Hz, 1H). 13C
NMR (125 MHz, CDCl3) d 148.1, 147.5, 135.1, 131.9,
131.8, 130.8, 130.5, 130.3, 128.2, 127.2, 125.7, 128.3,
115.7, 114.0. MS (EI) m/z 272 (100), 237 (15), 202 (26),
175 (10). IR (KBr): 2218 cmꢀ1 (CN). Anal. Calcd for
C14H6N2Cl2: C, 61.57; H, 2.21; N, 10.26; Cl, 25.96. Found:
C, 61.67; H, 2.29; N, 10.29; Cl, 25.87. HRMS (EI) calcu-
lated for C14H6N235Cl2: 271.9908. Found: 271.9915.
4.5. 2-Bromoacridine-9-carbonitrile (3c)
Yield 418 mg, 74% (procedure B). Yellow crystals, mp 212–
1
214 ꢁC (ethanol). H NMR (500 MHz, CDCl3) d 8.53 (d,
J¼2.1 Hz, 1H), 8.35 (d, J¼8.6 Hz, 1H), 8.29 (d, J¼8.6 Hz,
1H), 8.17 (d, J¼9.3 Hz, 1H), 7.92 (dd, J¼9.3, 2.1 Hz, 1H),
7.92 (m, 1H), 7.80 (ddd, J¼8.6, 6.7, 1.2 Hz, 1H). 13C
NMR (125 MHz, CDCl3) d 148.4, 146.7, 134.8, 132.0,
131.3, 130.6, 129.8, 127.1, 126.8, 126.3, 125.2, 124.1,
114.7, 114.2. MS (EI) m/z 282 (100), 203 (38), 176 (210),
102 (15), 88 (17). IR (KBr): 2223 cmꢀ1 (CN). Anal. Calcd
for C14H7N2Br: C, 59.39; H, 2.49; N, 9.89; Br, 28.22. Found:
C, 58.78; H, 2.32; N, 9.92; Br, 27.68. HRMS (EI) calculated
for C14H7N279Br: 281.9793. Found: 281.9789.
4.10. 2,3-Dichloroacridine-9-carbonitrile (3h)
Yield 109 mg, 20% (procedure C). Yellow crystals, mp
1
246 ꢁC (AcOEt). H NMR (500 MHz, CDCl3) d 8.48 (s,
1H), 8.45 (s, 1H), 8.34 (d, J¼8.8 Hz, 1H), 8.29 (d,
J¼8.8 Hz, 1H), 7.92 (ddd, J¼8.8, 6.7, 1.3 Hz, 1H), 7.81
(ddd, J¼8.8, 6.7, 1.3 Hz, 1H). 13C NMR (125 MHz,
CDCl3) d 149.0, 146.5, 136.3, 134.6, 131.8, 131.0, 130.6,
130.0, 126.3, 125.5, 125.2, 124.8, 114.5, 114.4. MS (EI)
m/z 272 (100), 237 (18), 202 (29), 175 (12). IR (KBr):
2226 cmꢀ1 (CN). Anal. Calcd for C14H6N2Cl2: C, 61.57;
H, 2.21; N, 10.26; Cl, 25.96. Found: C, 61.57; H, 2.29; N,
10.01; Cl, 25.74. HRMS (EI) calculated for C14H6N235Cl2:
271.9908. Found: 271.9915.
4.6. 2-Trifluoromethyl-9-carbonitrile (3d)
Yield 320 mg, 59% (procedure B). Yellow crystals, mp 190–
191 ꢁC (hexane). 1H NMR (500 MHz, CDCl3) d 8.68
(s, 1H), 8.43 (d, J¼9.2 Hz, 1H), 8.41 (d, J¼8.6 Hz, 1H),
8.35 (d, J¼8.8 Hz, 1H), 8.02 (dd, J¼9.2, 1.3 Hz, 1H),
7.97 (ddd, J¼8.8, 6.7, 1.3 Hz, 1H), 7.84 (ddd, J¼8.6,
6.7, 1.3 Hz, 1H). 13C NMR (125 MHz, CDCl3) d 149.7,
148.4, 132.3, 132.0, 130.7 (q, JCF¼33.2 Hz), 130.6, 135.5,
126.6, 126.3 (q, JCF¼2.7 Hz), 125.4, 124.5, 123.6 (q,
JCF¼4.8 Hz), 123.5 (q, JCF¼273 Hz), 117.2, 114.4. MS
(EI) m/z 272 (100), 253 (8). IR (KBr): 2224 cmꢀ1 (CN).
Anal. Calcd for C15H7N2F3: C, 66.18; H, 2.59; N, 10.29;
F, 20.94. Found: C, 65.98; H, 2.41; N, 10.18; F, 20.76.
HRMS (EI) calculated for C15H7N2F3: 272.05613. Found:
272.05679.
4.11. 7-Chloro-2,3-dimethoxyacridine-9-carbonitrile
(3i)
Yield 395 mg, 66% (procedure A). Yellow crystals, mp 262–
1
263 ꢁC (AcOH). H NMR (400 MHz, CDCl3) d 8.23 (d,
J¼2.2 Hz, 1H), 8.13 (d, J¼9.1 Hz, 1H), 7.73 (dd, J¼9.1,
2.2 Hz, 1H), 7.46 (s, 1H), 7.36 (s, 1H), 4.15 (s, 3H), 4.11
(s, 3H). 13C NMR (100 MHz, CDCl3) d 154.9, 153.7,
146.6, 144.7, 134.1, 131.1, 131.0, 125.1, 124.5, 123.2,
115.2, 110.7, 107.0, 100.8, 16.6, 56.5. MS (EI) m/z
300 (33), 298 (100), 283 (11), 255 (30), 192 (24). IR
(KBr): 2225 cmꢀ1 (CN). HRMS (EI) calculated for
C16H11N2O235Cl: 298.0509. Found: 298.0505.
4.7. 2-Methoxy-9-carbonitrile (3e)
Yield 148 mg, 32% (procedure D). Yellow crystals, mp 177–
180 ꢁC (hexane), lit.19 mp 185 ꢁC (EtOH). 1H NMR
(500 MHz, CDCl3) d 8.31 (d, J¼8.5 Hz, 1H), 8.27 (d,
J¼8.5 Hz, 1H), 8.17 (d, J¼9.5 Hz, 1H), 7.82 (ddd, J¼8.5,
6.7, 1.3 Hz, 1H), 7.75 (ddd, J¼8.5, 6.7, 1.3 Hz, 1H), 7.54
(dd, J¼9.5, 2.3 Hz, 1H), 7.45 (d, J¼2.3 Hz, 1H), 4.07 (s,
3H). 13C NMR (125 MHz, CDCl3) d 160.1, 146.4, 145.8,
132.1, 130.4, 129.7, 129.1, 128.2, 126.7, 126.3, 124.7,
115.6, 112.3, 100.3, 56.0. MS (EI) m/z 234 (100), 191
(73), 164 (15). IR (KBr): 2222 cmꢀ1 (CN). HRMS (EI) cal-
culated for C15H10N2O: 234.0793. Found: 234.0799.
4.12. 6-Bromo-2-chloroacridine-9-carbonitrile (3j)
Yield 473 mg, 75% (procedure A). Yellow crystals, mp
1
260 ꢁC (AcOEt). H NMR (400 MHz, CDCl3) d 8.54 (m,
1H), 8.35 (dd, J¼2.2, 0.5 Hz, 1H), 8.27 (d, J¼9.4 Hz, 1H),
8.23 (dd, J¼9.2, 0.5 Hz, 1H), 7.87 (dd, J¼9.2, 2.0 Hz,