H. Fu et al.
13C NMR ([D6]DMSO, 75 MHz): d=176.4, 163.9, 143.4, 141.5, 133.6,
128.6, 126.5, 121.5, 121.2, 117.6, 115.6, 112.0, 98.5, 56.0 ppm; ESI-MS:
[M+H]+ m/z 225.9.
[4,5-b]acridin-10(5H)-one (2p):[28] Eluent: petroleum ether/
ACHUTGTNREN[NUG 1,3]DioxoloACHUTNGTRENNGUN
ethyl acetate (3/1). Yield 41 mg (85%). Light yellow solid, m.p.>3008C
(lit.[28] >3008C). 1H NMR ([D6]DMSO, 300 MHz): d=11.64 (s, 1H), 8.16
(d, 1H, J=8.1 Hz), 7.64 (td, 1H, J=7.6 Hz, J=1.3 Hz), 7.49 (s, 1H), 7.46
(d, 1H, J=8.3 Hz), 7.20 (td, 1H, J=7.0 Hz, J=0.8 Hz), 6.94 (s, 1H),
6.12 ppm (s, 2H); 13C NMR ([D6]DMSO, 75 MHz): d=175.6, 153.2,
144.3, 140.8, 139.0, 133.1, 126.3, 121.5, 120.5, 117.6, 115.9, 102.6, 102.5,
96.3 ppm; ESI-MS: [M+H]+ m/z 240.1.
4-Fluoroacridin-9ACHTUNGTRENNUNG
(10H)-one (2h):[24] Eluent: petroleum ether/ethyl ace-
1
tate (3/1). Yield 22 mg (51%). Light yellow solid, m.p.>3008C. H NMR
([D6]DMSO, 300 MHz): d=11.68 (s, 1H), 8.24 (dd, 1H, J=8.1 Hz, J=
1.2 Hz), 8.05 (d, 1H, J=8.0 Hz), 7.84–7.73 (m, 2H), 7.68 (ddd, 1H, J=
7.8 Hz, J=7.8 Hz, J=1.2 Hz), 7.30 (td, 1H, J=7.5 Hz, J=1.3 Hz),
7.24 ppm (td, 1H, J=8.0 Hz, J=4.9 Hz); 13C NMR ([D6]DMSO,
75 MHz): d=176.6, 153.3, 150.1, 141.3, 134.3, 132.4, 132.0, 131.0, 130.8,
126.5, 123.0, 123.0, 122.3, 121.1, 120.8, 120.7, 118.6, 118.4, 118.2 ppm;
ESI-MS: [M+H]+ m/z 214.1.
8-MethylACHTGNUTREN[NNUG 1,3]dioxoloACHTUNTRGEG[NNUN 4,5-b]acridin-10ACTHNUGTREN(NUGN 5H)-one (2q): Eluent: petroleum
ether/ethyl acetate (3/1). Yield 36 mg (71%). Light yellow solid, m.p.>
3008C. 1H NMR ([D6]DMSO, 300 MHz): d=11.56 (s, 1H), 7.95 (s, 1H),
7.48 (s, 1H), 7.46 (d, 1H, J=1.7 Hz), 7.38 (d, 1H, J=8.4 Hz), 6.92 (s,
1H), 6.12 (s, 2H), 2.38 ppm (s, 3H); 13C NMR ([D6]DMSO, 75 MHz): d=
175.4, 153.0, 144.1, 138.9, 134.6, 130.6, 125.4, 120.4, 117.6, 115.8, 102.6,
102.5, 96.2, 21.2 ppm; HRMS (ESI) calcd for [C15H11NO3+H]+: 254.0812;
found: 254.0814.
2-Fluoroacridin-9
(3/1). Yield 28 mg (65%). Light yellow solid, m.p.>3008C (lit.[25]
ACHTUNGTRENNUNG
(10H)-one (2i):[25] Eluent: petroleum ether/ethyl acetate
>
3478C). 1H NMR ([D6]DMSO, 300 MHz): d=11.88 (s, 1H), 8.24 (d, 1H,
J=7.9 Hz), 7.89 (dd, 1H, J=9.3 Hz, J=2.5 Hz), 7.76 (t, 1H, J=7.2 Hz),
7.67–7.60 (m, 2H), 7.56 (d, 1H, J=8.3 Hz), 7.28 ppm (t, 1H, J=7.5 Hz);
13C NMR ([D6]DMSO, 75 MHz): d=176.7, 159.0, 155.8, 141.3, 138.2,
134.2, 126.4, 123.1, 122.8, 121.8, 121.5, 121.4, 120.6, 120.5, 120.1, 118.0,
110.4, 110.1 ppm; ESI-MS: [M+H]+ m/z 214.2.
7,9-DimethylACTHUNRTGENNUG[1,3]dioxoloACHTUNGTRNE[NUGN 4,5-b]acridin-10(5H)-one (2r): Eluent: petrole-
um ether/ethyl acetate (3/1). Yield 32 mg (59%). Light yellow solid, m.p.
308–3108C. 1H NMR ([D6]DMSO, 300 MHz): d=11.33 (s, 1H), 7.46 (s,
1H), 7.06 (s, 1H), 6.88 (s, 1H), 6.76 (s, 1H), 6.12 (s, 2H), 2.82 (s, 3H),
2.36 ppm (s, 3H); 13C NMR ([D6]DMSO, 75 MHz): d=177.4, 152.7,
144.0, 142.7, 142.3, 140.5, 138.0, 125.9, 117.2, 117.1, 115.1, 103.0, 102.3,
95.8, 24.1, 21.8 ppm; HRMS (ESI) calcd for [C16H13NO3+H]+: 268.0968;
found: 268.0973.
2-Chloroacridin-9ACHTUNGTRENNUNG
(10H)-one (2j):[20] Eluent: petroleum ether/ethyl ace-
tate (3/1). Yield 31 mg (68%). Light yellow solid, m.p.>3008C (lit.[20]
3298C). 1H NMR ([D6]DMSO, 300 MHz): d=11.87 (s, 1H), 8.20 (d, 1H,
J=8.1 Hz), 8.11 (d, 1H, J=2.1 Hz), 7.72 (dd, 2H, J=8.5 Hz, J=1.8 Hz),
7.54 (t, 2H, J=9.6 Hz), 7.27 ppm (t, 1H, J=7.8 Hz); 13C NMR
([D6]DMSO, 75 MHz): d=176.3, 141.3, 140.0, 134.4, 134.0, 126.6, 125.9,
125.3, 122.1, 121.8, 120.8, 120.4, 118.1 ppm; ESI-MS: [M+H]+ m/z 230.2.
8-ChloroACTHUNTGRENNUG[1,3]dioxoloHCATUNGTREN[NGUN 4,5-b]acridin-10(5H)-one (2s): Eluent: petroleum
ether/ethyl acetate (3/1). Yield 29 mg (54%). Light yellow solid, m.p.>
3008C. 1H NMR ([D6]DMSO, 300 MHz): d=11.93 (s, 1H), 8.08 (d, 1H,
J=2.3 Hz), 7.67 (dd, 1H, J=8.9 Hz, J=2.4 Hz), 7.52 (d, 1H, J=8.8 Hz),
7.48 (s, 1H), 6.97 (s, 1H), 6.15 ppm (s, 2H); 13C NMR ([D6]DMSO,
75 MHz): d=174.5, 153.5, 144.7, 139.3, 139.1, 133.1, 125.9, 125.0, 121.3,
120.1, 115.9, 102.7, 102.5, 96.4 ppm; HRMS (ESI) calcd for
[C14H8ClNO3+H]+: 274.0271; found: 274.0275.
1-Chloroacridin-9
tate (3/1). Yield 25 mg (55%). Light yellow solid, m.p.>3008C (lit.[26b]
ACHTUNGTRENNUNG
(10H)-one (2k):[26] Eluent: petroleum ether/ethyl ace-
>
3608C). 1H NMR ([D6]DMSO, 300 MHz): d=11.84 (s, 1H), 8.19 (d, 2H,
J=8.6 Hz), 7.73 (t, 1H, J=7.7 Hz), 7.54 (d, 1H, J=1.9 Hz), 7.51 (d, 1H,
J=8.3 Hz), 7.29–7.22 ppm (m, 2H); 13C NMR ([D6]DMSO, 75 MHz): d=
176.8, 142.2, 141.4, 138.6, 134.4, 128.9, 126.6, 122.2, 121.9, 121.2, 119.7,
118.0, 116.9 ppm; ESI-MS: [M+H]+ m/z 230.2.
11H-PyridoACTHNUTRGNEUNG
[2,1-b]quinazolin-11-one (2t):[29] Eluent: petroleum ether/
ethyl acetate (3/1). Yield 29 mg (74%). Light yellow solid, m.p. 207–
2108C (lit.[29] 210–2128C). 1H NMR ([D6]DMSO, 300 MHz): d=8.72 (d,
1H, J=6.2 Hz), 8.24 (d, 1H, J=7.1 Hz), 7.84 (t, 1H, J=6.6 Hz), 7.66 (t,
2H, J=7.4 Hz), 7.44 (d, 2H, J=8.2 Hz), 7.00 ppm (t, 1H, J=6.0 Hz);
13C NMR ([D6]DMSO, 75 MHz): d=158.8, 148.7, 147.9, 135.7, 135.5,
127.2, 127.0, 126.4, 125.5, 116.2, 113.7 ppm; ESI-MS: [M+H]+ m/z 197.3.
Acridine (5):[30] From reaction of 1 mmol of acridine-9-carboxylic acid (4)
under nitrogen atmosphere with heating. Eluent: petroleum ether/ethyl
acetate (5/1). Yield 131 mg (73%). White crystal, m.p. 105–1088C.
1H NMR (CDCl3, 300 MHz): d=8.79 (s, 1H), 8.25 (d, 2H, J=8.8 Hz),
8.01 (d, 2H, J=8.5 Hz), 7.79 (td, 2H, J=7.6 Hz, J=1.3 Hz), 7.55 ppm (t,
2H, J=7.5 Hz); 13C NMR (CDCl3, 75 MHz): d=149.2, 136.2, 130.4,
129.5, 128.3, 126.7, 125.8 ppm; ESI-MS: [M+H]+ m/z 180.2.
9-Oxo-9,10-dihydroacridine-2-carbonitrile (2l): Eluent: petroleum ether/
ethyl acetate (3/1). Yield 33 mg (75%). Light yellow solid, m.p.>3008C.
1H NMR ([D6]DMSO, 300 MHz): d=12.09 (s, 1H), 8.50 (s, 1H), 8.18 (d,
1H, J=8.0 Hz), 7.96 (d, 1H, J=8.7 Hz), 7.76 (t, 1H, J=7.6 Hz), 7.60–
7.51 (m, 2H), 7.30 ppm (t, 1H, J=7.4 Hz); 13C NMR ([D6]DMSO,
75 MHz): d=176.4, 143.6, 141.2, 135.4, 134.9, 132.6, 126.6, 123.0, 121.5,
120.5, 119.5, 119.4, 118.4, 103.4 ppm; HRMS (ESI) calcd for
[C14H8N2O+H]+: 221.0709; found: 221.0711.
2-Bromoacridin-9
tate (3/1). Yield 50 mg (91%). Light yellow solid, m.p.>3008C (lit.[27]
ACHTUNGTRENNUNG
(10H)-one (2m):[27] Eluent: petroleum ether/ethyl ace-
>
3008C). 1H NMR ([D6]DMSO, 300 MHz): d=11.88 (s, 1H), 8.26 (d, 1H,
J=2.1 Hz), 8.19 (d, 1H, J=8.0 Hz), 8.12 (dd, 1H, J=8.8 Hz, J=2.3 Hz),
7.73 (t, 1H, J=7.7 Hz), 7.51 (t, 2H, J=8.0 Hz), 7.26 ppm (t, 1H, J=
7.5 Hz); 13C NMR ([D6]DMSO, 75 MHz): d=176.2, 141.3, 140.3, 136.5,
134.4, 128.5, 126.6, 122.3, 122.1, 120.9, 120.6, 118.1, 113.7 ppm; ESI-MS:
[M+H]+ m/z 274.1.
Acknowledgements
2-Bromo-7-methylacridin-9ACTHNUGRTENUNG(10H)-one (2n): Eluent: petroleum ether/
The authors wish to thank the National Natural Science Foundation of
China (Grant Nos. 21172128 and 21105054), the Ministry of Science and
Technology of China (Grant No. 2012CB722605) and the Doctoral Pro-
gram of Higher Education (No. 20090002110058) for financial support.
ethyl acetate (3/1). Yield 39 mg (67%). Light yellow solid, m.p.>3008C.
1H NMR ([D6]DMSO, 300 MHz): d=11.81 (s, 1H), 8.25 (d, 1H, J=
3.3 Hz), 7.98 (s, 1H), 7.80 (dd, 1H, J=8.9 Hz, J=2.3 Hz), 7.56 (dd, 1H,
J=8.5 Hz, J=1.7 Hz), 7.48–7.42 (m, 2H), 2.39 ppm (s, 3H); 13C NMR
([D6]DMSO, 75 MHz): d=176.0, 140.2, 139.4, 136.3, 135.9, 131.3, 128.5,
125.6, 122.2, 120.8, 120.5, 118.1, 113.4, 21.1 ppm; HRMS (ESI) calcd for
[C14H10BrNO+H]+: 288.0019; found: 288.0021.
[2] For recent reviews, see: a) C. Jia, T. Kitamura, Y. Fujiwara, Acc.
2002, 417, 507; c) J. Hassan, M. Sevignon, C. Gozzi, E. Schulz, M.
2-Bromo-7-chloroacridin-9ACTHNUTRGNE(NUG 10H)-one (2o): Eluent: petroleum ether/ethyl
acetate (3/1). Yield 38 mg (61%). Light yellow solid, m.p.>3008C.
1H NMR ([D6]DMSO, 300 MHz): d=12.13 (s, 1H), 8.32 (d, 1H, J=
2.2 Hz), 8.18 (d, 1H, J=2.4 Hz), 7.93 (dd, 1H, J=8.9 Hz, J=2.3 Hz),
7.83 (dd, 1H, J=9.0 Hz, J=2.4 Hz), 7.63 (d, 1H, J=8.9 Hz), 7.57 ppm
(d, 1H, J=8.9 Hz); 13C NMR ([D6]DMSO, 75 MHz): d=175.3, 140.3,
140.0, 137.0, 134.5, 128.6, 126.6, 125.4, 122.2, 121.8, 120.9, 120.7,
114.3 ppm; HRMS (ESI) calcd for [C13H7BrClNO+H]+: 307.9472; found:
307.9468.
4276
ꢀ 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Chem. Eur. J. 2013, 19, 4271 – 4277