(white precipitate was formed). The reaction mixture in a tightly
capped pressure tube was stirred for 12 h at 130 °C and then
cooled to rt. Water was carefully added to the mixture and
allowed to stand for 30 min at rt. The resulting precipitate was
filtered, washed with water, and dried under suction for 5 h to
give 2-chloroquinolines 2a -j.
6-Ch lor o-2-n itr o-7,8,9,10-tetr ah ydr oph en an th r idin e (2g):
63% yield as a white solid; mp 185-186 °C; 1H NMR (200 MHz,
CDCl3) δ 8.83 (d, 1H, J ) 2.6 Hz), 8.37 (dd, 1H, J ) 9.2, 2.6 Hz),
8.02 (d, 1H, J ) 9.2 Hz), 3.17 (t, 2H, J ) 5.2 Hz), 2.90 (t, 2H,
J ) 4.8 Hz), 1.96 (q, 4H, J ) 2.9 Hz); 13C NMR (50 MHz, CDCl3)
δ 156.3, 147.7, 146.9, 145.5, 131.3, 130.5, 126.2, 122.6, 119.7,
27.4, 25.9, 21.9, 21.4; MS (EI) m/z (relative intensity) 264 (M+),
262 (M+, 100), 234, 180, 152, 76; HRMS (CI) m/z C13H12ClN2O2
(MH+) calcd 263.0585, found 263.0588.
2-Ch lor oqu in olin e (2a ): commercially available; 75% yield
1
as a white solid; H NMR (200 MHz, CDCl3) δ 8.10 (d, 1H, J )
8.6 Hz), 8.03 (d, 1H, J ) 8.8 Hz), 7.82 (d, 1H, J ) 7.8 Hz), 7.70-
7.78 (m, 1H), 7.52-7.60 (m, 1H), 7.39 (d, 1H, J ) 8.6 Hz).
2,6-Dich lor oqu in olin e (2b): 84% yield as a white solid; mp
4-Ch lor o-8-n itr ofu r o[3,2-c]qu in olin e (2h ): 78% yield as a
white solid; mp 208-209 °C; 1H NMR (200 MHz, CDCl3) δ 9.19
(d, 1H, J ) 2.6 Hz), 8.50 (dd, 1H, J ) 9.4, 2.6 Hz), 8.26 (d, 1H,
J ) 9.6 Hz), 7.94 (d, 1H, J ) 2.4 Hz), 7.11 (d, 1H, J ) 2.4 Hz);
13C NMR (50 MHz, CDCl3) δ 156.3, 148.3, 146.9, 146.6, 145.7,
130.6, 122.7, 121.4, 117.2, 115.9, 106.7; MS (EI) m/z (relative
intensity) 250 (M+), 248 (M+, 100), 202, 190, 174, 139, 88. Anal.
Calcd for C11H5ClN2O3: C, 53.14; H, 2.03; N, 11.27. Found: C,
53.43; H, 1.97; N, 11.94.
1
164-165 °C (lit.20 mp 161.5 °C); H NMR (200 MHz, CDCl3) δ
8.03 (d, 1H, J ) 9.0 Hz), 7.96 (d, 1H, J ) 9.0 Hz), 7.81 (d, 1H,
J ) 2.4 Hz), 7.67 (dd, 1H, J ) 9.0, 2.4 Hz), 7.41 (d, 1H, J ) 8.6
Hz); 13C NMR (50 MHz, CDCl3) δ 151.0, 146.2, 137.8, 132.8,
131.4, 130.1, 127.4, 126.3, 123.3; MS (EI) m/z (relative intensity)
201 (M+), 199 (M+), 197 (M+, 100), 162, 127, 99, 81, 75.
2-Ch lor o-6-m et h ylq u in olin e (2c): 57% yield as a yellow
solid; mp 111-114 °C (lit.20 mp 113-114 °C); 1H NMR (200 MHz,
CDCl3) δ 8.00 (d, 1H, J ) 8.4 Hz), 7.90 (d, 1H, J ) 9.4 Hz), 7.52-
7.57 (m, 2H), 7.33 (d, 1H, J ) 8.4 Hz), 2.52 (s, 3H); 13C NMR
(50 MHz, CDCl3) δ 149.6, 146.3, 138.0, 136.8, 132.6, 128.1, 126.7,
126.3, 122.1, 21.4; MS (EI) m/z (relative intensity) 179 (M+), 177
(M+, 100), 142, 115, 89, 70.
4-Ch lor o-8-n itr oth ien o[3,2-c]qu in olin e (2i): 36% yield as
a white solid; mp 253-254 °C; 1H NMR (200 MHz, CDCl3) δ
9.00 (d, 1H, J ) 2.4 Hz), 8.48 (dd, 1H, J ) 9.0, 2.2 Hz), 8.25 (d,
1H, J ) 9.2 Hz), 7.76 (s, 2H); 13C NMR (50 MHz, CDCl3) δ 149.5,
147.3, 146.1, 133.5, 131.1, 128.4, 124.7, 123.1, 122.8, 119.7, 115.9;
MS (ESI) m/z (relative intensity) 267 (MH+), 265 (MH+, 100),
250, 235, 216, 214, 204. Anal. Calcd for C11H5ClN2O2S: C, 49.91;
H, 1.90; N, 10.58; S, 12.11. Found: C, 49.93; H, 1.82; N, 10.92;
S, 12.53.
2-Ch lor o-6-tr iflu or om eth ylqu in olin e (2d ): 98% yield as
1
a white solid; mp 97-99 °C; H NMR (200 MHz, CDCl3) δ 8.20
(d, 1H, J ) 8.8 Hz), 8.12-8.16 (m, 2H), 7.92 (dd, 1H, J ) 8.7,
1.9 Hz), 7.50 (d, 1H, J ) 8.4 Hz); 13C NMR (50 MHz, CDCl3) δ
153.0, 148.7, 139.3, 129.7, 128.8 (q, J ) 32.6 Hz), 126.2 (q, J )
2.9 Hz), 125.4 (q, J ) 4.3 Hz), 123.7, 123.7 (q, J ) 270.8 Hz),
121.0; MS (CI) m/z (relative intensity) 234 (MH+), 232 (MH+,
100), 212, 168; HRMS (CI) m/z C10H6ClF3N (MH+) calcd 232.0116,
found 232.0148.
4-Ch lor o-8-n itr oth ien o[2,3-c]qu in olin e (2j): 48% yield as
a pale yellow solid; mp 288-289 °C; 1H NMR (200 MHz, CDCl3)
δ 9.19 (d, 1H, J ) 2.2 Hz), 8.52 (dd, 1H, J ) 9.2 Hz), 8.28 (d,
1H, J ) 9.0 Hz), 8.12 (d, 1H, J ) 5.6 Hz), 8.07 (d, 1H, J ) 5.4
Hz); 13C NMR (50 MHz, CDCl3) δ 173.2, 172.8, 147.4, 144.3,
134.8, 130.8, 130.7, 128.9, 123.1, 122.6, 120.1; MS (ESI) m/z
(relative intensity) 267 (MH+), 265 (MH+), 225, 204 (100); HRMS
(CI) m/z C11H6ClN2O2S (MH+) calcd 264.9820, found 264.9845.
2-Ch lor o-6-n itr oqu in olin e (2e): 86% yield as a white solid;
mp 236-237 °C (lit.20 mp 235 °C); 1H NMR (200 MHz, CDCl3) δ
8.80 (d, 1H, J ) 2.6 Hz), 8.52 (dd, 1H, J ) 9.2, 2.6 Hz), 8.30 (d,
1H, J ) 8.6 Hz), 8.16 (d, 1H, J ) 9.6 Hz), 7.57 (d, 1H, J ) 8.8
Hz); 13C NMR (50 MHz, CDCl3) δ 152.6, 148.3, 144.5, 140.8,
128.8, 125.0, 123.9, 123.3, 123.0; MS (EI) m/z (relative intensity)
210 (M+), 208 (M+), 162, 127 (100). Anal. Calcd for C9H8N2O3:
C, 51.92; H, 2.42; N, 13.43. Found: C, 51.99; H, 2.42; N, 13.14.
2-Ch lor o-4-m eth yl-6-n itr oqu in olin e (2f): 65% yield as a
white solid; mp 214-215 °C; 1H NMR (200 MHz, CDCl3) δ 8.92
(d, 1H, J ) 2.6 Hz), 8.49 (dd, 1H, J ) 9.2, 2.6 Hz), 8.13 (d, 1H,
J ) 9.2 Hz), 7.40 (d, 1H, J ) 0.8 Hz), 2.79 (d, 3H, J ) 1.2 Hz);
13C NMR (50 MHz, CDCl3) δ 154.4, 150.0, 149.6, 145.6, 130.9,
126.2, 124.5, 123.8, 120.7, 18.6; MS (EI) m/z (relative intensity)
224 (M+), 222 (M+), 192, 164, 140 (100), 114, 89, 75; HRMS (CI)
m/z C10H8ClN2O2 (MH+) calcd 223.0271, found 223.0275.
Ack n ow led gm en t. This research was supported by
the Korea Science and Engineering Foundation (No. 97-
03-01-01-5-L) and National Research Laboratory Pro-
gram.
Su p p or tin g In for m a tion Ava ila ble: Characterization
information of 1a -j and time courses of percentage of conver-
sions of 4-nitro-2-vinylaniline (1e) depended on the equiv of
diphosgene and1H and 13C NMR spectra of 2a -j. This material
(20) Balli, H.; Schelz, D. Helv. Chim. Acta 1970, 53, 1903.
J O016196I
7886 J . Org. Chem., Vol. 67, No. 22, 2002