The Journal of Organic Chemistry
Note
6-(4-Chlorophenyl)-5-iodobenzo[b]naphtho[2,1-d]-
thiophene (6i). Yield 60.3 mg, 76%; A yellow solid: Rf = 0.52 (Hex);
1H NMR (400 MHz, CDCl3) δ 6.54 (d, J = 8.4 Hz, 1H), 7.13 (td, J =
5-Chloro-6-pentylbenzo[b]naphtho[2,1-d]thiophene (8c).
Yield 42.1 mg, 83%; A white solid: Rf = 0.59 (Hex); H NMR (500
1
MHz, CDCl3) δ 0.98 (t, J = 7.5 Hz, 3H), 1.48 (x, J = 7.5 Hz, 2H), 1.64
(p, J = 7.5 Hz, 2H), 1.82−1.89 (m, 2H), 3.59 (t, J = 8.0 Hz, 2H),
7.47−7.54 (m, 2H), 7.58−7.67 (m, 2H), 7.97 (d, J = 8.0 Hz, 1H), 8.12
(d, J = 8.0 Hz, 1H), 8.33 (d, J = 8.5 Hz, 1H), 8.43 (d, J = 8.5 Hz, 1H);
13C NMR (125 MHz, CDCl3) δ 14.1, 22.6, 28.2, 31.5, 32.0, 123.1,
124.6, 124.7, 124.8, 125.7, 125.8, 126.5, 127.4, 127.9, 129.0, 129.3,
131.4, 135.4, 136.4, 137.4, 139.2; mp 90−91 °C; MS (70 eV) m/z (%)
61 (100), 178 (98), 338 (76) [M+], 340 (28) [M+2]; HRMS (ESI-
TOF) Calcd for C21H19ClS, 338.0896, found 338.0893.
8.0, 1.2 Hz, 1H), 7.26−7.29 (m, 2H), 7.37 (td, J = 8.4, 1.2 Hz, 1H),
7.59−7.69 (m, 4H), 7.89 (d, J = 8.4 Hz, 1H), 8.13−8.15 (m, 1H),
8.43−8.46 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 104.7, 122.7,
124.4, 124.7, 124.8, 126.0, 127.6, 128.4, 128.5, 129.5, 131.0, 131.3,
132.5, 134.4, 134.5, 136.0, 138.8, 139.2, 141.4, 143.8; mp 163−164 °C;
MS (70 eV) m/z (%) 472 (38) [M+2], 470 (100) [M+], 308 (65);
HRMS (ESI-TOF) Calcd for C22H12ClIS, 469.9393, found 469.9391.
6-(4-Bromophenyl)-5-iodobenzo[b]naphtho[2,1-d]-
thiophene (6j). Yield 58.5 mg, 67%; A yellow solid: Rf = 0.52 (Hex);
1H NMR (400 MHz, CDCl3) δ 6.55 (d, J = 8.8 Hz, 1H), 7.14 (td, J =
5-Chloro-6-(o-tolyl)benzo[b]naphtho[2,1-d]thiophene (8e).
1
Yield 44.6 mg, 83%; A yellow oil: Rf = 0.47 (Hex); H NMR (500
MHz, CDCl3) δ 2.03 (s, 3H), 6.54 (d, J = 8.5 Hz, 1H), 7.07 (t, J = 8.0
Hz, 1H), 7.24−7.26 (m, 1H), 7.33−7.52 (m, 4H), 7.67−7.72 (m, 2H),
7.89 (d, J = 8.0 Hz, 1H), 8.20−8.22 (m, 1H), 8.48−8.50 (m, 1H); 13C
NMR (125 MHz, CDCl3) δ 122.6, 124.0, 124.6, 124.8, 125.9, 126.1,
126.7, 127.3, 127.5, 128.7, 128.7, 128.7, 129.2, 129.3, 130.4, 131.2,
134.6, 136.4, 136.7, 137.0, 138.2, 139.1; mp 124−127 °C; MS (70 eV)
m/z (%) 61 (100), 70 (35), 358 (24) [M+], 360 (9) [M+2]; HRMS
(ESI-TOF) Calcd for C23H15ClS, 358.0583, found 358.0584.
8.8, 1.2 Hz, 1H), 7.20−7.24 (m, 2H), 7.37 (td, J = 8.0, 1.2 Hz, 1H),
7.65−7.70 (m, 2H), 7.74−7.78 (m, 2H), 7.89 (dd, J = 8.0, 0.8 Hz,
1H), 8.12−8.16 (m, 1H), 8.43−8.47 (m, 1H); 13C NMR (100 MHz,
CDCl3) δ 104.6, 122.6, 122.7, 124.4, 124.7, 124.8, 126.0, 127.6, 128.4,
128.5, 131.2, 131.4, 131.4, 132.5, 134.5, 136.0, 1138.8, 139.3, 141.3,
144.2; mp 175−177 °C; MS (70 eV) m/z (%) 516 (64) [M+2], 514
(60) [M+], 69 (100); HRMS (ESI-TOF) Calcd for C22H12BrIS,
513.8888, found 513.8889.
5-Chloro-6-(m-tolyl)benzo[b]naphtho[2,1-d]thiophene (8f).
5-Iodo-6-(4-(trifluoromethyl)phenyl)benzo[b]naphtho[2,1-
d]thiophene (6k). Yield 73.7 mg, 86%; A yellow solid: Rf = 0.52
(Hex); 1H NMR (400 MHz, CDCl3) δ 6.39 (d, J = 8.4 Hz, 1H), 7.09
(td, J = 8.0, 0.8 Hz, 1H), 7.37 (td, J = 8.0, 0.8 Hz, 1H), 7.48 (d, J = 8.4
Hz, 2H), 7.66−7.72 (m, 2H), 7.90 (dd, J = 8.0, 0.4 Hz, 3H), 8.14−
8.18 (m, 1H), 8.43−8.47 (m, 1H); 13C NMR (100 MHz, CDCl3) δ
104.0, 122.8, 124.4, 124.5, 124.9, 126.2, 126.2, 126.2, 127.7, 128.5,
128.6, 130.2, 132.4, 134.5, 135.8, 138.9, 139.4, 141.1, 148.9; mp 153−
156 °C; MS (70 eV) m/z (%) 504 (12) [M+], 77 (28), 151 (100);
HRMS (ESI-TOF) Calcd for C23H12F3IS, 503.9656, found 503.9654.
3-Iodo-2-(2-(pent-1-yn-1-yl)phenyl)benzo[b]thiophene (7b).
1
Yield 36.5 mg, 68%; A yellow oil: Rf = 0.47 (Hex); H NMR (500
MHz, CDCl3) δ 2.47 (s, 3H), 6.61 (d, J = 8.0 Hz, 1H), 7.08 (t, J = 8.5
Hz, 1H), 7.21−7.22 (m, 2H), 7.34 (t, J = 7.0 Hz, 1H), 7.39−7.41 (m,
1H), 7.50 (t, J = 7.5 Hz, 1H), 7.67−7.72 (m, 2H), 7.89 (d, J = 8.0 Hz,
1H), 8.19−8.21 (m, 1H), 8.48−8.49 (m, 1H); 13C NMR (125 MHz,
CDCl3) δ 21.6, 122.6, 124.2, 124.7, 124.8, 125.8, 126.1, 126.4, 127.3,
127.6, 128.7, 128.8, 128.9, 129.0, 129.1, 130.0, 131.5, 135.5, 136.4,
136.8, 138.8, 138.8, 139.1; MS (70 eV) m/z (%) 61 (96), 358 (100)
[M+], 360 (39) [M+2]; HRMS (ESI-TOF) Calcd for C23H15ClS,
358.0583, found 358.0585.
1
5-Chloro-6-(p-tolyl)benzo[b]naphtho[2,1-d]thiophene (8g).
Yield 58.1 mg, 85%; A yellow oil: Rf = 0.49 (Hex); H NMR (400
1
Yield 40.3 mg, 75%; A yellow oil: Rf = 0.47 (Hex); H NMR (500
MHz, CDCl3) δ 0.75 (t, J = 7.2 Hz, 3H), 1.35−1.44 (m, 2H), 2.23 (t, J
= 7.2 Hz, 2H), 7.36−7.50 (m, 5H), 7.54−7.57 (m, 1H), 7.82 (d, J =
8.0 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ
13.1, 21.5, 21.8, 79.2, 95.2, 119.0, 122.1, 122.3, 124.8, 124.9, 125.3,
127.3, 128.8, 131.0, 132.6, 134.0, 135.6, 136.9, 137.7; MS (70 eV) m/z
(%) 402 (41) [M+], 245 (77), 247 (89), 275 (100); HRMS (ESI-
TOF) Calcd for C19H15IS, 401.9939, found 401.9937.
MHz, CDCl3) δ 2.55 (s, 3H), 6.66 (d, J = 8.5 Hz, 1H), 7.09 (t, J = 8.0
Hz, 1H), 7.29−7.31 (m, 2H), 7.34 (t, J = 8.0 Hz, 1H), 7.41−7.43 (m,
2H), 7.67−7.71 (m, 2H), 7.89 (d, J = 8.0 Hz, 1H), 8.19−8.21 (m,
1H), 8.47−8.49 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 122.6,
124.2, 124.7, 124.8, 125.8, 126.2, 127.3, 127.6, 128.7, 129.0, 129.1,
129.3, 129.8, 131.6, 135.4, 135.9, 136.5, 136.8, 138.0, 139.1; MS (70
eV) m/z (%) 57 (37), 358 (100) [M+], 360 (40) [M+2]; HRMS (ESI-
TOF) Calcd for C23H15ClS, 358.0583, found 358.0585.
2-(2-(3,3-Dimethylbut-1-yn-1-yl)phenyl)-3-iodobenzo[b]-
thiophene (7d). Yield 49.5 mg, 70%; A brown oil: Rf = 0.57 (Hex);
1H NMR (400 MHz, CDCl3) δ 0.99 (s, 9H), 7.36−7.53 (m, 6H), 7.81
5-Chloro-6-(4-methoxyphenyl)benzo[b]naphtho[2,1-d]-
thiophene (8h). Yield 43.7 mg, 78%; A yellow solid: Rf = 0.19 (Hex);
1H NMR (500 MHz, CDCl3) δ 3.97 (s, 3H), 6.71 (d, J = 8.5 Hz, 1H),
(dd, J = 8.0, 0.8 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 27.8, 30.4,
77.5, 82.6, 103.4, 122.0, 125.0, 125.2, 125.3, 125.8, 127.2, 128.9, 130.6,
131.8, 137.3, 139.3, 141.1, 142.0; MS (70 eV) m/z (%) 416 (28) [M+],
258 (61), 259 (71), 289 (100); HRMS (ESI-TOF) Calcd for
C20H17IS, 416.0096, found 416.0097.
7.09−7.15 (m, 3H), 7.32−7.36 (m, 3H), 7.66−7.71 (m, 2H), 7.89 (d, J
= 8.0 Hz, 1H), 8.20 (d, J = 9.0 Hz, 1H), 8.48 (d, J = 9.0 Hz, 1H); 13
C
NMR (125 MHz, CDCl3) δ 55.4, 114.5, 122.6, 124.3, 124.7, 124.8,
125.8, 126.2, 127.3, 127.5, 128.7, 129.1, 129.4, 130.6, 131.2, 131.9,
135.0, 136.5, 136.8, 139.1, 159.5; mp 180−182 °C; MS (70 eV) m/z
(%) 57 (100), 71 (68), 374 (84) [M+], 376 (33) [M+2]; HRMS (ESI-
TOF) Calcd for C23H15ClOS, 374.0532, found 374.0533.
5-Chloro-6-(4-chlorophenyl)benzo[b]naphtho[2,1-d]-
thiophene (8i). Yield 49.9 mg, 88%; A yellow solid: Rf = 0.45 (Hex);
1H NMR (500 MHz, CDCl3) δ 6.69 (d, J = 8.5 Hz, 3H), 7.13 (t, J =
8.0 Hz, 1H), 7.35−7.39 (m, 3H), 7.59 (d, J = 8.5 Hz, 2H), 7.69−7.73
(m, 2H), 7.91 (d, J = 8.0 Hz, 1H), 8.20−8.22 (m, 1H), 8.46−8.48 (m,
1H) ; 13C NMR (125 MHz, CDCl3) δ 122.8, 124.4, 124.5, 124.8,
126.0, 126.2, 127.6, 127.7, 128.8, 129.0, 129.0, 129.4, 131.0, 131.1,
133.9, 134.3, 136.1, 137.0, 137.3, 139.1; mp 156−158 °C; MS (70 eV)
m/z (%) 61 (100), 378 (22) [M+], 380 (16) [M+2]; HRMS (ESI-
TOF) Calcd for C22H12Cl2S, 378.0037, found 378.0038.
5-Chloro-6-phenylbenzo[b]naphtho[2,1-d]thiophene (8a).
Yield 39.2 mg, 76%; A yellow solid: Rf = 0.48 (Hex); 1H NMR
(500 MHz, CDCl3) δ (d, J = 8.0 Hz, 1H), 7.06 (t, J = 8.0 Hz, 1H),
7.34 (t, J = 7.5 Hz, 1H), 7.41−7.43 (m, 2H), 7.60−7.62 (m, 3H),
7.68−7.72 (m, 2H), 7.90 (d, J = 8.0 Hz, 1H), 8.20−8.22 (m, 1H),
8.48−8.50 (m, 1H); 13C NMR (125 MHz, CDCl3) δ 122.6, 124.2,
124.7, 124.7, 125.9, 126.2, 127.3, 127.6, 128.3, 128.7, 128.9, 129.1,
129.1, 129.5, 131.4, 135.3, 136.4, 136.9, 138.9, 139.1; mp 141−143 °C;
MS (70 eV) m/z (%) 61 (100), 70 (55), 344 (64) [M+], 346 (26) [M
+2]; HRMS (ESI-TOF) Calcd for C22H13ClS, 344.0426, found
344.0428.
5-Chloro-6-propylbenzo[b]naphtho[2,1-d]thiophene (8b).
1
Yield 40.9 mg, 88%; A white solid: Rf = 0.57 (Hex); H NMR (400
MHz, CDCl3) δ 1.24 (t, J = 7.6 Hz, 3H), 1.86−1.96 (m, 2H), 3.58−
3.63 (m, 2H), 7.48−7.56 (m, 2H), 7.60−7.69 (m, 2H), 7.99 (d, J = 7.6
Hz, 1H), 8.15 (d, J = 8.0 Hz, 1H), 8.33 (d, J = 7.6 Hz, 1H), 8.45 (d, J
= 8.0 Hz, 1H); 13C NMR (100 MHz, CDCl3) δ 14.2, 21.9, 33.4, 123.1,
124.6, 124.6, 124.9, 125.7, 125.9, 126.6, 127.4, 127.9, 129.1, 129.3,
131.5, 135.2, 136.5, 137.4, 139.3; mp 102−104 °C; MS (70 eV) m/z
(%) 245 (30), 281 (81), 310 (100) [M+], 312 (34) [M+2]; HRMS
(ESI-TOF) Calcd for C19H15ClS, 310.0583, found 310.0580.
6-(4-Bromophenyl)-5-chlorobenzo[b]naphtho[2,1-d]-
thiophene (8j). Yield 53.8 mg, 85%; A yellow solid: Rf = 0.46 (Hex);
1H NMR (500 MHz, CDCl3) δ 6.69 (d, J = 8.5 Hz, 1H), 7.13 (t, J =
8.0 Hz, 1H), 7.30 (d, J = 8.5 Hz, 2H), 7.37 (t, J = 8.0 Hz, 1H), 7.68−
7.75 (m, 4H), 7.90 (d, J = 8.5 Hz, 1H), 8.19−8.21 (m, 1H), 8.46−8.47
(m, 1H); 13C NMR (125 MHz, CDCl3) δ 122.5, 122.8, 124.4, 124.5,
124.8, 126.0, 126.2, 127.6, 127.7, 128.2, 128.9, 129.0, 131.0, 131.3,
132.4, 133.9, 136.1, 137.1, 137.8, 139.1; mp 176−177 °C; MS (70 eV)
4709
dx.doi.org/10.1021/jo500377v | J. Org. Chem. 2014, 79, 4704−4711