Y. Isogai et al. / Tetrahedron 65 (2009) 9575–9582
9579
127.3,126.7, 126.5, 125.0; IR (KBr) 1491,1443, 1331, 1242,1069, 1024,
970, 866, 818, 748, 700 cmꢁ1; GC–MS (EI) m/z (%) 234 (Mþ, 100);
Anal. Calcd for C16H11Cl: C, 80.50; H, 4.65, found: C, 80.41; H, 4.70;
mp 85 ꢀC.
NMR (CDCl3, 100 MHz)
d
139.5, 139.2, 135.3, 133.6, 130.5, 129.5,
129.1, 128.3, 127.3, 127.2, 126.7, 126.5, 126.3, 124.8, 21.9; IR (neat)
3057, 1489, 1445, 1258, 920, 880, 847, 750 cmꢁ1; GC–MS (EI) m/z (%)
252 (Mþ, 100); Anal. Calcd for C17H13Cl: C, 80.79; H, 5.18, found: C,
80.63; H, 5.38.
4.4.2. 1-Chloro-2-(4-(trifluoromethyl)phenyl)naphthalene
(3b). White solid; 1H NMR (CDCl3, 400 MHz)
d
8.41 (d, J¼8.5 Hz,1H),
4.4.9. 1-Chloro-2,3-dipropylnaphthalene (3h). White solid; 1H NMR
7.91 (d, J¼7.8 Hz, 1H), 7.85 (d, J¼8.3 Hz, 1H), 7.74 (d, J¼8.3 Hz, 2H),
(CDCl3, 400 MHz)
d
8.25 (d, J¼8.5 Hz, 1H), 7.73 (d, J¼7.8 Hz, 1H),
7.69–7.58 (m, 4H), 7.43 (d, J¼8.5 Hz, 1H); 13C NMR (CDCl3, 100 MHz)
7.54 (s, 1H), 7.52–7.42 (m, 2H), 2.98–2.93 (m, 2H), 2.80–2.76 (m,
d
143.7, 136.4, 133.8, 131.1, 130.1, 129.64 (q, J¼33.0 Hz), 129.57, 128.1,
2H), 1.77–1.60 (m, 4H), 1.10–1.03 (m, 6H); 13C NMR (CDCl3,
127.8, 127.6, 127.1, 126.9, 125.03, 124.99, 124.2 (q, J¼270.0 Hz); IR (KBr)
100 MHz) d 139.6, 137.4, 132.7, 131.1, 129.9, 127.3, 126.2, 126.0,
1655, 1614, 1560, 1499, 1406, 1327, 1167, 1123, 1082, 1063, 816 cmꢁ1
;
125.6, 124.3, 35.9, 32.7, 24.3, 23.0, 14.6, 14.2; IR (KBr) 2960, 1489,
1450, 1251, 935, 894, 748 cmꢁ1; GC–MS (EI) m/z (%) 246 (Mþ, 100);
Anal. Calcd for C16H19Cl: C, 77.87; H, 7.76, found: C, 77.88; H, 7.74;
mp 32–33 ꢀC.
GC–MS (EI) m/z (%) 306 (Mþ,100); Anal. Calcd for C17H10ClF3: C, 66.57;
H, 3.29, found: C, 66.58; H, 3.46; mp 121–122 ꢀC.
4.4.3. 1-Chloro-2-(4-methoxyphenyl)naphthalene (3c). White solid;
1H NMR (CDCl3, 400 MHz)
d
8.40 (d, J¼8.5 Hz, 1H), 7.88 (d,
4.4.10. 1-Chloro-2-cyclohexenylnaphthalene (3i). White solid; 1H
J¼9.3 Hz, 1H), 7.80 (d, J¼8.3 Hz, 1H), 7.63 (dd, J¼8.0, 8.0 Hz, 1H),
NMR (CDCl3, 400 MHz)
d
8.33 (d, J¼7.8 Hz, 1H), 7.82 (d, J¼8.0 Hz,
7.55 (dd, J¼7.6, 7.6 Hz, 1H), 7.46–7.44 (m, 3H), 7.01 (d, J¼2.4 Hz, 2H),
1H), 7.71 (d, J¼8.3 Hz, 1H), 7.58 (tt, J¼1.5, 8.3 Hz, 1H), 7.49 (tt, J¼1.2,
7.1 Hz, 1H), 7.29 (d, J¼8.5 Hz, 1H), 5.74 (sept, J¼1.9 Hz, 1H), 2.37 (m,
2H), 2.44 (m, 2H), 1.83 (m, 2H), 1.74 (m, 2H); 13C NMR (CDCl3,
3.89 (t, J¼2.4 Hz, 3H); 13C NMR (CDCl3, 100 MHz)
d 159.0, 137.4,
133.4, 132.5, 131.2, 130.9, 129.4, 128.6, 127.9, 127.3, 126.7, 126.3,
124.9, 113.5, 55.3; IR (KBr) 1607, 1514, 1495, 1460, 1439, 1286, 1252,
1177, 1024, 972, 821 cmꢁ1; GC–MS (EI) m/z (%) 268 (Mþ, 100); Anal.
Calcd for C17H13ClO: C, 75.98; H, 4.88. Found: C, 75.99; H, 5.13; mp
103–104 ꢀC.
100 MHz)
d 140.7, 138.1, 133.2, 131.1, 128.9, 127.83, 127.75, 127.4,
126.9, 126.5, 125.9, 124.6, 29.3, 25.5, 23.0, 22.1; IR (KBr) 1497, 1435,
1325, 978, 918, 860, 810, 772 cmꢁ1; GC–MS (EI) m/z (%) 242 (Mþ,
92), 179 (100); Anal. Calcd for C16H15Cl: C, 79.17; H, 6.23, found: C,
78.95; H, 7.74; mp 49–50 ꢀC.
4.4.4. 2-Butyl-1-chloronaphthalene (3d). Colorless oil; 1H NMR
(CDCl3, 400 MHz)
d
8.31 (d, J¼8.3 Hz, 1H), 7.81 (d, J¼8.0 Hz, 1H),
4.4.11. 3-Bromo-1-chloro-2-styrylnaphthalene (3j). White crystal;
7.69 (d, J¼8.3 Hz, 1H), 7.57 (tt, J¼1.5, 8.0 Hz, 1H), 7.48 (tt, J¼1.2,
8.0 Hz, 1H), 7.34 (d, J¼8.5 Hz, 1H), 2.95 (t, J¼7.8 Hz, 2H), 1.69 (quint,
J¼7.8 Hz, 2H), 1.44 (sext, J¼7.3 Hz, 2H), 0.97 (t, J¼7.3 Hz, 3H); 13C
1H NMR (CDCl3, 400 MHz)
d
8.31 (d, J¼8.0 Hz, 1H), 8.11 (s, 1H), 7.75
(d, J¼8.0 Hz, 1H), 7.64–7.52 (m, 4H), 7.42 (t, J¼7.2 Hz, 2H), 7.33 (t,
J¼7.2 Hz, 1H), 7.28–7.24 (m, 1H), 7.08 (d, J¼16 Hz, 1H); 13C NMR
NMR (CDCl3,100 MHz)
d
137.8,133.0,131.2,130.1,128.0,127.8,126.8,
(CDCl3, 100 MHz) d 137.2, 136.6, 133.7, 133.5, 131.2, 130.5, 130.3,
126.5, 125.6, 124.3, 34.2, 32.2, 22.7, 14.1; IR (neat) 3053, 2957, 2930,
128.7, 128.2, 127.5, 127.3, 127.0, 126.7, 125.5, 125.2, 121.3; IR (KBr)
2862, 1560, 1504, 1466, 1377, 1354, 1339, 1259, 1225, 988, 812 cmꢁ1
;
1767, 1553, 1487, 1450, 1250, 1184, 964, 847, 779, 764, 737 cmꢁ1
;
GC–MS (EI) m/z (%) 218 (Mþ, 43),175 (100); Anal. Calcd for C14H15Cl:
GC–MS (EI) m/z (%) 344 (Mþ, 18), 228 (100); Anal. Calcd for
C18H12BrCl: C, 62.91; H, 3.52, found: C, 62.60; H, 3.84; mp 108–
109 ꢀC.
C, 76.88; H, 6.91, found: C, 76.86; H, 7.08.
4.4.5. 2-tert-Butyl-1-chloronaphthalene (3e). Colorless oil; 1H NMR
(CDCl3, 400 MHz)
d
8.45 (d, J¼8.5 Hz, 1H), 7.80 (d, J¼8.0 Hz, 1H),
4.4.12. 1-Bromo-2-phenylnaphthalene (4a). Colorless oil; 1H NMR
7.40 (d, J¼8.8 Hz, 1H), 7.63 (d, J¼9.0 Hz, 1H), 7.57 (tt, J¼1.5, 8.5 Hz,
(CDCl3, 400 MHz)
(tt, J¼8.0, 1.2 Hz, 1H), 7.57 (tt, J¼6.8, 1.2 Hz, 1H), 7.54–7.42 (m, 6H);
13C NMR (CDCl3, 100 MHz)
142.2, 140.7, 133.5, 132.4, 129.6, 128.4,
d
8.42 (d, J¼7.8 Hz, 1H), 7.87–7.66 (m, 2H), 7.65
1H), 7.49 (tt, J¼1.2, 8.0 Hz, 1H), 1.62 (s, 9H); 13C NMR (CDCl3,
100 MHz)
d
143.7, 132.9, 132.2, 130.7, 127.5, 126.8, 126.5, 125.8,
d
125.3, 124.6, 36.7, 30.2; IR (neat) 2961, 2924, 1483, 1364, 1335, 1240,
976, 812 cmꢁ1; GC–MS (EI) m/z (%) 218 (Mþ, 59), 218 (100); HRMS
(EI) calcd for C14H15Cl (Mþ) 218.0862, found 218.0862.
128.0, 127.91, 127.88, 127.6, 127.5, 127.4, 126.5, 122.5; IR (neat) 1491,
1441, 1323, 1240, 1024, 955, 864, 816, 758 cmꢁ1; GC–MS (EI) m/z (%)
282 (Mþ, 100); HRMS (EI) calcd for C16H11Br (Mþ) 282.0044, found
282.0040.
4.4.6. (4-Chloronaphthalen-2-yl)trimethylsilane (3f). Colorless oil;
1H NMR (CDCl3, 400 MHz)
d
8.35 (d, J¼8.3 Hz, 1H), 7.83 (d, J¼7.8 Hz,
4.4.13. 1-Bromo-2-butylnaphthalene (4b). Colorless oil; 1H NMR
1H), 7.74 (d, J¼8.3 Hz, 1H), 7.50–7.61 (m, 3H), 0.46 (s, 9H); 13C NMR
(CDCl3, 400 MHz)
d
8.32 (d, J¼8.5 Hz, 1H), 7.79 (d, J¼8.0 Hz, 1H),
(CDCl3, 100 MHz)
d
139.3, 135.9, 135.0, 130.9, 130.7, 127.9, 126.9,
7.72 (d, J¼8.5 Hz, 1H), 7.58 (tt, J¼1.2, 6.8 Hz, 1H), 7.47 (tt, J¼1.2,
8.0 Hz, 1H), 7.34 (d, J¼4.1 Hz, 1H), 2.99 (t, J¼7.8 Hz, 2H), 1.69 (quint,
J¼5.9 Hz, 2H), 1.51 (sext, J¼7.3 Hz, 2H), 0.98 (t, J¼7.3 Hz, 3H); 13C
126.8, 126.0, 124.4, ꢁ0.4; IR (neat) 2953, 1304, 1247, 973, 866, 835,
810 cmꢁ1; MS (EI) m/z (%) 234 (Mþ, 18), 183 (100); HRMS (EI) calcd
for C13H15ClSi (Mþ) 234.0632, found 234.0631.
NMR (CDCl3,100 MHz) d 140.3,133.0,132.6,128.1,127.9,127.3,127.2,
127.1, 125.6, 123.5, 37.2, 32.4, 22.7, 14.1; IR (neat) 3057, 1488, 1445,
1352, 1258, 920, 880, 847, 775 cmꢁ1; GC–MS (EI) m/z (%) 262 (Mþ,
58), 219 (100); Anal. Calcd for C14H15Br: C, 63.89; H, 5.74, found: C,
63.84, H, 5.74.
4.4.7. (1-Chloronaphthalen-2-yl)trimethylsilane (3f0). Colorless oil;
1H NMR (CDCl3, 400 MHz)
d
8.25 (d, J¼8.3 Hz, 1H), 7.90 (s, 1H), 7.86
(d, J¼8.1 Hz, 1H), 7.65 (s, 1H), 7.60 (dd, J¼6.8, 7.1 Hz, 1H), 7.54 (ddd,
J¼1.0, 6.8, 7.8 Hz, 1H), 0.36 (s, 9H); 13C NMR (CDCl3, 100 MHz)
d
138.7, 134.2, 132.7, 131.5, 130.8, 129.8, 128.2, 127.3, 126.6, 124.2,
4.5. 1-Chloro-2,6-diphenylbenzene (11)
ꢁ1.09; IR (neat) 2954, 1249, 1096, 974, 819, 746 cmꢁ1; MS (EI) m/z
(%) 234 (Mþ, 26), 219 (100); HRMS (EI) calcd for C13H15ClSi (Mþ)
234.0632, found 234.0630.
To a suspension of CuCl2 (135 mg, 1 mmol) in CH3NO2 (2 mL)
were added 1c (116 mg, 0.5 mmol) and 2a (0.07 mL, 0.6 mmol)
successively at room temperature under an Ar atmosphere. The
mixture was stirred at 60 ꢀC for 2 h and then cooled to room
temperature. The resulting mixture was transferred to a silica gel
column, and the product was isolated using hexane as eluent; 10
4.4.8. 1-Chloro-3-methyl-2-phenylnaphthalene (3g). Colorless oil;
1H NMR (CDCl3, 400 MHz)
d
8.29 (d, J¼7.6 Hz, 1H), 7.81 (d, J¼7.3 Hz,
1H), 7.79 (s, 1H), 7.67–7.41 (m, 5H), 7.25 (m, 2H), 2.20 (s, 3H); 13C