The Journal of Organic Chemistry
Article
130.8, 130.1, 130.0, 129.9, 128.3, 127.9, 126.7, 126.6, 126.3, 124.9,
123.2, 122.5, 115.4, 115.2, 38.8; IR (film) 3024, 2923, 2850, 2358,
1602, 1508, 1218, 1014, 743, 661 cm−1; HRMS (EI) calcd for C21H16F
[(M + H)+] 287.1231, found 287.1235.
1461, 1205, 1155, 1067, 747 cm−1; HRMS (EI) calcd for C23H21O2
[(M + H)+] 329.1536, found 329.1538.
9-(2-Chloro-4-(trifluoromethyl)benzyl)phenanthrene (8o). White
powder (51 mg, 69%); mp 119−120 °C; Rf = 0.45 (petroleum ether/
EtOAc = 60:1); 1H NMR (400 MHz, CDCl3) δ 8.72 (dd, J = 8.2, 27.9
Hz, 2H), 7.89 (d, J = 8.1 Hz, 1H), 7.79 (d, J = 7.7 Hz, 1H), 7.69−7.63
(m, 2H), 7.60−7.57 (m, 3H), 7.46 (d, J = 8.3 Hz, 1H), 7.40 (s, 1H),
7.27 (s, 1H), 4.59 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 139.0,
138.0, 132.3, 131.6, 130.9, 130.8, 130.1, 130.0, 128.4, 127.9, 127.5,
127.4, 126.9, 126.8, 126.6, 124.7, 124.6, 124.3, 123.3, 122.5, 36.8; IR
(film) 2928, 2856, 2333, 1612, 1332, 1170, 1083, 742 cm−1; HRMS
(EI) calcd for C22H15ClF3 [(M + H)+] 371.0809, found 371.0808.
9-(2-(Allyloxy)benzyl)phenanthrene (8p). White waxy liquid (45
mg, 70%); Rf = 0.43 (petroleum ether/EtOAc = 60:1); 1H NMR (400
MHz, CDCl3) δ 8.70 (dd, J = 8.1, 23.4 Hz, 2H), 8.05 (d, J = 8.1 Hz,
1H), 7.79 (d, J = 7.6 Hz, 1H), 7.64−7.52 (m, 5H), 7.19−7.15 (m,
1H), 6.92 (d, J = 8.8 Hz, 2H), 6.78 (dd, J = 5.8, 13.4 Hz, 1H), 6.13−
6.03 (m, 1H), 5.44 (dd, J = 1.5, 17.3 Hz, 1H), 5.26 (dd, J = 1.4, 10.5
Hz, 1H), 4.64 (d, J = 5.0 Hz, 2H), 4.50 (s, 2H); 13C NMR (100 MHz,
CDCl3) δ 156.1, 134.8, 133.5, 131.9, 131.6, 130.7, 130.1, 129.0, 128.2,
127.7, 127.2, 126.5, 126.1, 126.0, 125.1, 123.0, 122.4, 120.7, 117.1,
111.5, 68.8, 33.1; IR (film) 3033, 2962, 2927, 1726, 1560, 1490, 1451,
1260, 1019, 746 cm−1; HRMS (EI) calcd for C24H21O [(M + H)+]
325.1587, found 325.1595.
5-(Phenanthren-9-ylmethyl)benzo[d][1,3]dioxole (8q). Pale-white
solid (39 mg, 63%); mp 127−129 °C; Rf = 0.42 (petroleum ether/
EtOAc = 60:1); 1H NMR (400 MHz, CDCl3) δ 8.69 (dd, J = 8.1, 23.9
Hz, 2H), 8.02 (d, J = 8.1 Hz, 1H), 7.82 (d, J = 7.4 Hz, 1H), 7.64−7.54
(m, 5H), 7.35−7.12 (m, 3H), 5.89 (s, 2H), 4.39 (s, 2H); 13C NMR
(100 MHz, CDCl3) δ 147.7, 145.9, 134.8, 134.1, 131.7, 131.3, 130.8,
129.9 128.8, 128.2, 127.8, 126.6, 126.5, 126.2, 124.9, 123.1, 122.5,
121.6, 109.2, 108.2, 100.8, 39.3; IR (film) 2926, 2855, 2322, 1727,
1502, 1259, 1039, 799 cm−1; HRMS (EI) calcd for C22H17O2 [(M +
H)+] 313.1223, found 313.1228.
9-(4-Cyanobenzyl)phenanthrene (8h). White solid (36 mg, 61%);
1
mp 164−165 °C; Rf = 0.45 (petroleum ether/EtOAc = 30:1); H
NMR (400 MHz, CDCl3) δ 8.71 (dd, J = 8.2, 25.1 Hz, 2H), 7.85 (dd, J
= 7.8, 12.2 Hz, 2H), 7.68−7.52 (m, 7H), 7.33 (d, J = 8.3 Hz, 2H), 4.53
(s, 2H); 13C NMR (100 MHz, CDCl3) δ 146.1, 133.0, 132.3, 131.5,
130.9, 130.8, 130.1, 129.4, 128.4, 128.3, 126.9, 126.8, 126.7, 126.5,
124.7, 123.3, 122.5, 118.9, 110.2, 39.7; IR (film) 2960, 2925, 2854,
2227, 1606, 1260, 1020, 800 cm−1; HRMS (EI) calcd for C22H15NNa
[(M + Na)+] 316.1097, found 316.1103.
9-(4-Methoxybenzyl)phenanthrene (8i). Pale-white powder (42.5
1
mg, 71%); mp 114−115 °C; Rf = 0.32 (hexane/EtOAc = 19:1); H
NMR (400 MHz, CDCl3) δ 8.61 (dd, J = 8.1, 24.2 Hz, 2H), 7.96 (d, J
= 7.8 Hz, 1H), 7.73 (d, J = 7.5 Hz, 1H), 7.57−7.45 (m, 5H), 7.10 (dd,
J = 8.7, 14.8 Hz, 2H), 6.71 (dd, J = 8.7, 23.0 Hz, 2H), 4.34 (s, 2H),
3.67 (s, 3H); 13C NMR (100 MHz, CDCl3) δ 158.0, 135.2, 132.2,
131.8, 131.4, 130.8, 130.0, 129.7, 128.2, 127.7, 126.6, 126.5, 126.2,
126.1, 125.0, 123.1, 122.4, 113.9, 55.2, 38.7; IR (film) 3027, 1603,
1410, 1261, 798, 695, 667 cm−1; HRMS (EI) calcd for C22H19O [(M +
H)+] 299.1430, found 299.1432.
9-(4-(Trifluoromethyl)benzyl)phenanthrene (8j). White powder
(54 mg, 80%); mp 126−127 °C; Rf = 0.48 (petroleum ether/EtOAc =
60:1); 1H NMR (400 MHz, CDCl3) δ 8.63 (dd, J = 8.2, 24.6 Hz, 2H),
7.85 (d, J = 8.1 Hz, 1H), 7.75 (d, J = 7.6 Hz, 1H), 7.58−7.43 (m, 7H),
7.28−7.17 (m, 2H), 4.45 (s, 2H); 13C NMR (100 MHz, CDCl3) δ
144.47, 133.64, 131.6, 131.0, 130.9, 130.0, 129.0, 128.3, 128.2, 126.8,
126.7, 126.5, 126.4, 125.4 (q, J = 3.8 Hz, CF3), 124.8, 123.2, 122.5,
39.4; IR (film) 2961, 2926, 2322, 1616, 1326 cm−1; HRMS (EI) calcd
for C22H16F3 [(M + H)+] 337.1199, found 337.1203.
9-(3-Nitrobenzyl)phenanthrene (8k). Pale-white solid (30 mg,
48%); mp 103−104 °C; Rf = 0.30 (EtOAc/petroleum ether = 30:1);
1H NMR (400 MHz, CDCl3) δ 8.71 (dd, J = 8.2, 25.5 Hz, 2H), 8.15
(s, 1H), 8.06 (d, J = 8.1 Hz, 1H), 7.87 (dd, J = 7.9, 25.3 Hz, 2H),
7.68−7.53 (m, 6H), 7.41 (t, J = 7.9 Hz, 1H), 4.57 (s, 2H); 13C NMR
(100 MHz, CDCl3) δ 148.5, 142.5, 133.8, 133.0, 131.5, 130.8, 130.1,
129.4, 128.5, 128.3, 126.9, 126.8, 126.7, 126.6, 124.6, 123.5, 123.4,
122.5, 121.5, 39.3; IR (film) 2960, 2923, 2854, 1528, 1348, 1260, 1017,
799 cm−1; HRMS (EI) calcd for C21H16NO2 [(M + H)+] 314.1176,
found 314.1181.
2-(Phenanthren-9-ylmethyl)thiophene (8r). Pale-yellow solid (29
1
mg, 54%); mp 134−135 °C; Rf = 0.48 (petroleum ether); H NMR
(400 MHz, CDCl3) δ 8.70 (dd, J = 8.3, 25.3 Hz, 2H), 8.09 (d, J = 8.1
Hz, 1H), 7.84 (d, J = 7.6 Hz, 1H), 7.67−7.56 (m, 4H), 7.25 (s, 1H),
7.14 (dd, J = 1.1, 5.1 Hz, 1H), 6.91 (dd, J = 3.5, 5.1 Hz, 1H), 6.82−
6.81 (m, 1H), 4.65 (s, 2H); 13C NMR (100 MHz, CDCl3) δ 143.4,
134.3, 131.7, 130.9, 130.8, 130.1, 128.4, 127.5, 126.9, 126.7, 126.4,
126.3, 125.4, 124.7, 123.8, 123.2, 122.5, 34.0; IR (film) 2925, 2854,
1453, 1022, 656 cm−1; HRMS (EI) calcd for C19H15S [(M + H)+]
275.0889, found 275.0895.
N,N-Dimethyl-4-(phenanthren-9-ylmethyl)aniline (8l).24 Pale-red
powder (33 mg, 53%); mp 131−132 °C; Rf = 0.32 (petroleum ether/
EtOAc = 40:1); 1H NMR (400 MHz, CDCl3) δ 8.69 (dd, J = 8.1, 23.4
Hz, 2H), 8.08 (d, J = 8.1 Hz, 1H), 7.81 (dd, J = 1.1, 7.8 Hz, 1H),
7.64−7.53 (m, 5H), 7.24−7.11 (m, 2H), 6.69 (d, J = 8.5 Hz, 2H), 4.40
(s, 2H), 2.90 (s, 6H); 13C NMR (100 MHz, CDCl3) δ 135.6, 131.9,
131.5, 130.7, 129.8, 129.4, 128.2, 127.5, 126.5, 126.1, 126.0, 125.1,
123.0, 122.4, 113.0, 40.8, 38.6; IR (film) 2960, 2922, 2850, 1615, 1520,
1260, 1019, 800 cm−1.
3-(Phenanthren-9-ylmethyl)pyridine (8s). Pale-green powder (39
mg, 72%); mp 125−126 °C; Rf = 0.30 (petroleum ether/EtOAc =
1:1); 1H NMR (400 MHz, CDCl3) δ 8.70 (dd, J = 8.2, 26.3 Hz, 2H),
8.64 (s, 1H), 8.47 (d, J = 4.1 Hz, 1H), 7.96 (d, J = 8.1 Hz, 1H), 7.81
(d, J = 7.9 Hz, 1H), 7.66−7.56 (m, 4H), 7.54 (s, 1H), 7.46 (d, J = 7.8
Hz, 1H), 7.16 (dd, J = 4.9, 7.7 Hz, 1H), 4.47 (s, 2H); 13C NMR (100
MHz, CDCl3) δ 150.2, 147.7, 136.1, 135.7, 133.4, 131.6, 130.9, 130.0,
128.3, 128.1, 126.8, 126.5, 126.4, 124.7, 123.4, 123.2, 122.5, 36.7; IR
(film) 2925, 1725, 1422, 1260, 1026, 749 cm−1; HRMS (EI) calcd for
C20H16N [(M + H)+] 270.1277, found 270.1280.
9-(3,4-Dichlorobenzyl)phenanthrene (8m). White powder (44.5
mg, 66%); mp 141−142 °C; Rf = 0.42 (petroleum ether/EtOAc =
1
100:1); H NMR (400 MHz, CDCl3) δ 8.70 (dd, J = 8.2, 24.1 Hz,
10-Benzyl-2-(tert-butyl)phenanthrene (9a). White powder (40
mg, 62%); mp 101−102 °C; Rf = 0.44 (petroleum ether/EtOAc =
100:1); 1H NMR (400 MHz, CDCl3) δ 8.72 (d, J = 1.9 Hz, 1H), 8.70
(d, J = 8.4 Hz, 1H), 7.96 (d, J = 8.7 Hz, 1H), 7.79 (dd, J = 0.9, 7.8 Hz,
1H), 7.63−7.53 (m, 3H), 7.49 (s, 1H), 7.27−7.23 (m, 4H), 4.46 (s,
2H), 1.47 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 148.9, 140.4,
134.5, 132.0, 130.5, 130.1, 129.3, 128.8, 128.5, 128.3, 127.8, 127.2,
126.4, 126.1, 126.0, 124.9, 124.7, 122.3, 118.8, 39.6, 35.1, 31.5; IR
(film) 3026, 2962, 1602, 1494, 1260, 1028, 802, 699 cm−1; HRMS
(EI) calcd for C25H25 [(M + H)+] 325.1951, found 325.1958.
10-(4-Bromobenzyl)-2-(tert-butyl)phenanthrene (9b). White pow-
der (53 mg, 66%); mp 122−123 °C; Rf = 0.44 (petroleum ether/
EtOAc = 100:1); 1H NMR (400 MHz, CDCl3) δ 8.70 (d, J = 10.0 Hz,
2H), 7.88 (8, J = 8.7 Hz, 1H), 7.80 (d, J = 7.6 Hz, 1H), 7.64−7.54 (m,
3H), 7.48 (s, 1H), 7.38 (d, J = 8.3 Hz, 2H), 7.11 (d, J = 8.3 Hz, 2H),
4.39 (s, 2H), 1.47 (s, 9H); 13C NMR (100 MHz, CDCl3) δ 149.1,
2H), 7.89 (d, J = 7.8 Hz, 1H), 7.83 (dd, J = 1.0, 7.8 Hz, 1H), 7.66−
7.53 (m, 5H), 7.32−7.24 (m, 2H), 7.05 (dd, J = 1.9, 8.2 Hz, 1H), 4.41
(s, 2H); 13C NMR (100 MHz, CDCl3) δ 140.6, 133.4, 132.5, 131.6,
130.9, 130.8, 130.5, 130.4, 130.2, 130.1, 128.3, 128.2, 128.1, 126.8,
126.7, 126.6, 126.5, 124.7, 123.3, 122.5, 38.8; IR (film) 2963, 2927,
2356, 1452, 1325, 1260, 1029, 727 cm−1; HRMS (EI) calcd for
C21H15Cl2 [(M + H)+] 337.0545, found 337.0550.
9-(3,5-Dimethoxybenzyl)phenanthrene (8n). Brown powder (39
mg, 60%); mp 108−109 °C; Rf = 0.35 (petroleum ether/EtOAc =
30:1); 1H NMR (400 MHz, CDCl3) δ 8.69 (dd, J = 8.1, 22.4 Hz, 2H),
8.03 (d, J = 7.9 Hz, 1H), 7.82 (d, J = 7.5 Hz, 1H), 7.64−7.24 (m, 5H),
6.42 (d, J = 2.1 Hz, 2H), 6.32 (t, J = 2.1 Hz, 1H), 4.41 (s, 2H), 3.71 (s,
6H); 13C NMR (100 MHz, CDCl3) δ 160.9, 142.7, 134.4, 131.8,
131.4, 130.8, 130.0, 128.3, 127.9, 126.6, 126.5, 126.2, 125.0, 123.1,
122.4, 107.1, 98.0, 55.2, 39.9; IR (film) 2958, 2927, 2851, 1723, 1595,
I
dx.doi.org/10.1021/jo501489c | J. Org. Chem. XXXX, XXX, XXX−XXX