2024 Bull. Chem. Soc. Jpn., 76, No. 10 (2003)
Substitution of Alkylidene Carbenoids
Colorless oil; IR (ZnSe) 1485, 1254, 862, 816, 584 cmÀ1
272 Hz), 127.4, 128.5, 128.5 (q, JCF ¼ 32 Hz), 137.7, 141.9,
143.1, 144.5, 146.0; HRMS (EIþ) Found: m=z 304.1096. Calcd
for C18H15F3O2: Mþ, 304.1075.
(2,4-Dimethyl-3-indenyl)phenylmethanol (30d): Colorless
oil; IR (ZnSe) 3423, 1448, 1390, 1011, 1003, 762, 696 cmÀ1
;
1H NMR (500 MHz, CDCl3) ꢁ 2.08 (3H, s), 2.37 (2H, t, J ¼ 8:0
Hz), 2.77 (2H, t, J ¼ 8:0 Hz), 6.78 (1H, dd, J ¼ 2:7, 8.8 Hz),
6.86 (1H, ddd, J ¼ 2:7, 8.6, 8.6 Hz), 7.53 (1H, dd, J ¼ 5:6, 8.6
Hz); 13C NMR (125 MHz, CDCl3) ꢁ 24.4, 28.0, 31.2, 112.9 (d,
JCF ¼ 21 Hz), 113.8 (d, JCF ¼ 22 Hz), 117.1, 128.0 (d, JCF ¼ 8
;
1H NMR (500 MHz, CDCl3) ꢁ 2.15 (3H, s), 2.18 (3H, s), 2.24
(1H,br), 3.39 (1H, d, J ¼ 23:0 Hz), 3.45 (1H, d, J ¼ 23:0 Hz),
6.31 (1H, s), 6.96 (1H, d, J ¼ 7:5 Hz), 7.05 (1H, dd, J ¼ 7:2,
7.5 Hz), 7.26 (1H, t, J ¼ 7:3 Hz), 7.26 (1H, d, J ¼ 7:2 Hz),
7.33 (2H, dd, J ¼ 7:3, 7.7 Hz), 7.41 (2H, d, J ¼ 7:7 Hz);
13C NMR (125 MHz, CDCl3) ꢁ 15.1, 21.7, 43.6, 69.0, 120.9,
124.1, 126.0, 126.9, 128.3, 129.6, 130.4, 138.7, 142.5, 142.6,
143.2, 144.0; HRMS (EIþ) Found: m=z 250.1370. Calcd for
C18H18O: Mþ, 250.1358.
Hz), 130.5 (d, JCF ¼ 3 Hz), 136.0 (d, JCF ¼ 2 Hz), 137.5 (d, JCF
¼
8 Hz), 161.7 (d, JCF ¼ 247 Hz); Anal. Found: C, 54.90; H, 4.14%.
Calcd for C11H18BrF: C, 54.80; H, 4.18%.
4-Bromo-3,5-dimethyl-1,2-dihydronaphthalene (33d): Col-
1
orless oil; IR (ZnSe) 1460, 893, 771 cmÀ1; H NMR (500 MHz,
CDCl3) ꢁ 2.13 (3H, s), 2.21–2.24 (2H, m), 2.57 (3H, s), 2.63–
2.66 (2H, m), 6.96–7.00 (1H, m), 7.01–7.02 (2H, m); 13C NMR
(125 MHz, CDCl3) ꢁ 23.7, 24.4, 29.8, 31.9, 114.8, 124.3, 126.7,
130.7, 134.0, 134.9, 138.8, 140.4; Anal. Found: C, 60.82; H,
5.65%. Calcd for C12H13Br: C, 60.78; H, 5.53%.
3-Methyl-1,2-dihydronaphthalene (32a):37
Colorless oil;
1H NMR (500 MHz, CDCl3) ꢁ 1.90 (3H, s), 2.21–2.25 (2H, m),
2.80 (2H, t, J ¼ 8:2 Hz), 6.19–6.21 (1H, m), 6.94–6.95 (1H, m),
7.03–7.07 (2H, m), 7.09–7.13 (1H, m); 13C NMR (125 MHz,
CDCl3) ꢁ 23.5, 28.0, 28.8, 122.7, 125.1, 125.9, 126.3, 127.1,
134.0, 135.0, 138.2.
(2-Methyl-3,4-dihydronaphthalen-1-yl)phenylmethanol
ꢁ
(34a): White solid; mp 97–98 C (hexane); IR (neat) 3410 (br),
1
1633, 1012, 704 cmÀ1; H NMR (500 MHz, CDCl3) ꢁ 2.01 (3H,
s), 2.19–2.20 (1H, m), 2.29 (1H, ddd, J ¼ 6:7, 6.9, 16.5 Hz),
2.40 (1H, ddd, J ¼ 6:4, 11.3, 16.5), 2.71–2.83 (2H, m), 6.14
(1H, d, J ¼ 5:4 Hz), 6.93–6.96 (1H, m), 7.00–7.03 (1H, m),
7.07 (1H, J ¼ 7:8 Hz), 7.11 (1H, d, J ¼ 7:3 Hz), 7.21–7.24
(1H, m), 7.30–7.34 (2H, m), 7.44–7.45 (2H, m); 13C NMR (125
MHz, CDCl3) ꢁ 20.5, 28.4, 31.4, 70.8, 124.6, 125.5, 125.9,
126.0, 126.7, 127.4, 128.4, 131.5, 133.2, 136.5, 137.6, 142.9;
Anal. Found: C, 86.20; H, 7.29%. Calcd for C18H18O: C, 86.36;
H, 7.25%.
7-Methoxy-3-methyl-1,2-dihydronaphthalene (32b):38 Col-
orless oil; IR (neat) 1608, 1498, 1252, 1153, 1039, 854 cmÀ1
1H NMR (500 MHz, CDCl3) ꢁ 1.86 (3H, m), 2.19 (2H, t,
J ¼ 8:2 Hz), 2.78 (2H, t, J ¼ 8:2 Hz), 3.77 (3H, s), 6.15 (1H,
m), 6.63–6.65 (2H, m), 6.87 (1H, d, J ¼ 7:7 Hz); 13C NMR
(125 MHz, CDCl3) ꢁ 23.3, 28.5, 28.6, 55.2, 111.0, 113.5, 122.0,
125.9, 128.3, 135.4, 135.7, 158.0.
;
7-Fluoro-3-methyl-1,2-dihydronaphthalene (32c):
less oil; IR (ZnSe) 1491, 1265, 1230, 856, 561 cmÀ1
Color-
1H NMR
;
(6-Methoxy-2-methyl-3,4-dihydronaphthalen-1-yl)phenyl-
methanol (34b): White solid; IR (ZnSe) 3460(br), 1606, 1496,
;
1252, 1039, 1030, 702 cmÀ1 1H NMR (500 MHz, CDCl3) ꢁ
(500 MHz, CDCl3) ꢁ 1.88 (3H, s), 2.20 (2H, t, J ¼ 8:2 Hz),
6.16 (1H, d, J ¼ 1:2 Hz), 6.75–6.80 (2H, m), 6.87 (1H, dd,
J ¼ 5:7, 9.1 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 23.3, 28.2 (d,
JCF ¼ 2 Hz), 28.3, 112.6 (d, JCF ¼ 24 Hz), 114.3 (d, JCF ¼ 22
Hz), 121.7, 126.1 (d, JCF ¼ 8 Hz), 131.1 (d, JCF ¼ 3 Hz), 136.3
1.99 (3H, s), 2.14 (1H, d, J ¼ 5:4 Hz), 2.26 (1H, ddd, J ¼ 6:6,
6.7, 16.4 Hz), 2.38 (1H, ddd, J ¼ 6:5, 11.7, 16.4 Hz), 2.70 (1H,
ddd, J ¼ 6:5, 6.7, 15.2 Hz), 2.77 (1H, ddd, J ¼ 6:6, 11.7, 15.2
Hz), 3.71 (3H, s), 6.12 (1H, d, J ¼ 5:4 Hz), 6.47 (1H, dd,
J ¼ 2:8, 8.6 Hz), 6.67 (1H, d, J ¼ 2:8 Hz), 6.99 (1H, d,
J ¼ 8:6), 7.20–7.23 (1H, m), 7.29–7.33 (2H, m), 7.42–7.44 (2H,
m); 13C NMR (125 MHz, CDCl3) ꢁ 20.2, 28.8, 31.2, 55.1, 70.7,
110.4, 113.7, 125.5, 125.9, 126.0, 126.6, 128.3, 130.9, 134.8,
138.4, 143.0, 157.5; HRMS (EIþ) Found: m=z 280.1493. Calcd
for C19H20O2: Mþ, 280.1463.
(d, JCF ¼ 7 Hz), 137.2 (d, JCF ¼ 2 Hz), 161.2 (d, JCF
¼
244 Hz); HRMS (EIþ) Found: m=z 162.0817. Calcd for C11H11F:
Mþ, 162.0845.
3,5-Dimethyl-1,2-dihydronaphthalene (32d): Colorless oil;
1H NMR (500 MHz, CDCl3) ꢁ 1.93 (3H, d, J ¼ 1:2 Hz), 2.18
(2H, t, J ¼ 8:1 Hz), 2.28 (3H, s), 2.76 (2H, t, J ¼ 8:1 Hz), 6.39
(1H, q, J ¼ 1:2 Hz), 6.91–6.95 (3H, m); 13C NMR (125 MHz,
CDCl3) ꢁ 19.0, 24.0, 28.6, 28.7, 119.4, 125.0, 125.5, 128.2,
132.1, 133.0, 134.2, 138.5; HRMS (EIþ) Found: m=z 158.1074.
Calcd for C12H14: Mþ, 158.1096.
(6-Fluoro-2-methyl-3,4-dihydronaphthalen-1-yl)phenyl-
methanol (34c): White solid; IR (ZnSe) 3384(br), 1493, 1244,
;
702, 565 cmÀ1 1H NMR (500 MHz, CDCl3) ꢁ 2.01 (3H, s),
4-Bromo-3-methyl-1,2-dihydronaphthalene (33a): Color-
less oil; IR (ZnSe) 1477, 1452, 1248, 937, 756 cmÀ1 1H NMR
;
2.13 (1H, d, J ¼ 4:0 Hz), 2.29 (1H, ddd, J ¼ 6:7, 7.1, 16.6 Hz),
2.38 (1H, ddd, J ¼ 6:6, 10.7, 16.6 Hz), 2.71 (1H, ddd, J ¼ 6:6,
7.1, 15.2 Hz), 2.77 (1H, ddd, J ¼ 6:7, 10.7, 15.2 Hz), 6.14 (1H,
d, J ¼ 4:0 Hz), 6.61 (1H, ddd, J ¼ 2:8, 8.7, 8.7 Hz), 6.79 (1H,
dd, J ¼ 2:8, 9.1 Hz), 7.07 (1H, dd, J ¼ 5:8, 8.7 Hz), 7.20–7.24
(1H, m), 7.29–7.33 (2H, m), 7.40–7.42 (2H, m); 13C NMR (125
MHz, CDCl3) ꢁ 20.3, 28.5, 31.0, 70.7, 112.3 (d, JCF ¼ 21 Hz),
114.3 (d, JCF ¼ 21 Hz), 125.4, 126.5 (d, JCF ¼ 8 Hz), 126.8,
128.4, 129.2 (d, JCF ¼ 4 Hz), 130.8, 136.5 (d, JCF ¼ 2 Hz),
139.1 (d, JCF ¼ 7 Hz), 142.6, 160.8 (d, JCF ¼ 246 Hz); HRMS
(EIþ) Found: m=z 268.1279. Calcd for C18H17FO: Mþ, 268.1263.
(2,8-Dimethyl-3,4-dihydronaphthalen-1-yl)phenylmethanol
(500 MHz, CDCl3) ꢁ 2.10 (3H, s), 2.39 (2H, t, J ¼ 7:9 Hz),
2.80 (2H, t, J ¼ 7:9 Hz), 7.06 (1H, d, J ¼ 7:3 Hz), 7.10–7.13
(1H, m), 7.19–7.24 (1H, m), 7.58 (1H, d, J ¼ 7:8 Hz); 13C NMR
(125 MHz, CDCl3) ꢁ 24.5, 27.9, 31.6, 118.2, 126.3, 126.6, 126.7,
127.0, 134.2, 135.3, 137.0; Anal. Found: C, 58.99; H, 5.15%.
Calcd for C11H11Br: C, 59.22; H, 4.97%.
4-Bromo-7-methoxy-3-methyl-1,2-dihydronaphthalene
(33b): Colorless oil; IR (ZnSe) 1606, 1489, 1255, 1119, 1041,
592 cmÀ1 1H NMR (500 MHz, CDCl3) ꢁ 2.06 (3H, s), 2.35
;
(2H, t, J ¼ 7:9 Hz), 2.76 (2H, t, J ¼ 7:9 Hz), 3.78 (3H, s), 6.63
(1H, d, J ¼ 2:7 Hz), 6.71 (1H, dd, J ¼ 2:7, 8.6 Hz), 7.49 (1H,
d, J ¼ 8:6 Hz); 13C NMR (125 MHz, CDCl3) ꢁ 24.3, 28.3, 31.4,
55.3, 110.9, 113.0, 117.6, 127.5, 127.6, 134.1, 136.9, 158.8;
HRMS (EIþ) Found: m=z 252.0133. Calcd for C12H13BrO: Mþ,
252.0150.
ꢁ
(34d): White solid; mp 113–114 C (hexane); IR (ZnSe) 3438
1
(br), 2929, 1448, 773, 706 cmÀ1; H NMR (500 MHz, CDCl3) ꢁ
1.77 (3H, s), 2.02 (1H, ddd, J ¼ 5:4, 6.3, 15.3 Hz), 2.14 (1H,
ddd, J ¼ 5:5, 11.3, 15.3 Hz), 2.20 (1H, brs), 2.42 (3H, s), 2.60
(1H, ddd, J ¼ 5:5, 6.3, 14.8 Hz), 2.65 (1H, ddd, J ¼ 5:4, 11.3,
14.8 Hz), 5.89 (1H, s), 7.01–7.04 (3H, m), 7.18–7.21 (1H, m),
4-Bromo-7-fluoro-3-methyl-1,2-dihydronaphthalene (33c):