3
448 J . Org. Chem., Vol. 63, No. 10, 1998
Katritzky et al.
1
raphy on silica gel, light yellow oil; H NMR δ 2.38 (s, 3H),
2
3
1H), 4.09 (dd, J ) 9.3 and 14.1 Hz, 1H), 5.61 (dd, J ) 6.0 and
1
3
.95-3.02 (m, 1H), 3.13-3.19 (m, 1H), 3.82-3.89 (m, 1H),
.96-4.03 (m, 1H), 6.42 (t, J ) 7.5 Hz, 1H), 6.56 (d, J ) 2.6
9.3 Hz, 1H), 6.89-7.49 (m, 17H), 7.96 (d, J ) 6.6 Hz, 1H); C
NMR δ 39.8, 63.8, 109.8, 120.2, 124.1, 126.9, 127.3, 127.3,
127.7, 127.8, 128.4, 129.0, 129.5, 130.5, 131.2, 133.4, 134.7,
Hz, 1H), 6.80 (d, J ) 8.0 Hz, 2H), 6.89-6.93 (m, 2H), 7.22 (t,
J ) 7.6 Hz, 2H), 7.31 (t, J ) 7.1 Hz, 1H), 7.39 (t, J ) 8.0 Hz,
139.3, 141.8, 142.5, 146.2. Anal. Calcd for C26
21 3
H N : C, 83.17;
1
H), 7.50 (d, J ) 8.3 Hz, 1H), 8.04 (d, J ) 8.3 Hz, 1H); 13
C
H, 5.64; N, 11.19. Found: C, 83.34; H, 5.50; N, 10.80.
2-[2-(1H -Ben zot r ia zol-1-yl)-2-(4-N,N-d im et h yla m in o-
ph en yl)eth yl]biph en yl (20c): recrystallized from ethyl ether,
NMR δ 15.2, 35.3, 55.6, 63.7, 109.8, 114.5, 120.0, 121.0, 123.9,
24.8, 126.1, 127.2, 129.4, 132.5, 138.8, 140.7, 146.1, 158.3.
Anal. Calcd for C20 OS: C, 68.74; H, 5.48; N, 12.02.
1
1
H
19
N
3
gray powder, mp 145.0-146.1 °C; H NMR δ 2.84 (s, 6H), 3.83
Found: C, 68.81; H, 5.54; N, 12.39.
(dd, J ) 6.0 and 14.2 Hz, 1H), 4.05 (dd, J ) 9.6 and 13.5 Hz,
1H), 5.59 (t, J ) 8.8 Hz, 1H), 6.51 (d, J ) 8.2 Hz, 2H), 6.88 (d,
J ) 8.2 Hz, 2H), 7.00-7.54 (m, 12H), 7.94 (d, J ) 7.1 Hz, 1H);
N -{4-[1-(1H -B e n zo t r ia zo l-1-y l)-3-p h e n o x y p r o p y l]-
p h en yl}-N,N-d im eth yla m in e (10c): white microcrystals;
mp 106.1-107.2 °C (hexanes/ethyl acetate, 10:1); H NMR δ
1
13
C NMR δ 39.2, 40.3, 63.1, 109.6, 112.1, 119.6, 123.4, 126.4,
2
3
8
7
.89 (s, 6H), 2.89-2.97 (m, 1H, overlapped), 3.18-3.27 (m, 1H),
.96 (t, J ) 5.6 Hz, 2H), 6.08 (t, J ) 7.2 Hz, 1H), 6.63 (d, J )
.7 Hz, 2H), 6.83 (d, J ) 8.4 Hz, 2H), 6.91 (t, J ) 7.2 Hz, 1H),
.21-7.36 (m, 5H), 7.42 (d, J ) 8.0 Hz, 1H), 8.02 (d, J ) 8.4
126.6, 126.7, 127.1, 127.3, 127.4, 128.4, 129.1, 130.0, 130.7,
132.8, 134.7, 141.5, 142.0, 145.8, 150.1. Anal. Calcd for
28 26 4
C H N : C, 80.34; H, 6.27; N, 13.39. Found: C, 80.12; H,
6.51; N, 13.49.
1
3
Hz, 1H); C NMR δ 34.8, 40.3, 59.6, 64.0, 110.0, 112.3, 114.5,
2-[2-(1H -Ben zot r ia zol-1-yl)-2-m et h oxyet h yl]b ip h en yl
(22): oil separated by gradient column chromatography on
1
1
19.7, 120.8, 123.7, 125.9, 126.9, 127.8, 129.4, 132.9, 146.1,
50.3, 158.5. Anal. Calcd for C23 O: C, 74.17; H, 6.49;
1
H
24
N
4
silica gel, light yellow; H NMR δ 3.09 (s, 3H), 3.43 (dd, J )
N, 15.04. Found: C, 74.23; H, 6.35; N, 15.11.
-(3-P h e n o x y -1-p h e n y lp r o p y l)-1H -b e n z o t r i a z o le
10d ): separated by gradient column chromatography on silica
gel, light yellow oil; H NMR δ 2.91-2.96 (m, 1H), 3.26-3.30
m, 1H), 3.94-3.99 (m, 2H), 6.16 (dd, J ) 6.6 and 8.7 Hz, 1H),
.83 (d, J ) 8.7 Hz, 2H), 6.92 (t, J ) 7.2 Hz, 1H), 7.21-7.41
m, 10H), 8.04 (d, J ) 7.8 Hz, 1H); C NMR δ 35.0, 59.8, 63.9,
09.7, 114.5, 119.9, 121.0, 123.9, 126.8, 127.2, 128.4, 128.9,
29.4, 133.1, 138.8, 146.1, 158.4. Anal. Calcd for C21 O:
C, 76.57; H, 5.81; N, 12.76. Found: C, 76.61; H, 6.10; N, 13.10.
-(1-Bu t yl-3-p h en oxy-1-p h en ylp r op yl)-1H -b en zot r i-
a zole (12): separated by gradient column chromatography on
6.9 and 14.1 Hz, 1H), 3.63 (dd, J ) 6.6 and 14.1 Hz, 1H), 5.94
(t, J ) 6.9 Hz, 1H), 7.15-7.34 (m, 12H), 7.99-8.02 (m, 1H);
1
1
3
(
C NMR δ 38.0, 56.6, 92.2, 110.8, 119.9, 124.0, 127.0, 127.1,
1
127.3, 127.5, 128.2, 129.1, 130.0, 130.2, 131.3, 132.5, 141.0,
142.6, 146.5. Anal. Calcd for C21 O: C, 76.57; H, 5.81;
(
19 3
H N
6
(
N, 12.76. Found: C, 76.37; H, 5.79; N, 12.57.
1
3
2-[2-(1H-Ben zotr ia zol-1-yl)-2-n -bu tyl-2-p h en yleth yl]bi-
p h en yl (24): separated by gradient column chromatography
1
1
1
H
19
N
3
on alumina, colorless solid, mp 66.3-69.0 °C; H NMR δ
-0.01-0.04 (m, 1H), 0.55 (t, J ) 7.1 Hz, 3H), 0.55-0.67 (m,
1H, overlapped), 0.89-1.04 (m, 2H), 2.12-2.32 (m, 2H), 4.20
(d, J ) 13.5 Hz, 1H), 4.38 (d, J ) 13.8 Hz, 1H), 6.09 (d, J )
7.7 Hz, 1H), 6.55 (d, J ) 8.2 Hz, 1H), 6.86 (d, J ) 7.3 Hz, 2H),
6.87-6.91 (m, 1H, overlapped), 7.04-7.38 (m, 12H), 8.06 (d,
J ) 8.2 Hz, 1H); 13C NMR δ 13.5, 22.5, 25.2, 36.6, 38.5, 71.4,
112.3, 119.7, 123.3, 126.1, 126.3, 126.5, 126.6, 126.7, 127.5,
128.1, 128.2, 129.4, 130.5, 131.0, 132.3, 132.5, 141.5, 142.0,
1
1
alumina, white solid; mp 105.7-107.7 °C; H NMR δ 0.79 (t,
J ) 6.9 Hz, 3H), 0.70-0.90 (m, 1H, overlapped), 1.12-1.39
(
m, 3H), 2.63-2.83 (m, 2H), 3.08-3.26 (m, 2H), 3.54-3.62 (dd,
J ) 6.9 and 16.5 Hz, 1H), 3.97-4.05 (m, 1H), 6.66 (t, J ) 8.3
Hz, 3H), 6.88 (t, J ) 7.4 Hz, 1H), 7.10-7.37 (m, 9H), 8.06 (d,
1
3
J ) 8.7 Hz, 1H); C NMR δ 13.8, 22.7, 25.4, 36.2, 37.5, 63.2,
29 3
143.5, 146.6. Anal. Calcd for C30H N O: C, 83.49; H, 6.77;
N, 9.74. Found: C, 83.29; H, 6.97; N, 9.66.
6
1
9.4, 112.1, 114.2, 120.0, 120.7, 123.6, 126.3, 126.5, 128.0,
28.8, 129.3, 132.1, 142.1, 146.9, 158.3. Anal. Calcd for
1-[4-(3-Meth yl-1H-in d ol-1-yl)-1-p h en ylbu tyl]-1H-ben zo-
tr ia zole (27): separated by gradient column chromatography
on silica gel, light yellow microcrystals, mp 120.9-122.2 °C;
C
25
H
27
N
3
O: C, 77.89; H, 7.06; N, 10.90. Found: C, 78.17; H,
.37; N, 11.21.
-[1-(4-Met h ylp h en yl)-3-p h en ylp r op yl]-1H -b en zot r i-
a zole (15): separated by column chromatography on silica gel
with hexanes/ethyl acetate, 4:1, colorless oil; H NMR δ 2.29
s, 3H), 2.58-2.82 (m, 3H), 3.11-3.24 (m, 1H), 5.72 (dd, J )
.0 and 9.6 Hz, 1H), 7.11 (d, J ) 8.9 Hz, 2H), 7.18-7.39 (m,
0H), 8.07 (d, J ) 7.8 Hz, 1H); 13C NMR δ 21.0, 32.4, 36.2,
2.3, 109.8, 119.9, 123.8, 126.2, 126.7, 127.0, 128.5, 129.5,
7
1
1
H NMR δ 1.70-1.75 (m, 2H), 2.25 (s, 3H), 2.31-2.40 (m, 1H),
2.72-2.79 (m, 1H), 3.96 (t, J ) 6.8 Hz, 2H), 5.36 (dd, J ) 6.3
and 8.9 Hz, 1H), 6.69 (s, 1H), 7.00-7.24 (m, 11H), 7.54 (d, J )
7.5 Hz, 1H), 7.97 (d, J ) 8.7 Hz, 1H); C NMR δ 9.8, 27.2,
32.7, 45.7, 63.2, 109.3, 109.9, 110.6, 118.9, 119.3, 120.0, 121.8,
124.1, 125.5, 126.9, 127.3, 128.5, 129.0, 133.0, 136.4, 139.1,
1
1
3
(
6
1
6
1
146.3. Anal. Calcd for C25
24 4
H N : C, 78.92; H, 6.36; N, 14.73.
32.8, 136.1, 138.0, 140.4, 146.2. Anal. Calcd for C22
H
21
N
3
:
Found: C, 78.85; H, 6.53; N, 14.49.
C, 80.70; H, 6.48; N, 12.84. Found: C, 80.50; H, 6.47; N, 13.04.
-(1,3-Dip h en ylh ep t yl)-1H -b en zot r ia zole (17): sepa-
1-[1-Meth yl-4-(3-m eth yl-1H-in d ol-1-yl)-1-p h en ylbu tyl]-
1H-ben zotr ia zole (29): separated by gradient column chro-
matography, light yellow oil; H NMR δ 1.35-1.41 (m, 1H),
3
1
rated by column chromatography on silica gel with hexanes/
1
ethyl acetate, 4:1, yellow oil; H NMR δ 0.82 (t, J ) 7.6 Hz,
1.71-1.77 (m, 1H), 1.94 (s, 3H), 2.16 (s, 3H), 2.41-2.51 (m,
1H), 2.56-2.66 (m, 1H), 3.80-3.89 (m, 2H), 6.46 (d, J ) 8.5
Hz, 1H), 6.56 (s, 1H), 6.91-7.03 (m, 6H), 7.06-7.16 (m, 4H),
3
2
H), 0.80-0.84 (m, 1H, overlapped), 1.18-1.32 (m, 3H), 1.98-
.08 (m, 1H), 2.52-2.69 (m, 2H), 2.79-3.02 (m, 3H), 6.69 (d,
1
3
J ) 8.3 Hz, 1H), 7.02 (d, J ) 7.4 Hz, 2H), 7.08-7.34 (m, 10H),
7.42 (d, J ) 8.7 Hz, 1H), 7.93 (d, J ) 8.3 Hz, 1H); C NMR δ
9.5, 24.7, 26.7, 37.9, 45.6, 67.2, 108.9, 110.2, 111.9, 118.4, 118.9,
119.8, 121.3, 123.5, 124.9, 125.6, 126.5, 127.8, 128.6, 128.7,
1
3
8
3
1
.08 (d, J ) 8.2 Hz, 1H); C NMR δ 13.8, 22.7, 25.3, 29.8 36.9,
8.9, 70.2, 112.1, 119.9, 123.5, 125.9, 126.3, 127.8, 128.2, 128.3,
28.6, 132.2, 141.1, 142.4, 146.8. Anal. Calcd for C25
H
27
N
3
:
26 4
132.0, 136.1, 142.9, 146.8. Anal. Calcd for C26H N : C, 79.16;
C, 81.26; H, 7.38; N, 11.37. Found: C, 81.03; H, 7.57; N, 11.16.
-[2-(1H-Ben zotr ia zol-1-yl)-2-(5-m eth yl-2-th ien yl)eth -
H, 6.64; N, 14.20. Found: C, 79.22; H, 6.94; N, 14.24.
Gen er a l P r oced u r e for th e Syn th esis of Com p ou n d s
11a -d , 13, 16, 18, 21a -c, 23, 25, 28, a n d 30. To a solution
of the appropriate 10, 12, 15, 17, 20, 22, 24, 27, or 29 (1 mmol)
in the appropriate solvent (Table 1) (50 mL) was added the
appropriate Lewis acid (for the type and amount see Table 1).
The mixture was stirred at the temperature indicated (Table
1) until the intermediates were consumed (indicated in Table
1). The solvent was removed under reduced pressure, and the
residue was treated with dichloromethane (10 mL) and sodium
hydroxide aqueous solution (2 M, 25 mL). The aqueous layer
was extracted with dichloromethane (3 × 15 mL) and dried
2
yl]bip h en yl (20a ): white needles, mp 107.8-108.5 °C (hex-
1
anes/ethyl acetate, 1:15); H NMR δ 2.32 (s, 3H), 3.89-3.96
(
1
m, 2H), 5.88 (dd, J ) 6.6 and 8.8 Hz, 1H), 6.44 (d, J ) 3.4 Hz,
H), 6.49 (d, J ) 2.6 Hz, 1H), 7.00-7.06 (m, 3H), 7.12-7.17
(m, 2H), 7.24-7.29 (m, 4H), 7.38-7.43 (m, 3H), 7.96 (d, J )
1
3
7
1
1
.5 Hz, 1H); C NMR δ 15.1, 39.8, 59.2, 109.5, 119.8, 123.6,
24.6, 125.5, 126.9, 127.0, 127.2, 127.4, 128.5, 129.0, 130.1,
30.4, 132.4, 133.8, 138.9, 140.3, 141.2, 142.0, 145.9. Anal.
Calcd for C25
5.77; H, 5.38; N, 10.65.
-[2-(1H -Be n zot r ia zol-1-yl)-2-p h e n yle t h yl]b ip h e n yl
20b): separated by gradient column chromatography on silica
21 3
H N S: C, 75.92; H, 5.35; N, 10.62. Found: C,
7
2
4
(MgSO ). The crude product was purified accordingly.
(
1-(5-Meth ylth iop h en -2-yl)-1,2,3,4-tetr a h yd r on a p h th a -
len e (11a ): separated by column chromatography on silica
1
gel, colorless oil; H NMR δ 3.86 (dd, J ) 6.3 and 14.4 Hz,