9286 J . Org. Chem., Vol. 61, No. 26, 1996
Arcadi et al.
p-Cyan o-o-((tr im eth ylsilyl)eth yn yl)ph en yl acetate (5c):
mp 47-48 °C; IR 2200, 2120, 1760, 820 cm-1; 1H NMR δ 7.76-
7.18 (m, 3H), 2.34 (s, 3H), 0.25 (s, 9H); 13C NMR δ 167.5, 154.8,
136.6, 132.8, 124.6, 123.4, 116.9, 109.9, 102.6, 96.9, 20.5, -0.51;
MS m/ e (relative intensity) 257 (M+, 8), 200 (100), 184 (22).
Anal. Calcd for C14H15NO2Si: C, 65.34; H, 5.87; N, 5.44.
Found: C, 65.58; H, 5.83; N, 5.49.
(100). Anal. Calcd for C16H11ClO2: C, 70.99; H, 4.10.
Found: C, 70.65; H, 4.07.
p-Ben zoyl-o-((17â-acetylan dr osta-3,5-dien -3-yl)eth yn yl)-
p h en yl a ceta te (12e): mp 164-165 °C; IR 2160, 1770,1760,
1700, 780, 710, 700 cm-1; 1H NMR δ 7.91-7.18 (m, 8 H), 6.35
(s, 1H), 5.56 (bs, 1H), 2.36 (s, 3H), 2.12 (s, 3H), 1.05 (s, 3H),
1.84 (s, 3H); 13C NMR δ 209.4, 194.8, 168.2, 154.1, 141.0, 136.5,
134.5, 130.5, 128.9, 127.2, 122.3, 97.5, 83.4; MS m/ e (relative
intensity) 560 (M+, 6), 518 (6), 105 (100). Anal. Calcd for
C38H40O4: C, 81.40; H, 7.19. Found: C, 81.15; H, 7.15.
p-Ben zoyl-o-(h ex-1-yn yl)p h en yl a ceta te (12f): oil; IR
p-Meth yl-o-eth yn ylp h en ol (3b): oil; IR (neat) 3500, 3370,
1
2160, 790 cm-1; H NMR δ 7.04-6.69 (m, 3H), 5.72 (s, 1H),
3.26 (s, 1H), 2.09 (s, 3H); 13C NMR δ 157.0, 134.0, 133.5, 131.4,
116.6, 109.8, 85.7, 80.5, 22.0; MS m/ e (relative intensity) 132
(M+, 100), 103 (43). Anal. Calcd for C9H8O: C, 81.79; H, 6.10.
Found: C, 81.49; H, 6.14.
2190, 1765, 1660, 1270, 700 cm-1 1H NMR δ 7.89-715 (m,
;
8H), 2.37 (t, 3H), 2.33 (s, 3 H), 1.52 (m, 4H), 0.92 (t, 3H); 13C
NMR δ 194.5, 166.0, 154.3, 136.8, 134.9, 134.6, 132.3, 131.7,
130.0, 128.6, 128.2, 126.1, 122.0, 116.2, 96.5, 74.6, 30.3, 21.6,
20.5, 18.8, 13.3; MS m/ e (relative intensity) 320 (M+, 8), 278
(100), 105 (60). Anal. Calcd for C21H20O3: C, 78.73; H, 6.29.
Found: C, 79.01; H, 6.32.
p-Ben zoyl-o-eth yn ylp h en ol (3c): mp 145-146 °C; IR
3260, 1630, 1370, 820, 690 cm-1; 1H NMR δ 7.91-7.02 (m, 9H),
3.48 (s, 1H); 13C NMR δ 194.8, 160.9, 137.6, 135.1, 133.3, 132.2,
129.7, 128.3, 128.2, 114.9, 108.5, 85.0, 76.4; MS m/ e (relative
intensity) 222 (M+, 72), 145 (100), 105 (32). Anal. Calcd for
C15H10O2: C, 81.07; H, 4.54. Found: C, 81.38; H, 4.56.
p-Cya n o-o-eth yn ylp h en ol (3d ): mp 129-130 °C; IR 3350,
3270, 2200, 875, 805, 760 cm-1; 1H NMR δ 7.70-7.04 (m, 3H),
6.58 (bs, 1H), 3.57 (s, 1H); 13C NMR δ 160.7, 136.5, 133.3,
118.1, 116.2, 110.0, 104.0, 86.2, 76.2; MS m/ e (relative
intensity) 143 (M+, 100), 115 (66). Anal. Calcd for C9H5NO:
C, 75.52; H, 3.52; N, 9.78. Found: C, 75.68; H, 3.48; N, 9.72.
p-Meth yl-o-(p h en yleth yn yl)p h en ol (9b): mp 59-60 °C;
1
IR 3520, 2180, 765, 690 cm-1; H NMR δ 7.49-6.83 (m, 8H),
5.95 (s, 1H), 2.22 (s, 3H); 13C NMR 154.3, 131.7, 131.4, 131.0,
129.4, 128.5, 128.3, 122.4, 121.8, 114.5, 109.1, 95.6, 83.4; MS
m/ e (relative intensity) 208 (M+, 100), 178 (34). Anal. Calcd
for C15H12O: C, 86.51; H, 5.81. Found: C, 86.23; H, 5.78.
o-(P h en yleth yn yl)p h en ol (9c): mp 47-48 °C; IR 3500,
1
2115, 820, 660 cm-1; H NMR δ 7.53-6.68 (m, 9H), 5.91 (bs,
Typ ica l P r oced u r e for th e P r ep a r a tion of o-Alk y-
n ylp h en yl Aceta tes 12 a n d o-Alk yn ylp h en ols 9. p-Ben -
zoyl-o-(p h en yleth yn yl)p h en yl Aceta te (12a ) a n d p-Ben -
zoyl-o-(p h en yleth yn yl)p h en ol (9a ). To a stirred solution
of p-benzoyl-o-acetoxyphenyl iodide (4b) (1.670 g, 4.56 mmol)
and Et3N (10 mL) in DMF (2 mL) were added phenylacetylene
(0.930 g, 9.12 mmol) and Pd(OAc)2(PPh3)2 (0.068 g, 0.09 mmol).
The reaction mixture was stirred at 80 °C for 4.5 h under
nitrogen. EtOAc and 0.1 N HCl were added, and the organic
layer was separated, washed with water, dried (Na2SO4), and
concentrated under reduced pressure. The residue purified
by flash chromatography (silica gel, n-hexane) afforded 12a
(1.380 g, 89% yield): mp 106-107 °C; IR 1755, 1660, 1380,
1H); 13C NMR 156.4, 131.6, 131.5, 130.4, 128.7, 128.4, 122.3,
120.4, 114.7, 109.5, 96.3, 83.0; MS m/ e (relative intensity) 194
(M+, 100), 165 (61). Anal. Calcd for C14H10O: C, 86.57; H,
5.19. Found: C, 86.29; H, 5.22.
p-Ch lor o-o-(p h en yleth yn yl)p h en ol (9d ): mp 92-93 °C;
1
IR 3400, 790, 730, 660 cm-1; H NMR δ 7.52-6.85 (m, 8H),
5.90 (bs, 1H); 13C NMR 155.0, 131.5, 130.9, 130.3, 128.5, 128.4,
116.0, 97.1, 81.8; MS m/ e (relative intensity) 230 (M+, 25),
228 (M+, 100), 165 (79). Anal. Calcd for C14H9ClO: C, 73.53;
H, 3.97. Found: C, 73.77; H, 4.00.
p-Ben zoyl-o-((17-a cetyla n dr osta -3,5-d ien -3-yl)eth yn yl)-
p h en ol (9e): mp 84-87 °C; IR 3350, 2160, 1700, 1650, 1590,
780, 690 cm-1; 1H NMR δ 7.85-7.01 (m, 8H), 6.40 (s, 1H), 5.57
(bs, 1H), 2.04 (s, 3H), 0.95 (s, 3H), 0.85 (s, 3H); 13C NMR δ
209.6, 194.4, 159.8, 141.0, 137.8, 136.7, 134.4, 132.0, 128.8,
127.4, 116.0, 110.4, 99.1, 81.9; MS m/ e (relative intensity) 518
(M+, 19), 105 (100). Anal. Calcd for C36H38O3: C, 83.36; H,
7.38. Found: C, 83.59; H, 7.41.
1
730, 695 cm-1; H NMR δ 8.01-7.26 (m, 13 H), 2.41 (s, 3H);
13C NMR δ 194.8, 166.4, 154.4, 137.1, 135.3, 134.6, 132.7,
131.8, 131.6, 131.0, 126.9, 126.4, 122.4, 121.5, 117.7, 95.1, 93.4,
20.9; MS m/ e (relative intensity) 340 (M+, 19), 298 (89), 221
(100). Anal. Calcd for C23H16O3: C, 81.16 ; H, 4.74. Found:
C, 80.88; H, 4.71.
12a was dissolved in acetone (25 mL), 2 N HCl (7 mL) was
added, and the reaction mixture was stirred for 12 h at 60 °C.
Then, EtOAc and water were added, and after workup, the
residue was purified by flash chromatography (silica gel, 75/
25 v/v n-hexane/EtOAc mixture) to give 9a (0.484 g, 40%
yield): mp 139-140 °C; IR 3240, 1630, 1580, 1560, 1500, 1310,
1300, 1260, 810, 745, 690 cm-1; 1H NMR δ 7.94-7.08 (m, 13H),
7.04 (bs, 1H); 13C NMR δ 195.1, 160.2, 137.6, 134.8, 132.1,
131.6, 129.9, 129.7, 129.0, 128.4, 128.3, 128.2, 121.9, 114.9,-
109.9, 96.7, 82.7; MS m/ e (relative intensity) 298 (M+, 22),
221 (80), 77(100). Anal. Calcd for C21H14O2: C, 84.54; H, 4.73.
Found: C, 81.24; H, 4.70.
p-Meth yl-o-(p h en yleth yn yl)p h en yl a ceta te (12b): oil;
IR (neat) 1760, 1490, 1200, 1180, 810, 740, 670 cm-1; 1H NMR
δ 7.48-6.96 (m, 8H), 2.34 (s, 3H), 2.32 (s, 3H); 13C NMR δ
169.1, 149.3, 135.8, 132.2, 131.5, 130.2, 128.5, 128.4, 126.3,
123.5, 121.9, 116.9, 93.7, 84.4, 20.8, 20.7; MS m/ e (relative
intensity) 250 (M+, 9), 208 (100), 77 (11). Anal. Calcd for
C17H14O2: C, 81.58; H, 5.64. Found: C, 81.29; H, 5.60.
p-Ben zoyl-o-(h ex-1-yn yl)p h en ol (9f): oil; IR 3300, 1650,
1
770, 695 cm-1; H NMR δ 7.64-6.61 (m, 8H), 5.65 (bs, 1H),
2.45 (t, 2H), 1.59 (m, 4H), 0.94 (t, 3H); 13C NMR 196.6, 161.4,
160.2, 132.2, 129.9, 128.8, 128.6,126.1, 127.4, 114.3, 110.5,
102.2, 30.5, 28.5, 22.1, 13.7; MS m/ e (relative intensity) 278
(M+, 80), 235 (100), 105 (50). Anal. Calcd for C19H18O2: C,
81.99; H, 6.52. Found: C, 81.71; H, 6.49.
Typ ica l P r oced u r e for th e P r ep a r a tion of 2-Su bsti-
tu ted -ben zo[b]fu r a n s 7 fr om o-Eth yn ylp h en ols 3. P r o-
ced u r e A. 2-(Ch olesta -3,5-d ien -3-yl)ben zo[b]fu r a n (7a ).
To a stirred solution of o-ethynylphenol (3a ) (0.174 g, 1.47
mmol) and Et3N (4 mL) in DMF (4 mL) were added cholesta-
3,5-dien-3-yl triflate (6a ) (0.630 g, 1.22 mmol), Pd(OAc)2(PPh3)2
(0.046 g, 0.06 mmol), and CuI (0.012 g, 0.06 mmol). The
reaction mixture was stirred at 80 °C for 1 h under nitrogen.
Diethyl ether and 0.1 N HCl were added, and the organic layer
was separated, washed with water, dried (Na2SO4), and
concentrated under reduced pressure. The residue purified
by flash chromatography (silica gel, 97/3 v/v n-hexane/EtOAc)
afforded 7a (0.460 g, 78% yield): mp 210-212 °C; IR 2950,
1620, 1470,1450, 780, 740, 730 cm-1; 1H NMR δ 7.50-715 (m,
4H), 6.78 (s, 1H), 5.71 (bs, 1H); 13C NMR δ 157.2, 154.6, 141.5,
129.3, 127.2, 126.6, 123.9, 125.5, 122.5, 120.4, 110.7, 101.1;
MS m/ e (relative intensity) 484 (M+, 100), 131 (63). Anal.
Calcd for C35H48O: C, 86.72; H, 9.98. Found: C, 86.99; H,
10.01.
o-(P h en yleth yn yl)p h en yl a ceta te (12c): mp 36-37 °C;
IR 2180, 1760, 1260, 730, 670 cm-1; 1H NMR δ 7.58-7.08 (m,
9H), 2.34 (s, 3H); 13C NMR δ 166.6, 151.5, 132.8, 131.4, 128.4,
128.3, 125.8, 122.8, 122.2, 122.1, 117.3, 94.1, 84.2; MS m/ e
(relative intensity) 236 (M+, 11), 194 (100), 165 (45). Anal.
Calcd for C16H12O2: C, 81.34; H, 5.12. Found: C, 81.65; H,
5.15.
p-Ch lor o-o-(p h en ylet h yn yl)p h en yl a cet a t e (12d ): mp
53-54 °C; IR 1770, 1275, 730, 675 cm-1; 1H NMR δ 7.53-
7.01 (m, 8 H), 2.33 (s, 3H); 13C NMR δ 168.6, 150.0, 132.45,
129.41, 128.9, 128.4, 123.5, 122.3, 119.0, 95.3, 83.0, 20.7; MS
m/ e (relative intensity) 272 (M+, 3), 270 (M+, 9), 230 (31), 228
2-(17â-(Ben zoyloxy)a n d r ost -2-en -3-yl)b en zo[b]fu r a n
1
(7b): mp 203-204 °C; IR 1710, 1260, 770, 725, 695 cm-1; H
NMR δ 8.07-8.02 (m, 2H), 7.72-7.14 (m, 7H), 6.49 (s, 2H),
4.82 (t, 1H), 4.23 (m, 1H); 13C NMR δ 166.5, 157.9, 154.4, 132.7,
128.5, 126.3, 122.5, 110.7, 100.1, 83.3; MS m/ e (relative