670
Stará et al.:
ph y on silica gel (h exan e–eth er–aceton e 80 : 10 : 10 to 50 : 30 : 20) afforded 32 (98 m g,
72%) as an oil. IR (CHCl3): 3 628 w (sh ), 3 607 m , 3 459 w (br), 3 068 w, 1 608 m , 1 600 w,
1 583 w, 1 570 w (sh ), 1 497 vs, 1 480 w (sh ), 1 452 w, 1 424 w, 1 384 w, 1 275 m , 1 233 m ,
1 152 w, 1 102 w, 1 090 w, 1 034 m , 1 020 m (br), 948 w, 825 m . 1H NMR (500 MHz,
CDCl3): 2.45 (brs, 1 H, OH); 2.82 (brs, 1 H, OH); 4.86 (brs, 2 H, CH2Ar′); 4.87 (brs, 2 H,
CH2Ar); 7.01 (dt, 1 H, J = 8.4, 8.4, 2.7, 5′-H); 7.19 (ddt, 1 H, J = 9.2, 2.7, 0.5, 0.5, 3′-H); 7.32
(dt, 1 H, J = 7.4, 7.4, 1.5, 4-H); 7.37 (dt, 1 H, J = 7.5, 7.5, 1.5, 5-H); 7.44 (ddq, 1 H, J = 7.4,
1.4, 0.6, 0.6, 0.6, 6-H); 7.54 (dd, 1 H, J = 8.5, 5.6, 6′-H); 7.56 (ddd, 1 H, J = 7.3, 1.6, 0.6,
3-H). 13C NMR (CDCl3): 63.79 (t, CH2Ar′), 64.50 (t, CH2Ar), 90.58 (s, C≡C–Ar′), 91.25 (s,
C≡C–Ar′), 114.75 (dd, JC–F = 22.0, C-3′), 115.11 (dd, JC–F = 22.9, C-5′), 117.60 (d, JC–F = 3.2,
C-1′), 121.87 (s, C-2), 127.90 (d, C-4), 128.09 (d, C-6), 128.89 (d, C-5), 132.39 (d, C-3),
134.14 (dd, JC–F = 8.2, C-6′), 142.10 (s, C-1), 145.23 (d, JC–F = 7.8, C-2′), 162.71 (d, JC–F
=
250.9, C-4′). 19F NMR (CDCl3): –110.29 (ddd, JF–H = 9.2, 8.3, 5.6). EI MS (m/z, rel. in ten sity):
256 (M+•, 9), 238 (96), 220 (11), 209 (100), 196 (22), 189 (16), 183 (40), 137 (21), 119 (17),
109 (11), 91 (13), 77 (11), 63 (7), 51 (8). HR EI MS: calculated for C16H13FO2 256.0899;
foun d 256.0886.
{2-[2-(5-Fluoro-2-h ydroxym eth ylph en yl)eth yn -1-yl]ph en yl}m eth an ol (33)
Method F). Com poun d 6b (170 m g, 0.726 m m ol), 30 (109 m g, 0.726 m m ol, 1.0 equiva-
len t), Pd(PPh 3)4 (84 m g, 0.073 m m ol, 10 m ole %), piperidin e (3 m l), 80 °C, 2 h . Flash ch ro-
m atograph y on silica gel (h exan e–eth er–aceton e 80 : 10 : 10) afforded 33 (184 m g, 99%) as
an oil. IR (CHCl3): 3 608 m , 3 465 w (br), 3 072 w, 2 933 w, 2 882 w, 2 209 vw, 1 581 vs,
1 508 s, 1 496 vs, 1 480 w (sh ), 1 464 w, 1 418 w, 1 384 w, 1 345 vw, 1 308 m , 1 263 w,
1 199 m , 1 138 w, 1 108 w, 1 083 w, 1 011 s, 1 034 m , 950 m , 875 m , 829 m , 607 w, 538 w.
1H NMR (500 MHz, aceton e-d6): 4.94 (brd, 2 H, J = 6.3, CH2Ar); 4.97 (brd, 2 H, J = 6.3,
CH2Ar′); 7.27 (dt, 1 H, J = 8.6, 8.6, 2.7, 4′-H); 7.38 (dd, 1 H, J = 9.4, 2.7, 6′-H); 7.40 (dtt, 1 H,
J = 7.6, 7.6, 1.5, 0.7, 0.7, 5-H); 7.51 (dt, 1 H, J = 7.6, 7.6, 1.5, 4-H); 7.64 (brdd, 1 H, J = 7.6,
1.5, 6-H); 7.70 (ddt, 1 H, J = 8.6, 5.9, 0.9, 0.9, 3′-H); 7.70 (ddt, 1 H, J = 7.6, 1.5, 0.9, 0.9,
3-H). 13C NMR (aceton e-d6): 62.71 (t, CH2Ar), 63.25 (t, CH2Ar′), 91.02 (d, JC–F = 3.2,
C≡C–Ar′), 93.21 (s, C≡C–Ar′), 116.35 (dd, JC–F = 21.1, C-4′), 118.73 (dd, JC–F = 22.9, C-6′),
121.23 (s, C-2), 123.46 (d, JC–F = 9.7, C-1′), 127.63 (d, C-6), 127.73 (d, C-4), 129.69 (d, JC–F
=
8.2, C-3′), 129.84 (d, C-5), 132.78 (d, C-3), 141.03 (s, C-1), 145.02 (d, JC–F = 3.4, C-2′),
162.16 (d, JC–F = 242.7, C-5′). 19F NMR (aceton e-d6): –112.99 (tt, JF–H = 8.8, 5.4). EI MS (m/z,
rel. in ten sity): 256 (M+•, 3), 238 (100), 221 (13), 209 (65), 207 (18), 196 (16), 189 (9), 183
(25), 137 (13), 119 (13), 109 (5), 91 (9), 77 (6). HR EI MS: calculated for C16H11FO (M – H2O)
238.0794; foun d 238.0799.
2-[2-(2-Hydroxym eth ylph en yl)eth yn -1-yl]-4-(m eth oxycarbon yl)ben zyl Acetate (34)
Method F). Com poun d 6b (105 m g, 0.449 m m ol), 31 (104 m g, 0.448 m m ol, 1.0 equiva-
len t), Pd(PPh 3)4 (26 m g, 0.022 m m ol, 5 m ole %), diisopropylam in e (5 m l), 80 °C, 1 h . Flash
ch rom atograph y on silica gel (petroleum eth er–eth er–aceton e 80 : 10 : 10) afforded 34 (99 m g,
65%) as an oil. IR (CHCl3): 3 607 w, 2 954 w, 2 880 vw, 2 210 vw, 1 746 m (sh ), 1 724 vs,
1 608 w, 1 572 w, 1 497 w, 1 483 w, 1 450 w, 1 438 m , 1 413 w, 1 380 w, 1 363 w, 1 318 m ,
1 282 m , 1 255 s, 1 156 w, 1 133 w (sh ), 1 106 w, 1 043 w, 1 030 w, 1 008 w, 989 w, 916 w,
845 vw. 1H NMR (500 MHz, CDCl3): 2.15 (s, 3 H, CH3CO2); 2.51 (brs, 1 H, OH); 3.95 (s, 3 H,
Collect. Czech. Chem. Commun. (Vol. 64) (1999)