0.329 g, 1.76 mmol). Light-brown powder after trituration with diethyl ether. Yield 0.15 g (39 %),
mp 154-156 °C; IR (film) ν = 3902, 3752, 3674, 3420 (OH), 3058, 2922, 2855, 2749, 2710, 2593,
1964, 1891, 1810, 1750, 1589, 1479, 1435, 1411, 1379, 1334, 1280, 1249, 1223, 1149, 1111, 1076,
1
1045, 1017, 948, 901, 820, 753, 693, 634, 580, 544, 508, 486, 441 cm-1. H NMR (DMSO-d6, 600
3
MHz) δ = 10.08 (br. s, 1H, OH), 7.76 (dd, 3JPH 13.2, JHH 7.6 Hz, 2H, o-PhH), 7.67 (br. t, 3JHH 7.5
3
3
4
Hz, 1H, p-PhH), 7.62 (br. t, JHH 7.8 Hz, 1H, H18), 7.56 (ddd, JHH 7.7, JPH 3.3 Hz, 2H, m-PhH),
7.43 (d, JHH 7.5 Hz, 2H, H16), 7.40-7.34 (m, 2H, H23,24), 7.36 (d, JHH 7.4 Hz, 2H, H17), 7.07 (d,
3
3
2JPH 18.1 Hz, 1H, H3), 7.08-7.05 (m, 1H, H26), 7.01 (dd, JHH 7.9, JHH 6.2 Hz, 1H, H25), 6.84 (dd,
3JHH 8.6, 4JHH 2.2 Hz, 1H, H7), 6.70 (d, 3JHH 8.6 Hz, 1H, H8), 6.53 (d, 4JHH 2.1 Hz, 1H, H5), 3.75 (s,
3H, OCH3), 2.43 (d, 2JPH 14.1 Hz, CH3) ppm. 13C, 13C{1H} NMR (DMSO-d6, 151 MHz) δ = 160.7
3
3
(m (br. s), C4), 160.6 (m (d), JPC 2.0 Hz, C22), 153.0 (br. dd (d), JHC 9.0, JHC 8.7, JPC 1.3 Hz,
2
3
3
4
C8a), 138.6 (m (d), JPC 17.7 Hz, C15), 136.6 (dd (br. d), JHC 161.9, JHC 8.1, JPC 2.0 Hz, C24),
3
1
3
4
133.7 (dm (d), 1JHC 163.9, 2JPC 8.8 Hz, C26), 133.4 (br. dm (d), 1JHC 164.1, 4JPC 3.1 Hz, C12), 131.7
(dm (d), JHC 162.7, JPC 10.1 Hz, C10), 130.2 (dm (s), JHC 161.7 Hz, C18), 129.9 (dd (s), JHC
1
2
1
1
165.8, 3JHC 6.0 Hz, C7), 129.0 (ddd (d), 1JHC 164.5, 3JHC 7.4, 3JPC 13.1 Hz, C11), 128.5 (dd (s), 1JHC
164.3, JHC 4.5 Hz, C5), 128.2 (dd (s), JHC 162.0, JHC 7.4 Hz, C17), 127.3 (br. dm (s), JHC 160.3,
3
1
3
1
3JHC 6.5 Hz, C16), 123.7 (m (d), JPC 7.6 Hz, C4a), 122.1 (dt (s), JHC 11.0, JHC 3.6 Hz, C6), 121.3
(ddd (d), 1JHC 165.6, 3JHC 7.2, 3JPC 13.0 Hz, C25), 120.6 (dm (d), 1JPC 93.0 Hz, C9), 116.9 (d (s), 1JHC
164.0 Hz, C8), 111.5 (dm (d), 1JHC 163.4, 3JPC 5.4 Hz, C23), 106.6 (dm (d), 1JPC 92.0 Hz, C21), 106.5
3
3
2
(dd (d), JHC 162.6, JPC 92.5 Hz, C3), 55.7 (q (s), JHC 146.3 Hz, OCH3), 9.2 (qd (d), JHC 134.7,
1JPC 60.4 Hz, CH3) ppm. 31P{1H} NMR (CDCl3, 202 MHz) δ = 10.7 ppm. Anal. Calcd. for
C28H25Cl2O2P (%): C 67.89; H 5.09; Cl 14.31; P 6.25. Found (%): C 67.88; H 5.05; Cl 14.34; P
6.26. ESI-MS: m/z = [M – Cl]+ 459.2 (calculated for C28H25ClO2P+ 459.1).
1
1
1
1
(Z)-(2-(5-Chloro-2-hydroxyphenyl)-2-phenylvinyl-(4-methoxyphenyl)(methyl)(phenyl)phos-
phonium chloride (7b). Synthesized from 0.31 g of compound 6a and Grignard reagent, prepared
from magnesium turnings (0.05 g, 1.76 mmol) and 4-bromoanisol (0.22 ml, 0.329 g, 1.76 mmol).
Light-brown powder after trituration with diethyl ether. Yield 0.23 g (58 %), mp 152-155 °C; IR
(KBr) ν = 3392 (OH), 3055, 2969, 2699, 2564, 1596, 1568, 1505, 1462, 1439, 1408, 1301, 1266,
1
1218, 1187, 1156, 1115, 1022, 949, 901, 826, 768, 746, 690, 632, 578, 526, 504 cm-1. H NMR
3
(CDCl3, 400 MHz) δ = 7.67-7.62 (m, 3H, ArH), 7.56-7.52 (m, 4H, ArH), 7.44 (br. d, JHH 6.8 Hz,
2H, H16), 7.40-7.31 (m, 3H, H17,18), 7.14 (d, 3JHH 8.7 Hz, 1H, H8), 7.00 (br. d, 3JHH 6.7 Hz, 2H, H24),
3
4
2
4
6.89 (dd, JHH 8.8, JHH 2.4 Hz, 1H, H7), 6.84 (d, JPH 18.7 Hz, 1H, H3), 6.39 (d, JHH 2.6 Hz, 1H,
H5), 3.86 (s, 3H, OCH3), 2.45 (d, JPH 13.5 Hz, 3H, CH3) ppm. C, C{1H} NMR (CDCl3, 101
MHz) δ = 164.4 (m (d), 4JPC 2.9 Hz, C24), 163.4 (m (d), 2JPC 1.6 Hz, C4), 153.6 (br. dd (d), 3JHC 8.7,
3JHC 8.4, 4JPC 1.3 Hz, C8a), 139.2 (m (d), 3JPC 17.4 Hz, C15), 134.6 (br. dm (d), 1JHC 163.5, 2JPC 12.1
2
13
13
Hz, C22), 134.3 (br. dm (d), JHC 161.2, JPC 2.8 Hz, C10), 132.3 (dm (d), JHC 162.0, JPC 10.4 Hz,
1
4
1
2
C10), 131.2 (dm (s), JHC 161.2 Hz, C18), 130.7 (dd (s), 1JHC 164.6, 3JHC 5.4 Hz, C7), 130.1 (br. ddd
1
(d), JHC 166.0, JHC 6.3, JPC 12.7 Hz, C11), 129.0 (br. dm (d), JHC 165.6, JPC 1.3 Hz, C5), 128.9
1
3
3
1
4
(dd (s), 1JHC 161.2, 3JHC 6.1 Hz, C17), 128.3 (br. dm (s), 1JHC 161.7 Hz, C16), 124.2 (m (d), 3JPC 6.9
Hz, C4a), 123.6 (dt (s), JHC 11.3, JHC 4.0 Hz, C6), 121.7 (dm (d), JPC 90.5 Hz, C9), 118.8 (d (s),
3
2
1
1JHC 163.7 Hz, C8), 115.9 (br. ddd (d), 1JHC 163.4, JHC 1.8, 3JPC 14.1 Hz, C23), 109.7 (dm (d), JPC
97.2 Hz, C21), 106.7 (dd (d), 1JHC 160.4, 1JPC 92.8 Hz, C3), 56.0 (q (s), 1JHC 145.4 Hz, OCH3), 10.6
(qd (d), 1JHC 136.0, 1JPC 61.0 Hz, CH3) ppm. 31P{1H} NMR (162 MHz, CDCl3) δ = 11.5 ppm. Anal.
Calcd for C28H25Cl2O2P (%): C 67.89; H 5.09; Cl 14.31; P 6.25. Found (%): C 67.83; H 5.12; Cl
14.24; P 6.27. ESI-MS: m/z = [M – Cl]+ 459.2 (calculated for C28H25ClO2P+ 459.1).
2
1
(Z)-(2-(5-chloro-2-hydroxyphenyl)-2-phenylvinyl)(methyl)(phenyl)(thiophen-2-yl)phosphonium
chloride (7c). Synthesized from 0.31 g of compound 6a and Grignard reagent, prepared from
magnesium turnings (0.05 g, 1.76 mmol) and 2-bromothiophene (0.17 ml, 0.29 g, 1.76 mmol).
Light-grey powder after trituration with diethyl ether. Yield 0.37 g (97 %), mp 146-149 °C; IR
(KBr) ν = 3381 (OH), 3054, 2895, 2694, 2563, 1894, 1762, 1601, 1586, 1562, 1493, 1438, 1404,