Al-Bashir et al.
1551
ratio, as shown in procedure A. The obtained colourless ma-
terial was recrystallized from ethyl acetate to give 2.59 g
(ca. 64%) of the ylide: mp 232–234 °C. IR υmax (cm–1):
1584, 1485, 1436, 1269, 1104, 1018, 935, 757, 732, 694,
by phenylmethanesulfonyl fluoride in a 2:2:1 ratio. Yield:
78%; mp 210–212 °C (1, 3). IR υmax (cm–1): 1590, 1484,
1
1435, 1266, 1240, 1094, 1021, 939, 708, 692, 545, 526. H
NMR (CDCl3) (1) δH: 4.00 (2H, s), 7.03–7.15 (4H, m),
7.26–7.37 (12H, m), 7.47–7.54 (9H, m). 13C NMR (CDCl3)
(JP-C) (1) δC: 46.80 (d, J = 129 Hz, P=C), 61.83 (CH2),
125.85 (d, J = 2 Hz), 127.91, 128.09 (d, J = 92 Hz, C-1 of
P-Ph), 128.13, 128.50, 128.73 (d, J = 12 Hz, C-3 of P-Ph),
131.70, 131.94 (d, J = 3 Hz, C-4 of P-Ph), 134.27 (d, J =
10 Hz, C-2 of P-Ph), 135.20 (d, J = 9 Hz), 135.29 (d, J =
9 Hz), 135.94 (d, J = 4 Hz). 31P NMR (CDCl3) δP: 19.61 (1).
MS m/z: 506 (M+·, 60), 416 (57), 415 (48), 368 (64), 351
(90), 273 (18), 165 (64), 105 (100). Anal. calcd. for
C32H27O2PS (%): C 75.89, H 5.34, S 6.32; found: C 75.85,
H 5.44, S 6.21.
1
542. H NMR (CDCl3) δH: 3.97 (2H, s), 6.98 (2H, d, J =
8 Hz), 7.05–7.15 (4H, m), 7.27–7.30 (2H, m), 7.35–7.39
(7H, m), 7.48–7.53 (9H, m). 13C NMR (CDCl3) (JP-C) δC:
46.6 (d, J = 129 Hz, P=C), 62.06 (CH2), 127.68 (d, J =
92 Hz, C-1 of P-Ph), 128.05 (2C), 128.17 (d, J = 1.4 Hz),
128.63, 128.68 (d, J = 1.9 Hz), 128.89 (d, J = 12 Hz, C-3 of
P-Ph), 131.61, 131.69, 132.18 (d, J = 3 Hz, C-4 of P-Ph),
134.16 (d, J = 3.6 Hz), 134.28 (d, J = 10 Hz, C-2 of P-Ph),
136.63 (d, J = 4 Hz). 31P NMR (CDCl3) δP: 19.61. MS m/z:
542/540 (M+· + 2/M+·, 35/60%), 415 (30), 401 (45), 385
(80), 351 (40), 277 (100), 262 (75), 201 (45), 199 (42), 183
(80), 139 (58), 1 (64). Anal. calcd. for C32H26ClO2PS (%): C
71.04, H 4.81, S 5.92; found: C 71.21, H 4.92, S 6.03.
[(Benzylsulfonyl)(4-methylphenyl)methylene](triphenyl)-
phosphorane (7)
[(Benzylsulfonyl)(3-chlorophenyl)methylene](triphenyl)-
phosphorane (5)
Obtained by treating the obtained salt with BuLi followed
by phenylmethanesulfonyl fluoride in a 2:2:1 ratio. Yield:
74%; mp 186–189 °C (1). IR υmax (cm–1): 1625, 1502, 1483,
1435, 1264, 1244, 1144, 1106, 1094, 1043, 1028, 935, 864,
788, 754, 714, 694 (1). 1H NMR (CDCl3) (1) δH: 2.24
(3H, s), 3.99 (2H, s), 6.87 (2H, d, J = 8 Hz), 7.13–7.16
(4H, m), 7.24–7.36 (9H, m), 7.45–7.52 (9H, m). 13C NMR
(CDCl3) (JP-C) δC: 21.5 (CH3), 46.6 (d, J = 129 Hz, P=C),
61.6 (CH2), 128.30 (d, J = 92 Hz, C-1 of P-Ph), 128.58 (d,
J = 12 Hz, C-3 of P-Ph), 128.63, 128.75, 128.97 (d, J =
1 Hz), 131.73, 131.86 (d, J = 3 Hz, C-4 of P-Ph), 131.96,
132.01, 134.26 (d, J = 10 Hz, C-2 of P-Ph), 135.63 (d, J =
2 Hz), 136.11 (d, J = 4 Hz). 31P NMR (CDCl3) δP: 19.49.
MS m/z: 520 (M+·, 60), 429 (50), 416 (5), 380.7 (40), 365
(100), 277 (5), 262 (30), 165 (65), 119 (90), 91 (75). Anal.
calcd. for C33H29O2PS (%): C 76.15, H 5.58, S 6.15; found:
C 76.17, H 5.64, S 5.79.
The quaternary salt, 3-chlorobenzyltriphenylphosphonium
chloride (Ph3P+CH2m-Cl-C6H4Cl–), was prepared by
refluxing 10.49 g of triphenylphosphine (0.04 mol) with
6.44 g of 3-chlorobenzyl chloride (0.04 mol) in benzene for
48 h to obtain 13.90 g (ca. 82%) of the salt: mp 320–323 °C
1
(19). H NMR (CDCl3) δH: 5.66 (2H, d, J = 15.2 Hz), 6.87
(1H, d, J = 2 Hz), 7.02 (1H, t, J = 8 Hz), 7.12 (1H, d, J =
7.6 Hz), 7.15 (1H, d, J = 7.6 Hz), 7.57–7.61 (6H, m), 7.71–
7.81 (9H, m). 13C NMR (CDCl3) (JP-C) δC : 30.62 (d, J =
46.5 Hz, P-CH2), 118.30 (d, J = 85.40 Hz, C-1 of P-Ph),
128.91 (d, J = 3.8 Hz), 130.35 (d, J = 8.4 Hz), 130.55 (d,
J = 3.3 Hz, C-4 of P-Ph), 130.70 (d, J = 12.5 Hz, C-3 of P-
Ph), 130.76, 131.73 (d, J = 5.3 Hz), 134.72 (d, J = 3.8 Hz),
134.98 (d, J = 10 Hz, C-2 of P-Ph), 135.51 (d, J = 2.7 Hz).
31P NMR (CDCl3) δP: 25.05. MS m/z: 389/387 (M+· + 2/M+· –
Cl–). Anal. calcd. for C25H21Cl2P (%): C 70.92, H 4.96;
found: C 70.96, H 4.96.
[(Benzylsulfonyl)(4-methoxyphenyl)methylene](triphenyl)-
phosphorane (8)
Obtained by treating the obtained salt with BuLi followed
The target ylide 5 was prepared by treating the obtained
salt with BuLi and phenylmethanesulfonyl fluoride accord-
ing to procedure A, in a 2:2:1 ratio. The obtained colorless
material was recrystallized from ethyl acetate to obtain
3.25 g of the pure colorless crystals (ca. 80%) of the target
ylide mp 216–218 °C. IR υmax(cm–1): 1584, 1436, 1270,
1103, 811, 760, 542, 503. 1H NMR (CDCl3) δH: 3.99
(2H, s), 6.90–7.00 (2H, m), 7.04 (1H, s), 7.10–7.15 (2H, m),
7.25–7.31 (4H, m), 7.37–7.40 (6H, m), 7.48–7.55 (9H, m).
13C NMR (CDCl3) (JP-C) δC: 47.5 (d, J = 129 Hz, P=C),
62.29 (CH2), 125.6 (d, J = 2 Hz), 127.53 (d, J = 92 Hz, C-1
of P-Ph), 128.13, 128.64, 128.71, 128.89 (d, J = 12 Hz, C-3
of P-Ph), 128.98, 131.59 (d, J = 2.1 Hz), 132.06 (d, J =
2.9 Hz), 132.24 (d, J = 3 Hz, C-4 of P-Ph), 134.17, 134.30
(d, J = 10 Hz, C-2 of P-Ph), 134.89 (d, J = 4.1 Hz), 137.7
(d, J = 9 Hz). 31P NMR (CDCl3) δP: 19.84. MS m/z: 542/540
(M+· + 2/M+·, 8/18%), 451/449 (37/35Cl – M+ – PhCH2, 35/100),
401 (50), 385 (85), 351 (40), 262 (46), 241 (40), 183 (85),
165 (78), 139 (75). Anal. calcd. for C32H26ClO2PS (%): C
71.04, H 4.81, S 5.92; found: C 71.17, H 4.96, S 5.66.
by phenylmethanesulfonyl fluoride in a 2:2:1 ratio. Yield:
86%; mp 193–195 °C (3). IR
1438, 1242, 1095, 1049, 750, 694 (3). H NMR (CDCl3) (3)
υmax
(cm–1): 2829, 1598, 1503,
1
δ
H: 3.75 (3H, s), 4.13 (2H, s), 6.62 (2H, d, J = 8 Hz), 7.16–
7.18 (4H, m), 7.27–7.29 (2H, m), 7.32–7.35 (7H, m), 7.45–
7.50 (9H, m). 13C NMR (CDCl3) (JP-C
)
δ
C: 45.85 (d, J =
129 Hz, P=C), 55.61 (CH3), 61.55 (CH2), 113.72, 126.97 (d,
J = 8.4 Hz), 127.86, 128.28 (d, J = 92 Hz, C-1 of P-Ph),
128.60, 128.71 (d, J = 12 Hz, C-3 of P-Ph), 131.70, 131.87
(d, J = 3 Hz, C-4 of P-Ph), 132.04, 134.20 (d, J = 10 Hz, C-
2 of P-Ph), 137.94 (d, J = 3 Hz), 158.35 (d, J = 2 Hz). 31P
NMR (CDCl ) : 19.80. MS m/z: 536 (M+·, 40), 397.1 (25),
δP
3
365 (30), 381 (100), 278 (50), 262 (55), 183 (70), 152 (40),
121 (50), 91 (75). Anal. calcd. for C33H29O3PS (%): C
73.88, H 5.41, S 5.97; found: C 73.80, H 5.51, S 5.55.
[(Benzylsulfonyl)(methyl)methylene](triphenyl)phosphorane
(9)
Obtained by treating the obtained salt with BuLi followed
[(Benzylsulfonyl)(phenyl)methylene](triphenyl)phosphorane
(6)
Obtained by treating the obtained salt with BuLi followed
by phenylmethanesulfonyl fluoride in a 2:2:1 ratio. Yield:
1
62%; mp 170–172 °C (1). H NMR (CDCl3) (1) δH: 1.58
(3H, d, J = 14 Hz), 3.97 (2H, s), 7.27 (5H, s), 7.7–7.4
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