1944
Černovská, Nič, Pihera, Svoboda:
Triph en yl{2-[(2-th iocyan atoben zoyl)oxy]ben zyl}ph osph on ium Brom ide (8b)
To a stirred m ixture of ph osph on ium brom ide 6 (ref.14) (1.75 g, 3.89 m m ol), 2-th io-
cyan atoben zoyl ch loride32 (1.01 g, 5.11 m m ol) an d ch loroform (4 m l), dry pyridin e (0.65 g,
8.05 m m ol) was added dropwise un der coolin g to 0 °C. Stirrin g was con tin ued for 45 m in ,
th e solution was diluted with ch loroform (50 m l), wash ed with water an d dried with an h y-
drous m agn esium sulfate. Evaporation of th e filtrate an d trituration of th e residue with
eth er (10 m l) afforded 2.0 g (84%) of ph osph on ium brom ide 9b, m .p. 162–166 °C. 1H NMR
(DMSO-d6): 5.23 d, 2 H, J = 15.4 (CH2-P+); 7.00–7.90 m , 23 H (Ar-H). IR (KBr): 2 154 (SCN);
1 711 (C=O). For C33H25BrNO2PS (610.5) calculated: 64.92% C, 4.13% H, 2.29% N; foun d:
65.22% C, 4.33% H, 2.01% N.
In an an alogous m an n er, th e followin g ph osph on ium brom ides were obtain ed:
P,P,P,P′,P′,P′-Hexaphenyl-P,P′-{disulfanediylbis[(1,2-phenylene)carbonyloxy(1,2-phenylene)methy-
lene]}bisphosphonium bromide (8c). Yield 97%, m .p. 148–152 °C. 1H NMR (DMSO-d6): 5.26 d,
2 H, J = 15.4 (CH2-P+); 7.05–7.95 m , 23 H (Ar-H). IR (KBr): 1 717 (C=O).
{2-[(2-Chlorobenzoyl)oxy]benzyl}triphenylphosphonium bromide (8d). Yield 90%, m .p. 173–175 °C.
1H NMR (DMSO-d6): 5.13 d, 2 H, J = 14.8 (CH2-P+); 7.05–7.85 m , 23 H. IR (KBr): 1 736
(C=O). For C32H25BrClO2P (587.9) calculated: 65.38% C, 4.29% H, 13.59% Br, 6.03% Cl;
foun d: 65.52% C, 4.50% H, 11.10% Br, 6.78% Cl.
{2-[(2-Bromobenzoyl)oxy]benzyl}triphenylphosphonium bromide (8e). Yield 92%, m .p. 188–190 °C;
ref.16, m .p. 189–192 °C.
1-[(2-Ben zylsulfan yl)ph en yl]-2-(2-h ydroxyph en yl)eth an -1-on e (9a)
A solution of 2-(ben zylsulfan yl)ben zoyl ch loride33 (1.30 g, 4.94 m m ol) in ch loroform (10 m l)
was added dropwise to a stirred m ixture of ph osph on ium brom ide 6 (1.73 g, 3.85 m m ol),
pyridin e (0.78 g, 9.9 m m ol) an d ch loroform (15 m l) at 0 °C. Stirrin g was con tin ued at room
tem perature for 1 h an d th e reaction m ixture was worked up as for 8b. Th e crude product
was purified by colum n ch rom atograph y (silica gel, elution with a h exan e–toluen e, 1 : 1) to
afford 0.93 g (72%) of eth an on e 9a, m .p. 115.5–117 °C (toluen e–h exan e). 1H NMR: 4.16 s,
2 H (CH2S); 5.37 s, 2 H (CH2CO); 7.14 t, 1 H, J = 7.6; 7.25–7.48 m , 12 H; 8.01 d, 1 H, J = 7.7.
IR: 1 708 (C=O). For C21H18O2S (334.4) calculated: 75.42% C, 5.43% H, 9.59% S; foun d:
75.32% C, 5.54% H, 9.84% S.
2-(2-Hydroxyph en yl)-1-(2-th iocyan atoph en yl)eth an -1-on e (9b)
To a slurry of ph osph on ium brom ide 8b (1.88 g, 3.88 m l) in dry 1,2-dim eth oxyeth an e,
trieth ylam in e (0.65 m l, 4.66 m m ol) was added an d th e m ixture was stirred at room tem pera-
ture for 1 h . Trieth ylam m on ium brom ide was filtered off an d th e filtrate was evaporated to
dryn ess. Colum n ch rom atograph y (silica gel, toluen e–tert-butyl m eth yl eth er, 10 : 1) af-
forded 0.52 g (63%) of com poun d 9b, m .p. 159–162 °C (eth yl acetate). 1H NMR: 4.33 s, 2 H
(CH2CO); 5.90 s, 1 H (OH); 6.90 m , 2 H; 7.18 m , 2 H; 7.50 dd, 1 H, J1 = 7.7, J2 = 7.1; 7.68 dd,
1 H, J1 = 7.7, J2 = 6.6; 7.99 d, 1 H, J = 8.2; 8.27 d, 1 H, J = 7.7. 13C NMR (on e quatern ary car-
bon was n ot detected): 41.0 (CH2), 112.9, 117.4 (C-H), 121.0, 122.0 (C-H), 128.3 (C-H),
129.5 (C-H), 129.9 (C-H), 131.9 (C-H), 132.1, 132.4 (C-H), 135.2 (C-H), 154.9 (C-OH), 200.4
(C=O). IR: 3 453 (OH); 2 146 (SCN); 1 666 (CO). MS, m/z (%): 242 (30) [M+ – HCN], 226 (50)
[M+ – HCN – O], 162 (100) [C8H4NOS]+, 134 (20) [C7H4NS]+, 107 (70), 77 (20), 57 (20). For
Collect. Czech. Chem. Commun. (Vol. 65) (2000)