J ones et al.
product (0.99 g). Additional silica gel chromatography (7%
EtOAc in petrol 40-60) provided pure phosphorylated product
(0.75 g, 74%). IR (film) 1589 (s), 1488 (s), 1475 (s), 1311 (s),
1200 (s) cm-1; 1H NMR (300 MHz, CDCl3) δ 7.61 (m, 1H), 7.49
(m, 1H), 7.40-7.25 (m, 11H), 7.09 (m, 1H); 13C NMR (75.5
MHz, CDCl3) δ 150.7 (d, J C-P ) 7.7 Hz), 148.1 (d, J C-P ) 6.1
Hz), 134.3, 130.3, 129.1, 127.1, 126.2, 121.6 (d, J C-P ) 2.3 Hz),
120.6 (d, J C-P ) 4.8 Hz), 114.8 (d, J C-P ) 8.5 Hz); 31P NMR
(121.5 MHz, CDCl3) δ -17.26; EI-MS m/z 404 (M+, 8), 326 (21),
325 (100), 77 (22); exact mass calcd for C18H14BrO4 403.9813,
found 403.9799. Anal. Calcd for C18H14BrO4: C, 53.36; H, 3.48.
Found: C, 53.36; H, 3.56.
Er goca lcifer ol Dip h en yl P h osp h a te (20). Ergocalciferol
(0.25 mmol, 0.10 g) was added to a solution of titanium tert-
butoxide (0.1 M, 10 mol %, 0.25 mL) in dry CH2Cl2 (1.25 mL)
under nitrogen. Et3N (0.38 mmol, 0.05 mL) and diphenyl
chlorophosphate (0.25 mmol, 0.05 mL) were added sequentially
via syringe. The reaction mixture was stirred at room tem-
perature for 20 h before being filtered through a layered plug
of silica and MgSO4 (ratio 20:1). Washing with EtOAc in petrol
(35%, 50 mL) followed by evaporation yielded the pure phos-
phorylated product (0.10 g, 63%). [R]D +34.3 (c 1.4, CHCl3);
IR (film) 2995 (m), 1580 (m), 1480 (m), 1390 (m), 1005 (m)
cm-1; 1H NMR (300 MHz, CDCl3) δ 7.28-7.21 (m, 4H), 7.18-
7.07 (m, 6H), 6.09 (d, J ) 11.2 Hz, 1H), 5.91 (d, J ) 11.2 Hz,
1H), 5.11 (m, 2H), 4.98 (m, 1H), 4.81-4.70 (m, 2H), 2.70-1.14
(m, 21H), 0.93 (d, J ) 6.6 Hz, 3H), 0.82 (d, J ) 6.9 Hz, 3H),
0.74 (d, J ) 6.8 Hz, 3H), 0.70 (d, J ) 6.8 Hz, 3H), 0.49 (s, 3H);
13C NMR (75.5 MHz, CDCl3) δ 151.0 (d, J C-P ) 7.2 Hz), 144.4,
143.1, 136.0, 133.7, 132.3, 130.1, 125.6, 123.6, 120.6 (d, J C-P
) 3.5 Hz), 117.8, 113.4, 78.4 (d, J C-P ) 6.3 Hz), 56.9, 46.2,
43.9 (d, J C-P ) 4.6 Hz), 43.2, 40.8, 33.7, 31.9, 29.5, 28.2, 24.0,
22.5, 21.5, 20.3, 20.0, 18.0, 12.6; 31P NMR (121.5 MHz, CDCl3)
δ -12.25; EI-MS m/z 628 (M+, 2), 378 (100), 363 (6), 250 (43),
199 (10), 94 (46); exact mass calcd for C40H53O4P 628.3681,
found 628.3665. Anal. Calcd for C40H53O4P: C, 76.40; H, 8.50.
Found: C, 76.32; H, 8.31.
17â-Hyd r oxy-5r-a n d r osta n -3-on e Dip h en yl P h osp h a te
(21). 5R-Androstan-17â-ol-3-one (0.34 mmol, 0.10 g) was added
to a solution of titanium tert-butoxide (0.1 M, 10 mol %, 0.34
mL) in dry DCM (2.0 mL) under nitrogen. Et3N (0.51 mmol,
0.07 mL) and diphenyl chlorophosphate (0.34 mmol, 0.07 mL)
were added sequentially via syringe. The reaction mixture was
stirred at room temperature for 20 h before being filtered
through a layered plug of silica and MgSO4 (ratio 20:1).
Washing with EtOAc in petrol (35%, 50 mL) followed by
evaporation yielded the pure phosphorylated product as a
white solid (0.10 g, 56%). Mp 123-124 °C, [R]D +19.3 (c 1.0,
CHCl3); IR (film) 2935 (s), 1712 (s), 1489 (s), 1295 (s), 1286
(s), 1192 (s) cm-1; 1H NMR (300 MHz, CDCl3) δ 7.29-7.24 (m,
4H), 7.17-7.08 (m, 6H), 4.38 (dt, J P-H ) 7.8 Hz and J ) 7.8
Hz, 1H), 2.36-1.88 (m, 6H), 1.74-0.60 (m, 17H), 0.92 (s, 3H),
0.73 (s, 3H); 13C NMR (125 MHz, CDCl3) δ 211.7, 150.7, 129.7,
125.1, 120.0 (d, J C-P ) 4.0 Hz), 88.3 (d, J C-P ) 7.1 Hz), 53.6,
49.8, 46.6, 44.6, 43.3, 43.2, 38.4, 38.1, 36.3, 35.7, 35.2, 31.1,
28.7, 28.3, 23.3, 20.8, 11.6, 11.4; 31P NMR (121.5 MHz, CDCl3)
δ -11.22; EI-MS m/z 522 (M+, 8), 272 (26), 251 (100), 220 (6),
174 (10), 149 (12); exact mass calcd for C31H39O5P 522.2535,
found 522.2529. Anal. Calcd for C31H39O5P: C, 71.24; H, 7.52.
Found: C, 71.10; H, 7.72.
Ack n ow led gm en t. We thank Pfizer for a Summer
Studentship (K.J .T.) and the University of Newcastle
upon Tyne for support (S.M.T.).
Su p p or tin g In for m a tion Ava ila ble: 1H, 13C, and 31P
NMR data of known phosphate products 2, 4b, 5-16, 19, and
22 and copies of all 1H NMR spectra. This material is available
J O034331G
5216 J . Org. Chem., Vol. 68, No. 13, 2003