4
398 J . Org. Chem., Vol. 61, No. 13, 1996
Hudrlik et al.
8.6 Hz, 2 H), 3.85 (m, 1 H, on addition of D
2
O, becomes an
(
60-100 mesh, Fisher). Elemental analyses were carried out
1
3
by Desert Analytics, Tucson, AZ.
apparent quintet), 7.3-7.4 (9 H), 7.5-7.6 (6 H); C NMR δ
Anhydrous ether and THF were freshly distilled from
sodium/benzophenone. Magnesium was purchased as mag-
nesium chips (99.98%) from Aldrich. (Triphenylsilyl)ethylene
9.986 (CH ), 22.737 (CH ), 33.588 (CH ), 70.445 (CH), 127.914
3
2
2
1
1
(CH), 129.478 (CH), 135.048 (C), 135.693 (CH); 2-D ( H- H)
NMR (δ correlated with δ) 0.88 with 1.50; 1.50 with 0.88 and
3.85; 1.72 with 3.85; 3.85 with 1.50 and 1.72; GC/MS (CI, NH )
3
2
,30
oxide (1) was prepared by treatment of triphenylvinylsilane
with m-chloroperbenzoic acid. (Triphenylsilyl)acetaldehyde
m/ z (tentative assignment, relative intensity) 350 [(M +
3
+
+
+
4
(8) was prepared by treatment of 1 with magnesium bromide
NH
(Ph
4
) , 31], 332 (M , 38), 294 [(Ph
3
SiOH + NH
) , 10], 276
+
3
) , 12]; GC/MS (EI)
+
etherate in benzene (reflux, 1.25 h).
Rea ction of (Tr ip h en ylsilyl)eth ylen e Oxid e (1) w ith
Ma gn esiu m Br om id e Eth er a te: Isola tion of 2-Br om o-2-
3
SiOH , 100), 216 [(Ph
2
SiOH + NH
SiOH , 10), 259 (Ph Si , 70), 199 (Ph SiOH ,
3 3 2
+
+
+
m/ z 276 (Ph
+
+
100), 181 (20), 155 (10), 122 (PhSiOH , (10), 105 (C Si , 10),
+
77 (C H , 10). GC analysis [150 °C (1 min), 10 °C/min to 270
6 5
6
H
5
(
tr ip h en ylsilyl)eth a n ol (9). Magnesium bromide was pre-
pared from 0.292 g (12 mmol) of magnesium and 0.85 mL (1.85
g, 9.9 mmol) of 1,2-dibromoethane in 7 mL of anhydrous ether.
A 4-mL portion of the lower layer was added to an ice-cooled
solution of 0.604 g (2.00 mmol) of epoxy silane 1 in 10 mL of
anhydrous ether. The mixture was stirred at 0 °C for 30 min
and at room temperature for 30 min and was then heated at
reflux for 1 h. The reaction mixture was then added to 40
°C (5 min), C24
min (100%).
H50 at 8.83 min] showed a major peak at 9.36
Rea ction of (Tr ip h en ylsilyl)a ceta ld eh yd e (8) w ith
Eth ylm a gn esiu m Br om id e: Isola tion of 1-(Tr ip h en ylsi-
lyl)-2-bu ta n ol (4). Ethylmagnesium bromide in ether (from
0.146 g (6.00 mmol) of magnesium, 7 mL of anhydrous ether,
and 0.37 mL (0.540 g, 5.00 mmol) of bromoethane) was added
slowly to 0.150 g (0.496 mmol) of aldehyde 8 in 10 mL of
anhydrous ether. The reaction was stirred at room temper-
mL of saturated NH
organic layer was extracted with saturated NaHCO
and saturated NaCl and then dried (MgSO ). The solvent was
4
Cl overlaid with 70 mL of ether. The
3
, water,
ature for 1 h and then added to 40 mL of saturated NH
overlaid with 40 mL of ether. The organic layer was washed
with saturated NaHCO , water, and saturated NaCl and then
dried (Na SO ). The solvent was removed on a rotary evapo-
4
Cl
4
removed on a rotary evaporator, giving 0.75 g of a light yellow
crystalline solid, mp 85-90 °C. Purification by vacuum liquid
3
3
1
chromatography (0.50 g of crude product in 2 mL of toluene
applied to 20 g of silica gel (200-425 mesh) using a 5 × 13 cm
funnel with 20 mL fractions of petroleum ether followed by
2
4
rator, giving 0.19 g of a colorless liquid that solidified.
Chromatography on Florisil using 20% ether in petroleum
ether gave 0.117 g (73% yield) of â-hydroxy silane 4 as white
2
0% ether in petroleum ether) gave aldehyde 8 (0.13 g) and
bromohydrin 9 (0.133 g of mp 99-101 °C and 0.12 g of mp
03-105 °C). The bromohydrin was further purified by
1
1
1
crystals, mp 70-71 °C. The IR, H NMR, 2-D H- H NMR,
1
3
1
3
C NMR with DEPT (45/90/135), GC/MS (CI, NH ), and GC/
vacuum liquid chromatography (5 × 10 cm funnel, 20 mL
fractions of 20% ether in petroleum ether), giving 0.11 g (22%
adjusted yield) of bromohydrin 9 as off-white needles, mp 103-
MS (EI) of this sample were equivalent to those of the sample
of 4 prepared from epoxy silane 1 and EtMgBr. GC analysis
[150 °C (1 min), 10 °C/min to 270 °C (5 min), C24
min] showed a major peak at 9.53 min (99%). Anal. Calcd
for C22 24OSi: C, 79.47, H, 7.27. Found: C, 79.59, H, 7.30.
H50 at 8.91
1
6
05 °C: IR (KBr) 3369 (br), 3050, 1427, 1110, 1051, 997, 742,
-
1
1
98 cm ; H NMR (D
2
O added) δ 3.96 (dd, J ) 12.88, 9.69
H
Hz, 1 H), 4.10 (dd, J ) 12.88, 2.90 Hz, 1 H), 4.22 (dd, J )
.68, 2.90 Hz, 1 H), 7.35-7.5 (complex, 9 H), 7.6-7.7 (6 H) [in
the absence of D
.48 Hz, 1 H); multiplets at 3.96 and 4.10 more complex]; 13
Rea ction of (Tr ip h en ylsilyl)eth ylen e Oxid e (1) w ith
P h en ylm a gn esiu m Br om id e: Isola tion of 1-P h en yl-2-
(tr ip h en ylsilyl)eth a n ol (7). Phenylmagnesium bromide in
ether (from 0.851 g (35.0 mmol) of magnesium, 15 mL of
anhydrous ether, and 3.2 mL (4.77 g, 30 mmol) of bromoben-
zene) was transferred to an ice-cooled solution of 0.604 g (2.00
mmol) of epoxy silane 1 in 10 mL of anhydrous ether. The
reaction mixture was stirred at 0 °C for 15 min and was then
heated at reflux for 1 h. The cooled mixture was added to 40
9
2
O, an additional peak at 2.22 (dd, J ) 8.87,
4
C
NMR δ 43.582 (CH), 64.673 (CH
2
), 128.068 (CH), 130.181 (CH),
1
31.920 (C), 136.145 (CH); GC/MS (CI, NH
3
) m/ z (tentative
+
assignment, relative intensity) 400, 402 [(M + NH
4
) , 92, 100],
) , 50], 294 [(Ph SiOH +
SiOH , 30), 216 [(Ph SiOH + NH
SiOH , 30), 260 (30), 259 (Ph
SiOH 40), 181 (20), 155 (10), 122 (PhSiOH ,
+
3
NH
22 (80), 320 [(Ph
4
3
SiCH
) , 14], 276 (Ph
GC/MS (EI) m/ z 276 (Ph
2
CHO + NH
4
3
+
+
+
3
3
2
) , 20];
+
+
3
3
Si ,
mL of saturated NH
organic layer was washed twice with 5% NaOH, with saturated
NaHCO , water, and saturated NaCl and then dried (MgSO ).
4
Cl overlaid with 50 mL of ether. The
+
+
1
2
[
00), 199 (Ph
0), 105 (C
2
+
+
6
H
5
Si , 10), 77 (C
6
H
5
, 10), 51 (10). GC analysis
50 at 8.20
min] showed the major peak at 10.94 min (97%) and a minor
3
4
150 °C (1 min), 10 °C/min to 270 °C (5 min), C24
H
The solvent was removed on the rotary evaporator to give 1.00
g of yellow liquid that partially solidified. Chromatography
on Florisil using 30% ether in petroleum ether gave 0.18 g
(24% yield) of â-hydroxy silane 7 as white crystals, mp 124-
125 °C. The product was further purified by triturating with
10 mL of pentane, giving 0.124 g of white crystals, mp 126-
peak at 8.607 min (2%, aldehyde 8). Anal. Calcd for C20
19
H -
BrOSi: C, 62.66; H, 5.00. Found: C, 62.92; H, 5.04.
Rea ction of (Tr ip h en ylsilyl)eth ylen e Oxid e (1) w ith
Eth ylm a gn esiu m Br om id e: Isola tion of 1-(Tr ip h en ylsi-
lyl)-2-bu ta n ol (4). Ethylmagnesium bromide in ether (from
128 °C (lit.2
9a,c
mp 131-133 °C, lit.
(KBr) 3567, 3049, 1426, 1108, 728, 700 cm ; H NMR δ 1.74
(d, J ) 3.5 Hz, 1 H, exchanged with D O), 1.94 (dd, J ) 15.0,
4.6 Hz, 1 H), 2.12 (dd, J ) 15.0, 9.6 Hz, 1 H), 4.94 (m, 1 H; in
the presence of D O, dd, J ) 9.6, 4.6 Hz, 1 H), 7.2-7.6
(complex, 15 H); 13C NMR δ 25.782 (CH
), 71.650 (CH), 125.476
29b
mp 135-137 °C): IR
-
1 1
0
.49 g (20 mmol) of magnesium, 20 mL of anhydrous ether,
and 1.4 mL (2.03 g, 19 mmol) of bromoethane) was transferred
to an ice-cooled solution of 0.604 g (2.00 mmol) of epoxy silane
2
1
in 7 mL of anhydrous ether. The reaction mixture was
2
stirred at 0 °C for 40 min and was heated at reflux for 1 h.
The mixture was allowed to cool to room temperature and was
2
(CH), 127.321 (CH), 127.893 (CH), 128.418 (CH), 129.476 (CH),
134.929 (C), 135.792 (CH), 136.241 (small, impurity), 146.789
then added to 30 mL of saturated NH
of ether. The organic layer was extracted with saturated
NaHCO , water, and saturated NaCl and then dried (MgSO ).
4
Cl overlaid with 50 mL
(C); GC/MS (CI, NH
intensity) 398 [(M + NH
10), 294 [(Ph SiOH + NH
3
) m/ z (tentative assignment, relative
+
+
+
3
4
4
) , 10], 380 (M , 10), 363 (M - OH,
+
+
The solvent was removed on the rotary evaporator to give 0.63
g of light yellow liquid that partially solidified. Chromatog-
raphy on Florisil using 30% ether in pentane gave 150 mg (25%
yield) of â-hydroxy silane 4 as a colorless liquid that solidified.
Recrystallization from ligroin (bp 60-80 °C) gave 90 mg (14%
yield) of 4 as white crystals, mp 74-75 °C: IR (KBr) 3587,
3
4
) , 10], 276 (Ph
3
SiOH , 100), 216
+
(10); GC/MS (EI) m/ z 362 (M - H
2
O, 2), 301 (20), 259 (Ph
3
-
+
+
+
Si , 63), 199 (Ph
2
SiOH , 100), 181 (27), 105 (C
6
H
5
Si , 17), 104
+
(18), 77 (C
6
H
5
, 16). GC analysis [70 °C (5 min), 10 °C/min to
270 °C (10 min), C28
26.05 min (92%).
H58 at 24.17 min] showed a major peak at
3
7
1
061, 2912, 1427, 1108, 728, 700 cm-1; 1H NMR δ 0.88 (t, J )
Rea ction of (Tr ip h en ylsilyl)a ceta ld eh yd e (8) w ith
P h en ylm a gn esiu m Br om id e: Isola tion of 1-P h en yl-2-
(Tr ip h en ylsilyl)eth a n ol (7). Phenylmagnesium bromide in
ether (from 0.150 g (6.20 mmol) of magnesium, 7 mL of
anhydrous ether, and 0.5 mL (0.745 g, 4.8 mmol) of bromoben-
zene) was slowly transferred to an ice-cooled solution of 0.150
g (0.496 mmol) of aldehyde 8 in 10 mL of anhydrous ether.
.4 Hz, 3 H), 1.32 (d, J ) 4.0 Hz, 1 H, exchanged with D
2
O),
.50 (m, 2 H), 1.72 (appears as overlapping doublets, J ) 5.5,
(
(
30) Eisch, J . J .; Trainor, J . T. J . Org. Chem. 1963, 28, 487-492.
31) Pelletier, S. W.; Chokshi, H. P.; Desai, H. K. J . Nat. Prod. 1986,
4
9, 892-900.