5
536 J . Org. Chem., Vol. 61, No. 16, 1996
Bonafoux et al.
resulting mixture was transferred under argon to a two-necked
1-(Tr im eth ylsiloxy)cycloh ex-1-en e (17). 1H NMR:
δ
0.11 (s, 9H), 1.38-2.29 (m, 2H), 4.78 (s, 1H). 13C NMR: δ 0.3,
22.3, 23.1, 24.5, 30, 104.1, 150.3. IR (neat): 1668 cm-1. MS
round-bottomed flask and cooled to -75 °C. Then, the ketone
(20 mmol) was added. After 3 h of stirring at this temperature,
Me
magnesium enolate mixture and the temperature was held
constant for 30 min. DME and excess Me SiCl were evapo-
3
SiCl (20 mL, 150 mmol) was added to the resulting
+
+
m/ z: 170 (M ), 155 (M - CH
-Meth yl-1-(tr im eth ylsiloxy)p en t-1-en e (18). 1H NMR:
δ 0.17 (s, 9H), 0.99 (d, 3H, J ) 6.9 Hz), 1.2-1.5 (m, 2H), 2-2.5
3
), 75 (100).
5
3
rated. The residue was extracted with 80 mL of cold pentane
and washed with ice-cold water. The aqueous layer was
extracted several times with pentane (3 × 50 mL). The
combined pentane extracts were washed with cold 5% aqueous
HCl, then with water until neutrality, and dried over magne-
sium sulfate. After evaporation of pentane, the silyl enol
(
1
m, 3H), 4.53 (m, 1H). 13C NMR: δ -0.1, 18.6, 26.7, 30.4, 39.2,
00.5, 158.5. IR (neat): 1646 cm . MS m/ z: 170 (M ), 155
-
1
+
+
(M - CH
3
), 73 (100). All NMR, IR, and mass spectra are in
accordance with ref 6a.
-Met h yl-1-(t r im et h ylsiloxy)cycloh ex-1-en e (20). 1H
NMR: δ 0.16 (s, 9H), 0.99 (d, 3H, J ) 6.9 Hz), 1.25-1.8 (m,
6
ethers were separated from Me
3 3
SiOSiMe and HMDS by
1
distillation. Analysis of the products was achieved by GC, H,
1
3
4
H), 1.93-2.09 (m, 2H), 2.1-2.21 (m, 1H), 4.81 (m, 1H,).
C
1
3
1
13
C, IR, and mass spectroscopies. The H and C NMR and
1
13
NMR: δ 0.1, 18.4, 20.0, 24.0, 31.3, 33.3, 103.1, 153.8. IR
IR spectra of 12-15 and H and C NMR spectra of 16 and
1
-
1
+
+
4
(neat): 1660 cm . MS m/ z: 184 (M ), 169 (M - CH
100). All NMR, IR, and mass spectra are in accordance with
ref 6a.
-Meth yl-2-(tr im eth ylsiloxy)p en t-1-en e (22). 1H NMR:
δ 0.25 (s, 9H), 0.75 (d, 6H, J ) 6.5 Hz), 1.93 (m, 3H), 4.05 (s,
3
), 73
7 are identical with these previously reported for samples
(
obtained from ketones 2-7 respectively using the 2-pyrroli-
done magnesium salt as EGB.
2
-(Tr im eth ylsiloxy)-1,3-diph en ylpr op-1-en e (12). A sole
4
1
isomer was formed. H NMR: δ 0.24 (s, 9H), 3.62 (s, 2H), 5.53
1
3
(
1
1
s,1H), 7.3-7.63 (m, 10H). C NMR: δ 1.1, 44.3, 110.5, 125.9,
13
2
1
H). C NMR: δ 0.1, 22.0, 25.2, 45.8, 90.5, 158.2. IR (neat):
H NMR and IR spectra are in accordance with
3
ref 10. MS m/ z: 172 (M ), 157 (M - CH ), 115 (100), 73.
26.8, 127.3, 128.2, 128.4, 128.7, 129, 129.2, 129.5, 129.8, 137,
-1
1
660 cm
.
-
1
+
38.2, 152. IR (neat): 1650 cm . MS m/ z: 282 (M ), 267
+
+
+
(
M
- CH
-(Tr im eth ylsiloxy)-1,2-d ip h en yleth ylen e (Z) (13). 1H
NMR: δ 0.25 (s, 9H), 6.34 (s, 1H), 7.38-7.8 (m, 5H), 7.85-
3
), 73 (100).
2-(Tr im eth ylsiloxy)p en t-1-en e (24). 1H NMR: δ 0.14 (s,
9H), 0.85 (t, 3H, J ) 7.4 Hz), 1.51 (m, 2H), 1.93 (t, 2H, J ) 7
1
1
3
13
7
.88 (m, 5H), in accordance with ref 9a for the Z isomer.
C
Hz), 3.97 (s, 2H). C NMR: δ 1.8, 13.5, 19.9, 38.5, 89.8, 160.
IR (neat): 1662 cm-
1
.
1
H NMR and IR spectra are in
NMR: δ 0.9, 110.7, 126.3, 126.4, 127, 128.2, 128.3, 128.4,
-
1
1
28.9, 129.7, 133.3, 136.8, 139.8, 151.1. IR (neat): 1630 cm
.
+
+
accordance with ref 10. MS m/ z: 158 (M ), 143 (M - CH
5, 45 (100).
-Meth yl-6-(tr im eth ylsiloxy)n on a -4-on e (26). 1H NMR:
δ 0 (s, 9H), 0.79 (t, 6H), 1.18 (s, 3H,), 1.22-1.46 (m, 6H,), 2.3-
.49 (m, 4H, J AB ) 12.8 Hz). 13C NMR: δ 2.4, 13.7, 14.4, 16.9,
17.5, 27.8, 45.5, 47.0, 53.9, 75.8, 210.8; DEPT experiments
were performed to confirm this structure showing five CH at
16.9, 17.5, 45.5, 47, and 53.9 ppm and no CH. IR (neat): 1721
3
),
+
+
MS m/ z: 268 (M , 100), 253 (M - CH
3
), 73.
7
2
-(Tr im et h ylsiloxy)-1-p h en ylp r op -1-en e (Z) (14). 1H
6
NMR: δ 0.24 (s, 9H), 1.97 (s, 3H), 5.41 (s, 1H), 7-7.5 (m, 5H),
1
3
in accordance with refs 9a and 10 for the Z isomer. C NMR:
δ 1.0, 24.1, 108.5, 125.3, 127.1, 127.8, 128.1, 137.1, 149.4. IR
2
-
1
+
+
(
7
neat): 1650 cm . MS m/ z: 206 (M , 100), 191 (M - CH
3
),
3.
2
1
-(Tr im et h ylsiloxy)-1-p h en ylp r op -1-en e (Z) (15). 1H
3
3
-1
+
NMR: δ 0.13 (s, 9H), 1.76 (d, 2H, J ) 6.8 Hz), 5.34 (q, 1H, J
cm . MS m/ z: 229 (M - CH ), 71 (100). Anal. Calcd for
3
1
3
)
1
6.8 Hz), 7.24-7.5 (m, 5H). C NMR: δ 0.5, 11.6, 105.1,
13 28 2
C H O Si: C, 63.93; H, 11.47; O, 13.11; Si, 11.47. Found:
C, 63.9; H, 11.52; O, 13.2.
27.2, 127.8, 127.9, 128.4, 149.8, in accordance with ref 9a.
-
1
+
+
IR (neat): 1655 cm . MS m/ z: 206 (M ), 191 (M - CH
3
),
7
5 (100), 73.
1
-(Tr im eth ylsiloxy)cyclop en t-1-en e (16). 1H NMR: δ
Ack n ow led gm en t. Financial support for this work
by Electricit e´ de France, Rh oˆ ne-Poulenc, CNRS, and
R e´ gion Aquitaine is gratefully acknowledged.
0
.13 (s, 9H), 2.0-2.14 (m, 2H), 2.16-2.25 (m, 4H), 4.53 (s, 1H).
1
3
C NMR: δ -0.1, 21.2, 28.6, 33.4, 101.8, 154.9. IR (neat):
-
1
+
+
1
7
667 cm . MS m/ z: 156 (M ), 155 (100), 141 (M - CH
3
),
5.
J O960493J