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K.D. Safa et al. / Journal of Organometallic Chemistry 694 (2009) 2448–2453
NMR (400 MHz, CDCl3): d ꢀ0.28 (s, 9H, SiMe3), ꢀ0.29 (s, 9H, SiMe3),
6.45, 6.80 (m, 3H, Ar), 7.1 (s, 1H, vinyl); 13C NMR (CDCl3): d ꢀ0.5
(SiMe3), 0.61 (SiMe3), 124.4–147.8 (Ar and C@C); m/z (EI): 254
(23%, [M]+), 239 (30%, [MꢀMe]+), 181 (36%, [MꢀSiMe3]+), 141
(100%), 73 (40%, [SiMe3]+). Anal. Calc. for C12H22Si2S: C, 71.7; H,
8.7. Found: C, 71.9; H, 8.3%.
m.p. 92 °C). 7a: FT-IR (KBr cmꢀ1), 3065 (Ar–H), 1674 (C@O),
1594, 1500 (Ar and C@C), 1249, 841 (Si–CH3); 1H NMR (400 MHz,
CDCl3): d 0.26 (s, 9H, SiMe3), 2.08 (s, 3H, CH3), 6.90-7.83 (m, 8H, vi-
nyl and Ar); 13C NMR (CDCl3): d ꢀ2.6 (SiMe3), 30.2 (CH3), 124.8–
149.7 (Ar and C@C), 215.6 (C@O); m/z (EI): 268 (42%, [M]+), 253
(100%, [MꢀMe]+), 179 (58%).
Compound 8a: FT-IR (KBr cmꢀ1), 3053 (Ar–H), 1667 (C@O),
1615, 1503 (Ar and C@C), 1244, 823 (Si–CH3); 1H NMR (400 MHz,
CDCl3): d 2.43 (s, 3H, CH3), 6.8 (d, 1H, J=16 Hz, ArHC@CH), 7.50-
7.69 (m, 8H, ArCH= CH and Ar); 13C NMR (CDCl3): d -2.6 (SiMe3),
30.2 (CH3), 124.8-149.7 (Ar and C@C), 209.6 (C@O); m/z (EI): 268
(42%, [M]+), 253 (100%, [MꢀMe]+), 179 (58%).
4.3.3. Preparation of 1,1-bis(trimethylsilyl)-2-[2-(5-
methyl)furyl]ethene (3)
A yellowish liquid: Rf = 0.40 (n-hexane); Yield: 52%; FT-IR (KBr
cmꢀ1): 2955 (Ar–H), 1559, 1483 (C@C), 1250, 841 (Si–CH3); 1H
NMR (400 MHz, CDCl3): d 0.17 (s, 9H, SiMe3), 0.18 (s, 9H, SiMe3),
2.34 (s, 3H, CH3), 6.00–6.22 (d, 2H, JHH = 3 Hz, Ar), 7.16 (s, 1H, vi-
nyl); 13C NMR (CDCl3): d ꢀ0.40 (SiMe3), 0.64 (SiMe3), 12.6 (CH3),
106.8–152.4 (Ar and C@C); m/z (EI): 252 (23%, [M]+), 237 (30%,
[MꢀMe]+), 179 (36%, [MꢀSiMe3]+), 139 (100%), 73 (40%, [SiMe3]+).
Anal. Calc. for C13H24OSi2: C, 61.7; H, 10.5. Found: C, 61.3; H, 10.2%.
4.4.2. Reaction of 1 with C2H5COCl
The reaction of 1 with 2b (0.31 g). TLC on silica gel (5:1 n-hex-
ane:diethyl ether as eluant) gave 7b (Rf = 0.55) and 8b (Rf = 0.19,
m.p. 78 °C). 7b: FT-IR (KBr cmꢀ1), 3056 (Ar–H), 1673 (C@O),
1592, 1504 (Ar and C@C), 1250, 839 (Si–CH3); 1H NMR (400 MHz,
3
4.3.4. Preparation of 1,1-bis(trimethylsilyl)-2-(3-pyridyl)ethene (4)
A yellowish liquid: Rf = 0.64 (2:1 n-hexane:ethyl acetate as elu-
ent); Yield: 70%; FT-IR (KBr cmꢀ1): 3030, 3078 (Ar–H), 1253, 832
(Si–CH3), 1551, 1470 (C@C); 1H NMR (400 MHz, CDCl3): d 0.08 (s,
9H, SiMe3), 0.16 (s, 9H, SiMe3), 7.17–8.45 (m, 5H, Ar and vinyl);
13C NMR (CDCl3): d ꢀ0.7 (SiMe3), 0.9 (SiMe3), 121.5ꢀ149.3 (Ar and
C@C); m/z (EI): 249 (38%, [M]+), 248 (75%, [MꢀH]+), 234 (100%,
[MꢀMe]+), 176 (27%, [MꢀSiMe3]+), 73 (64%, [SiMe3]+). Anal. Calc.
for C13H23NSi2: C, 62.7; H, 9.6; N, 5.6. Found: C, 62.2; H, 10; N, 5.4%.
CDCl3): d 0.31 (s, 9H, SiMe3), 1.02 (t, 3H, JHH = 7, CH3), 2.34–2.36
(q, 2H, CH2), 7.03–7.86 (m, 8H, vinyl and Ar); 13C NMR (CDCl3): d
ꢀ2.5 (SiMe3), 6.98 (CH3), 35.5 (CH2), 124.8–149.6 (Ar and C@C),
212.3 (C@O); m/z (EI): 282 (17%, [M]+), 267 (20%, [MꢀMe]+), 253
(100%, [MꢀEt]+), 73 (35%, [SiMe3]+).
Compound 8b: FT-IR (KBr cmꢀ1), 3051 (Ar–H), 1667 (C@O),
1618, 1503 (Ar and C@C); 1H NMR (400 MHz, CDCl3): d 1.20 (t,
3H, JHH = 7, CH3), 2.71–2.76 (q, 2H, CH2), 6.91 (d, 1H, J = 16 Hz,
ArHC@CH), 7.50–7.96 (m, 8H, ArC@CH and Ar); 13C NMR (CDCl3):
d 7.5 (CH3), 33.1 (CH2), 122.5–141.2 (Ar and C@C), 199.8 (C@O).
4.3.5. Preparation of 1,1-bis(trimethylsilyl)-2-(4-chloro)phenylethene
(5)
4.4.3. Reaction of 1 with i-C3H7COCl
A
colorless liquid: Rf = 0.48 (n-hexane); Yield: 74%; FT-IR
The reaction of 1 with 2c (0.36 g). TLC on silica gel (4:1 n-hex-
ane:diethyl ether as eluant) gave 7c (Rf = 0.64) and 8c (Rf = 0.36,
m.p. 86-88 °C). 7c: FT-IR (KBr cmꢀ1), 3056 (Ar–H), 1671 (C@O),
1588, 1504 (Ar and C@C), 1250, 841 (Si–CH3); 1H NMR (400 MHz,
(KBr cmꢀ1): 3027 (Ar–H), 1551, 1484 (C@C), 1251, 837 (Si–CH3),
927 (C–Cl); 1H NMR (400 MHz, CDCl3): d 0.01 (s, 9H, SiMe3), 0.23
(s, 9H, SiMe3), 7.1–7.3 (d, 4H, JHH = 8 Hz, Ar), 7.7 (s, 1H, vinyl);
13C NMR (CDCl3): d ꢀ0.5 (SiMe3), 1.0 (SiMe3), 126.9–152.3 (Ar
and C@C); m/z (EI): 267 (64%, [MꢀMe]+), 193 (60%, [MꢀPhꢀC]+),
169 (71%,), 73 (100%, [SiMe3]+). Anal. Calc. for C14H23ClSi2: C,
59.8; H, 8.4. Found: C, 59.2; H, 8.2%.
3
CDCl3): d 0.31 (s, 9H, SiMe3), 1.00 (d, 6H, JHH = 7, CH (CH3)2),
2.49–2.52 (m, 1H, CH(CH3)2), 7.17–7.86 (m, 8H, vinyl and Ar); 13C
NMR (CDCl3): d ꢀ1.9 (SiMe3), 17.7 (CH (CH3)2), 39.8 (CH(CH3)2),
125.1–149.1 (Ar and C@C), 215.1 (C@O); m/z (EI): 224 (22%,
[MꢀHCOCH(CH3)2]+), 181 (100%, [ArCH@CCOH]+), 152 (29%,
[ArCHC]+).
4.3.6. Preparation of 1,1-bis(trimethylsilyl)-2-(2,6-
dichloro)phenylethene (6)
8c: FT-IR (KBr cmꢀ1), 3058 (Ar–H), 1677 (C@O), 1603, 1462 (Ar
3
A
colorless liquid: Rf = 0.28 (n-hexane); Yield: 70%; FT-IR
and C@C); 1H NMR (400 MHz, CDCl3): d 1.22 (d, 6H, JHH = 7,
(KBr cmꢀ1): 3057 (Ar–H), 1600, 1427 (C@C), 1253, 840 (Si–CH3),
930 (C–Cl); 1H NMR (400 MHz, CDCl3): d ꢀ0.10 (s, 9H, SiMe3),
0.25 (s, 9H, SiMe3), 7.1–7.3 (m, 4H, vinyl and Ar), 13C NMR (CDCl3):
CH(CH3)2), 2.96–3.00 (m, 1H, CH(CH3)2), 6.94 (s, 1H, ArHC@CH),
7.50–7.96 (m, 8H, Ar and ArHC@CH); 13C NMR (CDCl3): d 17.5
(CH(CH3)2), 38.3 (CH(CH3)2), 122.5–141.4 (Ar and C@C), 202.8
(C@O).
d
ꢀ0.6 (SiMe3), ꢀ0.5 (SiMe3), 126.4–149.2 (Ar and C@C); m/z (EI):
301 (100%, [MꢀMe]+), 227 (56%, [MꢀPhꢀC]+), 73 (72%, [SiMe3]+).
Anal. Calc. for C14H22Cl2Si2: C, 52.6; H, 6.5. Found: C, 52.4; H, 6.9%.
4.4.4. Reaction of 1 with i-C4H9COCl
The reaction of 1 with 2d (0.41 g). TLC on silica gel (8:1 n-hex-
ane:diethyl ether as eluant) gave 7d (Rf = 0.56) and 8d (Rf = 0.21).
Compound 7d: FT-IR (KBr cmꢀ1), 3056 (Ar–H), 1675 (C@O), 1589,
1505 (Ar and C@C), 1249, 841 (Si–CH3); 1H NMR (400 MHz, CDCl3):
4.4. General procedure for Friedel–Crafts reactions using 1,1-
bis(trimethylsilyl)-2-(2-naphthyl)ethene as a precursor
3
A
solution of 1,1-bis(trimethylsilyl)-2-(2-naphthyl)ethene
d 0.28 (s, 9H, SiMe3), 0.81 (d, 6H, JHH = 6 Hz, CH(CH3)2), 2.11–2.19
3
(1.0 g, 3.7 mmol) in dry CH2Cl2 (20 ml) was added during 15 min
at 0 °C under argon to a stirred solution of anhydrous aluminum
trichloride (7.1 g, 15.3 mequiv.) in dry CH2Cl2 (30 ml) containing
acyl chloride (3.36 mmol), and the mixture was stirred at 0 °C for
a further 105 min. The reaction mixture was poured into water
(50 ml) and extracted twice with 50 ml of ether. The combined or-
ganic layers were dried (Na2SO4) and filtered. The solvent was
evaporated and the residue was then purified by preparative TLC
(silica gel) to give the products.
(m, 1H, CH2CH(CH3)2), 2.22 (d, 2H, JHH = 6 Hz, COCH2CH(CH3)2),
6.98–7.90 (m, 8H, vinyl and Ar); 13C NMR (CDCl3): d ꢀ2.4 (SiMe3),
21.6 (CH(CH3)2), 22.4 (CH(CH3)2), 50.7 (CH2CH(CH3)2), 125.1–149.7
(Ar and C@C), 210.7 (C@O); m/z (EI): 310 (64%, [M]+), 295 (73%,
[MꢀMe]+), 267 (87%, [MꢀCH(CH3)2]+), 253 (100%, [MꢀCH2CH-
(CH3)2]+), 73 (59%, [SiMe3]+).
Compound 8d: FT-IR (KBr cmꢀ1), 3056 (Ar–H), 1687 (C@O),
1605, 1464 (Ar and C@C); 1H NMR (400 MHz, CDCl3): d 1.02 (d,
3
6H, JHH = 6 Hz, CH(CH3)2), 2.24-2.34 (m, 1H, CH2CH(CH3)2), 2.58
3
(d, 2H, JHH = 6 Hz, COCH2CH(CH3)2), 6.86 (s, 1H, ArHC@CH),
4.4.1. Reaction of 1 with CH3COCl
The reaction of 1 with 2a (0.27 g). TLC on silica gel (7:2 n-hex-
ane:diethyl ether as eluant) gave 7a (Rf = 0.25) and 8a (Rf = 0.27,
7.46–7.94 (m, 8H, Ar and ArCH@CH); 13C NMR (CDCl3): d 21.7
(CH(CH3)2), 24.2 (CH(CH3)2), 48.9 (CH2CH(CH3)2), 122.4–153.7 (Ar
and C@C), 199.1 (C@O).