I. Matsuda et al. / Journal of Organometallic Chemistry 574 (1999) 133–141
139
4.2.12. (Z)-2-Acetoxymethyl-3-dimethyl-
phenylsilylpropenal (8a)
2.40 (t, 3H, J=0.95 Hz, CH3), 6.96–7.02 (m, 3H,
Ph), 7.21–7.37 (m, 7H, Ph), 10.30 (s, 1H,
CHO). 13C-NMR (50 MHz) l: −2.43 (SiCH3),
15.91 (CH2), 19.70 (CH3), 126.98 (Ph meta), 127.55
(Ph para), 127.66 (Ph ortho), 128.58 (Ph meta),
128.85 (Ph para), 133.72 (Ph ortho), 135.91 (Ph ipso),
139.19 (Ph ipso), 143.37 (ꢁC q), 152.97 (ꢁC q), 191.92
(CHO).
A colorless liquid (b.p. 135°C/0.1 torr). 1H-NMR
(200 MHz) l: 0.54 (s, 6H, Si(CH3)2), 2.11 (s, 3H,
C(ꢁO)CH3), 4.82 (d, J=1.5 Hz, 2H, OCH2), 7.13 (d,
J=1.5 Hz, 1H, ꢁCH), 7.35–7.41 (m, 3H, Ph), 7.49–
7.55 (m, 2H, Ph), 9.77 (s, 1H, CHO). 13C-NMR (50
MHz) l: −0.69 (SiCH3), −0.60 (SiCH3), 20.70
(C(ꢁO)CH3), 62.35 (OCH2), 128.43 (Ph meta), 129.89
(Ph para), 133.71 (Ph ortho), 137.23 (Ph ipso), 150.07
(ꢁC q), 150.35 (ꢁCH), 170.63 (OC(ꢁO)), 191.89 (CHO).
Anal. calc. for C14H18O3Si: C, 64.09%; H, 6.91%.
Found: C, 63.87%; H, 6.83%.
4.2.9. 2-(Dimethylphenylsilylmethyl)-3,3-diph-
enylpropenal (3h)
A yellow–orange oily liquid (b.p. 200°C/6 torr). IR:
1
1669 cm−1 (wCꢁO). H-NMR (200 MHz) d: 0.21 (s, 6H,
Si(CH3)2), 2.24 (s, 2H, SiCH2), 6.94–7.00 (m, 1H,
Ph), 7.03–7.08 (m, 2H, Ph), 7.24–7.38 (m, 12H, Ph),
9.46 (s, 1H, CHO). 13C-NMR (75 MHz) l: −2.02
(SiCH3), 17.59 (SiCH2), 127.62 (Ph), 127.96
(Ph), 128.05 (Ph), 128.32 (Ph), 128.56 (Ph), 128.85 (Ph),
129.24 (Ph), 130.96 (Ph), 133.67 (Ph), 138.37 (Ph
ipso), 138.63 (ꢁC q), 139.48 (Ph ipso), 141.44 (Ph ipso),
159.90 (ꢁC q), 194.07 (CHO). Anal. Calc. for
C24H24OSi: C, 80.85%; H, 6.78%; Found C, 80.74%; H,
6.70%.
4.2.13. (Z)-2-(1-Acetoxyethyl)-3-dimethyl-
phenylsilylpropenal (8b)
A colorless liquid (b.p. 150°C/0.2 torr). IR: 1748,
1
1687 cm−1 (wCꢁO). H-NMR (200 MHz) l: 0.52 (s, 6H,
Si(CH3)2), 1.34 (d, J=6.5 Hz, 3H, CHCH3), 2.07 (s,
3H, C(ꢁO)CH3), 5.70 (dq, J=6.5 and 1.0 Hz, 1H
CHCH3), 7.10 (d, J=1.0 Hz, 1H, ꢁCH), 7.33–7.41 (m,
3H, Ph), 7.46–7.55 (m, 2H, Ph), 9.76 (s, 1H, CHO).
13C-NMR (50 MHz) l: −0.65 (SiCH3), −0.60
(SiCH3), 20.22 (CH3), 20.98 (C(ꢁO)CH3), 67.92
(OCH), 128.38 (Ph meta), 129.79 (Ph para), 133.66 (Ph
ortho), 137.45 (Ph ipso), 147.41 (ꢁCH), 156.10 (ꢁC q),
169.91 (OC(ꢁO)), 191.64 (CHO). Anal. Calc. for
C15H20O3Si: C, 65.18%; H, 7.29%. Found: C, 65.19%;
H, 7.28%.
4.2.10. (Z)-2-(Methoxycarbonyloxymethyl)-3-
dimethylphenylsilylpropenal (7a)
A colorless liquid (b.p. 120°C/0.15 torr). IR: 1753,
1
1682 cm−1 (wCꢁO). H-NMR (300 MHz) l: 0.54 (s, 6H,
Si(CH3)2), 3.81 (s, 3H, OCH3), 4.88 (d, J=1.5 Hz, 2H,
OCH2), 7.20 (t, J=1.5 Hz, 1H, ꢁCH), 7.34–7.43 (m,
3H, Ph), 7.49–7.55 (m, 2H, Ph), 9.76 (s, 1H, CHO).
13C-NMR (75 MHz) l: −0.38 (SiCH3), 55.03 (OCH3),
65.56 (OCH2), 128.17 (Ph meta), 129.64 (Ph para),
133.42 (Ph ortho), 136.80 (Ph ipso), 149.40 (ꢁC q),
150.10 (ꢁCH), 155.12 (OC(ꢁO)), 191.13 (CHO). Anal.
Calc. for C14H18O4Si: C, 60.40%; H, 6.52%. Found: C,
60.34%; H, 6.54%.
4.2.14. (Z)-2-(1-Methoxycarbonyloxyhexyl)-3-
dimethylphenylsilylpropenal (8c)
A pale yellow oily liquid (b.p. 120°C/0.15 torr). IR:
1
1737, 1684 cm−1 (wCꢁO). H-NMR (300 MHz) l: 0.51
(s, 3H, SiCH3), 0.52 (s. 3H, SiCH3), 0.87 (t, J=6.6 Hz,
3H, CH3), 1.24–1.32 (m, 6H, 3×CH2), 1.59–1.67 (m,
2H, CH2), 2.08 (s, 3H, C(ꢁO)CH3), 5.61 (ddd, J=6.9,
4.8, and 0.9 Hz, 1H, OCH), 7.03 (d, J=0.9 Hz, 1H,
ꢁCH), 7.35–7.41 (m, 3H, Ph), 7.46–7.52 (m, 2H, Ph),
9.75 (s, 1H, CHO). 13C-NMR (75 MHz) d: −0.25
(SiCH3), −0.20 (SiCH3), 14.03 (CCH3), 21.18
(C(ꢁO)CH3), 22.52 (CH2), 25.05 (CH2), 31.43 (CH2),
34.37 (CH2), 71.61 (OCH), 128.12 (Ph meta), 129.50
(Ph para), 133.38 (Ph ortho), 137.24 (Ph ipso), 147.53
(ꢁCH), 155.00 (ꢁC q), 169.66 (OC(ꢁO)), 191.12 (CHO).
Anal. Calc. for C19H28O3Si: C, 68.63%; H, 8.49%.
Found: C, 68.34%; H, 8.53%.
4.2.11. (Z)-2-(1-Methoxycarbonyloxyhexyl)-3-
dimethylphenylsilylpropenal (7c)
A pale yellow liquid (b.p. 130°C/0.2 torr). IR: 1748,
1
1683 cm−1 (wCꢁO). H-NMR (300 MHz) l: 0.52 (s, 3H,
SiCH3), 0.53 (s, 3H, SiCH3), 0.87 (t, J=6.9 Hz, 3H,
CH2CH3), 1.20–1.38 (m, 6H, 3×CH2), 1.60–1.75 (m,
2H, CH2), 3.77 (s, 3H, OCH3), 5.52 (ddd, J=6.3, 6.0
and 0.6 Hz, 1H, OCH), 7.14 (d, J=0.6 Hz, 1H, ꢁCH),
7.33–7.42 (m, 3H, Ph), 7.45–7.53 (m, 2H, Ph), 9.75 (s,
1H, CHO). 13C-NMR (75 MHz) l: −0.42 (SiCH3),
−0.34 (SiCH3), 13.91 (CH2CH3), 22.41 (CH2), 24.78
(CH2), 31.34 (CH2), 34.48 (CH2), 54.79 (OCH3), 75.15
(OCH2), 128.25 (Ph meta), 129.66 (Ph para), 133.52
(Ph ortho), 137.26 (Ph ipso), 148.14 (ꢁCH), 154.70 (ꢁC
q), 154.80 (OC(ꢁO)), 191.21 (CHO). Anal. Calc. for
C19H28O4Si: C, 65.48%; H, 8.10%. Found: C, 65.30%;
H, 8.16%.
4.2.15. (Z)-2-(1-Methoxycarbonyloxy-1-methylethyl)-3-
dimethylphenylsilylpropenal (8d)
A colorless liquid (b.p. 100°C/0.2 torr). IR: 1729,
1
1688 cm−1 (wCꢁO). H-NMR (300 MHz) l: 0.50 (s, 6H,
Si(CH3)2), 1.63 (s, 6H, 2×CH3), 2.00 (s, 3H,
C(ꢁO)CH3), 6.90 (s, 1H, ꢁCH), 7.35–7.40 (m, 3H, Ph),
7.50–7.56 (m, 2H, Ph), 9.76 (s, 1H, CHO). 13C-NMR
(75 MHz) l: −0.34 (SiCH3), 21.97 (C(ꢁO)CH3), 27.05