518
K. Miura et al. / Journal of Organometallic Chemistry 692 (2007) 514–519
J = 7.0 Hz, 9H), 0.95 (d, J = 6.6 Hz, 3H), 1.28–1.35 (m,
12H), 1.53 (br s, 1H), 1.71–1.83 (m, 1H), 3.35 (dd,
J = 10.3, 6.9 Hz, 1H), 3.44 (dd, J = 10.3, 5.6 Hz, 1H);
13C NMR (CDCl3) d 13.20 (CH2 · 3), 13.75 (CH3 · 3),
16.86 (CH2), 19.46 (CH3), 26.65 (CH2 · 3), 27.44
(CH2 · 3), 33.17 (CH), 70.79 (CH2). Anal. Calc. for
C16H36GeO: C, 60.61; H, 11.44. Found: C, 60.31; H,
11.37%.
Bu, 44). Anal. Calc. for C16H34GeO2: C, 58.05; H, 10.35.
Found: C, 58.10; H, 10.39%.
4.2.8. 4-(Tributylgermyl)octane (3h)
Bp 200 ꢁC (1 Torr, bath temp.). IR (neat) 2956, 2924,
1
2856, 1464 cmꢀ1; H NMR (CDCl3) d 0.67–0.73 (m, 6H),
0.85–0.91 (m, 15H), 0.97–1.06 (m, 1H), 1.20–1.42 (m,
22H); 13C NMR (CDCl3) d 12.16 (CH2 · 3), 13.76
(CH3 · 3), 14.12 (CH3), 14.48 (CH3), 22.22 (CH2), 23.08
(CH2), 25.67 (CH), 26.85(CH2 · 3), 27.67 (CH2 · 3),
30.71 (CH2), 31.41 (CH2), 33.51 (CH2); MS m/z (relative
intensity) 301 (M+ – Bu, 5.4), 299 (M+ – Bu – 2, 4.0),
297 (M+ – Bu – 4, 2.9), 189 (100). Anal. Calc. for
C20H44Ge: C, 67.25; H, 12.42. Found: C, 67.16; H, 12.79%.
4.2.4. 1-(Tributylgermyl)undecane (3d)
Bp 180 ꢁC (1.3 Torr, bath temp.). IR (neat) 2956, 2924,
1
2854, 1464 cmꢀ1; H NMR (CDCl3) d 0.65–0.71 (m, 8H),
0.86–0.94 (m, 12H), 1.12–1.52 (m, 30H); 13C NMR
(CDCl3) d 11.86 (CH2), 12.49 (CH2 · 3), 13.79 (CH3 · 3),
14.12 (CH3), 22.71 (CH2), 25.23 (CH2), 26.67 (CH2 · 3),
27.54 (CH2 · 3), 29.32 (CH2), 29.38 (CH2), 29.67 (CH2),
29.68 (CH2), 29.74 (CH2), 31.95 (CH2), 33.71 (CH2); MS
m/z (relative intensity) 343 (M+ – Bu, 33), 341 (M+ – 2 –
Bu, 21), 339 (M+ – 4 – Bu, 17), 57 (100). Anal. Calc. for
C23H50Ge: C, 69.19; H, 12.62. Found: C, 69.29; H, 12.71%.
4.2.9. 1-Tributylgermyl-2-(trimethylsiloxy)cyclohexane (3i,
single isomer)
Bp 230 ꢁC (1 Torr, bath temp.). IR (neat) 2956, 2925,
1
2871, 1738, 1252 cmꢀ1; H NMR (CDCl3) d 0.10 (s, 9H),
0.65–0.75 (m, 6H), 0.89 (t, J = 6.9 Hz, 9H), 1.13–1.81 (m,
21H), 4.03–4.06 (m, 1H); 13C NMR (CDCl3) d 0.68
(CH3 · 3), 12.13 (CH2 · 3), 13.80 (CH3 · 3), 20.94 (CH2),
23.78 (CH2), 26.93 (CH2 · 3), 27.64 (CH2), 27.71
(CH2 · 3), 33.28 (CH), 35.05 (CH2), 70.31 (CH); MS m/z
4.2.5. 1-Butoxy-2-(tributylgermyl)ethane (3e)
Bp 130 ꢁC (2 Torr, bath temp.). IR (neat) 2956, 2925,
2854, 1107 cmꢀ1 1H NMR (CDCl3) d 0.68–0.74 (m, 6
;
H), 0.85–0.94 (m, 12H), 1.05–1.12 (m, 2H), 1.28–1.44 (m,
14H), 1.50–1.60 (m, 2H), 3.39 (t, J = 6.6 Hz, 2H), 3.45–
3.51 (m, 2 H); 13C NMR (CDCl3) d 12.67 (CH2 · 3),
13.74 (CH3 · 3), 13.94 (CH3), 14.21 (CH2), 19.46 (CH2),
26.56 (CH2 · 3), 27.41 (CH2 · 3), 32.03 (CH2), 68.65
(CH2), 70.07 (CH2); MS m/z (relative intensity) 289 (M+
– Bu, 13), 287 (M+ – 2 – Bu, 9.5), 285 (M+ – 4 – Bu,
6.9), 261 (100). Anal. Calc. for C18H40GeO: C, 62.64; H,
11.68. Found: C, 62.52; H, 11.76%.
(relative intensity) 277 (M+ – Bu – C6H10, 47), 275 (M+
–
2 – Bu – C6H10, 32), 273 (M+ – 4 – Bu – C6H10, 25), 73
(100). Anal. Calc. for C21H46GeOSi: C, 60.74; H, 11.16.
Found: C, 60.68; H, 11.10%.
4.2.10. 1-Methyl-2-(tributylgermylmethyl)cyclopentane
(6a, cis:trans = 3:1)
Bp 220 ꢁC (1 Torr, bath temp.). IR (neat) 2954, 2924,
1
2870, 1462 cmꢀ1; H NMR (CDCl3) d 0.62–0.95 (m, 20H)
including 0.80 (d, J = 9.2 Hz), 0.88 (t, J = 7.0 Hz), and
0.94 (d, J = 6.1 Hz), 1.01–1.36 (m, 16H), 1.45–1.95 (m,
4H); 13C NMR (CDCl3) for the major isomer d 13.09
(CH3 · 3), 13.51 (CH2), 13.80 (CH2 · 3), 14.85 (CH3),
22.63 (CH2), 26.77 (CH2 · 3), 27.57 (CH2 · 3), 32.33
(CH2), 33.07 (CH2), 38.39 (CH), 40.25 (CH), for the minor
isomer d 13.13 (CH3 · 3), 13.80 (CH2 · 3), 17.59 (CH2),
18.72 (CH3), 23.13 (CH2), 26.77 (CH2 · 3), 27.57
(CH2 · 3), 34.22 (CH2), 34.92 (CH2), 44.38 (CH), 45.09
(CH); MS m/z (relative intensity) for the major isomer
285 (M+ – Bu, 23), 283 (M+ – Bu – 2, 15), 281 (M+ – Bu
– 4, 14), 55 (100), for the minor isomer 285 (M+ – Bu,
17), 283 (M+ – Bu – 2, 10), 281 (M+ – Bu – 4, 12), 55
(100). Anal. Calc. for C19H40Ge: C, 66.89; H, 11.82.
Found: C, 66.59; H, 11.90%.
4.2.6. Cyclohexyl 3-(tributylgermyl)propanoate (3f)
Bp 230 ꢁC (1 Torr, bath temp.). IR (neat) 2927, 2858,
1
1732 (C@O), 1454, 1200 cmꢀ1; H NMR (CDCl3) d 0.69–
0.75 (m, 6H), 0.89 (t, J = 7.0 Hz, 9H), 0.96–1.02 (m, 2H),
1.23–1.50 (m, 18H), 1.69–1.90 (m, 4H), 2.26–2.32 (m,
2H), 4.71–4.78 (m, 1H); 13C NMR (CDCl3) d 7.71 (CH2),
12.25 (CH2 · 3), 13.72 (CH3 · 3), 23.79 (CH2 · 2), 25.41
(CH2), 26.57 (CH2 · 3), 27.35 (CH2 · 3), 30.47 (CH2),
31.66 (CH2 · 2), 72.43 (CH), 174.66 (C); MS m/z (relative
intensity) 261 (M+ – Bu –C6H10, 54), 259 (M+ – 2 – Bu –
C6H10, 44), 257 (M+ – 4 – Bu – C6H10, 32). Anal. Calc.
for C21H42GeO2: C, 63.19; H, 10.61. Found: C, 63.18; H,
10.76%.
4.2.7. Methyl 3-(tributylgermyl)propanoate (3g)
Bp 130 ꢁC (2 Torr, bath temp.). IR (neat) 2956, 2923,
4.2.11. 1,1-Bis(methoxymethyl)-3-methyl-4-
(tributylgermylmethyl)cyclopentane (6b, cis:trans = 4:1)
Bp 250 ꢁC (1 Torr, bath temp.). IR (neat) 2954, 2924,
1
2856, 1741 (C@O), 1464, 1205 cmꢀ1; H NMR (CDCl3) d
0.68–0.76 (m, 6H), 0.89 (t, J = 6.8 Hz, 9H), 0.97–1.04 (m,
2H), 1.32 (br s, 12H), 2.32–2.49 (m, 2H), 3.67 (s, 3H);
13C NMR (CDCl3) d 7.68 (CH2), 12.22 (CH2 · 3), 13.72
(CH3 · 3), 26.56 (CH2 · 3), 27.33 (CH2 · 3), 29.92 (CH2),
51.54 (CH3), 175.62 (C); MS m/z (relative intensity) 275
(M+ – Bu, 100), 273 (M+ – 2 – Bu, 78), 271 (M+ – 4 –
1
2871, 1458, 1113 cmꢀ1; H NMR (CDCl3) d 0.35–0.95 (m,
20H), 1.15–1.34 (m, 14H), 1.53–1.78 (m, 2.4H), 1.89–2.08
(m, 1.6H), 3.17 (s, 2.4H), 3.24 (br s, 1.6H), 3.33 (s, 6H);
13C NMR (CDCl3) for the major isomer d 13.00
(CH2 · 3), 13.41 (CH2), 13.76 (CH3 · 3), 15.81 (CH3),