1562
R. Takagi et al. / Journal of Organometallic Chemistry 696 (2011) 1556e1564
4.3. 13-Methyltetradecanyl 2-propenyl amine (4b)
1H NMR (500 MHz, CDCl3)
1 H), 0.87 (d, J ¼ 6.6 Hz, 6 H), 0.86 (d, J ¼ 6.6 Hz, 6 H); 13C NMR
(125 MHz, CDCl3)
d 71.3, 71.0, 39.1, 35.3, 29.9, 29.8, 29.7, 29.6, 29.5,
d
5.91 (ddt, J ¼ 17.2, 10.3, 6.0 Hz, 1 H),
28.0, 27.9, 27.7, 27.4, 26.2, 22.7, 22.6; HR-APCIMS m/z calcd for
5.19 (dq, J ¼ 17.2, 1.5 Hz, 1 H), 5.10 (dq, J ¼ 10.3, 1.5 Hz, 1 H), 3.27 (dt,
J ¼ 6.0, 1.5 Hz, 2 H), 2.61 (t, J ¼ 7.3 Hz, 2 H), 1.54e1.45 (m, 2 H),
1.35e1.18 (m, 20 H), 1.18e1.11 (m, 1 H), 0.86 (d, J ¼ 6.7 Hz, 6 H);
C21H45O [M þ H]þ 313.3465, found 313.3469.
4.10. 13-Methyltetradecanyl 4-pentenyl amine (7b)
13C NMR (125 MHz, CDCl3)
d 136.6, 116.1, 52.4, 49.4, 39.1, 29.9, 29.7,
1H NMR (500 MHz, CDCl3)
d
5.82 (ddt, J ¼ 17.1, 10.3, 6.6 Hz, 1 H),
29.6, 29.5, 28.0, 27.4, 27.3, 22.7; HR-EIMS m/z calcd for C18H37
N
[Mþ] 267.2926, found 267.2932; Anal. Calcd for C18H37N: C, 80.82;
H, 13.94; N, 5.24. Found: C, 80.80; H, 14.12; N, 5.13.
5.02 (dq, J ¼ 17.1, 1.6 Hz, 1 H), 4.96 (ddt, J ¼ 10.3, 1.6, 1.2 Hz, 1 H),
2.67e2.58 (m, 4 H), 2.14e2.06 (m, 2 H), 1.67e1.58 (m, 2 H),
1.57e1.46 (m, 4 H), 1.35e1.22 (m, 18 H), 1.18e1.11 (m, 1 H), 0.86
(d, J ¼ 6.6 Hz, 6 H); LR-EIMS m/z (%): 55 (15), 70 (29), 85 (16), 98
(100), 112 (1.5), 140 (1.6), 154 (1.3), 224 (1.3), 240 (16), 280 (5), 295
(0.3) [Mþ].
4.4. 14-Hydroxy-13-methyltetradecanyl 2-propenyl amine (4b0)
1H NMR (500 MHz, CDCl3)
d
5.92 (ddt, J ¼ 17.5, 10.3, 6.3 Hz, 1 H),
5.21 (dq, J ¼ 17.5, 1.4 Hz, 1 H), 5.14 (tq, J ¼ 10.3, 1.4 Hz, 1 H), 3.50 (dd,
J ¼ 10.5, 5.7 Hz, 1 H), 3.41 (dd, J ¼ 10.5, 6.6 Hz, 1 H), 3.30 (dt, J ¼ 6.2,
1.4 Hz, 2 H), 3.18 (bs,1 H), 2.64 (t, J ¼ 7.5 Hz, 2 H), 1.66e1.49 (m, 3 H),
1.44e1.19 (m, 19 H), 1.16e1.04 (m, 1 H), 0.91 (d, J ¼ 6.7 Hz, 3H); LR-
EIMS m/z (%): 63 (3), 77 (6), 89 (2), 102 (5), 142 (8), 165 (1), 207 (3),
229 (2), 115 (15), 128 (100), 258 (21), 283 (0.1) [Mþ].
4.11. 14-Hydroxy-13-methyltetradecanyl 4-pentenyl amine (7b0)
1H NMR (500 MHz, CDCl3)
d
5.80 (ddt, J ¼ 17.1, 10.2, 6.6 Hz, 1 H),
5.03 (dq, J ¼ 17.1,1.6 Hz,1 H), 4.97 (ddt, J ¼ 10.2, 1.6, 1.2 Hz,1 H), 3.50
(dd, J ¼ 10.7, 5.7 Hz, 1 H), 3.41 (dd, J ¼ 10.3, 6.5 Hz, 1 H), 2.82e2.70
(m, 1 H), 2.70e2.61 (m, 4 H), 2.14e2.06 (m, 2 H), 1.72e1.51 (m, 4 H),
1.34e1.20 (m, 21 H), 0.91 (d, J ¼ 6.8 Hz, 3 H); LR-EIMS m/z (%): 55
(21), 70 (32), 79 (32), 85 (17), 98 (100), 112 (4), 124 (4), 140 (2), 254
(9), 294 (3) [Mþ ꢁ 17].
4.5. 13-Methyltetradecanyl 2-propenyl sulfide (4c)
1H NMR (500 MHz, CDCl3)
d
5.79 (ddt, J ¼ 16.8, 10.1, 7.2 Hz, 1 H),
5.11e5.06 (m, 2 H), 3.12 (dt, J ¼ 7.2, 1.1 Hz, 2 H), 2.50 (t, J ¼ 7.5 Hz,
2 H), 1.60e1.46 (m, 4 H), 1.40e1.32 (m, 2 H), 1.32e1.22 (m, 16 H)
1.18e1.10 (m, 1 H), 0.82 (d, J ¼ 6.6 Hz, 6 H); 13C NMR (125 MHz,
4.12. 4-Methylpropanyl 13-methyltetradecanyl amine (9b)
CDCl3)
d 134.6, 116.6, 39.0, 34.8, 30.8, 29.9, 29.7, 29.6, 29.5, 29.4,
29.3, 29.2, 28.9, 27.9, 27.4, 22.6; HR-EIMS m/z calcd for C18H36S [Mþ]
1H NMR (500 MHz, CDCl3)
d 2.60e2.54 (m, 4 H), 1.63e1.20 (m,
267.2926, found 267.2932.
28 H), 0.88 (d, J ¼ 6.6 Hz, 6 H), 0.86 (d, J ¼ 6.8 Hz, 6 H); LR-EIMS m/z
(%): 77 (5), 89 (2), 102 (5), 115 (14), 128 (100), 142 (8), 165 (1), 215
(1), 230 (2), 239 (1), 258 (19).
4.6. 14-Hydroxy-13-methyltetradecanyl 2-propenyl sulfide (4c0)
1H NMR (500 MHz, CDCl3)
d
5.80 (ddt, J ¼ 16.8, 10.1, 7.1 Hz, 1 H),
4.13. 13-Methyltetradecanyl 4-pentenyl sulfide (7c)
5.11e5.06 (m, 2 H), 3.54e3.48 (m, 1 H), 3.45e3.38 (m, 1 H), 3.13 (dt,
J ¼ 7.1, 1.1 Hz, 1 H), 2.45 (t, J ¼ 7.6 Hz, 1 H), 1.65e1.49 (m, 4 H),
1.43e1.32 (m, 2 H), 1.32e1.20 (m, 18 H), 1.16e1.05 (m, 1 H), 0.91
(d, J ¼ 6.8 Hz, 3 H); LR-EIMS m/z (%): 57 (55), 69 (45), 83 (35), 97
(25), 111 (8), 145 (1.7), 159 (1.8), 173 (2.3), 187 (2.3), 201 (2.3), 215
(1.3), 227 (2.5), 257 (100), 283 (0.3), 300 (0.3) [Mþ].
1H NMR (500 MHz, CDCl3)
d
5.80 (ddt, J ¼ 17.1, 10.2, 6.7 Hz, 1 H),
5.03 (dq, J ¼ 17.1, 1.8 Hz, 1 H), 4.98 (ddt, J ¼ 10.2, 1.8, 1.2 Hz, 1 H), 2.51
(t, J ¼ 7.0 Hz, 2 H), 2.50 (t, J ¼ 7.0 Hz, 2 H), 2.18e2.13 (m, 2 H),
1.72e1.64 (m, 2 H), 1.62e1.47 (m, 4 H), 1.41e1.33 (m, 2 H), 1.33e1.20
(m, 16 H), 1.18e1.11 (m, 1 H), 0.86 (d, J ¼ 6.6 Hz, 6 H); 13C NMR
(125 MHz, CDCl3) d 137.9, 115.0, 39.1, 32.8, 32.1, 31.5, 29.9, 29.7, 29.6,
4.7. 13-Methyltetradecanyl 4-pentenyl ether (7a)
29.5, 29.2, 28.9, 27.9, 27.4, 22.6; Anal. Calcd for C20H40S: C, 76.84; H,
12.90. Found: C, 76.58; H, 13.16.
1H NMR (500 MHz, CDCl3)
d
5.82 (ddt, J ¼ 17.1, 10.2, 6.6 Hz, 1 H),
5.02 (dq, J ¼ 17.1, 1.8 Hz,1 H), 4.96 (ddt, J ¼ 10.2, 1.8, 1.3 Hz, 1 H), 3.41
(t, J ¼ 6.6 Hz, 2 H), 3.39 (t, J ¼ 6.7 Hz, 2 H),2.15e2.09 (m, 2 H),
1.72e1.62 (m, 2 H), 1.60e1.52 (m, 2 H), 1.40e1.20 (m, 20 H),
1.18e1.11 (m, 1 H), 0.86 (d, J ¼ 6.6 Hz, 6 H); 13C NMR (125 MHz,
4.14. 14-Hydroxy-13-methyltetradecanyl 4-pentenyl sulfide (7c0)
1H NMR (500 MHz, CDCl3)
d
5.79 (ddt, J ¼ 17.0, 10.1, 6.6 Hz, 1 H),
5.04 (dq, J ¼ 17.0, 1.7 Hz, 1 H), 4.98 (ddt, J ¼ 10.1, 1.7, 1.2 Hz, 1 H), 3.51
(dd, J ¼ 10.5, 5.6 Hz, 1 H), 3.42 (dd, J ¼ 10.5, 6.5 Hz, 1 H), 2.51 (t,
J ¼ 6.7 Hz, 2 H), 2.50 (t, J ¼ 6.9 Hz, 2 H), 2.19e2.12 (m, 2 H),1.72e1.64
(m, 2 H), 1.64e1.53 (m, 3 H), 1.43e1.32 (m, 2 H), 1.32e1.18 (m, 18 H),
1.15e1.06 (m, 1 H), 0.92 (d, J ¼ 6.6 Hz, 3 H); 13C NMR (125 MHz,
CDCl3) d 138.4,114.6, 71.0, 70.1, 39.0, 30.4, 29.8, 29.7, 29.6, 29.5, 28.9,
27.9, 27.4, 26.2, 22.7; HR-EIMS m/z calcd for C20H40O [Mþ]
296.3079, found 296.3089.
4.8. 14-Hydroxy-13-methyltetradecanyl 4-pentenyl ether (7a0)
CDCl3)
d 137.9, 115.0, 68.4, 35.8, 33.2, 32.9, 32.2, 31.5, 29.9, 29.7,
1H NMR (500 MHz, CDCl3)
d
5.82 (ddt, J ¼ 17.0, 10.1, 6.6 Hz, 1 H),
29.6, 29.5, 29.3, 28.9, 27.0, 16.6; HR-APCIMS m/z Calcd for C20H41
S
[M þ H]þ 329.2873, found 329.2875.
5.02 (dq, J ¼ 17.0, 1.6 Hz, 1 H), 4.96 (ddt, J ¼ 10.1, 2.1, 1.2 Hz, 1 H), 3.51
(dd, J ¼ 10.6, 5.7 Hz, 1 H), 3.44e3.37 (m, 3 H), 2.15e2.09 (m, 2 H),
1.70e1.63 (m, 2 H),1.63e1.52 (m, 3 H),1.43e1.21 (m, 22 H),1.14e1.03
(m, 1 H), 0.91 (d, J ¼ 6.7 Hz, 3 H); LR-EIMS m/z (%): 55 (70), 69 (100),
81 (32), 99 (25), 109 (13), 123 (5), 137 (3), 294 (0.1) [Mþ ꢁ 18].
4.15. 4-Methylpentanyl 13-methyltetradecanyl sulfide (9c)
1H NMR (500 MHz CDCl3)
d
2.50 (t, J ¼ 7.2 Hz, 2 H), 2.49 (t,
J ¼ 7.2 Hz, 2 H), 1.62e1.46 (m, 6 H), 1.43e1.33 (m, 2 H), 1.32e1.19 (m,
19 H), 1.18e1.11 (m, 1 H), 0.88 (d, J ¼ 6.6 Hz, 6 H), 0.86 (d, J ¼ 6.6 Hz,
4.9. 4-Methylpentanyl 13-methyltetradecanyl ether (9a)
6 H); 13C NMR (125 MHz, CDCl3)
d 39.1, 38.2, 32.2, 29.8, 29.5, 29.3,
1H NMR (500 MHz, CDCl3)
J ¼ 6.8 Hz, 2 H),1.62e1.46 (m, 8 H),1.38e1.17 (m,19 H),1.17e1.11 (m,
d
3.39 (t, J ¼ 6.8 Hz, 2 H), 3.38 (t,
27.6, 22.7, 22.5. HR-EIMS m/z calcd for C21H44S [Mþ] 328.3164,
found 328.3152.