Transesterification by Oxotitanium and Vanadyl Species
141.3, 127.6, 127.0, 125.1, 119.9, 66.9, 65.5, 65.4, 52.6, 47.2,
41.9, 31.9, 29.7, 29.3, 29.2, 29.0, 28.5, 25.8, 24.8, 22.8, 22.7,
21.9; TLC Rf 0.30 (EtOAc/hexane, 1/9); HR-MS (FAB+) calcd
for C39H59NO4 + H: 606.4522, found: 606.4524. Anal. Calcd
for C39H59NO4: C, 77.31; H, 9.82; N, 2.31. Found: C, 77.55;
H, 9.63; N, 2.18.
Octadecyl Pyridine-2-carboxylate, 2n.51 Data: mp 49-
52 °; IR (KBr) 2959 (m), 2915 (s), 2849 (s), 1720 (s), 1594 (w),
1473 (m), 1425 (w), 1300 (m), 1237 (w), 1189 (w), 1134 (m),
1
1093 (w), 1030 (w), 957 (w); H NMR (400 MHz, CDCl3) 9.21
(d, J ) 1.3, 1H), 8.75-8.73 (m, 1H), 8.29-8.26 (m, 1H), 7.37-
7.34 (m, 1H), 4.33 (t, J ) 6.7, 2H), 1.76 (quint, J ) 7.0, 2H),
1.44-1.23 (m, 30H), 0.83 (t, J ) 6.8, 3H); 13C NMR (100 MHz,
CDCl3) 165.3, 153.3, 150.9, 137.0, 126.4, 123.2, 65.6, 31.9, 29.7,
29.64, 29.55, 29.5, 29.3, 29.2, 28.6, 26.0, 22.7, 14.1; MS (20
eV) 376 (M + 1+, 5), 124 (100), 106 (56), 78 (40); TLC Rf 0.35
(EtOAc/hexane, 1/10); HR-MS (FAB+) calcd for C24H41NO2 +
H: 376.3216, found: 376.3214.
Octadecyl Acetoacetate, 2k (Including Enol Isomer).49
Data: mp 39-40 °C; IR (KBr) 2959 (m), 2915 (s), 2849 (s),
1746 (s), 1709 (m), 1465 (w), 1414 (w), 1370 (w), 1322 (m), 1263
(m), 1159 (m), 1053 (w), 1038 (w); 1H NMR (400 MHz, CDCl3)
12.08 (s, 1H, enol), 4.94 (s, 1H, enol), 4.09 (t, J ) 6.8, 2H),
4.07 (t, J ) 6.9, 2H, enol), 3.40 (s, 2H), 2.22 (s, 3H), 1.60 (quint,
J ) 7.1, 2H), 1.22 (bs, 30 H), 0.84 (t, J ) 6.6, 3H); 13C NMR
(100 MHz, CDCl3) 200.3, 175.2, 172.6, 167.0, 89.6, 65.4, 63.9,
50.0, 31.8, 29.9, 29.61, 29.58, 29.55, 29.5, 29.4, 29.3, 29.2, 29.1,
28.4, 25.8, 25.7, 25.6, 14.0; TLC Rf 0.38 (EtOAc/hexane, 1/9);
HR-MS (FAB+) calcd for C22H42O3 + H: 355.3212, found:
355.3219.
4-(Tetrahydropyran-2-yloxy)butyl 3-(3,5-Di-tert-butyl-
4-hydroxy)phenylpropanoate, 3a. Data: IR (CH2Cl2) 3635
(s), 3005 (w), 2921 (s), 1727 (s), 1605 (w), 1469 (m), 1361 (m),
1
1318 (m), 1265 (m), 1250 (s), 1122 (s), 1075 (s), 1033 (s); H
NMR (400 MHz, CDCl3) 7.00 (s, 2H), 5.09 (s, 1H), 4.59 (dd, J
) 4.3, 2.5, 1H), 4.13 (t, J ) 6.3, 2H), 3.85 (dt, J ) 6.4, 2.5,
1H), 3.80-3.74 (m, 1H), 3.53-3.49 (m, 1H), 3.44-3.38 (m, 1H),
2.88 (t, J ) 7.6, 2H), 2.61 (t, J ) 7.5, 2H), 1.84-1.51 (m, 10H),
1.44 (s, 18H); 13C NMR (100 MHz, CDCl3) 173.1, 152.1, 135.9,
131.1, 124.7, 98.7, 66.8, 64.2, 62.1, 36.4, 34.2, 30.9, 30.6, 30.2,
26.2, 25.6, 25.4, 19.5; MS (20 eV) 435 (M + H+, 5), 352 (10),
350 (57), 295 (30), 219 (22), 147 (16), 85 (100); TLC Rf 0.52
(EtOAc/hexane, 1/10); HR-MS calcd for C26H42O5: 434.3032,
found: 434.3021. Anal. Calcd for C26H42O5: C, 71.85; H, 9.74.
Found: C, 71.99; H, 9.52.
Octadecyl Furan-2-carboxylate, 2l.50 Data: mp 47-48
°C; IR (KBr) 3151 (m), 3122 (m), 2967 (m), 2923 (s), 2841 (s),
1709 (s), 1639 (m), 1580 (m), 1484 (s), 1469 (s), 1381 (m), 1296
(s), 1233 (m), 1174 (s), 1126 (s), 1078 (m), 1012 (m), 957 (m),
920 (m); 1H NMR (400 MHz, CDCl3) 7.57-7.56 (m, 1H), 7.16-
7.15 (m, 1H), 6.50-6.49 (m, 1H), 4.29 (t, J ) 6.8, 2H), 1.74
(quint, J ) 6.8, 2H), 1.42-1.25 (m, 30H), 0.87 (t, J ) 6.7, 3H);
13C NMR (100 MHz, CDCl3) 158.9, 146.1, 145.0, 117.6, 111.7,
65.1, 31.9, 29.7, 29.64, 29.57, 29.5, 29.4, 29.3, 28.7, 25.9, 22.7,
14.1; MS (70 eV) 364 (M+, 5), 113 (100), 95 (84), 67 (36), 57
(58); TLC Rf 0.38 (EtOAc/hexane, 1/10); HR-MS (FAB+) calcd
for C23H40O3 + H: 365.3056, found: 365.3050.
4-(tert-Butyldimethylsilanyloxy)butyl 3-(3,5-Di-tert-
butyl-4-hydroxy)phenylpropanoate, 3b. Data: IR (Nujol)
3638 (s), 3065 (w), 2949 (s), 2881 (s), 1732 (s), 1602 (w), 1436
(s), 1388 (s), 1358 (s), 1307 (m), 1249 (s), 1232 (s), 1198 (s),
1151 (s), 1123 (s), 1076 (s), 1028 (s), 987 (m), 974 (m), 902 (m);
1H NMR (400 MHz, CDCl3) 7.05 (s, 2H), 5.14 (s, 1H), 4.17 (t,
J ) 6.4, 2H), 3.69 (t, J ) 6.4, 2H), 2.94 (t, J ) 7.5, 2H), 2.66
(t, J ) 7.5, 2H), 1.79-1.72 (m, 2H), 1.65-1.58 (m, 2H), 1.49
(s, 18H), 0.96 (s, 9H) 0.12 (s, 6H); 13C NMR (100 MHz, CDCl3)
173.1, 152.1, 135.9, 131.1, 124.7, 64.2, 62.5, 36.4, 34.2, 31.0,
30.3, 29.1, 25.9, 25.2, 18.2, -5.4; MS (70 eV) 465 (M + H+, 5),
407 (10), 220 (26), 219 (100), 187 (58); TLC Rf 0.3 (EtOAc/
hexane, 1/5); HR-MS calcd for C27H48SiO4: 464.3322, found:
464.3325.
Octadecyl Thiophene-2-carboxylate, 2m. Data: mp 38-
39 °C; IR (KBr) 3107 (m), 2959 (s), 2923 (s), 2849 (s), 2686
(m), 1716 (s), 1701 (s), 1524 (m), 1476 (m), 1421 (m), 1384 (m),
1359 (m), 1259 (s), 1229 (m), 1100 (m), 1078 (m), 957 (w), 861
(w); 1H NMR (400 MHz, CDCl3) 7.81-7.80 (m, 1H), 7.55-7.54
(m, 1H), 7.12-7.09 (m, 1H), 4.30 (t, J ) 6.7, 2H), 1.75 (quint,
J ) 6.9, 2H), 1.43-1.24 (m, 30H), 0.89 (t, J ) 6.8, 3H); 13C
NMR (100 MHz, CDCl3) 162.3, 134.2, 133.2, 132.1, 127.7, 65.3,
31.9, 29.7, 29.6, 29.5, 29.4, 29.2, 28.7, 26.0, 23.0, 22.7, 14.1;
MS (20 eV) 381 (M+, 39), 111 (100), 55 (58); TLC Rf 0.40
(EtOAc/hexane, 1/10); HR-MS (FAB+) calcd for C23H40O2S +
H: 381.2827, found: 381.2830. Anal. Calcd for C23H40O2S: C,
72.58; H, 10.59. Found: C, 72.51; H, 10.65.
2-Ethylhexyl 3-(3,5-Di-tert-butyl-4-hydroxy)phenyl-
propanoate, 3c. Data: IR (CH2Cl2) 3636 (w), 3061 (s), 2986
1
(s), 1725 (s), 1425 (s), 1280 (s), 1251 (s); H NMR (400 MHz,
CDCl3) 7.06 (s, 2H), 5.13 (s, 1H), 4.10-4.02 (m, 2H), 2.94 (t, J
) 7.5, 2H), 2.67 (t, J ) 7.4, 2H), 1.65-1.58 (m, 1H), 1.49 (s,
18H), 1.44-1.34 (m, 8H), 0.95 (t, J ) 7.5, 3H), 0.93 (t, J ) 7.5,
3H); 13C NMR (100 MHz, CDCl3) 173.4, 152.1, 135.9, 131.2,
(49) (a) Mauz, O. Justus Liebigs Ann. Chem. 1974, 345. (b) Baindur,
N.; Rutledge, A.; Triggle, D. J. J. Med. Chem. 1993, 36, 3743.
(50) Castells, J.; Pujol, F.; Llitjos, H.; Moreno-Manas, M. Tetrahe-
dron 1982, 38, 337.
(51) Carey E. J. Econ. Entomol. 1949, 42, 798.
J. Org. Chem, Vol. 70, No. 4, 2005 1337