E. Colacino et al. / Tetrahedron 64 (2008) 5569–5576
5575
a white solid in 92% yield. Mp 115–117 ꢀC; 1H NMR (CDCl3) d 7.89 (s,
1H), 7.50 (br d, 1H), 7.45 (br d, 1H), 7.17 (dd, J¼3.8 Hz, J¼5.0 Hz, 1H),
3.92 (s, 3H); 13C NMR (CDCl3) d 132.41, 130.82, 129.25, 128.99,
126.47, 51.71; IR (KBr): 3425.1 (br s), 3064.0 (w), 2967.64 (w),
1585.4 (s), 1389.7 (s), 1253.6 (m), 1228.8 (m), 1162.4 (s), 1092.9 (w),
1044.8 (m), 952.9 (s), 855.4 (s), 763.6 (s), 702.9 (s), 599.8 (m), 537.3
(m) cmꢁ1; ESIMS m/z 142.1 [MþH]þ; FAB(þ) m/z 142.0 [MþH]þ;
HRMS Calcd for C6H8NOS [MþH]þ: 142.0327. Found 142.0314.
(m), 1666.6 (s), 1601.9 (m), 1572.0 (m), 1498.5 (m), 1420.9 (s), 1348.1
(s), 1195.9 (w), 1158.9 (s), 949.0 (m), 921.8 (s), 862.2 (w), 782.9 (s),
754.3 (s), 649.1 (m), 637.6 (m), 468.9 (m) cmꢁ1; ESIMS m/z 187.1
[MþH]þ; FAB(þ) m/z 187.1 [MþH]þ; HRMS Calcd for C11H11N2O
[MþH]þ: 187.0871. Found 187.0872.
4.2.28. (Z)-N-(n-Butylidene)methylamine N-oxide (30)
(Table 2, entry 14)
Method A. The condensation reaction between aldehyde 1q and
N-methylhydroxylamine hydrochloride 2 afforded 47 mg of 30 as
a colorless oil in 93% yield. 1H NMR (CDCl3) d 6.71 (t, J¼5.8 Hz, 1H),
3.71 (s, 3H), 2.51 (br q, J¼7.4 Hz and 1.3 Hz, 2H), 1.58 (septet,
J¼7.5 Hz, 2H), 0.99 (t, J¼7.3 Hz, 3H); 13C NMR (CDCl3) d 140.63,
52.32, 28.73, 18.89, 13.93; IR (KBr): 3399.4 (br s), 2963.7 (s), 2875.4
(s), 1660.6 (s), 1459.1 (s), 1386.9 (m),1080.3 (w), 947.2 (w), 627.1 (w)
cmꢁ1; ESIMS m/z 203.2 [Mþ2H]þ, 102.0 [MþH]þ; FAB(þ) m/z 102.1
[MþH]þ; HRMS Calcd for C5H12NO [MþH]þ: 102.0910. Found
102.0922.
4.2.24. (Z)-N-(Benzofuran-2-ylmethylidene)methylamine N-oxide
(26) (Table 2, entry 10)
Method A. The condensation reaction between aldehyde 1n and
N-methylhydroxylamine hydrochloride 2 afforded 87 mg of 26 as
a pale yellow solid in 100% yield. Mp 108–110 ꢀC; 1H NMR (CDCl3)
d 8.18 (br s, 1H), 7.71–7.67 (m, 1H), 7.51–7.45 (m, 1H), 7.41 (dd,
J¼6.96 Hz and 1.41 Hz, 1H), 7.33 (dd, J¼4.71 Hz and 1.41 Hz, 1H),
7.28 (dd, J¼6.96 Hz and 1.33 Hz, 1H), 3.92 (s, 3H); 13C NMR (CDCl3)
d 154.40, 147.68, 128.35, 126.54, 126.24, 123.42, 122.44, 111.08,
110.91, 53.44; IR (KBr): 3419.5 (br w), 3141.1 (w), 3028.9 (w), 2947.4
(w), 1593.6 (m), 1543.4 (m), 1450.5 (m), 1409.6 (s), 1392.6 (m),
1343.9 (m), 1266.1 (m), 1247.3 (s), 1203.5 (s), 1134.6 (m), 955.9 (s),
4.2.29. (Z)-N-(n-Heptylidene)methylamine N-oxide (31)
(Table 2, entry 15)43
867.7 (s), 780.1 (s), 753.9 (s), 747.3 (s), 655.0 (m), 518.6 (m) cmꢁ1
;
Method A. The condensation reaction between aldehyde 1r and
N-methylhydroxylamine hydrochloride 2 afforded 64 mg of 31 as
a colorless oil in 90% yield. 1H NMR (CDCl3) d 6.67 (t, J¼5.8 Hz, 1H),
4.71 (s, 3H), 2.45 (br q, J¼6.8 Hz, 2H), 1.55 (m, 2H), 1.50–1.20 (m,
6H), 0.89 (t, J¼7.1 Hz, 3H); 13C NMR (CDCl3) d 140.92, 52.31, 31.44,
29.11, 26.85, 25.43, 22.47, 13.98; IR (KBr): 3297.6 (br s), 2927.3 (s),
2860.1 (s), 1668.1 (s), 1461.33 (s), 1378.9 (w), 1102.4 (w), 947.8 (w),
728.48 (w) cmꢁ1; ESIMS m/z 287.2 [Mþ2H]þ, 144.2 [MþH]þ;
FAB(þ) m/z 144.1 [MþH]þ; HRMS Calcd for C8H18NO [MþH]þ:
144.1388. Found 144.1378.
ESIMS m/z 176.1 [MþH]þ; FAB(þ) m/z 176.1 [MþH]þ; HRMS Calcd
for C10H10NO2 [MþH]þ: 176.0712. Found 176.0713.
4.2.25. (E)-N-(Napht-2-ylmethylidene)methylamine N-oxide (27)
(Table 2, entry 11)42
Method A. The condensation reaction between aldehyde 1o and
N-methylhydroxylamine hydrochloride 2 afforded 85 mg of 27 as
a deep yellow solid in 92% yield. Mp 108–110 ꢀC (lit.39 106–108 ꢀC);
1H NMR (CDCl3) d 9.22 (s, CH]N, 1H), 7.95–7.88 (m, 1H), 7.85–7.78
(m, 3H), 7.55–7.45 (m, 3H), 3.92 (s, 3H); 13C NMR (CDCl3) d 162.59,
135.23, 134.12, 133.13, 129.21, 128.42, 127.98, 127.72, 127.55, 127.36,
126.51, 125.66, 54.51; IR (KBr): 3420.6 (br w), 3078.5 (w), 3057.9
(w), 2996.8 (w), 2941.4 (w), 1578.2 (m), 1566.5 (w), 1502.2 (w),
1416.77 (s), 1404.3 (m), 1380.3 (m), 1364.2 (m), 1274.5 (w), 1125.5
(m), 968.8 (m), 957.5 (m), 904.9 (m), 869.9 (s), 841.9 (s), 753.4 (s),
482.7 (s) cmꢁ1; ESIMS m/z 371.1 [Mþ2H]þ, 208.1 [MþNa]þ, 186.2
[MþH]þ; FAB(þ) m/z 186.1 [MþH]þ; HRMS Calcd for C12H12NO
[MþH]þ: 186.0919. Found 186.0918.
Acknowledgements
We thank Dr. Lydie Viau from the Institut Charles Gerhardt
(UMR 5253, CMOS group, Montpellier, France) for DSC experi-
ments, MENRT, CNRS, the Ligue Contre le Cancer and the Fondation
d’Entreprise EADS for financial support.
Supplementary data
4.2.26. (Z)-N-(Napht-2-ylmethylidene)benzylamine N-oxide (28)
(Table 2, entry 12)28,55
Supplementary data associated with this article can be found in
Method A. The condensation reaction between aldehyde 1o and
N-benzylhydroxylamine hydrochloride 4 afforded 131 mg of 28 as
a pale orange solid in 100% yield. Mp 104–106 ꢀC (lit.28 107–
108 ꢀC); 1H NMR (CDCl3) d 9.25 (s, CH]N, 1H), 7.92–7.77 (m, 4H),
7.68–7.32 (m, 8H), 5.11 (s, 2H); 13C NMR (CDCl3) d 134.34, 134.14,
133.40, 133.14, 129.56, 129.26, 129.00, 128.61, 128.32, 127.94, 127.73,
127.56, 127.39, 126.54, 125.95, 71.28; IR (KBr): 3441.5 (br w), 3056.8
(w), 3028.9 (w), 1572.4 (m), 1497.1 (w), 1451.5 (m), 1353.9 (m),
1229.9 (m), 1183.6 (m), 1161.3 (m), 1142.2 (m), 945.5 (m), 901.6 (m),
866.6 (s), 829.9 (m), 732.2 (s), 701.4 (s), 479.3 (s) cmꢁ1; ESIMS m/z
523.0 [Mþ2H]þ, 262.1 [MþH]þ; FAB(þ) m/z 262.1 [MþH]þ; HRMS
Calcd for C18H16NO [MþH]þ: 262.1232. Found 262.1234.
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