SCHEME 2. Mechanistic Proposal for the Conversion of 2 into 3
5.60 (m, 3H), 4.88-4.77 (m, 4H), 4.08 (m, 2H), 1.94-1.87
(m, 4H), 1.75-1.06 (m, 28H); 13C NMR (75 MHz, CDCl3): δ )
139.0 (2 × CH), 114.0 (2 × CH2), 86.3 (CH), 81.5 (CH), 73.2
(CH), 72.5 (CH), 33.6 (2 × CH2), 33.5 (2 × CH2), 31.8 (2 × CH2),
29.2 (2 × CH2), 29.0 (2 × CH2), 28.9 (2 × CH2), 28.7 (2 × CH2),
25.0 (CH2), 24.7 (CH2); IR (neat) 3416, 2926, 2855, 1640, 1567,
1465, 1356 cm-1; Rf 0.20 (hexane/EtOAc 10/1); Anal. Calcd for
C12H22BrNO3: C, 46.76; H, 7.19; N, 4.54. Found: C, 47.01; H,
6.99; N, 4.45.
1380 cm-1; Rf 0.4 (hexane/EtOAc 5/1); Anal. Calcd for C6H11-
NO2: C, 55.80; H, 8.58; N, 10.84. Found: C, 55.91; H, 8.50; N,
10.87.
(E)-3-Phenyl-1-nitroprop-1-ene (3e): Yellow oil; 1H NMR (300
MHz, CDCl3): δ ) 7.48-7.05 (m, H), 6.85 (d, J ) 13.5 Hz, 1H),
3.49 (d, J ) 7.05 Hz, 2H); 13C NMR (75 MHz, CDCl3): δ ) 141.0
(CH), 140.2 (CH), 135.6 (C), 128.9 (2 × CH), 128.6 (2 × CH),
127.3 (CH), 34.5 (CH2); HRMS (70 eV) calc. for C9H9NO2
163.0633, found 163.0639; IR (neat) 3015, 2925, 2833, 1561, 1467,
1355 cm-1; Rf 0.5 (hexane/EtOAc 5/1); Anal. Calcd for C9H9NO2:
C, 66.25; H, 5.56; N, 8.58. Found: C, 66.55; H, 5.43; N, 8.46.
(Z)-1-Bromo-1-nitroundec-7-en-2-ol (2g): Pale yellow oil; 1H
NMR (300 MHz, CDCl3): δ ) 5.87 (d, J ) 3.4 Hz, 1H), 5.61
(d, J ) 7.9 Hz, 1H), 5.28-5.13 (m, 4H), 4.16-4.06 (m, 2H), 2.92
(br s, 1H), 1.95-1.66 (m, 8H), 1.44-1.08 (m, 16H), 0.82 (t, J )
7.3 Hz, 6H); 13C NMR (75 MHz, CDCl3): δ ) 131.7 (2 × CH),
128.7 (2 × CH), 86.3 (CH), 81.5 (CH), 73.2 (CH), 72.5 (CH), 33.5
(CH2), 31.8 (CH2), 29.3 (2 × CH2), 28.6 (2 × CH2), 26.7 (2 ×
CH2), 24.9 (CH2), 24.6 (CH2), 20.3 (2 × CH2), 14.2 (2 × CH3);
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(E)-1-Nitrododeca-1,11-diene (3f): Brown oil; H NMR (300
MHz, CDCl3): δ ) 7.15 (dt, J ) 7.3, 13.0 Hz, 1H), 6.85 (d, J )
13.0 Hz, 1H), 5.74-5.60 (m, 1H), 4.85 (d, J ) 20.0 Hz, 1H), 4.79
(d, J ) 11.3 Hz, 1H), 2.2-2.1 (m, 2H), 1.99-1.87 (m, 2H), 1.51-
1.11 (m, 12 H); 13C NMR (75 MHz, CDCl3): δ ) 142.7 (CH),
139.4 (CH), 138.9 (CH), 114.1 (CH2), 33.6 (CH2), 29.1 (CH2), 29.0
(CH2), 28.9 (CH2), 28.8 (CH2), 28.7 (CH2), 28.3 (CH2), 27.6 (CH2);
IR (neat) 2927, 2855, 1641, 1557, 1527, 1465, 1352 cm-1; Rf 0.25
(hexane/EtOAc 10/1); Anal. Calcd for C12H21NO2: C, 68.21; H,
10.02; N, 6.63. Found: C, 68.55; H, 10.22; N, 6.56.
IR (neat) 3424, 3005, 2930, 2857, 1638, 1567, 1462, 1357 cm-1
;
Rf 0.20 (hexane/EtOAc 10/1); Anal. Calcd for C11H20BrNO3: C,
44.91; H, 6.85; N, 4.76. Found: C, 44.85; H, 6.93; N, 4.79.
(E)-1-Nitronon-1-ene (3a): Pale yellow oil; 1H NMR (300 MHz,
CDCl3): δ ) 7.27 (dt, J ) 6.4, 13.6 Hz, 1H), 6.97 (d, J ) 13.6
Hz, 1H), 2.29-2.22 (m, 2H), 1.53-1.05 (m, 10H), 0.87 (t, J )
6.8 Hz, 3H); 13C NMR (75 MHz, CDCl3): δ ) 142.8 (CH), 139.5
(CH), 31.55 (CH2), 28.9 (CH2), 28.8 (CH2), 28.3 (CH2), 27.6 (CH2),
22.5 (CH2), 13.9 (CH3); HRMS (70 eV) calc. for [C9H17NO2-Me]
156.1025, found 156.1010; IR (neat) 2927, 2856, 1558, 1528, 1466,
1357 cm-1; Rf 0.4 (hexane/EtOAc 5/1); Anal. Calcd for C9H17-
NO2: C, 63.13; H, 10.01; N, 8.18. Found: C, 63.02; H, 10.25; N,
8.11.
(1E,7Z)-1-nitroundeca-1,7-diene (3g): Brown oil; 1H NMR (300
MHz, CDCl3): δ ) 7.14 (dt, J ) 7.3, 13.8 Hz, 1H), 6.85 (d, J )
13.8 Hz, 1H), 5.28-5.12 (m, 2H), 2.17-2.10 (m, 2H), 1.94-1.85
(m, 4H), 1.45-1.12 (m, 6H), 0.81 (t, J ) 7.6 Hz, 3H); 13C NMR
(75 MHz, CDCl3): δ ) 142.6 (CH), 139.4 (CH), 131.8 (CH), 128.5
(CH), 29.1 (CH2), 28.5 (CH2), 28.3 (CH2), 27.5 (CH2), 26.7 (CH2),
20.4 (CH2), 14.2 (CH3); IR (neat) 3004, 2936, 2857, 1649, 1556,
1527, 1462, 1352 cm-1; Rf 0.25 (hexane/EtOAc 10/1); Anal. Calcd
or C11H19NO2: C, 66.97; H, 9.71; N,7.10. Found: C, 67.05; H,
9.55; N, 7.15.
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(E)-4-Methyl-1-nitropent-1-ene (3b): Colorless oil; H NMR
(300 MHz, CDCl3): δ ) 7.15-7.05 (m, 1H), 6.83 (dt, J ) 1.1,
13.6 Hz, 1H), 2.03-1.98 (m, 2H), 1.75-1.62 (m, 1H), 0.81 (d, J
) 6.8 Hz, 6H); 13C NMR (75 MHz, CDCl3): δ ) 141.7 (CH),
139.9 (CH), 37.0 (CH2), 27.5 (CH), 22.0 (2 × CH3); HRMS
(70 eV) calc. for C6H11NO2 129.0790, found 129.0794; IR (neat)
2929, 1732, 1645, 1556, 1523, 1450, 1350 cm-1; Rf 0.37 (hexane/
EtOAc 5/1); Anal. Calcd for C6H11NO2: C, 55.80; H, 8.58; N,
10.84. Found: C, 55.55; H, 8.67; N, 10.92.
Acknowledgment. We thank the Ministerio de Educacio´n
y Ciencia (CTQ2004-1191/BQU) for financial support. J.M.C.
thanks Carmen Ferna´ndez-Flo´rez for her time. H.R.S. and C.C.
thank the Ministerio de Educacio´n y Ciencia for a Ramo´n y
Cajal Contract (Fondo Social Europeo) and a predoctoral FPI
fellowship, respectively. Our thanks to Euan C. Goddard for
his revision of the English.
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(E)-3-Methyl-1-nitropent-1-ene (3c): Colorless oil; H NMR
(300 MHz, CDCl3): δ ) 7.04 (dd, J ) 8.4, 13.5 Hz, 1H), 6.79
(dd, J ) 1.1, 13.5 Hz, 1H), 2.25-2.15 (m, 1H), 1.39-1.29 (m,
2H), 0.98 (d, J ) 6.7 Hz, 3H), 0.77 (t, J ) 7.3 Hz, 3H) 13C NMR
(75 MHz, CDCl3): δ ) 147.3 (CH), 138.5 (CH), 34.9 (CH), 28.4
(CH2), 18.4 (CH3), 11.3 (CH3); HRMS (70 eV) calc. for C6H11-
NO2 129.0790, found 129.0755;IR (neat) 2924, 1718, 1557, 1462,
Supporting Information Available: General information, and
1
copies of H and 13C NMR spectra for all new compounds 2 and
3. This material is available free of charge via the Internet at
JO0706271
J. Org. Chem, Vol. 72, No. 14, 2007 5423