Page 15 of 27
The Journal of Organic Chemistry
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δ 193.6, 140.3, 139.2, 135.3, 134.1, 132.8, 132.3, 129.5, 127.7, 120.3, 44.6, 30.2 (one 13C signal lost for
overlap); HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C15H13ClN2O2Na, 311.0563; found, 311.0562.
N-(4-Bromophenyl)-N-(2-formylphenethyl)nitrous amide (2g)
Compound 2g was isolated in 81% yield (269 mg, yellow solid); m.p.: 110-112 oC; 1H NMR (400 MHz,
CDCl3) δ 10.09 (s, 1H), 7.76 (dd, J = 7.5, 1.3 Hz, 1H), 7.64 – 7.48 (m, 5H), 7.45 (td, J = 7.4, 1.1 Hz,
1H), 7.28 (d, J = 7.4 Hz, 1H), 4.20 (t, J = 7.6 Hz, 2H), 3.23 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (101 MHz,
CDCl3) δ 193.6, 140.8, 139.2, 135.4, 134.1, 132.5, 132.3, 127.7, 120.6, 120.5, 44.5, 30.3 (one 13C signal
lost for overlap); HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C15H13BrN2O2Na, 355.0058; found,
355.0049.
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N-(4-Cyanophenyl)-N-(2-formylphenethyl)nitrous amide (2h)
Compound 2h was isolated in 94% yield (262 mg, yellow solid); m.p.: 153-156 oC; 1H NMR (400 MHz,
CDCl3) δ 10.08 (s, 1H), 7.87 (d, J = 8.8 Hz, 2H), 7.82 – 7.66 (m, 3H), 7.59 – 7.40 (m, 2H), 7.30 (d, J =
7.3 Hz, 1H), 4.21 (t, J = 7.6 Hz, 2H), 3.20 (t, J = 7.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 194.0,
145.1, 138.7, 135.9, 134.2, 134.1, 133.6, 132.4, 127.9, 118.3, 110.1, 43.63, 30.40; HRMS (ESI-TOF)
m/z: [M + Na]+ Calcd for C16H13N3O2Na, 302.0906; found, 302.0893.
Methyl 4-((2-formylphenethyl)(nitroso)amino)benzoate (2i)
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Compound 2j was isolated in 92% yield (287 mg, light yellow solid); m.p.: 65-68 C; Mixture of two
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rotamors. H NMR (400 MHz, CDCl3) δ 10.08 (s, 1H), 8.09 (d, J = 8.5 Hz, 2H), 7.87 – 7.59 (m, 3H),
7.59 – 7.35 (m, 2H), 7.26 (d, J = 6.3 Hz, 1H), 4.23 (t, J = 7.6 Hz, 2H), 3.90 (s, 3H), 3.22 (t, J = 7.6 Hz,
2H); 13C{1H} NMR (101 MHz, CDCl3) δ 193.7, 193.6, 166.2, 145.2, 139.1, 135.5, 135.3, 134.1, 132.3,
132.2, 131.1, 131.0, 128.3, 127.9, 127.6, 118.0, 117.8, 52.3, 52.1, 44.0, 30.3; HRMS (ESI-TOF) m/z: [M
+ Na]+ Calcd for C17H16N2O4Na, 335.1008; found, 335.1003.
Ethyl 4-((2-formylphenethyl)(nitroso)amino)benzoate (2j)
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Compound 2j was isolated in 99% yield (323 mg, light yellow solid); m.p.: 70-75 C; Mixture of two
rotamors. 1H NMR (400 MHz, CDCl3) δ 10.10 (s, 1H), 8.22 – 8.02 (m, 2H), 7.86 – 7.64 (m, 2H), 7.63 –
7.36 (m, 2H), 7.28 (d, J = 7.4 Hz, 1H), 4.38 (q, J = 7.1 Hz, 2H), 4.25 (t, J = 7.6 Hz, 2H), 3.24 (t, J = 7.6
Hz, 2H), 1.40 (t, J = 7.1 Hz, 3H); 13C{1H} NMR (101 MHz, CDCl3) δ 193.7, 193.6, 165.8, 145.1, 139.1,
135.5, 135.4, 134.1, 132.4, 132.2, 131.0, 130.9, 128.7, 127.8, 127.7, 118.0, 117.9, 61.1, 44.0, 30.3, 14.3;
HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C18H18N2O4Na, 349.1164; found, 349.1160.
N-(2-Formylphenethyl)-N-(4-(trifluoromethyl)phenyl)nitrous amide (2k)
Compound 2k was isolated in 91% yield (293 mg, yellow solid); m.p.: 102-104 oC; 1H NMR (400 MHz,
CDCl3) δ 10.10 (s, 1H), 7.83 (d, J = 8.6 Hz, 2H), 7.77 (d, J = 7.4 Hz, 1H), 7.72 (d, J = 8.6 Hz, 2H), 7.53
(t, J = 7.4 Hz, 1H), 7.47 (t, J = 7.4 Hz, 1H), 7.31 (d, J = 7.4 Hz, 1H), 4.24 (t, J = 7.6 Hz, 2H), 3.24 (t, J
= 7.6 Hz, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 193.8, 144.4, 139.0, 135.6, 134.1, 134.1, 132.3, 128.8
(q, JC-F = 32.8 Hz), 127.8, 126.7 (q, JC-F = 3.8 Hz), 123.9 (q, JC-F = 271.9 Hz), 118.5, 110.0, 44.1, 30.4;
HRMS (ESI-TOF) m/z: [M + Na]+ Calcd for C16H13F3N2O2Na, 345.0827; found, 345.0814.
N-(2-Fluorophenyl)-N-(2-formylphenethyl)nitrous amide (2l)
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Compound 2l was isolated in 90% yield (245 mg, yellow solid); m.p.: 86-88 C; Mixture of two
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rotamors. H NMR (400 MHz, CDCl3) δ 10.08 (s, 1H), 10.05 (s, 0.3H), 7.81 – 7.66 (m, 1.3H), 7.55 –
7.32 (m, 4H), 7.32 – 7.11 (m, 5H), 7.08 – 6.97 (m, 0.3H), 4.79 – 4.67 (m, 0.6H), 4.30 – 4.09 (m, 2H),
3.53 – 3.40 (m, 0.6H), 3.35 – 3.14 (m, 2H); 13C{1H} NMR (101 MHz, CDCl3) δ 193.1, 192.8, 158.1,
156.9, 155.6, 154.4, 139.7, 139.2, 135.2, 134.0, 133.9, 133.9, 132.0, 131.8, 131.2, 131.1, 130.3, 130.2,
129.5, 129.4, 127.8 (two 13C), 127.6, 127.5, 126.9, 124.8, 124.8, 124.8, 124.7, 117.0, 116.8, 116.7, 116.5,
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