ORDER
REPRINTS
2,4-DINITROPHENYLHYDROXYLAMINE
3093
(dd, J ¼ 9.4, 2.8 Hz, 1H), 8.79 (br, 1H), 9.13 (d, J ¼ 2.8 Hz, 1H); 13C NMR
47.2, 114.3, 114.6, 124.2, 125.9, 128.6, 128.8, 130.3, 137.8, 141.8, 148.2; IR
(KBr) 813, 1315, 1340, 1523, 1540, 1523, 1620, 2927, 2971, 3110, 3395 cmÀ1
;
MS (EI, 12 eV DIP, m/z, rel. intensity) 299 (Mþ, 45), 253 (100), 207 (6), 163
(10), 103 (30); High resolution FAB for C15H14N3O4 300.0998 (Mþ þ 1),
calc. 300.2917.
2c. Yield 63%; mp 100–101ꢀC; H NMR (acetone-d6) 0.84 (s, 3H),
1
1.16 (d, J ¼ 8.4 Hz, 1H), 1.27 (s, 3H), 2.08–2.13 (m, 1H), 2.18–2.22 (m,
1H), 2.23–2.30 (m, 2H), 2.40–2.46 (m, 1H), 4.14 (br s, 2H), 5.55 (br s,
1H), 7.20 (d, J ¼ 9.6 Hz, 1H), 8.27 (dd, J ¼ 9.6, 2.6 Hz, 1H), 8.90 (br, 1H),
8.97 (d, J ¼ 2.8 Hz, 1H); 13C NMR (acetone-d6) 21.3, 26.3, 31.7, 32.1, 38.7,
41.5, 44.5, 48.3, 116.3, 119.9, 124.2, 130.4, 143.9, 149.6; IR (KBr) 808, 1311,
1339, 1526, 1592, 1621, 2898, 2884, 2927, 2998, 3106, 3376 cmÀ1; MS (EI,
12 eV DIP, m/z, rel. intensity) 316 (MþÀ1, 19), 282 (28), 271 (100), 196 (27),
134 (24), 133 (55), 119 (24), 105 (59), 91 (62); High resolution FAB for
C16H20N3O4 318.1445 (Mþ þ 1), calc. 318.3501.
1
2d. Yield 30%; H NMR (acetone-d6) 1.85 (s, 3H), 3.94 (br s, 2H),
4.35 (dd, J ¼ 11.0, 5.0 Hz, 1H), 4.45 (br s, 1H), 5.02 (br s, 1H), 5.05 (br s,
1H), 7.07 (d, J ¼ 9.6 Hz, 1H), 8.25 (dd, J ¼ 9.6, 2.8 Hz, 1H), 8.98 (d,
J ¼ 2.8 Hz, 1H), 9.11 (br, 1H); 13C NMR (acetone-d6) 19.7, 61.3, 63.5,
113.9, 114.1, 116.8, 124.2, 130.6, 142.5, 149.1; IR (KBr) 830, 1335, 1528,
1594, 1630, 2878, 2932, 3094, 3353, 3465 cmÀ1; MS (EI, 12 eV DIP, m/z, rel.
intensity) 267 (Mþ, 11), 237 (4), 236 (100), 183 (4).
2e. Yield 30%; 1H NMR (acetone-d6) 1.78 (s, 3H), 2.03–2.05 (m, 2H),
2.15 (s, 3H), 2.69(t, J ¼ 7.0 Hz, 2H), 4.33 (dd, J ¼ 13.6, 6.8 Hz, 1H), 5.03 (br
s, 1H), 5.07 (br s, 1H), 7.16 (d, J ¼ 9.6 Hz, 1H), 8.26 (dd, J ¼ 9.6, 2.8 Hz, 1H),
8.64 (br, 1H), 8.97 (d, J ¼ 2.8 Hz, 1H); 13C NMR (acetone-d6) 18.0, 27.7,
30.4, 39.8, 59.7, 114.2, 116.5, 116.6, 124.2, 130.6, 144.2, 148.4; IR (KBr) 800,
1261, 1334, 1522, 1591, 1618, 1717, 2851, 2927, 2965, 3110, 3363 cmÀ1; MS
(EI, 12 eV DIP, m/z, rel. intensity) 307 (Mþ, 6), 259(12), 246 (10), 236 (100),
219 (10), 183 (11), 167 (93), 140 (32), 99 (38).
Reaction of Secondary N-(2,4-Dinitrophenyl)-N-allyl
Amine 2b withNucleophilic and Acidic Reagents
Amine 2b (0.10 g, 0.33 mmol) was dissolved in the given solvent system
(THF, MeOH, or acetone, 10 mL) at room temperature. To this was added
the required reagent. The reaction mixture was stirred for 6–24 h at room
temperature and (if no reaction was observed) then heated at reflux for
an additional 10–30 h. After this, the mixture was cooled to room tempera-
ture and the solvent was removed by rotary evaporation. The residue was