I. Gallardo, G. Guirado, J. Marquet
that only the substitution products and starting material were pre- 0.70 Hz, 1 H), 7.80 (td, 1 H), 7.56 (td, 1 H), 3.89 (t, J ϭ 6.80 Hz,
FULL PAPER
sent.
2 H), 1.68 (m, J ϭ 6.80 Hz, J ϭ 7.50 Hz, 2 H), 1.44 (m, J ϭ
7.50 Hz, J ϭ 6.90 Hz, 2 H), 0.96 (t, J ϭ 6.90 Hz, 3 H). MS (70 eV):
m/z (%) ϭ 289 (58) [M]ϩ, 290 (10), 246 (38), 230 (24), 229 (100),
212 (22), 199 (14), 184 (10), 169 (19), 155 (24), 154 (20), 142 (12),
141 (30), 140 (22), 130 (13), 129 (16), 128 (34), 126 (25), 116 (14),
115 (19), 114 (27), 113 (16), 102 (13), 101 (14), 77 (12), 75 (13), 63
(13), 55 (10), 43 (22), 41 (36).
Generation of 15 by Preparative Electrolysis: A solution of 1,3-di-
nitronaphthalene (70 mg) in DMF (7 mL), which contained 0.1
Et4NBF4 (0.1519 g) as a supporting electrolyte, was prepared under
nitrogen. The corresponding σH complex was prepared by careful
addition of the nucleophile (butylamine, 510 mg) to the solution of
the nitroarene under nitrogen. The crude product [or mixture of
product(s) and reactants] was purified or separated by silica gel
chromatography using chloroform as the eluent. N-Butyl-2,4-di-
nitro-1-naphthalenamine (15) was obtained as the main product
(65 mg, 70%). As a minor product, 2,4-dinitro-1-naphthalenamine
(28, 5 mg, 7%) was also obtained. Moreover, (10 mg, 14%) of the
unreacted starting material, 2,4-dinitronaphthalene (6), was reco-
vered.
1
N-Hexyl-2,4-dinitroaniline (16):[7] Table 2, Entry 4. H NMR (250
MHz, CD3CN): δ ϭ 8.96 (d, J ϭ 2.68 Hz, 1 H), 8.22 (dd, J ϭ
9.55 Hz, 2.68 Hz, 1 H), 7.10 (d, J ϭ 9.55 Hz, 1 H), 3.45 (q, J ϭ
6.25 Hz, 2 H), 1.75 (m, 2 H), 1.38 (m, 6 H), 1.13 (t, J ϭ 7.25 Hz,
3 H). MS (70 eV): m/z (%) ϭ 267 (14) [M]ϩ, 232 (4), 204 (3), 196
(100), 190 (9), 180 (19), 177 (12), 166 (11), 150 (10), 104 (11), 92
(7), 77 (10), 43 (12).
Reaction Products
N-(2,4-Dinitrophenyl)acetamide (17):[21] Table 2, Entry 5. 1H NMR
(250 MHz, CD3CN): δ ϭ 10.10 (s, 1 H), 8.91 (s, 1 H), 8.72 (d, J ϭ
8.80 Hz, 1 H), 8.21 (d, J ϭ 8.80 Hz, 1 H), 3.01 (s, 3 H). MS (70 eV):
m/z (%) ϭ 224 (12) [M]ϩ, 226 (2), 183 (27), 167 (3), 153 (11), 137
(1), 107 (7), 91 (8), 63 (11), 53 (8), 43 (100). Quality identification
91%.[22]
N-Butyl-2,4-dinitroaniline (10):[16] Table 1, Entry 1 and Table 2,
Entries 1Ϫ3. 1H NMR (250 MHz, CD3CN): δ ϭ 8.96 (d, J ϭ
2.9 Hz, 1 H), 8.39 (s, 1 H), 8.20 (dd, J ϭ 9.50, J ϭ 2.20 Hz, 1 H),
7.05 (d, J ϭ 9.50 Hz, 1 H), 3.13 (t, J ϭ 6.25 Hz, 2 H), 1.58 (m,
J ϭ 6.25 Hz, J ϭ 7.50 Hz, 2 H), 1.39 (m, J ϭ 7.50 Hz, J ϭ 6.90 Hz,
2 H), 1.13 (t, J ϭ 6.90 Hz, 3 H). MS (70 eV): m/z (%) ϭ 239 (17)
[M]ϩ, 197 (10), 196 (100), 180 (6), 178 (5), 166 (7), 150 (10), 150
(10), 104 (9), 92 (6), 77 (9), 65 (5), 51 (5), 43 (5).
N-Butyl-1-nitro-2-naphthalenamine (18):[23] Table 2, Entry 6. MS
(70 eV): m/z (%) ϭ 244 (75) [M]ϩ, 245 (13), 211 (5), 209 (6), 202
(10), 201 (75), 184 (15), 182 (10), 173 (16), 171 (15), 168 (14), 156
(30), 155 (100), 153 (31), 143 (11), 129 (20), 128 (58), 127 (34), 116
(12), 115 (37), 114 (12), 101 (15), 77 (16), 41 (17).
4-Butylamine-3,5-dinitrobenzonitrile (11a):[17] Table 1, Entry 2. 1H
NMR (250 MHz, CD3CN): δ ϭ 9.15 (s, 1 H), 8.75 (s, 1 H), 3.13
(t, J ϭ 6.25 Hz, 2 H), 1.58 (m, J ϭ 6.25 Hz, J ϭ 7.50 Hz, 2 H),
1.38 (m, J ϭ 7.50 Hz, J ϭ 6.90 Hz, 2 H), 1.13 (t, J ϭ 6.90 Hz, 3
H). MS (70 eV): m/z (%) ϭ 264 (16) [M]ϩ, 265 (12), 221 (75), 205
(32), 163 (16), 130 (15), 88 (17), 76 (13), 71 (35), 55 (15), 43 (100),
41 (58).
4-Butylamine-5-nitro-2-thiophenecarbonitrile (19):[23] Table 2, Entry
1
7. H NMR (250 MHz, CD3CN): δ ϭ 7.61 (s, 1 H), 7.21 (s, 1 H),
3.14 (t, J ϭ 6.25 Hz, 2 H), 1.59 (m, J ϭ 6.25 Hz, J ϭ 7.50 Hz, 2
H), 1.39 (m, J ϭ 7.50 Hz, J ϭ 6.90 Hz, 2 H), 0.97 (t, J ϭ 6.90 Hz,
3 H). MS (70 eV): m/z (%) ϭ 225 (46) [M]ϩ, 226 (6), 227 (3), 180
(8), 182 (100), 187 (7), 156 (16), 164 (10), 154 (10), 152 (31), 137
(14), 136 (24), 125 (18), 152 (31), 137 (14), 136 (24), 125 (18), 124
(13), 110 (13), 109 (42), 96 (12), 83 (19), 77 (26), 71 (23), 70 (37),
51 (13), 45 (16), 43 (45), 41 (45).
2-Butylamine-3,5-dinitrobenzonitrile (11b): Table 1, Entry 2. MS
(70 eV): m/z (%) ϭ 264 (13) [M]ϩ, 265 (3), 222 (11), 221 (100), 205
(13), 191 (10), 163 (9), 129 (24), 117 (15), 102 (18), 75 (10), 71 (18),
56 (14), 43 (27), 41 (30).
N-Butyl-2,6-dinitro-4-(trifluoromethyl)aniline (12):[18] Table 1, Entry
3. H NMR (250 MHz, CD3CN): δ ϭ 9.09 (s, 1 H), 8.50 (s, 1 H),
N-Butyl-2-chloro-3-nitro-4-pyridinamine (20):[23] Table 2, Entry 8.
1H NMR (250 MHz, CD3CN): δ ϭ 8.37 (d, J ϭ 9.00 Hz, 1 H),
6.45 (d, J ϭ 9.00 Hz, 1 H), 6.06 (s, 1 H), 3.30 (t, J ϭ 6.25 Hz, 2
H), 1.58 (m, J ϭ 6.25 Hz, J ϭ 7.50 Hz, 2 H), 1.40 (m, J ϭ 7.50 Hz,
J ϭ 6.90 Hz, 2 H), 0.94 (t, J ϭ 6.90 Hz, 3 H). MS (70 eV): m/z
(%) ϭ 230 (2) [M]ϩ, 231 (6), 229 (16), 200 (13), 194 (16), 188 (32),
187 (19), 186 (100), 173 (22), 154 (6), 140 (20), 140 (60), 112 (11),
76 (11), 41 (19).
1
3.00 (t, J ϭ 6.25 Hz, 2 H), 1.68 (m, J ϭ 6.25 Hz, J ϭ 7.50 Hz, 2
H), 1.44 (m, J ϭ 7.50 Hz, J ϭ 6.90 Hz, 2 H), 0.96 (t, J ϭ 6.90 Hz,
3 H). MS (70 eV): m/z (%) ϭ 307 (13) [M]ϩ, 308 (2), 272 (16), 265
(8), 264 (81), 249 (4), 248 (37), 235 (9), 231 (10), 206 (21), 189 (12),
188 (12), 187 (12), 174 (13), 171 (15), 160 (17), 159 (23), 146 (10),
144 (22), 142 (11), 127 (7), 126 (10), 125 (7), 105 (13), 95 (6), 75
(11), 71 (57), 57 (10), 56 (10), 44 (13), 43 (100), 41 (66).
N-(2,4,6-Trinitrophenyl)acetamide (21):[24] Table 2, Entry 9. 1H
NMR (250 MHz, CD3CN): δ ϭ 10.28 (s, 1 H), 9.22 (s, 1 H), 2.28
(s, 3 H). MS (70 eV): m/z (%) ϭ 240 (1), 238 (1), 237 (5), 236 (37),
198 (14), 195 (3), 194 (32), 122 (2), 148 (5), 77 (2), 67 (2), 52 (3),
43 (100). MS (chemical ionization, CH4, NH3): m/z (%) ϭ 270 (100)
[M]ϩ, 284 (15), 253 (47), 235 (78), 223 (31), 205 (47), 187 (15),
141 (84).
N-Butyl-3-chloro-2,6-dinitroaniline (13): Table 1, Entry 4. This
product could not be isolated and was tentatively assigned by GC/
MS. MS (70 eV): m/z (%) ϭ 273 (17) [M]ϩ, 275 (5), 274 (4), 230
(100), 214 (15), 213 (13), 184 (10), 171 (8), 156 (9), 137 (16), 126
(14), 102 (10), 90 (8), 75 (18), 71 (17), 51 (5), 43 (24).
N-Butyl-2,4,6-trinitroaniline (14):[19] Table 1, Entry 5. 1H NMR
(250 MHz, CD3CN): δ ϭ 9.19 (s, 1 H), 8.67 (s, 1 H), 3.13 (t, J ϭ
6.25 Hz, 2 H), 1.58 (m, J ϭ 6.25 Hz, J ϭ 7.50 Hz, 2 H), 1.39 (m,
J ϭ 7.50 Hz, J ϭ 6.90 Hz, 2 H), 1.13 (t, J ϭ 6.90 Hz, 3 H). MS
(70 eV): m/z (%) ϭ 284 (17) [M]ϩ, 249 (23), 241 (100), 225 (47),
212 (13), 149 (17), 137 (19), 91 (16), 71 (34), 43 (54).
2-Hexylamine-3,5-dinitrobenzonitrile (22): Table 2, Entry 10. This
product could not be isolated and was tentatively assigned. 1H
NMR (250 MHz, CD3CN): δ ϭ 9.06 (d, J ϭ 2.85 Hz, 1 H), 8.96
(s, 1 H), 8.63 (d, J ϭ 2.85 Hz, 1 H), 3.45 (q, J ϭ 6.25 Hz, 2 H),
1.75 (m, 2 H), 1.38 (m, 6 H), 1.13 (t, J ϭ 7.25 Hz, 3 H). MS (70 eV):
m/z (%) ϭ 292 (6) [M]ϩ, 257 (3), 245 (3), 221 (100), 217 (10), 208
N-Butyl-2,4-dinitro-1-naphthalenamine (15):[20] Table 1, Entry 6. 1H
NMR (250 MHz, CD3CN): δ ϭ 9.73 (s, 1 H), 9.16 (s, 1 H), 8.75 (11), 205 (39), 191 (15), 175 (14), 163 (10), 129 (19), 117 (11), 102
(dd, J ϭ 8.60 Hz, J ϭ 0.70 Hz, 1 H), 8.32 (dd, J ϭ 8.60 Hz, J ϭ (12), 99 (12), 81 (14), 56 (12), 43 (25).
258
Eur. J. Org. Chem. 2002, 251Ϫ259