4
Y.-S. Feng et al. / Tetrahedron xxx (2015) 1e6
reduced pressure. The crude products were purified by chroma-
tography on silica gel, eluting with ethyl acetate/petroleum ether
(5/1-2/1).
d
149.65, 134.72, 129.98, 127.97, 123.90, 116.02. Mp 202e203 ꢀC
(lit.15 198e202 ꢀC).
4.1.9. 3-(2,4-Dinitrophenyl amino) propionitrile (2i). Following
4.1.1. 2,4-Dinitro-N-ethylphenylamine (2a).12 Following general
general procedure, yellow solid (78%, 55.3 mg); 1H NMR
procedure, yellow solid (92%, 58.3 mg); 1H NMR (600 MHz, CDCl3)
(600 MHz, CDCl3)
d
8.23 (d, J¼2.5 Hz, 1H), 8.09 (dd, J¼9.1, 2.5 Hz,
d
9.13 (d, J¼2.2 Hz, 1H), 8.50 (s, 1H), 8.27 (dd, J¼9.5, 2.5 Hz, 1H), 6.91
1H), 6.65 (d, J¼9.1 Hz, 1H), 5.33 (s, 1H), 3.69 (q, J¼6.4 Hz, 2H),
(d, J¼9.5 Hz, 1H), 3.47 (dt, J¼14.4, 7.2 Hz, 2H), 1.43 (t, J¼7.2 Hz, 3H).
2.73 (t, J¼6.6 Hz, 2H). 13C NMR (151 MHz, CDCl3)
d 147.47, 138.58,
13C NMR (151 MHz, CDCl3)
d
148.20, 135.81, 130.30, 126.30, 124.28,
125.78, 124.69, 118.79, 117.02, 108.76, 39.20, 18.10. HRMS calcd for
C9H8N4O4 (Mþ): 236.0546; found: 236.0545. Mp 134e136 ꢀC
(lit.21e 134e135 ꢀC).
113.84, 38.32, 14.04. Mp 111e112 ꢀC (lit.12 112e114 ꢀC).
4.1.2. N-Methyl-2,4-dinitroaniline (2b).13,17 Following general pro-
cedure, brown-red solid (92%, 54.4 mg); 1H NMR (600 MHz, CDCl3)
4.1.10. N-Ethyl-2,4-dinitro-1-naphthylamine (2j). Following general
d
9.14 (d, J¼2.5 Hz, 1H), 8.57 (s, 1H), 8.30 (dd, J¼9.5, 2.3 Hz, 1H), 6.92
procedure, yellow solid (81%, 63.5 mg); 1H NMR (600 MHz, CDCl3)
(d, J¼9.5 Hz, 1H), 3.15 (d, J¼5.1 Hz, 3H). 13C NMR (151 MHz, CDCl3)
d
9.65 (s, 1H), 9.16 (s, 1H), 8.75 (d, J¼8.7 Hz, 1H), 8.32 (d, J¼8.5 Hz,
d
149.11, 136.10, 130.41, 124.23, 113.51, 30.24. Mp 172e174 ꢀC (lit.21a
1H), 7.84e7.73 (m, 1H), 7.60e7.54 (m, 1H), 3.98e3.93 (m, 2H), 1.46
171 ꢀC).
(t, J¼7.1 Hz, 3H). 13C NMR (151 MHz, CDCl3)
d 151.86, 132.75, 129.92,
128.22, 126.13, 124.93, 124.53, 123.61, 45.94, 16.88. HRMS calcd for
4.1.3. N-Isopropyl-2,4-dinitroaniline (2c).12 Following general pro-
C
12H11N3O4 (Mþ): 261.0750; found: 261.0752. Mp 169e171 ꢀC
cedure, yellow solid (84%, 56.8 mg); 1H NMR (600 MHz, CDCl3)
(lit.21f 172 ꢀC).
d
9.13 (d, J¼2.6 Hz, 1H), 8.50 (s, 1H), 8.25 (dd, J¼9.6, 2.6 Hz, 1H), 6.92
(d, J¼9.6 Hz, 1H), 3.93 (dq, J¼13.1, 6.5 Hz, 1H), 1.39 (d, J¼6.4 Hz, 6H).
4.1.11. N-Benzyl-2,4-dinitroaniline (2k).16 Following general pro-
13C NMR (151 MHz, CDCl3)
d
147.47, 135.56, 130.25, 130.02, 124.54,
cedure, yellow solid (84%, 68.9 mg); 1H NMR (600 MHz,CDCl3)
114.09, 44.96, 30.94, 22.39. Mp 93e95 ꢀC (lit.21b 94 ꢀC).
d
9.15 (d, J¼2.6 Hz, 1H), 8.91 (s, 1H), 8.23 (dd, J¼9.5, 2.5 Hz, 1H), 7.38
(dt, J¼17.6, 7.5 Hz, 5H), 6.91 (d, J¼9.5 Hz, 1H), 4.65 (d, J¼5.6 Hz, 2H).
4.1.4. N-Butyl-2,4-dinitroaniline (2d).14 Following general pro-
13C NMR (151 MHz, CDCl3)
d 148.16, 136.43, 135.51, 130.33, 129.24,
cedure, yellow solid (89%, 63.9 mg)1; H NMR (600 MHz, CDCl3)
128.33, 127.03, 124.17, 114.36, 47.54. Mp 114e116 ꢀC (lit.16 116 ꢀC).
d
9.14 (d, J¼2.6 Hz, 1H), 8.55 (s, 1H), 8.26 (dd, J¼9.5, 2.6 Hz, 1H), 6.92
(d, J¼9.5 Hz, 1H), 3.41 (td, J¼7.1, 5.3 Hz, 2H), 1.76 (dt, J¼12.9, 7.4 Hz,
4.1.12. Bis(2,4-dinitrophenyl)amine (2m). Following general pro-
2H), 1.50 (dq, J¼14.8, 7.4 Hz, 2H), 1.00 (t, J¼7.4 Hz, 3H). 13C NMR
cedure, pale yellow solid (81%, 84.9 mg); 1H NMR (600 MHz,CDCl3)
(151 MHz, CDCl3)
d
148.36, 135.84, 130.28, 124.32, 113.87, 43.29,
d
11.77 (s,1H), 9.18 (d, J¼2.4 Hz, 2H), 8.46 (dd, J¼9.1, 2.4 Hz, 2H), 7.77
30.66, 20.10, 13.64. Mp 88e90 ꢀC (lit.21c 89e90 ꢀC).
(d, J¼9.1 Hz, 2H). 13C NMR (101 MHz, CDCl3)
d 142.00,140.25,137.87,
129.63, 123.54, 119.99. HRMS calcd for C12H7N5O8 (Mþ): 349.0295;
4.1.5. N-Hexyl-2,4-dinitroaniline (2e). Following general pro-
found: 349.0293. Mp 193e195 ꢀC (lit.21g 198 ꢀC).
cedure, yellow solid (89%, 71.4 mg); 1H NMR (600 MHz, CDCl3)
d
9.08 (d, J¼2.6 Hz, 1H), 8.54 (s, 1H), 8.23 (dd, J¼9.3, 2.4 Hz, 1H),
4.1.13. 2-Methoxy-N-methyl-4,6-dinitroaniline
general procedure, brown-red solid (72%, 49.1 mg); 1H NMR
(600 MHz, CDCl3)
8.75 (d, J¼2.5 Hz, 1H), 7.64 (d, J¼2.5 Hz, 1H),
(2n).17 Following
6.91 (d, J¼9.5 Hz, 1H), 3.40 (td, J¼7.2, 5.4 Hz, 2H), 1.76 (dt, J¼15.0,
7.4 Hz, 2H), 1.49e1.41 (m, 2H), 1.38e1.27 (m, 4H), 0.89 (t,
d
J¼7.1 Hz, 3H). 13C NMR (151 MHz, CDCl3)
d
148.33, 135.74, 130.21,
3.94 (s, 3H), 3.36 (s, 3H). 13C NMR (151 MHz, CDCl3)
d 150.05,143.30,
124.22, 113.89, 43.56, 31.26, 28.57, 26.51, 22.41, 13.88. HRMS calcd
for C12H17N3O4 (Mþ): 267.1219; found: 267.1222. Mp 51e53 ꢀC
(lit.21d 52 ꢀC).
135.06, 131.14, 116.80, 108.39, 56.70, 34.08. Mp 217e219 ꢀC (lit.17
220e222 ꢀC).
4.1.14. N-Methyl-2,4-dinitroaniline (2o).13 Following general pro-
4.1.6. N-Cyclohexyl-2,4-dinitroaniline (2f).12 Following general
cedure, brown-red solid (62%, 36.6 mg); 1H NMR (600 MHz, CDCl3)
procedure, yellow solid (86%, 68.4 mg); 1H NMR (600 MHz,
d
9.14 (d, J¼2.6 Hz, 1H), 8.57 (s, 1H), 8.30 (dd, J¼9.5, 2.4 Hz, 1H), 6.92
CDCl3)
d
9.14 (d, J¼2.4 Hz, 1H), 8.60 (s, 1H), 8.23 (dd, J¼9.5,
(d, J¼9.5 Hz, 1H), 3.15 (d, J¼5.1 Hz, 3H). 13C NMR (151 MHz, CDCl3)
2.6 Hz, 1H), 6.92 (d, J¼9.6 Hz, 1H), 3.59 (s, 1H), 2.11e2.03 (m, 2H),
d
149.11, 136.11, 130.41, 124.24, 113.50, 30.24. Mp 172e174 ꢀC (lit.21a
1.83 (t, J¼6.6 Hz, 2H), 1.61 (d, J¼66.5 Hz, 2H), 1.45 (t, J¼9.8 Hz,
175e176 ꢀC).
4H). 13C NMR (151 MHz, CDCl3)
d 147.45, 135.59, 130.17, 124.64,
114.16, 51.86, 32.39, 31.90, 29.67, 25.26, 24.32. Mp 153e155 ꢀC
4.1.15. N,3-Dimethyl-2,4-dinitroaniline (2p). Following general
(lit.12 155 ꢀC).
procedure, pale yellow solid (26%, 16.5 mg); 1H NMR (600 MHz,
CDCl3)
d
8.08 (d, J¼9.4 Hz, 1H), 6.68 (d, J¼9.4 Hz, 1H), 5.94 (s, 1H),
4.1.7. N-(1-Ethylhexyl)-2,4-dinitroaniline (2g). Following general
2.99 (s, 3H), 2.55 (s, 3H). 13C NMR (151 MHz, CDCl3)
d
145.54,139.00,
procedure, brown-red liquid (86%, 76.2 mg); 1H NMR (600 MHz,
137.32,131.57,129.64,109.41, 30.15,16.66. HRMS calcd for C8H9N3O4
CDCl3)
d
9.10 (dd, J¼4.1, 2.6 Hz, 1H), 8.62 (s, 1H), 8.24 (d, J¼9.4 Hz,
(Mþ): 211.0593; found: 211.0595. Mp 80e81 ꢀC (lit.21h 81 ꢀC).
1H), 6.92 (d, J¼9.6 Hz, 1H), 3.31 (t, J¼5.7 Hz, 2H), 1.74e1.70 (m, 1H),
1.47 (dd, J¼13.6, 7.0 Hz, 2H), 1.44e1.37 (m, 2H), 1.34e1.29 (m, 4H),
0.94 (t, J¼7.4 Hz, 3H), 0.89 (dd, J¼6.9, 5.7 Hz, 3H). 13C NMR
4.1.16. N,5-Dimethyl-2,4-dinitroaniline (2p0).18 Following general
procedure, yellow solid (58%, 36.7 mg); 1H NMR (600 MHz, CDCl3)
(151 MHz, CDCl3)
d
148.55, 135.72, 130.26, 124.27, 113.88, 46.55,
d
9.06 (s, 1H), 8.37 (s, 1H), 6.67 (s, 1H), 3.11 (d, J¼5.1 Hz, 3H), 2.69 (s,
38.70, 31.09, 28.74, 24.42, 22.84, 13.92, 10.81. HRMS calcd for
14H21N3O4 (Mþ): 295.1532; found: 295.1536.
3H). 13C NMR (151 MHz, CDCl3)
d 147.70, 143.12, 136.81, 129.13,
C
125.94, 115.83, 30.06 22.44. Mp 170e172 ꢀC (lit.17 173 ꢀC).
4.1.8. 2,4-Dinitrophenylhydrazine (2h).15 Following general pro-
4.1.17. 5-Cl-N-Methyl-2,4-dinitroaniline (2q). Following general
cedure, brown-red solid (69%, 41.0 mg); 1H NMR (600 MHz, DMSO)
procedure, yellow solid (65%, 41.7 mg); 1H NMR (600 MHz, CDCl3)
d
9.95 (s, 1H), 8.74 (d, J¼2.7 Hz, 1H), 8.18 (ddd, J¼9.7, 2.7, 0.7 Hz, 1H),
d
9.05 (s, 1H), 8.40 (s, 1H), 6.95 (s, 1H), 3.12 (d, J¼5.1 Hz, 3H). 13
C
7.62 (d, J¼9.7 Hz, 1H), 4.99 (s, 2H). 13C NMR (151 MHz, DMSO)
NMR (151 MHz, DMSO) d 147.84, 134.39, 133.23, 128.92, 127.08,