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With ammonium hydroxide; In ethanol; water; at 20.0℃; for 4.0h;
EXAMPLE 23B; 4-Amino-2-chloro-5-nitrobenzonitrile; To a solution of EXAMPLE 23A (10.0 g, 50 mmol) in ethanol (100 mL) was added ammonium hydroxide solution (28% in water, 50 mL) and suspension was stirred at room temperature for 4 hours. The precipitate was filtered and air-dried to afford the title compound. NMR (300 MHz, dimethylsulfoxide-d6) delta ppm 8.58 (s, 1 H) 8.21 (s, 2 H) 7.22 (s, 1 H).
REFERENCE EXAMPLE 4 STR12 4-Cyano-3-(4-oxo-4H-pyridin-1-yl)-6-nitroaniline First, a mixture containing 1.0 g of <strong>[172455-36-6]3-chloro-4-cyano-6-nitroaniline</strong>, 507 mg of 4-hydroxypyridine, 330 mg of 86% potassium hydroxide, and 5 ml of dimethylsulfoxide was heated in an oil bath at 110 C. for 3 hours. The subsequent processes were conducted in the same way as in Reference Example 3 to give 836 mg of crystals of 4-cyano-3-(4-oxo-4H-pyridin-1-yl)-6-nitroaniline. Melting point: 354-357 C. (decomposition) Elemental analysis (analyzed as C12 H8 N4 O3) Calculated: C,56.25; H,3.15; N,21.87 (%) Found: C,56.25; H,3.27; N,21.83 (%) H1 -NMR (d6 -DMSO)delta: 6.28 (2H, d, J=8 Hz), 7.13 (1H, s), 7.92 (2H, d, J=8 Hz), 8.24 (2H, br.s), 8.68 (1H, s).
lambda/-(4-Chloro-5-cyano-2-nitro- phenyl)-acetamide (1.06 g, 4.415 mmol) was added to 2 M HCI (45 ml_) and heated to reflux for 2 h, then kept at 60 0C for 16 h. The reaction mixture was cooled and brought to pH 9 with saturated aqueous sodium bicarbonate. This was extracted with EtOAc (3 x 50 ml_), washed with brine (1 x 15 ml_), dried, filtered, and concentrated to yield the titled compound (0.868 g, 99%). This compound did not yield MS data. 1H NMR (400 MHz, CDCI3): 8.49 (s, 1 H), 7.23 (br s, 2H), 7.02 (s, 1 H), 2.40 (s, 3H).
tert-butyl (5-chloro-4-cyano-2-nitrophenyl)carbamate[ No CAS ]
Yield
Reaction Conditions
Operation in experiment
59%
Stage #1: 2-chloro-4-amino-5-nitrobenzonitrile With lithium hexamethyldisilazane In tetrahydrofuran at 0 - 0.2℃; for 0.166667h;
Stage #2: di-<i>tert</i>-butyl dicarbonate In tetrahydrofuran at 0 - 0.2℃;
161.1 Step 1: Tert-butyl (5-chloro-4-cyano-2-nitrophenyl)carbamate:
4-amino-2-chloro-5- nitrobenzonitrile (0.5 g, 2.53 mmol) was dissolved in THF (2 ml) and cooled to 0 °C before the addition of 1 M LiHDMS in THF (2.5 ml, 2.50 mmol). The reaction mixture was allowed to warm to RT and stirred for 10 min then cooled to 0 °C before the addition of di-tert-butyl dicarbonate (0.6 g, 2.75 mmol). The resultant solution was allowed to warm to RT and stirred overnight. The reaction mixture was quenched by portionwise addition to a cooled solution of acetic acid (1 ml) in THF (4 ml). The reaction mixture was concentrated in vacuo and purified by chromatography on silica gel (40 g cartridge, 0-100% EtOAc/lsohexane) and then on silica gel (40 g cartridge, 0-100% DCM/lsohexane) to afford (443 mg, 1.49 mmol, 59% yield, 100%) as a white solid. UPLC-MS (Method 2): m/z 296.1 (M-H)- at 1.70 min.
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