4-Methoxy-1,2-phenylenediamine

Dark Brownish Black Solid

Approximately 360 mg (2.14 mmol) of 4-methoxy-2-nitroanniline was placed in a hydrogenator and 65 mL ethanol was added. A pinch of 10percent palladium on activated carbon was added and the reaction mixture hydrogenated at room temperature under 50 Psi pressure for 24 hrs. The reaction mixture was filtered and concentrated on rotovap to give TZ10-55 as dark purple oil (294 mg, 2.12 mmol, 99percent). Example 68: T-chloro-B-oxo-B^-dihydro^H-benzon^lthiazine--carboxylic acid {1- [2-f7-methoxy-3-methyl-quinoxalin-2-yloxy)-ethyll-piperidin-4-yl}-amide: Preparation of 4-methoxy-benzene-l , 2-diamine: 10percent Palladium on activated carbon (1.0 g, 9.4 mmol, 0.15 eq) is added at room temperature to a stirred solution of 4-methoxy-2-nitro-phenylamine (10.0 g, 59.5 mmol, 1.0 eq) in methanol (70 mL). The mixture is hydrogenated for 72 hours, then filtered through decalite. Solvent is removed to afford 4-methoxy-benzene-l, 2-diamine as a dark brown oil (8.0 g, 97percent yield).To a stirred solution of 4-methoxy-2-nitroaniline (8.7 g, 51.73 mmol) in EtOHJH2O(3:1, 105 mL) was added portion wise Fe powder (20.5 g, 36.73 mmol) followed byNH4C1 at room temperature. The reaction mixture was heated at reflex for 24h. Aftercompletion of the reaction, filtered through a small pad of Celite and washed withEtOH (3 X 30 mL), solvent was evaporated under reduced pressure. The obtainedcrude was dissolved in H20 (50 mL) and extracted with EtoAc (3 X 60 mL). Thecombined organic layers were dried over anhydrous Na2504, filtered and concentrated under reduced pressure to get a 84.5 percent yield of dark brown colour solid, which was used in the next step without any further purification. ‘H NMR (500 MHz, DMSO-d6):5 6.50 (d, 1H), 6.20 (d, 1H), 6.00 (dd, 1H), 3.50 (s, 3H). LC-MS [mlz]: 139.2 [M+H], 91.670percent purity.To a mixture of compound 1 (33.6 g, 0.020 mol) and Pd/C (6.72 g) in MeOH (400 mL) was hydrogenated under 50 psi of HIntermediate 35:[0166] To a solution of 4-methoxy-2-nitroaniline (10 g, 59.4 mmol) in EtOH (200 mL) and water (80 mL) was added iron (12 g, 210 mmol) and ammonium chloride (9.63 g, 180 mmol). The mixture was then heated to reflux and stirred overnight. The mixture was filtered and the filtrate was evaporated to remove the EtOH and the residue was purified by flash chromatography on silica gel column (elution with DCM/MeOH = 80:1) to give 4- methoxybenzene-l, 2-diamine (intermediate 35) (5.65 g, 69percent) as a yellow solid.General procedure: Hydrazine hydrate was chosen as the hydrogen donor for the low emission of pollutants. In a typical procedure, hydrazine hydrate (4 equiv) was added into the reactor which containing fresh prepared catalyst as described above. Then the reactor was put into a preheated oil bath with a stirring speed of 500 rpm, and the substrate (1 mmol)dissolved in 1 mL ethanol was added drop-wisely under argon. The reactions were monitored by TLC. After the reaction, the reaction mixture was vacuum filtered through a pad of silica on a glass-fritted funnel and an additional 15 mL of ethyl acetate (5 mL portions) was used to rinse the product from the silica, the filtrate was concentrated in vacuum and analyzed by GC. Products were purified by column chromatography and identified by 1H NMR and 13C NMR.32 g of 5-methoxy-2-nitroaniline was added to 350 ml of methanol, 3.2 g of 10percent palladium carbon was added, hydrogen was bubbled in, stirred overnight, filtered, the filtrate was collected, and concentrated to give 24 g of 4-methoxy-1 2-diphenylamine.

Molecular Weight:138.17
XLogP3:0.6
Hydrogen Bond Donor Count:2
Hydrogen Bond Acceptor Count:3
Rotatable Bond Count:1
Exact Mass:138.079312947
Monoisotopic Mass:138.079312947
Topological Polar Surface Area:61.3
Heavy Atom Count:10
Complexity:108
Covalently-Bonded Unit Count:1
Compound Is Canonicalized:Yes