97% |
With hydrogen In methanol |
|
95% |
With hydrogen In ethyl acetate |
|
93% |
With hydrogen In ethyl acetate for 1.5h; Ambient temperature; |
|
82.9% |
With water; iron; ammonium chloride In ethanol at 80℃; for 1h; |
4 6-picoline-2,3-diamine
Dissolve 2-amino-3-nitro-6-picoline 4a (3.0g, 19.6mmol) in 30mL ethanol, add reduced iron powder (5.5g, 98mmol), ammonium chloride (0.5g, 9.8mmol) And 6mL water, the temperature was raised to 80°C and reacted for 1 hour. The reaction solution was filtered with Celite, and the filtrate was concentrated under reduced pressure to obtain 6-picoline-2,3-diamine 4b (2.0 g, oily liquid) with a yield of 82.9%. |
75% |
With platinum on activated charcoal; hydrogen In methanol at 18 - 25℃; for 4h; |
246.1 Step 1: Intermediate 1
Step 1: Intermediate 1 [00803j A mixture of 6-methyl-3-nitropyridin-2-amine (500 mg, 3.26 mmol) and Pt/C (250 mg) in MeOH (12 mL) was stirred at room temperature for 4 h under hydrogen atmosphere. The reaction mixture was filtered, and the filtrate was concentrated to afford yellow solid (300 rng, 75% yield) LCMS: 124.3 [M+1]. |
|
With palladium on activated charcoal; ethanol; hydrazine hydrate |
|
|
With palladium on activated charcoal; ethanol Hydrogenation; |
|
|
With hydrogen In methanol |
|
|
With hydrogen In ethanol |
|
|
In methanol |
20.b b
b 2,3-Diamino-6-methylpyridine 2-Amino-6-methyl-3-nitropyridine (754 mg, 4.92 mmol) was suspended in MeOH, and 10% Pd/C was added. The mixture was stirred briskly at RT under H2 (balloon). After 4 h, the reaction was filtered through CELITE, and the filtrate was concentrated under vacuum to afford the title compound (677. mg, quantitative). |
|
With hydrogen In methanol at 0℃; for 2h; |
536.A
Step A: A mixture of 6-methyl-3-nitro-2-pyridinamine (3 g, 19.8 mmol) and Raney Ni (1 g) in MeOH (150 ml) was stirred in an autoclave filled with H2 (50 psi) at 0 °C for 2 hours. When TLC showed the reaction was completed, the mixture was filtered, and the filtrate was concentrated to give 6-methyl-2,3-pyridinediamine. |
7 g |
With palladium 10% on activated carbon; hydrogen In tetrahydrofuran; methanol for 5h; |
Intermediate 7
Intermediate 7: Commercially available 2-amino-6-methyl-3-nitropyridine (12 g, 78.36 mmol) was dissolved in a mixture of dry THF/MeOH (1 :1 , 60 ml_) and hydrogenated in the presence of Pd/C (10%, 1 .2 g) under 5 bar hydrogen atmosphere for 5 h. Catalyst was filtered, solvent evaporated under reduced pressure to obtain 7 g of the title compound. HPLC-MS (Method 2): Rt = 0.77 min MS : m/z = 154(M |
7 g |
With palladium 10% on activated carbon; hydrogen In tetrahydrofuran; methanol for 5h; |
Intermediate 7
10612] Commercially available 2-amino-6-methyl-3-nitro- pyridine (12 g, 78.36 mmol) was dissolved in a mixture of dry THF/MeOH (1:1, 60 mE) and hydrogenated in the presence of Pd/C (10%, 1.2 g) under 5 bar hydrogen atmosphere forh. Catalyst was filtered, solvent evaporated under reduced pressure to obtain 7 g of the title compound.10613] HPEC-MS (Method 2): R=0.77 mm10614] MS: mlz=154 (M+H) |
|
With palladium 10% on activated carbon; hydrogen at 20℃; Inert atmosphere; Sealed tube; |
|
|
With palladium on activated charcoal; hydrogen In ethanol; ethyl acetate for 0.333333h; |
|
|
In methanol |
46.b b
b 2,3-Diamino-6-methylpyridine 2-Amino-6-methyl-3-nitropyridine (754 mg, 4.92 mmol) was suspended in MeOH, and 10% Pd/C was added. The mixture was stirred briskly at RT under H2 (balloon). After 4 h, the reaction was filtered through Celite, and the filtrate was concentrated under vacuum to afford the title compound (677 mg, quantitative): 1 H NMR (250 MHz, CD3 OD) δ 6.82 (d, 1H), 6.36 (d, 1H), 2.25 (s, 3H). |