ChemicalBook CAS DataBase List N-(2-Chloropyrimidin-4-YL)-2,3-dimethyl-2H-indazol-6-amine

N-(2-Chloropyrimidin-4-YL)-2,3-dimethyl-2H-indazol-6-amine synthesis

5synthesis methods

Product Name:N-(2-Chloropyrimidin-4-YL)-2,3-dimethyl-2H-indazol-6-amine
CAS Number:444731-74-2
Molecular formula:C13H12ClN5
Molecular Weight:273.72

2,3-dimethyl-6-amino-2H- indazole 5.00g,2,4-Dichloropyrimidine 13.9g and sodium bicarbonate 10.4g were dissolved in 100mL absolute ethanol and heated to 79°C.After refluxing for 4 h, cool to room temperature and filter. The cake was washed well with ethyl acetate, and the filtrate was collected. Concentrate under reduced pressure, remove the solvent, and fully beat with ethyl acetate and filter to give an off-white solid. Recrystallization from methanol gave 7.64 g of product N-(2-Chloropyrimidin-4-YL)-2,3-dimethyl-2H-indazol-6-amine as a white solid, yield: 90.0%.

N-(2-chloropyriMidin-4-yl)-2,3-diMethyl-2H- indazol-6-aMine

3934-20-1 Synthesis

3934-20-1
738 suppliers
$9.00/1g

444731-72-0 Synthesis

444731-72-0
222 suppliers
$8.00/1g

444731-74-2
153 suppliers
$11.00/1g

Yield:444731-74-2 90%

Reaction Conditions:

Stage #1: 2,3-dimethyl-2H-indazol-6-aminewith hydrogenchloride in 2-methoxy-ethanol;water at 20;
Stage #2: 2,6-Dichloropyrimidinewith sodium hydrogencarbonate in tetrahydrofuran;ethanol at 77; for 4 h;

Steps:

1

2,3-dimethyl-6-nitro-2H-indazole (0.48g, 2.5mmol, 1 equiv) was dissolved in 2- methoxyethylether (4.3ml) with heating then cooled down to 0⁰C. Tin chloride (1.6g, 7.1 mmol, 2.8 equiv) was added under nitrogen. Concentrated HCl (3.2ml) was added dropwise keeping the temperature below 5⁰C. When all the HCl was added, the reaction was allowed to warm up to room temperature and stirred for 45 min. Ether (14ml) was added and a precipitate was collected too yield the desired product as an hydrochloride salt (0.35g, 86.8%). 1H NMR (d6-DMSO, 400 MHz) δ= 7.67 (d, J = 8Hz, IH), 7.12 (s, I H), 6.79 (d, J = 8Hz, IH), 4.56 (br s, 2H), 2.50 (s, 3H).Preparation of N-(2-chloropyrimidin-4-yl)-2,3-dimethyl-2H-indazol-6-amine (VI) 2,3-dimethyl-2H-imidazole-6-amine HCl (0.58g, 3mmol) was stirred with sodium bicarbonate (1.02g, 12 mmol, 4 equiv) in THF (3ml) and ethanol (12ml). 2,4- dichloropyrimidine (1.37g, 9 mmol, 3 equiv) was added and the reaction mixture was stirred at 77⁰C under nitrogen for 4 hrs. The reaction was cooled down to room temperature and filtered. The grey solid was washed with ethyl acetate to yield the desired compound (0.74g, 90%). 1H NMR (d6-DMSO, 400MHz) δ= 10.6 (br s, IH, 8.15 (d, J = 8Hz, IH), 8.05 (br s, IH), 7.6 (d, J = 9Hz, IH), 7.15 (d, J = 9Hz, IH), 7.0 (d, J = 8Hz, IH), 4.0 (s, 3H), 2.52 (s, 3H).

References:

WO2009/62658,2009,A1 Location in patent:Page/Page column 34; 1/10

3934-20-1 Synthesis

3934-20-1
738 suppliers
$9.00/1g

635702-60-2 Synthesis