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Structure of 92406-50-3

Chemical Structure| 92406-50-3

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Product Details of [ 92406-50-3 ]

CAS No. :92406-50-3
Formula : C9H10N4
M.W : 174.20
SMILES Code : NC1=CC(C2=NC=CC=C2)=NN1C
MDL No. :MFCD08059967

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Application In Synthesis of [ 92406-50-3 ]

* All experimental methods are cited from the reference, please refer to the original source for details. We do not guarantee the accuracy of the content in the reference.

  • Downstream synthetic route of [ 92406-50-3 ]

[ 92406-50-3 ] Synthesis Path-Downstream   1~5

  • 1
  • [ 24078-12-4 ]
  • [ 68-11-1 ]
  • [ 92406-50-3 ]
  • [ 1616363-72-4 ]
YieldReaction ConditionsOperation in experiment
68% In acetonitrile; at 150℃; for 0.416667h;Sealed tube; Microwave irradiation; A mixture of 1-methyl-3-(2-pyridyl)pyrazol-5-amine (1.74 g, 10 mmol), <strong>[24078-12-4]4-bromo-2-methylbenzaldehyde</strong> (2.0 g, 10 mmol, Ark Pharm Inc.), and thioglycolic acid (3.90 g, 32 mmol) in acetonitrile (15 mL) was heated, in a sealed microwave vessel, for about 25 min, at about 150 C., in a microwave. After cooling to rt the precipitated solid was collected by filtration and washed with acetonitrile and diethyl ether to afford 4-(4-bromo-2-methyl-phenyl)-1-methyl-3-(2-pyridyl)-4,8-dihydropyrazolo[3,4-e][1,4]thiazepin-7-one (2.92 g, 6.8 mmol, 68%), which was used as such. 1H-NMR (CDCl3, Bruker 400 MHz) delta 2.56 (3H, s), 3.29 (1H, d, J=15 Hz); 3.37 (1H, d, J=15 Hz); 3.95 (3H, s); 6.58 (1H, s); 6.66 (1H, d, J=8 Hz); 7.03 (2H, m); 7.24 (1H, d, J=11 Hz); 7.56 (1H, dt, J=8 Hz, 2 Hz); 7.75 (1H, m), 8.30 (1H, d, J=4 Hz).
  • 2
  • [ 24078-12-4 ]
  • [ 92406-50-3 ]
  • [ 24653-75-6 ]
  • [ 1616361-85-3 ]
YieldReaction ConditionsOperation in experiment
69% With toluene-4-sulfonic acid; In water; acetonitrile; at 150℃; for 0.666667h;Sealed tube; Microwave irradiation; A mixture of 1-methyl-3-(2-pyridyl)pyrazol-5-amine (0.30 g, 1.72 mmol, Example No.2, step B), <strong>[24078-12-4]4-bromo-2-methyl-benzaldehyde</strong> (0.34 g, 1.72 mmol, Ark Pharm), 1-sulfanylpropan-2-one (0.31 g, 3.44 mmol, Enamine), and p-toluenesulfonic acid monohydrate (0.098 g, 0.52 mmol) in acetonitrile (3 mL) was heated, in a sealed microwave vessel, for about 40 min, at about 150 C., in a microwave. After cooling to rt the mixture was concentrated in vacuo. The residue was dissolved in ethyl acetate (40 mL) and methanol (2 mL), and washed with 5% aqueous sodium bicarbonate (20 mL). The aqueous layer was extracted with ethyl acetate (40 mL). The combined organic layers were washed with water (10 mL), dried (MgSO4), filtered and concentrated in vacuo. The residue was purified by column chromatography (SiO2, ethyl acetate/hexanes 1:4) to afford 4-(4-bromo-2-methylphenyl)-1,7-dimethyl-3-(pyridin-2-yl)-4,6-dihydro-M-pyrazolo[3,4-e][1,4]thiazepine (0.507 g, 1.19 mmol, 69%), as a yellow oil: 1H-NMR (CDCl3, Bruker 400 MHz) delta 2.36 (3H, s) 2.60 (3H, s) 3.15 (1H, d, J=16 Hz) 3.29 (1H, dd, J=16, 2 Hz) 4.03 (3H, s) 6.44 (1H, d, J=9 Hz) 6.59 (1H, d, J=1.5 Hz) 6.98-7.06 (2H, m) 7.29 (1H, d, J=2 Hz) 7.56 (1H, td, J=8, 2 Hz) 7.86 (1H, d, J=8 Hz) 8.34 (1H, d, J=4 Hz).
  • 3
  • [ 24078-12-4 ]
  • [ 92406-50-3 ]
  • [ 1616360-33-8 ]
YieldReaction ConditionsOperation in experiment
64% With toluene-4-sulfonic acid; In water; acetonitrile; at 45℃; for 0.25h; A suspension of 1-methyl-3-(pyridin-2-yl)-1H-pyrazol-5-amine (4.50 g, 25.8 mmol, Example No.2 step B), <strong>[24078-12-4]4-bromo-2-methylbenzaldehyde</strong> (5.14 g, 25.8 mmol, Astatech) and 4-methylbenzenesulfonic acid hydrate (0.491 g, 2.58 mmol) in MeCN (36 ml) was warmed up to about 45 C. for about 15 min to give a solution then the reaction was allowed to cool to rt. The precipitate was filtered and washed with MeCN to give 4-(4-bromo-2-methylbenzylidene)-1-methyl-3-(pyridin-2-yl)-1H-pyrazol-5(4H)-imine (5.88 g, 16.55 mmol, 64%) as a beige solid: LC-MS (Table 1, Method g) Rt=2.55 min, m/z 355/357 (M+H)+; 1H-NMR (DMSO-d6, Bruker 400 MHz) delta 9.07 (s, 1H), 8.60-8.57 (m, 1H), 8.02-7.95 (m, 2H), 7.91-7.86 (m, 1H), 7.61-7.50 (m, 2H), 7.40-7.31 (m, 1H), 7.19 (s, 1H), 3.96 (s, 3H), 2.62 (s, 3H).
  • 4
  • [ 24078-12-4 ]
  • [ 92406-50-3 ]
  • [ 1616361-49-9 ]
  • 5
  • [ 24078-12-4 ]
  • [ 1616363-97-3 ]
  • [ 92406-50-3 ]
  • rac-(4S,7S)-4-(4-bromo-2-methylphenyl)-1-methyl-3-(pyridin-2-yl)-7-(trifluoromethyl)-4,6,7,8-tetrahydro-1H-pyrazolo[3,4-e][1,4]thiazepine [ No CAS ]
  • rac-(4S,7R)-4-(4-bromo-2-methylphenyl)-1-methyl-3-(pyridin-2-yl)-7-(trifluoromethyl)-4,6,7,8-tetrahydro-1H-pyrazolo[3,4-e][1,4]thiazepine [ No CAS ]
YieldReaction ConditionsOperation in experiment
0.204 g; 0.192 g A solution of 1-methyl-3-(pyridin-2-yl)-1H-pyrazol-5-amine (0.300 g, 1.72 mmol, Example 2, step B), <strong>[24078-12-4]4-bromo-2-methylbenzaldehyde</strong> (0.343 g, 1.72 mmol, Astatech) and 4-methylbenzenesulfonic acid hydrate (0.033 g, 0.172 mmol) in MeCN (4 mL) was stirred at rt for about 2 h. 2,2-Diethoxy-3,3,3-trifluoropropane-1-thiol (1.139 g, 1.72 mmol) was added to the reaction and was heated at about 90 C. for about 20 h. The reaction was allowed to cool to rt and was concentrated in vacuo. The residue was dissolved in MeOH (20 mL), cooled to 0 C. and sodium tetrahydroborate (0.130 g, 3.44 mmol) was added. The reaction was stirred at rt for about 2 h. Sodium tetrahydroborate (0.130 g, 3.44 mmol) was added to the reaction. The reaction was stirred at rt for about 2 h. The reaction was quenched with NH4Cl (10 mL) and extracted with EtOAc (10 mL). The organic layer was washed with brine (10 mL), dried over Na2SO4, filtered and concentrated in vacuo. The residue was purified by column chromatography (SiO2, 0-2.5% MeOH/DCM) and column chromatography (SiO2, 0-20% EtOAc/heptanes) to give rac-(4R,7R)-4-(4-bromo-2-methylphenyl)-1-methyl-3-(pyridin-2-yl)-7-(trifluoromethyl)-4,6,7,8-tetrahydro-M-pyrazolo[3,4-e][1,4]thiazepine compound (0.204 g, 0.422 mmol, 24%) as a white solid: LC-MS (Table 1, Method g) Rt=2.80 min, m/z 483/485 (M+H)+; 1H-NMR (CDCl3, Bruker 400 MHz) delta 8.37 (d, J=4.3 Hz, 1H), 7.82 (d, J=8.0 Hz, 1H), 7.66-7.57 (m, 1H), 7.31-7.25 (m, 1H), 7.14-7.03 (m, 2H), 6.83 (d, J=8.3 Hz, 1H), 6.51 (s, 1H), 4.04 (d, J=7.7 Hz, 1H), 3.94 (s, 3H), 3.75-3.60 (m, 1H), 3.05-2.94 (m, 2H), 2.65 (s, 3H) and rac-(4R,7S)-4-(4-bromo-2-methylphenyl)-1-methyl-3-(pyridin-2-yl)-7-(trifluoromethyl)-4,6,7,8-tetrahydro-1H-pyrazolo[3,4-e][1,4]thiazepine compound (0.192 g, 0.397 mmol, 23%) as a white solid: LC-MS (Table 1, Method g) Rt=2.87 min, m/z 483/485 (M+H)+; 1H-NMR (CDCl3, Bruker 400 MHz) delta 8.39-8.37 (m, 1H), 7.83-7.80 (m, 1H), 7.64-7.62 (m, 1H), 7.32 (d, J=1.8, 1H), 7.15-7.03 (m, 2H), 6.76 (d, J=8.2 Hz, 1H), 6.52 (s, 1H), 3.93 (s, 3H), 3.83-3.75 (m, 2H), 3.00-2.89 (m, 2H), 2.61 (s, 3H).
 

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