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Chemical Structure| 13535-01-8

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Product Details of 3-Amino-5-bromopyridine

CAS No. :13535-01-8
Formula : C5H5BrN2
M.W : 173.01
SMILES Code : NC1=CC(Br)=CN=C1
MDL No. :MFCD01646060
InChI Key :MDQXGHBCDCOOSM-UHFFFAOYSA-N
Pubchem ID :817681

Safety of 3-Amino-5-bromopyridine

GHS Pictogram:
Signal Word:Warning
Hazard Statements:H302-H315-H319-H335
Precautionary Statements:P261-P305+P351+P338

Application In Synthesis of 3-Amino-5-bromopyridine

* 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 [ 13535-01-8 ]

[ 13535-01-8 ] Synthesis Path-Downstream   1~11

  • 1
  • [ 13535-01-8 ]
  • [ 191162-40-0 ]
  • [ 1202550-08-0 ]
YieldReaction ConditionsOperation in experiment
With dicyclohexyl-(2',6'-dimethoxybiphenyl-2-yl)-phosphane; potassium phosphate;tris-(dibenzylideneacetone)dipalladium(0); In toluene; at 85℃; for 3h; A flask is charged with 3-amino-5-bromopyridine (0.173 g, 0.950 mmol), Λ/-methyl-indole boronic acid (0.262 g, 1.425 mmol), s-Phos (0.030 g, 0.071 mmol), finely crushed potassium phosphate (0.407 g, 1.900 mmol) and toluene (4 ml_). After degassing for 30 min, Pd2dba3 (0.018 g, 0.019 mmol) is added, the flask is flushed with nitrogen and the mixture is heated to 85 0C. After 3 h, the mixture is allowed to cool to r.t., diluted with ethyl acetate and filtered through a plug of silica gel (elution with ethyl acetate). The <n="133"/>residue is purified by silica gel flash chromatography (heptane-ethyl acetate, 3:7 to 0:1 ) to give 2-(5-amino-pyridin-3-yl)-1-methyl-1 H-indole as an off-white powder. 1H NMR (400 MHz, DMSO-cfe) δ ppm 3.74 (s, 3 H), 5.49 (s, 2 H), 6.56 (s, 1 H), 7.05 - 7.09 (m, 1 H), 7.09 - 7.10 (m, 1 H), 7.17 - 7.21 (m, 1 H), 7.49 (d, J=7.6 Hz, 1 H), 7.57 (d, J=7.6 Hz, 1 H), 7.94 (d, J=2.0 Hz, 1 H), 7.99 (d, J=2.5 Hz, 1 H). MS (ESI) m/z 224 (M+H)+.
  • 2
  • [ 13535-01-8 ]
  • [ 89635-82-5 ]
  • [ 1239131-83-9 ]
  • 3
  • [ 13535-01-8 ]
  • [ 628-36-4 ]
  • [ 1272357-00-2 ]
YieldReaction ConditionsOperation in experiment
33% at 150℃; for 16h; A mixture of 3-bromo-5-amino pyridine (0.30 g, 1.7 mmol) and N,N- diformaylhydrazine (0.15 g, 1.7 mmol) was heated at 150 °C in sealed tube for 16 h. A precipitate formed which was dissolved in hot ethanol and then filtered. Diethyl ether was added to the filtrate at room temperature and the slurry was stirred overnight. The resulting solid was separated and purified by silica gel column chromatography using ethyl acetate and hexanes mixture as the eluent to provide 3- bromo-5-(4H-l,2,4-triazol-4-yl)pyridine (130 mg, 33 percent yield) as a white solid. lH NMR (400 MHz, DMSO-i3/4) delta (ppm): 9.24 (s, 2H); 9.03 (d, 1H, J = 2Hz); 8.79 (d, lH, J = 2Hz); 8.60 (t, lH, J = 2Hz).
  • 4
  • [ 13535-01-8 ]
  • [ 68947-43-3 ]
  • [ 1314734-62-7 ]
YieldReaction ConditionsOperation in experiment
43% Steps 1-2[00200] Oxalyl chloride (8.67 mmol) followed by DMF ( 2drops) was added to a solution of 1 -methyl piperidine-4-carboxylic acid (XLIII) (5.78 mmol) in DCM and stirred 30 min at room temperature under argon. The volatiles were evaporated under vacuum by avoiding contact with air. Pyridine was added to the residue followed by addition of 3-amino-5-bromopyridine (XL) (5.20 mmol). The solution was further stirred at room temperature for 3 h under argon. The pyridine was evaporated under vacuum. The residue was treated with water, basified by saturated NaHC03 solution and washed with DCM. The aqueous layer was extracted with n-butanol. The combined organic layer was evaporated. The residue was dissolved in DCM with the addition of few drops of MeOH. The insoluble inorganic solids were filtered off. The filtrate was concentrated under vacuum to get N-(5-bromopyridin-3-yl)-l-methylpiperidine-4-carboxamide (XLIV) as a brown viscous liquid (0.74 g, 43percent yield). 1H NMR (DMSO-d6) 1.61-1.69 (m, 2H), 1.77-1.79 (m, 2H), 1.93-1.97 (m, 2H), 2.20 (s, 3H), 2.29-2.35 (m, 1H), 2.84- 2.87 (m, 2H), 8.36 (d, J = 1.6 Hz, 1H), 8.39 (m, 1H), 8.66 (d, J = 1.6 Hz, 1H), 10.33 (s, 1H); ESIMS found Ci2Hi6BrN30 mlz 299 (M+H).
  • 5
  • [ 13535-01-8 ]
  • [ 628692-15-9 ]
  • [ 1258620-56-2 ]
YieldReaction ConditionsOperation in experiment
47.5% With tetrakis(triphenylphosphine) palladium(0); potassium carbonate; In N,N-dimethyl-formamide; at 120℃;Inert atmosphere; The mixture of 5-bromo-pyriden-3-ylamine (2.6 g, 15 mmol), boronic acid (1.9 g, 12.5 mmol), Pd(PPh3)4 (1.45g, 1.25 mmol), K2C03 (5.18 g, 37.5 mmol) in DMF (50 mL) was stirred at 120°C under N2 overnight. The reaction mixture was concentrated in vacuum. The residue was purified by chromatography on silica gel eluting with EA, to give 1.2 g (yield: 47.5percent) of 5-(2-methoxypyrimidn-5-yl)-3-pyridylamine as yellow solid. [00824] 1H NMR (CDC13, 400 MHz): delta = 8.70 (2H, s), 8.17 (IH, d), 8.13 (IH, d), 7.07 (IH, dd), 4.07 (3H, s).
  • 6
  • [ 13535-01-8 ]
  • [ 628692-15-9 ]
  • [ 1451274-22-8 ]
  • 7
  • [ 13535-01-8 ]
  • [ 1309774-03-5 ]
  • [ 97267-61-3 ]
  • 8
  • [ 13535-01-8 ]
  • [ 1180678-40-3 ]
YieldReaction ConditionsOperation in experiment
42% With N-iodo-succinimide; acetic acid;Reflux; General procedure: NIS (24.75 g, 110.0 mmol) was added to a solution of 2-chloropyridin-4-ylamine (12.85 g, 100.0 mmol) in MeCN (400 mL),and the mixture was stirred and held at reflux overnight. Uponcooling to r.t. the solvent was removed in vacuo and the residuepartitioned between EtOAc (250 mL), sat. Na2S2O3 (100 mL), andH2O (250 mL). The organic layer was separated, washed withH2O (2 × 250 mL), separated, and the solvent removed in vacuoto afford an orange oil that was subjected to column chromatographyon silica gel. Elution with 30-50% EtOAc in PE afforded apale orange solid that was rinsed with 25% EtOAc in PE (80 mL).The solids were collected by filtration and sucked dry to afford2-chloro-5-iodopyridin-4-ylamine (7.32 g) as an off-white solid.The mother liquors were concentrated to dryness in vacuo andthe residues subjected to column chromatography on silica.Elution with 30-50% EtOAc in PE afforded further pure material(1.90 g)
11.5 g With N-iodo-succinimide; acetic acid; at 20℃;Inert atmosphere; 3-Amino-5-bromopyridine (13.8 g, 79.8 mmol) was dissolved in acetic acid (440 mL) and placed under a nitrogen atmosphere. N-lodosuccinimide (16.15 g, 71.8 mmol) was charged to the reaction which was stirred at room temperature overnight. The reaction wasconcentrated and the residue partitioned between EtOAc (200 mL) and saturated aqueous sodium hydrogen carbonate (200 mL). The layers were separated and the organic phase was washed with saturated aqueous sodium hydrogen carbonate (200 mL). The aqueous phase was extracted with EtOAc (3 x 200 mL). The organic extracts were dried over magnesium sulfate, filtered and concentrated. Chromatography (silica; 1.4 Kg packed in70% DCM:30% heptane, eluting with 70-100% DCM in heptane) gave the title compound (11.5 g). 1H NMR (270 MHz, CDCI3): 7.83 (1H, m), 7.04 (1H, m), 4.33 (2H, brs).
11.5 g With N-iodo-succinimide; acetic acid; at 20℃;Inert atmosphere; Preparation 14: 5-Bromo-2-iodo-pyridin-3-ylamine 3-Amino-5-bromopyridine (13.8 g, 79.8 mmol) was dissolved in acetic acid (440 mL) and placed under a nitrogen atmosphere. N-lodosuccinimide (16.15 g, 71.8 mmol) was charged to the reaction which was stirred at room temperature overnight. The reaction was concentrated andthe residue partitioned between EtOAc (200 mL) and saturated aqueous sodium hydrogen carbonate (200 mL). The layers were separated and the organic phase was washed with saturated aqueous sodium hydrogen carbonate (200 mL). The aqueous phase was extracted with EtOAc (3 x 200 mL). The organic extracts were dried over magnesium sulfate, filtered and concentrated. Chromatography (silica; 1.4 Kg packed in 70% DCM:30% heptane, eluting with70-100% DCM in heptane) gave the title compound (11.5 g). 1H NMR (270 MHz, CDCI3): 7.83 (1H, m), 7.04 (1H, m), 4.33 (2H, brs).
11.5 g With N-iodo-succinimide; acetic acid; at 20℃;Inert atmosphere; Preparation II: 5-Bromo-2-iodo-pyridin-3-ylamine H2N3-Amino-5-bromopyridine (13.8 g, 79.8 mmol) was dissolved in acetic acid (440 mL) and placed under a nitrogen atmosphere. N-lodosuccinimide (16.15 g, 71.8 mmol) was charged to the reaction which was stirred at room temperature overnight. The reaction wasconcentrated and the residue partitioned between EtOAc (200 mL) and saturated aqueous sodium hydrogen carbonate (200 mL). The layers were separated and the organic phase was washed with saturated aqueous sodium hydrogen carbonate (200 mL). The aqueous phase was extracted with EtOAc (3 x 200 mL). The organic extracts were dried over magnesium sulfate, filtered and concentrated. Chromatography (silica; 1.4 Kg packed in70% DCM:30% heptane, eluting with 70-100% DCM in heptane) gave the title compound (11.5g). 1H NMR(27OMHz, CDCI3): 7.83(1H, m), 7.04(1H, m),4.33(2H, brs).

  • 9
  • [ 13535-01-8 ]
  • [ 1309774-03-5 ]
  • 10
  • [ 13535-01-8 ]
  • [ 1201645-46-6 ]
  • 11
  • [ 13535-01-8 ]
  • [ 72040-64-3 ]
  • N-(4-((5-bromopyridin-3-yl)amino)-4-oxobutyl)-5-(2-oxohexahydro-1H-thieno[3,4-d]imidazol-4-yl)pentanamide [ No CAS ]
YieldReaction ConditionsOperation in experiment
55.4% Thionyl chloride (20equiv) was added dropwise to dry solid 7 (1equiv) at 0°C. The solution was stirred overnight at room temperature. The thionyl chloride in excess was removed under reduced pressure. Then the product was dissolved in DCM and added dropwise to 3-amino-5-bromopyridine (1equiv) in DCM at 0°C. The resulting mixture was stirred overnight at room temperature. The product was filtered, washed with saturated solution of NaHCO3, and dried under vacuum.
 

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