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CAS No. :25813-25-6 MDL No. :MFCD00082969
Formula : C5H3Br2NO Boiling Point : -
Linear Structure Formula :- InChI Key :-
M.W : 252.89 Pubchem ID :-
Synonyms :

Safety of [ 25813-25-6 ]

Signal Word:Warning Class:N/A
Precautionary Statements:P261-P280-P305+P351+P338 UN#:N/A
Hazard Statements:H302-H315-H319-H332-H335 Packing Group:N/A
GHS Pictogram:

Application In Synthesis of [ 25813-25-6 ]

* 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.

  • Upstream synthesis route of [ 25813-25-6 ]
  • Downstream synthetic route of [ 25813-25-6 ]

[ 25813-25-6 ] Synthesis Path-Upstream   1~15

  • 1
  • [ 25813-25-6 ]
  • [ 36953-41-0 ]
YieldReaction ConditionsOperation in experiment
60%
Stage #1: With n-butyllithium In tetrahydrofuran; hexanes at -90℃;
Stage #2: With water In tetrahydrofuran; hexanes at -90℃;
Step 36-2.; To a solution of T96-2 (8.0 g, 31.3 mmol) in THF (307 mL) at -90° C. was added slowly a solution of n-BuLi (1.15 M in hexanes, 71 mL). The mixture was stirred for 40 min, then water (10 eq) was added and the mixture warmed to room temperature. The solvent was removed under reduced pressure and the resulting residue purified by flash chromatography (acetone:MeOH, 10:1) to give 3.22 g (60percent) of T 96-3.
Reference: [1] Patent: US2010/93720, 2010, A1, . Location in patent: Page/Page column 58
[2] Synlett, 2003, # 11, p. 1678 - 1682
[3] Patent: WO2012/148808, 2012, A1, . Location in patent: Page/Page column 51
  • 2
  • [ 626-64-2 ]
  • [ 36953-41-0 ]
  • [ 25813-25-6 ]
Reference: [1] Synthesis, 2001, # 14, p. 2175 - 2179
  • 3
  • [ 25813-25-6 ]
  • [ 74-88-4 ]
  • [ 2683-35-4 ]
Reference: [1] Yakugaku Zasshi, 1952, vol. 72, p. 274[2] Chem.Abstr., 1953, p. 6416
  • 4
  • [ 25813-25-6 ]
  • [ 13626-17-0 ]
YieldReaction ConditionsOperation in experiment
99% With N-ethyl-N,N-diisopropylamine; trichlorophosphate In acetonitrile for 17 h; Cooling with ice; Reflux Compound (M-41) (10.0 g, 39.5 mmol) was suspended in acetonitrile (50 mL), DIPEA (15 mL, 87 mmol) wasadded at room temperature, phosphoryl chloride (7.4 mL, 79 mmol) was added under ice-cooling, and the mixture wasstirred with heating under reflux for 17 hr. The mixture was allowed to cool, and the reaction mixture was added dropwiseto ice water, and neutralized with sodium carbonate (11.6 g, 138 mmol). Thereafter, the mixture was extracted with ethylacetate, and the organic layer was washed with saturated brine, and dried over anhydrous sodium sulfate. The solventwas evaporated under reduced pressure to give a chloro compound (yield 10.6 g, 99percent) as a brown solid. The chlorocompound (10.6 g, 39.1 mmol) was dissolved in THF (70 mL), sodium methoxide (28percent methanol solution, 14 mL, 59mmol) was added, and the mixture was stirred at 60°C for 30 min. The mixture was allowed to cool, water was addedto the reaction mixture, and the mixture was extracted with ethyl acetate. The organic layer was washed successivelywith water and saturated brine, and dried over anhydrous sodium sulfate. The solvent was evaporated under reducedpressure to give compound (VII-46) (yield 9.21 g, 88percent) as a yellow solid
91% at 70℃; for 3 h; Inert atmosphere In a round-bottom flask, equipped with a stirrer, thermometer and reflux condenser, mix under nitrogen in the specified order: 120 mL of phosphoryl chloride and 38 g (150 mmol) of BCD-BTK-104-9. Stir the reaction mass at 70 °C for 3 hours, cool it to 40 °C, and pour on ice, while stirring vigorously. Filter the precipitate, wash with water, and dry under vacuum at 40 °C. Yield: 36.7 g (91percent).
75% at 140℃; for 2.5 h; Inert atmosphere; Schlenk technique 3,5-dibromopyridin-4-ol (239) (1.00 g, 3.95 mmols) was combined with phosphoryl chloride (921.45 µl, 9.89 mmols) in a pressure stable vessel. The vessel was closed and the solution heated to 140 °C under stirring for 2.5 h. Afterwards the reation vessel was cooled down to rt and the reaction solution combined with ice cold water (75 mL). The aqueous layer was extracted with EtOAc (5 x 15 mL) and the combined organic layers were dried over anhydrous magnesium sulfate. The product was dried in vacuo. Purification of the crude was performed by silica gel column chromatography (1percent EtOAc/n‑pentane) to obtain the product (805 mg, 2.97 mmols, 75percent) as a white solid. Rf: 0.32 (5percent EtOAc/PE). 1H NMR (500 MHz, CDCl3) δ = 8.63 (s, 2H). 13C NMR (126 MHz, CDCl3) δ = 150.97, 144.13, 121.93. GC-MS: tR = 4.59 min; m/z = 268.8, 270.8, 272.8, 274.8 [M ]+. HRMS (ESI): calculated for C5H3N 79Br2 35Cl: m/z = 269.83153 [M+H]+, found: m/z = 269.83155 [M+H]+. calculated for C5H3N 79Br2 37Cl: m/z = 271.82858 [M+H]+, found: m/z = 271.82878 [M+H]+. calculated for C5H3N 79Br 81Br 37Cl: m/z = 273.82653 [M+H]+, found: m/z = 273.82597 [M+H]+. calculated for C5H3N 81Br2 35Cl: m/z = 275.82449 [M+H]+, found: m/z = 275.82316 [M+H]+.
Reference: [1] Patent: EP3351533, 2018, A1, . Location in patent: Paragraph 0676; 0678
[2] Patent: WO2018/92047, 2018, A1, . Location in patent: Page/Page column 94-95
[3] Tetrahedron, 2018, vol. 74, # 35, p. 4531 - 4537
[4] Justus Liebigs Annalen der Chemie, 1932, vol. 4942, p. 284,299
  • 5
  • [ 626-64-2 ]
  • [ 25813-25-6 ]
YieldReaction ConditionsOperation in experiment
100% With N-Bromosuccinimide In tetrachloromethane at 20℃; for 24 h; Step 36-1.; To a solution of 4-hydroxypyridine (T96-1, 7.0 g, 74 mmol) in CCl4 (360 mL) at rt was added NBS (26.2 g, 0.147 mol). The solution was stirred for 24 h in the dark (covered with aluminum foil). The mixture was concentrated under reduced pressure and the resulting residue triturated with MeOH, then with acetone to give 18.9 g (100percent) of T96-2.
88% With N-Bromosuccinimide In tetrachloromethane at 25℃; for 30 h; Inert atmosphere In a round-bottom flask, equipped with a stirrer, thermometer and reflux condenser, mix under nitrogen in the specified order: 500 mL of tetrachloromethane, 23.75 g (250 mmol) of 4-hydroxypyridine, and 89 g (500 mmol) of N-bromosuccinimide. Stir at 25 °C for 30 hours. Filter the precipitate, wash with 50 mL of tetrachloromethane; stir the precipitate in a mixture of 500 mL of acetone and 150 mL of methanol for 15 minutes. Filter the suspension; stir the precipitate in a mixture of 400 mL of acetone and 400 mL of dichloromethane for 15 minutes. Filter the suspension; mix the precipitate vigorously in 400 mL of acetonitrile for 20 minutes. Filter the suspension; dry the precipitate under vacuum at 40 °C. Yield: 56 g (88percent).
86% With N-Bromosuccinimide In tetrachloromethane at 20℃; for 24 h; 4-Pyridinol (M-40) (20.0 g, 210 mmol) was suspended in carbon tetrachloride (400 mL), NBS (77.0 g, 431mmol) was added, and the mixture was stirred under shading at room temperature for 24 hr. The solvent was evaporatedunder reduced pressure, and the residue was suspended in acetone (400 mL)/methanol (120 mL), and the mixture wasstirred at room temperature for 30 min. The precipitated solid was collected by filtration and suspended in acetonitrile(1.0 L), and the suspension was stirred at room temperature for 1 hr. The solid were collected by filtration, and driedunder reduced pressure to give compound (M-41) (yield 46.0 g, 86percent) as a white solid
86% With N-Bromosuccinimide In tetrachloromethane at 20℃; for 24 h; 4-pyridinol (M-40) (20.0 g, 210 mmol)Was suspended in carbon tetrachloride (400 mL)NBS (77.0 g, 431 mmol) was added and, under light shielding,And the mixture was stirred at room temperature for 24 hours.After distilling off the solvent under reduced pressure,The residue was suspended in acetone (400 mL) / methanol (120 mL) and stirred at room temperature for 30 minutes.The precipitated solid was collected by filtration,This was suspended in acetonitrile (1.0 L)And the mixture was stirred at room temperature for 1 hour. After collecting the solid by filtration,After drying under reduced pressure, the compound (M-41)(Yield 46.0 g, yield 86percent)As a white solidIt was.
68% With N-Bromosuccinimide In tetrachloromethane at 20℃; for 24 h; Darkness To a stirring solution of pyridine-4-ol (5g, 52.6 mmol) in CC14 (100 mL) at room temperature was added N-bromosuccinimide (18.72g, 105 mmol). The reaction mixture was allowed to stir under cover of darkness for 24 hours. The solvent was removed under reduced pressure, and the obtained solid was dissolved with acetone (100 mL) and MeOH (30 mL) and stirred for 5 min. The resulting slurry was filtered and the solid was rinsed with excess acetone/CH2Cl2. The solid material was vigorously stirred with acetonitrile, and filtered to yield Intermediate 31A (9.04g, 35.7 mmol, 68percent yield) as an off-white solid. MS (ES): m/z=253.8 [M+H]+. 3/4 NMR (400 MHz, MeOD) δ ppm 8.30 (2 H, s).

Reference: [1] Patent: US2010/93720, 2010, A1, . Location in patent: Page/Page column 58
[2] Synthesis, 2001, # 14, p. 2175 - 2179
[3] Patent: WO2018/92047, 2018, A1, . Location in patent: Page/Page column 94
[4] Patent: EP3351533, 2018, A1, . Location in patent: Paragraph 0676; 0677
[5] Patent: JP2018/145180, 2018, A, . Location in patent: Paragraph 0633; 0634; 635
[6] Tetrahedron Letters, 1997, vol. 38, # 14, p. 2467 - 2470
[7] Patent: WO2012/15723, 2012, A1, . Location in patent: Page/Page column 92; 93
[8] Patent: WO2012/148808, 2012, A1, . Location in patent: Page/Page column 51
  • 6
  • [ 626-64-2 ]
  • [ 36953-41-0 ]
  • [ 25813-25-6 ]
Reference: [1] Synthesis, 2001, # 14, p. 2175 - 2179
  • 7
  • [ 110-89-4 ]
  • [ 25813-25-6 ]
Reference: [1] Chemische Berichte, 1879, vol. 12, p. 988
  • 8
  • [ 1124-33-0 ]
  • [ 25813-25-6 ]
Reference: [1] Recueil des Travaux Chimiques des Pays-Bas, 1951, vol. 70, p. 581,587
  • 9
  • [ 108-96-3 ]
  • [ 25813-25-6 ]
Reference: [1] Gazzetta Chimica Italiana, 1948, vol. 78, p. 873,876
  • 10
  • [ 694-59-7 ]
  • [ 25813-25-6 ]
Reference: [1] Recueil des Travaux Chimiques des Pays-Bas, 1951, vol. 70, p. 581,587
  • 11
  • [ 25813-25-6 ]
  • [ 124-41-4 ]
  • [ 25813-24-5 ]
YieldReaction ConditionsOperation in experiment
88%
Stage #1: With N-ethyl-N,N-diisopropylamine; trichlorophosphate In acetonitrile at 20℃; for 17 h; Cooling with ice; Reflux
Stage #2: at 60℃; for 0.5 h;
Compound (M-41) (10.0 g, 39.5 mmol)Was suspended in acetonitrile (50 mL)DIPEA (15 mL, 87 mmol) was added at room temperature,Phosphoryl chloride (7.4 mL, 79 mmol)Was added under cooling with ice, and the mixture was stirred under heating reflux for 17 hours. After allowing to cool, the reaction solution was added dropwise to ice water,And neutralized with sodium carbonate (11.6 g, 138 mmol).Thereafter, the mixture was extracted with ethyl acetate,The organic layer was washed with saturated brine,And dried over anhydrous sodium sulfate.The solvent was distilled off under reduced pressure,Chloro compound (yield 10.6 g, yield 99percent)As a brown solid.Chloro form (10.6 g, 39.1 mmol)Was dissolved in THF (70 mL)Sodium methoxide (28percent methanol solution,14 mL, 59 mmol) was added,Followed by stirring at 60 ° C. for 30 minutes. After cooling down,Water was added to the reaction solution, and the mixture was extracted with ethyl acetate.The organic layer was washed successively with water and saturated brine,And dried over anhydrous sodium sulfate.The solvent was distilled off under reduced pressure,Compound (VII-46) (yield 9.21 g, yield 88percent)As a yellow solid.
Reference: [1] Patent: JP2018/145180, 2018, A, . Location in patent: Paragraph 0633; 0634; 635
  • 12
  • [ 25813-25-6 ]
  • [ 74-88-4 ]
  • [ 25813-24-5 ]
Reference: [1] Patent: WO2014/152213, 2014, A2, . Location in patent: Page/Page column 57
[2] Patent: WO2014/152278, 2014, A2, . Location in patent: Page/Page column 56
  • 13
  • [ 25813-25-6 ]
  • [ 25813-24-5 ]
Reference: [1] Patent: WO2012/15723, 2012, A1,
[2] Tetrahedron, 2018, vol. 74, # 35, p. 4531 - 4537
[3] Patent: EP3351533, 2018, A1,
  • 14
  • [ 109-72-8 ]
  • [ 25813-25-6 ]
  • [ 124-38-9 ]
  • [ 1052114-83-6 ]
Reference: [1] Journal of Medicinal Chemistry, 2008, vol. 51, # 17, p. 5330 - 5341
  • 15
  • [ 25813-25-6 ]
  • [ 124-38-9 ]
  • [ 1052114-83-6 ]
Reference: [1] Patent: US2013/281428, 2013, A1, . Location in patent: Paragraph 0526; 0527
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