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Chemical Structure| 70232-59-6 Chemical Structure| 70232-59-6

Structure of 70232-59-6

Chemical Structure| 70232-59-6

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Product Details of [ 70232-59-6 ]

CAS No. :70232-59-6
Formula : C6H6BrN3O2
M.W : 232.03
SMILES Code : O=[N+](C1=CC(Br)=CN=C1NC)[O-]
MDL No. :MFCD07375006
InChI Key :KOPIJZGJPUGTHU-UHFFFAOYSA-N
Pubchem ID :10868149

Safety of [ 70232-59-6 ]

GHS Pictogram:
Signal Word:Danger
Hazard Statements:H302-H318
Precautionary Statements:P280-P305+P351+P338
Class:8
UN#:1759
Packing Group:

Application In Synthesis of [ 70232-59-6 ]

* 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.

  • Downstream synthetic route of [ 70232-59-6 ]

[ 70232-59-6 ] Synthesis Path-Downstream   1~1

  • 1
  • [ 70232-59-6 ]
  • [ 89415-54-3 ]
YieldReaction ConditionsOperation in experiment
~ 100% Step 2. 5-bromo-N2-methylpyridine-2,3-diamine; The crude material was dissolved in acetic acid (10 ml) and water (2.5 ml) and iron (445 mg, 7.97 mmol) was added. The reaction was stirred at room temperature for 40 minutes and then poured into 5 N NaOH (40 ml), and the suspension was cooled briefly in an ice water bath. Then, the suspension was filtered through a Celite (diatomaceous earth), pad, which was washed with water, EtOAC, and 10: 1 DCM / MeOH. The biphasic solution was separated, and the aqueous phase was extracted with 10: 1 DCM / MeOH. The Celite (diatomaceous earth), pads were washed again with MeOH, and this filtrate was combined with the organic extracts, concentrated, and dried under high vacuum in water bath (~ 60 C) to afford 5-bromo-N2-methylpyridine-2,3-diamine (427 mg, ~ 100%). LCMS supports structure of compound (peak at 0.7 minutes with m/e of 202 and 204). Compound isolated in ~ 100% yield over 2 steps. MS (ESI pos. ion) m/z: 202 (MH+, 79Br), 204 (MH+, 81Br). Calculated exact mass for C6H8BrN3 201 (79Br), 203 (81Br).
92.5% With hydrogen;aluminum nickel; In ethyl acetate; d. 3-amino-5-bromo-2-methylamino-pyridine Prepared analogously to Example 3d from 5-bromo-3-nitro-2-methylamino-pyridine and Raney nickel/hydrogen in ethyl acetate. Yield: 92.5% of theory, Rf value: 0.18 (silica gel; methylene chloride/ethanol=19:1).
77% 63b (2.95 g, 1 eq) is dissolved in THF (51 mL) and 1N aq HCl (50 mL, 3.9 eq) and tin powder (2.57 g, 1.70 eq) are added and stirred at RT for 3 h. 1N NaOH (50 mL) is added, followed by brine. The mixture is extracted with EtOAc (3×). The organic layer is washed with brine, dried over Na2SO4, filtered and concentrated under vacuum. The obtained 63c is dried under high vacuum and used in the subsequent step without further purification (1.98 g, 77%).
A suspension of (5-brorno-3-nitro-py?din-2-yl)-methylamine (Stage 67.1.5, 4.58 g, 19.75 mmol) and tin dichloride dihydrate (Acros, Basel, Switzerland, 13.38 g, 59 3 mmol) in 200 ml of THF was heated at 7OC for 220 mialpha The solvent was removed by evaporation and the residue taken in CH2CI2 (100 ml) and 5 M aqueous NaOH (50 ml) and stirred until all the solid was dissolved. The organic layer was separted and the aqueous layer was extracted with CH2CI2 The combined organic layers were washed with brine, dried over Na?SO4l ftltered and evaporated to give the tie compound as a brown solid. (HPLC tR 1 69 min (Method A), M+H = 202, 204 MS-ES)
With tin(II) chloride dihdyrate; In ethyl acetate; for 3.5h;Reflux; [00134] SnCI2*2H2O (4.71 g, 20.9 mmol) is added to a solution of (5-bromo-3-nitro- pyridin-2-yl)-methyl-amine (0.97 g, 4.2 mmol) in EtOAc and the mixture is heated to reflux for 3.5 h. The mixture is then cooled, diluted with saturated aqueous NaHCO3 solution and extracted with EtOAc. The organic phase is dried over anhydrous Na2SO4 and evaporated to dryness to give sufficiently pure 5-Bromo-N*2*-methyl-pyridine-2,3- diamine.
With iron; ammonium chloride; In ethanol; water; for 2h;Reflux; A mixture of the 5-bromo-/V-methyl-3-nitro-2-pyridinamine (1.14 g, 4.21 mmol assumed). and ammonium chloride (1.103 g, 20.62 mmol) in EtOH^O (8.5 mL of a 1 :1 solution) was stirred as iron (1 .152 g, 20.62 mmol) was added. The mixture was heated to reflux for ~ 2 hours. The mixture was allowed to cool to room temperature then diluted with EtOH and filtered through Celite. The filtrate was concentrated to yield a black tar which was diluted with EtOH then concentrated three times. The residue was slurried in EtOH then filtered. The filtrate was concentrated to yield a black solid which was dissolved in pyridine (15.1 mL). N, N dimethylaminopyridine (0.060 g, 0.49 mmoL) was added followed bybenzenesulfonylchlonde (0.63 mL, 4.91 mmol). The resulting mixture was stirred for one hour under a nitrogen atmosphere. The mixture was then concentrated. The residue diluted with EtOAc, washed with water two times, then saturated NaHC03 followed by brine, dried(Na2S0 ) and concentrated. The residue was purified by silica gel chromatography (0-100% EtOAc in hexanes). Fractions containing the product were combined and concentrated to yield A/-[5-bromo-2-(methylamino)-3-pyridinyl]benzenesulfonamide (0.859 g, 2.51 mmol 60% over 3 steps) as a grey solid. 1H NMR (400 MHz, DMSO-d6) delta ppm 9.58 (br. s., 1 H) 7.94 (br. s., 1 H) 7.75 - 7.64 (m, 3 H) 7.62 - 7.55 (m, 2 H) 6.92 (d, J=2.3 Hz, 1 H) 6.25 (br. s., 1 H) 2.68 (d, J=4.5 Hz, 3 H) LCMS: m/z 344 (M+1 ).
With tin(II) chloride dihdyrate; In ethanol; at 20 - 80℃; for 4h; 5-Bromo-N2-methylpyridine-2,3-diamineTo a solution of 5-bromo-N-methyl-3-nitropyridin-2-amine (800 mg, 3.45 mmol) in EtOH (20 ml_) at RT, SnCI2-2 H20 (31 12 mg, 13.79 mmol) was added. The reaction mixture was stirred for the 4 h at 80 C. The solvent was evaporated under reduce pressure and saturated NaHC03solution was added to pH=7 then was extracted with EtOAc (2x), and the combined organic layers were washed once with brine. The organic layer was concentrated to give 720 mg (103%) of the title compound. LC-MS m/z 202.1 , 203.9 (M+H)+, 0.33 (ret. time).
With ammonium metavanadate; platinum on carbon; hydrogen; hypophosphorous acid; In tetrahydrofuran; ethanol; water; at 20 - 45℃; under 15201.0 Torr; for 1.5h; Into a pressure reactor was charged with Pt/C (5% wt, 78.7 g, 10.6% w/w), aq. H3PO2 (50 % wt, 5.8 g), NH4VO3 (2.1 g), THF/EtOH (V/V = 1/1, 12.1 L) and 5-bromo-N-methyl-3-nitropyridin-2-amine (740 g, 3.19 mol). The reactor was purged with hydrogen and pressurized to 20 atm followed by stirring at 20 to 30 C for about 0.5 h. Then the mixture was re-pressurized to 20 atm with hydrogen and stirred at 30 to 45 C for 1 h. The reaction mixture was cooled to room temperature and filtered through a pad of Celite followed by washing the cake with THF (1 L). The combined filtrate was concentrated at 40 to 45 C under vacuum. Solvent chasing distillation by n-heptane (1 L × 2) and dilution with ACN (3 L) afforded a dark solution of the title compound in ACN which was used in the next step without further purification

 

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