Bromine → HCID 86697419, compound

HRID 1478246Notes

Reaction equation

HRID 1478246 reaction equation
C([O-])(=O)C.[Na+].[CH2:6]([NH:10][C:11]1[CH:16]=[CH:15][N:14]2[N:17]=[CH:18][CH:19]=[C:13]2[N:12]=1)[CH2:7][CH2:8][CH3:9].[Br:20]Br.C(=O)(O)[O-].[Na+]>C(O)(=O)C.O>[Br:20][C:19]1[CH:18]=[N:17][N:14]2[CH:15]=[CH:16][C:11]([NH:10][CH2:6][CH2:7][CH2:8][CH3:9])=[N:12][C:13]=12

Participants

7

Reactant 4

HCID 24408Bromine2×HCID 516892Sodium BicarbonateHCID 517045Sodium AcetateHCID 86697416HCID 86697416, compound

Product 1

HCID 86697419HCID 86697419, compound

Reagents, catalysts & solvents 2

HCID 176Acetic AcidSolvent2×HCID 962WaterSolvent

Procedure

Sodium acetate [127-09-3] (0.7 g, 8.9 mmol) was added to a solution of butyl-pyrazolo[1,5-a]pyrimidin-5-yl-amine (1.1 g, 5.9 mmol) in glacial acetic acid (100 mL) and allowed to stir at ambient temperature until all of the solid had dissolved. Bromine [7726-95-6] (0.3 mL, 6.4 mmol) was added drop by drop into the ambient temperature, buffered, acetic acid reaction solution over 5 minutes. Upon completion of the bromine addition, the suspension was allowed to stir for a further 15 minutes then was slowly poured into 500 mL of stirred water. Saturated aqueous sodium bicarbonate was added to the stirred suspension until pH of the supernatant was determined to be approximately 8 by pH paper, then the suspension was extracted with ethyl acetate. The extract was dried (MgSO4) and flash chromatographed (silica gel eluted with 60% (v/v) ethyl acetate/heptane) to provide 1.2 g of off white solid, mp. 94-95° C. 1 H NMR (400 MHz, DMSO-d6) δ ppm 0.93 (t, J=7.33 Hz, 3 H) 1.31-1.44 (m, 2 H) 1.56 (quin, J=7.20 Hz, 2 H) 3.31-3.38 (m, 2 H) 6.28 (d, J=7.58 Hz, 1 H) 7.61 (t, J=5.05 Hz, 1 H) 7.85 (s, 1 H) 8.42 (d, J=7.58 Hz, 1H). 13C NMR (100 MHz, DMSO-d6) δ ppm 13.67, 19.64, 30.53, 76.99, 100.87, 135.14, 143.03, 145.13, 156.09. LRMS (ESI) m/z 269.0/271.0 [(M+H)]+, calc'd for C10H13BrN4: 269.15.

Workup

  1. dissolutionhad dissolved
  2. stirringto stir for a further 15 minutes
  3. extractionthe suspension was extracted with ethyl acetate
  4. dry with materialThe extract was dried (MgSO4) and flash
  5. customchromatographed
  6. wash(silica gel eluted with 60% (v/v) ethyl acetate/heptane)
  7. customto provide 1.2 g of off white solid, mp. 94-95° C

Sources & evidence

ORD record
ord-9b858133a87b43288e444ae4fa70f8e4
Source dataset
uspto-grants-2016_08
Patent number
US09403832B2

Reaction notes

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