Acetic Acid → HCID 86696412, compound

HRID 870710Notes

Reaction equation

HRID 870710 reaction equation
C(O)(=O)C.[Br:5][C:6]1[N:10]2[N:11]=[C:12]([NH:15][CH2:16][CH2:17][NH2:18])[CH:13]=[CH:14][C:9]2=[N:8][CH:7]=1.[CH3:19][C:20]([CH3:22])=O.C([BH3-])#N.[Na+].N#N>>[Br:5][C:6]1[N:10]2[N:11]=[C:12]([NH:15][CH2:16][CH2:17][NH:18][CH:20]([CH3:22])[CH3:19])[CH:13]=[CH:14][C:9]2=[N:8][CH:7]=1

Participants

6

Reactant 5

HCID 176Acetic AcidHCID 180AcetoneHCID 947NitrogenHCID 5003444Sodium cyanoborohydrideHCID 86696413HCID 86696413, compound

Product 1

HCID 86696412HCID 86696412, compound

Procedure

Glacial acetic acid [64-19-7] (1.6 mL, 28.0 mmol) was added to a stirred suspension of N1-(3-bromoimidazo[1,2-b]pyridazin-6-yl)ethane-1,2-diamine (7.0 g, 27.2 mmol), acetone [67-64-1] (2.4 mL, 32.6 mmol), sodium cyanoborohydride [25895-80-7] (1.8 g, 27.2 mmol) and powdered, activated 4 Angstrom molecular sieve (4 g). The flask was N2 blanketed, closed with a septum, and the mixture allowed to stir at ambient temperature for 3d, then filtered. The filtrate was evaporated, and the residue partitioned between 10% (w/v) aqueous NaHCO3 and ethyl acetate. The extract was dried (CaSO4), and evaporated to afford a clear orange oil. This oil was triturated in heptane to precipitate N1-(3-bromoimidazo[1,2-b]pyridazin-6-yl)-N2-isopropylethane-1,2-diamine as 2.3 g of yellow powder, mp. 87-88° C. 1H NMR (400 MHz, DMSO-d6) δ ppm 0.99 (d, J=6.32 Hz, 5H) 1.60 (br. s., 1H) 2.71-2.81 (m, 3H) 3.34 (q, J=6.32 Hz, 2H) 6.73 (d, J=9.85 Hz, 1H) 7.07 (t, J=5.31 Hz, 1H) 7.47 (s, 1H) 7.68 (d, J=9.60 Hz, 1H). 13C NMR (100 MHz, DMSO-d6) δ ppm 22.92, 41.48, 45.29, 47.81, 98.98, 112.99, 125.26, 130.24, 136.53, 154.24. LRMS (ESI) m/z 297.9/299.9 [(M+H)]+, calc'd for C11H16BrN5. 289.19.

Workup

  1. customclosed with a septum
  2. filtrationfiltered
  3. customThe filtrate was evaporated
  4. customthe residue partitioned between 10% (w/v) aqueous NaHCO3 and ethyl acetate
  5. dry with materialThe extract was dried (CaSO4)
  6. customevaporated
  7. customto afford a clear orange oil
  8. customThis oil was triturated in heptane
  9. customto precipitate N1-(3-bromoimidazo[1,2-b]pyridazin-6-yl)-N2-isopropylethane-1,2-diamine as 2.3 g of yellow powder, mp. 87-88° C

Sources & evidence

ORD record
ord-68a1e40902314c4492a426a196b45a3b
Source dataset
uspto-grants-2015_03
Patent number
US08969565B2

Reaction notes

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