2-Bromopropane → 7-Nitro-2-Isopropyl-4-bromo-2H-phthalazin-1-one

HRID 1783708Notes

Reaction equation

HRID 1783708 reaction equation
[N+]([C:4]1[CH:5]=C2C(=C[CH:13]=1)C(=O)NN=C2Br)([O-])=O.[N+:16]([C:19]1[CH:28]=[C:27]2[C:22]([C:23]([Br:30])=[N:24][NH:25][C:26]2=[O:29])=[CH:21][CH:20]=1)([O-:18])=[O:17].[H-].[Na+].BrC(C)C>CN(C=O)C>[N+:16]([C:19]1[CH:28]=[C:27]2[C:22]([C:23]([Br:30])=[N:24][N:25]([CH:4]([CH3:5])[CH3:13])[C:26]2=[O:29])=[CH:21][CH:20]=1)([O-:18])=[O:17]

Participants

6

Reactant 4

HCID 63582-BromopropaneHCID 24758Sodium hydride2×HCID 211065897-Nitro-4-bromo-2H-phthalazin-1-oneHCID 689788776-nitro-4-bromo-2H-phthalazin-1-one

Product 1

HCID 211065877-Nitro-2-Isopropyl-4-bromo-2H-phthalazin-1-oneYield 40%

Reagents, catalysts & solvents 1

HCID 6228DimethylformamideSolvent3×

Procedure

A mixture of 6-nitro-4-bromo-2H-phthalazin-1-one and 7-nitro-4-bromo-2H-phthalazin-1-one (84 g, 0.31 mol) was dissolved in DMF (400 ml). To this was added NaH (60%, 7.5 g, 0.31 mol) as a DMF suspension (200 ml). The mixture was stirred at RT for 30 min then 2-bromo-propane (7.7 g, 62 mmol) was added in one portion as a solution in DMF (250 ml). The reaction mixture was stirred for 24 hours whereupon LC-MS showed 40% starting material remaining. To this was added NaH (3.75 g, 0.15 mol) and the reaction stirred for a further 24 hours. The DMF was removed under vacuum and the resulting crude material purified by successive column chromatography (elution: 92% heptane, 8% EtOAc) to give the title compound (38.8 g, 40% yield) as a light yellow solid. δH (400 MHz, DMSO), 8.88 (1H, d), 8.87 (1H, dd), 8.16 (1 H, d), 5.19 (1H, m), 1.13 (6H, d).

Workup

  1. stirringThe reaction mixture was stirred for 24 hours whereupon LC-MS
  2. stirringthe reaction stirred for a further 24 hours
  3. customThe DMF was removed under vacuum
  4. customthe resulting crude material purified by successive column chromatography (elution: 92% heptane, 8% EtOAc)

Sources & evidence

ORD record
ord-08aa941a4c3d4dc4bcd7a1998e8308f1
Source dataset
uspto-grants-2009_03
Patent number
US07501410B2

Reaction notes

Loading…