O-(Diphenylphosphinyl)hydroxylamine → 2-amino-4-isopropylphthalazin-1(2H)-one

HRID 469515Notes

Reaction equation

HRID 469515 reaction equation
[CH:1]([C:4]1[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:7](=[O:14])[NH:6][N:5]=1)([CH3:3])[CH3:2].CC([O-])(C)C.[K+].C1(P(O[NH2:36])(C2C=CC=CC=2)=O)C=CC=CC=1>C1COCC1.CCOC(C)=O>[NH2:36][N:6]1[N:5]=[C:4]([CH:1]([CH3:3])[CH3:2])[C:13]2[C:8](=[CH:9][CH:10]=[CH:11][CH:12]=2)[C:7]1=[O:14]

Participants

6

Reactant 3

HCID 10955453O-(Diphenylphosphinyl)hydroxylamineHCID 109762454-isopropylphthalazin-1(2H)-oneHCID 23665647Potassium tert-butoxide

Product 1

HCID 671616462-amino-4-isopropylphthalazin-1(2H)-oneYield 109.2%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of the product of Example 1A (30.0 mg, 0.159 mmol) and KOtBu (1 M in THF, 0.32 mL, 0.32 mmol) in THF (1 mL) was stirred for 45 minutes, and O-(diphenylphosphoryl)hydroxylamine (57.6 mg, 0.247 mmol) [Klotzer, W.; Stadlwieser, J.; Raneburger, J. Organic Syntheses 1986, 64, 96-103] was added and stirred overnight. The mixture was diluted with EtOAc, washed with saturated aqueous NaHCO3 and brine, dried (Na2SO4), and concentrated to give 35.3 mg of crude product as a tan solid, which was used without purification. 1H NMR (300 MHz, DMSO-d6) δ 8.31 (dd, 1H), 8.09 (d, 1H), 7.92 (ddd, 1H), 7.84 (ddd, 1H), 6.31 (s, 2H), 3.63 (quin, 1H), 1.30 (d, 6H); LC/MS (APCI) M/Z 204.1 (M+H)+.

Workup

  1. stirringstirred overnight
  2. washwashed with saturated aqueous NaHCO3 and brine
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated

Sources & evidence

ORD record
ord-af0a9fd2f5184c0b9c168fe1223a7639
Source dataset
uspto-grants-2014_01
Patent number
US08629143B2

Reaction notes

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