Hydroxylamine → HCID 67966837, compound

HRID 527597Notes

Reaction equation

HRID 527597 reaction equation
[CH3:1][C:2]12[CH2:12][CH:11]1[C:10]1[C:9]([O:13][C:14]3[CH:19]=[CH:18][C:17]([N+:20]([O-])=O)=[CH:16][N:15]=3)=[CH:8][CH:7]=[CH:6][C:5]=1[O:4][CH2:3]2.O.[Cl-].[NH4+].ON>O1CCCC1.[Fe]>[CH3:1][C:2]12[CH2:12][CH:11]1[C:10]1[C:9]([O:13][C:14]3[N:15]=[CH:16][C:17]([NH2:20])=[CH:18][CH:19]=3)=[CH:8][CH:7]=[CH:6][C:5]=1[O:4][CH2:3]2

Participants

7

Reactant 4

HCID 787HydroxylamineHCID 962WaterHCID 25517Ammonium Chloride2×HCID 67966839HCID 67966839, compound2×

Product 1

HCID 67966837HCID 67966837, compoundYield 66.7%

Reagents, catalysts & solvents 2

HCID 23925IronCatalyst2×HCID 8028TetrahydrofuranSolvent

Procedure

To a solution of 2-[(1a-methyl-1,1a,2,7b-tetrahydrocyclopropa[c]chromen-7-yl)oxy]-5-nitropyridine (Intermediate 126, 250 mg) in tetrahydrofuran (6 ml)/water (3 ml) were added iron (234 mg, 4.19 mmol) and ammonium chloride (224 mg, 4.19 mmol). The reaction mixture was stirred at room temperature overnight at which time UPLC showed partial formation of the target compound with some hydroxyl-amine intermediate, therefore additional 3 equivalents of ammonium chloride and iron were added and the reaction was left stirring for an other 5 hours. The iron was then filtered off over a pad of celite and the solution was diluted with an aqueous saturated solution of NaHCO3 (100 ml) and ethyl acetate (200 ml). Two phases were separated and the aqueous layer was extracted with ethyl acetate. Organic layers were combined, dried over sodium sulphate, filtered and evaporated. The residue was purified by silica gel chromatography (Companion system, with a gradient from cyclohexane/ethyl acetate 8:2 to cyclohexane/ethyl acetate 1:1) to give the title compound as a light brown solid (150 mg).

Workup

  1. waitthe reaction was left
  2. stirringstirring for an other 5 hours
  3. filtrationThe iron was then filtered off over a pad of celite
  4. additionthe solution was diluted with an aqueous saturated solution of NaHCO3 (100 ml) and ethyl acetate (200 ml)
  5. customTwo phases were separated
  6. extractionthe aqueous layer was extracted with ethyl acetate
  7. dry with materialdried over sodium sulphate
  8. filtrationfiltered
  9. customevaporated
  10. customThe residue was purified by silica gel chromatography (Companion system

Sources & evidence

ORD record
ord-f53512ea13ae471faa8ae2ecb8d4b366
Source dataset
uspto-grants-2016_05
Patent number
US09346790B2

Reaction notes

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