Ammonium Chloride → HCID 178507999, compound

HRID 1257681Notes

Reaction equation

HRID 1257681 reaction equation
[C:1]1([S:7]([N:10]2[C:14]3=[N:15][CH:16]=[C:17]([N+:27]([O-])=O)[C:18]([NH:19][C@H:20]4[CH2:25][CH2:24][C@H:23]([OH:26])[CH2:22][CH2:21]4)=[C:13]3[CH:12]=[CH:11]2)(=[O:9])=[O:8])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.[Cl-].[NH4+]>C(O)C.O.[Fe]>[NH2:27][C:17]1[C:18]([NH:19][C@H:20]2[CH2:21][CH2:22][C@H:23]([OH:26])[CH2:24][CH2:25]2)=[C:13]2[CH:12]=[CH:11][N:10]([S:7]([C:1]3[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=3)(=[O:9])=[O:8])[C:14]2=[N:15][CH:16]=1

Participants

6

Reactant 2

HCID 25517Ammonium ChlorideHCID 178526773HCID 178526773, compound

Product 1

HCID 178507999HCID 178507999, compoundYield 33.2%

Reagents, catalysts & solvents 3

HCID 23925IronCatalystHCID 702EthanolSolventHCID 962WaterSolvent

Conditions

Temperature
50 °C

Procedure

Crude trans 4-(1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridin-4-ylamino)-cyclohexanol (65.0 g, approx. 148 mmol) was suspended in ethanol (1000 mL, IMS grade) and water (300 mL). Ammonium chloride (47.5 g, 888 mmol) was added, and the mixture was stirred at 50° C. Powdered iron (33.0 g, 592 mmol) was added slowly and the resulting mixture was stirred at reflux for 2 h, then cooled to room temperature. The mixture was filtered and the filter cake washed with further ethanol, then the combined filtrate was concentrated under vacuum. The residue was suspended in water and extracted with dichloromethane (×2) and the combined organic extracts were dried (Na2SO4) and concentrated under vacuum. The residue was triturated with methanol then water to give 19.0 g (33%) of trans 4-(5-amino-1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridin-4-ylamino)-cyclohexanol. The methanol mother liquor was concentrated and the resulting residue triturated with acetonitrile to give a further 11.0 g (19%) of trans 4-(5-amino-1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridin-4-ylamino)-cyclohexanol. NMR (400 MHz, DMSO) δ: 8.04 (m, 2H), 7.68 (m, 2H), 7.59 (m, 3H), 6.76 (d, 1H), 5.68 (br s, 1H), 3.71 (br s, 1H), 1.91 (m, 2H), 1.84 (m, 2H), 1.34 (m, 4H), further signals partially obscured residual water peak.

Workup

  1. stirringthe resulting mixture was stirred
  2. temperatureat reflux for 2 h
  3. temperaturecooled to room temperature
  4. filtrationThe mixture was filtered
  5. washthe filter cake washed with further ethanol
  6. concentrationthe combined filtrate was concentrated under vacuum
  7. extractionextracted with dichloromethane (×2)
  8. dry with materialthe combined organic extracts were dried (Na2SO4)
  9. concentrationconcentrated under vacuum
  10. customThe residue was triturated with methanol

Sources & evidence

ORD record
ord-ab3c26dddbea46f2a2ab7577bdf035b9
Source dataset
uspto-grants-2013_06
Patent number
US08461328B2

Reaction notes

Loading…