HCID 178472427, compound → HCID 178472426, compound

HRID 1257640Notes

Reaction equation

HRID 1257640 reaction equation
[CH2:1]([O:3][C:4]([C@H:6]1[CH2:11][CH2:10][C@H:9]([NH:12][C:13]2[C:18]([N+:19]([O-])=O)=[CH:17][N:16]=[C:15]3[N:22]([S:25]([C:28]4[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=4)(=[O:27])=[O:26])[CH:23]=[CH:24][C:14]=23)[CH2:8][CH2:7]1)=[O:5])[CH3:2]>C(O)(=O)C.[OH-].[Pd+2].[OH-]>[CH2:1]([O:3][C:4]([C@H:6]1[CH2:11][CH2:10][C@H:9]([NH:12][C:13]2[C:18]([NH2:19])=[CH:17][N:16]=[C:15]3[N:22]([S:25]([C:28]4[CH:29]=[CH:30][CH:31]=[CH:32][CH:33]=4)(=[O:27])=[O:26])[CH:23]=[CH:24][C:14]=23)[CH2:8][CH2:7]1)=[O:5])[CH3:2]

Participants

4

Reactant 1

HCID 178472427HCID 178472427, compound

Product 1

HCID 178472426HCID 178472426, compoundYield 83%

Reagents, catalysts & solvents 2

HCID 9942167Palladium hydroxideCatalystHCID 176Acetic AcidSolvent

Conditions

Temperature
50 °C

Procedure

Palladium hydroxide (20% wt on carbon, 2.5 g) was added to a solution of trans 4-(1-benzenesulfonyl-5-nitro-1H-pyrrolo[2,3-b]pyridin-4-ylamino)-cyclohexane carboxylic acid ethyl ester (assumed to be 44.4 mmol) in acetic acid (150 mL) under nitrogen. The reaction was evacuated and purged with hydrogen and the reaction warmed to 50° C. for 8 hours. The reaction vessel was recharged with hydrogen gas and stirred at room temperature for 18 hours. The mixture was then filtered through Celite® and the filtrate concentrated to dryness under vacuum. The resulting residue was partitioned between DCM and sodium hydrogen carbonate (sat. aq.), the organic layer dried with sodium sulphate and concentrated under vacuum. The residue was purified by column chromatography on silica gel (eluting: ethyl acetate) to give 16.2 g (83%) of trans 4-(5-amino-1-benzenesulfonyl-1H-pyrrolo[2,3-b]pyridin-4-ylamino)-cyclohexanecarboxylic acid ethyl ester as a purple solid. 1H NMR (400 MHz, CDCl3) δ: 8.13 (m, 2H), 7.83 (s, 1H), 7.53 (m, 1H), 7.45 (m, 3H), 6.54 (d, 1H), 4.75 (br s, 1H), 4.14 (q, 2H), 3.68 (m, 1H), 2.65 (br s, 2H), 2.32 (m, 1H), 2.20 (m, 2H), 2.09 (m, 2H), 1.63 (m, 2H), 1.33-1.20 (m, 5H).

Workup

  1. customThe reaction was evacuated
  2. custompurged with hydrogen
  3. filtrationThe mixture was then filtered through Celite®
  4. concentrationthe filtrate concentrated to dryness under vacuum
  5. customThe resulting residue was partitioned between DCM and sodium hydrogen carbonate (sat. aq.)
  6. dry with materialthe organic layer dried with sodium sulphate
  7. concentrationconcentrated under vacuum
  8. customThe residue was purified by column chromatography on silica gel (eluting: ethyl acetate)

Sources & evidence

ORD record
ord-c1c46f7e2c194779a736808c04a13f61
Source dataset
uspto-grants-2013_06
Patent number
US08461328B2

Reaction notes

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