Nitromethane → HCID 44223285, compound

HRID 2196661Notes

Reaction equation

HRID 2196661 reaction equation
[Cl-].[Cl-].[Cl-].[Al+3].[F:5][C:6]1[C:23]([NH:24][S:25]([CH2:28][CH2:29][CH3:30])(=[O:27])=[O:26])=[CH:22][CH:21]=[C:20]([F:31])[C:7]=1[C:8]([NH:10][C:11]1[CH:12]=[C:13]2[CH:19]=[CH:18][NH:17][C:14]2=[N:15][CH:16]=1)=[O:9].[Cl:32][C:33]1[CH:34]=[C:35]([CH:39]=[CH:40][C:41]=1[Cl:42])[C:36](Cl)=[O:37].C[N+]([O-])=O>C(Cl)Cl>[Cl:32][C:33]1[CH:34]=[C:35]([CH:39]=[CH:40][C:41]=1[Cl:42])[C:36]([C:19]1[C:13]2[C:14](=[N:15][CH:16]=[C:11]([NH:10][C:8](=[O:9])[C:7]3[C:20]([F:31])=[CH:21][CH:22]=[C:23]([NH:24][S:25]([CH2:28][CH2:29][CH3:30])(=[O:27])=[O:26])[C:6]=3[F:5])[CH:12]=2)[NH:17][CH:18]=1)=[O:37]

Participants

6

Reactant 4

HCID 6375NitromethaneHCID 76403Benzoyl chloride, 3,4-dichloro-HCID 6451240Aluminum(III) ChlorideHCID 441994082,6-difluoro-3-(propylsulfonamido)-N-(1H-pyrrolo[2,3-b]pyridin-5-yl)benzamide

Product 1

HCID 44223285HCID 44223285, compoundYield 22%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent

Conditions

Temperature
0 °C

Procedure

A slurry of aluminum trichloride (0.078 g, 0.59 mmol) was added to a slurry of 2,6-difluoro-3-(propylsulfonamido)-N-(1H-pyrrolo[2,3-b]pyridin-5-yl)benzamide (0.029 g, 0.074 mmol) in DCM (1.2 mL) at 0° C., and the reaction mixture was allowed to stir at 0° C. for 40 minutes. 3,4-Dichlorobenzoyl chloride (0.023 g, 0.11 mmol) was added, and the mixture was allowed to slowly warm to room temperature overnight. CH3NO2 (300 μL) was added, and the reaction mixture was sonicated for 2 minutes. The reaction mixture was then stirred at room temperature overnight. The reaction mixture was quenched with ice and then partitioned between aqueous sodium bicarbonate and EtOAc. The organic layers were dried over Na2SO4 and concentrated under reduced pressure. The residual solids were triturated with 5% MeOH/EtOAc to provide N-(3-(3,4-dichlorobenzoyl)-1H-pyrrolo[2,3-b]pyridin-5-yl)-2,6-difluoro-3-(propylsulfonamido)benzamide (9 mg, 22%). 1H NMR (400 MHz, CD3OD) δ 8.98-8.99 (m, 1H), 8.66-8.68 (m, 1H), 8.09 (s, 1H), 7.63-7.79 (m, 3H), 7.13-7.17 (m, 1H), 3.11-3.15 (m, 2H), 1.85-1.91 (m, 2H), 1.05-1.09 (m, 3H); m/z (APCI-pos) M+1=567.0.

Workup

  1. temperatureto slowly warm to room temperature overnight
  2. customthe reaction mixture was sonicated for 2 minutes
  3. stirringThe reaction mixture was then stirred at room temperature overnight
  4. customThe reaction mixture was quenched with ice
  5. custompartitioned between aqueous sodium bicarbonate and EtOAc
  6. dry with materialThe organic layers were dried over Na2SO4
  7. concentrationconcentrated under reduced pressure
  8. customThe residual solids were triturated with 5% MeOH/EtOAc

Sources & evidence

ORD record
ord-2c1e2e085587468783a84f48647f3399
Source dataset
uspto-grants-2012_12
Patent number
US08338452B2

Reaction notes

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