Dimethylformamide → HCID 67102595, compound

HRID 2079846Notes

Reaction equation

HRID 2079846 reaction equation
[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([NH:11][C:12]2[CH:13]=[C:14]3[C:18](=[CH:19][C:20]=2[Br:21])[NH:17][CH:16]=[CH:15]3)(=[O:10])=[O:9])=[CH:4][CH:3]=1.[CH3:22][Si]([N-][Si](C)(C)C)(C)C.[Na+].[CH3:32]I.C(=O)(O)[O-].[Na+].[CH3:39][N:40]([CH:42]=O)[CH3:41]>CO.ClCCl>[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]([C:12]2[CH:13]=[C:14]3[C:39](=[CH:19][C:20]=2[Br:21])[N:40]([CH3:41])[CH:42]=[CH:15]3)[CH3:32])(=[O:10])=[O:9])=[CH:4][CH:3]=1.[NH2:1][C:2]1[CH:7]=[CH:6][C:5]([S:8]([N:11]([C:12]2[CH:13]=[C:14]3[C:18](=[CH:19][C:20]=2[Br:21])[NH:17][CH:16]=[CH:15]3)[CH3:22])(=[O:10])=[O:9])=[CH:4][CH:3]=1

Participants

8

Reactant 5

HCID 6228DimethylformamideHCID 6328Methyl iodideHCID 516892Sodium BicarbonateHCID 2724254Sodium bis(trimethylsilyl)amideHCID 57829222HCID 57829222, compound

Product 2

HCID 67102595HCID 67102595, compoundHCID 67102640HCID 67102640, compound

Reagents, catalysts & solvents 1

HCID 21226129Dichloromethane methanolSolvent2×

Procedure

To a DMF (6 mL) solution of 4-Amino-N-(6-bromo-1H-indol-5-yl)-benzenesulfonamide (750 mg, 2.05 mmol) was added NaHMDS (2.77 mL, 1M in THF) and stirred for 20 min at RT. Methyl iodide (0.153 mL, 2.46 mmol) was added in a single portion. After stirring for 2.5 hr at RT TLC analysis (10% MeOH/dichloromethane) shows two new less-polar products. The reaction mixture was poured into 75 mL of saturated sodium bicarbonate solution and extracted with EtOAc (2×50 mL). The organic layers were combined, washed with brine, dried over MgSO4, and concentrated to give a yellow oil. Chromatography (SiO2; 0%-5% MeOH/dichloromethane) gives 4-amino-N-(6-bromo-1-methyl-1H-indol-5-yl)-N-methyl-benzenesulfonamide as the less-polar product (MS=394, 396 [M+H]) and 4-amino-N-(6-bromo-1H-indol-5-yl)-N-methyl-benzenesulfonamide (only 85% pure) as the more-polar product (MS=380, 382 [M+H]). The corresponding boronates were separately prepared following general procedures as described in these Examples: 4-Amino-N-methyl-N-[1-methyl-6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-indol-5-yl]-benzenesulfonamide: (MS=442 [M+H]); 4-Amino-N-methyl-N-[6-(4,4,5,5-tetramethyl-[1,3,2]dioxaborolan-2-yl)-1H-indol-5-yl]-benzenesulfonamide, following chromatography (SiO2; 1%-5% MeOH/dichloromethane): (MS=428 [M+H]).

Workup

  1. extractionextracted with EtOAc (2×50 mL)
  2. washwashed with brine
  3. dry with materialdried over MgSO4
  4. concentrationconcentrated
  5. customto give a yellow oil

Sources & evidence

ORD record
ord-e2bbde9650754fa59a67e9e3d15547d5
Source dataset
uspto-grants-2011_04
Patent number
US07932254B2

Reaction notes

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