Iodine → 1H-Pyrrolo[2,3-b]pyridine, 5-fluoro-2-iodo-1-[(4-methylphenyl)sulfonyl]-

HRID 490460Notes

Reaction equation

HRID 490460 reaction equation
[Li+].CCC[CH2-].[F:6][C:7]1[CH:8]=[C:9]2[CH:15]=[CH:14][N:13]([S:16]([C:19]3[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][CH:20]=3)(=[O:18])=[O:17])[C:10]2=[N:11][CH:12]=1.[I:26]I>CCCCCC.O1CCCC1.C(OCC)(=O)C>[F:6][C:7]1[CH:8]=[C:9]2[CH:15]=[C:14]([I:26])[N:13]([S:16]([C:19]3[CH:24]=[CH:23][C:22]([CH3:25])=[CH:21][CH:20]=3)(=[O:17])=[O:18])[C:10]2=[N:11][CH:12]=1

Participants

7

Reactant 3

HCID 807IodineHCID 61028n-Butyl lithiumHCID 497588891H-Pyrrolo[2,3-B]pyridine, 5-fluoro-1-[(4-methylphenyl)sulfonyl]-

Product 1

HCID 671475501H-Pyrrolo[2,3-b]pyridine, 5-fluoro-2-iodo-1-[(4-methylphenyl)sulfonyl]-Yield 71.7%

Reagents, catalysts & solvents 3

HCID 8028TetrahydrofuranSolvent2×HCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-75 °C

Procedure

7.54 ml of a solution of N-butyllithium at 1.6 N in hexane is added, dropwise, maintaining the temperature of the medium in the region of −75° C., to a solution, cooled to approximately −78° C., of 3.5 g of 5-fluoro-1-(toluene-4-sulfonyl)-1H-pyrrolo[2,3-b]pyridine in 100 ml of tetrahydrofuran. After agitation for approximately one hour at the same temperature, a solution of 6.12 g of bisublimated iodine in 50 ml of tetrahydrofuran is run in dropwise. After the temperature has returned to around 20° C., the reaction mixture is diluted with 600 ml of ethyl acetate, washed three times with 100 ml of a 5% aqueous sodium thiosulfate solution, dried over magnesium sulfate, treated with vegetable black, filtered, and concentrated to dryness under reduced pressure (13 kPa). The residue is taken up with 30 ml of diisopropyl ether, filter-dried, washed with three times 5 ml of diisopropyl ether, and dried under reduced pressure (13 kPa). 3.6 g of 5-fluoro-2-iodo-1-(toluene-4-sulfonyl)-1H-pyrrolo[2,3-b]pyridine are obtained in the form of a solid, the characteristics of which are as follows:

Workup

  1. customhas returned to around 20° C.
  2. washwashed three times with 100 ml of a 5% aqueous sodium thiosulfate solution
  3. dry with materialdried over magnesium sulfate
  4. additiontreated with vegetable black
  5. filtrationfiltered
  6. concentrationconcentrated to dryness under reduced pressure (13 kPa)
  7. customfilter-dried
  8. washwashed with three times 5 ml of diisopropyl ether
  9. customdried under reduced pressure (13 kPa)

Sources & evidence

ORD record
ord-064bf3a1a04d49728bf892e10baee3d8
Source dataset
uspto-grants-2009_05
Patent number
US07528147B2

Reaction notes

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