Thiophenol → 5-(Phenylsulfanyl)-1H-pyrrolo[2,3-b]pyridine

HRID 1991093Notes

Reaction equation

HRID 1991093 reaction equation
Br[C:2]1[CH:3]=[C:4]2[C:8](=[N:9][CH:10]=1)[NH:7][CH:6]=[CH:5]2.[C:11]1([SH:17])[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1.CC(C)([O-])C.[Na+]>CCO.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[C:11]1([S:17][C:2]2[CH:3]=[C:4]3[CH:5]=[CH:6][NH:7][C:8]3=[N:9][CH:10]=2)[CH:16]=[CH:15][CH:14]=[CH:13][CH:12]=1

Participants

6

Reactant 3

HCID 7969Thiophenol2×HCID 103079325-bromo-1H-pyrrolo[2,3-b]pyridineHCID 23676156Sodium t-butoxide2×

Product 1

HCID 591287095-(Phenylsulfanyl)-1H-pyrrolo[2,3-b]pyridineYield 25%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalyst2×HCID 702EthanolSolvent

Procedure

A mixture of 5-bromo-7-azaindole (1)(0.5 g, 2.54 mmol; preparation disclosed in WO2004/078757), benzenethiol (274 μL, 2.66 mmol), sodium t-butoxide (488 mg, 5.07 mmol) and Pd(PPh3)4 (235 mg, 0.20 mmol) in EtOH (25 mL) was heated at reflux for 19 h. More benzenethiol (274 μL, 2.66 mmol), sodium t-butoxide (488 mg, 5.07 mmol) and Pd(PPh3)4 (235 mg, 0.20 mmol) were added and reflux continued for a further 24 h. The reaction mixture was filtered, concentrated, and the residue was extracted with CH2Cl2:hexane=1:1 (v/v). The extract was concentrated and purified by preparative LCMS (column LUNA 10 μ C18(2) 00G-4253-V0 250×50 mm) using water—acetonitrile (0.1% AcOH) as eluent (in gradient; flow 80 mL/min) to afford 2 as a white solid (142 mg, 25%); 1H NMR (400 MHz, CDCl3) δ 6.53 (dd, J=3.5, 2.0 Hz, 1H), 7.10-7.30 (m, 5H), 7.41 (dd, J=5.9, 2.5 Hz, 1H), 8.16 (dd, J=2.0, 0.6 Hz, 1H), 8.48 (d, J=2.0 Hz, 1H), 10.00-10.20 (bs, NH).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 19 h
  3. temperaturereflux
  4. filtrationThe reaction mixture was filtered
  5. concentrationconcentrated
  6. extractionthe residue was extracted with CH2Cl2
  7. concentrationThe extract was concentrated
  8. custompurified by preparative LCMS (column LUNA 10 μ C18(2) 00G-4253-V0 250×50 mm)

Sources & evidence

ORD record
ord-c2b3b31047114fa695c088637042c9b9
Source dataset
uspto-grants-2010_01
Patent number
US07645769B2

Reaction notes

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