Hydrochloric Acid → HCID 58382001, compound

HRID 1627993Notes

Reaction equation

HRID 1627993 reaction equation
[Cl:1][C:2]1[CH:7]=[CH:6][N:5]=[C:4]2[N:8]([Si:13]([CH:20]([CH3:22])[CH3:21])([CH:17]([CH3:19])[CH3:18])[CH:14]([CH3:16])[CH3:15])[CH:9]=[C:10]([CH2:11][CH3:12])[C:3]=12.[Li]C(CC)C.CN([CH:31]=[O:32])C.Cl.C([O-])(O)=O.[Na+]>C1COCC1.CCOC(C)=O>[Cl:1][C:2]1[C:7]([CH:31]=[O:32])=[CH:6][N:5]=[C:4]2[N:8]([Si:13]([CH:14]([CH3:15])[CH3:16])([CH:20]([CH3:21])[CH3:22])[CH:17]([CH3:19])[CH3:18])[CH:9]=[C:10]([CH2:11][CH3:12])[C:3]=12

Participants

8

Reactant 5

HCID 313Hydrochloric AcidHCID 6228DimethylformamideHCID 516892Sodium BicarbonateHCID 58382052HCID 58382052, compoundHCID 178418400CID 53628100

Product 1

HCID 58382001HCID 58382001, compoundYield 91.1%

Reagents, catalysts & solvents 2

HCID 8028TetrahydrofuranSolventHCID 8857Ethyl AcetateSolvent

Conditions

Temperature
-70 °C

Procedure

4-Chloro-3-ethyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine (1.5 g, 4.45 mmol) in THF (25 mL) was cooled to about −70° C. then the sec-BuLi (1.4 M in cyclohexane, 6.36 mL, 8.90 mmol) was added over about 10 min. The mixture was stirred for about 1.25 h at about −70° C. then DMF (1.00 mL, 13.4 mmol) was added over about 5 min. The mixture was stirred for about 30 min then HCl (4.0 M in 1,4-dioxane, 1.11 mL, 4.45 mmol) was added. The mixture was allowed to warm to rt then saturated aqueous NaHCO3 (50 mL) and EtOAc (50 mL) were added. The layers were separated then the aqueous layer was extracted with EtOAc (25 mL) then the combined organics were extracted with saturated aqueous NaCl (25 mL), dried over anhydrous MgSO4, filtered and concentrated under reduced pressure. The material was purified on a 80 g silica gel column with 9:1 heptane/EtOAc as an eluent to give 4-chloro-3-ethyl-1-(triisopropylsilyl)-1H-pyrrolo[2,3-b]pyridine-5-carbaldehyde (1.48 g, 91%): LC/MS (Table 2, Method g) Rt=2.44 min; MS m/z 365 (M+H)+.

Workup

  1. stirringThe mixture was stirred for about 30 min
  2. temperatureto warm to rt
  3. customThe layers were separated
  4. extractionthe aqueous layer was extracted with EtOAc (25 mL)
  5. extractionthe combined organics were extracted with saturated aqueous NaCl (25 mL)
  6. dry with materialdried over anhydrous MgSO4
  7. filtrationfiltered
  8. concentrationconcentrated under reduced pressure
  9. customThe material was purified on a 80 g silica gel column with 9:1 heptane/EtOAc as an eluent

Sources & evidence

ORD record
ord-247498361eec4ab68ab7541c9d9ddcef
Source dataset
uspto-grants-2014_07
Patent number
US08785639B2

Reaction notes

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