Tetrabutylammonium Fluoride → 2-tert-butyl-5-chloro-1H-pyrrolo[2,3-c]pyridine

HRID 513070Notes

Reaction equation

HRID 513070 reaction equation
C(OC(=O)[NH:7][C:8]1[CH:9]=[N:10][C:11]([Cl:20])=[CH:12][C:13]=1[C:14]#[C:15][C:16]([CH3:19])([CH3:18])[CH3:17])(C)(C)C.CCCC[N+](CCCC)(CCCC)CCCC.[F-]>C1COCC1>[C:16]([C:15]1[NH:7][C:8]2=[CH:9][N:10]=[C:11]([Cl:20])[CH:12]=[C:13]2[CH:14]=1)([CH3:19])([CH3:18])[CH3:17]

Participants

4

Reactant 2

HCID 2724141Tetrabutylammonium FluorideHCID 57908146[6-Chloro-4-(3,3-dimethyl-but-1-ynyl)-pyridin-3-yl]-carbamic acid tert-butyl ester

Product 1

HCID 579081512-tert-butyl-5-chloro-1H-pyrrolo[2,3-c]pyridineYield 87%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of [6-chloro-4-(3,3-dimethyl-but-1-ynyl)-pyridin-3-yl]-carbamic acid tert-butyl ester (15.8 g, 51 mmol) and TBAF (26.6 g, 0.1 mol) in THF (200 mL) was heated at reflux for 24 hours. After cooling, the mixture was poured into ice water and extracted with CH2Cl2 (300 mL×3). The combined organic layers were dried over anhydrous Na2SO4 and evaporated under reduced pressure to obtain a residue, which was purified by column chromatography (petroleum ether/ethyl acetate=10/1) to give 2-tert-butyl-5-chloro-1H-pyrrolo[2,3-c]pyridine (9.2 g, 87%). 1H NMR (300 MHz, CDCl3) δ 9.15 (br s, 1H), 8.43 (s, 1H), 7.44 (s, 1H), 6.25 (dd, J=0.6, 2.1 Hz, 1H), 1.42 (s, 9H).

Workup

  1. temperaturewas heated
  2. temperatureat reflux for 24 hours
  3. temperatureAfter cooling
  4. extractionextracted with CH2Cl2 (300 mL×3)
  5. dry with materialThe combined organic layers were dried over anhydrous Na2SO4
  6. customevaporated under reduced pressure
  7. customto obtain a residue, which
  8. customwas purified by column chromatography (petroleum ether/ethyl acetate=10/1)

Sources & evidence

ORD record
ord-8404b6554d0544659d27518bb009579a
Source dataset
uspto-grants-2015_08
Patent number
US09102672B2

Reaction notes

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