Dimethyl oxalate → HCID 21055225, compound

HRID 2215790Notes

Reaction equation

HRID 2215790 reaction equation
[CH3:1][N:2]1[C:10]2[C:5](=[CH:6][C:7]([F:12])=[CH:8][C:9]=2Br)[CH:4]=[CH:3]1.C([Li])(C)(C)C.[C:18](OC)(=[O:23])[C:19]([O:21][CH3:22])=[O:20]>C1COCC1>[CH3:22][O:21][C:19](=[O:20])[C:18]([C:9]1[CH:8]=[C:7]([F:12])[CH:6]=[C:5]2[C:10]=1[N:2]([CH3:1])[CH:3]=[CH:4]2)=[O:23]

Participants

5

Reactant 3

HCID 11120Dimethyl oxalateHCID 219500637-Bromo-5-fluoro-1-methyl-1H-indoleHCID 178418306HCID 178418306, compound

Product 1

HCID 21055225HCID 21055225, compoundYield 49.1%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of 1-methyl-5-fluoro-7-bromoindole (8.3 g, 36.4 mmol) in THF (250 mL) was cooled to −78° C. and a solution of tert-butyl lithium in pentanes (1.7 M, 47 mL, 80.1 mmol) added dropwise over 30 min. After 30 min at −78° C., the mixture was treated with dimethyl oxalate (10.75 g, 91 mmol) in one portion. After 15 min, the mixture was allowed to warm to room temperature and stirred 4 h. The reaction mixture was quenched with water, extracted with ethyl acetate and the extract washed with brine, dried (Na2SO4) and concentrated. Flash chromatography (EtOAc/hexanes) afforded the title compound (4.2 g, 49%). 1H NMR (400 MHz, CDCl3) 3.83(s, 3H), 4.01 (s, 3H), 6.56 (d, J=3.13 Hz, 1H), 7.15 (d, J=3.13 Hz, 1H), 7.35 (dd, J1=2.0 Hz, J2=9.4 Hz, 1H), 7.57 (dd, J1=2.34 Hz, J2=8.21 Hz, 1H); MS (ES, m/z): C12H10FNO3: 235.22 (M++1).

Workup

  1. waitAfter 15 min
  2. customThe reaction mixture was quenched with water
  3. extractionextracted with ethyl acetate
  4. washthe extract washed with brine
  5. dry with materialdried (Na2SO4)
  6. concentrationconcentrated

Sources & evidence

ORD record
ord-9691322cf4cf4f58993b56e73995e591
Source dataset
uspto-grants-2006_09
Patent number
US07109229B2

Reaction notes

Loading…