Dimethylformamide → HCID 59644137, compound

HRID 2252234Notes

Reaction equation

Br[C:2]1[CH:3]=[C:4]2[C:11](=[CH:12][CH:13]=1)[C:7]1[NH:8][N:9]=[CH:10][C:6]=1[CH2:5]2.[Li]C1C=CC=CC=1.C1CCCCC1.C[CH2:28][O:29]CC.[Li]C(CC)C.C1CCCCC1.CN(C=O)C>C1COCC1>[NH:8]1[C:7]2[C:11]3[C:4]([CH2:5][C:6]=2[CH:10]=[N:9]1)=[CH:3][C:2]([CH:28]=[O:29])=[CH:13][CH:12]=3

Participants

Conditions

Temperature: -78 °C

Procedure

To a solution of 6-bromo-1,4-dihydro-indeno[1,2-c]pyrazole (0.100 g, 0.425 mmol, see U.S. Pat. No. 6,297,238 for preparation) in THF (3 mL) at −78° C. was added PhLi in cyclohexane/ether (1.8 M, 0.71 mL, 1.28 mmol) followed by s-BuLi in cyclohexane (1.3 M, 0.98 mL, 1.28 mmol) 30 minutes later. The reaction mixture was stirred at −78° C. for 60 minutes and DMF (0.33 mL, 4.25 mmol) was added. The dry ice bath was removed after 30 minutes. After an additional 30 minutes, the reaction was quenched with water. The reaction mixture was extracted with EtOAc, washed with 50% brine, dried over MgSO4, filtered, and concentrated. The concentrate was purified by flash chromatography eluted with EtOAc/hexane (7:3 to 8:2) to give 0.053 g (68%) of the desired product as brown solid. MS (DCI/NH3) m/z: 185.0 (M+H)+; 1H NMR (300 MHz, CD3OD) δ ppm 3.76 (s, 2H), 7.63 (s, 1H), 7.62-7.97 (m, 2H), 8.04 (s, 1H), 10.00 (s, 1H).

Workup

customThe dry ice bath was removed after 30 minutes
waitAfter an additional 30 minutes
customthe reaction was quenched with water
extractionThe reaction mixture was extracted with EtOAc
washwashed with 50% brine
dry with materialdried over MgSO4
filtrationfiltered
concentrationconcentrated
customThe concentrate was purified by flash chromatography
washeluted with EtOAc/hexane (7:3 to 8:2)

Sources & evidence

ORD record: ord-85120b4f4e844530bcb741b5773a76f0
Source dataset: uspto-grants-2008_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07320986B2

Reaction notes

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