Ethoxalyl chloride → HCID 70818356, compound

HRID 591083Notes

Reaction equation

C([Mg]Cl)(C)C.Br[C:7]1[C:8]([C:28]([F:31])([F:30])[F:29])=[N:9][N:10]([CH:22]2[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]2)[C:11]=1[C:12]1[CH:13]=[CH:14][C:15]2[O:20][CH2:19][CH2:18][CH2:17][C:16]=2[CH:21]=1.Cl[C:33](=[O:39])[C:34]([O:36][CH2:37][CH3:38])=[O:35]>O1CCCC1.O>[CH:22]1([N:10]2[C:11]([C:12]3[CH:13]=[CH:14][C:15]4[O:20][CH2:19][CH2:18][CH2:17][C:16]=4[CH:21]=3)=[C:7]([C:33](=[O:39])[C:34]([O:36][CH2:37][CH3:38])=[O:35])[C:8]([C:28]([F:31])([F:30])[F:29])=[N:9]2)[CH2:27][CH2:26][CH2:25][CH2:24][CH2:23]1

Participants

Conditions

Temperature: -20 °C

Procedure

Under nitrogen, isopropyl magnesium chloride 2M in tetrahydrofuran (0.47 mL, 0.94 mmol) was dropwise added to a solution of 4-bromo-1-cyclohexyl-5-(3,4-dihydro-2H-1-benzopyran-6-yl)-3-(trifluoromethyl)-1H-pyrazole (54b) (134 mg, 0.31 mmol) in anhydrous tetrahydrofuran (1.0 mL), previously cooled to −20° C. After 90 minutes stirring at the same temperature, ethyl chlorooxoacetate (70 μL, 0.62 mmol) was added dropwise. The mixture was stirred at −20° C. for 40 minutes before being poured in water (2 mL). The mixture was extracted with ethyl acetate (2×3 mL) and the organic layer was dried over sodium sulfate and concentrated in vacuo. The residue was purified by preparative TLC (cyclohexane/ethyl acetate 75/25) to provide the desired keto-ester (54c) (104 mg, 0.23 mmol, 74%).

Workup

additionwas added dropwise
extractionThe mixture was extracted with ethyl acetate (2×3 mL)
dry with materialthe organic layer was dried over sodium sulfate
concentrationconcentrated in vacuo
customThe residue was purified by preparative TLC (cyclohexane/ethyl acetate 75/25)

Sources & evidence

ORD record: ord-d822c7360ff946c7a9ab6e329cab7ceb
Source dataset: uspto-grants-2016_01
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09238026B2

Reaction notes

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