Nitrogen → Diethyl (2,5-difluoro-4-nitrophenyl)propanedioate

HRID 2173387Notes

Reaction equation

[H-].[Na+].[CH2:3]([C:9]([O:11][CH2:12][CH3:13])=[O:10])[C:4]([O:6][CH2:7][CH3:8])=[O:5].N#N.[F:16][C:17]1[CH:22]=[C:21]([N+:23]([O-:25])=[O:24])[C:20]([F:26])=[CH:19][C:18]=1F>CN(C=O)C.O>[F:16][C:17]1[CH:22]=[C:21]([N+:23]([O-:25])=[O:24])[C:20]([F:26])=[CH:19][C:18]=1[CH:3]([C:4]([O:6][CH2:7][CH3:8])=[O:5])[C:9]([O:11][CH2:12][CH3:13])=[O:10]

Participants

Conditions

Temperature: -6 °C

Procedure

To an ice-cooled slurry of NaH (475 mg, 11.8 mmol, 60%) in dry DMF (10 mL) was added CH2(COOEt)2 dropwise under an N2 atmosphere. After 20 minutes, 1,2,4-trifluoro-5-nitrobenzene (1 g, 5.6 mmol) was added dropwise over 10 minutes and the mixture was stirred at −6° C. overnight. After the reaction was completed, the mixture was diluted with water and extracted with EtOAc. The organic layer washed with brine, dried over anhydrous Na2SO4 and concentrated. The residue was purified chromatography to give diethyl (2,5-difluoro-4-nitrophenyl)propanedioate. 1H-NMR (400 MHz, CDCl3) δ ppm 7.87˜7.84 (m, 1H), 7.54˜7.58 (m, 1H), 4.98 (s, 1H), 4.23˜4.27 (m, 4H), 1.28 (t, J=7.0 Hz, 6H).

Workup

extractionextracted with EtOAc
washThe organic layer washed with brine
dry with materialdried over anhydrous Na2SO4
concentrationconcentrated
customThe residue was purified chromatography

Sources & evidence

ORD record: ord-91b68bd4d025436dbddddc30eb4f2fd6
Source dataset: uspto-grants-2015_06
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09056859B2

Reaction notes

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