Tetrahydrofuran → Diethyl (3-iodo-5-nitropyridin-2-yl)malonate

HRID 1894902Notes

Reaction equation

[H-].[Na+].[C:3]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:4][C:5]([O-:7])=[O:6].Cl[C:13]1[C:18]([I:19])=[CH:17][C:16]([N+:20]([O-:22])=[O:21])=[CH:15][N:14]=1.O1CC[CH2:25][CH2:24]1>CCOC(C)=O.O.CC(O)=O>[I:19][C:18]1[C:13]([CH:4]([C:5]([O:7][CH2:24][CH3:25])=[O:6])[C:3]([O:9][CH2:10][CH3:11])=[O:8])=[N:14][CH:15]=[C:16]([N+:20]([O-:22])=[O:21])[CH:17]=1

Participants

Conditions

Temperature: 25 °C

Procedure

To a round-bottom flask containing sodium hydride (0.56 g, 0.014 mol) suspended in tetrahydrofuran (25 mL) was added ethyl malonate (2.0 mL, 0.013 mol) dropwise, and was stirred at 25° C. for 5 minutes. To this reaction mixture was added 2-chloro-3-iodo-5-nitropyridine (2.5 g, 0.00879 mol) and was stirred at 25° C. for 4 hours. The reaction was diluted with EtOAc and water and was acidified with a few drops of AcOH. Then it was extracted with EtOAc and the organic extracts were washed with water, saturated NaCl, dried (MgSO4) and stripped in vacuo. The reaction was chromatographed on silica gel using 10% EtOAc/hexanes, followed by 20% EtOAc/hexanes to give the product (2.66 g, 74%). 1H NMR (400 MHZ, CDCl3): δ 9.35 (d, 1H), 8.89 (d, 1H), 5.27 (s, 1H), 4.31 (q, 4H), 1.30 (t, 6H); MS (ES) (M+H)=409.

Workup

stirringwas stirred at 25° C. for 4 hours
extractionThen it was extracted with EtOAc
washthe organic extracts were washed with water, saturated NaCl
dry with materialdried (MgSO4)
customThe reaction was chromatographed on silica gel using 10% EtOAc/hexanes

Sources & evidence

ORD record: ord-2bca295d6f1d4645bcff3e7b7733bf2a
Source dataset: uspto-grants-2013_08
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08513270B2

Reaction notes

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