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

HRID 77730Notes

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-438677a5d2584cf6b5c2c74b2176d806
Source dataset: uspto-grants-2014_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08841318B2

Reaction notes

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