Triethylamine → (E)-Diethyl 2-(4-amino-3-methyl-2-nitrobenzylidene)succinate

HRID 2378594Notes

Reaction equation

I[C:2]1[CH:7]=[CH:6][C:5]([NH2:8])=[C:4]([CH3:9])[C:3]=1[N+:10]([O-:12])=[O:11].[C:13]([O:23][CH2:24][CH3:25])(=[O:22])[C:14]([CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])=[CH2:15].C(N(CC)CC)C>CN(C)C=O.[Cl-].C([N+](CCCC)(CCCC)CCCC)CCC.C([O-])(=O)C.[Pd+2].C([O-])(=O)C>[NH2:8][C:5]1[CH:6]=[CH:7][C:2](/[CH:15]=[C:14](\[CH2:16][C:17]([O:19][CH2:20][CH3:21])=[O:18])/[C:13]([O:23][CH2:24][CH3:25])=[O:22])=[C:3]([N+:10]([O-:12])=[O:11])[C:4]=1[CH3:9]

Participants

Conditions

Temperature: 80 °C

Procedure

To a solution of 4-iodo-2-methyl-3-nitrobenzenamine (59 mmol) in dimethylformamide (100 mL) was added diethyl itaconate (13.2 g, 71 mmol), tetrabutylammonium chloride (16.4 g, 59 mmol), triethylamine (236 mmol) and palladium acetate (675 mg, 3 mmol) under nitrogen. The reaction mixture was heated to 80° C. for 2 h. The crude reaction mixture was then filtered, diluted with ether (250 mL), washed with water (2×300 mL). The crude product was purified by flash chromatography using 20% ethyl acetate in hexane to give 8.5 g of the title compound. 1H NMR (500 MHz, CDCl3): in δ 7.58 (s, 1H), 7.10 (d, J=8.5 Hz, 1H), 6.73 (d, J=8.5 Hz, 1H), 4.24-4.15 (m, 4H), 3.40 (s, 2H), 2.06 (s, 3H), 1.30-1.23 (m, 6H).

Workup

customThe crude reaction mixture
filtrationwas then filtered
additiondiluted with ether (250 mL)
washwashed with water (2×300 mL)
customThe crude product was purified by flash chromatography

Sources & evidence

ORD record: ord-caa7df884e644e26a905f5ceac4a08d7
Source dataset: uspto-grants-2008_12
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07470679B2

Reaction notes

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