Diethyl (ethoxymethylene)malonate → Diethyl 2-((2-iodophenylamino)methylene)malonate

HRID 719530

Reaction equation

[I:1][C:2]1[CH:8]=[CH:7][CH:6]=[CH:5][C:3]=1[NH2:4].[CH2:9]([O:11][C:12](=[O:23])[C:13](=[CH:19]OCC)[C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH3:10]>ClCCl>[CH2:9]([O:11][C:12](=[O:23])[C:13](=[CH:19][NH:4][C:3]1[CH:5]=[CH:6][CH:7]=[CH:8][C:2]=1[I:1])[C:14]([O:16][CH2:17][CH3:18])=[O:15])[CH3:10]

Participants

Conditions

Temperature: 110 °C

Procedure

2-Iodoaniline (50 g, 228.3 mmol) and 2-ethoxymethylene-malonic acid diethyl ester (50 mL, 251.1 mmol) were mixed and the solution was stirred at 110° C. for 3 h. The crude was dissolved in dichloromethane and it was purified by silica plug. The product was eluted with ethyl acetate/hexanes (10–50%) and the solvent removed under reduced pressure to afford 2-[(2-iodo-phenylamino)-methylene]-malonic acid diethyl ester as an off-white powder (81.4 g, 91.6%). 1H NMR (CDCl3, 400 MHz) δ 1.49 (t, 3H), 1.54 (t, 3H), 4.40 (q, 2H), 4.52 (q, 2H), 7.01–7.05 (m, 1H), 7.36–7.39 (m, 1H), 7.52–7.56 (m, 1H), 8.59 (d, 1H). Exact mass calculated for C14H16INO4 389.01, found 390.1 (MH+).

Workup

customit was purified by silica plug
washThe product was eluted with ethyl acetate/hexanes (10–50%)
customthe solvent removed under reduced pressure

Sources & evidence

ORD record: ord-e19b4793b4364ee1aa15ab49844c4ded
Source dataset: uspto-grants-2006_11
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07132426B2

Linked notes

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