Pyridine → Ethyl 3-(2-amino-3,5-bis(trifluoromethyl)phenylamino)-3-oxopropanoate

HRID 641591Notes

Reaction equation

[F:1][C:2]([F:16])([F:15])[C:3]1[C:4]([NH2:14])=[C:5]([NH2:13])[CH:6]=[C:7]([C:9]([F:12])([F:11])[F:10])[CH:8]=1.N1C=CC=CC=1.Cl[C:24](=[O:31])[CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27]>C(Cl)Cl>[NH2:14][C:4]1[C:3]([C:2]([F:15])([F:16])[F:1])=[CH:8][C:7]([C:9]([F:12])([F:11])[F:10])=[CH:6][C:5]=1[NH:13][C:24](=[O:31])[CH2:25][C:26]([O:28][CH2:29][CH3:30])=[O:27]

Participants

Conditions

Temperature: 0 °C

Procedure

An ice-cold solution of 3,5-bis(trifluoromethyl)-1,2-phenylenediamine (880 mg, 3.6 mmol) and pyridine (104 mg, 1.3 mmol) in methylene chloride (20 mL) was treated with ethyl 3-chloro-3-oxopropionate (181 mg, 1.2 mmol). The mixture was stirred at 0° C. for 3 h, then allowed to warm to room temperature and stirred for four days. The solution was diluted to 100 mL with methylene chloride, washed with saturated NH4Cl (3×20 mL), water (20 mL), and brine (20 mL), then dried over sodium sulfate and concentrated in-vacuo. The residue was purified over silica gel, eluting with 20%-30%-40% EtOAc/heptane, to yield 330 mg of a white solid as product. 1H NMR (500 MHz, DMSO) δ ppm 1.22 (t, J=7.15 Hz, 3 H) 3.52 (s, 2 H) 4.14 (q, J=7.15 Hz, 2 H) 6.16 (s, 2 H) 7.54 (s, 1 H) 7.71 (m, 1 H) 9.60 (s, 1 H).

Workup

temperatureto warm to room temperature
stirringstirred for four days
washwashed with saturated NH4Cl (3×20 mL), water (20 mL), and brine (20 mL)
dry with materialdried over sodium sulfate
concentrationconcentrated in-vacuo
customThe residue was purified over silica gel
washeluting with 20%-30%-40% EtOAc/heptane

Sources & evidence

ORD record: ord-a660e98db1cd49829fc7d875de3b0d9a
Source dataset: uspto-grants-2010_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US07696205B2

Reaction notes

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