4-Bromoaniline → HCID 178471906, compound

HRID 2271513Notes

Reaction equation

HRID 2271513 reaction equation
[CH3:1][CH:2]([CH3:11])[C:3](=[O:10])[CH2:4][C:5]([O:7][CH2:8][CH3:9])=[O:6].[CH:12](OCC)(OCC)OCC.[Br:22][C:23]1[CH:29]=[CH:28][C:26]([NH2:27])=[CH:25][CH:24]=1>>[Br:22][C:23]1[CH:29]=[CH:28][C:26]([NH:27][CH:12]=[C:4]([C:3](=[O:10])[CH:2]([CH3:1])[CH3:11])[C:5]([O:7][CH2:8][CH3:9])=[O:6])=[CH:25][CH:24]=1

Participants

4

Reactant 3

HCID 78074-BromoanilineHCID 31214Ethyl orthoformate2×HCID 81583Ethyl isobutyrylacetate

Product 1

HCID 178471906HCID 178471906, compoundYield 53%

Conditions

Temperature
150 °C

Procedure

A mixture of ethyl 4-methyl-3-oxopentanoate (31.6 g, 0.200 mol), triethyl orthoformate (41.6 mL, 0.250 mol), and 4-bromoaniline (36.1 g, 0.210 mol) was heated at 150° C. for 2 h with a Dean Stark trap. After this time triethyl orthoformate (20.8 mL) was added and the reaction mixture was stirred for 16 h. The reaction was cooled to room temperature, diluted with 1:1 methylene chloride/hexanes (200 mL), and filtered through a plug of silica. The filtrate was concentrated, triturated with hexanes and filtered to afford the desired product (33.2 g, 53%) as a pale yellow solid: 1H NMR (300 MHz, CDCl3) δ 12.80 (d, J=11.9 Hz, 1H), 8.46 (d, J=13.0 Hz, 1H), 7.55-7.42 (m, 2H), 7.12-6.96 (m, 2H), 4.27 (q, J=7.1 Hz, 2H), 3.89-3.72 (m, 1H), 1.35 (t, J=7.1 Hz, 3H), 1.13 (d, J=6.8 Hz, 6H).

Workup

  1. temperatureThe reaction was cooled to room temperature
  2. filtrationfiltered through a plug of silica
  3. concentrationThe filtrate was concentrated
  4. customtriturated with hexanes
  5. filtrationfiltered

Sources & evidence

ORD record
ord-3c98defd1f984641991aa24541088d6c
Source dataset
uspto-grants-2015_09
Patent number
US09120749B2

Reaction notes

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