4-Bromoaniline → HCID 178471905, compound

HRID 2271525Notes

Reaction equation

[C:1]([CH2:5][C:6]([O:8][CH2:9][CH3:10])=[O:7])(=[O:4])[CH2:2][CH3:3].[CH:11](OCC)(OCC)OCC.[Br:21][C:22]1[CH:28]=[CH:27][C:25]([NH2:26])=[CH:24][CH:23]=1>>[Br:21][C:22]1[CH:28]=[CH:27][C:25]([NH:26][CH:11]=[C:5]([C:1](=[O:4])[CH2:2][CH3:3])[C:6]([O:8][CH2:9][CH3:10])=[O:7])=[CH:24][CH:23]=1

Participants

Reactant 3

HCID 78074-Bromoaniline

HCID 31214Ethyl orthoformate

HCID 78656Ethyl 3-oxovalerate

Product 1

HCID 178471905HCID 178471905, compoundYield 33.5%

Conditions

Temperature: 150 °C

Procedure

A stirred mixture of ethyl propionylacetate (33 g, 0.23 mol), triethyl orthoformate (46 mL, 0.28 mol), and 4-bromoaniline (42 g, 0.24 mol) were heated at 150° C. for 2 h with a Dean Stark trap. The reaction was cooled to room temperature. Trituration with 1:1 hexanes/diethyl ether afforded the desired product (25.1 g, 33%) as a tan solid: 1H NMR (300 MHz, DMSO-d6) δ 12.44 (d, J=13.1 Hz, 1H), 8.42 (d, J=13.1 Hz 1H), 7.64-7.51 (m, 2H), 7.50-7.34 (m, 2H), 4.17 (q, J=7.1 Hz, 2H), 2.86 (q, J=7.3 Hz, 2H), 1.27 (t, J=7.1 Hz, 3H), 1.02 (t, J=7.3 Hz, 3H).

Workup

temperatureThe reaction was cooled to room temperature

Sources & evidence

ORD record: ord-5ea70abd151c42e1986b8be864392521
Source dataset: uspto-grants-2015_09
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US09120749B2

Reaction notes

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