Diethyl Malonate → Ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate

HRID 648790Notes

Reaction equation

HRID 648790 reaction equation
[C:1]([O:9][CH2:10][CH3:11])(=[O:8])[CH2:2][C:3]([O:5]CC)=O.[Br:12][C:13]1[CH:19]=[CH:18][C:16]([NH2:17])=[C:15]([CH3:20])[CH:14]=1>>[Br:12][C:13]1[CH:19]=[CH:18][C:16]([NH:17][C:3](=[O:5])[CH2:2][C:1]([O:9][CH2:10][CH3:11])=[O:8])=[C:15]([CH3:20])[CH:14]=1

Participants

3

Reactant 2

HCID 7761Diethyl MalonateHCID 114234-Bromo-2-methylaniline

Product 1

HCID 14150214Ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoateYield 62.5%

Conditions

Temperature
160 °C

Procedure

Into a 500 milliliter four-necked round-bottom reaction flask equipped with a mechanical stirrer, Dean-Stark trap/condenser, thermometer and heating mantle was added 320 grams (2.0 mol) of diethyl malonate and 37.2 grams (0.2 mol) of 4-bromo-2-methylaniline. The resulting mixture was heated at a temperature of 160° C. for a period of four hours and then cooled to a temperature of about 0° C. to form a precipitate. After filtering on a fritted glass funnel, the wet-cake was washed with heptane and air dried to give 37.6 grams (0.125 mol) of ethyl 3-[(4-bromo-2-methylphenyl)amino]-3-oxopropanoate. Liquid chromatographic analysis indicated 97 percent purity by comparison with an authenic sample of pure material. NMR analysis of the product indicated the following: 'H NMR (CDCl3) δ9.52 (1H, bs), 8.02 (1H, d, J=9 Hz), 7.2-7.5 (2H, m), 4.30 (2H, q, J=7 Hz), 3.50 (2H, s), 2.30 (3H, s), 1.30 (3H, t, J=7 Hz).

Workup

  1. customInto a 500 milliliter four-necked round-bottom reaction flask equipped with a mechanical stirrer
  2. temperatureDean-Stark trap/condenser, thermometer and heating mantle
  3. temperaturecooled to a temperature of about 0° C.
  4. customto form a precipitate
  5. filtrationAfter filtering on a fritted glass funnel
  6. washthe wet-cake was washed with heptane and air
  7. customdried

Sources & evidence

ORD record
ord-f6e766cb5d4c4730941e5ae9d3323ea8
Source dataset
uspto-grants-1988_04
Patent number
US04736056

Reaction notes

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