2,4-Dinitroaniline → 4-(2,4-Dinitro-phenylcarbamoyl)-butyric acid methyl ester

HRID 1967481Notes

Reaction equation

[N+:1]([C:4]1[CH:10]=[C:9]([N+:11]([O-:13])=[O:12])[CH:8]=[CH:7][C:5]=1[NH2:6])([O-:3])=[O:2].[CH3:14][O:15][C:16](=[O:23])[CH2:17][CH2:18][CH2:19][C:20](Cl)=[O:21]>C(#N)C>[CH3:14][O:15][C:16](=[O:23])[CH2:17][CH2:18][CH2:19][C:20](=[O:21])[NH:6][C:5]1[CH:7]=[CH:8][C:9]([N+:11]([O-:13])=[O:12])=[CH:10][C:4]=1[N+:1]([O-:3])=[O:2]

Participants

Conditions

Temperature: 75 °C

Procedure

To a solution of 2,4-dinitroaniline (6.00 g, 32.76 mmol) in acetonitrile (60 mL) was added methyl-5-chloro-5-oxo-valerate (5.44 mL, 39.31 mmol, 1.2 equiv) at 20° C. in one portion. The reaction mixture was then heated to 75° C. Reaction progress was monitored periodically by HPLC (HPLC Method A). The reaction was complete after stirring for 23 hours at 75° C. to give 4-(2,4-dinitro-phenylcarbamoyl)-butyric acid methyl ester. This reaction mixture was cooled to 20° C. and a portion of the solvent was then removed in vacuo to yield a total reaction volume of approximately 25 mL. To the concentrated mixture was then added potassium carbonate (13.58 g, 98.26 mmol, 3.0 equiv) and methyl iodide (10.20 mL, 163.48 mmol, 5.0 equiv.) at 20° C. Reaction progress was monitored periodically by HPLC Method A. The reaction was complete after 17 hours at 20° C. to give 4-[(2,4-dinitro-phenyl)-methyl-carbamoyl]-butyric acid methyl ester. The reaction mixture was filtered to remove excess K2CO3 and the filtrate was poured into cold water (200 mL) to yield off-white solids. The solid product was collected by vacuum filtration and dried at 60° C. under vacuum/N2 sweep overnight to give 8.914 g, (84% yield) as a light tan solid.

Workup

customReaction progress

Sources & evidence

ORD record: ord-7faee7f2098743beb3f6128228181d45
Source dataset: uspto-grants-2013_04
DOI: 10.6084/m9.figshare.5104873.v1
Patent number: US08420829B2

Reaction notes

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