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Formic Acid → Formamide, N-(4-bromophenyl)-

HRID 22868
Notes
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Reaction equation

HRID 22868 reaction equation
C(O[C:5](=[O:7])C)(=O)C.C(O)=O.[Br:11][C:12]1[CH:18]=[CH:17][C:15]([NH2:16])=[CH:14][CH:13]=1>C1COCC1>[Br:11][C:12]1[CH:18]=[CH:17][C:15]([NH:16][CH:5]=[O:7])=[CH:14][CH:13]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

5

Reactant 3

HCID 284Formic Acid2×HCID 78074-BromoanilineHCID 7918Acetic Anhydride

Product 1

HCID 17474Formamide, N-(4-bromophenyl)-Yield 99.2%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent2×

Conditions

Temperature
0 °C

Procedure

A 5-Liter round bottom flask was charged with acetic anhydride (488 mL, 5.2 mol) and cooled to 0° C. Formic acid (240 mL, 6.4 mol) was then added at a rate that did not elevate the temperature of the reaction mixture above 10° C. After the formic acid was added, the temperature of the reaction was raised to 50-60° C. and stirred for 3 hours. The reaction was then cooled to 0° C. and 400 mL of THF was added. A solution of 4-bromoaniline (344 g, 2.0 mol) in 800 mL of THF was added dropwise. After the addition was complete, the reaction was allowed to stir at this temperature for 4 hours. The reaction was checked by thin-layer chromatography and found to be complete. The reaction mixture was transferred to a round bottom flask and the solvent was removed in vacuo. When the solvent had been removed, the residue crystallized. The solid was triturated with heptane and filtered. Obtained 396.8 grams of desired N-(4-bromo-phenyl)-formamide. Yield 99.2% The spectral properties of the solid were consistent with the desired material. Step (2): (4-bromo-phenyl)-methyl-amine

Workup

  1. customthe temperature of the reaction mixture above 10° C
  2. temperaturethe temperature of the reaction was raised to 50-60° C.
  3. temperatureThe reaction was then cooled to 0° C.
  4. additionAfter the addition
  5. stirringto stir at this temperature for 4 hours
  6. customThe reaction mixture was transferred to a round bottom flask
  7. customthe solvent was removed in vacuo
  8. customWhen the solvent had been removed
  9. customthe residue crystallized
  10. customThe solid was triturated with heptane
  11. filtrationfiltered

Sources & evidence

ORD record
ord-46bb61989247402b83f957372f1f9da2
Source dataset
uspto-grants-2005_02
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US06849648B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes