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p-Toluenesulfonic acid → 4-methoxy-3-[(N-chloro-benzimidoyl)-amino]-benzoic acid methyl ester

HRID 349467
Notes
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Reaction equation

HRID 349467 reaction equation
C1(C)C=CC(S(O)(=O)=O)=CC=1.[CH3:12][O:13][C:14](=[O:24])[C:15]1[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[C:17]([NH2:23])[CH:16]=1.[C:25](#[N:32])[C:26]1[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=1.C([O-])(O)=O.[Na+].[O-][Cl:39].[Na+]>>[CH3:12][O:13][C:14](=[O:24])[C:15]1[CH:20]=[CH:19][C:18]([O:21][CH3:22])=[C:17]([NH:23][C:25](=[N:32][Cl:39])[C:26]2[CH:31]=[CH:30][CH:29]=[CH:28][CH:27]=2)[CH:16]=1
ParticipantsConditionsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 5

HCID 6101p-Toluenesulfonic acidHCID 7505BenzonitrileHCID 516892Sodium BicarbonateHCID 2734814Methyl 3-Amino-4-methoxybenzoateHCID 23665760Sodium Hypochlorite

Product 1

HCID 691195744-methoxy-3-[(N-chloro-benzimidoyl)-amino]-benzoic acid methyl ester
Yield 88%

Conditions

Temperature
180 °C

Procedure

Anhydrous p-toluene sulfonic acid (41.99 g, 220.8 mmol) was melted at 120° C. and 3-amino-4-methoxy benzoic acid methyl ester (20 g, 110.38 mmol) obtained in step 1 and benzonitrile (22.77 g, 220.8 mmol) were added thereto and stirred at 180° C. for 5 hours. The resulting solution was cooled to room temperature and the reaction was stopped by adding NaHCO3 thereto. The resulting mixture was extracted with ethyl acetate, the extract was dried over MgSO4 and concentrated under a reduced pressure. The concentrate was dissolved in 50% methanol and 5% NaOCl (56 Ml, 37.65 mmol) was added dropwise thereto. After 5 min, the resulting mixture was extracted with ethyl acetate, the extract was dried over MgSO4 and concentrated under a reduced pressure. The resulting residue was purified by silica gel column chromatography (eluent—MeOH/CDCl3=5:95, Merck, Silicagel 60) to obtain the title compound (31 g, 25.10 mmol) in a yield of 88%;

Workup

  1. additionwere added
  2. temperatureThe resulting solution was cooled to room temperature
  3. extractionThe resulting mixture was extracted with ethyl acetate
  4. dry with materialthe extract was dried over MgSO4
  5. concentrationconcentrated under a reduced pressure
  6. dissolutionThe concentrate was dissolved in 50% methanol
  7. waitAfter 5 min
  8. extractionthe resulting mixture was extracted with ethyl acetate
  9. dry with materialthe extract was dried over MgSO4
  10. concentrationconcentrated under a reduced pressure
  11. customThe resulting residue was purified by silica gel column chromatography (eluent—MeOH/CDCl3=5:95, Merck, Silicagel 60)

Sources & evidence

ORD record
ord-355faa56b66949f6b215a49bf9a90720
Source dataset
uspto-grants-2007_02
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US07179832B2

Reaction notes

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On this pageParticipantsConditionsProcedureWorkupSources & evidenceReaction notes