3-Aminobenzoic Acid → 3-(3,5-DI-T-Butyl-4-hydroxyanilino)benzoic acid

HRID 1165061Notes

Reaction equation

HRID 1165061 reaction equation
[C:1]([C:5]1[C:6](=[O:16])[C:7]([C:12]([CH3:15])([CH3:14])[CH3:13])=[CH:8][C:9](=O)[CH:10]=1)([CH3:4])([CH3:3])[CH3:2].[NH2:17][C:18]1[CH:19]=[C:20]([CH:24]=[CH:25][CH:26]=1)[C:21]([OH:23])=[O:22].C1COCC1.[O-]S(S([O-])=O)=O.[Na+].[Na+]>C(O)(=O)C.O>[C:1]([C:5]1[CH:10]=[C:9]([NH:17][C:18]2[CH:26]=[CH:25][CH:24]=[C:20]([C:21]([OH:23])=[O:22])[CH:19]=2)[CH:8]=[C:7]([C:12]([CH3:15])([CH3:14])[CH3:13])[C:6]=1[OH:16])([CH3:4])([CH3:3])[CH3:2]

Participants

7

Reactant 4

HCID 74193-Aminobenzoic AcidHCID 8028TetrahydrofuranHCID 128672,6-Di-t-butyl-p-benzoquinoneHCID 24489Sodium Dithionite

Product 1

HCID 601943-(3,5-DI-T-Butyl-4-hydroxyanilino)benzoic acidYield 65.5%

Reagents, catalysts & solvents 2

HCID 176Acetic AcidCatalystHCID 962WaterSolvent3×

Procedure

A mixture of 6.6 g of 2,6-di-tert-butyl-1,4-benzoquinone, 4.2 g of m-aminobenzoic acid and 6 drops of acetic acid was stirred with heating at a temperature of 150°-160° C. for 2 hours and then allowed to cool. To the reaction mixture were added about 50 ml of water and then 200 ml of THF. Further a solution of 50 g of Na2S2O4 in 300 ml of water was also added to the red mixture at room temperature, and the mixture was stirred for about 15 minutes until a decoloration took place. Then the mixture was poured into water and extracted with ethyl acetate. The organic layer was treated in the same manner as in Example 1 and the resulting crude product was purified by silica gel column chromatography (eluent: CH2Cl2 -THF=5:1), giving 6.7 g of the title compound. The title compound will be referred to as "Compound 24."

Workup

  1. temperaturewith heating at a temperature of 150°-160° C. for 2 hours
  2. temperatureto cool
  3. stirringthe mixture was stirred for about 15 minutes until a decoloration
  4. extractionextracted with ethyl acetate
  5. additionThe organic layer was treated in the same manner as in Example 1
  6. customthe resulting crude product was purified by silica gel column chromatography (eluent: CH2Cl2 -THF=5:1)

Sources & evidence

ORD record
ord-aa24325171224a4e8c7390a211c5f7b2
Source dataset
uspto-grants-1990_03
Patent number
US04906662

Reaction notes

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