Hydrochloric Acid → 3-amino-N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-6-methylphenyl]-2-methoxybenzamide

HRID 570759Notes

Reaction equation

HRID 570759 reaction equation
[CH2:1]([C:3]1[CH:8]=[C:7]([C:9]([F:21])([C:17]([F:20])([F:19])[F:18])[C:10]([F:16])([F:15])[C:11]([F:14])([F:13])[F:12])[CH:6]=[C:5]([CH3:22])[C:4]=1[NH:23][C:24](=[O:36])[C:25]1[CH:30]=[CH:29][CH:28]=[C:27]([N+:31]([O-])=O)[C:26]=1[O:34][CH3:35])[CH3:2].[Sn](Cl)(Cl)(Cl)Cl.Cl>C(O)(C)C>[NH2:31][C:27]1[C:26]([O:34][CH3:35])=[C:25]([CH:30]=[CH:29][CH:28]=1)[C:24]([NH:23][C:4]1[C:5]([CH3:22])=[CH:6][C:7]([C:9]([F:21])([C:17]([F:18])([F:19])[F:20])[C:10]([F:15])([F:16])[C:11]([F:14])([F:13])[F:12])=[CH:8][C:3]=1[CH2:1][CH3:2])=[O:36]

Participants

5

Reactant 3

HCID 313Hydrochloric AcidHCID 24287Tin tetrachlorideHCID 86673889N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphenyl]-2-methoxy-3-nitrobenzamide

Product 1

HCID 866738903-amino-N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethyl-propyl)-6-methylphenyl]-2-methoxybenzamideYield 48%

Reagents, catalysts & solvents 1

HCID 3776IsopropanolSolvent

Conditions

Temperature
0 °C

Procedure

To a solution of N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphenyl]-2-methoxy-3-nitrobenzamide (Example I 4.1) (5.1 g, 9.57 mmol) in isopropanol (50 ml) was added tin chloride (6.5 g, 34.5 mmol) at ambient temperature. The mixture was cooled to 0° C. and concentrated aqueous hydrochloric acid (10 ml) was added slowly. The reaction mixture was stirred at 80° C. for 0.5 hours. One third of the total volume of isopropanol was evaporated. Water (100 ml) was added to the concentrated mixture and aqueous sodium hydroxide (4N) was added to adjust the pH to 7 to 8. The aqueous phase was extracted three times with ethyl acetate (3×200 ml). The combined organic extracts were dried over sodium sulfate and concentrated. The residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 2:1 to 1:1) to give 3-amino-N-[2-ethyl-4-(1,2,2,3,3,3-hexafluoro-1-trifluoromethylpropyl)-6-methylphenyl]-2-methoxy benzamide (2.3 g, 48% yield).

Workup

  1. customat ambient temperature
  2. customOne third of the total volume of isopropanol was evaporated
  3. additionWater (100 ml) was added to the concentrated mixture and aqueous sodium hydroxide (4N)
  4. additionwas added
  5. extractionThe aqueous phase was extracted three times with ethyl acetate (3×200 ml)
  6. dry with materialThe combined organic extracts were dried over sodium sulfate
  7. concentrationconcentrated
  8. customThe residue was purified by column chromatography on silica gel (eluent: cyclohexane/ethyl acetate 2:1 to 1:1)

Sources & evidence

ORD record
ord-6e65445c33d74a749b0092738ee297d7
Source dataset
uspto-grants-2015_05
Patent number
US09023873B2

Reaction notes

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