HCID 11100765, compound → HCID 10877966, compound

HRID 2404891Notes

Reaction equation

HRID 2404891 reaction equation
C([N:8](CC1C=CC=CC=1)[C:9]1[CH:14]=[CH:13][C:12]([C:15]([F:18])([F:17])[F:16])=[C:11]([O:19][CH3:20])[N:10]=1)C1C=CC=CC=1>CO.CC(O)=O.[OH-].[Pd+2].[OH-]>[CH3:20][O:19][C:11]1[N:10]=[C:9]([NH2:8])[CH:14]=[CH:13][C:12]=1[C:15]([F:18])([F:16])[F:17]

Participants

5

Reactant 1

HCID 11100765HCID 11100765, compound

Product 1

HCID 10877966HCID 10877966, compoundYield 90.4%

Reagents, catalysts & solvents 3

HCID 9942167Palladium hydroxideCatalystHCID 176Acetic AcidSolventHCID 887MethanolSolvent

Conditions

Temperature
25 °C

Procedure

To a solution of N,N-dibenzyl-6-methoxy-5-(trifluoromethyl)pyridin-2-amine (3.0 g, 8.056 mmol) in a mixture of methanol (30 mL) and AcOH (3 mL) was added palladium hydroxide (0.3 g, 0.43 mmol) under a nitrogen atmosphere. The mixture was stirred under hydrogen atmosphere (55 psi, 25° C.) overnight. The catalyst was removed by filtration through a pad of celite and the filtrate was neutralized by saturated Na2CO3. The aqueous layer was extracted with CH2Cl2 (30 mL×3) and the combined organic layers were concentrated under vacuum to give 6-methoxy-5-(trifluoromethyl)pyridin-2-amine (1.4 g, 90%) as a pale yellow solid. 1H NMR (400 MHz, CDCl3) δ 7.56 (d, J=8.4 Hz, 1H), 6.03 (d, J=8.0 Hz, 1H), 4.64 (brs, 2H), 3.93 (s, 3H). MS (ESI) m/e (M+H+) 193. 13C NMR (100 MHz, CDCl3) 159.4, 138.0 (d, J=5.9 Hz), 125.9, 122.3, 101.9 (d, J=44.4 Hz), 98.3, 53.6. 19F NMR (282.4 MHz, CDCl3) −62.6.

Workup

  1. customThe catalyst was removed by filtration through a pad of celite
  2. extractionThe aqueous layer was extracted with CH2Cl2 (30 mL×3)
  3. concentrationthe combined organic layers were concentrated under vacuum

Sources & evidence

ORD record
ord-37bff57fe7a54b838af284e0252799c0
Source dataset
uspto-grants-2014_08
Patent number
US08802700B2

Reaction notes

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