Hydrochloric Acid → 3,5-Bis(m-trifluoromethylphenyl)-4-(2-hydroxyethoxy)benzoic acid ethyl ester

HRID 324052Notes

Reaction equation

HRID 324052 reaction equation
C(N[C:14](=[O:45])[C:15]1[CH:20]=[C:19]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([C:27]([F:30])([F:29])[F:28])[CH:22]=2)[C:18]([O:31][CH2:32][CH2:33][OH:34])=[C:17]([C:35]2[CH:40]=[CH:39][CH:38]=[C:37]([C:41]([F:44])([F:43])[F:42])[CH:36]=2)[CH:16]=1)CCCCCCCCCCC.C[N+]1([O-])CC[O:50][CH2:49][CH2:48]1.OS([O-])=O.[Na+].Cl>CC#N.CCC[N+](CCC)(CCC)CCC.[O-][Ru](=O)(=O)=O>[CH2:49]([O:50][C:14](=[O:45])[C:15]1[CH:16]=[C:17]([C:35]2[CH:40]=[CH:39][CH:38]=[C:37]([C:41]([F:44])([F:42])[F:43])[CH:36]=2)[C:18]([O:31][CH2:32][CH2:33][OH:34])=[C:19]([C:21]2[CH:26]=[CH:25][CH:24]=[C:23]([C:27]([F:28])([F:29])[F:30])[CH:22]=2)[CH:20]=1)[CH3:48]

Participants

7

Reactant 4

HCID 313Hydrochloric AcidHCID 82029Methyl morpholine oxide2×HCID 22237575N-dodecyl-3,5-bis(m-trifluoromethylphenyl)4-(2-hydroxyethoxy)benzamideHCID 23665763Sodium Bisulfite

Product 1

HCID 540981933,5-Bis(m-trifluoromethylphenyl)-4-(2-hydroxyethoxy)benzoic acid ethyl esterYield 44.6%

Reagents, catalysts & solvents 2

HCID 178419074HCID 178419074, compoundCatalyst2×HCID 6342AcetonitrileSolvent

Procedure

To a solution of N-dodecyl-3,5-bis(m-trifluoromethylphenyl)-4-(2-hydroxyethoxy)benzamide (0.254 g, 0.40 mmol) in CH3CN was added NMO (0.145 g, 0.89 mmol) and TPAP (0.014 g, 0.04 mmol). The reaction was stirred at room temperature overnight. Additional NMO (0.045 g, 0.38 mmol) and TPAP (0.013 g, 0.04 mmol) were required as indicated by TLC. After stirring 48 h, 10% NaHSO3 solution was added and the resulting biphasic mixture was stirred vigorously for 30 min. Conc. HCl (2 mL) was added and stirring was continued for 10 min. The layers were separated and the aqueous layer was extracted with EtOAc. The combined organics were washed with brine, dried over Na2SO4, and concentrated in vacuo. The residue was purified by flash chromatography (30% EtOAc:Hexane+1% Formic acid) followed by preparatory plate chromatography (30% EtOAc:Hexane+1% Formic acid) to afford the title compound (0.089 g, 34%) as a white solid. mp 154.3-158.2° C.; 1H NMR (DMSO-d6) δ8.55 (t, 1H); 7.98-7.88 (m, 6H); 7.78-7.67 (m, 4H); 3.57 (s, 2H); 3.25 (m, 2H); 1.50 (m, 2H); 1.23 (m, 18H); 0.82 (t, 3H); IR (KBr) 3275, 2900, 1725, 1600, 1575, 1460, 1325, 1190, 1125, 1075, 775, 725, 700, 625 cm−1; mass spectrum [(−)ESI], m/z 650 (M−H)−; Anal. Calcd. for C35H39F6NO4: C, 64.51; H, 6.03; N, 2.15, Found: C, 62.50; H, 5.99; N, 2.01.

Workup

  1. stirringAfter stirring 48 h
  2. stirringthe resulting biphasic mixture was stirred vigorously for 30 min
  3. stirringstirring
  4. waitwas continued for 10 min
  5. customThe layers were separated
  6. extractionthe aqueous layer was extracted with EtOAc
  7. washThe combined organics were washed with brine
  8. dry with materialdried over Na2SO4
  9. concentrationconcentrated in vacuo
  10. customThe residue was purified by flash chromatography (30% EtOAc:Hexane+1% Formic acid)

Sources & evidence

ORD record
ord-e1470e89e21b49c3ba45bec09bad7bf1
Source dataset
uspto-grants-2001_04
Patent number
US06214877B1

Reaction notes

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