Water → [3,5,3'',5''-Tetramethyl-5'-(8-phenyl-octylcarbamoyl)-[1,1':3',1'']terphenyl-2'-yloxy]acetic Acid

HRID 1743461Notes

Reaction equation

HRID 1743461 reaction equation
[C:1]1([CH2:7][CH2:8][CH2:9][CH2:10][CH2:11][CH2:12][CH2:13][CH2:14][NH:15][C:16](=[O:43])[C:17]2[CH:22]=[C:21]([C:23]3[CH:28]=[C:27]([CH3:29])[CH:26]=[C:25]([CH3:30])[CH:24]=3)[C:20]([O:31][CH2:32][CH2:33][OH:34])=[C:19]([C:35]3[CH:40]=[C:39]([CH3:41])[CH:38]=[C:37]([CH3:42])[CH:36]=3)[CH:18]=2)[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.C[N+]1([O-])CC[O:48]CC1.O.S(=O)(O)[O-].[Na+].S(S([O-])=O)([O-])=O.[Na+].[Na+]>C(#N)C.CCC[N+](CCC)(CCC)CCC.[O-][Ru](=O)(=O)=O.CC(O)=O.CCOC(C)=O>[CH3:29][C:27]1[CH:28]=[C:23]([C:21]2[CH:22]=[C:17]([C:16](=[O:43])[NH:15][CH2:14][CH2:13][CH2:12][CH2:11][CH2:10][CH2:9][CH2:8][CH2:7][C:1]3[CH:2]=[CH:3][CH:4]=[CH:5][CH:6]=3)[CH:18]=[C:19]([C:35]3[CH:40]=[C:39]([CH3:41])[CH:38]=[C:37]([CH3:42])[CH:36]=3)[C:20]=2[O:31][CH2:32][C:33]([OH:48])=[O:34])[CH:24]=[C:25]([CH3:30])[CH:26]=1

Participants

9

Reactant 4

HCID 962WaterHCID 82029Methyl morpholine oxide3×HCID 22237505N-8-Phenyloctyl-3,5-bis-(3,5-dimethylphenyl)-4-(2-hydroxyethoxy)benzamideHCID 86583660Sodium bisulfite sodium dithionite

Product 1

HCID 9873259[3,5,3'',5''-Tetramethyl-5'-(8-phenyl-octylcarbamoyl)-[1,1':3',1'']terphenyl-2'-yloxy]acetic AcidYield 23%

Reagents, catalysts & solvents 4

HCID 178419074HCID 178419074, compoundCatalyst2×HCID 176Acetic AcidSolventHCID 6342AcetonitrileSolventHCID 8857Ethyl AcetateSolvent

Procedure

To a solution of N-8-phenyloctyl-3,5-bis-(3,5-dimethylphenyl)-4-(2-hydroxyethoxy)benzamide (850 mg, 1.47 mmol) in 15 mL of acetonitrile was added NMMO (415 mg, 3.05 mmol) and TPAP (52 mg, 0.149 mmol). The reaction was stirred for 2 hours then an additional 40 mg, 0.3 mmol NMMO and 52 mg, 0.149 mmol TPAP were added. The reaction was stirred overnight and an additional 40 mg, 0.3 mmol, NMMO was added. The reaction was stirred an additional two hours then water was added followed by the addition of sodium bisulfite/sodium dithionite. The aqueous mixture was stirred for 1 hour then it was extracted with EtOAc (3×). The combined extracts were dried with Na2SO4 and concentrated to give a black oil. This oil was subjected to flash chromatography (20% EtOAc: 80% Hexanes acidified with 1% CH3COOH) on HCOOH pretreated silica gel. There yielded 200 mg of the desired acid plus a fraction consisting of the desired acid and other impurities. This fraction was chromatographed again using the same solvent system to give 30 mg more of the acid for a total yield of 230 mg, 26.4% of the desired acid. 1H NMR (DMSO-d6) δ 1.27 (bs, 8H); 1.45–1.60 (m, 4H); 2.31 (s, 12H); 2.53 (t, J=7.58 Hz, 2H); 3.23 (quartet, J=6.37 Hz, 2H); 3.81 (s, 2H); 7.00–7.01 (m, 2H); 7.13–7.15 (m, 3H); 7.19–7.25 (m, 6H); 7.76 (s, 2H); 8.48 (t, J=6.00 Hz, 1H); 12.35 (bs, 1H); IR 3325, 2935, 2875, 1750, 1645, 1605, 1580, 1545, 1480, 1460, 1430, 1400, 1385, 1380, 1295, 1250, 1200, 1150, 850, and 700 cm−1; mass spectrum [(+)APCI], m/z 592 [M+H]+; Anal Calcd for C39H45NO4.C2H4O2.C4H8O2: C, 73.03; 7.63; H, 7.63; N, 1.89. Found: C, 73.32, H, 7.88; N, 2.04.

Workup

  1. stirringThe reaction was stirred overnight
  2. stirringThe reaction was stirred an additional two hours
  3. stirringThe aqueous mixture was stirred for 1 hour
  4. extractionit was extracted with EtOAc (3×)
  5. dry with materialThe combined extracts were dried with Na2SO4
  6. concentrationconcentrated
  7. customto give a black oil

Sources & evidence

ORD record
ord-ffc99f4cf1924137833aae0de426e86b
Source dataset
uspto-grants-2006_03
Patent number
US07008636B2

Reaction notes

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