HCID 22004977, compound → HCID 22005363, compound

HRID 324887Notes

Reaction equation

HRID 324887 reaction equation
[CH:1]([C:4]1[C:5]([CH:25]([OH:27])[CH3:26])=[C:6]([C:18]2[CH:23]=[CH:22][C:21]([F:24])=[CH:20][CH:19]=2)[C:7]([CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])=[C:8]([CH:10]([CH3:12])[CH3:11])[CH:9]=1)([CH3:3])[CH3:2].[Cr](Cl)([O-])(=O)=O.[NH+]1C=CC=CC=1>ClCCl.C(OCC)(=O)C.CCCCCC>[CH:1]([C:4]1[C:5]([C:25](=[O:27])[CH3:26])=[C:6]([C:18]2[CH:19]=[CH:20][C:21]([F:24])=[CH:22][CH:23]=2)[C:7]([CH2:13][CH2:14][CH2:15][CH2:16][CH3:17])=[C:8]([CH:10]([CH3:11])[CH3:12])[CH:9]=1)([CH3:2])[CH3:3]

Participants

6

Reactant 2

HCID 22004977HCID 22004977, compoundHCID 178418287HCID 178418287, compound

Product 1

HCID 22005363HCID 22005363, compoundYield 99%

Reagents, catalysts & solvents 3

HCID 6344DichloromethaneSolventHCID 8058HexaneSolventHCID 8857Ethyl AcetateSolvent

Procedure

A mixture of 3,5-diisopropyl-2-(1-hydroxyethyl)-6-pentyl-4′-fluoro-1,1′-biphenyl (Example 192, 13.7 g, 37.1 mmol), Celite (26 g), and pyridinium chlorochromate (14.9 g, 69.3 mmol) in dichloromethane (750 mL) was stirred for 45 minutes. The mixture was diluted with ethyl acetate (750 mL) and hexane (1.5 L) and filtered through a plug of silica (100 mm×2″) topped with Celite (100 mm×0.5″). Elution was continued with ethyl acetate:hexanes (1:1 mixture, 3L×2). The combined filtrates were concentrated in vacuo to afford the desired product as a white solid (13.5 g, 99%). 1H NMR (300 MHz, CDCl3): δ 0.75-0.80 (m, 3H), 1.06-1.31 (m, 18H), 1.95 (s, 3H), 2.33-2.39 (m, 2H), 2.78 (septet, J=7.0 Hz, 1H), 3.18 (septet, J=7.0 Hz, 1H), 7.03-7.09 (m, 2H), 7.17-7.22 (m, 2H) 7.26 (s, 1H). 13C NMR (75 MHz, CDCl3): δ 13.75, 22.02, 24.32, 24.37, 28.99, 29.10, 29.28, 30.60, 31.04, 32.06, 33.03, 114.85 (d, J=20.8 Hz, 2C), 122.06, 132.03 (d, J=7.3 Hz, 2C), 135.52 (d, J=2.4 Hz, 1C) 135.58, 135.76, 140.13, 140.85, 147.66 161.99 (d, J=246.6 Hz, 1C), 208.23. EI-MS: calculated for C25H33OF 368; found 368 (M+). Anal. calc for C25H33OF: C, 80.86; H, 8.96. Found: C, 81.04; H, 9.06. Rf=0.65 (9:1 hexanes:ethyl acetate). HPLC: (C-18, A=0.05% aqueous trifluoroacetic add, B=CH3CN; linear gradient: 75%-100% B over 30 min; 254 nm, 1 mL/min): R.T. 22.7 min (94.0 area %). mp 123.0-124.5° C.

Workup

  1. filtrationfiltered through a plug of silica (100 mm×2″)
  2. washElution
  3. concentrationThe combined filtrates were concentrated in vacuo

Sources & evidence

ORD record
ord-4c68f86345d44454ad74a1cd5bde1906
Source dataset
uspto-grants-2001_04
Patent number
US06218431B1

Reaction notes

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