Acetone → HCID 86718445, compound

HRID 633652Notes

Reaction equation

HRID 633652 reaction equation
CC(C)=O.[OH:5][C@@H:6]1[C@@:13]([CH3:20])([CH2:14][CH2:15][CH:16]=[C:17]([CH3:19])[CH3:18])[C@@H:12]2[C@:21](O)([O:22]C)[C@@:8]([CH2:28][CH:29]=[C:30]([CH3:32])[CH3:31])([C:9]([O:26][CH3:27])=[CH:10][C:11]2=[O:25])[CH2:7]1.C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.CCCCCC>O.CCOC(C)=O>[OH:5][C@@H:6]1[C@@:13]([CH3:20])([CH2:14][CH2:15][CH:16]=[C:17]([CH3:18])[CH3:19])[C@@H:12]2[C:21](=[O:22])[C@@:8]([CH2:28][CH:29]=[C:30]([CH3:32])[CH3:31])([C:9]([O:26][CH3:27])=[CH:10][C:11]2=[O:25])[CH2:7]1

Participants

7

Reactant 4

HCID 180AcetoneHCID 8058HexaneHCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)HCID 90123964HCID 90123964, compound

Product 1

HCID 86718445HCID 86718445, compoundYield 90%

Reagents, catalysts & solvents 2

HCID 962WaterSolvent2×HCID 8857Ethyl AcetateSolvent

Procedure

A 1:1 acetone:H2O (4 mL) solution of 19 (65 mg, 0.17 mmol, 1 equiv.) and pyridinium para-toluenesulfonate (208 mg, 0.83 mmol, 5 equiv.) was heated to reflux in a 10-mL recovery flask with an affixed reflux condenser. After stirring at reflux for 15.5 h, the solution was cooled, diluted with H2O, and extracted thrice with 1:1 hexane:EtOAc. The organic extracts were combined, washed with H2O and brine, dried over Na2SO4, filtered, and concentrated in vacuo to give a faint yellow oil. Flash column chromatography (20 mL SiO2, 7:3 hexane:EtOAc) afforded 54 mg (0.15 mmol, 90% yield) of 20 as a colorless oil. TLC Rf 0.50 (1:1 hexane:EtOAc). 1H NMR (600 MHz; CDCl3): δ 5.67 (s, 1H), 5.08 (t, J=7.1 Hz, 1H), 4.98 (t, J=7.0 Hz, 1H), 3.82-3.80 (m, 1H), 3.75 (s, 3H), 3.19 (s, 1H), 2.49 (dd, J=14.5, 6.3 Hz, 1H), 2.40 (dd, J=14.6, 7.6 Hz, 1H), 2.34 (tt, J=12.6, 6.3 Hz, 1H), 2.11 (dd, J=13.4, 5.4 Hz, 1H), 1.91 (tt, J=12.4, 6.2 Hz, 1H), 1.75 (dd, J=13.3, 11.6 Hz, 1H), 1.67 (s, 2H), 1.66 (s, 3H), 1.65 (s, 3H), 1.64 (s, 3H), 1.61-1.59 (m, 1H), 1.56 (td, J=12.8, 4.8 Hz, 1H), 1.32 (td, J=12.7, 4.8 Hz, 1H), 0.91 (s, 3H). 13C NMR (126 MHz; CDCl3): δ 205.2, 193.1, 177.5, 134.5, 132.2, 124.3, 119.0, 106.0, 72.1, 69.2, 57.1, 56.0, 45.9, 39.4, 38.1, 29.5, 26.1, 25.9, 21.8, 18.1, 17.9, 15.7. HRMS-ESI (m/z): [M+H]+ calculated for C22H32O4, 361.2373. found, 361.2357.

Workup

  1. temperatureto reflux in a 10-mL recovery flask with an affixed reflux condenser
  2. temperatureat reflux for 15.5 h
  3. temperaturethe solution was cooled
  4. extractionextracted thrice with 1:1 hexane
  5. washwashed with H2O and brine
  6. dry with materialdried over Na2SO4
  7. filtrationfiltered
  8. concentrationconcentrated in vacuo
  9. customto give a faint yellow oil

Sources & evidence

ORD record
ord-dfd520eaff984dada296b494a47d3d8b
Source dataset
uspto-grants-2016_04
Patent number
US09321713B2

Reaction notes

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