HCID 14702771, compound → HCID 22406459, compound

HRID 440225Notes

Reaction equation

HRID 440225 reaction equation
[OH:1][C:2]1([C:12]#[C:13]/[C:14](/[CH3:18])=[CH:15]/[CH2:16][OH:17])[CH:7]([CH3:8])[CH2:6][C:5](=[O:9])[CH2:4][C:3]1([CH3:11])[CH3:10]>[O-2].[O-2].[Mn+4].CC(C)=O>[OH:1][C:2]1([C:12]#[C:13]/[C:14](/[CH3:18])=[CH:15]/[CH:16]=[O:17])[CH:7]([CH3:8])[CH2:6][C:5](=[O:9])[CH2:4][C:3]1([CH3:10])[CH3:11]

Participants

4

Reactant 1

HCID 14702771HCID 14702771, compound

Product 1

HCID 22406459HCID 22406459, compoundYield 58%

Reagents, catalysts & solvents 2

HCID 178418406HCID 178418406, compoundCatalystHCID 180AcetoneSolvent

Procedure

A mixture of (±)-E-4-hydroxy-4-(5-hydroxy-3-methylpent-3-en-1-ynyl)-3,3,5-trimethylcyclohexanone (2.0 g, 8.0 mol), manganese dioxide (14 g, 160 mmol), and acetone (50 mL) were combined and strred for 1.5 h. The mixture was filtered, the solvent removed by evaporation, and the residue chromatographed over silica eluting with 75% ether and 25% hexane to afford 1.17 g (±)-E-4-hydroxy-4-(5-oxo-3-methylpent-3-en-1-ynyl)-3,3,5-trimethylcyclohexanone (58%), as an oil, that gave ir: 3600 (strong), 220 (weak), 1710, 1660, 900 cm-1; gc/eims: 248 (M+, 15%) 233 (9), 219 (19), 205 (16), 192 (42), 163 (95) and 121 (100); 1H nmr -∥: 0.99 and 1.20 (s, gem CH3, 6H), 1.14 (d, J=5.9 Hz, HCCH3, 3H), 2.11 (dd, J=14.3, 2.3 Hz, H-2 eq, 1H), 2.18 (m, H-6eq, 1H), 2.3 (m, 2H), 2.32 (d, J=1.5 Hz, =CCH3, 3H), 2.60 (d, J=14.3 Hz, H-2ax, 1H), 6.22 (dq, J=7.7, 1.5 Hz, =CH, 1H), and 10.03 (d, J=7.7 Hz, CHO, 1H).

Workup

  1. filtrationThe mixture was filtered
  2. customthe solvent removed by evaporation
  3. customthe residue chromatographed over silica eluting with 75% ether and 25% hexane

Sources & evidence

ORD record
ord-1d573a9c175d434192ab4d8aac9837b7
Source dataset
uspto-grants-1996_05
Patent number
US05518995

Reaction notes

Loading…