p-Toluenesulfonic acid → HCID 66730804, compound

HRID 1802833Notes

Reaction equation

HRID 1802833 reaction equation
[CH3:1][C:2]1([CH3:17])[CH2:7][CH:6]([OH:8])[CH:5]([OH:9])[CH:4]2[C:10]([CH3:16])([CH3:15])[CH:11]3[CH2:14][C:3]12[CH2:13][CH2:12]3.CO[C:20](OC)([CH3:22])[CH3:21].C1(C)C=CC(S(O)(=O)=O)=CC=1.C(=O)(O)[O-].[Na+].CCCCCCCCCCCCCC>C1COCC1>[CH3:1][C:2]1([CH3:17])[CH2:7][CH:6]2[CH:5]([O:9][C:20]([CH3:22])([CH3:21])[O:8]2)[CH:4]2[C:10]([CH3:16])([CH3:15])[CH:11]3[CH2:14][C:3]12[CH2:13][CH2:12]3

Participants

7

Reactant 5

HCID 6101p-Toluenesulfonic acidHCID 64952,2-DimethoxypropaneHCID 12389TetradecaneHCID 516892Sodium BicarbonateHCID 66730781HCID 66730781, compound

Product 1

HCID 66730804HCID 66730804, compoundYield 24%

Reagents, catalysts & solvents 1

HCID 8028TetrahydrofuranSolvent

Procedure

A solution of diols from Example 1d (3.0 g, ˜6.5 mmol of the main diastereomeric pair of enantiomers of 5a), 2,2-dimethoxypropane (4.0 g, 0.38 mol) lithium bromide (0.1 g) and p-toluenesulfonic acid (0.1 g) in THF (40 ml) was stirred at r. t. for 2 h, then poured onto saturated aqueous sodium bicarbonate solution (100 ml) and extracted with MTBE (2×100 ml). The combined organic phases were washed with water (2×100 ml), dried (Na2SO4), concentrated in vacuo and the residue (3.0 g) purified by flash chromatography (MTBE/hexane 1:20) to afford a mixture of isomeric diols (0.60 g, colourless oil) in which the main diastereoisomeric pair of enantiomers of 2,2,6,6,10,10-hexamethyl-5,7-dioxatetracyclo[9.2.1.01.9, 04.8]tetradecane (Ia) constituted 73% (24% yield).

Workup

  1. extractionextracted with MTBE (2×100 ml)
  2. washThe combined organic phases were washed with water (2×100 ml)
  3. dry with materialdried (Na2SO4)
  4. concentrationconcentrated in vacuo
  5. customthe residue (3.0 g) purified by flash chromatography (MTBE/hexane 1:20)
  6. customto afford

Sources & evidence

ORD record
ord-437e22fec3fd462597faa920ca5c210a
Source dataset
uspto-grants-2013_01
Patent number
US08349890B2

Reaction notes

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