Toluene → Di[(5-ethyl-2-vinyl-[1,3]dioxan-5-yl)methyl]ether

HRID 983358Notes

Reaction equation

HRID 983358 reaction equation
[CH3:1][CH2:2][C:3]([CH2:8][O:9][CH2:10][C:11]([CH2:16][OH:17])([CH2:14][OH:15])[CH2:12][CH3:13])([CH2:6][OH:7])[CH2:4][OH:5].C(O[CH:21](OCC)[CH:22]=[CH2:23])C.[C:27]1(C)[CH:32]=CC=C[CH:28]=1>C1(C)C=CC(S([O-])(=O)=O)=CC=1.[NH+]1C=CC=CC=1.CC(C)([O-])C.[K+]>[CH2:2]([C:3]1([CH2:8][O:9][CH2:10][C:11]2([CH2:12][CH3:13])[CH2:14][O:15][CH:21]([CH:22]=[CH2:23])[O:17][CH2:16]2)[CH2:4][O:5][CH:32]([CH:27]=[CH2:28])[O:7][CH2:6]1)[CH3:1]

Participants

6

Reactant 3

HCID 1140TolueneHCID 624773,3-Diethoxy-1-propeneHCID 90038Ditrimethylolpropane

Product 1

HCID 11624015Di[(5-ethyl-2-vinyl-[1,3]dioxan-5-yl)methyl]etherYield 91%

Reagents, catalysts & solvents 2

HCID 466102Benzenesulfonic acid, 4-methyl-, compd. with pyridine (1:1)CatalystHCID 23665647Potassium tert-butoxideCatalyst

Procedure

To 300 mL toluene in an 500 mL flask with condenser under a nitrogen atmosphere were added 30 g (120 mmol) di(trimethylolpropane), 4, 45.6 mL (38.9 g, 300 mmol) acrolein diethyl acetal, and 1.5 g (6 mmol) pyridinium p-toluenesulfonate. The mixture was refluxed for 4 hours, then cooled to room temperature, and 0.67 g (6 mmol) potassium tert-butoxide added. The toluene was removed by evaporation under reduced pressure, and the residue distilled in a Kugelrohr apparatus (pressure 1-3 mbar, pot temperature 142-180° C.) to give 35.35 g (91% yield) of crude di[(5-ethyl-2-vinyl-[1,3]dioxan-5-yl)methyl]ether, 5, as a light yellow oil. The crude product, 30 g, was purified by chromatography on 1 Kg Merck Silica Gel 60 in a 2 L glass fritted funnel, eluting with 20:80 ethyl acetate/heptane, to give 27.8 g (71% yield) of purer product, which was re-purified by a second chromatography on 1 Kg MERCK® Silica Gel 60 in a 2 L glass fritted funnel, eluting with 10:90 ethyl acetate/heptane, to give 16.44 g (42% yield) of essentially pure di[(5-ethyl-2-vinyl-1,3dioxan-5-yl)methyl]ether. This material was used in the photoisomerization.

Workup

  1. temperatureThe mixture was refluxed for 4 hours
  2. customThe toluene was removed by evaporation under reduced pressure
  3. distillationthe residue distilled in a Kugelrohr apparatus (pressure 1-3 mbar, pot temperature 142-180° C.)

Sources & evidence

ORD record
ord-696ed745194a49a0a344a5d36ad2a15e
Source dataset
uspto-grants-2005_03
Patent number
US06863782B2

Reaction notes

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