Sodium Bicarbonate → 4,4',4''-(1-Vinyl-2-ylidene)trianisole

HRID 2050951Notes

Reaction equation

HRID 2050951 reaction equation
CC1C=CC(S(O)(=O)=O)=CC=1.O.[CH3:13][O:14][C:15]1[CH:20]=[CH:19][C:18]([C:21]([C:32]2[CH:37]=[CH:36][C:35]([O:38][CH3:39])=[CH:34][CH:33]=2)(O)[CH2:22][C:23]2[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=2)=[CH:17][CH:16]=1.C([O-])(O)=O.[Na+]>C1C=CC=CC=1>[CH3:39][O:38][C:35]1[CH:34]=[CH:33][C:32]([C:21]([C:18]2[CH:17]=[CH:16][C:15]([O:14][CH3:13])=[CH:20][CH:19]=2)=[CH:22][C:23]2[CH:28]=[CH:27][C:26]([O:29][CH3:30])=[CH:25][CH:24]=2)=[CH:37][CH:36]=1

Participants

5

Reactant 3

HCID 516892Sodium BicarbonateHCID 521998p-Toluenesulfonic acid monohydrateHCID 198342771,1,2-Tris(4-methoxyphenyl)ethan-1-ol

Product 1

HCID 815434,4',4''-(1-Vinyl-2-ylidene)trianisole

Reagents, catalysts & solvents 1

HCID 241BenzeneSolvent

Procedure

To the Grignard reagent prepared from 20 g 4-bromoanisole (107 mmol) and 2.43 g Mg turnings (107 mg-atom) in 20 mL Et2O was added 19.25 g dry (P2O5) desoxyanisoin (76 mmol) as a solid in four portions, each followed by a 50 mL wash of Et2O. The mixture was stirred at reflux 17 h, cooled to room temperature, poured onto 200 g ice and 40 mL 1N H2SO4, and filtered into a separatory funnel. 100 mL Et2O was added and the organic layer was washed with 100 mL H2O and saturated NaHCO3 (2×100 mL). The organic layer was dried (MgSO4), filtered, and the Et2O was removed under reduced pressure to give crude 1,1,2-Tris(4-methoxyphenyl)ethanol as an orange oil which crystallized (25 mL EtOH with a trace of NH4OH) as an orange solid, 18.6 g (67% crude yield), mp: 109°-127° C.; NMR δ7.47 to 6.63 (m, 12H, ArH), 3.73 (3 overlapping s, 9H, OCH3), 3.48 (s, 2H, CH2), 2.27 (s, 1H, OH). p-TsOH.H2O (2 g; 10.5 mmol) and 18.5 g of the crude carbinol (50.8 mmol) were dissolved in 50 mL C6H6, heated to reflux 2 h, cooled to room temperature, and poured onto 75 mL 5% NaHCO3. The organic layer was washed with 75 mL 5% NaHCO3. The combined aqueous layers were extracted with 25 mL C6H6. The combined organic layers were washed with 100 mL H2O, dried (Na2SO4), filtered, and the solvent removed to give a dark oil. The oil was purified on 80 g flash SiO2 (gradient elution with petroleum ether-CH2Cl 2) yielding an amber oil which solidified at room temperature to yield 1,1,2-Tris(4-methoxyphenyl)ethene as white cubes (11.3 g, 64%), mp: 100°-101° C. (lit. 100°-101° C.). NMR δ7.29 to 6.55 (m, 13H, ArH and C=CH), 3.78 (s, 3H, geminal ring OCH3), 3.75 (s, 3H, vicinal ring OCH3), 3.69 (s, 3H, central ring OCH3).

Workup

  1. customcrystallized (25 mL EtOH with a trace of NH4OH) as an orange solid, 18.6 g (67% crude yield), mp: 109°-127° C.
  2. temperatureheated
  3. temperatureto reflux 2 h
  4. washThe organic layer was washed with 75 mL 5% NaHCO3
  5. extractionThe combined aqueous layers were extracted with 25 mL C6H6
  6. washThe combined organic layers were washed with 100 mL H2O
  7. dry with materialdried (Na2SO4)
  8. filtrationfiltered
  9. customthe solvent removed
  10. customto give a dark oil
  11. customThe oil was purified on 80 g flash SiO2 (gradient elution with petroleum ether-CH2Cl 2)
  12. customyielding an amber oil which
  13. customsolidified at room temperature

Sources & evidence

ORD record
ord-6f7ed4f2d65b418a957ee9688417405d
Source dataset
uspto-grants-1991_05
Patent number
US05015666

Reaction notes

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