Triethylamine → 5-ethenyl-2,2-dimethyl-4H-1,3-benzodioxin-4-one

HRID 1583108Notes

Reaction equation

HRID 1583108 reaction equation
[CH3:1][C:2]1([CH3:21])[O:7][C:6]2[CH:8]=[CH:9][CH:10]=[C:11](OS(C(F)(F)F)(=O)=O)[C:5]=2[C:4](=[O:20])[O:3]1.[CH2:22]([Sn](CCCC)(CCCC)C=C)[CH2:23]CC.[Cl-].[Li+].C(N(CC)CC)C>O1CCOCC1.C1C=CC([P]([Pd]([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)([P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)[P](C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)(C2C=CC=CC=2)C2C=CC=CC=2)=CC=1>[CH:22]([C:11]1[C:5]2[C:4](=[O:20])[O:3][C:2]([CH3:21])([CH3:1])[O:7][C:6]=2[CH:8]=[CH:9][CH:10]=1)=[CH2:23]

Participants

7

Reactant 4

HCID 8471TriethylamineHCID 81998TributylvinyltinHCID 433294Lithium ChlorideHCID 108927482,2-Dimethyl-4-oxo-4H-benzo[D][1,3]dioxin-5-YL trifluoromethanesulfonate

Product 1

HCID 113677065-ethenyl-2,2-dimethyl-4H-1,3-benzodioxin-4-oneYield 81%

Reagents, catalysts & solvents 2

HCID 178418397HCID 178418397, compoundCatalystHCID 312751,4-DioxaneSolvent

Conditions

Temperature
100 °C

Procedure

A mixture of 2,2-dimethyl-5-trifluoromethanesulfonyloxy-4H-1,3-benzodioxin4-one (9.90 g, 30.3 mmol), tributyl(vinyl)tin (10.10 g, 31.9 mmol), lithium chloride (8.70 g, 205 mmol), and triethylamine (5.0 mL, 36.0 mmol) in 1,4-dioxane (300 mL) was deoxygenated by bubbling nitrogen through the mixture for 1 h. To the mixture was added tetrakis(triphenylphosphine)palladium (3.40 g, 2.90 mmol) and the mixture was heated at 100° C. for 3 h. The mixture was allowed to cool to rt and was filtered. The filtrate was concentrated and purified by flash chromatography (1:12, EtOAc/hexanes) to provide 5-ethenyl-2,2-dimethyl-4H-1,3-benzodioxin-4-one (5.00 g, 81%) as a yellow oil: 1H NMR: (CDCl3) δ1.72 (s, 6H), 5.43 (dd, J=11.0, 1.3 Hz, 1), 5.72 (dd, J=17.5, 1.3 Hz, 1 Hz, 1H), 6.89 (d, J=8.0 Hz, 1H), 7.27 (d, J=8.0 Hz, 1H), 7.47 (t, J=8.0 Hz, 1H), 7.73 (dd, J=17.5, 11.0 Hz, 1H).

Workup

  1. customwas deoxygenated
  2. customby bubbling nitrogen through the mixture for 1 h
  3. temperatureto cool to rt
  4. filtrationwas filtered
  5. concentrationThe filtrate was concentrated
  6. custompurified by flash chromatography (1:12, EtOAc/hexanes)

Sources & evidence

ORD record
ord-ac9870afc73846da890d4a4ecf3e11f7
Source dataset
uspto-grants-2004_05
Patent number
US06740777B2

Reaction notes

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