Thionyl Chloride → HCID 21852188, compound

HRID 617419Notes

Reaction equation

HRID 617419 reaction equation
[CH3:1][O:2][C:3]1[CH:8]=[CH:7][C:6]([C:9]2[CH:17]=[CH:16][C:12]3[O:13][CH2:14]O[C:11]=3[C:10]=2[C:18]([OH:20])=O)=[CH:5][CH:4]=1.[Cl-].[Al+3].[Cl-].[Cl-].S(Cl)(Cl)=[O:26]>C(Cl)Cl>[CH3:1][O:2][C:3]1[CH:4]=[C:5]2[C:6]([C:9]3[CH:17]=[CH:16][C:12]4[O:13][CH2:14][O:26][C:11]=4[C:10]=3[C:18]2=[O:20])=[CH:7][CH:8]=1

Participants

5

Reactant 3

HCID 24386Thionyl ChlorideHCID 6451240Aluminum(III) ChlorideHCID 21852183HCID 21852183, compound

Product 1

HCID 21852188HCID 21852188, compoundYield 45%

Reagents, catalysts & solvents 1

HCID 6344DichloromethaneSolvent2×

Procedure

Crude 5-(4-methoxyphenyl)-1,3-benzodioxole-4-carboxylic acid was dissolved in thionyl chloride (10 mL) and refluxed for 6 h. The reaction was cooled to ambient temperature and the solvent was removed by rotary evaporation to give the crude acid chloride. The acid chloride was dissolved in methylene chloride (10 mL) and added to a suspension of aluminum chloride (0.67 g, 5.00 mmol) in methylene chloride (10 mL). The reaction was stirred at ambient temperature for 4 h and quenched with a mixture of ice and concentrated HCl. The mixture was extracted with methylene chloride and dried with magnesium sulfate and concentrated by rotary evaporation to afford 89 mg of 8-methoxy-10H-fluoreno[1,2-d]-1,3-dioxol-10-one (0.35 mmol, 45% yield). 1H NMR (300 MHz, CDCl3) δ 7.54 (d, J=8.3 Hz, 1H), 7.10 (d, J=8.3 Hz, 1H), 7.06 (d, J=2.2, 1H), 6.88 (dd, J=8.3, 2.2 Hz, 1H), 6.90 (d, J=8.3 Hz, 1H), 6.15 (s, 2H), 3.86 (s, 3H). Sodium hydride (21 mg, 0.53 mmol) was suspended in THF (5 mL) and diethyl cyanomethylphosphonate (94 mg, 0.53 mmol) was slowly added to the suspension. After 15 min a yellow solution resulted and a solution of 8-methoxy-10H-fluoreno[1,2-d]-1,3-dioxol-10-one (89 mg, 0.35 mmol) in THF (5 mL) was added dropwise. The solution was allowed to stir at ambient for 16 h. The solvent was removed by rotary evaporation and the residue was taken up in methylene chloride, washed with water, and dried with magnesium sulfate. The solvent was removed by rotary evaporation to yield the crude Horner-Emmons product as an orange solid.

Workup

  1. temperaturerefluxed for 6 h
  2. customthe solvent was removed by rotary evaporation
  3. customto give the crude acid chloride
  4. customquenched with a mixture of ice and concentrated HCl
  5. extractionThe mixture was extracted with methylene chloride
  6. dry with materialdried with magnesium sulfate
  7. concentrationconcentrated by rotary evaporation

Sources & evidence

ORD record
ord-4acd838e2e7a42428f0803e202c31409
Source dataset
uspto-grants-1999_09
Patent number
US05948817

Reaction notes

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