Methanol → Methyl Spiro(cyclopropane-1,12'(12'H)-dibenzo[d,g][1,3]dioxocin)-6'-carboxylate

HRID 359181Notes

Reaction equation

HRID 359181 reaction equation
[CH:1]1[C:12]2[C:11]3([CH2:14][CH2:13]3)[C:10]3[CH:15]=[CH:16][CH:17]=[CH:18][C:9]=3[O:8][CH:7]([C:19]([OH:21])=[O:20])[O:6][C:5]=2[CH:4]=[CH:3][CH:2]=1.S(=O)(=O)(O)O.[CH3:27]O>>[CH:15]1[C:10]2[C:11]3([CH2:13][CH2:14]3)[C:12]3[CH:1]=[CH:2][CH:3]=[CH:4][C:5]=3[O:6][CH:7]([C:19]([O:21][CH3:27])=[O:20])[O:8][C:9]=2[CH:18]=[CH:17][CH:16]=1

Participants

4

Reactant 3

HCID 887MethanolHCID 1118Sulfuric AcidHCID 14839706Spiro(cyclopropane-1,12'(12'H)-dibenzo[d,g][1,3]dioxocin)-6'-carboxylic Acid

Product 1

HCID 14839707Methyl Spiro(cyclopropane-1,12'(12'H)-dibenzo[d,g][1,3]dioxocin)-6'-carboxylate

Procedure

The crude spiro(cyclopropane-1,12'(12'H)-dibenzo[d,g][1,3]dioxocin)-6'-carboxylic acid from Example 3 was dissolved in 500 ml of methanol and 2.0 ml of sulfuric acid added. The mixture was heated at reflux and stirred for 3 hours. About half of the methanol was removed by evaporation under reduced pressure and the remaining solution was diluted with 1.5 1 of ether. The solution obtained was extracted several times with water and then with brine and was then dried over magnesium sulfate, filtered, and concentrated by evaporation under reduced pressure to obtain the title compound in impure form. This was purified by filtration chromatography, eluting with a 9:1 mixture of hexane and ether to obtain the product as a pale yellow crystalline solid. This was recrystallized from methanol to obtain 9.55 g of the title compound as pale tan crystals melting at 123°-126° C. The proton and carbon NMR and infrared spectra were consistent with the assigned structure.

Workup

  1. temperatureThe mixture was heated
  2. temperatureat reflux
  3. customAbout half of the methanol was removed by evaporation under reduced pressure
  4. additionthe remaining solution was diluted with 1.5 1 of ether
  5. customThe solution obtained
  6. extractionwas extracted several times with water
  7. dry with materialwith brine and was then dried over magnesium sulfate
  8. filtrationfiltered
  9. concentrationconcentrated by evaporation under reduced pressure

Sources & evidence

ORD record
ord-a53d987bc8e540d29be5b0d1943bc919
Source dataset
uspto-grants-1991_03
Patent number
US04999448

Reaction notes

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