Isopropanol → Ethyl 12,12-Dimethyl-12H-dibenzo[d,g][1,3]dioxocin-6-carboxylate

HRID 1110655Notes

Reaction equation

HRID 1110655 reaction equation
[C:1]([C:11]1[CH:16]=[CH:15][CH:14]=[CH:13][C:12]=1[OH:17])([C:4]1[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=1[OH:10])([CH3:3])[CH3:2].[OH-].[K+].Cl[CH:21](Cl)[C:22]([OH:24])=[O:23].[OH-].[Na+].[CH:28](O)(C)[CH3:29]>O.CO.O>[CH3:2][C:1]1([CH3:3])[C:4]2[CH:9]=[CH:8][CH:7]=[CH:6][C:5]=2[O:10][CH:21]([C:22]([O:24][CH2:28][CH3:29])=[O:23])[O:17][C:12]2[CH:13]=[CH:14][CH:15]=[CH:16][C:11]1=2

Participants

8

Reactant 5

HCID 3776IsopropanolHCID 6597Dichloroacetic Acid2×HCID 14797Potassium Hydroxide2×HCID 14798Sodium HydroxideHCID 5771572,2-Bis(2-hydroxyphenyl)propane

Product 1

HCID 22153853Ethyl 12,12-Dimethyl-12H-dibenzo[d,g][1,3]dioxocin-6-carboxylate

Reagents, catalysts & solvents 2

HCID 962WaterSolventHCID 22242641Methanol--water (1/1)Solvent

Procedure

A mixture of 2,2'-isopropylidene bisphenol (3.65 g, 0.01594 mol), potassium hydroxide (2.68 g of 85 percent, 0.0478 mol) and dichloroacetic acid (1.31 ml, 0.01594 mol) in 65 ml cf isopropyl alcohol is heated at reflux. After 20 hours at reflux, an additional 1.79 g of 85 percent KOH and 1.31 ml of dichloroacetic acid are added and the reaction mixture is heated at reflux for 2 days. The reaction mixture is then diluted with 200 ml of H2O, acidified by the addition of concentrated HC1 (10 ml) and extracted into ethyl acetate. The ethyl acetate solution is washed with brine, dried over MgSO4 and concentrated. The residue is washed with petroleum ether to afford 3.7 g of crude product as a red-brown syrup. This material is then purified by an esterification-saponification-esterification procedure (esterification agent methanol, H2SO4). Dry column chromatography yields 0.97 g of crude product, which is saponified (NaOH, MeOH-H2O ), and purified by dry column chromatography to afford 0.60 g of a white solid. Esterification of this material (EtOH, H2SO4) and purification by preparative thin layer chromatography (elution with 1:4 ethyl acetate-hexanes) yields 0.25 g of product as a clear syrup: IR (neat) 3.34, 5.65, 6.95, 8.2, 13.2 cm-1; 1H NMR (CDCl3) δ1.28 (t, 3, CH2CH3), 1.75 and 1.9 (2s, 6, (CH3)2C), 4.24 (q, 2 CH2CH3), (s, 1, CH), 6.9-7.6 (m, 8, Ar--H); m/e 312.

Workup

  1. temperatureis heated
  2. temperatureat reflux
  3. temperatureAfter 20 hours at reflux
  4. temperaturethe reaction mixture is heated
  5. temperatureat reflux for 2 days
  6. additionacidified by the addition of concentrated HC1 (10 ml)
  7. extractionextracted into ethyl acetate
  8. washThe ethyl acetate solution is washed with brine
  9. dry with materialdried over MgSO4
  10. concentrationconcentrated
  11. washThe residue is washed with petroleum ether
  12. customto afford 3.7 g of crude product as a red-brown syrup
  13. customThis material is then purified by an esterification-saponification-esterification procedure (esterification agent methanol, H2SO4)
  14. customDry column chromatography
  15. customyields 0.97 g of crude product, which
  16. custompurified
  17. customby dry column chromatography

Sources & evidence

ORD record
ord-2afce5381bba4d569507cc847c3cedd5
Source dataset
uspto-grants-1990_12
Patent number
US04976770

Reaction notes

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