1,2-Dichloroethane → 2,2-Dicarbethoxy-1-(3',4',5'-trimethoxyphenyl)-6,7-methylenedioxytetralin

HRID 1112554Notes

Reaction equation

HRID 1112554 reaction equation
F[C:2](F)(F)[C:3]([O-:5])=[O:4].[Tl+3].FC(F)(F)[C:11]([O-:13])=[O:12].F[C:17](F)(F)[C:18]([O-])=O.C([C:28]([CH2:45][C:46]1[CH:51]=[C:50]([O:52][CH3:53])[C:49]([OH:54])=[C:48]([O:55][CH3:56])[CH:47]=1)([CH2:34][CH2:35][C:36]1[CH:41]=[CH:40][C:39]2OCO[C:38]=2C=1)C(OCC)=O)(OCC)=O.S(=O)(O)[O-].[Na+].S(OC)(O[CH3:66])(=O)=O.[C:69](=[O:72])([O-])[O-:70].[K+].[K+].Cl[CH2:76][CH2:77]Cl>CC(C)=O.O>[C:3]([C:2]1([C:69]([O:70][CH2:17][CH3:18])=[O:72])[CH2:38][CH2:39][C:40]2[C:28](=[CH:34][C:35]3[O:13][CH2:11][O:12][C:36]=3[CH:41]=2)[CH:45]1[C:46]1[CH:47]=[C:48]([O:55][CH3:56])[C:49]([O:54][CH3:66])=[C:50]([O:52][CH3:53])[CH:51]=1)([O:5][CH2:76][CH3:77])=[O:4]

Participants

9

Reactant 6

HCID 111,2-Dichloroethane2×HCID 6497Dimethyl SulfateHCID 11430Potassium CarbonateHCID 90200Thallium(III) trifluoroacetateHCID 12409760Ethyl 2-Carbethoxy-2-(3,5-dimethoxy-4-hydroxybenzyl)-4-(3,4-methylenedioxyphenyl)butyrateHCID 23665763Sodium Bisulfite

Product 1

HCID 227636672,2-Dicarbethoxy-1-(3',4',5'-trimethoxyphenyl)-6,7-methylenedioxytetralin

Reagents, catalysts & solvents 2

HCID 180AcetoneSolventHCID 962WaterSolvent

Procedure

Thallium (III) trifluoroacetate (6.5 g; 11.96 mmoles) was suspended in 1,2-dichloroethane (75 ml) and heated to reflux under nitrogen. Ethyl 2-carbethoxy-2-(3,5-dimethoxy-4-hydroxybenzyl)-4-(3,4-methylenedioxyphenyl)butyrate (XIII) (4.2 g, 8.86 mmoles) in 5 ml of 1,2-dichloroethane was then added and the reaction mixture became deep red. Refluxing was continued for 30 min. The solution was cooled, poured into saturated sodium bisulfite, and turned yellow. The aqueous layer was extracted with ethyl acetate and the organic layer was washed with saturated sodium bicarbonate, water, and saturated brine, and was dried over sodium sulfate. Filtration and evaporation gave a brown oil which was dissolved in 50 ml of acetone. To this was added 3 ml of dimethyl sulfate and 18 g of anhydrous potassium carbonate. This mixture was refluxed overnight, cooled and poured into water. The aqueous phase was extracted with chloroform and the chloroform was washed with water and saturated brine, and dried over sodium sulfate. Filtration and evaporation gave a brown oil which, when triturated with methanol, gave 1.8 g of the title product (XIV-b; R2 = ethyl). Chromatography of the methanol residue on silica gel (1/l ether/cyclohexane) gave an additional 0.5 g (55% total yield). Recrystallization from methanol gave a white solid (mp 149°-152°).

Workup

  1. temperatureheated
  2. temperatureto reflux under nitrogen
  3. temperatureRefluxing
  4. temperatureThe solution was cooled
  5. extractionThe aqueous layer was extracted with ethyl acetate
  6. washthe organic layer was washed with saturated sodium bicarbonate, water, and saturated brine
  7. dry with materialwas dried over sodium sulfate
  8. filtrationFiltration and evaporation
  9. customgave a brown oil which
  10. temperatureThis mixture was refluxed overnight
  11. temperaturecooled
  12. extractionThe aqueous phase was extracted with chloroform
  13. washthe chloroform was washed with water and saturated brine
  14. dry with materialdried over sodium sulfate
  15. filtrationFiltration and evaporation
  16. customgave a brown oil which, when
  17. customtriturated with methanol

Sources & evidence

ORD record
ord-2da76db653ba49bb8afd60d531d30a79
Source dataset
uspto-grants-1978_10
Patent number
US04122092

Reaction notes

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