Potassium Iodide → 2,2-Dicarbethoxy-1-(4'-hydroxy-3',5'-dimethoxyphenyl)-6,7-methylenedioxytetralin

HRID 1112553Notes

Reaction equation

HRID 1112553 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.B(F)(F)F.C[CH2:62][O:63][CH2:64][CH3:65].[I-].[K+].C(=O)([O-])[O-:69].[Na+].[Na+].S(S([O-])=O)([O-])(=O)=O.[Na+].[Na+]>ClCCl.CCOCC>[C:3]([C:2]1([C:62]([O:63][CH2:64][CH3:65])=[O:69])[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]([OH:54])=[C:50]([O:52][CH3:53])[CH:51]=1)([O:5][CH2:17][CH3:18])=[O:4]

Participants

9

Reactant 6

HCID 4875Potassium IodideHCID 8000Boron trifluoride etherateHCID 10340Sodium CarbonateHCID 90200Thallium(III) trifluoroacetateHCID 656671Sodium PyrosulfiteHCID 12409760Ethyl 2-Carbethoxy-2-(3,5-dimethoxy-4-hydroxybenzyl)-4-(3,4-methylenedioxyphenyl)butyrate

Product 1

HCID 124097622,2-Dicarbethoxy-1-(4'-hydroxy-3',5'-dimethoxyphenyl)-6,7-methylenedioxytetralin

Reagents, catalysts & solvents 2

HCID 3283Diethyl EtherSolventHCID 6344DichloromethaneSolvent

Procedure

A suspension of thallium (III) trifluoroacetate (733 mg 1.35 mmoles) in dichloromethane (12 ml) was cooled in an ice bath, under nitrogen. Ethyl 2-carbethoxy-2-(3,5-dimethoxy-4-hydroxybenzyl)-4-(3,4-methylenedioxyphenyl)butyrate (XIII; R2 = ethyl) (474 mg, 1.00 mmoles) and boron trifluoride etherate (1.45 ml, 11.49 mmoles) were added quickly, the mixture was allowed to come to room temperature, and stirred overnight. Excess aqueous potassium iodide was added, the mixture was stirred for 30 min., made basic with sodium carbonate, and sodium metabisulphite (300 mg, 1.58 mmoles) was added. The thallium (I) iodide was removed by filtration, and washed thoroughly with chloroform. Ethyl acetate was added to the combined filtrate and washings, the organic phase was dried (brine, sodium sulphate) and the solvents were removed. An ether solution of the resulting brown solid (430 mg) was percolated through Florisil. Removal of the solvent gave a yellow oil which deposited fine white needles (260 mg, 55%) on trituration with ether. Crystallization from ether gave 2,2 -dicarbethoxy-1-(4'-hydroxy-3',5'-dimethoxyphenyl)-6,7-methylenedioxytetralin as white needles m.p. 147°-148°.

Workup

  1. temperaturewas cooled in an ice bath, under nitrogen
  2. customto come to room temperature
  3. stirringthe mixture was stirred for 30 min.
  4. additionwas added
  5. customThe thallium (I) iodide was removed by filtration
  6. washwashed thoroughly with chloroform
  7. additionEthyl acetate was added to the combined filtrate and washings
  8. dry with materialthe organic phase was dried (brine, sodium sulphate)
  9. customthe solvents were removed
  10. customRemoval of the solvent
  11. customgave a yellow oil which
  12. customCrystallization from ether

Sources & evidence

ORD record
ord-7dd47d8ceb23433e97f6006d33cd1020
Source dataset
uspto-grants-1978_10
Patent number
US04122092

Reaction notes

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