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Diiodomethane → Ethyl [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate

HRID 223794
Notes
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Reaction equation

HRID 223794 reaction equation
[CH2:1](I)I.[Cl:4][C:5]1[C:17]([Cl:18])=[C:16]([O:19][CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH:15]=[C:14]2[C:6]=1[C:7]1[C:12]([CH:26]=[CH2:27])([CH2:13]2)[CH2:11][CH2:10][C:9](=[O:28])[CH:8]=1>O1CCCC1.C1(C)C=CC=CC=1.[Cu].[Zn]>[Cl:4][C:5]1[C:17]([Cl:18])=[C:16]([O:19][CH2:20][C:21]([O:23][CH2:24][CH3:25])=[O:22])[CH:15]=[C:14]2[C:6]=1[C:7]1[C:12]([CH:26]3[CH2:1][CH2:27]3)([CH2:13]2)[CH2:11][CH2:10][C:9](=[O:28])[CH:8]=1
ParticipantsProcedureWorkupSources & evidenceReaction notes

Participants

6

Reactant 2

HCID 6346DiiodomethaneHCID 86738256Ethyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate

Product 1

HCID 86738255Ethyl [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]acetate

Reagents, catalysts & solvents 3

HCID 10290809Zinc copper coupleCatalystHCID 1140Toluene
Solvent
HCID 8028TetrahydrofuranSolvent

Procedure

A mixture of the zinc-copper couple, prepared as described above, (48 gm.) and methylene iodide (37.5 gm.) in tetrahydrofuran (300 ml.) is heated under reflux in a nitrogen atmosphere for an hour. Ethyl [(5,6-dichloro-3-oxo-9a-vinyl-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetate (8.2 gm., 0.02 mole) is added to the cooled mixture and stirring continued at 25° C. for 24 hours. The mixture is diluted with toluene (200 ml.), filtered and the filtrate is washed successively with saturated aqueous solutions of ammonium chloride and sodium bicarbonate and then with water. The organic lager is dried over anhydrous magnesium sulfate and the solvent removed using a rotary evaporator at reduced pressure. The residue is purified by column chromatography using a silica-gel column to give ethyl [(5,6-dichloro-9a-cyclopropyl-3-oxo-1,2,9,9a-tetrahydro-3H-fluoren-7-yl)oxy]-acetate.

Workup

  1. customprepared
  2. temperatureis heated
  3. temperatureunder reflux in a nitrogen atmosphere for an hour
  4. filtrationfiltered
  5. washthe filtrate is washed successively with saturated aqueous solutions of ammonium chloride and sodium bicarbonate
  6. dry with materialThe organic lager is dried over anhydrous magnesium sulfate
  7. customthe solvent removed
  8. customa rotary evaporator at reduced pressure
  9. customThe residue is purified by column chromatography

Sources & evidence

ORD record
ord-d3a1e9862eb24150ac83cd257af94940
Source dataset
uspto-grants-1982_10
DOI
10.6084/m9.figshare.5104873.v1
Patent number
US04356313

Reaction notes

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On this pageParticipantsProcedureWorkupSources & evidenceReaction notes