Tetrahydrofuran → 5-Chloro-9-isopropylidene-1,4-dihydro-1,4-methano-naphthalene

HRID 39410

Reaction equation

HRID 39410 reaction equation
Br[C:2]1[C:7](Cl)=[CH:6][CH:5]=[CH:4][C:3]=1[Cl:9].C([Mg]Cl)(C)C.O1CCCC1.[CH3:20][C:21]([CH3:27])=[C:22]1[CH:26]=[CH:25][CH:24]=[CH:23]1>C1(C)C=CC=CC=1>[Cl:9][C:3]1[CH:4]=[CH:5][CH:6]=[C:7]2[C:2]=1[CH:23]1[C:22](=[C:21]([CH3:27])[CH3:20])[CH:26]2[CH:25]=[CH:24]1

Participants

6

Reactant 4

HCID 8028TetrahydrofuranHCID 295681-Bromo-2,6-dichlorobenzeneHCID 1374671,3-Cyclopentadiene, 5-(1-methylethylidene)-HCID 178418918HCID 178418918, compound

Product 1

HCID 578576065-Chloro-9-isopropylidene-1,4-dihydro-1,4-methano-naphthaleneYield 87.8%

Reagents, catalysts & solvents 1

HCID 1140TolueneSolvent

Procedure

A solution of 2-bromo-1,3-dichlorobenzene (22.59 g, 0.1 mol) in dry toluene (100 ml) under a nitrogen atmosphere was reacted at −8 to −15° C. with 2M isopropylmagnesium chloride in tetrahydrofuran (50 ml, 0.1 mol) for 1 hour. Subsequent addition of 6,6-dimethylfulvene (13.03 g, assay 97.8%, 0.12 mol) at 0° C. was followed by heating to reflux temperature for 10 hours. Aqueous work up with saturated aqueous ammonium chloride and ethyl acetate extraction followed by washings with brine and water and drying over sodium sulphate gave the crude material which was purified by chromatography on silica gel in hexane to give the desired product (19.03 g, assay 95.2% by g.l.c., 83.6% yield) as a yellow solid. This reaction is also disclosed in WO 2007/068417.

Workup

  1. temperatureby heating
  2. temperatureto reflux temperature for 10 hours
  3. extractionAqueous work up with saturated aqueous ammonium chloride and ethyl acetate extraction
  4. washfollowed by washings with brine and water
  5. dry with materialdrying over sodium sulphate
  6. customgave the crude material which
  7. customwas purified by chromatography on silica gel in hexane

Sources & evidence

ORD record
ord-0153af4bec6c4c0a81eca3ce9422b924
Source dataset
uspto-grants-2013_09
Patent number
US08524915B2

Linked notes

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