Ethyl Acetate → HCID 15158793, compound

HRID 2392969Notes

Reaction equation

HRID 2392969 reaction equation
[H-].[Al+3].[Li+].[H-].[H-].[H-].[CH:7]12[CH2:16][CH:11]3[CH2:12][CH:13]([CH2:15][CH:9]([CH2:10]3)[C:8]1=O)[CH2:14]2.[Si:18]([O:25][C:26]1[CH:27]=[C:28]([CH:35]=[CH:36][CH:37]=1)[C:29]([O:31][CH2:32][CH2:33][Cl:34])=O)([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19].C(OCC)(=O)C>C1COCC1.CCCCCC.[Cl-].[Cl-].[Cl-].[Ti+3]>[Cl:34][CH2:33][CH2:32][O:31][C:29](=[C:8]1[CH:9]2[CH2:15][CH:13]3[CH2:12][CH:11]([CH2:16][CH:7]1[CH2:14]3)[CH2:10]2)[C:28]1[CH:35]=[CH:36][CH:37]=[C:26]([O:25][Si:18]([C:21]([CH3:24])([CH3:23])[CH3:22])([CH3:20])[CH3:19])[CH:27]=1

Participants

8

Reactant 4

HCID 8857Ethyl AcetateHCID 64151AdamantanoneHCID 151587922-Chloroethyl 3-t-butyldimethylsilyloxybenzoateHCID 21226445Aluminium lithium hydride2×

Product 1

HCID 15158793HCID 15158793, compound

Reagents, catalysts & solvents 3

HCID 10313229titanium(III) trichlorideCatalystHCID 8028TetrahydrofuranSolventHCID 8058HexaneSolvent2×

Procedure

A three neck flask was purged with argon and charged with 400 mL of anhydrous THF. Titanium trichloride (48 g, 0.3 mol) was added with stirring and the flask was cooled in an ice bath. Lithium aluminum hydride (6.0 g, 0.16 mol) was added in small portions causing a brief exothermic reaction. After all of the LAH was added, the cooling bath was removed and the mixture warmed to room temperature. Triethylamine (30 mL) was added and the black mixture was refluxed for 1.5 hours under argon. A solution of adamantanone (14 g, 93 mmol) and 2-chloroethyl 3-t-butyldimethylsilyloxybenzoate (10 g, 31 mmol) in 50 mL of dry THF was added dropwise while reflux was continued. After an additional 10 min, TLC (5% ethyl acetate in hexane) indicated conversion of the ester to new material so the mixture was cooled and diluted with 3 L of hexane. The hexane was decanted, filtered through filter paper and evaporated leaving an oil which was purified by column chromatography on silica gel, eluting with 0-3% ethyl acetate in hexane yielding 8.68 g of alkene (65% based on ester); 1H NMR (CDCl3) δ0.195 (s,6H), 0.983 (s,9H), 1.78-1.98 (m,12H), 2.65 (br s,1H), 3.334 (br s,1H), 3.55 (t,2H), 3.66 (t,2H), 6.85-7.29 (m,4H). ##STR14##

Workup

  1. customA three neck flask was purged with argon
  2. additioncharged with 400 mL of anhydrous THF
  3. temperaturethe flask was cooled in an ice bath
  4. customa brief exothermic reaction
  5. customthe cooling bath was removed
  6. additionTriethylamine (30 mL) was added
  7. temperaturethe black mixture was refluxed for 1.5 hours under argon
  8. temperaturewhile reflux
  9. temperaturewas cooled
  10. customThe hexane was decanted
  11. filtrationfiltered
  12. filtrationthrough filter paper
  13. customevaporated
  14. customleaving an oil which
  15. customwas purified by column chromatography on silica gel
  16. washeluting with 0-3% ethyl acetate in hexane yielding 8.68 g of alkene (65% based on ester)

Sources & evidence

ORD record
ord-7626406b8c814e5f88f839d210d86fa7
Source dataset
uspto-grants-1998_09
Patent number
US05804103

Reaction notes

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