Sodium hydride → HCID 54450935, compound

HRID 1731557Notes

Reaction equation

HRID 1731557 reaction equation
[H-].[Na+].[H][H].[Br-].[C:6]([CH2:9][CH2:10][CH2:11][CH2:12][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([OH:8])=[O:7].O[CH:33]1[CH:41]2[CH:36]([CH:37]3[CH2:42][CH:40]2[CH2:39][CH2:38]3)[CH2:35][O:34]1>CS(C)=O.O>[OH:34][CH2:35][CH:36]1[CH:37]2[CH2:42][CH:40]([CH2:39][CH2:38]2)[CH:41]1[CH:33]=[CH:12][CH2:11][CH2:10][CH2:9][C:6]([OH:8])=[O:7]

Participants

7

Reactant 4

HCID 24758Sodium hydrideHCID 161236(4-Carboxybutyl)triphenylphosphonium bromideHCID 13504705Octahydro-4,7-methano-2-benzofuran-1-olHCID 178418361HCID 178418361, compound

Product 1

HCID 54450935HCID 54450935, compoundYield 129.7%

Reagents, catalysts & solvents 2

HCID 679Dimethyl SulfoxideSolvent3×HCID 962WaterSolvent

Procedure

12 g (0.4 mole) of 80% strength NaH are added to 240 ml of absolute dimethylsulphoxide under an inert gas, and the mixture is warmed at 60° to 70° C. until the evolution of hydrogen has ended. Thereafter, 88.4 g (0.2 mole) of 4-carboxybutyl-triphenyl-phosphonium bromide in 200 ml of absolute dimethylsulphoxide are added at 15° to 16° C. After the mixture has been subsequently stirred for 10 minutes, 15.4 g (0.1 mole) of 1-hydroxyoctahydro-4,7-methano-iso-benzofuran in 50 ml of absolute dimethylsulphoxide are allowed to run in and the mixture is stirred at 20° C. for 3 hours. 20 ml of water are then added, the solvent is distilled off in vacuo and the evaporation residue is partitioned between 200 ml of water and 4×400 ml of diethyl ether. The aqueous phase is brought to pH 3.5 with 5N hydrochloric acid and the precipitate which deposits is separated off and washed 3, times with 200 ml of diethyl ether. The aqueous phase which remains is saturated with sodium chloride and extracted 5 times with 200 ml of diethyl ether. After the combined ethereal extracts have been dried, the solvent is evaporated off in vacuo and the residue is chromatographed on silica gel using methylene chloride/tetrahydrofuran/acetic acid (10:1:0.5). 30.9 g of 6-(3-hydroxymethylbicyclo[2.2.1]-hept-2-yl)-hex-5-enoic acid are obtained in this manner (65% yield).

Workup

  1. stirringis stirred at 20° C. for 3 hours
  2. distillationthe solvent is distilled off in vacuo
  3. customthe evaporation residue is partitioned between 200 ml of water and 4×400 ml of diethyl ether
  4. customthe precipitate which deposits is separated off
  5. washwashed 3, times with 200 ml of diethyl ether
  6. extractionextracted 5 times with 200 ml of diethyl ether
  7. customAfter the combined ethereal extracts have been dried
  8. customthe solvent is evaporated off in vacuo
  9. customthe residue is chromatographed on silica gel

Sources & evidence

ORD record
ord-22b38f1cff1e49f9b8ac8a5758595124
Source dataset
uspto-grants-1986_11
Patent number
US04622339

Reaction notes

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