反応 #1818739

反応方程式

1-hydroxyoctahydro-4,7-methano-iso-benzofuran

4-carboxybutyl-triphenyl-phosphonium bromide

hydrogen

NaH

→

6-(3-hydroxymethylbicyclo[2.2.1]-hept-2-yl)-hex-5-enoic acid

収率 129.7%

溶媒

dimethylsulphoxide

dimethylsulphoxide

water

dimethylsulphoxide

反応条件

後処理

1. 1
   workup.STIRRINGis stirred at 20° C. for 3 hours
2. 2
   workup.DISTILLATIONthe solvent is distilled off in vacuo
3. 3
   その他the evaporation residue is partitioned between 200 ml of water and 4×400 ml of diethyl ether
4. 4
   その他the precipitate which deposits is separated off
5. 5
   洗浄washed 3, times with 200 ml of diethyl ether
6. 6
   抽出extracted 5 times with 200 ml of diethyl ether
7. 7
   その他After the combined ethereal extracts have been dried
8. 8
   その他the solvent is evaporated off in vacuo
9. 9
   その他the residue is chromatographed on silica gel

実験手順

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).

出典