Réaction #436374

Équation de réaction

lithium

7-bromo-bicyclo[2.2.1]heptane

dry ice

→

desired compound

Bicyclo[2.2.1]heptane-7-carboxylic Acid

Solvants

tetrahydrofuran

tetrahydrofuran

Conditions de réaction

Traitement

1. 1
   Autrereaction
2. 2
   Températurecooled in an ice bath
3. 3
   workup.STIRRINGstirred for an additional 4 hours
4. 4
   TempératureThe resulting blue solution was cooled with a dry ice/acetone bath
5. 5
   workup.STIRRINGThe reaction mixture was stirred for 20 minutes, during which time the blue color
6. 6
   AutreThe dry ice bath/acetone bath was removed
7. 7
   workup.STIRRINGthe reaction was stirred for 2 hours, during which time it
8. 8
   Autrecame up to room temperature
9. 9
   workup.ADDITION2.5 N aqueous sodium hydroxide (200 mL) was added
10. 10
    workup.STIRRINGthe mixture was stirred for 5 minutes
11. 11
    AutreThe layers were separated
12. 12
    Extractionthe aqueous layer was extracted twice with diethyl ether (50 mL)
13. 13
    workup.ADDITIONmade acidic by addition of concentrated HCl
14. 14
    Extractionextracted with three portions of diethyl ether (75 mL)
15. 15
    SéchageThe combined organic layers were dried over anhydrous magnesium sulfate
16. 16
    Concentrationconcentrated

Mode opératoire

To a solution of 4-4′-di-t-butylbiphenyl (8.25 g, 31 mmol) in anhydrous tetrahydrofuran (70 mL) under a nitrogen atmosphere was added freshly cleaned lithium wire (0.21 g, 30 mmol). The resulting mixture was stirred at room temperature for 15 minutes to initiate reaction, then cooled in an ice bath and stirred for an additional 4 hours. The resulting blue solution was cooled with a dry ice/acetone bath and a solution of 7-bromo-bicyclo[2.2.1]heptane (2.0 g, 11.4 mmol) in anhydrous tetrahydrofuran (5 mL) was added in one portion. The reaction mixture was stirred for 20 minutes, during which time the blue color changed to orange. Solid dry ice was then added to the reaction, which became colorless. The dry ice bath/acetone bath was removed and the reaction was stirred for 2 hours, during which time it came up to room temperature. 2.5 N aqueous sodium hydroxide (200 mL) was added and the mixture was stirred for 5 minutes. The layers were separated and the aqueous layer was extracted twice with diethyl ether (50 mL). The aqueous layer was then made acidic by addition of concentrated HCl and extracted with three portions of diethyl ether (75 mL). The combined organic layers were dried over anhydrous magnesium sulfate and concentrated to yield the desired compound of formula (VIII) as a white solid (1.54 g, 96%), mp=74–75 ° C. (lit. mp=77.5–785° C., J. Am. Chem. Soc. 1954, 76, 4072).

Source