Реакция #93451
ord-d74292f5e3e445ac84a57d79d918cf8e
Уравнение реакции
Реактанты
Реагенты
Условия реакции
Обработка
- 1workup.ADDITIONAfter completion of the addition
- 2Температураthe mixture was heated
- 3Температураto reflux for another 30 minutes
- 4workup.WAITThe yellow colouration which appeared initially disappeared after a few minutes
- 5ТемператураThe mixture, warmed to -15° C.
- 6Экстракцияextracted three times with 50 ml of diethyl ether each time
- 7ПромывкаThe organic phases were washed with 50 ml of saturated sodium chloride solution
- 8Сушкаdried over magnesium sulphate
- 9Концентрированиеconcentrated
Методика
122 mg of magnesium shavings were covered with 3 ml of absolute tetrahydrofuran in a sulphonation flask under argon gasification, and, after the addition of a crystal of iodine, treated with a solution of 1.24 g of trans-1-(bromomethyl)-4-pentylcyclohexane in 7 ml of absolute tetrahydrofuran. After completion of the addition, the mixture was heated to reflux for another 30 minutes and then the mixture, cooled to -78° C., was treated with 0.7 ml of a 0.1N solution of dilithium tetrachlorocuprate in tetrahydrofuran and subsequently with a solution of 670 mg of 4,4'-bis(bromomethyl)biphenyl in 10 ml of absolute tetrahydrofuran. The yellow colouration which appeared initially disappeared after a few minutes. The mixture, warmed to -15° C., was subsequently stirred for a further 17 hours, then treated with 25 ml of 2N hydrochloric acid and extracted three times with 50 ml of diethyl ether each time. The organic phases were washed with 50 ml of saturated sodium chloride solution, dried over magnesium sulphate and concentrated. Low-pressure chromatography (0.5 bar) of the residue (1.06 g) on silica gel with hexane and subsequently with hexane/diethyl ether (19:1) as the eluent gave in sequence 1,1'-ethylene-bis(trans-4-pentylcyclohexane), 228 mg (22%) of 4,4'-bis[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl, 78 mg (9 %) of 4-(bromomethyl)-4'-[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl as well as 4,4'-bis(bromomethyl)biphenyl. A single crystallization of the 228 mg of 4,4'-bis[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl from hexane yielded 194 mg of colourless needles having a clearing point above 300° C. (further phase transitions at 68° C., 84° C., 161° C., 203° C., 221° C. and 224° C.). Rf-values (hexane): 4,4'-bis(bromomethyl)biphenyl 0.14; 4-(bromomethyl)-4'-[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl 0.24; 4,4'-bis[2-(trans-4-pentylcyclohexyl)ethyl]biphenyl 0.40.