金属有机-1.ppt

金 属 有 机 化 学 程延祥 Storage and transfer: Forced over by nitrogen pressure Or syphoned(虹吸) The transfer procedure: The syringe is flushed with inert gas. If the organomeganesium solution is being withdrawn from a closed vessel, a positive internal pressure is maintained by passing inert gas through the septum. (alternatively, the syringe is filled with inert gas, which is forecd into the vessel before the solution is withdrawn.). Slightly more than the required volume of solution is drawn into the syringe. The tip of the needle is then raised above the surface of the solution, and some inert gas is drawn into the syringe. The syringe is withdrawn and immediately inverted, and the plunger is advanced until the barrel is just filled by the solution. The required amount of the solution is dispensed into the receiver. The excess of solution is discharged into a quenching medium(e.g. an ethyl acetate or acetone-hydrocarbon mixture) and the syringe is immediately flushed out, disassembled, cleaned and dried.(hydrolysis and oxidation products of organomagnesium compounds can rapidly “seize” syringes, taps, stoppers, etc.) Typical assemblies for reactions: Detection and estimation: Preparation: 1. By reactions of metallic magnesium Mg: turnings, chips, powder; Activation: mechanical; by halogens; by alloying; by “entrainment”(MeI, EtBr) Cyclohexylmagnesium chloride(traditional Grignard reagent): Magnesium turnings (Grignard grade; 26.7g, 1.1mol) and sodium-dried ether(100ml) are placed in a 1 litre flask, fitted with a dropping funnel, condenser, and stirrer, and with calcium chloride guard tubes protecting the dropping funnel and condenser. Redistilled chlorocyclohexane(15ml) and a crystal of iodine are added, and the mixture is heated gently without stirring until the reaction starts (~5-10min). Ether (125ml) is added , and the stirrer is started. A cooling bath is prepared. The remainder of a total of 118.5g (121ml, 1.0mol) of chlorocyclohexane, mixe