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A number of reactions require the slow and controlled addition of a solution containing one reagent to another. Attempting to control the flow rate over a number of hours using a conventional constant pressure addition funnel is a frustrating exercise; commercially available constant volume addition funnels are expensive and must be adjusted by trial and error each time a reaction is carried out. The use of an (expensive) peristaltic pump or syringe pump overcomes these problems but can introduce other complications. We have recently had occasion to carry out the synthesis of thioether macrocycles and cages requiring the slow and controlled addition of DMF solutions of (offensively odoriferous) thiols or (air-sensitive) thiolates to a reactant solution under nitrogen(1), Although the use of a syringe pump was called for, there are obvious difficulties associated with purging the solution and assembling such an apparatus under nitrogen, and we report a simple and inexpensive solution.
A Male Luer Lock tip (recovered from a broken syringe) was sweated onto the flattened tip of a pressure-equalizing addition funnel and a syringe needle was attached. Judicious selection of needle length, bore size, and reactant volume can be used to control the addition time simply and reproducibly. With a 250-mL funnel, the flow rate changes by <25% from the beginning to the end of the addition. (In fact, a reduction in the rate of addition may even be advantageous as the reaction proceeds, the reagent in the receiving flask is consumed, its concentration drops, and the rate of reaction will decrease). A piece of fine Teflon tubing of appropriate length attached to the needle can be used to reduce the flow rate even further, but this is only necessary for very slow rates of addition. For example, the time of addition of 200 mL, of an ethanolic solution could be varied from approximately 5 minutes (150mm/17 gauge) to approximately 5 h (200mm/22 gauge), and once the addition time for a particular needle length/bore is determined, the tap on the addition funnel is turned fully on, so no adjustment is necessary. When needles with a particularly fine bore are used, a small plug of glass wool should be inserted in the constriction above the tap, to filter the solution and prevent blockage of the needle. An inert atmosphere is readily maintained throughout the system. The elimination of atmospheric contamination, containment of odors and controlled slow addition have led to improved yields and less complaints from fellow inhabitants of the laboratory!
Literature Cited
1. Osvath, P.; Sargeson, A. M.; Skelton, B. W.; White, A. H. J. Chem. Soc., Chem. Commun. 1991, 1036. Osvath. P.; Sargeson, A. J. Chem. Soc., Chem. Commun. 1993, 40.
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