Mirah Gertz Prof. Blackford Chem 3BL 20 March 2024 1. CHEM 3BL Lab G: Chemoselectivity in Transfer-Hydrogenation Reactions (Exp. 36) 2. Safety Considerations a. Make sure that the piece of tubing is not clogged and that the damp cotton is packed loosely in the inverted test tube to prevent the buildup of pressure Substrates and the reaction products are mild irritants and dermal contact should be minimized. If you spill any on your skin, wash the affected area with soap and water and inform the instructor. Do not weigh the Pd/C and the ammonium formate on the same weighing paper. Hydrogen gas is generated when the two come in contact and a fire can occur. Hydrogen is also generated during these reactions, so make sure that there are no flames. Palladium on carbon can be pyrophoric when exposed to air, especially when it is dry. Immediately after use, the weigh paper used for the Pd/C should be submerged in the container of water for Pd/C waste in the hood. Make sure you put the top back on. the container of Pd/C. d. Do not place your face over the reaction flask when sampling for TLC. The ammonia generated is an irritant. e. Itis important that the sand bath temperature remain below 80°C to prevent the ammonium formate from subliming and clogging the gas trap tubing which would result ina closed system. A closed system will cause pressure to build up and the septum to blow off.{. Palladium on carbon can be pyrophoric when exposed to air, especially when itis dry. Immediately after use, the Pasteur pipette containing the Pd/C should be put in the specially labeled container of water in the fume hood. 3. Reaction Table a a ris “gy 3 my ea { OS boa ye CO oe - ree im oe Ww - yur F wna WL yw 3 “Sg 2-ppert-wne —Uingrin oy Woy! ga yinsl £8.06 gle Ls Dy Ht my woe OT. mmol 31 ine! y 2 ronan BER 4. Procedure a. Spot a solution of your substrate in lane 1 of a TLC plate that can accommodate three lanes. b. Set up a gas trap as described. Insert the tubing into the septum and then attach the septum to the side arm of an inverted distillation head. Place a second septum on the top of the distillation head. c. Weigh 150 mg of the assigned substrate and place it in a 5-mL long-neck round-bottom flask along w! a stir bar. Add 30 mg of 10% palladium on carbon and 1 mL. of methanol Calculate number of mmol of the substrate weighed and add 7.5 equivalents of ammonium formate followed by an additional 1 mL of methanol 4. Spot the reaction mixture in lane 2 of the TLC plate and label itAttach the inverted distillation head that is connected to the gas trap. Heat the reaction on the sand bath while stirring the reaction mixture. Monitor the reaction every 10 minutes by TLC using lane 3 of the first TLC plate and additional plates as necessary, AI TLC plates of cinnamic acid derivatives should be developed in 98:2 ethyl acetate:acetic acid and all plates of the ketone should be developed in 80:20 hexane:ethyl acetate. The plates should be visualized using UV light and iodine. When the TLC indicates that the reaction is complete or after 50 minutes, whichever comes first, remove the reaction mixture from the sand bath and allow it to cool to room temperature. Filter the reaction mixture into a large test tube using the glass-fiber Pasteur pipette method. Rinse the reaction flask with an additional 0.5 mL of methanol and pass this, through the filter. Coo! the filtrate in an ice-water bath for 10 minutes. If crystals are apparent after ten minutes, allow the system to stand undisturbed until no more crystals appear to be forming. Isolate the crystals by filtering on a Hirsch funnel ‘and wash them with cold 2-propanol. Dry the crystals and obtain a weight and a melting Point, Dissolve some of the crystals in an appropriate solvent and spot the solution on a TLC plate. Compare the result obtained with the first TLC plate that contained the starting material and the reaction mixture. If no crystals are apparent after ten minutes, transfer the filtrate to a fiter flask and remove the methanol by evaporation using a vacuum source that is equipped with a cold trap and heating gently. Do not overheat the solution. The product may be an cil Add 4.5 mL of 1M HCI to the flask and 3 mL of ether. Swirl the contents of the flask until everything has dissolved. Transfer this mixture to a centrifuge tube, cover it, and shaketo mix the contents well. After the layers separate, transfer the organic layer to a large test tube. m. Extract the aqueous layer with an additional 1.5 mL of ether and add the ether layer to the organic layer in the large test tube. Dry the combined organic layers with sodium sulfate. Spot some of this solution on a TLC plate. 1. Transfer the dried ether solution to a tared 10-mL beaker and evaporate the ether in the fume hood using a stream of air. ©. If you obtain a solid product after evaporation of the ether, take a melting point and dissolve some of the crystals in an appropriate solvent. Spot the solution on a TLC plate. Compare the result obtained with the first TLC plate that contained the starting material and the reaction mixture. p. If you obtain an oil, compare the TLC result obtained from the dry ether solution with the first TLC plate that contained the starting material and the reaction mixture. 4. Note: rather than puncturing your septum with a syringe needle, use a prevented septum with plastic tubing already inserted Observations [Mean Lee 0.82 y, | ose” ye “a8 by | Uiiwe Ath a mot, 08 Y ° 0 Jue 1 HO tg |