204 Introduction to Organic Laboratory Techniques: A Microscale Approach dle Davi, Lampman, Kei Engel Ea EXPERIMENT 24 Elimination Reactions: Dehydration and Dehydrohalogenation Dehydration Dehydrobromination Collection of gaseous products Gas chromatography Regiochemistry Zaitsev's Rule Alkenes can be prepared by elimination reactions such as the dehydration of alcohols and the dehydrobromination of alkyl bromides. Dehydration reactions follow an E1 mechanistic pathway, whereas dehydrobromination occurs by an E2 mechanism. In this experiment, you will study both meth- ods for preparing alkenes. In the first reaction, an alcohol undergoes dehydration in the presence of strong acid to form an alkene. In many cases, alcohols give a mixture of alkenes, including cis and trans isomers. For example, 2-butanol gives a mix- ture of L-butene, cis-2-butene, and trans-2-butene. The class will study the dehydration of 1-butanol and 2-butanol. The general reaction for dehydra- tion is the following: R-G-E-R a aC + 0 HR teat’ is The second reaction is an example of a dehydrobromination reaction conducted in the presence of potassium hydroxide dissolved in ethanol. You will study the dehydrobromination of 1-bromobutane and 2-bromobutane, The general reaction for dehydrobromination is the following: ia r R—C—C—R —_kou + KBr+H,O TT CH,CH,OH HR eat OR R The products of the dehydration and dehydrobromination reactions, which are gases at room temperature, can be analyzed by gas chromatogra~ phy. For each reaction, the relative percentages of the alkenes can then be calculated. Using your knowledge of the mechanisms of dehydration and dehydrobromination, and by applying Zaitsev’s Rule, you should be able to explain the regiochemistry of these reactions.Experiment 24 m Elimination Reactions: Dehydration and Dehydrotalegenation 2 REQUIRED READING Review: Techniques 5, 6, and 22 New: Technique 7 Reaction Methods, Section 7.9 Before beginning this experiment, review the appropriate chapters on eli ination reactions in your lecture textbook. Pay special attention to dehydr tion of alcohols, dehydrohalogenation of alkyl halides, E1 and E2 reactior and Zaitsev’s Rule. SPECIAL INSTRUCTIONS ‘These experiments can be conveniently scheduled with another experime because the time required for each experiment is 30-45 minutes. By sche: uling these experiments over two laboratory periods, the waiting time f the gas chromatograph will also be minimized. You may be given a choi of doing one of the reactions in this experiment, of your instructor me assign one to you. In either case, you will need to share your results wi other students so that you can write the laboratory report. SUGGESTED WASTE DISPOSAL Dispose of all halide wastes in the halogenated waste container. The alcoh: mixtures from the dehydration reactions should be placed in the contain designated for that purpose. NOTES TO THE INSTRUCTOR Because of the logistics involved, consider pairing students for this exper ment. This experiment was designed to use a specific apparatus for collec ing the products (see figure in this experiment). Depending on the type « glassware used by your students, it may be necessary to modify the appar tus described here. See Technique 7, Section 7.9, page 610, for possible moc ifications. You might find it useful to prepare the gas-collection apparatus i advance of the class and to reuse it in future classes. Itis particularly difficu to insert sections of Pasteur pipets into the plastic tubing, and this should b prepared for the students in order to avoid accidents. It is also recommende to keep the 16 X 90-mm sections of glass tubing used for collecting gases. ‘A Gow-Mac model 69-350 or another traditional type of thermal cor ductivity gas chromatograph may be prepared as follows: column, injecto « detector, and outlet should be at room temperature; carrier gas flow rat , 20 mL/min. An 8-foot column containing 20% DC-710 gives good separé “ tion. Retention times: I-butene, 7 min; trans-2-butene, 8 min; and cis-2 butene, 9 min. Conditions for a Hewlett Packard model 5890 with thermal conductiv ity detector are as follows: 6-foot X %-inch column filled with 3% SP-210 (a methyl silicone) on 100/120 Supelcoport, available from Supelco; over temperature cryogenically cooled to ~20°C with COp; helium carrier gas flov : rate, 14.1 mL/min; detector temperature, 101°C; injector temperature, 40°C column head pressure, 17 psi. A capillary gas-chromatographic column i206 Introduction 1 Organic Laboratory Techniques: A Microscale Approach fe w Pavia, Larapman, Kriz, Engel not recommended, Packed columns, such as the one indicated, work better. A Hewlett Packard model 3393A Integrator may be set at attenuation 3; chart speed 2; area rejection 0; threshold 0; peak width 0.04. Retention times: I-butene, 1.4 min; trans-2-butene, 1.6 min; and cis-2-butene, 1.8 min. ‘The percentages of alkenes obtained from each reaction are listed in the Instructor’s Manual Determine in advance how much gaseous sample to inject into your gas. chromatograph. The syringe mentioned in the experimental procedure works well with the Gow-Mac chromatograph. With the Hewlett Packard chromatograph, a 5-L sample works well. It is recommended that you use a gas-tight syringe for small samples. PROCEDURE Apparatus Assemble the apparatus shown in the figure (p. 207), but do not connect the coni- al vial to the thermometer adapter (see individual experiments for the size of the conical vial needed). The section of the Pasteur pipet that fits into the thermometer adapter is prepared from a 5%-inch Pasteur pipet. Your instructor may have pre- pared the gas-collecting equipment for you. Ifa collection device is unavailable, then break off the wide end of the pipet about 1 inch from where the constriction begins. Connect the narrow end of the Pasteur pipet to the %-inch flexible plastic tubing. Heat the plastic tubing briefly above a flame before attaching it to the Pasteur pipet. This holps to soften and expand the tubing. While the tubing is stil soft, twist it until itis firmly attached to the Pasteur pipet. Accidental cuts or gouges to the skin may occur If the plastic tubing is not softened prior to attachment. Insert the wide end of the Pasteur pipet into the thermometer adapter. Use a tight- fitting O-ring to create a better seal around the section of the Pasteur pipet and tighten the cap on the thermometer adapter. Be sure the connection between the pipet and the thermometer adaptor is gas-tight. If there is a leak, you will not collect any gaseous products. Make a mark on both the test tube and the glass tube corresponding toa volume of 4 mL. This can be done by inserting a rubber septum into the 16-mm (.D,) glass tube and then filing each tube with 4 mL. of water. Using a water- resistant: marking pen, mark each tube at the level-of the water. Fill 2 400-ml. beaker with water. Place one end of the flexible plastic tubing into the beaker so that it points slightly upward. (You may want to hold it in position by wrapping the plastic tubing with wire or by inserting the plastic tubing into a section of glass tubing bent into a U shape.) Now fill he test tube completely with water ‘and, while holding your thumb over the opening, invert the test tube and place the open end into the beaker. Once the tube is in the water, you can release your thumb and allow the test tube to rest on the bottom of the beaker. Lift the test tube slightly and position it over the end of the plastic tubing without allowing air to enter the test tube. Repeat ths filing operation with the glass tube sealed by the rubber septum, but do not insert the flexible tubing into it. The test tubeExperiment 24 m Elimination Reactions: Dehydration and Dehydrohalogenation 20 |— casos removed wa yringe Futbor sopt Fron ass ube (.0. 16 mm eaten)” aly fed wath war Main air I Tes oe 1% 100 mn poo iy tod wah ator ot Patou pipet IY cap wan oving — thermometer aasptor ~ cap with O-ing + conicat vial ‘Screen and ion ring Apparatus for collecting products. will be used to collect the first 2-4 ml of gas, which will consist mainly of Then insert the flexible tubing into the open end of the glass tube to collect the gaseous products. Proceed to Experiment 24A or 24B and adjust the temperature of the alu- minum block or sand bath to the temperatures listed in that experiment. Dehydration of 1-Butanol and 2-Butanol PROCEDURE Adjust the aluminum block or sand bath to the following initial temperatures, depending on which aleohol you are using: 140°C for 1-butanol 80°C for 2-butanol To a 3-ml‘conical-vial, add 0.20 mL of either 1-butanol or 2-butanol and a mag netic spin vane, Using the graduated pipet provided, add 0.90 mL of the mixtureIntroduction to Organic Laboratory Technique A Microscale Approach e Pavia, Lampman, Ki, Engel of concentrated phosphoric acid and concentrated sulfuric acid" to the vial. Stir the mixture for a few seconds, Connect the thermometer adapter to the vial and place the vial in the alu. minum block or sand bath as shown in the figure. If you are using a sand bath, Secure the assembly with a clamp. Stir the mixture and increase the heat slowly until 4 mL of gas (mainly ait) are collected in the inverted test tubo. Carefully remove the test tube from the flexible tubing and place the glass tube with the rubber septum over the flexible tubing. Continue heating the reaction mixture (increasing the temperature if necessary) until you collect 45 ml. of the gaseous Products. It should not be necessary to heat the reaction mixture much above 170°C for 1-butanol or 100°C for 2-butanol Before turning the heat down or removing the vial from the heating device, You must first remove the flexible tubing from both the gas-collection tube and Water bath or disconnect the thermometer adapter from the conical vial. Otherwise, water may be sucked back into the vial as the reaction mixture cools. Be sur to {eave the tube containing the product in the water when you perform this oporatio With minimal delay, analyze your gaseous mixture on the gas chromatograph, Using a i-ml. syringe, remove about 0.5 ml. of gaseous product by injecting the needle through the rubber septum. (Note: Your instructor may want you to use a different type of syringe or different amount of gaseous sample; see Notes to {he Instructor.) With assistance from the instructor or lab assistant, analyze thie ‘sample on the gas chromatograph. The order of elution will be 1-butene, trans. 2-butene, and cis-2-butene, Once the gas chromatograph has been obtained, determine the relative amounts of the products (see Technique 22, Section 22.12, p. 810). Triangulation is the preferred method of determining the rolative areas under the peaks (use a millimeter ruler). Record the percentage of the three alkenes in the product. BEET cxeceimens 248 Dehydrobromination of 1-Bromobutane and 2-Bromobutane °ROCEDURE. Adjust the aluminum block or sand bath to the following initial temperatures, depending on which bromoalkane you are using: 90°C for 1-bromobutane 80°C for 2-bromobutane {te id mixture should be prepared or the entire clas by mixing 6 mio concen trated phosphoric acl anc 5.0 aL of concentrated sultan sell ioe once eh Provide enough acid for 20 students, assuming lite spillage osatier ge een Bispense hss witha gradcatel pen ea ‘its[Experiment 24 a Elimination Reactions: Dehydration and Dehydrohalogenation —2{ Dehydrobromination of 1-Bromobutane Using the graduated pipet provided, add 3.0 mL. of an ethanolic potassiu hydroxide solution? to a 5-mL conical vial. Avoid getting any of the base on th ground-glass joint. Put a thin layer of stopcock grease on the ground-glass joint the thermometer adapter. Add 0.32 mL of 1-bromobutane and a spin vane to th vial, (Alternatively, at your instructor's option, use 3.0 mL of 1M potassium ter butoxide solution and 0.32 mL. of 1-bromobutane.®) Attach the thermometer adapt to the vial and place this assembly in an aluminum block or sand bath as shown i the figure. If using a sand bath, clamp the apparatus to hold it more securely. While stiring, slowly increase the temperature of the heating source until ga begins to collect in the test tube. Continue heating the reaction mixture at this ter perature or slightly higher until about 2 mL. of gas (mainly air) are collected in th test tube. Carefully remove the test tube from the flexible tubing and place th glass tube with the rubber septum over the flexible tubing. Continue to heat the r ‘action mixture until you collect 4 ml. of gaseous product in the tube or until ga evolution ceases. Ethanolic potassium hydroxide produces less gaseous produc than the reaction with potassium fert-butoxide. With minimal delay, analyze you gaseous mixture on the gas chromatograph, as described in Experiment 244, Before turning down the heat or removing the heating source, you must first, remove the flexible tubing from both the gas-collection tube and water bath or disconnect the thermometer adapter from the conical vial. Otherwise, water may be sucked back into the vial. Be sure to leave the tube containing the product in the water when you pertofm this operation. Dehydrobromination of 2-Bromobutane Using the graduated pipet provided, add 2.0 mL of an ethanolic potassiun hydroxide solution? to a 3-mL. conical vial. Put a thin layer of stopcock grease or the ground-glass joint of the thermometer adapter. Add 0.16 mL of 2-bromobutan land a spin vane to the vial. Attach the thermometer adapter to the vial and place this assembly in an aluminum block or sand bath as shown in the figure. If using sand bath, clamp the apparatus to hold it more securely. While stirring, slowly increase the temperature of the heating source until ga begins to collect in the test tube. Continue heating the reaction mixture at this tem perature or slightly higher until 2 ml. of gas (mainly air) are collected in the tube Carefully remove the test tube from the flexible tubing and place the glass tube with the rubber septum over the flexible tubing. Continue to heat the reaction mix ture until 4~5 mL. of gaseous product are collected in the tube, 2), Read the caution statement on page 208 before turning down the heat. Jo prepare enough solution for 20 students (assuming litle spillage or other types o waste), add 15.0 g of potassium hydroxide to 50.0 mL of 95% ethanol. Stir the mixture “until the potassium hydroxide is completely dissolved. Dispense this solution with a ‘graduated pipet and bulb. "The 1M potassium tert-butoxide in 2-methyl-2-propanol is available from Aldrich Chemical €o,, catalog number 33,134-1. Dispense this solution with a graduated pipet and bulb. The reagent is extremely moisture-sensitive and must be kept tightly stop- pered when not in use.210 Introduction to Ongenic Laboratory Techmiques: A Microscale Approach tle Pavia, Lampman Kriz, Engel With minimal time delay, analyze your gaseous mixture on the gas chromato- graph, as described in Experiment 24A. Determine the percentages of three alkenes produced by the dehydrobromination of 2-bromobutane. REPORT (EXPERIMENTS 24A AND 24B) Tho data from all students will be collected and shared with everyone so that your laboratory report will reflect the results obtained by the class. Record your percent ‘age composition and the average percentages of the isomeric butenes obtained bby the class for 1-butanol, 2-butanol, 1-bromobutane, and 2-bromobutane. Using your knowledge of the mechanisms of dehydration and dehydrobromination, and by applying Zaitsev’s Rule, you should be able to explain the regiochemistry of these reactions. Compare the amount of trans-2-butene to ois-2-butene and com- are the total amount of the 2-butenes to 1-butene, Are these relative amounts Consistent with Zaitsev's Rule and the mechanisms of the reactions? Make this com- parison for all four compounds and then, in a general way, compare the results ‘obtained from the dehydration of 1-butano! and 2-butanol with the results obtained from the dehydrobromination of 1-bromobutane and 2-bromobutane. Provide mech- anisms for each reaction, -REFERENCES Leone, S. A., and Davis, J. D. “The Dehydrohalogenation of 2-Bromobutane: A Simple Illustration of Anti-Saytzeff Elimination as a Laboratory Experiment for Organic ‘Chemisty.” Journal of Chemical Education, 69 (1992): A175. Gilow, Hi. M. “Microscale Elimination Reactions.” Journal of Chemical Education, 69 : (1992): A265. QUESTIONS 7 1. Give the mechanism for the dehydration of 1-butanol. Why might you expect that the dehydration of 2-butanol would produce a similar composition of alkenes? 2. Give the mechanism for the dehydrobromination of L-bromobutane in the presence of either potassium fert-butoxide or alcoholic potassium hydroxide. 3. Why is there a big difference in the regioselectivity of the dehydration of 1-butanol compared with the dehydrobromination of 1-bromobutane? oc 4. Explain the order of elution you observed while performing the gas chromatog- raphy for this experiment. What property of the product molecules seems to be the ‘most important in determining the relative retention times? 5. What alkenes (including cis and trans isomers) would be produced by the dehydra- tion of the following alcohols? Where possible, predict the relative amounts of each product according to Zaitsev’s Rule. G@) 3-Pentanol (b) 2-Methyl-2-butanol : (© 1-Butanol (@) 2-Methyl-1-butanol 6. What alkenes (including cis and trans isomers) would be produced by the dehydro- bromination of the following alkyl bromides? Where possible, predict the relative amounts of each product according to Zaitsev’s rule. (@) 2-Bromo-2-methylbutane (b) 1-Bromobutane (© 2-Bromo-23-dimethylbutane . (@) 3-Bromopentane