Fred Ernsberger Chem 203, section 2 TA: Travis Lap Report 6 Due 10/20/2010

Infrared and Mass Spectrum Analyses of Distillation products of Acid-catalyzed Elimination Reactions of 2-Methyl Cyclohexanol and 4-Methyl Cyclohexanol

Ernsberger 2 The purpose of this experiment was to perform an acid catalyzed elimination reaction of a Cyclohexanol, as well as distillations and analyses of the product(s). Several runs of steam distillations were used to help purify and increase the yield of the reaction. Mass Spectrum (MS) and infrared spectrum (IR) analyses were used to determine the identity of the products and their relative abundances. Purification of products formed from elimination reactions of secondary alcohols can be difficult to achieve. The reason being the two products have very similar chemical properties. The only difference between them is where the double bond forms. Figure 1. shows how the bond can be formed on neighboring bonds. When the hydrogen ion interacts with the alcohol group, it pulls the lone pair of electrons off and forms water. This single molecule elimination reaction causes the water molecule to separate from the molecule leaving behind a positively charged carbon atom. Since this molecule is unstable (due to the carbocation), there will be bond rearrangements to establish stability. This will cause the hydrogens on neighboring carbons to lose their bond. This allows for the formation of a double bond. Since there are two neighboring carbons with hydrogens, both of them will be inclined to form double bonds in this manner. For the 2-methyl cyclohexanol there are two main products; methyl cyclohexene and 3-methyl cyclohexene. Due to the possible substitutions, the 3-methyl cyclohexene is the most likely substitution. This is due to the two chances (two hydrogen bonds) for substitution on the third carbon from the methyl. The 1-methyl cyclohexene only has one possible substitution, the hydrogen attached to the same carbon as the methyl group. Therefore it is expected that the 3-methyl cyclohexene would be twice as likely as the as the 1-methyl cyclohexene. The expected ratio would be 66% 3-methyl cyclohexene to 33% 1-methyl cyclohexene. The best way to remove the product is to distill it out of the solution. As the product is removed from reaction, it will push the equilibrium to produce more products according to Le Chatelier's principle. This will increase the yield of the product and will remove more of the reactant from the organic layer. Thus when aqueous layer is removed there should be a higher concentration of the products. Once the products are formed a mass spectrum and infrared spectrum analysis can prove to be useful tools for determining the identity of the products and their ratios. The

Ernsberger 3 mass spectrum allows the user to determine the molecular weight of the products and the mass of some of the fragments. Thus a molecule can have a distinct molecular weight and molecular weight for its fragments. The relative area of the peaks corresponding to the molecules and their fragments can show the proportion of all of the components. The infrared analysis allows the analysis of molecular bonds by irradiation with electromagnetic energy. When the bonds are irradiated they only accept a certain frequency of radiation which then gives off a distinct infrared spectrum. Thus by interpreting the reaction to the radiation the functional groups of the molecule can be determined. If the infrared spectrum (IR spectrum) does not have a peak in the 3400-3650 cm-1 range then there is no alcohol left and all of the products have been converted.

Materials And Methods

Synthesis of Methylcyclohexenes: Mixed 15ml of 4-methylcyclohexanol and 4 ml of 85%phosphoric acid. Used the Hayden McNeil setup for a steam distillation apparatus (Hayden McNeil et. al. page 139-140,145), distilled the heated mixture until there were only a few millimeters of solution left. The temperature was not allowed to exceed 120 degrees centigrade. A separatory funnel was used to drain off the aqueous layer. Then this was washed twice with 5ml of saturated sodium chloride and twice again with 10 ml of .5M sodium bicarbonate. Then the organic layer was allowed to dry over anhydrous sodium sulfate for 10 minutes. Purification of Methylcyclohexenes: The product from the synthesis was then distilled again using the Hayden McNeil apparatus (Hayden McNeil et. al. pg 139-140,145). The product was collected when the temperature stabilized around 70 degrees Celsius. The distillation was not run to dryness.

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Results: Percent yield for the individual products based on GC/MS analysis:
Table 1: Relative abundance of products from 4-methyl cyclohexanol reaction. 3-Methyl 1-Cyclohexene 16.5% 4-Methyl 1-Cyclohexene 16.5% 1- Methyl 1-Cyclohexene 38% Table 1: Summary of the percent abundance from figure 3 A and B. Percent abundance readings from a Gas chromatography analyses of an acid-catalyzed elimination reaction of 4-methyl cyclohexanol. The synthesis reaction and purification was run with the steam distillation set up from the Hayden and McNeil lab notebook pages 139-140,145.

Table 2: Relative abundance of products from 2-methyl Cyclohexanol reaction: figure 5 A, B, and C 3-Methyl 1-Cyclohexene 34% figure 5c Methylene Cyclohexane 21 % figure 5b 1-Methyl 1-Cyclohexene 42% figure 5a Table 2: Summary of the percent abundance from figure 5 A, B, and C. Percent abundance readings from a Gas chromatography analyses of an acid-catalyzed elimination reaction of 2-methyl cyclohexanol. The synthesis reaction and purification was run with the steam distillation set up from the Hayden and McNeil lab notebook pages 139-140,145. Table 3: Percent yield values from 4-methyl hexanol products:

RT Value 3.47 4.17 9.15

area 8567 774 1950

total area 11291 11291 11291

percent 8567/11291= 75.9 6.8 17.3

Table 4: Percent yield values from 2-methyl hexanol products: RT 3.58 4.34 16.06 16.34 Area 685 10708 165 123 Total area 11681 11681 11681 11681 Percent yield 5.864 91.67 1.41 1.053

Ernsberger 5 Figure 1. Synthesis of 1-Methyl Cyclohexene and 3-Methyl Cyclohexene from 2- Methyl Cyclohexane.

The addition of hydrogen to the mixture draws off the lone pair of electrons from the oxygen on the hydroxyl group. When this happens water is formed and the bond holding the water molecule to the cyclohexane breaks. From there, the reaction proceeds in two possible directions. With a positive charge formed on the second carbon in the ring, one of the hydrogens loses its bond which allows the formation of a double bond. This causes bond between either the first and second carbon, or the second and third carbon.

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Figure 2. GC Analysis of the Relative Abundance of products and reactants of acid-catalyzed elimination of 4-methyl Cyclohexanol

The above figure shows a gas chromatography analysis of the products and reactants from an acid-catalyzed elimination of 4-methyl Cyclohexanol. The products were synthesized with a steam distillation apparatus from the Hayden McNeil Lab book. The products were then purified at a constant temperature to give the final distillate. Percent yield of all of the products was determined by subtracting the starting alcohol material and dichloromethane percentages from 100 percent. Data from Group 2 and 3 (Chem 203, Fall 2011).

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Figure 3 (A and B). GC Analysis of Relative Abundance of the products for an acid-based elimination reaction of 4-methylcyclohexanol. A.

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B.

Figure 3 A and B show the Gas chromatograph analysis of the acid based elimination of 4-methyl Cyclohexanol. The relative abundance of each of the products and their fragments can be determined from the figures. The products were synthesized with a steam distillation apparatus from the Hayden McNeil Lab book. The products were then purified at a constant temperature to give the final distillate. Data from Group 2 and 3 (Chem 203, Fall 2011).

Ernsberger 9 Figure 4. GC Analysis of the Relative Abundance of products and reactants of acid-catalyzed elimination of 2-methyl Cyclohexanol

The above figure shows a gas chromatography analysis of the products and reactants from an acid-catalyzed elimination of 2-methyl Cyclohexanol. The products were synthesized with a steam distillation apparatus from the Hayden McNeil Lab book. The products were then purified at a constant temperature to give the final distillate. Percent yield of all of the products was determined by subtracting the starting alcohol material and dichloromethane percentages from 100 percent. Data from Group 2 and 3 (Chem 203, Fall 2011).

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Figure 5 A, B, and C. GC Analysis of Relative Abundance of the products for an acid-based elimination reaction of 2-methylcyclohexanol

A.

B.

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C.

Figure 5 A, B, and C show the Gas chromatograph analysis of the acid based elimination of 4-methyl Cyclohexanol. The relative abundance of each of the products and their fragments can be determined from the figures. The products were synthesized with a steam distillation apparatus from the Hayden McNeil Lab book. The products were then purified at a constant temperature to give the final distillate. Data from Group 2 and 3 (Chem 203, Fall 2011).

Discussion: Both of the products for 4-methyl cyclohexanol and 2-methyl cyclohexanol had 3 methyl cyclohexens. The 4-methyl cyclohexanol had relative abundance values of: 3-methyl cyclohexene (16.5%), 4-methyl cyclohexene (16.5%), and 1-methyl cyclohexene (38%) (Table 1). The 2-methyl cyclohexanol had relative abundance values of: 3-Methyl 1-Cyclohexene (34%), Methylene Cyclohexane (21 %), and 1-Methyl 1-Cyclohexene (42%) (Table 2.). Neither reaction yielded the expected products in their expected ratios. This may have been due to the constant heating and heat fluctuations. Further experiments could look into whether there are any effects of heat on the ratio of the products. Both of the reactions yielded both 3-methyl cyclohexene and 1-methyl cyclohexene. The 4-methyl cyclohexanol yielded; 75.9% 1-methyl 1-cyclohexene, while the other two products could not be distinguished because they had the same relative abundance (table 1 and 3). The 2-methyl cyclohexanol yielded 91.67 1-methyl

Ernsberger 12 cyclohexene, 5.864% 3-methyl cyclohexene, 1.41% methylene cyclohexane (based off table 4 and 2). The fourth product was the original alcohol. There were two products that were not shared between the two elimination reactions. Methylene cyclohexane was only synthesized through the 2-methyl cyclohexnol reaction (table 2). Whereas, 4-methyl cyclohexene only formed from the 4-methyl cyclohexanol reaction (table 1). Given the results, it would be advisable to only use either 2-methyl cyclohexanol or 4-methyl cyclohexanol if the goal would be the formation of their respective unique products. If either the 3-methyl cyclohexene or the 2-methyl cyclohexene are the desired product, then 2-methyl cyclohexanol would be the advised starting reactant, it has a higher overall percent yield and specific yield for the two common products. Some of the problems with isolating and purifying the products came from the setup of the steam distillation apparatus. The temperature was difficult to control, often it would require temperatures close to the 120 degree limit in order to get the distillate to travel to the condenser tube without condensing too soon and dripping back down into the heated mixture. However, when the temperature rose to the upper limit of 120 degrees, the solution ran the risk of running a heavy boil which could affect the quality of the product. If the temperature was too low, no distillate would form at all. Future experiments should use a longer condenser tube with a smaller diameter. This would increase the cooling surface area to heated vapor volume ratio. This would allow for a faster cooling of the distillate which may increase the speed of the system.