Experiment #4 11/1/12

Bryan Edwards TA: Yanran Ai

Alkanes and Alkenes: Preparation, Reactions and Properties

Introduction: In the first part of this experiment, 1-Chlorobutane was used to investigate the reactivity of an alkane in free-radical chlorination. Sulfuryl chloride was used to form four isomeric dichlorobutanes, and the results were determined by gas chromatography analysis. Main Reaction and Mechanism:

Free-radical chain chlorination of 1-chlorobutane Table of Reagents: Compound Sulfuryl chloride 1-chlorobutane 1,1-azobis(ABCN) M.W. (g/mol) 134.97 92.57 244.34 Physical Properties Colorless liquid/Chlorine provider Alkyl halide/more reactive than just and alkane Efficient radical initiator

Table 1: Reagents with their molecular weights and physical properties and functions

Table of Products: Compound 1,1 dichlorobutane 1,2 dichlorobutane 1,3 dichlorobutane 1,4 dichlorobutane

M.W. (g/mole) 127.01

Physical properties Clear liquid

Table 2: Provides intended products with their molecular weights and physical properties

Yield Data: Theoretical: 5mL of 1-chlorbutane = 5mL * (.88g/mL) = 4.4g = 4.4g/(92.57g/mol) = 0.0475mol 1-chlorobutane 2mL of sulfuryl chloride = 2mL * (1.67g/mL) = 3.34g = 3.34g/(134.97g/mol) = 0.0247mol sulfuryl chloride 1:1 stoichiometry between sulfuryl chloride and 1-chlorobutane reveals sulfuryl chloride as the limiting reagent. 0.0247mol sulfuryl chloride results in 0.0247mol various isomers of dichlorobutane and 0.0228mol (0.0475mol-0.0247mol) excess 1-chlorobutane. Final weight: 0.0247mol * (127.01g/mol) + 0.0228mol * (92.57g/mol) = 3.14g (dichlorobutanes) + 2.11g (1-chlorobutane) = 5.25g 7.74g initially 5.25g expected final = 2.49g loss expected *(.9) = 2.24g loss is 90% of expected loss Observed: A total of 2.26g of product and original compound was left in the final solution. (2.26g/5.25g)*100 = 43.0% yield Experimental Procedure: Apparatus was set up in hood as specified in the user manual 25-mL round-bottomed flask in thermowell heater attached to condenser and gas trap Added 0.1g of cyclohexanitrile to round-bottomed flask Measured 5mL 1-chlorobutane and then 2mL of sulfuryl chloride into the flask Stoppered and weighed flask Heated solution under gentle reflux for 20 minutes Added another 0.1 gram of cyclohexanitrile and heat for another 10 mins Weighed flask after to make sure it has lost at least 90% mass Cooled reaction mixture in ice bath and poured into 15mL ice cold saturated aqueous sodium chloride in Erlenmeyer flask Added resulting solution to separatory funnel and separated layers Washed organic layer with 10mL of 0.5M sodium bicarbonate Tested the aqueous layer for basicity Added 1mL of brine to organic mixture Added to vial containing one or two spatula tips of sodium sulfate Stirred regularly for 10-15 minutes to expedite drying process signified by liquid becoming clear Transferred dried mixture to a dry, tared sample vial using Pasteur filter-tip pipet

Weighed container and calculate amount of material isolated Performed gas chromatography test

Synopsis of Procedure: After the first heating stage, only 0.3g were lost Only lost 1.0g by the end of the distillation process The solution in the water trap never quite turned red meaning it was not absorbing much HCl The cloudy product became clear with the addition of sodium sulfate Observed Properties of Products Product was a mixture of all possible dichlorobutane isomers and the original 1-chlorobutane compound The mixture was clear and tested with gas chromatography Slightly less yield than expected, and most of product was the original compound Significant Side Reactions No significant side reactions occurred Method of Purification The final solution after the heating was placed in a separatory funnel and he organic layer was washed with the addition of sodium bicarbonate The organic mixture was then dried with sodium sulfate Finally the product was decanted into a tared vial

Flow-chart describing purification process

Interpretation of Instrumental Data

Figure 1: Gas chromatography results for products of reaction of 1-chlorobutane with sulfuryl chloride

Figure 1 shows the experimental results of the reaction described above. The top peak indicates the amount of original compound (1-chlorobutane), which is clearly the most prevalent. Unfortunately, because not all 4 peaks of the potential isomers were integrated in this GC reading, a more proper GC reading was provided by our TA that was analyzed in calculations to follow, and can be seen in figure 2 below.

Figure 2: GC readout from an experiment with good yield

Conclusions: It is clear that the second peak, which represents the original compound of 1-chlorobutane was the most prevalent in the final solution tested by the GC. Because this compound was not of any interest in calculating the relative reactivity of the different hydrogens, this peak was excluded from calculations. The very top peak is the peak associated with the solvent, and thus, was also excluded from calculations. There is also the least amount of 1,1-dichlorobutane present in the final mixture. This is most likely because the relative reactivity of the hydrogens present on the first carbon are least reactive. This is primarily due to the instability of a radical on a primary carbon. However, this reasoning applies to both 1,1-dichlorbutane and 1,4-dichlorobutane. The reason why there is less of 1,1-dichlorbutane is because chlorine has an inductive effect that makes the closest C-H bonds stronger than those further away. There is the most 1,3-dichlorobutane because radicals are more stable on secondary carbons than primary carbons. There is more of 1,3-dichlorobutane than 1,2-dichlorebutane for the same reasoning as above. The inductive effect of the chlorine on the first carbon helps to stabilize the radical on the secondary carbon further away and destabilizes the radical on the closer one. These conclusions correspond to what was expected before performing the experiment. However, the inductive effect on the carbon chain had a slightly more pronounced effect on the reactivity of hydrogens than expected. The original GC print-out portrayed an experiment with a fairly low yield. This was most likely a result of the reaction not going far enough under reflux heating. Had the reaction been heated to a greater capacity or for a longer extent of time, maybe there would have been more product. It is doubtful that more catalyst would have much of an effect on the quantity of product because there was already quite a lot of catalyst added throughout the heating. Questions: 6. ABCN was only required in a catalytic amount because it was only used in the initiation step of the mechanism. Beyond that point, chloride radicals would form from the propagation step of the mechanism. Therefore, many chlorine radicals can be created from one molecule of ABCN. 9. Caution must be used when adding the crude reaction mixture into the brine because it is possible that the mixture still contain sulfuryl chloride with reacts vigorously with water in an extremely exothermic reaction. The low temperature of the brine will limit the intensity of the heat exerted from the reaction. 15. Compound % of product Per hydrogen available Normalized 1,1-dichlorobutane 5.09 2.545% .29 1,2-dichlorobutane 21.81 10.905% 1.25 1,3-dichlorobutane 46.90 23.45% 2.69 1,4-dichlorobutane 26.20 8.73% 1
Table 3: Shows relative reactivity of hydrogen atoms throughout 1-chlorobutane

22a. The three peaks downfield at about 3.62 ppm signify the two hydrogens on carbon-1, which is bonded to the chlorine. This can be concluded for several reasons. First and foremost there is a chemical shift that has pushed these peaks downfield. What this means is that the chlorines ability to draw in the electrons has deshielded the protons causing a downfield shift. There is also a splitting pattern designated by the three peaks meaning that each hydrogen is coupled with 2 adjacent hydrogens. The area also integrates to 2 meaning there are 2 hydrogens at that carbon. The next grouping upfield is clearly the 2 hydrogens on carbon-2 because the inductive effect of the chlorine persists for its adjacent hydrogens, slightly deshielding them. There is also

a sum of 5 peaks corresponding with the 4 adjacent hydrogens on neighboring carbons. Next upfield is the other secondary carbon, which should have about peaks designating its coupling with 5 hydrogens. It should feel less of the deshielding effect of the chlorine because it is further away. Lastly, the three peaks at around 0.95 ppm signify the three hydrogens on carbon-4 as displayed by the splitting pattern resulting from the coupling with the 2 neighboring hydrogens and least deshielding from the chlorine atom.

Alcohol Dehydration to Form an Alkene

Introduction: The purpose of this lab was to explore a synthetic method for the preparation of alkenes through the acid-catalyzed dehydration of alcohols. A specific compound, 2-methylcyclohexanol was converted to boh 1-methylcyclohexene and 3-methylcyclohexene via this method. Main Reaction and Mechanism:

Figure 3: Shows the mechanism at hand in this experiment

Table of Reactants:
Compound 2-methylcyclohexanol (cis and trans) Sulfuric Acid Mol. Wt. (g/mol) 114.19 Amounts Used (mL) grams 5.0 4.65 Moles used 0.0407 required 0.0407 Theoretical Physical Properties Bp: 171-173 C Density: 0.93g/mL Corrosive Acid, colorless to slightly yellow
o

98.08

3.0

0.027

0.027

Table 4: Shows all the reagents in the mechanism above

Limiting Reagent = 2-methylcyclohexanol Table of Products:

Compound Mol. Wt. (g/mol) Theoretical Yields 1(or 3)-methyl96.17 3.91g cyclohexene Table 5: Shows a table of the expected products and their yield.

Physical Properties Colorless liquid, irritant

Yield Data: Theoretical: 0.0407 moles of 2-methylcyclohexanol will theoretically all be converted to 1- or 3-cylcohexene. Therefore, 0.0407mol*96.17g/mol = 3.91g of both products combined. Observed: 2.58g of product (2.58g/3.91)*100 = 66.0% yield Synopsis and Notes on Experimental Procedure: Added 5mL of cis-/trans- mixture of 2-methylcyclohexanol in 50-mL round-bottomed flask Added 3mL of 9M sulfuric acid Attached to a fractional distillation apparatus with steel sponge Collected distillation in 10mL graduated cylinder in ice-bath Recorded distillate volume and temperatures periodically Washed with 10mL of water then 10mL of aqueous sodium hydroxide, then 10mL of water Drained organic layer into 25mL Erlenmeyer and dry with calcium chloride Stirred, then transferred to tared vial Final solution must was clear after it was dried Weighed product and calculate percent yield Then performed saturation tests via bromine test and Baeyer test Added a drop of product into 0.1M bromine Solution was colorless after many drops of bromine meaning there was unsaturation Cyclohexane turned orange immediately Baeyer test resulted in a brown precipitate immediately with product Obtained IR and GC of product Observed Physical Properties of Product Obtained: Final solution was colorless and passed as a positive test for unsaturation in both bromine and Baeyer tests Achieved a fairly high yield for the colorless liquid Significant Side Reactions: There were no significant side reactions. (The production of methylenecyclohexane was not significant) Method of Purification: Crude organic mixture was first washed in a separatory funnel with water, then sodium hydroxide, then water. Organic mixture was separated then dried with calcium chloride.

Flow-chart of purification process Interpretation of Instrumental Data:

Figure 4: Gas chromatography printout for the 2 isomers of methylcyclohexene

Figure 4 shows that 3-methylcyclohexene made up a smaller percentage of the product and has a shorter retention time than 1-methylcyclohexene.

Figure 5: Infrared Radiation spectrum for product printout

The peak at 332.50cm-1 symbolizes the stretching of C-H bonding for sp2 hybridized carbons. The broad peak at 2940.01cm-1 represents the C-H stretching for sp3 hybridized carbons. The theoretical IR charts in the manual specifying pure samples of each product individually reveal that the 3-methylcyclohexene had more of a peak above the 3000cm-1 range which makes sense because there are more hydrogen atoms in this isomer that are bonded to an sp2 carbon. There are 2 in that isomer and only 1 in the 1methylcyclohexene molecule. Conclusions: