XXXXXX XXX Organic Chemistry Lab 2203 011 XX XX, 2013

Experiment 9: The E1 Elimination of Reaction: Dehydration of 2-Butanol performed on XX/XX/2013 Objective: The dehydration of 2-butanol to produce a mixture of gaseous alkene products. The alkene gases are then separated and identified using gas chromatography (GC). The results of the GC illustrate the variety of pathways that are available to acid-catalyzed elimination reactions of secondary alcohols via carbocation to create different structural isomers. Experimental Procedure: Experiment 9 was followed as described in Mayo, pages 209216, with the following modifications: The volume of the reagents was doubled from 100L of 2-butanol and 50L of concentrated sulfuric acid to 200 L and 100L respectively. A modified gas collection modified gas collection apparatus consisting of needles and a flexible cannula instead of a glass delivery tube. Did not mark volume measurements on the side of the gas collection reservoir since the entire container is to be filled with gas. Small 150mL beaker was used instead of a 250mL beaker to immerse the gas collection reservoir in water.

. Reaction Scheme:

Data and Results Table:

2-butanol Mol. Formula Amount (mg) Amount (L) mmoles Molar Mass Concentration** Density (g/mL) C4H10O 161.6 200L 2.18 74.12g/mol N/A 0.808g/ml sulfuric acid H2SO4 183.4 100L 1.87 98.08g/mol 18 M 1.834g/ml trans-2-butene, cis-2-butene, 1-butene C4H8 105mg* N/A N/A 56.11g/mol N/A N/A

*Theoretical yield of butenes, regardless of product ratio. **Needed in this case because one of the reactants, H2SO4, is a solution. For most experiments, concentration will not be included in the Data Table.

Observations: 1:35pm: Water level in gas collection reservoir dropped a couple of cm above the water line of the beaker. 1:55pm: Water line fluctuates between being level with and being a few cm above the water line of the beaker. 2:02pm: Water leave did not decrease any further. Collected gas sample directly from the conical vial containing the reagents.

Calculations: 1)Theoretical yield of butene products 1:1:1 stoichiometric ratio for reactants and products with sulfuric acid as the limiting reactant at 1.87 mmol as opposed to 2-butanol at 2.18mmol.
(100L
H2SO4

/1)(1mL

H2SO4

/1000L)(1.834g
C4H8

H2SO4

/1mL)(1 mol

H2SO4

/98.08g) (1mol

C4H8

/1mol

H2SO4

(56.11g

C4H8

/1mol)(1000g

/1g)=105mg C4H8

2) Because the products are gases, you will not determine a yield or a % yield for this reaction (but you will do so for future experiments). 3) Gas chromatography Retention Time, in minutes (chart speed = 1 cm/min) P1=(2cm/1)(1min/1cm)=2 min P2=(.75cm/1)(1min/1cm)=0.75 min P3=(.20cm/1)(1min/1cm)=0.20 min P4=(.20cm/1)(1min/1cm)=0.20 min 4) Gas chromatography Peak Area, in mm2 Estimate by the triangle method.
P1=(21mm)(1mm)=21mm2 P2=(3mm)(1mm)=3mm2 P3=(19mm)(1mm)=19mm2 P3=(15mm)(2mm)=30mm2

Questions: 1. Write a mechanism for the E1 elimination reaction of 2-butanol with sulfuric acid. Be as complete as possible and show electron flow for all steps. You should clearly indicate the mechanistic pathways that lead to each of the products formed in the reaction (there is no need to duplicate common steps, but at some point the pathways diverge).

2. 1-Butanol also undergoes an acid-catalyzed dehydration reaction. a) Draw the product or products of this reaction.

b) The reaction likely does NOT occur via an E1 elimination process. What type of mechanism operates in this case? The reaction proceeds by an E2 mechanism. c) Explain why the acid-catalyzed dehydration reactions of 1-butanol and 2-butanol do not proceed via the same type of mechanism. The reason that 1-butanol and 2-butanol do not have the same mechanism is because 1-butanol is a primary substrate and 2-butanol is a secondary substrate.

3.

Assign the identities of the peaks that eluted from the gas chromatograpy (GC)

instrument after injection of your product sample. For each peak, list the retention time and peak area (see Calculations). It may be useful to present this data in tabular format.

Compound 1-butene trans-2-butene cis-2-butene 4. More GC a)

Retention Time 0.75 min 0.20 min 0.20 min

Peak Area 3mm2 19mm2 30mm2

What are the relative peak areas of the GC peaks observed for your products? The first large peak is most likely some air from a pocket that was in the syringe. The other 3 peaks in order are 1-butene (the smallest) trans-2butene (The largests) and cis-2-butene.

b)

Are the relative peak areas consistent with your expectations of the product

distribution for the dehydration of 2-butanol? Yes, 1-butene is the least stable so there is less of it in the gas sample. This shows as the smallest peak in the GC. Trans-2-butene is the most stable and most abondent compond in the sample. This is reflected by the largest peak on the GC. Cis-2-butene is slightly less stable than trans-2-butene so there is a bit less of it in the sample. Cis-2-butenes peak is slightly smaller than trans-2butenes.

5.

Provide an explanation for the expected (and hopefully, experimentally

observed) product distribution. The isomers of butene all similar boiling points. Works Cited: 1. Mayo, D. W.; Pike, R. M.; Forbes, D. C. Microscale Organic Laboratory with Multistep and Multiscale Syntheses, 5th ed.; John Wiley & Sons, Inc., 2011; pp 209-217.