Bryce Wellnitz Ian Melzar 1/23/2012

Dehydrobromination
Purpose: To determine the major and minor products for reactions involving alkyl halides under varying conditions such has substitution of the carbon bonded to the halide and the size and strength of base and solvents. Results are collected through the use of gas chromatography. Procedure: for the analysis of products of 2-bromobutane and OH/EtOH, using a 5ml conical vile add a magnetic stir vain, start a hot water bath raising the temperature to 80C and maintain at this temperature. Once the water bath is heated prepare the lid to the vial with a S shaped glass tube and insert so that its opening leads to a test tube filled with water and inverted into a beaker of water, in the same beaker have a gas collection vial filled with water and also placed inverted into the beaker (use clamps to hold it in place so the bottom does not go above the water line). Add .33ml of the halide and 3ml of the base to the conical vial and quickly attach top and place in water bath, after 1ml of air has escaped into the test tube switch the end of the S glass tube to the glass collecting vial and collect 4-5ml of gas. Using a syringe collect .05 - .1ml of gas and quickly transfer to a GC machine for analysis. Results:
*1-Bromobutane + -Ot-Bu Group 1-Butene trans-2Butene cis-2Butene 2-Bromobutane + -OtBu 1-Butene 54.1 % 52 % trans-2Butene 30.7 % 34 % cis-2Butene 15.2 % 14 % 2-Bromobutane + -OH/ EtOH 1-Butene 21.7 % trans-2Butene 59.9 % cis-2Butene 18.4 %

1 100 % 2 !00% 3 4 Average 100%

53.05%

32.35%

14.6%

21.7%

59.9%

18.4%

Calculations : (example using data for 2-bromobutane+ -OH/EtOH) Using triangulation the area under the curve could be calculated like so. Area =, (height of triangle* width of triangle at half height) After Collecting all the areas and add them together then to determine the percent composition you divide the area of 1 compound by the total area and multiply by 100 to get the percent composition (Area of 1 compound)/(area of all compounds)*100=percent composition of that compound Discussion:

Reaction of 1-bromobutane and t-butoxide, the reaction is an E2 reactions, this is because the halide is a primary and the base/solvent is aprotic and fairly strong. The results seemed to follow Zaitsevs rule because in a E2 reaction this would be the only possible product. Reaction of 2-bromobutane and t-butoxide, this reaction was primarily E2, determined by the fact that it is in a aprotic solvent and has a relatively strong base. Zaitsevs rule did not seem to be accurate this time has the major product was the least substituted 1butene (53.05%) not the more substituted 2butene (less than 50%). Of the 2-butene produced the major product of the 2 isomers was Trans (32.35%) far more than the cis product (14.6%) and this is consistent with the theory that the more stable product should be formed. Reaction of 2-bromobutane and OH/EtOH, this reaction will undergo primarily a E1 reaction because the reactants are in a protic solvent, Zaitsevs rule was correct in this case, the major product was the 2butene isomers (over 70%) the more substituted product was formed. Trans was formed (59.9%) and cis only (18.4%) this agrees with the theory that if nothing causes the reaction to favor one isomer the more stable of the two (trans) will form in greatest quantity)

Refrences: References
Introduction to organic laboratory techniques a mircroscale approach 4th edition, Donald L. Pavia, Gary M Lampman, Geore S. Kirz, Randall G. Engel 2007 Wolframalpha.com Post lab questions:
1. ( point) Briefly discuss how in gas chromatography the retention time is related to boiling point of the compounds being separated.

The simplest way to put it is that retention time is how long until the compound hits the sensor, the compound that boils fastest ( has the lowest boiling point) should reach the sensor first and will have the lowest retention time.
2. ( point) Explain what an elimination reaction is. What is the different between E1 and E2?

A elimination reaction is when the leaving group ( in these cases the halide) is removed along with a hydrogen (removed by a base) from a carbon at the beta position from that carbon and the electrons from that hydrogen go to the bond between these carbons and a double bond is formed. In a E2 reaction the new double bond is formed at the same time has the leaving groups bond is breaking but a E1 reaction has the leaving group break its bond and leave forming a carbocation before the hydrogen is taken off by a base and the double bond forms.
3. (1 point) What is Zaitevs rule? What are the exceptions to Zaitevs rule?

Zaitevs rule states that the major product of a elimination reaction will be the product with the most substituted double bond. The exceptions to this rule are, the E2 reactions involving fluorine has the leaving group, this forms a carboanion which will act opposite of a carbocation and will lead to a less substituted product, the second exception is when conjugation is possible if it is possible for the product to form or become part of a conjugated system then it will do this instead of favoring the most substituted product. Third exceptions is that if due to stereochemistry the reaction that would favor the most substituted product is not possible due to the leaving group and the beta hydrogen not being anti pari planer to each other than a less substituted product may be formed instead. The final exception to zaitevss rule is that if the base is large and bulky and the alkyl halide has substituents that are in the way of the beta hydrogens position the product might not form the most substituted product..
4. (1 point) Questions 2, p. 210 in Pavia.

5.

(1 point) Question 6 (indicate major product), p.210 in Pavia.

A) B)

minor

major

c) d)

minor

major