Adriana English

Sec 5: Sara
CHM 2211L
POST LAB 10
Purpose: The goal of this experiment was to explore SN1 and SN2 reactions. An unknown halide was
identified using HNMR and qualitative tests. Alkyl halide reactivity was tested and compared using different
reagents.

Data and Calculations:

Alkyl Halide AgNO3 in ethanol SN1 NaI in Acetone  SN2
1-chlorobutane - (+) with heat
2-chlorobutane (+) with heat, 5 min -
2-bromobutane + (2 min) (+) with heat
t-butylchloride + instant w/o heat -
bromobenzene (+) with heat, 5 min -

UNKNOWN #2 Unknown
AgNO3 in ethanol + instant
NaI in Acetone - No rxn

Discussion:
It was found that t-butylchloride prefers to go through the SN1( AgNO3 in ethanol) mechanism
because of its stable carbocation intermediate. 1-Chlorobutane preferred SN2 (NaI in Acetone) because it’s
unable to have a stable carbocation and are better suited with the quicker mechanism. In AgNO3 in ethanol at
room temperature 2-bromobutane and t-butylchloride both reacted and turned a cloudy white color. When put
in an 80 degree C hot bath, we noticed that the two others; 2-chlorobutane, and bromobenzene all yielded a
reaction as well. Once added to the hot bath the t-butylchloride showed a chunky precipitate in the vial. None
of the alkylhalides showed a precipitate in NaI at room temperature, however 1-chlorobutene and 2-
bromobutene formed white and yellow cloudy precipitates after a few minutes in the hot bath. We were not
surprised by these results, as we know the SN1 reactions are faster and more stable due to the nitrate
stabilizing the intermediate. We expected the heat to produce precipitates. Na is not as electronegative as Ag,
so the SN2 reaction was expected to be less precipitate yielding. Due to sterics the addition of heat did not aid
the SN2 reaction very much. Lastly it should be noted that when the R groups are carbons, SN2 did not work
(t-butylchloride for example). The unknown was found to use SN1 vs. SN2. Along with the HNMR, the data
concludes that the unknown is t-butylchloride. T-butylchloride is a tertiary alkyl halide so it can undergo an
SN1 scheme because it gives a 3 degree carbocation which is more stable, hence increasing its reactivity.

Error Analysis:
Error occurred when recording start and stop times for 2-bromobutane and bromobenzene which may alter the
order of which the reaction took place. Another human error was when observing the precipitates before
placing in the hot bath which may also skew results. During the hot bath, our 10mL glass vials fell over
constantly. We noticed a bubbling of air meaning the lids were not tight enough, so our results could be
skewed if the tested solution escaped and or if water from the water bath entered the vials. It should also be
noted that maintaining the temperature of the water baths was difficult, which could cause some
inconsistencies in the reaction rate.
Conclusion:
Using our knowledge of functional groups and NMR we were able to identify our unknown as t-butylchloride
and analyzed the halides reactivity. This lab was successful in testing our ability to determine our unknown
and successful in furthering our knowledge to recognize similarities and differences in SN1 and SN2 reactions.

Questions
1. [A] It would be Sn1 because it is a tertiary halide. There is steric hinderance on the carbon in the 1
position, so the Sn1 mechanism is going to be more favorable than the Sn2 mechanism.
[B] This will be Sn2 since it is a primary halide. This is going to be a good leaving group in addition
to the fact that there is little steric hinderance.
[C] Sn2 or Sn1 could likely happen. It is a secondary halide which means, when under certain
conditions, either mechanism could occur because it has a stable carbocation intermediate as well as
being able to run a backside attack.
2. Benzyl bromide is a primary alkyl halide and can easily undergo an SN2 reaction. However it can
also run an SN1 mechanism because it’s allylic and resonance occurs in the compound. This
resonance allows for either Sn1 or Sn2.
3. The bulky benzene ring in bromobenzene will prevent a Sn2 reaction because the bulkiness will
prevent a backside attack. When the bromine leaves, the carbocation is then too unstable so Sn1 is not
desirable. In addition, there is little hydrogen availability which prevents the reaction from starting.
4. A higher mass and more bulkiness of an atom will lead it to be a better leaving group. From this, we
can conclude that Br is a better leaving group than Cl. Similarly, the conjugate base of a bromine is
going to be weaker than the chlorine conjugate base. Bromine would be a stronger acid as well. Also,
bromine is generally a more polarized molecule than chlorine. Bromine also has a longer bond length
which allows it to break easier and allow bromobenzene to react quicker than chlorocyclohexane.
5. Like question four, Iodide is going to have a greater mask and be a bulkier atom. It will be a stronger
acid than bromine thus will be a better leaving group. Iodide’s larger size allows it to better stabilize
the negative charge.
6. The stability of the carbocation is based on the type of solvent used. While in the solution, Ag is going
to form a bond with a halide in order to create a carbocation. A polar, protic solvent would allow the
carbocation to stabilize and favor the Sn1 mechanism.

7.
SPARTAN
Carbocation Molecule Energy (kcal/mol)
2-bromo-2-methylbutane -303.06
2-bromo-3-methylbutane -304.61
1-bromo-3-methylbutane -310.21
1-chlorobutane -338.11
2-chlorobutane -335.74
t-butyl chloride -337.09

1. It appears that 2-bromo-2-methyl butane (-495.242 kcal/mol) is going to be more likely to dissociate since
it has the lesser difference in energy. 1-bromo-3-methylbutane (-513.987) will likely dissociate the least
because it has the greatest difference in energies compared to the rest of the alkyl bromides. We can also
conclude, based on its smaller energy difference, that t-butyl chloride (-538.004 kcal/mol) is going to
dissociate the most readily. Whereas 1-chlorobutane (-557.996) will likely dissociate the least or longest
time based on its energy difference compared to all the other alkyl chlorides.
2. The highest localization of a positive charge is located on the tertiary carbon of 2-bromo2-methylbutane
and t-butyl chloride. This leads to a higher fixed charge and increased reactivity. The cation on 1-bromo-3-
methylbutane cation and 1-chlorobutane has the greatest delocalization of a positive charge since the
charge is coming from the primary carbon. This leads to less stability and more reactivity. From this we
can conclude that a hydride/possibly methyl shift(s) will happen so that it can form a more stable
molecule and a more stable carbocation.
3. Yes, there are visible structural changes. This suggests that the cation is aiming to stabilize the charge via
geometric alterations. The molecule’s structure is changed via hyperconjugation so that stability can take
place through the interaction of the electrons. The electrons are sigma bonded with a neighboring pi orbital
which extends for stability purposes. The halide also gives an inductive effect.

BONUS:
1. As we learned, hyperconjugation leads to altering geometries and can thereby increase stability. In this
case, it will go from tetrahedral to a double bonded trigonal planar with the hyperconjugation that
happens.
2. The carbon-carbon bond is going to be shorter with the cation.
3. Conformation can change depending on bond length. The charge of the cation and its location is anti-
proportional compared to the bond length.
4. As we know, when hydrogens are on the same plane, they will typically have shorter bonds. Likewise,
bonds on different planes will be longer. This originates from electronegativity of the carbon atoms that
pull on the hydrogens. In this case, the carbon-hydrogen bond that is outside of the plane will have H’s
that are capable of hyperconjugation. This leads to electron donating and the overall stabilization of the
cation.
5. Molecular energy is affected by many things, such as conjugation for example. Stability, on the other
hand, is affected by hyperconjugation. Hyperconjugation especially leads to more stability in cases where
a given molecule lacks stability due to steric hinderance. Both hydrogen-hydrogen and carbon-carbon
bonds can be involved in hyperconjugation.