Exam

2 Study Guide

Below is a list of things you should know for Exam 2. This list is only a study guideline. Recognize that all
topics discussed in lecture, in the textbook, or in the suggested problems are fair game for the exam.

Equations that will be provided:

Chapter 4:
kr = Ae-Ea / RT
G = H - TS
G = -RT(lnKeq) = -2.303RT (log Keq)

Information you should know:

Chapter 5 (Sections 5.9 5.16):
Be able to recognize if a compound is chiral even if it does not have any asymmetric carbons
Be able to draw Fischer projections
to represent the stereochemistry of compounds with one or more asymmetric carbons
Be able to identify pairs of enantiomers, diasteromers, and meso compounds and explain how
they differ in their physical and chemical properties
Be able to explain how different types of stereoisomers can be separated.

Chapter 4 (Sections 4.1 4.16):
Be able to propose a mechanism for the free-radical halogenation of an alkane
o 3 main steps: initiation, propagation (usually has 2 parts), and termination
Be able to predict the major halogenation products based on the stability of the intermediates and
the selectivity of the halogenation
o 3 free radical intermediates are more stable than 2 free radicals which are more stable
than 1 free radicals which are more stable than methyl free radicals. The more stable the
intermediate, the more likely the reaction will follow that pathway
o A double bond next to a free radical carbon will also help to stabilize the radical
o Bromination is much more selective than chlorination
! Bromination will react almost entirely at the most highly substituted carbon
! Chlorination will react at all viable carbons, though the major product will most
likely be the most substituted carbon
!
Be able to draw a reaction-energy diagram for a mechanism, and point oit the corresponding
transition states, activation energies, intermediates, and rate-limiting steps.
Be able to use bond-dissociation enthalpies to calculate the enthalpy change for each step of a
reaction, and the overall enthalpy change for a reaction
Be able to calculate free energy changes from equilibrium constants, and calculate the position of
an equilibrium from the free-energy changes
Be able to determine the kinetic order of a reaction based on its rate equation

Be able to use the Hammond postulate to predict whether a transition state will be reactant-like or
product-like, and explain how this distinction affects the selectivity of a reaction.
Be able to understand the structures of carbocations, carbanions, free radicals, and carbenes and
the structural features that stabilize them. Explain which are electrophilic and which are
nucleophilic
o Carbocations
! Properties: electrophilic and strong acids
! Stability: 3 > 2 > 1 > methyl
o Carbanions
! Properties: nucleophilic and strong bases
! Stability: methyl > 1 > 2 > 3
o Free radicals
! Properties: electron deficient (electrophilic)
! Stability: 3 > 2 > 1 > methyl
o Carbenes
! Can be both electrophilic and nucleophilic

Chapter 6 (Sections 6.1 6.16):
Be able to correctly name alkyl halides, summarize their physical properties, and identify them as
1, 2, and 3
Show how free-radical halogenation might be used for the synthesis of some alkyl halides
(essentially what we learned in chapter 4)
o Should also be able explain allylic free radical halogenation (when a double bond is
present)
! Free radical will typically form next to the double bond since the double bond can
induce resonance stabilization
! NBS (N-bromosuccinimide) is a common source of bromine in free-radical
brominations, especially in allylic brominations so there isnt a build up of bromine
Predict the products of SN1 and SN2 reactions involving alkyl halides, including stereochemistry.
o SN1 reactions:
! Occurs as a 2 step process: (1) leaving group leaves to form a carbocation. (2)
nucleophile attacks carbocation to form new group
! First order kinetics reaction
rate = k[halide]
! The more substituted the carbon with the leaving group, the more stable the
carbocation, therefore SN1 reactions favor more substituted alkyl halides
! 3 undergo SN1 reactions only
! Methyl and 1 halides do not undergo SN1 reactions
! Weak nucleophiles favor a SN1 process
Solvolysis is when the solvent serves as the nucleophile (very common for
SN1 reactions since many solvents are weak nucleophiles)
! The better the leaving group, the faster the rate
! SN1 reactions favor polar protic solvents because the ionic intermediates are
stabilized by solvation

Carbocations can rearrange to form a more stable carbocation

Hydride shift: H- on adjacent carbon bonds with C+
Methyl shift: CH3- moves from adjacent carbon if no Hs are available
! Racemization will occur in SN1 reactions because the nucleophilic attack can occur
on either side of the trigonal planar carbocation intermediate
o SN2 reactions:
! Occurs as a 1 step process: nucleophile attacks and leaving group leaves all in the
same step
! Second order kinetics reaction
rate = k[halide][Nuc]
! The less substituted the carbon with the leaving group, the less sterically hinder the
site of nucleophilic attack, therefore SN2 reactions favor less substituted alkyl
halides
! Methyl and 1 halides undergo SN2 reactions only
! 3 do not undergo SN2 reactions
! Strong nucleophiles favor a SN1 process
! The better the leaving group, the faster the rate
! SN2 reactions favor polar aprotic solvents because the nucleophiles are not well
solvated, and will therefore more nucleophilic
! No rearrangements occur as we see in SN1 reactions
! With a nucleophile attacks a chiral carbon in an SN2 process, the product will have
inverted chirality compared to the starting material;
Be able to draw mechanisms and energy profiles of SN1 and SN2 reactions
o See bullet 3, 10, 11, and 12 for tips on reactivity for the mechanisms
Be able to predict and explain the stability and rearrangements of cations in first-order reactions
o i.e. hydride shift and methyl shift
Be able to predict which substitution reaction will be faster for a particular process, based on
differences in substrate, base or nucleophile, leaving group, and solvent.
o See bullet 3, 10, 11, and 12 bullets for hints
Be able to predict whether a reaction will be first order or second order
o SN1 = first order, SN2 = second order
If given a set of reaction conditions, be able to identify the possible mechanisms, and predict which
mechanism(s) and product(s) are most likely.
o See bullet 3, 10, 11, and 12 for help
Should be able to show how substitution reactions of alkyl halides can be used to prepare other
types of compounds.
Be able to understand trends in nucleophilicity
o A species with a negative charge is a stronger nucleophile than a similar neutral species
! In particular, a base is a stronger nucleophile than its conjugate acid
! Example: OH- > H2O
o Nuclephilicyity decreases from left to right in the periodic table
! This follows the increase in electronegativity from left to right. The more
electronegative an element, the more tightly held are the nonbonding electrons,
which are then less reactive toward forming new bonds
!

! Example: NH2- > OH- > F-

o Nucleophilicity increases down the periodic table, following the increase in size and
polarizability, and the decrease in electronegativity
! Moving down the periodic table, the electrons are more loosely held due to atom
size, causing the atom to be more polarizable
! Example: I- > Br- > Cl- > F-
o See table 6.3 on page 237 for examples of strong and weak nucleophiles
Know the differences between a polar protic solvent and an polar aprotic solvent
o Polar protic solvents has solvent molecules that have hydrogens available for hydrogen
bonding
! Favored by SN1 reactions
o Polar aprotic solvents cannot hydrogen bond, but still exhibit dipole-dipole interactions
! Favored by SN2 reactions
! Should know abbreviations given in notes (DMSO, THF, etc.)
Be able to understand the what makes a good leaving group
o Should be electron withdrawing so that it will create a partial positive charge on the carbon
atom, making the carbon an electrophile. This will also help to stabilize a negatively
charged transition state in the single step of SN2 reactions and the first step of SN1 reactions
o Should be stable once it has left (with the electrons from the carbonleaving group bond)
! Means that they are typically weak bases
o See table 6.4 on page 241 in text for good leaving groups