Dr.

Sheppard
CHEM 4201
Fall 2014
Exam I Study Guide

Some questions to consider, topics to review….

I. Conjugated Systems, Pericyclic Reactions, MO Theory, UV Spectroscopy

● What are conjugated/cumulated/isolated double bonds? Which are more stable?

● Describe the structure of 1,3-butadiene (bond length, shape, etc.).
● Describe the s-cis and s-trans conformations. Which is more stable?
● What is the difference between a 1,2- and 1,4-addition product (in electrophilic addition)?
Under what circumstances are you likely to see each product form?
● Compare kinetic control to thermodynamic control.
● What is a pericyclic reaction?
● Describe electrocyclic reactions (starting materials, products, mechanism, conditions,
stereochemistry, etc.).
● Which electrocyclic reactions will be conrotatory? Disrotatory?
● Describe the Diels-Alder cycloaddition reaction (starting materials, products, mechanism,
conditions, stereochemistry, regiochemistry, etc.).
● What is a diene? Dienophile?
● Which starting material in a Diels-Alder reaction is likely to contain an EDG? EWG?
● What is the endo rule?
● How does the Diels-Alder reaction relate to insecticides? Read the provided Essay.
● Which cycloaddition reactions are favored thermally? Photochemically?
● What is a sigmatropic rearrangement? Given a sigmatropic rearrangement reaction,
classify it as a [#,#] reaction (e.g. [1,5], [3,3], etc.)
● What happens in the Claisen and Cope sigmatropic rearrangements? What are the
mechanisms for these rearrangements?
● What are molecular orbitals?
● What does it mean for a MO to be bonding? Antibonding? Which is lower in energy?
● Describe constructive and destructive overlap.
● Describe the MOs of ethylene and 1,3-butadiene (bonding vs. antibonding, number of
nodes, etc.). be able to identify the HOMO and LUMO in both the ground state and excited
state.
● How do you predict if an electrocyclic reaction is disrotatory or conrotatory? Be able to
answer this question for both thermal and photochemical reactions.
● How do you predict if a cycloaddition reaction is allowed or forbidden? Be able to
answer this question for both thermal and photochemical reactions.
● What do suprafacial and antarafacial mean? How do you know if a reaction is
antarafacial or suprafacial?
● What is the UV region of the EM spectrum?
● How does UV spectroscopy work?
● What is the relationship between max and molecular structure?
● Be able to predict max for a given molecule.

II. Polymers

● What is a polymer? Copolymer? Monomer, dimer, oligomer?

Dr. Sheppard
CHEM 4201
Fall 2014
Exam I Study Guide

● What are the different types of copolymers?

● Describe the structures of natural rubber and synthetic rubber. What is vulcanized rubber?
● Describe the different types of structures and properties of polymers.
● What does it mean if a polymer is biodegradable? How can biodegradability be
controlled?
● What structural features tend to be associated with rigid polymers? Elastic polymers?
● How are polymers recycled? What are some problems with the recycling processes?
● How are polymers classified?
● What are thermoplastics? Thermoset plastics? Plasticizers?
● Describe chain/addition polymerization reactions, including the radical, cationic and
anionic mechanisms. Which monomers are likely to undergo this type of polymerization?
● Describe step-growth/condensation polymerization reactions. Which polymers are likely
to be synthesized by this type of polymerization?
● Be familiar with the structures and give some examples of uses for the following
polymers:
Dr. Sheppard
CHEM 4201
Fall 2014
Exam I Study Guide
o Polyethylene (HDPE and LDPE)
o Polystyrene (PS)
o Polyvinyl chloride (PVC)
o Polytetrafluoroethylene (PTFE)
o 1,1-Dichloroethylene
o Polypropylene (PP)
o Polymethyl methacrylate
(PMMA)
o Polyethyl acrylate (PEA)
o Poly(2-hydroxyethyl
methacrylate)
o Cyanoacrylates
o Nylons
o Kevlar
o Poly(ethylene
terephthalate) (PETE)
o Spandex
o Polyurethanes
o Polycarbonates
o Poly(dimethylsiloxane)
o Polyglycolide (PGA)
o Polylactide (PLA)
Dr. Sheppard
CHEM 4201
Fall 2014
Exam I Study Guide

● How are acryalates named?

● How are polymers chosen/designed for a particular application? What properties are
important?

III. Carbonyl Condensation Reactions

● What is the aldol condensation reaction? Be able to draw the products from a reaction (given
starting materials) and be able to draw the starting materials (given products).
● What is a -hydroxy carbonyl? -unsaturated carbonyl? -diketone? -ketoester?
● What is an enolate? What is the best base to use to create an enolate from a neutral carbonyl?
● How does the enolate react with an electrophile? Be able to draw a mechanism.
● What is the haloform reaction?
● What does the product look like if the aldol product is dehydrated? What is the catalyst used
in the dehydration step?
● What is a mixed or crossed aldol condensation reaction? How many products can be formed?
Why are benzaldehyde and formaldehyde good choices as starting materials for this type of
aldol reaction?
● What happens if the aldol reaction is intramolecular? What types of ring structures are
formed?
● What is the Claisen condensation reaction? How is it different from the aldol condensation
reaction?
● If both a ketone and an ester are used in a Claisen reaction, which one is more likely to act as
the enolate?