Chem 232 – Quiz 5 Practice

1. Terminal alkynes are very important starting material to synthesize a variety of more
complex molecules. Starting from acetylene (HCCH) in the presence of appropriate
conditions and reagents provide products in the following synthetic scheme.

NaNH2 NaNH2
(a) H H
Br Br
A B

(b) Alkyne B can be further transformed to different diastereomers, a cis-alkene C

and a trans-alkene D under different reaction conditions. Provide specific
reaction conditions for the formation of C and D and describe in detail
(mechanism) how trans-alkene D is produced.

2. Allylic substitution reaction is very useful synthetic tool to introduce bromine atom on
alkenes at the allylic carbon.
(a) Provide expected product of the following reaction. Based on the information
about the mechanism of this reaction, determine whether the reactant and
product are optically active or inactive.
O

N Br
H
O (NBS)

peroxide, CCl4, 60 °C

Optically Optically
active inactive Optically Optically
active inactive

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 (b) Propose a synthesis of 3-bromocyclopent-1-ene from bromopentane.

Br Br

3. Consider the products from the photochemical bromination of optically active (R)-4-
methyl-1-cyclohexene. What are the possible monobromo regioisomers expected?
Will they be optically active?

H N Br
H3C
O

peroxide

4. It is important to have ways of describing structural classes of substituent groups and

reactive intermediates. Here are some you have encountered recently. Draw Lewis
structures for the following intermediates showing all carbons and hydrogens, multiple
bonds (= π-bonds), lone pairs of electrons, and formal charges at atoms.

(a) An allylic radical having the formula C4H7

(b) An acetylide anion having the formula C4H5-

(c) A vinylic cation having the formula C3H5+

(d) A conjugated diene having the formula C5H8

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5. Sketch the molecular orbitals of the allyl cation. Indicate the energies of the
orbitals relative to an isolated p-orbital on carbon. Indicate which of the π-molecular
orbitals are filled. Indicate the highest occupied molecular orbital (HOMO) and the
lowest unoccupied molecular orbital (LUMO).

energy

H
H C H
C C p orbital
H H
Allyl Cation

6. The π-molecular orbitals of 1,3-butadiene are shown below. Arrange them in terms
of their energy relative to the given p orbital. CIRCLE the orbitals that are filled.
Draw a BOX around the highest occupied molecular orbital (HOMO).

energy

p orbital

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7. The addition of HBr to the enyne shown below produces a mixture of monobromide
addition products. Write the major organic product of the following reactions. Clearly
show the stereochemistry of the product(s) where isomers are possible.

HBr
(a)

HBr
(b)

8. Indicate how you would make the following compound starting from compounds with
6-carbons or less.

H H
CO2CH 3
HCO2CH 3 CO2CH 3
CO2CH 3 H

9. Write the major organic product of the following Diels-Alder reaction. Clearly show
the stereochemistry of the product and indicate the product whether you have is an
endo or an exo product.

CHO
+

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10. Write the major organic products of the following reactions. Clearly show the
stereochemistry of the products where isomers are possible.

O O
(a) + H3CO OCH3

NC
(b) + C
NC

O
+ C OCH
(c) 3

(d) + O