Organic Chemistry II: Sessler CH320N Midterm 2

K E Y

Please write the first three letters of

Organic Chemistry II
Midterm 2
Dr. Jonathan L. Sessler - CH320N
Thursday, March 22, 2018

Question Points
Page 2 _____/ 10
Name:___________________________
Page 3 _____/ 16
Page 4 _____/ 14
UT EID:__________________________
Page 5 _____/ 15

Signature:________________________ Page 6 _____/ 15

a) Name the following molecule according to the IUPAC system of nomenclature. Don't forget to
designate stereochemistry using R/S, E/Z or cis/trans if relevant. (5 pts)

OH O

Name: _____________(S)-3-hydroxy-3-phenylpropanal_______________________________

b) Draw the line angle formula for methanedicarboxylic acid (also known as malonic acid). (5pts)

O O

HO OH

c) Provide the name of the functional groups highlighted below. (2pts each)

N
(E) O

O
OH

_____Hemiacetal________ ______Enamine_________ _______Enolate_________

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Organic Chemistry II: Sessler CH320N Midterm 2
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II. Chemical transformations

For the following reactions, fill in the missing carbon containing reactants and products into the
corresponding boxes (3 points per box). Below each reaction, indicate whether it is catalytic (using
less than stoichiometric amounts) in acid/base or promoted (using at least one equivalent) of
acid/base by ticking the corresponding box (1 point per reaction).

O O
KOH, H2O
a) O O + OH

Catalytic in KOH: Promoted by KOH:

O MeOH, HCl O
HO
b)

Catalytic in HCl: Promoted by HCl:

O H O
O HCl
c) +
H
H H

Catalytic in HCl: Promoted by HCl:

O O
HCl, H2O H
d) NH OH + H N H
CH3

Catalytic in HCl: Promoted by HCl:

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Organic Chemistry II: Sessler CH320N Midterm 2
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III. Reactivity of Functional Groups

In the diagram below, fill in the boxes with the appropriate reagents and products respectively.
Make sure to include ALL carbon containing reaction products, but you don’t have to show
inorganic side products. Where applicable, aqueous workup is assumed (e.g., after reactions with
organometallic reagents and various condensations and hydrolyses). (15 pts; 2 per product, 1 per
reaction condition)

OH O NH2 , H+ O
excess CH3MgBr
O N
H

CH3Li EtOH, H+ NH2

O Cl2, KOH O SOCl2 O

CuLi

2
O
HO HO CN NaCN OH O O
Ph H
Ph Ph mild H+, no heat

LiAlH4

NH2
OH

Ph
OH

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Organic Chemistry II: Sessler CH320N Midterm 2
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IV. Mechanisms of Chemical Transformations

Provide an arrow pushing mechanism for the following two reactions (part b) is on the next page).
Draw out all intermediates and side products including any inorganic side products (e.g., chloride
ions). After you have shown a particular side products once, you may drop it in further steps. Pay
attention to reaction arrows and show equilibrium reactions as such! (15 pts each)

Hint: Both reactions are performed in a basic environment. Make sure your mechanism takes this
into account at all steps!

a)
O O
(E)
O KOH
+ H
heat

OH
O
OH
H O O
O O O OH
H H

H
H2O

OH

O
(E)

H2O
OH

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Organic Chemistry II: Sessler CH320N Midterm 2
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b) Fill in the three empty boxes with the two missing intermediates and the final product. Make
sure to include eventual side products in each box (if any). You may also have to add solvent/base
molecules next to the reaction arrows to aid protonation/deprotonation as appropriate.

Hint: The reaction below is called “Dieckmann condensation” and initially follows the same
mechanism as the Claisen condensation we discussed in class. The only difference is that
nucleophile and electrophile are both on the same molecule, so instead of performing the
nucleophilic attack on a second ester molecule, do so on the second ester functionality of the
same molecule. While the first steps are all in equilibrium, the reaction is overall irreversible due
an irreversible deprotonation in the last step. Your final product will thus be a resonance stabilized
anion!

O O
O O NaOEt
OEt + OH
EtO OEt EtOH
H

O O
O O H
OH + OEt
+ O
EtO OEt

O OEt O

OEt

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Organic Chemistry II: Sessler CH320N Midterm 2
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V. Synthesis

Provide a synthetic procedure that allows us to transform efficiently the given starting materials
to the desired product. Indicate all reagents used along the way and draw out all intermediate
products that you need to prepare. You don’t have to provide mechanisms for any of the
transformations. (20 pts)

O
O
+ HO
O

H2SO4
Li AlH4 mCPBA or other per acid
H2O

O OH O O
(E)
PCC

cat. acid or base

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Organic Chemistry II: Sessler CH320N Midterm 2
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VI. True/False Statements

Indicate the following statements as either true or false. Right answers reward +1, wrong -1 and
left blank ± 0 points. If you tick more often incorrect than correct, you will receive 0 points for the
entire page.

1. In an 1H-NMR spectrum, the introduction of electron withdrawing substituents generally

2. In an 1H-NMR spectrum, protons on aldehydes and carboxylic acids are usually the
furthest downfield on the spectrum (at the highest ppm numbers).
True Wrong

3. When heated, the majority of alpha-hydroxy carboxylic acids rapidly decarboxylate with
release of carbon dioxide. The product of this transformation is the primary alcohol.
True Wrong

4. Sodium borohydride and lithium aluminum hydride have almost identical reactivity and can
both be employed for the reduction of carboxylic acids to primary alcohols.
True Wrong

5. Grignard, alkyl lithium and Wittig reagents as well as terminal alkynes and enolates are all
chemical species that we have already learned to use in carbon-carbon bond forming
reactions.
True Wrong

6. A hemiacetal forms when a ketone reacts with an alcohol under mildly acid or basic
conditions.
True Wrong

7. An acetal forms when an aldehyde reacts with an alcohol under basic conditions.
True Wrong

8. Carboxylic amides are usually less reactive then their respective ester counterparts. This
may also explain why proteins are linked via amides rather than esters.
True Wrong

9. The acyl chloride is the most reactive acid derivative that we talked about and can be used
to synthesize amides, esters, carboxylic acids and acid anhydrides.
True Wrong

10. Organic chemistry is challenging yet insightful and fun. Attending the lecture as well as
the recitation session and office hours helps to keep up with the new material (ticking “true”
rewards you a free point here, ticking “wrong” will help the TAs to remember you).
True Wrong

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