Exam IIIOS

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Exam IIIOS

Name: ANSWER KEY First and Last Name

Chem 345
Fall 2016
Exam IIIOS
1.) Single Step Breakdown Problem: Each of these molecules can be made
by an Aldol, Michael, Claisen, Mannich, or Umpolung reaction/mechanism.
Write the name of the reaction above the arrow, and write the starting
material(s) for the reaction. (3 pts each, 15 points total).
OH
A. O
Aldol

O
O

B. Aldol

O
O O

O O
C.
O O Claisen HO
MeO
HO or
O O
HO
OMe

O O
D.
Michael or
O O

O O

O
E. Mannich
H
N
N

O
O

For problems C and D where there are more than one option, just draw one
of the options
Exam IIIOS

2.) Predict the major carbon containing product(s) of the following sequence.
You do not have to worry about stereochemistry for this question.
(3 points each, 12 points total).
1.) excess
O H2 C PPh3
A.
O 2.) PCy3
Cl
Ru CH2
Cl
PCy3

1.) O
O O
B. O

OMe O

2.) H3O+

O
C. O
NaOMe
O
MeOH

C9H14O

D. 1.) MeLi, Et2O OH

2.) H3O+
N
3.) NaBH4,EtOH

racemic
Exam IIIOS

3.) Fill in the boxes. The second box in each sequence may represent one,
two, or three steps, but no more (3 points each, 12 points total).

O
A.) B.)

OH

Br
MeO

1.) POCl3, DMF

1.) excess MeLi, THF
2.) H2O
2.) H3O+
Vilsmeier-Haack Reaction

Me

Br

MeO

Zn(Hg), HCl 1.) H2SO4, HNO3

or 2.) NaBH4, EtOH
Δ, KOH, NH2NH2

O2N
OH

Br
racemic
MeO
Exam IIIOS

4.) Write the mechanism for the following reaction. Draw all curved arrows.
Draw the major resonance structure of resonance stabilized carbocations or
carbanions except in umpolung reactions. (15 points).

O O O
H2SO 4
H 2O
O
Exam IIIOS

5.) Provide an efficient synthesis of the following molecule. All carbons

must ultimately come from benzene or materials containing five carbons or
less. Your sole sources of deuterium are DCl, NaBD4, LiAlD4, D2O, and
CD3OD. Show intermediate products along the way. Any Grignard reagent
or organolithium except BuLi must be synthesized. (14 points total)

O D D

Br
N
H
Exam IIIOS

6.) Using the indicated starting material and any molecules that do not
contain deuterium, write an efficient synthesis of the indicated target.
Show intermediate products along the way. Any Grignard reagent must
or organolithium must be synthesized except for BuLi.
(10 points total)
Exam IIIOS

7.) Write the missing reactant(s) for each of the following. Some of these
require multiple steps. Be sure to delineate separate steps with 1.), 2.), etc…
(4 points each, 12 points total)

O
A. Robinson Annulation

O + O

KOH
EtOH

1.) NaNO2, HCl,

B.
2.) CuCN, H2O
+ 3.) LiAlH4, Et2O
NH2 4.) H3O+
5.) NEt3
NH
O

O
Cl

C. 1.) CD3MgBr, Et2O

2.) H3O+
O OH

O + CD3
CD3
Exam IIIOS

8a.) Compound 8 has the formula C8H7N.

Calculate the DBE 6 (2 points) (8*2+2+1-7)/2=6

The IR shows an absorbance at 2226 cm-1.

Nitrile
1
8b.) Use the H NMR spectrum to solve compound 8’s structure. Write your
structure in the rectangle provided. All signals are shown. Assign protons a-
e to the corresponding protons on your structure. Only the structure and
assignments in the rectangle on this page will be graded. (8 points).

a N
d C

c e