Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 1

DO NOT OPEN THIS TEST UNTIL EVERYONE HAS ONE

I encourage following instructions:
ten (10) points will be deducted if your name is not legibly written below.

Your name:

Your signature (required for grading):

Instructions:
1. In fairness to all, do not open this test until everyone has one.
2. Relax!! Put your name and signature on this page.
3. This test is designed to last 2 hours.
4. Nothing other than writing implements are allowed.
5. If you finish early, quietly give the test to Prof. Goletiani.

Problem 1-4 ________/16 total

Problem 5 ________/20
Problem 6 ________/8
Problem 7 ________/13
Problem 8 ________/14
Problem 9 ________/15
Problem 10 ________/20
Problem 11 ________/10
Problem 12 ________/34

Extra point problem

TOTAL ________/150
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 2

1. Pick the true statements about the following reaction. Bond dissociation energies in kJ per mole:
C6H5-H 474; Br-Br 193; H-Br 366; C6H5-Br 346 kJ/mol.

FeBr3 catalyst Br
+ Br2 + HBr

(A) the reaction is endothermic

(B) the reaction is exothermic
(C) the activation energy of the reaction is zero
(D) the first step of the reaction is exothermic
(E) the first step of the reaction is endothermic

2. Consider the resonance forms O O O O

shown for the arenium ion
formed from the bromination of
acetanilide. Which resonance HN HN N HN
form contributes most to the
overall resonance hybrid?

(a) I
(b) II
(c) III Br H Br H Br H Br H
(d) IV
(e) All contribute equally. I II III IV

3. In electrophilic aromatic substitution, the attacking species (the electrophile) must be :

(a) a neutral species.

(b) a positively charged species.
(c) a Lewis acid.
(d) a Bronsted-Lowry acid.
(e) a carbocation.

4. What is the chief product of the Friedel-Crafts alkylation of benzene with 1-bromobutane and
AlCl3?

(a) butylbenzene
(b) 2-phenylbutane
(c) 2-methyl-1-phenylpropane
(d) t-butylbenzene
(e) 2,2-diphenylbutane
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 3

5. Please give correct IUPAC names for the following compounds.

(a)
O

(b)
CHO

Cl
CH3

Please draw the correct structures of the following compounds.

(c) 7-bromo-1-octyn-4-one

(d) meta-nitrotoluene.

(e) 3-phenylpropanal
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 4

6. For the following molecules, draw all resonance structures. If a structure that has a sextet of
electrons around a non-hydrogen atom explains the reactivity of the molecule, include it. Show all lone
pairs and formal charges. If a compound is ionic, show each ion separately. Points will be deducted
for extra answers.

If there is more than one resonance structure indicate their relative importance.

Part A:
LiAlH(OtBu)3

Part B: the reactive intermediate formed from CH3COCl that attacks the benzene ring during Friedel-
Crafts acylation.
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 5

While answering the following problems, remember: "write the mechanism" means drawing correct
Lewis structures with all lone pairs and formal charges, and correctly using arrows to indicate
the flow of electrons.

7. Write the mechanism of the reaction below. Show reaction only at the most-favored position.

CH3
O C
HNO3, H2SO4
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 6

8. Write the mechanism of the reaction between the compounds below.

CH3COOH catalyst
(to make writing easier
H3C call it HA)
C CH3 + (CH3)2NH
O
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 7

9. Propose a reasonable synthesis of the following compounds from the indicated organic starting
materials, using any inorganic reagents or organic reagents.
(a)

CH3O
from phenol

(b)
O

O CH3

from benzene

NO2

(c)

H2N
from starting material of your choice
NO2
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 8

10. Propose a reasonable synthesis of the following compounds from the indicated organic starting
material(s), using any inorganic reagents or organic reagents.
(a)

O O OH
Br
H H

(b)
OH
OH

(c)
from benzene and any molecule with 4 carbons or less

(d)

from benzaldehyde and any organic

molecules with 3 carbons or less
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 9

11. Explain the following results. The reaction shown works very well – almost 100% yield within an
hour at room temperature. A similar reaction starting with the 1-methylimidazole (i.e. with methyl not
H at position 1) does NOT work. (Note: we learned in Chapter 15 that I2 by itself does not react with
benzene, but does react when nitric acid is added – see Extra Point problem at the end of this exam.)
(“Explain” means use a combination of mechanism, showing arrow-pushing, and words describing
application of basic chemical principles you have learned in general chemistry, 232, and now 432)
H 2 I2 H
R N 2 NaOH R 2 N1
I
N solvents = N 5
water and 4
I
O
O
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 10

12. Correctly predict and draw all organic product(s) from the following reactions. If no reaction
would occur, say so. If more than one isomer would be produced, draw them and predict which one
would be the major one.

(a)
NH2NH2, KOH, heat

(b)
NH2 Br2 (>2 equiv)

(c) CN DIBAL-H dilute aq HCl

ether, -78 oC

(d) CHO
cat. CH3COOH
+
H2N

(e)
CHO
HCN

(f)
CHO
Ag2O
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 11

(g)
O CH3COOH cat.
+ NHNH2

(h)
SO3H
H2O, heat

NO2

(i)
H2O, KMnO4 , KOH, heat
NO2

(j) concentrated H2SO4

(k)
O
H2O, H2SO4 (cat.)

(l) O
concentrated HI, heat

(m) O
Cl
O OOH
Chem 432-G Second Midterm – 5 March 2018 --- Professor Grotjahn 12

Extra point question:

Problem #1 asked about bromination of benzene (reaction at bottom of the page).

Iodination of benzene under the same conditions does NOT happen. Why not? Explain.

Bond dissociation energies in kJ per mole:

C6H5-H 474; I-I 151; H-I 298; C6H5-I 276 kJ/mol.

Iodination DOES work in the presence of HNO3. Is nitric acid acting as a catalyst? Explain your
answer.

Bond dissociation energies in kJ per mole:

C6H5-H 474; Br-Br 193; H-Br 366; C6H5-Br 346 kJ/mol.

FeBr3 catalyst Br
+ Br2 + HBr