Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/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
Problem 2 ________/12
Problem 3 ________/4
Problem 4 ________/9
Problem 5 ________/9
Problem 6 ________/9
Problem 7 ________/10
Problem 8 ________/12
Problem 9 ________/16
Problem 10 ________/16
Problem 11 ________/10
Problem 12 ________/10
Problem 13 ________/31
Problem 14 ________/10

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

1. Which of the CH3

following compounds H3C O H3C
CH3
C
will react the fastest C C CH3
in electrophilic O O O CH3
O NH2
O O CH3
aromatic substitution
with Br2 and FeBr3?

(A) (B) (C) (D) (E)

2. List the reactive intermediates responsible for electrophilic aromatic substitution using the following
reagents. (For the real midterm, you should know the mechanisms leading to each of the reactive
intermediates)

(a) HNO3/H2SO4

(b) (CH3CO)2O / AlCl3

(c) cyclohexene / HF

(d) sulfur trioxide / sulfuric acid

(e) 2-methyl-2-chloropropane / AlCl3

(f) chlorine / iron(III) chloride

3. Pick the true statement(s). (Please note: this is a multiple choice question, and all you have to do
for the test is answer it. However, for your own learning, you should be able to EXPLAIN to someone
else the reasons for your answers!)

(A) an amino group is electron-donating because of inductive effects

(B) an amino group is electron-donating because of resonance effects
(C) all ortho, para directors are activating in electrophilic aromatic substitution
(D) all meta directors are deactivating in electrophilic aromatic substitution
(E) in electrophilic aromatic substitution, meta directors enhance reactivity at the meta position
compared with reactivity of benzene itself
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 3

4. For the following molecules, draw all resonance structures which have octets of electrons around
each non-hydrogen atom. Show all lone pairs and formal charges. Points will be deducted for extra
answers (such as those which have sextets of electrons).

Part A:
CH2CH3
O
H H

H H
H

Part B: product of Lewis acid-base reaction of AlCl3 and the ketone at the O
right.
C
CH3
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 4

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.

5. Write the mechanism of the synthetic reaction below. For the first synthetic step, show reaction only
at the most-favored position.
O
H3C 1.
CH3 C + AlCl3
C Cl CH3
H3C
2. H2O
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 5

6. Write a reasonable mechanism for the following reaction, a direct way to introduce a chloromethyl
group. You only need to draw one resonance form of the non-aromatic intermediate (arenium ion).
What is the product not shown on the right side of the equation?
H
CH3O + C O + HCl CH3O CH2Cl
H
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 6

7. Write the mechanism of the synthetic reaction below. How many products form and what is their
relationship? Explain, using the correct mechanism.

0.01 equiv

SO3H
+ HO

O CH2Cl2
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 7

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

(a) 2-phenylbutane (racemic) from benzene

(b) para-isopropylpropylbenzene from benzene

(c) 4-bromoacetophenone [ could also be called (4-bromophenyl)methyl ketone ] from styrene

Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 8

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

CHO

from benzene

(b)
CH3
Br Br
from benzene

(c)

from toluene - no other aromatic compounds allowed

O

(d)

from compounds with 3 carbons or less

O
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 9

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

from benzene

(b) (problem is too difficult,

CHO
ignore)
from haloalkanes of 3 carbons or less

(c) O

OH from OCH2CH3

O O

(d)
from organic molecules with 3 carbons or less
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 10

11. Explain the following results. Don’t worry about the specific yields or number of equivalents. Just
explain how and why the reaction gives different product(s) depending on conditions.
(“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)
NOTE in corrected version: I went back to the original source and see that I made a mistake, and I also
decide to add one more piece of information. This problem is relatively hard but that’s OK on a
practice MT – you have more time to think about it than during a 2-hour midterm.
Br Br

H +
Br2 (3.0 equiv)
N Br N N
NaHCO3 (2 equiv)
OCH3 CH3OH, H2O CH3O OCH3 OCH3
10 min, RT 51% yield 25% yield

Br

H
Br2 (3.0 equiv),
N Br N
NaHCO3 (3.5 equiv)
OCH3 CH3OH, H2O CH3O OCH3
65% yield
10 min, RT
Br Br

Br2 (3.0 equiv), H

N
NaHCO3 (3.5 equiv) Br N Br N
O OH CH3CN O O O OH
10 min, RT
30% 12%
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 11

12. Chloride is a better leaving group than fluoride. If that is true, in a substitution of X for OH, why
does the fluoro compound react faster than the chloro compound, with a reagent such as sodium
bicarbonate in water? Explain. (“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)

O2N F O2N Cl
reacts faster than
NO2 NO2
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 12

13. Correctly predict and draw 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)
Br2 (1 equiv), FeBr3

(b)
start with the product
Mg, (CH3CH2)2O
from (a) that shows two
1
signals in H NMR between
6.5 and 8 ppm

(c) CN

dilute aq HCl
product from (b)

(d) benzaldehyde + CH3OH + CH3ONa catalyst

(e) propylbenzene + Cl2 + FeBr3

(f) acetophenone + hydrazine + NaOH and heat

Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 13

(g) butanal + HOCH2CH2OH + p-TsOH, heat

(h)
catalytic CH3COOH
O + NH

(i)
H2O, H2SO4 catalyst
D

(j) O Ag(NH3)2
+

CH3O
H H2O

(k)
O CH3CH2NH2, HCl (pH 5-6)
O2N
H

(l) concentrated HI, heat

OCH2CH3

(m)
H
O
NaH O
P OCH2CH3
OCH2CH3
Chem 432-G PRACTICE Second Midterm – CORRECTED- --- February/March 2018 --- Professor Grotjahn 14

14. The infrared spectrum of two isomeric compounds shows a strong absorption at about 1715 cm-1,
so IR does not tell them apart. Therefore the chemist acquired proton NMR spectra. Propose structures
for the two isomers, showing your work. There are a total of 12 hydrogens in each molecule.

Isomer 1

Isomer 2