Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb.

2018 – Your name: ___________________ 1

DO NOT OPEN THIS TEST UNTIL EVERYONE HAS ONE

You will need to show picture ID to take the test.

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 from 10:00 am to 12:00 pm.
4. Nothing other than writing implements are allowed.
5. Problems 1-65are multiple choice. Some problems may have more than one answer. Answers
are to be recorded on the test -- no Scantron needed.
6. If you finish early, quietly give the test to Grotjahn or a TA.

Problems 1-5 (4 points each) ________/20

Problem 6 ________/10
Problem 7 ________/10
Problem 8 ________/10
Problem 9 ________/10
Problem 10 ________/10
Problem 11 ________/10
Problem 12 ________/16
Problem 13 ________/12
Problem 14 ________/14
Problem 15 ________/14
Problem 16 ________/14

TOTAL ________/150
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 2

1. Which of the following compounds are NOT aromatic? (remember, "not aromatic" is neither
the same as "antiaromatic" nor the same as “nonaromatic” -- maximum of two answers)
H H
S N O
N H N

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

2. Which of the following compounds are aromatic? (maximum of two)

H

H O

H H
H
- -
C7H7 C6H6 C4H3 C7H8 C7H7O+
(A) (B) (C) (D) (E)

3. Pick the true statement(s) (maximum 2) about the C-H bonds in the molecule below.

H
b
H a
H
H H H d
h
i e c
H f H
j g H
H

(A) bonds d, e, f, and g are the weakest

(B) bonds h and j are the weakest
(C) homolysis of bond d gives the same product as homolysis of bond e
(D) bonds a, b and c are the weakest
(E) homolysis of bond d gives the same product as homolysis of bond a
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 3

4. Select the correct ranking of the compounds shown according to their acidity.
"A > B" means A is more acidic than B.
O O O O
Cl C C C C
C OH H3C CH3 H2C OH H3C OH
Cl
Cl Cl
1 2 3 4

(A) 1 > 2 > 3> 4

(B) 1 > 3 > 4 > 2
(C) 1 > 3 > 2 > 4
(D) 2 > 4 > 3 > 1
(E) none of the above

5. Which compound or compounds are Lewis acids? (pick as many as are correct!)
O
(A) AlCl3 (B) (C) BH4 (D) (CH3)3C (E) (CH3)4N

6. How many molecular orbitals does the pi system of cyclohexa-1,3-diene have?

How many molecular orbitals does the pi system of this cation have?
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 4

7. 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:

Part B:
H
N
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 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.

8. Correctly identify the products and write the mechanism of the synthetic sequence below.
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 6

9. More than one stereoisomer is produced; show the mechanism for formation of one and just
show the other isomeric product. What is the ratio of isomers formed? Why this ratio?

1. NaBH4
O 2. H3O+
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 7

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

b) Predict and draw product(s) from the following reaction. Use arrow-pushing. Draw the
structure of the anion shown. Explain why a reaction would happen.

PF6
+

11. Explain why H3O+ is the strongest acid present in any significant concentration in aqueous
solutions of a very strong acid such as HCl or H2SO4. Your answer needs to include the relevant
chemical equilibrium for credit.
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 8

12. 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)

b)
O

+ O

c) Br H
CH3OH, heat
CH3

d) NBS, ROOR

e)

f)
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 9

13. How many 13C NMR signals for each compound below? Answer in blank space ONLY.

(a) Answer_________

(b) Answer_________

(c) Answer_________

(d) Answer_________

(e) Answer_________

(f) Answer_________ [8]annulene

Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 10

14. Identify the relationships of the protons indicated (using the correct one of the four “-topic”
terms), and whether the two protons would give the same NMR signal, or not.
USE THE TABLES. Do not expect credit if you use other ways of answering the problems.

(a)
a
H
d b
H H
c
H
e
H

Relationship Same signal? Yes or no.

a
H and bH
c
H and bH
c
H and aH
c
H and dH
d
H and eH

(b)
Br CaH3

CH CH
CcH3 C CbH3
H2

Relationship Same signal? Yes or no.

a
H and bH
c
H and bH
c
H and aH
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 11

15. Predict the NMR spectra of the following molecules, USING THE TABLE FORMAT.
Note: Do not expect full credit if you use other ways of answering the problems. Assume that in
cases where there are complicated signals (e.g. triplet of quartet) that all of the peaks can be seen.
The tables are provided for your answers. You may or may not need all of the rows!

Example: bromoethane, BrC(aH)2C(bH)3

Expected integration Chemical shift somewhere Multiplicity
in the range of
a
H 2H 3.0-4.1 ppm quartet
b
H 3H 0.8-1.8 ppm triplet

(a) OH

Expected integration Chemical shift somewhere Multiplicity

in the range of

(b)
Br

Expected integration Chemical shift somewhere Multiplicity

in the range of
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 12

16. Identify the following compounds using the data shown. SHOW YOUR WORK OR GIVE
A BRIEF EXPLANATION of how you got your answer. If you just draw the right structure
without showing some of your work, you will not get full credit.

(a)

A compound with the molecular formula C10H13Cl gave the following 1H NMR spectrum:
singlet,  1.6 (6H)
singlet,  3.1 (2H)
multiplet,  7.2 (5H)

(b) A compound gave the following NMR spectrum:

Two singlets, at  2.3 and 7.2 ppm, with integral ratio 3 to 2.

Its mass spectrum showed a parent ion of mass 106. The peak of mass 107 was 9% as intense as
the one of mass 106.
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 13

(c) What is the structure of the compound in the following 1H-NMR spectrum with the molecular
formula C5H11NO, which shows a characteristic stretch in the IR around 1700 cm-1, and a
characteristic peak at 202 ppm in the 13C-NMR? Relative integrations are shown. Splittings for
the signals, going from left to right: triplet, triplet, singlet, doublet of triplet
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 14
Chemistry 432 Spring 2018 – PRACTICE Midterm 1 – Feb. 2018 – Your name: ___________________ 15
Chemistry 232 – Midterm 4 – 23 November 2013 – Your name: 16

For S N2: polar aprotic The nucleophiles (Nu)

Substitution vs. Elimination: SN1, SN2, E1, E2 gives f aster rates than Nucleophiles in bold are strong bases
Chem 232 -- Spring 2016 -- Prof essor Douglas Grotjahn
polar protic I -, Br -, N3-
For halides in polar
HS-, RS- -C N
(with thanks to Prof . Patrick Walsh) aprotic solvents: Good/strong
Substrate HO-, RO- , R2N-
the  carbon the  carbon F - > Cl - > Br- > I- nucleophiles
Is there a good leaving group?
PR - C C R
3
H None of this Cl-
yes no applies...unless you can O
C C + Nu
? turn a poor leaving
group into a good one!
Moderate
nucleophiles
RSH, R2S
R3N, R2NH, - C
O R
X the leaving group RNH 2, NH 3
Substrate What is substitution
pattern of the  carbon? F-
H2O, ROH
Poor/weak
primary secondary O
tertiary nucleophiles
C
HO R
Is Nu a hindered and strong base? Is there a Is Nu a strong base?
(3o alkoxide = hindered) strong base present? (e.g. alkoxide RO-)

no
yes yes
no yes no
Is Nu a good or
Mostly alkene moderate
f ormation nucleophile?
Alkene Is the solvent polar?
by E2 mechanism,
f ormation
some SN2 yes no
Is Nu a good (look at the  C-H)
nucleophile? (Mostly) alkene
by E2 in nonpolar yes no f ormation (look at SN 2 Is the
solvent, E1 or E2
the  C-H) by E2 reaction solvent
yes no in polar solvent
mechanism; + SN2 polar?
Note:
Rapid SN1 Slow reaction
Rapid SN2 Slower SN2
higher temp. yes no
usually reaction, with
reaction increases
some E1 if Nu Slow reaction
proportion of Substitution by SN1
If Nu: = strong base,
some E2 also
elim. over subst. is poor/weak
Chem 432 PRACTICE Midterm 1 --- February 2018 --- Professors Grotjahn and Cole 17
Chem 432 PRACTICE Midterm 1 --- February 2018 --- Professors Grotjahn and Cole 18