216 S10-Exam #1 Page 2.

Name ___________Key_____________

I. (3 points) Arrange the following four compounds in order of their Rf values when analyzed by thin-
layer chromatography (TLC) on silica gel-coated plates using CH2Cl2 as the developing solvent. No partial
credit is given to this question.
O O

HO H HO

1 2 3 4

Answer: 4 < 2 < 3 < 1

lowest Rf highest Rf

II. (9 points) Silica gel thin-layer chromatography (TLC) is often used to monitor the progress of an
organic reaction. For the following ester hydrolysis reaction, a solvent system is selected to give the
starting material an Rf value of about 0.5. (1) Provide in the box below the structure of the expected
product 7. (2) Fill in the spots that would be expected when the reaction is 50% compete and 100%
complete. Make sure to assign each spot you draw to the corresponding compound number (5, 6, or 7).
Consider only the compounds that can be visualized as a spot on TLC upon exposure of each solvent-
dried plate to a 254 nm-UV lamp.

CH3 H2SO4 (cat)

O H2O O CH3
(heat)
O OH +
HO
5 6
7 3

50% completion 100% completion

solvent
front

On each TLC plate, a student has placed

a sample of the starting material (5) as a
reference on the left of the plate, a spot
5
of the reaction mixture (after acidic work-
up) on the right, and a co-spot in the center
of each. Co-spotting is where some of 5 7
and some of the reaction mixture are
spotted together in order to make better 6
comparisons.

5 co-spot 5 co-spot
reaction mixture reaction mixture
216 S10-Exam #1 Page 3. Name _______Key___________

III. (17 points) N-Benzylaniline can be prepared by reaction of benzyl chloride and aniline in the presence
of aqueous sodium bicarbonate (NaHCO3).
NH2
Cl + + NaHCO3 N
+ NaCl + H2O + CO2
H
benzyl chloride aniline
N-benzylaniline

The procedure calls for 372 g of aniline, 127 g of benzyl chloride, and 105 g of sodium bicarbonate
dissolved in 100 mL of water, and produces 160 g of N-benzylaniline.

Write an answer in the box provided to each of the following questions.

(1) (3 points) Calculate as to how many moles of each of the reagents are used in this procedure. Use the
following atomic weights: C = 12, H = 1, N = 14, O = 16, Na = 23, Cl = 35.5

benzyl chloride: _1.00___ moles; aniline: _4.00__ moles; NaHCO3: _1.25___ moles

(2) (2 points) What is the limiting reagent?

benzyl chloride
(3) (3 points) What is the theoretical yield of N-benzylaniline?

183
______________ g

(4) (2 points) What is the percentage yield of N-benzylaniline?

87
______________ %

(5) (2 points) About 260 g of aniline can be recovered from the reaction. Does this affect the calculation
of theoretical yield? Explain.
The recovered amount of aniline corresponds to 2.80 moles. Since in this experiment,
4 mol equiv of aniline is used relative to the limiting reagent, benzyl chloride, it does
not affect the calculation of theoretical yield.
(6) (2 points) What volume of benzyl chloride (density 1.10 g/mL) is required for the reaction?

115.4
________________ mL

(7) (3 points) Why is it necessary to use such a large excess of aniline for the reaction? Explain.

As N-benzylaniline is more nucleophilic than the starting aniline, it can undergo

multiple benzylations. By the use of a large excess of aniline, the overall
reaction can be directed toward the monobenzylation of aniline.
216 S10-Exam #1 Page 4. Name________Key_____________
IV. (18 points) For each of the following reactions, provide in the box below a step-by-step mechanism
through the use of the curved-arrow convention.
(1) O
O OH
CH3 NaBH4 H3O+ workup
O O ethanol (i.e., protonation) O O CH3

O H O H H O

Mechanism including the H3O+ workup step:

O
O
O
CH3 O
CH3
O O each intermediate: 1 pt
O O each set of mech. arrows: 1pt
O H H
H O H
H B H
H H
Na
H O H
CH3
O O
O OH
O O O O CH3
O O CH3
O H H O H H O
O H H O 7

(2) O OH O
OH O
TsOH* (catalytic)
H H + H2O
benzene, reflux
4h
H H
O
TsOH* = H3C S OH You may use HA and A as your Broensted acid
Mechanism: (pKa = - 0.51) O and its conjugate base.

H OTs each intermediate: 1 pt

H each set of mech. arrows: 1pt
O OH O OH TsO
OH OH H O
O
H H
H H
H
H H O
HO H
H OTs O
OH OH
HO H HO H
O OTs O O
H O
H H
H
H H
H 11
216 S10-Exam #1 Page 5. Name ______Key_______________
V. (6 points) For each of the following sets of compounds, match the expected IR frequencies for the
C=O bond stretching vibration to the wavenumbers given.
(1) 1694, 1686, or 1666 cm-1
O O O

O
H3CO N
O
1686 cm-1 1666 cm-1 1694 cm-1
(2) 1763, 1719, or 1687 cm-1
O O
O
O O
O
H2N

1719 cm-1 1687 cm-1 1763 cm-1

VI. (3 points) A mixture of chlorobenzene (bp 132 C) and water (bp 100 C) could be steam distilled at
90 C. The vapor pressure of water at 90 C is measured to be 526 mmHg. What would be the vapor
pressure of chlorobenzene at 90 C? Write your answer in the box below.

234
____________ mmHg 760 - 526 = 234 mmHg

VII. (12 points) For each of the following synthetic reactions, draw the structure of the expected product
in the box provided.
(1)

NH3 H
O O N CH3 O
+ +
HO H3C O CH3 O H3C OH
HO
3 3

(2)
H3C OH
OH O
O
(solvent)
H3C H3C
+ NaOCl + H2O + NaCl
HO HO
CH3 CH3
3

(3)
O N
TsOH (catalytic) OH
H3C
+ H2N OH
H3C + H2O
H3C H3C
3
216 S10 Exam #1 Page 6 Name_______Key_____________
VIII. (12 points). Given below are infrared (IR) spectra of four compounds. The compounds are among
those structures given on page 8. Assign each spectrum to its compound by putting the letter
corresponding to the compound in the answer box next to the spectrum. The tables of characteristic
infrared frequencies appear on pages 9 and 10.

(1) (liquid film) Answer L CC or CN at 2231 cm-1, no alkynic C

(2) (liquid film) Answer E of R(=O)OH in the 3200-2500 cm-1; no C=C

216 S10 Exam #1 Page 7. VIII. (continued) Name ______Key_______________
N-H at 3416 cm-1; Both arom. C-H and alkanic C-H
(3) (liquid film) Answer I
no C=O (can't go down to 1606 cm-1)

Two kinds of O-Hs (inter and intramol H-bonded OH);

(4) (KBr disc) Answer A
many arom C=C's in the 1600-1400 cm-1 region.
216 S10 Exam #1 Page 8 Name _______Key_____________

VIII. (continued)

NH2
A H
H3C
HO OH H
N
I CH3
B OH

O
J
C CH3 N CH3
CH3 CH3

H
O
D H3C
OH K N
O H3C
E N
OH H3C
L N
O
H3C
F
CH3
H3 C O
H3C O CH3 M
H3 C
G H3 C O CH3
O O