solvent

front
(10 points) Silica gel thin layer chromatography (TLC) is often used to monitor the progress of an
organic reaction. For the following hydrolysis reaction, a solvent system is selected to give the starting
material an R
f
value of about 0.5. (1) (2 points) Provide in the box below the structure of compound 1.
(2) (8 points) Fill in the spots that would be expected when the reaction is 50% compete and 100%
complete.
Name ____Key____________________
I.
1
2
On each TLC plate, a student has placed
a sample of the starting material (1) as a
reference on the left of the plate, a spot
of the reaction mixture on the right, and
a co-spot in the center of each. Co-spotting
is where some of 1 and some of the reaction
mixture are spotted together in order to
make better comparisons. Spots of
compounds 1 - 3 are visible under a 254
nm-UV lamp
(3)
50% completion
1
co-spot
reaction mixture
co-spot
reaction mixture
II. (6 points) What would be the expected order of R
f
values for each of the following sets of organic
compounds when subjected to TLC analysis on silica gel? For each set, circle the compound that is
expected to give the higher R
f
value. Assume dichloromethane is used as the developing solvent for the
TLC analysis.
H
O
(1)
O OH
(2)
OH OH
100% completion
1
A B
A B
B
A
OH
O
OH
H
3
CO
3
+
H
2
SO
4
(catalytic)
H
2
O (large excess)
70 C
216 W09 - Page 2.
O
O
OCH
3


216 W09 - Page 4. Name ______Key___________________

V. (5 points) Treatment of aldehyde ester 6 with sodium borohydride in ethanol produces lactone 7.
Provide in the box below a stepwise mechanism using the curved-arrow convention for the formation of 7
from 6.

O
H
O
O
6 7
O
O
NaBH
4
(1 mol equiv)
HOCH
2
CH
3
room temperature
2 h
5
O
H
O
O
6
B H
H
H
H
Mechanism:
O
H
O
O
H
O
O
O
7
O
O
mechanistic arrows: 1 pt for each step; each intermediate: 1 pt

VI. (12 points) Treatment of 292 mg of dimethyl methylmalonate (8) with 1 mol equivalent of NaOCH
3

dissolved in CH
3
OH resulted in the quantitative formation of its sodium salt, 9. Sodium salt 9 was further
treated with excess benzyl bromide (10) to provide 400 mg of benzylated product 11.
CH
3
O
O
OCH
3
O
H CH
3
CH
3
O
O
OCH
3
O
CH
3
Na
CH
3
O
O
OCH
3
O
CH
2
CH
3
8 (Mw 146 g/mol)
(1.0 mol equiv)
NaOCH
3
HOCH
3
9
10
11
CH
2
Br
(1.5 mol equiv)

(1) (4 points) In this experiment, a 25 weight % solution of NaOCH
3
in HOCH
3
(d = 0.945 g/mL) was
used. What is the molarity of NaOCH
3
in this solution? Show your work.
1 L of 25% weight % solution of NaOCH
3
: 1,000 mL x 0.945 g/mL = 945 g
25% of 945 g is NaOCH
3
= 0.25 x 945 g = 236.3 g
Therefore, the molarity is: 236.3 g / 54 g/mol = 4.38 mol. Answer: M = 4.38 (mol/L or mmol/L)

(2) (3 points) How many mL of this 25 weight % solution of NaOCH
3
in HOCH
3
was used in this
experiment? Show your work.
2.0 mmol each of 8 and NaOCH
3
used.
4.38 mmol/mL x X mL = 2.0 mmol Thus, X = 0.457 mL Answer: 0.457 mL

(3) (3 points) What is the theoretical yield of compound 11? Show your work.
2.0 mmol of 11 should be formed. Mol. Wt of 11 = 236 mg/mmol
Therefore, the theoretical yield of 11 is: 2.0 mmol x 236 mg/mmol = 472 mg Answer: 472 mg


(4) (2 points) What is the % chemical yield for the formation of 11 in this experiment. Show your work.
400 mg / 472 mg x 100 = 85% Answer: 85%


216 W09 Page 5 Name ____Key_________________

VII. (4 points) For each of the following pairs of compounds, match the expected IR frequencies for the
C=O bond stretching absorption to the wavenumbers given.

CH
3
O
N
O
O
CH
3
O
H
3
CO
(1) 1702 or 1682 cm
-1
(2) 1735 or 1760 cm
-1
O O
O O
1682 1702 1735 1760



VIII. (10 points) The pKa value of the conjugate acid of aniline (Ar-NH
3
+
) is determined to be 4.60.
Match the pKa values of 1.00 and 2.47 to the conjugate acids of 3- and 4-nitroaniline, 12 and 13,
respectively. Provide in the box below an explanation for your answer with the use of pertinent
resonance structure(s).


NH
3
NH
3
N
N
O
O
O
O
3
4
12 13
1 1
1.00 2.47




Explanation for 12:
Explanation for 13:
4 4
NH
3
N
O
O
3
NH
3
N
O
O
4
NH
3
N
O
O
4
highly destabilizing
charge charge
repulsion
NH
3
N
O
O
3
Thus, making the NH3+
more acidic.
Although these are de-
stabilizing, + chargrs are
not on the two adjacent atoms.
Therefore, these are
less destabilizing than
the interaction seen
in 13.




216 W09 - Page 8 Name ________________________

IX. (continued)




A.
B.
C.
D.
E.
F.
G.
H.
I.
J.
OH
OH
O
O
K.
L.
OH
O
O
O
O
O
O
O
C
N
N
H
O
H