Chemistry 303

fall, 1996
FIRST EXAMINATION
7:30 PM, OCTOBER 8TH, 1996
Duration: 2 hr
Name____________________________________________________________
Lab TA___________________________________________________________
(if you do not know his/her name, give day of lab section)
This is an "open book" examination; you may use anything which is not alive.
Note: if you do not know the complete or specific answer, give a partial or general answer-WRITE SOMETHING
Write only in the space provided for each question.
Score:
1___________/16
2___________/20
3___________/20
4___________/18
5___________/26
Total:

/100

There are 7 pages in this exam; please check now to be sure you have a complete set.
Please be aware that a small number of students will be taking the exam at different times up until the afternoon
on Wednesday. It would be well not to discuss the exam until after that time.

Pledge:_________________________________________________________________________________
1

1. (16 pts) Easy warm up.

A. Following is a collection of four molecules (1-4) and also a list of four boiling points, with no
relationship implied between the two lists except that each bp is correct for one of the molecules listed.
Match the bp with the structure, and explain the basis for your assignment.
It will be clearest if you start with the lowest bp structure and compare with the second lowest, and so on until
you finish with the highest bp. If there is ambiguity, explain briefly your thinking.
O
N
H

1
bp

____

bp: 810 , 1000, 1060 , 1290C

O

2
____

4
____

____

Explain lowest vs second lowest bp

_____________________________________________________________________________________
Explain second lowest vs second highest bp

_____________________________________________________________________________________
Explain second highest vs highest bp

_____________________________________________________________________________________
B. 1. Write the three possible isomers for C2H2Cl2. No net charge, no formal charge.

2. Which isomer has the lowest molecular dipole moment? Explain.

2. (20 pts). Draw the conjugate base for each molecule in each pair; show carefully which proton has been
lost. Circle the most acidic molecule in each pair and explain the single most important reason for your
choice in terms of differential resonance, inductive (electronegativity), or hybridization effects.
OCH3

A.

CH3

vs
OH

OH

_____________________________________________________________________________________
B.
vs

_____________________________________________________________________________________
C.

vs

N
H

N
H

_____________________________________________________________________________________
O

D.

vs
O

3. (20 pts). Consider the following pairs of molecules. Note the bond indicated by the arrow in each
structure.
For each pair, circle the one in which the indicated bond is longer and give one important reason for the
difference (hybridization, delocalization, steric effects, inductive effects. Explain briefly. If you choose
delocalization, draw the relevant structure(s).
O

A.

vs

_____________________________________________________________________________________
B. H3 C C C CH3
H C C CH2 CH3
1

_____________________________________________________________________________________
C.

vs
1

_____________________________________________________________________________________
D. In a related analysis, draw the structure of a molecule with six carbons, any number of hydrogens, no
other atoms , and no formal charge which has the SHORTEST carbon-carbon SINGLE BOND distance.
Explain your choice briefly. Indicate clearly which bond you think is the shortest.

4. (18 pts). The following three compounds (1,2,3) are dissolved together in dichloromethane and need to be
separated. All are insoluble in water. A clever Orgo student devised the following separation scheme based on
information she learned in lab and lecture. This is on the last page of the exam, and you may rip it off for
convenience. She claims the compounds are separated during this sequence and appear separately in three of
the final solutions (consider solutions C-J). Some of the solutions do not contain any organic molecules.
Some of the solutions contain organic salts (of 1, 2, or 3) which is obviously the object of this plan. Note the
questions below. "Salts" refers to organic salts of 1,2, or 3. Not NaCl, etc.
N

C
CO2H
N

Cl

1. Which molecules or salts are present in Solution A? 1 2

CIRCLE BEST ANSWER(S)

3 none

a salt (draw below)

2. Which molecules or salts are present in Solution B? 1 2 3 none

a salt (draw below)

3. Which molecules or salts are present in Solution C? 1 2 3 none

a salt (draw below)

4. Which molecules or salts are present in Solution D? 1 2 3 none

a salt (draw below)

5. Which molecules or salts are present in Solution E? 1 2

a salt (draw below)

3 none

6. Which molecules or salts are present in Solution F? 1 2 3 none

a salt (draw below)

7. Which molecules or salts are present in Solution G? 1 2 3 none

a salt (draw below)

8. Which molecules or salts are present in Solution H? 1 2 3 none

a salt (draw below)

9. Which molecules or salts are present in Solution I? 1 2

3 none

10. Which molecules or salts are present in Solution J? 1 2 3 none

a salt (draw below)

a salt (draw below)

5

5. (26 pts) The following molecule is one representation of a highly delocalized structure. Even though this
structure is dipolar, with no overall charge, the molecule is very stable. It is called "munchnone" not because of
some resemblance to munchkins, but rather because it was discovered in Munich.
1. Add any formal charges required by the bonding and non-bonding electrons as shown on the structure
below.
2. Label each atom in the ring (not the external O atom) with its hybridization
3. Draw as many additional resonance structures as you can which all have the same number of bonds.
There
should be a total of five (four additional). Be sure to indicate carefully formal charges, bonds, and nonbonding electrons on each structure. Label all of the structures 1-5 for reference in discussion
4. Identify the"best " resonance structure, and explain your choice.
5. On your choice for the best structure, indicate the hybridization at each atom in the ring (ignore the oxygen
outside of the ring)

H
H
C

N
C
O

O
munchnone

Chart for question 4:

(you may rip it off)
All HCl (acid) and NaOH (basic) solutions are in water.

N
C

CO2H
N

Cl

[1,2,3] dissolved in CH2 Cl2

1. extract with 10% HCl solution
separate layers
CH2Cl 2 solution

acid solution
Solution B

Solution A

3. make basic with NaOH

2. extract with 10% NaOH

solution
separate layers

4. extract with CH2Cl2

separate layers

CH2Cl 2 solution

basic solution

Solution C

Solution D
5. make
acidic with HCl
6. extract with
CH2Cl 2
separate layers

basic solution

CH2Cl 2 solution

Solution E

Solution F
7. make acidic
with HCl
8. extract with CH2Cl2
separate layers

CH2Cl 2 solution

acid solution

acid solution

CH2Cl 2 solution

Solution G

Solution H

Solution I

Solution J