Name ________________________ Section ______

Chem 227 / Sample Exam 1

Questions #1-30: Answer on Scantron; multiple choice (4 pts. each); T/F (2 pts. each).
Questions #31 & #32 answer on the exam, point values indicated. [Exam=130 raw pts. total]

1. In the following compound, (I) how many chemically equivalent carbon atoms [i.e. the # of
13
C NMR signals], (II) the number of enantiotopic protons, and (III) the number of
diastereotopic protons are there respectively?
I II III
A. 4 0 0
B. 5 2 0
C. 5 0 2
  D. 6 2 0
E. 6 0 2

2. Which compound (M+/. m/z = 114) would show major fragment ions in its mass spectrum at
m/z 85 and 57?

A) CH3CH2CH2COCH2CH2CH3 B) CH3CH2CH2CH2CH2COCH3

C) CH3CH2COCH2CH2CH2CH3 D) CH3CH2CH2CH2CH2CH2CHO

3. Barry Bonds is due go on trial for lying to a Grand Jury that he did not use an illegal growth
promoting steroid, tetrahydrogestrinone (THG), the “Clear”. THG is one of the steroids
below, which UV Spectroscopy can distinguish. What is the correct order of λmax values for
the 3 steroids. [THG has the highest λmax value.]

OH OH OH

H H H

H H H
O O O

         I II III

I II III
A. 239 nm 271 nm 314 nm
B. 271 nm 314 nm 239 nm
C. 314 nm 271 nm 239 nm
D. 314 nm 239 nm 271 nm
E. 271 nm 239 nm 314 nm
4. Which of the following absorption bands can be most easily used to distinguish between
CH3CH2C(=O)-NH-CH3 and CH3C(=O)-N(CH3)2?

  A) ~1700 cm-1 B) ~3000 cm-1 C) ~3300 cm-1

D) ~1450 cm-1 E) ~2950 cm-1

5. Two unknown isomeric alkenes, X & Z, have a molecular formula of C10H20. They have
nearly identical 1H NMRs. Each has one singlet and 2 doublets with very similar chemical
shifts. The signals for the 2 doublets are downfield. Compound X has J = 16 Hz and
Compound Z has J = 10 Hz. One Chem 227 student considered that the compounds must be
two of the following three possibilities. Which are they?

CH3 CH CH3 CH3

3 CH3 CH3 CH
H C 3 CH C CH
CH3 C C
3
H 3
CH3 C C CH3 C C CH3 C C CH3
C H H H H C
CH3
CH3 CH3 CH3
I II III
A) X = I; Z = III B) X = II; Z = I C) X = II; Z = III

D) X = I; Z = II E) X = III; Z = II

6. How many signals are predicted for the 1H NMR of the following compound?

CH3 CH3

CH3 CH2CHNHCCH3

CH3

A) 4 B) 5 C) 6 D) 7 E) 8

7. What is the multiplicity of the methylene hydrogens indicated in the proton NMR of the
following compound?

A. singlet
B. doublet
C. triplet
D. quartet
E. pentet
8. Which of the following would react the fastest with a strong base, such as NaNH2, to form a
carbanion?

9. Which of the structures can be classified as aromatic?

A. I and III
B. II and IV
C. II and III
D. III and IV
E. II only

10. Rank the following compounds in order of increasing rate of reaction when they are
respectively reacted with a mixture of acetyl chloride and aluminum chloride.

NH2 Br CH3
H2N O

I II III IV

A) IV < III < II < I B) I < IV < II < III C) III < II < IV < I D) III < II < I < IV

11. How many isomeric tribromobenzenes are possible? 

A) one B) two C) three D) four C) five

12. Which point on the potential energy diagram corresponds to the species shown to the right for
the electrophilic bromination of benzene with Br2/FeBr3?

13. Which of the following reactions is not a reduction?

A. reaction of an 1-butyne with sodium and liquid ammonia

B. reaction of an butyraldehyde with sodium borohydride
C. reaction of 2-butene first with borane (BH3) followed by OH- / H2O2
D. reaction of 2-butyne with sodium and liquid ammonia
E. reaction of acetophenone with hydrazine and NaOH

14. An unknown compound has the following 13C NMR. Identify the compound from the list of
structures below it.

O
CCH2 CH3 CH3 CH2 CH3 OH
OCH2 CH3
CH2 CH3

CH3
A B C D
O
H
15. The IR of an unknown indicates an ester with the molecular formula of C7H14O2. The
compound’s proton NMR follows. Identify the compound from the list of structures below.

mulitplet

O
O O
O CH3
O O
A B C
O O

O O
D E

16. Starting with toluene, which of the following is the best method to make the ether shown
below? (Assume you can separate ortho and para isomers.)

 
17. Which of the following is in the correct order of increasing oxidation number?

A. butyne < butene < butanol < butanone < butanoic acid
B. butyne < butene < butanol < butanoic acid < butanone
C. butanoic acid < butanone < butanol < butene < butyne
D. butene < butyne < butanol < butanone < butanoic acid
E. butanoic acid < butanone < butanol < butyne < butene

18. Which of the following has the lowest heat of reaction on catalytic hydrogenation? (4 moles
of H2 per mole of hydrocarbon)

19. Which one of the following reactions does not produce tert-butylbenzene? 

A. benzene + (CH3)3CH/AlCl3
B. benzene + (CH3 )2C=CH2/H2SO4
C. benzene + (CH3)3CCl/AlCl3
D. benzene + (CH3 )2CHCH2OH/H2SO4
E. benzene + (CH3)3COH/H2SO4

20. The respective 13C NMR chemical shifts for the compound below are δ 15.8, 40.1, 51.8,
170.2 ppm. Which of the carbon assignments is correct?

1 2 3 4
O
H3 C O C N CH2 CH3
A 51.8 40.1 170.2 15.8 H
1 2 3 4
B 170.2 15.8 51.8 40.1
C 51.8 170.2 40.1 15.8
D 40.1 170.2 51.8 15.8

End of Multiple Choice

True (A ) / False (B)

21. 3-hexen-2-one has a higher IR carbonyl frequency than 2-hexanone.

22. Lithium aluminum hydride will reduce 3-hexen-2-one but sodium borohydride will not.

23. In Electrophilic Aromatic Substitution reactions all electron withdrawing groups de-activate
and most direct to the meta position.
24. 1,1,2-trifluoroethyl benzene reacts slower than 1,1,2-trichloroethyl benzene with iron (III)
bromide plus bromine.

25. There is better value in burning benzene vs. cyclobutadiene as fuel in an automobile.
(Assuming the same relative amounts and the same prices per gallon).

26. There are 0 nodes in the following bonding orbital diagram of benzene.

27. The following 2D-NMR represents Carbon Hydrogen Correlation Spectroscopy (COSY),
which allows identification of coupled protons.

28. The 1H NMR of primary alcohols will have one more peak in the NMR when D2O is added.

29. The compound below is best named as 1-methyl-2-nitrobenzene.

CH3
NO2

30. Tylenol, aspirin, ibuprofen, and several other analgesics all have a substituted aromatic ring
in their respective structures, as does the compound above. Therefore, if the compound above
were taken after completing this exam, it would definitely cure my headache.

End of True/False
 31. (15pts) Friedl-Crafts acylation of para-chloroanisole produces predominately one product
with tiny amounts of a minor by-product. Provide structures for the major and minor products
and their respective intermediates. The electrophile is shown.

O
OCH3 +C CH3 - H+

Cl
O

+C CH3 Intermediate I major product

- H+

Intermediate II minor product

Label the reaction coordinate diagram below for the two products: label the major product (X),
the minor product (Y), the respective intermediates as (I) and (II), and all Transition States as
(TS). Draw the resonance structure of the starting material in the box which explains the
formation of the major product.

Resonance Structure:

ΔG

Reaction progress

The reactions are endergonic / exergonic. (Circle one.)

Briefly explain why the major product forms over the minor.
32. (15pts) a) Provide a synthesis of the product below from benzene using as many steps and
reagents as you find necessary. Be certain that the reaction chemistry for each step is correct
and indicate all of the reagents in each step. [NOTE: Four steps would likely be average.]

Cl

O2 N

a) Provide structures and reagents for the reaction sequence below.

OH
CH3
Na2 Cr2 O7 PCC
+
H

OCH3 OCH3