NAME: ________________________________ CHEM 3362

Haseltine/Spring 2011
DO NOT REMOVE ANY PAGES FROM THIS EXAM. Exam #2

I. Multiple Choice (4 pts. each): select the best answer for each question.

1. Of the following, which would be the most reactive compound under

aromatic nitration conditions?

2. How many signals (kinds of protons) are there in the proton NMR spectrum
of 2,2-difluoropentane? (Ignore solvent and any other compounds present.)
(a) two (b) three (c) four (d) five

3. Lithium dimethylcuprate (Me2CuLi) acts readily as a nucleophile with all of

the following types of organohalides except:
(a) 1-iodopropane. (c) iodobenzene.
(b) 2-bromopropene. (d) Actually, it acts as a Nu with all of these.

4. Which of the following reactions requires a stoichiometric (non-catalytic)

amount of its Lewis acid in order to obtain a good yield of product?
5. How many signals are there in the carbon-13 NMR spectrum of the
following alkane? (Ignore solvent and any other compounds present.)

(a) two (b) three (c) four (d) five

6. Wolff-Kishner conditions (H2N-NH2, KOH, alcohol, heat) are typically used

to cause what functional group transformation?
(a) C=O to CH2 (c) CH2OH to CH3
(b) alcohol to ether (d) NO2 to NH2

7. A good aromatic reactant for nucleophilic aromatic substitution should have

at least one of these attached directly to the ring:
(a) electron donating group (c) methoxy group
(b) electron withdrawing group (d) methyl group

8. Which alkylating agent will most likely lead to rearrangement during

Friedel-Crafts alkylation of benzene?
9. Adding any alkyl Grignard reagent to formaldehyde (H2C=O) is expected to
give, after the subsequent quench with dilute acid, a/an:
(a) primary alcohol. (c) tertiary alcohol.
(b) secondary alcohol. (d) aldehyde.

10. Adding methyllithium to ethyne (H-CC-H) leads to lithium acetylide

(Li-CC-H) and:
(a) methane. (c) water.
(b) H2. (d) no other product.

11. You should expect the proton NMR spectrum of the following compound to
consist of:

(a) two singlets. (c) two doublets.

(b) two triplets. (d) one doublet.

12. If I want to deuterate just one position in benzene, a good method would be
to react phenylmagnesium bromide (PhMgBr) with:
(a) t-butyllithium. (c) deuteromethane (CD4).
(b) D2O. (d) deuteroethane (C2D6).
13. Which method below is a standard way of making organometallic compounds
from organohalides?
(a) R-X + Li (c) R-X + 2 Mg
(b) R-X + 2 Li (d) both b and c

14. Carey says that in a typical 13C NMR spectrum, signals for carbons that
carry no protons usually show:
(a) unusually low intensities. (c) unusually complex splitting.
(b) unusually low frequencies. (d) unusually large integrations.

II. (8 pts.) Give two different combinations of Grignard reagent and

electrophile that would yield the following alcohol (after a suitable
aqueous quench). If you give more than two combinations, circle the
two that you want me to grade.
III. (12 pts.) Propose a specific structure for the following data set. If
you cannot deduce a specific structure, please assign as many
spectral signals as possible. SHOW YOUR REASONING - no
credit for the structure alone. IR and NMR reference tables are
attached below.

C4H8O2
IR includes 2980 cm-1 (broad), 1720 cm-1 (strong) implies OH and C=O
NMR
11.51 ppm, singlet (1H) implies OH
2.33 ppm, triplet (2H) implies X-CH2-CH2
1.67 ppm, app sextet (2H) implies CH2CH2CH3
0.98 ppm, triplet (3H) implies CH2-CH3

These bits can be assembled in only one way:

 IV. (12 pts.) Predict the proton NMR spectrum for the structure shown. In
table form, list clearly the expected chemical shifts for each kind of
proton as well as the respective signal integrations and multiplicities.

Type shift int mult

a 9.5-9.8 ppm 1H triplet

b 2.3 2H app. triplet
c 1.5 1H app. nine lines
d 0.9 6H doublet

V. (12 pts.) Give reagents suitable for carrying out the following reactions,
and give the major organic products. If an ortho,para mixture is
expected, show both products. If the meta isomer is the expected major
product, show only that isomer. (from Carey problem 12.34)

a) bromination of toluene

b) sulfonation of anisole (methoxybenzene)

Bonus question (4 pts.; please answer on the Scantron sheet):

15. What combination of ingredients represents a standard preparation of an
alkylzinc halide (as illustrated here for ICH2ZnI)?
(a) CH2I2, Zn, ether (c) I2, CH4, Zn, ether
(b) CH4, ZnI2, ether (d) CH2I2, ZnI2, ether