Organic Chemistry 432 Practice Exam #2-3

Cole

March 5, 2019 Name

First Last Name

Circle Lab Section:

TA Lab
1 Monday 1-4 PM
2 Tuesday 8-11 AM
3 Tuesday 1-4 PM
4 Wednesday 1-4 PM
5 Thursday 8-11 AM
No lab Students not attending any lab section this semester

Notes: Before starting exam, please check that you all 6 questions on 6 pages, with an additional 1 scratch
pages and table of spectroscopic data. Be sure that you have answered the entire question and be brief and
concise as possible. Approach each problem systematically and stepwise. Finally, reread the question and your
answer, did you fully answer the question?

PERIODIC TABLE OF THE ELEMENTS

H He
1.008 4.00

Li Be B C N O F Ne
6.94 9.01 10.81 12.011 14.00 15.999 18.99 20.18

Na Mg Al Si P S Cl Ar
22.99 24.30 26.98 28.08 30.97 32.06 35.45 39.95

K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
39.10 40.08 44.96 47.90 50.94 51.99 54.94 55.85 58.93 58.71 63.54 65.37 69.72 72.59 74.92 78.96 79.91 83.80

Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
85.47 87.62 88.91 91.22 92.91 95.94 [99] 101.07 102.91 106.4 107.87 112.40 114.82 118.69 121.75 127.60 126.90 131.30

Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
132.90 137.34 138.91 178.49 180.95 183.85 186.2 190.2 192.2 195.09 196.97 200.59 204.37 207.19 208.98 [210] [210] [222]

Fr Ra Ac
[223] [226] [227]
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu
140.12 140.91 144.24 [147] 150.35 151.96 157.25 158.92 162.50 164.93 167.26 168.93 173.04 174.97

Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lw
232.04 [231] 238.03 [237] [242] [243] [247] [247] [249] [254] [253] [256] [254] [257]

1
Point Summary (For graders only):

#1(20) #2(28) #3(10) #4(12) #5(28) #6(12) (110) Total

1.(20) Propose an acceptable mechanism for the formation of the imine from α-tetralone and tert-butylamine
under buffered acidic conditions at pH ~ 4.5 using p-toluenesulfonic acid, TsOH. Clearly show all
intermediates, indicating all electron pair movement using curved arrows and indicating the reversible steps.
DO NOT combine steps, unless they are concerted.

O N
SO3H
H2 N
+ + H2 O
pH ~ 4-5

2
2.(28) Indicate the expected major products that are formed in the following reactions. Include whether other
regioisomeric products will be formed as well as stereochemistry if required.

OH

A. + HNO3 /H2 SO4

O
B. t-BuOH
+ Na
NH3 (l)
-33 °C

CN +
+ Et2 O H3 O
C. MgBr

OH

D. + H2 SO4 (conc)

CH3

OCH3 hexane H2 O
E. + H Al
-78 °C
DIBAL-H

HCl(g) Raney
F. + HS SH
Nickel

O
+
Cl + Et2 O H3 O
G. Li HAl(Ot-Bu)3
-78 °C

3
3.(12) D-Ribose can exist in two forms, the open-chain form that contains an aldehyde group and its
hemiacetal form as a five-membered ring. Give in detail an acceptable mechanism for the acid catalyzed
formation of the hemiacetal, showing all intermediates, indicating all electron pair movement using arrows. DO
NOT combine steps unless they are concerted.

OH OH O
H3 O
+
HO OH
O
H + H2 O
OH OH OH
HO

4
4.(28) Give in detail an acceptable mechanism for the acid catalyzed hydrolysis of the propylene glycol of 2-
butanone showing all intermediates, indicating all electron pair movement using arrows. DO NOT combine
steps unless they are concerted.

O
+
O O H3 O HO OH
+ H2 O +

5
6.(12) Propose a laboratory synthesis of the following compounds starting with the indicated starting material
and any organic compound containing four or fewer carbons, oxygens, halogens, etc and any inorganic
reagents. Note, the desired product may require more than one step. Be sure to include all steps and stable
intermediates along with necessary reaction conditions to form the products. Assume that ortho/para mixtures
can readily be separated.

Br
A.
HO

NO2