228 Exam Kevin Burgess, September 13, 14 1

Exam 3, Chem 228 (512) Burgess

name: __________________________________________
email address: _______________________________________

Answer all the questions. No books, notes, or models allowed. Calculators are allowed.
Circle correct options for parts that give two choices underlined.

1 __________________ (2 pts)
2 __________________ (2 pts)
3 __________________ (2 pts)
4 __________________ (2 pts)
5 __________________ (2 pts)
6 __________________ (2 pts)
7 __________________ (2 pts)
8 __________________ (2 pts)
9 __________________ (2 pts)
10 _________________ (2 pts)

total _______________ (20 pts)

228 Exam Kevin Burgess, September 13, 14 2

1 Draw the products of the following reactions.












(1 perfectly correct, 1 pt, 2 or 3 perfectly correct 2 pts, but they have to be perfect and clear!)
228 Exam Kevin Burgess, September 13, 14 3
2 Show the Grignards that could be used to make the following alcohols
from methanal.













(3 perfectly correct, 1 pt; 5 or 6 perfectly correct 2 pts)
228 Exam Kevin Burgess, September 13, 14 4
3 Predicting the products of the following reactions (after protonation).















(2 perfectly correct, 1 pt, 3 or 4 perfectly correct 2 pts, but structures have to be very clear!)
228 Exam Kevin Burgess, September 13, 14 5
4 Show the Grignards and aldehydes that could be used to make the
following alcohols. If there are two ways of doing this, indicate both.

















(There are considered to be 3 parts to this question. 1 perfectly correct 1 pt, 2 or more
correct 2 pts)
228 Exam Kevin Burgess, September 13, 14 6
5 Predict the products and intermediates in the following sequence, and
carefully show the electron flow.














Tetrahedral intermediates formed from Grignard reagents and carboxylic esters expel
alkoxides to give a ketone or aldehyde / acid anhydride / nitrile in situ, but this intermediate is
more / less reactive than the ester starting material so the product is usually a primary /
secondary / tertiary alcohol where at least two / three substituents are the same.

(0,1 or 2 mistakes or omissions 2 pts, 3-4 mistakes or omissions 1 pt, no pts if there are 5 or
more mistakes or omissions, eg missing or improperly drawn arrows)

228 Exam Kevin Burgess, September 13, 14 7
6 Predict the product of the following reactions.















(5 parts; 2 perfectly correct, 1 pt: 4 or more perfectly correct, 2 pts)
228 Exam Kevin Burgess, September 13, 14 8
7 Predict the major products of these reactions.









.. and draw the cyclic intermediate in the following reaction.



(4 part question: 2 perfectly correct, 1 pt, 3 or more perfectly correct 2 pts)
228 Exam Kevin Burgess, September 13, 14 9
8 Draw mechanism for the following conjugate additions.










Conjugate additions to the -carbon are favored for soft / hard nucleophiles while soft / hard
nucleophiles tend to add to the carbonyl group. Both dimethyl cuprate and methyl
magnesium halides are sources of nucleophilic methyl groups, but the copper-based reagent
is softer / harder.

(0 or 1 mistakes or omissions 2 pts, 2-3 mistakes or omissions 1 pt, no pts if there are 4 or
more mistakes or omissions, eg missing or improperly drawn arrows)


228 Exam Kevin Burgess, September 13, 14 10
9 Draw the mechanism for ketal formation from acetone and methanol.













(0 or 1 mistakes or omissions 2 pts, 2-3 mistakes or omissions 1 pt, no pts if there are 4 or
more mistakes or omissions, eg missing or improperly drawn arrows)
10 Refer to the spectra attached for compound 1 which is made from an
aldehyde and an alcohol, and answer the following.
228 Exam Kevin Burgess, September 13, 14 11
(i) double bond equivalents ______
(ii) number of
1
H environments (multiplet around 7.2 ppm counts as one) ______
(iii) number of
13
C environments ______
(iv) carbon types present (just tick) C ______ CH
2
______ CH or CH
3
______
(v) show structure of one fragment cation formed in the MS:


(1 pt for 3 or more correct)


(g) give structure here













To check for your answer, assign important IR peaks, important MS fragments, proton
NMR,
13
C NMR by indicating on structure. (1 pt for correct structure with 4 reasonable
assignments clearly marke
228 Exam Kevin Burgess, September 13, 14 12
COMPOUND 1