CHEM 213 FALL 2016

MIDTERM EXAM 2 - VERSION B KEY

Answer multiple choice questions on the green computer sheet provided with a PENCIL.
Be sure to encode both your NAME and Registration Number (V#).

You will draw the structures of Molecules BA-BB on the Separate Double-Sided
STRUCTURE ANSWER SHEET. You will also enter your selection for Molecule U
(bonus question) on that sheet. Be sure to put your NAME on that sheet as well.

There should be 8 pages (double-sided) in this examination AND you should have a
green Scantron form, PLUS a STRUCTURE ANSWER SHEET (double-sided).

There are 14 graded multiple choice questions worth 21 marks and two structure
solutions worth 24 marks for a TOTAL of 45 MARKS. There is also a BONUS
QUESTION (molecule U) on the last page worth 5 extra marks. There are 50 minutes
available for this examination so ration your time accordingly.

YOU MAY ONLY USE A Non-Programmable CALCULATOR.

Substituent constants for 13C and 1H chemical shift prediction:

δ aromatic C = 128.5 + Δipso + Δortho + Δmeta + Δpara δ arom H = 7.27 + Δortho + Δmeta + Δpara

R Δipso Δortho Δmeta Δpara Δortho Δmeta Δpara

OH 26.9 -12.7 1.4 -7.3 -0.49 -0.13 -0.20
F 34.8 -12.9 1.4 -4.5 -0.30 -0.02 -0.23
NHCOCH3 11.1 -9.9 0.2 -5.6 0.65 0.20 0.22
CH=CH2 9.5 -2.0 0.2 -0.5 0.00 -0.03 -0.10
N(CH3)2 23.0 -16.0 1.0 -12.0 -0.60 -0.10 -0.62
CH2CH3 15.6 -0.4 0 -2.6 -0.15 -0.06 -0.18
CHEM 213 Midterm 2 Version B November 22, 2016 Page 2 of 8

1. This is exam VERSION B, mark B on the computer sheet as the answer to question 1

Consider Molecule R when

answering Questions 2-8;
hydrogens are numbered and
carbons are lettered.

2. How many unique 13C signals will Molecule R show in the 13C DEPT-135 spectrum? i
(a) 8 (b) 9 (c) 10 (d) 11 (e) 12
(f) 3 (g) 4 (h) 5 (i) 6 (j) 7

13
3. Which of the following best matches the appearance of the carbon C in the C DEPT-135
spectrum of R? d
(a) 128 ↑ (b) 123 ↑ (c) 114 ↑ (d) 114 ↓ (e) 30 ↓
(f) 42 ↑ (g) 42 ↓ (h) 65 ↑ (i) 65 ↓ (j) absent

4. Which of the following statements correctly reflects the relationship between H8 and H9 in the 1H
NMR spectrum of R? (assume couplings greater than 3J are zero) b
(a) chemically and magnetically nonequivalent
(b) chemically and magnetically equivalent
(c) diastereotopic
(d) chemically equivalent and magnetically nonequivalent
(e) chemically nonequivalent and magnetically equivalent
CHEM 213 Midterm 2 Version B November 22, 2016 Page 3 of 8

5. Which choice represents ALL the carbons to which H10 shows long range HMQC (J = 10 Hz) for
molecule R? i
(a) G (b) H (c) I (d) K (e) L
(f) M (g) N (h) H and L (i) H and M (j) K and M

6. What is the predicted chemical shift of carbon-G in the 13C NMR of R (using the data on page 1)? b
(a) 108.5 (b) 110.0 (c) 110.5 (d) 112.5 (e) 119.0
(f) 124.5 (g) 128.9 (h) 139.2 (i) 147.0 (j) 151.9

7. What pattern is possible for H14 in the low temperature 1H NMR spectrum of R? d
(a) s (b) d (c) t (d) q (e) pentet
(f) sextet (g) dd (h) tt (i) d of pentet (j) dq

8. What is the chemical shift of H7 in the 1H NMR of R? (using the data on page 1). c
(a) 6.35 (b) 6.55 (c) 6.65 (d) 7.17 (e) 7.27
(f) 8.47 (g) 7.94 (h) 7.89 (i) 7.49 (j) 7.37
CHEM 213 Midterm 2 Version B November 22, 2016 Page 4 of 8

Consider Molecule S when

answering Questions 9-11.
Assume 4JHF coupling is
resolvable at about 3 Hz.

9. How many lines in total would you expect to observe in the 13C DEPT-135 spectrum of S? (note,
for example that a doublet is 2 lines in total while two doublets would be 4 lines in total). f
(a) 0 (b) 1 (c) 2 (d) 3 (e) 6
(f) 9 (g) 12 (h) 18 (i) 27 (j) 36

19
10. What pattern(s) would you expect to see in the F NMR spectrum of Molecule S at room
temperature? d
(a) s (b) d (c) t (d) dd (e) ddd
(f) two d (g) two dd (h) two t (i) four s (j) dddd

11. What is the appropriate spin system label for the coupled spins in Molecule S (ignore the OH group
in answering this)? f
(a) A2X4 (b) A2B4 (c) A2B2B’2 (d) AA’B2B’2
(e) AA’X4 (f) AA’X2X’2 (g) AA’BB’B’’B’’’ (h) AA’MM’XX’
CHEM 213 Midterm 2 Version B November 22, 2016 Page 5 of 8

________________________________________________________________________________
For EACH STRUCTURE below, DRAW your answer on the separate structure sheet.
________________________________________________________________________________
Compound BA C11H15NO IR: 3390, 2738, 1708, 811 cm-1 [10 pts]

12. One of these functional groups is present in Compound BA; which one is it? (note: there could be
other unlisted functional groups present) e
(a) terminal alkyne (b) conjugated ketone (c) primary amide
(d) secondary amide (e) secondary amine (g) meta-substituted aromatic

13. How many double bond equivalents are there in Compound BA? f
(a) 0 (b) 1 (c) 2 (d) 3 (e) 4 (f) 5 (g) 6 (h) 7 (i) 8 (j) 9

1
H NMR:
Note: the s at
δ 3.9 becomes a
triplet at low T

13
C NMR:

DEPT-135 phasings
shown

Selected 1H-1H COSY: δ 2.6 ppm with δ 9.75 and 3.45 ppm
NOTE: the H at δ 1.25 ppm shows coupling to the C at δ 135 ppm in the long range HMQC.
CHEM 213 Midterm 2 Version B November 22, 2016 Page 6 of 8

Compound BB C10H16O2 [14 pts]

IR: 1735 cm-1

14. How many double bond equivalents are there in Compound BB? d
(a) 0 (b) 1 (c) 2 (d) 3 (e) 4 (f) 5 (g) 6 (h) 7 (i) 8 (j) 9

15. What functional group could be present in Compound BB from all the information given? b
(a) alkyne (b) ketone (c) aldehyde (d) ester
(e) acid (f) alcohol (g) aromatic ring (h) trans-alkene

1
H NMR:

13
C{1H} and
DEPT-135
CHEM 213 Midterm 2 Version B November 22, 2016 Page 7 of 8

Short range HMQC (J = 135 Hz): 6.1 s ------ 147.9(+)

4.3 t ------ 71.8(-)
2.7 septet --- 40.4(+)
2.65 t ------ 41.6(-)
2.5 t ------ 33.0(-)
2.3 t ------ 24.3(-)
1.15 d ------ 20.3(+)

Long range HMQC (J = 10 Hz): 6.1 s ------ 71.8(-), 33.0(-), 24.3(-)

4.3 t ------ 147.9(+), 122.6(x)
2.7 septet --- 41.6(-)
2.65 t ------ 122.6(x), 40.4(+)
2.5 t ------ 147.9(+), 24.3(-)
2.3 t ------ 213.9(x), 147.9(+), 33.0(-)
1.15 d ------ 213.9(x), 20.3(+)

Don’t forget to enter your structures for BA and BB on the separate structure sheets!

THIS IS A BONUS QUESTION: 1H, 13C{1H| and DEPT NMR data to select the correct structure for
Molecule U and Enter your selection in the space provided on the separate structure answer sheet.
[5 pts]

1
H NMR (300 MHz):
CHEM 213 Midterm 2 Version B November 22, 2016 Page 8 of 8

13
C{1H} NMR with

DEPT-135 phasing:

Choices: A B C D
O O O
O O O O
O
O O O
O O O O
O

E F G H
O O O O
O O O
O
O
O O O
O O O O

I J K L
O O O
O O O O O O
O O O
O
O O
O

Don’t forget to enter your selection on the separate structure sheet!

END
Structure Key and solutions – Chem 213 Midterm 2 Version B

Structure of BA C11H15NO
DBE = ((11x2+3)-15)/2 = 5 (Aromatic + 1)
IR 3390 probably NH (exchangeable, 1H integration, only O is in a carbonyl)
2738 aldehyde CH stretch
1708 non-conjugated aldehyde so not on ring
811 para-disubstituted aromatic (matches 1H NMR)

1
H 9.75 aldehyde H is a narrow triplet so must be HC(=O)CH2 and coupling/COSY
say this is the one at 2.6 ppm. Since the CH2 at 2.6 is a td it must be next to
another CH2 (3.45) and we must have an isolated CH2CH2C(=O)H chain. The
downfield chemical shift of this 2nd CH2 is strongly suggestive that it is on N so
we have an –NHCH2CH2C(=O)H chain.
Besides this chain, we also have a 2H q around 2.85 ppm and a 3H t at about
1.25 ppm which must be coupled to each other giving us an ethyl group,
CH2CH3.
That accounts for everything and we just have to connect the pieces to get BA:

O
H H
N

O
H
N H

We can check the position of the ethyl group by noting that there is a long range HMQC
correlation between the ethyl CH3 protons and an aromatic ring C (135x) as expected.
Structure of BB C10H16O2
DBE = ((10x2+2)-16)/2 = 3
IR 1735 could be ester or a ketone (not aldehyde as no 2750) but it is a ketone
from the 13C chemical shift (>190 ppm)
If this is the carbonyl, the other O has to be in an ether (no OH so not an alcohol)

We need some DBE so check unsaturated region of 13C first. There are two C in this
region: 122x (so =C) and 147.9+ (=CH) meaning we also have a tri-substituted alkene,
C=CH. Note too, that the C with the H is unusually far downfield; this is suggestive of an
O directly on this C and since the lone alkene H is a singlet, we may have C=CH-O- but
we can check this later.
We are still short one DBE and there is nothing else that can be unsaturated so we
must have a ring (note the symmetry is obviously very low so there is no way we can
have two identical carbonyls or alkenes).
Rings can be tricky to locate properly so it is usually advisable to find all the other parts
first and then the ring will (hopefully) be obvious.

Looking at the 1H NMR, it is clear there is a CH2 on an ether oxygen (t) and it must
be connected to another CH2 giving us a –OCH2CH2 unit. All of the other CH2 groups
are simple triplets so that means this group is isolated. Using the same logic, the two
remaining CH2 must be linked together too and isolated: -CH2CH2-.
What else is left? A 6H d and a 1H septet. This is the classic pattern for an isopropyl
group: -CH(CH3)2.

That means we have all the pieces located since this totals to C10H16O2:
Since all of these units are bi- or higher functionality, it makes sense to start form the
known terminal unit (the isopropyl) and see where it is connected. Long range HMQC
comes in very handy here: by seeing which C the isopropyl CH3 protons how LR HMQC
to, we establish what the isopropyl is connected to:
 1.15 with 213.9(x) and 20.3(+). The 20.3 is just the other CH3 carbon but the 213.9 is
the carbonyl so now we know the i-Pr group is on the carbonyl.
We can use the i-Pr CH protons in the same way to establish what is on the other side
of the carbonyl:
2.7 septet with 41.6(-) which is a CH2 and the short range HMQC establishes this
as the one at 2.65 t, another CH2 group which is a triplet and therefore part of one of
the CH2CH2 units.
If you now use the 2.65 t in the long range HMQC you can find out what is on the other
side of the CH2 next to it:
 2.65 t with 122.6(x) and 40.4(+). The 40.4(+) is the CH of the i-Pr from the short range
HMQC (we already knew that direction) but the 122.6(x) is the fully substituted end of
the alkene. This makes sense in that there could not be a CH2 on the alkene CH end or
the alkene H would not be a singlet. So, we have made a lot of progress and now know
we have the following:

All that is needed is to connect the remaining chain to the alkene C to form the ring that
we need for our last DBE. Although there are two ways to connect this chain, it must be
connected as shown or the alkene H would not be a singlet and we also noted before
that the alkene CH carbon was much further downfield than usual which is consistent
with the structure as shown.
Structure of Bonus Molecule U

This problem is very straightforward as long as you pay attention to symmetry. The fact
that the 1H NMR shows only two simple triplets but in 4H to 4H ration means there must
be two identical –CH2CH2- units. The chemical shift of one is far downfield so it must be
–OCH2CH2- x 2.

The 13C NMR shows one type of acid-derivative carbonyl C but two alkene C. The
latter fact means that the alkene ends are different and tetra-substituted.

With the above information, we can assess each structure and identify the correct
choice:
A, B, H have singlets in the 1H NMR so are eliminated
E, G have alkene H in the 1H NMR and are eliminated
C, D, F are ketones and do not match the 13C shift of the carbonyl
L does not have a CH2 on O and the ends of the alkene are the same
K does not have a CH2 on O
J has chemically equivalent C for each end of the alkene
I fits everything and is the correct choice