1

CP203 LecLure 17
CcLober 14, 2014

13
C nM8
8lLs and pleces
2
3
4
1
CH203 Fall 2014 NMR Practice Quiz

1. Consider the
1
H NMR spectrum below


a. How many types of hydrogen are present, assuming no serious overlap between different
types? _____

b. What is the chemical shift of the hydrogen type that is most shielded? ______

c. Consider the multiplicity, which derives from spin-spin coupling. What best describes the
most shielded hydrogen type?
____Singlet
____Doublet
____Triplet
____Quartet
____Doublet of doublets

d. What does this multiplicity indicate about the most shielded hydrogens?
_____There is one hydrogen present at this position
_____There are two hydrogens present at this position
_____There are three hydrogens present at this position
_____There are two hydrogens on the neighboring carbon
_____There are three hydrogens on the neighboring carbon

e. If the molecular formula of the compound is C3H7Br, what does the integration show about the
most shielded hydrogens?
_____There is one hydrogen present at this position
_____There are two hydrogens present at this position
3
13
C nM8 and Lhe lourler 1ransform
1here are Lwo klnds of nM8 specLromeLers: conunuous wave specLromeLers and
pulse specLromeLers.
ln a CW specLromeLer, Lhe sample ls placed ln a sLauc magneuc eld and swepL wlLh
radlofrequency (8f) energy. 1he CW nM8 specLrum shows peaks aL frequencles where
Lhere ls absorpuon of 8f energy.
ln a pulsed specLromeLer, Lhe sample ls placed ln a sLauc magneuc eld and Lhen hlL
wlLh a pulse of 8l waves powerful and wlde enough Lo slmulLaneously exclLe all nuclel ln
Lhe sample. Aer Lhe pulse Lhe nuclel reLurn Lo Lhelr ground sLaLes by radlaung Lhe
absorbed energy. 1he pulsed specLromeLer deLecLs Lhls reradlaLed energy as a lree
lnducuon uecay (llu) slgnal. 1he compuLer uses Lhe lourler 1ransform (l1) Lo converL Lhe
llu ume daLa lnLo frequency daLa whlch ls presenLed llke Lhe orlglnal CW specLra.
6
13
C nM8
!"#$%&'( *+,- #$,.+/+/0
12
3 456 (7&8,".

13
C makes up only 1 of Lhe carbon ln a sample.
1he gyromagneuc rauo of
13
C ls one-fourLh of LhaL of
1
P.

1hls means LhaL Lhe
1
P slgnal ls 1000 umes sLronger Lhan Lhe
13
C slgnal.

1o geL a useable specLrum, Lhe l1-nM8 pulses Lhe sample muluple umes and Lhe
compuLer sums Lhe llus Lo enhance peaks and mlnlmlze nolse.



7
13
C nM8
1he
13
C resonance slgnal ls also spllL by Lhe proLons auached Lo lL. ln Lhe Lop specLrum of
norbornane, carbons 2,3,4, and 6, whlch are all equlvalenL and all have Lwo hydrogens
bound, appear as a LrlpleL.

A pulse specLromeLer ls able Lo lrradlaLe Lhe sample wlLh a second radlofrequency energy
whlch ls absorbed by all Lhe hydrogens and decouples Lhelr spln sLaLes from Lhe carbon spln
sLaLes. 1he spln decoupled specLrum ls on Lhe bouom. Lach seL of equlvalenL carbons ls seen
as one peak.
8
9
ulse sequences
DEPT
Goto
66 Bruker AVANCE Users Guide
Figure 18: DEPT Pulse Sequence
Acqui sition and Processing 6.3
Insert the sample in the magnet. Lock the spectrometer. Readjust the Z and Z
2
shims
until the lock level is optimized. Tune and match the probehead for
13
C observation,
1
H decoupling.
Reference spectra
Since DEPT is a
13
C-observe,
1
H-decouple experiment, the first step would be to
obtain a reference
1
H spectrum of the sample to determine the correct o2 for
1
H
decoupling. The second step would then be to obtain a
1
H-decoupled
13
C spectrum
to determine the correct o1 and sw for the DEPT experiments. However, both of
these steps were already carried out in Section 4.3 starting on page 37. So, a
1
H-
decoupled
13
C reference spectrum of this sample can be found in carbon/3/1. (The
one thing to be aware of is that broadband decoupling was used in carbon/3/1, but
here the cpd sequence WALTZ-16 will be used).
Create a new file directory for the data set
Enter re carbon 3 1 to call up the reference spectrum. Enter edc and change the
following parameters:
NAME dept
EXPNO 1
PROCNO 1 .
Click SAVE to create the data set dept/1/1.
Set up the acquisition parameters
Enter eda and set the acquisition parameters as shown in Table 22. Use the values
determined in Chapter 5 Pulse Calibration for the parameters pl1 and p1 (
13
C
observe high power level and 90 pulse time), pl2 and p3 (
1
H decouple high power
level and 90 pulse time), and pl12 and pcpd2 (
1
H decouple low power level and
cpd
acq
!
! "
!
2
!
2
13
C
1
H
1
2J
XH
1
2JXH
1
2J
XH
t
rd
p1 p2
p3 p4 p0
d2 d1 d2 d2
Slmple pulse sequence
ulse sequence for a uL1
(9lsLoruonless :nhancemenL by
!olarlzauon ;ransfer) experlmenL.
10
ulse sequences - uL1
11
ulse sequences - A1
12
13
C nM8 examples
13
13
C nM8 examples
14
13
C nM8 examples
13
WhaL ls lL?
C
6
P
8
C
4
1
P
13
C
(
13
C slgnals are noL proporuonal Lo Lhe
number of carbons aL LhaL ppm.)
2P
6P
16
WhaL ls lL?
C
6
P
8
C
4
1
P
13
C
(
13
C slgnals are noL proporuonal Lo Lhe
number of carbons aL LhaL ppm.)
2P
6P
H
H
O
O
OCH
3
OCH
3
ulmeLhyl maleaLe
17
WhaL ls lL?
C
4
P
4
S

(
13
C slgnals are noL proporuonal Lo Lhe
number of carbons aL LhaL ppm.)
1
P
2P 2P
13
C
18
WhaL ls lL?
C
4
P
4
S

(
13
C slgnals are noL proporuonal Lo Lhe
number of carbons aL LhaL ppm.)
1
P
2P 2P
13
C
S
1hlophene
19
P
a
P
b
P
c
vs. P
a
P
b
P
a
sysLems
1.5 2.0 2.5 3.0 3.5
http://www.nmrdb.org/new_predictor/
1 of 1 10/13/14 12:11 AM
2.0 3.0 4.0
http://www.nmrdb.org/new_predictor/
1 of 1 10/13/14 12:14 AM
H
3
C
O O
CH
3
H
3
C
O N
H
CH
3
20
Pz and ppm
1he operaung frequency of an nM8 lnsLrumenL depends on Lhe sLrengLh of Lhe
magneL and ls a funcuon of Lhe gyromagneuc rauo of Lhe nuclel belng observed.

An lnsLrumenL labeled 300 MPz means LhaL lL has a magneL whlch generaLes a
eld of abouL 7.03 1. (8
o
= 7.03 1)

AL 7.03 1,
1
P resonance ls abouL 300 MPz.
13
C resonance ls abouL 73 MPz.
AL 11.73 1,
1
P resonance ls abouL 300 MPz.
13
C resonance ls abouL 123 MPz.





! =
difference between observed peak and TMS in Hz
operating frequency of instrument
360 Hz
300 x 10
6
Hz
1.2
= 1.2 ppm
10
6
=
21
1
P nM8 examples
H
H
H
22
1
P nM8 examples
23
1
P nM8 examples
O
24
1
P nM8 examples
A 6.639 8 3.836 C 2.433 u 1.873 L 1.169
23
1
P nM8 examples
-70
o
C




22
o
C
26
CH
3
CH
3
CH
3
CH
3
CH
3
CH
3
27
CH
3
NO
2
CH
3
NO
2
28
1
P nM8 problem
Compound wlLh a molecular formula of C
4
P
9
Cl

1
P nM8:
3.38 ppm (d, !=6 Pz, 2P)
1.93 ppm (m, 1P)
1.01 ppm (d, !=6.6 Pz, 6P)

13
C nM8:
32.49 ppm
31.06 ppm
20.08 ppm
29
1
P nM8 problem
Compound wlLh a molecular formula of C
4
P
9
Cl

1
P nM8:
3.38 ppm (d, !=6 Pz, 2P)
1.93 ppm (m, 1P)
1.01 ppm (d, !=6.6 Pz, 6P)

13
C nM8:
32.49 ppm
31.06 ppm
20.08 ppm
1he Ml glves an lPu of 0, Lells me Lhere are no rlngs or double bonds.

1he
13
C nM8 conLalns Lhree slgnals, buL Lhe Ml conLalns four carbons, so Lwo
of Lhe carbons musL be equlvalenL.
30
1
P nM8 problem
Compound wlLh a molecular formula of C
4
P
9
Cl

1
P nM8:
3.38 ppm (d, !=6 Pz, 2P)
1.93 ppm (m, 1P)
1.01 ppm (d, !=6.6 Pz, 6P)

13
C nM8:
32.49 ppm
31.06 ppm
20.08 ppm
1he 6P aL 1.01 mlghL be Lwo CP3 groups spllL by one P, meanlng Lhe 1P aL
1.93 could be LhaL one P belng spllL by 6Ps lnLo a sepLeL. A sepLeL ls
someumes reporLed as 'm', a mulupleL, lf Lhe ouLer slgnals are losL ln Lhe
basellne nolse and Lhe exacL mulupllclLy ls noL clear.
31
1
P nM8 problem
Compound wlLh a molecular formula of C
4
P
9
Cl

1
P nM8:
3.38 ppm (d, !=6 Pz, 2P)
1.93 ppm (m, 1P)
1.01 ppm (d, !=6.6 Pz, 6P)

13
C nM8:
32.49 ppm
31.06 ppm
20.08 ppm
1here ls probably an lsopropyl group presenL based on Lhe double and
mulupleL slgnals. 1he Lwo CP3 groups are equlvalenL ln Lhe
13
C nM8. 1hey
would show as one slgnal. 1hls mlghL explaln Lhe loss of one slgnal ln Lhe
13
C
nM8.
R CH
3
CH
3
H
32
1
P nM8 problem
Compound wlLh a molecular formula of C
4
P
9
Cl

1
P nM8:
3.38 ppm (d, !=6 Pz, 2P)
1.93 ppm (m, 1P)
1.01 ppm (d, !=6.6 Pz, 6P)

13
C nM8:
32.49 ppm
31.06 ppm
20.08 ppm
1he lsopropyl group ls C3P7, so Lhere ls only CP2Cl Lo be accounLed for ln Lhe
sLrucLure. 1he slgnal aLe 3.38 ppm mlghL be hydrogens on a carbon also
bound Lo a chlorlne. 1hls glves a fragmenL of Cl-CP2-8
R CH
3
CH
3
H
33
1
P nM8 problem
Compound wlLh a molecular formula of C
4
P
9
Cl

1
P nM8:
3.38 ppm (d, !=6 Pz, 2P)
1.93 ppm (m, 1P)
1.01 ppm (d, !=6.6 Pz, 6P)

13
C nM8:
32.49 ppm
31.06 ppm
20.08 ppm
R CH
3
CH
3
H
Cl R
+
Cl
CH
3
CH
3
Comblne fragmenLs and check posslble nal sLrucLures agalnsL nM8 daLa.
34