1he prevlous sllde may be found aL

hup://www.[kwchul.com/2011/12/lnLerpreung-proLon-nmr-overvlew/
CP203 LecLure 16
CcLober 10, 2014

Complex coupllng
13
C nM8
1960: 8ruker klS-1 nM8 (23 MPz)
Pow much lnformauon have we gouen ouL of Lhe nM8 so far?
1. 1he locauon of Lhe hydrogen resonance ln ppm
(chemlcal shl). 1ells us Lhe local elecLronlc
envlronmenL of Lhe hydrogen.
2. 1he number of dlerenL hydrogen resonances. 1ells
us how many seLs of nonequlvalenL hydrogens are
presenL.
3. 1he number of hydrogens ln each nonequlvalenL seL
by lnLegrauon.
4. 1he number of nelghborlng hydrogens.
3. 1he orlenLauon of Lhe nelghborlng hydrogens
(coupllng consLanL).

Spln-spln coupllng ln a vlclnal Lwo hydrogen sysLem
vocabulary
C C
H H
C C
H H
C C
H
H
C C
H
H
H
H
C C
H
C H
H
H
H
H
H
H
!
", vlclnal
6-8 Pz
!
", vlnyllc #$%
3-10 Pz
!
", vlnyllc '()*%
11-18 Pz
+
", vlnyllc ,-.$*)/
0-3 Pz
+
", ,-.$*)/
0-3 Pz
0
", allyllc
0-1 Pz
+
", 1('21
7-9 Pz
!
", meLa
2-3 Pz
0
", 3)()
0-1 Pz
8eporung nM8 daLa
10
1he eLhyl group
11
1he lsopropyl group
Complex coupllng
1he Pb slgnal ls spllL by Pa ("
ab
) and Lhen by Pc ("
bc
) Lo glve a doubleL of doubleLs.
(1hls only applles lf "
ab
and "
bc
are noL equal or close Lo equal.)
Complex coupllng
1he Pb slgnal ls spllL by Pa (!ab) and Lhen by Lwo Pc (!bc) Lo glve a doubleL of LrlpleLs.
(1hls only applles lf "
ab
and "
bc
are noL equal or close Lo equal.)
WhaL happens when Lhe "s are equal or close Lo equal?
When "
ab
and "
bc
are close Lo Lhe same magnlLude, Lhe spllmng Lree does noL generaLe Lhe
expecLed nlne slgnals of a LrlpleL of LrlpleLs. Cnly ve peaks are seen due Lo overlap.
WhaL happens when Lhe "s are equal or close Lo equal?
ln Lhls case, "
ab
and "
bc
are close Lo Lhe same
magnlLude because Lhey are ln a exlble chaln.
8oLauon averages Lhe coupllng consLanLs Lo
abouL Lhe same value.

ln general, where you would expecL Lo see
(n +1) x (m +1) peaks, a exlble sysLem llke Lhls
wlll glve (n + m +1) peaks.

(n +1) x (m +1) = 9 peaks expecLed

(n + m +1) = 3 peaks observed
WhaL happens when Lhe "s are equal or close Lo equal?
ln 1-chloro-3-bromopropane, "
ab
and "
bc
are almosL equal. We do noL see Lhe expecLed
nlne peaks [(n +1) x (m + 1)] of a LrlpleL of LrlpleLs for Pc. Cnly ve peaks (n + m +1) are
observed.


WhaL happens when Lhe "s are equal or close Lo equal?
ln 1-chloropropane, "
ab
and "
bc
are almosL equal. We do noL see Lhe expecLed Lwelve peaks
[(n +1) x (m + 1)] of a LrlpleL of quarLeLs for Pb. Cnly slx peaks (n + m +1) are observed.


Cemlnal coupllng ln an alkene
nM8 of eLhyl propenoaLe. 1he reglon around 6 ppm needs Lo be expanded Lo see Lhe
spllmng pauerns and measure Lhe coupllng consLanLs.
Cemlnal coupllng ln an alkene
nM8 of eLhyl propenoaLe. 1he slgnals for Lhe Lhree vlnyllc hydrogens are each a doubleL
of doubleLs. 1he pauern changes as Lhe coupllng consLanL changes.
Cemlnal coupllng ln a rlng
2-meLhyl-2-vlnyloxlrane. 1he Lwo P aLoms on Lhe oxlrane rlng are nonequlvalenL, so
Lhey exhlblL gemlnal coupllng.
1oplclLy
Pydrogens are homoLoplc lf replacemenL does noL generaLe a new chlral cenLer. u
(
2
P) ls someumes used as Lhe LesL replacemenL.

ln dlbromomeLhane, Lhe hydrogens are homoLoplc and so are always ldenucal.
Br
C
Hb
Br Ha
Br
C
D
Br Ha
Br
C
Hb
Br D
1oplclLy
Pydrogens are enanuoLoplc lf replacemenL does generaLe a new chlral cenLer.

ln bromouoromeLhane, Lhe hydrogens are enanuoLoplc and so are ldenucal ln
achlral envlronmenLs.
Br
C
Hb
F Ha
Br
C
D
F Ha
Br
C
Hb
F D
1oplclLy
Croups are dlasLereoLoplc lf replacemenL does generaLe a new chlral cenLer ln a
molecule wlLh aL leasL one exlsung chlral cenLer.

ln 3-meLhyl-2-buLanol, Lhe Lwo meLhyl groups bonded Lo C3 are dlasLereoLoplc and
so are noL equlvalenL. ulasLereoLoplc groups wlll exhlblL dlerenL chemlcal shls.
C
OH
CH
3
H
3
C
H
3
C
C C
OH
CH
3
H
3
C
D
3
C
C C
OH
CH
3
D
3
C
H
3
C
1oplclLy
O
CH
3
H
3
C
H
3
C
1he Lwo meLhyl groups aL C3 ln 3-meLhyl-2-buLanone are noL dlasLereoLoplc and appear
as a clean doubleL aL abouL 1 ppm.
1oplclLy
1he Lwo meLhyl groups aL C3 ln 3-meLhyl-2-buLanol are dlasLereoLoplc and appear
as Lwo doubleLs aL abouL 1 ppm.
OH
CH
3
H
3
C
H
3
C
1oplclLy
PomoLoplc: replacemenL does noL generaLe a new chlral cenLer
always ldenucal
same chemlcal shls

LnanuoLoplc: replacemenL does generaLe a new chlral cenLer
ldenucal ln achlral envlronmenLs
same chemlcal shls ln achlral nM8 experlmenL

ulasLereoLoplc: replacemenL does generaLe a new chlral cenLer ln a molecule
wlLh aL leasL one exlsung chlral cenLer
dlerenL chemlcal shls

WhaL ls an achlral nM8 experlmenL?
!"#$ &' (")* "+ ",-./"0 123 *+4./'+(*+&

Chlral solvenL: noL many avallable, very expenslve

Chlral addluve: shl reagenLs" are chlral molecules whlch complex wlLh Lhe LargeL
molecule and shl Lhe proLon slgnals ln one enanuomer

Chlral derlvauves: chemlcally add a chlral group Lo Lhe mlxLure of enanuomers Lo
generaLe a mlxLure of dlasLereomers whlch wlll have dlerenL nM8s
WhaL ls an achlral nM8 experlmenL?
Sodlum [(8)-1,2-ulamlnopropane-n,n,n',n'-LeLraaceLaLo]samaraLe(lll), hydraLe
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.
13
C nM8
5/'60*($ 7.&- '6&".+.+8
9:
; 123 $<*,&/"

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.



13
C nM8
1he 13C 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.
13
C chemlcal shls
13
C chemlcal shls compared Lo
1
P
=>
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
(=lsLoruonless >nhancemenL by
5olarlzauon ?ransfer) experlmenL.
ulse sequences - uL1
ulse sequences - A1
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
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
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
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