NATIONAL QUALIFICATIONS CURRICULUM SUPPORT

Chemistry
Proton (
1
H) NMR Spectroscopy
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< PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=)
8 Cro%n copyri/ht <71<
Contents
Proton en0ironments @
Assi/nin/ pe#s A
)r%in/ spectr B
An-ysin/ spectr C
PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=) D
8 Cro%n copyri/ht <71<
LEARNER WORKBOOK
Proton environments
For the e:mp-es $e-o%5
() 3r% the .,-- str,ct,r- .orm,-
($) circ-e the 3i..erent proton en0ironments1
11 Propn>1>o-
<1 Propn><>o-
D1 E,tne
@ PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=)
8 Cro%n copyri/ht <71<
C C C O
H
H
H H
H
H
H
H
C C C
H
H
H H H
H
O
H
H
C C C C
H
H
H H
H
H
H
H
H
H
LEARNER WORKBOOK
4. E,t><>ene
F1 Methy- $enGene
PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=) F
8 Cro%n copyri/ht <71<
C C C C
H
H
H H H H
H
H
C
C
C
C
C
C
C
H
H
H
H
H
H
H
H
LEARNER WORKBOOK
Assigning peaks
Use the
1
H NMR corre-tion t$-e in the 3t $oo# to pre3ict the chemic-
shi.t o. the protons in the e:mp-es in the $o0e 4,estion1
The shi.ts re /i0en s rn/e in the 3t $oo#1 Lerners sho,-3 $e
enco,r/e3 to 4,ote on-y one 0-,e .or shi.t in this e:ercise n3 it sho,-3 $e
%ithin the rn/e /i0en $e-o%1
11 Propn>1>o-
Group Cemical si!t "ppm#
CH
D
11<
CH
<
11FH71C
(-e.t o. CH
D
3,e to pro:imity to OH)
CH
<
D1CHD1F
OH F17H117
<1 Propn><>o-
Group Cemical si!t "ppm#
CH
D
11FH71C
CH D1CHD1F
OH F17H117
D1 E,tne
Group Cemical si!t "ppm#
CH
D
11FH71C
CH
<
11FH71C
@1 E,t><>ene
Group Cemical si!t "ppm#
CH
D
<1AH11A
CH A17H@1F
F1 Methy- $enGene
Group Cemical si!t "ppm#
CH
D
D17H<1D
CH I17HA1A
A PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=)
8 Cro%n copyri/ht <71<
LEARNER WORKBOOK
$rawing spectra
For the e:mp-es $o0e2 3r% the -o% reso-,tion NMR spectr,m yo, %o,-3
e:pect to see1 Remem$er to 3r% in the pproprite pe# hei/hts H yo, cn
ss,me the pe# hei/ht is the sme s the re ,n3er the c,r0e i. the pe# is
0ery nrro%1
The spectr 3r%n sho,-3 mtch the shi.t 0-,es inc-,3e3 in the $o0e
e:ercise1 Hei/hts sho,-3 $e pproprite .or the proton en0ironment1
11 Propn>1>o-
<1 Propn><>o-
PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=) B
8 Cro%n copyri/ht <71<
LEARNER WORKBOOK
D1 E,tne
@1 E,t><>ene
F1 Methy- $enGene
I PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=)
8 Cro%n copyri/ht <71<
LEARNER WORKBOOK
Anal%sing spectra
For ech o. the .o--o%in/ e:mp-es n-yse the hi/h reso-,tion proton NMR
spectr,m n3 s,//est str,ct,r- .orm,- .or ech compo,n31
PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=) C
8 Cro%n copyri/ht <71<
LEARNER WORKBOOK
E&ample '
17 PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=)
8 Cro%n copyri/ht <71<
CH
3
CH
2
OH
CH
3
Triplet due to neighbouring
CH
3
group.
CH
2
Quartet due to
neighbouring CH
3

group. The OH proton
does not interact with
the CH2 protons and
so does not affect the
splitting.
OH
The OH proton and the
protons on the next door
carbon do not interact with
each other (under normal
circumstances) and so no
splitting is seen for the OH
proton.
LEARNER WORKBOOK
E&ample (
PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=) 11
8 Cro%n copyri/ht <71<
CH
3
CH
2
CHO
CHO
Triplet due to
splitting from
CH
2
xpanded pea!
cluster at ".#"
ppm
CH
3
Triplet due to
neighbouring
CH
2
xpanded pea!
cluster at 2.$% ppm
CH
2
Quartet of
doublets arises
due to splitting
from CH
3
and
CHO protons
xpanded
pea! cluster
at &.&& ppm
The integral ratios on this spectrum do not
'uite wor! out as &(2(3 but this is a real
spectrum. The CHO pea! is not appearing
as a full proton.
LEARNER WORKBOOK
E&ample )
1< PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=)
8 Cro%n copyri/ht <71<
CH
3
COOCH
2
CH
3
xpanded pea!
cluster at $.&2 ppm
CH
2
Quartet due to
CH
3
CH
3
)inglet as there are no
protons on the ad*acent
carbon atom.
CH
3
Triplet due to
CH
2
xpanded
pea! cluster
at &.2+ ppm
LEARNER WORKBOOK
E&ample *
PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=) 1D
8 Cro%n copyri/ht <71<
CH3CH2COOCH2CH3
CH2
Quartet due to next door CH3. This is
shifted down field due to the proximit,
to the C-O.
CH2
Quartet due to next
door CH3.
CH3
Triplet due to
next door
CH2.
CH3
Triplet due to
next door
CH2.
xpanded pea!
cluster at $.&3 ppm
xpanded pea!
cluster at 2.32 ppm
xpanded
pea! clusters
at &.2+ and
&.&$ ppm
LEARNER WORKBOOK
E&ample +
1@ PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=)
8 Cro%n copyri/ht <71<
CH
3
COCH
2
CH
2
CH
3
CH
3
CH
2
Triplet due to
next door CH
2
.
CH
3
Triplet due to next
door CH
2
.
CH
2
This is appearing as a
.complicated/ 'uartet due to
CH
3
group howe0er the CH
2

has an effect as well and so the
pattern is more complicated
and should be regarded as a
multiplet.
LEARNER WORKBOOK
E&ample ,
PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=) 1F
8 Cro%n copyri/ht <71<
C
+
H
1
CH
3
CH
3
C
+
H
1
The chemical shift tells us these protons are the
aromatic protons and this is confirmed b, the ratio
of the integral cur0es. The pattern for phen,l
protons is complex. 2n this spectrum it seems there
are two proton en0ironments for the phen,l groups.
The two protons either side of the meth,l branch
and the rest of the phen,l protons.
LEARNER WORKBOOK
E&ample -
1A PROTON (
1
H) NMR SP'CTROSCOP= (AH2 CH'MISTR=)
8 Cro%n copyri/ht <71<
C
+
H
1
COOCH
2
CH
3
2 phen,l H
C
C
C
C
C
C
C
H
H
H
H
H
O
O CH
2
CH
3
CH
2
Quartet due to
next door CH
3
CH
3
Triplet due to
next door CH
2
xpanded pea!
cluster at &.3# ppm
xpanded pea!
cluster at $.3+ ppm
3 phen,l H