Lecture 1 Supplement

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1
 Lecture 1 Supplement
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2
 Lecture 2 Supplement
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3
 Lecture 2 Supplement

NMR Overlay of selected molecules depicting changes in chemical shift as more

electronegative atoms are added

CH4
0.23

- --- --·-----·-------- ----- ------------·------. --- ------- ..

I
� 2
PPM
r /
0.89
- - ·-- - --·· ·----·-·--- - ·- - -----·- -···- -··-······ ··-- -- ·- -·---·-·-·-·-···

,,CH3C(CH3)3
,t
2 PPM
1 I
� 1.13
CH2(C(CH3bh II
___,

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1

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�
I
·-- I J,

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1 I

2.47

1 0

4 2 0
PPM
CH30H

339

4 2 0
PPM

4
 Lecture 2 Supplement
annotated
Lectr,,rc 1 Sq,Plartgart A
NMR Overlay of selected molecules depicting changes in chemical shift.s more
electroncgativ. atoms are addcd

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5
 Lecture 2 supplement

Diamagnetic Anisotropy

Integration – area under the curve and relative to the number of protons
producing the resonance.
The integral at 3.5 ppm is twice as large as the integral at 2.3 ppm. This is
because the 4 protons of b give rise to the resonance at 3.5 ppm and the 2
protons of a give rise to the resonance at 2.3 ppm.

6
 Lecture 2 Supplement

14.7 The Characteristic Values of Chemical�

pROBLEM 11 ♦
a. Which proton or set of protons in each of the following compounds is the least shielded?
b. Which proton or set of protons in each compound is the most shielded?
0
II
2. .,,,.c " OCH 3. CH3 CHCHBr
CH CH 3 2 3 I I
Br Br

THE CHARACTERISTIC VALUES OF

CHEMICAL SHIFTS
Approximate values of chemical shifts for different kinds of protons are listed in Table 14.1. (A more
extensive compilation can be found in Appendix V.)

Table 14.1 Approximate Values of Chemical Shifts (ppm I for 1H NMR*

Type of proton ppm Type of proton ppm Type of proton ppm Type of proton ppm

ev
- - -- -- - -- - -- -
I
0.85 2.3 I-C-H 2.5-4 R-OH Variable, 2-5
� I
I Variable, 4-7
-CH2 - 1.20 -C=C-H 2.4 Br-C-H 2.5- 4 0-oH
I
I I 0-H 6.5-8
-CH- 1.55 R-O-CH3 3.3 Cl-C-H 3-4
I
0
= I II
-y y-@ 1.7 R-C=CH2
R
I -=
4.7 F-C-H 4-4.5 -C-H 9.0-10

0 R-C=C-H 0
I I I Variable, II
-C-@
CH3 2.1 R R 5.3 R -NH2 1.5-4 -C-OH Variable, 10-12
0
II
-C-NH2 Variable, 5-8
'The values are approximate because they are affected by neighboring substituents.

An 1 H NMR spectrum can be divided into seven regions, one of which is empty. If you can
remember the kinds of protons that appear in each region, you will know how to tell what kinds of
protons a molecule has from a quick look at its NMR spectrum.

0 H

6
0 II I
II H . H z c-c- I I
-C-H "c=c/ -C-C-H
-C-H
0 /. "
I I I I
II vinylic
Z = 0, N, halogen
C=C-C- saturated
-C-OH .1
12
allyJk I
9.0 8.0 6.5 4.5 2.5 1.5 0 -CH-
8 (ppm) methine

Methine, Methylene, and Methyl Protons

Carbon is more electronegative than hydrogen (Table 1.3 on page 46). Therefore, the chemical
�hift of a methine proton (a hydrogen bonded to an sp 3 carbon that is attached to three carbons) -CH3
- 18 more
deshielded and so shows a chemical shift at a higher frequency than the chemical shift methyl
. 7
 Lecture 3 supplement
Integration

Diamagnetic Anisotropy

Integration – area under the curve and relative to the number of protons
producing the resonance.
The integral at 3.5 ppm is twice as large as the integral at 2.3 ppm. This is
because the 4 protons of b give rise to the resonance at 3.5 ppm and the 2
protons of a give rise to the resonance at 2.3 ppm.

8
Lecture 3 Supplement
Equivalence

9
 i. ·
J CHAPTER 14 NMR Spectroscopy Lecture 4 Supplement
Splitting patterns and
CH3 CHC12 Multiplicity
,.-c-h-=em-
i c_al_s-h-_o_f -th_e_s-ig_ n _ al__fo_r-----,
ift
direct i on of the methyl protons. if there were
the applied , no protons on the adjacent
field , l, carbon

if the magnetic field of the
methine proton is in the
same direction as the
applied magnet i c f ield, it
will add to the applied
magnetic field, so the
adjacent methyl protons w ill
show a s i gnal at a ·slightly
higher frequency
=igure 14.11
signal for the methyl protons of
dichloroethane is split into a doublet
:he methine proton.
tf l+
' '
if the magnetic field
of the methine proton is
lined up against the applied
magnetic field, it wi ll subtract
from the applied magnetic
field, so the adjacent methyl
protons will show a s ignal at
a slightly lower frequency
-+---- frequency

Therefore, the signal for the methyl protons is split into two peaks, one at a higher frequency and
at a lower frequency. Because the a- and /3-spin states have almost the same population (Figure 14 ..
page 657), about half the methine protons are lined up with the applied magnetic field and about hati
lined up against it. As a result, the two peaks of the doublet have approximately the same height and a

Forming a Quartet
Similarly, the frequency at which the methine proton shows a signal is influenced by the magnetic fo
of the three protons bonded to the adjacent carbon. The magnetic fields of all three methyl protons
align with the applied magnetic field, two can align with the field and one against it, one can align,
it and two against it, or all three can align against it (Figure 14.12). Because the magnetic field that
methine proton senses is affected in four different ways, its signal is a quartet (Figure 14.13 ).

chem i cal shift of the methine

proton if there were no protons
on the adjacent carbon

,,",,
,, \\

,,
,, ,,,,
' ',, ,,,,
'
2 with 2 against
and and
all with 1 against 1 with all against

ttt tt+ ++t +++

..-'----.. ,-4-------,, -----. �

t+t it+
itt t++
-+---- frequency ---- frequency

Figure 14.12 A Figure 14.13

The different ways in which the magnetic The signal for the methine proton of 1,1-dichloroethane is
fields of three protons can be aligned. split into a quartet by the methyl protons.

Why does the signal for the methine proton in Figure 14.13 have peaks of different intensitie
that is, why are the inner peaks more intense than the outer peaks?
The relative intensities of the peaks in a signal reflect the number of ways the neighboring prot
can be aligned relative to the applied magnetic field (Figure 14.12). There is only one way to align
magnetic fields of three protons so that they are all lined up with the applied magnetic field and c
one way to align them so that they are all lined up against the applied field. However, there are tr

10
 Lecture 5 Supplement
Sketching spectra

a. C. · Cl-f
0 b. 3
' \
C i-t�Cl-12. )�ocH 2, c.l-t 3 C. L+?> - C.i-t
I
B ,.-

cl+2 B-Y
I
C 1-l 3 - C - 0"-2. Sr-
\
C 1+2- 16-v-

11
Lecture 5 supplement

12
Lecture 5: Supplement

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Lecture 5: Supplement

14
Lecture 5: Supplement

15
Lecture 6: Supplement

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Lecture 6: Supplement

17
Lecture 7: Supplement

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Lecture 7: Supplement

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Lecture 7: Supplement

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