CHEM 430 NMR Spectroscopy Chapter 3

NMR
Spectrosc
opy
Fall
4
1
0
2
CHEM 430
NMR - The
Chemical
Shift
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FACTORS THAT INFLUENCE PROTON

SHIFTS
Local Fields
Shielding by e- that surround the resonating nuclei arise from
local fields
They are a simple function of e- density affected by induction,
resonance and hybridization effects

The magnetic field at the nucleus is altered from B0 to a
quantity B0(1-) where is called the shielding
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SHIFTS
Local Fields
Electronegativity effects
A nearby e- withdrawing atom or group with decrease edensity moving the observed resonance downfield to higher
Conversely, a nearby e- donating atom or group will
increase e- density moving the observed resonance upfield

OH
to lower
CH
3
B0(1 )
OH <
CH3
E = h
B0
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NMR - The
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SHIFTS
Local Fields
B0(1 )
O < C
E = h
B0
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SHIFTS
Local Fields
The trend follows Pauling electronegativity (EN) scale:
EN
of H
CH3F
CH3O-
CH3Cl
CH3Br
CH3I
CH4
(CH3)4Si
CH3Li
4.0
3.5
3.1
2.8
2.5
2.1
1.8
1.0
4.26
3.40
3.05
2.68
2.16
0.23
0.0
-0.4
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SHIFTS
Local Fields
The effect is cumulative:
of H
CH3Cl
CH2Cl2
CHCl3
3.05
5.30
7.27
The effect drops sharply with distance:
of H
-CH2Br
-CH2CH2Br
-CH2CH2CH2Br
3.30
1.69
1.25
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SHIFTS
Local Fields
The effect is a useful tool in quickly deducing simple
aliphatic chains:
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NMR - The
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SHIFTS
Local Fields
Resonance effects
Donation or withdrawal of e- through resonance will have
shielding or deshielding effects, respectively:
resonance donation
shielding effect
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Spectroscopy
resonance withdrawal
deshielding effect
NMR - The
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Shift
31

SHIFTS
Local Fields
Hybridization effects
Hybridization of the carbon atom influences e- density
As proportion of s-character increases (sp3 sp2 sp)
bonding electrons move toward C and away from hydrogen

- deshielding
This effect however is secondary to the influence of the -
cloud of electrons from the unhybridized p-orbitals as we

will see
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NMR - The
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SHIFTS
Nonlocal Fields
Purely magnetic effects from a neighboring group can influence
nuclear shielding
As we saw earlier the combined effects of local and nonlocal fields:
Nonlocal fields have a major influence on chemical shift only if the
group has a non-spherical shape

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SHIFTS
Nonlocal Fields
The electrons in a spherical substituent also precess in the
applied field, creating a non-local field
As the molecule tumbles the lines of magnetic force will
remain lined up with the applied field, but the position of the
attached nuclei will change
The effect cancels itself out leaving only the effect on the
local field by the substituent
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NMR - The
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SHIFTS
Nonlocal Fields
The electrons in a non-spherical substituent also precess in
the applied field, creating a non-local field
In benzene, the 6-p-orbitals overlap to allow full circulation of
electrons; as these electrons circulate in the applied magnetic

field they oppose the applied magnetic field at the center:
B0
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NMR - The
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SHIFTS
Nonlocal Fields
At the ring periphery, the effect is opposite and the protons
are deshielded :
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13
NMR - The
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SHIFTS
Nonlocal Fields
The benzene system is not spherical, but an oblate ellipsoid
As the molecule tumbles in in solution there is either the
effect of shielding inside the ring or deshielding outside the

ring if the ring is perpendicular to the applied field
OR
No effect if the ring is parallel to the applied field
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NMR - The
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SHIFTS
Nonlocal Fields
Groups that have appreciably different currents induced by B0
resulting from different orientations in space are said to have
diamagnetic anisotropy
Just as the local effect can result in shielding (electron
donation) or deshielding (electron withdrawal) the nonlocal

effect can result in either permutation
Regions of shielding are indicated by (+) and deshielding (-)
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SHIFTS
Nonlocal Fields
The effect was modeled quantitatively by McConnell
The following equation relates shielding to the influence of a
magnetic dipole on the point in space where a proton(nuclei)

resides:
A shielding for a proton at
(r, )
L and T are the diamagnetic
susceptibilities of the group
longitudinal and transverse to
B0
At = 54o 44 the expression (3cos2 1) goes to zero
On either side of this magic angle A changes sign
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SHIFTS
Nonlocal Fields
The protons of benzene reside on the periphery of the ring
within the deshielding cone
Molecules have been constructed for the purpose of
confirming the shielding effect predicted by the model:

H2
C
-0.5
CH2
H -3.0
9.3 H
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SHIFTS
Nonlocal Fields
4n + 2 -electrons (aromatic) result in the diamagnetic
circulation of e-s
Pople demonstrated that 4n -systems have the opposite or
paramagnetic circulation:
5.2
10.3
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SHIFTS
Nonlocal Fields
For a prolate ellipsoid it is sometimes not as clear as to
which arrangement has the stronger induced current
The acetylene system provides a simple example
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SHIFTS
Nonlocal Fields
We say the shift for the terminal acetylene proton experiences
magnetic anisotropy. Usual shifts for this H are 1.8-3.0. For
reference sp3 ethane is at 0.86 and sp2 ethene at 5.28
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SHIFTS
Nonlocal Fields
Alkanes do not possess the same degree of electron
circulation as alkynes but do exert nonlocal fields on adjacent
nuclei
The CC -bond shields a proton on its side more than its end
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SHIFTS
Nonlocal Fields
The result of which is a deshielding of equatorial protons in
conformationally locked systems:
Even simple alkane systems show anisotropy:
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SHIFTS
Nonlocal Fields
The result of which is a deshielding of equatorial protons in
conformationally locked systems:
Even simple alkane systems show anisotropy:
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SHIFTS
Nonlocal Fields
The highly shielded position of cyclopropane resonances may
be attributed either to an aromatic-like ring current or to the
anisotropy of the bond that is opposite to a group in the threemembered ring:
The effect is much larger than the indicated 1.2 ppm ,
because the cyclopropane carbon orbital to hydrogen

( compared with the orbital in cyclohexane) deshields the
proton.
A cyclopropane ring also can shield more distant hydrogens:
Heq 1.2 less than Hax
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NMR - The
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SHIFTS
Nonlocal Fields
Most common single bonds (C-N, C-O) have shielding
properties that parallel those of the bond, although the
geometry is more complex than that for the C-C bond.
Lone electron pairs can have a special effect:
In N-methylpiperidine the axial lone pair shields the vicinal H ax
by an n * interaction without any effect on Heq. As a result,

Hax increases to about 1.0 ppm or more in similar systems.
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SHIFTS
Nonlocal Fields
The anisotropy of double bonds is more difficult to assess,
because they have three nonequivalent axes (the McConnell
equation, with only two axes, does not apply).
Protons situated over double bonds are, in general, more
shielded than those in the plane both for alkenes and for
carbonyl groups
The position of the methylene protons in norbornene may be
explained in this fashion since the syn and endo protons,

respectively, are shielded with respect to the anti and exo
protons.
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NMR - The
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SHIFTS
Nonlocal Fields
The highly deshielded position of aldehydes ( ca. 9.8) is
attributed to a combination of a strong polar effect and the
diamagnetic anisotropy of the carbonyl group.
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NMR - The
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SHIFTS
Nonlocal Fields
The nonspherical array of lone pairs of e- may exhibit
diamagnetic anisotropy, although, alternatively, the effect

may be considered a perturbation of local currents.
A proton that is H-bonded to a lone pair is invariably
deshielded.
For example: the -OH proton in ethanol
CCl4 resonates at 0.7 (dilute no H-bonding)
CD3CD2OH resonates at 5.3 (H-bonding)
Carboxylic protons resonate at extremely high frequency
(11 14), because every proton is H-bonded within a dimer

or higher aggregate.
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NMR - The
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SHIFTS
Nonlocal Fields
Lone- pair anisotropy also has been invoked to explain trends in ethyl
groups :
For XCH2CH3:
-CH2-
CH3
4.36
1.24
Cl
3.47
1.33
Br
3.37
1.65
3.16
1.86
The resonance position of CH2- attached to X is explained by the polar
effect
The trend for the more distant CH 3 group is opposite; as X increases
size, the lone pair moves closer to the CH 3 group and deshields it.
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NMR - The
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SHIFTS
Summary
Functional group effects on proton chemical shifts are explained
largely by two general effects.:
1. Local Effects: Electron withdrawal or donation by
induction (including hybridization) or by resonance alters
the electron density and hence the local field around the
resonating proton.
Higher electron density shields the proton (lower ,
upfield)
Low electron density deshields the proton (higher
downfield)
2. Nonlocal Effects: Diamagnetic anisotropy of nonspherical
substituents is largely responsible for the proton resonance

positions of aromatics, acetylenes, aldehydes,
cyclopropanes, cyclohexanes, alkenes, and hydrogenbonded species.
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NMR - The
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PROTON CHEMICAL SHIFTS AND

STRUCTURE
3-2a Saturated Aliphatics

Alkanes.
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NMR - The
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STRUCTURE

Functionalized Alkanes.
Oxygen:
Nitrogen:
Sulfur and the Halides:
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NMR - The
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NMR - The
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STRUCTURE

After years of collective observation of 1H (and 13C) NMR it is possible
to predict chemical shift to a fair precision using Shoolery Tables
These tables use a base value for 1H (and
C) chemical shift to which

are added adjustment increments for each group on the carbon atom
= 0.23 + X + Y +
H
X C H
H
methyl
13
Z
H
X C Y
H
methylene
H
X C Z
Y
methine
The tables work well for methyl and methylene but diverge greatly
with methine due to the increased interaction between effects

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NMR - The
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STRUCTURE

Functionalized Alkanes. Example Shoolery Table - Methylene
X or Y
Increment
X or Y
Increment
-H
0.34
-OC(=O)OR
3.01
-CH3
0.68
-OC(=O)Ph
3.27
-CC
1.32
-C(=O)R
1.50
-CC-
1.44
-C(=O)Ph
1.90
-Ph
1.83
-C(=O)OR
1.46
-CF2-
1.12
-C(=O)NR2 or H2
1.47
-CF3
1.14
-CN
1.59
-F
3.30
-NR2 or H2
1.57
-Cl
2.53
-NHPh
2.04
-Br
2.33
-NHC(=O)R
2.27
-I
2.19
-N3
1.97
-OH
2.56
-NO2
3.36
-OR
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2.36Spectroscopy
-SR or H
-OPh
2.94
-OSO R
35
1.64
3.13
NMR - The
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STRUCTURE

Functionalized Alkanes. Example Shoolery Table - Methine
X ,Y or Z
Increment
X, Y or Z
Increment
-F
1.59
-OC(=O)OR
0.47
-Cl
1.56
-C(=O)R
0.47
-Br
1.53
-C(=O)Ph
1.22
-NO2
1.84
-CN
0.66
-NR2 or H2
0.64
-C(=O)NH2
0.60
-NH3+
1.34
-SR or H
0.61
-NHC(=O)R
1.80
-OSO2R
0.94
-OH
1.14
-CC-
0.79
-OR
1.14
-C=C
0.46
-C(=O)OR
-OPh
2.07
CHEM 430 NMR
Spectroscopy
1.79
-Ph
36
0.99
NMR - The
Chemical
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32

STRUCTURE

After years of collective observation of 1H (and 13C) NMR it is possible
to predict chemical shift to a fair precision using Shoolery Tables
These tables use a base value for 1H (and
C) chemical shift to which

are added adjustment increments for each group on the carbon atom
= 0.23 + X + Y +
H
X C H
H
methyl
13
Z
H
X C Y
H
methylene
H
X C Z
Y
methine
The tables work well for methyl and methylene but diverge greatly
with methine due to the increased interaction between effects

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NMR - The
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STRUCTURE
3-2b Unsaturated Aliphatics

Alkynes.
Anisotropy of CC results in a low frequency for terminal-H (1.8 3.0)
Alkenes.
Anisotropy of C=C results in a higher frequency for alkenylic (vinyl)-H
Range is very large (4.5 7.7) and highly subject to other groups on
C=C
Reference value used for ethene is 5.28
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STRUCTURE

Alkenes.
Conjugation usually increases the observed frequency
Angle strain increases s-character and therefore moves the
resonance to higher frequency
The presence of a C=O group w/d electrons by both
resonance and induction:
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NMR - The
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STRUCTURE

Alkenes.
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STRUCTURE

Alkenes.
These effects were quantified by Tobey and of Pascual, Meier,
and Simon,
Using an empirical approach they tabulated a series of
geminal, cis and trans substituents relative to the proton

being observed:
= 5.28 + Zgem + Zcis + Ztrans

Although the parameters incorporate inductive and resonance
effects, steric effects can cause deviations from observed

positions.
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STRUCTURE

Alkenes.
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STRUCTURE
3-2c Aromatics
Diamagnetic anisotropy from aromatic ring current shifts the
protons to high frequency benzene is used as a reference (7.27)
Rings with only aliphatic substituents tend to bunch the
resonances about this frequency (toluene, ~ 7.2)

Conjugating substituents tend to spread the aromatic resonances
based on contributing resonance structures and inductive effects:
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STRUCTURE
3-2c Aromatics
The -protons in aromatic heterocycles are shifted due to the
polar effect of the heteroatom:
As with the alkane and alkene systems a systematic
observation has been made of aromatic H-resonances. They

can be predicted from the following:
= 7.27 + Si
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STRUCTURE
3-2c Aromatics
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STRUCTURE
3-2c Aromatics
Aromatics:
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STRUCTURE
3-2c Aromatics
Heteroaromatics:
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STRUCTURE
3-2d Protons on Oxygen and Nitrogen

Chemical shifts of protons attached to highly electronegative atoms
such as O or N are influenced strongly by acidity, basicity, and

hydrogen-bonding
Protons on Oxygen
For OH, minute amounts of acidic or basic impurities can bring
about rapid exchange
They are averaged with other exchangeable protons, either in
the same molecule or in other molecules, including the solvent.
Only a single resonance is observed for all the exchangeable pro-
tons at a weighted-average position and no coupling is observed.
The resonance varies from sharp to slightly broadened,
depending on the exchange rate.

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STRUCTURE

-OH may be determined by exchange experiments described
earlier (shaking the NMR sample with D2O)
At infinite dilution in (no H-bonding), the OH resonance of
alcohols may be found at about 0.5.

Under more normal conditions of 5% to 20% solutions, hydrogen
bonding results in resonances in the 2 4 range.

More acidic phenols (ArOH) have resonances downfield at 4 8.
Interaction with an ortho group shifts this to 10 or higher.
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STRUCTURE

Most carboxylic acids exist as H-bonded dimers or oligomers, even
in dilute solution.
Hydrogen bonding coupled with the strong deshielding of the
carboxlate group places the acid protons resonate far downfield

(11 14)
Likewise, other highly H-bonded acidic protons also may be found
in this range, such as sulfonic, phosphonic and enolic protons
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STRUCTURE
Protons on nitrogen
Similar properties to -OH
Lower
electronegativity of N results upfield shifts than those OH protons:

0.5 3.5 for aliphatic amines, - NH 2
3 5 for aromatic amines ( anilines), Ar-NH 2
4 8 for amides, pyrroles, and indoles
6 8.5 for ammonium salts, -NH3+ (amino acid protons can
exchange rapidly with solvent or other exchangeable protons to
achieve an averaged position)
The most common nuclide
N is quadrupolar and possesses unity spin

(could split the resonance of attached protons into a 1: 1: 1 triplet) - rapid
relaxation of quadrupolar 14N averages the spin states usually appearing
as a broadened resonance
14
Broadening may render NH resonances almost invisible.

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STRUCTURE
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STRUCTURE
3-4 Factors That Influence Carbon Shifts

Carbon is the defining element in organic compounds, but its major
nuclide 12C has a spin of zero.
Advent of pulsed FT-methods allowed practical examination of the
low- abundance nuclide
13
C ( 1.11%)
The low probability of having two adjacent nuclei (0.01%) in a single
molecule removes complications from carboncarbon couplings.

When C-H couplings are removed by decoupling techniques, the
spectrum is essentially free of all spinspin coupling, and one singlet

arises for each distinct type of carbon.
Integration is rarely done as
C has a much larger range of relaxation

times than 1H and because the decoupling field perturbs intensities
13
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STRUCTURE

Analysis therefore is simpler for 13C than for 1H spectra but
Diamagnetic shielding (d) which is responsible for 1H chemical shifts,
is caused by circulation of the electron cloud about the nucleus 1Hs

are surrounded solely by s electrons ( lacking angular momentum)
and consequently exhibit only diamagnetic shielding
In carbon 2p electrons have angular momentum that can hinder free
circulation - hindrance to free electron circulation creates an

additional mechanism called paramagnetic shielding (p)
Because p serves to reduce d the two mechanisms have opposite
signs
C nuclei (and almost all other nuclides as well) additionally are

surrounded by p electrons and exhibit both forms of shielding.
13
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STRUCTURE
The paramagnetic component can be quite large!

Chemical-shift range for 1H is only a few ppm, while
paramagnetic shifts for other nuclei can extend over a

range of hundreds or even thousands of ppm.
Qualitatively, angular momentum can arise from excited
electronic states and from bonding. The effects are larger

when electron density about the nucleus increases.
These three considerations were gathered by Ramsay,
Karplus, and Pople into the simple empirical relationship

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STRUCTURE
= average energy of excitation of certain electronic transitions, such
as the n * transition for many
13
C and
15
N nuclei.
The radial term includes the average distance r from the nucleus of the
2p electrons - this term serves as a measure of electron density.

Qij represents -bonding to carbon. The negative sign in the equation
indicates that paramagnetic shielding is in the opposite direction from

d .
Structural changes can affect all three components of the equation.
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STRUCTURE
The quantity E represents the weighted- average energy
difference between the ground and certain excited states.
Because of symmetry considerations, the * transition is
often excluded
Low-lying excited states (with small E) make the largest
contribution, since E appears in the denominator.

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STRUCTURE
Saturated molecules, such as alkanes, typically have no low-lying excited
states ( and hence possess a large E), so that p is small and alkane
carbon resonances are found upfield
*Note that paramagnetic shielding causes shifts to high frequency,
whereas diamagnetic shielding causes shifts to low frequency
On the other hand carbonyl carbons have a low-lying excited state
involving the movement of electrons from the oxygen lone pair to the
antibonding orbital that generates a paramagnetic current.
This n * transition causes the large shift to high frequency that
characterizes carbonyl groups up to 220 ppm

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STRUCTURE
The radial term is responsible for effects related to electron density
that parallel polar effects on proton chemical shifts.

P is larger when the p-electrons are closer to the nucleus. Thus,
substituents that donate or withdraw electrons influence the

paramagnetic shift.
e- donation increases repulsion between electrons, which can be
relieved by an increase in r, P decreases, causing an upfield
shift
e-withdrawal permits electrons to move closer to the nucleus,
increasing P ,causing an upfield shift
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STRUCTURE
Qij is related to charge densities and bond orders and can be
considered a measure of multiple bonding. The greater the

degree of multiple bond-ing, the greater the downfield shift
This term provides a rationale for the series:
CH3CH3 ( 6) < H2C=CH2 (123) < H2C=C=CH2 ( 214)

Arene shifts are similar to those of alkenes (benzene, 129) -
The effects of diamagnetic anisotropy on carbon chemical

shifts are similar in magnitude to the effects on protons, but
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are small in relation
to the range of carbon shifts.
Spectroscopy
NMR - The
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34

STRUCTURE
Alkynes do not follow this pattern, but are at an intermediate
position (72 for acetylene), because their linear structure has zero
angular momentum about the axis.
There are exceptions, the most prominent being the effect of
heavy atoms. The series ( CH3Br (10), CH2Br2 (22), CHBr3 (12), and
CBr4 (-29) defies any explanation based on electronegativity,
unlike the analogous series given before for chlorine.
This so- called heavy- atom effect has been attributed to a new
source of angular
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from spinorbit
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coupling.
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STRUCTURE
3-5 Carbon Chemical Shifts and Structure

You should know the most basic of shift tables:
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Replacement of H on carbon () or an adjoining carbon () will
shift the resonance by 9 ppm
The replacement at the -position however shifts -2.5 ppm
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STRUCTURE

For this reason 13C shifts lend themselves readily to empirical
analysis:
Each Ai or substituent parameter is added to -2.5 ppm (shift
for CH4) for a maximum set of five carbons:
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STRUCTURE

In general CH3 resonances appear at 5-20, -CH2- at 15-35 and
CH- at 25-45
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Some complications: Corrections must be applied if branching
is present
The
13
The
13
The
13
C methyl is corrected for the presence of an adjacent 3o

carbon by adding -1.1 and for an adjacent 4o carbon by
adding -3.4.
C methylene has corrections of and -2.5 and -7.2,
respectively, for adjacent 3o and 4o carbons.
C methine has respective corrections of -3.7, -9.5 and
-1.5 for adjacent 2o, 3o, and 4o carbons.
4o carbons have corrections of -1.5 and -8.4 for adjacent 1 o
and 2o carbons. Corrections for adjacent tertiary and

CHEM
430 NMR are significant, but are not
quaternary carbons
undoubtedly
68
Spectroscopy
known accurately.
NMR - The
Chemical
Shift
35

STRUCTURE
3-5a Cyclic Alkanes.

For small cycloalkanes: -3.8 , cyclopropane has the most upfield
resonance of hydrocarbons. Cyclobutane and cyclopentane are
higher.
Larger cycloalkanes generally resonate within 2 ppm of
cyclohexane, at 27.7.
The fixed stereochemistry of cyclohexane requires a set of
empirical parameters that depend on the axial or equatorial

nature of the substituents, as well as on the distance from the
resonating carbon.
CHEM 430 NMR
Spectroscopy
69
NMR - The
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35

STRUCTURE

The following table lists parameters for methyl substitution are
added to the value for cyclohexane ( 27.7).
The substituent parameter for -axial methyl is large and
negative , reflecting the pure gauche stereochemistry between

the perturbing and resonating carbons.
A - equatorial group represents - anti effect and has little
perturbation
CHEM 430 NMR

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70
NMR - The
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35

STRUCTURE

Corrections again are needed for branching.
Geminal methyls: = -3.4, = -1.2
Example: the calculated resonance for C2 of 1,1,3-
trimethylcyclohexane :
27.7 + 5.2 + (8.9 * 2) - 1.2 = 49.5 ( observed 49.9)
Other examples:
CHEM 430 NMR
Spectroscopy
71
NMR - The
Chemical
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35

STRUCTURE
3-5a Functionalized Alkanes.

The replacement of a hydrogen atom on carbon with a
heteroatom or an unsaturated group usually results in
downfield shifts due to polar effects on the radial term.
The effect parallels the same structural change on 1H
chemical shifts but arises from a different mechanism.
CHEM 430 NMR

Spectroscopy
72
NMR - The
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35

STRUCTURE

Alkyl Halides.
Strongly EWGs have large positive effects. In the halogen
series:
CH3F 75.4 CH3Cl 25.1 CH3Br 10.2 CH3I -20.6
Multiple substitution results in larger effects 77.7 for CHCl3
Recall that the effect of heavy atoms such as iodine or bromine
is influenced by a spin orbit mechanism and hence may not

follow the simple order of electronegativity.
The general range for the halogen effect in hydrocarbons
extends from the values given above for the simple systems to
about a 25- ppm downfield shift for CH2X and CHX systems,
since the and effects of the unspecified hydrocarbon pieces
CHEM 430shift
NMR
contribute to the downfield
73
Spectroscopy
NMR - The
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Shift
35

STRUCTURE

Alcohols and Ethers:
The range for HO- substituted carbons is 49 75. (MeOH at
49.2)
The range for RO-substituted carbons is 59 80. (CH3OCH3 at
59.5)
The ether range is translated a few ppm downfield from
alcohols, because each ether must have one additional -effect

with respect to the analogous alcohol.
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Spectroscopy
74
NMR - The
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35

STRUCTURE

Amines:
The lower EN of nitrogen moves the amine range somewhat
upfield (CH3NH2 at 28.3), the range for amines extending
some 30 ppm higher
The amine range is larger than the alcohol range because
nitrogen can carry up to three substituents, with more and

effects possible
Other EN groups:
CH3SCH3 at 19.5, CH3CN at 1.8, and CH3NO2 at 62.6, with the
respective ranges for thioalkoxy, cyano, and nitro substitution
extending some 25 ppm downfield
The anomalous low- frequency position for -CN substitution is
CHEM 430
NMRof the group and its reduced
related to the cylindrical
shape
75
Spectroscopy
angular momentum.
NMR - The
Chemical
Shift
35

STRUCTURE

Attached C=C or C=O
An attached double bond has only a small effect on a methyl
group.
For example, the position for the methyls of trans-2-butene is
17.3, and that for the methyl of toluene is 21.3.

The range for carbons on double bonds is about 15 40.
Methyls on carbonyl groups are at a slightly downfield: 30.8 for
acetone and 31.2 for acetaldehyde, with a range of about 30

45.
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Spectroscopy
76
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STRUCTURE

Introducing heteroatoms or unsaturation into alkane chains
requires completely new sets of empirical parameters that
depend on the substituent, on its distance from the resonating
carbon ( ), and on whether the substituent is terminal or
internal:
These parameters on the next slide represent the effect on a
resonating carbon of replacing a hydrogen atom with X:
CHEM 430 NMR

Spectroscopy
77
NMR - The
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35

STRUCTURE
CHEM 430 NMR

Spectroscopy
78
NMR - The
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STRUCTURE

With the exception of cyano-, acetyleno-, and the heavy atom
iodine, the -effects are determined largely by the ENof the
substituent.
The -effects are all positive and generally of similar
magnitude ( 6 to 11 ppm) and that the -effects are all

negative and generally of similar magnitude (-2 to -5 ppm).
Although the details are not entirely understood, it is clear
that simple polar considerations do not dominate the - and effects.
CHEM 430 NMR

Spectroscopy
79
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35

STRUCTURE

Examples:
To use the substituent parameters given in the table, one
adds the appropriate values to the chemical shift of the 13C in
the unsubstituted hydrocarbon analogue (already having the
C-effects):
In the first example 16 is the base value for the 1-carbon in
propane and 27 is the base value for the carbons in

cyclopentane
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STRUCTURE
3-5b Unsaturated Compounds.

The effects of diamagnetic anisotropy on a carbon and a
proton have similar magnitudes, but the much larger
paramagnetic shielding renders the phenomenon relatively
unimportant for carbon.
Thus, benzene (128.4) and the alkenic carbon of cyclohexene
(127.3) have almost identical carbon resonance positions, in

contrast to the situation with their protons.
The full range of alkene and aromatic resonances is about
100 170.
CHEM 430 NMR

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81
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35

STRUCTURE

Alkenes
Alkenic carbons that bear no substituents resonate at 104 115
for hydrocarbons (isobutylene [ (CH3)2C=CH2] at 107.7)
Alkenic carbons that have one substituent resonate in the range
120 140 (trans-2-butene at 123.3)

Finally, disubstituted alkenic carbons resonate the most
downfield at 140 165 (isobutylene [ (CH3)2C=CH2] at 146.4)

Polar substituents on double bonds, especially those in
conjugation, can alter the resonance position appreciably.

Unsaturated ketones, such as 3- 33 and 3- 34, have lowerfrequency a resonances and higher- frequency b resonances.
The effect is d ( CRR ) d d d ( CHR) ( CH3) 2C CH2 d d (
CH2).
CHEM 430 NMR
82
Spectroscopy
NMR - The
Chemical
Shift
35

STRUCTURE

Alkenes
Polar substituents on double bonds, especially those in
conjugation, can alter the resonance position appreciably; edonation or w/d alters the radial term through resonance.
Unsaturated ketones have more upfield resonances and
more downfield resonances.
The effect is reduced in acyclic molecules

Electron donation in enol ethers reverses the trend:
CHEM 430 NMR
Spectroscopy
CH2=CHOCH3 ( = 153.2,
= 84.2)
83
NMR - The
Chemical
Shift
35

STRUCTURE

Alkenes
Alkene chemical shifts may be estimated from substituent
parameters added to the shift for ethene ( 123.3).
For and carbons on the same end of the double bond as
the resonating carbon, respective increments of 10.6, 7.2, and

-1.5 are added.
For and carbons on the opposite end of the double bond
from the resonating carbon, respec-tive increments of -7.9,

-1.8 and -1.5 are added.
An increment of -1.1 is added if any two substituents are cis
to each other.
CHEM 430 NMR
Spectroscopy
84
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35

STRUCTURE

Alkenes
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Spectroscopy
85
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STRUCTURE

Alkynes and Nitriles
Terminal alkyne carbon generally resonates in the narrow range
67 70.
An alkyne carbon that carries a carbon substituent resonates at
a slightly higher frequency ( 74 85), because of and effects

from the R group.
Effects of conjugating, polar substituents expand the range to
20 90.
Nitriles resonate in the range 117 130 (CH 3CN at 116.9). The
n * transition pushes the range downfield.
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Spectroscopy
86
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35

STRUCTURE

Aromatics
Alkyl substitution has its major effect on the ipso carbon.
Because this carbon has no attached proton, its relaxation time
is much longer than those of the other carbons, and its intensity
is usually lower.
Conjugating substituents like NO2 have strong perturbations on
the aromatic resonance positions, as the result of a combination

of traditional and effects and changes in e- density through
delocalization
CHEM 430 NMR

Spectroscopy
87
NMR - The
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35

STRUCTURE

Aromatics
Heteroaromatics display a similar interplay of effects:
Aromatic resonances may be calculated empirically by adding
increments to the benzene chemical shift (128.4) for each

substituent that is ipso, ortho, meta, or para to the resonating
carbon as seen on the following table:
CHEM 430 NMR

Spectroscopy
88
NMR - The
Chemical
Shift
35

STRUCTURE

Aromatics
CHEM 430 NMR

Spectroscopy
89
NMR - The
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Shift
35

STRUCTURE

Aromatics
CHEM 430 NMR

Spectroscopy
90
NMR - The
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35

STRUCTURE

Aromatics
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Spectroscopy
91
NMR - The
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STRUCTURE
3-5c Carbonyl Groups

General
Carbonyl groups have no direct representation in 1H NMR
spectra, so 13C NMR provides unique information for their
analysis.
The entire carbonyl chemical shift range, 160 220, is well
removed to high frequency from that of almost all other

functional groups, on account of the effect of the n *
transition on the magnitude of the paramagnetic shift.
Like aromatic ipso carbons and nitriles, carbonyl carbons other
than those in aldehydes carry no attached protons and hence

relax more slowly and tend to have low intensities.
CHEM 430 NMR

Spectroscopy
92
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35

STRUCTURE

Aldehydes and Ketones
Aldehydes resonate toward the middle of the carbonyl range, at
about 190 205 (acetaldehyde at 199.6)
Unsaturated aldehydes, in which the carbonyl group is
conjugated with a double bond or phenyl ring, are shifted upfield

(benzaldehyde at 192.4)
The , and effects of substituents on ketones add to the
carbonyl chem-ical shift and hence are found on the downfield

end of the carbonyl range from195 220 (acetone at 205.1 and
cyclohexanone at 208.8)
Again, adjacent unsaturation shifts the resonances to lower
frequency.
CHEM 430 NMR
Spectroscopy
93
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35

STRUCTURE

Carboxylic Acid Derivatives
Carboxylic derivatives fall into the range 155 185.
The resonances for the series carboxylate , carboxyl , and ester
often are well defined:

NaOAc (181.5), HOAc(177.3), and CH3OAc(170.7)
The range for esters is about 165 175, and that for acids is d
170 185.
Acid chlorides are at slightly upfield at 160 170, (168.6 for
AcCl) .
Anhydrides have a similar range: 165 175 (167.7 for Ac2O).
CHEM 430 NMR
Spectroscopy
94
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35

STRUCTURE

Carboxylic Acid Derivatives
Lactones overlap the ester range, with the six- membered
lactone at 176.5.
Amides have a similar range: 160 175 (172.7 for AcNH2) .
Oximes have a larger range, from 145 165.
CHEM 430 NMR

Spectroscopy
95
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35

STRUCTURE
CHEM 430 NMR

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96
NMR - The
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STRUCTURE
CHEM 430 NMR

Spectroscopy
97

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NMR

FACTORS THAT INFLUENCE PROTON

resonance and hybridization effects

quantity B0(1-) where is called the shielding

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

Conversely, a nearby e- donating atom or group will

increase e- density moving the observed resonance upfield

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

FACTORS THAT INFLUENCE PROTON

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

The effect drops sharply with distance:

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

bonding electrons move toward C and away from hydrogen

cloud of electrons from the unhybridized p-orbitals as we

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

Nonlocal fields have a major influence on chemical shift only if the

group has a non-spherical shape

FACTORS THAT INFLUENCE PROTON

local field by the substituent

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

electrons; as these electrons circulate in the applied magnetic

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

effect of shielding inside the ring or deshielding outside the

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

donation) or deshielding (electron withdrawal) the nonlocal

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

magnetic dipole on the point in space where a proton(nuclei)

FACTORS THAT INFLUENCE PROTON

Molecules have been constructed for the purpose of

confirming the shielding effect predicted by the model:

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

The acetylene system provides a simple example

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

Even simple alkane systems show anisotropy:

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

Even simple alkane systems show anisotropy:

CHEM 430 NMR

FACTORS THAT INFLUENCE PROTON

The effect is much larger than the indicated 1.2 ppm ,

because the cyclopropane carbon orbital to hydrogen