NMR Info Tables 12-31-09

Beauchamp Spectroscopy - NMR 1
1 13
H and C NMR Material
(Chem 318, 319, 422, 424)
Beauchamp
(updated 9-14-10)
Z:\classes\318\NMR_Info_Tables_9-9-14.DOC
1 13
Nuclear Magnetic Resonance (NMR): H = proton NMR and C = carbon-13 NMR
1
H-NMR
Provides information on:
1. The types of protons present (δ = chemical shift is given in parts per million,
the usual range = 0-10 ppm, a few chemical shifts extend to 10-15 ppm).
2. The number of such protons (integration counts the relative numbers of hydrogen
atoms as a ratio by summing the area under the peaks).
3. How many neighbor protons are immediately adjacent to a specific center.
a. splitting patterns = multiplicity = number of peaks (singlet, doublet, triplet, quartet,
quintet, etc.) can indicate how many neighbor protons there are. When simple (first
order) the number of peaks is one more than the number of neighbors (N+1 rule).
When complicated (second order) the appearance of the peaks is hard to interpret.
b. J values = coupling constants (distance in Hz that peaks are separated, given in
frequency units, Hz = cycles per second).
13
C-NMR
Provides information on:
1. The types of carbon atoms present (chemical shift is given in parts per million,
the usual range = 0-250 ppm).
2. The number of distinct kinds of carbon atoms present equals the number of peaks in proton
decoupled spectra. All carbon peaks appear as singlets when decoupled from the protons.
3. Reveals how many protons are on each carbon.
a. DEPT experiment (Distortionless Enhancement by Polarization Transfer) is a series of
four 13C experiments with different mixing of proton coupling to display CH, CH2 or
CH3’s as distinct patterns. Carbons without hydrogen do not show up and are
determined by comparison with a normal proton decoupled 13C spectrum.
b. Off resonance experiment (coupling between protons and carbons shows up in a
multiplicity of a 13C peak as a singlet, doublet, triplet or quartet “= N+1 rule”). This is
an old fashioned method that is seldom used anymore, but much simpler to
understand.
As in other spectroscopy, detection is due to energy transitions. In NMR, the detection is
observed in the relaxation of the excited state. The transitions in NMR are of very low energy
(radiowaves). They are a result of two magnetic quantum states resulting from the spin of nuclear
particles (protons and/or neutrons) in the presence of a magnetic field.
higher higher A excess higher

energy energy molecules energy
absorption relaxation
(energy input) (energy released)
excitation relaxtion
IR, UV, Vis
NMR detects
detect transitions here
transitions here lower
lower A excess lower A excess
energy energy energy molecules
molecules
Energy = Electromagnetic Radiation
ultraviolet visible infrared radiowave

kcal
∆E mole 100 40 10 0.000006
ν (frequency) 1015 1015 1014 107

(per sec. = Hz) NMR Bold units are
"typical" units
λ (wave length) 300 600 3000 20,000,000,000 for that
spectrocsopic
(nm) UV VIS (20m)
method.
ν = (1/λ) 30,000 17,000 3300 0.0005
-1
(cm , wavenumber) IR
∆E = energy ν = frequency λ = wavelength ν = wavenumber
∆E = hν = hc(1/λ) = hcν c = (ν)(λ) = 3.0 x 108 m/sec = 3.0 x 1010 cm/sec
Proton (1H) and carbon (13C) "magnets"
“I” is the spin quantum number.
Number of Spin States = 2(I) + 1
In practice, I = 1/2 is the most commonly encountered spin state, which is the value for both
1
H and 13C, the nuclei presented in this book. Other commonly used nuclei include N-15, P-31
and F-19. These are especially useful in biochemistry and pharmaceutical chemistry.
Number of spin states = 2(1/2) + 1 = 2 spin states for both proton and carbon nuclei
I = 1/2 = 1H, 13C, 15N, 19F, 31P,....(these are all observable on a typical broadband NMR)
Spinning electrical charge

generates an oscillating higher
magnetic field. β = -1/2 energy
In the presence of a magnetic

field these two magnetic quantum
external states are different in energy.
magnetic ∆ = 1 The spin aligned with the field is
field lower in energy than the spin
Nuclear spin states, up and down,
Bo alligned against the field.
are degenerate (equal) energies in
the absence of a magnetic field.
α = +1/2 lower
For our purposes we can think of
these as the "north" and "south" energy
poles of a magnet.
12
Some nuclei only have one spin state. We are fortunate that most of carbon is isotope C
and most of oxygen is isotope 16O. Both have and even number of protons and neutrons and are
magnetically invisible. This greatly simplifies our interpretation of routine 1H and 13C NMR
spectra.
12
I = 0 = C, 16O, = no magnetic moment (magnetically invisible)
The two magnetically degenerate energy states become split in the presence of an external
magnetic field. We can stimulate energy transitions between these two energy states (∆E) via an
input of radiowaves. Most NMR instruments describe ∆E in MHz based on a proton nucleus.
The size of ∆E depends on:
1. the size of the external magnetic field and
2. the size of the nuclear magnet
∆E1= hν1 ∆E2= hν2 ∆E3= hν3 ∆E4= hν4

∆E = 0
(degenerate) Bo
Bo = 0
Gauss = 0
Tesla = 0
νH(MHz) = 0 Gauss = 14,100 23,500 70500 176,300
Size of external Tesla = 1.4 2.4 7.1 17.7
magnetic field νH(MHz) = 60* 100* 300* 750*
Original Largest Our Instrument Largest known instrument
6 commercial solid core cost (1990) (2004) about 1000 MHz = 1 Giga Hz
M = mega = 1,000,000 = 10
instrument electromagnetic $220,000 cost? probably $ millions
(1960) * assumes a proton nucleus
The ∆E between the energy states depends on two magnets:
a. the external field = Bo (This is what you buy when purchasing the instrument.)
b. the nuclear magnet = γ i (γ1H, γ13C,..),(This is the nucleus observed when a sample is placed in the
instrument.)
Relative Boltzman Energy Populations (protons)
Because ∆E is very small in NMR transitions, there is not much of a difference in the populations
of the two energy states.
300 MHz – a bigger magnetic field and a bigger energy difference
∆E (0.028 cal / mole)

Ni = number of nuclei in a
N2 particular energy state.
= exp RT
= exp (1.98 cal / mol-K)(289 K) 0.99995
N1 =
1.00000
E2 = -------------- 9,999 ---------- We see a difference of 1 out of about

20,000 because of ∆E. This is the signal
E1 = ------------- 9,999 + 1 ----- we detect, but, the population levels are
essentially 50/50.
The NMR Radio Dial
The energy difference (∆E) of a 300 MHz NMR instrument is in the radiowave region of the
electromagnetic spectrum. Think of the other nuclei as appearing at different positions on your radio dial
and γi as the number you tune into. You can tune in a nuclei, like you tune in a radio station.
∆E = hν = ( h ) ( γ i) (Bo) = (constants) x (type of nucleus) x (external magnetic field)

2π
15 29 13 31 19 1
N Si C P F H
The spread in each region shows

all nuclei of a certain type (e.g.
protons) are not the same. The
18,000 Hz spread is due to nonhomogeneous 3,000 Hz
δ = ppm = 240 ppm magnetic environments of each δ = ppm = 10 ppm
0 = TMS (Ref.) type of nucleus. 0 = TMS (Ref.)
Protons
1 ppm depends on Bo (size of external magnetic field, 1 / 1,000,000 of ∆E of ν in Hz) 10 ppm
1 3000 Hz
x 300,000,000 Hz = 300 Hz = 1 ppm
1,000,000 0 ppm
Bo 1.0 ppm (= Hz)
The range of differences in chemical shifts
60 MHz 60 Hz
(about 3000 Hz = 10 ppm) is only a small portion ∆E = 300,000,000 Hz
100 MHz 100 Hz
of the total energy to cause a proton to flip (about
300 MHz 300 Hz
300,000,000 Hz = 300 MHz) on a 300 MHz
600 MHz 600 Hz
instrument.
Most protons are detected within a 10 ppm range of the entire ∆E of excitation.
Carbon-13 - (µ13C) = 1/4 x (µ 1H) in the same external magnetic field (the carbon magnet = 1/4 the proton magnet)
1 ppm depends on Bo (size of external magnetic field, 1 / 1,000,000 of ∆E of ν in Hz) 220 ppm
1 16,500 Hz
x 75,000,000 Hz = 75 Hz = 1 ppm
1,000,000 0 ppm
Bo 1.0 ppm (= Hz) The range of differences in chemical shifts (about
16,500 Hz = 220 ppm) is only a small portion of the
15 MHz 15 Hz ∆E = 75,000,000 Hz
total energy to cause a carbon to flip (about 75,000,000
25 MHz 25 Hz
Hz = 75 MHz) on a 75 MHz instrument. The differences
75 MHz 75 Hz
among the carbons is wider than the differences
150 MHz 150 Hz
among the protons in ppm (greater dispersion).
Most 13Cs are detected within a 220 ppm range of the entire ∆E of excitation.
Why are there differences in chemical shifts? – Two main reasons below.
1. Electronegativity Effects
Some typical chemical shifts for methyl groups attached to different atoms are shown below.
Clearly there is some sort of electronegativity effect working.
CH3-F CH3-OR CH3-Cl CH3-Br CH3-I CH3-H (CH3) 4Si = TMS
chemical
shift (δ) = 4.27ppm 3.39ppm 3.06ppm 2.69ppm 2.16ppm 0.23ppm 0.0ppm
zero by definition = relative
reference point for both
hydrogen and carbon NMR.
Electrons moving in chemical bonds create their own small opposition magnetic field to the
external magnetic field. The more electron density there is, the stronger is this opposition field. Any
nearby electron withdrawing groups can steal some of this electron density away from sigma bonds with
protons and change the net magnetic field each proton experiences, which then changes the chemical
shift where a proton is excited (detected).
Shielding region of
the small magnetic
field in opposition
direction to Bo.
deshielding
region
C H
deshielding
region
Bσ
shielding
region
Bo = external
magnetic field
Sigma, σ, is a shielding constant that includes a variety of factors that change the energy of
transition of nuclei. Diamagnetic shielding is most important for spherical shapes, like the proton
(1s orbital), but paramagnetic shielding becomes important when electrons are in orbitals that are not
spherical, like carbon-13 (2p orbitals). We will not discuss this aspect, except to point out that this weak
shielding effect produces a small variable reduction in the size of the external field, Bo, and produces a
net effective field, Bnet, because of shielding by electrons. Differences in σ lead to differences in the
chemical shifts of protons in H-NMR (or differences in carbon shifts in 13C NMR).
Because the electronegativity of silicon is less than carbon, the carbon and the protons are more
electron rich, thus more shielded than in routine organic compounds. The peak for both carbon and
hydrogen in TMS is far to the right of most signals and defined as “zero” parts per million.
Differences in proton chemical shifts (due to electronegativity or inductive effects)
F R3Si
C H C H more electron
less electron opposing field = Bσ
density
density
These protons are
These protons are shielded most.
shielded least (deshielded). CH3
∆δmax = 0-3000 Hz
hugely exaggerated CH3F CH3Cl CH3Br CH3I CH3H H3C Si CH3
CH3
E2
Bσ Bσ Bσ Bσ Bσ Bσ
δ6 δ5 δ4 δ3 δ2 δΤΜS = 0
Ref = 0
∆E to flip a proton's spin,
here = 300,000,000 Hz
∆Eactual = hν6 ∆Eactual = hν ∆Eactual = hν4 ∆Eactual = hν3 ∆Eactual = hν2 ∆Eactual = hν1
5
E1
δx (ppm) = 4.27 ppm 3.06 ppm 2.69 ppm 2.16 ppm 0.23 ppm 0.0 ppm
Hz (300 MHz) = 1281 Hz 918 Hz 807 Hz 648 Hz 69 Hz 0 Hz
more shielded
larger frequency shift from the TMS reference Ref = 0
more more
deshielded shielded
∆E = 300,000,000 Hz (energy to flip proton spin) constant magnetic field strength

∆δ = 0-3000 Hz (scale greatly exaggerated above), of Bo (= 70,500 gauss) assumed
we can see these to about ± 0.1Hz out of 300,000,000 Hz
10 9 8 7 6 5 4 3 2 1 0 = δ = ppm
Differences in carbon chemical shifts (due to electronegativity or inductive effects)
F R3Si
C H C H more electron
less electron opposing field = Bσ
density
density
a peculiar This carbon is
This carbon is shielded reversal shielded most.
least (deshielded). because
CH3
∆δmax = 0-16,500 Hz of iodine
hugely exaggerated RCH2F RCH2Cl RCH2Br CH3R RCH2I H3C Si CH3
CH3
E2
Bσ Bσ Bσ
Bσ Bσ Bσ
δ6 δ5 δ4 δ2 δ3 δΤΜS = 0
Ref = 0
∆E to flip a proton's spin,
here = 75,000,000 Hz
∆Eactual = hν6 ∆Eactual = hν5 ∆Eactual = hν4 ∆Eactual = hν3 ∆Eactual = hν2 ∆Eactual = hν1
E1
δx (ppm) = 84 ppm 45 ppm 34 ppm 10 ppm 7 ppm 0.0 ppm
Hz (75 MHz) = 6,300 Hz 3,375 Hz 2,550 Hz 750 Hz 525 Hz 0 Hz
more shielded
larger frequency shift from the TMS reference Ref = 0
more more
deshielded shielded
Constant "external" magnetic field
∆E = 75,000,000 Hz (energy to flip carbon spin)
strength of Bo (= 70,500 gauss) assumed.
∆δ = 0-16,500 Hz (scale greatly exaggerated above),
we can see these to about ± 1Hz out of 75,000,000 Hz
200 180 160 140 120 100 80 60 40 20 0 = δ = ppm
2. π bond anisotropy = a second type of effect causes changes in local magnetic environments
Certain molecule orientations (relative to Bo) add and others cancel relative to the external
magnetic field. The molecules are tumbling and changing orientations to Bo on the order of 108-1012 times
per second (how fast depends on the size, shape, solvent viscosity, temperature, etc.) The net contributing
orientations are shown below for pi systems (alkenes, aromatics and terminal alkynes).
π bond anisotropy: certain orientations (relative to Bo) add, others cancel with a net contribution of what is shown in the
following diagrams.
shielding shielding shielding

cone cone cone
deshielding C
deshielding C C deshielding
region region region
C C H C C
higher δ higher δ higher δ
C
H C C
H
Bshield Bshield Bshield
shielding shielding shielding
cone cone cone
Bo Bo
Bo
typical: alkene protons aromatic protons terminal alkyne protons
δ = 4-6 ppm δ = 7-8 ppm δ = 2-3 ppm
Protons to the side of an alkene Ring current in aromatics has a larger Alkyne protons have a smaller
pi bond are deshielded and shifted effect than a single pi bond in a typical δ than expected based on the
to a larger chemical shift, δ. alkene and aromatic protons usually greater electronegativity of an
Allylic protons are shifted in a have a larger chemical shift than alkene sp orbital, but the net orientation
similar direction by a smaller amount protons. Benzylic protons are shifted in of the pi bonds causes the end of
because they are farther away. a similar direction by a smaller amount a triple bond to be shielded.
because they are farther away. Nitriles show similar effects.
Examples δ = 8.9 ppm deshielded
δ = 5.7 ppm deshielded δ = -1.8 ppm highly shielded region outside of ring
region outside of π bonds region inside of ring
δ = - 4.2 ppm highly shielded
H region above and inside
H H of ring
H
H CH3
H
HH
H H H3C
1,3,5,7-cyclooctatetrene [18]-annulene
(a cycloalkene) trans-10b,10c-dimethyldihydropyrene
(aromatic)
3
Calculation of chemical shifts for protons at sp carbons
Estimation of sp3 C-H chemical shifts with multiple substituent parameters for protons within 3 C's of consideration.
H
C α Cβ C γ α = directly attached substituent, use these values when the hydrogen and substituent are attached to the same carbon
β = once removed substituent, use these values when the hydrogen and substituent are on adjacent (vicinal) carbons
γ = twice removed substituent, use these values when the hydrogen and substituent have a 1,3 substitution pattern
Starting value and equations for CH3's

X = substituent α β γ
R- (alkyl) 0.0 0.0 0.0
R2C=CR- (alkenyl) 0.8 0.2 0.1 δ CH3 = 0.9 + α H3C α
RCC- (alkynyl) 0.9 0.3 0.1
Ar- (aromatic) 1.4 0.4 0.1
F- (fluoro) 3.2 0.5 0.2 δ CH3 = 0.9 + ∑(β + γ) H3C Cβ Cγ
Cl- (chloro) 2.2 0.5 0.2
Br- (bromo) 2.1 0.7 0.2
I- (iodo) 2.0 0.9 0.1
∑ is the summation symbol for all substituents considered
HO- (alcohol) 2.3 0.3 0.1
RO- (ether) 2.1 0.3 0.1
epoxide 1.5 0.4 0.1 Starting value and equation for CH2's
R2C=CRO- (alkenyl ether) 2.5 0.4 0.2
ArO- (aromatic ether) 2.8 0.5 0.3 In a similar manner we can calculate chemical shifts
RCO2- (ester, oxygen side) 2.8 0.5 0.1 for methylenes (CH2) using the following formula
ArCO2- (aromatic ester, oxygen side) 3.1 0.5 0.2
ArSO3- (aromatic sulfonate, oxygen) 2.8 0.4 0.0 δ CH2 = 1.2 + ∑(α +β + γ) H
H2N- (amine nitrogen) 1.5 0.2 0.1 H Cα C β C γ
RCONH- (amide nitrogen) 2.1 0.3 0.1
O2N- (nitro) 3.2 0.8 0.1
∑ is the summation symbol for all substituents considered
HS- (thiol, sulfur) 1.3 0.4 0.1
RS- (sulfide, sulfur) 1.3 0.4 0.1 Starting value and equation for CH's
OHC- (aldehyde) 1.1 0.4 0.1
RCO- (ketone) 1.2 0.3 0.0
ArCO- (aromatic ketone) 1.7 0.3 0.1 In a similar manner we can calculate chemical shifts
HO2C- (carboxylic acid) 1.1 0.3 0.1 for methines (CH) using the following formula
RO2C- (ester, carbon side) 1.1 0.3 0.1 H
δ CH = 1.5 + ∑(α +β + γ)
H2NOC- (amide, carbon side) 1.0 0.3 0.1
C α Cβ C γ
ClOC- (acid chloride) 1.8 0.4 0.1
NC- (nitrile) 1.1 0.4 0.2
RSO- (sulfoxide) 1.6 0.5 0.3 ∑ is the summation symbol for all substituents considered
RSO2- (sulfone) 1.8 0.5 0.3
a. methine b. methylene
Calculations are generally close to
CH2 CH3 actual chemical shifts for a single
d. methyl HO
O CH N substituent, but are less reliable as
the number of substituent factors
H2C H goes up. Multiple substituent factors
H3C H2C c. methyl
tend to overestimate an actual chemical
shift.
e. methylene
f. methylene
a. methine = 1.5 + (1.4)α + (2.3)α + (0.2)β = 5.4 ppm d. methyl = 0.9 + (0.1)α = 1.0 ppm
actual = 5.2 actual = 1.0
b. methylene = 1.2 + (1.5)α + (0.4)β + (0.3) β = 3.4 ppm e. methylene = 1.2 + (0.3)α = 1.5 ppm
actual = 3.0 and 3.2 actual = 1.7
c. methyl = 0.9 + (1.5)α = 2.4 ppm f. methylene = 1.2. + (1.7)α = 2.9 ppm
actual = 2.6 actual = 2.9
2
Estimated chemical shifts for protons at alkene sp carbons
Substituent α geminal α cis α trans Substitution relative to calculated "H"

cis
H- 0.0 0.0 0.0 H
Hydrogen C C
R- 0.5 -0.2 -0.3
trans gem
Alkyl
C6H5CH 2- 0.7 -0.2 -0.2 δ(ppm) = 5.2 + α gem + α cis + α trans
Benzyl
X-CH2- 0.7 0.1 0.0
Halomethyl Example Calculation
(H)/ROCH2- 0.6 0.0 0.0
alkoxymethyl gem
(H)2/R2NCH2- 0.6 -0.1 -0.1 H
aminomethyl trans
C H
RCOCH2- 0.7 -0.1 -0.1 C
α-keto H
NCCH2- 0.7 -0.1 -0.1 CH3O cis
α-cyano
R2C=CR- 1.2 0.0 0.0
Alkenyl δ gem = 5.2 + 1.4 = 6.6
C6H5- 1.4 0.4 -0.1 actual = 6.6
Phenyl
F- 1.5 -0.4 -1.0 δ trans = 5.2 - 0.1 = 5.1
Fluoro actual = 5.1
Cl- 1.1 0.2 0.1
δ cis = 5.2 + 0.4 = 5.7
Chloro
actual = 5.6
Br- 1.1 0.4 0.6
Bromo
I- 1.1 0.8 0.9 c d e
Iodo bH H H H
RO- 1.2 -1.1 -1.2 C C C C
akoxy (ether) aH Hf
O C
RCO2- 2.1 -0.4 -0.6
O-ester O
(H)2/R2N- 0.8 -1.3 -1.2 δa = 5.2 + (-0.4) = 4.8
N-amino actual = 4.9 (J = 14, 1.6 Hz)
RCONH- 2.1 -0.6 -0.7
N-amide δb = 5.2 + (-0.6) = 4.6
O2N- 1.9 1.3 0.6 actual = 4.6 (J = 6, 1.6 Hz)
Nitro δc = 5.2 + 2.1 = 7.3
RS- 1.1 -0.3 -0.1 actual = 7.4 (J = 14, 6 Hz)
Thiol
OHC- 1.0 1.0 1.2 δd = 5.2 + 0.8 = 6.0
Aldehyde actual = 6.2 (J = 18, 11 Hz)
ROC- 1.1 0.9 0.7 δe = 5.2 + 0.5 = 5.7
Ketone actual = 5.8 (J = 11, 1.4 Hz)
HO2C- 0.8 1.0. 03
C-acid δf = 5.2 + 1.0 = 6.2
RO2C- 0.8 1.0 0.5 actual = 6.4 (J = 18, 1.4 Hz)
C-ester
H2NOC- 0.4 1.0 0.5
C-amide
NC- 0.3 0.8 0.6
Nitrile
2
Estimated chemical shifts for protons at aromatic sp carbons
Substitution relative to calculated "H"
Substituent α ortho α meta α para
meta ortho
H- 0.0 0.0 0.0
Hydrogen
CH3- -0.2 -0.1 -0.2 para H
Methyl
ClCH2- 0.0 0.0 0.0 meta ortho
Cholromethyl
Cl3C- 0.6 0.1 0.1 δ(ppm) = 7.3 + α ortho + α meta + α para
Halomethyl
HOCH 2- -0.1 -0.1 -0.1
Hydroxymethyl
R2C=CR- 0.1 0.0 -0.1 Example Calculation
Alkenyl 2
C6H5- 1.4 0.4 -0.1 H
1
Phenyl 3 5
CH3O H
F- -0.3 0.0 -0.2 H
Fluoro
Cl- 0.0 0.0 -0.1 H 6
Chloro 2H CH2
H 4 H
Br- 0.2 -0.1 0.0
Bromo 3 7
I- 0.4 -0.2 0.9
Iodo 1. δ (CH3) = 0.9 + 2.8 = 3.7
HO- -0.6 -0.1 -0.5 actual = 3.8
Hydroxy
RO- -0.5 -0.1 -0.4 2. δ (2) = 7.3 + (-0.5) ortho + (-0.1) para = 6.7
Alkoxy actual = 6.8
RCO 2- -0.3 0.0 -0.1
O-ester 3. δ (3) = 7.3 + (-0.2) ortho + (-0.4) para = 6.7
(H)2/R2N- -0.8 -0.2 -0.7 actual = 7.1
N-amino
RCONH- 0.1 -0.1 -0.3 4. δ (CH 2) = 1.2 + (0.8)α + (1.4)α = 3.4
N-amide actual = 3.3
O 2N- 1.0 0.3 0.4
Nitro 5. δ (5) = 5.2 + (0.7) gem = 5.9
RS- -0.1 -0.1 -0.2 actual = 5.9
thiol/sulfide
OHC- 0.6 0.2 0.3 6. δ (6) = 5.2 + (-0.2) trans = 5.0
Aldehyde
ROC- 0.6 0.1 0.2 actual = 5.1
Ketone
HO2C- 0.9 0.2 0.3 7. δ (7) = 5.2 + (-0.2) cis = 5.0
C-acid actual = 5.1
RO2C- 0.7 0.1 0.2
C-ester
H 2NOC- 0.6 0.1 0.2
C-amide
NC- 0.4 0.2 0.3
Nitrile
H 7.67
H
7.32
X
8 1 8 1
X
2 starting values for calculations: starting values for calculations:
7 7 2
H1, H4, H5, H8 = 7.67 H1, H4, H5, H8 = 7.67
3 H2, H3, H6, H7 = 7.32 3 H2, H3, H6, H7 = 7.32
6 6
5 4 5 4
Naphalene position H-2 H-3 H-4 H-5 H-6 H-7 H-8 Naphalene position H-1 H-3 H-4 H-5 H-6 H-7 H-8
H H
hydrogen 0.0 0.0 0.0 0.0 0.0 0.0 0.0 hydrogen 0.0 0.0 0.0 0.0 0.0 0.0 0.0
CH3- (R-) CH3- (R-)
methyl (alkyl) -0.2 -0.1 -0.2 0.0 0.0 0.0 0.1 methyl (alkyl) -0.2 -0.1 -0.1 0.0 0.0 0.0 0.0
F- F-
fluoro -0.2 0.0 -0.1 0.1 0.1 0.2 0.4 fluoro -0.4 -0.3 0.0 0.0 0.0 0.0 0.0
Cl- Cl-
chloro 0.2 0.0 0.0 0.1 0.1 0.2 0.5 chloro 0.1 0.1 0.1 0.1 0.1 0.2 0.0
Br- Br-
bromo 0.4 -0.1 0.0 0.0 0.1 0.2 0.5 bromo 0.2 0.1 -0.1 -0.1 0.1 0.1 0.1
I- I-
iodo 0.1 -0.5 0.2 -0.2 -0.1 0.0 0.3 iodo 0.1 -0.5 0.2 -0.2 -0.1 0.0 0.3
HO- HO-
hydroxy -0.7 -0.2 -0.4 0.0 0.0 0.1 0.4 hydroxy -0.7 -0.3 0.0 0.0 -0.1 0.0 -0.1
RO- RO-
alkoxy -0.7 -0.1 -0.4 0.0 0.0 0.0 0.5 alkoxy -0.7 -0.3 0.0 0.0 -0.1 0.0 -0.1
RCO2- RCO2-
O-ester -0.2 0.1 -0.1 0.0 -0.1 0.1 0.2 O-ester -0.2 -0.1 0.0 0.1 0.0 0.1 0.1
(H2) / R2N- (H2) / R2N-
amino -0.8 -0.2 -0.5 -0.1 0.0 0.0 0.0 amino -0.9 -0.6 -0.2 -0.1 -0.2 -0.1 -0.2
RCONH- RCONH-
N-amide 0.4 0.2 0.1 0.3 0.2 0.2 0.4 N-amide 0.5 0.1 0.1 0.1 0.1 0.1 0.1
O2N- O2N-
nitro 0.8 0.1 0.2 0.3 0.2 0.3 0.7 nitro 1.0 0.8 0.2 0.2 0.3 0.2 0.3
NC- NC-
nitrile 0.5 0.1 0.3 0.2 0.2 0.3 0.5 nitrile 0.5 0.2 0.2 0.2 0.3 0.3 0.2
OHC- OHC-
aldehyde 0.4 0.1 0.2 0.1 0.1 0.2 1.5 aldehyde 0.6 0.6 0.2 0.2 0.3 0.2 0.3
RCO- RCO-
ketone 0.4 -0.1 0.1 0.0 0.0 0.1 1.1 ketone 0.8 -0.7 0.2 0.2 0.3 0.2 0.3
HO2C- HO2C-
acid 1.1 0.2 0.4 0.2 0.2 0.3 1.4 acid 1.0 0.7 0.4 0.4 0.4 0.3 0.5
RO2C- RO2C-
C-ester 0.8 0.0 0.2 0.1 0.1 0.2 1.3 C-ester 0.8 0.7 0.1 0.1 0.2 0.1 0.2
ClOC- ClOC-
acid chloride 1.2 0.2 0.4 0.2 0.2 0.3 1.0 acid chloride 1.0 0.7 0.4 0.5 0.3 0.4 0.4
Starting point chemical shifts for a few common heterocycles.
6.30 6.05 6.96 7.64 7.54
7.08
6.62 7.25 7.12
7.38 7.20
N S
O 8, broad H 2.25 8.60 2.55
N 8.48 N
2.01 2.01 6.87
6.21 5.93
2.35
7.17 6.86 7.46 2.32
7.30 7.17 6.55 6.42 7.16
S
O
7.10
N
9, broad H
6.89 6.75
6.23 5.93 8.42 8.44 8.46
N N
7.07 2.50
7.25 2.26 not
available S
O N
H
Real Examples of Combination Effects on Chemical Shifts
π bond anisotropy 0.8 shielded σ bond example too
(CH2)
0.8, shielded
H shielding cone
from σ bond
CH2
2.6
H deshielded H
7.2 1.5
electronegativity and π bond 10-12 15, hydrogen
H bonded enol
O O H O O O
C H 9.5 C C C C
H 3C C CH3
O H O hydrogen
bonding H
electronegative substituent and distance from protons
O CH2CH 2CH2CH2CH 3 CH3 Cl CH3CH2 Cl CH3CH2CH2 Cl CH3CH2CH 2CH2 Cl CH3CH2 R
3.6 1.5 1.3 1.3 0.9 3.0 1.3 1.0 0.9 0.9
multiple substituents
CH4 CH3Cl CH2Cl2 CHCl3 CCl4
0.2 ∆ = 2.8 3.0 ∆ = 2.3 5.3 ∆ = 1.9 7.2 ∆=? ? (oops)

substituents at methyl (CH3), methylene (CH2) and methine (CH) O O O
CH3Cl CH3CH2Cl (CH3)2CHCl H 3C C Ph H3CH 2C C Ph (H3C)2CH C Ph
3.0 3.5 4.1 2.6 3.0 3.5

alkene substituent resonance and inductive effects
3.7 O
0.9 1.4 2.0 3.8 O 4.2 4.9
H H CH CH CH H 5.0 6.4 C O H
3 2 2 CH3O C H H 2 C O H
C C C C H 3C C C H 3C C C
C C 2.1
H H H H 1.3 H H H H
H H
5.3 5.8 4.9 6.1 5.8 6.5 4.0 7.3 4.6
aromatic resonance and inductive effects
H H 7.3 6.6 7.1 8.2 7.5
H H H H H H H H
6.7 O 7.7 O
H H
H 2N H H 2N H N H N H
O O
H H
π bond anisotropy H H H H H H H H
produces deshielding Extra electron density via resonance produces Withdrawal of electron density via resonance
effect on aromatic shielding effect on aromatic protons, especially produces deshielding effect on aromatic protons,
protons. at ortho/para positions. especially at ortho/para positions.
sp C-H RO H alcohol H = 1-5 R2N H amine H = 1-5 enol H = 10-17 H O
H C C H 2.4 ArO H phenol H = 4-10 C C
O O
R C C H 1.9 RS H thiol H = 1-2.5 amide H = 5-8
R C R C
Ar C C H 3.0 ArS H aromatic thiol H = 3-4 NH2 O H acid H = 10-13
3
Problem– Calculate the expected chemical shifts for the following protons attached to sp carbon.
b c d
a O
O
H OH Cl
O2N
O O
e O g
f
O
H2N
N O2N S
O O
h i h O
N H3C O
C O OH
F
O
Problem
a. How many different isomers are there in C5H12? How many different types of hydrogen atoms are there
in each isomer? How many different types of carbon atoms are there in each isomer?
isomer 1 isomer 2 isomer 3

number of distinct
kinds of 1H
number of distinct
kinds of 13C
b. How many different isomers are there for C5H11Br? (Hint: Use the carbon skeletons generated in part a
as a starting point.) How many different types of hydrogen atoms (and carbon atoms) are there in each
isomer of C5H11Br? Nuclei can be nonequivalent, chemically equivalent and magnetically equivalent.
There can also be several types of groups: homotopic, heterotopic, enantiotopic, diastereotopic and
rototopic. The types of protons (or carbons) present will affect the appearance of the NMR spectrum,
sometimes dramatically. The interpretation is sometimes straight forward, but occasionally it is very
complicated. Some of the details are too complicated for us to easily evaluate, but we need to be aware of
them so that we know exceptions exist for our simplistic rules (e.g. the N+1 rule that we will study later).
Generally each distinct type of 1H (and 13C) will have its own chemical shift (δ). Occasionally two
different types of 1H (and 13C) will fall on top of one another and obscure the information. This is much
more common in 1H NMR (spread over 10 ppm) than 13C NMR (spread over 220 ppm) because the proton
range is so much smaller. As you are working out the different types of protons, do the same with the
carbon atoms.
isomer 1 isomer 2 isomer 3 isomer 4 isomer 5 isomer 6 isomer 7 isomer 8
number of distinct
kinds of 1H
number of distinct
kinds of 13C
Problem x – How many different types of hydrogen atoms and carbon atoms are in the following
structures. Classify each comparison as homotopic, heterotopic, enantiotopic or diastereotopic
atoms.
a. b. c. d.
HO CH3 CH3 CH3 CH3
H CH3 CH3 H Cl
Different
types of H = ?
Different
types of C = ?
e. H
f.
Cl
Different
types of H = ?
Different
types of C = ?
g. h. i. j.
X X X X
X
Different
types of H = ?
Different
types of C = ?
l. m.
k. X X n. X
Y X
X Y Y
Different
types of H = ?
Different
types of C = ?
Summary of Generic Proton Shifts
Proton chemical shifts of hydrogen on sp3 carbons depend on two main factors (electronegativity and pi bond
anisotropy). All values listed below are only approximate and have a small plus or minus range about the listed
value.
All things being equal, methine protons (CH) have greater chemical shifts than methylene
protons (CH2) which have greater chemical shifts than methyl protons (CH3).
H H
C H C H C H
H
δ 1.5 ppm δ 1.2 ppm δ 0.9 ppm
methine protons methylene protons methyl protons
Chemical shifts in an only "alkane" environment.
1. sp3 C-H Electronegative atoms in the vicinity of hydrogen deshield protons and produce a larger chemical
shift. If the electronegative atom is in resonance with an adjacent pi system that further withdraws electron
density, and the chemical shift is increased (look at ethers vs. esters).
a. next to a halogen
H H H H
C F C Cl C Br C I
δ 4.1 - 4.7 ppm δ 3.1 - 3.7 ppm δ 3.0 - 3.6 ppm δ 2.9 - 3.5 ppm
fluoro alkanes chloro alkanes bromo alkanes iodo alkanes
b. next to a oxygen
O O
H H H O H H
C R C
C OH C OR C O C C O C O
H
δ 3.1 - 3.7 ppm δ 3.0 - 3.6 ppm δ
3.7 - 4.3 ppm δ 2.5 - 3.2 ppm δ 3.7 - 4.3 ppm δ 4.0 - 4.6 ppm
alcohol alkyl ether aromatic ether alkyl ester aromatic ester
epoxide ether (oxygen side)
(resonance withdrawal) (oxygen side)
(resonance withdrawal) (resonance withdrawal)
c. next to a sulfur or nitrogen
O
H H H H
C
C SH C SR C N C N
δ 2.2 - 2.8 ppm δ 2.2 - 2.8 ppm δ 2.3 - 3.1 ppm δ 3.0 - 3.6 ppm
thiol alkyl ether amines (r esonance withdrawal)
amides
2. sp3 C-H Pi bonds in the vicinity of hydrogen also deshield protons via pi bond anisotropy and produce a larger
chemical shift. The closer the sp3 C-H is to the pi bond the greater chemical shift observed. When an
electronegative atom is part of the pi bond, the chemical shift further increases (look at C=C vs C=O).
H O
H O H H O
O
C C
C C C C C N
Cl O
δ 1.9 - 2.7 ppm
aldehydes, ketones, δ 2.6 - 3.3 ppm δ 2.7 - 3.4 ppm δ 2.7 - 3.4 ppm
carboxylic acids, amides, aromatic ketones acid chlorides nitro compounds
alkyl ester (oxygen side) (resonance withdrawal) (resonance withdrawal) (resonance withdrawal)
H H H
H C
C C C C C N C
C C
δ 1.8 - 2.4 ppm δ 2.3 - 2.8 ppm δ
δ 1.7 - 2.3 ppm 2.3 - 2.9 ppm
propargylic protons propargylic protons allylic protons benzylic protons
2
3. sp C-H Hydrogens at the side of a pi bond are deshielded even more than above via pi bond
anisotropy. An aldehyde produces the largest effect due to the electronegative oxygen, followed by
an aromatic ring, followed by alkenes and finally terminal alkynes. (sp C-H, partially shielded)
δ 4.0 - 4.6 ppm
alkene C-H H H δ 5.5 - 6.5 ppm H H
H
O C H O C H C H C H
C H C C C C RO C RO C
R C H H H
H
H δ 6.0 - 6.3 ppm δ 6.4 - 7.4 ppm
δ 5.7 ppm vinylic protons (resonance vinylic protons (resonance donation
simple vinylic protons and inductive withdrawal) and inductive withdrawal)
aromatic C-H δ 7.9 - 8.3 ppm
δ 6.7 - 7.0 ppm δ 6.5 - 7.0 ppm
δ 7.1 - 7.3 ppm H H H
H
O N
C O
R
simple aromatic protons aromatic protons (resonance aromatic protons (resonance donation
and inductive withdrawal) and inductive withdrawal)
aldehyde C-H alkyne C-H pyridine C-H pyrrole C-H furan C-H
O H δ 8.6 ppm Hδ 7.0 ppm
C C C H Hδ 6.3 ppm
H δ 6.6 ppm
H
δ 7.4 ppm H
δ 9 - 10 ppm δ 1.9 - 3.2 ppm N H
H O
aldehydes terminal alkyne protons N Hδ 8 ppm δ 7.4 ppm
δ 8.6 ppm broad
4. There are several kinds of hydrogen attached to heteroatoms. Some of these are listed below. Often
these hydrogens do not follow the N+1 rule because they exchange very fast on the NMR time scale
via acid/base proton exchanges and are not next to neighbor protons long enough to allow coupling to
be observed. They are often observed as broad singlets (sometimes so broad they are not easily seen
in a spectrum). If the exchange rate is very fast among all of the exchangeable protons on the NMR
time scale, all of the exchangeable protons may appear together at a single, averaged chemical shift.
O O O
O
O H H
S
N
H H
O H N H
H
δ ≈ 1-5 ppm δ ≈ 1-3 ppm δ ≈ 5-15 ppm

alcohols phenols and δ ≈ 1-2 ppm δ ≈ 10-12 ppm δ ≈ 1-6 ppm
thiols carboxylic acids amides
enol protons amines
The actual chemical shift (δ) depends on solvation, hydrogen bonding, exchange, etc.
Splitting patterns of coupled protons
1. Zero nearest neighbor proton
increasing δ
zero neighbor
H1 protons increasing ∆E (ν, Bo)
C
observed
proton
There is only
∆Eto flip proton ∆E1 (observed) one population
and one peak
Bo (called a singlet).
H1 There are no neighbor protons

to perturb the spin population.
C If there is no coupling, there are
no coupling constants (J, in Hz).
N + 1 rule (N = # neighbors)
# peaks = N + 0 = 1 + 0 = 1 peak
δ (ppm)
2. One nearest neighbor proton

increasing δ
one neighbor
H1 increasing ∆E (ν, Bo)
Ha proton = Ha
C C the ratio of these
observed perturbation(s) by
proton two populations
neighbor proton(s) is about 50/50 (or 1:1)
∆Eto flip proton H1
∆E2 (observed)
Bo ∆E1 (observed)
J1a
1 1
Protons in this environment have a small cancellation H1 H1 Protons in this environment have a small
of the external magnetic field, Bo, and produce a additional increment added to the external
smaller energy transition by that tiny amount. C C C C magnetic field, Bo, and produce a higher
energy transition by that tiny amount.
J = coupling constant N + 1 rule (N = # neighbors)

small difference in
energy due to differing J (Hz)
# peaks = N + 1 = 1 + 1 = 2 peaks
neighbor's spin (in Hz)
δ (ppm)
3. Two nearest neighbor protons (both on same carbon or one each on separate carbons)
the ratio of these
two neighbor four populations
H1
Ha protons is about 1:2:1
C C Hb H1
observed
proton ∆Eto flip proton ∆E1
∆E2 J1a
∆E3
Bo J1b J1b
two equal energy 1 2 1
H1 two neighbor protons are like
populations here
two small magnets that can be
C C arranged four possible ways N + 1 rule (N = # neighbors)
(similar to flipping a coin twice)
J (Hz) J (Hz) # peaks = N + 1 = 2 + 1 = 3 peaks
δ (ppm)
4. Three nearest neighbor protons (on same carbon, or two on one and one on another, or one each on separate carbons)
three neighbor the ratio of these
H1
Ha protons eight populations
is about 1:3:3:1
C C Hb
observed H1
proton Hc
∆E1
∆Eto flip proton ∆E2 J1a
∆E3
∆E4
Bo
J1b J1b
H1 three neighbor protons are like J1c J1c J1c

three small magnets that can be three equal energy 1 3 3 1
C C arranged eight possible ways populations at each
(similar to flipping a coin thrice) of middle transitions
N + 1 rule (N = # neighbors)
J (Hz) J (Hz) J (Hz)
# peaks = N + 1 = 3 + 1 = 4 peaks
δ (ppm)
Typical Coupling Constants (for this book, reality is more complicated)
Range Typical Range Typical
Ha Ha C Hb 0-3 Hz 1 Hz
C 0-30 Hz 12 Hz
C C (0 Hz, for us)
Hb
geminal protons - can have different chemical shifts cis / allylic coupling,
and split one another if they are diastereotopic notice through 4 bonds
Ha Hb Ha
6-8 Hz 7 Hz C C 0-3 Hz 1 Hz
C C
C Hb
(0 Hz, for us)
vicinal protons are on adjacent atoms, when freely trans / allylic coupling,
rotating coupling averages out to about 7 Hz notice through 4 bonds

θ = dihedral C C
Ha Hb
angle
H 0-12 Hz 7 Hz C C 9-13 Hz 10 Hz
C C
Ha Hb
depends on dihedral
H angle, see plot of sp2 vicinal coupling
Karplus equation (different π bonds)

Ha Hb Ha Hb
0-1 Hz 0 Hz 1-3 Hz 2 Hz
C C C C C
O
protons rarely couple through 4 chemical bonds sp3 vicinal aldehyde coupling
unless in a special, rigid shapes (i.e. W coupling)
Ha 0-3 Hz 2 Hz Ha Hb
5-8 Hz 6 Hz
C C C C
Hb C O
2
sp2 geminal coupling sp vicinal aldehyde coupling

Ha Hb
Ha
C C 5-11 Hz 10 Hz 2-3 Hz 2 Hz
C C C Hb
sp2 cis (acylic) coupling (always sp / propargylic coupling

smaller than the trans isomer) notice through 4 bonds

Ha
C C Ha Hb
11-19 Hz 17 Hz 2-3 Hz 3 Hz
Hb C C C C
sp2 trans coupling (always bis-propargylic coupling

larger than the cis isomer) notice through 5 bonds
Range Typical ortho, meta and H Range Typical

Ha para coupling to
Hortho
C C 4-10 Hz 7 Hz this proton ortho 6-10 Hz 9 Hz
C Hb meta 1-3 Hz 1 Hz
Hmeta para 0-1 Hz 0 Hz
sp2 / sp3 vicinal coupling H para (Jmeta & Jpara = 0 Hz, for us)
When J values are less than 1 Hz, it is often difficult to resolve them and a peak may merely appear wider and shorter.
Multiplets when the N + 1 rule works.
1 peak = 100%
s = singlet 1 edge peak = 50% of total area
d = doublet 1 1 edge peak = 25% of total area
t = triplet 1 2 1
edge peak = 12%
q = quartet 1 3 3 1 edge peak = 6%
qnt = quintet 1 4 6 4 1 edge peak = 3%
sex = sextet 1 5 10 10 5 1 edge peak = 1.5%
sep = septet 1 6 15 20 15 6 1
o = octet edge peak = 0.8%
1 7 21 35 35 21 7 1
Combinations or these are possible.
dd = doublet of doublets
ddd = doublet of doublet of doublets
dddd = doublet of doublet of doublet of doublets
dt = doublet of triplets
td = triplet of doublets
etc.
Predicted appearance of proton NMR spectrum (J values can all be different or J values can coincidently be the same = N+1 rule)
Protons A, B and C are coupled to one another, but not to protons D and E. Protons D and E are coupled to one another.
JAC = 10 Hz
(actual = 7) approximate chemical shifts (from tables)
A C
H H δA = 5.2 - 1.2 = 4.0 ppm (actual = 4.0)
JAB = 2 Hz C C δB = 5.2 - 1.1 = 4.1 ppm (actual = 4.2)
(actual = 2) H O CH2 CH3
B δC = 5.2 + 1.2 = 6.4 ppm (actual = 6.5)
D E
JBC = 17 Hz JDE = 7 Hz δD = 1.2 + 2.5 = 3.7 ppm (actual = 3.7)
(actual = 14) (actual = 7) δE = 0.9 + 0.4 = 1.3 ppm (actual = 1.3)
J values are all different. See 2n peaks, where HD J values are coincidently
n = number of neighbors. the same = N+1 rule.
HE
HC HA
HB
JBC = 17 Hz
JBC = 17 Hz JAC = 10 Hz
JDE = 7 Hz JDE = 7 Hz
JAC = 10 Hz JAB = 2 Hz JAB = 2 Hz
6.4 ppm 4.1 ppm 4.0 ppm 3.7 ppm 1.3 ppm
Calculated proton and carbon chemical shifts ( δ ) from our data are also shown in parentheses.
2.0
1.52
The simple N+2 rule works. OH
δ=3.5, 2H δ=1.0, 3H 0.9
t, J=7 t, J=7 0.96 3.53
+ 0.1
1.0
1.2
+ 2.3 25.3
3.5 OH
1.2
+ 0.3 10.1 65.1
1.5
δ=1.5, 2H 16 16 16
sex, J=7 _6
+ 10 + 48
δ=2.0 10 26 64
broad s
Starting 13C
shifts for propane
15.8
3 2 1 0 16.3 16.3
PPM
Br
The simple N+2 rule works.
3.78
δ=1.7, 6H
d, J=7
1.74 1.74
0.9
Br
+ 0.7
1.6
44.5
1.5
29.0 29.0
+ 2.1
3.6
16 16 16
δ=3.7, 1H +10 + 28 + 10
sep, J=7 26 44 26
3 2 1 0
PPM
* = chiral center
The simple N+2 rule does not work. Br
Diastereotopic protons of CH2 have
2.0
different chemical shifts and couple δ=1.8 3.69
one another with large J value. Second d,J=7 OH
δ estimated by δcalculated - 0.3 = 4.2 - 0.3 *
0.9
= 3.9 ppm 0.7 1.79 4.12;3.87
+ 0.1 Br
1.7
_ 4.2 1.5
0.3
3.9 2.1 52.7
OH
+ 0.3
1.2 δ=3.9, dd 3.9 *
2.3 1H, J=12, 4
δ=3.7, 1H 22.8 71.2
+ 0.7
4.2 sex, J=9, 7 ,4
δ=2.0 16
δ=4.1, dd broad s
16 16
J=12, 9 10 28 10
_6 + 10 + 48
20 54 74
4 3 2 1 0
PPM
Problem - Predict approximate NMR’s for the following compounds. Draw a sketch of your
estimated NMR. Include calculations of 1H chemical shifts, estimates of coupling constants (J
values) and multiplicities (s, d, t, q, dd, etc.), as well as the number of hydrogens to be integrated
at each chemical shift (by writing the appropriate number of hydrogens above the multiplet, e.g.
2H). The actual chemical shifts are written by each type of hydrogen to check your calculations.
a. b. c. d.
4.2
4.6 1.7 0.9 2.3 2.1 H H 6.5 1.2 1.3
2.6
H CH3 2.1 O O
C C
C C 1.5 H2 H2 H2 3.7
3.5 4.2
H2 H O C C C CH3
H H2C C CH3 0.9 O O
4.0 3.7 1.6 1.4 0.9
4.7
2.0 0.9
e 1.5-1.8 f g h * = chiral center

2.2 2.8 1.0 7.6
H O
OH 1.1
2.6 4.0 O 2.7 2.2
3.6
1.0 2.5 H HO *
H N
9.9 2.7
2.0 C
2.6 2.8 3.7
N HO H 3.8 O
>12 8.1
NO2
i j H k 2.4 l
6.8 7.2-7.7 CH3
J=16,7 H 8.0
O H H 6.8
1.5 O H S 2.4 2.1 1.1
7.2-7.7 3.3 CH3 O2N
H
H OH
1.0 2.3 9.5 2.8 H3C 4.4 1.5
J=8 11.4
H H O O H 7.2
6.1 3.7
J=16,8,1 8.0
H 6.7
m. 7.9 n.
H O
6.5 4.3 10.4

H 7.1 H 4.7
1.3 N O
O 7.3 1.3
1.4 3.1 4.1
0.9 1.6 O
N H 7.2
H 2.0
4.1
H
o. p.
1.9 Jallyl = 1.0 Hz 5.7
H
2.6 2.8 2.0
O H 5.6 2.3
1.0 O
N 1.0 0.9
4.2 Jgem = 1.6 Hz 4.5
1.7 1.4
O H
6.1 O H 5.6
Examples of Functional Group Possibilities
1. One point connection to isolated spin systems.
O O O O
N Ph Cl Br I
HO HS H2N O2N
C C C C C
HO Cl H2N H
carboxylic acid acid chloride 1o amide aldehyde nitrile alcohol thiol 1o amine nitro phenyl chloro bromo iodo
2. Two point connection to isolated spin systems.

R2 R1
O C
O O O O
C
H C
C C C C C O S N C
N
alkenes with 2H
O O H and 2 substituents
sulfide disubstituted disubstituted
anhydride ester 2o amide ketone ether 2o amine as geminal, cis or
alkyne aromatic (o, m, p)
trans
3. Three point connection to isolated spin systems (just a sampling).

R2 R1
O
C
N N
R3
o
trisubstituted
3 amide 3o amine aromatic
Consider a diastereotopic CH2 or C(CH3)2 next to a chiral center to have different chemical shifts. Calculate the δ1
chemical shift and then subtract 0.3 ppm to estimate a value for the δ2 chemical shift.
Use the following “typical” J values in your prediction of spectra. By keeping our values “typical” we simplify our
analysis of presented spectra. Real examples can be much more complicated, with every single coupling constant
different from “typical” leading to an undecipherable number of peaks that we end up calling a multiplet, because of
its complexity.
2
Jgeminal = 2 Hz O
3 O H H
2 3 Jortho = 9 Hz
Jgeminal = 12 Hz Jcis = 10 Hz C
4
C H C H C H
3 3 Jpara = 0 Hz C H
Jvicinal = 7 Hz Jtrans = 17 Hz H C C C C
(in this book,but H C
4
4
J = 0 Hz
Jallylic = 0 Hz typicall ≈ 1 Hz) C
(in this book,but
5
typicall ≈ 1 Hz) Jpara = 0 Hz 3
Jvicinal = 2 Hz 3 3 4
Jpropargylic = 2 Hz
Jvicinal = 6 Hz Jvicinal = 7 Hz
sp3 coupling alkene coupling aromatic coupling

miscellaneous coupling
Ha Hb Ha and Hb are diastereotopic in a

chiral environment. If they have
C different chemical shifts they will
split one another with Jgeminal = 12 Hz.
*
* = chiral center
3
Examples of possible sp spin systems (C1 through C6) that could be connected to the functional group patterns
shown above. There are a LOT of possibilities when di- or trisubstituted. We will try “some” of these. For
possible specific examples consider: Br, CN and Ar (in any combinations). (Remember, in our course Jvicinal = 7 Hz
and Jgeminal = 12 Hz when diastereotopic)
1 Carbon - mono-, di-, trisubstituted 2 Carbons - mono-, di-, trisubstituted
2 3 X
X 5 Y 6 Y
1 X=Y=Z 7 X=Y=Z
4
CH2 Y C H or or
H3C X X, Y, Z varies Y
Z X, Y, Z varies
X X X
Y X
Z (1,1-) (1,2-)
(1-) (1,1,2-)
3 Carbons - mono-, di-, trisubstituted

X=Y=Z
or Y
X, Y, Z varies 13 14 Y 15
9 10 Y 11 12
8 X
X Z X
Y X
Z X
X X X
Y 1,2- 1,3- Y
1- 2- 1,1- Z 1,1,2- 1,1,3- 1,2,3-

18 X 20 X 21 X
16 X 17 X 19 X 22 X Z
Y
Y
Y (1,2-) (1,1,2-) Y
(1,4-) (1,1,3-)
( 1-) (1,1-) (1,3-) Z
Y Y
27 Y
23 X 24 X Z 25 X 26
X=Y=Z
Y or
(1,2,3-) (1,2,4-) X X, Y, Z varies
(1,1,4-) ( 2-) X (2,3-)
Z Y Y Z
Only using examples with continuous spin systems

X
( 1-substituted,
disubstituted = 1,1-, 1,2-, 1,3-, 1,4-, 1,5-,
2 4 trisubstituted = 1,1,2-, 1,1,3-, 1,1,4-, 1,1,5-, 1,2,3-, 1,2,4-, 1,2,5-, 1,3,4-, 1,3,5- )
1 3 5
X
2 4
1 3 5 ( 2-substituted,
4 ( 3-substituted )
disubstituted = 2,3-, 2,4- ) 2
X 1 3 5
X X
4 ( 1-substituted, 2 4 ( 3-substituted,
2 1 disubstituted = 3,4-,
1 3 disubstituted = 1,1-, 1,3-, 1,4-, 1,5-, 3
trisubstituted = 1,1,3-, 1,1,4-, 1,1,5-, 1,3,4-, 1,3,5-, 1,4,4-, 1,4,5- ) trisubstitued = 3,4,4-, 2,3,4- )
5 5
2 4
1 3 X
( 4-substituted ) No continuous spin system possible.
5 X

X
( 1-substituted,
4 disubstituted = 1,1-, 1,2-, 1,3-, 1,4-, 1,5-, 1,6-,
2 6
1 3 5 trisubstituted = 1,1,2-, 1,1,3-, 1,1,4-, 1,1,5-, 1,1,6-, 1,2,3-, 1,2,4-, 1,2,5-, 1,2,6-, 1,3,4-, 1,3,5-, 1,3,6- )
X
2 4 ( 1-substituted,
1 3 5 disubstituted = 1,1-, 1,3-, 1,4-, 1,5-, 1,6-,
trisubstituted = 1,1,3-, 1,1,4-, 1,1,5-, 1,1,6-, 1,3,4-, 1,3,5-, 1,3,6-, 1,4,5-, 1,5,5-, 1,5,6- )
6
X
2 4
2 4 ( 3-substituted, 1 3 5 ( 4-substituted,
1 3 5 disubstituted = 3,4-, 3,5-, disubstitituted = 4,5-,
trisubstituted = 3,4,5-, 3,5,5- ) trisubstituted = 4,5,5- )
6 X
6
X 5
X
2 4 (1-substituted,
1 ( 5-substituted, 2 4
3 5 disubstituted = 5,5- ) 1 3 disubstituted = 1,5-, 1,6-,
trisubstituted = 1,1,5-, 1,1,6-, )
6 6
Alkene sp2 H & C example patterns

1 Y 3 7 8
2 4 5 6 O O X O Y
X Y
Y
X X
X
X Y
mono- trans- H X H H X
geminal- cis- Z tri-
9 O 10 Y 14
11 12 13 15
X H2 X
H2 H2
C C
H2 C H3C
H X Y X C Z X H3C
Z X X
Y
Y Y
Jgem ≈ 2 Hz
16 Y 17 Jcis ≈ 10 Hz
H3C X=Y=Z Jtrans ≈ 17 Hz
H3C X
or Jallylic ≈ 0 (for us), (typically = 1 Hz)
X, Y, Z varies Jsp3-sp2 = 7 Hz
X
Y Jald-sp2 = 6 Hz
Aromatic sp2 H & C example patterns

b a a a
1 H H 2 3 bH a H 5
H Y Y H 4 Z Y
C C C C C C C C C C
c a
H C C X bH C C X
b H C C X
H C C X Y C C X
C C C C C C C C C C
d c H bH
H e H d H c H c H
dH bH aH
(1-) (1,4-) (1,2,3-)
(1,2-) (1,3-)
6
a 7
H Y a 8 a a
Y H Z Y 9 10 a
Z Y H Y
C C
C C C C
C C C C
Z C C X b b
H C C X W C C X b b
H C C X Z C C X
C C
C C C C
C C C C
b H
cH
Z H H H
W H W H
(1,2,4-) (1,3,5-) (1,2,3,4-) (1,2,3,5-) (1,2,5,6-)
Jortho ≈ 9 Hz X=Y=Z=W
Jmeta ≈ 0 Hz (for us), (typically = 1 Hz) or
Jpara ≈ 0 Hz X, Y, Z, W varies
13 13
C NMR - Appearance of C carbons with directly attached proton neighbors (not commonly done)
1. Full coupling = larger J values, (versus off resonance decoupling = partially proton decoupled =
smaller J values, not common anymore.)
Full one bond Coupling (1JCH) is large (140-250 Hz), gives multiplets similar to H NMR’s N+1 rule
H H
13 13
13 13
C H C H C
C H
H
J = 140 Hz J = 140 Hz no coupling

J = 140 Hz (sp3 carbon)
Each of these peaks can be further split by protons 2-3 bonds
away (J = 7 Hz). We won't consider that complication factor here.
2. Off Resonance Coupling (reduced one bond coupling by partial irradiation of protons, smaller 1JCH = 5-10 Hz)
(used to be common and simple to interpret from the N+1 rule, but not used much now, DEPT is used instead)
13 1
C region H region irradiation near proton region partially decouples protons from
carbons in an off resonance experiment and shrinks the coupling
constant to a much smaller value so there is less overlap and it
is easier to interpret.
3 proton neighbors 2 proton neighbors 1 proton neighbors 0 proton neighbors
J = 5-10 Hz J = 5-10 Hz J = 5-10 Hz J = 5-10 Hz

R
CH3 C O C OH
CH2 C H
C H R O C
CH2 H R R
2-3 bond coupling disappears and C C C C C R OR
1 bond coupling is greatly reduced. C C H R O C
information appears as: H R
NH2
s = 0 attached protons O C
C C R O C
d = 1 attached proton C N
t = 2 attached protons R
q = 3 attached protons (methyl group)
3. Fully Proton Decoupled Carbon Spectrum only have singlets for each carbon (the usual way of
running a carbon 13 NMR).
All carbons above would appear as singlets in a fully proton decoupled 13C spectrum. Strong irradiation of the
proton region can be thought of as rapid interchange of population states so each carbon sees an average of
up/down proton spins with no net splitting (coupling). Simplifies spectrum ,but lose C-H information.
13
C region
CH3 CH2 C H C
1
H region
proton coupling disappears when direct irradiation of proton region
proton region is irradiated, all fully decouples protons from carbons
carbons become singlets
DEPT = distortionless enhanced by polarization transfer: This is a more recent multiple pulse
experiment. It is easier to read and interpret than off resonance 13C. However, it is much more difficult
to understand the theory behind the DEPT experiment (and we won’t try). The data can be presented in
unprocessed (shown below) or processed form (not shown). DEPT is equivalent to running multiple
carbon-13 NMR’s and it takes more time.
A full spectrum is needed to determine all distinct types of carbon
11 C15H24O2
4 3
p-butylbenzaldehyde diethyl acetal O 6
1 2 ppm
7 5 143.0
9 6
Fully decoupled 13C, all carbons show as singlets. 8
O 136.4
4 3 128.2
10 11 126.5
3 4 6 11 101.7
61.0
5 35.4
78 9 10 33.6
1 22.3
2
15.2
13.9
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
Variation 1 of DEPT: All protonated carbons appear as singlet up peaks, but C's without hydrogen do not appear.
3 4 6
5 78 9 10 11 All protonated
carbons are up.
1 2
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
Variation 2 of DEPT: All CH3's and CH's appear as singlet up peaks and CH 2's are singlet down peaks.
Again, C's without hydrogens do not appear.
3 4 5 All CH 3 & CH
10 11
carbons are up.
1 2
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

All CH2 carbons
6 7 8 9 are down.
Variation 3 of DEPT: Only CH's show as singlet up peaks. No other C's appear in this spectrum.
3 4 5 6 78 9 10 11
Only CH
1 2 carbons are up.
150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

Variation 3 shows the CH carbons. Variation 2 - Variation 3 leaves only CH3 carbons pointing up and CH2 carbons pointing down.
A processed DEPT separates out each type of carbon and displays them as up peaks in a separate
spectrum (not shown here).
Chemical shifts of carbons vary based on similar reasons used to explain differing proton chemical shifts (i.e.
electronegativity of environment and π bond anisotropy). Carbon chemical shifts occur over a wider range than
proton chemical shifts showing greater dispersion due to σpara. This means there is less chance of overlap in
decoupled 13C spectrum, (but occasionally it is still happens).
Typical 13C shift values are provided below. As with proton chemical shifts, 13C chemical shift values can be calculated
(predicted) with a fair amount of accuracy and there are a variety of ways to do so.
Generic values of 13C chemical shifts relative to TMS = 0 ppm
220 200 180 160 140 120 100 80 60 40 20 0 - 20

C CH3
N CH3
O CH3
C CH2
Br CH2
Cl CH2
N CH2
O CH2
C CH
Br CH
Cl CH
N CH
O CH
C C
Br C
Cl C
N C
O C
alkynes
C C
nitriles
C N
aromatics and alkenes
C C
heteroaromatics
Ar H
anhydrides
O C
esters
O C
amides
O C
carboxylic acids
O C
aldehydes
O C
ketones
O C
220 200 180 160 140 120 100 80 60 40 20 0 - 20
Similar chemical shift information presented in a different format. Remember, proton decoupled
carbons appear as singlets. When carbons are coupled to their hydrogens, carbons follow the N+1 rule.
Methyls = q, methylenes = t, methines = d, and carbons without hydrogen appear as singlets = s.
DEPT provides the same information. Carbon chemical shifts are spread out over a larger
range than proton chemical shifts (they are more dispersed), so it is less likely that two different carbon
shifts will fall on top of one another. The relative positions of various types of proton and
carbon shifts have many parallel trends (shielded protons tend to be on shielded carbons, etc.)
CH2 CH C
Simple alkane CH3
carbons
d 0 - 30 ppm d 20 - 40 ppm d 30 - 50 ppm d 30 - 60 ppm
(q) (t) (d) (s)
CH3 O CH2 O CH O
sp3 carbon C O
next to oxygen
d 50 - 60 ppm d 55 - 80 ppm d 60 - 80 ppm d 70 - 90 ppm
(q) (t) (d) (s)
CH2 N CH N
sp3 carbon CH3 N C N
next to nitrogen d 35 - 55 ppm
d 10 - 50 ppm
d 50 - 70 ppm d 50 - 70 ppm
(q) (t) (d) (s)
CH2 X CH X
sp3 carbon next to C X
bromine or chlorine
(X = Cl, Br) d 25 - 50 ppm d d 60 - 80 ppm
60 - 80 ppm
(t) (d) (s)
sp carbon (alkynes) C C sp carbon (nitriles) C N

δ 70 - 90 ppm δ 110 - 125 ppm
sp2 carbon (alkenes

and aromatics) C H C X C X
C H
δ 100 - 140 ppm δ 140 - 160+ ppm

simple sp2 carbon sp2 carbon attached to an electronegative atom
(X = oxygen, nitrogen, halogen) or Cβ carbon
resonance donation moves δ lower,
conjugated with a carbonyl group
resonance withdrawal moves δ higher
O O O
C C C
X H R
δ 160 - 180 ppm δ 180 - 210 ppm δ 180 - 220 ppm
carboxyl carbons aldehyde carbons, lower ketone carbons, lower
(acids, esters, amides) values when conjugated values when conjugated
(s) (d) (s)
13
Calculations of alkane C chemical shifts not listed above.
sp3 Carbon Chemical Shift Calculations
Calculations for sp3 carbon 13C chemical shifts of functionalized carbon skeletons can be performed starting
from the actual shifts found in the corresponding alkane skeleton, and introducing corrections factors based on the
functionality present in the molecule. This assumes that the alkane 13C shifts are available, which is why several
examples are provided below.
Examples of Cn alkanes as possible starting points for calculation 13C shifts in ppm.
Steric Corrections for sp3 carbon chemical shift calculations Approximate 13C shift calculation from scratch.
The attached Cα carbons are:
The calculated δC = -(2) + 9x(#α + #β) - 2x(#γ ) + steric corrections

carbon atom is:
primary secondary tertiary quaternary
C1 = -2 + 9(1+3) - 2(2) + (-3) = 29 (actual = 28.3)
primary 0 0 -1.1 -3.4
C2 = -2 + 9(4+2) - 2(2) + [3x(-1.5)+(-15.0)] = 28 (actual = 34.0)
secondary 0 0 -2.5 -7.5 2 4 C3 = -2 + 9(3+5) - 0(2) + [(-9.5)+(-15.0)] = 45 (actual = 47.9)
3
0 -3.7 -9.5 -15.0 1 5
tertiary C4 = -2 + 9(3+2) - 3(2) + (-9.5) = 27 (actual = 27.2)
-1.5 -8.4 6
-15.0 -25.0 C5 = -2 + 9(1+2) - 2(2) + (-1) = 20 (actual = 19.5)
quaternary
C6 = -2 + 9(1+2) - 5(2) + (-1) = 14 (actual = 8.5)
13
C shifts for various carbon alkane skeletons - useful starting points for calculating sp3 carbon chemical shifts
22.3
C2 C3 C4 C5
16.3 25.4 22.6 32.0
25.0 30.2 11.8 29.7
CH4
25.0
-2.3 5.9 15.8 14.1 34.4 31.9 32.0
13.8
C6 29.0
22.7 11.5
22.9
19.5
27.9 20.6 8.9
30.4
14.1 32.9 18.8 33.9
36.3
41.5 14.4 29.3 36.5
19.2 29.8 48.3 14.7 15.0

C7 22.7 11.4 20.3
22.9 29.3 12.0
29.9 14.1 31.8
33.4 17.5 18.1
34.4 40.6
14.1 32.1 28.1 29.7 39.2 14.5 26.9
39.0 23.1
22.9 48.9 27.0

27.0
11.0 37.2 17.9
25.6 9.1
38.0
35.3 42.3
25.2
36.4
C8
14.5 39.6
22.9 29.5 22.7 29.6 36.5 19.3
27.2 22.8 34.6 10.9 40.3 20.1
20.3 32.4
14.1 32.1 28.1 11.5 29.7 14.1
39.2 32.3 14.1 25.6 35.4 14.6
19.7
C9 C10
22.8 29.6 22.9 29.6
14.1 32.1 29.8 14.2 32.2 29.9
13
If such a starting point is not available, then calculations of the individual C shifts of the
corresponding alkane can be approximated starting from the chemical shift of methane (-2.3 ppm).
Correction factors are included for directly attached carbon atoms (Cα = +9.1), once removed carbon
atoms (Cβ = +9.4) and twice removed carbon atoms (Cγ = -2.5). Steric corrections are also made when
there is a greater density of highly substituted carbons near one another. Finally, the alkane 13C shift
values are then modified by correction factors for any appropriate substituent(s). The example alkane,
just below, is not present in those listed above. The actual chemical shifts of this alkane are known, so we
can check how accurate our calculated values compare with the real values. Once we have demonstrated
how to calculate the 13C chemical shifts of an alkane, we will introduce a few substituents to show how
they change the chemical shifts of nearby carbons.
An alkane carbon atom’s 13C shift is affected most by the directly attached carbons (Cα), and
carbons once removed (Cβ). Both types of carbon neighbors are deshielding by about 9 ppm. Any carbon
atoms just beyond the Cβ carbons are called Cγ carbons, and are slightly shielding by about -2.5 ppm.
Finally, there is a steric correction factor required when there is a dense collection of near-by Cα and Cβ
carbon atoms.
The starting point (methane) for 13C chemical shift calculations = -2.3 ppm
There is a Cα correction for all directly attached carbon atoms, Cα = +9.1 ppm
There is a Cβ correction for carbons attached to Cα, Cβ = +9.4 ppm
There is a Cγ correction for carbons attached to Cβ, Cγ = -2.5 ppm
Steric corrections are made according to substitution patterns of the carbon for which the
calculation is being made and substitution patterns of all Cα positions, as indicated in the table below.
Include a steric correction factor for each Cα carbon attached, if it is indicated.
The attached Cα carbons are:
The calculated
carbon atom is:
primary secondary tertiary quaternary
primary 0 0 -1.1 -3.4

secondary 0 0 -2.5 -7.5
tertiary 0 -3.7 -9.5 -15.0
quaternary -1.5 -8.4 -15.0 -25.0
The “more precise” formula for calculating an sp3 carbon13C chemical shift is as follows.
δC = (-2.3) + (#Cα)(9.1) + (#Cβ)(9.4) + (#Cγ)(-2.5) + (steric corrections) ppm
The 13C chemical shift calculations of 2,2,3,5-tetramethylpentane are provided as examples. The
actual chemical shifts are also provided for comparison. The calculated carbon shifts in this example
range from 0.4 ppm to 5.6 ppm off.
δC = -2.3 + (#Cα)(9.1) + (#Cβ)(9.4) + (#Cγ)(-2.5) + (steric corrections) ppm
6
CH3 CH3 CH3
1 2 3 4 5
H3C C C C CH3
H H
CH3
Cα Cβ Cγ steric δcalculated (δreal)

C1 = -2.3 + (1)(9.1) + (3)(9.4) + (2)(-2.5) + (-3.4) ppm = 26.7 (actual = 28.3)
C2 = -2.3 + (4)(9.1) + (2)(9.4) + (2)(-2.5) + (-15.0) + (3)(-1.5) ppm = 28.4 (actual = 34.0)
C3 = -2.3 + (3)(9.1) + (5)(9.4) + (0)(-2.5) + (-15.0) + (-9.5) ppm = 47.5 (actual = 47.9)
C4 = -2.3 + (3)(9.1) + (2)(9.4) + (3)(-2.5) + (-9.5) ppm = 26.8 (actual = 27.2)
C5 = -2.3 + (1)(9.1) + (2)(9.4) + (2)(-2.5) + (-1.1) ppm = 19.5 (actual = 17.7)
C6 = -2.3 + (1)(9.1) + (2)(9.4) + (5)(-2.5) + (-1.1) ppm = 12.0 (actual = 8.5)

As mentioned above, the known or calculated chemical shifts of a similar alkane structure can serve as a
starting point for estimating the chemical shifts of a similar functionalized carbon skeleton. This requires making a
correction to the carbons near-by the functional group. Two correction values are provided for each substituent,
depending on whether the substituent is at the end of a chain (terminal) or in the middle of a chain (internal).
Several substituent values are provided in side-by-side tables that follow.
An example showing how a substituent value can be estimated.

butane 13C chemical shifts = starting values
13.8 25.0
25.0 13.8
X is attached to a terminal carbon atom of a freely X is attached to a terminal carbon atom of a freely
rotating chain. rotating chain.
X
3 1
4 2
X 4 2
3 1
X = -OH compare to butane X = -OH compare to butane
OH
19.1 62.3
10.1
OH X = OH 22.8 X = OH
13.9 34.9 69.3
32.1
δ (ppm) - δ (alkane) = ∆(correction factor) δ (ppm) - δ (alkane) = ∆(correction factor)
1 = 62.3 - 13.8 = +48.5 Cα correction 1 = 22.8 - 13.8 = + 9.0 Cβ correction
2 = 34.9 - 25.0 = + 9.9 Cβ correction 2 = 69.3 - 25.0 = +44.3 Cα correction

3 = 19.1 - 25.0 = - 5.9 Cγ correction 3 = 32.1 - 25.0 = + 7.1 Cβ correction
4 = 13.9 - 13.8 = + 0.1 Cδ correction 4 = 10.1 - 13.8 = - 3.7 Cγ correction
A table of corrections factors for “X” substituents on alkane skeletons (in terminal and internal positions) is
provided on the next two pages. Average correction factors for Cα, Cβ and Cγ carbons relative to substituent. Cδ is
assumed small enough to ignore (not always true). We are also not considering the influence of conformational
factors (shapes), which can be significant in relatively rigid systems (e.g. chair conformations can influence
chemical shifts).
R α γ
X α γ β
β
X
X is attached to a terminal carbon atom (ppm) X is attached to an internal carbon atom (ppm)
Substituent = X Cα correction Cβ correction Cγ correction Cα correction Cβ correction Cγ correction
CH3 9 9 -2 6 8 -2
CH2CH3 18 7 -2 9 6 -2
CH(CH3)2 26 4 -2 14 3 -2
C(CH3)3 32 2 -2 20 1 -2
C CH2 20 6 -1 15 5 -1
H
C CH 5 5 -4 2 6 -4
23 9 -2 17 7 -2
OH 48 10 -6 44 7 -4
OR 60 7 -6 57 5 -6
O
O C 51 6 -6 5 -6
49
NH2 28 10 -5 24 8 -5
NH(CH3) 38 8 -5 32 5 -4
N(CH3)2 5 -5 37 3 -4
45
O
H
N C 26 7 -5 5 -5
21
R
NO2 62 5 -5 58 2 -5
F 70 8 -7 67 5 -7
Cl 31 10 -5 36 8 -5
Br 20 10 -4 28 10 -4
I -7 11 -2 7 11 -2
O
C 30 0 -3 24 -1 -3
H
O
C 31 1 -3 26 0 -3
CH3
O
C 22 2 -3 18 1 -3
OH
O
C 20 2 -3 16 2 -3
OCH3
O
C 25 3 -3 19 2 -3
NH2
C N 3 3 -3 3 3 -3
O
C 33 2 -3 30 2 -3
Cl
SH 11 10 -3 12 8 -3
SR 22 8 -3 20 6 -3
13
Possible starting point values for calculating C chemical shifts (ppm) in cycloalkanes. Use internal
substituent corrections from table above. Rigid or preferred conformations may alter these calculated
values in a real structure.
-2.3 21.6 26.0 27.1 28.5
26.9 26.4 25.0
Correction factors for calculating alkene 13C chemical shifts. The starting point value is 123.3
from ethane (ethlylene). The first table assumes a hydrocarbon skeleton, which can then be
modified using the alkane substituent correction factors above. The second table looks at specific
substituents on alkene carbon atoms. Two columns are listed in each table. One column (α, β, γ)
for when the substituent is directly attached to the carbon whose chemical shift is being
calculated, and a second column (α’, β’, γ’) for when the substituent is on the other carbon of the
double bond.
Alkene corrections for alkane branches.
C1 C2
Cγ Cβ Cα Cα' Cβ' Cγ'
δC1 calculated chemical shift = 123.3 + [10.6α + 7.2 β - 1.5γ] - [7.9 α' + 1.8β' - 1.5 γ'] + (steric corrections)
Steric corrections:
Cα and Cα' are trans 0
Cα and Cα' are are cis -1.1
2 x alkyl substituents at C1 -4.8
2 x alkyl substituents at C2 +2.5
(2 or more) x substituents at Cβ +2.3
Alkene corrections for specific substituents. If you don’t find an exact match for your
substituent, you might be able to approximate it using one of the values below.
C1 C2
A B
δC1 calculated chemical shift = 123.3 + any corrections listed below.
Substituent A B
-H 0 0
-CH3 12.9 -7.4
-CH2CH3 19.2 -9.7
-CH2CH2CH3 15.7 -8.9
-CH(CH3)2 12.9 -7.4
-C(CH3)3 26.5 -14.5
-CH=CH2 13.6 -7
-C6H5 12.5 -11
-CCH -6.5 +5.2
-CH2Cl 10.2 -6
-CH2Br 10.9 -4.5
-CH2 I 14.2 -4.0
-CH2OH 14.2 -8.4
-CH2NH2 16.7 -9.8
-CH2OCH3 29.4 -38.9
-CH2OCH2CH3 28.6 -36.9
-CH2C5H6 14.2 -7.5
-COOH 5.0 -9.8

-COOCH3 5.2 +7.3
-CONH2 6.0 +7.1
-COCl 8.1 +14.0
-CH=O 15.3 +14.0
-COCH3 13.8 +4.7
-CN -15.1 +14.2
-OCH3 29.4 -38.9

-OCH2CH3 28.6 -36.9
-OCOCH3 18.4 -26.7
-NO2 22.3 -0.9

-Si(CH3)3 16.9 +6.7
-F 24.9 -34.3
-Cl 2.6 -6.1
-Br -8.6 -0.9
-I -38.1 7.0
-H 12.9 -7.4
13
Correction factors for calculating aromatic C chemical shifts. The starting point value is 128.5
from benzene. Four columns are listed. The first column is called “ipso” corrections and is used
when the substituent is directly attached to the carbon in the benzene ring. The other columns are
used when the carbon shift being calculated is ortho, meta or para to the substituent carbon.
Multiple corrections should be made when multiple substituents are present. Each substituent
may have a different relationship with each of the carbon atoms in the benzene ring. The more
substituents that are present, the less reliable is the chemical shift calculation.
δC calculated chemical shift = 128.5 + any corrections listed below.

S = substituent
Substituent ipso ortho meta para
ipso
ortho ortho -H 0 0 0 0
-CH3 9.3 0.7 -0.1 -2.9
-CH2CH3 11.7 -0.5 0 -2.6
meta meta -CH2CH2CH3 14.2 0 -0.2 -2.8
-CH(CH3)2 20.3 -2.1 -0.2 -2.7
para -C(CH3)3 22.5 -3.1 -0.3 -3.1
-CH=CH2 9.2 -2.3 0 -0.7
-C6H5 8.1 -1.1 -0.5 -1.1
-CCH -6.3 3.6 -0.2 -0.2
-CH2F 7.9 -1 0.1 0.2

-CH2Cl 9.0 0.2 0 -0.2
-CH2Br 9.2 0.5 0.2 -0.2
-CH2OH 12.4 -1.5 -0.1 -1.1
-CH2NH2 14.9 -1.5 0 -1.8
-CH2OCH3 9.8 -0.1 -0.8 -0.9
-CH2C5H6 12.9 0.4 -0.1 -2.5
-COOH 2.1 -1.6 -0.1 5.2

-COOCH3 2.0 1.2 -0.1 4.3
-CONH2 5.7 -1.0 0.4 3.7
-COCl 4.7 2.9 0.5 6.9
-CH=O 8.2 1.2 0.6 5.8
-COCH3 8.9 -0.1 -0.1 4.4
-CN -16.0 3.6 0.6 4.3
-OCH3 33.5 -14.4 1.0 -7.7

-OCH2CH3 30.5 -13.9 0.9 -7.9
-OCOCH3 22.4 -7.1 -0.4 -3.2
-NO2 19.8 -5.0 0.9 6.2

-Si(CH3)3 11.9 4.8 -0.7 0.3
-F 33.6 -13.0 1.6 -4.5

-Cl 5.3 0.4 1.4 -1.9
-Br -5.4 3.4 2.2 -1.0
-I -31.2 8.9 1.6 -1.1
13
C NMR Problems Name
Beauchamp
Use the molecular formulas along with the 13C chemical shifts and multiplicities to determine a
reasonable structure for the following molecules (There may be more than one reasonable possibility.)
The multiplicities are s = singlet, d = doublet, t = triplet, q = quartet. The degree of unsaturation can help
determine the possible number of rings and/or π bonds. Draw an approximate sketch of each spectrum.
Use arrows drawn from each type of carbon pointing to the appropriate chemical shift to indicate the
correct correspondence.
1. C8H18 - 24.9d, 25.5q, 30.2q, 31.2s, 53.4t
2. C5H11Cl - 22.0q, 25.7d, 41.6t, 43.1t
3. C4H8O2 - 14.4q, 20.9q, 60.4t, 170.7s
4. C4H7Br - 17.5q, 32.9t, 127.8d, 131.0d
5. C6H8O - 18.7q, 130.2d, 130.4d, 141.6d, 153.3d, 193.0d
6. C9H12 - 21.2q, 127.2d, 137.5s
7. C6H15NO - 27.0t, 27.9t, 34.2t, 34.9t, 43.2t, 62.9t
8. C9H10O - 8.2q, 31.6t, 128.0d, 128.6d, 132.8d, 137.2s, 200.0s
9. C5H8O2 - 14.4q, 60.4t, 129.3t, 130.0d, 166.0s
10. C9H10O3 - 56.0q, 56.1q, 109.4d, 110.7d, 126.5d, 130.3s, 149.8s, 154.6s, 190.7d
11. C12H14O4 - 14.2q, 61.5t, 129.0d, 131.1d, 132.7s, 167.5s
12. C9H8O3 - 115.4d, 115.9d, 125.4s, 130.0d, 144.2d, 159.7s, 168.1s
13. C8H11N - 13.0q, 23.9t, 115.4d, 118.6d, 126.8d, 128.0s, 128.4d, 144.3s
14. C11H14O - 14q, 23t, 26t, 38t, 128d, 129d, 132d, 136s, 201s
15. C4H11N - 13q, 44q, 52t
16. C4H8O - 14q, 16t, 45t, 202d
17. C5H12O - 22q, 24t, 42d, 62t
18. C10H9NO2 - 15q, 62t, 116s, 118s, 129d, 132d, 134s, 165s
19. C9H9ClO - 39t, 41t, 127d, 128d, 133d, 136s, 196s
20. C13H20N2O2 - 12q(x2), 46t(x2), 51t, 63t, 114d, 120s, 131d, 151s, 166s
21. C11H14O - 27q, 44s, 127d, 127.5d, 131d, 138s, 209s
22. C3H4Br2O2 - 28.8t, 40.4d, 173.6s
23. C3H5Br - 32.6t, 118.8t, 134.2d
24. C3H6Cl2 - 22.4q, 49.5t, 55.8d
Possible approach for solving a structure problem.
Each structure is a puzzle made of an unknown number of pieces that you create. Your goal is to use the
spectral data to make the pieces of your puzzle as few as possible (big pieces make fewer pieces). It’s easier to
solve a 25 piece puzzle than a 1000 piece puzzle. Your goal is to make a two piece puzzle that only fits together
one way. It’s not always possible, but that’s the goal. The more pieces there are, the more difficult your choices.
The Goal: only one way to connect. A B A B
...two ways to connect,
A C D B A C D B or A D C B
...or more ways? ( six ways here)
E
A B C D F 6 ways to connect these pieces
If you have access to some of the more modern NMR experiments, it can make your job of structure
determination relatively straightforward. However, there is a lot of information to organize (organized = easy,
unorganized = impossible). My strategy for “organizing” the information is provided in the next pages.
1. From the 13C and DEPT data identify each carbon piece. Look for aspects of symmetry that will make some
carbon atoms equivalent. Chemical shifts of protons and carbons provide clues about nearby functionality.
2. Use the HETCOR to pair up carbons with their attached protons. Double check assignments with DEPT.
3. Use the COSY cross peaks to connect the coupled proton/carbon pieces from the HETCOR data (#2). Double
check the COSY fragment patterns with the multiplicities in the proton NMR spectrum to see if they are
consistent.
4. Proton and carbon chemical shifts provide hints and suggestions about nearby heteroatoms (N,O,halogens,etc.)
and pi bond patterns (alkenes, alkynes, aromatics, carbonyl groups, nitriles, etc.). Multiple functionality
producing smaller shifts can produce a large shift from a single stronger influencing functional group. Using
chemical shifts this way may help locate quaternary carbon centers and heteroatoms (e.g. next to ester carbon side
or next to ester oxygen side). HMBC (explained later) is very helpful for placing quaternary carbon atoms.
O O
C C N
C
C C
C C R X
sp2 carbon sp carbon
sp3 carbon alkenes & ketones carboxylic acids
alkynes &
aromatics nitriles & derivatives
These are all considered "quaternary" centers (carbon atoms without any attached hydrogen atom). The lack
of an attached hydrogen takes away connectivity clues in the COSY and HETCOR spectra (explained later).
Remember resonance effects can be both shielding (more electron density, smaller δ) and deshielding (less
electron density, larger δ).
O R O R
δ=5.2+1.2=6.4 NH2 NH2 C C
H H δ=7.3 - 0.8=6.5 δ=7.3+0.6=7.9
δ=5.2-1.1=4.1 C H C H C H C H
C H C H C C C C
O C O C
Inductive withdrawing effects are deshielding and not usually completely additive.
H Cl Cl Cl
R C H R C H R C Cl R C Cl
H H H Cl
proton shifts: 0.9 ppm ∆=2.6 3.5 ppm ∆=2.6 5.9 ppm ∆=NA no protons
carbon shifts 14 ppm ∆=31 45 ppm ∆=24 69 ppm ∆=26 95 ppm

:
5. Look for symmetry features in the proton and carbon NMR spectra. Count the number of carbon atoms in the
13
C NMR and the number of protons in the H NMR to help make a formula (rule of 13). Estimate the number
of heteroatoms (N,O,halogens) to modify your formula (use the IR functional groups and the H NMR and 13C
NMR chemical shifts). Calculate a degree of unsaturation and use the 13C to estimate the number of pi bonds,
and by difference determine the number of rings in your structure.
6. Look for end pieces of your puzzle that only connect one way, and middle pieces that connect 2, 3, or more ways and
try to fit them together based on expected chemical shifts.
A possible worksheet to help solve your structure problems is provided just below.
Structure Problem Worksheet
13
C / DEPT HETCOR COSY HMBC NOE and/or NOESY
Advantages of other 1D and 2D NMR experiments: DEPT, COSY, HETCOR, HMBC – An Example
1
H NMR – Integration indicates the number of hydrogen atoms at each chemical shift. The chemical shift provides
information about the functional group environment around the protons, and the multiplicity provides information
about neighboring “coupled” protons having different chemical shifts. Typical coupling includes geminal (2 bond
coupling, both hydrogen atoms attached to the same carbon atom, as =CH2 or as *-CH2, where * = chiral center),
vicinal coupling (3 bond coupling) and a few 4 bond couplings (allylic, meta, para, etc.) that we mostly ignore.
MW = 223.1 (bromine is present)
0.96,3H
t,J=7
3.53,2H 2.45,2H
t,J=7 t,J=7
1.79,2H
qnt,J=7
1.76,2H
qnt,J=7
3.65,1H
qnt,J=7 3.04,1H 2.79,1H
dd,J=12,7 dd,J=12,7
2.0
broad s
3 2 1 0
PPM
13
C NMR and DEPT (distortion enhancement by polarization transfer) data
The 13C NMR shows each distinct type of carbon atom. If atoms are equivalent, by symmetry, they will appear as a
single peak, often at approximately “n” times the intensity, where “n” is the number of similar carbons. When a carbon
atom does not have any attached hydrogen atom its intensity is often weaker (a smaller peak appears), because it
relaxes so slowly it does not give a full intensity response with each pulse (excitation). Such carbons are often referred
to as “quaternary” carbon atoms. DEPT shows the number of hydrogens on each carbon, as indicated below.
Top spectrum = DEPT-135 13C NMR - CH3 and CH appear (up) and CH2 appears (down)
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
13
Middle spectrum = DEPT-90 C NMR - only C-H appears (up)
210.1
62.4
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0 49.3
38.1
Bottom spectrum = proton decoupled 13C NMR spectrum - shows all types of carbon
37.0
solvent
32.6
25.5
10.0
210 200 190 180 170 160 150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0
HH COSY spectrum (Proton-Proton Correlation Spectroscopy)
The diagonal peaks show the same peaks and chemical shifts that are seen in the normal proton NMR, and
are not helpful. However, the cross peaks (off diagonal peaks) show proton/proton correlations with
“coupled neighbor” protons, and can trace out a path of connectivity in each spin system (a spin system is a
continuous path of coupled protons). Connect the dots to construct the spin systems within a structure.
COSY: H-H correlations: diagonal peaks do not provide any additional information, but cross peaks appear whereever
different neighbor protons are coupled.
3.53 2.79 2.0 1.79 0.96
3.65 3.04 2.45 1.76
10.0 9.0 8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0.0
0.0
1.0
0.96
1.76
1.79
2.0
2.0
2.45
2.79
3.0
3.04
3.53
3.65
7.0
9.0
10.04.0
5.0
6.0
8.0
HETCOR spectrum
The peaks (dots) show carbon atoms and proton atoms that are directly attached to one another (one bond
coupling), as in a direct C-H bond. This is detected via one bond C-H coupling constants (1JCH), which are large
(around 120-160 Hz). In a sense, you could say that we are looking for the coupling patterns about 140 times per
second and these interactions are repeatedly reinforced, while other coupling is random (sometimes + and
sometimes -) and cancels out. Once you have made these C-H connections, the COSY spectrum will not only show
neighbor protons, but it will also show neighbor carbon atoms attached to those protons.
1.79
3.53 2.0 0.96
3.65 3.04 2.79 2.45 1.76
10.0 9.0 6.0 5.0 4.0 3.0 2.0 1.0 0
8.0 7.0
HETCOR correlations
10 10.0
20
25.5
30
32.6
37.0
40 38.1
49.3
50
60
62.4
70
80
90
100
110
120
130
140
150
160
170
180
190
200
210 210.1
220
HMBC spectrum
The peaks (dots) show carbon atoms and proton atoms that are two and three bonds away from one another
(2 and/or 3 bond coupling). This is detected via two and three bond C-H coupling constants (2/3JCH around 7-10
Hz), which are much smaller than one bond coupling. This is especially helpful for quaternary carbon atoms which
do not show coupling to neighbor carbons or protons, (in our course).
2
JCH 3
JCH HMBC = heteronuclear multiple bond correlation
H H Detection of CH coupling is timed to the approximate coupling between
13 13 the coupled atoms. In this case of HMBC this is approximately 10 Hz.
C C C C C In a sense we are looking for a signal 10 times per second. Smaller or larger
coupling usually tends to average towards zero. It is possible that expected
coupling will not be present and unexpected coupling will appear. These
JCH ≈ 7-10 Hz
2
JCH ≈ 7-10 Hz
3 complications are excluded in our simple approach to problems. Correlations
with quaternary carbons (no attached hydrogen atoms) are especially helpful.
HMBC correlations = Shows carbon couplings to protons 2 and 3 bonds away.

3.53 2.79 1.79
3.65 3.04 2.45 1.76 0.96
10.0 9.0 6.0 5.0 4.0 3.0 2.0 1.0 0
8.0 7.0
10.0
25.5
32.6
37.0
38.1
49.3
62.4
210.1
If you organize all of this information in a compact way (the one page worksheet) so you can confirm or reject
structure possibilities, it becomes quite straight forward to construct a reasonable structure of the molecule. Left
out of our discussion are issues of relative stereochemistry. There are other NMR experiments (NOE, NOESY,
ROESY) that help resolve these details, but we will not discuss them in this course.
Structure Problem Worksheet
13
C / DEPT HETCOR COSY HMBC NOE and/or NOESY
C=O
210.1 3.65, 3.04, 2.79, 2.45, 1.76
ketone
62.4 CH2-O 3.53 1.76 3.65, 2.45, 1.76
49.3 CH2 2.79 3.04 , 3.65

3.04 3.65, 2.45, 1.79
2.79 , 3.65
38.1 CH2 2.45 1.76 3.53, 3.04, 2.79, 1.76
37.0 CH 3.65 3.04, 2.79, 1.79 3.04, 2.79, 2.45, 1.76
32.6 CH2 1.79 3.65, 0.96 3.65, 3.04, 2.79, 1.79, 0.96
25.5 CH2 1.76 2.45, 3.53 3.53, 2.45
10.0 CH3 0.96 1.79 3.65, 1.79
Answer
13
Proton Data C Data
Br O Br O
0.96 2.0 10.0 210.8 25.5
3.65 1.76 37.6
OH OH
1.79 3.04;2.79 2.45 3.53 32.6 49.3 37.9 62.4

NMR Info Tables 12-31-09

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Beauchamp Spectroscopy - NMR 1

(Chem 318, 319, 422, 424)

higher higher A excess higher

ultraviolet visible infrared radiowave

ν (frequency) 1015 1015 1014 107

∆E = energy ν = frequency λ = wavelength ν = wavenumber

∆E = hν = hc(1/λ) = hcν c = (ν)(λ) = 3.0 x 108 m/sec = 3.0 x 1010 cm/sec

Proton (1H) and carbon (13C) "magnets"

“I” is the spin quantum number.

Number of Spin States = 2(I) + 1

Spinning electrical charge

In the presence of a magnetic

∆E1= hν1 ∆E2= hν2 ∆E3= hν3 ∆E4= hν4

The ∆E between the energy states depends on two magnets:

∆E (0.028 cal / mole)

E2 = -------------- 9,999 ---------- We see a difference of 1 out of about

∆E = hν = ( h ) ( γ i) (Bo) = (constants) x (type of nucleus) x (external magnetic field)

The spread in each region shows

CH3-F CH3-OR CH3-Cl CH3-Br CH3-I CH3-H (CH3) 4Si = TMS

larger frequency shift from the TMS reference Ref = 0

∆E = 300,000,000 Hz (energy to flip proton spin) constant magnetic field strength

larger frequency shift from the TMS reference Ref = 0

200 180 160 140 120 100 80 60 40 20 0 = δ = ppm

shielding shielding shielding

Starting value and equations for CH3's

Substituent α geminal α cis α trans Substitution relative to calculated "H"

0.2 ∆ = 2.8 3.0 ∆ = 2.3 5.3 ∆ = 1.9 7.2 ∆=? ? (oops)

3.0 3.5 4.1 2.6 3.0 3.5

isomer 1 isomer 2 isomer 3

δ ≈ 1-5 ppm δ ≈ 1-3 ppm δ ≈ 5-15 ppm

H1 There are no neighbor protons

2. One nearest neighbor proton

J = coupling constant N + 1 rule (N = # neighbors)

H1 three neighbor protons are like J1c J1c J1c

Range Typical Range Typical

Range Typical Range Typical

Range Typical Range Typical

sp2 cis (acylic) coupling (always sp / propargylic coupling

Range Typical Range Typical

sp2 trans coupling (always bis-propargylic coupling

Range Typical ortho, meta and H Range Typical

Combinations or these are possible.

JAC = 10 Hz JAB = 2 Hz JAB = 2 Hz

e 1.5-1.8 f g h * = chiral center

6.5 4.3 10.4

2. Two point connection to isolated spin systems.

3. Three point connection to isolated spin systems (just a sampling).

sp3 coupling alkene coupling aromatic coupling

Ha Hb Ha and Hb are diastereotopic in a

3 Carbons - mono-, di-, tri- substituted

4 Carbons - mono-, di-, tri- substituted

Only using examples with continuous spin systems

6 Carbons - mono-, di-, tri- substituted

Alkene sp2 H & C example patterns

Aromatic sp2 H & C example patterns

J = 140 Hz J = 140 Hz no coupling

J = 5-10 Hz J = 5-10 Hz J = 5-10 Hz J = 5-10 Hz

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0

150 140 130 120 110 100 90 80 70 60 50 40 30 20 10 0