Moc Spectroscopy Pack

https://MasterOrganicChemistry.
com
Summary Sheet - Index of Unsaturation
(AKA "Index of Hydrogen Deficiency", "Degrees of Unsaturation")
1. Hydrocarbons With No Rings or Multiple Bonds 4. What Happens When You Add Oxygen?
For molecules containing only carbon and hydrogen, and no double bonds or rings, there Oxygen has no effect on the calculated number of hydrogens. C=O double bonds count as a "degree of unsaturation".
is a straightforward relationship between the # of carbons and the # of hydrogens: 1 degree of unsaturation
CH3OH 4 = (2 × 1) + 2 H 2C O C 1H 2O Two fewer hydrogens than methane, CH4
# Hydrogens = 2 × (# of Carbons) + 2 O
H3C–CH2OH 6 = (2 × 2) + 2
H2C CH2
C 2H 4O Two fewer hydrogens than ethane, C2H6 1 degree of unsaturation
Try it! H2 H2 H2
C C CH3 18 = (2 × 8) + 2 C CH2OH 10 = (2 × 4) + 2 O
CH4 4 = (2 × 1) + 2 H 3C C C C C 4H 4O Six fewer hydrogens than butane, C4H10 3 degrees of unsaturation
H 3C
H 3C CH3 H2 H2
H3C–CH3 6 = (2 × 2) + 2 Note that each of these
H2 cases have zero degrees of unsaturation
H2 CH3(CH2)8CH3 22 = (2 × 10) + 2
C C CH3 14 = (2 × 6) + 2
H 3C C C
H2 H2 CH3(CH2)20CH3 46 = (2 × 22) + 2 5. Halogens (Cl, Br, I, F) : Similar To Hydrogen
Halogens (Cl, Br, I, F) can be treated as if they were hydrogens.
2. Each Double Bond [π bond] Reduces The "Expected" Hydrogen Count By 2, Introducing A
"Degree of Unsaturation"
CCl4 same as CH4 4 = (2 × 1) + 2
Every additional double bond reduces the hydrogen count by two. We call this a "degree of unsaturation"
H2C CH2 C 2H 4 1 π bond Two fewer hydrogens than ethane, C2H6 1 degree of unsaturation H Cl 1 degree of unsaturation
C C same as C2H4
Br H
HC CH C 2H 2 2 π bonds Four fewer hydrogens than ethane, C2H6 2 degrees of unsaturation
CF3CF2CF2CF3 same as C4H10 0 degrees of unsaturation
H
H C CH3 C 4H 8 1 π bond
C C Two fewer hydrogens than butane, C4H10 1 degree of unsaturation
H H2 same as C6H6 4 degrees of unsaturation
H Br Cl
H C CH2 C 4H 6
C 2 π bonds Four fewer hydrogens than butane, C4H10 2 degrees of unsaturation
C
H H
3. Each Ring Also Reduces The "Expected" Hydrogen Count By 2 6. Nitrogen - The Only "Weird" Case
This is also the case for every ring introduced.
CH3NH2 C 1H 5N 0 degrees of unsaturation The equation [H = 2 C + 2]
works if you count N as a carbon
C5H10 1 ring Two fewer hydrogens than pentane, C5H12 1 degree of unsaturation H and expect 1 fewer hydrogen
N
H2C CH2 C 2H 5N 1 degree of unsaturation
C6H12 1 ring Two fewer hydrogens than hexane, C6H14 1 degree of unsaturation
7. A Unified Equation
Knowing these patterns, and that each loss of 2H represents a double bond or ring, we can use this equation to
C6H10 2 rings Four fewer hydrogens than hexane, C6H14 2 degree of unsaturation calculate the degrees of unsaturation:
C = Carbons
Degrees of 2C + 2 + N – X – H N = Nitrogens
C10H18 2 rings Two fewer hydrogens than decane, C10H22 2 degrees of unsaturation Unsaturation = 2
X = Halogens
H = Hydrogens
4. The Effect Is Additive! 8. Solved Examples
Molecules will have a "degree of unsaturation" equal to the total number of double bonds and rings Degrees of unsaturation
H 3C
N C8H14O2 = 2 (8) + 2 + 0 – 0 – 14 = 2
C 5H 8 1 ring Four fewer hydrogens than pentane, C5H12 2 total degrees of unsaturation Cl
N 2
1 double bond
C 5H 5N C4H8NCl C6H7BrO2 = 2 (6) + 2 + 0 – 1 – 7 = 3
C6H12 1 ring Four fewer hydrogens than hexane, C6H14 2 total degrees of unsaturation
2
1 double bond Degrees of unsaturation Degrees of unsaturation
= 2 (5) + 2 + 1 – 0 – 5 = 2 (4) + 2 + 1 – 1 – 8 C9H20O3 = 2 (9) + 2 + 0 – 0 – 20 = 0
C 6H 6 1 ring Eight fewer hydrogens than hexane, C6H14 4 total degrees of unsaturation 2
2 2
3 double bonds HELPFUL HINT: Seeing 4 degrees Remember - the degree of unsaturation doesn't tell you whether
of unsaturation often indicates an = 4 = 1 they're rings or double bonds, just what the sum of rings + double
aromatic ring! bonds are.
Reach out with feedback:
james@masterorganicchemistry.com
https://MasterOrganicChemistry.com
UV-Vis Spectroscopy
Example of a UV-Vis spectrum The Electromagnetic Spectrum

Key points: • UV-Vis spectroscopy measures a molecule's absorption of light at different wavelengths λ
• The wavelength of maximum absorbance (λmax) is largely determined by the # of consecutive conjugated pi λmax at 277 nm O 400 nm 700 nm
A
bonds (π bonds) b
• Generally: the greater the number of conjugated pi bonds, the higher the λmax ("lambda max") UV Infrared
s
o 2-butanone Violet Blue Green Yellow Orange Red
• The lambda max (λmax) tells us the energy ΔE required to promote an electron from the highest-energy occupied molecular
orbital (HOMO) of the pi system to the lowest-energy unoccupied molecular orbital (LUMO). r
p ← Shorter wavelength Longer wavelength →
• As the number of consecutive pi bonds increases, this HOMO-LUMO energy gap (ΔE) decreases. Many important t
pigments (e.g. heme, chlorophyll, carotene) have multiple conjugated pi bonds and absorb in the visible region. We see the i ← Higher energy Lower energy →
"complementary" color (e.g. chlorophyll absorbs in yellow, but we see it as green). o
• C=O bonds also absorb UV light (typically around 300 nm) n
ν=E/h E = hν λ= hc /E
200 250 300 350 nm
Examples Wavelength, λ
Ethene Butadiene Hexatriene An extreme example:
("ethylene") ("1,3 butadiene") ("1,3,5 hexatriene") Lycopene - the red pigment of tomatoes Absorption of C=O Bonds
H H • Molecules with C=O bonds will also absorb UV light, however
H H H H H C C O the observed transition is slightly different.
C C C C C C H
H H C • For a non-conjugated aldehyde or ketone like 2-butanone, the
H H H H
C C C C
H H H H π to π* transition occurs beyond the detection limit (< 190 nm)
1 pi bond 2 conjugated pi bonds 3 conjugated pi bonds 11 conjugated pi bonds Other great examples • However a different type of transition, n to π* ,where n is the
- carotene (carrot pigment) non bonding electron pair, is observed with C=O bonds.
λmax 180 nm λmax 217 nm λmax 258 nm λmax 450 nm - chlorophyll (leaves) • Typical absorbance is around 300 nm
- heme (blood) (e.g. 277 nm for 2-butanone)
(UV) (UV) (UV) (blue)
As # of conjugated pi bonds increases, λmax increases, representing a smaller HOMO-LUMO energy gap (ΔE)
Pi Systems - Conjugated Pi Bonds What's meant by "Conjugation" ?
What do pi (π) bonds have to do with absorption of light ? It's important that the pi bonds are adjacent (conjugated).
The larger the number of adjacent p orbitals, the larger the
• Molecules with pi bonds will have filled pi orbitals (lower energy) and empty pi orbitals "pi system" that can form. A system of N consecutive p orbitals For example, both molecules below have two pi bonds, but A
(higher energy) separated by an energy gap ΔE will contain N pi molecular orbitals will absorb at a longer wavelength than B because of
H H conjugation.
H H H C C
• If the molecule is exposed to a photon of energy E equal to the energy gap ΔE, H A B
H H H C C H C C
it can absorb the photon and promote an electron from the lower energy level to the C C H H CH3 H
C C C C H
higher energy level H H H H H H C C H C H
H H
C C H H C C
Promoting an electron with a photon of energy ΔE Ethene Butadiene Hexatriene H
H H C C sp3 carbon
(two p orbitals) (four p orbitals) (six p orbitals)
unoccupied orbital H H
(higher energy) Electron has been promoted Two π orbitals Four π orbitals Six π orbitals
in the π system in the π system in the π system Double bonds are conjugated Double bonds NOT conjugated
from lower-energy orbital (adjacent)
π2 π2 The sp3 hybridized carbon
photon with (HOMO) to higher energy orbital
(LUMO) The larger the pi system, the smaller the ΔE gap will be
energy energy ΔE attached to 4 atoms has
between the highest occupied molecular orbital (HOMO)
gap and the lowest unoccupied molecular orbital (LUMO). no p orbitals available for
ΔE overlap with the pi system
π1 π1 This translates into a longer wavelength for λ max (i.e. Note: atoms w/ lone pairs can
towards the visible) contribute to the pi system
occupied orbital Compare ethene (180 nm) vs butadiene (217 nm). Butadiene has a
Typical Questions
(lower energy) smaller HOMO-LUMO energy gap, which means a less energetic 1. What will absorb at longer wavelength?
(i.e. longer-wavelength) photon is required to promote an electron:
• Since E = hν we can relate this energy E to frequency ν. ν=E/h
Ethene Butadiene
A - double bonds are
• Since frequency is related to wavelength by c = ν λ we
λ= hc /E π4* conjugated in A, but not in B
can relate it to wavelength)
π* LUMO
π3* LUMO A B
Bottom Line energy 2. What will absorb at longer wavelength?
energy
As # of conjugated pi bonds increases → decrease ΔE → increase λmax to longer wavelengths gap
gap
ΔE
ΔE
As # of conjugated pi bonds decreases → increase ΔE → decrease λmax to shorter wavelengths π2 HOMO B - has more conjugated
π HOMO
double bonds (3, vs. 2 for A)
π1 A B
Large energy gap ---> high ν , short λ Smaller energy gap ---> lower ν , longer λ (e.g.
ΔE (ethene) > ΔE (butadiene)
(e.g. ethene, absorbs in UV at 180 nm) lycopene, absorbs in visible at 450 nm)
This translates into the λmax gradually
H H
C C λmax (ethene) < λmax (butadiene) increases as the size of
H H the pi system increases
180 nm 217 nm Reach out with feedback:
Mass Spectrometry - Key Concepts
The One Thing Mass Spectrometry Is Great For How It Works
• Mass spectrometry (MS) is the best tool available for determining the
molecular mass of an unknown sample. With skill, one can use the
information to determine the molecular formula. "High resolution" mass
spec (advanced topic) gives the molecular formula directly.
Sample Injection
→ Ionization
→ Acceleration
→ Deflection
(Separation) → Detection
• The "Molecular Ion", M (or " M+ " because it represents a positively charged
species) is the most important peak to identify: this is the mass of the parent The sample (as a dilute The sample is hit with a high- The molecular ion M (and The stream of ions is The ions hit a detector
molecule minus an electron. solution) is injected energy electron beam, knocking whatever fragments it deflected by a magnetic which converts the arrival
into a receptor, and then an electron off of the molecule may have broken into) is field located along a bend in of each ion into an electrical
"nebulized" into gaseous and forming a positive ion accelerated in an electric the tube. signal, which is amplified and
What Else Can Be Learned From Mass Spectrometry?
form (molecular ion, M+ ). field. recorded.
Two main things besides the molecular mass: This separates the ions The instrument can be
• One can quickly determine if certain halogens (Br, Cl) are present in a [There are many different [neutral fragments can't according to their "tuned" to optimize sampling
sample by analyzing the [M+2] peaks. [See section on "exact mass"]. An even more types of ionization techniques - be accelerated by mass/charge ratio (M/Z), as of fragments with a particular
detailed analysis can determine the # of carbon atoms, plus the presence of S or Si. electron ionization (EI) is just the electric field, and lighter ions will be "bent" range of masses.
one of them] won't be detected] more than heavier ones.
• The fragmentation pattern provides clues about the structure of the molecule.
Molecules break at their weakest points: the question, "what is the most stable
free radical that can be formed" is a good place to start (see section on "fragments") Exact Mass Versus Molar Mass: The Importance of Isotopes Some Tips on Determining the molecular formula
Some Misconceptions To Avoid from M :
Mass spectra give exact masses, not molar masses. What's the difference?
• It's very rare to be able to discern the structure of a compound from MS data With a sample of unknown structure it can still be a challenge
alone. There generally isn't enough information to narrow down all possibilities. Here's an example: Bromine has an atomic weight of 79.90 g/mol . to determine the molecular formula even knowing the value of M.
(it can be useful for distinguishing between a few possibilities, however) The atomic mass of 79.9 for bromine reflects that it naturally occurs as about a For example, if you know M is 108, it could correspond to
a 1:1 mixture of the 79Br and 81Br isotopes. Averaged over a mole (6.02 x 1023 C7H8O or C8H12 - both are reasonable formulae for this mass.
• Not all peaks are equally useful or important. In fact it's common that some atoms) bromine has a mass of 79.9 g.
peaks can not be confidently assigned - some represent ions of unknown So how do you determine between multiple possibilities?
structure. Generally we try to focus on a few important peaks. We use this number when calculating the molar mass of, say, bromobenzene. If you have a table of peak heights for different values of m/z,
C6H5Br Molecular weight (MW) = 157.01g/mol. then you can do the following:
Reading a Mass Spectrum 1. The M+1 peak height will tell you the number of carbons
However, when you take the mass spectrum of bromobenzene, you actually see For every carbon present the M+1 peak will be 1.1% of the
The 3 key types of information one can get from a mass spectrum are highlighted below: masses at 156 and 158 - almost nothing at 157 (*). Why? height of M. To get the # of carbons, divide the M+1 peak by 1.1%.
• The molecular ion M. 108 in this case. This is key! So if M is 108 and M+1 is 8.8% the height of M, you have 8 carbons
M M+1 M+2
(note: you need to correct the height of M to 100 for this to work).
• Fragment masses [M–X ("M minus X") . For example losing water (H2O) Br (*) "Almost" nothing at 157
because of 13C (see below) 2. The M+2 peak can tell you if Br or Cl is present. If M+2 is about
would result in an [M–18] fragment. The parent ion is the highest intensity
equal to M, one bromine is present. If M+2 is about 1/3 the height of M,
peak (assigned intensity of 100) usually representing the most favorable
one chlorine is present.
fragmentation of the molecule.
Note that the M+2 peak 3. Sulfur also has a significant M+2 peak, although at about 4%
• Isotope masses [M+1], [M+2], etc. give information about # of carbons is about the same
(M+1) or presence of halogens (M+2) or (rarely) other atoms (like S and Si). the intensity of M for each S present, it is much smaller.
156 157 158 size as the M peak . This
Individual molecules will contain either 79Br or is a tell-tale sign of
bromine being present 4. If M is odd, the number of nitrogens in the sample is odd.
81Br (there is no naturally occuring 80Br isotope)
in a molecule! 5. Using these clues is often enough to determine the carbon count
So for bromobenzene we can have: and whether N, S, Cl, or Br is present. Whatever mass is left over is
likely H and O. Using the index of unsaturation (see sheet) with some
C6H579Br : mass = 156 common sense can help you get to the formula from this point.
C6H581Br : mass = 158
[Advanced: High Resolution Mass Spectrometry]
Some notable isotope distributions (less important ones in grey)
Protons and neutrons are assigned a mass of 1 atomic mass
Atom Main Isotope Others For every carbon in a molecule, unit - that's why we speak of 13C or 35Cl where the mass of
12C 13C
the M+1 peak will increase by about 1% protons and neutrons are summed. However, when protons
C (98.9%) (1.1%) due to 13C [e.g. for C6H5Br would expect and neutrons bind together in nuclei, subtle differeces
1H 2H [M+1] to be about 6% of M ] in the nuclear strong force result in small differences
H (99.99%) (0.01 %)
in mass (measured in the thousandths of atomic mass
O 16O (100.0%) units) that allow individual nuclei to be distinguished.
Important to know:
N 14N (99.6%) 15N (0.4%) For example, a high-resolution
Molcules containing one Cl will have mass spectrometer can distinguish between
35Cl 37Cl a M+2 peak with a height 1/3 of the M peak C7H8O and C8H12 because they have slightly
Cl (75.77%) (24.23%)
Molecules containing one Br will have different exact masses.
• Note that here the molecular ion M, m/z = 108 is very strong, but the base peak Br 79Br (50.7%) 81Br (49.3%) a M+2 peak with a height equal to the M peak
at 77 is even stronger (this is loss of the relatively stable radical •CH2OH , giving C6H5+ C 7H 8O 108.0575
Si 28Si (92.2%) 29Si (4.7%), 30Si (3.1%) C8H12 108.0939
• The minor M+1 peak represents a small amount of naturally occuring 13C present more rarely encountered, but
(see section on Isotopes) significant M+1 and M+2 peaks
S 32S (94.9%) 34S (4.3%), 33S (0.8%)
• The strength of the M peak varies considerably. It's strong for alcohols, but can be very
weak for aldehydes.
Mass Spectrometry: Fragmentation
Understanding Fragmentation Carbocation (and Radical) Stability Trends Help Predict Fragmentation Patterns
· When the sample is hit by the electron beam, it results in an unstable high-energy
species (the molecular ion) which may fragment before detection.
MOST STABLE LEAST STABLE
Fragmentations that form these Fragmentations that form these
· When fragmentation occurs, it forms a cation (which is detected) and a
(neutral) free radical (which is not)
species will tend to be favored species will tend to be disfavored
adjacent to tertiary
· Therefore an important clue to understanding which fragments will form
is understanding "what are the most stable carbocations/radicals that
heteroatom alllylic secondary primary methyl vinyl / aryl
(O, N, S) benzylic
can be formed through breaking bonds in the molecule?" F+ (charged fragment) + F• (neutral radical fragment) H H
n C
atio >
high m ent fragmentation may occur R C C >
CH2
> CH3
C
energy frag to give a neutral fragment (a radical) H 3C
C
O
R
H H
electron not detected and a cation fragment
M beam M+ + e- fra
(which can be detected) CH2 sp2 hybridized
gm
ent carbocations
atio
The resulting n
CH2 very unstable
The molecule is hit by a high F+ (charged) + F• These trends apply both
energy electron beam cation is an unstable to carbocations and carbon-
and an electron is ejected high energy species based radicals
from the sample, creating a which has a very Many different fragmentations may
cation short lifetime and might occur, but ones that result in relatively stable This turns out to be a pretty decent guide to fragmentation. Avoid forming unstable fragments
fragment before detection fragments will be most likely
Some Examples
· Carbocations and radicals have similar stability trends (see right) so for the purposes
of analysis, it does no harm to imagine that bonds fragment into two carbocations or two radicals.
A B
→
Analysis of a simple mass spectrum: Hexane (C6H14, m/z = 86)
→
CH3 Break bond A H 2C
phenyl
→
cation propyl cation
· First, look for the molecular ion M, usually the peak at furthest right. Here, it's at 86. C (unstable) (primary)
· Second, look for the highest intensity fragments (57, 43, 29 and 71) and try to figure out how they might
have formed from hexane. Propylbenzene
CH2 CH3 This results in the
Break bond B H 2C least unstable fragments,
Note the series from 29, 43, 57, 71 all separated
and will likely be the
by 14 (corresponding to mass of CH2). This is most favored
characteristic of long chain hydrocarbons benzyl cation ethyl cation
(primary) fragmentation
(resonance
Note that the M-15 fragmentation (loss of methyl) stabilized)
has much lower intensity than M-29 or M-43 peaks
CH3
Interpretation Break bond C CH2
methyl
m/z fragment
M 86 hexane molecular ion primary (unstable)
carbocation
M-15 71 loss of CH3 [note how small it is!] Ethyl isopropyl ether
A
M-29 57 loss of CH2CH3 [parent ion] Breaking bond A Caveat: It's not always clear why certain fragmentations
→
would be more favorable "win"more than others. In benzyl alcohol the dominant
→
M-43 43 loss of CH2CH2CH3 O than B because it would fragmentation is of bond A, which results in a relatively
B result in a secondary (versus stable fragment (+CH2OH) and a relatively unstable fragment
29 CH2CH3 fragment primary) carbocation (the phenyl carbocation, C6H5+)
t-butyl propyl ether
A
Fragment Analysis of Hexane A B Breaking bond B more
→
→ H 2C
→
O favorable than A because it OH Fragment OH

Here's some ways that the C–C bonds in hexane could fragment to give carbocations / radicals.
would result in a tertiary (versus
primary) carbocation
fragmentation 1 primary carbocation ← this fragmentation
is less favored due relatively relatively
+ CH3 + methyl fragment (very unstable) to formation of the Benzyl alcohol unstable stable
CH2 3,3,-dimethylheptane
m/z 71 m/z 15 unstable methyl
radical (or cation) A Breaking bond A would be favored parent ion
over breaking bond B (formation
→
fragmentation 2 (m/z = 77)

two primary carbocations of a tertiary carbocation vs. formation
→
CH2 CH3 ↑ Note: It isn't strictly correct to of primary carbocation)

H 2C
these are the most favored show them breaking into two B
Hexane m/z 57 m/z 29 fragmentations for hexane carbocations (or two radicals)
↓ but since either fragment F1 or
fragmentation 3 H2
C two primary carbocations F2 could be a cation or radical,
CH2 H 2C CH3 it works for these purposes.
m/z 43 m/z 43 Reach out with feedback:
Introduction to Infrared (IR) Spectroscopy
Key Points About IR Spectroscopy Interpreting The IR Spectrum

One mistake many students make is to think that they can determine the In IR spectroscopy, the sample (often a thin film) is exposed to a burst of infrared light, and the absorbance of the sample is measured
structure of the entire molecule from the IR spectrum - or think they need versus the frequency of light.
to identify every single peak. Not every peak is equally useful or important ·
The spectrum is usually plotted as "transmittance" on the y-axis versus "wavenumber" on the x-axis measured in cm-1 which correlates with frequency.
Also, it is generally not possible to identify the structure of a molecule
solely from an IR spectrum without more information.
· Wavenumber is the inverse of wavelength, corresponding to the number of wavelengths per unit distance. For instance a value of 3000 cm -1
is equal to a wavelength of 1/ 3000 or 3.3 x 10-4 cm. 1

Wavenumber =
λ (wavelength)
Practically, IR spectroscopy is great for identifying certain
functional groups: Wavelength is related to frequency by λ = c where ν is frequency
ν and c is the speed of light
· It is most useful for determining the presence (or absence)
of hydroxyl (OH) and carbonyl (C=O) groups. · This gives a spectrum that goes from 0-4000 cm-1 on the x axis, with 4000 cm-1 representing high frequency. [This has the advantage of being
· More rarely, it is also useful for determining the presence (or absence)
of amines and amides (N-H bonds) as well as terminal alkynes.
more intuitive to read because a high number correlates with higher frequency. If we plotted against wavelength, higher numbers would correlate
with lower frequency, which seems weird ]
· It can be useful for determining the presence of alkenes / aromatics
(C-H stretch above 3000 cm-1), as well as CC and CN
Typical Infrared Absorption Values For Various Types of Bonds
triple bonds (around 2200 cm-1) 100
3200-3400 cm-1 2850-3100 cm-1 2100-2260 cm-1 1650-1800 cm-1 500-1000 cm-1
O-H stretch C-H stretch C=O stretch
The best way to use IR is by asking a series of questions. "Is a % C C C N
hydroxyl group present? Is a carbonyl present? Are there any T
triple bonds? Is an amine or amide present?". These questions r "Fingerprint" region
are fairly straightforward to answer using IR. a (generally not useful)
n also in this
s region: Exception: 680- 860 cm-1
A Helpful Mental Model m N-H stretch region can help determine
Atoms connected by a chemical bond behave similarly i 3300-3500 cm-1 ortho-meta-para substitution
to balls (of varying mass) connected by springs (of varying stiffness) t patterns for aromatics.
t 3300 cm-1
Just like balls connected by springs, the vibrational energy (and thus the frequency of IR a alkyne C-H
light that is absorbed) will be influenced by two main factors: n stretch
c
• the stronger the bond (analogous to the strength of the spring) the higher the frequency. e < 3000 cm-1
> 3000 cm-1
For instance, C-O double bonds vibrate at higher frequency ( 1700 cm-1) than C-O single bonds alkyl C-H stretch
alkenyl C-H
(about 1000 cm-1)
0 stretch
• the lighter the atoms (analogous to the masses of the balls) the higher the frequency. For
instance C-H bonds vibrate at higher frequency (3000 cm -1) than C-C bonds (<1000 cm -1)
4000 3500 3000 2500 2000 1500 1000 500
Wavenumber (cm-1)
IR Radiation And Vibrational Energy Levels
You may recall that electrons can be promoted to higher energy levels (i.e orbitals)
when a molecule absorbs UV or visible light of frequency ΔE (where ΔE is the Table of Notable IR Frequencies (s) strong (m) medium (w) weak (v) varies
difference between energy levels)
Like balls on springs, chemical bonds can vibrate in several different ways, with Alkyl C-H stretch 2950- 2850 (m or s) Aldehyde C=O stretch 1740-1690 (s)
3000 cm-1 is a useful
different energies depending on the masses of atoms, their bond strengths, and the Ketone C=O stretch 1750 - 1680
"mode" of vibration. dividing line between
Alkenyl C-H stretch 3100-3010 (m)
alkyl and alkenyl C-H Ester C=O stretch 1750 - 1735 (s)
Like orbitals, vibrational energy levels are "quantized" - they go up in discrete levels, like steps on a
staircase. The separation in energy levels is on the order of 1-10 kcal/mol, which is in the range of Alkenyl C-C stretch 1680 - 1620 (v)
photons in the infrared region of the electromagnetic spectrum (lower energy than UV-visible) Carboxylic acid C=O 1780 - 1710 (s)
stretch
Thus, molecules can absorb infrared light and be excited to higher vibrational energy levels . The Alkyne C-H stretch ~3300 (s) Terminal alkyne C-H
details of these energy levels along with their selection rules are a bit of an advanced topic - there Amide C=O stretch 1690 - 1630 (s)
are "modes" of vibration such as "stretches", "bends", "scissoring", "rocking" and "waggles" which Alkyne C C stretch 2260 - 2100 (v) Only triple bonds appear
result in a change in dipole moment. in this region
Aromatic C-H stretch 3030 (v) Note: A table like this is a
useful reference, BUT it
Can help determine
→
Aromatic C-H bend 860 - 680 (s) doesn't really help you
→
→
→
ortho/meta/para
→
prioritize anything. See

→
Alcohol O-H stretch 3550 - 3200 (broad, s) Very diagnostic peak next page for a useful
protocol to follow.
Carboxylic Acid O-H 3000 - 2500 (broad, v) Often obscures C-H
Stretch Stretch stretch region - can be very broad
(symmetric) (asymmetric) Bend Scissoring Rocking
Amine N-H stretch 3500 - 3300 (m) Primary amines produce two N-H peaks,
The bottom line secondary amines produce one N-H peak
Nitrile C N 2260 - 2220 (m) Appears in same region as alkyne C C stretch
Different bonds absorb IR radiation at characteristic frequencies and we can use these patterns to
identify certain functional groups present in an unknown sample. Primary amides produce two N-H peaks,
Amide N-H stretch 3500 - 3700 (br)
secondary amides produce one N-H peak
Some Pointers On Analyzing IR Spectra
1. First, Examine The Region > 3000 cm-1 for Broad Peaks 2. Next, Look At The Region between 1650-1800 cm-1 for C=O peaks
i) 3200-3550 cm-1 : Alcohol O-H stretch Why it's important: Carbonyl groups (C=O) have a very strong, sharp, distinctive peak in the region around 1700 cm-1. The
exact position of the C=O vibration varies somewhat according to the type of functional group.
One of the most prominent and distinctive IR peaks to look for is the OH absorbance around
FREQUENCY (cm-1)
3200-35500 cm-1. It usually appears as a broad, featureless hump.
Some examples 1850 1800 1750 1700 1650
Example below is 1-hexanol:
(click for external link to IR spectrum)
To see real examples of IR spectra with this absorbance,
click the links below the molecules (external page) Ketone O Carboxylic acid
O
OH OH
HO
3-methyl 2 butanone Acetic acid
benzyl alcohol 2-octanol Anhydride Ester

O O O
OH
O O
Acetic anhydride Ethyl acetate
phenol ANHYDRIDES
1815 and 1750
(2 peaks)
ii) 3000 cm-1 and below (variable): Carboxylic Acid O-H stretch
Carboxylic acids appear as a broad peak with jagged edges that takes up the entire area of the spectrum, Note - these are ranges. Subtle
factors can influence the ESTERS ALDEHYDES CARBOXYLIC
and often obscure the C-H stretching peaks around 3000 cm-1. ACIDS
position of the carbonyls. 1735-1750 1720-1740 AMIDES
1705-1720
1630-1695
See more examples: KETONES
1710-1720
Acetic acid
3. Less Important, but check these other regions for potentially important clues
methoxyphenyl acetic acid
a) The C-H stretch region around 3000 cm-1
butanoic acid IR
Why it's useful: Can indicate the presence of double bonds
3000 cm-1 happens to be a useful "dividing line" between C-H stretch frequencies in alkenes/aromatics/alkynes
(which appear above 3000 cm-1) and C-H stretch frequencies in alkanes (which typically appear below 3000 cm-1).
sp2 and sp-hybridized C-H bonds are stronger than sp3-hybridized C-H bonds and will vibrate at a higher frequency.
Examples:
iii) Less Commonly Seen, But Distinctive: Amines, Amides, and Terminal Alkynes
Primary Amines Secondary Amines Terminal Alkyne C-H stretch Hexane 1-hexene benzene
(3300-3500 cm-1) (3300-3500 cm-1) (around 3300 cm-1)
H (note peaks just below 3000 cm-1) (note appearance of (all C-H above 3000)
R-NH2 N R C C H
R R peak above 3000 cm-1)
Often appears as Appears as a single broad Appears as a strong, sharp peak. b) The triple bond region between 2100 and 2260 cm-1.
two closely spaced peak (but sharper than O-H)
peaks. Sharper than O-H Why it's useful: Can indicate the presence of triple bonds. Nothing else shows up in this region.
but still somewhat broad.
Usually this is a relatively weak C C

N CH
peak. (click on molecules for
external links to examples) Butyronitrile 1-hexyne
Examples of real IR spectra Examples: Examples:

4. What About The Rest Of The Spectrum?
(click for external link) H There are more subtle details in an IR spectrum (examples below) but the law of diminishing returns starts to apply. By covering sections 1, 2 and 3
N (above) you'll get the most useful information you'll obtain from an IR spectrum.
NH2 CH3 C
C
1-hexyne H
benzylamine N-methylaniline
NH2 NH2 C
(not technically C ortho-disubstituted meta-disubstituted monosubstituted
an "amine", Phenylacetylene H para-disubstituted
N arene: arene: 700-750 cm-1 (strong)
but still has N-H 750–800 cm-1 (strong) arene:
H 750 cm-1 (strong) -1
stretch) 800-860 cm-1 (strong) 690-710 cm (strong)
aniline cyclohexylamine pyrrole Note that only terminal alkynes will show this. 860–900 cm-1 (strong)
An "internal" alkyne like 2-propyne will not. Reach out with feedback:
Nuclear Magnetic Resonance (NMR) - Background
Nuclear Spin - The Basis of NMR What's The "Chemical Shift"?
Nuclei in molecules are not "bare" nuclei. They're surrounded by electrons, which bear a negative charge.
· Atomic nuclei (hydrogen, carbon, boron, etc.) are composed of protons and neutrons. In a magnetic field, charged particles (like electrons) create a small magnetic field of their own that oppose the applied field.
· Recall that a given element can have different isotopes owing to different numbers of neutrons. For example,
1 2
hydrogen can exist as H ("protium": 1 proton, 0 neutrons) H ("deuterium" : 1 proton, 1 neutron) and H 3
That means that nuclei will feel a lower magnetic field than the applied field.
In other words, the nucleus is "shielded" from the external magnetic field by its surrounding electrons.
("tritium" : 1 proton, 2 neutrons). Therefore the magnetic field felt by a nucleus will be "shifted" somewhat by the magnetic field created by its
· Each nucleus possesses a property called "spin" which arises from the arrangement of protons
and neutrons in the nucleus. [Nuclear physics explains this - there's no simple formula to predict it for all cases]
electron cloud.
This equation states that the field felt by the nucleus will be the field due to the magnet minus
Beff = Bo – Be
the field induced by the electrons (the chemical shift)
· This can lead to different values of "spin" for each isotope. For example, carbon has two naturally occuring ↑
↑
12 13
isotopes: C (98.9% abundance) which has a spin of 0, and C (1.1%) which has a spin of 1/2 . "effective" applied the "chemical shift"
· Values of nuclear spin range from 0 all the way up to 8. For our purposes we care most about nuclei with spin
1 13
1/2: protons ( H) and C. Other nuclei have been studied, and have their uses, but won't be covered here.
magnetic field field (i.e.
felt by nucleus strength of
magnet)
Energy of nuclei in a magnetic field Revisiting the previous diagram: the red arrows sketch how the ΔE changes as a result of the chemical shift.
The nucleus will absorb at a slightly lower energy (lower ΔE) since it feels a slightly smaller magnetic field.
·A nucleus with spin 1/2 has two possible values for the spin: + 1/2 and – 1/2 .
· In the absence of a magnetic field, the energy of these two states is identical. high energy →
(nucleus aligned
The effect of the chemical shift is quite small -
·However in the presence of a magnetic field, nuclei with spin behave like tiny magnets. The
orientation where the nucleus is "aligned" with the magnetic field will be lower in energy and the
against field)
on the order of parts per million or less. Still,
this is enough for us to measure!
Energy ΔE
orientation where the nucleus opposes the magnetic field will be higher in energy. (E)
ΔE
In other words in a field where 1H resonates at
·The difference between the two energy levels is proportional to the strength of the magnetic field (" B0") low energy
(nucleus aligned 400 MHz (9.3 T) we can detect chemical shift
· The diverging lines in the figure below show how the energy gap ΔE between the two spin states + 1/2
← differences of less than 0.4 Hz (1 part per
with field)
and - 1/2 increases as the applied magnetic field increases in strength. billion of field)
magnetic field B0
This sketch represents NMR is a very sensitive technique!
the orientation of the nuclear spin (down)
Chemical shift is expressed in δ (parts per million)
aligned against -γΒ
E=–mh
m = – 1/2 0
field (high energy, Imagine a machine which irradiates the sample with energy across a range of ΔE (i.e. frequencies) and measures
excited state) The stronger the the absorbance at each frequency. We could then plot absorbance versus frequency.
magnet the better - γΒ
ΔE = h Energy (MHz)
Energy ΔE the separation 0 A
b This isn't usually done. Why not?
(E) between energy levels. s Because NMR spectrometers range from 200 MHz (smaller
m = + 1/2 aligned with o magnet, cheaper) up to 1 GHz (bigger magnet, expensive) and
-γΒ r using frequency for the X-axis makes comparisons difficult
B0 field (low energy, E=–mh b
ground state)
0 between spectra taken at different field strengths.
a
Applied magnetic field (B0) n To better allow for comparison, a "field independent" unit for chemical
c
e shift is used, δ , where δ is expressed in parts per million (or ppm)
(Advanced : Energy Calculations) · In a magnetic field of 9.3 T where H resonates at 400 MHz, one part per million (ppm) would be
1 [400 x 106]
·The energy of each state can be calculated
-
using the equation E= -γΒ
–mh 0
· For a magnetic field where H resonates at 300 MHz, 1 ppm = 300 Hz
1 [1 x 106]
= 400 Hz.
where E is energy, m is the spin , h is Planck's constant, γ is the gyromagnetic ratio (unique for
200 MHz, 1 ppm = 200 Hz
each type of nucleus) and B0 is the applied magnetic field.
·The difference in energy between the two spin- states turns out to be ΔE = h- γ Β 0 ·As the field strength goes up, so does the resolution: 1 ppm at 400 MHz covers twice as much resolution as 1 ppm at 200 MHz.
·For 1
H in a magnetic field of 9.3 T (Tesla) this corresponds to an energy difference of about 400 MHz ,
-5 -4
about 3.81 x 10 kcal/mol or 1.59 x 10 kJ / mol. The difference in energy is extremely small!
The NMR spectrum The range of a typical 1H spectrum is from about 0 to 15 parts per million ppm, with the molecule
tetramethylsilane (TMS) set as a reference at 0 ppm.
This is in the UHF region of the electromagnetic spectrum (walkie-talkies and cordless phones use it). 1Hspectrum of
Collecting the spectrum mesitylene, C9H12 CH3 "UPFIELD" REGION
H H (lower ppm)
·When a nucleus in the ground state is exposed to a photon with energy ΔE, it will absorb the photon and the
nuclear spin will flip to the "excited state". We can thus expose the sample to a range of frequencies, measure
"DOWNFIELD" REGION
(higher ppm)
H
chemical shift
"SHIELDED" CH3
the absorption at each one and thus get information about each nucleus in the sample. H 3C CH3 H3C Si CH3
"DESHIELDED" of 2.27 ppm
H CH3
[In practice a sample is exposed to every frequency at once and then processed in an operation called a
Fourier Transform. We won't get into those details here.] H
Tetramethylsilane
chemical shift (TMS) reference
·Over time, in a process we call 'relaxation', the spins will "flip back" and the energy distribution between
the ground state and excited state will re-establish itself.
of 6.89 ppm set as 0 ppm
Measuring nuclei other than 1H

·The frequency each nucleus absorbs at is a function of its "gyromagnetic ratio" γ which is different for each nucleus. 0
· Ingyromagnetic 1
13
ratio ( γ )of C is about 1/4 of that for the H nucleus. 1
13
a magnet where H resonantes at 400 MHz, the frequency for C is different (100 MHz) due to the fact that the Q. Why only two signals when
this molecule has 12 protons?
(See "how many signals?"
sheet for answer)
·Measuring 1
nuclei other than H is possible. Basically it involves "tuning" the spectrometer to a differerent
frequency - much like one would change a radio station.
Interpreting NMR: "How Many Signals?" (13C Version)
Note: This sheet will focus on 13C signals, but the same principles apply to 1H signals as well as other nuclei. 3. Equivalence through fast rotation
Chemical Shift Equivalence Principle: carbons that can be interconverted through bond rotation(s) are chemically shift equivalent.
Just because a molecule has 2 or more carbons does not necessarily mean that the At room temperature, molecules are in constant flux, interconverting between conformations thousands of times per second.
13C spectrum will show multiple signals (i.e. "peaks")
NMR is a bit like a camera that has a slow "shutter speed". Like spokes on a bicycle wheel that get blurred in a camera,
For example, the 13C spectrum of cyclopropane shows a single carbon signal , not three. NMR is too "slow" for us to see individual conformations since they interconvert so rapidly.
Some other examples are shown, with the corresponding number of 13C signals for each. The result is that we observe an "averaged" signal - a "blur" between all conformations.
Cl Another example: butane undergoes
H H CH3 Example: cyclohexane "chair flips" are fast
Even though the axial methyl fast interconversion between the staggered,
C CH3 CH3 and equatorial methyl are not
H3C CH3 H 3C H 3C gauche, and eclipsed conformations.
H C C H fast chemically shift equivalent as
H H interconversion → drawn, we observe only one Fast rotation averages out the signal.
H 3C signal (their average) due to staggered gauche eclipsed
cyclopropane ethane benzene chlorobenzene trans-2-butene trans-2-methyl-2-butene fast interconversion. They
CH3 CH3 H H 3C
1 signal (13C) 1 signal 1 signal 4 signals 2 signals 5 signals are equivalent through fast H 3C H 3C
equatorial rotation H CH3
axial methyl CH3
methyl [At very low temperatures
Q. Why only 1 signal for cyclopropane and not 3? Note that the eclipsed conformation has a
These two methyl groups are only interconversion stops, and we mirror plane. If a conformation has a mirror
A. Note that the arrangement of bonds around each carbon is completely identical (2 carbons and 2 chemically shift equivalent because they observe two separate signals] plane then you can consider "the whole
hydrogens, same bond angles). If we rotate cyclopropane 60 degrees, it is completely superimposable can interconvert through fast rotation molecule" to have a mirror plane.
on the first version (one carbon is labelled red just to indicate that rotation has occurred).
Another example: t-butyl and isopropyl groups The two methyl groups in an isopropyl
H H rotate H H rotate H H
60 o 60o The three methyls in a t-butyl group appear as group appear as one carbon signal due to
C C C one carbon signal due to fast rotation. fast rotation:
H C C H H C C H H C C H The three methyl groups in a
H H H H H H O t-butyl group are not always
Since every carbon is in identical environment, each carbon should "feel" the same magnetic equivalent through symmetry,
field. In other words they will have the same chemical shift. This is called "chemical shift BUT they exchange places so
equivalence", or sometimes just "chemical equivalence" [or "equivalence" if we are really lazy.] Cl rapidly they can be considered
to be equivalent. 6 signals 5 signals
There are 4 key principles to apply in order to evaluate whether carbon atoms are "chemically shift equivalent". 8 signals 4 signals
in 13C NMR in 13C NMR Think of it like a 3-bladed ceiling in 13C NMR in 13C NMR
fan that spins so fast, it's a blur!
1. Equivalence Through Rotation of the Whole Molecule 4. Inequivalence due to stereochemistry

Atoms are chemically equivalent if their positions can be superimposed by rotation of the molecule, like
CH3 CH3
cyclopropane above [color added to show effect of rotation]. Technical note: this is sometimes called "C2 symmetry"
CH3 H 3C CH3
H 3C
Butane (C4H10) trans-2-butene trans-1,2-dimethylcyclopropane CH3
H Br Br
rotate rotate rotate Each of these three
H2 H2 H H H H 180o H H None of these methyl groups
CH3 180o CH3 180o H 3C H 3C Each carbon of methyl groups is in a distinct
C C C CH3 C CH3 C C C C are equivalent through symmetry environment (none are equivalent)
H 3C C H 3C C H 3C C H 3C C or rotation [we can't rotate along the cyclopropane
H C CH3 H C CH3
H 2 signals H
H H a pi bond] is distinct, since we CH3 is trans to CH3
2 2 H H
can't interconvert
2 signals, since the two CH3 and two 2 signals, since the two CH3 and two CH3 groups are equivalent, since they cis and trans through CH3 is trans to CH3 and cis to CH3
We observe one 13C signal for
CH2 carbons are equivalent through rotation CH groups are equivalent through rotation are superimposable through rotation rotation.
each CH3 group (5 signals total CH3 is cis to CH3
(3 total signals for molecule) [4 total 13C signals]
when you count the alkene carbons) 9 total 13C signals for the molecule
Cyclobutane Benzene
rotate rotate
90o 60o 5. A Few Illustrative Examples ("signals" refers to 13C signals)
CH3 Cl CH3
CH3
1 signal, since all CH2 carbons are 1 signal, since all C-H carbons are note with benzene rings: these
equivalent through 90o rotations equivalent through 60o rotations two molecules are the same H 3C CH3
due to resonance (aromaticity)
CH3 Cl
2. Equivalence Through Symmetry [Mirror Planes] CH3
3 signals (can flip 3 signals (can flip 4 signals (can flip 2 signals 5 signals 8 signals
Carbon atoms are also "equivalent" if they can be interconverted by reflection along a (no mirror
whole molecule) whole molecule - also whole molecule)
mirror plane. (Note that this is the same as a roation of 180 degrees out of the plane of plane to
has mirror plane)
the page. Atoms can be equivalent for mutlple reasons. ) reflect through)
Slightly tricky OH
Cl Cl equivalent to: Another slightly tricky one:
O example:
H H H H H O OH O HO OH
C C C C
* *
CH3 HO
H C H H 3C CH3 OH O OH
H * * Cl H 3C O OH O
CH3
Cl
2 carbon signals 2 carbon signals 4 carbon signals 6 carbon signals CH3 2 signals, because conformation
6 carbon signals on right has "C2 symmetry" Reach out with feedback:
[Cyclopropane has 2 additional mirror [No mirror plane] 4 carbon 4 signals
signals (can flip whole molecule) james@masterorganicchemistry.com
planes in this axis, not shown] (no mirror plane)
Interpreting NMR Spectra -How Many Signals? (1H Version)
Note: This sheet will focus on 1H signals, and builds on concepts from the 13C sheet (see also)
Chemical Shift Equivalence 4. Homotopic, Enantiotopic, and Diastereotopic Hydrogens (protons)
If two 1H nuclei ("protons") are in the same chemical environment, they will "feel" the same magnetic field, and What is this and when does it apply?
therefore have the same chemical shift. It is a relationship between 2 or more protons on the same carbon, which allows us to determine if two protons will have the same
What's meant by the same "chemical environment" ? chemical shifts (i.e. are chemically equivalent) or not.
It only applies for the case of 2 or more protons on the same carbon.
Simplest example: the protons All protons in benzene are also equivalent, as they are superimposable
in methane (CH4) are all equivalent How To Determine The Relationship between two (or more) hydrogens on the same molecule:
through rotation, or by reflection through mirror planes (a type of rotation)
H Let's call the two protons A and B.
All are superimposable 1. Take proton A and replace it with some group we'll call X. Call this "Molecule 1".
H H H
either by rotation
through 109.5o One 1H NMR signal observed 2. Take proton B and replace it with the same group X. Call this "Molecule 2."
C H at 7.15 ppm (in CDCl3 solvent)
H or by reflection H H If molecules 1 and 2 are the same, the two protons are homotopic. They are chemically equivalent and will have the
H through one of H same chemical shifts.
the 4 mirror planes
If 1 and 2 are enantiomers, the two protons are enantiotopic. They are chemically equivalent in an achiral environment, which
applies to 99% of cases you'll see (excaption: a chiral solvent, or the presence of a chiral shift reagent).
1. Equivalence Through Fast Rotation If 1 and 2 are diastereomers, the two protons are diastereotopic. They are chemically
inequivalent and will therefore have different chemical shifts.
For our purposes, all protons in a methyl group are also considered to be equivalent. This is because rotation of the
methyl group is fast relative to the detection speed of NMR (like a photo that is "blurred" when trying to photograph a Homotopic example:
fast ceiling fan). Cyclohexane: replace each H in turn with some group "X"
How are molecules 1 and 2 related? They are the same
So even though the three protons in this methyl group are not equivalent in this conformation, they "average out" H H X H H X
through fast rotation (like a blurred photo of a ceiling fan or propeller) (can be interconverted through rotation).
The same is true for any two protons superimposable through Therefore the two hydrogens H and H are homotopic
rotate fast rotation (i.e. change of conformation)
about They will have the same chemical shifts
fast
this bond
→H H H H H H
H
chair flip
H
Molecule "1" Molecule "2"
C C C H H H 3C H Other examples:
H H H H H
CH3 H H Note that in all these cases we've seen
OH OH OH Also true for protons on other CH2 groups H H that the protons are equivalent due to fast rotation
C H
(not shown for clarity) H or symmetry: protons can be equivalent for more
R 1
H 2
3
H than one reason!
All methyl two hydrogens CH2 protons on alkenes with
2. Chemical Equivalence Through Reflection In A Mirror Plane group protons on C-3 of pentane a plane of symmetry
If protons can be interconverted through reflection in a mirror plane, they are equivalent, and will have the
same chemical shifts. Note that here,"reflection in a mirror plane" is equivalent to a rotation of 180∞.
Enantiotopic examples:
Br Cl CH3 H CH3 C-2 of pentane: replace each H in turn with some group "X".
H H H
H Cl H
H H H H H How are molecules 1 and 2 related? They are enantiomers.
H H H
CH3 Therefore the two hydrogens H and H are enantiotopic
H H H H H H H H H H X H H X
CH3 H CH3 They will have the same chemical shifts (in the absence of a
Cl Cl CH3 chiral solvent).
Two signals One signal Two signals Five signals Four signals Other examples:
Equivalent through Two mirror planes Reflection No mirror plane Two mirror planes H H H H O
reflection in (one horizontal, through mirror (the mirror plane in the [note: the protons on the CH3
H 3C HO
mirror plane one vertical) plane plane of the molecule doesn't CH2 are "diastereotopic": OH
see section on right]. H H
count for our purposes since O
it doesnt result in an exchange
of H atoms
Diastereotopic examples:
3. Chemical Equivalence Through Rotation of the Whole Molecule Three key situations to watch for: terminal alkenes, substituted rings, and moleules with a chiral center.
1) Terminal alkenes (e.g. 1-propene) without a mirror plane 2) Substituted rings (e.g. 1-methylcyclopentane)
Some protons that are not interconvertible through reflection through a mirror plane can be interconverted through
rotation of the whole molecule. [Technical note you likely don't need to know: this is called C2-symmetry] H X H Molecules 1 and 2 CH3 CH3 CH3
H H H are diastereomers. H X H
H H X
H H CH3 The two protons are H H X
H CH3 CH3 CH3 diastereotopic.
CH3 H 3C CH3 They'll have different H H H
H 3C H H Molecule "1" Molecule "2" H H H
H 3C CH3 chemical shifts. Molecule "1" Molecule "2"
H
CH3 3) Molecules with a chiral center Diastereomers: therefore the two H protons are
Rotation of 180o Rotation of 180o Rotation of 180o Molecules 1 and 2 diastereotopic and will have different chemical shifts.
in the plane out of the plane out of the plane methyl groups are OH OH OH are diastereomers. (note that the H protons are also diastereotopic)
of the page of the page equivalent through H 3C H 3C H 3C The two protons are
rotation of whole molecule CH3 CH3 CH3
diastereotopic.
H H X H H X
They'll have different
chemical shifts. Reach out with feedback:
13C NMR - Key Points https://MasterOrganicChemistry.com
A Few Key Points About Carbon NMR Chemical Shift Trends

The most abundant isotope of carbon is 12C,
which has a nuclear spin of 0. Carbon chemical shift values range from a little less than 0 (TMS reference) Terminology when referring to carbons attached hydrogens
in other words, it's NMR-inactive! to over 200 ppm for the carbon in C=O
Only about 1.1% of naturally occuring carbon is the NMR active 13C isotope which H H H R
has a spin of 1/2. A few key ranges to keep in mind: R C H R C H R C R R C R
The 13C nucleus has about 1/4 the sensitivity of the 1H nucleus for NMR purposes. Less than 0 ppm: Rare, but seen in certain organometallics H R R R
[the technical term for this is that the 13C has 1/4 the "gyromagnetic ratio", γ of 1H ] and carbons attached to heavy atoms (e.g. CH3I )
"methyl" "methylene" "methine" quaternary
Basically, because of this, in a magnet where the freqency of 1H is 400 MHz, the 0 ppm TMS reference peak carbon carbon carbon carbon
frequency of 13C will be 1/4 of this, or about 100 MHz .This is in the range of FM radio. (3 attached H) (2 attached H) (1 attached H) (0 attached H)
10-70 ppm General range for sp3 hybridized carbon.
Similarities and Differences between 1H NMR and 13C NMR Generally, methyl carbons (CH3) appear at the bottom of this
range, and the chemical shift gradually increases as hydrogens
Splitting in 13C NMR
• Chemical Shift are replaced with carbon. • Just as in 1H NMR,13C signals can be split by adjacent nuclei with spin 1/2.
Attached electron withdrawing groups (such as O or N) will (see section in 1H NMR for more detail on how splitting works).
Unlike 1H, where the range of signals goes from about 0 ppm to 15 ppm, the range in
13C NMR is about -10 ppm to 220 ppm. further increase the chemical shift.
• Because 13C is only 1.1% abundant, 13C-13C coupling is unimportant. However,
77 ppm Solvent peak of deuterated chloroform (CDCl3) appears
Like 1H NMR, the molecule tetramethylsilane (TMS) is set as the reference at 0 ppm. C-H coupling does occur.
as a 1:1:1 triplet (due to splitting of 13C by deuterium)
Like 1H NMR, attached electron withdrawing groups lead to "deshielding" and higher • A 13C signal will be split into (n+1) peaks, where n is the number of attached
ppm values 110-150 ppm Alkene carbons (sp2) tend to appear in this range. hydrogens.
160-210 ppm C=O (carbonyl) carbons tend to appear in this range, from For example a methine carbon (1 attached H) will be split into a doublet.
• Integration [Bottom line: we generally don't integrate 13C NMR spectra] 160-185 (carboxylic acids, esters) • This can be used to infer the number of attached hydrogens. For example, if
Unlike 1H NMR, integration of peaks is not a reliable guide to their population. up to 190-215 (aldehydes/ ketones). we see a quartet pattern (see below) for a carbon, we can infer that the carbon
The reason is somewhat complex, but boils down to the fact that carbon nuclei 13C is attached to (4-1) or 3 hydrogens.
can differ greatly in the rate at which they re-magnetize ("relax"), and due to the The same factors that affect chemical shifts also
time constraints of aquiring 13C NMR spectra (where hundreds or thousands of affect 1H shifts
scans will be taken, we don't want to waste time waiting around for complete Example: attached electron withdrawing groups will increase chemical shift Quartet (1:3:3:1) of a 13C nucleus split by 3 attached protons.
relaxation to occur) , the intensity measured for each signal will not reflect its due to deshielding effects. Compare the halogens
population. CH3Br CH3Cl CH3F
most →
deshielded • In 13C NMR, splitting is somewhat annoying because it leads to smaller
• Splitting ("J-coupling"): Not Important for C-C, But Important for C-H Chemical shift, δ 26 50 72 (highest peaks and longer sample times in order to see the signal above the noise.
Because the natural abundance of 13C is only 1.1%, there is only a 1% chance that any chemical
Electronegativity 2.8 3.2 4.0 shift) What's often done instead is to use a technique called "decoupling" that removes
given 13C nucleus will be adjacent to another 13C nucleus such that 13C-13C splitting can
the splitting. The result is a "proton-decoupled" spectrum which is easier to read.
occur. Since the signal is so weak it usually can't be separated from the noise. Bottom
Also compare CH3 in pentane versus acetone: Most 13C NMR spectra you will encounter will be "proton-decoupled"
line: splitting between carbons is ignored.
O about 15 ppm
However there can be splitting between 13C and any attached protons (1H). This will CH3CH2CH2CH2CH3 more deshielded Advanced: The Attached Proton Test and DEPT
lead to 13C-1H splitting. We can use this to determine the number of attached H 3C CH3
→
→ due to the electron

hydrogens; more commonly the splitting is zapped out in a process called "decoupling".
29.9 ppm withdrawing C=O Proton decoupling results in an easier-to-read spectrum, but removes useful
[See section at right.] 14.1 ppm information about the number of attached protons.
Several types of somewhat complex NMR experiments have been developed
A useful (rough) dividing line: to display this information in a useful format.
APT (attached proton test): CH and CH3 peaks appear above the baseline, CH2 and
higher than 100 ppm : sp2 Lower than 100 ppm: sp3 quaternary C peaks appear below.
DEPT: in the DEPT-135 version, CH and CH3 peaks appear above the baseline,
O O alkenes
sp2 sp3 quaternary methine methylene methyl CH2 appear below, and quaternary carbon peaks do not appear at all. In DEPT-90,
→
C C
aromatics
→ only CH peaks appear (above the baseline). Another variant of DEPT is called
R OR R OH R H H H INEPT (the origin of the terms are obscure, but the PT stands for "polarization
C C C C transfer".)
Esters, R R H R H R H
carboxylic
C
acids C Some typical 13C peak ranges (approximate)
O O Alkane
C C C
R OH CH3 C=O (ketones) 200-215 RCH2O– (alcohol) 50-75
R R R H
H3C Si CH3 C=O (aldehydes) 190-200
Ketones Alcohols RCH2NH2 (amine) 30-65
Alkenes, aromatics CH3
Aldehydes C=O (carboxylic acids, esters) 160-185 R3CH ("methine" carbon) About 25-40
CDCl3 TMS (reference)
(solvent) C=C (aromatic rings) 125-150 R2CH2 ("methylene" carbon) About 15-30
C=C (alkenes) 115-140 RCH3 ("methyl" carbon) About 10-25
"Deshielded" "Shielded"
Downfield = higher chemical shift Upfield = lower chemical shift Reach out with feedback:
Understanding NMR Spectra: Chemical Shift and Integration https://MasterOrganicChemistry.com
1. The Chemical Shift 2. Integration: The Area Under The Signal Is Proportional To the Number of Protons.
· The chemical shift in 1H NMR spectroscopy ranges from about 0 ppm to 15 ppm. Area under the peak (signal) is proportional to the number of protons. For example, in ethyl chloride CH3CH2Cl, the methyl signal
· The region with low chemical shift (around 0 ppm) we sometimes call "shielded", "upfield", or "high field". integrates to 3 and the CH2 signal integrates to 2.
· The region with high chemical shift (> 10 ppm) we sometimes call "deshielded", "downfield", or "low field".
Some examples:
By far the most useful property of the chemical shift is that it allows us to assign functional groups to different
types of protons: carboxylic acids, aldehydes, aromatics, alkenes, alkanes, etc. Propane 2-bromo propane Pentane 3,3-dimethyl-2-butanol
"deshielded" "shielded" H H H Br H H H CH3

"downfield" H
"upfield" C C C C CH3
"low field" "high field" H 3C CH3 H 3C CH3 H 3C H 3C C
C CH3 C CH3
2 signals: 6H 2 signals: 6H H H H
OH
2H 1H 3 signals: 6H
4 signals: 9H
Should see two peaks Should see two peaks 4H
with ratio of integration 3:1 3H
with integration 2H
1H
Integration provides the ratio to ratio 6:1 1H
3 signals, with ratios
the lowest common denominator. 6:4:2 (3:2:1) 4 signals in ratio 9:3:1:1
Without a signal representing 1H
in the spectrum, we must use Note: integration of protons in
our judgement whether we hydroxyl groups (OH) is often
are looking at 3:1, 6:2, 9:3, etc. smaller than 1.
Good Rule Of Thumb: With very rare exceptions, a peak that integrates to 3 in the region 0.8 to 4 ppm is a methyl
group.
Note: Integration is independent of whether the Appearance of Integration on spectra takes several forms
peak is split or not
The value of 1 ppm in Hz depends on the field strength. For a spectrometer operating at 400 MHz, 1 ppm is 400 Hz.
For a spectrometer operating at 300 MHz, 1 ppm is 300 Hz. Stronger magnets (higher MHz) result in better Written out, above... ...or below or with
resolution. [This becomes more relevant when we cover "coupling constants", next page] C H C H
Integration curve
peaks are half 3H
singlet doublet
With a little practice, one can quickly use chemical shifts to determine if alkene / aromatic / aldehyde / carboxylic acids as high, but 2H
are present. area is constant.
A second note about chemical shift: electron withdrawing groups increase the chemical shift. Same would be true for
a C-H split to a triplet,
quartet, etc.
2.056
3.082
Examples:
O O CH3 H2
C
CH3 H 3C CH3 OCH3 H 3C Cl
Dealing with Integration Curves Advaned note: Integration of OH is often less than 1. Keep this in
Integrations are sometimes just given as curves, without mind if your calculations don't work out: using the OH peak as the
0.89 0.93 ppm 2.1 ppm 0.9 ppm 3.6 ppm 2.1 ppm 3.5 ppm lowest common denominator will lead to fractional proton counts.
Even attachment Similar effect numbers. In these cases you have to measure the heights
Value of chemical Note how methyl Methyl butanoate. to get the ratios.
to a benzene wth a CH2
shift for methyl group next to ketone is Note that the methyl ring results in attached to
in pentane is typical Common sense is important:
much more deshielded group directly attached some deshielding electronegative To convert curves into integration values:
for a "normal" methyl Given a formula of C6H4BrCl and two peaks
(2.1 ppm) than methyl to electronegative O is (2.1 ppm). Similar chlorine 1. Measure their heights
at other end (0.93 ppm) of height "1", obviously each peak actually
even more deshielded effect for alkenes. 2. Determine the lowest common denominator
represents two protons.
than in 2-pentanone. 3. If you get some values close to 0.5 , multiply
by 2. Chances are you're dealing with a 2:3 ratio
In general, the appearance of an alkyl proton shifted downfield (2-4 ppm) is generally a clue that it is attached to Integration of 1.5 : 1 actually means a ratio of 2: 3 . height = 1
an electron withdrawing group of some form. A signal can't be half a proton. Br
Other peaks that tend to be broad: If you see a ratio of 1.5 : 1 or similar, it's likely a CH2 and a CH3 H H
Hydroxyl peaks (O-H)
(2:3)
Hydroxyl groups have some Carboxylic acids: Primary and secondary amines height = 1.5 height = 1 H H
interesting properties in 1H NMR. The 10-13 ppm 1-5 ppm
chemical shift can vary due Cl
height = 1
to subtle factors (such as trace water). O H H
H N N
O R H R R
O O
R H H
Primary and secondary amides
5-8 ppm Advanced note: OH,
Alcohol OH Phenol OH (5-8 ppm) O O COOH and CONH2 peaks
(1-5 ppm) H H will "disappear" when D2O
N N
is added, due to chemical
Peaks tend to be broad, and tend not H R exchange of H for D.
to split (see next page) unless sample is Reach out with feedback:
rigorously dry. james@masterorganicchemistry.com
Understanding NMR Spectra: Splitting (Multiplicity)
Key points Why does splitting occur? Simple Applications of the N+1 Rule
• Rather than appear as single peaks, signals are often "split" into multiple peaks due Quick summary of this section: a signal will be split by N spins split by 3 protons:
to an interaction called "spin-spin coupling". (protons) into N+1 peaks. This section explains why. split by 6 protons: split by 2 protons: quartet
• Splitting occurs due to interaction of a signal with neighbouring spins that are in a septet triplet split by 0 protons: ↑
In addition to the influence of the local electron cloud on a signal (which we call singlet*
different chemical environment [i.e. have a different chemical shift]. the chemical shift), the magnetic field felt by a nucleus can be influenced by the ↑ ↑ singlet
O ↑ H O H
spins of nearby nuclei, which themselves act like tiny bar magnets. C H 3C C
H3C CH3 H Cl H 3C C CH3
CH3CH2Cl For example, let's look at a simple system adjacent to a single nucleus . C C CH3
H 3C
↑↑ ↑↑ H 3C CH3 H2
↑ CH3 ↑
these methyl protons do not split each Splitting can occur between these H
C
Cl The methyl group CH3 has a chemical shift of 1.1 ppm ↑ ↑ ↑
split by 3 protons:
split by
split by 0 protons: 1 proton:
other because they are chemically protons because they are chemically H 3C CH3 split by 1 proton:
quartet singlet doublet
equivalent (i.e. have identical chemical inequivalent doublet
shifts) The methyl protons are three bonds away from the H proton and will feel
the influence of the spin of H. * OH peaks: generally don't participate in splitting under most circumstances
• Splitting interactions weaken with distance. Generally we only observe
interactions when protons are 2 or 3 bonds apart. [4 bond couplings can occur H Cl The spin of H can have two possible values: be aligned with the Applying splitting rules in reverse is useful: thinking backwards
but are usually weak, and for our purposes we will mostly ignore them]. C field or be opposed to the field.
H 3C CH3 Thinking backwards can be useful for structure determination!
• Analysis of splitting patterns is useful in that it can tell us about the neighboring groups -
specifically, the number of protons on neighboring carbons. In each case the CH3 group will "feel" a slightly different magnetic field. For a signal split into X peaks by a single neighbor, the number
Since there is a 50% distribution of each spin state, there will be two energy levels, of neighboring protons will be X-1.
• The N+1 rule is crucially important. A signal will be split into (N+1) peaks
and thus two peaks, with half the intensity of the original.
by a neighbour with N protons. For example, in CH3CH2Cl above, the CH3 H neighboring C-H
chemical shift δ is at this midpoint doublet indicates
signal will be split into 3 peaks by the CH2 protons (2+1 = 3). The CH2 signal one neighboring proton
C
will be split into 4 peaks by the CH3 protons (3+1 = 4). JHH 1 = (2-1)
The separation between the two peaks can
• Note that if there are no neighboring protons, the signal will appear as a singlet.
be measured in Hz. We call this the coupling
triplet indicates H H
• The distance between two split peaks A and B is called the "coupling constant, JHH C neighboring CH2
two neighboring protons
constant" JAB and is measured in Hertz (Hz) since its strength is independent (A typical value here would be 8-10 Hz).
unsplit split 2 = (3-1)
of the applied magnetic field. Values can range from 1 Hz to 20 Hz.
Note that splitting by the single proton H results in 2 peaks (a doublet).
Some common patterns quartet indicates H H neighboring CH3
three neighboring protons C
singlet doublet triplet quartet multiplet Splitting by two equivalent protons H
3 = (4-1)
If a signal is adjacent to two equivalent spins (e.g. CH2 ), there are three
possible spin states that an adjacent signal can feel: "up-up", "down-down", and The splitting pattern gives clues as to what "neighbors" a given signal has.
two different ways of "up down". [Great analogy to flipping two coins, which This exercise is helpful in assembling the "pieces" found in a spectrum into
gives 3 outcomes: 2 heads, 2 tails, or 1 head + 1 tail] larger fragments of the whole structure.
A common example is a triplet that integrates to 3 accompanied by a quartet

One peak two peaks three peaks four peaks what we call that integrates to 2. This likely indicates a CH2CH3 .
1:1 height ratio 1:2:1 ratio 1:3:3:1 ratio overlapping
peaks too hard For some practical examples, see the page on Solving Problems.
(not split) split by 1 H split by 2 H split by 3 H to deconvolute
Note: another name to refer to splitting is "multiplicity". For example we often say the down Splitting By More Than One Signal
up up up down down
"multiplicity" of a peak is a singlet, doublet, triplet, quartet, etc. Analyzing signals which are split by multiple neighbors is more difficult.
(2 ways)
For example, in bromoethene, each of the signals is split twice.
• Splitting does not affect the area under the signal (integration). A signal due to a In other words splitting by the two protons CH2 results in 3 peaks
methyl group (CH3) will have the same integration regardless of whether it (a triplet). For example, the proton H is split by H into a doublet (with
is a singlet, doublet, triplet, etc - the signal is just spread out over a wider area. coupling constant JHH) and each peak of this doublet is further
Because the "down-up" possibility is twice as likely, this splitting will have an split by H into a second pair of doublets
• If there are multiple neighboring signals then multiple splitting can intensity twice as high as the other two possibilities.
occur. This can lead to complex signals. (with coupling constant JHH.)
H H JHH
For example, in pentane, the CH2 signal is split both by the methyl The chemical shift of the The result is a doublet of doublets.
signal remains in the middle C C
signal CH3 (into a quartet) and by the CH2 group on C-3 (into a triplet). (note: the order in which we apply the
of the split signal. H Br
H H HH JHH JHH splitting does not matter - the appearance will
H C C H JHH JHH be the same).
H C C C
H The appearance of a doublet of doublets can vary
H H H H
depending on the strength of the coupling
The methyl group CH3 is split only by the CH2 protons (into a triplet) but not the unsplit split contstants. If the two values of J are very
CH2 (because they are 4 bonds away). Doublet of doublets similar, the doublet of doublets might appear to be
Splitting by more than two protons a triplet.
Likewise, the CH2 group on C-3 is only split by the CH2 protons (into a quintet,
A useful tool for predicting patterns and peak heights for different multiplicities
since there are 4 CH2 protons) and not the CH3 (4 bonds away, too far). The "cheater's" N+1 rule
is "Pascal's Triangle".
• If multiple signals overlap, or if one signal is split in multiple complex ways, singlet It is sometimes taught that the splitting is obtained by adding up all the
1 For example the quintet of the CH2 in pentane neighboring protons and then adding 1. For example, since H has two
it might not be possible to fully analyze ("deconvolute") the splitting. We (leftmost column) would have the intensities 1: 4: 6 : 4 : 1
1 1 doublet neighbors H and H, it will appear as a triplet. While simple, this is not strictly
often use the term "multiplet" to describe these complex situations.
1 2 1 triplet correct since the coupling constants JHH and JHH will be different.
1 3 3 1 quartet Shortcut: the N+1 rule, which tells us that
1 4 6 4 1 quintet a signal is split by N protons into (N+1) peaks.
Understanding NMR Spectra: More On Splitting (Multiplicity)
A Relatively Simple Case Study: Predicting Splitting Patterns in Disubstituted Aromatics Splitting: A More Complex Example
Here we'll go through the three possible isomers for a disubstituted aromatic compound (a very commonly
This molecule has 4 signals, we will call:
encountered situation) and analyze the splitting pattern we will expect. Note that this analysis holds for the HH H H (3 protons)
case where the benzene is substituted with two different groups (ortho, meta, para disubstitution) C
H H (1 proton)
para disubstituted: 2 signals H (2 protons)
Very characteristic pattern!! This doublet of doublet H (2 protons)
(e.g. p-bromochlorobenzene ) pattern is very characteristic of p-disubstituted aromatics H H
H H
(if you're not sure why it has 4 signals, consult the "How many signals" sheet)
Cl Ha is split by Hb into a doublet
JAB (typically about 8-10 Hz)
Ha Ha The H signal (methyl protons)
Hb Hb
This is an idealized view. For a "real view", · The 3 protons H are each 3 bonds away from the methine proton H.
Br Hb is split by Ha into a doublet click here to see the 1H NMR spectrum of · It will thus be split by H into a doublet (N +1 = 2) [with coupling constant JHH]
p-bromochlorobenzene. · No splitting occurrs between H and H or H (4 bonds away - too far)
Ha is distinct from Hb (Ha next to Cl, Hb next to Br)
Doublet separated by JHH hertz
ortho disubstituted: 4 signals
Cl Ha is split by Hb into a doublet The H signal (methine H)

Ha Br Hb is split by Ha into a doublet 1H 1H · The methine proton H is three bonds away from the three methyl protons H
and further split by Hc into a doublet It will thus be split by H into a quartet (N+1) = 4 [ with coupling constant JHH ,
Hb Hd Result: doublet of doublets identical to above example].
Hc
Hc is split by Hb into a doublet
1H 1H · This signal will be further split by the two H protons into another triplet (N+1
= 3) with coupling constant JHH
and further split by Hd into a doublet
· ...and further split by the two H protons into another triplet (N + 1 = 3) with
coupling constant JHH
Result: doublet of doublets
Hd is split by Hc into a doublet The result will be a quartet of triplets of triplets (in theory). [In practice there
will likely be overlap between signals]
Chemical shift of signal H
1H
meta disubstituted: 4 signals
Splitting into quartet JHH
with coupling constant JHH
Cl Ha is split by Hb into a doublet 1H 1H
Ha Hd
Hb is split by Ha into a doublet
1H Further splitting into
and further split by Hc into a doublet triplet with coupling
Hb Br JHH
Result: doublet of doublets constant JHH
Hc
Hc is split by Hb into a doublet
Hd is not split: singlet Further splitting
into triplet with
→
coupling constant JHH JHH
Theory versus Practice δ
Result is a quartet
This is what it would look like if JHH > JHH > JHH (not accounting for intensities).
· Due to signal overlap, there is a large variation between the "predicted" chemical shift patterns we have of triplets of triplets
gone through here and the ones observed in practice. [In practice, it will likely be a mess ("multiplet")]
· The most recognizable and distinctive pattern is the doublet of doublets observed in the para disubstituted. The H signal
If nothing else, learn this!
· The two protons H are each two bonds away from the other protons H . They will
· Ortho and meta often have a lot of overlap and can be difficult to tell apart in many cases. thus be split by H into a triplet (N+1 = 3) [with coupling constant JHH ]
If one very strong peak is seen, meta is a good guess. · The signal will be further split by the methine H proton into a doublet with
coupling constant JHH .
(Advanced): Doublet of triplets or triplet of doublets? · No splitting occurs between H and the methyl protons H (they
The order in which we analyze the splitting does not matter - the appearance are 4 bonds away, too far)
is the same. Whether it is called a "doublet of triplets" or a "triplet of doublets"
is not too important, although it will often be obvious based on appearance. · The result will be a doublet of triplets.
H
Example: The H signal
C C
C The same analysis would apply as for H, although H will occur at a different
Appearance of H signal H H Appearance of H signal
2 chemical shift.
If JHH is large and JHH is small: If JHH is large and JHH is small:
JHH
JHH Reference: Some Coupling Constant Values
´ JHH ´ JHH JHH
Two bond coupling, "geminal coupling" (2JH-H) 12-18 Hz

Looks like 2 triplets: a Looks like 3 doublets: a
Three-bond coupling, "vicinal coupling" (3JH-H) 8-10 Hz
"doublet of triplets". "triplet of doublets" Reach out with feedback:
Four bond couplings (weak) james@masterorganicchemistry.com
1-2 Hz
Analyzing 1H NMR Spectra https://MasterOrganicChemistry.com
A Key Skill: Making Tables From 1H NMR Spectra A More Complex Case
It's not always possible to fill out the "splitting" and "neighbors" portion of the table, because splitting patterns can be complex.
Anatomy of a simple spectrum In these cases we just do the best we can with what we have and move on.
Multiplicity (splitting) A slightly more complex spectrum

C4H10O number of individual peaks
per signal C6H12O2
[No IR peaks >3000 cm-1]
3 (triplet)
Strong IR peak at 1745 cm-1 D
4 (quartet)
Integration:
area under each signal
(proportional to # of H) 3H
reference peak E A
solvent peak 2H 0 ppm (TMS)
(ignore) reference peak
CDCl3 7.24 ppm 0 ppm (TMS)
(ignore) (ignore)
C B
ppm
12 10 8 6 4 2 0
Chemical shift: location of the signal 5 4 2 1
ppm
3 0
on the horizontal scale, measured in ppm
Signal CS (ppm) Integration Splitting Neighbors Identity Notes
As we've seen, there are 3 key pieces of information in a 1H NMR spectrum:
A 0.85 3H triplet 2 [= 3-1] CH3
The chemical shift - which gives clues about the functional groups present and the environment around the proton CH2
B 1.40 2H multiplet -
The integration - which tells you the number of protons in the signal (hard to tell)
The splitting (multiplicity) - which gives you clues about the neighbors to a given signal. C 1.65 2H multiplet - CH2
D 1.84 3H singlet 0 CH3 slightly high chem shift

From the splitting, you can often deduce a fourth key piece of information: the number of neighboring protons,
for CH3
which in simple cases is equal to [M-1] where M is the multiplicity. So for a triplet, the # of neighbors is [3-1 = 2 ].
E 3.85 2H triplet 2 CH2 large chemical
A very helpful way to analyze all this information is to make a table, with these four columns plus two additional shift for CH2
columns: we give an arbitrary name to each signal (e.g. A, B, C...) and a last column where we
can write in the identity of the signal if we figure it out. Once we make the table we don't have to look at the spectrum anymore. Peaks with an integration of 3H are a good bet for methyl groups, so we can put CH3 in the identity column
for A and D.
We can build this table for the spectrum above [C4H10O].
Peaks B and C are complex multiplets, but each integrate to 2. It seems reasonable to assign these as CH2 .
Signal CS (ppm) Integration Splitting Neighbors Identity Notes
Peak E is a triplet, and seems likely to be CH2. It also has a large chemical shift (3.85). Could be next to an
CH3 seem like high chemical electronegative atom like O.
A 2.05 3H triplet 2 [= 3-1]
shifts for CH3 and CH2 groups!
B 4.10 2H quartet 3 [= 4 - 1] CH2 Putting It Together O
C O
Here, we're told there's an IR peak at 1745, which indicates a C=O peak (in the ester region).
For signal A, we have an integration of 3. This is almost always a methyl group. So we can put a CH3 in the "identity" column. If we add up the CO2 from the ester, the two CH3 groups, and the three CH2 groups, we get C6H12O2 . There's one
Note that it has a relatively high chemical shift for CH3, meaning that an electron withdrawing group is likely nearby degree of unsaturation which can be accounted for by the C=O . Therefore we're not missing any other atoms and
we can get started on putting the pieces together.
For signal B, we have an integration of 2. This is likely a CH2 , which we can put in the identity column. Also has a very high
A
chemical shift for a CH2 (4.10 ppm) meaning that it is likely attached to an electron withdrawing group.
CH3CH2 Peak A is a triplet and therefore must be next to a CH2 , either B, C, or E.
Putting It Together
Note that signal A has a neighbor with 2H, and signal B has a neighbor with 3H. So it would make Peak E is a triplet and therefore must be next to a CH2. It also has a large chemical shift so it
O E
sense that the CH2 and CH3 are adjacent to each other. makes sense to attach it to the oxygen of the ester (this will lead to more deshielding than
B A C O C C
H H attaching it to the C=O )
CH2CH3 2 2
Note that by itself CH2CH3 is not a viable structure. We need additional information to solve the structure of the molecule. D E
(This is why it's helpful to do NMR last, so we have this information at hand).
O Peak D is a singlet and therefore has no neighboring H. It is also slightly
H 3C C O C C deshielded (high chemical shift) so it makes sense to attach it to the C=O .
H H
We're told here that the molecular formula is C4H10O [zero degrees of unsaturation] We're also told that the IR spectrum 2 2
showed no broad peaks in the 3200-3400 region [i.e. no OH]. We also see no OH peaks in the 1H NMR. O
D E C B A Peaks B and C are multiplets. This would make sense if they were split by two neighbors
H 3C C O C C C CH3 with different chemical shifts. We've already established that peak A (the methyl group) is
In that case it would make sense that the oxygen is part of an ether. O H H attached to B or C.
H 2
2 2
B A
Then, it would make sense that the CH2CH3 would be attached to the oxygen. O CH2CH3 It makes the most sense to put C next to E since it is slightly more deshielded (higher chemical shift) than B and
thus closer to the oxygen.
However this still only leaves us with C2H5O. We are missing C2H5 . So what's going on? This is our final structure! Do a last check to make sure everything makes sense.
If we attached an additional CH2CH3 to the oxygen, we would get an ether, and we would have the right molecular
formula C4H10O. Furthermore, we would still see only 2 signals in the NMR because of symmetry. Note: it takes practice to get good at this. But over time these problems
are very logical and are rewarding to do!
A A Reach out with feedback:
B B
[So why don't we see 10 protons in the 1H NMR? We do actually! It's just that 3:2 is the lowest
CH3CH2 O CH2CH3 james@masterorganicchemistry.com
common denominator of 6:4 . Something to watch out for when molecules have symmetry! ]
Solving Spectroscopy Problems From Scratch - An Overview https://MasterOrganicChemistry.com
This sheet gives an overview of how to use all the data you will receive from various sources and put it all together into a final structure.
Note: it assumes you are given the molecular formula (or at least some way to deduce the molecular formula).Problems that require solving an
unknown structure without giving the molecular formula or molecular weight are generally exercises in sadism.
The purpose of spectroscopy is to determine the structure of an unknown molecule. It's like solving a jigsaw
puzzle, but with a difference: you aren't given the box, and you aren't given pieces. You are given some cryptic
squiggly lines that give you clues as to what the pieces are and how they are connected. Your job is to convert This will probably seem a bit vague without examples. For a
those squiggly lines into pieces, and then assemble the pieces in a way that is consistent with the data. video showing how to use this method with several worked
examples, scan the QR code or go to https://bit.ly/spec-video
Part 1: Start With The Easy Stuff First
The most time-consuming spectra to analyze are 1H NMR spectra. So do that last. Squeeze as much as you can out of
the other information you're given. This will help when you have to assemble the "pieces" later.
This table gives some of the "80/20" analysis you can apply to each technique.
Small time
investment
(low Given... 80/20 Analysis (80% of results from 20% of work) Notes
complexity)
Molecular formula Determine the index of unsaturation This provides the number of (double bonds + rings). When you propose a final structure, don't forget to back-check that it is consistent with
this number.
UV-Vis (uncommon) Determine if there's conjugated double bonds
(examine λmax)
IR Look for the presence of OH and C=O groups If O is in molecular formula, absence of OH or C=O peaks could indicate that an ether is present. C=O, ether oxygens, and esters (CO2R) don't
Look at the position of C-H peaks around 3000 show up in 1H NMR, so look to IR for help in assigning the relevant functional group.
MS Identify molecular ion. Look for M+2 peaks Should be in agreement with molecular formula.
that indicate presence of Br or Cl
13C Obtain the # of carbon signals; determine if the presence of Best way to directly identify if quaternary carbons are present (since they will have no attached H to show up in 1H NMR)
C=C, C=O, and alkyl carbons. Attached proton test (APT) or
DEPT, if available, helps identify various types of alkyl carbon.
1H No 80/20 here, unfortunately. Every detail is important. Make a table to organize chemical shift, integration, splitting, and # of implied neighbors. After assigning each
signal, compare the total of carbons/protons with the molecular formula to make sure you aren't missing any
Large time "pieces" like C=O, O, quaternary C, halogens etc.
investment
(high complexity)
Example for an unknown molecule with formula C7H14O2

Part 2: Idenfity The Pieces
So the first goal of analyzing all the spectra is to account for all the pieces (i.e. the carbon skeleton and functional groups)
1H Pieces CH2 CH3 CH3 CH3 CH3
NMR will get you most of the way there, in that it will help you identify CH3, CH2, CH groups and so on. from 1H NMR
Pay special attention to "pieces" that don't show up in the 1H NMR, like C=O groups, halogens, ethers, quaternary carbons and other atoms (quartet) (triplet) (singlet, 9H)
not attached to hydrogen.
O
Pieces from IR C O (ester at 1750 cm-1)
For instance if IR tells you that you have a C=O bond present, that's a "piece" that you'll have to fit in somewhere. Likewise if MS or
the molecular formula tells you there's a Cl or Br present, it must be accounted for.
Total mass: C6H14O2
Part 3: Put The Pieces Together
There's nothing more frustrating than trying to solve a jigsaw puzzle that's missing some pieces. Similarly, it can be extremely difficult to solve Oops! Missing
quaternary carbon C
a structure if you haven't accounted for all the atoms (i.e. carbons with attached hydrogens + functional groups).
Before putting all the pieces together, double check that the molecular formula of your "pieces" adds up to the molecular formula of the molecule. C7H14O2 (agrees with formula given)
Total:
It can be easy to miss quaternary carbons and other atoms that don't show up in 1H NMR.
Once you've accounted for all the pieces, THEN try to piece them together. The best tool for this is by looking at the "splitting" and "neighbors"
Assembling the pieces (using splitting patterns - see 1H page for examples)
columns of your table.
A second source of information is the chemical shift of the signals. An unusally high chemical shift usually indicates that it is attached to an O CH3 CH3
electron withdrawing group such as O, Cl, Br, or C=O C O CH2 C CH3
CH3
Part 4: Final Double Check
Once you have a final structure, ask: 1) are all the atoms accounted for? 2) does the degree of unsaturation make sense?
CH3 O CH3
3) do the splitting patterns make sense? 4) do the chemical shifts make sense?
Final structure H 3C C C O CH2 Reach out with feedback:
CH3 james@masterorganicchemistry.com

Moc Spectroscopy Pack

Uploaded by

Document Information

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Moc Spectroscopy Pack

Uploaded by

Copyright:

Available Formats

https://MasterOrganicChemistry.

Example of a UV-Vis spectrum The Electromagnetic Spectrum

O favorable than A because it OH Fragment OH

fragmentation 2 (m/z = 77)

CH2 CH3 ↑ Note: It isn't strictly correct to of primary carbocation)

Key Points About IR Spectroscopy Interpreting The IR Spectrum

is equal to a wavelength of 1/ 3000 or 3.3 x 10-4 cm. 1

prioritize anything. See

benzyl alcohol 2-octanol Anhydride Ester

Usually this is a relatively weak C C

Examples of real IR spectra Examples: Examples:

Measuring nuclei other than 1H

1. Equivalence Through Rotation of the Whole Molecule 4. Inequivalence due to stereochemistry

A Few Key Points About Carbon NMR Chemical Shift Trends

→ due to the electron

C=C (alkenes) 115-140 RCH3 ("methyl" carbon) About 10-25

"deshielded" "shielded" H H H Br H H H CH3

A common example is a triplet that integrates to 3 accompanied by a quartet

ortho disubstituted: 4 signals

Cl Ha is split by Hb into a doublet The H signal (methine H)

Two bond coupling, "geminal coupling" (2JH-H) 12-18 Hz

Multiplicity (splitting) A slightly more complex spectrum

D 1.84 3H singlet 0 CH3 slightly high chem shift

Example for an unknown molecule with formula C7H14O2

You might also like