1

Infrared spectroscopy
Infrared light is of the exact frequency to resonate with the covalent bonds of organic
molecules.
Plancks theory of quantization shows us that only the exact energy will resonate with
the bond. Too much or too little energy will not cause it to resonate(too little may cause
rotation(microwaves) or too much may cause fragmentation(UV)).
The resonance of IR radiation with organic molecules is seen as stretching and bending
of the covalent bonds. Stretching can be symmetric or asymmetric. Bending can be
scissoring or twisting. The actual types do not concern us much. Lighter atoms absorb
at a higher frequency. Stiffer atoms absorb at a higher frequency.
IR spectra are incredibly complicated; however certain regions are more important.
2500-3600
Single bond stretches of hydrogen appear in this region
OH stretches occur either 3590-3650 if non- hydrogen bonded or 3200-3550 if hydrogen
bonded or 2500-3000 if part of a carboxylic acid.
NH appears between 3300-3500. NH2 would appear as a pair of peaks.
Alkane CH stretches appear at 2853-2962. Alkene CH stretches appear at 3010-3095.
Alkyne CH stretches appear at 3300.
2100-2300
Triple bond stretches appear in this region.
Alkyne CC stretches appear at 2100-2260. Nitrile CN stretches appear at 2220-2260.
1400-1800
Double bond stretches appear in this region.
Carbonyl CO stretches appear at 1630-1780. Esters and Acids appear at the high end of this
region. Ketones and aldehydes in the middle and Amides at the low end.
Alkene CC stretches appear at 1620-1680. Aromatic CC stretches appear at 1400-1500.
1300-1400
Single bond stretches of carbon appear in this region.

8. Match the spectra to the compounds. Also circle the peak on the spectra that led you to the identification.

A
A. Butanenitrile

B. Butanol

C. Butanone (ketone)

D. Butene

SpectroscopyChapter 9
Light spectrum
PlanckEnergy is quantized.
Light can behave as both a particle and a wavedual nature of light
Photoelectric effectEinstein Nobel Prize
Electrons can behave both as a wave and a particleMatter waves
DeBroglieNobel Prize
SchrodingerQuantum mechanics to solve the equations for the movement and location
of electrons. What is life? GenesBiochemistry. Nobel prize.
Light is a source of energy. How the energy of light interacts with matter is called
Spectroscopy.
Types of light energy.
1 nm 400 nm

X-rays

UV

700nm

visible(VBGYOR)

4000nm

km

IR Radio(, TV and radio)

wavelength increases in this direction

frequency and strength increases in this direction

E
c
h

cm

= h; = c/;
= 3.00 x 10 8 m/s
= 6.63 x 10 -34 Js
= frequency(Hz or s -1)
= wavelength(nm or m)

HISTORY OF NUCLEUS
Maxwell(1831-1879)
Invented color photography. Rings of saturn are many small particles. Created the
single comprehensive theory of electricity and magnetism. Died in 1879(same year as
Einstein born). Coincidence Newton born same year Galileo died.

Hertz(1857-1894)
Created the first radiowave in 1887.

Roentgen
1895Discovered X-rays accidently. Cathode ray tube on his desk cause fluorescent
screen to flash. Nothing short of lead blocked the invisible, unknown rays. Forerunner
of modern X-ray.

Marconi
Transmitted radiowaves over the English channel and the Atlantic ocean, 1899 and
1901. Discovered the ionosphere.

Becquerel/Curie
Discovered radiation and the elements Radium and Polonium(Poland). Marie won 2
nobel prizes(1903 and 1912). Pierres nobel prize speech.

Planck
Came up with the theory of quantization(1900).

Einstein
1905Quantum Theory of Light, Photoelectric effect, Dual Nature of Light, Brownian
Movement and the Theory of Relativity. 1916General Theory of Relativity. Einstein
came up with the theory and the mathematics on how to turn radioactive elements into
energy. E = mc2 . He also furthered our understanding of light/electromagnetic
radiation.

Rutherford
1911Discovered the nucleus. Showed that it was mostly empty space.

DeBroglie
1924Theorized the existence of matter waves. Matter waves are particles of matter
behaving as a wave. Einstein said light could be a wave or a particle. In other words
light could behave like a particle(matter). De Broglie said electrons could behave like
light. The electron microscope.

Schrodinger
1926Invented quantum mechanics to solve the mathematical calculations of how
atoms behave. Quantum mechanics revolutionized physics and chemistry. It produced
the highest level of understanding of the physical world. After solving the most
complicated problem in math, chemistry and physics, Schrodinger set out to solve the
most complicated problem in biology, What is Life? Which is the title of his book
which gave the blueprint to solve the mystery of life. He hypothesized the existence of
the genetic code and of molecules whose different structure carried vital
information(genes). He laid out a blueprint on how to break the genetic code. James
Watson and Francis Crick were inspired by his ideas and in 1953 discovered the
structure of DNA.

Heisenberg
1927Heisenbergs Uncertainty Principle. You can not know both the speed and the
momentum of a particle at the same time.

Meitner/Hahn/Strassman/Frisch
Hahn and Strassman converted Uranium into Barium. They could not explain it
however. Meitner(and her nephew Frisch) were sent copies of the results and Meitner
figured out that the Uranium had undergone fission(her word) and been turned into the
Barium. Although, Meitners paper(1939) on the topic is only one page long it is
considered one of the great papers of all time. Niels Bohr(the unofficial head of the
scientific community) brought the paper over to the United States by boat to make sure
it got here before it was published. Why????

Fermi
Italian scientist. Discovered chain reaction in 1942. 1st Nuclear reactor at University of
Chicago. This leads to ??? in 1945.

Chapter 9NMR and MS

NMR
NMR stands for Nuclear Magnetic Resonance. Basically the nuclei of atoms are made to
resonate with an energy source. In this case magnets help create the resonance.
There are two types of magnets that can be usedelectromagnets and superconducting
magnets. Electromagnets are artificial magnets created by using an electrical source.
Electromagnets usually consist of a coil of wire surrounding an iron(or metal) core.
Electricity is passed through the coil. This creates a magnetic field around the wire that is
amplified by the number of coils and by the iron core. Electromagnets are utilized in most
devices. Any device with a motor usually involves an electromagnet. Telephones,
electronics, computers, turbines and powerplantsall use electromagnets(a simple
electromagnet can be made by coiling a wire around a screwdriver and hooking it to a
battery).
Superconducting magnets are naturally occurring magnets whose power is greatly increased
by cooling it to very low temperatures(4.3 K). Superconductors have no electrical/heat
resistance(conductors have low electrical/heat resistance; semiconductors have limited
electrical/heat resistance; insulators have high electrical/heat resistance). A loop of ordinary
wire has so much resistance that an electron will stop moving around the loop within a
second of the power being turned off(i.e. flip off the light switch and the light goes off
immediately it doesnt linger). In a superconducting loop the electron would go on
forever(theoretically it would never stop; there was an experiment where an electron was
placed in a loop and let go. It went for years without ever stopping). So if the wiring in your
house was superconducting wire. You would need to start the electrons moving and then no
added electricity would be needed to keep it going(eventually the resistance of the light bulb
itself would stop the electron moving).
The magnets are kept cool by the use of a Dewar chamber(see page 367).
NMR magnets have to have incredible field strength to function properly. Most operate at a
level 70,000 to 140,000 times the strength of the earths magnetic field(MS, which does not
require the same strength as NMR often, uses permanent magnets or even quadrupoles to
operate). MRIs use a much smaller magnetic field also usually 10,000 to 20,000 times the
strength of the earths magnetic field.
Magnetic quenchingthe bane of NMR. As the temperature in the coil heats up resistance
builds up in the wire causing heat to be generated which boils away the liquid helium. This
quenches the magnetic field. A simple NMR costs from 250,000 to multiple millions of
dollars. Quenching a magnet can lead to repair costs in the tens of thousands of dollars.
At UNO we spend $7,500-10,000/year on the cryogens to keep the NMR cool.

Operation
When nuclei of atoms are placed in a magnetic field they will become aligned with or
against the magnetic fie ld of the NMR. When an electromagnetic pulse(Rf) is applied to
the compound, the nuclei will absorb energy from the pulse. Different types of nuclei
absorb energy at different energy levels. This differentiation can be used to identify
different nuclei on NMR spectra.

Types of NMR
Continuous wave(CW) vs. Fourier Transform(FT)
CW was predominant when NMR was in its infancy in the 70s and 80s. CW use
electromagnets instead of superconducting magnets. They do not need to be cooled. So
there is no cost for cryogens. Spectra take 2-5 minutes to develop. In CW, the sample is
irradiated with a constant value electrical impulse while the magnetic field strength is
varied. Different nuclei absorb at different field strength. When nuclei absorb, the y
generate a current in the wire surrounding the sample. This current is amplified and
graphed on the corresponding spectra. CW only work on proton NMR. Other modern
techniques do not work with CW. Signal to noise ratio is very low. Most magnets were
60 or 90 MHz.
FT is the standard today. FT-NMR use superconducting magnets. So there is the need
to keep the magnet cool. Spectra develop in seconds instead of minutes. Multiple
spectra are taken and analyzed and combined too greatly increase the signal to noise
ratio. Therefore, FT-NMR can be done with much less concentration of sample. Nuclei
other than hydrogen can be analyzed. In FT-NMR, an electromagnetic pulse irradiates
and excites all the nuclei at the same time. This generates a complex current pattern for
all the excited nuclei that is amplified and detected. The data is then analyzed by a
computer program(Fourier Transform) that provides spectra indicating the different
types of nuclei.

Nuclear Spin
Different nuclei will have a different spin value in magnetic fields. If you remember
from general chemistry, electrons were given a quantum number value for ms of + or
.
The different nuclei that organic chemists deal with have different spin quantum
numbers, I. Different isotopes of each nuclei have different spin numbers also. 1 H,
ordinary hydrogen; 13 C, isotopic carbon, 19 F and 31 P, normal fluorine and phosphorous
all have spin quantum numbers of +/. Therefore these are all observable by NMR.
12
C, 16 O, 32 S and 2 H all have spin quantum numbers of +/1 and are not observable by
NMR. Remember electrons have spin = +/. Electricity is a flow of electrons.
Therefore if a nuclei also has a spin of +/ then it can resonate with the magnetic field
to generate a current(similar to the flow of electrons). As stated previously when the
protons are placed in a magnetic field they will either align with(lower
energy/stable/ground state) or against(higher energy/unstable/excited state) the magnetic
field. In NMR we want all the protons to be aligned. So energy is added to flip all the
protons aligned with the field to be aligned against the field(excited state). The amount
of energy needed to do this varies depending on the strength of the magnet. The
stronger the magnet the larger the separation will be between ground and excited states.
The energy is provided by an electromagnetic pulse. Once the protons absorb the
energy they are aligned(resonating) with the magnetic field(called magnetic resonance).
The value of the pulse corresponds to the magnets strength. In an older magnet(1.41
tesla), the pulse needed to flip all the protons is 60,000,000 Hz(cycles/second) or 60
MHz. For modern NMR(7.04 tesla) the pulse needed to flip all the protons is
300,000,000 Hz or 300 MHz(recall if you have a cordless phone at home they operate at
900 MHz; AM radio is measured in kHz1280 on the AM dial is 1,280,000 Hz or 1.28
MHz; 99.5 on the FM dial is 99,500,000 Hz or 99.5 MHz).

Solvent
To run a NMR a sample must be dissolved in a liquid. Since the sample is organic an
organic liquid is usually used. But it has to be an isotopic solvent. Ordinary
dichloromethane can not be used because the Hs on the dichloromethane would show
up in the spectra. Since the solvent is always much higher in concentration the Hs for
dichloromethane would swamp out the spectra of the compound. Instead CD2 Cl2 or
CDCl3 or CD3 COCD3 or D2 Oare used. These are called deuterated solvents.
However carbon tetrachloride can be used nondeuterated. Why???

10

Chemical Shifts
In IR we saw that different functional groups absorb IR at different frequencies. In
NMR different nuclei absorb magnetic radiation at different frequencies also. In NMR
this is called chemical shifts. Chemical shifts of different hydrogens are given on page
378. Chemical shifts are classified as downfield(deshielded/less magnetic field strength)
or upfield(shielded/larger magnetic field strength). Most NMR read out in ppm scale
from 0-10. If the hydrogen lies closer to 10, then it is called downfield. If it lies closer
to 0 it is called upfield. A sample of tetramethylsilane is added to the NMR solvent to
set the 0 line. Two factors, electron density and electron circulation can determine the
position of the proton in the spectra. The movement of electrons in a magnetic field
generates their own magnetic fields. The magnetic fields of moving electrons shield the
proton from the magnetic field of the NMR itself(think about two south poles of a
magnet repulsing each other; or all those star trek movies where a magnetic pulse
actually moves the space ship). The induced magnetic field of the electrons surrounding
the proton shields it from the external magnetic field of the NMR. Basically they feel
less the presence of the external magnetic field. This is called shielding. Since the
proton is shielded it does not absorb as much magnetic radiation as it normally should
and stronger field strength is needed to make the proton absorb and resonate. Thus its
signal is seen upfield(close to 0 ppm). The more electron density around the proton the
more it will be shielded and the larger the magnetic field to which it must be subjected
in order for the proton to resonate. If a proton is attached to a carbon with an
electronegative group or attached directly to an electronegative group it will be
deshielded as the electron density is drawn away. The other factor is circulation of
delocalized(from conjugation) electrons. As seen on page 377, the circulation of
electrons around pi bonds causes a field to be developed. In terminal alkynes that field
shields the protons and move them upfield. In aromatic rings such as benzene, the
protons are often deshielded and moved downfield.
TMS has 12 protons. So a small concentration yields a large signal. The Hs attached to
the silicon are more shielded since Si is less electronegative than C(why???). Therefore
they appear way upfield where no other ordinary organic compounds normally appear.
The chemical shift is a ratio of the shift away from TMS/frequency of the instrument:
= (obs. shift from TMS(Hz)) x 106 /(freq. of the instrument(Hz))
The units are ppm.

Integration
Each peak on the spectra takes up a certain area of the paper. Taking the integral of the
peak gives us the relative number of hydrogens in that peak. By comparing integrations
we can determine how many hydrogens are represented by each peak. I.E. if we
integrate the area under the peaks we may get an integral of 2. This could correspond to
a CH2 .

11

Signal Splitting
In addition to chemical shift data and integration to help us understand NMR, there is a
third important feature called signal splitting. Hydrogens within in 3 sigma() bonds of
each other will split each others signal into doublets, triplets, quartets and multiplets. If
hydrogens are equivalent or enantiotopic they will not split each other. If they are in a
different environment or diastereotopic they will split each other. This is the N+1 rule.
If a hydrogen is next to 3 other hydrogens its signal will be split into 4(3+1) peaksa
quartet. The 3 hydrogens(assuming they are equivalent) will be split into 2(1+1)
peaksa doublet. Therefore on the spectra, the peak that corresponds to a CH next to a
CH3 , will appear as a quartet. The CH3 peak will appear as a doublet. The integral of
the quartet peak will be 1(remember it represents 1 H). The integral of the doublet peak
will be 3(it represents 3 H). So integral and splitting are not related.
Why doesnt the carbons split the hydrogens? If a methyl hydrogen is split by a
hydrogen on a carbon next to it, why not by the carbon itself?

Equivalent/Nonequivalent protons
Homotopic protons are protons with the same chemical shift. Homotopic protons must be in
the exact same environment as each other. Therefore 2 sets of CH3 s or 2 sets of CHSee
example page 379. If you have 2 sets of protons that you think are the same replace one
hydrogen in one set with another group(Cl). Then redraw the molecule and replace one
hydrogen in the other set with another group(Cl). If the two molecules you have drawn are
the same new compound then they are homotopic.
Enantiotopic and diastereotopic are hydrogens on the same atom that may have a different
environment. For example, a methylene carbon with 2 Hs on it may have different
environments and give different shifts. To determine if they are enantiotopic or
diastereotopic switch the hydrogens for new groups like in the homotopic case. If the new
pictures are enantiomers of each other then the Hs will have the same chemical shift. If the
new pictures are diastereomers of each other then the Hs will have different chemical shifts.

Spin-spin Coupling
Spin-spin coupling gives rise to signal splitting we talked about earlier. We are not
going to go into the details of the coupling other than to talk about field strength of the
magnets. The splitting of the proton peaks into quartetsis the same in all field
strength. The coupling constant(which determines how far apart the peaks are in the
quartet) is the same in all magnetic field strengths. However high field strength NMRs
allow for greater separation of the chemical shifts of the protons. In other words, 2 sets
of protons that may overlap in a 60 MHz instrument can be resolved in a 300 MHz
instrument.

12

Process Rate
Because of the speed of the relaxation of protons after being bombarded by em pulse,
NMR can not usually detect rapidly interconverting processes. I.e. a chair flip from
equatorial to axial hydrogen should yield two separate chemical shifts. The NMRs
processing is so slow however that it will not observe the interconversion and give only
one shift. Lowering the temperature can slow the interconve rsion and allow the
instrument to detect it.

Carbon NMR
Because carbon has a spin quantum number of 1 it can not ordinarily be detected by
NMR. But the isotope of carbon has a spin quantum number of so it can be detected.
Since only 1.1% of all carbon is isotopic 13-Carbon the signal is much weaker. It can
only be done on a FT-NMR. Carbon-carbon splitting is possible. However the chance,
of having an isotopic carbon next to each other is 1 in 10,000. Therefore carbons
usually show up as one unsplit peak. Each carbon will have its own unique chemical
shifts. Isotopic carbons can be split by hydrogen. But a special type of probe is used
that cuts out the proton coupling(called a broadband proton decoupled probe). If the
decoupling is turned off, the splitting pattern of carbons can be used to determine the
nature of the carbons. The chemical shifts of the different types of carbon are found on
page 394. These carbons are all considerable downfield from the hydrogens. The same
principles of shie lding/deshielding apply. On the spectra on page 396 explain why the
solvent shows up here and not on proton NMR.

Special Types of NMR

DEPT 13 C NMR
DEPT spectra yields information concerning the protons attached to the carbon. In
DEPT, four different spectra are taken. The first shows only CH3 s. The second shows
only CH2 s. The third shows only CHs and the fourth shows only Cs. The four
spectra are then converted into one spectra as shown on page 397.
2D and 3D NMR(HETCOR/COSY)
COSY
COSY(1 H- 1 H correlation spectroscopy) is a NMR technique where the protons of a
compound are plotted against themselves. Protons that are coupled to protons on a
different carbon show up in the spectra as a high-density area in a contour-style map.
HETCOR
HETCOR(Heterogenous correlation spectroscopy) is similar to COSY except it
correlates the protons to the carbon it is attached to.

13

H3C
H2C

singlet integration of 2

HC

singlet integration of 1

H3C

CH

H2C

CH

HC

CH
CH2

triplet integration of 2
CH2

triplet integration of 1
HC

CH2

H3C

CH3

H2C

CH3

HC

CH3

C
H2

appears as doublet
of triplet with int.
of 2

doublet integration of 2

triplet integration of 3

H2C

C
H

doublet integration of 3

doublet integration of 1

H3C

H2
C

singlet integration of 3

quartet integration of 3

H
C

Br
CH
CH3

doublet due to CH, quartet due to CH3,

integration of 1.

quartet integration of 2
quartet integration of 1

H2
C
H3C

appears as quartet due to CH3 and triplet because of CH2 with integration of 2

C
H2

H2
C

H2
C
CH

Cl

appears as triplet due to CH2 to the left and triplet due to CH2 on the right.
with integration of 1.

14

NMR examples
a

a The CH3's labeled A have only one neighbor that

e
c

being the CH at B. Since 1 + 1 = 2. A appears

as a doublet. Since the carbons at A are not next
to anything other than sp3 carbons, they appear
between 0 and 1 with an integration of 6.
b The CH at B has 6 neighbors, 3 each from Carbons
A. This could appear as a group of 7 peaks or as
a quartet of quartets with integration of 1.
c as
c The CH3's at C have no neighbors so they appear
a singlet with integration of 6.
d This is a CH attached to a double bond. This will

appear in the 5-6 region. It has one neighbor from

the CH on E so it will be a doublet, integration of 1.
This is a CH attached to a double bond. This will
appear in the 5-6 region. It has one neighbor from
the CH on D so it will be a doublet, integration of 1.
This is a CH3 next to a ketone. It will appear around
2.0. It has no neighbors so it will be a singlet with
an integration of 3.

f
e

6.0

5.0

2.0

1.0

0.5

15

11

10

16

15

14

O
9

13

1
2

4
3

6
5

Cl

Proton NMR

H
17

8
12

H
O

T
M
S

4 singlets at 0.8 integration of three, represents hydrogens on carbon 13, 14, 15 and 16 with no neighbors
triplet at 0.9, integration of three, represents hydrogens on carbon 11 with 2 neighbors from carbon 10
doublet at 0.9, integration of three, represents hydrogens on carbon 12 with 1 neighbor from carbon 8
doublet at 0.9, integration of three, represents hydrogens on carbon 17 with 1 neighbor from carbon 5
quartet at 1.7, integration of one, represents hydrogens on carbon 5 with 3 neighbors from carbon 17
quartet at 2.4, integration of two, represents hydrogens on carbon 10 with 3 neighbors from carbon 11
quartet at 2.5, integration of one, represents hydrogens on carbon 8 with 3 neighbors from carbon 12
singlet at 3.1 integration of one, represents hydrogens on carbon 1 with no neighbors
singlet at 3.8 integration of one, represents hydrogens on carbon 3 with no neighbors

16

MORE NMR PROBLEMS

5

10

11
9

13

14

10 11
15

12

15

14

12

6, 7 and 8 have integral of 1. 2, 12 and 14 have integral of 2 and 1, 5, 10, 11 and 15 have integral
of 3
2

Cl

9
8

10

6
10

1, 3 and 9 have integral of 1. 4, 6, 8 and 10 have integral of 2.

2
1

Br

10
9

11

6
7

10

1.5

5 and 9 have integral of 1. 2, 3, 6 and 10 have integral of 2. 1, 7 and 11 have integral of 3.

11 7

0.8

17

3
2

6
4

4
5

O
6

1.0

2.5

2.9

3.5

8
1

2
1

7
6

9
3

5.0

2.6

2.1

4
2

1.9

1.6

1.2

1.0

.8

18

14

10

2
3

O
O

11

12

11

13

7 8

10

2.6

3.5

2
1

5
4

7
6

3.5

11

11

5.0

1.0

2.0

10
8

10

13

14

12

5 6

14

14
12

13

13
8

2.6

2.1

1.9

1.6

1.0

.8

19

H-NMR
0-2
CH3, CH2 and CH attached to other R groups.
1.5-2 CH3, CH2 and CH allylic to a double bond.
2-2.5 CH3, CH2 and CH next to benzene or ketone.
2.5-3.5 H attached directly to a triple bond.
3-3.5 CH3, CH2 and CH attached to F, Br, I.
3.5-4 CH3, CH2 and CH attached to Cl.
3.3-4 CH3, CH2 and CH attached to O(alcohol or ether).
4-6
H attached directly to double bond
6-9
H attached directly to benzene ring.
9-11 H attached to aldehyde or to O of carboxylic acid.
C-NMR
0-50
50-100
bond.
100-150
150-200

Carbon attached to R group.

Carbon attached to heteroatom(O, N, Cl, Br) or carbon as part of a triple
Carbon is part of a double bond(alkene, benzene).
Carbon is part of a carbonyl(ketone, aldehyde, acid, ester).

IR
3400-3600
3300
3030
2900
1620-1780
1480-1600

OH
Alkyne Hs
Benzene/aromatic Hs
CHs
Carbonyls
Alkene

20

MS Data
m/z
202(M+)
203(M+ +1)
204(M+ +2)

% intensity
89.45
13.78
87.69

IR Data
Sharp peak at 3030
Strong peak at 1720

Strong multiplet at 2900

Multiple, Medium peaks from 1480-1550

NMR Data

3.5

Peaks doublet at 0.6 has integral of 3

doublet at 2.0 has integral of 2
doublet at 2.2 has integral of 2
doublet at 2.4 has integral of 2
tripled triplet at 3.1 has integral of 1
singlet at 3.5 has integral of 3
tripled quartet at 3.9 has integral of 1
5 singlets at 7.1, 7.2, 7.3, 7.4, 7.5 all with integral of 1
DEPT spectra indicates that there are 14 carbon peaks. At 180 is a Carbon with no
Hydrogens. At 145, 143, 142, 141 and 140 are Carbons with 1 hydrogen. At 150 is a
Carbon with no Hydrogens. At 80 is a carbon with 1 Hyrogen. At 75 is a carbon with 3
hydrogens. At 70 is a carbon with 1 hydrogen. At 35, 30 and 25 are carbons with 2
hydrogens. At 28 is a carbon with 3 hydrogens.

What is the structure?

21

MS Data
m/z
299(M+)
203(M+ +1)
204(M+ +2)

% intensity
89.45
13.78
87.69

(13.78/89.45)*100 = 15.4/1.1 = 14
(87.69/89.45)*100 = 98 = Br
MF = C 14H19BrO2

IR Data
Sharp peak at 3030--Aromatic Ring Strong multiplet at 2900CHs
Strong peak at 1720--Ketone
Multiple, Medium peaks from 1480-1550-Alkene
NMR Data

3.5

Peaks doublet at 0.6 has integral of 3 CH3 next to CH

doublet at 2.0 has integral of 2 CH2 next to CH and ketone
doublet at 2.2 has integral of 2 CH2 next to CH and ketone
doublet at 2.4 has integral of 2 CH2 next to CH and benzene
tripled triplet at 3.1 has integral of 1 CHBr between 2 CH2
singlet at 3.5 has integral of 3 OCH3
tripled quartet at 3.9 has integral of 1 CHO between CH3 and CH2
5 singlets at 7.1, 7.2, 7.3, 7.4, 7.5 all with integral of 1 Benzene CH's
DEPT spectra indicates that there are 14 carbon peaks. At 180 is a Carbon with no
Hydrogens. At 145, 143, 142, 141 and 140 are Carbons with 1 hydrogen. At 150 is a
Carbon with no Hydrogens. At 80 is a carbon with 1 Hyrogen. At 75 is a carbon with 3
hydrogens. At 70 is a carbon with 1 hydrogen. At 35, 30 and 25 are carbons with 2
hydrogens. At 28 is a carbon with 3 hydrogens.

22

FRAGMENTS FROM NMR

HC

H2
C

CH3

H2
C

H2
C

HC

CH

HC

0.6

2.0

2.2

2.4

O
H

Br
CH3
O

CH
H2C

CH3

7.1-7.
5

CH

CH2

3.5

3.1

H2 C

O
H

3.9

H
H

H
H2
C

H2
C

CH3

CH

CH
H

HC

CH3

H2 C

H2
C
C
H

2.0 to 2.2

0.6 to 3.9 and 3.5 to 3.9

7.1-7.5 with 2.4

H
H2
C

H2
C

CH2

H2
C

HC

C
H

O
CH

O
H

CH3

CH3

Br

B to C
H

A to 3.1

H
H2
C

H2
C

H2
C

HC
Br
H

H
H

O
CH

CH3

CH3

23

MS Data
m/z
122(M+)
123(M+ +1)
124(M+ +2

% intensity
84.20
3.70
27.79

IR Data
Strong multiple peaks at 2900
Strong Peak at 1740

T
M
S
10
0

Peaks 2.2 has integral of 1.8,

3.4 has integral of 1.8
3.8 has integral of 2.7

DEPT spectra indicates that there are 4 carbon peaks. At 185 is a C with no Hydrogens. At 80 is a carbon with 3 Hydrogens. At 65 is a
carbon with 2 Hydrogens and at 15 is a carbon with 2 Hydrogens.

NMR Data
What is the structure?

24

MS Data
m/z
122(M+)
123(M+ +1)
124(M+ +2)

% intensity
84.20 (3.70/84.20)*100 = 4.4/1.1 = 4 Carbons
3.70 (27.70/84.20)*100 = 33% = 1 Chlorine
27.79 Based on DEPT = 7 Hydrogens
C4H7Cl = 90
122 90 = 32 = 2 Oxygens
C4H7O2Cl

IR Data

Strong multiple peaks at 2900CHs

Strong Peak at 1740 Carbonyl(C double bond O) Ketone or ester due to
lack of aldehyde or carboxylic acid peak in proton NMR.
NMR Data
4

2
TMS

10
2

9
1

Peaks 2.2 has integral of 1.8,

3.4 has integral of 1.8
3.8 has integral of 2.7

Peak at 2.2 = 2 Hydrogens with 2 neighbors next to ketone(CH 2)

Peak at 3.4 = 2 Hydrogenswith 2 neighbors next to chlorine(CH2Cl)
Peak at 3.8 = 3 Hydrogens with no neighbors but next to Oxygen(OCH3 )

DEPT spectra indicates that there are 4 carbon peaks. At 185 is a C with no Hydrogens. At 80 is a carbon with 3 Hydrogens. At 65 is a
carbon with 2 Hydrogens and at 15 is a carbon with 2 Hydrogens.
O

80 = C next to O(OCH3) 65 = C next to Cl(CH 2Cl) 15 = CH2

185 =
C

O
4

Cl

2
3

25

Problem #1

MS Data
m/z
86(M+)
87(M+ +1)
88(M+ +2

% intensity
54.30
2.99
0.05

IR Data
Strong peak at 2900
Strong peak at 1725

TM
S

10
0

Peaks triplet at 0.8 has integral of 7.8,

triplet of quartet at 1.3 has integral of 5.2
singlet at 2.1 has integral of 7.8
triplet at 2.4 has integral of 5.2
DEPT spectra indicates that there are 5 carbon peaks. At 200 is a C with no Hydrogens. At
50 is a carbon with 2 Hydrogens. At 40 is a carbon with 3 Hydrogens. At 35 is a carbon with
2 Hydrogens and at 15 is a carbon with 3 Hydrogens.
NMR Data

What is the structure?

26

MS Data
m/z
86(M+)
87(M+ +1)
88(M+ +2

% intensity
54.30 (2.99/54.30)*100 = 5.5/1.1 = 5 Carbons
2.99 (0.05/54.30)*100 = 0.09% = Nothing
0.05 Based on DEPT = 10 Hydrogens
C5H10 = 70
86 70 = 16 = 1 Oxygen
C5H10O

IR Data

Strong peak at 2900 CHs

Strong peak at 1725 Carbonyl(C double bond O) Ketone or ester due to lack
of aldehyde or carboxylic acid peak in proton NMR.
NMR Data
P
3
1
4
5
TM
S

10
0

Peak at 2.4 is next to ketone with 2 neighbors.

Peak at 2.1 is next to ketone with no neighbors.
Peak at 1.3 is nex t to 2 and 3 hydrogens.
Peak at 0.8 is next to 2 hydrogens

Peaks triplet at 0.8 has integral of 7.8,

triplet of quartet at 1.3 has integral of 5.2
singlet at 2.1 has integral of 7.8
triplet at 2.4 has integral of 5.2

DEPT spectra indicates that there are 5 carbon peaks. At 200 is a C with no Hydrogens. At
50 is a carbon with 2 Hydrogens. At 40 is a carbon with 3 Hydrogens. At 35 is a carbon with
2 Hydrogens and at 15 is a carbon with 3 Hydrogens.
200 = carbonyl, 50 = CH2 next to ketone, 40 = CH3 next to ketone, 35 = CH2 and 15 = CH3
O

2
1

4
3

27

MS Data
m/z
271(M+)
272(M+ +1)
273(M+ +2

% intensity
75.80
10.01
74.28

IR Data
Small, sharp peak at 3030
Strong multiplet at 2900
Strong peak at 1680
Medium set of peaks in 1500 and 1600s
NMR Data

TMS

10
0

Peaks triplet at 1.0 has integral of 9.75

triplet at 1.2 has integral of 9.75
singlet at 2.2 has integral of 9.75
quartet at 2.5 has integral of 6.5
quartet at 3.8 has integral of 6.5
singlet at 8.2 has integral of 3.25
singlet at 8.8 has integral of 3.25

DEPT spectra indicates that there are 12 carbon peaks. At 180 is a Carbon with no
Hydrogens. At 165 and 160 are Carbons with 1 hydrogen each. At 150, 152, 156 and 158
are Carbons with no Hydrogens. At 50 is a carbon with 2 Hyrogens. At 45 is a carbon with 2
hydrogens. At 40 is a carbon with 3 Hydrogens. At 35 is a At carbon with3 Hydrogens and
at 30 is a carbon with 3 Hydrogens.

What is the structure?

28

MS Data
m/z
271(M+)
272(M+ +1)
273(M+ +2

% intensity
75.80 (10.01/75.80)*100 = 13.2/1.1 = 12 Carbons
10.01 (74.28/75.80)*100 = 98% = 1 Bromine
74.28 Based on DEPT = 15 Hydrogens
C12 H15 Br= 239
271 239 = 32 = 2 Oxygens
C12 H15 O2 Br

IR Data

Small, sharp peak at 3030

Aromatic Hs
Strong multiplet at 2900
CHs
Strong peak at 1680 Ester or Ketone(lack of aldehyde/acid in H-NMR)
Medium set of peaks in 1500 and 1600sAromatic double bonds

NMR Data
7
3
1

10
0

TM
S

P ea k s triple t a t 1.0 h a s in teg ral o f 9.75 3 p ro nto ns w ith 2 n eig hb ors (C H 3 C H 2 )

trip le t a t 1.2 ha s inte gral o f 9 .7 5 3 p roton s w ith 2 ne igh bo rs (C H 3 C H 2 )
sing le t a t 2.2 h a s integ ral o f 9 .7 5 3 p roton s n ex t to k e ton e or a ro m a tic rin g(no n e ig hb o rs )
q ua rte t at 2 .5 h as in teg ra l o f 6.5 2 p roton s n ex t to ke ton e or a rom atic rin g(3 ne igh bo rs )
q ua rte t at 3 .8 h as in teg ra l o f 6.5 2 p roton s n ex t to eth er(es ter) (3 ne igh bo rs )
sin gle t a t 8.2 h a s in teg ral o f 3 .25 1 a ro m a tic p roto n
sin gle t a t 8.8 h a s in teg ral o f 3 .25 1 a ro m a tic p roto n
D E PT s pe c tra ind ica tes th at th ere are 1 2 c a rbo n p e ak s. A t 18 0 is a C a rb o n w ith n o H y drog e ns .
A t 1 6 5 a n d 16 0 are C a rbo ns w ith 1 h yd ro ge n e ac h. A t 15 0 , 1 52 , 1 5 6 a n d 15 8 are C a rbo ns
w ith no H yd ro g en s . A t 5 0 is a c arbo n w ith 2 H y ro ge n s. A t 45 is a ca rbo n w ith 2 hy dro ge ns .
A t 4 0 is a ca rb o n w ith 3 H yd ro g en s. A t 35 is a A t c a rb on w ith 3 H yd ro ge n s an d at 3 0 is a
c arbo n w ith 3 H y drog e ns .
1 8 0 = k eton e or ester , 16 5, 1 60 , 1 58 , 15 6, 1 52 , 1 5 0 = b enzen e rin g , 5 0 = C H 2 n ext t o eth er , 45 = CH 2 nex t to rin g, 4 0 = C H 3 n ext to ri ng ,
3 5 = C H 3 an d 3 0 = C H 3

H
H

Br

Bo th ar e p o ssi ble. A lso the g ro u ps

co u ld b e a rr an ged d if f er en tly aro u nd
the r ing .

Br

O
7

5
6

29

MS Data
m/z
172(M+)
173(M+ +1)
174(M+ +2)

% intensity
69.95
6.93
0.56

IR Data
Strong multiple peaks at 2900CHs
Strong Peak at 1740
Strong Peak at 1600
NMR Data

6
1

Peaks triplet at 0.8 has integral of 3,

triplet of triplet at 1.3 has integral of 2
triplet at 2.4 has integral of 2
triplet at 3.3 has integral of 2
quartet at 3.5 has integral of 2
doublet at 3.6 has integral of 2
triplet of triplet at 5.3 has integral of 1
doublet at 5.8 has integral of 2

DEPT spectra indicates that there are 9 carbon peaks. At 200 is a C with no Hydrogens. At
120 is a carbon with 2 Hydrogens and at 110 is a carbon with 1 Hydrogen. At 95, 85 and 75
are carbons with 2 Hydrogens. At 45 is a carbon with 2 Hydrogens. At 25 is a carbon with 3
Hydrogens and at 15 is a carbon with 2 hydrogens.

30

MS Data
m/z
172(M+)
173(M+ +1)
174(M+ +2)

% intensity (6.93/69.95)*100 = 9.9/1.1 = 9 Carbons

69.95 (0.56/69.95)*100 = 0.8% = No Cl, Br or S
6.93 Based on DEPT = 16 Hydrogens
0.56 C9H16 = 124
172 - 124 = 48 = 3 Oxygens
C9H16O3

IR Data

Strong multiple peaks at 2900CHs

Strong Peak at 1740 Carbonyl(C double bond O) Ketone or ester due to lack
aldehyde or carboxylic acid peak in proton NMR.
Strong Peak at 1600 ALKENE
NMR Data
9

6
1

Peaks triplet at 0.8 has integral of 3,

triplet of triplet at 1.3 has integral of 2
triplet at 2.4 has integral of 2
triplet at 3.3 has integral of 2
quartet at 3.5 has integral of 2
doublet at 3.6 has integral of 2
triplet of triplet at 5.3 has integral of 1
doublet at 5.8 has integral of 2

Peak at 0.8 is next to CH2.

Peak at 1.3 has CH2's on each side.
Peak at 2.4 is next to ketone and CH2.
Peak at 3.3 is next to oxygen and CH2.
Peak at 3.5 is next to oxygen and CH3
Peak at 3.6 is next to oxygen and CH
Peak at 5.3 is alkene and has CH2's on each side.
Peak at 5.8 is alkene and next to CH

DEPT spectra indicates that there are 9 carbon peaks. At 200 is a C with no Hydrogens. At
120 is a carbon with 2 Hydrogens and at 110 is a carbon with 1 Hydrogen. At 95, 85 and 75
are carbons with 2 Hydrogens. At 45 is a carbon with 2 Hydrogens. At 25 is a carbon with 3
Hydrogens and at 15 is a carbon with 2 hydrogens.

O
2
1

5
4

8
7

31

MS Data
m/z
150(M+)
151(M+ +1)
152(M+ +2)

% intensity
88.69
5.85
29.27

IR Data
Strong multiplet at 2900
Strong peak at 1680

NMR

3.8

3.5

3.3

2.5

0.
8

Peaks doublet at 0.8 with integral of 3

doublet at 2.5 with integral of 2
singlet at 3.3 with integral of 3
singlet at 3.5 with integral of 2
triplet of quartet at 3.8 with integral of 1

DEPT spectra indicates that there are 6 carbon peaks. At 200 is a C with no hydrogens. At
90 is a carbon with 3 hydrogens and at 85 is a carbon with 2 hydrogens. At 50 is a carbon
with 1 hydrogen. At 45 is a carbon with 2 hydrogens and at 15 is a carbon with 3 hydrogens.

32

MS Data
m/z
150(M+)
151(M+ +1)
152(M+ +2)

% intensity
88.69 (5.85/88.69)*100 = 6.6/1.1 = 6 Carbons
5.85 (29.27/88.69)*100 = 33% = 1 Cl
29.27 Based on DEPT = 11 Hydrogens
C6H11Cl = 118
150 118 = 32 = 2 Oxygens
C6H11ClO 2

IR Data
Strong multiplet at 2900 CHs
Strong peak at 1680
Carbonyl
NMR
2
4

3.8

Peaks doublet at 0.8 with integral of 3

doublet at 2.5 with integral of 2
singlet at 3.3 with integral of 3
singlet at 3.5 with integral of 2
triplet of quartet at 3.8 with integral of 1

3.5

3.3

2.5

0.
8

Peak at 0.8 is next to CH.

Peak at 2.5 is between ketone and CH.
Peak at 3.3 is CH3 next to O.
Peak at 3.5 is CH2 next to O.
Peak at 3.8 is a CHCl between a CH2 and a CH3.

DEPT spectra indicates that there are 6 carbon peaks. At 200 is a C with no hydrogens. At
90 is a carbon with 3 hydrogens and at 85 is a carbon with 2 hydrogens. At 50 is a carbon
with 1 hydrogen. At 45 is a carbon with 2 hydrogens and at 15 is a carbon with 3 hydrogens.

Cl

O
1

4
2

33

MS Data
m/z
210(M+)
211(M+ +1)
212(M+ +2)

% intensity
91.56
12.09
30.21

IR Data
Small, sharp peak at 3030
Strong multiplet at 2900
Strong peak at 1680
Medium set of peaks in 1500 and 1600s

NMR

Peaks singlet at 2.1 with integral of 3

singlet at 2.2 with integral of 3
singlet at 2.3 with integral of 3
triplet at 2.5 with integral of 2
triplet at 3.7 with integral of 2
singlet at 7.0 with integral of 1
singlet at 7.5 with integral of 1

DEPT spectra indicates that there are 12 carbon peaks. At 200 is a C with no Hydrogens. At
170, 165, 160 and 155 there are carbons with 0 Hydrogens and at 150 and 145 are carbons
with 1 Hydrogen. At 50 is a carbon with 2 Hydrogens. At 45 is a carbon with 2 Hydrogens.
At 40, 35 and 30 are carbons with 3 hydrogens.

34

MS Data
m/z
210(M+)
211(M+ +1)
212(M+ +2)

% intensity
91.56 (12.09/91.56)*100 = 13.2/1.1 = 12 Carbons
12.09 (30.21/91.56)*100 = 33% = 1 Cl
30.21 Based on DEPT = 15 Hydrogens
C12H15Cl = 194
210 - 194 = 16 = 1 Oxygen
IR Data
C12H15ClO
Small, sharp peak at 3030
Aromatic Protons = Benzene
Strong multiplet at 2900
CHs
Strong peak at 1680
Carbonyl
Medium set of peaks in 1500 and 1600s
Double bonds = Benzene

NMR
3 4 5
7

Peak s sing let at 2.1 with in teg ral o f 3

sing let at 2.2 with integral o f 3
sing let at 2.3 with integral o f 3
triplet at 2.5 w ith in teg ral of 2
triplet at 3.7 w ith in teg ral of 2
sing let at 7.0 with integral o f 1
sing let at 7.5 with integral o f 1

Peak at 2.1 is CH 3 n ex t to ring .

Peak at 2.2 is CH 3 n ex t to ring .
Peak at 2.3 is CH 3 n ex t to ring .
Peak at 2.5 is in between keto ne an d CH2
Peak at 3.7 is in between CH2 an d Cl.
Peak at 7.0 is CH of benzene ring .
Peak at 7.5 is CH of benzene ring .
Peaks at 7.0 a nd 7 .5 are singlets. T his m ea ns
they a re n ot next to each o ther.

D EPT spectra indicates that ther e are 12 car bon peaks. At 200 is a C with no Hydrogens. At
170, 165, 160 and 155 there are carbons with 0 Hydrogens and at 150 and 145 are carbons
w ith 1 Hydrogen. At 50 is a carbon with 2 Hydrogens. At 45 is a carbon with 2 Hydrogens.
A t 40, 35 and 30 are carbons with 3 hydrogens.

Cl

H
4

35

MS Data
m/z
202(M+)
203(M+ +1)
204(M+ +2)

% intensity
65.60
7.94
21.60

IR Data
Strong multiplet at 2900
Strong peak at 1680
Medium peak at 1580
NMR Data

Peaks doublet at 0.6 has integral of 3

triplet at 0.7 has integral of 3
tripled quartet at 0.8 has integral of 2
doublet at 0.9 has integral of 3
singlet at 1.5 has integral of 3
doubled quartet at 2.3 has integral of 1
triplet at 2.4 has integral of 2
quartet at 3.6 has integral of 1
doublet at 5.7 has integral of 1
DEPT spectra indicates that there are 11 carbon peaks. At 180 is a Carbon with no
Hydrogens. At 145 is a Carbon with 1 hydrogen. At 140 is a Carbon with no
Hydrogens. At 80 is a carbon with 1 Hyrogen. At 45 is a carbon with 1 hydrogen. At
40 and 35 are carbons with 2 hydrogens. At 30, 25, 20 and 15 are carbons with 3
hydrogens.

What is the structure?

36

m/z
11 Cs
202(M+)
203(M+ +1)
204(M+ +2)

% intensity

(7.94/65.6)*100 = 12.1/1.1 =

65.60
7.94
21.60

(21.60/65.6)*100 = 33% = Cl
Dept indicates 19 Hs
C11H19Cl = 186
202 - 186 = 16 = 1 Oxygen
C11H19OCl

IR DATAStrong multiplet at 2900CHs bonds

Strong peak at 1680Ketone (only 1 oxygen so not ester and no Hs at 911 on
NMR so not Aldehyde or Acid)
Medium peak at 1580Alkene
NMR Data

P e ak s
0 .6 = C
0 .7 = C
0 .8 = C
0 .9 = C
1 .5 = C
2 .3 = C
2 .4 = C
3 .6 = C

H
H
H
H
H
H
H
H

D E P T s p e c tr a i n d ic a te s t h a t th e re a r e
1 1 c a rb o n p e a k s . A t 1 8 0 is a C a rb o n
w it h n o H y d ro g e n s . A t 1 4 5 is a
C a r b o n w ith 1 h y d ro g e n . A t 1 4 0 is a
C a r b o n w ith n o H y d ro g e n s . A t 8 0 is
a c a rb o n w ith 1 H y ro g e n . A t 4 5 is a
c a rb o n w i th 1 h y d ro g e n . A t 4 0 a n d
3 5 a r e c a rb o n s w ith 2 h y d ro g e n s . A t
3 0 , 2 5 , 2 0 a n d 1 5 a r e c a rb o n s w ith 3
h y d ro g e n s .

d o u b le t a t 0 .6 h a s in te g ra l o f 3
t r i p l e t a t 0 .7 h a s i n t e g r a l o f 3
trip le d q u a rt e t a t 0 .8 h a s i n te g ra l o f 2
d o u b le t a t 0 .9 h a s in te g r a l o f 3
s i n g l e t a t 1 .5 h a s i n t e g r a l o f 3
d o u b l e d q u a r t e t a t 2 .3 h a s i n t e g r a l o f 1
t r i p l e t a t 2 .4 h a s i n t e g r a l o f 2
q u a r t e t a t 3 .6 h a s i n t e g r a l o f 1
d o u b le t a t 5 .7 h a s in te g r a l o f 1

3 n e x t t o C H , n o f u n c ti o n a l g r o u p s c lo s e
3 n e x t t o C H 2 , n o f u n c ti o n a l g r o u p s c lo s e
2 b e t w e e n C H 2 a n d C H 3 , n o f u n c t io n a l g r o u p s c lo s e
3 n e x t t o C H , n o f u n c ti o n a l g r o u p s c lo s e
3 n e x t t o C H o f a d o u b le b o n d
b e t w e e n C H , C H 3 a n d k e to n e
2 n e x t t o C H 2 a n d k e to n e
n ex t to C H 3 a n d C l a n d C

Cl

2
4

37

Test #5NMR
MS Data
m/z
164(M+)
165(M+ +1)
166(M+ +2)

Name:

% intensity
44.86
5.43
0.18

IR Data
Small, sharp peak at 3030
Strong multiplet at 2900
Multiple, Medium, sharp peaks at 1400-1500

NMR Data

What is the structure?

38

KEY
MS Data
m/z
164(M+)
165(M+ +1)
166(M+ +2)

% intensity
44.86
5.43
0.18

(5.43/44.86)x100 = 12.1/1.1 = 11 carbons

(0.18/44.86)x100 = 0.4% = no chlorine, bromine, sulfur
C11H16 = 148; 164 148 = 16; = 1 oxygen
C11H16O

IR Data
Small, sharp peak at 3030
Strong multiplet at 2900
Multiple, Medium, sharp peaks at 1400-1500

NMR Data

Aromatic hydrogen peaks

CH peaks(no carbonyls detected)
Aromatic double bond peaks

39

NMR data
H-NMR
0-2

CH3, CH2 and CH attached to other R groups.

1.5-2 CH3, CH2 and CH allylic to a double bond.

2-2.5 CH3, CH2 and CH next to benzene or ketone.
2.5-3.5 H attached directly to a triple bond.
3-3.5 CH3, CH2 and CH attached to F, Br, I.
3.5-4 CH3, CH2 and CH attached to Cl.
3.3-4 CH3, CH2 and CH attached to O(alcohol or ether).
4-6

H attached directly to double bond

6-9

H attached directly to benzene ring.

9-11

H attached to aldehyde or to O of carboxylic acid.

C-NMR
0-50

Carbon attached to R group.

50-100

Carbon attached to heteroatom(O, N, Cl, Br) or carbon as part of a triple bond.

100-150

Carbon is part of a double bond(alkene, benzene).

150-200

Carbon is part of a carbonyl(ketone, aldehyde, acid, ester).

IR
3400-3600

OH

3300-3500

NH

3300

Alkyne Hs

3000-3100

Alkene H2

3030

Benzene/aromatic Hs

2900

CHs

1620-1780

Carbonyls

1620-1680

Alkene