Chapter 17

What is an unknown compd?

determination oI
determination oI the presence oI certain
Iunctional groups
spectrometer degradation to simpler compds
mass spectrometer
molecule
electron
beam
many Iragments
some are positive ions
(1 Ior most oI them)
each ion has a particular
m/e value
CH
3
C H
3
C CH
3
CH
3
(C
5
H
12
)
e
2e C
5
H
12
m/e 72
molecular ion
C
4
H
9
C
3
H
5
C
2
H
5
C
2
H
3

and etc
m/e 57 41 29 27
relative intensity
100 41.5 38.5 15.7
base peak
mass spectrum
Eig 17.1
all compds have their characteristic mass spectra
(useIul Ior identiIication)
give an exact M.W. molecular Iormula
the presence oI certain
structural units
molecular weight (M.W.)
molecular Iormula
conversion into derivatives
synthesis by an unambiguous route

the peak oI highest m/e value
oI a mass spectrum
M (molecular ion) peak ?
no due to
isotopes
isotope peaks are
useIul to determine
the molecular
Iormula
ex) benzene
M

: m/e 78
C
6
H
6
M1 : m/e 79
M2 : m/e 80
C
5
13
CH
6
or C
6
H
5
D 6.75
C
4
13
C
2
H
6
, C
5
13
CH
5
D or C
6
H
4
D
2
0.18
ex) Table 17.2
Irom the study oI mass spectrum
oI known compd
preIerential Iormation oI more stable carbocations
elimination oI small stable molecules
(H
2
O, NH
3
, CO etc)
rearrangement toward more stable ions
the accumulated knowledge is applied
to deducing the structure oI an unknown compd.
microwave
- ray
X - ray
visible
IR
10
-4
0.2 0.4 0.72 2.5 16 200
electronic
4000 625
vibrational
stretching
bending
each compd has its own
speciIic spectrum
IR spectrum
(Iinger-print region : 1300 ~ 650 cm
1
)
absorbance ( log 1/T)
or transmittance ( I/I
o
)
characteristic absorption band :
O H
C O
C N
stretch
stretch
2250 cm
1
CH
2
H
Eig 17.2 stretch
bending

Table 17.1

UV
(10
4
cm) wavelength

cm
1
wave number
wavelengh or wave number
3200 ~ 3600 cm
1
1710 cm
1
(ketone)
2950 ~ 2850 cm
1
1450 ~ 1375 cm
1

not simple to interpret IR spectrum : overtones, combination tones
shiIted by various structural Ieatures
(conjugation, inductive eIIect, angle strain
steric strain, resonance eIIect etc)
Table 17.3
ex)
O
R R'
O
R R'
1710 cm
1
1670 cm
1

IR
stretch
aromatic : 1500~1600
sp
2
: 1650 (~1600 by conjugation)
sp

: 2100
may not appear
due to 0
C C
stretch C H
sp
3
: 2800~3000
sp
2
, aromatic : 3000~3100
sp

: 3300
bending C H
1370 CH
3
1450 CH
2
, CH
3

990 970 910 890 700

RCH CH
2
t-RCH CHR
R
2
C CH
2
c-RCH CHR
830 780 750 700
p-di
m-di
o-di
mono
in plane : 1000~1100cm
1
out oI plane (stronger) : 1000~650cm
1




Iar UV near UV visible
200 nm 400 nm 750 nm
(nm 10
7
cm)
UV spectrometer
electronic exitation
accompanied by vibrational & rotational exitation
broad band
intensity oI
absorption
( log )

max
wavelength
( logI
o
/I A cl )

absorbance molar extinction coeIIicient

highest energy ( Iar UV )

n

C O
C O C O
C O
ethylene : Iar UV
more conjugation lowers the transition energy
absorption moves to longer wavelengths
resonance stabilizes
the excited state more
than the ground state

proton : spinning charged particle generate magnetic moment
a proton in an external magnetic Iield
has two energy states
( I 1/2, 2I 1 states )
0 h = H
o
/ 2
Irequency (Hz)
H
o
14092 gauss
60 MHz
(sec
1
)
H
o
NMR (PMR, CMR)
protons under the same environment (equivalent protons) : Ieel the same
Iield strength
need the same
Irequency
Ior resonance
protons under diIIerent environments : Ieel diIIerent Iield
strength
need diIIerent
Irequency
Ior resonance
gauss
CH
3
CH
2
Cl
a b c
a b a
C C
H
3
C
H
3
C
C C
Br
H
H
H
a b
c
H
CH
3
H
H
H
H
a
c
c
d d
b
CH
3
CHCl C
H
H
Cl
a b
c
d
*
c, d are diastereotopic
diIIerent
enantiotopic
identical
diIIerent kinds oI protons have
diIIerent electronic environment
electrons in a molecule circulate and
generate secondary magnetic Iields in a
magnetic Iield (induced magnetic Iield)
a
a
CH
3
CH
3
Cl CH
3
CH
2
H
H
b
b


circulation oI electrons
about the proton itselI
generate an induced Iield
opposed to the applied Iield
the proton Ielt a
diminished Iield
(the proton is shielded)
the proton with more electron
density is more shielded
it requires a higher
applied Iield strength
( or a lower radioIrequency)
Ior resonance.
circulation oI electrons
about nearby nuclei
generate an induced Iield
which can oppose or reinIorce
the applied Iield at the proton
depends on the proton's
location ( Eig 17.9 )
reIerence point
Me
4
Si : 0.00ppm
Ior 60 MHz
chemical
shiIt
upIield shiIt shielding
downIield shiIt
deshielding
( induced secondary Iield applied Iield)
observed shiIt (Hz) 10
6
/ 60 10
6
(Hz)
Table 17.4
R
R
2
CH
2
R
3
CH
Ar H
0.9
1.3
1.5
6 ~ 8.5
CH
3
Cl
RCH
2
Cl
R
2
CHCl
3.0
3.4
4.0
CH
3
CH
3
C Cl
RCH
2
C Cl
R
2
CH C Cl
1.5
1.7
1.6
Eig 17.10
the ratio oI the peak areas the ratio oI the proton numbers
Eig 17.11

Eig 17.13 splitting oI NMR signals (multiplicity) caused by
spin - spin coupling
ex)
CH CH
2
a secondary proton Ieels slightly
increased or decreased magnetic
Iield by the spin oI the neighboring
tertiary proton.
Ior halI the molecules,
absorption is shiIted
slightly downIield.
Ior the other halI oI
the molecules, absorption
is shiIted slightly upIield.
the signal is split
into two peaks with
equal peak intensities.
( doublet)
triplet with
relative peak
intensities
1 : 2 : 1
Eig 17.16
( J coupling constant)
Ior
C
H
CH
3
H
o
quartet ( 1 : 3 : 3 : 1 )
Br C
Br
H
CH
2
Br Br CH C H
2
Br Br C
Br
H
CH
3
CH C H
3
downIield triplet upIield doublet downIield quartet upIield doublet
BrC H
2
CH
3
BrCH
2
C H
3
downIield quartet upIield triplet
Eig on p 616
H
o
Ior the
tertiary
proton
H
o
Br Br
Br

Which protons in a molecule
can be coupled ?
nonequivalent
neighboring protons
most commomly
protons on adjacent carbon.
sometimes protons Iurther
removed Irom each other.
(particularly through -bond)
no coupling
CH
2
CH
2
Cl Cl
C C
H
3
C
H
3
C
H
H
no coupling
C C
Br
H
3
C
H
H
coupling H
3
C C CH
2
Br
CH
3
Br
no coupling
cI)
C C Cl
E
E
H
H
p 618, 619
triplet
coupling constant J : independent oI applied
magnetic Iield
H
H
H
H
J 5 ~ 14 Hz
C C
H
H
H
J 10 ~ 21 Hz
J 2 ~ 6 Hz
J 2 ~ 15 Hz
J 0 ~ 7 Hz
C
C
H
H
gauche anti
vicinal protons
vinylic protons
J 2 ~ 13 Hz
Cl
the eIIectiveness oI
spin-spin coupling
Eig 17. 18-17.22
Eig 17-23 : impossible to do complete analysis with other kinds oI evidence
NMR is useIul to determine
the right structure.
OD H
D
2
H
2
H
2
D
2
D
2
CH
3
CH
2
CH
2
D CH
2
CH
3
CHD
Eig 17.24
much smaller
magnetic moment deuterium
double resonance
(irradiation)
(decoupling method)
instrumental techniques
chemical method
absorb at a much
highler Iield
weak coupling
H
H
H
H
a
H
b
a
H
b
rotation about single bonds
inversion R
*
O H
*
R O H

R
*
O H R O H
*

proton exchange
a given proton changes electronic and protonic environment,
which can change its chemical shiIt and its coupling with other protons.
Which does NMR spectometer see, the proton in each environment
or in an average oI all oI them?
depending on the temperature
labeling


H
H
g
H
Cl
H
g
H
a
two gauche protons
one anti protons
not equivalent single NMR signal
Cl
H
a
Cl
H
H
b
Cl
H
a
and H
b
have an indentical
average environment.
NMR spectrometer sees an
average environment by rotation
about the single bond.
H
H
a
Cl
CH
3
H
b
Cl
H
a
and H
b
are not identical.
H
a
H
a
two kinds oI protons 6-equatorial
6-axial
a single NMR signal : in an identical
average environment
H
a
and H
b
have diIIerent environments
the stabilities oI the two conIormations
are diIIerent
their populations are diIIerent
lowering temperature slows down rotation about single bonds
H
H
H
H
H
H
a
H
b
Br
H
a
H
b
H
Br

lower T


R O H
: shiIted downIield by hydrogen bonding
chemical shiIt depends on the degree oI hydrogen bonding (1~5ppm)
concn, temp, solvents
R
*
O H
*

R O H R
*
O H

R O H
*
proton exchange is so Iast cannot see nearby protons in their
various combinations oI spin alignments.
sees a single average alignment
13
C : 1.1 natural abundance can couple with nearby
13
C
with protons
13
C
13
C 0.01
decoupled by instrument
no coupling
X
1 BS 7.5 ppm
sp
3
: ( + ) 7.5 ppm
X : eIIect
eIIect
eIIect
downIield
upIield
eIIect
premium method
SN method
eIIect
1 ~ 0 BS
electronegative
C X
E : 8 BS
O : 5 BS
Cl, N : 3 BS
Br : 2 ~ 3 BS
CC : BS
C X
NO
2
: 8.5 BS
CO : 4 BS
COOR : 2.6 BS
C C : BS
C N : 0 BS
( ~ 120 ppm)
1/2
2/3




eIIect ( steric eIIect )
O sp
3
: 1 BS
O sp
2
: BS CH
3
: BS
Cl
2/3 1/3
sp
2
C C
reIerence point : 121.5ppm

121.5 7.5 |( + ) '|

cis : eIIect

2/3 BS
sp reIerence point : 72.5ppm
72.5 7.5 | () + 2/3() 2/3(') |
: 125~130 ppm
ESR (electron spin resonance)