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CH 13
CH 13
1
13.24: Mass Spectrometry:
molecular weight of the sample formula
proton 1.00728 u
electron beam neutron 1.00866 u
70 eV
(6700 KJ/mol) electron 0.00055 u
2
B= magnetic field strength
mass m B2 r2
= = r = radius of the analyzer tube
charge z 2V
V= voltage (accelerator plate)
Ionization
chamber
3
The Mass Spectrometer
Exact Masses of Common Natural Isotopes
4
Molecular Ion (parent ion, M) = molecular mass of the analyte;
sample minus an electron
m/z=78 (M+)
(100%)
C6H6
m/z = 78.04695
m/z=79 (M+1)
(~ 6.6% of M+)
5
The radical cation (M+•) is unstable and will fragment into
smaller ions
m/z=15
H +
m/z=16 (M+) H
-e
_ H
Relative abundance (%)
H C H H C H H C+ + H
H H H charge neutral
m/z = 16 m/z = 15 not detected
+
m/z=17 H C H +
m/z=14 H
(M+1)
m/z = 14 charge neutral
not detected
m/z
H H H _ + H H H
-e H H H
H C C C H +
m/z=29 H C C C H H C C C + H
Relative abundance (%)
H H H H H H
H H H charge
_ m/z = 43 neutral not
-e m/z = 44 detected
m/z=43 m/z=44 H H H
+ H H H
(M) H C C C H
H C C
+ + C H
H H H
H H H
charge neutral
m/z=15 m/z = 29
not detected
m/z=45
(M+1) H H H
H C C + +C H
H H H 6
charge neutral m/z = 15
m/z not detected
Cl m/z=112 35Cl 34.96885 75.77
(M+) 37Cl 36.96590 24.23 (32.5%)
m/z=114
(M+ +2)
m/z=77 m/z=113
(M+ +1)
m/z=115
(M+ +3)
m/z
Br
m/z=77
79Br 78.91839 50.69
m/z=156 m/z=158 81Br 80.91642 49.31 (98%)
(M+) (M+ +2)
m/z=157 m/z=159
(M+ +1) (M+ +3)
m/z 7
Mass spectra can be quite complicated and interpretation difficult.
8
13.25: Molecular Formula as a Clue to Structure
9
Degrees of unsaturation
saturated hydrocarbon CnH2n+2
cycloalkane (1 ring) CnH2n
alkene (1 -bond) CnH2n
alkyne (2 -bonds) CnH2n-2
For each ring or -bond, -2H from the formula of the saturated alkane
C6H14 C6H14 H
H H H H
H
H H
H - C6H12 - C6H6
H H
H
H
H H
H
H
H2 Hydrogen Deficiency H8 H
1
1
2 2=1 Degrees of Unsaturation 2 8=4
10
Correction for other elements:
For Group VII elements (halogens): subtract 1H from the
H-deficiency for each halogen,
For Group VI elements (O and S): No correction is needed
C10H14N2 C12H4O2Cl4
11
13.1: Principles of molecular spectroscopy:
Electromagnetic radiation
organic light organic relaxation organic
molecule molecule + h
molecule
(ground state) h (excited state) (ground state)
h•c
E=
15
13.23 Ultraviolet-Visible (UV-Vis) Spectroscopy
UV Vis
200 400 800 nm
16
-molecular orbitals of butadiene
4: 3 Nodes
0 bonding interactions
3 antibonding interactions
ANTIBONDING MO
3: 2 Nodes
1 bonding interactions
2 antibonding interactions
ANTIBONDING MO
2: 1 Nodes
2 bonding interactions
1 antibonding interactions
BONDING MO
1: 0 Nodes
3 bonding interactions
0 antibonding interactions
BONDING MO
Butadiene
Butadiene
18
Molecular orbitals of conjugated polyenes
A
n
tib
o
n
d
in
g
E
n
rg
e
y
B
o
n
d
in
g
H2C CH2
180 nm 217 nm 258 nm 290 nm
19
Molecules with extended conjugation move toward the visible region
Color of Color
absorbed light observed
violet 400 nm yellow
blue 450 orange
blue-green 500 red
yellow-green 530 red-violet
yellow 550 violet
orange 600 blue-green
red 700 green 20
Many natural pigments have conjugated systems
OH
OH
+
N HO O
OH
N Mg N O
O
N O OH OH OH
HO O
CO2CH3
OH
O
Chlorophyll anthocyanin
-carotene
lycopene 21
Chromophore: light absorbing portion of a molecule
A=cl A = absorbance
c = concentration (M, mol/L)
l = sample path length (cm)
= molar absorptivity (extinction coefficient)
a proportionality constant for a specific
absorbance of a substance
22
13.20: Introduction to Infrared Spectroscopy
23
Stretch: change in bond length
http://www2.chem.ucalgary.ca/Flash/photon.html
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4000 cm-1 2500 cm-1 2000 cm-1 1500 cm-1 600 cm-1
26
Fingerprint region (600 - 1500 cm-1)- low energy single bond
stretching and bending modes. The fingerprint region is
unique for any given organic compound. However, there are
few diagnostic absorptions.
Double-bond regions (1500 - 2000 cm-1)
C=C 1620 - 1680 cm-1
C=O 1680 - 1790 cm-1
Triple-bond region: (2000 - 2500 cm-1)
CC 2100 - 2200 cm-1 (weak, often not observed)
CN 2240 - 2280 cm-1
X-H Single-bond region (2500 - 4000 cm-1)
O-H 3200 - 3600 cm-1 (broad)
CO-OH 2500-3600 cm-1 (very broad)
N-H 3350 - 3500 cm-1
C-H 2800 - 3300 cm-1
sp3 -C-H 2850 - 2950 cm-1
sp2 =C-H 3000 - 3100 cm-1
sp C-H 3310 - 3320 cm-1 27
13.22 Characteristic Absorption Frequencies
Table 13.4, p. 554
Alkenes
=C-H 3020 - 3100 cm-1 medium - strong
C=C 1640 - 1680 cm-1 medium
Aromatic
=C-H 3030 cm-1 strong
C=C 1450 - 1600 cm-1 strong
Alkynes
C-H 3300 cm-1 strong
CC 2100-2260 cm-1 weak - medium
Alcohols
C-O 1050 - 1150 cm-1 strong
O-H 3400 - 3600 cm-1 strong and broad
Amines
C-N 1030 - 1230 cm-1 medium
N-H 3300 - 3500 cm-1 medium
Carbonyl
C=O 1670 - 1780 cm-1 strong
Carboxylic acids
O-H 2500 - 3500 cm-1 strong and very broad
Nitrile
CN 2240 - 2280 cm-1 weak-medium
28
H
C H
H3CH2CH2CH2C C
H
% transmittance
% transmittance
=C-H
C=C
C-H hexane C-H
cm-1 cm-1
% transmittance
CC
% transmittance
CC
C-H
C-H H3CH2CH2CH2C C C H
C-H H3CH2CH2C C C CH3
cm-1 cm-1
29
CH3(CH2)4CH2OH
CN
C-H H3C(H2C)4CH2CN
O-H C-H C-O
CH3(CH2)4CH2NH-CH3
CH3(CH2)4CH2NH2
N-H
N-H
C-H
C-H
30
O O
C C
(H3C)3CH2C OH H3C(H2C)3H2C OCH2CH3
O-H
C=O
1705 cm-1 C=O
1710 cm-1
O O
C C
H3C(H2C)3H2C H H3C(H2C)2H2C CH3
O
C
H
31
Typical IR Absorptions for Funtional Groups
difficult to interpret
C-H C C
O-H C C
C O
N-H C N
C N
Alkenes Amide
=C-H 3020-3150 N-H 3180-3350
C=C 1600-1700
Carbonyl Group
Alkynes C=O 1650-1780
C-H 3300
CC 2100-2200
Carboxylic Acids
Alkyl Halides O-H 2500-3100
C-Cl 600-800
C-Br 500-600
C-I 500 Nitriles
CN 2210-2260
Alcohols
O-H 3400-3650
C-O 1050-1150 Nitro Group
-NO2 1540
Aromatics
=C-H 3030
32
1600, 1500
13.3: Introduction to 1H NMR
direct observation of the H’s of a molecules
+
+
organic chemistry
Natural Abundance
1H 99.9% 13C 1.1%
12C 98.9% (not NMR active)
33
(a) Normally the nuclear magnetic fields are randomly oriented
(b) When placed in an external magnetic field (Bo), the nuclear
magnetic field will either aligned with (lower energy) or
oppose (higher energy) the external magnetic field
+ +
36
Continuous wave
(CW) NMR
Pulsed (FT) NMR
37
13.4: Nuclear Shielding and 1H Chemical Shift
Different nuclei absorb EM radiation at different wavelength
(energy required to bring about resonance)
Nuclei of a given type, will resonate at different energies
depending on their chemical and electronic environment.
The position (chemical shift, ) and pattern (splitting or multiplicity)
of the NMR signals gives important information about the
chemical environment of the nuclei. The integration of the
signal is proportional to the number of nuclei giving rise to
that signal
H O H H
H C C O C C H
H H H
38
Chemical shift: the exact field strength (in ppm) that a nuclei comes
into resonance relative to a reference standard (TMS)
Electron clouds “shield” nuclei from the external magnetic field causing
them to resonate at slightly higher energy
Shielding: influence of neighboring functional groups on the electronic
structure around a nuclei and consequently the chemical shift
of their resonance.
Cl CH3 Tetramethylsilane (TMS);
C
H3C Si CH3 Reference standard = 0
H Cl
CH3 for 1H NMR
Cl
H–CCl3
downfield = 7.28 ppm
upfield
lower magnetic field higher magnetic field
less shielded more shielded
(deshielded)
TMS
39
Chemical shift (, ppm)
downfield NCCH2OCH3 upfield
lower magnetic field higher magnetic field
less shielded more shielded
(deshielded) = 3.50 ppm
= 4.20 ppm
3H
2H
TMS
C Cl C Cl C
H H H H
H H
Cl
O O O
H Cl Cl
CH3CH2O H H Cl
CH3CH2O CH3CH2O
H H H
42
Typical 1H NMR chemical shifts ranges; additional substitution
can move the resonances out of the range
12 11 10 9 8 7 6 5 4 3 2 1 0
H
1H NMR Shift Ranges R2N CR2
O H X H
12 11 10 9 8 7 6 5 4 3 2 1 0
(ppm)
H
O H H H H
C C H C C H H3C CH3
H H H H H
H
H H
N C C O C H
H H
TMS
45
H3C H
C C
H3C CH3
46
Test of Equivalence:
1. Do a mental substitution of the nuclei you are testing with an
arbitrary label
2. Ask what is the relationship of the compounds with the
arbitrary label
3. If the labeled compounds are identical (or enantiomers), then the
original nuclei are chemically equivalent and do not normally
give rise to a separate resonance in the NMR spectra
If the labeled compounds are not identical (and not enantiomers),
then the original nuclei are not chemically equivalent and can
give rise to different resonances in the NMR spectra
H H H H H H H H
H C CH3 H C CH3 H C CH3 H C CH3
C C C C C C C C
H3C CH3 H3C CH3 H3C CH3 H3C CH3
H3C H
C C
H3C CH3
48
H
H CH2CH3
H H
H
49
H Cl
H3C C C CH3
H H
Homotopic: equivalent
Enantiotopic: equivalent
Diastereotopic: non-equivalent 50
Integration of 1H NMR resonances: The area under an NMR
resonance is proportional to the number of equivalent
nuclei that give rise to that resonance.
H H
N C C O C H
H H
= 4.20,
2H = 3.50,
3H
TMS
51
13.7: Spin-spin splitting in 1H NMR spectroscopy
protons on adjacent carbons will interact and “split” each others
resonances into multiple peaks (multiplets)
n + 1 rule: equivalent protons that have n equivalent protons
on the adjacent carbon will be “split” into n + 1 peaks.
H O H H = 2.0
H C C O C C H 3H
= 1.2
H H H
3H
= 4.1
2H
-CH2- -CH3-
1:2:1
1:3:3:1 53
The resonance of a proton with n equivalent protons on the adjacent
carbon will be “split” into n + 1 peaks with a coupling constant J.
Coupling constant: distance between peaks of a split pattern; J is
expressed in Hz. Protons coupled to each other have the same
coupling constant J.
H O H H = 2.0
H C C O C C H s, 3H
= 1.2
H H H
t, J=7.2 Hz, 3H
= 4.1
q, J=7.2 Hz, 2H
3J 3J 3J 3J
3J
ab ab ab ab ab 54
13.8: Splitting Patterns: The Ethyl Group
= 7.4-7.1, = 8.0,
m, 5H = 2.6, q, 2H
J= 7.0, 2H
= 7.6-7.3,
m, 3H
55
13.8: Splitting Patterns: The Isopropyl Group
= 7.4-7.1, = 2.9, s,
m, 5H J= 6.9, 1H
= 8.1, d, = 7.4, d
J= 6.1 Hz, J= 6.1 Hz,
2H
2H = 3.0, s,
J= 6.9, 1H
56
13.10: Splitting Patterns: Pairs of Doublets
H O
H C
OCH3
= 1.2, s, 9H
H 3C = 8.0, d, = 7.4, d, = 3.9,
C H
H3C CH H J= 9.0 2H J= 9.0 2H s, 3H
3
fig 13.19,
p. 537
57
13.11: Complex Splitting Patterns: when a protons is adjacent
to more than one set of non-equivalent protons, they
will split independently
J1-2 = 7.0
J1-2 = 7.0
J2-3 = 16.0
J2-3 = 16.0 H O
C C
C H
H
H H H
J1,2
C C C H = 0.9, t,
H H H J = 7.4, 3H
= 2.6, 2H = 1.6, 2H
J2,3
59
13.12: 1H NMR Spectra of Alcohols
Usually no spin-spin coupling between the O–H proton and
neighboring protons on carbon due to exchange reaction
H A
C O H C O H + H A
H H
62
13CNMR Spectroscopy: O
Natural Abundance H3C C OCH3
1H 99.9% (I= 1/2) 12C 98.9% (I= 0)
13C 1.1% (I= 1/2)
1.1 % 1.1 % 1.1 %
time
Signal-averaging: pulsed NMR allows for many FID’s (NMR
spectra) to be accumulated over time. These FID’s are added
together and averaged. Signals (resonances) build up while the
“noise” is random and cancels out during the averaging.
Enhanced signal to noise ratio and allows for NMR spectra to
be collected on insensitive nuclei such as 13C and small samples.
13C-spectra of CH3CH2CH2CH2CH2OH
after one scan average of 200 scans
64
Chemical shifts give an idea of the chemical and electronic
environment of the 13C nuclei due to shielding and
deshielding effects range: 0 - 220 ppm from TMS
13C NMR spectra will give a map of the carbon framework. The
number of resonances equals the number of
non-equivalent carbons.
128.0 O
128.5 C CH2CH2CH3
132.8 128.0
137.1
128.5
CDCl3 TMS
200.3 137.1
65
Chemical Shift Range of 13C
R3C-Br
Typical 13C NMR Shift Ranges
R3C-F R3C-Cl R3C-I
R2N-CR3
R3C OH O
nitriles
RC CR3
aromatics RO CR3 Ar-CR3
vinyl alkyne
carbonyls
saturated
ketones & esters, amides alkanes
aldehydes & acids
67
8 3
OH Broad-band decoupled
2 4 8 7
6 5
4 2 1
7 5 3 1 6
CH3
DEPT CH CH3
CH CH3
CH2 CH2
70
Problem 13.42 (Fig. 14.46, p. 573)
71
13.43 (Fig. 13.47, p. 574): C5H10O
13C NMR:
7.9
35.5
212.1
72
C10H14 127.0
31.2
128.2 125.7
41.7 21.8
12.3
147.6
= 2.61 = 2.61
(d, 3H) (t, 3H)
= 2.61
= 2.61 (pentet,
(sextet, J=7, 2H)
J=7, 1H)
= 7.4-7.1
(m, 5H)
73
15.14 Spectroscoic Analysis of Alcohols and Thiols:
Infrared (IR): Characteristic O–H stretching absorption at
3300 to 3600 cm 1
Sharp absorption near 3600 cm-1 except if H-bonded:
then broad absorption 3300 to 3400 cm 1 range
Strong C–O stretching absorption near 1050 cm 1
H
O
%T
O-H
C-O
74
cm-1
1H NMR: protons attached to the carbon bearing the hydroxyl
group are deshielded by the electron-withdrawing nature
of the oxygen, 3.3 to 4.7
H3C H H = 0.9,
H3C C C C OH d, 3H
H H H = 1.5,
q, 2H
= 3.65, = 1.7,
= 2.25, m, 1H
t, 2H
br s, 1H
61.2 22.6
41.7 24.7
CDCl3
O-H C-O
75
Usually no spin-spin coupling between the O–H proton and
neighboring protons on carbon due to exchange reaction
H A
C O H C O H + H A
H H
76
13C NMR: The oxygen of an alcohol will deshield the carbon
it is attached to. The chemical shift range is 50-80 ppm
14 19 35 62
CH3 — CH2 — CH2 — CH2 — OH
OH HO OH
H H 145.2
H C C C H DMSO-d6
H H H (solvent)
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77
15.48 (fig 15.8, p. 658)
13C: 138.6
129.4
128.4
126.3
68.8
45.8
22.7
13C: 145.2
128.8
127.8
126.5
76.3
32.3
10.6
78
Magnetic Resonance Imaging (MRI): uses the principles of
nuclear magnetic resonance to image tissue
Alzheimer’s
Normal Normal
Disease
25 years old 86 years old
78 years old
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fMRI: 80