Electron-impact ionization
ionization chamber e_
proton 1.00728 u
electron beam
70 eV
neutron 1.00866 u
(6700 KJ/mol) electron 0.00055 u
2
1
mass m B= magnetic field strength
B2 r2
= = r = radius of the analyzer tube
charge z 2V
V= voltage (accelerator plate)
Ionization
chamber
3
The Mass Spectrometer
2
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+)
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 + H
m/z=14
(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
m/z = 29 charge neutral
m/z=15 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
3
m/z=112 35Cl 34.96885 75.77
Cl
(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=158 81Br 80.91642 49.31 (98%)
m/z=156
(M+) (M+ +2)
m/z=157 m/z=159
(M+ +1) (M+ +3)
m/z 7
4
13.25: Molecular Formula as a Clue to Structure
Degrees of unsaturation
saturated hydrocarbon CnH2n+2
cycloalkane (1 ring) CnH2n
alkene (1 π-bond) CnH2n
alkyne (2 π-bonds) CnH2n-2
For each ring or π-bond, -2H from the formula of the saturated alkane
C6H14 C6H14 H
H H
H
H H
H - C6H12 - C 6H 6 H H
H
H
H H
H
H
H2 Hydrogen Deficiency H8 H
H
H
1
2 2=1 Degrees of Unsaturation
1
2 8=4
10
5
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
6
Quantum: the energy of a photon
c
E = hν ν=
λ
h•c
E=
λ
E α ν E α λ−1 ν α λ−1
7
organic light organic relaxation organic
molecule molecule + hν
molecule
(ground state) hν (excited state) (ground state)
15
UV Vis
λ 200 400 800 nm
Recall bonding of a π-bond from Chapter 10.16
16
8
π-molecular orbitals of butadiene
Ψ4: 3 Nodes
0 bonding interactions
3 antibonding interactions
ANTIBONDING MO
Ψ3: 2 Nodes
1 bonding interactions
2 antibonding interactions
ANTIBONDING MO
Ψ2: 1 Nodes
2 bonding interactions
1 antibonding interactions
BONDING MO
Ψ1: 0 Nodes
3 bonding interactions
0 antibonding interactions
BONDING MO
Butadiene
Butadiene
18
9
Molecular orbitals of conjugated polyenes
Antibonding
Energy
Bonding
H2C CH2
180 nm 217 nm 258 nm 290 nm
19
Color of Color
absorbed light λ 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
10
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
β-carotene
lycopene 21
A=εcl A = absorbance
c = concentration (M, mol/L)
l = sample path length (cm)
ε = molar absorptivity (extinction coefficient)
a proportionality constant for a specific
absorbance of a substance
22
11
13.20: Introduction to Infrared Spectroscopy
23
>
>
>
>
>
>
> >
12
Bond Stretch:
X Y
Hooke’s Law
_
! = vibrational frequency
1 c = speed of light
f 2 mx = mass of X
_ 1 my = mass of Y
!= mx my
2"c mx + my mx my
= reduced mass (µ)
mx + my
4000 cm-1 2500 cm-1 2000 cm-1 1500 cm-1 600 cm-1
26
13
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)
C≡C 2100 - 2200 cm-1 (weak, often not observed)
C≡N 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
2
sp =C-H 3000 - 3100 cm-1
sp ≡C-H 3310 - 3320 cm-1 27
14
H
C H
H3CH2CH2CH2C C
H
% transmittance
% transmittance
=C-H
C=C
C-H hexane C-H
cm-1 cm-1
% transmittance
C≡C
% transmittance
C≡C
≡C-H
C-H H3CH2CH2CH2C C C H
C-H H3CH2CH2C C C CH3
cm-1 cm-1
29
CH3(CH2) 4 CH2 OH
C≡N
N-H
N-H
C-H
C-H
30
15
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
Alkenes Amide
=C-H 3020-3150 N-H 3180-3350
C=C 1600-1700
Carbonyl Group
Alkynes C=O 1650-1780
!C-H 3300
C!C 2100-2200
Carboxylic Acids
Alkyl Halides O-H 2500-3100
C-Cl 600-800
C-Br 500-600
C-I 500 Nitriles
C!N 2210-2260
Alcohols
O-H 3400-3650
C-O 1050-1150 Nitro Group
-NO2 1540
Aromatics
=C-H 3030
32
1600, 1500
16
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
17
The energy difference between aligned and opposed to the external
magnetic field (Bo) is generally small and is dependant upon Bo
Applied EM radiation (radio waves) causes the spin to flip and the
nuclei are said to be in resonance with Bo
+ +
36
18
Continuous wave
(CW) NMR
Pulsed (FT) NMR
37
38
19
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 δ = 0
Cl
H CH3 for 1H NMR
Cl
H–CCl3
downfield δ = 7.28 ppm upfield
lower magnetic field higher magnetic field
less shielded more shielded
(deshielded)
TMS
39
Chemical shift (δ, ppm)
TMS
20
13.5: Effect of Molecular Structure on 1H Chemical Shift
H3C-F
C-F H3C-O-
C-O-CH
CH3 (H3C)3-N H3C-CH3 (H3C)4-Si
δ 4.3 δ 3.2 δ 2.2 δ 0.9 δ 0.0
The deshielding effect of a group drops off quickly with distance
(number of bonds between the substituent and the proton)
H3C-H2C-H2C-H2C-O-C-O-CH
CH2-CH2-CH2-CH3
δ= 1.37 3.40
0.92 1.55 41
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
21
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
22
13.6: Interpreting 1H NMR Spectra
Equivalence (chemical-shift equivalence): chemically and
magnetically equivalent nuclei resonate at the same
energy and give a single signal or pattern
H H
N C C O C H
H H
TMS
45
H3C H
C C
H3C CH3
46
23
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
47
Identical, so the methyl groups are equivalent
H3C
C C
H H3C
C C
H
These are geometric
H3C CH3 H3C CH3 isomers (not identical and
H3C H H3C H H3C H
not enantiomers). The three
H3C
C C
CH3
C C C C methyl groups are therefore
H3C CH3 H3C CH3
not chemically equivalent
and can give rise to different
H3C H H3C H
C C C C resonances
H3C CH3 H3C CH3
H3C H
C C
H3C CH3
48
24
H
H CH2CH3
H H
H
49
H Cl
H3C C C CH3
H H
Homotopic: equivalent
Enantiotopic: equivalent
Diastereotopic: non-equivalent 50
25
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
δ= 4.20,
2H δ= 3.50,
δ3H
TMS
51
H O H H δ= 2.0
H C C O C C H 3H
δ= 1.2
H H H 3H
δ= 4.1
2H
26
The multiplicity is defined by the number of peaks and the pattern
(see Table 13.2 for common multiplicities patterns and relative
intensities)
H O H H δ= 2.0
H C C O C C H s, 3H
δ= 1.2
H H H t, 3H
δ= 4.1
q, 2H
-CH2- -CH3-
1:2:1
53
1:3:3:1
H O H H δ= 2.0
H C C O C C H s, 3H
δ= 1.2
H H H t, J=7.2 Hz, 3H
δ= 4.1
q, J=7.2 Hz, 2H
3J 3J
3J
ab
3J 3
ab Jab ab ab 54
27
13.8: Splitting Patterns: The Ethyl Group
δ= 7.4-7.1, δ= 8.0,
m, 5H δ= 2.6, q, 2H
J= 7.0, 2H
δ= 7.6-7.3,
m, 3H
55
δ= 7.4-7.1, δ= 2.9, s,
m, 5H J= 6.9, 1H
δ= 8.1, d, δ= 7.4, d
J= 6.1 Hz, J= 6.1 Hz,
2H 2H
δ= 3.0, s,
J= 6.9, 1H
56
28
13.10: Splitting Patterns: Pairs of Doublets
H O
H C δ= 1.2, s, 9H
OCH3
H3C δ= 8.0, d, δ= 7.4, d, δ= 3.9,
C H
H3C CH H J= 9.0 2H J= 9.0 2H s, 3H
3
fig 13.19,
p. 537
57
J1-2 = 7.0
J1-2 = 7.0
J2-3 = 16.0
J2-3 = 16.0 H O
C C
C H
H
29
J1,2 = J2,3
H H H
J1,2
C C C H δ= 0.9, t,
H H H J = 7.4, 3H
δ= 2.6, 2H δ= 1.6, 2H
J2,3
59
H A
C O H C O H + H A
H H
30
Summary of 1H-1H spin-spin coupling
• chemically equivalent protons do not exhibit spin-spin
coupling to each other.
• the resonance of a proton that has n equivalent protons on
the adjacent carbon is split into n+1 peaks (multiplicity)
with a coupling constant J.
• protons that are coupled to each other have the same
coupling constant
• non-equivalent protons will split a common proton
independently: complex coupling.
62
31
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
32
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
65
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
33
13.18: Using DEPT to Count Hydrogens Attached to 13C
1H-13C spin-spin coupling: spin-spin coupling tells how many
67
8 3
OH Broad-band decoupled
2 4 8 7
5
6 4 2 1
7 5 3 1 6
CH3
DEPT CH CH3
CH CH3
CH2 CH2
34
Solving Combined Spectra Problems:
Mass Spectra:
Molecular Formula
Nitrogen Rule → # of nitrogen atoms in the molecule
M+1 peak → # of carbons
Degrees of Unsaturation: # of rings and/or π-bonds
Infrared Spectra:
Functional Groups
C=O O-H
C=C N-H
C≡C CO-OH
C≡N
1H NMR:
70
35
Problem 13.42 (Fig. 14.46, p. 573)
71
35.5
212.1
72
36
C10H14 127.0
31.2
128.2 125.7
41.7 21.8
12.3
147.6
δ= 2.61 δ= 2.61
(d, 3H) (t, 3H)
δ= 2.61
δ= 2.61 (pentet,
(sextet, J=7, 2H)
J=7, 1H)
δ= 7.4-7.1
(m, 5H)
73
37