Beruflich Dokumente
Kultur Dokumente
Bo
Atomic nuclei in
The absence of
a magnetic field
spin
spin
Ho
resonance
no resonance
Rf
no resonance
Observable Nuclei
Odd At. Wt.; s = 1/2
1
13
Nuclei
H1
C6
Abundance (%) 99.98 1.1
H1
14
N7
Unobserved Nuclei
12
C6
16
O8
32
S16
N7 19F9
0.385 100
15
31
P15 .
100
E = h
h = Plancks constant:1.58x10-37kcal-sec
E = h/2(Bo)
Thus:
= /2(Bo)
For a proton,
if Bo = 14,092 gauss (1.41 tesla, 1.41 T),
= 60x106 cycles/sec = 60 MHz
and
EN = Nh= 0.006 cal/mole
60 MHz
100 MHz
1.41 T
2.35 T
E = h/2(Bo)
500 MHz
11.74 T
Bo
13
Rf (MHz)
Bo (T)
/2 (MHz/T)
500.00
11.74
42.58
125.74
11.74
10.71
76.78
11.74
6.54
19
470.54
11.74
40.08
31
202.51
11.74
17.25
60 MHz
60,000,000 Hz
60,000,600 Hz
upfield
downfield
240 Hz
deshielded
10
Me4Si
shielded
60 Hz
0 scale (ppm)
}
at 500 MHz
500 Hz
chemical
shift
12 ppm
1
H (TMS)
~380 ppm
P (H3PO4)
~220 ppm
31
76.78
220 ppm
F (CFCl3)
19
13
PX3
CPH2
500.00
-SO2F
100
125.74
-CF2-CF2470.54
202.51
R2C=O
CH4
RCH3
200
300
400
500 MHz
10
10
CHCl3
CH2Cl2
CH3Cl
CH4
=7.26
=5.30
=3.05
=-0.20
CHBr3
CH2Br2
CH3Br
=6.83
=4.95
=2.68
0
TMS
4.0
area = 2
10
homotopic
protons: chemically
and magnetically
equivalent
enantiotopic protons:
chemically and
magnetically equivalent
Spin-Spin Splitting
= 1.2
area = 9
anticipated spectrum
= 6.4
area = 1
10
TMS
= 4.4
area = 1
Spin-Spin Splitting
= 1.2
area = 9
observed spectrum
= 6.4
area = 1
= 4.4
area = 1
H
10
TMS
J is a constant
and independent
of field
Spin-Spin Splitting
= 6.4
= 4.4
J = 1.5 Hz
J = 1.5 Hz
H
H
local
H
local
observed
observed
8
applied
5
applied
spin (1/2)
multiplicity
pattern
(a + b)n
symbol
singlet (s)
1/2
1:1
doublet (d)
2/2 = 1
1:2:1
triplet (t)
3/2
1:3:3:1
quartet (q)
4/2 = 1
1:4:6:4:1
quintet (qt)
CH3CH2Br
for H spins
for H spins
= 1.68
area = 3
= 3.43
area = 2
90 Hz/46 pixels
= 3J/12 pixels
: J= 7.83 Hz
(CH3)2CHOH
1H septuplet; no coupling to OH
6H, d, J = 7.5 Hz
(4.25-3.80)x90/6 = 7.5 Hz
1H, s
4.25
3.80
(CH3)2CHOD
homotopic sets
of protons
pro-R
H
H
H
H
H
Diastereotopic protons
pro-S
H
H
H
H
1.03 (3H, t)
1.70 (3H, d)
1.82 (1H, m)
1.84 (1H, m)
4.09 (1H, m (sextet?))
H
O
No!
H
O
7.3 Hz
7.3 Hz
7.3 Hz
1.4 Hz
H
H
H
7.3 Hz
quartet of doublets
7.3 Hz
= 1.9 Hz
= 6.9 Hz
H
H
3H, t, J = 7.0 Hz
= 14.4 Hz
2H, q, J = 7.0 Hz
6.46
14.4
6.9
4.17
H
H
1.9
14.4
Another example
1.9
6.9
triplet of triplets
He
3.0
3.0
2.7
2.7
He H
e4.03,
4.03,J(H
J(H
)=
3.0
3.0
HzHz
a) a=
J(H
J(H
)=
2.7
2.7
HzHz
e) e=
11.4 Hz
400 Hz
triplet of triplets
Ha
11.1
11.1
4.3
4.3
30.8 Hz
10
>> J
~= J
10
9
= 0
10
Magnetic Anisotropy
H
H
Bo
Magnetic Anisotropy
R
C
C
H
Bo
13
13
C Chemical Shifts
WheresWaldo?
Onecarbonin3moleculesofsqualeneis13C
What are the odds that two 13C are bonded to one another?
~10,000 to 1
13
C1
JCH = 3 Hz
C2
JCH = 5 Hz
30
20
26.6
18.3
10
ppm ()
TMS
JCH = 118 Hz
13
JCH = 126 Hz
Broadband decoupling
removes all C-H coupling.
C1
C2
JCH = 5 Hz
30
20
26.6
18.3
JCH = 3 Hz
10
ppm ()
TMS
JCH = 118 Hz
13
13
The End
F. E. Ziegler, 2004