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Proton NMR
Index
NMR-basics
H CH3 H H H
H
H H H H
H H H H
H H H H
H H H
Anisotropy: Aromatic
Electronic effects
H2C O H3C
Deshielded
+ H2C O H3C
O H
H
O
COOEt
COOEt
7.10 ppm
H
6.28 ppm
H COOEt EtOOC H
6.83 ppm
O
O
6.10 ppm
6.38 ppm
7.71 ppm
6.28 ppm
O
7
3 5 6 4 2
O
1
O
1 2
deshielded
4 6 5
7.75 6.20
H C
+ O
H
S
shielded
S
6.06 ppm
H H
5.81 ppm
O
H O
H 5.78 ppm
4.82 ppm H
6.5
6.0
5.5
5.0
4.5
4.0
3.5
shielded
2.65 2.60 2.55
6.35
6.30
4.95
4.90
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
o
p
CH3
deshielded
7.5
deshielded
8.0
Shielded
shielded
o
p
7.3
7.2
7.1
7.0
6.9
6.8
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
H3C NH
m p
o
shielded
Shielded
7.0
6.5
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2.5
7.5
7.4
Cl
7.3
7.2
7.1
7.0
6.9
7.4
Br
7.3
7.2
7.1
7.6
7.5
7.4
7.3
7.2
7.1
Hydrogen bond
Protons on Heteroatoms
OH
Aliphatic d 0.5-4.0 ppm (depend on Concentration) Intramolecular hydrogen bonding deshield OH and render it less sensitive to concentration
Usually OH exchange rapidly (no coupling with neighbors In DMSO or Acetone, the exchange rate is slower => there is coupling with neighbors Phenols : d 7.5-4.0 ppm Intramolecular bond 12-10 ppm Carboxylic Acids: Exist as Dimers 13.2-10 ppm
OH in DMSO
CH3-CH2-OH OH CH2 qd
(CH3)2 -CH-OH OH CH
Protons on Heteroatoms
NH : 14N: I=1 => 2I+1 lines NH has different rate of exchange 14N can relax quickly. Depending on relaxation rate, heteronuclear coupling will be visible or produce broadened peaks. R-NH : Aliphatic amines => rapid exchange
Sharp singlets : no coupling to N: d~3-0.5 ppm
NH
Amide
Protonated Amines
Formamide
H{14N}-NMR
H-CO-NH2 H-NMR
In Amine Salt: Moderate Rate of exchange => broad peaks ~ d 8.5-6.0 ppm CHa => show coupling to NH+ Sometimes broad [NHx+] consist of 3 broad hump due to 14N coupling
1J NH
~ 50 Hz
SH
Slow exchange SH couple to CHa When shaken with D2O, SH Disapear d ~ 1.6 1.2 ppm Aliphatic SH d ~ 3.6 2.8 ppm Aromatic SH
An example: C10H12O2
O CH3 CH3
J=8 Hz
2H 2H
H3C
O O O
2H
CH3
3H
3H
O
H3C CH3
Me-C=C
X 4 = 12
H3C
CH3
2nI + 1 lines
a doublet
H3C CH3
4 6 4 1 1 5 10 10 5 1 1 6 15 20 15 6 1
b septet
2.70
2.5
2.0
1.5
2nI + 1 lines
m p o o b a a
Br
4 6 4 1 1 5 10 10 5 1 1 6 15 20 15 6 1
p
7.50 7.40 7.30 7.20 7.10 7.00
2 x triplet b
3.40
3.30
3.20
3.10
3.00
7.5
7.0
6.5
6.0
5.5
5.0
4.5
4.0
3.5
3.0
2nI + 1 lines
4 6 4 1 1 5 10 10 5 1 1 6 15 20 15 6 1
a
b a
Br
2 x triplet 1 quintet
c
b
3.0
2.5
2.0
C7 H14 O2 I = 7 -14/2 + 1 = 1
mult triplet triplet sixtet quintet quartet triplet J (Hz) 7 7 7 7 7 7 COMMENT CH3->(CH2) CH3->(CH2) CH2 (CH3, CH2) CH2 (CH2, CH2) =C- CH2 (CH3) CH2 -O (CH2)
4 6 4 1 1 5 10 10 5 1 1 6 15 20 15 6 1
Int 3H 3H 2H 2H 2H 2H
CH3
Triplet: Roof effect CH2 0.9 ppm 1.35
CH2
CH2
2 x triplet 3H 3H
2H
Quartet:
2H
Quintet: Sixtet:
2H 2H
4.0
3.5
3.0
2.5
2.0
1.5
1.0
2nI + 1 lines
4 6 4 1 1 5 10 10 5 1 1 6 15 20 15 6 1
H3C
1 2
3 4
CH3
6
Triplet:
O
Quartet:
2 x triplet 6 1
Quintet: 3 Sixtet:
4.0
3.5
3.0
2.5
2.0
1.5
1.0
Hb
C
Hb Hb
C
Ha
C
Hb
C
Hb
Hb Ha
C
Hb
Hb
C
Hb Hb
C
Hb
C
Ha
C
Ha
C
Hb
C
Hb
Hb
Hc Hb Hb
C Jab Jab C
Ha
C
Hb
C
Hb
qd
Hb
C
Ha
C
Hb
Jab
td
Hb
C
Ha
C
Hb
C
Hc Hb
C
Ha
C
Hb
C
Hb
Geminal Coupling
Vicinal Coupling
3J
=> Perch
3J 3J
=> tool 1
=> Mestrec tool
Ha
Jab Jad
Jac
H
5
4J
N H
7
4J
H-H
= 9 Hz
C C H
H
1
5J
H-H
= 3 Hz
H H
4J
H-H
= 1-2 Hz
4J
H-H
C
= 3 Hz
C C H
4J
H-H
= 1.1 Hz
5J
H
H-H
= 3 Hz
Partial spectrum
-CH-CH3
A3X
3.0 2.5 2.0 1.5
CH2-CH2-CH3
A3M2X2
2.0 1.5 1.0
Each chemical shift is represented by a letter (far way letter for very large shift difference compare with the size of the coupling)
Dn / J
J
Dn J
3 4
5.0
1 2
4.0 3.0
nA and nB : center of gravity of doublet Chemical shift Dn = (1-4) * (2-3) SpinWorks => load AB
2.0
1.0
0.5
AB-Spectra
AMX
AMX
AMX
Substituants : 2 OMe (~ 3.9 ppm) CHO (~ 9.8 ppm) J Meta Para J Ortho Meta J Ortho Para OMe
H
OMe
OMe
H H
7.58 ppm
CHO
H
CHO
H
7.58 ppm
OMe
H
H
A
H
C
N H
D
+ -
dHC=7.31
dHD=8.19
HA HB HD HC
8.5
8.0
7.5
AFMX
d J
Me
CHO
H H
8 7 6
Cl
5
H
3 4 2 9
Cl
1
Me Cl
O
CHO-9 J = 2.0 Hz
3J 3J
H-1(s)
Jcis=10.5
H
8
H
7
dd
R
6
J =17 H trans
Hz
3,4=15.5 4,5
=8.5
H-4 dd
3J
PH
3J
HH
3J
HH
4J
FH
{31P}
R C C
P
P
H P H
dd
NMR From Spectra to Structures An Experimental approach Second edition (2007) Springler-Verlag Terence N. Mitchellm Burkhard Costisella
CH3
1H 1H
CH2
NMR From Spectra to Structures An Experimental approach Second edition (2007) Springler-Verlag Terence N. Mitchellm Burkhard Costisella
P31 NMR
C6D6
CDCl3
Me
=CH2 C6D6
H2 C OH Me
CH2 CH-OH
CH2 ABX
Decoupling
Me CH2
Me
=CH2 CDCl3
H2 C OH Me
CH2 ABX
CH-OH
CH2 AB
Spin-Spin Decoupling
dq
dq
dd
NMR From Spectra to Structures An Experimental approach Second edition (2007) Springler-Verlag Terence N. Mitchellm Burkhard Costisella
Homo decoupling
JPH
JHH
H-2
H-1
Several Decoupling
NOE
nOe
{A}
ba
X2 A1 aa
A2 X1
ab
X1 Dp = 2 X2 Dp = 2
X1 Dp = 2 X2 Dp = 2
Immediately after irradiation, there is NO change in the intensity of X Turning on the Decoupler do not change population of the X transition
X1 Dp = 2 X2 Dp = 2
X1
delay
bb
bb A2 X1
ba
X2 A1
ab
T1
ba
X2 A1
W2
aa
A2 X1
ab
aa
Dec. continue
X1 Dp = 3 After W2 relaxation, there is a net increase in the intensity of X (50%) X2 Dp = 3 Relaxation takes time to establish a new equilibrium: T1 process
X1 Dp = 2 X2 Dp = 2
X1
delay
ab
bb
bb A2 X1
ba
X2 A1
W0
aa
ab
T1
ba
X2 A1
W0
aa
A2 X1
ab
Dec. continue
X1 Dp = 1 After W0 relaxation, there is a net decrease in the intensity of X (50%) negative NOE X2 Dp = 1 Relaxation takes time to establish a new equilibrium: T1 process
W0
bb W2 A2
X1 aa
ab
If W2 is efficient (small molecule fast motion large frequency ) Level increase level increase also with decoupler continuing W2 pathway yield positive nOe If W0 is efficient (large molecule slow motion small freq. Diff.) Level increase level increase also with decoupler continuing
W0 pathway yield negative nOe
NOE difference: nOe-d NOE is a kinetic effect: need delay ~ T1 It take time to develop It takes time to decay d1
Dec on frq
Cl C H C
Me Me
AQ irr
d1
Dec off frq
AQ
irr
control nOe
difference
NOE
H3C H
H3C
COOH
Ph
{OH}
CH3 H
OMe
{OMe}
OMe H
6 5 1 2 3 4
Ph
CH3
H6 H3
H5
OH
NMR From Spectra to Structures An Experimental approach Second edition (2007) Springler-Verlag Terence N. Mitchellm Burkhard Costisella
NOEd
Cl
O CH P O O
CH3 CH3
Cl
NOEd example
Shift to low field when the metal is heavier (SnH4 - d = 3.9 ppm)
At low temperature, hydrogens form an A2B2X spin system At higher temperature germanium hop from one C to the next
Index
NMR-basics
NMR-Symmetry