from last lecture - cook groupcook.chem.ndsu.nodak.edu/.../handouts/lecture-04... · from last...
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![Page 1: From Last Lecture - Cook Groupcook.chem.ndsu.nodak.edu/.../handouts/lecture-04... · From Last Lecture. 2 Proton NMR Scale Range 0-10 ppm 10 C H H H H H δ 4 1 0ppm CX 9 8 7 6 5 3](https://reader034.vdocument.in/reader034/viewer/2022050513/5f9d4391af9c6b0c353f1dd4/html5/thumbnails/1.jpg)
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The intensity of the peaks roughly correlates with the number of hydrogens on the carbon.
DEPT-C13 NMR can tell you exactly how many H’s are on the carbons.
Reactions can be followed by watching functional group changes.
Symmetry (# of different carbons) is very useful information.
Proton NMR similar - but more information.
From Last Lecture
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Proton NMR Scale
Range 0-10 ppm
10
CH
H H
HH
4 1 0δ ppm
C X
5 239 678
HH
HH
H
H
H
CCH
C OH
C OOH
1H NMR
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NMR Correlation Chart
C H
C C
O H
Functional Group
Type 1H Chemical Shift (ppm)
Alkane
Allylic or next to carbonyl 1.6 - 2.4
alcohol varies widelywill exchange with D2O
Typical NMR Chemical Shifts
0.7 -1.8
H
CX Hnext to halogen or alcohol
2.5 - 4.0
CO Hnext to oxygen of an ester 4.0 - 5.0C
O
C Hvinylic 4.5 - 6.5
CH
aromatic 6.5 - 8.0
C HO
aldehyde 9.7 - 10.0
C XO
carbonyl of ester, amide, or carboxylic acid (X = O, N)
165 - 185
CO carbonyl of
ketone or aldehyde
190 - 220
30 - 60
10 - 60
20 - 85
50 - 85
110 - 150
110 - 140
190 - 220
13C Chemical Shift (ppm)
N/A
N/A
N/A
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Methyl Acetate
H3CC
OCH3
O
Area under peak corresponds to the number of H’s for that resonance
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Triphenyl Methanol
OH
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Ethyl Acetate
H3CC
O
H2C
O
CH3
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Protons on adjacent carbons also have an effect
Resonances will split into n+1 number of peaks
Spin Spin Splitting
C CHa Hb
Hb
1H NMR (without coupling)
1H NMR (with coupling)
Ha Hb
J J
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Spin Spin Splitting
Two hydrogens split neighbors into a triplet
C C Hb
Ha Hb
Hb
1H NMR (without coupling)
1H NMR (with coupling)
Ha Hb
J JJ
1 11 : 2 1:
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Spin Spin Splitting
Every splitting can be broken down into a series of doublets 1H NMR
(without coupling)
1H NMR (with coupling)
Ha
J
1 11 : 2 1:
J J
1 1
C C Hb
Ha Hb
Hb
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Spin Spin Splitting
Three neighbors - Quartet
C CHb
Hb
Ha Hb
Hb
1 11 : 3 3:
1H NMR (without coupling)
1H NMR (with coupling)
Ha Hb
JJ
JJ
11:
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Higher Spin Spin Splitting
singlet 11 1doublet
1 2 1triplet1 3 3 1quartet
1 4 6 4 11 5 10 10 5 1
1 6 15 20 15 6 1
quintetsextetseptet
C CHb
Hb
Ha Hb
CHb
Hb
Hb
Ha will split into 7 peaks
Pascal’s Triangle
64 different combinations
of 6 spins
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Summary of Spin Spin Splitting
Proton resonance split into n+1 number of peaks
Relative ratio of peaks depends on number of spin states of the neighbors.
Adjacent protons will couple with the same coupling constant.
Protons farther away usually do not couple.
Chemically equivalent protons cannot couple (eg. ClCH2CH2Cl).
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Doublet Splitting
Methyl sees 1 neighbor, Methine sees 3
CH3C NH3Cl
CO O
CH3
H
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Ethanol
Note that the OH (and NH) usually don’t couple.
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1,1,2-Trichloroethane
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2-Bromopropane
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Butanone
O
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para-Methoxypropiophenone
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Toluene
Sometimes peaks overlap