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Objectives:
To learn how to interpret IR and NMR spectra. To use IR and NMR spectra to propose a structure for an unknown, given the molecular formula.
Go to the website: www.ochem.com From the left menu, select TUTORIALS. From the right column, PRELECTURES, scroll of the way down the page. Watch the following:
IR SPECTROSCOPY
THINGS TO CONSIDER
OH CH3
What kinds of bonds do I have? If they appeared in the IR spectrum, where would they be?
CH3
IR SPECTROSCOPY
IR SPECTROSCOPY
Full IR Absorption Correlation Table in Appendix J
O-H
3200-3600
C-O
C-H (sp2) C-H (sp3) Aldehyde C-H Amide N-H
1000-1200
(Esters have two!)
3150-3350
C=O
C-X
1650-1740
500-700
DU = (2c + 2) (h n + x) 2
1o unsaturation = 1 C=C or 1 ring 2o unsaturation = 2 C=C, 2 rings, or CC, or combination of C=C & rings 3o unsaturation = combination of double bonds, triple bonds, rings 4o unsaturation = typically indicates an aromatic ring
13C-NMR
SPECTROSCOPY
B.Presence of symmetry
190-220d
aldehydes, ketones
esters, amides, carboxylic acids, acyl halides arenes, alkenes
160-190d
110-160d
50-110d
0-50d
13C
O C O C
O C O C
OR R
O C O C
NR2
C C
C
Fn Csp3
sp3C
o o
Csp3
o
OH R
160-190d
110-160d
190-220d
50-110d
220
210
200
180
160
140
120
100
80
60
40
20
1H-NMR
SPECTROSCOPY
Information provided:
A. Functionality
chemical shift tells the type of hydrogen Via position on x-axis via the # signals Integration
B. Presence of symmetry
via the splitting patterns n+1 rule, where n=# of protons on neighboring carbons
10-12d 9-10d
carboxylic acid
aldehyde
aromatic
alkene
0-2.0d
1H
Notice that there are 8H according to the MF, but we only see 3 signals. This is because some of the hydrogens are equivalent. Number of signals = number of different types of hydrogens present There are 3 different signals because the hydrogens are in 3 different environments.
O Ha C Ha Ha C O H b Hb C C Hc Hc Hc
C4H8O2
INTEGRATION
2H
O C O Ha H b Hb C C Hc Hc Hc
C4H8O2
3H
SPLITTING
Splitting of a signal occurs b/c the chemical shift of a signal can be affected by neighboring protons. Splitting = n + 1, where n = # neighboring protons. Must be within 3 bonds or less. Equivalent hydrogens DO NOT split each other, so Ha would not split each other. Protons cannot see through atoms such as oxygens or nitrogens.
n=0, so n+1 = 1 (singlet)
s q t
O Ha C Ha Ha C O
H b Hb C C Hc Hc
n=2, so n+1 = 3 (triplet)
Hc
TABLE 14.1
Name Molecular Formula Structure Degree of Unsaturation Functional Group
4acetamidophenol
www.chemexper.com
Look up using
www.chemexper.com
Look up using
OMIT
Once you have completed Table 14.1, you will notice 3 questions, followed by 3 sets of combined spectral problems. Each page contains a 1H NMR spectrum, a 13C NMR spectrum, and an IR spectrum pertaining to one of the compounds in Table 14.1. You must identify which set of spectra belong to which compound, and complete the tables by recording actual chemical shift values and IR absorptions.
EXAMPLE TABLE
IR Data* Type of Absorption sp3 CH stretch sp2 CH stretch C-O stretch
H6
Structure
enter chemical shift values from spectra
Frequency (cm-1)
use actual
H3
C1
O
H4,5 C5
3 4 2
C
1
CH3
6
C2
C=O stretch
OH stretch
C6
5 4
3
C3
C4
PROPOSING A STRUCTURE
The final part of the experiment is to practice the ability to propose a structure, given only the molecular formula (MF) and a set of IR and NMR spectra. The best place to start is to calculate the degrees of unsaturation using the provided MF, and use this information as a starting point in the proposal of possible structures.
PROPOSING A STRUCTURE
information gathered from the degrees of unsaturation. Identify how many signals would appear in the spectra of each of the possible proposed structures based on symmetry and equivalent protons. Identify approximate chemical shifts where these types of carbons/protons would appear based on correlation tables. Identify splitting patterns of each type of proton present in each of your proposed structures. Observe the spectra. Using the information you have, eliminate possible structures until you have identified the actual structure.
The FINAL LAB REPORT for Experiment 14 will be due at the beginning of class! The PRE-LAB notebook entry for Experiment 15 will be due at the beginning of class!