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Experiment 14:

IR AND NMR IDENTIFICATION OF AN UNKNOWN

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.

Before coming to lab

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:

SPECTROSCOPY (Part 3 of 4) SPECTROSCOPY (Part 4 of 4)

(YOULL BE GLAD YOU DID! )

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

Now, look at the spectrum. Are they there?

IR SPECTROSCOPY

IR SPECTROSCOPY
Full IR Absorption Correlation Table in Appendix J

Base values for Absorptions of Bonds (cm-1)

O-H

3200-3600

C-O
C-H (sp2) C-H (sp3) Aldehyde C-H Amide N-H

1000-1200
(Esters have two!)

3000-3100 2850-3000 2700 & 2800


(there are two!)

3150-3350

C=O
C-X

1650-1740
500-700

CALCULATING DEGREE OF UNSATURATION CcHhNnOoXx

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

Information provided: A.Functionality (Chemical Shift)


tells the type of carbon via position of signal on x-axis via # of signals

B.Presence of symmetry

C.Presence of non-protonated carbons


via small signals sometimes useful, not always!

TYPICAL CHEMICAL SHIFTS

190-220d

aldehydes, ketones
esters, amides, carboxylic acids, acyl halides arenes, alkenes

160-190d

110-160d

50-110d

alkynes, sp3C attached to functional groups


sp3C-Csp3, where 4o>3o>2o>1o

0-50d

13C

NMR CHEMICAL SHIFT CORRELATION CHART

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

4 --3 --2 --1o


0-50d

110-160d
190-220d

50-110d

220

210

200

180

160

140

120

100

80

60

40

20

p. 118 in lab manual

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

C. Number of protons of each type per signal

D. Number of neighboring protons per signal


via the splitting patterns n+1 rule, where n=# of protons on neighboring carbons

TYPICAL CHEMICAL SHIFTS


10-12d 9-10d

carboxylic acid
aldehyde

6.5-8.5d 5.0-6.5d 2.0-4.5d

aromatic
alkene

0-2.0d

alkyne, hydrogens on carbons attached to functional groups


sp3C-H, typically 3o>2o>1o

1H

NMR CHEMICAL SHIFT CORRELATION CHART

SYMMETRY & EQUIVALENCE

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

The integration is proportional to the # hydrogens causing that signal.


There are 3 Ha protons There are 2 Hb protons There are 3 Hc protons


3H
Ha C Ha

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

n=3, so n+1 = 4 (quartet)

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

Must be calculated using MF

OMIT

propyl acetate benzaldehyde

COMBINED SPECTRAL PROBLEMS

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

numerical values from spectra

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

Using the MF, calculate the degrees of unsaturation.

Propose possible structures based on the MF and

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.

For next lab

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!

Safety goggles and closed toe shoes are MANDATORY!