LAB REPORT TIPS!!

Use a Laboratory Book!!!!

Do not describe standard techniques such as:
How to take a melting point
How to do a recrystallisation
The type of glassware you use
How to prepare an IR sample
How to do a filtration

Remember to be concise when writing reports. Don´t show me you calculations. I can
assume by now that you know how to calculate % yield!!! Don´t write “I did this..”

READ THE AUTHORS INSTRUCTIONS !!!!!!!!

The yields are often not more accurate than 0 decimal places. So I don´t expect to see
23.22%. This is 23%. The same applies to masses 2.0054 g should be in your Lab Book.
Your report will show 2.01 g or 2.0 g or even 2 g.

Please try to read and understand the presentation of experimental details and
spectroscopic data that is recommended in the Authors Instruction that you have been
supplied with. There is no other correct way to write an Experimental. How you arrive
at your spectroscopic assignments should be discussed briefly in your Results and
Discussion section

MECHANISM

Try to be efficient! Proton transfers can be implied. The more detail you propose for any
mechanism the more support you must have. There are often many possible solutions.

Acetylation

HO+ O O O
+ + H+
O OH OR

ROH

Esterification

O
O
+
OH2 + H3O +
OR
ROH
The longer routes are equally correct.
 IR SPECTROSCOPY

IR spectroscopy for the organic chemist is a primary tool (cheap and fast) to detect the
presence of (or lack of) functional groups. Try to identify the characteristic vibrations
only. Most of these are found between 4000 and 1400cm-1, some other functional groups
such as nitro, sulphone, and sulfoxide stretches appear between 1400 and 1000cm-1.
Ultimately there are very few stretching frequencies to remember, LEARN THEM. A
good spectroscopy book can help you differentiate between certain very similar
functional groups but it will only be a tentative assignment, BE CAREFUL. Many of you
have listed peaks which are not on your spectra!!! DO NOT DO THIS IN FUTURE. Do
not include peaks that are masked (hidden) by the Nujol resonances. Learn these by
heart!! Nujol is a hydrocarbon therefore it masks many stretches that arise from alkyl
groups!!

Aspirin

The IR spectrum of Aspirin immediately indicates that the expected hydroxy group
ν(O-H) is difficult to identify, IT MAY NOT BE PRESENT. However, you may suggest
it is hidden under the Nujol stretches (2950-2850cm-1) between 3000 and 2500cm-1. The
aromatic ν(C-H) stretch usually around 3100 and 3030cm-1 has not appeared in many of
your specta presumably due to the poor quality. If you can´t see it don´t list it! The alkyl
stretches from the methyl group will be hidden by the Nujol.

The most important stretching frequencies to identify are from the carbonyl ν(C=O)
groups. There are TWO carbonyl groups, one from the carboxylic acid and one from the
acetyl group. Identify them and try to predict which is which. Not so easy…

I found from your spectra 1755 and 1685cm-1 as the two carbonyl stretching frequencies.
To identify which belongs to which carbonyl group requires careful comparison with
similar compounds. Looking at the IR spectra of salicylic acid, aspirin and its methyl
ester my tentative conclusion was that the acetyl carbonyl belonged to 1755cm-1 and that
the aromatic carboxylic acid belonged to 1685cm-1. This makes sense if you consider that
the aryl group can contribute resonance forms to the ester which reduces the double bond
character of the carbonyl group. Less double bond character, gives a weaker bond, and a
lower stretching frequency.
 O
CH3 O
O
vrs
H3C O

The aryl ν(C=C) stretches are clearly visible at 1605cm-1. The next two stretches are from
Nujol, 1460 and 1378cm-1. After these peaks the only main stretches that remain are the
asymmetric and symmetric ν(C-O) stretches of the ester groups. The range for these
stretches is approximately between 1330 and 1050cm-1. From spectroscopy books the
asymmetric stretch is reported to be more intense and higher in frequency than the
symmetric stretch. So we may assign ν(C-O) asym to 1300cm-1 and ν(C-O) sym to
1185cm-1. From a good spectroscopy book we could go further!! The asymmetric stretch
for acetates is around 1240cm-1, and we have in our spectra a stretch near this at
1220cm-1, however, such assignments are very dangerous.

The fingerprint region from 1000-400cm-1 is harder to assign. But as its name suggests is
used to pin point the identity of many organic structures.

NMR SPECTROSCOPY
Methyl Salicylate

Mp –8 to –7oC
Bp 222oC
Colourless Oil
1
H NMR analysis

In the Results and Discussion section of your reports I expect a similar analysis, this will
be different from the presentation of the data in the Experimental section.

H3 O

H4 3 CH3
7 O 8
4 2

H5 5 1 OH
6

H6

Phenol OH ca. 9.3 ppm

Acetate CH3 ca. 3.5-4.0 ppm

Ignoring the meta and para couplings which are small and may or may not appear then
we observe:

Chemical Shift Pattern Coupling Integration Assignment Hydrogen

(ppm) Constant
(J/ Hz)
10.79 singlet - 1 Hydroxy OH
7.82 doublet 8.0 1 Ar H H or H6
3

7.44 triplet 7.8, 7.8 1 Ar H H4 or H5

6.98 doublet 8.4 1 Ar H H3 or H6
6.87 triplet 7.6, 7.6 1 Ar H H4 or H5
3.92 singlet - 3 Methyl CH3

The phenolic hydroxyl group is strongly ortho- and para- activating and therefore
increases electron density in these position. (Draw some resonance structures if your not
convinced!) Increased electron density causes shielding which results in an upfield shifts
of the expected NMR signal. Tentatively we expect 6.87 ppm signal to correspond to H4
and 6.98 ppm to correspond to H6. Therefore 7.44 ppm could be H5 and 7.82 ppm H3.

The methyl ester group is strongly ortho- and para- deactivating (meta-directing) and
therefore decreases electron density in these positions. Decreased electron density causes
deshielding which results in a down field shift of the expected NMR signals. Tentatively
we expect 7.44 ppm signal to correspond to H5 and 7.82 ppm to correspond to H3.
Therefore 6.87 ppm could be H4 and 6.98 ppm H6.

Both analysis agree on the proton assignments but such a qualitative analysis is not
conclusive.

Benzene substituent effects are additive and a semi-quantitative analysis can be carried
out.

δ
4 X Hi = 7.26 + Zi

3 2

Substituent X Z2 Z3 Z4
H 0 0 0
OH -0.56 -0.12 -0.45
CO2Me 0.71 0.11 0.21

Therefore for methyl salicylate the position of protons around the aromatic ring can be
tentatively predicted.

H6 = 7.26 + (-0.56) + (0.11) = 6.81 ppm vrs 6.98 ppm

 H5 = 7.26 + (-0.12) + (0.21) = 7.35 ppm vrs 7.44 ppm
H4 = 7.26 + (-0.45) + (0.11) = 6.92 ppm vrs 6.87 ppm
H3 = 7.26 + (-0.12) + (0.71) = 7.85 ppm vrs 7.82 ppm

Not Perfect but Not Bad. The qualitative approach gave different assignments for
protons H6 and H4, however, their splittings H6 (doublet) and H4 (triplet) allows strong
support of their identity. The additive approach is, however, a useful aid in NMR
assignment. 1H NMR data is typically presented to 2 decimal places (2 d.p.) in the
following manner and at the end of the Experimental:

δH(300 MHz, CDCl3) 10.79 (1H, s, Ar OH), 7.82 (1H, d, J 8.0 Hz, H3), 7.44 (1H, t, J 7.8,
7.8 Hz, H5), 6.98 (1H, d, J 8.4 Hz, H6), 6.87 (1H, t, J 7.6, 7.6 Hz, H4), 3.92 (3H, s, CH3);
13
C NMR analysis

Typically the same type of analysis can be carried out for 13C NMR.

H3 O
H4 3 CH3
7
4 2 O 8

H5 5 1 OH
6

H6
Decoupled, Eight peaks are observed, (ignoring the solvent peaks!!). The methyl carbon
is immediately recognizable due to its high field chemical shift. The carbonyl group is
typically down field (from Tables) and could be either 170.44 or 161.45 ppm. Since
quaternary carbons do not relax as quickly as tertiary, secondary and primary carbons
then the peak intensities (and the chemical shifts!) indicate which peaks correspond to Ar
CH and which to Ar quaternary carbons. The following information becomes available:

Chemical Shift Assignment Dept 135

(ppm) (ppm)
170.44 C=O or Ar quaternary
161.45 C=O or Ar quaternary
135.55 Ar CH 135.55
129.77 Ar CH 129.77
119.01 Ar CH 119.02
117.40 Ar CH 117.40
112.21 Ar quaternary
52.12 CH3 52.13
The 13C DEPT 135 NMR experiment shows all tertiary R3CH and primary RCH3 carbons
up and secondary R2CH2 carbons down. Analysis of the spectrum supports the above
assignments.

Again, the hydroxy group is ortho- and para-activating so the carbon signals at C-2, C-4
and C-6 should experience upfield shifts. The methyl ester group is ortho- and para-
deactivating and so the carbon signals at C-1, C-3 and C-5 should experience downfield
shifts. Since the chemical shift for carbon in benzene is 128.5 ppm we can derive more
information from our qualitative analysis:

Peaks 112.21, 117.40 and 119.01 ppm correspond to either C-2, C-4 or C-6. We know
that 112.21 must be the quaternary carbon C-2.

Peaks 170.44 and 161.45 ppm correspond to either C=O or C-1 and 135.55 and 129.77
ppm correspond to either C-3 or C-5.

The Table can be updated to show the new information.

Chemical Shift Assignment Dept 135 Qualitative

(ppm) (ppm) analysis
170.44 C=O or Ar quaternary C=O or C-1
161.45 C=O or Ar quaternary C=O or C-1
135.55 Ar CH 135.55 C-3 or C-5
129.77 Ar CH 129.77 C-3 or C-5
119.01 Ar CH 119.02 C-4 or C-6
117.40 Ar CH 117.40 C-4 or C-6
112.21 Ar quaternary C-2
52.12 CH3 52.13 CH3

The inductive effect, which decreases with through bond distance operates counter to the
resonance effect. Thus shielding effects are more pronounced for ortho- positions than
for para-positions. This argument may not always be the case.

If this were true then a further qualitative assessment can be made: 117.40 is C-6, 119.01
is C-4, 129.77 is C-5 and 135.55 is C-3. Tentatively the furthest down field peak would
most probably be the carbonyl peak at 170.44 and hence C-1 is 161.45 ppm.

Such assignments are very very risky!!!!

Correlations with Tables can support such assignments. Benzene substituent effects are
additive and a semi-quantitative analysis can be carried out!
 δ
4 X Ci = 128.5 + Zi
1

3 2

Substituent X Z1 Z2 Z3 Z4
H 0 0 0 0
OH 26.9 -12.8 1.4 -7.4
CO2Me 2.0 1.2 -0.1 4.3

C-1 = 128.5 + (26.9) + (1.2) = 156.6 ppm vrs 161.45 ppm

C-2 = 128.5 + (-12.8) + (-0.1) = 115.6 ppm vrs 112.21 ppm
C-3 = 128.5 + (1.4) + (4.3) = 134.2 ppm vrs 135.55 ppm
C-4 = 128.5 + (-7.4) + (-0.1) = 121.0 ppm vrs 119.01 ppm
C-5 = 128.5 + (1.4) + (1.2) = 131.1 ppm vrs 129.77 ppm
C-6 = 128.5 + (-12.8) + (2.0) = 117.7 ppm vrs 117.40 ppm

Not Bad!!!

So just from a decoupled C NMR and a Dept NMR, a little experience and access to
Tables from the literature lot of information can be deduced allowing for a tentative
assignment of all peaks. The ability to perform such analysis is CRUCIAL!!

Can we do better??
13
C Coupled NMR

The coupled 13C NMR experiment shows the splitting effect protons have on
neighbouring carbon environments. Just like a normal H NMR. Lets work through the
NMR from Left to Right.

170.43 ppm shows up as a singlet and this strongly supports the above carbonyl
assignment.
161.46 ppm is poorly resolved but some splitting is tentatively observed. a doublet, J 2
Hz. The splitting is weak and this is expected for a quaternary carbon that is at least 2
bonds from its nearest H.
135.55 ppm is double doublet (dd), J 9, 158 Hz. The large splitting is typical for a one-
bond coupling (1JC-H 159 Hz for benzene) and suggests the carbon is directly attached to
Hydrogen. The smaller splitting is typical for a three-bond coupling!! (3JC-H 7-10 Hz for
13
C labeled benzene) and suggests the signal belongs to either carbons C-3, C-4, C-5 or
C-6. Two bond couplings are very weak and often not observed (2JC-H 1 Hz for 13C
labeled benzene).
129.77 ppm is double doublet (dd), J 8, 162 Hz. This suggests the signal belongs to either
carbons C-3, C-4, C-5 or C-6.
119.01 ppm is double doublet (dd), J 8, 162 Hz. This suggests the signal belongs to either
carbons C-3, C-4, C-5 or C-6.
117.40 ppm is double triplet (dt), J 8, 8, 161 Hz. This is tricky and suggests the signal
belongs to carbons C-6, since only the phenolic hydrogen, which is three bonds removed,
can explain the extra coupling of 8 Hz.
112.21 ppm is complex, tentatively a quintet (quin), J 4 Hz. In reality this carbon which
is C-2 should show 3 three-bond couplings and hence should be a double doublet of
doublets (ddd). Coupling with the hydrogens at C-4, C-6 and OH. The complexity
creates some overlap of peaks in the spectrum and this is reflected by the unusual J value
and the apparent quintet multiplicity.
52.12 ppm is a quartet (q), J 147 Hz and corresponds to the methyl group with 3
hydrogens.

As you can see, the coupled NMR gives us information but not much more than could be
deduced from the decoupled NMR and the DEPT. Coupled NMR is rarely used
nowadays and decoupled NMR remains the standard for Carbon NMR spectroscopy.
More useful information can be obtained from 2-D NMR experiments, such as NOSY
and COSY experiments. I hope you will encounter these shortly :o)

In the Experimental section the data should be presented in the following manner:

δH(300 MHz, CDCl3) 10.79 (1H, s, Ar OH), 7.82 (1H, d, J 8.0 Hz, H3), 7.44 (1H, t, J 7.8,
7.8 Hz, H5), 6.98 (1H, d, J 8.4 Hz, H6), 6.87 (1H, t, J 7.6, 7.6 Hz, H4), 3.92 (3H, s, CH3);
δC(75 MHz, CDCl3) 170.44 (C=O), 161.45 (C-1), 135.55 (C-3), 129.77 (C-5), 119.01
(C-4), 117.40 (C-6), 112.21 (C-2), 52.12 (CH3); δC(75 MHz, 135 DEPT, CDCl3) 135.55
(C-3), 129.77 (C-5), 119.01 (C-4), 117.40 (C-6), 52.12 (CH3); δC(75 MHz, Coupled,
CDCl3) 170.44 (s, C=O), 161.45 (m, C-1), 135.55 (dd, J 9, 158 Hz, C-3), 129.77 (dd, J 8,
162 Hz, C-5), 119.01 (dd, J 8, 162 Hz, C-4), 117.40 (dt, J 8, 8, 162 Hz, C-6), 112.21
(apparent quintet, J 4 Hz, C-2), 52.12 (q, J 147 Hz, CH3); …………

Aspirin
Mp 140 to 141oC
Colourless Plates

In an analogous manner the 1H and 13C spectra of Aspirin can be evaluated.

 H3 O

H4 3
7 OH
4 2

H5 5 1 O
6

H6 8
9
O CH3

Carboxylic acid OH ca. 10-13 ppm

Acetyl CH3 ca. 2.0-2.5 ppm

With this spectrum the meta and para couplings are quite clear, but for simplicity I shall
not include them here.

Chemical Shift Pattern Coupling Integration Assignment Hydrogen

(ppm) Constant
(J/ Hz)
11.20 singlet - 1 Hydroxy OH
8.13 doublet 7.9 1 Ar H H3 or H6
7.63 triplet 7.8, 7.8 1 Ar H H4 or H5
7.36 triplet 7.6, 7.6 1 Ar H H4 or H5
7.14 doublet 8.1 1 Ar H H3 or H6
2.35 singlet - 3 Methyl CH3

The acetylated phenolic hydroxyl group is no longer strongly ortho- and para- activating
since the lone pair of electrons on the phenolic oxygen are now conjugated with the
carbonyl group of the acetyl. (Check this with resonance structures). However the lone
pair of the oxygen can still conjugate with the aryl ring and therefore moderately ortho-
and para- activating. Tentatively we expect 7.36 ppm signal to correspond to H4 and 7.14
ppm to correspond to H6. Therefore 7.63 ppm could be H5 and 8.13 ppm H3.

The carboxylic acid group is similar to the methyl ester group and therefore is strongly
ortho- and para- deactivating. (Check this with resonance structures). Tentatively we
expect 7.63 ppm signal to correspond to H5 and 8.13 ppm to correspond to H3. Therefore
7.36 ppm could be H4 and 7.14 ppm H6.

Checking the above with the additive rules of mono-substituted benzene we find.
 δ
4 X Hi = 7.26 + Zi

3 2

Substituent X Z2 Z3 Z4
H 0 0 0
OH -0.56 -0.12 -0.45
OAc -0.25 0.03 -0.13
CO2Me 0.71 0.11 0.21
CO2H 0.85 0.18 0.27

Therefore for methyl salicylate the position of protons around the aromatic ring can be
tentatively predicted.

H6 = 7.26 + (-0.25) + (0.18) = 7.19 ppm vrs 7.14 ppm

H5 = 7.26 + (0.03) + (0.27) = 7.56 ppm vrs 7.63 ppm
H4 = 7.26 + (-0.13) + (0.18) = 7.31 ppm vrs 7.36 ppm
H3 = 7.26 + (0.03) + (0.85) = 8.14 ppm vrs 8.13 ppm

Not Bad. The qualitative and the semi-quantitative approach gave fairly good agreement
for the 1H NMR assignments. VERY NICE

δH(300 MHz, CDCl3) 11.20 (1H, s, Ar CO2H), 8.13 (1H, d, J 7.9 Hz, H3), 7.63 (1H, t, J
7.8, 7.8 Hz, H5), 7.36 (1H, t, J 7.6, 7.6 Hz, H4), 7.14 (1H, d, J 8.1 Hz, H6), 2.35 (3H, s,
CH3);

13
C NMR analysis

H3 O

H4 3
7 OH
4 2

H5 5 1 O
6

H6 8
9
O CH3
Decoupled, Nine peaks are observed, (ignoring the solvent peaks!!). The methyl carbon
is immediately recognizable due to its high field chemical shift. The carbonyl groups are
typically down field. Since quaternary carbons do not relax as quickly as tertiary,
secondary and primary carbons then the peak intensities (and the chemical shifts!)
indicate which peaks correspond to Ar CH and which to Ar quaternary carbons. The
DEPT 135 confirms the Ar CH and CH3 assignment. Furthermore, taking into
consideration the substituents activating and deactivating effects on the aryl ring a
qualitative assignment can be proposed for the aryl carbons. The following information
becomes available:

Chemical Shift Assignment Dept 135

(ppm) (ppm)
170.15 C=O
169.73 C=O
151.25 Ar quaternary, C-1
134.88 Ar CH, C-3 134.88
132.50 Ar CH, C-5 132.50
126.15 Ar CH, C-4 126.15
124.00 Ar CH, C-6 124.00
122.22 Ar quaternary, C-2
20.98 CH3 20.98

Correlations with Tables just to check!!

δ
4 X Ci = 128.5 + Zi
1

3 2

Substituent X Z1 Z2 Z3 Z4
H 0 0 0 0
OH 26.9 -12.8 1.4 -7.4
OAc 22.4 -7.1 0.4 -3.2
CO2Me 2.0 1.2 -0.1 4.3
CO2H 2.1 1.6 -0.1 5.2

C-1 = 128.5 + (22.4) + (1.6) = 152.5 ppm vrs 151.3 ppm

C-2 = 128.5 + (-7.1) + (-0.1) = 121.3 ppm vrs 122.2 ppm
C-3 = 128.5 + (0.4) + (5.2) = 134.1 ppm vrs 134.9 ppm
C-4 = 128.5 + (-3.2) + (-0.1) = 125.2 ppm vrs 126.2 ppm
C-5 = 128.5 + (0.4) + (1.6) = 130.5 ppm vrs 132.5 ppm
C-6 = 128.5 + (-7.1) + (2.1) = 123.5 ppm vrs 124.0 ppm

Not Bad!!!
Differentiating between the two carbonyl peaks can be done with the 13C coupled NMR.
The peak at 170.15 ppm is a doublet (2JC-H = 4.5 Hz), and this splitting has to be due to
the hydroxy proton, therefore 170.15 is C-7. The peak at 169.73 ppm is a quartet (2JC-H =
7.0 Hz), and this splitting has to be due to the 3 methyl protons, therefore 169.73 is C-8.
Finally present the data in the Experimental section in standard journal format.

Lastly….

START READING THE JOURNALS!!!