1

Taj Taher
Steve Oh
CHEM 242 AM
5 June 2014
Unknown 2 Lab Report (TYR 2)
Introduction
The identity of TYR 2 is 1-tetradecanol, otherwise known as myristyl alcohol.

In the following sections, a compilation of qualitative, derivative, and spectroscopic data is

presented to justify the identification of TYR 2 as such.

Qualitative Tests
Physical Properties:
TYR 2 is a solid compound that is white in color. It forms little pebbles, very much like
miniature white chocolate chips. These are not difficult to crush with a spatula, and the solid
adheres to itself like a paste when crushed. TYR 2 has no odor.
Beilstein:
Negative test. Large red flames produced instead of green flames. Br, Cl, or I not present.
Ignition Test:
Negative test. No black smoke at all, compound mostly just boiled away and some steam was
present. TYR 2 most likely does not contain unsaturation or aromatic groups; not a phenol.
2,4-DNP:
Negative test. When all reagents have been mixed together, the reaction mix becomes a
transparent light orange color. This strongly resembles the 2-butanol control, which means that
TYR 2 does not contain a ketone or aldehyde group which could participate in a reaction with
hydrazine.
Chromic Acid:
Positive test. A murky green colored solution is present when all the reagents are combined,
signaling that chromous sulfate has formed due to the oxidation of TYR 2. This means that TYR
2 could be an aldehyde or a primary/secondary alcohol. However, because the DNP test was
negative, this means that TYR 2 is not an aldehyde, but most likely a primary/secondary alcohol.

Taher 2
Solubility:
Insoluble in NaOH, Insoluble in HCl. Based on PLKE (5/e) Chart on Page 462, the compounds
with such solubility are alkenes, esters, alkynes, ethers, alcohols, amides, ketones, aldehydes, or
nitro compounds. However, the negative DNP disqualified ketones and aldehydes, and the
chromic acid test made primary/secondary alcohols the more likely candidate, which this
solubility test supports.
Lucas Test (Additional):
Upon vigorous shaking of reagents, a top foamy layer formed with an opaque bottom layer. After
allowing the mixture to settle however, the bottom layer seemed far more translucent than
cloudy. A cloudy liquid would imply a tertiary or secondary alcohol, but because the liquid
appears mostly transparent, a primary alcohol seems likely.

Possible Compounds
Melting Point of TYR 2: 31.6 C 35.6 C
Possible Compound

MP (C)

Dodecyl alcohol
Menthol
1-Tetradecanol
1-Hexadecanol

24-27
28-30
35-39
48-50

Table 1
3,5dinitrobenzoate MP
(C)
60
153
67
66

Phenylurethane
MP (C)
74
111
74
73

Structures of Possible Compounds:

Menthol

1-tetradecanol (dodecyl alcohol and hexadecanol are very

similar in structure, just +/- two carbons respectively)

Based on the qualitative tests, an aldehyde or ketone were not likely to be TYR 2, and a
primary/secondary alcohol seemed to be the best candidate. With the Lucas Test however, a
primary alcohol seemed even more likely. The four compounds listed above were the only ones
closest in terms of melting point to that of TYR 2 (+/- 5 C). Alcohols alone were considered
because none of the other solid compounds on the list of possible unknowns shared the same
qualitative test results; carboxylic acids and amines were ruled out due to solubility results,
aldehydes and ketones were ruled out due to the DNP test, unsaturated alcohols were ruled out
due to the negative ignition test, and esters were ruled out due to the positive chromic acid test.
Therefore, it was clear that the plan for derivatives was to synthesize a 3,5-dinitrobenzoate
derivative and a phenylurethane derivative of TYR 2.

Taher 3
Derivative 1: 3,5-Dinitrobenzoate
Reaction:

R
+ R OH

+ HCl

TYR 2

3,5-Dinitrobenzoyl Chloride

Data:

A 3,5-Dinitrobenzoate

Table 2

Compound
TYR 2
Crude Product
1st Recrystallization
2nd Recrystallization

Mass (g)
0.255 used
0.404 produced
0.271 produced
0.230 produced

Melting Point (C)

31.6 35.6
N/A
54.3 57.9
61.3 63.8

Derivative 2: Phenylurethane
Reaction:

Phenyl Isocyanate

R OH

TYR 2

Data:
Compound
TYR 2
Crude Product
Recrystallized Product

Phenylurethane

Table 3
Mass (g)
0.255 used
0.120 produced
0.053 produced

Melting Point (C)

31.6 35.6
61.2 63.8
66.4 68.9

Taher 4

TYR 2 Identification Conclusions Based on Qualitative and Derivative Tests

Here, the results of the qualitative and derivative tests will be synthesized and discussed in order
to justify the conclusion that TYR 2 is 1-tetradecanol (see Introduction for structure).
The qualitative tests narrowed down the field of possible compounds considerably. The solubility
test ruled out the possibility of carboxylic acids, amines, or any low molecular weight
compounds since TYR 2 was insoluble in NaOH and HCl. The negative DNP test made it clear
that an aldehyde or a ketone was not possible, but because the chromic acid test was positive, it
was evident that a primary/secondary alcohol was the main functional group present in TYR 2.
This is because chromic acid oxidizes alcohols and aldehydes, but since the DNP test was
negative, TYR 2 had to be an alcohol. Then, using the Lucas Test, it was concluded that TYR 2
was a primary alcohol. Additionally, the Bielstein test showed that no halide was present, and the
Ignition test showed that there was no aromaticity or unsaturation.
The melting point of TYR 2 (31.5 36.5 C) combined with the qualitative test results showed
that only a few alcohols qualified to be the unknown. From Table 1, these compounds were
Dodecyl Alcohol, Menthol, 1-Tetradecanol, and 1-Hexadecanol. Of these, menthol is the only
secondary alcohol (the rest are primary), and was included in the possible compounds despite the
results of the Lucas Test; this was just to be safe in case the Lucas Test was misinterpreted. Aside
from these alcohols, the other alcohols within range of the melting point for TYR 2 had some
degree of unsaturation (Cinnamyl Alcohol) and were not considered.
The qualitative tests allowed for the scope of possible compounds to be narrowed down to just
four, but the derivative tests and original melting point of TYR 2 provided the definitive answer.
First, the twice purified 3,5-Dinitrobenzoate product of TYR 2 had a melting point of 61.3 63.8
C, as shown in Table 2. This result immediately ruled out menthol since from Table 1 it has
a literature derivative melting point of 153 C. Unless the derivative was still extremely impure
after two recrystallizations, it is unlikely that menthol was TYR 2. This also supports the Lucas
Test result, as menthol is a secondary alcohol and the test provided a primary alcohol result. The
3,5-dinitrobenzoate melting point of TYR 2 also ruled out Dodecyl Alcohol, as its literature
derivative melting point is 60 C. Melting points for an impure compound are always lower, so
the fact that after recrystallizing the melting point was higher than that of Dodecyl Alcohols
derivative shows that TYR 2 cannot be Dodecyl Alcohol. This is also reflected in the fact that the
melting point for Dodecyl Alcohol is at 24-27 C, which is far lower than that of TYR 2. Once
again, if TYR 2 was impure, then its melting point would have be lower than 24-27. That said,
the 3,5-Dinitrobenzoate derivative test ruled out two of the four possible compounds, leaving
only 1-tetradecanol and 1-hexadecanol.
The phenylurethane derivative, however, was not useful in helping distinguish TYR 2 as one of
those two compounds, because the literature value of the phenylurethane for 1-tetradecanol is 74
C and for 1-hexadecanol it is 73 C. The melting point of the phenylurethane derivative of TYR
2 was 66.4-68.9 C, which strongly supported that it was one of the two. However, the deciding
factor for 1-Tetradecanol being TYR 2 was that its original melting point of 31.5-36.5 C was
much closer to the literature value of 1-Tetradecanol (35-39C) than that of 1-Hexadecanol (4850 C). While TYR 2 may have had some impurities, it probably was not so impure as to depress

Taher 5
its melting point by more than 20 degrees. This methodological approach from qualitative test, to
original melting point, to derivative values is how TYR 2 was determined to be 1-tetradecanol.
Contradictory Tests
There were no contradictory test results during this process. Every single test that was performed
was useful in determining the identity of the compound, and every single test (as described in
detail in the previous pages) supports 1-tetradecanol as being TYR 2.

Spectroscopic Data
In the following sections, the attached IR and NMR data of TYR 2 will be analyzed in order to
support 1-tetradecanol as being the identity of TYR 2.
IR:
On the IR (Figure 1, attached), there are really only two major absorptions. One is at 3236.9 cm1
, and it is medium sized while being quite broad. This is characteristic of an alcohol functional
group. Based on the structure of 1-tetradecanol, this makes sense as it is a primary alcohol. The
only other major peaks are a sharp cluster of large peaks at 2850.9, 2919.9, and 2957.8 cm-1
which are all indicative of an alkyl stretch. This also follows the structure of 1-tetradecanol, as it
is comprised almost entirely of an alkyl chain. Finally, the absence of any other significant peaks
in the IR shows that no other functional group is present in TYR 2, just as there are no other
additional functional groups in 1-tetradecanol. The IR, on the level of functional groups, supports
1-tetradecanol as TYR 2.
NMR:
On Figure 2 there is an NMR of TYR 2 with a structure of 1-tetradecanol labeled with
corresponding hydrogens. The NMR of TYR 2 strongly matches the structure of 1-tetradecanol.
1-tetradecanol has 30 Hs, and when the integrations on the NMR of 1.70, 11.90, 1.11, and 1.00
are rounded, scaled up by two, and added, they sum to 31. This is a minor difference (and 1Hexadecanol, the only other possible compound, has 34 Hs, which is even further off).
The peaks themselves also show that TYR 2 is 1-tetradecanol. The peak labeled HD at about
0.8ppm integrates and is scaled up to 3, and thus represents the methyl group at the end of the
chain. It has a triplet splitting pattern, which makes sense as it is neighbored by only two
hydrogen. The peak HA on the other hand is at around 3.6ppm, corresponds to the hydrogens
bonded to the carbon directly attached to the alcohol. This makes sense as this chemical shift is
characteristic of such an arrangement, due to the electron withdrawing of oxygen. The splitting
pattern of HA is a quartet, which is somewhat unexpected since the hydrogen directly attached to
the hydrogen typically does not split neighboring hydrogens. In this case however, it seems that
HB and the H on the alcohol are the three hydrogens that give a quartet splitting pattern. As for
HB itself, its ppm is at about 1.6. The pair of hydrogens this peak corresponds to are on Carbon 2
of 1-tetradecanol, and this chemical shift is typical of hydrogens that are this particular distance
from the electron withdrawing tendency of oxygen. HB is just the distance from the oxygen to
have a chemical shift not as high as HA, but not nearly as low as a simple alkyl hydrogen. The
splitting pattern is hard to distinguish, as it is being split by HA and HC.

Taher 6
Interpreting HC was tricky. The first thing to note is that there are 22 HCs labeled on the structure
of 1-tetradecanol, but the peak integrates and scales up to 24. One will also notice that a peak for
the hydrogen of the alcohol does not appear on the NMR. Both are connected, as the peak for the
H-O probably blended into the peak for HC. If this were true, then the combined peaks would
integrate to 23, and since we scaled up by 2, the peak on the NMR for TYR 2 should be 11.5,
which is very close to the 11.9 that is actually on the NMR. Therefore, the reason that number of
hydrogens adds up to 31 instead of the 30 of 1-tetradecanol is because these two peaks combined
and because there was a rounding issue. Also, NMR is hardly ever perfect, and this may have
been an error in the solvent or when running the sample. However, this supports the notion that
TYR 2 is indeed 1-tetradecanol, for in addition HC is at a chemical shift that matches all the
hydrogens in the long alkyl chain, and is supported by the relevantly large integration. For these
reasons, the NMR of TYR 2 clearly matches up with the structure of 1-tetradecanol as all the
peaks and hydrogens correspond and are accounted for.