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Taj Taher
Steve Oh
CHEM 242 AM
5 June 2014
Unknown 1 Lab Report (TYR 1)
Introduction
The identity of TYR 1 is 4Allyl2methoxyphenol (eugenol).

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


presented to justify the identification of TYR 1 as such.

Qualitative Tests
Physical Properties:
TYR 1 is a liquid compound that has a rich golden color. It is oily and somewhat viscous in
nature and gives off a strong spice-like odor. It is not unpleasant, but it is quite pungent.
Beilstein:
Negative test. Large red flames produced instead of green flames. Br, Cl, or I not present.
Ignition Test:
Positive test. Bright red flames produced upon contact with burner, and black smoke was visible
in fairly good quantities. Aromatic or unsaturation present, phenol possible.
2,4-DNP:
Negative test. A dark orange but transparent liquid forms when all reagents are mixed, no sign of
precipitate. The mixture resembles the 2-butanol control. A ketone or an aldehyde are not likely.
Chromic Acid:
(False?) Positive test. There is a distinct color change, but instead of the green color to be
expected of a positive test, the reaction mixture is dark brown. This may just be a darker shade of
green, or perhaps some impurities within the mixture (if the acetone reacted with the chromic
acid even though it is not supposed to). Tentatively, an aldehyde or a primary/secondary alcohol
are possible, but this may just be a false positive.

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Solubility:
Soluble in NaOH, Insoluble in NaHCO3. Based on PLKE (5/e) Chart on Page 462, the
compounds with such solubility are phenols.
Cerium (IV) Test (Additional):
Positive Test. A very dark red color forms, verging on almost scotch color. Phenol is clearly
present, but no dark brown precipitate forms indicating a simple phenol. TYR 1 from this test
seems to be a substituted phenol.

Possible Compounds
Boiling Point of TYR 1: 254 C

Table 1

Possible Compound

Boiling Point
243
253

Napthylurethane MP
(C)
129
122

Bromo Derivative
MP (C)
104 tri
118 tetra

3Methoxyphenol
4-Allyl-2-methoxy
phenol
2Methoxy4
propenylphenol

268

150

N/A

Structures of Possible Compounds:

3-Methoxyphenol

4-Allyl-2-methoxy phenol

2Methoxy4propenylphenol

The solubility test and the Cerium (IV) test confirmed that TYR 1 was a phenol. As such, only
phenols were considered as possible compounds. Since TYR 1 has a boiling point of 254 C, it
seemed immediately clear that it was probably eugenol. But for the sake of being accurate, 2Methoxy-4-propenylphenol and 3-Methoxyphenol were considered in case the boiling point was
not recorded accurately, as these two compounds are closest to the boiling point of TYR 1 and
share the same chemical properties as defined by the qualitative tests.
Even though it was clear that TYR 1 was most likely eugenol based on boiling point, synthesis of
the napthylurethane derivative and bromo derivative would potentially help confirm this
identification.

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Derivative 1: -Napthylurethane
Reaction:

+
-Napthyl isocyanate

Phenol
(like TYR 1)

An -Napthylurethane

Data:
Table 2
Compound
TYR 1
Crude Product
1st Recrystallized Product
2nd Recrystallized Product

Mass (g)
0.275 used
0.204 produced
0.251
0.014

Melting Point (C)


N/A
98.6 - 102.4
99.4 - 105.6
113.5 - 116.8

Derivative 2: Bromo Derivative


Reaction:

Results:
Unfortunately, after many attempts, the synthesis of a bromo derivative from TYR 1 was
unsuccessful. Rather than making a white precipitate, TYR 1 created a black oil, regardless of
the amount of brominating solution added. This may be due to TYR 1s intrinsic physical
qualities of being oil-like, and thus not easily dissolved in the mixture of methanol and water.

Derivative 3: 3,5-Dinitrobenzoate
Reaction:
+

Results:

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After the unsuccessful bromo derivative, a dinitrobenzoate derivative of TYR 1 was attempted.
This too proved futile however, for rather than forming a precipitate, an oil formed both times
this derivative was attempted.
TYR 1 Identification - Conclusions Based on Qualitative and Derivative Test Results
The results of the qualitative and derivative tests will be synthesized and discussed below in
order to justify the identification of TYR 1 as 4-Allyl-2-methoxyphenol (eugenol). The structure
is provided in the introduction.
The most important qualitative tests in helping to identify eugenol were the solubility test, the
ignition test, and the Cerium (IV) test. The fact that TYR 1 was soluble in NaOH heavily
narrowed down the field to just carboxylic acids and phenols. But then, since TYR 1 was
insoluble in NaHCO3, it was clear that TYR 1 was most likely a phenol. The ignition test helped
support this result, as TYR 1 tested positive because of the presence of sooty flames when
burned. This demonstrates that TYR 1 had some degree of unsaturation or aromaticity, which is
an inherent part of the phenol from the benzene ring. Finally, the Cerium (IV) test gave a positive
test in the form of a deep red color forming upon mixing, which indicated the presence of a
phenol. Since no dark brown precipitate formed, an unsubstituted phenol was unlikely; in
addition, although the Cerium (IV) test also provides positive results for alcohols, TYR 1 was
already determined to not be a simple alcohol due to the solubility results.
The other qualitative tests support eugenol as being TYR 1. The Bielstein Test was negative,
indicating that no halide groups such as Br, Cl, or I are present. The DNP test was negative,
showing that TYR 1 has no aldehyde or ketone group, which matches up with eugenol. Finally,
the Chromic Acid test gave a false positive as it did form a precipitate, but not the green color
that is expected from the oxidation of an aldehyde or primary/secondary alcohol. The only guess
to explain why TYR 1 produced a dark brownish precipitate is that the phenol in eugenol did
interact with the Chromic Acid to some degree.
Once the qualitative tests made it clear that TYR 1 was a phenol, the boiling point determination
helped narrow the field considerably. With a boiling point of 254 C, 3-Methoxyphenol, eugenol,
and 2Methoxy4propenylphenol were the only phenols that came close to the boiling point of
TYR 1. Of these, eugenol was the closest with a boiling point of 253 C. This fact became very
important because the synthesis of derivatives was problematic. Both the Bromo Derivative and
the 3,5-Dinitrobenzoate Derivative did not synthesize properly from TYR 1. The
Napthylurethane Derivative was more successful however. The derivative synthesized from TYR
1 and napthyl isocyanate yielded a melting point after two purifications of 113.5 116.8 C.
Based on the literature values of the derivatives in Table 1, this derivative is closest in melting
point to that of eugenols (122 C). There is a small chance that the synthesized product was not
pure enough and that the melting point was depressed, but since the derivative from 2Methoxy
4propenylphenol is a good 30 C above this value, it seems unlikely. However, 3Methoxyphenol has a decent chance of being TYR 1 since the literature melting point of its
napthylurethane derivative is 129 C, which is much closer to TYR 1s napthylurethane
derivative. However, the boiling point of eugenol and TYR 1 match up almost perfectly, while 3Methoxyphenol has a boiling point that is 10 C lower. For this reason and the fact that the
derivative melting point of eugenol and TYR 1 match up, TYR 1 is most likely eugenol.
Contradictory Tests

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Aside from the baffling Chromic Acid test, none of the test results contradicts eugenol as being
TYR 1. All qualitative and derivative tests confirm eugenol as TYR 1 through the reasons
detailed above.
Spectroscopic Data
In the following sections, the attached IR and NMR data of TYR 1 will be analyzed in order to
support eugenol as being the identity of TYR 1.
IR:
The IR on Figure 1 for TYR 1 has several major absorptions that strongly support the
identification as eugenol. The first and most obvious is the short, broad peak at 3517.9 cm-1
which corresponds to the alcohol functional group of eugenol. The next absorption is a series of
peaks centralized at 2939.1 cm-1. This falls on the edge of two regions, the C-H alkane region
(generally from 2850-3000 cm-1) and the C-H alkene region (generally from 3000-3100). The
fact that this absorption is not particularly strong makes sense for eugenol, as there are only three
carbons at the para position of the aromatic ring, with one carbon having alkane C-H bonds and
two carbons with alkene C-H bonds. The aromatic ring is greatly emphasized however,
particularly by the sharp peaks at 1432.3, 1514.0, and (to a lesser degree) 1612.6 cm-1, which
result from the aromatic C-C bond vibrations.
One peak that should have been marked even though it falls within the > 1400 cm-1 fingerprint
region is a larger sharp absorption between 1000 and 1500 cm-1. While its exact position may not
be known, an estimate would place it around 1250 or 1300 cm-1. This absorption is significant
because it may represent the C-O bond of the ether group attached at the ortho position of
eugenol. Aside from this however, there are no other significant absorptions in the IR of TYR 1
to suggest the presence of any other functional groups, and so this IR matches with the structure
and functional groups of eugenol.
NMR:
The NMR of TYR 1 found on Figure 2 strongly corresponds with the structure of eugenol. The
provided structure of eugenol on Figure 2 is labeled with hydrogens that correspond to the
distinct peaks of the NMR. To begin with, there are 12 hydrogens in eugenol, and the sum of the
integrated peak areas of the NMR is 11.7, which is rounded up to 12. Thus, at the very basic
level, TYR 1 and eugenol match with the same number of hydrogens.
The number of peaks, chemical shifts, and splitting patterns also link eugenol with this NMR of
TYR 1. Beginning on the ring, HA corresponds to the singlet peak at about 5.6ppm. Phenolic
hydrogens can have chemical shifts from 4-12ppm, so this certainly falls within that range. HB
denotes the three methyl hydrogens attached to the ether substituent at the ortho position of the
ring. The integration of 3.1 matches the three hydrogens on the structure of eugenol, and the
chemical shift of about 4.0ppm is typical of hydrogens near an electron withdrawing oxygen. In
addition, since there are no adjacent hydrogens, the peak is simply a singlet. The last two signals
from the aromatic ring are HC and HD. HC is the hydrogen in the other ortho position of the ring,
with a chemical shift of 6.9ppm which is typical of aromatic hydrogens. Its splitting pattern most
resembles a doublet, which makes sense since there is only one hydrogen adjacent to it. Finally,
HD corresponds to the two hydrogens at the meta position of the ring. These hydrogens have
chemical shifts of 6.8ppm. It follows that these two hydrogens would have a lower ppm than HC,

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which is no doubt being deshielded by the neighboring oxygen of the alcohol. HD appears to be a
broad singlet, and this splitting pattern may be occurring because the HD closer to the ether
substituent may have a slightly different chemical shift than the other HD.
Moving on from the ring to the para substituent, HE is a peak that integrates to 2.04 hydrogens,
has a chemical shift of about 3.4ppm, and corresponds to the two hydrogens at the benzylic
carbon. Generally, benzylic hydrogens have a chemical shift of 2.2-3ppm, but since these
hydrogens are also at an allylic position, they undergo some further deshielding. The splitting
pattern is a doublet, which makes sense since only HF is adjacent to it.
As for HF itself, it has a chemical shift around 6ppm, which is close to the 4.6-5.9ppm range of
vinylic hydrogens, so this makes sense when looking at where it is in the structure of eugenol. Its
splitting pattern appears to be a sextet, which would imply that there are five neighboring
hydrogens. However, the only adjacent neighboring hydrogens are the two HEs and the two
HGs, which would create a splitting pattern of a pentet for HF. One explanation of this may be
that what appears to be a sextet is not really a sextet at all, but a multiplet. Because HG and HE
are not chemically equivalent, they would each split HF differently. The resulting multiplet would
be a triplet of triplets. It is very hard to discern whether this is actually the case because the NMR
provided is not magnified very much, but the splitting pattern of HF alone does not deem it
impossible for TYR 1 to be eugenol. The chemical shift and the integration still match up.
Finally, HG is the most interesting peak on the NMR of TYR 1. This peak corresponds to the two
vinylic hydrogens at the very end of the allyl substituent. The chemical shift of about 5.1ppm
makes sense as it is within the 4.6-5.9ppm range of vinylic hydrogens. Its splitting pattern,
however, is quite unique. There are three peaks, but rather than the 1:2:1 ratio characteristic of a
triplet, the ratio is 1:1:2. This is probably due to the fact that the two protons of HG are not
actually chemically equivalent, since one is cis and one is trans to the larger portion of the
eugenol molecule. If the two protons of HG were chemically equivalent, then the splitting pattern
would be a simple doublet since only HF is adjacent. But since the two protons of HG are not
chemically equivalent, they split each other, which is why the multiplet pattern occurs. Ideally
then, we would expect to see a doublet of doublets for each of these distinct hydrogens at HG, but
this is not the case either. This may just be for the same reason the two hydrogens were dumped
together in one integration in the first place: taking an NMR does not guarantee a perfect result,
and there may have been some error in calibration or with the solvent. Whatever the case, HG
along with all the other hydrogens on the NMR have chemical shifts, integration, and (for the
most part) splitting patterns that we would expect to see in an NMR of eugenol. From that, it is
apparent then that TYR 1 is indeed eugenol.