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Synthesis and Chromatographic Separation of Fluorenone from

Flourene
Charlie Page
Introduction
Chromatography has long been used in chemistry as a cheap and easy way to
separate compounds in a mixture. All chromatography utilizes a stationary and a mobile
phase to separate substances based on their propensity to bind to one phase or another. In
thin layer chromatography (TLC), the stationary phase is a cheap polar material like
paper (cellulose) or silica bound to a strip of plastic or metal. The mobile phase is a
nonpolar solvent in which the mixture to be separated is dissolved. The nonpolar phase is
allowed to run up the stationary phase, with each mixture component traveling a
characteristic distance relative to the solvent front based on its comparative attraction to
the stationary phase versus the mobile phase (its Rf value). TLC cannot be used to purify
materials, but it is a useful assay to quickly check for the number of different substances
in a mixture and their qualitative amounts and polarity (2).
Column chromatography (CC) is another form of chromatography in which the
paper or silica strip is replaced by a column of uniform powder such as silica. The mobile
phase is soaked throughout the stationary phase to ensure regularity, and the sample is
then allowed to run down the column along with more mobile phase. Small portions or
fractions of the mobile phase runoff are collected and analyzed, often by TLC, to
determine which mixture components are present (2).
Column chromatography can be slow and sometimes imprecise, but is a cheap
way to separate a mixture, and modifications to the process have made it more efficient
2
over time. For example, in 1978, Still et al. developed flash chromatography, in which
the mobile phase is pumped through the column using pressure from an inert gas such as
nitrogen. This allows CC to be done relatively quickly, making it more practical for
common lab use (5).
Another component of this lab is oxidation. Oxidation, the electron-losing half of
a redox reaction, is a cornerstone of chemistry, involved in most useful reactions. For
example, the oxidation of glucose to carbon dioxide is used in organisms for energy.
Many industrial processes also use oxidation (1). Among many significant examples, the
oxidation of impurities in iron in the Bessemer process allowed the cheap production of
steel in the 19
th
century, sparking the building of iconic buildings like the Eiffel tower.
Oxidation can be accomplished in many ways. Since it is thermodynamically
favorable for a compound to be oxidized in the presence of an electronegative or
electron-deficient reagent, it is usually enough to oxidize a compound to simply expose it
to an oxidizing agent such as hydrogen peroxide or oxygen, perhaps in the presence of
heat (as in the Bessemer process). Acid catalysis is often useful in oxidation reactions, as
it can increase the electrophilicity of an oxidizer (1).
Other catalysts may often be useful, such as phase-transfer catalysts. These are
catalysts that speed reactions by pulling one or more reactants into a new phase, such as
the organic layer of a solvent mixture, where they can react with other reactants. Phase-
transfer catalysts are often molecules with hydrophobic sections bound to polar or ionic
sections. For example, in Starks catalyst, the positively charged nitrogen can bond to
anions such as hydroxide in the aqueous phase; the now neutral molecule can then
dissolve in the organic layer where the hydroxide can react (3,4).
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Figure 1: Electron Pushing Mechanism and Balanced Chemical Equation for
Fluorene Oxidation

The oxidation of fluorene is a radical chain reaction utilizing the hydroxide
catalyst made available in the organic solvent via Starks catalyst. An oxygen molecule
abstracts a benzyllic hydrogen from fluorene, generating a radical (reaction 1). The
fluorene radical bonds with an oxygen molecule (reaction 2), which also abstracts a
hydrogen from another fluorene (reaction 3), perpetuating the reaction. At this point, the
hydroxide catalyst (soluble due to Starks catalyst) pulls off the remaining benzyllic
hydrogen, pushing electrons into a carbonyl system, pushing out hydroxide,
regenerating the catalyst and generating fluorenone and water (reaction 4).
The purpose of this experiment was to conduct the fluorene oxidation reaction
described above to ~50% completion, and to isolate and analyze the products. The
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isolation of the products was conducted using column chromatography, while the
products were analyzed by mass and by infrared spectroscopy (IR).

Experimental

Fluorene (0.069g, 0.415 mmol), 10M aqueous NaOH (5 mL, 50mmol), Toluene (5 mL,
46.9 mmol), and 2 drops of Starks catalyst were stirred while being monitored by TLC
every 5 minutes. After 10 minutes, it was determined that the reaction had reached ~50%
completion.
Figure 1: Developed TLC plates of Fluorene standard and Reaction Mixture (F and
Rxn respectively)






The organic layer of the reaction mixture was then extracted and washed with 5 % HCl
(3 x 5 mL, 6.686 mmol) and saturated NaCl (3 x 5 mL, 50 mmol) solution. The toluene
solution was then dried with sodium sulfate and the toluene evaporated. The reaction
mixture was dissolved in 10 drops of dichloromethane and the components separated via
flash chromatography using silica gel stationary phase and hexanes mobile phase,
resulting in a calculated 280.8% yield of fluorenone (0.105 g, 0.583 mmol) and a 1060%
F Rxn
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yield of fluorene (0.371g, 2.23 mmol. An IR spectrum was obtained for fluorene, while
an 100 MHz NMR spectrum was obtained for fluorenone due to the low amount
recovered.
Table 1: IR data, Obtained from Fluorene (Significant Peaks)
Observed Bond Strength
2918.8 cm
-1
Sp3 C-H
1442.1 cm
-1
Sp3 C-C

Table 2:
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H-NMR Data, Obtained with Deuterated Chloroform Solvent on a 100 MHz
NMR (Significant Peaks)*
Observed Type of Hydrogen
2.028 ppm Alpha to carbonyl
2.125 ppm Alpha to carbonyl
2.170 ppm Alpha to carbonyl
*The splitting pattern of the peaks was indiscernible due to low resolution.
Results and Discussion
As was noted in the experimental section, the sodium hydroxide solution and the
Starks catalyst were added to the reaction to serve as catalysts. The hydroxide serves, as
seen in the electron pushing mechanism, to pull off the second hydrogen from fluorene
and donate electrons to the oxygen, while Starks catalyst is a phase transfer catalyst that
moves the hydroxide into the organic layer where it can react. The toluene was used
merely as a volatile solvent for the reaction to occur in. It should also be noted that, in
addition to the fluorene, atmospheric oxygen was used as a reactant.
The toluene was washed with acid to neutralize any remaining base, and to
remove water, hydroxide and Starks catalyst from the solution. The NaCl solution wash
served to further remove polar impurities, with the sodium sulfide removed any last trace
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of aqueous contamination. This left behind a simple solution of fluorene and fluorenone
in toluene, which could then be evaporated off, leaving behind the product.
TLC monitoring of the reactions progress served to qualitatively indicate when
the reaction was about half done. However, this method was very imprecise, as the TLC
did not give any results until about one minute after the sample was taken. Furthermore,
the fluorene and fluorenone spots, while clear and distinct, were of different sizes, with
the fluorene spot large and diffuse and the fluorenone spot small and dense. This made it
difficult to compare the relative amounts of each substance, making the estimation of
50% completion very rough.
The column chromatography procedure served to separate the fluorene in
fluorenone. This was possible because the fluorenone is significantly more polar than
fluorene, giving it a much lower Rf value, as was seen in TLC (Table 1). Thus, the
fluorenone remained in the column far longer than the fluorene, allowing all of the
fluorene to be eluted while the visible yellow fluorenone band had hardly moved. In
order to speed the recovery of the fluorenone, the solvent was switched from hexanes to a
50/50 hexanes and dichloromethane mixture. This allowed the remaining fluorenone to
be quickly separated. There was no risk of contamination as all of the fluorene had
already been removed in the hexane fractions. The procedure appeared to go smoothly,
with the yellow fluorenone clearly visible in its fraction and not apparent in the fluorene
fractions.
There were difficulties, however, in the removal of fluorene and fluorenone from
their containers for massing. There were miniscule amounts of each substance in their
containers, and they were firmly attached to the glass. In an attempt to get all of each
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compound removed, the fluorene and fluorenone were dissolved in hexanes and acetone
respectively and transferred to their tared containers before being blown with nitrogen for
about one hour to evaporate the solvent.
The IR spectrum for fluorene (figure 1, addendum) looks disappointing, with
major peaks only at 2918.8 cm
-1
and 1442.1 cm
-1
. These correspond with sp3 carbon
and hydrogen bonds, not the sp2 bonds expected for fluorene, which would be in the
3300-3000 cm
-1
region. However, this does not mean the product was not
separated. There is indeed a minor peak in the 3300-3000 cm
-1
region that is
consistent with a minor quantity of fluorene. Furthermore, TLC analysis of the CC
fractions indicated a single compound with Rf of .29, similar to the value of .35
found in TLC of fluorene standard during the synthesis reaction. Different solvents
were used for each TLC, which could account for the difference.
The major peaks could be accounted for by leftover hexane solvent that was
not fully evaporated after being used to transfer the fluorene. The peaks are
consistent with the sp3 C-H and C-C bonds that are present in hexanes. This would
also agree with the impossibly high percent yield of fluorene (discussed later).
Likewise, the
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H-NMR spectrum for fluorenone (Figure 2, addendum) seems
at first glance to be off, with massive peaks for hydrogens alpha to a carbonyl (2.1-
2.4 ppm) and miniscule peaks in the 6.5-8 ppm region where the aromatic
hydrogens in fluorenone would show up. However, these peaks are significant
enough to suggest the presence of fluorenone, which confirms visual observations of
the yellow substance. The large carbonyl peaks, in turn, are likely due to
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unevaporated acetone solvent, which would also explain the impossibly high
percent yield of fluorenone.
As mentioned, the percent yields of fluorene and fluorenone are impossibly
high, at 1060% and 280.8% yield respectively. This seems puzzling, as both
substances appeared to be present only in small amounts after column
chromatography. However, the high percent yields can be explained by
contamination by the hexane and acetone solvents used to remove them from their
containers. Although both solvents appeared to have evaporated, both the spectra
and percent yield data suggest high amounts of contamination by each. A second,
less significant factor may also have been an erratic scale used to mass each
compound. This makes true percent yield difficult to ascertain.
However, based on the very small amounts of fluorene and fluorenone visible
after CC, it can reasonably be assumed that the true percent yield was fairly low,
likely indicating high purity. Purity is also suggested by the single spots present in
TLC of the CC fractions.
Losses could have occurred during many steps in the procedure. For
instance, small amounts of organic solution and thus product could have been lost
during the washing of the toluene. Some product, especially fluorenone, which
appeared to have a lower percent yield than fluorene, may even have dissolved in
the disposed aqueous layers. Further losses could have occurred due to trace
amounts of product in disposed CC fractions, or in the CC stationary phase itself.
Thus, while an unsuccessful attempt to extract the fluorene and fluorenone
with volatile solvents skewed much of the data, it appears likely that fluorenone was
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successfully synthesized, and that both fluorene and fluorenone were initially
successfully isolated with reasonable purity. This lab also highlights the risks of
excessive solvent use.

References.
1. Hughes, M. et al. Tunable gold catalysts for selective hydrocarbon oxidation
under mild conditions. Nature 2005, 437, 20, 1132-1135.
2. Lab Guide for Chemistry 213: Introductory Organic Laboratory Minard, Masters,
Halmi, Williamson, and Bortiatiynski, published by Hayden McNeil, 3
rd
Edition.
3. Metzger, O. Solvent-Free Organic Synthesis. Angewandte Chemie International
Edition, 1998, 37, 21.
4. Mieczyslaw, M. Phase-transfer catalysis. A general green methodology in organic
sythesis. Pure Appl. Chem 2000, 72, 7, 1399-1403.
5. Still, W. Rapid Chromatographic Technique for Preparative Seperations with
Moderate Resolution. J. Org. Chem 1978, 43, 14, 2923-2925.

Addendum
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