A Grignard reaction synthesis of Triphenylmethanol

29/01/25

Mason Ralph

Wyn Rolls
Objectives:

The purpose of this experiment was to demonstrate a Grignard reaction by adding an

alkyl group to a carbonyl compound. In this experiment the Grignard reagent was prepared from

bromobenzene, which reacted with benzophenone to synthesize triphenylmethanol.

Reaction:

Table of Physical Constants:

Chemical Magnesium Bromobenzene Benzophenone Triphenyl

(Mg) (C6H5Br) ((C6H5)2CO) methanol
((C6H5)3COH)
Mass used (g) 0.60 3.92 6.01 NA
Molar mass 24.31 157.01 183.24 260.33
(g/mol)
Mole Ratio 1 1 1 1
Moles used 2.47x10-2 2.50x10-2 3.73x10-2 2.47x10-2
(mol)
Melting point1 650 -30.74 48.0 162.3
(OC)
Boiling point1 1090 155.9 305.9 380
(OC)
Density1 1.74 1.4950 1.11 1.199
(g/cm3)
Theoretical NA NA NA 6.43
yield (g)
 Crude yield (g) NA NA NA 1.93
Percentage NA NA NA 8.1%
yield
Calculation of Theoretical Yield:

Procedure:

The procedure followed as described in pages 12-15 in the lab manual.

Observations:

When the clear colorless bromobenzene solution was mixed with clear and colorless

anhydrous ethoxyethane it remained a clear and colorless solution. This was then added to

metallic grey magnesium metal in anhydrous ethoxyethane. After scratching the metal’s surface

the solution turned cloudy and a gas was produced. After the addition of the remaining

bromobenzene and about 20 minutes of reflux, the reaction mixture turned a translucent brown.

Following this, coarse white benzophenone powder was dissolved in anhydrous ethoxyethane

producing a clear colorless solution. This solution was then added to the reaction mixture

forming a clear pink solution and a clumpy off-white precipitate. After adding this mixture to a

beaker of clear colorless sulfuric acid and ice and letting it set for a week, a cloudy solution and

off-white precipitate was left. This was placed into a separatory funnel with clear colorless

ethoxyethane, then shaken producing two layers: a yellow and clear organic top layer, and a clear
colorless aqueous lower layer. These were separated and the top layer was kept. The separations

were repeated with deionized water, then in clear colorless sodium bicarbonate solution and once

more in deionized water. All these separations produced a clear yellow upper layer containing the

product and a lower clear colorless aqueous layer that was discarded. The clear yellow solution

then had white crystalline sodium sulfate drying agent added to it. After drying and filtering the

sodium sulfate out the solution remained yellow and clear but lost some of the yellow vibrance.

This solution was then placed in the Rotavapor to remove excess solvent resulting in the solution

forming a white precipitate. Clear colorless ligroin was added to this resulting in the solution

turning cloudy. This was then placed in an ice bath; after doing so white solid precipitated out.

The crystals were then collected via suction filtration. The collected crystals were then

recrystallized in clear colorless hot methanol which created a clear colorless solution that upon

cooling in an ice bath produced fine white crystals of product that were collected via suction

filtration.
Results:

Starting material used: 0.60g (2.47x10-2 mols) Mg metal, 6.01g (3.73x10-2

mols) of benzophenone and 3.92g (2.50x10-2 mols) of bromobenzene

Crude yield obtained: 1.93g

Pure yield obtained: 0.52g

Percent yield: 8.1%

Melting point: 158-159ºC

Compound Rf Values

Pure triphenylmethanol (PT) 0.02

Crude triphenylmethanol (CT) 0.02, 0.78

Pure biphenyl (PB) 0.55

The mother liquor (ML) 0.05, 0.55

TLC Plate:

PT: Pure triphenylmethanol

PB: Pure biphenyl

CT: Crude triphenylmethanol

ML: The mother liquor

FTIR Spectra:

A B C D E

O-H (Stretching) C=C-H C=C (Aromatic C-O (Stretching) C-H (Aromatic

(Aromatic ring motion) bending)

stretching)
A B C D

C=C-H (Aromatic C=C (Aromatic C=C (Aromatic ring C-H (Aromatic

stretching) stretch) motion) bending)

A B C D

C=C-H (Aromatic C=O (Ketone C=C (Aromatic ring C-H (Aromatic

stretching) stretching) motion) bending)

NMR Spectra:

A B C

Aromatic ring hydrogens Oxygen attached hydrogen TMS

A B C

β- Hydrogen on Arene ring γ- Hydrogen on Arene ring Furthest hydrogen on arene

ring
A B C

β- Hydrogen on Arene ring γ- Hydrogen on Arene ring Furthest hydrogen on arene

ring
Discussion:

This experiment was a demonstration of a Grignard reaction. Where a Grignard reagent

was prepared from bromobenzene to react with benzophenone to form the tertiary alcohol

triphenylmethanol.

A Grignard reagent consist of an alkyl or aryl group bonded with a halogen

reacted with magnesium metal to form a reagent with the general formula R-Mg-X. The

electronegativity difference between the alpha carbon and the magnesium metal creates a partial

negative charge on the carbon. Such that the partial negative charge on the alpha carbon makes it

a potent nucleophile, that can react with the positive charge on a carbon of a carbonyl compound

as the electrons localize toward the oxygen. Additionally, it should be noted that this type of

reaction must occur in anhydrous conditions, as any labile hydrogen present will protonate the

Grignard reagent and produce unintended byproducts. Hence anhydrous ethoxyethane was used

as a solvent in this experiment. In the case of this experiment the Grignard reagent was prepared

from bromobenzene reacted with magnesium metal. During the addition of bromobenzene to the

magnesium metal a color change occurred from clear and colorless to brown and opaque

indicative of the formation of the phenyl magnesium bromide Grignard reagent. Another color

change occurred upon the addition of the clear colorless benzophenone. After adding the

carbonyl compound to the Grignard reagent mixture, the solution turned pink, and a considerable

amount of pinkish precipitate formed. This color change is indicative of the reaction progression

as the phenyl group of the Grignard reagent is added to the carbonyl carbon of benzophenone

and a magnesium salt intermediate is formed. At this point in the reaction the intended product is

a triphenyl methanolate intermediate2. It must be protonated by acid, and as such the solution and

precipitate containing the product was poured into a beaker of sulfuric acid and ice. The product,
now protonated as the intended triphenylmethanol was separated from the solution via separatory

funnel by isolating it in the organic phase in upper layer when mixed with, then separated from

diethyl ether, deionized water and sodium bicarbonate solution. Then in deionized water once

again from which the ethereal layer containing the product was collected. Any remaining water

was removed by adding anhydrous sodium sulfate; that was removed afterward by gravity

filtration. The excess solvent was then removed under reduced pressure and temperature via

Rotovap causing the product to precipitate out. This solution of product then had ligroin added to

it, in which the product is insoluble causing the product to precipitate out. After cooling this

solution in an ice bath, the solid product was collected by suction filtration. The collected solid

was then recrystallized a minimal volume of hot ethanol to remove impurities in the final

product.

After recrystallization, various methods were employed to determine the identity and

purity of the product. In determining the identity of the product two means were used. Firstly, the

recrystallized product was compared by TLC plate analysis to the mother liquor filtrate obtained

during suction filtration, the crude product, and a standard of biphenyl to determine the presence

of the biphenyl byproduct. The TLC plate showed some identical spotting for the mother liquor

and crude and pure product indicating that a pure product was obtained and isolated in the

recrystallized sample. Additionally, the pure biphenyl and mother liquor showed identical

spotting confirming the presence of the biphenyl byproduct. However, the crude product also had

a spot higher than the rest, indicating the presence of some other byproduct. Likely some kind of

substituted benzene due to its lessened polarity making it travel the furthest up the TLC plate in

the nonpolar (ligroin) dominant eluting solvent. A sulfuric acid test was then administered to

confirm the identity of our intended triphenyl methanol product by comparing it to biphenyl,
which may have been produced instead. To differentiate between them concentrated sulfuric acid

was added to a sample of standard biphenyl and our synthesized product. The biphenyl displayed

no reaction due to it possessing no sites to be protonated at room temperature. However, a

reaction occurred in the product sample as evident from a rapid color change to yellow from

being colorless. This indicates we have synthesized triphenyl methanol as the bright yellow color

is a sign of the trityl cation being formed when the acid protonates the hydroxyl group on

triphenyl methanol, and it leaves as water3.

Finally, a melting point was collected for a sample of product. The melting point

observed was 158-159 ºC which is about 4 degrees less than what would be expected of triphenyl

methanol (162.3 ºC). however, the lower-than-expected melting point may be due to trace

amounts of solvent remaining in the crystal structure of the product.

Also of note, analysis of FTIR and NMR spectra can be used to differentiate

amongst the compounds used and synthesized in the laboratory. IR spectra (provided) for

triphenyl methanol shows a peak at strong broad peak around 3400 cm-1 corresponding to and O-

H bond stretch. As there is no peak present near 1710 cm-1 corresponding to a carbon-oxygen

double bond we can tell that this is an alcohol as opposed to carboxylic acid. There are additional

peaks corresponding to the carbon-carbon double bonds and carbon bonds to hydrogen indicative

of the phenyl structures attached to the alcohol group. Further differentiation can be made

between spectra of biphenyl and benzophenone. As both structures contain two aromatic rings,

they possess similar peaks corresponding to the phenyl structure of carbon double bonds and

hydrogen bonds. However, a strong narrow peak is present in the spectrum of benzophenone

around 1650 cm-1 indicating the presence of a carbonyl (ketone) that is not found in biphenyl.

This is lower than the expected value of 1715 cm-1 due to conjugation with the pi bond system of
the aromatic rings4.

The NMR spectra (provided) for triphenyl methanol displays two prominent

peaks. One near 7.5 ppm indicative of the quite deshielded hydrogens of the aromatic ring and

another near 2.5 ppm corresponding to the hydrogen connected to the oxygen of the hydroxyl

group. The aromatic equivalent hydrogens are the most deshielded due to the cyclic nature of the

pi electrons creating an induced magnetic field that adds to the effects of the applied field thus

the field’s effect is intensified5. Hence there is more deshielding in aromatic rings than that

provided by the electronegative oxygen. Additionally, it should be mentioned that the NMR

spectra of biphenyl and benzophenone appear very similar, with peaks in the same range and

distribution. This is due to the similar electronic environment the protons are in. all of the

protons in question are located on the aromatic rings of both compounds (no hydrogen present on

the carbonyl of benzophenone). Both are ring structures on either compound are

monosubstituted, which increases the chemical shift of the protons closest to the substituted

carbon. Thus, the peaks for both spectra can be interpreted in order of proximity to the

substituted site. With hydrogens β- Hydrogens on the aromatic ring being the most deshielded

and furthest downfield peak, then γ- Hydrogens being the next peak up field and the furthest

hydrogens on the aromatic ring creating the least deshielded peak up field. Also, the chemical

shifts of benzophenone are slightly higher than that of biphenyl due to the additional deshielding

provided by the oxygen atom’s electrons. The yield produced from this experiment

was considerably lower than the theoretical yield. This is likely due to two factors. Firstly, this

experiment required the product and reaction mixture to be transferred between many different

pieces of glassware to synthesis and isolate the product, thus a large contributor to the decreased

yield may be due to reaction materials and product lost on glassware. Additionally, the
production of biphenyl byproduct during the preparation of the Grignard reagent may have used

up an appreciable amount of starting material contributing to the low yield of the intended

product. The green chemistry implications of

a Grignard synthesis such as this are very interesting. Although it makes use of magnesium metal

in the preparation of the Grignard reagent, which is quite reactive with water, and benzene

compounds (bromobenzene and benzophenone) that are highly toxic to aquatic systems; all of

which must be appropriately disposed of. However, it is a rather efficient means to produce

alcohols and organic acids from ketones and aldehydes respectively at a low temperature,

conserving energy while using most of the starting materials in a 1:1 ratio.

Conclusion:

The purpose of this experiment was to demonstrate a Grignard reaction via the formation

of triphenyl methanol from the prepared Grignard reagent phenyl magnesium bromide and

benzophenone. The product obtained from this experiment displayed various evident factors such

as TLC plate observations, sulfuric acid testing and a comparable melting point indicative that

the triphenyl methanol product was synthesized and isolated at a reasonable level of purity.
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(1)

Haynes, W. M. CRC Handbook of Chemistry and Physics, 95th Edition, 95th ed.; Taylor &

Francis Ltd, 2014.

(2)

PubChem. Magnesium;triphenylmethanolate;bromide. pubchem.ncbi.nlm.nih.gov.

https://pubchem.ncbi.nlm.nih.gov/compound/10992115.

‌(3)

Nishiuchi, T.; Sotome, H.; Fukuuchi, R.; Kamada, K.; Miyasaka, H.; Kubo, T. Optical Nature of

Non‐Substituted Triphenylmethyl Cation: Crystalline State Emission, Thermochromism, and

Phosphorescence. Aggregate 2021, 2 (6). https://doi.org/10.1002/agt2.126.

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