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CHEM 2425-85201
Synthesis of Triphenylmethanol and the Trityl Carboction (Grignard)
INTRODUCTION
The Complementary Colors Company manufactures synthetic dyes, including
triphenylmethane dyes. In order to develop some new products, Gilda Lillie has learned that
having two para-dimethylamio grops on two of the three benzene rings in the parent structure
yields a green dye (Malachite Green), and having three of them yields a violet dye (Crystal
violet). The experiment is to prepare triphenylmethanol and convert it to trityl fluoborate, a salt
which contains the trityl carbocation to know how positions of substituents on the parent
tripheylmethyl ring affect the color of triphenylmethane dyes.
DISCUSSION
Step 1: Reaction of Bromobenzene with Magnesium
The phenylmagnesium bromide will be prepared by adding a solution of bromobenzene
in anhydrous diethyl ether to magnesium metal. During this reaction, it is needed to avoid water
because phenylmagnesium bromide reacts rapidly with water to form benzene.
Weight 22.0 mmol (0.535g) of clean, dry Mg turnings. The actual weight: 0.539g (0.022
mol)
Leave them in 100-mL round-bottom flask (R.b. Flask) for 5 minutes of drying (by
Thermowell, heat 35-40).
In the meanwhile, weight 22.0 mmol (3.454g) of dry bromobenzene into the dried
Erlenmeyer flask (E. flask) and dissolve it in 5.0 mL of anhydrous diethyl ether.
The actual weight of Bromobenzene: 3.460g (0.022 mol)
Transfer this solution to the separatory-addition funnel (S. funnel) and stopper it, with a
strip of paper in the between of stopper and the neck of S. funnel.
Prepare 6.5 mL of anhydrous diethyl ether in a graduated cylinder (grad. cylinder).
Add 1 chip of iodine into the R.b. flask. After seeing purple gas in the flask, remove the
heat and let it cool down.
Mg0 + I2 Mg0/I2(g)
Assemble an apparatus for reflux [OP-11]. Insert the drying tube [OP-12a] in the top of
the reflux condenser. Insert the S. funnel to the claisen attached.

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Add the bromobenzene solution all at once to the R.b. flask (reaction flask). Close the
vent. Add 6.5 mL of anhydrous Et2O into the S. funnel.
Br

Mg

Mg
Br

P h e n y lm a g n e s iu m b r o m id e

Remove the R.b. flask, crush and rub the magnesium turnings by stirring rod for 30
seconds (until all Mg turnings reacts with the solution). Reattach the funnel to the
reaction apparatus.
Observe evidence of a reaction: Bubbling
When reaction mixture begins boil vigorously without external heating: Add the ether,
drop by drop at rate to keep the reaction mixture boiling.
Let the reaction continue until the boiling has nearly stopped. Reflux [OP-7] for 15
minutes.
Check for the loss of volume of the ether: Replace the loss with fresh anhydrous ether.
Volume of ether that used to replace the loss: 4 mL
Step 2: Reaction of Phenylmagnesium Bromide with Benzophenone
Weight 20.0 mmol (3.644g) benzophenone in 10 mL Et2O (anhydrous) in E. flask. The
actual weight: 3.646g (0.020 mol). Place the solution in the S. funnel.
When the reaction mixture is cooled, no more boiling, add this solution, drop by drop,
with magnetic stirring [OP-10], but fast enough for the ether boiling gently without
external heat.
O

Br
Mg

O
Mg Br

When complete addition, heat the reaction under gently reflux for 15 minutes.
When the mixture is cooled to room temperature:
Add 5.0 mL (0.27 mol) of water, drop by drop, through S. funnel while stirring.

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Mg Br
O

H2O

OH

+ HO

Mg
Br

Add dropwise 15 mL of 5% (1.4M) HCl,

Stirring until all the white solid has dissolved. If undissolved white solid: break the solid
by spatula, add solvent-grade Et2O or 5% HCl or both until dissolve all the solid.
Replace the loss of Et2O by solvent-grade Et2O.
Step 3: Separation
If there is undissolved magnesium present: Gravity filtration [OP-15], wash with solventgrade Et2O. The Buchner funnel was used instead of long stem funnel, which leads to the
loss of 10 mL over 30 mL product. The percent loss is 30%.
Transfer the reaction mixture into S. funnel, shake gently to mix the layers, drain and
discard the aqueous layer.
Wash the Et2O layer with 15 mL NaHCO3(5%).
Wash with 15 mL of NaCl (saturated).
Dry [OP-25] the ether solution over anhydrous MgSO4. The filter paper and the long stem
funnel still distribute another 30% loss of product. 20 mL of product now has only 10
mL.
Evaporate the ether under vacuum [OP-19] (Rotavap), cold trap.
Add 10 mL of hexanes (or high-boiling Petroleum ether) to the solid residue, then use the
spatula/flat-bottomed stirring rod to triturate [OP-26a] in 2-3 minutes.
Collect product by vacuum filtration [OP-16], wash it [OP-26a] with fresh solvent.
Air dry on the filter.
Step 4: Purification and Analysis
Recrystallize [OP-28] the crude triphenylmethanol from a 2:1 hexanes (or petroleum
ether) with absolute ethanol: 30 minutes
Dry [OP-26b] the purified triphenylmethanol.
Weight it: 0.648g
Step 5: Melting point
Expectation of melting point: 164oC
Melting point [OP-33]: The 1st time: 158oC, the 2nd time: 160oC

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Step 5: IR spectrum
Strong absorption peak at 695 cm-1 and 755 cm-1 indicates =C-H stretch which should be
in the range from 769-691 cm-1. The weak absorption peak at 1597 cm-1 indicates -C=C- stretch,
which should be in the range from 1616-1492 cm-2.
The broad peak at 3465 cm-1 indicates the -O-H stretch.
A weak peat at 3050 cm-1 indicates the C-H sp2 stretch of benzene ring.
RESULTS AND CALCULATIONS
Due to the chain of the reactions as below, the limiting reagent is benzophenone.
0 .2 7 m o l

0 .0 2 0 m o l
O

Br

Mg

Mg

Br

H2O

OH

0 .0 2 2 m o l

0 .0 2 2 m o l

0 .0 2 0 m o l

0.020 mol benzophenone will produce theoretically 0.020 mol of triphenylmethanol,

which equal to 5.206 gram. Since the mass of the obtained crude product is 0.648g, the
percent yield is
Crude=

0.648
100=12.45
5.206

CONCLUSION
The IR spectrum 1 and melting point confirm the characteristics of triphenylmethanol,
which was synthesized. The loss of product was high due to a half of the Grignard procedure was
stopped in the middle, the wrong using of Buchner funnel in the gravity filtration step distribute
the large loss of the product.
EXERCISE
1. Reactions:
(a) Bromobenzen + Metal to form biphenyl:

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(b) Phenylmagnesium bromide and trityl fluoborate with water:

2. Compare the product IR with Bromobenzene IR and benzophenone IR:

The product IR has O-H stretch at 3465 cm-1, but none of bromobenzene nor
benzophenone IR has it.
All of the spectrums have C-H sp2 stretch at the region above 3000 cm-1.
The peaks at 1660 cm-1, which indicates C=O stretch, disappear on the product IR
spectrum.
The peak around 1600 cm-1 are on all the IR spectrum, which indicates the -C=C- stretch.
The peaks at 769 cm-1 to 691 cm-1 of =C-H stretch appear on all the IR spectrum.
3. Mechanism for reactions: