LAB REPORT 1

Synthesis and characterization of Grignard Reagent

 Apparatus
Drying tube
Dropping funnel
Three Neck flask
Stand with clamp
Funnel
Cotton wool
Condenser
Glass rods
Claisen head adapter
5 mL conical vial
Magnetic spin vein
 Chemicals
Diethyl ether (sodium dries)
Calcium chloride
Magnesium turnings
Bromobenzene
Water
 Principle
The basic principle is the reduction of carbonyl-containing compound benzophenone to the
alcohol compound triphenylmethanol. This reduction was done by the nucleophilic addition of
the Grignard reagent: phenyl magnesium bromide, in a nonreactive ethyl ether solution.
 Theory
Grignard reagents, such as organomagnesium halides, were discovered in 1910 by French
chemist Victor Grignard. The Grignard reaction is one of the most general methods for carbon
carbon bond formation in all organic chemistry.
  Uses
The Grignard reaction is a useful tool for the formation of carbon-carbon bonds in organic
synthesis.
 Reaction
 Mechanism
In the first stage, an organic halide reacts with magnesium metal to form an
organomagnesium compound, which is known as a Grignard reagent. This is an organic
redox reaction.
The carbon atom that was initially bonded to the halide is reduced by two electrons, and the
magnesium is oxidized by two electrons. The polarity of the bond to carbon is reversed, since
carbon has a higher electronegativity than the metal magnesium, the C-Mg sigma bond is
highly polarized, placing a partial negative charge on carbon. As a result. Grignard reagents
act as carbanion equivalents, and they are both strong nucleophiles and strong bases. This
means that great care must be taken to exclude even relatively weak acids (such as water or
alcohols) from the reaction mixture in order to avoid the formation of byproducts arising
from proton transfer.

Once formed, Grignard reagents can react with a wide variety of carbonyl-containing
compounds to form new carbon-carbon bonds in a general process known as nucleophilic
addition: The C-0 band is tightly polarized, making carbonyl compounds electrophilic at
 carbon. If the Grignard reagent reacts with an aldehyde, ketone or ester, the ultimate product
is an alcohol.

 Procedure:

 Equipment preparation

A significant amount of water will adhere to the surface of glassware. Therefore, all glassware
used in the Grignard reaction must be scrupulously cleaned and dried. In preparation wash all
glassware, rinse with acetone, and place dry glassware in the oven overnight.

Note disposable dram vials need not be washed, but should be rinsed with acetone.

Just prior to your experiment carefully remove dry glassware from the oven, assemble and
immediately cap it with a septum. The hard side of the septum is the solvent resistant Teflon side
and should be place downward. Stopper the disposable dram vials with corks. Allow all
glassware to cool to room temperature before proceeding with the experiment. Keep the vessel
capped throughout the course of the experiment unless you need to add something to it.

 Preparation of Grignard reagent

Obtain 3 mL of anhydrous diethyl ether in one of the oven dried dram vials. Weigh magnesium
powder (50 mg, 2 mmol) and add in reaction vessel. Using a 1.0 mL syringe inserted through the
septum add 0.5 mL of anhydrous diethyl ether to the reaction vessel.

In a separate oven dried vial, add bromobenzene (330 mg, 2.1 mmol) and 0.7 mL of anhydrous
diethyl ether and transfer 0.1 mL of this solution into the reaction tube.

The solution should turn cloudy and start to boil, indicating that the reaction has started. To
prevent the ether from boiling away, wrap a damp paper towel around neck of the Claisen
adapter. Over several minutes, slowly add the remaining bromobenzene/ether solution, making
sure that the reaction does not boil too vigorously.
It is important to control the addition of bromobenzene to avoid the rapid evolution of heat. After
boiling slows, add a magnetic stir bar to the reaction tube and stir. The reaction is complete when
none of the magnesium remains. If the level of the ether has decreased, add more.

To prevent decomposition of the Grignard reagent it will be used immediately in the solution that
it is in; there is no isolation or purification of the phenyl magnesium bromide.

 Formation of triphenylmethanol

In an oven dried vial, dissolve benzophenone (364 mg, 2 mmol) in 1 mL of anhydrous ether.
With a dry 1 mL syringe, slowly add the solution to the reaction vessel containing the Grignard
reagent, thus maintaining a gentle reflux.

Rinse the benzophenone vial with a small amount of anhydrous ether and add this to the reaction
tube also. Vent the reaction vessel with a needle as necessary to release pressure. Allow the
reaction mixture to stand at room temperature and observe a color change. The reaction is
complete when the red color disappears.

When the reaction is completed, cool the tube in ice and add to it drop wise (with stirring) 2 mL
of 3M HCl.

It may be necessary to transfer the reaction mixture to a larger container before completing the
addition. As the acid is added the triphenylmethanol will separate from solution as a white
precipitate.

Add additional ether to re-dissolve all the precipitate, it need not be anhydrous. Remove the
aqueous layer using a pipette and add an equal volume of saturated aqueous sodium chloride
solution (brine) to the diethyl ether layer.

Remove the aqueous layer and dry the ether layer by adding anhydrous calcium chloride until the
drying agent no longer clumps. Carefully shake or swirl the vial occasionally over 5-10 minutes.
Remove the ether from the reaction tube and place it in a tared, dry reaction tube. Use additional
ether to wash the drying agent and combine all the ether extracts.

Evaporate the ether in a hood by blowing nitrogen or air onto the solution. After all the solvent
has been removed, determine the weight of the crude product.

There will also be some pale yellow-colored biphenyl present from the reaction of
bromobenzene and phenyl magnesium bromide.

To remove the biphenyl, add 0.5 mL of petroleum ether to the residue, cool in an ice bath
briefly while stirring and remove the solvent (process is called trituration). The remaining
residue (the crude triphenylmethanol) should then be recrystallized from 2-propanol.
Determine the weight, melting point, and percent yield of the triphenylmethanol.
Dichloromethane is a good TLC solvent for comparing triphenylmethanol and biphenyl.

 Characterization

IR spectra for triphenylmethanol:

Defining peaks and analysis

o 3468.05 -OH bond 3035.33 Sp3 hybridized C-H bond

o 1597.79 C=O bond 3062.16 Aromatic C-H bond

Chromatographic analysis:
3.06
4
= 0.77
Discussion
 Use of solvent

Grignard reagents are almost always synthesized in ethereal solvents such as diethyl ether or
tetrahydrofuran (THF) for two very important reasons:
1. ethers do not generally react with Grignard reagents (i.e. they are stable to strong bases
and nucleophiles).
2. The lone pairs on oxygen help to stabilize the partial positive charge on magnesium and
facilitate formation of the Grignard reagent
 Biproduct

Biphenyl, which is formed from a coupling reaction between unreacted bromobenzene and
Grignard reagent, is often observed as a major impurity in this reaction. Formation of the side
product is favored by high concentrations of bromobenzene and increased reaction
temperature. Biphenyl is yellowish in color and can be separated from the triphenylmethanol
product.
  If the reaction doesn’t start quickly, remove the septum and crush the magnesium
with a dry stirring rod. Replace the septum, making sure to release pressure as
necessary using a needle to vent as necessary.
 Precautions
 Grignard reaction is extremely moisture sensitive; oven dry all glassware if possible for
twenty to thirty minutes before starting the reaction.
 Polish magnesium before using to ensure a reactive surface.
 The volume of anhydrous ether must be maintained for a successful Grignard synthesis.
 Do not use flame near the reaction as ether is highly flammable
 mmol

 References
https://www.studocu.com/en-us/document/university-of-louisville/organic-chem-lab-
ii/assignments/orgo-2-lab-experiment-67/7422104/view