Grignard Benzoic RXN

Grignard Reagent / Reactions
Preparation of a Grignard Reagent

(Phenylmagnesiumbromide) and reaction
with Carbon Dioxide to form Benzoic Acid
through an Electrophilic Addition reaction
References:
Slayden p. 99 - 102
Pavia p. 303 309; 313 314
Schornick
http://classweb.gmu.edu/~jschorni/chem318
09/16/15
09/16/15
Synthesis of Benzoic Acid Electrophilic Addition

reaction between a freshly prepared Grignard Reagent
(Organomagnesium Halide) acting as the Nucleophilie
(Lewis Base) and the Carbonyl group of Carbon Dioxide
acting as the positively charged Electrophile
The Grignard Reagent must be prepared and reacted
with the solid Carbon Dioxide before the end of the day
Sonication of mixture of Magnesium, Bromobenzene
& Ether (Ether acts as solvent and Grignard stabilizer)
Reaction between Grignard Reagent and Carbon
Dioxide
Hydrolysis of Acid Salt
Product Separation
Liquid/Liquid Extraction
Precipitation
Vacuum Filtration
Product Purification
Recrystallization
Product Verification
Melting Point
2
Laboratory Report:
Synthesis Experiment
Mass, Moles, Molar Ratio, Limiting Reagent,

Theoretical Yield
Procedures
Title Concise: Simple Distillation, Dry Sample, IR

Spectrum, etc.
Materials & Equipment (2 Columns in list (bullet)

form)
Note: include all reagents & principal
equipment used
09/16/15
Description:
Descriptions must be detailed, but concise
Use list (bullet) form
Use your own words (dont copy book)

3
Laboratory Report: (Cont)
Summary
09/16/15
Results Neat, logically designed template to

present results
Paragraph summarizing experimental
observations, computed results, and principal
absorptions from IR & NMR
Analysis & Conclusions
Limiting reagent
Discuss the reaction in context with the results

you obtained; what evidence do you have to
indicate you got the intended product?
Yield How could the experimental process be

improved?
4
Background:
Grignard Reagents, aka, Organomagnesium Halides
Prepared by Reaction of an Organic Halide and

Magnesium metal turnings, usually in an Ether
solvent
Relative Reactivity of Halides is important

RI > RBr > RCl > RF
09/16/15
Very few Organomagnesium Fluorides are produced.
Aryl Grignards are more easily prepared from Aryl

Bromides and Aryl Iodides than Aryl Chlorides
Grignard Reagents are seldom isolated, but they

can be stabilized briefly in Ether solution and then
used in the preparation of other compounds
The preparation of a Grignard Reagent usually

produces a high yield (85 95%)
5
Reactions:
09/16/15
+
+
09/16/15
Reactions (Cont):
The Alkyl portion of the Grignard reagent behaves

as if it had the characteristics of a Carbanion
the carbon atom bears a formal negative charge
The Magnesium portion bears the positive charge
Grignard Reagent, thus, acts as a Strong Base

and is a strong Nucleophile that acts as a Lewis
Base donating an Electron pair to a positively
charged Electrophile
Especially useful in Nucleophilic Addition

reactions of the Carbonyl group, which has
electrophilic character where the positive charge
of the carbonyl carbon atom is attractive to the
Grignard Nucleophile
7
Reactions (Cont):
Grignard & CO2 to produce Benzoic Acid
Grignard & Ketone to Produce Tertiary Alcohol
09/16/15
Reactions (Cont)
Grignard & Aldehyde to Produce Secondary

Alcohol
Grignard & Formaldehyde to Produce Primary Alcohol
09/16/15
Grignard with Benzophenone to form

Triphenylmethanol
09/16/15
10
Grignard with Dry Ice (Solid CO2 ) to form Benzoic

Acid Salt, which is then hydrolyzed with HCL to
form Benzoic Acid
Todays Experiment
09/16/15
11
Preparation of Benzoic Acid:
Experimental Precautions
The Grignard reaction is very reactive. It must be

used in a reaction as soon as it is created.
Moisture must be avoided. Water acts as an Acid in

this reaction; thus the acid proton competes for
the Magnesium in an acid base reaction.
Therefore, moisture could result in the formation of
a Hydrocarbon R-H
R:MgX + H:OH R-H
Stronger
Base
09/16/15
Stronger
Acid
Weaker
Acid
HO-
+ Mg+2 + X-
Weaker
Base
Anhydrous Ether is used to stabilize the Grignard
12
Use as little heat as possible to avoid formation of Biphenyl
Note: The Biphenyl produced from excessive heat is

not the same as the Hydrocarbon formed in an acid
- base reaction above.
09/16/15
The Organic Ether layer contains Benzoic

Acid, Biphenyl and Inorganic Salts.
The Benzoic Acid is separated from the

Biphenyl by converting it to an aqueous
soluble form by washing with NaOH
13
Grignard Benzoic Acid

Procedure (Ultrasonic Bath Version)
Procedure
NOTE: Water/Moisture must be avoided:

All glassware must be dry
09/16/15
Weigh a little more than 0.5g of Magnesium (Mg)

(MW 24.31) to the nearest 0.001 g and place
the Magnesium in a large oven-dried Test Tube or
Centrifuge Tube
Obtain a vial of Bromobenzene (MW 157.01)

and weigh it to the nearest 0.001g
Transfer the Bromobenzene to the test tube

containing the Magnesium filings
Reweigh the empty vile to obtain the net mass of

Bromobenzene
14

Procedure (Ultrasonic Bath Version) (Cont)
Procedure
Add about 10 mL of Anhydrous Ether to the test
tube containing the Bromobenzene and
Magnesium
09/16/15
Add a very small piece of Iodine to the mixture
Add a cotton ball to the top of the test or loosely

screw a cap on the Centrifuge tube (if used)
Place the tube in the Sonication Bath to stimulate

the reaction. The solution will begin to turn
brownish/gray as the reaction proceeds
After about 5 minutes in the Sonication bath, remove the

tube and gently swirl the mixture to insure maximum
exposure of the Magnesium filings to the Bromobenzene
15
09/16/15

Procedure (Ultrasonic Bath Version) (Cont)
Procedure
Replace the tube in the Sonication bath for

about 40 minutes or so
Remaining in the Hood, remove the tube

containing the Grignard reaction mixture from
the Sonication Bath
Pour the solution over approximately 10 g of

Dry Ice (solid CO2) in a labeled 150 mL beaker.
Leave the unreacted Magnesium particles in the
Centrifuge tube
Rinse the tube with a few mL of Ether and add

the Ether to the beaker containing the product
Store labeled beaker containing your product in

the hood until next lab session
16

Week 2 - Hydrolysis & Purification of Benzoic Acid
Procedure
Slowly add about 10 mL of 6 M HCl to the beaker

containing the product
09/16/15
Stir and scrape contents of the beaker with the spatula

until the solids and liquid form a uniform mixture
The mixture may show some reaction activity, such as

frothing and increased temperature, which might
include the reaction between any remaining
Magnesium and the HCl to evolve Hydrogen
add 10 mL Methyl t-Butyl Ether to the beaker
Continue to stir and scrape the mixture with a spatula
If solids still persist in the solution, use a medicine

dropper and add small additional amounts of Methylt-Butyl Ether and stir
17

Week 2 - Hydrolysis & Purification of Benzoic Acid
Procedure
If some solids are still insoluble in either the

ether layer or the aqueous layer, add small
amounts of the 6 M HCl and stir.
Keep track of the volume of HCL added
There should be two distinct clear layers in the

beaker
Note: The Benzoic Acid (and any by-product
Biphenyl) is soluble in the Ether
The inorganic compounds (MgX2) are
soluble
in the aqueous phase
09/16/15
18

Week Two - Hydrolysis & Purification of Benzoic Acid
Procedure
09/16/15
Liquid/Liquid Extraction:
Transfer the mixture to a 125 mL Separatory

funnel
Rinse sides of beaker with additional ether and

add to Separatory funnel
Insert stopper and secure it with your finger
Shake the mixture gently, invert funnel, point

stem up and away from your face and slowly
open stopcock to vent any gas
Allow the layers to separate (remove stopper)
Discard the aqueous (lower) phase into a

separate waste beaker and put aside
19

Week Two - Hydrolysis & Purification of Benzoic
Procedure
Acid
Liquid / Liquid Extraction with Distilled Water

(Cont)
Add 5 mL distilled water to the organic
solution
Shake the mixture gently, invert the funnel,
and slowly open stopcock to vent any gas
Discard aqueous phase
Repeat the liquid/liquid extraction with an
additional 5 mL of distilled water
09/16/15
20
09/16/15

Procedure
Liquid / Liquid Extraction with Sodium Hydroxide
To the organic layer, which contains the

Benzoic Acid and by-product Biphenyl, add 5
mL 5% NaOH
Shake the mixture gently, invert funnel

pointing away from your face, and slowly open
stopcock to vent any gas
Drain aqueous (bottom) layer into clean, dry

100 ml beaker
Repeat liquid/liquid extraction with another 5

ml 5% Sodium Hydroxide, draining bottom
layer into your beaker
Repeat liquid/liquid extraction a 3rd time with

5% Sodium Hydroxide
21

Procedure
Acid
Liquid / Liquid Extraction with Sodium Hydroxide

(cont)
Note: The Sodium Hydroxide converts the Benzoic

Acid to the water-soluble Sodium
Benzoate salt
The Sodium Benzoate is thus transferred
to the aqueous phase
09/16/15
Discard the organic Ether layer into the waste jar

in the hood
22

Procedure
Acid
Remove Excess Ether
Gently heat the combined aqueous extracts

(about 15 mL) containing the Benzoic Acid
salt on a hot plate (set setting at 3-4) until
formation of small bubbles (Ether) ceases.
This removes any residual Ether, which is
slightly soluble in water
Note:
Dont overheat; heat just enough
to boil off
Ether
09/16/15
23

Procedure
Cool the solution to room temperature
Add 10.0 mL 6 M HCl and stir (a precipitate forms

in the beaker)
Note: If little or no precipitate forms add an
additional 3 ml HCL. If no precipitate forms inform
instructor
09/16/15
Cool mixture in water/ice bath
Vacuum Filtration
Vacuum filter the product using a Buchner Funnel
Wash crystals on the filter 2 times with 5 mL cold

distilled water
24

Procedure
Recrystallize product from hot (near boiling) water
Transfer solid from Buckner Funnel to 100-150

mL beaker using cold Distilled Water to insure
complete transfer
Add an additional 15 mL of distilled water to

mixture
Heat solution to just below boiling point,

swirling the mixture occasionally until all solids
go into solution
Note: The Benzoic Acid solution gives off a strong

pungent vapor; avoid proximity to nose
09/16/15
Check with instructor if you feel additional

Distilled Water is needed to effect total solution
25

Procedure
Acid
09/16/15
Recrystallize Product (Cont)
Allow solution to cool slowly to room

temperature effecting recrystallization of the
purified product (Soluble impurities remain in
solution
If the cooled solution does not appear to have

sufficient water to suspend the purified crystals as a
slurry, add 10 ml of Distilled Water, redissolve the
mixture, and cool again slowly to room temperature
After mixture has reached room temperature, place

the beaker in an ice/water bath for about a minute
26

Procedure
Acid
2nd Vacuum Filtration

Clean
and dry the Buckner Funnel, add a new

filter, and weigh it to the nearest 0.001g
Assemble the Buckner Funnel and vacuum

filter the product
Wash crystals on the filter with 5 mL cold
Distilled Water
Dry the product in a pre-weighed weighing
tray in the class drawer until next week
09/16/15
27

Procedure
Weigh the dried product & weighing tray to the

nearest 0.001g
Compute the mass of product (Benzoic Acid) by

difference
Determine the % yield
Determine the melting point of the product
(MP of Benzoic Acid 122.4oC)

NOTE:
see next
09/16/15
If little or no yield was obtained,

slide
28

The Experiment was a Bust!!
Procedure
Occasionally students get little or no yield for the

Grignard / Benzoic Acid experiment
The principal reason for this is the failure of the

original reaction between Bromobenzene and
Magnesium to form the Grignard Reagent
There are two main indications of a failed

reaction:
09/16/15
No precipitate forms upon the addition of the 6

M HCL to the aqueous NaOH washings
The precipitate largely disappears after the first

vacuum filtration
29

The Experiment Was a Bust
Procedure
09/16/15
In order to give the students full exposure to

the complete procedure, the following steps
should be performed:
Weigh out to the nearest 0.001 g approximately

3 grams of Benzoic Acid supplied by the
instructor
Dissolve the Benzoic Acid in 15 mL Anhydrous

Ethyl Ether.
Wash the Ether phase 3 times with 5 mL 5%

NaOH as before combining the 3 aqueous
washings in a beaker
Discard the Ether

30

The Experiment Was a Bust
Procedure
Gently
heat the NaOH solution, approximately 15

mL, to drive off any residual Ether
Cool
Add
bath
A
the solution to room temperature

10 mL HCL, as before, and place in water-ice
precipitate should form
Separate
Wash
the precipitate by vacuum filtration
product on filter with 5 mL cold water
Recrystallize
Vacuum
Dry
Filtration
the Product
Determine
09/16/15
the product from hot distilled water
the Melting Point

31

Note: Lab procedure
sequence vs. Lab report
Procedure
procedure sequence
09/16/15
The writing of the laboratory report does not

always follow the exact physical sequence of
procedures used in the lab
The measurement of the Mass of a reagent may

be immediately followed by an apparatus set-up
or transfer of the sample to a piece of apparatus
This same process could be repeated with the

second or a third reagent used in the experiment
In your report, however, all determinations of

Mass are followed immediately by all calculations
that can be based on the Mass values, i.e. moles,
molar ratios, limiting reagent, theoretical yield,
etc.
32

In the Grignard experiment the following
Procedure
calculations are carried out before any
procedure dealing with the mixing of the

reagents and subsequent processing of the
reaction mixture
09/16/15
Mass of first reagent
Mass of second reagent (HCL Vol & Density)
Moles of both reagents (1 procedure)
Set up Balanced Stoichiometric Equation
Determine Molar Ratio
Determine Limiting Reagent
Compute Theoretical Yield

33

Use the following table form (handout) as a
Procedure
substitute for the
table in the Lab Manual Data
Report.
Balanced
Equation
Mg
Ether
CO2
HCl
Mixed
Salts
Mol Wgt
Grams
Moles
09/16/15
34

Hydrolysis of
Procedure
Benzoic Acid Salt
Ether Layer
8 mL 6 M HCL
20 mL Anhydrous Ether
Separatory Funnel (Shake Gently)
Benzoic Acid
Biphenyl
Aqueous Layer
Inorganic Salts (Discard)
Add 5 mL 5% NaOH
Aqueous Layer
(Repeat 3 Times)
Biphenyl (Discard)
Soluble Benzoic Acid Salt

(Trace of Ether)
Heat on Hot Plate in Hood to Drive off Ether

Cool to Room Temperature
Add 10 mL 6 M HCl
09/16/15
35

Grignard Benzoic RXN

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Grignard Reagent / Reactions

Preparation of a Grignard Reagent

Grignard Reagent / Reactions

Synthesis of Benzoic Acid Electrophilic Addition

Grignard Reagent / Reactions

Mass, Moles, Molar Ratio, Limiting Reagent,

Title Concise: Simple Distillation, Dry Sample, IR

Materials & Equipment (2 Columns in list (bullet)

Descriptions must be detailed, but concise

Use list (bullet) form

Use your own words (dont copy book)

Grignard Reagent / Reactions

Laboratory Report: (Cont)

Results Neat, logically designed template to

Analysis & Conclusions

Discuss the reaction in context with the results

Yield How could the experimental process be

Grignard Reagent / Reactions

Grignard Reagents, aka, Organomagnesium Halides

Prepared by Reaction of an Organic Halide and

Relative Reactivity of Halides is important

Very few Organomagnesium Fluorides are produced.

Aryl Grignards are more easily prepared from Aryl

Grignard Reagents are seldom isolated, but they

The preparation of a Grignard Reagent usually

Grignard Reagent / Reactions

Grignard Reagent / Reactions

The Alkyl portion of the Grignard reagent behaves

The Magnesium portion bears the positive charge

Grignard Reagent, thus, acts as a Strong Base

Especially useful in Nucleophilic Addition

Grignard Reagent / Reactions

Grignard & Ketone to Produce Tertiary Alcohol

Grignard Reagent / Reactions

Grignard & Aldehyde to Produce Secondary

Grignard & Formaldehyde to Produce Primary Alcohol

Grignard Reagent / Reactions

Grignard with Benzophenone to form

Grignard Reagent / Reactions

Grignard with Dry Ice (Solid CO2 ) to form Benzoic

Grignard Reagent / Reactions

Preparation of Benzoic Acid:

The Grignard reaction is very reactive. It must be

Moisture must be avoided. Water acts as an Acid in

Anhydrous Ether is used to stabilize the Grignard

Grignard Reagent / Reactions

Use as little heat as possible to avoid formation of Biphenyl

Note: The Biphenyl produced from excessive heat is

The Organic Ether layer contains Benzoic

The Benzoic Acid is separated from the

Grignard Benzoic Acid

NOTE: Water/Moisture must be avoided:

Weigh a little more than 0.5g of Magnesium (Mg)

Obtain a vial of Bromobenzene (MW 157.01)

Transfer the Bromobenzene to the test tube

Reweigh the empty vile to obtain the net mass of

Grignard Benzoic Acid

Add a very small piece of Iodine to the mixture

Add a cotton ball to the top of the test or loosely

Place the tube in the Sonication Bath to stimulate

After about 5 minutes in the Sonication bath, remove the

Grignard Benzoic Acid

Replace the tube in the Sonication bath for