Module 9 Exp 34A
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Module 9: Experiment 34A Haloform Reaction: Benzoic Acid
Performed on November 1, 2023
Objective:
Perform a haloform reaction using acetophenone to obtain benzoic acid and
chloroform. Observe and analyze the product through IR spectrum and melting point.
Procedure:
1.
To a 5 mL conical vial containing a spine vane and equipped with an air condenser add
90
l of acetophenone and 3.2 mL of sodium hypochlorite
2.
Stir the acetophenone-bleach mixture for 30 minutes at room temperature
3.
Add 35 mg of sodium sulfite and stir briefly
4.
Extract resulting mixture with two 0.5 mL portions of ether
5.
Acidify the aqueous layer by adding 3M HCl dropwise (monitor pH frequently while
acidifying)
6.
Cool in an ice bath for 10 minutes and then collect the solid using Hirsch funnel. Wash
the filter cake with 3 0.5 mL portions of cold water and leave in Hirsch funnel for 5-10
minutes to dry
7.
Weigh the product and find melting point plus the IR spectrum
Reaction Scheme:
Results and Data:
Molecular
Formular
Molecular
Weight
Amount
mmol
Boiling
Point
Melting
Point
Densit
y
Acetophenon
e
C
8
H
8
O
120.4
g/mol
90
l
51
mmol
202.6
C
1.03
g/cm
3
Sodium
Hypochlorite
NaClO
74.44
g/mol
3.2 mL
101
C
1.11
g/cm
3
Sodium
Sulfite
Na
2
SO
3
126. 04
g/mol
35 mg
33.4
C
Benzoic Acid
C
7
H
6
O
2
122.12
g/mol
TY: 94
mg
EY: 38
mg
122.3
C
Calculations:
1) Theoretical yield of benzoic acid:
90
l (1 mL/1000
l)(1.03g/mL)(1 mol C
8
H
8
O/120.4 g)(1 mol C
7
H
6
O
2
/1 mol C
8
H
8
O)(122.12
g/mol)= 0.094 g = 94 mg
2) Yield of benzoic acid
0.038 mg = 38 g
3) % Yield of benzoic acid
(0.038 mg /0.094 mg)(100)= 40.4%
4) Melting Point: 122
C
Observations:
-
No change with stirring acetophenone and sodium hypochlorite solution for 30 minutes
-
When HCl was added it solidified and bubbled until mixed into solution fully
-
Litmus paper kept bleaching so added 10-15 mg of sodium sulfite
-
Took longer than expected to fully crystallize in ice bath
Questions
: Answer the following questions. Be as complete as possible, and always explain your
reasoning.
1. Write a mechanism for the formation of benzoic acid from acetophenone via the haloform
reaction. Be as complete as possible and show electron flow for all steps.
Use Cl
2
as the halogenating agent in your mechanism
(you do not need to write a
mechanism for the formation of Cl
2
from NaOCl).
Be as complete as possible and show
electron flow for ALL
steps
.
NOTE: This mechanism involves several enolate formation and subsequent reaction
steps. To earn full credit,
all steps must be written
. For the first enolate formation,
show both possible enolate resonance structures. For subsequent enolates, you may draw
a single resonance structure, with the negative charge on the -carbon.
Do NOT simply write out the book mechanism without any critical review. It may not be
complete in terms of showing ALL electron flow (proton transfers, in particular, are often
assumed and not drawn out fully). You are responsible for writing complete
reaction
mechanisms that are inspired by the rules and guidelines set forth in both the lab AND
lecture
courses.
2. The mechanism of the haloform reaction involves a
carbanion
leaving group
, an exception
to the general rule.
a)
Draw the chemical structure of the carbanion leaving group.
b) Explain why, in the case of the haloform reaction, this leaving group is reasonable (why it
is an exception to the rule).
The carbanion is surrounded by chlorines which have an
electron-withdrawing nature due to its electronegativity. The
chlorine atoms can then release electrons through resonance.
The stability of this carbanion allows it to be an exception to
the rule because the delocalization of the negative charge
which allows for functioning of a leaving group.
3. Using the
1
H NMR spectrum shown below.
a) Confirm the identity of the compound using the NMR provided. Is this consistent with
acetophenone (starting material) or the benzoic acid (product)?
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