Академический Документы
Профессиональный Документы
Культура Документы
Methyl Benzoate
In your study of aromaticity, you learned that not all aromatic chemical
species are derivatives of benzene but many are. In fact, most aromatic compounds
can be considered derivatives of benzene, and we shall use benzene to explore the
differences in reactivity between aromatic hydrocarbons, known as arenes, and the
aliphatic hydrocarbons called alkenes. We know from first-semester organic
chemistry that alkenes undergo addition reactions to the double bond.
Alkenes are electron rich because of the two electrons in the bond of the
double bond. These electrons are seeking a positive charge or the positive end of
a reagent, and the positive charge or positive end of the reagent is seeking the
electrons. Thus, the reagent is an electrophile, and we describe the addition of the
reagent to the double bond as an electrophilic addition reaction.
negative electrons in bond seek positive reagent
H Br
BrH
cyclohexene
carbocation
intermediate
Br
H
bromocyclohexane
+
benzene
aromatic
H Br
Br
H
5-bromo-1,3-cyclohexadiene
non-aromatic
This reaction does not occur, because the product is not aromatic.
Lab 5
H
H
E+
slow
Step 1
fast
Step 2
Lab 5
H O N
O
+
H O S
H O N
O H
nitric acid
+
O
O S
O H
sulfuric acid
O N O
H O H
nitronium ion
H
H
benzene
+NO
2
slow
Step 1
NO2
carbocation
intermediate
fast
Step 2
NO2
nitrobenzene
is bonded to the ring, and a three-bonded carbon atom in the ring has a positive
charge (i.e., it is a carbocation). A carbocation is a carbon atom that has only three
bonds and a vacant p orbital. Thus, a carbocation is not a stable chemical species.
In Step 2, aromaticity is restored when the pair of electrons from the H atom fills
the vacant p orbital of the carbocation. This is shown by the second curved arrow.
The final product is nitrobenzene. The hydrogen atom (proton) that leaves in Step 2
is bonded to the same carbon atom as the NO2 group, making the reaction a
substitution reaction.
Nitration of Methyl Benzoate
In our lab reaction, the substrate is methyl benzoate an ester rather than
benzene, because benzene is carcinogenic. When a group such as the
carbomethoxy group in methyl benzoate is bonded to the benzene ring, the group
determines where the electrophile, E+, will bond on the ring. Groups that can
donate electron density to the ring are called electron-donating groups, EDGs.
Electron donating groups cause the electron density in a benzene ring to be altered
so that the carbon atoms ortho and para to the EDG have more electron density
than do the carbon atoms meta to the EDG. On the other hand, groups that
withdraw electron density from a benzene ring when they are bonded to it are
called electron withdrawing groups or EWGs. Electron withdrawing groups alter
the electron density of the ring by making the ortho and para carbon atoms positive
relative to the carbon atoms meta to the EWG. This means that an electrophile will
bond to the ortho or para position of an EDG and meta to an EWG. This is shown
in Figure 7.
EWG
EDG
ortho, para
director
meta director
Lab 5
n
O CH3
Lab 5
with a vacant p orbital. When a three-bonded carbon has eight valence electrons, it
is a carbanion. Applying these constraint rules to methyl benzoate, we can
determine whether it is possible to form a double bond at the green bond (i.e.,
whether the carbomethoxy group is an EDG or EWG). We find that it is impossible
to draw a structure with a double bond to the ring by using the blue electrons (
or n electrons outside the ring). However, it is possible to draw a structure with a
double bond to the ring by using red electrons ( electrons from the ring). If you
cannot draw the resonance structures that prove that the CO2Me group is an EWG,
then please review the tutorial entitled Resonance that accompanies this lab
manual.
Mechanism for the Nitration of Methyl Benzoate
The mechanism for the nitration of methyl benzoate is the same as that
shown in Figure 6 except that we must make the NO2 (nitro group) go to a meta
position relative to the CO2Me group that is already bonded to the ring. This means
that the positive charge in the carbocation intermediate must be on an ortho or para
carbon relative to the CO2Me group.
CO2Me
H
H
methyl benzoate
NO2+
slow
CO2Me
H
Step 1
NO2
carbocation
intermediate
CO2Me
fast
Step 2
NO2
methyl m-nitrobenzoate
Lab 5
Procedure
Precaution Nitric acid and sulfuric acid are both strong acids that can burn
skin. Be careful not to spill either acid on yourself. If you do, wash the area
quickly and thoroughly with water.
1. Place a 4-mL conical (V-shaped) reaction vial from a microkit on a balance and
tare it to zero.
2. Add 10 drops of methyl benzoate to the reaction vial while the vial is still on the
balance. Record the mass of the added methyl benzoate directly on your lab data
sheet and then take the vial to your bench.
3. Add 12 drops of concentrated sulfuric acid, H2SO4, to the vial and mix it
thoroughly with the methyl benzoate.
4. Attach the condenser form the microkit to the conical vial.
5. Clamp the condenser to a ring stand.
The following photo shows a conical vial immersed in an ice-water bath.
6. Prepare and ice-water bath in a 250-mL beaker by adding both ice and water to
the beaker.
7. Adjust the condenser so that the reaction vial is immersed in the ice-water bath.
Lab 5
8. Add six drops of concentrated nitric acid, HNO3, and six drops of concentrated
sulfuric acid, H2SO4, to a small test tube.
This mixture of concentrated nitric and sulfuric acids is called the nitrating
mixture, because both acids are required for a successful nitration.
9. Cool the test tube containing your nitrating mixture in your ice-water bath.
10. Transfer one drop of the cold nitrating mixture to the reaction vial. Instead of
unscrewing the reaction vial to add the nitrating mixture, add it through the open
tube in the condenser.
11. Carefully swirl the condenser/reaction vial setup to ensure good mixing of the
reactants.
12. Add one drop of the nitrating mixture through the condenser about every thirty
seconds until all of the nitrating mixture has been added.
13. After all of the nitrating mixture has been added, remove the condenser from
the ice-water bath but leave it clamped to the ring stand for about 10 min.
14. Place about two grams of crushed ice in a 50-mL beaker.
15. Carefully pour the reaction mixture from the reaction vial over the crushed ice.
The ice is solid water, which will effectively absorb the heat of solvation of
the excess acids in the mixture. The ice will melt in the process, and the product
is a solid that is insoluble in water.
16. After the ice melts, collect the solid product of methyl m-nitrobenzoate on a
Hirsh funnel.
17. Continue the suction until the solid is as dry as possible then record its mass
directly on your data sheet. Conduct any addition tests as directed.
18. Wash and rinse all glassware and return it to the microkit or to its proper
storage location. Replace the ring stands to their storage locations. Check the
Lab 5
balance area. Turn off all balances and return any chemicals to their proper
locations.
Electrophilic Aromatic Substitution
Stu No___ Sec___Stu last name_________________________, First___________
1. What chemical is added to nitric acid and to sulfur trioxide to make them
suitable electrophiles for nitrating and sulfonating a benzene ring?
Ans._____________________________________
2. What is the electrophile in the nitration of methyl benzoate? Ans. __________
3. Draw a resonance structure of chlorobenzene that shows it to be an EDG by
resonance.
Cl
6. Starting with the structure of nitrobenzene, draw one resonance structure that
shows it to be an EWG by resonance.
O
N
Lab 5
10
7. Primary carbocations are too unstable (require too much energy) to form in a
typical lab reaction. When propyl chloride reacts with benzene in the presence of
aluminum chloride, isopropylbenzene is obtained. Write an equation for this
reaction.
Cl 2
AlCl3
9.
10.
Br2
CHCl3
Lab 5
11