Experiment: # 5

Nitration of Chlorobenzene

Name: Ali Marzuk, 4855366

CHM 2123, Section B24

TA: Kirk Mulligan

Date: October 20th, 2008

Department of Chemistry

University of Ottawa

1. Theory and mechanism: The reaction that occurred in this experiment was the electrophilic addition of NO2 to chlorobenzene. To have this occur, we must (1), protonate nitric acid by mixing it with sulfuric acid. This produces NO2+ which can be (2), added to chlorobenzene to form chloronitrobenzene at the ortho or para position. NO2 attacks the ortho and para positions due to the effect of the chlorine substituent. It has a weak deactivating effect, which means (3) it has some resonance stability at the ortho and para positions.
+

Balanced Chemical Equation:

Cl Cl Cl NO2 Cl

NO2(+)

NO2

Chlorobenzene

Ortho isomer (1,2)

Meta isomer (1,3)

Para isomer (1,4)

NO2

Mechanisms: Activation of the nitric acid using sulfuric acid:

O N HO
+

O OH N H2O
+ +

+
O
-

O H

S O

S O

OH

Nitric Acid

Sulfuric Acid

Nitronium Ion

Reaction of electrophillic nitronium ion with nucleophilic benzene:

+
Benzene
H

O CH
+

H N O
+

+
O
-

NO2

Nitrobenzene

2. Table of reactants and solvents: Compound Molecular weight ( g/mol) 63.0128 98.0734 112.5585 46.1 Mass (g) 2.107 Density(g/ml) Volume (mL) 6.0 6.0 2.0 Enough to dissolve crude product Mmol (millimoles) 0.113 0.094 0.018 Eq (equivalents ) 6.3 5.2 1 -

Concentrated nitric acid Concentrated Sulfuric acid Chlorobenzene Ethanol

1.42 1.84 1.11 -

3. Experimental procedure: For the complete procedure, please refer to lab manual Organic Chemistry Laboratory: CHM 2123, fall 2008, pg: 40-41. 4. Observation: Nitration of chlorobenzene Procedure Nitric acid, sulfuric acid and chlorobenzene mixed After cooling in ice water bath Crude after filtration Observation Cloudy, translucent, white

Pale yellow chunks in cloudy/white solution Product was extremely yellow and chunky and hard in texture

Separation of p-chloronitrobenzene from o-chloronitrobenzene Procedure Dissolving the crude product in ethanol on a hot plate After letting the crude product stand at room temperature undisturbed for 7-10 minutes After addition of distilled water Observation Light , clear yellow solution Large needles of about length 1-1.5 cm grew at the bottom of the flask White needle-like crystals formed

5. Results : Data Mass of crude product Mass of refined product Ratio of para to ortho isomer Percent yield Melting point obtained Theoretical melting point 6. TLC Plates: Results 3.54 g 0.66 g 7:3 33.67 % 90-91.5 oC 83-84 oC

7. Sample Calculations: Amount of chlorobenzene = 2.0 g (0.018 mol) Amount of HNO3 = 6.0 mL x 1.42 g/mL = 8.52 g No. of moles of chlorobenzene = no. of moles of chloronitrobenzene Mass of chlorobenzene = (0.018 mol)(157.45 g/mol) = 2.8 g The p-isomer is 70% of the product So the theoretical yield of the p-chloronitrobenzene = 0.70 x 2.8 g = 1.96g % yield = 0.66 g/ 1.96 g x 100% = 33.67 % Rf (A) = A/x = 3.4 cm/ 4.6 cm = 0.739 8. Discussion:

The percent yield is 33.7 % for this experiment. The product isolated was needlelike crystals that were white in color and appeared to have a flaky texture. In this reaction, the chlorobenzene reacts with the nitronium ion in a preferential fashion. This is because there is a directing effect produced by the chloro group on the benzene. The literature melting point for 1-chloro-4-nitrobenzene is 83C-84C, whereas the experimental melting point was 90.0 C 91.5C. This slight change and broadening of the melting point range shows that the product isolated was not in its purest form, however it is still relatively pure. The slight impurity is also seen in the TLC slide that shows a small amount of by-product that has a smaller RF than the desired compound of 1-chloro-4-nitrobenzene. It is believed that some of the ortho product remained as a part of the re-crystallized product. The para isomer is less polar and thus had a larger RF value in the TLC analysis than did the ortho isomer, which is more polar and was adsorbed more strongly to the surface of the silica plate. This polarity difference is due to the fact that the para product (1-4) is more of a symmetrical molecule with the electron withdrawing groups of chlorine and nitronium having a canceling-out effect on one another, thus reducing the overall polarity of the molecule. On the other hand, in the ortho (1,2) isomer, the two electron withdrawing groups are close to one another and there is no symmetry to the molecule, thus the overall polarity of the molecule is increased, as proven in the TLC analysis.

The general mechanism for the electrophilic addition starts when the electrons form a double bond from the resonance benzene ring attacks a great electrophile attached to a great leaving group. The electrophile attaches to one side of the double bond, which leaves the other side with a positive carbocation. This ion of this intermediate step is known as the arenium ion. Next a base, most likely the leaving group deprotonated or attacks the hydrogen that is bonded to the same carbon as the electrophile. The electrons from the hydrogen go back into the ring reforming the benzene ring. 9. Questions: