Experiment #33: Aromatic nitration 33.2 Part B http://www.orgsyn.org/orgsyn/orgsyn/prepContent.asp?

?prep=cv1p0372 Introduction: The purpose of the lab was to understand the aromatic electrophilic substitution reaction of nitration. In such a reaction, the active electrophilic species was the nitronium derived from the reaction with sulfuric acid. The attack by the nitronium ion was the slow rate-determining step followed by the loss of a proton. Nitration is dependent on the substituents attached to the benzene ring. For instance, electron withdrawing groups slow down the reaction while electron releasing groups aid the reaction. The final product of methyl m-nitrobenzene was weighed, and its melting point and IR were taken. STRUCTURES

Procedure: 3 ml of concentrated sulfuric acid was placed in a 50 ml Erlenmeyer flask, and then cooled in an ice bath. 1.3 mL of methyl benzoate was added to the solution while swirling. Drop by drop addition of the cold 1 mL concentrated sulfuric acid and 1 mL concentrated nitric acid mixture followed. After the addition, the solution was swirled for about 10 minutes. The mixture was poured over a handful of ice in a 250 mL beaker. After all the ice melted, it was filtered through a Buchner funnel. The mixture was washed three times with 3 mL portions of water, followed by two 1 mL portions of ice-cold methanol. The residue was weighed, and the melting point and IR were taken. Table of chemicals: Chemical Conc. Sulfuric Acid Methyl benzoate Conc. Nitric acid Water Methanol Crude methyl m-nitrobenzoate (product) Mechanism:

Quantity 3 mL; 1 mL 1.3 mL 1 mL (3x) 3 mL (2x) 1 mL 1.667

MW 98.079 136.15 63.01 18.01 32.04 181.13

MP (actual) -----74-76

MP (experimental) -----69.2-71.4

Density 1.08 g/mL

Observation: Sulfuric acid was clear and colorless but viscous. Metyl benzoate was not was viscous but was clear and colorless. When combined, the solution was clear and colorless. Nitric acid was clear and colorless. When nitric acid and sulfuric acid combined, the solution was pale yellow and viscous. After adding drop by drop, the solution turned pale yellow and clear. When precipitating out over ice, the solution was at first a milky, grainy, faint yellow solution, and then it curdled into chunks. After filtration, the filtrate was clear and colorless; while the residue was pale yellow curd chunks. After water and methanol washing, the residue was less yellow. ATTACH THE IR SPECTRUM Percent yield:

Results: 1. Crude mass was 1.667 g; 89.25% yield; should be lower due to improper drying techniques and possible ortho/para isomers (improper washing); excess water can be identified through IR; the theoretical percent yield is not specific towards the meta position (it suggests the entire product would contain ortho, para, and meta positions which makes sense as to why my mass was so high). 2. Melting point was lower because of impurities of sulfuric and nitric acid (improper washing): An impurity causes
the melting point to deviate from the standard. Actually, it makes the magnitude of the melting point lower. For example, the melting point of benzoic acid is 122.4 degree Celcius. When we did this in the laboratory, we got 120 degree Celcius because of the impurity present which is sodium sulfate. An impurity also causes the melting point to become a melting range. The melting point is not anymore sharp, but a range of values. The more impurities present, the greater the range of values. For example, when we purified crude acetanilide via recrystallization, we obtained a melting range of 105-116 degree Celcius. By the way, the standard melting point of acetanilide is 113-115 degree Celcius. So basically, those are the two effects that impurities have on melting point iof a pre compound. I learned that it is because the impurities "defect" the crystal lattice of the compound. A pure compound is a structure of high molecular symmetry. An impurity is rather assymetrical, or is a poorly organized structure. If the impurites are present with the pure compound, the melting point will deviate because melting point is also dependent on the

high symmetry and organization of molecular structures, just as the vapor pressure. This is the principle involved in Sublimation and Melting point determination.

3. IR: peak at 1525.77 cm-1 indicate NO2 group; 1715.53 cm-1 result of carbonyl group; 1074 C-O bond; Questions: 1. Why is sulfuric acid used in nitration? Sulfuric acid was used to produce the nitronium ion which would be able to react with the benzene ring. 2. What position will be taken by the entering nitro group when the following substances are nitrated? Which will react most rapidly? Which is least reactive? a. Bromobenzene b. Nitrobenzene c. Toluene d. Tert-butylbenzene e. Ethyl benzoate f. Benzoic acid 3. Look up and write the structural formula of: a. Picric acid b. TNT c. Tetryl