Nitration of Methyl Benzoate

Janel Pauline G. Chua HUB21

De La Salle University Dasmarias Dasmarias City, Cavite, Philippines

ABSTRACT In Nitration of Methyl Benzoate Experiment, methyl m-nitrobenzene will be synthesized from methyl benzoate and will be purified by recrystallization with methanol. To avoid the formation of other byproducts, the reaction conditions must be controlled carefully. The melting point and TLC profile will also be obtained to ensure that only methyl m-nitrobenzene is formed. Nitration is a general chemical process for the introduction of a nitro group into a chemical compound. The dominant application of nitration is for the production of nitrobenzene, the precursor to methylene diphenyl diisocyanate. Nitrations are famously used for the production of explosives, for example the conversion of glycerin to nitroglycerin and the conversion of toluene to trinitrotoluene. Methyl benzoate undergoes reactions both at the ring and the ester. Illustrative of its ability to undergo electrophilic substitution, methyl benzoate undergoes nitration with nitric acid in the presence of sulfuric acid to give methyl 3nitrobenzoate.

INTRODUCTION Aromatic hydrocarbons are a class of chemical substances which are characterized by having molecular structures which are called benzene rings. The chemically simplest aromatichydrocarbon is benzene, and the structure of this hydrocarbon lent its name to the benzene ring. Many aromatic hydrocarbons are toxic, and they are unfortunately among the most widespread of organic pollutants. A benzene ring is a molecular structure which is created when six carbon atoms connect with each other in a linked ring. Each carbon atom has four electrons; two electrons link up with neighboring carbon atoms, while one goes to a hydrogen atom. The fourth is what is known as a delocalized electron, meaning that it is not directly involved with a specific atom. Benzene rings are often drawn as hexagonal shapes with a circle in the middle to represent these delocalized electrons. Benzene happens to be a particularly toxic form of aromatic hydrocarbon.(1) Methyl benzoate is an ester with the chemical formula C6H5COOCH3. It is formed by the condensation of methanol and benzoic acid, in presence of a strong acid such as hydrochloric acid. It is a colorless liquid that is poorly soluble in water, but miscible with organic solvents. Methyl benzoate undergoes reactions both at the ring and the ester. Illustrative of its ability to undergo electrophilic substitution, methyl benzoate undergoes nitration with nitric acid in the presence of sulfuric acid to give methyl 3-nitrobenzoate. Methyl benzoate also undergoes hydrolysis with addition of aqueous NaOH to give methanol and sodium benzoate, which can be acidified with aqueous HCl to form benzoic acid. Methyl benzoate has a pleasant smell, strongly reminiscent of the fruit of the feijoa tree, and it is used in perfumery. It also finds use as a solvent and as a pesticide used to attract insects. It is one of many compounds that is attractive to males of various species of orchid bees, which apparently gather the chemical to synthesize pheromones; it is commonly used as bait to attract and collect these bees for

study. Cocaine hydrochloride hydrolyzes in moist air to give methyl benzoate; drug-sniffing dogs are thus trained to detect the smell of methyl benzoate.(2) MATERIALS AND METHODS The conical flask was pre weighed. 10 drops of methyl benzoate was added and the weight of methyl benzoate used by difference was determined. The conical flask containing the methyl benzoate was placed in an ice bath. 2 ml of concentrated H2SO4 was added dropwise to the conical flask while swirling. The nitrating agent (1 ml concentrated HNO3 and 1 ml concentrated H2SO4) was prepared in a clean test tube that has been chilled in an ice bath. Using a Pasteur pipet, the nitrating agent was added slowly to the methyl benzoate solution. The reaction vessel was chilled in an ice bath and the mixture was constantly stirred. Addition of the nitrating agent must not be less than 15 minutes. The reaction mixture was placed in a water bath at room temperature. 10 grams of crushed ice was added into the reaction mixture and was stirred vigorously. Once all the ice has been melted, the solid product formed was separated by vacuum filtration. The product obtained was washed with cold distilled water followed by 5% NaHCO3 and finally again with cold distilled water until the filtrate becomes neutral. The product was placed ijn a pre weighed watch glass and was dried after steam bath. The weight of the product was determined. The product was re-crystallized with methanol as directed in Appendix Aand the percentage yield was calculated. The TLC profile (Appendix B) and melting point (Appendix C) of the re-crystallized product was obtained. And lastly, the product was labeled. (The complete schematic diagram for the procedures was shown in Figure 1.)

Conical Determine nitrating Ice aside chilled Set bath theweightto Prepare flask + 10 + nitrating agentin ice Testml concentrated 2 tube drops agent (1 methyl ml concentrated bath of methyl H2SO4benzoate benzoate solution HNO3and 1 ml concentrated H2SO4

Vacuum Filtration Set-Up

-reaction vessel chilled in ice bath -mixture constantly stirred

+ few drops of concentrated H2SO4 until mixture becomes clear IF cloudiness occurs

15 minutes water bath

+ 10 g of crushed ice into reaction mixture

Sti

Separate solid product formed when ice has melted by Vacuum

Wash product with cold distilled water, 5% NaHCO3, cold distilled water again until

Place product in watch glass

Dry over steam bath Re-crystallize Calculate Obtain TLC profile and Label the percentage yield melting with product point of remethanol crystallized product

Determine weight of

Figure 1. Schematic Diagram RESULTS AND DISCUSSION A. Percentage Yield of methyl m-nitrobenzoate Mass of Erlenmeyer flask: 90.6829 g Mass of methylbenzoate and Erlenmeyer flask: 90.8624 g Mass of methyl benzoate: 0.1795g Mass of re-crystallized methyl m-nitrobenzoate: 0.2629g % yield: 68.28 % B. Melting Point Melting point of re-crystallized methyl m-nitrobenzoate: 80C True melting point of methyl m-nitrobenzoate: 78C

O C OCH3 HNO3 / H2SO4

O C OCH3

NO2

Figure 2. The overall reaction for the nitration of methyl benzoate Benzene rings are components of many important natural products and other useful organic compounds. Therefore, the ability to put substituents on a benzene ring, at specific positions relative to each other, is a very important factor in synthesizing many organic compounds. The two main reaction types used for this are both substitutions: Electrophilic Aromatic Substitution (EAS) and Nucleophilic Aromatic Substitution (NAS). The benzene ring itself is electron-rich, which makes NAS difficult, unless there are a number of strongly electron-withdrawing substituents on the ring. EAS, on the other hand, is a very useful method for putting many different substituents on a benzene ring, even if there are other substituents already present. Electrophilic Aromatic Substitution chapter describes the factors involved in the regioselectivity for EAS reactions using benzene rings, which already have substituents on them.

Nitro (NO2) group was added to the benzene ring, which already has an ester group, attached to it (methyl benzoate). The actual electrophile in the reaction is the nitronium ion (NO2+), which is generated in situ ("in the reaction mixture" HNO3/H2SO4) using concentrated nitric acid and concentrated sulfuric acid.

HONO2 + H2SO4 H2ONO2+ H2O + H2SO4

H2ONO2+ + HSO4 NO2+ + H2O H3O+ + HSO4 -

Figure 3. Reaction Mechanism The carbomethoxy group (-CO2CH3) directs the aromatic substitution reaction to the position that are meta to it. As a result the m-nitrobenzoate is the principal product from this reaction. Formation of dinitro products from this reaction is unlikely under the conditions in which you carry out your reaction. The reason for this is that both carbomethoxy groups as well as the nitro group (on the mono nitrated product) are deactivating groups making the second nitration less favorable. Concentrated sulfuric acid is the solvent for this reaction and is involved in the formation of nitronium ion (NO2+) from concentrated nitric acid. Water has a retarding effect on the nitration since it interferes with the nitric acid-sulfuric acid equilibrium (shown in Figure 3) that generates the required nitronium ion (NO2+).

HO-NO2 + H - HSO4

NO2 +
Figure 4. Overall Reaction

HSO4 -

+ H2O

Temperature also has an effect on the product distribution from this reaction. Higher the temperature, greater will be the amounts of dinitration products formed from this reaction.

Figure 5. Electrophilic Aromatic Substitution Unlike nucleophilic substitutions, which proceed via several different mechanisms, electrophilic aromatic substitutions (EAS) generally occur via the same process. Because of the high electron density of the aromatic ring, during EAS reactions electrophiles are attracted to the ring's system and protons serve as the leaving groups. Usually, by the interaction of a compound containing the potential electrophile and a catalyst. During Step II, the aromatic system donates an electron pair to the electrophile, forming a bond ( an arenium cation) followed by deprotonation in step III in the present of a base ( HSO4-) affording the substituted arene. EAS reactions are generally second-order processes, i.e., first order in electrophile and first order in arene. Thus, Step II. is the rate-determining step (rds); rate = k2 [arene][electrophile]. The reaction condition must be maintained at a very low temperature and all reagents must be added very slowly to avoid production of dangerous thermal release or heat which will greatly affect the whole reaction condition. Benzene mixed with nitric acid and sulfuric acid forms nitrobenzene, the sulfuric acid (H2SO4) acting as a catalyst. The basic formula is C6H6 + HNO3 ---> C6H5NO2 + H2O. Most nitrobenzene is used to make aniline, which is used to make methylene diphenyl diisocyanate, a chemical component of polyurethane foam insulation. (3)

Figure 6 Nitration of phenyl benzoate is an electrophilic aromatic substitution reaction. Because the -COOacts as an electron withdrawing group to one phenyl group and a moderate electron donating group to the other pheny group the nitration will occur on the pheny group where the COO- is acting as an electron donating group. The major product of the nitration will have the -NO2 in the para position because the ortho position is partially blocked by the large COPh group. (4)

REFERENCE (1) http://www.wisegeek.com/what-are-aromatic-hydrocarbons.htm

(2) http://en.wikipedia.org/wiki/Methyl_benzoate (3) http://wiki.answers.com/Q/What_product_is_formed_by_the_nitration_of_benzene (4) http://uk.answers.yahoo.com/question/index?qid=20061119174111AAPDsm1 *http://d.web.umkc.edu/drewa/Chem322L/Handouts/EXP %207%20nitration_methylbenzoate%20SP2008.pdf