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Janel Pauline G. Chua HUB21
De La Salle University – Dasmariňas Dasmariňas 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
The product was placed ijn a pre weighed watch glass and was dried after steam bath. 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 complete schematic diagram for the procedures was shown in Figure 1. Using a Pasteur pipet. 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. 10 grams of crushed ice was added into the reaction mixture and was stirred vigorously. Addition of the nitrating agent must not be less than 15 minutes. The weight of the product was determined. the product was labeled. The reaction mixture was placed in a water bath at room temperature. Once all the ice has been melted. 10 drops of methyl benzoate was added and the weight of methyl benzoate used by difference was determined. drug-sniffing dogs are thus trained to detect the smell of methyl benzoate. Cocaine hydrochloride hydrolyzes in moist air to give methyl benzoate. 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 solid product formed was separated by vacuum filtration. The product was re-crystallized with methanol as directed in Appendix Aand the percentage yield was calculated. the nitrating agent was added slowly to the methyl benzoate solution.study. And lastly. The TLC profile (Appendix B) and melting point (Appendix C) of the re-crystallized product was obtained.) 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 . The reaction vessel was chilled in an ice bath and the mixture was constantly stirred.(2) MATERIALS AND METHODS The conical flask was pre weighed.
cold distilled water again until Place product in watch glass . 5% NaHCO3.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.
1795g Mass of re-crystallized methyl m-nitrobenzoate: 0. The two main reaction types used for this are both substitutions: Electrophilic Aromatic Substitution (EAS) and Nucleophilic Aromatic Substitution (NAS). even if there are other substituents already present. at specific positions relative to each other. is a very important factor in synthesizing many organic compounds. .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. The overall reaction for the nitration of methyl benzoate Benzene rings are components of many important natural products and other useful organic compounds.8624 g Mass of methyl benzoate: 0. EAS. Electrophilic Aromatic Substitution chapter describes the factors involved in the regioselectivity for EAS reactions using benzene rings. Schematic Diagram RESULTS AND DISCUSSION A. on the other hand. which already have substituents on them. which makes NAS difficult. Percentage Yield of methyl m-nitrobenzoate Mass of Erlenmeyer flask: 90. Melting Point Melting point of re-crystallized methyl m-nitrobenzoate: 80⁰C True melting point of methyl m-nitrobenzoate: 78⁰C O C OCH3 HNO3 / H2SO4 O C OCH3 NO2 Figure 2. Therefore.2629g % yield: 68.6829 g Mass of methylbenzoate and Erlenmeyer flask: 90. The benzene ring itself is electron-rich.28 % B. is a very useful method for putting many different substituents on a benzene ring. unless there are a number of strongly electron-withdrawing substituents on the ring. the ability to put substituents on a benzene ring.
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+). Higher the temperature. .HSO4 NO2 + Figure 4. Overall Reaction + HSO4 - + H2O Temperature also has an effect on the product distribution from this reaction. As a result the m-nitrobenzoate is the principal product from this reaction. 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. greater will be the amounts of dinitration products formed from this reaction. Formation of dinitro products from this reaction is unlikely under the conditions in which you carry out your reaction. which already has an ester group. attached to it (methyl benzoate). Reaction Mechanism The carbomethoxy group (-CO2CH3) directs the aromatic substitution reaction to the position that are meta to it.Nitro (—NO2) group was added to the benzene ring. 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. HO-NO2 + H . Concentrated sulfuric acid is the solvent for this reaction and is involved in the formation of nitronium ion (NO2+) from concentrated nitric acid. HONO2 + H2SO4 H2ONO2+ H2O + H2SO4 H2ONO2+ + HSO4 NO2+ + H2O H3O+ + HSO4 - Figure 3.
Benzene mixed with nitric acid and sulfuric acid forms nitrobenzene. (3) . EAS reactions are generally second-order processes. which proceed via several different mechanisms. is the rate-determining step (rds). The basic formula is C6H6 + HNO3 ---> C6H5NO2 + H2O. the sulfuric acid (H2SO4) acting as a catalyst. forming a σ bond ( an arenium cation) followed by deprotonation in step III in the present of a base ( HSO4-) affording the substituted arene. During Step II. by the interaction of a compound containing the potential electrophile and a catalyst. which is used to make methylene diphenyl diisocyanate. Step II. electrophilic aromatic substitutions (EAS) generally occur via the same process. Electrophilic Aromatic Substitution Unlike nucleophilic substitutions.e. i.Figure 5. Most nitrobenzene is used to make aniline. the aromatic π system donates an electron pair to the electrophile. first order in electrophile and first order in arene. Because of the high electron density of the aromatic ring. 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. during EAS reactions electrophiles are attracted to the ring's π system and protons serve as the leaving groups. Usually. rate = k2 [arene][electrophile]. Thus. a chemical component of polyurethane foam insulation..
umkc. 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.edu/drewa/Chem322L/Handouts/EXP %207%20nitration_methylbenzoate%20SP2008.wikipedia.org/wiki/Methyl_benzoate (3) http://wiki.wisegeek.htm (2) http://en.is acting as an electron donating group.com/Q/What_product_is_formed_by_the_nitration_of_benzene (4) http://uk.Figure 6 Nitration of phenyl benzoate is an electrophilic aromatic substitution reaction.answers.answers. (4) REFERENCE (1) http://www.pdf . 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.com/what-are-aromatic-hydrocarbons.web.yahoo.com/question/index?qid=20061119174111AAPDsm1 *http://d.