Nitration of Methyl Benzoate

Palaya, Gerard Pintor, Karlo Sena De La Salle University Dasmarinas Dasmarinas City, Cavite, Philippines BS!" C! In Nitration of Methyl Benzoate Experiment, methyl m-nitrobenzene is synthesized from methyl benzoate and purified by recrystallization with methanol. To reduce the probability of formation of other -products, the reaction conditions must be processed carefully. The meltin point and T!" profile will also be obtained to confirm that only methyl m-nitrobenzene is the final product. Nitration is a chemical process for the introduction of a nitro roup into a chemical compound. The dominant application of nitration is for the production of nitrobenzene. Methyl benzoate under oes reactions both at the rin and the ester. Illustrati#e of its ability to under o electrophilic substitution, methyl benzoate under oes nitration with nitric acid in the presence of sulfuric acid to i#e methyl $-nitrobenzoate.

#N!"$DUC!#$N %romatic hydrocarbons are a chemical substances which are &nown by ha#in molecular structures which are called benzene rin s. The chemically fundamental aromatic hydrocarbon is benzene, and the structure of this hydrocarbon a#e its name to the benzene rin . Many aromatic hydrocarbons are toxic, and they are amon the most widespread of or anic pollutants. % benzene rin is a molecular structure which is created when six carbon atoms connect with each other in a lin&ed rin . Each carbon atom has four electrons' two electrons lin& up with nei hborin carbon atoms, while one oes to a hydro en atom. The fourth is &nown as a delocalized electron, meanin that it is not directly in#ol#ed with a specific atom. Benzene rin s are often drawn as hexa onal shapes with a circle in the middle to represent the delocalized electrons. Benzene happens to be a particularly toxic form of aromatic hydrocarbon. Methyl benzoate is an ester with the chemical formula "()*"++")$. It is formed by condensation of methanol and benzoic acid, in presence of a stron acid li&e hydrochloric acid. It is a colorless li,uid and poorly soluble in water, but miscible with or anic sol#ents. Methyl benzoate under oes reactions both at the rin and the ester. Illustrati#e of its ability to under o electrophilic substitution, methyl benzoate under oes nitration with nitric acid in the presence of sulfuric acid to form a methyl $-nitrobenzoate. Methyl benzoate also under oes hydrolysis with addition of a,ueous Na+) to i#e methanol and sodium benzoate, which can be acidified with a,ueous )"l to form benzoic acid. Methyl benzoate has a ood smell, a reminiscent of the fruit of the fei-oa tree, and it is commonly used in perfumes. It also use as a sol#ent and as a pesticide used to attract insects. It is one of many compounds that is attracti#e to males of #arious species of orchid bees, which apparently ather the chemical to synthesize pheromones' it is commonly used as bait to attract and collect these bees for study. "ocaine hydrochloride hydrolyzes in moist air to i#e methyl benzoate' dru -sniffin do s are thus trained to detect the smell of methyl benzoate.

M !%"# LS ND M%!&$DS The conical flas& was pre wei hed. ./ drops of methyl benzoate was added and the wei ht of methyl benzoate used by difference was determined. The conical flas& containin the methyl benzoate was placed in an ice bath. 0 ml of concentrated was added drop wise to the conical flas& while swirlin . The nitratin a ent 1. ml concentrated and . ml concentrated2 was prepared in a clean test tube that has been chilled in an ice bath. 3sin a 4asteur pipette, the nitratin a ent was added slowly to the methyl benzoate solution. The reaction #essel was chilled in an ice bath and the mixture was constantly stirred. %ddition of the nitratin a ent must not be less than .* minutes. The reaction mixture was placed in a water bath at room temperature. ./ rams of crushed ice was added into the reaction mixture and was stirred #i orously. +nce all the ice has been melted, the solid product formed was separated by #acuum filtration. The product obtained was washed with cold distilled water followed by *5 and finally a ain with cold distilled water until the filtrate becomes neutral. The product was placed in a pre-wei hed watch lass and was dried after steam bath. The wei ht of the product was determined. The product was recrystallized with methanol. %nd the percenta e yield was calculated. The T!" profile and meltin point of the re-crystallized product was obtained. %nd lastly, the product was labeled. "%SUL!S ND D#SCUSS#$N %. 4ercenta e 6ield of methyl m-nitro benzoate Mass of Erlenmeyer flas&7 8/.(908 Mass of methyl benzoate and Erlenmeyer flas&7 8/.9(0: Mass of methyl benzoate7 /.$. Mass of re-crystallized methyl m-nitro benzoate7 /.0. 5 yield7 (95 B. Meltin 4oint Meltin point of re-crystallized methyl m-nitro benzoate7 ;( " True meltin point of methyl m-nitro benzoate7 ;9 "

O C OCH3 HNO3 / H2SO4

O C OCH3

NO2
<i ure .. The general reaction for the nitration of methyl benzoate Benzene rin s are constituents of numerous si nificant natural products and other #aluable or anic compounds. )ence, the aptitude to put substituents on a benzene rin at precise locations relati#e to each other, is a #ital factor in synthesizin or anic compounds. The two &ey reaction types used for this are both substitutions7 Electrophilic %romatic =ubstitution 1E%=2 and Nucleophilic %romatic =ubstitution 1N%=2.

Nitro roup was introduced to the benzene rin , which pre#iously has an ester roup attached to it. The real electrophile in the reaction is the nitronium ion, which is usin concentrated nitric acid and concentrated sulfuric acid.

HONO2 + H2SO4 H2ONO2+ H2O + H2SO4

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

<i ure 0. Reaction Mechanism The carbomethoxy roup leads the aromatic substitution reaction to the spot that are meta to it. %s a result, the m-nitro benzoate is the prime product from this reaction. Both carbomethoxy roups as well as the nitro roup are deacti#atin roups ma&in the second nitration unfa#orable. "oncentrated sulfuric acid is the sol#ent of the reaction where in the formation of nitronium ion is from the concentrated nitric acid. >ater has a delayin effect on the nitration as it restricts the nitric acidsulfuric acid e,uilibrium that enerates the re,uired nitronium ion.

HO-NO2 + H - HSO4

NO2 +
<i ure $. Overall Reaction

HSO4 -

+ H2O

Temperature is also a factor on the outcome from this reaction. )i her the temperature will result in a lar er amount of dinitration products. Thus the reaction condition must be maintained at a #ery low temperature and all rea ents must be added #ery slowly to a#oid production of dan erous thermal release or heat which will reatly affect the whole reaction condition.

"%'%"%NC%S 1.2 http://www.wisegeek.com/what-are-aromatic-hydrocarbons.htm

(2) http://en.wikipedia.org/wiki/Methyl_benzoate (3) http://wiki.answers.com/ /!hat_prod"ct_is_#ormed_by_the_nitration_o#_benzene