Nucleophilic Acyl Substitution: The Synthesis of Esters

Frances Abegail G. Quezon Department of Chemical Engineering, University of the Philippines, Diliman, Quezon City 1101 Philippines Date/s Performed !ugust 1", #01$ % Date &u'mitted !ugust #(,#01$ The objective of the experiment was to synthesize an ester, particularly benzyl acetate or benzyl ethanoate. The reaction was a Fischer esterification reaction. Since this type of reaction needed constant heating, a reflux set-up was used in order to prevent loss of product. The volume of the yield was .! m", and upon conversion to grams, .##g. $ased from the theoretical yield, %.& g, the ' yield was %%.() '. *onsidering that the reaction involved is reversible, the ' yield obtained could be seen as a good value. Introduction The aim of the experiment, +ucleophilic ,cyl Substitution- The Synthesis of .sters, was to synthesize an ester from an alcohol and an acid. The general formula of an ester is The percent yield was calculated by the formula below'enzylethanoate:exp; ' yield = )(&& :(; 'enzylethanoate:theo; E!peri"ental #etails <n a )=-m" round bottom flas3, >.= m" of benzyl alcohol was mixed with ). m" of acetic acid. ?hile swirling the flas3, drops of concentrated 6)S4> was added. The flas3 was submerged in a hot water bath with boiling chips and connected to a reflux condenser. ,n ice bath was prepared and a pump was used so that the cool water from the bath would flow through the condenser. The mixture was allowed to reflux for >= mins.

Figure . /eneral formula of an ester0(1 2any esters are used in the perfume and food industry because of their pleasant odor. .xamples are butyl acetate which smells li3e bananas0(1 and benzyl acetate which smells li3e peaches. $enzyl acetate, otherwise 3nown as benzyl ethanoate, was the ester synthesized in the experiment. The process involved in this experiment is called esterification. .sterification is the reaction between alcohols and acids to form esters. 4 4 7 55 6 55 8-*-46 7 8946 8-*-489 7 6)4 :(; This reaction is reversible, thus some of the product will decompose bac3 to the starting reactants.0)1 For this experiment, benzyl alcohol and acetic acid were used to synthesize benzyl ethanoate with benzyl alcohol in excess. The yield was measured with a graduated cylinder and then converted to grams by stoichiometry.

Figure $. 8eflux set-up0 1

,fter the reflux, the mixture was allowed to cool to room temperature and transferred to a &-m" separatory funnel. The reaction flas3 was rinsed with cold water and its washings were added to the separatory funnel. This was done repeatedly until the a@ueous layer is twice the volume of the organic layer. The separatory funnel was sha3en and the layers were allowed to stratify. Saturated +a*l solution may be added to hasten separation. Solid +a6*4 was added next to remove excess acid. ,fter this, the layers were then separated. The organic layer was collected and dried with approximately (.&&g anhydrous +a)S4>. ,dditional drying agent could be added if the drying agent clumps, the solution is cloudy, or there are still obvious water droplets. The mixture was decanted to a graduated cylinder and the volume of the yield was measured. Asing stoichiometry, the volume was converted to grams of benzyl ethanoate. Stoichiometry was also used to figure out the theoretical yield. Then, the 'yield was computed using e@uation :(;. %esults and #iscussion <n this experiment, an ester with a peach scent is to be synthesized. This ester is benzyl acetate or benzyl ethanoate. The reactants to be used are acetic acid and benzyl alcohol. The reaction mechanism for this reaction is-

Figure &. Fischer .sterification 8eaction 2echanism0>1 The particular reaction referred to in the experiment was-

:);0>1

This 3ind of reaction is a Fischer esterification reaction. <t is a type of reaction that converts carboxylic acids to esters by reacting it with alcohol. The oxygen in the acyl group of the carboxylic acid is protonated by the 67 catalyst. .lectrons from the pi bond are attracted to the positive charge, thus brea3ing the double bond in the acyl group and moving the positive charge to *. This causes the lone pair electrons in the 4 in the alcohol to be attracted to * and attach to it. The 4 in the alcohol obtains a positive charge. Transfer of a proton from one 4 atom to another converts an B46 group to a B6 )47 group. The water molecule would then be expelled from the intermediate. Simultaneously, 67 would also be expelled from the remaining B46 group.0=1 This reaction type is called nucleophilic acyl substitution reaction because one acyl group is substituted with a nucleophile.0%1 <n this case, the nucleophile is the lone pair containing oxygen atom of the alcohol. The reaction for the formation of benzyl ethanoate is reversible. Since according to "e *hatelier9s Crinciple, by increasing the amount of moles of the reactant, the reaction will be pushed forward0D1, one of the reactants was in excess. The reactant in excess was the benzyl alcohol since it is cheaper. The limiting reagent was acetic acid. ,nother method favoring the formation of esters is adding acetic acid in excess. ?ater, a by-product of the reaction could also be removed using a dehydrating agent. 8emoval of a product could also push the reaction forward, according to "e *hatelier9s Crinciple. This is also the reason why, in preparing esters from ethanol, it is necessary

to use absolute ethanol. ?ater from the reagent increases the amount of water in the solution and pushes the reaction bac3ward. Asing absolute ethanol prevents this because absolute ethanol contains no water. *oncentrated 6)S4> was added next to the solution. The acid donated 67 which served as a catalyst for the reaction. ,fter this, the round-bottom flas3 containing the solution was immersed in a hot water bath. $oiling chips were used in the bath to avoid superheating, which is a phenomenon where li@uids reach temperatures above their boiling point without boiling. ,ddition of boiling chips provided nucleation points for bubbles and lessens the probability of violent boiling.0!1 The flas3 was then attached to a reflux condenser. The Fischer esterification reaction re@uires constant heating in order to progress.0=1 6owever, constant heating might cause some of the product to volatilize. To avoid this, the solution is made to reflux. 8eflux is the process of boiling the reactants while continually condensing the vapor. The process was used to continually heat a mixture for a long period of time without it evaporating completely. 0#1 To ma3e sure that all vapor condenses bac3 to li@uid form, water from an ice bath was made to flow through the condenser. For this purpose, a pump was used. ,fter the >=-minute reflux procedure, the flas3 was allowed to cool to room temperature and poured to a separatory funnel. *old water washings of the flas3 were added too in order to obtain product stuc3 on the sides of the flas3. To facilitate layer separation between the organic and a@ueous layer, a few drops of saturated +a*l solution was added. This increases the <2F, difference between layers and causes better layer separation. Solid +a6*4 was also added to react the excess acid. The reaction for this is6*4 - 7 67 *4):g; 7 6)4:l; :); ,n evidence of this reaction was the formation of bubbles because of *4) buildup. ?hen bubbles stop to form, it means excess acid is already completely reacted. <f +a46

was used, *4) would not form and there would no be signal when the acid is already completely reacted. The solid state of +a6*4 was important in this part because if its a@ueous form was used the unreacted +a6*4 could not be separated. The organic layer was then recovered. , gram of anhydrous +a)S4> was added to remove excess water. The solution was decanted to a graduated cylinder to measure the yield. The volume measured turned out to be .! m". Asing stoichiometry, the volume of the yield was converted to grams. The value was .##g. The theoretical yield was also computed with the value being %.& g. Then using e@uation :(;, the 'yield was computed. The 'yield was %%.() '. Tabulated below are possible sources of error in the experiment. Table . Sources of .rrors Error 'ara"eter Effect 8eaction is 'yield Eecrease reversible "oss of 'yield Eecrease product in transferring containers Anreacted 'purity Eecrease alcohol (onclusion The objective of the experiment was to synthesize an ester, in particular, benzyl acetate or benzyl ethanoate. The yield turned out to be .##g. The expected yield, provided that the reaction goes to completion, was %.& g. The 'yield was %%.() '. The experimental yield was more than half of the theoretical yield, and considering that the reaction is reversible, this could be seen as a good value. The experiment could be considered a success. Eistillation of the crude product is recommended since the excess reactant, benzyl alcohol, is non-polar and would not separate, even upon addition of saturated +a*l solution. $y not distilling the product, the 'purity of the solution decreases.

%eferences 0(1 2c*arty, C.". F Car3in, /.F. F Sawyer, *.+. Chemistry for Environmental Engineering and &cience, =th ed.F 2c/raw 6ill- +ew Gor3, )&& F pp. ) =-) % 0)1 $all, E.?. F 6ill, H.?. F Scott, 8.H. *he +asics of ,eneral, -rganic, and +iological Chemistry (st ed.F 2c/raw 6ill- +ew Gor3, )&((F pp. (= . 0 1 ?hat ?hen 6ow .eflu) /a'oratory 0anual http-IIwhat-when-how.comIorganicchemistry-laboratory-survival-manualIrefluxlaboratory-manualI :accessed ,ugust )&, )&( ;. 0>1 ?i3imedia 1ischer Esterification 0echanism http-IIupload.wi3imedia.orgIwi3i pediaIcommonsIthumbIdIdDIFischerJesterifica tionJmechanism.svgI=(!px-FischerJesteri ficationmechanism.svg.png :accessed ,ugust )&, )&( ;. 0=1 2c2urry H. 1undamentals of -rganic Chemistry Dth edF $roo3sI*ole- $elmont-)&(( pp. #- >&. 0%1 A* Eavis *hem?i3i &ection 1#21 3ntroduction to car'o)ylic acid derivatives and nucleophilic su'stitution reaction http-IIchemwi3i.ucdavis.eduI4rganicJ*hemist ryI4rganicJ*hemistryJ?ithJaJ$iologicalJ. mphasisI*hapterJ()' aJ,cylJsubstitutionJr eactionsISectionJ().(' aJ<ntroductionJtoJca rboxylicJacidJderivativesJandJtheJnucleophil icJacylJsubstitutionJreaction:accessed ,ugust )(, )&( ;. 0D1 A* Eavis *hem?i3i /e Chatelier4s Principle http-IIchemwi3i.ucdavis.eduIChysi calJ*hemistryI*hemicalJ.@uilibriumI"eJ*ha telierKsJCrinciple :accessed ,ugust )(, )&( ;. 0!1 +ewton ,s3 a Scientist +oiling Chips http-IIwww.newton.dep.anl.govIas3asci Ichem&&Ichem&&%>&.htm :accessed ,ugust )(, )&( ;. 0#1 A? 2adison Eepartment of *hemistry .eflu)ing http-IIwww.chem.wisc.eduIareasIorg anicIorglabItechIreflux.htm :accessed ,ugust )(, )&( ;.

Appendices !ppendi) ! 5E)perimental Data6 )olu"e Acetic Acid ,enzyl Alcohol ,enzyl Ethanoate +eight of ester .##g !ppendi) + 5Calculations6 >&.(!mmol7-!c (mmol'enzylethanoate (mol (=&.(! g L %.& >) g :theoretical; (mmol7-!c (mmol (mol ). m" >.= m" .! m" *olecular +eight %&.&= gImol (&!.(> gImol (=&.(! gImol - yield %%.() ' #ensity (.&># gIm" (.&>> gIm" (.&= gIm" ""ol >&.(! mmol > .>> mmol )%.=D mmol ,oiling point )()*

'yield L

.## g (&& L %%.() ' %.& >) g