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EXPERIMENT NO. 2 AROMATIC SIDE-CHAIN OXIDATION: PHTHALIC ACID FROM XYLENE Abid, Princess Alyssa S.

Cabilao, Jaea Alexis P. Chem 35.1, FEG, Group 1 Bayongan, Kristine Clarisse M. Mr. Dmitri Cordova Sarsagat, Jian Kristin D. February 21, 2014 I. ABSTRACT The oxidation of an aromatic side chain is an important reaction that results in the activation and increased reactivity of benzene rings. The oxidation of the alkyl groups attached to the benzene ring into electron-withdrawing groups increase the susceptibility of the benzene ring to react. In this experiment, the transfer of electrons between two chemical species is involved, where phthalic acid was obtained from the oxidation-reduction reacts of xylene with potassium permanganate. Unlike other oxidizing agents, KMnO 4 converts only the benzene rings substituents into carboxylic acids. In the case of xylene, the alkyl groups were oxidized to carboxylic acids. II. KEYWORDS: Aromatic side-chain oxidation, Oxidation-reduction, Recrystallization, Reflux III. INTRODUCTION Oxidations are an important group of organic reactions because organic chemists used it to synthesize a large variety of compounds. It consists of those that involve the transfer of electrons from one molecule to another. A heteroatom in a reduced state or carbon-carbon pi bond is required in most oxidations. If the reaction decreases the number of C-H bonds or increases the number if CO, C-N, or C-X bonds, the compound has been oxidized (Bruice, 2013). Aromatic side-chain oxidation is another means of imparting functionality. A benzylic carbon with at least one hydrogen attached to it is needed for the oxidation of the aromatic side chain. Chromic acid and potassium permanganate can be used as an oxidizing agent. The permanganate reaction requires work up with acid because the permanganate reaction generates a basic solution as a by product. Moreover, the vigorous oxidation of alkyl-substituted aromatic rings with hot aqueous KMnO4 results in oxidative cleavage of the side chain, forming a carboxylic acid group, irrespective of the length or branching of the side chain (Fox, 2004). Furthermore, the oxidation of aromatic side chain is also an industrially important process. However, the transformation of toluenes to benzaldehyde and benzoic acid is really difficult to perform in real situation. The most demanding stage is the introduction of the intial oxygen, as subsequent conversion between oxidation levels is easier. The products of such oxidations are useful intermediates such as agrochemical, perfumery, pharmaceutical, and polymer chemicals (Jones, 1999). The objective of this experiment is to oxidize phthalic acid from xylene using potassium permanganate as an oxidizing agent. IV. METHODOLOGY The experiment was divided into two major parts, the preparation of phthalic acid and the recrystallization and analysis of the phthalic acid. A. Preparation of Phthalic Acid In an appropriately sized round-bottomed flask, 1.5 g of potassium permanganate (KMnO4), about 0.50 g of xylene and 35 mL of water were mixed. The reaction mixture was refluxed with a few added boiling chips for about 1.5 hours. The reflux set-up is shown as follows:

Figure 1: Reflux set-up (From http://what-when-how.com/)

CHEM 35.1, Aromatic Side-Chain Oxidation: Phthalic Acid from Xylene

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The filtrate was then collected using suction filtration. When the purple color was no longer present, the reaction mixture was filtered using vacuum filtration as shown in Figure 1. When the filtrate was not colorless after the initial filtration, addition of sodium bisulfite and repetition of the filtration were done to produce a clear filtrate for the isolation of the aromatic acid.

V. RESULTS Observations in the experiment included changes in the color of the solution. Upon heating through reflux, the deep purple mixture changed to a solution with a brown precipitate sticking on the sides of the flask. Filtration separated the insoluble substance from the solution with a tint of purple. The addition of sodium bisulfite made the filtrate colorless. Upon the addition of HCl, the solution turned white. Upon crystallization, the product was a white crystalline compound. The product was minimal in amount. The second part of the experiment was not done because the crystals left in the oven for one week disappeared. The theoretical results are mentioned in the discussion. VI. DISCUSSION

Figure 2: Vacuum filtration set-up (From http://www.nclabs.com)

The clear and colorless solution was placed in the ice bath. The mixture was then acidified through the addition of about 2.5 mL concentrated hydrochloric acid (HCl) dropwise with constant swirling. The pH was checked using Litmus paper to ensure that the solution is acidic. The precipitated organic product was collected using vacuum filtration. Small amounts of water were used to wash the solid material in the filter to remove any remaining solids from the crystallization container, prior to drying. The solid product was stored in the drying oven. B. Recrystallization and Analysis of the Phthalic Acid The product was recrystallized using xylene as solvent. Enough xylene was added to ensure that the solid dissolves at a higher temperature but some stays undissolved at room temperature. When too much xylene was added or whenthe acid crystals were not observed upon cooling in an ice bath, some of the xylene was evaporated in the hood. Prior to filtration, the crystals were suspended fully in xylene. The phthalic acid was analyzed through determining the melting temperature. The observed value was compared to the literature value. The percent yield was determined.

Figure 3. Reactions of different aromatic hydrocarbons with KMnO4

The oxidation of an alkyl group bonded to an aromatic compound proceeds through the use of oxidizing agents, such as KMnO4 and acidic + solutions of sodium dichromate (H , Na2Cr2O7). Since the aromatic compound is stabilized by resonance, only the alkyl substituent, regardless of its length, is oxidized to a carboxyl group. However, in the absence of hydrogen bonded to the benzylic carbon, the reaction does not occur since the first step includes the removal of the benzylic hydrogen (Bruice, 2011). Thus, not all aromatic hydrocarbons produce benzoic acid upon oxidation as shown in Figure 3 above. The mixture of xylene, KMnO4 and water produced a purple solution. The permanganate ion becomes reduced to manganese dioxide (MnO 2), an insoluble compound, in water. This causes the oxidation of the alkyl substituent to a carboxylic

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group (Pankaj & Ashokkumar, 2010).The reactions are shown as follows: 2KMnO4 + H2O 2MnO2 + 2KOH + 3[O] Eq.1

Figure 5: Formation of carboxylic acid salt

Figure 4: Oxidation of xylene

In this experiment, potassium permanganate was preferred compared to sodium dichromate because it is a stronger oxidizing agent than dichromate. Manganese is in its highest oxidation state, which is +7, thus making it more electronegative. Moreover, dichromate is a very toxic carcinogenic making it unsafe to use. Also, with dichromate, the color change observed from orange to green wouldnt be as distinct compared to if permanganate is used. With the use of permanganate, the color change observed would be from purple to colorless.(Tojo & Fernandez, 2007). Heating under reflux retains the solvent in the mixture since the reflux condenser allows the volatile materials to continuously return to the flask despite reaching the boiling point(Gilbert & Martin, 2011). Due to the presence of heat, the reaction proceeds faster. Before refluxing the mixture, a boiling chip was added to prevent superheating where the solution is heated above its boiling point without actually boiling and to control boiling from sudden occurrence of boiling (Williamson & Masters, 2011). This allows air trapped in the porous porcelain to be released as fine air bubbles, reducing the tendency of bumping in the hot solution (Pedersen & Myers, 2011). The heated solution is filtered through vacuum filtration where liquid is pulled, allowing the mixture to be filtered at a faster rate (Ledgard, 2012).This promotes the removal of insoluble impurities. The residue is composed of the brown insoluble MnO2. The filtrate must not be purple in color since this shows the presence of permanganate ion. The addition of sodium bisulfite, an activating form of carbon,allows the reduction of the permanganate ion as given in Equation 2 (Thompson, 2008). Thus, the colorless solution indicates the removal of colored impurities. Cooling the solution allows the formation of crystals since solids are less soluble in lower temperatures. 2MnO4 (aq) +3HSO3 + OH 2 MnO2(s) + 3SO4 (aq) + 2H2O(l) Eq. 2

Figure 5 shows that a salt is formed from the carboxyl group and the sodium ion. However, in the presence of concentrated hydrochloric acid, the aqueous base is neutralized and the phthalic acid is formed. Drying the solid product prioritizes the removal of water before the evaporation of the solvent. Recrystallization is accomplished through the dissolution of the solid in an appropriate solvent, in this case xylene, at a higher temperature. Since almost all solids are less soluble in lower temperatures, the solution recrystallization takes place upon cooling, allowing most impurities to stay in the solution (Gilbert & Martin, 2010). Thus, this technique can be summarized as (1) the choice of an appropriate solvent, (2) the dissolution of the solid in the solvent about its boiling point, (3) the removal of impurities through an activating form of carbon and filtration, (4) the crystallization of the solid during cooling, (5) the isolation of the purified product through filtration and (6) the drying the solid product. The oxidation of xylene to phthalic acid is done through reduction-oxidation reactions. This reaction involves the transfer of electrons between two chemical species. The compound that gains an electron is reduced the other one losing the electron is oxidized (Bruice, 2011). The balanced half redox equations in this experiment are the following: [MnO4 + 4H + 3e MnO2+ 2H2O] x 4 H3CC6H4CH3 + 4H2O HOOCC6H4COOH + + 12H + 12e The overall redox reaction is then given by: + 4MnO4 + 4H + CH3C6H4CH3 4MnO2+ 4H2O + HOOCC6H4COOH Examining closely the reaction, the oxidation states of the compounds are determined. The benzylic carbon has been oxidized from (-3) to a (+3) oxidation state, meaning it lost 6 electrons for each benzylic carbon in the reaction. While manganese has been reduced from (+7) to a (+4) oxidation state, meaning it gained 3 electrons per mole in the process. Thus, 12 electrons were used in the overall redox experiment of oxidizing xylene to phthalic acid and reducing the permanganate ion at the same time.
(-3) (-3) (+3) (+3) (+7)
+ -

(+4)

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The determination of the melting point of a crystal is essential in for the identification of the organic compound. Impurities are considered as a factor that influences the melting temperature (Ahluwalia & Dhingra, 2001). According to Eagleston (1994), the melting temperature of o phthalic acid is known to be 191 C in a closed tube. The pure compound melts at a temperature where the vapor pressures of both the solid and the liquid are equal. The organic compound is said to have the presence of other substances when the determined melting point is lower than the theoretical result. This is because in the mixture of solid and other substances, the attractive forces are less. Thus, the melting point is lower (Williamson & Masters, 2011). VII. CONCLUSIONS AND RECOMMENDATIONS The result obtained in the experiment is a minimal amount of phthalic acid, also called 1,2benzenedicarboxylic acid, a colorless, crystalline organic compound and is one of the three isomers of benzenedicarboxylic acid. Oxidation of alkyl benzenes occur in the presence of an oxidizing agent followed by work up in acidic conditions. For oxidation to occur, at least one benzylic hydrogen is required. For better results, enough sodium bisulfite must be added slowly to remove the purple color. The solvent added must not be too little or too much because crystallization may not be observed. For every experiment, it is recommended to take precautionary measures in handling reagents. Gloves and masks must be worn all the time. Potassium permanganate is known as a strong oxidizer and a corrosive substance which can also stain the skin. Sodium bisulfite, on the other hand, is an irritant. Concentrated HCl is not only corrosive but also toxic. Furthermore, the reaction between sodium bisulfite and potassium permanganate is highly exothermic. Thus, careful mixing must be done because the release of energy through heat is expected to occur. The boiling chips should also be added before heating through reflux since superheating or sudden bumping may occur. For a better understanding of the concept of aromatic side-chain oxidation, it is recommended to extend this experiment by using different oxidizing agents, such as nitric acid, and by using toluene as the solvent for comparison of the results. VIII. REFERENCES Ahluwalia, V. K., & Dhingra, S. (2001). Comprehensive practical organic chemistry: Qualitative analysis. London: Sangam.

Bruice, P. Y. (2011). Organic chemistry(6 ed.). Upper Saddle River, N.J: Prentice Hall. Eagleson, M. (1994). Concise encyclopedia chemistry. Berlin: Walter de Gruyter. Fernandez, M., &Tojo, G. (2007).Oxidation of primary alcohols to carboxylic acids: A guide to common practice. New York, USA: Springer Science+Business Media, LLC. Fox, M. A., &Whitesell, J. K. (2004). Organic chemistry. Sudbury, Mass: Jones and Bartlett Publishers. Gilbert, J.,& Martin, S. (2010). Experimental organic chemistry: A miniscale and microscaleapproach. Boston, M.A: Cengage Learning. Jones, C. W. (1999). Applications of hydrogen peroxide and derivatives. Cambridge, UK: Royal Society of Chemistry. Ledgard, J. B. (2010). The preparatory manual of explosives: Radical, extreme, experimental explosives chemistry, Vol. 1.S.I: s.n. Pankaj, & Ashokkumar, M. (2011). Theoretical and experimental sonochemistry involving inorganic systems. Dordrecht: Springer. Pedersen, S.,& Myers, A. (2011).Understanding the principles of organic chemistry: A laboratory course.Selmont, C.A: Cengage Learning. Thompson, R. B. (2008). Illustrated guide to home chemistry experiments: All lab, no lecture.Beijing: Make:Books/OReilly. Williamson, K. L., & Masters, K. M. (2011).Macroscale and microscale organic th experiments (6 ed.). Pacific Grove, Calif: Brooks/Cole. I hereby certify that I have given substantial contribution to this report.

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ABID, PRINCESS ALYSSA S.

CABILAO, JAEA ALEXIS P.

BAYONGAN, KRISTINE CLARISSE M.

SARSAGAT, JIAN KRISTIN D.

CHEM 35.1, Aromatic Side-Chain Oxidation: Phthalic Acid from Xylene

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