Experiment 9 Title Objective : Preparation of Dibenzalacetone : Preparation of dibenzalacetone

Date: 28 March 2006

Chemical Equation and Structural Formula of Organic Substances Involved :

Cyclohexanol Molecular weight (gmol-1) Weight (g) Moles# Limiting reagent Theoretical yield 100 10 0.1 /

Sodium dichromate 262 20 0.076

Sulphuric acid 98 17.31* 0.177

Cyclohexanone 98

9.8 g (0.1 mol)@

Given density of Concentrated sulphuric acid (H2SO4) Mass of sulphuric acid

= 1.84 g/mL

= Volume Density Mass concentration = 9.6 mL 1.84 g solution/mL 98 g H2SO4/100 g solution = 17.31 g H2SO4 = 10 g / 100 gmol-1 = 0.1 mol = 20 g / 262 gmol-1 = 0.076 mol = 17.31 g / 98 gmol-1 = 0.177 mol
3 mol cyclohexanone 98 g cyclohexanone

Moles of cyclohexanone Moles of sodium dichromate Moles of sulphuric acid

@ Theoretical yield = 0.1 mol cyclohexanol 3 mol cyclohexanol mol cyclohexanone = 9.8 g cyclohexanone

Apparatus : Round-bottomed flask (50 mL, 250 mL), measuring cylinder (50 mL), beaker (100 mL, 250 mL), conical flask (50 mL, 250 mL), glass rod, dropper, spatula, cork stand, thermometer, thermometer adapter, Liebig condenser, distillation adapter, still distillation head, separatory funnel, funnel supporting ring, retort stand, retort clamps, electrothermal heater, hot plate, fluted filter paper, oven, glass funnel, stemless glass funnel, electronic weigh, glass vial Chemicals : Dehydrated sodium dichromate (20 g), concentrated sulphuric acid (9.6 mL), distilled water (100 mL + 80 mL), cyclohexanol (10.6 mL), common salt, ether (25 mL), anhydrous magnesium sulphate, ice, boiling chips Procedure :

Dehydrated sodium dichromate (Na2Cr2O7.2H2O) (20 g) is weighed using an electronic weigh and a beaker. Distilled water (100 mL) is measured using a graduated measuring cylinder and poured into the beaker containing the dichromate and stirred using a glass rod to dissolve it thoroughly. Concentrated sulphuric acid (9.6 mL) is measured using the measuring cylinder and a dropper and mixed with the dichromate solution in portions and stirred. The mixture is cooled to about 20C in an ice bath. Cyclohexanol (10.6 mL) is measured into a 250 mL conical flask. The chromic acid mixture is poured into the flask in portions and swirled. The temperature of the mixture in the flask is ensured to be between 55C and 60C by either heating it using a hot plate or cooling it using the ice bath. The mixture is allowed to cool for 45 minutes. Meanwhile, a 250 mL round-bottomed flask is clamped to a retort stand with an electrothermal heater beneath it. After the cooling time has elapsed, the mixture is transferred into the round-bottomed flask using a glass funnel. Distilled water (80 mL) is measured and added into the flask. Three to four pieces of boiling chips are also put into the flask. The distillation apparatus is then assembled and set up. The still distillation head is connected to a Liebig condenser and its exiting adapter, which are clamped to another retort stand at a lower height. The thermometer together with its adapter is inserted into the still head, with the top of the thermometer bulb aligned with the bottom of the side-arm of the still head. A 100 mL beaker is placed below the exiting adapter to collect the distillate. Water is run through the condenser from the pipe with the inlet near the exiting adapter and the outlet near the side-arm of the still head. The distilland (contents of the flask) is heated. Heating is stopped and the heater is taken away immediately after 80 mL distillate is collected. The still head, Liebig condenser and the exiting adapter are dismantled and their internal walls are washed with acetone before being put into an oven. Meanwhile, a piece of filter paper is folded into fluted form. A spatula of common salt is added to the distillate and stirred to dissolve it. The separatory funnel is suspended using a supporting ring clamped to a retort stand. The distillatesalt solution is poured into the separatory funnel with the stopcock tap closed. The funnel is closed using its stopper before being shaken gently. The funnel is then inverted with finger over stopper and the stopcock tap is opened to release the pressure inside the stopper, i.e. a hissing sound of gas released is heard. The shaking and venting of the funnel is repeated a few times until the audible hiss is no longer heard. The funnel is put back into the ring and left for a certain time period to let the organic and aqueous layers to form. The stopper is opened and the stopcock tap is turned to a vertical position to drain the lower aqueous layer into a clean, empty 50 mL beaker. The upper organic layer is drained into another empty 50 mL beaker. The aqueous layer is poured back into the funnel with the stopcock closed. Ether (25 mL) is measured and poured into the funnel, which is shaken and vented a few times. After the organic and aqueous layers have formed, the aqueous layer is drained off into an empty beaker, while the upper organic layer is drained into a conical flask and mixed with the organic layer from the first extraction. A spatula of anhydrous magnesium sulphate is poured into the flask and left for about 5 minutes. The mixture is then filtered via gravity filtration using the fluted filter paper in a stemless glass funnel into an empty, clean 50 mL round-bottomed flask. Three to four boiling chips are added into the flask. The distillation components are taken out of the oven and together with the flask, assembled for a second distillation. An empty glass vial together with is cap is weighed and its mass is recorded. The distilland is heated and the temperature is observed. Any distillate produced before 150C is collected into an empty beaker. Distillate produced in the range of 150C 156C is collected into the vial. The vial is capped as soon as possible after the temperature increases past 156C and the electrothermal heater is removed. During the process, the temperature that reaches to a point where it stops increasing within the 150C 156C range is taken as the boiling point temperature. The

vial is weighed to obtain the net mass of the distillate and labelled with details of the experimental results, i.e. boiling point, net mass, etc. written on it. Observation : Dehydrated sodium dichromate when dissolved in water and sulphuric acid produces an orange solution (chromic acid). Chromic acid mixed with cyclohexanol produces a blackish-green solution. Mass of empty vial + cap Mass of empty vial + cap + cyclohexanone Net mass of cyclohexanone Characteristics of cyclohexanone Experimental boiling point = 16.20 g = 20.24 g = (20.24 16.20) g = 4.04 g : Colourless liquid : 155C

Distillation of crude cyclohexanone gave pure cyclohexanone (4.04 g, 41.22 %) as colourless liquid with boiling point of 155.0C (reference: 150.0 156.0C).

Discussion : This experiment incorporates the use of aldol condensation reaction. Generally defined in the simplest way, aldol condensation is the condensation of two molecules of the same aldehyde or ketone, resulting in the formation of a new carboncarbon bond (CC) joining the carbonyl carbon of one molecule to the -positioned carbon of the other molecule. The reaction requires the molecule to possess a reactive carbonyl group and able to lose a proton (or hydrogen) from the position to form an enolate ion or carbanion. For this experiment, since benzaldehyde, an aromatic aldehyde, does not have any hydrogen atom in the -position and thus cannot give simple aldol condensation. However, benzaldehyde is capable of participating in mixed (crossed) aldol condensation with aliphatic aldehydes or ketones that can form carbanions. This crossed aldol condensation is called ClaisenSchmidt condensation. In this experiment, acetone, an aliphatic ketone is used. Aldol condensations are usually catalyzed by acids or bases but basic catalysts are generally preferred, one of those effective catalysts being ethanolic sodium hydroxide (CH 3CH2OH + NaOH), as in this case. The hydroxide ion of the base extracts the -hydrogen from acetone and resonance stabilizes the carbanion intermediate before reacting further with benzaldehyde as a strong nucleophile. In the presence of base, the -hydroxyketone produced initially undergoes dehydration spontaneously to form the resonance-stabilized , -unsaturated ketone and a separate water molecule. The unsaturated ketone has a double bond conjugated to both the aromatic ring and the carbonyl group, thus the resonance-stability. The mechanism of the aldol condensation between benzaldehyde and acetone is depicted below: Step 1: Base (NaOH) removes proton (H+) from -carbon of acetone, forming an enolate ion. Step 2: Enolate ion adds to carbonyl group in benzaldehyde, forming an alkoxide. Step 3: Protonation of alkoxide by ethanol (CH3CH2OH) produces -hydroxyketone. Step 4: Removal of proton from -carbon of -hydroxyketone by base, forming a resonancestabilized enolate. Step 5: Elimination of hydroxide produces benzalacetone. As acetone has two methylene groups, aldol condensation is complicated by the possibility of mono or disubtitution. In cases where acetone is excessive, the mono-condensation product, benzalacetone, is obtained. However, since it is dibenzalacetone (IUPAC name: 1,5-diphenyl-1,4pentadien-3-one) that is wanted in this experiment, benzaldehyde is used in excess instead, so that 2 moles of benzaldehyde react with 1 mole of acetone to produce 1 mole of dibenzalacetone. The mechanism continues after formation of benzalacetone. Step 6: Base (NaOH) removes proton (H+) from -carbon of benzalacetone, forming an enolate ion. Step 7: Enolate ion adds to carbonyl group in benzaldehyde, forming an alkoxide. Step 8: Protonation of alkoxide by ethanol (CH3CH2OH). Step 9: Removal of proton from -carbon by base, forming a resonance-stabilized enolate. Step 10: Elimination of hydroxide produces dibenzalacetone.

During the preparation process, all four reagents and catalytic chemicals were mixed in a 25 mL conical flask. Using a small conical flask prevents any of the reagents or catalysts from escaping in vapour form. The mixture initially turns pale yellow. It is only after about 15 minutes when the mixture turns red. The internal walls of the conical flask are scratched using the glass rod to hasten crystallization. Scratching however produced pale yellow crystals. The mixture is left undisturbed for about a further 10 minutes, to allow the mixture to cool and more crystals to form. Having done this, the crystal liquid mixture is passed through the Hirsch funnel which is connected to the aspirator, together with its specific filter paper, to suck dry the crystals via vacuum filtration. Any leftover crystals in the conical flask are washed with distilled water to facilitate its flow into the Hirsch funnel and increase the yield. Furthermore, distilled water is able to dissolve any impurities without affecting the product. Having allowed the crystals to be sucked dry for about 10 minutes, the crystals are transferred into a round-bottomed flask for recrystallization. Crude organic compounds in solid state at room temperature are purified via recrystallization whereby the compound is dissolved in a hot organic solvent. For that purpose, ethanol is used as it dissolves most polar and nonpolar substances. Furthermore, it is chemically inert towards dibenzalacetone. As ethanol is a volatile solvent with a boiling point of 78C, an electrothermal heater is used to heat the mixture instead of the Bunsen burner to avoid fire accidents. In addition, ethanol evaporates easily during the heating process and therefore, a water condenser is set up to cool down most of the ethanol vapour back to liquid form. This is done to ensure that hardly any dissolved dibenzalacetone in ethanol escapes in vapour form and also to maintain the temperature throughout the heating process. Addition of boiling chips into the round-bottom flask before the heating process is to minimize the explosiveness of sudden boiling should the ethanol is heated to above its boiling point. Filtering the mixture immediately after dissolving of crude dibenzalacetone by gravity through a preheated stemless glass funnel with fluted filter paper inside into a beaker hinders premature crystallization of dibenzalacetone in the filter paper or funnel, thus preventing any loss of material. Filtration of the mixture while still hot also serves to remove any insoluble solid impurities while the mixture is still in liquid form. The hot mixture should be poured onto the upper portion of the filter paper as the larger surface area at this portion enables the mixture to be filtered more rapidly, thus increasing the efficiency of filtration. By folding the paper into fluted form, the rapidity of filtration is increased as almost the entire surface area of the filter paper is being used. It also clogs up any possible tiny pores in the filter paper so that the results of filtration are maximized. Using a stemless glass funnel is to allow the product come out in liquid form so that the product will not crystallize prematurely and block the flow of the filtrate. After filtration, the filtrate is allowed to cool slowly at room temperature. Under cooler conditions, dibenzalacetone is no longer soluble in ethanol and crystallizes. Insoluble impurities are excluded from the growing crystals. While sucking the crystals dry using vacuum filtration, cool ethanol is used to rinse any leftover crystals off from inside the beakers walls and also the funnel to maximize the yield. In the process of determining the melting point, a small portion of the crystals is grinded into powdery form using a capillary tube and about 2 mm height of crystals is collected inside the tube, which is later passed through a long glass tube so that the crystals are collected at the bottom of the closed end of the capillary tube when it hits onto the surface below the long tube repeatedly. The capillary tube is then inserted into the melting point apparatus and observed from the magnifying lens of the apparatus. Heating of the crystals is then initiated as the temperature reading of the apparatus is being observed. The temperature when the crystals are noticed to start to melt or the height of the collected crystals starts to drop suddenly is being recorded as Ti and the temperature

when the crystals have completely transformed into liquid form is recorded as Tf. Ti Tf marks the range of the melting point of the dibenzalacetone crystals. Upon completion of the experiment, the percentage yield of the crystalline product was found to be 34.88 %, as shown in the calculations below: Percentage yield = =
Actual yield 100% Theoretical yield 1.35 g 100% 3.87 g

= 34.88 % Such a low percentage of yield could be due to several reasons listed below: a. The carbanion intermediate produced could have attacked other acetone molecules instead of benzaldehyde, thus producing by-products. b. A small amount of the product had been left in the conical flask when transference to the Hirsch funnel. The same occurs when transference from the funnel to the round-bottomed flask and from the watch glass to the vial. c. The acetone might have not reacted completely with the ethanolic sodium hydroxide catalyst thus the low number of carbanions present to attack benzaldehyde. d. Crystallization of the product might have been incomplete and that some of the product could have been left behind in liquid form. In the process of determining the melting point, the range of the melting point obtained from the experiment was found to be 105.3C 107.6C. The reference melting point temperature, as according to Donald L. Robertsons Aldol Condensation: Preparation of Dibenzalacetone (1,5Diphenyl-1,4-pentadien-3-one) (2006), is 107C, which is located in that range. Thus, it can be concluded that the product is sufficiently pure but not 100% pure. To minimize the above errors, several steps of precaution need to be taken. First of all, after vacuum filtration, crude dibenzalacetone should be transferred from the Hirsch funnel directly into the round-bottom flask used for heating. During gravity filtration, the mixture to be filtered is ensured to be still hot to avoid any premature crystallization on the fluted filter paper. Other than that, the pure crystals need to be ensured to be dry enough and free of impurities so that the actual net mass of pure dibenzalacetone and a satisfactory melting point range can be obtained. If one wants to obtain the maximum results, it is advised that the collection process be repeated as a second crop of crystals might be obtained. Conclusion : Crossed ClaisenSchmidt aldol condensation between excessive benzaldehyde and acetone and dehydration of the aldol produced produces dibenzalacetone (1.35 g, 34.88%) with a melting point of 105.3C 107.6C in the form of pale yellow, shiny flakes. The product is not exactly 100% pure, due to the possibility of impurities in the product and also errors in techniques used during the experiment. References : Svoronos, Paris; Sarlo, Edward; Kulaweic, Robert J., (1997), Organic Chemistry Laboratory Manual 2nd ed. United States of America: McGraw-Hill Company, 243 245.

Wade, L.G., Jr. (2005), Organic Chemistry 6th ed. United States of America, Pearson Education, Inc., 1056 1057, 1060. Wilcox, Charles F., Jr.; Wilcox, Mary F., (1995), Experimental Organic Chemistry: A Small-Scale Approach 2nd ed. United States of America: Prentice Hall, 397 399. Zubrick, James W., (1992), The Organic Chem Lab Survival Manual: A Students Guide to Techniques 3rd ed. United States of America: John Wiley & Sons, Inc., 121. McBride, Katherine, (2005), Synthesis of Dibenzalacetone by the Aldol Condensation. Retrieved April 2, 2006, from http://www.susqu.edu/students/m/mcbride/organic%20lab%208.htm. Robertson, Donald L., (2006), Aldol Condensation: Preparation of Dibenzalacetone (1,5Diphenyl-1,4-pentadien-3-one). Retrieved April 2, 2006, from http://www.miracosta.edu/home/dlr /211exp5.htm.