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EXP- 4

CHEM 233L THE DIELS-ALDER REACTION Synthesis of endo-Norbornene-5, 6-cis-dicarboxylic Anhydride and Endo-Nobornene-5, 6-cis-dicarboxylic acid

Introduction: The purpose of this experiment was to perform the Diels-Alder reaction which is one of the most powerful reactions in organic chemistry. The Diels-Alder reaction is a cycloaddition reaction between a diene and a dienophile to produce a six-membered-ring. In part A, maleic anhydride and cyclopentadiene were used as the dienophile and the diene, respectively. Part A reaction synthesized endo-norbornene-5, 6-cis-dicarboxylic Anhydride which then used as a reactant of the part B reaction. Part B reaction was the hydrolysis of the anhydride in boiling water to form endo-Nobornene-5, 6-cisdicarboxylic acid. Main Reactions: Part A: H H Heat 2

O + O O Part B:
H H + H2O H2SO4 H O

H O

O O

O OH OH

H O

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Table of Physical Properties: Compound Name

O

Maleic anhydride White solid O O Ethyl acetate

Colorless liquid with fruity odor

Molecular Melting Boiling Density Solubility Weight Point ( point ( (g/ml) o o (grams) C) C) 98.058 52.8-60 200 1.314 Soluble; decompose in hot solvent 88.106 -83.6 77.1 0.8945 Soluble 8 g/100mL

Precautions corrosive

Flammable liquid

86.1766 Hexane
Colorless liquid with a mild gasoline-like odor

-95

69

0.6548

Slightly Flammable soluble .0009 liquid 47 g/ 100mL Water insoluble

66.1024 Cyclopentadiene
Colorless liquid with a sweet odor.

-85

42

0.8

182.18
O OH OH

175

H O

Endo-Norbornene-5,6cis-dicarboxylic acid.

164.16
O O

164

H O

Endo-Norbornen-5,6cis-dicarboxylic anhydride.

Page 3 _______________________________________________________________________ _ Safety Notes: - Maleic anhydride is corrosive. Wash your hands well after using it. - Ethyl acetate and Hexane are flammable liquid. Pay attention when using them. Procedure: EXP- 4A: endo-Norbornene-5, 6-cis-dicarboxylic Anhydride 1. In a dry 50 ml Erlenmeyer flask with a stir bar, dissolve 1.0 g of maleic anhydride in 5ml of ethyl acetate by warming it in a hot water bath at around 50-60 oC. 2. Add 5 ml of ligroin or hexane in the flask; cool it in an ice-bath with swirling. 3. 1 ml of freshly distilled cyclopentadiene was prepared by your instructor in your dry and clean 10 ml graduated cylinder. 4. Using a clean Pasteur pipette, add the amount of cyclopentadine dropwise to the maleic andhydride solution. 5. Stir the mixture continuously and warm slowly to room temperature until the product crystallizes for solution. If crystallization does not occur, scratch the inside of the flask with a glass stirring rod to induce crystallization. 6. After crystallization, heat the solution to re-dissolve the product and allow to recrystallize. The hot plate should not be set too high. 7. Collect the product by suction filtration and weigh to get the experimental mass. 8. Determine the % yield of the dry material, take the I.R and m.p as well. EXP-4B: endo-norbornene-5,6-dicarboxylic acid. Place the remaining product from part A in a 50 ml round bottom flask with a boiling chip. 2. Add 10 ml of water to every 1.0 g of product and add three drops of concentrated sulfuric acid as well. (Your calculation should be included in your lab report). 3. Reflux the mixture for 10 minutes. 4. As the reaction proceeds, the anhydride will become soluble in water. Allow the mixture to cool to room temperature, and then place in an ice bath. 5. If crystals of the diacid do not form, scratch the inside of the flask with a stirring rod or spatula. 6. Collect the product by vacuum filtration. 7. Recrystallize the diacid from a minimum amount of boiling water. Add the water slowly by using a Pasteur pipette until all dissolves. 8. Allow slow formation of crystals to occur. 9. Collect the product by using vacuum filtration, wash the crystals with a small amount of cold water and dry overnight. 10. Calculate the % yield, mp and IR of the final product. Reference: www.chemfinder.com http://ptcl.chem.ox.ac.uk/MSDS http://www.aist.go.jp/RIODB/SDBS/sdbs/owa/sdbs_sea.cre_frame_sea 1.