Diels-Alder Reaction Furan and Maleic Anhydride

Introduction: The objective of the experiment is to perform the Diels-Alder [4+2] cycloaddition of Furan and Maleic Anhydride and use NMR spectroscopy to determine the product formed. This type of reaction has the possibility of forming both endo or exo furan-maleic anhydride adducts. Theory: The Diels-alder reaction occurs when a conjugated diene and an isolated alkene are added together in one step. The bonding electrons redistribute forming two carbon-carbon bonds to create a cyclic product. With a cyclic diene and cyclic dienophile, two products form that have different stereochemistries. They are the exo and endo-adducts. The endo-adduct is the kinetic product as it is faster and takes less energy to form. It is less stable than the exo-adduct, which is the thermodynamic product, so the endo is easily reversible in equilibrium conditions. When equilibration occurs, the fast reversal of the endo allows for gradual build up of the exo so that the exo will be the major product. Furan (C4H4O), the diene of the reaction, is a five-membered conjugated ring. It reacts with maleic anhydride (C4H2O3), the dienophile of the reaction, which has a five-membered ring with an isolated pi bond. The possible products formed are the endo and exo furan-maleic anhydride adducts (C8H6O4).

The experiment can be carried out under specific conditions in order to contol what the major product will be. If the reaction is done quickly, isolating the endo, it will be the major product. If the reaction is done over a longer period of time, exo will be the major product.

Materials: Maleic anhydride, furan, ethyl acetate, acetone, hexane, dueterated chloroform or acetone-d6, pipet, vials, graduated cylindar, NMR tube, cotton, glass pipet, test tube Procedure: Day 1: Dissolve 400mg maleic anhydride with 2ml ethyl acetate in a vial. Add 0.4ml furan. Seal vial and place in refrigerator until next lab so that it crystallizes. Day2: Pipette out excess liquid from the crystals. Dissolve the crystals in a minimal amount of acetone. Add just enough hexane for the solution to get cloudy. Let it recrystallize for next lab. Day 3: Pipette out any solvent left in vial wih crystals then leave vial open in drawer. Day 4: After crystals have dried, prepare for NMR. Dissolve crystals in a minimal amount of soplvent and filter 1ml through cotton in glass pipet into the NMR tube. HNMR spectroscopy. Hazards/MSDS: Maleic Anhydride Furan Acetone Hexanes Acetone d6 Deuterated chloroform Ethyl acetate Discussion: We ran into many obstacles when trying to carry out this experiment and we needed to repeat it. The first time we performed the experiment, the crystals did not recrystallize for day three. We eventually got crystals and when we completed the experiment and viewed the HNMR spectrum, only acetone was visible. Errors could have been made in adding too much solvent, the wrong solvent or even in the preparation for NMR. We repeated the experiment and it went much better than the first time. We made sure to use minimal amounts of each solvent as we thought that may have been our original error. The HNMR spectrum showed the major product we expected. There were additional peaks for unreacted starting material in addition to the peaks indicating the solvents.

The exo product was the major product. The experiment was done over the length of a few weeks and had time to equilibrate so that the exo product would build up.

Data:

Peaks: Chemical Shifts(ppm): ~3.1 ~5.5 ~6.4 ~6.5 ~7.1~7.3~7.5 (solvent and unreacted starting material?)

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