Linjia Jia TA: Hong Zhao

Experimental Date: 2/02/2012 Section: 210 The Diels-Alder Reaction of 3-sulfolene and maleic anhydride in production of 4-cyclohexene-cis-1,2, dicarboxylic anhydride

Results Mass of adduct: 0.715 g Melting point of adduct: 102-105 C To calculate the percent yield, first the theoretical adduct mass must be calculated. In this experiment, 0.0127 moles 3-sulfolene and 0.0095 moles of maleic anhydride react, and because the reactants are in 1:1 ratio, maleic anhydride is the limiting reactant. Calculations 0.0095 moles maleic anhydride (limiting reactant) reacts with 0.0095 moles 3-sulfolene (0.0032 moles in excess); molar mass of adduct 4-cyclohexene-cis-1,2 dicarboxylic anhydride is 152.14 g Theoretical yield = mole of limiting reactant x molar mass of adduct Theoretical yield = 0.0095 mol x 152.14 g Theoretical yield = 1.45 g % yield = % yield = x 100% x 100%

% yield = 49.31% Discussion & Conclusion Several factors could explain the relatively poor yield. In transferring the adduct from Buchner funnel onto watchglass, some adduct has been stuck on filter paper and is therefore not accounted for in the mass. However, filter paper fibers too could have been accounted in the mass during the same transfer. Some experimental errors also contribute to low yield, such as not enough time was not given for reflux and that filter paper did not cover Buchner filter complete and some adduct was lost during washes. Further, butadiene gas could have been produced during reflux due to rapid heating, which would not react with maleic anhydride and therefore no adduct would be produced. Though the yield is less than 50%, it still indicates that mini-scale reflux was quite successful in producing the adduct.

The melting point range of the adduct is taken to be 102-105 C, while the actual melting point of 4-cyclohexene-cis-1,2 dicarboxylic anhydride is 103-104 C. The cited melting point falls within the range of experimental melting point range, which means that the purity of the adduct is quite high and that reflux was successful in inducing the DielsAlder reaction between sulfolene and maleic anhydride, and that reaction itself was successful in producing 4-cyclohexene-cis-1,2 dicarboxylic anhydride in high purity. Post-Lab In this experiment, 3-sulfolene is used instead of butadiene because at room temperature, 3-sulfolene is in solid form whereas butadiene is a gas (its boiling point is -4.5 C) and therefore would not react with maleic anhydride (also in solid phase at room temperature). In comparison to butadiene, 3-sulfolene is much easier to handle and it ensures the best yield possible (both reactants would be in solid phase). If butadiene were used, the current experiment set up would need to be adjusted significantly, as it would be very inefficient otherwise. To ensure good yield, both butadiene and maleic anhydride must be in the same physical phase, which means that either the experiment takes place at extremely low temperature (below the melting point of butadiene, -108.9 C) so that both are in solid phase or extremely high temperature (above the boiling point of maleic anhydride, 202 C) so that both are in gaseous phase. The Diels-Alder reaction is a concerted mechanism, which means that stereochemistry is conserved. This also means that there cannot be more than one stereochemical product due to syn-addition. Because the diene must be in s-cis conformation, the product retains also the s-cis conformation.
Product 4-cyclohexene-cis-1,2 dicarboxylic anhydride in s-cis conformation

Post-Lab Questions Gilbert & Martin, Pg 433-434 1. A cyclic 1,3-diene dimerizes much more readily than does an acyclic one because it is already in the required s-cis conformation for a Diels-Alder reaction, whereas an acyclic 1,3-diene is free to rotate across the bond and requires some energy to rotate into the s-cis conformation. Further, an adduct formed from a Diels-Alder reaction from a diene in the s-trans conformation would have much steric strain and therefore is much less likely than one produced from a diene in s-cis conformation. 4.

8. a. diene:

dienophile:

b. diene:

dienophile:

NMR Analysis

H1 = 3.52 H2 = 2.39 H3 = 2.26 H4 = 5.95 Reference Gilbert, John C. & Martin, Stephen F. Experimental Organic Chemistry: A Miniscale and Microscale Approach, Fifth Edition, 2011.