Matthew Adams SRJC Chem 12B Lab TTh 12-3 Prof.

George 4/21/11 Experiment 42 A Wittig Reaction of trans-Cinnamaldehyde Abstract: The objective of this experiment was to prepare (E,E)-1,4-diphenyl-1,3-butadiene from trans-cinnamaldehyde by means of a Wittig reaction. The ylide for the Wittig reaction, benzyltriphenylphosphonium chloride, was prepared and reacted with transcinnamaldehyde in a solution of NaOH and dichloromethane. The final product had a melting a range of 120-142C suggesting a mixture of the (E,E) and (E,Z) isomers of 1,4diphenyl-1,3-butadiene which melt at 153C and 88C respectively. The H-NMR and IR spectrum s where characteristic of 1,4-diphenyl-1,3-butadiene. The IR spectrum did contain absorption peaks in the typical range of both cis and trans disubstituted alkenes indicating the (E,E) and (E,Z) isomers where present. The percent yield for the procedure was 21.9%. Discussion/Results: The evidence for the identity of the final product came from analysis of melting point, H-NMR and IR spectrums. The melting range of the product was 120-142C which is very broad and lower then the expected products melting point of 153C. This melting range could be do to the product being a mixture of the (E,E) and (E,Z) isomers of 1,4diphenyl-1,3-butadiene which melt at 153C and 88C respectively or the triphenylphosphine byproduct which melts at 80.5C. The IR spectrum contains absorption peaks at approximately 990 cm-1 and 686 cm-1 which are characteristic of trans and cis disubstituted alkenes, supporting the conclusion that the product is a mixture of (E,E) and (E,Z) isomers. The rest of the signals on the IR and H-NMR are characteristic of 1,4diphenyl-1,3-butadiene (Tables 1 and 2). While the exact purity is unknown, based on the melting range leaning more towards the (E,E) isomer and the reactions preference for that isomer the product likely

contained more then 50% (E,E) with the rest being the and (E,Z) isomer. The separation and purification steps should have easily removed all other byproducts. Removal of (E,Z)-1,4-diphenyl-1,3-butadiene should have occurred during the recrystallization but did not for unknown reasons. The percent yield for this procedure was 21.9%. Most product loss occurred during extraction, filtering and recrystallizing steps, as well as from transferring the product between glassware. The mechanism for the witting reaction is a [2+2] cycloaddition. The nucleophilic carbon of the ylide adds to the carbonyl carbon of trans-cinnamaldehyde while the carbonyl oxygen adds to the electrophilic phosphorus of the ylide forming a cyclic transition state. Then triphenylphosphine oxide is eliminated forming the alkene product (Figure 1).

Analysis of H-NMR Spectrum: Table 1: Summery of H-NMR spectrum of (E,E)-1,4-diphenyl-1,3-butadiene Chemical Shift (PPM) Multiplicity Neighbors Integration Assignment 6.8 Triplet 4 4 H-C=CH-CH=C-H 7.4 Singlet 2 10 Ar-H Analysis of IR Spectrum: Table 2: Summery of IR spectrum of (E,E)-1,4-diphenyl-1,3-butadiene Wavenumber (cmIntensity Bond Type 1) (%T) 3015.16 64.1772 Csp2-H stretch 1620.58 73.5728 C=C stretch alkene 1489.74 60.3862 C=C stretch aromatic 990.268 35.7803 C-H(bend) trans-disubstituted alkenes 738.603 31.6362 Ar-H(bend)monosubstituted benzene *686.534 22.9642 C-H(bend) cis-disubstituted alkenes * Caused by (E,Z)-1,4-diphenyl-1,3-butadiene impurity.

Assignment Ar -H C=C Ar H-C=C-H Ar-H H-C=C-H

Conclusion: A mixture of (E,E) and (E,Z)-1,4-diphenyl-1,3-butadiene was created from benzyltriphenylphosphonium chloride and trans-cinnamaldehyde by a Wittig reaction. The percent yield was 21.9%.