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Catherine MacLean CHEM 258-06 Wednesday Night Diels-Alder Reaction in Water 4/8/13 Abstract

H2O + diene dienophile This experiment demonstrates a Diels-Alder reaction in water. The reaction was completed through reflux of anthracene-9-methanol and N-ethylmaleimide in water. The reaction yielded a Diels-Alder product in 78.5% yield with a melting point of 184.8 -186.3C. Extensive 1H and 13C NMR analysis revealed clear evidence of a product with multiple chiral centers and a cyclohexene species, which indicated the success of the Diels-Alder reaction. The narrow melting range and indication of purity in the spectra provides convincing evidence of the formation of a Diels-Alder product. Introduction This lab experiment is a demonstration of the Diels-Alder reaction carried out in water. Diels-Alder is a concerted reaction between a diene and a dienophile that results in a cyclohexene.1 The reaction can involved molecules with a large variety of substituents, so long as there is a diene with high electron density and a dienophile with low electron density. This reaction breaks the bonds of the starting materials and forms two and one bond.1 A critical facet of the Diels-Alder reaction is the retention of stereochemistry of both the starting materials in the final product. In many cases, this result in chirality of the final product, with all carbons and hydrogens on the core of the molecule rendered inequivalent.1 This specific reaction, involving anthracene-9-methanol and N-ethylmaleimide does indeed form a new chirality center which renders all its carbons and all the protons on the core of the molecule inequivalent.1 The concerted mechanism of a generalized Diels-Alder reaction is shown in Figure 1. Additional key features of this experiment are its perfect atom economy and the environmentally friendly reagents being used. Every atom in both starting materials is used in the final product, with no byproducts generated whatsoever. Water and methanol are the only reagents used besides the starting materials. Neither will give off harmful gases or byproducts when heated and both are very safe for disposal. The very favorable nature of bond formation in a Diels-Alder reaction means that this reaction will proceed without harsh conditions.1 The product will be analyzed for purity by 1H and 13C NMR and melting point determination. It is expected that the product spectra will display peaks characteristic of the cyclohexene created in the product, and that the preserved stereochemistry will render all of the central carbons and protons unequal. It is expected that the correct number of protons and carbons will fall within the aromatic regions of both spectra to show the breaking of bonds that is characteristic of a Diels-Alder equation. Full predictions and assignments of these peaks, 1

based on additive substituent parameters can be found on pages 8-9 of this report.2,3 While this products melting point has not been well characterized in the literature, the melting range is still a useful determinant of relative purity.

+ diene dienophile Figure 1. A generalized Diels-Alder reaction mechanism, involving reaction of diene and dienophile to create a cyclohexene. Experimental Methods Anthracene-9-methanol in the amount of 0.0650 g ( 3.12*10-4 mol) along with 25 mL (1.38 mol) water and 0.1162 g (9.3*10-4mol) N-ethylmaleimide were measured into a 100 mL round-bottom flask. the mixture was heated to reflux with stirring and refluxed for 30 minutes. The flask was then removed from the heat and cooled to room temperature before being placed on ice. Once crystals had formed, the crystals were collect via suction filtration, and were washed with water and ethanol during this process. After the crystals were collected and pressed between filter paper to remove excess moisture, they were dried on the suction filtration set up for fifteen minutes. The product was massed and found to be 0.0817 g for a 78.5% yield. 1H and 13 C NMR were completed on the product and the melting point was determined to be 184.8 186.3C.
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C NMR (CDCl3, 75 MHz, Diels-Alder Product): 177.022, 176.865, 142.327, 142.251, 139.484, 139.141, 127.075, 127.044, 126.872, 126.785, 125.525, 124.293, 123.400, 122.679, 60.822, 49.618, 47.943, 46.428, 45.940, 33.408, 12.256
1

H NMR (CDCl3, 300 MHz, 400 MHz, Diels-Alder Product): see attached peak assignments, page 8 Discussion The protons and carbons were given an assigned labeling scheme according to that on page 7 of this report. The predicted values for the ppm of the peak representing each carbon and type of proton were made with the aid of additive parameters for substituents as found in Mohrig.2,3 These predictions, along with actual assigned values are found on pages 8-9 of this report. The 1H NMR spectra showed a first peak at 7.609 ppm, signifying the a proton on the aromatic ring. While the value here was predicted to be 7.14 ppm, the downfield shift of this proton can be attributed to deshielding due to its proximity to the OH group. The peak displays J 3 of 7.6 Hz due to the b protons, and this produces the doublet splitting that is observed. Both the splitting and the integration of one align with predictions. The b proton displays a peak at 7.267 ppm, which again deviates from the predicted value of 7.08 due to proximity to the OH group. Its signal is split by both the a and c proton, yielding a triplet with an integration of one. The appearance of the peak is altered somewhat by its overlap with the peak corresponding CDCl3 which was used as a solvent in this NMR.1,2 Next, the Hc proton displays a peak at approximately 2

7.147 ppm, a very slight deviation from the predicted value of 7.08. It appears to display triplet like splitting, but overlap with the peaks corresponding to Hf make it impossible to determine the coupling constant. The signal is expected to be split by both Hb and Hd. It is once again the only proton of its kind, and its peak therefore displays an integration of one. Hd displays a peak at 7.195 ppm, a very slight variation from the predicted value of 7.14. Due to both J3 and J4 coupling which is characteristic of aromatic rings, it is a doublet of doublets through splitting by Hc and Hi. The coupling constants are 1.4 Hz and 3.87 Hz. Due to the conserved stereochemistry of Diels Alder and the chirality center of the product, this proton is also unique and its peak integrates to one. He displays a similar pattern with a peak at 7.23 ppm, again slightly downfield fromt eh predicted value of 7.14 ppm, likely due to deshielding due to three dimensional proximity to other substituents. Its peak is split by Hf and Hi to give a doublet of doublets and given that it is the only proton of its type, the peak integration is one. Hf is also a unique proton type with a peak integration of one, though its peak overlaps with that of Hc. These are nonequivalent protons, and thus this is a coincidental overlap. Due to the overlap, the location of the individual peaks is approximate, at roughly 7.147 ppm and the coupling constants cannot be determined. The individual protons were each predicted to produce a triplet and the resulting overlapping peak resembles a multiplet. Given the very similar splitting and location relative to other substituents of these two protons, the overlap is logical. Hg appears as a multiplet peak at 7.314 ppm, which varies from the predicted value of 7.08 ppm. The multiplet is most likely due to fine splitting of adjacent protons, which also contributes to the integration of one since Hg does not have any equivalent protons. The final aromatic proton, Hh displays a peak at 7.39, which is considerably downfield from the predicted value of 7.14, due to its proximity in space to the carbonyl groups. It appears with integration of one and as a doublet of doublets as predicted, due to J3 splitting of 7.2 Hz from the g proton and J4 splitting of 1.2 Hz due to the f proton.2,3 Beyond the aromatic region, the Hk protons appear as a doublet of doublets at 5.157 ppm with integration one. This is great deal further downfield than predicted due to the effects hydrogen bonding with the OH group which locks the k proton very close to both the OH and the adjacent carbonyl. It displays J3 coupling of 11.55 Hz from the j proton, and J4 of 5.157 Hz. Next, the j protons peak appears at 4.99 ppm as a doublet of doublets with integration one. Again, this is downfield of the predicted value due to proximity to the OH group. It displays coupling constants of 5.55 Hz and 5.925 Hz. Next, at 4.764 ppm is the peak corresponding to the Hm proton. As predicted, it is a doublet with integration one, but its value is considerably shifted from the predicted value of 2.5ppm by proximity to the OH group. It displays J 3 coupling of 3 Hz. While the i proton was predicted to appear at 4.3ppm, it actually appears upfield at 3.329 ppm due to shielding from the two aromatic rings that surround it. This peak is a doublet with J3 coupling of 4.05 Hz due to coupling with Hp. The next peak appears at 3.266 ppm and it represents the p proton, which is shifted downfield from the predicted value of 2.5 by proximity to the carbonyl group. It displays coupling due to both Hm and Hi of 4.2 Hz and 3.3 Hz. It is a doublet of doublets and integrates to one as predicted. Hl appears as a triplet with J3 coupling of 6.45 Hz at 2.773 ppm due to the effects of Hj and Hk. This ppm is within the predicted range for an alcohol proton. The remaining protons are part of alkane groups with few substituents. Due to mutual splitting, the Hn and Ho protons appear in a quartet-triplet pattern, as is characteristic of CH3CH2. The Hn peak appears at 3.166 ppm, very close to the predicted value of 3.3 ppm and integrates to 2, reflecting the two protons of that type. It couples with Ho protons with constants of 7.7275 Hz and 7.05 Hz, reflecting the adjacent alkane proton arrangement.4 The Ho proton is 3

the most upfield of them all appearing at 0.419, a bit upfield of the predicted value of 0.9 ppm. It integrates to three reflecting the three equivalent protons and displays J3 coupling with the n protons with a constant of 6.6 Hz.2,4 The key findings of the 1H NMR spectrum are the lack of any additional aromatic protons that might indicate the presence of existing starting material, and the presence of all expected protons in the correct regions of chemical shift. This provides evidence that the product was successfully formed. While there was a peak signifying the presence of water at 1.566 ppm, demonstrating some impurity, the compound does appear from the spectra to be pure relative to the starting material. In the 13C NMR, many of the predicted values based on additive parameters were quite similar, especially for the aromatic carbons. Due to very similar substituents, corresponding pairs of carbons on the two aromatic rings had the same predicted values. But in practice, the effects of different functional groups and the distance or proximity of a given carbon to them created some variance in the chemical shifts.3 The two highest values are that of C10 and C13 at 177.022 ppm and 176.865 respectively. These are in the appropriate ranges for carbonyl carbons as predicted, and C10 appears slighty higher due to its proximity to the OH group of the molecule. The next aromatic pair of protons are C21 and C6, which were both predicted to have values of 148.7 ppm, and had assigned peak values of 142.327 and 142.251 ppm, respectively. The fact that each is bonded mainly to other carbons creates the shielding that moves the peaks to a lower value than predicted, and C21 has the higher value due to its proximity to the carbonyl groups. C16 and C5 were both given predicted values of 145.4 ppm, and their actual assigned values fell at 139.484 and 139.141 ppm, respectively. This is due to the proximity that C16 has to the carbonyl carbons, and the degree to which both carbons are shielded by the distance they are at from other functional groups. Another pair of aromatic protons, C17 and C4, was assigned at 127.075 and 127.044 ppm respectively, values that differed very slightly from the predicted shift at 125.9 ppm. Again, the proximity to the carbonyl groups made C17 slightly more deshielded, giving it the higher chemical shift. The next pait, C19 and C2, fall immediately below them on the scale, at 126.872 ppm and 126.785 ppm respectively, quite close to their predicted shift of 125.3 ppm. C19 appears at a slightly higher shift, again due to proximity to the carbonyl groups and the OH group. The predicted chemical shift for C18 and C3 was 125.1 ppm. However, the actual values assigned were 125.525 and 124.293 respectively. The difference in chemical shift was again caused by the proximity of C18 to the OH group. The final pair of aromatic protons with the same predicted shift was C1 and C20 at 124.9 ppm. In the product spectra, the peaks were assigned at 122.679 ppm and 123.400 ppm respectively. C20 is in much greater proximity to the carbonyl and alcohol functional groups, which causes the difference in shift and its downfield position. C7 is the next peak in the spectra, appearing at 60.822 ppm, incredibly close to the predicted value of 60.9 ppm. Following that is the peak representing C8, which comes in at 49.618 ppm as compared to the predicted value of 56.2 ppm. This may be due to shielding effects from the hydrogen bonding of the adjacent Oh group which lock C8 into a relatively guarded position. The peaks for C11, 15, and 9 follow in rapid succession at 47.943 ppm, 46.428 ppm, and 45.940 ppm respectively. The predicted values for these peaks were 43.5 ppm, 51.8 ppm, and 36.4 ppm. C11 varies from its predicted value due to its proximity to the nitrogen and the two carbonyl groups with little to no shielding. C15 comes in lower than its predicted value, and C9 higher, due to the effects of the groups they are adjacent too. For C9, the hydrogen bonding effects of the alcohol group are highly relevant. C14 was predicted to have a chemical 4

shift of 36.4 ppm but its assigned shift was 33.408 ppm. Finally, C12 had a predicted shift of 6.8 but its peak on the spectra appears at 12.256 due to the effects of the nitrogen that is a substituent. The appearance of so many of these carbons in the alkane region and only twelve in the aromatic region is very convincing evidence of the successful formation of the product. Again, in the 13C NMR, the evidence suggests that the product was successfully formed, with the correct number of peaks appearing and an accurate correspondence between the predictions, the three dimensional structure of the molecule and the spectra. No impurities were noted on the 13C NMR. Upon melting point determination, the melting point was found to be 184.8 -186.3C. Although no conclusive account has been published of this compounds melting point, the narrowness of the range is an indicator of purity. Conclusion This experiment successfully demonstrated the completion of Diels-Alder reaction in water. The product spectra displayed values in accordance with those expected and did display the proper chirality and inequivalence of both carbon and hydrogen molecules. The presence of both protons and carbons in the alkane regions of the spectra was indicative of successful product formation. The number and chemical shift of protons and carbons in the aromatic region was in accordance with the predicted values. While this products melting point is not well known, the melting range determined from the prepared product was of a very narrow range, indicating purity. Taken together, the spectra and melting point analysis suggest that this product was successfully produced at a high level of purity. In the future, exploration of the Diels-Alder reaction with N-methylmaleimide could be instructive as a demonstration of the importance of electron withdrawing groups on the dienophile to the reaction rate. References 1. Roberts, Andrea. Chemistry 258. Diels Alder in Water Lecture. Wesleyan University, Middletown. CT. 29 Mar 2013. 2. Mohrig, J, Christina Noring Hammond, Paul F. Schatz. Techniques in Organic Chemistry, 3rd ed;W.H. Freeman and Co.: New York, 2010. pp 333-337. 3. Mohrig, J, Christina Noring Hammond, Paul F. Schatz. Techniques in Organic Chemistry, 3rd ed;W.H. Freeman and Co.: New York, 2010. p 381-387. 4. Mohrig, J, Christina Noring Hammond, Paul F. Schatz. Techniques in Organic Chemistry, 3rd ed;W.H. Freeman and Co.: New York, 2010. pp 351.

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