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Molecules 2016, 21, 24 5 of 11 2.2. Synthesis of n-Propyl, Benzophenone(BP) Imine Molecules 2016, 21, 24 5 of 10 Titanium(IV) isopropoxide is a low cost mediator in BP imine synthesis [42–46]. According to Figure 2, the initial BP concentration of 0.45 M is slowly reduced to 0.26 M after 3 h and finally 0.11 M after 24 h as the reaction proceeds. Gas chromatography (GC) was used to determine an overall yield of 75% for the non-protected amine while a 25% yield is obtained for the protected and 50% for de-protected propylamine. Once again, a similar trend is seen with the de-protected amines falling short of the original product yield, which is attributed to the incomplete reversal of carbamates or propylamine volatilization during the de-protection process. Figure 2. Plot of benzophenone (BP) concentration determined via gas chromatography (GC) for the non-protected, protected and de-protected propylamine reactions at 3, 6 and 24 h. Although FTIR is not commonly used as a powerful quantitative tool, it was used to confirm the presence of our imine species, as well as, calculate the BP conversion. Figure 3 shows the strongly absorbing C=N shift to 1620 cm−1 from the C=O at 1660 cm−1 of the original BP [47]. This shift in absorbance demonstrates that the desired imine species was obtained during the BP-propylamine 1 reactFiiognusrean2.dPtlhotisofwbaesnzfuoprtheenroenvei(dBePn)cceodncveinatrHatiNonMdRetearnmdinGedCv-MiaSg.as chromatography (GC) for the Molecules 2016, 21, 24 5 of 10 Figure 2. Plot of benzophenone (BP) concentration determined via gas chromatography (GC) for the non-protected, protected and de-protected propylamine reactions at 3, 6 and 24 h. The qualitative analysis was conducted over a period of 12 h, during which time ATR-FTIR non-protected, protected and de-protected propylamine reactions at 3, 6 and 24 h. spectra of aliquots of the reaction vessels were collected and analyzed to confirm the appearance of the Although FTIR is not commonly used as a powerful quantitative tool, it was used to confirm imine product. As the reaction proceeds forward, the concentration of imine in the reaction solution Although FTIR is not commonly used as a powerful quantitative tool, it was used to confirm the the presence of our imine species, as well as, calculate the BP conversion. Figure 3 shows the strongly will increase until equilibrium has been reached. By analyzing the absorbance ratio of C=O to C=N, presenceofouriminespecies,as−1wellas,calculatetheBPco−n1version.Figure3showsthestrongly absorbing C=N shift to 1620 cm from the C=O at 1660 cm of the original BP [47]. This shift in the percentage of imine in the reaction vessel was determined (Table 3). These calculated values absorbing C=N shift to 1620 cm ́1 from the C=O at 1660 cm ́1 of the original BP [47]. This shift in absorbance demonstrates that the desired imine species was obtained during the BP-propylamine correlate very well to the percentage conversion obtained via GC and support our initial hypothesis absorbancedemonstratesthatthedesiredimin1especieswasobtainedduringtheBP-propylamine reactions and this was further evidenced via H NMR and GC-MS. that CO2 is a viable tool for the protection and inhibition of free primary amines to undergo coupling reactions and this was further evidenced via H1NMR and GC-MS. The qualitative analysis was conducted over a period of 12 h, during which time ATR-FTIR reactions. spectra of aliquots of the reaction vessels were collected and analyzed to confirm the appearance of the imine product. As the reaction proceeds forward, the concentration of imine in the reaction solution will increase until equilibrium has been reached. By analyzing the absorbance ratio of C=O to C=N, the percentage of imine in the reaction vessel was determined (Table 3). These calculated values correlate very well to the percentage conversion obtained via GC and support our initial hypothesis that CO2 is a viable tool for the protection and inhibition of free primary amines to undergo coupling reactions. Figure 3. FTIR of pure BP (dashed) compared to isolated BP imine product (solid). Figure 3. FTIR of pure BP (dashed) compared to isolated BP imine product (solid). Table 3. Determined BP conversion from GC analysis compared to BP conversion calculated from IR The qualitative analysis was conducted over a period of 12 h, during which time ATR-FTIR spectral C=N/C=O absorbance ratio. spectra of aliquots of the reaction vessels were collected and analyzed to confirm the appearance of the Sample Time (h) Calculated IR Conversion (%) Conversion from GC (%) imine product. As the reaction proceeds forward, the concentration of imine in the reaction solution Non-protected 3 35 33 will increase until equilibrium has been reached. By analyzing the absorbance ratio of C=O to C=N, the Non-protected 12 55 65 percentage of imine in the reaction vessel was determined (Table 3). These calculated values correlate Figure 3. FTIR of pure BP (dashed) compared to isolated BP imine product (solid). Protected 3 16 18 Protected 12 26 20 * Table 3. Determined BP conversion from GC analysis compared to BP conversion calculated from IR * denotes a value that was estimated using Figure S7. spectral C=N/C=O absorbance ratio. In a separate set of experiments, imine formation was observed to take place without the presence Sample Time (h) Calculated IR Conversion (%) Conversion from GC (%) of mechanical stirring (Figure S7). Here, the benzophenone, Ti catalyst and propylamine were combined Non-protected 3 35 33PDF Image | Amines vs Nucleophilic Substitution Reversible Reaction CO2
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