## 3 Results and Discussion
### Catalyzed Oxidation of \(\beta\)-Myrcene
#### 3.4.3 Effect of TBHP as Oxidant with Organic Salts of POMs  
Using TBHP\({}_{\mathrm{aq}}\), similar or lower conversions were observed in comparison to H\({}_{2}\)O\({}_{2\mathrm{aq}}\), but this was associated with a significant increase in myrrene oxide yields in all cases, being  
\begin{table}
\begin{tabular}{l l l l l l} \hline \hline
**Catalysts** & **Entry** & **T (\({}^{\circ}\)C)** & **Oxidant** & \
\begin{tabular}{l} \(\beta\)**-Myrrene** \\ **Conv (\%)** \\ \end{tabular} &
\begin{tabular}{l} **Myrrene** \\ **Oxide Yield (\%)** \\ \end{tabular} \\ \hline
**MRImd@PMo\({}_{12}\)O\({}_{40}\)** & M26 & 70 & H\({}_{2}\)O\({}_{2\mathrm{aq}}\) & 94 & 6 \\  & M27 & 80 & TBHP\({}_{\mathrm{aq}}\) & 64 & 6 \\ \hline
**MRPyr@PMo\({}_{12}\)O\({}_{40}\)** & M28 & 70 & H\({}_{2}\)O\({}_{2\mathrm{aq}}\) & 94 & 5 \\  & M29 & 80 & TBHP\({}_{\mathrm{aq}}\) & 95 & 5 \\ \hline
**MRImd@PMo\({}_{11}\)VO\({}_{40}\)** & M30 & 70 & H\({}_{2}\)O\({}_{2\mathrm{aq}}\) & 98 & 9 \\  & M31 & 80 & TBHP\({}_{\mathrm{aq}}\) & 88 & 9 \\  & M32 & 80 & TBHP\({}_{\mathrm{dec}}\) & 75 & 26 \\ \hline
**MRPyr@PMo\({}_{11}\)VO\({}_{40}\)** & M33 & 70 & H\({}_{2}\)O\({}_{2\mathrm{aq}}\) & 95 & 5 \\  & M34 & 80 & TBHP\({}_{\mathrm{aq}}\) & 85 & 5 \\ \hline \hline \end{tabular}  
* Few drops of CH\({}_{3}\)CN were added. \({}^{2}\)\(\beta\)-myrrene was heated without oxidant. DA *: Diels–Alder product detected in GC-MS. Catalytic conditions: For ionic salts of POMs: cat/sub/ox: 0.25/100/200, and at 80 \({}^{\circ}\)C with TBHP\({}_{\mathrm{aq}}\) and TBHP\({}_{\mathrm{dec}}\) and at 70 \({}^{\circ}\)C with H\({}_{2}\)O\({}_{2\mathrm{aq}}\) for 5 h. Toluene and ethyl acetate were added as solvents with H\({}_{2}\)O\({}_{2\mathrm{aq}}\) in some cases. For grafted POMs: 0.1 g of **MROrg@POMs** was used in which cat/sub/ox were 0.25 \(\times\) 10\({}^{-3}\)/100/200, and at 80 \({}^{\circ}\)C with TBHP\({}_{\mathrm{aq}}\) and at 70 \({}^{\circ}\)C with H\({}_{2}\)O\({}_{2\mathrm{aq}}\) for 5 h.  
\end{table}
Table 2: _Cont._in the range of 7-10% (M4 and M8) in the case of (PMo\({}_{12}\)O\({}_{40}\))\({}^{3-}\) and 41-53% (M21, M14) for the (PMo\({}_{11}\)VO\({}_{40}\))\({}^{4-}\) salts; the highest yield was for the BmIm salt.  
The highest conversion was obtained for all salts when using TBHP in decane, proving the positive role of apolar and aprotic solvents. In terms of yields towards myrcene oxide, the best results are obtained with **(BmIm)\({}_{3}\)PMo\({}_{12}\)O\({}_{40}\)** (39% yield, M4) and **(BmIm)\({}_{4}\)PMo\({}_{11}\)VO\({}_{40}\)** (41% yield, M15) as catalysts.  
TBHP seems to be more effective for epoxidation than H\({}_{2}\)O\({}_{2}\). This is certainly due to the fact that TBHP is more soluble in apolar organic media. With TBHP in decane (TBHP\({}_{\rm dec}\)), conversion improved further in all cases (Entries M4, M15 and M9) with good oxide yields in the cases of BmIm salts compared to BuPyr ones. For example, 89% conversion with a 39% yield of oxide was obtained with **(BmIm)\({}_{3}\)PMo\({}_{12}\)O\({}_{40}\)** (Entry M5), which was much higher than that with the same POM. However, within the other organic part, a high conversion (80%) but lower yield of oxide (15%) was observed (Entry M9).  
On the other hand, with the best-chosen conditions and with TBHP\({}_{\rm dec}\), only 39% conversion was observed with naked **MR** (Entry M25), with no oxide formed, which could be due to the Diels-Alder reaction (as described before), highlighting the crucial role of the POM in the oxide formation process.