ed. 1 H NMR (400 MHz, D O/NaOH-Benzoic acid) 7.66 (m, 2H, Ar-H), 7.29 (m, 3H, 2 Ar-H), 3.42 (q, J = 7.1 Hz, 0.03H, CH2 ), 3.12 (s, 0.03H, CH3 ), 1.99 (m, 0.12H, CH2 ), 1.02 (t, J = 7.1 Hz, 0.04H, CH3 ), 0.46 (m, 0.13H, CH2 ). 29 Si CP MAS-NMR: -58.eight ppm (T2 ), -68.four ppm (T3 ), -91.9 ppm (Q2 ), -101.eight ppm (Q3 ), -111.six ppm (Q4 ). 13 C CP MAS-NMR: 177.9 ppm (COOH), 59.9 ppm (CH2 O), 49.five ppm (CH2 O), 16.7 ppm (CH3 ), six.7 ppm (CH2 Si).IR (ATR, (cm-1 )): 3709852 (OH), 1717 (C=O), 1046 (Si-O-Si), 932 (Si-OH), 785 and 450 (Si-O-Si). (COOH) = 0.31 mmol/g. COOH) = three.2 functions/nm2 . three.five. Catalytic Experiments three.5.1. Basic Procedure of Catalysis with CH3 COOH A measure of 1 mmol of substrate (CO, CH. CYol), 0.84 g (14 mmol or 0.14 mmol) of CH3 COOH, 0.01 mmol of complexes ((L)MnCl2 , (L)Mn(OTf)2 , (L)Mn(p-Ts)two , [(L)FeCl2 ](FeCl4 )) and some drops of an internal common (acetophenone) had been mixed in two mL of CH3 CN at room temperature. A measure of 0.13 mL of H2 O2 (35 wt. in H2 O) diluted into 0.87 mL of CH3 CN was gradually added in to the mixture for two h at 0 C. The mixture was left for 1 h at 0 C. three.five.2. Basic Procedure of Catalysis with SiO2 @COOH A measure of 1 mmol of substrate (CO, CH, CYol), 300 mg of SiO2 @COOH(E) (13.5 mg for SiO2 @COOH(M) (0.14 mmol of carboxylic function), 0.01 mmol of complexes ((L)MnCl2 , (L)Mn(OTf)2 , (L)Mn(p-Ts)2 , [(L)FeCl2 ](FeCl4 )) and a few drops of an internal typical (acetophenone) were mixed in 2 mL of CH3 CN at room temperature. A measure of 0.13 mL of H2 O2 (35 wt. in H2 O) diluted in 0.87 mL of CH3 CN was gradually added towards the mixture for 3 h at 50 C. Then the mixture was left at 60 C for 2 h. four. Conclusions It has been feasible to replace acetic acid with silica beads with carboxylic functions in the reaction in the epoxidation of olefins. The study showed lower activity together with the silicaMolecules 2021, 26,22 ofbeads in the case of cyclooctene and cyclohexene oxidation with manganese complexes and selectivity seemed to be linked for the nature of the ion on the complicated. With cyclohexene, the activity together with the beads was MMP-10 custom synthesis greater reasonably to cyclooctene. Even so, for the Fe complicated, the beads were more active than acetic acid. With 5-HT6 Receptor Modulator supplier cyclohexanol, the course of action worked significantly superior with acetic acid. The size on the bead seemed to have no relevant impact with regards to efficiency, except that the quantity of carboxylic functions brought into the reaction was one hundred instances less than the quantity of acetic acid. It should be noted that beneath a lower quantity of acetic acid, the reaction didn’t perform. Although less active, this approach is the very first step towards the replacement of an organic volatile reagent.Supplementary Materials: The following are obtainable on the net, Table S1: Crystal data. Table S2: Bond lengths [ and angles [ ] for (L)Mn(p-Ts)two . Table S3: Bond lengths [ and angles [ ] for [(L)FeCl2 ](FeCl4 ). Table S4: Relevant solid-state NMR data. Table S5: 1 H NMR chemical shifts (in ppm) observed with SiO2 , SiO2 @CN and SiO2 @COOH in D2 O/NaOH (pH = 13) option. Figure S1: 13 C MAS NMR spectra of SiO2 (bottom), SiO2 @CN (middle) and SiO2 @COOH (leading) for beads from SiO2 beads developed in EtOH (left) and MeOH (proper). Figure S2: 29 Si MAS NMR spectra of SiO2 (top) SiO2 @CN (middle), SiO2 @COOH (bottom) from SiO2 beads created in EtOH (left) and MeOH (proper). Author Contributions: Conceptualization, D.A. and P.G.; methodology, D.A. and P.G.; validation, Y.W., P.G., F.G., J.-C.D. and D.A.; formal analysis, Y.W
