Table 1.
Solution a) or ONP b) |
Conditions | % epoxide | % enol | % enone | TON | Comments |
---|---|---|---|---|---|---|
Solution | 125 mL O2 | 16 | 29 | 55 | 158 | 36% porphyrin left |
Solution | 125 mL O2 | 20 | 27 | 53 | 147 | 72 h, no porphyrin left |
Solution | 125 mL O2, 1.73 atm | 13 | 32 | 55 | 129 | No porphyrin left |
Solution | 125 mL O2, 40 °C | 8 | 35 | 57 | 140 | No porphyrin left |
Solution | 125 mL O2, 50 °C | 6 | 38 | 56 | 123 | No porphyrin left |
ONP | 125 mL O2 | <1 | 29 | 70 | 670 | 26% porphyrin left |
ONP | 125 mL O2 | <1 | 32 | 67 | 350 | 72 h, no porphyrin left |
ONP | 125 mL O2, 1.73 atm | <1 | 31 | 68 | 305 | No porphyrin left |
ONP | 125 mL O2, 40 °C or 50 °C |
X | X | X | X | No porphyrin left |
Reactions were run at room temperature and 1 atm for 24 h unless noted;
Solution reactions: 0.4 mL (1 × 10−3 m, 4 × 10−7 mol of porphyrin) of catalyst was mixed with 2.5 mL of methanol: acetonitrile (1:3) and 0.2 mL of cyclohexene to a final concentration of 0.13 × 10−3 m. 125 mL of O2 , porphyrin: cyclohexene: O2 = 1:4800:13000 was used;
ONP reactions with O2: 15–20 nm diameter ONP suspension (2.5 mL, 70 × 10−6 M, 1.75 × 10−7 mol of porphyrin) mixed with cyclohexene (0.2 mL) and O2 (125 mL); porphyrin: cyclohexene: O2 = 1:11300: 29000. TON = molproducts/molporphyrin has an error of ±5%. Products were extracted into CH2Cl2 and analyzed by using an Agilent 5975 series GC – MS. Control reactions: neither H2O2 nor O2 react directly with cyclohexene under these conditions (Table S1, Supporting Information).