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. Author manuscript; available in PMC: 2013 Jul 26.
Published in final edited form as: Macromol Rapid Commun. 2012 Apr 20;33(14):1220–1226. doi: 10.1002/marc.201200107

Table 1.

Fe(III)TPPF 84 catalysis of cyclohexene oxidation.

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;

a)

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;

b)

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).