Supplementary Material

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1 Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry. This journal is The Royal Society of Chemistry 214 Supplementary Material Inverse solvent effects in the heterogeneous and homogeneous epoxidation of cis heptene with [2 percarboxyethyl] functionalized silica and meta chloroperbenzoic acid Rossella Mello, a Jeymy T. Sarmiento Monsalve, a Diana Vargas Oviedo, a Rafael Acerete, b María Elena González Núñez, a * Gregorio Asensio a a Departmento de Química Orgánica. Facultad de Farmacia. Universidad de Valencia. Avda. Vicente Andrés Estellés s.n., 461 Burjassot, Valencia, Spain b Departmento de Química Inorgánica. Facultad de Farmacia. Universidad de Valencia. Avda. Vicente Andrés Estellés s.n., 461 Burjassot, Valencia, Spain General. Solvents and reagents were purified before use by following standard procedures. 1 Glassware was successively washed with an aqueous EDTA solution (.125 g L ), ultrapure water and acetone purified by distillation from KMnO 4. Peroxydic reagents 1 were stored at 3ºC in the dark. The GC analyses were performed with a capillary column Agilent HP1 (3 m length, internal diameter.32 mm and film thickness.25 m), with an injector temperature of 25 º C and FID temperature 28 o C. [2 Percarboxyethyl] functionalized silica () was prepared by the sol gel method following reported procedures. 2,3 Prior to each kinetic experiment, solid peracid was dried under vacuum (.1 mm Hg) at room temperature until it reached a constant weight, and its peroxydic content was determined by standard iodometric titration. meta Chloroperbenzoic acid (mcpba) () 96 99% w/w was obtained by treating commercial samples (6 7%) with a K 2 HPO 4 /NaH 2 PO 4 buffer solution at ph 7.5 and at room temperature for 6 h, followed by recrystallization at o C from /diethyl ether 3:1. The mcpba solutions () (.5 M) in the different solvents were prepared at the same temperature of the experiments using a thermostatted bath. The peroxydic content of the solution was determined prior to each kinetic experiment. Solutions of cis heptene (.1 M) and adamantane, as an internal standard (.5 M), in the different solvents (Table 1) were prepared at the kinetic experiment temperature with a thermostatted bath. The reaction conditions for each kinetic experiment were previously optimized for each peracid and solvent, and depended mainly on the boiling point of the solvent and the solubility of mcpba () in each case. The kinetic experiments were performed at least three times for each solvent and temperature. S1

2 Kinetic experiments for. General procedure. To a solution (4 ml) of cis heptene (.1 M) and adamantane (.5 M), as an internal standard in dichloromethane, placed in a jacketed flask thermostatted at 2. ±.1 o C by a recirculating bath, solid peracid (.4 mmol) was added at once under stirring (4 rpm). The aliquots (.2 ml) withdrawn from the reaction mixture were quenched with.4 ml of a.25 M solution of thoanisol in dichloromethane, filtered through a Teflon syringe filter (.2 m) and analyzed by gas chromatography. Substrate conversions were determined from the ratio of peak areas cis heptene/adamantane found for the starting solution and the corresponding aliquot. Kinetic experiments for. General procedure. To a solution (2.5 ml) of cis heptene (.1 M) and adamantane (.5 M), as an internal standard in dichloromethane, placed in a jacketed flask thermostatted at 2. ±.1 o C by a recirculating bath, a.5 M solution of mcpba () (5 ml,.25 mmol) in the same solvent, thermostatted at the same temperature, was added under stirring (4 rpm). The aliquots (.4 ml) withdrawn from the reaction mixture were quenched with.1 ml of a 1 M solution of thoanisol in dichloromethane, and were analyzed by gas chromatography. Substrate conversions were determined from the ratio of peak areas cis heptene/adamantane found for the starting solution and the corresponding aliquot. Figures S12 show the pseudofirst order plots Ln ([olefin] t /[olefin] ) versus time obtained for the epoxidations of cis hexene with [2 percarboxyethyl] functionalized silica () and metachloroperbenzoic acid () in, carbon tetrachloride, dichloromethane, chloroform and acetonitrile at 2. o C, and in, dichloromethane and chloroform at 3./39.6 o C, 1./5. o C, and 1./35. o C, respectively. Figures S238 show the temperature dependence of the rate constants for the reactions of and with cis hexene in chloroform (1./2./35. o C), dichloromethane (./5./2. o C) and (2./3./39.6 o C). Activation parameters were calculated from these plots by applying the following equations. [4] k = A exp [E a / RT] H ǂ = E a RT S ǂ = R Ln A R Ln ( T / h) R References 1 D. D. Perrin, W. L. F. Armarego, Purification of Laboratory Chemicals, 3rd Edition, Pergamon, New York, J. A. Elings, R. Ait Meddour, J. H. Clark, D. J. Macquarrie, Chem. Commun. 1998, a) R. Mello, A. Alcalde Aragonés, A. Olmos, M. E. González Núñez, G. Asensio J. Org. Chem. 212, 77, b) R. Mello, A. Alcalde Aragonés, M. E. González Núñez, G. Asensio J. Org. Chem. 212, 77, K. A. Connors, Chemical Kinetics. The Study of Reaction Rates in Solution. VCH, Weinheim, 199. S2

3 Figure S1 Figure S3,5,5,5,5,5,5,5,5,5, y =,442x R² =, o C y =,367x R² =,9957 y =,3349x R² =, y =,4544x R² =,99696 y =,2764x R² =, y =,2992x R² =,97512 CCl 4 2. o C Figure S2 Figure S4,5,5,5,5,5,5,5,5,5, o C y =,319x R² =, y =,93x R² =, y =,272x R² =, y =,384x R² =, y =,845x R² =,92861 y =,779x R² =, CCl 4 2. o C S3

4 Figure S5,5,5,5,5,5 Figure S7,5,5,5,5, y =,852x R² =, y =,892x R² =, o C y =,834x R² =, o C y =,1786x R² =, y =,27x R² =, y =,1911x R² =,99178 Figure S6 Figure S8,5,5,5,5,5,5,5,5,5, o C y =,3186x R² =,9955 y =,2121x R² =, y =,2685x R² =, y =,2934x R² =, y =,2256x R² =, y =,2273x R² =, o C S4

5 Figure S9,5,5,5,5, y =,258x R² =,63496 y =,275x R² =,44349 y =,29x R² =,17931 CH 3 CN 2. o C Figure S1,5,5,5,5, y =,269x R² =,81827 y =,155x R² =,59283 CH 3 CN 2. o C y =,177x R² =, Figure S11 Ln [S ]t/[ S],5,5,5,5, o C y =,35x R² =, y =,4266x R² =, y =,43x R² =, Figure S12,5,5,5,5, o C y =,119x R² =,97671 y =,657x R² =, y =,78x R² =, S5

6 Figure S13,5,5,5,5,5 Figure S15,5,5,5,5, o C y =,3646x R² =, y =,4433x R² =, y =,4547x R² =, y =,298x R² =, y =,317x R² =, o C y =,324x R² =,98227 Figure S14,5,5,5,5,5 Figure S ,5,5,5,5, o C y =,1388x R² =, y =,1679x R² =, y =,1249x R² =,99225 y =,1566x R² =, y =,1388x R² =, o C y =,1387x R² =, S6

7 Figure S17,5,5,5,5,5 Figure S19,5,5,5,5, o C y =,312x R² =, y =,273x R² =, y =,2598x R² =, o C y =,154x R² =, y =,216x R² =, y =,199x R² =,99444 Figure S18 Figure S2,5,5,5,5,5,5,5,5,5, y =,7636x R² =,99848 y =,285x R² =, y =,8159x R² =, y =,863x R² =, o C y =,35x R² =, y =,323x R² =, o C S7

8 Figure S21,5,5,5,5, o C y =,61x R² =,99379 y =,558x R² =,9951 y =,526x R² =,99571 Figure S22,5,5,5,5, y =,866x R² =, o C y =,792x R² =, y =,673x R² =, Figure S23 Figure S24 y =.65,82277x + 14, R² =,99785 HCCl 3 5, 2, 35 o C y =.86,15274x + 2, R² =,999996,32,33,34,35,36,3,32,34,36 S8

9 Figure S25 Figure S26 y =.822,875713x + 15, R² =, y =.27,964294x + 14, R² =,986689, 5, 2 o C, 5, 2 o C,32,34,36,38,4,32,34,36,38,4 Figure S27 Figure S28 y = 32,558855x 1, R² =, y =.329,3442x + 16,52756 R² =, n Hexane 2, 3, 39.6 o C n Hexane 2, 3, 39.6 o C,3,32,34,36,3,32,34,36 S9

10 S1