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Supporting Information

Poly(N-vinylpyrrolidone)-Hydrogen Peroxide and Poly(4-

vinylpyridine)-Hydrogen Peroxide Complexes: Solid Hydrogen

Peroxide Equivalents for Selective Oxidation of Sulfides to

Sulfoxides and Ketones to gem-Dihydroperoxides

G. K. Surya Prakash,*

a Anton Shakhmin,

a Kevin G. Glinton,

a Sneha Rao,

a Thomas Mathew*

a

and George A. Olaha

aLoker Hydrocarbon Research Institute and the Department of Chenistry, University of Southern

California, Los Angeles, CA 90089, USA.

gprakash@usc.edu, tmathew@usc.edu

Table of Contents

General remarks S2

General Procedures S2-S4

1H, and

13C NMR Spectral data of sulfoxides S5-S7

1H and

13C NMR Spectral data of gem-dihydroperoxides S7-S9

References S10

Representative 1

H, and 13

C NMR Spectra of sulfoxides S11-S20

Representative 1

H and 13

C NMR Spectra of gem-dihydroperoxides S21-S30

Electronic Supplementary Material (ESI) for Green Chemistry.This journal is © The Royal Society of Chemistry 2014

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Experimental Part

General Remarks

Unless otherwise mentioned, all chemicals were purchased from commercial sources and

used as received. Poly(N-vinylpyrolidone)-hydrogen peroxide and poly(4-vinylpyridine)

hydrogen peroxide were both prepared from previously described procedures.1 Products were

identified by the analysis of 1H,

13C, and

19F NMR spectra recorded on a 400 MHz Varian NMR

spectrometer. 1HNMR chemical shifts were determined relative to TMS as the internal standard

at δ 0.0 ppm. 13

C NMR chemical shifts were determined relative to CDCl3 at δ 77.0 ppm.

Column chromatography, when necessary, was carried out using Siliaflash G60 silica gel (70-

230 mesh). HRMS analysis for 6h-j was carried out at the Mass Spectrometry Facility,

University of Arizona, Tucson, AZ.

As with all peroxides, the peroxide complexes and gem-dihydroperoxide products must

be handled with extreme caution and stored between 0-5 °C. Although we found gem-

dihydroperoxide products stable, such compounds are known to be shock sensitive and to

decompose violently upon heating. As such, they must be kept away from direct heat sources,

transition metal salts, mechanical shocks and strong light sources. Both the complexes can be

stored in the refrigerator for years without losing its activity.

Preparation of PVD-H2O2 and PVP-H2O2 Complexes1

Cross-linked poly(N-vinylpyrrolidone) (PVD) was slowly added in portions to a 50%

H2O2 (34 g, 0.5 mol) aqueous solution in a Nalgene container with vigorous shaking and

efficient cooling using a dry ice-acetone bath (caution! exothermic). The morphology of the

polymer complex changed during the course of the addition and formed a fine wet powder until

the ratio of PVD monomer to H2O2 went up to 1:4.5. The complex was kept under cool (-20 oC)

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and dry conditions. The PVP-H2O2 complex was also prepared in a similar way using 2% cross-

linked poly(4-vinylpyridine) and 50%H2O2 (1:3.5 molar ratio).

Preparation of PVP:H2SO4 (1:5) complex

Concentrated sulfuric acid (0.5 mol) was taken in a 500 mL Nalgene bottle, cooled to -78

°C and poly(4-vinyl pyridine) 2% cross-linked (10.5 g, 0.1 mol based on monomer) was

gradually added in small portions to the cold acid with constant stirring. After complete addition,

the temperature was slowly brought to room temperature with stirring and swirling until a fluffy

free-flowing solid was obtained (since the complex formation is exothermic, cool intermittently

to avoid overheating). The mixture was finally capped and stored in the refrigerator for further

use.

General Procedure for the Oxidation of Sulfides to Sulfoxides: In the case of

benzylphenylsulfide, 2 mmol (0.400 g) of the substrate was first added to a pressure tube and

supplemented with 1 mL of acetonitrile. Following this, 0.5 g of PVD:H2O2 (1:4.5) was then

added to the mixture along with an additional 2 mL of acetonitrile. The tube was then capped and

heated, with stirring, to 70 °C. The reaction’s progress was followed by thin layer

chromatography (30% hexanes: 70% ethyl acetate) and, upon completion, 30 mL of

dichloromethane was added and filtered. The residue was then dried over anhydrous sodium

sulfate and concentrated under vacuum. The resultant product was then purified by column

chromatography to remove any residual starting material using a 7:3 mixture of ethyl acetate and

hexanes and finally confirmed as benzylphenylsulfoxide by comparing the spectral data with

those of the authentic sample.2-6

General Procedure for the Oxidation of Ketones to gem-Dihydroperoxides: For cyclohexanone,

2 mmol (0.196 g) was added to a vial (8 dr, ~ 30 mL) and then dissolved in 1 mL of THF. To this

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was added 0.2 g of PVP:H2SO4 (1:5) and another 1 mL of THF after which the solution was

placed in an ice bath and stirred. After approximately 5 min, 0.5 g of PVD:H2O2 (1:4.5) was

added to the tube along with 1 mL of THF. The tube was then capped and allowed to stir in the

ice bath for a further 5 min. The mixture was then allowed to come to room temperature and

stirring was continued for 24 h. Progress of the reaction was monitored by TLC (3:7, ethylacetate

and hexanes). Upon completion, the reaction mixture was diluted with 60 mL of

dichloromethane and filtered. The filtrate was then washed with 30 mL of saturated sodium

bicarbonate solution, 30 mL of brine solution followed by 30 mL of distilled water. The organic

layer was dried over anhydrous sodium sulfate, concentrated under vacuum and the residue was

then purified by column chromatography (3:7 mixture of ethyl acetate and hexanes). The product

was identified by using NMR spectroscopy as 1,1-Dihydroperoxycyclohenxane. All products

(except 6h-j) were known and were characterized by comparing their spectral data with those of

the known authentic samples.7-12

Compounds 6h-j were extremely unstable under the conditions

of HRMS analysis and only molecular ions that lost water and oxygen molecules were detected.

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1H, and

13C NMR Spectral data of sulfoxides

1-(Methylsulfinyl)benzene (4a)2,3

O

S

1H NMR (400 MHz, CDCl3): δ 7.59 – 7.50 (m, 2H), 7.45 – 7.36 (m, 3H), 2.61 (s, 3H).

13C NMR

(101 MHz, CDCl3): δ 145.41, 130.80, 129.12, 123.24, 43.68.

1-(Ethylsulfinyl)benzene (4b)2

O

S

1H NMR (400 MHz, CDCl3): δ 7.65 – 7.59 (m, 2H), 7.56 – 7.47 (m, 3H), 2.98 – 2.70 (m, 2H),

1.20 (t, J = 7.4 Hz, 3H). 13

C NMR (101 MHz, CDCl3): δ 143.31, 131.02, 129.23, 124.25, 50.37,

6.07.

1-Methyl-4-(methylsulfinyl)benzene (4c)2

O

S

1H NMR (400 MHz, CDCl3): δ 7.56 – 7.52 (m, 2H), 7.35 – 7.30 (m, 2H), 2.70 (s, 3H), 2.41 (s,

3H). 13

C NMR (101 MHz, CDCl3): δ 142.37, 141.35, 129.90, 123.40, 43.86, 21.27.

4-(Methylsulfinyl)benzenamine (4d)2

O

S

H2N

1H NMR (400 MHz, CDCl3): δ 7.41 (d, J = 8.7 Hz, 2H), 6.72 (d, J = 8.7 Hz, 2H), 2.67 (s, 3H).

13C NMR (101 MHz, CDCl3): δ 150.13, 132.00, 125.67, 114.86, 43.37.

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1-methoxy-4-(methylsulfinyl)benzene (4e)2

O

S

H3CO

1H NMR (400 MHz, CDCl3): δ 7.59 (d, J = 9.0 Hz, 2H), 7.03 (d, J = 8.9 Hz, 2H), 3.84 (s, 3H),

2.70 (s, 3H). 13

C NMR (101 MHz, CDCl3): δ 161.44, 136.08, 124.94, 114.35, 55.03, 43.47.

1-Chloro-4-(methylsulfinyl)benzene (4f)4

S

O

Cl

1H NMR (400 MHz, CDCl3): δ 7.53 – 7.49 (m, 2H), 7.43 – 7.39 (m, 2H), 2.64 (d, J = 1.7 Hz,

3H). 13

C NMR (101 MHz, CDCl3): δ 143.23, 136.10, 128.58, 123.97, 42.97.

1-Bromo-4-(methylsulfinyl)benzene (4g)2

S

O

Br

1H NMR (400 MHz, CDCl3): δ 7.67 (d, J = 8.7 Hz, 2H), 7.53 (d, J = 8.7 Hz, 2H), 2.73 (s, 3H).

13C NMR (101 MHz, CDCl3): δ 144.79, 132.48, 125.35, 125.10, 43.92.

1-((Phenylsulfinyl)methyl)benzene (4h)5

S

O

1H NMR (400 MHz, CDCl3): δ 7.50 – 7.35 (m, 5H), 7.32 – 7.21 (m, 3H), 7.01 – 6.96 (m, 2H),

4.04 (dd, J = 39.1, 12.6 Hz, 2H). 13

C NMR (101 MHz, CDCl3): δ 142.91, 131.27, 130.47,

129.25, 128.96, 128.56, 128.36, 124.55, 63.72.

S7

1-(Allylsulfinyl)benzene (4i)6

S

O

1H NMR (400 MHz, CDCl3): δ 7.62 – 7.58 (m, 2H), 7.54 – 7.47 (m, 3H), 5.74 – 5.54 (m, 1H),

5.34 – 5.30 (m, 1H), 5.19 (dq, J = 17.0, 1.3 Hz, 1H), 3.54 (dtd, J = 20.3, 12.6, 7.3 Hz, 2H). 13

C

NMR (101 MHz, CDCl3): δ 142.48, 130.82, 128.76, 124.93, 124.01, 123.60, 60.41.

1-(2-Chloroethylsulfinyl)benzene (4j)2

S

O

Cl

1H NMR (400 MHz, CDCl3): δ 7.68 – 7.61 (m, 2H), 7.58 – 7.49 (m, 3H), 3.96 (dt, J = 11.6, 7.5

Hz, 1H), 3.66 (ddd, J = 11.7, 6.7, 5.6 Hz, 1H), 3.24 – 3.11 (m, 2H). 13

C NMR (101 MHz,

CDCl3): δ 142.58, 131.31, 129.37, 123.74, 59.13, 36.64.

1H and

13C NMR Spectral data of gem-dihydroperoxides

1,1-Dihydroperoxycyclopentane (6a)7, 11

OOH

OOH

1H NMR (400 MHz, D2O): δ 9.67 (s, 2H), 2.03 – 1.96 (m, 4H), 1.79 – 1.71 (m, 4H).

13C NMR

(101 MHz, D2O): δ 122.66, 33.25, 24.71.

1,1-Dihydroperoxycyclohexane (6b)7, 8, 9, 11

OOH

OOH

1H NMR (400 MHz, D2O): δ 9.28 (s, 2H), 1.89 – 1.80 (m, 4H), 1.64 – 1.53 (m, 4H), 1.51 – 1.40

(m, 2H) 13

C NMR (101 MHz, D2O): δ 111.27, 29.59, 25.36, 22.50.

1,1-Dihydroperoxy-4-methylcyclohexane (6c)7, 8, 9, 11, 12

OOH

OOH

S8

1H NMR (400 MHz, D2O): δ 9.31 (s, 2H), 2.28 – 2.16 (m, 2H), 1.69 – 1.59 (m, 2H), 1.56 – 1.41

(m, 3H), 1.31 – 1.13 (m, 2H), 0.93 (d, J = 6.5 Hz, 3H). 13

C NMR (101 MHz, D2O): δ 111.00,

31.75, 30.73, 29.19, 21.56.

4-tert-Butyl-1,1-dihydroperoxycyclohexane (6d)7, 8, 9, 11

OOH

OOH

1H NMR (400 MHz, D2O): δ 9.35 (s, 2H), 2.30 (br. d, J = 12.1 Hz, 2H), 1.72 (br. d, J = 13.2 Hz,

2H), 1.45 (td, J = 13.7, 4.1 Hz, 2H), 1.33 – 1.19 (m, 2H), 1.11 – 1.00 (m, 1H), 0.87 (s, 9H). 13

C

NMR (101 MHz, D2O): δ 110.96, 47.52, 32.43, 29.85, 27.72, 23.46.

1,1-Dihydroperoxycycloheptane (6e)7, 10, 11, 12

OOH

OOH

1H NMR (400 MHz, CDCl3): δ 9.56 (s, 2H), 1.97 – 1.89 (m, 4H), 1.59 – 1.47 (m, 8H).

13C NMR

(101 MHz, CDCl3): δ 116.26, 32.99, 29.83, 22.75.

2,2-Dihydroperoxyadamantane (6f)7, 8, 9, 11, 12

OOH

OOH

1H NMR (400 MHz, CDCl3): δ 8.28 (s, 2H), 2.34 – 2.26 (m, 2H), 1.98 – 1.86 (m, 4H), 1.85 –

1.72 (m, 2H), 1.69 – 1.57 (m, 6H). 13

C NMR (101 MHz, CDCl3): δ 112.67, 36.98, 33.69, 31.12,

26.95.

2,2-Dihydroperoxyhexane (6g) 7, 10, 11

OOHHOO

1H NMR (400 MHz, CDCl3): δ 9.45 (s, 2H), 1.78 – 1.71 (m, 2H), 1.44 (s, 3H), 1.43 – 1.29 (m,

4H), 0.92 (t, J = 7.1 Hz, 3H). 13

C NMR (101 MHz, CDCl3): δ 112.77, 32.70, 26.02, 22.81, 17.84,

13.92.

2,2-Dihydroperoxy-1,3-diphenylpropane (6h)

OOHHOO

PhPh

S9

1H NMR (400MHz, CD3CN): δ 9.50 (s, 2H), 7.43 – 7.19 (m, 10H), 2.89 (s, 4H).

13C NMR (100

MHz, CD3CN): δ 135.58, 130.95, 128.22, 126.83, 112.34, 35.86. HRMS (EI): Found [M+-H2O-

O2] = 210.2687

2,2-Dihydroperoxybicyclo[3.2.1]octane (6i)

OOHHOO

1H NMR (400 MHz, CDCl3): δ 8.86 (s, 1H), 8.79 (s, 1H), 2.55 – 2.47 (m, 1H), 2.20 – 2.11 (m,

1H), 1.96 – 1.32 (m, 10H). 13

C NMR (100 MHz, CDCl3): δ 113.69, 38.21, 34.61, 33.82, 29.05,

27.61, 25.85, 24.18. HRMS (EI): Found [M+-H2O-O2] = 124.0892

8,8-Dihydroperoxytricyclo[5.2.1.02,6

]decane (6j)

OOH

OOH

1H NMR (400 MHz, CDCl3): δ 8.92 (s, 1H), 8.75 (s, 1H), 2.25 (s, 1H), 2.03 – 1.76 (m, 6H), 1.68

– 1.56 (m, 1H), 1.48 – 1.36 (m, 2H), 1.30 – 0.78 (m, 4H). 13

C NMR (100 MHz, CDCl3): δ

119.91, 47.01, 46.71, 40.38, 40.21, 38.85, 32.31, 31.52, 31.33, 27.41. HRMS (EI): Found [M+-

H2O-O2] = 150.2215

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References

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G. A. Olah, Adv. Synth. Catal., 2009, 351, 1567-1574.

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2008, 284, 116-119.

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Representative 1

H, and 13

C NMR Spectra of sulfoxides

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S13

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S15

S16

S17

S18

S19

S20

S21

Representative 1

H and 13

C NMR Spectra of gem-dihydroperoxides

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S23

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S26

S27

S28

S29

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