Magnetic Iron Oxide Nanoparticles As an Efficient and Recyclable Catalyst for the Solvent-Free

Magnetic iron oxide nanoparticles as an efficient and recyclable catalyst for the solvent-free synthesis of sulfides, vinyl sulfides, thiol esters, and thia-Michael adducts

BarahmanMovassagh,*Ali Yousefi

Department of Chemistry, K.N. Toosi University of Technology, P.O. Box 16315-1618, Tehran, Iran

E-Mail:

Supporting information

Experimental S2

General S2

Characteristic data S4

(4-Chlorophenethyl)(phenyl)sulfane (Table 2, entry 2) S6

(4-Methoxyphenethyl)(phenyl)sulfane (Table 2,entry 4) S7

Ethyl 3-(phenylthio)propanoate(Table 2,entry 7) S8

3-(Phenylthio)propanenitrile(Table 2,entry 8) S9

Phenyl(2,2-diphenylethyl)sulfane(Table 2,entry 10) S10

4-(p-Tolylthio)butan-2-one (Table 2, Entry 11) S11

(4-Methoxyphenyl)(phenethyl)sulfane(Table 2,entry 12) S12

(4-Chlorophenyl)(phenethyl)sulfane(Table 2,entry 13) S13

Phenethyl(o-tolyl)sulfane(Table 2, entry 14) S14

(4-Methoxyphenethyl)(4-chlorophenyl)sulfane(Table 2, entry 16) S15

(2-Phenylpropyl)(p-tolyl)sulfane(Table 2,entry 17) S16

(4-Chlorophenyl)(2-phenylpropyl)sulfane(Table 2,entry 18) S17

Phenyl(styryl)sulfane (Table 2, entry 24) S18

(E)-3-(Phenylthio)prop-2-en-1-ol (Table 2, entry 25) S19

Benzyl(phenyl)sulfane(Table 2,entry 26) S20

Allyl(4-chlorophenyl)sulfane(Table 2,entry 27) S21

S-4-Methoxyphenyl benzothioate(Table 2,entry 29) S22

1-(Phenylthio)butan-2-ol (Table 2, entry 31) S23

Experimental

General

All chemicals were purchased from Merck company and used as received except for Fe3O4 (magnetite) nanopowder (<50 nm particle size (TEM),98%) which was bought from Sigma-Aldrich company. Melting points were determined using Büchi B-540 apparatus. FT-IR spectra were obtained as neat or KBr pellets using an ABB Bomem model FTLA 2000 instrument. 1H NMR (300 and 500 MHz) and 13C NMR (75 and 125 MHz) spectra were recorded with Bruker AQS-300 and DRX-500 Avance spectrometers. TEM images were obtained on a Zeiss-Em10c transmission electron microscope with an accelerating voltage of 80 kV.Atomic absorption spectra (AAS) were recorded on a GBC 932 plus spectrophotometer using a flame approach. XRD data were collected on an Xpert MPD diffractometer employing Cu Kα radiation.

TEM images of Fe3O4 MNPs (a) before reaction, and (b) after five cycles of reaction between thiophenol and styrene

Powder XRD patterns of Fe3O4 MNPs: (a) before reaction, and (b) after five cycles of reaction between thiophenol and styrene.

(4-Chlorophenethyl)(phenyl)sulfane (Table 2, entry 2):Yield: 233 mg (94%), yellow oil; 1H NMR (300 MHz, CDCl3): δ 2.96 (t, J = 7.6 Hz, 2H), 3.21 (dd, J = 8.6, 6.9 Hz, 2H), 7.16-7.46 (m, 9H) ppm; 13C NMR (75 MHz, CDCl3): δ 34.9, 35.0, 126.2, 128.7, 129.1, 129.4, 130.0, 132.3, 136.2, 138.8 ppm; IR (neat) 3075, 1586, 1488, 1237 cm-1.

(4-Methoxyphenethyl)(phenyl)sulfane (Table 2, entry 4): Yield: 224 mg (92%), yellow oil; 1H NMR (500 MHz, CDCl3): δ 2.94 (t, J = 7.8 Hz, 2H), 3.21 (dd, J = 8.7, 7.5 Hz, 2H), 3.85 (s, 3H), 6.91 (d, J = 8.5 Hz, 2H), 7.18 (d, J = 8.5 Hz, 2H), 7.25 (t, J = 7.3 Hz, 1H), 7.36 (t, J = 7.5 Hz, 2H), 7.42 (d, J = 7.5 Hz, 2H) ppm; 13C NMR (125 MHz, CDCl3): δ 35.2, 35.8, 55.7, 114.4, 126.4, 129.4, 129.6, 129.9, 132.8, 136.9, 158.7 ppm; IR (neat) 3008, 1601, 1488, 1211 cm-1.

Ethyl 3-(phenylthio)propanoate (Table 2, entry 7):Yield: 206 mg (98%), colorless oil; 1H NMR (300 MHz, CDCl3): δ 1.26 (t, J = 7.1 Hz, 3H), 2.63 (t, J = 7.4 Hz, 2H), 3.18 (t, J = 7.4 Hz, 2H), 4.15 (q, J = 7.1 Hz, 2H), 7.19-7.39 (m, 5H) ppm; 13C NMR (75 MHz, CDCl3): δ = 14.2, 29.0, 34.4, 60.7, 126.5, 129.0, 130.1, 135.3, 171.8 ppm; IR (neat) 2983, 1735, 1483, 1370, 1242, 744 cm-1.

3-(Phenylthio)propanenitrile (Table 2, entry 8): Yield: 148 mg (91%), colorless oil; 1H NMR (300 MHz, CDCl3): δ 2.60 (t, J = 7.2 Hz, 2H), 3.14 (t, J = 7.2 Hz, 2H), 7.27-7.45 (m, 5H) ppm; 13C NMR (75 MHz, CDCl3): δ 18.3, 30.3, 118.0, 127.8, 129.4, 131.5, 133.3 ppm; IR (neat) 2926, 2248, 1586, 1478, 1442, 749, 697 cm-1.

Phenyl(2,2-diphenylethyl)sulfane (Table 2, entry 10):Yield: 224 mg (87%), yellow oil; 1H NMR (300 MHz, CDCl3): δ 3.81 (d, J = 7.9 Hz, 2H), 4.44 (t, J = 7.9 Hz, 1H), 7.38-7.54 (m, 15H) ppm; 13C NMR (75 MHz, CDCl3): δ 39.8, 50.8, 126.3, 126.9, 128.2, 128.8, 129.2, 129.6, 136.8, 143.3 ppm; IR (neat) 3019, 1586, 1493, 1216 cm-1.

4-(p-Tolylthio)butan-2-one (Table 2, entry 11): Yield: 182 mg (94%), colorless oil; 1H NMR (300 MHz, CDCl3): δ 2.14 (s, 3H), 2.33 (s, 3H), 2.74 (t, J = 7.3 Hz, 2H), 3.09 (t, J = 7.4 Hz, 2H), 7.11 (d, J = 9.0 Hz, 2H), 7.27 (d, J = 9.0 Hz, 2H) ppm; 13C NMR (75 MHz, CDCl3): δ 21.0, 28.2, 30.1, 43.2, 129.8, 130.5, 131.7, 136.6, 206.9 ppm; IR (neat) 2921, 1714, 1492, 1361, 1158, 806, 494 cm-1.

(4-Methoxyphenyl)(phenethyl)sulfane (Table 2, entry 12): Yield: 237 mg (97%), yellow oil; 1H NMR (500 MHz, CDCl3): δ 2.94 (dd, J = 9.1, 7.5 Hz, 2H), 3.14 (dd, J = 9.1, 7.5 Hz, 2H), 3.87 (s, 3H), 6.92 (d, J = 6.7 Hz, 2H), 7.23 (d, J = 7.2 Hz, 2H), 7.28 (t, J = 7.4 Hz, 1H), 7.35 (t, J = 7.6 Hz, 2H), 7.44 (d, J = 6.7 Hz, 2H) ppm; 13C NMR (125 MHz, CDCl3): δ 36.4, 37.7, 55.8, 115.1, 126.8, 128.9, 129.0, 133.7, 140.8, 159.4 ppm; IR (neat) 3008, 1591, 1493, 1247 cm-1.

(4-Chlorophenyl)(phenethyl)sulfane (Table 2, entry 13): Yield: 230 mg (93%), yellow oil; 1H NMR (300 MHz, CDCl3): δ 2.96 (dd, J = 9.1, 6.0 Hz, 2H), 3.18 (dd, J = 9.1, 7.3 Hz, 2H), 7.22-7.38 (m, 9H) ppm; 13C NMR (75 MHz, CDCl3): δ 35.4, 35.5, 126.6, 128.55, 128.61, 129.1, 130.5, 131.9,135.0, 139.9 ppm; IR (neat) 3013, 1606, 1478, 1216 cm-1.

Phenethyl(o-tolyl)sulfane (Table 2, entry 14): Yield: 210 mg (92%), yellow oil; 1H NMR (300 MHz, CDCl3): δ 2.49 (s, 3H), 3.04 (dd, J = 9.2, 7.2 Hz, 2H), 3.25 (dd, J = 9.2, 6.6 Hz, 2H), 7.17-7.44 (m, 9H) ppm; 13C NMR (75 MHz, CDCl3): δ 20.5, 34.3, 35.6, 125.7, 126.51, 126.54, 127.8, 128.58, 128.61, 130.2, 135.8, 137.6, 140.4 ppm; IR (neat) 3029, 1591, 1468 cm-1.

(4-Methoxyphenethyl)(4-chlorophenyl)sulfane (Table 2, entry 16):Yield: 253 mg (91%), yellow oil; 1H NMR (300 MHz, CDCl3): δ 2.90 (t, J = 7.7 Hz, 2H), 3.16 (dd, J = 9.1, 7.3 Hz, 2H), 3.83 (s, 3H), 6.89 (d, J = 8.6 Hz, 2H), 7.15 (d, J = 8.6 Hz, 2H), 7.30 (s, 4H) ppm; 13C NMR (75 MHz, CDCl3): δ 34.6, 35.6, 55.2, 113.9, 129.1, 129.5, 130.4, 131.8, 132.0, 135.2, 158.3; IR (neat) 3019, 1576, 1478, 1211 cm-1.

(2-Phenylpropyl)(p-tolyl)sulfane (Table 2, entry 17): Yield: 225 mg (93%), yellow oil; 1H NMR (300 MHz, CDCl3): δ 1.50 (d, J = 6.6 Hz, 2H), 2.42 (s,3H), 3.02-3.16 (m, 2H), 3.30 (dd, J = 11.9, 5.8 Hz, 1H), 7.19 (d, J = 8.3 Hz, 2H), 7.27-7.44 (m, 7H) ppm; 13C NMR (75 MHz, CDCl3): δ 21.05, 21.11, 39.5, 42.8, 126.6, 127.1, 128.6, 129.8, 130.0, 133.1, 136.0, 145.7 ppm; IR (neat) 3024, 1611, 1504 cm-1.

(4-Chlorophenyl)(2-phenylpropyl)sulfane (Table 2, entry 18):Yield: 228 mg (87%), yellow oil; 1H NMR (300 MHz, CDCl3): δ 1.41 (d, J = 6.7 Hz, 3H), 2.92-3.10 (m, 2H), 3.21 (dd, J = 12.4, 6.4 Hz, 1H), 7.20-7.37 (m, 9H) ppm; 13C NMR (75 MHz, CDCl3): δ 21.1, 39.5, 42.3, 126.7, 126.9, 128.6, 129.0, 130.5, 131.8, 135.4, 145.2 ppm; IR (neat) 3013, 1591, 1493 cm-1.

Phenyl(styryl)sulfane (Table 2, entry 24):Yield: 208 mg (98%); Light yellow oil; (E)-isomer: 1H NMR (300 MHz, CDCl3): δ 6.78 (d, J = 15.4 Hz, 1H), 6.94 (d, J = 15.4 Hz, 1H), 7.27-7.51 (m, 10H) ppm; 13C NMR (75 MHz, CDCl3): δ 123.4, 126.1, 127.0, 127.7, 128.8, 129.2, 129.9, 131.9, 135.3, 136.6 ppm; IR (KBr) 3058, 1599, 1582, 1477, 945cm-1.

(E)-3-(Phenylthio)prop-2-en-1-ol (Table 2, entry 25):Yield: 151mg (91%), Light yellow oil; (E)-isomer: 1H NMR (300 MHz, CDCl3): δ 2.23 (br s, 1H), 4.12 (dd, J = 6.2, 1.2 Hz, 2H), 5.92 (dt, J = 15.6, 6.2 Hz, 1H), 6.68 (dt, J = 15.6, 1.2 Hz, 1H), 7.19-7.42 (m, 5H) ppm; 13C NMR (75 MHz, CDCl3): δ 62.5, 126.5, 127.9, 129.2, 129.7, 133.1, 135.2 ppm; IR (KBr) 3436, 3061, 1582, 1474, 740 cm-1.

Benzyl(phenyl)sulfane (Table 2, entry 26): Yield: 168 mg (84%), colorless crystals;mp 42-43 °C; 1H NMR (300 MHz, CDCl3): δ 4.17 (s, 2H), 7.22-7.38 (m, 10 H) ppm; 13C NMR (75 MHz, CDCl3): δ 39.0, 126.3, 127.2, 128.5, 128.9, 129.8, 136.4, 137.5 ppm; IR (KBr) 1447, 1360, 1185, 1047, 846 cm-1.

Allyl(4-chlorophenyl)sulfane (Table 2, entry 27):Yield: 173 mg (94%), light yellow oil; 1H NMR (500 MHz, CDCl3): δ 3.46 (d, J = 6.6 Hz, 2H), 5.01 (d, J = 10.1 Hz, 1H), 5.05 (d, J = 16.5 Hz, 1H), 5.75-5.83 (m, 1H), 7.19 (d, J = 9.1 Hz, 2H), 7.21 (d, J = 9.1 Hz, 2H) ppm; 13C NMR (125 MHz, CDCl3): δ 37.9, 118.4, 129.3, 131.8, 132.7, 133.7, 134.8 ppm; IR (neat) 1642, 1483, 1386, 1221, 1103, 1005, 923, 810 cm-1.

S-4-Methoxyphenyl benzothioate (Table 2, entry 29):Yield: 224 mg (92%), colorless crystals; mp 89-91°C; 1H NMR (300 MHz, CDCl3): δ 3.87 (s, 3H), 7.01 (d, J = 8.7 Hz, 2H), 7.44(d, J = 8.7 Hz, 2H), 7.5 (t, J = 7.3 Hz, 2H), 7.62 (t, J = 7.3 Hz, 1H), 8.05 (d, J = 7.2 Hz, 2H) ppm; 13C NMR (75 MHz, CDCl3): δ 55.4, 114.9, 117.9, 127.5, 128.7, 133.6, 136.7, 160.8, 191.1 ppm; IR (KBr) 2966, 2835, 1668, 1488, 1257, 1170, 903, 687 cm-1.

1-(Phenylthio)butan-2-ol (Table 2, entry 31): Yield: 167 mg (92%), light yellow oil; IR (neat): =3410, 1584, 1471, 1021, 740, 690 cm-1; 1H NMR (300 MHz, CDCl3): δ=0.98 (t, J = 7.4 Hz, 3H), 1.53-1.64(m, 2H), 2.64(br s, 1H), 2.86 (dd, J = 13.6, 8.6 Hz, 1H), 3.18 (dd, J = 13.6, 3.5 Hz, 1H), 3.59-3.67 (m, 1H), 7.21-7.42 (m, 5H) ppm; 13C NMR (75 MHz, CDCl3): δ = 9.9, 28.9, 41.7, 70.6, 126.5, 129.1, 129.9, 135.4 ppm.

1S