Acid-induced chemoselective arylthiolations sodium ... · Chemical Engineering College, Nanjing...

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Acid-induced chemoselective arylthiolations of electron-rich arenes in ionic liquids from sodium arylsulfinates: The reducibility of

halide anions in [Hmim]Br

Zhu-bing Xu, Guo-ping Lu*, Chun Cai

Chemical Engineering College, Nanjing University of Science and Technology, Xiaolingwei 200, Nanjing, 210094, China

* Corresponding Author E-mail: [email protected]

1. Characterization data ........................................................................2

2. NMR Spectra of All Products ............................................................................12

1. Characterization data

Electronic Supplementary Material (ESI) for Organic & Biomolecular Chemistry.This journal is © The Royal Society of Chemistry 2017

mailto:[email protected]

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OHS

Chemical Formula: C16H12OSMass: 252

1-(Phenylthio)naphthalen-2-ol 3a.1 Yellow solid, mp 63-65 °C (lit. 65-67 °C), yield 86%, 108.4 mg. 1H NMR (500 MHz, CDCl3) δ 8.18 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 9.0 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.45 (t, J = 7.5 Hz, 1H), 7.29-7.33 (m, 2H), 7.10-7.15 (m, 3H), 7.05 (t, J = 7.0 Hz, 1H), 6.98 (d, J = 7.5 Hz, 2H). 13C NMR (125 MHz, CDCl3) δ 157.2, 135.6, 135.6, 133.0, 129.7, 129.4, 128.8, 128.1, 126.6, 126.1, 124.9, 124.1, 117.1, 108.3. GC-MS (EI) m/z: 252.

SOH


1-(p-Tolylthio)naphthalen-2-ol 3b.1 Yellow solid, mp 78-80 °C (lit. 77-79 °C), yield 90%, 119.7 mg. 1H NMR (500 MHz, CDCl3) δ 8.20 (d, J = 8.5 Hz, 1H), 7.83 (d, J = 8.9 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.43-7.46 (m, 1H), 7.29-7.33. (m, 2H), 7.20 (s, 1H), 6.90-6.94 (m, 4H), 2.19 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 157.0, 136.0, 135.6, 132.8, 131.9, 130.1, 129.6, 128.7, 128.0, 126.8, 124.9, 124.0, 117.0, 108.8, 21.0. GC-MS (EI) m/z: 266.

OHS


1-(o-Tolylthio)naphthalen-2-ol 3c.1 Yellow solid, mp 63-65 °C (lit. 65-67 °C), yield 88%, 117.0 mg. 1H NMR (500 MHz, CDCl3) δ 8.07 (d, J = 8.4 Hz, 1H), 7.86 (d, J = 8.9 Hz, 1H), 7.77 (d, J = 8.0 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.29-7.33 (m, 2H), 7.13 (d, J = 7.4 Hz, 1H), 7.03 (s, 1H), 6.95 (t, J = 7.4 Hz, 1H), 6.80 (d, J = 7.5 Hz, 1H), 6.32 (d, J = 7.8 Hz, 1H), 2.53 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 156.2, 134.6, 134.2, 133.4, 131.9, 129.4, 128.6, 127.7, 127.0, 125.8, 124.5, 123.8, 123.0, 116.0, 106.4, 19.2. GC-MS (EI) m/z: 266.

OHS

O

Chemical Formula: C17H14O2SMass: 282

1-((4-Methoxyphenyl)thio)naphthalen-2-ol 3d.1 Yellow solid, mp 69-71 °C (lit. 68-70 °C), yield 89%, 125.5 mg. 1H NMR (500 MHz, CDCl3) δ 8.22 (d, J = 8.5 Hz, 1H), 7.81 (d, J = 8.9 Hz, 1H), 7.73 (d, J = 8.1 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H), 7.27-7.32 (m, 3H), 6.99 (d, J = 9.0 Hz, 2H), 6.66 (d, J = 8.0 Hz, 2H), 3.63 (s, 3H). 13C NMR

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(125 MHz, CDCl3) δ 158.6, 156.9, 135.6, 132.7, 129.7, 129.0, 128.8, 128.0, 126.1, 125.0, 124.0, 117.1, 115.1, 110.0, 55.4. GC-MS (EI) m/z: 282.

OHS

F

Chemical Formula: C16H11FOSMass: 270

1-((4-Fluorophenyl)thio)naphthalen-2-ol 3e.2 Light yellow solid, mp 113-115 °C, yield 94%, 126.9 mg. 1H NMR (500 MHz, CDCl3) δ 8.13 (d, J = 8.5 Hz, 1H), 7.83 (d, J = 8.9 Hz, 1H), 7.74 (d, J = 8.5, 1H), 7.44 (t, J = 7.5 Hz, 1H), 7.26-7.32 (m, 2H), 7.12 (s, 1H), 6.93-6.96 (m, 2H), 6.79-6.83 (m, 2H). 13C NMR (125 MHz, CDCl3) δ 161.6 (d, J = 245.0 Hz, 1C), 157.1, 135.4, 133.1, 130.5, 129.7, 128.7 (d, J = 30.0 Hz, 1C), 128.5, 128.2, 124.7, 124.1, 117.0, 116.5 (d, J = 22.5 Hz, 1C), 108.7. GC-MS (EI) m/z: 270.

OHS

Cl

Chemical Formula: C16H11ClOSMass: 286

1-((4-Chlorophenyl)thio)naphthalen-2-ol 3f.1 Yellow solid, mp 83-86 °C (lit. 85-87 °C), yield 90%, 128.7 mg. 1H NMR (500 MHz, CDCl3) δ 8.19 (d, J = 8.4 Hz, 1H), 7.93 (d, J = 8.9 Hz, 1H), 7.84 (d, J = 8.1 Hz, 1H), 7.52 (ddd, J = 8.4, 6.9, 1.2 Hz, 1H), 7.43 – 7.34 (m, 2H), 7.18 – 7.11 (m, 3H), 6.99 – 6.93 (m, 2H). 13C NMR (125 MHz, CDCl3) 157.2, 135.3, 134.1, 133.3, 132.0, 130.0, 129.7, 129.4, 128.8, 128.3, 127.8, 124.6, 124.2, 117.1, 107.8. GC-MS (EI) m/z: 286.

OHS

Br

Chemical Formula: C16H11BrOSMass: 330

1-((4-bromophenyl)thio)naphthalen-2-ol 3g.1 Yellow solid, mp 106-108 °C (lit. 103-105 °C), yield 80%, 132.0 mg. 1H NMR (500 MHz, CDCl3) δ 8.07 (d, J = 8.5 Hz, 1H), 7.84 (d, J = 8.9 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.25-7.32 (m, 2H), 7.18 -7.21 (m, 2H), 7.01 (s, 1H), 6.80 (d, J = 8.5 Hz, 2H). 13C NMR (125 MHz, CDCl3) δ 157.2, 135.3, 134.8, 133.3, 132.3, 129.7, 128.8, 128.3, 128.0, 124.6, 124.1, 119.8, 117.1, 107.6. GC-MS (EI) m/z: 330.

OH

S Chemical Formula: C19H18OSMass: 294

Elemental Analysis: C, 77.51; H, 6.16; O, 5.43; S, 10.89

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1-(Mesitylthio)naphthalen-2-ol 3h. Yellow solid, mp 105-107 °C, yield 86%, 126.4 mg. 1H NMR (500 MHz, CDCl3) δ 8.04 (d, J = 8.5 Hz, 1H), 7.76 (d, J = 8.8 Hz, 2H), 7.44 (t, J = 7.7 Hz, 1H), 7.33 (t, J = 7.5 Hz, 1H), 7.22 (d, J = 8.9 Hz, 1H), 6.89 (s, 2H), 6.81 (s, 1H), 2.36 (s, 6H), 2.25 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 155.3, 140.7, 137.9, 134.7, 130.9, 129.7, 128.7, 127.3, 124.5, 123.6, 117.1, 111.5, 21.8, 21.0. GC-MS (EI) m/z: 294. Anal. Calcd for C19H18OS: C, 77.51%; H, 6.16%. Found: C, 77.17%; H, 6.52%.

OS Chemical Formula: C17H14OS

Mass: 266

(2-Methoxynaphthalen-1-yl)(phenyl)sulfane 3i.2 White solid, mp 77-80 °C (lit. 79-80 °C), yield 97%, 129.0 mg. 1H NMR (500 MHz, CDCl3) δ 8.48 (d, J = 8.6 Hz, 1H), 7.98 (d, J = 9.0 Hz, 1H), 7.84 (d, J = 8.1 Hz, 1H), 7.51 (ddd, J = 8.4, 6.8, 1.3 Hz, 1H), 7.43 – 7.36 (m, 2H), 7.14 (t, J = 7.7 Hz, 2H), 7.08 – 7.00 (m, 3H), 3.97 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.4, 138.3, 136.4, 132.2, 129.7, 128.8, 128.4, 127.9, 126.4, 125.6, 124.9, 124.3, 113.6, 113.1, 57.1. GC-MS (EI) m/z: 266.


Mass: 280

(2-Methoxynaphthalen-1-yl)(p-tolyl)sulfane 3j.1 Yellow solid, mp 58-61 °C (lit. 57-59 °C), yield 91%, 127.4 mg. 1H NMR (500 MHz, CDCl3) δ 8.40 (d, J = 8.5 Hz, 1H), 7.88 (d, J = 9.0 Hz, 1H), 7.74 (d, J = 8.0 Hz, 1H), 7.42 (t, J = 7.5 Hz, 1H), 7.27-7.32 (m, 2H), 6.86 (br, s, 4H), 3.89 (s, 3H), 2.15 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.3, 136.4, 134.7, 134.7, 132.0, 129.6, 128.4, 127.8, 126.8, 125.7, 124.2, 113.8, 113.6, 57.1, 21.0. GC-MS (EI) m/z: 280.


Mass: 280Elemental Analysis: C, 77.11; H, 5.75; O, 5.71; S, 11.44

(2-Methoxynaphthalen-1-yl)(o-tolyl)sulfane 3k. Light yellow solid, mp 126-127 °C, yield 95%, 133.0 mg. 1H NMR (500 MHz, CDCl3) δ 8.38 (d, J = 8.6 Hz, 1H), 7.99 (d, J = 9.0 Hz, 1H), 7.84 (d, J = 8.0 Hz, 1H), 7.48 (t, J = 7.6 Hz, 1H), 7.39 (dd, J = 8.2, 4.0 Hz, 2H), 7.15 (d, J = 7.4 Hz, 1H), 6.96 (t, J = 7.4 Hz, 1H), 6.82 (t, J = 7.6 Hz, 1H), 6.41 (d, J = 7.9 Hz, 1H), 3.96 (s, 3H), 2.57 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.62, 137.3, 136.4, 135.0, 132.1, 130.0, 129.8, 128.4, 127.8, 126.3, 125.6, 125.4, 124.5, 124.3, 113.6, 112.9, 57.1, 20.3. GC-MS (EI) m/z: 280. Anal. Calcd for C18H16OS: C, 77.11%; H, 5.75%. Found: C, 76.98%; H, 6.07%.

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OS

O


2-Methoxy-1-(4-methoxyphenylsulfanyl)naphthalene 3l.3 White solid, mp 81-82 °C (lit. 80–82 °C), yield 97%, 143.6 mg. 1H NMR (500 MHz, CDCl3) δ 8.6 (d, J = 8.6 Hz, 1H), 7.9 (d, J = 9.0 Hz, 1H), 7.8 (d, J = 8.1 Hz, 1H), 7.6 – 7.5 (m, 1H), 7.4 (t, J = 7.5 Hz, 1H), 7.3 (d, J = 9.0 Hz, 1H), 7.1 – 7.1 (m, 2H), 6.8 – 6.7 (m, 2H), 4.0 (s, 3H), 3.7 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.1, 157.9, 136.3, 131.8, 129.7, 129.3, 128.9, 128.4, 127.7, 125.7, 124.2, 115.0, 114.6, 113.7, 57.1, 55.4. GC-MS (EI) m/z: 296.

OS

F

Chemical Formula: C17H13FOSMass: 284

Elemental Analysis: C, 71.81; H, 4.61; F, 6.68; O, 5.63; S, 11.28

(4-Fluorophenyl)(2-methoxynaphthalen-1-yl)sulfane 3m. Light yellow oil, yield 94%, 133.5 mg. 1H NMR (500 MHz, CDCl3) δ 8.48 (dd, J = 8.6, 1.0 Hz, 1H), 7.97 (d, J = 9.0 Hz, 1H), 7.86 – 7.80 (m, 1H), 7.52 (ddd, J = 8.4, 6.8, 1.3 Hz, 1H), 7.43 – 7.33 (m, 2H), 7.07 – 7.01 (m, 2H), 6.89 – 6.81 (m, 2H), 3.97 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 162.0, 160.1, 159.3, 136.2, 133.2, 132.2, 129.7, 128.7, 128.7, 128.5, 127.9, 125.4, 124.3, 116.0, 115.8, 113.9, 113.6, 57.0. GC-MS (EI) m/z: 284. Anal. Calcd for C17H13FOS: C, 71.81%; H, 4.61%. Found: C, 71.56%; H, 4.83%.

OS

Br

Chemical Formula: C17H13BrOSMass: 344

(4-Bromophenyl)(2-methoxynaphthalen-1-yl)sulfane 3n.4 White solid, mp 113-114 °C, yield 87%, 149.6 mg. 1H NMR (500 MHz, CDCl3) δ 8.32 (d, J = 8.5 Hz, 1H), 7.91 (d, J = 9.0 Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.43 (t, J = 7.5 Hz, 1H), 7.34 – 7.27 (m, 2H), 7.15 (d, J = 8.6 Hz, 2H), 6.79 (d, J = 8.6 Hz, 2H), 3.89 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.4, 137.6, 136.2, 132.5, 132.3, 131.8, 128.5, 128.3, 128.0, 125.3, 124.4, 118.4, 113.5, 112.5, 57.0. GC-MS (EI) m/z: 344.

O O

S

O



(2,4-Dimethoxy-6-methylphenyl)(4-methoxyphenyl)sulfane 3o. Light yellow solid, mp 102-103 °C, yield 86%, 124.7 mg. 1H NMR (500 MHz, CDCl3) δ 6.99 (d, J = 8.8

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Hz, 2H), 6.74 (d, J = 8.7 Hz, 2H), 6.49 (d, J = 2.5 Hz, 1H), 6.40 (d, J = 2.6 Hz, 1H), 3.84 – 3.78 (m, 6H), 3.73 (d, J = 1.3 Hz, 3H), 2.43 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 161.9, 161.4, 157.6, 146.0, 129.4, 128.2, 114.6, 112.0, 107.4, 96.9, 56.3, 55.4, 21.9. GC-MS (EI) m/z: 290. Anal. Calcd for C16H18O3S: C, 66.18%; H, 6.25%. Found: C, 66.47%; H, 5.95%.

O O

S

O



2,4-(Dimethoxyphenyl)(4-methoxyphenyl)sulfane 3p.5 Light yellow oil, yield 86%, 118.7 mg. 1H NMR (500 MHz, CDCl3) δ 7.29 – 7.23 (m, 2H), 7.08 (d, J = 8.5 Hz, 1H), 6.87 – 6.80 (m, 2H), 6.49 (d, J = 2.5 Hz, 1H), 6.43 (dd, J = 8.5, 2.5 Hz, 1H), 3.83 (s, 3H), 3.79 (d, J = 4.5 Hz, 6H). 13C NMR (125 MHz, CDCl3) δ 160.8, 159.0, 158.9, 133.5, 132.8, 126.4, 115.9, 114.8, 105.4, 99.2, 56.0, 55.6, 55.5. GC-MS (EI) m/z: 276. Anal. Calcd for C15H16O3S: C, 65.19%; H, 5.84%. Found: C, 65.42%; H, 6.18%.

O O

S

O



(2,4-Diethoxyphenyl)(4-methoxyphenyl)sulfane 3q. Light yellow oil, yield 91%, 138.3 mg. 1H NMR (500 MHz, CDCl3) δ 7.3 (d, J = 8.8 Hz, 2H), 7.1 (d, J = 8.5 Hz, 1H), 6.8 (d, J = 8.8 Hz, 2H), 6.5 (d, J = 2.5 Hz, 1H), 6.4 (dd, J = 8.5, 2.5 Hz, 1H), 4.0 (dq, J = 14.1, 7.0 Hz, 4H), 3.8 (s, 3H), 1.4 (dt, J = 21.2, 6.9 Hz, 6H). 13C NMR (125 MHz, CDCl3) δ 160.0, 159.0, 158.2, 133.2, 133.0, 126.6, 116.3, 114.7, 105.8, 100.7, 64.4, 63.8, 55.4, 14.9, 14.7. GC-MS (EI) m/z: 304. Anal. Calcd for C17H20O3S: C, 67.08%; H, 6.62%. Found: C, 66.91%; H, 6.87%.

OO O

SChemical Formula: C16H18O3S

Mass: 290

p-Tolyl(2,3,4-trimethoxyphenyl)sulfane 3r.6 Light yellow oil, yield 87%, 126.2 mg. 1H NMR (500 MHz, CDCl3) δ 7.2 (d, J = 7.9 Hz, 2H), 7.1 (d, J = 7.9 Hz, 2H), 6.9 (d, J = 8.7 Hz, 1H), 6.6 (d, J = 8.7 Hz, 1H), 3.9 (s, 3H), 3.8 (s, 6H), 2.3 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 153.8, 153.0, 143.0, 136.7, 132.6, 130.7, 130.0, 127.5, 108.0, 61.2, 61.1, 56.2, 21.2. GC-MS (EI) m/z: 290.

O

OO

SChemical Formula: C17H20O3S

Mass: 304Elemental Analysis: C, 67.08; H, 6.62; O, 15.77; S, 10.53

p-Tolyl(2,3,4-trimethoxy-6-methylphenyl)sulfane 3s. Light yellow oil, yield 91%, 138.3 mg. 1H NMR (500 MHz, CDCl3) δ 7.00 (d, J = 8.0 Hz, 2H), 6.91 (d, J = 8.2 Hz, 2H), 6.66 (s, 1H), 3.88 (d, J = 13.0 Hz, 6H), 3.77 (s, 3H), 2.37 (d, J = 2.0 Hz, 3H), 2.26 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 155.9, 154.4, 141.0, 139.6, 135.3, 134.6, 129.7, 126.3, 117.3, 109.5, 61.6, 61.1, 56.1, 21.5, 21.0. GC-MS (EI) m/z: 304. Anal.

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Calcd for C17H20O3S: C, 67.08%; H, 6.62%. Found: C, 66.74%; H, 6.93%.

O O

SO


p-Tolyl(2,4,6-trimethoxyphenyl)sulfane 3t.7 White solid, mp 112-114 °C (lit. 111-112 °C), yield 92%, 133.4 mg. 1H NMR (500 MHz, CDCl3) δ 7.01 – 6.90 (m, 4H), 6.21 (s, 2H), 3.87 (s, 3H), 3.81 (s, 6H), 2.25 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 162.8, 162.6, 135.2, 134.2, 129.4, 126.2, 99.6, 91.4, 56.4, 55.5, 21.0. GC-MS (EI) m/z: 290.OH

SChemical Formula: C17H20OS

Mass: 272

4-(tert-Butyl)-2-(p-tolylthio)phenol 3u.8 Yellow oil, yield 73%, 99.3 mg. 1H NMR (500 MHz, CDCl3) δ 7.5 (d, J = 2.5 Hz, 1H), 7.4 (dd, J = 8.6, 2.5 Hz, 1H), 7.1 (d, J = 8.0 Hz, 2H), 7.0 (dd, J = 8.5, 2.9 Hz, 3H), 6.4 (s, 1H), 2.3 (s, 3H), 1.3 (s, 9H). 13C NMR (125 MHz, CDCl3) δ 155.0, 144.3, 136.1, 133.5, 132.6, 130.1, 129.4, 127.1, 116.1, 115.0, 34.3, 31.6, 21.0. GC-MS (EI) m/z: 272.

NH2

O O

S Chemical Formula: C15H17NO2SMass: 275

Elemental Analysis: C, 65.43; H, 6.22; N, 5.09; O, 11.62; S, 11.64

3,5-dimethoxy-2-(p-tolylthio)aniline 4a. Brown oil, yield 52%, 71.5 mg. 1H NMR (500 MHz, CDCl3) δ 7.00 (d, J = 8.3 Hz, 2H), 6.96 (d, J = 8.3 Hz, 2H), 6.05 – 5.91 (m, 2H), 4.49 (s, 2H), 3.79 (d, J = 10.4 Hz, 6H), 2.26 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 164.2, 154.2, 137.1, 134.9, 133.6, 129.7, 125.9, 94.5, 85.6, 56.2, 29.9, 29.5, 21.0. GC-MS (EI) m/z: 275. Anal. Calcd for C15H17NO2S: C, 65.43%; H, 6.22%; N, 5.09%. Found: C, 65.68%; H, 6.01%; N, 4.88%.

NH2

O O

SSChemical Formula: C22H23NO2S2

Mass: 397Elemental Analysis: C, 66.47; H, 5.83; N,

3.52; O, 8.05; S, 16.13

3,5-Dimethoxy-2,6-bis(p-tolylthio)aniline 4a’. White solid, mp 131-133 °C, yield 37%, 73.4 mg. 1H NMR (500 MHz, CDCl3) δ 7.01 (d, J = 8.1 Hz, 4H), 6.97 (d, J = 8.3 Hz, 4H), 6.03 (s, 1H), 5.39 (s, 2H), 3.88 (s, 6H), 2.27 (s, 6H). 13C NMR (125 MHz, CDCl3) δ 162.8, 151.6, 134.7, 129.7, 125.8, 92.2, 89.6, 56.2, 55.4, 21.0. GC-MS (EI) m/z: 397. Anal. Calcd for C22H23NO2S2: C, 66.47%; H, 5.83%; N, 3.52%. Found: C, 66.75%; H, 5.62%, N, 3.24%.

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SNH2

Chemical Formula: C17H15NSMass: 265

1-((4-Methoxyphenyl)thio)naphthalen-2-amine 4b.1 Red solid, mp 110-112 °C (lit. 113-115 °C), yield 92%, 121.9 mg. 1H NMR (500 MHz, CDCl3) δ 8.34 (d, J = 8.5 Hz, 1H), 7.76 (dd, J = 11.6, 8.4 Hz, 2H), 7.29 (ddd, J = 8.0, 6.9, 1.1 Hz, 1H), 7.06 (d, J = 8.8 Hz, 1H), 6.99 (m, 4H), 4.36 (s, 2H), 2.27 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 148.5, 136.9, 135.0, 133.4, 131.8, 129.9, 128.6, 128.5, 127.9, 126.3, 124.5, 122.7, 117.8, 105.5, 21.0. GC-MS (EI) m/z: 265.

NH2

S


Elemental Analysis: C, 76.20; H, 8.41; N, 4.68; S, 10.71

2,6-Diisopropyl-4-(p-tolylthio)aniline 4c. Brown oil, yield 52%, 77.7 mg. 1H NMR (500 MHz, CDCl3) δ 7.19 (s, 2H), 7.04 (s, 4H), 3.87 (s, 2H), 2.90 (p, J = 6.8 Hz, 2H), 2.29 (s, 3H), 1.25 (d, J = 6.8 Hz, 12H). 13C NMR (125 MHz, CDCl3) δ 141.0, 136.4, 135.0, 133.5, 129.7, 129.5, 127.4, 120.7, 28.2, 22.4, 21.0. GC-MS (EI) m/z: 299. Anal. Calcd for C19H25NS: C, 76.20%; H, 8.41%, N, 4.68%. Found: C, 76.48%; H, 8.33%, N, 4.76%.

N

S


N, N-dimethyl-4-(p-tolylthio)aniline 4d.9 Yellow solid, mp 44-47 °C (lit. 43-47 °C), yield 74%, 89.9 mg. 1H NMR (500 MHz, CDCl3) δ 7.35 (d, J = 8.4 Hz, 1H), 7.13 (d, J = 8.3 Hz, 1H), 6.99 (d, J = 8.2 Hz, 1H), 6.69 (d, J = 7.8 Hz, 1H), 2.98 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 150.8, 139.1, 136.2, 130.9, 128.9, 128.2, 116.9, 113.2, 101.5, 40.47. GC-MS (EI) m/z: 243.

O

HO

S



3-Hydroxy-13-methyl-2-(p-tolylthio)-6,7,8,9,11,12,13,14,15,16-decahydro-17H-

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cyclopenta[a]phenanthren-17-one 5a. White solid, mp >240 °C, yield 73%, 143.1 mg. 1H NMR (500 MHz, CDCl3) δ 7.42 (d, J = 1.2 Hz, 1H), 7.04 (d, J = 8.1 Hz, 2H), 6.99 (d, J = 8.4 Hz, 2H), 6.79 (s, 1H), 6.32 (s, 1H), 3.01 – 2.82 (m, 2H), 2.50 (dd, J = 19.0, 8.8 Hz, 1H), 2.38 – 2.30 (m, 1H), 2.27 (s, 3H), 2.19 – 2.10 (m, 1H), 2.09 – 1.97 (m, 2H), 1.95 – 1.88 (m, 1H), 1.67 – 1.39 (m, 7H), 0.91 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 220.9, 155.1, 141.4, 136.1, 133.7, 133.2, 132.8, 130.1, 127.2, 115.3, 114.1, 50.5, 48.1, 44.0, 38.2, 36.0, 31.6, 29.6, 26.5, 26.1, 21.7, 21.1, 14.0. MS (ESI) m/z: 391 [M-H]-. Anal. Calcd for C25H28O2S: C, 76.49%; H, 7.19%. Found: C, 76.43%; H, 7.32%.

NH

S Chemical Formula: C15H13NSMass: 239

3-(p-Tolylthio)-1H-indole 5b.10 White solid, mp 122-124 oC (lit. 125-126 oC), yield 86%, 102.8 mg. 1H NMR (500 MHz, CDCl3) δ 8.21 (s, 1H), 7.61 (d, J = 7.4 Hz, 1H), 7.35 (d, J = 8.7 Hz, 2H), 7.23 (t, J = 7.5 Hz, 1H), 7.14 (t, J = 7.4 Hz, 1H), 7.05 – 6.98 (m, 2H), 6.95 (d, J = 6.8 Hz, 2H), 2.22 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 135.5, 134.6, 133.8, 129.6, 128.6, 128.2, 125.3, 122.1, 119.9, 118.7, 110.7, 102.3, 20.0. GC-MS (EI) m/z: 239.

NH

NCS Chemical Formula: C16H12N2S

Mass: 264

3-(p-tolylthio)-1H-indole-5-carbonitrile 5c.11 White solid, mp 202-203 oC (lit. 201-203 oC), yield 93%, 122.3 mg. 1H NMR (500 MHz, DMSO-d6) δ 12.08 (s, 1H), 7.86 (d, J = 2.7 Hz, 1H), 7.69 (d, J = 1.5 Hz, 1H), 7.53 (d, J = 8.4 Hz, 1H), 7.40 (dd, J = 8.5, 1.6 Hz, 1H), 6.92 – 6.82 (m, 4H), 2.05 (s, 3H). 13C NMR (125 MHz, DMSO-d6) δ 138.0, 134.3, 134.2, 133.9, 129.1, 128.0, 125.8, 124.4, 123.1, 119.7, 113.3, 101.8, 101.4, 19.9. GC-MS (EI) m/z: 264.

NH

OS Chemical Formula: C16H15NOS

Mass: 269

5-methoxy-3-(p-tolylthio)-1H-indole 5d.11 Light oil, yield 89%, 120 mg. 1H NMR (500 MHz, CDCl3) δ 8.24 (s, 1H), 7.34 (d, J = 2.7 Hz, 1H), 7.22 (d, J = 8.8 Hz, 1H),

10

6.99 (d, J = 2.5 Hz, 1H), 6.98 – 6.90 (m, 4H), 6.84 (dd, J = 8.8, 2.5 Hz, 1H), 3.72 (s, 3H), 2.19 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 154.1, 134.7, 133.6, 130.4, 130.2, 129.0, 128.6, 125.1, 112.6, 111.5, 101.8, 99.9, 54.9, 19.9. GC-MS (EI) m/z: 269.

NH

SS Chemical Formula: C20H21NS2Exact Mass: 339.1115

Elemental Analysis: C, 70.75; H, 6.23; N, 4.13; S, 18.89

2,5-dimethyl-3,4-bis(p-tolylthio)-1H-pyrrole 5e. White solid, mp 189-191 oC, yield 92%, 156 mg. 1H NMR (500 MHz, DMSO-d6) δ 11.36 (s, 1H), 6.81 (d, J = 7.9 Hz, 4H), 6.66 (d, J = 7.9 Hz, 4H), 2.08 (s, 6H), 2.05 (s, 6H). 13C NMR (125 MHz, DMSO-d6) δ 135.6, 132.9, 132.5, 128.7, 124.6, 107.6, 19.9, 11.1. GC-MS (EI) m/z: 339. Anal. Calcd for C20H21NS2: C, 70.75%; H, 6.23%; N, 4.13%. Found: C, 70.54%; H, 6.59%; N, 4.28%.

Br

OO

Chemical Formula: C8H9BrO2Mass: 216

1-Bromo-2,4-dimethoxybenzene 7.12 Colorless oil. 1H NMR (500 MHz, CDCl3) δ 7.35 (d, J = 8.7 Hz, 1H), 6.43 (d, J = 2.8 Hz, 1H), 6.34 (dd, J = 8.7, 2.7 Hz, 1H), 3.81 (s, 3H), 3.74 (s, 3H). 13C NMR (125 MHz, CDCl3) δ 159.3, 155.6, 132.2, 104.9, 101.5, 99.0, 55.2, 54.6. GC-MS (EI) m/z: 216.

References[1] Kang, X.; Yan, R.; Yu, G.; Pang, X.; Liu, X.; Li, X.; Xiang, L.; Huang, G., Iodine-mediated thiolation of substituted naphthols/naphthylamines and arylsulfonyl hydrazides via C(sp2)-H bond functionalization. The Journal of Organic Chemistry 2014, 79 (21), 10605-10. [2] Xiao, F.; Chen, S.; Tian, J.; Huang, H.; Liu, Y.; Deng, G.-J., Chemoselective cross-coupling reaction of sodium sulfinates with phenols under aqueous conditions. Green Chem. 2016, 18 (6), 1538-1546.[3] Kundu, D.; Chatterjee, T.; Ranu, B., Magnetically Separable CuFe2O4 Nanoparticles Catalyzed Ligand-Free C-S Coupling in Water: Access to (E)- and (Z)-Styrenyl-, Heteroaryl and Sterically Hindered Aryl Sulfides. Advanced Synthesis & Catalysis. 2013, 355(11-12), 2285-1546.[4] Commercial chemical, CAS number: 1466548-02-6. [5] Prasad Ch, D.; Balkrishna, S. J.; Kumar, A.; Bhakuni, B. S.; Shrimali, K.; Biswas, S.; Kumar, S., Transition-metal-free synthesis of unsymmetrical diaryl chalcogenides from arenes and diaryl dichalcogenides. The Journal of organic chemistry 2013, 78 (4), 1434-43.[6] Yan, K.; Yang, D.; Sun, P.; Wei, W.; Liu, Y.; Li, G.; Lu, S.; Wang, H., Direct thiolation of methoxybenzenes with thiols under metal-free conditions by iodine catalysis. Tetrahedron Letters 2015, 56 (33), 4792-4795.[7] Parumala, S. K. R.; Peddinti, R. K., Iodine catalyzed cross-dehydrogenative C–S coupling by C(sp2)–H bond activation: direct access to aryl sulfides from aryl thiols.

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Green Chem. 2015, 17 (7), 4068-4072.[8] Tian, H.; Zhu, C.; Yang, H.; Fu, H., Iron or boron-catalyzed C-H arylthiation of substituted phenols at room temperature. Chemical Communications 2014, 50 (64), 8875-7.[9] Pang, X.; Xiang, L.; Yang, X.; Yan, R., Iodine-Mediated Synthesis of Aromatic Thioethers with Aromatic Amines and Sulfonyl Hydrazides in High Regioselectivity via C(sp2)–H Bond Functionalization. Advanced Synthesis & Catalysis 2016, 358 (2), 321-325.[10] Xiao, F.; Xie, H.; Liu, S.; Deng, G.-J., Iodine-Catalyzed Regioselective Sulfenylation of Indoles with Sodium Sulfinates. Advanced Synthesis & Catalysis 2014, 356 (2-3), 364-368.[11] Liu, Y.; Zhang, Y.; Hu, C.; Wan, J.-P.; Wen, C., Synthesis of 3-sulfenylated indoles by a simple NaOH promoted sulfenylation reaction. RSC Advances 2014, 4 (67), 35528.[12] Song, S.; Sun, X.; Li, X.; Yuan, Y.; Jiao, N., Efficient and Practical Oxidative Bromination and Iodination of Arenes and Heteroarenes with DMSO and Hydrogen Halide: A Mild Protocol for Late-Stage Functionalization. Organic letters 2015, 17 (12), 2886-9.

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2. NMR Spectra of All Products

1H NMR of 3a

13C NMR of 3a

13

1H NMR of 3b

13C NMR of 3b

14

1H NMR of 3c

13C NMR of 3c

15

1H NMR of 3d

13C NMR of 3d

16

1H NMR of 3e

13C NMR of 3e

17

1H NMR of 3f

13C NMR of 3f

18

1H NMR of 3g

13C NMR of 3g

19

1H NMR of 3h

13C NMR of 3h

20

1H NMR of 3i

13C NMR of 3i

21

1H NMR of 3j

13C NMR of 3j

22

1H NMR of 3k

13C NMR of 3k

23

1H NMR of 3l

13C NMR of 3l

24

1H NMR of 3m

13C NMR of 3m

25

1H NMR of 3n

13C NMR of 3n

26

1H NMR of 3o

13C NMR of 3o

27

1H NMR of 3p

13C NMR of 3p

28

1H NMR of 3q

13C NMR of 3q

29

1H NMR of 3r

13C NMR of 3r

30

1H NMR of 3s

13C NMR of 3s

31

1H NMR of 3t

13C NMR of 3t

32

1H NMR of 3u

13C NMR of 3u

33

1H NMR of 4a

13C NMR of 4a

34

1H NMR of 4a’

13C NMR of 4a’

35

1H NMR of 4b

13C NMR of 4b

36

1H NMR of 4c

13C NMR of 4c

37

1H NMR of 4d

13C NMR of 4d

38

1H NMR of 5a

13C NMR of 5a

39

1H NMR of 5b

13C NMR of 5b

40

1H NMR of 5c

13C NMR of 5c

41

1H NMR of 5d

13C NMR of 5d

42

1H NMR of 5e

13C NMR of 5e

43

1H NMR of 7

13C NMR of 7

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