CC BY 4.0 · SynOpen 2018; 02(03): 0229-0233
DOI: 10.1055/s-0037-1610360
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Aqueous Medium Preparation of Dialkyldiselenides

Tapasi Manna
,
Anup Kumar Misra*
Further Information

Publication History

Received: 20 April 2018

Accepted after revision: 26 May 2018

Publication Date:
19 July 2018 (online)


Abstract

One-pot, two-step reaction conditions have been developed for the preparation of dialkyl diselenides by the treatment of alkyl halides with potassium selenocyanate followed by alkaline hydrolysis of the in situ generated alkyl selenocyanate in water. The reaction is reasonably fast and the yields of the products were very good. Several functional groups present in the substrates were unaffected under the reaction conditions.

 
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  • 25 General method for the preparation of dialkyl diselenides:To a solution of alkyl halide (1.0 mmol) in H2O (5 mL) were added TBAB (0.1 mmol) and KSeCN (1.05 mmol) and the reaction mixture was stirred vigorously at 65 °C for the time detailed in Table 1. K3PO4 (5.0 mmol) was then added and the mixture was stirred at 65 °C for the time detailed in Table 2. The reaction mixture was cooled and extracted with EtOAc (2 × 25 mL), and the organic layer was dried (Na2SO4), filtered and concentrated. Chromatographic purification of the crude product over SiO2 furnished pure products. Analytical data of known compounds match with the data reported in the literature.
  • 26 Analytical data of novel compounds:Di-(2-phenoxyethyl) diselenide (2h): Yellow oil; 1H NMR (500 MHz, CDCl3): δ = 7.29–7.21 (m, 4 H, Ar-H), 6.96–6.87 (m, 6 H, Ar-H), 4.22 (t, J = 7.0 Hz, 4 H, OCH2), 3.28 (t, J = 7.0 Hz, 4 H, SeCH2); 13C NMR (125 Hz, CDCl3): δ = 157.2–113.6 (Ar-C), 66.6 (2 C), 27.1 (2 C); ESI-MS: m/z = 402.9 [M+H]+; Anal. Calcd. for C16H18O2Se2 (401.96): C, 48.01; H, 4.53; found: C, 47.84; H, 4.75.Di-(2-(4-methoxyphenoxy)ethyl) diselenide (2i): Yellow oil; 1H NMR (500 MHz, CDCl3): δ = 6.86–6.74 (m, 8 H, Ar-H), 4.20 (t, J = 7.0 Hz, 4 H, OCH2), 3.76 (s, 6 H, OCH3), 3.25 (t, J = 7.0 Hz, 4 H, SeCH2); 13C NMR (125 Hz, CDCl3): δ = 153.0–113.6 (Ar-C), 67.4 (2 C), 54.5 (2 C, OCH3), 27.2 (2 C); ESI-MS: m/z = 462.9 [M+H]+; Anal. Calcd. for C18H22O4Se2 (461.98): C, 46.97; H, 4.82; found: C, 46.80; H, 5.00.Di-(2-(4-nitrophenoxy)ethyl) diselenide (2j): Yellow oil; 1H NMR (500 MHz, CDCl3): δ = 8.22–8.17 (m, 4 H, Ar-H), 6.98–6.92 (m, 4 H, Ar-H), 4.33 (t, J = 7.0 Hz, 4 H, OCH2), 3.30 (t, J = 7.0 Hz, 4 H, SeCH2); 13C NMR (125 Hz, CDCl3): δ = 162.0–113.4 (Ar-C), 67.3 (2 C), 26.2 (2 C); ESI-MS: m/z = 492.9 [M+H]+; Anal. Calcd. for C16H16N2O6Se2 (491.93): C, 39.20; H, 3.29; found: C, 39.00; H, 3.50.Di-(2-(2-naphthalenyloxy)ethyl) diselenide (2k): Yellow oil; 1H NMR (500 MHz, CDCl3): δ = 7.78–7.63 (m, 6 H, Ar-H), 7.42–7.37 (m, 2 H, Ar-H), 7.32–7.30 (m, 2 H, Ar-H), 7.14–7.08 (m, 4 H, Ar-H), 4.38 (t, J = 7.0 Hz, 4 H, OCH2), 3.36–3.31 (t, J = 7.0 Hz, 4 H, SeCH2); 13C NMR (125 Hz, CDCl3): δ = 155.2–105.9 (Ar-C), 66.7 (2 C), 27.0 (2 C); ESI-MS: m/z = 02.9 [M+H]+; Anal. Calcd. for C24H22O2Se2 (501.99): C, 57.61; H, 4.43; found: C, 57.45; H, 4.60.Di-(4-(phenylthio)butyl) diselenide (2l): Yellow oil; 1H NMR (500 MHz, CDCl3): δ = 7.31–7.13 (m, 10 H, Ar-H), 2.91 (t, J = 7.0 Hz, 4 H), 2.89 (t, J = 7.0 Hz, 4 H), 1.90–1.80 (m, 4 H), 1.79–1.71 (m, 4 H); 13C NMR (125 Hz, CDCl3): δ = 135.5-124.8 (Ar-C), 32.1 (2 C), 28.8 (2 C), 28.1 (2 C), 27.8 (2 C); ESI-MS: m/z = 490.9 [M+H]+; Anal. Calcd. for C20H26S2Se2 (488.47): C, 49.18; H, 5.37; found: C, 49.00; H, 5.58.
  • 27 Bis-(p-methoxyphenyl 2,3,4-tri-O-benzyl-β-d-glucopyranosyl)-(6,6′)-diselenide (2m): Yellow oil; 1H NMR (500 MHz, CDCl3): δ = 7.32–7.19 (m, 30 H, Ar-H), 7.01 (d, J = 9.0 Hz, 4 H, Ar-H), 6.77 (d, J = 9.0 Hz, 4 H, Ar-H), 5.04 (d, J = 11.0 Hz, 2 H, PhCH), 4.92 (d, J = 11.0 Hz, 2 H, PhCH), 4.84 (d, J = 11.0 Hz, 2 H, PhCH), 4.78 (d, J = 11.0 Hz, 2 H, PhCH), 4.75 (d, J = 7.5 Hz, 2 H, H-1, H-1′), 4.73 (d, J = 11.0 Hz, 2 H, PhCH), 4.58 (d, J = 11.0 Hz, 2 H, PhCH), 3.74 (s, 6 H, OCH3), 3.68–3.64 (m, 4 H, H-2, H-2′, H-3, H-3′), 3.62–3.57 (m, 2 H, H-5, H-5′), 3.42–3.38 (m, 2 H, H-4, H-4′), 3.37–3.34 (m, 2 H, H-6a, H-6′a), 3.12–3.06 (m, 2 H, H-6b, H-6′b); 13C NMR (125 Hz, CDCl3): δ = 155.37–114.5 (Ar-C), 102.8 (2 C, C-1, C-1′), 84.4 (2 C), 82.2 (2 C), 80.8 (2 C), 75.7 (2 C, PhCH2), 75.2 (2 C), 75.0 (2 C, PhCH2), 74.9 (2 C, PhCH2), 55.5 (2 C, OCH3), 33.3 (2 C, C-6, C-6′); ESI-MS: m/z = 261.3 [M+Na]+; Anal. Calcd. for C68H70O12Se2 (1238.31): C, 66.01; H, 5.70; found: C, 65.82; H, 5.54.Bis-(p-methoxyphenyl 2,3,4-tri-O-benzyl-β-d-galactopyranosyl)-(6,6′)-diselenide (2n): Yellow oil; 1H NMR (500 MHz, CDCl3): δ = 7.40–7.22 (m, 30 H, Ar-H), 7.06–7.04 (m, 4 H, Ar-H), 6.77–6.74 (m, 4 H, Ar-H), 5.27 (d, J = 3.0 Hz, 2 H, H-1, H-1′), 4.93–4.47 (m, 12 H, 6 PhCH2), 4.13–4.04 (m, 4 H, H-2, H-2′ and H-3, H-3′), 4.00–3.96 (m, 2 H, H-5, H-5′), 3.70 (br s, 6 H, 2 OCH3), 3.66 (br s, 2 H, H-4, H-4′), 3.07–3.03 (m, 2 H, H-6a, H-6′a), 2.72–2.68 (m, 2 H, H-6b, H-6′b); 13C NMR (125 Hz, CDCl3): δ = 155.2–114.5 (Ar-C), 98.3 (2 C, C-1, C-1′), 79.1 (2 C), 76.4 (2 C), 76.0 (2 C), 74.9 (2 C), 73.6 (2 C), 73.2 (2 C), 71.2 (2 C), 55.4 (2 C, OCH3), 30.6 (2 C, C-6, C-6′); ESI-MS: m/z = 261.3 [M+Na]+; Anal. Calcd. for C68H70O12Se2 (1238.31): C, 66.01; H, 5.70; found: C, 65.80; H, 5.55.Bis-(2,3-di-O-benzyloxy-(R)-propyl) diselenide (2o): Yellow oil; 1H NMR (500 MHz, CDCl3): δ = 7.34–7.22 (m, 20 H, Ar-H), 4.63–4.48 (m, 8 H, PhCH2), 3.81–3.77 (m, 2 H), 3.62–3.56 (m, 4 H), 3.19–3.15 (m, 4 H); 13C NMR (125 Hz, CDCl3): δ = 138.2–127.6 (Ar-C), 78.0 (2 C), 73.4 (2 C), 72.0 (2 C), 71.3 (2 C), 32.4 (2 C), 29.7 (2 C); ESI-MS: m/z = 71.1 [M+H]+; Anal. Calcd. for C34H38O4Se2 (670.11): C, 61.08; H, 5.73; found: C, 60.90; H, 5.95.