Aqueous Medium Preparation of Dialkyldiselenides

Tapasi Manna; Anup Kumar Misra

doi:10.1055/s-0037-1610360

SynOpen, Inhaltsverzeichnis

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

letter

Copyright with the author

Aqueous Medium Preparation of Dialkyldiselenides

Tapasi Manna

,

Anup Kumar Misra*

Abstract

Alle Artikel dieser Rubrik

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.

Key words

selenium - alkyl halides - dimerization - sustainable chemistry - water

Volltext

Referenzen

References and Notes

1a Devillanova FA. Handbook of Chalcogen Chemistry - New Perspectives in Sulfur, Selenium and Tellurium. Royal Society of Chemistry; Cambridge: 2007
1b Wirth T. Organoselenium Chemistry - Modern Developments in Organic Synthesis. Springer-Verlag; Heidelberg: 2000
1c Derek WJ. Risto L. Selenium and Tellurium Chemistry-From Small Molecules to Biomolecules and Materials. Springer-Verlag; Berlin, Heidelberg: 2011
1d Oae S. Organic Chemistry of Sulfur. Springer Science & Business Media; Berlin: 2012

2a Nogueira CW. Zeni G. Rocha JB. T. Chem. Rev. 2004; 104: 6255
2b Ibrahim M. Hassan W. Meinerz DF. Dos Santos M. Klimaczewski CV. Deobald AM. Costa MS. Noqueira CW. Barbosa NB. Rocha JB. Mol. Cell. Biochem. 2012; 371: 97
2c Saito G. Swanson JA. Lee K.-D. Adv. Drug Delivery Rev. 2003; 55: 199
2d Stefanello ST. Prestes AS. Ogunmoyole T. Salman SM. Schwab RS. Brender CR. Dornelles L. Rocha JB. T. Soares FA. A. Toxicol. in Vitro 2013; 27: 1433

3a Mugesh G. duMont WW. Sies H. Chem. Rev. 2001; 101: 2125
3b Geiger PG. Lin F. Girotti AW. Free Radical Biol. Med. 1993; 14: 251
3c Stadtman TC. Annu. Rev. Biochem. 1980; 49: 93
3d Gucchait A. Joardar N. Parida PK. Roy P. Mukherjee N. Dutta A. Yesuvadian R. SinhaBabu SP. Jana K. Misra AK. Eur. J. Med. Chem. 2018; 143: 598
3e Plano D. Baquedano Y. Moreno-Mateos D. Font M. Jiménez-Ruiz A. Palop JA. Sanmartín C. Eur. J. Med. Chem. 2011; 46: 3315

4a Guy RG. In The Chemistry of Cyanates and their Thio- Derivatives, Part 2. Patai S. John Wiley & Sons; New York: 1977. Chapter 18, p 819
4b Erian AW. Sherif SM. Tetrahedron 1999; 55: 7957

5a Klayman LD. Griffin TS. J. Am. Chem. Soc. 1973; 95: 197
5b Lewicki JW. Günther WH. H. Chu JY. C. J. Org. Chem. 1978; 43: 2672
5c Krief A. Van Wemmel T. Redon M. Dumont W. Delmotte C. Angew. Chem. Int. Ed. 1999; 38: 2245
5d Doudin KI. Berge RK. Frøystein N. Å. Songstad J. J. Chem. Soc., Perkin Trans. 1 2000; 723

6a Gladysz JA. Hornby JL. Garbe JE. J. Org. Chem. 1978; 43: 1204
6b Salama P. Bernard C. Tetrahedron Lett. 1995; 36: 5711
6c Syper L. Mlochowski J. Tetrahedron 1988; 44: 6119

7 Li JQ. Bao WL. Lue P. Zhou X.-J. Synth. Commun. 1991; 21: 799

8a Krief A. Delmotte C. Dumont W. Tetrahedron 1997; 53: 12147
8b Krief A. Derock M. Tetrahedron Lett. 2002; 43: 3083

9 Salama P. Bernard C. Tetrahedron Lett. 1998; 39: 745
10 Singh D. Deobald AM. Camargo LR. S. Tabarelli G. Rodrigues OE. D. Braga AL. Org. Lett. 2010; 12: 3288
11 Tian F. Yu Z. Lu S. J. Org. Chem. 2004; 69: 4520
12 Wang J.-X. Cui W. Hu Y. J. Chem. Soc., Perkin Trans. 1 1994; 2341
13 Krief A. De Mahieu AF. Dumont W. Trabelsi M. Synthesis 1988; 131
14 Logan G. Igunbor C. Chen G.-X. Davis H. Simon A. Salon J. Huang Z. Synlett 2006; 1554

15a Krief A. Dumont W. Delmotte C. Angew. Chem. Int. Ed. 2000; 39: 1669
15b Mülar J. Terfort A. Inorg. Chim. Acta 2006; 359: 4821
15c Heredia AA. Peñéñory AB. RSC Adv. 2015; 5: 105699
15d Heredia AA. Peñéñory AB. Beilstein J. Org. Chem. 2017; 13: 910

16 Yavuz S. Disli A. Yildirir Y. Türker L. Molecules 2005; 10: 1000

17a Guan Y. Townsend SD. Org. Lett. 2017; 19: 5252
17b Prabhu K. Chandrasekaran S. Chem. Commun. 1997; 1021

18 Nishiyama Y. Hamanaka S. Ogawa A. Murai S. Sonoda N. Synth. Commun. 1986; 16: 1059
19 Baker JW. Moffitt WG. J. Chem. Soc. 1930; 1722
20 Anastas PT. Warner JC. Green Chemistry: Theory and Practice. Oxford University Press; New York: 1998

21a Freudendahl DM. Santoro S. Shahzad SA. Santi C. Wirth T. Angew. Chem. Int. Ed. 2009; 48: 8409
21b Santi C. Jacob RG. Monti B. Bagnoli L. Sancineto L. Lenardão EJ. Molecules 2016; 21: 1482

22 Soleiman-Beigi M. Yavari I. Sadeghizadeh F. Phosphorus, Sulfur Silicon Relat. Elem. 2018; 193: 41
23 Li Z. Ke F. Deng H. Xu H. Xiang H. Zhou X. Org. Biomol. Chem. 2013; 11: 2943

24a Chanda A. Fokin VV. Chem. Rev. 2009; 109: 725
24b Sarma BK. Mugesh G. Chem. Eur. J. 2008; 14: 10603
24c Li C.-J. Chem. Rev. 2005; 105: 3095
24d Hailes HC. Org. Process Res. Dev. 2007; 11: 114
24e Dallinger D. Kappe CO. Chem. Rev. 2007; 107: 2563

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.