Synthesis of (Thio)substituted -1,3-Butadienes and -Butenynes

Year 2019, , 201 - 206, 15.06.2019

Aysecik Kacmaz

https://doi.org/10.18596/jotcsa.536853

Abstract

In this study, 2H-1,1,3,4,4-pentachloro-1,3-butadiene (1) reacted with different thiols
(2-Methyl-2-propanethiol 2a, Benzyl
mercaptan 2b,
4-tert-butylbenzenethiol 2c,
4-Nitrothiophenol 2d) in ethanol in
the presence of NaOH to afford mono-thio-substituted-1,3-butadienes and mono-
and tris-thio-substituted-1-buten-3-ynes. Among them,
(4-tert-butylphenyl)(1,3,4,4-tetrachlorobuta-1,3-dienyl)sulfane (4c) exhibited two isomers of mono
products. And, the reaction of compound (1)
with 2-Hydroxythiophenol (2e) in
dimethylformamide in the presence of triethylamine took place formation of OH
protected butadiene structure
2-((Z)-1,3,4,4-tetrachlorobuta-1,3-dienylthio)phenol (4e) and ring-closed butadiene structure
(E)-2-(2,3,3-trichloroallylidene)benzo[d][1,3]oxathiole (6), together and with two isomers of each. Their structures
identified on the basis of GC-MS(+EI) analysis with different retention times
(RT). Characterization of the synthesized compounds was done using different
methods, mass spectrometry
(GC-MS(+EI)), ¹H-, ¹³C-, APT- NMR, IR and elemental
analysis.

 

Keywords

Thioethers, 1-buten-3-ynes, 1, 3-butadienes, GC-MS, thiols

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. J. Org. Chem. 2014; 79: 10605-10.
• 2. Clayden J, MacLellan P. Asymmetric synthesis of tertiary thiols and thioethers. Beilstein J. Org. Chem. 2011; 7: 582-95.
• 3. Auger S, Merand Y, Pelletier JD, Poirier D, Labrie F. Synthesis and biological activities of thioether derivatives related to the antiestrogens tamoxifen and ICI 164384. J. Steroid. Biochem. Mol. Biol. 1995; 52(6): 547-65.
• 4. Schopfer U, Schlapbach A. A general palladium-catalysed synthesis of aromatic and heteroaromatic thioethers. Tetrahedron. 2001; 57: 3069-73.
• 5. Leroux F, Jeschke P, Schlosser M. α-Fluorinated Ethers, Thioethers, and Amines: Anomerically Biased Species. Chem. Rev. 2005; 105(3): 827-56.
• 6. H. Bluestone, Polyunsaturated sulfides and sulfones and method of preparing same. US Patent 3,021,370, Feb. 13. 1962.
• 7. Schmidt A, Rahimi A, Gjikaj M. Sulfanyl-Substituted [3]Cumulenes and Buta-1,3-dienes from a Tetrakis(pyridinium)-Substituted Butadiene. Synthesis. 2009; 14: 2371-8.
• 8. Zapol’skii VA, Nutz E, Namyslo JC, Adam AEV, Kaufmann DE. Chemistry of Polyhalogenated Nitrobutadienes, 2: Synthesis of N-Tetrachloro¬allylidene-N′-arylhydrazines by a Formal Synproportionation Reaction, Synthesis. 2006; 17: 2927-33.
• 9. Yoshimatsu M, Kinoshita S, Sugimoto T. Palladium-Catalyzed Terminal Alkyne Coupling Reaction of β-Bromo-β-phenylthio or β-Methylthio-α-trifluoromethyl Enol Ethers: a Convenient Synthesis of 2-Sulfonyl-1-buten-3-ynes. Chem. Pharm. Bull. 1999; 47(10): 1497-500.
• 10. Backvall JE, Chinchilla R, Najera C, Yus M. The Use of Sulfonyl 1,3-Dienes in Organic Synthesis. Chem. Rev. 1998; 98: 2291-312.
• 11. Padwa A, Bullock WH, Norman BH, Perumattam J. (Nitroaryl)sulfinyl-substituted allenes. Novel and convenient propargyl alcohol synthons in 4 + 2 cycloaddition chemistry. J. Org. Chem. 1991; 56: 4252-9.
• 12. Ibis C, Şahinler Ayla S. Mono-, bis-, tris-, and tetrakis(thio)substituted butenynes from halogenated butenes and butadienes. Phosphorus Sulfur Silicon Relat Elem. 2017; 192(6): 597-601.
• 13. Ibis C, Beyazit N. The synthesis of new thiosubstituted butadienes, butenynes and butatrienes Arkivoc. 2010; ix: 244-56.
• 14. Ibis C, Sahinler Ayla S, Beyazit N, Bahar H, Synthesis of Novel Thioethers and Sulfoxide Compounds, Phosphorus. Sulfur. Silicon. Relat. Elem. 2013; 188: 1643-51.
• 15. Ibis C, Ozkok F. The Synthesis of Novel S-, S,S-, S,S,S-, S,O-, N,S-Substituted Halogenobuta-1,3-dienes. Acta Chim. Slov. 2012; 59:294-301.
• 16. Ibis C, Yilmaz N. Neue N,S-substituierte Dienverbindungen aus reaktionen von mono(arylthio)substituierten polyhalo-2-nitrodienen mit aminen. Phosphorus Sulfur Silicon Relat Elem. 2000; 159: 87-98.
• 17. Ibis C, Göksel FS, Aydınlı G. New N,S-Substituted Dienes from the Reactions of Some Aliphatic Mono(thio)substituted Nitrodienes with Aromatic Primary Amines and Cyclic Amines. Phosphorus Sulfur Silicon Relat Elem. 2003; 178: 777-83.
• 18. Ibis C, Yildirim H. The Synthesis of Novel S-, S,S-, S,S,S-, and N,S-Substituted Nitrodienes from Polyhalonitrodienes and Thiols. Phosphorus Sulfur Silicon Relat Elem. 2011; 186: 2236-49.
• 19. Ibis C, Sahin A, The Synthesis and Characterization of Some Novel Thioethers: Thio-Subsituted [3]Cumulenes, -1-Buten-3-ynes and Buta-1,3-dienes. Bull. Korean Chem. Soc. 2010; 31, 2255-60.
• 20. Ibis C, Sahin A, Synthesis of new sulfanyl-, sulfinyl-, and sulfonyl-substituted polychlorobuta-1,3-dienes. Russ. J. Org. Chem. 2016; 52(6): 897-902.
• 21. Roedig A, Zaby G. Untersuchungen zum Mechanismus der Bildung von Tetrakis-(organylthio)buteninen und -butatrienen aus Perchlorbutenin bzw. -butatrien mit Thiolaten. Liebigs Ann. Chem. 1979; 1979(10): 1626-34.
• 22. Roedig A, Zaby G. Pentakis(organylthio)-1,3-butadiene aus Perchlorbutenin und Tetrakis(organylthio)butatrienen oder -buteninen mit Thiolen und Thiolaten. Liebigs Ann. Chem. 1979; 1979(10): 1614-25.
• 23. Roedig A, Zaby G. Reaktionen von Poly(organylthio)buteninen und -butatrienen mit Elektrophilen. Chem. Ber. 1980; 113: 3342-51.
• 24. Roedig A, Ibis C, Zaby G. Reaktionen von Polychlor‐1,3‐butadienen und Polychlorbutenen mit Thiolaten. Chem. Ber. 1981; 114: 684-98.
• 25. Ibis C. Neue Thioether und Disulfidverbindungen aus mono(arylthio)substitutiertem 2-nitrotetrachlor-1,3-butadien und neue thioether mit butadien-, butin und butenin struktur aus hexachlorbuten. Phosphorus Sulfur Silicon Relat Elem. 1996; 118: 49-60.
• 26. Roedig A, Zaby G, Scharf W. Tetrakisthiobutatriene aus Perchlorbutenin und Thiolate. Chem. Ber. 1977; 110: 1484-91.
• 27. Roedig A, Zaby G. Tetrakis(organylthio)butenine aus Perchlorbutenin und Tetrakis(organylthio)butatrienen mit Thiolaten. Liebigs Ann. Chem. 1979; 1979(10): 1606-13.
• 28. Ibiş C, Gurun C. Neue Sulfide mit Btin-, Butenin- Und Butadien Struktur. Sulfur Letters. 1992; 14: 251-7.
• 29. Ibis C. Review of Faculty of Science, University of Istanbul, Serie C, 1989; 53: 19.
• 30. Ibis C, Sahinler Ayla S, The synthesis and spectral investigation of new thiosubstituted butadienes and butenynes. Arkivoc. 2008; xvi: 29-37.