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Synthesis of Aromatic Thiols

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Aromatic Thiols and Their Derivatives

Abstract

Synthesis of aromatic thiols and their derivatives is a rather poorly explored area of ​​organosulfur chemistry. Meanwhile, with the rapid progress in industrial organic synthesis, aromatic thiols and their derivatives attract an ever-increasing attention from wide circles of chemical community.

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References

  1. Houben-Weyl: Die methoden der organischen chemie. Stuttgart: Thieme, 1337 (1955)

    Google Scholar 

  2. Boeseken, J.M., Koning, D.A.: Contribution a la connaissance de la reaction de Friedel et Crafts. Recl. Trav. Chim. Pays-Bas. 30, 116–136 (1911)

    Article  CAS  Google Scholar 

  3. Glass, H.B., Reid, E.E.: The direct introduction of sulfur into aromatic hydrocarbons. J. Am. Chem. Soc. 51, 3428–3430 (1929)

    Article  CAS  Google Scholar 

  4. Taboury, M.F.: Action du soufre et du selenium sur le bromure de phenylmagnesium et sur le bromure, -naphtylmagnesium. Bull. Soc. Chim. Fr. 3, 761–765 (1903)

    Google Scholar 

  5. Taboury, M.F.: Action du soufre et du selenium sur lea combinaisons organomagnesiennes des hydrocarbyres aromatigues mono- et dihalogenes dans le’ noyau. C.R. Acad. Sci., Ser. IIc: Chim. 138, 982–985 (1904)

    Google Scholar 

  6. Zhang, M., Ryckman, D., Chen, G., MacMillan, E., Duquette, J.: Practical and scaleable syntheses of 3-hydroxythiophenol. Synthesis. 1, 0112–0116 (2003)

    Google Scholar 

  7. Jiang, Y., Qin, Y., Xie, S., Zhang, X., Dong, J., Ma, D.: A general and efficient approach to aryl thiols: CuI-catalyzed coupling of aryl iodides with sulfur and subsequent reduction. Org. Lett. 11, 5250–5253 (2009)

    CAS  Google Scholar 

  8. Xu, H.J., Liang, Y.F., Cai, Z.Y., Qi, H.X., Yang, C.Y., Feng, Y.S.: CuI-nanoparticles-catalyzed selective synthesis of phenols, anilines, and thiophenols from aryl halides in aqueous solution. J. Org. Chem. 76, 2296–2300 (2011)

    Article  CAS  Google Scholar 

  9. Voronkov, M.G., Deryagina, E.N., Ivanova, G.M.: High-temperature organic synthesis. II. Reaction of hydrogen sulfide with bromophenol and its derivatives. Zh. Org. Khim. 12, 2179–2184 (1976)

    Google Scholar 

  10. Voronkov, M.G., Deryagina, E.N., Klochkova, L.G., Nakhmanovich, A.S.: High-temperature organic synthesis. I. Reactions of hydrogen sulfide with chlorine derivatives of the aromatic and thiophene series. Zh. Org. Khim. 12, 1515–1521 (1976)

    Google Scholar 

  11. Voronkov, M.G., Deryagina, E.N., Klochkova, L.G.: High-temperature organic synthesis. III. Reactions of hydrogen sulfide with chlorophenols. Zh. Org. Khim. 13, 1055–1057 (1977)

    Google Scholar 

  12. Shagun, L.G., Deriglazova, E.S., Kashik, T.V., Deryagina, E.N., Voronkov, M.G.: High-temperature organic synthesis. VII. On the effect of the substituents nature on the reaction of hydrogen sulfide with chlorine derivatives of aromatic and thiophene series. Zh. Org. Khim. 14, 187–192 (1978)

    Google Scholar 

  13. Weigand-Hilgetag: Experimental methods in organic chemistry. M.: Khimiya, p 944 (1969)

    Google Scholar 

  14. Vasil’tsov, A.M., Trofimov, B.A., Amosova, S.V.: Synthesis of thiols from alkyl halides and sodium hydrosulfide in dimethyl sulfoxide. Zh. Org. Khim. 19, 1339–1340 (1983)

    CAS  Google Scholar 

  15. Ellis, L.M., Reid, E.E.: The preparation and properties of a double series of aliphatic mercaptans 1,2,3. J. Am. Chem. Soc. 54, 1674–1687 (1932)

    Article  CAS  Google Scholar 

  16. Bost, R.W., Starnes, P.K., Wood, E.L.: 2,4-Dinitrothiophenol as a reagent for the characterization of organic halogen compounds. J. Am. Chem. Soc. 73, 1968–1970 (1951)

    Article  CAS  Google Scholar 

  17. Vasil'tsov, A.M., Trofimov, B.A., Amosova, S.V., Voronkov, M.G.: Divinyl sulfide. IX. Kinetics and mechanism of reaction of phenylacetylene with sodium hydrosulfide in dimethyl sulfoxide. Bull. Acad. Sci. USSR, chem. sci. 31, 2155–2160 (1982)

    Google Scholar 

  18. Trofimov, B.A., Musorin, G.K., Amosova, S.V.: Peculiarities of sodium sulfide dissolution in the system water-dimethyl sulfoxide. Zh. Prikl. Khim. 51, 1133–1136 (1978)

    Google Scholar 

  19. Trofimov, B.A., Vasil’tsov, A.M., Amosova, S.V.: A useful synthesis of deuterium-labelled methyl Vinyl Sulfide. Sulfur Letters. 2, 59–62 (1984)

    Google Scholar 

  20. Arnett, E.M., Small, L.E.: Ionization of group 6 and 7 protonic acids in dimethyl sulfoxide. J. Am. Chem. Soc. 99, 808–816 (1977)

    Google Scholar 

  21. Mayer, P.: Derivative Der Thiosalicylsaure Und Des Thioxanthon. Ber. 42, 3046–3067 (1909)

    Google Scholar 

  22. Gilman, H., Gainer, G.C.: Some 6-quinolyl sulfides and sulfones. J. Am. Chem. Soc. 71, 1747–1751 (1949)

    Google Scholar 

  23. Palani, T., Park, K., Song, K.H., Lee, S.: Palladium-catalyzed synthesis of (Z)-3-arylthioacrylic acids and thiochromenones. Adv. Synth. Catal. 355, 1160–1168 (2013)

    Google Scholar 

  24. Testaferri, L., Tingoli, M., Tiecco, M.: A convenient synthesis of aromatic thiols from unactivated Aryl Halides. Tetrahedron Lett. 21, 3099–3100 (1980)

    Google Scholar 

  25. Testaferri, L., Tiecco, M., Tingoli, M., Chianelli, D., Maiolo, F.: Selective Cleavage of the Carbon-Sulphur and Carbon-Oxygen Bonds in Methoxythioanisoles. Tetrahedron. 38, 2721–2724 (1982)

    Google Scholar 

  26. Testaferri, L., Tiecco, M., Tingoli, M., Chianelli, D., Montanucci, M.: Selective dealkylations of Aryl Alkyl Ethers and Thioethers by Sodium in HMPA. Tetrahedron. 38, 3687–3692 (1982)

    Google Scholar 

  27. Testaferri, L., Tiecco, M., Tingoli, M., Chianelli, D., Montanucci, M.: Simple syntheses of aryl alkyl thioethers and of aromatic thiols from unactivated aryl halides and efficient methods for selective dealkylation of aryl alkyl ethers and thioethers. Synthesis. 751–755 (1983)

    Google Scholar 

  28. Shaw, J.E.: Preparation of thiophenols from unactivated aryl chlorides and sodium alkanethiolates in N-methyl-2-pyrrolidone. J. Org. Chem. 56, 3728–3729 (1991)

    Google Scholar 

  29. Bieniarz, C., Cornwell, M.J.: A facile, high-yielding method for the conversion of halides to mercaptans. Tetrahedron Lett. 34, 939–942 (1993)

    Google Scholar 

  30. Yi, J., Fu, Y., Xiao, B., Cui, W.C., Guo, Q.-X.: Palladium-catalyzed synthesis of Aryl Thiols: Sodium Thiosulfate as a cheap and nontoxic Mercapto Surrogate. Tetrahedron Lett. 52, 205–208 (2011)

    Google Scholar 

  31. Argüello, J.E., Schmidt, L.C., Peñéñory, A.B.: “One-pot” two-step synthesis of aryl sulfur compounds by photoinduced reactions of thiourea anion with aryl halides. Org. Lett. 5, 4133–4136 (2003)

    Google Scholar 

  32. Takagi, K.: Synthesis of aromatic thiols from aryl iodides and thiourea by means of nickel catalyst. Chem. Lett. 14, 1307–1308 (1985)

    Google Scholar 

  33. Qiao, S., Xie, K., Qi, J.: Copper-catalyzed coupling of thiourea with aryl iodides: The direct synthesis of aryl thiols. Chin. J. Chem. 28, 1441–1443 (2010)

    Google Scholar 

  34. Liu, Y., Park, S.K., Xiao, Y., Chae, J.: Copper(ii)-catalyzed C-O coupling of aryl bromides with aliphatic diols: synthesis of ethers, phenols, and benzo-fused cyclic ethers. Org. Biomol. Chem. 12, 4747–4753 (2014)

    Google Scholar 

  35. Sawada, N., Itoh, T., Yasuda, N.: Efficient copper-catalyzed coupling of Aryl Iodides and Thiobenzoic Acid. Tetrahedron Lett. 47, 6595–6597 (2006)

    Google Scholar 

  36. Newman, M.S., Karnes, H.A.: The conversion of phenols to thiophenols via dialkylthiocarbamates. J. Org. Chem. 31, 3980–3984 (1966)

    Google Scholar 

  37. Flores-Figueroa, A., Arista, M.V., Talancon-Sanchez D., Castillo I.: Synthesis of 2, 4-disubstituted thiophenols and solid structures of thiocarbamate precursors. J. Braz. Chem. Soc. 16, 397–403 (2005)

    Google Scholar 

  38. Arnould, J.C., Didelot, M., Cadilhac, C., Pasquet, M.J.: Convenient synthesis of Aromatic Thiols from Phenols. Tetrahedron Lett. 37, 4523–4524 (1996)

    Google Scholar 

  39. Kopylova, B.V., Yashkina, L.V., Freidlina, P.Kh.: Arylation of thiourea with diazonium salts. Bull. Acad. Sci. USSR, chem. sci. 22, 2663–2665 (1973)

    Google Scholar 

  40. Petrillo, G., Novi, M., Garbarino, G., Filiberti, M.: The reaction between Arenediazonium Tetrafluoroborates and Alkaline Thiocarboxylates in DMSO: a convenient access to Aryl Thiolesters and other Aromatic Sulfur Derivatives. Tetrahedron. 45, 7411–7420 (1989)

    Google Scholar 

  41. Aliyev, I.A.: Chemistry and physical chemistry of arene thiols, their derivatives and analogs. Diss. Dr. Chem. Sci, Irkutsk (1990)

    Google Scholar 

  42. Becht, J.M., Wagner, A., Mioskowski, C.: Facile introduction of SH group on aromatic substrates via electrophilic substitution reactions. J. Org. Chem. 68, 5758–5761 (2003)

    Article  CAS  Google Scholar 

  43. Karyakin, Yu.V., Angelov I.I.: Pure chemicals. M.: Khimiya, p 408 (1974)

    Google Scholar 

  44. Dumont, J.M., Pumpf, P.: Recherches sur la preparation dessulfones mixtes aromatiques-aliphatigues. Bull. Soc. Chim. Fr. 1213–1218 (1962)

    Google Scholar 

  45. General practical course on organic chemistry, M.: Mir, p 678 (1965)

    Google Scholar 

  46. Harris, J.O., Vaughn, W.A.: Manufacture of thiophenols. Pat. US2792422 (A), (1957)

    Google Scholar 

  47. Vogt, C.: Ueber Benzylmercaptan und zweifach-schwefel benzyl. Liebigs Ann. Chem. 119, 142–153 (1861)

    Google Scholar 

  48. Greenfield, H.: Preparation of aryl thiols. Pat. US3399238 (A), (1968)

    Google Scholar 

  49. Divna, C., Dirk, P.: Electrochemical production of organic thiols. Pat. US4072584 (A), (1978)

    Google Scholar 

  50. Ratcliffe, C.T.: Catalytic reduction of aromatic sulfonyl halides with hydrogen sulfide to yield aromatic thiols. Pat. US4128586 (A), (1978)

    Google Scholar 

  51. Nose, A., Kudo, T.: Reductions of sodium borohydride. IV. Reduction of aromatic sulfonyl chlorides with sodium borohydride. Chem. Pharm. Bull. 35, 1770–1776 (1987)

    Google Scholar 

  52. Tietze, L.F., Eicher, T.: Reaktionen und synthesen im organisch-chemischen praktikum und forschungslaboratorium. Thieme, p 636 (1991)

    Google Scholar 

  53. Jacobson, S.E.: Hydrogen reduction of sulfonyl chlorides to thiols. Pat. US6667421(B2), (2003)

    Google Scholar 

  54. Kuliyev, A.M.: Chemistry and technology of additives to oils and fuels. M.: Khimiya, p. 358 (1972)

    Google Scholar 

  55. Kuliyev, A.M., Mamedov, F.N.: Derivatives of phenols and thiols, p. 225. Elm, Baku (1981)

    Google Scholar 

  56. Borodkin, V.F.: Chemistry of dyes. M.: Khimiya, p. 248 (1981)

    Google Scholar 

  57. Almasi, L., Hantz, A.A.: Procedeu de preparare a ariltiofenolilor. Pat. FR.53360, (1971)

    Google Scholar 

  58. Brown, H.C., Rao, B.C.S.: A new powerful reducing agent—sodium borohydride in the presence of aluminum chloride and other polyvalent metal halides. J. Am. Chem. Soc. 78, 2582–2588 (1956)

    Article  CAS  Google Scholar 

  59. Wagner, A.W.: Notiz uber line vereifachte methode zur darstellung von thiophenolen. Chem. Ber. 99, 375–376 (1966)

    CAS  Google Scholar 

  60. Bellale, E.V., Chaudhari, M.K., Akamanchi, K.G.: A simple, fast and chemoselective method for the preparation of arylthiols. Synthesis. 3211–3213 (2009)

    Google Scholar 

  61. Dmitriev, A.K.: Chemical disparity of hydrogen upon its release. Zh. Obshch. Khim. 18, 1267–1277 (1948)

    CAS  Google Scholar 

  62. Dmitriev, A.K.: Chemical disparity of hydrogen upon its release. II. Zh. Obshch. Khim. 22, 545–551 (1952)

    Google Scholar 

  63. Prins, H.J.: The mechanism of reduction. Part 1. Recl. Trav. Chim. Pays-Bas. 42, 473–481 (1923)

    Google Scholar 

  64. Vanderzee, C.E., Edgell, W.F.: The kinetics of the reduction of aromatic nitro compounds with tin and hydrochloric acid. J. Am. Chem. Soc. 71, 2916–2923 (1950)

    Article  Google Scholar 

  65. Brewster, J.H.: Mechanisms of reductions at metal surfaces. I. A general working hypothesis. J. Am. Chem. Soc. 76, 6361–6363 (1954)

    Google Scholar 

  66. Ookawa, A., Yokoyama, S., Soai, K.: Chemoselective reduction of diaryl bisulfides to thiols with sodium borohydride in mixed solvent containing methaxol. Synth. Commun. 16, 819–825 (1986)

    CAS  Google Scholar 

  67. Eom, T., Khan, A.: Disulfides as mercapto-precursors in nucleophilic ring opening reaction of polymeric epoxides: establishing equimolar stoichiometric conditions in a thiol–epoxy ‘click’ reaction. Chem. Commun. 56, 7419–7422 (2020)

    CAS  Google Scholar 

  68. Krishnamurthy, S., Aimino, D.: Rapid and selective reduction of functionalized aromatic disulfides with lithium tri-tert-butoxyaluminohydride. A remarkable steric and electronic control. Comparison of various hydride reagents. J. Org. Chem. 54, 4458–4462 (1989)

    Google Scholar 

  69. Lukesh, J.C., Palte, M.J., Raines, R.T.: A potent, versatile disulfide-reducing agent from aspartic acid. J. Am. Chem. Soc. 134, 4057–4059 (2012)

    Article  CAS  Google Scholar 

  70. Humphrey, R.E., Hawkins, J.M.: Reduction of aromatic disulfides with triphenylphosphine. Anal. Chem. 36, 1812–1814 (1964)

    CAS  Google Scholar 

  71. Cline, D.J., Redding, S.E., Brohawn, S.G., Psathas, J.N., Schneider, J.P., Thorpe, C.: New water-soluble Phosphines as reductants of Peptide and Protein Disulfide bonds: Reactivity and membrane permeability. Biochemistry. 43, 15195–15203 (2004)

    Google Scholar 

  72. Hotelling, E., Windgassen, R., Previc, E., Neuworth, N.: Notes—synthesis of mercaptophenols and alkyl derivatives. J. Org. Chem. 24, 1598–1600 (1959)

    Google Scholar 

  73. Ullrich, F.W., Fiege, H.: Method for producing aryl thiols by hydrogenating diaryldisulphides. Pat. WO9920602 (A1), (1999)

    Google Scholar 

  74. Bauman, E., Fromm, E.: Ueber Die Einwirkung Von Schwefelammonium Auf Acetophenon. Ber. 28, 907–914 (1895)

    Google Scholar 

  75. Bogert, M.T., Smidth, L.: A further study of the interaction of sulfur and para-toluidine in the presence of litharge: thio-para-toluidine and related compounds. J. Am. Chem. Soc. 50, 428–436 (1928)

    Article  CAS  Google Scholar 

  76. Cooke, W.H., Heilbron, I.M., Walker, G.H.: CCCVII.-meso-Thioanthracene derivatives. Part II. Dianthranyl disulphide and dianthranyl tetrasulphide. J. Chem. Soc. 127, 2250–2255 (1925)

    Google Scholar 

  77. Loven, J.M.: Ueber die thiomilchsauren und die thiodilactylsauren. J. Prakt. Chem. 29, 366–378 (1884)

    Article  Google Scholar 

  78. Bernthsen, A.: Studien in der Methylenblaugruppe. Amidodimethylanilinmercaptan und nahere derivate desselben. A. Aminodimethylanilinmercapta. Liebigs. Ann. Chem. 251, 23–26 (1889)

    Google Scholar 

  79. Fromm, E., Jorg, H.: Abkömmlinge Des Monothio-Athylenglykols Abkömmlinge Des Monothio-Athylenglykols. Ber. 58, 304–309 (1925)

    Google Scholar 

  80. Friedlander, P.: Ueber Schwefelhaltige Analoga Der Indigogruppe. Ber. 39, 1060–1066 (1906)

    Google Scholar 

  81. Schultz, C., Beyschlag, H.: Ueber die einwirkung von schwefelauf m-toluylendiamin. I. Ber. 42, 743–752 (1909)

    Google Scholar 

  82. Schwalbe, C.: Reduction vonaromatisen sulfosauren zu mercaptanen vermittelst alkalisulfhydrat. Ber. 39, 3l02–3105 (1906)

    Google Scholar 

  83. Burawoy, A., Turner, C.: o-Mercapto-azo-compounds. Part I. The coupling of tetrazotised 2 : 2[prime or minute]-diaminodiphenyl disulphide with [small beta]-naphthol. J. Chem. Soc. (Resumed) 469–477 (1950)

    Google Scholar 

  84. Parker, A.J., Kharasch, N.: The science of the sulfur–sulfur bond. Chem. Rev. 59, 583–628 (1959)

    Google Scholar 

  85. Kalinkin, M.I., Parnes, Z.N., Kursanov, D.N.: Disulfide cleavage during ionic hydrogenation. Dokl. Akad. Nauk. Ser. Khim. 180, 1370–1371 (1968)

    Google Scholar 

  86. Eckert-Maksic, M., Margetic, D.: Ionic Hydrogenation of Organosulfur Compounds. Energy Fuels. 5, 327–332 (1991)

    Google Scholar 

  87. Deryagina, E.N., Russavskaya, N.V., Papernaya, L.K., Levanova, E.P., Sukhomazova, E.N., Korchevin, N.A.: Synthesis of organochalcogen compounds in basic-reductive systems. Russ. Chem. Bull. 54, 2473–2483 (2005)

    Article  CAS  Google Scholar 

  88. Levanova, E.P., Grabelnykh, V.A., Elaev, A.V., Russavskaya, N.V., Klyba, L.V., Albanov, A.I., Tarasova, O.A., Korchevin, N.A.: The domino reaction of 2,3-dichloro-1-propene with diphenyl disulfide in the hydrazine hydrate—KOH system. Russ. J. Gen. Chem. 83, 1341–1344 (2013)

    Article  CAS  Google Scholar 

  89. Trofimov, B.A., Oparina, L.A., Gusarova, N.K., Belogorlova, N.A., Chernysheva, N.A., Ivanova, N.I., Parshina, L.N., Henkelmann, J.: An expedient synthesis of methyl vinyl sulfide from dimethyl disulfide and acetylene. J. Sulf. Chem. 25, 395–399 (2004)

    Article  CAS  Google Scholar 

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Aliyev, I.A., Trofimov, B.A., Oparina, L.A. (2021). Synthesis of Aromatic Thiols. In: Aromatic Thiols and Their Derivatives. Springer, Cham. https://doi.org/10.1007/978-3-030-69621-4_1

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