Chemical Papers

, Volume 66, Issue 4, pp 295–303 | Cite as

Formation of dioxospiroindene[1,3]thiazine and thioxoindeno[2,1-d]imidazolone derivatives from alkenylidene-hydrazinecarbothioamides

  • Alaa A. HassanEmail author
  • Ahmed M. Nour El-Din
  • Fathy F. Abdel-Latif
  • Sara M. Mostafa
  • Stefan Bräse
Original Paper


The reaction of (substituted) alkenylidene-hydrazinecarbothioamides with 2-(1,3-dioxo-2,3-dihydro-1H-inden-2-ylidene)propanedinitrile led to the formation of 1,3-dioxospiroindene[1,3]-thiazine and thioxoindeno[2,1-d]imidazolone derivatives in modest yields. In addition, 1,3-dihydroxyindan-2-ylidenepropanedinitrile was found. Explanations of these conversions involving nucleophilic reactions and condensations are presented.


alkenylidene-hydrazinecarbothioamides dioxospiroindene[1,3]thiazine thioxoindeno [2,1-d]imidazolone 


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  1. Aly, A. A., Brown, A. B., Ramadan, M., Abdel-Aziz, M., Abuo-Rahma, G. E. A. A., Radwan, M. F., & Gamal-Eldeen, A. M. (2010). Selectivity of N-aroyl-N′-arylthioureas towards 2-(1,3-dioxo-1H-inden-2(3H)-ylidene)malononitrile. New synthesis of (Z)-N-((E)-4-amino-1-aryl-5-cyano-6-oxo-1H-indeno[1,2-d][1,3]thiazepine-2(6H)-ylidene)-4-arylamides of antitumor and antioxidant activities. Journal of Heterocyclic Chemistry, 47, 503–508. DOI: 10.1002/jhet.344.CrossRefGoogle Scholar
  2. Aziz, S. A., Anwar, H. F., El-Apasery, M. A., & Elnagdi, M. H. (2007). Studies with pyridazines and condensed pyridazines: Routes for synthesis of 3-amino-5-aryl-2,5-dihydropyridazine, 10aH-pyridazino[1,6-a]quinazoline and thieno[3,4-d]pyridazinone. Journal of Heterocyclic Chemistry, 44, 877–881. DOI: 10.1002/jhet.5570440421.CrossRefGoogle Scholar
  3. Bespalov, B. P., Getmanova, E. V., & Abolin, A. G. (1980). Substitution of nitrile groups in a dicyanomethylene fragment. Journal of Organic Chemistry of the USSR, 16, 1896–1901.Google Scholar
  4. Boila-Göckel, A., Fabian, W. M. F., & Junek, H. (1996). Synthesis with nitriles, XCVIII synthesis and characterization of (aminocyanomethylene)indanedione and -pyrazolone chromoinophores as extractants for alkali metal ions. Liebigs Annalen, 3, 397–402. DOI: 10.1002/jlac.199619960315.Google Scholar
  5. Chaterjee, S. (1969). Studies of the charge-transfer complexes of 2- dicyanomethyleneindan-1,3-dione. Journal of the Chemical Society (B): Physical Organics, 1969, 725–729. DOI: 10.1039/j29690000725.CrossRefGoogle Scholar
  6. Darehkordi, A., Saidi, K., & Islami, M. R. (2007). Preparation of heterocyclic compounds by reaction of dimethyl and diethyl acetylene dicarboxylate (DMAD, DEAD) with thiosemicarbazone derivatives. ARKIVOC, 2007(i), 180–188.Google Scholar
  7. Diez, E., Fernández, R., Gasch, C., Lassaletta, J. M., Llera, J. M., Martín-Zamora, E., & Vásquez, J. (1997). Formaldehyde dialkylhydrazones as neutral formyl anion and cyanide equivalents: Nucleophilic addition to conjugated enones. Journal Organic Chemistry, 62, 5144–5155. DOI: 10.1021/jo970481d.CrossRefGoogle Scholar
  8. Döpp, D., Gomaa, M. A., Henkel, G., & Nour El-Din, A. M. (1996). Reaction of N 1,N 2-diarylamidines with dicyanomethylene compounds. Journal of the Chemical Society, Perkin Transactions 2,4, 573–576. DOI: 10.1039/p29960000573.Google Scholar
  9. Döpp, D., Hassan, A. A., Nour El-Din, A. M., Mourad, A. E., Lehmann, C. W., & Rust, J. (2006). Reaction of (1,3-dioxo-2,3-dihydro-1H-inden-2-ylidene)propanedinitrile with N-arylisoindolines. Tetrahedron, 62, 11618–11626. DOI: 10.1016/j.tet.2006.09.070.CrossRefGoogle Scholar
  10. Döpp, D., Jüschke, S., & Henkel, G. (2002). Dicyanomethylene compounds as cyanation reagents. Zeitschrift für Naturforschung B, 57b, 460–470.Google Scholar
  11. El-Kaïm, L., Gautier, L., Grimaud, L., & Michaut, V. (2003). New insight into the azaenamine behaviour of N-arylhydrazones: First aldol and improved Mannich reactions with unactivated aldehydes. Synlett, 12, 1844–1846. DOI: 10.1055/s-2003-41441.CrossRefGoogle Scholar
  12. Ernst, S., Richter, C., Hobert, A., Mariam, G. G., & Schulze, K. (1995). Synthesis of new 1,2,4-triazolines and 1,3,4-thiadiazolines from bithioureas. Journal of Heterocyclic Chemistry, 32, 275–281. DOI: 10.1002/jhet.5570320147.CrossRefGoogle Scholar
  13. Gewald, K., & Schindler, R. (1990). Cyclisierungen mit Cyanthioacetamid in Gegenwart von Schwefel. Journal für Prak tische Chemie, 332, 223–228. DOI: 10.1002/prac.19903320213.CrossRefGoogle Scholar
  14. Gomaa, M. A., & Döpp, D. (1998). Reaction of N 1,N 2-diarylacetamidines with (2,4,7-trinitro-9H-fluoren-9-ylidene) propandinitrile. Journal of Heterocyclic Chemistry, 35, 339–341. DOI: 10.1002/jhet.5570350214.CrossRefGoogle Scholar
  15. Gomaa, M. A., Hassan, A. A., & Shehatta, H. S. (2006). Synthesis of novel thiazole and pyrrolothiadiazine derivatives from aldehyde thiosemicarbazones. Heteroatom Chemistry, 17, 261–266. DOI: 10.1002/hc.20198.CrossRefGoogle Scholar
  16. Grammaticakis, P. (1950). The spectral study of the nitrogen derivatives of aromatic aldehydes and ketones. VI. Thiosemicarbazones and 4-phenylthiosemicarbazones of aldehydes. Bulletin de la Société Chimique de France, 1950, 504–506. (in French)Google Scholar
  17. Grammaticakis, P. (1953). The absorption in the middle ultraviolet and visible of α,β-disubstituted hydrazines and their oxidation product. Diacylhydrazine, diacyldiimides, and 1,3,4-oxadiazoles. Bulletin de la Société Chimique de France, 1953, 86–87. (in French)Google Scholar
  18. Gruttadauia, M., Buccheri, F., Cusmano, G., Lo Meo, P., Noto, R., & Werber, G. (1993). Oxidation cyclization of some aldehyde semicarbazones induced by metallic salts. Journal of Heterocyclic Chemistry, 30, 765–770. DOI: 10.1002/jhet.5570300327.CrossRefGoogle Scholar
  19. Hafez, E. A. A., Abdul Galil, F. M., Sherif, S. M., & Elnagdi, M. H. (1986). Nitriles in heterocyclic synthesis. A novel synthesis of spiropyran-4-ylindolidene derivatives. Journal of Heterocyclic Chemistry, 23, 1375–1378. DOI: 10.1002/jhet.5570230523.CrossRefGoogle Scholar
  20. Hanefeld, W., Schlitzer, M., Debski, N., & Euler, H. (1996). 3-(2,5-Dioxopyrrolidin-1-yl), 3-(2,6-dioxopiperidin-1-yl), and 3-(1,3-dioxoisoindolin-2-yl)rhodanines. A novel type of rhodanine derivatives. Journal of Heterocyclic Chemistry, 33, 1143–1146. DOI: 10.1002/jhet.5570330423.CrossRefGoogle Scholar
  21. Hassan, A. A., Aly, A. A., & El-Sheref, E. M. (2007). Nucleophilic reactions of 1-substituted-2,5-dithiobiureas with chlorinated benzo- and naphthoquinones as well as (1,3-dioxo-2,3-dihydro-1(H)-inden-2-ylidene)propanedinitrile. ARKIVOC, 2007(xiv), 229–244.Google Scholar
  22. Hassan, A. A., & Döpp, D. (2006). Thermolysis of N,N″-1,ω-alkenediyl-bis[N′-organylthiourea] derivatives. Journal of Heterocyclic Chemistry, 43, 593–598. DOI: 10.1002/jhet.5570430311.CrossRefGoogle Scholar
  23. Hassan, A. A., Ibrahim, Y. R., & Shawky, A. M. (2009). Dicyanomethylene compounds and heterocyclization of substituted carbohydrazides. Journal of Heterocyclic Chemistry, 46, 616–622. DOI: 10.1002/jhet.115.CrossRefGoogle Scholar
  24. Hassan, A. A., Ibrahim, Y. R., Shawky, A. M., & Döpp, D. (2006). Reaction of 4-substituted thiosemicarbazides with (2,4,7-trinitro-9H-fluoren-9-ylidene)propanedinitrile. Journal of Heterocyclic Chemistry, 43, 849–854. DOI: 10.1002/jhet.5570430406.CrossRefGoogle Scholar
  25. Hassan, A. A., Mohamed, N. K., Aly, A. A., & Mourad, A. E. (1997). A novel synthesis of heterocycles from thiocarbohydrazides. Monatshefte für Chemie, 128, 61–70. DOI: 10.1007/bf00807639.CrossRefGoogle Scholar
  26. Hassan, A. A., Mourad, A. E., & Abou-Zeid, A. H. (2008a). Dicyanomethylene compounds and heterocyclization of acylthiosemicarbazides. Journal of Heterocyclic Chemistry, 45, 323–328. DOI: 10.1002/jhet.5570450205.CrossRefGoogle Scholar
  27. Hassan, A. A., & Shehata, H. S. (2007). Indenoxadiazine, indenopyrazole and spiro triazole derivatives from (substituted ylidene)-N-phenylhydrazine carbothioamides. Journal of Chemical Research, 2007, 629–635. DOI: 10.3184/0308234 07x262472.CrossRefGoogle Scholar
  28. Hassan, A. A., Shehata, H. S., & Döpp, D. (2008b). Formation of 5-alkylidenepyrazol-4-(1H)-ones and 3-amino-6-aryl-5-cyanopyridazine-4-carboxylates form arenealdehyde thiosemicarbazones and unsaturated 1,2-diesters. Journal of Chemical Research, 2008, 725–730. DOI: 10.3184/030823408x390208.CrossRefGoogle Scholar
  29. Invidiata, F. P., Furná, G., Lampronti, I., & Simoni, D. (1997). 1,2,4-Triazoles. Improved synthesis of 5-substituted 4-amino-3-mercato-(4H)-1,2,4-triazoles and a facile route to 3,6-disubstituted 1,2,4-traiazolo[3,4-b][1,3,4]thiadiazoles. Journal of Heterocyclic Chemistry, 34, 1255–1258. DOI: 10.1002/jhet.5570340427.CrossRefGoogle Scholar
  30. Junek, H., Aigner, H., & Fischer-Colbrie, H. (1972). Farbstoffe durch Amin-HCN-Austauschreaktion am 2-Dicyanmethylen-1,3-indandion, I Synthesen mit Nitrilen, 32. Mitt. Monatshefte für Chemie, 103, 639–648. DOI: 10.1007/bf00905425.CrossRefGoogle Scholar
  31. Junek, H., Fischer-Colbrie, H., & Hermetter, A. (1977). Synthesen mit Nitrilen, XLVIII. Merocyanine und Oxonole von Phenyl-indanyliden-acetonitrilen. Zeitschrift für Naturforschung (B), 32b, 898–903.Google Scholar
  32. Junek, H., Klad, M., Biza, P., Geringer, M., & Sterk, H. (1990). Synthesen mit Nitrilen, LXXXVII. Chromoinophore durch Addition von N-Phenyl(aza-15-krone-5) an reaktive Dicyanomethyleneverbindungen. Liebigs Annalen der Chemie, 8, 741–744. DOI: 10.1002/jlac.1990199001139.CrossRefGoogle Scholar
  33. Kalinowski, H. O., Berger, S. & Braun, S. (1984). 13 C NMR-Spektroskopie. Stuttgart, Germany: Thieme Verlag.Google Scholar
  34. Noto, R., Gruttadauria, M., Lo Meo, P., Frenna, V., & Werber, G. (1995). A study of the mechanism of the oxidation cyclization of benzaldehyde semicarbazones induced by cupric perchlorate in acetonitrile. Journal of Heterocyclic Chemistry, 32, 1277–1282. DOI: 10.1002/jhet.5570320430.CrossRefGoogle Scholar
  35. Noto, R., Lo Meo, P., Gruttadauria, M., & Werber, G. (1996). A quantitative study of substituted effects on oxidative cyclization of some 2-methylsubstituted aldehydes. Thiosemicarbazones induced by ferric chloride. Journal of Heterocyclic Chemistry, 33, 863–872. DOI: 10.1002/jhet.5570330353.CrossRefGoogle Scholar
  36. Noto, R., Lo Meo, P., Gruttadauria, M., & Werber, G. (1999). A quantitative study of substituted effects on oxidative cyclization of some 2-aryl-substituted aldehyde thiosemicarbazones induced by ferric chloride and cupric perchlorate. Journal of Heterocyclic Chemistry, 36, 667–674. DOI: 10.1002/jhet.5570360315.CrossRefGoogle Scholar
  37. Rappoport, Z., & Ladkani, D. (1973). Nucleophilic attacks on carbon-carbon double bonds. Part XVIII. Reaction of 2-dicyanomethyleneindane-1,3-dione with anilines in acetonitriles. Journal of the Chemical Society, Perkin Transaction 2,7, 1045–1052. DOI: 10.1039/p29730001045.CrossRefGoogle Scholar
  38. Shah, I. D., & Trivedi, J. P. (1963). Synthesis of thiazolidones. I. Synthesis of 4-oxo-3-aryl-5-substituted thiazolin-2-ylhydrazones. Journal of the Indian Chemical Society, 40, 889–893.Google Scholar
  39. Tsoungas, P. G., & Diplas, A. I. (2003). Oxidation cyclization in the synthesis of 5- and 6-membered N,O-heterocycles. Heteroatom Chemistry, 14, 642–670. DOI: 10.1002/hc.10200.CrossRefGoogle Scholar

Copyright information

© Institute of Chemistry, Slovak Academy of Sciences 2012

Authors and Affiliations

  • Alaa A. Hassan
    • 1
    Email author
  • Ahmed M. Nour El-Din
    • 1
  • Fathy F. Abdel-Latif
    • 1
  • Sara M. Mostafa
    • 1
  • Stefan Bräse
    • 2
  1. 1.Chemistry Department, Faculty of ScienceMinia UniversityEl-MiniaEgypt
  2. 2.Institute of Organic ChemistryKarlsruhe Institute of TechnologyKarlsruheGermany

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