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

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Abstract

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.

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References

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    CAS  Google Scholar 

  • 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 

  • 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.

    Article  Google Scholar 

  • 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 

  • 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.

    Article  CAS  Google Scholar 

  • 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 

  • 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.

    Article  Google Scholar 

  • Döpp, D., Jüschke, S., & Henkel, G. (2002). Dicyanomethylene compounds as cyanation reagents. Zeitschrift für Naturforschung B, 57b, 460–470.

    Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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 

  • 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 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    CAS  Google Scholar 

  • 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.

    Article  Google Scholar 

  • Kalinowski, H. O., Berger, S. & Braun, S. (1984). 13 C NMR-Spektroskopie. Stuttgart, Germany: Thieme Verlag.

    Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

  • 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.

    Article  Google Scholar 

  • 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.

    CAS  Google Scholar 

  • 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.

    Article  CAS  Google Scholar 

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Authors and Affiliations

  1. Chemistry Department, Faculty of Science, Minia University, 61519, El-Minia, Egypt

    Alaa A. Hassan, Ahmed M. Nour El-Din, Fathy F. Abdel-Latif & Sara M. Mostafa

  2. Institute of Organic Chemistry, Karlsruhe Institute of Technology, Fritz-Haber-Weg 6, 76131, Karlsruhe, Germany

    Stefan Bräse

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  1. Alaa A. Hassan
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  2. Ahmed M. Nour El-Din
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  3. Fathy F. Abdel-Latif
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  4. Sara M. Mostafa
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  5. Stefan Bräse
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Correspondence to Alaa A. Hassan.

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Hassan, A.A., Nour El-Din, A.M., Abdel-Latif, F.F. et al. Formation of dioxospiroindene[1,3]thiazine and thioxoindeno[2,1-d]imidazolone derivatives from alkenylidene-hydrazinecarbothioamides. Chem. Pap. 66, 295–303 (2012). https://doi.org/10.2478/s11696-012-0145-3

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