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DOI: 10.1055/s-0029-1217059
The Synthesis of 2-Cyano-cyanothioformanilides from 2-(4-Chloro-5H-1,2,3-dithiazol-5-ylideneamino)benzonitriles Using DBU
Publication History
Publication Date:
19 October 2009 (online)

Abstract
A series of 2-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)benzonitriles were prepared from the reaction of 4,5-dichloro-1,2,3-dithiazolium chloride (Appel salt) and the corresponding anthranilonitriles. Reaction of the 1,2,3-dithiazolimines with DBU (3 equiv) at -5 ˚C gave the corresponding 2-cyano-cyanothioformanilides in near quantitative yields. Treatment of 2-(4-chloro-5H-1,2,3-dithiazol-5-ylideneamino)benzonitrile with DBU (4 equiv) at -5 to +20 ˚C gave 2-isothiocyanatobenzonitrile in 96% yield. The latter compound was also formed directly from 2-cyano-cyanothioformanilide on treatment with DBU (1 equiv) in 95% yield. A tentative mechanism for the DBU-mediated dithiazole to cyanothioformanilide transformation is proposed and all compounds were fully characterized.
Key words
Appel salt - DBU - Cyanothioformanilide - isothiocyanate
- 1
Olin JF. inventors; US Patent 3287102.MissingFormLabel - 2a
El-Sharief AMSh.Ammar YA.Mohamed YA.El-Gaby MSA. Phosphorus, Sulfur Silicon Relat. Elem. 1999, 148: 117MissingFormLabel - 2b
Elagamey AA.El-Taweel FMA.El-Enein RANA. Phosphorus, Sulfur Silicon Relat. Elem. 2006, 181: 2155MissingFormLabel - 3a
Singer MS. inventors; US Patent 3655689.MissingFormLabel - 3b
Huang L.Graves MD. J. Heterocycl. Chem. 1987, 24: 1781MissingFormLabel - 3c
El-Sharief AMSh.Ammar YA.Zahran MA.Sabet HKh. Phosphorus, Sulfur Silicon Relat. Elem. 2004, 179: 267MissingFormLabel - 3d
Ketcham R.Schumann E. J. Org. Chem. 1980, 45: 3748MissingFormLabel - 3e
Kinzel P, andWilhelm M. inventors; Ger Offen. 3000130.MissingFormLabel - 3f
Kinzel P. inventors; Ger Offen. 3437853.MissingFormLabel - 3g
Ammar YA.El-Sharief AMSh.Ali MM.Mohamed YA.Mohamed ShI. Phosphorus, Sulfur Silicon Relat. Elem. 2000, 166: 173MissingFormLabel - 3h
El-Sharief AMSh.Ammar YA.Mohamed YA.Ali MM.El-Gaby MSA.Ali AS. Phosphorus, Sulfur Silicon Relat. Elem. 2001, 173: 39MissingFormLabel - 3i
El-Sharief AMSh.Ammar YA.El-Gaby MSA.Zahran MA.Khames AA. Afinidad 2003, 60: 47MissingFormLabel - 3j
El-Gaby MSA.El-Sharief AMSh.Atalla AA.El-Adasy AAAM. J. Chin. Chem. Soc. (Taipei) 2004, 51: 327MissingFormLabel - 3k
Kobayashi-Matsunaga Y.Ishii T.Hamaguchi T.Osada H.Sato M. Lett. Drug Des. Discovery 2005, 2: 224MissingFormLabel - 4a
Ketcham R. Synthesis 1980, 11: 869MissingFormLabel - 4b
El-Sharief AMSh.Ammar YA.Mohamed YA.El-Gaby MSA. Phosphorus, Sulfur Silicon Relat. Elem. 1999, 148: 215MissingFormLabel - 4c
El-Sharief AMSh.Ammar YA.Zahran MA.Sabet HKh. J. Chem. Res., Synop. 2003, 162MissingFormLabel - 5
Mahran AM.Hassan NA. Arch. Pharm. Res. 2006, 29: 46 - 6a
Deck LM.Papadopoulos EP.Smith KA. J. Heterocycl. Chem. 2003, 40: 885MissingFormLabel - 6b
El-Sharief AMS.Ammar YA.Mohamed YA.El-Gaby MSA. Heteroat. Chem. 2002, 13: 291MissingFormLabel - 6c
Besson T.Rees CW. J. Chem. Soc., Perkin Trans. 1 1996, 2857MissingFormLabel - 7a
Kattak I.Ketcham R.Schaumann E.Adiwidjaja G. J. Org. Chem. 1985, 50: 3431MissingFormLabel - 7b
El-Sharief AMSh.Hussein AM.Atalla AA.El-Gaby MSA.Hassan AA. Phosphorus, Sulfur Silicon Relat. Elem. 2000, 160: 141MissingFormLabel - 7c
El-Sharief AMSh.Hussein AM.El-Gaby MSA.Atalla AA.Ahmed AA. Phosphorus, Sulfur Silicon Relat. Elem. 2001, 170: 47MissingFormLabel - 7d
El-Sharief AMSh.Mahmoud FF.Taha NM.Ahmed EM. Phosphorus, Sulfur Silicon Relat. Elem. 2005, 180: 573MissingFormLabel - 7e
El-Sharief AMSh.El-Gaby MSA.Atalla AA.El-Adasy A.-BAAM. Afinidad 2003, 60: 475MissingFormLabel - 7f
El-Sharief AMS.El-Gaby MSA.Atalla AA.El-Adasy A.-BAAM. Heteroat. Chem. 2005, 16: 218MissingFormLabel - 7g
El-Sharief AMS.Al-Amri AM.Al-Raqa SY. J. Sulfur Chem. 2006, 27: 245MissingFormLabel - 8a
Friedrich K.Zamkanei M. Tetrahedron Lett. 1977, 18: 2139MissingFormLabel - 8b
Friedrich K.Zamkanei M. Chem. Ber. 1979, 112: 1867MissingFormLabel - 8c
Friedrich JD. J. Org. Chem. 1987, 52: 2442MissingFormLabel - 9
Friedrich K.Zamkanei M. Chem. Ber. 1979, 112: 1916 - 10
Friedrich K.Zamkanei M. Chem. Ber. 1979, 112: 1873 - 11
Grabenko AD.Danchenko MN.Pel’kis PS. J. Org. Chem. USSR (Engl. Transl.) 1972, 8: 532 - 12
El-Gaby MSA.Ammar YA.El-Sharief AMSh.Zahran MA.Khames AA. Heteroat. Chem. 2002, 13: 611 - 13a
Gonda J.Kristian P. Coll. Czech. Chem. Commun. 1988, 53: 1761MissingFormLabel - 13b
Walter W.Hell P.-M. Liebigs Ann. 1969, 727: 22MissingFormLabel - 13c
Walter W.Bode K.-D. Liebigs Ann. 1966, 698: 131MissingFormLabel - 13d
Reissert A.Brüggemann K. Chem. Ber. 1924, 57: 981MissingFormLabel - 14
Kantlehner W.Haug E.Isak H.Schulz W.Hippich S.Baur R.Hagen H. Chem. Ber. 1982, 115: 1721 - 15
Reissert A. Chem. Ber. 1904, 37: 3708 - 16
Besson T.Rees CW. J. Chem. Soc., Perkin Trans. 1 1995, 1659 - 17
Lee H.Kim K. Bull. Korean Chem. Soc. 1992, 13: 107 - 18
English RF.Rakitin OA.Rees CW.Vlasova OG. J. Chem. Soc., Perkin Trans. 1 1997, 201 - 19
Chang Y.-G.Kim K. Heterocycles 1999, 51: 2653 - 20
Lee H.-S.Chang Y.-G.Kim K. J. Heterocycl. Chem. 1998, 35: 659 - 21
Mohanta PK.Kim K. Tetrahedron Lett. 2002, 43: 3993 - 22
Pereira M.-F.Thiéry V.Besson T. Tetrahedron 2007, 63: 847 - 23
Lee H.-S.Kim K. Tetrahedron Lett. 1996, 37: 869 - 24a
Besson T.Emayan K.Rees CW. J. Chem. Soc., Chem. Commun. 1995, 1419MissingFormLabel - 24b
Besson T.Emayan K.Rees CW. J. Chem. Soc., Perkin Trans. 1 1995, 2097MissingFormLabel - 24c
Cottenceau G.Besson T.Gautier V.Rees CW.Pons A.-M. Bioorg. Med. Chem. Lett. 1996, 6: 529MissingFormLabel - 24d
Besson T.Rees CW.Cottenceau G.Pons A.-M. Bioorg. Med. Chem. Lett. 1996, 6: 2343MissingFormLabel - 24e
Le V.-D.Rees CW.Sivadasan S. Tetrahedron Lett. 2000, 41: 9407MissingFormLabel - 24f
Besson T.Guillard J.Rees CW. J. Chem. Soc., Perkin Trans. 1 2000, 563MissingFormLabel - 24g
Le V.-D.Rees CW.Sivadasan S. J. Chem. Soc., Perkin Trans. 1 2002, 1543MissingFormLabel - 24h
Besson T.Guillard J.Rees CW.Thiéry V. J. Chem. Soc., Perkin Trans. 1 1998, 889MissingFormLabel - 25
Besson T.Guillard J.Rees CW.Thérisod M. J. Chem. Soc., Chem. Commun. 1997, 881 - 26
Christoforou IC.Koutentis PA.Michaelidou SS. ARKIVOC 2006, (vii): 207 - 27
Oediger H.Möller F.Eiter K. Synthesis 1972, 591 - 28
Cowley AH. Acc. Chem. Res. 1984, 17: 386 - 29a
Fujii M.Ozaki K.Sekine M.Hata T. Tetrahedron 1987, 43: 3395MissingFormLabel - 29b
Reed R.Réau R.Dahan F.Bertrand G. Angew. Chem. Int. Ed. 1993, 32: 399MissingFormLabel - 29c
Lesnikowski ZJ.Zabawska D.Jaworska-Maslanka MM.Schinazi RF.Stec WJ. New J. Chem. 1994, 18: 1197MissingFormLabel - 29d
Dyer P.Guerret O.Dahan F.Baceiredo A.Bertrand G. J. Chem. Soc., Chem. Commun. 1995, 2339MissingFormLabel - 29e
Bouhadir G.Reed RW.Réau R.Bertrand G. Heteroat. Chem. 1995, 6: 371MissingFormLabel - 29f
Karsch HH.Rupprich T.Heckle M. Chem. Ber. 1995, 128: 959MissingFormLabel - 29g
Merckling FA.Rüedi P. Tetrahedron Lett. 1996, 37: 2217MissingFormLabel - 29h
Kers A.Stawiński J.Dembkowski L.Kraszewski A. Tetrahedron 1997, 53: 12691MissingFormLabel - 29i
Kers A.Kers I.Bollmark M.Stawinski J. Acta Chem. Scand. 1998, 52: 1405MissingFormLabel - 29j
Kers A.Kers I.Stawinski J. J. Chem. Soc., Perkin Trans. 2 1999, 2071MissingFormLabel - 29k
Blättner M.Nieger M.Ruban A.Schoeller WW.Niecke E. Angew. Chem. Int. Ed. 2000, 39: 2768MissingFormLabel - 29l
Ionkin AS.Marshall WJ. Heteroat. Chem. 2003, 14: 197MissingFormLabel - 29m
Dąbkowski W.Tworowska I.Kazimierczak Ł.Michalski J. Pol. J. Chem. 2005, 79: 467MissingFormLabel - 30a
Richter R. Chem. Ber. 1968, 101: 3002MissingFormLabel - 30b
House HO.DeTar MB.VanDerveer D. J. Org. Chem. 1979, 44: 3793MissingFormLabel - 30c
McCoy LL.Mal D. J. Org. Chem. 1981, 46: 1016MissingFormLabel - 30d
Alder RW.Sessions RB. Tetrahedron Lett. 1982, 23: 1121MissingFormLabel - 30e
Juneja TR.Garg DK.Schäfer W. Tetrahedron 1982, 38: 551MissingFormLabel - 30f
Forlani L.Sintoni M.Todesco PE. J. Chem. Res., Synop. 1986, 344MissingFormLabel - 30g
Collina G.Forlani L. J. Phys. Org. Chem. 1988, 1: 351MissingFormLabel - 30h
Forlani L.Cimarelli C. J. Phys. Org. Chem. 1989, 2: 653MissingFormLabel - 30i
Reid JG.Runge JMR. Tetrahedron Lett. 1990, 31: 1093MissingFormLabel - 30j
Reisch J.Iding M.von Bassewitz I. Monatsh. Chem. 1993, 124: 1225MissingFormLabel - 30k
Schenk WA.Urban P.Dombrowski E. Chem. Ber. 1993, 126: 679MissingFormLabel - 30l
Chambers RD.Roche AJ.Batsanov AS.Howard JAK. J. Chem. Soc., Chem. Commun. 1994, 2055MissingFormLabel - 30m
Lammers H.Cohen-Fernandes P.Habraken CL. Tetrahedron 1994, 50: 865MissingFormLabel - 30n
Ma L.Dolphin D. Tetrahedron 1996, 52: 849MissingFormLabel - 30o
Johnson MG.Foglesong RJ. Tetrahedron Lett. 1997, 38: 7003MissingFormLabel - 30p
Lönnqvist J.-ES.Jalander LF. J. Chem. Res., Miniprint 1999, 0430MissingFormLabel - 31
Sekine M.Kume A.Hata T. Tetrahedron Lett. 1981, 22: 3617 - 32a
Bard RR.Strauss MJ. J. Am. Chem. Soc. 1975, 97: 3789MissingFormLabel - 32b
Miller J.Miyata Y.Sakazaki E.de Santos TW. J. Chem. Res., Synop. 1986, 396MissingFormLabel - 33a
Appel R.Janssen H.Siray M.Knoch F. Chem. Ber. 1985, 118: 1632MissingFormLabel - 33b
Koutentis PA. Molecules 2005, 10: 346MissingFormLabel