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Synlett 2014; 25(17): 2475-2479
DOI: 10.1055/s-0034-1379041
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© Georg Thieme Verlag Stuttgart · New York

Substituent Effects and Structural Features of α,α-Dicyanoolefins and Ketene Dithioacetals on Directing Polyfunctionalized 2,6-Dicyanoanilines or Pyrazolo[1,5-a]pyridines

Abdolali Alizadeh*
Department of Chemistry, Tarbiat Modares University, P. O. Box 14115-175, Tehran, Iran   Fax: +98(21)88006544   Email: abdol_alizad@yahoo.com   Email: aalizadeh@modares.ac.ir
,
Seyed Yasub Hosseini
Department of Chemistry, Tarbiat Modares University, P. O. Box 14115-175, Tehran, Iran   Fax: +98(21)88006544   Email: abdol_alizad@yahoo.com   Email: aalizadeh@modares.ac.ir
,
Amir Hossein Vahabi
Department of Chemistry, Tarbiat Modares University, P. O. Box 14115-175, Tehran, Iran   Fax: +98(21)88006544   Email: abdol_alizad@yahoo.com   Email: aalizadeh@modares.ac.ir
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Publication History

Received: 15 June 2014

Accepted after revision: 06 August 2014

Publication Date:
10 September 2014 (online)

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Abstract

An efficient and facile synthesis of pyrazolo[1,5-a]pyridine and polyfunctionalized 2,6-dicyanoaniline derivatives via vinylogous Michael addition of cyclic or acyclic α,α-dicyanoolefins to electron-deficient ketene dithioacetals in the presence of hydrazine at room temperature is described. The prominent feature of this one-pot procedure is an apparent dichotomy in the nature of products, which is dictated by the structure and functionality of substrates.

Key words

α,α-dicyanoolefins - ketene dithioacetals - pyrazolo[1,5-a]pyridines - 2,6-dicyanoaniline - vinylogous Michael addition

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    for this article is available online at http://www.thieme-connect.com/products/ejournals/journal/ 10.1055/s-00000083.
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  • 18 2,7-Diamino-5-phenylpyrazolo[1,5-a]pyridine-3,6-dicarbonitrile (3a) – General Procedure for the Preparation of Compounds 3a,b,e,f and 4a–d To a solution of α,α-dicyanoolefin 1 (1 mmol) and ketene dithioacetal 2 (1 mmol) in EtOH (3 mL) was added Et3N (1 mmol), and the solution was stirred for 30 min at r.t. Then, excess hydrazine was added to mixture. Upon completion (2 h, monitoring by TLC), the mixture was filtered and the precipitate washed with EtOH (2 × 4 mL) to afford the pure products 3a,b,e,f and 4a–d. Representative Analytical Data 2,7-Diamino-5-(phenyl)pyrazolo[1,5-a]pyridine-3,6-dicarbonitrile (3a) White powder; yield 0.24 g, (87%); mp >300 °C. IR (KBr): 3426, 3331 and 3234 (NH2), 2209 (CN), 1612, 1543 and 1490 (Ar) cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 6.56 (s, 2 H, NH2), 6.66 (s, 1 H, CH), 7.52 (t, 2 H, 3 J HH = 6.0 Hz, 2 CH meta of Ph), 7.54 (t, H, 3 J HH = 6.0 Hz, CH para of Ph), 7.61 (d, 2 H, 3 J HH = 5.6 Hz, 2 CH ortho of Ph), 7.82 (s, 2 H, NH2). 13C NMR (100.0 MHz, DMSO-d 6): δ = 69.29 (C6CN), 75.14 (C3CN), 100.16 (CH), 114.17(CN), 116.62 (CN), 128.40 (2 CH meta of Ph), 128.55 (2 CH ortho of Ph), 129.11 (CH para of Ph), 137.03 (C5-Ph), 143.50 (C ipso of Ph), 144.31 (C3a), 146.95 (C7-NH2), 160.17 (C2-NH2). MS: m/z = 274 (46) [M+], 246 (3), 219 (7), 204 (7), 194 (8), 178 (9), 164 (23), 151 (19), 140 (35), 127 (36), 100 (37), 88 (38), 77 (100), 63 (92), 51 (84). Anal. Calcd (%) for C15H10N6: C, 65.69; H, 3.67; N, 30.64. Found: C, 65.58; H, 3.57; N, 30.56. 2-Amino-4-methylsulfanyl-6-phenylisophthalonitrile (4a) White powder; yield 0.20 g (76%); mp 248–250 °C. IR (KBr): 3462, 3368 and 3229 (NH2), 2212 (CN), 1629, 1554 and 1432 (Ar) cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 2.61 (s, 3 H, CH3), 6.58 (s, 1 H, CH), 6.82 (s, 2 H, NH2), 7.52–7.59 (m, 5 H, CH of Ar). 13C NMR (100.0 MHz, DMSO-d 6): δ = 13.93 (SCH3), 91.28 (C1 and C3), 112.80 (CH), 114.46 (CN), 116.14 (CN), 128.41 (2 CH meta of Ph), 128.50 (2 CH ortho of Ph), 129.42 (CH para of Ar), 137.61 (C ipso of Ph), 149.67 (C6), 151.17 (CSCH3), 153.48 (C2-NH2). MS: m/z = 265 (100) [M+], 249 (6), 232 (50), 220 (12), 205 (24), 191 (13), 178 (8), 164 (15), 152 (13), 140 (8), 128 (4), 113 (4), 102 (4), 88 (4), 77 (13), 63 (8), 51 (15). Anal. Calcd (%) for C15H11N3S: C, 67.90; H, 4.18; N, 15.84. Found: C, 67.81; H, 4.19; N, 15.78