Synlett 2020; 31(09): 895-898
DOI: 10.1055/s-0040-1708001
letter
© Georg Thieme Verlag Stuttgart · New York

Hantzsch-Like One-Pot Three-Component Synthesis of Heptaazadicyclopenta[a,j]anthracenes: A New Ring System

Amr M. Abdelmoniem
a   Department of Chemistry, Faculty of Science, Cairo University, P.O. 12613 Giza, Egypt   Email: ismail_shafy@yahoo.com
,
b   Organometallic and Organometalloid Chemistry Department, National Research Centre, 12622 Cairo, Egypt
,
Muhammed A. Ramadan
a   Department of Chemistry, Faculty of Science, Cairo University, P.O. 12613 Giza, Egypt   Email: ismail_shafy@yahoo.com
,
Said A. S. Ghozlan
a   Department of Chemistry, Faculty of Science, Cairo University, P.O. 12613 Giza, Egypt   Email: ismail_shafy@yahoo.com
,
a   Department of Chemistry, Faculty of Science, Cairo University, P.O. 12613 Giza, Egypt   Email: ismail_shafy@yahoo.com
› Author Affiliations
Further Information

Publication History

Received: 27 January 2020

Accepted after revision: 02 March 2020

Publication Date:
17 March 2020 (online)


Abstract

A concise and efficient approach to novel tetrahydroheptaazadicyclopenta[a,j]anthracene-5,7-diones, by the reaction of aldehydes with two moles of 7-amino-2-methyl-3-phenylpyrazolo[1,5-a]pyrimidin-5-one is reported. Also, pyrazolo[1,5-a]pyrido[3,2-e]pyrimidine-7-carbonitrile derivatives were prepared by a three-component reaction of aldehydes, 7-amino-2-methyl-3-phenylpyrazolo[1,5-a]pyrimidin-5-one, and 3-aminocrotononitrile.

Supporting Information

 
  • References and Notes

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  • 27 Heptaazadicyclopenta[a,j]anthracene-5,7-diones 7ae; General Procedure A mixture of 7-amino-2-methyl-3-phenylpyrazolo[1,5-a]pyrimidin-5(4H)-one (5; 0.54 g, 2.25 mmol) and the appropriate aromatic aldehyde 6 (1 mmol) was refluxed in glacial HOAc (15 mL) for 12 h. The solvent was evaporated under reduced pressure and the residue was treated with 2 N aq NaHCO3 (25 mL). The collected crude products were purified by crystallization from EtOH–1,4-dioxane (2:1; 15 mL). 6-(4-Chlorophenyl)-2,10-dimethyl-3,9-diphenyl-4,6,8,11a,12,12b-hexahydro-1,4,8,11,11a,12,12b-heptaazadicyclopenta[a,j]anthracene-5,7-dione (7c) Yellow powder; yield: 0.48 g (79%); mp 240–242 °C. IR (KBr): 3394 (2NH), 3316 (br, 2NH2) 1651 (2CO) cm–1. 1H NMR (400 MHz, DMSO-d 6): δ = 2.30 (s, 6 H, 2CH 3), 5.83 (s, 1 H, CH), 7.17–7.42 (m, 14 H, ArH), 11.87 (br s, 3 H, 3NH). 13C NMR (100 MHz, DMSO-d 6): δ = 13.7, 34.9, 88.6, 101.9, 126.5, 128.6, 128.8, 129.3, 129.4, 131.7, 132.9, 141.8, 145.3, 149.7, 161.1, 167.5. MS (EI, 70 eV): m/z 586 [M]+. Anal. Calcd for C33H24ClN7O2: C, 67.63; H, 4.13; N, 16.73. Found: C, 67.82; H, 4.34; N, 16.92.
  • 28 Pyrazolo[1,5-a]pyrido[3,2-e]pyrimidine-7-carbonitriles 14ac; General Procedure A mixture of 7-amino-2-methyl-3-phenylpyrazolo[1,5-a]pyrimidin-5(4H)-one (5; 0.24 g, 1 mmol), the appropriate aromatic aldehyde 6 (1 mmol), and 3-aminocrotononitrile (13; 0.08 g, 1 mmol) in anhyd pyridine (10 mL) was refluxed for 5 h. The solvent was evaporated under reduced pressure and the residue was treated with 0.2 N aq HCl (25 mL). The collected crude products were purified by crystallization from 2:1 EtOH­–1,4-dioxane (15 mL). 2,8-Dimethyl-5-oxo-3,6-diphenyl-4,5,6,9-tetrahydropyrazolo[1,5-a]pyrido[3,2-e]pyrimidine-7-carbonitrile (14a) Yellow powder; yield: 0.32 g (82%); mp >300 °C. IR (KBr): 3402 (br, 2NH), 2206 (CN), 1622 (CO) cm–1. 1H NMR (300 MHz, DMSO-d 6): δ = 2.25 (s, 3 H, CH 3), 2.34 (s, 3 H, CH 3), 4.61 (s, 1 H, CH), 7.21–7.41 (m, 10 H, ArH), 10.50 (br s, 1 H, NH), 11.60 (br s, 1 H, NH). 13C NMR (75 MHz, DMSO-d 6): δ = 12.8, 17.9, 40.3, 86.5, 89.0, 107.2, 120.9, 126.4, 126.8, 127.6, 128.3, 128.4, 129.1, 129.3, 130.2, 138.9, 144.7, 146.6, 155.2, 159.3. MS (EI, 70 eV): m/z 393 [M]+. Anal. Calcd for C24H19N5O: C, 73.27; H, 4.87; N, 17.80. Found: C, 73.47; H, 4.69; N, 17.68.