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Synlett 2002(5): 0823-0825
DOI: 10.1055/s-2002-25346
LETTER
© Georg Thieme Verlag Stuttgart · New York

A Facile Synthesis of 4-Diarylmethyl-1-(2H)phthalazinones from 2,2-Diaryl-1,3-indanediones

Sandip Kumar Kundu, Animesh Pramanik*, Amarendra Patra*
Department of Chemistry, University of Calcutta, 92, Acharya Prafulla Chandra Road, Kolkata -700 009, India
e-Mail: animesh@cucc.ernet.in; e-Mail: amarendra@satyam.net.in;
Further Information

Publication History

Received 15 March 2002
Publication Date:
07 February 2007 (online)

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Abstract

Refluxing of 2,2-diaryl-1,3-indanediones in hydrazine hydrate for a brief period affords 4-diarylmethyl-1-(2H)phthalazinones in very high yield.

Key words

2,2-diaryl-1,3-indanediones - 4-diarylmethyl-1-(2H)-phthalazinones - arylation - heterocycles - nucleophilic additions

    References

  • 1 Engelbrecht HJ, and Lenke D. inventors; German (East) patent  19629.  ; Chem. Abstr. 1961, 55, 22346.
  • 2 Abd El-Fattah B. Al-Ashmani MI. El-Feky S. Roeder E. Egypt. J. Pharm. Sci.  1987,  28:  383 
    Search in Google Scholar
  • 3 Horn H, Unverferth K, Laban G, and Lohmann D. inventors; German (East) patent  286354.  ; Chem. Abstr. 1991 , 115, 8820.
  • 4 inventors; Fujsawa Pharmaceutical Co. Ltd.; Japan patent  62252774.  ; Chem. Abstr. 1988, 109, 6531.
  • 5 Marcaccini S. Pepino R. Polo C. Pozo MC. Synthesis  2001,  85 
    Thieme Connect
  • 6 Epsztajn J. Malinowski Z. Brzezinki JZ. Karzatka M. Synthesis  2001,  14:  2085 
    Thieme ConnectSearch in Google Scholar
  • 7 Saito Y. Sakamoto T. Kikugawa Y. Synthesis  2001,  2:  221 
    Search in Google Scholar
  • 8 Abdel-Khalik MM. Agamy MS. Elnagdi MH. Synthesis  2001,  12:  1861 
    Thieme ConnectSearch in Google Scholar
  • 9 Patel NR. In Condensed pyridazines Including Cinnolines and Phthalazines   Castle RN. Wiley-Interscience; New York: 1973.  p.383-385  
  • 10 Horn H, Unverferth K, Koerner B, Lohmann D, and Laban G. inventors; German (East) Patent  274218.  ; Chem Abstr. 1990, 113, 23938.
  • 11 Horn H. Morgenstern E. Unverferth K. Pharmazie  1990,  45:  724 
    Search in Google Scholar
  • 12 Klumpp DA. Fredrick S. Lau S. Jin KK. Bau R. Surya Prakash GA. Olah GA. J. Org. Chem.  1999,  64:  5152 
    CrossrefSearch in Google Scholar
13

General Procedure for Preparation of 4a-4g, 5a-5c : The appropriate substrate 1a-1g, 3a-3c (1.4 mmol) was added to hydrazine hydrate (10mL, 99%) and the mixture refluxed for about 15 minutes. The cooled reaction mixture was acidified with 6 N HCl to pH 6. The solid product separated was extracted with CHCl3 and worked up as usual. The residue from the CHCl3 layer was purified by column chromato-graphy over silica gel and CHCl3 eluate fractions afforded pure solid products 4a-4g, 5a-5c which were crystallised from CHCl3 -light-petroleum.

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2,2′- Diaryl-1,3-indanediones 3a-3c were synthesized following step-a and step-b (Scheme [1] ). Initially the mono-arylated ninhydrin adducts, 2a-2c were synthesised by stirring ninhydrin (1.4 mmol) and the appropriate hydro-carbon Ar-H (4.2 mmol) in a mixture of acetic acid (10 mL) and concd H2SO4 (1.0 mL) for about 0.5 h at room temperature. The solid product separated was filtered out and washed thoroughly with acetic acid and then with water. The product was purified by silica-gel column chromato-graphy using acetone as the eluent (yield ˜85%).
For the 2nd arylation of 2a-2c, the appropriate hydrocarbon Ar′-H (4.2 mmol) was added to a solution of monoarylated ninhydrin 2a-2c (1.4 mmol) in a mixture of acetic acid (10 ml) and concd H2SO4 (3-4 mL). The mixture was stirred at 25 °C for 6 h and then poured over ice. The product was extracted into CHCl3 and the organic phase was washed twice with water, twice with brine, further washed with water, dried over Na2SO4, and concentrated in vacuo. The resulting solid was further purified by recrystallisation from CHCl3 (yield ˜70%).

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Spectral data for 4c: IR (KBr): (cm-1) 1659 (CO), 3170 (NH); 1H NMR (δ): 10.8 (1 H, s, NH), 8.46 (1 H, m, H-8), 7.73 (3 H, m, H-5, H-6, H-7), 7.28 (4 H, apparent d, J = 8.6 Hz, H-3′, H-3′′, H-5′, H-5′′), 7.13 (4 H, apparent d, J = 8.6 Hz, H-2′, H-2′′, H-6′, H- 6′′), 5.90 (1 H, s, H-α); 13C NMR (δ): 159.9 (C-1), 147.2 (C-4), 139.1 (C-1′, C-1′′), 133.6 (C-6), 133.2 (C-4′, C-4′′), 131.5 (C-7), 130.6 (C-2′, C-2′′, C-6′, C-6′′), 129.7 (C-9 or C-10), 128.9 (C-3′, C-3′′, C- 5′, C-5′′), 128.5 (C-10 or C-9), 127.3 (C-8), 124.8 (C-5), 52.0 (C-α). Anal. Calcd for C21H14Cl2N2O: C 66.15; H 3.70; Cl 18.60; N 7.35. Found: C 66.06; H 3.78; Cl 18.52; N 7.29%.
Spectral data for 4f: IR (KBr): (cm-1) 1667 (CO), 3176 (NH); 1H NMR (δ): 10.4 (1 H, br, NH), 8.45 (1 H, m, H-8), 7.79 (1 H, m, H-6), 7.71 (2 H, m, J = 8.6 Hz, H-5, H-7), 7.12 (4 H, apparent d, J = 8.7 Hz, H-2′, H-2′′, H-6′, H-6′′), 6.84 (4 H, apparent d, J = 8.7 Hz, H-3′, H-3′′, H-5′, H-5′′), 5.88 (1 H, s, H-α), 3.77 (6 H, s, 2 × OCH3); 13C NMR (δ): 159.9 (C-1), 158.6 (C-4′, C-4′′), 148.6 (C-4), 133.4 (C-6), 133.3 (C-1′, C-1′′), 131.1 (C-7), 130.2 (C-2′, C-2′′, C-6′, C-6′′), 130.1 (C-9 or C-10), 128.5 (C-10 or C-9), 127.1 (C-8), 125.2 (C-5), 114.1 (C-3′, C-3′′, C-5′, C-5′′), 55.2 (2 × OCH3), 51.7 (C-α). Anal. Calcd for C23H20N2O3: C 74.17; H 5.41; N 7.52. Found: C 74.14; H 5.37; N 7.48%.