Synthesis of Benzocyclobutanes through Ring Transformation Reactions of 2H-pyran-2-ones

Diptesh Sil; Ashoke Sharon; Ramendra Pratap; Prakas R. Maulik; Vishnu Ji Ram

doi:10.1055/s-2004-831292

LETTER

Synthesis of Benzocyclobutanes through Ring Transformation Reactions of 2H-pyran-2-ones [1]

Diptesh Sil^a, Ashoke Sharon^b, Ramendra Pratap^a, Prakas R. Maulik^b, Vishnu Ji Ram*^a
^a Medicinal Chemistry Division, Central Drug Research Institute, Lucknow-226001, India
Fax: +91(522)2223405; e-Mail: vjiram@yahoo.com;
^b Molecular & Structural Biology Division, Central Drug Research Institute, Lucknow-226001, India

Abstract

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Abstract

A one-pot synthesis of benzocyclobutane (3a-n) has been developed through base-induced ring transformation reactions of 6-aryl-4-substituted-2H-pyran-2-one-3-carbonitriles (1a-c) and methyl 6-aryl-4-methylsulfanyl-2H-pyran-2-one-3-carboxylate (1d) by cyclobutanone.

Key words

ring transformation reactions - ring closure - benzocyclobutanes - synthesis

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References

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Typical Procedure of 3: A mixture of 2H-pyran-2-one 1
(1 mmol), cyclobutanone (1 mmol) and powdered KOH (1.5 mmol) in dry DMF was stirred for 24 h at r.t. The reaction mixture was poured onto ice-water with vigorous stirring and finally neutralized with 10% HCl. The separated solid was filtered, washed with H₂O and dried. The crude product was purified by silica gel column chromatography. Compound 3c: mp 144-145 °C. Yield: 61%. IR (KBr): 2215 cm^-1. ¹H NMR (200 MHz, CDCl₃): δ = 2.58 (s, 3 H, SCH₃), 3.29-3.31 (m, 4 H, CH₂), 4.07 (s, 5 H, ArH), 4.42-4.44 (m, 2 H, ArH), 4.66-4.68 (m, 2 H, ArH), 7.27 (s, 1 H, ArH). FAB (MS): 360 [M⁺ + 1]. Further details of the crystal structure investigation of 3c can be obtained from the Cambridge Crystallographic Data Centre, 12 Union Road, Cambridge, CB2 1EZ, UK (CCDC deposition No. of 3c: 235153).