Facile Preparation of the Water-Soluble Singlet Oxygen Traps Anthracene-9,10-divinylsulfonate (AVS) and Anthracene-9,10-diethylsulfonate (AES) via a Heck Reaction with Vinylsulfonate

Abstract

An easy 2-step method for the synthesis of the water-soluble singlet oxygen trap AES has been developed. The method is based on a novel Heck reaction with sodium vinylsulfonate followed by vinyl hydrogenation. It is shown that the Heck product AVS is also suitable as a water-soluble and colored singlet oxygen trap that allows singlet oxygen to be detected specifically and simply by visual inspection. The cumulative amount of ¹O₂ generated into the solution can be determined unambiguously by measuring the concentration of the endoperoxides AVSO₂ or AESO₂ by HPLC or by ¹H NMR.

Heck reaction - hydrogenation - palladacycle - oxidation - catalysis

References

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Preparation of AVS·4H ₂ O.
A mixture of 9,10-dibromoanthracene (29.45 g, 87.6 mmol), NaOAc (17.60 g, 214.6 mmol), and trans-di(µ-acetato)- bis[o-(di-o-tolylphosphino)benzyl]dipalladium(II) (0.81 g, 0.9 mmol) in a mixed solvent system of DMF (330 mL) and NMP (330 mL) was heated at 100 °C until a clear solution was obtained. A 25% aqueous solution of sodium vinylsulfonate (110 mL, 248.6 mmol) was evaporated to a volume of ca. 80 mL. This concentrated solution was added to the hot reaction mixture in one portion, and the resulting solution was heated for 18 h under reflux (110 °C). The precipitate formed on cooling the reaction mixture to r.t. was filtered off. Insoluble metallic Pd residues were removed from the precipitate by hot filtration from a refluxing H₂O (300 mL) and EtOH (350 mL) mixture. Cooling of the hot filtrate to r.t. yielded, after filtration and drying, the product as yellow crystals (30.93 g, 70% yield). Anal. Calcd (%): C, 42.7; H, 4.0. Found: C, 43.0; H, 4.0. MS-FAB (negative ion mode): 389 [M - 2 Na + H], 411 [M - Na]. ¹H NMR (D₂O): δ = 7.74 (m, 4 H), 7.46 (m, 4 H), 7.29 (d, 2 H), 6.31 (d, 2 H).

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Available from Johnson-Matthey, plc.

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Preparation of AES·2H ₂ O.
An autoclave was charged with AVS·4H₂O (16.50 g, 32.6 mmol), 5% Pd/C (type 39)⁶ (1.60 g), MeCN (300 mL) and H₂O (300 mL). The mixture was stirred at r.t. for 6 h under 6 bar hydrogen. The mixture was filtered over Celite and the filter residue was washed with H₂O. The filtrate was evaporated to dryness. The solid residue was recrystalized 3 times from EtOH-H₂O, 5:4 v/v. Yield 11.60 g (75%). Analytical data are in accordance with ref. 3a.

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NMR Data of AVSO₂ (3): ¹H NMR (D₂O): δ = 7.43 (d, 2 H), 7.29 (m, 4 H), 7.24 (m, 4 H), 6.73 (d, 2 H).

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