Photochemistry of 9-acridinecarboxaldehyde in aqueous media

Abstract

Dark and photolysis reactions in solution were investigated for 9-acridinecarboxaldehyde (ACL). ACL reacts in the dark at T = 20 °C and pH = 7.0 in an air saturated solution to the main product 9-acridinecarboxylic acid (ACA) and to the minor product 9-acridinemethanol (ACM) with a lifetime of τ = 4.3 days. The dissociation constant of the base ACLH⁺ was determined to be pK_a ± σ = 4.38 ± 0.04. The photolysis of ACL was investigated using a polychromatic Xe-light source. The quantum yield in aqueous solution at T = 20 °C in a concentration range of c₀(ACL) = 0.18–16.6 μM for pH > pK_a and for nitrogen, air and oxygen aerated solutions was found to be Φ ± σ = (0.015 ± 0.003) mol/mol, independent from concentration. The quantum yield of ACLH⁺, i.e. for pH ≪ pK_a, is by a factor of 2 higher (Φ = 0.029 mol/mol). Quantum yields in methanol and isopropanol are slightly lower compared to water and in acetone lower by about a factor of 20. In acetonitrile ACL was found to be practically photostable. Minimum lifetimes in sunlight for a measurement on September 5, 2017 were in the range of τ = 5–10 minutes. The diurnal photolysis of ACL in sunlight was satisfactory explained using the mean quantum yield, the absorption spectrum and photon fluxes with suitable corrections for cloudiness and the dimensions of the setup. For low concentrations ACR is formed with a yield of practically 100% in the photolysis reaction. However, with increasing concentration of ACL yields of ACR decrease and yields of ACA increase. 9(10H)-Acridinone and ACM were always detected as minor products with yields below 2%. 9-Methylacridine was never detected in any reaction of ACL. Strong indications are presented of a photolysis reaction of ACL in a river located in Lower Saxony (Germany) with a corresponding equimolar formation of ACR. ACL is therefore a direct precursor of ACR in natural surface water.