Heck reaction synthesis of anthracene and naphthalene derivatives as traps and clean chemical sources of singlet molecular oxygen in biological systems

Abstract

Our study shows that new anthracene and naphthalene derivatives function as compounds for trapping and chemically generating singlet molecular oxygen [O2(1Δg)], respectively. The syntheses of these derivatives are described, as well as some localization testing in cells.

Synthesis and Structural Studies of Two New Anthracene Derivatives

“…As related by Oliveira et al [13,14], the absorption and emission spectra of DEADP, gives three well-defined absorption bands at 356, 375 and 396 nm, and emission bands at 400, 424 and 449 nm, whereas DADB has a broad band of absorption and fluorescence spectra, due to the presence of the double bonds at the 9,10 position of the anthracene ring producing an electron delocalization in the structure, with a maximum absorption at 260 and 405 nm and a maximum fluorescence emission at 525 nm with excitation at 405 nm in acetonitrile. The quantum yield of fluorescence at room temperature to DADB and DEADP compared to Rhodamine B (at a concentration of 1 × 10 −6 mol•L −1 in MeCN; λ ex = 400 nm, Φ = 0.65) was Φ = 0.230 ± 0.002 and 0.352 ± 0.01 in MeCN, respectively [13,14] The infrared spectrum of the DADB derivative obtained is presented along with the spectrum of the DEADP derivative in Figure 2. The spectrum shows peaks in the region of 2900-3000 cm −1 referring to the C-H and C=C groups and it is observed the influence of double bond in the intensity of signals in this region, the presence of the C=O at 1600 cm −1 and peaks in the 1200 cm −1 region characteristic of the C-O group.…”

“…Anthracene derivatives diethyl-(2E,2 E)-3,3 -(anthracene-9,10-diyl)di(prop-2-enoate) (DADB) and diethyl-(2E,2 E)-3,3 -(anthracene-9,10-diyl)di(prop-2-enoate) (DEADP) were synthesized by the methodology presented by Oliveira et al [13,14]. Spectroscopic analysis by Fourier-Transform Infrared (FTIR).…”

“…The DADB derivatives were synthesized by C-C coupling Heck reaction following the procedure described by Oliveira et al [13,14]. In terms of this mechanism, it is important to mention that the preference of structural form obtained is the trans-trans DADB.…”

“…In recent years, an anthracene derivative-the 3,3′-(9,10anthracenediyl) bisacrylate (DADB) with fluorescent properties-was synthesized using the Heck reaction and shown to be able to cross the plasma membrane. However, the reduction of the double bonds of DADB produces a derivative, the diethyl 9,10anthracenedipropionate (DEADP) (Figure 1), with higher fluorescence intensity and better reactivity with O2 ( 1 Δg), by the difference in the reactivity constant, kt (2.20 × 10 6 and 2.65 × 10 7 M −1 s −1 ) [13,14]. With that in mind, the study of the properties of anthracene derivatives and their crystallographic characterization will be useful in understanding the characteristics of these compounds and the properties to be used as an O2 ( 1 Δg) chemical trap and in assisting the development of other compounds with modifications in the anthracene ring to be used in biological systems.…”

Simultaneous Determination of the Chemical (kr) and the Physical (kq) Quenching Rate Constants of Singlet Oxygen in Aqueous Solution by the Chemiluminescence‐quenching Method†

“…Na 2 MoO 4 ,2H 2 O (99.9%) and H 2 O 2 (50 wt%) were purchased from Sigma-Aldrich. The naphthalenic substrates NDP (29,30), Me-NDP (31,32) and DHPN (27,33) were synthesized according to known procedures. The 1 O 2 trap, Me-DHPN, was prepared as DHPN by replacing the starting compound 1-chloromethyl-4bromomethylnaphthalene by 1-methyl-2,4-dichloromethylnaphthalene obtained by double chloromethylation of 1-methylnaphthalene (31).…”