Development of C-Arylcalix[4]resorcinarenes and C-Arylcalix[4]pyrogallolarenes as Antioxidant and UV-B Protector

Abstract

Indonesia is rich with essential oils such as anise and clove leave oils. In respect to explore the potential utilization of these resources, it has been conducted the transformation of p-hydroxybenzaldehyde and vanillin (4-hydroxy-3-methoxy benzaldehyde) respectively derived from anise oil and clove leaves oil to a series of Carylcalix [4]resorcinarenes and C-arylcalix[4]pyrogallolarene macrocycles. Treatment of these aldehydes with resorcinol in the presence of HCl in absolute ethanol at reflux for 8 h afforded C-4-hydroxyphenylcalix[4]resorcinarene (3a) and C-4-hydroxy-3-methoxy phenyl-calix[4]resorcinarene (3b) in good yields. When the aldehydes were treated with pyrogallol under the similar condition, the products were C-4-hydroxyphenyl calix[4]pyrogallolarene (3c) and C-4-hydroxy-3-methoxyphenylcalix[4]pyrogallolarene (3d) which were also obtained in excellent yields. Treatment of these calix[4]resorcinarenes and calix[4]pyrogallolarenes with cinnamoyl chloride and benzoyl chloride in pyridine afforded the corresponding cinnamate esters and benzoate esters in high yields. The resulted C -arylcalix-[4]resorcinarenes and C-arylcalix[4]pyrogallol arenes were subjected to antioxidant activity test using DPPH method and showed strong activity with IC50 values of 15-80 μg/mL. In terms of the synthesized calix cinnamates, the compounds showed UV-B absorption with SPF values of 15-30 at a concentration of 25 ppm which demonstrate their potential to be applied as a UV-B protector. Furthermore, these compounds were also tested for their photostability on the UV-B region and the results showed that the compounds were still unstable under irradiation for 30 min.

Sintesis dan Uji Aktivitas Senyawa C-4-benziloksifenilkaliks[4]pirogalaril Dodekasinamat sebagai Bahan Aktif Tabir Surya

“…Golongan senyawa ini memiliki stabilitas yang relatif tinggi (Jumina et al, 2022), sitotoksisitas yang rendah (Bowley, 2008), dan dapat difungsionalisasi dengan berbagai kromofor untuk mendapatkan serapan yang diinginkan (Jumina et al, 2019). Beberapa turunan senyawa kaliks[4]pirogalarena telah disintesis dan difungsionalisasi dengan kromofor benzoat dan sinamat menghasilkan senyawa dengan serapan pada daerah UVC dan UVB, serta serapan molar yang tinggi (Harizal et al, 2018;Jumina et al, 2019).…”

Synthesis and High Antioxidant Activity of C-Alkyl Calix[4]resorcinarene and C-Alkyl Calix[4]pyrogallolarene Derivatives

“…When the IC50 value is lower than 50 µg mL -1 , the antioxidant activity is categorized to be very strong. Strong, moderate, and weak antioxidant activity are determined when the IC50 value is 50-100 µg mL -1 , 101-150 µg mL -1 , and more than 150 µg mL -1 , respectively (Jumina et al, 2019). The antioxidant agents derived from natural sources usually exhibit weak antioxidant activity (Lukitaningsih et al, 2014;Fidrianny et al, 2012;Asirvatham and Akhil, 2017;Chandra et al, 2020).…”

“…It was known that the hydroxyl group is reactive to donate its proton to the free radicals (Ahangarpour et al, 2019). In our previous study, calix [4]resorcinarenes and calix[4]pyrogallolarenes were prepared from a cyclo-condensation reaction from resorcinol (1,3-dihydroxybenzene) and pyrogallol (1,2,3trihydroxybenzene), respectively (Jumina et al, 2019(Jumina et al, , 2020a(Jumina et al, , 2020b(Jumina et al, , 2021. These synthetic compounds exhibit strong antioxidant activity.…”

“…These synthetic compounds exhibit strong antioxidant activity. For example, C-4-hydroxyphenylcalix [4]resorcinarene and C-4-hydroxyphenylcalix[4]pyrogallolarene exhibit high antioxidant activity with IC50 values of 22.7 and 88.2 µg mL -1 , respectively (Jumina et al, 2019). The antioxidant activity of calix-[4]resorcinarenes and calix[4]pyrogallolarenes depend on the type and location of the attached functional group.…”

“…The antioxidant activity of calix-[4]resorcinarenes and calix[4]pyrogallolarenes depend on the type and location of the attached functional group. The antioxidant activity of C-4-hydroxyphenylcalix [4]resorcinarene (IC50 = 22.7 µg mL -1 ) was stronger than C-2hydroxyphenylcalix[4]resorcinarene (IC50 = 77.4 µg mL -1 ) and also stronger than C-4methoxyphenylcalix[4]resorcinarene (IC50 = 79.0 µg mL -1 ) (Handayani et al, 2016;Ngurah, 2018;Jumina et al, 2019).…”