SINTESIS SENYAWA TABIR SURYA DAN ANTIOKSIDAN TURUNAN KALIKS[4]RESORSINARENA SERI BENZOIL DAN SINAMOIL DARI SALISILALDEHIDA

SANTI NUR HANDAYANI, Prof. Drs. Jumina,Ph.D; Prof. Dr. Mustofa, M.Kes., Apt.; Dr. Respati Tri Swasono, S.Si., M.Phil

2017 | Disertasi | S3 Kimia

Telah dilakukan sintesis senyawa baru seri benzoil-sinamoil fenilkaliks[4]resorsinarena dan benzoat-sinamat fenilkaliks[4]resorsinarena. Sintesis dilakukan dari salisilaldehida dan resorsinol melalui reaksi alkilasi, substitusi elektofilik aromatik-siklisasi, reaksi esterifikasi, reaksi asilasi Friedel-Craft dengan AlCl3, dan reaksi hidrolisis. Elusidasi struktur dilakukan dengan spektrofotometer FTIR dan NMR, GC-MS,dan LC-MS. Sintesis senyawa turunan benzoil-sinamoil fenilkaliks[4]resorsinarena yang diuji aktifitas tabir surya dan antioksidan terdiri atas senyawa benzoil C-2-hidroksifenilkaliks[4]resorsinarena (BCHFKR atau senyawa 13), benzoil C-2-metoksifenilkaliks[4]resorsinarena (BCMFKR/14), benzoil C-2-etoksi-fenilkaliks[4]resorsinarena (BCEFKR/15), sinamoil C-2-hidroksifenilkaliks[4]-resorsinarena (SCHFKR/16), sinamoil C-2-metoksifenilkaliks[4]resorsinarena (BCMFKR/17), sinamoil C-2-etoksifenilkaliks[4]resorsinarena (BCEFKR/18). Seri benzoat-sinamat fenilkaliks[4]resorsinarena hanya diuji aktifitas sebagai tabir surya terdiri atas 2-hidroksifenilkaliks[4]resorsinaril oktabenzoat (CHFKROB/19), C-2-metoksifenilkaliks[4]resorsinaril oktabenzoat (CMFKROB/20), C-2-etoksifenil-kaliks[4]resorsinaril oktabenzoat (CEFKROB/21), C-2-hidroksifenilkaliks[4]-resorsinaril oktasinamat, (CHFKROS/22), C-2-metoksifenilkaliks[4]resorsinaril oktasinamat (CMFKROS/23), dan 2-etoksifenilkaliks[4]resorsinaril oktasinamat (CEFKROS/24). Senyawa awal fenilkaliks[4]resorsinarena yang diuji sebagai antioksidan antara lain C-2-hidroksifenilkaliks[4]resorsinarena (CHFKR/1), C-2-metoksifenilkaliks[4]resorsinarena (CMFKR/2) dan C-2-etoksifenilkaliks[4]-resorsinarena (CEFKR/3). Pengujian aktifitas tabir surya dilakukan dengan metode in vitro menggunakan spektrofotometer dan MTT assay, sedangkan uji antioksidan dilakukan dengan DPPH assay. Rendemen reaksi senyawa fenilkaliks[4]resorsinarena yang diperoleh berturut- turut : 93,14 % (1); 96,93 % (2) dan 99,26 % (3). Rendemen reaksi seri benzoil-sinamoil fenilkaliks[4]resorsinarena berturut-turut : 88,65 % (13); 88,65 % (14); 74,56% (15); 44,27 % (16); 67,81 % (17) dan 79,26% (18). Rendemen reaksi seri benzoat-sinamat fenilkaliks[4]resorsinarena berturut-turut: 67,06% (19); 81,60% (20); 74,32% (21); 63,12% (22); 80,87% (23) dan 54,20% (24). Uji aktifitas tabir surya dengan menggunakan spektrofotometer UV-Vis menghasilkan nilai sun protection factor (SPF) tinggi berturut-turut 162,93 (CHFKROS/20); 57,41 (CMFKROS/22); 30,20 (SCEFKR/18) dan 12,08 (CEFKROS/24) pada konsentrasi 20 ppm. Senyawa dengan tabir surya tinggi memiliki nilai EC50 berturut-turut 0,88 ppm (CHFKROS/20); 1,23 ppm (CMFKROB/21) dan 1,47 ppm (SCEFKR/18). Sebagai pembanding nilai EC50 Sunzone dan Parasol masing-masing 1,10 dan 0,88 ppm. Nilai IC50 senyawa terhadap sel Vero berturut-turut adalah : 6486,60 ppm (BCMFKR/13); 3800,89 ppm (CEFKROS/24); 2626,96 ppm (CEFKROB/23); 1949,40 ppm (CMFKROB/21); 1823,27 ppm (SCHFKR/15) dan 1522,79 ppm (CMFKROS/22). Data tersebut menunjukkan bahwa BCMFKR/13, CEFKROS/24, CEFKROB/23, CMFKROB/21, SCHFKR/15 dan CMFKROS/22 bersifat relatif tidak toksik terhadap sel Vero. Uji aktifitas antioksidan dengan DPPH diperoleh senyawa yang memiliki sifat antioksidan kuat yaitu CMFKR, CHFKR, dan CEFKR dengan nilai ES50 berturut-turut : 43,45; 49,88 dan 54,58 µg/mL. Senyawa BCMFKR/13 memiliki aktivitas antioksidan sedang dengan nilai ES50 123,87 µg/mL dan senyawa yang mempunyai aktivitas antioksidan yang lemah beserta nilai ES50 antara lain: SCMFKR/17 (151,64 µg/mL); BCHFKR/13 (198,29 µg/mL); BCEFKR/15 (642,37 µg/mL) dan SCEFKR/18 (740,08 µg/mL). Sebagai pembanding nilai ES50 BHT sebesar 21,67 µg/mL.

Synthesis of benzoate-cinnamate and benzoyl-cinnamoyl phenylcalix[4]resorcinarene series has been conducted. The synthesis was carried out from salicylaldehyde and recorcinol via alkylation, aromatic electrophilic substitution-cyclization, esterification, Friedel-Craft acylation reaction with AlCl3 catalyst, and hydrolysis reaction. Structural elucidation of product was performed using FTIR and NMR spectrophotometer, GC-MS and LC-MS. The benzoyl-cinnamoyl calix[4]resorcinarene series compound consist of the benzoyl C-2-hidroxyphenyl-calix[4]resorcinarene (BCHFKR/13 compound), benzoil C-2-methoxyphenylcalix[4]-resorcinarene (BCMFKR/14), benzoyl C-2-ethoxyphenylcalix[4]resorcinarene (BCEFKR/15), cinnamoyl C-2-hidroxyphenylcalix[4]resorcinarene (SCHFKR/16), sinamoil C-2-methoxyphenylcalix[4]resorsinarene (BCMFKR/17), cinnamoyl C-2-ethoxyphenyl-calix[4]resorcinarene (BCEFKR/18) were assay activity of sunscreen and antioxidant. The benzoate-cinnamate phenylcalix[4]resorcinarene series were examined as sunscreen consist of C-2-hidroxyphenylcalix[4]resorcinaryl octabenzoate (CHFKROB/19), C-2-hidroxyphenylcalix[4]resorcinaryl octacinnamate, (CHFKROS/ 20), C-2-methoxyphenylcalix[4]resorcinaryl octabenzoate (CMFKROB/21), C-2-methoxy-phenylcalix[4]resorcinaryl octacinnamate (CMFKROS/22), C-2-ethoxy-phenylcalix[4]resorcinaryl octabenzoate (CEFKROB/23), and 2-ethoxyphenyl-calix[4]resorcinaryl octacinnamate (CEFKROS/24). The initial phenylcalix[4]-recorcinarene was examined antioxidant activity consist of C-2-hidroxyphenylcalix[4]-resorcinarene (CHFKR/1), C-2-methoxyphenylcalix[4]resorcinarene (CMFKR/2), and C-2-ethoxy-phenylcalix[4]resorcinarene (CEFKR/3). The examination of sunscreen activity was done by in vitro method using UV-Vis spectrophotometer and MTT assay, while that of antioxidant assay was done using DPPH methods. The percent yields the reaction of the phenylcalix[4]resorcinarene series were 93.14% (1); 96.93% (2) and 99.26% (3) respectively. Whereas percent yields of benzoyl-cinnamoyl phenylcalix[4]resorcinarene series were 88.65% (13); 88.65% (14); 74.56% (15); 44.27% (16); 67.81% (17) and 79.26% (18). The yield of benzoate-cinnamate phenylcalix[4]resorcinarene series were: 67.06% (19); 81.60% (22); 74.32% (20); 63.12% (23); 80.87% (21) and 54.20% (24) respectively. The result of activity test as suncreen using UV-Vis spectrophotometer were SPF (sun protection factor) enough high value of 162.93 (CHFKROS/20); 57.41 (CMFKROS/22); 30.20 (SCEFKR/18) and 12.08 (CEFKROS/24) at concentration 20 ppm respectively. The compounds have high activity as suncreen using MTT assay with effective concentration 50 (EC50) values of 0.88 ppm (CHFKROS/20); 1.23 ppm (CMFKROB/21) and 1.47 ppm (SCEFKR/18) respectively. Whereas the EC50 value of Sunzone and Parasol are 1.1 and 0.88 ppm. The compound have the high inhibitor concentration 50 (IC50) ie : 6486.60 ppm (BCMFKR/13); 3800.89 ppm (CEFKROS/24); 2626.96 ppm (CEFKROB/23); 1949.40 ppm (CMFKROB/21); 1823.27 ppm (SCHFKR/16) and 1522.79 ppm (CMFKROS/22). The compound of BCMFKR/13, CEFKROS/24, CEFKROB/23 and CMFKROB/21 shown relatively not toxic toward Vero cell. The result antioxidant activity of the compound with high activity are CMFKR/2, CHFKR/1 and CEFKR/3 with the effective scavenging 50 (ES50) value 43.45; 49.88 and 54.58 µg/mL respectively. The BCMFKR/13 has enough activity with ES50 123.87 µg/mL. Another compound of SCMFKR/17, BCHFKR/13, BCEFKR/15 and SCEFKR/18 have weak activity antioxidant with ES50 value 151.64; 198.2; 642.37 and 740.08 µg/mL respectively. Whereas the ES50 value of BHT is 21.67 µg/mL.

Kata Kunci : sintesis, tabir surya, antioksidan, turunan kaliks[4]resorsinarena, benzoil, sinamoil dan salisilaldehida.