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Abstract
The addition reaction had been done on the terminal alkynes of 17α-ethynylestradiol with ZnCl2 and HCl catalyst mediated by dichloromethane. The reaction conditions were carried out at a temperature of 70°C for 29 h, the separation of the reaction properties was carried out using Gravity Column Chromatography, and the reaction products were identification using by Nuclear Magnetic Resonance (NMR). The catalyst used was a cationic ligand coordinate, where Zn acts as the central ion and 2-propanol as the ligand. In the reaction mechanism, the reaction begins with the formation of dimeric ether. ZnCl3 catalyst acts as Lewis acid which converts alcohol to dimeric ether and forms a complex with ZnCl3. The nucleophilic terminal alkyne then attacks the C-O bond of the ether to form a vinyl carbocation which then attracts a chlorine atom from ZnCl3 which was complex bound with ether, resulting in a reaction product of 17α(chlorovinyl-3-methyl-butene)estradiol
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References
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References
E.V. Anslyn, D.A. Dougherty.Modern Physical Organic Chemistry. University science books; 2006.
T.W.G. Solomons, C.B. Fryhle , S.A. Snyder. Organic Chemistry. 12ed. John Wiley & Sons, Inc.; 2016.
S. Biswas, S. Maiti, U. Jana. New and Efficient Iron Halide Mediated Synthesis of Alkenyl Halides through Coupling of Alkynes and Alcohols. Eur. J. Org. Chem., (14) (2009) 2354-2359. doi:10.1002/ejoc.200900104
S.R. Chemler, D. Trauner, S.J. Danishefsky. The B-Alkyl Suzuki–Miyaura Cross-Coupling Reaction: Development, Mechanistic Study, and Applications in Natural Product Synthesis. Angew. Chem .Int. Ed., 40(24) (2001) 4544-4568.
G.W. Kabalka,M.L. Yao, S. Borella, Z. Wu. Alkenylation of allylic alcohols using alkenylboron dihalides: a formal transition-metal free Suzuki reaction. Chem Commun., (19) (2005) 2492-2494.
Y.R. Yang, Q. Zhang, F.T. Du, J.X. Ji. Fe powder catalyzed highly efficient synthesis of alkenyl halides via direct coupling of alcohols and alkynes with aqueous HX as exogenous halide sources. Tetrahedron, 71(25) (2015) 4304-4311.
R. Maroni, G. Melloni, G. Modena. The stereochemistry of the electrophilic additions to triple bonds via linear vinyl cations. J. Chem. Soc. Chem. Commun., (15) (1972) 857-858.
M. Hanack, E. Weber. Vinylkationen, 39. Zinkchlorid-katalysierte Chlorwasserstoff-Additionen an Cyclopropylalkine. Chem Ber., 116(2) (1983) 777-797.
E.J. Pongoh, R.J. Rumampuk, N.S. Dwiyanti. Mechanism of Addition Reaction of Cyclohexanol on 17α-ethinylestradiol (EE2) with FeCl3 Media. NeuroQuantology, 20(19) (2022) 603-608
S.A. Bhawani, O. Sulaiman, R. Hashim, M.N. Mohamad Ibrahim. Thin-layer chromatographic analysis of steroids: A review. Trop. J. Pharm. Res., 9(3) (2010) 301-313. doi:10.4314/tjpr.v9i3.56293
A.R. Fakhari, A.R. Khorrami, M. Shamsipur. Stability-indicating high-performance thin-layer chromatographic determination of levonorgestrel and ethinyloestradiol in bulk drugs and in low-dosage oral contraceptives. Anal. Chim. Acta., 572(2) (2006) 237-242. doi:10.1016/j.aca.2006.05.029
R. Rumampuk. Elucidation of saponin structures from seeds of Barringtonia asiatica (L.) Kurz. Padjadjaran University, Bandung.
A. Lommen, R. Schilt, J. Weseman, A.H. Roos, J.W.V. Velde. Application of 1D 1 HNMR for fast non-targeted screening and compositional analysis of steroid cocktails and veterinary drug formulations administered to livestock. J. Pharm. Biomed. Anal., 28 (2002) 87-96.
J.A. Franca, A. Navarro-Vázquez, X. Lei, H. Sun, C. Griesinger, F. Hallwass. Complete NMR assignment and conformational analysis of 17-α-ethinylestradiol by using RDCs obtained in grafted graphene oxide. Magn. Reson. Chem., 55(4) (2017)297-303.
M.R. Silverstein, F.X. Webster. Spectrometric Identification of Organic Compounds. Wiley & Sons, Inc.; 1981.