Sintesis Dihidropirimidinon Tanpa Pelarut Menggunakan Katalis Iodin

Pratama, Landaeta Yolga (2025) Sintesis Dihidropirimidinon Tanpa Pelarut Menggunakan Katalis Iodin. Masters thesis, Institut Teknologi Sepuluh Nopember.

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Abstract

Dihidropirimidinon dengan struktur pirimidin yang mengandung dua atom nitrogen dan satu gugus karbonil dapat disintesis melalui reaksi multikomponen antara aldehida, urea, dan β–keto ester. Reaksi ini dapat dilakukan dengan berbagai pelarut, penambahan katalis yang berbeda, dan dengan berbagai teknik sintesis. Studi literatur mengungkap bahwa sintesis dihidropirimidinon tanpa pelarut dengan penambahan iodin sangat terbatas. Penelitian ini melaporkan sintesis dihidropirimidinon 4a tanpa pelarut melalui reaksi aldehida 1a, urea 2, dan etil asetoasetat 3 sebagai model reaksi pada suhu yang berbeda (suhu ruang, 100°C, 133°C, 200°C), jumlah penambahan iodin yang bervariasi (1%, 2,5%, 5%, 10%, 20%), dan selama 6, 7, 8, 9, 10 jam. Kondisi reaksi terbaik yang diperoleh dari model reaksi selanjutnya digunakan dalam sintesis dihidropirimidinon 4b-g. Reaksi pada suhu 100°C selama 5 jam dengan penambahan iodin 5 mol% memberikan senyawa etil 4-fenil-6-metil-2-okso-1,2,3,4-tetrahidropirimidin-5-karboksilat 4a dengan yield 61% yang lebih tinggi dari produk senyawa 4a hasil reaksi pada suhu ruang, 133°C, dan 200°C. Reaksi yang sama dengan penambahan iodin 0 dan 2,5 mol% memberikan produk 4a dengan yield tertinggi (66,8%) diantara reaksi dengan iodin 1%, 5%, 10%, dan 20%. Model reaksi dilakukan pada suhu 100°C dengan iodin 2,5% selama 7 jam memberikan senyawa 4a dengan yield 69,9%, lebih tinggi dibandingkan hasil reaksi selama 5, 6, 8, 9, dan 10 jam. Reaksi aldehida aromatis berupa 3-hidroksibenzaldehida 1b, 4-hidroksi-3- metoksibenzaldehida 1c, 4-nitrobenzaldehida 1d, 4-metilbenzaldehida 1e, 4- klorobenzaldehida 1f, dan 4-metoksibenzaldehida 1g dengan urea 2 dan etil asetoasetat 3 pada suhu 100°C selama 7 jam menggunakan iodin 2,5% berturut-turut menghasilkan senyawa etil 4-(3-hidroksifenil)-6-metil-2-okso-1,2,3,4- tetrahidropirimidin-5-karboksilat 4b, etil 4-(4-hidroksi-3-metoksifenil)-6-metil-2- okso-1,2,3,4-tetrahidropirimidin-5-karboksilat 4c, etil 6-metil-4-(4-nitrofenil)-2-okso- 1,2,3,4-tetrahidropirimidin-5-karbosilat 4d, etil 6-metil-2-okso-4-(p-tolil)-1,2,3,4-tetrahidropirimidin-5-karboksilat 4e, etil 4-(4-klorofenil)-6-metil-2-okso-1,2,3,4-tetrahidro-pirimidin-5-karboksilat 4f, dan etil 4-(4-metoksifenil)-6-metil-2-okso-1,2,3,4-tetrahidropirimidin-5-karboksilat 4g dengan yield sebesar 74,09, 51,81, 72,00,iv 75,08, 42,32, 39,16%. Struktur dihidropirimidina 4a-g hasil sintesis ditetapkan melalui analisis dengan spektrometer inframerah dan NMR (1H dan 13C) serta analisis massa.
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Dihydropyrimidinones with a pyrimidine structure containing two nitrogen atoms and one carbonyl group can be synthesized via a multicomponent reaction between aldehyde, urea, and β-keto ester. This reaction can be performed using different solvents, by adding different catalyst, and by using different synthesis techniques. From literature research, it appears that the solventless synthesis of dihydropyrimidinones with addition of iodine is very limited. In this study, the solventless synthesis of dihydropyrimidinone 4a is reported via the reaction of aldehyde 1a, urea 2, and ethyl acetoacetate 3 as a model reaction at different temperatures (room temperature, 100°C, 133°C, 200°C), varying amounts of iodine addition (1%, 2.5%, 5%, 10%, 20%), and for 6, 7, 8, 9, 10 hours. The best reaction conditions obtained from the model reaction were then used in the synthesis of dihydropyrimidinones 4b-g. The reaction at 100°C for 5 hours with the addition of 5 mol% iodine gave the ethyl 4-phenyl-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5- carboxylate compound 4a in 61% yield, which was higher. The amount of compound 4a product from the reaction at room temperature, 133°C, and 200°C. The same reaction with the addition of 2.5 mol% iodine gave product 4a in the highest yield (66.8%) from the reactions with 1%, 5%, 10%, and 20% iodine. The reaction model was carried out at a temperature of 100°C with 2.5% iodine for 7 hours to produce compound 4a with a yield of 69.9%, higher than the reaction results for 5, 6, 8, 9, and 10 hours. The reaction of aromatic aldehydes in the form of 3-hydroxybenzaldehyde 1b, 4-hydroxy-3-methoxybenzaldehyde 1c, 4-nitrobenzaldehyde 1d, 4- methylbenzaldehyde 1e, 4-chlorobenzaldehyde 1f, and 4-methoxybenzaldehyde 1g with urea 2 and ethyl acetoacetate 3 at a temperature of 100°C for 7 hours with 2.5% iodine successively, gives ethyl 4-(3-hydroxyphenyl)-6-methyl-2-oxo-1,2,3,4- tetrahydropyrimidine-5-carboxylate 4b, ethyl 4-(4-hydroxy-3-methoxyphenyl)-6- methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate 4c, ethyl 6-methyl-4-(4-nitrophenyl)-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate 4d, ethyl 6-methyl-2-oxo-4-(p-tolyl)-1,2,3,4-tetrahydropyrimidine-5-carboxylate 4e, ethyl 4-(4-vichlorophenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5-carboxylate 4f, dan ethyl 4-(4-methoxyphenyl)-6-methyl-2-oxo-1,2,3,4-tetrahydropyrimidine-5- carboxylate 4g and with yields of 74,09, 51,81, 72,00, 75,08, 42,32, 39,16%.. The structure of the synthesized dihydropyrimidines 4a-g was determined by infrared spectrometer and NMR (1H and 13C) analysis and mass analysis.

Item Type:	Thesis (Masters)
Uncontrolled Keywords:	Dihydropyrimidine, iodine, without solven, dihidropirimidinon, iodin, tanpa pelarut
Subjects:	Q Science Q Science > QD Chemistry Q Science > QD Chemistry > QD251.2 Chemistry, Organic. Biochemistry
Divisions:	Faculty of Science and Data Analytics (SCIENTICS) > Chemistry > 47101-(S2) Master Thesis
Depositing User:	Landaeta Yolga Pratama
Date Deposited:	07 Feb 2025 06:29
Last Modified:	07 Feb 2025 06:29
URI:	http://repository.its.ac.id/id/eprint/118543

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