ONE-POT SYNTHESIS OF BIOACTIVE 3-BENZYLIDENEISOINDOLIN-1-ONES FROM BENZYLIDENEPHTHALIDE UNDER ULTRASOUND IRRADIATION
Abdulrahman Abdullahi, Dr. M. Idham Darussalm Mardjan
2023 | Tesis | S2 Ilmu Kimia
Penelitian ini melibatkan sintesis reaksi
one-pot yang dilakukan mengunakan radiasi ultrasonik pada suhu 50 °C. Reaksi
dimulai dengan adisi nukleofilik amina primer ke 3-benzilidenftalida untuk
menghasilkan zat antara 3-hidroksiisoindolin-1-on. Reaksi kemudian diikuti dengan
penambahan larutan HCl 6M menyebabkan reaksi ?-eliminasi dari
3-hidroksiisoindolin-1-on menjadi 3-benzilideneisoindolin-1-on. Produk
dikarakterisasi dengan spectrometer 1H-NMR, 13C-NMR,
FTIR dan CHNS analyzer.
Metode sonikasi menghasilkan 2-benzil-3-benzilidenisoindolin-1-on
dengan persen hasil 75?lam waktu 90 menit, sedangkan pemanasan konvensional
membutuhkan 22 jam untuk persen hasil yang sama. Efek sterik dipelajari dengan
menggunakan 2-metoksibenzilamina, 3-metoksibenzilamina dan 4-metoksibenzilamina.
Pada 2-metoksibenzilamina dan 4-metoksibenzilamina keduanya didapatkan hasil
88%, sedangkan 3-metoksibenzilamina didapatkan hasil yang sedikit lebih rendah
yaitu 82%. Efek nukleofilisitas dipelajari dengan mengunakan 4-metilbenzilamina,
4-fluorobenzilamina, furfurilamina, 2-tiofenemetilamina, dan butilamin. Persen
hasil yang didapatkan untuk substrat masing-masing adalah 95%, 96%, 86%, 94%,
dan 97%. Gugus amina yang sangat nukleofilik, seperti butilamina dan
2-tiofenemetilamina, menghasilkan hasil yang lebih tinggi, sedangkan substrat
dengan nukleofilisitas yang lebih rendah, seperti furfurilamina menunjukkan
hasil yang sedikit lebih rendah.
The one-pot synthesis of
3-benzylideneisoindolin-1-ones from benzylidenephthalide and primary amines under
ultrasound irradiation has been conducted. The objectives of the research were to
study the effect of synthetic method, the steric effect of primary amines and
the nucleophilicity of primary amines on the synthesis of 3-benzylideneisoindolin-1-ones.
The
research involved a one-pot stepwise synthesis which was carried out under
ultrasound irradiation at a temperature of 50 °C. The reactions began with the
nucleophilic addition of primary amines to 3-benzylidenephthalide to generate
the corresponding 3-hydroxyisoindolin-1-one intermediates within 30 min. This
was followed by an acidic treatment with aqueous solution of HCl 6M which
promoted the ?-elimination reaction of the 3-hydroxyisoindolin-1-ones. The corresponding
3-benzylideneisoindolin-1-ones were generated within 1h of sonication. The
products were elucidated with 1H-NMR, 13C-NMR, FTIR and
CHNS analyzer.
The
sonication method for the synthesis of 2-benzyl-3-benzylidenisoindolin-1-one
gave a yield of 75% within 90 min, while the conventional heating took 22h for
the same yield. The steric effect was investigated by using
2-methoxybenzylamine, 3-methoxybenzylamine, and 4-methoxybenzylamine. Both
2-methoxybenzylamine and 4-methoxybenzylamine produced the corresponding products
in 88%, while 3-methoxybenzylamine gave a yield of 82%. The nucleophilicity
effect of different substrates of 4-methylbenzylamine, 4-fluorobenzylamine,
furfurylamine, 2-thiophenemethylamine and butylamine, were investigated. The yields
for the substrates were 95%, 96%, 86%, 94%, and 97% respectively. Highly
nucleophilic primary amines, such as butylamine and 2-thiophenemethylamine,
resulted in higher yields, while amines with lower nucleophilicity like
furfurylamine gave lower yields.
Kata Kunci : sintesis one-pot, sonikasi, 3-benzilideneisoindolin-1-on, nukleofilisitas dan efek steri. / one-pot synthesis, sonication, 3-benzylideneisoindolin-1-one, nucleophilicity, and steric effect
