Physical chemistry
Venugopal Rajendran; Varathan Selvaraj; Pachaiyappan Abimannan
Volume 6, Issue 1, pp. 1-108, Serial No. 18 , January 2018, , Pages 55-61
Abstract
The present work describes, the reaction between disodium salt of 1,3-dihydroxybenzene (in situ formation) and propargyl bromide was carried out in a solid-liquid biphasic phase transfer catalytic system at 50°C. Higher selectivity of the bis-derivative (1,3-bis(prop-2-ynyloxy)benzene) was obtained ...
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The present work describes, the reaction between disodium salt of 1,3-dihydroxybenzene (in situ formation) and propargyl bromide was carried out in a solid-liquid biphasic phase transfer catalytic system at 50°C. Higher selectivity of the bis-derivative (1,3-bis(prop-2-ynyloxy)benzene) was obtained under solid-liquid PTC condion. The conversion of propargyl bromide of more than 99% was achieved in the presence of tetra-n-butylammonium bromide (TBAB) as catalyst. From the experimental evidence there is no mono-dervative observed. Experiments were conducted to increase the conversion of propargyl bromide such as, stirring speed, various PTCs, temperature, various solvents and amount of TBAB loading. All the experiments were conducted to obey pseudo-first order rate law. Apparent activation energy was also determined from the Arrhenius plot.
Physical chemistry
Venugopal Rajendran; Varathan Selvaraj; Kuppusamy Harikumar
Volume 5, Issue 4, pp. 364-493, Serial No. 17 , October 2017, , Pages 381-396
Abstract
A new multi-site phase-transfer catalyst (MPTC), viz., N,N’-dioctyl-4,4’-bipyridium dibromide containing bi-site was prepared and proved by FT-IR, 1H NMR, 13C NMR, mass and elemental analysis. The enhancement of C-N+ peak intensity at 1179 cm−1 noticed in FT-IR, the agreement of m/z ...
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A new multi-site phase-transfer catalyst (MPTC), viz., N,N’-dioctyl-4,4’-bipyridium dibromide containing bi-site was prepared and proved by FT-IR, 1H NMR, 13C NMR, mass and elemental analysis. The enhancement of C-N+ peak intensity at 1179 cm−1 noticed in FT-IR, the agreement of m/z values, viz., 542.43 bi-site respectively with their theoretical values and the percentage of C, H, N elements noticed in elemental analysis has strongly supported the presence of tri-site MPTC catalysts. Further, the presence of number of active-sites in the catalyst was again confirmed by determining their pseudo-first order rate constant for dichlorocarbene addition to 1,3-bis(allyloxy)-5-methylbenzene in the presence of ultrasonic irradiation/mechanical stirring. The comparative study reveals that the kapp determined with the combination of ultrasound and mechanical stirring has shown more activity than with their individual effect. Further, the detailed kinetic study performed with superior di-site MPTC reveals that the kapp are dependent with the stirring speed, [substrate], [catalyst], [NaOH] and temperature. Based on the kinetic results, thermodynamic parameters are evaluated.