Sonication effect on the reaction of 4-bromo-1-methylbenzene with sodium sulfide in liquid-liquid multi-site phase-transfer catalysis condition - kinetic study.

The synthesis of di-p-tolylsulfane from the reaction of 4-bromo-1-methylbenzene (BMB) with sodium sulfide was carried out using a multi-site phase-transfer catalyst (MPTC) viz., 1,4-dihexyl-1,4-diazoniabicyclo[2.2.2]octanium dibromide and ultrasonic irradiation in a liquid-liquid reaction condition. The overall reaction rate is greatly enhanced when catalyzed by multi-site phase-transfer catalyst (MPTC) combined with sonication (40 kHz, 300 W) in a batch reactor than catalyzed by MPTC without sonication. Effects on the reaction due to various operating conditions, such as agitation speed, different ultrasound frequencies, different phase-transfer catalysts, different organic solvents, the amount of MPTC, temperature, amount of sodium sulfide, effect of sodium hydroxide, volume of n-hexane and the concentration of 4-bromo-1-methylbenzene. The reaction obeys a pseudo first-order rate law and a suitable mechanism was proposed based on the experimental observation.

Effect of ultrasound in the free radical polymerization of acrylonitrile under a new multi-site phase-transfer catalyst - a kinetic study.

The kinetics of polymerization of acrylonitrile (AN) was carried out under heterogeneous condition using a new multi-site phase-transfer catalyst (MPTC), viz., N,N'-dihexyl-4,4'-bipyridinium dibromide in the presence of water soluble initiator, potassium peroxydisulphate (PDS) under chlorobenzene/water two phase system assisted by ultrasound irradiation at constant temperature 60+1°C under nitrogen atmosphere. The rate of polymerization increases with an increasing the concentrations of AN, MPTC and PDS. The order with respect to [AN], [MPTC], and [PDS] were found to be 1.01, 1.03 and 0.52, respectively. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations followed by a discussion on its significance.

Ultrasound assisted arylation of benzyl alcohol with 4-nitrochlorobenzene under a new multi-site phase-transfer catalyst in solid-liquid condition.

The ultrasound assisted preparation of 1-(benzyloxy)-4-nitrobenzene from the reaction of 4-chloronitrobenzene (CNB) and benzyl alcohol was carried out successfully using potassium hydroxide and catalyzed by a new multi-site phase-transfer catalyst (MPTC) viz., 1,3,5-triethyl-1,3,5-trihexyl-1,3,5-triazinane-1,3,5-triium trichloride in a solid-liquid reaction condition (SL-MPTC). The advantage of using SL-MPTC is to avoid a serious hydration of potassium salt of benzyl alcohol in the reaction between 4-chloronitrobenzene (CNB) and benzyl alcohol. The reaction is greatly enhanced in the solid-liquid system, catalyzed by multi-site quaternary ammonium salt (MPTC) and ultrasound irradiation (40 kHz, 300 W) in a batch reactor, it shows that the overall reaction greatly enhanced with ultrasound irradiation than without ultrasound. The reaction mechanism is proposed and verified by examining the experimental evidence. A kinetic model is proposed in which a pseudo first-order rate law is sufficient to describe the results, such as the effects of agitation speed, ultrasound, different phase transfer catalysts and the effect of organic solvents, the amount of newly prepared MPTC, the effect of temperature, the amount of water, the concentration of 4-chloronitrobenzene (CNB) and potassium hydroxide concentrations. The apparent rate constant (kapp) were investigated in detail. Rational explanations to account for the phenomena on the results were made.

Ultrasound assisted the preparation of 1-(4-nitrophenyl) imidazole under a new multi-site phase-transfer catalyst--kinetic study.

In this work, the nitroarylation of imidazole catalyzed by a new novel dual-site phase-transfer catalyst was carried out in an alkaline solution/imidazole in chlorobenzene two-phase medium with ultrasonic irradiation (40 kHz, 300 W). This new synthesized phase-transfer catalyst, N(1),N(6)-diethyl-N(1),N(1),N(6),N(6)-tetraisopropylhexane-1,6-diaminium dichloride (MPTC), which possesses two-site activity, was obtained from the reaction of 1,6-dichlorohexane and N-ethyl-N-isopropylpropane-2-amine. The reaction of imidazole and alkali was carried out at the interface to generate sodium imidazole anion which can further react with MPTC form quaternary ammonium imidazole anion along with ultrasonic irradiation (40 kHz, 300 W). This ion-pair further react with 1-chloro-4-nitrobenzene which is present in the organic phase to produce 1-(4-nitropheny) imidazole. The reaction follows a pseudo first-order rate law. Kinetics of the reactions such as effect of the catalysts, ultrasonic effect, agitation speed, temperature, alkaline concentration, amount of 4-nitrochlorobenzene and the solvent effect on the reaction rate were investigated in detail. Peculiar phenomenon for the dependence of the reaction rate on the amount of MPTC and ultrasonication are explained satisfactorily.

Ultrasound assisted the preparation of 1-butoxy-4-nitrobenzene under a new multi-site phase-transfer catalyst--kinetic study.

In the present research work deals with the preparation of 1-butoxy-4-nitrobenzene was successfully carried out by 4-nitrophenol with n-butyl bromide using aqueous potassium carbonate and catalyzed by a new multi-site phase-transfer catalyst (MPTC) viz., N(1),N(4)-diethyl-N(1),N(1),N(4),N(4)-tetraisopropylbutane-1,4-diammonium dibromide, under ultrasonic (40 kHz, 300 W) assisted organic solvent condition. The pseudo first-order kinetic equation was applied to describe the overall reaction. Under ultrasound irradiation (40 kHz, 300 W) in a batch reactor, it shows that the overall reaction greatly enhanced with ultrasound irradiation than without ultrasound. The present study provides a method to synthesize nitro aromatic ethers by ultrasound assisted liquid-liquid multi-site phase-transfer catalysis condition.

Propargylation of indene-1,3-dione under a new phase-transfer catalyst combined with ultrasonication--a kinetic study.

In the present study, kinetics of synthesis of 2,2-di(prop-2-ynyl)-1H-indene-1,3(2H)-dione was successfully carried out by propargylation of indene-1,3-dione with propargyl bromide using aqueous potassium hydroxide and catalyzed by a newly synthesized phase-transfer catalyst viz., N-benzyl-N-ethyl-N-isopropylpropan-2-ammonium bromide, PTC under ultrasonic (40 kHz, 300 W) assisted organic solvent condition. The pseudo first-order kinetic equation was applied to describe the overall reaction. Under ultrasound irradiation (40 kHz, 300 W) in a batch reactor, it shows that the overall reaction rate can be greatly enhanced with ultrasound irradiation than without ultrasound.

Preparation of 1,3-bis(allyloxy)benzene under a new multi-site phase-transfer catalyst combined with ultrasonication--a kinetic study.

In the present work, kinetics of synthesis of 1,3-bis(allyloxy)benzene was successfully carried out by O-allylation of resorcinol with allyl bromide using aqueous potassium hydroxide and catalyzed by a new multi-site phase-transfer catalyst viz., 1,3,5,7-tetrabenzylhexamethylenetetraammonium tetrachloride, MPTC under ultrasonic (40 kHz, 300 W) assisted organic solvent condition. The pseudo first-order kinetic equation was applied to describe the overall reaction. Under ultrasound irradiation (40 kHz, 300 W) in a batch reactor, it shows that the overall reaction rate can be greatly enhanced to seven fold faster with ultrasound irradiation than without ultrasound. The present study provides a method to synthesize ethers by ultrasound assisted liquid-liquid phase-transfer catalysis condition.

Ultrasound assisted polymerization of N-vinyl imidazole under phase-transfer catalysis condition--a kinetic study.

The kinetics of phase-transfer catalyzed radical polymerization of N-vinyl imidazole (NVI) using potassium peroxy disulfate (PDS) as water soluble initiator and tetraoctylammonium chloride (TOAC) as PTC has been investigated in ethyl acetate/water two phase system assisted by ultrasound irradiation at constant temperature 60 + 1 °C under nitrogen atmosphere. and. The rate of polymerization increases with an increase in concentrations of NVI, PTC and PDS. The order with respect to [NVI], [PTC], and [PDS] were found to be 1.01, 1.03 and 0.52 respectively. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations followed by a discussion on its significance.

Polymerization of ethyl methacrylate under the influence of ultrasound assisted a new multi-site phase-transfer catalyst system--a kinetic study.

The kinetics of multi-site phase-transfer catalyzed free radical polymerisation of ethyl methacrylate (EMA) using potassium peroxy disulphate (PDS) as a water soluble initiator and newly synthesized 1,4-dihexadecylpyrazine-1,4-diium dibromide as multi-site phase-transfer catalyst (MPTC) has been investigated in ethyl acetate/water two phase system at constant temperature 55 ± 1 °C under nitrogen atmosphere and ultrasound irradiation conditions. The rate of polymerization increases with an increase in concentrations of EMA, PDS and MPTC. The order with respect to monomer, initiator and MPTC were found to be 1.03, 0.52 and 0.53, respectively. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations and its significance was discussed.

Ultrasound assisted free radical polymerization of glycidyl methacrylate by a new disite phase-transfer catalyst system: A kinetic study.

The kinetics of multi-site phase-transfer catalyzed free radical polymerisation of glycidyl methacrylate (GMA) using potassium peroxy disulphate (PDS) as water soluble initiator and newly synthesized 1,4-dihexadecylpyrazine-1,4-diium dibromide as multi-site phase-transfer catalyst (MPTC) has been investigated in ethyl acetate/water two phase system at constant temperature 65±1°C under nitrogen atmosphere and ultrasound irradiation conditions. The rate of polymerization increases with an increase in concentrations of GMA, PDS and MPTC. The order with respect to monomer, initiator and MPTC were found to be 1.0, 0.5 and 1.0, respectively. The comparative study reveals that the Rp of GMA determined in the presence of PTC combined with ultrasound has shown more enhancements in the activity than PTC alone. Based on the observed results a suitable mechanism has been proposed to account for the experimental observations and its significance was discussed.

Ultrasound assisted phase-transfer catalytic epoxidation of 1,7-octadiene - a kinetic study.

An ultrasound assisted phase-transfer catalyzed epoxidation of 1,7-octadiene is greatly enhanced by using a cocatalyst of phosphotungstic acid in the presence of hydrogen peroxide in an organic solvent/aqueous solution two-phase medium. An active intermediate of the catalyst (Q3PW12(O)nO40, where Q = R4N+) produced from the reaction of phosphotungstic acid, hydrogen peroxide, and Aliquat 336. A rational mechanism of epoxidation is proposed to account for the reaction from the experimental evidence. The organic-phase reactions, including two series reactions, are the rate-controlling steps to produce two products, viz., 1,2-epoxy-7-octene and 1,2,7,8-diepoxyoctane. The kinetics of epoxidation, including the characteristics of the catalyst and the effect of the amount of cocatalyst, agitation speed, quaternary ammonium salts, amount of Aliquat 336, amount of hydrogen peroxide, amount of chloroform, pH value, organic solvents, and temperature on the conversion of 1,7-octadiene were investigated in detail. A kinetic model was built, from which a pseudo-first-order rate law is sufficient to describe the behavior of the reaction.

Ethoxylation of p-chloronitrobenzene using phase-transfer catalysts by ultrasound irradiation: a kinetic study.

Ethoxy-4-nitrobenzene was synthesized by the reaction of 4-chloronitrobenzene with potassium ethoxide in a homogeneous system using benzyltriethylammonium chloride (QCl) as a phase-transfer catalyst at 50 degrees C under ultrasound irradiation conditions. The use of phase-transfer catalysts and ultrasound has been compared and demonstrated in this nucleophilic substitution reactions. The kinetics of the reaction depends on the effect of amount of catalyst, quaternary ammonium salts, agitation speed, amount of potassium hydroxide, amount of ethanol, temperature and the frequency of the ultrasound waves on the conversion of the reaction.