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

doi:10.1016/j.ultsonch.2013.02.011

Ultrasonics Sonochemistry

Volume 20, Issue 5, September 2013, Pages 1236-1244

https://doi.org/10.1016/j.ultsonch.2013.02.011 Get rights and content

Highlights

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A new multi-site phase-transfer catalyst was used for allylation of resorcinol.
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Effect of ultrasound was studied in this reaction.
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Different electric power of 40 kHz ultrasound irradiation was tested.
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A suitable reaction mechanism was proposed for this reaction.

Abstract

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.

Introduction

Phase-transfer catalysis (PTC) is an effective tool for synthesis of organic chemicals from two immiscible reactants [1]. As the chemical reactants reside in immiscible phases, phase-transfer catalysts have the ability to carry one of the reactants as a highly active species for penetrating the interface, into the other phase where the reaction takes place, and to give a high conversion and selectivity for the desired product under mild reaction conditions. Ever since Jarrouse [2] found that quaternary ammonium salts acts as an effective catalyst for enhancing the two-phase reaction, this methodology occupies a unique niche in organic synthesis and it is a commercially matured discipline with over 600 applications [3], [4], [5], [6], [7] covering a wide spectrum of industries such as pharmaceuticals, agrochemicals, dyes, perfumes, flavors, specialty polymers, pollution control, etc. As the application of PTC grew, much effort was placed on the development of phase-transfer catalysts with higher catalytic efficiency. To this end, researchers have developed a “multi-site” phase transfer catalyst (MPTC). Recently, the catalytic behavior of multi-site phase-transfer catalysts have attracted much attention, due to the fact that multiple molecules of the aqueous reactant can be carried into the organic phase once a reaction cycle, thus the catalytic efficiency is enhanced [8], [9], [10], [11], [12].

Currently, ingenious new analytical and process experimental techniques which are environmental benign techniques viz., ultrasound and microwave irradiation have become immensely popular in promoting various organic reactions [13], [14], [15], [16], [17]. Ultrasound irradiation is a transmission of a sound wave through a medium and is regarded as a form of energy that enhances the rate of the reaction due to mass transfer and effective mixing [18], [19], [20].

Application of ultrasonic waves in organic syntheses (homogeneous and heterogeneous reactions) has been boosted in recent years [21], [22], [23], [24], [25], [26], [27]. Sonication of multiphase systems accelerates the reaction by ensuring a better contact between the different phases [28], [29]. Further, they also increase the reaction rate and avoid the use of high reaction temperatures [30]. These days this environmental benign technology is combined with PTC with primary objective of optimizing reaction conditions [31], [32], [33].

For the first time, we are evaluating the influence of ultrasound in association with multi-site phase-transfer catalyst (MPTC) on the synthesis of 1,3-bis(allyloxy)benzene by O-allylation of resorcinol using allyl bromide (AB) as a limiting agent. Since, the kinetic study of O-allylation of resorcinol using allyl bromide under controlled MPTC reaction conditions will be interesting and challenging, we followed the kinetic study of O-allylation using 1,3,5,7-tetrabenzylhexamethylenetetrammonium tetrachloride (MPTC), as catalyst under ultrasonic condition (40 kHz; 300 W). Further, to the best of our knowledge, there are no literature reports regarding O-allylation of resorcinol with allyl bromide under MPTC-ultrasonic condition.

Section snippets

Chemicals

All reagents, including resorcinol, allyl bromide, tetrabutylammonium bromide (TBAB), tetraethylammonium chloride (TEAC), tetraethylammonium bromide (TEAB), benzyltreithylammonium bromide (BTEAB), benzyltreithylammonium chloride (BTEAC), potassium hydroxide, toluene, chlorobenzene, biphenyl and other reagents for synthesis, were guaranteed grade (GR) chemicals and were used as received without further purification.

Instrumentation

FT-IR spectra were recorded on a Brucker-Tensor 27 FT-IR spectrophotometer. ¹H

Ultrasonic process equipment

Ultrasonic energy is transmitted to the process vessel through the liquid medium, usually water in the tank. For safety purpose, the sonochemical reactor consisted of two layers of stainless steel body. The sonochemical reactor configuration used in the present work is basically an ultrasonic bath. The internal dimension of the ultrasonic cleaner tank is 48 cm × 28 cm × 20 cm with liquid holding capacity of 5 L. Two types of frequencies of ultrasound were used in these experiments, which are 28 kHz and

General procedure for the synthesis of 1,3-bis(allyloxy)benzene under mechanical stirring

To the mixture of KOH (15 g, 0.26 mol) in water (15 mL) and MPTC (0.25 g, 3.86 × 10⁻⁴ mol), resorcinol (2.5 g, 0.022 mol) was added under overhead stirring to generate the phenoxide anion. Then allyl bromide (6.34 g, 0.052 mol) in chlorobenzene (40 mL) was added slowly. The reaction mixture was heated at 45 °C for 6 h with vigorous stirring. The crude product was isolated by simple extraction with diethyl ether (3 × 25 mL). The organic layer was collected and the solvent was evaporated under reduced pressure.

Sonicated kinetics of the bi-phase reaction system

The reactor was a 150 mL three-necked Pyrex flask, serving the purposes of agitating the solution, inserting the thermometer, taking samples and feeding the feed. A known quantity of KOH (30 g, 0.53 mol) was dissolved in deionised water (30 mL) to prepare an aqueous alkaline solution. Known quantities of MPTC (0.50 g, 7.73 × 10⁻⁴ mol), resorcinol (5 g, 0.0454 mol) and biphenyl (internal standard, 0.2 g) were added to reaction vessel, which was suspended in the middle of ultrasonic bath to get the maximum

Reaction mechanism and kinetic model

For synthesizing 1,3-bis(allyloxy)benzene compound, the overall reaction of resorcinol and allyl bromide (AB) was catalyzed by MPTC (Q⁺Cl⁻) in the aqueous alkaline (KOH) bi-phase medium and is represented in Scheme 2. The reaction is carried out under MPTC-assisted ultrasonic irradiation condition. In the current investigation, the kinetics was followed in the presence of an excess amount of resorcinol and by fixing allyl bromide as limiting agent. The main reason for investigating this

Results and discussion

The reaction was conducted on a 150 mL three-necked Pyrex round-bottomed flask which permits agitating the solution, inserting the water condenser to recover organic reactant, and taking samples and feeding the reactants. This reaction vessel was suspended at the center of the sonicator. A known quantity of chlorobenzene (30 mL, solvent), potassium hydroxide (0.53 mol), 0.2 g biphenyl IS, (internal standard) were introduced into the reactor. Then, 0.0454 mol, 5 g of resorcinol and 0.1040 mol 12.5 g of

Mechanism

Generally, mechanism [41], [68], [69] for hydroxide ion-initiated PTC reactions are classified into two types viz., (i) Starks extraction mechanism and (ii) Maksoza interfacial mechanism. In the extraction, mechanism is more likely to be a part of reactions when they depend on agitation speed only up to a certain level (300 rpm) and there after the rate will be a constant factor. Also, the energy of activation calculated from the Arrhenius plot will be below 42.8 kJ mol⁻¹. On the other hand, if

Conclusion

In the present study, the reaction was controlled to study the kinetic aspects of the formation of the 1,3-bis(allyloxy)benzene from resorcinol and allyl bromide under ultrasonic-MPTC condition. The apparent reaction rates were observed to obey the pseudo-first order kinetics. Performing the reaction in ultrasonic condition resulted in shorter reaction time, selectivity high yield, etc. The reaction mechanism and the apparent rate constants were obtained from the experimental results. The

Acknowledgments

The authors would like to thank The Pachaiyappa’s Trust, Chennai, Tamil Nadu 600 030, India and Sri Chandrashekarendra Saraswathi Viswa Maha Vidyalaya, Deemed University, Enathur, Kanchipuram, Tamil Nadu 631 561, India for their grant of permission to do this research work.

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

Highlights

Abstract

Introduction

Section snippets

Chemicals

Instrumentation

Ultrasonic process equipment

General procedure for the synthesis of 1,3-bis(allyloxy)benzene under mechanical stirring

Sonicated kinetics of the bi-phase reaction system

Reaction mechanism and kinetic model

Results and discussion

Mechanism

Conclusion

Acknowledgments

Tetrahedron

Tetrahedron

J. Mol. Catal. A: Chem.

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Ultrason. Sonochem.

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Tetrahedron

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Tetrahedron

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Tetrahedron Lett.

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J. Mol. Catal. A: Chem.

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Tetrahedron Lett.

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