Terpenes as Renewable Resources for Organic and Macromolecular Chemistry

With the goal to develop innovative science and technology to significantly reduce our dependence on fossil fuel, the use of the renewable resources via green procedures are discussed. Implementation of efficient approaches, such as thiol-ene reactions and organocatalysis provides the potential to achieve sustainability. Thus, a considerable amount of novel monomers and polymers are prepared from terpenes or vanillin in combination with fatty acid derivatives

GREEN CHEMISTRYAPPLICATION FOR THE SYNTHESIS OF (1)-N-4\u27-METHOXYBENZVL-1,1O-PHENANTHROLINIUMBROMIDE

ABSTRACT A simple, energy-efficient, and relatively quick synthetic procedure for the synthesis of (1)-N-4\u27- methoxybenzyJ-1,10-phenanthroliniumbromide, based on green chemistry principles has been carried out. The synthesis was started by solvent-free reduction of p-anisaldehyde with NaBH4to give 4-methoxybenzyl alcohol in 98% yield to be followed by solvent-free treatment of the resulted alcohol with PBr3 to yield 4-methoxybenzyl bromide (86%). Furthennore, the obtained bromide was reacted with 1,10-phenanthrolinein acetone at reflux for 12 h to give the phenanthrolinium salt target in 68%yield. Keywords:green chemistry, p-anisaldehyde,(1)-N-4\u27-methoxybenzyl-1, 1Q-phenanthroliniumbromid

SYNTHESIS OF POLY-5,7-DIALLYL-25,26,27,28-TETRAHYDROXYCALIX[4]ARENE

The synthesis of poly-5,7-diallyl-25,26,27,28-tetrahydroxycalix[4]arene were performed in experimental series as follows: (1) Cyclotetramerization of p-t-butylphenol with NaOH and paraformaldehyde to p-butylcalix[4]arene, (2) Debutylation of p-butylcalix[4]arene using AlCl3 and phenol to tetrahydroxycalix[4]arene, (3) Allylation reaction using allylbromide to diallyloxy-dihydroxycalix[4]arene, (4) Claisen rearrangement reaction, (5) Cationic polymerization to diallylcalix[4]arenes. All of the synthesized products were analyzed by means of IR spectrometer and 1H-NMR spectrometer. The result of 25,27-diallyloxy-26,28-dihydroxycalix[4]arene synthesis was white crystals having m.p. 205-207 °C in 80.95% yield. The synthesis of 5,7-diallyl-25,26,27,28-tetrahydroxy-calix[4]arene gave light yellow crystals having m.p. 214-216 °C in 78.67% yield. The polymerization gave poly(5,7-diallyl-25,26,27,28-tetrahydroxycalix[ 4]arene) having m.p. 338-340 °C, in 60% yield. Its estimated has a relative molecular weight of 18,738 g/mol with the number of unit repetition about 37 monomer units. Keywords: Diallylation, polymerization, Poly-5,7-diallyl-25,26,27,28-tetrahydroxycalix[4]aren

SYNTHESIS OF POLY -5,7 -DIALL YL-25,26,27,28-TETRAHYDROXYCALlX[4]ARENE

ABSTRACT The synthesis of poly-5,7-diallyl-25,26,27,28-tetrahydroxycalix[4]arenewere performed in experimental series as follows: (1) Cyclotetramerizationof p-t-butylphenol with NaOH and paraformaldehyde to p-butylcalix[4]arene, (2) Debutylation of p-butylcalix[4]arene using AICI3and phenol to tetrahydroxycalix[4]arene,(3) Allylation reaction using allylbromide to diallyloxy-dihydroxycalix[4]arene,(4) Claisen rearrangement reaction, (5) Cationic polymerization to diallylcalix[4]arenesA.ll of the synthesizedproductswere analyzedby meansof IR spectrometerand 1H-NMR spectrometer. The result of 25,27-diallyloxy-26,28-dihydroxycalix[4]arenesynthesis was white crystals having m.p. 205-207 °C in 80.95% yield. The synthesis of 5,7-diallyl-25,26,27,28-tetrahydroxy-calix[4]arenegave light yellow crystals having m.p. 214-216 °C in 78.67% yield. The polymerization gave poly(5,7-diallyl-25,26,27,28-tetrahydroxycalix[ 4]arene)having m.p. 338-340 °C, in 60% yield. Its estimated has a relative molecular weight of 18,738 glmol with the number of unit repetition about 37 monomer units. Keywords: Diallylation, polymerization, Poly-5, 7-diallyl-25, 26, 27,28-tetrahydroxycalix[4]aren

Synthesis of 2,2,4-Trimethyl-2,3-dihydro-1H-1,5-benzodiazepine using Treated Natural Zeolite Catalyst

The cyclocondensation of 1,2-phenylenediamine and acetone in the presence of treated natural zeolite catalyst (TNZ) under solvent-free condition has been done. The research consisted of three steps. The first step was treatment of natural zeolite by mixing this material in hydrochloric acid solution at 50 °C for 1 hour to be followed by soaking the zeolite in ammonium chloride solution for 5 days. The second step was solvent-free condensation of 1,2-phenylenediamine and acetone using TNZ at 50 °C for 2 hours with weight ratio variation of catalyst, i.e. 15, 30, 45, and 60% (wt/wt). The third step was to study catalyst reusability for the condensation reaction. Based on TLC, FTIR, and 1H NMR analyses, the condensation afforded 2,2,4-trimethyl-2,3-dihydro-1H-1,5-benzodiazepine as the product in 73% yield with the optimum of catalyst loading at 30% (wt/wt). The reusability test showed that the catalyst can be reused for the cyclocondensation for four times. Copyright © 2019 BCREC Group. All rights reserve

Cellulose Ethers from Banana (<i>Musa balbisiana</i> Colla) Blossom Cellulose: Synthesis and Multivariate Optimization

Cellulose ethers are biocompatible polymers which have attracted considerable attention for various applications due to their physical and mechanical properties. The present work aims to find the optimum condition for synthesizing cellulose ethers from banana blossom cellulose (BBC) such as methylcellulose (MC), carboxymethyl cellulose (CMC) and hydroxypropyl cellulose (HPC). The ultrasonication-assisted method as an energy source is used to shorten the synthesis time at room temperature and obtain high yields. The influences of various parameters (NaOH concentration, etherification agents, and sonication time) were analyzed using a multivariate statistical modeling response surface methodology (RSM). The materials were characterized by FTIR, SEM, and TGA. The cellulose ethers obtained have the potential as food additives with DS values of 2.0, 0.7, and 0.86, respectively. MC was synthesized optimally with a yield of 96.52% using a composition of cellulose (0.4 g), 50% (w/v) NaOH (10 mL) and dichloromethane (6 mL). CMC was synthesized optimally with a yield of 98.26% using a composition of cellulose (0.4 g), 30% (w/v) NaOH (2 mL) and monochloroacetic acid (1 g). HPC was synthesized optimally with a yield of 97.51% using a composition of cellulose (0.4 g), 10% (w/v) NaOH (2 mL) and propylene oxide (1.5 mL)

The Mechanical Properties Of Green Polyblend Based On Waste Polypropylene Filled In Variation Particle Size Natural Fiber And Initiator Concentration

Synthesis of green polyblend from waste polypropylene (recycle polypropylene, rPP) filled reinforcing husk rice powder (HR) in weight ratio rPP/HR (8/2) using multifunctional acrylic acid (AA) processed reactively in internal mixer had been carried out. To understand the effect of initiator concentration, some concentration variations of benzoyl peroxide (BPO) initiator had been done in 5 levels (0; 0.02; 0.05; 0.07; and 0.10 phr). Based on the mechanical properties (tensile strength, TS) and the melt flow index (MFI) in thermoplastic condition, it was found that the best concentration was 0.02%. To study the effect of particle size, four level variations (40; 70; 100 and 120 mesh) of the HR particle size using 0.02 phr BPO was prepared. It has been found that decreasing the particle size (40 to 120 mesh) decrease the MFI accordance with ASTM andincrease the TS value. To understand the correlation between particle size and biodegradability of the green polyblend, firstly, it was performed water absorption characterization to the polyblend specimen. Water absorption(WA) studies showed an increase in water uptake with increase in particle size. Biodegradation of the green polyblend (reflected by the lost of weight, LW) was done by burying the specimen in cellulolytic bacteria enriched garbage soil for four months. The result showed that increasing the HR particle size (120 to 40 mesh) increase the biodegradation properties.

Green synthesis of renewable dimethyl terephthalate-like monomer from eugenol

Dimethyl terephthalate, a diester monomer derived from petroleum-based resources, plays important role in the production of polyester such as polyethylene terephthalate (PET), resins for polyester, fibres, and films as well as engineering polymers. High demand on PET together with environmental concerns require to find alternative for renewable monomers urgently whenever or wherever to substitute the exhausting crude oil-based monomers. A simple and highly efficient method to prepare PET analogue monomer, methyl 2-[2-methoxy-4-[3-(2-methoxy-2-oxoethyl)] thiopropyl]phenoxy acetate (4), from renewable eugenol is described. The key step involves successive Williamson etherification, esterification, to be followed by thiol-ene reaction. Remarkably, it turned out that the thiol-ene reaction has proven to be effective in the introduction of the ester group to the olefinic substrate without the use of solvent and initiator leading to diester 4. The technique offered here comprises advantages i.e. excellent yields, mild reaction condition, and easy to perform, thus, provide a sustainable alternative to synthesize diester from eugenol

Oxygen Reduction Reaction (ORR) of Pt/C Standard in Different Electrolyte Solutions and Terbium(III) Monoporphyrinato Complex

Electrocatalytic parameters of a Pt/C standard and a sample of terbium(III) monoporphyrinato were investigated in different solutions. N electron transfer, Tafel slope, Eonset, and overpotential of the catalyst of Pt/C in different solutions were calculated and analyzed using a rotating ring disk electrode (RRDE) in 0.5 M H2SO4, 0.1 M HClO4 and 0.1 M NaOH. In the RRDE measurements, a bipotentiostat at a potential range of 1.03 to 0.05 V vs RHE (Ering = 1.2 V vs RHE) with a scan rate of 5 mV/s and rotation rates of 200, 400, 900, 1600 and 2500 rpm was used. Hereafter, the test of terbium(III) monoporphyrinato compound formulated in [Tb(TPP)(cyclen)]Cl (TPP = 5,10,15,20-tetraphenylporphyrinato; cyclen = 1,4,7,10-tetraazacyclododecane) as a candidate material for ORR electrocatalyst was also done. The results showed that the measurement of Pt/C standards was satisfactory according to the literature for all parameters with the n electron transfer close to 4 in all electrolytes media. [Tb(TPP)(cyclen)]Cl had an n electron transfer value of 2.38, suggesting that the [Tb(TPP)(cyclen)]Cl compound has less potential for ORR catalysts

Synthesis and Characterization of Anethole-lauryl Methacrylate Copolymer via Cationic Polymerization

The synthesis of anethole-lauryl methacrylate (LMA) copolymer had been carried out by cationic polymerization using BF3O(C2H5)2 as the initiator without the use of solvent at room temperature (28-30 °C) over atmospheric N2 conditions. Polymerization was conducted by varying LMA concentration i.e. 2%, 4%, and 6%, (w/w) with respect to the anethole weight. Structural determination of co-poly(anethole-LMA) was done using FTIR and 1H-NMR spectrophotometer. The relative molecular weight (Mv) of co-poly (anethole-LMA) was measured by an Ostwald Viscometer at room temperature. Morphological characterization and surface area analysis of co-poly(anethole-LMA) was performed using SEM and SAA, respectively. The successful synthesis of co-poly(anethole-LMA) was proven by the disappearance of vinyl group absorption at 1696, 1638, 965, and 938 cm-1 of the FTIR spectra, as well as the loss of vinyl group proton signals at 6.4-5.5 ppm in the 1H-NMR spectra. Increasing the weight of the LMA affected the characteristics of co-poly(anethole-LMA). The relative molecular weight of co-poly(anethole-LMA) was found to rise by increasing the weight of LMA. The Mv of co-poly(anethole-LMA) 2%, 4%, and 6% were 32378.62, 50611.05, and 65133.79 g/mol, respectively. The morphology of co-poly(anethole-LMA) showed that the surface distance between particles was getting tighter and the highest surface area in co-poly(Anethole-LMA) 6% was 233.80 m2/g