An efficient and practical synthesis of bis(indolyl)methanes catalyzed by aminosulfonic acid under ultrasound

Synthesis of bis(indolyl)methanes via electrophilic substitution reactions of indoles with aromatic aldehydes and ketones catalyzed by aminosulfonic acid was carried out in 23-96% yield at 30-38 degrees C in EtOH aqueous solution under ultrasound irradiation.     

A practical and efficient synthesis of bis(indolyl)methanes in water,and synthesis of di-, tri-, and tetra(bis-indolyl)methanes under thermal conditions catalyzed by oxalic acid dihydrate

A simple, clean, and highly efficient green protocol has been developed for synthesis of bis(indolyl), di(bis-indolyl), and tris-indolyl methanes by the reaction of indole with aldehydes and ketones irn the presence of oxalic acid dihydrate [(CO₂H)₂·2H₂O] and N-cetyl-N, N, N-trimethylammonium bromide (CTAB) in water. Also, tri(bis-indolyl) and tetra(bis-indolyl)methanes as new bis(indolyl)methanes were prepared under thermal conditions.     

Ultrasound assisted lipase catalyzed synthesis of poly-6-hydroxyhexanoate

Ultrasonic irradiation greatly improved the Candida antarctica lipase B mediated ring opening polymerization of ε-caprolactone to poly-6-hydroxyhexanoate in the ionic liquid 1-ethyl-3-methylimidazolium tetraflouroborate. Compared to the conventional nonsonicated reaction, sonication improved the monomer conversion by 63% and afforded a polymer product of a narrower molecular weight distribution and a higher degree of crystallinity. Under sonication, the polydispersity index of the product was ∼1.44 compared to a value of ∼2.55 for the product of the conventional reaction. With sonication, nearly 75% of the monomer was converted to product, but the conversion was only ∼16% for the reaction carried out conventionally. Compared to conventional operation, sonication enhanced the rate of polymer propagation by >2-fold and the turnover number of the lipase by >3-fold.     

Improved synthesis of 2,2'-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) derivatives catalyzed by urea under ultrasound

Synthesis of 2,2′-arylmethylene bis(3-hydroxy-5,5-dimethyl-2-cyclohexene-1-one) derivatives catalyzed by urea via the condensation of aromatic aldehydes and 5,5-dimethyl-1,3-cyclohexanedione was carried out in 80-98% yields at 50 °C in aqueous media under ultrasound. This method provides several advantages such as environment friendliness, high yields and simple work-up procedure.     

Ultrasound mediated,iodine catalyzed green synthesis of novel 2-amino-3-cyano-4H-pyran derivatives

An efficient synthesis of a novel series of twelve substituted 2-amino-3-cyano-4H-pyran derivatives was achieved by a one-pot three-component cyclocondensation reaction of heteroaryl aldehydes, malononitrile and active methylene compounds catalyzed by iodine in aqueous medium under ultrasound irradiation. In comparison with conventional methods, our protocol is convenient and offers several advantages, such as shorter reaction time, higher yields, milder conditions and environmental friendliness. We have herein successfully demonstrated the synergistic outcome of multi-component reaction (MCR) and sonication to offer a facile route for the design of these derivatives.     

Ultrasound assisted enzyme catalyzed synthesis of glycerol carbonate from glycerol and dimethyl carbonate

The present work illustrates the transesterification of glycerol to glycerol carbonate (GlyC) from dimethyl carbonate (DMC) using commercial immobilized lipase (Novozym 435) under ultrasonic irradiation. The experiments were performed in a batch reactor placed in an ultrasonic water bath using a sequence of experimental protocol to evaluate the effects of temperature, molar ratios of substrates, enzyme loading, duty cycle and ultrasound power on the conversion of glycerol to GlyC. It has been found that ultrasound-assisted lipase-catalyzed transesterification of glycerol would be a potential alternative to conventional alkali-catalyzed method, as high conversion (99.75%) was obtained at mild operating conditions: molar ratio of DMC to glycerol 3:1, catalyst amount of 13% (w/w), lower power input (100 W), duty cycle 50% and temperature (60 °C) in a relatively short reaction time (4 h) using Novozym 435 as catalyst. Ultrasound reduces the reaction time up to 4 h as compared to conventional stirring method (14 h) catalyzed by Novozym 435. The repeated use of the catalyst under the optimum experimental condition resulted in decay in both enzyme activity and product conversion.     

Ultrasound assisted the chemoselective 1,1-diacetate protection and deprotection of aldehydes catalyzed by poly(4-vinylpyridinium)hydrogen sulfate salt as a eco-benign,efficient and reusable solid acid catalyst

Poly(4-vinylpyridinium) hydrogen sulfate solid acid was found to be efficient catalyst for preparation of 1,1-diacetate using ultrasound irradiation at ambient temperature and neat condition. Deprotection of the resulting 1,1-diacetates were achieved using the same catalyst in methanol solvent under ultrasound irradiation at room temperature. This new method consistently has the advantage of excellent yields and short reaction times. Utilization of solvent free, simple reaction conditions, isolation, and purification makes this manipulation very interesting from an economic and environmental perspective. Further, the catalyst can be reused and recovered for several times.     

Ultrasound assisted synthesis of isopropyl esters from palm fatty acid distillate

Esterification is one of the most preferred synthesis routes for organic esters which are most frequently used as plasticizers, solvents and perfumery and flavour chemicals. The present work deals with acid catalyzed synthesis of isopropyl esters from palm fatty acid distillate (PFAD) in the presence of ultrasonic irradiations operating at 25kHz frequency and 1kW of supplied power. Effect of different operating parameters such as molar ratio of reactants, catalyst quantity and operating temperature has been studied with an aim of optimization. It has been observed that ultrasound enhances the rate of reaction and the extent of equilibrium conversion. The optimum parameters for this process have been found to be 1:5 molar ratio of PFAD to isopropanol, catalyst concentration of 5% of PFAD and 60 degrees C reaction temperature. Maximum conversion levels of about 80% have been obtained in 6h of reaction time under these optimized conditions. Analysis of the kinetic data indicates that the reaction follows first order reversible path.     

A simple and efficient route for the synthesis of di and tri(bis(indolyl) methanes) as new triarylmethanes

Preparation of di and tri(bis(indolyl) methanes) from di and trialdehydes and indoles in the presence of silica sulfuric acid was described. Reactions proceeded in good to excellent yields in acetonitrile as solvent at room temperature.     

Ultrasonic assisted synergetic green synthesis of polycyclic imidazo(thiazolo)pyrimidines by using Fe3O4@clay core-shell

A practical and green approach for the ultrasound-enhanced one-pot multicomponent synthesis of tetraheterocyclic imidazo(thiazolo)pyrimidines is described via the condensation of an 2-aminobenzimidazole or 2-aminobenzothiazole, dimedone and various aldehydes in the presence of Fe₃O₄@clay as an environmentally benign and reusable core/shell nanocomposite catalyst in relatively quantitative yields. This novel eco-friendly protocol includes several advantages such as avoiding hazardous solvents, reusability of the catalyst, easy work-up, short reaction times, room temperature and mild reaction conditions. Furthermore, ultrasonic irradiation and synergistic catalyst showed considerable superiority vs. traditional heating or stirring conditions.     

Ultrasound assisted synthesis of performic acid in a continuous flow microstructured reactor

The present work establishes in depth study of ultrasound assisted preparation of performic acid (PFA) in a continuous flow microstructured reactor. The influence of various parameters viz. formic acid: hydrogen peroxide molar ratio, flow rate, temperature and catalyst loading on the PFA formation were studied in a continuous flow microstructured reactor. In a continuous microstructured reactor in the presence of ultrasonic irradiation, the formation of PFA was found to be dependent on the molar ratio of formic acid: hydrogen peroxide, flow rate of reactants, temperature and catalyst loading (Amberlite IR-120H). The optimized parameter values are 1:1 M ratio, 50 mL/h, 40 °C and 471 mg/cm³ respectively. Further, the performance of Amberlite IR-120H catalyst was evaluated for three successive cycles in continuous microstructured reactor. The performance of catalyst was found to be decreased with the usage of the catalyst and is attributed to neutralization of the sulfonic acid groups, catalyst shrinkage, or loss in pore sites. The experimental results revealed that, for an ultrasound assisted synthesis of PFA in continuous microstructured reactor the observed reaction time was even less than 10 min. The observed intensification in the PFA synthesis process can be attributed to the intense collapse of the cavities formed at low temperature during ultrasonic irradiations, which further improved the heat and mass transfer rates with the formation of H₂O₂ during the reaction. The combined use of ultrasound and a continuous flow microstructured reactor has proved beneficial process of performic acid synthesis.     

Theoretical investigation of a series of bis(1H-tetrazol-5-yl)furazan and bis(1H-tetrazol) derivatives as high-energy-density materials

Using density functional theory (DFT), a series of bis(1H-tetrazol-5-yl)furazan and bis(1H-tetrazol) derivatives with different linkages and substituents are investigated theoretically as potential high-energy-density materials (HEDMs). The heat of formation (HOF), detonation properties, natural bond orbital (NBO) and thermal stabilities are calculated and reported. The introduction of a furazan ring, an –N=N– bridge group and an –N₃ substituent is beneficial to increase the HOF of the title compounds. NBO analysis shows that there are electronic delocalisation effects among the bridge groups, furazan and tetrazole rings, and substituted groups. The conjugation effects and electronic transitions are influenced by the different linkages and substituents. The estimated detonation velocities and pressures indicate that the –ONO₂ and –NO₂ groups and the –N=N– linkage play important roles in enhancing the detonation properties. The bond dissociation energy (BDE) calculations reveal that the –NO₂ group is the substituent group which causes the least thermal stability. The bond between the substituent group and the tetrazole ring is the weakest bond in the title molecules. Considering the detonation performance and the thermal stability, 17 compounds may be promising candidates for HEDMs with good performance. Eight of them (A3, A4, C3, C4, D3, F3, G1 and G3) have better detonation properties than HMX.     

Piperidin-1-yl-phosphonic acid and (4-phosphono-piperazin-1-yl) phosphonic acid: A new class of iron corrosion inhibitors in sodium chloride 3% media

The inhibiting effect of the piperidin-1-yl-phosphonic acid (PPA) and (4-phosphono-piperazin-1-yl) phosphonic acid (PPPA) on the behavior of iron in 3% NaCl media has been examined by electrochemical and gravimetric measurements. Potentiodynamic polarization studies clearly reveal the fact that the addition of increasing concentrations of phosphonic acids moves the corrosion potential towards negative values and reduces the corrosion rate. In uninhibited and inhibited solutions, the increasing of temperature reduces the inhibition efficiency. Changes in impedance parameters (R_t and C_dl) are indicative of adsorption of PPA and PPPA on the metal surface leading to the formation of protective films. Gravimetric measurements reveal that the presence of PPA and PPPA increases the inhibition efficiency by decreasing the corrosion rate. The results obtained by corrosion weight loss tests reveal that adsorption of compounds tested on the ARMCO iron surface obeys to Langmuir adsorption isotherm.     

An expeditious synthesis of beta-indolylketones catalyzed by p-toluenesulfonic acid (PTSA) using ultrasonic irradiation

PTSA catalyzes the Michael addition of indole to alpha,beta-unsaturated carbonyl ketones under ultrasonic irradiation to afford the corresponding product beta-indolylketones in excellent yields (up to 94%).     

Ultrasound assisted acid catalyzed lactose hydrolysis: Understanding into effect of operating parameters and scale up studies

The current work deals with the value addition of lactose by transforming into hydrolyzed lactose syrup containing glucose and galactose in major proportion using the novel approach of ultrasound assisted acid catalyzed lactose hydrolysis. The hydrolysis of lactose was performed in ultrasonic bath (33 kHz) at 50% duty cycle at different temperatures as 65 °C and 70 °C and two different hydrochloric acid (HCl) concentrations as 2.5 N and 3 N. It was observed that acid concentration, temperature and ultrasonic treatment were the major factors in deciding the time required to achieve ∼90% hydrolysis. The ultrasonic assisted approach resulted in reduction in the reaction time and the extent of intensification was established to be dependent on the temperature, acid concentration and time of ultrasonic exposure. It was observed that the maximum process intensification obtained by introduction of ultrasound in the lactose hydrolysis process performed at 70 °C and 3 N HCl was reduction in the required time for ∼90% hydrolysis from 4 h (without the presence of ultrasound) to 3 h. The scale-up study was also performed using an ultrasonic bath with longitudinal horn (36 kHz as operating frequency) at 50% duty cycle, optimized temperature of 70 °C and acid concentration of 3 N. It was observed that the reaction was faster in the presence of ultrasound and stirring by axial impeller at rpm of 225 ± 25. The time required to complete ∼90% of hydrolysis remained almost the same as observed for small scale study on ultrasonic bath (33 kHz) at 50% duty cycle. The use of recovered lactose from whey samples instead of pure lactose did not result in any significant changes in the progress of hydrolysis, confirming the efficacy of the selected approach. Overall, the work has presented a novel ultrasound assisted approach for intensified lactose hydrolysis.     

Development of practical methodologies for the synthesis of novel 3(4-oxo-4H-chromen-3-yl)acrylic acid hydrazides

We report a new environmentally-benign, convenient and facile methodology for the synthesis of new series of 3(4-oxo-4H-chromen-3-yl)acrylic acid hydrazides derivatives designed by exploring the molecular hybridization approach between isoniazide and 3(4-oxo-4H-chromen-3-yl)acrylic acids by using EDCl/HOBt under ultrasound irradiation in very short reaction time. Utilization of easy reaction conditions, isolation and purification makes this manipulation very interesting from an economic perspective.     

Thioglycolic acid (TGA) assisted hydrothermal synthesis of SnS nanorods and nanosheets

Nanorods and nanosheets of tin sulfide (SnS) were synthesized by a novel thioglycolic acid (TGA) assisted hydrothermal process. The as prepared nanostructures were characterized by X-ray diffraction (XRD) study, scanning electron microscopy (SEM) and transmission electron microscopy (TEM). XRD study reveals the formation of well-crystallized orthorhombic structure of SnS. Diameter of the SnS nanorods varied within 30-100 nm. High-resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED) patterns identify the single crystalline nature for the SnS nanocrystals. The mechanism for the TGA assisted growth for the nanosheets and nanorods have been discussed.     

Ethylene glycol promoted catalyst-free pseudo three-component green synthesis of bis(coumarin)s and bis(3-methyl-1-phenyl-1<Emphasis Type="Italic">H</Emphasis>-pyrazol-5-ol)s

An ethylene glycol promoted catalyst-free practically efficient and sustainable approach has been developed for the synthesis of several benzylidene-bis-(4-hydroxycoumarin)s and 4,\(4^{\prime }\)-(arylmethylene)-bis(3-methyl-1-phenyl-1H-pyrazol-5-ol)s by the pseudo three-component reaction of an aldehyde with 4-hydroxycoumarin and 3-methyl-1-phenylpyrazol-5-one, respectively. Inexpensive, non-toxic, and easily available ethylene glycol used as the reaction solvent and promoter renders an efficient protocol in terms of catalyst-free reaction conditions, short reaction time, high yield, practical utility, and green approach.