ACYLATION OF BENZIMIDAZOLINE-2-ONES WITH AROMATIC ACIDS CHLORIDES IN THE PRESENCE OF SMALL AMOUNTS OF FERRIC CHLORIDE HEXAHYDRATE

The article is devoted to the study of phenol cycloalkylation reactions 1-methylcyclopentene in a in periodical action installation in the presence of zeolite-containing catalyst KN-30 and acylation reactions of obtained p-(1-methylcyclopentyl)phenol with acetyl and benzoyl chlorides in the presence of a ZnCl2 catalyst. First of all, the influence kinetic parameters (temperature, time, molar ratios starting components, the amount of catalyst) on the yield and selectivity reactions of cycloalkylation of phenol with 1-methylcyclopentene in the presence of catalyst KN-30 was investigated. In the found optimal conditions for the cycloalkylation reaction: temperature – 110 оС, time – 5 hours, molar ratio of phenol to MCF 1:1, amount of catalyst 12 %, yield of the target product – p-(1-methylcyclopentyl)phenol is 77.3 % (based on phenol), the selectivity of the target product is 92.6 %. Acylation reactions of the obtained p-(1-methylcyclopentyl)phenol with acetyl- and benzoyl chlorides were performed in the presence of anhydrous catalyst ZnCl2. In order to obtain effective conditions for acylation reactions, the influence of the reaction temperature, duration, and molar ratio of the starting components on the yield and selectivity of methylcyclopentylaceto- and benzophenones was studied. As a result, it was found that for acylation reactions of p-(1-methylcyclopentyl)phenol with acetyl and benzoyl chloride in the presence of a ZnCl2 catalyst, the reaction temperature is 140–150 оC, the duration should be 35–40 minutes, and the molar ratio phenol AC(BC) should be 1:2. Under these conditions, the yield of target products is 57.2–61.7 % (based on the taken alkylphenol).

Renewable energy and its many forms, have been the focus of major interests because of their energy potential and environmental benefits, are now emerging as subjects that need more investigation, particularly in relation to biodiesel fuel. This is due to the uncertainty surrounding oil prices and emission regulations. The study included NaOH concentration (0.6, 0.8, 1, and 1.2 wt.%), ethanol:oil molar ratio (6:1, 8:1, 10:1, and 12:1), temperature of reaction (30, 45, 60, and 75 °C), and duration of reaction (30, 45, 60, and 75 min) as significant parameters influencing the yield of ethyl ester. For the first time, to the best of our knowledge, the L16 orthogonal design matrix of the Taguchi method approach was applied in the present research to optimize the transesterification step parameters from linseed oil. ANOVA validation studies determined the relative influence of the process parameters. A maximum biodiesel yield of 95.20% was obtained under optimum reaction conditions: 1 wt% NaOH, 10:1 ethanol:oil molar ratio, 75°C reaction temperature and 60 min reaction time. The highest contribution ranking of the four variables was 48.95% with the ethanol:oil molar ratio, 22.32% with NaOH loading, 18.24% with the temperature of the reaction, and 9.59% with the duration of the reaction. The fuel properties of synthesized linseed oil ethyl ester, at the specified ideal reaction conditions, were met the range of the standard EN14214.

Synthesis of Dihydroisoquinoline and Dihydropyridine Derivatives via Asymmetric Dearomative Three-Component Reaction

A series of novel acylpyrazole derivatives containing 1,2,3‐thiadiazole ring 3a–3m were synthesized by the condensations of 1‐phenyl‐3‐methyl‐4‐(substituted benzal or 4‐methyl‐1,2,3‐thiadiazole‐5‐carbonyl)‐5‐hydroxypyrazole 2 with 4‐methyl‐1,2,3‐thiadiazole‐5‐carbonyl chloride or substituted benzoyl chloride. Their structures were confirmed by IR, 1H‐NMR, mass spectroscopy, and elemental analyses. The results of preliminary bioassays showed that some of the title compounds 3 exhibited moderate to good herbicidal activities against dicotyledonous plants (Brassica campestris L.) at the concentration of 100 mg/L. For example, compounds 3e, 3f, 3g, and 3k possessed 74.6%, 72.2%, 70.3%, and 84.5% inhibition against B. campestris L., respectively, whereas commercially available herbicide Sulcotrione showed only 35.0% inhibition at the same concentration. Moreover, these compounds displayed higher herbicidal activity against B. campestris L. than Echinochloa crus‐galli. However, these compounds showed weak activities at the concentration of 10 mg/L.

Chiral colorimetric sensor 4 has been synthesized, and the structure characterized by IR and 1H NMR spectroscopy, mass spectrometry, and elemental analysis. The chiral recognition of the receptor was studied by 1H NMR and UV-vis spectroscopy. The results of non-linear curve fitting indicate that the receptor 4 and l- or d-mandelate and alanine anions form a 1:1 stoichiometric complex. The obvious colour change of receptor 4 can be observed by the naked eye when the enantiomers of mandelate and alanine anions are added, which demonstrates that receptor 4 may be used as the colorimetric sensor for the two carboxylic anions.

Soluble poly(ferrocenylenevinylene) (PFV) 6 was synthesized via ring-opening metathesis polymerization (ROMP) of ansa-(vinylene)ferrocene Fe(η-C5H3tBu)2C2H2 (5) with tBu substituents on the cyclopentadienyl (Cp) ligands. Monomer 5 was obtained through intramolecular dicarbonyl coupling of the corresponding ferrocene-dicarbaldehyde, 1,1‘-di-t-butyl-3,3‘-dicarbaldehyde, Fe(η-C5H3tBu)(CHO)2 (4) in the presence of the McMurry reagent. Both monomer precursor 4 and monomer 5 were structurally characterized by 1H and 13C NMR spectroscopy, X-ray crystallography, mass spectrometry, and elemental analysis. ROMP of 5 was investigated using molybdenum-based (Schrock-type) and ruthenium-based (Grubbs-type) initiators under various conditions and was monitored by 1H NMR spectroscopy. Soluble polymers with low or high molecular weight were obtained and completely characterized. Photolytic and thermal ring-opening polymerizations of 5 were also attempted, but only unreacted monomer was isolated under these conditions. Th...

Eleven new and three reported half-sandwich Ru(II) arene complexes were synthesized using [Ru(η6-benzene)Cl(μ-Cl)]2 and [Ru(η6-toluene)Cl(μ-Cl)]2 and four pyridine carboxylic acid-based ligands (dicarboxylic acids and halogen derivatives). The structures and purity of synthesized compounds were confirmed using 1H and 13C NMR spectroscopy, infrared spectroscopy, mass spectrometry, and elemental analysis. The stability of synthesized compounds in dimethyl sulfoxide solution was confirmed using 1H NMR spectroscopy. The seven ligands, two complex precursors (CP1 and CP2), and 14 half-sandwich Ru(II) picolinate complexes (C1–C14) were evaluated for in vitro antibacterial and antifungal activity against pathogens, such as Staphylococcus aureus, Bacillus cereus, Proteus mirabilis, Klebsiella pneumoniae, Ecsherichia coli, Pseudomonas aeruginosa, Salmonella enteritidis, Enterobacter aerogenes, and yeast Candida albicans, using the microwell-dilution method. Among the tested samples, the ligands showed better inhibitory effect against Gram-positive bacteria when compared to the metal complexes. The most susceptible Gram-negative bacteria was Ecsherichia coli, with a MIC value of 1.25 mg/mL, for C3, C6, and C10. All synthesized complexes showed similar, slightly better activity against Candida albicans.

Facile Access to Polar-Functionalized Ultrahigh Molecular Weight Polyethylene at Ambient Conditions

Acylation of o-Cresol with Pyromellitic Dianhydride

Synthesis and properties of novel diisocyanate based optically active polyimides

Exploration of Oxidative Ritter-Type Reaction of α-Arylketones and Its Application for the Collective Total Syntheses of <i>Erythrina</i> Alkaloids

Supramolecular Template-Assisted Catalytic [2+2] Photocycloaddition in Homogeneous Solution

Upcycling Polytetrahydrofuran to Polyester

Amides are valuable functional groups in biological, agrochemical, and pharmaceutical molecules. Several amides such as Weinreb amides, morpholine amides, and pyrrolidine amides are useful intermediates for the synthesis of aldehydes or ketones. Among them, morpholine amides are a cheap and good substitute for Weinreb amides. A large number of synthetic methods for making amides from various carboxylic acid derivatives have been reported. Among these, the aminolysis of acid chlorides in the presence of non-nucleophilic tertiary amines is generally considered to be the method of choice. Amides can also be synthesized using metals such as zinc, indium and samarium instead of tertiary amines from acid chlorides. Herein, we wish to report an alternative direct conversion of acid chlorides to secondary and tertiary amides (including morpholine amides), which proceeds under mild reaction conditions (0 °C) with an almost stoichiometric amount of amine and a short reaction time, and gives very good to excellent yields (Scheme 1). To demonstrate the feasibility of performing the desired reaction under a variety of conditions, we first carried out the synthesis of tertiary amides from benzoyl chloride. The corresponding morpholine amides could be obtained in 99% yield by reaction with benzoyl chloride under optimized reaction conditions in the presence of diisobutyl(morpholino)aluminum, which was easily prepared from morpholine and diisobutylaluminum hydride (DIBALH). The results are summarized in Table 1. We next synthesized various secondary and tertiary amides from other acid chlorides under the optimal conditions deduced from the previous experimental results. The results obtained for the reaction of benzoyl chloride with various primary and secondary amines are summarized in Table 2. As shown in Table 2, various noncyclic and cyclic primary amines underwent smooth conversion to the corresponding secondary amides in 90-99% yields (entries 1-5). Furthermore, the secondary amines also afforded the corresponding tertiary amides in 75-99% yields under similar reaction conditions (entries 6-10). From these results, we anticipated that the treatment of diisobutyl(morpholino)aluminum with representative acid chlorides would be effective for the direct synthesis of morpholine amides. Table 3 summarizes the results of the one-pot synthesis of morpholine amides from various acid chlorides. As expected, various aromatic acid chlorides with electronwithdrawing and electron-donating substituents underwent the conversion to the corresponding morpholine amides smoothly, in 89-99% yields (entries 1-7). A polyaromatic acid chloride such as naphthoyl chloride and a heterocyclic aromatic acid chloride such as furoyl chloride gave the corresponding morpholine amides in 92% and 91% yields, respectively, via the same methodology (entries 8 and 9). Furthermore, aliphatic acid chloride such as caproyl chloride smoothly afforded the corresponding morpholine amide in 96% under the same reaction conditions (entry 10). A proposed mechanism for this reaction is shown in Scheme 2 for the conversion of benzoyl chloride to the corresponding piperidine amide. Initially, the intermediate 2 is produced through the attack on the acid chloride by the secondary amino anion in diisobutyl(piperidino)aluminum 1 to give intermediate 3, with the release of an aluminum complex from intermediate 2. Finally, the hydrolysis of the Table 1. Optimization of reaction conditions for the synthesis of tertiary amides from acid chlorides

Amides are valuable functional groups in biological, agrochemical, and pharmaceutical molecules. Several amides such as Weinreb amides, morpholine amides, and pyrrolidine amides are useful intermediates for the synthesis of aldehydes or ketones. Among them, morpholine amides are a cheap and good substitute for Weinreb amides. A large number of synthetic methods for making amides from various carboxylic acid derivatives have been reported. Among these, the aminolysis of acid chlorides in the presence of non-nucleophilic tertiary amines is generally considered to be the method of choice. Amides can also be synthesized using metals such as zinc, indium and samarium instead of tertiary amines from acid chlorides. Herein, we wish to report an alternative direct conversion of acid chlorides to secondary and tertiary amides (including morpholine amides), which proceeds under mild reaction conditions (0 °C) with an almost stoichiometric amount of amine and a short reaction time, and gives very good to excellent yields (Scheme 1). To demonstrate the feasibility of performing the desired reaction under a variety of conditions, we first carried out the synthesis of tertiary amides from benzoyl chloride. The corresponding morpholine amides could be obtained in 99% yield by reaction with benzoyl chloride under optimized reaction conditions in the presence of diisobutyl(morpholino)aluminum, which was easily prepared from morpholine and diisobutylaluminum hydride (DIBALH). The results are summarized in Table 1. We next synthesized various secondary and tertiary amides from other acid chlorides under the optimal conditions deduced from the previous experimental results. The results obtained for the reaction of benzoyl chloride with various primary and secondary amines are summarized in Table 2. As shown in Table 2, various noncyclic and cyclic primary amines underwent smooth conversion to the corresponding secondary amides in 90-99% yields (entries 1-5). Furthermore, the secondary amines also afforded the corresponding tertiary amides in 75-99% yields under similar reaction conditions (entries 6-10). From these results, we anticipated that the treatment of diisobutyl(morpholino)aluminum with representative acid chlorides would be effective for the direct synthesis of morpholine amides. Table 3 summarizes the results of the one-pot synthesis of morpholine amides from various acid chlorides. As expected, various aromatic acid chlorides with electronwithdrawing and electron-donating substituents underwent the conversion to the corresponding morpholine amides smoothly, in 89-99% yields (entries 1-7). A polyaromatic acid chloride such as naphthoyl chloride and a heterocyclic aromatic acid chloride such as furoyl chloride gave the corresponding morpholine amides in 92% and 91% yields, respectively, via the same methodology (entries 8 and 9). Furthermore, aliphatic acid chloride such as caproyl chloride smoothly afforded the corresponding morpholine amide in 96% under the same reaction conditions (entry 10). A proposed mechanism for this reaction is shown in Scheme 2 for the conversion of benzoyl chloride to the corresponding piperidine amide. Initially, the intermediate 2 is produced through the attack on the acid chloride by the secondary amino anion in diisobutyl(piperidino)aluminum 1 to give intermediate 3, with the release of an aluminum complex from intermediate 2. Finally, the hydrolysis of the Table 1. Optimization of reaction conditions for the synthesis of tertiary amides from acid chlorides