Substituted Benzoyl Chlorides Research Articles

Unexpected migration of a benzoyl group in the intramolecular Wittig reaction of o-acyloxybenzylidenephosphoranes with benzoyl chlorides: One-pot synthesis of isomeric 3-benzoyl-2-phenylbenzofurans

The reaction of o-acyloxybenzylidenetriphenylphosphoranes with substituted benzoyl chlorides in an aprotic solvent led, together with the expected 2-phenylbenzofuran, to isomeric 3-benzoyl-2-phenylbenzofuran derivatives. This result formally corresponds to intramolecular migration of the benzoyl group from the ortho oxygen atom to the ylide carbanion via cyclization and ring opening of the starting o-acyloxybenzylidenetriphenylphosphoranes.

Synthesis of Novel Triazolyl Thiourea Derivatives and Their Antibacterial Activity

4-Amino-5-methyl-2,4-dihydro-3H-1,2,4-triazole-3-thione was synthesized in three steps from carbon disulfide, hydrazine hydrate, and acetic acid. Its reaction with benzoyl isothiocyanates prepared from substituted benzoyl chlorides and ammonium thiocyanate afforded the corresponding N-benzoyl-N′-triazolyl-thioureas. The obtained compounds were screened for antibacterial activity against Staphylococcus aureus (ATCC 25923), Staphylococcus epidermidis (ATCC 12228), Enterococcus faecalis (ATCC 29212), Escherichia coli (ATCC 25922), and Pseudomonas aeruginosa (ATCC 27853). Their antibacterial activity against gram-positive bacteria was higher than against gram-negative bacteria, and derivatives containing electron-withdrawing groups were more active than those with electron-donating substituents.

Synthesis and comparative study of catalytic activity between Pd-metallodendrimer and Pd/Cu-bimetallodendrimer nanoparticle-based on triazine

Triazine-based heterogeneous Pd/Cu-bimetallodendrimer Nanoparticle (Pd/Cu-BMDNP) has been synthesized by sequential loading method from palladium containing metallodendrimer (Pd-MD) which was prepared by the reaction of 2,4,6-Triamine-1,3,5-triazine (melamine) with substituted benzoyl chloride using (Ph3P)2PdCl2 in DMSO at 90 °C. SEM and EDX of Pd/Cu-BMDNP showed the nanosized aggregated spherical surface morphology and the presence of Palladium and copper of the NP. Also, the phase was detected as Face Centered Cubic (FCC) structure by XRD analysis. In addition, the average particle size of Pd/Cu bimetallic catalyst was identified as 12–13 nm by TEM investigation. Greater thermal stability of Pd/Cu-BMDNP than Pd-MD was detected from TG and DSC experiments. The Pd-metallodendrimer has been also characterized by IR, 1H NMR, 13C NMR, SEM, EDX, Mass, TG and DSC techniques. The simple recoverability, high reusability, low amount of catalyst loading, negligible amount of catalyst leaching of the heterogeneous Pd/Cu-BMDNP have made more effective catalyst than homogeneous Pd-metallodendrimer for the C–C cross-coupling reaction such as Heck, Glaser, Sonogashira and Suzuki-Miyaura in excellent yields.

Reactions of an Isolable Dialkylgermylene with Acyl Chlorides Forming Acyl(chloro)germanes and Diacylgermanes

The reactions of isolable dialkylgermylene 1 with benzoyl and substituted benzoyl chlorides afford the corresponding aroyl(chloro)germanes in high yields. While 2,2-dimethylpropanoyl chloride reacts similarly, the reactions of more reactive alkanoyl chlorides such as acetyl, propanoyl, and butanoyl chlorides give rather unexpectedly the corresponding dialkanoylgermanes 3 together with alkanoyl(chloro)germanes 2 (2:3 = 4:1). Aroyl- and alkanoyl(chloro)germanes 2a–2g and dialkanoylgermanes 3e–3g obtained were fully characterized by multinuclear NMR spectroscopy, high-resolution mass spectrometry (HRMS), and by single-crystal X-ray diffraction studies for 2a and 3f. UV–vis spectra of 3e–3g and a TDDFT study of the model diacylgermanes showed two separated n → π* absorption bands, suggesting significant electronic interaction between the two carbonyl groups in a molecule through the central germanium atom.

Synthesis, Characterization and catalytic activity of Palladium-Based Metallodendrimer with Triazine

A novel Pd-based metallodendrimer has been directly prepared by the reaction of substituted triazine with substituted benzoyl chloride in good yields using (Ph3P)2PdCl2 and DMF at 70 oC. This procedure avoids the use of high temperature and severe reaction conditions. The surface morphology like as entangled nanofibers from SEM image and the presence of Palladium ions of the compound from EDX analysis were obtained in addition TG and DSC showed the good thermal stability of the compound. This white solid compound was found to be an effective homogeneous catalyst for the synthesis of ynones in where the synthetic route was copper and phosphine ligand-free.

Synthesis, Crystal Growth, and Optical Characterization of a Novel Nonlinear Optical Organic Material: N,N‐Diarylbenzamide

AbstractNonlinear optical organic materials of N,N‐diphenylbenzamide (NNDPB) and 4‐fluoro‐N,N‐diphenylbenzamide (FNNDPB) are synthesized from benzoylation of N,N‐diphenylamine using the substituted benzoyl chlorides. The single crystals of NNDPB and FNNDPB are grown by a slow evaporation technique. Single‐crystal X‐ray diffraction shows that both the crystals belong to orthorhombic crystallographic system with space group Pbca. Fourier transform infrared spectrum shows the chemical bonding and various functional groups, the carbonyl peak appeared at 1647 and 1651 cm−1 in NNDPB and FNNDPB compounds, respectively. 1H and 13C nuclear magnetic resonance analysis examines the placement of aromatic protons and carbons are identified to the synthesized materials. UV–vis near IR spectra analysis showed 100% transmission in the visible region for both NNDPB and FNNDPB crystals. As‐grown crystal dielectric constant and dielectric loss are inversely proportional to the frequency at all the temperatures. The thermal properties of NNDPB and FNNDPB crystals are studied from thermogravimetric analysis/differential thermal analysis analysis, it is thermally stable up to 483 and 503 K. Crystal growth mechanism and defects are observed from etching studies. The relative second harmonic generation efficiency is measured by Kurtz–Perry powder technique and is found to be 1.55 and 1.7 times as that of potassium dihydrogen phosphate.

Synthesis of 4-aryl-1,3,4a-Triazaphenanthrene-2-Selones via Three-Component Condensation of Quinolin-2-Amine, Potassium Selenocyanate and an Acyl Chloride

A three-component reaction between quinolin-2-amine, potassium selenocyanate and variously substituted benzoyl chlorides in acetone at room temperature provided a simple and efficient one-pot route for the synthesis of six 4-aryl-1,3,4a-triazaphenanthrene-2-selones in good yields.

Unexpected one-step synthesis of 3-benzoyl-2-phenylbenzofurans under Wittig conditions

The reaction of 2-hydroxybenzyltriphenylphosphonium bromide with substituted benzoyl chlorides under Wittig conditions, led to 2-phenylbenzofuran derivatives 4a–p and the unexpected formation of 3-benzoyl-2-phenylbenzofuran derivatives 5a–p. Benzoyl chlorides possessing electron-withdrawing groups afforded 3-benzoyl-2-phenylbenzofuran derivatives in higher yields than those with electron-donating groups. This reaction represents a simple and regioselective, one-pot route towards the preparation of deactivated 3-benzoyl-2-phenylbenzofuran compounds which are difficult to obtain by the direct acylation of 2-phenylbenzofurans.

Synthesis of 1-aryl-2,4,10a-Triazaphenanthrene-3-Selones Via a Three-Component Condensation of Isoquinolin-1-Amine, Potassium Selenocyanate and an Acyl Chloride

A simple, one-pot synthesis of six 1-aryl-2,4,10a-triazaphenanthrene-3-selones has been achieved with moderate to good yields via a three-component condensation of isoquinolin-1-amine, potassium selenocyanate and variously substituted benzoyl chlorides in acetone at room temperature.

Synthesis, Characterization, and Evaluation of Cancer Prevention Activity of Novel Modified Heterocyclic Compounds

Anticancer approaches may employ change of molecular structure to enhance preventive influence of chemical agents. The present examination concerned the potential anticancer impact of modified heterocyclic compounds. A strategy was developed to combine tetrazole moieties from different diamines with 2-aminobenzoic and substituted benzoyl chloride compounds with attention to synthesis, characterization and assessment of cancer preventive activity, applying IR, 1HNMR, 13CNMR and Mass spectra.

Synthesis, structural, optical and thermal properties of N-methyl–N-aryl benzamide organic single crystals grown by a slow evaporation technique

The organic materials, N-methyl–N-aryl benzamides were synthesized from benzoylation of N-methyl-4-nitrobenzenamine (MNBA) using suitably substituted benzoyl chlorides. The products were purified by recrystallization and their single crystal were grown by a slow evaporation technique. The crystals were characterized by FTIR, UV–Vis–NIR, 1H &13C NMR, and single & powder X-ray diffraction. Thermal stability of the crystals was studied by thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC). Dielectric and NLO properties of MNPB, FMNPB and MMNPB crystals were studied. The second harmonic generation (SHG) has been confirmed by the Kurtz powder test for all these crystals and the SHG efficiency of MMNPB crystal was found to be 2.25 times higher than that of KDP crystal.

Insertion of an Isolable Dialkylstannylene into C–Cl Bonds of Acyl Chlorides Giving Acyl(chloro)stannanes

The reactions of isolable dialkylstannylene 1 with 1-adamantanoyl, 2,2-dimethylpropanoyl, benzoyl, and substituted benzoyl chlorides afford the corresponding acyl(chloro)stannanes in good yields. Similar reactions with more reactive acetyl and propanoyl chlorides do not give the corresponding insertion products but the corresponding dichlorostannane by the overreaction. The benzoyl(chloro)stannane reacts with acetyl chloride to afford the corresponding 1,2-dione and the dichlorostannane quantitatively. Acyl(chloro)stannanes obtained were fully characterized by multinuclear NMR spectroscopy, high-resolution mass spectrometry, and by single-crystal X-ray diffraction studies.

Synthesis of new 4-amino-5-(1,4-benzodioxan-2-yl)-4H-1,2,4-triazole-3-thiol derivatives

Acylation and cyclization reactions of 4-amino-5-(1,4-benzodioxan-2-yl)-4H-1,2,4-triazole-3-thiol were studied. Acylation of the title compound with substituted benzoyl chlorides gave the corresponding amides, whereas its reactions with substituted benzoic acids in the presence of POCl3 were accompanied by cyclization with formation of triazolothiadiazoles containing a 1,4-benzodioxane substituent. 4-Amino-5-(1,4-benzodioxan-2-yl)-4H-1,2,4-triazole-3-thiol reacted with substituted benzaldehydes to afford the corresponding Schiff bases, and its alkylation with chloroacetic acid in ethanol in the presence of sodium acetate gave S-ethoxycarbonylmethyl derivative.

A Concise Synthesis of Novel Aryl Pyrimidine C‐Nucleoside Analogs from Sugar Alkynes

AbstractAryl‐ and amino‐substituted pyrimidine C‐nucleoside analogs have been synthesized in good to excellent yields by one‐pot coupling of terminal sugar alkynes, substituted benzoyl chlorides, and amidine salts. The reaction conditions are tolerant of various structurally complex sugars having sterically bulky groups, unprotected hydroxyl groups, and sensitive substituents. The sugar alkynes include structurally diverse pyranosides, acyclic glycosides, and furanosides. The substituted benzoyl chlorides bear electron‐withdrawing and ‐donating substituents with different steric hindrance. The amidine salts include acetamidine hydrochloride, benzamidine hydrochloride, and guanidine hydrochloride.

Synthesis, structure-activity relationships studies of benzoxazinone derivatives as α-chymotrypsin inhibitors

A series of benzoxazinones 1–28 were synthesized via reaction of anthranilic acid with various substituted benzoyl chlorides in the presence of triethylamine in chloroform. Compounds 1–18 showed a good inhibition of α-chymotrypsin with IC50±SEM values between 6.5 and 341.1μM. Preliminary structure-activity relationships studies indicated that the presence of substituents on benzene ring reduces the inhibitory potential of benzoxazinone. Also the increased inhibitory potential due to fluoro group at phenyl substituent was observed followed by chloro and bromo substituents. Compounds with strong electron donating or withdrawing groups on phenyl substituent, showed a good inhibitory potential at ortho>meta>para position. Kinetics studies showed diverse types of inhibition, except uncompetitive-type inhibition. The Ki values ranged between 4.7 and 341.2μM. Interestingly, most of these compounds were non-cytotoxic to 3T3 cell line at 30μM, except compounds 6, 14 and 15. Competitive inhibitors of chymotrypsin are like to inhibit other α-chymotrypsin-like serine proteases due to structural and functional similarities between them. The inhibitors identified during the current study deserve to be further studied for their therapeutic potential against abnormalities mediated by chymotrypsin or other serine protease.

Unified Approach to (Thio)chromenones via One-Pot Friedel-Crafts Acylation/Cyclization: Distinctive Mechanistic Pathways of β-Chlorovinyl Ketones.

A facile synthetic method to chromenones and thiochromenones has been developed using a one-pot Friedel-Crafts acylation of alkynes with suitably substituted benzoyl chlorides. This unified approach to (thio)chromenones is readily applicable to aryl- and alkylalkynes where the stereochemically well-defined β-chlorovinyl ketone intermediates undergo distinctively different cyclization pathways. The ready availability of both starting materials, alkynes and benzoyl chlorides, coupled with the experimental simplicity makes the current synthetic method to (thio)chromenones fast, efficient, and practical.

Synthesis of 10-(R-benzoyl)-2,4-dimethyl-6-(R-phenyl)-8,9-dihydropyrimido[5,4-e]pyrrolo[1,2-c]pyrimidine-1,3(2H,4H)-diones and 2,4-dimethyl-9,10-dihydro-6λ4-pyrimido[5,4-d]pyrrolo- [1,2-b][1,2,6]thiadiazine-1,3,6(2H,4H,8H)-trione

6-Imino-1,3-dimethyl-5-(pyrrolidin-2-ylidene)-5,6-dihydropyrimidine-2,4(1H,3H)-dione reacted with substituted benzoyl chlorides in the presence of triethylamine to give the corresponding 10-(R-benzoyl)-2,4-dimethyl-6-(R-phenyl)-8,9-dihydropyrimido[5,4-e]pyrrolo[1,2-c]pyrimidine-1,3(2H,4H)-diones. Analogous reaction with thionyl chloride afforded 2,4-dimethyl-9,10-dihydro-6λ4-pyrimido[5,4-d]pyrrolo[1,2-b][1,2,6]-thiadiazine-1,3,6(2H,4H,8H)-trione.

Positioning solvolyses within the SN2‐SN1 and SN3‐SN2 spectrum of reaction mechanisms

A simple linear regression (Q equation) is devised to position solvolyses within the established SN2‐SN1 spectrum of solvolysis mechanisms. Using 2‐adamantyl tosylate as the SN1 model and methyl tosylate as the SN2 model, the equation is applied to solvolyses of ethyl, allyl, secondary alkyl and a range of substituted benzyl and benzoyl tosylates. Using 1‐adamantyl chloride as the SN1 model and methyl tosylate as the SN2 model, the equation is applied to solvolyses of substituted benzoyl chlorides in weakly nucleophilic media. In some instances, direct correlations with methyl tosylate were employed. Grunwald–Winstein l values and kinetic solvent isotope effects are also used to locate solvolyses within the spectrum of mechanisms. Product selectivities (S) for solvolyses at 50 °C of p‐nitrobenzyl tosylate in binary mixtures of alcohol–water and of alcohol–ethanol for five alcohols (methanol, ethanol, 1‐propanol and 2‐propanol and t‐butanol) are reported and show the expected order of solvent nucleophilicity (RCH2OH > R2CHOH > R3COH). The data support the original assignments establishing the NOTs scale of solvent nucleophilicity. Copyright © 2016 John Wiley & Sons, Ltd.

Synthesis and spectroscopic characterization of fluorescent 4-aminoantipyrine analogues: Molecular docking and in vitro cytotoxicity studies

Two substituted aromatic carbonyl compounds (compounds 1 and 2) of 4-aminoantipyrine were synthesized by condensation of fluorine substituted benzoyl chlorides and 4-aminoantipyrine. The structures of synthesized derivatives were established on the basis of UV–Vis, IR, and Mass, 1H, 13C NMR and Fluorescence spectroscopy. Both compounds showed significant fluorescence emission and two broad emission bands were observed in the region at 340nm and 450nm on excitation at 280nm. Theoretically to prove that the molecule has anticancer activity against cervical cancer cells, the compounds were analyzed for molecular docking interactions with HPV16-E7 target protein by Glide protocol. Furthermore, 4-aminoantipyrine derivatives were evaluated for their in vitro cytotoxic activity against human cervical cancer cells (SiHa) by MTT assay. Compound 1 showed two fold higher activity (IC50=0.912μM) over compound 2, and its activity was similar to that of Pazopanib, suggesting that although the two compounds were chemically very similar the difference in substituent on the phenyl moiety caused changes in properties.

Synthesis, structural characterization, antimicrobial and antifungal activity of substituted 6-fluorobenzo[d]thiazole amides

A series of novel 1-[(1R)-1-(6-fluoro-1,3-benzothiazol-2-yl)ethyl]-3-substituted phenyl amides was synthesized by the condensation reaction of (1R)-1-(6-fluoro-1,3-benzothiazol-2-yl)ethanamine with substituted benzoyl chlorides under mild conditions. Their structures were confirmed by 1H NMR, 13C NMR and 19F NMR spectra, elemental analyses and in three cases also by single-crystal X-ray diffraction techniques. The optical activities were confirmed by optical rotation measurements. All the synthesized compounds were screened for antibacterial and antifungal activity against a variety of bacterial and fungal strains. Some of the compounds reveal antibacterial and antifungal activity comparable or slightly better to that of chloramphenicol, cefoperazone and amphotericin B used as medicinal standards.