CuO nano-particles supported on silica,a new catalyst for facile synthesis of benzimidazoles,benzothiazoles and benzoxazoles

A facile synthetic route for benzimidazoles, benzothiazoles and benzoxazoles comprising the reaction of corresponding o-phenylenediamine, o-aminothiophenol and o-aminophenol with various aldehydes using silica supported nano-copper (II) oxide as a catalyst has been described. The catalyst exhibited a clean reaction profile with excellent yields in a short reaction time. The catalyst can be recycled effectively after use.     

Dehalogenation of o-dihalogen substituted arenes and α,α′-dihalogen substituted o-xylenes with lanthanum metal

It was found that lanthanum metal caused the dehalogenation of o-dihalogen substituted arenes and α,α′-dihalogen substituted o-xylenes to generate the corresponding benzynes and o-quinodimethanes. When o-dihalogen substituted arenes were allowed to react with lanthanum metal in the presence of dienes, the Diels-Alder products between benzyne and dienes were formed in moderate to good yields. Similarly, the Diels-Alder adducts of o-quinodimethane with dienophiles were obtained, in the reaction of α,α′-dibromo-o-xylenes with lanthanum metal in the presence of dienophiles.     

The oxidation of benzidine, o,o′-tolidine and o,o′-dianisidine by manganese dioxide

The oxidation of benzidine, o,o′-tolidine, and o,o′-dianisidine by manganese dioxide was studied in an acidic medium. It has been shown that the studied substances are quantitatively oxidized by the reagent to the corresponding quinonediimines and that this reaction can be utilized for the indirect titrimetric determination of benzidine and o,o′-tolidine, based either on ferrometric titration of unconsumed manganese dioxide or on ascorbinometric titration of the quinonediimine formed.     

The dissociation energies of gaseous SmLi,EuLi, TmLi and YbLi

The Knudsen-cell mass-spectrometric method has been used to study reactions of the type: M(g)+Li(g) = MLi(g) and M(g)+Li₂(g) = MLi(g)+Li(g), where M = Sm, Eu, Tm or Yb. The dissociation energies (in kJ mol^?1) of the gaseous lithide molecules determined from the measured reaction enthalpies are: D_o⁰(SmLi) = 45.3±4.5. D_o⁰(EuLi) = 63.2±3.0. D_o⁰(TmLi) = 65.1±3.5 and D_o⁰(YbLi) = 33.4±3.0.     

Chiral,non-racemic diols,and α-amino acid-derived β-amino alcohols as templates for chiral catalysts in the Tsuji–Trost reaction

A commercially available collection of β-amino alcohols have been converted to their corresponding β-(o-diphenylphosphino) benzoyloxy(o-diphenylphosphino) benzamides and have been employed in the Tsuji–Trost asymmetric alkylation reaction with 1,3-diphenylpropenyl acetate. The best ligand was derived from l-tert-leucinol and when applied to the asymmetric allylic alkylation reaction, yielded the product in an enantiomeric ratio of 99.5:0.5 favoring the (S)-enantiomer.     

A practical synthesis of new S,N-disubstituted derivatives of 5-(4-methylpiperidino)methyl-2-thiouracil

5-(4-Methylpiperidino)methyl-2-thiouracil (1) has been obtained via the Mannich reaction between 2-thiouracil, paraformaldehyde, and a cyclic secondary amine such as 4-methylpiperidine (4-MP) in ethanol. New S,N(1)-di-o-(m- and p-)bromo-(nitro-) benzyl-substituted derivatives have been synthesized successfully in the reactions of 1 with the corresponding o-(m- and p-)bromobenzyl bromides or o-(m- and p-) nitrobenzyl chlorides in DMF solution in the presence of K₂CO₃. The opposite method of synthesis, that is, the reaction between 2-o-(m- and p-)bromobenzylthio-1-o-(m- and p-)bromobenzyluracils and 2-o-(m- and p-)nitrobenzylthio-1-o-(m- and p-) nitrobenzyluracils (8), with paraformaldehyde and 4-methylpiperidine in ethanol failed, indicating the important role of the enol form of 2-thiouracil for the Mannich reaction to be successful.     

The use of redox reactions in the analysis of dyes and dye industry intermediates: IV. Oxidation of benzidine,o-tolidine,and o-dianisidine with chloramine T and N-bromosuccinimide

The oxidation of benzidine, o-tolidine, and o-dianisidine with chloramine T and N-bromosuccinimide was studied, the stoichiometry was established, and a mechanism was proposed. An extraction-photometric determination of these diamines was developed, based on the reaction with excess chloramine T or N-bromosuccinimide and the measurement of the absorbance of the N,N′-dihalogeno-diphenoquinonediimines formed, after their extraction into chloroform.     

Novel formation of indoles and 3,1-benzoxazines from o-alkenylanilides and dimethyl(methylthio)sulfonium trifluoromethanesulfonate

The reaction of dimethyl(methylthio)sulfonium trifluoromethanesulfonate (DMTST) with o-allylphenol gave 2-methylthiomethyl-2,3-dihydrobenzofuran in 97% yield. The reaction of DMTST with N-tosyl-o-isopropenylanilide followed by the addition of aq sodium carbonate afforded N-tosyl-3-methylindole in 88% yield, whereas N-tosyl-o-vinylanilide afforded N-tosylindoline in 85% yield.     

A simple relationship between the hammett acidity function,Ho, and the thermodynamic pKa values of unsubstituted aromatic carboxamides

The well-known failure of the Hammett H_o function to describe the prototropic reaction isotherms of aromatic carboxamides can be corrected by taking account of the hydration requirements of the prototropic reactions of the carboxamides relative to the hydration requirements of the dissociations of the primary amines used as indicators to establish the H_o scale. This approach has been successfully applied to benzamide and the naphthamides. For up to a 4:1 molar ratio of water to sulfuric acid, the amide acidity scale, H_A and the H_o scale are simply related by H_A = H_o — 2 log a_w , where a_w is the activity of water.     

General procedure for the synthesis of ortho-vinylbenzyl-substituted amines, ethers, and sulfides

A convenient procedure has been proposed for the synthesis ortho-vinylbenzyl-substituted ethers, amines, and sulfides via reaction of o-(2-bromoethyl)benzyl bromide with various nucleophiles.     

On the reaction of 3-bromo-2-nitrobenzo[b]thiophene with some ortho-substituted anilines: an analysis of the products of reaction and of their NMR and MS properties

The title reaction, carried out in DMF in the presence of triethylamine or potassium carbonate, has furnished the ‘expected’ 3-amino-2-nitrobenzo[b]thiophenes 2o together with the ‘unexpected’ 2-amino-3-nitrobenzo[b]thiophenes 3o, thus recalling the situation observed with other weak nucleophiles in the presence of non-nucleophilic bases. The effects (electronic as well as steric) of the ortho-substituent (OH, NH₂, OMe, Me, Et, F, Cl and Br) on the course of the reaction have been investigated, determining their influence on yields and product ratios (2o/3o). An analysis of ¹³C NMR and MS spectra of 2o and 3o has been carried out. Ab initio computations on 2of, 2oi, 3of and 3oi at DFT level have furnished informations on their geometry and stability in the gas phase, thus allowing to assign a role to their stability on the course of the reaction as well as on some EI-MS results.     

Synthesis of novel dipodal-benzimidazole,benzoxazole and benzothiazole from cyanuric chloride: Structural,photophysical and antimicrobial studies

In the present study, new benzimidazole, benzoxazole and benzothiazole derivatives were prepared and screened for antimicrobial activity. The structure of 4,4′-((6-(4-(diethylamino)phenyl)-1,3,5-triazine-2,4-diyl)bis(oxy))dibenzaldehyde (DIPOD) 5 was established from p-hydroxy benzaldehyde 4 and 4-(4,6-dichloro-1,3,5-triazin-2-yl)-N,N-diethylaniline 3. The reaction of DIPOD 5 with different o-phenylenediamine or o-amino phenol or o-amino thiophenol in ethanol gave benzimidazole, benzoxazole and benzothiazole 7. Novel heterocycles showed excellent broad-spectrum antimicrobial activity against bacterial strain (Escherichia coli, Staphylococcus aureus) and fungal strain (Candida albicans, Aspergillus niger) cultures. Activity data was compared with standard Streptomycin and Fluconazole drug. Photophysical and thermal properties of synthesized compounds were also studied.     

Low-temperature oxidation of 3,6-di-tert-butyl-o-benzoquinone and 3,6-di-tert-butylpyrocatechol with tert-butyl hydroperoxide in the presence of aluminum, titanium, and zirconium tert-butylates

Systems consisting of metal (Al, Ti, Zr) tert-butylate and tert-butyl hydroperoxide oxidize 3,6-di-tert-butyl-o-benzoquinone under mild conditions (room temperature, benzene). With (t-BuO)₃Al and (t-BuO)₄Zr, the major reaction products are 5-hydroxy-3,6-di-tert-butyl-2,3-epoxy-p-benzoquinone, and with (t-BuO)₄Ti, 2-hydroxy-3,6-di-tert-butyl-p-benzoquinone. Under the conditions of this reaction, 3,6-di-tert-butylpyrocatechol initially transforms into 3,6-di-tert-butyl-o-benzoquinone. The reactions involve metalcontaining peroxides.     

Synthesis of o-(diphenylphosphinoyloxy)anilines by the rhodium-catalyzed reaction of nitroarenes and diphenylphosphine oxide

A rhodium complex Rh₂(OAc)₄ catalyzed the reaction of nitrobenzenes and diphenylphosphine oxide HP(O)Ph₂ giving o-(diphenylphosphinoyloxy)anilines predominantly, which were accompanied by small amounts of the p-isomers. Nitorobenzenes possessing a bulky o-substituent, particularly o-(t-butyl)nitrobenzenes, underwent the reaction in high yields. The reaction is considered to involve the reductive formation of O-phosphinoyl-N-arylhydroxyamines from nitrobenzenes, and o-phosphinoyloxylation by the rearrangement.     

Facile synthesis of isoquinolines by imination and subsequent palladacycle-catalyzed iminoannulation of internal alkynes

An efficient and facile synthesis of isoquinolines has been described via a tandem reaction of imination of o-halobenzaldehydes with tert-butyl amine and subsequent palladacycle-catalyzed iminoannulation of internal alkynes. This tandem reaction could be carried out successively in one pot without any special operation, and the annulation step could afford isoquinolines derivatives in moderate to good yields with high regioselectivity. In addition, the simple synthesis of indoles was realized by palladacycle-catalyzed annulation of o-iodoaniline or o-bromoanilines with internal alkynes.     

Synthesis of o-halogenophenylacetylenes via the dianion of phenylacetylene (1)

The o-halogenophenylacetylenes o-iodophenylacetylene,o-bromophenylacetylene and o-chlorophenylacetylene can be prepared by regiospecific reaction of iodine, bromine, and hexachloroethane respectively with the dianion of phenylacetylene.     

Base and catalyst-free synthesis of nitrobenzodiazepines via a cascade N-nitroallylation-intramolecular aza-Michael addition involving o-phenylenediamines and nitroallylic acetates

A [4+3] annulation of o-phenylenediamines with primary nitroallylic acetates affords nitrobenzodiazepines (NBDZs) in good to excellent yield. The reaction which proceeds in MeOH at room temperature in the absence of any base or catalyst involves a cascade S_N2 N-nitroallylation-intramolecular aza-Michael addition sequence. In the case of mono-N-arylated o-phenylenediamines and o-aminobenzamides, the reaction stops at the S_N2 stage affording nitroallylic amines. On the other hand, reaction of o-aminobenzamides with secondary nitroallylic acetates delivers S_N2′ products. Formation of stable S_N2 and S_N2′ products provides insights into the reactivity of primary and secondary nitroallylic acetates and also the mechanism of formation of nitrobenzodiazepines.     

A one-pot, non-catalytic approach to 1,2,4-benzothiadiazine-1,1-dioxides

Condensations of o-halo-substituted benzenesulfonyl chlorides with 2-aminopyridines and amidines may give the corresponding 1,2,4-benzothiadiazine-1,1-dioxides under mild, non-catalytic conditions in nearly quantitative yields. The successful one-pot cyclization depends on three factors: (i) the nature of the o-halogen, (ii) the electronic character of the benzene ring substituent, and (iii) the steric load around the amidine unit. O-Fluorobenzenesulfonyl chlorides bearing methylcarboxyl- or nitro-group and o-chloro- and o-bromobenzenesulfonyl chlorides bearing nitro-group are reactive enough to give the desired 1,2,4-benzothiadiazine-1,1-dioxides in a one-pot base-promoted reaction. In all other cases, open-chain sulfonylated amidine intermediates are isolated. The latter are converted to the title compounds either in the presence of potassium carbonate or upon the addition of a copper(I) catalyst.     

Synthesis and chemistry of the phenoxasilins and dihydro-dibenzo-oxasilepins

Formation of both sila-functional and carbo-functional phenoxasilins from diphenyl ether and o,o′-dibromodiphenyl ether precursors is described. Tricyclic oxasilepins are formed from o,o′-dibromobenzylphenyl ether by metallation with n-BuLi followed by reaction with dichlorosilanes as well as by ring expansion of an appropriate phenoxasilin. Reactions at the silicon center and at the ring methylene carbon of the oxasilepins are reported, as well as attempts to generate oxasilocins.     

A methodology for synthesis of primary o-phenylenebisphosphines and o-chlorophenylphosphines

On the basis of the reaction of ethynediylbisphosphonates and chloroethynylphosphonates with classical donor alka-1,3-dienes, a general strategy for synthesis of o-bisphosphanylbenzenes and o-chlorophosphanylbenzenes, which includes two consecutive steps: Diels-Alder condensation → aromatization of the carbocyclic phosphonate (bisphosphonate) formed → reduction of the phosphonate groups, was developed. Convenient procedures are devised for aromatization of phosphorus-containing cyclohexa-1,4-dienes and for reduction of o-phenylenebisphosphonates and o-clorophenylphosphonates to primary phosphines. A series of new alkylsubstituted phosphonic chlorides were prepared, and a possibility of functionalization of methylsubstituted o-phenylenebisphosphonates and o-clorophenylphosphonates by the methyl groups is demonstrated.