Orthoformic Ester Research Articles

Synthesis and the Antimicrobial Activity of Salt Carbenoid Compounds

Aim. To synthesize aliphatic and aromatic derivatives of salt carbenoid compounds of the series of imidazole, benzimidazole, pyridine, pyrimidine and 1,3,4-oxadiazole containing fluorophenyl, cetyl or adamantyl substituents, and study their antimicrobial (antibacterial and antifungal) activities.Results and discussion. New derivatives of heterocyclic carbenoid salts and zwitterions based on the imidazole, benzimidazole, pyridine, pyrimidine and 1,3,4-oxadiazole heterocyclic systems containing fluorophenyl, cetyl or adamantyl substituents were synthesized. For this purpose, reactions of cyclization of the corresponding diimines with ethoxymethyl chloride (imidazolium salts), quaternization of the corresponding azoles with cetyl bromide or 1-adamantyl bromide in organic solvents (benzimidazolium, pyridinium and 1,3,4-oxadiazolium salts), cyclization of di(1-adamantylamino)alkanes hydrobromides with the orthoformic ester (4,5-dihydroimidazolium and tetrahydropyridinium salts) were used. Zwitterionic compounds were obtained by the reaction of the corresponding azolium salts with phenyl isothiocyanate in the presence of potassium carbonate. Some macrocyclic and adamantyl substituted heterocyclic compounds showed antifungal and antibacterial activities.Experimental part. The structure of the compounds synthesized was proven by 1H and 13C NMR spectroscopy methods. The antimicrobial activity was studied out by the agar diffusion method to determine diameters of the growth inhibition zones of microorganisms (bacteria and fungi) and by the method of serial dilutions to determine the minimum inhibitory concentration and minimum bactericidal and fungicidal concentrations.Conclusions. The synthesis of new heterocyclic carbenoid salts and zwitterions based on the imidazole, benzimidazole, pyridine, pyrimidine and 1,3,4-oxadiazole heterocyclic systems containing fluorophenyl, cetyl or adamantyl substituents has been performed. Compounds of macrocyclic and adamantyl heterocyclic series with antifungal and antibacterial activities have been found. 1,3-Dicetylimidazolium bromide, macrocyclic bis(decylenebenzimidazolium) bromides, azolium-N-phenylthiocarboximides have been proven to be the most active.

Synthesis and structure elucidation of novel 5-dinitromethyl-7-alkylamino-1,2,4-triazolo[4,3-a]-1,3,5-triazines

Abstract Synthesis of the novel potassium salts of 5-dinitromethyl-7-alkylamino-1,2,4-triazolo[4,3-a]-1,3,5-triazines 9a–c was performed by heating (in DMSO) 2-alkylamino-4-ethoxymethylidenehydrazino-6-dinitromethyl-1,3,5-triazines 8a–c, obtained by treating of the corresponding 2-alkylamino-4-hydrazino-6-dinitromethyl-1,3,5-triazines 5a–c with orthoformic ester. 2-Alkylamino-4-hydrazino-6-dinitromethyl-1,3,5-triazines were obtained by a sequential substitution of the methoxy groups of the potassium salt of 2,4-dimethoxy-6-dinitromethyl-1,3,5-triazine with an alkylamine (dimethylamine, morpholine, pyrrolidine) and hydrazine.

Molecular polarizability of organic compounds and their complexes: LVI. Molar volume and structure in a solution of the compounds with several axes of intramolecular rotation

Molar volumes in solutions of compounds like orthoformic esters, trialkyl phosphates, trialkylphosphites, substituted aziridines, cyclopropanes, cyclohexanes, boroxines, N-aryl-4-pyridones, decalines, and cyclooctane were determined and discussed. Conformations of alkyl substituents in the esters were found to be similar to the conformations of the corresponding alkanes. Molar volumes of aziridines and cyclopropanes were found to be additive with respect to the molar volumes of bond and group increments. The nature of solvation of the molecules of these compounds was found to be similar to that in the model systems which served for the calculations of the increments. Molar volumes of cyclohexane, decaline, and cyclooctane also were found to be additive with respect to the contributions of the molar volumes of increments of the corresponding bonds and groups. The solvation and the steric structure of substituted boroxines were found to be similar to those of the structurally analogous substituted benzenes. Conformations of N-aryl-4-pyridone and its substituted derivatives in solutions were found to be similar to the conformations of biphenyl and its derivatives. A possibility of simplification of the methods for determining the dipole moments and Kerr constants of compounds from their additive molar volumes was demonstrated.

Steric structure of N-(2-Hydrazono-2-hydroxyethyl)-d-pseudoephedrine and its intramolecular heterocyclization under the action of orthoformic ester

An X-ray structural investigation of N-(2-hydrazono-2-hydroxyethyl)-d-pseudoephedrine is performed, and intramolecular heterocyclization of this compound with orthoformic ester is studied. The final reaction product is found to be a compound containing a morpholone ring rather than substituted 1,3,4-oxadiazole.

New reaction of di- and trichloromethylbenzenes with orthoformic esters

New reaction of di- and trichloromethylbenzenes with orthoformic esters

Reaction of O,O-diisopropyl phosphorodithioic acid and its trimethylsilyl ester with orthoformic ester

Reaction of O,O-diisopropyl phosphorodithioic acid and its trimethylsilyl ester with orthoformic ester

Photosynthesis and properties of halomethyl derivatives of azinobenzimidazoles

Photocyclization of 2-(pentafluoroanilino)-, 2-(4-chloro-2-iodoanilino)-, 2-(2-chloro-4-iodo-anilino)-4,6-dimethylpyrimidines, as well as 2-(2-chloro-3-methylanilino)pyridine was used to prepare con-densed azinobenzimidazoles, including previously unknown 8-chloro-1,3-dimethylpyrimido[1,2-a]benzimidazole and 9-methylpyrido[1,2-a]benzimidazole. With isomeric chloroiodoanilinopyrimidines as example it was shown that the iodine atom affects photocyclization direction. Quaternization of 6,7,8,9-tetrafluoro-1,3-dimethylpyrimido[1,2-a]benzimidazole, 8-chloro-1,3-dimethylpyrimido[1,2-a]benzimidazole, and 9-methylpyrido[1,2-a]benzimidazole with alkylating agents and C-H activity of alkyl groups in the quaternary salts in reactions with orthoformic ester were studied.

Synthesis and reactions of 4-amino-3-carbethoxy-1,2-dihydrospiro(naphthalene-2,1′-cyclopentane)

Addition of benzylmagnesium chloride to cyclopentylidenecyanoacetic ester gives 1-benzyl-1-(cyanocarbethoxymethyl)cyclopentane and this can be cyclized to 4-amino-3-carbethoxy-1,2-dihydrospiro-(naphthalene-2,1′-cyclopentane). Acylation of the obtained aminoester with carboxylic acid chlorides produces the corresponding amides (which can react with an excess of benzoyl chloride). It can also react with orthoformic ester. In both cases the product can then react with hydrazine hydrate. Treatment of the same aminoester with caprolactam gives a tetrahydrospiro(benzo[h]quinazoline-5,1′-cyclopentane) derivative.

Reaction of 3,5-diamino-4-nitropyrazole with electrophilic reagents

The interaction of 3,5-diamino-4-nitropyrazole with such electrophilic reagents as acetic anhydride, dimethylformamide acetal, orthoformic ester, and ketones has been studied. Derivatives of pyrazolol[1,5-a]pyrimidines were formed on reaction with 1,3-diketones and some of their properties have been studied.

Nickel(II) and copper(II) complexes with amidrazone-based ligands: Structure and catalytic activity

Nickel(II) and copper(II) complexes MeL, where H 2LL = [9-(2′-hydroxyphenyl)-6-methyl-3-acetyl-5,7,8-triazanona-3,6,8-trien-2-one], have been synthesized by template reaction of salicylaldehyde acetamidrazone with corresponding Me(acac) 2 and Hacac in the presence of the orthoformic ester at 110°C. The crystal structure of CuL has been determined by X-ray diffraction. The square-planar mode of coordination is realized in CuL. Comparison of geometrical parameters of CuL with those of the corresponding derivative based on S--allylisothiosemicarbazide showed that substitution of the -SR group by methyl in the quadridentate ligand does not affect the mode of binding nor the main interatomic distances and angles in the ligand. The data from magnetic measurements, 1HH NMR and EI mass spectra indicate that NiL has a similarly structured coordination polyhedron. Epoxidation of norbornene can be performed efficiently with molecular oxygen (1 atm) in THF (or THF-EtOAc) in the presence of CuL at 70°C. The corresponding copper(II) derivatives based on S--substituted isothiosemicarbazides are much less active as catalysts.

Synthesen neuer Chinolon‐Chemotherapeutika. V [5] Methodische Untersuchungen zur Synthese von Chinoloncarbonsäuren

Synthesis of Novel Quinolone‐Chemotherapeutics. V. Methodical Investigations on the Synthesis of Quinolone Chemotherapeutics.The synthesis of 6, 7‐dihalogen‐N‐ethyl‐4‐oxo‐l, 4‐dihydroquinoline‐3‐carboxylic acids (3a, b) from 3, 4‐dihalogen‐anilines is a three‐step processes: (a) N‐ethylation, (b) reaction with ortho formic ester and Meldrum's acid, (c) intramolecular cyclization. An increase of the total yields in comparison with known methods is mainly connected with the third step. Here the Meldrum's method allows reactions in solution at temperatures ≥ 100°C. With application of special Lewis acids the 6, 7‐dihalogen‐substituted products are formed in relatively high yields (6, 7‐difluoro‐l‐ethyl‐4‐oxo‐1, ‐4‐dihydro‐quinoline‐3‐carboxylic acia (3a): 71%; 7‐chloro‐6‐fluoro‐1 ‐ethyl‐4‐oxo‐1, 4‐dihydro quinoline‐3‐carboxylic acid (3b): 60%) without impurities of the corresponding 5, 6‐dihalogen substituted isomers. Anhydrides (5) of 4‐oxo‐1, 4‐dihydro‐quinolone‐3‐carboxylic acids with dibromo and difluoro‐boric acid were synthesized and shown to facilitate the aromatic nucleophilic substitution. The kinetics of two reactions (5a → 6 and 3b → 7) were determined and relative reaction rates established.

Synthesis and properties of phenylenebis-1H-tetrazoles

Heterocyclization of m- and p-phenylenediamines with orthoformic ester and sodium azide has given phenylenebis-1H-tetrazoles. Under these conditions, o-phenylenediamine gives benzimidazole. o-, m-, and p-Phenylenebis-1H-tetrazoles were also obtained from the nitroanilines via the intermediate nitro- and aminophenyltetrazoles. The reactions of the bistetrazoles examined were basic hydrolysis, aminomethylation, and complex formation with copper salts.

Reactions of acetophenones and boron trifluoride etherate in the presence of homologs of orthoformic ester

It was established that homologs of orthoformic ester (orthoacetic and orthopropionic esters), in contrast to it, do not undergo reaction with substituted acetophenones and boron trifluoride etherate to give γ-alkylpyrylium salts; the products obtained are 2,4,6-triarylpyrylium tetrafluoroborates.

Preparation of substituted 4-(3-methyl-3-hydroxy-1-butynyl)-2-ethoxy-1,3-dioxolanes

A method has been developed for the preparation of 4-(3-hydroxy-1-alkynyl)-substituted 2-ethoxy-1,3-dioxolanes (which are novel flotation reagents for coal) based on the reaction between acetylene 1,2,5-triols and orthoformic ester in the presence of catalytic quantities of benzoic acid.

Synthesis and equilibrium of stereoisomers of 5-phenyl-2-ethoxy-1,3,5-dioxaphosphorinane

The reaction of bis(hydroxymethyl)phenylphosphine with orthoformic ester gave 5-phenyl-2-ethoxy-1, 3, 5-dioxaphosphorinane, representing a mixture of two stereoisomers. The preferred conformations of these differ in the orientation of the phenyl residue on the phosphorus atom. The stereoisomer with the equatorial orientation of the phenyl radical predominantes in the equilibrium.

Synthesis of 1-substituted tetrazoles by heterocyclization of primary amines, orthoformic ester, and sodium azide

It has been shown that the reaction of heterocyclization of primary amines with orthoformic acid and sodium azide in acetic acid has a rather general character and is a convenient method for the synthesis if 1-substituted tetrazoles. On the basis of experimental data, a probable reaction mechanism is proposed.

Acetals of lactams and amides. 42. Reactions of enamino amides and enamino esters with some formylating agents. Synthesis of derivatives of 2-pyridone and of pyrimidin-4- and -6-ones

The reactions of enamino esters and enamino amides with the diethyl acetal of dimethylformamide and with orthoformic ester have been investigated and it has been shown that the process takes place in two directions — with the formation of pyrimidone or 2-pyridone derivatives and with the replacement of an aminopropylene (or N,N-dimethylaminopropylene) fragment of the enamine by a dimethylaminomethylene (or ethoxymethylene) group. Some conditions favoring the occurrence of one or other of these processes have been determined.

Einfache Darstellung von N(2′‐Hydroxy)‐aryliden‐nitro‐anilinen als Cumarin‐Synthone

A Simple Route to N(2′‐Hydroxy)‐arylidene‐nitroanilienes‐Versatile Synthones for CoumarinesIn a three‐component reaction with ortho formic esters and nitroaniline activated phenols are easily transferred to N(2′‐hydroxy)‐arylidene‐nitroanilines. The reaction is commonly applicable and gives the N(2′‐hydroxy‐4′‐N,N‐dialkylamino)‐benzylidene‐nitroanilines 10 in good yields also with the air‐unstable m‐N,N‐dialkylaminophenols 8. The prepared 2‐hydroxy‐azomethines are convertable into boroncomplexes 14 and coumarine derivatives 17, respectively.

Citral oxide and some of its reactions

1. A new method was proposed for the synthesis of citral oxide by the oxidation of citral with hydrogen peroxide under interphase catalysis conditions. 2. Citral oxide condenses with acetoacetic ester under interphase catalysis conditions without opening the oxirane ring. 3. The reaction of citral oxide with orthoformic ester, ethyl chloroacetate, and carbethoxymethylenephosphorane proceeds only at the carbonyl group. 4. The epoxidation and dichloromethylenation of the ethyl ester of 4,5-epoxy-5,9-dimethyl-2, 8-decadienoic acid is realized only at the more remote double bond.

The behaviour of alkylcobalt carbonyls under “oxo” conditions

Alkylcobalt carbonyls, synthesized under oxo conditions from alkyl halides and sodium tetracarbonylcobaltate, give the corresponding aldehydes on treatment with CO and H 2. The alkylcobalt carbonyls do not isomerize significantly under oxo conditions. Alkylcobalt carbonyls prepared from alkyl halides and sodium tetracarbonylcobaltate or from orthoformic esters dicobalt octacarbonyl, CO and hydrogen do not isomerize even in the presence of an excess of olefin.