6H-anthra[1,9,8-c,d,e,f]-2,7-naphthyridine derivatives

Derivatives of a new heterocyclic system- 6H-anthra[1,9,8-c,d,e,f]-2,7-naphthyridine-were obtained by condensation of 1,8-diaminoanthraquinone with malonic ester, acetoacetic ester, and benzoylacetic ester.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 679–681, May, 1974.     

A facile synthesis for functional perfluoropolyether oligomers,diacids, diesters,and surfactants

Linear polyester precursors provide a convenient low cost synthesis for flurocarbon surfactants, diacids, diesters, and intermediates. A reaction scheme starting with hydrocarbon linear polysters followed by conversion of the ester to a perfluoro ester by direct fluorination and subsequent treatment with nonstoichiometric amount of sulfur tetrafluoride produce upon hydrolysis of ester units remaining in the polymer, low molecular weight perfluropolyether diacids. Alternatively, this technique can be altered slightly to produce diesters and other functional perfluorocarbon intermediates.     

Investigation of condensed pyrimidine,pyrazine, and pyridine systems

The reaction of 5-hydroxy-6-aminopyrimidines with chloromalonic ester in alcohol or with bromomalonic ester in dimethylformamide leads to 6-carbethoxypyrimido-7-oxazinones, whereas a mixture of 6-carbethoxypyrimido-7-oxazinones and 6,6-spirodipyrimido-7-oxazinones is formed in the reaction with bromomalonic ester in alcohol. The latter oxazinones were obtained by reaction of 5-hydroxy-6-aminopyrimidines with dibromomalonic ester. Some of the properties of the synthesized compounds were studied.See [1] for communication XXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 391–396, March, 1978.     

Studies on heterobifunctional cross-linking reagents, 6-maleimidohexanoic acid active esters

6-maleimidohexanoic acid N-hydroxysuccinimide ester has been used widely for preparation of enzyme immunoconjugates as a unique heterobifunctional cross-linking reagent. Its heterobifunctional reactivity is good, but its ester portion hydrolyzes easily in the presence of water. Several 6-maleimidohexanoic acid active esters (6-maleimidohexanoic acid 4-nitrophenyl ester, 6-maleimidohexanoic acid N-hydroxy-5-norbornene-endo-2,3-dicarboximide ester, and 6-maleimidohexanoic acid pentafluorophenyl ester) were prepared and their reactivity and stability in an aqueous media were tested. Of the synthetic esters, the pentafluorophenyl ester exhibited the highest reactivity and stability in aqueous media.     

tert-Butyl Tetraethylphosphorodiamidite in Reactions with α,β-Unsaturated Dicarbonyl Compounds

Reactions of tert-butyl tetraethylphosphorodiamidite with benzylideneacetylacetone, benzylideneacetoacetic ester, and benzylidenemalonic ester are studied. It is shown that the reaction pathway significantly depends on the solvent and temperature. The reaction with benzylidenacetylacetone in ether gives rise to a stable diketophosphonate, while the same reaction in boiling benzene involves elimination of diethylamine and yields a phospholene. The reaction with benzylideneacetoacetic ester proceeds analogously, while with benzylidenemalonic ester the corresponding phospholene is formed exclusively.     

Lipase-Catalyzed Synthesis,Antioxidant Activity,Antimicrobial Properties and Molecular Docking Studies of Butyl Dihydrocaffeate

Green chemistry approaches, such as lipase-catalyzed esterification, are promising methods for obtaining valuable chemical compounds. In the case of the use of lipases, unlike in aqueous environments, the processes of the ester bond formations are encountered in organic solvents. The aim of the current research was to carry out the lipase-catalyzed synthesis of an ester of dihydrocaffeic acid. The synthesized compound was then evaluated for antioxidant and antimicrobial activities. However, the vast majority of its antioxidant activity was retained, which was demonstrated by means of DPPH· (2,2-diphenyl-1-picrylhydrazyl) and CUPRAC (cupric ion reducing antioxidant capacity) methods. Regarding its antimicrobial properties, the antifungal activity against Rhizopus oryzae is worth mentioning. The minimum inhibitory and fungicidal concentrations were 1 and 2 mM, respectively. The high antifungal activity prompted the use of molecular docking studies to verify potential protein targets for butyl ester of dihydrocaffeic ester. In the case of one fungal protein, namely 14-α sterol demethylase B, it was observed that the ester had comparable binding energy to the triazole medication, isavuconazole, but the interacted amino acid residues were different.     

Synthesis of 2-Hydroxy-3-methyl-2-cyclo-pentenone,Corylone, from 2-Ketoglutaric Acid

Treatment of 2-ketoglutaric acid with diazomethane gave 2-(metoxycarbonyl)-oxiranepropanoic acid methyl ester (2) wich lead to 2-hydroxy-2-methyl-glutaric acid dimethyl ester (3) by catalytic hydrogenation, wich was further processed to the title compound.     

The Stereoselective Synthesis of Disubstituted E,Z-Diene Ester

The new method for the stereoselective synthesis of disubstituted diene ester was successfully applied to a highly stereoselective synthesis of E, Z-diene ester (1).     

Synthesis,Surface Activity,and Antifogging Property of Triethanolamine Monolaurate Ester

Triethanolamine monolaurate ester was synthesized by lauric acid and triethanolamine (TEA) with a molar ratio around 1:1 and the esterification process was investigated and optimized. The esterification product of lauric acid with TEA was characterized by infrared spectra and nuclear magnetic resonance. The surface tension (γ_CMC) at the critical micelle concentration (CMC) was determined, and the antifogging properties of triethanolamine laurate ester on low-density polyethylene (LDPE) films were also measured. The results indicated that the yield of triethanolamine monolaurate ester was more than 69% under optimized esterification condition, the CMC value and γ_CMC of esterification product was 0.91 μg/mL and 22.1 mN/m in aqueous solution at 25 ^oC, respectively. The first-drop time and ten-drop time was 257 and 86 s, respectively, and the antifogging duration of triethanolamine laurate ester on the surface of LDPE film at 60 ^oC was more than 150 h.     

Stereoselective Synthesis of syn-and anti-3a-Hydroxyl-1,2,3,3a,8,8a-hexahydropyrrolo[2,3-b] indole-2-carboxylic Acid

The structure of syn-and anti-N^b-(p-toluenesulfonyl)-3a-hydroxyl-1,2,3,3a,8,8a-hexahydro pyrrolo[2,3,-b]indole-2-carboxylic t-butyl ester was stercoselectively synthesized by oxidative ring formation of N^b-(p-toluenesulfonyl)-L-tryptophan t-butyl ester in methylene chloride containing dimethyldioxirane(DMDO),the p-toluenesulfonly group and t-butyl group can be easily removed by sodium naphthalenide and trifluoroacetic acid,respectively.     

Synthesis,isolation, and purification of benzylpenicillin β-diethylaminoethyl ester hydroiodide

Processes of synthesis, isolation, and purification of benzylpenicillin β-diethylaminoethyl ester hydroiodide were studied. The optimal conditions of benzylpenicillin esterification with chloroethyldiethylamine in dimetylformamide and acetonitrile were found. Processes for isolation of the target product were developed and its physicochemical properties were studied. Product stabilization conditions providing a stable pH value in solutions of benzylpenicillin β-diethylaminoethyl ester hydroiodide were found.     

Total synthesis of (+/-)-alpha- and beta-lycoranes by sequential chemoselective conjugate addition-stereoselective nitro-Michael cyclization of an omega-nitro-alpha,beta,psi,omega-unsaturated ester

[reaction: see text] An omega-nitro-alpha,beta,psi,omega-unsaturated ester underwent a chemoselective conjugate addition of a nitroolefin moiety with aryllithium to produce a psi-aryl-omega-nitro-alpha,beta-unsaturated ester, which was then stereoselectively cyclized by intramolecular nitro-Michael reaction giving a functionalized cyclohexane applicable to the total synthesis of (+/-)-alpha- and beta-lycoranes.     

Synthesis of 5,6-dihydroxy-2-phenyl-4-pyrimidinecarboxylic acid,methyl ester,a corrected structure

Pyrolysis of the adduct of benzamide oxime and dimethyl acetylenedicarboxylate leads to 5,6-dihydroxy-2-phenyl-4-pyrimidinecarboxylic acid methyl ester ( 4a ) rather than 4,5-dihydro-α,4-dioxo-2-phenyl-1H-imidazole-5-acetic acid, methyl ester ( 1 ).     

Dynamic light scattering, interfacial properties, and conformational analysis of biodegradable quarternary ammonium surfactants

Aggregation properties of biodegradable ammonium surfactants containing amide and ester groups in the bulk and at the air-water interface were investigated as a function of surfactant tail length m using dynamic light scattering and surface tension experimental methods. The results indicate that surfactants containing an ester group in the structure display higher aggregation ability in the volume and form more densely packed layer of molecules at the air-water interface than those with an amide group. The results of physical measurements were correlated with 3D models of respective surfactant molecules. As the results indicate, a surfactant molecule headgroup containing an ester group shows higher flexibility than that with an amide group in its structure, which is documented by somewhat smaller headgroup size and denser packing at the air-water interface.     

Determination of total biodiesel fatty acid methyl, ethyl esters, and hydrocarbon types in diesel fuels by supercritical fluid chromatography-flame ionization detection

A method for determining total biodiesel methyl and ethyl ester content in diesel fuels by supercritical fluid chromatography-flame ionization detection (SFC-FID) is developed. A silica column typically used for determining aromatics in conventional diesel fuels by ASTM D5186 is back-flushed after separation of the hydrocarbons to allow elution of the various esters as a single "total biodiesel" distinct peak. The modification concurrently allows the determination of total aromatic hydrocarbons and their distribution as mono- and polynuclear compounds, as described in the current version of D5186. The instrument response is linear from 1.0% to 50% biodiesel esters with a signal-to-noise ratio of 25 at the 0.1% level. The short-term relative standard is 0.8%. Normalized percent quantitation using a hydrocarbon response factor of 1.00 and an ester response factor of 1.19 provide an average percentage error of 1.8% when measuring actual biodiesel/hydrocarbon fuel blends. The ester response factor is the average of the response factors of 10 pure ester compounds. These responses are calculated from respective solutions of each ester and the four compounds, hexadecane, toluene, tetralin, and naphthalene, as used for the D5186 response factor mixture.     

Syntheses and reactivities of non-symmetrical "active ester" bi-dentate cross-linking reagents having a phthalimidoyl and acid chloride, 2-benzothiazole, or 1-benzotriazole group

We have newly synthesized the non-symmetrical "phthalimidoyl active ester" bi-dentate cross-linking reagents having an acid chloride, 2-benzothiazole, or 1-benzotriazole group (i.e., 9, 15, and 16) on the basis of the reactivity study of the "active ester" model compounds, 11-14, toward the various nucleophiles and examined their reaction selectivity towards the same nucleophiles. Then, we applied for the modification of cholesterol at the more reactive site of the bi-dentate linkers to give 3β-cholesteryl 4-(phthalimidoyloxycarbonyl)butyrate (39), and the subsequent reaction of 39 with several amines, such as benzylamine, 4-chlorobenzylamine, 2-phenylethylamine, L-phenylalanine methyl ester, or diphenylalanine benzyl ester as a protein model of the cholesterol antigen.     

Kinetics and mechanism of the addition of nucleophiles to alpha,beta-unsaturated thiol esters

Compounds containing the UV-absorbing chromophores p-methoxycinnamate, p-methoxycinnamide, or anthranilate and an alpha,beta- or alpha,beta,gamma,delta-unsaturated thiol ester (crotonyl or sorboyl) have been prepared. These compounds are subject to nucleophilic attack at the C=C conjugated to the thiol ester carbonyl group. The kinetics of the reactions of these thiol esters with N-acetyl-l-cysteine (NAC), N-acetylcysteamine, and N(2)-acetyl-L-lysine (NAL) have been studied, and the thiol addition products have been identified. The reaction rates increased at higher pH, and the reaction of NAC thiolate with a crotonyl thiol ester in 1:1 (v/v) acetonitrile/aqueous HEPES exhibited buffer catalysis as a result of protonation of the enolate intermediate. At the same concentration, NAC underwent approximately 300-fold more reaction than NAL with a crotonyl thiol ester at pH 9.8. Additionally, a crotonyl thiol ester was found to be 7.9 times more reactive than a sorboyl thiol ester toward NAC addition. These unsaturated thiol esters may serve as a means of covalently binding UVA and UVB sunscreens to the outer layer of skin to provide long-lasting protection.     

Michael additions to acrylonitrile,methyl acrylate and methyl vinyl ketone to Nb-benzylidenetryptophan methyl ester

Michael addition to methyl acrylate and methyl vinyl ketone of N_b-benzylidene-L-tryptophan methyl ester 1 gave 2-(3-indolylmethyl)glutamic dimethyl ester 2a and α-(3-oxobutyl)tryptophan methyl ester 2b respectively. Addition to acrylonitrile of 1 yielded α,N_a-dicyanoethyltryptophan methyl ester 3 .     

Alkaline Earth Metallocenes Coordinated with Ester Pendants: Synthesis,Structural Characterization,and Application in Metathesis Reactions

A variety of ester‐substituted cyclopentadiene derivatives have been synthesized by one‐pot reactions of 1,4‐dilithio‐1,3‐butadienes, CO, and acid chlorides. Direct deprotonation of the ester‐substituted cyclopentadienes with Ae[N(SiMe₃)₂]₂ (Ae=Ca, Sr, Ba) efficiently generated members of a new class of heavier alkaline earth (Ca, Sr, Ba) metallocenes in good to excellent yields. Single‐crystal X‐ray structural analysis demonstrated that these heavier alkaline earth metallocenes incorporated two intramolecularly coordinated ester pendants and multiply‐substituted cyclopentadienyl ligands. The corresponding transition metal metallocenes, such as ferrocene derivatives and half‐sandwich cyclopentadienyl tricarbonylrhenium complexes, could be generated highly efficiently by metathesis reactions. The multiply‐substituted cyclopentadiene ligands bearing an ester pendant, and the corresponding heavier alkaline earth and transition‐metal metallocenes, may have further applications in coordination chemistry, organometallic chemistry, and organic synthesis.     

Synthesis,antimicrobial activity,and structure–activity relationships of eugenol,menthol, and genistein esters

This study concentrates on the extraction of eugenol, menthol, and genistein, and the synthesis, antimicrobial activity, and structure-activity relationships of their ester derivatives. The esters were tested for antimicrobial activity against several bacteria and yeast, and the correlation between biological properties and various physicochemical properties was examined. The ester derivatives gave intense emissions upon irradiation by UV light and have photoluminescence quantum yields of 39, 35, and 36% and long excited-state lifetimes of 3.62, 3.23, and 3.40 ns, respectively. These esters may be used in herbal medicinal therapy, and additionally as a base for the development of new drugs for phytomedicine.