MAOS of D‐Gluconic Acid,D‐Glucono‐1,4‐ and 1,5‐Lactones,Esters, Hydrazides,and Benzimidazoles Thereof

Microwave‐assisted organic synthesis (MAOS) of D‐gluconic acid can be efficiently done by oxidation of D‐glucose with bromine water, upon irradiation with microwave (MW). It was also used for the conversion of D‐gluconic acid to ethyl D‐gluconate, D‐glucono‐1,4‐ and 1,5‐lactones, gluconyl hydrazide, and gluconyl phenylhydrazide in yields comparable to those obtained by conventional methods, but in much shorter times. A convenient microwave‐mediated condensation of D‐gluconic acid with o‐phenylenediamines provided the respective acyclonucleoside benzimidazole in short time and good yield.      

Synthesis of 1,2,4‐Triazinediones, 1,2,4,3‐Triazaphospholines,and 1,2,4,3‐Triazaphospholine‐3‐oxide Derivatives

The reaction of N ¹‐tosylamidrazones 1 with oxalyl dichloride, phosphorus trichloride, and phosphoryl chloride leads to 1,2,4‐triazinediones 3 , 1,2,4,3‐triazaphospholines 4 , and 1,2,4,3‐triazaphospholine‐3‐oxides 5 , respectively. The structures of the new products have been established by IR; ¹H, ¹³C, and ³¹P NMR studies; and elemental analysis.     

Synthesis,Structures, and Properties of Novel N‐Aryl‐phenanthren‐o‐iminoquinones

The interaction of 9,10‐phenanthrenquinone with primary amines has been studied. Use of sterically hindered anilines gave the phenanthren‐o‐iminoquinones in good yields. These compounds are structural analogues of o‐benzoquinones. Using single‐electron reduction, o‐iminoquinones may synthesize metal's free‐radical complexes.     

Formation of 1,2,5‐Oxadiazole,Isoxazole, Isothiazole, 1,2,3‐Triazole,and Pyrrole Rings from N‐(5,5‐Dimethyl‐3‐oxocyclohexenyl)‐S,S‐diphenylsulfilimine

Reactions of N‐(5,5‐dimethyl‐3‐oxocyclohexenyl)‐S,S‐diphenylsulfilimine, a kind of enaminone, with isopentyl nitrite, isocyanates, isothocyanates, benzenediazonium chloride, and 1,1,1‐trifluoro‐4‐ethoxy‐3‐buten‐2‐one gave 1,2,5‐oxadiazole, isoxazole, isothiazole, 1,2,3‐triazole, and pyrrole derivatives condensed with cyclohexane, respectively, in one pot.     

Iodine‐Mediated Synthesis of 2‐Arylbenzoxazoles, 2‐Arylbenzimidazoles,and 1,3,5‐Trisubstituted Pyrazoles

2‐Arylbenzoxazoles and 2‐arylbenzimidazoles were synthesized by the reaction of aldehydes with 2‐aminophenol and O‐phenylenediamines in the presence of iodine. 1,3,5‐Trisubstituted pyrazoles were synthesized from chalcones and hydrazines in the presence of iodine.     

Comparative Analysis of the Properties of Tween‐20, Tween‐60, Tween‐80, Arlacel‐60, and Arlacel‐80

Foamability and foam stability, emulsifying power, surface tension, and interfacial tension were investigated for Tween‐20 (polyoxyethylene sorbitan monolaurate), Tween‐60 (polyoxyethylene sorbitan monostearate), Tween‐80 (polyoxyethylene sorbitan monooleate), Arlacel‐60 (Sorbitan stearate), and Arlacel‐80 (Sorbitan oleate). Among all the surfactants tested for their foaming power and foamabilty, Arlacel‐60 and Arlacel‐80 showed the best results; the foaming power and foamability was found to be 100%. The surfactants having foam stability more than 50% can be considered as metastable and those less than 50% are considered as low‐stability foams. In case of surface tension and interfacial tension property measurements, Arlacel‐80 showed the best results. At 1% surfactant concentration, the surface tension and interfacial tension of Arlacel‐80 was found to be 29.9 dynes/cm and 1.1 dynes/cm at 30°C ambient temperature. Also, Arlacel‐60 was found to exhibit the best emulsifying power among all the surfactants tested. At 30°C, the emulsifying property of Arlacel‐60 was 6 hours.     

N‐Chlorosulfonyloxazolidin‐2‐ones: Synthesis,Structure, and Reactivity Toward Aminoesters

Abstract

Synthesis, structure, and reactivity of chiral N‐chlorosulfonyloxazolidin‐2‐ones are described. Their synthesis were easily carried out starting from the corresponding chiral oxazolidin‐2‐ones and sulfuryl chloride to afford the title compounds 1 in high yields.     

Simple,Efficient, and Stereoselective Oxidation of Triphenylfurans to cis‐But‐2‐ene‐1,4‐diones

Triphenylfurans are stereoselctively oxidized to cis‐but‐2‐ene‐1,4‐diones, suitable precursors of 3(2H)‐furanones, in very good yields using ammonium nitrate or potassium nitrate in 80% aqueous acetic acid.     

Synthesis and Amphiphilic Behavior of N,N‐Bis‐glucosyl‐1,5‐benzodiazepin‐2,4‐dione

Abstract

Glucosyl‐1,5‐benzodiazepin‐2,4‐diones were synthesized in order to study the influence of the glucidic moiety on the amphiphilic behaviour. The glucosyl groups include 6‐deoxy‐D‐glucopyranos‐6‐yl and 6‐deoxy‐3‐O‐R‐D‐glucopyranos‐6‐yl (R = n ? C _n H _2n+1; n = 1, 8, 10 and 12). Variation in the length of the hydrocarbon chain allowed comparison of such amphiphilic data as water solubility (Sw) and surface tension (γ) values. At 25°C, the glucopyranosyl benzodiazepines with R = H and CH₃ show a higher water solubility than the starting 1,5‐benzodiazepin‐2,4‐diones. Some other glucidic benzodiazepine derivatives with an appropriate alkyl chain at C‐3 carbon of the D‐glucopyranose present a variable hydrosolubility and surface tension γ values close to 43 to 46 mN · m^?1 at the corresponding saturation. Moreover, according to preliminary tests, these compounds seem to show a better affinity for the blood brain barrier.     

Copolymers of 2‐(3‐(6‐tetralino)‐3‐methyl‐1‐cyclobutyl)‐2‐Hydroxyethyl Methacrylate with Acrylonitrile and 4‐Vinylpyridine: Synthesis,Characterization, and Monomer Reactivity Ratios

The copolymerization of 2‐(3‐(6‐tetralino)‐3‐methyl‐1‐cyclobutyl)‐2‐hydroxyethyl methacrylate (TCHEMA), monomer with acrylonitrile and 4‐vinylpyridine were carried out in 1,4‐dioxane solution at 65°C using AIBN as an initiator. The copolymers were characterized by FTIR, ¹H‐NMR, and ¹³C‐NMR spectroscopic techniques. Thermal properties of the polymers were also studied by thermogravimetric analysis and differential scanning calorimetry. The copolymer compositions were determined by elemental analysis. The monomer reactivity ratios were calculated by the Fineman‐Ross and Kelen‐Tüdös method. Also, the apparent thermal decomposition activation energies were calculated by the Ozawa method with a Shimadzu TGA 50 thermogravimetric analysis thermobalance.     

Practical Synthesis of N‐Alkyl‐N‐alkyloxycarbonylaminomethyl Prodrug Derivatives of Acetaminophen,Theophylline, and 6‐Mercaptopurine

We report a novel synthesis of N‐alkyl‐N‐alkyloxycarbonylaminomethyl (NANAOCAM) prodrugs of acetaminophen, theophylline, and 6‐mercaptopurine by alkylation of the corresponding drug molecule with N‐alkyl‐N‐alkyloxycarbonylaminomethyl chlorides in good yield. Most of the alkylating agents were efficiently synthesized by chloromethylation of N‐alkyl carbamic acid alkyl esters, which in turn were made from alkyl amines and alkyl chloroformates. In cases where the alkyl chloroformates were not available, synthesis of N‐alkyl carbamic acid alkyl esters was accomplished by converting an alcohol to a chloroformate or to an activated acylating agent such as acyl imidazoles or p‐nitrophenylcarbonate esters, followed by their reaction with alkyl amines.     

Oligo‐Ortho‐Chloroazomethinephenol and its Metal Complexes: Synthesis,Characterization, Antimicrobial and Thermal Properties

The new Schiff base oligomer (oligo‐ortho‐chloroazomethinephenol) was synthesized by the condensation of ortho‐chloroaniline with oligosalicylaldehyde (OSA). Oligomer‐metal complexes of oligo‐ortho‐chloroazomethinephenol (OKAP) with Cu(II), Zn(II) and Co(II) were synthesized. The properties of OKAP and oligomer‐metal complexes were studied by elemental, UV‐Vis, ¹H‐NMR, FT‐IR, magnetic susceptibility analyses. The number average molecular weight and mass average molecular weight OKAP were found to be 1494 g · mol^?1 and 5418 g · mol^?1, respectively. Elemental analyses of oligomer‐metal complexes suggest that the ratio of metal to oligomer is 1∶2. The results indicate that the OKAP coordinate through azomethine nitrogen and phenolic oxygen to the metal ions. Antimicrobial activity of OKAP was tested against S. cerevisiae, B. subtilis, E. coli, K. pneumoniae, M. luteus and S. aureus. The thermal stabilities of the OKAP and oligomer‐metal complexes were compared by thermogravimetric (TG) analyses. According to TG, OKAP, and oligomer‐metal complexes were stable against temperature and thermooxidative decomposition. The weight losses of OKAP and oligomer‐metal complexes were found to be at 400 and 800°C at 20.2 and 50.0 (OKAP), 17.1 and 41.1 (Cu(II)), 13.4 and 38.5 (Zn(II)), 18.3 and 68.2 (Co(II)), %, respectively. Based on half degradation temperature (T_50%) parameters, Cu(II) and Zn(II) complexes were more resistant than the OKAP and Co(II) complex.     

Novel Copolymers of Styrene and Some Ring‐Substituted 2‐Cyano‐N,N‐Dimethyl‐3‐Phenyl‐2‐Propenamides

Electrophilic trisubstituted ethylene monomers, ring‐substituted 2‐cyano‐N,N‐dimethyl‐3‐phenyl‐2‐propenamides, RC₆H₄CH?C(CN)CON(CH₃)₂ (where R is 3‐benzyloxy, 4‐benzyloxy, 3‐ethoxy‐4‐methoxy, 3‐bromo‐4‐methoxy, 5‐bromo‐2‐methoxy, 2‐chloro‐6‐fluoro) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and N,N‐dimethyl cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 300–450°C range.     

Synthesis of Anomerically Pure,Furanose‐Free α‐Benzyl‐2‐amino‐2‐deoxy‐d‐altro‐ and d‐manno‐pyranosides and Some of Their Derivatives

The anomerically pure benzyl α‐d‐glycoside of 2‐amino‐2‐deoxy‐mannopyranoside was synthesized from d‐glucopyranose via 2‐amino‐2‐deoxy‐d‐altrose intermediates. Unlike the direct synthesis from mannosamine in the literature, our method provides furanose‐free products. A new method for the preparation of cis‐2,3‐oxazolidinones of 2‐amino‐2‐deoxy‐sugars was developed. A selective removal of the glycosidic benzyl group in the presence of 4,6‐O‐benzylidene protection was developed, which may provide new routes for the synthesis of oligosaccharides. Furanose‐free derivatives of α‐benzyl‐2‐amino‐2‐deoxy‐mannopyranuronic acids synthesized here offered possibilities for direct comparisons to prior literature preparations.     

Improved Syntheses of N‐Desmethylcitalopram and N,N‐Didesmethylcitalopram

An improved and efficient synthesis of N‐desmethylcitalopram (2) and N,N‐didesmethylcitalopram (3) is presented. The method involved N‐demethylation of citalopram (1) using 1‐chloroethyl chloroformate to give 2 in 87% yield. Synthesis of 3 was accomplished by alkylation of 8 with 1‐(3‐bromopropyl)‐2,2,5,5‐tetramethyl‐1‐aza‐2,5‐disilacyclopentane (9).     

Novel Copolymers of Styrene and Halogen Ring‐Substituted 2‐Cyano‐N,N‐Dimethyl‐3‐Phenyl‐2‐Propenamides

Electrophilic trisubstituted ethylene monomers, halogen ring‐substituted 2‐cyano‐N,N‐dimethyl‐3‐phenyl‐2‐propenamides, RC₆H₄CH [dbnd]C(CN)CON(CH₃)₂ (where R is 2‐Br, 3‐Br, 4‐Br, 2‐Cl, 3‐Cl, 4‐Cl, 2‐F, 3‐F, 4‐F), were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and N,N‐dimethyl cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C NMR, GPC, DSC, and TGA. High T _g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 300–450°C range.     

Synthesis,Characterization and Thermal Degradation of Oligo‐2‐[(4‐hydroxyphenyl) Imino Methyl]‐1‐naphtol and Oligomer‐Metal Complexes

The oxidative polycondensation of 2‐[(4‐hydroxyphenyl) imino methyl]‐1‐naphtol (4‐HPIMN) has been accomplished by using NaOCl, H₂O₂ and air O₂ oxidants in aqueous alkaline medium. Optimum reaction conditions of the oxidative polycondensation and the main parameters of the process were established. At optimum reaction conditions, yield of the products were found to be 77.0%, 91.6% and 99.0% for H₂O₂, air O₂ and NaOCl oxidants, respectively. The structures of the obtained monomer and oligomer were confirmed by FT‐IR, UV‐Vis, ¹H‐ and ¹³C‐NMR and elemental analysis. The characterization was made by TG‐DTA, SEC and solubility tests. The ¹H‐ and ¹³C‐NMR data shows that the polymerization proceeded by the C–C coupling of ortho positions according to –OH group of 4‐HPIMN. The molecular weight distribution values of the product were determined by using size exclusion chromatography (SEC). The number‐average molecular weight (M_n), weight‐average molecular weight (M_w) and polydispersity index (PDI) values of O‐4‐HPIMN were found to be 1777, 2225 and 1.252; 1790, 2250 and 1.257; 4540, 5139 g mol^?1, and 1.132 for NaOCl, H₂O₂ and air O₂ oxidants, respectively. According to TG analyses, the carbonaceous residue of 4‐HPIMN and O‐4‐HPIMN was found to be 28.02% and 44.22% at 1000°C, respectively. Thermal analyses of O‐4‐HPIMN‐Cd, O‐4‐HPIMN‐Co, O‐4‐HPIMN‐Cu, O‐4‐HPIMN‐Fe, O‐4‐HPIMN‐Mg, O‐4‐HPIMN‐Mn, O‐4‐HPIMN‐Ni, O‐4‐HPIMN‐Pb and O‐4‐HPIMN‐Zn oligomer‐metal complex compounds were investigated in N₂ atmosphere between 15–1000°C.     

Novel Copolymers of Styrene and Some Ring‐Substituted 2‐Cyano‐N,N‐Dimethyl‐3‐Phenyl‐2‐Propenamides

Electrophilic trisubstituted ethylene monomers, ring‐substituted 2‐cyano‐N,N‐dimethyl‐3‐phenyl‐2‐propenamides, RC₆H₄CH?C(CN)CON(CH₃)₂ (where R is 4‐(CH₃)₂N, 4‐CH₃CO₂, 4‐CH₃CONH, 2‐CN, 3‐CN, 4‐CN, 4‐(C₂H₅)₂N) were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and N,N‐dimethyl cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 300–450°C range.     

Novel Copolymers of Styrene and Alkoxy Ring‐Substituted 2‐Cyano‐N,N‐Dimethyl‐3‐Phenyl‐2‐Propenamides

Electrophilic trisubstituted ethylene monomers, alkoxy ring‐substituted 2‐cyano‐N,N‐dimethyl‐3‐phenyl‐2‐propenamides, RC₆H₄CH?C(CN)CON(CH₃)₂ (where R is 2‐OCH₃, 3‐OCH₃, 4‐OCH₃, 2‐OCH₂CH₃, 3‐OCH₂CH₃, 4‐OCH₂CH₂CH₃, 4‐OCH₂CH₂CH₂CH₃), were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and N,N‐dimethyl cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ACBN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 300–450°C range.     

Novel Copolymers of Styrene and Halogen Ring‐Disubstituted 2‐Cyano‐N,N‐Dimethyl‐3‐Phenyl‐2‐Propenamides

Electrophilic trisubstituted ethylene monomers, halogen ring‐disubstituted 2‐cyano‐N,N‐dimethyl‐3‐phenyl‐2‐propenamides, RC₆H₃CH?C(CN)CON(CH₃)₂ (where R is 2,3‐dichloro, 2,4‐dichloro, 2,6‐dichloro, 3,4‐dichloro, 3,5‐dichloro, 2,3‐difluoro, 2,4‐difluoro, 2,6‐difluoro, 3,4‐difluoro, 3,5‐difluoro), were synthesized by potassium hydroxide catalyzed Knoevenagel condensation of ring‐substituted benzaldehydes and N,N‐dimethyl cyanoacetamide, and characterized by CHN elemental analysis, IR, ¹H‐ and ¹³C‐NMR. Novel copolymers of the ethylenes and styrene were prepared at equimolar monomer feed composition by solution copolymerization in the presence of a radical initiator, ABCN at 70°C. The composition of the copolymers was calculated from nitrogen analysis, and the structures were analyzed by IR, ¹H and ¹³C NMR, GPC, DSC, and TGA. High T_g of the copolymers in comparison with that of polystyrene indicates a substantial decrease in chain mobility of the copolymer due to the high dipolar character of the trisubstituted ethylene monomer unit. The gravimetric analysis indicated that the copolymers decompose in the 300–450°C range.