Synthesis of imidazo[4,5-e][1,4]diazepine-8-one

We have developed a method for synthesis of 1-methyl-4,5,7, 8-tetrahydro-6H-imidazo[4,5-e][1,4]diazepin-8-one. We have shown that in intramolecular cyclization of N-(2-hydroxyethyl)- or N-(2-chloroethyl)amides of 1-methyl-4-aminoimidazolyl-5-carboxylic acids it is not the corresponding tetrahydroimidazo[4,5-e][1,4]diazepin-8-ones which are formed but rather the isomeric 4-amino-5-(oxazolin-2-yl)imidazoles.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1203–1206, September, 1993.     

Misincorporation of alkylated amino acids into hemoglobin--a possible source of background alkylations

Misincorporation of 2-hydroxyethylated amino acids into hemoglobin during de novo synthesis was studied by injecting mice with radiolabelled N-(2-hydroxyethyl)valine, S-(2-hydroxyethyl)cystine or N tau-(2-hydroxyethyl)histidine. The results showed that S-(2-hydroxyethyl)cysteine and N tau-(2-hydroxyethyl)histidine were misincorporated, whereas N-(2-hydroxyethyl)valine was not. Monitoring of in vivo doses of hydroxyethylating agents by determination of N-(2-hydroxyethyl)valine was free of the disturbing influence of such misincorporation.     

Saturated Nitrogen-containing Heterocycles. 20. Catalytic Reduction of N-Hydroxyethylpyridinium and Quinolinium Salts

Previously unknown N-(2-hydroxyethyl)perhydroquinolines and N-(2-hydroxyethyl)piperidines were synthesized by catalytic reduction of N-(2-hydroxyethyl)tetrahydroquinolinium and N-(2-hydroxyethyl)tetrahydropyridinium tetrafluoroborates. A scheme for the formation of the hydrogenation products is presented.     

Diazabicycloalkanes with nitrogen atoms in the junction positions. 11. Synthesis of dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene

The reaction of ethylene oxide with phenazine followed by treatment with HCl gives N-(2-hydroxyethyl)phenazinium chloride, which yields N-2-haloethyl derivatives of phenazine in a mixture with products of their one-electron reduction when the hydroxyl group is exchanged for a halogen. Heating of these mixtures in the presence of sodium borohydride results in intramolecular cyclization with the formation of a new heterocyclic system, viz., dibenzo[b,e]-1,4-diazabicyclo[2.2.2]octadiene.For report 10 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1407–1411, October, 1984.     

Diazabicycloalkanes with nitrogen atoms in the nodal positions. 3. The benzo[b]-1,4-diazabicyclo [2.2.2]-octene system

Benzo[b]-1,4-diazabicyclo[2.2.2]octene and 4′-methylbenzo[1′,2′-b]-1,4-diazabicyclo[2.2.2]octene were synthesized by the reaction of N-acetyl-6-H- and 6-methyl-1,2,3,4-tetrahydroquinoxalines with ethylene oxide and subsequent cyclization of the N-(β-hydroxyethyl)-N'-acetyl derivatives in refluxing HBr. The errors of the published data on the benzo[b]-1,4-diazabicyclo[2.2.2]octene system are demonstrated. See [1] for communication 2. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 827–830.     

C-hydroxyalkylation of N-adamantylanilines by hexafluoroacetone and methyl trifluoropyruvate

N-(1-Adamantyl)-4-(1-hydroxy-1-trifluoromethyl- 2,2,2- trifluoroethyl)aniline (III) and N-(1-adamantyl)-4-(1-hydroxy-1-methoxycarbony 1-2,2,2-trif luoroethyl) aniline (IV) were obtained by the reaction of N-(1-adamantyl)aniline with ketone (I) and ketoester (II). Analogous procedures gave N-(2-adamantyl)- 4- (1-hydroxy- 1-trifluoromethyl- 2, 2,2-trifluoroethyl)aniline (V) and N-(2-adamantyl)-4-(1-hydroxy-1-methoxycarbonyl-2,2,2-trifluoroethyl)aniline (VI). The action of hydrogen peroxide on (III) in the presence of sodium tungstenate gave N- (1- adamantyl)- 4- (1- hydroxy- 1- trifluoromethyl- 2,2,2- trifluoroethyl)aniline N-oxide (VII).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2348–2350, October, 1989.     

2-Polyfluoroalkylchromones. 8. 2-Trifluoromethyl- and 6-nitro-2-trifluoromethylchromones in reactions with amines

The reactions of 6-nitro-2-trifluoromethylchromone with benzylamine, ethanolamine, and aniline afforded 3-benzyl(2-hydroxyethyl,phenyl)amino-4,4,4-trifluoro-1-(2-hydroxy-5-nitrophenyl)but-2-en-1-ones, respectively, whereas the reactions with ethylenediamine and diethylenetriamine gave rise to 5-(2-hydroxy-5-nitrophenyl)-7-trifluoromethyl-2,3-dihydro-1H-1,4-diazepine and 5-(2-hydroxy-5-nitrophenyl)-7-trifluoromethyl-1,4,8-triazabicyclo[5.3.0]dec-4-ene, respectively. Morpholine added at the double bond of 2-trifluoromethyl- and 6-nitro-2-trifluoromethylchromones to form 2-morpholino-2-trifluoromethylchroman-4-one and its 6-nitro-substituted analog, respectively, whereas piperidine reacted only with 2-trifluoromethylchromone to yield 2-piperidino-2-trifluoromethylchroman-4-one.     

Diazabicycloalkanes with nitrogen atoms in nodal positions. 14. Synthesis of dibenzo[1′,2′-b,e]-1,4-diazabicyclo[2.2.2]octadienes containing a tertiary amino group in the aromatic ring

The corresponding 2-amino derivatives of phenazinium salts were obtained by the action of dimethylamine and morpholine on N-(2-hydroxyethyl)phenazinium chloride. The subsequent exchange of the hydroxyl group for chlorine and the reductive cyclization of 2-amino derivatives of N-(2-chloroethyl)phenazinium salts leads to 4-aminodibenzo[1,2-b,e]-1,4-diazabicyclo[2.2.2]octadienes, together with unsubstituted dibenzo-[b,e]-1,4-diazabicyclo[2.2.2]octadiene and the corresponding 2-aminophenazines.For Communication 13, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1658–1661, December, 1986.     

Schiff’s bases as inhibitors of mild steel corrosion in hydrochloric acid

Mass loss and thermometric methods are used to study the inhibition of corrosion of mild steel in hydrochloric acid by Schiff’s bases N-(furfurlidine)-4-methoxy aniline, N-(furfurlidine)-4-methylaniline, N-(salicylidine)-4-methoxy aniline, N-(cinnamalidine)-4-methoxy aniline, and N-(cinnamalidine)-2-methylaniline. Results of inhibition efficiency yielded by the two methods are in good agreement and depend on the inhibitor and acid concentration. Maximum inhibition efficiency is 98%. The efficiency increases with the inhibitor concentration and acid strength. Published in Russian in Elektrokhimiya, 2007, Vol. 43, No. 2, pp. 252–256. The text was submitted by the authors in English.     

Reaction between isoprene and aniline on complex palladium catalysts

Isoprene and aniline have been reacted on the catalytic system Pd(acac)₂-Ph₃P to form a mixture of isomeric telomers: N-(dimethyloctadien-2,7-yl-1)anilines and N-(dimethyloctadien-1,7-yl-3)anilines but on the catalytic system Pd(acac)₂-Ph₃P-CF₃COOH the main product is a mixture of N-(methylbuten-2-yl)aniline adducts. The reaction between N-methylaniline and isoprene on the latter catalyst also gives a mixture of N-methyl and N-(methylbuten-2-yl)aniline adducts.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1794–1798, August, 1992.     

Acid-catalyzed Conversions of N-(4-Nitrobenzylidene)-2-cyclopropyl- and N-(4-Nitrobenzylidene)-2-alkenylanilines. A new Method for the Synthesis of Dihydroquinolines and Quinolines

The acid-catalyzed conversions of N-(4-nitrobenzylidene)-2-cyclopropyl- and N-(4-nitrobenzylidene)-2-alkenylanilines have been studied. It has been established that the protonated azomethine unit of N-(4-nitrobenzylidene)-2-cyclopropylanilines is not capable of initiating intramolecular heterocyclization with participation of the three-membered ring. Conversion of N-(4-nitrobenzylidene)-2-(1-methylcyclopropyl)aniline to derivatives of quinoline is possible under the influence of concentrated H₂SO₄. Under the same conditions 2-methylcyclopropyl- and cyclopropyl-substituted Schiff's bases form only the corresponding alkenylazomethines (isomerization of the three-membered ring). Under the influence of more moderate acids (trifluoroacetic, polyphosphoric) N-(4-nitrobenzylidene)-2-propenyl- and N-(4-nitrobenzylidene)-2-buten-2-yl)anilines are converted to the corresponding dihydroquinolines and quinolines in high yields. N-(4-Nitrobenzylide! ne)- 2-(2,2-dimethylvinyl)aniline does not form derivatives of quinoline under the influence of the same acids in the given conditions.     

New radiopharmaceuticals based on N-substitution of nitrilotriacetic acid

In this paper, the labeling characteristics and biological behavior of five aminopolycarboxylic acid derivatives have been studied: N-(phosphonomethyl) nitrilodiacetic acid (^99mTc-MPIDA), N,N-(diphosphono) aminoacetic acid (^99mTc-GDP), N-(2-carbamoylethyl) nitrilodiacetic acid (^99mTc-KEIDA), N-(2,3-dihydroxypropyl) nitrilodiacetic acid (^99mTc-DPKA), 2-[N-(2-hydroxyethyl)-N-carboxymethyl] aminopropanoic acid (^99mTc-EAPA).     

Polyesters derived from 1,4-oxathian-2-ones

1,4-Oxathian-2-one ( 1a ) was prepared in high yield by oligomerization of methyl(2-hydroxyethyl)mercaptoacetate ( 3 ) followed by catalytic depolymerization in vacuo. A similar sequence starting with methyl(2-hydroxyethyl)sulfonylacetate ( 5 ) afforded the corresponding sulfone, 1,4-oxathian-2-one-4,4-dioxide ( 1c ), however, 1,4-oxathian-2-one-4-oxide ( 1b ) could not be obtained by this procedure. Ring opening melt polymerization of 1a and 1c afforded low molecular weight crystalline polyesters 2a and 2c . Oxidation of 2a with m-chloroperoxybenzoic acid produced the corresponding polyester 2b containing sulfoxide groups. Thermogravimetric analyses and visual observations indicated 2b to be thermally unstable relative to 2a and 2c .     

Synthesis of 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides

Four 6-phenyl-5,6,7,8-tetrahydro-4H-1,3,2,6-dioxathiazocine 2-oxides were synthesized by the reaction of the corresponding N,N-bis(2-hydroxyethyl)aniline with thionyl chloride in the presence of triethylamine.     

Diazabicycloalkanes with nitrogen atoms in the nodal positions. 4. Intramolecular cyclization of N-(β-x-ethyl)-1,2,3,4-tetrahydroquinoxalines and behavior of benzo[b]-1,4-diazabicyclo[2.2.2]octenes in acidic media

The intramolecular cyclization of N-(β-hydroxyethyl)-N'-acetyl-1,2,3,4-tetrahydroquinoxaline in refluxing HBr was investigated by liquid microcolumn chromatography. Under these conditions the amide group undergoes rapid hydrolysis, the hydroxy groups undergo relatively slow exchange by bromine, and the resulting N-(β-bromoethyl)-1,2,3,4-tetrahydroquinoxaline undergoes cyclization to give benzo[b]-1,4-diazabicyclo[2.2.2]octene. These transformations terminate with the establishment of equilibrium between VII and I. 7-Methyl-N-(β-chloroethyl)-1,2,3,4-tetrahydroquinoxaline similarly forms an equilibrium reaction mixture in HBr. The effect of various factors (the acid and bromide ion concentrations, the character of the acid, and the temperature) on the position of the equilibrium of the compounds obtained and on the occurrence of side reactions (hydrolysis and dealky lation) was studied. See [1] for communication 3. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 831–836, June, 1980.     

Synthesis and Characterization of Some Novel Higher C,N-Diphenyl Nitrones,Isoxazolines, and Mercaptobenzimidazoles as Oleochemicals

Abstract

Some novel long-chain nitrones, isoxazolines, and (1H-benzo[d]-imidazol-2-ylthio) derivatives were synthesized. Nitrones, N-{4-[2-(tetradecylthio)acetoxy]benzylidene}aniline oxide, and N-[4-(12-oxo-2,5,8,11-tetraoxadocosan-22-yloxy)benzylidene]aniline oxide were prepared via the reaction of β-phenylhydroxylamine with the corresponding aromatic aldehydes. The isoxazolines were prepared from undec-10-en-1-ol and benzonitrile-N-oxide which was generated in situ. The 1H-benzo[d]-imidazol-2-ylthio derivatives were synthesized via the replacement reaction of ω-bromo esters and 2-mercaptobenzimidazole.     

Reaction of hydroxy derivatives of piperidines and pyridines with acetylene under pressure

Methods for the synthesis of vinyl ethers of N-(β-hydroxyethyl)-piperidine, 3-hydroxy-N-methylpiperidine, 2-(β-hydroxyethyl)pyridine, and 2-(hydroxypyridine) based on the addition of the corresponding derivatives to acetylene have been developed. Their hydrogenation forms the corresponding ethyl ethers.     

The Formation of Intermediate Lactones During Aminolysis of Diethyl Xylarate

Abstract

The aminolysis of diethyl xylarate was found to proceed through intermediate lactones. In dimethyl sulfoxide at 30°C in the presence of etha-nolamine/ the 1,5-diester is rapidly converted into ethyl d, l-xylaro-1,4-lactone, which reacts with the primary amine to give ethyr N-(2-hydroxyech-yl)-d, l-xylaramide. This compound then forms N-(2-hydroxyethyl)-d, l-xylara-mide-2T5-lactone, which in turn reacts with ethanolamine to produce the final product, N,N'-bis-(2-hydroxyethyl)-d-l-xylaramide. This sequence of reactions was established by ¹³C NMR spectroscbpy.     

High-capacity chitosan-based chelating resin for on-line collection of transition and rare-earth metals prior to inductively coupled plasma-atomic emission spectrometry measurement

High-capacity chitosan-based chelating resin, N-(2-hydroxyethyl)glycine-type chitosan, was synthesized using chloromethyloxirane (CMO) as a cross-linker and a coupling arms and hydroxylethylamine and bromoacetic acid as a synthesizer for the N-(2-hydroxyethyl)glycine chelating moiety. The CMO could bind with both of hydroxyl and amino group of the chitosan resin, and then couple with the chelating moiety. Increasing the amounts of chelating moiety could increase the capacity of the resin toward metal ions. Most transition and rare-earth metals could adsorb quantitatively on the resin at wide pH ranges and could be separated from alkaline and alkaline-earth metals. The resin was packed in a mini-column (40 mm length × 2 mm i.d.) which was installed in a Multi-Auto-Pret system. The Multi-Auto-Pret system coupled with ICP-AES was successfully applied to the determination of transition and rare-earth metals in river water samples.     

Indole derivatives

The influence of dehydrogenating dehydrating (deaminating) additives on the composition and yield on the products of the cyclization of N-(-hydroxyethyl)aniline and N,N-diphenylethylenediamine has been studied. The closure of the indole and pyrrole rings takes place through the dehydration and deamination, respectively, of the starting material on oxide catalysts. A reaction scheme explaining the formation of all the products observed has been suggested.For Communication L see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 766–769, June, 1970.