Reactions of <Emphasis Type="Italic">N</Emphasis>-Allyl- and <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Diallyltrifluoromethanesulfonamides with Carboxylic Acid Amides under Oxidizing Conditions

Reactions of acetamide and benzamide with N-allyltrifluoromethanesulfonamide in the presence of t-BuOCl–NaI afforded exclusively 2,5-bis(chloromethyl)-1,4-bis(trifluoromethanesulfonyl)piperazine. Analogous reaction with N,N-diallyltrifluoromethanesulfonamide gave mixed halogenation product at only one C=C double bond of the substrate.     

Synthesis and structure of silicon-containing <Emphasis Type="Italic">N</Emphasis>-methyland <Emphasis Type="Italic">N</Emphasis>-benzoylamides of diisopropylphosphoric acid

Diisopropyl N-benzoyl-N-(trimethylsilyl)phosphoramidate reacts with ClCH₂SiMe₂Cl under mild conditions to form diisopropyl N-benzoyl-N-[(chlorodimethylsilyl)methyl]phosphoramidate (III). Diisopropyl N-methyl-N-(trimethylsilyl)phosphoramidate with ClCH₂SiMe₂Cl affords an N-transsilylation product which does not rearrange into diisopropyl N-[(chlorodimethylsilyl)methyl]-N-methylphosphoramidate (XV) even under severe conditions (4 h, 130°C). Compound XV was prepared by the reaction of diisopropyl phosphorochloridate with N-[(methoxydimethylsilyl)methyl]-N-methylamine followed by treatment of diisopropyl N-[(methoxydimethylsilyl)methyl]-N-methylphosphoramidate with boron trichloride. Analysis of experimental and calculated ²⁹Si chemical shifts points to a five-coordinate silicon atom in compound III and a fourcoordinate silicon atom in compound XV. According to B3LYP calculations with due regard to solvent effects, compound III is an isomer with a C=O→Si bond. By variation of substituents at silicon, phosphorus, and carbonyl carbon atoms, chelate structures with either C=O→Si or P=O→Si dative bonds can be obtained.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-Aryl- and <Emphasis Type="Italic">N,N</Emphasis>-diethyl-2-methyl-3-phenyl-4-sulfanylidene-3,4,5,6-tetrahydro-2<Emphasis Type="Italic">H</Emphasis>-2,6-methano-1,3,5-benzoxadiazocine-11-carboxamides

N-Aryl- and N,N-diethyl-3-oxobutanamides reacted with salicylaldehyde and N-phenylthiourea in ethanol in the presence of sodium hydrogen sulfate as catalyst to give the corresponding N-substituted 2-methyl-3-phenyl-4-sulfanylidene-3,4,5,6-tetrahydro-2H-2,6-methano-1,3,5-benzoxadiazocine-11-carboxamides.     

Syntheses,structures, and solid-state phosphorescence characteristics of <Emphasis Type="Italic">trans</Emphasis>-bis(salicylaldiminato)Pt(II) complexes bearing perpendicular <Emphasis Type="Italic">N</Emphasis>-aryl functionalities

The syntheses, structures, and solid-state emission characteristics of trans-bis(salicylaldiminato)Pt(II) complexes bearing N-aromatic functionalities are described herein. A series of Pt complexes bearing various N-phenyl (1) and N-(1-naphthyl) (2) groups on the salicylaldiminato ligands were prepared by reacting PtCl₂(CH₃CN)₂ with the corresponding N-salicylidene aromatic amines, and the trans-coordination and crystal packing of these complexes were unequivocally established based on X-ray diffraction (XRD). Complexes with 2,6-dimethylphenyl (1c), 2,6-diisopropylphenyl (1d), 1-naphthyl (2a), and 1-(2-methylnaphthyl) (2b) groups on the N atoms exhibited intense phosphorescent emission at ambient temperature in the crystalline state, while those with phenyl (1a), 2,6-dibromophenyl (1b), and 2,6-bis(N,N-dimethylamino)phenyl (1e) functionalities were either less emissive or non-emissive under the same conditions. XRD analyses identified significant intramolecular interactions between Pt and H atoms of the N-aryl functionalities in the emissive crystals of 1c, 1d, and 2a. These interactions were evidently an important factor associated with intense emission at ambient temperature.     

Cycloaminomethylation of dihydric phenols catalyzed by <Emphasis Type="Italic">d</Emphasis>- and <Emphasis Type="Italic">f</Emphasis>-metal compounds

An efficient method has been developed for the synthesis of 7,16,25-triaryl-7,8,16,17,25,26-hexahydro-6H,15H,24H-tribenzo[f,m,t][1,5,8,12,15,19,3,10,17]hexaoxatriazacyclohenicosines, 3,8-diaryl-2,3,4,7,8,9-hexahydrobenzo[1,2-e:4,3-e′]bis[1,3]oxazines, 3,9-bis(chlorophenyl)-3,4,9,10-tetrahydro-2H,8H-benzo[1,2-e:3,4-e′]bis[1,3]oxazines, and 2,9-bis(chlorophenyl)-1,2,3,8,9,10-hexahydrobenzo[1,2-e:6,5-e′]bis-[1,3]oxazines via cycloaminomethylation of pyrocatechol, resorcinol, and hydroquinone with N,N-bis(methoxymethyl) anilines in the presence of samarium catalysts.     

Activated sterically strained C=N bond in <Emphasis Type="Italic">N</Emphasis>-substituted <Emphasis Type="Italic">p</Emphasis>-quinone mono- and diimines: XV. Synthesis,structure, and reactions with alcohols of <Emphasis Type="Italic">N</Emphasis>-carbamoyl-1,4-benzoquinone imines

The reaction of 4-aminophenols with N-nitrourea or with sodium cyanate in acetic acid gave the corresponding 4-ureidophenols which were oxidized to N-carbamoyl-1,4-benzoquinone imines, substituted N-(4-oxocyclohexa-2,5-dien-1-ylidene)ureas. N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-ylidene)urea possessing activated sterically strained C=N bond reacted with alcohols to afford N-(1-alkoxy-2,6-dimethyl-4-oxocyclohexa-2,5-dienyl)ureas.     

Reductive acylamination of pyridine <Emphasis Type="Italic">N</Emphasis>-oxide with ethylenediamine and phenylenediamines

Reactions of pyridine N-oxide with ethylenediamine and o- and p-phenylenediamines in the presence of p-toluenesulfonyl chloride in alkaline medium lead to the formation of the corresponding N,N′-bis-(p-tolylsulfonyl)-N,N′-bis(pyridin-2-yl)diamines as a result of reductive acylamination.     

<Emphasis Type="Italic">N</Emphasis>-aryl-<Emphasis Type="Italic">o</Emphasis>-iminobenzoquinones as novel regulators of radical polymerization

The effect of a number of quinoid compounds on methyl methacrylate polymerization initiated by azo-bis(isobutyronitrile) has been studied. It has been revealed that N-aryl-o-iminobenzoquinones, in contrast to o-benzoquinones, can provide radical polymerization of methyl methacrylate in controllable mode. The efficiency of the compounds as chain growth regulators has been found to depend on their composition and reaction conditions. It has been established that 4,6-di-tert-butyl-N-(2,6-diethylphenyl)-o-iminobenzoquinone and 4,6-di-tert-butyl-N-(2,6-diisopropylphenyl)-o-iminobenzoquinone under radical initiation conditions provide the synthesis of poly(methyl methacrylate) with wide-range molecular weight, retaining polydispersity indices about ~1.4–1.8 up to deep conversions.     

<Emphasis Type="Italic">N</Emphasis>-allyl and <Emphasis Type="Italic">N</Emphasis>-propargyl trifluoromethanesulfonimides. Theoretical analysis

Tautomers of N-allyl- and N-propargyl-substituted trifluoromethanesulfonimides (CF₃SO₂)₂NR (R = CH₂CH=CH₂, Z/E-CH=CHMe, CH₂C≡CH, CH=CH=CH₂, C≡CCH₂) were calculated by the DFT (B3LYP, wB97XD, PBE1PBE), MP2, and CBS-QB3 methods. The results were compared with the theoretical data for the corresponding amines and amides NHRR¹ (R¹ = H, CF₃SO₂). It was shown that there is no conjugation between the nitrogen atom and C=C bond and that conjugation exists with the C≡C bond with electron density displacement toward the nitrogen atom. The calculations of anions derived from N-allyl- and N-propargyl-trifluoromethanesulfonimides revealed the possibility of their rearrangement with elimination of trifluoromethanesulfinate anion and formation of its H-complex with N-(prop-2-en-1-ylidene)trifluoromethanesulfonamide or N-(prop-2-yn-1-ylidene)trifluoromethanesulfonamide.     

Viscosities and Surface Tensions of Phenetole with <Emphasis Type="Italic">N</Emphasis>-Methyl-2-pyrrolidone, <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-Dimethylformamide and Tetrahydrofuran Binary Systems at Three Temperatures

Viscosities, η, and surface tensions, σ, of binary systems of phenetole (ethoxy benzene or ethyl phenyl ether) with N-methyl-2-pyrrolidone, N,N-dimethylformamide or with tetrahydrofuran were measured over the entire mole fraction range and at (298, 303 and 308) K. The experimental data was used to compute the deviations in viscosity, Δη, and surface tension, Δσ. Values of the excess Gibbs energy of activation G*^E, surface entropy S _σ and surface enthalpy H _σ were calculated. Viscosity data of the binary systems were calculated using the Grunberg and Nissan and the three-body and four-body McAllister correlations. The Redlich–Kister method was used for evaluation of coefficients and standard deviations for Δη, Δσ and G*^E. The results were interpreted in terms of the probable effect of molecular interactions between components as well as polarity.     

Reactions of <Emphasis Type="Italic">N</Emphasis>-(Polychloroethylidene)arene-and - trifluoromethanesulfonamides with indoles

N-(Polychloroethylidene)arene-and -trifluoromethanesulfonamides reacted with indole and N-substituted indoles to give the corresponding N-[2,2-dichloro(or 2,2,2-trichloro)-1-(1H-indol-3-yl)ethyl]-substituted sulfonamides. Unlike N-(2,2,2-trichloroethylidene)trifluoromethanesulfonamide, less electrophilic N-(poly-chloroethylidene)arenesulfonamides failed to react with 1-(4-nitrophenyl)-1H-indole. Previously unknown N,N’-bis(2,2-dichloroethylidene)biphenyl-4,4’-disulfonamide reacted with 1-benzyl-1H-indole at both azomethine fragments. Likewise, reactions of 1,6-bis(1H-indol-1-yl)hexane and 1,4-bis(1H-indol-1-ylmethyl)-benzene with N-sulfonyl trichloroacetaldehyde imines involved both indole rings in the former.     

Synthesis of N-aryl- and <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diethyl-9-methyl-11-sulfanylidene-8-oxa-10,12-diazatricyclo[7.3.1.0<Superscript>2,7</Superscript>]trideca-2,4,6-triene-13-carboxamides

Three-component condensation of N-aryl- and N,N-diethyl-3-oxobutanamides with salicylaldehyde and thiourea in ethanol in the presence of sodium hydrogen sulfate afforded N-aryl- and N,N-diethyl-9-methyl-11-sulfanylidene-8-oxa-10,12-diazatricyclo[7.3.1.0^2,7]trideca-2,4,6-triene-13-carboxamides. Reaction of the same compounds in the absence of a catalyst under solvent-free conditions gave N-aryl-6-(2-hydroxyphenyl)-4-methyl-2-sulfanylidene-1,2,3,6-tetrahydropyrimidine-5-carboxamides.     

Chemosensors based on <Emphasis Type="Italic">N</Emphasis>-(2-aminophenyl)-<Emphasis Type="Italic">N</Emphasis>-(9-anthrylmethyl)amine: II

A series of N-(9-anthrylmethyl)arylimines was prepared by condensation of N-(2-aminophenyl)-N-(9-anthrylmethyl)amine with aromatic aldehydes. The study of the luminescent and complexing properties of compounds obtained showed that 2-{[2-(9-anthrylmethylamino)phenylimino]methyl}-1-naphthol and 1-{[2-(9- anthrylmethylamino)phenylimino]methyl}-6-bromo-2-naphthol were efficient highly selective chemosensors of cations Hg²⁺.     

Properties and <Emphasis Type="Italic">N</Emphasis>-glycosylation of recombinant endoglucanase II from <Emphasis Type="Italic">Penicillium verruculosum</Emphasis>

Cellulases are the main components of enzyme complexes used in biotransformation processes of plant raw materials into valuable commercial products. Endoglucanase II (EG II) from the Penicillium verruculosum fungus was cloned into Penicillium canescens. The homogeneous recombinant EGII form is isolated and its properties are studied in comparison with the native enzyme. The N-glycosylation sites and the structure of the N-linked glycans are been determined using mass spectrometry. The biochemical and catalytic properties, as well as the N-glycosylation type of the obtained recombinant EGII form, appear to be close to the native enzyme. At the two potential N-glycosylation sites (N42 and N194) of both forms of the enzyme, N-linked high mannose glycans (or their enzymatic “trimming” products) according to the general formula (Man)_1–9(GlcNAc)₂ are detected. No glycosylation is found at the third potential site (N19).     

Copolymer of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-diallyl-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimethylammonium chloride with maleic acid as drug carrier

A copolymer of N,N-diallyl-N,N-dimethylammonium chloride with maleic acid of constant composition was prepared under the conditions of radical initiation. The possibility of the functionalization of the copolymer with drugs containing amino groups by polymer-analogous transformations was examined. Conditions were found for preparing conjugates of the copolymer with isoniazid. The structures and the quantitative compositions of the conjugates were determined by ¹³С NMR spectroscopy, and the possibility of preparing conjugates with controlled drug content was demonstrated.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-aryl-2-methyl-4-oxo-3,4,5,6-tetrahydro-2<Emphasis Type="Italic">H</Emphasis>-2,6-methano-1,3,5-benzoxadiazocine-11-carboxamides

N-Aryl-2-methyl-4-oxo-3,4,5,6-tetrahydro-2H-2,6-methano-1,3,5-benzoxadiazocine-11-carboxamides were synthesized by three-component reactions of N-aryl-3-oxobutanamides with salicylaldehyde and urea in ethanol in the presence of NaHSO₄ as catalyst. The product structure was determined by IR and ¹H NMR spectroscopy and X-ray analysis.     

Synthesis of <Emphasis Type="Italic">ortho</Emphasis>-carboranyl derivatives of (<Emphasis Type="Italic">S</Emphasis>)-asparagine and (<Emphasis Type="Italic">S</Emphasis>)-glutamine

(S)-Asparagine and (S)-glutamine ortho-carboranyl derivatives with free amino and carboxy groups in the α-position were synthesized. By an example of N ^γ-(1,2-dicarba-closo-dodecarboran-3-yl)-(S)-glutamine it was demonstrated that the developed synthetic approach carboranyl derivatives of amino acids allowed the preparation of optically pure isomers.     

Synthesis and membrane-protective activity of 2,6-diisobornylphenol derivatives with <Emphasis Type="Italic">N</Emphasis>- and <Emphasis Type="Italic">O</Emphasis>-containing fragments at position 4

Two series of new amide derivatives containing 2,6-diisobornylphenol moiety were synthesized based on 3,5-diisobornyl-4-hydroxybenzoic acid and 4-butylaminomethyl-2,6-diisobornylphenol. Toxicity, membrane-protective (MP) and antioxidant (AO) activity of the obtained compounds were evaluated using red blood cells of laboratory mice as the test object. The tests demonstrated the absence of hemolytic activity for all the synthesized derivatives and the presence of high MP and AO activity under conditions of acute H₂O₂-induced oxidative stress for (3,5-diisobornyl-4-hydroxyphenyl)(morpholino)methanone and N-n-butyl-N-(3,5-diisobornyl-4-hydroxybenzyl)acetamide. A comparison of the data of the newly obtained compounds and those of described earlier 2,6-diisobornylphenol derivatives with N- and O-containing fragments at position 4 (alkoxymethyl, carboxy, and aminomethyl derivatives) led to a conclusion that the most promising for further studies of pharmacological activity are compounds containing methoxycarbonyl, methoxymethyl, ethoxymethyl, morpholinomethyl, di-n-butylaminomethyl, (azepan-1-yl)methyl, or N-acetyl-N-alkylaminomethyl function, which provide low toxicity and high MP and AO activity.     

Synthesis of cyclic sulfonamides by reaction of <Emphasis Type="Italic">N</Emphasis>-sulfinyl-3-(trifluoromethyl)aniline with norbornenes

N-Sulfinyl-3-(trifluoromethyl)aniline reacted with bicyclo[2.2.1]hept-2-ene and bicyclo[2.2.1]-hepta-2,5-diene to give the corresponding Diels?Alder adducts which were oxidized to 8-trifluoromethyl-2,3,4,4a,6,10b-hexahydro-5λ⁶-1,4-methanodibenzo[c,e][1,2]thiazine-5,5(1H)-diones. The cycloaddition occurred predominantly with participation of the S=N–C¹=C⁶ fragment of N-sulfinyl-3-(trifluoromethyl)aniline and exclusively at the endo side of bicyclo[2.2.1]heptenes.     

Synthesis and reduction of <Emphasis Type="Italic">N</Emphasis>-substituted 5-nitrosoquinolin-8-amines

N-Substituted 5-nitrosoquinolin-8-amines were synthesized for the first time by amination of 5-nitrosoquinolin-8-ol with primary aliphatic amines. The amination of 5-nitrosoquinolin-8-ol with hexamethylenediamine afforded N¹,N⁶-bis(5-nitrosoquinolin-8-yl)hexane-1,6-diamine. The resulting nitrosoquinolinamines were reduced with hydrazine hydrate over Pd/C to N⁸-alkylquinoline-5,8-diamines and N¹,N⁶-bis-(5-aminoquinolin-8-yl)hexane-1,6-diamine.