Synthesis of hydrogels from a polymeric N,N′-diallyl-N,N′-dimethylammonium salt

Feasibility in principle has been demonstrated for obtaining hydrogels with controlled parameters of the three-dimensional network by copolymerization of N,N-methylenebisacrylamine with macromolecules of poly-N,N-diallyl-N,N-dimethylammonium chloride containing terminal double bonds, i.e., with macromonomers of N,N-diallyl-N,N-dimethylammonium chloride. The hydrogels that are obtained have high anion-exchange capacities.A. V. Topchiev Institute of Petrochemical Synthesis, Academy of Sciences of the USSR, Moscow 117912. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 4, pp. 851–854, April, 1992.     

Synthesis of N′-phosphinatodiazene N-oxides

We have developed a regiospecific method for synthesis of N-phosphinatodiazene N-oxides, a previously unknown type of azoxy compounds in which the diazene oxide fragment is directly connected with the phosphinate group. The method involves reaction of amidoesters of alkyl- and arylphosphonic acids with nitroso compounds in the presence of dibromoisocyanurate.N. D. Zelinskii Institute of Organic Chemistry, Russian Academy of Sciences, 117913 Moscow. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 11, pp. 2648–2656, November, 1992.     

Organocatalytic Enantioselective Synthesis of Axially Chiral N,N′-Bisindoles

This study establishes the first organocatalytic enantioselective synthesis of axially chiral N,N′-bisindoles via chiral phosphoric acid-catalyzed formal (3+2) cycloadditions of indole-based enaminones as novel platform molecules with 2,3-diketoesters, where de novo indole-ring formation is involved. Using this new strategy, various axially chiral N,N′-bisindoles were synthesized in good yields and with excellent enantioselectivities (up to 87 % yield and 96 % ee). More importantly, this class of axially chiral N,N′-bisindoles exhibited some degree of cytotoxicity toward cancer cells and was derived into axially chiral phosphine ligands with high catalytic activity. This study provides a new strategy for enantioselective synthesis of axially chiral N,N′-bisindoles using asymmetric organocatalysis and is the first to realize the applications of such scaffolds in medicinal chemistry and asymmetric catalysis.     

Synthesis and study of N,N′-disubstituted derivatives of pyromellitic diimide

Russian Chemical Bulletin - New N, N′-bis(4,6-dimethylpyrimidin-2-yl)- and N, N′-bis(2,3,5,6-tetrafluorophenyl)-substituted pyromellitic diimides were synthesized. Their properties were...     

Efficient Synthesis of N,N′‐Disubstituted Ureas/Thioureas Catalyzed by Iodine

Iodine is an efficient catalyst for the synthesis of symmetrically N,N′‐disubstituted ureas/thioureas by heating respective amines or phenyl hydrazine and urea/thiourea on a preheated hot plate at 90–95°C, under solvent‐free conditions. The yields are excellent, and the reactions go to complete within 5–10 min.     

Olefin Synthesis via,the Li-Derivative of N,N,N′,N′-Tetramethyldimides of Arylmethanephosphonic Acids

Abstract

The high erythro-stereoselective reaction of Li-tetramethyldiamides of arylmethanephosphonic acids with carbonyl compounds is used for synthesis of (Z)-alkenes by thermolysis of the erythro-adducts as well as in acidic media.     

Synthesis of chiral N,N′-disubstituted 1,2-benzenediamines from o-dibromobenzene

Palladium-catalyzed amination of o-dibromobenzene provided chiral N,N′-disubstituted 1,2-benzenediamines in good to excellent yields. The amination was executed stepwise and in one pot to give unsymmetrically and symmetrically substituted 1,2-benzenediamines. Incorporation of chiral primary amines was possible without racemization using catalytic Pd₂dba₃–BINAP.     

Synthesis and Crystal Structure of Complexes of Lanthanide Picrates With N,N ′-Dimethyl-N,N ′-Diphenyl-1,2-PhenylenediOxydiacetamide

Lanthanide picrate complexes with the ligand N,N'-dimethyl-N,N'-diphenyl-1,2-phenylenedioxydiacetamide (L) [Ln(Pic)₃L] (Ln=La,Gd,Er,Y) have been prepared in nonaqueous medium and characterized by elemental analysis, IR and ¹H spectra. The Gd(III) complex [Gd(Pic)₃L]·3CH₃CN is triclinic, space group P&1macr;, with a=14.292(1), b=14.967(2), c=16.571(2)Å, α=97.855(9), γ=113.070(9)°, ν=28706(6)ų, D _c=1.584g/cm³ for Z=2. The structure was refined to R=0.0318 based on 8409 observed reflections.     

A Convenient Synthesis of Unsymmetrical N,N′-Disubstitutedα,ω-Diaminoalkanes

A general procedure is described for regiospecific construction of unsymmetrical N-alkyl (or aralkyl)-N′-aryl-α,ω-diaminoalkanes 3 (n=2,3,4) by reduction of N-(ω -arylaminoalkyl)amides 2 with borane. Compounds 2 are readily obtained by condensation of N-(ω-haloalkyl)amides 1 with aromatic amines.     

Synthesis and Crystal Structure of 4,4′-Diamino-N,N′-diethyl Bisbenzenesulfamide

A new compound of 4,4′-diamino-N,N′-diethyl bisbenzenesulfamide (C18H26N4O4S2, Fw = 426.55) has been synthesized and its structure was determined by X-ray crystallography method. The crystal belongs to the monoclinic system, space group P21/c with a = 10.0623(9), b = 13.6759(13), c =15.5309(14) , β = 100.482(2)o, V = 2101.6(3) 3, Dc = 1.348 g/cm3, F(000) = 904, μ = 0.285 mm–1, Z = 4, the final R = 0.0512 and wR = 0.1363 for 3485 observed reflections with I > 2σ(I). The structure of the title compound is pseudo secondary axisymmetric, and the two sulfamide-groups show distorted tetrahedral configurations.     

Microwave‐Assisted Synthesis of N,N′‐Disubstituted Acetamidine Ligands

Under microwave activation, triethylorthoacetate reacts with the substituted anilines in the presence of acetic acid as a catalyst, producing acetamidine in moderate to high yields. The X‐ray structures of the new amidines, N,N′‐bis(3,5‐dimethylphenyl)‐acetamidine and N,N′‐bis(p‐tolyl)acetamidine, are also reported, revealing polymeric chains supported by intramolecular H‐bonds.     

Synthesis of N,N′-di(tert-butyl)bispidin-9-ones

Condensation of 1,3,5-tri(tert-butyl)-1,3,5-triazacyclohexane with acetone gave 3,7-di(tert-butyl)-1,5-bis[(tert-butylamino)methyl]bispidin-9-one. Reactions with ethyl methyl ketone and other ketones of the formula RCH₂COCH₃ yielded 5-R-3,7-di(tert-butyl)-1-[(tert-butylamino)methyl]bispidin-9-ones, while reactions with diethyl ketone and other symmetrical ketones of the formula RCH₂COCH₂R afforded 1,5-R-3,7-di(tert-butyl)bispidin-9-ones.     

Vibrational spectra of N,N-dimethyl/diethylaniline,N,N,N′,N′-tetramethyl/tetraethyl-p-phenylenediamine and N,N,N′,N′-tetramethyl/tetraethylbenzidine derivatives

The ground state and protonated state (quaternized salt) vibrational spectra (200–1800 cm⁻¹) of the title amines are reported for various ring and/or methyl deuterated derivatives. Complete assignments are proposed and compared to those established for the parent hydrocarbons, benzene and biphenyl, and for the parent primary amines, aniline, p-phenylenediamine and benzidine. The electronic distribution, N(n)→ring(π) charge-transfer character and inductive effects are characterized from a vibrational point of view. Finally changes in the vibrational and electronic conformation upon protonation of the nitrogen atom are discussed. These results provide a fundamental basis for the vibrational investigation of excited states and reactive transients of aromatic amines.     

Synthesis and Crystal Structure of N,N′-4-aminomethyl-pyromellitic diimide

The title compound N,N′-4-aminomethyl-pyromellitic diimide (4-pmpmd) crystallizes in monoclinic, space group P21/c with a = 4.785(1), b = 6.200(1), c = 29.907(2) (A), β =93.583(11)°, V= 885.5(2) (A)3, Dc = 1.494 g/cm3, Z = 2, C22H14N4O4, Mr = 398.37,μ(MoKα) = 0.106mm-1 and F(000) = 412, and its structure was refined to R = 0.0469 and wR = 0.1017 for 1194observed reflections (Fo ＞ 4σ(Fo)). The X-ray diffraction shows the existence of the staggered multi-dimensional supramolecular network based on the Z-mode conformation of the title compound.     

Synthesis and Crystal Structure of N,N′-4-aminomethyl-pyromellitic diimide

1 INTRODUCTION N,N?-4-aminomethyl-pyromellitic diimide (4-pmpmdwas firstly obtained[1] in 1989 as one of the bypro-ducts by refluxing equimolar quantities of pyrome-llitic anhydride, n-hexylamine and 4-aminomethyl py-ridine in dry DMF to assemble electronic donor-spa-cer-acceptor systems, but its structure and coordina-tion chemistry did not receive attention at that time.For 4-pmpmd, the entity of two methylene groups(-CH2-) between the rigid pyromellitic diimide (PMDcore and two fre…     

Synthesis of guanidines via the I2 mediated desulfurization of N,N′-di-Boc-thiourea

The I₂ mediated desulfurization of N,N′-di-Boc-thiourea was developed. Various primary amines, including sterically and electronically deactivated primary amines, were transformed into the corresponding bis-Boc protected guanidines under mild conditions.     

A Facile Synthesis of N′-Benzoyl Thiophosphoryluras

Twelve title compounds 3a-l were synthesized by nuclophilic addition of thiophosphoramide 1 to benzoylisocyanate 2. The yield of compounds 3a-f and 3g-l is 72–83% and 18–33%.