Directed Aminomethylation of Pyrrole,Indole, and Carbazole with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N′</Emphasis>,<Emphasis Type="Italic">N′</Emphasis>-Tetramethylmethanediamine

Catalytic aminomethylation of pyrrole and indole with N,N,N′,N′-tetramethylmethanediamine in the presence of 5 mol % of ZrOCl₂·8H₂O proceeds selectively at the positions 2, 5 of pyrrole and 1, 3 of indole. Carbazole under the same conditions affords 3-formyl-9-aminomethyl derivative. The reaction in the presence of 5 mol % of K₂CO₃ occurs as monoaminomethylation: for pyrrole at the position 2, for indole at the position 3, and for carbazole at the nitrogen atom of the substrate. Water-soluble 1,1′-(1H-pyrrole-2,5-diyl)bis(N,N-dimethylmethanamine) exhibits a fungistatic activity with respect to phytopathogenic fungi Rhizoctonia solani.     

Transformations of the extra ring in pheophorbide <Emphasis Type="Italic">a</Emphasis> methyl ester in the reaction with <Emphasis Type="Italic">N,N,N′,N′</Emphasis>-tetramethylmethanediamine

The reaction of N,N,N′,N′-tetramethylmethanediamine with pheophorbide a methyl ester gave the corresponding 13″-dimethylaminomethyl derivative and 13-N,N-dimethylamide derivative of chlorin e ₆ having a methyl acrylate moiety in the 15-position. Conditions were found for the synthesis of the latter both directly from pheophorbide a methyl ester and from its aminomethylation product. Probable mechanisms of the examined reactions were proposed.     

Complexation and extraction properties of <Emphasis Type="Italic">N′,N′</Emphasis>-dibutyloctanohydrazide

A new extractant for copper(ii) extraction, viz., N′,N′-dibutyloctanohydrazide, was synthesized. Its acid-base, extraction, and complexation properties were studied. The introduction of two butyl substituents into the hydrazide group weakens the acidic properties of the compound synthesized compared to the unsubstituted hydrazide, shifts the region of efficient copper(ii) extraction from an acidic medium to weakly acidic and ammonia media, and forms an uncharged extractive copper complex. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 380–384, February, 2008.     

<Emphasis Type="Italic">N′, N′</Emphasis>-dialkylhydrazides as inhibitors of acid corrosion of steel

The effect of N′,N′-dialkylhydrazides of aliphatic carboxylic acids of the general formula C₄H₉CH(C₂H₅)C(O)NHN(R)₂ on the corrosion behavior of St.20 steel in 0.1 and 1 M HCl was studied by electrochemical and gravimetric methods.     

X-ray and computational structural study of neutral <Emphasis Type="Italic">bis</Emphasis>(<Emphasis Type="Italic">N,N,N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-tetramethylthiophosphoramidoyl)-methylamine

The structure of bis(N,N,N′,N′-tetramethylthiophosphoramidoyl)-methylamine 1 has been determined by single-crystal X-ray diffraction. The compound 1 crystallizes in the monoclinic system, with a space group P2₁/c, a = 11.836(2) Å, b = 11.659(2) Å, c = 12.796(5) Å and β = 95.28(3)°, V = 1758.3(5) Å³ and Z = 4. The X-ray crystallographic data have been assessed by semi-empirical and ab-initio density functional theory and by Hartree–Fock molecular orbital methods. A comparative study of the results of the different methods is given.     

10<Emphasis Type="Italic">α</Emphasis>-Hydroxy-<Emphasis Type="Italic">β</Emphasis>-isomorphine,a by-product of the synthesis of 10<Emphasis Type="Italic">α</Emphasis>-hydroxymorphine

Abstract  A new compound was isolated from the reaction mixture after O-demethylation of 6-O-acetyl-10α-acetoxycodeine with boron tribromide. The structure of this compound, 10α-hydroxy-β-isomorphine, was elucidated by spectral data, and its spatial arrangement was deduced from an NOE experiment. Capillary zone electrophoresis was used for separation of morphine and its 10-hydroxy analogues. Graphical abstract        

Cyclization of the substituted <Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">Ortho</Emphasis>-cyclopropylphenyl)-<Emphasis Type="Italic">N′</Emphasis>-aryl ureas and thioureas in the gas phase and solution

Electron ionization (EI), chemical ionization (CI), tandem mass spectrometry, high-resolution measurements, and labeling studies as well as quantum chemical calculations were used to understand the behavior of the molecular radical cations (EI) and protonated molecules (CI) of substituted N-(ortho-cyclopropylphenyl)-N'-aryl ureas and N-(ortho-cyclopropylphenyl)-N'-aryl thioureas in a mass spectrometer. Fragmentation schemes and possible mechanisms of primary isomerization were proposed. According to the fragmentation pattern, formation of the corresponding benzoxazines and benzothiazines was considered as the major process of isomerization of the original M(+.) and MH(+), although some portions of these ions definitely transformed into other structures. The treatment of N-(ortho-cyclopropylphenyl)-N'-phenyl urea and N-(ortho-cyclopropylphenyl)-N'-phenylthiourea in solution with strong acids formed predicted 4-ethyl-N-phenyl-4H-3,1-benzoxazin-2-amin and 4-ethyl-N-phenyl-4H-3,1-benzothiazin-2-amine as principal products.     

<Emphasis Type="Italic">N</Emphasis>′-tetrazolylmethoxyl derivatives of <Emphasis Type="Italic">N</Emphasis>-methyldiazene <Emphasis Type="Italic">N</Emphasis>-oxides

A preparation method was developed for previously unknown tetrazole derivatives containing in the 1, 2, and/or 5 positions of the tetrazole ring N-methyldiazene-N-oxide-N′-oxymethyl groups.     

Synthesis and structure of the cobalt(II) coordination compounds with <Emphasis Type="Italic">N,N</Emphasis>-dimethyl-<Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dimethylthiocarbamoylsulfenamide

The CoLX₂ complexes were obtained by the reaction of N,N-dimethyl-N′,N′-dimethylthio-carbamoylsulfenamide (L) with CoX₂ (X = Cl, Br, I, NCS). The complexes were investigated by elemental and X-ray analysis, IR, ¹H NMR, and electron spectroscopy, conductometry, magnetochemistry, thermogravimetry. It is found that these compounds are high-spin complexes of pseudotetraedral structure with bidentate coordination of L through the thione sulfur atom and sulfenamide nitrogen atom.     

Study of<Emphasis Type="Italic"> β</Emphasis>–<Emphasis Type="Italic">α</Emphasis> recrystallization of the polypropylene

The crystalline modifications and of polypropylene (PP) were studied by using polarized light microscopy (PLM), wide-angle X-ray diffraction (WAXD), and differential scanning calorimetry (DSC). Typically crystals surrounded by spherulites were observed at low temperature. With increasing temperature the crystals melted and a new crystal appeared. More interestingly, the melting temperature of the new crystal was about 5 ° higher than that of spherulites originally present in the sample formed isothermally. It was assumed that this new crystal was the recrystalline crystal. This assumption was supported by the DSC results. Furthermore, the crystallization kinetics of the PP used was studied on the basis of the traditional Avrami analysis. As a result, the Avrami exponents of crystallization temperature from 120 to 130 °C ranged between 4.21 and 3.60, indicating that the crystallization mechanism of PP order melt was spherulitic growth and random nucleation.     

<Emphasis Type="Italic">N,N,N′,N′</Emphasis>-tetramethylmethanediamine—A new reagent for aminomethylation of acetylenes

A new procedure has been developed for aminomethylation of terminal acetylenes with N,N,N′,N′-tetramethylmethanediamine in the presence of transition metals and lanthanide complexes and salts. The procedure ensures formation of the corresponding N,N-dimethylprop-2-yn-1-amines with high yield and selectivity.     

Thermodynamic characteristics of protolytic equilibria of trimethylenediamine-<Emphasis Type="Italic">N,N,N′,N′</Emphasis>-tetraacetic acid

The thermal effects of the neutralization of betainic protons of trimethylenediamine-N,N,N′,N′-tetraacetic acid (H₄L) at 298.15 K and ionic strength of 0.3, 0.5, and 1.0 (KNO₃) were directly measured by calorimetry. The standard thermodynamic characteristics of the protolytic equilibria of H₄L were calculated from a combination of thermochemical and potentiometric data obtained under identical experimental conditions. The results obtained were compared with the corresponding data for related compounds taking into account the specific structure of diamine complexones.     

<Emphasis Type="Italic">N′,N′</Emphasis>-dialkylhydrazides and their protonated forms: <Emphasis Type="Italic">ab initio</Emphasis> calculations and studies by physical methods

RHF/6-31G(d) and MP2/6-31G(d) quantum-chemical calculations of N′,N′-dimethylethanohydrazide molecule and also MP2/6-31G(d) calculations of its protonated forms were performed. With the use of IR and ¹H NMR spectroscopy the series of N′,N′-dialkylhydrazides and their salts with HCl and H₂SO₄ were studied. The position of proton addition was determined. The experimental results were compared with the calculated findings.     

Influence of the force interaction on accumulation of macroscopic correlations in elementary reaction <Emphasis Type="Italic">A</Emphasis> + <Emphasis Type="Italic">B</Emphasis> → <Emphasis Type="Italic">C</Emphasis>

The applicability of the Encounter Theory (ET) (the prototype of the Collision Theory) concepts for widely occurring diffusion assisted irreversible bulk reaction A + B →C (for example, radical reaction) in dilute solutions taking account of initial microscopic correlations and force interactions between reactants has been treated theoretically with modern many-particle method for the derivation of non-Markovian binary kinetic equations. The method shows that taking into consideration initial correlations and force interactions leads to the redefinition of the Markovian rate constant only in the expressions derived earlier. Thus, just as in the reaction A + A →C and the reaction A + B →C neglecting force and initial correlations, the Modified Encounter Theory (MET), when reduced to equations of a Regular Form, both extends the time applicability range of ET homogeneous rate equation, and yields the inhomogeneous equation of the Generalized Encounter Theory (GET). It reveals macroscopic correlations induced by the encounters in the reservoir of free walks in full agreement with physical considerations. Time accumulation of macroscopic correlations obeys the same time law as in the previously considered case neglecting force interactions. Just the rate of the process will change, according to traditional redefinition of the steady-state constant of the reaction.     

Copper(II) complexing with <Emphasis Type="Italic">N′,N′</Emphasis>-diethylbenzohydrazide

Copper(II) complexing with N′,N′-diethylbenzohydrazide (DEBH) in aqueous isopropanol was studied. The formation of cationic complexes with the ratio [Cu²⁺]: [DEBH] = 1: 1 and 1: 2 in week acid solution and an uncharged complex with the ratio [Cu²⁺]: [DEBH] = 1: 2 in neutral and alkaline solutions was established. Their stability constants K _st were determined. The complexes were isolated in a solid state and characterized by IR spectroscopy and elemental analysis for copper.     

1,3-Diamino-2-Hydroxypropane-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-Tetraacetic Acid: Crystal and Molecular Structures

The synthesis, IR spectroscopic study, and X-ray diffraction analysis (CIF file CCDC no. 1574078) are carried out for 1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetraacetic acid (I). The structural units of a crystal of compound I are (H_4.5HPdta)^0.5– anions, (H_5.5HPdta)^0.5+ cations, and molecules of water of crystallization joined by a branched network of hydrogen bonds: strong intermolecular O–H…O and intramolecular N–H…O bonds.     

Phase Diagrams of the <Emphasis Type="Italic">n</Emphasis>-Decane–<Emphasis Type="Italic">n</Emphasis>-Hexadecane–Cyclododecane, <Emphasis Type="Italic">n</Emphasis>-Decane–Cyclododecane,and <Emphasis Type="Italic">n</Emphasis>-Hexadecane–Cyclododecane Systems

The n-decane–n-hexadecane–cyclododecane, n-decane–cyclododecane, and n-hexadecane–cyclododecane systems are studied by means of low-temperature differential thermal analysis using a differential scanning heat flow calorimeter. It is noted that all studied systems belong to the eutectic type. It is concluded that in the n-decane–n-hexadecane–cyclododecane system, the eutectic composition contains 85.0 wt % n-С₁₀Н₂₂, 4.0 wt % n-С₁₆Н₃₄, and 11.0 wt % С₁₂Н₂₄. It has a melting point of ?35.0°C.     

Microstructure of Polymers Prepared in the Presence of Tri-<Emphasis Type="Italic">n</Emphasis>-butylboron–<Emphasis Type="Italic">p</Emphasis>-Quinone System

The microstructure of polystyrene, poly(methyl acrylate), and poly(tert-butyl acrylate) obtained in the presence of tri-n-butylboron in combination with naphthoquinone-1,4 and 2,3-dimethylbenzoquinone is studied. The stereoregularity of polymers formed under these conditions may be described in the framework of the first-order Markov chain model. The use of p-quinones in combination with tri-n-butylboron favors an increase in the content of isotactic triads in the polymers. The causes of the observed deviations are discussed.