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.     

Kinetics of the Decomposition of α-Phenylethyl Hydroperoxide in the Presence of <Emphasis Type="Italic">N,N,N′,N′</Emphasis>-Tetramethyl-<Emphasis Type="Italic">para</Emphasis>-Phenylenediamine

It is found that the tertiary amine N,N,N′,N′-tetramethyl-para-phenylenediamine (TMPD) causes the decomposition of α-phenylethyl hydroperoxide (ROOH), and the interaction between the components occurs in accordance with a complicated rate law. It is demonstrated that more than 30 hydroperoxide molecules (n) can be degraded at a molecule of TMPD; this fact suggests that the amine has a catalytic effect on the process. The value of n increases with the [ROOH]₀/[TMPD]₀ ratio. The initial rates of consumption of ROOH and TMPD linearly increase with the initial concentrations of both of the reactants. The apparent rate constant of the reaction is k = 0.4 l mol^?1 s^?1 (393 K), as calculated from the initial rates of ROOH consumption. As a result of the interaction, TMPD is converted into an inhibitor. The rate constant of the reaction of this inhibitor with ethylbenzene peroxy radicals is about 2 × 10⁴ l mol^?1 s^?1.     

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.     

An efficient synthesis of <Emphasis Type="Italic">β</Emphasis>-methoxycarbonyl-<Emphasis Type="Italic">γ</Emphasis>-butyrolactones

β-Methoxycarbonyl-γ-butyrolactones bearing a γ-aromatic substituent were prepared via copper-catalyzed reductive aldol addition/lactonization domino reactions of ketones with α,β-unsaturated dicarboxylate esters and a silane under ambient temperature. The reaction has advantage of using readily available reagents, mild conditions and high efficiency.     

<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.     

Reaction of 1-hetaryl-4-phenylthiosemicarbazides with <Emphasis Type="Italic">N,N′</Emphasis>-dicyclohexylcarbodiimide

1,2,4-Triazolo[3,4-b][1,3]benzothiazole, 1,2,4-triazolo[4,3-a]pyrimidine, and thieno[3,2-e][1,2,4]-triazolo[4,3-a]pyrimidine derivatives were synthesized by reactions of 1-hetaryl-4-phenylthiosemicarbazides with N,N′-dicyclohexylcarbodiimide.     

Nenitzescu synthesis of carbamate indole derivatives from <Emphasis Type="Italic">N,N′</Emphasis>-bis(methoxycarbonyl)-<Emphasis Type="Italic">p</Emphasis>-benzoquinone diimine

N,N′-Bis(methoxycarbonyl)-p-benzoquinone diimine reacted with 4-(cyclohex-1-en-1-yl)-and 4-(cyclopent-1-en-1-yl)morpholines in methylene chloride at room temperature to give morpholino-substituted cyclohexane-and cyclopentane-fused indole derivatives. Heating of the latter in boiling 10% hydrochloric acid led to the formation of methyl 6-(methoxycarbonylamino)-1,2,3,4,4a,9a-hexahydro-9H-carbazole-9-carboxylate and methyl 7-(methoxycarbonylamino)-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indole-4-carboxylate, respectively. The reaction of N,N′-bis(methoxycarbonyl)-p-benzoquinone diimine with 4-benzylaminopent-3-en-2-one in CH₂Cl₂ in the presence of BF₃·Et₂O on heating gave methyl 3-acetyl-2-methyl-(5-methoxy-carbonylamino)-1H-indole-1-carboxylate.     

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.     

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.     

Thermophysical properties of <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>-dimеthylacetamide mixtures with <Emphasis Type="Italic">n</Emphasis>-butanol

The refraction, dielectric, viscosity, density, data of the binary mixtures of N,N-dimethylacetamide (DMA) with n-butanol at 308.15 and 313.15 K. The measured parameters used to obtain derived properties like Bruggeman factor, molar refraction and excess static dielectric constant, excess inverse relaxation time, excess molar volume and excess viscosity, excess molar refraction. The variation in magnitude with composition and temperature of these quantities has been used to discuss the type, strength and nature of binary interactions. Results confirm that there are strong hydrogen-bond interactions between unlike molecules of DMA+ n-butanol mixtures and that 1: 1 complexes are formed and strength of intermolecular interaction increases with temperature.     

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.     

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.     

Copper(II) complexation and extraction with 2-ethylhexanoic acid <Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dialkylhydrazides

2-Ethylhexanoic acid N′,N′-dibutylhydrazide (DBH) and N′,N′-diheptylhydrazide (DHH) were synthesized. The existence regions of copper (II), zinc(II), nickel(II), and cobalt(II) complexes formed upon extraction with DBH in kerosene were studied. The neutral complex ML₂ extracted over a wide pH range (from pH ～ 6 to \(c_{NH_3 } \) ～ 4 mol/L) is formed only by copper(II), while zinc(II), nickel(II), and cobalt(II) react with DBH to yield precipitates that float at pH 7–9, 9–10.5, and 9.5–11, respectively. On the basis of IR spectra, elemental analysis, and properties, a structure was suggested for the CuL₂ complex with DBH. The DBH and DHH complexes with copper(II) are readily stripped with H₂SO₄ and H₂SO₄ + CuSO₄ solutions. The capacity of a 1.5 mol/L DHH in kerosene with respect to copper(II) is 26 g/L.     

Extraction-photometric determination of <Emphasis Type="Italic">N</Emphasis>′,<Emphasis Type="Italic">N</Emphasis>′-dialkylbenzhydrazides as its complexes with copper

A procedure for extraction-photometric determination of N′,N′-dialkylbenzhydrazides has been proposed; the procedure is based on the formation of its colored complex with copper (II) followed by extraction with p-xylene and absorbance measurements at 460 nm (0.1–0.4 mmol of analyte in the sample) or at 330 nm (0.005–0.025 mmol of analyte in the sample).     

Complex formation of magnesium and calcium ions with trimethylenediamine-<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>’,<Emphasis Type="Italic">N</Emphasis>’-tetraacetic acid

Stability constants and heat effects of the formation reactions of magnesium and calcium trimethylenediaminetetraacetates at 298.15 K and ionic strength of 0.1, 0.5, and 1.0 (mol/L KNO₃) have been determined by means of potentiometry and calorimetry. Standard thermodynamic parameters (log K⁰, Δ_rG⁰, Δ_rH⁰, and Δ_rS⁰) of the studied equilibriums have been determined.     

Synthesis of <Emphasis Type="Italic">α</Emphasis>-chloropyridine derivatives of <Emphasis Type="Italic">γ</Emphasis>-aminobutyric acid

The sodium salt of N-(6-chloronicotinoyl)-γ-aminobutyric acid, a structural analog of the known nootropic and vasidilating drug picamilon, was synthesized via Schotten–Baumann acylation of γ-aminobutyric acid with 6-chloronicotinoyl chloride and subsequent neutralization of the N-(6-chloronicotinoyl)-γ-aminobutyric acid that was obtained in >60% yield.     

<Emphasis Type="Italic">β</Emphasis>-Chloro-<Emphasis Type="Italic">α</Emphasis>,<Emphasis Type="Italic">β</Emphasis>-unsaturated carbonyls as convenient precursors of highly substituted benzenes

The Diels–Alder reactions of three β-chloro-α,β-unsaturated carbonyl compounds 1–3 with different dienes were carried out to afford highly functionalized cyclohexenes 4–9, bearing quaternary centers, in good yields. These cycloadducts (CAs) undergo dehydrochlorination with subsequent aromatization in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene DBU to produce new substituted benzenes 11–14. Compound 10 is the product of lactonization and removal of an HCl molecule from compound 7. All products were characterized by NMR, IR, elementary analysis and some of them by MS. Structure assignments of isomers were carried out on the basis of NMR chemical shifts and coupling constants using 1D, 2D and heteronOe NMR techniques.