Reaction of Long-Chain Vanillyl Esters with CH-Acids and 2-Naphthylamine

The previously unknown 4-(alkyl-11-oxo-7,8,9,10,11,12-hexahydrobenzo[a]acridin-12-yl)- and 4-(alkyl-1,8-dioxo-2,3,4,5,6,7,8,9-octahydro-1H-xanthen-9-yl)-2-methoxyphenyl esters of aliphatic (C₅-C₇, C₁₂) carboxylic acids were synthesized via cascade heterocyclization of cyclohexane-1,3-dione and dimedone with 2-naphthylamine and long-chain vanillyl esters.     

Reactions of <Emphasis Type="Italic">N</Emphasis>-and <Emphasis Type="Italic">C</Emphasis>-Alkenylanilines: VII. Synthesis of Indole Heterocycles from Products of Reaction between <Emphasis Type="Italic">N</Emphasis>-Mesyl-2-(1-alken-1-yl)anilines and Halogens

N-Mesyl-2-(1-methyl-1-butenyl)-6-methylaniline reacted with Br₂ to afford N-mesyl-2-(3-bromo-1-penten-2-yl)aniline that under treatment with NH₃ or amines underwent cyclization into N-mesyl-7-methyl-3-methylene-2-ethylindoline. The reaction of N-mesyl-2-(1-methyl-1-buten-1-yl)-4-methyl- and 2-(1-methyl-1-buten-1-yl)aniline with Br₂ gave rise to the corresponding N-mesyl-2-(2-bromo-1-methyl-1-buten-1-yl)anilines. Under the similar conditions N-tosyl-2-(1-cyclohexen-1-yl)aniline was converted into N-tosyl-2-(6-bromo-1-cyclohexen-1-yl)aniline that under treatment with NH₃ furnished N-tosyl-1,2,3,9a-tetrahydrocarbazole. The reaction of N-mesyl-1,2,3,9a-tetrahydrocarbazole with CuBr₂ in MeOH afforded N-mesyl-4-methoxy-1,2,3,4-tetrahydrocarbazole. N-Mesyl-6-methyl-2-(1-cyclopenten-1-yl)aniline in reaction with Br₂ in the presence of NaHCO₃ was oxidized into the corresponding cyclopentenone, and with NBS it gave N-mesyl-2-(2-bromo-1-cyclopenten-1-yl)aniline.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 730–737.Original Russian Text Copyright © 2005 by Gataullin, Sotnikov, Spirikhin, Abdrakhmanov.     

Palladium(II)-catalyzed Amination of Isoprene with Aniline

The reaction of isoprene with aniline, catalyzed by the Pd(acac)₂-(RO)₃P-CF₃CO₂H system, 1 : 4 : 4 [R = Me, Et; acac = (CH₃CO)₂CH], in MeCN provides N-(3-methylbut-2-en-1-yl)aniline with a high selectivity (up to 84%) and a nearly quantitative yield (75%). At 1 : 4 : 20 and 1 : 4 : 40 molar component ratios in the catalytic system, up to 28–31% of N,N-(2,3-dimethylprop-2-en-1-yl)aniline is formed. Telomeric reaction products appear at 1 : 2 : 4 and 1 : 1 : 10 ratios.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 963–968.Original Russian Text Copyright © 2005 by Petrushkina, Mysova, Orlinkov.     

Reaction of the Reformatskii reagent obtained from bromotetrahydrofuran-2-one with 2-oxochromene-3-carboxylic or 3-oxo-3<Emphasis Type="Italic">H</Emphasis>-benzo[<Emphasis Type="Italic">f</Emphasis>]chromene-2-carboxylic acid derivatives

The Reformatskii reagent obtained from 3-bromotetrahydrofuran-2-one reacts with alkyl esters of 6-bromo- and 6,8-dibromo-2-oxochromene-3-carboxylic acid or alkyl esters and N-benzylamide of 3-oxo-3H-benzo[f]chromene-2-carboxylic acid to form alkyl esters of 6-bromo- and 6,8-dibromo-2-oxo-4-(2-oxotetrahydrofuran-3-yl)chroman-3-carboxylic acid or alkyl esters and N-benzylamide of 2,3- dihydro-3-oxo-1-(2-oxotetrahdrofuran-3-yl)-1H-benzo[f]chromene-2-carboxylic acid as a mixture of two diastereomers.Translated from Zhurnal Obshchei Khimii, Vol. 74, No. 9, 2004, pp. 1513–1515.Original Russian Text Copyright © 2004 by Shchepin, Fotin, Shurov.This revised version was published online in April 2005 with a corrected cover date.     

Arylbiguanides in Heterocyclization Reactions

The reactions of arylbiguanides with acetyacetone derivatives were used to obtain N-(pyrimidin-2-yl)-N′-arylguanidines, and the reactions with acetoacetic ester derivatives (depending on the structure of the keto esters), N-aryl-N′-(4-oxo-3,4-dihydropyrimidin-2-yl)guanidines or 2-amino-4-arylamino-6-aryl(heteryl)-sulfanylmethylene-1,3,5-triazines. The N-aryl-N′-heterylguanidines formed by the reactions with anhydrides, acyl halides, and aryl isocyanates give rise to the corresponding triaza derivatives.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 2, 2005, pp. 331–339.Original Russian Text Copyright © 2005 by Kryl’skii, Shikhaliev, Shestakov, Liberman.     

Reaction of Malonic Acid Derivatives with Acetylenic Diphosphonates

The primary addition products in the reactions of malonic esters, cyanoacetic esters, and malononitrile with acetylenediphosphonates in acetonitrile in the presence of anhydrous potassium carbonate are potassium derivatives, viz. esters and nitriles of the corresponding 2-alkoxycarbonyl(or 2-cyano) -3,4-bis(di-alkoxyphosphinoyl)-2-potassiobut-3-enoic acid. Further hydrogen replacement for potassium in the nitriles is accompanied by isomerization involving double-bond shift and geometry change. (E)- and (Z)-3,4-bis(dial-koxyphosphinoyl)-2-cyano-2-potassiobut-3-enenitriles (the alkoxy groups are CH₃O and C₂H₅O) are crystalline compounds; they were isolated and characterized.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 1, 2005, pp. 11–20.Original Russian Text Copyright © 2005 by Shekhadeh, Didkovskii, Dogadina, Ionin.     

Dipolar Cycloaddition of Carbonyl Ylides Generated from Methyl cis-2-Diazoacetyl-1-cyclopropanecarboxylates

Carbonyl ylide generated from methyl cis-3-diazoacetyl-2,2-diphenyl-1-cyclopropanecarboxylate in the presence of Rh₂(OAc)₄ when brought into reaction of 1,3-dipolar cycloadditionя with N-arylmaleimides afforded substituted 4-aryl-7-methoxy-9,9-diphenyl-12-oxa-4-azatetracyclo-[5.4.1.0^2,6.0^8,10]dodecene-3,5,11-triones. Concurrent processes resulted in formation of cycloheptatrienes, hydroxyacetylcyclopropanecarboxylates, and benzophenone. Carbonyl ylide generated from methyl cis-2-diazoacetyl-1-cyclopropanecarboxylate in the same reaction gave rise to exo- and endo-4-aryl-7-methoxy-12-oxa-4-azatetracyclo[5.4.1.0^2,6 .0^8,10] dodecene-3,5,11-triones.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 2, 2005, pp. 205–213.Original Russian Text Copyright © 2005 by Molchanov, Diev, Kopf, Kostikov.     

Synthesis of 4-[(1<Emphasis Type="Italic">R</Emphasis>,4<Emphasis Type="Italic">R</Emphasis>)-3-Oxo-<Emphasis Type="Italic">p</Emphasis>-menthan-2-ylidenemethyl]benzoic Acid and Its Esters

Carbonylation of (E)-2-(4-halobenzylidene)-p-menthan-3-ones, catalyzed by PdCl₂(PPh₃)₂, gave a distereometric mixure of 4-[(1R,4R)- and (1R,4S)-3-oxo-p-menthan-2-ylidenemethyl]benzoic acids, whose reaction with phenols gave 1R,4R diastereomers of the corresponding esters.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 4, 2005, pp. 659–664.Original Russian Text Copyright © 2005 by Drushlyak, Kutulya, Pivnenko, Vashchenko.     

Synthesis and characterization of a new soluble conducting polymer and its electrochromic device

A mixture of isomers 2,5-di(4-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole, 2-(4-methyl-thiophen-2-yl)-5-(3-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole and 2,5-di(3-methyl-thiophen-2-yl)-1-(4-nitrophenyl)-1H-pyrrole (Me-SNS(NO₂)) were synthesized. Resulting monomers were polymerized chemically, producing soluble polymers in common organic solvents. The average molecular weight has been determined by gel permeation chromatography (GPC) as Mn=5.6×10³ for the chemically synthesized polymer. The monomers were also electrochemically polymerized in the presence of LiClO₄, NaClO₄ (1:1) as the supporting electrolyte in acetonitrile solvent. Resulting polymers were characterized via CV, FTIR, NMR, SEM and UV–Vis spectroscopy. Spectroelectrochemistry analysis of polymer revealed Π–Π^* transition below 300 nm, with an electronic band gap of 2.18 ev. Switching ability of the polymer was evaluated by kinetic study measuring percent transmittance (%T) at the maximum contrast point, indicating that poly(Me-SNS(NO₂)) is a suitable material for electrochromic devices.     

Reaction of 3-formyl-2-methoxy-1,6-dioxaspiro[4.4]nonanes with 3-amino-1,2,4-triazole: synthesis of 2-(1,2,4-triazolo[1,5-a]pyrimid-6-yl)methylenetetrahydrofurans

The reaction of 3-formyl-2-methoxy-1,6-dioxaspiro[4.4]nonanes with 3-amino-1,2,4-triazole gives 2-(1,2,4-triazolo[1,5-a]pyrimid-6-yl)methylenetetrahydrofurans in 51–65% yields.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2004–2005, November, 1993.     

Synthesis of elastomeric polypropylene in bulk using C 1-symmetric ansa-metallocenes. New aspects of the synthesis of 1-(fluoren-9-yl)-2-(2-methyl-5,6-dihydrocyclopenta [f]-1H-inden-1-yl)ethane and complexes of zirconium and hafnium with this ligand

Isomeric 1-(fluoren-9-yl)-2-(2-methyl-5, 6-dihydrocyclopenta [f]-1 H-indenyl) ethanes 1a,b and C ₁-symmetric metallocenes, viz., rac-1-(η⁵-fluoren-9-yl)-2-(2-methyl-5, 6-dihydrocyclopenta [f]-η⁵-inden-1-yl) ethanezirconium dichloride (9) and rac-1-(η⁵-fluoren-9-yl)- 2-(2-methyl-5, 6-dihydrocyclopenta [f]η⁵-inden-1-yl)ethanehafnium dichloride (10), with these ligands were synthesized by modified procedures. The structures of compounds 1b (two crystalline modifications) and 10 were established by X-ray diffraction analysis. The synthesis of polypropylene (PP) in bulk was studied in the presence of polymethylalumoxane-activated metallocenes 9 and 10 in the temperature range of 30–70°C. It was demonstrated that triisobutylaluminum can be used as a cocatalyst. In this case, the molecular weight of PP increases by a factor of ∼2. An increase in the reaction temperature leads to an increase in stereoregularity and crystallinity of PP. The polymer synthesized at high temperatures crystallizes in the γ form. The resulting PP is characterized by a wide range of properties from rigid crystalline thermoplastic to amorphous elastomeric. Samples, which have a high molecular weight and moderate isotacticity, exhibit high elastomeric and durability properties.__________Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 400–413, February, 2005.     

Crystallographic study and molecular modeling on the oxidation product of <Emphasis Type="Italic">N</Emphasis>-[(8<Emphasis Type="Italic">R</Emphasis>)-2-methoxy-5,6,7,8,9,10-hexahydro-6,9-methanocyclohepta[<Emphasis Type="Italic">b</Emphasis>]indol-8-yl]acetamide

Crystallization of N-[(8R)-2-methoxy-5,6,7,8,9,10-hexahydro-6,9-methanocyclohepta[b]indol-8-yl]acetamide was accompanied by oxidation at the C^5a–C^10a bond with formation of N-[(5S)-10-methoxy-2,8-dioxo-1,2,3,4,5,6,7,8-octahydro-3,6-methano-1-benzazecin-5-yl]acetamide whose structure was determined by X-ray analysis. Docking of this compound into melatonin-binding pocket of MT_1A receptor was simulated by computer-assisted molecular modeling.     

Pentacyclic triterpenes from <Emphasis Type="Italic">Sarcostemma clausum</Emphasis>

A homologous series of alkanoic acid (C₂–C₅) esters of germanicol was isolated from the methanolic extract of Sarcostemma clausum, of which germanicol-3-propionate and 3-pentanoate have not been previously described in the literature. In addition, taraxasterol, multiflorenol, and bauerenol were also isolated for the first time from the genus Sarcostemma. Structures were elucidated by chemical and spectroscopic methods (NMR, IR, SM) and by comparison with literature data.Published in Khimiya Prirodnykh Soedinenii, No. 6 pp. 464–466, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Reactivity of 3,5-bis-(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole

Alkylation of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole with haloalkanes afforded N-CH₂R derivatives, and nitration furnished the corresponding bis-N-nitramine isolated as a trisodium salt. Treatment of the latter with CH₃I resulted in denitration. Diazotization and oxidation of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4- triazole, its N-methyl and N-carboxy derivatives gave rise to the corresponding azido and nitro derivatives. Salts of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazol-5-acetic acid with nitrogen-containing bases were synthesized. It was established that the character of reaction products of 3,5-bis(4-amino-1,2,5-oxadiazol-3-yl)-1,2,4-triazole with formaldehyde depended on the acid-base properties of the medium.__________Translated from Zhurnal Organicheskoi Khirmii, Vol. 41, No. 2, 2005, pp. 270–276.Original Russian Text Copyright © 2005 by Sergievskii, Romanova, Mel’nikova, Tselinskii.     

Alternative Routes to the Pyrazolo[4,3-<Emphasis Type="Italic">e</Emphasis>][1,2,4]triazolo-[1,5-<Emphasis Type="Italic">c</Emphasis>]pyrimidine System

Formimidic acid esters derived from 1-substituted 5-aminopyrazole-4-carbonitriles reacted with carboxylic acid hydrazides on heating to give 2,7-disubstituted pyrazolo[4,3-e][1,2,4]triazolo[1,5-c]pyrimidine derivatives as a result of double heterocyclization. The same compounds were obtained by thermal recyclization of 1-aroyl-2-(1-R-pyrazolo[3,4-d]pyrimidin-4-yl)hydrazines.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 6, 2005, pp. 934–938.Original Russian Text Copyright © 2005 by Tyurin, Vorob’ev, Minyaeva, Krasnikov, Mezheritskii.     

Rearrangements in haloalkoxy (thio,amino)-sym-triazines

The reaction of [2-methoxy-6-dialkylamino-sym-triazin-4-yl]trimethylammonium chlorides with ethylene chlorohydrin gives 2-methoxy-4-(2-chloroethoxy)-6-dialkylamino-sym-triazones, which eliminate CH₃Cl when they are heated to give 2-dialkylamino-4-oxo-4,5,6,7-tetrahydrooxazolo[3,2-a]-sym-triazines. Data from the UV, IR, PMR, and mass spectra are presented.See [1] for communication I.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 989–992, July, 1977.     

Homolytic replacement of a hydrogen atom in 2-methylquinoline by A 1,3-dioxolanyl residue

The reaction of 1,3-dioxolane with sulfuric-acid-protonated 2-methylquinoline initiated by the ROOH + Fe²⁺ system [where R = H, (CH₃)₃C, or C₆H₅C(CH₃)₂] at 5–10 °C in water forms 4-(1,3-dioxacyclopent-2-yl)-2-methylquinoline and 4-(1,3-dioxacy-clopent-4-yl)-2-methylquinoline. The selectivity of the formation of the first reaction product increases on passing from hydrogen peroxide to cumyl and tert-butyl hydroperoxide and with an increase in the pH of the medium.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 25–28, January, 1984.     

Synthesis of 3-(6-R-Benzothiazol-2-yl)-4-methyl-1,2,5-oxadiazoles

The nitrosation of N-aryl-3-oxobutanethioamides afforded 1-(6-R-benzothiasol-2-yl)-1-hydroxyimino-2-propanones that at oximation with hydroxylamine were converted into 1-(6-R-benzothiazol-2-yl)-1,2-dihydroxyiminopropanes. The latter were dehydrated by heating with succinic anhydride at 140°C yielding therewith 3-(6-R-benzothiazol-2-yl)-4-methyl-1,2,5-oxadiazoles.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 5, 2005, pp. 759–761.Original Russian Text Copyright © 2005 by Britsun, Borisevich, Samoilenko, Lozinskii.     

Über Reaktionen von Arylbiguaniden mit Benzoin beimpH der Biguanidbasen

Summary Arylbiguanides2 a–e react with benzoin (1) at thepH of the base to two different products.1 undergoes in presence of the base2 a–e oxidation to benzil and benzoic acid, which reacts fast with the arylbiguanides2 a–e to yield N-[4-(arylamino)-6-phenyl-1,3,5-triazine-2-yl]benzamides3 a–d. After lowering thepH of the reaction mixture, the bases2 b–e react with benzil to yield 2-[1-aryl-5-oxo-4,4-diphenyl-2-imidazoline-2-yl]guanidine4 b–e. The mechanism of the formation is discussed. The structure of4b was established from a single crystal x-ray structure analysis. The analysis was carried out at 100K: C₂₃H₂₁N₅O,M _r=383.5, monoclinic, C 2/c,a=15.842(6),b=8.419(3),c=30.223(10) Å, =98.44(3)°,V=3 987.3(9) ų,Z=8,d _x=1.277 g/cm³, =0.81 cm^–1,R=5.89%R _w=4.97% (1 537 observations, 233 parameters).

     

New unsymmetrical μ-phenoxo bridged binuclear copper(II) complexes

A series of binuclear Cu^II complexes [Cu₂XL] ⁿ⁺ having two copper(II) ions bridged by different motifs (X = OH^–, MeCO₂ ^–, or Cl^–) have been prepared using the ligands: H₂L¹ = 4-methyl-2-[N-(2-{dimethylamino}ethyl-N-methyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol, H₂L² = 4-nitro-2-[N-(2-{dimethylamino}ethyl-N-methyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol, H₂L³ = 4-methyl-2-[N-(2-{diethylamino}ethyl-N-ethyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol and H₂L⁴ = 4-nitro-2-[N-(2-{diethylamino}ethyl-N-ethyl)aminomethyl]-6-[(prolin-1-yl)methyl]phenol. The complexes have been characterized by spectroscopic, analytical, magnetic and electrochemical measurements. Cryomagnetic investigations (80–300 K) revealed anti-ferromagnetic exchange between the Cu^II ions (–2J in the range –50 to –182 cm^–1). The strength of anti-ferromagnetic coupling lies in the order: OAc > OH > Cl. Cyclic voltammetry revealed the presence of two redox couples, assigned to Cu^II/Cu^II/Cu^II/Cu^I/Cu^I/Cu^I. The first reduction potential is sensitive to electronic effects from the aromatic ring substituents and steric effect on the donor nitrogens (side arm) of the ligand systems.