A selective synthesis of 2-([2,2]paracyclophan-5-yl)pyrrole from 5-acetyl[2,2]paracyclophane via the Trofimov reaction

Rearrangement of 5-(1-vinyloxyiminoethyl)[2,2]paracyclophane, the key intermediate of the Trofimov reaction (pyrrole formation from ketoximes and acetylene), gives (120 °C, 30 min, DMSO) 2-([2,2]paracyclophan-5-yl)pyrrole in 74% yield. The intermediate 5-(1-vinyloxyiminoethyl)[2,2]paracyclophane has been synthesised in 78% yield by vinylation of the Cs-derivative of the oxime of 5-acetyl[2,2]paracyclophane with acetylene under pressure in the DMSO-n-pentane two-phase system (70 °C, 5 min).     

Lactam and acid amide acetals. 64. Acylation of enamino ketones of the indolin-3-one and 2-pyrrolin-4-one series and synthesis of 2-indolyl- and 5-pyrrolylacrylic acid derivatives

The reaction of 2-(N,N-dimethylaminomethylene)indolin-3-one and 2-methyl-3-ethoxycarbonyl-5-(N,N-dimethyl aminomethylene)-2-pyrrolin-4-one with acyl halides was used to synthesize immonium salts, the aqueous hydrolysis of which leads to 2-formyl-3-hydroxyindole and 4-hydroxy-5 formylpyrrole derivatives. -Cyano--(2-indolyl)- and -cyano--(5-pyrrolyl)acrylic acid derivatives were synthesized by reaction of immonium salts of the pyrrole series, 4 acyloxy-5-formylpyrrole and 2-formyl-3-acyloxyindole derivatives, with compounds that contain an active methylene group.See [1] for Communication 63.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 343–348, March, 1991.     

Investigation of some nitrogen compounds of 2,2′-dithienyl

The acetylation and formylation of the methyl ester of the dithienyl analog of cinchophen gave 5-acetyl- and 5-formyl-5-(4-methoxycarbonyl-2-quinolyl)-2,2-dithienyls.See [1] for communication IV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 773–774, June, 1972.     

Study of some nitrogen compounds of 2,2′-dithienyl

5-Formyl-5-nitro-2,2-dithienyl and 5-formyl-3-nitro-2,2t'-dithienyl were obtained by nitration of 5-formyl-2,2t'-dithienyl with copper nitrate in acetic anhydride. The structures of the nitroaldehydes were established by their oxidation to the corresponding nitro acids of the 2,2-dithienyl series, the decarboxylation of which yielded 5-nitro- and 3-nitr o-2,2 -dithienyls.See [1] for communication II.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 918–919, July, 1971.     

Influence of onium substituent in phthaloyl ring on thermodynamic parameters of equilibrium between dimer and free radicals of 2-(4-dimethylaminophenyl)-1,3-indandiones

2,2-Bis[2-(4-dimethylaminophenyl)-5-trimethylammonio-1,3-indandione] diperchlorate and 2,2-bis[2-(4-dimethylaminophenyl)-5-(2,4,6-triphenylpyridinio)-1,3-indandione] diperchlorate have very definite thermochromic and mechanochromic properties, owing to reversible dissociation into free radicals. The rupture energy of the central bond C²-C² in 5-substituted 2,2'-bis[2-(4-dimethylaminophenyl)-1,3-indandiones] in acetonitrile is 63–75 kJ/mole; in the dimer with the bulky 5-(2,4,6-triphenylpyridinium) substituent, the rupture energy is 51 kJ/mole. The equilibrium constants follow the Hammett equation (p=1.53, acetonitrile, 293 K). Radicals with onium substituents are thermodynamically the most stable of the arylindandionyl radicals that are thus far known, owing to the significant contribution of electrostatic interactions.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1525–1531, July, 1990.     

Synthesis of trichloro-1,4-benzoquinonyl-substituted 2,2′-bithiazoles

2,2-Bi[5-(2,5-dihydroxy-3,4,6-trichlorophenyl)thiazole] and 6-(2,5-dihydroxy-3,4,6-trichlorophenyl)-2-imino-3,4-dihydro-4H-1,4-thiazin-3-thione are synthesized from 2,5-dihydroxy-3,4,6,7-tetrachloro-2,3-dihydrobenzo[b]furan and dithiooxalyldiamide. The products are oxidized by FeCl₃ to the corresponding trichloro-1,4-benzoquinonyl-substituted sulfur-containing heterocycles. N-Methylation of 2,2-bithiazole by dimethyl sulfate gives 2,2-bi[5-(2,5-dihydroxy-3,4,6-trichlorophenyl)-3-methylthiazolium] bismonomethyl sulfate. The last compound is readily transformed to 2,2-bi[5-(2-hydroxy-5-oxido-3,4,6-trichlorophenyl)-3-methylthiazolium] bisbetaine.Riga Technical University, Riga LV-1048, Latvia, Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 988–992, July, 1999.     

Spatial and Electronic Structure of 2-(2-Furyl)- and 2-(2-Thienyl)pyrroles According to 1H and 13C NMR Data

In 2-(2-furyl)- and 2-(2-thienyl)pyrroles the heterocycles are in efficient ,-conjugation. The presumably possible for this compounds intramolecular hydrogen bond N-H···O or N-H···S is lacking. The COCF₃ group in position 2 of the pyrrole ring is syn-oriented with respect to pyrrole fragment, and the orientation is fixed by an intramolecular hydrogen bond N-H···O. However no bifurcating hydrogen bonds arise in the molecules containing COCF₃ group.     

Synthesis of chlorinated 2-(aminomethyl)- and 2-(alkoxymethyl)pyrroles

The synthesis of chlorinated 2-(hydroxymethyl)-, 2-(alkoxymethyl)- and 2-(aminomethyl)pyrroles via aromatization of 2-aryl-3,3-dichloro-5-(bromomethyl)pyrrolines and via reduction of 2-formyl- and 2-cyanopyrroles is described. The former methodology also provided new 2-[(alkyl- or phenylamino)methyl]pyrroles and a 2-(phosphonomethyl)pyrrole. Halogenated and methylene-spaced functionalized pyrroles are of particular interest for their pronounced physiological activities.     

Palladium(II) chloride compounds with stable biradicals of imidazoline

Conclusions The first coordination compounds of stable nitroxyl biradical imidazolines have been synthesized. From the spectral data obtained, the paramagnetic ligand 4,4-(ethyleneiminomethyl)di-2, 2,5,5-tetramethyl-3-imidazoline-1-oxyl acts as a tetradentate bridge in a binuclear coordination compound with Pd(II), while the azine ligand 4-formyl-2,2,S,5-tetramethyl-3-imidazoline-1-oxyl acts as a bidentate bridge.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 11, pp. 2581–2584, November, 1988.The authors thank E. G. Boguslavskii, I. M. Oglezneva, and V. A. Shipachev for help in obtaining the spectra of the compounds.     

Benzimidazole derivatives

-(1,3-Dimethyl-5-benzimidazolonyl)acrylic acid, -(1,3-dimethyl-5-benzimidazolonyl)propiolic acid, and 5-ethynyl-1,3-dimethylbenzimidazolone were synthesized via the Wittig reaction from 5-formyl-1,3-dimethylbenzimidazolone. The UV and IR spectra are presented.See [1] for communication XXV.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 122–123, January, 1971.     

Reaction of sulphur dioxide with chlorocarbonyls of ruthenium,rhodium and iridium

Summary The reactions of SO₂ with chlorocarbonyls of rhodium and iridium ([M(CO)₂Cl₂]^– and ruthenium ([Ru(CO)_2–Cl₂]_n) ions were studied. Addition of either the Ph₄As⁺ cation or the nitrogen-donor ligands 2,2-bipyridine (bipy),o-phenylenediamine (opd), 1,10-phenanthroline (phen), 2,2,6,2-terpyridine (terpy) or 6,7-dihydro-1,4-di(2-pyridyl)-5H-cyclopenta {d}-pyridazine (5-dppn) to the SO_2– treated chlorocarbonyl solutions resulted in the formation of various complexes according to the nature of metal and ligand. The products have been characterized by physicochemical methods.     

Synthesis,structure, and spectral properties of some bioxazoles

Syntheses of systems containing two oxazole rings [2-phenyl-, 2-(2-furyl)-, and 2-(2-thienyl)-2,5-bioxazoles, and 2,2-(2,5-furylene)bisoxazole] from aldehydes obtained by formylating 2-phenyl-, 2-(2-furyl)-, and 2-(2-thienyl)oxazole have been developed. Terephthalate and thiophen-2,5-dicarboxylate esters have been used to obtain 2,2-(1,4-phenylene)- and 2,2-(2,5-thienylene)bisoxazoles. The PMR, UV, and luminescence spectra of these systems have been examined, and quantum chemical calculations carried out in the PPP approximation.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 826–836, June, 1986.     

Reaction of 1-[2-(vinyloxy)ethyl]-1<Emphasis Type="Italic">H</Emphasis>-pyrroles with trifluoroacetic anhydride

Chemo- and stereoselectivity of the reaction of 1-[2-(vinyloxy)ethyl]-1H-pyrroles with trifluoroacetic anhydride have been studied. The reaction with an equimolar amount of trifluoroacetic anhydride chemoselectively involves the free α-position of the pyrrole ring with formation of the corresponding α-trifluoroacetylpyrroles. In the reaction with 2 equiv of trifluoroacetic anhydride, acylation of both α-position of the pyrrole ring and β-position of the vinyloxy group leads to the formation of 1-(2-{[(1E)-4,4,4-trifluoro-3-oxobut-1-en-1-yl]oxy}ethyl)-2-trifluoroacetyl derivatives with high stereoselectivity.     

Synthesis of 2-[β-(5′-halogenofur-2′-yl)vikyl]benzimidazoles

2-[-(5-halogenofur-2-yl)vinyl]benzimidazoles (I) have been synthesized by the condensation of o-phenylenediamine with 5-halogeno-fur-2-ylacroleins or of 2-methylbenzimidazole with 5-halogenofurfurals. The methiodides of the 1-methyl-substituted derivatives ofI readily react with secondary amines (piperidine, dimethylamine)giving methiodides of 2-[-(5-dialkylaminofur-2-yl)vinyl]-1-methylbenzimidazoles.     

Five-membered 2,3-dioxo heterocycles: LIII. Reaction of 3-Aroyl-1<Emphasis Type="Italic">H</Emphasis>-pyrrolo[2,1-<Emphasis Type="Italic">c</Emphasis>][1,4]benzoxazine-1,2,4-triones with substituted 1,3,3-trimethyl-3,4-dihydroisoquinolines. A new approach to 13-aza analogs of steroids

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones reacted with substituted 1,3,3-trimethyl-3,4-dihydroisoquinolines to give the corresponding 3-aroyl-4-hydroxy-1-(2-hydroxyphenyl)-5′,5′-dimethyl-5′,6′-dihydro-1H-spiro[pyrrole-2,2′-pyrrolo[2,1-a]isoquinoline]-3′,5-diones. 7′,8′-Benzo derivatives of the latter may be regarded as 13-azagonane analogs having a spiro-fused pyrrole ring at C¹⁶.     

Acetals of lactams and acid amides. 47. Investigation of the behavior of substituted 6-(Β-dimethylamino) vinyl-4-pyrimidinones in acidic media. Synthesis of 3-cyano-4-anilino-5-formyl-2-pyridone and 3-chloro-4-cyanobenzo[b] [1,6]-naphthyridine

The hydrolysis of 1-substituted 5-cyano-6-(-dimethylamino)vinyl-4-pyrimidinones in acidic media was studied. It was shown that the 1-benzyl derivative is converted to a mixture of -cyano--benzylamino-crotonamide and 3-cyano- and 3-carbamido-4-benzyl-amino-2-pyridones. The principal product in the hydrolysis of the 1-phenyl derivative is 3-cyano-4-anilino-5-formyl-2-pyridone. Cyclization of the latter by heating in phosphorus oxychloride leads to 3-chloro-4-cyanobenzo[b] [1, 6]naphthyr idine.See [1] for Communication 46.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1118–1123, August, 1986.     

Direct functionalization of the cyclometalated 2-(2′-pyridyl)phenyl ligand bound to iridium(III)

Treatment of [Ir(ppy)₂(μ-Cl)]₂ and [Ir(ppy)₂(dtbpy)][OTf] (ppy = 2-(2′-pyridyl)phenyl; dtbpy = 4,4′-di-tert-butyl-2,2′-bipyridine; OTf = triflate) with pyridinium tribromide in the presence of Fe powder led to isolation of [Ir(4-Br-ppy)(μ-Br)]₂ (1) and [Ir(4-Br-ppy)₂(dtbpy)][OTf] (2), respectively. Pd-catalyzed cross-coupling of 2 with RB(OH)₂ afforded [Ir(4-R-ppy)₂(dtbpy)][OTf] (R = 4′-FC₆H₄ (3)), 4′-PhC₆H₄ (4), 2′-thienyl (5), 4′-C₆H₄CH₂OH (6). Treatment of 4 with B₂(pin)₂ (pin = pinacolate) afforded [Ir{4-(pin)B-ppy}₂(dtbpy)][OTf] (7). The alkynyl complexes [Ir(4-PhCC-ppy)₂(dtbpy)][OTf] (8) and [Ir{4-Me₂(OH)CC-ppy}(4-Br-ppy)(dtbpy)][OTf] (9) were prepared by cross-coupling of 2 with PhCCSnMe₃ and Me₂C(OH)CCH, respectively. Ethynylation of [Ir(fppy)₂(dtbpy)][OTf] (fppy = 5-formyl-2-(2′-pyridyl)phenyl) with Ohira’s reagent MeCOC(N₂)P(O)(OEt)₂ afforded [Ir{5-HCC-ppy}₂(dtbpy)][OTf] (10). The solid-state structures of 2, 5, 7, and 10 have been determined.     

Synthesis of new imidazo[2,1-<Emphasis Type="Italic">b</Emphasis>][1,3]thiazole derivatives from 2-amino-4-(2,2-dichlorovinyl)-1,3-thiazole and <Emphasis Type="Italic">N</Emphasis>-(2,2-dichloro-2-phenylethylidene)arenesulfonamides

2-Amino-4-(2,2-dichlorovinyl)-1,3-thiazole reacted with highly electrophilic N-(2,2-dichloro-2-phenylethylidene)- and N-(2,2,2-trichloroethylidene)arenesulfonamides through the exocyclic amino group to give products of nucleophilic addition to the azomethine bond, N-[2,2-di(or 2,2,2-tri)chloro-1-(1,3-thiazol-2-ylamino)ethyl]arenesulfonamides in good yields. Intramolecular heterocyclization of the latter afforded N-[3-(2,2-dichloroethyl)-6-phenylimidazo[2,1-b][1,3]thiazol-5-yl]arenesulfonamides.     

Direct nitration and acetylation of the furan nucleus of 1-alkyl-2-[Β -(2′-furyl) vinyl]-benzimidazoles

The direct nitration and acetylation of 1-methyl-, 1-ethyl-, and 1-benzyl-2-[-(2-furyl)vinyl]benzimidazoles has given the corresponding 1-alkyl- and 1-benzyl-2-[-(5-nitro-2-furyl)vinyl]benzimidazoles and 1-alkyl- and 1-benzyl-2-[-(5-acetyl-2-furyl)vinyl]benzimidazoles. The UV spectra of these compounds have been recorded and their ionization constants have been determined.Translated from Khimiya Geterotsiklicheskikh Soedinenii, Vol. 6, No. 6, pp. 832–834, June, 1970.     

Preparation of twelve 1-methyl-2-formyl-5-substituted pyrroles and their hydrazones

Preparation of twelve 1-methyl-2-formyl-5-substituted pyrroles (2a-1), with five of them as new compounds, is described. Their derivatives, i.e., 1-methyl-2-formyl-5-substituted pyrrole phenyl hydrazones (3a-1) and 1-methyl-2-formyl-5-substituted pyrrole (4-nitrophenyl) hydrazones (4a-1) are all new compounds. They have also been prepared and further identified.