Synthesis,stereochemistry, and isomeric transformations of 4-aryl-5-aroyl-2-methylthio-2-imidazolines

The corresponding 4-aryl-5-aroyl-2-methylthio-2-imidazolines were obtained by the reaction of complexes of cis- and trans-3-aroylaziridines and boron trifluoride with methyl thiocyanate. It is shown on the basis of spectral data that the aziridine ring is opened regiospecifically at the C(₂) atom and stereospecifically with inversion of the configuration.Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1484–1488, November, 1988.     

Boron fluorides of cis- and trans-2-aryl-3-aroylaziridines

The reaction of boron trifluoride etherate with cis- and trans-2-aryl-3-aroylaziridines yields the respective complexes in high yield. According to PMR spectral data the methyl group of boron trifluoride trans-1-methyl-3-aroylaziridines is located in syn-position, and in the cis-aziridine complexes in anti-position, to the carbonyl group.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1047–1049, August, 1987.     

Synthesis and stereochemistry of 2,2,3-trimethyl-5-aryl-4-aroyloxazolidines

cis-2,2,3-Trimethyl-5-aryl-4-aroyloxazolidines were obtained by heating complex boron trifluoride salts of trans-1-methyl-2-aryl-3-aroylaziridines with acetone. The reaction of complex boron trifluoride salts of cis-1-methyl-2-aryl-3-aroyl-aziridines leads to substituted benzaldehydes and -N-methylaminoacetophenones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 38–42, January, 1981.     

Cyclopropanation of N-substituted 3-aryl-2-cyanoprop-2-enamides and derivatives of 5,5-Dimethyl-2-oxo-2,5-dihydrofuran-3-carboxylic acid and 2-oxochromene-3-carboxylic acid with bromine-containing zinc enolates

Zinc enolates derived from 1-aryl-2,2-dibromoalkanones react with N-substituted 3-aryl-2-cyanoprop-2-enamides and 5,5-dimethyl-2-oxo-2,5-dihydrofuran-3-carboxylic and 2-oxochromene-3-carboxylic acid derivatives to give, respectively, N-substituted 2-alkyl-3-aryl-2-aroyl-1-cyanocyclopropane-1-carboxamides, 6-(4-bromobenzoyl)-4,4,6-trimethyl-2-oxo-3-oxabicyclo[3.1.0]hexane-1-carboxylic acid ethyl ester and morpholide, and 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropla[c]chromene-1a-carboxylic acids as a single geometric isomer. Treatment of 1-alkyl-1-aroyl-2-oxo-1a,7b-dihydrocyclopropa[c]chromene-1a-carboxylic acids with carboxylic acid anhydrides leads to the formation of the corresponding 9c-alkyl-1-aryl-3,4-dioxo-9b,9c-dihydro-2,5-dioxacyclopenta[2,3]cyclopropa[1,2-a]naphthalen-1-yl carboxylates.     

Reaction of 1-alkyl-2-aryl-3-(2-methyl-2,3-epoxypropionyl)aziridines with boron trifluoride etherate in methanol

The reaction of boron trifluoride etherate in methanol with trans-1-methyl(ethyl)-or cis-1-cyclohexyl-2-aryl-3-(2-methyl-2,3-epoxypropionyl)aziridines leads to the formation of the corresponding boron fluoride complexes on the nitrogen atom of the aziridine ring. Reaction with trans-1-cyclohexyl-2-phenyl-3-(2-methyl-2,3-epoxypropionyl)aziridines occurs with stereospecific opening of the aziridine ring to give diastereomeric 2-methyl-5-methoxy-5-phenyl-4-cyclohexylamino-1,2-epoxypen-tan-3-ones, as well as products from the opening of the epoxide and aziridine rings — tetrahydrofuranones and tetrahydropyranones.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 596–600, May, 1986.     

Five-membered 2.3-dioxo heterocycles: LXVIII. Three pathways in the reaction of methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with 3-amino-5,5-dimethylcyclohex-2-en-1-one

Methyl 3-aroyl-1-aryl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with 3-amino-5,5-dimethylcyclohex-2-en-1-one having no substituent on the nitrogen atom to give 3-aroyl-4-arylamino-6′,6′-dimethyl-6′,7′-dihydro-5H-spiro[furan-2,3′-indole]-2′,4′,5′(1′H,5′H)-triones or methyl 12-aroyl-11-aryl-9-hydroxy-5,5-dimethyl-3,10-dioxo-8,11-diazatricyclo[7.2.1.0^2,7]dodec-2(7)-ene-1-carboxylates. The latter underwent thermal recyclization to 3′-aroyl-1′-aryl-4′-hydroxy-6,6-dimethyl-6,7-dihydrospiro[indole-3,2′-pyrrole]-2,4,5′(1H,1′H,5H)-triones.     

Reactions of bromine-containing organozinc compounds derived from α,α-dibromo ketones with 2-arylmethylideneindan-1,3-diones and 5-arylmethylidene-2,2-dimethyl-1,3-dioxane-4,6-diones

Bromine-containing organozinc compounds generated from 1,1-dibromo-3,3-dimethylbutan-2-one reacted with 2-arylmethylideneindan-1,3-diones and 5-arylmethylidene-2,2-dimethyl-1,3-dioxane-4,6-diones to give 3-aryl-2-(2,2-dimethylpropanoyl)spiro[cyclopropane-1,2′-indan]-1′,3′-diones and 1-aryl-6,6-dimethyl-2-(2,2-dimethylpropanoyl)-5,7-dioxaspiro[2.5]octan-4,8-diones, respectively. Reactions of 2-arylmethylideneindan-1,3-diones with bromine-containing zinc enolates derived from 1-aryl-2,2-dibromopropan-1-ones and 2,2-dibromo-1,2,3,4-tetrahydronaphthalen-1-one resulted in the formation of 2-aroyl-3-aryl-2-methylspiro-[cyclopropane-1,2′-indan]-1′,3′-diones and 2,3: 8,9-dibenzo-12-phenyldispiro[4.0.5.1]dodecane-1,4,7-trione, respectively.     

Synthesis and properties of ethyl esters of some 1,2-dihydropyridine-3,5-dicarboxylic acids

The oxidation of diethyl 1-methyl- or 1-aryl-2,6-dimethyl-4-aryl-1,4-dihydropyridine-3,5-dicarboxylates with hydrogen peroxide in the presence of perchloric acid gave the perchlorates of the corresponding pyridinium ions, the reduction of which with NaBH₄ is a preparative method for the synthesis of diethyl esters of 1-substituted 2,6-dimethyl-1,2-dihydropyridine-3,5-dicarboxylic acids. Derivatives of the 5-carboxylic acid of the corresponding 1,2-dihydropyridine are formed by alkaline hydrolysis of these esters.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1225–1228, September, 1982.     

Chemistry of acyl(imidoyl)ketenes. 7. Synthesis and thermolysis of 5-aryl-4-quinoxalinyl-2,3-dihydrofuran-2,3-diones

3-Aryl-Z-2-aroylmethylidene-1,2-dihydroquinoxalines react with oxalyl chloride to form 3-aryl-2-(2-aryl-4,5-dioxo-4,5-dihydro-3-furyl)quinoxalines, whose thermal decarbonylation generate 5-aryl-2-3(arylquinoxalin-2-yl)-4-aroyl-3-aroyloxy-1H-pyrido[1,2-a]quinoxalin-1-ones. The crystal and molecular structures of one of them (Ar = Ph) were established by X-ray diffraction analysis.     

Chemistry of iminofurans: V. Synthesis,structure, and cyclization of 4-R-4-oxo-2-[2-(2-oxo-1,2-diphenylethylidene)hydrazino]but-2-enoic acids

Reactions of 1,2-diphenylethane-1,2-dione hydrazone with 4-aryl-2-hydroxy-4-oxobut-2-enoic and 2-hydroxy-5,5-dimethyl-4-oxohex-2-enoic acids provided 4-aryl-4-oxo-2-[2-(2-oxo-1,2-diphenylethylidene) hydrazino]but-2-enoic and 5,5-dimethyl-4-oxo-2-[2-(2-oxo-1,2-diphenylethylidene)hydrazino]hex-2-enoic acids. The acids derivatives can exist in solutions as Z- and β-enehydrazino-or β-ketohydrazone forms, and under the treatment with acetic anhydride they undergo cyclization into 5-aryl- and 5-tert-butyl-3-[2-(2-oxo-1,2-diphenylethylidene)hydrazono]-2,3-furandiones.     

Highly convenient amine-free sonogashira coupling in air in a polar mixed aqueous medium by trans- and cis-[(NHC)2PdX2] (X=Cl, Br) complexes of N/O-functionalized N-heterocyclic carbenes

Two new trans- and cis-[(NHC)(2)PdX(2)] (X=Cl, Br) complexes of N/O-functionalized N-heterocyclic carbenes employed in a highly convenient amine-free Sonogashira cross-coupling reaction in air in a polar mixed aqueous medium are reported. Specifically, the trans-[{1-benzyl-3-(3,3-dimethyl-2-oxobutyl)imidazol-2-ylidene}(2)PdBr(2)] (3) and cis-[{1-benzyl-3-(N-tert-butylacetamido)imidazol-2-ylidene}(2)PdCl(2)] (4) complexes effectively catalyzed the Sonogashira cross-coupling reaction of aryl iodides with substituted acetylenes in air in a mixed solvent (DMF/H(2)O, 3:1 v/v) under amine-free conditions. Interestingly, these trans- and cis-[(NHC)(2)PdX(2)] (X=Cl, Br) complexes, with two N-heterocyclic carbene ligands, exhibited superior activity compared with the now popular PEPPSI (pyridine enhanced precatalyst preparation, stabilization and initiation)-themed analogues, trans-[(NHC)Pd(pyridine)X(2)] (X=Cl, Br), 3 a and 4 a, with one N-heterocyclic carbene ligand and a "throw away" pyridine ligand in a trans disposition to each other. The higher activities of 3 and 4 compared with PEPPSI analogues 3 a and 4 a are attributed to more-electron-rich metal centers, as revealed by DFT studies, in the former complexes and is in concurrence with a more electron-rich metal center being effective in facilitating the oxidative addition of aryl halide, often a rate-determining step in palladium-mediated cross-coupling reactions. Complexes 3 and 4 were prepared from the corresponding silver analogues by transmetalation with [(cod)PdCl(2)], whereas the corresponding PEPPSI analogues 3 a and 4 a were obtained directly from the imidazolium halide salts by reaction with PdCl(2) in pyridine in the presence of K(2)CO(3) as base.     

Synthesis of annelated [a]aza-anthracenones and thieno[3,2-g]aza-naphthalenones through ring transformation of 2H-pyran-2-one followed by photocyclization

A concise synthesis of some new classes of heterocycles (4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a-diaza-cyclopenta[a]anthracen-6-carbonitriles and 5-aryl-12-oxo-1,3,4,12-tetrahydro-2H-1,4a-diazabenzo[a]anthracene-7-carbonitriles) has been developed by the ring transformation of suitably functionalized 2H-pyran-2-one with α-oxoketene cyclic aminals to intermediates (8-aroyl-5-aryl-2,3-dihydro-1H-imidazo[1,2-a]pyridine-7-ylidene)-acetonitriles and (9-aroyl-6-aryl-1,2,3,4-tetrahydropyrido[1,2-a]pyrimidin-8-ylidene)-acetonitriles) followed by their photocyclization either in CHCl₃ or acetonitrile. This reaction was further explored for the synthesis of methyl 4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a,9-triaza-cyclopenta[a]anthracene-6-carboxylate, 4-aryl-11-oxo-1,2,3,11-tetrahydro-1,3a,9-triaza-cyclopenta[a]anthracene-6-carbonitriles, 5-aryl-12-oxo-1,3,4,12-tetrahydro-2H-1,4a,10-triazabenzo[a]anthracene-7-carbonitriles, 4-aryl-10-oxo-1,2,3,10-tetrahydro-9-thia-1,3a-diazadicyclopenta[a,g]naphthalene-6-carbonitriles and 5-aryl-11-oxo-1,3,4,11-tetrahydro-2H-10-thia-1,4a-diazacyclopenta[b]phenanthrene-7-carbonitriles from the similar reactions.     

Tungsten(VI) complexes with aminobis(phenolato) [O,N,O] donor ligands

The reaction between trisdiolatotungsten(VI) complex [W(eg)(3)] (1) (eg = 1,2-ethanediolato dianion) and phenolic ligand precursor methylamino-N,N-bis(2-methylene-4,6-dimethylphenol) (H(2)L(Me)) or methylamino-N,N-bis(2-methylene-4-methyl-6-tert-butylphenol) (H(2)L(tBu)) affords monomeric oxotungsten complex [WO(eg)(L(Me))] (2) or [WO(eg)(L(tBu))] (3), respectively. These complexes react further with chlorinating reagents, which leads to the displacement of ethanediolato ligands from the complex units and formation of cis and trans isomers of the corresponding dichloro complexes [WOCl(2)(L(Me))] (4) and [WOCl(2)(L(tBu))] (5), respectively. Identical dichloro complexes were also prepared by the reaction between the above-mentioned phenolic ligand precursors and [WOCl(4)]. Molecular structures of 3, cis-4, trans-4, and cis-5 were verified by X-ray crystallography. Complexes 2-5 can be activated by Et(2)AlCl to catalyze ring-opening metathesis polymerization of norbornene.     

Synthesis of cis-1-methyl-2-aryl-3-aroylaziridines

trans-1-Methyl-2-aryl-3-aroylaziridines readily undergo epimerization to give the corresponding cis isomers in high yields in the presence of catalytic amounts of quaternary ammonium bases (trimethylbenzylammonium or triethylmethylammonium hydroxide). The structures of the compounds obtained were established on the basis of the IR and PMR spectra and the results of elementary analysis.Translated from Khimiya Geterotsilicheskikh Soedinenii, No. 10, pp. 1353–1355, October, 1980.     

线型1,2-邻二萘醌-1-肟(1-nqo)钌配合物的合成

报道了含C_(16)长碳链线型1,2-邻二萘醌-1-肟(1-nqo)钌配合物trans-，cis- 及cis-，cis-[Ru(1-nqo)_2(CO)(spy)] (3)及(4)含C_(18)长碳链线型1-nqo钌配合 物cis-，cis-[Ru(1-nqo)_2(CO)(opy)] (5)，trans-，trans-[Ru(1-nqo)_2(opy) _2] (6)的合成。利用红外、FAB质谱、核磁共振氢谱及紫外-可见吸收光谱表征配 合物的结构，利用~1H-~1H偶合二维核磁技术对核磁共振峰进行指认。     

Synthesis and properties of a dithiirane trans-1,2-dioxide, a three-membered vic-disulfoxide

cis- and trans-3-(1-adamantyl)-3-tert-butyldithiirane 1-oxides were oxidized with dimethyldioxirane to give the trans-1,2-dioxide. Thermal decomposition of the 1,2-dioxide yielded the corresponding (E)- and (Z)-sulfines, thioketone, and cis- and trans-dithiirane 1-oxides. In the thermolysis, decomposition to the sulfines and SO was the main path and that to the thioketone and SO(2) was the minor one. The two decomposition processes and epimerization to the cis-1,2-dioxide were analyzed theoretically. SO generated in situ reacted with thioketones as additives to give the corresponding dithiirane 1-oxides.     

Isolation and properties of the products of the covalent hydration of 4H-imidazoles

The neutralization of 5-hydroxy-4,4-dimethyl-2-imidazolinium chlorides yields in the free state the products of the covalent hydration of the corresponding 4H-imidazoles — 5-hydroxy-4, 4-dimethyl-2-imidazolines. On being heated, the compounds obtained undergo various transformations, depending on the presence and position of oxygen-containing functions: 5-hydroxy-2-imidazoline gives 2-acetylamino-2-methyl-1-phenylpropan-1-ol; 3,5-dihydroxy-2-imidazoline dehydrates to 4H-imidazole 3-oxide; and 1,5-dihydroxy-2-imidazolines are converted into 2,3-dihydro-4H-1,2,5-oxadiazines.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1087–1092, August, 1973.     

Bis(acetylacetonato)ruthenium(II) complexes containing alkynyldiphenylphosphines. Formation and redox behaviour of [Ru(acac)2(Ph2PC triple bond CR)2] (R=H, Me, Ph) complexes and the binuclear complex cis-[{Ru(acac)2}2(micro-Ph2PC triple bond CPPh2)}2

Two equivalents of Ph(2)PC triple bond CR (R=H, Me, Ph) react with thf solutions of cis-[Ru(acac)(2)(eta(2)-alkene)(2)] (acac=acetylacetonato; alkene=C(2)H(4), 1; C(8)H(14), 2) at room temperature to yield the orange, air-stable compounds trans-[Ru(acac)(2)(Ph(2)PC triple bond CR)(2)] (R=H, trans-3; Me=trans-4; Ph, trans-5) in isolated yields of 60-98%. In refluxing chlorobenzene, trans-4 and trans-5 are converted into the yellow, air-stable compounds cis-[Ru(acac)(2)(Ph(2)PC triple bond CR)(2)] (R=Me, cis-4; Ph, cis-5), isolated in yields of ca. 65%. From the reaction of two equivalents of Ph(2)PC triple bond CPPh(2) with a thf solution of 2 an almost insoluble orange solid is formed, which is believed to be trans-[Ru(acac)(2)(micro-Ph(2)PC triple bond CPPh(2))](n) (trans-6). In refluxing chlorobenzene, the latter forms the air-stable, yellow, binuclear compound cis-[{Ru(acac)(2)(micro-Ph(2)PC triple bond CPPh(2))}(2)] (cis-6). Electrochemical studies indicate that cis-4 and cis-5 are harder to oxidise by ca. 300 mV than the corresponding trans-isomers and harder to oxidise by 80-120 mV than cis-[Ru(acac)(2)L(2)] (L=PPh(3), PPh(2)Me). Electrochemical studies of cis-6 show two reversible Ru(II/III) oxidation processes separated by 300 mV, the estimated comproportionation constant (K(c)) for the equilibrium cis-6(2+) + cis6 <=> 2(cis-6(+)) being ca. 10(5). However, UV-Vis spectra of cis-6(+) and cis-6(2+), generated electrochemically at -50 degrees C, indicate that cis-6(+) is a Robin-Day Class II mixed-valence system. Addition of one equivalent of AgPF(6) to trans-3 and trans-4 forms the green air-stable complexes trans-3 x PF(6) and trans-4 x PF(6), respectively, almost quantitatively. The structures of trans-4, cis-4, trans-4 x PF(6) and cis-6 have been confirmed by X-ray crystallography.     

Reactions of zinc enolates derived from 1-aryl-2-bromo-alkanones and 1-aryl-2-bromo-2-phenylethanone with 3-aroyl-6-bromochromen-2-ones and 2-benzoylbenzo[f]chromen-3-one

3-Aroyl-6-bromochromen-2-ones and 2-benzoylbenzo[f]chromen-3-one reacted with zinc enolates derived from 1-aryl-2-bromoalkanones and 1-aryl-2-bromo-2-phenylethanone to give, respectively, 4-(1-alkyl-2-aryl-2-oxoethyl)-3-aroyl-6-bromochroman-2-ones and 1-(2-aroyl-1-methyl-2-oxoethyl)-2-benzoyl-1,2-dihydrobenzo[f]chromen-3-ones as a single stereoisomer. Treatment with acetic anhydride of the intermediate product obtained from 3-benzoyl-6-bromochromen-2-one and [1-(4-chlorophenyl)-2-phenylethen-1-yloxy]-zinc(II) bromide resulted in the formation of 3-(1-acetoxy-1-phenylmethylidene)-6-bromo-4-[2-(4-chlorophenyl)-2-oxo-1-phenylethyl]chroman-2-one.     

Reduction and alkaline hydrolysis of 5-oxoindeno[1,2-b]pyridinium salts

5,9b-Dihydro derivatives of indeno[1,2-b]pyridine were obtained by the reduction of the corresponding 1,2-dimethyl-4-aryl-5-oxoindeno[1,2-b]pyridinium perchlorates. 1,2-Dimethyl-3-ethoxycarbonyl-4-phenyl-5-oxoindeno[1,2-b]pyridinium perchlorate forms in alkaline medium with splitting, recyclization and deamination products.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp 86–89, January, 1987.