Reaction of 3,4,4-Trichloro-1-(4-methylphenyl)-3-buten-1-one with Amines

Reaction of 3,4,4-trichloro-1-(4-methylphenyl)-3-buten-1-one with amines results in replacement of the internal chlorine atom and is accompanied by prototropic allyl rearrangement leading to formation of the corresponding 3-amino-4,4-dichloro-1-(4-methylphenyl)-2-buten-1-ones. The reaction of the title compound with 2,4-dinitrophenylhydrazine yields 3,4,4-trichloro-1-(4-methylphenyl)-3-buten-1-one 2,4-dinitrophenylhydrazone and is not accompanied by allyl rearrangement.     

5-(Naphth-1-yl)- and 5-[(1,1′-biphenyl)-4-yl]isoxazole-3-carbaldehyde oximes: Synthesis,complexes with palladium,and application in catalysis

1-(Naphth-1-yl)- and 1-[(1,1′-biphenyl)-4-yl-3,4,4-trichloro-3-buten-1-ones were synthesized by acylation of naphthalene and biphenyl with 3,4,4-trichloro-3-butenoyl chloride. Further reaction with hydroxylamine led to 5-(naphth-1-yl)- and 5-[(1,1′-biphenyl)-4-yl]isoxazole-3-carbaldehyde oximes. The latter form complexes with palladium, which possess high catalytic activity in the Suzuki reaction in aqueous and aqueous-alcoholic media.     

Reaction of 5-arylfuran-2(3<Emphasis Type="Italic">H</Emphasis>)-ones with amines

5-(4-Chlorophenyl)- and 5-phenylfuran-2(3H)-ones reacted with guanidine carbonate at the methylene group in the unsaturated lactone molecule, leading to the formation of 4-(2-aryl-5-oxo-2,5-dihydrofuran-2-yl)-5-aryltetrahydrofuran-2-ones, while 5-(4-methylphenyl)furan-2(3H)-one under analogous conditions gave rise to N,N′-bis[4-(4-methylphenyl)-4-oxobutanoyl]guanidine. The reactions of 5-arylfuran-2(3H)- ones with thioacetamide afforded 4-aryl-N-{1-[5-aryl-2-oxo-2,3-dihydrofuran-3-ylidene]ethyl}-4-oxobutanamides. The corresponding N-(4-aryl-4-oxobutanoyl)thioureas were obtained by heating 5-arylfuran-2(3H)-ones with thiourea.     

Reactions of 3-amino-1-phenyl- and 3-amino-1-(thien-2-yl)-4,4,4-trifluorobut-2-en-1-ones with 1,2-diaminopropane and 1,2-diamino-3,3,3-trifluoropropane

The reactions of 3-amino-1-phenyl-and 3-amino-1-(thien-2-yl)-4,4,4-trifluorobut-2-en-1-ones with 1,2-diaminopropane under kinetically controlled conditions afford mixtures ofcis andtrans isomers of 2-aroylmethyl-4-methyl-2-trifluoromethylimidazolidines. Analogous reactions with 1,2-diamino-3,3,3-trifluoropropane yieldcis-2-aroylmethyl-2,4-bis(trifluoro-methyl)imidazolidines. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2135–2139, November, 1999.     

Chemosensor activity of 2-(anthracen-9-yl)-substituted imidazolidines and hexahydropyrimidines

A number of 2-(anthracen-9-yl)-substituted imidazolidines and hexahydropyrimidines were synthesized by reaction of N,N′-bis[aryl(hetaryl)methyl]ethylene-1,2-diamines and N,N′-bis[aryl(hetaryl)methyl]-propane-1,3-diamines with anthracene-9-carbaldehyde. The obtained compounds showed chemosensor activity toward Cd²⁺, Cu²⁺, and Hg²⁺ ions.     

Synthesis of 2-(2-hydroxyaroylmethylene)hexahydropyrimidines from 2-trichloromethylchromones and trimethylenediamine

The reactions of 2-trichloromethylchromones with trimethylenediamine in ethanol at room temperature afford 2-(2-hydroxyaroylmethylene)hexahydropyrimidines. Under analogous conditions, 2-methylchromone gives a mixture ofN,N′-trimethylenebis[3-amino-1-(2′-hydroxyphenyl)-2-buten-1-one] andN,N′-trimethylenebis(imine) of 2-hydroxyacetophenone. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2140–2143, November, 1999.     

Haloacetylated enol ethers. 13. Synthesis of N-[1-aryl(alkyl)-3-oxo-4,4,4-trichloro-1-buten-1-yl]-o-phenylenediamines and 2-trichloromethyl-4-aryl-3H-1,5-benzodiazepines

The synthesis and isolation of the intermediates N-[1-aryl(alkyl)-3-oxo-4,4,4-trichloro-1-buten-1-yl]-o-phenylenediamines 2a-f and the corresponding 2-trichloromethyl-4-aryl-3H-1,5-benzodiazepines 3c-g or benzimidazoles 4a-b derivatives obtained from the intramolecular cyclization of 2a-f or from direct cyclo-condensation reaction of β-alkoxyvinyl trichloromethyl ketones 1a-g with o-phenylenediamine, is reported. Depending of the structure of the β-alkoxyvinyl trichloromethyl ketones or the N-[1-aryl(alkyl)-3-oxo-4,4,4-trichloro-buten-1-yl]-o-phenylenediamines and the reactions conditions, benzimidazoles or 3H-1,5-benzodiazepines were obtained.     

Synthesis and properties of z-1,3-bis-(aryl)-4-bromo-2-buten-1-ones

Bromination of 1,3-bis(aryl)-2-buten-1-ones by N-bromosuccinimide in anhydrous carbon tetrachloride gives Z-1,3-bis(aryl)-4-bromo-2-buten-1-ones. The effect of the nature of substituent in the benzene ring on the course of a reaction with nucleophiles has been studied. Heating an alcohol solution of these ketones (Ar = 4-MeOC₆H₄, 4-ClC₆H₄) in the presence of acid or in the presence of base (Ar = Ph) gave 2,4-bis(aryl)furans. Treatment of 1,3-bis(aryl)-4-bromo-2-buten-1-ones with thioacetamide gave 2,4-bis(aryl)thiophenes. The oxidation of the halo-substituted dypnones with H₂O₂/NaOH gave (3-bromomethyl-3-aryl-2-oxiranyl)(aryl)methanones. The reaction of halo-substituted dypnones with aryl hydrazines gave 1,3,5-triaryl-1,6-dihydropyridazines or 1,3,5-triarylpyridazinium bromides depending on the structure of the reagents.     

Synthesis of Polysubstituted Pyridopyrimidines,Pyrimidines, and Pyrazoles Based on 1,1-Bis(1H-benzotriazol-1-yl)-and 1,1-Bis(3,5-dimethyl-1H-pyrazol-1-yl)-3,4,4-trichloro-2-nitrobuta-1,3-dienes

Russian Journal of Organic Chemistry - The reaction of 3,4,4-trichloro-1,1-bis(3,5-dimethyl-1H-pyrazol-1-yl)-2-nitrobuta-1,3-diene with 2-aminopyridine gave a polysubstituted...     

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.     

Synthesis and nitration of <Emphasis Type="Italic">N,N</Emphasis>´-bis(3-R-furoxan-4-yl)methylenediamines

A Mannich reaction of 4-amino-3-R-furoxans with paraformaldehyde in 10% aqueous H₂SO₄ led to the high yields of N,N′-bis(3-R-furoxan-4-yl)methylenediamines, whose structure (using R = Me as an example) was confirmed by X-ray diffraction study. The N,N′-bis-(3-R-furoxan-4-yl)methylenediamines obtained were nitrated to N,N′-dinitro-N,N′-bis-(3-R-furoxan-4-yl)methylenediamines upon the action of 100% HNO₃ in acetic or trifluoroacetic anhydride.     

Synthesis and characterization of novel 2-(1-benzyl-3-[4-fluorophenyl]-1H-pyrazol-4-yl)-7-fluoro-4H-chromen-4-one derivatives

Novel 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehydes 3a to 3e were synthesized via Vilsmeier-Haack reaction of the appropriate 1-benzyl-2-(1-(4-fluorophenyl)ethylidene)hydrazines, derived from 4-fluoroacetophenone 1 with substituted 2-benzylhydrazines 2a to 2e . The base catalyzed condensation of 1-benzyl-3-(4-fluorophenyl)-1H-pyrazole-4-carbaldehydes 3a to 3e with 1-(4-fluoro-2-hydroxyphenyl)ethanone 4 gave (E)-3-(1-benzyl-3-(4-fluorophenyl)-1H-pyrazol-4-yl)-1-(4-fluoro-2-hydroxyphenyl)prop-2-en-1-ones 5a to 5e . On cyclization with dimethyl sulfoxide (DMSO)/I₂, compounds 5a to 5e gave 2-(1-benzyl-3-(4-fluorophenyl)-1H-pyrazol-4-yl)-7-fluoro-4H-chromen-4-ones 6a to 6e . Structures of all novel compounds were confirmed by infrared (IR), proton nuclear magnetic resonance (¹H NMR), carbon nuclear magnetic resonance (¹³C NMR), and mass spectral data. All the synthesized compounds were screened for their antibacterial activities.     

The behavior of <Emphasis Type="Italic">p</Emphasis>-bis{3-[N-(3-chloro-buten-2-yl)pyrrolidinio(piperidinio or morpholinio)]propyn-1-yl}benzene dichlorides in an aqueous base medium

In aqueous base medium p-bis{3-[N-(3-chlorobuten-2-yl)pyrrolidinio (piperidinio or morpholinio)]-propyn-1-yl}benzene dichlorides undergo a two-way dehydrochlorination-cyclization reaction to form benzo[5,6-a:5′,6′-c]bis(2,2-tetramethylene- or -2,2-pentamethylene-4-methylisoindolinium) and benzo-[5,6-a:5′,6′-c]bisspiro(4-methylisoindoline-2,4′-morpholinium) dichlorides. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 546–549, April, 2009.     

Reaction of sulfene and dichloroketene with open-chain N,N-disubstituted α-aminomethyleneketones. Synthesis of 4-dialkylamino-3,4-dihydro-6-methyl-5-phenyl-1,2-oxathiin 2,2-dioxides and of N,N-disubstituted 4-amino-3-chloro-(6-methyl-5-phenyl)(6-benzyl)-2H-pyran-2-ones

Cycloaddition of sulfene to N,N-disubstituted 4-amino-3-phenyl-3-buten-2-ones (III) occurred in good yield only in the case of aliphatic N-substitution to give 4-dialkylamino-3,4-dihydro-6-methyl-5-phenyl-1,2-oxathiin 2,2-dioxides, whereas N,N-disubstituted 4-amino-1-phenyl-3-buten-2-ones (IV) did not react at all. Polar 1,4-cycloaddition of dichloroketene to III and IV occurred partly in the case of aromatic N-substitution, with the exception of the morpholino derivative IVd, giving in low yield N,N-disubstituted 4-amino-3,3-dichloro-3,4-dihydro-(6-methyl-5-phenyl)(6-benzyl)-2H-pyran-2-ones, which were dehydrochlorinated with DBN to the corresponding 4-amino-3-chloro-(6-methyl-5-phenyl)(6-benzyl)-2H-pyran-2-ones (VII) in good yield. In some cases of aliphatic N,N-disubstitution of III and IV, cycloaddition led directly to N,N-dialkyl derivatives VII in low yield.     

Reaction of methyl 1-bromocycloalkanecarboxylates with zinc and 2,6-bis(arylmethylene)cyclohexanones

Methyl 1-bromocyclopentane-, 1-bromocyclohexane-, and 1-bromocycloheptanecarboxylates react with zinc and 2,6-bis(arylmethylene)cyclohexanones to afford 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cyclopentan]-2(4H)-ones, 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cyclohexan]-2(4H)-ones, and 4-aryl-8-(arylmethylene)-5,6,7,8-tetrahydrospiro[chromene-3,1′-cycloheptan]-2(4H)-ones, respectively.     

Functionalization of highly electrophilic <Emphasis Type="Italic">N</Emphasis>-(2,2,2-trichloroethylidene)- and <Emphasis Type="Italic">N</Emphasis>-(2,2-dichloro-2-phenylethylidene) arenesulfonamides with dithiooxamide

Depending on the reactant ratio, dithiooxamide (ethanedithioamide) reacted as N-nucleophile or N,N′-binucleophile with highly electrophilic aldimines, N-(2,2,2-trichloroethylidene)- and N-(2,2-dichloro-2-phenylethylidene)arenesulfonamides, to give the corresponding mono- or bis-adducts, N-[2-polychloro-1-(arylsulfonylamino) ethyl]ethanedithioamides or N,N′-bis[2-polychloro-1-(arylsulfonylamino)ethyl]ethanedithioamides, in good yield.     

Lanthanide Complexes of Polyacid Ligands derived from 2, 6-bis(pyrazol-1-yl)pyridine,pyrazine, and 6, 6′-bis(pyrazol-1-yl)-2, 2′-bipyridine: Synthesis and luminescence properties

The synthesis of three novel pyrazole-containing complexing acids, N,N,N′,N′-{2, 6-bis[3-(aminomethyl)pyrazol-1-yl]-4-methoxypyridine}tetrakis(acetic acid)( 1 ), N,N,N′,N′-{2, 6-bis[3-(aminomethyl)pyrazol-1-yl]pyrazine}-tetrakis(acetic acid) ( 2 ), and N,N,N′,N′-{6, 6′-bis[3-(aminomethyl)pyrazol-1-yl]-2, 2′-bipyridine}tetrakis(acetic acid) ( 3 ) is described. Ligands 1–3 formed stable complexes with Eu^III, Tb^III, Sm^III, and Dy^III in H₂O whose relative luminescence yields, triplet-state energies, and emission decay lifetimes were measured. The number of H₂O molecules in the first coordination sphere of the lanthanide ion were also determined. Comparison of data from the Eu^III and Tb^III complexes of 1–3 and those of the parent trisheterocycle N,N,N′,N′-{2, 6-bis[3-(aminomethyl)pyrazol-l-yl]pyridine}tetrakis(acetic acid) showed that the modification of the pyridine ring for pyrazine or 2, 2′-bipyridine strongly modify the luminescence properties of the complexes. MeO Substitution at C(4) of 1 maintain the excellent properties described for the parent compound and give an additional functional group that will serve for attaching the label to biomolecules in bioaffinity applications.     

Synthesis and structures of complexes ofN-2-nitroxyethylpicolinamide and 2-(2-pyridyl)-2-oxazoline with PdCl2

The reaction ofN,N′-bis(2-nitroxyethyl)pyridine-2,6-dicarboxamide with PdCl₂ afforded previously unknowncis-(N-2-nitroxyethylpicolinamide-N,N′)dichloropalladium(II) andcis-[2-(2-pyridyl)-2-oxazoline-N,N′]dichloropalladium(II), which were isolated as a cocrystallizate of the molecular compounds. Its structure was established by X-ray diffraction analysis. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1604–1606, August, 1999.     

Reaction of sulfene and dichloroketene with open-chain N,N-disubstituted α-aminomethyleneketones. Synthesis of 4-dialkylamino-3,4-dihydro-5,6-dimethyl-1,2-oxathiin 2,2-dioxides and of 6,(5)(di)alkyl-3-chloro-4-methylphenylamino-2H-pyran-2-ones

Cycloaddition of sulfene to N,N-disubstituted 4-amino-3-methyl-3-buten-2-ones (III) occurred in fair to good yield only in the case of aliphatic N-substitution to give 4-dialkylamino-3,4-dihydro-5,6-dimethyl-1,2-oxathiin 2,2-dioxides, whereas N,N-disubstituted 1-amino-1-penten-3-ones (II) did not react at all. Cycloaddition of dichloroketene to II, III and N,N-disubstituted 4-amino-3-buten-2-ones occurred only in the case of the methylphenylamino derivative, giving in good to moderate yield 6,(5)(di)alkyl-3,3-dichloro-3,4-dihydro-4-methylphenylamino-2-Hpyran-2-ones, which were dehydrochlorinated with DBN to 6,(5)(di)alkyl-3-chloro-4-methylphenylamino-2H-pyran-2-ones.     

Spirocyclohexadienones: XII. Dienone-phenol rearrangement of 1-substituted 2-azaspiro[4.5]undeca-1,6,9-trienes and their analogs

Hydrolytic cleavage of 1-substituted 2-azaspiro[4.5]undeca-1,6,9-trienes in acid medium is accompanied by dienone-phenole rearrangement with formation of substituted N-[2-(p-hydroxyphenyl)ethyl] carboxylic acid amides. 1,2-Dimethoxy-3-oxo-15-phenyl-14-azadispiro[5.1.5.2]pentadeca-1,4,14-triene and 2′-R-7a′-methyl-3a′,4′,5′,6′,7′,7a′-hexahydrospiro[cyclohexa[2,5]diene-1,3′-indol]-4-ones undergo analogous cleavage.