Reaction of <Emphasis Type="Italic">N</Emphasis>-sulfonyl-1,4-benzoquinone imines with sodium azide

Depending on the conditions and the order of addition of the reactants, reactions of N-sulfonyl-1,4-benzoquinone imines with sodium azide afforded N-(3-azido-4-hydroxyphenyl)alkane(arene)sulfonamides, N-(3-azido-4-oxocyclohexa-2,5-dienylidene)alkane(arene)sulfonamides, and N-(3,5-diazido-4-hydroxyphenyl)-alkanesulfonamides. Quantum chemical calculations showed that the reactions begin with addition of azide ion to the quinone imine.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-chloro-1,4-benzoquinone imines with thiols

N-Chloro-1,4-benzoquinone imines reacted with arenethiols to give different products, depending on the conditions and initial quinone imine structure. N-(Arylsulfanyl)-1,4-benzoquinone imines were obtained as a result of nucleophilic substitution of the chlorine atom, and 1,4-benzoquinone imines containing an aryl-sulfanyl substituent in the quinoid ring were formed according to the radical mechanism. The reactions of N-chloro-1,4-benzoquinone imines with heterocyclic thiols afforded only the corresponding chlorine substitution products.     

Thiocyanation of <Emphasis Type="Italic">N</Emphasis>-arylsulfonyl-, <Emphasis Type="Italic">N</Emphasis>-aroyl-, and <Emphasis Type="Italic">N</Emphasis>-[(<Emphasis Type="Italic">N</Emphasis>-arylsulfonyl)benzimidoyl]-1,4-benzoquinone imines

Reactions of thiocyanate ion with N-aroyl-, N-arylsulfonyl-, and N-(N-arylsulfonylbenzimidoyl)-1,4-benzoquinone imines follow the 1,4-addition pattern, and the adducts undergo intramolecular cyclization to give the corresponding N-substituted 5-amino-1,3-benzoxathiol-2-ones as final products.     

Reactions of arylsulfinyl chlorides and <Emphasis Type="Italic">N</Emphasis>-(arylsulfonyl)arylsulfinimidoyl chlorides with <Emphasis Type="Italic">p</Emphasis>-aminophenols

In reactions of arylsulfinyl chlorides and N-(arylsulfonyl)arylsulfinimidoyl chlorides with p-aminophenols formed N-arylthio-1,4-benzoquinone imines, evidently through a stage of N-arylsulfinyl-4-aminophenols and N-(N-arylsulfonyl)arylsulfinylimidoyl-4-aminophenols that under the reaction conditions eliminate respectively H₂O and ArSO₂NH₂.     

Activated sterically strained C=N bond in <Emphasis Type="Italic">N</Emphasis>-substituted <Emphasis Type="Italic">p</Emphasis>-quinone mono- and diimines: XV. Synthesis,structure, and reactions with alcohols of <Emphasis Type="Italic">N</Emphasis>-carbamoyl-1,4-benzoquinone imines

The reaction of 4-aminophenols with N-nitrourea or with sodium cyanate in acetic acid gave the corresponding 4-ureidophenols which were oxidized to N-carbamoyl-1,4-benzoquinone imines, substituted N-(4-oxocyclohexa-2,5-dien-1-ylidene)ureas. N-(2,6-Dimethyl-4-oxocyclohexa-2,5-dien-1-ylidene)urea possessing activated sterically strained C=N bond reacted with alcohols to afford N-(1-alkoxy-2,6-dimethyl-4-oxocyclohexa-2,5-dienyl)ureas.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-arenesulfonyl-1,4-benzoquinone imines with acetylacetone

N-Arenesulfonyl-1,4-benzoquinone imines reacted with acetylacetone to afford different products, depending on the isolation procedure. Crystallization from polar protic solvents gave N-[4-hydroxy- 3-(2-hydroxy-4-oxopent-2-en-3-yl)phenyl]arenesulfonamides and 6-(2-oxopropyl)-4-(arenesulfonamido)phenyl acetates, whereas N-(3-acetyl-2,6-dimethyl-1-benzofuran-5-yl)arenesulfonamides were isolated by crystallization from nonpolar aprotic solvents.     

Reaction of N-substituted 2,5-dialkyl-1,4-benzoquinone imines with arenesulfinic acids

Reactions of N-aroyl-, N-arylsulfonyl-, and N-(N-arylsulfonylbenzimidoyl)-2,5-dialkyl-1,4-benzoquinone imines with sodium arenesulfinates in acetic acid gave the corresponding 1,4-, 6,1-, and 1,6-addition products. Variation of the size and donor power of substituents in positions 2 and 5 of the quinoid ring almost does not affect the ratio of the addition products, which is determined mainly by the nature of substituent on the nitrogen atom.     

Reactions of <Emphasis Type="Italic">N</Emphasis>-(Polychloroethylidene)arene-and - trifluoromethanesulfonamides with indoles

N-(Polychloroethylidene)arene-and -trifluoromethanesulfonamides reacted with indole and N-substituted indoles to give the corresponding N-[2,2-dichloro(or 2,2,2-trichloro)-1-(1H-indol-3-yl)ethyl]-substituted sulfonamides. Unlike N-(2,2,2-trichloroethylidene)trifluoromethanesulfonamide, less electrophilic N-(poly-chloroethylidene)arenesulfonamides failed to react with 1-(4-nitrophenyl)-1H-indole. Previously unknown N,N’-bis(2,2-dichloroethylidene)biphenyl-4,4’-disulfonamide reacted with 1-benzyl-1H-indole at both azomethine fragments. Likewise, reactions of 1,6-bis(1H-indol-1-yl)hexane and 1,4-bis(1H-indol-1-ylmethyl)-benzene with N-sulfonyl trichloroacetaldehyde imines involved both indole rings in the former.     

Molecular complexes of 4-nitropyridine and 4-nitroquinoline <Emphasis Type="Italic">N</Emphasis>-oxides with boron trifluoride and hydrogen chloride as intermediates in S<Subscript>N</Subscript>Ar reactions

Complexation of 4-nitropyridine N-oxides with ν- (BF₃, HCl) and π-acceptors (tetracyanoethylene, chloranil, 2,3-dichloro-5,6-dicyano-1,4-benzoquinone, 7,7,8,8-tetracyanoquinodimethane) activates the nitro group to nucleophilic replacement by chlorine. Adducts formed by 4-nitropyridine and 4-nitroquinoline N-oxides with boron trifluoride and hydrogen chloride were studied by IR spectroscopy. It was shown that these complexes belong to the n,ν type and that the donor-acceptor interaction therein involves the oxygen atom of the N-oxide group.     

3,5-Di-<Emphasis Type="Italic">tert</Emphasis>-butyl-1,2-benzoquinone in the synthesis of quinolino[4,5-<Emphasis Type="Italic">bc</Emphasis>][1,5]benzoxazepines,aminophenols, and phenoxazines

Reaction of 3,5-di-tert-butyl-1,2-benzoquinone with 5-amino-4-chloroquinolines gave derivatives of a new fused heterocyclic system, substituted quinolino[4,5-bc][1,5]benzoxazepines. The molecular structure of 9,11-di-tert-butyl-2,4,6-trimethyl-7H-quinolino[4,5-bc][1,5]benzoxazepine was determined by X-ray analysis. 3,5-Di-tert-butyl-1,2-benzoquinone reacted with o-nitro-, o-acyl-, and o-methoxycarbonylanilines and some amino-substituted nitrogen-containing heterocycles to form the corresponding sterically hindered N-aryl-(hetaryl)-o-aminophenols. Di-tert-butyl-substituted phenoxazines were obtained as a result of thermal cyclization of intermediately formed quinone imines.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-sulfonyl derivatives of 1,4-benzoquinone monoimine with substituted hydrazines

Reaction direction of N-sulfonyl derivatives of 1,4-benzoquinone monoimine with substituted hydrazines depends on the redox potential of the quinone imine and on the basicity of the hydrazine. Aryl (alkyl)hydrazines of high basicity favor the reduction of quinone monoimine. In reactions with less basic aroylhydrazones N'-(4-oxocyclohexa-2,5-dienylidene)aroylhydrazides were obtained only from the alkylsubstituted in the quinoid ring N-sulfonyl derivatives possessing a lower redox potential.     

Cyclization of trifluoro-<Emphasis Type="Italic">N</Emphasis>-(prop-2-yn-1-yl)methanesulfonamides to <Emphasis Type="Italic">N</Emphasis>-(hydroxymethyl)-1,2,3-triazoles

Three-component heterocyclizations of trifluoro-N-(prop-2-yn-1-yl)methanesulfonamide, trifluoro-N-pheny-N-(prop-2-yn-1-yl)methanesulfonamide, and trifluoro-N,N-di(prop-2-yn-1-yl)methanesulfonamide with formaldehyde and sodium azide afforded N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-, N-{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}-N-phenyl-, and N,N-bis{[2-(hydroxymethyl)-2H-1,2,3-triazol-4-yl]methyl}trifluoromethanesulfonamides as the major products together with minor 1-(hydroxymethyl)-1H-1,2,3-triazole isomers.     

Oxidative trifluoroacetamidation of (1<Emphasis Type="Italic">E</Emphasis>,3<Emphasis Type="Italic">E</Emphasis>)-1,4-diphenylbuta-1,3-diene and 1,1,4,4-tetraphenylbuta-1,3-diene

Reactions of trifluoroacetamide with (1E,3E)-1,4-diphenylbuta-1,3-diene and 1,1,4,4-tetraphenylbuta-1,3-diene in the oxidative system t-BuOCl–NaI have been studied. The reaction with (1E,3E)-1,4-diphenylbuta-1,3-diene afforded three products, N,N′-(phenylmethylene)bis(trifluoroacetamide), 3-chloro-4-iodo- 2,5-diphenyl-1-(trifluoroacetyl)pyrrolidine, and trifluoro-N-[(3E)-2-hydroxy-1,4-diphenylbut-3-en-1-yl]acetamide, with a high overall yield. 1,1,4,4-Tetraphenylbuta-1,3-diene failed to react with trifluoroacetamide.     

Reaction of N-arylcarbamoyl-1,4-benzoquinone imines with sodium azide

N-Arylcarbamoyl-1,4-benzoquinone imines reacted with sodium azide in completely regioselective fashion according to the 1,4-addition pattern with formation of 1-(3-azido-4-hydroxyphenyl)-3-arylureas. The reaction of N-arylcarbamoyl-2,6-dichloro-3,5-dimethyl-1,4-benzoquinone imines with sodium azide afforded N-arylcarbamoyl-2,6-diazido-3,5-dimethyl-1,4-benzoquinone imines as a result of nucleophilic substitution of the chlorine atoms.     

Hetero-diels–alder reaction of 5-ylidene-4-sulfanylidene-1,3-thiazolidin-2-ones with <Emphasis Type="Italic">N</Emphasis>,<Emphasis Type="Italic">N</Emphasis>′-bis(methoxycarbonyl)-1,4-benzoquinone diimine

Hetero-Diels–Alder reaction of 5-(propan-2-ylidene)-4-sulfanylidene-1,3-thiazolidin-2-one with N,N′-bis(methoxycarbonyl)-1,4-benzoquinone diimine in boiling toluene afforded 87% of dimethyl 9,9-dimethyl-2-oxo-8a,9-dihydro-2H-thiochromeno[2,3-d][1,3]thiazole-5,8(3H,4aH)-diylidenedicarbamate. Analogous reactions of 5-benzylidene-, 5-{[4-(dimethylamino)phenyl]methylidene}-, and 5-[(2-hydroxyphenyl)-methylidene]-4-sulfanylidene-1,3-thiazolidin-2-ones led to the formation of the corresponding dimethyl 9-aryl-2-oxo-3,9-dihydro-2H-thiochromeno[2,3-d][1,3]thiazole-5,8-diyldicarbamates in 64–82% yield.     

Reaction of polychloroacetaldehyde arylsulfonylimines with 2-amino-6<Emphasis Type="Italic">H</Emphasis>-1,3-thiazine-6-thiones and 2-amino-4-phenyl-6<Emphasis Type="Italic">H</Emphasis>-1,3-thiazin-6-one

2-Amino-4-R-6H-1,3-thiazine-6-thiones and 2-amino-4-phenyl-6H-1,3-thiazin-6-one react with highly electrophilic N-arylsulfonylimines of chloral and phenyldichloroacetic aldehyde at the exocyclic amino group affording in good yields products of nucleophilic addition to the azomethine group of imines: N-[2-polychloro-1-(6-thioxo-4-R-6H-1,3-thiazin-2-ylamino)ethyl]- or -[2-polychloro-1-(6-oxo-4-phenyl-6H-1,3-thiazin-2-ylamino)ethyl]arenesulfonamides.     

Rearrangements of <Emphasis Type="Italic">N</Emphasis>-ethoxycarbonylmethyl-1,2,3,4-tetrahydroquinolinium halogenalkylates effected by sodium hydride. Synthesis of 2,3,4,5-tetrahydro-1<Emphasis Type="Italic">H</Emphasis>-3-benzazepines

Quaternary salts obtained from N-alkyl-1,2,3,4-tetrahydroisoquinolines and ethyl haloacetates or diethyl bromomalonate under the action of sodium hydride in boiling 1,4-dioxane were converted into N-alkyl-N-ethoxycarbonyl-2,3,4,5-tetrahydro-1H-3-benzazepines in 49–60% yield. From the reaction mixture by column chromatography products of β-elimination by Hofmann reaction, 2-(N-methyl-N-ethoxycarbonylmethyl)-aminomethylstyrenes were also isolated (yield 0.6–16%).     

Diels-alder reactions of alumina-and magnesacyclopentadienes

[4π + 2π]-Cycloaddition of substituted alumina-and magnesacyclopenta-2,4-dienes with such dienophiles as maleic anhydride, N-methylmaleimide, 1,4-benzoquinone, and 1,4-naphthoquinone resulted in the formation of the corresponding fused alumina-and magnesanorbornenes whose hydrolysis gave isobenzofuran, isoindole, naphthalene, and anthracene derivatives in high yields.     

Free-Radical Co-Oligomerization of <Emphasis Type="Italic">N</Emphasis>-Vinylpyrroles with <Emphasis Type="Italic">N</Emphasis>-Vinylpyrrolidone: A Route to New Bioactive Oligomers

Co-oligomerization of N-vinylpyrroles (N-vinyl-2,3-dimethylpyrrole, N-vinyl-2-phenylpyrrole, N-vinyl-2,3-diphenylpyrrole, N-vinyl-2-(2-thienyl)pyrrole, and N-vinyl-2-[1-(4,5,6,7-tetrahydroindolyl) ethyl]-4,5,6,7-tetrahydroidole) with N-vinylpyrrolidone in the presence of a radical initiator (AIBN) gives co-oligomers with molecular masses of 1600–5200 in up to 87% yield. The products are readily soluble in organic solvents (benzene, 1,4_dioxane, and chloroform), and in the case of high N-vinylpyrrolidone content, also in ethanol and in water. The co-oligomers are non-toxic or have low toxicity (the lethal dose LD₅₀ = 1300–2000) and possess biological activity.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-alkyl(aryl)aminocarbonyl-1,4-benzoquinone monoimines with alcohols

Reactions of N-alkyl(aryl)aminocarbonyl-3,5-dimethyl-1,4-benzoquinone monoimines with alcohols led to the formation of products of 1,2-addition, quinolide compounds. They are the final products in reactions with alkyl derivatives, but in event of aryl derivatives they underwent cyclization with the subsequent elimination of the alcohol molecule to provide 4,7a-dimethyl-1-aryl-7,7a-dihydro-1H-benzimidazole-2,6-diones.