Cycloaminomethylation of dihydric phenols catalyzed by <Emphasis Type="Italic">d</Emphasis>- and <Emphasis Type="Italic">f</Emphasis>-metal compounds

An efficient method has been developed for the synthesis of 7,16,25-triaryl-7,8,16,17,25,26-hexahydro-6H,15H,24H-tribenzo[f,m,t][1,5,8,12,15,19,3,10,17]hexaoxatriazacyclohenicosines, 3,8-diaryl-2,3,4,7,8,9-hexahydrobenzo[1,2-e:4,3-e′]bis[1,3]oxazines, 3,9-bis(chlorophenyl)-3,4,9,10-tetrahydro-2H,8H-benzo[1,2-e:3,4-e′]bis[1,3]oxazines, and 2,9-bis(chlorophenyl)-1,2,3,8,9,10-hexahydrobenzo[1,2-e:6,5-e′]bis-[1,3]oxazines via cycloaminomethylation of pyrocatechol, resorcinol, and hydroquinone with N,N-bis(methoxymethyl) anilines in the presence of samarium catalysts.     

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.     

Synthesis and conformational analysis of 6-[N,N-bis(dihydroxyphosphorylmethyl)amino]methyl-2-hydroxy-2-oxido-1,4,2-oxazaphosphorinane-4-methylphosphonic acid by NMR spectroscopy

The Kabachnik—Fields methylphosphorylation of 1,3-diaminopropan-2-ol affords a mixture of 1,3-diamino-2-hydroxypropane-N,N,N′,N′-tetrakismethylphosphonic acid and its intramolecular cyclic ester. Subsequent heating of this mixture led to the thermal dehydration of the acid with the 1,4,2-oxazaphosphorinane ring closure and the formation of 6-[N,N-bis(dihydroxyphosphorylmethyl)amino]methyl-2-hydroxy-2-oxido-1,4,2-oxazaphosphorinane4-methylphosphonic acid. A predominant chair conformation of the formed six-membered heterocycle was inferred from the data of 2D homonuclear (¹H, ¹H; J-resolved) and heteronuclear (¹H, ¹³C; HSQC, HMBC) NMR correlation spectra.     

Synthesis of New Cyclopenta[<Emphasis Type="Italic">b</Emphasis>]quinoline Derivatives

A series of new 11-(R-phenyl)-8,9-dihydro-7H-benzo[f]cyclopenta[b]quinolin-10(11H)-ones and 7,14-bis(R-phenyl)-2,3,9,10,11,14-hexahydrocyclopenta[2,3]quinolino[8,7-h]cyclopenta[b]quinoline-1,8(4H,7H)-diones were synthesized by three-component condensation of naphthalen-2-amine or naphthalene- 1,5-diamine with substituted benzaldehydes and cyclopentane-1,3-dione in one step through intermediate formation of unstable arylaminoketoenol.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-aryl-3-oxobutanethioamides with 2-amino-1,3-thiazole and 2-amino-1,3-benzothiazole

N-Aryl-3-oxobutanethioamides react with 2-amino-1,3-thiazole (2-amino-1,3-benzothiazole) in acetic acid to give mixtures of 7-methyl-5H-[1,3]thiazolo[3,2-a]pyrimidine-5-thione (2-methyl-4H-pyrimido-[2,1-b][1,3]benzothiazole-4-thione) and 5-arylimino-7-methyl-5H-[1,3]thiazolo[3,2-a]pyrimidines (4-arylimino-2-methyl-4H-pyrimido[2,1-b][1,3]benzothiazoles), whose ratio depends on the nature of the aryl substituent in the initial butanethioamide.     

Alkylation of 2-methylimidazole with iodomethylsilanes

2-Methyl-1,3-bis[(1-methylsilolan-1-yl)methyl]-1H-imidazolium triiodide, 1,3-bis{[dimethyl-(phenyl)silyl]methyl}-2-methyl-1H-imidazolium iodide and triiodide, and cyclic 3,3,5,5,10-pentamethyl-4-oxa-7-aza-1-azonia-3,5-disilabicyclo[5.2.1]deca-1(10),8-diene iodide were synthesized by solvent-free reactions of 2-methyl-1H-imidazole with 1-(iodomethyl)-1-methylsilolane, (iodomethyl)(dimethyl)phenylsilane, and ethynyl(iodomethyl)(dimethyl)silanes, respectively, in the absence of base catalyst.     

Asymmetric oxidation of verbenone ethylene dithioacetal

Asymmetric oxidation of verbenone ethylene dithioacetal with m-chloroperoxybenzoic acid at different substrate-to-oxidant ratios in methylene chloride at ?10°C gave previously unknown (1S,1′S,2S,3′S,5S)-4,6,6-trimethylspiro[bicyclo[3.1.1]hept-3-ene-2,2′-[1,3]dithiolane] 1′,3′-dioxide, (1S,2S,3′S,5S)-4,6,6-trimethylspiro[bicyclo[3.1.1]hept-3-ene-2,2′-[1,3]dithiolane] 1′,1′,3′-trioxide, and (1S,5S)-4,6,6-trimethylspiro[bicyclo-[3.1.1]hept-3-ene-2,2′-[1,3]dithiolane] 1′,1′,3′,3′-tetraoxide whose structure was determined by X-ray analysis.     

Reactions of 1,3-Dialkyl-5-amino-1,3-dihydro-2<Emphasis Type="Italic">H</Emphasis>-imidazo-[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-2-ones with acetylacetone and ethyl acetoacetate

1,3-Dialkyl-5-amino-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-ones reacted with acetylacetone to give the corresponding 4-(1,3-dialkyl-2-oxo-1,3-dihydro-2H-imidazo[4,5-b]pyridin-5-ylamino)pent-3-en-2-ones which underwent intramolecular cyclization to 1,3-dialkyl-5,7-dimethyl-1,3-dihydro-2H-imidazo[4,5-b]-[1,8]naphthyridin-2-ones on heating in polyphosphoric acid or diphenyl ether. Analogous reaction of 1,3-dialkyl-5-amino-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-ones with ethyl acetoacetate led to the formation of ethyl 3-(1,3-dialkyl-2-oxo-1,3-dihydro-2H-imidazo[4,5-b]pyridin-5-ylamino)but-2-enoates whose cyclization afforded 1,3-dialkyl-8-hydroxy-7-methyl-1,3-dihydro-2H-imidazo[5,4-b][1,8]naphthyridin-2-ones.     

Halocyclization of 3-{[2-methyl(bromo)prop-2-en-1-yl]-sulfanyl}-5<Emphasis Type="Italic">H</Emphasis>-[1,2,4]triazino[5,6-<Emphasis Type="Italic">b</Emphasis>]indoles

Reactions of 3-[(2-bromoprop-2-en-1-yl)sulfanyl]-5H-[1,2,4]triazino[5,6-b]indole with bromine and of 3-[(2-methylprop-2-en-1-yl)sulfanyl]-5H-[1,2,4]triazino[5,6-b]indole with iodine and bromine afforded 3-halomethyl-10H-[1,3]thiazolo[3′,2′: 2,3][1,2,4]triazino[5,6-b]indol-4-ium halides whose structures were determined by ¹H NMR and X-ray analysis.     

Reaction of thiourea with formaldehyde and simplest aliphatic diamines

N,N′-Bis(hydroxymethyl)thiourea reacted with propane-1,3-diamine at a molar ratio of 2 : 1 to give 5,5′-propane-1,3-diylbis(1,3,5-triazinane-2-thione), whereas 1,3,5,7,11,13,15,17-octaazatricyclo[15.3.1.1^7,11]-docosane-4,14-dithione was obtained in the reaction with equimolar amounts of the reactants. Tricyclic product was also formed in the three-component condensation of thiourea with formaldehyde and propane-1,3-diamine at a ratio of 1 : 3 : 1. The reactions of N,N′-bis(hydroxymethyl)thiourea with ethane-1,2-diamine (2 : 1) and of thiourea with formaldehyde and butane-1,4-diamine (1 : 2 : 1) afforded 5,5′-(ethane-1,2-diyl)bis(1,3,5-triazinane-2-thione) and 5,5′-(butane-1,4-diyl)bis(1,3,5-triazinane-2-thione), respectively.     

Synthesis of 1-(1,3-dialkyl-2-oxo-2,3-dihydro-1<Emphasis Type="Italic">H</Emphasis>-imidazo-[4,5-<Emphasis Type="Italic">b</Emphasis>]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acids

Nitration of 2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-one gave its 5-nitro derivative which was subjected to alkylation with dimethyl sulfate, diethyl sulfate, and benzyl(dimethyl)phenylammonium chloride. The resulting 1,3-dimethyl-, 1,3-diethyl-, and 1,3-dibenzyl-5-nitro-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones were reduced to the corresponding 1,3-dialkyl-5-amino-2,3-dihydro-1H-imidazo[4,5-b]pyridin-2-ones, and the latter reacted with itaconic acid to produce 1-(1,3-dialkyl-2-oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acids. 1-(2-Oxo-2,3-dihydro-1H-imidazo[4,5-b]pyridin-5-yl)-5-oxopyrrolidine-3-carboxylic acid was obtained by analogous reaction with 5-amino-2,3-dihydro-1H-imidazo[4,5-b]-pyridin-2-one.     

<Emphasis Type="Italic">N,N′</Emphasis>-Bis(9-anthrylmethyl)diamines as fluorescent chemosensors for transition metal cations

N,N′-Bis(9-anthryl)-substituted diamines, imidazolidines, and hexahydropyrimidines were synthesized, and their luminescence properties and complexing ability were studied. N,N′-Bis(9-anthrylmethyl)ethane-1,2-diamine and N,N′-bis(9-anthrylmethyl)butane-1,4-diamine were found to be effective and selective PET chemosensors for Zn²⁺ and H⁺, respectively. 2-[1,3-Bis(9-anthrylmethyl)hexahydropyrimidin-2-yl]-6-methoxyphenol can be used as fluorescent chemosensor for mercury(II) cations.     

Reaction of Potassium 1,1,3,3-Tetracyano-2-(2,2-dimethylpropanoyl)propenide with 2-Sulfanylethanol

The reaction of potassium 2-(2,2-dimethylpropanoyl)-1,1,3,3-tetracyanopropenide with an equimolar amount of 2-sulfanylethanol afforded 2-{5-amino-2-(tert-butyl)-4-cyano-2-[(2-hydroxyethyl)sulfanyl]- 2,3-dihydrofuran-3-ylidene}propanedinitrile, whereas 4-amino-1-(tert-butyl)-1,6-bis[(2-hydroxyethyl)- sulfanyl]-3-imino-1,3-dihydrofuro[3,4-c]pyridine-7-carbonitrile was obtained in the reaction with excess 2-sulfanylethanol.     

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.     

Azines and azoles: CXXVI. First example of a novel heterocyclic system: Pyrimido[1,6-<Emphasis Type="Italic">a</Emphasis>][1,5]benzodiazepines

4-Hydroxy-5-(2-R-2,3-dihydro-1H-1,5-benzodiazepin-4-yl)-2H-1,3-thiazine-2,6-diones readily undergo acylation at the N¹ atom of the benzodiazepine system by the action of acetic anhydride. Heating of the acetylated products in boiling dimethylformamide leads to the formation of 75–93% of the corresponding 7-acetyl-6-R-6,7-dihydropyrimido[1,6-a][1,5]benzodiazepine-1,3-diones that are derivatives of hitherto unknown fused heterocyclic system, pyrimido[1,6-a][1,5]benzodiazepine. 4-Hydroxy-5-(2-R-2,3-dihydro-1H-1,5-benzodiazepin-4-yl)-2H-1,3-thiazine-2,6-diones are converted into 1-(2-aminophenyl)-6-(2-R-vinyl)uracils on heating in boiling DMF.     

Synthesis,structure, and antimicrobial activity of a cadmium(II) complex derived from N,N′-<Emphasis Type="Italic">bis</Emphasis>(5-chlorosalicylidene)propane-1,3-diamine

The Schiff base, N,N′-bis(5-chlorosalicylidene)propane-1,3-diamine (H₂L) derived from 5-chlorosalicylaldehyde and propane-1,3-diamine, and its cadmium(II) complex, bis(μ₂-acetato)bis(μ₂-N,N′-bis(5-chlorosalicylidene)-1,3-propanediamine)tricadmium(II) Cd[Cd(CH₃COO)L]₂ (I), have been prepared and characterized by elemental analyses, IR, and single-crystal X-ray diffraction analysis. The crystal of H₂L is monoclinic: space group P2₁/n, a = 11.252(4), b = 8.972(3), c = 16.981(6) Å, β = 96.005(4)°, V = 1705.0(10) ų, Z = 4. The crystal of complex I is monoclinic: space group P2₁/c, a = 11.056(1), b = 22.284(2), c = 8.398(1) Å, β = 91.779(1)°, V = 2068.0(3) ų, Z = 2. Complex I is a centrosymmetric trinuclear cadmium(II) complex. The deprotonated Schiff base ligand coordinates to the Cd atoms through the phenolate O and imine N atoms. The effect of the Schiff base ligand and the complex on the antimicrobial activity against Staphylococcus aureus, Escherichia coli, and Candida albicans was studied.     

Microwave synthesis of new azolyl-substituted thiazolo[5,4-<Emphasis Type="Italic">d</Emphasis>]thiazoles

One-pot condensation of dithiooxamide with 4,5-dichloro-1,2-thiazole-3-carbaldehyde and 5-phenyl-1,2-oxazole-3-carbaldehyde, followed by oxidation of intermediate 2,5-dihydro[1,3]thiazolo[5,4-d]-[1,3]thiazoles with selenium dioxide, afforded previously unknown 2,5-bis(4,5-dichloro-1,2-thiazol-3-yl)- and 2,5-bis(5-phenyl-1,2-oxazol-3-yl)[1,3]thiazolo[5,4-d][1,3]thiazoles as first representative of bis-isothiazolyl- and bis-isoxazolyl thiazolothiazoles.     

Synthesis and antimicrobial activity of novel fused [1,2,4]triazino[5,6-<Emphasis Type="Italic">b</Emphasis>]indole derivatives

Synthesis of new fused systems of triazino[5,6-b]indole starting with preparation of 3-amino[1,2,4]-triazino[5,6-b]indole 1 by reaction of isatin with 2-aminoguanidinium carbonate in boiling acetic acid is presented [1]. Intermediate compound 1 reacted with aldehyde, ethyl chloroformate, triethyl orthoformate, and ninhydrine and gave new heterotetracyclic nitrogen systems, such as 3-(N ²-guanidinylimino)indole-2(1H)-one 2, 3-(N-ethoxycarbonylamino)-4H-[1,2,4]triazino[5,6-b]indole 3, 3-(N-ethoxymethyleneamino)-4H-[1,2,4]-triazino[5,6-b]indole 4, 3-(hydrazinothiocarbonylamino)-4H-[1,2,4]triazino[5,6-b]indole 5, respectively. N-(1,3-dioxoindene-2-ylidene)-4H-[1,2,4]triazino[5,6-b]indol-3-amine 6 was synthesized by reaction of compound 1 with aldehyde, ethyl chloroformate, triethyl orthoformate, and ninhydrine. New fused indole systems, pyrimido[2′,1′:3,4][1,2,4]triazino[5,6-b]indol-3(4H)-one 8, 9, 11, 12 and 1H-imidazo[2′,1′:3,4][1,2,4]triazino-[5,6-b]indol-2(3H)-one 10, were synthesized in the reaction of the intermediate 1 with bifunctional compounds. Structures of the products were elucidated from their elemental analysis and spectral data (IR, ¹H and ¹³C NMR and mass spectra). Antimicrobial activity of some synthesized compounds was tested.     

Electrophilic heterocyclization of 6-alken(yn)ylsulfanyl-pyrazolo[3,4-<Emphasis Type="Italic">d</Emphasis>]pyrimidin-4(5<Emphasis Type="Italic">H</Emphasis>)-ones

6-Allylsulfanyl-1-arylpyrazolo[3,4-d]pyrimidin-4(5H)-ones react with iodine and sulfuric acid to give angular pyrazolothiazolopyrimidine derivatives. The reaction of 6-(prop-2-yn-1-ylsulfanyl)-1-(4-tolyl)-pyrazolo[3,4-d]pyrimidin-4(5H)-one with sulfuric acid gives angularly fused pyrazolo[4,3-e][1,3]thiazolo-[3,2-a]pyrimidin-4-one, whereas in the reaction with sodium methoxide linearly fused pyrazolo[3,4-d][1,3]-thiazolo[3,2-a]pyrimidin-4-one was formed. Linearly fused pyrazolo[3′,4′:4,5]pyrimido[2,1-b][1,3]thiazole derivatives were also obtained by reaction of 1-aryl-6-(3-phenylprop-2-en-1-ylsulfanyl)pyrazolo[3,4-d]pyrimidin-4(5H)-ones with sulfuric acid.     

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.