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.     

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.     

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.     

Thermal Rearrangements of 3<Emphasis Type="Italic">H</Emphasis>- and 4<Emphasis Type="Italic">H</Emphasis>-Pyrazoles Prepared by Reactions of 9-Diazofluoren with Methyl Tetrolate and Methyl 3-Phenylpropiolate

9-Diazofluoren adds in Et₂O at 20°C to methyltetrolate in keeping with Auwers rule and nonregioselectively adds to methyl-3-phenylpropiolate with the formation of spirocyclic 3H-pyrazoles. The methyltetrolate adduct at boiling in toluene converts into methyl 3a-methyl-3aH-dibenzo[e,g]indazole-3-carboxylate, at 190°C in benzene, into methyl 3-methyl-2H-dibenzo[e,g]indazole-2-carboxylate, and at 160°C in methanol, into 3-methyl-2H-dibenzo[e,g]indazole. Auwers adduct of methyl 3-phenylpropiolate at boiling in benzene gives cyclopropene derivative and at boiling in methanol isomerizes into methyl 3a-phenyl-3aHdibenzo[e,g]indazole-3-carboxylate. Anti-Auwers adduct at boiling in benzene isomerizes into methyl 2-phenylpyrazolo[1,5-f]phenanthridine-3-carboxylate.     

Hetero-Diels–Alder Reaction of Aroylpyrrolo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinoxalinetriones with Styrene

Hetero-Diels–Alder reaction of 3-aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones with styrene afforded diastereoisomeric (5R*,6aR*)- and (5S*,6aR*)-3,5-diaryl-5,6-dihydropyrano[4′,3′:2,3]pyrrolo[1,2-a]-quinoxaline-1,2,7(8H)-triones.     

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.     

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.     

Synthesis of Pyrano[4′,3′:2,3]pyrrolo[1,2-<Emphasis Type="Italic">a</Emphasis>]quinoxalines by Reaction of Aroylpyrroloquinoxalines with Alkyl Vinyl Ethers

Thermally induced [4 + 2]-cycloaddition of 3-aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones with alkyl vinyl ethers afforded mixtures of diastereoisomeric (5S*,6aR*)- and (5R*,6aR*)-5-alkoxy-3-aryl-5,6-dihydropyrano[ 4′,3′: 2,3]pyrrolo[1,2-a]quinoxaline-1,2,7(8H)-triones.     

Convenient Way to the Synthesis of Polycyclic Fused Benzimidazole Derivatives with a Bridgehead Nitrogen Atom

Effective synthesis was developed for 1,2,3,4-tetrahydropyrido- and pyrido[1,2-a]benzimidazole-7,8-diamines that underlie the preparation of new polyazaheterocycles: pyrido[1,2-а]imidazo[4,5-f]-benzimidazole, 7Н-pyrido[1,2-а]imidazo[4,5-f]benzotriazole, pyrido[1,2-а]imidazo[4,5-g]quinoxaline.     

Chlorokomplexe von Ti(III), V(III) und Cr(III) in Propandiol-1,2-carbonat und Trimethylphosphat

Addition of chloride ions to the hexasolvated ions of Ti(III), V(III) and Cr(III) in propandiol-1,2-carbonate (PDC) and trimethylphosphate (TMP) may lead to the following complexes: [TiCl]²⁺ (inPDC), [TiCl₂]⁺ (inTMP), TiCl₃ (inPDC andTMP, low solubility inTMP), [TiCl₄]^? (inPDC andTMP?), [TiCl₆]^3? (inPDC); [VCl]²⁺ (inPDC andTMP), VCl₃ (inPDC andTMP, low solubility inTMP), [VCl₄]^? (inPDC); [CrCl]²⁺ (inTMP), [CrCl₂]⁺ (inPDC), CrCl₃ (inPDC andTMP), [CrCl₄]^? (inPDC).     

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.     

2-amino-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-<Emphasis Type="Italic">a</Emphasis>]pyrimidines: Synthesis and reactions with electrophilic reagents

The hydrogenation of 2-amino-5-R-7-R′-4,7-dihydro-1,2,4-triazolo[1,5-a]pyrimidines with NaBH₄ led to the formation of 2-amino-5-R-7-R′-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]pyrimidines. Acylation, sulfonylation, and alkylation of these compounds depending on conditions and the reagent character occur at the amino group, atoms N³ or N⁴. The treatment with alkali of 2-amino-3-benzyl-5-R-7-R′-4,5,6,7-tetrahydro-1,2,4-triazolo-[1,5-a]pyrimidinium bromide resulted in 2-amino-3-benzyl-5-R-7-R′-3,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]-pyrimidine, similar reaction of 2-acetamido-3-benzyl-5-R-7-R′-4,5,6,7-tetrahydro-1,2,4-triazolo[1,5-a]-pyrimidinium bromide gave a mesoionic product of a hydrogen elimination from the amide nitrogen atom.     

Diastereoselective 1,3-Dipolar Cycloaddition of Nitrones to 1<Emphasis Type="Italic">H</Emphasis>-Pyrrole-2,3-diones. Synthesis of pyrrolo[3,2-<Emphasis Type="Italic">d</Emphasis>]isoxazoles

1H-pyrrol-2,3-diones react with nitrones affording substituted pyrrolо[3,2-d]isoxazoles. The structures of ethyl (3R*,3aR*,6aR*)-6-benzyl-3-(4-bromophenyl)-4,5-dioxo-2,6a-diphenylhexahydro-3aHpyrrolo[ 3,2-d]isoxazole-3a-carboxylate and dimethyl (3R*,3aR*,6aS*)-3-(4-bromophenyl)-4,5-dioxo-2,6-diphenyltetrahydro-3aH-pyrrolo[3,2-d]isoxazole-3a,6a(4H)-dicarboxylate were proved by single-crystal X-ray analysis.     

Chloro- und Azidokomplexe des Vanadyl(IV)-Ions in Acetonitril,Propandiol-1,2-carbonat,Trimethylphosphat und Dimethylsulfoxid

The formation of chloro- and azidocomplexes of VO²⁺(IV) is investigated in acetonitrile (AN), propanediol-1,2-carbonate (PDC), trimethyl phosphate (TMP) by spectrophotometric, potentiometric and conductometric methods. The following coordination forms are indicated: [VOCl]⁺ inAN, PDC andDMSO), [VOCl₂] (inAN, PDC andTMP), [VOCl₃]^? (inPDC andTMP[?]), [VOCl₄]^2? (inAN, PDC andTMP); [VON₃]⁺ (inAN, PDC andDMSO), [VO(N₃)₂] (inAN, PDC, TMP andDMSO), [VO(N₃)_2+n]^n? (inAN, PDC, TMP andDMSO). The results are interpreted by the donor numbers and sterical properties of the solvent molecules.     

Synthesis of Bisthiacalix[4]arene: Reaction of Piperazine with Monoacrylamide Derivative of <Emphasis Type="Italic">p</Emphasis>-<Emphasis Type="Italic">tert</Emphasis>-Butylthiacalix[4]arene

The reaction of acryloyl chloride with the monoamine derivative of p-tert-butylthiacalix[4]arene was used to synthesize p-tert-butylthiacalix[4]arene monoacrylamide in the 1,3-alternate conformation. The effect of the nature of the amine on the result of its Michael reaction with the synthesized p-tert-butylthiacalix[4]arene monoacrylamide was studied. The latter was reacted with piperazine to obtain bisthiacalix[4]arene with the macrocyclic fragments in the 1,3-alternate conformation.     

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.     

Synthesis of oxo derivatives of <Emphasis Type="Italic">N</Emphasis>-(<Emphasis Type="Italic">p</Emphasis>-tolysulfonyl)hexahydrocycloalka[<Emphasis Type="Italic">b</Emphasis>]indoles

Hydroxymercuration-demercuration of N-p-tolysulfonyl-4,4a,9,9a-tetrahydro-3H-carbazoles and N-p-tolyl(or methyl)sulfonyl-1,3a,4,8b-tetrahydrocyclopenta[b]indoles leads to the formation of the corresponding N-p-tolylsulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-2-ols and N-p-tolyl(or methyl)sulfonyl-1,2,3,3a,4,8b-hexahydrocyclopenta[b]indol-2-ols. The latter are oxidized to 2-oxo derivatives with potassium dichromate. The oxidation of 2-methoxy-8-methyl-N-p-tolylsulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-1-ol under analogous conditions gives 2-methoxy-8-methyl-N-p-tolysulfonyl-2,3,4,4a,9,9a-hexahydro-1H-carbazol-1-one.     

Synthesis of arylmethylpyrimidinetriones and pyrimidoquinolinediones with fluorescent and nonlinear-optical properties

5-Arylmethyl-2,4,6-(1H,3H,5H)pyrimidinetriones and 12-aryl-8,12-dihydrobenzo[f]pyrimido[4,5-b]quinoline-9,11-(7H,10H)diones were synthesized, and their spectral-luminescence and nonlinear-optical properties were examined.     

Condensation of fluorine-substituted benzaldehydes with amines and cyclic ketones

Condensation of fluorine-containing benzaldehydes with naphthalen-2-amine or quinolin-6-amine and cyclic ketones (cyclopentanone, cyclohexanone, and 4-methylcyclohexanone) gave new fluorine-containing derivatives of cyclopenta[c]benzo[f]quinoline, benzo[a]phenanthridine, and cyclopenta[a]- and benzo[a]-[4,7]phenanthroline. Intermediate products, 2-[(fluorophenyl)(2-naphthylamino or quinolin-6-ylamino)methylidene] cyclohexanones, dihydrobenzo[f]quinolines, and dihydro-4,7-phenanthrolines, were isolated.