Synthesis of triazoles and tetrazoles condensed with spiro(benzo[h]quinazoline-5,1′-cyclohexane)

Condensation of 3-R-4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]quinazoline-5,1-cyclohexanes) with 2-ethanolamine, 3-propanolamine, and hydrazine hydrate gives the corresponding 2-ethanolamino, 2-propanolamino, and 2-hydrazino derivatives. Triazoles and tetrazoles, a- or b-condensed with benzo[h]quinazolines were obtained from 2-hydrazinobenzo[h]quinazolines depending on the presence of a substituent at position 3.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Armenian Republic Academy of Sciences, Yerevan 375014. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 396–400, March, 2000.     

Synthesis of triazoles and tetrazoles condensed with spiro(benzo[h]quinazoline-5,1′-cycloalkanes)

3-p-Tolyl- and 3-cyclohexyl-4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]quinazoline-5,1-cycloalkanes) react with hydrazine hydrate to give 2-hydrazino-3-substituted 4-oxo-3,4,5,6-tetrahydrospiro(benzo[h]quinazoline-5,1-cycloalkanes), from which the corresponding triazoles and tetrazoles were subsequently obtainedA. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, 375014 Yerevan, Armenia Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1540–1543, November, 1999.     

Synthesis of 2,3-disubstituted 4-oxo-3,4,5,6-tetrahydrospiro-(benzo[h]quinazoline-5,1′-cyclopentanes)

3-Substituted 4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]quinazoline-5,1-cyclopentanes) were obtained by the reaction of 4-amino-3-ethoxycarbonyl-1,2-dihydrospiro(naphthalene-2,1-cyclopentane) with methyl, phenyl, and benzyl isothiocyanates and cyclization of the obtained thioureas. Condensation of the products with various halides gave 2,3-substituted 4-oxo-3,4,5,6-tetrahydrospiro(benzo[h]quinazoline-5,1-cyclopentanes). The reaction of 4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]quinazoline-5,1-cyclopentane) with 1,2-dibromoethane and 1,3-dibromopropane led to 6-oxo-7,8-dihydrospiro(benzo[h]thiazolidino[2,3-b]quinazoline-7,1-cyclopentane) and 7-oxo-8,9-dihydrospiro(benzo[h]-perhydrothiazino[2,3-b]quinazoline-8,1-cyclopentane) respectively.A. L. Mndzhoyan Institute of Fine Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Erevan. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 663–667, May, 2000.     

Synthesis of 4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]quinazoline-5,1′-cyclohexane and its reaction with dibromoalkanes

4-(N-Benzoylthioureido)-3-ethoxycarbonyl-1,2-dihydrospiro(naphthalene-2,1-cyclohexane), which was synthesized from 4-amino-3-ethoxycarbonyl-1,2-dihydrospiro(naphthalene-2,1-cyclohexane) and benzoyl isothiocyanate, cyclized to give 4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]quinazoline-5,1-cyclohexane). Reaction of the latter with 1,2-dibromoethane or 1,3-dibromopropane gave products of intramolecular dialkylation at the S and N₍₃₎ atoms.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Armenian National Academy of Sciences, Erevan 375014, Armenia. Center for the Investigation of Molecular Structure, Armenian National Academy of Sciences, Erevan 375014, Armenia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, 105–109, January, 1999.     

Synthesis of 2-alkyl thio-substituted 4-oxo-3-p-tolyl-3,4,5,6-tetrahydrospiros-(Benzo[h]quinazoline-5,1′-cycloalkanes)

Reaction of 4-amino-3-carbethoxy-1,2-dihydrospiro(naphthalene-2,1-cycloalkanes) with p-tolylisothio-cyanate gave 4-oxo-2-thioxo-3-p-tolyl-1,2,3,4,5,6-hexahydro(benzo[h]quinazoline-5,1-cycloalkanes) which could be alkylated using various halo compounds to yield the corresponding S-alkyl derivatives.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Armenian Academy of Sciences, Yerevan 375014; e-mail:msrc@ipia.sci.am. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1655–1658, December, 1999.     

Quantum chemical study of 2-substituted 4-oxo-and 4-thioxospiro(benzo[h]quinazoline-5,1′-cycloalkanes) in alkylation reactions

The steric and electronic structures of 2-substituted 4-oxo- and 4-thioxospiro(benzo[h]quinazoline-5,1-cycloalkanes and their deprotonated forms have been calculated by the semiempirical PM-3 quantum chemical method. Using the conclusions of limiting orbital theory, a quantum chemical explanation has been derived, based on the calculations made, for the selectivity of alkylation of the systems investigated.A. L. Mndzhoyan Institute of Fine Organic Chemistry, Armenian Academy of Sciences, Erevan 375014, Armenia. M. V. Lomonosov Moscow State University, Moscow 119899, Russia. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1118–1124, August, 1998.     

Synthesis and structure of 2-methyl-6-oxo-7,8-dihydrospiro(benzo[h]-triazolo[3,4-b]quinazoline-7,1′-cyclopentane)

The reaction of 4-amino-3-ethoxycarbonyl-1,2-dihydrospiro(naphthalene-2,1-cyclopentane) with benzoyl isothiocyanate led to the corresponding 4-(N-benzoylthioureido) derivative, the cyclization of which gave 4-oxo-2-thioxo-1,2,3,4,5,6-hexahydrospiro(benzo[h]qquinazoline-5,1-cyclopentane). Condensation of the latter with hydrazine hydrate gave 2-hydrazino-3,4,5,6-tetrahydrospiro(benzo[h] quinazoline-5,1-cyclopentane), which formed 6-oxo-1H-7,8-dihydrospiro(benzo[h] triazolo[3,4-b] quinazoline7,1-cyclopentane) in reaction with orthoformice ester. Methylation of the product with methyl iodide led to its 2-methyl derivative.Communication 1, see ref. [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 658–662, May, 2000.     

Synthesis of Spiro[benzo[h]chromene-4,3′-indoles] and Spiro[benzo[f]chromene-1,3′-indoles]

Russian Journal of Organic Chemistry - New spiro heterocycles, spiro[benzo[h]chromene-4,3′-indoles] and spiro[benzo[f]chromene-1,3′-indoles], have been synthesized in 50–60% yield...     

Synthesis of new pyrido[2′,3′:3,4]pyrazolo[5,1-c]-[1,2,4]triazin-4(6H)-one derivatives

Russian Chemical Bulletin - New pyrido[2′,3′:3,4]pyrazolo[5,1-c][1,2,4]triazin-4(6H)-one derivatives were synthesized from accessible 1,2,4-triazine and pyrazolo[5,1-c][1,2,4]triazine...     

Synthesis of new heterocyclic systems—substituted spiro[chromene-4,3′-indoles] and spiro[indole-3,4′-quinolines]

Methods have been developed for the synthesis of new heterocyclic systems, spiro[chromene-4,3′- indoles] and spiro[indole-3,4′-quinolines] by the base-catalyzed domino reaction of isatins with 5,5-dimethylcyclohexane- 1,3-dione (or 5,5-dimethyl-3-anilinocyclohex-2-en-1-one) and ethyl cyanoacetate.     

Synthesis of 4′H-spiro[adamantane-2,3′-isoquinoline] derivatives

Russian Journal of Organic Chemistry -     

Synthesis of spiro[isoquinoline-4,4′-pyran]-3-imines

A method has been developed for the synthesis of 4-[2-(bromomethyl)phenyl] tetrahydro-2H-4-pyrancarbonitrile and a study was carried out on the reaction of this compound with primary amines, which, depending on the conditions, leads to either 4-[2-(R-aminomethyl)phenyl]tetrahydro-2H-4-pyrancarbonitriles or hydrobromides of 2-R-aryl-2,3,2,3,5,6-hexahydrospiro[isoquinoline-4(1H),4-pyran]-3-imines.Taras Shevchenko Kiev University, 252017 Kiev, Ukraine; e-mail: vkysil@mail.univ.kiev.ua. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1035–1041, August, 2000.     

Synthesis of novel spiro[indole-3,3′-pyrrolidin]-2(1H)-ones

Diastereoselective [3+2] cycloaddition of azomethine ylide to 1,3-dimethyl-6-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5-e]thiazolo[3,2-b]-[1,2,4]triazine-2,7(1H,6H)-dione yields hitherto unknown 1,1′,3-trimethyl-3a,9a-diphenyl-3,3a,9,9a-tetrahydrodispiro(imidazo[4,5-e]thiazolo[3,2-b][1,2,4]triazine-6,3′-pyrrolidine-4′,3″-indole)-2,2″,7(1H,1″H)-triones.     

Synthesis of novel benzo[h][1,6]naphthyridine derivatives from 4-aminoquinoline and cyclic β-ketoester

This paper describes the synthesis of 2,8-dichloroquinolin-4-amine 4 and 4,5,7-trichloro-3-(2-chloroethyl)-2-methylbenzo[h][1,6]naphthyridine 8 as novel class of building blocks. Also describes the regioselective S_NAr reactions of 2,4,8-trichloroquinoline 2 on C₂ and C₄ positions with azide, similarly S_NAr reactions of benzo[h][1,6]naphthyridine 8 at C₄, C₅ positions, and S_N2 reactions on C₃-(2-chloroethyl) side chain with nucleophiles such as primary aromatic amines, methoxide/ethoxide, and azide at different temperatures.     

A new rearrangement of spiro[indane-1,3′-thiophene] and spiro[naphthalene-1,3′-thiophene] derivatives accompanied by opening of the cycloalkane ring

Abstract  

The new thioamides 2-oxoindane-1-carbothioamides and 2-oxo-1,2,3,4-tetrahydronaphthalene-1-carbothioamides underwent conjugated addition to (E)-β-nitrostyrenes followed by cyclization to give products containing 5-hydroxyimino-2-aryliminothiophene rings spiro-annulated to the 2-indanone or 2-tetralone system. On treatment with hydrochloric acid in boiling methanol the compounds underwent a new rearrangement, involving transformation of the 2-aryliminothiophene ring to a pyrrole and an opening of the alicyclic ring in the proximity of the carbonyl group, affording 2-(1,3-diaryl-2-oxo-5-thioxopyrrol-4-yl)benzeneacetic or 2-(1,3-diaryl-2-oxo-5-thioxopyrrol-4-yl)benzenepropanoic acid methyl esters. The structures of two selected pyrrole derivatives were determined by X-ray crystal analyses. The thioamides derived from 2-indanone showed unexpected reactivity towards primary alcohols and underwent conversion to 2-hydroxy-1H-indene-3-thiocarboxylic acid O-esters.     

Cu(II)-β-cyclodextrin-catalyzed synthesis of spiro[indoline-3,4′-pyrano[3,2-c]chromene]-3′-carbonitrile derivatives

Cu(II)-β-cyclodextrin-catalyzed synthesis of spiro[indoline-3,4′-pyrano[3,2-c]chromene]-3′-carbonitriles through the reaction of isatin derivatives, 4-hydroxycoumarin, and malononitrile in ethanol at room temperature.     

Efficient Catalytic Synthesis of α,ω-Di(spiro[adamantane2,3′-[1,2,4,5,7]tetroxazocan]-7′-yl)alkanes

Russian Journal of Organic Chemistry - An efficient method has been developed for the synthesis of α,ω-di(spiro[adamantane-2,3′[1,2, 4,5,7]tetroxazocan]-7′-yl)alkanes by...     

Synthesis of spiro[furan-3,3′-indolin]-2′-ones by PET-catalyzed [3+2] reactions of spiro[indoline-3,2′-oxiran]-2-ones with electron-rich olefins

An efficient procedure for the synthesis of spiro[furan-3,3′-indolin]-2-ones and dispiro[cycloalkane-1,2′-furan-3′,3″-indolin]-2″-ones has been achieved in high yields and stereoselectivity by photoinduced electron transfer-catalyzed [3+2] reactions of substituted spiro[indoline-3,2′-oxiran]-2-ones with olefins. The reactions proceed by ring opening of spiro[indoline-3,2′-oxiran]-2-ones via C_β–O bond cleavage and subsequent cycloaddition with olefins by using 2,4,6-triphenylpyrylium tetarfluoroborate (TPT) as a sensitizer.