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 spiro(benzo[h]quinazoline-5,1′-cyclohexane) derivatives

3-p-Methoxyphenyl-4-oxo-2-mercapto-3, 4, 5, 6-tetrahydrospiro(benzo[h]quinazoline-4,1 -cyclohexane) wassynthesized by the reaction of 4-amino-3-ethoxycarbonvl-1, 2-dihydrospiro(naphthalene-2,1 '-cyclohexane) (1) with p-methoxyphenvl isothiocyanate without separation of the thioureido derivative. Amino ester 1 is transformed byacetamide and formamideinto 2-methyl-4-oxo-3, 4, 5, 6-tetrahydrospiro(benzo[h]quinazoline-5,1 -cyclohexane) and 4-oxo-3, 4, 5, 6-tetrahydrospiro(benzo[h]quinazoline-5,1-cyclohexane (11), respectively. Alkylation of quinazoline 11 with methyl iodide results in formation of 3-methyl-4-oxo-3, 4, 5, 6-tetrahydro-spiro (benzo[h]quinazoline-5,1 -cyclohexane). Amino ester 1 reacts with caprolactam with formation of 2, 3 pentamethylene-4-oxo-3, 4, 5, 6-tetrahydrospiro(benzo[h]quinazoline-5,1-cyclohexane). 4-Ethoxymethyleneamino-3-ethoxy-carbonyl-1,2-dihydrospiro(naphthalene-2,1-cyclohexane) was synthesized by the reaction of amino ester 1 with o-formic ester, and was converted into 3-amino-4-oxo-3, 4,5, 6-tetrahydro-spiro(benzo[h]quinazoline-5,1-cyclohexane) (VIII) by hydrazine hydrate. Aminoquinazoline VIII is acylated by acid chlorides with formation of 3-acylamino-4-oxo-3,4,5,6-tetrahydrospiro(benzo[h]quinazoline-5,1-cyclohexanes) and forms 3-benzyl-ideneamino-4-oxo-3,4,5,6-teirahydrospiro(benzo[h]quinazoline-5,1-cyclohexane) with benzaldehyde.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 530–533, April, 1996     

Synthesis of Spiro[indole-3,2′-pyrroles] from Pyrrolopyrazinetriones and Aminocyclohexenones

Russian Journal of Organic Chemistry - 8-Benzoyl-2-phenyl-3,4-dihydropyrrolo[1,2-a]pyrazine-1,6,7(2H)-trione reacted with 3-(alkylamino)-5,5-dimethylcyclohex-2-en-1-ones to give...     

Green Aspect for Multicomponent Synthesis of Spiro[4H-indeno[1,2-b]pyridine-4,3′-[3H]indoles]

An efficient, four-component reaction of isatin, 1,3-indanedione, ethyl acetoacetate, and ammonium acetate in ethanol/water (9:1) system furnished spiro[4H-indeno[1,2-b]pyridine-4,3′-[3H]indoles] at room temperature. Merits of the method are mild reaction conditions, simple workup procedure, and ambient temperature. The synthesized compounds exhibit excellent fluorescence properties.     

A Large-Scale Synthesis of Spiro [Cyclopropane-1,9′- [9H] Fluorene] and Derivatives

Our studies of the conjugative properties of cyclopropanes required the synthesis of large quantities of spiro [cyclopropane-1,9′- [9H] fluorene] (1) and its derivatives.¹ The method of Corey² is suited for the preparation of modest (1–5 g) amounts of 1 in one step. This procedure has failed to produce the desired cyclopropane when applied to substituted fluorenones.³     

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 New Spiro[1,4,2-dioxazole-5,3′-indolin]-2′-one by 1,3-Dipolar Cycloaddition

Novel spiro[1,4,2-dioxazole-5,3′-indolin]-2′-one derivatives were synthesized by 1,3-dipolar cycloaddition reactions of the isatin derivative with aryl nitrile oxide. The cycloadducts were characterized by spectral data including ¹H NMR, ¹³C NMR, infrared, mass spectra, and elementary analysis.     

Synthesis and Reactivity of 2-(Furan-2-yl)benzo[1,2-d:4,3-d′]bis[1,3]thiazole

Russian Journal of Organic Chemistry - Acylation of 1,3-benzothiazol-6-amine with furan-2-carbonyl chloride in propan-2-ol gave N-(1,3-benzothiazol-6-yl)furan-2-carboxamide which was converted to...     

Antifertility Agent: Stereoselective Synthesis of Spiro[cyclopropane-1,7′-yuehchukene]

A facile synthesis of 6′β-(indol-3″-yl)-9′- methyl-5′,6′,-6′αβ,7′,8′,10′ αβ-hexahydrospiro[cyclopropane-1,7′-indeno[2,1-b]indole] (2), an analogue of yuehchukene (1), is described.     

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.     

Novel Fluorinated Spiro [Indole-indazolyl-thiazolidine]-2,4′-diones: Design and Synthesis

The reaction of indol-2,3-diones ( 1a–i ) with 5-aminoindazole ( 2 ) has resulted in the formation of hitherto unknown 3-(indazol-5-yl)iminoindol-2-ones ( 3a–i ) in quantitative yields which, on 1,3-dipolar cyclocondensation with mercaptoacetic acid ( 4 ), has afforded a series of new spiro heterocycles, 3′-(indazol-5-yl) spiro[3H, indol-3, 2′ -thiazolidine]-2,4′-diones* ( 5a–i ).     

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 and Investigation of Mass Spectra of 3-[5′-(2′-Substituent)thienyl]benzo[5,6]coumarins

3-[5'-(2'-Hydroxycarbonyl)thienyl]benzo[5,6]coumarin ( 3 ) was prepared via condensation of 2 with thioglycolic acid in the presence of AcONa and Ac 2 O. Esterification of 3 with alcohols gave 3-[5'-(2'-alkoxycarbonyl)thienyl]benzo[5,6]-coumarins ( 4a , b ). The chemical behavior of 4 toward nucleophilic reagents (such as ammonia, hydroxyl amine, and hydrazine derivatives) is described. The electron impact ionization mass spectra of compounds 4b , 5 , and 8a , b show a weak molecular ion peak and a base peak of m / z 278 resulting from a cleavage fragmentation. In contrest compounds 3 and 4a show a base peak of m / z 250 and m / z 74 resulting from fragmentation. Compounds 9 and 10 give a characteristic fragmentation pattern with a very stable fragment of m / z 305.     

Synthesis of Novel Spiro[indol-2,2′-pyrroles] Using Isocyanide-Based Multicomponent Reaction

An efficient and facile method for the synthesis of novel spiro[indole-2,2′-pyrroles] from N-methyl-3-isatin imines, t-butyl isocyanide, and dialkyl acetylenedicarboxylate has been achieved by [3 + 2] cyclo addition reaction. All the products were purified by column chromatography as yellow solids and confirmed with ¹H NMR, ¹³C NMR, fast atom bombardment, mass, and infrared. Compound 11 was further confirmed with x-ray analysis.     

Three-Component Spiro Heterocyclization of Pyrrolediones with Aminoindenones. Synthesis of Spiro[diindeno[1,2-b:2′,1′-e]pyridine-11,3′-pyrroles]

Russian Journal of Organic Chemistry - 4,5-Dibenzoyl-1H-pyrrole-2,3-diones and 4-benzoyl-5-phenyl-1H-pyrrole-2,3-diones reacted with 3-arylamino-1H-inden-1-ones at a molar ratio of 1:2 to give...     

Synthesis and Crystal Structure of 2-Amino- 5,6-dihydro-4-（3,4-dimethoxyphenyl）-4H- benzo[h]chromene-3-carbonitrile

1 INTRODUCTION 2-Aminochromene is an important class of com- pounds found as the main compounds of many natu- rally occurring products employed as cosmetics and pigments and utilized as potential biodegradeable agro- chemicals[1～3]. In recent years, montmorillonite in natural and ex- changed forms has received considerable attention in different organic syntheses because of its environ- mental compatibility, low cost, high selectivity, reusa- bility and operational simplicity[4], such as …     

Reaction of Pyrrolooxazinetriones with Diphenylguanidine. Synthesis of Substituted Spiro[imidazole-4,2′-pyrroles]

Russian Journal of Organic Chemistry - 8-Aroyl-3,4-dihydropyrrolo[2,1-c][1,4]oxazine-1,6,7(1H)-triones reacted with 1,3-diphenylguani­dine to give...     

Synthesis of Green Colored Photochromic 6′-Arylamino Spiro [2H]Naphth[1,2-b]oxazines

The published route to a series of 6′-arylamino substituted photochromic spirooxazines has been investigated with improvements made to perform the synthesis in satisfactory yield. The route has been exemplified with several novel derivatives prepared (including hydroxyl functionalised). Additionally, a one-pot procedure for the conversion of suitably functionalized 1,2-naphthoquinones into the photochromic compounds is reported.     

Synthesis of spiro[furo[3,4-b]pyran-4,3′-pyrroles] by reaction of pyrrolediones with malononitrile and tetronic acid

Russian Journal of Organic Chemistry - Substituted ethyl...