Synthesis of New 2′-(2- and 3-Aminopropanoyl)-6′,7′-dimethoxy-2′,3′-dihydro-1′H-spiro[cyclopentane-1,4′-isoquinoline]-1′-carboxamides

Russian Journal of Organic Chemistry - 6′,7′-Dimethoxy-N-methyl-2′,3′-dihydro-1′H-spiro[cyclopentane-1,4′-isoquinoline]-1′-carboxamide reacted with...     

5′,5′,6,6-Tetramethyl-6,7-dihydro-3′H-spiro[1,3-benzodithiole-2,1′-cyclohexane]-3′,4(5H)-dione

Russian Journal of Organic Chemistry -     

Three-component synthesis of 1-substituted 6′,7′-dimethoxy-4′H-spiro[adamantane-2,3′-isoquinolines]

Russian Journal of Organic Chemistry -     

Efficient one-pot synthesis of novel 6′,9′-dihydro-2H,7′H-spiro[pyrimidine-5,8′-[1,3]dioxolo[4,5-f]quinoline]-2,4,6(1H,3H)-trione derivatives under mild and “green” reaction conditions

In this paper, an efficient method is introduced for the synthesis of 7′,9′-disubstituted 6′,9′-dihydro-2H,7′H-spiro[pyrimidine-5,8′-[1,3]dioxolo[4,5-f]quinoline]-2,4,6(1H,3H)-trione derivatives under mild and “green” reaction conditions. The method is based on one-pot multicomponent reaction of an aldehyde, barbituric acid, and benzo[d][1,3]dioxol-5-amine in ethanol as a green and environmentally friendly solvent. The reaction has given the products in the highest isolated yield in the presence of acetic acid as catalyst under reflux conditions. Various aldehydes, bearing electron-donating or -withdrawing functionalities have been used under the optimized conditions and successfully gave the desired products (13 examples) in high isolated yields.     

Investigations in the region of 2,3′-biquinoline. 3. Synthesis of 2′-alkyl(aryl)-1′,2′-dihydro-2,3′-biquinolines and 2′-alkyl(aryl)-2,3′-biquinolines

A method was developed for the synthesis of 2-alkyl(aryl)-1,2-dihydro-2,3-biquinolines, based on the addition of organolithium compounds to 2,3-biquinoline in the presence of tetramethylethylenediamine. Their oxidation with manganese dioxide led to 2-alkyl(aryl)-2,3-biquinolines.For Communication 2, see [1].Stavropol State University, Stavropol 355009, Russia. Russian Chemical-Technology University, Moscow 125190. Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 3, pp. 350–354, March, 1998.     

Synthesis of 2-[(E)-Hex-1′-enyl]tetrahydropyran Starting from 3-Nitro-4,5-dihydro-6H-pyran

The four steps preparation of 2-[(E)-hex-1′-enyl]tetrahydropyran starting from 3-nitro-4,5-dihydro-6H-pyran has been carried out in 40% overall yield.     

Synthesis of functionalized 5H-spiro[furan-2,2′-indene]-1′,3′,5-triones from primary amines, acetylenic esters and ninhydrin

An effective route to functionalized 5H-spiro[furan-2,2??-indene]-1??,3??,5-triones is described via tandem reaction of primary amines, acetylenic esters and ninhydrin.     

An expeditious access of 2,5′-dioxo-5′,6′,7′,8′-tetrahydro-1′H-spiro[indoline-3,4′-quinoline]-3′-carboxylate by reaction of isatin,ethyl cyanoacetate and enaminone in water

We have demonstrated three component reaction of isatin, enaminone and ethyl cyanoacetate leading to sprirooxindole scaffold without catalyst in water. The synthetic protocol has several advantages like wide substrate scope, atom-economy and operationally simple experimental procedures which provides rapid access to library of compounds. The mechanistic details of the reaction has been investigated during the course of study.     

Five-membered 2,3-dioxo heterocycles: LX. Reaction of 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones with cyclic enehydrazino ketones. Crystalline and molecular structure of N-[3′-benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6, 6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]-3-nitrobenzamide

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with N′-(5,5-dimethyl-3-oxocyclohex-1-en-1-yl)benzohydrazides to give the corresponding N-[3′-aroyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]benzamides. The molecular and crystalline structure of one of the products, N-[3′-benzoyl-4′-hydroxy-1′-(2-hydroxyphenyl)-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]-3-nitrobenzamide, was determined by X-ray analysis.     

Reactions of 2′-oxo-1′,2′-dihydrospiro[cyclopropane-1,3′-indole]-2,2,3,3-tetracarbonitriles with nucleophiles

2′-Oxo-1′,2′-dihydrospiro[cyclopropane-1,3′-indole]-2,2,3,3-tetracarbonitriles reacted with oxygencentered nucleophiles to form addition products at the cyano groups with conservation of the three-membered ring. Reactions of the title compounds with alcohols required the presence of base catalyst, and the products, 2-amino-4,4-dialkoxy-2′-oxo-1′,2′-dihydrospiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicarbonitriles, were converted into the corresponding 2-imino-2′,4-dioxospiro[3-azabicyclo[3.1.0]hexane-6,3′-indole]-1,5-dicarbonitriles and 2,2′,4-trioxospiro[3-azabicyclo[3.1.0]hexane-6,3′-indole]-1,5-dicarbonitriles by the action of acetic and sulfuric acids, respectively. The reactions with ketone oximes occurred in the absence of a catalyst, yielding 2-amino-4,4-bis(alkylideneaminooxy)-2′-oxo-1′,2′-dihydrospiro[3-azabicyclo[3.1.0]hex-2-ene-6,3′-indole]-1,5-dicarbonitriles. The reactions with thiols, aliphatic amines, and anilines were accompanied by opening of the three-membered ring. In the reactions with triphenylphosphine and thiols 2-(2-oxo-2,3-dihydro-1H-indol-3-ylidene)malononitrile was obtained, while morpholine and N,N-dimethylaniline gave rise, respectively, to 3,3-diaryl-and 3,3-dimorpholino-1H-indol-2(3H)-ones and tri- and dicyanoethylene derivatives.     

Synthesis of N-Aryl-2-(1′,6′-dihydro-6′-pyridazinone-3′-carbonyl) Thiosemicarbazides and Their Related Heterocyclic Compounds

Introduction Somepyridazineshavebeenexaminedforac- tivityagainstsporozoanandflagellateparasitesand forantiamebicactivity[1]. 6-Aryl-4,5-dihydro-3(2H)-pyridazinonesex- hibitvariousbiologicalpropertiesincludingreduc- tionofbloodpressure,inhibitionofplateletaggre- gation,antiinflammation,andstrongplateletag- gregationinhibitingactioncoupledwithahypoten- siveaction.Italsopossessesweakpositiveinotrop- icactivityforthemanagementofcongestiveheart failure.Threepara-substitueddihydropyridazi- nonesare…     

Pyrido[2,3-d]dipyrimidines 8. Synthesis of pyrrolo(2′,3′∶4,5)pyrido[2,3-d]pyrimidines

The reaction of 1,3-dimethyl-5-chloro-6-nitropyrido[2,3-d]pyrimidine-2,4-dione with CH-acids yielded 5-substituted pyridol[2,3-d]pyrimidines which were used in the synthesis of pyrrolo(2,34,5)pyrido[2,3-d]pyrimidines.For Communication 7, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 800–803, June, 1993.     

Five-membered dioxo heterocycles: CIV. Reaction of methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates with cyclic enehydrazines. Crystal and molecular structure of N-[3′-benzoyl-1′-(4-chlorophenyl)-4′-hydroxy-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro-[indole-3,2′-pyrrol]-1(2H)-yl]benzamide

Methyl 1-aryl-3-benzoyl-4,5-dioxo-4,5-dihydro-1H-pyrrole-2-carboxylates reacted with N′-(5,5-dimethyl-3-oxocyclohex-1-en-1-yl)benzohydrazides and N′-(5,5-dimethyl-3-oxocyclohex-1-en-1-yl)-2,2-diphenylacetohydrazide to give substituted N-[1′-aryl-3′-benzoyl-4′-hydroxy-6,6-dimethyl-2,4,5′-trioxo-1′,4,5,5′,6,7-hexahydrospiro[indole-3,2′-pyrrol]-1(2H)-yl]benz- and -diphenylacetamides.     

Formation of 3a′,8′-dimethyl-3a′,5′-dihydro-1′H,3′H-dispiro-[cyclohexane-1,3′-furo[3,4-f][2]benzofuran-5′,1″-cyclohexane]-1′,7′(4′H)-dione in the reaction of 3-acetyl-4-methyl-1-oxaspiro[4.5]dec-3-en-2-one with potassium hydroxide

3a′,8′-Dimethyl-3a′,5′-dihydro-1′H,3′H-dispiro[cyclohexane-1,3′-furo[3,4-f][2]benzofuran-5′,1″-cyclohexane]-1′,7′(4′H)-dione was synthesized by reaction of 3-acetyl-4-methyl-1-oxaspiro[4.5]dec-3-en-2-one with potassium hydroxide in water.     

Synthesis,characterization, and investigations of antimicrobial activity of 6,6-dimethyl-3-aryl-3′,4′,6,7-tetrahydro-1′H,3H-spiro[benzofuran-2,2′-naphthalene]-1′,4(5H)-dione

Chalcone-like compounds 3a–l, 2-(benzylidene)-3,4-dihydronaphthalen-1(2H)-one, were synthesized from the addition of different benzaldehyde derivatives (2a–l) to 1,2,3,4-tetrahydro-1-napthalone (1) in basic medium. Mn(OAc)₃-mediated addition of dimedone (4) to chalcone-like compounds gave the spirobenzofuran derivatives (5a-l), 6,6-dimethyl-3-aryl-3′,4′,6,7-tetrahydro-1′H,3H-spiro[benzofuran-2,2′-naphthalene]-1′,4 (5H)-dione, in good yields. The structures of synthesized compounds 5a–l were elucidated on basis of spectral data (NMR, IR) and elemental analysis. In addition, their antibacterial activities were screened against some human pathogenic microorganisms.     

Efficient synthesis of 5,6-dihydrothieno[3′,2′:4,5]-thieno[2,3-d]pyrimidin-4(3H)-ones via an iminophosphorane

5,6-Dihydrothieno[3′,2′:4,5]thieno[2,3-d]pyrimidin-4(3H)-ones 6 were synthesized in yields of 71-87%by a consecutive method,which includes aza-Wittig reaction of iminophosphorane 3 with aromatic isocynate to give carbodiimide 4 and subsequent reaction of 4 with various amines,phenols or alcohols in the presence of catalytic amount of sodium ethoxide or solid potassium carbonate.     

Diels-alder reactions with cyclic sulfones: VIII. Organic catalysis in the synthesis of spiro[1-benzothiophene-4,5′-pyrimidine]-2′,4′,6′-trione 1,1-dioxides and 2′-thioxospiro[1-benzothiophene-4,5′-pyrimidine]-4′,6′-dione 1,1-dioxides

5-Isopropenyl-2,3-dihydrothiophene 1,1-dioxide reacted with 5-methylidenepyrimidine-2,4,6-triones and 5-methylidene-2-thioxopyrimidine-4,6-diones in the presence of chiral amines or amino acids with high regio- and stereoselectivity to give optically active derivatives of barbituric and thiobarbituric acids spirofused at the 5-position to 1-benzothiophene 1,1-dioxide fragment. The reaction of 5-isopropenyl-2,3-dihydrothiophene 1,1-dioxide with 5-(2-methoxybenzylidene)-2-thioxopyrimidine-4,6-dione (generated in situ from 2-methoxybenzaldehyde and thiobarbituric acid) in the presence of (?)-ephedrine or L-4-(tert-butyldimethylsiloxy) proline gave the corresponding 2-thioxospiro[1-benzothiophene-4,5′-pyrimidine]-4′,6′-dione 1,1-dioxide with an enantiomeric excess of 80%.     

Five-membered 2,3-dioxo heterocycles: LXX. Spiro heterocyclization of 1H-pyrrole-2,3-diones by the action of 1,5-binucleophiles. Crystalline and molecular structure of ethyl 1′-benzyl-7-methoxy-3,3-dimethyl-1,2′-dioxo-5′-phenyl-1′,2,2′,3,4,10-hexahydro-1H-spiro[acridine-9,3′-pyrrole]-4′-carboxylate

Ethyl 1-alkyl-4,5-dioxo-2-phenyl-4,5-dihydro-1H-pyrrole-3-carboxylates reacted with 3-arylamino-5,5-dimethylcyclohex-2-en-1-ones as carbon-centered 1,5-binucleophiles to give the corresponding substituted ethyl 1′-alkyl-3,3-dimethyl-1,2′-dioxo-5′-phenyl-1′,2,2′,3,4,10-hexahydro-1H-spiro[acridine-9,3′-pyrrole]-4′-carboxylates whose structure was proved by X-ray analysis.     

Group 6 metal carbonyl complexes of 3′H-spiro[indole-3,2′-[1,3]benzothiazole-2(1H)]-one

The spiro-compound 3′H-spiro[indole-3,2′-[1,3]benzothiazole-2(1H)-one (IBTH₂) was synthesized and its structure was determined using spectroscopic techniques (FTIR, ¹H NMR and mass) and X-ray crystallography. This ligand possesses different centers for coordination. Reactions of [M(CO)₆], M = Cr, Mo or W with IBTH₂ in THF under reduced pressure were studied. For chromium a complex with molecular formula [Cr(ITP)₂] was isolated; where ITP is the opened form of the ligand which occurred through C_spiro–S bond, while [Mo(CO)₅(IBTH₂)] and [W(CO)₅(IBTH₂)] were isolated from the reaction of IBTH₂ with molybdenum and tungsten carbonyls, respectively. All complexes were characterized by elemental analysis, IR, mass and ¹H NMR spectroscopy. The biological activity of the ligand and its complexes were studied and compared with the parent compound isatin.     

Acylation of 2′,5′,5′-trimethyl-4′,5′-dihydro-4H-spiro-[naphthalene-1,3′-pyrrol]-4-one with 5-arylfuran-2,3-diones

Russian Journal of Organic Chemistry -