Five-membered 2,3-dioxoheterocycles: LXIV. Reactions of 1-methyl-3,4-dihydroisoquinolines with 5-arylfuran-2,3-diones and (Z)-alkyl 4-aryl-2-hydroxy-4-oxobut-2-enoates. Crystal and molecular structure of (2Z,5Z)-3-hydroxy-5-{8,8-dimethyl-2,3,8,9-tetrahydro[1,4]dioxino[2,3-g]isoquinolin-6(7H)-ylidene}-1-phenylpent-2-ene-1,4-dione

5-Arylfuran-2,3-diones and (Z)-alkyl 4-aryl-2-hydroxy-4-oxobut-2-enoates react with 3,3-dialkyl-1-methyl-3,4-dihydroisoquinolines to give (2Z,5Z)-1-aryl-3-hydroxy-5-[3,3-dialkyl-3,4-dihydroisoquinolin-1(2H)-ylidene]pent-2-ene-1,4-diones whose structure has been proved by XRD analysis.     

Direct heterocyclization of tetrahydroisoquinolin-1-ylideneacetic acids by the action of 5-arylfuran-2,3-diones

Aroylketenes generated in situ by thermolysis of 6-aryl-2,2-dimethyl-4H-1,3-dioxin-4-ones reacted with 3,3-dialkyl-1-methyl-3,4-dihydroisoquinolines to give (1Z,3Z)-4-aryl-4-hydroxy-1-[3,3-dialkyl-3,4-dihydroisoquinolin-1(2H)-ylidene]but-3-en-4-ones. The crystalline and molecular structure of (1Z,3Z)-4-hydroxy-1-[6,7-dimethoxy-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]-4-phenylbut-3-en-2-one was studied by X-ray diffraction.     

Five-membered 2,3-dioxo heterocycles: LVII. Recyclization of 3-pivaloylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones by the action of o-phenylenediamine. Crystalline and molecular structure of 3-[3,3-dimethyl-2-oxo-1-(3-oxo-3,4-dihydroquinoxalin-2-yl)butyl]-1-phenylquinoxalin-2(1H)-one

3-[(Z)-3,3-Dimethyl-2-oxobutylidene]-3,4-dihydroquinoxalin-2(1H)-one and its 1-phenyl-substituted analog reacted with oxalyl chloride to give the corresponding 3-pivaloylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones. Reactions of the latter with o-phenylenediamine led to the formation of 3,3′-(3,3-dimethyl-2-oxobutane-1,1-diyl)di[quinoxalin-2(1H)-ones]. Original Russian Text ? K.S. Bozdyreva, Z.G. Aliev, A.N. Maslivets. 2008, published in Zhurnal Organicheskoi Khimii, 2008, Vol. 44, No. 4, pp. 612–616. For communication LVI, see [1].     

Synthesis, crystal structure, and spectra of 9(E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]hydrazone and its cation-anion complex with copper(I) bromide

The reaction of 1-hydrazino-3,3-dimethyl-3,4-dihydroisoquinoline with 9,10-phenanthrenequinone gave (9E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]hydrazone (L). The reaction of L with copper(II) bromide gave the complex (LH)[CuBr₂]. The crystal structures of the monohydrate L · H₂O (I) and the isolated complex (LH)[CuBr₂] (II) were determined by X-ray diffraction. The structural units of I are pseudo-centrosymmetric dimers in which the L and water molecules are combined by strong hydrogen bonds. The active H atom is located at the N(1) atom of the isoquinoline fragment of the L molecule. The L molecule occurs in the crystal as the cis, trans isomer with respect to exocyclic C=N bonds at the isoquinoline and phenanthrenequinone fragments, respectively. Complex II has a cation-anion structure. The LH⁺ cation as the cis, cis isomer is protonated at N(2) and stabilized by two intramolecular hydrogen bonds. In the CuBr₂⁻ anion, the copper atom in the oxidation state +1 has a linear coordination, the C-Br bond length is 2.185(4) ± 0.005 ?, and the BrCuBr angle is 179.8(4)°. The main ion-ion interactions in structure II are shortened contacts involving bromine atoms, which combine cations and anions into a three-dimensional framework. Original Russian Text ? V.V. Davydov, V.I. Sokol, N.V. Rychagina, R.V. Linko, M.A. Ryabov, Yu.V. Shklyaev, V.S. Sergienko, 2009, published in Zhurnal Neorganicheskoi Khimii, 2009, Vol. 54, No. 6, pp. 958–970.     

Synthesis,crystal structure,and electronic structure of a copper(II) chloride complex with 9(E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]hydrazone [Cu2(L-H)2Cl2]

The [Cu₂(L-H)₂Cl₂] compound (I) has been obtained by the reaction of 9(E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]hydrazone with copper(II) chloride. The crystal and molecular structure of I has been determined by X-ray crystallography. The L-H anion acts as a tridentate chelating ligand and is coordinated to the Cu atom through the O(1) atoms of the phenanthrenequinone moiety, the N(1) atom of the dihydroisoquinoline moiety, and the N(3) atom of the azo group to form two five-membered chelate rings. Complex I is a dimer with a double chloride bridge. The coordination polyhedron of the Cu atom is completed to a distorted pyramid by two chlorine atoms. The molecular and electronic structures of the L molecule and the model [Cu(L-H)Cl] complex have been determined by the density functional theory method. Spectroscopic characteristics of I have been determined.     

Five-membered 2,3-dioxoheterocycles: LXXIII. Synthesis and thermolysis of 3-acylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones

Reactions of (Z)-3-(phenacylidene-2-oxo)-3,4-dihydroquinoxalin-2(1H)-ones and (Z)-3-(3,3-dimethyl-2-oxobutylidene)-3,4-dihydroquinoxalin-2(1H)-one with oxalyl chloride led to the formation of 3-acyl-1Hpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones that at the thermal decarbonylation generated acyl(3-oxoquinoxalin-2-yl)ketenes which underwent the intramolecular stabilization giving 3-acylfuro[3,2-b]quinoxalin-2(4H)-ones.     

Five-membered 2,3-dioxo heterocycles: XCII. Reaction of 3-aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones with ethyl (2Z)-(3,3-dimethyl-8-oxo-2-azaspiro[4.5]deca-6,9-dien-1-ylidene)ethanoate. Synthesis of bridged analogs of pyrrolizidine alkaloids

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones reacted with ethyl (2Z)-(3,3-dimethyl-8-oxo-2-azaspiro[4.5]deca-6,9-dien-1-ylidene)acetate to give ethyl 6′-aryl-2′-(2-hydroxyphenyl)-11′,11′-dimethyl-3′,4,4′,13′-tetraoxospiro[2,5-cyclohexadiene-1,9′-(7′-oxa-2′,12′-diazatetracyclo[6.5.1.0^1,5.0^8,12]tetradec-5′-ene)]-14′-carboxylates whose structure was confirmed by X-ray analysis. The products may be regarded as bridged analogs of pyrrolizidine alkaloids, 7′-oxa-2′,12′-diazatetracyclo[6.5.1.01,5.08,12]tetradecanes.     

[3 + 2]-Cycloaddition of azomethine ylide at 1,3-dimethyl-6-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5-e][1,3]thiazolo[3,2-b][1,2,4]triazine-2,7(1H,6H)-diones

[3 + 2]-Cycloaddition of azomethine ylide generated from formaldehyde and sarcosine at the double bond of 1,3-dimethyl-6-(2-oxo-1,2-dihydro-3H-indol-3-ylidene)-3a,9a-diphenyl-3,3a,9,9a-tetrahydroimidazo[4,5e][1,3]thiazolo[3,2-b][1,2,4]triazine-2,7(1H,6H)-diones occurs stereospecifically at the face opposite to the phenyl substituents. Product 3a crystallizes as a conglomerate.     

Five-membered 2,3-dioxo heterocycles: CVI. Acylation of substituted (Z)-2-[1,3,4,4a,5,10b-Hexahydrophenanthridin-6(2H)-ylidene]acetamide with aroylketenes. crystal and molecular structure of substituted N-{(Z)-2-[1,3,4,4a,5,10b-Hexahydrophenanthridin-6(2H)-ylidene]acetyl}acrylamide

Aroylketenes generated by thermolysis of 6-aryl-2,2-dimethyl-4H-1,3-dioxin-4-ones reacted with (Z)-2-[4a,7,10-trimethyl-1,3,4,4a,5,10b-hexahydrophenanthridin-6(2H)-ylidene]acetamide to give (Z)-3-aryl-3-hydroxy-N-{(Z)-2-[4a,7,10-trimethyl-1,3,4,4a,5,10b-hexahydrophenanthridin-6(2H)-ylidene]acetyl}acrylamides whose structure was confirmed by X-ray analysis.     

[3,4]-annulated pyrroles 1. Polynuclear heterocyclic systems based on pyrrolo[3,4-d]pyrimidine-2,4-dione

The intramolecular electrophilic substitution in 6-functionalized 1,3-dimethyl-1H-pyrrolo[3,4-d]pyrimidine-2,4(3H,6H)-diones was used for the synthesis of pyrimido[4′,5′:3,4]-pyrrolo[1,2-a]quinoxaline-8,10(7H,9H)-dione, pyrimido[4′,5′:3,4]pyrrolo[2,1-c][1,2,4]benzo-triazine-8,10(7H,9H)-dione, and 2H-pyrimido[4′,5′:3,4]pyrrolo[1,2-a]indole-2,4,11(1H, 3H)-trione derivatives. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2180–2185, December, 2006.     

New organic nitrates. II. Synthesis of 2H-pyrido[2,3-e]-1,3-oxazine-2,4(3H)-diones, 2H-pyrido[4,3-e]-1,3-oxazine-2,4(3H)-diones, 2H-pyrido[4,3-e]-1,3-oxazin-4(3H)-ones, 2H-thieno[2,3-e]-1,3-oxazin-4(3H)-ones and 2H-thieno[3,4-e]-1,3-oxazin-2,4(3H)-diones

The preparation and the physico-chemical characterization of 2H-pyrido[2,3-e]-1,3-oxazine-2,4(3H)-diones, 2H-pyrido[4,3-e]-1,3-oxazine-2,4(3H)-diones, 2H-pyrido[4,3-e]-1,3-oxazin-4(3H)-ones, 2H-thieno[2,3-e]-1,3-oxazin-4(3H)-ones and 2H-thieno[3,4-e]-1,3-oxazine-2,4(3H)-diones are reported.     

Synthesis,crystal structure,and spectra of the trichloromethane solvate of nickel(II) 9(E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]hydrazonate

The complex [Ni(L-H)₂] · CHCl₃ (I), where L-H is the (9E)-phenanthrene-9,10-dione[(1Z)-3,3-dimethyl-3,4-dihydroisoquinolin-1(2H)-ylidene]hydrazone anion (L), was synthesized for the first time. The crystal structure of I was solved. The L-H and L-H′ anions exist as cis- and trans-isomers and are linked to the central Ni²⁺ atom in a tridentate chelating mode giving rise to two conjugated five-membered metal rings of different composition (NiN₃C and NiONC₂) at each anion. The Ni²⁺ coordination polyhedron is a highly distorted octahedron whose axial positions are occupied by N(3) and N(3)′ atoms. The vertices of the tetrahedrally distorted equatorial base of the octahedron are occupied by the N(1) and N(1)′ atoms of the dihydroisoquinoline fragment (A) and the O(1) and O(1)′ atoms of the phenanthrenequinone fragment (B). Complex I occurs as the cis-isomer. The conformations of the L-H anions in I and the L molecules in L · H₂O do not differ much. The randomly disordered CHCl₃ solvent molecules in I occupy crystal voids between the centrosymmetric dimeric associates. Spectroscopic (IR and UV-Vis) characteristics of I were obtained.     

Five-Membered 2,3-dioxoheterocycles: XCV. Recyclization of 4-benzoyl-5-phenylfuran-2,3-dione at the action of substituted 1,3,3-trimethyl-2-azaspiro[4.5]dec-1-enes. Crystal and molecular structure of substituted 5-(2-azaspiro[4.5]dec-1-ylidene)cyclopent-3-ene-1,2-dione

4-Benzoyl-5-phenylfuran-2,3-dione reacts with 2′,5′,5′-trimethyl-4′,5′-dihydro-4H-spiro[naphthalene-1,3′-pyrrol]-4-one and 8-(2-methoxy-5-methylphenyl)-1,3,3,9-tetramethyl-2-azaspiro[4.5]deca-1,7-dien-6-one with the formation of (Z)-3-benzoyl-5-(5′,5′-dimethyl-4-oxo-4H-spiro[naphthalene-1,3′-pyrrolidin]-2′-ylidene)-4-phenylcyclopent-3-ene-1,2-dione, whose structure was proved by XRD analysis, and of (Z)-3-benzoyl-5-{8-(2-methoxy-5-methylphenyl)-3,3,9-trimethyl-6-oxo-2-azaspiro[4.5]dec-7-en-1-ylidene}-4-phenylcyclopent-3-ene-1,2-dione.     

Rearrangement of furo[2,3-c]quinoline-2,4(3aH,5H)-diones to furo[3,4-c]quinoline-3,4(1H,5H)-diones

Thermally assisted base-catalyzed rearrangement of furo[2,3-c]quinoline-2,4(3aH,5H)-diones 1 to the corresponding furo[3,4-c]quinoline-3,4(1H,5H)-diones 2 is reported, and a mechanism of the transformation is proposed.     

Rearrangement in the series of 3-(2-aryl-2-oxoethyl)-3,4-dihydroquinoxalin-2(1H)-ones

4-Acetyl- and 4-succinyl-3-(2-aryl-2-oxoethyl)-3,4-dihydroquinoxalin-2(1H)-ones undergo the rearrangement into (Z)-2-(3-arylquinoxalin-2-ylidene)acetic acids accompanied by the elimination of the acyl groups. The nitration of 3-(2-oxo-2-phenylethyl)-3,4-dihydro-quinoxalin-2(1H)-one affords 5-nitro- and 7-nitro-2-carboxymethylidenequinoxalines. The bromination of quinoxalin-2-ones in AcOH gives 3-aryl-2-carboxymethylidenequinoxalines and the corresponding 7-bromo derivatives, with the former products predominating.     

Synthesis of New 1,2,3,4-Tetrahydroisoquinoline Derivatives. 2-(2,3,3-Trimethyl-1,2,3,4-tetrahydroisoquinolin-1-yl)anilines

A four-step procedure has been developed for the synthesis of new 2-(2,3,3-trimethyl-1,2,3,4-tetrahydroisoquinolin-1-yl)anilines by acylation of 2-(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)anilines at the amino group with isobutyryl chloride, reduction of the endocyclic C=N bond in N-[2-(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)phenyl]isobutyramides, N-alkylation of N-[2-(3,3-dimethyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phenyl]isobutyramides to N-[2-(2,3,3-trimethyl-1,2,3,4-tetrahydroisoquinolin-1-yl)phenyl]isobutyramides, and acid hydrolysis of the latter.     

Five-membered 2,3-dioxoheterocycles: LXXXIV. [4+2]-Cycloaddition of styrene to 4,5-diaroyl-1H-pyrrole-2,3-diones. Crystal and molecular structures of 7a-(2,5-dimethylbenzoyl)-4-(2,5-dimethylphenyl)-1-(4-methoxyphenyl)-6-phenyl-7,7a-dihydropyrano[4,3-b]-pyrrole-2,3(1H,6H)-dione

1-Aryl-4,5-diaroyl-1H-pyrrole-2,3-diones react with styrene to form substituted 7,7a-dihydropyrano[4,3-b] pyrrole-2,3(1H,6H)-diones whose structure was confirmed by XRD analysis. The crystal and molecular structure of 7a-(2,5-dimethylbenzoyl)-4-(2,5-dimethyl-phenyl)-1-(4-methoxyphenyl)-6-phenyl-7,7a-dihydropyrano[4,3-b] pyrrole-2,3(1H,6H)dione was examined.     

Synthesis of 4-(2-hydroxy-1-methyl-5-oxo-1H-imidazol-4(5H)-ylidene)-5-oxo-1-aryl-4,5-dihydro-1H-pyrrole-3-carboxylates, a new triazafulvalene system

(2E,3Z)-2-(1-Methyl-2,5-dioxoimidazolidin-4-ylidene)-3-[(arylamino- or heteroarylamino)methylene]succinate 5 obtained by [2+2] cycloaddition of (5Z)-5-[(dimethylamino)methylene]-3-methylimidazolidine-2,4-dione (1) and dimethyl acetylenedicarboxylate (2) followed by substitution of the dimethylamino group with aromatic or heteroaromatic amines, afforded by heating in ethanol in the presence of potassium hydroxide, potassium salts 6. Acidification of 6 with hydrochloric acid afforded mixtures of (E)- and (Z)-isomers of methyl 4-(2-hydroxy-1-methyl-5-oxo-1H-imidazol-4(5H)-ylidene)-5-oxo-1-phenyl-4,5-dihydro-1H-pyrrole-3-carboxylates. On the other hand, alkylation of compounds 6 with methyl iodide or benzyl bromide produced the corresponding methyl (E)-4-(2-methoxy- or 2-benzyloxy-1-methyl-5-oxo-1H-imidazol-4(5H)-ylidene)-5-oxo-1-phenyl-4,5-dihydro-1H-pyrrole-3-carboxylates 9, derivatives of a new triazafulvalene system.     

Five-membered 2,3-dioxoheterocycles: XCVI. Reactions of 3-aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5h)-triones with substituted 1,3,3-trimethyl-2-azaspiro[4.5]dec-1-enes

3-Aroylpyrrolo[1,2-a]quinoxaline-1,2,4(5H)-triones react with 1,3,3,7,9-pentamethyl-2-azaspiro-[4.5] deca-1,6,9-trien-8-one and 2′,5′,5′-trimethyl-4′,5′-dihydro-4H-spiro[naphthalene-1,3′-pyrrol]-4-one providing 3-aroyl-2-hydroxy-3a-{(3,3,7,9-tetramethyl-8-oxo-2-azaspiro[4.5]deca-1,6,9-trien-1-yl)methyl}pyrrolo[1,2-a-quinoxaline-1,4(3a H,5H)-diones and 3-aroyl-2-hydroxy-3a-{(5′,5′-dimethyl-4-oxo-4′,5′-dihydro-4H-spiro[naphthalene-1,3′-pyrrol]-2′-yl)methyl}pyrrolo[1,2-a]-quinoxaline-1,4(3aH,5H)-diones.     

Reaction of dichlorocarbene with substituted 3,4-dihydroisoquinolines and 1-methylene-1,2,3,4-tetrahydroisoquinolines

Reaction of dichlorocarbene with 3,3-dialkyl-3,4-dihydroisoquinolines results in the formation of gemdichloroazirino[2,1-a]isoquinolines, which are in turn converted to 3-benzazepinones upon hydrolysis. Reaction of dichlorocarbene with the ethyl ester or amide of (3,3-dimethyl-1,2,3,4-tetrahydroisoquinolin-1-ylidene)acetic acid is accompanied by rearrangement of the intermediate carbene adducts at the enamine C=C bond and results in the formation of a 1-azadiene, 3-(3,3-dimethyl-3,4-dihydroisoquinolin-1-yl)-3-chloroacrylic acid ethyl ester, and a spirolactam, 3,3-dimethyl-3-chlorospiro[1,2,3,4-tetrahydroisoquinoline-1,2-pyrrole]-5(2H)-one, respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1086–1091, August, 1990.