Features of reactions between (3,5-dioxo-4-azatricyclo-[5.2.1.0<Superscript>2-<Emphasis Type="Italic">endo</Emphasis>,6-<Emphasis Type="Italic">endo</Emphasis></Superscript>]dec-8-en-4-yl)carboxylic acids and <Emphasis Type="Italic">p</Emphasis>-nitrophenyl azide

Reactions were performed of (3,5-dioxo-4-azatricyclo[5.2.1.0^{2-endo,6-endo} ]dec-8-en-4-yl)carboxylic acids and their derivatives with p-nitrophenyl azide. A significant fact of the involvement of the carboxy group into the formation of aziridine ring was established and the intermolecular character of this process was confirmed. The structure of compounds synthesized was proved by IR and ¹H NMR spectra.     

New derivatives of 2-(3,5-Dioxo-4-azatricyclo[5.2.1.0<Superscript>2,6-<Emphasis Type="Italic">endo</Emphasis></Superscript>]dec-8-en-4-yl)acetic acid. Synthesis and reactivity

New urea, carbamates, and carboxamides of the norbornene series were synthesized on the basis of 4-isocyanatomethyl-4-azatricyclo[5.2.1.0^2,6-endo ]dec-8-ene-3,5-dione, and their behavior in reactions with various electrophiles was studied. The structure of the isolated compounds was confirmed by the IR and ¹H NMR spectra.     

Reactions of 4-amino-4-azatricyclo[5.2.1.0<Superscript>2,6-<Emphasis Type="Italic">endo</Emphasis></Superscript>]dec-8-ene-3,5-dione with dicarboxylic acid anhydrides

Reactions of 4-amino-4-azatricyclo[5.2.1.0^2,6-endo ]dec-8-ene-3,5-dione (hydrazinolysis product of endic anhydride) with succinic, maleic, cis-cyclohexane-1,2-dicarboxylic, endic, phthalic, and 1,8-naphthalic anhydrides were studied. Procedures for the preparation of the corresponding hydrazido acids and bis-imides were proposed. Their reactions with peroxyformic acid, depending on the substrate nature, led to the formation of both epoxy hydrazido acids and epoxy imides. The unsaturated adducts reacted with p-nitrophenyl azide to give the corresponding triazole derivatives.     

Hydrogenolysis of 7-phenyltricyclo[4.1.0.0<Superscript>2,7</Superscript>]heptan-1-carboxylic acid. Synthesis of ketones with tricyclo[4.4.0.0<Superscript>2,7</Superscript>]decane and tricyclo[5.4.0.0<Superscript>2,8</Superscript>]undecane skeletons

Hydrogenation of 7-phenyltricyclo[4.1.0.0^2,7]heptane-1-carboxylic acid over Raney nickel occurred in the syn-stereoselective fashion to give anti-7-phenylbicyclo[3.1.1]heptane-exo-6-carboxylic acid. The latter was used to synthesize 4,5-benzotricyclo[4.4.0.0^2,7]dec-4-en-3-one and two isomeric higher homologs, 5,6-benzotricyclo[5.4.0.0^2,8]undec-5-en-3-and-4-ones.     

Synthesis of 5-(Benzylamino)-<Emphasis Type="Italic">exo</Emphasis>-3-azatricyclo-[5.2.1.0<Superscript>2,6</Superscript>]decan-4-one derivatives

5-(Benzylamino)-exo-3-azatricyclo[5.2.1.0^2,6]decan-4-one derivatives were synthesized in up to 94% yield by condensation of norbornane-fused 3-aminopyrrolidin-2-one with aromatic aldehydes.     

Catalytic hydrogenation of methyl 3,4-diazatricyclo-[5.2.1.0<Superscript>2,6</Superscript>]dec-4-ene-5-carboxylate

The hydrogenation at Raney nickel of the pyrazoline ring in methyl exo-3,4-diazatricyclo-[5.2.1.0^2,6]dec-4-ene-5-carboxylate takes place quantitatively with the preferential formation of the trans isomer of 5-amino-exo-3-azatricyclo[5.2.1.0^2,6]decan-4-one. The 3-methoxycarbonylmethyl-, 3-acetyl-, and 3-nitroso-substituted esters are not hydrogenated under these conditions.     

Fused pyrimidine systems: XVI. Electrophilic intramolecular cyclization of 2-(alkenylsulfanyl)pteridin-4(3<Emphasis Type="Italic">H</Emphasis>)-ones

2-[Allyl(but-3-en-1-yl, pent-4-en-1-yl)sulfanyl]pteridin-4(3Н)-ones at heating in polyphosphoric acid undergo an intramolecular cyclization affording respectively 9-methyl-8,9-dihydro-5H-[1,3]thiazolo[3,2-a] pteridin-5-one and 10-methyl(ethyl)-9,10-dihydro-5Н,8Н-[1,3]thiazino[3,2-a]pteridin-5-ones of angular structure. The cyclization of 2-(alkenylsulfanyl)pteridin-4(3Н)-ones under the action of iodine or arylsulfenyl chlorides afforded iodo(arylsulfanyl) derivatives of angularly fuzed thiazolo- and thiazinopteridines.     

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.     

Synthetic transformations of higher terpenoids: XXIII. Synthesis of diterpenoid-based dihydroisoindolones

Vilsmeier-Haak reaction of phlomisoic acid methyl ester gave a mixture of 15- and 16-formyllabdanoids. In addition, methyl 2-formyldodecahydrophenanthro[1,2-b]furan-6-carboxylate was isolated, and its structure was determined by X-ray analysis. Reductive amination of 16-formyllabdanoid with benzylamine or α-amino acid methyl esters led to the formation of labdanoid furfurylamines which reacted with maleic anhydride to produce N-substituted 4-oxo-10-oxa-3-azatricyclo[5.2.1.0^1,5]dec-8-ene-6-carboxylic acids. Acylation of labdanoid furfurylamines with (E)-but-2-enoyl chloride afforded the corresponding unsaturated amides which were converted into 10-oxa-3-azatricyclo[5.2.1.0^1,5]dec-8-en-4-ones via intramolecular Diels-Alder reaction. Treatment of the oxa adducts with boron trifluoride-diethyl ether complex gave dihydroisoindol-1-one derivatives containing a diterpene fragment.     

Reactions of Bi-, Tri-, and tetracyclic amines with succinic anhydride

Succinic anhydride reacted with cage-like amines {bicyclo[2.2.1]hept-5-en-exo-and-endo-2-yl-methanamines, 2-(bicyclo[2.2.1]hept-5-en-endo-2-yl)ethanamine, exo-5,6-epoxybicyclo[2.2.1]heptan-exo-2-yl-methanamine, tetracyclo[6.2.1.1^3,6.0^2,7]dodec-9-en-endo-4-ylmethanamine, 1-(bicyclo[2.2.1]heptan-2-yl)ethanamine, and 4-azatricyclo[5.2.1.0^2,6]dec-8-ene} to give the corresponding amido acids having a cage-like fragment. The latter were converted into carboximides by the action of hexamethyldisilazane in boiling benzene in the presence of zinc(II) chloride and then into epoxy derivatives. The structure of the newly synthesized compounds was confirmed by IR and NMR spectroscopy.     

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.     

Five-membered 2,3-dioxo heterocycles: LVI. Reaction of 3-aroyl-1<Emphasis Type="Italic">H</Emphasis>-pyrrolo[2,1-<Emphasis Type="Italic">c</Emphasis>][1,4]benzoxazine-1,2,4-triones with acyclic enamino ketones

3-Aroyl-1H-pyrrolo[2,1-c][1,4]benzoxazine-1,2,4-triones react with 4-arylaminopent-3-en-2-ones and 3-amino-1,3-diphenylprop-2-en-1-ones to give substituted 4-aroyl-3-hydroxy-1-(o-hydroxyphenyl)-1,7-diazaspiro[4.4]nona-3,8-diene-2,6-diones.     

Synthesis of 3-N-substituted <Emphasis Type="Italic">exo</Emphasis>-3,4 diazatricyclo[5.2.1.0<Superscript>2,6</Superscript>]dec-4-enes

Treatment of exo-3,4-diazatricyclo[5.2.1.0^2,6]dec-4-ene with methyl acrylate, acrylonitrile, ethylene oxide, acetic acid and nitrosonium cation gave a series of 3-N-substituted exo-3,4-diazatricyclo[5.2.1.0^2,6]dec-4-enes. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 533–537, April, 2007.     

Halocyclization of 3-{[2-methyl(bromo)prop-2-en-1-yl]-sulfanyl}-5<Emphasis Type="Italic">H</Emphasis>-[1,2,4]triazino[5,6-<Emphasis Type="Italic">b</Emphasis>]indoles

Reactions of 3-[(2-bromoprop-2-en-1-yl)sulfanyl]-5H-[1,2,4]triazino[5,6-b]indole with bromine and of 3-[(2-methylprop-2-en-1-yl)sulfanyl]-5H-[1,2,4]triazino[5,6-b]indole with iodine and bromine afforded 3-halomethyl-10H-[1,3]thiazolo[3′,2′: 2,3][1,2,4]triazino[5,6-b]indol-4-ium halides whose structures were determined by ¹H NMR and X-ray analysis.     

Alkylations of tricyclo[5.2.1.0]deca-4,8-dien-3-one by a cuprate reaction

Alkylation at C₆ of tricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one (R=H) was achieved by treatment of 6-bromotricyclo[5.2.1.0^2,6]deca-4,8-dien-3-one with lithium dimethylcuprate and subsequently with an appropriate electrophile. The best results were obtained in THF as the solvent. A wide range of alkyl halides, bromo ketones and esters, and acetyl chloride resulted in C₆-tricyclo[5.2.1.0^2,6]deca-4,8-dien-3-ones in moderate to good yields. This alkylation reaction proceeds via a C₆-carbanionic Cu intermediate, which is likely stabilized by the enone olefinic bond. 6-Bromo-endo-tricyclo[5.2.1.0^2,6]dec-8-en-3-one, which lacks this double bond, behaves differently. Treatment with lithium dimethylcuprate leads to dehydrobromination to give tricyclo[5.2.1.0^2,6]deca-2(6),8-dien-3-one in high yield.     

Formation of mononuclear rhodium(III) sulfates: <Superscript>103</Superscript>Rh and <Superscript>17</Superscript>O NMR study

It was shown that the monomeric rhodium sulfate complexes [Rh(H₂O)₄(SO₄)]⁺, trans-[Rh(H₂O)₂(SO₄)₂]^?, cis-[Rh(H₂O)₂(SO₄)₂]^?, and [Rh(SO₄)₃]^3? were not predominant forms in aqueous solutions. The ¹⁰³Rh NMR chemical shifts of the complexes were assigned, and the conditions for their formation in solutions, concentration parameters, and acidity at which the fraction of the monomers was maximal were determined. The constants of formation of the complexes and ion pair (IP) were estimated: K _IP = 8 ± 3.5, K ₁ ≈ 8, K _2trans ≈ 1, K _2cis ≈ 1, and K ₃ ≈ 2.     

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.     

Synthesis of 4-alkyl(aryl,hetaryl)-2-thioxo-5,6,7,8-tetrahydroquinoline-3-carbonitriles and their derivatives by cross-recyclization of 4-alkyl(aryl,hetaryl)-2,6-diamino-4<Emphasis Type="Italic">H</Emphasis>-thiopyran-3,5-dicarbonitriles with 4-(cyclohex-1-en-1-yl)-morpholine,alkyl halides,and cyclohexanone

Cross recyclization of 4-substituted 2,6-diamino-4H-thiopyran-3,5-dicarbonitriles with 4-(cyclohex-1-en-1-yl)morpholine, alkyl halides, and cyclohexanone gave the corresponding substituted 2-thioxo-1,2,5,6,7,8-hexahydroquinoline-3-carbonitriles, 2-alkylsulfanyl-5,6,7,8-tetrahydroquinoline-3-carbonitriles, 3-amino-5,6,7,8-tetrahydrothieno[2,3-b]quinoline-2-carboxamides, and 4-oxo-2,2-pentamethylene-1,2,3,4,7,8,9,10-octahydropyrimido[4′,5′:4,5]thieno[2,3-b]quinolines. The structure of 3-(4-bromophenyl)-2,2-pentamethylene-11-(2-thienyl)-1,2,3,4,7,8,9,10-octahydropyrimido[4′,5′:4,5]thieno[2,3-b]quinoline was proved by X-ray analysis.     

Synthesis,scope, <Superscript>1</Superscript>H and <Superscript>13</Superscript>C spectral assignments of isomeric dibenzofuran carboxaldehydes

Two isomeric dibenzofuran carboxaldehydes, namely 2-methoxydibenzo[b,d]furan-1-carbaldehyde (4) and 2-methoxydibenzo[b,d]furan-3-carbaldehyde (5), were synthesized. Formylation of 2-methoxydibenzo[b,d]furan (3) with α,α-dichloromethyl methyl ether and tin(IV) chloride gave a mixture of aldehydes 4 and 5 in 95 % yield and in a 35:65 ratio. Their ¹H and ¹³C NMR spectral signals were not sufficiently resolved in CDCl₃ solution to achieve their complete assignment, but this was possible in DMSO-d ₆ with the help of 2D-NMR techniques: NOESY for ¹H–¹H interactions and HSQC and HMQC experiments for ¹H–¹³C correlations. These aldehydes were used in the synthesis of novel β-phenylethylamines and NBOMe derivatives, which are undergoing biological evaluation.     

Synthesis of novel 4<Emphasis Type="Italic">H</Emphasis>-furo[3,2-c]pyran-4-ones and 4<Emphasis Type="Italic">H</Emphasis>-furo[3,2-<Emphasis Type="Italic">c</Emphasis>]chromen-4-ones

It was found that the condensation of two equivalents of 4-hydroxy-6-methyl-2H-pyran-2-one or 4-hydroxycoumarin with arylglyoxals in boiling formic acid leads to 4H-furo[3,2-c]-pyran-4-ones or 4H-furo[3,2-c]chromen-4-ones, respectively.