Photochemical reactions of 7-aminocoumarins. 6. Reaction of 7-dialkylaminocoumarins with halo derivatives

3-Substituted 7-dialkylaminocoumarins were synthesized as a result of the photoreaction of 7-diethylaminocoumarin, 4-trifluoromethyl-7-diethylaminocoumarin, 4-chloro-7-diethylaminocoumarin, 4-(N-morpholino)-7-diethylaminocoumarin, and coumarin-102 (2,3,6,7-tetrahydro-9-methyl-1H,5H,11H-[1]-benzopyrano[6,7,8-ij]quinolizin-11-one) with iodobenzene, 3,4-dimethoxyiodobenzene, isopropyl iodide, and ethyl -bromoacetate. It was established that electron-acceptor and electron-donor substituents in the 4 position accelerate photosubstitution. The spectral-luminescence characteristics of the compounds obtained were investigated.For Communication 5, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 1028–1032, August, 1990.     

Chemistry of Thienopyridines. XXIV. Two Transformations of Thieno[ 2,3-b] pyridine 7-Oxide

Refluxing thieno[2,3-b ]pyridine 7-oxide ( 1 ) with aeetic anhydride plus subsequent hydrolysis produced a mixture of thieno[2,3-b]pyrid-6(7H)one ( 2 ) (13%) and 5-hydroxythieno[2,3-b]-pyridine ( 4 ) (4%). Refluxing 1 with phosphorus oxychloride yielded a mixture of 4- and 6-chloro-thieno[2,3-b]pyridines, ( 5 ) (54%) and ( 6 ) (31%), respectively. Compound 6 was also obtained directly from 2 (31%). A mechanistic rationalization for the isomerization of 1 to form 2 and 4 is presented. Marked differences in the mass spectral fragmentations of these three isomeric compounds are noted.     

Mass spectrometric study of diazoketone cyclization. 7. Phthalimidoalkyl-α-diazoketones

The molecular ions of phthalimidoalkyl--diazoketones that form in the gas phase under electron impact split out a nitrogen molecule and rearrange by a Wolff mechanism to ketenic ions. The alternative intramolecular heterocyclization does not occur. The decomposition mechanism of [M-N₂]⁺ions was studied. The structures of some charged fragments that form when the phthalimide nucleus decomposes were established by high resolution spectrometry,Communication No. 6, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 788–793, June, 1985.     

Photochemical reactions of 7-aminocoumarins. 7. Reaction of 3-iodo-4-methyl-7-diethylcoumarin with olefins

A number of new 7-aminocoumarins having an unsaturated substituent in the 3 position were obtained as a result of photolysis of 3-iodo-4-methyl-7-diethylaminocoumarin with olefins, viz., styrene, acrylonitrile, methyl acrylate, methyl methacrylate, 4-vinylpyridine, 2-ethoxypropene, indent, ethyl -anilinocrotonate, and 2,5-norbornadiene, as well as with phenylacetylene. Regiospecificity and stereospecificity of the investigated photoreactions were established. The spectral-luminescence characteristics of the synthesized compounds are presented.For Communication 6, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1033–1041, August, 1990.     

Spirocyclohexadienones. 7. Three-component condensation of 1- or 2-methoxynaphthalene with isobutyraldehyde and nitriles

1-R-3,3-Dimethylbenzo[i]-2-azaspiro[4.5]deca-1,6-dien-8-ones or 1-R-3,3-dimethylbenzo[i]-2-azaspiro[4.5]deca-1,7-dien-6-ones were synthesized by three-component condensation of 1- or 2-methoxynaphthalene, isobutyraldehyde (or isobutylene oxide), and nitrile RCN in concentrated sulfuric acid.     

Synthesis of nitrogen-containing heterocycles. 7 Reaction of aliphatic diaminomethylenehydrazones with hindered ethoxymethylenecyanoacetate

Aliphatic diaminomethylenehydrazones 1 were reacted with ethyl 2-cyano-3-ethoxy-2-pentenoate 2 to give a number of heterocycles in low to moderate yields, according to the substitution pattern and the size of substituent. When 1 carried a single methyl group on the terminal nitrogen, it gave preferentially 6-oxo-1,6-dihydropyrimidines 4 incorporating N(4) into the ring. In contrast, the reaction between 1c or 1d and 2 led to 6-imino- and 6-oxo-1, 6-dihydropyrimidines 7 and 8 along with 3 . When the alkylidene moiety was bulky, 1e and 1f , the similar reaction gave 3 in high yields without any cyclized product. Upon exposure to acid, compound 3 yielded 6-oxo-1,6-dihydropyrimidines 6 , [1,2,4]triazolo[1,5-c]pyrimidine-8-carboxylate 5 and N-alkenyl-1,2,4-triazoles 9 in addition to 7 and 8 in proportions dictated by the nature of the substituents of 1 . The structural assignment and reaction mechanism are discussed.     

Furopyridines. XVIII. Photocycloaddition of furo[2,3-c]pyridin-7(6H)-one with acrylonitrile

The photocycloaddition of furo[2,3-c]pyridin-7(6H)-one ( 1 ) and its N-mefhyl derivative ( 1-Me ) to acrylonitrile has been studied. The structures of the photoadducts isolated by colum chromatography were determined by the nuclear magnetic resonance spectroscopy and single crystal X-ray analysis. The cyclo-addition of 1 afforded an adduct 2 at the carbonyl oxygen and 8-cyano-8,9-dihydrofuro[d]azocin-7(6H)-one ( 3 ), and the addition of 1-Me the N-methyl derivative 3-Me of 3 , (9S*)-9-cyano-6-methyl-3a,7a-dihydro-3a,7a-ethanofuro[2,3-c]pyridin-7(6H)-one ( 4 ), (2S*, 2aR*, 7bR*)- ( 5 ) and (1R*, 2aS*, 7bS*)-2-cyano-3-methyl-4-oxo-1,2,2a,3,4,7b-hexahydrocyclobuta[e]furo[2,3-c]pyridine ( 6 ).     

Synthesis of 1-p-Methoxyphenyl and 1-p-Methoxyphenyl-4-methylbicyclo-[2.2.1]heptan-7-one. The Oxidation of 7-Hydroxy-1-p-methoxyphenyl-4-methylbicyclo[2.2.1]heptan-7-carboxylic Acid with Lead Tetraacetate

A simple synthetic route to 1-p-methoxyphenyl and 1-p-methoxyphenyl-4-methylbicyclo [2.2.1]heptan-7-one 6b,a has been developed through benzilic acid rearrangement of the bicyclo[2.2.1]octandiones 2b,a. The oxidation of 7-hydroxy-1-p-methoxyphenyl-4-methylbicyclo[2.2.1]heptan-7-carboxylic acid 3a with lead tetraacetate gives the carbolactone 7a which is also formed by the reaction of the ketone 6a with m-chloroperbenzoic acid.     

Synthesis of analogs of 5(4)-aminoimidazole-4(5)-carboxamide and purines. 7. 7-(β-d-ribofuranosyl)-4-methylthioimidazo[4,5-d]-1,2,3-triazine

The synthesis of 7-(-D-ribofuranosyl)-4-methylthioimidazo[4,5-d]-1,2,3-triazine, 7-methyl-4-methylthioimidazo[4,5-d]-1,2,3-triazine, and 5-methyl-4-methylthioimidazo [4,5-d]-1,2,3-triazine is described. The structures of the synthesized compounds were confirmed by ¹³C NMR spectroscopy.See [1] for communication 6.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 6, pp. 836–838, June, 1979.     

Synthesis and isomerization of epoxides derived from 7-phenylsulfonyl-and 7-methylsulfonyl-6-methylidenebicyclo[3.1.1]heptanes

Oxidation of exo-7-phenylsulfonyl-and exo-7-methylsulfonyl-6-methylidenebicyclo[3.1.1]heptanes with m-chloroperoxybenzoic acid gave the corresponding epoxy derivatives, anti-7-phenylsulfonyl-and anti-7-methylsulfonyl-endo-2′-oxaspiro[bicyclo[3.1.1]heptane-6,2′-cyclopropanes]. Treatment of the phenylsulfonyl-substituted epoxide with potassium tert-butoxide in THF led to the 1,3-cyclization product, 7-phenylsulfonyltricyclo[4.1.0.0^2,7]hept-1-ylmethanol. anti-7-Methylsulfonyl-endo-2′-oxaspiro[bicyclo[3.1.1]heptane-6,2′-cyclopropane] under analogous conditions underwent 1,6-cyclization, being converted into 6-hydroxy-3λ⁶-thiatricyclo[4.4.0.0^2,7]decane 3,3-dioxide.     

Indolizines. 6. Relative reactivities of isomeric 6-, 7-, and 8-ethoxycarbonylindolizine derivatives

The kinetics of the alkaline hydrolysis of 2-phenyl-6-, -7-, and -8-ethoxycarbonylindolizines were studied. The rate constants for the hydrolysis of these compounds and the indexes of the dissociation constants of 2-phenylindolizine-6-,-7-, and -8-carboxylic acids were determined by spectrophotometry. The indexes of the electronic structures and reactivities of 2-methyl-6-, -7-, and -8-ethoxycarbonylindolizines were calculated from theory.See [1] for Communication [5].Deceased.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 627–633, May, 1979.     

Synthesis and thermal decomposition of haloalkoxy-sym-triazines. 7. Thermal decomposition of 2-dialkylamino-4-(2-chloroethoxy)-6-methoxyamino-sym-triazines

Two 2-dialkylamino-4-(2-chloroethoxy)-6-methoxyamino-sym-triazines were synthesized. It was established that when they are heated at 120° C, the 2-chloroethoxy group undergoes rearrangement with cyclization to give 2-dialkylamino-4-oxo-8-methoxy-6, 7-dihydroimidazo [1,2-a]-sym-triazines, the structure of which was confirmed by data from the IR, PMR, and mass spectra.See [6] for Communication 6.Translated from Khimiya Geterotsilicheskikh Soedinenii, No. 8, pp. 1122–1124, August, 1981.     

Bisindoles. 7. Synthesis of di(5-indolyl) sulfone

The parent compound of a new heterocyclic system, viz., di(5-indolyl) sulfone, was synthesized by the classical scheme of the Fischer reaction by means of polyphosphoric acid. The starting dihydrazine was obtained from 4,4'-dichlorodiphenyl sulfone.See [1] for Communication 6.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 11, pp. 1508–1510, November, 1980.     

Condensed Pyridopyrimidines. 7. Synthesis of Condensed Triazolo[4,3-c]- and Tetrazolo[1,5-c]pyrimidines

Novel dihydro-5H-pyrano[3',4':5',6']pyrido[2,3-d]-1,2,4-triazolo[4,3-c]pyrimidines and 1,2,3,4-tetrazolo[1,5-c]pyrimidines have been synthesized from 2-amino-3-cyano-7,7-dimethyl-7,8-dihydro-5H-pyrano[4,3-b]pyridine.     

Condensed benzopyrans. IV. Synthesis of some derivatives of 7H- and 9H-pyrano[3,2-E]indoles

The hydrazones derived from coumarin-6-ylhydrazine and ethyl 6-hydrazinochromone-2-carboxylate undergo facile indolization to give 3H,7H-pyrano[3,2-e]indol-7-ones (IIIb-IIIg) and ethyl 9-oxo-3H,9H-pyrano[3,2-e]indole-7-carboxylates (IVb-IVd), respectively, in good yields. Compounds IVb-IVd are derivatives of a new ring system.     

Diazocarbonyl derivatives of heterocycles. 7. Synthesis,properties, and structure of 2,4-diazido-6-diazoacetylpyrimidine

The reaction of 2,4-dichloro-6-diazoacetylpyrimidine with sodium azide to give 2,4-diazido-6-diazoacetylpyrimidine has been examined, and the crystal structure of the latter, and its 1,3-dipolar cycloadditions at the carbonyl group, studied.For Communication 6, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 4, pp. 515–519, April, 1990.     

Macroheterocycles. 7. Synthesis and extraction capacity of some dibenzo-18-crown-6-derivatives

Derivatives that contain vinyl, formyl, acetyl, carboxy, carbethoxy, -carboxyvinyl, or -carbethoxyvinyl groups in the benzene rings were synthesized from dibenzo-18-crown-6. The ability of the synthesized crown ethers to extract picrates of alkali metals from the aqueous phase to the chloroform phase was investigated.See [1] for Communication 6.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 5, pp. 599–603, May, 1981.     

The thermal rearrangement of endo-7-methyl-exo-7-vinylbicyclo[3.2.0]Hept-2-ene

Gas-phase thermolysis of the title compound in the temperature range of 150°–166°C yields predominantly cis-6-methyl-4,7,8,9-tetrahydroindene by tandem [1,3]–[3,3) sigmatropic shifts: however, we cannot exclude some direct conversion by an alternative [1,3] sigmatropic migration.     

Azaindoles. 69. Some reactions of 5-cyano-6-chloro-7-azaindoles and lactam-lactim tautomerism in 5-cyano-6-hydroxy-7-azaindolines

Electrophilic substitution in the 3-position of 1-benzyl-4-methyl-5-cyano-6-chloro-7-azaindole requires more severe conditions than in 7-azaindoles without the 5-cyano-substituent. Increased ease of nucleophilic replacement of the chlorine atom by the methoxy group has been observed in 1-benzyl- (and 1-butyl)-4-methyl-5-cyano-6-chloro-7-azaindoles, and the cyano-group in these compounds has been found to be resistant to hydrolysis and alcoholysis. The introduction into 1-benzyl- (and 1-butyl)-4-methyl-6-hydroxy-7-azaindoles of a 5-cyano-substituent results in a shift of the lactam-lactim tautomeric equilibrium towards the lactim forms.For communication 68, see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 1, pp. 100–106, January, 1987.     

A Diastereoselective Preparation of 7-Ethyl-7-methylbicyclo[3.2.0]HEPT-2-en-6-one(1)

Alkylation of 7-endo-ethylbicyclo[3.2.0]hept-2-en-6-one (2a) and 7-endo-methylbicyclo[3.2.0]hept-2-en-6-one (2b) with lithium diisopropylamide (LDA) and the appropriate alkyl iodide (methyl and ethyl iodide, respectively) afforded the title compound such that alkylation had occurred exclusively on the exo face of the bicyclo[3.2.0] system.