Synthesis and reactivity of 2-(porphyrin-2-yl)-1,3-dicarbonyl compounds

A simple and efficient procedure for the synthesis of porphyrins bearing 1,3-dicarbonyl moieties at the β-position is described. The new compounds were further functionalized and new derivatives containing an heterocyclic ring, an ethyl acetate residue or a 2-oxopropyl group at the β-position have been obtained.     

Synthesis of (1,3-adamantylene)bis-1,3-dicarbonyl compounds

Reactions of 1,3-dihydroxyadamantane with 1,3-dicarbonyl compounds in the presence of 5 mol % of In(OTf)₃ afforded a series of (1,3-adamantylene)bis-1,3-dicarbonyl compounds in yields of 25–83%.     

The synthesis of 2-(2-furyl) 1,3-dicarbonyl compounds

2-furyl derivatives are easily synthesised by intermolecular condensation of 2,5-dihydro-2,5-dimethoxy furan (DHDMF) with active methylene compounds by a simple and cheap procedure. The reaction applies only to 1,3-dicarbonyl compounds and a general mechanism is proposed.     

Synthesis of 1,3-dialkyl-5-(hetaryl-1-yl)-1,3-dihydrobenzimidazol-2-ones

Reactions of 5-amino-1,3-dialkyl-1,3-dihydrobenzimidazol-2-ones with 2,5-dimethoxytetrahydrofuran and 2,6-dimethyl-γ-pyranone led to the formation of 1,3-dialkyl-1,3-dihydro-5-(pyrrol-1-andл)benzimidazol-2-ones and 1-(1,3-dialkyl-2-oxo-1,3-dihydrobenzimidazol-5-yl)-2,6-dimethylpyridin-4-ones.     

Reaction of 5-(1-bromo-2-aryl-vinyl)-3-methyl-4-nitro-isoxazoles and 1,3-dicarbonyl compounds

The preparation of E-5-(1-bromo-2-aryl-vinyl)-3-methyl-4-nitro-isoxazoles and their reaction with 1,3-dicarbonyl compounds to give cyclopropanes or dihydrofurans is described.     

Synthesis and properties of 2-azahetarylaminomethylidene 1,3-dicarbonyl compounds

Reactions of 2-ethoxymethylidene 1,3-dicarbonyl compounds with pyridine-2,6- and pyrimidine-4,5-diamines gave the corresponding 2-hetarylaminomethylidene derivatives. Depending on the initial reactant structure, the formation of mono-and/or bis-condensation products is possible. Hetarylaminomethylidene derivatives showed a moderate tuberculostatic effect. 2-Pyridinylaminomethylidene 3-oxo esters were used as ligands to obtain coordination compounds with d- and f-metal ions.     

Photochemical Synthesis of Cyclic 2-(2,2-Dimethylpropylidene)-1,3-dicarbonyl Compounds

Photolysis (λ = 254 nm) of 4-(t-Bu)-substituted [b]-fused bi- and tricyclic pyrandiones 5 affords title compounds 4 in good yields as well as small amounts of spiroalkanediones 8 . The alkyl-substitution pattern at C(4) of the pyran ring in 5 determines the relative amount of α vs. β-cleavage products obtained from the primarily formed acyl-vinyloxy biradical.     

Synthesis of New 2-(Oxiran-2-yl)-1,3-oxazoles

Russian Journal of General Chemistry - Reaction of 2-chloro-N-(2,2-dichloro-1-cyanovinyl)acetamide with dimethylamine gave 5-(dimethylamino)-2-[(dimethylamino)methyl]-1,3-oxazole-4-carbonitrile,...     

Synthesis and properties of 1,3-diphenyl-5-(benzothiazol-2-yl)-6-R-verdazyls

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New copper(II) coordination compounds with 1,3-bis(5-(pyridin-2-yl)-1,2,4-triazol-3-yl)propane

Two new copper(II) complexes with 1,3-bis(5-(pyridin-2-yl)-1,2,4-triazol-3-yl)propane (H₂L), [Cu₂(HL)Cl₃] · H₂O (I) and [Cu(H₂L)](ClO₄)₂ (II), were described. The compounds were characterized by elemental analysis, IR spectroscopy, and magnetochemical data. According to X-ray diffraction data (CIF files CCDC nos. 1497511 (I), 1497512 (II)), complex I is binuclear and the metal cations are bound by the nitrogen atoms of the triazole ring and by the chloride anion. Complex II is mononuclear. Analysis of the temperature dependence of the magnetic susceptibility of I attests to the antiferromagnetic coupling of paramagnetic centers (–2J = 18 cm^–1). Exchange channels are analyzed by means of density functional theory (B3LYP/6-311G(d)) using the broken symmetry approach.     

Synthesis of 3-nitropyrid-2(1H)-ones fromC-nitroacetamide and 1,3-dicarbonyl compounds

The reaction of nitroacetamide with 1,3-dicarbonyl compounds afforded 3-nitropyrid-2(1H)-ones. The chemical reactivities of nitroacetamide and nitroacetohydrazide were compared.     

Synthesis and characterization of functionalized 1,3-bis(2- alkyltetrazol-5-yl)triazenes

A series of 1,3-bis(2-alkyltetrazol-5-yl)triazenes have been synthesized in high yields by treatment of sodium nitrite and hydrochloric acid with substituted-5-aminotetrazoles. All compounds were fully characterized using IR spectroscopy,~1H NMR and~(13) C NMR spectroscopy and high resolution mass spectrometer(HRMS). Most of these triazenes exhibit good detonation performance comparable with TNT and low melting points ranging from 81°C to 106°C, which are suitable for melt-cast explosives.Among these compounds, 1,3-bis(2-azidoethyltetrazol-5-yl)triazene(2g) displays a low melting point(106°C), moderate onset decomposition temperature(183°C) and good detonation performance(D:7087 m/s; P: 17.6 GPa).     

Iodoenolcyclisation of 2-(1,3-disubstituted-1-allyl)-1,3-dicarbonyl compounds: diastereoselective synthesis of tetrasubstituted dihydrofurans

The I₂-induced cyclisation of 2-alkenyl-1,3-dicarbonyl compounds with the mono- and di-substituted double bond occurred with good diastereoselectivity. A study of stereochemical aspects for different substituents on the allyl side chain was carried out. When the substituents were alkyl groups, the trans isomers formed preferentially, in the case of aromatic substituents the reaction lead instead to cis isomers.     

Synthesis and transformations of polyhedral compounds. Synthesis of 2-[quinolin-3(2)-yl]-1,3-diazaadamantanes

A number of new 1,3-diazaadamantane derivatives containing quinoline fragments on C² have been synthesized by condensation of 1,5-dialkyl-3,7-diazabicyclo[3.3.1]nonan-9-one, 1,5-dimethyl-3,7-diazabicyclo-[3.3.1]nonan-9-ol, and 1,5-dimethyl-3,7-diazabicyclo[3.3.1]nonane with 2-oxo-1,2-dihydroquinoline-3-carbaldehyde, 2-chloro- and 2-iodoquinoline-3-carbaldehyde, and quinoline-2-carbaldehyde.     

New liquid crystal compounds ( )-4-[5-(2-Methylbutyl)-1,3-dioxan-2-yl]phenyl 4-alkoxybenzoate

New liquid crystal compounds, (+)-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl] phenyl 4-alkoxybenzoates (5), were synthesized. The mesomorphic behaviour of these compounds is compared with that of (+)-4-(5-alkyl-1,3-dioxan-2-yl)-phenyl 4-(2-methylbutoxy)benzoates (6). While compounds 6 exhibited a chiral smectic C phase, the corresponding compounds 5 did not. This might mean that for the appearance of a chiral smectic C phase in these types of compounds, it is necessary that the carbonyl and the chiral groups exist at nearby positions. Transition temperatures to those isotropic state for compounds 5 were lower than those for compounds 6. This result is common in both cases of (+)-4-alkoxycarbonylphenyl-4-[5-(2-methylbutyl)-1,3-dioxan-2-yl]benzoates (7), and (+)-4-(2-methylbutoxy-carbonyl)phenyl 4-(5-alkyl-1,3-dioxan-2-yl)-benzoates (8).     

Synthesis of novel 1,3-bis(5-diarylaminothiophen-2-yl)isothianaphthenes

We report the synthesis, electrochemical and optical properties of novel 1,3-bis(5-diarylaminothiophen-2-yl)isothianaphthenes obtained by palladium-catalysed amination of 1,3-bis(5-bromothiophen-2-yl)isothianaphthene with diarylamines.     

Synthesis and isomerization reaction of 2-(benzoxazol-2-yl)-1,3-tropolones

An acid-catalyzed reaction of 2-methylbenzoxazole with 3,4,5,6-tetrachloro-1,2-benzoquinone leads to 2-(benzoxazol-2-yl)-5,6,7-trichloro-1,3-tropolone and 2-(benzoxazol-2-yl)-4,5,6,7-tetrachloro-1,3-tropolone. 1,3-Tropolones upon reflux in ethyl alcohol undergo the rearrangement resulted in the seven-membered ring contraction to form ethyl 2-(benzoxazol-2-yl)-5,6-dichloro-3-hydroxybenzoate and ethyl 2-(benzoxazol-2-yl)-4,5,6-trichloro-3-hydroxybenzoate. The molecular structure of the latter was established by X-ray diffraction analysis.     

Synthesis of 1,3-dialkyl-5-(pyrrol-1-yl)-1,3-dihydro-2H-imidazo[4,5-b]pyridin-2-ones

Russian Journal of Organic Chemistry -