Reaction of 2-hydrazinoperimidine with acetylacetone

Heating 2-hydrazinoperimidine ( 2 ) with acetylacetone in absolute ethanol gave exclusively 2-(3,5-dimethyl-1-pyrazolyl)perimidine ( 4 ) via a [2 + 3] cyclization. The possible [4 + 3] condensate, 3,5-dimethyl-1H-1,2,4-triazepino[4,3-a]perimidine ( 5 ) was not produced. Spectral analyses were applied to the structure elucidation of the products.     

Reaction of acetylacetone with diethylphosphorous acid

Conclusions The reaction of equimolar amounts of acetylacetone and diethylphosphorous acid at room temperature in the presence of sodium alcoholate gives the diethyl ester of 1-methyl-1-hydroxy-3-ketobutylphosphonic acid. When heated or when treated with water-removing agents the latter cleaves water with the formation of the diethyl ester of 1-methyl-3-keto-1-buten-1-yl-phosphonicacid. The reaction of two moles of diethyl-phosphorous acid with one mole of acetylacetone under the same conditions gave 2-oxo-2-ethoxy-3,5-dimethyl-3-hydroxy-5-diethoxyphosphono-1-oxa-2-phospholane.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 12, pp. 2757–2761, December, 1971.We wish to thank T. A. Zyablikova and É. I. Gol'dfarb, co-workers at the A. E. Arbuzov Institute of Organic and Physical Chemistry of the Academy of Sciences of the USSR, for taking the NMR spectra.     

Reaction of the framework 3d-organometallosiloxanes with acetylacetone

A reaction of acetylacetone with the framework sandwich-type metallosiloxanes (MOS) of general formula [PhSiO₂]₆M₆[PhSiO₂]₆, where M = Cu, Ni, Mn, was studied by GPC, ¹H and ²⁹Si NMR spectroscopy, X-ray diffraction, elemental and functional analysis. The reaction involved replacement of the metal atoms with the hydrogen atoms and is accompanied by the formation of the corresponding chelate complexes M(acac)₂. Displacement of the metal from the framework MOS leads to the destruction of molecular skeleton and formation of phenylsiloxanes containing Si-OH groups. The yield and composition of the reaction products considerably depend on the nature of the metal in [PhSiO₂]₆M₆[ThSiO₂]₆. A selective substitution of the metal leads to the stereoregular hexahydroxyhexaphenylcyclohexasiloxane, [PhSiO(PH)]₆, cis-isomer. The structure and composition of the crystalline hexahydroxyhexaphenylcyclohexasiloxane obtained were confirmed by ²⁹Si NMR spectroscopy, X-ray diffraction study, and functional analysis, while its TMS derivative was studied with ¹H NMR spectroscopy and GPC. Using a framework manganese phenylsiloxane as an example, a reversible character of the process has been established and an alternative synthesis of this compound from hexahydroxyhexaphenylcyclohexasiloxane and Mn(acac)₂ has been accomplished for the first time.     

Reaction of 4-iminothiazolidin-2-one with acetylacetone

By the reaction of acetylacetone and arylazoacetylacetones with 4-iminothiazolidin-2-one thiazolo[4,5-b]pyridines were obtained in good yields. Optimum reaction conditions were chosen and some properties of compounds obtained were studied.     

Reaction of 6-methyluracyl derivatives with acetylacetone and ethyl acetoacetate

Reaction of acetylacetone and ethyl acetoacetate with 1-(ω-bromoalkyl)-3,6-dimethyluracyls and 1,3-bis(ω-bromoalkyl)-6-methyluracyls lead to the formation of uracyl derivatives containing the ketone and ketoester fragments. Conditions leading to the highest yields of the compounds synthesized were found.     

Reaction of o-quinones of the benzofuran and indole series with acetoacetic ester and acetylacetone

The reaction of o-quinones of the benzofuran and indole series with acetoacetic ester and acetylacetone in the presence of zinc chloride leads to derivatives of 4,5-dihydroxybenzofuran and 4,5-dihydroxyindole with acetoacetic ester and acetylacetone residues, in the 7 position.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1356–1357, October, 1982.     

Reaction of acetylacetone with cyanamide in the presence of catalytic amounts of nickel acetylacetonate

Conclusions The reaction of acetylacetone with cyanamide in the presence of Ni(acac)₂ involves the addition of the CH₂ group at the nitrile group of cyanamide with the formation of 3-(diaminomethylene)pentane-2,4-dione (III) and the products of its transformations, namely, N-acylketenaminals (IV) and (V).Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1431–1434, June, 1988.     

Reaction of trichlorides of phosphono carboxylic acids with acetylacetone,acetoacetic ester,and phenols

Reactions of trichloride of phosphono carboxylic acid with β-dicarbonyl compounds proceed at the active methylene group with the formation of the С-acylation product with a small admixture of the product of O-acylation. The C-acylation products undergo intramolecular condensation to form 1,2-oxophosphorines and compounds of the phosphate structure. The condensation of trichlorides with phenols proceeds selectively at the carbonyl carbon atom leading to C-phenyl esters. With more acidic phenols the splitting of the Р–С bond in the substitution product occurs.     

Reaction of 6-aryl-2,2-dimethyl-1,3-dioxin-4-ones with acetylacetone and methyl acylpyruvates

Aroyl ketenes formed in the thermolysis of 6-aryl-2,2-dimethyl-1,3-dioxin-4-ones undergo a [4+2]-cycloaddition reaction with acetylacetone and methyl acylpyruvates to give 2-methyl- and 2-methoxycarbonyl-3-acyl-6-arylpyran-4-ones, respectively.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 161–163, February, 1989.     

Cyclocondensation of 2-methylbenzimidazole with acetylacetone

Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 12, pp. 1695–1696, December, 1989.     

Condensation of acetylacetone with formaldehyde and thiols

Acetylacetone reacted with formaldehyde and thiols in aqueous medium or in the presence of 0.1 equiv of sodium hydroxide to give the corresponding 3-[(alkylsulfanyl)methyl]pentane-2,4-diones which exist in solution as mixtures of diketone and enol tautomers. Four-component condensation of acetylacetone with formaldehyde, methanethiol, and sodium sulfide, depending on the reaction time, led to the formation of a mixture of 1,1-bis(methylsulfanylmethyl)propan-2-one with 1,1′-{3-[(methylsulfanyl)methyl]tetrahydro-2H-thiopyran-3,5-diyl}diethanone or with 8-methyl-5-(methylsulfanylmethyl)-3-thiabicyclo[3.3.1]non-7-en-6-one.     

Condensation of oxindole with acetoacetic ester and acetylacetone

4-Methylpyrano[2,3-b]indol-2-one is formed on thermal condensation of oxindole with acetoacetic ester. The condensation of oxindole with acetylacetone proceeds in position 3 of oxindole without closure in the pyrane ring. __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1167–1169, August, 2006.     

Vibrational assignment of acetylacetone

The infrared and Raman spectra of acetylacetone and its deuterated analogues have been analyzed by the aid of ab initio calculations at post Hartree-Fock level and considering the spectral behavior upon deuteration. By deconvolution of the infrared spectra of acetylacetone and d6-acetylacetone at 1600 cm(-1) region a broad and strong band is found and correlated with the strong Raman lines observed for these compounds in this region. The broadness of this infrared band at room temperature and it's splitting at low temperature is attributed to free rotation of methyl group attached to carbonyl group at room temperature. Furthermore it is found that all ring modes in 1200-1600 cm(-1) region more or less are mixed with the OH in plane bending motion.     

Reaction of <Emphasis Type="Italic">N</Emphasis>-arenesulfonyl-1,4-benzoquinone imines with acetylacetone

N-Arenesulfonyl-1,4-benzoquinone imines reacted with acetylacetone to afford different products, depending on the isolation procedure. Crystallization from polar protic solvents gave N-[4-hydroxy- 3-(2-hydroxy-4-oxopent-2-en-3-yl)phenyl]arenesulfonamides and 6-(2-oxopropyl)-4-(arenesulfonamido)phenyl acetates, whereas N-(3-acetyl-2,6-dimethyl-1-benzofuran-5-yl)arenesulfonamides were isolated by crystallization from nonpolar aprotic solvents.     

Reactions of hydrogen peroxide with acetylacetone and 2-acetylcyclopentanone

A reaction of acetylacetone with equimolar amount of concentrated aqueous H₂O₂ in both organic solvents (Bu^tOH, AcOH) and water at various temperatures gave the corresponding 3,5-dihydroxy-1,2-dioxolanes with different configuration of stereogenic centers. In the presence of an excess of H₂O₂, 3,5-dihydroxy-1,2-dioxolanes were converted to a mixture of 5-hydroperoxy-3-hydroxy-1,2-dioxolanes and further to a mixture of dimeric 1,2-dioxolan-3-ylperoxides. All the peroxides formed exist in solutions as equilibrium mixtures with the starting reagents. A prolonged reflux of solutions of 3,5-dihydroxy-1,2-dioxolanes in Bu^tOH in the presence of a large excess of H₂O₂ led to the skeletal rearrangements of the substrates to a mixture of propionic acid and hydroxyacetone, which underwent further oxidative transformations. Unlike acetylacetone, 2-acetylcyclopentanone reacted with H₂O₂ in aqueous phase or in solutions in Bu^tOH under thermodynamic or kinetic control with the formation of the corresponding 5-hydroperoxy-3-hydroxy-1,2-dioxolanes, rather than 3,5-dihydroxy-1,2-dioxolanes. Thermodynamically controlled process in solution in AcOH gave a mixture of all four possible hydroperoxyhydroxy-1,2-dioxolanes. These cyclic peroxides in solutions in ButOH or AcOH readily converted to a mixture of AcOH, glutaric, α-methyladipic, and α-hydroxy-α-methyladipic acids. An active α-hydroxylation of the substrate was observed upon reflux of a solution of 2-acetylcyclopentanone and H₂O₂ in AcOH.     

Oligomerization in the reaction of acetylacetone with organic diisocyanates

Russian Journal of Organic Chemistry -