Reaction of 2,2,3,3-tetracyanocyclopropyl ketones with water

3-Benzoylcyclopropane-1,1,2,2-tetracarbonitrile reacted with water to give 2-benzoyl-1,3-dicyanocyclopropane-1-carboxamide as a result of hydrolysis of the cyano group in the trans position with respect to the carbonyl group and subsequent decarboxylation. The reaction of 3-benzoyl-3-methylcyclopropane-1,1,2,2-tetracarbonitrile with water involved heterocyclization with participation of the carbonyl group and cis-cyano groups, leading to 8-methyl-3,6-dioxo-1-phenyl-2,7-diazatricyclo[3.2.1.0^4,8]octane-4,5-dicarbonitrile. Hydrolysis of 3-alkylcyclopropane-1,1,2,2-tetracarbonitrile followed both reaction paths to produce mixtures of products, including 7-alkyl-4-amino-7-hydroxy-1,9-dioxo-3,8-diazatricyclo[4.3.0.0^1,5]non-3-ene-5-carbonitriles. In all cases, the three-membered ring was retained.     

New procedures for preparing 2,2,3,3-tetracyanocyclopropyl ketones

New procedures were developed for preparing 2,2,3,3-tetracyanocyclopropyl ketones, based on reactions of substituted glyoxals with bromomalononitrile.     

Synthesis of 2,2,3,3-tetracyanocyclopropyl ketones and their reactions with oxygen-centered nucleophiles

A procedure for the synthesis of 2,2,3,3-tetracyanocyclopropyl ketones has been developed on the basis of three-component Wideqvist reaction of dihydroxymethyl ketones, 2-bromomalononitrile, and malononitrile. The presence of five electron-withdrawing groups in the resulting cyclopropyl ketones determines high acidity of proton in the cyclopropane ring. Facile deprotonation by the action of bases promotes opening of the three-membered ring with formation of either 1,1,3,3-tetracyanopropenides or (in the presence of alcohols or oximes), [2-alkoxy(aminooxy)-5-amino-4-cyanofuran-3(2H)-ylidene]malononitriles. The reaction with acetone oxime was not accompanied by cleavage of the three-membered ring, and nucleophilic attack was directed at the cyano groups in the trans position with respect to the carbonyl group to give the corresponding (1R*,5S*,6R*)-4-amino-2,2-bis(prop-2-ylideneaminooxy)-3-azabicyclo[3.1.0]hex-3-ene-1,5-dicarbonitriles.     

Reaction of 1-(tetracyanocyclopropyl)alkanones with sodium and potassium hydroxides

Enolizable 1-(tetracyanocyclopropyl)alkanones reacted with aqueous alkali metal hydroxides to give, depending on the alkali concentration, 2-(5-amino-2-alkylidene-4-cyano-2,3-dihydrofuran-3-ylidene)-propanedinitriles or 2-(4-alkyl-3-amino-2-cyano-5-oxo-cyclopent-2-en-1-ylidene)propanedinitriles.     

Hydration phenomena of sodium and potassium hydroxides by water molecules

The hydrated structures, dissociation energies, thermodynamic quantities, infrared spectra, and electronic properties of alkali-metal hydroxides (MOH, M = Na and K) hydrated by up to six water molecules [MOH(H(2)O)(n=1-6)], are investigated by using the density functional theory and M?ller-Plesset second-order perturbation theory. Further accurate analysis based on the coupled cluster theory with singles, doubles, and perturbative triples excitations is more consistent with the MP2 results. NaOH shows a peculiar trend in dissociation: it begins to form a partially dissociated structure for n = 3, and it dissociates for n = 4 and 6, whereas it is undissociated for n = 5. However, for n = 5, the dissociated structure is nearly isoenergetic to the undissociated structure. For KOH, it begins to show partial dissociation for n = 5, and complete dissociation for n = 6.     

Reaction of 2,2,3,3-tetrafluoropropyl dichloro-phosphite with 1,1,2-trichloro-1-nitrosoethane

Conclusions Depending on the reaction conditions, 2,2,3,3-tetrafluoropropyi dichlorophosphate and 1,1,2-trichloro-1-nitrosoethane give either O-chloromethylchloroformiminodichlorophosphate or O-chloromethylchloroformimino-O-2,2,3,3-tetrafluoropropylchlorophosphate.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1422–1423, June, 1987.     

Reaction of difluoronitroacetyl fluoride with ketones

Conclusions A method was developed for the preparation of -diketones that contain the CF₂NO₂ grouping.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2350–2351, October, 1973.     

Reaction of perfluoro ketones with hexamethyldisilazane

Conclusions Perfluoro ketones react with hexamethyldisilazane under mild conditions to give 2-trimethylsilyloxy-2-trtmethylsilylaminoperfluoropropanes.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 10, pp. 2352–2353, October, 1972.     

Reaction of ethynyl ketones with o-phenylenediamine

2,4-Diaryl-3H-benzo-1,5-diazepines were obtained by reaction of ethynyl ketones with o-phenylenediamine.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1421–1422, October, 1973.     

Reaction of cyclic ketones with KOH-DMSO

Upon reaction of cycloalkanones with a KOH-DMSO system 2-methylenecycloal-kanols are formed, the yield (10–37%) of which decreases in the series: cyclohexanone > cycloheptanone > cyclooctanone > cyclododecanone.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 7, pp. 1601–1605, July, 1990.     

Activity coefficients and diffusion coefficients of dilute aqueous solutions of lithium,sodium, and potassium hydroxides

A simplified version of Harned's conductimetric technique has been used to measure binary diffusion coefficients of aqueous lithium, sodium, and potassium hydroxides at 25°C from 0.002 to 0.14 mol-dm^–3. Because of the large difference in mobility between OH^– and the cations, the electrophoretic effect tends to reduce the rate of diffusion of the alkali metal hydroxides; the largest effect is observed for LiOH solutions. The measured diffusion coefficients are in excellent agreement with predictions of the Onsager-Fuoss theory of ion transport. Precise activity coefficients determined from the diffusion measurements are compared with activity coefficients obtained previously by emf methods.     

Reaction of o-phenylenediamine with α-bromoacetylenic ketones

Conclusions 1,2-Di-(acylethynylaza)benzenes and 2-acylmethylenebenzo-1,3-imidazoline hydrobromides were obtained by the reaction of o-phenylenediamine with-bromoacetylenic ketones.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 5, pp. 1173–1175, May, 1984.     

Reaction of 2-acyloxiranes with cyclic ketones

Acyloxiranes react with cyclopentanone and cyclohexanone in the presence of catalytic amounts of boron trifluoride etherate to give the corresponding 2-acyl-1,4-dioxaspiro[4,4]-nonanes and 2-acyl-1,4-dioxaspiro[4,5]decanes. The corresponding cis-2,3-dimethyl-2 acetyl-1,4-dioxaspiroalkanes are formed from trans-2,3-dimethyl-2-acetyloxirane.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 7, pp. 885–888, July, 1974.