Electrochemical transformation of cyanoacetic ester and alkylidenecyanoacetic esters into 3-substituted 1,2-dicyanocyclopropane-1,2-dicarboxylates

Electrolysis of cyanoacetic ester and alkylidenecyanoacetic esters in an undivided cell in the presence of mediators (alkali metal halides) gives rise to 3-substituted, 1,2-dicyanocyclopropane-1,2-dicarboxylates in 60–95% yields. Translated fromIzvestiya Akademii Nauk, Seriya Khimicheskaya, No. 6, pp. 1165–1168, June, 1998.     

Synthesis of 1,2-azaphospholanes containing an amino acid fragment

2-Oxo-1,2-azaphospholanes and 1,2-azaphospholanium salts containing an amino acid fragment were synthesized by intramolecular P-alkylation of N-3-chloropropyl-substituted tricoordinate phosphorus amides. Hydrolysis of 2-oxo-1,2-azaphospholanes at the P-N bond gives rise to γ-aminopropylphosphonic acid derivatives. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2557–2562, November, 2005.     

Mild template synthesis of copper(II)-containing macrocyclic compounds in the CuII–1,2-diaminoethanedithione-1,2–ethanedione-1,2 and CuII–1,2-diamino-ethanedithione-1,2–butanedione-2,3 triple systems into Cu2[Fe(CN)6]-gelatin-immobilized matrix implantates

The complexing processes in the Cu^II–1,2-diaminoethanedithione-1,2–ethanedione-1,2 and Cu^II–1,2-diaminoethanedithione-1,2–butanedione-2,3 triple systems occuring in the copper(II)hexacyanoferrate(II) gelatin-immobilized matrix in contact with aqueous alkaline solutions (pH~12) containing 1,2-diaminoethanedithione-1,2 and ethanedione-1,2 or butanedione-1,2 under room temperature, and between MCl₂, 1,2-diaminoethanedithione-1,2 and ethanedione-1,2 or butanedione-1,2 in the ethanol solutions, upon heating up to ~80 °C, have been studied. In both systems indicated, template synthesis occurs in the gelatin-immobililized matrix but does not occur in the ethanol solution. As a result of template synthesis, macrocyclic Cu^II chelates with 2,7-dithio-3,6-diazaoctadien-3,5-dithioamide-1,8 and its 4,5-dimethylsubstituted derivative are formed in the gelatin-immobililized matrix. 1,2-diaminoethanedithione-1,2 and ethanedione-1,2 or butanedione-2,3 are the ligand synthons in the processes indicated.     

A reaction of 6-bromo-1,2-naphthoquinone with tri(<Emphasis Type="Italic">n</Emphasis>-butyl)phosphine: A convenient route to phosphorus-containing 1,2-naphthoquinones and 1,2-dihydroxynaphthalenes

A reaction of 6-bromo-1,2-naphthoquinone with tri(n-butyl)phosphine gave 2-hydroxy-4-tri(n-butyl)phosphonionaphth-1-olate (betaine with the P—C bond). When treated with bromine, this betaine changed into (6-bromo-1,2-dihydroxy-4-naphthyl)tri(n-butyl)phosphonium bromide and (6-bromo-1,2-dioxo-1,2-dihydro-4-naphthyl)tri(n-butyl)phosphonium bromide in the ratio ∼1: 1. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 534–536, March, 2007.     

Reaction of Z isomers of alkylaromatic 1,2-hydroxylamino oximes with 1,2-diketones

The reactions of Z isomers of alkylaromatic 1,2-hydroxylamino oximes containing the hydroxylamino group at the primary or secondary carbon atom with diacetyl afford 6-acetyl-5,6-dihydro-4H-1,2,5-oxadiazines. The reactions of these compounds with alkylaromatic 1,2-diketones produce N-substituted α-aroylnitrones or 6-aroyl-5,6-dihydro-4H-1,2,5-oxadiazines or, alternatively, their tautomeric mixtures. Dedicated to the memory of Academician V. A. Koptyug on the occasion of the 75th anniversary of his birth. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1008–1013, June, 2006.     

Synthesis of 5-mercapto-1,2-dithiole-3-thiones and their transformation into 5-chloro-1,2-dithiol-3-ones

A number of 4-dialkylamino-5-mercapto-1,2-dithiole-3-thiones were synthesized by reactions of alkyl(diisopropyl)amines with S₂Cl₂. Their reactions with S₂Cl₂—DABCO unexpectedly gave 5-chloro-4-dialkylamino-1,2-dithiol-3-ones. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 1, pp. 143–147, January, 2006.     

Synthesis of enamino ketones from <Emphasis Type="Italic">N</Emphasis>-(2-vinyloxyalkyl)-ethane-1,2-diamines

Condensation of N-(2-vinyloxyethyl)ethane-1,2-diamine with aromatic aldehydes gave mixtures of 2-aryl-1-(2-vinyloxyethyl)imidazolidines and N-arylmethylidene-N′-(2-vinyloxyethyl)ethane-1,2-diamines in an overall yield of 79–84%, while analogous condensation with cyclic and acyclic ketones resulted in the formation of only the corresponding Schiff bases (yield 53–83%).     

Reactions of 3-hydroxy-1,2-dihydroquinazolin-4-ones with aldehydes

The reactions of 3-hydroxy-2-(2-hydroxyalkyl)- [or (2-hydroxyaryl)]-1,2-dihydro-quinazolin-4-ones with formaldehyde or acetaldehyde afford 1,3-oxazino[3,4-a]quinazolin-4-one derivatives. The reactions with other aldehydes RCHO and 3-hydroxy-2-R′-1,2-dihydroquinazolin-4-ones can give 3-hydroxy-2-R-1,2-dihydroquinazolin-4-ones, 2-substituted quinazolin-4-ones, or dianthranilide. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2523–2526, December, 1998.     

Reactions of 4-morpholino-1,2-naphthoquinone with enamines ando-phenylenediamine

The reactions of 4-morpholino-1,2-naphthoquinone with enamines, cyclohexanone derivatives, afford 7a-amino-5-morpholinohexahydrobenzo[b]naphtho[1,2][1,4]dioxines, while the reaction witho-phenylenediamine yields 5-morpholinobenzo[a]phenazine. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 729–732, April, 2000.     

Reactions of 2-polyfluoroacylcyclohexanones with 1,2-diaminoarenes

Reactions of 2-polyfluoroacylcyclohexanones with 1,2-diaminoarenes yield, depending on the reaction conditions, various 2-polyfluoroalkyl-substituted benzimidazoles. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 562–565, March, 1999.     

Phosphorus-containing disiloxanes: Synthesis and thermal rearrangement of the 1,2-shift type

Methods for the synthesis of tetramethylbis(ω-phosphoryloxyalkyl)disiloxanes were developed. Thermal rearrangement of the 1,2-shift type of tetramethylbis(phosphoryloxymethyl)disiloxanes was studied. The 1,2-shift rearrangement of dimethyl(diphenoxyphosphoryloxymethyl)silyl hydrogen sulfate was found. Dedicated to Academician N. K. Kochetkov on the occasion of his 90th birthday. __________ Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1210–1214, May, 2005.     

Complete basis set,hybrid-DFT study,and NBO interpretations of the conformational behavior of 1,2-dihaloethanes

The conformational behavior of 1,2-difluoroethane (1), 1,2-dichloroethane (2), 1,2-dibromoethane (3), and 1,2-diiodoethane (4) have been analyzed by means of complete basis set CBS-QB3, hybrid-density functional theory (B3LYP/Def2-TZVPP) based methods and natural bond orbital (NBO) interpretation. Both methods showed the expected greater stability of the gauche conformation of compound 1 compared to its anti conformation. Contrary to compound 1, the anti conformations of compounds 2–4 are more stable than their gauche conformation. The stability of the anti conformation compared to the gauche conformation increases from compound 1 to compound 4. The NBO analysis of donor–acceptor (σ → σ*) interactions showed that the generalized anomeric effect (GAE) is in favor of the gauche conformation of compound 1. Contrary to compound 1, GAE is in favor of the anti conformations of compounds 2–4. The GAE values calculated (i.e., GAE_anti − GAE_gauche) increase from compound 1 to compound 4. On the other hand, the calculated dipole moment values for the gauche conformations decrease from compound 1 to compound 4. In the conflict between the GAE and dipole moments, the former succeeded in accounting for the increase of the anti conformation stability from compound 1 to compound 4. There is a direct correlation between the calculated GAE, ∆[r _c–c(G) − r _c–c(A)] and ∆[r _c–x(A) − r _c–x(G)] parameters. The correlations between the GAE, bond orders, total steric exchange energies (TSEEs), ΔG _{Anti–Gauche}, ΔG ^‡(Gauche → Gauche′, C _2v), ΔG ^‡(Anti → Gauche, C ₂), dipole–dipole interactions, structural parameters, and conformational behaviors of compounds 1–4 have been investigated.     

Conformational Analysis,Infrared, and Fluorescence Spectra of 1-Phenyl-1,2-propandione 1-oxime and Related Tautomers: Experimental and Theoretical Study

Summary. Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers: 1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol. Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G^* and 6-311G^** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH₃, PhC(NOH)–C(O)CH₃, and PhC(N–OH)C(O)CH₃. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH₃, PhC(N–O)C(OH)CH₃, and PhC(NO)C(–OH)CH₃. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone: Ph–CH(NO)C(O)CH₃, PhCH(–NO)C(O)CH₃, and PhCH(NO)–C(O)CH₃. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH₂, PhC(N–OH)C(OH)CH₂, PhC(NOH)–C(OH)CH₂, and Ph-C(NOH)C(–OH)CH₂. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH₂, PhCH(–NO)C(OH)CH₂, PhCH(NO)–C(OH)CH₂, and PhCH(NO)C(–OH)CH₂. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3 techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone > 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated λ_max for the first excited singlet state (S₁) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λ_max of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental spectra.     

Conformational Analysis, Infrared, and Fluorescence Spectra of 1-Phenyl-1,2-propandione 1-oxime and Related Tautomers: Experimental and Theoretical Study

Conformational analysis and frequency calculation were achieved for 1-phenyl-1,2-propandione 1-oxime and its four tautomers: 1-nitroso-1-phenyl-1-propen-2-ol, 1-nitroso-1-phenyl-2-propanone, 2-hydroxy-1-phenyl-propenone oxime, and 3-nitroso-3-phenyl-propen-2-ol. Calculations were carried out at the Hartree–Fock (HF), Density Functional Theory (B3LYP), and the second-order M?ller–Plesset perturbation (MP2) levels of theory using 6-31G^* and 6-311G^** basis sets. Five conformers with no imaginary vibrational frequency were obtained by free rotations around three single bonds of 1-phenyl-1,2-propandione-1-oxime: Ph–C(NOH)C(O)CH₃, PhC(NOH)–C(O)CH₃, and PhC(N–OH)C(O)CH₃. Similarly, eight structures with no imaginary vibrational frequency were encountered upon rotations around three single bonds of 1-nitroso-1-phenyl-1-propen-2-ol: Ph–C(NO)C(OH)CH₃, PhC(N–O)C(OH)CH₃, and PhC(NO)C(–OH)CH₃. In the same manner, six minima were found through rotations around three single bonds of 1-nitroso-1-phenyl-2-propanone: Ph–CH(NO)C(O)CH₃, PhCH(–NO)C(O)CH₃, and PhCH(NO)–C(O)CH₃. Also, two minima were found through rotations around four single bonds of 2-hydroxy-1-phenyl-propenone oxime: Ph–C(NOH)C(OH)CH₂, PhC(N–OH)C(OH)CH₂, PhC(NOH)–C(OH)CH₂, and Ph-C(NOH)C(–OH)CH₂. Finally, two minima were found through rotations around four single bonds of 3-nitroso-3-phenyl-propen-2-ol: Ph–CH(NO)C(OH)CH₂, PhCH(–NO)C(OH)CH₂, PhCH(NO)–C(OH)CH₂, and PhCH(NO)C(–OH)CH₂. Interconversions within the above sets of conformers were probed through scanning (one and/or two dimensional), and/or QST3 techniques. The order of the stability of global minima encountered was: 1,2-propandione-1-oxime > 1-nitroso-1-phenyl-2-propanone > 1-nitroso-1-phenyl-1-propen-2-ol > 2-hydroxy-1-phenyl-propenone oxime > 3-nitroso-3-phenyl-propen-2-ol. Hydrogen bonding appears significant in tautomers of 1-nitroso-1-phenyl-1-propen-2-ol and 2-hydroxy-1-phenyl-propenone oxime. The CIS simulated λ_max for the first excited singlet state (S₁) of 1-phenyl-1,2-propandione 1-oxime is 300.4 nm, which was comparable to its experimental λ_max of 312.0 nm. The calculated IR spectra of 1-phenyl-1,2-propandione 1-oxime and its tautomers were compared to the experimental spectra.     

Reactions of 3-hydroxy-1,2-dihydroquinazolin-4-ones with acid chlorides

The reactions of 3-hydroxy-1,2-dihydroquinazolin-4-ones with acid chlorides can afford compounds of different types. The structures of the products depend on the type of acid chloride used and on the nature of the substituent at position 2 of the 3-hydroxy-1,2-dihydroquinazolin-4-one. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 7, pp. 1346–1349, July, 1999.     

Alkoxylation of 3,6-di-<Emphasis Type="Italic">tert</Emphasis>-butyl-1,2-benzoquinone. New bis-1,2-benzoquinones

Alkoxylation of 3,6-di-tert-butyl-1,2-benzoquinone with a number of diols, including propane-1,3-diol, butane-1,4-diol, di-, and triethylene glycols, and cyclohexane-1,4-diyldimethanol, was studied. Nine new 4-alkoxy-3,6-di-tert-butyl-1,2-benzoquinones were synthesized, four of which were bis-1,2-benzoquinones with different tethers (6–13 atoms) between the quinone fragments. Depending on the length of the chain between the hydroxy groups in glycols, bicyclic 4,5-disubstituted 3,6-di-tert-butyl-1,2-benzoquinones were formed or their stepwise alkoxylation occurred. The newly synthesized o-benzoquinone derivatives can be reduced with alkali metals to give radical anions and converted into semiquinone chelates with manganese carbonyl.     

Nitroxide Radicals of some N-Phenyl Substituted 1,4- and 1,2-Phenylenediamines

Summary.  Several N-phenyl substituted 1,4- and 1,2-phenylenediamines were oxidized using radicals and 3-chloroperbenzoic acid. EPR spectroscopy confirmed the generation of nitroxide radicals originating from the oxidation of the bridging -NH-group. No radical products suggesting the simultaneous reaction with the NH₂-group were observed. Only in the case of 1,4-phenylenediamine, a low concentration of nitroxide radical H–NO–C₆H₄–NH₂ was obtained. In o-aminodiphenylnitroxide the steric effect of the NH₂-group causes a partially asymmetrical spin density distribution in both phenyl rings. Corresponding author. E-mail: omelka@fch.vutbr.cz Received September 30, 2002; accepted October 4, 2002     

Effect of the temperature on the composition and ratio of hydrolysis products of 1,2-dichlorotetramethyldisilane

The hydrolysis of 1,2-dichlorotetramethyldisilane was studied at different temperatures. At reduced temperatures, the hydrolysis gave permethylcyclo(oxadisilanes) [(Me₂Si)₂O]_n (n = 2 and 3) and α,ω-dihydroxypermethyloligo(oxadisilanes) HO[(SiMe₂)₂O]_mH (m = 1–5). The formation of the latter was proved by the GC-MS method. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 4, pp. 722–724, April, 2006.     

Syntheses, characterization and solid state thermal studies of N-propyl-1,2-diaminoethane (L) and N-isopropyl-1,2-diaminoethane (L′) complexes of nickel(II) nitrite: X-ray single crystal structure of trans-[NiL2(NO2)2]

Linkage isomers trans-bis(N-propyl-1,2-diaminoethane)dinitronickel(II) (brown, 1), trans-bis(N-isopropyl-1,2-diaminoethane)dinitritonickel(II) (blue-violet, 2a) and trans-bis(N-isopropyl-1,2-diaminoethane)dinitronickel(II) (brown, 2b) have been synthesized from solution and X-ray single crystal structure analysis of complex (1) has been performed. Simultaneous TG-DTA analyses reveal that complex (1) exhibits two successive phase transitions before to undergo decomposition (initial temperature of decomposition, Ti = 215 °C). The first one is reversible (82–98 °C; ΔH = 1.75 kJ mol⁻¹ for heating and 93–77 °C; ΔH = −1.65 kJ mol⁻¹ for cooling) and the second one is irreversible endothermic (135–150 °C kJ mol⁻¹; ΔH = 1.80 kJ mol⁻¹) phase transition. No visual color changes are observed in any of the two transitions. The causes related to the first phase transition remain unexplored. However, on the basis of IR spectral studies the second phase transition is supposed to be due to conformational changes of the diamine chelate rings. On the other hand, complexes (2a) and (2b) undergo decomposition without showing any phase transition [Ti = 185 and 195 °C for (2a) and (2b), respectively].     

[1,2]-Wittig Rearrangement of Acetals III [1]. New 1,2-Alkoxyalcohols, 1,2-Alkoxyaminesand 1,2-Dialkoxy Compounds as Chiral Ligands for Organomagnesium and Organolithium Compounds and forLithium Aluminum Hydride

Summary.  Eight O-substituted 1,2-diols and one O,N-substituted 1,2-aminoalcohol derived from 2-alkoxyoctahydro-7,8,8-trimethyl-4,7-methanobenzofurans via a [1,2]-Witting rearrangement and subsequent substitution were synthesized and tested as additives for the enantioselective addition of butyllithium and butylmagnesium chloride to benzaldehyde and for the reduction of acetophenone with lithium aluminum hydride. The selectivity of the reactions was determined by GC of the obtained 1-phenyl-1-pentanol and 1-phenylethanol on a chiral phase. Best results with regard to selectivity (52% ee and 94% ee, resp.) were achieved in the formation of 1-phenyl-1-pentanol by addition of the substituted 1,2-aminoalcohol to the organometallic reagent and in the reduction of acetophenone using an α-alkoxyalcohol (62%ee). Received March 10, 2000. Accepted March 23, 2000