S 53 Shchegol'kov, E. V. The transformations of fluoroalkyl-containing 2-arylhydrazono-1,3-dicarbonyl compounds with methylamine [Electronic resource] / E. V. Shchegol'kov, Ya. V. Burgart, V. I. Saloutin> // Journal of Fluorine Chemistry. - 2007. - Vol. 128, № 7. - P779-788 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Fluoroalkylated 1,2,3-triketone 2-arylhydrazones and 2-arylhydrazono-3-oxo esters react variously with methylamine depending on the structure of the fluorinated substituent. 2-Arylhydrazono-1,3-dicarbonyl compounds having "short" fluoroalkyl substituents condense with methylamine at the carbonyl group attached to the non-fluorinated substituent whereas ones containing a lengthy polyfluoroalkyl substituent undergo haloformic cleavage as a result of the amine addition at the carbonyl group bearing such a substituent. The resulting 2-arylazo-3-(N-methyl)amino-1-polyfluoroket-2-en-1-ones and 1-(N-methyl)amino-2-arylhydrazono-3-fluoroalkyl-3-oxopropanamides have complexing properties, and they can bind to nickel(II) and copper(II) ions. Nickel chelates can be obtained by a three-component condensation of 2-arylhydrazono-1,3-dicarbonyl compounds and methylamine in the presence of nickel(II) cations. \\\\Expert2\\nbo\\Journal of Fluorine Chemistry\\2007, v.128. p.779.pdf |
H 10 H-1 and C-13-NMR investigations on-adduct formation of 1,2,4-triazine 4-oxides and 3-chloro-6-phenyl-1,2,4-triazine with liquid ammonia and alkylamines [Text] / A. Rykowski, O. N. Chupakhin, D. N. Kozhevnikov, V. N. Kozhevnikov, V. L. Rusinov, der Plas H. C. Van> // Heterocycles. - 2001. - Т. 55, № 1. - P127-133 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: 1H- and 13C-NMR spectra of the ?-adducts formed between 6-phenyl-1,2,4-triazine 4-oxide (1a), 3-ethyl-6-phenyl-1,2,4-triazine 4-oxide (1b) and liquid ammonia, methylamine or dimethylamine are described, together with 1H NMR spectra of 3-chloro-6-phenyl-1,2,4-triazine (7) in liquid ammonia. The results of the NMR study have shown that the carbon C-5 in 1a-b and 7 is the preferred site for nucleophilic attack by liquid ammonia and alkylamines at low temperatures (from -75° to -20°C). The ?-adduct (5e) formed between 1a and dimethylamine at -75°C on heating to -20°C irreversibly converts to open-chain product (3a), via intermediary C-3 ?-adduct (6). The amination of 7 into 3-amino-6-phenyl-1,2,4-triazine (10) occurs via SN(AE) mechanism involving the isomerisation of the C-5 ?-adduct (8) into the C-3 ?-adduct (9) as confirmed by a 15N study with labeled liquid ammonia. |
C 73 Condensation of fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones with methylamine [Electronic resource] / E. V. Shchegol'kov, Ya. V. Burgart, P. A. Slepukhin, O. N. Kazheva, V. I. Saloutin> // Russian Journal of Organic Chemistry (Translation of Zhurnal Organicheskoi Khimii). - 2007. - Vol. 43, № 12. - P1788-1796 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones react with methylamine in different ways, depending on the substrate structure. Arylhydrazones having a short fluoroalkyl substituent (RF = CF3, HCF2CF2) react at the carbonyl group adjacent to the nonfluorinated substituent to give 3-alkyl(aryl)-2-aryldiazenyl-3-methylamino-1-polyfluoroalkylprop-2-en-1-ones. Arylhydrazones with a long-chain fluoroalkyl group (RF = C3F7 and longer) and a bulky nonfluorinated group take up methylamine molecule at the carbonyl group linked to the fluorinated substituent, and the subsequent haloform reaction yields N-methyl-2-arylhydrazono-3-oxobutanamides. Both types of products are formed in reactions of methylamine with 1,2,3-triketone 2-arylhydrazones having a long fluoroalkyl group and methyl group at the other carbonyl group. Template condensation of fluoroalkyl-containing 1,2,3-trione 2-arylhydrazones with methylamine over Ni(II) template gives bis[3-alkyl(aryl)-1-polyfluoroalkyl-3-methylamino-2-aryldiazenylprop-2-en-1-onato-N,N?]-nickel(II), regardless of the size of the fluoroalkyl substituent. The same complexes and their copper analogs can be obtained by treatment of 3-alkyl(aryl)-2-aryldiazenyl-3-methylamino-1-polyfluoroalkylprop-2-en-1-ones with the corresponding metal salts \\\\Expert2\\nbo\\Russian Journal of Organic Chemistry\\2007, 43 (12), 1788.pdf |
S 53 Shchegol'kov, E. V. Reactions of 5,6,7,8-Tetrafluoro-4-hydroxy-2H-chromen-2-ones with methylamine [Electronic resource] / E. V. Shchegol'kov, Ya. V. Burgart, V. I. Saloutin> // Russian Journal of Organic Chemistry (Translation of Zhurnal Organicheskoi Khimii). - 2006. - Vol. 42, № 12. - P1838-1844 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: 5,6,7,8-Tetrafluoro-4-hydroxy-2H-chromen-2-one reacts with methylamine to give methylammonium 5,6,7,8-tetrafluoro-2-oxo-2H-chromen-4-olate, regardless of the solvent. The reaction of 3-acetyl-5,6,7,8-tetrafluoro-4-hydroxy-2H-chromen-2-one with the same amine in ethanol or acetonitrile leads to the formation of methylammonium 3-acetyl-5,6,7,8-tetrafluoro-2-oxo-2H-chromen-4-olate, while in dimethyl sulfoxide 5,6,8-trifluoro-7-methylamino-3-(1-methylaminoethylidene)-3,4-dihydro-2H-chromene-2,4-dione is formed. The latter is also formed in the reaction of 5,6,7,8-tetrafluoro-4-hydroxy-3-(1-iminoethyl)-2H-chromen-2-one with methylamine in DMSO, whereas in ethanol and acetonitrile 5,6,7,8-tetrafluoro-3-(1-methylaminoethylidene)-3,4-dihydro-2H-chromene-2,4-dione is obtained. 5,6,7,8-Tetrafluoro-3-(1-methylaminoethylidene)-3,4-dihydro-2H-chromene-2,4-dione reacts with methylamine, yielding 7-mono-or 5,7-bis(methylamino)-substituted derivatives \\\\Expert2\\nbo\\Russian Journal of Organic Chemistry\\2006, 42 (12), 1838.pdf |
S 53 Shcherbakov, K. V. Reactions of 2(3)-ethoxycarbonyl-5,6,7,8-tetrafluorochromones with methylamine [Electronic resource] / K. V. Shcherbakov, Ya. V. Burgart, V. I. Saloutin> // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2005. - Vol. 54, № 9. - P2157-2162. - Bibliogr. : p. 2162 (18 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): CHROMONE -- METHYLAMINE -- NUCLEOPHILIC SUBSTITUTION -- RING OPENING Аннотация: 2-Ethoxycarbonyl-5,6,7,8-tetrafluorochromone reacts with methylamine differently, depending on the solvent nature and the amount of the amine: in DMSO and MeCN, the fluorine atom at the C(7) atom is initially replaced and then the C(2) and/or C(9) are attacked, while in ethanol, the reaction involves the C(2) atom with opening of the pyrone ring. The reaction of 3-ethoxycarbonyl-5,6, 7,8-tetrafluoro-2-methylchromone with methylamine results, regardless of the solvent, in opening of the chromone ring and the formation of intermediate ethyl 3-(3,4,5,6-tetrafluoro-2-hydroxyphenyl)-2-(1-methylamino)ethylidene-3- oxopropionate, which undergoes intramolecular cyclization to give 5,6,7,8-tetrafluoro-3-(1-methylamino)ethylidene-3,4-dihydro-2H-benzopyran-2, 4-dione. \\\\Expert2\\nbo\\Russian Chemical Bulletin\\2005, 54 (9), 2157-2162.pdf |
R 30 Reactions of 2-ethoxycarbonyl(carboxy)-5,6,7,8-tetrafluorochromones with N-nucleophiles [Electronic resource] / V. I. Saloutin, I. T. Bazyl, Z. E. Skryabina, O. N. Chupakhin> // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 1994. - Vol. 43, № 5. - P849-853 Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): 2-ETHOXYCARBONYL(CARBOXY)-5,6,7,8-TETRAFLUOROCHROMONES -- N-NUCLEOPHILES -- ETHYLENEDIAMINE -- AMINES -- NUCLEOPHILIC REPLACEMENT Аннотация: The direction of reactions of 2-ethoxycarbonyl-5,6,7,8-tetrafluoro- and 2-carboxy-5,6,7,8-tetrafluorochromones with ammonia, methylamine, hexylamine, and aniline depends on the inductive effect of the substituent at position C-2 of the chromone and on the basicity of the amine. Nucleophilic aromatic substitution of a fluorine atom takes place in the interaction of 2-ethoxycarbonyl-5,6,7,8-tetrafluorochromone with secondary amines (morpholine, N-methylpiperazine) and ethylenediamine. \\\\Expert2\\nbo\\Russian Chemical Bulletin\\1994, 43 (5), 849.pdf |