K 66 Kodess, M. I. Reactions of 3-(polyfluoroacyl)chromones with hydroxylamine : synthesis of novel R - containing isoxazole and chromone derivatives [Electronic resource] / M. I. Kodess, V. Ya. Sosnovskikh, V. S. Moshkin // Tetrahedron. - 2008. - Vol. 64, № 34. - P7877-7889 : рис. - Библиогр. : с. 7888-7889 (32 назв.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Reaction of 3-(polyfluoroacyl)chromones with hydroxylamine free base proceeds via nucleophilic 1,4-addition followed by opening of the pyrone ring and subsequent cyclization to 4-(polyfluoroalkyl)-4H-chromeno[3,4-d]isoxazol-4-ols in good yields. On treatment with trifluoroacetic acid, the isoxazole ring of this annulated heterocyclic system opens to give 3-cyano-2-(polyfluoroalkyl)chromones, which were successfully hydrolyzed with concentrated H2SO4 to afford 3-carbamoyl-2-(polyfluoroalkyl)chromones. On the other hand, oximation of 3-(polyfluoroacyl)chromones with hydroxylamine hydrochloride occurs either at the carbonyl carbon atom connected to the RF group or at the C-2 atom to give 3-RFC(NOH)-chromones and 5-RF-4-salicyloylisoxazole oximes, respectively. The former were easily converted to 3-RF-4-salicyloylisoxazoles by simple heating in dimethyl sulfoxide.?? \\\\Expert2\\nbo\\Tetrahedron\\2008, v. 64, N34, p. 7877.pdf |
N 57 Ni(II)-Mediated nitrosation of oximes bearing an alfa-CH2 group [Electronic resource] / A. V. Makarycheva-Mikhailova, P. V. Gushchin, M. N. Kopylovich, I. N. Ganebnuikh, V. N. Charushin, M. P. Haukka, J. L. Armando , V. Yu. Kukushkin // Inorganic Chemistry Communications. - 2006. - Vol. 9, № 8. - P869-871 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Heating of NiCl2 · 6H2O with 10-fold excess of an oxime having an CH2 group (1–4) at 100 °C for 1 day in air leads to the formation of the dioxime/ato complexes [Ni(dioxime/ato)2] (5–8) formed due to a novel type of metal-mediated nitrosation. Compounds 5–8 were characterized by elemental analyses, FAB (5–7) or APCI (8) mass-spectrometry, IR, 1H and 13C{1H} spectroscopies (for 8), and X-ray structural study has been performed for 5 and 8; the corresponding ketones (9–12) were identified by LC–MS. \\\\Expert2\\nbo\\Inorganic Chemistry Communications\\2006, v.9, p.869.pdf |
N 89 Novel chemical modifications at the 4-position of chromones. Synthesis and reactivity of 4H-chromene-4-spiro-5-isoxazolines and related compounds [Text] / V. Ya. Sosnovskikh, B. I. Usachev, A. Yu. Sizov, M. I. Kodess // Tetrahedron Letters. - 2004. - Vol. 45, № 39. - P7351-7354 : ил. - Библиогр.: с. 7353-7354 (22 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): CHROMONES -- DILITHIOOXIMES -- 4H-CHROMENE-4-SPIRO-5'-ISOXAZOLINES; -- ALFA,BETA-UNSATURATED OXIMES -- BECKMANN REARRANGEMENT -- NITROSATION -- BROMINATION Аннотация: Reactions of chromones with dilithiooximes proceed via nucleophilic 1,2-addition to give, on acidification, 4H-chromene-4-spiro-5-isoxazoline derivatives in high yields. On treatment with concentrated H2SO4 the isoxazoline ring of this novel spiroannulated heterocyclic system opens to give alfa,beta-unsaturated oximes, which undergo nitrosation, bromination, and the Beckmann rearrangement to the corresponding spiroisoxazolines and alfa,beta-unsaturated amides, respectively. The latter can be obtained directly by the Beckmann rearrangement of 4H-chromene-4-spiro-5`-isoxazolines \\\\Expert2\\nbo\\Tetrahedron Letters\\2004, v. 45, p.7351.pdf |
S 78 Spiro[4H-chromene-4,5-isoxazolines] and related compounds: Synthesis and reactivities [Electronic resource] / V. Ya. Sosnovskikh, A. Yu. Sizov, B. I. Usachev, M. I. Kodess, V. A. Anufriev // Russian Chemical Bulletin (Translation of Izvestiya Akademii Nauk, Seriya Khimicheskaya). - 2006. - Vol. 55, № 3. - P535-542 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Reactions of chromones with methyl ketoximes in the presence of lithium diisopropylamide follow the nucleophilic 1,2-addition mechanism to give spiro[4H-chromene-4,5?-isoxazolines] in good yields. The isoxazoline ring in spiro[4H-chromene-4,5?-isoxazolines] undergoes opening under the action of conc. H2SO4, yielding ?,?-unsaturated oximes. Their nitrosation and bromination lead to the corresponding spiroisoxazolines, while the Beckmann rearrangement, to ?,?-unsaturated amides. The latter are also formed directly from spiro[4H-chromene-4,5?-isoxazolines] under the action of PCl5. N-Substituted acetophenone hydrazones in the presence of lithium diisopropylamide react at the C(4) atom of 2-trifluoromethylchromone, while acetophenone anil under the same conditions, at the C(2) atom \\\\Expert2\\nbo\\Russian Chemical Bulletin\\2006, 55 (3), 535.pdf |
C 52 Chiral palladium complexes with monoterpenoids oximes [Electronic resource] / O. A. Gur'eva, O. A. Zalevskaya, L. L. Frolova, I. N. Alekseev, P. A. Slepukhin, A. V. Kuchin // Russian Journal of General Chemistry. - 2014. - Vol.84, №1. - С. 137-142. - Bibliogr. : p. 142 (16 ref.) Рубрики: ХИМИЧЕСКИЕ НАУКИ Кл.слова (ненормированные): CIS-VERBANONE -- MENTHONE -- OXIMES Аннотация: Oximes of cis-caran-4-one, 3α- and 3β-hydroxycaran-4-ones, cis-verbanone, menthone, and 2β-hydroxybornan-3-one have been synthesized. The obtained oximes react with lithium tetrachloropalladate to give new chiral palladium complexes containing mono-or bidentate oxime ligands \\\\expert2\\nbo\\Russian Journal of General Chemistry\\2014, V. 84, N 1, p. 137–142.pdf |
Step by step and one-pot syntheses of 5-hydroxy-5-(polyfluoroalkyl)isoxazol-4(5h)-one oximes / N. V. Palysaeva, A. B. Sheremetev, N. S. Boltacheva, P. A. Slepukhin, M. G. Pervova, V. I. Filyakova, V. N. Charushin // Mendeleev Communications. - 2018. - Vol. 28, № 1. - P126-127 Рубрики: ХИМИЧЕСКИЕ НАУКИ |
Gyrdymova, Y. V. Synthesis of caryophyllane oximes and hydrazone and their O- and N-acylated derivatives / Y. V. Gyrdymova, S. A. Rubtsova, P. A. Slepukhin // Chemistry of natural compounds. - 2021. - Vol. 57. - P72–78 Рубрики: ХИМИЧЕСКИЕ НАУКИ |
Oximes of fluoroalkyl-containing 1,3-diketones: specific features of synthesis, analysis, and thermal stability / N. S. Boltacheva, P. A. Slepukhin, M. G. Pervova [et al.] // Russian chemical bulletin. - 2022. - Vol. 71, № 7. - P1464-1473 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Nitrosation of lithium 1,3-diketonates bearing fluoroalkyl and aryl (or hetaryl) substituents in positions 1 and 3 results in 3-polyfluoroalkyl-1,2,3-propanetrione 2-oximes (from this point on, oximes). Under similar conditions, lithium (Z)-1,1,1-trifluoro-4-oxo-4-(thien-2-yl)-2-buten-2-olate forms a hydration product of the corresponding oxime. Nitrosation of fluoroalkyl-containing lithium 1,3-diketonates is accompanied by retro-decomposition of the initial lithium 1,3-diketonates and the target oximes (or their hydration products) followed by oxidation and hydrolysis of the reaction products. Under the GC-MS conditions, the oximes undergo partial thermal decomposition to 2-aryl(hetaryl)-2-oxoethanenitriles. An analysis of solutions of the oximes in DMSO-d6 by 1H and 19F NMR spectroscopies revealed isomerization and hydration of these compounds. The temperature ranges of stability of the oximes were determined by thermogravimetric analysis and differential thermal analysis. The molecular and crystal structures of 4,4-difluoro-1-(4-methoxyphenyl)-1,2,3-butanetrione 2-oxime and 4,4,4-trifluoro-1-(thien-2-yl)-1,2,3-butanetrione 2-oxime were determined by X-ray diffraction. |
Oximes of fluoroalkyl-containing 1,3-diketones: specific features of synthesis, analysis, and thermal stability / N. S. Boltacheva, P. A. Slepukhin, M. G. Pervova [et al.] // Russian chemical bulletin. - 2022. - Vol. 71, № 4. - P1464-1473 Рубрики: ХИМИЧЕСКИЕ НАУКИ Аннотация: Nitrosation of lithium 1,3-diketonates bearing fluoroalkyl and aryl (or hetaryl) substituents in positions 1 and 3 results in 3-polyfluoroalkyl-1,2,3-propanetrione 2-oximes (from this point on, oximes). Under similar conditions, lithium (Z)-1,1,1-trifluoro-4-oxo-4-(thien-2-yl)-2-buten-2-olate forms a hydration product of the corresponding oxime. Nitrosation of fluoroalkyl-containing lithium 1,3-diketonates is accompanied by retro-decomposition of the initial lithium 1,3-diketonates and the target oximes (or their hydration products) followed by oxidation and hydrolysis of the reaction products. Under the GC-MS conditions, the oximes undergo partial thermal decomposition to 2-aryl(hetaryl)-2-oxoethanenitriles. An analysis of solutions of the oximes in DMSO-d6 by 1H and 19F NMR spectroscopies revealed isomerization and hydration of these compounds. The temperature ranges of stability of the oximes were determined by thermogravimetric analysis and differential thermal analysis. The molecular and crystal structures of 4,4-difluoro-1-(4-methoxyphenyl)-1,2,3-butanetrione 2-oxime and 4,4,4-trifluoro-1-(thien-2-yl)-1,2,3-butanetrione 2-oxime were determined by X-ray diffraction. |