Synthesis and structure of 2-ethoxy- and 2-aminomethylidene-3-fluoroalkyl-3-oxopropionates

Pryadeina, M. V.; Burgart, Yanina V.; Салоутин, В. И.; Слепухин, П. А.; Kazheva, Olga N.; Шилов, Г. В.; D’yachenko, O. A.; Чупахин, О. Н.

doi:10.1134/s1070428007070019

Cited by 23 publications

(20 citation statements)

References 4 publications

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“…The E,E-and Z,Z-isomeric forms in the 1 H and 19 F NMR spectra were attributed in accordance with our previous work [19] in which CH-and NH-protons of EE-isomer are observed at lower field compared to that of Z,Z-isomer.…”

supporting

confidence: 76%

“…The IR diffuse reflectance spectra were recorded on a Perkin Elmer Spectrum One Fourier FT-IR instrument in the interval 400-4000 cm -1 in the solid state as powders on a stick using a diffuse reflectance attachment (DRA). The 1 H (400 MHz) and 19 F (376 MHz) NMR spectra were recorded on a Bruker DRX-400 spectrometer with (CH 3 ) 4 Si and C 6 F 6 as internal standarts, respectively. Elemental analyses were performed on a Perkin Elmer PE 2400 series II elemental analyzer.…”

Section: Equipmentmentioning

confidence: 99%

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Novel Polydentate Macroacyclic Schiff Base Ligands Based on 2,6-Diformylphenol

Kudyakova¹,

Burgart²,

Салоутин³

2014

MHC

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[1+2] Condensation of 2,6-diformylphenol (1) with ethyl-2-[(2-aminophenyl) IntroductionDirected synthesis of polydentate organic compounds with various donor centers followed by metal complexes formation, their structures' definition and evaluation of regioselective coordination factors play an important role in design of artificial models of biologically important objects [1,2] and searching for compounds with required physicochemical and applied properties, [3][4][5] e.g. magnetic, [6,7] catalytic, [8][9][10] medicobiological, [11] etc. Previously we have reported on macroacyclic polydentate ligands via diethyl-2-[(2-aminophenyl)-aminomethylidene]malonate or ethyl-2-[(2-aminophenyl)aminomethylidene]-3-oxo-3-(polyfluoro)alkylpropionates with thiophene-2,5-dicarboxaldehyde. [12,13] It was shown the structure of their coordination centers depends on the symmetry of 1,3-dicarbonyl fragment. These compounds were expected to form complexes with 3d metal ions; however our attempts to isolate stable chelates were unsuccessful because of sulfur atom in thiophene cycle seems to have the low donor ability for the formation of strong donor-acceptor bond with metal ion. [14] Unlike thiophene-2,5-dicarboxaldehyde 2,6-diformylphenol have a hydroxy group that can provide the covalent bonding with metal ions. It is worth noting that 2,6-diformylphenol and its derivatives are widely used in the design of polydentate ligands which can form polynuclear complex systems having magnetic interaction between the metal centers. Due to the study of stereochemical, electronic, magnetic, catalytic, spectroscopic and biological properties one can suggest for them some important applications. [15][16][17][18] In this paper we describe the synthesis, coordination properties and tuberculostatic activity of new macroacyclic Schiff base ligands based on 2,6-diformylphenol 1 and ethyl-2-[(2-aminophenyl)aminomethylidene]-1,3-dicarbonyl compounds 2a-d. Results and DiscussionIt was found the reaction of dialdehyde 1 with amines 2a-d in ethanol at room temperature proceeds regioselectively and gives [1+2] condensation productsdiazomethines 3a-d in good yields (Scheme 1). Structures of 3a-d were characterized by IR, 1 H, 19 F NMR spectroscopy and elemental analysis.An important point is that compounds 3a-d have labile hydrogen atom and therefore they can be involved in keto-enol and amine-imine tautomerism. The imino-enone, imino-enol, and/or amino-enone tautomers are possible for their structure. Furthermore, amino-enone tautomers of 3-oxoesters derivatives 3c,d can exhibit Z,E-isomerism because of different position of non-equivalent substituents relative to C=C bond. ). In this case absorption bands are either doublet or broadened. Based on the IR spectra analogy we suggested for compounds 3c,d E,Eisomeric structure in which bis(amino-enone) fragments stabilized with IMHB are in trans-position relative to aromatic spacer similarly to described earlier [13] thiophene derivatives.According to the 1 H and 19 F NMR spectral data azomethines 3c,d in C...

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supporting

confidence: 76%

Section: Equipmentmentioning

confidence: 99%

Novel Polydentate Macroacyclic Schiff Base Ligands Based on 2,6-Diformylphenol

Kudyakova¹,

Burgart²,

Салоутин³

2014

MHC

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“…22 The X ray diffraction studies of compounds 2b, 4b, and 5а,d were performed on an Xcalibur 3 diffractometer equipped with a CCD detector (λ(Mo Кα) = 0.71073 Å, graphite monochro mator, 295(2) K (120(2) K for 2b), ω scan mode, scan increment 1°, time of frame measurement 20 s). A fragment of the red 3 , ρ max /ρ min filament crystal 0.29Ѕ0.15Ѕ0.06 mm in size was used for the study of compound 5a, and a fragment of the red filament crystal 0.22Ѕ0.13Ѕ0.06 mm in size was used for studying compound 5d.…”

Section: Methodsmentioning

confidence: 99%

“…The signals were assigned to the Z or E isomeric form according to the principles established earlier. 22 According to this, the shifts of the protons of the СН and NH groups are determining in the 1 Н NMR spectra: for the Е isomer the signals of these groups are observed in a weaker field compared to the signals of the protons corresponding to the Z isomer. In the 19 F spectra, the signals of the fluorine atoms of the α CF 3 and α CF 2 groups of the Z form are characterized by a more downfield shift compared to the corresponding signals of the fluorine atoms of the Е isomer.…”

mentioning

confidence: 97%

“…The signals were assigned to the E,E , E,Z , Z,E , and Z,Z forms using the data obtained by us earlier. 22 Based on the structure of ligands 2a-c, one may assume that they are able to form metallocomplex com pounds due to coordination involving the tridentate N 2 O moiety. However, the treatment of ester 2b with copper(II) and nickel(II) acetates gave no desirable metal complexes, unlike the transformations of the non fluorinated analog.…”

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confidence: 99%

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New enamine ligands derived from ethyl 2-ethoxymethylidene-3-oxo-3-polyfluoroalkylpropionates and o-phenylenediamine

et al. 2010

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Diethyl 2,2´ [1,2 phenylenebis(aminomethylidene)]bis(3 oxo 3 polyfluoroalkylpropion ates) were synthesized by the condensation of a double excess of ethyl 2 ethoxymethylidene 3 oxo 3 polyfluoroalkylpropionates with o phenylenediamine. The use of equimolar ratios of the starting reactants affords ethyl 2 [(2 aminophenyl)aminomethylidene] 3 oxo 3 polyfluoroalkylpropionates from which nonsymmetric biscondensation products were syn thesized by the reaction with related reactants containing different polyfluoroalkyl substituent. The copper(II), nickel(II), and cobalt(II) complexes were obtained on the basis of new ligands.Interest in synthesis of metal complexes based on azomethine compounds is caused by their catalytic activity in polymerization reactions 1-3 and magnetic 4-7 and luminescence 8,9 properties. Non fluorinated 2 ethoxy methylidene 1,3 dicarbonyl compounds in reactions with 1,2 diamines form biscondensation products at the ethoxymethylidene moiety 10-12 and related metal com plexes. 13-16 It is possible to obtain monocondensation products 17-19 from which symmetric and asymmetric ligands 20 were synthesized, including the macrocyclic ligands 15,17-20 used in the synthesis of the metallocomplex compounds. 17-20 Schiff bases obtained by transformations of 2 ethoxymethylidene 3 oxo 3 fluoroalkylpropionates with different diamines can also serve as organic mol ecules forming the ligand shell. It is known 21 that the introduction of the fluorine atom into organic molecules changes their physicochemical properties, reactivity, bio logical activity and other characteristics caused by the presence of electronegative fluorine atoms and important in practical and theoretical aspects. However, published data on the participation of polyfluorinated analogs in similar polycondensation reactions are lacking.In the present work, we studied the reactions of ethyl 2 ethoxymethylidene 3 oxo 3 polyfluoroalkylpropion ates 1 with o phenylenediamine with the purpose to syn thesize new ligands and analyzed a possibility of the prepa ration of related metallocomplex compounds with a series of transition metals.It was found that the reaction of compounds 1a-c with 1 equiv. of o phenylenediamine in diethyl ether at room temperature afforded the monoadducts, viz., ethyl 2 [(2 aminophenyl)aminomethylidene] 3 fluoroalkyl 3 oxopropionates 2a-с, as a result of the nucleophilic attack of the amino group at the ethoxymethylidene moiety (Scheme 1). The use of a double excess of esters 1a-c results in the formation of symmetric products 3a-c due to the condensation of two molecules of ester 1a-c with one diamine molecule.Monosubstitution products 2а-c contain free NH 2 groups, which makes it possible to carry out their further transformations. The condensation of compounds 2а,с with the corresponding substrates 1a,b (see Scheme 1)

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Toward Continuous‐Flow Synthesis of Biologically Interesting Pyrazole Derivatives

2019

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A two‐step continuous‐flow synthesis of substituted pyrazole derivatives has been developed via the formation of vinylidene keto esters as key intermediates. Heterogeneous Ni2+‐montmorillonite was found to be an efficient catalyst for orthoester condensation of 1,3‐dicarbonyls under flow conditions. The intermediate reacted with methylhydrazine to afford pyrazole derivatives, for which suitable selection of a solvent played a key role in achieving high yields and excellent regioselectivities of the desired products. An application of this protocol has been demonstrated by the synthesis of a key intermediate for biologically active pyrazoles such as Bixafen.magnified image

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Synthesis and structure of 2-ethoxy- and 2-aminomethylidene-3-fluoroalkyl-3-oxopropionates

Cited by 23 publications

References 4 publications

Novel Polydentate Macroacyclic Schiff Base Ligands Based on 2,6-Diformylphenol

Novel Polydentate Macroacyclic Schiff Base Ligands Based on 2,6-Diformylphenol

New enamine ligands derived from ethyl 2-ethoxymethylidene-3-oxo-3-polyfluoroalkylpropionates and o-phenylenediamine

Toward Continuous‐Flow Synthesis of Biologically Interesting Pyrazole Derivatives

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