Ketone Azine Research Articles

Reactions of bicyclo[2.2.1]heptane-2-endo,3-endo-dicarbohydrazide and its 5-endo,6-endo- and 5-endo,6-exo-dihydroxy derivatives with 7-oxooctyl 7-oxooctanoate and bis(7-oxooctyl) hexanedioate

The condensation of 7-oxooctyl 7-oxooctanoate and bis(7-oxooctyl) hexanedioate with bicyclo-[2.2.1]heptane-2-endo,3-endo-dicarbohydrazide and its 5-endo,6-endo- and 5-endo,6-exo-dihydroxy derivatives obtained from dimethyl norbornene-2-endo,3-endo-dicarboxylate gave the corresponding macrocyclic lactones containing a ketone azine fragment instead of the expected hydrazide moiety.

Coordination complexes and polymers from the initial application of phenyl-2-pyridyl ketone azine in mercury chemistry

A series of new mercury(II) azine Schiff base complexes have been synthesized and characterized from the initial use of phenyl-2-pyridyl ketone azine in HgII chemistry. The synthetic/crystallization technique utilized involved the use of a branched tube, where temperature differential allowed for the slow crystallization of the products. The synthesized compounds are the mononuclear [Hg(L)Cl2] (1), [Hg(L)Br2] (2), [Hg(L)(NO2)2] (3), and the dinuclear [Hg2(μ-L)(SCN)4] (4) coordination compounds, as well as a 1D coordination polymer [Hg(L)(μ-I)2HgI2]n (5) (L=phenyl-2-pyridyl ketone azine). From the X-ray data, it is evident that this versatile ligand functions as a bi- or tridentate chelate, and is also able to bridge two HgII centers. The crystal structures of 1 and 2 are similar, both containing two crystallographically independent HgII molecules, one tetrahedrally coordinated and one exhibiting trigonal bipyramidal geometry. The heptacoordinated HgII center in 3 adopts a distorted capped trigonal prismatic coordination sphere, while in the dinuclear complex 4, the metal ions are bridged via the bis(bidentate) L and each center is also bound to two S-bonded thiocyanate units. The one-dimensional coordination polymer in 5 consists of a tetrahedral HgI4 and a trigonal bipyramidal HgN3I2 chromophore unit, bridged by μ-I− bridges. The thermal stability of the crystal lattice in 1–5 follows the pattern 3>1>2>5>4, as studied by TG/DTA, while the TG data of 1, 2, and 5 are similar, but different than the respective ones for 3 and 4, between which important similarities are observed. In the solid state, the ligand and compounds 1–5 exhibit intraligand π→π∗ fluorescence at room temperature.

Crystal structures and spectral properties of two polyoxometalate-based inorganic–organic compounds from silver–azine building blocks with bis-bidentate and tridentate ligands

Two polyoxometalate-based inorganic–organic hybrid compounds constructed from silver(I)-L species and saturated Keggin type polyoxoanion, [Ag2L21]2(SiMo12O40)·1.5DMF·0.5CH3OH⋅H2O 1 and [{Ag4L22(DMF)5}(SiMo12O40)] 2 (L1=phenyl 2-pyridyl ketone azine, L2=3-phenyltriazolo[1,5-a]pyridine), have been synthesized and structurally characterized by IR, UV, elemental analysis, XRPD and complete single crystal structure analyses, where the ligands L1 and L2 are bis-bidentate and tridentate azines synthesized with the same materials under different conditions. The structure of 1 exhibits a dinuclear double-helicate with [SiMo12O40]4− anions as counter ions, where all of the Ag centers coordinate to bis-bidentate chelating ligands. Compound 2 displays a two-dimensional sheet formed by the Ag–organic infinite chains and the [SiMo12O40]4− alternately arranged in a “rail-like” fashion. The luminescent properties of 1 and 2 in the solid state were investigated.

Dinuclear Lanthanide(III) Complexes by Metal-Ion-Assisted Hydration of Di-2-pyridyl Ketone Azine

The initial employment of di-2-pyridyl ketone azine in 4f metal chemistry has led to a unique ligand transformation; the resulting anionic ligand is able to bridge two Ln(III) ions, affording neutral and cationic dinuclear complexes with interesting properties.

Assembly of one novel polyoxometalate-based inorganic–organic compound from copper-Schiff base building block: Synthesis, crystal structure and spectral properties

A novel copper(II) inorganic–organic hybrid compound [CuL(DMF)(CH3OH)]2(PMoVMoVI11O40)·2DMF (L=phenyl 2-pyridyl ketone azine) 1 has been synthesized and characterized by IR, UV, elemental analysis and X-ray crystallography. Cu(II) atom has a distorted square pyramidal environment interconnecting with N3O2 donor set. In solid-state there are three types of CH⋯π interactions between adjacent [CuL(DMF)(CH3OH)]2+, which generate a two-dimensional (2D) layer. Adjacent 2D layers form porous channels in which polyoxoanions as templates are filled. Simultaneously, the oxygen atoms of polyoxoanion as electron acceptors feather multiple intermolecular hydrogen bonds, through which giving rise to a 3D supramolecular network. The luminescent properties of the compound 1 were investigated in the solid state and in aqueous solution at room temperature, respectively.

Iodine-catalyzed ketazines cyclization into 2-pyrazolines

Ketazines are known to undergo cyclization into 2-pyrazolines under the action of protonic acids. Dicarboxylic acids are considered to be the most active catalysts for ketazines cyclization [1, 2]. The reaction is performed in the presence of an equimolar amount of the acid and often requires additional heating. The pyrazoline forms not in the form of a base but as a pyrazolinium salt of the corresponding acid, therefore the reaction mixture should be treated with strong bases. Yield of pyrazolines reaches from 50 to 81% [2]. We found that by adding to acetone azine (Ia) 0.5 wt% of crystalline iodine a strong self-heating was observed (to 125–130°C), and after maintaining the reaction mixture at this temperature for 1 h the GLC analysis showed a complete conversion of the azine into 3,5,5-trimethylpyrazoline (IIa). The pyrazoline was isolated by distillation in 94% yield. Compare the acetone azine cyclization with anhydrous oxalic acid at azine to acid molar ratio 1:1.1: After 4-hour heating on a water bath the pyrazoline forms in 78% yield [2]. It is presumable that initially forms a complex of azine with iodine A where (same as in the catalysis with acids) because of a positive charge arising on the nitrogen the intramolecular condensation of crotonic type is facilitated and leads to a complex pyrazoline–iodine B, which reacting with azine Ia provides the base pyrazoline IIa and the azine complex with iodine A. Evidently since the iodine unlike the proton is a mild acid [3] the equilibrium (2) is more shifted to the right than the similar equilibrium involving the protonated azine and pyrazoline. This event provides for the reaction proceeding in the presence of the catalytical quantity of iodine. 3,5,5-trimethyl-2-pyrazoline (IIa). To 11.22 g (0.1 mol) of acetone azine (Ia) was added at room temperature while stirring 0.05 g (0.2 mmol) of I2. The reaction mixture self-heated to 125–130°C and was kept at 130°C for 1 h. After a vacuum distillation the yield of the product was 10.55 g (94%), bp 57–59°C (20 mm Hg), d4 0,9011, nD 1.4571 {bp 52.5°C (15 mm Hg), d4 0.9025, nD 1.4573 [2]}. 1H NMR spectrum, δ, ppm: 1.24 s [6H, C(CH3)2], 1.92 s (3H, N=CCH3), 2.40 s (2H, CH2), 4.01 br.s (NH). Found, %: C 64.30; H 10.69; N 25.01. C6H12N2. Calculated, %: C 64.24; H 10.78; N 24.97. 5-Methyl-3,5-diethyl-2-pyrazoline (IIb). To 14.2 g (0.1 mol) of methyl ethyl ketone azine (Ib) was added at room temperature while stirring 0.05 g (0.2 mmol) of I2. The reaction mixture self-heated to 50–60°C, then it was heated for 1 h at 140°C. After a vacuum distillation the A

Anion dependent formation of Ag(I) complexes of multidentate azine ligands: Synthesis and structural study

The extended structures of Ag-complexes of the azine based ligands phenyl-2-pyridyl ketone azine ( L 1 ) and di-2-pyridyl ketone azine ( L 2 ) are reported, and focus is made on the investigation of the influence of the anion and supramolecular interactions on the self-assembly. Using AgNO 3, AgClO 4 and CF 3COOAg salts as starting materials for both ligands in acetonitrile, we observed the formation of the dinuclear complexes [Ag 2( L 1 ) 2](NO 3) 2 ( 1a), [Ag 2( L 1 ) 2](ClO 4) 2 ( 1b), from L 1 , the tetranuclear complexes [Ag 4( L 2 ) 2 (NO 3)(CH 3CN) 2](NO 3) 3 ( 2a), [Ag 4( L 2 ) 2(CF 3COO) 3CH 3CN](CF 3COO) ( 2b) and the linear chain polynuclear complex {[Ag 3( L 2 ) 2] (ClO 4) 3} n ( 3) from L 2 . The X-ray structures show that the molecular geometry depends on the choice of anion. The silver centers have distorted tetrahedral coordination geometry in all the complexes. Weak hydrogen bonding and other interactions result in 2-D and 3-D networks in these complexes.

Fused Nitrogen-Containing Heterocycles: IV. 3-Benzoyl-2-oxo-1,2-dihydroquinoxaline Hydrazones and Flavazoles Derived Therefrom

3-Benzoyl-1,2-dihydroquinoxalin-2-one reacts with hydrazine and thiosemicarbazide to give the corresponding hydrazone and thiosemicarbazone. The reaction with arylhydrazines yields 3-(α-arylazobenzylidene)-1,2,3,4-tetrahydroquinoxalin-2-ones which are tautomeric to the respective arylhydrazones. On heating in boiling acetic acid, the products of both types undergo intramolecular cyclocondensation with formation of 3-phenylpyrazolo[3,4-b]quinoxalines (3-phenylflavazoles). 3-Benzoyl-1,2-dihydroquinoxalin-2-one thiosemicarbazone gives rise to flavazole structure only in the presence of methyl 3-chloro-2-oxo-3-phenylpropionate as a trap of thiocarbamoyl moiety. The cyclization of 3-(α-hydrazonobenzyl)-1,2-dihydroquinoxalin-2-one is accompanied by formation of quinoxalyl ketone azine.

Synthesis and structural studies of symmetric and unsymmetric adamantylmethyleneazines

The synthesis and spectroscopic properties (1H, 13C and 15N NMR, in solution and in the solid state) of six new 1-adamantylmethylene azines are reported. The crystal and molecular structures of 1-adamantylcarbaldehyde azine and 1-adamantyl methyl ketone azine, which exist in the solid state in the E,E-configuration, were determined by x-ray analysis. The geometric characteristics of the azine central bridge and the preferred configuration with regard to it (E,E, E,Z or Z,Z) were investigated by means of the crystallographic data retrieved from the Cambridge Structural Database and ab initio quantum chemical calculations. Copyright © 1999 John Wiley & Sons, Ltd.

Ligand behaviour and reactivity of phenyl 2-pyridyl ketone azine. Structures of two polymorphic forms of the azine and a copper complex of the 3-phenyltriazolo[1,5-a]pyridine *

Two polymorphic forms of phenyl 2-pyridyl ketone azine (L1) and the complex [ZnL1Cl2] have been synthesized and characterized by X-ray diffraction analysis. In the reaction with copper(II) chloride both isomers of the azine undergo hydrolytic and oxidative processes, giving rise to the complex [CuL22Cl2] (L2 = 3-phenyltriazolo[1,5-a]pyridine). In order to clarify this process, phenyl 2-pyridyl hydrazone (L3) has been synthesized and treated with copper(II) chloride; in this way CuL2(Cl)·H2O and CuL3Cl2 were isolated.

The yttrium ion as a template in the synthesis of the macrocyclic and acyclic complexes formed in the reactions with 2,6-diacetylpyridine and hydrazine

The macrocyclic tetradentate NNNN donor yttrium nitrate complex of formula [YL 1(NO 3) 3]·2H 2O, where L 1 is 2,5,11,14-tetramethyl-3,4,12,13,19,20-hexaaza-tricyclo[13.3.1.1 6,10]eicosa-1(19),2,4,6,8,10(20),11,13,15,17-decaene, has been prepared by the condensation of 2,6-diacetylpyridine with hydrazine in the presence of a metal ion template and characterized by spectral and analytical data. Different experimental conditions (the type of counterion, ratio of starting materials) lead to the isolation of acyclic tetradentate NNNO or terdentate NNN donor complexes of yttrium with uncondensed carbonyl or amino groups. They are formulated as [YL 2(H 2O) 2]Cl 3·2H 2O and [YL 2(H 2O) 2](ClO 4) 3·2H 2O, where L 2 is (6-acetyl-pyrid-2-yl)methyl ketone azine, and [YL 3(NO 3) 3]·2H 2O, [YL 2 3]ClO 4) 3·2H 2O, where L 3 is 2,6-diacetylpyridinedihydrazone. The 2,6-diacetylpyridine (L) complexes isolated as minor products, are regarded as possible intermediates in the formation of macrocyclic L 1 and ring-opened L 2 complexes of yttrium.

Spectrofluorimetric kinetic determination of copper based on the autoxidation of 2,2'-dipyridyl ketone azine or hydrazone or phenyl-2-pyridyl ketone hydrazone

Kinetic methods for determination of ppm levels of copper are based on its catalytic effect on the autoxidation of the hydrazone and the azine of 2,2'-dipyridyl ketone and the hydrazone of phenyl-2-pyridyl ketone. The reaction is followed by measuring the rate of appearance of fluorescence. The methods suffer very few interferences.

The synthesis and characterization of the macrocyclic and ring-opened complexes formed in the reaction of the lanthanides with 2,6-diacetylpyridine and hydrazine

Abstract Complexes, [LnL1(H2O)2] (ClO4)3·4H2O, where L1 is 2,5,11,14-tetramethyl-3,4,12,13,19,20-hexaazatricyclol[13.3.1.1.6,10] eicosa-1(19),2,4,6,8,10(20),11,13,15,17-decaene and Ln is Tb, Dy, Ho, Er, Tm, Yb or Lu, have been prepared by the condensation of 2,6-diacetylpyridine with hydrazine in the presence of metal-ion templates and characterized by spectral data, thermal and elemental analysis. They are proposed to have six-coordinate and octahedral geometry with four nitrogen donor atoms occupying the equatorial plane and two water molecules in the axial positions. In contrast, analogous reactions involving the lighter lanthanides yield ring-opened complexes [LnL22] (ClO4)3·2H2O, where L2 is (6-acetyl-pyrid-2-yl)methyl ketone azine, Ln is La, Pr, Nd or Sm and [LnL2(H2O)2] (ClO4)3·2H2O, where Ln is Eu or Gd. In addition to the above major products small amounts of lanthanide complexes of 2,6-diacetylpyridine (L3) have been isolated from the reaction and identified by spectral, thermal, and elemental analysis. These complexes are formulated as [LnL34](ClO4)3·2H2O, where Ln is La, Pr, Nd or Sm, [LnL33(H2O)](ClO4)3·2H2O, where Ln is Eu or Gd, and [LnL33](ClO4)3·3H2O, where Ln is Tb, Dy, Ho, Er, Tm, Yb or Lu. Treatment of [LnL1(H2O)2](ClO4)3·4H2O with water yields complexes of the ring-opened ligand L2 of general formula [LnL2(H2O)2](ClO4)3·2H2O, where Ln is Tb, Dy, Ho, Er, Tm, Yb or Lu.

Analytical study of the phenyl-2-pyridyl ketone azine-palladium system. Photometric determination of palladium

Phenyl-2-pyridyl ketone azine reacts with palladium(II) to produce a yellow 1:1 complex ( λ max = 425 nm, ϵ = 10.4 × 10 3 M −1 cm −1 in aqueous ethanolic solution) and a red-violet 3:1 complex ( λ max = 530−540 and 380−390 nm). The yellow complex in aqueous ethanolic solution has been used for the spectrophotometric determination of trace amounts of palladium. The method has been applied to the determination of palladium in some catalysts and one mineral.

Di-2-pyridyl ketone azine as an analytical reagent and its application to the determination of iron(II)

The synthesis, characteristics and analytical applications of di-2-pyridyl ketone azine are described. This compound reacts with iron(II) to produce a red 3: 1 complex (λmax. 460 nm, ε= 9·3 × 103 l mol–1 cm–1 in aqueous ethanolic solution) and a green 3: 1 complex (λmax. 750 nm, ε= 4·5 × 103 l mol–1 cm–1 in aqueous ethanolic solution and 6·4 × 103 l mol–1 cm–1 in chloroform). The green complex, extracted into chloroform, has been used for the spectrophotometric determination of trace amounts of iron. The method is selective and has been applied to the determination of iron in some industrial waste waters.