Transition-metal complexes with hydrazides and hydrazones

Several new complexes of dioxomolybdenum(VI) of the general formula [MoO₂(L)S], whereL is the dianion of salicylaldehydep-hydroxybenzoylhydrazone andS denotes H₂O, MeOH, py, PPh₃, DMSO or DMF, were synthesized and characterized by elemental analysis, electronic UV-VIS and IR spectra, thermal analysis, molar conductivity and magnetic susceptibility measurements. Salicylaldehydep-hydroxybenzoylhydrazone participates in the coordination as a tridentate ligand with the ONO set of donor atoms. The complexes contain acis-MoO₂ group and are of octahedral geometry. Complexes of the MoO₂L type were also prepared by synthesis in CHCl₃ solution and by isothermal heating of [MoO₂(L)S] complexes. The MoO₂L complex synthesized in CHCl₃ solution has most probably a pentacoordinated structure while the complex obtained by isothermal heating of [MoO₂(L)S] has a polymeric hexacoordinated structure.The authors are grateful to the Serbian Republic Research Fund for financial support and to academician Prof. M. ui for his interest in this work.     

Transition metal complexes with hydrazides and hydrazones

A study was made of the thermal decomposition of octahedral Co(II) complexes of the type CoL_n X ₂·mH₂O, wheren=2 and 3,m=1,2 and 5 andX=Cl, Br, I, NCS, OAc andv ₂So₄, in both air and nitrogen atmospheres. It was established that the complexes are completely decomposed below 800° and CoO is formed as final product. The most probable decomposition mechanism was proposed. The tris(ligand) complexes were characterized by elemental analysis, and spectral and magnetic measurements, and all the data suggested the presence of a point group symmetry of type O_h.

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Zusammenfassung Sowohl in Luft als auch in Stickstoffatmosphäre wurde die thermische Zersetzung von oktaedrischen Co(II)-Komplexen der allgemeinen Formel CoL_nX₂· mH₂O (n=2 und 3,m=1, 2 und 5,X=Cl, Br, I, NCS, OAc und SO₄) untersucht. Es wurde festgestellt, daß sich die Komplexe unterhalb 800°C vollkommen zu CoO als Endprodukt zersetzen. Der wahrscheinlichste Zersetzungsmechanismus wurde unterbreitet. Die tris-Ligandenkomplexe wurden mittels Elementaranalyse sowie Spektral- und magnetischen Untersuchungen charakterisiert, alle Angaben deuten auf eine Punktsymmetriegruppe vom Typ Oh hin.

     

Synthesis of hydrazones derived from 2-substituted-10-carboxyphenothiazine hydrazides

2-Substituted-10-carboxyphenothiazine hydrazides 3 were found to yield hydrazones 5 on reaction with aromatic aldehydes. However, a similar reaction of hydrazides 3 with aliphatic ketones in refluxing ethanol failed to give the expected hydrazones 6 . The corresponding phenothiazines 1 were isolated in this reaction, apparently through alcoholysis of the amide bond to the ring nitrogen atom in 3 .     

A new ‘one-pot’ synthesis of hydrazides by reduction of hydrazones

A new, high-yielding methodology for reducing hydrazones to hydrazines is described, which allows the synthesis of different mono-, di- and trisubstituted hydrazines. Moreover, the reduction step can be followed by an in situ reaction with a carboxylic acid making possible a ‘one-pot’ synthesis of trisubstituted hydrazides. The method is relatively general and, in principle, suitable for industrial applications.     

Simple and efficient approach for synthesis of hydrazones from carbonyl compounds and hydrazides catalyzed by meglumine

A simple, environmentally benign protocol for synthesis of hydrazones from carbonyl compounds and hydrazides has been developed in the presence of meglumine in aqueous-ethanol media at room temperature. The salient features of the present protocol are mild reaction conditions, short reaction time, high yields, operational simplicity, metal-free, applicability toward large-scale synthesis, and biodegradable and inexpensive catalyst.     

Autoxidation of hydrazones. Some new insights

Autoxidation of hydrazones is a generally occurring reaction, leading mostly to the formation of alpha-azohydroperoxides. All structural kinds of hydrazones, having at least one hydrogen atom on nitrogen, are prone to autoxidation; however, there are marked differences in the rate of the reaction. Hydrazones of aliphatic ketones are 1-2 orders of magnitude more reactive than analogous derivatives of aromatic ketones. Even less reactive are the hydrazones of chalcones, which function also as efficient inhibitors of autoxidation of other hydrazones. These differences can be attributed to the reduction of the rate of the addition of oxygen to a hydrazonyl radical, which is a reversible reaction. In the case of conjugated ketones, it becomes endothermic, making this elementary step slow down and the chain termination reactions become important. Substituents influence the stability of hydrazonyl radicals and, consequently, the bond dissociation energies of the N-H bonds. In acetophenone phenylhydrazones, the substituents placed on the ring of hydrazine moiety exhibit a higher effect (Hammett rho = -2.8) than those on the ketone moiety (rho = -0.82), which denotes higher importance of the structure with spin density concentrated on nitrogen in delocalized hydrazonyl radical. Electronic effects of the substituents also affect the transition state for the abstraction of hydrogen atom by electrophilic peroxy radicals; NBO analysis display a negative charge transfer of about 0.4 eu from hydrazone to a peroxy radical in the transition state.     

二茂铁基取代酰腙的一些过渡金属配合物

本文制备了两个金属有机配位体,肉桂醛二茂铁基甲酰腙(HL^1)和二[(1-肉桂酰肼基乙基)环戊二烯基]铁(H~2L^2)及它们与一些过渡金属的配合物:ML~2^1[M=Cu(II)],ML^2[(M=Cu(II)和Zn(II)],M(HL^1)~2Cl~2[M=Cd(II),Co(II)和Ni(II)],M(H~2L^2)Cl~2[M=Mn(II),Zn(II),Co(II)和Cd(II)]。这两个配位体以烯醇式与M(OAc)~2.nH~2O中心离子配位,与MCl~2.nH~2O则以酮式配位。     

New uranyl(VI) complexes with hydrazones derived from aliphatic and aromatic acid hydrazides containing dihydroxo bridges

Summary Several new uranyl(VI) complexes of hydrazones, derived from formoyl-, acetoyl-, butroyl-, caproyl-, salicyloyl-, oxaloyldi-, malonoyldi-, and adipolyldi-hydrazines and benzaldehyde or salicylaldehyde have been prepared in absolute EtOH and in the presence or absence of AcONa. The complexes have been characterized by elemental analyses, molar conductivities, spectral (u.v., i.r, n.m.r.,) and magnetic measurements. I.r. spectral data suggest that the ligands coordinate in a bi-, tri- and/or tetradentate fashion in the enol form, and that proton displacement proceedsvia the enolized carbonyl oxygen solely in the benzaldehyde hydrazone complexes and through the OH (phenolic) in the salicylaldehyde hydrazone complexes. Moreover, the spectral data show the existence of dihydroxo bridges for benzaldehyde hydrazone complexes. The role of the OH (phenolic) as well as the presence or absence of NaOAc on the properties of the latter complexes is discussed.     

Some N-methyl-N-(4-chloro-1-phthalazinyl)hydrazones

N-Methyl-N-(4-chloro-1-phthalazinyl)-(E)-hydrazones of the corresponding carbonyl compounds were obtained by condensation of 1-methyl-1-(4-chloro-1-phthalazinyl)hydrazine with carbonyl compounds. The PMR spectra of the products in a number of solvents at various temperatures and the UV spectra in solution and in the solid form were recorded. It was established that a change in the nature of the substituents in the ylidene fragment leads to a change in the three-dimensional structure and the reaction center (C_pht-Cl, C_pht-N, C=N) in acid hydrolysis reactions.Communication LVII from the series Hydrazones. See [1] for communication LVI.Translated from Khimiya Geterotsiklicheskikh Soedenii, No. 4, pp. 530–536, April, 1978.     

Derivatives of heterocyclic α-iminocarboxylic acids. 1. Syntheses of hydrazides of heterocyclic α-iminocarboxylic acids and their hydrazones

By the interaction of esters of L-proline, L-thioproline, pipecolic acid, and tetrahydro-1,4-thiazine-3-carboxylic acid with hydrazine, the corresponding hydrazides were obtained, which react with equimolar quantities of carbonyl compounds to form hydrazones consisting of mixtures of rotational isomers relative to the amide bond.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 9, pp. 1277–1282, September, 1993.     

Potential anticonvulsants. IX. Some isatin hydrazones and related compounds

A number of hydrazines, hydrazides, and related compounds have been condensed with isatin and substituted isatins. The anticonvulsant activity of these compounds is reported.     

The preparation of substituted 1,2,4-triazolines and substituted picolinic acid methylene hydrazides by the action of certain carboxamide hydrazones with ketones

The action of certain ketones with carboxamide hydrazones, yielding, depending on conditions, 1,2,4-triazolines or substituted picolinic acid methylene hydrazides, has been investigated. Also the preparation of 3-subsliluted-5-phenyl-1,2,4-triazines from the action of phenyl glyoxal and certain carboxamide hydrazones is described.     

Potential anticonvulsants. VIII. Some hydrazones of indole-3-carboxaldehyde

Indole-3-carboxaldehyde and some additional aldehydes were condensed with various hydrazines, hydrazides, and related compounds. A number of the products exhibited low levels of anticonvulsant activity.     

Synthesis,physicochemical study,and quantum-chemical simulation of hydrazones based on 2-hydrazinoimidazoline

2-Imidazolinylhydrazones of salicylic aldehyde, 2-N-tosylaminobenzaldehyde, and 1-phenyl-3-methyl-4-formylpyrazolone-5 are synthesized and studied by the IR, NMR, and electronic spectroscopy. Quantum chemical calculations of geometry and total energy of possible tautomers in a vacuum and ethanol solution are carried out. It is shown that in all cases diazine tautomers are the most stable.     

Hole-transporting hydrazones

This tutorial review covers recent contributions in the area of hole-transporting hydrazones, which are widely used in optoelectronic devices. It is addressed to students and researchers interested in the synthesis and properties of organic electroactive materials. The thermal, charge transport and other properties of electroactive hydrazones are compared and the relationships between the molecular structures and properties are emphasized. The first part discusses the low-molar-mass hydrazones and presents examples of their synthetic routes and chemical structures. In the second part, polymeric arylaldehyde hydrazones containing hydrazone moieties as the side substituents and in the main-chain are described.     

Kinetic and mechanistic study of N-aminopiperidine formation via the raschig process

Formation of N-aminopiperidine (NAPP) in the reaction of monochloramine with piperidine was studied by varying the reagents concentrations, pH and temperature. The study was carried out in diluted solutions, recording simultaneously monochloramine concentration by UV spectrophotometry at 243 nm and hydrazine concentration at 237 nm after treatment with formaldehyde. The presence of two competitive reactions: formation of NAPP and a complex parallel reaction limiting the yield of hydrazine, was established. Reaction products were characterized by GC/MS analysis. The rate constant of NAPP formation and activation parameters were determined, k ₁ = 56 × 10^?3 M^?1 s^?1 (25°C) and k ₁ = 9.3 × 10⁶ exp(?46.5/RT) M^?1 s^?1, respectively.     

Kinetic modelling of synthesis of N-aminopiperidine from hydroxylamine-O-sulfonique acid and piperidine

A new route to synthesize N-aminopiperidine (NAPP) from hydroxylamine-O-sulfonique acid (HOSA) and piperidine was described. Kinetics of the reaction was investigated to optimize the conditions of the synthesis. Since the reaction is fast, this study was carried out in a diluted medium (10⁻³ to 10⁻² mol/l). To determine the concentration of the reaction product, NAPP was allowed to react with formaldehyde and the product was analysed by UV and HPLC techniques. The formation of NAPP is consistent with the first-order reaction to two reagents, governed by the nucleophilic substitution via SN2 mechanism. Oxidation of NAPP by HOSA was identified as the main secondary reaction which consistently reduced the yield of NAPP. A number of differential equations were elaborated and solution of these equations serves to predict the behavior of the system as a function of the reagent concentrations, pH and temperature. From the corresponding mathematical treatment a unique implicit expression was derived that characterizes the reaction medium. It was found that the [PP]₀/[HOSA]₀ molar ratio (p), the initial concentrations of [PP]₀ and [HOSA]₀, the ratio of rate constants k ₂/k ₁ and temperature are the only parameters that affect the yield of NAPP from HOSA. The results calculated from this model are in good agreement with the experimental data and they can be used to determine the optimal conditions of the reaction.     

Configurational and constitutional information storage: multiple dynamics in systems based on pyridyl and acyl hydrazones

The C=N group of hydrazones can undergo E/Z isomerization both photochemically and thermally, allowing the generation of a closed process that can be tuned by either of these two physical stimuli. On the other hand, hydrazine-exchange reactions enable a constitutional change in a given hydrazone. The two classes of processes: 1) configurational (physically stimulated) and 2) constitutional (chemically stimulated) give access to short-term and long-term information storage, respectively. Such transformations are reported herein for two hydrazones (bis-pyridyl hydrazone and 2-pyridinecarboxaldehyde phenylhydrazone) that undergo a closed, chemically or physically driven process, and, in addition, can be locked or unlocked at will by metal-ion coordination or removal. These features also extend to acyl hydrazones derived from 2-pyridinecarboxaldehyde. Similarly to the terpydine-like hydrazones, such acyl hydrazones can undergo both constitutional and configurational changes, as well as metal-ion coordination. All these types of hydrazones represent dynamic systems capable of acting as multiple state molecular devices, in which the presence of coordination sites furthermore allows the metal ion-controlled locking and unlocking of the interconversion of the different states.     

Substituted hydroxycarboxylic hydrazides

The ethyl ester of oxalic acid piperylhydrazide has been synthesized, and its reactions with organomagnesium compounds investigated. The piperylhydrazides of diaryl-, dialkyl-, and dithienylglycolic acids have been obtained, and their properties examined. The IR and UV spectra of the compounds obtained, and the spectra of the halochromic salts and the basicity of the diaryl- and dithienylglycolic piperylhydrazides, were studied.For part LI, see [1].     

Synthesis,spectroscopic and thermal studies on ruthenium(III), rhodium(III) and iridium(III) complexes with hydrazones derived from 2,6-diacetylpyridine and different aromatic hydrazides

Summary The reactions of MCl₃·3H₂O (M=Ru, Rh or Ir) with hydrazones have been studied by three different methods and complexes of the types [M(LH₂)(H₂O)₂]Cl₃, [M(L)Cl(H₂O)] and [M(LH₂)Cl₂]Cl·H₂O have been isolated. Tentative structural conclusions are drawn for these products based upon elemental analysis, electrical conductance, magnetic moment, and i.r. and¹H n.m.r. data. The thermal stability and mode of decomposition for the complexes have been studied by t.g.a., d.t.g. and d.s.c. techniques.