Si-Containing Amides of Phosphoric Acid

Summary. The first representative of the N-silylmethylamides of phosphoric acid O=P[NMe(CH₂SiMe _n (OEt)_3-n ]₃ have been synthesized by interaction of MeNHCH₂SiMe _n (OEt)_3-n (n = 2, 3) with POCl₃. The interaction of the N,N′,N″-trimethyl-N,N′,N″-tris[(ethoxydimethyl- silyl)methyl]triamide phosphoric acid with BF₃·Et₂O or BCl₃ results in the formation of the N,N′,N″-trimethyl-N,N′,N″-tris[(fluorodimethyl-silyl)methyl]triamide phosphoric acid or N,N′,N″-trimethyl-N,N′,N″-tris[(chlorodimethylsilyl)methyl]triamide phosphoric acid. NMR data show on the tetracoordinate state of silicon in these products. Professor Vadim Aleksandrovich Pestunovich, our chief, teacher and friend died on July 4^th, 2004     

N,N,N′,N′,N″‐Pentamethyl‐N″‐[(trifluorosilyl)methyl] phosphoric triamide. First example of the existence of intramolecular PO→Si coordination bond in the Si‐containing phosphoric triamides

The N,N,N′,N′,N″‐pentamethyl‐N″‐(trifluorosilylmethyl)phosphoric triamide O?P(NMe₂)₂N(Me) CH₂SiF₃ with intramolecular P?O→Si coordination was formed by the reaction of N,N,N′,N′,N″‐pentamethyl‐N″[(triethoxysilyl)methyl]phosphoric triamide with BF₃·Et₂O. Copyright © 2007 John Wiley & Sons, Ltd.     

Synthesis of Si-containing cyclic ureas

1,3-Bis[(triethoxysilyl)methyl]tetrahydropyrimidin-2-one and 1,3-bis[(dimethoxysilyl)methyl]tetrahydro-pyrimidin-2-one have been synthesized on interacting urea with N,N′-bis(silylmethyl)propylenamines (EtO)³⁻ⁿMe_nSiCH₂NH(CH₂)₃NHCH₂SiMe_n(OEt)_3−n (n = 0, 2). Their interaction with boron trichloride has been studied. The structures of all the compounds synthesized have been demonstrated by multinuclear NMR spectroscopy. Dedicated to the 50^th Anniversary of the Latvian Institute of Organic Synthesis __________ Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 2, pp. 238–244, February, 2007.     

A novel chromone-substituted trimeric dihydroflavonol from <Emphasis Type="Italic">Anogeissus pendula</Emphasis>

A new chromone-substituted dihydrotriflavonol, (2S,3S)[6-{(3S) 3″,5″-dihydroxy-6″-methoxydihydrochromone}5,3′,4′,5′-tetrahydroxy-7-methoxy-3-O-8-dihydroflavone]₂ 3-O-8[6-{(3S) 3″,5″-dihydroxy-6″methoxydihydrochromone}3,5,3′,4′,5′-pentahydroxy-7-methoxydihydroflavonol] was isolated from the leaves of Anogeissus pendula. The structure was determined by UV, ¹H NMR, ¹³C NMR, HMBC, and CD data.     

Stabilities and coordination modes of glycinephosphonic acid in copper(II) heteroligand complexes with ethylenediamine, diethylenetriamine or N,N,N′,N′,N″-pentamethyldiethylene triamine in aqueous solution

Solution equilibrium studies on the Cu(II)-polyamine-(aminomethyl)phosphonic acid (glycinephosphonic acid) ternary systems (polyamine: ethylenediamine (en), diethylenetriamine (dien), N,N,N′,N′,N″-pentamethyldiethylenetriamine (Me₅dien)) have been performed by pH-potentiometry, UV–vis spectrophotometry and EPR methods. The obtained results suggest the formation of the heteroligand complexes with [Cu(A)(Gly(P))] stoichiometry in all studied systems. Additionally, in the systems with dien the protonated [Cu(dien)(H–Gly(P))]⁺ species also exists in acid solution and in the system with en the [Cu(en)(Gly(P))H_-1]⁻ species is formed in the basic solution. Our spectroscopic results indicate the tetragonal geometry for the [Cu(en)(Gly(P))] species, the geometry slightly deviated from square pyramidal for the [Cu(dien)(Gly(P))] complex and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me₅dien)(Gly(P))] species. The coordination modes in these heteroligand complexes are discussed.     

Reactions of bis(trimethylsilyl)amine and -amide with MoOCl4

Oxo-Mo(VI) imido-chloride, [MoOCl₂(NH)(Et ₂O)] _n and nitrido-chloride, [Mo₂O₂Cl₂(N)₂(Et ₂O)] _n have been synthesized by equimolar reactions of MoOCl₄ with HN(SiMe ₃)₂ and LiN(SiMe ₃)₂, respectively. Higher molar reactions of HN(SiMe ₃)₂ lead to imido-silylamido derivatives, [Mo₂OCl₃(NH)₃(NHSiMe ₃)] _n , whereas those of LiN(SiMe ₃)₂ give silylimido bridged compounds, Mo₄O₄Cl₄(NSiMe ₃)₆ and Mo₄O₄(NSiMe ₃)₈. Elemental analyses, redox titration, magnetic moment, molecular weight, molar conductance, infrared,¹H-NMR and TG-DTG-DTA studies are reported.

---

Reaktionen von Bis(trimethylsilyl)amin und -amid mit MoOCl₄

Zusammenfassung Durch equimolare Reaktionen von MoOCl₄ mit HN(SiMe ₃)₂ und LiN(SiMe ₃)₂ wurden die Oxo-Mo(VI) Imido-chloride [MoOCl₂(NH)(Et ₂O)] _n und die Nitrido-chloride [Mo₂O₂Cl₂(N)₂(Et ₂O)] _n dargestellt. Höhermolekulare Reaktionen von HN(SiMe ₃)₂ führen zu Imido-silylamido Derivaten [Mo₂OCl₃(NH)₃(NHSiMe ₃)] _n , währenddessen die von LiN(SiMe ₃)₂ silylimidoüberbrückte Verbindungen ergeben: Mo₄O₄Cl₄(NSiMe ₃)₆ und Mo₄O₄(NSiMe ₃)₈. Die Strukturen sind mit Elementaranalysen, Redoxtitrationen, Messung der magnetischen Momente, Molekulargewichten, molarer Leitfähigkeit, Infrarot,¹H-NMR und TG-DTG-DTA-Untersuchungen charakterisiert.

     

Electrospray mass spectrometric studies of a potential antitumor drug and its analogous platinum(II) and platinum(IV) complexes with the ethylenediamine-N,N′-di-3-propanoato ligand and its dibutyl ester

Abstract  The electrospray mass spectrometric (ESI–MS) behavior of the complexes trans-dichloro(ethylenediamine-N,N′-di-3-propionato)platinum(IV), trans-dibromo(ethylenediamine-N,N′-di-3-propionato)platinum(IV), dichloro(ethylenediamine-N,N′-di-3-propionic acid)platinum(II), tetrachloro(O,O′-di-n-butyl-ethylenediamine-N,N′-di-3-propanoate)platinum(IV), chlorotribromo(O,O′-di-n-butyl-ethylenediamine-N,N′-di-3-propanoate)platinum(IV), and dichloro(O,O′-di-n-butyl-ethylenediamine-N,N′-di-3-propanoate)platinum(II), with the formulae trans-[PtCl₂(eddp)] (1), trans-[PtBr₂(eddp)] (2), [PtCl₂(H₂eddp)] (3), [PtCl₄(Bu₂eddp)] (4), [PtBr₃Cl(Bu₂eddp)] (5), and [PtCl₂(Bu₂eddp)]·H₂O (6), is reported. The deprotonated molecular ions or halide adducts are usually observed. ESI–MS data demonstrate the usefulness of the method for efficient characterization of metal complexes in solution. Graphical Abstract        

Reaction of 2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-carbaldehyde with naphthalen-1-amine,quinolin-8-amine,and 1,3-diketones

Condensation of 2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-carbaldehyde with naphthalen-1-amine and cyclohexane-1,3-dione, methyl 2,2-dimethyl-4,6-dioxocyclohexane-1-carboxylate, or dimedone gave the corresponding 7-(2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-yl)-7,8,9,10,11,12-hexahydro-12H-benzo[c]acridin-8-ones. The reaction of 2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-carbaldehyde with naphthalen-1-amine and indan-1,3-dione produced 7-(2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-yl)-8H-benzo[h]indeno[1,2-b]quinolin-8-one. 7-(2′-Hydroxy-1,1′: 3′,1″-terphenyl-5′-yl)-7,8,9,10,11,12-hexahydrobenzo[b][1,10]phenanthrolin-8-ones were obtained by three-component condensation of 2′-hydroxy-1,1′: 3′,1″-terphenyl-5′-carbaldehyde with quinolin-8-amine and cyclohexane-1,3-dione, methyl 2,2-dimethyl-4,6-dioxocyclohexane-1-carboxylate, or dimedone.     

A theoretical investigation on structures of tripodal thiourea derivatives and their anion recognition

The structural geometries of three tripodal thiourea receptors, i.e. 1,3,5-triethyl-2,4,6-tris[(N′-methylthioureido)methyl]benzene (1), tris[N′-methyl-N-(2-aminoethyl)thiourea]methane (2), tris[N′-methyl-N-(2-aminoethyl)thiourea]amine (3), and their complexes with F⁻, Cl⁻, Br⁻, I⁻, NO₃ ⁻, CO₃ ²⁻, SO₄ ²⁻, HSO₄ ⁻, PO₄ ³⁻, HPO₄ ²⁻ and H₂PO₄ ⁻ were obtained using the density functional theory calculations. Electronic and thermodynamic properties of anion binding complexes of the receptors 1, 2 and 3 were investigated. Recognition abilities of all the receptors in terms of selectivity coefficients are reported. Intermolecular interactions in all the studied complexes occurring via multi-point hydrogen bonding were found. The receptors 1, 2 and 3 were found to be excellent selectivity for phosphate ion and their binding free energy for the phosphate ion are −292.57, −291.77 and −295.01 kcal/mol, respectively.     

Synthesis,characterization, and antimicrobial activity of new benzoylthiourea ligands

In this study, new benzoylthiourea derivatives, (E)-N-[(2-benzamidomethyleneamino)ethylcarbamothioyl]benzamide H₃L′, N-(1-(3-benzoylthioureido)propan-2-ylcarbamothioyl)-benzamide H₄L″, (E)-N-[4-(benzamidomethyleneamino)phenylcarbamothioyl]benzamide H₃L‴, were synthesized. Structures of the compounds were identified by spectroscopic techniques. In addition, all synthesized compounds were evaluated for in vitro antibacterial and antifungal activity. Compound H₃L‴ exhibited antibacterial activity.     

Thermodynamic study of Cd(II) complex formation with tripodal N-donor ligands in DMSO

The complex formation of Cd(II) with N-donor ligands in dimethylsulfoxide (DMSO) is investigated by means of potentiometry and titration calorimetry. The ligands considered in this work are tripodal polyamines and polypyridines: 2,2′,2″-triaminotriethylamine (TREN), tris(2-(methylamino)ethyl)amine (Me₃TREN), tris(2-(dimethylamino)ethyl)amine (Me₆TREN), tris[(2-pyridyl)methyl]amine (TPA) and 6,6′-bis-[bis-(2-pyridylmethyl)aminomethyl]-2,2′-bipyridine (BTPA). These ligands are characterized by a systematic modification of the donor groups to relate their structure to the thermodynamics of the complexes formed. The TREN and Me₃TREN ligands form highly stable species. The stability of the complex formed with the fully methylated Me₆TREN is much lower than with other polyamines and the enthalpic and entropic terms suggest an incomplete coordination to the metal ion. In general, the TPA ligand forms complexes less stable than TREN and Me₃TREN as a result of the combination of higher structural rigidity of TPA and lower basicity of pyridine moiety with respect to primary and secondary amines. Pyridine-containing ligands display, in general, a less unfavorable formation entropy than tripodal polyamines here considered. In particular, TPA forms a more stable 1:1 species with respect to Me₆TREN due to the entropic term, being the enthalpy less negative. The ligand BTPA is able to form only a monometallic complex, where the metal ion is likely to be encapsulated as indicated by the obtained thermodynamic parameters.     

Synthesis, molecular structure, and catalytic activity of borohydride complexes [(Me3Si)2NC(NPri)2]2Nd(BH4)2Li(thf)2 and [(Me3Si)2NC(NPri)2]2Sm(BH4)2Li(thf)2

The reactions of lanthanide tris(borohydrides) Ln(BH₄)₃(thf)₃ (Ln = Sm or Nd) with 2 equiv. of lithium N,N′-diisopropyl-N′-bis(trimethylsilyl)guanidinate in toluene produced the [(Me₃Si)₂NC(NPrⁱ)₂]Ln(BH₄)₂Li(thf)₂ complexes (Ln = Sm or Nd), which were isolated in 57 and 42% yields, respectively, by recrystallization from hexane. X-ray diffraction experiments and NMR and IR spectroscopic studies demonstrated that the reactions afford monomeric ate complexes, in which the lanthanide and lithium atoms are linked to each other by two bridging borohydride groups. The complexes exhibit catalytic activity in polymerization of methyl methacrylate. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 441–445, March, 2007.     

Synthesis of new carbamate derivatives of indole and their modification

Oximation of indoles having a methoxycarbonylamino group on C⁵ and an acyl group on C³ with hydroxylamine hydrochloride in the presence of pyridine gave the corresponding oximes. The reduction of the 3-C=O group with sodium tetrahydridoborate in the presence of sodium hydroxide was accompanied by removal of the methoxycarbonyl group at the pyrrole nitrogen atom with formation of racemic alcohols. 1,4-Addition of 1-(pyridin-3-yl)butane-1,3-dione to dimethyl 1,4-benzoquinone diimine N,N′-dicarboxylate in dioxane in the presence of sodium methoxide, followed by heating in boiling 22% hydrochloric acid, afforded methyl 2-methyl-5-(methoxycarbonylamino)-3-(pyridin-3-ylcarbonyl)-1H-indole-1-carboxylate. 3-(Dimethylamino)-1-(4-methyl-1,2,5-oxadiazol-3-yl)prop-2-en-1-one reacted with N,N′-bis(methoxycarbonyl)- and N,N′-bis(phenylsulfonyl)-1,4-benzoquinone diimines in methylene chloride and acetic acid, respectively, in the presence of BF₃ · Et₂O to produce indoles having a 1,2,5-oxadiazolylcarbonyl group on C₃.     

Darstellung und Eigenschaften von Chromtricarbonyl-Komplexen strukturisomerer Borazin-Derivate

The new hexaalkylborazine chromium tricarbonyls (n-Pr)₃B₃N₃Me₃Cr(CO)₃ (V), Me₃B₃N₃(n-Pr)₃Cr(CO)₃ (VI), (i-Pr)₃B₃N₃Me₃Cr(CO)₃ (VII) and Me₃B₃N₃(i-Pr)₃Cr(CO)₃ (VIII) have been prepared from fac-Cr(CO)₃(MeCN)₃ and the corresponding borazine in dioxane or without solvent. They are much more labile than the isomeric complex Et₃B₃N₃Et₃Cr(CO)₃ (IV) which can be readily obtained from Et₃B₃N₃Me₃Cr(CO)₃ and Et₃B₃N₃Et₃ by ring ligand exchange. The NMR., IR., UV. and Mass spectroscopic data of the complexes IV–VIII will be briefly discussed. The preparation of the borazine derivatives (n-Pr)₃B₃N₃Me₃ (IX) and Me₃B₃N₃(n-Pr)₃ (X) is also reported.     

Preparation of a zwitterionic trichloroplatinum(II) complex with an alkylbipyridinum ligand and its reaction in dmso-<Emphasis Type="BoldItalic">d</Emphasis><Subscript>6</Subscript> solution

A zwitterionic trichloroplatinum(II) complex PtCl₃(4,4′-bpy-N-ⁿBu) (1) was prepared by an aqueous reaction of [4,4′-bpy-N-ⁿBu]Cl with K₂PtCl₄, and was characterized by ¹H-n.m.r. and IR spectroscopy as well as elemental analysis. Dissolving (1) into dmso-d ₆ at 25 °C yields a mixture of the complexes, cis-PtCl₂(4,4′-bpy-N-ⁿBu)(dmso-d ₆) (2-cis), trans-PtCl₂(4,4′-bpy-N-ⁿBu)(dmso-d ₆) (2-trans), [4,4′-bpy-N-ⁿBu]Cl and PtCl₂(dmso-d ₆)₂. Ratio of the products in the dmso-d ₆ solution changed depending on the temperature and the total concentration of the complexes. These compounds are in equilibrium via isomerization reaction between (2-cis) and (2-trans) and via displacement reaction of the alkylbipyridinium ligand of (2-cis) and (2-trans) with dmso-d ₆ to form [4,4′-bpy-N-ⁿBu]Cl and PtCl₂(dmso-d ₆)₂.     

Stabilities and Coordination Modes of α-Alaninephosphonic Acid in Copper(II) Heteroligand Complexes with Ethylenediamine, Diethylenetriamine or N,N,N′,N′,N″-Pentamethyldiethylene Triamine in Aqueous Solution

Solution equilibrium studies on Cu²⁺–L₁–L₂ ternary systems have been performed by pH-potentiometry, UV–Vis spectrophotometry and EPR methods (L₁ corresponds to polyamines such as ethylenediamine (en), diethylenetriamine (dien), or N,N,N′,N′,N″-pentamethyldiethylenetriamine (Me₅dien) and L₂ represents 1-aminoethylphosphonic acid (α-alaninephosphonic acid)). The obtained results suggest the formation of heteroligand complexes with [Cu(L₁)(α-Ala(P))] stoichiometry in all studied systems. Additionally, in the system with en the [Cu(en)(α-Ala(P))H₋₁]⁻ species is formed in basic solution. Our spectroscopic results indicate tetragonal geometry for the [Cu(en)(α-Ala(P))] species, geometry slightly deviated from square pyramidal for the [Cu(dien)(α-Ala(P))] complex and strongly deviated from square pyramidal towards trigonal bipyramidal for the [Cu(Me₅dien)(α-Ala(P))] species. The coordination modes in these heteroligand complexes are discussed.     

Affinity of Tripodal and Linear Tetraamines for Silver(I) in Dimethyl Sulfoxide

The thermodynamic functions of the complexation of Ag(I) by the tripodal ligands, tris(2-(methylamino)ethyl)amine (Me₃tren) and tris(2-(dimethylamino)ethyl)amine (Me₆tren) (L), are determined in dimethyl sulfoxide (DMSO) by potentiometric and calorimetric techniques at 298.0 K and 0.1 mol⋅dm⁻³ ionic strength (Et₄NClO₄). A comparison is made between previous data concerning Ag(I) complex formation with the non-alkylated tripodal 2,2′,2″-triaminotriethylamine (tren), in order to analyze the influence of N-methylation on this type of branched donor, and with those relative to the linear triethylenetetramine (trien) and 1,1,4,7,10,10-hexamethyltriethylenetetramine (Me₆trien). The results are discussed taking into account different σ-donating properties, geometric arrangement of the ligands, steric repulsions and solvation effects.     

Studies of Co(II), Ni(II), Cu(II) and Cd(II) chelates with different phosphonic acids

Co(II), Ni(II), Cu(II) and Cd(II) chelates with 1-aminoethylidenediphosphonic acid (AEDP, H₄L¹), α-amino benzylidene diphosphonic acid (ABDP, H₄L²), 1-amino-2-carboxyethane-1,1-diphosphonic acid (ACEDP, H₅L³), 1,3-diaminopropane-1,1,3,3-tetraphosphonicacid (DAPTP, H₈L⁴), ethylenediamine-N,N′-bis(dimethylmethylene phosphonic)acid (EDBDMPO, H₄L⁵), O-phenylenediamine-N,N′-bis(dimethyl methylene phosphonic)acid (PDBDMPO, H₄L⁶), diethylene triamine-N,N,N′,N′,N″N″-penta(methylene phosphonic)acid (DETAPMPO, H₁₀L⁷) and diethylene triamine-N,N″-bis(dimethyl methylene phosphonic)acid (DETBDMPO, H₄L⁸) have been synthesised and were characterised by elemental and thermal analyses as well as by IR, UV–VIS, EPR and magnetic measurements. The first stage in the thermal decomposition process of these complexes shows the presence of water of hydration, the second denotes the removal of the coordinated water molecules. After the loss of water molecules, the organic part starts decomposing. The final decomposition product has been found to be the respective MO·P₂O₅. The data of the investigated complexes suggest octahedral geometry with respect to Co(II) and Ni(II) and tetragonally distorted octahedral geometry with respect to Cu(II). Antiferromagnetism has been inferred from magnetic moment data. Infrared spectral studies have been carried out to determine coordination sites.     

Synthesis of azoles from 3,3′-[(4-alkoxyphenyl)imino]bis(propanoic acid hydrazides)

Abstract  

Reaction of 3,3′-[(4-alkoxyphenyl)imino]bis(propanoic acid hydrazides) with CS₂ in alkaline solution and subsequent acidification gave 5,5′-[[(4-alkoxyphenyl)imino]diethane-2,1-diyl]bis(1,3,4-oxadiazole-2(3H)-thiones). The same dihydrazides on reaction with phenyl isocyanates or phenyl isothiocyanates were converted to bis[N′-(phenylaminocarbonyl)propanoic acid hydrazides] and bis[N′-(phenylaminocarbonothioyl)propanoic acid hydrazides], which underwent cyclization in alkaline medium to produce 5,5′-[[(4-alkoxyphenyl)imino]diethane-2,1-diyl]bis(4-phenyl-2,4-dihydro-3H-1,2,4-triazol-3-ones) and their 3-thio analogues, whereas in sulfuric acid or POCl₃ 5,5′-[[(4-alkoxyphenyl)imino]diethane-2,1-diyl]bis(N-phenyl-1,3,4-oxadiazol-2-amines) and 5,5′-[[(4-alkoxyphenyl)imino]diethane-2,1-diyl]bis(N-phenyl-1,3,4-thiadiazol-2-amines) were obtained.     

Synthesis and characterization of mono- and bicyclic heterocyclic derivatives containing 1,2,4-triazole, 1,3,4-thia-, and -oxadiazole rings

A series of new N- and S-substituted 1,3,4-oxadiazole derivatives were synthesized. 5-Pyridin-3-yl-3-[2-(5-thioxo-4,5-dihydro-l,3,4-thiadiazol-2-yl)ethyl]-1,3,4-oxadiazole-2(3H)-thione and 5-[(5-(pyridin-3-yl)-1,3,4-oxadiazol-2-ylthio)methyl]-N-phenyl-1,3,4-thiadiazol-2-amine were formed by cyclization of 3-(5-pyridin-3-yl-2-thioxo-1,3,4-oxadiazol-3(2H)-ylpropanimidohydrazide and 2-[(5-pyridin-3-yl-1,3,4-oxadiazol-2-yl)thio]thiosemicarbazide with CS₂ and H₂SO₄. On the other hand, a number of new bicyclic 1,2,4-triazolo[3,4-b][1,3,4]thiadiazole derivatives were synthesized. 6-Pyridin-3-ylbis[1,2,4]‐triazolo[3,4-b:4′,3′-d][1,3,4]thiadiazole-3(2H)-thione was synthesized by reaction of 6-(hydrazino)-3-pyridine-3-yl[1,2,4]triazolo[3,4-b][1,3,4]thiadiazole with CS₂/KOH/EtOH. The structures of the newly synthesized compounds were elucidated by the spectral and analytical data IR, Mass, and ¹H NMR spectra. Correspondence: Adel A.-H. Abdel-Rahman, Department of Chemistry, Faculty of Science, Menoufia University, Shebin El-Koam, Egypt; Wael A. El-Sayed, National Research Centre, Department of Photochemistry, Cairo, Egypt.