Coordination chemistry of f-block elements with imine acids. Part IV. Synthetic and chiroptical studies on lanthanide(III) complexes of imine acids derived from L-alanine,L-valine,L-tyrosine and L-glutamic acid

Summary N-(orthovanillidene)L-alanine (OVAlaH₂), N-(salicylidene)L-valine (SValH₂), N-(orthovanillidene)L-valine (OVValH₂), N-(orthovanillidene)L-tyrosine (OVTyrH₃) and N-(salicylidene)L-glutamic acid (SGluH₃) react with La^III, Pr^III, Nd^III and Sm^III to yield new chiral complexes. Their dominant conformers were determined from c.d. spectra supported by¹H n.m.r. data, except for the L-glutamic acid derived complexes which were insoluble.     

Synthesis of furan compounds with amino and imino groups at theβ-position of the side chain by the catalytic hydroformamination of 2-vinylfuran

The hydroformamination of 2-vinylfuran in the presence of HRh(CO)(PPh₃)₃ was used for the first time to give N- [2- (2- furyl)propyl]- N,N- dialkylamines and N- [2- (2-furyl)propylidene]- N- alkylimines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1448–1449, June, 1990.     

Acid-catalyzed Conversions of N-(4-Nitrobenzylidene)-2-cyclopropyl- and N-(4-Nitrobenzylidene)-2-alkenylanilines. A new Method for the Synthesis of Dihydroquinolines and Quinolines

The acid-catalyzed conversions of N-(4-nitrobenzylidene)-2-cyclopropyl- and N-(4-nitrobenzylidene)-2-alkenylanilines have been studied. It has been established that the protonated azomethine unit of N-(4-nitrobenzylidene)-2-cyclopropylanilines is not capable of initiating intramolecular heterocyclization with participation of the three-membered ring. Conversion of N-(4-nitrobenzylidene)-2-(1-methylcyclopropyl)aniline to derivatives of quinoline is possible under the influence of concentrated H₂SO₄. Under the same conditions 2-methylcyclopropyl- and cyclopropyl-substituted Schiff's bases form only the corresponding alkenylazomethines (isomerization of the three-membered ring). Under the influence of more moderate acids (trifluoroacetic, polyphosphoric) N-(4-nitrobenzylidene)-2-propenyl- and N-(4-nitrobenzylidene)-2-buten-2-yl)anilines are converted to the corresponding dihydroquinolines and quinolines in high yields. N-(4-Nitrobenzylide! ne)- 2-(2,2-dimethylvinyl)aniline does not form derivatives of quinoline under the influence of the same acids in the given conditions.     

Reaction between isoprene and aniline on complex palladium catalysts

Isoprene and aniline have been reacted on the catalytic system Pd(acac)₂-Ph₃P to form a mixture of isomeric telomers: N-(dimethyloctadien-2,7-yl-1)anilines and N-(dimethyloctadien-1,7-yl-3)anilines but on the catalytic system Pd(acac)₂-Ph₃P-CF₃COOH the main product is a mixture of N-(methylbuten-2-yl)aniline adducts. The reaction between N-methylaniline and isoprene on the latter catalyst also gives a mixture of N-methyl and N-(methylbuten-2-yl)aniline adducts.A. N. Nesmeyanov Institute of Organoelemental Compounds, Russian Academy of Sciences, 117813 Moscow. Translated from Izvestiya Akademii Nauk, Seriya Khimicheskaya, No. 8, pp. 1794–1798, August, 1992.     

Dinuclear peroxo complexes of molybdenum(VI) containing Mannich base ligands

Dinuclear molybdenum(VI) peroxo complexes containing Mannich base ligands having formulae [Mo₂O₄(O₂)₂L-L(H₂O)₂] · H₂O [where L-L = N-[1-morpholinobenzyl] acetamide (MBA), N-[1-piperidinobenzyl] acetamide (PBA), N-[1-morpholino(-4-nitrobenzyl)] benzamide (MPNBB), N-[1-piperidino(-3-nitrobenzyl)] benzamide (PMNBB), N-[1-morpholino(-2-nitrobenzyl)] acetamide (MONBA), and N-[1-morpholino(-3-nitrobenzyl)] acetamide (MMNBA)] have been synthesized by stirring ammonium heptamolybdate with excess 30% aqueous hydrogen peroxide followed by treatment with ethanolic solution of corresponding ligands. The complexes have been characterized by elemental analysis, molar conductance, magnetic measurements, infrared (IR), electronic, TGA/DTA, mass spectral, and ¹H NMR studies. The complexes are non-electrolytes and diamagnetic. The IR spectral studies suggest that the ligands are bidentate to metal through carbonyl oxygen and ring nitrogen. Thermal analyses provide conclusive evidence for the presence of coordinated, as well as lattice water in the complexes. Dinuclear complexes preserve the individuality of the molybdenum oxo peroxo core. The complexes exhibit higher antibacterial activity against bacterium Ralastonia solanacearum (Pseudomonas solanacearum) than the free ligands.     

N-1-ALKYLITACONAMIC ACIDS-CO-STYRENE COPOLYMERS. 1. SYNTHESIS,CHARACTERIZATION AND MONOMER REACTIVITY RATIOS

Copolymers containing N-1-ethylitaconamic acid, N-1-propyl-itaconamic acid, N-1-butylitaconamic acid, N-1-hexylitaconamic acid, N-1-octylitaconamic acid and N-1-decylitaconamic acid with styrene of different comonomer compositions were synthesized and characterized. Copolymer composition was determined by elemental analysis following the nitrogen content in the resulting copolymers. Monomer reactivity ratios r₁ and r₂ of the different copolymers were estimated using straight line intersection procedures such as Fineman-Ross (F-R) and Kelen-Tüdos (K-T) and by a nonlinear one, according to the reactivity ratios error-in-variables model (RREVM). Good agreement between the different procedures for r₁ and r₂ determination was found. Differences in the reactivity of N-1-alkylitaconamic acids (NAIA) relative to styrene were found i.e., ethyl and propyl derivative are less reactive with itself than butyl, hexyl, octyl, and decyl derivatives with itself. Copolymers with some tendency toward small block formation are found.     

Synthesis and spectroscopic studies of novel mononuclear and binuclear ruthenium(III) complexes with bidentate and tridentate acyclic hydrazones

Nine novel acyclic hydrazone ligands, FINH?=?N-(furylidene)-N′-isonicotinoylhydrazine, FNH?=?N-(furylidene)-N′-nicotinoylhydrazine, PINH?=?N-(pyrienylidene)-N′-isonicotinoylhydrazine, PNH?=?N-(pyrienylidene)-N′-nicotinoylhydrazine, TINH?=?N-(thienylidene)-N′-isonicotinoylhydrazine, TNH?=?N-(thienylidene)-N′-nicotinoylhydrazine, FSH?=?N-(furylidene)-N′-salicyloylhydrazine, PSH?=?N-(pyrienylidene)-N′-salicyloylhydrazine and TSH?=?N-(thienylidene)-N′-salicyloylhydrazine, have been synthesized. Their corresponding mononuclear and binuclear ruthenium(III) complexes have been prepared by the reaction of the ligand with RuCl₃·3H₂O in 1?:?2 and 2?:?2 molar ratio and are characterized by elemental analyses, thermogravimetric analyses (TGA and DTG), IR, electronic, magnetic susceptibility and electrical conductance measurements. Electronic spectra and magnetic susceptibility measurements of the solid complexes (both mono- and binuclear) indicate an octahedral geometry around ruthenium(III). Particular emphasis is given to the binuclear complexes in which FSH, PSH and TSH behave as tridentate ligands and chloride bridges the Ru(III) ions. Conductance measurements show the mononuclear complexes are electrolytic and binuclear complexes are of non-electrolytic. The fungicidal activities of the ligands and metal complexes against Fusarium oxysporium and Aspergillus niger are described.     

Synthesis and characterization of substituted aminobiphenylglyoximes and their complexes with some transition metals

In this study, four different new vic-dioximates, [L¹H₂] N-(4-ethylphenyl)amino-biphenylglyoxime, [L²H₂] N-(4-butylphenyl)aminobiphenylglyoxime, [L³H₂] N-(4-aminoacetanilide)aminobiphenylglyoxime, and [L⁴H₂] N-(thiazol-2-yl-aminobiphenylglyoxime are synthesized from anti-4′-biphenylchloroglyoxime and the corresponding substituted aromatic amines. The Co(II), Ni(II), and Cu(II) complexes of these ligands are prepared. The structures of these new ligands and their complexes are proposed based upon IR, ¹H, and ¹³C NMR spectral data, mass spectroscopy, magnetic susceptibility measurement, and elemental analyses. The text was submitted by the authors in English.     

Rational synthesis and X-ray structural study of manganese–pyridine–alcohol derivatives

Systematic syntheses of manganese derivatives with 2-pyridineethanol, 2-pyridinemethanol and 2,6-pyridinedimethanol as chelating ligands have been undertaken to produce [trans-Mn(C₅H₄N-2-CH₂CH₂OH)₂Cl₂] (1), [cis-Mn₂(μ-Cl)₂(Cl)₂(C₅H₄N-2-CH₂CH₂OH)₂(OH₂)₂] (2), [cis-Mn₂(μ-Cl)₂(C₅H₄N-2-CH₂OH)₄]Cl₂ (3) and [MnCl{η₃-C₅H₃N-2,6-(CH₂OH)₂}{η₂-(C₅H₃N-2,6-(CH₂OH)₂)}]Cl (4). The complexes were characterized by single-crystal X-ray diffraction. The oxidation state of the manganese ions in these complexes is 2+. Magnetic data are measured down to 2?K; in dimer complexes (2 and 3) a significant antiferromagnetic interaction is observed between two manganese ions.     

Über Chalkogenolate. 196. Untersuchungen über N-(Methoxycarbimidoyl)guanidin 2. Umsetzungen mit Chlordithioameisensäureestern

On Chalcogenolates. 196. Studies on N-(Methoxycarbimidoyl)guanidine. 2. Reactions with Esters of Chlorodithioformic Acid N-(Methoxycarbimidoyl)guanidine reacts with esters of chlorodithioformic acid to produce the hitherto not known esters of N-(Methoxycarbimidoyl)guanidinedithiocarbonic acid (MCGT-R; formula see ?Inhaltsübersicht”?). By-product is the corresponding 2-amino-4-methoxy-6-alky(aryl)thio-1,3,5-triazine. MCGT-R, where R = CH₃, C₂H₅, C₆H₅, have been characterized by means of electron absorption, infrared, nuclear magnetic resonance, and mass spectra. The spectra and the related tautomeric structures of the dithioesters are discussed.     

Polystyrene bis[N-(2-pyridyl) sulfonamide] palladium(II): Synthesis,characterization as a catalyst for coupling reactions

The [N-(2-pyridyl)] para-styrene sulfonamide (PSS) was prepared as a monomer, from the reaction of para-styrene sulfonyl chloride and 2-amino pyridine in the presence of potassium hydroxide solution 0.5 M as a base, and CH₃Cl. Polystyrene [N-(2-pyridyl) sulfonamide] (PPSS) was synthesized from the polymerization of [N-(2-pyridyl)] para-styrene sulfonamide (PSS). The Polystyrene bis [N-(2-pyridyl) sulfonamide] palladium (II) as a polymer- supporting palladium complex was also prepared from the reaction of PdCl₂ (CH₃CN)₂ with PPSS in the presence of KOH 0.5 M. Polystyrene bis [N-(2-pyridyl) sulfonamide] palladium (II) is produced as a novel heterogeneous catalyst for coupling reactions for C-C bond formation. This method includes higher yield and has an easier work-up procedure. The structures of the monomer, polymer and its Pd complex were confirmed by using FT-IR and ¹H-NMR spectroscopy. Elemental analysis of Pd by inductively coupled plasma (ICP) technique and hot filtration test showed loading of the metal into solution from the catalyst The heterogeneous catalyst was recycled without any loss in its properties.     

New morpholine- and piperazine-functionalized triphenylantimony(V) catecholates: The spectroscopic and electrochemical studies

Novel functionalized triphenylantimony(V) catecholates - Ph₃Sb[4-O(CH₂CH₂)₂N-3,6-DBCat] (1), Ph₃Sb[4-PhN(CH₂CH₂)₂N-3,6-DBCat] (2), Ph₃Sb[4-Ph₂CHN(CH₂CH₂)₂N-3,6-DBCat] (3), Ph₃Sb[4,5-Piperaz-3,6-DBCat] (4) and binuclear bis-catecholate Ph₃Sb[3,6-DBCat-4-N(CH₂CH₂)₂N-4-3,6-DBCat]SbPh₃ (5) were synthesized by the oxidative addition reaction of corresponding o-quinones with triphenylantimony. The [4-O(CH₂CH₂)₂N-3,6-DBCat]²⁻, [4-PhN(CH₂CH₂)₂N-3,6-DBCat]²⁻, [4-Ph₂CHN(CH₂CH₂)₂N-3,6-DBCat]²⁻ and [4,5-Piperaz-3,6-DBCat]²⁻ are 4-(morpholin-1-yl)-, 4-(4-phenyl-piperazin-1-yl)-, 4-(4-dephenylmethyl-piperazin-1-yl)-, and 4,5-(piperazin-1,4-diyl)-3,6-di-tert-butyl-catecholate dianionic ligands, correspondingly. Complexes 1-5 were characterized in details by IR-, ¹H and ¹³C NMR spectroscopy and cyclic voltammometry. Molecular structure of 4·CH₃OH was determined by X-ray crystallography to be a distorted tetragonal-pyramidal. The NMR spectroscopic and electrochemical investigations of complexes in the presence of air reveal the reactions of complexes with dioxygen leading to the formation of spiroendoperoxides of 1,2,4,3-trioxastibolane type in a NMR yield of 25-37%.     

Synthesis of <Emphasis Type="Italic">N</Emphasis>-(2-aminoethyl)- and <Emphasis Type="Italic">N</Emphasis>-(3-aminopropyl)cytisine

2-(N-cytisinyl)acetamide or 3-(N-cytisinyl)propanamide were prepared by treatment of the methyl esters of N-cytisinylacetic or 3-(N-cytisinyl)propanoic acids with aqueous NH₄OH. N-(2-Aminoethyl)-or N-(3-aminopropyl)cytisine was synthesized by reduction of the amide with (i-Bu)₂AlH.     

VINYL RADICAL POLYMERIZATION INITIATED WITH CERIC ION AND N-(SUBSTITUTED PHENYL) ACETAMIDE SYSTEMS

The polymerization of acrylamide (AAM)in H_2O/DMF or in H_2O/CH_3CN mixed solvent initiated with ceric ion (Ce~(4+) )/N-(substituted phenyl)-acetamide systems have been studied. The redox polymerization was revealed by the low value of overall activation energy (E_α) of AAM polymerization using ceric ion/N-(substituted phenyl) acetamide system as an initiator. The end group of polymer formed was detected by IR spectrum analysis method, it revealed the presence of N-(m-acetoxy-methylphenyl) acetamide (m-AAe) moiety end group in the polymer obtained with ceric ion/m-AAe initiation system.     

Telomerization of formamide with butadiene,catalyzed by palladium complexes

Conclusions It was shown that the N-2,7- and N-1,7-octadienylformamides can be obtained by the telomerization of formamide with butadiene using the four-component catalyst Pd²⁺-Ph₃P-AlEt₃-CF₃CO₂H.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khlmicheskaya, No. 3, pp. 703–704, March, 1984.     

Selective introduction of a fluorine atom into carbohydrates and a nucleoside by ring-opening fluorination reaction of epoxides

Ring-opening fluorination reactions of epoxides using tetrabutylammonium bifluoride (TBABF)-KHF₂, or Et₃N-3HF under microwave irradiation were applied for the introduction of a fluorine atom into the carbohydrate molecules. When TBABF-KHF₂ was used as the fluorination reagent, a fluorine atom was introduced regioselectively and various functional groups can tolerate the conditions. When Et₃N-3HF was used under microwave irradiation, the reaction time could be remarkably shortened compared with the conventional oil-bath heating.     

The synthesis and characterization of some new vic-dioximes and their transition metal complexes

In this study, three new vic-dioximes, [L¹H₂], N-(5-chloro-2-methoxyphenyl)amino-1-acetyl-1-yclohexenylglyoxime, [L²H₂],N-(3-chloro-4-methoxyphenyl)amino-1-acetyl-1-cyclohexenylgly-oxime and [L³H₂], N-(3-chloro-2-methoxyphenyl)amino-1-acetyl-1-cyclohexenylglyoxime were synthesized from 1-acetyl-1-cyclohexeneglyoxime and the corresponding substituted aromatic amines. Metal complexes of these ligands were also synthesized with Ni(II), Cu(II) and Co(II) salts. The structures of these new compounds (ligands and complexes) were characterized with FT-IR, magnetic susceptibility measurement, molar conductivity measurements, mass spectrophotometer measurements, thermal methods (TGA), ¹H NMR and ¹³C NMR spectral data and elemental analyses.     

Analysis and applications of 13C NMR lanthanide induced shifts of 1,4-benzodiazepines

Lanthanide induced shifts using Yb(fod)₃ and Pr(fod)₃ were used for the signal assignments of the ¹³C spectra of the 1,4-benzodiazepines diazepam, desmethyldiazepam, prazepam and flurazepam, and for characterizing their solution conformation with respect to the substituents at N-1 and C-5. The phenyl substituent at C-5 is found to be nearly coplanar with the π-bond between C-5 and N-4, and the substituents at N-1 seem to be orientated towards the carbonyl group with dihedral angles of either 60° or 120° between the bonds N-1 and C-2 and C-12 and C-13. The metal ions seem to bind to O-2 with metal-oxygen distances between 0.19 and 0.26 nm and bond angles between 117° and 167°. Contact shifts induced by Pr(fod)₃ are slightly larger than obtained for Yb(fod)₃, whereas the latter reagent causes a stronger broadening.