Oxidation of 1-alkylcycloalkanols with PbIV and MnIII compounds under mechanical activation

A mechanoactivated solid-state oxidative decyclization of 1-alkylcycloalkanols under the action of the Pb(OAc)₄?MX or Mn(OAc)₃?MX systems (MX is a metal halide) was carried out for the first time. The reaction affords exclusively ω-haloalkanones.     

Electrochemical oxidative ring opening of 1-methylcyclobutanol

The manganese(III) acetate-mediated electrooxidative ring opening of 1-methylcyclobutanol (1) in acetic acid affords pentane-2-one (2) as the major product. The reaction of 1-methylcyclobutanol with Mn(OAc)₃-LiCl gives 5-chloropentane-2-one (4.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 1306–1307, May, 1996     

Homolytic oxoalkylation of protonatedN-heteroaromatic compounds

The oxoalkylation of pyridine, 2-methyl-, 4-methyl-, 2,4-dimethyl-, 2,6-dimethylpyridines, quinoline, 4-methylquinoline, isoquinoline, and pyrazine with oxoalkyl radicals generated from 1-methylcyclobutanol or 1-methylcyclopentanol under the action of Pb(OAc)₄ or Mn(OAc)₃ has been carried out. The reaction products are isomers with 2-(6)- and 4-positions of the oxoalkyl group in theN-heteroaromatic ring. The isomer ratios have been determined as a function of the structure of theN-heteroaromatic compound and the reaction conditions.For the preliminary communication, see Ref. 10.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 1923–1927, November, 1993.     

Azoimidazole Complexes of Manganese(II)-thiocyanate. X-ray Structures of 2-(p-tolylazo)imidazole and Bis-[1-methyl-2-(p-tolylazo)imidazole]- Di-thiocyanato-manganese(II)

The reaction of Mn(OAc)₂ · 4H₂O and 1-alkyl-2-(arylazo)imidazole [RaaiR′ where R = H (a), Me (b); R′ = Me (1/3/), Et (2/4/)] and NH₄NCS in MeOH in a 1:2:2 mole ratio afforded [Mn(RaaiR′)₂(NCS)₂] (3) and (4) complexes. They were characterized by different physicochemical methods and the structure has been confirmed by single crystal X-ray diffraction study for title compound. One of the primary ligands was also characterised by an X-ray diffraction study.     

Complexation in Binary Cd2[Fe(CN)6]–M(II) Systems (M = Mn,Co, Ni,Cu, Zn) in Gelatin-Immobilized Cadmium(II) Hexacyanoferrates(II)

Complexation processes that occur between cadmium(II) hexacyanoferrate(II) (Cd₂[Fe(CN)₆]) and 3d-metal ions M(II) (M = Mn, Co, Ni, Cu, Zn) in thin gelatin layers with the immobilized cadmium(II) hexacyanoferrates when brought in contact with aqueous solutions of d-metal chlorides are studied. Cd²⁺ ions were found to be replaced to some extent by M²⁺ ions of the indicated d metals (except for Mn(II)) and form binuclear (dd)-metal hexacyanoferrates(II). A complete replacement of Cd(II) and formation of M₂[Fe(CN)₆] was observed in none of the cases.     

The structures of 1-(2′-hydroxybenzoyl)piperidine and 4-(2′-hydroxybenzoyl)morpholine

1-(2-hydroxybenzoyl)piperidine, C₁₂H₁₅NO₂, orthorhombic, Pbc2₁-C _2v ⁵ ;a=9.529 (1),b=10.001 (1),c=11.652 (1) Å;Z=4. The structure was determined from 1 510 single crystal X-ray data by direct methods and the refinement of the structure parameters yieldedR=0.040. There is one molecule in the asymmetric unit.4-(2-hydroxybenzoyl)morpholine, C₁₁H₁₃NO₃, orthorhombic, P2₁2₁2₁-D ₂ ⁴ ;a=13.006 (1),b=17.258 (2),c=9.125 (1) Å;Z=8. The structure parameters of the isotypic compound 4-(2-hydroxythiobenzoyl)morpholine were used in a starting set of refinement; finallyR=0.054 was obtained for 1 900 single crystal X-ray data. There are two molecules in the asymmetric unit.In both compounds the hydrogen atoms could be located by means of differenceFourier summations. The intermolecular hydrogen bonds with O ... O distances of 2.649 (2) Å for the piperidine derivate and 2.688 (3) resp. 2.754 (3) Å for the morpholine derivate are typical for intermediate bond strengths.

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Die Strukturen von 1-(2-hydroxybenzoyl)piperidin und 4-(2-hydroxybenzoyl)morpholin

Zusammenfassung 1-(2-hydroxybenzoyl)piperidin, C₁₂H₁₅NO₂, orthorhombisch, Pbc2₁-C _2v ⁵ ;a=9.529 (1),b=10.001 (1),c=11.652 (1) Å;Z=4. Die Struktur wurde aus 1 510 Einkristallröntgendaten mittels direkter Methoden bestimmt; die Strukturverfeinerung ergabR=0.040. Es ist ein Molekül in der asymmetrischen Einheit.4-(2-hydroxybenzoyl)morpholin, C₁₁H₁₃NO₃, orthorhombisch, P2₁2₁2₁-D ₂ ⁴ ;a=13.006 (1),b=17.258 (2),c=9.125 (1) Å;Z=8. Die Strukturparameter der isotypen Verbindung 4-(2-hydroxythiobenzoyl)morpholin wurden als Startsatz für die Strukturverfeinerung benutzt. Es wurdeR=0.054 aus 1 900 Einkristallröntgendaten erreicht. Es befinden sich zwei Moleküle in der asymmetrischen Einheit.In beiden Verbindungen konnten mittels Differenz-Fourier-Summierungen die Wasserstoffatome lokalisiert werden. Die intermolekularen Wasserstoffbrükken mit O ... O-Distanzen von 2.649 (2) Å für das Piperidinderivat und 2.688 (3) bzw. 2.754 (3) Å für das Morpholinderivat sind typisch für mittlere Bindungsstärken.

     

Complexation of octa(bromophenyl)tetraazaporphyrin with Mn(II) salts in DMF and pyridine

Reactions of octa(bromophenyl)tetraazaporphyrin (H₂OBPTAP) and octaphenyltetraazaporphyrin with Mn(II) acetate and chloride in DMF and pyridine are studied by spectrophotometric method. In the course of formation of octaphenyltetraazaporphyrin complexes, pyridine stabilizes an oxidation state of Mn (+2), and in addition to Mn(II) complex, its radical form is likely to be obtained also in this case. In DMF, the octaphenyltetraazaporphyrinatomanganese(III) complexes are produced. Kinetic studies showed that the complexing capability of Mn acetate in reaction with azaporphyrins drastically differs from that of Mn chloride. H₂OBPTAP does not react with MnCl₂ in pyridine, while its reaction with Mn(OAc)₂ has k_eff²⁹⁸ = (3.1 ± 0.2) × 10^-3 s^-1. Reaction of H₂OBPTAP with Mn(OAc)₂ in DMF occurs instantaneously, whereas in the case of its reaction with MnCl₂, k_eff²⁹⁸ = (1.9 ±0.2) × 10^-3 s^-1.Translated from Koordinatsionnaya Khimiya, Vol. 31, No. 1, 2005, pp. 22–27.Original Russian Text Copyright © 2005 by Klyueva, Repina, Chizhova, Berezin.     

peri-Naphthylenediamines 18. 1,8-Bis(dimethylamino)-4-vinylnaphthalene

The 1-[1,8-bis(dimethylamino)-4-naphthyl[ethyl carbocation generated from the corresponding alcohol in benzene in the presence of Al₂O₃ undergoes elimination according to theE1 mechanism to give previously unknown 1,8-bis(dimethylami no)-4-vinyl naphthalene in a good yield. This compound was also synthesized from 1,8-bis(dimethylamino)-4-formylnaphthalene by the Wittig reaction. Polymerization of the vinylic derivative obtained was studied.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 9, pp. 2297–2300, September, 1996.     

Oxygenation of saturated and unsaturated hydrocarbons with sodium periodate catalyzed by manganese(III) tetra-arylporphyrins, to study the axial ligation of imidazole

Competitive oxygenation of cyclooctene and tetralin with sodium periodate catalyzed by Mn^(III)(TPP)OAc, TPP = meso-tetraphenylporphyrin; Mn^(III) (TNP)OAc, TNP =meso-tetrakis(1-naphthyl) porphyrin; Mn^(III) (TMP)OAc, TMP =meso-tetrakis(2,4,6-trimethyl-phenyl)porphyrin; Mn^(III) (TDCPP)OAc, TDCPP =meso-tetrakis(2,6-dichlorophenyl) porphyrin, and Mn^(III) (TPNMe₂-TFPP)OAc, TPNMe₂-TFPP =meso-tetrakis(para-NMe₂-tetrafluorophenyl)porphyrin, was carried out in the presence or absence of imidazole. This study showed that, in the absence of imidazole, selectivity for epoxide formation was high with electron-rich catalysts such as Mn(TPP)OAc, Mn(TNP)OAc and Mn(TMP)OAc, but low with electron-deficient catalysts such as Mn(TDCPP)OAc and Mn(TPNMe₂-TFPP)OAc. Presumably, not only the axial ligation of imidazole to the four-coordinate Mn(III)-center, but also the steric and electronic influences of aryl-substituents on the porphyrin periphery affect the selectivity of the catalytic oxidation reaction.     

The solid state reactions of o-aminobenzoic acid with Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Mn(Ⅱ) acetate hydrate at room temperature

The solid-solid state reactions of o-aminobenzoic acid with Zn(OAc)2.2H2O, Cu(OAc)2 .H2O, Ni(OAc)2.4H2O and Mn(OAc)2.4H2O result in the formation of corresponding complexes M(OAB)2 (M = Zn(Ⅱ), Cu(Ⅱ), Ni(Ⅱ), Mn(IⅡ)). XRD, IR and elemental analysis methods have been used to characterize the solid products. The activation energies of these reactions, which are calculated from the kinetic data obtained by means of the isothermal electrical conductivity measurement method, have been found to increase in the order: Cu(OAc)2.H2O(37.7 kJ.mol-1)~Mn(OAc)2.4H2O (39.7kJ.mol-1) < Zn(OAc)2.2H2O (56.3 kJ.mol-1) < Ni(OAc)2.4H2O (85.2 kJ.mol-1). The trend is related to their crystal structures.     

Synthesis and antibacterial activities of metal(II) complexes with Schiff bases derived from 3,5-diiodosalicylaldehyde

Two new Schiff bases (2,4-diiodo-6-[(2-morpholin-4-yl-ethylimino)-methyl]-phenol and 2,4-diiodo-6-[(3-morpholin-4-yl-propylimino)-methyl]-phenol), condensed from 3,5-diiodosalicylaldehyde with 2-morpholinoethylamine and 3-morpholinopropylamine, have been designed and synthesized. Reaction of the Schiff bases with Zn(OAc)₂ · 2H₂O, Cu(OAc)₂ · H₂O, Ni(OAc)₂ · 4H₂O, Co(OAc)₂ · 4H₂O, Cd(OAc)₂ · 2H₂O, Mn(OAc)₂ · 4H₂O, Fe(SO4)₂ · 7H₂O, and Hg(OAc)₂ led to the formation of 16 new mononuclear complexes. The complexes were characterized by UV, Infrared, ESI-MS, and elemental analyses, and 3,5-diiodosalicylalidene-2-morpholinoethylaminozinc(II) (1) and 3,5-diiodosalicylalidene-2-morpholinoethylaminocopper(II) (2) were characterized by single crystal X-ray diffraction. Based on crystal structural analysis of 1 and 2, coupled with their spectral similarity with 3–16, it can be concluded that 3–16 have structures similar to 1 and 2. All the complexes were assayed for antibacterial activities against three Gram positive bacterial strains (Bacillus subtilis, Staphylococcus aureus, and Streptococcus faecalis) and three Gram negative bacterial strains (Escherichia coli, Pseudomonas aeruginosa, and Enterobacter cloacae) by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyl tetrazolium bromide method. Among the complexes tested, 8 and 16 showed the most favorable antibacterial activity with minimum inhibitory concentration of 0.781, 12.5, 6.25, 3.125, 3.125, 6.25 and 1.562, 6.25, 1.562, 3.125, 3.125, 1.562 µg mL^?1 against B. subtilis, S. aureus, S. faecalis, P. aeruginosa, E. coli, and E. cloacae, respectively.     

On the mechanism of the Fe(CO)5-catalyzed Kharasch reaction

Regioselectivity and diastereoselectivity of the addition of BrCCl₃ to (R)-3-(E)-cinnamoyl-4-phenyloxazolidin-2-one (1) and (R)-3-(E)-acryloyl-4-phenyloxazolidin-2-one (2) catalyzed by Fe(CO)₅ or initiated with benzoyl peroxide were investigated. Stereochemistry of the reaction of BrCCl₃ with the a-complexes (4R,S,S)-²-(3-(E)-cinnamoyl-4-phenyl-oxazolidin-2-one)irontetracarbonyl (3a) and (4R,R)-²-(3-acryloyl-4-phenyloxazolidin-2-one)irontetracarbonyl (4b) was also studied. The results obtained allow the following conclusions to be drawn: (1) the thermal Kharasch reaction catalyzed by Fe(CO)₅ proceeds by a redox catalysis mechanism; (2) iron (in any of its oxidation states) is not coordinated to olefins in the transition state of the reaction; (3) the transfer of the halogen atom on the radical adduct probably occurs inside a radical-iron cation pair.Yu. T. Struchkov is deceasedTranslated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 3, pp. 640–648, March, 1996.     

Synthesis and Oxidation of N‐Aminoglyconolactams: A Synthesis of Mannostatin A

The N‐amino‐ribono‐1,5‐lactam 4 was prepared in two high‐yielding steps from the known methanesulfonate 2 . Oxidation of 4 with t‐BuOCl in the presence of 2,6‐lutidine afforded the tetrazene 6 (63%). Oxidation with MnO₂ gave the deaminated lactam 7 (40%), which was also obtained, together with the lactone 8 , upon oxidation of 4 with PhSeO₂H. Oxidation with Mn(OAc)₃/Cu(OAc)₂ provided the lactam 7 as the major and the dimer 9 as the minor product. Oxidation of 4 with 3 equiv. of Pb(OAc)₄ in toluene at room temperature gave two cyclopentanes, viz. the acetoxy epoxide 10 and the diazo ketone 11 in a combined yield of 78%. Oxidation with Pb(OBz)₄ provided 11 and the crystalline benzoyloxy epoxide 12 . The crystal structure of 12 was established by X‐ray analysis. The N‐amino‐glyconolactams 41, 46 , and 51 were prepared similarly to 4 . Their oxidation with Pb(OAc)₄ provided the diazo ketones 56, 57 , and 58 as the only isolable products. Oxidation of the N‐amino‐mannono‐1,5‐lactam 55 with Pb(OAc)₄ in the presence of DMSO gave the sulfoximine 59 . Mannostatin A, a strong α‐mannosidase inhibitor, was synthesized from the acetoxy epoxide 10 (obtained in 48% from 4 ) in seven steps and in an overall yield of 45%.     

Production and isolation of ligated metal(IV)‐oxo ions by tandem mass spectrometry

High valent metal(IV)‐oxo species, [M(?O)(MeIm)_n(OAc)]⁺ (M = Mn–Ni, MeIm = 1‐methylimidazole, n = 1–2), which are relevant to biology and oxidative catalysis, were produced and isolated in gas‐phase reactions of the metal(II) precursor ions [M(MeIm)_n(OAc)]⁺ (M = Mn–Zn, n = 1–3) with ozone. The precursor ions [M(MeIm)(OAc)]⁺ and [M(MeIm)₂(OAc)]⁺ were generated via collision‐induced dissociation of the corresponding [M(MeIm)₃(OAc)]⁺ ion. The dependence of ozone reactivity on metal and coordination number is discussed. Copyright © 2010 John Wiley & Sons, Ltd.     

Stereospecific syntheses of new manganese(I) isocyanide derivatives

Three series of cationic manganese(I) carbonyls are reported: [Mn(CO)_5-n(CNMe)_n(CNPh)]PF₆ (n = 1 → 4), [Mn(CO)_5-n(CNMe)(CNPh)_n]PF₆ (n = 1 → 4), and [Mn(dpe)(CO)_4-n(CNMe)_n]PF₆ (n = 1 → 4). Most of these compounds were prepared from a substituted metal carbonyl halide by replacement of halide ion by an added ligand (CNR or CO), such reactions requiring an added halide ion acceptor (Ag⁺ or AlCl₃). The added ligand enters the site of departing halide ion. It was possible to prepare isomers of many compounds reported, taking advantage of this stereospecificity. Structures of the products were defined, often unequivocally, by infrared and nmr spectroscopic data. Cyclic voltammetry showed that these compounds undergo one electron oxidations, the ease of oxidation determined by the nature of the ligand groups and the stereochemistry.     

Crystal and Molecular Structure of Cu(II) Bis-(2-methoxy-2,6-dimethyl-3-imino-5-heptanonate)

A new compound from the series of alkoxyketoiminates, Cu(II) bis-(2-methoxy-2,6-dimethyl-3-imino-5-heptanonate), has been synthesized and studied by X-ray crystallography. Crystal data for CuO₄N₂C₂₀H₃₆: a=10.154(1), b=9.921(1), c=11.684(2) , =96.17(1)°, space group P2₁/c, Z=2, dcalc =1.226 g/cm³, R=0.037. The structure is molecular and built from isolated trans-complexes. The copper atom has a plane square environment of two oxygen atoms (Cu–O 1.93 ) and two nitrogen atoms (Cu–N 1.90 ). The O–Cu–N chelate angle is 91.7°. The complex has an intramolecular hydrogen bond, N–H...O 2.16 , involving the alkoxy oxygen atom. The molecular packing in the crystal is close to that of copper(II) dipivaloylmethanate. The calculated van der Waals intermolecular interaction energies and thermogravimetric characteristics of the complexes are compared.     

Molecular Docking,DFT Calculations,Effect of High Energetic Ionizing Radiation,and Biological Evaluation of Some Novel Metal (II) Heteroleptic Complexes Bearing the Thiosemicarbazone Ligand

New Pb(II), Mn(II), Hg(II), and Zn(II) complexes, derived from 4-(4-chlorophenyl)-1-(2-(phenylamino)acetyl)thiosemicarbazone, were synthesized. The compounds with general formulas, [Pb(H₂L)₂(OAc)₂]ETOH.H₂O, [Mn(H₂L)(HL)]Cl, [Hg₂(H₂L)(OH)SO₄], and [Zn(H₂L)(HL)]Cl, were characterized by physicochemical and theoretical studies. X-ray diffraction studies showed a decrease in the crystalline size of compounds that were exposed to gamma irradiation (γ-irradiation). Thermal studies of the synthesized complexes showed thermal stability of the Mn(II) and Pb(II) complexes after γ-irradiation compared to those before γ–irradiation, while no changes in the Zn(II) and Hg(II) complexes were observed. The optimized geometric structures of the ligand and metal complexes are discussed regarding density functional theory calculations (DFT). The antimicrobial activities of the ligand and metal complexes against several bacterial and fungal stains were screened before and after irradiation. The Hg(II) complex has shown excellent antibacterial activity before and after γ-irradiation. In vitro cytotoxicity screening of the ligand and the Mn(II) and Zn(II) complexes before and after γ-irradiation disclosed that both the ligand and Mn(II) complex exhibited higher activity against human liver (Hep-G2) than Zn(II). Molecular docking was performed on the active site of MK-2 and showed good results.     

Mn(OAc)3-promoted sulfur-directed addition of an active methylene compound to alkenes

Various alkenes substituted at the 1,2-positions by phenyl, thiophene and furan rings were reacted with 3-(4-methoxyphenyl)-3-oxopropanenitrile in the presence of Mn(OAc)₃·2H₂O. The exact structure and configuration of the dihydrofuran derivatives formed were determined. In all cases only one regioisomer was formed. The observed regioselectivity was explained on the basis of the formation of a complex between Mn(OAc)₃, alkene, and 3-(4-methoxyphenyl)-3-oxopropanenitrile, which directs the mode of the addition to the double bond.     

Synthesis and antimicrobial activities of metal(II) complexes with bis(2,4-diiodo-6-propyliminomethyl-phenol)-pyridine

Seven new mononuclear complexes have been synthesized from 2,4-diiodo-6-propyliminomethyl-phenol in pyridine and Cu(OAc)₂ · H₂O, Ni(OAc)₂ · 4H₂O, Co(OAc)₂ · 4H₂O, Zn(OAc)₂ · 2H₂O, Cd(OAc)₂ · 2H₂O, Mn(OAc)₂ · 4H₂O, and Hg(OAc)₂. The complexes were characterized by UV, IR, ESI-MS, and elemental analyses; bis(2,4-diiodo-6-propyliminomethyl-phenol)-pyridine-copper(II) (1) was characterized by X-ray crystallography. The central metal in each complex is five-coordinate by two nitrogens and two oxygens from two 3,5-diiodosalicylaldehyde Schiff-base ligands and one nitrogen from pyridine. The 3,5-diiodosalicylaldehyde Schiff base is bidentate. All the complexes were assayed for antibacterial (Bacillus subtilis, Staphylococcus aureus, Streptococcus faecalis, Pseudomonas aeruginosa, Escherichia coli, and Enterobacter cloacae) activities by the MTT method. Complex 1 showed the most favorable antimicrobial activity with minimum inhibitory concentrations of 6.25, 3.125, 6.25, 3.125, 6.25, 3.125 µg mL^?1 against B. subtilis, S. aureus, S. faecalis, P. aeruginosa, E. coli, and E. cloacae, respectively.     

solid-state reaction of a lead tetraacetate-metal halide system with naphthalene under mechanical activation

A mechanically activated solid-state reaction of halogenation of naphthalene with a Pb(OAc)₄—alkaline or alkaline-earth metal halide system was carried out to yield 1-halonaphthalene as the main reaction product and 1,4-dihalonaphthalene. The solid-state halogenation of naphthalene is more selective than a liquid-phase reaction.