FeCl3-catalyzed Ritter reaction. Synthesis of amides

A safe and inexpensive synthesis of amides, from benzylic alcohols and nitriles and from t-butyl acetate and nitriles, using a Ritter reaction catalyzed by FeCl₃·6H₂O is described.     

Asymmetric Michael addition promoted by (R,R)-trans-1,2-diaminocyclohexane in ionic liquids

In tetrafluoroborate based ionic liquids fair yields and enantiomeric excesses up to 91% were obtained in the Michael addition of ethyl cyclohexanone-2-carboxylate to methyl vinyl ketone, using (R,R)-trans-1,2-diaminocyclohexane as chiral auxiliary (37% mol/mol with respect to the donor). The presence of catalytic amounts of metal sources [Ni(OAc)₂ · 4H₂O, Co(acac)₂, FeCl₃ · 6H₂O, LaCl₃, Cu(OAc)₂ · H₂O] did not improve the activity, and, in some instances, caused a drop of enantioselectivity. Reactions carried out in the absence of any metal and with a Michael donor/diamine molar ratio of 20 allowed us to ascertain that the reaction can be performed catalytically.     

Selective 1,2-dihalogenation and oxy-1,1-dihalogenation of alkynes by N-halosuccinimides

1,2-Dihalogenation and oxy-1,1-dihalogenation of alkynes by N-halosuccinimides can be selectively realized through using different reaction conditions. α,β-Dihalo alkenes were obtained exclusively using THF as solvent without using any catalyst, while α,α-dihalo ketones were synthesized using a mixed solvent of THF and H₂O in the presence of FeCl₃·6H₂O. Terminal aromatic alkynes are smoothly transformed into α,α-dihalo ketones on water without a catalyst.     

Conservation of [(C2H4NH3)3N]2·(ZrF7)2·H2O layers during the topotactic dehydration of [(C2H4NH3)3N]2·(ZrF7)2·9H2O

Tren amine cations [(C₂H₄NH₃)₃N]³⁺ and zirconate or tantalate anions adopt a ternary symmetry in two hydrates, [H₃tren]₂·(ZrF₇)₂·9H₂O and [H₃tren]₆·(ZrF₇)₂·(TaOF₆)₄·3H₂O, which crystallise in R32 space group with a_H = 8.871 (2) Å, c_H = 38.16 (1) Å and a_H = 8.758 (2) Å, c_H = 30.112 (9) Å, respectively. Similar [H₃tren]₂·(MX₇)₂·H₂O (M = Zr, Ta; X = F, O) sheets are found in both structures; they are separated by a water layer (O_w(2)-O_w(3)) in [H₃tren]₂·(ZrF₇)₂·9H₂O. Dehydration of [H₃tren]₂·(ZrF₇)₂·9H₂O starts at room temperature and ends at 90 °C to give [H₃tren]₂·(ZrF₇)₂·H₂O. [H₃tren]₂·(ZrF₇)₂·H₂O layers remain probably unchanged during this dehydration and the existence of one intermediate [H₃tren]₂·(ZrF₇)₂·3H₂O hydrate is assumed. O_w(1) molecules are tightly hydrogen bonded with -NH₃⁺ groups and decomposition of [H₃tren]₂·(ZrF₇)₂·H₂O occurs from 210 °C to 500 °C to give successively [H₃tren]₂·(ZrF₆)·(Zr₂F₁₂) (285 °C), an intermediate unknown phase (320 °C) and ZrF₄.     

FeCl3·6H2O-promoted skeleton-rearrangement of 1-substituted-3-benzazepines: substrate extension and product utilization

FeCl₃·6H₂O-promoted skeleton-rearrangement of 1-substituted-3-benzazepines was further exploited. Both 1-aryl- and 1-alkyl- or 1-alkenyl-benzazepines underwent this reaction smoothly. The rearrangement products were used to prepare a series of novel derivatives containing both tetrahydroisoquinoline (THIQ) and tetrahydropyrimidin-4(1H)-one scaffolds through a Mannich-type process.     

Selective cleavage of sugar anomeric O-acyl groups using FeCl3·6H2O

A convenient method has been developed for regioselective anomeric deacylation of carbohydrate derivatives using FeCl₃·6H₂O in CH₃CN. Operational simplicity, economic consideration, high yield, and low toxicity are key features associated with this protocol.     

Thermal and spectral studies of 5-(phenylazo)-2-thiohydantoin and 5-(2- hydroxyphenylazo)-2-thiohydantoin complexes of cobalt(II), nickel(II) and copper(II)

Complexes of 5-(phenylazo)-2-thiohydantoin (L¹) and 5-(2-hydroxyphenylazo)-2-thiohydantoin (HL²) with Co(II), Ni(II) and Cu(II) salts have been synthesised and characterized by elemental analysis, conductivity, magnetic susceptibility, UV-Vis, IR, ESR and TG studies. The magnetic and spectral data suggested octahedral geometry for [L¹M(OAc)₂(H₂O)₂]·xH₂O {M=Ni^ll and Cu^ll} and [L¹CuCl₂(H₂O)]·H₂O (dimeric form for the latter), trigonal bipyramidal geometry for [L²Co(OAc)(H₂O)]·2H₂O, square pyramidal geometry for [L²Ni(OAc)(H₂O)]·H₂O and square planar geometry for [L²CuCl]·2H₂O. TG studies confirmed the chemical formulations of these complexes and showed that their thermal degradation takes place in three to five steps, depending on the type of the ligand and the geometry of the complex. The kinetic parameters (n, E^#, A, ΔH^#, ΔS^# and ΔG^#) of the thermal decomposition stages were computed using the Coats-Redfern and other standard equations and are discussed.     

Syntheses and characterization of the samarium(III)-copper(II) 3D coordination network constructed by iminodiacetic acid

The hydrothermal reaction of Sm₂O₃ with iminodiacetic acid (H₂Idad), CuO, and H₂O with a mole ratio of 1:2:4:300 resulted in the formation of one nanoporous 3D open framework Cu(II)-Sm(III) coordination polymer, [{Sm₂Cu₃(Idad)₆}·8H₂O]_n. Investigation shows that the coordination polymer possesses high thermal and structural stability. Temperature-dependent magnetic susceptibilities of the coordination polymer with the similar structure, [{Gd₂Cu₃(Idad)₆}·8H₂O]_n, were studied.     

Degradation of perfluorinated sulfonic acid films: An in-situ infrared spectro-electrochemical study

The in-situ Fourier transform infrared (FTIR) spectro-electrochemical method was used to evaluate the degradation mechanism of perfluorinated sulfonic acid (PFSA) polymer for the first time. The effect of H₂O₂ concentration in Fenton's reagent on the PFSA film degradation was studied. It was found that the effect of the H₂O₂ concentration on the chemical degradation of the PFSA film was limited, whereas, the electrochemical degradation was obviously enhanced at higher H₂O₂ concentrations. The chemical degradation of PFSA film in Fenton's reagent was similar to that in pure H₂O₂ solution. However, the results indicated that the electrode potential is the dominating factor affecting the degradation of the PFSA film. It is clear that the electrochemical degradation of PFSA film in Fenton's reagent is more serious than that in pure H₂O₂ solution. Moreover, it is indicated that the main cause of the membrane degradation is the instability of the backbone of the polymer chain under electrochemical conditions and secondarily the loss of sulfuric groups in the side-chains. It is concluded that the in-situ FTIR spectro-electrochemical method could be used to evaluate more objectively the degradation of the polymer film.     

Fe-exchanged fluorotetrasilicic mica as an active and reusable catalyst for Michael reaction

Fe³⁺-exchanged fluorotetrasilicic mica acts as a highly effective and reusable catalyst for the solventless Michael reaction of β-ketoesters with vinyl ketones under mild condition. The immobilized catalyst shows higher activity than homogeneous Fe³⁺ catalysts, FeCl₃·6H₂O and Fe(NO₃)₃·9H₂O.     

Synthesis of tertiary-butyl acrylate polymers and preparation of diblock copolymers using atom transfer radical polymerization

The synthesis of tert-butyl acrylate by atom transfer radical polymerization (ATRP) is reported. This polymer was prepared using FeCl₂ · 4H₂O(PPh₃)₂ catalyst system in conjunction with methyl 2-bromopropionate as initiator, in bulk and in solution using acetone as a solvent. The addition of solvent was necessary in order to decrease the polymerization rate and to afford low polydispersity polymers. The number-average molecular weights of the resulting polymers increased in direct proportion to the monomer conversion, and the polydispersities (M_w/M_n) were as low as 1.2. In addition, the preparation of an AB diblock copolymer of poly (n-butyl methacrylate)-block-poly (tert-butyl acrylate) by ATRP is reported. The resulting polymers and copolymers were characterized by means of size exclusion chromatography and ¹H-NMR Spectroscopy.     

Selective anion-exchange intercalation of isomeric benzoate anions into the layered double hydroxide [LiAl2(OH)6]Cl·H2O

All the geometric isomers of the benzoate derivatives, XC₆H₄CO₂⁻ (X=F, Cl, Br, OH, OCH₃, NO₂, CO₂CH₃, NH₂, N(CH₃)₂) can be intercalated into the layered double hydroxide [LiAl₂(OH)₆]Cl·H₂O in 50% (v/v) water/ethanol solution at 80 °C to give fully anion-exchanged first stage intercalation compounds [LiAl₂(OH)₆]G·yH₂O (G=a substituted benzoate). The observed interlayer separations of the intercalates vary from 14.3 Å for [LiAl₂(OH)₆](4-nitrobenzoate)·2H₂O to 20.6 Å for [LiAl₂(OH)₆](3-dimethylaminobenzoate)·3H₂O. Competitive intercalation studies using mixtures of isomeric benzoates showed that the 4-isomers and 2-isomers are the most and the least preferred anions, respectively. Comparing the calculated dipole moments of the anions with the observed isomeric intercalation preferences suggests that dipole moment may be a good general index for the preference; however, it should be remembered that the bulkiness and electronegativity of the other substituent could be very important factors that affect the preferential intercalation.     

Two-dimensional composition diagram of the Al(OH)3-dien-HFaq.-ethanol system: Evidence of a new tetrahedral (Al4F18) polyanion

Six domains appear in the 2D composition diagram of the Al(OH)₃-dien-HF_aq.-ethanol system at 190 °C and [Al³⁺] = 1 mol L⁻¹ under microwave heating. Four organic-inorganic fluorides crystallise: [H₃dien]·(AlF₆) (P2₁/c, Z = 4), [H₃dien]₂·(AlF₅(H₂O))₃·2H₂O (P2₁/n, Z = 4), [H₃dien]·(AlF₆)·2H₂O, which was previously known, and [H₃dien]₂·(Al₄F₁₈) (C2/c, Z = 4). A new (Al₄F₁₈)⁶⁻ polyanion, which results from the tetrahedral association of four AlF₆ octahedra linked by corners, is evidenced in [H₃dien]₂·(Al₄F₁₈).     

On the Lanthanide Ferrocyanides KLnFe(II)(CN)6·xH2O (Ln=La-Lu): Characterization and Thermal Evolution

The properties of a series of lanthanide hexacyanoferrate(II) n-hydrates were studied by thermal analysis, IR spectroscopy and X-ray diffraction. Thermal analysis results show that there are three kinds of complexes in this series, KLn[Fe(CN)₆]·4 H₂O (Ln=La-Nd), KSm[Fe(CN)₆]·3H₂O and KLn[Fe (CN)₆]·3.5H₂O (Ln=Eu-Lu). On the basis of IR spectra, only two different types of complexes show obvious differences. Indeed for the tetrahydrates, there is one OH stretching band; on the other hand, for the samarium phase and the 3.5 hydrates a splitting of HOH stretching mode is observed. The splitting of the H₂O band is correlated to a symmetry modification. The crystal structures of the three complexes KLn[Fe(CN)₆]·3.5H₂O (Ln=Eu, Er and Lu) were determined; they belong to orthorhombic symmetry (space group Cmcm). Heat-treated powders have been investigated by X-ray analysis which show the formation of thin needles of LnFeO₃ at 600°C.     

Nickel(IV) dithiocarbamato complexes of the [Ni(ndtc)3]X type: X-ray structure of [Ni(hmidtc)3][FeCl4]

A series of fourteen octahedral nickel(IV) dithiocarbamato complexes of the general formula [Ni(ndtc)₃]X·yH₂O {ndtc stands for the appropriate dithiocarbamate anion, X stands for ClO₄⁻ (1-8; y = 0) or [FeCl₄]⁻ (9-14; y = 0 for 9-12, 1 for 13 and 0.5 for 14} was prepared by the oxidation of the corresponding nickel(II) complexes, i.e. [Ni(ndtc)₂], with NOClO₄ or FeCl₃. The complexes, involving a high-valent Ni^IVS₆ core, were characterized by elemental analysis (C, H, N, Cl and Ni), UV-Vis and FTIR spectroscopy, thermal analysis and magnetochemical and conductivity measurements. The X-ray structure of [Ni(hmidtc)₃][FeCl₄] (9) was determined {it consists of covalently discrete complex [Ni(hmidtc)₃]⁺ cations and [FeCl₄]⁻ anions} and this revealed slightly distorted octahedral and tetrahedral geometries within the complex cations, and anions, respectively. The Ni(IV) atom is six-coordinated by three bidentate S-donor hexamethyleneiminedithiocarbamate anions (hmidtc), with Ni-S bond lengths ranging from 2.2597(5) to 2.2652(5) Å, while the shortest Ni···Cl and Ni···Fe distances equal 4.1043(12), and 6.2862(6) Å, respectively. Moreover, the formal oxidation state of iron in [FeCl₄]⁻ as well as the coordination geometry in its vicinity was also proved by ⁵⁷Fe Mössbauer spectroscopy in the case of 9.     

Synthesis and thermochemistry of MgO·3B2O3·3.5H2O

A new magnesium borate MgO·3B₂O₃·3.5H₂O has been synthesized by the method of phase transformation of double salt and characterized by XRD, IR and Raman spectroscopy as well as by TG. The structural formula of this compound was Mg[B₆O₉(OH)₂]·2.5H₂O. The enthalpy of solution of MgO·3B₂O₃·3.5H₂O in approximately 1 mol dm⁻³ HCl was determined. With the incorporation of the standard molar enthalpies of formation of MgO(s), H₃BO₃(s), and H₂O(l), the standard molar enthalpy of formation of −(5595.02±4.85) kJ mol⁻¹ of MgO·3B₂O₃3.5H₂O was obtained. Thermodynamic properties of this compound was also calculated by group contribution method.     

IrCl3 or FeCl3-catalyzed convenient synthesis of 3-hydroxyphthalates

IrCl₃·3H₂O or FeCl₃-catalyzed convenient synthesis of 3-hydroxyphthalates has been achieved by a Diels-Alder reaction of furans with dimethyl acetylenedicarboxylate, followed by ring-opening aromatization reaction of the Diels-Alder adducts, 7-oxabicyclo[2.2.1]hepta-2,5-diene derivatives. In addition, 7-azabicyclo[2.2.1]hepta-2,5-diene derivative, derived from N-Boc-pyrrole and dimethyl acetylenedicarboxylate, also converted into 3-aminophthalate derivative.     

Viscosity of Potassium Trioxalato Complexes of Al(III), Fe(III), Co(III), and Cr(III) in Aqueous Solution Between 15° and 35°C

The viscosity of dilute aqueous solutions of K₃[AI(ox)₃]·3H₂O, K₃[Fe(ox)₃]·3H₂O, K₃[Co(ox)₃]·3H₂O, and K₃[Cr(ox)₃]·3H₂O complexes, as well as K₂(ox)·H₂O, were measured between 15 and 35°C. Those of CoCl₂, 6H₂O, FeCl₃, A1₂(SO₄)₃·18H₂O, and CrCl₃·6H₂O were measured at 25°C. These data were analyzed by the Jones–Dole equation. The ionic B coefficients of the above complex anions were discussed in terms of ion–solvent interactions and the overall change in B associated with complex formation.     

A novel one-pot oxidative cyclization of 2′-amino and 2′-hydroxychalcones employing FeCl3·6H2O-methanol. Synthesis of 4-alkoxy-2-aryl-quinolines and flavones

A simple, inexpensive, and efficient oxidative cyclization of 2′-amino and 2′-hydroxychalcones has been carried out by employing FeCl₃·6H₂O-methanol under mild conditions. This method has been investigated for the synthesis of 2-(1,3-diphenyl-1H-pyrazol-4-yl)-4-methoxyquinolines.