Thermochemical data for n-alkylmonoamines functionalization into lamellar silicate Al-kanemite

Al-kanemite was synthesized by using inorganic salts as a source for silicon and aluminum in the hydrothermal synthesis of the material. The resulting solid was used as hosts for functionalization of polar n-alkylamine molecules of the general formula H₃C(CH₂)_n?NH₂ (n = 1 to 5) in aqueous solution. The compound was calorimetrically titrated with amine in 1,2-dichloroethane, requiring three independent operations: (i) titration of matrix with amine, (ii) matrix salvation, and (iii) dilution of the amine solution. From those thermal effects the variation in enthalpy was calculated as: (?6.81, ?7.76, ?8.97, ?9.94, and ?11.83) kJ · mol^?1, for n = 1 to 5, respectively. The exothermic enthalpy values reflected a favorable energetic process of amine-host functionalization in 1,2-dichloroethane. The original and modified Al-kanemite samples were characterized by elemental analysis, scanning electron microscopic (SEM), and nuclear magnetic nuclei of silicon-29 and carbon-13. The negative Gibbs free energy results supported the spontaneity of all these functionalization reactions. The positive favorable entropic values, as carbon chain size increased, are in agreement with the free solvent molecules in the solution, as the amines are progressively bonded to the crystalline inorganic matrix at the solid/liquid interface.     

Green synthesis of 4,6-bisarylpyrimidin-2(1H)-ones and azo-linked 4-arylpyrimidin-2(1H)-ones using NiFe2O4@SiO2nPr@glucose amine as a mild nano catalyst

The clean, environmentally benign and effective synthesis of novel azo-linked 4-arylpyrimidin-2(1H)-one derivatives and 4,6-bisarylpyrimidin-2(1H)-ones via three-component reaction of various aldehydes or synthetized azo-linked aldehydes, urea, and acetophenone promoted by NiFe₂O₄@SiO₂ⁿPr@glucose amine at room temperature (25 °C) was reported. NiFe₂O₄@SiO₂ⁿPr@glucose amine were synthesized and characterized by transmission electron microscope (TEM), fourier transform infrared spectroscopy (FT-IR), vibrating sample magnetometry (VSM), X-ray powder diffraction (XRD) and X-ray spectroscopy (EDX). These compounds were obtained in high yields and short reaction times. The catalyst could be easily recovered and reused for six cycles with almost consistent activity. The structures of the synthesized 4,6-bisarylpyrimidin-2(1H)-one compounds were confirmed by ¹H NMR, ¹³C NMR and FTIR spectral data and elemental analyses.     

Bismuth(III) bis(trifluoromethanesulfonyl)amide

Bismuth(III) bis(trifluoromethanesulfonyl)amide (Bi(NTf₂)₃, 3) has been prepared from the reaction of protiodemetallation of tri-p-tolylbismuth by a stoichiometric amount of bis(trifluoromethanesulfonyl)amine (1). The intermediates BiPh_3−n(NTf₂)_n (n=2 (4), 1 (5)) resulting from the reaction of 1 with triphenylbismuth have also been isolated. The amide 3 was able to catalyze the benzoylation and the benzenesulfonylation of toluene.     

Nano-ferrous ferric oxide (nano-Fe3O4): Powerful,reusable, and stable catalyst for N-Boc protection of amines

Nano-ferrous ferric oxide (nano-Fe₃O₄) efficiently catalyzed N-boc protection of amines in high yields and acceptable reaction times. Nano-Fe₃O₄ was applied as an efficient, green, heterogeneous and reusable magnetite catalyst. Clean reaction, simple purification, short reaction time and high yield were some other advantages of this compound.     

Synthesis, characterization and intercalation property of layered zirconium benzylamino-N,N-dimethylphosphonate phosphate materials

Layered zirconium benzylamino-N,N-dimethylphosphonate phosphate (ZBMPA) was prepared by the reaction of zirconyl chloride with benzylamino-N,N-dimethylphosphonic acid (H₂BMPA) and phosphoric acid in the presence of hydrofluoric acid. The intercalation of n-alkylamines (n-butylamine, n-heptylamine and n-decylamine) into ZBMPA was primarily investigated at room temperature. These materials were characterized by elemental analysis, ICP, XRD, SEM, FT-IR, Raman spectra, TG and DSC. The composition of ZBMPA is Zr(HPO₄)(C₆H₅CH₂N(CH₂PO₃)₂)_0.5 · 2.0H₂O. The interlayer distance of ZBMPA, n-butylamine, n-heptylamine and n-decylamine intercalation compounds is 2.03, 2.58, 2.52 and 3.17 nm, respectively. ZBMPA and the n-alkylamine intercalation compounds are different in the morphology and vibration spectra. Thermogravimetries of all materials obtained reveal three step mass losses at temperatures of up to 1000 °C. These results indicate that n-alkylamines are intercalated into the galleries of host ZBMPA.     

Michael addition polymerizations of difunctional amines (AA′) and triacrylamides (B3)

Novel hyperbranched poly(amido amine)s containing tertiary amines on the backbones and acryl or secondary amines as the surface groups were successfully synthesized via the Michael addition polymerizations of a triacrylamide [1,3,5‐triacryloylhexahydro‐1,3,5‐triazine (TT)] and a difunctional amine [n‐butylamine (BA)] NMR techniques were used to clarify the structures of hyperbranched polymers and polymerization mechanism. The reactivity of the secondary amine formed in situ was much lower than that of the primary amines in BA. When the feed molar ratio was 1:1 TT/BA, the secondary amine formed in situ was almost kept out of the reaction before the BA (AA′) and TT (B₃) monomers were consumed, and this led to the formation of A′B₂ intermediates containing one secondary amine group and two acryl groups. The self‐polymerization of the A′B₂ intermediates produced hyperbranched polymers bearing acryl as surface groups. For the polymerization with the feed molar ratio of 1:2 TT/BA, A′₂B intermediates containing one acryl group and two secondary amine groups were accumulated until self‐polymerization started; the self‐polymerization of the intermediates formed hyperbranched polymers with secondary amines as their surface groups. Modifications of surface functional groups were studied to form new hyperbranched polymers. The hyperbranched poly(amido amine)s were amorphous. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6226–6242, 2006     

Complexes amines du rhodium(I) : I. Complexes du type chloro-monoamine cyclooctadiène- 1,5 rhodium(I) et leurs produits de réaction avec l''oxyde de carbone

The reaction of amines with [(RhClCod)₂] (Cod = 1,5-cyclooctadiene) gives monomeric compounds [RhCl(Am)Cod](Am = amine). Elementary analyses as well as IR and NMR spectra are consistent with their structure.On treatment with carbon monoxide at atmospheric pressure these compounds give a series of complexes, [RhCl(Am)(CO)₂], identified by elementary analyses and IR spectra.The thermolysis of [RhCl(Aam)(CO)₂] with Aam = allyamine gives [{RhCl(Aam)CO_n}] not perfectly isolated. The reaction of [{RhCl(CO)₂}₂] with 2-vinylpyridine leads to the same kind of compound [{RhCl(Vpy)CO_m}] with Vpy = 2 -vinylpyridine. This latter complex is identified by elementary analysis. The IR spectra of these two complexes show that the olefinic double bond of amines β,γ-insaturated interacts with a rhodium atom. Their properties are discussed.     

Re-cyclization of 3-(E)-methyl 3-(4-oxo-4H-chromen-3-yl)acrylate with amines and their potential mechanism

The synthesis of 2-pyridone derivatives from different substituted amines and various 3-(E)-methyl 3-(4-oxo-4H-chromen-3-yl)acrylate derivatives was proposed and described. The optimized reaction conditions and the generality of the reaction were investigated, respectively. Moreover, less side products could be formed than the traditional method. Finally, based on the fact that (E)-methyl 2-(7-methoxy-4-oxo-3-((phenylamino)methylene)chroman-2-yl)acetate was separated and determined via X-ray single crystal diffraction, we could propose an interesting and reasonable reaction mechanism for the first time. The reaction could render this method particularly attractive for the efficient preparation of biologically and medicinally interesting molecules.     

Gallium(III) triflate-catalyzed one-pot selective synthesis of 2,3-dihydroquinazolin-4(1H)-ones and quinazolin-4(3H)-ones

A series of 2,3-dihydroquinazolin-4(1H)-ones and quinazolin-4(3H)-ones have been synthesized in good to excellent yields and high selectivity by one-pot reaction using isatoic anhydride, ammonium acetate (or amines), and aldehydes in ethanol or in DMSO under mild conditions, respectively. The reaction was efficiently promoted by 1 mol % Ga(OTf)₃ and the catalyst could be recovered easily after the reactions and reused without evident loss of reactivity.     

Complexes olefiniques du ruthenium : IV. Etude des complexes [RuClH(diène)(amine)2], structure cristalline de [RuClH(cod)(pipéridine)2]

The polymer [RuCl₂(diene)]_n undergoes bridge cleavage reaction with amines giving, at temperatures dependant on the nature of the diene moiety, the monomer [RuClH(diene)(amine)₂]. The crystal structure of the compound [RuClH(cod)(pip)₂] has been determined from three dimensional X-ray data.The complex crystallizes in space group Pmcn of the orthorhombic system, a 16.808(4), b 11.520(2), c 9.744(2) Å D_m 1.44 D_c 1.46 g cm^?3; Z 4. The structure was solved by standard heavy atom methods and has been refined by least squares to a conventional R factor of 0.039 based on 3280 refections. The complex has a crystallographically C_s imposed symmetry. The coordination geometry around the ruthenium atom is octahedrally distorted with cis amine ligands, the chloro and the hydrido ligands being trans to each other and the cyclooctadiene moiety bound through the two double bonds. The CC distances of the olefinic bonds are longer (1.394(4) Å) than was to be expected according to the Dewar—Chatt—Duncanson model. Principal bond lengths are: RuH 1.57(4); RuCl 2.555(1) (demonstrating a high structural trans influence of the hydrido ligand); RuN, 2.240(2) Å. An order of increasing structural trans influence for RuCl distances is proposed. In the IR spectrum ν(RuH) was observed at 2040 cm^?1. Decomposition of the complexes in chlorinated solvents prevented NMR studies.     

Attachment of NH3 clusters to Hg(6P0)

The ultraviolet luminescence from the Hg-photosensitised reaction of ammonia was investigated at pressures up to 10 atmospheres. From a variation of the wavelength distribution on the [NH₃], it was concluded that Hg(6³P₀) can attach clusters of NH₃ molecules to form Hg(NH₃)_n^* with n up to at least 5. The emission profiles of the stabilized complexes with n = 1–4 were determined, and also the profile from unstabilised HgNH₃^* formed in a bimolecular encounter of Hg(6³P₀) with NH₃. Dissociation constants for complexes with n = 2, 3 and 4 were measured.     

Synthesis of conformationally diverse tetrathiacalix[4]arene(amido)crowns and tetrathiacalix[4]arene amides with pendant amine functions

A series of conformationally diverse novel tetrathiacalix[4]arene(amido)crowns and amides from tetrakis((ethoxycarbonyl)methoxy)p-tert-butyl tetrathiacalix[4]arene and its debutylated analog have been prepared by their reaction with diamines [H₂N(CH₂)_nNH₂; n=2,3,4, and 6] and polyamines. It has been determined that the length of the alkyl spacer in diamines is pivotal for the formation of either the tetrathiacalix[4]arene bis(amido)crowns or tetrathiacalix[4]arene amides with pendant amine functions. The synthesized compounds represent potential building blocks for achieving sophisticated molecular assemblies for molecular organization and recognition. Single crystal X-ray analysis of tetrathiacalix[4]arene bis(amido)crown 6a revealed that it has a 1,3-alternate conformation, which forms supramolecular complexes with chloroform.     

Reactions of palldium(II) compounds with carbon monoxide in alcohol/amine systems : a new route to palladium(O) carbonyl and carboalkoxy-palladium(II) complexes

Palladium(O) carbonyl complexes, Pd(CO)(PPh₃)₃ Pd₃(CO)₃(PPh₃)₃ and Pd₃(CO)₃(PPh₃)₄, can conveniently be prepared by the reaction of (PPh₃)₂PdCl₂ with carbon monoxide at room temperature in methanol/amine systems involving primary and secondary amines such as diethylamine and cyclohexylamine. These carbonyl complexes are interconvertible under suitable conditions. On the other hand, use of tertiary amine such as triethylamine and tri-n-butylamine in place of the above amines give selectively a carbomethoxy complex (PPh₃)₂PdCl(COOCH₃).     

Reaction of Elemental Phosphorus (P4) with Thiophenol in the Presence of Amines

Elemantal phosphorus (P₄) reacts with thiophenol and amines at elevated temperature in acetonitrile to give ammonium or acetimidamidium S,S-diphenyl phosphorodithioates, depending on the nature of the amine. Analogous salts were isolated in the reaction of triphenyl phosphorotrithioite with thiophenol and corresponding amines in acetonitrile. The molecular and crystal structures of the acetimidamidium salt was confirmed by X-ray diffraction. With two different types of intermolecular interactions taken into account, a 1D supramolecular structure formed by infinite cylinders, rather that 0D structures, dimers of anion-cation pairs formed by classical hydrogen bonds exclusively, was obtained. S,S,S-Triphenyl phosphorotrithioate is formed by the reactions of P₄ with thiophenol and a catalytic amount of an amine or in the presence of diphenyl disulfide.__________Translated from Zhurnal Obshchei Khimii, Vol. 75, No. 6, 2005, pp. 886–892.Original Russian Text Copyright © 2005 by Badeeva, Batyeva, Gubaidullin, Litvinov, Sinyashin.     

Synthese und Eigenschaften von Bis(Dimethylarsino)-aminen

Synthesis and Properties of Bis(dimethylarsino) Amines Primary amines react with cacodyl halides (CH₃)₂AsX (X = Cl, J) under formation of Bis(dimethylarsino)amines RN[As(CH₃)₂]₂. Nine amines were prepared. The compounds were characterized by IR, ¹H-nmr and mass-spectroscopy. In the reactions with acid molecules cleavage of the As? N bond was observed. Formation of amine RNH₂ or ammoniumsalt (RNH₃)X and cacodyl derivates took place in all cases. The reactions of the arsinoamines with some carbonyles are reported.     

Network diversity and supramolecular isomerism in copper(II)/1,2-bis(4-pyridyl)ethane coordination polymers

Reactions of copper(II) sources with 1,2-bis(4-pyridyl)ethane (bpe) yielded metal-organic networks with diverse topologies and dimensionalities. Compounds [Cu(bpe)₂(dmf)₂]_n(ClO₄)_2n·2ndmf (1·2ndmf), [Cu(bpe)₂(dmf)₂]_n(ClO₄)_2n·3.5ndmf (2·3.5ndmf), [Cu(bpe)₂(NO₃)₂]_n·2nH₂O (4·2nH₂O) and [Cu₂(bpe)(O₂CMe)₄]_n·0.7nH₂O (5·0.7nH₂O) have been isolated by altering the copper(II) source, the reaction solvent and the crystallization process. Compounds 1·2ndmf and 2·3.5ndmf consist of cationic [Cu(bpe)₂(dmf)₂]²⁺ repeating units assembled to 1D and 2D (4,4) networks, respectively, and represent supramolecular isomers due to the conformational isomerism of the bridging bpe molecules. Compound 4·2nH₂O consists of neutral mononuclear [Cu(dpe)₂(NO₃)₂] repeating units assembled to inclined interpenetrating (4,4) sheets describing an overall entanglement that is 3D in nature, and compound 5·0.7nH₂O consists of neutral dinuclear repeating units assembled to cross-linked 1D chains.     

[Cu(mim)4]2[α-Mo8O26] – A layer-type octamolybdate framework

By reaction of (NH₄)₆Mo₇O₂₄·4H₂O, Cu(NO₃)₂·2.5H₂O and 1-methylimidazole (mim) under hydrothermal conditions the novel copper molybdate [Cu(mim)₄]₂[α-Mo₈O₂₆] is obtained in the form of blue, rectangular-shaped crystals. The title compound crystallizes with monoclinic lattice symmetry in the space group P2₁/n. The predominant structural feature of the title compound is a two-dimensional framework that is constituted by [α-Mo₈O₂₆]^4?octamolybdate units as framework nods and the copper complex [Cu(mim)₄]²⁺ as a linker. In addition to single-crystal structure analysis [Cu(mim)₄]₂[α-Mo₈O₂₆] is characterized by powder diffraction as well as by FT-IR and UV–vis spectroscopy.     

Zum verhalten von Pb(OAc)4-n(N3)n gegenüber androsta-4,9(11)-dien-3,17-dion : Pb(OAc)4-n(N3)n Als oxigenierungsmittel

An entirely new property of Pb(OAc)_4-n(N₃)_n consists in direct transfer of an O atom to the 9-,11-doublebond of the title compound with formation of the oxirane 2 and the introduction of an OH function in the allylic position at C 12 with formation of 1. In addition to the new concept,² 12α-azide 3 and the triketon 4 were also formed.     

Coulometric titrations with mercury(I) and (II) determinations of secondary amines and mercaptans

A study of the titration of aliphatic amines and mercaptans with electrolytically generated mercury(II) reagent is reported. Amines were titrated after conversion to their corresponding dithio-carbamic acids by reaction with carbon disulfide. Using this procedure, a 3.10^-4F solution of secondary amine was titrated with an accuracy of better than 1% and a concentration of 3.10^-6F with an accuracy of better than 2%. Primary amines constituted an interference in this procedure but were removed prior to the titration with salicylaldehyde. Tertiary amines were found not to interfere. Comparable titrations with generated silver ion did not give quantitative results.The application of electrolytically generated rnercury(II) reagents for the titration of another organic functional group, sulfhydryl, was also studied. The titration of a sulfhydryl compound (cysteine) was studied briefly. Amounts of cysteine down to 1. 29 mg in 100 ml of solution (1.3.10^-4F) were determined with an accuracy of better than 1%. Smaller amounts of cysteine down to 0.26 mg (2.10^-5F) were determined with about 3% accuracy.     

Ionic Liquid Promoted Eco-friendly and Efficient Synthesis of 2,3-Dihydroquinazolin-4(1H)-ones

2,3-Dihydroquinazolin-4(1H)-ones were efficiently synthesised by the reaction of isatoic anhydride, a primary amine or ammonium acetate, and different aromatic aldehydes in 1-butyl-3-methylimidazolium tetrafluoroborate ([bmim]BF₄) without using any acidic catalyst. Also a bis-derivative of the title compound as a polyheterocyclic system was synthesised successfully in high yield.