Primary Aliphatic Diamines Research Articles

Cu(I) coordination by N,N,N’,N’-tetra(di-ortho-anisylphosphanylmethyl) ethylene and propylene diamine: First example of a sandwiched CuCl-tetramer

New chelating α-aminophosphanes were obtained by Mannich-type reactions between formaldehyde, bis(2-methoxyphenyl)phosphane and aliphatic primary diamines bearing either a C2 or C3 carbon bridge between the amine functionalities. The reaction conditions, and in particular, the reaction sequence was found to significantly depend on the length of the carbon bridge of the diamine. Both obtained α-aminophosphanes (i.e. N,N,N’,N’-tetra(di-ortho-anisylphosphanylmethyl)-1,2-diaminoethane (L1) and N,N,N’,N’-tetra(di-ortho-anisylphosphanylmethyl)-1,3-diaminopropane (L2)) gave along with neocuproine cationic dinuclear Cu(I) complexes. The Cu(I) complex with L2 as ligand was further converted by the aid of NiCl2(DME) (DME = 1,2-dimethoxyethane) into a tetranuclear copper cluster showing a new type of CuCl-tetramer molecular structure. All synthesized compounds were characterized in solution by multinuclear NMR-, UV/Vis-spectroscopy, mass spectrometry and in the solid state by elemental analysis and some of them by single crystal structure analysis.

Reinvestigations of the reactions of hexachlorocyclotriphosphazene with difunctional primary amines leading to novel dangler, ansa and bridged derivatives. Spectroscopic studies of the derived products

Abstract In an extension of the research on the nucleophilic substitution reactions of hexachlorocyclotriphosphazene (1) with linear aliphatic primary diamines, NH2-(CH2)n –NH2 (n = 3, 5, 6 and 8) are surveyed. In the presence of pyridine, NaH and in excess of the used amine as base, at 0 °C and room temperature, we subjected the reactions of 1, to a systematic reinvestigation with aliphatic propane-1,3-, pentane-1,5-, hexane-1,6- and octane-1,8-diamines (2, 3, 4 and 5 respectively) and we isolated a total of 18 compounds which include examples of all four structural types (open chain, spiro, ansa and the bino derivatives). The novel synthesized open chain (6), mono-ansa (8a), spiro-ansa (10), single-bridged (12a), double-bridged (13a) and tri-bridged (14a) cyclophosphazene derivatives are reported for the first time. The synthesized compounds are characterized by elemental analysis, MS, FT-IR, 1H and 31P NMR spectroscopy. Spectroscopic data, product types and the relative yields are compared with those of the previously reported cyclophosphazene derivatives derived from di-functional nucleophilic reagents.

Development of Fullerene Thin-Film Assemblies and Fullerene-Diamine Adducts towards Practical Nanocarbon-Based Electronic Materials

Abstract Fullerenes are attractive spherical aromatic molecules with good electron acceptor capabilities and good utility as an n-type organic semiconductor. By using a fullerene-amine addition reaction, it was possible to fabricate ultrathin-film assemblies of fullerene on the surface of substrates, which were confirmed by photoelectric conversion applications. Addition reactions between fullerenes and primary aliphatic diamines can also occur to form insoluble adduct particles consisting of fullerenes and diamines. In one example, C60-ethylenediamine adduct particles can be solubilized by addition of alkylacid chloride to residual amino groups of the adducts. Spin-coated or dip-coated thin-films of C60-ethylenediamine adducts from their solutions are useful as n-type organic semiconductors which was confirmed with solar cell application. In this account, the history of the fabrication and application of fullerene thin-film assemblies and fullerene-diamine adducts using the fullerene-amine addition reaction is introduced and summarized from the early studies to more recent developments.

Polythioamides of High Refractive Index by Direct Polymerization of Aliphatic Primary Diamines in the Presence of Elemental Sulfur

Sulfur-containing polymers have renewed widespread attention due to their fascinating properties like high refractive index and semiconducting character. However, examples of direct polymerization involving elemental sulfur are limited. Herein, a new strategy to prepare polythioamide (PTA) by direct polymerization of aliphatic primary diamines in the presence of sulfur is reported. The polymerization of p-xylylenediamine (1) and sulfur at 110 °C in N-methyl-2-pyrrolidinone afforded PTA1 of high Mw and high yield when the feed ratio of [1]:[S] ranged from 1:2 to 1:3. 1H NMR and 13C NMR spectra confirmed that there are three kinds of structural units among the PTA1 chains. Moreover, different diamines including m-xylylenediamine (2), 1,6-hexanediamine (3), ethylenediamine (4), and 1,4-cyclohexanediamine (5) were copolymerized with 1 in the presence of sulfur to obtain PTA copolymers. With an increase in 5 content, the copolymer PTA1/5 with an alternating sequence in the range of 56%–94% was prepared. Solubi...

Chromogenic Signaling of Amine and Diamine with Hyperbranched Polymer Bearing (Trifluoroacetyl)azobenzene Surface Units

Hyperbranched polymer 4 with peripherally appended (trifluoroacetyl) azobenzene reporter groups has been prepared for the first time. The resulting macromolecule is shown to be efficient chromogenic chemosensor for probing aliphatic primary diamines over a given set of amines.

Selective Formation and Structural Properties of Rhombic Dodecahedral [70]Fullerene Microparticles Formed by Reaction with Aliphatic Diamines

We have accomplished the selective formation of rhombic dodecahedral microparticles on the submicrometer to micrometer scale by the reaction of [70]fullerene (C(70)) with primary aliphatic diamines. The morphology of the resultant microparticles was analyzed by scanning electron microscopy, powder X-ray diffraction, and other spectroscopic methods, demonstrating that the resultant particles held a rhombic dodecahedral shape having a simple cubic lattice structure and that primary aliphatic amines were mostly trapped inside the particles through electronic interaction between C(70) and amines. Furthermore, we have discovered interesting structural characteristics in which the incorporated amines could be removed from the C(70) microparticles or exchanged with other primary aliphatic diamines.

Novel hydrogels from diepoxy‐terminated poly(ethylene glycol)s and aliphatic primary diamines: synthesis and equilibrium swelling studies

AbstractNew hydrogels were prepared from diepoxy‐terminated poly(ethylene glycol)s of approximate molecular weights 600, 1000, 2000, and 4000 Da and aliphatic primary diamines with different numbers of carbon atoms (ethylenediamine, 1,4‐diaminobutane, hexamethylenediamine, 1,8‐octanediamine, 1,10‐decanediamine, 1,12‐dodecanediamine), in water or ethanol–water mixture, depending on the amine solubility. The swelling behavior of these gels was tested in distilled water/aqueous solution at constant temperature and the equilibrium swelling degree (ESD) was determined for structurally different hydrogels and under various environmental conditions. It was shown that ESD was influenced by the molecular weight of PEG oligomers, amine/epoxy groups mole ratio, amine chain length, temperature, pH, and concentration of salts present in the swelling medium. Higher ESDs were obtained for either longer‐chain PEGs, non‐stoichiometric amine/epoxy groups ratio, shorter amines, acidic pH, lower temperatures, or in the absence of salts. Copyright © 2009 John Wiley & Sons, Ltd.

Influence of Low‐Molecular‐Weight Diamines in the Direct Imidation of Poly(propylene)‐Grafted Maleic Anhydride by Melt Reaction

AbstractAminated poly(propylene) was prepared by reacting aliphatic primary diamines with maleic‐anhydride‐functionalized poly(propylene) by in situ melt reaction. Around 60–70% of the initial acid groups had reacted to form amide and imide groups as confirmed by the almost complete disappearance of the maleic anhydride peak in FT‐IR spectra. The molecular weight of the diamines had an influence on changes in molecular structure of the PP‐g‐NH2 as a result of secondary reactions such as chain extension and cross‐linking. PP‐g‐NH2 and polycarbonate were pressed into two‐layer films and their adhesion strength was measured. The results showed that PP‐g‐NH2 was a very effective adhesion promoter.magnified image

Ab initio modeling of reaction of primary aliphatic diamines with CS2 in alkaline medium

AbstractSynthesis of bis‐derivatives of dithiocarbamatic structures was carried out with the use of some initial primary diamines in interactiing with carbon bisulfide (CS2) in the alkaline medium. Thus, the observance of various temperature modes results in different reaction products. In the present work, quantum chemical calculation was performed by the density functional theory (DFT) method in approximating B3LYP with the basic set LanL2DZ of modeling systems C2H4(NH2)2 + 2CS2 + 2KOH and C2H4(NH2)2 + CS2 + 2CH3COOH. As a result of the calculations, it has been established that ethylenediamine (EDA) does not interact directly with carbon bisulfide. This interaction occurs in the first case with two molecules of CS2 after the formation of an intermediate particle (chelating complex between bidentate ligands ethylenediamine with two molecules of potassium hydroxide, which promotes a separation of a proton from an amino group) and in the second case with one molecule of CS2 with rising of temperature, corresponding to the cis‐isomer EDA and its complexation with two molecules of an acetic acid. © 2006 Wiley Periodicals, Inc. J Quantum Chem, 2006

Stability, Vigor, and Inherent Versatility of Novel Amino Linker and Spacer Phosphoramidites

AbstractFor Abstract see ChemInform Abstract in Full Text.

Stability, Vigor, and Inherent Versatility of Novel Amino Linker and Spacer Phosphoramidites

Novel amino linker and spacer phosphoramidites were synthesized from methoxyoxalamido (MOX) percursors possessing a secondary hydroxyl, which when phosphitylated endowed stability to the corresponding phosphoramidites. The synthetic strategy is robust, and the chemistry is reactive towards a variety of primary aliphatic diamines and amino alcohols to produce distinctly unique phosphoramidites. The selection of building blocks determines the length and physico-chemical properties of the phosphoramidite tethering arms, and the synthesis can be specifically tailored to suit individual requirement.

Transition metal complexes of 20–22-membered octaazamacrocycles: Synthesis and characterization

A series of binuclear octaazamacrocyclic complexes [M 2L 1X 4]-[M 2L 2X 4] (M  Ni II, Co II and Zn II; X  Cl or NO 3) and [Cu 2L 1]X 4-[Cu 2L 2]X 4 (X  Cl or NO 3) have been synthesized by template condensation reaction of aliphatic primary diamines with 3,6-dimethyl-4,5-diazaocta-3,5-diene-2,7-dione in methanol. The overall geometry and stereochemistry of these complexes have been elucidated by IR, 1H NMR, EPR and electronic spectral studies, and magnetic susceptibility and conductance values. An octahedral geometry around the metal ion is suggested for nickel, cobalt and zinc complexes, whilst a square planar geometry is proposed for copper complexes.

Cross‐linking of poly(methyl methacrylate) by aminolysis of ester functions with diamines

AbstractThe cross‐linking of poly(methyl methacrylate) (PMMA) macromolecules by primary aliphatic diamines was carried out at 413–473 K, above the polymer glass transition temperature. The spherical grains of the suspension‐prepared polymer (0.25–0.8 mm) and the molar ratio to amine above 20 were used. The reaction is characterized by an induction period before the macroscopic gel was observed and by fast network formation. Both phenomena are temperature‐dependent (87± 2 kJ mol−1). The rate of gelation is dependent also on the type of diamine; the shorter induction period of gelation and the higher rate of cross‐linking were observed when amino groups were separated with longer alkyl chains. From the kinetics of amine uptake with PMMA, however, it can be concluded that gel formation is influenced also by the reactivity of amine in the transamination reaction and by the amount of bounded diamine. Aminolysis of PMMA ester groups proceeds from the very beginning of heating of the reaction charge. The polymer cross‐linking prevails when there is more than 60% of diamine attached to PMMA in dependence on the amine type used. © 1995 John Wiley & Sons, Inc.

Homogeneous and Heterogeneous Hydrogenation of Nitriles in a Liquid Phase: Chemical, Mechanistic, and Catalytic Aspects

Abstract Primary or alkylated amines are important chemicals and intermedi-ates. N-Alkylamines are used without further transformation as surface-active agents. Aliphatic primary diamines polymerize with aliphatic diacids to give linear polyamides which have conquered a large place in textile and mechanical industry [11. Mono- and polyamines are produced by catalytic hydrogenation of the corresponding nitriles [2]. In particular this pathway to hexamethylenediamine has been made easier since the synthesis of adi-ponitrile by hydrocyanation of butadiene was made possible [3]. The spec-ifications for production of amines are often very drastic from the point of view of purity, in particular for the diamines used in the textile industry. Thus the stress is put on selectivity of the reaction and most of industrial processes have a yield approaching stoichiometry. It exists few reviews on reduction of nitriles [4, 51, the literature dealing with this type of reaction being mostly published in patents [6–91, and practical knowledge is at the state of “know-how” [lo]. Up to now, two types of processes have been used industrially for the

Novel polyetherurethaneurea elastomers based on α,α,α′,α′‐tetramethyl‐m‐xylenediisocyanate: Synthesis, characterization, processability, and hydrolytic stability

AbstractA series of novel polyetherurethaneurea elastomers based on m‐TMXDI, polyether macrodiols containing 4, 6, 8, or 10 methylene groups between the ether linkages, and aliphatic and aromatic diamines was prepared by two‐step solution polymerization. All the materials were thermally processable at 120–160°C except one that was solvent‐castable. Mechanical properties and hydrolytic stability (at neutral pH) were found to depend on the macrodiol and chain extender. Poly(tetramethylene oxide)‐based polyetherurethaneureas that were chain‐extended with primary aliphatic diamines, other than 1,3‐propanediamine, exhibited significantly better mechanical properties than those chain‐extended with secondary aliphatic or aromatic diamines. The mechanical properties and hydrolytic stability of polyetherurethaneureas containing poly(hexa‐, octa‐, or decamethylene oxide) and 1,6‐hexamethylenediamine were considerably better than those containing 1,2‐ethylenediamine. The hydrolytic stability increased with the increasing C/O ratio of the macrodiol. With poly(hexamethylene oxide)‐based materials, the phase separation between soft and hard domains was higher than that of the other materials as determined by DSC. © 1993 John Wiley & Sons, Inc.

New polymer syntheses—43. Polyamides derived from aryloxy- or arylthioterephthalic acids and aliphatic diamines

The polyamides were synthesized by interfacial condensation from substituted terephthaloylchlorides and aliphatic α,ω-diamines. The following diacids were used: phenoxyterephthalic acid, 4-fluoro, 4-chloro and 4-bromophenoxyterephthalic acid, biphenyloxy- and phenylthioterephthalic acid. DSC- and WAXS-measurements showed that polyamides prepared from trimethylene-4,4-bispiperidine or 1,2-diaminoethane are amorphous. Polyamides derived from higher primary aliphatic diamines are slowly crystallizing semicrystalline materials. Relationships between chemical structure and glasstransition ( T g) or melting temperature ( T m) are discussed. The thermostabilities of several samples were measured in air.

ChemInform Abstract: Reactions of Organylthiochloroacetylenes with Aliphatic Diamines.

AbstractThe alkylthiochloroacetylenes (I) are coupled with the alkylenediamines (II) to give the diazaheterocycles (III).

Synthesis of aliphatic–aromatic polyamides by palladium‐catalyzed polycondensation of aliphatic diamines, aromatic dibromides, and carbon monoxide

AbstractAliphatic–aromatic polyamides were synthesized by the palladium‐catalyzed polycondensation of aliphatic diamines, aromatic dibromides, and carbon monoxide. The effects of variables, such as the kind and amount of base, reaction temperature, and the kind of palladium catalyst were investigated in detail on the reaction of hexamethylenediamine and bis(4‐bromophenyl) ether with carbon monoxide. Inherent viscosities of the polyamides were between 0.13 and 1.21 dL/g and varied markedly with the structure of the diamine component. Solubility of the polyamides decreased with increase of chain length of aliphatic diamines, and the polyamides derived from p‐dibromobenzene was insoluble in organic solvents except for m‐cresol. Polyamides obtained from primary aliphatic diamines began to decompose at 210–250°C in air due to decomposition of the aliphatic chain.

Reactions of organylthiochloroacetylenes with aliphatic diamines

Depending on the length of the hydrocarbon chain of the amine, the reaction of organylthiochloroacetylenes with aliphatic primary diamines gives various nitrogen-containing heterocycles, namely, imidazolines, tetrahydro-1,3-diazepines, and hexahydro-1,3-diazocines.

Chlorine-resistant membrane for reverse osmosis. I. Correlation between chemical structures and chlorine resistance of polyamides

Correlation between the chemical structure of polyamides and the reactivity to hypochlorous acid was investigated to evaluate their chlorine resistance as a membrane material for reverse osmosis. Modes of interaction of polyamides with hypochlorous acid were classified into three; no reaction, reversible chlorination at the amide nitrogen, and irreversible chlorination at the aromatic nucleus. These modes of interaction were dependent upon the amine component of polyamide. Secondary amines such as piperazine and N-methylaniline gave amides which were quite stable against hypochlorous acid. Thus, poly(isophthaloyl piperazine) was most stable among the polyamides investigated in this study. Polyamide derived from aliphatic primary diamines such as polyethyleneisophthalamide gave an N-chlorinated amide, which could be reversibly dechlorinated by the treatment with a reducing agent such as sodium hydrosulfite. Polyamides comprised of aromatic primary diamines such as poly(m-phenyle-neisophthalamide), on the other hand, gave a product with chlorinated m-phenylene nucleus which could not be dechlorinated by a reducing agent.