Studies on amidation and imidization processes of amine salts of aromatic tetracarboxylic acids and diamine

The amidation (A) and imidization (I) processes of several amine salts prepared from aromatic tetracarboxylic acids and diamine have been studied by means of thermal analysis (TG, DTA and DSC) and IR spectroscopy. The degrees of imidization (cyclization) of these salts, as estimated via thermal analysis under programmed heating, are 87–93%. The activation energies of these A–I processes, as determined from DSC curves, are 125 and 250 kJ mole⁻¹. From the thermal analysis curves and infrared absorption spectra, it appears that the amidation and imidization processes are superimposed, and the imidization process occurs before the completion of the amidation.     

Vinamidinium salts of N-substituted aminoacetic acids

Formylation of N-phthaloylglycine with the POCl3-DMF system afforded N,N,N′, N′-tetramethyl-2-(N-phthaloyl)vinamidinium perchlorate (2). X-ray diffraction study showed that molecule 2 is planar and contains two equivalent nitrogen atoms in the three-carbon vinamidinium fragment. Salt 2 undergoes transamination with primary aromatic amines to give the corresponding bis-azomethines. The reactions with hydrazines produce substituted 4-aminopyrazoles. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 5, pp. 832–835, May, 2006.     

Studies on polyimide imidization in far‐infrared radiation

In this paper, the monomers 4,4′‐oxydiphthalic anhydride (ODPA), 3,3′,4,4′‐biphenyl dianhydride (BPDA), 3,4′‐oxidianiline (3,4′‐ODA), and 4,4′‐oxidianiline (4,4′‐ODA) were selected to synthesize polyimides (PI) or copolyimides (co‐PI) in N,N‐dimethyl acetamide (DMAc) by two‐step method. To control the PI molecular weight (MW), phthalic anhydride (PA) was used as the end‐capping reagent. The effect of far‐infrared radiation (FIR) on PI imidization was investigated by Fourier transform infrared spectroscopy (FTIR). Some factors affecting imidization process in FIR were discussed, including PI imidization time and temperature, molecular structure, designed number average molecular weight, crystalline, imidization procedure, film thickness, polyamide acid (PAA) solid content, and so forth. The PI imidization process in FIR will be affected by all these factors. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 3621–3627, 2005     

Effect of curing accelerators on thermal imidization of polyamic acids at low temperature

The effect of new additives on the thermal conversion of a range of polyamic acids to polyimides at temperatures lower than 100°C was investigated using infrared spectroscopy. Additives such as m-hydroxybenzoic acid, p-hydroxyphenylacetic acid, and p-hydroxybenzenesulfonic acid were found to be highly effective as curing catalysts or accelerators. The degree of imidization of polyamic acids in the presence of additives increased with an increase in the reaction temperature, and complete imidization was achieved at 140–200°C. The reaction was characterized by a rapid rate that slowed with time. © 1996 John Wiley & Sons, Inc.     

Convenient preparation of O-linked polymer-bound N-substituted hydroxylamines, intermediates for synthesis of N-substituted hydroxamic acids

[reaction: see text] An efficient procedure for preparation of O-linked polymer-bound N-substituted hydroxylamines by reduction of resin-bound oximes with borane.pyridine complex in the presence of dichloroacetic acid is reported. Other reducing systems commonly used for imine or oxime reduction were ineffective, including borane.pyridine in the presence of acetic acid. Oximes derived from a variety of aromatic and aliphatic aldehydes and ketones were successfully reduced. The N-substituted products were acylated and cleaved from resin to afford N-substituted hydroxamic acids.     

Heteropoly acids of the Keggin type with N-substituted β-amminoethylphosphonic acids as coordinate center

Organophosphorus-heteropolytungstic acids of 1: 12 of P/W ratio, with N-substituted 2-amminoethylphosphonic acids R₂R’N⁺CH₂CH₂PO₃H⁻ (R = R’ = H; R′ = Me, R’ = H; R = R’ = Me; R = H, R ’ = Me₂CH; R′ = H, R’’ = CH₃(CH₂)₂CH₂) as coordinate centers were prepared, and characterized by means of elemental analysis, IR, UV spectroscopy, TG and DSC thermal analysis. The results indicate that these organophosphorous-HPAs possess Keggin type structure, and their stoichiometric formulation is R₂R’N⁺CH₂CH₂PO₃H⁻. W₁₂O₃₆.nH₂O. The organic side chain with the ammino-group R₂R’N⁺CH₂CH₂ ⁻ and the phosphono-group-PO₃H^- participate altogether in the formation of the primary structure of the heteropoly anion. In other words, the entirety of each compound R₂R ’N⁺CH₂CH₂PO₃H⁻ is as the core or coordinate center of the heteropoly anions. The number of crystal water in the HPA was affected obviously by the N-substituents of the organophosphonic acids.     

Synthesis and some conversions of N-substituted benzimidazole-2-sulfonic acids

A series of N-substituted benzimidazole-2-sulfonic acids was synthesized in good yield by the N-alkylation of benzimidazole-2-sulfonic acids by alkylation with simple and functionalized alkylating agents under mild conditions. The corresponding N-substituted benzimidazolones and also primary, secondary, and tertiary amines were obtained by the action on the obtained compounds of alkali, ammonia, ammonium acetate, and amines. __________ Translated from Khimiya Geterotsiklicheskikh, No. 4, pp. 528–534.     

Azides of N-substituted aziridine-2-carboxylic acids. Reaction with methyl esters of amino acids

The corresponding azide was obtained by nitrosation of 1-benzylaziridine-2-carboxylic acid hydrazide. Reaction of the azide with methyl esters of amino acids gave N-(1-benzyl-2-aziridinylcarbonyl)-substituted methyl esters of amino acids.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1350–1352, October, 1980.     

Absolute configuration of diastereomeric derivatives of N-substituted aziridine-2-carboxylic acids

Individual diastereomers of a number of anilides of N-substituted aziridine-2-carboxylic acids have been obtained. Conclusions regarding the spatial structure of the compounds indicated have been drawn on the basis of the ¹H NMR, ¹⁵N NMR, and CD spectra.Report 37 of the series entitled Asymmetric nonbridging nitrogen. For report 36 see [1].Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 10, pp. 1343–1348, October, 1984.     

Studies on the stability of dithiocarbamic acids

The influence of the substituent on the nitrogen atom with respect to the rate and pattern of decomposition of N,N-disubstituted dithiocarbamie acids has been studied. The rates of decomposition with respect to such variables as pH, temperature (activation parameters) and heavy water medium (solvent isotope effect), have been determined, and a mechanism to accommodate the observed results has been proposed.     

Synthesis of N-substituted amides by the Ritter reaction with heteropoly acids as catalysts

Reactions of a number of nitriles with camphene in the presence of the heteropoly acids H₃PW₁₂O₄₀, H₇PMo₁₂O₄₂, and H₄SiW₁₂O₄₀ as catalysts were studied. In all cases, N-substituted amides were obtained in sufficiently high yields. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 2, pp. 374–376, February, 2006.     

Reaction of N-substituted 2,5-dialkyl-1,4-benzoquinone imines with arenesulfinic acids

Reactions of N-aroyl-, N-arylsulfonyl-, and N-(N-arylsulfonylbenzimidoyl)-2,5-dialkyl-1,4-benzoquinone imines with sodium arenesulfinates in acetic acid gave the corresponding 1,4-, 6,1-, and 1,6-addition products. Variation of the size and donor power of substituents in positions 2 and 5 of the quinoid ring almost does not affect the ratio of the addition products, which is determined mainly by the nature of substituent on the nitrogen atom.     

Biocatalytic enantioselective synthesis of N-substituted aspartic acids by aspartate ammonia lyase

The gene encoding aspartate ammonia lyase (aspB) from Bacillus sp. YM55-1 has been cloned and overexpressed, and the recombinant enzyme containing a C-terminal His(6) tag has been purified to homogeneity and subjected to kinetic characterization. Kinetic studies have shown that the His(6) tag does not affect AspB activity. The enzyme processes L-aspartic acid, but not D-aspartic acid, with a K(m) of approximately 15 mM and a k(cat) of approximately 40 s(-1). By using this recombinant enzyme in the reverse reaction, a set of four N-substituted aspartic acids were prepared by the Michael addition of hydroxylamine, hydrazine, methoxylamine, and methylamine to fumarate. Both hydroxylamine and hydrazine were found to be excellent substrates for AspB. The k(cat) values are comparable to those observed for the AspB-catalyzed addition of ammonia to fumarate ( approximately 90 s(-1)), whereas the K(m) values are only slightly higher. The products of the enzyme-catalyzed addition of hydrazine, methoxylamine, and methylamine to fumarate were isolated and characterized by NMR spectroscopy and HPLC analysis, which revealed that AspB catalyzes all the additions with excellent enantioselectivity (>97 % ee). Its broad nucleophile specificity and high catalytic activity make AspB an attractive enzyme for the enantioselective synthesis of N-substituted aspartic acids, which are interesting building blocks for peptide and pharmaceutical synthesis as well as for peptidomimetics.     

Investigations of imidization of polypyromellitamido acids and thermal degradation of polypyromellitimides by mass spectrometric thermal analysis

Processes occurring when samples of fibers of polypyromellitamido acids and polypyromellitimides based on them are heated in vacuum have been investigated by mass spectrometric thermal analysis (MTA) over a wide temperature range.A combination of MTA methods with a comparative thermal analysis of polyimides and model compounds permits conclusions to be made concerning the main reactions responsible for the thermal stability and the start of degradation of a number of polyimide structures.