Action Of Primary Amines Research Articles

Microwave assisted synthesis of ion-imprinted polyacrylonitrile fibre via one-step phosphorylation for selective recovery of Dy(III) from wastewater

The selective recovery of Dy(III) from wastewater is highly desirable. Ion imprinted fibers are considered as attractive adsorbents due to their low flow resistance, high selectivity and ease of recovery. Phosphate groups with strong affinity to rare earth ions are widely used to construct ion imprinted polymers. However, current approaches for introducing phosphate groups into fibers suffer from the low grafting percentage and long reaction time because of the complicated procedures. Herein, a simple one-step phosphorylation method was explored to simultaneously introduce highly active primary amine and phosphate groups into polyacrylonitrile fiber (PANF) under microwave assisted conditions. Additionally, an unique Dy(III) ion-imprinted fibrous adsorbent (IIF-3) was fabricated by cross-linking of the aminated and phosphorylated PANF for selective capture of Dy(III) from wastewater. The advantages of this innovative technology in synthesizing fibrous adsorbent include: short reaction time, high phosphonic content and good mechanical property. In addition, batch sorption tests reveal that the uptake of Dy(III) onto IIF-3 is well described by the Langmuir isotherm and pseudo-second order models. Besides, IIF-3 exhibits a high adsorption selectivity for Dy(III) in multi-component system with different types of interfering ions. Importantly, benefiting from the protective effect of surface imprinting layer, the IIF-3 not only achieves enhanced mechanical property, but also shows satisfied reusability in six times application. This work opens a novel path to prepare phosphorylated ion-imprinted fibers and sheds light on their applications for selective capture of Dy(III) from wastewater.

Distinctive Features of 3‐Acetyl‐ and 3‐Benzoyl‐Isocoumarins’ Interaction with Active Primary Amines

AbstractIsoquinolones and isoquinolines are crucial natural and synthetic heterocyclic compounds exhibiting a range of biological activities. A less explored strategy for the recyclization of isocoumarins to isoquinolones involves the transformation of 1H‐isochromen‐1‐ones with a carbonyl group at position 3 using primary amines. This study presents a straightforward one‐pot protocol for the recyclization of 3‐acetyl‐ and 3‐benzoylisocoumarins into their corresponding isoquinolone derivatives using structurally diverse primary amines. This provides versatile and scalable routes for accessing a variety of 2‐R‐isoquinolin‐1(2H)‐ones. Interestingly, the acyl group also reacted with the hydroxyl group of 2‐aminoethanol, leading to the simultaneous formation of 3,4‐dihydro[1,4]oxazino[4,3‐b]isoquinolin‐6(1H)‐ones alongside lactone recyclization. Moreover, the recyclization process was accompanied by more complex alternative cyclizations, including an oxidative‐reductive stage. For instance, the recyclization of isocoumarins with benzylamine resulted in the formation of isochromeno[3,4‐c]pyrroles, whereas with glycine derivatives, 1,2‐dihydro‐6H‐pyrazino[1,2‐b]isoquinolin‐3,6(4H)‐diones were obtained.

Highly active primary amine ligated Ru(II)-arene complexes as selective catalysts for solvent-free N-alkylation of Anilines

Efficient Ru(II) catalysts with substituted aniline based ligands were synthesized having chemical formula [Ru(η6-p-cymene)Cl2(L1)] [Ru-1] and [Ru(η6-p-cymene)Cl2(L2)] [Ru-2] (where, L1 = 3,5-bis(trifluoromethyl)aniline and L2 = 3,4,5- trimethoxy aniline). The structural features of both the complexes were authenticated by ESI-MS, 1H and 13C NMR, FT-IR, elemental analyses, and single-crystal X-ray diffraction studies. Catalytic performance of both [Ru-1] and [Ru-2] was investigated for conversion of primary amine to secondary amine using alcohols under milder and solvent-free conditions and compared with the reported aniline-based Ru(II)-arene complex [Ru-3]. Among them, [Ru-1] could achieve 100% selectivity towards mono N-alkylated amines with > 99% conversion without formation of any imine derivatives. The results suggested that the lone pair of electrons of benzyl alcohol binds easily to the electron-deficient Ru(II) center of [Ru-1] catalyst making it more effective compared to electron-rich [Ru-2] and [Ru-3] catalysts. The catalytic performance of [Ru-1] demonstrates that it is one of the most active primary amine ligated Ru(II) based catalytic systems for N-alkylation of anilines under milder and solvent-free conditions.

Revisiting the Most Successful United States Food and Drug Administration-approved Anti-obesity Drug Sibutramine sulfate: A Comprehensive Pharmacotherapeutic Review

Introduction: Serotonin (5-HT) and noradrenaline (NA) reuptake inhibitor sibutramine work together. Sibutramine primarily affects food intake and energy expenditure by way of its two pharmacologically active metabolites, primary and secondary amines, which cause significant weight loss. In addition to stimulating thermogenesis and enhancing the physiological process of satiety, it can also increase the efferent sympathetic activity to brown fat that is thermochemically active. Aim: Revisiting the Most Successful United States Food and Drug Administration-approved Anti-obesity Drug Sibutramine sulfate. Methodology: For a duration of 10 years, literature is covered. Results: Clinical studies using sibutramine show a dose-related decrease in body weight, with weight loss up to 11% below the baseline that can last up to 18 months with ongoing therapy. Patients assigned to the sibutramine medication continued to lose weight throughout a 1-year period, reaching 15% below baseline, while the patients receiving the placebo treatment had some weight increase when weight loss is induced with a very low-calorie diet (VLCDL). By lowering the biochemical risk factors for obesity, such as plasma triglycerides, total cholesterol, low-density lipoprotein (LDL) cholesterol, glucose, and insulin, and raising HDL cholesterol, sibutramine enhances metabolic fitness. Conclusion: Sibutramine has been shown to be a beneficial treatment for obese people with moderately high blood pressure, and it has even been shown to reduce blood pressure on average as a result of weight reduction. The potential for misuse that is associated with amphetamine is not present with sibutramine, and in investigations evaluating abuse potential, it is identical to placebo.

The triple-sorbents solid-phase extraction for pharmaceuticals and estrogens determination in wastewater samples

In the presented study, the applicability of four sorbent materials (active carbon, neutral alumina, Primary and Secondary Amines (PSA), and Florosil) applied on top of a polymeric Strata-X column was tested to improve the solid-phase extraction of 15 analytes (pharmaceuticals and estrogens) from water. Deionized water and water fortified by humic acids (representatives of dissolved organic matter) were the tested matrices. The effect of water acidification was tested as well. The values of recovery show that sorbents often have different sorption features towards pharmaceuticals with acidic and basic functional groups. PSA shows sorption towards humic acids, thereby can minimize the matrix effect obtained during final quantification by chromatographic techniques coupled with mass spectrometry. The slight sorption of basic pharmaceuticals to humic acids was found out. Finally, a mixture of PSA and alumina was used, and the validated SPE-GC/MS(SIM) method was applied for raw and treated wastewater. A triple-sorbent solid-phase extraction cause lower matrix effect compared to the previous study. This small innovation in the SPE procedure (without any significant cost enhancement and extension of the duration) can have an impact on the quantification of the pharmaceuticals and estrogens, and improve the reliability of the results.

A Novel and Formaldehyde-Free Preparation Method for Lignin Amine and Its Enhancement for Soy Protein Adhesive

In this work, a novel two-step process to prepare primary lignin amine was developed. The lignin used in this study was obtained from the residue of cellulosic sugar fermentation for bioethanol (referred as “lignin”). The lignin was initially oxidized through Fenton oxidation. The oxidized lignin was further converted to lignin amine by reductive amination. Ammonia was used in the second step leading to give the highly active primary lignin amine. The oxidation and reduction exhibited relatively high yields of 80.0 and 91.2 % respectively. For comparison, lignin was partially depolymerized via mild hydrogenolysis and then the partial depolymerized lignin was also converted to lignin amine using the same method. The obtained lignin amines were characterized in detail using elemental analysis, proton nuclear magnetic resonance (1H NMR), and Fourier transform infrared spectroscopy (FTIR). Further, modification of soy protein adhesive by lignin amine was exemplified in wood bonding, and the results indicated that addition of lignin amine greatly increased water resistance of soy protein adhesives.

Comparative Study of Bifunctional Mononuclear and Dinuclear Amidoiridium Complexes with Chiral C-N Chelating Ligands for the Asymmetric Transfer Hydrogenation of Ketones.

A series of new bifunctional C-N chelating Ir complexes possessing a metal/NH group was synthesized by cyclometalation of optically active primary benzylic amines such as O-silylated (S)-2-amino-2-phenylethanols (1 a and 1 a'), (R)-5-amino-6,7,8,9-tetrahydro-5H-benzocycloheptene (1 b), and (R)-1-phenyl-2,2-dimethylpropylamine (1 c). Although treatment of KOtBu with the amine complexes originating from 1 a and 1 a' afforded amido-bridged dinuclear complexes (3 a and 3 a'), more sterically hindered complexes were solely transformed into the coordinatively unsaturated mononuclear amido complexes (3 b and 3 c), which can serve as real catalyst species in the asymmetric transfer hydrogenation. The structural difference in the C-N chelate framework markedly affected the catalytic performance. Among them, amido complex 3 c showed a pronounced ability to catalyze the transfer hydrogenation of acetophenone in 2-propanol, even at a low temperature of -30 °C. A hydridoiridium complex (4 c) was also identified in the reaction of 3 c in 2-propanol, which provides mechanistic insights into the enantiodiscriminating step in the hydrogen transfer to prochiral ketones.

A Novel Hybrid Polymer Network for Efficient Anticorrosive and Antibacterial Coatings

By in situ simultaneous polymerization of dopamine and hydrolytic polycondensation of 3-aminopropyltriethoxysilane in an aqueous solution, a novel hybrid polymer network coating on stainless steel was formed. The polydopamine and silica hybrid polymer (PDSHP) adhered strongly on the surface of stainless steel. The PDSHP film provides active catechol and primary amine groups. Branched polyethylenimine was grafted based on the PDSHP film. The structure and morphology of the multilayer coating were characterized by attenuated total reflectance Fourier transform infrared spectroscopy reflectance, X-ray photoelectron spectroscopy, and atomic force microscopy and scanning electron microscopy images. The coatings on the stainless steel substrates exhibited anticorrosion of seawater. By making use of the primary amine groups on the multilayer coating, a biocidal agent 3-chloro-2- hydroxypropyltrimethylammonium chloride (CHPTAC) was grafted. The grafted CHPTAC was effective in killing bacteria, extending the multilayer polymer coating with biocidal functionality.

Pyrylium Salts as Reactive Matrices for MALDI-MS Imaging of Biologically Active Primary Amines.

Many neuroactive substances, including endogenous biomolecules, environmental compounds, and pharmaceuticals possess primary amine functional groups. Among these are catecholamine neurotransmitters (e.g., dopamine), many substituted phenethylamines (e.g., amphetamine), as well as amino acids and neuropeptides. In most cases, mass spectrometric (ESI and MALDI) analyses of trace amounts of such compounds are challenging because of their poor ionization properties. We present a method for chemical derivatization of primary amines by reaction with pyrylium salts that facilitates their detection by MALDI-MS and enables the imaging of primary amines in brain tissue sections. A screen of pyrylium salts revealed that the 2,4-diphenyl-pyranylium ion efficiently derivatizes primary amines and can be used as a reactive MALDI-MS matrix that induces both derivatization and desorption. MALDI-MS imaging with such matrix was used to map the localization of dopamine and amphetamine in brain tissue sections and to quantitatively map the distribution of the neurotoxin β-N-methylamino-L-alanine.

ChemInform Abstract: A Novel Example of Double 6‐exo‐trig Heterocyclization: Nitrile Conversion to New Anticancer Active (HeLa Cells) Primary Amine Ionic Liquids.

AbstractDerivatives (II) are ionic liquids at room temperature.

Efficacy of Preserving Sea Foods Using <i>Marine Lactobacillus</i>

Scombroid food poisoning is a food borne illness that results from eating spoiled (decayed) fish. Histamine is the causative agent of scombroid poisoning, a food borne chemical intoxication. Histamine is one of the main biogenic amines and it is heterocyclic and biologically active primary amine, formed post-mortem in the muscles of scombroid and non-scombroid fish. The present study was carried out to isolate histamine-producing bacteria from a local fish and to test antibacterial activity of mangrove isolates of Lactobacillus species against the histamine producing bacteria. Fresh tuna fish (Euthinus affinis) obtained from Parangipettai coast and they were divided in to three groups. One group of the fish samples were stored directly and another two group of the fish samples were dipped in cold distilled water containing bacteriocin of Lactobacillus sp. and partially purified bacteriocin (10 ml, 1% v/v) respectively. The fish samples, after treatment were stored at 5, 15, 20 and 25 0C for the period of 24, 48, 72 and 96 h, respectively. Histamine quantification was performed at an interval of 24 h for four days. According to the results obtained it was proved that mangrove isolates of Lactobacillus species having high antimicrobial activity against histamine-producing bacteria which is responsible for spoilage of sea foods.

Correction to “Stereospecific Substitution of Allylic Alcohols To Give Optically Active Primary Allylic Amines: Unique Reactivity of a (P,alkene)Ir Complex Modulated by Iodide”

Correction to “Stereospecific Substitution of Allylic Alcohols To Give Optically Active Primary Allylic Amines: Unique Reactivity of a (P,alkene)Ir Complex Modulated by Iodide”

Mannich reaction in the synthesis of N,S-containing heterocycles. 16.*Synthesis of derivatives of tetra-hydropyrido[1,2-a][1,3,5]triazine and 5,6,12,13-tetra-hydro-1H,8H-dipyrido[1,2-a:1',2'-e][1,3,5,7]tetrazocine

The aminomethylation of 6-amino-4-aryl-2-thioxo-1,2-dihydropyridine-3,5-dicarbonitriles by the action of primary amines and an excess of formaldehyde under conditions of base catalysis was studied. It was found that the structure and yields of the products depend largely on the structure of the initial amine and also on the ratio of the reagents and reaction conditions. In the case of alkyl- or arylalkylamines, 8-aryl-3-alkyl(arylalkyl)-6-thioxo-1,3,4,6-tetrahydro-2H-pyrido[1,2-a][1,3,5]triazine-7,9-dicarbonitriles were obtained, whereas when aromatic amines were used 3,10-diaryl-1,8-dithioxo-5,6,12,13-tetrahydro-1H,8H-dipyrido[1,2-a:1′,2′-e][1,3,5,7]tetrazocine-2,4,9,11-tetracarbonitriles or their mixtures with the above-mentioned pyrido[1,2-a][1,3,5]triazines were obtained. Dipyrido[1,2-a:1′2′-e]-[1,3,5,7]tetrazocine derivatives were also synthesized by direct condensation of 6-amino-4-aryl-2-thioxo-1,2-dihydro-pyridine-3,5-dicarbonitriles with formaldehyde.

MANNICH REACTION IN THE SYNTHESIS OF N,S-CONTAINING HETEROCYCLES. 16. SYNTHESIS OF DERIVATIVES OF TETRAHYDROPYRIDO[1,2- a ][1,3,5]TRIAZINE AND 5,6,12,13-TETRAHYDRO-1 H ,8 H -DIPYRIDO[1,2- a :1',2'- e ][1,3,5,7]TETRAZOCINE

The aminomethylation of 6-amino-4-aryl-2-thioxo-1,2-dihydropyridine-3,5-dicarbonitriles by the action of primary amines and an excess of formaldehyde under conditions of base catalysis was studied. It was found that the structure and yields of the products depend largely on the structure of the initial amine and also on the ratio of the reagents and reaction conditions. In the case of alkyl- or arylalkylamines, 8-aryl-3-alkyl(arylalkyl)-6-thioxo-1,3,4,6-tetrahydro-2 H -pyrido[1,2- a ][1,3,5]triazine-7,9-dicarbonitriles were obtained, whereas when aromatic amines were used 3,10-diaryl-1,8-dithioxo-5,6,12,13-tetrahydro-1 H ,8 H -dipyrido[1,2- a :1′,2′- e ][1,3,5,7]tetrazocine-2,4,9,11-tetracarbonitriles or their mixtures with the above-mentioned pyrido[1,2- a ][1,3,5]triazines were obtained. Dipyrido[1,2- a :1′2′- e ]-[1,3,5,7]tetrazocine derivatives were also synthesized by direct condensation of 6-amino-4-aryl-2-thioxo-1,2-dihydropyridine-3,5-dicarbonitriles with formaldehyde. Authors: V. V. Dotsenko, S. Yu. Suikov, T. M. Pekhtereva, and S. G. Krivokolysko English Translation in Chemistry of Heterocyclic Compounds , 2013, 49 (7), pp 1009-1023 http://link.springer.com/article/10.1007/s10593-013-1339-5

The Mannich reaction in the synthesis of N,S-containing heterocycles 12. First example of aminomethylation involving 2-thioxonicotinamide derivative: synthesis of 3,5,7,11-tetraazatricyclo[7.3.1.02,7]tridec-2-ene-9-carboxamides

Piperidinium 6-amino-5-cyano-3-N-(4-methylphenyl)carbamoyl-4-phenyl-1,4-dihydro-pyridine-2-thiolate upon the action of primary amines and excess formaldehyde undergoes aminomethylation to form 3,5,7,11-tetraazatricyclo[7.3.1.02,7]tridec-2-ene-9-carboxamides in 36–52% yields.

ChemInform Abstract: Asymmetric Inverse‐Electron‐Demand Hetero‐Diels—Alder Reaction of Six‐Membered Cyclic Ketones: An Enamine/Metal Lewis Acid Bifunctional Approach.

AbstractThe reaction of cyclic ketones with β,γ‐unsaturated α‐ketoesters under catalysis of yttrium triflate and optically active primary amine PYR affords benzopyran, pyranopyran, and pyranothiopyran derivatives in a highly stereo‐ and chemoselective manner.

Synthesis, antifungal activity and semi-empirical AM1-MO calculations of some new 4-oxo-4H-chromene derivatives

Some new antifungal agents have been prepared through reaction of 4-oxo-4 H -chromene-3-carbaldehydes ( 1a , b ) with some active primary amines ( 2a - e ) and amides/thioamides ( 6a - d ) in different conditions. Structures of the products were established on the basis of elemental analysis, IR, 1 H NMR, mass spectra and semi-empirical AM1-MO calculations.

ChemInform Abstract: Stereospecific Substitution of Allylic Alcohols to Give Optically Active Primary Allylic Amines: Unique Reactivity of a (P,alkene)Ir Complex Modulated by Iodide.

AbstractThe reaction applies sulfamic acid as an aminating agent, Ir‐phosphoramidite catalyst, generated in situ, and LiI as an additive, the latter being crucial for the high optical purity of the isolated product.

Stereospecific Substitution of Allylic Alcohols To Give Optically Active Primary Allylic Amines: Unique Reactivity of a (P,alkene)Ir Complex Modulated by Iodide

A stereospecific allylic amination of unactivated secondary (secondary)-allylic alcohols is reported. The primary (primary)-allylic amine can be isolated directly or protected in situ. Spectroscopic studies have shed light on the structure of the catalytically active Ir x (P,olefin)2I complex.

The Mannich reaction in the synthesis of N,S-containing heterocycles 10. Recyclization of stable cyclic michael adducts, N-methylmorpholinium 6-R-6-hydroxy-1,4,5,6-tetrahydropyridine-2-thiolates, to pyrimido[4,3-b][1,3,5]thiadiazines under conditions of aminomethylation reaction

5-Substituted N-methylmorpholinium 4-aryl-6-R-3-cyano-6-hydroxy-1,4,5,6-tetrahydro-pyridine-2-thiolates upon the action of primary amines and HCHO in ethanol undergo recyclization to 3,7-disubstituted 8-aryl-3,4,7,8-tetrahydro-2H,6H-pyrimido[4,3-b][1,3,5]thiadiazine-9-carbonitriles in low yields (5–28%). The latter were also obtained by alternative method, viz., by sequential condensation of cyanothioacetamide with aromatic aldehydes, primary amines, and HCHO.