Structural and Dynamic Behaviour of Heterocycles Derived from Ethylenediamines with Formaldehyde: 1,3,5-Triazinanes and Bis(imidazolidinyl)methanes

Formaldehyde is a simple chemical compound that is used as a building block in obtaining a wide range of products. The versatility of formaldehyde in chemical synthesis becomes evident when it is reacted with N-alkylethylenediamines. Therefore, this paper reports the structure and reactivity of a series of compounds derived from easily accessible molecules, such as formaldehyde, sodium hydrosulphide, and N-alkylethylenediamines. The 1,3,5-triazines (1a-1d) and bis(3-alkyl-imidazolidin-1-yl)methanes (2a-2d) were obtained by simple reaction conditions. Additionally, different proportions of sodium hydrosulphide and formaldehyde were used with N-benzylamine to obtain N-benzyltriazinane (3), N-benzylthiadiazinane (4) and N-benzyldithiazinane (5). All these compounds were characterized by analytical, spectroscopic, and spectrometric techniques, such as melting point, solubility, one-dimensional and two-dimensional nuclear magnetic resonance (13C, 1H, 15N, COSY, HETCOR, NOESY, COLOC), elemental analysis, high- and low-resolution mass spectrometry, among others. The structures of compounds 4 and 5 were obtained by single-crystal X-ray diffraction. The results show that small variations in the stoichiometry and the reaction conditions significantly influence the products obtained.

[1]  Xiang Liu,et al.  Construction of Diverse N-Heterocycles by Formal (3 + 3) Cycloaddition of Naphthol/Thionaphthol/Naphthylamine and 1,3,5-Triazinanes. , 2022, The Journal of organic chemistry.

[2]  Xiang Liu,et al.  Lewis Acid-Catalyzed Synthesis of Polysubstituted Furans from Conjugated Ene-yne-ketones and 1,3,5-Triazinanes. , 2022, The Journal of organic chemistry.

[3]  Zhongxue Fang,et al.  Metal-free [2 + 1 + 3] Cycloaddition of Trifluoroacetaldehyde N-Sulfonylhydrazones with Hexahydro-1,3,5-triazines Leading to Trifluoromethylated 2,3,4,5-Tetrahydro-1,2,4-triazines. , 2022, The Journal of organic chemistry.

[4]  V. Dokichev,et al.  Synthesis and Cytotoxic Activity of 1,3,5-Triazinane Derivatives Based on Primary Amines and Amino Acids Esters , 2022, Russian Journal of General Chemistry.

[5]  Pedro Montes-Tolentino,et al.  Tin complexes derived from nitrogen-based 1,3,5-heterocyclohexanes bearing 2-hydroxypropan-1-yl, 2-diphenylphosphitepropan-1-yl and 2-diphenylphosphinepropan-1-yl as pendant N-substituents , 2022, Journal of Molecular Structure.

[6]  Pedro Montes-Tolentino,et al.  New 1,3,5-heterocyclohexanes bearing pendant phosphorus groups. Structure and N→P pnicogen interactions. , 2021, Journal of Molecular Structure.

[7]  Zhixing Cao,et al.  Formal [2+2+2] Cycloaddition Reaction of 1,3,5‐Triazinanes： Facile Approaches to Tetrahydropyrimidines , 2021, European Journal of Organic Chemistry.

[8]  Yuyang Jiang,et al.  Synthesis of α-Amino Tertiary Alkylperoxides by Lewis Acid Catalyzed Peroxidation of 1,3,5-Triazines. , 2021, Chemistry, an Asian journal.

[9]  Zhiyong Wang,et al.  Base-induced inverse-electron-demand aza-Diels-Alder reaction of azoalkenes and 1,3,5-triazinanes: Facile approaches to tetrahydro-1,2,4-triazines , 2021, Tetrahedron Letters.

[10]  A. Ibragimov,et al.  Sodium Sulfide in the Synthesis of N-Alkyl-1,3,5-dithiazinanes and 1,3,5-Thiadiazinanes , 2021, Russian Journal of General Chemistry.

[11]  M. G. da Rocha Pitta,et al.  Imidazolidine Derivatives in Cancer Research: What is known? , 2021, Anti-cancer agents in medicinal chemistry.

[12]  Huan Luo,et al.  Rhodium(II)‐Catalyzed [4+2] Annulation of Ester‐Tethered 1‐Sulfonyl‐1,2,3‐Triazoles and Hexahydro‐1,3,5‐Triazines , 2021 .

[13]  Zu-liang Liu,et al.  Effect of 2,4,6‐Triamino‐3,5‐Dinitropyridine‐1‐Oxide on the Properties of 1,3,5‐Trinitro‐1,3,5‐Triazinane‐based PBX Explosives , 2021 .

[14]  E. Denis,et al.  Vapor Pressures of RDX and HMX Explosives Measured at and Near Room Temperature: 1,3,5-Trinitro-1,3,5-triazinane and 1,3,5,7-Tetranitro-1,3,5,7-tetrazocane. , 2021, The journal of physical chemistry. A.

[15]  W. Xu,et al.  Synthesis of Hydrobenzoimidazoles from para ‐Quinamines and 1,3,5‐Triazinanes via a Formal [3+2] Annulation Reaction , 2020 .

[16]  D. S. Chauhan,et al.  Influence of hydrodynamic condition on 1,3,5-tris(4-methoxyphenyl)-1,3,5-triazinane as a novel corrosion inhibitor formulation for oil and gas industry , 2020 .

[17]  H. Zhai,et al.  Synthesis of 1,2,3,4‐Tetrahydrobenzofuro[3,2‐ d ]pyrimidines via [4+2] Annulation Reaction of 1,3,5‐Triazinanes and Aurone‐Derived α,β‐Unsaturated Imines , 2020 .

[18]  W. Xiao,et al.  Recent Advances of 1,3,5-Triazinanes in Aminomethylation and Cycloaddition Reactions , 2020, Synthesis.

[19]  W. Xiao,et al.  Inverse-electron-demand [4+2] cycloaddition of photogenerated aza-ortho-quinone methides with 1,3,5-triazinanes: access to perfluoroalkylated tetrahydroquinazolines. , 2020, Chemical communications.

[20]  Jun Xuan,et al.  [4+2]‐Cycloaddition of para ‐Quinone Methides with Hexahydro‐1,3,5‐Triazines: Access to 1,3‐Benzoxazine Derivatives , 2020 .

[21]  S. P. Swain,et al.  Imidazolidinones and Imidazolidine‐2,4‐diones as Antiviral Agents , 2019, ChemMedChem.

[22]  Haibo Yu,et al.  Towards an Accurate Prediction of Nitrogen Chemical Shifts by Density Functional Theory and Gauge‐Including Atomic Orbital , 2018, Advanced Theory and Simulations.

[23]  K. R. Babu,et al.  Growth and characterization of barium complex of 1,3,5-triazinane-2,4,6-trione in gel: a corrosion inhibiting material , 2018 .

[24]  Q. Kang,et al.  Enantioselective Mannich Reaction Employing 1,3,5‐Triaryl‐1,3,5‐triazinanes Catalyzed by Chiral‐at‐Metal Rhodium Complexes , 2017 .

[25]  P. Schreiner,et al.  Mild Aliphatic and Benzylic Hydrocarbon C-H Bond Chlorination Using Trichloroisocyanuric Acid. , 2017, The Journal of organic chemistry.

[26]  A. Vela,et al.  Theoretical approach to the conformational analyses of dithiazinane, thiadiazinane and triazinane, their N-borane adducts and N-H cations , 2016 .

[27]  R. Contreras,et al.  New N-[2-chloropropyl]-heterocyclohexanes. NMR long range shielding effects of chlorine substituent. Use of BH3 as freezing conformational agent , 2016 .

[28]  N. Amiano,et al.  New Green Synthesis and Antineoplastic Activity of Bis (3-Arylimidazolidinyl-1) Methanes , 2013 .

[29]  S. Maity,et al.  Trichloroisocyanuric acid (TCCA): an efficient green reagent for activation of thioglycosides toward hydrolysis. , 2013, Carbohydrate research.

[30]  N. Campillo,et al.  Artificial neural networks based on CODES descriptors in pharmacology: identification of novel trypanocidal drugs against Chagas disease. , 2013, Current computer-aided drug design.

[31]  V. V. Stankevich,et al.  Anticorrosion properties of products of N-(2-Vinyloxyethyl)-1,2-ethylenediamine condensation with carbonyl compounds , 2010 .

[32]  N. Mitzel,et al.  Two diamino-substituted lithiocarbanions in one molecule. , 2009, Chemical communications.

[33]  O. G. Nabiev,et al.  Derivatives of N-alkyl(aryl)-1,2(1,3)-diazacycloalkanes. Antimicrobial properties , 2009 .

[34]  Weilan Xue,et al.  Kinetics of Cyanuric Chloride Hydrolysis in Aqueous Solution , 2008 .

[35]  H. Cerecetto,et al.  Imidazolidines as new anti-Trypanosoma cruzi agents: biological evaluation and structure-activity relationships. , 2008, Bioorganic & medicinal chemistry.

[36]  Evangelina Repetto,et al.  Synthesis, spectroscopic and biological properties of bis(3-arylimidazolidinyl-1)methanes. A novel family of antimicrobial agents. , 2005, European journal of medicinal chemistry.

[37]  R. Contreras,et al.  2-(1,3,5-Dithiazinan-5-yl)ethanol Heterocycles, Structure and Reactivity. , 2005 .

[38]  J. Gálvez-Ruíz,et al.  2-(1,3,5-Dithiazinan-5-yl)ethanol heterocycles, structure and reactivity , 2004 .

[39]  E. Stevens,et al.  Synthesis, Lipophilicity and Structure of 2,5‐Disubstituted 1,3,5‐Dithiazine Derivatives. , 2004 .

[40]  R. Salas-Coronado,et al.  3(1,3-Heterazolidin-3-yl-methyl)-1,3-oxazolidines and their reduction with borane -THF , 2003 .

[41]  E. Stevens,et al.  Synthesis, lipophilicity and structure of 2,5-disubstituted 1, 3, 5-dithiazine derivatives , 2003 .

[42]  G. Kickelbick,et al.  Synthesis of Hexadentate Hexahydro-1,3,5-triazine-Based Ligands and their Copper(I) Complexes , 2002 .

[43]  G. Kickelbick,et al.  A mixed copper(I)/copper(II) complex coordinated by a multidentate amidato ligand , 2002 .

[44]  N. Peerzada,et al.  Benzotriazole Mediated Synthesis of Some 5-Alkyl-Dihydro-4H-1,3,5-Dithiazines , 2000 .

[45]  Pinhua Li,et al.  Electrochemical formal [3+2] cycloaddition of azobenzenes with hexahydro-1,3,5-triazines , 2022, Organic Chemistry Frontiers.

[46]  Qiong Tang,et al.  Enantioselective formal [2+2+2] cycloaddition of 1,3,5-triazinanes to construct tetrahydropyrimidin-4-one derivatives , 2021, Chemical Communications.

[47]  P. Puthiaraj,et al.  Covalent triazine polymers using a cyanuric chloride precursor via Friedel–Crafts reaction for CO2 adsorption/separation , 2016 .

[48]  G. Romeiro,et al.  Synthesis and Applications of 1,3,5-Triazinanes , 2013 .

[49]  R. Contreras,et al.  New dithiazinanes and bis‐dithiazinanes‐bearing pendant ethylamines: Structure and reactivity , 2011 .

[50]  M. Witanowski,et al.  Nitrogen Chemical Shifts in Organic Compounds , 1973 .