294-80-4Relevant articles and documents
The synthesis of 1,2-bis(1,5,9-triazacyclododecyl)ethane: A showcase for the importance of the linker length within bis(alkylating) reagents
Medina-Molner, Alfredo,Blacque, Olivier,Spingler, Bernhard
, p. 4829 - 4831 (2007)
(Chemical Equation Presented) The synthesis of 1,2-bis(1,5,9- triazacyclododecyl)ethane (1) showcases how different bis(alkylating) reagents change the reaction from an intra- to an intermolecular pathway. The isolation of the intermediate hexahydro-3a,6a-ethano-1H,4H,7H,9bH-9a-aza-3a,6a- diazoniaphenalene-3a,6a-diium (2) explained why initially the synthesis of 1 was not possible. Both isomers of 2 were found in solution. DFT calculations revealed that isomer 2a is 4.6 kcal/mol lower in energy than 2b. Synthesis of 1 was finally achieved by using oxalyl chloride.
Strongly basic macrocyclic triamines, 1,5,9-triazacyclododecanes for solvent extraction of gold(I) cyanide
Choi, Heung-Jin,Bae, Yoon-Kyung,Kang, Seok-Chan,Sil Park, Yeon,Won Park, Joon,Kim, Woong-Il,Bell, Thomas W
, p. 9385 - 9389 (2002)
Solvent extraction of gold(I) dicyanide anion from alkaline gold(I) cyanide solution using unusually basic amine extractants was conducted. 1,5,9-Triazacyclododecane (4) is known as an unusually basic macrocyclic amine having pKa=12.3-12.7, and is thus a good candidate as a basic amine extractant. Three lipophilic derivatives of 4 expected to stay in the organic phase during gold solvent extraction were synthesized. N-Dodecyl-1,5,9-triazacyclododecane (3) was prepared from 1,5,9-triazacyclododecane-2,4-dione (1) by N-alkylation with n-dodecyl iodide and then reduction with BH3-THF. N,N′-Didodecyl-1,5,9-triazacyclododecane (5) and N,N′,N′′-tridodecyl-1,5,9-triazacyclododecane (6) were efficiently synthesized by selective di-alkylation of 4 with n-dodecyl iodide, and by reductive alkylation of 4 with n-dodecanal, respectively. The extractants 3 and 6 showed pH50=10.5, which is the minimum value required for practical application.
SYNTHESIS AND COPPPER(I) COMPLEXES OF A SERIES OF 9- TO 13-MEMBERED N3 MACROCYCLES
Briellmann, Markus,Kaderli, Susan,Meyer, Charles J.,Zuberbuehler, Andreas D.
, p. 680 - 689 (1987)
Eight cyclic triamines with ring sizes between 9 and 13 were synthesized by the p-toluenesulfonate method.The open-chain triamines bis(2-aminoethyl)amine (dien) and bis(3-aminopropyl)amine (diprop) were used as starting materials.In some cases, the corresponding dimeric cyclic hexaamines have been isolated and characterized as major by-products.The complexation of Cu(I) by the triamines has been studied potenciometrically in CH3CN/H2O.All ligands L form ternary complexes .The corresponding association constants vary between 1E11 and 1E7, decreasing with increasing ring size.In addition , complexes yLH>(2+), y= 1 or 2, are found as less important species with maximum concentrations of 7 to 50 percent.
Synthesis of 24-, 26-, 32- and 36-membered Macrocyclic Polyamines via a (2+2) Cyclization Process
Panetta-Le Mer, V.,Yaouanc, J. J.,Handel, H.
, p. 2337 - 2340 (1994)
At high concentration, N-pertriflated polyamines and ω,ω'-dihalogenoalkanes react to yield large polyazamacrocycles according to a (2+2) cyclization mode.
Computational and experimental studies on the effect of conformational flexibility on bonding and photophysics of a triaza-macrocycle tripod
Verma, Rohini,Baral, Minati,Kanungo
, p. 253 - 273 (2021/06/30)
The effect of conformational flexibility on coordination and bonding of a chelator, [12N3Me5Ox], on the macrocyclic ring 1,5,9-tris(-5-methylene)-1,5,9-triazadodecane and its lanthanide complexes is depicted by synthesis, characterization, and theoretical techniques. The chelator and its complexes were prepared and characterized by physicochemical methods. Each lanthanide complex was eight coordinated with a pseudo-C3 symmetric distorted dodecahedron geometry. Density functional theory (DFT) studies suggest that Ln3+ ions can be easily incorporated into the chelator cavity without changing the basic geometry. Natural bonding orbitals (NBO) and energy decomposition analysis (EDA) indicate that M–L bonds have ~ 70% ionic character. Exciting and diverse behavior was observed when the results of 12N3Me5Ox were compared with 9N3Me5Ox; with the increase in the size of the macrocyclic ring, the covalency of the metal–ligand bond was increased. The luminescence properties of these complexes were different in the solid and solution state. The f–f transitions of the lanthanide were not observed for the complexes. The theoretical results are in good agreement with the experiments.
Synthesis of electron-rich sterically hindered P1 phosphazene bases by the staudinger reaction
Alexandrova, Anastasia V.,Masek, Tomas,Polyakova, Svetlana M.,Cisarova, Ivana,Saame, Jaan,Leito, Ivo,Lyapkalo, Ilya M.
, p. 1811 - 1823 (2013/04/10)
The synthesis of electron-rich P1 phosphazene bases with a sterically protected basic center by a Staudinger reaction is reported. The initial products of the reaction between peralkylated triaminophosphanes and bulky alkyl azides, phosphazides 1a-f, were isolated in all cases in good to quantitative yield. The structures of 1d and 1e were confirmed by single-crystal X-ray diffraction. Acidic hydrolysis of pyrrolidino-substituted phosphazide (pyrr)3PN3tBu 1d led to the quantitative formation of aminophosphonium salt (pyrr)3PNH2+· BF4- 8, a direct precursor to a Schwesinger's "building block" synthetic unit. Thermally induced denitrogenation of the phosphazides, which is the second step performed in most cases under solvent-free conditions gave P1 phosphazene bases 2a-f in moderate to excellent yields. A "one-pot" two-step synthesis of phosphazene bases from commercially available triaminophosphanes was discovered. Most of the syntheses were performed on a large laboratory scale. The basicities of the newly synthesized bases 2e and 2f were determined. X-ray crystal structures were obtained for base 2e and for protonated species 2d·HBF4, 2e·HBF4, and 2f·HOTs, which provided the crucial geometrical parameters around the basic center. A rationale for the higher basicity of the pyrrolidino- (pyrr)3P=NR than the piperidino- (pip)3P=NR phosphazenes is presented. A Staudinger reaction was successfully used for the synthesis of a number of sterically congested electron-rich P1 phosphazene bases in moderate to quantitative yield. The intermediate phosphazides were isolated and characterized in all cases; their application in the preparation of higher-order phosphazenes is described. Copyright
Syntheses, conformations, and basicities of bicyclic triamines
Bell, Thomas W.,Choi, Heung-Jin,Harte, William,Drew, Michael G. B.
, p. 12196 - 12210 (2007/10/03)
The multistep syntheses of several bicyclic triamines are described, all of which have an imbedded 1,5,9-triazacyclododecane ring. In 1,5,9-triazabicyclo[7.3.3]pentadecanes 12, 13, 15, and 16, two nitrogens are bridged by three carbons. The monoprotonated forms of these triamines are highly stabilized by a hydrogen-bonded network involving the bridge and both bridgehead nitrogens, producing a difference of more than 8 pKa units in acidities of their monoprotonated and diprotonated forms. The one- and zero-carbon bridges in 1,5,9-triazabicyclo[9.1.1]tridecane (23) and 7-methyl-1,5,9-triazabicyclo[5.5.0]dodecane (39) do not enhance the stabilities of their monoprotonated forms. X-ray crystal structures and computational studies of 12·HI and 16·HI reveal similar, but somewhat weaker, hydrogen-bonded networks, relative to 15·HI. The activation free energies for conformational inversion of 13·HI (14.4 ± 0.2 kcal/mol), 16·HI (15.0 ± 0.1 kcal/mol) and 16 (8.8 ± 0.3 kcal/mol) were measured by variable-temperature 1H and 13C NMR spectroscopy. These experimental barriers give an estimate of 6.2 kcal/mol for the strength of the bifurcated hydrogen bond between the bridge nitrogen and cavity proton in 16·HI. Computational studies support the hypothesis that N-inversion occurs in an open conformation, leading to an estimate of 10.32 kcal/mol for the enthalpy of the bifurcated hydrogen bond in 16·HI in the gas phase.
Anti-viral triaza compounds and compositions
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Page column 17, (2010/01/30)
The invention relates to a family of new synthetic triamine compounds which can be used in antiviral pharmaceutical compositions.
Synthesis of polyazamacrocyclic compounds via modified Richman-Atkins cyclization of β-trimethylsilylethanesulfonamides
Hoye,Hoye,Richman,Dantas,Lightbourne,Scott Shinneman
, p. 2722 - 2725 (2007/10/03)
The Richman-Atkins cyclization remains one of the most widely used methods for the preparation of macrocyclic polyamines. The use of β-trimethylsilylethanesulfonamides (SES-sulfonamides) for the preparation of polyazamacrocyclic compounds is described. This expands existing Richman-Atkins sulfonamide macrocyclization methodology, and it successfully enables preparation of labile polyaza[n](1,4)naphthalenophanes and polyaza[n](9,10)anthracenophanes, not previously available in appreciable quantities.
Simple preparations of tricyclic orthoamides and macrocyclic triamines
Kim,Wilson,Haseltine
, p. 3109 - 3114 (2007/10/02)
Hexahydropyrimidopyrimidine 3 is condensed with an alkyl ditosylate 4 at room temperature in DME or toluene. The resulting tricyclic salt is reduced with sodium borohydride to provide orthoamides 6a-c. Acidic hydrolysis of these orthoamides gives the corresponding macrocyclic triamines 8a-c in high yield.
