- Synthesis method of 1,4-bis(p-toluenesulfonyl)trinitrocyclononane
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The invention discloses a synthesis method of 1,4-bis(p-toluenesulfonyl)trinitrocyclononane. The synthesis method comprises the following steps: with 1,4-bis(p-toluenesulfonyl)-7-benzoyltrinitrocyclononane as a substrate, removing a protecting group of a benzoyl group under an alkaline condition, and conducting a reaction under the condition that two p-toluenesulfonyl groups do not participate in the reaction so as to obtain the 1,4-bis(p-toluenesulfonyl)trinitrocyclononane. Reaction conditions are that a reflux reaction is adopted and reaction time is 10-36 hours. Compared with the prior art, the synthesis method of the invention has the following beneficial effects: the use of a large amount of inorganic acid and organic acid is avoided, and the problems of safety, environmental protection and the like are effectively guaranteed essentially; and reaction yield can be up to 90% or above.
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Paragraph 0015-0022
(2021/08/21)
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- Using iSUSTAIN to validate the chemical attributes of different approaches to the synthesis of tacn and bridged (bis)tacn ligands
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Using green chemistry principles, alternative approaches for the synthesis of commercially important aza-macrocyclic tacn and (bis)tacn derivatives have been investigated to determine the step average and overall efficiency of these synthetic methods. Based on analytical metrics derived from the iSUSTAIN toolkit, the Richman-Atkins route for the synthesis of tacn (1) was found to be the more efficient; however an alternate route was shown to be preferable for the synthesis of (bis)tacn (2) compounds. The outcome of this study documents the importance of rigorous analysis of synthetic procedures for such aza-macrocyclic compounds in terms of their green chemistry attributes, in order to delineate how alternative synthetic methods can be ranked, more innovative procedures selected to improve productivity and yield, and synthetic methods deployed to achieve greater levels of waste reduction, reduced use of hazardous chemicals and lower environmental impact.
- Coghlan,Campi,Jackson,Hearn
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p. 5477 - 5484
(2016/10/21)
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- INTERMEDIATES FOR THE SYNTHESIS OF 1,2-BIS(4,7-DIMETHYL-1,4,7-TRIAZACYCLONON-1-YL)-ETHANE AND PREPARATION METHOD THEREOF
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The present invention provides intermediates for the synthesis of 1,2-bis(4,7-dimethyl-1,4,7-triazacyclonon-1-yl)-ethane and preparation method thereof. The intermediates are protonated salts of 1,4-ditosylate-1,4,7-triazacyclononane or 1,4-dibenzenesulph
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Page/Page column 9-10
(2012/02/01)
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- 1,2-BIS-(4,7-DIMETHYL-1,4,7-TRIAZACYCLONON-1-YL)-ETHANE AND INTERMEDIATE THEREOF
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The present invention provides improved processes for the synthesis of 1,4-ditosyl- 1,4,7-triazacyclonone and protected analogues thereof, and to synthesise bis(triazacyclononane) ligands.
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Page/Page column 15-16
(2012/02/01)
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- Tripodal tris-tacn and tris-dpa platforms for assembling phosphate-templated trimetallic centers
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Multidentate tripodal ligands, N(CH2-m-C6H 4-CH2tacn)3 (L1) and N(CH2-o-C 6H4-CH2N(CH2py)2) 3 (L2), have been devised for assembling high-nuclearity metal clusters. By using the same tripodal platform with different ligand appendages, either triazacyclononanes or dipicolylamines, and functionalizing either the ortho or the meta positions on the tris(xylyl) linker arms, discrete trimetal phosphate units of relevance to phosphate-metabolizing trimetallic centers in biology were prepared. Four such compounds, [(CuIICl) 3(HPO4)L1](PF6) (1), [(CuIICl) 3(HAsO4)L1](PF6) (2), Na2[Mn III6MnII2(H2O) 2(HPO4)6(PO4)4(L1) 2] (3), and [CoII3(H2PO 4)Cl2(MeCN)L2](PF6)3 (4), all containing three metal centers bound to a central phosphate or arsenate unit bridging oxygen atoms, have been synthesized and structurally characterized. These results demonstrate the propensity of this novel tripodal ligand platform, in the presence of phosphate or arsenate, to assemble {M3(EO 4)} units and thus structurally mimic trimetallic active sites of proteins involved in phosphate metabolism. Reactivity studies reveal that the tricopper complex 1 is more efficient than monocopper analogues in catalyzing the hydrolysis of 4-nitrophenyl phosphate.
- Cao, Rui,Mueller, Peter,Lippard, Stephen J.
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supporting information; experimental part
p. 17366 - 17369
(2011/02/23)
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- Complexes of cyclic polyaza chelators with cations of alkaline earth metals for enhanced biological activity
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Cyclic polyaza chelators that possess high affinity and specificity for first transition series metal cations exhibit an unanticipated improvement in biological activity when administered as complexes with cations of the alkaline earth metals, Ca(II) and Mg(II), most notably Ca(II). By virtue of this improvement, these complexes are particularly effective in the treatment of pathological conditions, including ischemia and ischemia-reperfusion injury.
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Page/Page column 6
(2010/02/11)
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- Neuroprotection and cardioprotection afforded by chelators with high affinity and specificity for cations of first transition series elements
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Compounds that demonstrate chelation affinity and selectivity for first transition series elements are administered to patients suffering from such conditions as ischemia, prolonged seizures and trauma to provide neuroprotection, cardioprotection, or both. These compounds when administered form complexes with chelatable iron and copper cations and thereby mitigate the ability of these cations to catalyze Haber-Weiss reactions that form toxic hydroxy free radicals that cause tissue injury. These compounds also form complexes with chelatable zinc cations thereby inhibiting the cytotoxicity associated with excess chelatable zinc.
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- An efficient route to symmetrically and unsymmetrically substituted azamacrocyclic ligands
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An extremely efficient cyclisation protocol has been developed for the synthesis of symmetrically (6) and unsymmetrically substituted (7) derivatives of 1,4,7-triazacyclononane (2). The optimised conditions can be successfully applied to the synthesis of larger macrocycles 15a and 18a. In contrast, the protocol is not generally applicable with benzylamine, and the cyclic carbamates 16 and 19, rather than larger azamacrocycles, are formed, indicating that cyclisation in CH3CN using K2CO3 is highly specific to the formation of 7.
- Pulacchini, Sonia,Watkinson, Michael
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p. 4233 - 4238
(2007/10/03)
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- Convenient synthesis of mono- and ditosylated 1,4,7-triazacyclononane
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Mono- and ditosylated 1,4,7-triazacyclononane (2, 3) were synthesized by rapid partial deprotection of 1,4,7-tritosyl-1,4,7-triazacyclononane (1) in vigorously stirred refluxing acetic acid-hydrobromic acid mixture.
- Lazar,Takacs
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p. 3141 - 3144
(2007/10/03)
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- Synthesis and characterisation of pendant-arm amino derivatives of 1,4,7-triazacyclononane and alkyl-bridged bis(1,4,7-triazacyclononane) macrocycles and complexation to Cu(II)
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The new pentadentate and bis(pentadentate) ligands 1-methyl-4,7-bis(3-aminopropyl)-1,4,7-triazacyclononane 6 and 1,2-bis[4,7-bis(3-aminopropyl)-1,4,7-triazacyclonon-1-yl]ethane 14 have been synthesised by reaction of acrylonitrile with the corresponding macrocyclic precursors and subsequent reduction of the nitrile groups with BH3*THF. Cu(II) complexes of the two ligands having formulations [Cu(6)][BF4]2 and [Cu2(14)][PF6]4*6MeCN, respectively, have been prepared and structurally characterised. Both complexes exhibit distorted square-based pyramidal geometries about the metal centres with the two primary amino groups belonging to the pendant arms occupying basal positions [Cu-Nap 2.257(6), Cu-Neq 2.026(6)-2.074(5) Angstroem for [Cu(6)]2+, and 2.337(2) and 2.038(3)-2.085(3) Angstroem for [Cu2(14)]4+]. The binuclear complex [Cu2(14)]4+ is centrosymmetric about the ethane bridge with the two pentadentate compartments oriented away from one another to give a transoid anti-configuration with a MeCN molecule interacting with each Cu(II) centre at 2.710(4) Angstroem. Both complexes have also been characterised by electronic and EPR spectroscopy and by cyclic voltammetry, and their properties compared to those of Cu(II) complexes of analogous macrocyclic ligands having 2-methylpyridyl pendant arms.
- Blake, Alexander J.,Danks, Jonathan P.,Li, Wan-Sheung,Lippolis, Vito,Schroeder, Martin
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p. 3034 - 3040
(2007/10/03)
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- An efficient one-pot route to symmetrically and unsymmetrically substituted 1,4,7-triazacyclononanes also results in the isolation of a stable macrocyclic aminal
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A one-pot methodology has been developed for the direct synthesis of symmetrically and unsymmetrically N-substituted derivatives of 1,4,7-triazacyclononane. In the course of these studies the unexpected eight-membered cyclic aminal 7 has been isolated via an acid-catalysed rearrangement of enamine 5.
- Pulacchini, Sonia,Watkinson, Michael
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p. 9363 - 9365
(2007/10/03)
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- Selective N-Protection of Medium-ring Triamines
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Efficient schemes for selective N-protection of 1,4,7-triazacyclononane and 1,5,9-triazacyclododecane and for synthesis of related bis-coronands are based upon the synthetic intermediacy of tricyclic orthoamides.
- Weisman, Gary R.,Vachon, David J.,Johnson, Van B.,Gronbeck, Dana A.
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p. 886 - 887
(2007/10/02)
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