41775-76-2Relevant academic research and scientific papers
Cation Binding Properties and Molecular Structure of the Crystalline Complex (Aza-12-crown-2)2*NaI
White, Banita D.,Arnold, Kristin A.,Garrell, Robin L.,Fronczek, Frank R.,Gandour, Richard D.,Gokel, George W.
, p. 1128 - 1133 (1987)
Aza-12-crown-4 forms a 2:1 sandwich complex similar to that known for 12-crown-4 sodium iodide, except that the presence of >NH in each ring makes Na-donor bonds unequal in strength and leads to hydrogen bonding with the counterion.The heteroatoms of each macroring are coplanar, and both nitrogens are on the same side of the complex (twist angle 43 deg from eclipsed).This may be due to a long (and weak) hydrogen bond to iodide, an interaction confirmed by analysis using Raman spectroscopy.The previously unreported 1:1 and 2:1 cation affinity constants (anhydrous MeOH , 25 deg C) for this macrocycle are logKS(1:1) = 1.3 +/- 0.1 and logKS(2:1) = 2.0 +/- 0.1, respectively.
Synthesis and Cation Complexing of N,N'-Bridged Bis-(1,4,7-Trioxa-10-azacyclododecanes
Calverley, Martin J.,Dale, Johannes
, p. 684 - 686 (1981)
Two molecules of monoaza-12-crown-4 can be linked through nitrogen in one step by direct double alkylation; the resulting bis-crown aminoethers give intramolecular alkali cation sandwich complexes which are particularly strong when the bridge is -CH2CH2- and the cation is sodium.
Synthesis of monoazacrown ethers under phase-transfer catalysis
Luk'yanenko,Basok,Kulygina, E. Yu.,Bogashchenko, T. Yu.,Yakovenko
, p. 1345 - 1352 (2013/02/22)
A procedure has been proposed for the synthesis of monoazacrown ethers by reaction of N-benzyldiethanolamine with oligo(ethylene glycol) bis-p-toluenesulfonates in a two-phase system aromatic hydrocarbon-50% aqueous alkali, followed by removal of the benzyl group by catalytic hydrogenolysis. The maximal yields of N-benzylaza-12-crown-4, -18-crown-6, and -21-crown-7 were achieved by adding 4-10 equiv of LiCl, BaBr2, and CsCl, respectively, to the reaction mixture, which probably indicated template effect. Pleiades Publishing, Ltd., 2012.
Ring-Side-Arm Cooperativity in Cation Inclusion Complexes of 12-Membered Ring Lariat Ethers: Effect of Side-Arm Chain Length and a Clarification of Long-Side-Arm Binding Strengths
Arnold, Kristin A.,Mallen, Jesus,Trafton, John E.,White, Banita D.,Fronczek, Frank R.,et al.
, p. 5652 - 5657 (2007/10/02)
The alkali metal and ammonium cation binding properties of N-pivot, 12-crown-4 lariat ethers are recorded here.A reinvestigation of N-pivot lariat ethers having (CH2CH2O)nCH3 side arms is presented, and data are reported for fresh samples of these long chain compounds.Details of the X-ray crystal structures obtained for N-aza-12-crown-4 are reported.The complex crystallizes in the tricyclic space group P1 with cell constants a = 8.712 (2) Angstroem, b = 8.694 (3) Angstroem, c = 11.740 (3) Angstroem, α = 111.44 (2) deg, β = 90.76 (2) deg, γ = 103.50 (2) deg, and Z = 2 for Dc = 1.591 gcm-1.Least-squares refinement based on 3723 observed reflections led to a final conventional R value of 0.052.All of the lariat ether donors bind to the alkali metal cation, with the macroring in the crown conformation.The 12-crown-4 system behaves, in many ways, like the 15- and 18-membered ring analogues.The presence of an octakis(ethyleneoxy) side arm does not diminish cation binding strength in this series as reported for the 15- and 18-membered ring compounds.Indeed, the fall off in binding constants previously reported for the longest chain examples of the latter families now appears to be due to sample decomposition rather than solvent encumbrance.
Chromogenic aza-12-crown-4 ethers and method of using same for the detection of lithium
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, (2008/06/13)
Chromogenic aza-12-crown-4 ethers which can be used for the spectrophotometric determination of lithium ion in aqueous solutions are disclosed. The compounds of the invention are particularly useful for the analysis of Li30 in the presence of Na+, a situation common in biological and geological systems. The compounds [e.g., 1-(2-oxy-5-nitrobenzyl)-1-hydro-1-aza-4,7,10-trioxacylclododecane], their methods of manufacture, and methods of utilizing the compounds for the analysis of lithium are disclosed and claimed.
Lipophilic Bis(monoaza crown ether) Derivatives: Synthesis and Cation-Complexing Properties
Sakamoto, Hidefumi,Kimura, Keiichi,Koseki, Yasuaki,Matsuo, Mitsunori,Shono, Toshiyuki
, p. 4974 - 4979 (2007/10/02)
Eleven lipophilic bis(monoaza crown ether) derivatives were synthesized, in which two monoaza crown ethers with 9-, 12-, 15-, or 18-membered rings are linked through the nitrogen atoms by an alkane-, diether-, or diester-type bridge chain bearing a dodecyl group.Sodium and potassium binding with the bis(monoaza crown ether) was determined potentiometrically and compared with those for previous bis(crown ethers) 5 (n = 1 - 3) and corresponding monocyclic analogues 4 and 6 (n = 1 - 3).Marked bis(crown ether) effect was observed only for the alkane-type bis(monoaza-12-crown-4) and bis(monoaza-15-crown-5) derivatives 1 (n = 1,2) on complexing Na+ and K+, respectively.It was suggested that in some of the other bis(monoaza crown ethers) lariat-ether effect works instead.Bis(monoaza-9-crown-3) derivatives 1 and 2 (n = 0) possess very poor cation-complexing ability.Acidity constant values gave some hints about the bis(crown ether) effect.
FORMATION OF COMPLEXES BETWEEN AZA DERIVATIVES OF CROWN ETHERS AND PRIMARY ALKYLAMMONIUM SALTS. PART 8. 12-CROWN-4, 15-CROWN5, 21-CROWN-7, AND 24-CROWN-8 DERIVATIVES
Johnson, Martin R.,Jones, Nigel F.,Sutherland, Ian O.
, p. 1637 - 1644 (2007/10/02)
The monoaza-crown ethers (3), (4), and (5) and the diaza-crown ethers (6), (7), (10), and (11) form complexes with primary alkylammonium thiocyanates in organic solvents.The diaza-15-crown-5 system (11) forms well defined 1:1 complexes with the cis-, cis-stereochemistry shown in (16) but the diaza-24-crown-8-derivative (7) forms a 2:1 complex (G:H ratio) with benzylammonium thiocyanate having the cis,cis,trans,trans-stereochemistry (17a).The diaza-24-crown-6 derivative (10) forms weak 1:1 complexes which apparently adopt the double nesting conformation (18).
SYNTHESES AND CATION BINDING PROPERTIES OF 12-MEMBERED RING NITROGEN-PIVOT LARIAT ETHERS
White, Banita D.,Dishong, Dennis M.,Minganti, Carlo,Arnold, Kristin A.,Goli, D.M.,Gokel, George W.
, p. 151 - 154 (2007/10/02)
The efficient synthesis of several 12-membered ring, N-pivot lariat ethers are reported and it is shown that binding to sodium cations is weak except when an oligoethyleneoxy sidearm is long enough to provide additional solvation.
Synthesis of Monoaza Crown Ethers from N,N-Diamines and Oligoethylene Glycol Di(p-toluenesulfonates) or Corresponding Dichlorides
Maeda, Hirokazu,Furuyoshi, Shigeo,Nakatsuji, Yohji,Okahara, Mitsuo
, p. 212 - 218 (2007/10/02)
Monoaza crown ethers were prepared in satisfactory yields by the one-step reaction between diethanolamine or N,N-diamines and oligoethylene glycol di(p-toluenesulfonates) or corresponding dichlorides in t-butyl alcohol/dioxane in the presence of sodium or potassium t-butoxide.The reaction conditions in the preparation of monoaza 15- and 18-crown ethers were studied.Various monoaza crown ethers having substituents were also prepared and their properties were investigated.
1,4,7-Trioxa-10-azacyclododecane and Some N-Substituted Derivatives; Synthesis and Cation Complexing
Calverley, Martin J.,Dale, Johannes
, p. 241 - 248 (2007/10/02)
Primary amines condense with 1,11-diiodo-3,6,9-trioxaundecane in acetonitrile solution containing dispersed Na2CO3 to give N-substituted derivatives of monoaza-12-crown-4, including several directly appended with an additional donor group.The unsubstituted azacrown and the N-methyl derivative were obtained from the N-benzyl derivative.The alkali cation complexing properties were studied by 13C NMR spectroscopy.It was found that the presence of an additional donor atom in the side-chain suppresses the formation of 2:1 in favour of 1:1 complexes.
