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DOI: 10.1055/s-0036-1590883
Synthesis of Dansyl-Substituted Cryptands Containing Triazacycloalkane Moieties and their Evaluation as Fluorescent Chemosensors
This work was financially supported by the RFBR grants N 17-53-16012 and 15-03-04698Publication History
Received: 28 June 2017
Accepted after revision: 28 July 2017
Publication Date:
21 September 2017 (online)
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Dedicated to Professor Victor Snieckus
Abstract
A method for the synthesis of a new family of cryptands containing 1,4,7-triazacyclononane and 1,5,9-triazacyclododecane moieties and dansyl fluorophore groups has been elaborated starting from free triazacycloalkanes and employing Pd(0)-catalyzed amination at the macrocyclization step. The dependence of the products yields on the nature of reagents has been established. The majority of synthesized macrobicycles have been evaluated as possible chemosensors for detecting metal cations. Compound comprising 1,4,7-triazacyclononane and dioxadiamine linker proved to be a prospective colorimetric sensor for Cu(II) by changing its absorption spectrum in the presence of this cation, while other cryptands demonstrated full quenching of fluorescence in the presence of Cu(II) and Al(III) what makes them promising fluorescent molecular probes for these metals.
Key words
triazacycloalkanes - cryptands - Pd catalysis - amination - fluorescence - cations detectionSupporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/s-0036-1590883.
- Supporting Information
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References and Notes
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21
Typical Experimental Procedure for the Synthesis of the Cryptands (14–16): A two-neck flask equipped with a magnetic stirrer and reflux condenser, flushed with anhyd argon, was charged with the corresponding triazacycloalkane derivative 8–10 (0.15–0.29 mmol), Pd(dba)2 (16 mol%), DavePhos (18 mol%), and absolute dioxane (10–15 mL). The mixture was stirred for 2–3 min, then the corresponding oxadiamine (0.15–0.29 mmol) was added followed by t-BuONa (0.45–0.9 mmol). The reaction mixture was stirred at reflux for 24 h, cooled to ambient temperature, the residue was filtered off, washed with CH2Cl2 (5 mL), combined organic fractions were evaporated in vacuo, and the residue was chromatographed on silica gel using a sequence of eluents CH2Cl2, CH2Cl2–MeOH (100:1–2:1), CH2Cl2–MeOH–NH3(aq) (100:20:1–10:4:1).
5-[10,13,16-Trioxa-6,20-diaza-3(1,4)-triazacyclononane-1,5(1,3)-dibenzenacycloicosaphan-37-ylsulfonyl]-N,N-dimethylnaphthalenyl-1-amine (14a): Compound 14a was obtained from compound 8 (140 mg, 0.2 mmo,), trioxadiamine 13a (44 mg, 0.2 mmol), in the presence of Pd(dba)2 (18 mg, 0.032 mmol), DavePhos (14 mg, 0.036 mmol), tBuONa (58 mg, 0.6 mmol) in dioxane (10 mL). Eluent: CH2Cl2–MeOH (3:1), yield: 37 mg (24%); yellow glassy solid. UV–vis (MeCN): λ max = 305 nm (logε 3.76), 340 (logε 3.48) nm. 1H NMR (400 MHz, CDCl3): δ = 1.85 (br quintet, 3 Jobs = 5.7 Hz, 4 H, CH2CH 2CH2), 2.86 (br s, 4 H, CH2N), 2.87 (s, 6 H, Me) 3.08–4.00 (br m, 12 H, CH2N, PhCH2N), 3.24 (br t, 3 Jobs = 4.8 Hz, 4 H, CH2NPh), 3.55–3.60 (br m, 8 H, CH2O), 3.61–3.66 (br m, 4 H, CH2O), 6.58 [br s, 2 H, H(Ph)], 6.60 [br d, 3 Jobs = 6.9 Hz, 2 H, H(Ph)], 6.84 [br s, 2 H, H2(Ph)], 7.10 [t, 3 J = 7.7 Hz, 2 H, H5(Ph)], 7.15 [d, 3 J = 7.6 Hz, 1 H, H6(Nf)], 7.49 [t, 3Jobs = 7.8 Hz, 1 H, H3(Nf)], 7.53 [t, 3 Jobs = 8.2 Hz, 1 H, H7(Nf)], 7.98 [br s, 1 H, H2(Nf)], 8.34 [d, 3 J = 7.6 Hz, 1 H, H8(Nf)], 8.54 [d, 3 J = 8.2 Hz, 1 H, H4(Nf)], two NH protons were not unambiguously assigned. 13C NMR (100.6 MHz, CDCl3): δ = 28.7 (2 × C, CCH2C), 41.4 (2 × C, CH2NPh), 45.3 (2 × C, Me), 47.0–57.0 (br m, 6 × C, CH2N), 61.7 (br s, 2 × C, Δν1/2 = 100 Hz, PhCH2N), 69.4 (2 × C, CH2O), 70.1 (2 × C, CH2O), 70.5 (2 × C, CH2O), 112.7 [br s, 2 × C, Δν1/2 = 60 Hz, CH(Ph)], 114.3 [br s, 2 × C, Δν1/2 = 30 Hz, CH(Ph)], 115.4 [1 × C, CH(Nf)], 118.1 [1 × C, CH(Nf)], 119.0 [br s, 2 × C, Δν1/2 = 30 Hz, CH(Ph)], 123.1 [1 × C, CH(Nf)], 128.2–131.0 [br m, 3 × CH(Nf), 2 × C5(Ph), 2 × C(Nf)], 134.4 [1 × C, C(Nf)], 137.5 [2 × C, C1(Ph)], 149.2 [br s, 2 × C, Δν1/2 = 20 Hz, C3(Ph)], 151.9 (1 × C, NC(Nf)]. HRMS (MALDI, dithranol, PEG-600): m/z [M + H]+ calcd for C42H59N6O5S: 759.4268; found: 759.4223. - 22a Averin AD. Uglov AN. Beletskaya IP. Chem. Lett. 2008; 37: 1074
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- 26 The experiments of metal cations detection were conducted as follows. The solutions of Zn(II), Cd(II), Pb(II), Hg(II), Ag(I), Cu(II), Co(II), Ni(II), Fe(II), Mn(II), Mg(II), Ba(II), Ca(II), Al(III), Li(I) Na(I), K(I) perchlorates and In(III), Y(III), Ga(III) nitrates were dissolved in MeCN (UHPLC grade) to make concentrations c = 0.01 M [in the case of Hg(II) perchlorate 0.005 M]. Macrocyclic ligands 14–17 were also dissolved in MeCN (UHPLC grade) to make concentrations c = 3.3 × 10–5 M. The solution of metal salt was added directly to the solution of the ligand in the spectrophotometric cuvette (1, 2, 5 equiv) and UV–vis and fluorescent spectra (excitation at 340 nm) were recorded after each addition.