Tripodal Tris-N-oxides: Synthesis and Hydrogen Bonding Capabilities

Dedicated with respect to Professor Steve Ley FRS, mentor and friend, on the occasion of his 70^th birthday

Abstract

A number of tripodal tris-N-oxide receptors were synthesized and their hydrogen-bonding capabilities were investigated. Particular success was seen with both the benzene- and mesitylene-linked trismorpholine N-oxide receptors, which exhibited significant hydrogen bonding to both water and urea, as well as the inclusion of a rare decameric water cluster, as demonstrated by X-ray crystallography.

Key words

tripodal receptors - amine oxides - hydrogen bonding - crystal structure - water clusters

• References and Notes

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• 16 Tris-N-oxides 4a–e and 8a–d; General Procedure mCPBA (2.20 mmol) was added to a stirred solution of triamine 3 or 7 (0.70 mmol) and K₂CO₃ (2.20 mmol) in CH₂Cl₂ (14 mL) under N₂ at –78 °C, and the reaction vessel was allowed to warm to r.t. After 48 h, the mixture was filtered, the residue was washed with CH₂Cl₂, and the solvent was removed in vacuo to give the desired compound. 4,4′,4′′-[Benzene-1,3,5-triyltris(methylene)]tris(morpholine) 4,4′,4′′-Trioxide (4b) White solid; yield: 201 mg (>100%). ¹H NMR (300 MHz, CD₃OD): δ = 7.89 (s, 3 H, 3Ar–H), 4.56 (s, 6 H, 3CH₂), 4.18 (t, J = 11.7 Hz, 6 H, 6CH α and syn to N⁺–O^–), 3.83 (d, J = 11.7 Hz, 6 H, 6CH α to O and syn to N⁺–O^–), 3.63 (t, J = 11.7, 6 H, 6CH α to O and anti to N⁺–O^–), 3.05 (d, J = 11.7, 6 H, 6CH α and anti to N⁺–O^–). ¹³C NMR (75 MHz, CD₃OD): δ = 138.7 (3 ring × C–CH₂), 129.1 (3 × ring C–H), 73.4 (6CH₂ α to O), 63.1 (3ArCH₂), 61.0 (6CH₂ α to N). MS (FAB): m/z = 424 (55) [M + H]⁺, 322 (43) [M + H]⁺ – C₄H₈NO₂, 220 (25) [M + H]⁺ –2[C₄H₈NO₂]. HRMS: m/z [M + H]⁺ calcd for C₂₁H₃₄N₃O₆: 424.24476; found: 424.24416. Crystal data: C₂₁H₃₃N₃O₆·3CH₄N₂O·3 H₂O: Stoe IPDS, T = 213 K, monoclinic, space group P2₁/c, a = 10.166(2) Å, b = 21.823(4) Å, c = 15.565(2) Å, β = 103.58(2)°, V = 3356.7(10) ų, 2θ_max = 45°; 4097 unique reflections, R1 [I > 2σ(I)] 0.081, wR2 (all data) = 0.242. Crystals diffracted very weakly; therefore data were truncated at 2θ_max = 45°; all three water molecules are disordered. Crystal data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html. 4b·3CH₄N₂O·3H₂O: CCDC 1439355. 4,4′,4′′-[(2,4,6-Trimethylbenzene-1,3,5-triyl)tris(methylene)-]tris(morpholine) 4,4′,4′′-Trioxide (8b) White solid; yield: 480 mg (85%); mp 128–130 °C. IR (nujol): 2924, (s, C–H), 1665 (s, C=C aryl), 1570 (s, C=C aryl), 1114 (s, C–N), 858 (s, N⁺–O^–) cm^–1; ¹H NMR (300 MHz, CD₃OD): δ = 2.85 (s, 9 H, 3CH₃ ), 3.05 (s, 6 H, 3 × ring C–CH₂ ), 3.46 (m, 6 H, 6 CH α to O and syn to N⁺–O^–), 3.66 (m, 6 H, 6 CH α to O and anti to N⁺–O^–), 4.35 (m, 6 H, 6 CH α to N and syn to N⁺–O^–), 4.81 (m, 6 H, 6 CH α to N and anti to N⁺–O^–). ¹³C NMR (75 MHz, CD₃OD): δ = 130.05 (3 × ring C–CH₂), 129.65 (3 × ring C–CH₃), 69.2 (3 × ring C–CH₂), 62.6 (6 CH₂ α to O), 61.4 (6 CH₂ α to N), 21.8 (3 CH₃). MS (ES,+ve): m/z (%) 488 (100) [M + Na]⁺, 472 (35%) [M + Na – O]⁺. HRMS: m/z [M + Na]⁺ calcd for C₂₄H₄₀N₃NaO₆: 488.2723; found: 488.2752. Crystal data: C₂₄H₃₉N₃O₆·7 H₂O: Bruker Smart Apex, T = 150 K, orthorhombic, space group Pbca, a = 17.8733(11) Å, b = 18.0114(11) Å, c = 18.6381(12) Å, V = 6000.0(6) ų, 2θ_max = 55°; 7125 unique reflections, R1 [I > 2σ(I)] = 0.050, wR2 (all data) = 0.130. H-atoms on water molecules were refined by using restraints. Crystal data can be obtained free of charge via www.ccdc.cam.ac.uk/conts/retrieving.html. 8b·7H2O: CCDC 1439354.� All other experimental procedures and characterization data can be found in the Supporting Information.
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