Synlett 2016; 27(01): 141-145
DOI: 10.1055/s-0035-1560533
letter
© Georg Thieme Verlag Stuttgart · New York

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

Gemma L. Nixon
Robert Robinson Laboratories, Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK   Email: ion@liverpool.ac.uk
,
Helen Billington
Robert Robinson Laboratories, Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK   Email: ion@liverpool.ac.uk
,
S. Barret Kalindjian
Robert Robinson Laboratories, Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK   Email: ion@liverpool.ac.uk
,
Alexander Steiner
Robert Robinson Laboratories, Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK   Email: ion@liverpool.ac.uk
,
Ian A. O’Neil*
Robert Robinson Laboratories, Department of Chemistry, University of Liverpool, Crown Street, Liverpool, L69 7ZD, UK   Email: ion@liverpool.ac.uk
› Author Affiliations
Further Information

Publication History

Received: 01 October 2015

Accepted after revision: 24 October 2015

Publication Date:
08 December 2015 (online)


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

Supporting Information

 
  • References and Notes

  • 3 O’Neil IA In Science of Synthesis . Vol. 40b. Schaumann E. Thieme; Stuttgart: 2008: 855
  • 4 Roth AJ. K, Tretbar M, Stark CB. W. Chem. Commun. 2015; 51: 14175
    • 9a O’Neil IA, Miller ND, Peake J, Barkley JV, Low CM. R, Kalindjian SB. Synlett 1993; 515
    • 9b O’Neil IA, Miller ND, Barkley JV, Low CM. R, Kalindjian SB. Synlett 1995; 617
    • 9c O’Neil IA, Miller ND, Barkley JV, Low CM. R, Kalindjian SB. Synlett 1995; 619
    • 9d O’Neil IA, Potter AJ. Tetrahedron Lett. 1997; 38: 5731
    • 9e O’Neil IA, Potter AJ, Southern M, Barkley JV, Steiner A. Chem. Commun. 1998; 2511
  • 13 Croxall WJ, Van Hook JO. US 2613208, 1949
  • 14 van der Made AW, van der Made RH. J. Org. Chem. 1992; 58: 1262
  • 15 Prasad KB, Al-Jallo HN, Al-Dulaimi KS. J. Chem. Soc. C 1969; 2134
  • 16 Tris-N-oxides 4ae 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) Å3, 2θmax = 45°; 4097 unique reflections, R1 [I > 2σ(I)] 0.081, wR2 (all data) = 0.242. Crystals diffracted very weakly; therefore data were truncated at 2θmax = 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) Å3, 2θmax = 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.
  • 18 Fucke K, Steed W. Water 2010; 2: 333