NH2), 7.79 (1H, s, NH2), 7.34 (3H, m, meta- and para-Ph), 7.15 (2H, m,
ortho- Ph), 5.12 and 3.81 (C3H2), 3.70 and 3.47 (C4H2), 3.50, 3.27, 3.74 and
3.39 (C6H2C7H2), 3.76 and 3.64 (C9H2), 2.77 and 2.02 (C10H2), 3.82 (1H,
s, C15H); dC(125 MHz, DMSO-d6, 25 °C) 166.54 (m, C1), 62.59 (t, 1JC-H
= 145.8 Hz, C3), 70.40 (t, 1JC-H = 140.8 Hz, C4), 70.41 and 71.94 (two t,
1JC-H = 140.8, 140.8 Hz, C6, C7), 67.89 (t, 1JC-H = 140.8 Hz, C9), 35.69
(t, 1JC-H = 134.6 Hz, C10), 44.25 (m, C11), 160.58 (tm, 2JC-H = 6.66 Hz,
C12), 61.52 (d, 2JC-H = 6.2 Hz, C14), 46.05 (d, 1JC-H = 138.7 Hz, C15),
117.82 (dd, 3JC-H = 9.46, 3.05 Hz, C16), 119.67 (d, 3JC-H = 4.90 Hz, C18),
137.73, 127.96, 127.66 and 127.58 (ipso-, meta-, ortho-, para- of Ph ring);
MS (CI) m/z 353 [M + H+]; Anal. calc. for C19H20N4O3, C, 64.77, H, 5.68,
N, 15.91. Found C, 64.95, H, 5.52, N, 16.15%.
∑ Crystals of 5, suitable for X-ray crystallography grown from ethyl acetate.
¯
Crystal data of 5. C19H20N4O3, Mt = 352.39, triclinic, space group P1, a =
9.377(1), b = 9.409(1), c = 11.909(1) Å, a = 68.17(2), b = 84.5(1), g =
60.62(2)°, V = 845.0(1)Å3, T = 293 K, Z = 2, m(MoKa) = 0.096 mm21
;
3225 measured reflections, 2976 were independent; R1 = 0.056 and wR2 =
0.118 (for 1623 reflections with F > 4s(F)).
CCDC 182/1757.
Fig. 1 View of the molecular structure of compound 5. Selected bond
lengths [Å] and angles [°]: C(1)–C(14) 1.343(5), C(1)–O(2) 1.352(4), C(1)–
N(13) 1.369(4), C(11)–C(12) 1.524(5), C(11)–C(15) 1.564(4), C(12)–
N(13) 1.298(4), C(12)–N(20) 1.330(4), C(14)–C(18) 1.411(5), C(14)–
C(15) 1.523(4), C(15)–C(21) 1.517(4), N(13)–C(12)–N(20) 119.0(3),
N(20)–C(12)–C(11) 119.0(3).
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The 1H NMR of 5¶ shows two multiplets for the Ph ring, one
singlet for the C15-H resonance and the three expected ABCD
spin systems with typical values of SSCC for CH2CH2 groups
of ansa-moiety, which were assigned by using the 1H J-
resolved, 2D-COSY 1H–1H and 2D-COSY 1H–13C spectra.†
The observation of two unequivalent protons for the NH2 group
at d = 8.5 and 7.8 ppm is due to very slow rotation around the
C12–N bond.
This work was supported by DGICYT (grant SAF96-
1704).
Notes and references
‡ The IUPAC name for [9](2,5)pyridinophane is 12-azabicyclo[9.2.2]pen-
tadeca-11,13,14-triene.
§ Measurement of reduction potential. The reduction potentials of the
2-amino-3,5-dicyano-6-methoxypyridine and 4, were measured by means
of cyclic voltammetry at 25 °C and at the scan rate of 0.2 V s21 using a
mercury cathode as the working electrode and Ag/AgCl as the reference
electrode.
¶ Selected data for 5: mp. 265–266 °C (from ethyl acetate–hexane, 15+1);
nmax(KBr)/cm21 3420, 3352, 2900, 2220 (weak), 2186, 1630, 1548, 1450,
1366, 1314, 1150, 1130, 702; dH(500 MHz, DMSO-d6, 25 °C) 8.49 (1H, s,
15 L. Horner and K. Dickerhof, Chem. Ber., 1983, 116, 1615.
16 S. Kambe, K. Saito, A. Sakurai and H. Midorikawa, Synthesis, 1981,
531.
1776
Chem. Commun., 2000, 1775–1776