U. Lüning, E. Mak, M. Zindler, B. Hartkopf, R. Herges
FULL PAPER
(t, J = 6.4 Hz, 4 H, CH21,10), 3.88 (s, 3 H, OCH3), 1.72 (mc, 4 H, 45-Methoxy-3,7,10,19-tetraoxa-1,9(1,4)-dibenzena-5(2,6)-pyridina-
CH22,9), 1.41 (mc, 4 H, CH23,8), 1.3–1.2 (m, 8 H, CH24,5,6,7) ppm.
cyclononadecaphan-14-ene (3a): According to general procedure H,
13C NMR (125 MHz, CDCl3): δ = 167.2 (s, Py-C4), 159.6 (s, Py- 2,6-bis[4-(pent-4-enyloxy)phenyloxymethyl]-4-methoxypyridine (15a,
C2,6), 158.8 (s, Bn-C4), 130.1 (d, Bn-C2,6), 129.3 (s, Bn-C1), 114.6 104 mg, 200 µmol) and benzylidenebis(tricyclohexylphosphane)-
(d, Bn-C3,5), 105.8 (d, Py-C3,5), 72.3 (t, Bn-CH2), 70.9 (t, Py-CH2), ruthenium dichloride (20.0 mg, 24.0 µmol) were allowed to react in
67.4 (t, CH21,10), 55.2 (s, OCH3), 29.4, 28.7, 28.6 (3t, CH22,4,5,6,7,9), dichloromethane (200 mL) for 7 d. Chromatography (dichloro-
25.6 (t, CH23,8) ppm. MS (MALDI-TOF, CCA): m/z = 558 [M + methane/ethyl acetate, 9:1; Rf = 0.26) yielded 44.0 mg (90.0 µmol,
K]+, 542 [M + Na]+, 520 [M + H]+. MS (EI, 70 eV): m/z (%) = 519
(4) [M]+, 152 (100) [C8H10NO2]+, 137 (37) [C8H11NO]+, 121 (22)
[C7H7NO]+, 107 (95) [C6H5NO]+. MS (CI, isobutane): m/z (%) =
45%) of 3a. M.p. 108 °C. H NMR (500 MHz, CDCl3, TMS): δ =
7.23 (d, J = 8.5 Hz, 4 H, Ar-H2,6), 6.88 (s, 2 H, Py-H3,5), 6.78 (d,
J = 8.0 Hz, 4 H, Ar-H3,5), 5.42 (mc, 2 H, CH=CH), 4.55 (s, 4 H,
PyCH2OCH2), 4.50 (s, 4 H, PyCH2), 3.92 (t, J = 6.7 Hz, 4 H,
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520 (56) [M + H]+, 97 (100) [C H ]+. IR (ATR): ν = 2925, 2852
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(aliph. C-H), 1597, 1580, 1509 (arom. C=C), 1238 (C-O-C), 835 OCH2), 3.69 (s, 3 H, OCH3), 2.16 (mc, 4 H, OCH2CH2), 1.81 [mc,
(isol. arom. H), 795 (1,4-disub. arom.) cm–1. HRMS (EI, 70 eV):
calcd. for C32H41NO5 519.29846; found 519.29596 (∆ = –4.8 ppm).
HRMS (EI, 70 eV): calcd. for C3113CH41NO5 520.30182; found
520.30177 (∆ = –0.1 ppm).
4 H, O(CH2)2CH2] ppm. 13C NMR (125 MHz, CDCl3): δ = 158.64
(s, Ar-C1)*, 158.60 (s, Py-C2,6)*, 130.30 (d, Ar-C3,5), 130.20 (d,
CH=CH), 129.40 (s, Ar-C4), 114.55 (d, Ar-C2,6), 107.06 (d, Py-
C3,5), 71.76 (t, PyCH2OCH2), 66.71 (t, PyCH2), 55.47 (q, OCH3),
28.44, 28.35 (2 t, OCH2CH2CH2) ppm. *Assignments can be re-
versed. The signal for Py-C4 could not be detected. MS (EI, 70 eV):
m/z (%) = 489 (4) [M]+, 152 (100) [M – C22H25O3]+, 107 (61) [M –
C24H30O4]+. MS (MALDI-TOF, CCA): m/z = 512 [M + Na]+, 490
45-Methoxy-3,7,10,22-tetraoxa-1,9(1,4)-dibenzena-5(2,6)-pyrid-
inadocosaphan (2c): According to general procedure C, 2,6-bis(bro-
momethyl)-4-methoxypyridine (8,[11] 177 mg, 600 µmol) in THF
(60 mL), 1,11-bis[(4-hydroxymethyl)phenoxy]undecane (7c,[15]
240 mg, 600 µmol) in THF (60 mL), and sodium hydride (400 mg,
10.0 mmol) in THF (400 mL). Time of addition: 6 h. Purification:
silica gel; CH2Cl2/methanol, 19:1; Rf = 0.57. Yield: 89.9 mg (28%).
[M + H]+. IR (ATR): ν = 2926, 2848 (aliph. C–H), 1602, 1576,
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1508 (arom. C=C), 1244 (C–O–C), 849 (1,4-disub. arom.) cm–1.
C30H35NO5 (491.27): calcd. C 73.59, H 7.21, N 2.86; found C
73.83, H 7.82, N 2.82.
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M.p. 72 °C. H NMR (500 MHz, CDCl3): δ = 7.22 (d, J = 8.6 Hz,
45-Methoxy-3,7,10,21-tetraoxa-1,9(1,4)-dibenzena-5(2,6)-pyridina-
cycloheneicosaphan-15-ene (3c): According to general procedure H,
2,6-bis[4-(hex-5-enyloxy)phenyloxymethyl]-4-methoxypyridine (15c,
55.0 mg, 100 µmol) and benzylidenebis(tricyclohexylphosphane)-
ruthenium dichloride (10.0 mg, 12.0 µmol) in dichloromethane
(200 mL) were allowed to react for 5 d. Chromatography (dichloro-
methane/ethyl acetate, 95:5; Rf = 0.14) yielded 26.0 mg (50.0 µmol,
4 H, Bn-H2,6), 6.89 (s, 2 H, Py-H3,5), 6.81 (d, J = 8.6 Hz, 4 H, Bn-
H3,5), 4.59 (s, 4 H, Py-CH2), 4.35 (s, 4 H, Bn-CH2), 3.95 (t, J =
6.2 Hz, 4 H, CH21,11), 3.88 (s, 3 H, OCH3), 1.73 (mc, 4 H, CH22,10),
1.43 (mc, 4 H, CH23,9), 1.4–1.3 (m, 10 H, CH24,5,6,7,8) ppm. 13C
NMR (125 MHz, CDCl3): δ = 167.1 (s, Py-C4), 159.7 (s, Py-C2,6),
158.9 (s, Bn-C4), 130.0 (d, Bn-C2,6), 129.3 (s, Bn-C1), 114.6 (d, Bn-
C3,5), 105.7 (d, Py-C3,5), 72.3 (t, Bn-CH2), 71.0 (t, Py-CH2), 67.6
(t, CH21,11), 55.2 (s, OCH3), 29.4, 29.0, 28.7, 28.6 (2 t,
CH22,4,5,6,7,8,10), 25.6 (t, CH23,9) ppm. MS (EI, 70 eV): m/z (%) =
533 (4) [M]+ 152 (100) [C8H10NO2]+, 137 (35) [C8H11NO]+, 121
(18) [C7H7NO]+, 107 (91) [C6H5NO]+. MS (CI, isobutane): m/z (%)
1
50%) of 3c. M.p. 88 °C. H NMR (500 MHz, CDCl3, TMS): δ =
7.21 (d, J = 8.4 Hz, 4 H, Ar-H2,6), 6.87 (s, 2 H, Py-H3,5), 6.79 (d,
J = 8.5 Hz, 4 H, Ar-H3,5), 5.41 (mc, 1 H, CH=CHcis), 5.38 (mc, 1
H, CH=CHtrans), 4.58 (s, 4 H, PyCH2OCH2), 4.44 (s, 4 H, PyCH2),
3.95 (mc, 2 H, OCH2), 3.88 (s, 3 H, OCH3), 2.04 [mc, 4 H,
O(CH2)2CH2], 1.73 (mc, 4 H, OCH2CH2), 1.57 [mc, 4 H, O(CH2)3-
CH2] ppm. 13C NMR (125 MHz, CDCl3, TMS): δ = 167.00 (s,
Py-C4), 158.88 (s, Ar-C1)*, 158.65 (s, Py-C2,6)*, 130.41, 130.11 (d,
CH=CH), 129.94 (d, Ar-C2,6), 129.34 (s, Ar-C4), 114.54 (d, Ar-
C3,5), 106.19 (d, Py-C3,5), 72.27 (t, PyCH2OCH2), 71.99 (t, PyCH2),
67.67 (t, OCH2), 55.33 (q, OCH3), 31.39 [t, O(CH2)2CH2], 28.38
(t, OCH2CH2), 25.90 [t, (OCH2)3CH2] ppm. *Assignments can be
reversed. MS (EI, 70 eV): m/z (%) = 517 (5) [M]+, 152 (100) [M –
C24H29O3]+, 107 (72) [C26H34O4]+. MS (CI, isobutane): m/z (%) =
518 (100) [M + H]+, 152 (11) [M – C24H29O3]+, 107 (5) [M –
C26H34O4]+. MS (MALDI-TOF, CCA): m/z = 556 [M + K]+, 540
= 534 (100) [M + H]+, 152 (12) [C H NO ]+. IR (ATR): ν = 2928,
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2850 (aliph. C-H), 1598, 1509 (arom. C=C), 1241 (C-O-C), 829
(isol. arom. H), 780 (1,4-disub. arom.) cm–1. C33H43NO5 (533.31):
calcd. C 74.27, H 8.12, N 2.62; found C 74.41, H 8.42, N 2.29.
45-Methoxy-3,7,10,23-tetraoxa-1,9(1,4)-dibenzena-5(2,6)-pyrid-
inatricosaphan (2d): According to general procedure C, 2,6-bis(bro-
momethyl)-4-methoxypyridine (8,[11] 177 mg, 600 µmol) in THF
(60 mL), 1,12-bis[(4-hydroxymethyl)phenoxy]dodecane (7d,[15]
328 mg, 600 µmol) in THF (60 mL), and sodium hydride (400 mg,
10.0 mmol) in THF (400 mL). Time of addition: 6 h. Purification:
silica gel; CH2Cl2/methanol, 19:1; Rf = 0.71. Yield: 151 mg (46%).
[M + Na]+, 518 [M + H]+. IR (ATR): ν = 3008 (arom. C–H), 2934,
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M.p. 62 °C. H NMR (500 MHz, CDCl3): δ = 7.23 (d, J = 8.7 Hz,
2847 (aliph. C–H), 1601, 1580, 1509 (arom. C=C), 1241 (C–O–C),
832 (1,4-disub. arom.) cm–1. C32H39NO5 (517.28): calcd. C 74.25,
H 7.59, N 2.71; found C 73.83, H 7.64, N 2.81.
45-Methoxy-3,7,10,31-tetraoxa-1,9(1,4)-dibenzena-5(2,6)-pyridina-
cyclohentriacontaphan-20-ene (3m): According to general pro-
cedure H, 2,6-bis[4-(undec-10-enyloxy)phenyloxymethyl]-4-meth-
4 H, Bn-H2,6), 6.89 (s, 2 H, Py-H3,5), 6.82 (d, J = 8.7 Hz, 4 H, Bn-
H3,5), 4.59 (s, 4 H, Py-CH2), 4.39 (s, 4 H, Bn-CH2), 3.96 (t, J =
6.4 Hz, 4 H, CH21,12), 3.88 (s, 3 H, OCH3), 1.74 (mc, 4 H, CH22,11),
1.43 (mc, 4 H, CH23,10), 1.4–1.3 (m, 12 H, CH24,5,6,7,8,9) ppm. 13C
NMR (125 MHz, CDCl3): δ = 159.6 (s, Py-C2,6), 158.8 (s, Bn-C4),
129.9 (d, Bn-C2,6), 129.4 (s, Bn-C1), 114.6 (d, Bn-C3,5), 105.9 (d,
Py-C3,5), 72.3 (t, Bn-CH2), 71.0 (t, Py-CH2), 67.6 (t, CH21,12), 55.3 oxypyridine (15m, 274 mg, 400 µmol), benzylidenebis(tricyclohex-
(s, OCH3), 29.6, 29.4, 29.3, 29.1, 29.0, 28.7, 28.7 (2 t,
CH22,4,5,6,7,8,9,11), 25.6 (t, CH23,10) ppm. The signal for Py-C4 could
not be detected. MS (EI, 70 eV): m/z (%) = 547 (5) [M]+ 152 (100)
ylphosphane)ruthenium dichloride (40.0 mg, 48.0 µmol) in dichlo-
romethane (300 mL) were allowed to react for 6 d. Chromatog-
raphy (dichloromethane/ethyl acetate, 9:1; Rf = 0.34) yielded
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[C8H10NO2]+, 137 (38) [C8H11NO]+, 121 (15) [C7H7NO]+, 107 (97) 67.0 mg (102 µmol, 26%) of 3m. M.p. 80 °C. H NMR (500 MHz,
[C6H5NO]+. MS (CI, isobutane): m/z (%) = 534 (24) [M + H]+, 152
CDCl3, TMS): δ = 7.25 (d, J = 8.5 Hz, 4 H, Ar-H2,6), 6.92 (s, 2 H,
Py-H3,5), 6.83 (d, J = 8.4 Hz, 4 H, Ar-H3,5), 5.37 (mc, 2 H,
(60) [C H NO ]+. IR (ATR): ν = 2919, 2850 (aliph. C–H), 1598,
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1510 (arom. C=C), 1242 (C-O-C), 834 (isol. arom. H), 807 (1,4- CH=CH), 4.59 (s, 4 H, PyCH2OCH2), 4.57 (s, 4 H, PyCH2), 3.92
disub. arom.) cm–1.
(mc, 2 H, OCH2), 3.88 (s, 3 H, OCH3), 2.04–1.96 [m, 4 H,
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Eur. J. Org. Chem. 2010, 4932–4940