H. Meier, S. Kim
FULL PAPER
2920, 2840, 1650, 1570, 1500, 1460, 1420, 1380, 1340, 1260, 1110, 29.5, 31.3, 31.4 (CH2), 69.6 (m-OCH2), 75.1 (p-OCH2), 106.8
1020, 960, 800. Ϫ 1H NMR (CDCl3): δ ϭ 0.89 (t, 27 H, CH3), (aromat. CH),[14] 126.0 (olefin HCe), 127.8 (aromat. HCc), 132.0
1.32Ϫ1.49 (m, 54 H, CH2), 1.72Ϫ1.85 (m, 18 H, CH2), 3.96Ϫ4.02
(aromat. Cq), 138.4 (olefin HCf), 138.6 (aromat. Ca), 138.9 (p-CqO),
(m, 18 H, OCH2), 6.71 (s, 6 H, aromat. H), 6.95/7.02 (AB, 3J ϭ 140.5 (aromat. HCb), 150.4 (aromat. Cd), 152.9 (m-CqO), 192.2
16.1 Hz, 6 H, olefin H, donor side), 7.10 (‘‘s’’, 6 H, olefin H), 7.30
(AAЈ part of AAЈBBЈ, 6 H, aromat. H), 7.45Ϫ7.47 (BBЈ and
AAЈBBЈ, 18 H, aromat. H). Ϫ 13C NMR (CDCl3): δ ϭ 14.0 (CH3),
22.6Ϫ31.8 (CH2, superimposed), 69.4, 73.6 (OCH2), 81.8 (CqOH),
105.6, 126.2, 126.7, 126.9, 128.3 (aromat. CH), 127.3, 128.0, 128.8,
129.0 (olefin CH), 132.0, 136.5, 136.6, 137.0, 138.8, 146.1, 153.4
(aromat. Cq). Ϫ UV (CHCl3): λmax (log ε) ϭ 372 nm (5.2). Ϫ MS
(FD): m/z (%) ϭ 1774 (100) [Mϩ·]. Ϫ C121H160O10 (1774.6): calcd.
C 81.90, H 9.09; found C 81.85, H 9.02.
(central C). Ϫ Vis (CHCl3): λmax (log ε) ϭ 746 nm (4.9).
all-(E)-Tris[phenyl-4-(2-{phenyl-4-[2-(3,4,5-trihexyl-
oxyphenyl)ethenyl]}ethenyl)]methylium Trifluoroacetate (6b): 1H
NMR (CDCl3/CF3CO2D, 7:3):
δ ϭ 0.90 (m, 27 H, CH3),
1.29Ϫ1.47 (m, 54 H, CH2), 1.79 (m, 18 H, CH2), 4.08 (t, 12
HϪOCH2), 4.13 (t, 6 H, p-OCH2), 6.82 (s, 6 H, aromat. H),[14]
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7.02/7.12 (AB, J ϭ 16.1 Hz, 6 H, olefin H), 7.35 (A part of olefin
AB, 3J ϭ 16.1 Hz, 3 H, He), 7.66 (B of AB, superimposed, 3 H,
Hf), 7.58Ϫ7.67 (m, 18 H, aromat. H), 7.88 (m, 6 H, Hb). Ϫ 13C
NMR (CDCl3/CF3CO2D, 7:3): δ ϭ 13.5, 13.5 (CH3), 22.3, 22.3,
25.2, 25.5, 28.9, 29.3, 31.3, 31.4 (CH2), 69.8 (m-OCH2), 75.3 (p-
OCH2), 105.5 (aromat. CH),[14] 126.0 (olefin HCe), 126.4, 127.2,
127.8, 128.5, 130.2 (aromat. and olefin CH), 133.7, 134.9, 136.1
(aromat. Cq), 138.3 (olefin HCf), 138.9 (p-CqO), 139.8 (Ca), 140.4
(HCb), 150.5 (Cd), 152.4 (m-CqO), 192.2 (central C). Ϫ NIR
(CHCl3): λmax (log ε) ϭ 815 nm (5.0).
all-(E)-Tris(phenyl-4-{2-[phenyl-4-(2-{phenyl-4-[2-(3,4,5-trihexyl-
oxyphenyl)ethenyl]}ethenyl)]ethenyl})methanol (5c): The preparation
was performed according to the procedure described for 5a. The
reaction time amounted to 3 days. The crude product was dissolved
in chloroform and precipitated by the addition of ethanol. Yield
65%, m.p. 175 °C. Ϫ IR (KBr): ν˜: ϭ 2940 cmϪ1, 2920, 2830, 1565,
1530, 1490, 1450, 1420, 1370, 1330, 1250, 1225, 1105, 1105, 1005,
960, 915, 830, 720, 620. Ϫ 1H NMR (CDCl3): δ ϭ 0.89 (t, 27
H, CH3), 1.32Ϫ1.49 (m, 54 H, CH2), 1.72Ϫ1.85 (m, 18 H, CH2),
3.69Ϫ4.02 (m, 18 H, OCH2), 6.71 (s, 6 H, aromat. H), 6.95/7.02
(AB, 3J ϭ 16.1 Hz, 6 H, olefin H, donor side), 7.10 (‘‘s’’, 12 H,
olefin H), 7.29Ϫ7.49 (m, 36 H, aromat. H). Ϫ 13C NMR (CDCl3):
δ ϭ 14.0 (CH3), 22.6Ϫ31.8 (CH2, superimposed), 69.4, 73.6
(OCH2), 81.8 (CqOH), 105.5, 126.2, 126.8Ϫ127.0, 127.3, 128.1,
128.3, 128.7, 129.0 (aromat. and olefin CH, partly superimposed),
132.6, 136.6Ϫ136.9, 138.7, 146.1, 153.4 (aromat. Cq, partly super-
imposed). Ϫ UV (CHCl3): λmax (log ε) ϭ394 nm (5.4). Ϫ MS (FD):
m/z (%) ϭ 2080 (100) [Mϩ·]. Ϫ C145H178O10 (2081.0): calcd. C
83.69, H 8.62; found C 83.67, H 8.59.
all-(E)-Tris(phenyl-4-{2-[phenyl-4-(2-{phenyl-4-[2-(3,4,5-
trihexyloxyphenyl)ethenyl]}ethenyl)]ethenyl})methylium
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Trifluoroacetate (6c): H NMR (CDCl3/CF3CO2D, 7:3): δ ϭ 0.88
(m, 27 H, CH3), 1.27Ϫ1.48 (m, 54 H, CH2), 1.79 (m, 18 H, CH2),
4.06 (t, 12 HϪOCH2), 4.10 (t, 6 H, p-OCH2), 6.74 (s, 6 H, aromat.
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H),[14] 6.97/ 7.03 (AB, J ϭ 16.0 Hz, 6 H, olefin H), 7.15/7.22 (AB,
3J ϭ 16.1 Hz, 6 H, olefin H), 7.33 (A part of olefin AB, 3J ϭ
16.1 Hz, 3 H, He), 7.61 (B of AB, superimposed, 3 H, Hf),
7.50Ϫ7.67 (m, 30 H, aromat. H), 7.87 (m, 6 H, Hb). Ϫ 13C NMR
(CDCl3/CF3CO2D, 7:3): δ ϭ 13.8, 13.8 (CH3), 22.4, 22.4, 25.3,
25.6, 29.1, 29.4, 31.4, 31.5 (CH2), 69.5 (m-OCH2), 74.9 (p-OCH2),
105.2 (aromat. CH),[14] 126.0 (olefin HCe), 126.8, 127.1, 127.2,
127.6, 127.8, 127.8, 128.0, 128.6, 130.3 (aromat. and olefin CH),
133.7, 134.9, 136.0, 136.3, 137.1 (aromat. Cq), 138.3 (olefin HCf),
138.8 (p-CqO), 140.0 (Ca), 140.4 (HCb), 150.3 (Cd), 152.6 (m-CqO),
190.6 (central C). Ϫ NIR (CHCl3): λmax (log ε) ϭ 850 nm (5.1).
all-(E)-Tris{phenyl-4-[2-(phenyl-4-{2-[phenyl-4-(2-{4-[2-(3,4,5-
trihexyloxyphenyl)ethenyl]}ethenyl)]ethenyl})ethenyl]}methanol (5d):
Preparation and purification analogous to 5c. Yield 65%, m.p.
Ͼ300 °C. Ϫ IR (KBr): ν˜ ϭ 3400 cmϪ1, 3000, 2920, 2900, 2840,
1565, 1530, 1495, 1450, 1415, 1370, 1330, 1245, 1220, 1120, 1100,
1105, 960, 915, 830, 785, 720, 690. Ϫ 1H NMR ([D8]THF): δ ϭ
0.89 (t, 27 H, CH3), 1.32Ϫ1.55 (m, 54 H, CH2), 1.71Ϫ1.85 (m, 18
H, CH2), 3.94Ϫ4.02 (m, 48 H, OCH2), 6.82 (s, 6 H, aromat. H),
all-(E)-Tri{phenyl-4-[2-(phenyl-4-{2-[phenyl-4-(2-{phenyl-4-[2-(3,4,5-
trihexyloxyphenyl)ethenyl]}ethenyl)]ethenyl})ethenyl]}methylium Tri-
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fluoroacetate (6d): Ϫ H NMR (CDCl3/CF3CO2D, 7:3): δ ϭ 0.89
(m, 27 H, CH3), 1.25Ϫ1.46 (m, 54 H, CH2), 1.79 (m, 18 H, CH2),
4.08 (m, 18 H, OCH2), 6.76 (s, 6 H, aromat. H),[14] 7.01Ϫ7.28 (m,
28 H, olefin H), 7.40Ϫ7.62 (m, 42 H, aromat. H and Hf), 8.06 (m,
6 H, Hb). Ϫ 13C NMR (CDCl3/CF3CO2D, 7:3): δ ϭ 13.9, 13.9
(CH3), 22.5, 22.7, 25.8, 25.8, 29.2, 29.5, 31.5, 31.6 (CH2), 69.8 (m-
OCH2), 75.3 (p-OCH2), 105.5 (aromat. CH),[14] 126.2 (olefin HCe),
126.6Ϫ131.0 (aromat. and olefin CH, superimposed), 134.4Ϫ138.4
(aromat. Cq, superimposed), 136.8 (olefin HCf), 139.5 (p-CqO),
140.3 (Ca), 140.8 (HCb), 150.5 (Cd), 152.6 (m-Cq), 191.5 (central
C). Ϫ NIR (CHCl3):[16] λmax ϭ 850 nm.
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7.05/ 7.12 (AB, J ϭ 16.1 Hz, 6 H, olefin H, donor side), 7.21 (m,
18 H, olefin H), 7.35Ϫ7.56 (m, 48 H, aromat. H). Ϫ 13C NMR
([D8]THF): δ ϭ 14.0 (CH3), 22.6Ϫ31.8 (CH2, superimposed), 69.4,
73.6 (OCH2), 81.8 (CqOH), 105.5, 126.3Ϫ129.1 (aromat. and olefin
CH, superimposed), 132.6, 136.6Ϫ136.9, 138.6, 146.1, 153.3
(aromat. Cq, partly superimposed). Ϫ UV (CHCl3): λmax (log ε) ϭ
403 nm (5.5). Ϫ MS (FD): m/z (%) ϭ 2387 (100) [Mϩ·]. Ϫ
C169H196O10 (2387.4): calcd. C 85.02, H 8.28; found C 85.42, H
7.98.
Isolation
of
all-(E)-Tris{phenyl-4-[2-(3,4,5-trihexyloxyphenyl)-
Generation of the Methylium Trifluoroacetates 6a؊d: The carbinols
5a؊d (about 50 mg) were dissolved in chloroform/trifluoroacetic
acid (7:3; about 0.7 mL). A spontaneous and quantitative forma-
tion of the salts 6a؊d occurred.
ethenyl]}methylium Tetrafluoroborate (6aЈ): The carbinol 5a (50 mg,
3.4 ϫ 10Ϫ2 mmol) was dissolved in 30 mL of CH2Cl2 and treated
with 2 mL of HBF4 and ca. 2 mL of acetic anhydride, until the salt
6aЈ precipitated quantitatively as a dark blue solid. The filtered
compound was purified by evaporation of the volatile parts in
vacuo (102 Pa). The salt is highly hygroscopic; it cannot be handled
in air and hydrolyses rapidly in aqueous solvents.
all-(E)-Tris{phenyl-4-[2-(3,4,5-trihexyloxyphenyl)ethenyl]}methylium
1
Trifluoroacetate (6a): H NMR (CDCl3/CF3CO2D, 7:3): δ ϭ 0.91
(m, 27 H, CH3), 1.32Ϫ1.49 (m, 54 H, CH2), 1.81 (m, 18 H, CH2),
4.08 (t, 12 HϪOCH2), 4.16 (t, 6 H, p-OCH2), 6.88 (s, 6 H, aromat.
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H),[14] 7.20 (A part of olefin AB, J ϭ 16.1 Hz, 3 H, He),[15] 7.55
Acknowledgments
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(B of AB, J ϭ 16.1 Hz, 3 H, Hf), 7.61 (AAЈ part of AAЈBBЈ, 6 H,
Hc), 7.86 (BBЈ of AAЈBBЈ, 6 H, Hb). Ϫ 13C NMR (CDCl3/ We are grateful to the Deutsche Forschungsgemeinschaft and the
CF3CO2D 7:3): δ ϭ 13.6, 13.7 (CH3), 22.3, 22.4, 25.3, 25.5, 29.0, Fonds der Chemischen Industrie for financial support.
1166
Eur. J. Org. Chem. 2001, 1163Ϫ1167