714
A. H. M. Elwahy / Tetrahedron Letters 43 (2002) 711–714
blue crystals, mp >250°C, MS (ESI): m/z (%) 945 [M+,
631–632; (b) Morgenroth, F.; Berresheim, A. J.; Wagner,
M.; Mu¨llen, K. Chem. Commun. 1998, 1139–1140; (c)
Morgenroth, F.; Mu¨llen, K. Tetrahedron 1997, 53, 15349–
15366.
1
100%]; H NMR: l 1.23 (s, 9H, C(CH3)3), 6.66–8.02
(m, 47H, aryl H, azulenyl H); 13C NMR: l 31.91, 38.43,
120.86, 125.37, 125.63, 126.23, 126.72, 126.86, 127.04,
127.61, 127.87, 128.19, 129.17, 129.48, 130.20, 131.42,
131.72, 131.79, 133.34, 134.94, 135.42, 136.29, 138.66,
140.22, 140.40, 140.48, 140.78, 141.67, 141.95, 161.16;
UV–vis (CH2Cl2): umax (log m)=246 nm (3.23), 284 (sh)
(2.98), 313 (2.97), 383 (2.34), 598 (4.29), 650 (sh) (4.20),
725 (sh) (3.73). 8: green crystals, mp 248–250°C, MS
5. (a) Dilthey, W.; Hurtig, G. Chem. Ber. 1934, 67, 2004–
2007; (b) Fieser, L. F. Organic Experiments, 1st ed.; Heath:
DC Boston, 1964; p. 307.
6. Diels–Alder reactions are today an important field of
research due to the increased interest in practical applica-
tions of the obtained materials. See e.g. Horn, T.; Wegener,
S.; Mu¨llen, K. Macromol. Chem. Phys. 1995, 196, 2463–
2474; Muller, A.; Stadler, R. Macromol. Chem. Phys. 1996,
197, 1373–1385; Diels, O.; Alder, K. Liebigs Ann. Chem.
1928, 460, 98–122.
7. The electrophilic halogenation of azulene seems to be
theoretically reasonable for the synthesis of 1-halo and
1,3-dihaloazulenes because the 1- and 3-positions of the
azulene ring are electronegative enough to react with
electrophiles. Ueno, T.; Toda, H.; Yasunami, M.; Yoshi-
fuji, M. Bull. Chem. Soc. Jpn. 1996, 69, 1645–1656; Ueno,
T.; Toda, H.; Yasunami, M.; Yoshifuji, M. Chem. Lett.
1995, 169; Zeller, K.-P. In Houben-Weyl: Methoden der
Organischen Chemie; Kropf, H., Ed.; Thieme: Stuttgart,
1985; Vol. 512C, pp. 127–418; Boothe, R.; Dial, C.;
Conaway, R.; Pagni, R.; Kabalka, G. W. Tetrahedron Lett.
1986, 27, 2207–2210; Hafner, K.; Patzelt, H.; Kaiser, H.
Liebigs Ann. Chem. 1962, 656, 24–33.
8. (a) Sonogashira, K.; Tohda, Y.; Hagihara, N. Tetrahedron
Lett. 1975, 4467–4470; (b) Tohda, Y.; Sonogashira, K.;
Hagihara, N. Synthesis 1977, 777–778; (c) Sonogashira, K.
In Metal Catalyzed Cross Coupling Reactions; Stang, P. J.;
Diederich, F., Eds.; Wiley-VCH: Weinheim, 1998; p. 203.
9. (a) Eglinton, G.; McRae, W. Adv. Org. Chem. 1963, 4,
225–328; (b) Behrr, O. M.; Eglinton, G.; Galbraith, A. R.;
Raphael, R. A. J. Chem. Soc. 1960, 3614–3625; (c)
Brandsma, L. Preparative Acetylene Chemistry, 2nd ed.;
Elsevier: Amesterdam, Oxford, New York, Tokyo, 1988;
p. 212ff.
1
(ESI): m/z (%) 1063 [M+, 100%]; H NMR: l 6.88–8.56
(m, 54H, aryl H, azulenyl H); UV–vis (CH2Cl2): umax
(log m)=246 nm (3.68), 311 (3.47), 422 (3.05), 462 (3.0),
616 (4.28). 9: deep green crystals, mp 223–225°C, MS
1
(ESI): m/z (%) 1039 [M+, 100%]; H NMR: l 6.68–8.59
(m, 54H, aryl H, azulenyl H); 13C NMR: l 90.2, 110.65,
123.78, 124.38, 125.49, 125.75, 126.38, 126.81, 127.05,
127.10, 127.75, 130.18, 130.69, 131.12, 131.66, 131.74,
133.03, 135.46, 136.58, 138.98, 140.24, 140.38, 140.50,
140.58, 140.97, 141.20, 141.86, 141.96; UV–vis
(CH2Cl2): umax (log m)=246 nm (3.27), 314 (3.21), 420
(2.56), 457 (2.54), 643 (4.58). 10: black crystals, mp
1
238–240°C, MS (ESI): m/z (%) 1245 [M+, 100%]; H
NMR: l 1.44 (s, 9H, C(CH3)3), 6.76–8.54 (m, 59H, aryl
H, azulenyl H); 13C NMR: l 29.83, 38.96, 89.73, 89.97,
110.57, 111.14, 123.46, 123.84, 124.41, 125.46, 125.74,
126.35, 126.77, 127.50, 127.73, 130.16, 130.69, 131.11,
131.65, 131.73, 132.99, 135.43, 136.61, 137.79, 138.97,
140.22, 140.34, 140.48, 140.56, 141.07, 141.20, 141.85,
141.96, 164.18; UV–vis (CH2Cl2): umax (log m)=247 nm
(3.36), 279 (sh) (3.23), 311 (3.20), 329 (sh) (3.19), 333
(sh) (3.18), 419 (2.89), 640 (4.85). 12: green crystals, mp
220–22°C, MS (ESI): m/z (%) 1598 [M+, 100%]; 1H
NMR: l 6.51–8.50 (m, 84H, aryl H, azulenyl H);
UV–vis (CH2Cl2): umax (log m)=246 nm (3.35), 308
(3.14), 383 (2.5), 618 (4.48), 675 (sh) (4.38).
10. (a) Handbook of Conducting Polymers; Skotheim, T. A.;
Elsenbaumer, R. L.; Reynolds, J. R., Eds.; Marcel Dekker:
New York, 1998; (b) Diederich, F. In Modern Acetylene
Chemistry; Stang, P. J.; Diederich, F., Eds.; VCH: Wein-
heim, 1995; pp. 443–471.
11. The described new compounds 3, 6, 8–10 and 12 were
purified by chromatography on silica using CH2Cl2/n-hex-
ane (1:5) or (1:3) as eluents.
Acknowledgements
The author is greatly indebted to Professor K. Hafner,
University of Darmstadt for his continuous help and
generous support. He also thanks the Alexander von
Humboldt Foundation for a research fellowship.
12. (a) Vollhardt, K. P. C. Acc. Chem. Res. 1977, 10, 1–8; (b)
Wakatsuki, Y.; Nomura, O.; Kitaura, K.; Morokuma, K.;
Yamazaki, H. J. Am. Chem. Soc. 1983, 105, 1907–1912; (c)
Vollhardt, K. P. C. Angew. Chem. 1984, 96, 525–541;
Angew. Chem., Int. Ed. Engl. 1984, 23, 539–555; (d)
Diercks, R.; Eaton, B. E.; Gu¨rtzgen, S.; Jalisatgi, S.;
Matzger, A. J.; Radde, R. H.; Vollhardt, K. P. C. J. Am.
Chem. Soc. 1998, 120, 8247–8248; (e) Hardesty, J. H.;
Koerner, J. B.; Albright, T. A.; Lee, G. Y. J. Am. Chem.
Soc. 1999, 121, 6055–6067; (f) Ville, G. A.; Vollhardt, K.
P. C.; Winter, M. J. Organometallics 1984, 3, 1177–1187.
13. All new compounds described gave correct elemental
analyses.
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