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cited therein.
4.4.2. Reaction of 1,2,4-trichloro-5-iodobenzene (1i) with
furan in the presence of lanthanum metal: the formation
of 1,2,4-trichloro-5-deuteriobenzene (4) by quenching
with D2O. Lanthanum powder (139 mg, 1.0 mmol) and
iodine (10 mg, 0.04 mmol) were placed in a round-
bottomed flask. Tetrahydrofuran (10 ml), furan (2.04 g,
30 mmol) and 1,2,4-trichloro-5-iodobenzene (307 mg,
1.0 mmol) were added into the flask, and the mixture was
stirred at 258C for 4 h under nitrogen atmosphere. The
reaction was quenched with DCl/D2O (5%), and the mixture
was extracted with diisopropylether (10 ml£3). The organic
layer was washed with aqueous sodium thiosulfate and dried
over MgSO4. The solution was filtered, and the filtrate was
concentrated. Purification of residue by column chroma-
tography on silica gel afforded 1,2,4-trichloro-5-deuterio-
benzene, 1,2,4-trichlorobenzene and the corresponding
naphthalene derivative.
2. (a) Imamoto, T.; Kusumoto, T.; Hatanaka, Y.; Yokoyama, M.
Tetrahedron Lett. 1982, 23, 1353. (b) Fukuzawa, S.; Fujinami,
T.; Sakai, S. J. Chem. Soc., Chem. Commun. 1986, 475.
(c) Fukuzawa, S.; Sumimoto, N.; Fujinami, T.; Sakai, S. J. Org.
Chem. 1990, 55, 1328.
3. (a) Yanada, R.; Bessho, K.; Yanada, K. Chem. Lett. 1994,
1279. (b) Yanada, R.; Bessho, K.; Yanada, K. Synlett 1995,
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Tetrahedron Lett. 1996, 37, 9313. (e) Yanada, R.; Negoro, N.;
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Chem. 1990, 55, 1328.
1,2,4-Trichloro-5-deuteriobenzene: 1H NMR d 7.382 (s,
1H), 7.461 (s, 1H); 13C NMR d 128.22, 130.53, 131.24,
131.34 (t), 131.85, 131.97.
4.5. General procedure of reaction of 1,2-bis(bromo-
methyl)benzene (7a) with alkene in the presence of
lanthanum metal
Lanthanum powder (208 mg, 1.5 mmol) and iodine (10 mg,
0.04 mmol) were placed in a three-necked flask. Tetra-
hydrofuran (10 ml), alkene (5.0 mmol) and o-bis(bromo-
methyl)benzene (263 mg, 1.0 mmol) were added into the
flask, and the mixture was stirred at 678C for 6 h under
nitrogen atmosphere. The reaction was quenched with
aqueous HCl (5%), and the mixture was extracted with
diisopropylether (10 ml£3). The organic layer was washed
with aqueous sodium thiosulfate and dried over MgSO4.
The solution was filtered, and the filtrate was concentrated.
Purification of residue by column chromatography on silica
gel afforded the corresponding naphthalene derivatives.
Products were characterized by comparison of their spectral
data (1H and 13C NMR and IR) with those of authentic
samples (8b,30 8c,30 8e,31 and 8f31).
5. Nishino, T.; Watanabe, T.; Okada, M.; Nishiyama, Y.;
Sonoda, N. J. Org. Chem. 2002, 67, 966.
6. Kawabata, H.; Nishino, T.; Nishiyama, Y.; Sonoda, N.
Tetrahedron Lett. 2002, 43, 4911.
7. (a) Kaelin D. K., Jr.; Lopez, O. D.; Martin, S. F. J. Am. Chem.
Soc. 2001, 123, 6937. (b) Knight, D. W.; Little, P. B. J. Chem.
Soc., Perkin Trans. 1 2000, 2343. and references cited therein.
8. (a) Wittig, G.; Pohmer, L. Angew. Chem. 1960, 72, 564.
(b) Wittig, G.; Pohmer, L. Chem. Ber. 1956, 89, 1334.
(c) Kitamura, T.; Yamane, M.; Inoue, K.; Todaka, M.;
Fukatsu, N.; Meng, Z.; Fujiwara, Y. J. Am. Chem. Soc.
1999, 121, 11674. (d) Kitamura, T.; Fukatsu, N.; Fujiwara, Y.
J. Org. Chem. 1998, 63, 8579. (e) Kitamura, T.; Yamane, M.
J. Chem. Soc., Chem. Commun. 1995, 983. (f) Hoffman, R. W.
Dehydrobenzene and Cycloalkynes; Academic: New York,
1967. (g) Gilchrist, T. L. In The Chemistry of Functional
Groups; Patai, S., Rappoport, Z., Eds.; Wiley: Chlichester,
1983; Chapter 11. (h) Hart, H. The Chemistry of Triple-bonded
Functional Groups, Supplement C2; Patai, S., Ed.; Willey:
Chichester, 1994; Chapter 18. (i) Himeshima, Y.; Sonoda, T.;
Kobayashi, H. Chem. Lett. 1983, 1211. and reference cited
therein.
1
4.5.1. Compound 8d. H NMR d 0.91 (t, J¼7.2 Hz, 3H),
2.98–3.14 (m, 4H), 3.18–3.23 (m, 2H), 3.87(q, J¼7.2 Hz,
2H), 7.09–7.33 (m, 9H); 13C NMR d 13.9, 33.1, 37.5, 43.8,
46.9, 60.2, 126.0, 126.7, 127.4, 128.3, 128.6, 134.2, 135.5,
143.3, 174.5; IR 700, 747, 1024, 1175, 1729, 2926, 2979,
3026, 3061 cm21
.
Acknowledgements
9. Lanthanum metal was commercially available high-grade
product and was used after powderization (ca. 240 mesh).
10. We have already shown that the addition of a catalytic amount
of iodine dramatically enhanced the reductive dimerization of
carbonyl compounds11 or imine12 with lanthanum metal.
11. Nishino, T.; Nishiyama, Y.; Sonoda, N. Heteroat. Chem. 2000,
11, 81.
We thank the Santoku Co. for supplying the lanthanum
metal. This work was supported by The Ministry of
Education, Culture, Sports, Science and Technology (No.
15550096).
References
12. Nishino, T.; Nishiyama, Y.; Sonoda, N. Heteroat. Chem. 2002,
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13. In the reaction used ytterbium or samarium metal, it was
disclosed that various reactions were promoted by the addition