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(a) Reinicke, M. G.; Pedaja, P. In The Chemistry of Heterocyclic Compounds: Thiophene and Its Derivatives; Weissberger, A., Taylor, E. C., Eds.; John Wiley & Sons: New York, 1986; Vol. 44, Part 2, pp 159-522.
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The three isomeric dibromothiophenes are commercially available. 2-Bromo-3-iodothiophene can be prepared according to ref 8c. 2-Bromo-4-iodothiophene can be prepared according to: Gronowitz, S.; Holm, B. Acta Chem. Scand. 1976, B30, 505-511.
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3-Bromo-2-chlorothiophene can be prepared according to: Gronowitz, S.; Holm, B. Acta Chem. Scand. 1976, B30, 423-429.
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43
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85069081349
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note
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The protonation of the active Grignard species resulting in 2-bromothiophene and 3-bromothiophene may be a result of elimination of hydrogen bromide and hydrogen iodide from ethyl bromide and ethyl iodide by reaction with 2-bromo-3-thienylmagnesium chloride and 3-bromo-2-thienylmagnesium chloride, respectively.
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45
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85069072438
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note
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1) δ 7.11 (d, J = 4.9 Hz, 1 H), 7.54 (d, J = 4.9 Hz, 1 H). These data are in accordance with the data observed for the byproduct in 8b.
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47
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4: Normant, J. F.; Cahiez, G. In Organomanganese Reagents in Modern Synthetic Methods; Scheffold, R., Ed.; John Wiley & Sons: New York, 1983; Vol. 3, pp 173-216. However, 2-bromo-3-thienylmanganese chloride did not react with acetic anhydride, indicating a very low reactivity of this organometallic species.
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53
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85069079532
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note
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3 = tri(tertbutyl)phosphine.
-
-
-
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54
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85069073340
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Pat. Appl. WO 0276983, 2002
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The compound has been prepared, but not isolated: Blackaby, P. W.; Castro Pinero, J. L.; Chambers, M. S.; Goodacre, S. C.; Hallet, D. J.; Jones, P.; Lewis, R. T.; MacLeod, A. M.; Maxey, R. J.; Moore, K. W.; Street, L. J. Pat. Appl. WO 0276983, 2002.
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Blackaby, P.W.1
Castro Pinero, J.L.2
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Jones, P.6
Lewis, R.T.7
MacLeod, A.M.8
Maxey, R.J.9
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Herr, R.J.1
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