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Azine byproducts were formed during the coupling reaction of nonbenzophenone-derived simple hydrazones, as determined by GC/MS. For discussions on the stability of simple hydrazones, see refs 31-33.
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0032560932
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We have also been able to couple benzophenone hydrazone with aryl chlorides employing a Pd/2-dicyclohexylphosphino-2′-dimethylaminobiphenyl-based catalyst system. By this method, hydrazone 4f was produced in 89% yield from benzophenone hydrazone and 4-chlorotoluene employing 1 mol % of this catalyst mixture. For a discussion on the use of this ligand for Pd-catalyzed cross-coupling reactions of aryl chlorides, see: Old, D. W.; Wolfe, J. P.; Buchwald, S. L. J. Am. Chem. Soc. 1998, 120, 9722.
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13044316348
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note
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The reaction of 4-bromoveratrole with benzophenone hydrazone requires 12 h to go to completion. In contrast, the coupling reactions to prepare hydrazones 4a-d are complete in 1.5-6 h.
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40
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84987274103
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13044290438
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Control experiments showed that, under typical reaction conditions in the absence of Pd, after 16 h approximately 40% of the benzophenone hydrazone undergoes base-promoted Wolff-Kishner reduction to form diphenylmethane. The formation of an N-aryl benzophenone hydrazone is not observed without the use of a Pd catalyst.
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42
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13044270782
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The use of aldehydes in this procedure does initially produce 2-H indole products. However, due to the low reaction pH, the 2-H indole products undergo oligomerization, resulting in low to moderate isolated yields of the desired indole product (see ref 45). We are currently investigating alternative approaches for the preparation of 2-H indoles from aldehydes and hydrazones 4.
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47
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13044316349
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note
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p-Methoxy-substituted arylhydrazines are particularly prone to N-N bond cleavage. See ref 3.
-
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48
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13044284528
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note
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In comparison, the bite angle of BINAP is 92°. See ref 49.
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