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The oxidation of bezaldehyde occurs spontaneously on contact with air: M. Hudlický, Oxidations in Organic Chemistry, American Chemical Society, Washington, DC, 1990, p. 174.
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23
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0343449313
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note
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To confirm the effect of carboxylic acid, the hydroacylation of 1-hexene with freshly purified benzaldehyde was performed with henzoic acid under the reaction conditions depicted in Equation (1). While it took 24 h to obtain a 72% yield without benzoic acid, the reaction time was shortened to 6 h with benzoic acid, and a 75% yield of heptanophenone 6 a was obtained.
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25
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0027504983
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27
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0343885112
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note
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The reactivity of 2a with 9 towards hydroiminoacylation was not enhanced by the addition of 7. This implies that carboxylic acid does not affect the hydroiminoacylation step. Therefore, we assume that the rate-determining step is the formation of 9.
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28
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0343885111
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note
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It is also possible that Ia condenses with 4 to form 9. However, the condensation of 1a with 8 is more facile than with 4. When an equimolar mixture of 1a, 4, and 8 was heated at 130°C for 10 min 1a was completely consumed and the ratio of 9:11 was determined as 10:90 by GC.
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0010840223
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36
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0342316832
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note
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It can be explained by the fact that the protonated aldimine is more electrophilic than the aldehyde. Since the aldimine is more basic than the aldehyde, it is the dominant reactant in the presence of acid.
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