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16944362497
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note
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For example, equally compatible with the UV and mass spectral data are the two diastereoisomers resulting from monohydrolysis of the scissile bond of the aziridine moiety of 9.
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28
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16944366677
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note
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This situation is complicated by the chance occurrence that the new substance (11) and the same retention time on HPLC as the major diastereoisomer of the initial products (13).
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29
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16944366623
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note
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The presence of iron(II) was critical: FR66979 is essentially inert to treatment with sodium borohydride alone, as evidenced by the fact that this is one method of preparing FR66979 from FR900482.
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30
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16944367306
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note
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This was confirmed by exposing freshly collected "13" from the HPLC to excess sodium borohydride, with the result that no 11 was produced.
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31
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16944362425
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This rate constant is probably the least reliable of those we have measured, because in the course of the incubation the pH rose from 8.9 to roughly 9.5.
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32
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16944366540
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note
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A variant of this experiment provided support for the hypothesis that the hydrolysis of the relatively long-lived intermediate was accelerated by exposure to the packing material of an HPLC column. The reductively activated sample was aged in the presence of some C-18 silica gel from a used HPLC column, resulting in roughly a doubling of the rate at which the intermediate was diverted to materials incapable of being converted to dihydroindole 11 during subsequent treatment with sodium borohydride.
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33
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16944361929
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note
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-1 at pH 7.5.
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34
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0005825454
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33947299959
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