A solution to the vexing problem of investigating solvent-mediated electron transfer under conditions of frozen solvent motion may be at hand with the synthesis of novel U-shaped systems such as 1 (R=CO(2)Me) and 2 (R=CH(2)OMe), in which the imide-functionalized cleft provides the point of attachment of the "solvent" molecule, either covalently or by hydrogen bonding.
A solution to the vexing problem of investigating solvent-mediated electron transfer under conditions of frozen solvent motion may be at hand with the synthesis of novel U-shaped systems such as 1 (R=CO(2)Me) and 2 (R=CH(2)OMe), in which the imide-functionalized cleft provides the point of attachment of the "solvent" molecule, either covalently or by hydrogen bonding.
Sterically hindered p-nitrobenzylic chlorides (1) and
(2) react with the sodium salts of 2,4,6-trialkylbenzenethiols (3a)–(5a)
by the SRN1 reaction to give good yields of the
corresponding p-nitrobenzylic aryl sulfides
(6)–(10). For example, the reaction of sodium
2,4,6-triisopropylbenzenethiolate (4b) with
α-t-butyl-a-methyl-p-nitrobenzyl chloride (2)
gives the sulfide (10) in over 80% yield after 2 h at room temperature
in Me2SO. Only in reactions involving
2,4,6-tri-t-butylbenzenethiol (5a) are low yields or failed reactions
encountered. Qualitative examination of the dynamic nuclear magnetic resonance
spectra of the sulfides prepared in these reactions shows that up to three
restricted rotational phenomena can be identified. These are rotation about
the benzylic-carbon to p-nitrophenyl ring bond, rotation
about the sulfur to aromatic ring bond, and rotation about the bond joining
the t-butyl group to the benzylic carbon. The last phenomenon produces, in the
sulfide (9), the relatively rare and unusual situation wherein the t-butyl
group appears as three distinct methyl resonances at low temperatures.
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