1-adamantyl 2-naphthyl

Fig. 38. Chemiluminescence properties of the phenolic anions of two substituted adamantyl naphthyl dioxetanes. The emission wavelength and half-life of compound (a) are 550 nm and 23 min, respectively, while the corresponding values for compound (b) are 459 nm and 9 sec. These data are taken from Edwards et at. (El).

However, if the nucleophiles have a low antibonding n MO, as in the case with the 1-naphthaleneselenate ion, the radical anion formed does not fragment because the odd electron is localized in the naphthyl moiety as a n radical anion. In this system only the substitution product 1-naphthyl-1-adamantyl selenide was formed in 50% yield122. 

Bulky amino acid side-chains (e.g., naphthyl, adamantyl, etc.)... 

Fig. 39. Illustration of how the delocalization of electronic charge in disubstituted naphthylate adamantyl dioxetanes can give rise to p-carbanions (2,7-derivative shown in (a)] or a-carbanions [2,6-derivative shown in (b)]. Only in the former case is there an efficient interaction between the electron cloud and the peroxy group.

Figure 37.1 Organocatalysts used in [3+2] cycloadditions of nitrones. (Ad = adamantyl, Bn = benzyl, Naph = naphthyl, Tf= trifluoromethanesulfonyl.)...

In the random copolymers shown in Scheme 1, hydrophobic associations occur completely in an intrapolymer mode [20-22] hence, the polymers form unimer micelles independent of the polymer concentration in water. The sequence distribution of electrolyte and hydrophobic monomer units in the polymer chain is a critical structural factor to determine whether the hydrophobic self-associations are an intra- or interpolymer mode. Block sequences of hydrophobic units have a strong tendency for interpolymer association, whereas random and alternating sequences tend to associate in an intrapolymer mode [20-22]. Even a subtle difference in the sequence distribution in random copolymers has a significant effect on the self-association mode [23]. If the sequence distribution is blocky in nature, there is a propensity for interpolymer association. Other important structural factors that induce polymers to form unimer micelles are that the hydrophobic groups should be bulky and have cyclic structures, such as cyclododecyl, adamantyl, and naphthyl groups, and their contents in the copolymers should be higher than about 30 mol%, as shown in Scheme 1 [20-22]. In addition. 

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