| Summary: | The study of isolated atoms or molecules inside a fullerene cavity provides a unique environment. It is likely to control the outer carbon cage and study the isolated species when molecules or atoms are trapped inside a fullerene. We report the Diels–Alder addition reaction of 9,10-dimethyl anthracene (DMA) to H<sub>2</sub>@C<sub>60</sub> while <sup>1</sup>H NMR spectroscopy is utilized to characterize the Diels–Alder reaction of the DMA with the fullerene. Through <sup>1</sup>H NMR spectroscopy, a series of isomeric adducts are identified. The obtained peaks are sharp, precise, and straightforward. Moreover, in this paper, H<sub>2</sub>@C<sub>60</sub> and its isomers are described for the first time.
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