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[2+2]环加成反应在有机合成中具有重要应用价值,其反应机理研究早已受到重视.现在β-二酮类的烯醇光环加成(即de Mayo反应)研究已从链烯扩展到芳核。乙酰丙酮和1-萘甲酸甲酯的光环加成的机理研究表明,这个反应不是一步完成的。光谱和~1H NMR数据基本确定中间体(1)的构型,但无法指定它的最终产物结构。X光单晶结构分析证明产物为具有张力的特殊碳架结构(2),而分子力学计算证明另一可能结构(3)具有更高的立体能。现在全面报导晶体结构和分子力学分析结果,从而揭示反应的全过程。
The [2 + 2] cycloaddition reaction has an important application value in organic synthesis, and its reaction mechanism has long been valued.Now the studies on the enol ring photodimerization of β-diketones (de Mayo reaction) To aromatic nuclear. The mechanism of photocycloaddition of acetylacetone and methyl 1-naphthoate shows that this reaction is not completed in one step. The spectra and ~ 1H NMR data basically confirmed the configuration of intermediate (1), but its final product structure could not be specified. The X-ray single crystal structure analysis proves that the product is a special carbon-frame structure with tension (2), while the molecular mechanics calculation proves that the other possible structure (3) has a higher stereoscopic energy. Now fully report the crystal structure and molecular mechanics analysis results, revealing the whole process of the reaction.