Palladium-Catalyzed Synthesis Of 2-Carbonyl-indene Derivatives And Their Application In Synthesis Of Novel Fungicides

2-Carbonylindene and 2-carbonyl-1-indanol derivatives were synthesized via palladium-catalyzed Heck-aldol reaction. A series of novel oxime ether compounds were designed and synthesized using 2-acetylindene derivatives as material. The structures of the synthesized compounds were confirmed by IR, NMR EA and MS and biological activities of the synthesized oxime ether compounds were tested.Twenty-one 2-carbonylindene derivatives were synthesized in good yields by the reaction of orthohalogenated aryl aldehyde (or orthohalogenated aryl ketone) with allylic alcohols via one-pot palladium-catalyzed reaction. Sixteen of these compounds were not found in literature. The influence of reaction factors, such as reactant structure, base, temperature, reaction time and additives (quaternary ammonium salt and lithium chloride) on this reaction was discussed. The reaction conditions of one-pot palladium-catalyzed synthesis of 2-carbonylindens were optimized and described as follows: using tetrabutylammonium chloride and lithium chloride as cocatalyst, sodium acetate as base and N,N-dimethylformamide as solvent, arylhalides were reacted with allylic alcohols at 110 ℃ for about 1.5—5 h (2-iodobenzaldehyde reacted with allylic alcohol at 50 ℃).Forty-five novel oxime ether compounds were designed and synthesized by modifying the side chain of oxime ether strobilurin fungicide with a benzopentatomic ring as the essential structure, among which thirty-five oxime ether compounds were synthesized using 2-acetylindene derivatives as intermediates. Greenhouse biological testing on these compounds showed that they all had excellent fungicidal activities. In particular, these oxime ether compounds had much better fungicidal activities for Pyricularia oyrzae (rice blast), Phytophthora infestans (tomoto late blight), Eryiphe graminis (wheat powdery mildew) and Colletotrichum lagenarium (cucumber anthracnose) than the aryl substituted unsaturated oxime ether fungicide SYP-Z071. Indene-substituted compounds had much better fungicidal activities for Eryiphe graminis (wheat powdery mildew) and Pseudoperonospora cubensis (cucumber downy mildew) than kresoxin-methyl. Some indene-substituted compounds also had insecticidal activity. Study of structure-reactivity relationship showed: (1) indene-substituted oxime ether compounds had higher fungicidal activity than the aryl substituted unsaturated oxime ether fungicide SYP-Z071 for some fungal diseases; (2)...