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The second chapter of this book provides information about all category of six membered ring system with N and/or O and /or sulfur atom, and their benzo derivatives. These six membered heterocycles and their benzo derivatives are not only present in drugs, vitamins, natural products, biomolecules, exhibiting antitumor, anti-inflammatory, anti-fungal, anti-bacterial, anti-depressant, anti-HIV anti-microbial, anti-malarial and anti-diabetic activities but they are also the key structural unit of pharmaceutical drugs and agrochemicals available in the market. Thus, each unit of this chapter gives due emphasis on the importance of a particular six membered heterocycle or its derivative under study in natural product, medicine and material. Each unit of the chapter also provides information about the structure of the individual heterocycle especially in terms of X-ray and spectroscopic data. After that synthesis, chemical reactivity and application of these heterocycles have been discussed. It is worth mentioning that wherever necessary, possible mechanism of the some typical reactions as well as name reactions have been discussed.