Environmentally Friendly Synthesis Of Homopropargyl Alcohols Mediated By Zn-Cu Couple

After 1985s, it realized that pollution prevention and cleaner production can be gradually increased, by changing the product design and the route of production process so that it did not generate harmful intermediate products and by-products, in order to achieve wastes or emissions internal circulation, to minimize pollution, conserve resources and energy purposes. In the early 1990s, the chemists put forward the concept of "green chemistry". Green chemistry is that apply the chemical techniques and methods to reduce or eliminate the use and generation of harmful materials, catalysts, solvents and reagents, the product, by-products those on human health, social security, ecological environment. The center questions of this research which are at to achieve the technical requirements of economic rationality, while attain a chemical reaction and its product has the following characteristics: (1) the use of harmless non-toxic raw materials or renewable resources; (2) the reaction conditions under the non-toxic harmless; (3) the reaction is enable to have highly selectivity, with minimal by-products, even attain to the extent of the "atom economy", that is, achieve 100% selectivity and "zero emissions" of the wastes; (4) the products is environmentally friendly. Green Chemistry, with the view of science, require the chemists to look at the traditional chemical research and chemical processes from a new perspective, it is the practice of basic chemical disciplines content; with the view of environment, it is the elimination of pollution at the source; with the view of economy, the rational use of resources and energy, reduce production costs; With the rapidly emerging and development of green chemistry, environmentally friendly-economics have become an important impetus of technology innovator, and make green organic synthesis face serious challenge. Developing more benign synthetic procedures in chemical synthesis is important in moving towards sustainable technologies. In reducing the amount of waste, energy usage, and the use of volatile, toxic and flammable solvents, several approaches are available including avoiding the use of organic solvents for the reaction media. Replacement media include non-volatile and recyclable ionic liquids, H2O, supercritical CO2, polyethylene and polypropulene glycol. An alternative approach avoids the use of a reaction medium as the so-called'solvent free'or'solventless'reaction.Being important building blocks and versatile synthons, homopropargyl alcohols are highly featured in the organic syntheses of many biological active molecules such as macrolides, polyhydroxylated natural products, and polyether antibiotics. Among the existing means to construct these synthetically and biologically important molecules, metal-mediated propargylation is one of the easiest and most convenient.From the view of environmentally friendly, this thesis achieved the solvent-free synthesis of homopropargyl alcohols through Zn-Cu couple mediated Barbier-Type reaction.This thesis includes three chapters:Chapter one: A Study on the Progress of Reaction for Carbon-Carbon Triple Bond FormationCarbon-carbon triple bond formation is the one of important reactions in organic synthesis. This chapter mainly investigated the recent progress in the formation carbon-carbon triple bond, especially depicted and reviewed the propargylation reaction of carbonyl compounds in detail.Chapter two: Study on Environmentally Friendly Reaction of Aldehydes and Propargyl Bromide Mediated by Zn-Cu coupleThis chapter summarized Barbier-Type reaction of aldehydes and propargyl bromide mediated by Zn-Cu couple under solvent-free conditions. The synthesis of homopropargyl alcohols can be achieved environmentally friendly through Zn-Cu couple mediated propargylation of carbonyl compounds without formation homoallenyl alcohols which detected by 1H-NMR. Compared to literature methods, the advantages of our methodology are moderate reaction conditions, shorter reaction time, higher yield and broader substrate scope.Chapter three: Study on Environmentally Friendly Reaction of Ketones and Propargyl Bromide Mediated by Zn-Cu coupleIn this section, we further studied the propargylation reaction of ketones at the basis of Barbier-Type reaction of aldehydes and propargyl bromide mediated by Zn-Cu couple under solvent-free conditions. homopropargyl alcohols also can be achieved environmentally friendly with formation homoallenyl alcohols which detected by 1H-NMR at room temperature, homopropargyl alcohols were produced as the unique product at -14oC ~ -16oC except the substrate was the benzophenone. Compared to literature methods, the advantages of our methodology are including simple procedure, shorter reaction time, higher yield and broader substrate scope. This is the excellent method for synthesis homopropargyl alcohols environmentally friendly under solvent-free conditions.