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Palladium-catalyzed Coupling Reaction In The Polyethylene Glycol

Posted on:2012-12-10Degree:MasterType:Thesis
Country:ChinaCandidate:J LuFull Text:PDF
GTID:2131330335473907Subject:Organic Chemistry
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Green chemistry is to point to in manufacturing chemical products that should be effective used of raw material, eliminated waste and avoided using toxic and dangerous reagents. Green chemistry also says "environmentally friendly chemistry" or "clean chemistry". At present many countries of the world have already put "Green Chemistry" as one of the direction of chemical development in the new century.Polyethylene Gglycol (PEG) has been emerging as a promising green solvent and receiving more attention for both combinatorialas well as for heterogeneous catalysts. The viscosity of PEG at ambient and higher temperatures gives them significant advantage to use for all general operations. In recent years, PEG has emerged as alternative green reaction medium with unique properties such as low toxicity, thermal stability, inexpensive and nonvolatile. Many organic reactions have been carried out using PEG as solvent or co-solvent, such as Heck reaction, Suzuki-Miyaura cross-coupling reaction, oxidation, reduction, addition, and asymmetric aldo reaction. The use of PEG as a recyclable solvent system has also been reported. PEG is a biologically acceptable polymer which has been used extensively in drug delivery and in bioconjugates as tools for diagnostics. It is also being extensively used in organic substrates. Lower-molecular weight liquid PEGs can be used as solvents with or without addition of water. PEGs are stable at high temperatures up to 150-200℃and show higher stability in acidic and basic conditions. It has previously been suggested that PEGs could be used as complexing solvents of inorganic salts, in order to enhance the reactivity of the anion with the organic substrate. In these systems, the anion could be brought into solution with higher reactivity. Additionally, it may be possible by utilizing the unique physicochemical properties of PEGs to realize reactivity and/or selectivity that cannot be attained in organic solvents. The use of PEG as a reaction solvent has received considerable attention in synthetic organic chemistry.Using green reaction media is green chemistry demand, and is also one of the development directions of organic synthesis chemistry. With these content as the goal, this paper studies reaction with polyethylene glycol (PEG)-600 for solvent, so that greatly reduces the pollution to the environment and can be reused. We successfully used polyethylene glycol (PEG)-600 as solvent and palladium as a catalyst in the synthesis of phenyl phosphate and phenyl boric acid ester compounds under the conditions. This method is suitable for operaction and experimental simplicity and various substrates. Most of compounds were characterized by IR, 1HNMR and 13CNMR.Phosphorus compounds containing the C-P bond are not particularly abundant in nature. Their diverse biological activities have for a long time attracted considerable interest of synthetic and pharmacological. Arylphosphonates and their derivatives are important classes of compounds with applications in medicinal, organic, and polymer chemistries. Compounds containing arylphosphonate moieties are used in designing fuel cell membranes, materials with special optical properties and in the synthesis of heterocyclic compounds. In recent years there has been a growing interest in these classes of phosphorus compounds in medicinal chemistry and nucleic acid chemistry due to biological activity that the presence of a C-P bond can confer to many organic compounds. This work with palladium as catalysts, polyethylene glycol (PEG)-600 as solvent, temperature at 130℃, Et3N as alkali, Halogen benzenes and diethyl phosphite synthesize phenyl phosphates.Arylboronic acids and their esters are versatile intermediates in organic synthesis to construct carbon-carbon, carbon-nitrogen and carbon-oxygen bonds due to their unique reactivity and air stability. In addition, attention has recently also been paid to their applications in molecular recognition and pharmaceutical candidates owing to their high stability and low toxicity. Arylboronic acids and their esters have found increasing application in organic synthesis and medical treatments. In biology, medicine or materials science, aryl boronic esters have been used for hydrocarbon sensors, nucleosides and enzyme inhibitors, but also in some brain tumor patients in therapy for the treatment agent. Besides determination of phenylboronic acid can also be made of sugar sensor. This work with palladium as catalysts, polyethylene glycol (PEG)-600 as solvent, temperature at 90℃, NaNO2 as alkali, Halogen benzenes and B2pin2 synthesize phenyl boric acid ester compounds.The above two kinds of compounds are important containing C-P bond and C-B key materials, and playing an important role in organic synthetic chemistry. Therefore, the research synthesis method of containing C-P bond and C-B key compounds has the vital significance. With the development of environmental science urgently requires people to develop green environmental conditions of organic synthesis method. This topic in concluded on the basis of previous work, studies the polyethylene glycol (PEG)-600 applications in organic synthesis. This work with polyethylene glycol (PEG)-600 as solvent, palladium as catalysts synthesizes phenyl phosphate and phenyl boric acid ester compounds. This topic in the synthesis method is easy to operate, solvent non-toxic, can recycling. This new method with green environmental protection, will promote the development of green chemistry.
Keywords/Search Tags:Green chemistry, Polyethylene glycol(PEG), Arylphosphonates, Arylboronic esters
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