Hydration Of Acetonitrile And Terminal Alkynes And Cyclotrimerization Of Alkynes Catalyzed By Ruthenium Complexes

Organic reactions often needs long reaction time and forms many side products, some reaction even requires a high temperature, high pressure and a catalyst. Traditional catalysts of nitrile and terminal alkyne hydration such as mercury salt in strong acid environment, not only pollute the environment, but also damage to the human body. The development of new hydration of nitriles and terminal alkynes catalyst has major significance. Ruthenium bipyridine complex can promote chemical reactions, especially involved in the promotion of photocatalytic and electron transfer reactions. In this paper, the hydration of acetonitrile and terminal alkynes catalyzed by the Ru (II) complexes, which was used instead of mercury, was studied. At the same tme, three novel water soluble Ru(III) complexes were synthesized, and their role on catalyzed cyclotrimerization of1-hexyne, phenylacetylene and ethyl propiolate was discussed. As to now, the catalyzed hydration of nitrile and terminal alkynes by bipyridine ruthenium complexes are known little.The main work can be summarized as follows:1. Synthesis of bipyridine ligand. With2-amino-6-methyl-pyridine as the feedstock through a diazotization reaction to generate the2-bromo-6-methyl-pyridine, followed by the symmetrical coupling reaction to generate the ligand6,6’-dimethyl-2,2’-bipyridine (dmbp). Then the ligand of dmbp oxidise to the ligand of2,2’-bipyridine-6,6’-dicarbaldehyde (bpda).2. Ruthenium complexes Cis-[RuⅡ(L)2Cl2]·2H2O (L=bipy, dmbp, bpda), were synthesized by the reaction of RuCl3·3H2O and the ligands2,2’-bipyridine (bipy), dmbp, bpda, respectively, in the reducing solvent DMF. Then dechlorination by AgOTf (OTf=CF3SO3) to get Cis-[RuⅡ(L)2(H2O)2](OTf)2. Finally, in the presence of DBU (1,8-Diazabicyclo [5.4.0] undec-7-ene), three novel water-soluble hydroxide ruthenium complexes Cis-[(RuⅡ(L)2(H2O)(OH)](OTf) were synthesized by deprotonation of Cis-[(RuⅡ(L)2(H2O)2](OTf)2. The hydration of acetonitrile to generating amide, and hydration of1-hexyne, phenyl acetylene and ethyl propiolate to generate the anti-Markovnikov rule products aldehydes catalyzed by Cis-[RuⅡ (L)2(H2O)(OH)](OTf) were studied. 3. Ruthenium complexes Cis-[RuⅢ(L)2Cl2]Cl·2H2O were synthesized by the reaction of RuCl3·3H2O and the ligands bipy, dmbp,and bpda. Further AgOTf was used to dechlorination of Cis-[RuⅢ(L)2Cl2]Cl·2H2O to get Cis-[Ru(L)2(H2O)2](OTf)3. Cyclotrimerization reaction of1-hexyne, phenylacetylene and ethyl propiolate, catalyzed by Cis-[Ru(L)2(H2O)2](OTf)3, was studied.