Study On The Reaction Of Alkynes Hydroamination And Homocoupling In The Condition Of Microwave Promotion

In this paper, we surveyed a lot of literatures on the basis of alkynes hydroamination reaction and coupling reaction, as well as the synthesis of propiolic acid ester, and put forward the design thought of this thesis.1. In this paper, alkynes hydroamination reaction of Dimethyl acetylenedicarboxylate, Ethyl propiolate, Methyl propiolate,3-butyne-2-ketone were put in the condition of microwave irradiation, the products of E-enamine were obtained in the high selectivity, and studyed the influence of different alkynes and various substituted amines to the activity of alkyne hydroamination addition reaction. And we found that the same product obtained between Dimethyl acetylenedicarboxylate reacting with DMF which was treated with sodium and not done with sodium, through designing the experiment, we proposed two kinds of mechanism of reaction between Dimethyl acetylenedicarboxylate and DMF.2. In this paper, we found that Phenylacetylene and4-Fluorophenylacetylene could generate conjugated diynes efficiently and highly yield by the catalyst of anhydrous cupric chloride. Propiolic acid ester under Microwave Promotion condition with two hydrated cupric chloride as catalyst or at room temperature with organic base N-methyl morpholine as catalyst to generate E-conjugated enynes in high yields. While in the condition of microwave irradiation, propargyl ester with organic base N-methyl morpholine as catalyst, but got another product of vinyl ether, so different products were obtained by changing the reaction conditions, this was a research about controllable reaction. At the same time, this paper conducted a preliminary exploration on these reaction mechanisms.3. This paper studied the using of dehydrating agent Dicyclohexylcarbodiimide (DCC) to catalyze esterification between propionic acid and phenol alcohol compounds at low temperature. Compared with the traditional esterification by the sulfuric acid as dehydrating agent, this method had less side reaction and obtained high yields. The yields of propiolic acid ester were related with the substituted groups on the phenols, high yields of propiolic acid ester were obtained when the phenols’ para-position existing electron-donating substituent. And bilateral propiolic acid esters were synthesized in the high selectivity by using such method.