Studies On The Carbonylation Of Compounds Containing N Catalyzed By Selenium

One-pot oxidative-reductive carbonylation of nitrobenzenes with anilines can lead to formation of ureas with CO/Se as a catalytic system. Such a method can replace traditional reaction with phosgene as the carbonylation reagent, involving the toxic reagent and drastic reaction conditions, the new herein studied method is environmentally benignancy and has atom economical selectivity. Recently, it has attracted more and more attention and become one of the challenging and attractive subjects in the field of C1 chemistry.The purpose of this theme is to study the score and limitation of this new catalytic reaction, and synthetic methodology of ureas of N-heterocyclic ring contained, to carry out a simple and effective catalytic synthetic method through the carbonylation with CO and cheap selenium to give out a series of useful fine chemicals. Through adjusting the co-catalysts, further more, the reductive substitution reaction of aromatic acylamide and nitrobenzenes in the system of carbon monoxide catalyzed by selenium with l,8-diazabicyclo[5, 4, 0]undec-7-ene (DBU) was also discussed; The carbonylation of substituted aminopyrimidine and aminopyridine derivatives as co-reagent with substituted nitrobenzenes and thecarbonylation of o-nitrophenol were studied; The technology of hormonelike pesticides-Fenoxycarb and Pyripoxyfen was researched.The cyclic carbonylation of o-nitrophenol and carbon monoxide catalyzed by selenium with l,8-diazabicyclo[5, 4, 0]undec-7-ene and triethylamine as co-catalysts were carried out. All kinds of elements to influence such reaction were investigated, a new method to synthesize the derivatives of benzoxazolinone was proposed and the highest yield of such reaction at the present conditions reached to 80%; At the same reaction conditions, the yield of benzoxazinone through the cyclic carbonylation of 2-nitrobenzyl alcohol and carbon monoxide catalyzed by selenium with l,8-diazabicyclo[5, 4, 0]undec-7-ene and triethylamine as co-catalysts were got to 87%.The electron withdrawing group on the contraposition of amino can greatly influence the yieds of the carbonylation of substituted aminopyridine derivatives as co-reagents with substituted nitrobenzenes. A series of pyridinylureas were synthesized.The highest yield of the selenium-catalyzed carbonylation of substituted nitrobenzenes with substituted aminopyrimidines as co-reagents reached 90% or so. The influence of the position of amino associated with pyrimidine on the reaction yields was discussed. At the same time, the effects of the reaction conditions, including temperature, pressure of CO, catalyst amount, the sorts of bases as co-catalyst and the sorts of solvents were investigated also.The reductive substitution reaction of aromatic acylamide and nitrobenzenes in the system of carbon monoxide catalyzed by selenium with l,8-diazabicyclo[5, 4, 0]undec-7-ene (DBU) and triethylamine as co-catalysts was also discussed and plausible mechanism was postulated.The technology of hormonelike pesticides-Fenoxycarb and Pyripoxyfen was empoldered. The phase transfer catalysis reaction to synthesize l-aryloxy-2-propanols was investigated, the precious phase transfer catalyst-tetrabutylammonium bromide can be replaced by cheap PEG in thisreaction; Above all, the intermediate of Fenoxycarb -2-chloroethylcarbamicacid ethyl ester can be synthesized by carbonylation of chloroethylamine and alcohol with CO catalyzed by selenium.