2141-58-4Relevant academic research and scientific papers
Method of producing hexamethylene diamine from butadiene
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Page/Page column 3, (2008/06/13)
The invention relates to the production of hexamethylene diamine from butadiene. The method comprises the successively performed stages of: (i) a catalytic epoxidation of butadiene to 1,2-epoxy-3-butene; (ii) a basically catalyzed addition of hydrogen cyanide to butadiene monoxide to form a reaction mixture containing 3-hydroxy-4-pentene nitrile (3HPN) and 2-hydroxymethyl-3-butene nitrile (2HMBN); (iii) an acidically catalyzed dehydration of the cyanohydrines 3HPN and 2HMBN of stage (ii) to cis/trans-pentadiene nitrile (PDN); (iv) a basically catalyzed addition of the products of stage (iii) to form cis/trans-1,4-dicyanobutene-1 and -2 (DCB); and (v) a catalytic hydrogenation of the isomeric cis/trans-1,4-dicyanobutene of stage (iv) to hexamethylene diamine.
Tail-to-Tail Dimerization of Acrylonitrile Catalyzed by Low-Valent Ruthenium Complexes
Fukuoka, Atsushi,Nagano, Takeyuki,Furuta, Shuichi,Yoshizawa, Michito,Hirano, Masafumi,Komiya, Sanshiro
, p. 1409 - 1415 (2007/10/03)
Zero-valent ruthenium complexes, [Ru(cod)(cot)] and [Ru(cod)(benzene)], are effective catalyst precursors for the tail-to-tail dimerization of acrylonitrile. Hydrogen pressure is necessary for the catalytic reaction, and the turnover number for dimers is greatly improved in neat acrylonitrile. Under the conditions of 150 °C and 25 atm of H2 (initial pressure at room temperature), the conversion of acrylonitrile is 61% and the yield of tail-to-tail dimers is 42% (selectivity 69%) in 3 h. The turnover number for the dimers is 2060, which is much higher than those reported so far. From the results of a catalytic reaction under D2 pressure, a reaction mechanism is proposed, in which two successive insertions of acrylonitrile into dihydridoruthenium complex are involved. A fast and reversible insertion of the third acrylonitrile is responsible for the H-D exchange of acrylonitrile in the deuterium labeling experiment.
The kinetics and mechanism of the phosphorus-catalysed dimerisation of acrylonitrile
Hall, C. Dennis,Lowther, Nicholas,Tweedy, Bruce R.,Hall, Adam C.,Shaw, Gordon
, p. 2047 - 2054 (2007/10/03)
Isopropyl diarylphosphinites (Ar2POPri) catalyse the dimerisation of acrylonitrile (AN) to a mixture of cis- and trans-1,4-dicyanobut-1-ene (cis,trans-DCB-1), trans-1,4-dicyanobut-2-ene (DCB-2) and 2,4-dicyanobut-1-ene (MGN). The kinetics and mechanism of the reaction, which is a potential source of hexamethylenediamine, are reported in detail and the factors which govern rate and selectivity to DCB-1 and DCB-2 rather than MGN are elaborated.
