Physico-Chemical nanomaterials science
Catalytic reductive amination of furfural with dibutylamine at presence of the Cu-containing composite 

Asaula V. M.,1 Gavrilenko K. S.,2,3 Pariiska O. O.,1 
Ryabukhin S. V.,2,3 Volochnyuk D. M.,2,3,4 Kolotilov S. V.1,3

1 L.V. Pisarzhevskii Institute of Physical Chemistry of the NAS of Ukraine. Prospect Nauki, 31, Kyiv-03028, Ukraine. 
E-mail : vitaliy.asaula@gmail.com
2 Enamine Ltd, 78 Chervonotkatska str., Kyiv 02660, Ukraine
3 National Taras Shevchenko University of Kyiv, 60 Volodymyrska str., Kyiv, 01033, Ukraine
4 Institute of Organic Chemistry of the National Academy of Sciences of Ukraine, Murmanska str., 5, Kyiv, 02000, Ukraine

Furfural is one of the furan derivatives that attracts attention as a biobased alternative for the production of a wide range of chemicals, from antacids and fertilizers to plastics and dyes. Reductive amination of furfural can be considered as an additional route for preparation of valuable compounds from the renewable resources. This reaction is usually carried out with a help of catalysts containing ed noble metals. Total replacement of noble metals by cheaper readily available and less toxic analogues (such as 3d metals), possessing high catalytic activity, is important task of chemical manufacturing. This task can be fulfilled using composites of the non-precious metals and carboneous materials, in particular graphene-like ones. 
The aim of this study was to develop new platinum group metals-free catalyst for reductive amination of furfural with dibutylamine. The composite, containing metallic Cu and carboneous material, was chosen as the candidate for this study.
The composite was prepared by pyrolysis Cu(II) complex with N-containing ligands - melamine - deposited on activated carbon. The composite contained metallic Cu as crystalline phase. It was found by transmission electronic microscopy that copper nanoparticles had the size of ca. 10 - 40 nm. Analysis of the Raman spectral data allowed to conclude that the composite contained graphene-like carboneous species. 
The catalytic activity of the obtained composite was tested in reaction of furfural with dibutylamine under H2 pressure (5 atm, 30°C). The reaction products were analyzed by 1H NMR and gas chromatogrpahy. It was found that the N-butyl-N-(tetrahydrofuran-2-ylmethyl)butan-1-amine formed with ca. 83 % yield, while N-butyl-N-(furan-2-ylmethyl)butan-1-amine was the minor product.  
This work has been partially funded by the NAS of Ukraine (Grant 0120U100182)