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Green Chemistry
Page 6 of 8
ARTICLE
Journal Name
formation of secondary and tertiary amines is less likely due to more detailed research on the influence of the reaction
a higher sterical hindrance.
conditions, elucidation of the kinetics anDdOpI:r1o0o.1f0o39f/cCo7nGcCe0p0t42f2oBr
The feasibility of formation of a 6-membered ring explains continuous processing are essential for future process
the high conversion of 90 % of pentane-1,5-diol with an development. Also the efficiency and environmental impact of
intramolecular ring closure. After a one-fold amination the ring the aqueous phase amination process have to be evaluated to
closure occurs during the N-alkylation reaction resulting in the assess and compare its performance regarding the principles
formation of a thermodynamically favored piperidine 6- of green chemistry and engineering. This issue is addressed in
membered ring with a selectivity of 95 %. In this special case ongoing work especially regarding an overall mass balance,
the production of piperidine has been mentioned before in the waste amounts and the overall energy requirements that can
patent literature based on copper and nickel catalysts for only be assessed with technical reliable data for the combined
reactions in the gas phase.46, 47 Nevertheless, the option to reactor and a suitable downstream processing.
carry out the reaction in liquid aqueous phase is still highly
advantageous.
Acknowledgements
The same effect was observed for the amination of hexane-
1,6-diol to hexamethylenediamine; a monomer of great
industrial importance in the production of Nylon 66. A
conversion of hydroxyl groups of up to 79 % was observed. As
We gratefully acknowledge financial support by the German
Federal Ministry of Food and Agriculture (FKZ: 22024111 and
22026615). We would like to thank Dr. A. Haji Begli and Dr. C.
Kröner from the company Südzucker AG for the fruitful
collaboration. Also, we thank Parr Instruments GmbH for
providing a Microbatch Reaction System (MBS) prototype for
catalytic screening experiments. Additionally, we thank the
analytical department of the ITMC for the continuous support
with the quantification of our reaction mixtures.
a
by-product the 7-membered heterocyclic alkyl amine
azepane was found. The production of hexamethylenediamine
from hexane-1,6-diol was used in the past by Celanese in an
industrial process until 1981.48 Also Evonik filed a patent for
this direct route based on Cu-Ni-Co catalysts supported on
ZrO2. However, both processes require a comparatively high
hydrogen pressure of up to 300 bar.48, 49 Hence, based on the
option to carry out the amination in the aqueous phase with
Ru/C as solid catalyst a high potential for efficient processing
conditions is revealed.
References
1
A. B. van Gysel and W. Musin, in Ullmanns's Encyclopedia
of Industrial Chemistry, Wiley-VCH, Weinheim, 2005.
S. A. Lawrence, Amines: Synthesis, Properties and
Application, Cambridge University Press, Cambridge,
2004.
2
Conclusions
In conclusion, we have presented the successful one-pot
amination of various biogenic alcohols using Ru/C as solid
catalyst. The influence of the catalyst was investigated in detail
based on the amination of the sugar-based diol isomannide.
Especially, the feasibility of using other support materials, that
are stable under the hydrothermal and basic conditions, was
proven. Also, it was shown that the activity and selectivity is
significantly influenced by using Ru-based bimetallic catalysts,
although elemental Ru/C is the most productive one.
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4
5
6
7
K. S. Hayes, Applied Catalysis A: General, 2001, 221, 187-
195.
K.-i. Shimizu, Catalysis Science & Technology, 2015, 5,
1412-1427.
M. H. S. A. Hamid, P. A. Slatford and J. M. J. Williams,
Advanced Synthesis & Catalysis, 2007, 349, 1555-1575.
C. Gunanathan and D. Milstein, Angewandte Chemie
International Edition, 2008, 47, 8661-8664.
J. C. Serrano-Ruiz, R. Luque and A. Sepulveda-Escribanoa,
Chem. Soc. Rev., 2011, 40, 5266-5281.
Most importantly, however, the reported catalytic systems
allow for the amination of primary and secondary alcohols at
temperatures below 200 °C and in aqueous solution. The
comparably low temperatures are of great interest for
biogenic sugar-based alcohols that often suffer from a limited
thermal stability. Being able to conduct the reaction in water
as solvent is essential regarding a holistic process development
and considering the fact that many biogenic alcohols can or
have to be produced in aqueous solutions. Hence, avoiding
one separation step of the alcohol intermediate from the
water is essential for the energy efficiency of such a process.
Thereby, a new access route towards biogenic amines
especially for monomers of novel bio-polyamides is exploited.
Is water a suitable solvent for the catalytic amination of
alcohols? For this route it can be answered with a “yes”.
Although it has to be considered that a suitable purification is
required to recycle or to dispose of the water after the process
especially regarding residual amines and ammonia. Overall,
8
9
P. Gallezot, Chem. Soc. Rev., 2012, 41, 1538-1558.
V. Froidevaux, C. Negrell, S. Caillol, J.-P. Pascault and B.
Boutevin, Chem. Rev., 2016, 116, 14181-14224.
M. Winnacker and B. Rieger, Macromol. Rapid Commun.,
2016, 37, 1391-1413.
I. Delidovich, P. J. C. Hausoul, L. Deng, R. Pfützenreuter,
M. Rose and R. Palkovits, Chem. Rev., 2016, 116, 1540-
1599.
M. Pera-Titus and F. Shi, ChemSusChem, 2014, 7, 720-722.
J.-Q. Li and P. G. Andersson, Chem. Commun., 2013, 49,
6131-6133.
M. Haniti S. A. Hamid, C. L. Allen, G. W. Lamb, A. C.
Maxwell, H. C. Maytum, A. J. A. Watson and J. M. J.
Williams, J. Am. Chem. Soc., 2009, 131, 1766-1774.
S. Bähn, S. Imm, L. Neubert, M. Zhang, H. Neumann and
M. Beller, ChemCatChem, 2011, 3, 1853-1864.
A. M. Rasero-Almansa, A. Corma, M. Iglesias and F.
Sánchez, ChemCatChem, 2014, 6, 1794-1800.
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14
15
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