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Green Chemistry
Page 6 of 7
DOI: 10.1039/C7GC02838E
ARTICLE
Green Chemistry
alcohols are intermediates. 53 We propose that the low energy
pathways will follow Steps A-D or E-H then C, D (Scheme 2).
Three of the compounds observed after shorter reaction times
4
5
P. W. Zheng, X. M. Duan, W. Wang, X. J. Wang, Y. P. Guo
and Q. D. Tu, Chinese J. Chem., 2006, 24, 825.
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Leitner, A. M. Z. Slawin and D. J. Cole-Hamilton, Chem. Eur.
J., 2013, 19, 11039.
(
10,
16 and 17) are contained within these two alternative
, is not within either pathway,
pathways. The diamide,
9
consistent with its being observed after short reaction times,
6
7
8
9
B. Zeynizadeh and M. Zabihzadeh, J. Iran. Chem. Soc., 2015,
12, 1221.
being formed by amidation of 16, being hydrogenated to give
1
but not reacting as fast as the diacid. However, control
R. J. Maya, S. Poulose, J. John and R. L. Varma, Adv. Synth.
Catal., 2017, 359, 1177.
reactions omitting aniline produce diol with high selectivity
under the same reaction conditions as used for amine
formation (Table 1, entry 5). Starting with diol and aniline
under the same conditions gave 98 % yield of the desired
H. Huang, Y. Zhao, Y. Yang, L. Zhou and M. Chang, Org. Lett.,
2017, 19, 1942.
Q. Yang, Q. Wang and Z. Yu, Chem. Soc. Rev., 2015, 44,
2305.
diamine, 1, after 20 hours (Table 4, entry 1). Thus, we cannot
exclude pathways including alcohols, since the rapid rate of 10
alcohol consumption would mean that the standing
G. Guillena, D. Ramon and M. Yus, Chem. Rev., 2010, 110,
1611.
concentration of alcohol intermediates would be very small.
11
12
13
14
15
16
17
18
J. J. A. Celaje, X. Zhang, F. Zhang, L. Kam, J. R. Herron and T.
J. Williams, ACS Catal., 2017, 7, 1136.
X.-J. Yu, H.-Y. He, L. Yang, H.-Y. Fu, X.-L. Zheng, H. Chen and
R.-X. Li, Catal. Commun., 2017, 95, 54.
Conclusions
R. Mamidala, V. Mukundam, K. Dhanunjayarao and K.
Venkatasubbaiah, Tetrahedron, 2017, 73, 2225.
N. Nakagawa, E. J. Derrah, M. Schelwies, F. Rominger, O.
Trapp and T. Schaub, Dalt. Trans., 2016, 45, 6856.
S. Elangovan, J. Neumann, J.-B. Sortais, K. Junge, C. Darcel
and M. Beller, Nat. Commun., 2016, 7, 12641.
A. A. Núñez Magro, G. R. Eastham and D. J. Cole-Hamilton,
Chem. Commun., 2007, 3154.
The hydrogenation of dicarboxylic acids and their esters in the
presence of amines provides a new methodology for the
synthesis of α,ω-diamines. Reaction of dicarboxylic acids and
their derivatives with aniline in the presence of [Ru(acac)3] and
1,1,1-tris(diphenylphosphinomethyl)ethane (triphos) gave
good to excellent yields of the N-phenyl diamines with 8 to 19
carbon chains. Although primary diamines could not be
obtained in a similar way using aqueous ammonia in place of
aniline, they were formed from the reaction between diols and
aqueous ammonia in very good yield and selectivity. They
could also be formed in good yield by a sequential one pot
reaction involving hydrogenation of the diacid or diester to the
diol, addition of aqueous ammonia and further reaction to the
diamine using the same catalyst. Renewable feedstocks can
hence be converted to important precursors to polyamides.
I. Sorribes, J. R. Cabrero-Antonino, C. Vicent, K. Junge and
M. Beller, J. Am. Chem. Soc., 2015, 137, 13580.
T. Toyao, S. M. A. H. Siddiki, Y. Morita, T. Kamachi, A. S.
Touchy, W. Onodera, K. Kon, S. Furukawa, H. Ariga, K.
Asakura, K. Yoshizawa and K. Shimizu, Chem. Eur. J., 2017,
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20
21
22
23
24
I. Sorribes, K. Junge and M. Beller, J. Am. Chem. Soc., 2014,
136, 14314.
M. Minakawa, M. Okubo and M. Kawatsura, Tetrahedron
Lett., 2016, 57, 4187.
Conflicts of interest
K. G. Andrews, D. M. Summers, L. J. Donnelly and R. M.
Denton, Chem. Commun., 2016, 52, 1855.
M.-C. Fu, R. Shang, W.-M. Cheng and Y. Fu, Angew. Chem.
Int. Ed., 2015, 54, 9042.
There are no conflicts to declare.
Acknowledgements
F. Stemp, D. Quinzler, I. Heckler and S. Mecking,
Macromolecules, 2011, 44, 4159.
We thank the EPSRC for the critical mass grant 'Clean Catalysis
for Sustainable Development' (EP/J018139/1), Sasol
Technology, UK for a case studentship (Y. S.) and the EPSRC UK
National Mass Spectrometry Facility at Swansea University for
mass spectrometric analysis
Y. Shi, P. C. J. Kamer, D. J. Cole-Hamilton, M. Harvie, E. F.
Baxter, K. J. C. Lim and P. Pogorzelec, Chem. Sci., 2017, 8,
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Wang and K. Whiston, Chem. Commun., 1999, 1877.
C. J. Rodriguez, D. F. Foster, R. Eastham and D. J. Cole-
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F. Stempfle, P. Roesle and S. Mecking, in Biobased
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6 | J. Name., 2012, 00, 1-3
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