10.1002/cssc.202000003
ChemSusChem
COMMUNICATION
Table 5. Catalytic conversion of furfural to furanic amine by one-reactor, two-step process[a]
Ketone
Time
1st
Yield / %
Carbon balance / %
NH3
/ g
Entry
Reagent
Catalyst
H2 /bar
Unsaturated
furanic
2nd
Amine
ketone
1
2
3
4
5
1a
-
Ru/C
14
0.3
0.3
0.3
0.3
0.3
0.3
0.3
15
15
15
30
15
15
15
< 1 (2a)
7 (2a)
6 (2a)
3 (2a)
18 (2a)
33
95 (2b)
71 (2b)
70 (2b)
74 (2b)
9 (2b)
95
78
76
77
27
58
80
Furfural
Furfural
Furfural
Furfural
Furfural
Furfural
MIBK
Ru/C + A26
Ru/C + A26
Ru/C + A26
Ru/C + A26
Ru/C + A26
Ru/C + A26
4
4
4
16
24
16
MIBK
MIBK
MIBK
14
6[b]
2-pentanone
2-heptanone
1.5
1.5
6
25 (3b)
57 (4b)
7[b]
14
23
[a] The furfural conversion was 100 % for all the reactions. (1st) All runs were carried out at 100 °C in 1 g EtOH with 162 mg furfural while keeping the molar ratio
of ketone:furfural – 1:1 and the mass ratio of base/furfural 40 wt%, 30 mg Ru/C; (2nd) the reductive amination reactions were all following the first step of aldol
condensation by inserting NH3 and H2.[b] not optimized result.
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In summary, we demonstrated that a new family of furan-derived
primary amines could be selectively prepared (95%) from bio-
derived ketones using NH3 as a nitrogen source, molecular H2 as
a reducing agent and commercially available Ru/C as catalyst.
This system efficiently catalyzed the hydrogenation of C=C bonds
together with the reductive amination of carbonyl groups at mild
reaction conditions. Besides, the catalyst remains stable during
the reaction for at least 4 consecutive runs. We also demonstrated
that furfural could be directly converted into furan-derived primary
amines by a one-reactor two-step process, achieving a high yield
of 74% and that it can be extended to other ketones than MIBK
(not optimized results). Thus our present work leads to the
production of opens a new avenue for producing biomass-derived
amines from products of biomass processing with potential
application as biosolvents or biosurfactants. Also, this work
provides a toolbox that enables the conversion of furfural into the
desired amine. The deposition of ruthenium species over a
multifunctional support, the design of a continuous flow process
and the transposition of the current results to a variety of amines
are topics under investigation.
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The authors would like to thank the French ANR agency for the
funding of FurCab Project ANR-15-CE07-0016. The authors are
also grateful to the Région Nouvelle Aquitaine for the funding of
this project through the FR CNRS INCREASE 3707, the chair
TECHNOGREEN and FEDER.
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Keywords: Amines • Biomass • Catalyst • Furfural • Ketones
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