Modulating: Trans -imination and hydrogenation towards the highly selective production of primary diamines from dialdehydes

Article abstract of DOI:10.1039/d0gc02280b

Bio-based primary diamines are important building blocks for sustainable bio-polymers, but their synthesis remains challenging due to the high susceptibility to polymerization. Herein, we have developed a new strategy to suppress the polymerization by employing a more nucleophilic alkylamine to scavenge the dialdehyde and a Co/ZrO2 catalyst to regulate the trans-imination and hydrogenation activity. With this strategy, 2,5-bis(aminomethyl)furan (BAMF), a promising monomer for the production of new polyamides and polyureas, is successfully synthesized via the reductive amination of biomass-derived 2,5-diformylfuran (DFF) under a H2 and NH3 atmosphere with an unprecedentedly high selectivity up to 95%. This strategy is applicable to the reductive amination of other biomass-derived dialdehydes, thus paving a new way to bio-based diamine monomers. This journal is

Full text of DOI:10.1039/d0gc02280b

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DOI: 10.1039/D0GC02280B
ARTICLE
Modulating trans-imination and hydrogenation towards the
highly selective production of primary diamines from dialdehydes
Received 00th January 20xx,
Accepted 00th January 20xx
a,b
a
a
a
a
a,b
a
a,c
Haifeng Qi, Fei Liu,* Leilei Zhang, Lin Li, Yang Su, Jingyi Yang, Rui Hao, Aiqin Wang* and
a,c
Tao Zhang,
DOI: 10.1039/x0xx00000x
Bio-based primary diamines are important building blocks for sustainable bio-polymers, but their synthesis remains
challenging due to the high susceptibility to polymerization. Herein, we develop a new strategy to suppress the
2
polymerization by employing more nucleophilic alkylamine to arrest dialdehyde and Co/ZrO catalyst to regulate the trans-
imination and hydrogenation activity. With this strategy, 2,5-bis(aminomethyl)furan (BAMF), a promising monomer for
production of new polyamides and polyureas, is successfully synthesized via reductive amination of biomass-derived 2,5-
2 3
diformylfuran (DFF) under H and NH atmosphere with an unprecedentedly high selectivity up to 95%. This strategy is
applicable to the reductive amination of other biomass-derived dialdehydes, thus paving a new way to the bio-based
diamine monomers.
obtained by oxidation of HMF, and got only 42.6% yield of
BAMF along with the formation of a large amount of oligomers
Introduction
1
6
and polymers over Raney Ni catalyst. Zhou et al. reported a
slightly higher yield of BAMF (60.7%) by directly using HMF as
Primary diamines are an important category of organonitrogen
chemicals. Beyond acting as key intermediates for synthesis of
pharmaceuticals and agrochemicals, they are more widely
used as monomers for production of polyamides and
polyureas.1 For example, 1,6-hexanediamine (HDA) is the
building block for production of PA-6,6, a commercial
1
7
the substrate. Recently, Shi and coworkers achieved a greatly
enhanced BAMF yield (85.9%) by means of a two-stage
1
8
consecutive reaction process;
nevertheless, the yield
-6
decreased dramatically to 63.7% during the third reuse and
the mass balance was also less than 70%, indicating the
occurrence of polymerization. Obviously, in spite of ready
availability of dialdehydes from biomass, the reductive
amination of dialdehydes remains a prohibitive challenge.
Therefore, it is keenly desired to innovate catalytic strategy
towards the highly selective production of primary diamines
from dialdehydes.
7
polyamide with annual production of several million tons.
While the current production of diamines is mainly based on
petroleum, there is great impetus to develop bio-based
diamines due to the ever increased concerns on the depletion
7
-10
of petroleum as well as the associated CO
Among a variety of potential bio-based diamine monomers,
,5-bis(aminomethyl)furan (BAMF) is one of the most
promising diamines as it can offer versatile possibilities in
2
emissions.
2
1
1-13
constructing new bio-polymers with distinctive functions.
In principle, BAMF can be produced from renewable
lignocellulose from the key platform molecule 5-
hydroxymethylfurfural (HMF) via reductive amination under H
2
1
1-15
and NH
3
atmosphere (Scheme 1a).
Unfortunately, the
selectivity to BAMF is far less satisfactory due to the high
propensity of diamines to polymerization with dialdehydes.
For example, Kim and coworkers investigated the direct
reductive amination of 2,5-diformylfuran (DFF), a dialdehyde
Scheme 1. Different approaches to BAMF from HMF.
Based on the reaction mechanism of the reductive
1
9-24
a. CAS Key Laboratory of Science and Technology on Applied Catalysis, Dalian
amination of aldehydes,
imines are formed first as the key
Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023
intermediate to the target primary amines even without
catalyst. However, this imination reaction is reversible, and the
primary amines are more nucleophilic than ammonia and
thereby tend to react with aldehydes to produce secondary
and ternary amines. What’s worse, in the case of dialdehydes,
(China), Email: aqwang@dicp.ac.cn; fei.liu@dicp.ac.cn.
b.
c.
University of Chinese Academy of Sciences, Beijing 100049 (China).
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese
Academy of Sciences, Dalian 116023 (China).
Electronic Supplementary Information (ESI) available: Experimental details,
catalyst characterization and tests. See DOI: 10.1039/x0xx00000x
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the primary di-imine intermediates are also prone to condense the support nature, e.g., redox or acid/base, does not
View Article Online
DOI: 10.1039/D0GC02280B
into oligomers before being hydrogenated into primary significantly affect the catalytic performance (entry 1-4)
diamines.16 In order to suppress these side reactions, the provided that the Co species is completely reduced to metallic
2
concentration of primary di-imines must be kept very low and phase and highly dispersed on the support surface (see H -TPR,
the unwanted high reactivity of the dialdehydes must be HRTEM and in-situ XRD, Fig 1 and Fig. S2-3). Different from Co
limited. In light of the higher nucleophilicity of alkylamine than and Ni, Cu was inactive at all for the reductive amination of
2
5-29
ammonia and the reversibility of trans-imination,
we DFF. In stark contrast to Co and Ni, all the noble metal
envisage that by using alkylamine as a scavenger of dialdehyde catalysts except for Ru failed to give BAMF (entry 8-11);
and transition metal catalyst as a modulator to regulate the instead, they preferentially catalysed the hydrogenation of
trans-imination and hydrogenation activity (Scheme 1b), side secondary di-imine, leading to the formation of N -butyl-2,5-
1
reactions between highly reactive dialdehyde and diamines bis(aminomethyl)furan
would be suppressed to a great extent so that high yields of bis(aminomethyl)furan (DBAF, 4a) or
(BBAF,
3a),
N
N
1
,N
,N
2
-dibutyl-2,5-
-dibutyl-2,5-
1
2
diamines might be achieved.
bis(aminomethyl)tetrohydrofuran (DBATHF, 5a) as the main
products. These results suggest that the hydrogenating
capability of noble metals is too strong to allow for the trans-
Results and discussion
imination between the secondary di-imine and NH
3
. Distinctive
from the other noble metals, Ru/ZrO offered a moderate
2
Reductive amination under the presence of butylamine
selectivity to BAMF (56%, and the optimization of solvent and
butylamine amount see Fig. S4 and Fig. S5) under the presence
of n-butylamine, in accordance with the superior activity of Ru
Table 1. Reductive amination of DFF over supported metal catalystsa
1
9, 20, 23
for reductive amination reactions.
Yield (%)c
Entry
Catalysts
2
91
95
85
73
75
n.d.
56
n.d.
n.d.
n.d.
n.d.
a
3a
3
4
n.d.
n.d.
5
n.d.
12
3
4a
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
68
5a
1
2
3
4
5
6
7
8
9
Co/ZrO
Co/ZrO
2
-R623
-R673
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
n.d.
16
2
Co/Nb
Co/SiO
Ni/ZrO
2
O
5
2
2
Cu/ZrO
Ru/ZrO
Pd/ZrO
2
2
2
2 2
Figure 1. H -TPR profile (a) and HAADF-STEM image (b) of Co/ZrO catalyst.
The success of this strategy is highly dependent on the
employment of alkylamine as the DFF scavenger. Without
alkylamine, one did not obtain any target product but only the
formation of a large amount of oligmers and polymers (Fig. S6)
irrespective of the catalyst nature. Moreover, short-chain
aliphatic amines that are more rapidly reactive with DFF
showed the more favourable effect in promoting the
formation of BAMF (Fig. S7), confirming the key role of
alkylamine as a scavenger in suppressing the polymerization
reactions. More importantly, during the reaction the
alkyamine was consumed only to a negligible extent (<5%),
which allows for its good recycling.
Pt/ZrO
2
12
7
65
61
n.d.
n.d.
63
1
1
0
1
Ir/ZrO
2
Rh/ZrO
2
5
25
aReaction conditions: 30 mg catalyst, 0.25 mmol DFF, 0.75 mmol butylamine, 3 g
methanol, 0.6 MPa NH
3
, 2 MPa H
2
, 373 K, 10 h, dodecane as internal standard;
n.d.: not detected; The catalyst was pre-reduced at 673 K. The conversions of
DFF were all >99%, and other products were oligomers and polymers.
b
c
We first investigated the reactivities of different alkylamines
with DFF to evaluate their capabilities for scavenging
dialdehydes. Short-chain aliphatic amines such as n-
propylamine and n-butylamine are able to react rapidly with
DFF immediately upon their mixing at RT, giving quantitative
formation of secondary di-imines (Schiff base) and
demonstrating their outstanding capability for scavenging
dialdehydes (Fig. S1). In contrast, either the long-chain
aliphatic amine (e.g., oleylamine) or secondary amine cannot
fast scavenge dialdehyde. With the suitable scavenger in hand,
we then evaluate various transition metal catalysts for the
reductive amination of DFF to BAMF under the presence of
excess amount of n-butylamine. To our delight, base metal
catalysts including Co and Ni delivered promising activity and
Modulating trans-imination and hydrogenation
2
selectivity to BAMF (Table 1); in particular, Co/ZrO afforded
Figure 2. Reaction kinetic profiles for the reductive amination of DFF over (a) Co/ZrO
2
the highest BAMF yield (95%, entry 2) hitherto. It appears that and (b) Pd/ZrO2 catalysts. Reaction conditions: 30 mg catalyst, 0.25 mmol DFF, 0.75
2
| Green Chem., 2013, 00, 1-3
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mmol butylamine, 3 g methanol, 0.6 MPa NH
standard.
3 2
, 2 MPa H , 373 K, dodecane as internal
uptake whereas Pd/ZrO
with H
interaction of Co with H
2
still maintained strong adsorption
. These results imply that the relatively weak
View Article Online
DOI: 10.1039/D0GC02280B
2
2
leave room for the trans-imination
Besides the key role of alkylamine in arresting DFF, the
capability of catalyst for modulating the trans-imination and
hydrogenation is another key factor governing the reaction
selectivity. Table 1 has clearly shown the dramatic difference
in BAMF selectivity achieved on various metal catalysts, which
should be due to their different capability for modulating the
trans-imination and hydrogenation activity. In order to
understand this process, we studied the reaction kinetics over
beween 6a and NH
3
, which agrees well with the calculation
17
result reported on Ni. Kinetically, the primary imine is easier
to be hydrogenated than the secondary imine. Even NH3
deactivates the strong hydrogenation sites of the Co/ZrO2
catalyst, the hydrogenation of primary imine can still proceed
on weak hydrogenation sites. To further demonstrate the
2
ability of Co/ZrO to modulate the trans-imination and
hydrogenation activity, we then used cyclopentanone as the
substrate as its single functional group would allow for the
detection of primary imine. When the secondary imine 1b
reacted with NH over Co/ZrO , primary imine 2b was formed
3 2
as a result of trans-imination with a selectivity of 22% (the
2 2 2
Co/ZrO and Pd/ZrO catalysts (Fig. 2). In the case of Co/ZrO ,
the secondary di-imine 6a was detected as the predominant
intermediate at the beginning stage as a result of the fast
reaction between n-butylamine and DFF, and it was then
3
gradually consumed through trans-imination with NH to form
other 78% was oligmer, Fig. S11). Then, the mixture of 1b and
the primary imine and di-imine, which, upon being produced,
must be immediately hydrogenated to the secondary
intermediate 7a and the final BAMF product (2a). During the
whole process, only a negligible amount of 3a was detected
implyting that the direct hydrogenation of secondary imine or
di-imine was sucessfully suppressed. In stark contrast to
2
2
b was submitted to hydrogenation over the Co/ZrO , and it
was found that the hydrogenation of 1b was completely
suppressed while 2b could be smoothly hydrogenated to the
corresponding amine (Fig. S12). This result strongly suggests
that, the competitive adsorption of the primary imine over the
bulky secondary imine promote the preferential
hydrogenation of the former, which in turn drive the trans-
imination equilibrium to the primary imine side, and
consequently lead to the high selectivity to the primary amine.
2 2
Co/ZrO , Pd/ZrO exhibits quite a different kinetic profile.
Owing to the super-capability of Pd for hydrogenation, the
secondary di-imine 6a, upon being formed, was instantly
hydrogenated to the secondary diamine (4a), which almost
completely prevented the occurrence of trans-imination, and
consequently the formation of primary diamine. Therefore,
2
the high selectivity of Co/ZrO can be attributed to its unique
capablity in modulating trans-imination and hydrogenation
activity of the Schiff base. The control experiment (Fig. S8)
revealed that, while DFF was quantitatively transformed into
6
a under the presence of n-butylamine and N
approximately 10% yield of 6a was obtained when NH
added to the system, along with the formation of a large
2
, only
3
was
amount of dark brown oligomers and polymers (Fig. S9). This Figure 3. Differential adsorption heat of H2 and NH3 as a function of coverage on
2 2 2
result suggests the occurence of trans-imination reaction Co/ZrO , Pd/ZrO and ZrO samples.
between 6a and NH , which leads to the slow formation of
3
primary di-imine (8a) and then causes the polymerization in Reaction mechanism
case 8a is not hydrogenated immediately. Furthermore, when
Based on these results, we propose the reaction mechanism
illustrated in Scheme 2. In the first step, the excess amount of
n-butylamine reacts quickly with DFF, forming secondary di-
imine (6a), by which all the unwanted reactions associated
with DFF such as condensation and polymerization can be
completely prevented. Then, reversible trans-imination took
we directly used Schiff base 6a as the substrate to investigate
the trans-imination behavior with or without catalyst (Fig. S10),
we found that the Co/ZrO catalyst could make the trans-
2
imination reaction more sluggish, leading to a slower
formation rate of the primary di-imine (8a), which is definitely
favorable to the suppression of polymerization reactions
associated with 8a.
3
place between 6a and 8a under the presence of NH , which
results in the sluggish formation of primary di-imine (8a) due
to the higher stability of 6a than 8a. Immediately upon its
formation, 8a can be instantly hydrogenated to the primary
diamine BAMF. During the whole reaction process the highly
reactive primary di-imine 8a was not detected (Fig. 2),
indicating it was consumed very rapidly by the subsequent
hydrogenation. The nearly zero concentration of 8a during the
whole reaction process could also successfully avoid its
condensation with the product 2a. It should be emphasized
In order to understand the unique capability of Co/ZrO
modulating the trans-imination and hydrogenation activity, we
2
for
subsequently measured the adsorption capablity for H
NH . As shown in Fig. 3 and Table S1, both Co/ZrO
Pd/ZrO exhibit strong adsorption capacity for NH
mainly reflects the strong interaction of support ZrO with NH
In contrast, they show different adsorption strength towards
; Pd/ZrO adsorbs H more strongly with a higher adsorption
heat and much more uptake than Co/ZrO . Moreover, after
pre-adsorption of NH , Co/ZrO did not show discernable H
2
and
and
3
2
2
3
, which
2
3
.
H
2
2
2
2
3
that the higher nucleophilicity of butylamine than NH not only
3
2
2
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Green Chem., 2013, 00, 1-3 | 3
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ensure the DFF react preferentially with butylamine instead of strategy is also applicable to the reductive amViinewatAiroticnle Oonflinae
NH
, but also gurantee the subsequent trans-imination broad scope of dialdehydes. As shownDiOnI:T1a0b.1l0e392/D, 0GaCro0m22a8t0iBc
proceed slowly towards the primary mono- and di-imine. On and cycloalkane dialdehydes substrates, which are potentially
3
3
0, 31
the other hand, the employment of Co/ZrO
2
catalyst enable derived from lignocellulose,
could be successfully
the trans-imination to proceed favorably over the transformed into the corresponding primary diamines with
hydrogenation of bulky secondary di-imine due to stronger excellent yields. More importantly, aliphatic dialdehydes such
adsorption of NH
the subsequent hydrogenation of the primary di-imine. in 63% yield, which provides an alternative pathway to HDA.
Moreover, the much lower concentration of 2a than NH in the
reaction system and the more bulky 2a than NH hinder the
reaction between 2a and 6a, making the reaction between 6a
and NH prevail. Evidently, the high selectivity to BAMF
3 2 2
than H on the Co/ZrO meanwhile allow for as 1,6-hexanedial could be successfully transformed into HDA
3
Table 2. Reductive amination of various dialdehydes over Co/ZrO
2
catalystsa
3
Entry
Substrate
Yield (%)
Diamines
3
critically relies on the regulation of trans-imination and
hydrogenation, which is accomplished by the employment of
short-chain alkylamine and transition metal catalysts such as
Co and Ni.
1
9
9
3
7
2
3
93
4b
8
1
5
9
6
0
3
6c
aReaction conditions: 30 mg Co/ZrO
catalyst, 0.25 mmol substrate, 0.75 mmol
2
butylamine, 3 g methanol, 0.6 MPa NH
internal standard; 3 g toluene as solvent, 1 MPa NH
3
, 2 MPa H
2
, 373 K, 10h, dodecane as
b
c
3
; 4 MPa H
2
, 393 K.
Conclusions
Scheme 2. Proposed mechanism for reductive amination of DFF over Co/ZrO
2
catalyst.
In summary, we have developed a new approach to the highly
selective synthesis of primary diamines from dialdehydes
through modulating the trans-imination and hydrogenation
activity, where the use of short-chain alkylamine to scavenge
the highly reactive dialdehyde is the key to suppressing
polymerization side reactions, and the suitable adsorption
Potential for practical application
3 2
strength of Co towards NH and H is crucial to regulate the
two competitive reactions. This strategy is expected to find
wide applications in the synthesis of a broad scope of bio-
Figure 4. Product of BAMF based on glucose. Reaction conditions: Step 1: 500 mg based primary amines and diamines, thus help to construct
, 5 g [EMIM]Cl (1-ethyl-3-methylimidazolium chloride) ionic liquid, sustainable polymer industry.
73 K, 3 h, after reaction, the product HMF was purified by extraction using glycol
dimethyl ether and distillation; Step 2: 50 mg Ru/AC catalyst (Commercial), purified
HMF from step 1, 5 g Toluene, 2 MPa O , 383 K, 10 h, after reaction, the product DFF
was purified by distillation; Step 3: 90 mg Co/ZrO catalyst, a half of purified DFF from
step 2, 2 mmol butyamine, 3 g methanol, 373 K, 10 h.
glucose, 53 mg CrCl
3
3
2
Conflicts of interest
2
There are no conflicts to declare.
In addition to the unprecedentedly high selectivity to the
primary diamines, this approach offers excellent reusability of Acknowledgements
the catalyst (Fig. S13a), and allows for the employment of
The authors are grateful for the support from the National Key
R&D Program of China (2018YFB1501602), the National
Natural Science Foundation of China (21690080, 21690084,
relatively high concentration of dialdehyde substrate (up to
0%, Table S2), showing its great potential for practical
1
application. The deactivation of 4th-run catalyst was attributed
slight carbon coke, but recalcination and reduction can make
Co/ZrO get recovered(Fig. S13b). To further demonstrate this
2
potential, we started from glucose and finally obtained 35%
yield of BAMF based on glucose (Fig. 4). Moreover, the above
2
1673228, 21721004, and 21878289), the Strategic Priority
Research Program of the Chinese Academy of Sciences
XDB17020100), and the Dalian National Laboratory for Clean
(
Energy (DNL) Cooperation Fund, the CAS (DNL 180303).
4
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DOI: 10.1039/D0GC02280B
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