Switchable synthesis of furfurylamine and tetrahydrofurfurylamine from furfuryl alcohol over RANEY nickel

Article abstract of DOI:10.1039/c7cy00981j

RANEY Ni proved to be an effective heterogeneous catalyst for switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine with NH₃ by simply adding or not adding 1.0 MPa H₂ into the reaction bulk. After further optimization of the reaction conditions, we finally obtained 94.0% yield of tetrahydrofurfurylamine and 78.8% yield of furfurylamine with high selectivity. By extensively studying the catalytic pathways and mechanism of catalyst deactivation with XRD and XPS characterization, we have confirmed that an excess amount of H₂ in the reaction bulk leads to the deep hydrogenation of the furan ring while an insufficient amount of H₂ leads to the formation of Ni₃N and the deactivation of the catalyst.

Full text of DOI:10.1039/c7cy00981j

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ISSN 2044-4753
PAPER
Qingzhu Zhang et al.
Catalytic mechanism of C–F bond cleavage: insights from QM/MM
analysis of fluoroacetate dehalogenase
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Catalysis science & Technology
Paper
Switchable synthesis of furfurylamine and tetrahydrofurfuryl-
amine from furfuryl alcohol over Raney Nickel
Received 00th January 20xx,
Accepted 00th January 20xx
a
a
a
a
b
b
∗b
YingxinLiu , KuoZhou , HuiminShu , Haiyan Liu , JiongtaoLou , DechaoGuo , Zuojun Wei ,
c
Xiaonian, Li
DOI: 10.1039/x0xx00000x
Raney Ni proved to be an effective heterogeneous catalyst for switchable reductive amination of furfuryl alcohol to
www.rsc.org/
3 2
tetrahydrofurfurylamine and furfurylamine with NH by simply adding or not adding 1.0 MPa of H into the reaction bulk.
After further optimization of the reaction conditions, we finally obtained 94.0% yield of tetrahydrofurfurylamine and 78.8%
yield of furfurylamine with high selectivity. By extensively studying the catalytic pathways and mechanism of catalyst
deactivation with XRD and XPS characterization, we have confirmed that excess amount of H
2
in the reaction bulk leads to
the deep hydrogenation of furan ring while insufficient amount of H
2
leads to the formation of Ni N and the deactivation
3
of catalyst.
required, while for step (2), an acid or base catalyst is preferred,
1
7
Introduction
although it can also occur without a catalyst . This reaction
process is generally carried out under a mixture of ammonia
and hydrogen. However, hydrogen is not stoichiometrically
Amine plays an important role in the bulk and fine chemical
industries for production of polymers, dyes, pharmaceuticals,
agrochemicals, surfactants and biologically active compounds.
Generally, primary amines can be synthesized by reductive
amination of either corresponding carbonyl compounds or
alcohols. Comparing with the former, amination of alcohols
takes advantage of using inexpensive starting material and
exhibiting higher atom efficiency, and deserves increasing
1
consumed due to the existence of a soꢀcalled “borrowing
hydrogen” or “hydrogen autoꢀtransfer” mechanism
5, 18
, from
which it is suggested that the “borrowed” hydrogen from the
dehydrogenation of alcohol is returned by reducing the imine
into the target amine. As a consequence, hydrogen is
theoretically unnecessary for conducting the amination of
alcohol, although it is claimed that excess hydrogen is
indispensable to prevent the catalyst from irreversible
1
, 2
attention
.
The reductive amination of hydroxyl compound with
ammonia can be catalyzed by metal complexꢀbased
homogeneous catalysts, such as Ruꢀ and Irꢀbased complex
solid acid catalysts, such as zeolites, phosphates, and oxides
1
9ꢀ22
deactivation caused by the formation of nickel nitride
and
2
3, 24
coking
.
3
ꢀ6
,
,
Furfurylamine and tetrahydrofurfurylamine are important
intermediates in the manufacture of pharmaceuticals, fibers and
perfumes . Similar to most primary amines, furfurylamine
can be synthesized through reductive amination of its
corresponding aldehyde, furfural, over metal catalysts
while tetrahydrofurfurylamine can be produced by deep
hydrogenation of furfurylamine or 2ꢀfurancarbonitrile
7
, 8
and metal hydrogenation catalysts, such as Pt, Ir, Ru, Os, Cu,
2
5ꢀ29
2, 9ꢀ13
Co and Ni
activate the alcohols by three consecutive steps (Scheme 1)
1) dehydrogenation of the alcohol to form corresponding
. It is widely accepted that metal catalysts
1
4ꢀ16
:
2
5, 26
,
(
carbonyl intermediate; (2) Condensation of the intermediate
with ammonia and followed by elimination of water to form an
imine, and (3) hydrogenation of the imine to produce the final
primary amine. For steps (1) and (3) a metal catalyst is
3
0, 31
.
Scheme 1 General pathway for reductive amination of alcohols
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ARTICLE
Table 1 Reductive amination of FA with different heterogeneous metal catalyst
Journal Name
Yield (Selectivity) (%)
Entry
catalyst
H
2
(MPa)
NH
3
(MPa)
Conversion (%)
Other byꢀ
products
1
2
3
4
5
6
7
8
9
Pd/C
Pt/C
Ru/C
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.35
0.35
ꢀ
0
0
0
0
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
Rh/C
Raney Co
Raney Ni
Pd/C
Pt/C
Ru/C
0
ꢀ
ꢀ
ꢀ
24.0
12.4
16.9
24.2
16.3
18.4
27.5
100
22.2(92.5)
1.8(7.5)
11.3(91.1)
12.2(72.2)
20.1(83.1)
16.2(99.4)
16.4(89.1)
15.5(56.4)
100
1
1
1
1
1
1
1
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
1.10(8.9)
4.70(27.8)
4.09(16.9)
0.2(0.6)
0.99(5.4)
0.99(3.6)
10
11
12
Rh/C
Raney Co
Raney Ni
Pd/C
0.99(5.4)
11.0(40.0)
a
1
3
a
3
Reaction conditions: FA, 0.5 g; THF, 15 ml; catalyst, 0.25 g; NH pressure, 0.35 MPa; temperature, 160 °C; reaction time, 24 h; stirring speed, 1200 rpm.
catalyst 0.05 g, 160 °C, 4 h, in absence of NH
3
.
Alternatively, they can also be synthesized through amination substrate, entry 13). Comparatively, in the similar reductive
of furfuryl alcohol and followed by the saturation of the furan amination process, such hydrogenation activity of the metals
ring (for tetrahydrofurfurylamine synthesis). To the best of our was greatly inhibited, as one can see that the conversion of
knowledge, no other catalyst except for homogeneous catalysts furfural alcohol over Pd/C was only 12.4% (entry 7). In a
3
such as
a
Ruꢀacridine complex and
a
triruthenium typical hydrogenation/dehydrogenation process, H atom is first
5
dodecacarbonyl complex have been reported for such reaction decomposed from either HꢀH bond or CꢀH bond and adsorbed
so far. The development of heterogeneous catalysts with base onto a metal active sites for the following reactions
3
3, 34
. The
metals taking advantage of easier separation and lower cost for deactivation of metals for hydrogenation/dehydrogenation in
the reductive amination of furfural to obtain furfurylamine and the reductive amination process can therefore be ascribed to the
tetrahydrofurfurylamine is therefore urgent and falls in our competitive occupation of NH
3
on the metal active sites. Fig. 1
interest. In this study, based on our previous work on summarized our calculated and the reported adsorption energy
3
2
2 3
hydroamination of isophorone nitrile to isophorone diamine , of H and NH on different facets of the metal active cites
we herein aimed at the reductive amination of furfuryl alcohol evaluated on the basis of the first principle calculations. The
as a model reaction to achieve high selectivity to furfurylamine differences of the averaged adsorption energy for noble metals
and tetrahydrofurfurylamine.
are higher than those of Co and Ni, indicating that more metal
active sites would be occupied by NH . This might be the main
reason that noble metals are less active in reductive amination,
3
Results and discussion
3
2, 35
which is also in agreement with our previous study
.
The reductive amination of furfuryl alcohol was conducted in
Given that H and NH may compete to adsorb on the same
2
3
absence of hydrogen over the commercially available Pt/C, metal active sites, variation of the ratio of H and NH may
2
3
Pd/C, Ru/C, Rh/C, Raney Co and Raney Ni. As shown in Table impact greatly on the reductive amination process. As shown in
, all the tested catalysts were totally inactive except for Raney
1
Ni (entries 1ꢀ6), over which the main product was
furfurylamine (92.5% in selectivity, entry 6), although the
conversion was low (24.0%, entry 6). After introducing 1 MPa
of hydrogen, as expected, the furan ring was saturated over
each tested catalyst and formed a considerable amount of
tetrahydrofurfuryl alcohol due to deep hydrogenation (entries 7ꢀ
1
2). Only tetrahydrofurfurylamine of the amination product was
found over Raney Co and Raney Ni, with the yields of 0.99%
and 11.0%, respectively.
It is well known that the metal catalysts we have used are
active in hydrogenation reactions. Taking Pd/C as an example,
deep hydrogenation product of furfuryl alcohol can 100%
convert to tetrahydrofurfuryl alcohol in the presence of pure H2
within 4 h over much less catalyst dosage (10 wt% in respect to
2 3
Fig. 1 Reported adsorption energy of H and NH on different
facets of the metal active cites evaluated on the basis of the
36-69
first principle calculations.
2
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Table 2 Effect of hydrogen pressure on amination of furfuryl alcohol
Yield (Selectivity) (%)
Conversion
Other byꢀproducts
Entry
H
2
(MPa)
(
%)
unidentified
compounds
1
2
3
4
2.0
1.0
0.5
0
69.3
27.5
27.8
24.0
ꢀ
ꢀ
21.3(30.7)
15.5(56.4)
12.0(43.2)
1.8(7.5)
7.5(10.8)
11.0(40.0)
7.5(27.0)
ꢀ
2.8(4.0)
31.8(45.9)
5.9(8.5)
1.0(3.6)
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
ꢀ
8.3(29.9)
22.2(92.5)
3
Reaction conditions: FA, 0.5 g; THF, 15 ml; Raney Ni, 0.25 g; NH pressure, 0.35 MPa; temperature, 160 °C; reaction time, 24 h; stirring speed, 1200 rpm.
Table 2, when Raney Ni was employed, we adjust the ratio of higher than 180 ºC, while it kept increasing in the case of 1.0
and NH by changing the partial pressure of H while the MPa of H (Figure 2(a)). This might be ascribed to the lower
partial pressure of NH was fixed at 0.35 MPa, a maximum thermostability of Raney Ni in pure NH atmosphere.
pressure the NH cylinder can provide. The reason we and other The reaction kinetics at 180 ºC in presence of 1.0 MPa and
is mainly to 0 MPa of H was further conducted in order to optimize the
H
2
3
2
2
3
3
3
1
7, 19, 70
publications
used the largest amount of NH
3
2
suppress the formation of secondary amines and tertiary amine. reaction time. As seen from Fig. 3(a), the yield of
It can be seen that the conversion of furfuryl alcohol was the tetrahydrofurfurylamine kept increasing linearly and reached
highest of 69.3% at 2.0 MPa of H . However, except for maximum (94.0%) at 48 h with selectivity of 95.7%. Further
2
tetrahydrofurfuryl alcohol and tetrahydrofurfurylamine, a large extension of reaction time resulted in other unwanted byꢀ
amount of ringꢀopening products such as, 2ꢀaminoꢀ1ꢀpentanol products and a decline of tetrahydrofurfurylamine selectivity.
and 1, 2ꢀpentanediol were formed, indicating that high H
2
While for furfurylamine synthesis (Fig. 3(b)), the
pressure resulted in overꢀhydrogenation. As a result, the transformation rate relatively slowed down during the late of
selectivity of tetrahydrofurfurylamine was only 10.8%. When the reaction and only 78.8% of yield was obtained. Further
the partial pressure of H
the conversion decreased remarkably from around 69.3% to furfurylamine. However, the reaction rate becomes rather slow,
7.5% while the selectivity of amine (mainly
2
dropped from 2.0 MPa to 1.0 MPa, extending the reaction time may obtain higher yield of
2
，
tetrahydrofurfurylamine) increased to 40% and no ringꢀopening
products were observed. When the partial pressure of H2
dropped to 0.5 MPa, the conversion of furfuryl alcohol almost
unchanged, but a new product, furfurylamine, with a selectivity
of 29.9% appeared and the selectivity of total amines increased
to 56.9% at the same time. In absence of hydrogen, the
selectivity of furfurylamine is the highest (92.5%), although the
conversion of furfuryl alcohol was only 24.0%. Meanwhile, it is
noteworthy that 1.8% yield of tetrahydrofurfuryl alcohol was
(a)
2
obtained even no H was introduced, which is also evidence of
the existence of dehydrogenation step in the reductive
amination process. These results show that the switchable
synthesis of tetrahydrofurfurylamine and furfurylamine from
furfural alcohol is feasible by conducting the reductive
amination of furfuryl alcohol over Raney Ni at 1.0 MPa and 0
MPa of H , respectively.
2
The optimization on amination temperature was tested in
the range of 160 °C to 200 °C for both synthesis of
tetrahydrofurfurylamine (in presence of 1 MPa of H
furfurylamine (in absence of H ), as shown in Fig. 2(a) and
(b), which exhibited similar trends of the product spectra. For
example, both target products, i.e., tetrahydrofurfurylamine and
furfurylamine, reached the highest yields at 180 ºC, which were
2
) and
(
b)
2
Fig. 2 Effects on temperature on reductive amination of
furfuryl alcohol for synthesis of (a) tetrahydrofurfurylamine
2
in 1.0 MPa of H
Reaction conditions: partial pressure of NH
.5 g; THF, 15 ml; Raney Ni, 0.25 g; reaction time, 24 h;
2
and (b) furfurylamine in absence of H
2
.
46.2 % and 47.7 %, respectively; a lower temperature at 160 °C
both resulted in a low furfuryl alcohol conversion while a
3
, 0.35 MPa; FA,
0
higher temperature at 200 °C both led to a noticeable increase stirring speed, 1200 rpm.
of unidentified byꢀproducts. Only one difference that might be Abbreviation: FAM, furfurylamine; THFA, tetrahydrofurfuryl
noticed is that the transformation of furfuryl alcohol in absence alcohol; THFAM, tetrahydrofurfurylamine
2
of H (Fig. 2(b)) stopped increasing when the temperature was
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Journal Name
Scheme
2 Proposed reaction pathway for reductive
(
a)
aminationof furfuryl alcohol
respectively. This demonstrates that another synthesis path
started by saturation of furan ring was switched on to finally
reach tetrahydrofurfurylamine. Since tetrafurfuryl alcohol
accumulated during the amination process, it is reasonable to
consider that the dehydrogenation of tetrafurfuryl alcohol is
also the rate limiting step in the “furanꢀring saturation path”.
Furfurylamine cannot be the terminal product in the presence of
2 2
H , as it will be saturated with H and gradually forms
tetrahydrofurfurylamine after 36 h of reaction. The possible
overall reaction pathway for amination of furfuryl alcohol is
therefore rationalized in Scheme 2.
(
b)
Fig. 3 Reaction kinetics of reductive amination of furfuryl
alcohol for synthesis of (a) tetrahydrofurfurylamine in 1.0
It should be noted that the dehydrogenation intermediates
furfural and tetrafurfural were not detectable in either H
presence or absence case. This is mainly because that the two
intermediates are quite reactive to condense with NH and then
be hydrogenated to the corresponding amines, which was also
2
MPa of H
conditions: partial pressure of NH
5 ml; Raney Ni, 0.25 g; reaction temperature, 180 ºC; stirring
speed, 1200 rpm.
2
and (b) furfurylamine in absence of H
2
. Reaction
3
, 0.35 MPa; FA, 0.5 g; THF,
3
1
17, 71
reported elsewhere.
However, when we replaced NH
3
with
cyclohexene as the H
2
acceptor (here NH forms imine with
3
indicating that the activity of Raney Ni may be getting poorer
along the reaction time without protection under H . Based on
aldehyde as the H
alcohol, the intermediate furfuralwith yield of 7.6% was clearly
observed (entry 2 in Table S3). In contrast, if neither NH nor
any other H acceptor was added, furfuryl alcohol remain
unchanged during the reaction and no furfural was detected
entry 3 in Table S3). From the above experiments, we
2
acceptor) in the dehydrogenation of furfuryl
2
the aforementioned amination mechanism in scheme 1, the
reductive amination of furfuryl alcohol undergoes
dehydrogenation to furfural, imidization to imine, and finally
hydrogenation to furfurylamine. In order to determine which
one is the rateꢀlimiting step, the reductive amination of furfural
was also conducted, which showed that furfural could be
completely converted even at the milder condition of 0.1 MPa
3
2
(
concluded that the aldehyde intermediates may be detected if
suitable H2 acceptor was selected, and the “borrowing H2”
pathway will not occur if no any H acceptor exists.
The reusability of Raney Ni was investigated for both
synthesis of furfurylamine and tetrahydrofurfurylamine. After
reaction, the catalyst was centrifugated, washed with THF, and
returned to the reactor for reuse at the previous reaction
conditions. As shown in Table 3, Raney Ni can maintain its
activity for synthesis of tetrahydrofurfurylamine synthesis at
2
2
H and 80 °C in 2 h (entry 1 in Table S2), with a furfurylamine
yield of 62.6%. In contrast, much harsher experimental
conditions (180 ºC and 30 h) were needed to reach the similar
yield of furfurylamine if furfurylalcohol was used as the
substrate (Figure 3(b)). The corresponding initial rate could be
ꢀ2
ꢀ1 ꢀ1
ꢀ2
approximately evaluated as 17.4×10 mol·L ·h and 1.4×10
ꢀ1
ꢀ1
mol·L ·h , respectively. This indicates that reaction rates from
furfuryl alcohol to furfurylamine is more than ten times lower
than that from furfural to furfurylamine, without regarding the
much harsher reaction conditions the former has been used. In
another word, dehydrogenation of furfuryl alcohol is the
slowest reaction step that controls the whole reductive
amination process, which is also in agreement with other
1
.0 MPa of H
without obvious deactivation. However, for synthesis of
furfurylamine in absence of H , the conversion of furfuryl
2
, which could be reused at least five times
2
alcohol dropped sharply from 78.5% at the first run to 53.4% at
the second run, showing the poor reusability of Raney Ni. We
observed this reused Raney Ni lost magnetism while the Raney
Ni reused in presence of H
XRD (Figure S3) and XPS (Figure S4) characterization also
showed that a new crystalline phase of Ni N was formed in the
firstꢀreused Raney Ni catalyst for furfurylamine synthesis,
2
did not (Figure S2). The followed
1
7, 24
publications
When amination of furfuryl alcohol was conducted under 1.0
MPa of H , two intermediates, i.e., tetrahydrofurfuryl alcohol
and furfurylamine were observed to peak at 6 h and 36 h,
.
3
2
19ꢀ22
which is in agreement with the prevous reports
.
4
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Table 3 Reusability test of Raney Ni for reductive amination of furfuryl alcohol
Yield (%)
Entry
Times
H
2
(MPa)
NH
3
(MPa)
Conversion (%)
Other byꢀ
products
1
2
3
4
5
6
7
1
2
3
4
5
1
1
1
1
1
ꢀ
0.35
0.35
0.35
0.35
0.35
0.35
0.35
66.2
67.6
64.5
64.4
63.9
78.5
53.4
8.8
10.0
10.1
9.7
9.2
76.5
52.7
7.3
7.6
4.8
7.6
8.0
1.0
ꢀ
45.1
46.7
43.6
43.5
44.1
ꢀ
5.0
3.3
6.0
3.6
2.6
1.0
a
1
a
2
ꢀ
ꢀ
0.7
a
Reaction conditions: FA, 0.5 g; THF, 15 ml; Raney Ni, 0.25 g; reaction temperature, 180 ºC; reaction time, 24 h; stirring speed, 1200 rpm.
Reaction time 48 h
0
.32 mm × 0.25 µm) and a flame ionization detector (FID). The
Conclusions
initial column temperature was 80 °C and held for 10 minutes. Then
the temperature was ramped at 10 °C/min until it reached 250 °C.
Both the injector temperature and the detector temperature were set
at 260 °C.
Structure of the reaction components were further identified by
GC/MS with an Agilent 6890 gas chromatography system coupled to
a mass spectrometer equipped with an Agilent 5973 quadrupole
mass analyzer.
The conversions and yields were simply calculated by peak areas
of the substrate, target product and the known byꢀproducts, which
was validated by the carbon balance analysis (carbon
recovery>94.8%, see the Supplementary Information ) using nꢀ
dodecane as an internal standard. The typical GC image with byꢀ
products and MS spectrums for the known substances were shown in
Figure S1.
In conclusion, Raney Ni proved to be an effective
heterogeneous catalyst for switchable reductive amination of
furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine
with NH by simply adding or not adding 1.0 MPa of H into
3
2
the reaction bulk. Its unique performance in reductive
amination can be attributed to the proper adsorption ability of
NH , H and furfuryl alcohol. After optimization, we finally
3
2
obtained 94.0% yield of tetrahydrofurfurylamine and 78.8%
yield of furfurylamine with high selectivity. For synthesis of
tetrahydrofurfurylamine in presence of 1 MPa of H , Raney Ni
2
catalyzed not only the amination of hydroxyl but also the
hydrogenation of the furan ring, and it can be reused at least
five times without obvious deactivation. While for
2
furfurylamine synthesis in absence of H , Raney Ni catalyzed
amination of furfuryl alcohol via the “borrowing hydrogen”
mechanism. The activity of Raney Ni dropped sharply. XRD
and XPS characterization shows that the formation of a new
Acknowledgements
3
Ni N contributes to the deactivation.
This work was supported by the National Natural Science
Foundation of China (21476211), the Zhejiang Provincial
Natural Science Foundation of China (LY14B060003and
LY16B060004).
Experimental
Chemicals
Furfuryl alcohol and Raney Ni catalyst were purchased from
Aladdin Industrial Co. Ltd, and used as received. Ammonia,
hydrogen and nitrogen gases were provided by Hangzhou Jingong
Special Gas Co. Ltd, with purity larger than 99.99%. Other
chemicals were analytical reagents and purchased from Sinoꢀpharm
Reagent Co. Ltd.
Notes and references
1
.
T. Takanashi, Y. Nakagawa and K. Tomishige, Chem. Lett.,
014, 43, 822-824.
2
2
.
T. Takanashi, M. Tamura, Y. Nakagawa and K. Tomishige,
RSC Adv., 2014, 4, 28664.
Typical procedures of catalytic reactions
3.
C. Gunanathan and D. Milstein, Angew. Chem., Int. Ed.,
2008, 47, 8661-8664.
Typically, 15 mL of THF (solvent), 0.5 g furfuryl alcohol, and 0.25
g Raney nickel were introduced into a 25 mL stainless steel
autoclave. After sealed and purged by N (5 times), ammonia was
introduced up to 0.35 MPa with continuous stirring at 1200 rpm.
Then, 1.0 MPa of hydrogen was introduced after filling the autoclave
with ammonia. Afterward, the reactor was heated to 180 °C and
retained for 24 h.
4
5
6
7
8
9
.
.
.
.
.
.
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Switchable reductive amination of furfuryl alcohol to tetrahydrofurfurylamine and furfurylamine
was realized by adding/not adding H over Raney Ni catalyst
2