Ru/ceria-catalyzed direct formylation of amines and CO to produce formamides

Article abstract of DOI:10.1039/c6gc02603f

We herein report a new strategy of directly converting amines and CO to formamides with 100% atom utilization efficiency. It is suitable for up to 25 amine substrates with no additives. Ru/ceria is found to be an excellent catalyst for this reaction due the efficient co-activation of CO and amine on Ru species.

Full text of DOI:10.1039/c6gc02603f

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Ru/ceria-Catalyzed Direct Formylation of Amines and CO to
Produce Formamides
Yehong Wang,a Jian Zhang,a Haijun Chen,a,b Zhixin Zhang,a Chaofeng Zhang,a,b Mingrun Li,a Feng
Wanga*
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
We herein report a new strategy of directly converting amines and suitable for a wide scope of substrates including primary and
CO to formamides with 100% atom utilization efficiency. It is
CO
suitable for up to 25 amine substrates with no additives. Ru/ceria
This work
is found to be an excellent catalyst for this reaction due the
Route A
Direct Route
efficient co-activation of CO and amine on Ru species.
Formamide is a class of key synthetic intermediate and
R1
R2
O
H
R1
R2
N
H
N
solvent. For decades, corrosive and dangerous NaOCH3
catalyst has been used for industrial production of
dimethylformamide (DMF),1which is a widely-used solvent and
a multipurpose building block for chemical synthesis.2 The
formamide synthesis is a fundamental chemical process.3
Previous studies have been focused on testing
transformylating reagents,4 such as DMF, HCOOH or in-situ-
generated HCOOH and derivatives. The principle of the
transformylation reaction lies in the C–X bond exchange
reaction between the pre-existing formyl group (R3-CHO) and
amine N–H bond (Scheme 1, Route B). This unavoidably
generates byproduct R3–H, lowering atom utilization efficiency
and leading to cumbersome product separation and waste
disposal. Some strategies have employed the oxidative
formylation reactions using CO and stoichiometric amount of
oxidants,5 such as O2 and NaIO4, with alkali, or using ionic
liquids combined with bases.6 Although these reactions
generated new C–N bond, they majorly produced urea instead
of formamides.7 Therefore, an ideal way is to develop
heterogeneous catalyst that is capable of directly converting
amines and CO to formamides with 100% atom utilization
efficiency, suppressing its further conversion to urea, as well as
the parallel reaction of amines to imines.
Route B
Transformylation
O
R3
C H
R3
H
Scheme 1. Formamides synthesis by direct route (Route A, the present study)
and by the transformylation route (Route B). One or two of R1 and R2 represents
CmHn- groups. R3 represents a CmHn-, RO-, HO-, or RN- group.
secondary amines. Ru/ceria catalyst is found to be active for
this direct formylation reaction. The excellent catalytic
performance of Ru/ceria is due to the co-activated of CO and
amine molecule on different Ru sites.
Due to its high oxygen storage and release capacity, facile
oxygen vacancy formation, ceria has attracted special interests
as catalyst or support8. Our initial test with CO and
benzylamine at 180 °C and under 0.5 MPa CO over pristine
ceria gave, after 4 h, merely 6% benzylamine conversion and
17% selectivity for N-benzylformamide (Figure 1). The major
product was imine. Further screening among other oxide and
zeolite catalysts still failed to give satisfactory results, which
made us believe that the reaction needed a metal center to
activate CO.7 We then prepared several ceria-supported Ru,
Rh, Pd, Pt and Au catalysts (Me/ceria) by an incipient wetness
impregnation method. Catalytic results showed the Me/ceria
catalysts gave no N-benzylformamide (Figure 1) except
Ru/ceria, which afforded 56% benzylamine conversion and
93% selectivity for N-benzylformamide. If calcining Ru/ceria at
500 °C, the resulting RuO2/ceria catalyst was unreactive for the
reaction. We also prepared several model nanocrystalline ceria
(rod, cube and octahedron) and the corresponding Ru/ceria
We herein report a new and direct route of converting
amines and CO to formamides without using additives,
hydrogen or oxygen (Scheme 1, Route A). This method is
a.Dalian National Laboratory for Clean Energy, Dalian Institute of Chemical Physics,
Chinese Academy of Sciences, 457 Zhongshan Road, 116023 Dalian, China
b.University of the Chinese Academy of Sciences, 100049 Beijing, China
* Correspondence to: F. Wang, Email: wangfeng@dicp.ac.cn
Electronic Supplementary Information (ESI) available: [details of any
supplementary information available should be included here]. See
DOI: 10.1039/x0xx00000x
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catalysts (2wt% loading). As a result, Ru/ceria (rod) gave much underwent cyclization reaction and majorly produced ureas.5b
better results (yield 46%) than that of Ru/ceria (cube) (yield
In this study, N,N'-(hexane-1,6-diyl) di-formamide was
obtained with > 99% selectivity (entry 5). Cyclic aliphatic
amines were obtained in high selectivities (entries 6-7). The N-
benzylformamide and its derivatives were obtained with > 95%
selectivity (entries 8-11). 1-Phenylethanamine was also
converted to the corresponding formamide with 98%
selectivity (entry 12). Bulky substituents were unfavorable, and
thus
a long reaction time was required for β-phenyl
ethylformamide (36 h) (entry 13). Amines with
tetrahydrofuran, furan and thiophene were converted with 25-
91% conversions and > 92% selectivities (entries 14-16). The
decrease in activity was possibly caused by restricting amine
adsorption by O or S atom opponent on active sites. Secondary
aliphatic amines were converted with 85-99% formamides
selectivities (entries 17-21). Steric hindrance could be
overcome by increasing reaction time and temperature. The
presence of hydroxyl groups facilitated the reaction (entry 20).
Formamides were obtained with > 99% selectivities from cyclic
secondary amines such as piperidine, morpholine (entries 22-
23). The rigid of piperazine and 1,4-diazepane majorly offered
the single-substituted formamide (entries 24-25). As shown
above, this strategy using heterogeneous catalyst is less
efficient in synthesizing bulky formamides.
Figure 1. Catalysts screening using the formylation of benzylamine with CO as model
reaction. Reaction conditions: 1.5 mmol amine in 2 mL methanol, 50 mg catalyst, 0.5
MPa CO, 180 °C, 4 h.
Current plants use NaOCH3 catalyst under oxidizing
conditions to produce DMF, which is corrosive, potentially
explosive and high energy consumption. In comparison, using
gaseous DMA and CO to produce liquid DMF is easily
separated and recycled. In this study we employed an
Figure 2. Isotopically labeling experiments. Reaction conditions: 1.5 mmol amine in 2
industrially widely-used fixed-bed reactor to realize
a
mL solvent, 50 mg Ru/ceria catalyst, 0.9 MPa CO, 150 °C, 6 h.
continuous DMF synthesis (Figure S2). Catalytic results showed
that the reaction at 180 °C and under a pressure of 2.7 MPa
offered the average 40% conversion of DMA with > 99% DMF
selectivity in the trapped liquid product. The continuous
reaction had a lower conversion than the batch reaction due
to shorter contact time, but comparably high selectivity.
Unreacted CO and DMA gas were recycled to upstream. The
21%) and Ru/ceria (octahedron) (yield 20%). This is consistent
with our previous discovery on ceria-supported nanogold
catalyst and is also found in other ceria-supported metal
catalysts.9
In order to test whether it was a direct formylation
reaction, we examined the C source of formamide (RN–CHO)
(Figure 2). The reaction at 150 °C for 6 h over 2 wt% Ru/ceria
[abbr. Ru/ceria hereinafter] offered 61% conversion and 99%
selectivity. No reaction occurred in 0.9 MPa N2 and without CO
gas. We hypothesized that methanol solvent might join the
reaction, which was reported in literatures.10 The possibility
was then excluded when by using tetrahydrofuran (THF) as
solvent (conv. 47%, select. 94%). A reaction in a mixed solvent
of THF:13CH3OH (5:1 v/v) gave no 13C-labeled product, but a
reaction with 13CO gas produced the 13C-labeled N-
benzylformamide (Figure S1), which indisputably confirmed C
in RN–CHO is from CO. More interestingly, 13CO or C18O is
readily accessed as is the CO isotopologue, offering
a
potentially economic route to the isotopically labeled
formamides. The preceding transformylation methods
converted the majority of the labeled elements into
byproducts.
We then extended this method to other amine substrates
(Figure 3). The reactions on primary aliphatic mono-amines
and di-amines proceeded remarkably well (entries 1-5). In
literatures, the formylation of a di-amine by CO and O2
2 | J. Name., 2012, 00, 1-3
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around 2030 cm-1, which is assigned to the linearly bonded CO
on Ru0 sites on large Ru nanoparticles.48,13 These experimental
results suggest that ceria support can well stabilize Ru clusters
during the reduction and restricting the Ru size growth. The
adsorption of amine was also investigated on Ru/ceria (Figure
5b). n-Butylamine was used as model molecule. We have
reported that when n-butylamine was adsorbed on ceria, the
bending stretching of N–H red-shifted from 1624 cm–1 of free n-
butylamine molecule to around 1560 cm–1. This shift was due to
the adsorbed n-butylamine on basic oxygen site of ceria via the
Ce–Oδ-•••Hδ+–N interaction.14 While when n-butylamine was
adsorbed on Ru/ceria, the bending stretching of N–H red-shifted
to much lower frequency around at 1530 cm–1, indicating the
stronger interaction between amine and Ru/ceria than pristine
ceria. This leads us to conclude that n-butylamine may be
preferentially activated on Ru sites. In order to further confirm
the active sites for amine activation, in situ IR tests of CO and n-
butylamine adsorption was conducted (Figure 5c). Addition of n-
butylamine to the CO-saturated Ru/ceria surface revealed that
the peak at 2145 cm–1 assigned to CO adsorbed on Ruδ+
gradually decreased in intensity and disappeared in 30 min at
room temperature. And no remark band related to formamide
product was observed at the same time. The IR peaks at 2080
and 2008 cm–1 remained but red-shifted. And these two bands
blue-shifted to the original positions upon desorbing n-
butylamine. Combined the result of amine adsorption IR, the
disappearing 2145 cm–1 could be due to that CO on Ruδ+ was
taken over by n-butylamine during competitive adsorption. Thus
we proposed that amine was activated on Ruδ+. As it is known
that rod and nano particle ceria contain more oxygen vacancies
than other ceria substrates,15 they might be beneficial for the
formation of finely dispersed Ru clusters and enhanced the
electronic and oxygen transfer in the interface, tuning the
electronic structure of noble metals supported on ceria.16 In this
formylation reaction system catalyzed Ru/ceria catalyst, the
transfer of electron and oxygen might create many more Ruδ+
sites for amine activation. Thus, the rod and particle ceria with
rich oxygen vacancy content showed excellent performance in
the direct formylation reaction than ceria cube and octahedron
(Figure 1). CO adsorption on Ru/ceria after calcination at 500 oC
was also investigated (Figure S6). The result suggested that there
was no chemical interaction between the Ru catalyst and CO. It
could be the reason that Ru/ceria after calcination could not
catalyze the formylation reaction efficiently (Figure 1).
Figure 3. Direct formylation reaction of various amines to formamides catalyzed by
Ru/ceria. Reaction conditions: 1.5 mmol amine in 2 mL methanol, 0.05 g Ru/ceria
catalyst, 0.9 MPa CO, 150 °C, 24 h.
60
100
80
40
60
40
20
20
0
0
0
50
100
150
200
250
300
350
Time on stream (h)
Figure 4. Continuous synthesis of DMF from DMA and CO in a fixed-bed reactor.
Reaction conditions: reaction pressure 2.7 MPa (back valve), 180 oC, feeding gas
composition: CO : N2 = 1 : 1 (volume ratio), DMA : CO = 1: 18 (molar ratio). Ru/ceria
catalyst 8 mL, GHSV 40 h–1
.
Figure 5. (a) IR of CO adsorption on Ru/ceria for 30 min at room temperature and then
desorption at 150oC (b) IR of liquid n-butylamine and IR of n-butylamine adsorption at
room temperature and then desorption at 150oC (c) In situ IR spectra of consecutive
adsorption of CO followed by n-butylamine.
reaction can be run for 288 h with merely <5% activity loss
(Figure 4). The TON achieved 6125 which was calculated
according to the reference,11 where the size of Ru particles is
about 1 nm from HR-TEM (Figure S5) We checked the used
catalyst and found a small amount of carbon deposit (Figure
S3-S4). The catalyst was regenerated by calcination and
reduction in H2 before reuse.
Kinetic analysis (Figure S7) was conducted in batch reactor
and it showed the first order for both the partial pressure of CO
(PCO: 0.6-0.8 MPa) and the n-butylamine concentration (0.50-
1.25 M), suggesting a possible concerted reaction mechanism.
In summary, we have reported a direct formylation
reaction of amines and CO to generate formamides. The co-
activation of amine and CO was achieved on different Ru
species supported on ceria. The present study represents a
new and convenient route for formamide synthesis,
developing new application for supported ceria catalyst.
The CO adsorption on Ru/ceria catalyst was investigated
(Figure 5a). There are three remarkable bands. Because of no
chemical interaction between CO and ceria support, thus, these
three bands were assigned to CO adsorption on Ru species. The
high-frequency band located at 2145 cm-1 and 2080 cm-1 were
assigned to multicarbonyl species on the oxidized Ru sites
[Ruδ+(CO)x] although there was no consensus regarding the
oxidation state of Ru (δ) and the number of carbonyl groups
(x).12 The low-frequency is located at 2008 cm-1 assigned to the
stretching of CO adsorbed Ru0 related to the highly dispersed Ru
atoms with defects.12a, 12b For comparison, when Ru is supported
on SiO2 or MgO support, the low-frequency band is observed at
Acknowledgements
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This work was supported by National Natural Science
Foundation of China (21422308, 21303189) and by Strategic
Priority Research Program of Chinese Academy of Sciences
(XDB17020300).
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