Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles by using Heterogeneous Catalysis

Article abstract of DOI:10.1002/cssc.201900365

The use of triglycerides as an important class of biomass is an effective strategy to realize a more sustainable society. Herein, three heterogeneous catalytic methods are reported for the selective one-pot transformation of triglycerides into value-added chemicals: i) the reductive amination of triglycerides into fatty amines with aqueous NH₃ under H₂ promoted by ZrO₂-supported Pt clusters; ii) the amidation of triglycerides under gaseous NH₃ catalyzed by high-silica H-beta (Hβ) zeolite at 180 °C; iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH₃ at 220 °C. These methods are widely applicable to the transformation of various triglycerides (C₄–C₁₈ skeletons) into the corresponding amines, amides, and nitriles.

Full text of DOI:10.1002/cssc.201900365

Accepted Article
Title: Selective Transformations of Triglycerides into Fatty Amines,
Amides, and Nitriles using Heterogeneous Catalysts
Authors: Md. A. R. Jamil, S.M.A. Hakim Siddiki, Abeda S. Touchy, Md.
Nurnobi Rashed, Sharmin S. Poly, Yuan Jing, Kah Wei Ting,
Takashi Toyao, Zen Maeno, and Ken-ichi Shimizu
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the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemSusChem 10.1002/cssc.201900365
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ChemSusChem
10.1002/cssc.201900365
Selective Transformations of Triglycerides into Fatty Amines, Amides, and Nitriles
using Heterogeneous Catalysts
a
a
a
a
Md. A. R. Jamil, S.M.A. Hakim Siddiki, * Abeda Sultana Touchy, Md. Nurnobi Rashed, Sharmin
a
a
a
a,b
a
a,b
Sultana Poly, Yuan Jing, Kah Wei Ting, Takashi Toyao, Zen Maeno, Ken-ichi Shimizu *
a
Institute for Catalysis, Hokkaido University, N-21, W-10, Sapporo 001-0021, Japan
b
Elements Strategy Initiative for Catalysts and Batteries, Kyoto University, Katsura, Kyoto 615-
8520, Japan
*Corresponding authors
S. M. A. Hakim Siddiki, Ken-ichi Shimizu
E-mail: hakim@cat.hokudai.ac.jp, kshimizu@cat.hokudai.ac.jp
Abstract
The use of triglycerides as an important class of biomass is an effective strategy to realize a more
sustainable society. Herein, we present three types of heterogeneous catalytic methods for the
selective one-pot transformation of triglycerides into value-added chemicals: (i) the reductive
amination of triglycerides to fatty amines with aqueous NH
clusters; (ii) the amidation of triglycerides under gaseous NH
zeolite at 180 °C; (iii) the Hβ-promoted synthesis of nitriles from triglycerides and gaseous NH
20 °C. These methods are widely applicable to the transformation of various triglycerides (C4-C18
3
under H
catalyzed by high-silica H-beta (Hβ)
at
2
promoted by ZrO
2
-supported Pt
3
3
2
skeletons) into the corresponding amines, amides, and nitriles.
KEYWORDS: Biomass, triglycerides, heterogeneous catalysis, amines, amides, nitriles.
1
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ChemSusChem
10.1002/cssc.201900365
Introduction
The alarming predictions for the rapid depletion of fossil-fuel resources have inspired researchers to
develop alternative technologies that exploit renewable energy sources.[1-13] Many studies have
focussed on the conversion of lignocellulosic biomass[14-21] and triglycerides[14,22,23] into various
platforms of value-added chemicals.[24-33] Industrially, triglycerides in oils and fats have been used as
feedstocks for the synthesis of fatty amines, amides, nitriles, and alcohols, which in turn are used for
the production of surfactants, polymers, and other useful commodity chemicals.[34]
Currently, fatty amines are produced industrially from triglycerides via fatty nitriles or fatty
alcohols.[1,34] In the former method (‘nitrile process’ in Scheme 1), triglycerides extracted from oilseeds
undergo hydrolysis to afford fatty acids, which are then treated with NH
oxide catalysts at high temperature to yield fatty nitriles; a subsequent metal-catalyzed high-
temperature hydrogenation of the nitriles under high pressure of H furnishes the targeted fatty
amines.[14,34,35] In the latter method, fatty acids or their methyl esters are hydrogenated to generate
fatty alcohols, which are then treated with NH
to produce fatty amines.[36] Henkel & Co Ltd. have
reported a direct conversion of triglycerides into amines using Zn-Al or Zn-Cr catalysts with
NH or short-chained alkyl amines. However, this method suffers from serious drawbacks, which
include harsh reaction conditions (200-400 °C; 50-400 bar H ) and the use of sub-stoichiometric
amounts of catalysts.[37] Recently, Beller and co-workers have reported the first homogenous catalytic
method for the direct synthesis of N-alkylated amines from triglycerides and amines under a H
pressure of 60 bar,[38] which employs the [Ru(acac)
]/Triphos/HNTf catalytic system (acac =
acetylacetonate; Triphos = 1,1,1-tris(diphenylphosphinomethyl)-ethane; HNTf = triflimide). Although
this study represents a significant step forward in this area, this catalytic system still requires additives
3
in the presence of metal-
2
3
2
O
3
2
O
3
3
2
2
3
2
2
and suffers from difficulties associated with catalyst/product separation. In addition, the use of NH
3
as
a nitrogen source was not addressed in this report.
Fatty amides are widely used as/in surfactants, lubricants, cosmetics, shampoos, foam-control
agents, fungicides, corrosion inhibitors, water repellents, detergents, and anti-blocking agents in the
plastics-processing industry.[39-41] Industrially, fatty amides are currently produced using a two-step
process (Scheme 2): the conversion of triglycerides into fatty acid esters, followed by a high-
temperature aminolysis to produce fatty amides.[42] Several studies have reported the direct amidation
of triglycerides with amino alcohols or isopropylamine using basic promoters such as methoxides,[43]
NaOH/CaO,[44] Na-doped Ca(OH)
However, reports on the direct amidation of triglycerides with NH
knowledge, only one report discusses the direct amidation of triglycerides to amides using NH
,[45] and Li-doped CaO,[46] or using solid acid or biocatalysts.[47]
2
3
remain scarce. To the best of our
3
-
saturated t-butyl alcohol and lipase (Novozym 435).[48] An environmentally benign method for the
synthesis of fatty amides based on reusable heterogeneous catalysts thus represents an attractive
research target.
2
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ChemSusChem
10.1002/cssc.201900365
Reports on the direct synthesis of fatty nitriles from triglycerides and NH remain equally
3
scarce. As summarized by Corma,[1] fatty nitriles are generally obtained from triglycerides via fatty
acids or their esters (Scheme 3).[1,49,50] Even though the direct synthesis of nitriles from renewable
triglycerides is highly desirable, only one method has been reported so far, and that method requires
high temperatures (400 °C).[51] Thus, the development of more viable catalytic methods for the direct
synthesis of nitriles from triglycerides is also desirable.
In general, benign manufacturing processes for the direct transformation of triglycerides into
fatty amines, amides, and nitriles are relatively rare.[1] Herein, we report three types of selective
heterogeneous catalytic methods for the direct transformation of triglycerides into amines, amides,
and nitriles. First, we show the direct synthesis of amines from triglycerides and aqueous NH
using a Pt-loaded ZrO (Pt/ZrO ) catalyst. Then, we demonstrate the direct conversion of
triglycerides with gaseous NH in to the corresponding amides or nitriles using a commercially
3
under
H
2
2
2
3
available H-beta zeolite (Hβ) catalyst.
Scheme 1. The currently used multi-step industrial pathway to fatty amines (nitrile process) and the
direct route presented in this study.
3
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ChemSusChem
10.1002/cssc.201900365
Scheme 2. Comparison of the amidation of triglycerides: the currently favored industrial multistep
process, the direct lipase (Novozym 435) catalyzed amidation using ammonia-saturated t-butyl
alcohol, and the Hβ-75-catalyzed direct amidation with gaseous NH (this work).
3
Scheme 3. Comparison of different nitrilation processes and this work (Hβ-75-promoted one-pot
nitrilation with NH ).
3
4
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ChemSusChem
10.1002/cssc.201900365
Results and Discussion
Characterization of Pt/ZrO
2
Figure 1 shows the results of the X-ray absorption near-edge structure (XANES) and extended X-ray
absorption fine structure (EXAFS) measurements for pre-oxidized PtO /ZrO , pre-reduced Pt/ZrO
and the corresponding reference compounds (Pt foil and PtO ). The distances and coordination
numbers for the Pt–O and Pt–Pt shells were determined by a curve-fitting analysis of the EXAFS data
Table 1). The XANES spectrum of PtO /ZrO shows an intense white-line peak that is quite similar
to that of PtO . The EXAFS spectrum of PtO /ZrO consists of a single Pt–O contribution at 2.02 Å
with a coordination number of 5.5. The XANES and EXAFS results show that the Pt species in
PtO /ZrO are platinum oxides. The XANES spectrum of the reduced Pt/ZrO is basically identical to
that of Pt foil. The EXAFS analysis of Pt/ZrO shows 4.5 Pt–Pt bonds at 2.65 Å. This distance is
X
2
2
,
2
(
X
2
2
X
2
X
2
2
2
shorter than the Pt–Pt distance in bulk Pt metal (2.76 Å), and the Pt–Pt coordination number (4.5) is
lower than that of bulk Pt metal (12). These features are similar to those of previously reported small
Pt metal clusters. [52]
Figure 2 shows the annular bright field scanning transmission electron microscopy (ABF-
STEM) image and high-angle annular dark-field STEM (HAADF-STEM) images of Pt/ZrO
show small Pt particles (diameter < 2 nm). In their entirety, the characterization data of the unreduced
precursor (PtO /ZrO ) and of reduced Pt/ZrO suggest that the former is composed of platinum oxides
on ZrO , while the latter consists of small Pt nanoparticles on ZrO
2
, which
X
2
2
2
2
.
3
Figure 1. Pt L -edge XANES (left) and EXAFS Fourier transforms (right) of the Pt catalysts and the
reference compounds.
5
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ChemSusChem
10.1002/cssc.201900365
Table 1. Curve-fitting analysis of the Pt L -edge EXAFS of the supported Pt catalysts.
3
a
R (Å) b
2.02
2.65
c
R
(%) d
0.8
0.3
Sample
PtO /ZrO
Pt/ZrO
Shell
O
Pt
N
σ (Å)
f
X
2
5.5
4.5
0.061
0.078
2
a
b
c
d
Coordination number. Bond distance. Debye-Waller factor. Residual factor.
Figure 2. ABF- and HAADF-STEM images for Pt/ZrO .
2
6
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ChemSusChem
10.1002/cssc.201900365
Transformation of triglycerides into amines
To optimize the catalysts and reaction conditions for the reductive amination of triglycerides, we
carried out a benchmark reaction, in which trilaurin (1a) was treated with aqueous ammonia under H
2
3
in a stainless-steel autoclave (dead space: 9.7 cm ). Catalyst screening tests (Table 2) were carried
out using a series of supported metal nanoparticle catalysts that were pre-reduced under a flow of H
at 300 °C: a mixture of 1a (0.2 mmol), 28% aqueous ammonia (30 mmol NH ), and the catalyst
containing 0.01 mmol of Pt (5 mol% with respect to 1a) was stirred for 36 h at 220 °C under 55 bar
. Table 2 summarizes the yields of dodecylamine (2a) and N,N-didodecylamine (3a) together with
2
3
H
2
those of the undesired side products N-dodecyldodecanamide (4a) and dodecylamide (5a). In the first
screening tests (entries 2-10), we tested 5 wt% Pt on various support materials. In the absence of a
catalyst (entry 1), only 5a was obtained in 72% yield. Using PtO
yield) as an unreduced side product (entry 2). However, when using the pre-reduced metallic catalyst
Pt/ZrO (entry 3), amines were observed as the major products (2a: 43% yield; 3a: 20%), together
x
/ZrO
2
also furnished only 5a (80%
2
with unreduced side products (4a: 18%; 5a: 17%). These results indicate that metallic Pt is the active
species for the present reductive amination, while Pt oxides are inactive. Exposure of the reduced
Pt/ZrO
a: 3%). The lower yields could potentially be attributed to a decrease in the superficial amount of Pt0
species due to a re-oxidation by O . The reactions using metallic Pt on carbon (entry 5) and various
other metal oxides (Al , CeO , TiO , Nb , and MgO; entries 6–10) afforded mixtures of 2a, 3a,
a, and 5a, and the yields of amines 2a and 3a were lower than those obtained from Pt/ZrO
Interestingly, the yields of the amines increased upon decreasing the Pt load from 5 wt% to 1 wt%
entries 12-20). The yield of 2a obtained from using 1 wt% Pt on ZrO (entry 12) was higher than
those obtained from other transition-metal-loaded ZrO catalysts (entries 13-20), which furnished the
unreduced amides 4a and 5a as the major products. The yield of 2a decreased in the order Pt > Pd
Ru > Rh > Ni > Ir > Re > Cu > Ag. Based on the screening results, we identified 1 wt% Pt/ZrO
entry 12) as the most suitable catalyst for the selective amination of 1a to amines (2a and 3a).
In separate catalytic experiments using Pt/ZrO catalysts with different Pt loadings (1, 3, and
wt%), we estimated the initial formation rates for the conversion of 1a into amines 2a and 3a under
2
catalyst to air at room temperature for 0.5 h (entry 4) resulted in lower amine yields (2a: 17%;
3
2
O
2 3
2
2
2
O
5
4
2
.
(
2
2
>
2
(
2
5
those conditions where the conversion of 1a was < 40%, and we calculated the rates per total number
of Pt atoms in the catalysts. We also carried out CO-adsorption experiments for the Pt/ZrO catalysts
2
0
in order to estimate the number of superficial Pt sites. The reaction rates per total number of Pt atoms
0
and the fraction of surface Pt sites per total number of Pt atoms in Pt/ZrO
2
(Figure 3) show similar
trends as a function of the Pt loading, and the catalyst with the lowest loading exhibits the highest
0
conversion rate and the highest fraction of superficial Pt sites. These results show that the high
0
activity of the 1 wt% Pt/ZrO
2
catalyst is due to the high dispersion of Pt in the catalyst.
7
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ChemSusChem
10.1002/cssc.201900365
Table 2. Catalyst screening for the amination of triglyceride 1a into amines (2a and 3a) and amides
(
4a and 5a).
Entry Catalyst
2a Yield [%] a
3a Yield [%] a
4a Yield [%] a
5a Yield [%] a
1
2
3
4
5
6
7
8
9
1
1
1
1
1
1
1
1
1
1
2
none
PtO /ZrO
0
0
43
17
3
0
0
20
3
0
2
26
8
6
0
0
18
1
5
7
11
7
4
1
17
7
7
2
1
3
5
2
1
72
80
17
77
79
82
46
60
79
87
9
x
2
Pt/ZrO
Pt/ZrO
Pt/C
2
-air b
2
Pt/Al
Pt/CeO
Pt/TiO
Pt/Nb
Pt/MgO
2
O
3
6
2
14
21
9
2
2
O
5
0
1
2
3
4
5
6
7
8
9
0
6
1
Pt/ZrO
Pt/ZrO
2
48
59
28
19
11
13
21
9
24
32
9
6
7
5
8
6
2
2
2
Pd/ZrO
Rh/ZrO
Ir/ZrO
2
45
57
69
71
53
73
86
85
2
2
Ni/ZrO
Ru/ZrO
Re/ZrO
Cu/ZrO
2
2
2
2
1
0
Ag/ZrO
2
0
0
a
Yields were determined by GC (error range: ±1.5%) Metal loading: 5 wt% for entries 2-10; 3 wt% for entry
1; 1 wt% for entries 12-20. b A pre-reduced Pt/ZrO
catalyst was exposed to air for 0.5 h at room temperature
1
2
prior to use.
8
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ChemSusChem
10.1002/cssc.201900365
Figure 3. Conversion rate for the amination of 1a into 2a and 3a per total number of Pt atoms in the
0
catalyst and fraction of the superficial Pt sites per total number of Pt atoms in Pt/ZrO
of the Pt loading in the catalyst.
2
as a function
Using the most effective catalyst, 1wt% Pt/ZrO
Figure 4 shows plots of the yields of amines 2a and 3a and amides 4a and 5a as a function of (A) the
reaction temperature (150-240 °C), (B) the H pressure (10-55 bar), (C) the amount of catalyst (0.5-
.0 mol%), and the reaction time (0-36 h) for the Pt/ZrO -catalyzed reductive amination of 1a with
. The temperature dependence of the yields under otherwise optimized conditions (55
2
, we then optimized the reaction conditions.
2
5
2
aqueous NH
3
bar H
results in a decreased yield of dodecylamide (5a) and an increased yield of amines (2a and 3a);
accordingly, 220 °C was identified as the optimal temperature. The effect of the H pressure on the
yields under otherwise optimized conditions (220 °C, 36 h, 5 mol% catalyst) in Figure 4B shows that
increasing the H pressure leads to a decreased yield of amide 5a, while the yield of the amines (2a
and 3a) is increased; accordingly, 55 bar was identified as the most suitable pressure. The effect of
the amount of catalyst on the yields under otherwise optimized conditions (220 °C, 55 bar H , 36 h)
2
, 36 h, 5 mol% catalyst) in Figure 4A shows that increasing the temperature (up to 220 °C)
2
2
2
in Figure 4C shows that increasing the amount of catalyst decreases the yield of amide 5a and
increases that of the amines (2a and 3a); accordingly, 5 mol% of the catalyst affords the highest yield
of the amines (2a and 3a). The time course of the reaction under the optimal conditions (Figure 4D)
shows the typical kinetic pattern of a consecutive reaction. In the early stages of the reaction (t < 5 h),
the amount of unreacted trilaurin (1a) decreases with time, accompanied by the formation of
dodecylamide (5a) and then N-dodecyldodecanamide (4a). The yields of 5a and 4a reach a maximum
at 5 h and 8 h, respectively, before they decrease with time, accompanied by the formation of the
9
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ChemSusChem
10.1002/cssc.201900365
amines (2a and 3a). After 36 h, the yields of the amines do not increase anymore. It should be noted
that the formation of glycerol was not observed during the time-course analysis of the amination
reaction. The kinetic results indicate that 2a and 3a are produced via the consecutive pathways shown
in eqn. (1): 1a undergoes a direct amidation with NH
3
to give 5a, which is then hydrogenated to give
a; part of 2a can react with free lauric acid to give the N-dodecyldodecanamide 4a. Dodecylamine
a partly can also undergo a self-coupling reaction to form N,N-didodecylamine 3a, which could also
2
2
partly be produced by the hydrogenation of N-dodecyldodecanamide 4a.
In order to demonstrate a gram-scale synthesis of an amine (eqn. 2), we treated 1 mmol of 1a
and 150 mmol of NH
3
(aq.) for 96 h under 55 bar of H
2
using 1 mol% of Pt/ZrO , which resulted in the
2
formation of dodecylamine (51%) and N,N-didodecylamine (36%). This result implies that the
developed method can most likely be applied to up-scaled conversions of triglycerides into
corresponding amines.
Under the optimized reaction conditions (220 °C, 36 h, 55 bar H
we examined the substrate scope for the reductive amination of triglycerides with ammonia (Scheme
). A series of triglycerides with different chain lengths (C4-C18) were converted into the
2
, 5 mol% of 1 wt% Pt/ZrO
2
),
4
corresponding primary and secondary fatty amines, whereby the yield of the former was moderate to
good (48-59%). It is noteworthy that thus obtained fatty amines are an important class of chemicals
for the industrial production of surfactants, germicides, and softeners. Although the reductive
amination of relatively reactive carbonyl compounds such as ketones and aldehydes into amines has
been studied extensively,[53-59] reports on the reductive amination of carboxylic acids and esters
including triglycerides remain relatively rare.[33,38,60-63] Our heterogeneous catalytic system using NH
3
as a nitrogen source and H does not require any additives and could thus serve as an effective
2
method for the direct transformation of triglycerides into fatty amines.
10
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ChemSusChem
10.1002/cssc.201900365
Figure 4. Optimization of the reaction conditions for the reductive amination of trilaurin 1a.
Scheme 4. Examination of the substrate scope for the reductive amination of various triglycerides
using 5 mol% of 1 wt% Pt/ZrO
2
.
11
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ChemSusChem
10.1002/cssc.201900365
Transformation of triglycerides into amides and nitriles.
Potentially, the reactions of triglycerides with NH could also represent useful synthetic routes to fatty
3
amides and nitriles. However, catalytic methods that afford fatty amides and nitriles in high yield
remain rare, mostly due to the low reactivity of triglycerides and the difficulties associated with
controlling the selectivity, i.e., the difficulties associated with preventing an over-dehydration to nitriles.
Classically, multi-step methods with low atom efficiency are used for the synthesis of fatty amides and
nitriles.[12] Thus, an operationally simple heterogeneous catalytic method for the selective synthesis
of primary fatty amides from triglycerides and ammonia represents an attractive research target.
To establish high-yield catalytic methods for the transformation of triglycerides into fatty
amides and nitriles, we carried out a catalyst screening on the model substrate trilaurin 1a (4 bar/ 4.8
mmol NH
Under the applied conditions and in the absence of any catalyst, 5a and 6a were not obtained (entry
). Various acid or base catalysts, including various types of heterogeneous catalysts (entries 2-17)
and three types of homogeneous catalysts (entries 18-20) were also tested for this reaction. Among
various single-metal oxides, ZrO (entry 6) and SiO (entry 8) afforded 5a in relatively high yield (67-
8%). We also screened Hbeta (Hβ) zeolites with different Si/Al ratios; Hβ-75, a zeolite with an
intermediate Si:Al ratio of 75:1, furnished the highest yield of 5a (95%). Among commercially available
acidic resins, Amberlyst-15 afforded 5a in higher yield (82%) than a Nafion/SiO composite (32%).
The water-tolerant homogeneous Lewis acid Sc(OTf) and the homogeneous Brønsted acids p-
toluenesulfonic acid (PTSA) and H SO furnished 5a in moderate to low yields (8-41%). Thus, Hβ-75
3
; 180 °C; 5 h). Table 3 summarizes the yields of dodecylamide 5a and dodecanenitrile 6a.
1
2
2
6
2
3
2
4
was identified as the best catalyst for the selective synthesis of amide 5a from trilaurin 1a and NH .
3
12
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ChemSusChem
10.1002/cssc.201900365
Table 3. Catalyst screening for the selective amidation of trilaurin (1a) to dodecylamide (5a).
Entry
Catalysts
none
5a Yield [%] a
6a Yield [%] a
1
2
3
4
5
6
7
8
9
0
0
10
6
3
4
5
4
7
5
6
4
4
3
5
2
7
5
7
3
1
2
Nb O
5
28
19
16
24
67
9
TiO
2
CeO
Al
ZrO
MgO
SiO
2
2
O
3
2
2
68
62
66
95
78
52
61
59
82
32
41
32
8
Hβ-12.5
Hβ-20
10
11
12
13
14
15
16
17
18
19
20
Hβ-75
Hβ-255
HZSM5-75
HY-50
HMOR-45
Amberlyst-15
Nafion/SiO
2
Sc(OTf)
PTSA
3
2
H SO
4
a
Yields were determined by GC (error range: ±1.5%)
Subsequently, we tested the effect of various reaction parameters on the yields of 5a and 6a
for this reaction (Figure 5). The effect of the reaction temperature on the yields of 5a and 6a shows
that the yield of 5a is highest at 180 °C (Figure 5A). The effect of the initial NH pressure on the yields
of 5a and 6a were tested by carrying out the reaction at 180 °C using different initial amounts of NH
mmol) in the reactor. The results (Figure 5B) show that increasing amounts of NH afford higher
yields of 5a. The time course of the reaction under 4 bar NH (4.8 mmol NH ) at 180 °C (Figure 5C)
shows that the yield of 5a reaches a maximum after 5 h. Based on these results, the optimal conditions
for the selective synthesis of fatty amides were determined as: 4 bar NH , 180 °C, 5 h, Hβ-75 (80 mg).
3
3
(
3
3
3
3
The Hβ-75-catalyzed reaction of triglycerides with gaseous ammonia is time-dependent, and
produces nitriles after prolonged reaction times. In order to demonstrate a gram-scale synthesis of
dodecanamide (eqn. 3), we treated 1 mmol of trilaurin 1a for 15 h with 4.6 mmol (considering 29.3
13
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ChemSusChem
10.1002/cssc.201900365
3
cm of dead space) of NH
3
(g) using 150 mg of Hβ-75 (optimized conditions for the complete
conversion of trilaurin to produce a minimum of the corresponding nitrile), which furnished
dodecanamide (89%) and dodecanenitrile (5%). Moreover, we have conducted a gram-scale reaction
for the synthesis of nitriles from trilaurin (eqn. 4). Using 80 mg of Hβ-75, the reaction between trilaurin
3
o
(
1 mmol) and NH (g) 4.6 mmol (considering 29.3 cm of dead space) for 96 h at 220 C resulted in
3
the formation of dodecanenitrile (91%) and dodecanamide (3%).
Under the optimized conditions, we examined the substrate scope of this catalytic amidation
using various triglycerides (Scheme 5). Triglycerides with different chain lengths (C4-C18) were
selectively transformed into the corresponding fatty amides in high yield (82-95%). A slightly longer
time (6 h) was required for the optimal transformation of the long-chain triglycerides (C13, C15, and
C17).
The time course data at 180 °C (Figure 5C) after 5 h shows that amide 5a is converted into
6
a in up to 78% yield (after 36 h). This indicates that 5a undergoes dehydration to form dodecanenitrile
a. This result motivated us to investigate the optimal conditions for the selective conversion of
6
triglycerides into nitriles using Hβ-75 as a catalyst. Figure 5D shows the time course of the same
reaction at higher temperature (220 °C). The formation rate of 6a and the final yield of 6a were higher
than those at 180 °C, i.e., the yield of nitrile 6a reached 96% after 40 h. It is interesting to note that
only by tuning the reaction conditions, the same zeolite works as a catalyst for the selective synthesis
of amides and nitriles.
Under the conditions stipulated in Figure 5D (40 h), we studied the substrate scope of the
direct nitrile synthesis using various triglycerides (Scheme 6). The C4-C18 triglycerides were
transformed into the corresponding fatty nitriles in high yield (86-98%). Conventionally, fatty nitriles
are produced from triglycerides via methyl esterification, followed by amidation with ammonia and
dehydration of the amides to the corresponding fatty nitriles.[1,49,50] This reaction represents a rare
example of a direct catalytic reductive nitrilation of various triglycerides with NH .
3
14
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ChemSusChem
10.1002/cssc.201900365
Figure 5. Optimization of the reaction conditions for the selective amidation of trilaurin (1a) to
dodecylamide (5a) and dodecylnitrile (6a).
Scheme 5. Hβ-75 catalyzed direct amidation of triglycerides with NH .
3
15
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ChemSusChem
10.1002/cssc.201900365
Scheme 6. Hβ-75 catalyzed direct nitrilation of triglycerides with NH .
3
We have also demonstrated the applicability of our catalytic systems to lauric acid as a
homologue of fatty acids. We carried out the amination, amidation, and nitrilation of lauric acid using
a Pt/ZrO catalyst as outlined in eqn. (5) and the Hβ-75 catalyst as outlined in eqns. (6) and (7),
2
respectively. In these reactions, the amount of lauric acid (0.6 mmol) was adjusted to that theoretically
generated from trilaurin (0.2 mmol) used in the respective model reactions, while the other reaction
parameters were kept identical to those of the model reactions. The reductive amination of lauric acid
produced dodecylamine 2a and N,N-didocecylamine 3a in 50% and 35% yield, respectively. The
amidation and nitrilation of lauric acid also afforded the corresponding amide 5a and nitrile 6a in high
yields as shown in eqns. (6) and (7).
16
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ChemSusChem
10.1002/cssc.201900365
Finally, we would like to discuss the factors affecting the catalytic activity of Hβ for the direct
conversion of triglyceride 1a into amides and nitriles using NH . Employing Hβ catalysts with different
3
Si/Al ratios, we estimated the initial formation rates of amide 5a and nitrile 6a at 180 °C and 220 °C,
respectively, under conditions where the conversion of 1a was < 40%. As shown in Figure 6, the
reaction rate per catalyst weight shows a volcano type dependence on the Si/Al ratio, in which Hβ
with a moderate Si/Al ratio (Hβ-75) gives the highest rate. Recently, we have studied the hydrophilicity
and acidity of such Hβ catalysts; [64-65] the number of acid sites was estimated by NH
3
-TPD
(
temperature programmed desorption) and the hydrophobicity was estimated by the number of n-
dodecane adsorbed on Hβ in water. The number of acid sites decreases with increasing Si/Al ratio,
while the hydrophobicity of Hβ increases with the Si/Al ratio (Figure 6). Using the number of the acid
sites, we calculated the turnover frequency (TOF) per acid site. The TOF for the formation of amides
and nitriles increases with increasing Si/Al ratio, i.e., similar to the trend observed for the
hydrophobicity of the zeolites.[66] These results indicate that the acidity and hydrophobicity are two
important factors affecting the activity of the Hβ catalysts in this direct and selective catalytic reductive
amidation/nitrilation of various triglycerides with NH . A larger number of acid sites and high
3
hydrophobicity can increase the reaction rates (relative to the weight of the catalyst), which is the
reason why the Hβ catalyst with a moderate Si/Al ratio (Hβ-75) exhibits the highest catalytic activity.
17
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ChemSusChem
10.1002/cssc.201900365
Figure 6. (A) Number of acid sites and amount of n-dodecane adsorbed in Hβ (hydrophobicity); (B)
formation rates of amide 5a and nitrile 6a in the reactions of 1a with NH at 180 °C and 220 °C,
3
respectively; (C) TOF per number of acid sites for the formation of amide 5a and nitrile 6a as a function
of the Si/Al ratio in Hβ.
18
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10.1002/cssc.201900365
Conclusions
This study presents three heterogeneous catalytic methods for the selective one-pot transformation
of triglycerides to value-added chemicals: (i) a reductive amination of triglycerides into fatty amines
with aqueous NH
amidation of triglycerides under gaseous NH
synthesis of nitriles from triglycerides and gaseous NH
3
under an atmosphere of H
using a high-silica Hβ zeolite at 180 °C, and (iii) a direct
using a high-silica Hβ zeolite at 220°C. These
2
using ZrO -supported Pt metal nanoparticles, (ii) an
2
3
3
methods selectively transform a wide variety of triglycerides (C4-C18) into the corresponding amines,
amides, and nitriles, and thus represent a milestone in chemical transformation of triglycerides. A
systematic analysis of reaction (ii) and (iii) reveals that the acidity and hydrophobicity of the zeolites
are two important factors that affect the catalytic activity of the Hβ catalysts. Specifically, increasing
the number of acid sites and increasing the hydrophobicity may lead to higher reaction rates per
weight of the catalyst.
19
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ChemSusChem
10.1002/cssc.201900365
Experimental
General
Chemical reagents were purchased from common commercial suppliers (Tokyo Chemical Industry,
Wako Pure Chemical Industries, Kishida Chemical, or Mitsuwa Chemicals) and used as received.
GC-FID (Shimadzu GC-2014) and GC-MS (Shimadzu GCMS-QP2010) analyses were performed
+
using an Ultra ALLOY capillary column UA -1 (Frontier Laboratories Ltd.) with N
2
or He as the carrier
1
13
gas. H and C NMR measurements were conducted on a JEOL-ECX 600 spectrometer operating
1
13
1
at 600.17 ( H) and 150.92 MHz ( C), or on a JEOL-ECX 400 spectrometer operating at 399.78 ( H)
13
and 100.52 MHz ( C), using tetramethylsilane as the internal standard.
Catalyst preparation
In the zeolites Hβ-x, x denotes the Si/Al ratio. The catalysts Hβ-75 (JRC-Z-HΒ150; originally supplied
from Clariant), Hβ-12.5 (JRC-Z-HΒ25), HMOR-45 (JRC-Z-HM90; originally supplied from Clariant),
2
-1
ZrO
were supplied by the Catalysis Society of Japan. Nb
Nb ·nH O (kindly supplied by CBMM). SiO (Q-10; 300 m g ) was kindly supplied by Fuji Silysia
Chemical Ltd. The carbon support (296 m g ; Kishida Chemical) was commercially obtained. γ-Al
2
(JRC-ZRO-5; 193.7 m g ), TiO
2
(JRC-TIO-4), CeO
2
(JRC-CEO-3), and MgO (JRC-MGO-3)
2
O
5
was prepared by calcination (500 °C; 3 h) of
2
-1
2
O
5
2
2
2
-1
2
O
3
was prepared by calcination of γ-AlOOH (Catapal B Alumina kindly supplied by Sasol; 900 °C; 3 h).
Hβ-20 (HSZ-940HOA), Hβ-255 (HSZ-980HOA) and HY-50 (HSZ-385HUA) were purchased from
Tosoh Co. HZSM5-75 was supplied from N.E. CHEMCAT Co.
Pt/ZrO
and an aqueous HNO
110 °C; 12 h) and reduction in a Pyrex tube under a flow of H
supported Pt catalysts with Pt loadings of 5 wt% were prepared by the same method. M/ZrO
Rh, Ir, Ru, Pd, Re, Cu, Ni, Ag) catalysts with a metal loading of 1 wt% were prepared by a similar
2
catalysts with a Pt loading of 1, 3, and 5 wt% were prepared by evaporating a mixture
of ZrO
2
3
solution of Pt(NH (NO at 50 °C, followed by consecutive drying
3
)
2
3 2
)
3
-1
(
2
(20 cm min ) at 300 °C (0.5 h). Other
(M =
2
method as for Pt/ZrO
solutions of metal nitrates (Ni, Cu, Ag), IrCl
PtO /ZrO
2
using aqueous HNO
3
solutions of Rh(NO
O, RuCl , or NH ReO
(NO -loaded ZrO
3
)
3
or Pd(NH
. Platinum-oxide-loaded ZrO
(300 °C; 0.5 h; in air).
3
)
2
(NO
3
) , aqueous
2
3
·nH
2
3
4
4
2
(
x
2
) was prepared by calcination of the Pt(NH
3
)
2
3
)
2
2
Characterization. ABF- and HAADF-STEM images for 1 wt% Pt/ZrO
ARM200F microscope (JEOL) using an acceleration voltage of 200 kV. The Cs-corrector CESCOR
CEOS) was used in the STEM mode. The pre-reduced catalyst powder that was exposed to air at
2
were recorded on a JEM-
(
room temperature, was mixed with ethanol, and this ethanolic suspension of the sample was dropped
on a carbon-supported copper grid.
3
Pt L -edge X-ray absorption near-edge structures (XANES) and extended X-ray absorption
fine structure (EXAFS) measurements were carried out in transmittance mode at the BL14B2
20
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ChemSusChem
10.1002/cssc.201900365
beamline of SPring-8 (8 GeV), using a Si(311) double crystal monochromator. The Pt/ZrO
2
catalyst,
(20 cm min ) for 0.5 h at 300 °C, was cooled to room temperature
and sealed in a polyethylene-cell under N , before the EXAFS spectrum was
recorded at room temperature. The curve-fitting EXAFS analysis was carried out using the REX ver.
.5 program (RIGAKU) and the parameters for the Pt–O and Pt–Pt shells provided by FEFF6.
3
-1
pre-reduced under a flow of H
under the flow of H
2
2
2
2
Catalytic reactions.
Before the catalytic tests for the amine synthesis, the metal catalysts were deposited in a glass tube
3
(
6.5 cm ) and reduced for 0.5 h under a flow of H
2
at 300 °C. Catalytic experiments were carried out
without exposing the reduced catalyst to air. Hexadecane (1 mmol) was added to the reduced catalyst
via a septum inlet; thus, the catalyst was covered with the hexadecane layer to avoid exposure to air.
After removal of the septum in air, triglycerides (0.2 mmol), an aqueous solution of 28 wt% NH (30
3
mmol) and a magnetic stirrer bar were added to the tube. The tube was then inserted into a stainless-
3
steel autoclave (dead space: 9.7 cm ) and pressurized with H
2
(55 bar), followed by heating the
autoclave to 220 °C for 36 h.
For the syntheses of amides and nitriles, triglycerides (0.2 mmol), n-hexadecane (0.25 mmol),
3
and a magnetic stirrer bar were deposited in a reaction tube (30 cm ) in air. The glass tube was then
3
inserted in a low-pressure autoclave (dead space: 30 cm ). Then, NH
3
(gas; 4.8 mmol) was added
into the closed autoclave, which was subsequently heated for 5 h to 180 °C to yield the amide, and
for 40 h to 220 °C to yield the nitriles.
After completion of the reaction, ethyl acetate (3 mL) was added and the products were
+
analyzed by GC (Shimadzu GC-14B; Ultra ALLOY capillary column UA -1 from Frontier Laboratories
+
Ltd.; N
2
) and GC-MS (SHIMADZU GCMS-QP2010; Ultra ALLOY capillary column UA -1 from Frontier
Laboratories Ltd.; He). The products were isolated by column chromatography on silica gel 60
(
spherical; 50-100 μm; Kanto Chemical Co. Ltd.) using hexane/ethyl acetate (75/25, v/v) as the eluent.
The isolated products were then analyzed by GC and GC-MS, as well as H and 13C NMR
spectroscopy. Isolated yields were determined relative to the starting triglycerides. Product yields
based on the amount of ester groups in the triglycerides were determined by GC analysis, where GC
sensitivities were estimated in comparison to the isolated products or to the commercial products
using n-hexadecane as an internal standard. Further careful analyses of GC conversions and yields
were also carried out affording an error range (±1.5 %) by exploiting the duplicated yields or
conversions of the same reaction. In the substrate-scope studies (Schemes 4-6), the product yields
are based on GC analysis, while the product identification was accomplished by GC-MS analysis.
To ensure the presence of glycerol in the reaction mixture of all three types of the reactions,
1
we worked-up each model reaction by adding ethyl acetate (3 mL) and D O (2 mL). Then, the aqueous
2
1
layer was analyzed by H NMR spectroscopy. The amination reaction did not show the presence of
glycerol using this reductive catalytic system, whereas the presence of glycerol was confirmed in the
21
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ChemSusChem
10.1002/cssc.201900365
reaction mixtures of the amidations and nitrilations. The formed glycerol could be separated from the
desired products simply by washing with water.
Acknowledgements
This study was supported by JSPS KAKENHI grants 17H01341, 18K14051, and 18K14057, by the
Japanese Ministry of Education, Culture, Sports, Science, and Technology (MEXT) within the projects
"
Integrated Research Consortium on Chemical Sciences (IRCCS)" and "Elements Strategy Initiative
to Form Core Research Center", as well as by the JST-CREST project JPMJCR17J3. The authors
are indebted to the technical division of the Institute for Catalysis (Hokkaido University) for
manufacturing experimental equipment. X-ray absorption measurements were performed at BL-14B2
of SPring-8 at the Japan Synchrotron Radiation Research Institute (JASRI) under proposal
2018A1757.
22
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ChemSusChem
10.1002/cssc.201900365
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Entry for the Table of Contents
FULL PAPER
Three heterogeneous catalytic
methods for the selective one-
Md. A. R. Jamil, S.M.A. Hakim
Siddiki,* Abeda S. Touchy, Md.
Nurnobi Rashed, Sharmin S. Poly,
Yuan Jing, Kah Wei Ting, Takashi
Toyao, Zen Maeno, Ken-ichi
Shimizu,*
pot
transformation
of
triglycerides into value-added
chemicals are presented: (i) the
reductive
triglycerides into fatty amines
with aqueous NH and H , (ii) the
amidation of triglycerides with
gaseous NH , and (iii) the direct
synthesis of nitriles with gaseous
NH
amination
of
3
2
Page No. – Page No.
3
Selective Transformations of
Triglycerides into Fatty Amines,
Amides, and Nitriles using
Heterogeneous Catalysts
3
.
26
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