Esters, Including Triglycerides, and Hydrogen as Feedstocks for the Ruthenium-Catalyzed Direct N-Alkylation of Amines

Article abstract of DOI:10.1002/anie.201603681

Triglycerides are used for the direct N-alkylation of amines with molecular hydrogen for the first time. A broad range of interesting and industrially relevant secondary and tertiary amines are obtained in the presence of an in situ formed Ru/Triphos complex. Notably, plant oil can be efficiently applied in this single-step process. Moreover, a variety of other methyl esters can be used as N-alkylation agents in the presence of hydrogen for the synthesis of more advanced building blocks.

Full text of DOI:10.1002/anie.201603681

Angewandte
Communications
Chemie
International Edition: DOI: 10.1002/anie.201603681
German Edition: DOI: 10.1002/ange.201603681
Homogeneous Catalysis
Esters, Including Triglycerides, and Hydrogen as Feedstocks for the
Ruthenium-Catalyzed Direct N-Alkylation of Amines
Rosa Adam+, Jose R. Cabrero-Antonino+, Kathrin Junge, Ralf Jackstell, and Matthias Beller*
Dedicated to Professor Avelino Corma on the occasion of his 65th birthday
Abstract: Triglycerides are used for the direct N-alkylation of
amines with molecular hydrogen for the first time. A broad
range of interesting and industrially relevant secondary and
tertiary amines are obtained in the presence of an in situ
formed Ru/Triphos complex. Notably, plant oil can be
efficiently applied in this single-step process. Moreover,
a variety of other methyl esters can be used as N-alkylation
agents in the presence of hydrogen for the synthesis of more
Scheme 1. Comparing a) the nitrile process (hydrolysis, formation of
advanced building blocks.
nitrile and hydrogenation) with b) this work (direct N-alkylation with
triglycerides).
T
he development of processes and technologies that make
use of sustainable feedstocks is an important goal for chemists
in academia and industry.[1] In this context, biomass formed
through CO2 fixation is an excellent alternative to petro-
leum,[2] which also offers possibilities for new chemical
transformations. Oils and fats, mainly composed of triglycer-
ides, are among the most important biomass materials for the
chemical industry.[2a–c,e–g,3] Currently, they are used as feed-
stocks for the production of bio-derived surfactants, polymers,
lubricants, and plasticizers.[2b,e,3a–c,e,f] Another important class
of compounds obtained from triglycerides are fatty amines,
with a broad range of applications as emulsifiers, surfactants,
corrosion inhibitors, anticaking agents, fuel additives, bacter-
icides, and sludge inhibitors.[2f,3f] So far, the most common
methodology for obtaining fatty amines is the nitrile proc-
ess[2a,f,3f,4] (Scheme 1a) in which a fatty acid, obtained after
triglyceride hydrolysis, reacts with ammonia in the presence
of a dehydrating catalyst, normally a metal oxide, at high
temperature (> 2508C) to afford the corresponding nitrile.
Subsequent hydrogenation, usually catalyzed by Raney-Ni or
-Co at high temperatures, gives the desired amine. Despite the
use of triglycerides as feedstocks, this process requires harsh
conditions and several steps.
in this field using mainly alcohols,[7] but also carbonyl
compounds[8] or carboxylic acids.[9] For example, our group
recently reported the first general N-alkylation of amines with
carboxylic acids and hydrogen.[9e,10] The optimal catalyst for
this procedure is the so-called ruthenium/Triphos catalyst
system
[Triphos = 1,1,1-tris(diphenylphosphinomethyl)-
ethane], also successfully applied in the methylation of
amines with CO2,[11] as well as in the reduction of carboxylic
acid derivatives and CO2.[10,12] Inspired by this work, we
started to explore the alkylation of primary and secondary
amines with triglycerides (Scheme 1b).
In a first approach to the direct N-alkylation of amines
with triglycerides, we decided to study the ethylation of N-
methylaniline 1 using ethylene glycol diacetate 2 as a model
compound (Table S1). The [Ru(acac)3]/Triphos/HNTf2 com-
bination was selected, as it has been shown to be effective in
the alkylation of amines with carboxylic acids in the presence
of H2.[9e] A first screening of the reaction at 1508C, 60 bar of
H2, and 2 mol% of ruthenium in THF as solvent using
different amounts of ethylene glycol diacetate 2 (Table S1,
entries 1–3), pointed out that improved yields of N-ethyl-N-
methylaniline 3 were obtained in the presence of 4 equiv-
alents of the diester 2. When the reaction was performed with
simple [Ru(acac)3] or [Ru(acac)3] with HNTf2, only aromatic
ring hydrogenation products were detected (Table S1,
entries 4 and 6). Moreover, no reaction occurred in the
absence of ruthenium or HNTf2 (Table S1, entries 5 and 7).
These experiments confirm that all three components of the
catalytic system ([Ru(acac)3]/Triphos/HNTf2) are required for
the reaction to proceed. Next, we explored the influence of
several Bronsted and Lewis acids (Table S2). Among the
different additives tested, HNTf2 afforded the highest yield of
N-ethyl-N-methylaniline 3, and only HOTf gave the product
in moderate yields (73%, Table S2, entry 4). Varying the
amount of co-catalyst (Table S3) revealed improved results
with 5 mol% of HNTf2 (2.5 equivalents with respect to Ru;
Table S3, entry 5). Several ruthenium pre-catalysts and phos-
Traditional procedures for the N-alkylation of amines
involve the use of toxic alkylating agents, such as alkyl halides
or sulfonates,[5] or the combination of carboxylic acids or
esters with stoichiometric amounts of metal borohydride
reagents.[6] In recent years, many advances have been reached
[*] Dr. R. Adam,[+] Dr. J. R. Cabrero-Antonino,[+] Dr. K. Junge,
Dr. R. Jackstell, Prof. M. Beller
Leibniz-Institut fꢀr Katalyse e.V.
Albert-Einstein-Str. 29a, 18059 Rostock (Germany)
E-mail: matthias.beller@catalysis.de
[+] These authors contributed equally to this work.
Supporting information and the ORCID identification number(s) for
the author(s) of this article can be found under
http://dx.doi.org/10.1002/anie.201603681.
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phine ligands were also evaluated for this transformation
(Tables S4 and S5) and it was demonstrated that the initially
used system with [Ru(acac)3]/Triphos was the most effective
one. Remarkably, [Ru(cod)(methylallyl)2] and [Ru(PPh3)3-
(CO)H2] (Table S4, entries 2 and 5) also afforded high yields
of N-ethyl-N-methylaniline 3. At this point, a more detailed
investigation of the temperature and pressure parameters was
interesting to us (Table S1, entries 8–10). Gratifyingly, the
reaction proceeded well at 1308C (Table S1, entry 8), while
with < 60 bar of H2 the yield of N-ethyl-N-methylaniline 3
notably decreased (Table S1, entry 10).
(Table 1). Gratifyingly, alkylated anilines were obtained in
high yields using 1 equivalent of shorter chain triglycerides
(Table 1, entries 2–4) or a larger excess for glyceryl triben-
zoate or octadecanoate (Table 1, entries 1 and 5). Then, the
Table 1: Ruthenium-catalyzed N-mono-alkylation of aromatic and ali-
phatic amines with triglycerides and H2.[a]
Next, the effect of different solvents was tested (Table S6).
The best results were obtained when THFor n-Bu2O was used
(Table S6, entries 1 and 4), whereas toluene or 1,4-dioxane
also gave high yields of the alkylated product 3 (Table S3,
entries 2 and 5). To our delight, even at lower catalyst loading
(1 mol%) excellent yields of N-ethyl-N-methylaniline 3 were
obtained (Table S1, entry 12, 96%). In all of these experi-
ments, ethylene glycol and ethanol were detected as byprod-
ucts. Interestingly, also ethanol formed by hydrogenation of
the ester can be used as alkylating agent under these
conditions, albeit in much lower yield (Table S1, entry 14).
From a mechanistic point of view, this demonstrates that the
major reaction pathway proceeds directly through the ester.
Once the catalytic system was established, it was interest-
ing to explore the N-alkylation of primary amines such as
aniline 4 (Scheme 2, Table S7). Interestingly, it is possible to
Entry
Alkylated Amine
R3
Eq. Trig. Conv. [%][b] Yield [%][b]
1
2
3
4
Ph
2.5
1
90
89
87
86
C2H5
C3H7
C7H15
C17H35
C7H15
C17H35
1
91
86
1
2
2
3.5
92
100
89
89
5
[76][c]
[69]
[68][c]
6[d,e]
7[d,e]
92
8[d]
C2H5
2.5
1
100
100
[85]
[65]
9
C7H15
10
11
C7H15
C17H35
1.5
2.5
95
100
[85]
[80][c]
12
13
C7H15
C7H15
1
97
93
[78]
[85]
0.5
14
15
C7H15
C17H35
2
2.5
84
100
[76]
[82][c]
Scheme 2. Ruthenium-catalyzed selective mono and di-alkylation of
aniline 4 with ethylene glycol diacetate 2. [a] Determined by GC using
hexadecane as internal standard.
16[f]
C3H7
0.5
95
[80]
perform both selective mono- and dialkylation simply by
tuning the reaction conditions. Thus, when the reaction was
carried out at 1308C, 1 mol% of Ru, and 1.5 equivalents of 2,
N-ethylaniline 5 was obtained in 83% yield with a 1:0.1 mono/
dialkylation ratio. By contrast, at 1508C using 6 mol% of Ru
and 6 equivalents of the diester 2, N,N-diethylaniline 6 was
formed in a 86%, with the inverse ratio.
To gain more insight in this process, yield/time kinetic
profiles corresponding to the alkylation of N-methylaniline 1,
and mono- and di-alkylation of aniline 4 were performed
(Figures S1–S3). No reaction intermediates were detected in
any of these experiments, nor were induction periods
observed. In the case of di-alkylation of aniline (Figure S3),
high concentrations of N-ethylaniline 5 were observed at
short reaction times that immediately reverted in favor of the
formation of N,N-diethylaniline 6.
17
18
C7H15
C17H35
1
2
100
100
[88]
[70][c]
19
20
C3H7
C7H15
1
1
97
98
[78]
[90]
21
22
23
24
25
26
C2H5
C3H7
C7H15
C17H35
C2H5
4
4
4
3
4
4
97
97
98
98
91
89
[79]
[90]
[87]
[80][c]
[75]
[74]
C7H15
27
28
C2H5
C7H15
4
4
90
90
[85]
[79]
29
C7H15
3
100
[90]
With these findings in hand, we decided to explore the
direct alkylation of amines using various triglycerides
2
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Table 1: (Continued)
Entry
Alkylated Amine
R3
Eq. Trig. Conv. [%][b] Yield [%][b]
30
31
C2H5
C7H15
4
4
100
100
[93]
[83]
32[d]
C7H15
4
88
[83]
Scheme 3. Ruthenium-catalyzed N-alkylation of aniline 4 using sun-
flower oil as triglycerides source. [a] Sunflower oil contains: 59%
R=C17H31, 30% R=C17H33, 6% R=C17H35, and 5% R=C15H31.
33
34
C2H5
C7H15
3.5
3.5
100
100
[94]
[96]
35
36
C3H7
C7H15
0.5
0.5
100
100
[89]
[92]
methyl esters was carried out (Scheme 4, Table S8). In
general, aliphatic and benzylic esters worked as alkylating
agents at 1308C, whereas for aromatic ones slightly higher
temperature (1508C) and/or higher catalyst loadings were
needed. For example, several fluorine-substituted amines can
be obtained through this methodology. Moreover, using
inexpensive dimethyl phthalate as the alkylating agent
allows obtaining N-phenylisoindolinone.
37[d]
38
C7H15
C3H7
0.5
3
94
94
80
92
39[d]
C7H15
2
100
98
[a] Standard reaction conditions: amine (0.5 mmol), [Ru(acac)3]
(2 mol%), Triphos (3 mol%), HNTf2 (5 mol%), triglyceride (0.5-
4 equiv), THF (2 mL), 60 bar H2, 1308C, during 18 h. [b] Determined by
GC using hexadecane as internal standard, values between brackets
correspond to isolated yields. [c] Alkylating agent was used as a glyceryl
tristearate: glyceryl tripalmitate (2:1) mixture, a 2:1 mixture of octade-
cylated and hexadecylated products was obtained. [d] 1508C. [e] Ru-
(acac)3 (4 mol%). [f]>99% selectivity for alkylation of the primary
amine.
alkylation of a series of aromatic and aliphatic amines was
explored (Table 1). Both electron-donating and electron-
withdrawing substituents were well tolerated. However, the
alkylation of electron-rich primary amines proceeds more
efficiently, and lower amounts of triglyceride were needed to
avoid overalkylation (Table 1, entries 9, 12, 13, 16–20). Ortho-
substituted fluorine- and phenylanilines were also alkylated in
good yields, but required either higher temperatures and/or
increased catalyst loading (Table 1, entries 6–8). Compared to
traditional alkylation procedures, this methodology is highly
selective (> 99%) towards the functionalization of primary
amines in the presence of secondary ones (Table 1, entry 16).
However, secondary amines can also be alkylated in the
presence of an excess of triglyceride (3–4 equiv; Table 1,
entries 21–36). Notably, benzylic and aliphatic amines
(Table 1, entries 29–31, 37–39), as well as amino alcohols
(Table 1, entries 9, 13, and 32), were also smoothly alkylated.
To demonstrate the practical utility of this procedure, we
envisioned using vegetable oil as the source of triglycerides.
Thus, the reaction of aniline with the Ru/Triphos/HNTf2
system was performed using original sunflower oil[13] as the
alkylating agent (Scheme 3). To our delight, this transforma-
tion proceeded smoothly to give a mixture of N-octadecylani-
line and N-hexadecylaniline in 95% of isolated yield (9.5:0.5
ratio of octadecylated: hexadecylated product). It should be
noted that, under the reductive conditions used, the natural
unsaturated fatty acids were completely hydrogenated.
Finally, to further demonstrate the synthetic applicability
of this methodology, N-alkylation of aniline 4 with a variety of
Scheme 4. Ruthenium-catalyzed N-alkylation of aniline 4 using methyl
esters and H2. Yields determined by GC using hexadecane as internal
standard, values between brackets correspond to isolated yields.
Standard reaction conditions: 4 (0.5 mmol), methyl ester (3 equiv),
[Ru(acac)3] (2 mol%), Triphos (3 mol%), HNTf2 (5 mol%), THF
(2 mL), H2 (60 bar), 1508C, 18 h. [a] 1308C. [b] [Ru(acac)3] (3 mol%)
over 40 h. [c] [Ru(acac)3] (4 mol%). [d] Dimethyl phthalate was used as
alkylating agent. N-phenylisoindoline was found as by-product (25%).
[e] N,N-diethylaniline was found as by-product (9%).
In conclusion, we have developed a new method for the
valorization of triglycerides, an important part of biomass.
With this method it is possible to perform the selective
reductive alkylation of amines with triglycerides in a single
step using molecular hydrogen. The in situ formed catalyst
(Ru/Triphos/HNTf2) enabled the selective N-mono-alkyla-
tion of a variety of primary and secondary amines with
triglycerides. In principle, the synthesis of primary fatty
amines from ammonia and triglycerides using this procedure
should be also possible, and the development of further
studies in this direction would be of high interest. Further-
more, plant oil can be employed as a benign and effective
alkylating agent. The synthetic utility of this methodology is
further demonstrated by the use of several methyl esters as
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a valuable catalytic system, it opens the door to the develop-
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fatty amines using triglycerides.
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Experimental Section
General procedure for the N-alkylation of amines with triglycerides:
A 8 mL glass vial containing a stirring bar was sequentially charged
with amine (0.5 mmol), n-hexadecane (50 mg) as an internal standard,
[Ru(acac)3] (2–4 mol%), Triphos (3–6 mol%), THF (2 mL) as
solvent, triglyceride (0.5-4 equiv), and a freshly prepared 0.2m in
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reaction vial was capped with a septum equipped with a syringe and
set in the alloy plate, which was then placed into a 300 mL autoclave.
Once sealed, the autoclave was purged three times with 30 bar of
hydrogen, then pressurized to 60 bar and placed into an aluminum
block, which was preheated at 130–1508C. After 18 h, the autoclave
was cooled in an ice bath, and the remaining gas was carefully
released. Finally, the reaction mixture was diluted with ethyl acetate
and analyzed by GC and GC-MS. To determine the isolated yield of
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mixture was purified by silica gel column chromatography (n-
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Acknowledgements
Financial support from the state of Mecklenburg-Vorpom-
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Keywords: amines · biomass · homogeneous catalysis ·
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Klankermayer, W. Leitner, Chem. Sci. 2015, 6, 693 – 704; f) J. R.
Cabrero-Antonino, E. Alberico, K. Junge, H. Junge, M. Beller,
Chem. Sci. 2016, 7, 3432-3442; g) J. R. Cabrero-Antonino, I.
Sorribes, K. Junge, M. Beller, Angew. Chem. Int. Ed. 2016, 55,
387 – 391; Angew. Chem. 2016, 128, 395 – 399.
Office. ISBN: 0-11-322682-322689, 2005.
Received: April 15, 2016
[13] Sunflower oil composition: 5% palmitic acid, 6% stearic acid,
30% oleic acid, 59% linoleic acid: “Ph Eur monograph 1371”
Revised: June 27, 2016
Published online: && &&, &&&&
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
5
These are not the final page numbers!

Angewandte
Communications
Chemie
Communications
Homogeneous Catalysis
Give me an alkyl group: Triglycerides are
used as bio-based N-alkylating agents. In
a single-step process with hydrogen,
a broad range of amines are synthesized
using a specific Ru catalyst.
R. Adam, J. R. Cabrero-Antonino,
K. Junge, R. Jackstell,
M. Beller*
&&&& — &&&&
Esters, Including Triglycerides, and
Hydrogen as Feedstocks for the
Ruthenium-Catalyzed Direct N-Alkylation
of Amines
6
www.angewandte.org
ꢀ 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2016, 55, 1 – 6
These are not the final page numbers!