Recycling of homogeneous catalysts in reactive ionic liquid-solvent-free aminofunctionalizations of alkenes

Article abstract of DOI:10.1039/c7gc02272g

The catalyst in homogeneously catalyzed aminofunctionalizations is often difficult to recycle, making these reactions expensive on an industrial scale. The use of dimethylammonium dimethylcarbamate (dimcarb) as a reactive ionic liquid provides an elegant solution to this challenge, as it is a substrate and polar phase at the same time. In this work, homogeneously transition-metal catalyzed reactions-specifically hydroamination, telomerization and hydroaminomethylation-are carried out in neat substrates without additional solvents. The ionic character of dimcarb enables the immobilization of the active catalysts in the reactive ionic liquid, using sulfonated ligands. Investigations regarding the hydroamination of 1,3-dienes led to a total turnover number (TTON) of more than 8700 with β-farnesene in 12 repetitive recycling experiments. The telomerization of 1,3-butadiene was carried out over 30 consecutive runs without any loss of activity, resulting in a TTON of more than 90 000.

Full text of DOI:10.1039/c7gc02272g

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DOI: 10.1039/C7GC02272G
Green Chemistry
PAPER
Recycling of Homogeneous Catalysts in Reactive Ionic Liquid –
Solvent-Free Aminofunctionalizations of Alkenes
Thiemo A. Faßbacha, Robin Kirchmanna, Arno Behra and Andreas J. Vorholta,*
Received 00th January 20xx,
Accepted 00th January 20xx
The catalyst in homogeneously catalyzed aminofunctionalizations is often difficult to recycle, making these reactions
expensive on an industrial scale. The use of dimethylammonium dimethylcarbamate (dimcarb) as a reactive ionic liquid
provides an elegant solution to this challenge, as it is substrate and polar phase at the same time. In this work,
DOI: 10.1039/x0xx00000x
www.rsc.org/
homogeneously transition-metal catalyzed reactions
-
specifically hydroamination, telomerization and
hydroaminomethylation - are carried out in neat substrates without additional solvents. The ionic character of dimcarb
enables the immobilization of the active catalysts in the reactive ionic liquid, using sulfonated ligands. Investigations
regarding the hydroamination of 1,3-dienes led to a total turnover number (TTON) of more than 8,700 with -farnesene in
12 repetitive recycling experiments. The telomerization of 1,3-butadiene was carried out over 30 consecutive runs without
any loss of activity, resulting in a TTON of more than 90,000.
In contrast to commonly used ionic liquids, dimcarb offers
several advantages. It can be prepared simply by distilling a CO2-
saturated aqueous dimethylamine solution, which makes it
Introduction
Methylamines are one of the most important building blocks in
the chemical industry. Among these, the demand for
dimethylamine as building block is the highest on the global
market.1 Its derivatives are used as solvents, agrochemicals and
surfactants, such as amine oxides (N-Oxides), betaines or
quaternary ammonium compounds (quats).2 Recent research
has demonstrated that building blocks for surfactants can be
obtained via the palladium-catalyzed hydroamination of the
significantly cheaper than, for instance, imidazolium salts.15
Most ILs cannot be purified by distillation.16 This means they are
prone to byproduct contamination, which can accumulate in a
continuous process. By contrast, dimcarb can be distilled with
ease at moderate temperatures (bp: 68 °C). Using dimcarb as a
reactive ionic liquid, i.e. as both the substrate and the solvent,
eliminates the need for additional solvents in this
homogenously catalyzed reaction. To date, there are several
approaches to catalyst recycling in hydroamination reactions,
terpene 
-farnesene with dimethylamine.3 Hydroaminations of
1,3-dienes are typically catalyzed by palladium or nickel
complexes with diphosphine ligands.4–12 The hydroamination of
e.g. the use of thermomorphic solvent systems (TMS)7,17
,
catalyst precipitation18, the immobilization on supported ionic
liquid phases (SILP)19 or other heterogeneous supports20. If it
were possible to overcome the opposing polarities of the ionic
dimcarb and the non-polar hydrocarbon farnesene during as
well as re-establish them after the reaction, an efficient catalyst
recycle would be possible. To realize this concept, three
fundamental conditions must be fulfilled:

-farnesene with secondary amines was originally carried out in
DMF. As a source for dimethylamine, the respective CO2-adduct
dimethylammonium dimethylcarbamate (in brief: dimcarb, see
Scheme 1) was used. Liquid dimcarb is easy to handle and can
be considered an ionic liquid (IL), as ionic form
predominates.13,14
I.
The substrates must be sufficiently solubilized in the
same phase as the catalyst.
II.
The reaction can only be catalyzed in the absence of a
solvent, if the substrates do not hamper the catalyst
both chemically and physically.
III.
After the reaction, products and catalyst must be
separated effectively and easily, e.g. by extraction or,
ideally, by spontaneous phase separation and
decanting.
Scheme
1
Synthesis and tautomeric forms of dimethylammonium
dimethylcarbamate (dimcarb).
Fakultät für Bio- und Chemieingenieurwesen, Lehrstuhl für Technische Chemie,
Technische Universität Dortmund
Emil-Figge-Straße 66, 44227 Dortmund (Germany)
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Green Chem., 2017, 00, 1-6 | 1
E-mail:
andreas.vorholt@bci.tu-dortmund.de
Electronic
Supplementary
Information (ESI) available: Characterization of all products and detailed results,
including leaching values. See DOI: 10.1039/x0xx00000x
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Results & Discussion
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DOI: 10.1039/C7GC02272G
Hydroamination
To address I., one must clarify whether the reaction is to take
place in one homogeneous phase or if there is a biphasic
reaction mixture. To clarify this, the substrates were weighed in
a 300 mL reactor with a sight glass, stirred and heated to 100 °C,
which is a typical reaction temperature for hydroaminations. At
the beginning both compounds are not miscible and build two
clear phases. After heating the mixture to approximately 90 °C,
phase behavior changes. Despite a continuously occurring
vaporization/condensation of the dimcarb, which makes the
solution turbid, the substrate mixture is one homogeneous
liquid phase at reaction temperature (Figure 1). This means that
the reaction mixture shows phase behavior that is quite similar
to thermomorphic solvent systems21,22 as opposed to
liquid/liquid biphasic systems.23 Another possible explanation
for the observed behavior might be the presence of a gas-
expanded liquid.24 In terms of II., the reaction must be carried
out in neat substrates. Hydroaminations are typically not
carried out in the neat substrates, since high concentrations of
amine inhibit the hydroamination catalyst.3,7,25 Surprisingly, the
hydroamination of farnesene with dimcarb not only works well
in DMF, but can be carried out easily without additional
solvents. Subsequent to optimizations to the reaction
parameters, the reaction was even carried out using only
0.1 mol% of palladium, which is an eighth of the original amount
Figure 2 Structure of the applied DPPB and the DPPBTS ligand.
In the present case, the upper layer consists almost exclusively
of the desired products and non-converted farnesene, while the
excess dimcarb forms the lower phase. The catalyst was
recycled successfully by removing the product phase, adding
new substrate and restarting the reaction, which showed
catalytic activity in three recycling experiments. Unfortunately,
from the second run on, the yields drop by one third after each
recycle (Figure 3).
ICP-OES measurements indicate that this is the result of severe
palladium leaching into the non-polar product phase in nearly
the same quantity (detailed results of yields and leaching can be
found in the supporting information). In order to effectively
immobilize the catalyst complex in dimcarb, which is
predominantly available in the ionic form, the tetra-sulfonated
analog ligand DPPBTS (=1,4-bis(diphenylphosphino)butane-
tetra-sulfonate, see Figure 2), was employed. The first recycling
run yielded slightly more product than in the initial run, which
was likely caused by small amounts of the product remaining in
the catalyst phase. After the dimcarb is saturated with products,
the isolated yields are maintained. The next eight runs show
consistently high catalytic activity, which is backed by very little
to no (< 0.1%) leaching of palladium and phosphorous into the
product phase (for detailed data of the ICP-OES measurements,
see supporting information). After the eighth run, the catalyst
phase turned from a light yellow color to dark orange, indicating
a decomposition of the catalyst. According to 31P-NMR the
of
palladium
and
diphosphine
ligand
DPPB
(=1,4-bis(diphenylphosphino)butane see Figure 2). The reaction
leads to N,N-dimethyl farnesylamines at a yield of 89% after
4 hours (Scheme 2). This constitutes an increase in the turnover
frequency (calculated as moles of products per mole of
palladium/hour) from 29 h-1 in the reaction carried out in DMF
to 223 h-1 in dimcarb. Research has shown that some transition
metal catalyzed reactions show higher reaction rates when
carried out in ionic liquids.26 Thus, it is plausible that these good
results are consequences of an interaction of the reactive ionic
liquid with the catalyst and/or a transition state in the catalytic
cycle. After the reaction takes place and the mixture is cooled
to room temperature, a spontaneous phase separation occurs.
This phase behavior is very favorable because it enables
ligand (
 = -15.25) was oxidized to the phosphine oxide
(
= +32.41), most probably due to oxygen contamination.27
product/catalyst separation, contributing to III.
.
Another plausible explanation would be the presence of
peroxides in one of the substrates.28
Figure 1 Dimcarb and -farnesene are biphasic at 40 °C (left) and one phase at
100 °C (right) at 10 bar, without stirring.
Scheme 2. Hydroamination of -farnesene with dimcarb using Pd/diphosphine
catalyst system yielding dimethyl farnesylamines.
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Table 1. The hydroamination of 1,3-dienes with dimcarb according to Scheme 3.
View Article Online
DOI: 10.1039/C7GC02272G
Average Yield over four
recycling experiments / %
DPPB
14
12
10
8
1,3-Diene
R
DPPBTS
isoprene
-myrcene
-farnesene
Me
C6H11
C11H19
77
72
88[a]
Reaction conditions: 0.1 mol% Pd(tfa)2; ligand=1,4-bis(diphenylphosphino)butane-
tetra-sulfonate, metal/ligand=1/4, ndimcarb=45 mmol, n1,3-diene=15 mmol, T=100 °C,
t=3 h, 500 rpm, results given based on substrate and determined by GC-FID using
dodecane (isoprene and -myrcene) and decane (-farnesene) as internal
standard.
6
Recycling conditions: Dimcarb was refilled to 45 mmol (addition of 7.5 mmol),
phase separation at room temperature under schlenk technique, addition of
15 mmol 1,3-diene, and restart of the reaction. The isoprene product was
extracted with 2 mL cyclohexane.
4
[a]: Average yield of the first 8 recycling runs, see Figure 3.
2
As is shown with the 1,3-dienes isoprene and -myrcene, the
catalytic system works well without optimizing the reaction
parameters. Recycling was carried out four consecutive times
for each substrate after the initial reaction. Again neither the
metal nor ligand was replenished and negligible leaching of the
palladium and phosphorous into the product phase occurred
0
0
1
2
3
4
5
6
7
8
9
10 11
Recycling No.
Figure 3. Isolated product yields of the palladium catalyzed hydroamination of

-farnesene using the DPPB-ligand (yellow bars) and the tetra-sulfonated analog
DPPBTS (green bars).
Reaction conditions: Pd(tfa)2, 0.1 mol%, metal/ligand=1/4, ndimcarb=45 mmol,
n-farnesene=15 mmol, T=100 °C, t=3 h, 500 rpm, results determined by GC-FID using
decane as internal standard.
according to ICP-OES measurements. With 72% (-myrcene)
and 77% (isoprene) respectively, the average yield of
hydroamination products over the course of four consecutive
recycling experiments (initial run is omitted, for detailed results,
see ESI) is high. The results using isoprene demonstrate that the
concept of the solvent-free reactions with subsequent recycling
works for short chain 1,3-dienes as well. The product of
dimethylamine and isoprene is soluble in the catalyst phase, but
can easily be separated by extraction with cyclohexane without
interfering with the homogeneous catalyst. This shows that the
products do not need to be insoluble in the dimcarb phase to
be effectively separated from the catalyst and to subsequently
recycle the latter.
DPPB = 1,4-bis(diphenylphosphino)butane;
DPPBTS = 1,4-bis(diphenylphosphino)butane-tetra-sulfonate
Recycling conditions: Dimcarb was refilled to 45 mmol (addition of 7.5 mmol),
phase separation at room temperature under schlenk technique, addition of
15 mmol -farnesene, restart of the reaction.
Oxidation from PIII to PV results in the decomposition of the
active catalyst, most probably due to the loss of the ligand’s
capability to coordinate to the palladium. This is also indicated
by increased palladium leaching into the non-polar phase at a
rate of 1% and 2% respectively in recycling runs 9 and 10. The
amount of leached palladium cannot explain the extent of the
loss in catalytic activity, but it proves the ligand required for
catalytic conversion is no longer intact. It should be clearly
stated that neither the metal nor the ligand was replenished at
any time. However, an average turnover frequency (TOF) of
293 h-1 (calculated as moles of products per mole of palladium
and hour) was achieved in the first eight recycling runs. This
significantly outperforms other approaches, such as SILP.29,30
Overall the total turnover number (TTON) in these recycling
experiments was 8,724 (calculated as moles of desired product
per mole of employed palladium), which represents a tenfold
increase as compared to batch experiments. The promising
Telomerization
The next step entailed converting short chain olefins, such as
1,3-butadiene, with amines using homogenous transition metal
catalysts. Telomerization is a promising reaction in connection
with very similar catalysts and substrates. It is a dimerization of
1,3-dienes to 2,7-octadienyls with the addition of an H-acidic
nucleophile.31,32 The most common 1,3-diene used is
1,3-butadiene, along with alcohols33–36, amines37,38 and even
carbon dioxide39,40. Besides 1,3-butadiene, a common diene is
isoprene41–44
-myrcene47,48 are reported as well. Palladium modified with
,
but 1,3-piperylene45, 1,3-hexadiene46, and
results achieved using -farnesene as a renewable substrate for
hydroamination led to the next step, in which the concept
presented was extended to other substrates with 1,3-diene
units (see Scheme 3 for reaction and Table 1 for results).

phosphine ligands is typically used as the catalyst, though in
recent years the use of N-heterocyclic ligands has been
investigated extensively.49–52 Although comprehensive studies
have been conducted on the separation of products and
catalysts in telomerization, only a few examples exist that
demonstrate efficient catalyst recycling.35,53–55 Carrying out the
telomerization of 1,3-butadiene with dimcarb means to work
with short-chain olefins, which are soluble in dimcarb and
relatively polar resulting products (Scheme 4), which are soluble
in the catalyst phase as well.
Scheme 3. General hydroamination reaction of conjugated 1,3-dienes with
dimcarb.
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Decreases in activity or selectivity were not observed. After the
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30th run, the recycling experiment was stopped deliberately. An
DOI: 10.1039/C7GC02272G
average desired product yield of 90% was obtained. The
selectivity in all runs was 99%, resulting in a product-related
TTON (converted moles of 1,3-butadiene to the desired
products per mole of palladium) of 90,712. The linearity of the
resulting products (calculated as the share of n-product among
the yielded products) was consistent at 92%. Regarding the ICP-
OES measurements, little to no palladium or phosphorous was
leached into the cyclohexane phase, which again made
replenishing the metal and ligand unnecessary. An average TOF
(calculated as converted moles of 1,3-butadiene per mole of
palladium and hour reaction time) of 1,436 h-1 was achieved
over the course of 31 consecutive reactions, which means this
reaction system is industrially viable.58
Scheme 4 Telomerization of 1,3-butadiene with dimcarb to the linear (n-) and the
branched (iso-) products
This provides opposing conditions compared to the case of the
hydroamination of -farnesene with dimcarb, in which only the
catalyst was soluble in the polar phase at room temperature.
Since triphenylphosphine is active for the telomerization of
1,3-butadiene with amines56 and the respective sulfonated
form TPPTS (= triphenylphosphine-trisulfonate) is widely used,
it has already been successfully used in the biphasic selective
mono-telomerization of 1,3-butadiene with ammonia57, which
was chosen as the catalytic system as a result. The recyclability
of the active catalyst was tested with this system. Cyclohexane
was used as extraction agent to overcome the miscibility of the
telomerization products with dimcarb. Stable catalytic activity
of the Pd/TPPTS complex was achieved for the telomerization
of 1,3-butadiene over the course of 30 runs (Figure 4).
Overall these results demonstrate that the reactive ionic liquids
approach, with its excellent total turnover numbers and space-
time-yields that lead to potential valuable products, is suitable
for industrial processes using cheap and readily available
catalysts and substrates.
Hydroaminamethylation
To open further perspectives for the presented approach,
hydroaminomethylation (HAM) was investigated, which is
completely different from the examples presented so far. HAM
is
a
tandem catalyzed reaction, consisting of the
hydroformylation of an olefin followed by a reductive amination
of the obtained aldehyde (Scheme 5).59,60 The intention was to
expand the presented method to other transition metals
(rhodium), substrates (olefins) and gaseous compounds
(syngas). In this case, 1-dodecene was used as the olefin and
[Rh(cod)Cl]2/sulfo-XantPhos as the catalytic system. After some
preliminary optimizations (for results, see Supporting
Information), particularly with regard to aldol condensation as
a side reaction, a yield of 40% of the dimethyl tridecylamine was
achieved. This reaction was carried out over the course of five
recycling runs after the initial reaction, with an average yield of
32%. Since the products are non-polar, no extracting agent was
required. Although a decrease in activity was observed, almost
no leaching of the precious catalyst into the product phase
(< 0.1%) was detected. Accordingly, reactions that include
gaseous components can be conducted using this system and
transition metals other than palladium are immobilized
effectively in the dimcarb phase as the catalytically active
species.
18
16
14
12
10
8
6
4
2
0
0
5
10
15
20
25
30
Recycling No.
Figure 4. Isolated product yields of the palladium catalyzed telomerization of
1,3-butadiene with dimcarb to N,N-dimethyl octadienylamines.
Reaction conditions: Precursor=Pd(acac)2, 0.03 mol% based on 1,3-butadiene,
ligand=TPPTS (=triphenylphosphine-trisulfonate), metal/ligand=1/4, ndimcarb=30 mmol,
n1,3-butadiene=38 mmol, T=80 °C, t =2 h, 500 rpm, results determined by GC-FID using
dibutyl ether as internal standard.
Recycling conditions: Extraction of the product with cyclohexane (2x2 mL), dimcarb was
refilled to 30 mmol (addition of 11 mmol), addition of 38 mmol 1,3-butadiene, restart of
the reaction.
Scheme 5. Linear hydroaminomethylation (HAM) of a terminal olefin with
dimethylamine.
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with 5 bar argon. The reaction mixture was transferred into a
Conclusion
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schlenk flask to recycle the catalyst. The DeOxtIr: a10c.t1i0o3n9/sCo7lGveCn02t2w72aGs
added and removed from the dimcarb phase after separation as
needed. The consumed dimcarb was replenished, the polar
phase was transferred back into the reactor and new substrate
was added. All products were purified by silica gel column
chromatography and calibrated for GC-FID analysis with
internal standard. Routine gas chromatographic analyses were
performed on an Agilent 7890B instrument (Santa Clara, USA)
equipped with a flame ionization detector (FID) and a HP-5
capillary column (30 m, diameter 0.32 mm, film thickness 0.25
µm) connected to an auto sampler (7693) and an injector
(G4513A). GC-MS analyses of the products were carried out on
an Agilent 5977A MSD (70 eV).
The investigations presented regarding amination reactions in
the
reactive
ionic
liquid
dimethylammonium
dimethylcarbamate (dimcarb) demonstrate two striking
advantages for homogenously catalyzed reactions. Firstly, the
reactions can be carried out without additional solvents,
because dimcarb, as a reactive ionic liquid, acts as both the
solvent and the substrate and does not interfere with the
catalyst in the examples presented. This is highly favorable and
rarely described for homogenously catalyzed amination
reactions. The system’s highly efficient catalyst recycling using
sulfonated ligands is the second advantage. Without the need
for auxiliaries, virtually no leaching of the metal or ligand into
the product phases occurs and the catalyst is retained as the
catalytically active species. This makes this new approach
suitable for continuously operated processes. In terms of
hydroaminations, this might be carried out using flow
conditions, as these have been proven to be an appropriate
mode for these reactions.17 Especially with regard to the
telomerization of 1,3-butadiene, continuously high conversions
and selectivities were achieved. A deeper understanding of this
reaction must be obtained at miniplant scale to investigate
long-term phenomena. Furthermore, the telomerization of
NMR spectra were recorded on Bruker DRX spectrometers.
CDCl3 was used as solvent and standard for chemical shifts,
purchased from Deutero.
Acknowledgements
The financial support provided by Clariant is gratefully
acknowledged. We thank Umicore for the donation of the palladium
and rhodium precursors. The investigations on hydroamination of
isoprene and myrcene were carried out by B.Sc. Lisa Goclik. The
authors thank M.Sc. René Kuhlmann for supplying the dimcarb.
The ICP-OES measurements were thoroughly conducted by Iris
Henkel.
other 1,3-dienes, such as isoprene and
in dimethyl branched C10-amines (isoprene) or highly branched
C20-amines ( -myrcene), which might be interesting products as
-myrcene, would result

well. The hydroaminomethylation results demonstrate that this
strategy is also compatible with carbonylation chemistry in
principle, as demonstrated with the hydroaminomethylation.
Future investigations will focus on broadening the spectrum of
applicable amines. Since most ammonium carbamates are solid
at room temperature61, conducting phase separation at
elevated temperatures must be considered. Furthermore,
additional reactions that may benefit from this method, e.g.
aminocarbonylations62,63 or aminations of alcohols64, will be
investigated.
Notes and references
1
2
3
4
P. Roose, Methylamines in Ullmann’s Encyclopedia of
Industrial Chemistry, Wiley-VCH, Weinheim, Germany,
2015, pp. 1–10.
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Industrial Chemistry, Wiley-VCH, Weinheim, Germany,
2000, vol. 34, pp. 431–505.
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B. Tamaddoni Jahromi, A. Nemati Kharat, S. Zamanian, A.
Bakhoda, K. Mashayekh and S. Khazaeli, Appl. Catal. A
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Experimental Section
Chemicals were purchased from Acros Organics (Geel, Belgium),
Sigma-Aldrich (Steinheim, Germany) and TCI (Tokyo, Japan).
1,3-butadiene was obtained from Messer (Bad Soden,
5
G. Kuchenbeiser, A. R. Shaffer, N. C. Zingales, J. F. Beck and
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Germany),
-farnesene was provided by Clariant (Frankfurt
a.M., Germany). All substrates (except 1,3-butadiene) and the
cyclohexane were dried over molecular sieves and degassed by
bubbling argon through the liquids prior to use.
6
7
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steel autoclave. The metal precursor and the ligand were
weighed directly into the pot. The reactor was flushed with
argon and DimCarb and the respective substrates were
subsequently added with an argon counter flow. For the
telomerization experiments the reactor was closed and
1,3-butadiene was added volumetrically via a pressure-resistant
tube. To determine the accurate mass of the added
1,3-butadiene, the reactor was weighed before and after adding
the 1,3-butadiene. The reactor was subsequently pressurized
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