Methylformate as replacement of syngas in one-pot catalytic synthesis of amines from olefins

Article abstract of DOI:10.1039/c3cy00862b

A new general approach for the one-pot hydroaminomethylation of olefins using methylformate as formylating agent instead of synthesis gas (syngas) has been proposed. Herein we report that a Ru-Rh catalytic system demonstrates high activity in a tandem conversion of a series of n-alkenes into amines using methylformate with yields 58-92% (6 h). The selectivity for the normal amine reached 96% with catalysis by the Ru carbonyl complex Ru₃(CO) ₁₂, with an overall yield of 55% with respect to amine in this instance. The addition of the Rh complex to Ru catalytic system, sharply increased the hydroaminomethylation rate of both the terminal and internal alkenes and increased the yield of amines to 82-93% (6-12 h). The Royal Society of Chemistry.

Full text of DOI:10.1039/c3cy00862b

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Methylformate as replacement of syngas in one-pot
catalytic synthesis of amines from olefins
Cite this: Catal. Sci. Technol., 2014,
4, 540
a
Eduard Karakhanov, Anton Maksimov,a Yulia Kardasheva,a Elena Runova,a
*
Roman Zakharov,a Maria Terenina,a Corey Kenneallyb and Victor Arredondob
A new general approach for the one-pot hydroaminomethylation of olefins using methylformate as
formylating agent instead of synthesis gas (syngas) has been proposed. Herein we report that a Ru–Rh
catalytic system demonstrates high activity in a tandem conversion of a series of n-alkenes into amines using
methylformate with yields 58–92% (6 h). The selectivity for the normal amine reached 96% with catalysis by
the Ru carbonyl complex Ru3(CO)12, with an overall yield of 55% with respect to amine in this instance. The
addition of the Rh complex to Ru catalytic system, sharply increased the hydroaminomethylation rate of
both the terminal and internal alkenes and increased the yield of amines to 82–93% (6–12 h).
Received 30th October 2013,
Accepted 14th November 2013
DOI: 10.1039/c3cy00862b
www.rsc.org/catalysis
application since they are used in the manufacture of surfac-
Introduction
tants, resins, plastics, crop protectors, etc.32
Tandem transformations provide important advantages such
as the formation of several bonds and elaboration of the
compound structure in a single step. This is an effective
pathway for economical synthesis. An important reaction of
this type is the hydroaminomethylation of olefins which is a
one-pot process that occurs through a sequence of hydro-
formylation of an unsaturated compound followed by reductive
amination of the resulting aldehydes as shown in Scheme 1.
The hydroaminomethylation has continued to draw the
attention of researchers since the time of its discovery
by Reppe at BASF.1 This is evident from the large number
of publications, both reviews and articles2–6 dedicated
to the syntheses of amines from olefins with terminal and
internal double bonds,7,8 complicated N-containing organic
compounds, e.g., heterocycles,9,10 N-containing macrocycles,11–13
and dendrimers.14–16 Reductive aminomethylation of olefins
while using Rh complexes with bidentate phosphine ligands
that are highly active in hydroformylation have been used for
the regioselective preparation of amines.17–20 The performance
of this process in alternative solvents, i.e., ionic liquids21 and
in supercritical ammonia22 has also been reported. The
amination reaction can be applied to the synthesis of various
compounds possessing biological activity including a variety
of drugs.23–31 Hydroaminomethylation of higher alkenes for
the preparation of “fatty” amines, is an especially valuable
Usually, hydroaminomethylation occurs at a high tempera-
ture and in presence of a high pressure of syngas enriched in
H2. The use of such a gaseous mixture is unfavorable primarily
from the context of ecological and technical safety.
The solution to this problem could be the use of com-
pounds that can act as alternate sources of CO and H2.33
Thus, a source of CO for the carbonylation of iodobenzene
could be 2-pyridylmethylformate,34 dimethylformamide (DMF)
for the carbonylation of p-bromotoluene and iodoaryls,35,36
various formamides and formates for the carbonylation
of norbornene,37 formic acid and its salts for the hydroxy-
carbonylation of vinyl, arylhalides and triflates,38,39 aldehydes
in the catalytic Pauson–Khand-type reactions,40 formaldehyde
in the hydroformylation of unsaturated compounds,41,42 and
metal carbonyls, in particular molybdenum carbonyl in the
carbonylation of haloaromatic compounds.43–45
Methylformate (MF) is promising replacements for syngas
in the hydroformylation and hydrocarbonylation reactions. It
is a highly reactive compound owing to the presence of both
an ester and a labile H atom, and is used as a source of high-
purity CO.46 It was shown that catalytic decomposition of
a Chemistry Department, M. V. Lomonosov Moscow State University, 1 Leninskie Gory,
Bld.3, Moscow 119991, Russia. E-mail: kar@petrol.chem.msu.ru;
Fax: +7 (495) 932 8846; Tel: +7 (495) 939 5377
b P&G Chemicals, 11530 Reed Hartman Highway Cincinnati, OH 45241, USA.
E-mail: kenneally.cj@pg.com, arredondo.vm@pg.com
Scheme 1 General route for the hydroaminomethylation of olefins.
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methylformate in the presence of water (the variation of the
water gas shift reaction) leads to the formation of a mixture
of gases, the principal components of which are CO and
H2.46–50 Methylformate was used as carbonylating agent
for the catalytic conversion of phenol to methyl phenyl
carbonate,51 in the hydroesterification of alkenes catalysed by
Ru complexes52–59 and hydroformylation of various linear
and cyclic (C5–C8) alkenes60,61 using Ru and bimetallic
catalytic systems. It should be emphasized that in all these
cases indicated the yields of final products (alcohols) rarely
exceeded 50% because of the formation of alkane, especially
for higher olefins. Thus the yield of octane was 76% in the
hydroformylation of 1-octene.61
This in turn substantially increases the effectiveness of
the process.
All the processes indicated can run on the Ru and
Rh complexes. We studied the hydroaminomethylation of
1-nonene in MF using a monometallic catalyst system where
carbonyl complexes of Ru and Rh acted as catalyst precursors
(Table 1). It should be emphasized that the Ru complexes are
more active than those of Rh in the hydroformylation of
alkenes with methylformate.48,52,55,60,61,63,64
Carbonyl complexes such as Ru3(CO)10 and Rh(acac)(CO)2
in combination with PPh3 were used as the catalysts in most
of the experiments. The reaction conditions and catalytic
systems were selected based on the decomposition data for
MF.48,61 The Rh and Ru catalysts actively catalyze this process
and formed a CO/H2 = 1/3 gas mixture at a MF/H2O ratio of 3
that was optimal for performing the hydroaminomethylation.
We used the excess of PPh3 because it increases both the
linear products yield in the hydroformylation and hydro-
aminomethylation64–68 with syngas and the conversion of
methylformate during its decomposition.47,64
Herein for the first time we report results of the effective
use of methylformate as green reagent in the hydroamino-
methylation reaction of olefins C5–C16 catalyzed by Ru and
Ru–Rh systems with excellent yields of amines with the
formation of alkane not exceeding 5%.
Results and discussion
In the course of the reaction with MF in the absence of
syngas, the principal linear and branched N,N-dimethyl-
decylamines in addition to intermediates such as aldehydes
and enamines of the normal and isomerized structures and
products originated from the hydrogenation and isomeriza-
tion of the double bond were identified as shown in
Scheme 3. Alcohols and products from the aldol condensa-
tion of aldehydes and other side products were not observed.
The use of the Ru catalyst was attractive as it leads to high
selectivity for the normal product only in conversion and
reaches as much as 60%. The best result was 55% total yield
of the amines with 96% selectivity and was achieved at a Ru
concentration of 2.52 mol% (Table 1, entry 4) due to the
essential difference in the rates of hydroformylation in inter-
nal and terminal double bonds. Thus the increase of the
reaction time from 12 to 36 h led to the increase of conver-
sion by 11% at the decrease of selectivity by 3% (Table 1,
entry 2 and 3). At high temperature the selectivity decreases
due to the partial involvement of isomeric alkenes in the
reaction. Neither aldehyde nor enamine was observed in the
final products while using Ru3(CO)12. The reaction occurred
much more slowly than that with rhodium because of
the lower activity of ruthenium phosphine complexes in
hydroformylation.69 The results are in good agreement with
literature data. The Ru systems are considerably more active
for the hydrogenation and much less active for the
hydroformylation reaction, especially of internal double
bonds.70–75 In addition the Ru-catalyst is much more effective
in syngas formation from MF. Its activity is twice as much in
the presence of the amines.76–78
The substitution of methylformate for syngas requires the
use of catalytic system which provides the realization of the
four processes simultaneously. The system should be active
both in the reaction of aqueous methylformate decomposi-
tion to form a mixture of CO and H2 via the gas-shift reaction
and in the hydroformylation of alkene to form aldehydes
which are the first intermediates in the hydroamino-
methylation. The metal complex should also participate effec-
tively in the hydrogenation of the second intermediate, which
is an enamine formed via the reaction of dimethylamine and
the aldehyde, in order to produce the final product (amine).
The metal centre should also be capable of carrying out these
steps with a high rate and specificity. Moreover, the side reac-
tion of DMF formation can run due to dimethylamine (DMA)
carbonylation and its interaction with MF. DMF is acting as
amine source instead of DMA when syngas used. While using
DMF as only formylating agent hydroaminomethylation does
not take place.62
The equilibrium reactions in the presence of the three
components are proposed to be as shown in Scheme 2.
Therefore similarly to the use of syngas the most
promising aminating agent is a solution of dimethylamine in
dimethylformamide.61 The use of DMF as the solvent avoids
the non-productive consumption of DMA and MF (Scheme 2).
The Rh system was more active. The use of the Rh
complex resulted in high yields of the amines, the fraction of
N,N-dimethyldecylamine was less than 30% at 130 °C and
only 15% at 170 °C (Table 1; entries 8, 9). A significant
amount of aldehydes (with an isomerized skeleton) and a
small amount of enamines remained after 12 h at 130 °C.
Scheme
hydroaminomethylation.
2 Equilibrium between the components of the
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Table 1 Hydroaminomethylation of 1-nonene using monometallic catalytic systemsa
Reaction mixture compositionb [%]
Time,
Entry
Mol%
Temperature [°C]
h
1-Nonene
Isononenes
Nonane
Aldehydes
Enamines
Amines
% n-aminec
Ru3(CO)12
1
2
3
4
5
6
0.63
130
130
130
130
170
170
12
12
36
12
12
12
4
3
4
2
4
3
52
44
25
32
26
31
5
6
13
7
7
15
0
0
0
0
1
0
0
0
0
3
1
0
39
47
58
55
61
51
92
91
88
96
66
82
1.26
1.26
2.52
0.63
1.26
Rh(acac)(CO)2
7
8
9
0.63
0.63
0.63
130
130
170
12
36
6
0
0
0
5
0
0
13
14
6
22
0
0
8
0
2
52
86
92
50
30
15
a
Reaction conditions: PPh3 (8.3 × 10−4 mol), 1-nonene (6.2 × 10−4 mol), DMA (5.6 × 10−3 mol), DMF (1 mL), methylformate (2 mL), H2O (0.2 mL),
12 h. b The yield of amines was determined using GC with n-decane as internal standard. c % n-amine = [(yield of n-amine)/(yield of amines)] × 100%.
Scheme 3 Products observed during the hydroaminomethylation using methylformate.
After 36 h the reaction went to completion and only amines
(total yield: 86%, Table 1, entry 8) were observed in the
products. The fraction of n-amine was 30%. The complexes
of rhodium and PPh3 in the hydroformylation with syngas
are very active both in the terminal and internal olefins.65
Due to the isomerisation of alkenes high amounts of iso-
amines are formed. In addition the Rh catalyst was most
active in the hydroformylation and far less active in the
hydrogenation of enamines.69
Bimetallic catalysts have been used successfully for many
catalytic processes, including olefin aminomethylation in the
presence of synthesis gas.79 Earlier we showed62 that the
addition of ruthenium carbonyl to rhodium systems leads to
the essential increase of catalytic activity at the retained selec-
tivity of N,N-dimethyldecylamine up to 74%. The most effective
was the system containing 3.9 × 10−6 mol Rh(acac)(CO)2
and between 3.9 × 10−6 mol and 15.6 × 10−6 mol Ru3(CO)12.
Therefore we studied the behavior of bimetallic Ru–Rh systems
in hydroaminomethylation by methylformate. We studied the
influence of the amount of Rh-complex in presence of a fixed
amount of Ru carbonyl on the yield and selectivity towards the
formation of normal amine (Fig. 1). The reaction with a low Rh
content occurred rather slowly but with excellent selectivity
(70–95% of normal amine). At a Ru/Rh ratio greater than three
(0.45 mol% Rh), the amount of isomerized nonenes decreased
sharply and the overall yield of amines reached 80% with the
yield of N,N-dimethyldecylamine remaining at the previous
level, i.e., the contribution of the reactions occurring at the
internal double bonds increased substantially upon reaching
this concentration (Fig. 1).
Thus, the principal product was the branched amine-1 that
can be formed from both 1-nonene and 2-nonene (Fig. 2).
Fig. 3 and 4 present the results obtained at 170 °C using
Ru/Rh ratios 3 and 12 in the catalytic system. Amines
produced almost quantitatively (>90%), the majority of it
was formed in the first two hours. The fraction of n-decanal
in the aldehydes was less than 2–3%. After two hours, the
overall yield of amines increased due to the accumulation of
branched products that were formed by the hydroformylation
of isomeric nonenes containing internal double bonds that
reacted more slowly. With this, the selectivity for the n-amine
did not actually change. The amount of unreacted aldehydes
that was converted into the isomeric amines decreased
sharply. A comparison for the change of selectivity for the for-
mation of aldehydes in case of the Ru/Rh = 3 and Ru/Rh = 12
catalytic system indicated that increasing the Ru concentration
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Fig. 1 Hydroaminomethylation of 1-nonene. Reaction conditions: Ru3(CO)12 (7.8 × 10−6 mol), PPh3 (8.3 × 10−4 mol), 1-nonene (6.2 × 10−4 mol),
DMA (5.6 × 10−3 mol), DMF (1 mL), methylformate (2 mL), H2O (0.2 mL), 130 °C, 12 h, conversion of 1-nonene 100%.
enabled the aldehydes to be consumed at much faster rates.
Even after conducting the reaction for 5 h the amount of
alkenes is 4% and that of aldehydes is 10% for the ratio
Ru/Rh = 3. At the ratio Ru/Rh = 12 the alkenes are not observed
at all, and the amount of aldehydes does not exceed 2%.
Our experiments on the use of different catalytic pre-
cursors showed (Fig. 5) that combinations of other complexes
and salts of Rh and Ru could also be used successfully to
perform this reaction with high chemoselectivity. However it
can be seen that the fraction of N,N-dimethyl-n-decylamine
formed decreased if Rh-cyclooctadienyl complexes or trivalent
Ru salts were used. This is because the complexes mentioned
facilitated isomerization.80
Fig. 2 Isomeric composition of amines after hydroaminomethylation of
The Ru–Rh catalytic system was highly active for the
1-nonene in MF. Reaction conditions: = Rh(acac)(CO)2 (3.9 × 10−6 mol),
hydroaminomethylation of a number of unsaturated com-
pounds (Table 2). The yields of amines from the linear C5–C9
alkenes reached 90% after 6 h. The reaction was slightly
Ru3(CO)12 (7.8 × 10−6 mol), PPh3 (8.3 × 10−4 mol), olefin (6.2 × 10−4 mol),
DMA (5.6 × 10−3 mol), DMF (1 mL), methylformate (2 mL), H2O (0.2 mL),
130 °C, 12 h.
Fig. 3 Hydroaminomethylation of 1-nonene at ratio Ru/Rh = 3. Reaction conditions: Rh(acac)(CO)2 (3.9 × 10−6 mol), Ru3(CO)12 (3.9 × 10−6 mol)
PPh3 (8.3 × 10−4 mol), 1-nonene (6.2 × 10−4 mol), DMA (5.6 × 10−3 mol), DMF (1 mL), methylformate (2 mL), H2O (0.2 mL), 170 °C. Conversion of
1-nonene 100% after 2 h.
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Fig. 4 Hydroaminomethylation of 1-nonene at ratio Ru/Rh = 12. Reaction conditions: Rh(acac)(CO)2 (3.9 × 10−6 mol), Ru3(CO)12 (15.6 × 10−6 mol)
PPh3 (8.3 × 10−4 mol), 1-nonene (6.2 × 10−4 mol), DMA (5.6 × 10−3 mol), DMF (1 mL), methylformate (2 mL), H2O (0.2 mL), 170 °C. Conversion of
1-nonene 100% after 2 h.
and was accompanied by the formation of the corresponding
formamide from the amine and MF.
A significant amount of unreacted aldehydes remained
in the reaction mixture even after 12 h at 130 °C when
morpholine and piperidine were used, in contrast to dimethyl
and diethylamines. In analogy with dimethylamine, the struc-
ture of the amines formed was determined from the isomeriza-
tion of the starting olefin. In all the instances, the maximum
fraction observed was that of the branched amine-1; followed
by the n-amine (Fig. 6).
Experimental
Fig. 5 Hydroaminomethylation of 1-nonene using various catalytic
precursors. Reaction conditions: PPh3 (8.3
(6.2 × 10−4 mol), DMA (5.6 × 10−3 mol), DMF (1 mL), methylformate
(2 mL), H2O (0.2 mL), 170 °C, 12 h. Conversion of 1-nonene – 100%.
a) Yields of amines were determined using GC with n-decane as internal
×
10−4 mol), 1-nonene
All reagents were purchased from either Aldrich Chemicals or
Acros Chemicals and were of high purity. Water was distilled
twice under a N2 atmosphere. All liquid reagents and solvents
were degassed by bubbling N2 for 15 min before use or by
two freeze–pump–thaw cycles.
standard. b)
% of N,N-dimethyl-n-decylamine = [(yield of % of
N,N-dimethyl-n-decylamine)/(yield of amines)] × 100%.
Ru3(CO)12,81 [Rh(COD)Cl]2 and [Rh(COD)2]+BF4 (ref. 82)
−
were prepared according to literature methods. Dimethyl-
amine (DMA) was used as a solution (25%) in DMF that was
prepared as follows: a two-necked flask equipped with a
dropping funnel and gas outlet tube was charged with base
(KOH or NaOH). A saturated solution of dimethylamine
hydrochloride in water was added dropwise. The released
gaseous DMA was passed into an ice-cooled container
containing DMF. The mass fraction of dissolved DMA in the
solution was determined from the change in mass of the
DMF and was monitored by GC.
The hydroaminomethylation was carried out in a steel
thermostatted custom-made autoclave (7 mL) equipped with
a magnetic stirrer. The following general order of operations
was carried out during the experiments: catalytic precursor
(Rh- and/or Ru in the required amounts), PPh3 (0.214 g,
0.83 mmol), olefin (0.614 mmol), MF (2 mL), H2O (0.2 mL),
25% DMA in DMF (1.3 mL) (or 0.056 mmol of a different
amine) were placed into the autoclave. Then the reactor was
slower for higher n-olefins (C10–C16 alkenes) and much worse
for cyclic ones. It is interesting that an internal alkene such
as 3-heptene was just as reactive as terminal 1-heptene. As
expected, only the yields of linear N,N-dimethyloctylamine
differed substantially (32 and 7%, respectively). In general,
the selectivity towards the formation of linear products
decreased with increasing length of the carbon chain from
50% (for 1-pentene) to 20% (for 1-nonene). This resulted
from the considerable increase in the number of possible iso-
meric alkenes with an internal double bond from which
amines with only the iso-structure can be formed. Thus, there
can be only one such olefin for 1-pentene (i.e. 2-pentene);
3 for 1-octene (i.e. 2-octene, 3-octene, and 4-octene); 4 for
1-decene (i.e. 2-decene, 3-decene, 4-decene, and 5-decene) etc.
The corresponding amines were also readily formed if other
amine components (Table 3) and MF were used. For these
instances, the reaction was carried out in MF/amine/alkene
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Table 2 Hydroaminomethylation of various substratesa
Reaction mixture compositionb [%]
%
Olefin
Time [h]
1-Alkene
Isoalkenes
Alkane
Aldehydes
Enamines
Amines
n-aminec
1-Pentene
1-Hexene
1-Heptene
3-Heptene
1-Octene
1-Nonene
1-Decene
1-Decene
1-Undecene
1-Tetradecene
1-Hexadecene
Cyclohexene
Cycloheptene
Vinylcyclohexane
Allylbenzene
Propenylbenzene
6
6
6
6
6
2
0
7
0
6
5
11
0
0
0
16
64
87
7
11
0
0
0
7
4
4
6
27
0
0
0
11
—
—
15
25
39
6
6
2
3
2
1
2
6
6
6
7
0
0
4
3
5
0
1
0
0
0
0
1
0
0
7
0
3
0
3
0
0
0
1
2
0
0
1
1
6
12
8
7
9
4
4
1
0
92
92
82
93
88
87
58
88
82
79
59
24
9
48
36
39
8
17
19
29
23
20
20
29
100
100
66
27
—
6
6
12
12
12
12
12
12
6
77
60
56
6
6
a
Reaction conditions: Rh(acac)(CO)2 (3.9 × 10−7 mol), Ru3(CO)12 (3.9 × 10−6 mol), PPh3 (8.3 × 10−4 mol), olefin (6.2 × 10−4 mol), DMA (5.6 × 10−3 mol),
b
DMF (1 ml), methylformate (2 ml), H2O (0.2 ml), 170 °C. The reaction mixture composition was determined using GC with n-decane or n-octane
as internal standard. c % n-amine = [(yield of n-amine)/(yield of amines)] × 100%.
Table 3 Hydroaminomethylation of 1-nonene with aminesa
Reaction mixture compositionb [%]
Amine
Temperature [°C]
Time [h]
Hydrocarbons
Aldehydes
Enamines
Amines
% n-aminec
130
6
12
6
53
25
14
4
15
1
4
—
5
43
60
80
91
72
36
170
130
6
12
6
35
22
5
47
48
7
2
4
18
15
26
70
87
85
31
170
130
170
6
12
6
29
22
7
22
19
3
8
7
11
41
52
79
68
62
33
a
Reaction conditions: Rh(acac)(CO)2 (3.9 × 10−6 mol), Ru3(CO)12 (7.8 × 10−6 mol), PPh3 (8.3 × 10−4 mol), 1-nonene (6.2 × 10−4 mol), amine
(5.6 × 10−3 mol), methylformate (2 ml), H2O (0.2 ml), 170 °C, 12 h. Reaction mixture composition was determined using GC with n-decane
as internal standard. % n-amine = [(yield of n-amine)/(yield of amines)] × 100%.
b
c
Fig. 6 Isomeric compositions of amines after hydroaminomethylation of 1-nonene in MF using various amines. Reaction conditions: Rh(acac)(CO)2
(3.9 × 10−6 mol), Ru3(CO)12 (7.8 × 10−6 mol), PPh3 (8.3 × 10−4 mol), 1-nonene (6.2 × 10−4 mol), amine (5.6 × 10−3 mol), methylformate (2 mL), H2O
(0.2 mL), 170 °C, 12 h.
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heated either to 130, 150, or 170 °C. The reaction time was
varied within the range of 2–36 h. After the reaction was
complete, the autoclave was cooled to room temperature and
the pressure was slowly released before opening it. An internal
standard was added before analyzing the products by GC. The
analysis was carried out on an HP 6990 chromatograph with a
flame-ionization detector, SE-30 column (30 m × 0.25 mm),
and temperature programming from 90 to 230 °C. Each
experiment was repeated a minimum of two times in order
to obtain reliable results.
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Conclusions
Ru–Rh catalytic systems were found to be highly active in a
tandem one-pot conversion of a series of alkenes into amines
using MF as the formylating agent instead of syngas. The
yields of the amines were >90%. The selectivity for the
formation of the normal amine reached 96% in case of catalysis
by the Ru carbonyl complex Ru3(CO)12, the overall yield of
amines in this instance was 55%. Adding a Rh complex with
a fixed amount of Ru sharply accelerated the hydroamino-
methylation of both the terminal and internal olefins.
The results indicate that the use of MF as an alternative
source of syngas for the development of new approaches
towards the synthesis of higher amines from alkenes is
promising.
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Acknowledgements
This work was supported financially by the Ministry of the
Russian Federation for Education and Science under the
auspices of the Federal Targeted Program “Scientific and
Scientific-Pedagogical Departments of Innovation Russia” for
2009–2013 (Program Activity 1.2.1, natural sciences; grant no.
8449/2012-1.2.1-12-000-1004-005). We thank Dr. Jeff Scheibel
(P&G Chemicals) who provided some technical insights to
the research programme.
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