Diamines for Polymer Materials via Direct Amination of Lipid- and Lignocellulose-based Alcohols with NH3

Article abstract of DOI:10.1002/cctc.201800365

Via an all-catalytic route, long-chain diamines were prepared by the catalytic direct amination of long-chain diols, derived from plant oils. High conversion was achieved with good selectivity, with the amount of nitrile impurities formed suppressed to a low level. From the lignocellulose-based 5-hydroxymethylfurfural (5-HMF), or from bis(hydroxymethyl)furan, 2,5-bis(aminomethyl)furan (BAMF) was generated. 5-HMF was converted in a one-pot, one-step direct amination and reductive amination using ammonia. In both cases, the reaction proceeded very efficiently. In the combined amination and reductive amination, the H₂ concentration is a rate-limiting factor. Reducing the partial pressure of H₂ also shortened the reaction time required significantly. Polycondensation of the long-chain diamines with long-chain diacids led to higher molecular weight polyamides, illustrating the quality of the diamines obtained by this synthetic approach as monomers.

Full text of DOI:10.1002/cctc.201800365

Accepted Article
Title: Diamines for Polymer Materials via Direct Amination of Lipid- and
Lignocellulose-based Alcohols with NH3
Authors: Dennis Pingen, Judith Barbara Schwaderer, Justus Walter,
Jiaqi Wen, George Murray, Dieter Vogt, and Stefan Mecking
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the VoR from the journal website shown below when it is published
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To be cited as: ChemCatChem 10.1002/cctc.201800365
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10.1002/cctc.201800365
ChemCatChem
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Diamines for Polymer Materials via Direct Amination of Lipid- and
Lignocellulose-based Alcohols with NH3
Dennis Pingen,[a] Judith B. Schwaderer, [a] Justus Walter, [a] Jiaqi Wen, [b] George Murray, [b] Dieter Vogt,
[c] Stefan Mecking*[a]
Abstract: Via an all-catalytic route, long-chain diamines were
prepared by the catalytic direct amination of long-chain diols, derived
from plant oils. High conversion was achieved with good selectivity,
with the amount of nitrile impurities formed suppressed to a low level.
From the lignocellulose-based 5-hydroxymethylfurfural (5-HMF), or
from bis(hydroxymethyl)furan, 2,5-bis(aminomethyl)furan (BAMF)
was generated. 5-HMF was converted via a one-pot, one-step direct
amination and reductive amination using ammonia. In both cases, the
reaction proceeded very efficiently. In the combined amination and
reductive amination, the H2 concentration is a rate limiting factor.
Reducing the partial pressure of H2 also shortened the reaction time
required significantly. Polycondensation of the long-chain diamines
with long-chain diacids led to higher molecular weight polyamides,
illustrating the quality of the diamines obtained by this synthetic
approach as monomers.
results in the selective formation of a terminal ester or
carboxylic acid group, far from the original site of the double
bond.[9,10] The products obtained fulfil the stringent
requirements
on
monomer
purity
required
for
polycondensation reactions, as given by the Carothers
equation, and high molecular weight long-chain polyesters
can be obtained.
Cellulose, and in particular hemicellulose as an abundant
low-cost feedstock can be converted into 5-
hydroxymethylfurfural (5-HMF, Scheme 1, right part) by acid-
catalysed dehydration.[11-20] Subsequent conversions of this
platform chemical provide desirable compounds such as
hexanediol,
2,5-furan
dicarboxylic
acid,
and dimethyl
2,5-
bis(hydroxymethyl)furan (BHMF)[21-23]
furan.[24,25] For example 2,5-furan dicarboxylic acid can be
used as an alternative for terephthalic acid in the production
of polyesters materials.[26,27] These possess beneficial traits
such as a higher gas barrier vs. poly(ethylene terephthalate)
(PET).
Introduction
The preparation of polymers from renewable resources is an
attractive prospect, not only considering the gradual
depletion of fossil feedstocks but more importantly because
nature also provides unique molecular structural motifs.
Notably, the particular methylene chain sequences of fatty
acids from plant oils can serve as the source of mid- and
long-chain monomers X-(CH2)n-X for polycondensates.[1]
The particular composition of carbohydrates via multiple
dehydration affords furanic building blocks X-CH2-furan-2,5-
diyl-CH2-X to be used as rigid segments in polyesters.[2]
In the synthesis of monomers from plant oils, the unsaturated
fatty acids or esters are especially interesting for further
functionalisation.[3] Long chain α,ω-diesters and α,ω-diols
are accessible already via various catalytic routes (Scheme
1, left part). An attractive chemical transformation towards
diesters is the isomerising alkoxycarbonylation.[4-6] In this
reaction, the entire fatty acid is effectively incorporated into
the product and no stoichiometric by-products are formed.[4,6-
lignocellulose
dehydration
unsaturated fatty acids
isom.
carbonylation
reduction
OH
O
OH
O
HO
O
HO
OH
BHMF
5-HMF
n
CATALYTIC AMINATION
+ NH3 [Ru]
NH2
O
H2N
H2N
NH2
n
long chain POLYMER MATERIALS
polyamides
cured
epoxies
Scheme 1. Overview of the synthesis of monomers and polymers pursued in
this work.
Compared to polyesters, fewer new polyamides[28,29] from
renewables have been studied or introduced over the last
decades. This is largely due to a lack of suitable routes to
novel diamine monomers. Polyamides are most commonly
generated by melt polycondensation of diacids with
diamines.[30,31] Polyamides generally have relatively high
melting points due to hydrogen bonding between the amide
groups. Compared to short-chain polyamides such as nylon-
6.6 (Tm ca. 260 °C), longer-chain monomers significantly
reduce the melting point and also the water-uptake which
enhances dimensional stability.[32,33] Beyond polyamides,
diamines (and multifunctional amines) are also widely
employed in epoxies and other resins, making use of the
high nucleophilicity and reactivity of amine groups.
8]
The highly kinetically controlled nature of the reaction
[a]
Prof. Dr. Stefan Mecking, Dr. Dennis Pingen, Judith Barbara
Schwaderer, Justus Walter, Chair of Chemical Materials Science,
Universitätsstrasse 10, University of Konstanz, Konstanz, Germany.
E-mail: Stefan.Mecking@uni-konstanz.de
[b]
[c]
Jiaqi Wen, George Murray, University of Edinburgh, Joseph Black
Building, David Brewster Road, Edinburgh EH9 3FJ, United
Kingdom
Prof. Dr. Dieter Vogt, Chair of Industrial Chemistry, Dortmund
University of Technology, Emil-Figge-Strasse 66, Dortmund,
Germany.
Supporting information for this article is given via a link at the end of
the document.
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10.1002/cctc.201800365
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However, as mentioned straightforward routes to diamines
based on renewable sources are lacking. Access to long-
chain α,ω-diamines for polyamides still require multi-step
procedures.[5,34] Commercial polyamides PA6,10, PA10,10
and PA11 are produced from ricinoleic acid, the major
component of castor oil, which is, however, a rather limited
resource.[1,35] Also in case of 5-HMF derived amines, no
direct catalytic, atom-efficient routes are currently available
and still rely on multi-step routes producing significant
amounts of waste.[34,36-39]
Alcohols and alcohol derivatives (ketones, aldehydes) are
easily accessible already from biomass and can be exploited
in the synthesis of amines via the direct amination of alcohols
with NH3. The reaction follows the so-called ‘Hydrogen
Shuttling’ or ‘Borrowing Hydrogen’ methodology with water
as the only by-product (Scheme 2).[40-42] To date, several
systems have been developed that efficiently convert
primary and secondary alcohols to primary amines.[40-45]
However, only two examples of a long-chain diol direct
amination have been reported, both for the case of 1,19-
nonadecane diol, and the conversion of the product to
polymers as a probe of their suitability to this purpose has
been lacking.[46,47,51] This is, however, crucial as it is also a
sensitive probe whether the amination reaction is sufficiently
selective and the formation of problematic (e.g.
monofunctional) side-products is below an appreciable limit.
reductive amination
O
O
HO
OH
O
NH2
reduction HO
O
0.5-1 mol% cat. H2N
excess NH3, solvent
150-170°C, 12-65 h
HO
N
OH
H2N
NH2
x
x
X = 12, 16, 17, 21
N
Ph2P
O
Cl
PPh2
Cl Ru PPh2
CO
P(iPr)2
Ph2P
H
PPh2
PPh3
P(iPr)2
P(iPr)2
(iPr)2P
Cl
Ru
H
Ru
H
CO
Ru3(CO)12 Ru:P = 1:1
CO
C1
C2
C3
C4
Scheme 3. Amination procedures and catalysts studied.
C1, reported early on in the development of catalytic
amination chemistry, is based on an acridine diphosphine
ligand developed by the Milstein group.[40] Moreover, this
system seems to be most promising as this and derivatives
of this, have been employed successfully in the direct
amination of various diols, including a branched dimer fatty
acid (C36) diol.[46, 51] System C2 is also based on the acridine-
based diphosphine ligand, but with ruthenium carbonyl as
metal source, providing a somewhat more robust system.[44]
Another system based on RuHCl(CO)(PPh3)3 and Xantphos
as ligand, developed by the group of Beller, was reported to
be effective for diols and long-chain (mono)alcohols.[43] The
most recent catalyst (C4) is based on RuHCl(CO)(PPh3)3
and the Triphos ligand,[45] which is also known to be a good
hydrogenation catalyst.[48]
OH
O
R1 R2
R1 R2
NH3
H2O
[LnM] [LnMH2]
NH2
NH
At 150°C with a catalyst loading of 0.5 mol% only C1 and C4
showed activity in the amination of the α,ω-diols. However,
C4 did not lead to full conversion in these experiments and
gave a broad mixture of products and was therefore not
pursued further here (Table S1 and S4, supporting
information).
R1 R2
R1 R2
R1, R2 = H, alkyl, Aryl
M = transition metal
Scheme 2. “Hydrogen shuttling” for direct amination of alcohols with
ammonia.[41]
We now report insights on the pathways, and side-products and
intermediates occurring in the target amination reactions. The
rational derived allows for a direct di-amination of 5-HMF, and of
plant oil-based long-chain diols to polymerization grade long
chain diamines.
Results and Discussion
Diamine synthesis
A set of ruthenium complexes were screened for the direct
amination of diols with NH3 to the target amines (Scheme 3).
The choice of catalysts was based on their proven utility for
direct amination reactions.
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Table 1. Screening and optimization of the direct amination of long chain diols with NH3 using C1.
Entry[a]
Diol (mmol)
Solvent (mL)
NH3 (mmol) [mL]
Conversion (%)[a]
Primary amine
selectivity[a]
Secondary/Cyclic
amine selectivity[a]
Nitrile Selectivity[a]
1[b]
2[c]
3[b]
4[c]
5[b]
6[c]
7[c]
1,14 (1.67)
1,14 (5)
5
15
5
97.5 (2.5)
585 (15)
97.5 (2.5)
585 (15)
97.5 (5)
99
92
11
89
11
87
74
95
96
83
6
6
5
9
9
9
5
4
1,18 (1.67)
1,18 (5)
99
80
4
15
5
99
1,19 (1.67)
1,19 (5)
100
100
100
17
0
15
20
585 (15)
585 (15)
1,23 (5)
0
Conditions: C1 (0.5 mol%), toluene, 150°C, 64 h. [a] determined by 1H NMR (298 K, 400 MHz, CDCl3) analysis based on the signal of NH2-CH2 (2.69 ppm) for
primary amine groups, CH2-NH-CH2 (2.59 ppm) for secondary and cyclic amine groups and NC-CH2 for nitrile groups (2.33 ppm). b) 1.67 mmol. c) 5 mmol.
Studying 1,14-tetradecanediol as a substrate, the diol was
completely converted but only 11% of primary diamine was
produced. To rationalize the amination procedure, the as-
obtained product mixture was fully characterized. Although
high conversion was achieved, mainly secondary and cyclic
amines were produced (Table 1Fehler! Verweisquelle
konnte nicht gefunden werden., Entry 1). This suggests
that the availability of ammonia is not sufficient in these
cases. In order to drive the reaction towards the primary
diamine product, a sufficiently high amount of ammonia of
120 eq. with respect to the diol was found to be key. This led
to a higher selectivity of 89% (Table 1, Entry 2). The
increased ammonia concentration strongly reduced the
formation of secondary and cyclic amines. One other notable
by-product, the mono-nitrile, remained present to a small
extent, which however did not hamper polycondensations
(vide infra). Essentially similar observations were made for
longer chain C18 to C23 diols. In all cases a large excess of
ammonia was necessary and led to high selectivity to the
corresponding diamines (entry 3 vs 4, 5 vs 6). Further
variations for optimization can be found in the supporting
information (Table S1, entry 8-12). Interestingly it was noted
that with increasing chain length, the selectivity also
increased.
resinify and to being oxidised relatively easily under ambient
conditions.[36,49] In general, it is a highly reactive amine, which
is advantageous for low temperature curing.[50]
Monitoring of the reaction over time revealed that BHMF was
consumed within 6 hours with considerable amounts of the
intermediate aminoalcohol accumulating, which was then
slowly converted to the diamine product. The reaction
eventually went to completion within about 7 hours (Graph
S1, Table S2, SI). After the solvent was removed, BAMF was
isolated as a brown oil.[51] As suspected by the colour of the
mixture, some impurities were found in the 1H NMR spectrum,
which were not observed by GC analysis. This suggests that
they are higher molecular weight secondary products formed
from BAMF.[49,52]
In view of a straightforward and efficient process, the
combined reductive amination-alcohol amination of 5-HMF
was studied, a reaction that was previously never performed.
Obviously this requires the combination of H2 and NH3 in
order to arrive at the diamine. After addition of NH3, the
pressure in the autoclave was 7.5 bar (the standard pressure
of ammonia at room temperature). The autoclave was further
pressurized to a total pressure of 10 bar with H2.
The amination of 2,5-bis(hydroxymethyl)furan (BHMF) has
been addressed in a recent patent application.[51] However,
a direct and combined reductive amination-alcohol amination
of 5-HMF as a one-pot procedure would be highly desirable
but has not been reported before. In view of this target the
aforementioned conditions for the amination of long chain
diols were adapted to the amination of BHMF as a model
reaction. These furan-based molecules can be susceptible to
various side reactions, especially at the reaction
temperatures required for the amination. In addition, the
product, 2,5-bis(aminomethyl)furan (BAMF) is known to
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100
A
100
90
80
70
60
50
40
30
20
10
0
A
90
80
70
60
50
40
30
20
10
0
0
15 30 45 60 75 90 105 120 135 150
Time [h]
0
1
2
3
4
5
6
7
8
9
10 11 12
Time [h]
100
90
80
70
60
50
40
30
20
10
0
B
100
90
80
70
60
50
40
30
20
10
0
B
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Time [h]
0.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
Time [h]
Graph 1. Reaction profile of the direct amination of 5-hydroxymethylfurfural with
NH3 and H2 using catalyst C1. Conditions: Milstein catalyst, C1 (0.5 mol%), 5-
HMF (5 mmol), tert-amyl alcohol (15 mL), NH3 (5 mL, 195 mmol), H2 (2.5 bar),
150°C. Full reaction profile (A), zoom in on the first 4 hours (B). ■= 5-HMF, ●=
aminoalcohol, ▲= BAMF diamine. Conversion and selectivity were determined
via GC-analysis.
Graph 2. Reaction profile of the amination of 5-hydroxymethylfurfural with NH3
and H2 using system C1 with a decreased H2 concentration. Conditions: Milstein
catalyst (0.5 mol%), 5-HMF (10 mmol), tert-amyl alcohol (55 mL), NH3 (10 mL,
390 mmol), H2 (2.5 bar), 150°C. Full reaction profile (A), zoom in on the first 4
hours (B). ■= 5-HMF, ●= aminoalcohol, ▲= BAMF diamine. Conversion and
selectivity were determined via GC-analysis.
The reaction profile shows a very fast consumption of 5-HMF
(Graph 1, B). In about 30 minutes all 5-HMF is converted to
the intermediate aminoalcohol. At the reaction temperature,
it can be expected that the aldehyde is immediately
converted to the imine, due to its high reactivity but also due
to the excess of ammonia. The hydrogenation step appears
to be fast, which indicates that the catalyst takes up the
added H2, and hydrogenates the imine.[53] The subsequent
conversion of the aminoalcohol to the diamine is much
slower. The amount of aminoalcohol gradually decreases
over 140 h, while the amount of produced diamine (BAMF)
constantly increases (Graph 1, A). This is a strong indication
that the catalyst is saturated by the hydrogen in the system,
and for a large part unavailable for the required alcohol
The 1H NMR spectrum of the product essentially is identical
to that of the product from amination of BHMF, with two
singlet resonances at 6.0 and 3.8 ppm, as anticipated (Graph
S16, SI). Some minor additional peaks reveal that the
reaction is not perfectly clean and some by-products occur
which do not show in GC. Therefore, the exact selectivity and
product purity were determined via 1H NMR and were found
to be slightly lower namely 85% selectivity while GC analysis
suggested a product purity of 90-100%. This compares
favourably to GC purity data reported in a patent by Schaub
and co-workers[51] for diamine produced from the separately
prepared diol. The minor additional signals in 1H NMR were
reduced by lowering the reaction temperature to 140°C,
which also decelerated the reaction, resulting in a reaction
dehydrogenation. In order to reduce the ratio of H2 to catalyst, time of 24 hours for complete conversion.
the reaction was scaled-up, while the H2 amount was kept
Polycondensation
constant. Under these conditions the reaction time was
reduced to 12 hours until completion (Graph 2, A). Again 5-
HMF was consumed rapidly (Graph 2, B), leaving only the
aminoalcohol after 30 min, which then smoothly converted to
BAMF.
Melt-polycondensations were carried out under elevated
pressure in a 25 mL stainless steel reactor.[54] Stoichiometric
amounts of the diamine and the diacid were reacted in the
initial presence of excess water as a reaction medium (Table
2).
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10.1002/cctc.201800365
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here (Graph 3), and matches with previous observations on
these polyamides generated through other routes.[1,56] As the
formation of hydrogen bonds also depends on the odd or
even number of carbon atoms in the chain, the melting points
of odd/odd, even/even and odd/even polyamides variate.
Table 2. Molecular weights and melting points of the polycondensation
products of various chain length diamines and diacids.
Entry
1[c]
2[c]
3
Polyamide PA
7,19
Mn (g/mol)[a]
13700
Tm (°C)[b]
180
Conclusions
8,19
19300
183
The direct amination of various long-chain diols is feasible
employing the acridine-based diphosphine ruthenium complex,
previously reported by Milstein. A high excess of ammonia is key
to prevent the formation of cyclic and secondary amines. In a
single amination step, long-chain diamines were obtained,
sufficiently pure for subsequent polycondensation, previously not
demonstrated in this type of catalytic synthesis of diamines. In
contrast to previous methods, no intensive purification was
12,12
12400
187
4
12,18
28100
171
5
12,19
19500
170
6
19,19
18700
158
7
23,23
21600
149
required.
A one-pot, combined reductive amination-alcohol
Polyamides were obtained by melt polymerisation in the presence of
degassed (mL) water pre-pressurized with 10 bar nitrogen pressure and
heated to 210°C for 2.5 hours, subsequently 2 hours vacuum. [a] molecular
weights determined by 1H NMR spectroscopy at 403 K in C2D2Cl4 with
addition of phenol via endgroup analysis. [b] melting points determined by
DSC. [c] Vacuum was applied for 1.75 hours.
amination of 5-HMF yielded 2,5-bis(aminomethyl)furan (BAMF).
The reaction requires additional hydrogen, which dramatically
slowed down the entire reaction. By minimizing the partial
pressure of H2 the diamine was produced at the same rate as in
the direct amination of the separately prepared diol. This new one-
step procedure is particularly attractive due to the ready
availability of 5-HMF as a lignocellulose-based platform chemical.
Lignocellulosic waste material does not compete with food use of
renewable feedstocks, and notably also the long-chain feedstocks
used here can be generated from microalgae oils.[62,63]
Generally, the obtained polyamides were white to yellow
materials. For comparison, with commercial monomers such
as 1,12-diamine and 1,18-diacid or with 1,19-diacid from
isomerizing carbonylation, molecular weights varying from
1.2×104 to 2.8×104 g mol-1 were obtained (Table 2, entry 1-
5). The polyamides with the (catalytically) synthesised long
chain diamines exhibited comparatively high molecular
weights of about 1.8×104 and 2.1×104 g mol-1, respectively
(entry 6 and 7, Table 2). Note that these molecular weights
match with those of typical commercial polyamides.[55]
Experimental Section
General considerations
All syntheses were carried out under inert gas atmosphere using standard
Schlenk or glovebox techniques unless stated otherwise. All catalytic
reactions were carried out under inert gas atmosphere. Toluene was dried
in a solvent purification system over aluminium oxide and stored under
inert gas. THF was dried over sodium benzophenone and stored under
inert gas. Water was distilled under nitrogen atmosphere and stored under
inert gas. The 4,5-bis-(di-iso-propylphosphinomethyl)acridine (Milstein
acridine Ligand) was prepared following a published procedure.[40] The
long-chain dimethyl esters C18, C19, C23 were available in the Mecking
Group and were prepared according to a published procedure.[5] 5-
190
12,12
180
12,18
12,19
170
160
150
140
(Hydroxymethyl)furfural,
bis(aminomethyl)furan
2,5-bis(hydroxymethyl)furan
bought from Carbosynth.
and
1,12-
were
19,19
18,18
Diaminododecane was purchased from TCI and 1,12-dodecanedioic acid,
1,12-diaminododecane (98%) from Sigma-Aldrich. 1,18-Octadecanedioic
acid was purchased from Elevance and recrystallized from toluene before
use. 1,6-diaminohexane (97%) and 1,8-diaminooctane (98%) were
purchased from Fluka. Ammonia was acquired from BOC in micrographic
grade 99.998% in a 5.0 L cylinder equipped with a BS10 dual port valve
and was dosed using a Bronkhorst Liquid-Flow mass flow controller.
Hydrogen for the amination was purchased from BOC in industrial grade
with a purity of 99.99%. Amination reactions were carried out in 75 mL
stainless steel autoclaves equipped with a Pt-100 thermocouple, a gas
inlet, a pressure gauge, a sampling unit for 50 μL samples and an inlet for
reagents. Polymerisations were performed in 20 mL autoclaves equipped
with a 15 mL glass inlay, two gas inlets and a pressure gauge. Deuterated
solvents were bought from Eurisotop except for CDCl3, which was received
from Sigma-Aldrich and stored over 4Å molecular sieves. CD3OD was
23,23
4.0
4.5
5.0
5.5
6.0
6.5
7.0
7.5
8.0
number of amide groups per 100 chain atoms
Graph 3. Variation of the melting point depending on the CH2 to CONH ratio.
Generally pronounced odd/even effects are found for the melting behaviour of
aliphatic polyamides.
The linear increase of the melting point with a lower chain-
length of the monomers is evident for the materials studied
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dried over 3Å molecular sieves. NMR spectra were recorded on Bruker
Avance III 400 MHz, Bruker Avance III 500 MHz, Bruker Avance DRX 600
spectrometers or a Varian Unity INOVA 400 MHz spectrometer. H NMR
298 K, 400 MHz, δ=ppm): 2.67 (t, 3JHH = 7.0 Hz, 4H, H-2), 1.42 (m, 4H, H-
3), 1.27 (m, 28H, H-6). See Graph S8 for assignment.
1
spectra were recorded at 400 MHz, 500 MHz, and 600 MHz. The splitting
patterns in the NMR spectra are listed as followed: chemical shift (δ) in
ppm, multiplicity, coupling constant in Hertz, integral, label of the protons.
Following abbreviations were used: (s) for singlet, (d) for doublet, (t) for
triplet and (m) for multiplet. Acquired data was processed and analysed
using MestReNova software. Amination of 5-HMF or BHMF as substrate
were monitored over time and analysis was conducted via gas
chromatography using a Shimadzu GC-2010 instrument equipped with a
flame-ionisation detector (FID) and an Ultra-19091B-102 column (25.0 m,
0.20 mm ID, 95% dimethyl polysiloxane, 5% phenylmethyl polysiloxane).
The column flow was 0.69 mL/min with helium as carrier gas and a linear
velocity of 26.1 cm/s. Injection was conducted at 270°C, and the sample
was detected at 290°C. The method started at 80°C and within 18 minutes
the temperature was increased to 215 °C and within 3 minutes the
temperature was raised to 270°C which was held for another 3 minutes.
Further GC analyses were carried out on a Perkin Elmer Clarus 500 GC
system equipped with a flame-ionisation detection (FID) over a Perkin
Elmer Elite-5 capillary column (30 m, 0.25 mm, 0.25 μm, 5% phenylmethyl
polysiloxane 95% dimethyl polysiloxane) and a Perkin Elmer Elite-5MS
column (15 m, 0.32 mm, 0.1 μm, 5% phenylmethyl polysiloxane 95%
dimethyl polysiloxane). The injection volume of the automatic sampler was
set to 1 μl. The sample was injected at 300°C and detected at 280°C. For
both columns the same method was used, which started at 90°C and
maintained this temperature for 1 min before heating to 280°C within 30
min. The final temperature was kept constant for another 8 min.
1,19-nonadecanediol to 1,19-nonadecane diamine:
Into a 75 mL autoclave, 1.50 g (5 mmol) of 1,19-nonadecane diol and 15.1
mg (0.025 mmol, 0.5 mol%) [RuHCl(acridine-iPr-PNP)(CO)] were weighed.
The autoclave was equipped with a cross-shaped stirring bar, closed and
purged several times with argon. Via syringe, 15 mL toluene was added.
Subsequently, 15 mL (585 mmol) of NH3(l) was added via a mass flow
controller. The autoclave was then heated to 150°C and stirred for 65
hours. After cooling to room temperature, the reactor was vented, and the
reaction mixture was transferred into a 100 mL round bottom flask. The
solvent was removed in vacuo and an off-white powder was obtained
consisting of 96% of the desired diamine with 4% of 1-amino-19-nitrile as
by-product and could not be purified further. 1H NMR (CDCl3, 298 K, 400
MHz, δ=ppm): 2.67 (t, 3JHH = 7.0 Hz, 4H, H-2), 1.42 (m, 4H, H-3), 1.27 (m,
30H, H-6). See Graph S9 for assignment.
1,23-tricosanediol to 1,23-tricosane diamine:
Into a 75 mL autoclave, 1.79 g (5 mmol) of 1,23-tricosane diol and 15.1 mg
(0.025 mmol, 0.5 mol%) [RuHCl(acridine-iPr-PNP)(CO)] was weighed. To
this, a cross-shaped stirring bar was added, and the autoclave was closed.
After purging several times with argon, 15 mL of toluene was added via
syringe. Subsequently, 15 mL (585 mmol) of NH3(l) was added via a mass
flow controller. The autoclave was then heated to 150°C and stirred for 65
hours. After cooling to room temperature, the reactor was vented, and the
reaction mixture was transferred into a 100 mL round bottom flask. The
solvent was removed in vacuo and an off-white powder was obtained
consisting of 90% of the desired amine with 10% of 1-amino-23-nitrile as
by-product. In 80 mL heptane, (1.66 g, 4.69 mmol) 1,23-diaminotricosane
was dissolved at 95°C. It should be noted that above 95°C, a brown, fluffy
solid precipitated from the solution. The solution was filtrated hot to remove
all insoluble parts. After cooling to 8°C, an off-white precipitate occurred
which was filtered off and dried under vacuum. The product was isolated
as an off-white solid in 1.40 g (3.955 mmol, 84%) yield with a purity of 94%
according to 1H NMR analysis. 1H NMR (CDCl3, 298 K, 400 MHz, δ=ppm):
2.67 (t, 3JHH = 7.0 Hz, 4H, H-2), 1.43 (m, 4H, H-3), 1.25 (m, 36H, H-6). See
Graph S10 for assignment.
1,14-tetradecanediol to 1,14-tetradecane diamine:
Into a 75 mL autoclave, 1.15 g (5 mmol) of 1,14-octadecane diol and 15.1
mg (0.025 mmol, 0.5 mol%) [RuHCl(acridine-iPr-PNP)(CO)] were weighed.
The autoclave was equipped with a cross-shaped stirring bar, closed and
purged several times with argon. Via syringe, 15 mL toluene was added.
Subsequently, 15 mL (585 mmol) of NH3(l) was added via a mass flow
controller. The autoclave was then heated to 150°C and stirred for 65
hours. After cooling to room temperature, the reactor was vented, and the
reaction mixture was transferred into a 100 mL round bottom flask. The
solvent was removed in vacuo and an off-white powder was obtained. The
powder (1.08 g, 4.73 mmol) was subsequently dissolved in 75 ml heptane
at 90-95°C. It should be noted that above 95°C, a brown, fluffy solid
precipitated. The solution was filtrated hot to remove all the insoluble parts.
After cooling to 8°C, an off-white precipitate formed which was filtrated and
dried under vacuum. The product was isolated as an off-white powder
(0.94 g, 4.12 mmol, 82%) in 90% purity. 1H NMR (CDCl3, 298 K, 400 MHz,
δ=ppm): 2.67 (t, 3JHH = 7.0 Hz, 4H, H-2), 1.45 (m, 4H, H-3), 1.28 (m, 28H,
H-6). See Graph S7 for assignment.
2,5-Bis(hydroxymethyl)furan to 2,5-bis(aminomethyl)furan (BAMF):
Into a 75 mL autoclave, 640 mg (5 mmol) of bis(hydroxymethyl)furan and
15.1 mg (0.025 mmol, 0.5 mol%) [RuHCl(acridine-iPr-PNP)(CO)] were
weighed. A cross-shaped stirring bar was placed in the autoclave after it
was closed and purged several times with argon. Via syringe, 15 mL of
tert-amylalcohol was added followed by 5 mL (195 mmol) NH3(l) via a mass
flow controller. The autoclave was then heated to 150°C and stirred for 7
hours. After cooling to room temperature, the autoclave was vented, and
the reaction mixture was transferred into a 100 mL round bottom flask. The
solvent was removed in vacuo and the diamine was isolated as a viscous
brown liquid (isolated: 410 mg, 3.25 mmol, 65%). The reaction was
monitored by taking samples at specific time intervals and GC analysis
was conducted subsequently. 1H NMR (CDCl3, 298 K, 400 MHz, δ=ppm):
6.04 (s, 2H, H-1), 3.79 (s, 4H, H-2). See Graph S16 for assignment.
1,18-octadecanediol to 1,18-octadecane diamine:
Into a 75 mL autoclave, 1.43 g (5 mmol) of 1,18-octadecane diol and 15.1
mg (0.025 mmol, 0.5 mol%) [RuHCl(acridine-iPr-PNP)(CO)] were weighed.
The autoclave was equipped with a cross-shaped stirring bar, closed and
purged several times with argon. Via syringe, 15 mL toluene was added.
Subsequently, 15 mL (585 mmol) of NH3(l) was added via a mass flow
controller. The autoclave was then heated to 150°C and stirred for 65
hours. After cooling to room temperature, the reactor was vented, and the
reaction mixture was transferred into a 100 mL round bottom flask. The
solvent was removed in vacuo and an off-white powder was obtained. The
powder (1.408 g, 4.949 mmol) was dissolved in 75 ml heptane at 90-95°C.
It should be noted that above 95°C, a brown, a fluffy solid precipitated. The
solution was filtrated hot to remove all the insoluble parts. After cooling to
8°C, an off-white precipitate formed which was filtrated and dried under
vacuum. The product was isolated as an off-white powder (1.00 g, 3.515
mmol, 71%) in 90% purity und could not be purified further. 1H NMR (CDCl3,
5-hydroxymethylfuran to 2,5-bis(aminomethyl)furan (BAMF):
Into a 75 mL autoclave, 1.280 g (10 mmol) 5-hydroxymethylfurfural and
30.2 mg (0.05 mmol, 0.5 mol%) [RuHCl(acridine-iPr-PNP)(CO)] were
weighed and a cross-shaped stirring bar was added. Then the autoclave
was closed and purged several times with argon. To the autoclave, 25 mL
tert-amylalcohol was added via syringe followed by 10 mL (390 mmol)
NH3(l) via a mass flow controller. Subsequently, the reactor was further
pressurised to 10 bar with H2(g). The autoclave was heated to 140°C and
stirred for 11 hours. After cooling to room temperature, the autoclave was
vented and the reaction mixture was transferred into a 100 mL round
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10.1002/cctc.201800365
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bottom flask. The solvent was removed in vacuo and the diamine was
isolated as a viscous brown liquid (isolated: 731.7 mg, 5.8 mmol, 85%).
The reaction was monitored by taking samples at specific time intervals
and GC analysis was conducted subsequently. 1H NMR (CDCl3, 298 K,
400 MHz, δ=ppm): 6.04 (s, 2H, H-1), 3.79 (s, 4H, H-2). See Graph S16 for
assignment.
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Long-chain diamines were prepared
in high conversion and selectivity by
the catalytic direct amination of long-
chain diols, derived from plant oils.
From the lignocellulose-based 5-
Dennis Pingen, Judith B. Schwaderer,
Justus Walter, Jiaqi Wen, George
Murray, Dieter Vogt, Stefan Mecking*
Page No. – Page No.
hydroxymethyl-furfural,
bis(aminomethyl)furan
generated via a one-pot, one-step
direct amination and reductive
2,5-
was
Diamines for Polymer Materials via
Direct Amination of Lipid- and
Lignocellulose-based Alcohols with
NH3
amination
using
ammonia.
Polycondensation of the long-chain
diamines with long-chain diacids led
to
higher
molecular
weight
polyamides, illustrating the quality of
the diamines.
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