Synthesis of 1-octanol and 1,1-dioctyl ether from biomass-derived platform chemicals

Article abstract of DOI:10.1002/anie.201203669

The happy medium: A new catalytic pathway for the synthesis of the linear primary C8?alcohol products 1-octanol and dioctyl ether from furfural and acetone has been developed using retrosynthetic analysis. This opens a general strategy for the synthesis of medium-chain-length alcohols from carbohydrate feedstock.

Full text of DOI:10.1002/anie.201203669

Angewandte
Chemie
DOI: 10.1002/anie.201203669
Biogenic Alcohols
Synthesis of 1-Octanol and 1,1-Dioctyl Ether from Biomass-Derived
Platform Chemicals**
Jennifer Julis and Walter Leitner*
[
1c,4]
As a consequence of diminishing fossil resources and global
endeavors to reduce anthropogenic carbon dioxide emissions,
biomass-derived substrates are receiving increasing attention
in the effort to establish renewable supply chains for trans-
drates,
at least in principle. This opens a general strategy
for the synthesis of medium-chain-length alcohols from
carbohydrate feedstock.
Recently, we proposed the concept of synthetic pathway
design for biomass-derived products in analogy to the
[
1]
portation fuels and chemical products. Carbohydrates con-
stitute the largest fraction of biomass feedstock. The con-
version of carbohydrates from a set of platform molecules
into tailor-made products can be envisaged through selective
[2]
retrosynthetic analysis used in modern organic synthesis.
Scheme 1 shows how 1-octanol can be traced back to furfural
and acetone as starting materials using this approach. These
compounds are readily converted into furfuralacetone (FFA)
[
1a,2]
catalytic transformation steps.
[
8]
Primary alcohols of medium chain length are very
important industrial products, as they are valuable com-
pounds for the production of detergents and surfactants, in
perfumery, and as flavors. 1-Octanol is of particular impor-
tance and is also used for the synthesis of 1-octene, an
important co-monomer for polyethylene. 1-Octanol is pre-
dominantly synthesized either by the reaction of ethylene
with triethylaluminum (Alfen process) or by oxo synthesis
starting from n-heptene, which are both petrochemical
by an aldol condensation; FFA can then be hydrogenated to
[
9]
4-(2-tetrahydrofuryl)-2-butanol (THFA), which might be
converted into 1-octanol (1-OL) by selective deoxygenation
and ring opening, provided that over-hydrogenation to the
[
5c,10]
alkane can be avoided.
Therefore, the challenge in
establishing this pathway lies in the development of a selective
catalytic system that can give access to 1-octanol from THFA
by deoxygenation of the secondary alcohol function coupled
with the selective ring-opening of the tetrahydrofuryl ring by
hydrogenolysis.
[3]
processes.
Aliphatic alcohols from biomass are accessible by the
reduction of fatty acids, but this is commercially exploited
[1a]
almost exclusively for long carbon chains (ꢀ C ). Carbo-
1
2
hydrate-based alcohols are currently limited to short carbon
[
1a,4]
chains (ꢁ C ) and are obtained through fermentation.
In
4
contrast, the formation of alcohols of medium chain length
from lignocellulosic platform chemicals is described in only
very few cases and is not yet synthetically exploited. 1-
Pentanol has been observed as a by-product, for example, in
the hydrogenolysis of tetrahydrofurfuryl alcohol and in the
selective transformation of levulinic acid into 2-methyltetra-
[5]
Scheme 1. Retrosynthetic analysis for a pathway to 1-octanol using
platform chemicals derived from lingocellulosic feedstock.
[
2,6]
hydrofuran.
Scheme 2 shows the possible products resulting from
hydrogenation and dehydration of THFA using a multifunc-
tional catalytic system that provides both transition-metal-
Herein, we describe the highly selective catalytic synthesis
of the linear primary C alcohol products 1-octanol and
8
[1d]
dioctyl ether from the biomass-derived platform molecule
based hydrogenation activity and Brønsted acidity.
2-
[
7]
furfural and acetone, which is also accessible from carbohy-
Butyltetrahydrofuran (BTHF) is obtained by removal of the
secondary hydroxy group. BTHF is an interesting molecule in
[
5c,11]
its own right, for example, as a potential fuel additive.
Full deoxygenation of THFA leads to n-octane.
[
*] Dipl.-Chem. J. Julis, Prof. Dr. W. Leitner
Institut fꢀr Technische und Makromolekulare Chemie, RWTH
Aachen University
[
5c,10a]
The
targets of the present study are the linear C alcohol products
8
Worringerweg 1, 52074 Aachen (Germany)
E-mail: leitner@itmc.rwth-aachen.de
Homepage: http://www.itmc.rwth-aachen.de
Prof. Dr. W. Leitner
Max-Planck-Institut fꢀr Kohlenforschung
45470 Mꢀlheim an der Ruhr (Germany)
[
**] This work was performed as part of the Cluster of Excellence “Tailor-
Made Fuels from Biomass”, which is funded by the Excellence
Initiative of the German federal and state government to promote
science and research at German universities.
Supporting information for this article is available on the WWW
under http://dx.doi.org/10.1002/anie.201203669.
Scheme 2. Possible C products accessible by catalytic conversion of
THFA by dehydration/hydrogenation reactions.
8
Angew. Chem. Int. Ed. 2012, 51, 1 – 6
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
1
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.
Angewandte
Communications
(
C -OL), which can be directly formed as free 1-octanol (1-
was possible to reduce the acid-catalyzed side reactions by
diluting the Ru@[BSO BIM][NTf ] catalyst with the inert IL
8
OL) by hydrogenolytic ring opening, or as dioctyl ether
3
2
(
DOE) upon reversible etherification.
[EMIM][NTf ], which resulted in significant formation of C -
2 8
Scheme 3 gives an overview of the components that were
OL (28% overall yield of 1-OL and DOE) and high
selectivity towards 1-OL (entry 3). Under the same condi-
tions, the use of Ru@[BSO BIM][OTf] or Ru@[BSO N444]-
selected for the generation of the catalytic systems in the
present study. Ruthenium was introduced as the metal
component for hydrogenation because of its proven activity
in transformations of FFA, THFA, and related mole-
3
3
[NTf ] resulted in a combination of hydrogenation and acid
2
catalysis that led to a remarkable BTHF yield of up to 75%,
with isomerization and etherification products of THFA as
the main side products (entries 4 and 5). Therefore, the
system of entry 3 was chosen as first lead structure for further
investigation.
Monitoring the reaction (Figure 1) revealed that acid-
catalyzed self-etherification and isomerization of the sub-
strate also occur with this system and dominate the con-
version during the first two hours (Scheme 4). However, the
hydrogenolysis of the secondary alcohol group in the side
chain of THFA reverses the etherification equilibrium, and
the deoxygenation product, BTHF, is accumulated with
a maximum of 80% conversion in the reaction mixture after
eight hours. Selective ring opening of the tetrahydrofuryl ring
in BTHF then yields 1-OL, which again subsequently under-
goes partial etherification under the acidic conditions to
[
2,8,12]
cules.
Ruthenium nanoparticles stabilized in ionic liquids
(
Ru@IL) were investigated for this application, along with
commercially available heterogeneous catalysts. Brønsted
acid additives, including functional ionic liquids (ILs) were
[
13]
chosen to control the acidity required for dehydration. In
the first series of experiments, the transformation of THFA
under hydrogen with ruthenium nanoparticles (particle size
2
–3 nm) was investigated. The nanoparticles were prepared
3
by hydrogenation of [(cod)Ru(h -C H ) ] in the presence of
different ILs.
4
7 2
[
8,13c]
Scheme 3. Metal components and acidic additives, including ionic
liquids (ILs), used for the multifunctional catalytic systems.
As seen in Table 1, the Ru@[BCO BIM][NTf ] catalyst
2
2
showed no activity in the hydrogenolysis of THFA, indicating
that the acidity of the carbonic acid function in the ionic liquid
is too weak for the dehydration (Table 1, entry 1). In contrast,
the performance of Ru@[BSO BIM][NTf ] was dominated by
Figure 1. Reaction monitoring of the hydrogenolysis of THFA with
3
2
Ru@[BSO BIM][NTf ]. Conversion (c
1
&
c), BTHF (c*c),
3
2
the acidity of the SO H function, resulting mainly in ether-
3
~
-OL (c*c), DOE (c c), condensate (c*c). For
ification and isomerization of THFA (entry 2). However, it
reaction conditions, see Table 1, entry 3. For structures, see Scheme 4.
Table 1: Hydrogenolysis of THFA with Ru@IL.
[
a]
Entry
Ionic liquid
Conv.
BTHF
[%]
1-OL
[%]
DOE Other
[%]
[%]
[%]
[
[
[
[
[
[
b]
b]
c]
c]
c]
c]
1
2
3
4
5
6
[BCO BIM][NTf ]
0
–
5.0
66.6
69.0
74.4
75.3
–
–
25
9.7
9.6
3.2
–
–
2.8
1.0
3.2
–
–
95
5.6
21.2
12.8
21.5
2
2
[BSO BIM][NTf ]
>99
>99
>99
>99
>99
3
2
[BSO BIM][NTf ]
3
2
[BSO BIM][OTf]
3
[BSO N444][NTf2]
3
[BSO N888][NTf2]
3
[a] Other=isomers and etherification products of THFA. [b] 1208C, H2
(
(
(
120 bar), 15 h, Ru (0.016 mmol), acidic IL (0.11 mmol), THFA
1.57 mmol). [c] 1208C, H (120 bar), 15 h, Ru (0.016 mmol), acidic IL
2
0.11 mmol), THFA (1.57 mmol), [EMIM][NTf ] (2.9 mL).
2
Scheme 4. Consecutive hydrogenation/deyhdration pathway of THFA.
2
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Chemie
À1
produce DOE. Further dehydration to n-octane remains
insignificant under these conditions, reflecting the greater
resistance of the primary alcohol versus secondary alcohols to
acid-catalyzed hydrogenolysis.
0.5 molL substrate concentration, a maximum yield of 45%
1-OL and an overall C -OL yield of 71.4% was obtained. In
8
particular, no over-hydrogenation to n-octane was observed.
Using the optimized conditions, a series of combinations
of Ru-based catalysts and acidic additives were evaluated for
the hydrogenolysis of THFA (Table 2, entries 1–5; see also
the Supporting Information). Ru@[N444BSO ] gave a slightly
higher combined yield for the C -OL products with a lower 1-
OL/DOE-ratio and small amounts of n-octane, as compared
to the imidazolium ionic liquid (entries 1 and 2). Commer-
cially available Ru/C and Ru/Alox (Alox = aluminum oxide)
catalysts also performed well (entries 3 and 4), providing up
The monitoring of the hydrogenolysis of THFA allowed
elucidation of the complex network of consecutive reactions,
which involve uni- and bimolecular transformations of the
substrate and product, respectively. Therefore, the reaction
parameters of temperature, reaction time, and substrate
concentration were selected for further optimization using
the simplex algorithm, with the yield of 1-OL as the target
value (Figure 2). The parameter limits were set to T= 120–
3
8
0
À1
1
608C, t = 10–25 h and c (THFA) = 0.2–0.8 molL , while
to 75% yield of C -OL with outstanding selectivity for the
8
hydrogen pressure and the substrate-to-catalyst ratio were
kept constant.
removal of the secondary hydroxy function. Results varied
significantly with the source of the catalysts (see the
Supporting Information for details) and the data presented
in Table 2 were obtained with Ru/C (5%) obtained from the
supplier abcr. They were found to be reproducible within
Æ 5.0% over three independent experiments and varied
Æ 7.0% between two different catalyst batches. In combina-
tion with p-toluenesulfonic acid (p-TsOH), a 77% overall
yield of C -OL was achieved within 15 h, whereby the larger
8
content of DOE and the formation of significant amounts of
n-octane reflect the higher acidity of the reaction mixture
(entry 5).
Once the transformation of THFA into C -OL had been
8
successfully demonstrated, further development of the syn-
thetic pathway shown in Scheme 1 was attempted. If the
reaction sequence was performed in individual steps with
intermediate isolation of the products, the cumulative yields
of the individual steps (97%, 98%, 77%) resulted in an
overall yield of 73%, based on furfural. A direct one-step
conversion of FFA into C -OL using the multifunctional
8
catalyst systems was not possible, because furfuralacetone
(
FFA) is very sensitive towards acidic conditions and forms
Figure 2. Optimization of reaction conditions for Ru@[BSO BIM][NTf ]
by the simplex algorithm (size of data points correspond to yields of 1-
OL).
3
2
humin-type products in the presence of p-TsOH or
[BSO BIM][NTf ].
3
2
However, a two-step one-pot process could successfully
be achieved when the acidic additive was introduced directly
into the reaction vessel after full hydrogenation of FFA to
THFA (entry 6). After FFA was hydrogenated at 1208C with
After 16 iteration steps, the alteration of the command
variables reached a stable output within error tolerance.
Under the optimized reaction conditions of 1508C, 15 h, and
H (120 bar) for two hours in the presence of Ru/C, the acidic
2
[
a]
Table 2: One-pot catalytic synthesis of linear C alcohol products (C -OL) from biomass-derived platform chemicals.
8
8
[
b]
Entry
Substrate
Steps
Catalyst
Additive
BTHF
%]
1-OL
[%]
DOE
[%]
Octane
[%]
Other
C8-OL
[%]
[
[%]
[
[
[
[
[
[
[
[
c]
c]
c]
c]
c]
d]
d]
e]
1
2
3
4
5
6
7
8
THFA
THFA
THFA
THFA
THFA
FFA
1
1
1
1
1
2
2
3
Ru@[BSO BIM][NTf ]
–
–
25.8
11.7
47.8
23.0
8.7
5.4
2.1
23.5
44.9
41.5
20.5
43.6
24.7
48.8
18.1
32.5
26.1
34.5
19.4
31.8
51.9
44.2
53.0
19.8
–
2.4
–
–
8.5
–
3.2
9.9
12.3
1.6
6.2
1.8
71.0
76.0
39.4
75.4
76.6
93.0
71.1
52.3
3
2
Ru@[BSO N444][NTf2]
3
Ru/C (5 wt% Ru)
Ru/Alox (5 wt% Ru)
Ru/C (5 wt% Ru)
Ru/C
Ru/C
Ru/C
[BSO BIM][NTf ]
[BSO BIM][NTf ]
p-TsOH
[BSO BIM][NTf ]
p-TsOH
[BSO BIM][NTf ]
3
2
3
2
3
2
FFA
furfural
16.9
–
10.8
[f]
24.2
3
2
[a] Mass distribution of the product mixture after pentane extraction according to GC analysis using n-tetradecane as internal standard; >99%
conversion was observed in all cases. [b] Other=other isomers, mainly 2-propyltetrahydropyran. [c] THFA (1.57 mmol), Ru (0.016 mmol), acidic
additive (0.11 mmol) in [EMIM][NTf ] (2.9 mL), 1508C, H (120 bar), 15 h. [d] 1st step: 1208C, H (120 bar), 2 h, neat FFA (1.57 mmol), Ru
2
2
2
(
0.016 mmol); 2nd step: as in [c], 60 h. [e] 1st step: furfural/acetone 1:10, RT, 15 h, NaOH (50 mL, 1.0m); 2nd and 3rd step: as in [c] and [d],
respectively. [f] Isomers of THFA. Alox=aluminum oxide.
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IL [BSO BIM][NTf ] and the [EMIM]-
3
2
[
NTf ] solvent were added, and the
2
reaction mixture was treated further at
508C with H2 (120 bar) for 45 h to
1
obtain 1-OL and DOE in excellent
combined yields of 93%. Considerable
amounts of n-octane were formed when
p-TsOH was used as an acidic additive to
Ru/C (entry 7). The ruthenium nanopar-
ticle catalysts could not be used in this
procedure, as they were found to be
deactivated by agglomeration during the
first part of the sequence.
Scheme 5. Integrated multi-step synthesis of linear C alcohol products (C -OL) from furfural
and acetone as biogenic platform chemicals.
8
8
It is even possible to conduct this reaction sequence as
a one-pot procedure starting from furfural as a platform
chemical (Scheme 5). Furfural was transformed to FFA by an
aldol condensation in the presence of excess acetone using
sodium hydroxide under standard conditions (see Table 2 for
details). After neutralization of the reaction mixture with
aqueous HCl and evaporation of acetone, Ru/C was added
and the hydrogenation was carried out as above. After 2 h, the
acidic IL [BSO BIM][NTf ] and the solvent IL were intro-
was activated at 808C with H
2
(100 bar) for 10 h prior to use. In
a typical hydrogenolysis reaction, 4-(2-tetrahydrofuryl)-2-butanol
THFA; 225.7 mg, 1.57 mmol), 1-ethyl-3-methylimidazolium bis(tri-
fluoromethylsulfonyl)imide (2.9 mL) and the acidic additive
0.11 mmol) were added to the metal catalyst and the reaction
(
(
mixture was stirred for 15 h at 1508C with H2 (120 bar). After
carefully venting the reactor, the reaction mixture was extracted with
pentane (3 ꢀ 20 mL). The colorless solution was concentrated under
reduced pressure and the molar composition of the product mixture
was analyzed by GC with n-tetradecane as an internal standard. Full
details of the experimental and analytical procedures are provided in
the Supporting Information.
3
2
duced directly for the final step. The overall yield for C -OL
8
was 54% with a higher 1-OL content, corresponding to
a remarkable 33% yield of the free alcohol. The somewhat
lower overall yield can be attributed at least partly to the
presence of the salt resulting from the neutralization process.
Received: May 11, 2012
Published online: && &&, &&&&
[
11]
Using a base-catalyzed protocol for the aldol condensation
and/or conducting the one-pot procedure in a flow system
Keywords: biomass conversion · homogeneous catalysis ·
[14]
.
hydrogenation · linear alcohols · multifunctional catalysts
are possibilities for further development towards a fully
integrated reaction sequence.
In summary, we have demonstrated for the first time the
selective conversion of tetrahydrofurfurylacetone (THFA)
and furfuralacteone (FFA) into 1-octanol and dioctyl ether by
dehydration/hydrogenation using a multifunctional catalyst
system comprised of a Ru hydrogenation catalyst together
with an acidic additive, including functional ionic liquids. Up
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reactor with a glass inlet. Metal catalysts and ionic liquids were
handled under an argon atmosphere. Ru@ILs were freshly prepared
3
before use by suspending [(cod)Ru(h -C H ) ] (5.0 mg, 0.016 mmol)
4
7 2
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Communications
Biogenic Alcohols
J. Julis, W. Leitner*
&&&& — &&&&
Synthesis of 1-Octanol and 1,1-Dioctyl
Ether from Biomass-Derived Platform
Chemicals
The happy medium: A new catalytic
pathway for the synthesis of the linear
thetic analysis. This opens a general
strategy for the synthesis of medium-
chain-length alcohols from carbohydrate
feedstock.
primary C alcohol products 1-octanol
8
and dioctyl ether from furfural and ace-
tone has been developed using retrosyn-
6
www.angewandte.org
ꢀ 2012 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed. 2012, 51, 1 – 6
These are not the final page numbers!