A versatile biobased continuous flow strategy for the production of 3-butene-1,2-diol and vinyl ethylene carbonate from erythritol

Article abstract of DOI:10.1039/c8gc02468e

A versatile, tunable and robust continuous flow procedure for the deoxydehydration (DODH) of biobased erythritol toward 3-butene-1,2-diol is described. The procedure relies on specific assets of multistep continuous flow processing. Detailed mechanistic and computational studies on erythritol show that either 3-butene-1,2-diol or butadiene are obtained in high selectivity and yield on demand, as a function of the DODH reagent/substrate ratio and of the process parameters. Short reaction times (1-15 min) at high temperature (225-275 °C) and moderate pressure are reported. 3-Butene-1,2-diol is then further converted downstream into its corresponding carbonate, i.e. 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate), an important industrial building block. The carbonation step uses a supported organocatalyst, and could be directly concatenated to the first DODH step. This unprecedented procedure also relies on a unique combination of on- and off-line analytical protocols for reaction monitoring and product quantification, and offers a biobased strategy toward important industrial building blocks otherwise petrosourced.

Full text of DOI:10.1039/c8gc02468e

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A versatile biobased continuous flow strategy for the production
of 3-butene-1,2-diol and vinyl ethylene carbonate from erythritol
Nelly Ntumba Tshibalonza,a Romaric Gérardy,a Zouheir Alsafra,b Gauthier Eppeb
and Jean-Christophe M. Monbaliua,*
<Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
A versatile, tunable and robust continuous flow procedure for the deoxydehydration (DODH) of biobased erythritol toward
3-butene-1,2-diol is described. The procedure relies on specific assets of multistep continuous flow processing. Detailed
mechanistic and computational studies on erythritol show that either 3-butene-1,2-diol or butadiene are obtained in high
selectivity and yield on demand, as a function of the DODH reagent/substrate ratio and of the process parameters. Short
reaction times (1-15 min) at high temperature (225-275 °C) and moderate pressure are reported. 3-Butene-1,2-diol is then
further converted downstream into its corresponding carbonate, i.e. 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate),
an important industrial building block. The carbonation step uses a supported organocatalyst, and could be directly
concatenated to the first DODH step. This unprecedented procedure also relies on a unique combination of on- and off-
line analytical protocols for reaction monitoring and product quantification, and offers a biobased strategy toward
important industrial building blocks otherwise petrosourced.
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Introduction
The deoxydehydration (DODH) reaction is a classical procedure
for the conversion of vicinal diols into olefins.1-5 In the actual
context of transitioning from petrobased to biobased chemical
processes, the DODH reaction on biobased polyols attracts
considerable attention.6-16 One of the most privileged
biobased polyol for DODH processes is glycerol (1), leading to
fundamental chemical building blocks such as allyl alcohol (
acrolein or acrylic acid.7,11,14,16,17
2),
Most DODH procedures require a metal catalyst, typically
rhenium-, molybdenum- and vanadium-based, often in the
presence of a sacrificial reductant such as triphenylphospine,
octanol or hydrogen (Figure 1a).8 Alternative metal-free DODH
procedures typically require a large excess of formic acid (FA
)
or triethylorthoformate (TEOF, Figure 1b).11,15,16 Our group
recently reported a robust process for the metal- and solvent-
free DODH of glycerol using the unique assets of continuous
flow processing and the reactivity of hybrid O,O,O-orthoesters
3 11
.
Quick exposure (1-6 min) to high temperature (250 °C)
(up to
Fig. 1 (a) Metal-catalyzed DODH13 and (b) metal-free DODH on vicinal diols.11
under continuous flow conditions gave high yield of
2
97%), and the DODH reaction proceeded extremely well with
only one equivalent of TEOF and a catalytic amount of FA
(Figure 1b).
Much less is reported on the DODH of other low value
biobased polyols, although it would expand significantly the
range of fundamental industrial building blocks obtained from
non-fossil resources.15,16,18 Substituted olefins, conjugated
olefins, and aromatic compounds are potentially accessible
from biobased polyols. Among biobased polyols, erythritol (
4),
a
C4-polyol widely accessible through yeast or fungal
fermentation of glucose or through the decarboxylation of
pentoses, has a promising forecast in biorefineries.18
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The DODH of
typically relied either on Re/V-catalyzed or metal-free authors next studied a MTO-process amenable to other polyols
strategies with long reaction times (up to 100 h, Figure 2a). that used hydroaromatic reductants. Erythritol ( ) gave in
Butadiene ( ) remained the privileged target so far, although 43% yield after 24 h at 150 °C in 1-butanol with indoline as
other high valued added industrial building blocks are also reductant.26 Tomishige developed
ceria-supported Re-
accessible. 2,5-Dihydrofuran (6a), 3-butene-1,2-diol (7a) and catalyst doped with Au nanoparticles. The catalyst was utilized
(E,Z)-2-butene-1,4-diol ((E,Z)-7 ) were often reported as trace on , and very high yield in were obtained after 60 h at 140
4
was scarcely reported in the literature, and (Z)-7b in 5-7% after 100 h of reaction at 150 – 160 °C.25 The
4
5
5
a
b
4
5
compounds or, in some instances, major impurities. One of the °C under ~80 bar of pressure. The main by-products were 7a
earliest reports dates back to 1996 with Andrews’ seminal and (E)-7b, accounting for 8% in total.27 De Vos reported a Mo-
work on the Re-catalyzed DODH of 4 19
authors reported up to 80% of
chlorobenzene with PPh3 as reductant. Other minor side- (200 °C in mesitylene, 2 h) and 15% (200 °C in octanol, 18 h),
products included 7a and (Z)-7b
respectively.28
A metal-free DODH procedure on biobased polyols such as
was first reported by Ellman using anaerobic conditions and
an excess of FA. The procedure was optimized on simple diols
and glycerol ( ), and next attempted on . 2,5-Dihydrofuran
6a) was obtained in 39% yield after about 24 h at 210 – 240
.
Upon optimization, the catalyzed DODH procedure on various diols; with erythritol,
5
after 28 h at 135 °C in butadiene and 2,5-dihydrofuran were obtained in up to 3%
.
4
1
4
(
°C.15 The authors then extended the procedure to quinic and
shikimic acids at 225 °C in sulfolane, thus providing biobased
benzoic acid.16 A similar procedure was described for the
DODH of xylitol toward 1,3-pentadiene.29 Another paper also
reported the conversion of
tosylation/elimination sequence (~53% overall yield).30
We describe herein the development of a versatile metal-
free DODH procedure for upgrading erythritol ( ) under
4
toward
5
using
a
4
intensified continuous flow conditions (Figure 1b). The
procedure relies on specific assets of multistep continuous
flow processing.31 This process is unique since it reports for the
first time the production of high value-added 3-butene-1,2-diol
(
7a) in good yield. The procedure is versatile and convenient,
and, unlike procedures of the prior Art, a simple adjustment of
the DODH reagent/substrate ratio, as well of the reaction
medium enables to shift the selectivity toward other valuable
chemicals, such as butadiene (5), 2,5-dihydrofuran (6a) and
but-2-enal (6b). Unprecedented short reaction times (1-15
min) at high temperature (225-275 °C) and moderate pressure
(6.9 bar) are reported. The reaction output critically depends
on the nature of the reaction medium: the formation of 3-
Fig. 2 (a) Previously reported procedures for the DODH of erythritol toward
butadiene and other important industrial building blocks; (b) This work:
metal-free DODH of erythritol toward 3-butene-1,2-diol, and other
important industrial building blocks.
butene-1,2-diol (7a) and butadiene (
5
) is favored in DMSO,
anh ), 2,5-
while in [EMIM][ES], anhydroerythritol
(
-4
dihydrofuran (6a) and but-2-enal (6b) become the major
products. Computations and mechanistic investigations on
model compounds give insight on product filiation. Eventually,
3-butene-1,2-diol (7a) is converted in high yield and selectivity
In
methyltrioxorhenium (MTO) process for the DODH of
anaerobic conditions that provided in 89% yield within 1.5 h
a
series of papers, Toste reported an efficient
4
under
5
of reaction at 170 °C in octanol. The procedure was also
amenable to xylitol, glucose and other polyols.20,21 Abu-Omar
reported a MTO-catalyzed DODH procedure in heptanol at 165
into 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene carbonate,
8)
using an organocatalyzed continuous flow process (Figure 1b).
The procedure includes a unique combination of on- and off-
line analytical procedure for reaction monitoring and product
°C. The authors reported 58% yield in 6a and but-2-enal (6b
)
was detected as a minor by-product.22,23 Gebbink used a 2,4-
quantification, and offers
a biobased strategy toward
tri(tert-butyl)cyclopentadienyl trioxorhenium catalyst for the
important industrial building blocks otherwise petrosourced.
DODH of
4, and demonstrated that the distribution of products
depends on the reaction conditions. Butadiene
(5)
was
obtained in 67% yield after 1.5 h at 170 °C in octanol. 2,5-
Dihydrofuran (6a), 7a and (Z)-7b were obtained in variable
amounts not exceeding 7%.24 Nicholas and colleagues reported
Experimental section
General information
a Re-catalyzed DODH on
4 giving 5 in 14-60%, 6a in 2-14% and
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The DODH reactor effluent was sampled at steady state and with Super Flangeless nuts and ferrules. The reactor for the
1
analyzed off-line by H NMR, by GC/MS or by GC/FID. H NMR heterogeneous carbonation reaction (Figures
1
9 and 10)
was conducted on a 400 MHz Bruker Avance spectrometer in featured a modular continuous flow assembly consisting of
d6-acetone or in d4-methanol with mesitylene as an internal plug-and-play thermoregulated stainless-steel (SS) coils (1.58
standard (Supporting Information). The chemical shifts are mm outer diameter, 500 µm internal diameter) equipped with
reported in ppm relative to TMS as internal standard or to SS connectors, ferrules and unions (Valco), and a SS packed-
solvent residual peak. Gas chromatography coupled with ion bed column (10 cm × 7 mm o.d. × 3.5 mm i.d.). Feed and
trap mass spectrometry (GC/MS) was performed on the collections lines consisted of PEEK tubing (1.58 mm outer
volatile fraction of the reactor effluent collected in air-tight diameter, 750 µm internal diameter) equipped with PEEK/ETFE
sealed vials. Headspace-Solid Phase Micro Extraction connectors and ferrules (IDEX/Upchurch Scientific). Feed
technique (HS-SPME) with Carboxen-PDMS fibers (Supelco, PA, solutions were handled with ThalesNano Micro HPLC pumps,
US) was carried out for the analysis of the volatile fraction equipped with 316 SS parts and check valves (IDEX/Upchurch
(Supporting Information). Some components of the liquid Scientific), or with high force Chemyx Fusion 6000 syringe
fraction (residual erythritol and anhydroerythritol) were pumps equipped with SS syringes and Dupont Kalrez O-rings.
analysed after derivatization. Gas Chromatography was Downstream pressure was regulated with
a dome-type
performed with a Trace-GC 2000 (Thermo-Scientific, Waltham, backpressure regulator (11 bar, Zaiput Flow Technologies). An
MA, USA). Mass spectrometric detection was performed with a on-line IR spectrometer was inserted downstream to enable
PolarisQ ion-trap (Thermo-Scientific, Waltham, MA, USA). Gas real-time reaction monitoring.
chromatography coupled with flame ionization detection
Computational study
(GC/FID) was performed to monitor the carbonation reaction
of 3-butene-1,2-diol. External calibration curves established Computations were performed at the MP2/6-31+G** level of
with pure commercial compounds were used to calculate theory with the Gaussian 09 package of programs (Revision
conversions and yields. Selectivity is defined as the ratio D.01).32 Computations were run with implicit solvent (PCM,
ε =
between the yield and the conversion. On-line reaction 46.826, DMSO). Stationary points were optimized with
monitoring was carried out by IR spectrometry, using a gradient techniques using very tight optimization convergence
FlowIRTM from Mettler-Toledo (Supporting Information). criteria. Transition states were localized using the Newton-
Glycerol, erythritol, formic acid (FA), triethyl orthoformate Raphson algorithm, and the nature of the stationary points
(
TEOF), 3-butene-1,2-diol, (E)-and (Z)-2-butene-1,4-diol, 2,5- was determined by analysis of the Hessian matrix. Activation
dihydrofuran, but-2-enal, furan, anhydroerythritol, butadiene, and reaction energies were obtained from the thermochemical
cis- and trans-cyclohexane-1,2-diol, dimethyl sulfoxide calculations (298.15 K, 1 atm). Intrinsic reaction coordinate
(DMSO),
1-ethyl-3-methylimidazolium
ethyl
([EMIM][Ac]),
EMIM
sulfate (IRC) calculations were performed on each transition state.
([EMIM][ES]),
trifluoroacetate
EMIM
acetate
EMIM
Typical runs
([EMIM][TFA]),
dicyanamide
([EMIM][DCA]), 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU),
polymer-supported DBU (PS-DBU), dimethyl carbonate (DMC)
and vinyl ethylene carbonate were obtained from commercial
sources, and used as received.
DODH on erythritol (4) toward butadiene (5). A feed solution (500
mL total volume) of erythritol (4) was prepared by mixing 4 (2.4 M
in DMSO), 2 equiv. of triethyl orthoformate, 0.1 equiv. of formic
acid in DMSO, and connected to a HPLC pump set at 0.2 mL min-1.
The reaction mixture was reacted for 6 min at 225 °C under 6.9 bar
of counter-pressure (Figure 3). The outlet of the reaction coil was
connected to a cooling SS capillary loop (2 min residence time). The
reactor effluent was collected and analyzed (42% yield in butadiene,
see Figures 4-6).
Experimental setup
The reactor for the DODH reaction (Figures 3 and 10) featured
a modular continuous flow assembly consisting of plug-and-
play thermoregulated stainless-steel (SS) coils (1.58 mm outer
diameter, 500 µm internal diameter) equipped with SS
connectors, ferrules and unions (Valco). Feed solutions were DODH on erythritol (4) toward 3-butene-1,2-diol (7a). A feed
handled with ThalesNano Micro HPLC pumps, equipped with solution (500 mL total volume) of erythritol (4) was prepared by
316 SS parts and check valves (IDEX/Upchurch Scientific), or mixing 4 (2.4 M in DMSO), 1 equiv. of triethyl orthoformate, 0.1
with high force Chemyx Fusion 6000 syringe pumps equipped equiv. of formic acid in DMSO, and connected to a HPLC pump set
with SS syringes and Dupont Kalrez O-rings. Downstream at 1.25 mL min-1. The reaction mixture was reacted for 1 min at 250
pressure was regulated with a spring-loaded backpressure °C under 6.9 bar of counter-pressure (Figure 3). The outlet of the
regulator (6.9 bar, IDEX/Upchurch Scientific) embedded in a SS reaction coil was connected to a cooling SS capillary loop (2 min
holder. Feed and collections lines consisted of PEEK tubing residence time). The reactor effluent was collected and analyzed
(1.58 mm outer diameter, 750 µm internal diameter) equipped (56% yield in 3-butene-1,2-diol, see Figures 4-6).
with PEEK/ETFE connectors and ferrules (IDEX/Upchurch
DODH on erythritol (4) toward 2,5-dihydrofuran (6a). A feed
Scientific).
solution (500 mL total volume) of erythritol (4) was prepared by
The reactor for the homogeneous carbonation reaction
mixing 4 (3.1 M in [EMIM][ES]), 1 equiv. of triethyl orthoformate,
(Figure 8) was constructed from high purity PFA capillary coil
0.1 equiv. of formic acid in [EMIM][ES], and loaded in a syringe
(1/16” outer diameter, 750 µm internal diameter) equipped
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pump set at 80 µL min-1. The reaction mixture was reacted for 15 delivered with an HPLC pump set at 0.1 mL min-1 (1 equiv. of 7a).
min at 275 °C under 6.9 bar of counter-pressure (Figure 3). The Neat DMC was delivered with an HPLC pump set at 0.4 mL min-1
outlet of the reaction coil was connected to a cooling SS capillary (5.5 equiv.) and both streams were mixed in a PEEK T-mixer using
loop (2 min residence time). The reactor effluent was collected and Super Flangeless nuts and ferrules. The mixture was preheated in a
analyzed (23% yield in 2,5-dihydrofuran, see Figures 4-6).
SS coil (1.58 mm o.d., 500 μm i.d., 0.65 mL internal volume), and
then reacted in a SS column (10 cm × 7 mm o.d. × 3.5 mm i.d.), both
heated at 160 °C. The SS column was loaded with 200 mg of PS-DBU
(1.5-2.5 mmol g-1 loading) dispersed with 1 g of glass beads (425-
600 μm). The reactor effluents were conveyed through an on-line IR
spectrometer for reaction monitoring. A dome-type back-pressure
regulator was connected downstream and set at 11 bar. The reactor
effluents were sampled, diluted with EtOH and analyzed by GC/FID
to complement IR data.
DODH on erythritol (4) toward but-2-enal (6b). A feed solution
(500 mL total volume) of erythritol (4) was prepared by mixing 4
(3.1 M in [EMIM][ES]), 2 equiv. of triethyl orthoformate, 0.1 equiv.
of formic acid in [EMIM][ES], and loaded in a syringe pump set at 80
µL min-1. The reaction mixture was reacted for 15 min at 275 °C
under 6.9 bar of counter-pressure (Figure 3). The outlet of the
reaction coil was connected to a cooling SS capillary loop (2 min
residence time). The reactor effluent was collected and analyzed
(35% yield in but-2-enal, see Figures 4-6).
Results
Preparation of 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene
carbonate, 8) from 3-butene-1,2-diol (7a) under homogeneous
conditions. The syringe pump used to deliver neat 3-butene-1,2-
diol (7a) was set to 31.2 μL min-1 (1 equiv.) and the syringe pump
used to deliver the 0.0791 M solution of DBU in DMC was set to
93.8 μL min-1 (2 mol% DBU, 3 equiv. DMC). Both streams were
mixed in a PEEK T-mixer using Super Flangeless nuts and ferrules.
The homogeneous mixture entered a PFA capillary coil (1/16” o.d.,
1/32” i.d., 0.5 mL internal volume) heated at 160 °C. The outlet of
the capillary coil reactor was connected to a dome-type back-
pressure regulator set at 11 bar (Figure 8). After equilibration, the
reactor effluent was collected, quenched with saturated aqueous
NH4Cl, diluted with EtOH, and analyzed by GC/FID (69% yield in vinyl
ethylene carbonate, see Table 2).
Unlike glycerol (
are solids. The strategy envisioned for the continuous flow
DODH of reported previously was therefore not directly
1), erythritol (4) and other biobased polyols
1
transposable to other biobased substrates.11 The first
challenge was to identify a suitable solvent that would enable
straightforward implementation under flow conditions while
keeping the environmental footprint acceptable. The solvent
of choice had to meet important selection criteria: (a) it must
ensure high solubility of the substrates (> 1 M) for high
throughput, (b) it must to be thermally (for short exposure
times at > 200 °C) and chemically stable and (c) it must ideally
be considered as a green solvent, or it must at least have a low
toxicity profile. Additionally, its viscosity (typ.
η
= << 1 N s m-2
at 22 °C) must not preclude simple and straightforward
pumping for long operation times. With these important
criteria in mind, we screened a large variety of solvents
including lower alcohols, DMSO, sulfolane, propylene
carbonate, acetic acid and ionic liquids based on the ethyl
methylimidazolium cation (EMIM) ([EMIM][Ac], [EMIM][TFA],
[EMIM][DCA] and [EMIM][ES]). Although most of these
solvents met the low viscosity requirement and at least two of
the selection criteria above-mentioned, only DMSO,
[EMIM][DCA] and [EMIM][ES] gave full satisfaction. For
Preparation of 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene
carbonate, 8) from 3-butene-1,2-diol (7a) with polymer-supported
DBU. The HPLC pump used to deliver the solution of 3-butene-1,2-
diol (7a) in DMSO was set at 0.1 mL min-1 (1 equiv.) and the HPLC
pump used to deliver neat DMC was set at 0.04 mL min-1 (3 equiv.).
Both streams were mixed in a PEEK T-mixer using Super Flangeless
nuts and ferrules. The mixture was preheated in a SS coil (1.58 mm
o.d., 500 μm i.d., 0.65 mL internal volume), and then reacted in a SS
column (10 cm × 7 mm o.d. × 3.5 mm i.d.), both heated at 160 °C.
The SS column was loaded with 200 mg of PS-DBU (1.5-2.5 mmol g-1
loading) dispersed with 1 g of glass beads (425-600 μm). A dome-
type back-pressure regulator was connected downstream the
reactor and set at 11 bar (Figure 9). After equilibration, the reactor
effluent was collected, diluted with EtOH and analyzed by GC/FID
(87% yield in vinyl ethylene carbonate, see Figure 9).
instance, erythritol
4 was soluble up to 7 M in DMSO in the
presence of TEOF (2 equiv.) and FA (10 mol%), without
affecting processability under continuous flow conditions.
The next step was to assess the DODH on a model
compound in the above-selected solvents. We selected
1,
since its DODH reaction toward allyl alcohol (2) was a well-
understood process, and performed the reaction under
Preparation of 4-vinyl-1,3-dioxolan-2-one (vinyl ethylene
carbonate, 8) from erythritol (4). A feed solution (500 mL total
volume) of erythritol (4) was prepared by mixing 4 (2.4 M in DMSO),
1 equiv. of triethyl orthoformate, 0.1 equiv. of formic acid in DMSO,
and connected to a HPLC pump set at 1.25 mL min-1. The reaction
mixture was reacted for 1 min at 250 °C under 6.9 bar of counter-
pressure (Figure 10). The outlet of the reaction coil was connected
to a cooling SS capillary loop (2 min residence time). The effluent of
the DODH reactor was collected in a surge under sonication, and
utilized without additional treatment for the preparation of vinyl
ethylene carbonate (8). The crude effluent of the DODH reactor was
continuous flow conditions with 1 equiv. of TEOF and 10 mol%
of FA as catalyst. The concentration of
1 in the feed was set at
2.4 M and 3.1 M in DMSO and [EMIM][ES], respectively, and
the reaction proceeded as expected (74 and 72% yield, 97 and
>93% selectivity, respectively). The reaction failed in
[EMIM][DCA] (no conversion). With a refined selection of
solvents, the optimization of the DODH on
4 commenced with
a
thorough screening of process parameters including
temperature, pressure, residence time, reagent ratio and
solvent nature (Figure 3). The overall progress of the reaction
was monitored off-line, and the results indicated that the no
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axis shows relative amount or TEOF (1 or 2 equiv.) and temperature (175 -
275 °C).
reaction occurred below 175 °C, and that significant DODH
occurred between 225 and 275 °C. The reactor effluent was
collected at steady state, and processed for analysis. The
volatile fraction (b.p. < 70 °C, including butadiene, 2,5-
dihydrofuran and furan) was collected in air-tight sealed vials
downstream through automated valves, and was analyzed by
by HS-SPME/GC-MS. The liquid fraction (b.p. > 70 °C, including
3-butene-1,2-diol, 2-butene-1,4-diol, anhydroerythritol and
but-2-enal) was collected after cooling and analyzed by high-
field 1H NMR or GC/MS after derivatization (Supporting
Information).
With a stoichiometric amount of TEOF, the amount of 3-
butene-1,2-diol (7a) increased progressively and plateaued at
275 °C with 56% yield (Figure 4). 2-Butene-1,4-diol (7b
)
remained below 6%, with a maximum at 275 °C with 1 equiv.
of TEOF. Anhydroerythritol (anh-4) reached a maximum of 2%
at 275 °C with 2 equiv. of TEOF. At higher temperature,
significant charring occurred, and solid material accumulated
in the reactor, giving inconsistent results and hence clogging
the reactor. The conversion, determined by GC/MS from the
residual amount of
4 after derivatization of the crude reactor
effluent increased up to 90% at 275 °C with 1 equiv. TEOF
,
while the conversion was complete with 2 equiv. TEOF
(Supporting Information).
Further optimization was considered with the residence
time and the amount of TEOF (Figure 5). Two additional
residence times were considered, namely, 1 and 15 min at 225,
250 and 275 °C with 1 or 2 equiv. TEOF. For the 225 - 275 °C
range of temperature, it is clear that the amount of diene
5
correlated with the excess of TEOF. A maximum of 42% yield in
butadiene was obtained at 250 °C with 2 equiv. of TEOF and
the longest residence time (15 min). Butadiene (5) appears as
a competitive side-product for the production of 3-butene-1,2-
diol (7a), and the best condition for reducing its formation
involved quick exposure (1 min) of
or 275 °C) in the presence of 1 equiv. of TEOF. Under such
conditions, the yield of remained under 10%, and the yield of
4 at high temperature (250
Fig. 3 Simplified setup for the DODH of erythritol (4) under continuous flow
conditions (major products are shown).
5
7a reached up to 56%. Isomeric 2-butene-1,4-diol (7b) was
formed in 1-6%, with the largest amounts being formed with 1
The first results were collected at 6 min of residence time
equiv. of TEOF
.
with
temperatures (Figure 4) in DMSO. The production of butadiene
) increased with the excess of TEOF, and reached a maximum
at 225 °C with about 42%, and then decreased. Under these
conditions, the volatile fraction contained almost exclusively
1 or 2 equiv. of TEOF with increasing process
(
5
5;
2,5-dihydrofuran (6a) and furan (6c) were barely detected
(Supporting Information).
Fig. 5 Composition of the reactor effluent (volatile and liquid fractions, yield
in %) for residence times ranging from 1 to 15 min, using 1 or 2 equiv. of
TEOF at temperatures ranging from 225 to 275 °C in DMSO. The dotted line
summarizes the evolution of the yield for 3-butene-1,2-diol (7a). Yields are
given for butadiene (5, white) and for 3-butene-1,2-diol (7a, black). The X
axis shows the process conditions: residence time (1, 6, 15 min), relative
amount or TEOF (1 or 2 equiv.) and temperature (225, 250 and 275 °C) in
DMSO.
The formation of but-2-enal (6b) became significant at 250
°C. The residence time had also an impact on its formation,
reaching a maximum of 11% at 275 °C with 2 equiv. of TEOF
within 15 min of residence time (1.8% within 1 min of
Fig. 4 Composition of the reactor effluent (volatile and liquid fractions, yield
in %) for 6 min of residence time using 1 or 2 equiv. of TEOF at temperatures
ranging from 175 to 275 °C in DMSO. The dotted line summarizes the
evolution of the yield for 3-butene-1,2-diol (7a) with 1 equiv. of TEOF. The X
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When the DODH reaction was attempted on
4 in
[EMIM][ES] (3.1 M) within the 175 – 275 °C range, the product
profile changed drastically. 3-Butene-1,2-diol (7a) or 2-butene-
1,4-diol (7b) were not anymore detected, irrespective of the
Table 1. DODH under continuous flow conditions on model substrates (1
equiv. TEOF, 10 mol% FA, 250 °C, 100 psi)
temperature and residence time. The production of diene
5
was suppressed for all experiments with 1 equiv. of TEOF
,
although its production increased linearly from 225 °C with 2
equiv. of TEOF to reach 25% yield at 275 °C with a residence
time of 15 min. In [EMIM][ES], it turned out that the main
products of the process included anhydroerythritol (anh-4, up
to 27%), 2,5-dihydrofuran (6a, up to 23%) and but-2-enal (6b
,
up to 35%). The amount of 6a increased linearly with 1 or 2
equiv. TEOF from 225 to 275 °C with 15 min of residence time,
although the yield was much higher with 1 equiv. TEOF (23%)
(Supporting Information). Larger amounts of 6b were observed
from 200 °C with 2 equiv. of TEOF and the longest residence
time (15 min).
To further understand product filiations, several control
experiments were carried out both in DMSO and [EMIM][ES]
with model substrates including commercial cis- and trans-
cyclohexanediol, anhydroerytritol (anh-4), 3-butene-1,2-diol
(
7a), as well as E- and Z-2-butene-1,4-diol (E,Z-7b) under DODH
conditions (Table 1). A preliminary requirement for vicinal diols
to undergo DODH is a relative cis configuration. It is thus
expected, as confirmed by computations at the MP2 level of
theory (see below) that anhydroerythritol (anh-4) forms 2,5-
dihydrofuran (6a) under such conditions, while anhydrothreitol
a in DMSO, 1 min; b in [EMIM][ES], 6 min; c the corresponding formates
were detected in 5-8%
does not. Cyclohexanediol (cis- and trans-
model compound. Under DODH conditions (1 min, 250 °C),
cyclohexene (10) was not formed starting from trans- , while
under the same conditions,
9) was utilized as a
residence time). Anydroerythritol (anh-4) was detected in 1-
2%, irrespective of the process conditions. A larger excess of
TEOF (3 equiv.) did not improve the selectivity or the yield.
Concentrations up to 7 M in DMSO were achievable, but it
significantly affected the reaction, and the yield dropped to
9
61% of 10 was observed from cis-
9
in agreement with previously reported data.2,3,15
Compound anh-4 gave 6a in 57-62% in DMSO and
[EMIM][ES], respectively, and furan (6c) was observed (1%) in
both cases within 6 min at 250 °C. Compound anh-4 is
13% and 16% for 7a and
5, respectively (15% and 42%,
respectively, with 2.4 M in DMSO).
Analysis of the volatile fraction (Fig. 6) indicates that 2,5-
dihydrofuran (6a) and furan (6c) are not produced below 225
°C in significant amounts (> 1%). Generally, the relative
amount of 6a and 6c increases with the residence time and
obtained from
4 by an acid-catalyzed cyclodehydration, which
appears to be favored in [EMIM][ES]. Further aromatization
proceeds at high temperature, leading to 6c. The direct
cyclodehydration of (Z)-2-butene-1,4-diol ((Z)-7b) toward 6a
was reported in the presence of Re-based catalysts,26 although
it is less likely to occur under our conditions. Control
experiments on 7a, (Z)-7b and (E)-7b further completed the
picture. Under DODH conditions (250 °C, 1 min, 1 equiv. of
with the temperature. At 225 and 250 °C with 2 equiv. of TEOF
the volatile fraction mostly contains , while at 275 °C, the
relative amount of 6a and 6c increases (3% combined yield).
,
5
TEOF), 7a gave up to 18% of diene
5, and less than 5% of its
formate esters. (Z)-7b only gave very low amounts of diene
5
(1%), 6a (2%) and the corresponding mono- and diformates
(7%). Under the same conditions, diol (E)-7b gave 34% of but-
2-enal (6b, 50:50 E/Z), and 3% of furan (6c), while
detected. These results clearly emphasize that the formation
of under these conditions proceeds mostly through a 1,2-
DODH process from 7a, and thus excludes the involvement of
1,4-DODH process from (E,Z)-7b 18
5 was not
5
.
Based upon our preliminary reports on the mechanism of
DODH on glycerol and derivatives, computations at the MP2/6-
31+G** level were carried out to gain further insight on the
selectivity and mechanism of the reaction. We assumed that
Fig. 6 Fractional composition of the volatile effluent (relative amounts in %).
The X axis shows the process conditions: residence time (1, 6, 15 min),
relative amount of TEOF (1 or 2 equiv.) and temperature (225, 250 and 275
°C) in DMSO.
hybrid orthoesters of type 3a from erythritol (4) behave
6 | J. Name., 2012, 00, 1-3
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similarly than those derived from 1, and form transient kcal mol-1) that reflects the emergence of a stereoelectronic
dioxolidin-2-ylidene carbenoid species under the reported effect further stabilizing the corresponding TS structure.
conditions. Such carbenoid species next undergo a concerted
fragmentation with concomitant CO2 extrusion and formation DODH of
of an alkene (Figure 7, Supporting Information). The formation DMSO, the output of the DODH on
A clear filiation of the major products observed upon
arose from these considerations (Scheme 1). In
depends essentially, at
4
4
of hybrid orthoesters 3a from polyols and alkylorthoformates the optimum temperature of 250 °C, on the excess of TEOF
in the presence of an acid catalyst is a dynamic and complex and of the reaction medium: with 1 equiv. TEOF, apical diol 7a
process33 that is simplified here for rationalizing the DODH is the main product, while with 2 equiv. TEOF, the formation of
reaction. The experimental selectivity of the reaction can be diene
correlated with the calculated activation parameters for the 250 °C in DMSO is most likely related to a catalytic dehydration
corresponding transition states. As a reference, we started first of internal diol (E)-7b 34
Diol (E)-7b is formed as a minor
with the DODH of in DMSO, yielding allyl alcohol ( ) and CO2, product at high temperature experiments in DMSO, most likely
G≠) of 10.7 kcal through an isomerization of (Z)-7b. Although it is difficult to
G≠ of 11.1 kcal mol- exclude the contribution of hybrid bisorthoester 3b to the
, it is clear that the emergence of favorable
G≠ for anh-4 was of stereoelectronic effects in TSD would contribute significantly to
11.6 kcal mol-1, and no transition state structures were isolable the formation of diene
from apical diol 7a. In [EMIM][ES], the
acid-catalyzed cyclodehydration of toward anh-4 becomes
competitive.18 Compound anh-4 next reacts with TEOF at high
temperature to yield 6a upon DODH, rather than 7a,b or . It is
5 becomes significant. The formation of aldehyde 6b at
.
1
2
which gave a Gibbs free activation energy (
ꢀ
mol-1. The DODH on cis-
9
proceeded with
ꢀ
1
, while on trans-9, CO2 extrusion costed an additional 30.5 kcal formation of 5
mol-1 to form alkene 10. The calculated
ꢀ
5
for its trans isomer.
4
5
worth mentioning that isomeric 2,3-dihydrofuran was never
observed during these experiments. The formation of
aldehyde 6b was reported upon metal-catalyzed DODH on
erythritol, although its formation remained below 10%.22 Here,
the formation of much larger amounts of 6b in [EMIM][ES] is
most likely related to the thermal isomerisation of 6a, rather
than the catalytic dehydration of diol (E)-7b since the latter
was not detected under these conditions.34
Fig. 7 Structures of representative transition states TSA-D involved in the
formation of 2,5-dihydrofuran (TSA, from anhydroerythritol), 3-butene-1,2-
diol (TSB, from erythritol), cis-2-butene-1,4-diol (TSC, from erythritol) and
butadiene (TSD, from 3-butene-1,2-diol) through thermal extrusion of EtOH
and CO2 from the corresponding hybrid ethyl orthoesters 3.
These results therefore confirm the requirement for vicinal
diols to be locked in a relative cis configuration. Starting now
from 4, from which two isomeric hybrid orthoesters 3a,a’, and
hence two isomeric dioxolidin-2-ylidene carbenoids, are likely
to form (Supporting Information), thus yielding either 7a or
(Z)-7b. The formation of diol 7a is associated with a free
energy of activation of 10.2 kcal mol-1, while the formation of
(Z)-7b through an isomeric TS is less favorable with a ꢀꢀG≠ =
3.1 kcal mol-1. These results emphasize that the selectivity
might be rationalized by the ꢀꢀG≠ between the two isomeric
pathways leading to 7a or (Z)-7b through CO2 extrusion, thus
explaining the slower formation of the internal olefin (Z)-7b 26
An additional DODH on apical olefin 7a leading to the products. Only major products were considered.
formation of diene comes with a significantly lower
G≠ (7.8
.
Scheme
1 Rationalization of the filiation between the various DODH
5
ꢀ
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Next, we envisioned the direct preparation of 4-vinyl-1,3- observed downstream the BPR (entries 5, 7-9), most likely as a
dioxolan-2-one (
butene-1,2-diol
8
, vinyl ethylene carbonate) from crude 3- consequence of the decarboxylation of
7a under continuous flow conditions. monoxide.
8 toward 1,3-butadiene
(
)
Carbonate
8 is an important commodity chemical that has
numerous applications, notably for the synthesis of
polymers35-37 and as additive in Li-ion batteries.38,39 It is
typically manufactured by the addition of CO2 to 1,3-butadiene
monoxide. The methodology was first patented in 1950,40 but
still stimulates considerable research efforts.41-44 However, this
route raises safety and environmental concerns as 1,3-
butadiene monoxide is toxic, unstable and exclusively
petrobased. An emerging alternative route consists in the
transesterification involving dialkyl carbonates with apical diol
7a. Literature data regarding such transesterification is scarce,
and only one patent reported a catalytic process using 1.5-3.1
wt% of NaOMe and 2 equiv. of dimethyl carbonate (DMC).45
Procedures for the carbonation of glycerol in the presence of
organocatalysts are increasingly reported.46,47 Based upon our
Table 2. Process optimization for the homogeneous continuous flow carbonation
of purified 3-butene-1,2-diol.
Residence
a
T
DMC
DBU
Conv. b
(%)
Selec.
b (%)
Entry
time
(°C)
(equiv.) (mol%)
(min)
1c
2c
3c
4c
5c
6c
7c
8c
9c
3
3
3
3
4
6
4
4
4
4
4
4
100
120
140
160
160
160
160
160
160
160
160
160
2
2
2
23
31
44
70
77
83
52
80
80
86
87
95
2
2
2
84
83
81
80
81
76
78
80
73
80
79
80
2
2
2
2
1
3
4
2
2
2
2
2
2
3
expertise,
we
developed
an
organocatalyzed
transesterification under continuous flow conditions.48
Scouting of reaction conditions started with commercial 7a
and DMC in the presence of DBU as an organocatalyst under
neat conditions. Both homogeneous and polymer-supported
10c
11c
12d
2
3.5
2
3
a
The loading of organocatalyst is relative to the number of moles of 3-
DBU were assessed for the organocatalytic carbonation of 7a
.
b
c
butene-1,2-diol. Conversion and yield were determined by GC-FID. 3-
d
In a representative homogeneous experiment, neat DMC
(containing DBU) and 7a were mixed through a static mixer,
and further reacted in a heated capillary coil reactor under 11
bar of counter-pressure, to enable superheated conditions in
DMC (Figure 8). DMC and 7a formed directly a homogeneous
solution. Process parameters such as temperature, residence
time, catalyst loading and DMC/7a molar ratio were
thoroughly assessed (Table 2 and Supporting Information for
full details of the optimization).
Butene-1,2-diol was pumped as a neat solution. 3-Butene-1,2-diol was
pumped as a 1.5 M solution in DMSO.
Tuning of the DMC/7a molar ratio in the 2-3.5 range
indicated that 3 equiv. of DMC gave the best results, with 86%
conversion and a 80% selectivity toward
8 (entries 5, 10-11).
The impact of DMSO on the reaction was then evaluated,
before attempting full concatenation from erythritol. To mimic
the effluent of the DODH reactor that provided 7a in 56% yield
(Figure 4), a solution of purified 7a in DMSO was reacted with
neat DMC (containing DBU). The optimized process
parameters established here above (160 °C, 4 min, 2 mol%
DBU and 3 equiv. of DMC) were utilized. The results indicated
that DMSO had a positive impact on the conversion (95%),
while the selectivity remained unchanged (Table 2, entries 11-
12). To maximize cost-efficiency and ease downstream
purification, polymer-supported DBU was assessed as
heterogeneous catalyst. The previous continuous flow setup
Fig. 8 Simplified continuous-flow setup for the homogeneous carbonation of
commercial 3-butene-1,2 diol.
was adapted for hosting
a packed-bed column and a
Increasing the temperature from 100 to 160 °C with 2
mol% of DBU and 2 equiv. of DMC drastically improved the
preheating loop at 160 °C for the substrates (Figure 9a). Similar
process conditions were utilized (7a in DMSO, 3 equiv. of neat
DMC, 160 °C, 11 bar). The packed-bed column was filled with a
mixture of glass beads (425-600 µm) and polystyrene-
supported DBU (PS-DBU). Increasing the Weight Hourly Space
Velocity (WHSV, Figure 9b) from 3.96 to 13.88 h-1 affected the
conversion, which decreased from 92 to 67%, while the
selectivity remained steady (90-95%).
conversion from 23 to 70%. The selectivity toward
8 was
barely affected and decreased from 84 to 80% (entries 1-4).
When the residence time was changed from 3 to 4 min, the
conversion was slightly improved up to 77% and the selectivity
was not affected (81%). A further increase in residence time
did not improve the overall yield (entries 4-6). Decreasing the
catalytic loading down to 1 mol% affected the conversion,
which dropped to 52%. The conversion plateaued at 80% while
increasing the amount of organocatalyst to 3 or 4 mol%. At
elevated DBU loading (4 mol%), the selectivity however
dropped to 73%, and an extensive amount of gas was
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11a illustrates the evolution of the transcarbonation reaction
of 7a as a function of the temperature (25-160 °C). On-line
a.
conversion of
4 to 8 was obtained by combining on-line IR
qualitative information and off-line quantitative GC/FID (Figure
11b). The concatenated continuous flow setup was operated
for 24 h to assess catalyst stability over time upon processing
crude 7a. The concentration in vinyl ethylene carbonate
remained quite stable over the first 10 h of operation, but
decreased drastically as TOS increased. Samples were collected
for off-line quantitative GC analysis, which indicated that the
conversion of 3-butene-1,2-diol was in the 65-73% range over
the first 10 h, but then dropped to 28% after 24 h (Supporting
Information). However, the selectivity was unaffected by the
operation time (90-99%). Catalyst deactivation was
rationalized by the presence of impurities from the DODH,
such as traces of formic acid and/or dissolved CO2, which
would poison the basic sites of the heterogeneous catalyst.
b.
a.
Fig.
9 (a) Simplified continuous flow setup for the heterogeneous
carbonation of commercial 7a; (b) Evolution of the conversion and
selectivity (off-line GC/FID) as a function of the WHSV for the heterogeneous
carbonation of commercial 7a. The WHSV is defined as the mass of 7a fed
per hour and per mass of PS-DBU.
Full concatenation of the DODH and carbonation steps was
then performed from
4 (Figure 10). The crude effluent from
the DODH reactor was collected, degassed, and further
reacted with DMC over PS-DBU without any additional
treatment or purification step. By comparison to the
experiments with commercial 7a, the conversion was slightly
affected, most likely a consequence of the presence of
impurities competing with the active sites of the
heterogeneous catalyst. For instance, at a WHSV of 2.14 h-1
and with 5.5 equiv. of DMC, the conversion of crude 7a was
73%, while it was 79% at a WHSV of 11.89 h-1 and with 3 equiv.
of DMC for commercial 7a (Figure 9). However, the selectivity
b.
(97%) toward carbonate 8 remained unaffected.
Fig. 11a. On-line IR reaction monitoring showing characteristic vibration
bands of interest (νC=O at 1810 cm-1 and νC=O at 1750 cm–1) for the
carbonation of neat 7a with DMC with homogeneous DBU at various
temperatures (11 bar; reaction parameters are described in Table 2, entries
1-4). The upper insert illustrates the relative increase in carbonate 8 from 25
to 160 °C. b. On-line reaction monitoring showing the decrease of the
conversion toward carbonate
8 by combining on-line IR qualitative
Fig. 10 Simplified concatenated flow process combining the DODH on
erythritol under the best conditions to maximize the production of 3-
butene-1,2-diol and its subsequent heterogeneous organocatalyzed
carbonation toward vinyl ethylene carbonate. The WHSV of 3-butene-1,2-
diol over PS-DBU is 2.14 h-1.
monitoring (blue series, relative intensity of the 1810 cm-1 band) and off-line
quantitative GC/FID (orange dots, GC conversion of 7a). The reaction was
monitored over 24 h of continuous operation. Reaction parameters are
described in Figure 10.
The unique profile of the reagents and products enabled
on-line reaction monitoring using IR spectroscopy. The
carbonation of diol 7a with DMC (νC=O at 1750 cm–1) toward
Conclusion
This work illustrates a versatile and robust continuous flow
procedure for the deoxydehydration (DODH) of biobased
carbonate
8 (
νC=O at 1810 cm–1) was monitored through the
evolution of the main characteristic vibration bands. Figure
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18 E. V. Makshina, M. Dusselier, W. Janssens, J. Degrève, P. A.
Jacobs and B. F. Sels, Chem. Soc. Rev., 2014, 43, 7917–7953.
erythritol toward 3-butene-1,2-diol, and its further
carbonation toward vinyl ethylene carbonate. The procedure
relies on advanced continuous flow techniques and the
combination of on- and off-line analytics. Computational and
mechanistic investigations provide insights on the various
products formed and their filiation, enabling a fine tuning of
the reaction parameters to push the conversion of erythritol
toward 3-butene-1,2-diol up to 56% yield. This procedure is
unique since (a) 3-butene-1,2-diol is obtained in amounts of
19 G. K. Cook and M. A. Andrews, J. Am. Chem. Soc., 1996, 118
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,
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preparative interest from
a biobased resource and (b)
unprecedented short reactions times are reported (1 min).
Process conditions can be easily tuned to form other valuable
industrial building blocks such as butadiene, 2,5-dihydrofuran
and but-2-enal. In addition, this work provides a simple,
selective and effective carbonation procedure from 3-butene-
1,2-diol toward vinyl ethylene carbonate. The procedure
accommodates either homogeneous or heterogeneous
organocatalysts, and is amenable to crude 3-butene-1,2-diol.
Both steps are directly concatenable after degassing of crude
3-butene-1,2-diol.
ChemistrySelect, 2016, 1, 4630–4632.
Acknowledgments
31 R. Gérardy, N. Emmanuel, T. Toupy, V. E. Kassin, N. N.
Tshibalonza, M. Schmitz and J. C. M. Monbaliu, Eur. J. Org.
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This work was supported by the University of Liège (Welcome
Grant WG-13/03, JCMM).
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Table of Content
A versatile, tunable and robust continuous flow procedure for the upgrading of erythritol
toward important industrial building blocks