Catalytic decarbonylation of biomass-derived carboxylic acids as efficient route to commodity monomers

Article abstract of DOI:10.1039/C2GC16115J

The palladium-catalyzed decarbonylation of bio-derived carboxylic acids to alkyl acrylates, styrene, and acrylonitrile is reported. The olefins were isolated by continuous distillation in yields up to 87% by heating a neat, equimolar mixture of pivalic anhydride with the appropriate carboxylic acid to 190 °C in the presence of a Pd-phosphine catalyst.

Full text of DOI:10.1039/C2GC16115J

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Green Chemistry
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PAPER
Catalytic decarbonylation of biomass-derived carboxylic acids as efficient
route to commodity monomers†
Maria O. Miranda,‡ Agostino Pietrangelo,‡ Marc A. Hillmyer* and William B. Tolman*
Received 6th September 2011, Accepted 18th November 2011
DOI: 10.1039/C2GC16115J
The palladium-catalyzed decarbonylation of bio-derived carboxylic acids to alkyl acrylates,
styrene, and acrylonitrile is reported. The olefins were isolated by continuous distillation in yields
up to 87% by heating a neat, equimolar mixture of pivalic anhydride with the appropriate
carboxylic acid to 190 ◦C in the presence of a Pd-phosphine catalyst.
Introduction
(1)
Escalating demands for resources derived from diminishing
fossil fuel reserves have made the quest for sustainable al-
ternatives of paramount importance. With an annual global
production of billions of metric tons per year,1 biomass (in
the form of carbohydrates, oils, lignins, and terpenes) has
emerged as a sustainable platform from which the generation of
commodity chemicals, fuel, and energy can be realized.2 As an
example, the production of olefins via transition-metal-catalyzed
decarbonylation is of considerable interest given the availability,
low toxicity, and structural diversity of bio-derived carboxylic
acids. Miller and coworkers were among the first to prepare
terminal alkenes from long chain fatty acids by heating the latter
to 250 ◦C (eqn (1)) neat with one equivalent of acetic anhydride,
(Ac2O), triphenylphosphine (PPh3, 0.5 mol%), and 0.01 mol%
of a Pd- or Rh-based catalyst.3 During this transformation, a
mixed anhydride (generated in situ) is postulated to undergo
oxidative addition onto a transition-metal species to yield an
acyl complex (Scheme 1).4 Subsequent decarbonylation followed
by b-hydride elimination affords the corresponding olefin along
with an equivalent of carbon monoxide and two equivalents
of acetic acid (in principle both the CO and acetic acid can
be recycled to make syngas and acetic anhydride, respectively).
Subsequent work by Gooben and Rodr´ıguez5 and Scott et al.6
showed that lower temperatures (ca. 110 ◦C) can be employed at
the expense of using a solvent and higher palladium (ca. 3 mol%)
and ligand (ca. 9 mol%) loadings; Maetani and coworkers have
recently reported similar results using Ir-based catalysts in lieu
of Pd.7
Scheme 1 Proposed decarbonylation mechanism.
Herein, we report a simple and facile method that con-
verts bio-sourced mono-alkyl succinates into alkyl acrylates,
monomers used extensively in the paint, coatings, adhesive, and
textile industries.8 Moreover, we have extended the scope of this
method to include the production of styrene and acrylonitrile
from bio-derived hydrocinnamic acid9 and 3-cyanopropanoic
acid,10 respectively. As is the case with alkyl acrylates, both
Department of Chemistry and Center for Sustainable Polymers,
University of Minnesota, 207 Pleasant St. SE, Minnneapolis, MN,
55455-0431, USA. E-mail: hillmyer@umn.edu, wtolman@umn.edu;
Fax: 612-626-8659; Tel: 612-625-4061
† Electronic supplementary information (ESI) available: Represen-
tative GC-MS traces for decarbonylation reactions. See DOI:
10.1039/c2gc16115j
‡ These authors contributed equally to this study.
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styrene and acrylonitrile are high volume11 petrochemically
derived commodity chemicals, which are used in the produc-
tion of many consumer items (i.e. toys, housings, computer
components, furniture, disposable tableware),12 fibers in the
textile industry and molded components in the automobile
and appliance industries.13 The bio-based synthesis of these
monomers has been achieved in recent years using routes
besides the decarbonylation of bio-based carboxylic acids. Most
recently, engineered E. coli produced styrene biosynthetically
from L-phenylalanine.14 The alkyl acrylates can be synthesized
from glucose-derived a- or b-hydroxy acids via acrylic acid,15
and acrylonitrile can be synthesized renewably from glycerol.16
In addition to the novel substrates studied and practical
application of the products, we also use lower catalyst and ligand
loadings and shorter reaction times than reported by Gooben,
Scott and co-workers,5,6 as well as a solvent-free reaction and
simple distillation procedure that avoids aqueous workup. In
contrast to the method of Miller,3 we have chosen a high-boiling
exogenous anhydride that avoids continuous addition to the
reaction. Finally, we demonstrate the robustness of the reaction
to air, water, and increased scale.
49.2 mol) and n-butanol (44 mL, 48.1 mol) were added and
a reflux condenser was attached. The mixture was heated to
120 ◦C and allowed to reflux for 3 h. After cooling overnight
to room temperature, a white precipitate was observed. The
unreacted succinic anhydride was removed by filtration, leaving
crude mono-n-butyl succinate. A portion of the crude material
(9.4 g) was chromatographed (column diameter = 7.6 cm,
column height = 56 cm) on silica using dichloromethane as the
eluent until the di-butyl succinate ester eluted. Ethyl acetate
was then added to the column to remove the desired product,
mono-n-butyl succinate. The product was dissolved in 50 mL
of dry ether and dried over MgSO4, which was removed by
filtration. The solvent was removed from the filtrate in vacuo
1
to afford the product as a yellow oil (5.04 g, 54%). H NMR
(300 MHz, CDCl3) d 11.49 (1H, s, OH), 4.07 (2H, t, J =
6.6 Hz, OCH2CH2CH2CH3), 2.62 (4H, m, COCH2CH2CO),
1.58 (2H, quintet, J = 7.3 Hz, OCH2CH2CH2CH3), 1.34 (2H,
sextet, J = 7.5 Hz, OCH2CH2CH2CH3), 0.89 (3H, t, J = 7.3 Hz,
OCH2CH2CH2CH3) ppm.
Standard reaction protocol
In a dinitrogen atmosphere glovebox, hydrocinnamic acid (1 g,
6.7 mmol), palladium(II) chloride (3 mg, 0.25 mol%), pivalic
anhydride (1.35 mL, 6.7 mmol), and phosphine ligand (2.2 mol%
or 4.4 mol%) were loaded into an oven-dried 15 mL round-
bottom flask equipped with a Teflon stir bar. Not all of
the reagents were soluble at room temperature, resulting in a
heterogeneous mixture. The round-bottom flask was attached to
an oven-dried short-path distillation apparatus, removed from
the glovebox and placed under an atmosphere of dinitrogen or
argon gas. The reaction flask was lowered into a 160 to 170 ◦C oil
bath and allowed to continue to heat until the oil bath reached
190 ◦C. In most cases, the reaction mixture became homogenous
and yellow after heating. Once the reaction mixture reached
Experimental
Materials and physical methods
All experiments were carried out in an inert atmosphere unless
otherwise noted. All organic reagents were purchased from
Sigma Aldrich and used without further purification unless oth-
erwise noted. Mono-methyl succinate17 and 3-cyanopropanoic
acid10 were prepared according to literature procedures. While
purchased from Sigma Aldrich, mono-tert-butyl succinate can
be prepared by reacting succinic anhydride with tert-butanol.18
Palladium(II) chloride was purchased from Strem Chemicals
and dried under vacuum for 24 h at 90 ◦C. Pivalic anhydride
was dried over molecular sieves. Hydrocinnamic acid was
recrystallized from dry pentane and sublimed prior to use.
All phosphine ligands were dried under vacuum for 24 h at
90 ◦C. PPh3, 1,3-bis(diphenylphosphino)propane (DPPP) and
1,2-bis(diphenylphosphino)ethane (DPPE) were recrystallized
from ethanol prior to drying under vacuum. 4-tert-Butyl cate-
chol was recrystallized from pentanes and dried under vacuum
for 24 h at 120 ◦C. Triethylamine was allowed to stir over CaH2
overnight prior to use. Ether and dichloromethane were passed
through a purification column (Glass Contour, Laguna, CA)
◦
about 185 C, it began to bubble vigorously, indicating loss of
carbon monoxide. The reaction was allowed to proceed for two
hours, during which time a distillate was collected. After 2 h,
heating was ceased and the reaction was exposed to air. Both
the colorless distillate and yellow residual reaction mixture were
1
analyzed using H NMR spectroscopy, and the distillate was
also analyzed using GC-MS.
Styrene separation protocol
1
A mixture comprised of styrene (3.13 g, 30.0 mmol), pivalic acid
(6.35 g, 62.1 mmol), and pivalic anhydride (0.63 g, 3.4 mmol)
was diluted with 35 mL of pentanes and washed with a 1.7
M aqueous NaOH solution (3 ¥ 50 mL). The organic phase
was diluted with an additional 15 mL of pentanes and dried
over MgSO4. After filtration, solvent was removed to afford a
mixture of styrene and pivalic anhydride (as characterized by 1H
NMR spectroscopy) that was then chromatographed (column
diameter = 5 cm, column height = 25 cm) on silica using pentane
as the eluent to yield styrene (2.03 g, 65%).
prior to use. All H NMR spectra were collected on either a
Varian VXR-500 or Varian VI-300 spectrometer and calibrated
to the residual protonated solvent at d 7.24 for deuterated
chloroform (CDCl3). All GC-MS experiments were conducted
on an Agilent Technologies 7890A GC system and 5975C VL
MSD. The GC column was a HP-5 ms with dimensions 30 m ¥
0.25 mm. The standard method used for all runs involved an
initial oven temperature of 50 ◦C (held for 2 min) followed by a
20 ◦◦C min-1 ramp to 70 ◦C (held for 6 min), followed by a final
20 C min-1 ramp to 230 ◦C (held for 3 min).
Mono-n-butyl succinate
N-Butyl pivalate ester20
In a modified version of a reported procedure,19 to a 250 mL
oven dried round bottom flask succinic anhydride (49.6 g,
N-butanol (6.2 mL, 67.8 mmol), pivaloyl chloride (10.1 mL,
82.1 mmol), 4-dimethylaminopyridine (0.4196 g, 3.4 mmol)
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Table 1 Yields (%) for the catalytic decarbonylation of mono-alkyl
and dry dichloromethane (140 mL) were added to an oven
dried 250 mL round bottom flask equipped with a stir bar. To
this, triethylamine was added (11.5 mL, 82.5 mmol). After an
exothermic reaction, a white precipitate formed. The reaction
was allowed to stir overnight, then 100 mL of dichloromethane
was added. The organic layer was washed with 250 mL water
twice, 250 mL of 1 M HCl, 250 mL of saturated aqueous
Na2CO3, and 250 mL saturated aqueous NaCl. The organic
layer was dried over MgSO4, filtered, and the dichloromethane
was removed from the filtrate in vacuo. A portion of the crude
product (2.44 g) was chromatographed (column diameter = 5
cm, column height = 25 cm) using dichloromethane as the eluent
(2.09 g, 86%). The 1H NMR spectrum of the product matched
data reported previously.21
succinates (eqn (3))a
Entry
Ligand
R
Acrylateb
PivORb
PivOHc
1
2
3
4
5
6
PPh3
DPEphos
PPh3
DPEphos
PPh3
DPEphos
Me
Me
n-Bu
n-Bu
t-Bu
t-Bu
50
64
62
45
31
18
3
12
8
21
11
10
71
49
62
60
79
90
a All experiments were carried out using dry reagents under an N2 or Ar
atmosphere unless otherwise noted. PdCl2 loading: 0.25 mol%, ligand
loading: 2.2 mol%, calculated based on succinic ester substrate. T ª
190 ◦C. All results calculated from GC-MS data. Representative GC-
MS traces can be found in the ESI, Figures S1–S3.† b Yields based on
the succinic ester substrate. c Yields based on the stoichiometry of eqn
(3) (2 moles PivOH per mole Piv2O used).
Results and discussion
Mono-alkyl succinates were readily prepared according to
eqn (2) by heating an alcohol (R = Me, t-Bu, n-Bu) with
succinic anhydride, the dehydration product of succinic acid,
a biorenewable resource produced from the fermentation of
sugars.2b,22 In our variation of Miller’s procedure,3 one equivalent
S5, see ESI†) detected succinic anhydride, PivOH, and methyl
pivalate (or t-butyl-pivalate). We hypothesize that the mono-
alkyl succinates undergo an intramolecular cyclization to reform
succinic anhydride and alcohol, with the latter reacting with
Piv2O to form PivOH and PivOR (eqn (4)).
◦
of pivalic anhydride (Piv2O, b.p. = 193 C) was used in lieu of
Ac2O (b.p. = 140 ◦C) at a reduced temperature of 190 ◦C to avoid
continuous addition of anhydride during each experiment. To
both compensate for the lower temperature and possibly increase
reaction rates, palladium (i.e., PdCl2) and ligand loadings were
initially increased to 0.25 mol% and 2.2 mol%, respectively,
as compared to Miller’s protocol. Using a standard short-path
distillation head under a moderate flow of N2 (or Ar), a clear
solution was isolated by continuous distillation after 2 h of
heating dry mono-succinate ester (1, 2 or 3), Piv2O, PdCl2, and
ligand (eqn (3)).
(4)
In an expansion of the scope to other bio-derived carboxylic
acids, we examined the production of styrene from hydrocin-
namic acid (eqn (5)). Both GC-MS and 1H NMR analyses of the
distillate (isolated under the aforementioned reaction conditions
using PPh3 as the ligand) revealed the formation of styrene
in 74% (GC-MS) yield (entry 1, Table 2). Distillation began
after approximately 30 min at 180–190 ◦C, and the reaction
was allowed to continue for 2 h. Isolation of pure styrene was
achieved by washing the diluted distillate with aqueous NaOH
to remove the pivalic acid, followed by a short silica column to
remove remaining pivalic anhydride.23 In the previous study by
Gooben and Rodr´ıguez, low yields (27%) were reported when
PPh3 was used as the ligand under their procedures.5
(2)
(3)
(5)
Analysis of the distillate by both GC-MS and 1H NMR
spectroscopy confirmed the presence of the desired alkyl acry-
late. Methyl acrylate (4) was prepared in 50% and 64% yield
when using PPh3 and bis[(2-diphenylphosphino)phenyl] ether
(DPEPhos) as the ligands, respectively (entries 1 and 2, Table
1). Results for the production of n-butyl acrylate (5) were
comparable, but the yields of t-butyl acrylate (6) from mono-
t-butyl succinate (3) were lower, 31% when using PPh3 and 18%
when using DPEphos (entries 5 and 6). Interestingly, minor
amounts of alkyl pivalates (PivOR) were also produced during
the course of these experiments, suggesting the presence of a
competitive reaction. Indeed, in a control experiment, Piv2O
and 1 (or 3) were heated in an equimolar ratio to 190 ◦C for
two hours. GC-MS analysis of the crude mixture (Figures S4,
The nature of the ligand and its effect on the product yield
were investigated by examining a number of bidentate phosphine
ligands (Table 2). Styrene formation was inhibited when DPPE
was used in lieu of PPh3 (entries 2 and 7). In these cases,
analysis of the crude reaction mixture by 1H NMR spectroscopy
revealed only the presence of the mixed anhydride formed from
hydrocinnamic acid and pivalic anhydride. In addition, palla-
dium black formed instantly upon heating to 160 ◦C suggesting
that the DPPE-palladium catalyst is not stable under these
conditions. Using DPPP as the ligand afforded styrene, although
lower yields and longer times for the onset of distillation (30–
45 min) were observed (entries 3 and 8). DPEphos (known
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(entry 4). Heating “wet” reagents26 under a moderate flow of
air (otherwise identical conditions) resulted in the formation of
styrene in comparable yields to using dry reagents under air
(entry 13). Using PPh3 in lieu of DPEphos as a ligand gave rise
to styrene in similar yields (entry 14). Reducing the wet27 PdCl2
and PPh3 loadings to 0.01 mol% and 0.5 mol%, respectively, on
a ca. 25 g scale of reagent-grade hydrocinnamic acid afforded
styrene in ~ 57% (GC-MS) yield (entry 15). Thus, in contrast
to previous studies that carried out decarbonylation reactions
using dried reagents and under a flow of inert gas, we have
demonstrated that this reaction is robust to both air and water;
rigorously dried reagents and a flow of inert gas do not markedly
improve yields or reduce reaction times. This obviously renders
the overall transformation less energy, solvent and time intensive.
In an effort to further improve the reaction efficiency for the
production of styrene, the Pd and ligand loadings were reduced
to 0.005 mol% and 0.025 mol%, respectively (entry 16). The yield
for this reaction is comparable to yields with higher loadings.
However, the reaction is slower, requiring 31 h to complete the
distillation, whereas reactions with double the Pd and ligand
loadings (0.01 mol% Pd, 0.5 mol% ligand) required a maximum
3 h to complete the distillation.
Table 2 Yields (%) for the catalytic decarbonylation of hydrocinnamic
acid (eqn (5))a
Entry
Ligand
Ligand mol%b
Styrenec
PivOHc
1
2
3
4
5
6
7
8
PPh3
DPPE
DPPP
DPEphos
Xantphos
PPh3
DPPE
DPPP
DPEphos
Xantphos
DPEphos
DPEphos
DPEphos
PPh3
2.2
2.2
2.2
2.2
2.2
4.4
4.4
4.4
4.4
4.4
0.5
2.2
2.2
2.2
0.5
0.25
74 (73)
0 (0)
55 (52)
81 (82)
80 (84)
65 (70)
0 (0)
48 (40)
84 (87)
87 (92)
68 (74)
72 (75)
78 (72)
71 (61)
57 (50)
54 (58)
65 (66)
0 (0)
52 (54)
83 (81)
85 (84)
81 (82)
0 (0)
60 (60)
85 (81)
86 (83)
88 (85)
73 (78)
84 (90)
66 (75)
60 (64)
70 (69)
9
10
11d
12e
13f
14f
15d,f
16g
PPh3
DPEphos
a All experiments were carried out using dry reagents under an N2 or
Ar atmosphere unless otherwise noted. PdCl2 loading: 0.25 mol% and
1 g scale of hydrocinnamic acid unless otherwise noted. T ª 190 ◦C
b Calculated based on hydrocinnamic acid substrate. c Percent yield in
distillate calculated from GC-MS (NMR) data. A representative GC-
MS trace can be found in the ESI, Figure S6.† d PdCl2 loading: 0.01 mol%
and 25 g scale of hydrocinnamic acid. e Air was used as carrier gas. f Air
was used as carrier gas. Reagents were left open to the atmosphere for at
least 24 h. g PdCl2 loading: 0.005 mol% and 50 g scale of hydrocinnamic
acid. Allowed to react for 31 h.
Finally, we have applied our methodology to the synthesis
of acrylonitrile from 3-cyanopropanoic acid. Using rather mild
reagents (NaOCl, NaBr, water), 3-cyanopropanoic acid can be
synthesized by the oxidative decarboxylation of glutamic acid,
a biorenewable resource.10 Subsequent decarbonylation of 3-
cyanopropanoic acid using our procedure (PdCl2 0.25 mol%,
PPh3 2.2 mol%) resulted in isolation of distillate that contained
acrylonitrile in 23% yield by GC-MS (see Figure S7 for
representative GC-MS trace, ESI†). The distillate also contained
PivOH and Piv2O. The low yields are explained by the presence
to be successful, vida supra) and 4,5-bis(diphenylphosphino)-
9,9-dimethylxanthene (Xantphos), also were considered since
both are strongly coordinating phosphine ligands that have
been shown to improve product yields for hydrocyanation24
and hydrocarbonylation25 of styrene and the decarbonylation
of phenylbutanoic acid to 3-phenylpropene.5 Consistent with
trends reported by Gooben and coworkers,5 Xantphos and
DPEphos were determined to be the most effective phosphines
in promoting decarbonylation, generating styrene in ca. 80%
yield (entries 4,5,9–13,16). Unlike the more sluggish PPh3 and
DPPP systems, the onset of distillation proceeded quickly (ca.
5 min.), and rapid evolution of CO was observed once the
reaction flask reached 190 ◦C. Increasing the ligand loading
to 4.4 mol% (entries 6–10) and/or adding the stabilizer t-butyl
catechol (data not shown) had a negligible effect on product
yield. In contrast to the stark difference in yields reported by
Gooben and Rodr´ıguez for the decarbonylation of phenylbutyric
acid (27% for PPh3 vs. 83–81% DPEphos),5 the improvements
in yields for the more expensive chelating phosphines DPEphos
and Xantphos relative to PPh3 were negligible in our system.
Scaling up the decarbonylation of hydrocinnamic acid was
successful; using much lower PdCl2 (0.01 mol%) and DPEphos
(0.5 mol%) loadings on a ca. 25 g scale afforded styrene in ~ 70%
yield (entry 11).
1
of polyacrylonitrile in the reaction mixture, as observed by H
NMR spectroscopy. Addition of t-butyl catechol to the reaction
mixture as an inhibitor did not improve the yield of isolated
acrylonitrile. Recently, similar results were obtained by Scott and
coworkers10 using a modified version of Gooben’s procedure.
Conclusions
Using palladium-catalyzed decarbonylation of bio-derived car-
boxylic acids we prepared alkyl acrylates, styrene, and acryloni-
trile in good yields. The developed procedure is applicable to a
diverse set of carboxylic acid substrates, and involves continuous
distillation of the desired products from the reaction mixture. In
addition, catalyst loadings can be lowered to 0.005 mol% and the
reaction scale increased to 50 grams with only a small reduction
in product yield. We also performed a careful ligand screening
using a variety of chelating phosphines, highlighting the im-
portance of the ligand on reaction efficacy. Interestingly, PPh3
was nearly as good a ligand at promoting the decarbonylation
reaction as the strongly coordinating diphosphines DPEphos
and Xantphos, demonstrating that a simple and inexpensive
system can be realized for the decarbonylation of bio-derived
carboxylic acids. Finally, we illustrated the robustness of this
system. Using reagent-grade and wet starting materials under
an air purge gives comparable yields to reactions using purified
and dried reagents and an inert (N2 or Ar) gas purge. We plan
to explore other bio-derived substrates28 and perform detailed
To test the robustness of the decarbonylation reaction, a series
of experiments were performed using a combination of non-
dry/dry reagents and air instead of N2 or Ar as the carrier
gas. Performing the reactions using dry reagents (i.e., PdCl2,
Piv2O, DPEphos) and reagent-grade hydrocinnamic acid under
a moderate flow of air afforded styrene in ~ 72% yield (entry 12,
Table 2), only ca. 9% less when compared to using N2 as a carrier
gas and recrystallized, sublimed and dried hydrocinnamic acid
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mechanistic studies on the decarbonylation reaction to optimize
the identity of the catalyst such that lower temperatures (to
prevent in situ polymerization of the product, have lower energy
input and avoid deleterious side-reactions) and catalyst loadings
(to minimize cost) can be achieved.
12 J. Maul and A. G. Hu¨ls, in Ullmann’s Encyclopedia of Industrial
Chemistry, VCH, New York, 1992, vol. A21, pp 615-663.
13 P. W. Langvardt, in Ullmann’s Encyclopedia of Industrial Chemistry,
VCH, New York, 1992, vol. A1, pp 177-184.
14 R. McKenna and D. R. Nielsen, Metab. Eng., 2011, 13, 544–554.
15 (a) L. Craciun, G. P. Benn, J. Dewing, G. W. Schriver, W. J. Peer, B.
Siebenhaar, and U. Siegrist, US Pat. 2005/0222458, 2005.; (b) J. W.
Johnson and P. W. Uhlianuk, US Pat. 2009/045606, 2009.
16 (a) V. Calvino-Casilda, M. O. Guerrero-Pe´rez and M. A. Ban˜ares,
Green Chem., 2009, 11, 939–941; (b) M. O. Guerrero-Pe´rez and M.
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Acknowledgements
We thank the National Science Foundation (grant CHE-
0842654 to W.B.T. and M.A.H. and a Graduate Research
Fellowship under Grant No. 00006595 to M.O.M.) and the
Center for Sustainable Polymers, a National Science Foundation
supported Center for Chemical Innovation (CHE-1136607) for
financial support of this research.
17 J. Cason, Organic Syntheses, Wiley & Sons, New York, 1955, vol III,
pp 169.
18 R. Srinivasan, M. Uttamchandani and S. Q. Yao, Org. Lett., 2006,
8, 713–716.
19 L. V. Yerino, M. E. Osborn and P. S. Mariano, Tetrahedron, 1982, 38,
1579–1591.
20 Procedure adapted from: E. M. Simmons and J. F Hartwig, J. Am.
Chem. Soc., 2010, 132, 17092–17095.
21 Q. Guo, T. Miyaji, R. Hara, B. Shen and T. Takahashi, Tetrahedron,
2002, 58, 7327–7334.
22 J. J. Beauprez, M. De Mey and W. K. Soetaert, Process Biochem.,
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B. E. Suttle and G. R. Richardson, Appl. Biochem. Biotechnol., 1997,
63–65, 565–576.
23 The separation of styrene from pivalic acid and pivalic anhydride
through fractional distillation was unsuccessful due to co-distillation
of styrene and pivalic acid and polymerization of styrene.
24 M. Kranenburg, P. C. J. Kamer, P. W. N. M. van Leeuwen, D. Vogt
and W. Keim, J. Chem. Soc., Chem. Commun., 1995, 2177–2178.
25 I. del R´ıo, N. Ruiz, C. Claver, L. A. van der Veen and P. W. N. M.
van Leeuwen, J. Mol. Catal. A: Chem., 2000, 39–48.
26 PdCl2, Piv2O, and ligands were left open to the atmosphere for 24
h. The hydrocinnamic acid was used as received without purification
and left open to the atmosphere for ~ 4 months.
27 PdCl2, Piv2O, and ligands were left open to the atmosphere for 48
h. The hydrocinnamic acid was used as received without purification
and left open to the atmosphere for ~ 4 months.
28 The bio-derived substrates levulinic acid, a- and b-angelica lactone
can be decarbonylated to methyl vinyl ketone over a solid acid catalyst
at high temperatures (290–500 ◦C), (see J. A. Dumesic, and R. M.
West, US Pat. 7 960 592, 2011) as well as photochemically (see O. L.
Chapman and C. L. McIntosh, J. Chem. Soc. D, 1971, 383–384) and
in the gas phase through a quartz tube at high temperatures (above
500 ◦C) (see; Z. P. Xu, C. Y. Mok, W. S. Chin, H. H. Huang, S. Li
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Notes and references
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4 T. A. Foglia and P. A. Barr, J. Am. Oil Chem. Soc., 1976, 53, 737–741.
5 L. J. Gooben and N. Rodr´ıguez, Chem. Commun., 2004, 724–725.
6 J. Le Noˆtre, E. L. Scott, M. C. R. Franssen and J. P. N. Sanders,
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7 S. Maetani, T. Fukuyama, N. Suzuki, D. Ishihara and I. Ryu,
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8 E. Penzel, in Ullmann’s Encyclopedia of Industrial Chemistry, VCH,
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9 Clostridia enzymatically produce hydrocinnamic acid from l-
phenylalanine. See C. W. Moss, M. A. Lambert and D. J. Goldsmith,
Appl. Microbiol., 1970, 19, 375–378; Hydrocinnamic acid can also
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10 3-cyanopropanoic acid can be prepared from glutamic acid, a
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11 M. A. Bomgardner, Chem. Eng. News, 2011, 89(27), 55–63.
494 | Green Chem., 2012, 14, 490–494
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