Accepted Manuscript

Recent developments in chemical degradation of lignin: catalytic oxidation and

ionic liquids

Jinhuo Dai, Antonio F. Patti, Kei Saito

PII: S0040-4039(16)31267-9
DOI: http://dx.doi.org/10.1016/j.tetlet.2016.09.084
Reference: TETL 48154

To appear in: Tetrahedron Letters

Received Date: 30 June 2016

Revised Date: 22 September 2016
Accepted Date: 26 September 2016

Please cite this article as: Dai, J., Patti, A.F., Saito, K., Recent developments in chemical degradation of lignin:
catalytic oxidation and ionic liquids, Tetrahedron Letters (2016), doi: http://dx.doi.org/10.1016/j.tetlet.2016.09.084

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 Tetrahedron Letters 2

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Recent developments in chemical degradation of lignin: Leave this area blank for abstract info.
catalytic oxidation and ionic liquids
Jinhuo Dai, Antonio F. Patti, and Kei Saito
 Tetrahedron Letters 1

Tetrahedron Letters

Recent developments in chemical degradation of lignin: catalytic oxidation

and ionic liquids
Jinhuo Dai, Antonio F. Patti, and Kei Saito
School of Chemistry, Monash University, Clayton, VIC 3800, Australia

A RT I C L E I N F O A BS T RA C T

Article history: Lignin, considered as the second most abundant resource of aromatic chemicals in nature, has
Received attracted a great deal of attention in academia and industry. Recently, numerous investigations
Received in revised form have been carried out to consider the production of aromatic chemicals with high value, sourced
Accepted from lignin. Among all these methods, oxidative treatments of the lignin show a promising way
Available online to generate highly functionalized monomeric or oligomeric chemicals, which can be further
applied in chemical industries. Moreover, ionic liquids, known as salts with melting point below
100 °C, have also been introduced into oxidative lignin depolymerisation as these are known to
Keywords: disrupt the lignocellulose structure as well as partially dissolving the lignin. Herein, we reviewed
Lignin various significant pathways of catalytic lignin oxidation and also discussed strengths and
Lignin oxidation weaknesses between different lignin oxidation routes reported in the recent literature. Several
Depolymerisation innovative strategies for oxidative lignin depolymerisation in ionic liquid are also discussed,
Ionic liquids along with some recommendations and pathways in the field of catalytic lignin oxidation and
Green Chemistry depolymerisation involving ionic liquids.
2009 Elsevier Ltd. All rights reserved .

Introduction weight, as well as dicarboxylic acids have been frequently

reported.4, 5 These were detected as the main depolymerisation
With the increasing demand for clean energy and renewable products from oxidative lignin degradation, which can be further
materials, biomass utilization has attracted significant research used as significant platform chemicals for chemical industries.6, 7
attention. As an energy source, biomass can not only be used for Organometallic catalysed oxidation methods, biomimetic
producing heat via combustion but can also be converted to oxidation methods and enzyme-based oxidation methods have
various fine chemicals and biofuel.1, 2 The biomass-to-biofuel also been widely studied and reported. 4 Some of these
conversion process has been studied for several decades. technologies targeted certain bonds, for example, β-O-4 linkages
However, converting biomass into valuable chemicals with an in lignin, to produce different products with high selectivity,8
acceptable cost is still a big challenge, and the conversion of the while others oxidized lignin without giving the mechanism due to
better understood carbohydrate components has achieved undefined lignin structure.
considerable success.
Ionic liquids, defined as salts with melting point below 100 °C,
Lignin, together with cellulose and hemicellulose, is known as have also been taken into consideration for lignin
a natural complex polymer containing the most abundant depolymerisation due to their non-flammability, recyclability and
aromatic structures in nature.3 Lignin is a special challenge, non-volatility.9, 10 Lignin is difficult to deal with because of its
because there is no defined structure, however it is made up of poor solubility in any green solvents. However, some lignins
three primary monomers with several typical linkages as showed have shown considerable solubility in some ionic liquids, which
in Figure 1. can be used for lignin depolymerisation. Ionic liquids have been
Lignin is a major by-product in the paper and pulp industry, introduced into lignin research with various applications 11, 12, for
and can be potentially used to generate valuable aromatic example, extracting lignin from biomass, dissolving lignin for
primary feedstock chemicals instead of the current practice of depolymerisation and catalyzing lignin depolymerisation.13 Many
being burnt to produce energy. Various strategies for lignin studies have been carried on the behavior of lignin when
degradation including lignin catalytic cracking, hydrolysis, lignin dissolved in ionic liquids. These studies showed that the lignin
reduction and lignin oxidation, have been reported to show the structure has been changed with the treatment in ionic liquids.
promise of utilization of lignin.2, 4 Among all these technologies, Moreover, oxidative lignin degradation in ionic liquids has
lignin oxidation has been widely studied and used in the also been reported 4, 13, 14, some of which showed β-O-4 bonds
papermaking industry in the bleaching process due to its
selectivity.4 Additionally, phenolic products with low molecular
———
 Corresponding author. Tel.: +61-3-9905-4600; fax: +61-3-9905-8501; e-mail: [email protected]
 Tetrahedron Letters 2

Scheme 1: Proposed catalytic cycle for TEMPO oxidation of

alcohols17.
scanning electron microscopy (SEM), x-ray powder diffraction
(XRD), x-ray photoelectron spectroscopy (XPS) and Raman
spectroscopy and the catalytic activity also proved to be similar
after four consecutive cycles. Other cobalt complexes, as well as
oxovanadium and copper complexes, have also been studied and
compared by Baker et al.16 These exhibited intriguing selectivity
for aerobic oxidation of lignin model compounds and organosolv
lignin. In particular, bis(8-oxy-quinoline)oxovanadium and
bis(phenolate)pyridine oxovanadium showed the best activity for
oxidation and depolymerisation of organosolv lignin when
compared to other catalysts, such as CuOTf/TEMPO, 4-
acetamido-TEMPO/acid and (salen)cobalt(II). The resulting
products were analysed by gel permeation chromatography
(GPC) and Q-HSQC nuclear magnetic resonance spectroscopy
(NMR), which showed the molecular weight of the organosolv
lignin was decreased with an increase of oxidized syringyl and
Figure 1: (a) proposed lignin structure with several linkages; guaiacyl units. Different selectivities for C-H, C-C and C-O
(b) three primary alcohol structures in lignin. bonds were shown by utilising acetamido-TEMPO, bis(8-oxy-
quinoline)oxovanadium and bis(phenolate)pyridine oxovanadium
were oxidized followed by C-C bond cleavage to selectively
respectively. CuOTf/TEMPO, also exhibited complementary
yield phenolic products.
selectivity to the oxovanadium catalyst involving radical
Several reviews have recently been published on lignin recombination. Stahl et al.17 presented a proposed mechanism of
depolymerisation which focused on chemical methods and TEMPO catalysed aerobic oxidation of alcohols (Scheme 1).
biotechnological strategies.4-6 In this publication, we will focus
Moreover Saito et al.18-21 showed that copper complexes
on the recent developments about catalytic lignin oxidation
catalysed lignin depolymerisation in water and ionic liquids
utilizing chemical methods, especially, the oxidation of β-O-4
involving the phenol radical redistribution mechanism. In their
bonds in lignin. Next, ionic liquid applications in lignin
work, 4-tert-butyl-2,6-dimethyl-phenol was transformed to a
chemistry will be discussed. In particular, several strategies for
phenol radical catalysed by copper complexes, which then
oxidative lignin depolymerisation in ionic liquids will be
attacked the lignin molecular leading to 4-O-5 bonds cleavage.
compared.
Lignin was oxidatively depolymerised in this case. In addition,
Lignin oxidation copper coordinating with different N-based ligands were also
investigated to oxidatively depolymerise lignin in ionic liquid
Oxidative lignin depolymerisation is a method to break involving the radical redistribution mechanism.20 In this work,
selected bonds, such as aryl ether bonds, carbon-carbon bonds or the molecular weight of organosolv lignin decreased from 12,000
β-O-4 bonds in lignin. This involves the application of different to 2,000 catalysed by copper and two certain N-based ligands
oxidants (e.g. oxygen gas, hydrogen peroxide and metal oxides). ((E)-N-(pyridin-2-ylmethylene) aniline and (E)-4-methoxy-N-
The functionalized products vary from aromatic aldehydes to (pyridin-2-ylmethylene) aniline). Copper, along with iron sulfate
carboxylic acids, for example, vanillin, vanillic acid, and and sodium hydroxyl, has also been used as a catalyst for
syringaldehyde hydrothermal oxidative depolymerisation of lignin. Qiu et al.22
studied the use of H2O2 as the oxidant and CuO/Fe2(SO4)3/NaOH
Organometallic catalysed oxidation
as catalyst for hydrothermal oxidative depolymerisation of lignin.
Much of the published research on oxidative degradation of In their work, the effect of various solvents, including water,
lignin reports the use of lignin model compounds to confirm the methanol, 1,4-dioxane, tetrahydrofuran, ethanol and their co-
strategies before applying these to natural lignin. Hussein Ali et solvents for the depolymerisation reaction was investigated. The
al.15 have reported a novel strategy for lignin oxidation, in which yield of phenolic monomer reached 17.9% by using 1:1(v/v) of
a mixed metal cobalt titanium oxide was prepared as a catalyst methanol/water as solvent for the depolymerisation reaction. The
for the oxidation of vanillyl alcohol. A radical mechanism was alkalinity of the reaction medium, the solubility of lignin, and
proposed in this work. A hydroperoxyl radical was generated demethoxylation during the oxidation reaction were affected by
with the presence of H2O2 to attack the activated carbon in the proportion of methanol to water. As for the products,
vanillyl alcohol resulting in the generation of final acid products monophenolic products, such as vanillin, vanillic acid,
with water as a by-product. In this study, CoTiO3 showed a high sryngaldehyde, syringic acid, acetosyringone), and para-
conversion of 99% and remarkable selectivity of 99.8% to hydroxybenzoic acid were detected along with some re-
vanillin in isopropanol and acetic acid solvents, independently. polymerised oligomers. These hydrothermal oxidation reactions
Additionally, the reusability of CoTiO3 was confirmed by
 Tetrahedron Letters 3

Figure 3. Oxovanadium(v) complexes (a), (salen)cobalt(II) (b),

4-acetamido-TEMPO/acid (c), CuTf/TEMPO (d) catalysts for
Figure 2: β-O-4 lignin model compounds.
oxidation of lignin model compounds (TEMPO = 2,2,6,6-
required high temperature and pressure for lignin tetramethylpiperidine-1-oxyl; OTf = trifluoromethanesulfonate).
depolymerisation.
acid showed a high selectivity for oxidative C-C bond cleavage
Another strategy for lignin oxidation catalysed by copper was with rather limited C-H bond cleavage.
also developed by De la Cruz et al.23 for quantification of lignin
The one-electron process was shown by the occurrence of
in municipal solid waste. This method involved cleavage of the
vanadium(v), which indicated that the carboxylic group could
lignin linkages producing phenolic aldehydes, ketones, and
coordinate to vanadium(v) via exchange with the acetylacetonato
carboxylic acids. This strategy has been mentioned by Sarkanen
ligand in the reaction. Hanson et al.27 also reported base metal
and Ludwig24 proposing that a phenyl radical formed with a one-
complexes, oxovanadium complexes, as catalysts for selective
electron transformation followed by eventual formation of
oxidation of lignin models and lignin extracts from plants.
quinone methide intermediates. In this study, a sample from
Several vanadium(v) complexes, as well as copper/TEMPO, have
municipal solid waste was oxidized by CuO followed by analysis
been investigated with β-O-4 type lignin model compounds. The
by high-performance liquid chromatography (HPLC) and gas
results demonstrated that the selected vanadium(v) complexes
chromatography-mass spectrometry (GC/MS) to quantify the
showed an effective alcohol oxidation catalytic ability involving
lignin monomers. The relationship between lignin and the sum of
a base-assisted dehydrogenation pathway, while the
monomers from CuO oxidation (Λ8) was evaluated to establish a
copper/TEMPO catalyst could catalyse the cleavage of C-C
calibration method for analysis. Similarly, Sun et al.25 also
bonds through a radical mechanism. However, when applied to
reported a simplified cupric oxide oxidation. Lignin samples
organosolv lignin, copper catalysed lignin oxidation showed a
were oxidatively hydrolyzed to generate 11 phenolic products
minor molecular weight decrease while vanadium(v) catalysed
including p-hydroxybenzoic acid (PAD), p-hydroxybenzaldehyde
lignin oxidation showed an obvious molecular weight decrease.
(PAL), vanillic acid (VAD), syringic acid (SAD), vanillin (VAL),
Among all these catalysts, the bis(quinolinate) vanadium(v)
p-hydroxyacetophenone (PON), syringaldehyde (SAL);
complex (HQ)2V(O)(OiPr) was considered as the most effective
acetovanillone (VON), acetosyringone (SON), p-coumaric acid
catalyst for the oxidative depolymerisation of organosolv lignin.
(CAD), and ferulic acid (FAD).
Mottweiler et al.28 also reported a strategy using
V(acac)3/Cu(NO3)23H2O mixtures and transition-metal-
containing hydrotalcites (HTc) as catalysts to catalyse the
β -O-4 linkages targeted oxidation oxidative cleavage of lignin with molecular oxygen as an oxidant.
The β-O-4 bond is the most abundant linkage in lignin, which The lignin model compound, erythro-1-(3,4-dimethoxyphenyl)-2-
accounts for more than half of the linkage structures in lignin. A (2-methoxyphenoxy)-1,3-propanediol, was firstly reacted with
significant amount of research has been carried out with a focus these two catalysts showing a high conversion in both catalytic
on lignin depolymerisation targeting the β-O-4 bond cleavage. oxidation reactions. Then four lignin samples were investigated
Generally, the hydroxyl group on the α-carbon in β-O-4 bond by using these two catalysts. The molar mass peak of lignin
was oxidized to ketone, which may lead to C-C bond cleavage. shifted from 1,400 Da to 300Da with the β-O-4 linkages,
Most of the reports have described the oxidation of lignin model acetylated β-O-4 linkages, resinol structures and p-
compounds to confirm the selectivity of different catalysts. The hydroxycinnamyl alcohols degraded during the reaction, which
model compounds synthesized have been listed in Figure 2 and was confirmed by 2D-NMR (HSQC).
some of the catalysts used are shown in Figure 3. Zhou29 has also reported the use of a zeolite-encapsulated copper
26 (II) tetrahydro-salen complex to catalyse oxidation and the
Xu et al. applied a vanadium catalyst in the presence of acetic
acid to selectively oxidize the β-O-4 bond in lignin model conversion of kraft lignin, generating phenolic products. Cu(II)
compounds, resulting in C-C bond cleavage. Aldehyde, acid and [H4]salen and [H2]salen complexes were synthesized and then
esterification products were detected after oxidation. In this study, immobilized on NaY to form the zeolite-encapsulated complexes.
the lignin model compound 2-phenoxy-1-phenylethanol was Acetic acid was used as the oxygen source giving several major
oxidized by using VO(acac)2 as catalyst with oxygen gas. After products including 2-methoxy phenol with yield over 70%,4-
reactions, phenol (53%), 2-phenoxy-1-phenylethanone (2.3%) hydroxy benzaldehyde, and 4-hydroxy-3,5-dimethoxyphenyl
were obtained as the main products. The solvent in this reaction ethanone. It has also been reported30 that the superoxo complex
affected the selectivity of oxidation and bond cleavage. Acetic (L-Cu-O-O) radical was formed with hydrogen abstraction
 Tetrahedron Letters 4
1 Table 1: Catalysts used for β-O-4 bond cleavage.

Entry Substrate Catalysts Conditions Conversion Products

1 2-phenoxy-1- VO(acac)2/acetic acid 80°C, 8h, 1 atm O2 94.2% Phenol(53%), 2-phenoxy-1-
phenylethanol (1)26 phenylethanone(2.3%), etc.
2 1-(3,5- (dipic)VV(O)(Oi Pr) 100°C, 48h, DMSO-d6 95% 1-(3,5-dimethoxyphenyl)-3-
dimethoxyphenyl)-2-(3- i hydroxy-2-(2-methoxy
methoxyphenoxy) (HQ)2V(O)(O Pr) phenoxy)propan-1-one(65%)
27, 31
propane-1,3-diol(4)
3 1-(3,4- Fe-DABCO 100°C, 16h, 95% 2-methoxyphenol(42%)
dimethoxyphenyl)-2-(2- DMSO/H2O(1:1),
methoxyphenoxy)propan H2O2， AcOH EtOAc 3,4-dimethoxy-
e-1,3-diol
32 benzaldehyde(35%)

4 1-(3,4- Transition-metal-containing 135°C, 16h, 5.9 atm 99% Veratraldehyde (38%),

dimethoxyphenyl)-2-(2- hydrotalcities(HTc), O2 O2, pyridine Veratric acid (31%), etc.
methoxyphenoxy) V(acac)3/Cu(NO3)2·3H2O
ethanol (2)28
5 Oragnosolv lignin28 Transition-metal-containing 135°C, 40h, 9.8 atm 80% Degraded products with a
hydrotalcities(HTc), O2 O2, pyridine mass of less than 300 Da
V(acac)3/Cu(NO3)2·3H2O

2
from phenolic groups, which then catalysed the cleavage of the In addition, the reaction required mild conditions (80°C), ethyl
β-O-4 ether resulting in 2-methoxy phenol (79%). Additionally, acetate/water, and air as an oxidant and the Pd/C catalyst was
this work demonstrated that the conversion of kraft lignin recyclable.
catalysed by encapsulated Cu([H4]salen) was higher than that
After the oxidation of β-O-4 bonds, Meier et al.35 have
from other traditional complexes tested in this work.
developed a strategy to further oxidize the products to convert
Another metal-salen catalyst, Co(salen) has also been widely ketones into their corresponding esters. In this research, they
studied. Gao et al.33 demonstrated a Co(salen) catalyst can be investigated iron porphyrin, 2,3-Dichloro-5,6-dicyano-1,4-
used for the catalytic conversion of kraft lignin. Their team benzoquinone(DDQ)/NaNO2, TEMPO/NaNO2, and
homogeneously scattered Co(salen) powders over a ceramic fiber (tetraphenylporphyrinato)iron(III) chloride(TPPFeCl)/H2O2
network to form a catalyst impregnated paper, which was further catalyst systems to catalyse oxidation of phenolic compounds.
applied for the oxidative depolymerisation of kraft lignin with These four catalysts showed different selectivity for oxidation of
H2O2 as an oxidant. The depolymerisation results showed the benzylic alcohol and benzylic -CH2- groups. The compounds
catalyst, with an interconnected 3D-network, performed more with unprotected phenolic hydroxyl groups were only compatible
efficiently in the oxidation of kraft lignin with a yield of 23.3% with DDQ/NaNO2, which could be further oxidized. Finally, the
compared with traditional Co(salen) powder with a yield of Baeyer-Villiger oxidation method was applied and successfully
10.6%. The phenolic products included 2,6-dimethoxyphenol, cleaves the Cα-Cβ bonds in the oxidized lignin model compounds
vanillin, and syringaldehyde due to the oxidative cleavage of β- (3) with a yield of 90%.
O-4 linkages, which has been proven by 2D-NMR (HSQC).
Moreover, this catalyst paper also showed excellent recyclability Ionic liquids in lignin chemistry
as a similar conversion of kraft lignin was obtained when the Ionic liquids were introduced into biomass processing due to
recovered catalysed paper was reused. their ability to selectively dissolve lignin or cellulose and assist in
Bolm et al.32 have investigated several FeCl3-derived iron the deconstruction of lignin and cellulose network. Ionic liquids,
catalysts for oxidative cleavage of lignin and β-O-4 linkages with due to their ability to solubilise lignocellulose biomass, have
peroxides in dimethyl sulfoxide(DMSO). Screening reactions been widely used in lignin chemistry. Moens et al.12 have
were carried out for the cleavage of lignin model compounds reported the application of ionic liquids as reaction media for
with different iron N-based ligands complex catalysts, such as lignin model compounds. Numerous applications of ionic liquids
Fe-tetramethylethylenediamine(TMEDA), Fe- in biomass chemistry have since appeared in the literature. 13, 36, 37
hexamethylenetetramine(HMTA), Fe-N,N,N’,N’’,N’’- Ionic liquids have been briefly classified based on their cations
pentamethyldiethylenetriamine(PMDTA), and Fe- 1,4- and anions.38-40 Ionic liquids used for biomass can also be sorted
diazabicyclo[2.2.2]octane(DABCO), and different oxidants out in this way. Organic cations includes 1-alkyl-
including tert-butyl hydroperoxide(TBHP) and H2O2. Among all 3methylimidazoliym, N-alkylpyridinium, tetraalkylammonium
these screening reactions, Fe-DABCO catalysed oxidation of and tetraalkylphosphonium. Anions can be divided into organic
lignin model compounds in DMSO with peroxides as oxidants parts and inorganic parts, such as hexafluorophosphate,
were the most effective, generating 42% of 2-methoxy-phenol tetrafluoroborate, trifluoromethylsulfonate, trifluoroethanoate,
and 35% 3,4-dimethoxy-benzaldehyde. Additionally, it was also ethanoate, nitrate and halide, as shown in Figure 4.
shown that methyl radicals generated from H2O2 and DMSO The recoverability of ionic liquids has also been investigated.
were the key reactive species facilitating this cleavage. Moreover, Koo et al.41 have reviewed numerous methods for recovery of
Samec et al.34 have also developed another metallic catalyst, ionic liquids, including distillation, extraction, adsorption,
palladium with carbon to selectively oxidize the β-O-4 linkages induced phase separation, and membrane-based methods. Earle et
under a mild condition with ethyl acetate and water as a solvent. al.42 have demonstrated the distillation and volatility of ionic
For some of the other catalysts mentioned above, the oxidation of liquids. In their work, a Kugelrohr oven and distillation apparatus
β-O-4 generally involved a C-O or C-C cleavage or γ-alcohol were used for the recovery of aprotic ionic liquids, with [Cnmin]+
dehydrogenation, while this pathway supplied a straightforward as cations, at the temperature of 200-300°C and pressure of 0.1
route to aryl ethyl ketones from benzylic alcohol with selective mbar. However, the protic ILs, which have halide, sulphate, or
dehydrogenation in 60-93% yield. The catalyst was deactivated carboxylate anions, decomposed during distillation. Palomar et
by the addition of glucose, which was presumably used to al.43, 44 presented some work using activated carbon to adsorb
stabilize the palladium resulting in preventing it from aggregation. ionic
 Tetrahedron Letters 5
cellulose as the insoluble part while the other one was to
dissolve cellulose instead of the lignin. Recent reports on lignin
separation and dissolution in ionic liquids have been listed in
Table 2. In all these works, many analytical methods have been
applied to characterize both lignin products and ILs. These
methods included 2D NMR (HSQC), ATR-FTIR, 31P NMR, GPC,
and GC-MS, etc.
Oxidation of lignin in ionic liquids
More recently, Rogers et al.13 provided a critical review covering
oxidized lignin depolymerisation in ionic liquids. Xue et
al.45reported a pathway to degrade lignin in two ionic liquids, 1-
methyl-3-benzylimidazolium chloride (BnMIMCl) and 1-methyl-
3-benzylimidazolium trichloroacetate (BnMIMTFA) with HCl as
a catalyst. The effect of reaction atmosphere, reaction time,
temperature, and composition of different ionic liquids have been
investigated. The best condition reported for this oxidative
degradation was 120°C, 8h reaction time and lignin to BnMIMCl
mass ratio of 1:10. Additionally, the products (yield=70%)
obtained were monomers including acetovanilone (9.00%),
vanillic acid (12.27%), and other phenolic products (21.27%).
Further research needs to focus on purifying the products.
Eshtaya et al.46 developed a strategy to depolymerise lignin in
[C2mim][C2SO4] with 2,2’-azino-bis(3-ethylbenthiazoline-6-
sulfonic acid) diammonium salt (ABTS) as a mediator. The
oxidation process was evaluated by cyclic voltammetry
measurements to improve the oxidation of vetratryl alcohol and
lignin in ionic liquids. The redox process of ABTS radical
cations were monitored by CVs to show that the oxidation
current increased with the addition of lignin samples. The
valence of ABTS increased due to the oxidation of hydroxyl
Figure 4: Cations and anions of ionic liquids
groups on the α-carbon or γ-carbon, which resulted in the
oxidative depolymerisation of lignin. This study described an
liquids. Additionally, ionic liquids were also recovered by adding electrochemical depolymerisation of lignin in the black liquor
acetone, which can only be used in diluted solutions and using two ionic liquids as extraction solvents (butylimidazolium
depolymerisation reactions between ionic liquids and acetone are hydrogen sulphate [HC4im][HSO4] and triethylammonium
easier to occur. Coutino et al.44 also demonstrated a strategy to hydrogen sulphate [Et3NH][HSO4]) with H2O2 as oxidant. Lignin
recover ionic liquids from a water stream by using aluminum was degraded to produce a higher yield of aromatic acids, such as
salts. vanillic acid, benzoic acid, and 1,2-benzenedicarboxylic acids,
using [HC4im][HSO4] as the pretreatment solvent. However, this
Welton11 has reviewed biomass pretreatment using ionic ionic liquid was also oxidized during the process, and could not
liquids. Most of the work reviewed presented two ways for be recovered. Another ionic liquid, [Et3NH][HSO4], was not
biomass pretreatment: one was to selectively dissolve lignin affected by H2O2 showing a possibility of recyclability to yield
leaving guaiacol as the main products.

Table 2: Ionic liquids used for lignin separation and dissolution.

Entry Substrate Ionic liquidsa Conditions Recyclability Results
1 Oil palm biomass 47
[bmim][Cl] 110 °C N2, 8h Recyclable Yield=54%, Mw=1331 g/mol

2 Corn stover [bmim][Cl] 20°C, 50°C, centrifuge Recyclable Yield=13%

hydrolysate48
3 Eucalyptus bark49 [Et4N][i-PrNHC3SO3], 100°C Recyclable Yield=40%, with more C=O,
[Et4N][Me2NC4SO3], etc. C=C structure generated.
4 Wheat straw, [C2min][OAc] 120°C, 160°C, 90 min Recyclable Yield=32% with decreased β-O-
andloblolly pine50 4 linkage contents.
5 Organosolv lignin51 [C4C1im]MeSO3, [C4C1im]Br, 60°C Unrecyclable Solubility of organosolv lignin is
etc. 70%.
6 Lignocellulosic [Py][Ac], [Mim][Ac], 90°C, 24h Recyclable Yield=75% with decreased β-O-4
biomass52 [Pyrr][Ac] linkage contents.
7 Kraft lignin53 [PyFor], [PyAc], [PyPro] 75°C, 1h Recyclable Yield=95% Mw=1738 g/mol
54
8 Apple tree pruning [Bmin][MeSO4] 180°C, microwave 3 min Recyclable Yield=33% Mw=15549 g/mol

a
Ionic liquids: [bmim][Cl]: 1-butyl-3-methylimidazolium chloride, [Et4N][i-PrNHC3SO3],[Et4N][Me2NC4SO3]: amine-sulfonate functionalized ionic liquids,
[C4C1im]MeSO3 and [C4C1im]Br: dialkylimidazolium-based ionic liquid, [Py][Ac]: pyridinium acetate, [Mim][Ac]: 1-methylimidazolium acetate, [Pyrr][Ac]:
pyrrolidinium acetate, [PyFor]: pyridinium formate, [PyPro]: pyridinium propionate, [Bmin][MeSO4]: methylsulphate 1-butyl-3- methylimidazolium
 Tetrahedron Letters 6
Wasserscheid et al.55 published a strategy to use metal catalysts Conclusion
and ionic liquids for the oxidative depolymerisation of lignin. In
this work, several ionic liquids and metal salts were investigated This review summarized recent work involving catalytic
to depolymerise lignin. The results showed lignin degradation in oxidation of lignin and the application of ionic liquids in lignin
1-ethyl-3-methylimidazolium trifluoromethanesulfonate chemistry. As we mentioned above, incredible research advances
[EMIM][CF3SO3] with Mn(NO3)2 was the most effective reaction have been made in many fields recently. A number of strategies
system resulting in a maximum conversion of 66.3%. The with different catalysts as well as solvents have been reported.
products could vary from syringaldehyde to 1,6-dimethoxy-1,4- With oxidative depolymerisation of lignin, more functionalized
benzoquinone (DMBQ) with different reaction conditions and monomeric products, including vanillin, vanillic acid,
catalyst loading to provide the selectivity. The yield of DMBQ syringaldehyde, and syringic acid, were obtained. However, some
was about 21%. However, this reaction was carried out under of the reaction conditions were still not mild enough for
84×105 Pa in air. industrial application and some of the solvents used were not
green.
β-O-4 linkages targeted oxidation in ionic liquids
The introduction of ionic liquids in biomass processing has
A significant number of papers have focused on the β-O-4 provided a new insight into the field of lignin utilization. These
linkages in lignin, and the oxidative degradation in ionic liquids. studies have shown that the structure of lignin changed during the
Hallett et al.56 investigated the structural changes of Miscanthus process of lignin dissolution in ionic liquids resulting the
giganteus lignin isolated after extraction with a protic ionic degradation of lignin to yield monomeric products. Additionally,
liquid，1-butylimidazolium hydrogen sulfate ([HC4im][HSO4]). the recyclability of ionic liquids has also been studied. These
Lignin was analysed before and after reaction by several recyclable ionic liquids have a great potential for industrial
analytical techniques including 13C-NMR, 2D-NMR(HSQC), 31P- application in the field of biomass processing.
NMR, Py-GC-MS, GPC and element analysis. The results
showed lignin was deconstructed by β-O-4 bonds cleavage, The challenges for future research include, more attention is
which was verified by the decrease of molecular weight and the required for separation and purification of monomeric products
β-O-4 bonds signal in 2D-NMR (HSQC) spectra. The molecular and milder conditions for lignin depolymerisation are required.
weight of lignin decreased from Mw = 12,400 g/mol to Mw = Moreover, recyclable ionic liquids for lignin oxidation as both
6,770 g/mol. However, only preliminary analysis was carried out solvents and catalysts could be promising.
to confirm that the products that included monomeric syringols,
guaiacols and phenols with some sugar degradation products. Acknowledgments
Similarly, An et al.57 studied the structural changes and the
thermal properties of kraft lignin during its dissolution in The financial support of the ARC Industrial Transformation
cholinium ionic liquids. The results showed β-O-4 linkages in Research Hub-Bioprocessing Advanced Manufacturing Initiative
kraft lignin were broken with the formation of new β-β’ and β-5’ (BAMI), Monash University and the China Scholarship Council
bonds, which were detected by 2D-NMR(HSQC). GPC was also (CSC) is gratefully acknowledged.
used to measure the molecular weight of kraft lignin, which was
decreased from Mw = 15,390 g/mol to Mw = 10,460 g/mol after References and notes
being treated by [Ch][Lys]. Sun et al.58 also studied the chemical
transformations of lignin involving the ionic liquid pretreatment. 1 Li, C.; Zhao, X.; Wang, A.; Huber, G. W.; Zhang, T. Chem. Rev.,
2015, 115, 11559.
This study described the effect of 1-ethyl-3-methylimidazolium 2 Zakzeski, J.; Bruijnincx, P. C. A.; Jongerius, A. L.; Weckhuysen,
acetate ([C2mim][OAc]) pretreatment at different temperatures B. M. Chem. Rev 2010, 110, 3552.
and reaction times on the chemical structure of lignin. The results 3 Azadi, P.; Inderwildi, O. R.; Farnood, R.; Kin, D. A. Renewable
showed β-O-4 linkages, as well as β-β’ and β-5’ bonds, were Sustainable Energy Rev. 2012, 21, 506.
cleaved with a molecular weight decrease. Meanwhile, the 4 Lange, H.; Decina, S.; Crestini, C. Eur. Polym. J. 2013, 49, 1151.
5 Behling, R.; Valange, S.; Chatel, G. Green Chem. 2016, 18, 1839.
selectivity of degradation and repolymerisation of G-type units 6 Ma, R.; Xu, Y.; Zhang, X. ChemSusChem 2015, 8, 24.
and S units depended on the reaction temperature. Fu et al.59 7 Sadual, R. R.; Badamali, S. K.; Dapurkar, S. E.; Singh, R. K.
demonstrated a pathway to oxidatively depolymerise eucalyptus World J. Nano Sci. Eng. 2015, 5, 88.
kraft lignin by molecular oxygen in 1-butyl-3-methyl 8 Mota, M. I. F.; Rodrigues Pinto, P. C.; Loureiro, J. M.; Rodrigues,
imidazolium chloride [BMIM]Cl with CuO as catalyst. The A. E. Sep. Purif. Rev. 2016, 45, 227.
9 Zhang, Z. C. Adv. Catal. 2006, 49, 153.
major products were vanillin, vanillic acid, syringaldehyde and 10 Olivier-Bourbigou, H.; Magna, L.; Morvan, D. Appl. Catal., A
syringic acid, and acedosyringone. The results showed Cα-Cβ and 2010, 373, 1.
C4-O bonds in β-O-4 linkages were cleaved. The optimal reaction 11 Welton, T. Chem. Rev. 1999, 99, 2071.
condition for this reaction was 150 °C with a pressure of oxygen 12 Moens, L.; Khan, N. In Green Industrial Application of Ionic
up to 6MPa. Diop et al.60 presented a novel strategy to liquids; Springer, 2003; Vol.92, pp 157-171.
13 Chatel, G.; Rogers, R. D. ACS Sustainable Chem. Eng. 2013, 2,
depolymerise lignin in butyl-1,8-diazabicyclo[5.4.0]undec-7- 322.
enium chloride ([DBUC4][Cl]) without a catalyst. In this work, 14 Chakar, F. S.; Ragauskas, A. J. Ind. Crops Prod. 2004, 20, 131.
kraft lignin was placed in [DBUC4][Cl] and the reaction was 15 Shilpy, M.; Ehsan, M. A.; Ali, T. H.; Hamid, S. B. A.; Ali, M. E.
performed in an oven at 150, 200 and 250 °C. The FTIR, 1H RSC Adv. 2015, 5, 79644.
NMR, and 31P NMR analyses indicated the β-O-4 bonds were 16 Díaz-Urrutia, C.; Chen, W.-C.; Crites, C.-O.; Daccache, J.;
Korobkov, I.; Baker, R. T. RSC Adv. 2015, 5, 70502.
cleaved and the demethylation of lignin occurred. The
17 Rahimi, A.; Azarpira, A.; Kim, H.; Ralph, J.; Stahl, S. S. J. Am.
depolymerised lignin products were analysed by GPC to give the Chem. Soc. 2013, 135, 6415.
molecular weight, which showed the molecular weight was 18 Nanayakkara, S.; Patti, A. F.; Saito, K. Aust. J. Chem. 2013, 66,
decreased by 23, 70, and 58% at the treatment temperature of 150, 60.
200, and 250°C, respectively. The major products from the 19 Nanayakkara, S.; Patti, A. F.; Saito, K. Green Chem. 2014, 16,
1897.
reaction were oligomers and the best reaction temperature was
20 Nanayakkara, S.; Patti, A. F.; Saito, K. ACS Sustainable Chem.
200 °C. Eng. 2014, 2, 2159.
 Tetrahedron Letters 7
21 Dai, J.; Nanayakkara, S.; Lamb, T. C.; Clark, A. J.; Guo, S.-X.; 43 Lemus, J.; Palomar, J.; Gilarranz, M. A.; Rodriguez, J. J.
Zhang, J.; Patti, A. F.; Saito, K. New J. Chem. 2016, 40, 3511. Adsorption. 2011, 17, 561.
22 Ouyang, X.; Ruan, T.; Qiu, X. Fuel Process. Technol. 2016, 144, 44 Palomar, J.; Lemus, J.; Gilarranz, M.; Rodriguez, J. Carbon 2009,
181. 47, 1846.
23 De la Cruz, F. B.; Dittmar, T.; Niggemann, J.; Osburn, C. L.; 45 Xue, L.; Yan, L.; Cui, Y.; Jiang, M.; Xu, X.; Zhang, S.; Gou, J.;
Barlaz, M. A. Environ. Eng. Sci. 2015, 32, 486. Zhou, Z. Environ. Prog. Sustainable Energy 2015, 35, 809.
24 Sarkanen, K. V.; Ludwig, C. H. In Lignins: occurrence, 46 Majd, E.; Ejigu, A.; Stephens, G.; Walsh, D.; Chen, G. Z.; Croft,
formation, structure and reactions. Sarkanen, K. V.; Ludwig, C. H. Eds.; A. Faraday. Discuss. 2016.
Wiley Interscience, 1971; Vol 1, pp.444-448. 47 Mohtar, S.; Busu, T. T. M.; Noor, A. M.; Shaari, N.; Yusoff, N.;
25 Sun, L.; Spencer, R. G.; Hernes, P. J.; Dyda, R. Y.; Mopper, K. Bustam, M.; Mutalib, M. A.; Mat, H. Bioresour. Technol. 2015, 192, 212.
Limnol. Oceanogr., Methods 2015, 13, 1. 48 Underkofler, K. A.; Teixeira, R. E.; Pietsch, S. A.; Knapp, K. G.;
26 Ma, Y.; Du, Z.; Liu, J.; Xia, F.; Xu, J. Green Chem. 2015, 17, Raines, R. T. ACS Sustainable Chem. Eng. 2015, 3, 606.
4968. 49 Yan, P.; Xu, Z.; Zhang, C.; Liu, X.; Xu, W.; Zhang, Z. C. Green
27 Hanson, S. K.; Baker, R. T. Accounts. Chem. Res. 2015, 48, 2037. Chem. 2015, 17, 4913.
28 Mottweiler, J.; Puche, M.; Räuber, C.; Schmidt, T.; Concepción, 50 Sathitsuksanoh, N.; Holtman, K. M.; Yelle, D. J.; Morgan, T.;
P.; Corma, A.; Bolm, C. ChemSusChem 2015, 8, 2106. Stavila, V.; Pelton, J.; Blanch, H.; Simmons, B. A.; George, A. Green Chem.
29 Zhou, X. F. Environ. Prog. Sustainable Energy 2015, 34, 1120. 2014, 16, 1236.
30 Shimazaki, Y.; Yamauchi, O. Indian J. Chem., Sect A. 2011, 50, 51 Wang, Y.; Wei, L.; Li, K.; Ma, Y.; Ma, N.; Ding, S.; Wang, L.;
383. Zhao, D.; Yan, B.; Wan, W. Bioresour. Technol. 2014, 170, 499.
31 edai, a -Urrutia, C.; Baker, R. T.; Wu, R.; Silks, L. P.; 52 Achinivu, E. C.; Howard, R. M.; Li, G.; Gracz, H.; Henderson, W.
Hanson, S. K. ACS Catal. 2011, 1, 794. A. Green Chem. 2014, 16, 1114.
32 Mottweiler, J.; Rinesch, T.; Besson, C.; Buendia, J.; Bolm, C. 53 Rashid, T.; Kait, C. F.; Regupathi, I.; Murugesan, T. Ind. Crops
Green Chem. 2015, 17, 5001. Prod. 2016, 84, 284.
33 Gao, T.-T.; Zhou, X.-F.; Zhu, Z.-L. Drewno: prace naukowe, 54 Prado, R.; Erdocia, X.; Labidi, J. J. Cleaner Prod. 2016, 111, 125.
doniesienia, komunikaty 2015, 58, 79. 55 Stärk, K.; Taccardi, N.; Bösmann, A.; Wasserscheid, P.
34 Dawange, M.; Galkin, M. V.; Samec, J. S. ChemCatChem 2015, 7, ChemSusChem 2010, 3, 719.
401. 56 Brandt, A.; Chen, L.; van Dongen, B. E.; Welton, T.; Hallett, J. P.
35 Patil, N. D.; Yao, S. G.; Meier, M. S.; Mobley, J. K.; Crocker, M. Green Chem. 2015, 17, 5019.
Org. Biomol. Chem. 2015, 13, 3243. 57 An, Y.-X.; Li, N.; Wu, H.; Lou, W.-Y.; Zong, M.-H. ACS
36 Pu, Y.; Jiang, N.; Ragauskas, A. J. J. Wood Chem. Technol. 2007, Sustainable Chem. Eng. 2015, 3, 2951.
27, 23. 58 Wen, J.-L.; Yuan, T.-Q.; Sun, S.-L.; Xu, F.; Sun, R.-C. Green
37 Earle, M. J.; Seddon, K. R. Pure Appl. Chem. 2000, 72, 1391. Chem. 2014, 16, 181.
38 Seddon, K. R.; Stark, A.; Torres, M.-J. Pure Appl. Chem. 2000, 59 Tian, J.; Fu, S.; Lucia, L. A. J. Wood Chem. Technol. 2015, 35,
72, 2275. 280.
39 Hussey, C. L. Pure Appl. Chem. 1988, 60, 1763. 60 Diop, A.; Jradi, K.; Daneault, C.; Montplaisir, D. BioResources
40 Carlin, R. T.; Wilkes, J. S. Chemistry of Nonaqueous Solutions: 2015, 10, 4933.
Current Progress, G. Mamantov, AI Popov, Eds. VCH:New York, NY, 1994,
Vol.72(3) pp 145-170.
41 Mai, N. L.; Ahn, K.; Koo, Y.-M. Process. Biochem. 2014, 49, 872.
42 Earle, M. J.; Esperança, J. M.; Gilea, M. A.; Lopes, J. N. C.;
Rebelo, L. P.; Magee, J. W.; Seddon, K. R.; Widegren, J. A. Nature 2006,
439, 831.
 Tetrahedron Letters 8
Recent developments in chemical degradation of lignin: catalytic oxidation
and ionic liquids
Jinhuo Dai, Antonio F. Patti, and Kei Saito
School of Chemistry, Monash University, Clayton, Victoria 3800, Australia.
Email: [email protected]

Highlights
 Various significant pathways of catalytic lignin oxidation were reviewed.
 Strengths and weaknesses between different lignin oxidation routes were discussed.
 Ionic liquids for the oxidative lignin depolymerisation were also introduced.

———
 Corresponding author. Tel.: +61-3-9905-4600; e-mail: [email protected]