Chemo- and Regioselective Synthesis of Arylated γ-Valerolactones from Bio-based Levulinic Acid with Aromatics Using H-β Zeolite Catalyst

Article abstract of DOI:10.1002/cctc.201801782

Catalytic coupling of biomass-based molecules to value-added chemical intermediates is an interesting area in biomass research. Arylated γ-valerolactones (Agvls), promising pharmaceutical intermediates that have significant biological activity, are primar

Full text of DOI:10.1002/cctc.201801782

Accepted Article
Title: Chemo- and regioselective synthesis of arylated γ-valerolactones
from bio-based levulinic acid with aromatics using H-β zeolite
catalyst
Authors: Sreedhar Gundekari and Kannan Srinivasan
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: ChemCatChem 10.1002/cctc.201801782
Link to VoR: http://dx.doi.org/10.1002/cctc.201801782
A Journal of
www.chemcatchem.org

Manuscript
Click here to
access/download;Manuscript;Revised_Manuscript_Clean_Kan
ChemCatChem
10.1002/cctc.201801782
FULL PAPER
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
Chemo- and regioselective synthesis of arylated γ-valerolactones
from bio-based levulinic acid with aromatics using H-β zeolite
catalyst
Sreedhar Gundekari,[a, b] and Kannan Srinivasan *[a,b]
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
Abstract: Catalytic coupling of biomass-based molecules to value-
is easily obtained from abundant waste/surplus carbohydrate (C6-
Glucose/C5-Xylose) biomass like sawdust, paper mill sludge,
tobacco chops, sugarcane bagasse and wheat by the acid
catalysed dehydration followed by subsequent hydration using
various homo/heterogeneous catalysts.[7] Multiple functionalities
like carboxyl, carbonyl, methyl, and methylene in LA ensures its
facile participation for several organic transformations.[8]
LA, being one of the carbohydrates derived building block
chemical identified by DOE,[9] is a promising biomass based
chemical platform for industrial use through R&D. Recently,
added chemical intermediates is an interesting area in biomass
research.
Arylated
γ-valerolactones
(Agvls),
promising
pharmaceutical intermediates that have significant biological activity,
are primarily synthesized currently through petro-route. In this paper,
we report successful biomass-based synthesis of Agvls using levulinic
acid (LA) and oxygen or sulphur- substituted aromatics over H-β
zeolite as catalyst under solvent-free conditions. Under optimized
condition, LA and anisole render 90% conversion of former with 82%
yield of para-substituted γ-lactone. C-C bond formation followed by
intra-molecular esterification is witnessed in the course of the reaction, organic transformations of LA in presence of other biomass
which is highly chemo- and regioselective. Though catalyst
deactivated while reuse due to deposition of organic carbon moieties
as deduced from several physicochemical techniques, it could be
regenerated by simple calcination.
derived molecules to industrially valuable products (Scheme 1)
are being pursued all over the world. Some prominent examples
are: polymer precursors (ketals) through condensation of LA with
glycerol,[10] diphenolic acid (a renewable plasticizer-alternative to
bisphenol A) from LA reacting with phenol,[11] alkyl levulinates
(
fuel oxygenates) via esterification of LA with C1-C4 linear and/or
[
12]
branched alcohols, and production of liquid alkanes (fuels) from
LA with formic acid via intermediate of γ-valerolactone (Gvl). It is
worth mentioning here that formic acid is the by-product in LA
synthesis from C6-sugars that can act as a hydrogen source for
Introduction
The ever-increasing demand for fossil fuels and petroleum-
derived products is causing
conventional fuel reserves. About 90% of today’s organics are
petrochemical based. This has escalated the need for alternative
and renewable sources for fuels and commodity chemicals.[1]
a
depletion of the Earth’s
[13]
the synthesis of Gvl, a key step in a bio-refinery.
Biomass is the most promising alternative feedstock for fuels and
value-added chemicals.[2] Use of biomass also increases the rural
economics and results in a decrease in greenhouse gas (GHG)
emissions compared to petroleum-based feedstock.[3] The major
components of biomass are plant cell wall (lignocellulose) and
plant seeds (triglycerides). The primary platform chemicals of
lignocellulose/triglyceride biomass are sugars, alcohols, furans,
alkenes, carboxylic acids, esters, carbonyl compounds, phenolics
and glycerol-derived molecules which could be obtained via
biological and/or chemical transformations.[4]
Catalytic transformations of biomass to organics like fuels,
chemicals, polymers etc. are likely to have an immense impact on
future generations.[5] Levulinic acid (LA), a biomass-derived keto
carboxylic acid, serves as an important building block for valuable
fuels and chemicals obtainable via catalytic transformations.[6] LA
Scheme 1. Valuable products from catalytic transformations of LA with
[a]
[b]
Sreedhar Gundekari, Kannan Srinivasan
other biomass-based molecules
Inorganic Materials and Catalysis Division
CSIR-Central Salt and Marine Chemicals Research Institute
GB Marg, Bhavnagar - 364 002, India
E-mail: skannan@csmcri.res.in; kanhem1@yahoo.com
Sreedhar Gundekari, Kannan Srinivasan
Moreover, LA in presence of furfural (hemicellulose-derived)
undergoes aldol condensation using base catalysts to form an
[14]
aldol adduct which is a precursor for polymer and fuel.
Li’s
Academy of Scientific and Innovative Research
CSIR-Central Salt and Marine Chemicals Research Institute
GB Marg, Bhavnagar - 364 002, India
Supporting information for this article is given via a link at the end of
the document.
research group reported lipase-catalyzed esterification of LA with
HMF (cellulose-derived) in 2-methyltetrahydrofuran (2-MeTHF)
medium, which formed HMF-levulinate that may be useful as fuel
[15]
additive. Furthermore, LA is used in catalysed ring opening of
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
epoxidized methyl oleate (EMO) for the preparation of branched
oleochemicals; in presence of LA, EMO formed two products
(
chosen for catalyst screening studies as their multifunctional
characteristics such as highly crystalline, thermally stable, tunable
acidity, reusability, and shape selectivity that are used in many
organic transformations including in petrochemical industry.[
Further, zeolites have been demonstrated for excellent activity for
diverse catalytic transformation of biomass/biomass-derived
compounds, and were also reported as good acidic supports.[24]
Screening of catalysts was performed with 20 wt% (w.r.t.
LA) of different zeolitic materials using 1:1 molar ratio of LA to
anisole (Table 1). Blank reaction (without catalyst) and among the
zeolites screened, only β-zeolites namely Na-β and H-β were
active towards the reaction, which showed 22 and 27%
conversion of LA with excellent selectivity of 91 and 92% to para-
substituted Agvl (Table 1, entries 2 and 5). The high activity of β-
zeolite is probably due to unique pore topology and presence of
local defects in their structures through octahedral extra-
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
ketal and ester) by varying the reaction conditions.[16] The
23]
dehydrated product of LA such as angelica lactone (AL) reacts
with another two AL and/or two 2-methylfuran in presence
catalysts form C-C bonded alkylated furan and lactone products
which are precursors for transportation fuels.[17] LA functionality is
also reported for the reductive amination reaction for the
preparation of pyrrolidones (industrial solvents) using amines
under H
2
.[18]
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
Among the mentioned LA-based products; Gvl has been
studied extensively for its preparation and applications. It can be
prepared through hydrocyclization of LA under H using metal
2
supported catalysts, and we reported recently this conversion
using in situ generated Ru catalyst via hydrous ruthenium
oxide.[ Gvl, a promising precursor for liquid alkanes, polymers
and itself a greener solvent, is a member of the class of γ-
lactones.[20] γ-lactone containing moieties are relevant in many
areas like pharmaceutical, agrochemicals, polymers, and
precursors to the production of furans, cyclopentenones and
natural products.[21] In particular, certain aryl/methyl substituted γ-
lactones have significant biological activity towards cytotoxicity
19]
6
framework aluminium (AlO ) that generates Lewis acidic
properties, which results in efficient conversion and product
selectivity in several organic transformations, as reported in the
literature.[ Between Na and H-β zeolite, the latter showed
comparatively better activity and thus the reaction parameter
variation studies were conducted further with this catalyst.
25]
(
against cancer cells), anti-inflammatory ability and helps in
increasing human growth hormone levels for enhancing the
quality of life.[22] Currently, such arylated γ-valerolactones (Agvls)
are prepared from petroleum-derived feedstock only. The
approach to synthesize both existing & novel Agvls from biomass
based chemicals is interesting and has been envisioned to have
a significant impact on pharmaceutical research.
Continuing our interest in the synthesis and value addition
of biomass-based chemicals, we report here an efficient
transformation of biomass-based LA with aromatics to Agvls
using recyclable H-β zeolite catalyst under solvent-free conditions.
Table 2. Optimization studies for Agvl formation from LA with anisole using
[a]
H-β zeolite catalyst
Entry
T.
Catalyst
Molar
ratio
Solvent
Conv. of
LA
(%)
Yield of
lactone
(%)
[b]
(˚C)
(wt
%)
w.r.t LA
1
2
3
4
5
6
7
8
9
40
80
10
10
10
10
10
10
10
10
10
10
10
10
30
30
30
30
50
50
50
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:1
1:2
1:4
1:6
1:4
1:4
1:4
1:4
1:4
1:4
1:4
Neat
Neat
Neat
1-2
4-5
16
80
n.r
n.r
n.r
n.r
34
51
63
61
78
52
39
33
85
90
89
trace
trace
15
n.o
-
-
-
-
30
47
59
58
70
43
27
18
77
82
81
Results and Discussion
120
120
120
120
120
120
150
150
150
150
150
150
150
150
150
150
150
3
CH -OH
Table 1. Screening of catalysts[a]
DMSO
ACN
THF
CH
Neat
Neat
Neat
Neat
Neat
Neat
Neat
Neat
Neat
Neat
Neat
1
1
0
1
12
13
14
15
16
[
d]
[e]
f]
[
Entry
Catalyst
Conv. of
LA (%)
Yield
lactone (%)
of
Sel. of lactone
(%)
17
[b]
[b]
[c]
18
19[
c] [h]
1
2
3
4
5
Blank
Na-β
Na-Y
Na-ZSM-5
H-β
n.r
22
n.r
n.r
27
-
20
-
-
25
-
91
-
-
92
[
2
a] LA (4.3 mmol, 500 mg), anisole (4.3-25 mmol (465.5-1793 mg)), H-β (50-
50 mg), solvent (2.5 ml), 6 h. [b] Theoretical conversion of LA and yield of
Agvl (isolated using column chromatography). [c] 12 h. [d, e, f] Reaction with
MeL, EtL, BuL respectively. [h] Reaction with isolated anisole (from product
mixture). n.r-No reaction, n.o- Not observed, ACN-Acetonirile, CH-
Cyclohexane.
[a] LA: anisole molar ratio-1:1 (LA (1g; 8.6 mmol), anisole (8.6 mmol)),
catalyst (20 wt% w.r.t LA), 120 °C, 6 h. [b] Theoretical conversion of LA and
yield of Agvl (isolated using column chromatography). n.r -No reaction.
Generally, an increase in the reaction temperature
increases the rate of the reaction, as this factor raises the average
kinetic energy of the reactant molecules that leads to effective
Formation of arylated γ-valerolactones (Agvls) from LA with
aromatics is an acid catalysed reaction. Thus, zeolites were
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
collision. By considering this fact, we varied reaction temperature
which revealed that the reaction is critically dependent on the
reaction temperature wherein the yield of γ-lactone gradually
increased from 2% to 30% with an increase in the temperature
from 40 to 150 °C under solvent-free conditions with 1:1 molar
ratio of reactants (Table 2, entries 1-3 and 9). In presence of either
polar (both protic and aprotic) or non-polar solvents, under similar
conditions, the catalytic activity for γ-lactone formation was
hampered; in the case of methanol as solvent, we observed
methyl levulinate with 80% conversion and 100% selectivity while
other solvents such as dimethyl sulfoxide, acetonitrile,
tetrahydrofuran, and cyclohexane did not show any conversion of
LA (Table 2, entries 4-8). Though the reasons are unclear, the
dielectric/polarity of the medium and the influence of solvent on
the acidic sites are probably the reasons for poorer interaction
between the reactant with zeolite, and in turn on the activity.
On increasing the anisole concentration from 1 to 6
equivalent w.r.t LA, we observed an increase in the conversion of
LA and with this yield of γ-lactone also increased up to 59% for 4
equivalent anisole (sufficient for optimal interaction) and stabilizes
even on a further increase (6 equivalent) in the amount of anisole
(Table 2, entries 9-12). Thus, we chose 1:4 (LA: anisole)
equivalent for further experiments. It is worth mentioning here that
during the reaction, the keto carbon of LA gets partial positive
charge (see mechanism); and to neutralize sufficient to excess of
aromatic molecules are needed.
Reaction conducted using LA esters such as methyl
levulinate (MeL), ethyl levulinate (EtL) and butyl levulinate (BuL)
showed lesser conversion towards the formation of γ-lactone
compared to that of LA (Table 2, entry 14-16). Mechanistically
when using LA as reactant, the cyclization step is an
intramolecular esterification while for levulinic ester cyclization
involves intramolecular trans-esterification. Compared to trans-
esterification, esterification is more favourable, and thus LA
showed higher conversion than levulinic esters and this is in
accordance with our earlier report with evidence on cyclization of
LA and its esters for Gvl production.[19b, 26] Furthermore, an
increase in the chain length (from MeL to BuL) influences the
diffusion of the molecules (besides subtle increase in the
molecular hydrophobicity) affects the approach of molecule to the
active acidic centres of the zeolite and thus could be reason for
the reduced activity. Interestingly, in all three LA esters, nearly 3-
5% of LA as side product was formed probably due to acidic
unreacted/excess amount of anisole was recovered while
separation of product (γ-lactone) using column chromatography,
and the recovered anisole is re-used for the reaction that showed
similar conversion of LA (89%) and yield of γ-lactone (81%) under
optimised reaction conditions (Table 2, entries 18 and 19).
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
Table 3. Synthesis of Agvls from LA with various aromatics using H-β zeolite
catalyst[
a]
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
2
hydrolysis of LA esters using H O formed during the reaction.
From the above discussion, we concluded that compared to LA
esters, the LA is an effective reactant for the formation of γ-
lactone, and thus used as reactant for further experiments.
Further, we varied the catalyst amount (10 - 50 wt% w.r.t
[a] LA to aromatic molar ratio is 1:4 (LA (4.3 mmol), aromatics (17.2 mmol)),
H-β (50 wt% w.r.t. LA), 150 °C for 12 h. [b] Theoretical conversion of LA and
yield of Agvls (isolated using column chromatography). [c] GC-MS
conversion and yield. [d] 110 °C, [e] 85 °C. n.r-No reaction, n.o-Not
observed.
LA), wherein a maximum of 77% γ-lactone yield was obtained at
The substrate scope for the synthesis of γ-lactones were
extended with molecules having linear alkoxy benzenes (ethoxy
to butoxy benzenes). Increasing the alkyl chain length slightly
increased the conversion of LA with the retention of selectivity of
para-substituted γ-lactones (Table 3, entries 2-4). We further
strived to extend the reactant scope using simple aromatic
hydrocarbon cumene, but in this case, no reaction was observed.
This could be due to the fact that the aromatic ring in cumene is
not electronically rich enough to participate in the nucleophilic
attack on the carbonyl carbon of LA. The increase in the ring
electron density is thus provided by the lone pair of electron
present on the heteroatom in the substrates with electron
donating substituents. Thus, the absence of such electron
50 wt% of catalyst (Table 2, entries 13 and 17). An increase in the
wt% of catalyst enhances the number of acidic sites and thereby
increases interaction of LA with the active centres and in turn
resulting in higher conversion of reactants towards the formation
γ-lactone. Reaction time variation studies showed a slight
increase in the product yield after 12 h reaction (Table 2, entries
17 and 18). From above parametric studies, the best yield of γ-
lactone was obtained with 4:1 molar ratio of anisole to LA under
solvent-free conditions at 150 °C using 50 wt% catalyst loading in
12 h (Table 2, entry 18). The excess equivalent amount of anisole
to the reaction generates waste while conducting bulk
experiments. Thus, to avoid this drawback, after the reaction the
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
donating substituent in cumene precludes the formation of γ-
lactone (Table 3, entry 5).
treatment showed similar catalytic activity as that of fresh catalyst
for several further cycles (Figure 1, cycle 6-9).
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
The above explanation was further supported by the
observation of 48% conversion of LA while using thioanisole as
aromatic moiety, that showed 83% selectivity of para isomeric γ-
lactone (Table 3, entry 7). Thus, the lone pair of electrons on a
heteroatom containing substituent on the benzene ring increases
the electron density on the para position and facilitates the
nucleophilic attack on the carbonyl carbon of LA. Further, we
explored the synthetic protocol by using sulphur containing five-
membered heterocycles, chosen owing to higher resonance
energy compared to oxygen and nitrogen-containing heterocycles.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
2-methylthiophene and thiophene showed excellent selectivity
towards the γ-lactone formation (90% and 80%) with 93% and
96% conversion of LA (Table 3, entry 8 and 9).
The nitrogen and phosphorous containing aromatics did not
show γ-lactone formation under the reaction conditions studied
over H-β catalyst. The N,N-Dimethyl aniline formed dimerised
product (tetramethyl-[1,1'-biphenyl]-diamine) as confirmed by
GC-MS analysis while triphenylphosphine resulted in the
formation of triphenylphosphine oxide as a product (Table 3, entry
Figure 1. Recyclable studies of H-β zeolite
LA to aromatic molar ratio is 1:4 (LA (4.3 mmol, 0.5 g), anisole (17.2 mmol,
1.86 g)), H-β (50 wt % w.r.t. LA), 150 °C for 6 h. Isolated yield of the product
has been considered here.
10 and 11). Para isomer was obtained as the exclusive product
for six-membered ring containing substrates, suggesting a
product shape selectivity exhibited by the catalyst. The para
isomers being less bulky can easily diffuse in the zeolitic pores
compared to ortho- and meta- isomers. To corroborate, we
conducted a reaction using 1-ethoxy-4-methoxybenzene in which
the para position of the methoxy is blocked. The absence of γ-
lactone supports the regioselectivity towards para isomer under
our experimental conditions (Table 3, entry 6).
Assessment of recyclability of the catalyst is beneficial for
industrial applications, as it helps in reducing the cost of the
process. After the reaction, the colour of the catalyst (H-β)
changed from white to red. The used catalyst was washed with
DCM and dried at 100 °C for 12 h. The oven dried catalyst (termed
UH-β) was reused under similar reaction conditions that showed
a decrease in the yield of γ-lactone up to 40% without any
compromise in selectivity (Figure 1, cycle 2). The decrease in the
catalytic activity is due to adherence of organic carbon that formed
during the reaction which probably blocked the acidic sites of the
catalyst, and in turn, decreased the catalytic activity. The detailed
study of organic carbon deposition in used β-zeolite is discussed
in the catalyst characterization section.
Catalyst characterization
Figure 2. Physical appearance of various stages of β-zeolites
The presence of organic carbon in the UH-β and its removal
in UH-βC on calcination were characterized using multiple
analytical tools like PXRD, FT-IR, CHNS, TOC, CP MAS-NMR
The used catalyst (UH-β) was calcined at 550 °C for 3 h to
remove the adhered organic carbon under air. After calcination,
the catalyst colour changed back to white from red (UH-β) and is
henceforth referred to as UH-βC. The UH-βC showed similar
reactivity for the synthesis of γ-lactone as that of fresh H-β catalyst,
resulting in similar yield and selectivity of the product (Figure 1,
cycle 3). However, the product yield/LA conversion marginally
decreased upon recycling (Figure 1, cycle 4 and 5). The decrease
in the activity is presumably due to the depletion of Brönsted
(13
C, and 27Al), SEM, textural measurements (specific surface
area and pore volume), TGA, TPD and UV-visible spectroscopy.
The physical appearance of different stages of β-zeolite (H-β, UH-
β, and UH-βC) are given in Figure 2.
The PXRD of the H-β matched well with the precursor Na-β
suggest that the crystalline structure of zeolite did not change
upon its conversion. Further, the crystallinity of the catalyst was
not affected even after several catalytic cycles with intermittent
calcination Figure 3.
+
acidic sites (H ) through their dissolution in water, a by-product
formed in the reaction. The calcined catalyst was treated with
dilute mineral acid followed by washing (with water) and drying at
The FT-IR of UH-β showed additional bands when
compared with that of fresh H-β zeolite in the region 1500-2000
120 °C for 3 h. The regenerated catalyst (UH-βC) after acid
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
cm-1 which disappeared upon calcination (UH-βC) (see Figure 1
in the ESI). In other words, FT-IR conforms the deposition of
organic carbon moiety in UH-β zeolite presumably having
been supported by TOC measurements (Table 4). Thus, the
removal of organic carbon moieties upon calcination causes the
calcined catalyst to behave similar to that of the fresh catalyst.
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
carbonyl/carboxy functional groups. The NH
3
-TPD analysis
showed a decrease in the total amount of NH adsorbed from 0.70
3
Table 4. CHNS and TOC analysis of β-zeolite catalysts
mmol/g for H-β to 0.58 mmol/g for UH-β, further supporting the
blockage of acidic sites in UH-β catalyst due to the presence of
organic carbon. The regenerated catalyst (UH-βC) showed
Element
CHNS
UH-β
8.89
TOC
UH-β
9.0
H-β
UH-βC
H-β
UH-βC
Carbon
0.79
0.26
-
-
3
restoration in acidity (0.69 mmol/g NH ) (see Figure 2 in the ESI).
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
TGA analysis of the catalysts (Figure 5a) showed 10%
weight loss for fresh H-β in the temperature range 50-150 °C, due
to desorption of physisorbed H
weight loss, UH-β showed weight loss around 160-320 °C and
50-620 °C which corresponds to the removal of deposited
2
O molecules. In addition to this
3
organic carbon moiety in the catalyst, amounting to ~20% loss in
weight. The weight loss mechanism of carbon under oxygen
environment is common for a typical organic compound, wherein
initially, the organic carbon material adsorbs oxygen with a gain
in weight while a further increase in the temperature leads to
oxidation with an evolution of CO
weight.[28] The calcined catalyst (UH-βC) showed weight loss
10%) similar like fresh H-β at the temperature range 50-150 °C,
2
/CO and thereby reduces the
(
as the organic carbon has already been removed by prior
calcination.
Figure 3. PXRD of β-zeolite catalysts
The Py-FTIR (Figure 4), showed bands at 1445 and 1595
-1
cm for fresh H-β catalyst indicating the presence of Lewis-acidic
sites,[27] that are responsible for facilitating this reaction. These
bands, however, disappeared for the used catalyst (UH-β) and
reappeared for the calcined catalyst (UH-β) augmenting the
relationship between Lewis acidity and catalytic activity. Thus, the
removal of deposited organic carbon moieties that adhere over
Lewis acidic sites upon calcination restores the acidic sites. In
other words, the organic carbon moieties formed in the course of
the reaction blocked the Lewis acidic sites of the UH-β zeolite
which could be restored by removing them by calcination. In so
forth, the absence of these sites is the likely reason for the poor
activity exhibited by Na-Y and Na-ZSM-5 (Figure 4a and b),
though their textural properties were not significantly different
from Na/H-β (Table 1 in the ESI).
Figure 4. Py-FTIR spectra of β-zeolite catalysts; (a) Na-Y, (b) Na-ZSM-5, (c)
Na-β, (d) H-β, (e) UH-β, and (f) UH-βC
Furthermore, Py-FTIR of both Na/H-β zeolite showed bands
at 1545 cm-1 ascribed to Brönsted acidic sites (probably due to
incomplete exchange) and the band at 1490 cm-1 attributed to the
mixture of both acidic sites (Brönsted and Lewis) (Figure 4).[18]
The slightly higher activity of H- β over Na- β is probably due to
cooperative mechanism of both sites (see mechanism).
Incidentally, for UH-β, though had Brönsted acidic sites (Figure 4
e), it was not enough to drive the reaction further necessitating
the requirement of Lewis acidic sites.
The organic carbon deposition in the used catalyst (UH-β)
has also been confirmed by the increase in carbon content
measured through CHNS and TOC (total organic carbon). The
CHNS analysis (Table 4) of catalysts showed an increase to 9%
carbon for UH-β from 0.8% for H-β. This value decreased to
The UV-visible spectra of fresh H-β catalyst did not show
any transitions in the entire wavelength range studied suggest the
obvious absence of UV active groups in β-zeolite. However, in the
case of used H-β catalyst (UH-β) three major transitions were
observed around 630, 515 and 390 nm corroborating the
presence of deposited organic carbon in the zeolite (Figure 5b).
From the above observation, one may conclude the presence of
UV active functional groups in such deposited organic moieties
corroborating FT-IR results. The reactivated catalyst (UH-βC), as
anticipated, did not show any transition in the UV-visible spectrum
similar to that of fresh catalyst (H-β). These results also clearly
provide conclusive support for the removal of deposited organic
carbon by calcination.
~0.5% for UH-βC. Such variation in the carbon content has also
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
The scanning electron microscopic (SEM) analysis of H-β,
calcination, a restoration of both surface area and pore volume
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
2
UH-β and UH-βC are shown in Figure 6. The catalyst (H-β)
depicted spherical morphology with regular arrangement. On the
contrary, UH-β catalyst showed irregular morphology with thread
and rod like structures of organic carbon moieties. In view of this,
LA and anisole molecules have diffusion limitation towards the
active acidic sites of the zeolite and thus causes a decrease in the
catalytic activity. However, on removal of the organic carbon for
the calcined catalyst (UH-βC), the rods and threads were absent
and the morphology obtained was also similar to that of the fresh
catalyst (H-β), the initial activity was restored.
was observed for UH-βC: surface area (535 m /g) and pore
3
volume (0.33 cm /g).
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
Figure 6. SEM images of zeolites
Solid state NMR is an important tool to predict the structural
changes in zeolite as a consequence of the catalytic reactions.
The 13C, and 27Al CP-MAS NMR of all three catalysts (H-β, UH-β,
1
3
and UH-βC) were studied. C CP-MAS NMR has earlier been
deployed for the identification of carbon deposition in the zeolites
like Y, β, and ZSM-5.[28e, 29] Absence of peaks in 13C CP-MAS
NMR spectrum of fresh H-β zeolite supported the absence of
carbon containing moieties in the catalyst. However, UH-β
catalyst showed peaks at 29, 50, 87, 114, and 181 δ ppm. The 29
and 50 δ ppm peaks may be of saturated alkyl carbon, the 87 and
Figure 5. TGA (a) and UV-visible spectra (b) of β-zeolite catalysts
114 δ ppm peaks correspond to alcohol/ether/alkyne carbon. The
181 δ ppm supports the presence of carboxylic acid group. Thus,
The SEM-energy dispersive X-ray elemental analysis
(SEM-EDX) of the catalysts were recorded and shown in Figure 3
in the ESI. All samples were analysed in a specimen stub that had
11% carbon. The EDX of UH-β showed 22% carbon, in other
words, suggest 11% of carbon in UH-β, whose value is closer to
the TOC and CHNS measurements. Furthermore, the EDX-maps
of UH-β zeolite revealed the location of organic carbon moiety in
zeolite matrix (see Figure 4 in the ESI).
the
deposited
organic
carbon
could
probably
be
alcoholic/carboxylic acid based material. The reactivated catalyst
(
(
UH-βC) also did not show any peaks in the 13C CP-MAS NMR
Figure 7a).
The 27Al CP-MAS NMR of catalysts given in Figure 7b,
showed primarily two peaks. The major peak approximately in the
range of 54-55 δ ppm attributed to 4-coordinated tetrahedral
framework of aluminium (AlO
of 0.15-0.62 δ ppm corresponding to octahedral extra-framework
aluminium (AlO
).[28e, 30] On comparing H-β and UH-βC, the
octahedral aluminium peak of UH-β zeolite showed larger
broadening indicating a structural distortion in the AlO framework
of the zeolite probably due to interaction of deposited organic
carbon moiety. The AlO is responsible for the Lewis acidic sites
4
) species and minor peak in range
The textural properties of zeolites (H-β, UH-β, and UH-βC)
are mentioned in Table 1 in the ESI. The BET surface area of
2
6
fresh H-β was found to be 501 m /g with a pore volume of 0.32
3
cm /g which decreased sharply for the used catalyst (UH-β) to
2
3
6
3
26 m /g and 0.27 cm /g. The organic carbon moiety have
blocked the pores and consequently, a decrease in the pore
volume/specific surface area of the zeolite was noted. After
6
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
in the β-zeolite and thus relevant to the reaction described in this
work. However, in the case of used zeolite (UH-β), the formed
organic moiety blocked/modified the extra-framework Lewis
A probable mechanism has been proposed for the formation
of arylated γ-lactones (Figure 9). First, the lone pairs of keto group
of LA interact with the Lewis-acidic sites of aluminium that are
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
[25, 31]
acidic sites of AlO
6
, and thus resulting in the observed decline in
present due to the local defects in zeolitic framework.
The
the catalytic activity. The reactivated catalyst (UH-βC) obtained
upon calcination showed a sharp peak at 0.6 δ ppm similar to the
fresh β-zeolite suggests the restoration of the structure of the
catalyst.
development of a partial positive charge on the keto carbon
initiates a nucleophilic attack via the electron rich para position of
anisole and/or other active substrates resulting in formation of γ-
hydroxy pentatonic acid intermediate. This being unstable
undergoes ring cyclization (intra-molecular esterification) to γ-
lactone with the removal of water.[32] The slightly higher activity of
H-β zeolite compared to Na-β is probably due to the presence of
protons (Brönsted acidic) on the surface of H-β zeolite that
facilitates the reaction.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
Figure 8. Scale up studies (γ-lactone yield and selectivity vs. time (h).
LA to aromatic molar ratio is 1:4 (LA (86 mmol, 10 g), anisole (344.8 mmol,
37.2 g)), H-β (50 wt% with respect to LA), 150 °C. Yields are determined by
gas chromatography.
Figure 9. β-zeolite catalysed mechanistic pathway for Agvls formation
1
The obtained Agvls were structurally confirmed by H and
C NMR spectroscopy, a representative example of H NMR of
1
3
1
Figure 7. CP-MAS NMR of β-zeolite catalysts; (a) 13C CP-MAS NMR (b)
27Al CP-MAS NMR
Agvl (anisole aromatic product: 5-(4-methoxyphenyl)-5-
methyldihydrofuran-2(3H)-one) is shown in Figure 10. The
presence of two doublets in the aromatic region (7.3-7.29 and 6.9-
6.88 δ ppm) confirmed selective para substitution. The 13C NMR
showed a peak at 86.9 δ ppm evince chemo- and regioselective
formation of Agvls contrary to the formation of 1,4-diketones
A scalability study for the synthesis of γ-lactone was carried
out at 10 g of LA with anisole. An increase in the yield of γ-lactone
was observed with an increase in time. After 6, 12, 18 and 24 h;
3
8, 62, 80 and 90% yield of para substituted γ-lactone was
obtained with 95, 94, 92 and 90% selectivity respectively (Figure
).
(
which would show peaks around 200 and 205 δ ppm for keto
groups which were absent in our 13C NMR) by Friedel-Crafts
acylation (Figure 5 in the ESI). The other six membered aromatic
8
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
products were also showed similar H and 13C NMR profile like
the above mentioned anisole product. The H and 13C NMR data
of the synthesized Agvls samples were re-recorded after 6
months of time to ascertain their bench stability. No noticeable
1
change in the spectral data was observed asserting that the
isolated products (Agvls) were stable for prolonged periods. The
spectral analysis of corresponding products are depicted in Figure
6A-L in the ESI.
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
1
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
Figure 10. H and 13C NMR representation for formation of ү-lactone formation from LA with anisole
1
Conclusions
Experimental Section
In summary, herein we report a green synthetic protocol for the
synthesis of arylated γ-valerolactones (Agvls) from LA and
oxygen or sulphur- containing electron rich aromatics using
recyclable β-zeolite as catalyst. The reaction is highly chemo- and
regioselective as evinced by H and 13C NMR. Reaction scope
studies with various aromatic compounds including five
membered heterocyclics unravelled the structural requirements
necessary in enabling this reaction. The reaction was successfully
scaled to 10 g that yielded 90% of the para isomer in 24 h. The
synthesized Agvls are stable in air for several months. The
formation of organic carbonaceous moiety during the reaction,
responsible for catalyst deactivation, was ascertained through
several physicochemical, spectroscopic and microscopic
techniques, whose removal by calcination regenerated the activity
of the catalyst. Sustainable preparation of Agvls demonstrated in
the present work is expected to spur interest among biomass
researchers and process chemists in rendering new/novel
products.
Materials and methods
Levulinic acid (98%), methyl levulinate (≥ 98%), ethyl levulinate
(
99%), and butyl levulinate (98%) were purchased from Sigma-
Aldrich, Some of the aromatics and solvents used such as
thiophene, anisole, cumene, N,N-Dimethyl aniline,
1
triphenylphosphine, methanol, and dichloromethane (DCM) were
purchased from local vendors in India. Different zeolites used
(
Table 1) were purchased from Zeochem, Switzerland. H-form of
zeolite and alkoxy benzenes except anisole were prepared using
the reported procedure.[33]
Catalytic reaction
The desired aromatic compound (17.27 mmol, 4 equiv.), LA (4.31
mmol, 1 equiv.), and H-β (250 mg, 50 wt% with respect to LA)
were stirred at 150 °C for 12 h at 600 rpm. After the completion
of the reaction, the reaction mixture was diluted with DCM under
stirring for 30 min. at room temperature. The mixture was then
centrifuged to collect the supernatant liquid and the catalyst was
separated. The collected catalyst was stirred with DCM and
2 4
centrifuged. The supernatant was dried over anhydrous Na SO
and filtered. The reaction progress was monitored with thin-layer
chromatography and the product mixture of γ-lactone was purified
by column chromatography on silica gel (100-200 mesh) with
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
ethyl acetate/hexane as the mobile phase. The isolated products
Thermogravimetric analysis (TGA) was carried out in
Mettler TGA/SDTA 851 and the data were processed using Star
software, in flowing oxygen and at a heating rate of 10 °C/min.
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
were characterised by 1H & 13C NMR spectroscopy (CDCl
e
e
3
solvent, Bruker, 500 MHz). In the case of thiophene, N,N-dimethyl
aniline and triphenylphosphine as reactants, the reaction products
were analysed using GC-MS. The reaction, analysis, and
separation were done in duplicate and the error in the
measurements were  2%.
The elemental analysis was carried out using Elementar,
Vario Micro Cube CHNS analyser with combustion range 1150 °C
in presence of He as the carrier gas. The gases from the
degraded samples were confirmed by using ADS resin column
with TCD detector.
The total organic carbon (TOC) present in the catalysts (H-
β, UH-β, and UH-βC) was measured by using Elementar
instrument, Germany with soil Boden-Standard (Art-No: 35.00-
Catalyst characterization
PXRD measurement was carried out in a Philips X‟Pert MPD
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
system using Cu K
and current were 40 kV and 30 mA, respectively. A step size of
.04° with a step time of 2 seconds was used for data collection.
α
radiation (λ=1.5406 Å). The operating voltage
0156). The sample reactor was maintained at 800 °C the CO
detected and measured by using NDIR detector.
2
was
0
The data were processed using the Philips X’Pert (version 2.2e)
software. Identification of the crystalline phases was made by
comparison with the JCPDS files.
Fourier transformed-infrared (FT-IR) spectra between 400
and 4000 cm-1 with an accumulation of 20 scans and 4 cm-1
resolution were recorded in a Perkin-Elmer, GX-FTIR instrument,
using KBr pellets. The acidity of the zeolites (Na-Y, Na-ZSM-5,
Na-β, H-β, UH-β, and UH-βC) were analysed through pyridine
adsorption and monitored using Fourier-transformed infra-red
Solid-state NMR spectra were acquired on Bruker Avance II
500 MHz spectrometer equipped with a double-resonance CP-
MAS probe. The 27Al MAS spectra were recorded at a spinning
3 2
frequency of 8 KHz with 1024 scans using AlCl .6H O as
reference and chemical shift range between 200 to -220 δ ppm.
The 13C MAS spectra were recorded at a spinning frequency of 8
KHz with 2048 scans using Tetramethylsilane (TMS) as reference
in the chemical shift range between 250 to -50 δ ppm.
The absorbance and transmittance were recorded using
Shimadzu UV-2500 spectrophotometer, Japan.
(
Py-FTIR) spectroscopic technique. For py-FTIR analysis, the
samples were initially oven-dried at 100 °C for 3 h. To the oven
dried sample (50 mg), 0.1 ml of pyridine was admixed directly. To
remove the physisorbed pyridine present in the sample, the
samples were dried in oven at 120 °C for 1 h. The samples were
cooled to room temperature and the spectra were recorded with
a nominal resolution of 4 cm-1 in the spectral range of 400-4000
cm-1 using a KBr background and 15 scans were accumulated for
each spectrum.
Specific surface area and pore size analysis of the samples
were measured by nitrogen adsorption at -196 °C using a
sorptometer (ASAP-2020, Micromeritics). The samples were
degassed under vacuum at 300 °C for 4 h prior to measurements
in order to expel the physiadsorbed water molecules. The BET
specific surface area was calculated by using the standard
Abbreviations
Short form
LA
Abbreviations
Levulinic acid
Gvl
γ-valerolactone
Agvls
MeL
Arylated γ-valerolactones
Methyl levulinate
EtL
BuL
Ethyl levulinate
Butyl levulinate
DCM
UH-β
UH-βC
Dichloromethane
Used H-β zeolite
Used H-β zeolite calcined at 550 °C for 3 h
Brunauer, Emmett and Teller (BET) method on the basis of Acknowledgements
adsorption data. Pore volume and micropore area were also
determined.
The electron microscopic study has been done with
CSIR-CSMCRI Article No. 075/2017. S.G. thanks CSIR, New
Delhi, for a Senior Research Fellowship. The authors thank CSIR,
New Delhi for financial support under the projects OLP-0031,
CSC-0123, and MLP-0028. The authors thank Analytical Division
Centralized Instrumental Facilities of this institute for analytical
support. The authors thank Dr. Joyee Mitra and Dr. Churchil A.
Antonyraj for proof correction of the manuscript.
scanning electron microscope (JEOL series JSM-7100F)
equipped with Oxford instruments energy dispersive X-ray
spectrometer (EDX) facility. The samples were coated with gold
using sputter coating before analysis to avoid charging effects
during recording. Analyses were carried out with an accelerating
voltage of 15 kV and a working distance of 10 mm, with
magnification values in-between 5000x to 30,000x.
&
Conflicts of interest
The acidity in β-zeolites (H-β, UH-β, and UH-βC) were
analysed by NH
920 instrument. Initially, the samples were activated at 150 °C
under a helium flow to removal of physisorbed H O molecules and
passed the ammonia gas at 50 °C temperature. After, NH get
observed in zeolites, the temperature was raised from 50 to
3
-TPD desorption on a Micromeritics Autochem
The authors declare no conflict of interest.
2
2
3
Keywords: Levulinic acid • arylated γ-valerolactones • β-zeolite •
chemo- and regioselectivity • catalyst deactivation
-1
5
00 °C with heating rate of 10 °C min and calculated desorbed
NH in each sample.
3
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
[
1] a) J. H. Clark, F. E. I. Deswarte, in Introduction to Chemicals
from Biomass (Eds.: J. H. Clark, F. E. I. Deswarte), John
Wiley & Sons, Ltd. 2008, pp. 1-20; b) D. B. Turley, in
Introduction to Chemicals from Biomass (Eds.: J. H. Clark, F.
E. I. Deswarte), John Wiley & Sons, Ltd. 2008, pp. 21-46.
Q. Bond, J. C. Serrano-Ruiz, J. A. Dumesic, Green Chem.
2010, 12, 992-999; c) S. Lomate, A. Sultana, T. Fujitani,
Catal. Lett. 2018, 148, 348-358.
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
[14] a) A. S. Amarasekara, T. B. Singh, E. Larkin, M. A. Hasan,
H.-J. Fan, Ind. Crops Prod. 2015, 65, 546-549; b) G. Liang,
A. Wang, X. Zhao, N. Lei, T. Zhang, Green Chem. 2016, 18,
3430-3438.
[15] Y. Z. Qin, M. H. Zong, W. Y. Lou, N. Li, ACS Sustain. Chem.
Eng. 2016, 4, 4050-4054.
[16] K. M. Doll, S. Z. Erhan, Green Chem. 2008, 10, 712-717.
[17] a) W. Wang, N. Li, S. Li, G. Li, F. Chen, X. Sheng, A. Wang,
X. Wang, Y. Cong, T. Zhang, Green Chem. 2016, 18, 1218-
1223; b) J. Xin, S. Zhang, D. Yan, O. Ayodele, X. Lu, J. Wang,
Green Chem. 2014, 16, 3589-3595.
[18] a) Y.-B. Huang, J.-J. Dai, X.-J. Deng, Y.-C. Qu, Q.-X. Guo,
Y. Fu, ChemSusChem 2011, 4, 1578-1581; b) A. Ledoux, L.
Sandjong Kuigwa, E. Framery, B. Andrioletti, Green Chem.
2015, 17, 3251-3254.
[2] a) F. H. Isikgor, C. R. Becer, Polym. Chem. 2015, 6, 4497-
4559; b) H. L. Wang, Y. Q. Pu, A. Ragauskas, B. Yang,
Bioresour. Technol. 2019, 271, 449-461.
[
3] a) P. Gallezot, Chem. Soc. Rev. 2012, 41, 1538-1558; b) G.
Fiorentino, M. Ripa, S. Ulgiati, Biofuels, Bioprod. Biorefin.
2017, 11, 195-214.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
[
4] a) A. Corma, S. Iborra, A. Velty, Chem. Rev. 2007, 107,
2411-2502; b) V. D. M. patel, B. Husing, L. Overbeek, F.
Terragni, E. Recchia, in Medium and Long-term
Opportunities and Risks of the Biotechnology production of
Bulk Chemicals from Renewable Resources-The Potential of
White Biotechnology, The BREW Project report, European
Commissions Growth Programme, 2006; c) S. Van de Vyver,
J. Geboers, P. A. Jacobs, B. F. Sels, ChemCatChem 2011,
[19] a) F. Liguori, C. Moreno-Marrodan, P. Barbaro, ACS Catal.
2015, 5, 1882-1894; b) S. Gundekari, K. Srinivasan, Appl.
Catal. A: Gen. 2019, 569, 117-125.
[20] D. M. Alonso, S. G. Wettstein, J. A. Dumesic, Green Chem.
2013, 15, 584-595.
3, 82-94; d) M. Rose, R. Palkovits, Macromol. rapid commun.
2011, 32, 1299-1311; e) D. M. Alonso, J. Q. Bond, J. A.
Dumesic, Green Chem. 2010, 12, 1493-1513; f) S. Li, W.
Deng, S. Wang, P. Wang, D. An, Y. Li, Q. Zhang, Y. Wang,
ChemSusChem 2018, 11, 1995-2028; g) Z. Sun, B. Fridrich,
A. de Santi, S. Elangovan, K. Barta, Chem. Rev. 2018, 118,
[21] a) B. M. Trost, J. R. Corte, Angew. Chem. Int. Ed. 1999, 38,
3664-3666; b) B. M. Trost, J. R. Corte, M. S. Gudiksen,
Angew. Chem. Int. Ed. 1999, 38, 3662-3664; c) W. C. C.
Bernhart, P. Gautier, Derivatives of γ-butyrolactone with an
anti-arrythmic activity and compositions, US Patent
4,542,134, 1985; d) H.-F. Chan, The preparation of
substituted gamma butyrolactones useful as intermeadiates
for making fungicidal imidazoles and triazoles, European
Patent 0162265 B1, 1990.
[22] a) C. Stone, Use of gamma substituted gamma-
butyrolactone to increase levels of their corresponding
substituted gamma-hydroxybutyrate derivatives in humans,
US Patent 0132846 A1, 2002; b) T. Dohi, N. Takenaga, A.
Goto, A. Maruyama, Y. Kita, Org. Lett. 2007, 9, 3129-3132;
c) J. D. Lambert, J. E. Rice, J. Hong, Z. Hou, C. S. Yang,
Bioorg. Med. Chem. Lett. 2005, 15, 873-876; d) A. Albrecht,
J. F. Koszuk, J. Modranka, M. Różalski, U. Krajewska, A.
Janecka, K. Studzian, T. Janecki, Bioorg. Med. Chem. 2008,
16, 4872-4882; e) C.-C. Tzeng, K.-H. Lee, T.-C. Wang, C.-H.
Han, Y.-L. Chen, Pharm. Res. 2000, 17, 715-719.
[23] a) J. Cejka, A. Corma, S. Zones, in Handbook of Zeolites and
Catalysis: Synthesis, Reactions and Applications, Wiley‐
VCH Verlag GmbH & Co. KGaA, 2010; b) R. A. Sheldon, I.
Arends and U. Hanefeld, in Handbook of Green chemistry
and Catalysis, Wiley‐VCH Verlag GmbH & Co. KGaA, 2007.
[24] a) T. P. Vispute, H. Zhang, A. Sanna, R. Xiao, G. W. Huber,
Science 2010, 330, 1222-1227; b) E. I. Gürbüz, J. M. R. Gallo,
D. M. Alonso, S. G. Wettstein, W. Y. Lim, J. A. Dumesic,
Angew. Chem. Int. Ed. 2013, 52, 1270-1274; c) Q. Guo, F.
Fan, E. A. Pidko, W. N. P. van der Graaff, Z. Feng, C. Li, E.
J. M. Hensen, ChemSusChem 2013, 6, 1352-1356; d) E.
Taarning, C. M. Osmundsen, X. Yang, B. Voss, S. I.
Andersen, C. H. Christensen, Energy Environ. Sci. 2011, 4,
793-804; e) S. Saravanamurugan, M. Paniagua, J. A. Melero,
A. Riisager, J. Am. Chem. Soc. 2013, 135, 5246-5249; f) W.
Luo, U. Deka, A. M. Beale, E. R. H. van Eck, P. C. A.
Bruijnincx, B. M. Weckhuysen, J. Catal. 2013, 301, 175-186;
g) P. Bhanja, A. Bhaumik, Fuel 2016, 185, 432-441.
[25] J. C. Jansen, E. J. Creyghton, S. L. Njo, H. van Koningsveld,
H. van Bekkum, Catal. Today 1997, 38, 205-212.
614-678; h) L. T. Mika, E. Csefalvay, A. Nemeth, Chem. Rev.
2018, 118, 505-613.
[5] a) P. N. R. Vennestrøm, C. M. Osmundsen, C. H.
Christensen, E. Taarning, Angew. Chem. Int. Ed. 2011, 50,
10502-10509; b) M. Pelckmans, T. Renders, S. Van de Vyver,
B. F. Sels, Green Chem. 2017, 19, 5303-5331; c) C. G. S.
Lima, J. L. Monteiro, T. de Melo Lima, M. Weber Paixao, A.
G. Correa, ChemSusChem 2018, 11, 25-47; d) K. Gupta, R.
K. Rai, S. K. Singh, ChemCatChem 2018, 10, 2326-2349.
[6] a) L. Yan, Q. Yao, Y. Fu, Green Chem. 2017, 19, 5527-5547;
b) F. D. Pileidis, M. M. Titirici, ChemSusChem 2016, 9, 562-
582.
[
7] a) D. W. Rackemann, W. O. S. Doherty, Biofuels, Bioprod.
Biorefin. 2011, 5, 198-214; b) A. Szabolcs, M. Molnar, G.
Dibo, L. T. Mika, Green Chem. 2013, 15, 439-445; c) J. J.
Bozell, L. Moens, D. C. Elliott, Y. Wang, G. G.
Neuenscwander, S. W. Fitzpatrick, R. J. Bilski, J. L. Jarnefeld,
Resour. Conserv. Recycl. 2000, 28, 227-239; d) S. M. Kang,
J. X. Fu, G. Zhang, Renew. Sustain. Energy Rev. 2018, 94,
340-362.
[
[
8] B. V. Timokhin, V. A. Baransky, G. D. Eliseeva, Russ. Chem.
Revi. 1999, 68, 73-84.
9] a) J. J. Bozell, G. R. Petersen, Green Chem. 2010, 12, 539-
554; b) A. Aden, J. Bozell, J. Holladay, J. White, A. Manheim,
in Top Value Added Chemicals from Biomass Volume I,
Results of Screening for Potential Candidates from Sugars
and Synthesis Gas, U.S. Department of Energy (DOE)
Report, 2004.
[
10] a) S. Selifonov, Glycerol levulinate ketals and their use in the
manufacture of polyurethanes, polyurethanes formed
therefrom, US Patent 0196947A1, 2012; b) A. S.
Amarasekara, S. A. Hawkins, Eur. Polym. J. 2011, 47, 2451-
2457.
11] Y. Guo, K. Li, J. H. Clark, Green Chem. 2007, 9, 839-841.
12] a) A. Démolis, N. Essayem, F. Rataboul, ACS Sustainable
Chem. Eng. 2014, 2, 1338-1352; b) S. Saravanamurugan, A.
Riisager, ChemCatChem 2013, 5, 1754-1757; c) Q. J. Luan,
L. J. Liu, S. W. Gong, J. Lu, X. Wang, D. M. Lv, Process Saf.
Environ. Prot. 2018, 117, 341-349.
[
[
[26] S. Gundekari, K. Srinivasan, Catal. Lett. 2018 (DOI:
10.1007/s10562-018-2618-7).
[13] a) J. Q. Bond, D. M. Alonso, D. Wang, R. M. West, J. A.
Dumesic, Science 2010, 327, 1110-1114; b) D. M. Alonso, J.
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
[
27] M. Varkolu, R. Chakali, V. P. Chodimella, D. R. Burri, R. R.
S. Kamaraju, RSC Adv. 2014, 4, 9660-9668.
28] a) O. A. Baturina, S. R. Aubuchon, K. J. Wynne, Chem. Mater.
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
[
2006, 18, 1498-1504; b) W.-F. Chiang, H.-Y. Fang, C.-H. Wu,
C.-J. Huang, C.-Y. Chang, Y.-M. Chang, C.-L. Chen, J. Air
Waste Manage. Assoc. 2009, 59, 148-154; c) V. Halperin, G.
E. Shter, V. Gelman, D. M. Peselev, M. Mann-Lahav, G. S.
Grader, Catal. Sci. Technol. 2015, 5, 1153-1162; d) J.
Adelene Nisha, M. Yudasaka, S. Bandow, F. Kokai, K.
Takahashi, S. Iijima, Chem. Phys. Lett. 2000, 328, 381-386;
e) A. Devaraj, M. Vijayakumar, J. Bao, M. F. Guo, M. A.
Derewinski, Z. Xu, M. J. Gray, S. Prodinger, K. K. Ramasamy,
Sci. Rep. 2016, 6, 37586; f) Y. Luo, Z. Wang, Y. Fu, C. Jin,
Q. Wei, R. Yang, J. Mater. Chem. A 2016, 4, 12583-12590;
g) E. Fiamegkou, E. Kollia, A. Vavouliotis, V. Kostopoulos, J.
Compos. Mater. 2015, 49, 3241-3250; h) Z. Wang, M. Liu, X.
Cheng, Y. He, Y. Hu, C. Ma, in International Journal of
Chemical Reactor Engineering, Vol. 16, 2018.
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
[
[
29] a) P. Castaño, G. Elordi, M. Olazar, A. T. Aguayo, B.
Pawelec, J. Bilbao, Appl. Catal. B 2011, 104, 91-100; b) A.
R. Pradhan, T.-S. Lin, W.-H. Chen, S.-J. Jong, J.-F. Wu, K.-
J. Chao, S.-B. Liu, J. Catal. 1999, 184, 29-38; c) W.-H. Chen,
A. Pradhan, S.-J. Jong, T.-Y. Lee, I. Wang, T.-C. Tsai, S.-B.
Liu, J. Catal. 1996, 163, 436-446.
30] a) S. Al-Khattaf, C. D'Agostino, M. N. Akhtar, N. Al-Yassir, N.
Y. Tan, L. F. Gladden, Catal. Sci. Technol. 2014, 4, 1017-
1027; b) K. Barbera, S. Sørensen, S. Bordiga, J. Skibsted, H.
Fordsmand, P. Beato, T. V. W. Janssens, Catal. Sci. Technol.
2012, 2, 1196-1206; c) P. Shestakova, C. Martineau, V.
Mavrodinova, M. Popova, RSC Adv. 2015, 5, 81957-81964.
31] Z. Zhao, S. Xu, M. Y. Hu, X. Bao, C. H. F. Peden, J. Hu, The
J. Phys. Chem. C 2015, 119, 1410-1417.
32] a) A. M. R. Galletti, C. Antonetti, V. De Luise, M. Martinelli,
Green Chem. 2012, 14, 688-694; b) W. R. H. Wright, R.
Palkovits, ChemSusChem 2012, 5, 1657-1667.
[
[
[33] a) A. M. Camiloti, S. L. Jahn, N. D. Velasco, L. F. Moura, D.
Cardoso, Appl. Catal. A 1999, 182, 107-113; b) J. C. Lee, J.
Y. Yuk, S. H. Cho, Synth. Commun. 1995, 25, 1367-1370.
This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.201801782
FULL PAPER
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
6
7
8
9
0
1
2
3
4
5
Entry for the Table of Contents
FULL PAPER
Sreedhar Gundekari[a, b], Kannan
Srinivasan*[
a, b]
1
1
1
1
1
1
1
1
1
1
2
2
2
2
2
2
2
2
2
2
3
3
3
3
3
3
3
3
3
3
4
4
4
4
4
4
4
4
4
4
5
5
5
5
5
5
5
5
5
5
6
6
6
6
6
6
Page No. – Page No.
Chemo- and regioselective synthesis
of arylated γ-valerolactones from bio-
based levulinic acid with aromatics
using H-β zeolite catalyst
Text for Table of Contents
H-β catalysed chemo- and regionselective synthesis of arylated γ-valerolactones
Herein, we report preparation of arylated γ-valerolactones for the first time from bio-based levulinic acid with aromatics using recyclable
H-β zeolite catalyst under solvent free conditions with good selectivity.
This article is protected by copyright. All rights reserved.