One Pot Synthesis of Phenylacetaldehyde From Styrene

Received: 19 October 2023 | Revised: 19 January 2024 | Accepted: 18 February 2024
DOI: 10.1002/ffj.3780
RESEARCH ARTICLE
One-pot synthesis of phenylacetaldehyde from styrene

via metal oxide catalysed oxidation in presence of cumene
hydroperoxide
Sudip Das1,2
1
Department of Chemical Engineering,
Indian Institute of Technology Bombay, Abstract
Mumbai, India
Phenylacetaldehyde (PhA) is an aromatic aldehyde which has a hyacinth-like flo-
2
Chemical and Biomolecular Engineering
Department, New York University, New
ral, sweet and green-leafy odour. PhA is used as a perfumery chemical and a rate-
York, USA controlling additive in cosmeceutical and polymer industries, respectively. The
Correspondence
conventional process of PhA manufacturing in industries involve hazardous and costly
Sudip Das, Department of Chemical feedstock and often lead to generation of substantial amount of waste. Moreover,
Engineering, New York University,
Mumbai 400076, India.
usage of stoichiometric reagents often makes the processes economically impractical.
Email: sd5830@nyu.edu This article illustrates the possibility of production of PhA from low-cost feedstock
Funding information
styrene through a single-step, one-pot method wherein various metal oxides have
Ministry of Education, India been utilized as catalysts for styrene oxidation under the influence of cumene hydrop-
eroxide (CHP). Ag2O is found to be the highest PhA-yielding catalyst and a promising
candidate for scaling up for its considerably good reusability up to 6 consecutive uses.
A maximum of ~45% PhA selectivity has been observed at ~60% styrene conversion.
Interestingly, this process does not require any alkaline/acid wash and hence does
not produce any organic/inorganic liquid effluent stream. Furthermore, all the major
byproducts found, that is styrene oxide, benzaldehyde and acetophenone, are them-
selves considered as valorized styrene derivatives. Overall, the metal oxide catalysed
styrene oxidation has potential to take over the conventional industrial process(es) for
sustainable selective production of PhA Along with a plausible mechanism of styrene
oxidation over Ag2O, a conceptualized reaction–separation framework has been re-
ported for intensified production of PhA from CHP-based styrene oxidation.
KEYWORDS
cumene hydroperoxide, heterogeneous catalysis, metal oxides, phenylacetaldehyde, styrene
1 | I NTRO D U C TI O N evident that the there exists a vivid spectrum of application of these
VSDs the cost of which are folds higher than that of styrene. In ac-
Heterogeneously catalysed styrene oxidation can produce valorized cordance with the proposed mechanism of styrene oxidation,6,7 STOX
styrene derivatives (VSD) like styrene oxide (STOX), benzaldehyde and BzA are considered as the primary products accumulated from
(BzA), phenyl acetaldehyde (PhA), benzoic acid (BzAc), acetophenone styrene oxidation. The other compounds on the other hand can be
(AcP) and phenylacetic acid (PhAc).1–3 Figure 1 illustrates possible considered as the secondary products. For instance, PhA and AcP are
product profile of styrene oxidation along with the applications of the produced by isomerization of primary product STOX whereas, acids
individual VSD and its approximated current market price.4,5 It is also are produced as product of deep oxidation of corresponding ketone.
Flavour Fragr J. 2024;00:1–9. wileyonlinelibrary.com/journal/ffj © 2024 John Wiley & Sons Ltd. | 1
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2 DAS
F I G U R E 1 Reactions involved in styrene oxidation along with approximate market price and applications of the valorized styrene
derivatives (Epoxidation—A; Catenation cleavage—B, C; Oxidation—D, G, H, I; Isomerization—E, F).
As shown in Figure 1, phenylacetaldehyde (PhA) is one of the acid materials, such as zeolites,20,21 supported phosphotungstic het-
VSDs which occurs extensively in nature because it can be biosyn- eropoly acid22 and Nafion-H23 have been applied as catalysts for se-
thetically derived from the amino acid phenylalanine. Natural sources lective production of PhA from STOX feedstock. The major issue with
of the compound include chocolate,8 buckwheat,9 flowers, and com- this process is the cost of reagent (i.e., STOX) itself along with other
munication pheromones from various insect orders.10 It is notable factors like selectivity to PhA, requirement of high amount of catalyst,
for being a floral attractant for numerous species of Lepidoptera; for etc.19–23 Selective production of PhA from a less costly feedstock—
example, it is the strongest floral attractor for the cabbage looper styrene (pathway D in Figure 1) has never been explored the potential
moth.11 The aroma of PhA can be described as honey-like, sweet, rose, to destabilize the current global business volume and cost pattern of
green, grassy and is added to fragrances to impart hyacinth, narcissi PhA. According to the published experimental works on styrene ox-
12
or rose nuances. For similar reasons, the compound can sometimes idation,6,7 heterogeneous catalysis has primarily been employed for
be found in flavoured cigarettes and beverages. Historically, before selective production of primary products (i.e., STOX and BzA). In a few
biotechnology approaches were developed, phenylacetaldehyde was works24–26 PhA has been reported to be produced as a by-product in
used to produce phenylalanine via the Strecker reaction as a pivotal smaller quantities. But, to the best of the author's knowledge, there
step in the production of aspartame sweetener. Phenylacetaldehyde is has been no work reported on one-pot selective production of PhA via
used in the synthesis of polyesters where it serves as a rate-controlling heterogeneous catalysed oxidation of styrene till date.
additive during polymerization.12 Moreover, PhA is responsible for the In this article, a greener one-pot alternative approach for synthetic
antibiotic activity of maggot therapy.13 PhA production via oxidation of styrene using cumene hydroperoxide
There exist numerous chemistries of synthetic PhA manufac- (CHP) as oxygen inducing reagent and heterogeneously catalysed by
turing such as isomerization of styrene oxide,12 dehydrogenation various metal oxides synthesis is reported. Use of CHP as oxidizing agent
of 2-phenylethanol over silver or gold catalysts,12 Darzens reaction for styrene oxidation has been delineated to have advantage of produc-
between benzaldehyde and chloroacetate esters,12 Hofmann rear- ing alpha cumyl alcohol (ACA) as value-added co-product upon break-
14,15
rangement of cinnamamide, oxidation of cyclooctatetraene with age of peroxy bond.6,7,25 Metal oxides have shown excellent catalytic
16,17
aqueous Mercury (II) sulfate, Strecker degradation of phenylala- activities for homologous reactions like styrene oxidation using other
nine.18 The industries that produce PhA using isomerization of STOX oxidants like hydrogen peroxide,27 tert-butyl hydroperoxide,28 and mo-
19
(pathway E in Figure 1), majorly via biocatalytic process. A few solid lecular oxygen.29 Based on observed experimental results and published
|
DAS 3
literature, plausible mechanism of the reaction is also proposed. At the details of the experimental rig, sample collection and sample anal-
end, a reaction–separation framework is ideated by amalgamation of ysis have been elaborated elsewhere.3 Every experimental run was
two industrially practiced processes with CHP-based styrene oxidation triplicated to check the repeatability of data and the results were
aiming selective industrial scale manufacturing of PhA. found to be consistent with an average standard deviation of <10%.
The expressions used for enumerating the performance parameters
(conversion, selectivity and yield) are expressed as,
2 | E X PE R I M E NTA L S EC TI O N
( ) Ni,0 − Ni,t
Conversion Xi = (1)
Ni,0
2.1 | Materials
Nj,t
(2)
( )
Selectivity Si =
Section S1 contains information on the purity, grade and manufac- Ni,0 − Ni,t
turer of all compounds utilized.
( ) Nj,t
Yield Yi = (3)
Ni,0
2.2 | Methodology
where. Ni,0 is the initial number of moles of reactant i, and Nj,t is the
The reactions were performed in batch mode under full reflux as number of moles of product j at any time t.
shown in Figure 2. Reactions under different operating conditions Elemental composition in the oxide samples were measured by
were carried out in a 150 mL glass batch reactor. The reactor is kept inductively coupled plasma—atomic emission spectrometry (ICP–AES,
in an electrically heated hot oil bath. Catalysts were preheated at ARCOS, SPECTRO Analytical Instruments) and Energy dispersive
573 K for 3 h under vacuum before being employed in the experi- spectroscopy (EDX Octane ELITE T70). The powder samples were
mental runs. Samples were collected at specific time intervals. The dissolved in aqua regia at 363 K before being tested in ICP–AES. For
samples were appropriately processed for GC (NUCON 5765, India XRD, the catalyst powder was analysed with an X'Pert diffractometer
gas chromatograph equipped with a highly polar 30-m-long Zebron (PANalytical, U.K.). The data were collected over a 2θ range of 10–90°
ZX Plus capillary column) analysis and iodometric titration to enu- using Cu Kα radiation (λ = 1.5418 Å) at 40 kV and 40 mA.
merate reaction performance. The details of the titration methodol-
ogy and GC sample preparation are elaborated in Section S2.
Furthermore, to have a closer look into the component distribu- 3 | R E S U LT S A N D D I S CU S S I O N S
tion in samples, a two-dimensional GC (Agilent Technologies 7890
gas chromatograph) equipped with a 30-m-long primary column (Rxi 3.1 | Product Profile
5–MS, nonpolar in nature) and a 1.2-m-long secondary column (Rxi
17Sil MS, polar in nature), coupled with a time-of-flight mass spec- Product profiling is a critical activity for any fine and specialty chemical-
trometer (Pegasus 4D, LECO Corporation, USA), was used. More manufacturing business, since the presence of certain chemicals can
F I G U R E 2 Schematic of the
experimental setup showing glass reactor
along with its overhead components like
condenser, sampling port etc., heating
loop and agitator assembly.
|
4 DAS
decrease the unique qualities of a desired product.1,3,30 Figure 3 de- styrene oxidation under the influence of CHP. The results are
picts a typical two-dimensional GC response of the reaction mixture. charted in Figure 4 wherein it is evident that higher temperature
The coupled mass spectrometry was used to identify the chemicals as (upto 363 K) and higher catalyst loading (upto 6% w/w of feed)
constituents of unconverted feed mixture (styrene, cumene), valorized aid the selective production of PhA. As shown for Run 4, drastic
styrene derivatives (STOX, BzA, PhA and AcP), coproducts (AMS, ACA) drop in VSD yield beyond 363 K may be attributed to the higher
and high boiling byproducts (dicumene, benzoic acid, phenylacetic oligomerization rate of styrene. As a consequence, the reaction
acid and styrene oligomers). Mass spectra of these compounds are mixture in case of Run 4 was found to be much more viscous
listed in Section S3. All the valorized styrene derivatives of the reac- than other runs at lower temperatures under otherwise identical
tion mixture were also confirmed by comparing the retention time of operating condition. As far as CHP content in feed and catalyst
peak occurrence in GC using the procured pure components. loading are concerned, further economic analyses are required
to find a suitable trade-off value. The error in styrene balance
[=(100 – ΣS i)/100] can be attributed to the unquantified amount
3.2 | Screening of catalyst of the high boilers.
Comparison of catalytic performances of 20 different commercially

available metallic oxides in the batch-stirred tank reactor operated at 3.4 | Catalyst reusability
353 K for 5 h in the presence of 4% (w/w of feed) catalyst loading has
been listed in Table 1. The uncatalyzed reaction of STY and CHP leads In industrial perspective, the reusability of the catalyst for any heter-
to a very low VSD yield as most of the styrene got converted into ogeneous catalytic reaction-based process is a key factor. To check
high boilers under influence of CHP. Oxides like Cu2O and PbO have the reusability of the catalyst, spent catalyst was filtered from the
shown selectivity towards STOX whereas Ag2O showed highest selec- reaction mixture, washed with 50 mL of demineralized water fol-
tivity towards PhA. Fe2O3, on the other hand, resulted in highest BzA lowed by 30 mL of acetone for 15 min each. The washed catalyst was
yield. A few oxides like MgO and CaO aided decomposition of CHP then dried under vacuum for 3 h at 383 K before being used in the
to various products like alphamethyl styrene (AMS), acetophenone next consecutive run. Figure 5A shows the scope of reusability of
(AcP), alphacumyl alcohol (ACA), dicumene, dicumylperoxide, etc. re- the catalyst from which it is evident that the catalyst can be used for
sulting in low styrene conversion. On the other hand, oxides like V2O5, at least five consecutive recycles without losing significant (>10%)
Nb2O5 and WO3 have been observed to be aiding styrene oligomeri- activity. In previously reported results3 it has been shown that the
zation resulting in high styrene conversion and low VSD selectivity. alteration of oxidation state of some fraction of the surface of the
Interestingly, AcP can be produced by styrene oxidation1,3 as well as bulk oxides in presence of reactive oxidizer species like CHP may af-
31
decomposition of CHP, and hence, the styrene-based selectivity fect the performance parameters.
calculation often resulted in cumulative selectivity value more than Unchanged oxidation state can also be validated from the results
100%. Though one-point analyses cannot be considered as the con- elemental composition analysis performed by ICP–AES and EDX analy-
clusive factor for catalyst screening, tendency of Ag2O to selectively ses (observed Ag content = 93.1 ± 1.6% w/w). These results can also be
convert styrene to PhA in the presence of CHP as the oxygen inducing asserted by the unaltered X-ray diffractograms of the fresh and spent
reagent can be observed from this exercise. Thus, Ag2O was chosen to catalyst powders as shown in Figure 6. The two major peaks of silver
be the catalyst to be utilized in further experimentations. (I) oxide were observed at 2θ = 27.94 and 32.27 which are responsible
for (110) and (111) facets (JCPDS file—76-1393). Also, smaller peaks at
2θ = 46.34, 54.92 and 67.48 indicates the presence of (211), (220) and
3.3 | Effect of operating parameters (222) facets, respectively. The ratio of the two major peaks is found
to have changed by only ~2% after 5th reuse. Furthermore, Scherrer
Effect of operating parameters like temperature, feedstock com- equation is used to enumerate the crystal sizes for the fresh and
position and catalyst loading have been tested on Ag 2O-c atalysed spent catalysts and were found to be ~5% different from each other,
F I G U R E 3 Typical 2-D GC response

of the reaction mixture ACA, alphacumyl
alcohol; AcP, Acetophenone; AMS,
Alphamethyl styrene; BzA, Benzaldehyde;
CUM, Cumene; PhA, Phenylacetaldehyde;
STOX, Styrene oxide; STY, styrene.
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DAS 5
TA B L E 1 Catalytic performance of different oxides for CHP-induced styrene oxidation (performed in glass stirred tank reactor; operating
temperature = 353 K; operating pressure = 1 atm; catalyst load = 4% (w/w of feed); feed (STY:CHP:CUM) = 1:2:2 (w/w); Reaction time = 5 h;
speed of agitator = 700 rpm).
Performance Parametersc (in %)
Catalyst Proca/prepb XSTY XCHP SSTOX SBzA SPhA SAcP
― ― 35.58 56.57 15.82 6.33 4.19 29.57

Ce2O3 Prep/Sulphate/500/5 50.79 86.63 0.41 4.81 ― 58.88
V2O5 Proc 54.42 98.84 1.46 12.33 6.17 32.41
Nb2O5 Proc 49.48 83.22 2.87 7.45 ― 27.17
WO3 Proc 58.35 78.91 9.49 9.45 ― 16.19
MoO3 Proc 43.11 88.16 3.87 13.17 11.05 63.16
Ag2O Proc 44.67 62.22 13.87 19.17 41.05 33.16
Bi2O3 Prep/Nitrate/500/5 30.55 78.12 21.03 62.54 4.12 42.14
ZnO Proc 42.03 55.84 18.42 16.54 6.28 19.48
Fe2O3 Proc 41.75 76.31 18.98 29.47 5.42 17.57
MgO Proc 40.29 83.05 20.28 6.14 ― 48.63
TiO2 Proc 31.25 58.19 28.29 33.25 4.19 38.52
Ga2O3 Proc 35.39 75.11 27.34 5.34 16.47 26.58
CaO Proc 35.44 97.06 30.08 9.19 ― 53.17
ZrO2 Proc 35.87 52.33 33.45 ― 18.36 16.41
La2O3 Proc 49.56 76.14 32.04 6.54 4.47 32.17
BaO Proc 42.82 58.88 37.38 13.45 7.11 26.33
NiO Prep/Nitrate/500/5 50.52 84.18 38.69 8.77 9.97 21.08
CuO Prep/Nitrate/500/5 51.25 70.06 41.59 9.74 11.64 28.96
CoO Prep/Nitrate/500/5 64.54 72.38 36.41 18.45 4.88 19.24
PbO Proc 56.26 60.08 50.92 16.64 3.18 23.17
Cu2O Proc 85.17 91.48 37.76 8.78 3.73 28.48
a
Used as it was procured.
b
Information on the oxides which were prepared by thermal decomposition of precursor salts have been incorporated in the form of
‘Prep/<Precursor salt>/<Calcination temperature/K-273>/<calcination duration/h>’.
c
All selectivity values are enumerated in reference to converted styrene.
F I G U R E 4 Results of CHP-induced
styrene oxidation (performed in
glass stirred tank reactor; Operating
pressure = 1 atm; Feed w/w content of
STY:CHP:CUM = 1:2:2, Catalyst used—
Ag2O; Speed of agitator = 700 rpm).
|
6 DAS
F I G U R E 5 (A) Results of catalyst

reusability and (B) hot filtration of Ag2O
for CHP-induced styrene oxidation
performed in glass stirred tank reactor;
operating temperature = 353 K; operating
pressure = 1 atm; catalyst load = 4% (w/w
of feed); feed (STY:CHP:CUM) = 1:2:2
(w/w); reaction time = 5 h; speed of
agitator = 700 rpm; All selectivity values
are enumerated in reference to converted
styrene.
indicating practically no change in crystal structure and size. Details of

XRD data analysis has been provided in Section S4.
As, only reuse of a bulky oxide is not a sufficient test for the hetero-
geneous character of the catalysis, to fathom the extent of leaching, hot
filtration of the liquid monitoring of the conversion of filtered solution
is always recommended.32,33 For hot filtration, the reaction mixture was
rapidly poured from the batch experimental setup to another identical
glass batch reactor kept on temperature-controlled hotplate operated
at temperature identical to that of the reaction temperature. During
pouring the reaction mixture, the solid phase was filtered by filter fun-
nel. In order to speed up the filtration process, vacuum was employed
using a vacuum pump. Hot filtration was performed under full reflux and
the samples were removed at specific time intervals by pipette pump.
Figure 5B illustrates the results of hot filtration wherein it is evident that
reaction progression practically stalled after the filtration of solids from
the liquid reaction mixture indicating true heterogeneity of Ag2O within
range of operating conditions employed in this work.
F I G U R E 6 Peak locations and corresponding facets observed
from X-ray diffractograms of fresh and spent Ag2O.
3.5 | Effect of free radical inhibitors
According to the literature, heterogeneously catalysed styrene oxida-

tion can occur either by adsorption of reactive species on the catalyst
surface followed by propagation of reaction on the surface itself there-
after34 or by formation of free radicals on the catalyst surface followed
by electronic rearrangements in the bulk phase.35 In order to compre-
hend the extent of free radical formation in this case, free radical in-
hibitors like tert-butyl catechol (TBC), 4-hydroxy-2,2,6,6-tetramethyl
piperidine 1-Oxyl (4HTEMPO), 4-methoxy phenol (4mPh) and N,N-
dibenzylhydroxylamine (DBHA) were employed. No notable change
in reaction performance was observed upon utilization of such widely
used free radical inhibitors (refer to Figure 7) which indicates that the
reaction is not free radical-based.
F I G U R E 7 Effect of using free radical inhibitors for Ag2O

4 | P OS S I B LE R E AC TI O N PATH WAY catalysed CHP-induced styrene oxidation performed in
glass stirred tank reactor; operating temperature = 353 K;
operating pressure = 1 atm; catalyst load = 4% (w/w of feed);
Depending upon the observations and previously reported feed (STY:CHP:CUM) = 1:2:2 (w/w); reaction time = 5 h; speed
data plausible reaction pathways of the CHP-induced styrene of agitator = 700 rpm. All selectivity values are enumerated in
oxidation on Ag 2O can be postulated to be initiated with the reference to converted styrene.
|
DAS 7
adsorption of CHP on the active site (TS1 in Figure 8). Oxygen or experimental analyses are needed to be performed to compre-
species required to form the oxo−/peroxo-s pecies is released hend the favourable pathway.
from CHP molecules which in turn get converted to ACA mol-
ecules stoichiometrically. The oxo-or peroxo-a ctive sites (TS2)
on the catalyst surface then attacked by the non-r ing C=C bond 5 | I N D U S TR I A L PE R S PEC TI V E
of styrene which results in alkyl-p eroxo transition state (TS3).
BzA is produced by simultaneously occurring catenation cleav- Industrial applicability of CHP-
induced catalytic styrene oxidation
age of the non-ring C–C entity of the corresponding transition for selective production of STOX has been elucidated in previous
state. The transition state responsible for generation of BzA may works.1–3 In the perfumery market, 50% (w/w) PhA in 2-phenylethanol
or may not be the same as PhA. 6,7 Furthermore, at this point it is (2PEA) is generally sold as the fragrant building block.36 Our previ-
unclear whether PhA is being produced on the catalytic surface ous work2 have revealed that under considerably mild operating
by electronic rearrangement from the formed transition state conditions (~333 K, <15 atm) a mixture of STOX, PhA and AcP can
directly, or via isomerization of styrene oxide. Traces of AMS be hydrogenized in such a way so that the keto compounds (PhA
found in the reaction mixture can be attributed to simultaneous and AcP) remain as they were while STOX almost stoichiometrically
occurrence of dehydration of ACA. Further computational and/ get converted into 2PEA in presence of commercial Pd/C catalyst.
F I G U R E 8 Possible catalytic cycle and transition states involved in CHP-induced styrene oxidation in presence of Ag2O for selective
production of PhA; AS—Active site; TS—Transition state.
F I G U R E 9 Conceptualized reaction–
separation framework for PhA production
via catalytic oxidation of styrene in
presence of CHP as oxidizing agent.
|
8 DAS
Under similar operating conditions, hydrogenation of CHP yields ACA AC K N OW L E D G E M E N T S

37,38
quasi-stoichiometrically, along with traces of AMS. Furthermore, The author acknowledges the critical input by Prof. Sanjay M
the VLE characteristics of the binary mixture of (2PEA + AcP) and Mahajani (Department of Chemical Engineering, IIT Bombay, India),
(2PEA + ACA)39 shows that no azeotropes are formed over the whole Prof. Ojus Mohan (Department of Chemical Engineering, IIT Bombay,
range of mole fraction of the constituents. Though vacuum services India), Harmony Organics Pvt. Ltd. (Pune, India) and Sophisticated
are recommended in order to ensure realistic resultant dimension of Analytical Instrument Facility (SAIF, IIT Bombay, India). Furthermore,
the distillation columns. As depicted in Figure 9, the first reactor (R1) the author sincerely thanks the Ministry of Education, Government
is the oxidation reactor whereas the second reactor (R2) facilitates the of India for required financial aid through ‘UAY/IITB-005’ and
hydrogenation. ‘RD/0522-RCCSH0-012’ schemes.
To further intensify the whole scheme, a reactor (R0) can be put
at the upstream to R1 wherein aerobic oxidation of cumene can take C O N FL I C T O F I N T E R E S T S TAT E M E N T
place for the generation of CHP. Out of three reactions shown in The author declares no competing financial interest.
Figure 9, aerobic oxidation of cumene for selective production of
CHP and catalytic hydrogenation of CHP and STOX are industrially DATA AVA I L A B I L I T Y S TAT E M E N T
practiced process. 2 Separation schemes SS0 is used to recycle un- The data that support the findings of this study are available from
converted cumene and thereby concentrate (upto ~50% w/w) the the corresponding author upon reasonable request.
CHP rich stream going into R1 to match the feed optimum condition
required for catalytic oxidation. SS1 should be designed to purify ORCID
styrene from the resultant reaction mixture at downstream to R2. Sudip Das https://orcid.org/0000-0002-5606-8421
At the outlet of the R2, the reaction mixture shall contain 2PEA,
PhA, AcP and ACA. Strikingly, PhA, AcP and ACA have close boiling REFERENCES
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One Pot Synthesis of Phenylacetaldehyde From Styrene

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Received: 19 October 2023 | Revised: 19 January 2024 | Accepted: 18 February 2024