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Contents lists available at ScienceDirect

Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Aqueous phase catalytic hydroformylation reactions of alkenes

Sumeet K. Sharma, Raksh V. Jasra ∗
Reliance Technology Group, Reliance Industries Limited, Vadodara 391 346, Gujarat, India

a r t i c l e i n f o a b s t r a c t

Article history: The present article provides an overview of the recent developments in the area of aqueous phase
Received 29 March 2014 hydroformylation of alkenes. The commercial application of aqueous phase hydroformylation reaction
Received in revised form 23 June 2014 is restricted to the lower carbon chain alkenes due to the solubility and mass transfer limitations of the
Accepted 30 July 2014
higher carbon chain alkenes in aqueous phase. The approaches which have been developed to improve
Available online xxx
the solubility of higher carbon chain length alkenes for aqueous phase hydroformylation reaction are
emphasized in this article.
Keywords:
© 2014 Elsevier B.V. All rights reserved.
Biphasic hydroformylation
Aqueous phase
Alkene
Aldehyde
Surfactant
Cyclodextrins

1. Introduction 2. Commercial significance

Hydroformylation or oxo reaction is a commercially important
reaction to produce aldehydes from the reaction of an alkene with
syn-gas (mixture of hydrogen and carbon monoxide) in the pres-
ence of a catalyst (Scheme 1).
The primary products of a hydroformylation reaction are linear
and branched aldehydes with an additional carbon atom added to
the reactant alkene. The obtained aldehydes can be converted into
other commercially important chemicals via subsequent reactions,
like hydrogenation, condensation, amination, and oxidation. Gen-
erally, linear (n) aldehydes are more valuable than the branched
(iso) aldehydes, therefore, the n to iso ratio of aldehydes and
the rate of formation are important parameters to be considered
in an industrial hydroformylation process. The alkene hydro-
formylation is an important reaction for C C bond formation and
functionalization of C C bonds with diverse functional groups to
produce fine chemicals [1–3]. The chiral compounds for the produc-
tion of pharmacologically active molecules and agrochemicals can
be synthesized by asymmetric hydroformylation with controlled
enantio-, chemo- and regio-selectivity [4,5].
∗ Corresponding author. Tel.: +91 265 6696313; fax: +91 265 6693934.
E-mail addresses: sumeet.sharma@ril.com (S.K. Sharma), rakshvir.jasra@ril.com,
rvjasra@gmail.com (R.V. Jasra).
World production and consumption of hydroformylation (oxo)
chemicals is about 11 million metric tons per year with expected
growth rate of 4.0% per year [6]. These oxo chemicals are used to
produce solvents, detergents, plasticizers, fragrances and interme-
diates for fine and specialty chemical industry.
Propanal produced by ethylene hydroformylation and its
derivatives is used as a solvent, pesticide intermediates and print-
ing ink applications. Propanol is used as a precursor for glycol ether
and surface coating applications. The other propanal derivatives,
sodium and calcium propionates finds application in the grain and
food preservatives, 3,4-dichloropropionanilide as a herbicide and
cellulose acetate propionate, as a plastic sheeting and molding pre-
cursor.
The market demand for C4 aldehydes which are synthesized by
hydroformylation of propylene is higher among all oxo chemicals
due to its consumption for the production of 2-ethylhexanol and
butanol. 2-Ethyhexanol is used for the production of dioctyl phtha-
late, other plasticizers, coatings, adhesives, stabilizers, perfumery
and specialty chemicals. 2-Ethylhexanol derivatives are used as
additives for diesel fuel to reduce emissions and for lube and mining
oil to improve its performance. n-Butanol is used for the production
of coating systems, cleaning fluids, herbicides, dyes, printing inks,
personal care products, pharmaceuticals, plasticizers, textiles and
lube additives.
Among C5 aldehydes, n-pentanal (valeraldehyde) is the fastest
growing oxo chemical, used for production of 2-propylheptanol.
Valeraldehyde derivatives are used predominantly to make lube oil

http://dx.doi.org/10.1016/j.cattod.2014.07.059
0920-5861/© 2014 Elsevier B.V. All rights reserved.

Please cite this article in press as: S.K. Sharma, R.V. Jasra, Aqueous phase catalytic hydroformylation reactions of alkenes, Catal. Today
(2014), http://dx.doi.org/10.1016/j.cattod.2014.07.059
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Scheme 1. Hydroformylation reaction.
additives, which find application especially in automotive sector.
n-Valeric acid, which is prepared by hydroformylation of butene
followed by subsequent oxidation, is the basis of new ester type
lubricants for CFC-substitution in refrigeration systems. Volatile
esters of valeric acid are used in perfumes and cosmetics due to
their pleasant odor. The ethyl valerate and pentyl valerate are used
in food industries due to their fruity flavors.
C6 –C13 aldehydes are consumed for the production of fine and
perfumery chemicals, C6 –C13 alcohols for the synthesis of plasti-
cizers. C7–9 oxo acids which are the main derivatives of C7–9 oxo
aldehydes are used mainly to produce neopolyol esters. The 1-
heptanal which is produced by hydroformylation of 1-hexene is
a perfumery chemical and is also used for the production of lubri-
cants.
Linear C12 –C18 aldehydes find their applications in the detergent
industries to synthesize detergent grade alcohols. The detergent
grade alcohols can be converted into alcohol sulfates, ethoxylates,
alcohol ether sulfates and fatty amines for the diverse applications.
3. Why aqueous phase hydroformylation
Typically, homogeneous catalysts comprising a transition metal
and a ligand have been used for the hydroformylation of alkenes.
These transition metal complexes interact with carbon monoxide
(CO) and hydrogen (H2 ) to form catalytically active metal car-
bonyl hydride species. The first generation of the hydroformylation
catalyst was exclusively based on the cobalt metal (Fig. 1). The sep-
aration of products from reaction mixture, lower catalyst activity,
higher reaction temperature and pressure are the major limitations
of the first generation processes.
The second generation of the hydroformylation processes com-
bined developments for ligand modification and replacement of
the cobalt metal by rhodium. The rhodium metal modified by
triphenylphosphine (PPh3 ) ligand is termed as Low Pressure Oxo
(LPO) process [7]. The selectivity and n/iso ratio of aldehydes
improved significantly with highly active and selective homo-
geneous rhodium based complexes in LPO process. However,
practical problems of separation of products from the reaction mix-
ture, catalyst recovery and loss of expensive rhodium metal due
to the lower thermal stability of the rhodium based complexes
continued in the second generation catalysts too. In the hydro-
formylation process, leaching of rhodium metal has significant
impact on the process economy. For example, leaching of 1 ppm
rhodium per kg of product from a 400 kTA plant may result into
the financial loss of several million euros [8]. These disadvantages
inspired the development of a water soluble ligand, trisodium salt
of tris(m-sulfonatophenyl)phosphine (TPPTS; P(m-C6 H4 SO3 Na)3 )
in the third generation (1980s) hydroformylation catalyst
Fig. 1. Development of hydroformylation catalysts.
Please cite this article in press as: S.K. Sharma, R.V. Jasra, Aqueous phase catalytic hydroformylation reactions of alkenes, Catal. Today
(2014), http://dx.doi.org/10.1016/j.cattod.2014.07.059
Fig. 2. Aqueous phase hydroformylation of alkene using HRh(CO)(TPPTS)3 complex.
development [9–11]. The TPPTS ligand is highly soluble in water
(c.a. 1.1 kg/L), mostly insoluble in common non-polar solvents and
sufficiently stable under reaction conditions [12]. The rhodium
complex of TPPTS ligand is a water soluble complex which can
be separated easily from the reaction mixture after the comple-
tion of hydroformylation reaction in the aqueous phase. Despite all
the limitations discussed above, all the three generations of hydro-
formylation processes are still in commercial operation. Besides,
cobalt and rhodium metals, ruthenium, iridium, platinum, palla-
dium and iron [13] have also been studied as alternative metals for
hydroformylation, but poor activity of these metals compared to
cobalt and rhodium has restricted their application for the com-
mercial hydroformylation process.
In the aqueous phase hydroformylation reaction, the active cat-
alyst for the reaction is dissolved in water and remains in the
aqueous phase, whereas, reactants and products reside in the
organic phase. The mixture of aqueous and organic phases forms
two layers in the vessel and the reaction takes place at the inter-
face as shown in Fig. 2. The separation of catalyst (water soluble)
from the products mixture containing relatively non-polar organic
compounds is carried out by simple decantation (phase separation).
The aqueous phase containing the catalyst is recycled to the reactor
and the organic phase is subjected for the purification of products.
As compared to conventional homogeneous hydroformylation pro-
cesses, further distillation is not required in the aqueous phase
hydroformylation process to separate the catalyst from reaction
mixture.
4. Commercial process for aqueous phase
hydroformylation of propylene and butene
The water soluble rhodium complex based on the TPPTS ligand
(1, Fig. 3) was commercialized in 1984 for the hydroformyla-
tion of propylene to produce C4 aldehydes at Oberhausen site
of Ruhrchemie AG (Ruhrchemie/Rhône-Poulenc (RCH/RP) pro-
cess) [11,14–19]. This process works at milder reaction conditions
(50 bar pressure and 120 ◦ C temperature) to give 95% propylene
conversion, 92–97% selectivity to the linear aldehyde with 99%
selectivity of total C4 aldehydes. The critical point in this pro-
cess is the production of TPPTS as it is highly unstable in the
presence of air/oxygen. In this process, TPPTS ligand is used
around 50 fold in the excess to rhodium metal to achieve higher
selectivity of n-aldehyde and to minimize rhodium leaching (less
than 1 ppb rhodium leaching throughout catalyst batch life). The
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Fig. 3. Water soluble ligands.
constant activity of catalyst can be maintained for several years by
adding fresh TPPTS solution continuously or occasionally as per the
process requirement. In 1995, RCH/RP process was extended to the
aqueous phase hydroformylation of raffinate-2 (generally 50–60%
n-butene, balance is cis/trans 2-butenes and butanes after separa-
tion of 1,3-butadiene) obtained from naphtha cracker to produce C5
aldehydes as 1-butene has acceptable solubility in water [18,20]. 1-
Butene rich cut and syn-gas are fed to the reactor in which rhodium
and TPPTS ligand were present in the aqueous phase. The selectiv-
ity to n-valeraldehyde was obtained up to 95% which is comparable
to the selectivity of n-butanal produced by hydroformylation of
propylene. However, the rate of reaction for aqueous phase hydro-
formylation of raffinate-2 was observed significantly lower than
the aqueous phase hydroformylation of propylene probably due
to the lower solubility of butene in the aqueous phase than that
of propylene. In aqueous phase hydroformylation of raffinate-2,
slightly higher concentration of catalyst (150–500 ppm rhodium),
reaction temperature (120–130 ◦ C) and pressure (40–60 bar) were
used to achieve the satisfactory level of valeraldehyde space time
yields. In this process, 2-butenes remain almost unreactive due to
steric and electronic nature of the TPPTS ligand.
4.1. Other water soluble ligands for aqueous phase
hydroformylation of propylene
Apart from the TPPTS ligand, other water soluble ligands
(2–11, Fig. 3) such as SulfoXantPhos (2,7-bis(SO3 Na)-4,5-bis
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3
(diphenylphosphino)-9,9-dimethylxanthene; 3, Fig. 3),
NORBOS-Na (trisodium salt of 3,4-dimethyl-2,5,6-tris(p-
sulfonatophenyl)-1-phosphanorborna-2,5-diene; 4, Fig. 3), BINAS-
Na (octasodium salt of 2,2 -bis[(m-sulfonatodiphenylphosphino)-
methyl]-4,4 ,8,8 -tetrasulfonato-1,1 -binaphthalene; 5,
Fig. 3) and BISBIS-Na (hexasodium salt of 2,2 -bis[(m-
sulfonatodiphenylphosphino)-methyl]-disulfonato-1,1 -biphenyl;
6, Fig. 3) were reported for aqueous phase hydroformylation of
alkenes [21–26].
The sulfonated diphosphane ligand (BISBIS-Na) gave excep-
tionally high n/iso ratio of butanals by aqueous phase rhodium
catalyzed hydroformylation of propylene [21]. Around 10–12 times
higher reactivity of the rhodium complex with BINAS-Na ligand was
observed than the conventional TPPTS ligand. The BINAS-Na ligand
also showed higher (98/2) n/iso ratio of aldehydes at lower ligand
to rhodium ratio (7/1) against 94/6 n/iso aldehydes ratio for TPPTS
ligand with 80/1 ligand to rhodium ratio (Fig. 4) [22,27,28]. Another
ligand, NORBOS-Na showed lower n/iso aldehydes ratio due to the
steric effect of ligand [22].
The observed higher reactivity of the BINAS-Na ligand may be
attributed to the electronic and steric effect of the ligand on the
hydroformylation reaction. The BINAS-Na ligand showed very high
n/iso ratio of aldehydes at lower ligand to rhodium ratio than the
conventional TPPTS ligand. The higher production cost and higher
decomposition rate of the BINAS-Na ligand are the main limiting
factors for its commercial application in the aqueous phase hydro-
formylation reaction.
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Fig. 4. Reactivity of ligand for aqueous phase hydroformylation of propylene. Repro-
duced with permission from [22]. Copyright (1995) Elsevier.
4.2. Drawbacks of existing aqueous phase hydroformylation
processes
The existing commercial aqueous phase hydroformylation pro-
cess is restricted to the hydroformylation of propylene and
1-butene due to their fair solubility in water. The rate of aqueous
phase hydroformylation of alkenes depends upon the alkene sol-
ubility in water which makes process practicable at commercial
scale. The higher carbon chain alkenes (>C6 ) have lower solu-
bility in the water which results into the lower reaction rates
and mass transfer limitations. These factors make them unfa-
vorable at commercial scale. To overcome these issues, other
approaches such as, use of co-solvents (mostly methanol, ethanol),
amphiphilic phosphine ligands, surfactants (cationic, anionic, dou-
ble long chain cationic), additives (cyclodextrins, activated carbon)
are reported. These approaches improved the interfacial area as
well as the solubility of alkenes in the water during aqueous phase
hydroformylation of alkenes. For example, solubility of 1-octene
increased significantly (104 times) using mixture of 50% ethanol
and 50% water as a solvent instead of pure water [29]. Formation
of the side products (e.g. acetals), decreased n/iso ratio of aldehy-
des, leaching of catalyst/metal are the major disadvantages of the
use of co-solvents in the aqueous phase hydroformylation reaction.
By using a buffer solution of sodium carbonate and bicarbonate
(pH = 10), the acetals formation could be minimized [29]. Recently
Obrecht et al. compiled the alternative approaches which have
been developed for the aqueous phase hydroformylation of alkenes
[30]. In the present review, recent developments for the aqueous
phase catalytic hydroformylation of the higher carbon chain length
alkenes to overcome the solubility and mass transfer limitations
are emphasized.
5. Rhodium metal complex catalyzed aqueous phase
hydroformylation of higher carbon chain (>C5 ) alkenes
The catalytic activity of HRh(CO)(TPPTS)3 and
HRh(CO)(TPPMS)3 (TPPMS; 2, Fig. 3) was studied by Baricelli
et al. for the hydroformylation of 1-hexene, 2,3-dimethyl-1-
butene, styrene and cyclohexene using mixture of water and
n-heptane (1:1 by volume) as a solvent [31]. Higher catalytic
activity of HRh(CO)(TPPTS)3 and HRh(CO)(TPPMS)3 complex
was reported for the hydroformylation of 1-hexene followed by
2,3-dimethyl-1-butene, styrene and cyclohexene at 80 ◦ C and
54 atm syn-gas pressure (CO/H2 = 1/1). Interestingly, this approach
was extended for the hydroformylation of mixed alkenes having
medium carbon chain length (C4 –C7 ) present in the naphtha
Please cite this article in press as: S.K. Sharma, R.V. Jasra, Aqueous phase catalytic hydroformylation reactions of alkenes, Catal. Today
(2014), http://dx.doi.org/10.1016/j.cattod.2014.07.059
Fig. 5. Rh-complex, ligand and ionic liquid as a solvent [35]. Reproduced with per-
mission from [35]. Copyright (2013) Elsevier.
cut. Alonso et al. carried out aqueous phase hydroformylation
of Venezuelan naphtha cut (42% C4 –C7 alkenes, 31% paraffins,
19% naphthenes, 7% aromatics) using HRh(CO)(TPPTS)3 com-
plex in the water [32]. Almost 86% conversion of alkenes was
achieved in 200 h reaction time at 80 ◦ C, 800 psi syn-gas pres-
sure. The mono- and di-substituted alkenes present in naphtha
cut reacted faster (50% conversion in 24 h reaction time) than
the sterically hindered alkenes. The concentration of paraffins,
naphthenes and aromatics remain constant during the reaction.
Very recently, aqueous phase hydroformylation of light naph-
tha which contain around 61.5% alkenes (linear, branched, cis,
trans, internal) was studied using HRh(CO)(TPPTS)3 complex [33].
Around 95.4% conversion of alkenes with 95% yield of aldehydes
was obtained in 6 h at 70 ◦ C reaction temperature and 100 bar
syn-gas pressure in water-toluene mixed solvent. The n/iso ratio
of aldehydes was found to be 0.11 which is very low for rhodium
based catalyst, even significantly lower than the cobalt based
catalyst.
The sulfonated bidentate ligands are very selective to linear
aldehyde not only for hydroformylation of lower carbon chain
alkenes but also for the hydroformylation of higher carbon
chain length alkenes. Hamerla et al. achieved higher selectiv-
ity to linear aldehyde (98/2) using SulfoXantPhos ligand with
Rh(CO)2 (acac) in the presence of surfactant for hydroformylation
of 1-dodecene (TOF > 300 h−1 ) [26]. Interestingly, apart from
hydroformylation, SulfoXantPhos ligand was also found to be
very active for aqueous phase hydroaminomethylation reaction
in the presence of an imidazolium-based ionic liquid. Upto 95%
yield of amines (n/iso ratio of amines = 78) were obtained with
16,000 h−1 TOF in the presence of piperidine as an aminating
agent [34]. Recently, up to 98% conversion of 1-octene with 94%
selectivity to the aldehydes (n/iso = 2.7) was reported for aqueous
hydroformylation of 1-octene using ionic complex, bis-[1-butyl-
2-diphenylphosphanyl-3-methylimidazolium]tetrachloride-
rhodium(III)hexafluorophosphate, 12, (Fig. 5) with ligand, 13,
(Fig. 5) and room temperature ionic liquid, 14, (Fig. 5) as a solvent
[35].
The effect of steric and electronic factors of phosphine ligand
was studied by Wang et al. for aqueous phase hydroformylation
of 1-dodecene [36]. Two ligands, 2-MOTPPTS (tri(2-methoxyl-3-
(sodium sulfonato)phenyl)phosphine; 8, Fig. 3), and 4-MOTPPTS
(tri(4-methoxyl-3-(sodium sulfonato)phenyl)phosphine; 9, Fig. 3)
were synthesized and used for aqueous phase hydroformylation
of 1-dodecene [36]. Both ligands showed very low activity for
rhodium catalyzed hydroformylation of 1-dodecene due to the
poor solubility of 1-dodecene in the aqueous phase. Activity of 2-
MOTPPTS and 4-MOTPPTS was observed to improve significantly by
addition of CTAB. However, it is still lower than the conventional
TPPTS ligand, perhaps, due to the presence of strong electron donat-
ing methoxyl groups on the aromatic ring of MOTPPTS ligands.
The higher basicity of 2- and 4-MOTPPTS ligands is another rea-
son for lower activity of the MOTPPTS ligands than the TPPTS. The
strong coordination of the MOTPPTS ligands with rhodium metal
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Fig. 6. Amphiphilic phosphine based ligands.
makes more difficult to dissociate one ligand molecule from the
rhodium complex to form active catalyst species for the hydro-
formylation reaction. In another study, rhodium polyethylene
glycolate complex was found highly active catalyst for the aqueous
phase hydroformylation of broad range of alkenes, C11 cut inter-
nal alkenes, cyclooctene, diisobutylene, 1-dodecene, 1-hexene,
1-octene, styrene, ␣-methylstyrene and 2,4,4-trimethylpent-1-ene
[37].
For the aqueous phase hydroformylation of terminal alkenes
(4-pentenoate and acetoxystyrene), Boulanger et al. synthe-
sized two ligands based on the diphosphadiazacyclooctane
(10–11, Fig. 3) [38]. Complete conversion of 4-pentenoate with
99% aldehydes (n/iso = 1.1) selectivity was reported for hydro-
formylation of 4-pentenoate, whereas, lower conversion of
acetoxystyrene (83%) with 98% selectivity to aldehydes (n/iso = 0.5)
was observed for Rh(CO)2 (acac) catalyzed hydroformylation of
acetoxystyrene using ligand (10) at 80 ◦ C and 50 bar syn-gas pres-
sure. The ligand (11) showed lower activity and selectivity to
aldehydes for the hydroformylation of 4-pentenoate and ace-
toxystyrene.
The water soluble dendrimers were also used as ligands
for the rhodium [RhCl(COD)]2 ; (COD = 1,5-cyclooctadiene) cat-
alyzed hydroformylation of 1-octene [39]. Hager et al. reported
the synthesis and activity of dendrimer based ligands (tris-
2-(5-sulfonato-salicylaldimine-ethyl)-amine; diaminobutane-(5-
sulfonato-salicylaldimine)) and water soluble mononuclear 5-
sulfonato propylsalicylaldimine Rh(I) complexes [39]. The den-
drimer base ligands were found to be more active (less rhodium
leaching) than the mononuclear based rhodium complexes for the
Please cite this article in press as: S.K. Sharma, R.V. Jasra, Aqueous phase catalytic hydroformylation reactions of alkenes, Catal. Today
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5
hydroformylation of 1-octene at 70 ◦ C and 40 bar syn-gas pres-
sure.
5.1. Amphiphilic phosphines based ligands
The amphiphilic phosphines (15–24, Fig. 6) are surface active
phosphines having a hydrophobic tail end and several hydrophilic
ends. These surface active phosphines work not only as a lig-
and for the rhodium or cobalt metal catalyzed hydroformylation
of alkenes but also as a surfactant to enhance the solubility of
alkenes in aqueous phase. Use of amphiphilic phosphine ligands
can show stronger stabilizing effect on metal species and effec-
tively decrease the interfacial resistances and phase separation
time.
The water soluble amphiphilic phosphine ligands (15–18,
Fig. 6) were synthesized by Solsona et al. for the aqueous
phase hydroformylation of 1-octene in the mixture of water
and methanol as a solvent [40]. Significantly lower selectiv-
ity to the aldehydes was observed using ligands (15–18) than
the commercial TPPTS ligand at 80 ◦ C and 1-octene to rhodium
molar ratios 500 and 1000. The water soluble amphiphilic lig-
and, sodium salt of sulfonated n-C12 H25 OC6 H4 P(C6 H4 -p-CH3 O)2
(DMOPPS; 19, Fig. 6) was also studied in combination of
RhCl(CO)(TPPTS)2 complex for the aqueous phase hydroformy-
lation of 1-octene, 1-decene, 1-dodecene, 1-tetradecene and
1-hexadecene [41].
The RhCl(CO)(TPPTS)2 complex with DMOPPS showed high
catalytic activity for the hydroformylation of long chain alkenes
(Table 1) due to the surface activity and micelle forming
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Table 1
Aqueous phase hydroformylation using RhCl(CO)(TPPTS)2 complex with DMOPPS. Reproduced with permission from [41]. Copyright (2008) Elsevier.
Entry Alkene % Conversion % Selectivity
Aldehydes
1 1-Octene 92.6 77.6
2 1-Decene 93.4 74.5
3 1-Dodecene 77.2 86.7
4 1-Tetradecene 97.1 83.9
5 1-Hexadecene 97.5 84.6
Reaction conditions: [RhCl(CO)(TPPTS)2 ] = 0.96 mmol/L, water = 2.5 mL, alkene/Rh molar ratio = 1875, DMOPPTS/Rh molar ratio = 6, syn-gas pressure = 3.0 MPa, T = 100 ◦ C,
600 rpm.
property of amphiphilic phosphine, DMOPPS, which assisted to
stabilize the aqueous/organic phase boundary and enhanced the
rate of hydroformylation reaction [41]. However, leaching of the
rhodium from aqueous phase to organic phase was observed in
the range of 0.021–0.12 ppm during the reusability experiments
for hydroformylation of 1-decene.
Goedheijt et al. prepared the amphiphilic diphosphine lig-
ands derived from the xantphos with surface active pendant
groups, -4-C6 H4 O(CH2 )nC6 H4 (SO3 Na)- (n = 0, 3, 6; 20, Fig. 6) [42].
The increased solubility of alkene in the aqueous phase was
reported using these surface active groups, which resulted into
the higher activity (upto 14 times higher than the xantphos)
and reusability of catalyst for the aqueous phase hydroformyla-
tion of 1-octene. Selectivity to linear aldehyde was reported in
the range of 94.7–96.9%. Other amphiphilic phosphine ligands
(tris[p-(10-psulfonatophenyl-decyl)phenyl]phosphine, and chelat-
ing phosphine tetrasulfonated 2,2 -bis[di[p-(10-phenyldecyl)-
phenyl]phosphinomethyl]-1,10-biphenyl) (21–22, Fig. 6) were
found to be more active than the TPPTS for the aqueous phase
hydroformylation of 1-octene and tetradecene [43]. The bio-ligands
based on amino acids (l-cysteine (24, Fig. 7), l-tryptophan (25,
Fig. 7), l-methionine (26, Fig. 7)) and oligopeptides (glutathione,
l-cystine and vancomycin) were also studied for the hydroformy-
lation reaction in aqueous medium [44].
5.2. Surfactants for the aqueous phase hydroformylation
Surfactants (surface active agent; micellar systems) are studied
for the aqueous phase hydroformylation reaction to increase the
interfacial area and solubility of an alkene in the aqueous phase. In
the aqueous phase hydroformylation of long chain alkenes, gen-
erally cationic surfactant increased the rate of reaction due to
presence of anionic HRh(CO)(TPPTS)3 catalyst [45]. However, phase
separation time may increase significantly due to the formation of
highly stable emulsions. The enhanced hydroformylation rate is not
only due to increased solubility of an alkene in the aqueous phase
but also due to electrostatic interaction between positively charged
head group of the surfactant with negatively charged ligand (sul-
fonate groups). The addition of nonionic surfactants to reaction
mixture did not affect the rate of 1-dodecene hydroformylation
whereas anionic surfactants showed adverse effect on hydroformy-
lation reaction [45].
Fig. 7. Bio-ligands based on amino acids for hydroformylation in aqueous medium.
Reproduced with permission from [44]. Copyright (2007) Elsevier.
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n/iso t (h) TOF (h−1 )
Alkane iso-Alkenes
5.8 16.6 2.4 2 673.7
7.1 18.4 2.2 2 652.3
4.6 8.7 2.5 2 627.5
4.1 12.0 2.6 22 69.4
3.8 11.6 2.3 22 70.3
Wang et al. studied the effect of TPPTS, HRh(CO)(TPPTS)2
catalyst and alkene concentration on the critical micelle concen-
tration (CMC) of cetyltrimethylammonium bromide (CTAB) [46].
The decrease in CMC and increase in the apparent molar mass
of micelle was reported on the addition of TPPTS ligand and
HRh(CO)(TPPTS)2 complex in the aqueous solution of CTAB. The
effect of reaction parameters such as, surfactant (CTAB) concen-
tration, degree of emulsification on the rate of reaction, n/iso ratio
of aldehydes was studied for the hydroformylation of 1-dodecene
using RhCl(CO)(TPPTS)2 complex at 100 ◦ C and 1.1 MPa pressure
[47]. The addition of TPPDS (di sulfonated) ligand along with the
CTAB enhanced the n/iso ratio of aldehydes for RhCl(CO)(TPPTS)2
catalyzed hydroformylation of 1-dodecene due to the small steric
volume of the hydrophilic group [48].
The double long chain cationic surfactants (Fig. 8) were found to
be more effective than the other surfactants to improve the reaction
rate for aqueous phase hydroformylation of long chain alkenes. The
double long chain cationic surfactants were synthesized by reflux-
ing the acetone or alcoholic solution of dimethyl alkyl amine and
n-alkyl bromide [49].
The conversion, selectivity to aldehydes, n/iso ratio of aldehydes
and turn over frequency (TOF) were observed to increase signifi-
cantly using the double long chain cationic surfactants as compared
to CTAB (Table 2) for the hydroformylation of 1-dodecene using
RhCl(CO)(TPPTS)2 as a catalyst with excess TPPTS ligand [49]. The
work was extended to study the promotion effect of the cationic
Gemini and trimeric surfactants on RhCl(CO)(TPPTS)2 catalyzed
hydroformylation of 1-decene [50].
5.3. Mass transfer additives for aqueous phase hydroformylation
Among the various approaches reported to increase solubility of
higher carbon chain length alkenes in aqueous phase, use of chemi-
cally modified ␤-cyclodextrins is an attractive approach to enhance
the rate of aqueous phase hydroformylation reaction. Cyclodex-
trins (Fig. 9) which are non-toxic, and inexpensive have been used
as mass transfer agents in the aqueous phase hydroformylation of
higher alkenes. Cyclodextrins work as carriers to transfer alkenes
from the organic phase to the aqueous phase. Pioneer work has
been done by Monflier et al. for the application of chemically modi-
fied cyclodextrins in the aqueous phase hydroformylation reaction.
Fig. 8. Double long chain cationic surfactants. Reproduced with permission from
[49]. Copyright (2006) Elsevier.
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Table 2
Double long chain cationic surfactants for aqueous phase hydroformylation of 1-dodecene. Reproduced with permission from [49]. Copyright (2006) Elsevier.
Entry Surfactant % Conversion
1 C22 H45 N(CH3 )2 C16 H33 Br 83.3
2 C22 H45 N(CH3 )2 C12 H25 Br 86.2
3 C22 H45 N(CH3 )2 C8 H17 Br 85.9
4 C16 H33 N(CH3 )2 C16 H33 Br 90.7
5 C16 H33 N(CH3 )2 C12 H25 Br 94.5
6 CTAB 20.9
Reaction conditions: 1-dodecene = 2 mL (9.0 mmol), [RhCl(CO)(TPPTS)2 ] = 9.6 × 10−4 mol/L, [TPPTS]/[Rh] = 18, H2 O = 4.0 mL, surfactant concentration = 5.0 mmol/L, syngas
pressure = 2.0 MPa, T = 100 ◦ C, t = 1 h at 400 rpm.
The use of chemically modified (methylated) ␤-cyclodextrins
for hydroformylation of 1-decene showed aldehyde selectivity
up to 95% with 100% conversion of 1-decene [51]. The forma-
tion of alkene/cyclodextrin inclusion complex and solubility of
chemically modified ␤-cyclodextrins in the aqueous and organic
phases are the key factors to enhance the alkene conversion and
selectivity to aldehydes. The formation of alkene/cyclodextrins
inclusion complex and cyclodextrins/ligand (m-TPPTC; tris(m-
carboxyphenyl)phosphane trilithium salt) interaction was studied
in detail by NMR spectroscopy for the aqueous phase hydro-
formylation of alkenes [52,53]. The quantum chemistry calculation
suggested that the ␤-cyclodextrins interact with either un-
substituted or substituted (para and/or meta-position) sulfophenyl
group of phosphines present in the ligand (TPPTS) [54]. Recently
Tran et al. demonstrated the use of cyclodextrins for Rh(acac)(CO)2
catalyzed hydroformylation of methyl 4-pentenoate (upto 99% con-
version and 98% selectivity to aldehydes) using TPPTS as a ligand
[55]. The mixture of randomly methylated cyclodextrins of varied
size also has significant effect on the conversion of 1-tetradecene
due to the formation of ternary inclusion complexes between ran-
domly methylated cyclodextrins and alkene [56]. Neutral or ionic
nature of the modified ␤-cyclodextrins plays an important role for
the aqueous phase hydroformylation reaction. Higher selectivity
to linear aldehyde (n/iso ratio of aldehydes = 8.6; rate of reaction
increased 4 times) was achieved using ionic ␤-cyclodextrins in
the stoichiometric quantities with ligand 23 (Fig. 6) for rhodium
catalyzed hydroformylation of 1-decene [57]. Increase in the rate
of reaction, chemoselectivity and n/iso ratio of aldehydes was
reported for the use of cationic ␣-cyclodextrins as mass-transfer
promoters for the Rh-TPPTS catalyzed hydroformylation reac-
tion [58]. The ␤-cyclodextrins are useful mass transfer additive
for hydroformylation of terminal alkenes with enhanced reac-
tion rate using water-soluble, Rh2 (␮-StBu)2 (CO)2 (TPPTS)2 complex
[59]. The modified ␤-cyclodextrins having methyl groups on the
secondary face and poly(ethylene oxide) chains on the primary
face were found to be more efficient mass transfer additives then
Fig. 9. Structure of ␤-cyclodextrins.
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7
% Selectivity n/iso Ratio TOF (h−1 )
Aldehydes Alkane iso-Alkenes
96.9 2.6 0.5 3.7 1951.7
91.7 5.4 2.9 3.3 2019.7
93.0 3.4 3.6 3.6 2012.6
91.4 3.4 5.2 3.1 2125.1
93.0 4.2 2.8 3.3 2214.1
80.4 10.0 9.6 2.8 489.7
the randomly methylated ␤-cyclodextrins for Rh(acac)(CO)2 -TPPTS
catalyzed hydroformylation of 1-decene in the aqueous phase [60].
Additives other than cyclodextrins have also been studied
to enhance the rate of hydroformylation reaction. The rate of
hydroformylation reaction accelerated significantly by adding 1-
octyl-3-methylimidazolium bromide as a mass transfer additive
for aqueous phase hydroformylation of 1-hexene, 1-octene and 1-
decene [61]. The nature of cationic head group of additive and its
alkyl side chain length has significant effect on the catalyst per-
formance for the aqueous phase hydroformylation reaction [62].
Chaudhari et al. reported that the organic solution (co-solvent) of
PPh3 can act as a promoter ligand for aqueous phase hydroformyla-
tion of 1-octene catalyzed by HRh(CO)(TPPTS)3 complex [63]. The
rate of reaction was observed to increase by a factor of 10–50 using
PPh3 as a promoter ligand due to enhanced interfacial area of two
phases (aqueous and organic). The activated carbon also has posi-
tive effect as a mass transfer additive in the aqueous phase reaction.
[64–68]. However, the exact role of activated carbon in the aqueous
phase hydroformylation is not well understood but it does increases
the interfacial area due to its mesoporous and hydrophobic nature.
6. Cobalt metal complex catalyzed aqueous phase
hydroformylation
Cobalt based homogeneous catalysts are cheaper than the
rhodium complex and are still commercially used to produce
detergent and plasticizer grade alcohols in the significant amount
(>2.5 million tons per annum) by hydroformylation of higher car-
bon chain length alkenes [13]. However, cobalt based catalysts
are less active compared to the rhodium based complexes and
require higher pressure and temperature. Guo et al. synthesized
Co2 (CO)6 (TPPTS)2 complex for aqueous phase hydroformylation of
1-hexene and used as a catalyst in the presence of excess TPPTS.
[69]. Leaching of cobalt from the aqueous phase to the organic
phase was observed during the reaction. Recently, Mika et al.
reported the recovery of cobalt from organic phase using aque-
ous solution of TPPTS ligand [70]. In another study, Beller et al.
reported the aqueous phase hydroformylation of 2-pentene (60%
E-2-pentene + 40% Z-2-pentene) using Co2 (CO)6 (TPPTS)2 complex
with 10 times excess TPPTS ligand in water and anisole mixture as
a solvent [71]. Upto 71.2% selectivity to the aldehydes was obtained
with 1.94 n/iso ratio of aldehydes at 190 ◦ C and 100 bar pressure.
The catalyst was recycled four times without any significant loss in
the activity. Parmar et al. prepared CoCl2 (TPPTS)2 complex for the
hydroformylation of 1-hexene in water as a solvent [72]. At 60 ◦ C,
63% conversion of 1-hexene with 83% selectivity to aldehydes (n/iso
ratio = 2.2) was reported under 9 MPa syn-gas pressure.
6.1. Effect of surfactants and mass transfer additives
The activity of cobalt complex, CoCl2 (TPPTS)2 was observed to
increase in the presence of surfactant and co-solvents (methanol
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Table 3
Aqueous phase hydroformylation of 1-octene and 1-decene. Reproduced with permission from Ref. [73]. Copyright (2008) Elsevier.

Entry
Alkene CTAB (mmol/L) TPPTS/Co molar ratio % Conversion % Selectivity n/iso Phases separation time (min)

Aldehydes iso-Alkenes Alkane

1 1-Octene 0 1 28 64 26 10 2.8 –
2 1-Octene 5.5 1 96 92 7 1 2.3 60
3 1-Octene 5.5 10 95 95 4 1 2.3 15
4 1-Decene 0 1 31 57 38 5 2.7 –
5 1-Decene 5.5 1 95 95 3 2 2.3 60
6 1-Decene 5.5 10 97 96 3 1 2.4 15

Reaction conditions: [CoCl2 (TPPTS)2 ] = 1.0 mmol/L, substrate/catalyst mol ratio = 700, T = 100 ◦ C, pressure = 8 MPa, solvent (water) = 25 mL, t = 5 h.

and ethanol) for the aqueous phase hydroformylation of 1-octene

and 1-decene [73]. Lower conversion of the alkene was reported in
the absence of surfactant. The concentration of surfactant plays an
important role not only on the alkene conversion but also on the
selectivity to aldehyde and phases separation time (Table 3).
On adding the CTAB, conversion of alkene, selectivity to alde-
hyde and phase separation time increased significantly [73]. The
phase separation time decreased from 60 min to 15 min using
excess TPPTS to the reaction mixture containing CoCl2 (TPPTS)2
and CTAB in the water. Leaching of the cobalt from aqueous
phase to organic phase was observed in CoCl2 (TPPTS)2 cat-
alyzed hydroformylation reaction. The leaching of cobalt was Scheme 2. Synthesis of florhydral using aqueous phase hydroformylation.
minimized by adding excess TPPTS ligand into the reaction
mixture. The catalyst was reused up to four times without
7. Synthesis of fine chemicals by aqueous phase
significant lose in alkene conversion, selectivity to aldehydes
hydroformylation
and n/iso ratio of aldehydes. Formation of alcohols up to 21%
was observed for Co/TPPTS catalyzed hydroformylation of 7-
Hydroformylation of functionalized alkenes is very use-
tetradecene (84% conversion) in microemulsion at 80 bar syn-gas
ful tool for the synthesis of fine and perfumery chemicals.
pressure and 160 ◦ C [74]. As observed for rhodium complex cat-
The 3-(3-isopropenylphenyl)butyraldehyde which is a fragrance
alyzed hydroformylation of alkenes, addition of cyclodextrins as
(Florhydral) precursor, was synthesized by rhodium catalyzed
mass transfer additives has significant effect on n/iso ratio of alde-
hydroformylation of m-diisopropenylbenzene (Scheme 2) in the
hydes for CoCl2 (TPPTS)2 catalyzed hydroformylation of 1-octene
mixture of water and toluene as a solvent using TPPTS and human
[75]. The conversion of alkene and selectivity to aldehydes was
serum albumin (HSA) as ligands [77].
reported almost similar to that when CTAB was used as a sur-
The [Rh(COD)Cl]2 with TPPTS ligand showed 81.3% conversion of
factant (without any cyclodextrins) but n/iso ratio of aldehydes
m-diisopropenylbenzene with 52.2% selectivity to the desired alde-
decreased from 2.3 observed for CTAB to 1.3 in case of randomly
hyde in water-toluene mixed solvent at 60 ◦ C and 70 atm syn-gas
methylated cyclodextrin, RAME-␤-CD as a mass transfer addi-
pressure. Florhydral can also be synthesized directly by the aque-
tive.
ous phase hydroformylation of 1-isopropyl-3-isopropenylbenzene.
In another study, TPPTS ligand was replaced by other water sol-
Almost complete conversion of 1-isopropyl-3-isopropenylbenzene
uble bulky ligand, trisulfonated tris(biphenyl)phosphine (BiphTS;
(99.6%) with 98.6% yield of Florhydral was achieved at 100 ◦ C
7, Fig. 3). The sodium salt of BiphTS has almost similar solubility
using Rh(CO)2 (acac)/TPPTS catalyst system. The HSA ligand showed
to TPPTS, more stable in air, easy to synthesize than TPPTS (98%
higher selectivity to aldehydes than TPPTS for aqueous phase
H2 SO4 used for synthesis of BiphTS against oleum (60%) for TPPTS).
Rh(CO)2 (acac) catalyzed hydroformylation of alkenes [78]. Another
Due to higher stability in air, 15–20% increased yields of BiphTS
fine chemical, 1,4-diacetoxy-2-formylbutane, an intermediate for
can be obtained than the TPPTS ligand [76]. The cobalt complex
the production of Vitamin A was synthesized by the selective
of BiphTS ligand, CoCl2 (BiphTS)2 showed lower conversion of 1-
aqueous phase hydroformylation of 1,4-diacetoxy-2-butene using
octene (23%) and 60% selectivity to aldehydes (n/iso = 2.5) than the
Rh-TPPTS catalyst (Scheme 3) [79,80].
CoCl2 (TPPTS)2 complex (29% conversion, 65% selectivity to alde-
Higher selectivity to the desired aldehyde and lower activity
hydes with n/iso = 2.8) under identical reaction conditions due to
of Rh/TPPTS was reported for aqueous phase hydroformylation of
strong coordination of BiphTS with metal (Co) than the TPPTS lig-
1,4-diacetoxy-2-butene than that of homogeneous Rh/PPh3 cata-
and [68]. The conversion of 1-octene increased to 95% with 86%
lyst [79]. Activity of Rh/TPPTS catalyst was observed to improve
selectivity to aldehyde (n/iso = 2.1) using 5.5 mol/L CTAB concen-
by adding the surfactant but it is still lower than the activity
tration with CoCl2 (BiphTS)2 catalyst. The conversion of 1-octene
observed with homogeneous Rh/PPh3 catalyst. Almost complete
decreased to 90% with 81% selectivity to aldehydes (n/iso = 1.3)
conversion of 1,4-diacetoxy-2-butene (99.9%) with 100% selectivity
using chemically modified cyclodextrin (RAME-␤-CD; 5 mol/L) as a
to 1,4-diacetoxy-2-formylbutane was achieved in the mixed sol-
mass transfer additive instead of CTAB [68].
vent (toluene and water) using [RhCl(COD)]2 /TPPTS catalyst [80].

Scheme 3. Synthesis of 1,4-diacetoxy-2-formylbutane by aqueous phase hydroformylation of 1,4-diacetoxy-2-butene.

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Scheme 5. Aqueous phase hydroformylation of dicyclopentadiene.

Scheme 4. Aqueous phase hydroformylation of acrylates.

The leaching of rhodium (less than 0.03%) was observed from aque-
ous phase to organic phase [80]. The disulfonated xantphos ligand
showed upto 82% yield of linear aldehyde for rhodium-catalyzed
aqueous phase hydroformylation of 2-vinyl-5-methyl-1,3-dioxane
at 120 ◦ C [81].
The role of water for aqueous phase hydroformylation of methyl
acrylate, ethyl acrylate, butyl acrylate, 2-ethoxyethyl acrylate and
2-ethylhexyl acrylate (Scheme 4) was studied by Fremy et al. [82].
Based on their results, it was observed that the water can also act
as a reactant or as a coordinating solvent to alter the catalytic cycle.
The activity of RhCl(CO)(TPPTS)2 catalyst was studied for the
aqueous phase hydroformylation of dienes (dicyclopentadiene;

Scheme 6. [Rh(CO)(Pz)(TPPMS)]2 catalyzed hydroformylation of allylbenzenes.

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Scheme 7. Aqueous phase hydroformylation of ␤-isophorone.

Scheme 8. Aqueous phase hydroformylation of various substituted olefins.

Scheme 5) in the presence of CTAB (1 mmol), which showed 99.3%
conversion of dicyclopentadiene with 95.2% selectivity to aldehy-
des at 140 ◦ C and 1.5 MPa syn-gas pressure [83].
Other than rhodium and cobalt metals, aqueous phase hydro-
formylation of alkenes was also studied using ruthenium based
catalysts. Baricelli et al. synthesized the ruthenium complex
(Fig. 10; HRu(CO)(CH3 CN)(TPPTS)3 ]BF4 ) and characterized by FT-IR,
31 P NMR, etc. [84].
The activity of ruthenium complex (Fig. 10) for aque-
ous phase hydroformylation of alkenes was reported in
the order of 1-hexene > allylbenzene > 2, 3-dimethyl-1-
butene > styrene > cyclohexene. The ruthenium complex showed
sulphur (thiophene) tolerance limit upto 500 ppm concentra-
tion without having significant effect on the catalytic activity
which makes it a prominent catalyst for the hydroformylation
of sulfur contaminated feed (e.g. alkenes rich naphtha cut). The
aqueous phase hydroformylation approach is extended to the
synthesis of perfumery chemicals by hydroformylation of eugenol,
estragole, safrole and trans-anethole (Scheme 6) under moder-
ate reaction conditions using binuclear water soluble rhodium
[Rh(CO)(Pz)(L)]2 complexes and ruthenium complexes with ionic
liquid [HRu(CO)(CH3 CN)(L)3 ][BF4 ] (L = TPPMS and TPPTS) [85].
Fig. 10. Ruthenium complex for aqueous phase hydroformylation of alkenes [84].
Selectivity to the aldehydes was observed to increase in the
presence of surfactant, cetyltrimethylammonium chloride (CTAC),
although, phases separation time increased significantly [85]. Con-
version of eugenol (98%) with 93% selectivity to aldehydes was
reported using [Rh(CO)(Pz)(TPPMS)]2 complex and 1.02 mmol con-
centration of CTAC at 80 ◦ C and 2.07 MPa syn-gas pressure. The
rhodium complex showed higher catalytic activity for the hydro-
formylation reaction than the ruthenium complex. Among the
studied ligands, TPPMS ligand was found to be more aldehyde selec-
tive than the TPPTS for hydroformylation of eugenol, estragole,
safrole and trans-anethole under studied experimental conditions.
The activity of ruthenium complex was observed in the order
of eugenol > estragole ∼ safrole  trans-anethole [85]. The rhodium
and ruthenium complexes with both of the studied ligands (TPPMS
and TPPTS) showed poor reusability of the catalyst for hydro-
formylation of eugenol. For aqueous phase hydroformylation of
limonene, the addition of small amount of PPh3 (PPh3 :TPPTS ratio
of 0.05) showed improved conversion of limonene (12% in 21 h)
as compared to 1% without PPh3 using dinuclear water soluble
[Rh2 (␮-St Bu)2 (CO)2 (TPPTS)2 ] complex [86]. The authors reported
pale yellow color of organic phase which may be due to the leaching
of catalyst from the aqueous phase to the organic phase on addition
of PPh3 .
4-Formyl-3,5,5-trimethylcyclohexan-1-one is an important
intermediate for the synthesis of ␦-damascone, a floral woody
perfume. Synthesis of 4-formyl-3,5,5-trimethylcyclohexan-1-one
was carried out by the hydroformylation of ␤-isophorone
using Rh/TPPTS catalyst (Scheme 7) [87]. The authors reported
91.7% conversion of ␤-isophorone in 72 h with 3.1% yield of
4-formyl-3,5,5-trimethylcyclohexan-1-one at 100 ◦ C, 100 atm syn-
gas pressure using mixture of water and toluene as a solvent. The
reported lower yield of 4-formyl-3,5,5-trimethylcyclohexan-1-one

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Scheme 9. Aqueous phase hydroformylation of 2-benzyloxystyrene.
is due to the faster isomerization (21.4% yield) and hydrogenation
(43.4% yield) of ␤-isophorone.
Paganelli et al. studied the hydroformylation of substituted
olefins (Scheme 8) for the synthesis of fine chemicals using
Rh/TPPTS catalyst.
The Rh/TPPTS catalyst showed lower reactivity (59–99% conver-
sion with more than 99% selectivity to the aldehyde in 24–70 h) for
the hydroformylation of 1,1-diarylethenes [88]. For aqueous phase
hydroformylation of 1,1 bis(p-fluoro-phenyl)-prop-2-en-1-ol, 99%

conversion with 92% selectivity to the aldehyde  reported
were
at 100 ◦ C and 50 atm syn-gas pressure pCO = pH2 . In case of
phenylvinylether, 98–99% conversion with 99% aldehyde selectiv-
ity was achieved in 24 h reaction time.
Later this study was extended to the aqueous phase hydro-
formylation of 2-benzyloxystyrene (Scheme 9) to produce
pharmacological active compounds using TPPTS (1, Fig. 3) and Sul-
foXantPhos (3, Fig. 3) ligands [89].
In case of TPPTS ligand, 99% conversion of 2-benzyloxystyrene
with 30% selectivity to linear aldehyde were achieved in 24 h reac-
tion time, whereas, SulfoXantPhos showed very slow reaction rate
(55.4% conversion of 2-benzyloxystyrene in 240 h) with higher
selectivity to the linear aldehyde (85.6%) than the TPPTS ligand.
8. Future directions
Subsequent to commercialization of aqueous phase hydro-
formylation of propylene and butene, numerous work have been
done for the development of aqueous phase catalytic process for
hydroformylation of higher carbon chain length alkenes. The poor
solubility of higher carbon chain alkenes in water, mass trans-
fer limitations and lower reaction rates are main disadvantages
of existing aqueous phase hydroformylation processes. Till today,
none of the catalyst/process is commercialized for aqueous phase
hydroformylation of higher carbon chain length alkenes. There is
still need to develop commercially feasible low cost water soluble,
stable and selective catalyst as well as approaches to increase the
solubility of alkene in aqueous phase, simple phase separation in
minimum holding time and negligible leaching of rhodium/cobalt
metal from aqueous phase to organic phase.
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