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Page 1 of 7 Catalysis Science & Technology

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Catalysis Science & Technology Accepted Manuscript

MINIREVIEW

Sn(IV)-based Organometallics as Catalysts for the

Cite this: DOI: 10.1039/x0xx00000x
Production of Fatty Acid Alkyl Esters
M. R. Meneghettia and S. M. P. Meneghettia

Received 00th January 2012, This paper discusses mechanistic aspects and applications of organotin(IV) catalysts.
Accepted 00th January 2012 Particularly, these complexes are employed in a series of industrial reactions in which esters
are obtained via (trans)esterification, e.g., polyesters, and lactones. Due to the recent results
DOI: 10.1039/x0xx00000x
pointed in the literature, the potential application of this type of catalysts in the synthesis of
www.rsc.org/ fatty acid alkyl esters (FAAEs) is also presented.

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 Catalysis Science & Technology Page 2 of 7

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Catalysis Science & Technology Accepted Manuscript

MINIREVIEW
R
Introduction R' Cl
Sn
R
R' NMe 2
R O R R
Although the chemistry of organotin compounds is not often R'O
Sn
O
Sn
R Cl O
R
R
R
Sn
O
R
Ph
Sn Sn O Sn O O Sn Sn
deeply discussed in organometallic textbooks, studies involving R
R
O OR' R O Cl
R
O
O
R R R
Me
R Br
tin compounds are quite old! The first organotin compound, R' Sn
Cl R
diethyltin dichloride, Et2SnCl2, was prepared by Frankland in R
1849, and this is often considered as the beginning of Fig. 2 Chemical structures showing the hypervalent property of
organometallic chemistry. However, it took almost one hundred organotin(IV) compounds.
years (1943) following the Frankland discovery for the first
commercial application of organotin compounds, in which they Most of the evidence used to elucidate the
were used for the stabilization of PVC against heat during (trans)esterification reaction mechanism with organotin(IV)
processing. From that time, a variety of industrial and complexes is based on exhaustive studies of the catalytic
biological applications have been subsequently developed. conversion of alcohols and isocyanides for polyurethane
Organotin compounds are currently the most widely produced production.5 Polyurethanes are polymers resulting from the
organometallic complexes in the world. In terms of catalytic reaction between polyols and polyisocyanates in the presence or
applications, they are employed as catalysts in a series of absence of catalysts (see Figure 3). Here, for the association
industrial reactions, in which esters are obtained via step, the isocyanate group can be seen as being analogous to the
(trans)esterification, e.g., in the synthesis of fatty acid alkyl carboxylate group.
esters (FAAEs),1 polyesters,2,3 and lactones.4
O H H O
The catalytic properties of organotin(IV) complexes arise HO OH + OCN NCO O O C N N C
due to their Lewis acid characteristics. Tin atoms are capable of
O O
coordinating additional molecules in solution, as well as HO OH + HOOC COOH O O C C
undergoing associative exchange of certain labile ligands with H 2O
O O
other compounds in solution (see Figure 1). HO OH + ROOC COOR O O C C
ROH

R' OR'' Fig. 3 Polyurethane and polyester formation from alcohols and
isocyanides, and alcohols and esters, respectively.
O
R X
R OOCR' As previously mentioned, the catalytic mechanisms for
Sn
Sn
''

R X transesterification and esterification in the presence of

R

R
O
'C

R OOCR'
O
O

organotin complexes are quite similar, but some particularities

'C
O
H

must be considered for a more rigorous mechanistic

X

R X proposition. For that reason, we will present our consideration

Exchanges Sn Coor dinat ions separately below.
R X It is worth mentioning that Lewis acid catalysts for
(trans)esterification reactions are, in general, milder than
H

R
' '' O

' 'O

H Brønsted acids and produce a stronger template effect because

R

H
H

R OR''' OR''' they are expected to be sterically bulkier than a proton.

R X
Sn Sn
R OR''' R X Transesterification – Catalytic Mechanism
Fig. 1 Coordination of additional ligands and associative ligand
There are at least two distinct mechanisms that can be proposed
exchange.
for organotin-catalyzed transesterification reactions: Lewis acid
mechanisms and exchange/insertion mechanisms, both of
These characteristics stem from the fact that tin is a metal
which will now be discussed further.5
having empty 5d orbitals, which allows it to expand its
coordination number via interaction with non-bonding electron
pairs of atoms, most notably oxygen and nitrogen. Even groups Lewis Acid Mechanism
bearing non-bonding electron pairs of atoms can act as The Lewis acid mechanism is the most common mechanism
additional ligands, resulting in intramolecular coordination or proposed for tin-catalyzed transesterification and is shown in
intermolecular association to give dimers, oligomers, or Figure 4. There are two possible variations of this mechanism.
polymers (see examples in Figure 2). Thus, all proposed In both, the tin compound behaves as a classic Lewis acid, first
catalytic (trans)esterification mechanisms involving coordinating to the ester through the carbonyl oxygen to
organotin(IV) complexes include ligand association and/or polarize the carbonyl.6 This coordination increases the
ligand exchange processes. electrophilicity of the carbonyl carbon toward inter or
intramolecular nucleophilic attack by an alcohol, as shown in
Figure 4 (A and B, respectively). This mechanism is normally
followed by systems in which ligand exchange with the alcohol
is not favored.

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undergo alcoholysis, as they appear to carry out the reaction

H
R' OR'' unchanged and to behave as Lewis acids.2,9
A O R''' B
R' OR'' R X
R'COOR'' R
O
X
Other interesting catalytic systems based on organotin(IV)
Sn
R X O Sn
complexes include various tetraorganodistannoxane

Catalysis Science & Technology Accepted Manuscript

R'COOR'' R X R X R X
Sn Sn
R X R X R'COOR'''
R'''OH compounds, [XR2SnOSnR2X]2. These compounds possess a
stable ladder-like dimeric structure (Figure 6) and are very
R'COOR''' R' OR''' R' OR''

H H
active in transesterification. The first studies related to the use
O O

R'
OR'''
OR''
R
Sn
X
H
R
Sn
O
R''' of these complexes in transesterification reactions were carried
out by the group of Otera in the beginning of the 1990s.10
R' OR''' R X R X
OR'''
R' OR'' X
O O
R X R X
Sn R''OH O
Sn R X
R X R X
R''OH R
Sn
X R R R R

Fig. 4 Illustration of the two organotin(IV)-based catalytic X Sn O Sn X

transesterification reactions taking place via the Lewis acid R= Bu, Me
mechanism: A) intermolecular nucleophilic attack and B) R X = Cl, OH, NCS, OMe, OAc
X Sn O Sn
intramolecular nucleophilic attack of the alcohol previously
coordinated on the metal. R R X R
Fig. 6 General structure of tetraorganodistannoxanes.
Exchange/Insertion Mechanism
This mechanism involves three basic steps, which are outlined The proposed mechanism for tetraorganodistannoxane-
in Figure 5: (1) Associative exchange of the alcohol onto the tin catalyzed transesterification has been discussed because their
compound; (2) Coordination and insertion of the carboxylic application in transesterification reactions. The reaction
group into the Sn-O bond of the tin alkoxide formed in (1); and mechanism for this set of compounds is also based on the two
(3) Associative exchange of the intermediate. general mechanisms, Lewis acid or exchange/insertion. The
primary mechanism followed depends on the nature of the X
R X
groups in the structure. Jousseaume and co-workers
Sn demonstrated that the tetraorganodistannoxane
R X [ClBu2SnOSnBu2Cl]2 is recovered unchanged after the
reaction, suggesting that its efficiency in the transesterification
HX R'''OH
comes more from its unique bidentate coordination properties
as Lewis acids than from its ability to transfer alkoxide groups.9
R ''' R OR'''
OO Esterification – Catalytic Mechanism
R'C Sn
R OR'''
R'COOR''
As previously mentioned, most organotin(IV)-based catalyzed
esterification reactions follow one of two general mechanisms
R'''OH
(Lewis acid and exchange/insertion: Figures 4 and 5). However,
R' OR'' it should be noted that in esterification reactions catalyzed by
R'
organotin(IV), the ligand exchange process is quite important
R O OR''' O because the protonolysis ability of a carboxylic acid is typically
R OR'''
Sn Sn higher than that of an alcohol.
R OR''' R OR''' It is additionally worth mentioning that although SnCl4, a
H popular Lewis acid, is not usually employed in esterification,
R' most other organotin(IV) compounds work quite well (their
R''OH OR'''
R O OR'' acidity is tuned by the presence of donating alkyl groups). For
Sn example, Me2SnO is commonly used to catalyze esterification,
R OR''' and the accepted catalytic mechanism is depicted in Figure 7.11
Fig. 5 Illustration of the organotin(IV)-based catalytic 1/n [Me2SnO] n
transesterification reaction via the exchange/insertion
O
mechanism. ROH
OR
Me2 SnO
Systematic studies of the use of organotin(IV) complexes as
catalysts for transesterification began at the end of the 1960s. In
one such study, Pereyre et al. demonstrated that tributyltin R
alkoxides, R3SnOR’, were able to catalyze transesterification at O OR
120 ºC after 40-100 hours.7 Later, Poller et al. carried out work Me2 Sn Me 2Sn
O OH
on the relative catalytic activity of a series of organotin O
compounds on the reaction between propyl acetate and O
methanol,8 and found that the activity decreases in the order OH
OR
R2Sn(OAc)2 > R2SnO > R2SnCl2 > R2SnS, R4Sn. The first two Me 2Sn H 2O
catalysts of this series should pass through a transesterification O
reaction via the exchange/insertion mechanism, and the latter
two follow the Lewis acid mechanism. It is worth mentioning O
that organotin chlorides are currently considered to not readily Fig. 7 Illustration of the organotin(IV)-based catalytic
esterification reaction using Me2SnO as a catalyst precursor.

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amounts of organotin catalysts are used, some examples of

Good yields of esters are also obtained when carboxylic which are displayed in Figure 9.17
acids are treated with catalytic amounts of
dichlorotetrabutyldistannoxanes, [ClBu2SnOSnBu2Cl]2;

Catalysis Science & Technology Accepted Manuscript

however, the dimeric structure is not stable in the presence of Cl OH
O
O
the carboxylic acid, and it is quite possible that the monotin Sn
Sn O O
Sn Sn O
compounds formed are responsible for catalyzing the OH OH
O
O
esterification. Furthermore, a release of Brønsted acids such as
HCl should also necessarily participate in the catalyzed
esterification upon reaction of the dimer with RCOOH.12
Fig. 9 Chemical structures of some organotin(IV) catalysts
employed in the polyesterification reaction of alkyd resins.
Industrial application of organotin(IV)
compounds as catalysts for (trans)esterification For the case of when these reactions are assisted by
reactions – Synthesis of alkyd resins complexes containing Lewis acid sites, a mechanism in which
The most important industrial use of organotin(IV) complexes the active species are generated by a vacant coordination site of
as catalysts for (trans)esterification is in the production of alkyd metal has been suggested.6
resins. Alkyd resins are polyesters modified by the presence of Most of the work regarding the synthesis of alkyd resins by
fatty acids (FAs) or triacylglycerides (TGs) and are largely used alcoholysis involving the use of catalysts has been performed in
in the paint industry. A general example of the synthesis of an industrial laboratories, and only a few reports are available in
alkyd resin is depicted in Figure 8. the literature.5,18 An example of a modified alkyd resin is that
produced by alcoholysis of soybean oil with pentaerythritol,
O n HO followed by esterification with pentaerythritol and phthalic
HO OH
O O O + 2 3
anhydride. Several catalysts (LiOH, dibutyltin oxide (Bu2SnO),
n O
n
O OH [cat. 1]
n
and dibutyltin dichlorid (Bu2SnCl2)) are used for alcoholysis
OH
O
O and/or esterification reactions. The catalytic system
TG Glycerol MG
LiOH/Bu2SnCl2 has proven to be more effective than the
conventional method, in which only LiOH is used.17
Nevertheless, as already mentioned, the industrial
O
HO OH O importance of these area leads to development of new materials
N + N O O O N
O O
O
composed by alkyd resins, and there is some examples of
[cat. 2]
n
O O n
patents that can illustrate these advances. Generally, process
O Alkyd resin
MG
Phthalic anhydride
modifications are claimed, but the use of well-established
tin(IV) catalytic system reinforces the importance of their
where: n= normally 14-16 performance even for new developments.
TG= triacylglyceride
M G= monoacylgliceride Bu2SnO was also employed as catalyst to obtain an alkyd
cat. 1= inorganic base
cat. 2= organotin(IV)
resin for room temperature or thermally curable paints.19
Dibutyltin dilaurate, Bu2Sn(Lau)2, was present in the
Fig. 8 General example of the synthesis of alkyd resins. The composition of the catalytic system used to obtain a alkyd wood
TG employed typically contains several unsaturated carbons in lacquer for home and office decoration, that is considered,
the alkyl chain. Figure adapted from Reference 13. environment-friendly, nontoxic and harmless, due the water and
alcohol solubility; furthermore, the resin obtained shows
Despite the fact that polyesters themselves generally exhibit suitable properties like: good fullness, good leak tightness, and
very interesting chemical and physical properties, chemical good hardness.20 The catalysts Bu2SnO, and Bu2Sn(Lau)2 were
stability, and weathering resistance, it is too difficult to use used in the preparation of acrylic-modified waterborne tall oil
them directly in paint applications. Therefore, modification of alkyd emulsion, used for coating metal and wood and this
polyesters with FAs or TGs improves some of their properties, material exhibits high corrosion resistance and mechanical
primarily durability and flexibility. From a chemical point of property.21
view, their main difference from other polyester resins is that Another field is the production of aqueous alkyd resin
alkyd resins contain unsaturated fatty acid side groups.14 dispersion used for a paint composition such as normal
Alkyd resins can be directly produced from FAs or TGs by temperature curing paints or thermosetting paints. In this case,
acidolysis or alcoholysis.13,15,16 In the case of synthesis from several organotin(IV) can be used as butyl stannoic acid
FAs, which is based on the displacement of fatty acids by (BuSn(O)OH), Bu2SnO, Bu2Sn(Lau)2, and SnO2.22 Also,
polyacids, a polyesterification among the FAs, polyacids, and Bu2Sn(Lau)2 is used to obtain aqueous alkyd resin that leads to
polyalcohols takes place without the addition of a catalyst. transparent, and free of turbidity dispersion,23 as well, to
On the other hand, catalysts can be used in the alcoholysis prepare alkyd resin emulsions that are useful as a binding
process (transesterification followed by polyesterification). agents for coatings for textiles, mineral materials, metal and
First, the transesterification of TGs in the presence of wood.24
polyalcohols generally occurs in the presence of Brønsted bases Another interesting application of organotin(IV) species is
(e.g., NaOH, KOH, LiOH, CaO, and PbO) between 240 and in the synthesis of alkyd resins in which recyclable raw material
270 ºC. If no catalysts are present, temperatures higher than 270 is used. In this case, a mixture of Bu2SnO, and Zn(OAc)2 is
ºC must be employed. For the second step, polyesterification, used into manufacture of an alkyd resin, using the polyester
the use of LiOH, Ca salts, and acidic catalysts such as H3PO4, resin recovered and regenerated from wastes, such as scrap
HCl, and H2SO4 have been reported. However, in industry large polyethylene terephthalate bottle. This resin presents

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thermosetting type coating feature, and exhibits a very good Table 1 Production of FAMEs (percentage yield) by
transparency.25 transesterification in the presence of BuSn(O)OH, Bu2SnO, and
Bu2Sn(Lau)2 using reflux conditions or a closed steel reactor
Potential industrial application – Synthesis of fatty acid under different reaction conditions (molar proportions of

Catalysis Science & Technology Accepted Manuscript

alkyl esters for biodiesel and green lubricants MeOH:soybean oil:catalyst = 400:100:1; constant magnetic
The use of organotin(IV) as a potential catalyst for the stirring = 1000 rpm).
production of fatty acid alkyl esters (FAAE) has become a new Catalyst
field of research.26 Green solvents and lubricants, as well as Temperature Time
Reactor
chemicals and biofuels can be obtained through the (ºC) (h) Bu Sn(Lau) Bu SnO BuSn(O)OH
2 2 2
esterification and transesterification of FAs and TGs,
respectively, catalyzed by organotin(IV) in the presence of 1 7 >5 >5
short-chain alcohols.1,27-30 Some of the catalysts that have been Reflux
65 2 11 5.3 >5
previously studied are presented in Figure 10. conditions
4 20 6.9 >5
O 1 47 35 -
O O
O
Sn Sn
OH
Sn 80 2 48 48 10
O
Bu 2SnO O
BuSn(O)OH 4 - 64 -
Bu 2Sn(Lau)2
Fig. 10 Molecular structures of butyl stannoic acid, dibutyltin 1 70 45 40
oxide, and dibutyltin dilaurate. Close steel
120 2 77 83 76
reactor
The catalytic mechanisms for esterification and 4 76 83 60
transesterification are based on one of the mechanisms
discussed above. It has been suggested that the mechanism 1 98 75 70
includes the formation of a Lewis acid-base complex
intermediate through the interaction of the substrate (FA, TG, 150 2 98 95 73
DG, or MG) with the metal center via the oxygen of the 4 80 74 74
carbonyl group, with subsequent nucleophilic attack by the
alcohol (intra or intermolecular) or alkoxide Adapted from reference 28
(intramolecular).1,31
While Bu2Sn(Lau)2 is a liquid at room temperature, Additionally, five different alcohols (methanol, ethanol, n-
BuSn(O)OH and Bu2SnO are insoluble solids in a series of butanol, iso-butanol, and iso-propanol) have been investigated
solvents and as previously mentioned are categorized as stable to determine the influence of the chemical nature on the
oligomeric structures at room temperature. However, on reaction yield. Surprisingly, the highest yields were obtained
increasing the temperature these particular arrangements can be when longer-chained alcohols are employed, mainly at higher
destabilized, resulting in more active molecular species.30,32 temperatures.28 Considering the mechanism proposed for the
It has been reported that these catalytic systems exhibit better transesterification reaction conducted in the presence of
performance at higher reaction temperatures because the catalysts containing Lewis acid sites31, the expected effects of
catalysts can be more effectively activated and their the chain size or branching in the alcohol chain for this type of
compatibility in the reaction medium can be improved.30 reaction are outweighed by the favorable phase equilibrium that
is established inside the reactor.
The use of castor oil instead of soybean oil in
FAAEs via transesterification with organotin(IV) transesterification was also explored because castor oil is
compounds composed almost entirely (ca. 90%) of triacylglycerides
Transesterification reactions have been investigated using these containing the unconventional fatty acid known as ricinoleic
Sn(IV) complexes (Bu2Sn(Lau)2, BuSn(O)OH, and Bu2SnO) acid (12-hydroxy-cis-octadec-9-enoic acid). The results
while varying several parameters: type of reactors, substrates revealed that regardless of the Sn(IV) catalyst used and reaction
(source of TG (soybean or castor oils) and various alcohols), conditions employed, the methanolysis of castor oil leads to
temperature, reaction time, and the amount of catalyst (Table lower yields than those observed when soybean oil is the source
1).28,30 of triacylglycerides. This lower reactivity of the reaction
The results from reactions conducted using a reactor systems based on castor oil cannot be related to mass transfer
operating at reflux conditions gave lower yields in comparison problems, but rather are due to the singular chemical
with those obtained using a closed steel reactor, in which more composition of this oil.27
severe reaction conditions can be attained (Table 1). This
explanation for this behavior can be traced to (i) the amount of FAAEs via esterification with organotin(IV) compounds
methanol present in the liquid phase inside a closed steel Esterification reactions of soybean FAs with methanol (and in
reactor (approximately 90-96%), compared with only 35% some cases with ethanol) in the presence of these organotin(IV)
using a reactor operating at reflux conditions28 and (ii) the complexes have been investigated, and the influence of
higher degree of solubility and activation of the catalysts that temperature, reaction time, and amount of catalyst was
can be reached at the higher temperatures inside the steel evaluated (Table 2).1 It is important to mention that
reactor. esterification can be self-catalyzed due to the presence of
Brønsted acid (the fatty acid itself) in the reaction media. For
this reason, the catalytic activity of each metal complex must

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ARTICLE Journal Name

always be compared with the same reaction conducted without

the presence of the metal compound.

Table 2 Production of FAAEs (percentage yield) by esterification in the presence of BuSn(O)OH, Bu2SnO, and Bu2Sn(Lau)2, and

Catalysis Science & Technology Accepted Manuscript

without any catalyst, at several reaction conditions.

Catalyst
Temperature Molar ratio Time
Alcohol
(ºC) (FFA:ROH:cat) (h) BuSn(O)OH Bu2SnO Bu2Sn(Lau)2 Without
120 100:400:1 1 MeOH 46 30 22 19

100:400:1 1 EtOH 27 - - 20

100:400:1 1 MeOH 68 40 35 29
100:400:1 1 EtOH 58 - - 29
140
100:400:2 1 MeOH 75 44 39 29
100:400:3 1 MeOH 90 67 40 29
1 MeOH 89 60 56 46
1 EtOH 63 - - 46
160 100:400:1 2 MeOH 91 88 78 67
3 MeOH 93 91 85 79
4 MeOH 94 92 90 81

The esterification reactions were run at 120, 140, and 160 It is also encouraging that these catalytic systems are able to
ºC using the molar ratio 400:100:1 (alcohol:FA:catalyst), and simultaneously perform esterification and transesterification
all of the complexes were found to be active because in their reactions of TG and FA. To demonstrate this, three mixtures of
presence better conversions were observed when compared FA:TG (50:50, 30:70, and 70:30 wt%) underwent methanolysis
with the self-catalyzed reaction.1 When the reaction in the presence of BuSn(O)OH as the catalyst at 160 °C for 1,
temperature was increased even better results were obtained 2, 3, or 4 hours (Figure 11).1
(Table 2).
The influence of the reaction time on the conversion was 100

evaluated at 160 ºC using durations of 1, 2, 3 and 4 hours. A 90

strong dependence of the conversion on the reaction time 80
during kinetic control of the reaction was observed.
70
BuSn(O)OH was found to be the most active catalyst, with
60
yields of approximately 90% achieved after 1 h. After 3 hours
FAMEs (%)

all of the catalysts showed virtually the same tendency, 50 100 TG

indicating that the system had reached the reaction equilibrium. 30 FA:70 TG
40
50 FA:50 TG
As expected, in all cases the reaction yields increased when 30 70 FA:30 TG
increasing the amount of catalyst, which can be clearly 100 FA
20
understood because there are more catalytic sites made
available. 10

The use of ethanol leads to lower yields in comparison to 0

0 1 2 3 4
those obtained when using methanol at the evaluated
conditions. This is because methanol is a stronger nucleophile Reaction time (h)
than ethanol, assisting the nucleophilic attack at the carbonyl Fig. 11 Yields in terms of FAMEs after methanolysis of
group of FA. soybean FAs, TG, and their mixtures using BuSn(O)OH as the
In general, during the kinetic control of the esterification catalyst at 160 ºC.
reaction, i.e., in the first 2 hours, the order of reactivity
observed is BuSn(O)OH >> Bu2SnO > Bu2Sn(Lau)2. This For the mixture containing 70% FA and 30% TG,
order cannot only be related to the different compatibilities of conversions of up to 90% after 1 h are achieved. In this case,
the organotin(IV) species in the reaction medium (see Table 2) better yields are obtained because under these experimental
because the most soluble one, Bu2Sn(Lau)2, is not the most conditions the esterification is kinetically favored.
active. The observed differences can be related to the different These observations demonstrate that this type of catalyst is
Lewis acidities of the organometallic species, acting directly in quite active for both esterification and transesterification
the formation of the Lewis acid-base complex intermediate that reactions, as well under simultaneous reaction conditions,
is formed by the interaction of the substrate (FA, TG, DG, or opening significant possibilities for their use in reactions
MG) with the metal center, via the oxygen of the carbonyl involving raw materials at low cost and containing a high
group.31

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amount of FAs such as palm oils, recycled oils, and animal Angew. Makromol. Chem. 1978, 68, 23.
fats.1,12,33 16 F. S. Guner, Y. Yagci, A. T. Erciyes, Prog. Polym. Sci. 2006, 31,
633.
Final considerations

Catalysis Science & Technology Accepted Manuscript

Mechanistic aspects and industrial applications of 17 D. Doulia, S. Rokotas, K. Georgopoulou, Surf. Coat. Int. B: Coat.
organotin(IV) catalysts, which are the most produced Trans. 2006, 89, 215.
organometallic complexes in the world, have been discussed 18 L. S. Ratliff, L.J. Prendny, Catalysts for use in the acidolysis,
from a critical point of view. A potential industrial application
of these catalytic systems, particularly for the synthesis of fatty alcoholysis and esterification reactions of polyesters for coating
acid alkyl esters, has been discussed and several promising resins, Advances in Coating Technology, ACT’98, International
results were shown, which demonstrate the importance of this Conference, 3rd, Katowice, Poland, 1998.
research area.
19 I. Kei, K. Tsutomu, N. Reijiro, N. Nobushige, Kansai Paint Co
Acknowledgements Ltd., JP2002179777-A 2002
Financial support from Brazilian research founding agencies, 20 Y. Guo, CN103013308-A 2013
such as Research and Projects Financing (FINEP), National
21 J. Yang, W. Kuang, Y. Liu, Y. Jia, C. Liu, CN102796228-A 2012
Counsel of Technological and Scientific Development (CNPq),
Federal District Research Support Foundation (FAPDF) and 22 C. Kawamura, K. Ito, K. P. C. Ito, EP1245603-A1 2002
Alagoas Research Support Foundation (FAPEAL), are grateful 23 C. Kawamura, K. Ito, I. Yoshihara, N. Numa, WO200125309-A
acknowledged. MRM and SMPM thank CNPq for research
2001
fellowships.
24 E. Urbano, M. Gobec, O. Ferk, EP1092742-A 2003
This paper is dedicated to Prof. Dr. Roberto Fernando de Souza (in 25 C. Kawamura, K. Ito, JP2002317035-A 2002
memoriam).
26 U. Schuchardt, R. Sercheli, R. M. Vargas, J. Brazil. Chem. Soc.
1998, 9, 199.
Notes and references
a
Grupo de Catálise e Reatividade Química, Instituto de Química e 27 T. M. Serra, D. R. de Mendonça, J. P. V. da Silva, M. R.
Biotecnologia, Universidade Federal de Alagoas, Campus A.C. Simões, Meneghetti, S. M. P. Meneghetti, Fuel 2011, 90, 2203.
Av. Lourival de Melo Mota, Maceió/AL CEP 57072-970, Brazil. 28 D. R. de Mendonca, J. P. V. da Silva, R. M. de Almeida, C. R.
E-mail – simoni.plentz@gmail Wolf, M. R. Meneghetti, S. M. P. Meneghetti, Appl. Catal. A-
Gen. 2009, 365, 105.
1 Y. C. Brito, D. A. C. Ferreira, D. M. A. Fragoso, P. R. Mendes, C. M.
29 J. Dupont, P. A. Z. Suarez, M. R. Meneghetti, S. M. P.
J. de Oliveira, M. R. Meneghetti, S. M. P. Meneghetti, Appl. Catal. A-
Meneghetti, Energy Environ. Sci. 2009, 2, 1258.
Gen. 2012, 443, 202.
30 D. A. C. Ferreira, M. R. Meneghetti, S. M. P. Meneghetti, C. R.
2 G. Deshayes, F. A. G. Mercier, P. Degee, I. Verbruggen, M.
Wolf, Appl. Catal. A-Gen. 2007, 317, 58.
Biesemans, R. Willem, P. Dubois, Chem-Eur. J. 2003, 9, 4346.
31 B. A. D. Neto, M. B. Alves, A. A. M. Lapis, F. M. Nachtigall, M.
3 S. Shyamroy, B. Garnaik, S. Sivaram, J. Polym. Sci. Pol. Chem. 2005,
N. Eberlin, J. Dupont, P. A. Z. Suarez, J. Catal. 2007, 249, 154.
43, 2164.
32 C. Elschenbroich, Organometallics, 3rd ed., Wiley-VCH,
4 I. Shiina, Chem. Rev. 2007, 107, 239.
Weinheim, Germany, 2006.
5 A. G. Davies, J. Chem. Res. 2010, 181.
33 M. B. Alves, F. C. M. Medeiros, P. A. Z. Suarez, Ind. Eng. Chem.
6 Y. Roman-Leshkov, M. E. Davis, Acs Catal. 2011, 1, 1566.
Res. 2010, 49, 7176.
7 M. Pereyre, G.Colin, J. P. Delvigne, B. Soc. Chim. Fr. 1969, 262.
8 R. C. Poller, S. P. Retout, J. Organomet. Chem. 1979, 173, C7.
9 B. Jousseaume, C. Laporte, M. C. Rascle, T. Toupance, Chem.
Commun. 2003, 1428.
10 J. Otera, N. Danoh, H. Nozaki, J. Org. Chem. 1991, 56, 5307.
11 G. W. Parshal, S. D. Ittel, Homogeneous Catalysis, 2ª ed., John
Wiley&Sons, 1982.
12 E. Crawford, T. Lohr, E. M. Leitao, S. Kwok, J. S. McIndoe, Dalton
Trans. 2009, 9110.
13 P. A. Z. Suarez, S. M. P. Meneghetti, M. R. Meneghetti, C. R. Wolf,
Quim. Nova 2007, 30, 667.
14 Z. W. Wicks, Organic Coatings: Science and Technology, 3rd ed.,
Wiley‐Interscience, Hoboken, New Jersey, USA, 2007.
15 K. H. Wolf, B. Kuster, H. Herlinger, C. J. Tschang, E. Schollmeyer,

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