Application of polydopamine sulfamic acid-functionalized magnetic Fe3O4 nanoparticles (Fe3O4@PDA-SO3H) as a heterogeneous and recyclable nanocatalyst for the formylation of alcohols and amines under solvent-free conditions

Article abstract of DOI:10.1039/c7nj00417f

Herein, formylation of structurally different amines and alcohols with ethyl formate was carried out in the presence of a catalytic proportion of sulfonic acid supported on polydopamine (PDA)-encapsulated Fe₃O₄ nanoparticles as a heterogeneous, recyclable, and greatly efficient catalyst; this method provided the corresponding N-formyl compounds in good to excellent yields under solvent-free conditions. The magnetically catalytic system was recovered, by-passing the time-consuming filtration operation using an external magnet device. This procedure also increases the purity of the product and promises economic and ecological advantages. Furthermore, the recovery and reuse of the catalyst was demonstrated five times without detectable loss in the activity.

Full text of DOI:10.1039/c7nj00417f

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Application of polydopamine sulfamic acid-functionalized magnetic Fe3O4
nanoparticles (Fe3O4@PDA-SO3H) as heterogeneous and recyclable
nanocatalyst for formylation of alcohols and amines under solvent‐free
conditions
Sepideh Taheri,a Hojat Veisi,*,b Malak Hekmatia
aDepartment of Pharmaceutical Chemistry, Faculty of Pharmaceutical Chemistry, Pharmaceutical Sciences
Branch, Islamic Azad University, (IAUPS), Tehran, Iran
bDepartment of Chemistry, Payame Noor University, Tehran, Iran
Email: hojatveisi@yahoo.com
Abstract
Enhancement of ethyl formate using structurally varied amines and alcohols in the presence
of a catalytic proportion of sulfonic acid supported on polydopamine (PDA)ꢀencapsulated
Fe3O4 nanoparticles as a heterogeneous, recyclable and greatly efficient catalyst provided the
corresponding Nꢀformyl compounds in good to excellent yields under solventꢀfree conditions.
The magnetically catalytic system was recovered byꢀpassing time consuming filtration
operation by using an external magnet device. This procedure also increases the purity of the
product and promises economic and ecological advantages. Furthermore, the recovery and
reuse of the catalyst was demonstrated five times without detectible loss in activity.
1. Introduction
In synthetic chemistry, some commonly applied conversions are the formylation of alcohols,
phenols and amines. Additionally, they are extensively employed as shielding groups in
multiꢀstep pharmaceutical synthesis and food or cosmetic industries.1ꢀ3 Furthermore, the
formyl group is able to be utilized as an aminoꢀprotecting group for the procurement of
peptides and Nꢀformylamino acid esters, which can then be used as initial materials in the
synthesis of peptides.4
A variety of approaches have been established for the manufacture of Nꢀformyl amines.5
They are able to be collected from reactions involving corresponding amines with formic acid
and acetic anhydride,6 in situ formed formic anhydride,7 chloral followed by elimination,8
ammonium formate,9 and different reagents. Despite this, a large portion of such strategies
are unfavorable due to issues including the costly and toxic formylating agents, formation of
byꢀproducts, difficult accessibility of the formylating agents, etc., and as a result, innovative
less harmful and efficient synthetic procedures are of significance for preparing these Nꢀ
formyl amines.
As ecological chemistry methods have advanced, heterogeneous solid acids have been
employed in a multitude of organic conversions as ecoꢀ and environmentally friendly
catalysts. Benefits of these solid acids include recyclability and nonꢀtoxicity, cleaner and
easier workꢀup methods, and decreased reaction times.11 Magnetic nanoparticles have
recently shown great potential and have received a lot of attention.12ꢀ14 The nature of these
magnetic particles allows for effective recycling and recovery of the catalysts via an external
magnetic field. This enhances the purity of the product and optimizes the cost of its
operation. However, a problem which cannot be averted is the instability of the “naked”
metallic or metal oxide nanoparticles over longer durations as a result of high initial chemical
activity, quickly being oxidized in the air, loss of magnetism, dispersion and agglomeration
due to the great surface area to volume ratio, and the dipoleꢀdipole attractions between the
1

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magnetic particles. Pure Fe3O4 NPs were found to be oxidized and was easily susceptible to
loss of their magnetism.15
A great number of applications demand a protection strategy that chemically stabilizes the
naked magnetic nanoparticles. Formation of passive coating of magnetic NPs was reported to
disallow their aggregation in solutions and therefore enhance chemical stability. The coating
strategies that were employed can be separated into two key groups: 1) coating using an
inorganic component, including carbon, silica, precious metals and calcium hydroxyapatite,16ꢀ
23
and 2) with an organic shell, including surfactants and polymers such as polydopamine
(PDA).24 PDAꢀcoated Fe3O4 nanoparticles (Fe3O4@PDA) have been utilized for a number of
various innovative applications, such as the parting and enhancement of proteins in proteomic
analysis,25 the uncovering of pollutants by matrix assisted laser desorption/ionization timeꢀofꢀ
flight mass spectrometry,26 and magnetic solidꢀphase extraction adsorbent for the
determination of trace polycyclic aromatic hydrocarbons in environmental samples.27
Quite recently, we prepared a magnetically solid acid composite with the assistance of PDA.
Initially a PDA layer was coated on the Fe3O4 NP’s exteriors via in situ spontaneous
oxidative polymerization to enhance the Fe4O4 scattering within aqueous solution by catechol
and nitrogenꢀcontaining sets. Afterwards a sulfonatedꢀpolydopamine coated Fe3O4
nanocomposite (Fe3O4@PDA) was produced as a significantly effective solid acid magnetic
nanocatalyst by chlorosulfonic acid and utilized as a magnetic nanocatalyst (Fe3O4@PDAꢀ
SO3H) for acetylation of alcohols, phenols, amine s and thiols with acetic anhydride.28a Since
we were interested in applying this innovative heterogeneous solid nanocatalyst, as a result of
the Nꢀformylation reaction being industrially significant, the catalytic behavior was studied
for formylation of alcohols, phenols and amines with ethyl formate (Scheme 1).
2. Experimental Section
2.1Preparation of Fe3O4, Fe3O4@PDA and Fe3O4@PDA-SO3H magnetic nanoparticles:
The magnetic Fe3O4 nanoparticles were prepared by the chemical coꢀprecipitation method,40
and the detailed procedure is described below. FeCl2·4H2O (2 g) and FeCl3·6H2O (5.2 g)
were dissolved into 25 mL deoxygenated water followed by adding 0.85 mL of concentrated
hydrochloric acid. The resulting solution was dropped into 250 mL of 1.5 M NaOH solution
under vigorous stirring and N2 protection at 353 K. The obtained magnetic nano particles
were separated from solution by a powerful magnet and rinsed with 200 mL deionized water
three times. Finally the products were dried at 40 °C to give Fe3O4 nanoparticles.
Fe3O4 nanoparticles (1g) were dispersed in 500 mL Tris buffer (10 mM, pH 8.5), then
dopamine (1 g) was added, and the mixture solution was mechanically stirred for 24 h at
room temperature. After reaction, the Fe3O4@PDA nanoparticles were isolated with a magnet
and washed with deionized water and anhydrous ethanol and dried at 40 °C to give
Fe3O4@PDA.
In the next step, the Fe3O4@PDA was sulfonated using chlorosulfonic acid (ClSO3H). The
Fe3O4@PDA composite (1 g) were dispersed in dry CH2Cl2 (20 mL) by ultrasonic bath for 20
min. Subsequently, chlorosulfonic acid (0.8 mL) was added drop wise over a period of 30
min at room temperature. Upon completion of the addition, the mixture was stirred for 5 h at
room temperature. The resulted magnetic nanocomposite was separated from the suspension
by an external magnet, washed several times with CH2Cl2 and ethanol and then dried at room
temperature to give Fe3O4@PDAꢀSO3H. The content of acid sites of Fe3O4@PDAꢀSO3H
nanocomposite was estimated by back titration using HCl (0.337 N). 10 mL of NaOH (0.130
2

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N) was added to 0.1 g of this composite and stirred for 30 min. The catalyst was separated
and washed with deionized water. The excess amount of NaOH was titrated with HCl (0.337
N) in the presence of phenolphthalein as indicator. The acid site content was 1.2 mmol gꢀ1.
2.2 General procedure for formylation reaction:
A 25 mL ballon containing a magnetic stir bar was charged with alcohol/amine (1 mmol) and
ethyl formate (3 mmol), Fe3O4@PDAꢀSO3H (1 mol%) as catalyst. The reaction mixture was
stirred (300 rpm) at 40 ºC under solventꢀfree condition and the reaction progress was
monitored on thinꢀlayer chromatography (TLC). After completion of the reaction, the
reaction mixture was diluted with ethyl acetate and catalyst was separated from reaction
mixture by using a strong magnet. The separated catalyst was washed with acetone several
times then dried in oven and reused for further reaction. The reaction mixture was dried over
Na2SO4 and evaporated under vacuum and the product, obtained, was subjected to column
chromatography. All the obtained products are well known in the literature.
3. Results and Discussion
The modification of Fe3O4 NPs with polydopamine was acquired by in situ polymerization of
dopamine in trisꢀbuffer solution (pH 8.5) with constant stirring. The successful generated
Fe3O4@PDA nanostructure was further sulfonated by chlorosulfonic acid to make
polydopamine sulfamic acidꢀfunctionalized magnetic Fe3O4 nanoparticles (Fe3O4@PDAꢀ
SO3H) with core/shell nanostructure as a novel solid acid magnetic nanocatalyst.28a The
catalytic activity of Fe3O4@PDAꢀSO3H was investigated as a novel solid acid magnetic
nanocatalyst for formylation of alcohols, phenols and amines with ethyl formate (Scheme 1).
R1R2XH
HO
R1 = alkyl, aryl
R2 = alkyl, aryl, H
H2N
N
R1R2XCHO
X = NH, O
HO
HO
NH
H
Ethyl formate
40 oC
N
H
HO
HO
OH HO
OH
SO3H
HO3S
HO3S
SO3H
SO3H
SO3H
PDA
PDA
HO
HO
NH2
ClSO3H
Fe3O4 NPs
HO3S
Fe3O4 NPs
Fe3O4 NPs
Fe3O4 NP
Tris, pH = 8.5
SO3H
SO3H
HO3S
HO3S
Fe3O4 NPs@PDA
SO3H
Fe3O4 NPs@PDA-SO3H
Scheme 1:Preparation ofFe3O4@PDAꢀSO3H and its application for formylation of alcohols,
phenols and amines
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The TEM and EDX measurements were applied to verify the nanostructure of Fe3O4@PDAꢀ
SO3H that was synthesized again. The TEM image of Fe3O4@PDAꢀSO3H demonstrated that
the catalyst formed in nanometerꢀsized particles as quasiꢀspherical and a continuous layer of
polymer could additionally be seen on the surface of the NPs (Fig. 1a). The existence of of
PDAꢀSO3H shell on the surface of Fe3O4 NPs was also confirmed by the EDX detector
coupled to the SEM which showed the presence of Fe, C, N, S, and O in Figure 1b.
Fig. 1. (a) TEM image and (b) EDX data for the Fe3O4@PDAꢀSO3H.
In this regard to find the optimal conditions, Fe3O4@PDAꢀSO3H as a nanocatalyst was tested
in the Nꢀformylation reaction of aniline and ethyl formate as model reaction under different
conditions. The effect of catalyst amount, solvent, temperature, and reaction time were
carefully monitored in the reaction under the comparable conditions. Accordingly, 1 mol% of
the catalyst (based on themols of H+ in the catalyst) was acquired as an optimum amount and
also under solventꢀfree conditions at 50 ºC during 2 h reached out the yield to maximum
amount (Table 1).When the amount of catalyst was lower, the yield of the product decreased
(Table 1, Entry 10), whereas raising the catalyst concentration did not lead to a pronounced
increase to the product yield (Table 1, Entry 9). In the absence of catalyst, no product's was
observed, even after prolonged reaction time (Table 1, Entry 11).
Table 1: Optimization conditions on the formylation of benzyl amine in the presence of the
Fe3O4@PDAꢀSO3Ha
NH2
NHCHO
O
Fe3O4@PDAꢀSO3H
Conditions
+
+
EtOH
H
OEt
Entry Solvent
Catalyst (mol%) T (ºC) Time (h) Yield (%)
1
2
3
4
5
6
7
8
EtOH
EtOH
1
1
1
1
1
1
1
1
r.t.
40
40
40
40
40
40
40
10
6
6
8
5
6
6
2
45
65
60
70
75
70
55
96
MeOH
CH2Cl2
Toluene
CH3CN
H2O
ꢀ
4

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9
ꢀ
ꢀ
ꢀ
ꢀ
2
0.5
ꢀ
40
40
40
r.t
2
4
12
5
90
65
0
10
11
10
1
70
a
Reaction conditions: Aniline (1 mmol), ethyl formate (3 mmol), and solvent (3 mL).
With consideration of the optimal conditions of formylation of aniline, a variety of
structurally varied alcohols, amines and thiols were subject to formylation, catalyzed by
Fe3O4@PDAꢀSO3H in order to investigate the generality and scope of the procedure. In Table
the results have been reported and in this manner we successfully developed a simple and
effective method of the production of formamides (Table 2, entries 1ꢀ11).Table 2 shows that
the yields are high. Aromatic and aliphatic primary and secondary amines can react under this
condition. For a variety of amines, e.g., hindered amine (Table 2, entry 6), heterocyclic amine
(Table 2, entry 7), amino acid (Table 2, entry 11), and diamines (Table 2, entries 7, 8), the
reaction shows good results without any significant influence of their structures on the
product yields. Reactions of aromatic amines bearing both electronꢀdonating and
withdrawing groups proceed smoothly to give the corresponding Nꢀformyl compounds in
quantitative yields (Table 2, entries 1ꢀ5). Primary amines are easily formylated to provide
their corresponding formamide in shorter reaction time and higher yields than secondary
amines.
Similarly, some different substituted aromatic and aliphatic hydroxyl groups were formylated
very smoothly using mild reaction conditions to provide the desired Oꢀformylated alcohols in
excellent yields. These procedures are uniformly effective for formylation of primary
saturated alcohol (Table 2, entry 19), benzylic alcohols (Table 2,entries 12ꢀ15) and secondary
alcohols (Table 2, entries 20ꢀ22,24), phenols (Table 2, entries 16, 17). In this reaction, we did
not observe chemoꢀselectivity for the reaction of ethanol amine having biꢀfunctional groups
of NH and OH (Table 2, entry 10).Our experiments also indicated that tertiary alcohols(Table
2, entry 23) and thiols (Table 2, entries 9, 25) did not formylated under this condition. Also,
cinnamyl alcohol, as an allyllic alcohol, was selectively converted to the corresponding
product, which carbon double bond was intact during the formylation reaction (Table 2, entry
18).
Table 2: O,Nꢀformylation with ethyl formate under solvent‐free conditions in the presence of
Fe3O4@PDAꢀSO3Ha
Entry Substrate
Product
Time (h) Yield (%)b
Ref.
38
1
0.5
98
NH2
NH2
NHCHO
2
1
1
2
98
38
NHCHO
H3C
H3C
3
96
96
44g
30
NH2
NHCHO
H3CO
H3CO
NH2
NHCHO
4
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NH2
CH3
NHCHO
5
3
95
44g
CH3
N
6
7
2
1
90
98
44g
44g
N
H
CHO
H
N
CHO
N
N
H
N
CHO
NH2
SH
NHCHO
SH
8
0.5
0.5
1
98
98
96
90
44g
44g
44g
44g
H2N
H2N
H2N
OHCHN
OHCHN
OHCHN
9
OH
OCHO
10
11
O
O
2
H2N CH C OH
CH3
OHCHN CH C OH
CH3
12
13
1
1
98
96
44g
44g
OH
OCHO
OH
OCHO
H3C
H3C
14
15
16
1
1
3
90
96
85
45
OH
OCHO
OCHO
MeO
Cl
MeO
Cl
44g
31
OH
OH
OH
OCHO
OCHO
17
3
80
44g
Cl
Cl
18
19
2
1
90
96
44g
44g
OH
OCHO
OCHO
OH
OH
OH
OCHO
OCHO
20
21
22
1
95
90
85
44g
44g
44g
1.5
2
OH
OCHO
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23
24
12
0
OH
OCHO
1.5
12
95
HO
OHCO
SCHO
SH
25
0
aReaction conditions: substrate (1 mmol), catalyst (1 mol%), ethyl formate (3 mmol) at 40 ºC under solvent free
conditions.
bIsolated yields.
The choice of the catalytic arrangement was assessed via a mixture of alcohols and phenols
and for this, an equimolar mixture of benzyl alcohol and phenol was reacted with ethyl
formate in the presence of the Fe3O4@PDAꢀSO3H catalyst. This experiment found that the
reaction proceeded with high chemoꢀselectivity towards the benzyl alcohol (Scheme 2). This
procedure could thus be applied for the chemoselective formylation of alcohols whilst in the
presence of phenols. Additionally, we studied the reaction between tertiary and secondary
alcohols and ethyl formate under listed conditions. For the transformation of secondary
alcohols in the presence of tertiary alcohols, such as 1ꢀadmatanol (Scheme 2), excellent
chemoꢀselectivity was observed.
OH
OCHO
OH
Fe3O4@PDAꢀSO3H
Ethyl formate, 40 oC
OCHO
+
+
Trace
Major product
OH
OCHO
OH
OCHO
Fe3O4@PDAꢀSO3H
Ethyl formate, 40 oC
+
+
Only product
0%
Scheme 2: Chemoselectivity of the formylationin the presence of Fe3O4@PDAꢀSO3H
In Scheme 3, the catalytic mechanism behind Fe3O4@PDAꢀSO3H is demonstrated. It
protonates the carbonyl group in ethyl formate and causes it to be more reactive under
nucleophilic attack of O or N groups. With the release of protons, the ethanol is formed to
regenerate catalyst structure through a proton transfer.
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PDA
O
Fe3O4 NPs
S
OH
OH
O
O
O
O
H
R
Fe3O4 NPs@PDA-SO3H
H
X
R
PDA
Fe3O4 NPs
PDA
O
S
O
OH
OH
H
O
Fe3O4 NPs
S
O
O
X
O
H
H
O
O
R XH
X = NH, O
Scheme 3: Plausible reaction mechanism of Fe3O4@PDAꢀSO3Hꢀcatalyzed formylation
The likelihood of magnetic recycling of the catalyst was evaluated. In doing so, the reaction
of aniline and ethyl formate in the presence of Fe3O4@PDAꢀSO3H was investigated. Upon
the reaction being completed, the catalyst was conveniently removed from the product
through the attachment of an external magnet onto the reaction vessel, after which, the
remaining solution was decanted. The recovered catalyst was washed using acetone to
remove residual product and then dried under vacuum and recycled in further reactions. In
the reaction between aniline and ethyl formate produced the corresponding formamide at
100% conversion and isolated yields of 96, 96, 95, 93 and 90% in five consecutive runs, thus
averaging a 94% chemical yield over the five consecutive runs. This undoubtedly highlights
the practical reusability and recyclability of the catalyst without loss of catalytic behavior
(Fig. 2). After 5 runs, the SEM and TEM images (Fig. 3) of the catalyst indicated a
conservation of its nanostructure.
100
80
60
40
20
0
5
4
3
2
1
Run
Fig. 2. Reusability of the nanocatalyst
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The reaction between aniline and ethyl formate at 40 ºC was carried out in the presence of
Fe3O4@PDAꢀSO3H for 20 min to evaluate the percent leaching of the acid and after that
point the catalyst was extracted via an external magnet. The remainder was then reacted, but
no major transformation was observed after 1 h. Consequently, this investigation rules out the
basic contribution of homogeneous conversion of an acid catalyst. It was thus determined that
no particular handling precaution regarding exposure to air/moisture was required to be
undertaken in the use of the Fe3O4@PDAꢀSO3H catalyst.
Fig. 3. a) SEM and b) TEM images of reused catalyst after the five run.
To illustrate the benefits of our procedure compared to other reported methods, we assessed
the results for Nꢀformylation of benzylamine under various conditions. The results listed in
Table 3 point out that our method by Fe3O4@PDAꢀSO3H was undertaken with a lower
reaction time and greater yield in comparison to the reactions catalysts by other previously
reported approaches. Hence, from the perspective of ‘green chemistry’ and for reasons of
pollution and economy, solventꢀfree methods are of significant value to ensure the classical
procedures are safer, cleaner and simplistic.
Table 3: Comparison present methodology with reported methods in the Nꢀformylation of
benzylamine.
Entry Reaction conditions
Time (h) Yield% Ref.
1
2
3
4
5
6
7
8
Fe3O4@PDAꢀSO3H, HCOOEt, 40 ºC, solventꢀfree
0.5
1.5
6
6
1.5
2
98
90
88
42
92
94
75
85
This work
ZnCl2 anhydrous, HCOOH, 70 ºC, Solventꢀfree
Ammonium formate, CH3CN, reflux
PEG, HCOOH, r.t., Solventꢀfree
HCOOH, Amberlite IRꢀ120,solventꢀfree, MW
Methylformate, toluene
Molybdate sulfuric acid,HCOEt3, EtOH, reflux
HCOONa, HCOOH, r.t., solventꢀfree
29
30
31
32
33
34
35
2.1
2.5
Conclusion
In conclusion, a highly effective and solventꢀfree Fe3O4@PDAꢀSO3H catalyzed technique
was advanced for Nꢀformylation of alcohols, phenols and amines with ethyl formate. The
mild reaction conditions, high yields, operational ease, practicality and applicability to a
number of substrates render this method as a valuable substitute to other previously utilized
approaches. In comparison to nonꢀmagnetic nanoparticle catalytic systems, the protocols
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listed combine the advantages of solid Brönsted acid and magnetic nanoparticles. Even after
four cycles the nanocatalyst was still entirely retrievable and the effectiveness of the catalyst
remained unchanged.
Acknowledgments
We are thankful to Payame Noor University and Pharmaceutical Sciences Branch, Islamic
Azad University, Tehran, Iran, for partial support of this work.
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Page 12 of 12
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DOI: 10.1039/C7NJ00417F
Graphical Abstract
Application of polydopamine sulfamic acid-functionalized magnetic Fe3O4
nanoparticles (Fe3O4@PDA-SO3H) as heterogeneous and recyclable nanocatalyst
for formylation of alcohols and amines under solvent‐free conditions
Sepideh Taheri, Hojat Veisi,* Malak Hekmati
R1R2XH
HO
R1 = alkyl, aryl
R2 = alkyl, aryl, H
H2N
N
H
R1R2XCHO
X = NH, O
HO
HO
NH
Ethyl formate
40 oC
N
H
HO
HO
OH
HO
OH
SO3H
HO3S
HO3S
SO3H
SO3H
SO3H
PDA
PDA
HO
HO
NH2
ClSO3H
Fe3O4 NPs
HO3S
Fe3O4 NPs
Fe3O4 NPs
Fe3O4 NP
Tris, pH = 8.5
SO3H
SO3H
HO3S
HO3S
Fe3O4 NPs@PDA
SO3H
Fe3O4 NPs@PDA-SO3H
12