Magnetically recoverable AlFe/Te nanocomposite as a new catalyst for the facile esterification reaction under neat conditions

Article abstract of DOI:10.1002/aoc.4167

In this work, a new Fe₃O₄/AlFe/Te nanocomposite was synthesized by a one-step sol–gel method. The Fe₃O₄ magnetic nanoparticles (MNPs) were prepared and then mixed with aluminum telluride (Al₂Te₃) in an alkali medium to produce the desired catalyst. After characterization of the Fe₃O₄/AlFe/Te nanocomposite by SEM, TEM, EDS, XRD, and ICP analyses, it was used in the esterification reaction. This heterogeneous catalyst showed high catalytic activity in the esterification of commercially available carboxylic acids with various alcohols to produce the desired esters at high conversions under neat conditions. The Fe₃O₄/AlFe/Te nanocomposites were separated from the reaction mixture via an external magnet and re-used 8 times without significant loss of catalytic activity.

Full text of DOI:10.1002/aoc.4167

Received: 7 August 2017
DOI: 10.1002/aoc.4167
Revised: 9 October 2017
Accepted: 9 October 2017
F U L L P A P E R
Magnetically recoverable AlFe/Te nanocomposite as a new
catalyst for the facile esterification reaction under neat
conditions
Seyed Jamal Alavi1
Hossein Eshghi1
| Hamid Sadeghian2,3
| Alireza Salimi1
| Seyed Mohammad Seyedi1
|
1 Department of Chemistry, Faculty of
Science, Ferdowsi University of Mashhad,
Mashhad, Iran
2 Neurogenic Inflammation Research
Center, Mashhad University of Medical
Sciences, Mashhad, Iran
3 Department of Laboratory Sciences,
School of Paramedical Sciences, Mashhad
University of Medical Sciences, Mashhad,
Iran
In this work, a new Fe3O4/AlFe/Te nanocomposite was synthesized by a one‐
step sol–gel method. The Fe3O4 magnetic nanoparticles (MNPs) were prepared
and then mixed with aluminum telluride (Al2Te3) in an alkali medium to pro-
duce the desired catalyst. After characterization of the Fe3O4/AlFe/Te nano-
composite by SEM, TEM, EDS, XRD, and ICP analyses, it was used in the
esterification reaction. This heterogeneous catalyst showed high catalytic activ-
ity in the esterification of commercially available carboxylic acids with various
alcohols to produce the desired esters at high conversions under neat condi-
tions. The Fe3O4/AlFe/Te nanocomposites were separated from the reaction
mixture via an external magnet and re‐used 8 times without significant loss of
catalytic activity.
Correspondence
Seyed Mohammad Seyedi, Department of
Chemistry, Faculty of Science, Ferdowsi
University of Mashhad, 91775‐1436
Mashhad, Iran.
Email: smseyedi@ferdowsi.um.ac.ir
KEYWORDS
aluminum telluride, esterification reaction, Fe3O4 magnetic nanoparticles, neat condition
Funding information
Ferdowsi University of Mashhad, Grant/
Award Number: 37712
1 | INTRODUCTION
as acid anhydrides or acid chlorides with alcohols, harsh
reaction conditions or expensive coupling agents were uti-
Synthesis of esters as an important intermediate from car-
boxylic acids or aldehydes is one of the popular transfor-
mations in organic chemistry. Esters are used as
versatile and valuable intermediates in industry, medi-
cine, pharmaceutical chemistry, natural products, biol-
ogy, polymers, and also as a protective group in organic
synthesis.[1–5]
The main factors causing a pleasant odor and flavor in
a number of flowers and fruits are simple esters with the
low‐ molecular weight that could be in the form of a sin-
gle ester or a complex mixture. For this property, the
application of esters has been extended in the food indus-
try for artificial flavors and fragrance.[6]
lized.[7–11] Traditionally, base/acid homogeneous catalysts
such as H2SO4, HCl, HfCl4, ZrCl4, ZrOCl2 and HfOCl2 were
appliedforthedirectesterificationofcarboxylicacids.[12–14]
In the recent years, heterogeneous catalysts had also been
reported which most of these catalytic systems are present
acidic nature.[15] Metal oxides such as Al2O3, Fe3O4, SnO,
ZnO, CaO, ZnO–La2O3, sulfated zirconia, sulfated
carbon,[16,17] copper methanesulfonate,[18] Fe2(SO4)3,[19]
Zn(ClO4)2/MgSO4,[20] zirconium titanium phosphate,[21]
Zno/SiO2,[22] N,N‐diphenylammoniumtriflate[23] and p‐
dodecylbenzenesulfonic acid[24] were used for catalytic
synthesis of esters from carboxylic acids and alcohols. In
the past ten years, direct esterification of aldehydes with
alcohols by using stoichiometric amounts of strong oxi-
dants have also been reported.[25,26] Pd/charcoal in
Commonly, for esterification reactions involving car-
boxylic acids or activated carboxylic acid derivatives such
Appl Organometal Chem. 2017;e4167.
wileyonlinelibrary.com/journal/aoc
Copyright © 2017 John Wiley & Sons, Ltd.
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https://doi.org/10.1002/aoc.4167

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ALAVI ET AL.
combination with bismuth (III) nitrate and tellurium metal
that promotes efficient aerobic oxidation of primary
alcohols to the corresponding methyl esters was also
reported.[27] A new magnetic separable nanocomposites
of ZrO2–Al2O3–Fe3O4 (ZAF) was reported as Leiws acidic
catalysts for esterification reactions and applied for other
various organic reactions such as Hantzsch, Biginelli and
Pechmann reaction.[28]
Intermetallic material Bi2Te3 increase the reaction
rate, selectivity, and overall product conversions. Bi2Te3‐
based materials were also applied for thermoelectric
applications in the temperature range of 200–400 K.[29]
Butadiene oxidation on a Pd–Te catalyst was carried out
in alcohol to obtain alcoholates[30] which revealed pro-
moting effect of tellurium. The nature of the promoting
effect of Te and other transition metals in supported bime-
tallic catalysts has been discussed previously.[27,31–33]
Transition metal telluride materials, including iron tellu-
ride (FeTe2), have been studied as materials for Na‐ion
batteries previously.[34] Alloys in the CuAlSe2–CuAlTe2
system were also synthesized for the optoelectronic appli-
cations particularly in solar cells and optical filters.[35,36]
In the present study, for first time a new nanocompos-
ite of Fe3O4 and Al2Te3 was synthesized which lead to the
Fe3O4/AlFe/Te MNPs. The catalytic properties of Fe3O4/
AlFe/Te nanocomposite were investigated in esterifica-
tion of various carboxylic acids with primary, secondary
and tertiary alcohols. The results show amazing perfor-
mance of designed catalyst in the synthesis of various
esters. Incorporation of Te and Al co‐catalysts into the
Fe3O4 crystalline phase significantly improves the activity
of catalyst in comparison with bare Fe3O4 and Al2Te3 due
to synergetic effect of these metallic centers. To the best of
our knowledge, this is the first report on heterogeneous
Fe3O4/AlFe/Te‐based nanocomposite for the esterifica-
tion of aliphatic carboxylic acids and alcohols.
2 | RESULTS AND DISCUSSION
2.1 | Characterization of Fe3O4/AlFe/Te
nanocomposite
The Fe3O4 MNPs were prepared by a hydrothermal tech-
nique[37] and then mixed with Al2Te3 to produce the
desired nanocomposite. Finally, the obtained Fe3O4/
AlFe/Te nanocomposite was used in an esterification
reaction. The magnetic nanocomposite was characterized
by several techniques. Figure 1 shows the morphology of
Fe3O4 MNPs and Fe3O4/AlFe/Te nanocomposites by
TEM and SEM images. The Fe3O4 MNPs are approxi-
mately multifaceted cubic and spherical particles with
average diameters of about 30 nm (Figure 1a). As shown
in Figure 1b, the TEM image of the nanocomposite shows
FIGURE 1 (a) TEM image of Fe3O4 MNPs, (b) TEM image, (c)
EDS result, and (d) SEM image of Fe3O4/AlFe/Te nanocomposite

ALAVI ET AL.
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that most have spherical‐like shape with sizes of about
30 nm. EDS analysis (Figure 1c) shows that the elemental
composition of the nanocatalyst are Fe, Te, O, and Al, and
was further studied with XRD analysis (Figure 2). EDS
analysis shows that Fe and Al are on the same layer
(named K layer) while Te is in a different Layer (named
L layer).Inductively coupled plasma analysis (ICP‐OES)
revealed that the final nanocomposite consists of 37.3%
Fe, 32.9% Te and 1.34% Al. Figure 1d shows the SEM
image of Fe3O4/AlFe/Te nanocomposite which confirms
the spherical‐like shape of the nanocomposite with an
average diameter of 35 nm which was aggregated due to
the magnetic nature of the catalyst.
The X‐ray diffraction patterns of the Fe3O4 MNPs and
Fe3O4/AlFe/Te nanocomposite are shown in Figure 2.
The diffraction of Fe3O4 crystal with an inverse spinel
structure (Ref code: 00‐003‐0863) from (220), (311),
(400), (422), (511), and (440) at peaks of 30.16, 35.45,
43.25, 53.54, 56.78, and 62.72° is shown in Figure 2a.
The X‐ray diffraction data of Fe3O4 MNPs shows the
absence of any impurities in the crystal plane. As shown
in Figure 2b, similar patterns of Fe3O4 MNPs data
(Figure 2a) were also identified showing the presence of
Fe3O4 MNPs crystalline phase in the final catalyst. Addi-
tional diffraction peaks at 23.02°, 27.55°, 38.25°, 40.44°,
43.34°, 49.63°, 62.79° and 82.03°assigned to the hexagonal
Tellurium crystalline phase (Ref. code: 01‐086‐2268) were
identified. In addition, diffraction peaks located at 30.91,
FIGURE 3 Synthesis of the ethyl acetate as a catalytic model
reaction
44.37, 54.93, 64.18, and 81.5° related to the cubic AlFe
crystalline phase (Ref code: 00‐001‐1257) were also identi-
fied. These results showed the presence of Fe3O4 MNPs in
the nanocomposite and AlFe, and Te crystalline phases
were obtained in addition to the MNPs as Fe3O4/AlFe/
Te nanocomposite (Figure 2b).The heavy atom effect of
Te and Al causes the characteristic peaks of Fe3O4 to
become weak (Figure 2b).
2.2 | Esterification reaction
The remarkable point for esterification reactions is the
low equilibrium constants. In order to obtain higher con-
version of esters, the reaction must be forced to comple-
tion by either removing the produced water or by using
an excess amount of acid or alcohol as substrates.[38] After
the preparation and full characterization of the Fe3O4/
AlFe/Te nanocomposite, catalytic performance of this
nanocatalyst was explored in the synthesis of ethyl acetate
from acetic acid and ethanol as a model reaction under
neat conditions (Figure 3). The molar ratio of carboxylic
acid to alcohol for the synthesis of esters is1:1/1. For
FIGURE 2 XRD patterns of (a) Fe3O4 MNPs and (b) Fe3O4/AlFe/Te nanocomposite

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ALAVI ET AL.
evaluating the efficiency of the Fe3O4/AlFe/Te nanocom-
posite, the influence of various parameters were studied
and optimized in neat conditions.
amount on the reaction was examined. Various amounts
(0.05 to 0.5 g) of catalyst were used for the synthesis of
ethyl acetate at room temperature for 12 h. With 0.05,
0.15, 0.3, and 0.5 g of catalyst 45, 54, 53, and 50% of prod-
uct were obtained, respectively (Table 1, entries 7‐10). By
increasing the amount of catalyst no obvious change in
product conversion was observed. Also, the conversion
of ethyl acetate increased with increasing temperature
from room temperature to reflux. Furthermore, the model
reaction was performed at reflux condition with 0.05, 0.15,
At the first, the model reaction was performed in the
absence of any catalyst at room temperature which does
not proceed even after 72 h. By increasing the reaction
temperature up to reflux, only 20% conversion for ethyl
acetate was observed after 72 h (Table 1; entries 1 and
2). The reaction progress was monitored by thin layer
chromatography (TLC). In addition, the reaction was
monitored with bare Fe3O4 MNPs, and Al2Te3as catalyst
at room temperature and reflux condition of which only
30‐40% conversion was observed (Table 1; entries 3‐6).
In the presence of 0.05 g of Fe3O4/AlFe/Te nanocompos-
ite after 12 h at room temperature, ethyl acetate was pro-
duced at 45% conversion. Thus, the effect of catalyst
TABLE 3 Reusability study of Fe3O4/AlFe/Te nanocomposite in
model reaction
Run
1
2
3
4
5
6
7
8
Conversion (%)
98
97
95
96
90
85
80
75
TABLE 1 Synthesis of ethyl acetate using different amount of catalyst at various time and temperatures
Entry
Catalyst
Cat. Amount (g)
Temp.
Time (h)
Conversion %
1
‐
‐
Rt.
72
Trace
2
‐
‐
Reflux
Rt.
72
48
48
48
48
12
12
12
12
3
20
35
40
30
35
45
54
53
50
80
98
98
95
3
Fe3O4
0.5
0.5
0.5
0.5
0.05
0.15
0.3
0.5
0.05
0.15
0.3
0.5
4
Fe3O4
Reflux
Rt.
5
Al2Te3
6
Al2Te3
Reflux
Rt.
7
Fe3O4/AlFe/Te
Fe3O4/AlFe/Te
Fe3O4/AlFe/Te
Fe3O4/AlFe/Te
Fe3O4/AlFe/Te
Fe3O4/AlFe/Te
Fe3O4/AlFe/Te
Fe3O4/AlFe/Te
8
Rt.
9
Rt.
10
11
12
13
14
Rt.
Reflux
Reflux
Reflux
Reflux
1
1
2
TABLE 2 Scope of the Fe3O4/AlFe/Te nanocomposite catalyzed esterification of carboxylic acids
Entry
1
X
R
Conversion
Entry
11
X
R
Conversion
H
Et
98
Cl
Et
96
2
H
n‐Bu
i‐pro
Hep
t‐Bu
Et
93
90
92
79
97
90
88
90
77
12
13
14
15
16
17
18
19
Cl
n‐Bu
i‐pro
Hep
t‐Bu
Et
94
88
91
80
96
91
82
70
3
H
Cl
4
H
Cl
5
H
Cl
6
Me
Me
Me
Me
Me
CN
CN
CN
CN
7
n‐Bu
i‐pro
Hep
t‐Bu
n‐Bu
i‐pro
t‐Bu
8
9
10

ALAVI ET AL.
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TABLE 4 Comparison of catalytic performance of different systems
Catalyst
Acid/alcohol
Cat. Amount
Solvent
T (°C)
Time (h)
Yield %
Ref.
[(cu(CH3SO3)2,*4H2O)]
1:1.1 mol
0.5 mol%
c.Hexane
Reflux
2.5
97
22
Fe2(SO4)3*4H2O/H2SO4
1:120 mol
1:1.1 mol
1.5:1 mol
1:6 mol
2 w% acid
5 mol%
0.15 g
‐
Reflux
80
2
96
95
78.3
88
94˃
93
89
69
74
96
98
23
24
25
26
13
27
28
16
16
18
Zn(ClO4)2·6H2O/MgSO4
‐
8
ZrP
c.Hexane
Reflux
80
8
ZnO/SiO2
1.25 w%
1 mol%
1 mol%
10 mol%
0.1 g
‐
3
HfCl4.2THF
1:1 mol
Toluene
Reflux
80
12
4
[(Ph2NH2)+OTf‐]
1:1 mol
Toluene
p‐dodecylbenzenesulfonic acid (DBSA)
1:2 mol
H2O
40
48
3
SnO
10:4 w/w
10:4 w/w
7:10 w/w
1.1:1 zmol
‐
160
Al2O3
0.1 g
‐
160
3
ZnO‐La2O3
Fe3O4/AlFe/Te
3 g
‐
200
3
0.15 g
Neat
Reflux
1
This work
0.3, and 0.5 g of catalyst. At optimized conditions, 0.15 g of
catalyst under neat condition and reflux produced 98%
conversion (Table 1; entries 11‐14). For calculating the
conversions, the reaction mixture was titrated by KOH‐
EtOH (0.1 M) according to the method of GB/T 1668‐
2008 after removal of the catalyst.[37]
The catalytic activity of Fe3O4/AlFe/Te nanocompos-
ite was comparable to those of previously reported homo-
geneous and heterogeneous systems (Table 4). The Fe3O4/
AlFe/Te nanocomposite can catalyze the reaction in very
short time and produce high yield. Also, the Fe3O4/
AlFe/Te nanocomposite could be separated from the reac-
tion mixture by an external magnet and reused 8 success-
ful cycles.
For further investigation of Fe/Al/Te nanocomposite
efficiency, the reaction of various carboxylic acids with
different substituted groups at the alpha position and
different types of alcohols was tested and the reaction
conversion was calculated. Different groups with electro‐
donating and electron‐withdrawing abilities at the alpha
position in carboxylic acids by methyl, chloro and cyano
groups were used. When various alcohols in the presence
of catalyst were mixed with acetic, propionic, chloroacetic,
and cyanoacetic acids, corresponding acetates (Table 2;
entries 1‐5), propionates (Table 2; entries 6‐10), chloro ace-
tates (Table 2; entries 11‐15), and cyano acetates (Table 2;
entries 16‐19) were produced respectively, in high conver-
sions. As shown in Table 2, ethanol (entries 1, 6, 11, 16),
n‐butanol (entries 2, 7, 12, 17) and heptanol (entries 4, 9,
14) were mixed with various carboxylic acids under opti-
mized reaction conditions and transformed to correspond-
ing esters at excellent conversion rates. Also, iso‐propanol
(Table 2, entries 3, 8, 13, 18) and tert‐butanol (Table 2;
entries 5, 10, 15, 19) reacted with various carboxylic acids
to produce corresponding esters at high conversions.
The reusability of Fe3O4/AlFe/Te nanocomposite was
also studied. Results show that the Fe3O4/AlFe/Te nano-
composite has recyclability in addition to its easy and sim-
ple recovery in the synthesis of ethyl acetate as a model
reaction. In this study, the catalyst has the ability to be
recycled for at least 8 runs (Table 3). After each run, the
solid catalyst was recovered by an external magnetic field,
extensively washed with acetone and dried at 80 °C.
3 | CONCLUSION
In summary, the Fe3O4/AlFe/Te nanocomposite as a new
and potent catalyst for esterification reaction was pre-
pared for the first time. The efficiency of Fe3O4/AlFe/Te
nanocomposite was investigated in the esterification of
various carboxylic acids with electron donating and with-
drawing groups at the alpha position of the carboxyl
group. Primary alcohols revealed higher conversion in
comparison with secondary and tertiary alcohols. Finally,
the catalyst can be removed by using the external mag-
netic source and does not to require the use of column
chromatography.
4 | MATERIALS AND METHODS
4.1 | Materials and instruments
All the materials such as acetic, propionic, chloroacetic
and cyanoacetic acid, alcohols and the other chemicals
used were of analytical grade from a commercial
source and Sigma‐Aldrich that were used without any
purification.

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ALAVI ET AL.
The prepared catalyst (Fe3O4@Al‐Te) nanoparticles
the catalyst was collected by an external magnet. The res-
idue was washed with sodium bicarbonate solution (10%),
brine, water and then the ester layer was separated and
dried with anhydrate sodium sulfate. The purification of
ester was carried out by distillation under the reduced
pressure.
were characterized by TEM and SEM experiments that
were conducted on a Leo 912AB microscope (Germany)
operated at 120 kV and Leo 1450VP (Germany), respec-
tively. Powder XRD patterns were recorded on a Bruker
D4 X‐ray diffractometer with Ni‐filtered Cu KR radiation
(40 kV, 30 mA).
The elemental analysis was studied using by induc-
tively coupled plasma optical emission spectrometry
(ICP‐OES) (USA).
4.3 | Characterization of esters:
4.3.1 | Ethyl acetate
1H NMR (300 MHz) spectra were obtained by using a
Bruker Avance DRX‐300 Fourier transformer spectrome-
ter. Chemical shifts are reported in parts per million (δ)
downfield from tetramethylsilane (TMS).
1
A colorless liquid with a strong fruity odor. H NMR
(301 MHz, Chloroform‐d) δ 4.9 (q, J = 7.1 Hz, 2H), 2.01
(s, 3H), 1.23 (t, J = 7.2 Hz, 3H); 13C NMR (75 MHz, Chlo-
roform‐d) δ 170.99, 60.28, 20.90, 14.10
4.1.1 | Synthesis of Fe3O4 magnetic nano-
particles (MNPs)
4.3.2 | n‐butyl acetate
Fe3O4 Magnetic nanoparticles were prepared by a hydro-
thermal technique as previously reported.[38] Briefly,
FeCl3.6H2O (1.6 g, 6 mmol), sodium acetate (4.0 g,
48.8 mmol) and (1.5 g, 5.8 mmol) trisodium citrate were
dissolved in ethylene glycol (75 ml). After vigorous
stirring for 1 h, the resulting yellow solution was trans-
ferred into a Teflon‐lined stainless‐steel autoclave with a
capacity of 100 ml, then sealed and heated to 200 °C. After
reaction for 12 h, the autoclave was cooled to room
temperature. The obtained black Fe3O4 MNPs were
collected with a magnet and washed several times with
water and ethanol, separately. Finally, the product was
dried under vacuum at 50 °C for 12 h.
1H NMR (301 MHz, Chloroform‐d) δ 4.07 (t, J = 6.7 Hz,
2H), 2.06 (s, 3H), 1.62 (p, J = 6.9 Hz, 2H), 1.50 – 1.28
(m, 2H), 0.94 (t, J = 7.3 Hz, 3H); 13C NMR (76 MHz, Chlo-
roform‐d) δ 171.22, 64.34, 30.63, 20.99, 19.11, 13.69.
4.3.3 | Heptyl acetate
NMR (301 MHz, Chloroform‐d) δ 3.95 (t, J = 6.5 Hz, 2H),
2.04 (s, 3H), 1.75 (p, J = 6.6 Hz, 2H), 1.45 – 1.20 (m, 8H),
0.82 (t, J = 7.3 Hz, 3H); 13C NMR (75 MHz, Chloroform‐d)
δ 171.44, 62.15, 31.10, 29.99, 29.09, 26.51, 23.89, 22.99,
13.99.
4.1.2 | Synthesis of Fe3O4/Al2Te3 magnetic
nanocomposite (Fe3O4/AlFe/Te)
4.3.4 | Isopropyl acetate
1
A colorless liquid with a strong fruity odor. H NMR
The Fe3O4/AlFe/Te nanocomposite was synthesized by a
facile sol–gel method. Typically, 0.2 g Fe3O4 was added
to the three‐neck round bottom flask followed by the
addition of 70 ml ethanol/water solution (1:1) containing
1 g Al2Te3. The mixture was sonicated for 15 min, and
then 30 ml 0.5 M NaOH ethanol solution was added to
the mixture and stirred for 30 min. The reaction was
maintained at 70 °C for 12 h. The black precipitate was
collected by an external magnet, and then dried at 80 °C
for 6 h.
(301 MHz, Chloroform‐d) δ 5.00 (heptet, J = 6.2 Hz,
1H), 2.06 (s, 3H), 1.19 (d, J = 6.2 Hz, 6H); 13C NMR
(75 MHz, Chloroform‐d) δ 170.79, 68.11, 41.22, 21.62.
4.3.5 | tert‐butyl acetate
1H NMR (301 MHz, Chloroform‐d) δ 1.98 (s, 9H), 1.45 (s,
3H); 13C NMR (76 MHz, Chloroform‐d) δ 170.53, 80.13,
28.05, 22.52.
4.2 | Synthesis of esters
4.3.6 | Ethyl propionate
In a typical reaction procedure, a 50 ml round bottomed
boiling flask equipped with reflux condenser was charged
with 0.11 mol of carboxylic acid, 0.1 mol of alcohol and
0.15 g of catalyst. The contents of the flask were refluxed
for 1 h to complete the reaction. After cooling the mixture,
1H NMR (301 MHz, Chloroform‐d) δ 4.04 (q, J = 7.1 Hz,
2H), 2.23 (q, J = 7.6 Hz, 2H), 1.17 (t, J = 7.2 Hz, 3H),
1.05 (t, J = 7.6 Hz, 3H); 13C NMR (75 MHz, Chloroform‐
d) δ 174.35, 60.09, 27.47, 14.10, 8.98.

ALAVI ET AL.
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4.3.7 | Butyl propionate
4.3.14 | Isopropyl 2‐chloroacetate
1
1H NMR (301 MHz, Chloroform‐d) δ 4.06 (t, J = 6.7 Hz,
2H), 2.32 (q, J = 7.6 Hz, 2H), 1.61 (p, J = 6.9 Hz, 2H),
1.44 – 1.35 (p, J = 7.1 Hz, 2H), 1.16 ‐1.11 (t, J = 7.6 Hz,
3H), 0.91 – 0.87 (t, J = 7.2 Hz, 3H); 13C NMR (75 MHz,
Chloroform‐d) δ 174.95, 64.46, 31.43, 27.56, 22.53, 13.94,
9.17.
An amber‐colored liquid with a strong odor. H NMR
(301 MHz, Chloroform‐d) δ 5.02 (heptet, J = 6.3 Hz,
1H), 3.96 (s, 2H), 1.21 (d, J = 6.3 Hz, 6H); 13C NMR
(75 MHz, Chloroform‐d) δ 166.79, 70.11, 41.22, 21.63.
4.3.15 | tert‐butyl 2‐chloroacetate
1H NMR (301 MHz, Chloroform‐d) δ 3.98 (s, 3H), 1.42 (s,
9H); 13C NMR (75 MHz, Chloroform‐d) δ 168.02, 81.7,
40.94, 40.4, 23.12
4.3.8 | Heptyl propionate
1H NMR (301 MHz, Chloroform‐d) δ 4.86 – 4.80 (q,
J = 7.5 Hz, 2H), 2.22 (q, J = 7.6 Hz, 2H), 1.59 – 1.38 (m,
2H), 1.20 (m, 8H), 1.06 (t, J = 7.6 Hz, 3H), 0.81 (t,
J = 6.6 Hz, 3H); 13C NMR (75 MHz, Chloroform‐d) δ
174.16, 70.78, 35.96, 31.75, 29.12, 27.94, 25.37, 22.58,
14.05, 9.22.
4.3.16 | Ethyl 2‐cyanoacetate
1H NMR (301 MHz, Chloroform‐d) δ 4.30 (q, J = 7.1 Hz,
2H), 3.51 (s, 2H), 1.25 (t, J = 7.2 Hz, 3H); 13C NMR
(75 MHz, Chloroform‐d) δ 163.33, 113.28, 67.82, 31.22,
14.04
4.3.9 | Isopropyl propionate
1H NMR (301 MHz, Chloroform‐d) δ 4.13 (dq, J = 13.3,
6.6 Hz, 1H), 2.30 (q, J = 6.9 Hz, 2H), 1.12 (t, J = 7.6 Hz,
3H), 0.90 (d, J = 6.6 Hz, 6H); 13C NMR (75 MHz, Chloro-
form‐d) δ 174.51, 62.90, 37.32, 22.41, 9.1.
4.3.17 | Butyl 2‐cyanoacetate
1H NMR (301 MHz, Chloroform‐d) δ 4.31 (t, J = 6.7 Hz,
2H), 3.51 (s, 2H), 1.68 – 1.57 (m, 2H), 1.41 (m, 2H), 0.90
(t, J = 7.3 Hz, 3H); 13C NMR (75 MHz, Chloroform‐d) δ
162.98, 113.10, 67.32, 31.04, 30.97, 19.10, 14.04
4.3.10 | tert‐butyl propionate
1
A colorless oil. H NMR (301 MHz, Chloroform‐d) δ 2.32
4.3.18 | Isopropyl 2‐cyanooacetate
(q,J = 7.5 Hz, 2H), 1.45 (s, 9H), 1.13 (t, J = 7. Hz, 3H);
13C NMR (75 MHz, Chloroform‐d) δ 174.60, 63.10, 35.32,
32.41, 9.2.
1H NMR (301 MHz, Chloroform‐d) δ 5.01 (heptet,
J = 6.3 Hz, 1H), 3.71 (s, 2H), 1.19 (d, J = 6.3 Hz, 6H);
13C NMR (75 MHz, Chloroform‐d) δ 162.99, 113, 67.11,
31.22, 21.63.
4.3.11 | Ethyl 2‐chloroacetate
1H NMR (301 MHz, Chloroform‐d) δ 4.25 (q, J = 7.1 Hz,
2H), 4.06 (s, 2H),1.30 (t, J = 7.2 Hz, 3H); 13C NMR
(75 MHz, Chloroform‐d) δ 167.28, 62.24, 40.94, 14.04.
4.3.19 | tert‐butyl 2‐cyanoacetate
1H NMR (301 MHz, Chloroform‐d) δ 3.47 (s, 3H), 1.42 (s,
9H); 13C NMR (75 MHz, Chloroform‐d) δ 163.00, 113.81,
80.10, 31.58, 21.99.
4.3.12 | Butyl 2‐chloroacetate
1H NMR (301 MHz, Chloroform‐d) δ 4.21 (t, J = 6.7 Hz,
2H), 3.97 (s, 2H), 1.54 (m, 2H), 1.18 (m, 2H), 0.84 (t,
J = 7.5 Hz, 3H); 13C NMR (75 MHz, Chloroform‐d) δ
166.97, 74.61, 41.16, 28.61, 19.23, 9.50.
ACKNOWLEDGMENT
The authors gratefully acknowledged for partially
financial support of this study (Grant No. 37712) by
Research Council of Ferdowsi University of Mashhad.
4.3.13 | Heptyl 2‐chloroacetate
ORCID
1H NMR (301 MHz, Chloroform‐d) δ 4.21 (t, J = 6.7 Hz,
2H), 4.01 (s, 2H), 1.69 (m, 2H), 1.33 (m, 8H), 0.90
(t, J = 5.2 Hz, 3H); 13C NMR (75 MHz, Chloroform‐d)
Seyed Jamal Alavi http://orcid.org/0000-0003-1571-5458
Hamid Sadeghian http://orcid.org/0000-0001-7894-5002
Seyed Mohammad Seyedi
http://orcid.org/0000-0001-
δ
167.28, 62.84, 40.55, 30.12, 28.51, 26.56, 24.58,
5542-5880
22.54, 14.04.
Hossein Eshghi http://orcid.org/0000-0002-8417-220X

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