Amidation and esterification of carboxylic acids with amines and phenols by N,N′-diisopropylcarbodiimide: A new approach for amide and ester bond formation in water

Article abstract of DOI:10.1016/j.tet.2018.06.064

The present study reports the successful synthesis of two important and abundant functional groups “ester and amide” by N,N′-diisopropylcarbodiimide (DIC) in water as a green solvent. A wide range of substrates could be employed with high functional group tolerance. The products were obtained in high yields after short reaction times. This method provides an efficient, economic, simple and very mild protocol for ester and amide bond formation in aqueous media. In addition, this work not only may lead to environmentally benign systems but also will provide a new aspect of organic chemistry in water.

Full text of DOI:10.1016/j.tet.2018.06.064

Accepted Manuscript
Amidation and esterification of carboxylic acids with amines and phenols by N,N'-
diisopropylcarbodiimide: A new approach for amide and ester bond formation in water
Nadia Fattahi, Morteza Ayubi, Ali Ramazani
PII:
S0040-4020(18)30779-8
10.1016/j.tet.2018.06.064
TET 29660
DOI:
Reference:
To appear in: Tetrahedron
Received Date: 31 March 2018
Revised Date: 14 June 2018
Accepted Date: 29 June 2018
Please cite this article as: Fattahi N, Ayubi M, Ramazani A, Amidation and esterification of carboxylic
acids with amines and phenols by N,N'-diisopropylcarbodiimide: A new approach for amide and ester
bond formation in water, Tetrahedron (2018), doi: 10.1016/j.tet.2018.06.064.
This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to
our customers we are providing this early version of the manuscript. The manuscript will undergo
copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please
note that during the production process errors may be discovered which could affect the content, and all
legal disclaimers that apply to the journal pertain.

ACCEPTED MANUSCRIPT
Graphical Abstract
Amidation and esterification of carboxylic acids with amines and phenols by N,N'-
diisopropylcarbodiimide: a new approach for amide and ester bond formation in water
Nadia Fattahi, Morteza Ayubi, and Ali Ramazani *
Department of Chemistry, University of Zanjan, P O Box 45195-313, Zanjan (Iran)

ACCEPTED MANUSCRIPT
Tetrahedron
journal homepage: www.elsevier.com
Amidation and esterification of carboxylic acids with amines and phenols by N,N'-
diisopropylcarbodiimide: a new approach for amide and ester bond formation in water
Nadia Fattahi, Morteza Ayubi and Ali Ramazani
Department of Chemistry, University of Zanjan, P O Box 45195-313, Zanjan, Iran
ARTICLE INFO
ABSTRACT
Article history:
Received
Received in revised form
Accepted
The present study reports the successful synthesis of two important and abundant functional groups
"ester and amide" by N,N'-diisopropylcarbodiimide (DIC) in water as a green solvent. A wide range of
substrates could be employed with high functional group tolerance. The products were obtained in
high yields after short reaction times. This method provides an efficient, economic, simple and very
mild protocol for ester and amide bond formation in aqueous media. In addition, this work not only
may lead to environmentally benign systems but also will provide a new aspect of organic chemistry
in water.
Available online
Keywords:
amidation
esterification
water
aqueous reactions
N, N'-diisopropylcarbodiimide
———
Corresponding author. Tel.: +98 241 5152572, fax: +98 241 5283100; e-mail: aliramazani@gmail.com ; aliramazani@znu.ac.ir

2
Tetrahedron
ACCEPTED MANUSCRIPT
1. Introduction
Amide and ester linkages are one of the most fundamental and
numerous chemical bonds in nature. Esterification reactions
suggest achieve to significant products in chemical and
pharmaceutical industries and can be found in natural products,
pharmaceuticals, bulk chemicals, fine chemicals and polymers .1
On the other hand, the amide moiety constitutes the backbone of
the biologically vital proteins, and it is ubiquitous in many
natural products, proteins, pharmaceuticals, and therapeutic
drugs.2
Due to the fundamental importance of ester and amide, to date
a variety of esterification and amidation conditions have been
developed.3-9 Among them, the use of DCC/DMAP or
DIC/DMAP is very common and interesting producer for their
formation.10 However, generally, ester and amide bond formation
by these methods require anhydrous solvents. Because in the
presence of water, the equilibrium is displaced to the reactant
side and hydrolysis of the desired products takes place.
Meanwhile, the progression of the reaction, especially in
esterification
reactions,
requires
the
use
of
4-
Dimethylaminopyridine as a strong Nucleophilic Catalyst.
Using water as an ideal solvent in organic reactions has
received notable attention in the arena of organic synthesis, due
to its many desirable attributes such as low cost, nontoxicity,
safety, and environmental friendliness compared with organic
solvents. In addition, organic synthesis in aqueous media offering
key benefits such as rate enhancement and insolubility of the
final products, which facilitates their isolation by simple filtration
due to unique physical and chemical properties of water.11-15
Furthermore, in aqueous media, it is unessential to dry solvents,
substrates, and reagents before use. Therefore, drying agents,
energy, and time can be saved.
Along with our continuous efforts on the development of organic
synthesis in aqueous media,16-28 we recently reported the
synthesis of N-acylurea derivatives from carbodiimides and
carboxylic acids in water as a green solvent.29
In continuation of this study, herein, we wish to report, for the
first time, new conditions for amide and ester bond formation by
using of N,N'-diisopropylcarbodiimide in water at room
temperature. This approach provides easy access to highly
functionalized ester and amide derivatives in environmentally
friendly and mild conditions (scheme 1).
Scheme 1. Esterification and amidation of carboxylic acids in
water

2. Results and Discussion
Table 1. Amidation reactions of carboxylic acids in watera
ACCEPTED MANUSCRIPT
From the economical and environmental point of view, the use
of water as an efficient and green solvent has attracted
considerable attention. It is obvious that, the acidity of carboxylic
acids in water are increased compared to organic solvents. We
used this property of water in previous study.29
In water a hydrogen ion is transferred from the -COOH group
to a water molecule. Thus, reactivity of carboxylic acids are
increased in aqueous media, therefore, carboxylate ion can react
rapidly with DIC. With this in mind, in the present study, we
selected water as an effective and green solvent and DIC as a
coupling reagent for preparation of two basic, important and
abundant functional groups in nature.
In order to investigation of amide and ester bond formation,
initially, we examined amidation reaction for a range of
carboxylic acids and amines. In this regard, treatment of
carboxylic acid (1mmol), amine (1 mmol) and N,N'-
diisopropylcarbodiimide (1 mmol) in water afford to generation
of related amide in excellent yield. The results are presented in
Table 1.
As shown in table 1, all carboxylic acids such as aromatic and
aliphatic samples react rapidly with DIC to afford N-acylurea
derivatives B,29 and then in the presence of amine moiety,
compounds B can be easily converted to the corresponding
amides in high yields.
After successfully synthesizing diverse amides in water, the
esterification of carboxylic acids with phenols was investigated
via similar pathway (table 2).
Entry
1
Product
Timeb (min)
Yieldc (%)
15
96
2
3
15
15
95
94
4
5
6
15
15
15
45
94
95
96
89
As expected, reaction time for conversion of
B to
7
corresponding ester increased as compared to amide formation,
due to less nucleophilicity of phenol than amine. According to
table 2, both electron-rich and electron-poor phenols gave
excellent yields of corresponding ester. Results are summarized
in the table 2. Shorter reaction time was observed with phenol
bearing electron-donating group (entry 5).
We also turned our attention to aliphatic alcohols such as
ethanol, hexanol and ethylene glycol instead of phenol, but no
reaction was observed even after prolonged reaction time. This
phenomenon can be explained due to more acidity and reactivity
of phenol than alcohol. It is noteworthy that, compared
to alcohol, phenol is about 1 million times more acidic. Thus, it
can lose H ion easily in water and then obtained phenolat anion
can rapidly react with compound B.
8
9
40
15
87
91
10
45
91
In addition, in order to prove the role of water as an effective
solvent in progress of amidation and esterification reactions,
additional experiments were performed in presence of
dichloromethane as an organic solvent.
11
12
13
30
15
15
93
92
90
O
NH
In the case of amidation reaction, we selected benzoic acid
and benzyl amine as acid and amine reagents, respectively. In
this case, the obtained yield from the reaction of acid and DIC
was lower than in water. Because in organic solvent, acid cannot
ionize, therefore, its activity is low and some acid remains in the
reaction vessel. As a result, the yield of the amide was decreased.
In order to esterification reaction, we used benzoic acid and 4-
methylphenol as acid and phenol reagents, respectively. As
mentioned above, the obtained yield from the first step of
reaction was lower than water and the final product was obtained
in low yield and long reaction time. It is necessary to mention
that in organic solvents phenol can not be ionized, therefore, in
organic solvents, it's nucleophilic reactivity was lower in
comparison with water.
Cl
aReaction conditions: carboxylic acid (1 mmol), amine (1 mmol), DIC (1
mmol), 2 mL H2O, R.T.
bReaction time: B→C
cIsolated yield

4
Tetrahedron
Table 2. Esterification reactions of carboxylic acids in water
On basis of previous literature results and our experiments, a
ACCEPTED MANUSCRIPT
plausible mechanism for amidation and esterification reaction in
presence of water is shown in Scheme 2. First, carboxylic acid A
ionize in water to form carboxylate ion and hydronium ion (the
acidic species in water). Then, carboxylate ion reacts with DIC E
to form the intermediate B. Finally, nucleophilic attack of amine
and phenolat anion to intermediate B provides amide C and ester
D, respectively.
Entry
1
Product
Timeb (h)
Yieldc (%)
O
O
Cl
12
93
Cl
2
4
92
3
4
5
6
7
10
10
3
94
89
92
92
89
Scheme 2. Proposed mechanism for esterification and amidation reactions
in water
In addition, we compared the efficiency of our method in amide
and ester bond formation with some other previous methods.
(Table 3 and 4). It can be clearly seen that our method is superior
to most of the previous methods in terms of reaction conditions,
yield and reaction time .
12
36
8
9
12
24
91
89
10
11
4
5
91
92
aReaction conditions: carboxylic acid (1 mmol), phenol (1 mmol), DIC (
mmol), 2 mL H2O, R.T.
bReaction time: B→D
Isolated yield.

Table 3. Comparison of the results with some other
previously methods in amidation reactions
Table 4. Comparison of the results with some other
previously methods in esterification reactions
ACCEPTED MANUSCRIPT
STARTING
Yield
(%)a
STARTING
MATERIAL
Catalyst &
Conditions
Yield
(%)a
NO
1
Catalyst & Conditions
Time
Ref.
NO
1
Time
Ref.
MATERIAL
PPh3, I2,
anhydrous
acetonitrile,
MW (85 °C).
PhCOOH
PPh3, I2, anhydrous
acetonitrile, MW (85
°C).
PhCOOH
30b
92
93
30
45b
82
92
30
PhCH2NH2
PhCONH2
PhCH2NH2
p-MeC6H4OH
31
2
3
MnO2, Neat, 150 °C
12c
20c
p-BrC6H4OH
(PhCO2)2
40
2
3
2.5c
24c
Imidazole,
CH3CN, reflux
Ph3P, CCl4,
(EtO)2MeSiH, bis(4-
nitrophenyl)phosphate,
anhydrous toluene,
110 °C
[Ru(p-
cymene)Cl2]2,
Cs2CO3 , dry
xylene under O2
, 130 °C
PhCOOH
32
60
p-MeC6H4CH2OH
p-NO2C6H4OH
41
86
PhCH2NH2
PhCOOEt
PhCH2NH2
PhCOOMe
PhCH2NH2
PhCH2OH
Ph-CN
LiOH, solvent-free,
200 °C
33
34
35
36
37
38
6
15b
20c
6c
78
78
91
77
95
79
63
94
96
Cu(OTf)2, urea,
EtOAc, 60 °C,
under air.
4
5
p-MeC6H4COOH
PhB(OH)2
42
43
4
5
12c
88
59
Cp2ZrCl2, anhydrous
toluene, 110 °C
p-NO2C6H4COOH
Ph2IOTf
KOt-Bu, reflux,
Toluene
1c
H-beta zeolite, 120 °C,
Toluene
6
PPh3/N-
Chlorobenzotria
zole (NCBT),
CH2Cl2, 0 °C to
r.t.
p-NO2C6H4COOH
PhOH
44
45
6
7
8
90b
90
72
PhCOOH
PhCH2NH2
PhCOH
PPh3, I2, iPr2NEt,
CH2Cl2, 0 °C to r.t.
7
1.5c
24c
8c
CoCl2.6H2O, PPh3,
NH2OH.HCl
Pivalonitriler, 135 °C
PhCOOH
PhOH
20b
Ph3P, I2, Et3N,
CH2Cl2, 0 °C to
r.t.
10
11
12
13
14
PhCH2NH2
PhCH2NH2
PhCOOMe
PhCOOH
PhCH2NH2
PhCH2OH
PhCH2N3
PhCOOH
PhCH2NH2
CaI2, anhydrous
toluene, 110 °C
PhCOOH
PhOH
9
60b
69
92
Tropylium
chloride, Et3N,
CH2Cl2, r.t.
Tropylium chloride,
Et3N, CH2Cl2, r.t.
60b
48c
75b
PhCOOH
This
Wor
k
N, N'-
diisopropylcarbo
diimide, water,
r.t.
10
4c
p-MeC6H4OH
RuH2(PPh3)4, NaH,
CH3CN, toluene,
reflux
39
aIsolated yield
bTime (min)
cTime (h)
N, N'-
diisopropylcarbodiimi
de, water, r.t.
This
Work
aIsolated yield
bTime (min)
cTime (h)

6
Tetrahedron
8.50 Hz, 2H); 13C NMR (62.90 MHz, CDCl3): δ 44.2, 126.2,
ACCEPTED MANUSCRIPT
3. Conclusions
127.7, 127.9, 128.6, 128.8, 131.8, 133.2, 137.9, 166.6.
In conclusion, we have developed an efficient, cost and
N-Benzyl-4-chlorobenzamide (entry 4, table 1)46
IR (KBr) 3314, 3084, 2923, 2852, 1638, 1552, 1420, 1256,
1092, 712 cm-1; 1H NMR (250.0 MHz, CDCl3) δ 4.64 (d, J = 4.75
Hz, 2H), 6.34 (bs, 1H), 7.35-7.42 (m, 7H), 7.73 (d, J = 8.00 Hz,
2H).
N-Benzyl-4-tert-butylbenzamide (entry 5, table 1)32
IR (KBr) 3286, 3059, 2963, 1633, 1548, 1321, 712 cm-1; 1H
NMR (250.0 MHz, CDCl3) δ 1.33 (s, 9H), 4.66 (d, J = 5.75 Hz,
2H), 6.34 (bs, 1H), 7.31-7.35 (m, 5H), 7.45 (d, J = 8.00 Hz, 2H),
7.73 (d, J = 8.25 Hz, 2H); 13C NMR (62.90 MHz, CDCl3): δ 31.1,
33.4, 44.0, 125.5, 126.8, 127.6, 127.9, 128.8, 131.4, 138.2, 155.1,
166.7.
ecofriendly method for amidation and esterification of carboxylic
acids based on N, N'-diisopropylcarbodiimide in water. The
present procedure is general as a wide range of carboxylic acids
and amines including aromatic and aliphatic examples to afford
the desired amides. In addition, this work also offers an efficient
and simple procedure for ester bond formation from carboxylic
acids and phenol moiety with a variety of functional groups.
Considering the importance of the amide and ester bond, we hope
that our new approach may inspire researchers to develop
alternative methods for the formation of amide and ester bonds in
the coming years. Moreover, the application of this method for
esterification and amidation of amino acids is currently underway
in our group and will be reported shortly.
N-benzyl-3-chlorobenzamide (entry 6, table 1)46
4. Experimental Section
IR (KBr) 3312, 3026, 2927, 1640, 1552, 1320, 715 cm-1; 1H
NMR (250.0 MHz, CDCl3) δ 4.63 (d, J = 5.00 Hz, 2H), 6.41 (bs,
1H), 7.35-7.49 (m, 7H), 7.65 (d, J = 7.00 Hz, 1H), 7.78 (s, 1H);
13C NMR (62.90 MHz, CDCl3): δ 44.2, 125.0, 127.3, 127.7,
127.9, 128.8, 129.9, 131.6, 166.2.
Materials and methods: Starting materials were obtained
from Merck (Germany), Fluka (Switzerland) and Sigma- Aldrich
(USA) and were used without further purification. The methods
used to follow the reactions are TLC. Fourier transform infrared
(FTIR) spectra were recorded by
a Jasco 6300 FTIR
N-benzyl-3-nitrobenzamide (entry 7, table 1)47
spectrometer. The FTIR spectra were measured in the 400–4000
1
IR (KBr) 3295, 3086, 3031, 1642, 1525, 1351, 693 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 4.65 (d, J = 5.75 Hz, 2H), 6.82
(bs, 1H), 7.34-7.65 (m, 6H), 8.17 (d, J = 7.75 Hz, 1H), 8.34 (d, J
= 8.25 Hz, 1H), 8.60 (s, 1H).
cm-1 region with samples dispersed in KBr pellets. H and 13C
NMR spectra (CDCl3) were recorded on a Bruker DRX-250
Avance spectrometer at 250.13 and 62.90 MHz, respectively.
Amide bond formation in water: To a magnetically stirred
solution of carboxylic acid (1 mmol) in H2O was added 1 mmol
of N, N'-diisopropylcarbodiimide and the reaction mixture was
stirred at room temperature for 1 h. after this period, the amine (1
mmol) was added and the reaction mixture was stirred at room
temperature for the indicated time until the starting materials
were totally consumed as checked by TLC. Then, the solvent was
separated by filtration and the solid washed several times with
lukewarm water in order to remove the by-product diisopropyl
urea (DIU).
N-phenylbenzamide (entry 8, table 1)30
1
IR (KBr) 3343, 1655, 1599, 1438, 1321, 749, 689 cm-1; H
NMR (250.13 MHz, CDCl3) δ 7.16 (m, 1H), 7.37 (m, 2H), 7.48-
7.51 (m, 3H), 7.64 (d, J = 7.75 Hz, 2H), 7.85 (m, 3H).
4-bromo-N-isobutylbenzamide (entry 9, table 1)48
IR (KBr) 3315, 2960, 2924, 1634, 1545, 1012, 844 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 0.98 (d, J = 6.50 Hz, 6H), 1.84-
1.95 (m, 1H), 3.28 (t, J = 6.25 Hz, 2H), 6.11 (bs, 1H), 7.56 (d, J
= 8.25 Hz, 2H), 7.63 (d, J = 8.00 Hz, 2H); 13C NMR (62.90 MHz,
CDCl3): δ 20.1, 28.6, 47.4, 128.1, 128.5, 131.7, 167.6.
Ester bond formation in water: To a magnetically stirred
solution of carboxylic acid (1 mmol) in H2O was added 1 mmol
of N, N'-diisopropylcarbodiimide and the reaction mixture was
stirred at room temperature for 1 h. after this period, the phenol
(1 mmol) was added and the reaction mixture was stirred at room
temperature for the indicated time until the starting materials
were totally consumed as checked by TLC. Then, the solvent was
separated by filtration and the solid washed several times with
lukewarm water in order to remove the by-product diisopropyl
urea (DIU).
N-benzylbenzamide (entry 1, table 1)32
IR (KBr) 3339, 2967, 1635, 2924, 1637, 1554, 1316, 1259,
695 cm-1; 1H NMR (250.0 MHz, CDCl3) δ 4.67 (d, J = 5.50 Hz,
2H), 6.35 (bs, 1H), 7.21-7.47 (m, 8H), 7.80 (d, J = 7.00 Hz, 2H).
N-isobutyl-3-nitrobenzamide (entry 10, table 1)49
IR (KBr) 3298, 2960, 1643, 1531, 1345, 1161, 704 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 1.00 (d, J = 5.50 Hz, 2H), 1.75-
1.93 (m, 1H), 3.33 (bs, 2H), 6.24 (bs, 1H), 7.65 (bs, 1H), 8.16 (d,
J = 5.5 Hz, 1H), 8.36 (d, J = 6 Hz, 1H), 8.57 (s, 1H); 13C NMR
(62.90 MHz, CDCl3): δ 20.1, 28.6, 47.6, 121.5, 125.9, 129.9,
131.1, 133.2, 137.1, 148.2, 167.6.
N-isobutyl-2-naphthamide (entry 11, table 1)50
IR (KBr) 3291, 2957, 1638, 1543, 1316, 1259, 781 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 1.02 (d, J = 6.00 Hz, 6H), 1.92-
1.97 (m, 1H), 3.38 (bs, 2H), 6.02 (bs, 1H), 7.45-7.92 (m, 6H),
8.29 (d, J = 7.00 Hz, 1H).
3-chloro-N-isobutylbenzamide (entry 12, table 1)51
N-Benzyl-4-iodobenzamide (entry 2, table 1)32
IR (KBr) 3301, 3074, 2965, 2925, 1633, 1544, 1465, 1321,
1
1012, 698 cm-1; H NMR (250.13 MHz, CDCl3) δ 0.99 (d, J =
IR (KBr) 3289, 3060, 1635, 1541, 1318, 1237, 1156, 698 cm-
1; 1H NMR (250.0 MHz, CDCl3) δ 4.62 (d, J = 5.25 Hz, 2H), 6.48
(bs, 1H), 7.22-7.52 (m, 5H), 7.65 (d, J = 7.25 Hz, 2H), 7.76 (d, J
= 6.50 Hz, 2H); 13C NMR (62.90 MHz, CDCl3): δ 44.2, 98.8,
125.0, 127.3, 127.7, 127.9, 128.5, 128.8, 129.9, 131.6, 137.8,
166.7.
6.50 Hz, 2H), 1.85-1.96 (m, 1H), 3.29 (t, J = 6.25 Hz, 2H), 6.12
(bs, 1H), 7.34-7.53 (m, 2H), 7.63 (d, J = 7.50 Hz, 1H), 7.74 (s,
1H); 13C NMR (62.90 MHz, CDCl3): δ 20.1, 28.5, 47.4, 125.0,
127.2, 129.8, 131.2, 134.3, 137.1, 166.6.
N-benzyloctadecanamide (entry 13, table 1)52
N-benzyl-4-bromobenzamide (entry 3, table 1)32
IR (KBr) 3293, 2952, 2917, 2848, 1632, 1552, 697 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 0.87 (bs, 3H), 1.25 (m, 28 H), 1.62
(m, 2 H), 2.23 (m, 2 H), 4.28 (d, J = 4.75 Hz, 2H), 5.72 (bs, 1H),
7.29 (m, 5H); 13C NMR (62.90 MHz, CDCl3): δ 14.1, 21.0, 22.7,
IR (KBr) 3315, 3084, 2923, 1641, 1549, 1257, 712 cm-1; 1H
NMR (250.0 MHz, CDCl3) δ 4.64 (d, J = 5.50 Hz, 2H), 6.34 (bs,
1H), 7.26-7.41 (m, 5H), 7.56 (d, J = 8.50 Hz, 2H), 7.66 (d, J =

1.
Allen, C. L.; Williams, J. M. Chem. Soc. Rev. 2011, 40,
3405-3415.
El-Faham, A.; Albericio, F. Chem. Rev. 2011, 111, 6557-
25.0, 25.8, 29.3, 29.5, 29.7, 31.9, 36.8, 43.6, 127.3, 127.5, 127.8,
128.7, 154.0.
ACCEPTED MANUSCRIPT
2.
3.
4.
3-chlorophenyl 3-chlorobenzoate (entry 1, table 2)53
IR (KBr) 3085, 2925, 1736, 1571, 1420, 1201, 892 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 7.13 (d, J = 7.25 Hz, 1H), 7.34-
7.64 (m, 4H), 7.13 (d, J = 7.25 Hz, 1H), 8.07 (d, J = 7.25 Hz,
1H), 8.16 (s, 1H).
4-nitrophenyl 3-chlorobenzoate (entry 2, table 2)54
IR (KBr) 2924, 1742, 1522, 1351, 1290, 1254, 1063, 734 cm-
1; 1H NMR (250.13 MHz, CDCl3) δ 7.41-7.53 (m, 3H), 7.66 (d, J
= 7.75 Hz, 1H), 8.09 (d, J = 7.75 Hz, 1H), 8.15 (s, 1H), 8.34 (d, J
= 9.00 Hz, 2H); 13C NMR (62.90 MHz, CDCl3): δ 122.5, 125.3,
128.4, 128.7, 129.6, 130.2, 130.4, 134.3, 135.0, 145.5, 155.4,
163.1.
6602.
Montalbetti, C. A.; Falque, V. Tetrahedron. 2005, 61,
10827-10852.
Rajabi, F.; Raessi, M.; Arancon, R. A.; Saidi, M. R.;
Luque, R. Catal. Commun. 2015, 59, 122-126.
Dhimitruka, I.; SantaLucia, J. Org. Lett. 2006, 8, 47-50.
Nguyen, T. V.; Lyons, D. J. Chem. Commun. 2015, 51,
3131-3134.
Nakatsuji, H.; Morita, J. i.; Misaki, T.; Tanabe, Y. Adv.
Synth. Catal. 2006, 348, 2057-2062.
Bahrami, K.; Khodaei, M. M.; Targhan, H.; Arabi, M. S.
Tetrahedron Lett. 2013, 54, 5064-5068.
Aschenbrenner, E. M.; Weiss, C. K.; Landfester, K. Chem.
Eur. J. 2009, 15, 2434-2444.
Neises, B.; Steglich, W. Angew. Chem. Int. Ed. 1978, 17,
522-524.
Li, C.-J.; Chan, T.-H. Organic reactions in aqueous media;
Wiley, 1997.
Simon, M.-O.; Li, C.-J. Chem. Soc. Rev. 2012, 41, 1415-
1427.
Tamura, M.; Tonomura, T.; Shimizu, K.-i.; Satsuma, A.
Green Chem. 2012, 14, 984-991.
Bao, Y.-S.; Wang, L.; Jia, M.; Xu, A.; Agula, B.; Baiyin,
M.; Zhaorigetu, B. Green Chem. 2016, 18, 3808-3814.
Li, M.; Qiu, B.; Kong, X.-J.; Wen, L.-R. Org. Chem.
Front. 2015, 2, 1326-1333.
Ramazani, A.; Khoobi, M.; Sadri, F.; Tarasi, R.; Shafiee,
A.; Aghahosseini, H.; Joo, S. W. Appl. Organomet. Chem.
2017.
Tabatabaei Rezaei, S. J.; Khorramabadi, H.; Hesami, A.;
Ramazani, A.; Amani, V.; Ahmadi, R. Ind. Eng. Chem.
Res. 2017, 56, 12256-12266.
Tabatabaei Rezaei, S. J.; Mashhadi Malekzadeh, A.;
Poulaei, S.; Ramazani, A.; Khorramabadi, H. Appl.
Organomet. Chem.
Jafari, A.; Ramazani, A.; Ahankar, H.; Asiabi, P. A.; Sadri,
F.; Joo, S. W. Phosphorus Sulfur Silicon Relat Elem. 2016,
191, 373-380.
Ebadzadeh, B.; Ramazani, A.; Azizkhani, V.;
Aghahosseini, H.; Joo, S. Bulg. Chem. Commun. 2016, 48,
187-193.
Ramazani, A.; Ayoubi, S.; Ahmadi, Y.; Ahankar, H.;
Aghahosseini, H.; Woo Joo, S. Phosphorus Sulfur Silicon
Relat Elem. 2015, 190, 2307-2314.
5.
6.
7.
8.
9.
Phenyl benzoate (entry 3, table 2)6
10.
11.
12.
13.
14.
15.
16.
IR (KBr) 3341, 1731, 1619, 1486, 1198, 704 cm-1; 1H NMR
(250.13 MHz, CDCl3) δ 7.20-7.30 (m, 2H), 7.41-7.64 (m, 5H),
8.21 (d, J = 7.50 Hz, 2H).
Phenyl 4-bromobenzoate (entry 4, table 2)55
IR (KBr) 3097, 2924, 1785, 1722, 1586, 1396, 1244, 1067,
752 cm-1; 1H NMR (250.13 MHz, CDCl3) δ 7.18-7.34 (m, 2H),
7.41-7.47 (m, 1H), 7.55-7.70 (m, 2H), 7.99 (d, J = 8.25 Hz, 2H),
8.07 (d, J = 8.25 Hz, 2H).
p-tolyl benzoate (entry 5, table 2)56
IR (KBr) 2968, 2923, 1734, 1627, 1260, 1074, 730 cm-1.
4-nitrophenyl benzoate (entry 6, table 2)57
IR (KBr) 2921, 1736, 1521, 1347, 1266, 1058, 711 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 7.41-7.57 (m, 5H), 8.20 (d, J =
7.25 Hz, 2H), 8.33 (d, J = 8.00 Hz, 2H); 13C NMR (62.90 MHz,
CDCl3): δ 122.6, 125.2, 126.0, 126.4, 128.8, 130.3, 134.2, 157.3,
164.1.
17.
18.
19.
20.
21.
phenyl 2-naphthoate (entry 7, table 2)42
IR (KBr) 3033, 2923, 1742, 1615, 1591, 1402, 1205, 749 cm-1.
Phenyl 4-chlorobenzoate (entry 8, table 2)55
IR (KBr) 2925, 1732, 1591, 1486, 1247, 1092, 755 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 7.20-7.49 (m, 5H), 8.08 (d, J =
8.00 Hz, 2H), 8.14 (d, J = 7.50 Hz, 2H); 13C NMR (62.90 MHz,
CDCl3): δ 121.6, 126.0, 128.9, 129.4, 129.5, 131.5, 131.9, 142.1,
148.2, 163.4.
4-nitrophenyl 3-bromobenzoate (entry 9, table 2)58
22.
23.
Ramazani, A.; Rouhani, M.; Joo, S. W. Ultrason.
Sonochem. 2016, 28, 393-399.
HASANPOUR, Z.; Maleki, A.; Hosseini, M.;
Gorgannezhad, L.; Nejadshafiee, V.; Ramazani, A.;
Haririan, I.; Shafiee, A.; Khoobi, M. Turkish Journal of
Chemistry 2017, 41.
IR (KBr) 3085, 2924, 1743, 1522, 1346, 1219, 749 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 7.43 (bs, 2H), 7.80 (bs, 2H), 8.07
(m, 2H), 8.25 (bs, 2H); 13C NMR (62.90 MHz, CDCl3): δ = 122.3,
122.9, 125.1, 129.1, 130.5, 133.4, 137. 7, 152.9, 160.9.
4-nitrophenyl 4-tert-butylbenzoate (entry 10, table 2)59
IR (KBr) 2966, 1732, 1529, 1489, 1265, 1160, 727 cm-1; 1H
NMR (250.13 MHz, CDCl3) δ 1.37 (s. 9H), 7.42 (bs, 2 H), 7.56
(bs, 2H), 8.13 (bs, 2H), 8.33 (bs, 2H).
24.
25.
Jafari, A.; Ramazani, A.; Rouhani, M. Bulg. Chem.
Commun 2015, 47, 156-160.
Sadri, F.; Ramazani, A.; Massoudi, A.; Khoobi, M.; Tarasi,
R.; Shafiee, A.; Azizkhani, V.; Dolatyari, L.; Joo, S. W.
Green Chemistry Letters and Reviews 2014, 7, 257-264.
Vessally, E.; Ramazani, A.; Shabrendi, H.; Ghadimi, R.;
Rouhani, M. J. Chem. 2013, 2013.
Khoobi, M.; Ma’mani, L.; Rezazadeh, F.; Zareie, Z.;
Foroumadi, A.; Ramazani, A.; Shafiee, A. J. Mol. Catal.
A: Chem. 2012, 359, 74-80.
Ramazani, A.; Rezaei, A.; Mahyari, A. T.; Rouhani, M.;
Khoobi, M. Helv. Chim. Acta. 2010, 93, 2033-2036.
Ramazani, A.; Nasrabadi, F. Z.; Rezaei, A.; Rouhani, M.;
Ahankar, H.; Asiabi, P. A.; Joo, S. W.; Ślepokura, K.; Lis,
T. J. Chem. Sci. 2015, 127, 2269-2282.
4-nitrophenyl 4-bromobenzoate (entry 11, table 2)60
26.
27.
IR (KBr) 3030, 2963, 1735, 1521, 1348, 1258, 860, 744 cm-1.
Acknowledgements
This work was supported by the "Iran National science
Foundation: INSF".
28.
29.
Conflicts of interest The authors declare that they have no
conflict of interest
References and notes
30.
Pathak, G.; Das, D.; Rokhum, L. RSC Adv. 2016, 6, 93729-
93740.

8
Tetrahedron
ACCEPTED MANUSCRIPT
31.
Yedage, S. L.; D'silva, D. S.; Bhanage, B. M. RSC Adv.
2015, 5, 80441-80449.
32.
33.
34.
35.
36.
37.
Lenstra, D. C.; Rutjes, F. P.; Mecinović, J. Chem.
Commun. 2014, 50, 5763-5766.
Miller, S. A.; Leadbeater, N. E. RSC Adv. 2015, 5, 93248-
93251.
Lenstra, D. C.; Nguyen, D. T.; Mecinović, J. Tetrahedron.
2015, 71, 5547-5553.
Gosai, K. A.; Bhatt, A. S.; Belani, M. R.; Somani, R.;
Bajaj, H. 2017.
Kumar, A.; Akula, H. K.; Lakshman, M. K. Eur. J. Org.
Chem. 2010, 2010, 2709-2715.
Kim, S. E.; Hahm, H.; Kim, S.; Jang, W.; Jeon, B.; Kim,
Y.; Kim, M. Asian Journal of Organic Chemistry 2016, 5,
222-231.
38.
39.
40.
Nguyen, D. T.; Lenstra, D. C.; Mecinović, J. RSC Adv.
2015, 5, 77658-77661.
Fu, Z.; Lee, J.; Kang, B.; Hong, S. H. Org. Lett. 2012, 14,
6028-6031.
Nowrouzi, N.; Alizadeh, S. Z. Tetrahedron Lett. 2013, 54,
2412-2414.
41.
42.
Zhang, D.; Pan, C. Catal. Commun. 2012, 20, 41-45.
Zhang, L.; Zhang, G.; Zhang, M.; Cheng, J. J. Org. Chem.
2010, 75, 7472-7474.
43.
44.
45.
46.
47.
Petersen, T. B.; Khan, R.; Olofsson, B. Org. Lett. 2011, 13,
3462-3465.
Rouhi-Saadabad, H.; Akhlaghinia, B. Journal of the
Brazilian Chemical Society 2014, 25, 253-263.
Phakhodee, W.; Duangkamol, C.; Pattarawarapan, M.
Tetrahedron Lett. 2016, 57, 2087-2089.
Vanjari, R.; Guntreddi, T.; Singh, K. N. Green Chem.
2014, 16, 351-356.
Kumar Achar, T.; Mal, P. Adv. Synth. Catal. 2015, 357,
3977-3985.
48.
49.
Blackburn, L.; Taylor, R. J. Org. Lett. 2001, 3, 1637-1639.
Fearn, J.; DeWitt, J. J. Agric. Food. Chem. 1965, 13, 116-
117.
50.
NIST Chemistry Web Book, SRD 69, 2017, Available at
https://webbook.nist.gov/cgi/inchi?ID=U407347&Mask=2
000#Gas-Chrom.
51.
52.
53.
54.
55.
56.
57.
58.
59.
60.
Rossi, S. A.; Shimkin, K. W.; Xu, Q.; Mori-Quiroz, L. M.;
Watson, D. A. Org. Lett. 2013, 15, 2314-2317.
Pan, Y.; Zhang, J.; Li, H.; Wang, Y.-Z.; Li, W.-Y. Food
Anal Methods 2016, 9, 1686-1695.
Brown, D. S.; Marples, B. A.; Spilling, C. D. J. Chem. Soc.
Perkin Trans. 1 1988, 2033-2036.
Colthurst, M. Journal of the J. Chem. Soc. Perkin Trans. 2
1997, 1493-1498.
Bauerová, I.; Ludwig, M. Collection of Czechoslovak
Chem. Commun. 2000, 65, 1777-1790.
Shi, L.; Liu, H.; Huo, L.; Dang, Y.; Wang, Y.; Yang, B.;
Qiu, S.; Tan, H. Org Chem Front. 2018, 5, 1312-1319.
Luo, F.; Pan, C.; Cheng, J.; Chen, F. Tetrahedron. 2011,
67, 5878-5882.
Os’kina, I.; Vlasov, V. Russ. J. Org. Chem. 2008, 44, 561-
569.
Suh, J.; Hah, S. S.; Lee, S. H. Bioorg. Chem. 1997, 25, 63-
75.
Os’kina, I.; Vlasov, V. Russ. J. Org. Chem. 2006, 42, 865-
872.