Ce(III) immobilised on aminated epichlorohydrin-activated agarose matrix - "green" and efficient catalyst for transamidation of carboxamides

Article abstract of DOI:10.1515/chempap-2015-0168

The present study reports the preparation and characterisation of Ce(III) immobilised on an aminated epichlorohydrin-activated agarose matrix (CAEA) as a "green" catalyst. The catalyst was synthesised by the reaction of the epichlorohydrin-activated agarose matrix with ammonia solution, which was then treated with Ce(NO₃)₃ · 6H₂O. The catalyst (CAEA) was characterised by FT-IR, far IR, CHN, XRD, TGA, and ICP techniques. CAEA is shown to be an effective and reusable heterogeneous catalyst for the transamidation of carboxamides with amines under solventfree conditions. The catalyst was successfully applied to the synthesis of a wide range of aromatic and aliphatic amides. High efficiency, mild reaction conditions, easy work-up, simple separation and also reusability are important advantages of this catalyst.

Full text of DOI:10.1515/chempap-2015-0168

Chemical Papers 69 (11) 1421–1437 (2015)
DOI: 10.1515/chempap-2015-0168
ORIGINAL PAPER
Ce(III) immobilised on aminated epichlorohydrin-activated agarose
matrix – “green” and efficient catalyst for transamidation
of carboxamides
Zeinab Zarei, Batool Akhlaghinia*
Department of Chemistry, Faculty of Sciences, Ferdowsi University of Mashhad, P.O. Box 9177948974, Mashhad, Iran
Received 25 February 2015; Revised 31 May 2015; Accepted 10 June 2015
The present study reports the preparation and characterisation of Ce(III) immobilised on an
aminated epichlorohydrin-activated agarose matrix (CAEA) as a “green” catalyst. The catalyst
was synthesised by the reaction of the epichlorohydrin-activated agarose matrix with ammonia
solution, which was then treated with Ce(NO3)3 · 6H2O. The catalyst (CAEA) was characterised
by FT-IR, far IR, CHN, XRD, TGA, and ICP techniques. CAEA is shown to be an effective and
reusable heterogeneous catalyst for the transamidation of carboxamides with amines under solvent-
free conditions. The catalyst was successfully applied to the synthesis of a wide range of aromatic
and aliphatic amides. High efficiency, mild reaction conditions, easy work-up, simple separation and
also reusability are important advantages of this catalyst.
c
ꢀ 2015 Institute of Chemistry, Slovak Academy of Sciences
Keywords: cerium(III) immobilised on aminated epichlorohydrin-activated agarose matrix (CAEA),
carboxamides, transamidation, amines
Introduction
sic strength of the amide C—N bond. In comparison
with other acyl derivatives, amides are relatively in-
ert, hence transamidation may be performed under
forced reaction conditions, such as using stoichiomet-
ric amounts of reagents, high temperature (> 250◦C),
and long reaction times.
Out of the vast array of useful molecules, such as
industrially and biologically active compounds includ-
ing pharmaceuticals and agrochemicals, the amides
are prevalent. Hence, there has been increased in-
terest in the synthesis of carboxamides. Formation
of the amide linkage has usually been performed by
the reaction of amines with carboxylic acid deriva-
tives (chlorides, anhydrides, esters, or acids), alcohols
or aldehydes, as well as by the direct amidation of
alcohols with nitroarenes, the aminocarbonylation of
aryl halides and alkynes, the umpolung reaction of
amines with α-halo nitro alkanes, the Beckmann re-
arrangement, and the cross-coupling of formamides
with alkyl/aryl halides (Lundberg et al., 2014). To
make use of the low cost and the available starting
materials such as amines and amides, transamidation
is rapidly acquiring prominence. On the other hand,
transamidation is a fairly unusual reaction due to the
presence of an acidic N—H bond and, also, the intrin-
Transamidation in the presence of an enzyme with
a limited range of substrates and requiring long re-
action times has also been reported (Sergeeva et al.,
2000). To overcome these drawbacks, new homoge-
neous (Stephenson et al., 2009; Hoerter et al., 2008;
Rao et al., 2013; Zhang et al., 2012; Allen et al., 2012;
Atkinson et al., 2012; Becerra-Figueroa et al., 2014)
and heterogeneous catalysts (Tamura et al., 2012;
Wang et al., 2014a) including niobium oxide, cerium
dioxide, manganese(II) complex, iron(III), ionic liq-
uid, and sulphuric acid immobilised on silica gel have
recently been reported for the transamidation reac-
tion (Ghosh et al., 2014; Singh et al., 2014; Ayub Ali
et al., 2014; Fu et al., 2014; Rasheed et al., 2015).
The need to use a solvent, followed by difficulties in
*Corresponding author, e-mail: akhlaghinia@um.ac.ir
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Z. Zarei, B. Akhlaghinia/Chemical Papers 69 (11) 1421–1437 (2015)
Fig. 1. Preparation of Ce(III) immobilised on aminated epichlorohydrin-activated agarose matrix (CAEA).
the separation and recycling of the catalysts used are
disadvantages posed by homogeneous catalysts which
are overcome by using heterogeneous catalysts in the
transamidation reaction. Many of the protocols re-
ferred to above suffer from some disadvantages like
the use of expensive reagents, low yields, long reac-
tion times, water sensitivity, tedious work-ups, and
difficulty in the separation and the recovery of the cat-
alyst. In view of the increasing demands for organic
syntheses, the development of a new, simple, fast, ef-
ficient, and highly profitable catalytic transamidation
of carboxamides with amines under mild reaction con-
ditions remains highly desirable and in demand.
Following a recent study in the preparation and use
of heterogeneous catalysts in organic reactions (Razavi
& Akhlaghinia, 2015) and considering that agarose
(as a “green”, biodegradable and mechanically sta-
ble polymer (Wu et al., 2009; Rhim, 2012)) which is
widely found in nature has been an ideal candidate
for numerous practices in different areas of science, an-
other heterogenous catalyst based on agarose was syn-
thesised, characterised and applied in the transamida-
tion reaction.
Experimental
The purity determinations of the products were ac-
complished by thin layer chromatography (preparative
TLC were carried out using a Merck GF 254 silica gel
on a glass support). The melting points of products
were determined using an Electrothermal Type 9100
melting point apparatus. The FT-IR spectra were
recorded on an Avatar 370 FT-IR Thermo Nicolet
spectrometer (USA). The far IR spectra in the region
600–300 cm−1 were obtained using a Thermo Nico-
let NEXUS 870 FT-IR spectrometer (USA) equipped
with DTGS/polyethylene detector and a solid sub-
strate beam splitter. The spectra were collected with a
resolution of 4 cm−1. NMR spectra were recorded us-
ing Bruker Avance 600, Bruker Avance 500, Bruker
Avance 400, Bruker DRX 400, Varian Inova 400
and Varian mercury 300 spectrometers (Germany)
in CDCl3. Mass spectra 70 eV were recorded using
a CH7A Varianmat Bremem instrument (Germany).
Elemental analysis were performed using a Costech
4010 CHNS Elemental Analyser instrument (Italy).
Thermogravimetric analysis (TGA) was performed
on a Shimadzu Thermogavimetric Analyser (TG-50,
Switzerland) under an air atmosphere, with a heat-
ing rate of 10◦C min−1. Inductively-coupled plasma
(ICP) measurements were carried out on a Varian,
VISTA-PRO, CCD (Australia). Most of the products
were known compounds characterised by FT-IR, NMR
spectroscopy, mass spectrometry, and by comparing
their melting points with the melting points of known
compounds. The commercially available agarose was
washed as previously reported in the literature (Cao
et al., 1997).
Agarose is
a
linear polymer made up of
D-galactose and 3,6-anhydro-L-galactopyranose units.
This polysaccharide has properties such as flexibility,
non-toxicity, low cost, solubility in hot water, car-
rying freely available hydroxyl groups to form hy-
drogen bonds. In the present study, the washed and
suction-dried agarose was treated with epichlorohy-
drin in an alkaline solution incubated with shaking
at 40◦C. The resulting epoxy-activated agarose (I )
was then treated with ammonia solution. To obtain
Ce(III) immobilised on the aminated epichlorohydrin-
activated agarose matrix (CAEA) (III ), the aminated
epichlorohydrin-activated agarose matrix (II ) which
was used as the support and ligand for entrapment
of Ce(III) reacted with a solution of Ce(NO3)3 · 6H2O
(Fig. 1).
Matrices preparation
Washed and suction-dried agarose (2 g) was added
to 8 mL of distilled water and mixed with 10 mL of
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Table 1. Characterisation data of newly prepared amide (N-(3-ethoxypropyl)benzamide)
wi(calc.)/mass %
wi(found)/mass %
Isolated yield
M.p.
◦C
Entry
26
Compound
Mr
C
H
N
%
C12H17NO2
207
69.54
69.34
8.27
8.28
6.76
6.78
80
(oil)
Fig. 2. Transamidation of various amides with various amines in the presence of Ce(III) immobilised on aminated epichlorohydrin-
activated agarose matrix (CAEA).
NaOH (2 mol L−1) at ambient temperature. Epichro-
rohydrin (6 mL) was added to the resulting suspen-
sion and incubated at 40◦C with shaking. After 36 h,
the suspension was cooled to ambient temperature, fil-
tered, and washed with distilled water (4 × 15 mL)
to remove the surplus amount of epichlorohydrin. The
epoxy-activated agarose (I ) was dried at ambient tem-
perature (1.80 g, 76 %).
The epoxy-activated agarose (1.80 g) was added to
a concentrated ammonia solution (20 mL) incubated
at 40◦C with shaking. After 36 h, the resulting suspen-
sion was cooled to ambient temperature and filtered.
The resulting gel was washed with water (4 × 15 mL),
brine (3 × 5 mL), and water (4 × 15 mL) until the
filtrate was neutral. The aminated epichlorohydrin-
activated agarose matrix (II ) was dried at ambient
temperature.
0.117 g) in a round-bottom flask equipped with a
condenser under solvent-free conditions. The reac-
tion mixture was stirred (250 min−1) at 140◦C. The
progress of the reaction was monitored by TLC. Fol-
lowing the reaction, the reaction mixture was cooled
and the resultant mixture was submitted to silica gel
preparative TLC using ethyl acetate/hexane (1/1) as
eluent. N-Benzylbenzamide was obtained with a 95 %
yield (0.198 g). The spectral data of the compounds
are given in Tables 1 and 2.
The reaction mixture was centrifuged (1000 min−1
,
10 min) and washed several times with ethyl acetate
and acetone to remove all the organic compounds then
the precipitate was dried at ambient temperature.
Results and discussion
To a solution of Ce(NO3)3 · 6H2O (1 mmol, 0.43
g) in CH3OH (10 mL), aminated epichlorohydrin-
activated agarose matrix (II ) (0.37 g) was added. The
reaction mixture was refluxed for 24 h and then al-
lowed to cool to ambient temperature. The Ce(III)
immobilised on aminated epichlorohydrin-activated
agarose matrix CAEA (III ) (0.47 g, 70 %) as a pale
yellow precipitate was filtered, washed with CH3OH,
and dried at ambient temperature.
In continuing efforts to develop efficient and en-
vironmentally benign amide formation methods (Gh-
odsinia et al., 2013), it was envisioned that CAEA
as a “green” catalyst could effectively catalyse the
transamidation of various primary amides with var-
ious primary and secondary amines to afford the cor-
responding N-alkylamides with high yields at 140◦C
under solvent-free conditions (Fig. 2).
First, the transamidation reaction between benza-
mide and benzylamine was examined in the presence
of CAEA under various reaction conditions (Table 3).
There was hardly any transamidation without a cat-
alyst (Table 3, entry 1). In the presence of CAEA
(0.01 g, 1.61 mole %, of CAEA contains 0.002 g,
0.01 mmol, of Ce), the desired product was obtained
with a low yield (Table 3, entry 2). To increase the con-
General procedure for transamidation of ben-
zamide with benzylamine using CAEA and re-
covery of CAEA
CAEA (0.01 g) was added to a mixture of benza-
mide (1 mmol, 0.121 g) and benzylamine (1.1 mmol,
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Table 2. Characterisation data of prepared amides
Entry
Characterisation data
1
N-Benzylbenzamide
White solid
IR, ν˜/cm−1: 3291 (NH), 3063 (Ph), 1638 (C O)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 7.81 (d, 2H, JHH = 8 Hz, Ph), 7.55–7.51 (m, 1H, Ph), 7.46 (t, 2H, JHH = 8 Hz,
3
Ph), 7.39–7.29 (m, 5H, Ph), 6.47 (brs, 1H, NH) D2O exchangeable, 4.67 (d, 2H, JHH = 5.6 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 167.3 (CO), 138.2, 134.3, 131.3, 128.6, 128.4, 127.7, 127.4, 126.9, 43.9 (CH2)
MS, m/z (Ir/%): 211 (8) (M+), 106 (20) (PhCH2NH), 104 (100) (PhCO), 90 (70) (PhCH2), 76 (88) (Ph)
2
N-Benzyl-4-methoxybenzamide
Yellow solid
IR, ν˜/cm−1: 3266 (NH), 3051 (Ph), 1632 (C O)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 7.76 (d, 2H, JHH = 8 Hz, Ph), 7.36–7.30 (m, 5H, Ph), 6.92 (d, 2H, JHH = 8 Hz,
3
Ph), 6.91 (brs, 1H, NH) D2O exchangeable, 4.62 (d, 2H, JHH = 5.6 Hz, CH2), 3.84 (s, 3H, OCH3)
13C NMR (125 MHz, CDCl3), δ: 166.9 (CO), 162.1, 138.4, 128.7, 128.5, 127.7, 127.3, 126.6, 113.6, 55.2 (CH3), 43.8
(CH2)
MS, m/z (Ir/%): 241 (18) (M+), 134 (100) (M+ – PhCH2NH), 106 (71) (PhCH2NH), 91 (73) (PhCH2), 76 (75)
(Ph), 28 (64) (CO)
3
4
N-Benzyl-3,5-dimethylbenzamide
Colourless solid
IR, ν˜/cm−1: 3237 (NH), 3064 (Ph), 3019 (Ph), 1643 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.42 (s, 2H, Ph), 7.40–7.38 (m, 4H, Ph), 7.36–7.31 (m, 1H, Ph), 7.16 (s, 1H, Ph),
3
6.38 (brs, 1H, NH) D2O exchangeable, 4.67 (d, 2H, JHH = 5.6 Hz, CH2), 2.37 (s, 6H, 2Me)
13C NMR (125 MHz, CDCl3), δ: 167.8 (CO), 138.3, 134.4, 133.2, 128.8, 127.9, 127.6, 124.7, 44.1 (CH2), 21.2 (CH3)
MS, m/z (Ir/%): 239 (90) (M+), 133 (95) (M+ – PhCH2NH), 105 (85) (PhCH2NH), 91 (35) (PhCH2), 77 (20) (Ph)
N-Benzyl-4-methylbenzamide
Yellow solid
IR, ν˜/cm−1: 3310 (NH), 3058 (Ph), 3027 (Ph), 1640 (C O)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 7.68 (d, 2H, JHH = 8 Hz, Ph), 7.37–7.30 (m, 5H, Ph), 7.23 (d, 2H, JHH = 8 Hz,
3
Ph), 6.42 (brs, 1H, NH) D2O exchangeable, 4.63 (d, 2H, JHH = 5.6 Hz, CH2), 2.39 (s, 3H, Me)
13C NMR (125 MHz, CDCl3), δ: 167.2 (CO), 141.8, 138.3, 131.5, 129.1, 128.6, 127.8, 127.4, 126.9, 44.0 (CH2), 21.3
(CH3)
MS, m/z (Ir/%): 211 (8) (M+), 105 (100) (PhCH2NH), 91 (63) (PhCH2), 77 (92) (Ph), 28 (87) (CO)
5
6
7
N-Benzyl-4-bromobenzamide
White solid
IR, ν˜/cm−1: 3312 (NH), 3055 (Ph), 3022 (Ph), 1640 (C O)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 7.64 (d, 2H, JHH = 8.8 Hz, Ph), 7.53 (d, 2H, JHH = 8.8 Hz, Ph), 7.35–7.30 (m,
3
5H, Ph), 6.70 (brs, 1H, NH) D2O exchangeable, 4.60 (d, 2H, JHH = 5.6 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 166.3 (CO), 137.9, 137.7, 132.7, 128.7, 128.4, 127.8, 127.6, 44.1 (CH2)
MS, m/z (Ir/%): 210 (5) (M+ – Br), 119 (98) (PhCONH), 106 (70) (PhCH2NH), 91 (85) (PhCH2), 77 (62) (Ph),
28 (80) (CO)
N-Benzyl-2-chlorobenzamide
Yellow solid
IR, ν˜/cm−1: 3257 (NH), 3087 (Ph), 3027 (Ph), 2917 (CH2), 1637 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.71–7.69 (m, 4H, Ph), 7.38–7.31 (m, 5H, Ph), 6.49 (brs, 1H, NH) D2O exchangeable,
3
4.68 (d, 2H, JHH= 5.6 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 167.3 (CO), 135.5, 134.2, 133.5, 131.5, 130.1, 129.4, 128.8, 128.5, 127.0, 126.9, 41.9
(CH2)
MS, m/z (Ir/%): 246 (18) (M+), 208 (97) (M+ – Cl), 138 (100) (M+ – PhCH2NH), 91 (44) (PhCH2), 28 (64) (CO)
N-Benzyl-3,4-dichlorobenzamide
Light orange solid
IR, ν˜/cm−1: 3320 (NH), 3080 (Ph), 3027 (Ph), 2921 (CH2), 2851 (CH2), 1643 (C O)
—
—
4
3
1H NMR (400 MHz, CDCl3), δ: 7.91 (d, 1H, JHH = 1.6 Hz, Ph), 7.64–7.62 (m, 1H, Ph), 7.52 (d, 1H, JHH = 8 Hz,
3
Ph), 7.41–7.29 (m, 5H, Ph), 6.47 (brs, 1H, NH) D2O exchangeable, 4.64 (d, 2H, JHH= 5.6 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 165.2 (CO), 137.6, 135.9, 134.1, 133.0, 130.6, 129.1, 128.8, 127.8, 127.7, 126.1, 44.3
(CH2)
MS, m/z (Ir/%): 279 (35) (M+), 172 (100) (M+ – PhCH2NH), 144 (95) (M+ – PhCH2NHCO), 106 (98) (PhCH2NH),
90 (89) (PhCH2), 77 (70) (Ph)
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Table 2. (continued)
Entry
Characterisation data
8
N-Benzyl-3-nitrobenzamide
Yellow solid
IR, ν˜/cm−1: 3295 (NH), 3084 (Ph), 3031(Ph), 2917 (CH2), 1642 (C O), 1351 (NO2)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 8.61 (s, 1H, Ph), 8.36 (d, 1H, JHH = 6.4 Hz, Ph), 8.18 (d, 2H, JHH = 8 Hz, Ph),
3
7.65 (d, 2H, JHH = 8 Hz, Ph), 7.37–7.26 (m, 3H, Ph), 6.69 (brs, 1H, NH) D2O exchangeable, 4.67 (s, 2H, CH2)
13C NMR (125 MHz, CDCl3), δ: 166.0 (CO), 137.8, 136.2, 134.3, 130.1, 130.0, 128.6, 127.7, 127.5, 125.5, 122.6, 44.0
(CH2)
MS, m/z (Ir/%): 258 (12) (M+), 207 (20) (M+ – NO2), 149 (92) (M+ – PhCH2NH), 104 (92) (PhCH2NH), 91 (63)
(PhCH2), 77 (67) (Ph), 29 (72) (CO)
9
N-Benzyl-4-nitrobenzamide
Yellow solid
IR, ν˜/cm−1: 3279 (NH), 3031(Ph), 1630 (C O), 1536 (NO2), 1346 (NO2)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 8.26 (d, 2H, JHH = 8.8 Hz, Ph), 7.94 (d, 2H, JHH = 8.8 Hz, Ph), 7.38–7.34 (m,
3
5H, Ph), 7.26 (brs, 1H, NH) D2O exchangeable, 4.65 (d, 2H, JHH= 5.6 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 165.4 (CO), 149.5, 139.8, 137.4, 128.8, 128.2, 127.8, 123.7, 44.3 (CH2)
MS, m/z (Ir/%): 256 (12) (M+), 207 (20) (M+ – NO2), 149 (92) (M+ – PhCH2NH), 104 (92) (PhCH2NH), 91 (75)
(PhCH2), 77 (78) (Ph), 29 (72) (CO)
10
N-Benzylisonicotinamide
White solid
IR, ν˜/cm−1: 3313 (NH), 3060 (Ph), 3027 (Ph), 2880 (CH2), 1648 (C O)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 8.91 (d, 2H, JHH= 4.4 Hz, pyridine ring), 7.77 (d, 2H, JHH= 4.4 Hz, pyridine
3
ring), 7.45–7.29 (m, 5H, Ph), 6.95 (brs, 1H, NH) D2O exchangeable, 4.64 (d, 2H, JHH= 5.2 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 165.6 (CO), 150.4, 141.3, 137.5, 128.9, 128.0, 127.7, 122.0, 44.3 (CH2)
MS, m/z (Ir/%): 212 (48) (M+), 106 (27) (PhCH2NH), 78 (13) (M+ – PhCH2NHCO), 57 (27) (CH2NHCO), 29
(94) (CO)
11
N-Benzylcinnamamide
White solid
IR, ν˜/cm−1: 3280 (NH), 3080 (Ph), 3031(Ph), 2917 (CH2), 1613 (C O)
—
—
3
3,4
1H NMR (400 MHz, CDCl3), δ: 7.63 (d, 1H, JHH = 15.6 Hz, CH=), 7.43 (dd, 2H,
J
HH
= 6.4 Hz, 2.8 Hz, Ph),
3
7.35–7.32 (m, 8H, Ph), 6.52 (brs, 1H, NH) D2O exchangeable, 6.45 (d, 1H, JHH = 15.6 Hz, CH=), 4.50 (d, 2H,
3JHH = 5.8 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 166.1 (CO), 141.3, 138.4, 134.0, 128.9, 128.1, 127.9, 127.6, 120.8, 43.9 (CH2)
MS, m/z (Ir/%): 237 (40) (M+), 130 (100) (M+ – PhCH2NH), 106 (95) (PhCH2NH), 91 (72) (PhCH2), 77 (95)
(Ph), 28 (75) (CO)
12
(E)-N-Benzyl-3-(4-chlorophenyl)acrylamide
White solid
IR, ν˜/cm−1: 3288 (NH), 3064 (Ph), 2929 (CH2), 1622 (C O)
—
—
3
1H NMR (400 MHz, CDCl3), δ: 7.65 (d, 1H, JHH = 15.6 Hz, CH=), 7.42–7.40 (m, 4H, Ph), 7.38–7.29 (m, 5H, Ph),
3
3
6.49 (d, 1H, JHH = 15.6 Hz, CH=), 6.24 (brs, 1H, NH) D2O exchangeable, 4.60 (d, 2H, JHH = 4.4 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 165.6 (CO), 140.1, 138.1, 135.6, 133.3, 129.1, 129.0, 128.8, 127.9, 127.6, 121.0, 43.9
(CH2)
MS, m/z (Ir/%): 273 (15) (M+ + 2), 271 (45) (M+), 164 (98) (M+ – PhCH2NH), 106 (85) (PhCH2NH), 90 (25)
(PhCH2)
13
(E)-N-Benzyl-3-(3-nitrophenyl)acrylamide
Yellow solid
IR, ν˜/cm−1: 3223 (NH), 3069 (Ph), 1656 (C O), 1530 (NO2), 1347 (NO2)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 8.31 (s, 1H, Ph), 8.15 (d, 1H, JHH = 8.2 Hz, Ph), 7.71 (d, 1H, JHH = 7.7 Hz,
3
3
Ph), 7.66 (d, 1H, JHH = 15.6 Hz, CH=), 7.52 (t, 1H, JHH = 8.2 Hz, Ph), 7.34–7.24 (m, 5H, Ph), 6.60 (d, 1H,
3JHH = 15.6 Hz, CH=), 6.48 (brs, 1H, NH) D2O exchangeable, 4.57 (d, 2H, JHH = 5.8 Hz, CH2)
3
13C NMR (125 MHz, CDCl3), δ: 165.1 (CO), 148.7, 138.8, 138.0, 136.7, 134.1, 130.0, 128.9, 128.0, 127.8, 124.1,
123.7, 121.8, 44.8 (CH2)
MS, m/z (Ir/%): 282 (5) (M+), 175 (25) (M+ – PhCH2NH), 160 (60) (M+ – PhNO2), 106 (65) (PhCH2NH), 91
(50) (PhCH2), 77 (22) (Ph), 28 (100) (CO)
14
N-Benzyl-2-(2,4-dichlorophenoxy)acetamide
Yellow–brown oily liquid
IR, ν˜/cm−1: 3287 (NH), 3096 (Ph), 3035 (Ph), 2933 (CH2), 2855 (CH2), 1661 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.39–7.34 (m, 5H, Ph), 7.23–7.21 (m, 1H, Ph), 7.10 (brs, 1H, NH) D2O exchangeable,
6.83–6.85 (m, 2H, Ph), 4.57–4.58 (m, 4H, CH2)
MS, m/z (Ir/%): 309 (15) (M+), 174 (8) (M+ – PhCH2NHCO), 147 (100) (PhCH2NHCOCH2), 107 (47)
(PhCH2NH), 91 (99) (PhCH2), 28 (68) (CO)
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Table 2. (continued)
Entry
Characterisation data
15
N-Benzyl-2,2-diphenylacetamide
Yellow solid
IR, ν˜/cm−1: 3311 (NH), 3064 (Ph), 3031(Ph), 2933 (CH2), 1641 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.33–7.31 (m, 5H, Ph), 7.28–7.20 (m, 10H, 2Ph), 5.91 (brs, 1H, NH) D2O exchange-
3
able, 4.97 (s, 1H, CH), 4.50 (d, 2H, JHH= 5.6 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 171.8 (CO), 139.4, 138.1, 128.9, 128.8, 128.7, 127.7, 127.5, 127.3, 59.2 (CH), 43.8
(CH2)
MS, m/z (Ir/%): 301 (88) (M+), 167 (100) (CH(Ph)2), 91 (52) (PhCH2)
16
N-Benzyloleamide
Light yellow oil
IR, ν˜/cm−1: 3302 (NH), 2921 (CH2), 2850 (CH2), 1640 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.33–7.28 (m, 5H, Ph), 5.76 (brs, 1H, NH) D2O exchangeable, 5.34 (s, 2H, CH2),
3
3
4.44 (d, 2H, JHH= 5.2 Hz, CH2), 2.22–2.18 (d, 2H, JHH = 15.2 Hz, CH=), 2.01 (s, 3H), 1.66 (s, 4H), 1.29–1.27
(m, 14H), 0.89–0.87 (m, 8H)
MS, m/z (Ir/%): 371 (11) (M+), 162 (23) (PhCH2NHCO(CH2)2), 149 (83) (PhCH2NHCOCH2), 106 (76)
(PhCH2NH), 91 (100) (PhCH2), 43 (65) (CONH), 28 (52) (CO)
17
N-(4-Methoxybenzyl)benzamide
White solid
IR, ν˜/cm−1: 3245 (NH), 3080 (Ph), 2929 (CH2), 1633 (C O)
—
—
3
3
1H NMR (400 MHz, CDCl3), δ: 7.79–7.77 (d, 2H, JHH= 8 Hz, Ph), 7.50–7.48 (d, 2H, JHH = 8 Hz, Ph), 7.44–7.43
3
3
(m, 1H, Ph), 7.30–7.28 (d, 2H, JHH= 8 Hz, Ph), 6.90–6.88 (d, 2H, JHH= 8 Hz, Ph), 6.35 (brs, 1H, NH) D2O
exchangeable, 4.59 (s, 2H, CH2), 3.81 (s, 3H, OCH3)
13C NMR (125 MHz, CDCl3), δ: 167.2 (CO), 159.0, 134.4, 131.3, 130.3, 129.1, 128.4, 126.9, 114.0, 55.2 (C), 43.5
(CH2)
MS, m/z (Ir/%): 241 (5) (M+), 135 (70) (M+ – PhCO), 120 (80) (PhCONH), 104 (100) (PhCH2NH), 76 (82) (Ph),
28 (97) (CO)
18
N-(2-Chlorobenzyl)benzamide
Light yellow solid
IR, ν˜/cm−1: 3287 (NH), 3062 (Ph), 3023 (Ph), 1632 (C O)
—
—
3
1H NMR (400 MHz, CDCl3), δ: 7.78 (d, 2H, JHH = 8 Hz, Ph), 7.51–7.45 (m, 1H, Ph), 7.41–7.36 (m, 4H, Ph),
3
7.26–7.22 (m, 2H, Ph), 6.77 (brs, 1H, NH) D2O exchangeable, 4.70 (d, 2H, JHH = 5.6 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 167.4 (CO), 131.6, 130.3, 129.5, 129.0, 128.6, 127.1, 127.0, 41.0 (CH2)
MS, m/z (Ir/%): 225 (8) (M+), 209 (32) (M+ – Cl), 105 (100) (PhCO), 91 (64) (PhCH2), 77 (91) (Ph), 28 (86)
(CO)
19
N-Phenylbenzamide
Colourless solid
IR, ν˜/cm−1: 3345 (NH), 3056 (Ph), 1655 (C O)
—
—
3
1H NMR (400 MHz, CDCl3), δ: 8.00 (brs, 1H, NH) D2O exchangeable, 7.87 (d, 2H, JHH = 8 Hz, Ph), 7.65 (d, 2H,
3JHH = 8 Hz, Ph), 7.55–7.53 (m, 1H, Ph), 7.47 (t, 2H, JHH = 8 Hz, Ph), 7.37 (t, 2H, JHH = 8 Hz, Ph), 7.16 (t,
3
3
3
1H, JHH = 8 Hz, Ph)
13C NMR (125 MHz, CDCl3), δ: 165.8 (CO), 137.9, 135.0, 131.7, 129.0, 128.7, 127.0, 124.5, 120.2
MS, m/z (Ir/%): 197 (11) (M+), 105 (100) (PhCO), 92 (14) (PhNH), 29 (35) (CO)
20
21
N-(4-Methoxyphenyl)benzamide
Colourless solid
IR, ν˜/cm−1: 3329 (NH), 2955 (Ph), 1642 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.91 (brs, 1H, NH) D2O exchangeable, 7.87 (d, 2H, JHH = 8 Hz, Ph), 7.56–7.52
3
3
(m, 3H, Ph), 7.48–7.45 (m, 2H, Ph), 6.89 (d, 2H, JHH = 8 Hz, Ph), 3.81 (s, 3H, OMe)
13C NMR (125 MHz, CDCl3), δ: 165.6 (CO), 156.6, 135.0, 131.6, 131.0, 128.6, 126.9, 122.1, 114.2, 55.4 (CH3)
MS, m/z (Ir/%): 227 (13) (M+), 121 (54) (M+ – PhCO), 104 (100) (PhCO), 76 (82) (Ph), 28 (66) (CO)
N-(3,4-Dimethylphenyl)benzamide
Colourless solid
IR, ν˜/cm−1: 3307 (NH), 3056 (Ph), 1648 (C O)
—
—
3
1H NMR (400 MHz, CDCl3), δ: 8.23 (brs, 1H, NH) D2O exchangeable, 7.86 (d, 2H, JHH = 8 Hz, Ph), 7.51–7.48
3
(m, 1H, Ph), 7.45 (s, 1H, Ph), 7.41–7.38 (m, 3H, Ph), 7.07 (d, 1H, JHH = 8 Hz, Ph), 2.24 (s, 3H, Me), 2.22 (s, 3H,
Me)
13C NMR (125 MHz, CDCl3), δ: 165.8 (CO), 137.0, 135.6, 134.9, 132.7, 131.4, 129.8, 128.4, 127.0, 121.8, 118.0, 19.6
(CH3), 19.0 (CH3)
MS, m/z (Ir/%): 225 (21) (M+), 121 (7) (M+ – PhCO), 105 (100) (PhCO), 77 (94) (Ph), 29 (68) (CO)
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Table 2. (continued)
Entry
Characterisation data
22
N-(p-Tolyl)benzamide
Colourless solid
IR, ν˜/cm−1: 3310 (NH), 3072 (Ph), 1647 (C O)
—
—
3
1H NMR (400 MHz, CDCl3), δ: 7.87 (d, 2H, JHH = 8 Hz, Ph), 7.70 (brs, 1H, NH) D2O exchangeable, 7.56–7.48
3
(m, 5H, Ph), 7.18 (d, 2H, JHH = 8 Hz, Ph), 2.34 (s, 3H, Me)
13C NMR (125 MHz, CDCl3), δ: 165.8 (CO), 135.3, 134.9, 134.0, 131.5, 129.4, 128.5, 127.0, 120.4, 20.8 (CH3)
MS, m/z (Ir/%): 211 (8) (M+), 106 (20) (M+ – PhCO), 104 (100) (PhCO), 90 (70) (PhCH3), 76 (90) (Ph)
23
24
N-(Furan-2-ylmethyl)benzamide
Light yellow solid
IR, ν˜/cm−1: 3301 (NH), 3080 (Ph), 1641 (C O)
—
—
3
1H NMR (400 MHz, CDCl3), δ: 7.79 (d, 2H, JHH = 8.5 Hz, Ph), 7.50–7.49 (m, 1H, CH, furan ring), 7.43–7.26 (m,
3
3H, Ph), 6.47 (brs, 1H, NH) D2O exchangeable, 6.33 (m, 2H, furan ring), 4.64 (d, 2H, JHH = 6 Hz, CH2)
13C NMR (125 MHz, CDCl3), δ: 167.3 (CO), 151.1, 142.2, 134.1, 131.5, 128.5, 127.0, 110.5, 107.6, 36.9 (CH2)
MS, m/z (Ir/%): 201 (29) (M+), 105 (100) (PhCO), 80 (27) (M+ – PhCONH), 77 (95) (Ph), 28 (62) (CO)
N-Cyclohexylbenzamide
White solid
IR, ν˜/cm−1: 3241 (NH), 3084 (Ph), 1627 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.69–7.42 (m, 2H, Ph), 7.42–7.30 (m, 3H, Ph), 6.03 (brs, 1H, NH) D2O exchangeable,
3.91–3.84 (m, 1H, CH), 1.95–1.92 (m, 2H), 1.68–1.55 (m, 3H), 1.40–1.28 (m, 2H), 1.22–1.09 (m, 3H)
13C NMR (125 MHz, CDCl3), δ: 169.2 (CO), 137.7, 133.8, 131.1, 129.4, 51.3 (CH2), 35.8 (CH2), 28.2 (CH2), 27.5
(CH2)
MS, m/z (Ir/%): 203 (42) (M+), 121 (98) (PhCONH), 104 (100) (PhCO), 77 (82) (Ph), 28 (89) (CO)
25
N-Butylbenzamide
Light yellow solid
IR, ν˜/cm−1: 3324 (NH), 3060 (Ph), 2959 (CH2), 2930 (CH2), 2872 (CH2), 1640 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.76 (d, 2H, JHH= 8 Hz, Ph), 7.48 (d, 1H, JHH= 8 Hz, Ph), 7.44–7.43 (m, 2H,
Ph), 6.17 (brs, 1H, NH) D2O exchangeable, 3.49–3.44 (m, 2H, CH2), 1.62–1.57 (m, 2H, CH2), 1.44–1.41 (m, 2H,
CH2), 0.98–0.94 (m, 3H, Me)
3
3
13C NMR (125 MHz, CDCl3), δ: 167.5 (CO), 134.8, 131.1, 128.4, 126.8, 39.7 (CH2), 31.6 (CH2), 20.1 (CH2), 13.7
(CH3)
MS, m/z (Ir/%): 177 (10) (M+), 105 (100) (PhCO), 72 (88) ((CH2)4NH), 57 (70) (CONHCH2), 28 (70) (CO)
26
N-(3-Ethoxypropyl)benzamide
Red wine oil
IR, ν˜/cm−1: 3311 (NH), 3068 (Ph), 2955 (CH2), 2925 (CH2), 2868 (CH2), 1643 (C O)
—
—
3
1H NMR (400 MHz, CDCl3), δ: 7.77 (d, 2H, JHH= 8 Hz, Ph), 7.46–7.21 (m, 3H, Ph), 7.21 (brs, 1H, NH) D2O
exchangeable, 3.60–3.49 (m, 4H, 2CH2), 3.42–3.41 (m, 2H, CH2), 1.82–1.81 (m, 2H, CH2), 1.24–1.21 (m, 3H, CH3)
13C NMR (125 MHz, CDCl3), δ: 167.1 (CO), 134.7, 131.1, 128.4, 126.8, 70.4 (CH2), 66.5 (CH2), 39.3 (CH2), 28.8
(CH2), 15.3 (CH3)
MS, m/z (Ir/%): 207 (15) (M+), 178 (5) (M+ – CH2CH3), 162 (20) (M+ – OCH2CH3), 106 (75) (PhCO), 60 (25)
(CH2OCH2CH3), 28 (58) (CO)
Composition for C12H17NO2, wi/mass %: C 69.54, H 8.27, N 6.76 (calc.); C 69.34, H 8.28, N 6.78 (found)
27
Phenyl(piperidin-1-yl)methanone
Colourless oil
IR, ν˜/cm−1: 3058 (Ph), 2998 (CH2), 2937 (CH2), 2855 (CH2), 1629 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.38–7.37 (m, 5H, Ph), 3.80 (s, 2H, CH2), 3.68 (s, 2H, CH2), 1.66–1.40 (m, 6H,
3CH2)
13C NMR (125 MHz, CDCl3), δ: 170.3 (CO), 136.6, 129.4, 128.4, 126.8, 48.8 (CH2), 43.1 (CH2), 25.7 (CH2), 24.6
(CH2), 22.6 (CH2)
MS, m/z (Ir/%): 189 (15) (M+), 105 (100) (PhCO), 86 (70) (M+ – PhCO), 77 (75) (Ph), 28 (72) (CO)
28
Morpholino(phenyl)methanone
Yellow oil
IR, ν˜/cm−1: 3080 (Ph), 2913 (CH2), 2858 (CH2), 1626 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.39–7.26 (m, 5H, Ph), 3.72 (s, 2H, CH2), 3.35 (s, 2H, CH2), 1.68 (s, 2H, CH2),
1.52–1.43 (m, 2H, CH2)
13C NMR (125 MHz, CDCl3), δ: 170.5 (CO), 135.3, 129.9, 128.6, 128.6, 128.5, 127.1, 127.1, 127.1, 66.9 (CH2), 48.2
(CH2), 42.5 (CH2)
MS, m/z (Ir/%): 191 (35) (M+), 105 (100) (PhCO), 86 (72) (M+ – PhCO), 77 (75) (Ph), 28 (72) (CO)
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Table 2. (continued)
Entry
Characterisation data
29
Phenyl(pyrrolidin-1-yl)methanone
Colourless oil
IR, ν˜/cm−1: 3027 (Ph), 2935 (CH2), 2854 (CH2), 1633 (C O)
—
—
1H NMR (400 MHz, CDCl3), δ: 7.52–7.51 (m, 2H, Ph), 7.40–7.39 (m, 3H, Ph), 3.65 (m, 2H, CH2), 3.42 (m, 2H,
CH2), 1.98–1.93 (m, 2H, CH2), 1.90–1.84 (m, 2H, CH2)
13C NMR (125 MHz, CDCl3), δ: 170.0 (CO), 139.0, 129.7, 128.2, 127.0, 49.6 (CH2), 46.1 (CH2), 26.4 (CH2), 24.4
(CH2)
MS, m/z (Ir/%): 175 (18) (M+), 104 (100) (PhCO), 70 (68) (M+ – PhCO), 28 (100) (CO)
30
N-Benzylhexanamide
White solid
IR, ν˜/cm−1: 3264 (NH), 3060 (Ph), 3027 (Ph), 2917 (CH2), 1615 (C O)
—
—
3
1H NMR (400 MHz, CDCl3), δ: 7.37–7.25 (m, 5H, Ph), 5.69 (brs, 1H, NH) D2O exchangeable, 4.45 (d, 2H, JHH
3
3
= 5.7 Hz, CH2), 2.21 (t, 2H, JHH = 7.4 Hz, CH2), 1.66 (p, 2H, JHH = 7.5 Hz, CH2), 1.37–1.24 (m, 4H, CH2),
3
0.89 (t, 3H, JHH = 6.8 Hz, CH3)
13C NMR (125 MHz, CDCl3), δ: 173.2 (CO), 138.5, 128.8, 127.9, 127.6, 43.6 (CH2), 36.9 (CH2), 31.6 (CH2), 25.6
(CH2), 22.5 (CH2), 14.1 (CH3)
MS, m/z (Ir/%): 205 (6) (M+), 107 (89) (PhCH2NH), 92 (88) (PhCH2), 45 (89) (CONH), 29 (100) (CO)
Table 3. Optimisation of conditions for CAEA-catalysed transamidation of benzamide with benzylamine
Catalyst content
mole %
Temperature
◦C
Time
h
Isolated yield
%
Entry
Molar ratio
benzamide/benzylamine
Solvent
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20a
21b
22c
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.1
1/1.0
1/1.2
1/1.5
1/1.1
1/1.1
1/1.1
0
–
–
–
–
–
–
–
–
–
–
–
–
100
100
110
120
130
140
150
160
140
140
140
140
140
140
140
140
140
140
140
140
140
140
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
5
trace
10
30
50
75
95
60
45
75
50
80
85
0
20
60
85
90
80
60
30
50
50
1.61
1.61
1.61
1.61
1.61
1.61
1.61
1.28
0.80
2.57
3.22
1.61
1.61
1.61
1.61
1.61
1.61
1.61
2.60
1.56
1.56
H2O
H2O/ethylenglycol
ethylenglycol
toluene
–
–
–
–
–
–
a) Reaction was performed in the presence of (II); b) reaction was performed in the presence of Ce(NO3)3 · 6H2O; c) reaction was
performed in the presence of a mixture of Ce(NO3)3 · 6H2O (1.56 mole %) and ethanolamine (2.50 mole %).
version of transamidation, the reaction was performed
at different temperatures and higher conversions were
found at 140◦C. Performing the transamidation reac-
tion at higher temperatures concomitant with the for-
mation of by-products and lower temperatures leads
to formation of the desired product in longer reaction
times (Table 3, entries 2–8). In order to introduce the
same catalyst equivalents in different experiments, the
exact amount of the catalyst used was determined on
the basis of the loading value in each experiment. The
effect of different amounts of catalyst was studied on
the reaction rate (Table 3, entries 9–12). The desired
product was obtained with a high yield in the pres-
ence of 0.01 g (1.61 mole % of CAEA contains 0.002 g,
0.01 mmol, of Ce) of the catalyst. By performing the
reaction in the presence of 0.008 g (1.28 mole % of
CAEA contains 0.001 g, 0.01 mmol, of Ce) and 0.005 g
(0.80 mole % of CAEA contains 0.001 g, 0.007 mmol,
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Fig. 3. Proposed mechanism of transamidation of carboxamides in the presence of Ce(III) immobilised on aminated
epichlorohydrin-activated agarose matrix (CAEA).
of Ce) of the catalyst, the transamidation reaction
proceeded with only 75 % and 50 % yields after 5 h
(Table 3, entries 9 and 10). When the transamida-
tion reaction was carried out in the presence of addi-
tional amounts of the catalyst (0.01 g, 2.57 mole %,
of CAEA and 0.02 g, 3.22 mole %, of CAEA), the for-
mation of by-products reduced the conversion of reac-
tants to the desired product (Table 3, entries 11 and
12). In order to investigate the effect of different sol-
vents, the transamidation reaction of benzamide with
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benzylamine was carried out in polar solvents such
as: H2O, H2O/ethylene glycol (ϕr = 50 : 50), ethy-
lene glycol, and toluene (Table 3, entries 13–16). It
was found that the best conversion was obtained un-
der solvent-free conditions. By considering the results
from Table 3, applying a 1/1.1 molar ratio of benza-
mide/benzylamine produced N-benzylbenzamide with
a high yield without the formation of any by-products
(Table 3, compare entry 6 with entries 17–19). In or-
der to ascertain the major role played by CAEA as a
catalyst in the transamidation reaction and by apply-
ing the optimal reaction conditions, two further reac-
tions between benzamide and benzylamine were per-
formed. The first reaction was performed in the pres-
ence of aminated epichlorohydrin-activated agarose
matrix (II ) (0.01 g, 2.60 mole %) and the second was
carried out in the presence of Ce(NO3)3 ·6H2O. After
an appropriate reaction time (5 h), the extent of for-
mer reaction was 30 % and that of the latter one, by
applying 0.006 g, 1.56 mole %, of Ce(NO3)3 · 6H2O,
was 50 % with the formation of by-products (Table 3,
entries 20 and 21). The result from entry 20 shows
the catalytic activity of the aminated epichlorohydrin-
activated agarose matrix (II ) in the transamidation
reaction. This activity which preceded the transami-
dation reaction to some extent is the result of the for-
mation of hydrogen bonding between OH and NH2
of (II ) with carboxamide and amine in the reaction
mixture (see Fig. 3). To better understand the cat-
alytic activity of CAEA, the reaction was carried out
with a mixture of Ce(NO3)3 ·6H2O (1.56 mole %) and
ethanolamine (2.50 mole %). The desired product was
obtained with a 50 % yield after 5 h (Table 3, entry
22). This result leads to the conclusion that the immo-
bilisation of Ce(III) on an aminated epichlorohydrin-
activated agarose matrix (II) improved the catalytic
activity of Ce(III) in the transamidation reaction.
The transamidation reaction of different carbox-
amides with various aliphatic and aromatic amines
was studied on the basis of the optimised reaction
conditions, 0.01 g of the catalyst (containing 0.002 g,
0.01 mmol, of Ce) at 140◦C under solvent-free con-
ditions and to show the general application and ver-
satility of the present protocol. The results are sum-
marised in Table 4. Because of the importance of sec-
ondary amides in synthetic and biological polymers,
attention was focused on the synthesis of this class
of substrates resulting from the current transamida-
tiom reaction. The transamidation reactions of ben-
zamide and substituted benzamide were performed
smoothly with benzylamine to deliver the correspond-
ing secondary amides (Table 4, entries 1–9). Benza-
mides substituted with electron-withdrawing groups
at para-position considerably enhanced the product
yields (Table 4, entries 8 and 9). Halogen-substituted
benzamide also performed well in the reactions (Ta-
ble 4, entries 5–7). As regards the steric effects, ben-
zamides having ortho substituent afforded the desired
products with longer reaction times (compare entries 6
and 7). Comparatively, electron-donating substituents
prolonged the transamidation reactions of benzamides
(Table 4, entries 2–4).
The transamidation of isonicotinamide with ben-
zylamine afforded its N-benzylated analogue, provid-
ing convenient access to this class of pharmaceuti-
cally important compounds (Table 4, entry 10). From
the results obtained from Table 4 and on the ba-
sis of the proposed mechanism in Fig. 3, the elec-
trophilicity of the carbonyl group of amides is thought
to play an essential role in the reaction rate. The
present system was further examined for the transami-
dation of aliphatic amides (Table 4, entries 11–16 and
30). The transamidation of aliphatic amides with ben-
zyl amine afforded their N-substituted analogues with
good yields but over a long period of time. The gener-
ality of this CAEA-catalysed transamidation was fur-
ther demonstrated in the reaction of benzamide with
a variety of aliphatic (primary and secondary) and
aromatic amines (Table 4, entries 19–29). Electron-
releasing groups on substituted benzyl amines acceler-
ate the reaction, as expected due to its increased nucle-
ophilicity (Table 4, entries 17). By contrast, the ortho-
halogenated benzyl amine with lower nucleophilicity,
possibly caused by the steric hindrance and inductive
effects of halogene, reacts slower than benzylamine
(Table 4, entry 18). With the methodology thus de-
veloped, attention turned to the transamidation of
benzamide with aromatic amines under the standard-
ised conditions (Table 4, entries 19–22). The reac-
tion was rapid with electron-rich aniline and was com-
pleted within 3 h affording a 90 % yield, but when
benzamide was treated with aniline the product was
obtained after 11 h with a 20 % yield (Table 4, en-
tries 19–22). Benzamide was also treated with furan-
2-ylmethylamine (Table 4, entry 23). The transami-
dation reaction was completed within 8 h giving a
92 % yield (Table 4, entry 23). Following these promis-
ing results, attention was directed to the reaction
of benzamide with primary and secondary aliphatic
amines such as: cyclohexylamine, butan-1-amine, 3-
ethoxypropylamine, piperidine, morpholine and pyrro-
lidine. In all cases, the reaction was smooth, giving the
corresponding N-substituted benzamides and the yield
ranged from 85 % to 95 % (Table 4, entries 24–29).
Mechanism of the present catalytic transamidation
requires elucidation, thus, the following mechanism
may be proposed for the catalytic transamidation of
carboxamides with amines in the presence of CAEA
(Fig. 3).
It may be seen that the transamidation reaction
is the activation of the electrophile (carboxamide) via
coordination to Ce(III) which subsequently generates
structure I (Fig. 3). On the other hand, the amine was
activated by coordination of Ce(III) and also by the
formation of hydrogen bonding with hydroxy groups
on the surface of catalyst. These interactions between
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Table 4. Transamidation reactions of various carboxamides and amines in the presence of CAEA (Fig. 2)
Time Isolated yield
M.p.
◦C
Compound R1
R2
Reference
h
5
%
1
2
Ph
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
PhCH2
95
101–102
(100–103)
Iranpoor et al. (2013)
Iranpoor et al. (2013)
Kunishima et al. (2004)
Iranpoor et al. (2013)
Kawagoe et al. (2013)
Tang and Chen (2012)
Wang et al. (2014b)
Fang et al. (2008)
4-MeOC6H4
3,5-Me2C6H3
4-MeC6H4
8
15
13
6
60
70
85
60
70
80
90
95
95
30
35
70
119–120
(118–122)
3
105–107
(107–108)
4
130–132
(129–132)
5
4-BrC6H4
167–168
(168)
6
2-ClC6H4
9
160–162
(161–163)
7
3,4-Cl2C6H3
3-NO2C6H4
4-NO2C6H4
pyridyl
4
103–105
(105–106)
8
4
94–96
(95)
9
3
138–140
(140)
Kawagoe et al. (2013)
Ghodsinia et al. (2013)
Iranpoor et al. (2013)
Kawagoe et al. (2013)
10
11
12
13
8
81–82
(81–83)
(E)-PhCH=CH
4-ClPhCH=CH
3-NO2PhCH=CH
16
13
9
134–137
(136–139)
149–151
(150–151)
184–186
Starkov and Sheppard (2011)
(185–186)
14
15
2,4-Cl2C6H3OCH2
(Ph)2CH
PhCH2
PhCH2
11
22
45
80
oil
Yamansarova et al. (2005)
Lanigan et al. (2013)
126–128
(127–128)
16
17
CH3(CH2)7CH=CH(CH2)6CH2 PhCH2
4-MeOC6H4CH2
25
2
90
90
oil
Ruiz-Méndez et al. (2001)
Iranpoor et al. (2013)
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
83–85
(82–85)
18
19
20
21
22
23
24
25
2-ClC6H4CH2
C6H5
6
11
4
80
20
60
50
60
92
90
85
106–108
(107–108)
Wang et al. (2014b)
Iranpoor et al. (2013)
Quan et al. (2014)
Du et al. (2014)
158–160
(160–162)
4-MeOC6H4
3,4-Me2C6H3
4-MeC6H4
furan-2-ylmethyl
cyclohexyl
butyl
163–165
(164–165)
5
147–149
(148–150)
9
156–158
(157–159)
Guo et al. (2013)
8
96–98
(98–99)
Wang et al. (2014b)
Rossi et al. (2013)
Wang et al. (2014b)
12
10
149–151
(150–152)
39–41
(37–38)
26
27
28
29
30
Ph
3-ethoxypropyl
piperidine
morpholine
pyrrolidine
PhCH2
14
15
10
16
4
80
95
90
95
95
oil
oil
oil
oil
present study
Ph
Schley et al. (2011)
Zhu et al. (2011)
Zhu et al. (2011)
Dam et al. (2010)
Ph
Ph
CH3(CH2)4
49–51
(50–52)
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Z. Zarei, B. Akhlaghinia/Chemical Papers 69 (11) 1421–1437 (2015)
Table 5. Transamidation of benzamide with benzylamine in
the presence of 0.01 g of reused CAEA
Time
h
Isolated yield
%
Entry
Run
1
2
3
4
5
6
1a
2
3
4
5
6b
5
5
5
5
5
5
95
95
95
95
95
85
a) Reaction was performed in the presence of 0.01 g, 1.61
mole %, of CAEA (contains 0.002 g, 0.01 mmol, of Ce); b) re-
action was performed in the presence of 0.01 g, 0.70 mole %, of
CAEA (contains 0.0009 g, 0.006 mmol, of Ce).
the two reactants (amide and amine) with CAEA
place them close together and lead to the formation
of structure II. Then, the facilitated nucleophilic at-
tack of amine on the amide carbonyl group leads to
the formation of structure III. The cleavage of III
leads to the rapid extrusion of ammonia and the re-
lease of N-alkylated amide. The catalyst re-enters the
catalytic cycle by making the active sites available for
further use. Further investigations into the mechanism
and scope of this reaction are currently underway.
A significant feature of this environmentally be-
nign and cost-effective straightforward protocol for
the transamidation of carboxamides with amines is
its reusability. Recovery of the CAEA in the reaction
of benzamide with benzylamine was achieved by cen-
trifugation and washing with ethyl acetate and ace-
tone several times to remove all organic compounds,
and then drying at ambient temperature. Table 5
shows the results obtained after six cycles. On the
basis of the results obtained, the efficiency of the cat-
alyst in the transamidation reaction remained after
five cycles. Inductively coupled plasma (ICP) analy-
sis shows that freshly prepared CAEA contains 0.22 g,
1.61 mmol, of Ce per 1 g of CAEA, while after the 6th
re-use the CAEA contains 0.09 g, 0.70 mmol, of Ce per
1 g of CAEA. In other words, during the recovery pro-
cess of the catalyst, the catalytic activity maintained
its effectivity after six reuses of CAEA. No significant
loss of activity of the catalyst was observed, despite
some leaching of Ce(III) during the recovery process
of the catalyst. Also, the FT-IR spectrum of the 6th
reused CAEA (Fig. 4, spectrum E) in comparison with
the freshly prepared CAEA shows that the intensities
of absorption bands (Ce—N and Ce—O frequencies)
decreased to a small extent.
Fig. 4. FT-IR spectra of washed agarose (A), epoxy-activated
agarose matrix (B), aminated epichlorohydrin-activa-
ted agarose matrix (C), Ce(III) immobilised on am-
inated epichlorohydrin-activated agarose matrix (D),
and reused Ce(III) immobilised on aminated epichloro-
hydrin-activated agarose matrix (E).
trix, the aminated epichlorohydrin-activated agarose
matrix (II) and Ce(III) immobilised on aminated
epichlorohydrin-activated agarose matrix (CAEA).
The principal bands for agarose were observed at
3553 cm−1 (O—H stretching ), 2893 cm−1 (CH2),
1655 cm−1 (H—O—H) attributed to the stretching vi-
bration of water bound to polysaccharide, 1082 cm−1
and 1035 cm−1 (attributed to anti-symmetric stretch-
ing vibrations of the C—O—C bridge), 929 cm−1
(characteristic of 3,6-anhydrogalactose), and 889 cm−1
(attributed to the C—H angular deformation of β
anomeric carbon) (Jegan et al., 2011). An absorp-
tion band at 1256 cm−1 due to the epoxy ring of
the epichlorohydrin-activated agarose matrix. The ap-
pearance of two absorption bands at 3560 cm−1 and
3472 cm−1 attributed to –NH2 stretching frequencies
and also two other absorption bands at 1593 cm−1 and
1245 cm−1 due to N—H bending vibration and C—N
stretching vibrations confirmed the ring-opening of
the epoxy ring with ammonia. The coordination of
the aminated epichlorohydrin-activated agarose ma-
trix by Ce(III) was corroborated by the absorption
bands at 588 cm−1, 539 cm−1, and 476 cm−1, 421cm−1
(which is attributed to Ce—N and Ce—O stretching
vibrations) in the FT-IR spectrum of CAEA. More-
over, the far IR spectrum of CAEA (Fig. 5) exhibited
not only the above-mentioned absorption bands but
also other bands at 597 cm−1, 568 cm−1 (Ce—N),
and 426 cm−1 (Ce—O) which confirmed the immo-
bilisation of Ce(III) on the support framework. The
coordination of nitrogen by Ce(III) was also estab-
lished by the appearance of the absorption bands of
Characterisation of catalyst
The catalyst structure was defined by FT-IR
spectroscopy. Fig. 4 illustrates the FT-IR spectra
of washed agarose, the epoxy-activated agarose ma-
–NH2 and C—N at a lower frequency (3542 cm−1
3458 cm−1, and 1190 cm−1, respectively) than the un-
,
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1433
Fig. 5. Far IR spectra of washed agarose (A), epoxy-activated agarose matrix (B), aminated epichlorohydrin-activated agarose
matrix (C), and Ce(III) immobilised on aminated epichlorohydrin-activated agarose matrix (D).
coordinated ligand form (II ). The characteristic fre-
quencies of the coordinated nitrate groups of CAEA
are 1744 cm−1 (which did not exist in the FT-IR
spectrum of the aminated epichlorohydrin-activated
agarose matrix (II ) due to the nitrate stretching
vibration), 1487 cm−1(due to the N O vibration)
—
—
which was overlapped by the C—H bending vibration
frequency of the aminated epichlorohydrin-activated
agarose matrix (II ), and 1326 cm−1 (which suggest
that nitrate anions as bidentate ligands in CAEA are
covalently bonded and are present inside the coor-
dination sphere). Another broad absorption band at
1376 cm−1 due to the ionic nitrate is also present in
the spectra (Gaye et al., 2003).
Thermogravimetric studies of the washed agarose,
the epoxy-activated agarose matrix (I ), the ami-
nated epichlorohydrin-activated agarose matrix (II),
Ce(III) immobilised on aminated epichlorohydrin-
activated agarose matrix (CAEA) at a heating rate
of 10◦C min−1 are shown in Figs. 6–9.
Fig. 6. TGA thermogram of washed agarose.
Three regions of mass loss are observed in the TGA
curve of the washed agarose. The first stage of degra-
dation represents the loss of the physically adsorbed
and hydrogen-bonded water (mass loss 10.0 %, from
22–180◦C). The major mass loss took place in the sec-
ond step (mass loss 76.0 %, 180–420◦C) and was fol-
lowed by a further mass loss in the third step (97.0 %,
420–514◦C). The second stage represents some chain
scission of washed agarose. In the third stage, com-
plete decomposition of the agarose main chains oc-
curred (Arnaouty et al., 2009; Anirudhan et al., 2012).
Similarly, the TGA thermogram of the epoxy-
activated agarose matrix (I ) exhibited three distinct
mass loss stages. As the introduction of the epoxy ring
to the main chain of the agarose decreases the hy-
Fig. 7. TGA thermogram of epoxy-activated agarose (I).
drophilicity of agarose, every stage of the mass loss
occurred at a lower temperature than in the case of
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Z. Zarei, B. Akhlaghinia/Chemical Papers 69 (11) 1421–1437 (2015)
moisture and the easily degraded components which
are strongly bonded to the polysaccaride chain via
hydrogen-bonding with the immobilised NH2 group on
the polymer chain. Water elimination also occurred at
a higher temperature than with (I ) and the washed
agarose. The evolution of ammonia and partial degra-
dation of the polysaccharide chain occurred in the
second stage (mass loss 74.0 %, 198–442◦C) as the
major mass loss in the thermogravimetric analysis of
(II ). The third stage of mass loss (98.0 %, 442–594◦C)
was predominantly the characteristic complete degra-
dation of the polysaccharide structure (breaking down
and cracking of the main chain).
By considering the TGA thermogram of the ami-
nated epichlorohydrin-activated agarose matrix (II )
and the elemental analysis data which are in good
agreement with each other, it was clear that 1.0 g of
the aminated epichlorohydri-activated agarose matrix
(II ) contains 0.0056 g, 0.4 mmol, of nitrogen (Fig. 8).
The TGA thermogram of CAEA with three steps
of mass loss differs from the previous samples. As the
hydrogen-bonding was decreased to some extent by
the coordination of –NH2 and –OH by Ce(III), re-
moval of the moisture and hydrogen-bonded water
(mass loss 8.0 %, 22–125◦C) occurred within a nar-
row temperature range. The second stage (mass loss
77.0 %, 125–292◦C) represents the exit of the water
coordinated by Ce(III) and degradation of the cerium
complex from 140◦C to 290◦C. Nitrate was also re-
moved in the second stage (Zahir, 2013). In the third
stage (mass loss 85.0 %, 292–480◦C), the complete
degradation of the polysaccharide chain occurred and
the char yield (15 %) corresponds to the remaining
cerium which was converted to CeO2 above 600◦C (Al-
ghool et al., 2013).
Fig. 8. TGA thermogram of aminated epichlorohdrin-activa-
ted agarose matrix (II).
Fig. 9. TGA thermogram of Ce(III) immobilised on aminated
epichlorohydrin-activated agarose matrix (III).
The cerium content of CAEA as obtained by in-
ductively coupled plasma (ICP) analysis was 0.22 g,
1.61 mmol of Ce per 1.0 g of CAEA.
the washed agarose. As can be seen, water elimina-
tion occurred at the first step (mass loss 8.0 %, from
23–153◦C). The second stage (mass loss 78.0 %, from
153–400◦C) can be attributed to the decomposition
of the epoxy ring and chemical degradation of some
C—C bonds of the agarose backbone. Because of the
existence of the epoxy ring, the third stage (mass loss
97 %, 400–620◦C) which corresponds to the complete
decomposition of the epoxy- activated agarose matrix
(I ) began at a lower temperature than in the case
of the washed agarose. Surprisingly, chemical degra-
dation of (I ) extended to a higher temperature than
with the washed agarose (Oza et al., 2012).
Agarose has a broad amorphous region in its natu-
ral structure, as indicated by its X-ray diffraction pat-
tern (Raphael et al., 2010). Fig. 10 shows the XRD
patterns for CAEA. One peak can be observed be-
tween 40◦ and 80◦ in the diffractogram, which indi-
cates a low amount of the cerium oxide crystal struc-
ture (Silveira et al., 2012) while no such peaks are
visible in the XRD of pure agarose between 40◦ and
80◦. A broad band centred at about 2θ = 20◦ confirms
the amorphous character of CAEA.
The TGA thermogram of the aminated epichloro-
hydrin-activated agarose matrix (II ) exhibited a
three-stage degradation pattern. Each stage of the
mass loss occurred at a higher temperature than with
(I ) and the washed agarose. This confirmed the mod-
ification of (I ) by the ring-opening of the epoxy ring
with ammonia which increased the thermal stability of
the polysaccharide. The first step (mass loss 12.0 %,
24–198◦C) may be attributed to evaporation of the
Conclusions
In conclusion, agarose was applied as a non-
toxic, low-cost, degradable natural support for the
entrapment and ligation with Ce(III) and a novel
method of the transamidation of carboxamides with
aliphatic, aromatic, cyclic, acyclic, primary, and sec-
ondary amines was developed using catalytic amounts
of CAEA as a “green” and effective catalyst under
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Z. Zarei, B. Akhlaghinia/Chemical Papers 69 (11) 1421–1437 (2015)
1435
Fig. 10. XRD pattern of Ce(III) immobilised on aminated epichlorohydrin-activated agarose matrix (III): agarose ( ), CeO2 (ꢀ).
•
solvent-free conditions. The catalyst is recyclable and
provides a wide range of amides. In view of the eco-
nomic attractiveness and the operational simplicity of
CAEA, the procedure which proceeds smoothly and
can tolerate a number of functionalities is proposed
as being of important synthetic value for access to a
variety of N-alkylated amides.
Ayub Ali, Md., Hakim Siddiki, S. M. A., Kon, K., & Shimizu,
K. i. (2014). Fe+3-exchanged clay catalyzed transamidation
of amides with amines under solvent-free condition. Tetrahe-
dron Letters, 55, 1316–1319. DOI: 10.1016/j.tetlet.2013.12.
111.
Becerra-Figueroa, L., Ojeda-Porras, A., & Gamba-Sánchez, D.
(2014). Transamidation of carboxamides catalyzed by Fe(III)
and water. The Journal of Organic Chemistry, 79, 4544–
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Cao, X. J., Zhu, J. W., Wang, D. W., Dai, G. C., & Wu, X.
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Dam, J. H., Osztrovszky, G., Nordstrøm, L. U., & Mad-
sen, R. (2010). Amide synthesis from alcohols and amines
catalyzed by ruthenium N-heterocyclic carbene complexes.
Supplementary information
The supplementary data associated with this arti-
cle can be found in the online version of this paper
(DOI: 10.1515/chempap-2015-0168).
Acknowledgements. The authors gratefully acknowledge the
partial support afforded to this study by Ferdowsi University of
Mashhad Research Council (grant no. p/3/29781).
Chemistry
- A European Journal, 16, 6820–6827. DOI:
10.1002/chem.201000569.
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through an oxidative amidation of tetrazoles with aldehy-
des under transition-metal-free conditions. RSC Advances,
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El-Arnaouty, M. B., Eid, M., Atia, A., & Dessouki, A. (2009).
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and polystyrene treated with epichlorohydrin coupled with
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