A simple and catalyst-free one-pot synthesis of α-aminophosphonates in polyethylene glycol

Article abstract of DOI:10.1080/10426507.2011.645174

A simple and efficient method has been developed for the one-pot synthesis of -aminophosphonates using polyethylene glycol (PEG) as a green reaction media.

Full text of DOI:10.1080/10426507.2011.645174

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Phosphorus, Sulfur, and Silicon and the
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A Simple and Catalyst-Free One-Pot
Synthesis of α-Aminophosphonates in
Polyethylene Glycol
M. Anil Kumar a & Kap Duk Lee a
a Department of Nanomaterial Chemistry , Dongguk University ,
Gyeongju , South Korea
Accepted author version posted online: 04 Jan 2012.Published
online: 07 Jun 2012.
To cite this article: M. Anil Kumar & Kap Duk Lee (2012) A Simple and Catalyst-Free One-Pot Synthesis
of α-Aminophosphonates in Polyethylene Glycol, Phosphorus, Sulfur, and Silicon and the Related
Elements, 187:8, 899-905, DOI: 10.1080/10426507.2011.645174
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Phosphorus, Sulfur, and Silicon, 187:899–905, 2012
Copyright ꢀC Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426507.2011.645174
A SIMPLE AND CATALYST-FREE ONE-POT SYNTHESIS OF
α-AMINOPHOSPHONATES IN POLYETHYLENE GLYCOL
M. Anil Kumar and Kap Duk Lee
Department of Nanomaterial Chemistry, Dongguk University, Gyeongju,
South Korea
GRAPHICAL ABSTRACT
Abstract A simple and efficient method has been developed for the one-pot synthesis of α-
aminophosphonates using polyethylene glycol (PEG) as a green reaction media.
Keywords α-Aminophosphonates; PEG; three-component reaction
INTRODUCTION
Conventional synthetic procedures invariably use organic solvents as a reaction media
to provide a homogeneous phase, which allows uniform molecular interactions to facilitate
the reaction efficiently. Generally, organic solvents are harmful to the environment and
human being. Development of a synthetic protocol that is nature-friendly, simple, efficient
and cost effective remains an ever-challenging objective.1
α-Aminophosphonates, being structural analogs to α-amino acids, have received
considerable interest as pharmacological agents,2 peptide mimetics,3 enzyme inhibitors,4
and also play an important role in hapten design for antibody generation.5 They also have a
wide range of antiviral6 and antifungal properties and are extensively used as insecticides
and herbicides.7 Therefore, greater attention has been paid to these compounds due to
their promising biological activity. Among the various synthetic methods reported for the
synthesis of α-aminophosphonates, a one-pot reaction starting from aldehyde, amine, and
dialkyl phosphite is the most direct and efficient one that avoids isolating an imine as
an intermediate.8 A variety of Lewis and Brønsted acid catalysts have been reported for
the synthesis of α-aminophosphonates.9 Ionic liquids have also been used as a reaction
media for three component synthesis of α-aminophosphonates.10 Recently, CoCl2.6H2O,11
[Yb(PFO)3],12 NanoFe3O4,13 KHSO4,14 and ZrOCl2.8H2O15 have also been reported for
the synthesis of α-aminophosphonates.
Received 26 September 2011; accepted 23 November 2011.
This work was supported by the Dongguk University Research Fund of 2011.
Address correspondence to Kap Duk Lee, Department of Nanomaterial Chemistry, Dongguk University,
Gyeongju -780714, South Korea. E-mail: kdlee@dongguk.ac.kr
899

900
M. A. KUMAR AND K. D. LEE
Table 1 The effect of various solvents in one-pot synthesis of 4a
Solvent
Time (h)
Yield (%)a
PEG
6
12
12
12
91
55
40
25
Toluene
Ethanol
THF
aIsolated yields.
Keeping in view the disadvantages associated in few of the earlier protocols, as well as
an increasing importance of α-aminophosphonates in pharmaceutical/industrial chemistry,
still there is a scope for the development of an efficient and environmentally benign protocol
for the synthesis of α-aminophosphonates.
Recently, polyethylene glycol (PEG) has received considerable attention in organic
synthesis as an alternative green reaction media with unique properties such as thermal
stability, nonvolatility, commercial availability, and recyclability.16 On the other hand, PEG
is nontoxic, inexpensive, nonhalogenated, and water soluble, which facilitates its removal
from the reaction product. Consequently, PEG has been utilized as a green reaction media
for various transformations such as carbon–carbon and carbon–heteroatom coupling,17
substitution,18 oxidation,19 addition,20 and reduction reactions.21
Owing to the numerous advantages associated with this cheap and green media, herein
we wish to report a green and efficient protocol for the synthesis of α-aminophosphonates
using PEG-400 as a reaction medium without adding any catalyst. To the best of our
knowledge, there are no reports for the synthesis of α-aminophosphonates using PEG-400
as a reaction medium under catalyst-free conditions.
RESULTS AND DISCUSSION
We first attempted the coupling of 10-ethyl-10H-phenothiazine-3-carbaldehyde, ani-
line, and diethyl phosphite in PEG-400 (1 g). Though the reaction was complete in 24 h at
room temperature, the corresponding product was obtained in low yield (30%). However,
the yield was dramatically increased by increasing the temperature to 100 ◦C. Under opti-
mized conditions, the reaction proceeds well at 100 ◦C and the desired α-aminophosphonate
4a was obtained in 91% yield (Scheme 1). Next, we carried out the above reaction in differ-
ent solvents such as toluene, ethanol, THF, and PEG-400 (Table 1) to know the efficiency
of PEG-400. Interestingly, PEG-400 was found to be more effective in the synthesis of 4a
in terms of reaction time (6 h) and yields (91%). PEG-400 not only acts as the solvent but
also accelerates the imine formation as well as phosphite nucleophilic addition to the imine
Scheme 1

ONE-POT SYNTHESIS OF α-AMINOPHOSPHONATES
901
Table 2 Synthesis of α-aminophosphonates using PEG as a reaction medium
Entry
a
Aldehyde
Amine
Product
Yield (%)a
91
b
c
88
90
d
e
89
87
f
86
92
93
90
88
g
h
i
j
k
l
82
80
aIsolated Yields.

902
M. A. KUMAR AND K. D. LEE
carbon by increasing its electrophilicity through hydrogen bonding by its hydroxyl group
with the imine nitrogen.
The scope and generality of the PEG-400 promoted three-component reaction, was
examined with various structurally diverse amines and diethyl phosphite. The results are
summarized in Table 2. This method works well not only with aromatic amines but also
with aliphatic amines such as benzyl amine and cyclohexylamine. All compounds were
1
1
characterized by H, 13C, 31P NMR, IR, and mass spectroscopy. H NMR spectra of
compounds 4a–j showed doublet in the region of 4.55–4.67 ppm (J = 21.4–24.2 Hz) that
is a characteristic peak for the methine proton.
CONCLUSION
In summary, we have developed a simple and efficient methodology for the one-
pot synthesis of a novel series of α-aminophosphonates under catalyst-free conditions
using PEG-400 as an environmentally benign medium. In this reaction, PEG-400 acts as an
efficient “green” promoter. The advantages of this method are simple and mild experimental
conditions, avoiding hazardous solvents and toxic organic reagents.
EXPERIMENTAL SECTION
The 10-Ethyl-10H-phenothiazine-3-carbaldehyde was prepared by the ethylation22
followed by formylation of phenothiazine.23 Melting points were determined in open cap-
illaries using Electrothermal (IA 9100) digital melting point apparatus and are uncorrected.
IR spectra were recorded on Bruker (Tensor 37) FT-IR spectrometer using KBr pellets.
∗∗∗1H, 13C, and 31P NMR spectra were recorded on a VARIAN 200 MHz instrument
with an internal standard of tetramethylsilane. Mass spectra (EI) were recorded on JEOL
JMS-700 mass spectrometer.
Experimental Procedure
A mixture of 10-ethyl-10H-phenothiazine-3-carbaldehyde (0.255g, 1 mmol), amine
(0.093g, 1 mmol), and diethyl phosphite (0.179g, 1.3 mmol) was added to PEG (1 g) and
◦
the mixture was heated to 100 C and stirred for 6–7 h. After completion of the reaction
as monitored by TLC, the mixture was then diluted with cold water and the resulting
precipitate was filtered and washed with water. The residue was dried and purified by
column chromatography over silica gel (ethyl acetate/hexane, 70–230 mesh) to give pure
α-aminophosphonate. In the case of oily products (4k and 4l), the products were extracted
with ethyl acetate, washed with water, and dried over sodium sulfate. Removal of the
solvent followed by purification on column chromatography over silica gel afforded pure
α-aminophosphonate.
◦
Entry 4a: pale yellow solid; Mp: 164–165 C; IR (KBr): 3308, 2982, 1600, 1266,
1024, 963 cm−1; 1H NMR (CDCl3): δ 1.17 (t, J = 7.4 Hz, 3H), 1.29 (t, J = 6.8 Hz, 3H),
1.38 (t, J = 6.8 Hz, 3H), 3.68–4.20 (m, 6H), 4.63 (d, J = 24.4 Hz, 1H), 6.55–6.60 (m,
2H), 6.65–6.91 (m, 4H), 7.06–7.24 (m, 6H); 13C NMR (CDCl3): δ 12.8, 16.3, 41.7, 55.1
(d, JP-C = 150.2 Hz), 63.2 (d, JP-C = 7.6 Hz), 113.8, 114.9, 118.4, 122.3, 123.8, 124.5,
126.5, 127.2, 129.1, 129.6, 144.5, 146.0, 146.3; 31P NMR (CDCl3): δ 23.6; MS (EI) m/z:
468 (M+); Anal. calcd for C25H29N2O3PS: C, 64.08; H, 6.24; N, 5.98; Found: C, 64.12; H,
6.18; N, 5.95.

ONE-POT SYNTHESIS OF α-AMINOPHOSPHONATES
903
◦
Entry 4b: pale yellow solid; Mp: 159–161 C; IR (KBr): 3316, 2982, 1525, 1273,
1022, 989 cm−1; 1H NMR (CDCl3): δ 1.17 (t, J = 7.8 Hz, 3H), 1.25–1.42 (m, 6H), 2.18 (s,
3H), 3.72–4.18 (m, 6H), 4.61 (d, J = 21.4 Hz, 2H), 6.49 (d, J = 8.0 Hz, 2H), 6.77–6.93
(m, 5H), 7.07–7.24 (m, 4H); 13C NMR (CDCl3): δ 12.8, 16.3, 20.3, 41.7, 55.4 (d, JP-C
151.7 Hz), 63.2, 113.9, 114.9, 122.3, 123.9, 124.4, 126.5, 127.2, 127.6, 129.6, 143.7, 144.0,
144.6; 31P NMR (CDCl3): δ 23.7; MS (EI) m/z: 482 (M+); Anal. calcd for C26H31N2O3PS:
C, 64.71; H, 6.47; N, 5.80; Found: C, 64.79; H, 6.40; N, 5.75.
=
Entry 4c: light brown solid; Mp: 60–62 ◦C; IR (KBr): 3301, 2956, 1522, 1235, 1022,
967 cm−1; 1H NMR (CDCl3): δ 1.13–1.20 (m, 9H), 1.28 (t, J = 7.6 Hz, 3H), 1.38 (t, J =
6.2 Hz, 3H), 2.64–2.85 (m, 1H), 3.68–4.20 (m, 7H), 4.60 (d, J = 23.6 Hz, 1H), 6.51 (d,
J = 8.0 Hz, 2H), 6.78–6.92 (m, 3H), 6.97 (d, J = 8.0 Hz, 2H), 7.08–7.23 (m, 4H); 13C NMR
(CDCl3): δ 12.8, 16.3, 24.1, 33.1, 41.8, 55.4 (d, JP-C = 151.7 Hz), 63.2 (d, JP-C = 6.0 Hz),
113.8, 114.9, 122.3, 123.9, 124.4, 126.5, 127.0, 127.2, 127.3, 129.9, 138.9, 144.0, 144.3,
144.6; 31P NMR (CDCl3): δ 23.7; MS (EI) m/z: 510 (M+); Anal. calcd for C28H35N2O3PS:
C, 65.86; H, 6.91; N, 5.49; Found: C, 65.81; H, 6.90; N, 5.45.
◦
Entry 4d: light brown solid; Mp: 132–134 C; IR (KBr): 3302, 2977, 1512, 1464,
1208, 1020, 975 cm−1; 1H NMR (CDCl3): δ 1.17 (t, J = 6.6 Hz, 3H), 1.29 (t, J = 7.2 Hz,
3H), 1.38 (t, J = 7.0 Hz, 3H), 3.68 (s, 3H), 3.78–4.16 (m, 6H), 4.56 (d, J = 23.8 Hz, 1H),
6.50–6.56 (m, 2H), 6.65–6.92 (m, 5H), 7.07–7.24 (m, 4H); 13C NMR (CDCl3): δ 12.8,
16.3, 41.8, 55.6, 56.1 (d, JP-C = 150.2 Hz), 63.2, 114.7, 114.9, 115.2, 122.3, 123.9, 124.5,
126.6, 127.2, 129.8, 140.1, 140.4, 144.6, 152.6; 31P NMR (CDCl3): δ 23.8; MS (EI) m/z:
498 (M+); Anal. calcd for C26H31N2O4PS: C, 62.63; H, 6.27; N, 5.62; Found: C, 62.69; H,
6.22; N, 5.68.
Entry 4e: yellow solid; Mp: 180–182 ◦C; IR (KBr): 3311, 2981, 1601, 1212, 1023,
1
968 cm−1; H NMR (CDCl3): δ 1.17 (t, J = 7.0 Hz, 3H), 1.29 (t, J = 6.6 Hz, 3H), 1.38
(t, J = 6.8 Hz, 3H), 2.24 (s, 3H), 3.70–4.19 (m, 7H), 4.56 (d, J = 24.0 Hz, 1H), 6.25 (dd,
J = 8.9, 2.2 Hz, 1H), 6.48 (d, J = 2.2 Hz, 1H), 6.77–6.92 (m, 3H), 7.07–7.21 (m, 5H);
13C NMR (CDCl3): δ 12.8, 16.3, 23.0, 41.8, 55.0 (d, JP-C = 151.7 Hz), 63.3, 112.7, 112.9,
114.9, 116.3, 122.3, 123.8, 124.6, 126.4, 126.6, 127.2, 129.2, 132.6, 138.2, 144.5, 144.7,
145.3, 145.6; 31P NMR (CDCl3): δ 23.3; MS (EI) m/z: 560 (M+), 562 (M+2); Anal. calcd
for C26H30BrN2O3PS: C, 55.62; H, 5.39; N, 4.99; Found: C, 55.58; H, 5.33; N, 4.95.
◦
Entry 4f: white solid; Mp: 160-161 C; IR (KBr): 3268, 2978, 1515, 1240, 1095,
967 cm−1; 1H NMR (CDCl3): δ 1.17 (t, J = 7.6 Hz, 3H), 1.28 (t, J = 7.4 Hz, 3H), 1.38 (t,
J = 7.4 Hz, 3H), 3.73–4.18 (m, 6H), 4.55 (d, J = 24.0 Hz, 1H), 6.46 (d, J = 8.4 Hz, 2H),
6.62 (d, J = 8.6 Hz, 2H), 6.76–6.93 (m, 3H), 7.07–7.21 (m, 5H); 13C NMR (CDCl3): δ
12.8, 16.2, 41.7, 56.1 (d, JP-C = 154.4 Hz), 63.4, 114.9, 115.4, 116.1, 122.3, 123.8, 124.3,
126.5, 127.2, 129.6, 139.4, 139.7, 144.5, 149.2; 31P NMR (CDCl3): δ 23.8; MS (EI) m/z:
484 (M+); Anal. calcd for C25H29N2O4PS: C, 61.97; H, 6.03; N, 5.78; Found: C, 61.94; H,
5.95; N, 5.75.
◦
Entry 4g: pale yellow solid; Mp: 184–186 C; IR (KBr): 3311, 2985, 1508, 1237,
1024, 970 cm−1; 1H NMR (CDCl3): δ 1.17 (t, J = 7.6 Hz, 3H), 1.30 (t, J = 7.4 Hz, 3H),
1.39 (t, J = 6.8 Hz, 3H), 3.68–4.19 (m, 6H), 4.56 (d, J = 24.0 Hz, 1H), 6.46–6.53 (m,
2H), 6.76–6.93 (m, 5H), 7.08–7.22 (m, 4H); 13C NMR (CDCl3): δ 12.8, 16.3, 41.8, 55.8
(d, JP-C = 151.7 Hz), 63.3 (d, JP-C = 4.5 Hz), 114.7, 114.9, 115.4, 115.8, 122.3, 123.8,
124.6, 126.5, 127.2, 129.4, 142.3, 142.6, 144.5, 144.7, 153.9, 158.6; 31P NMR (CDCl3): δ
23.5; MS (EI) m/z: 486 (M+); Anal. calcd for C25H28FN2O3PS: C, 61.72; H, 5.80; N, 5.76;
Found: C, 61.76; H, 5.86; N, 5.70.

904
M. A. KUMAR AND K. D. LEE
◦
Entry 4h: pale yellow solid; Mp:185–186 C; IR (KBr): 3330, 2981, 1598, 1274,
1
1054, 986 cm−1; H NMR (CDCl3): δ 1.17 (t, J = 7.2 Hz, 3H), 1.30 (t, J = 7.0 Hz,
3H), 1.39 (t, J = 7.2 Hz, 3H), 3.71–4.19 (m, 6H), 4.57 (d, J = 23.2 Hz, 1H), 6.47–6.53
(m, 2H), 6.78–6.93 (m, 3H), 7.02–7.21 (m, 6H); 13C NMR (CDCl3): δ 12.8, 16.3, 41.8,
55.3 (d, JP-C = 151.7 Hz), 63.3, 114.9, 122.4, 123.1, 123.8, 124.6, 126.5, 127.3, 129.0,
144.5, 144.6, 144.9; 31P NMR (CDCl3): δ 23.3; MS (EI) m/z: 502 (M+); Anal. calcd for
C25H28ClN2O3PS: C, 59.70; H, 5.61; N, 5.57; Found: C, 59.76; H, 5.55; N, 5.50.
Entry 4i: yellow solid; Mp: 172–174 ◦C; IR (KBr): 3308, 2981, 1593, 1463, 1235,
1023, 970 cm−1; 1H NMR (CDCl3): δ 1.17 (t, J = 6.8 Hz, 3H), 1.30 (t, J = 7.0 Hz, 3H),
1.39 (t, J = 6.8 Hz, 3H), 3.71–4.19 (m, 6H), 4.56 (d, J = 23.6 Hz, 1H), 6.45 (d, J = 8.4 Hz,
2H), 6.78–6.93 (m, 3H), 7.08–7.21 (m, 6H); 13C NMR (CDCl3): δ 12.8, 16.3, 41.8, 55.1
(d, JP-C = 151.7 Hz), 63.3, 110.1, 115.0, 115.5, 122.4, 123.8, 124.7, 126.5, 127.3, 129.1,
132.9, 144.5, 144.8, 145.1, 145.4; 31P NMR (CDCl3): δ 23.2; MS (EI) m/z: 546 (M+), 548
(M+2); Anal. calcd for C25H28BrN2O3PS: C, 54.85; H, 5.16; N, 5.12; Found: C, 54.89; H,
5.10; N, 5.06.
Entry 4j: yellow solid; Mp: 225–226 ◦C; IR (KBr): 3294, 2928, 1601, 1467, 1231,
1021, 989 cm−1; 1H NMR (CDCl3): δ 1.17 (t, J = 6.8 Hz, 3H), 1.27–1.42 (m, 6H), 3.67–4.17
(m, 6H), 4.67 (dd, J = 23.3, 7.2 Hz, 1H), 5.46–5.55 (m, 1H), 6.55 (d, J = 9.0 Hz, 2H),
6.79–6.94 (m, 3H), 7.07–7.22 (m, 4H), 8.02 (d, J = 9.0 Hz, 2H); 13C NMR (CDCl3): δ
12.8, 16.3, 41.8, 54.6 (d, JP-C = 153.2 Hz), 63.6 (d, JP-C = 24.2 Hz), 112.4, 115.1, 122.5,
123.6, 125.1, 126.0, 126.3, 126.5, 126.6, 127.3, 128.2, 139.0, 144.3, 145.1, 151.6, 151.9;
31P NMR (CDCl3): δ 22.3; MS (EI) m/z: 513 (M+); Anal. calcd for C25H28N3O5PS: C,
58.47; H, 5.50; N, 8.18; Found: C, 58.43; H, 5.43; N, 8.12.
1
Entry 4k: Viscous liquid; IR (KBr): 3435, 2979, 1495, 1239, 1052, 986 cm−1; H
NMR (CDCl3): δ 1.18 (t, J = 7.6 Hz, 3H), 1.28 (t, J = 7.4 Hz, 3H), 1.42 (t, J = 7.2 Hz,
3H), 3.52 (d, J = 13.0 Hz, 1H), 3.77–4.16 (m, 8H), 6.82–6.94 (m, 3H), 7.11-7.20 (m, 4H)
7.23-7.34 (m, 5H); 13C NMR (CDCl3): δ 12.8, 16.3, 41.8, 50.8 (d, JP-C = 16.6 Hz), 58.3
(d, JP-C = 154.7 Hz), 62.9, 114.8, 114.9, 122.3, 124.0, 124.4, 127.2, 127.5, 127.7, 128.4,
128.7, 138.5, 144.6, 144.7; 31P NMR (CDCl3): δ 25.5; MS (EI) m/z: 482 (M+); Anal. calcd
for C26H31N2O3PS: C, 64.71; H, 6.47; N, 5.80; Found: C, 64.65; H, 6.41; N, 5.74.
Entry 4l: Viscous liquid; IR (KBr): 3456, 2979, 2927, 1494, 1238, 1025, 964 cm−1
;
1H NMR (CDCl3): δ 1.01–1.21 (m, 7H), 1.30 (t, J = 7.2 Hz, 3H), 1.41 (t, J = 7.4 Hz, 3H),
1.45–1.89 (m, 8H), 2.26–2.39 (m, 1H), 3.76–4.20 (m, 7H), 6.80–6.94 (m, 3H), 7.10–7.24
(m, 4H); 13C NMR (CDCl3): δ 12.8, 16.3, 24.3, 24.8, 30.0, 31.8, 34.3, 41.7, 53.2 (d,
JP-C = 15.2 Hz), 56.5 (d, JP-C = 154.7 Hz), 62.6 (d, JP-C = 7.5 Hz), 63.1 (d, JP-C = 6.1
Hz), 114.7, 114.9, 122.2, 124.1, 127.1, 127.2, 130.5, 144.4, 144.6; 31P NMR (CDCl3): δ
25.2; MS (EI) m/z: 474 (M+); Anal. calcd for C25H35N2O3PS: C, 63.27; H, 7.43; N, 5.90;
Found: C, 63.21; H, 7.39; N, 5.84.
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