A Quick and Clean Procedure for Synthesis of α-Aminophosphonates in Aqueous Media

Article abstract of DOI:10.1002/hc.21263

A green and efficient procedure for the synthesis of α-aminophosphonates has been developed in water as a green and nonhazardous solvent, from condensation between aromatic aldehydes, aniline, and triphenyl phosphite at 80°C. This methodology has a number

Full text of DOI:10.1002/hc.21263

Heteroatom Chemistry
Volume 0, Number 0, 2015
A Quick and Clean Procedure for Synthesis
of α-Aminophosphonates in Aqueous Media
Ebrahim Mollashahi, Hamideh Gholami, Mehrnoosh Kangani,
Mojtaba Lashkari, and Malek Taher Maghsoodlou
Department of Chemistry, University of Sistan and Baluchestan, P.O. Box 98135-674, Zahedan,
Iran
Received 11 April 2014; revised 11 January 2015; accepted 29 January 2015
sulfate) [11], lithium perchlorate [12], zirconium
ABSTRACT: A green and efficient procedure for the
compounds [13, 14], Bønsted acids [15], lantanide
synthesis of α-aminophosphonates has been devel-
triflate [16], samarium diiodide [17], InCl3 [18],
oped in water as a green and nonhazardous solvent,
TaCl5–SiO2 [19], bromodimethylsulfonium bromide
from condensation between aromatic aldehydes, ani-
[20], montmorillonite KSF [21], alumina-supported
line, and triphenyl phosphite at 80°C. This methodol-
reagents as catalysts [22], amberlite-IR 120 [23],
ogy has a number of advantages including clean reac-
H3PW12O40 [24], oxalic acid [25], and TiO2 [26], were
tion conditions, easy work-up, and environmentally
reported to be effective catalysts for this one-pot re-
ꢀC
friendly.
2015 Wiley Periodicals, Inc. Heteroatom
action. However, some of these procedures suffered
from drawbacks such as the use of organic solvents,
long reaction times, difficulties in work-up proce-
dures, and relatively low yields and generally only di-
alkyl or trialkyl phosphites were used as phosphorus
reagents. According to the wide range of biological
properties of α-aminophosphonates, it is still neces-
sary to develop a new simple, efficient, and general
method, for this three-component reaction.
Recently, several procedures have been reported
for the synthesis of α-aminophosphonates under sol-
vent and catalyst free conditions with excellent yield,
or using easily available catalysts; moreover, these
procedures seems to be extremely simple [27–33].
In continuation with our investigation on the syn-
thesis of α-aminophosphonates [34–42], herein we
report a green and mild protocol for the synthesis of
α-aminophosphonates in aqueous media without a
catalyst (Scheme 1).
Chem. 0:1–6, 2015; View this article online at wiley-
onlinelibrary.com. DOI 10.1002/hc.21263
INTRODUCTION
α-Aminophosphonates have received much atten-
tion due to their biological activity. Their uses as
enzyme inhibitors, antibiotics, peptide mimics, her-
bicides, pharmacological agents, and many other
applications are well documented [1–5]. The tradi-
tional Lewis acid–catalyzed addition of diethyl phos-
phite to aldimines has provided a useful method
for the preparation of α-aminophosphonates [6–8].
However, these reactions cannot proceed smoothly
by a one-pot method from aldehydes, amines, and
diethyl phosphite since the water generated dur-
ing the reactions can deactivate or decompose
the catalysts [9]. Some new type of Lewis acids,
such as metal triflates [10], scandium tris(dodecyl
RESULTS AND DISCUSSION
We have performed a set of preliminary experiments
in the three-component reaction of benzaldehyde,
aniline, and triphenyl phosphite in different solvents
at different temperatures (25, 30, 40, 50, 60, 70, 80,
90°C) in the mixture of solvent. As shown in Table 1,
Correspondence to: Malek Taher Maghsoodlou; e-mail: mt_
maghsoodlou@chem.usb.ac.ir, mt_maghsoodlou@yahoo.com.
Contract grant sponsor: Research Council of the University of
Sistan and Baluchestan.
ꢀC
2015 Wiley Periodicals, Inc.
1

2
Mollashahi et al.
PhO
PhO
NH2
O
O
P
OPh
P
H2O
Ar
H
Ar
N
H
PhO
OPh
80 °C
3
2
4
1
SCHEME 1 Synthesis of α-aminophosphonates in aqueous media at 80°C.
TABLE 1 Optimization Reaction Conditions for the Synthesis of α-Aminophosphonates
PhO
PhO
NH2
O
O
P
OPh
P
Ph
H
Ph
N
H
PhO
OPh
3
2
4a
1
Entry
Solvent
Temperature (°C)
Time (h)
Isolated Yield (%)
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
–
25
80
80
80
80
25
30
40
50
60
70
80
90
40
80
72
7
–
Acetonitrile
Ethanol
Ethanol : H2O (1:1)
Ethanol : H2O (1:2)
H2O
H2O
H2O
H2O
H2O
H2O
H2O
H2O
Dichloromethane
Ethyl acetate
78
54
40
56
–
14
30
68
73
85
90
91
65
62
10
16
16
72
72
40
22
16
8
3
3
8
8
the best solvent is water and the best temperature is
80°C.
Using this optimized condition, we prepared
a wide variety of α-aminophosphonates using
arylaldehydes, aniline, and triphenyl phosphite
(Table 2).
in water at 80°C. This method has many advantages
such as clean reaction conditions, easy work-up, and
the absence of hazardous catalyst.
EXPERIMENTAL
Interestingly, a variety of aryl aldehydes includ-
ing electron-withdrawing or -releasing substituents
(ortho-, meta-, and para-substituted) participated
well in this reaction and gave the product in good
to excellent yield.
A plausible mechanism is shown in Scheme 2.
It is believed to involve the formation of activated
imine A by condensation of the aldehyde and amine
[43–46]. Then phosphite is added to the C═N bond
of imine A to give the phosphonium intermediate B.
This phosphonium intermediate undergoes a reac-
tion with water to give the α-aminophosphonate 4.
Melting points and IR spectra were measured on
an Electrothermal 9100 apparatus (UK) and a Shi-
madzu IR-460 spectrometer (Japan), respectively.
1H, 13C, and 31P NMR spectra were measured
on a Bruker DRX-400 Avance spectrometer (Ger-
many) with CDCl3 as a solvent. All reagents were
purchased from Merck (Darmstadt, Germany) and
Fluka (Buchs, Switzerland) and used without any
purification.
General Procedure for the Synthesis of
α-Aminophosphonates 4a–l
A mixture of arylaldehydes 1 (1.0 mmol), aniline 2
(1.0 mmol), and triphenyl phosphite 3 (1.0 mmol)
in H2O (1 mL) was stirred at 80°C for the appropri-
ate time (Table 2). After completion of the reaction
(as indicated by TLC), the solution was filtered and
CONCLUSION
α-Aminophosphonates derivatives have been pre-
pared via the one-pot three component reaction from
aromatic aldehydes, aniline, and triphenyl phosphite
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of α-Aminophosphonates in Aqueous Media
3
H2O
O
H
(PhO)3P
(PhO)3P
N
3
NH
Ph
Ph NH2
+
Ar
H
Ar
Ph
Ar
H2O
B
A
1
2
H
H
H
O
O
O
(PhO)3P
(PhO)2P OPh
NH
-H
(PhO)2P
-PhOH
NH
Ph
NH
Ph
Ar
Ar
Ph
Ar
C
D
4
SCHEME 2 Plausible mechanism for the synthesis of α-aminophosphonates derivatives.
the solid phase (product) was washed with water to
afford pure α-aminophosphonates. Spectral data for
the selected compounds are presented below.
Diphenyl(3-nitrophenyl)(phenylamino)
methylphosphonate 4c. 1H NMR (400 MHz;
CDCl3): δ 4.66 (1H, br, NH), 5.27 (1H, d, 2JHP = 25.3
Hz, CHP), 6.63–8.46 (19H, m, HAr); 13C NMR (100.6
1
MHz, CDCl3) δ: 55.5 (d, JCP = 152.4 Hz, CHP),
Diphenyl Phenyl(phenylamino)methylphospho-
114.0 (s, 2Cortho, NHPh), 119.5 (s, Cpara, NHPh),
nate 4a. 1H NMR (400 MHz; CDCl3): δ 4.82 (1H, br,
3
3
120.0 (d, JCP = 4.1 Hz, 2Cortho, OPh), 120.4 (d, JCP
2
NH), 5.21 (1H, d, JHP = 24.7 Hz, CHP), 6.69–7.62
3
= 4.1 Hz, 2Cortho, OPh), 123.1 (d, JCP = 5.6 Hz, C2,
(20H, m, HAr); 13C NMR (100.6 MHz, CDCl3) δ:
CAr), 123.4 (s, C4, CAr), 125.6 (s, Cpara, OPh), 125.7
(s, Cpara, OPh), 129.4 (s, 2Cmeta, NHPh), 129.6 (s,
2Cmeta, OPh), 129.7 (s, 2Cmeta, OPh), 130.4 (s, C5,
1
56.0 (d, JCP = 154.7 Hz, CHP), 114.0 (s, 2Cortho
,
3
NHPh), 118.8 (s, Cpara, NHPh), 120.2 (d, JCP = 4.5
3
Hz, 2Cortho, OPh), 120.6 (d, JCP = 4.5 Hz, 2Cortho
,
3
CAr), 134.0 (d, JCP = 5.1 Hz, C6, CAr), 137.6 (s, C1,
OPh), 125.1 (s, Cpara, OPh), 125.3 (s, Cpara, OPh),
CAr), 145.1 (d, 3JCP = 14.6 Hz, Cipso, NHPh), 148.5 (s,
3
128.1 (d, JCP = 5.8 Hz, 2Cortho, CAr), 128.3 (s, Cpara
,
2
C3, CAr), 150.0 (d, JCP = 9.4 Hz, Cipso, OPh), 150.1
4
CAr), 128.7 (d, JCP = 2.6 Hz, 2Cmeta, CAr), 129.2
(d, 2JCP = 9.4 Hz, Cipso, OPh).
(s, 2Cmeta, NHPh), 129.5 (s, 2Cmeta, OPh), 129.6 (s,
3
2Cmeta, OPh), 134.7 (s, C1, CAr), 145.8 (d, JCP
=
15.1 Hz, Cipso, NHPh), 150.1 (d, 2JCP = 9.2 Hz, Cipso
OPh), 150.3 (d, 2JCP = 9.2 Hz, Cipso, OPh).
,
Diphenyl(4-nitrophenyl)(phenylamino)
methylphosphonate 4d. 1H NMR (CDCl3, 400
MHz): δ 5.02 (1H, brs, NH), 5.25 (1H, d, 2JPH = 26.0
Hz, CHP), 6.61 (2H, d, J = 8.0 Hz, HAr), 6.81 (1H, t,
J = 8.0 Hz, HAr), 6.97–7.33 (11H, m, HAr), 7.78 (2H,
dd, J = 8.8, 2.4 Hz, HAr), 8.22 (2H, d, J = 8.0 Hz,
Diphenyl(2-nitrophenyl)(phenylamino)
methylphosphonate 4b. 1H NMR (400 MHz;
CDCl3): δ 4.59 (1H, br, NH), 6.62 (1H, d, 2JHP = 27.0
Hz, CHP), 6.70–8.10 (19H, m, HAr); 13C NMR (100.6
MHz, CDCl3) δ: 55.5 (d, 1JCP = 154.2 Hz, CHP), 113.8
(s, 2Cortho, NHPh), 119.3 (s, Cpara, NHPh), 119.9 (d,
HAr); 13C NMR (100.6 MHz, CDCl3) δ: 55.2 (d, JCP
1
= 152.4 Hz, CHP), 113.9 (s, 2Cortho, NHPh), 119.4
3
3
3JCP = 4.1 Hz, 2Cortho, OPh), 120.6 (d, JCP = 4.1
(s, Cpara, NHPh), 120.0 (d, JCP = 3.9 Hz, 2Cortho
,
3
Hz, 2Cortho, OPh), 125.4 (s, Cpara, OPh), 125.7 (s,
OPh), 120.4 (d, JCP = 3.9 Hz, 2Cortho, OPh), 123.8
4
Cpara, OPh), 125.5 (d, JCP = 2.1 Hz, C3, CAr), 129.1
(s, Cmeta, CAr), 125.6 (s, Cpara, OPh), 125.7 (s, Cpara,
3
3
(s, C4, CAr), 129.3 (d, JCP = 4.6 Hz, C6, CAr), 129.5
OPh), 128.9 (d, JCP = 5.4 Hz, Cortho, CAr), 129.3 (s,
(s, 2Cmeta, NHPh), 129.7 (s, 2Cmeta, OPh), 129.8 (s,
2Cmeta, NHPh), 129.8 (s, 4Cmeta, 2OPh), 142.7 (s,
2Cmeta, OPh), 131.02 (s, C5, CAr), 133.8 (d, 2JCP = 3.2
Cipso, CAr), 145.1 (d, JCP = 14.6 Hz, Cipso, NHPh),
3
3
2
Hz, C1, CAr), 144.8 (d, JCP = 14.7 Hz, Cipso, NHPh),
147.7 (s, Cpara, CAr), 149.8 (d, JCP = 9.1 Hz, Cipso
,
3
2
149.3 (d, JCP = 6.0 Hz, C2, Ar), 149.9 (d, JCP = 9.5
Hz, Cipso, OPh), 150.1 (d, 2JCP = 9.5 Hz, Cipso, OPh).
OPh), 150.0 (d, 2JCP = 9.1 Hz, Cipso, OPh); 31P NMR
(CDCl3, 161.97 MHz) δ: 13.3.
Heteroatom Chemistry DOI 10.1002/hc

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Mollashahi et al.
TABLE 2 Synthesis of α-aminophosphonates derivatives in H2O at 80°C
PhO
PhO
NH2
O
O
P
OPh
H2O
80 °C
P
Ar
H
Ar
N
H
PhO
OPh
3
2
4
1
Melting Point (°C)
Entry
Aldehyde
Product
Time (h)
Yield (%)a
Found
Literature [34]
PhO
PhO
O
CHO
P
1
3
90
148–149
149–150
134–136
N
H
4a
PhO
PhO
O
CHO
NO2
P
2
3
4
8
83
73
137–139
128–129
N
H
4b
NO2
PhO
O
CHO
PhO
NO2
P
N
128–129
H
NO2
4c
CHO
PhO
PhO
O
P
4
5
6
5
8
7
85
96
92
147–149
139–140
130–131
147–149
136–138
130–132
N
H
NO2
O2N
4d
4e
CHO
Cl
PhO
PhO
O
P
N
H
Cl
Cl
Cl
Cl
P
CHO
PhO
PhO
O
N
H
Cl
4f
PhO
PhO
O
P
CHO
N
H
7
8
9
4
6
9
71
80
76
121–123
100–103
111–113
119–121
103–105
110–112
F
4g
F
CHO
PhO
PhO
O
P
N
H
F
F
4h
PhO
O
CHO
OMe
PhO
P
N
H
OMe
OMe
4i
OMe
(Continued)
Heteroatom Chemistry DOI 10.1002/hc

Synthesis of α-Aminophosphonates in Aqueous Media
5
TABLE 2 Continued
PhO
O
NH2
O
PhO
P
OPh
P
H2O
Ar
H
Ar
N
PhO
OPh
80 °C
H
3
2
4
1
Melting Point (°C)
Entry
Aldehyde
Product
Time (h)
Yield (%)a
Found
Literature [34]
PhO
PhO
CHO
O
P
OMe
10
MeO
8
7
81
118–119
115–117
N
H
MeO
OMe
4j
PhO
PhO
CHO
Me
O
P
11
12
80
81
125–126
125–126
124–126
125–127
N
H
Me
4k
PhO
O
CHO
PhO
P
7
N
H
Me
4l
Me
aIsolated yield.
4
Diphenyl(2,4-dichlorophenyl)(phenylamino)
OPh), 129.0 (d, JCP = 2.0 Hz, C3, C5, CAr), 129.3 (s,
2Cmeta, NHPh), 129.5 (d, 3JCP = 5.9 Hz, C2, C6, CAr),
129.7 (s, 2Cmeta, OPh), 129.8 (s, 2Cmeta, OPh), 133.3
methylphosphonate 4e. 1H NMR (CDCl3, 400
3
MHz): δ 5.14 (1H, t, JNH = 9.2 Hz, NH), 5.74 (1H,
2
3
2
dd, JPH = 25.6, JNH = 8.4 Hz, CHP), 6.62 (2H,
d, J = 8.0 Hz, HAr), 6.78 (1H, t, J = 8.0 Hz, HAr),
6.94–7.42 (14H, m, HAr), 7.61 (1H, dd, J = 8.0, 2.8
Hz, HAr); 13C NMR (100.6 MHz, CDCl3) δ: 51.3 (d,
1JCP = 157.7 Hz, CHP), 113.9 (s, 2Cortho, NHPh),
(s, C4, CAr), 134.3 (d, JCP = 4.0 Hz, C1, CAr), 145.3
(d, 3JCP = 17.1 Hz, Cipso, NHPh), 150.0 (d, 2JCP = 9.7
Hz, Cipso, OPh), 150.2 (d, 2JCP = 9.7 Hz, Cipso, OPh).
Diphenyl(3-fuorophenyl)(phenylamino)
3
methylphosphonate 4g. 1H NMR (CDCl3, 400
MHz): δ 4.91 (1H, brs, NH), 5.15 (1H, d, 2JPH = 25.2
Hz, CHP), 6.65 (2H, dd, J = 8.4, 0.8 Hz, HAr), 6.79
(1H, t, J = 8.0 Hz, HAr), 6.93–7.38 (16H, m, HAr).
119.4 (s, Cpara, NHPh), 119.8 (d, JCP = 4.1 Hz,
2Cortho, OPh), 120.7 (d, 3JCP = 4.1 Hz, 2Cortho, OPh),
125.3 (s, Cpara, OPh), 125.6 (s, Cpara, OPh), 127.9
4
(d, JCP = 3.1 Hz, C5, CAr), 129.4 (s, 2Cmeta, NHPh),
129.6 (s, 2Cmeta, OPh), 129.8 (s, 2Cmeta, OPh), 130.1
3
(d, JCP = 4.12 Hz, C6, CAr), 131.7 (s, C3, CAr), 134.8
Diphenyl(4-fuorophenyl)(phenylamino)
(d, 2JCP = 4.2 Hz, C1, Ar), 134.9 (d, 3JCP = 7.8 Hz, C2,
methylphosphonate 4h. 1H NMR (CDCl3, 400
3
3
C4, CAr), 144.8 (d, JCP = 16.5, Cipso, NHPh), 150.1
MHz): δ 4.96 (1H, t, JNH = 8.8 Hz, NH), 5.16 (1H,
2
2
2
3
(d, JCP = 9.7 Hz, Cipso, OPh), 150.2 (d, JCP = 9.7
dd, JPH = 24.4, JNH = 8.0 Hz, CHP), 6.65 (2H,
d, J = 8.0 Hz, HAr), 6.79 (1H, t, J = 8.0 Hz, HAr),
6.92-7.58 (16H, m, HAr) 31P NMR (CDCl3, 161.97
MHz) δ: 14.9.
Hz, Cipso, OPh).
Diphenyl(4-chlorophenyl)(phenylamino)
methylphosphonate 4f. 1H NMR (CDCl3, 400
MHz): δ 4.97 (1H, brs, NH), 5.15 (1H, d, 2JPH = 24.0
Hz, CHP), 6.63–7.54 (19H, m, HAr); 13C NMR (100.6
MHz, CDCl3) δ: 55.6 (d, 1JCP = 153.9 Hz, CHP), 114.3
(s, 2Cortho, NHPh), 119.3 (s, Cpara, NHPh), 120.2 (d,
3JCP = 4.2 Hz, 2Cortho, OPh), 120.6 (d, 3JCP = 4.2 Hz,
Diphenyl(2,3-dimethoxyphenyl)(phenylamino)
methylphosphonate 4i. 1H NMR (CDCl3, 400 MHz):
δ 3.87 and 3.97 (6H, 2s, 2× OMe), 4.86 (1H, t, 3JNH
=
2
3
8.4 Hz, NH), 5.82 (1H, dd, JPH = 24.8, JNH = 10.0
Hz, CHP), 6.72–7.32 (18H, m, HAr); 13C NMR (100.6
1
2Cortho, OPh), 125.4 (s, Cpara, OPh), 125.5 (s, Cpara
,
MHz, CDCl3) δ: 48.7 (d, JCP = 157.9 Hz, CHP),
Heteroatom Chemistry DOI 10.1002/hc

6
Mollashahi et al.
OPh), 120.75 (d, 3JCP = 4.3 Hz, 2Cortho, OPh), 125.24
55.7, 61.0 (2s, 2× OCH3), 112.5 (s, C4, CAr), 114.2
(s, 2Cortho, NHPh), 119.0 (s, Cpara, NHPh), 120.1 (d,
3JCP = 4.6 Hz, C6, CAr), 120.2 (s, C5, CAr), 120.4 (d,
(s, Cpara, OPh), 125.39 (s, Cpara, OPh), 125.41 (s, C4),
3
3
128.71 (d, JCP = 2.1 Hz, C6), 128.95 (d, JCP = 6.2
Hz, C2), 129.25 (s, C5), 129.29 (s, 2 Cmeta, NHPh),
129.61 (s, 2Cmeta, OPh), 129.76 (s, 2Cmeta, OPh),
3
3JCP = 4.1 Hz, 2Cortho, OPh), 120.8 (d, JCP = 4.1
2
Hz, 2Cortho, OPh), 124.4 (d, JCP = 2.5 Hz, C1, CAr),
2
125.2 (s, Cpara, OPh), 125.4 (s, Cpara, OPh), 129.2
(s, 2Cmeta, NHPh), 129.6 (s, 2Cmeta, OPh), 129.7 (s,
2Cmeta, OPh), 147.3 (d, 3JCP = 14.5 Hz, Cipso, NHPh),
134.40 (s, C3), 138.51 (d, JCP = 2.5 Hz, C1),145.63
3
2
(d, JCP = 14.7 Hz, Cipso, NHPh), 150.29 (d, JCP
=
10.1 Hz, Cipso, OPh), 150.40 (d, 2JCP = 10.1 Hz, Cipso
,
150.3 (d, 2JCP = 9.7 Hz, Cipso, OPh), 150.5 (d, 2JCP
=
OPh). 31P NMR (161.97 MHz) δ: 15.51. MS m/z (%):
429 (17) [M+], 196 (100), 178 (15),140 (20), 104
(34), 77 (42). Anal. Calcd for C26H24NO3P: C, 72.72;
H, 5.63; N, 3.26. Found: C, 72.51; H, 5.70; N, 3.39.
9.7 Hz, Cipso, OPh), 152.4 (d, 3JCP = 1.3 Hz, C2, CAr),
156.04 (s, C3, CAr).
Diphenyl(2,5-dimethoxyphenyl)(phenylamino)
methylphosphonate 4j. 1H NMR (CDCl3, 400 MHz):
3
δ 3.70 and 3.85 (6H, 2s, 2× OMe), 4.93 (1H, t, JNH
2
3
= 8.8 Hz, NH), 5.77 (1H, dd, JPH = 25.2, JNH
=
REFERENCES
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(100.6 MHz, CDCl3) δ: 48.9 (d, JCP = 157.8 Hz,
4
CHP), 55.7, 56.3 (2s, 2× OCH3), 11.9 (d, JCP = 2.1
3
Hz, C5, CAr), 113.9 (s, C4, CAr), 114.2 (d, JCP = 4.9
Hz, C2, CAr), 114.7 (s, Cortho, NHPh), 118.9 (s, Cpara
,
NHPh), 120.1 (d, 3JCP = 4.4 Hz, 2Cortho, OPh), 120.7
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2
(d, JCP = 4.4 Hz, 2Cortho, OPh), 120.5 (d, JCP = 5.0
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,
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2
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2
OPh), 151.6 (d, JCP = 9.7 Hz, Cipso, OPh), 154.0 (d,
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Diphenyl(phenylamino)(p-tolyl)
methylphosphonate 4k. 1H NMR (400 MHz;
CDCl3): δ 2.35 (3H, s, CH3), 4.79 (1H, br, NH), 5.17
2
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3
NHPh), 118.9 (s, Cpara, NHPh), 120.3 (d, JCP = 4.3
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OPh), 125.2 (s, Cpara, OPh), 125.3 (s, Cpara, OPh),
3
125.4 (s, C4, CAr), 128.7 (d, JCP = 2.1 Hz, C6, CAr),
3
128.9 (d, JCP = 6.2 Hz, C2, CAr), 129.2 (s, C5, CAr),
129.2 (s, 2Cmeta, NHPh), 129.6 (s, 2Cmeta, OPh),
129.7 (s, 2Cmeta, OPh), 134.4 (s, C3, CAr), 138.5 (d,
2JCP = 2.5 Hz, C1, CAr), 145.6 (d, JCP = 14.7 Hz,
3
2
Cipso, NHPh), 150.2 (d, JCP = 10.1 Hz, Cipso, OPh),
150.4 (d, 2JCP = 10.1 Hz, Cipso, OPh).
Diphenyl(phenylamino)(m-tolyl)
methylphosphonate 4l. IR (KBr) (υmax
,
cm−1):
3342 (N-H); 1H NMR (CDCl3, 400 MHz): δ 2.35
2
(3H, s, CH3), 4.79 (1H, bs, NH), 5.17 (1H, d, JHP
=
24.6 Hz, CHP), 6.71–7.41 (19H, m, HAr); 13C NMR
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(CDCl3, 100.6 MHz) δ: 21.46 (s, CH3), 55.96 (d, JCP
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Heteroatom Chemistry DOI 10.1002/hc

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Heteroatom Chemistry DOI 10.1002/hc