A facile synthesis of α-aminophosphonates catalyzed by ytterbium perfluorooctanoate under solvent-free conditions

Article abstract of DOI:10.1016/j.jfluchem.2010.12.002

Three-component reactions of aldehydes, amines and diethyl phosphite are efficiently catalyzed by ytterbium perfluorooctanoate [Yb(PFO)₃] under solvent-free conditions, giving the corresponding α- aminophosphonates in good to excellent yields. The catalyst can be recovered and reused for several times without any significant loss of activity. Furthermore, a possible mechanism for this transformation is also presented.

Full text of DOI:10.1016/j.jfluchem.2010.12.002

Journal of Fluorine Chemistry 132 (2011) 102–106
Contents lists available at ScienceDirect
Journal of Fluorine Chemistry
journal homepage: www.elsevier.com/locate/fluor
A facile synthesis of
a
-aminophosphonates catalyzed by ytterbium
perfluorooctanoate under solvent-free conditions
a
a
a
a
Jun Tang a, Limin Wang a,b, , Wenbo Wang , Liang Zhang , Shengying Wu , Dan Mao
*
a Key Laboratory for Advanced Materials & Institute of Fine Chemicals, East China University of Science and Technology, 130 Meilong Road, Shanghai 200237, PR China
b Key Laboratory of Organofluorine Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, PR China
A R T I C L E I N F O
A B S T R A C T
Article history:
Three-component reactions of aldehydes, amines and diethyl phosphite are efficiently catalyzed by
Received 15 September 2010
Received in revised form 1 December 2010
Accepted 2 December 2010
Available online 9 December 2010
ytterbium perfluorooctanoate [Yb(PFO)3] under solvent-free conditions, giving the corresponding
a-
aminophosphonates in good to excellent yields. The catalyst can be recovered and reused for several
times without any significant loss of activity. Furthermore, a possible mechanism for this transformation
is also presented.
ß 2010 Elsevier B.V. All rights reserved.
Keywords:
Ytterbium perfluorooctanoate
a
-Aminophosphonate
Kabacknik–Fields reaction
One-pot reaction
1. Introduction
As a part of our program aiming at developing efficient and
environmentally friendly fluorous rare earth catalyst, we have
a
-Aminophosphonates have attracted much attention owing to
developed ytterbium perfluorooctanoate [Yb(PFO)3] as an easily
prepared, air stable, water tolerated and recyclable catalyst in
promoting condensations of indole with carbonyl compounds
efficiently as well as other multicomponent condensation reac-
tions [16]. In this paper, we report a facile and efficient method for
their biological activities. Their utilities as enzyme inhibitors,
antibiotics, peptide mimics, herbicides, pharmacological agents
and many other applications are well documented [1–5]. Thus, a
number of synthetic methods including enantioselective hydro-
phosphonylation reactions [6] have been developed during the last
decades. The traditional Lewis acid-catalyzed addition of diethyl
phosphite to aldimines has provided a useful method for the
synthesis of
a-aminophosphonates via one-pot Kabacknik–Fields
reaction of aldehydes, amines and diethyl phosphite promoted by
Yb(PFO)3 under solvent-free conditions.
preparation of
a-aminophosphonates [7–9]. However, these
reactions cannot proceed smoothly by a one-pot method from
aldehydes, amines, and diethyl phosphite since water generated
during the reactions can deactivate or decompose the catalysts
[10]. Some new type Lewis acids, such as metal triflates [11],
scandium tris(dodecyl sulfate) [12], lithium perchlorate [13],
zirconium compounds [14], and Brønsted acid [15] were recently
reported to be effective catalysts for this one-pot reaction.
However, some of these procedures suffered from drawbacks of
the use of organic solvents, long reaction times, difficulties in
work-up procedures and relatively low yields. Considering the
2. Results and discussion
The three-component reaction of benzaldehyde 1a, aniline 2a,
and diethyl phosphite was selected as a model reaction for the one-
pot synthesis of a-aminophosphonate 3a promoted by a variety of
Lewis acid catalysts (Scheme 1).
The reactions were carried out in ethanol at ambient tempera-
ture and the results are shown in Table 1. To our delight, Yb(PFO)3
provided as high as 87% yield within just 1 h. No significant
promoting effects were obtained even in the presence of 20 mol%
of the traditional Lewis acids as predicted (entries 2 and 3). Other
rare earth metal salts gave the desired product in moderate to good
yields (entries 4–7). Overall, ytterbium perfluorooctanoate
achieved the best result. Due to the current challenge for
developing environmentally benign solvent-free synthetic sys-
tems, we tried to carry out this reaction without solvent and
obtained higher yield of 3a (92%, entry 9). The yield was not
obviously changed when the amount of catalyst was reduced to
wide range of biological property of
a-aminophosphonates, it is
still necessary to develop a new method that is simple, efficient
and general for this three-component reaction.
* Corresponding author at: Institute of Fine Chemicals, Lab for Advanced
Materials, East China University of Science and Technology, 130 Meilong Road,
Shanghai 200237, PR China. Tel.: +86 21 64253881; fax: +86 21 64253881.
E-mail address: wanglimin@ecust.edu.cn (L. Wang).
0022-1139/$ – see front matter ß 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.jfluchem.2010.12.002

[
J. Tang et al. / Journal of Fluorine Ch
]
emistry 132 (2011) 102–106
103
NHR2
NHPh
O
P
OEt
O
P
OEt
O
O
Yb(PFO)3
neat / r.t.
cat.
R2-NH2
H
OEt
+
+
+
+
Ph-NH2
H
OEt
R1
P
O
(OEt)2
(OEt)2
Ph
P
R1
H
Ph
H
O
1
2
3
1a
2a
3a
Scheme 2.
Scheme 1.
Table 1
Table 2
Effect of different catalysts in the reaction of benzaldehyde (1 mmol), aniline
(1 mmol), and diethyl phosphite (1.2 mmol)a via Scheme 1.
Synthesis of different
Scheme 2.a
a-aminophosphonates in the presence of 1 mol% Yb(PFO)3 via
Entry
Catalyst
Amount of catalyst
(mol%)
Solvent
Yield (%)b
Entry
R1
R2
Product
Yield (%)b
1
2
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
Ph
3a
3b
3c
90
86
1
2
/
/
20
20
10
5
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
EtOH
neat
20
2-ClC6H4
3-ClC6H4
4-ClC6H4
4-FC6H4
4-NO2C6H4
4-CH3C6H4
4-OCH3C6H4
Ph
AlCl3
30
3
90
3
ZnCl2
26
4
3d
3e
3f
84
4
YbCl3
68
5
86
5
Yb(OTf)3
Sm(PFO)3
La(PFO)3
Yb(PFO)3
Yb(PFO)3
Yb(PFO)3
Yb(PFO)3
84
6
84
6
5
76
7
3g
3h
3i
90
7
5
72
87
8
92
8
5
9
2-NO2C6H4
3-NO2C6H4
4-NO2C6H4
4-ClC6H4
93
9
5
92
10
11
12
13
14
15
16
17
Ph
3j
90
10
11
1
neat
90
90,88,88c
Ph
3k
3l
95
1
neat
Ph
88
a
4-CH3C6H4
4-OCH3C6H4
4-OCH3C6H4
(CH3)2CH-
Ph
Ph
3m
3n
3o
3p
3q/4q
90
All reactions were carried out at room temperature for 1 h.
Isolated yields.
b
c
Ph
86
4-NO2C6H4
Ph
90
Catalyst was reused for three times.
50c
55/35d
Cyclohexyl
a
1 mol%. Furthermore, recovering and reusing the catalyst for 3
times, the catalytic activities were shown without any significant
loss (1st, 90%; 2nd, 88%; 3rd, 88% yield; respectively).
To establish generality, the reactions of various aldehydes and
amines with diethyl phosphite in the presence of 1 mol% of
Yb(PFO)3 under solvent-free conditions giving the corresponding
All reactions were carried out at room temperature for 1 h.
Isolated yields.
b
c
The reaction was heated at 50 8C for 6 h.
d
The products are
a-aminophosphonate (3q)/a-hydroxyphosphonate (4q).
a
-aminophosphonates were examined (Scheme 2). The results are
the above results, the pathway of this one-pot reaction depends
on the nature of the amines. Taking benzaldehyde as an example,
our proposed mechanism is depicted in Scheme 3.The amine and
diethyl phosphite form a complex which either one of the
partners may react with benzaldehyde. Often, the ability of the
formation of imines determines the reaction pathway. Aromatic
amines react with benzaldehyde very quickly, so the transfor-
shown in Table 2. Aromatic aldehydes provided excellent yields of
products, whereas aliphatic aldehydes afforded phosphonates in
moderate yields, which is expected that aromatic aldehydes have
higher reactivity than aliphatic aldehydes. Both electron-donating
and electron-withdrawing substitutions of aromatic amines
provided excellent yields showing slight influences on the
reactions. It is noteworthy to mention that, in the case of
mation goes to path a to afford the corresponding
a-aminopho-
cyclohexylamine, the corresponding
was obtained in only 55% yield, and another solid byproduct
was obtained in a very short time in 35% isolated yield, which was
a
-aminophosphonate 3q
sphonates. However, for cyclohexylamine, the imine is not
immediately formed in the three component reaction and
thus there is a competition between the addition of diethyl
characterized as the corresponding
While secondary amines (e.g. piperidine, diethyl amine and
morpholine) were utilized as substrates, the corresponding
hydroxyphosphonates were the only products.
a
-hydroxyphosphonate 4q.
phosphite on the aldehyde and on the imine. Once
xyphosphonate is generated, it will not react with amine to form
-aminophosphonate even with long time heating (path b).
While secondary amines are utilized, the only product
a-hydro-
a
-
a
a
-
The mechanism of Kabacknik–Fields reaction was studied and
explained by some researchers in recent years [17]. According to
hydroxyphosphonate is afforded, because the corresponding
imines cannot be formed.
[()TD$FIG]
Scheme 3. The proposed mechanism of the one-pot reaction promoted by Yb(PFO)3.

104
J. Tang et al. / Journal of Fluorine Chemistry 132 (2011) 102–106
3. Conclusion
4.3.3. Diethyl (3-chloroaniline)(phenyl)methylphosphonate (3c)
White solid; Mp: 122–123 8C [18a]. 1H NMR (400 MHz CDCl3)
d
In summary, Yb(PFO)3 was found to be an efficient catalyst in
one-pot reaction of aldehydes, amines, and diethyl phosphite to
1.09 (t, J = 7.2 Hz, 3H), 1.28 (t, J = 7.2 Hz, 3H), 3.59–3.69 (m, 1H),
3.87–3.97 (m, 1H), 4.06–4.20 (m, 2H), 4.74 (dd, J = 8.0 Hz,
J = 24.4 Hz, 1H), 5.36 (br, s, 1H), 6.46 (dd, J = 2.0 Hz, J = 8.4 Hz,
1H), 6.61–6.65 (m, 2H), 6.96 (t, J = 8 Hz, 1H), 7.25–7.33 (m, 3H),
afford
a-aminophosphonates in good to excellent yields under
solvent-free conditions. The procedure has many advantages such
as short reaction time, small amount of catalyst used and easily
recycled, especially the avoidance of harmful organic solvents in
the reaction process, which provides a green and efficient method
7.47 (d, J = 7.2 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d 147.86,
147.71, 135.57, 134.80, 130.11, 128.68, 128.59, 128.10, 128.07,
127.93, 127.88, 118.07, 113.81, 111.83, 63.84, 63.41, 63.31, 63.24,
56.57, 55.07, 16.50, 16.44, 16.24, 16.19.
for synthesis of
a-aminophosphonates.
4.3.4. Diethyl (4-chloroaniline)(phenyl)methylphosphonate (3d)
4. Experimental
White solid; Mp: 111–113 8C [18b]. 1H NMR (400 MHz CDCl3)
d
1.10 (t, J = 6.8 Hz, 3H), 1.29 (t, J = 6.8 Hz, 3H), 3.62–3.72 (m, 1H),
3.88–3.98 (m, 1H), 4.08–4.21 (m, 2H), 4.74 (d, J = 24 Hz, 1H), 5.20
(br, s,1H), 6.55 (d, J = 8.8 Hz, 1H), 7.03 (d, J = 9.2 Hz, 2H), 7.25–7.35
4.1. Method and apparatus
Melting points were determined on a Kofler hot plate.1H
and 13C spectra were recorded on
spectrometer using TMS as internal reference, operating at
400 MHz for 1H NMR, 100 MHz for 13C NMR. For 1H NMR,
(m, 3H), 7.48 (d, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
a
Bruker AVANCE 400
147.86, 147.71, 135.57, 134.80, 130.11, 128.67, 128.59, 128.10,
128.07, 127.93, 127.88, 118.07, 113.81, 111.83, 63.48, 63.41, 63.31,
63.24, 56.57, 55.07, 16.50, 16.44, 16.24, 16.19.
chemical shifts were reported downfield from CDCl3
(d:
7.26 ppm). For 13C NMR, chemical shifts were reported in the
4.3.5. Diethyl (4-fluoroaniline)(phenyl)methylphosphonate (3e)
scale relative to the solvent of CDCl3
internal reference.
(
d
: 77.0 ppm) used as an
White solid; Mp: 111–112 8C [18c]. 1H NMR (400 MHz CDCl3)
d
1.09 (t, J = 6.8 Hz, 3H), 1.27 (t, J = 6.8 Hz, 3H), 3.62–3.72 (m, 1H),
3.87–3.97 (m, 1H), 4.05–4.19 (m, 2H), 4.71(d, J = 24.4 Hz, 1H), 4.99
(br, s,1H), 6.53–6.56 (m, 2H), 6.78 (t, J = 8.8 Hz, 2H), 7.22–7.33 (m,
4.2. Catalyst preparation
3H), 7.47 (d, J = 7.2 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d 146.01,
The preparation and characterization of rare earth metal
catalysts have been reported in our previous works [16d].
144.87, 135.43, 129.00, 128.10, 128.07, 127.85, 127.85, 127.79,
123.02, 115.00, 63.48, 63.41, 63.36, 63.29, 56.90, 55.40, 16.46,
16.39, 16.20, 16.14.
4.3. General procedure for synthesis of
a-aminophosphonates
4.3.6. Diethyl (4-nitroaniline)(phenyl)methylphosphonate (3f)
A mixture of aldehyde (1 mmol, 1.0 equiv.), amine (1 mmol,
1.0 equiv.), diethyl phosphite (1.2 mmol, 1.2 equiv.), and ytterbi-
um perfluorooctanoate (1 mol%) under solvent-free conditions
was stirred under air. After completion of the reaction as
monitored by TLC, methylene chloride (5 ml) was added. The
catalyst was filtered and washed with methylene chloride (5 ml).
The combined filtrates and washing methylene chloride were
concentrated under reduced pressure and the following purifica-
Yellow solid; Mp: 145–146 8C [11c]. 1H NMR (400 MHz CDCl3)
d
1.12(t, J = 7.2 Hz, 3H), 1.32 (t, J = 7.2 Hz, 3H), 3.60–3.70 (m, 1H),
3.89–3.99 (m, 1H), 4.10–4.24 (m, 2H), 4.45 (dd, J = 7.6 Hz, J = 24 Hz,
1H), 6.34 (br s, 1H), 6.43 (d, J = 9.2 Hz, 1H), 7.29–7.38 (m, 3H), 7.50
(d, J = 7.2 Hz, 2H), 8.01(d, J = 9.2 Hz, 2H); 13C NMR (100 MHz,
CDCl3)
d 152.23, 138.84, 134.46, 128.59, 128.88, 128.50, 128.47,
127.86, 127.81, 126.04, 112.39, 63.90, 63.83, 63.39, 63.32, 56.26,
54.74, 16.47, 16.41, 16.21, 16.15.
tion on silica gel afforded pure
a-aminophosphonate 3. The filter
residue, which was the catalyst, was dried under vacuum and
reused in the next reaction. All the products were characterized by
spectral methods as well as by comparison of their spectral data
with those reported earlier.
4.3.7. Diethyl (4-methylaniline)(phenyl)methylphosphonate (3g)
White solid; Mp: 117–118 8C [11c]. 1H NMR (400 MHz CDCl3)
d
1.14 (t, J = 7.2 Hz, 3H), 1.31 (t, J = 7.2 Hz, 3H), 2.21 (s, 3H), 3.66–3.76
(m, 1H), 3.92–4.01 (m, 1H), 4.07–4.21 (m, 2H), 4.77 (d, J = 24 Hz,
1H), 6.55 (d, J = 8 Hz, 2H), 6.94 (d, J = 8 Hz, 2H), 7.26–7.30 (m, 1H),
7.36 (t, J = 7.4 Hz, 2H), 7.50 (d, J = 7.2 Hz, 2H); 13C NMR (100 MHz,
4.3.1. Diethyl (phenyl)(phenylamino)methylphosphonate (3a)
White solid; Mp: 91–93 8C [11a]. 1H NMR (400 MHz CDCl3)
d
CDCl3) d 136.04, 129.68,128.68, 128.59, 127.89, 127.84, 127.61,
1.13 (t, J = 6.8 Hz, 3H), 1.30 (t, J = 6.8 Hz, 3H), 3.66–3.75 (m, 1H),
3.91–4.00 (m, 1H), 4.06–4.21 (m, 2H), 4.80 (d, J = 24.4 Hz, 1H), 4.87
(br, s, 1H), 6.62 (d, J = 8.4 Hz, 2H), 6.70 (t, J = 6.8 Hz, 1H), 7.11 (t,
J = 7.6 Hz, 2H), 7.27–7.36 (m, 3H), 7.50 (d, J = 7.6 Hz, 2H); 13C NMR
113.99, 63.31, 63.26, 63.24, 63.19, 57.10, 55.61, 20.37, 16.48, 16.43,
16.24, 16.18.
4.3.8. Diethyl (4-methoxyaniline)(phenyl)methylphosphonate (3h)
(100 MHz, CDCl3)
d
146.39, 146.25, 135.92, 129.17, 128.61, 128.58,
Gray solid; Mp: 78–80 8C [18c]. 1H NMR (400 MHz CDCl3)
d
127.94, 127.88, 118.40, 113.86, 63.32, 63.29, 63.26, 63.22, 56.83,
55.33, 16.46, 16.40, 16.21, 16.16.
1.14(t, J = 6.8 Hz, 3H), 1.28 (t, J = 6.8 Hz, 3H), 3.66 (s, 3H), 3.68–3.78
(m, 1H), 3.89–3.99 (m, 1H), 4.06–4.19 (m, 2H), 4.72 (d, J = 24 Hz,
1H), 6.57 (d, J = 8.8 Hz, 2H), 6.69 (d, J = 8.8 Hz, 2H), 7.23–7.28 (m,
1H), 7.32 (t, J = 7.4 Hz, 2H), 7.47 (d, J = 7.2 Hz, 2H); 13C NMR
4.3.2. Diethyl (2-chloroaniline)(phenyl)methylphosphonate (3b)
White solid; Mp: 85–86 8C [11c]. 1H NMR (400 MHz CDCl3)
d
(100 MHz, CDCl3) d 152.64, 140.47, 140.31, 136.08, 128.56, 127.94,
1.09 (t, J = 7.2 Hz, 3H), 1.20 (t, J = 7.2 Hz, 3H), 3.67–3.77 (m, 1H),
3.90–3.98 (m, 1H), 3.98–4.10 (m, 2H), 4.78 (dd, J = 7.6 Hz,
J = 24.4 Hz, 1H), 5.41–5.46 (m, 1H), 6.43 (d, J = 8 Hz, 1H), 6.53 (t,
J = 7.6 Hz, 1H), 6.68 (t, J = 8 Hz, 1H), 7.17–7.28 (m, 4H), 7.42 (d,
127.89, 115.25, 114.72, 63.34, 63.27, 63.25, 63.18, 57.70, 56.20,
55.61, 29.68, 16.45, 16.39, 16.21, 16.15.
4.3.9. Diethyl (2-nitrobenzaldehyde)(phenylamino)
J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d
142.38, 142.24,
methylphosphonate (3i)
135.33, 135.30, 128.61, 128.01, 127.68, 127.63, 119.92, 118.46,
112.64, 63.44, 63.37, 63.32, 63.25, 56.52, 55.16, 16.39, 16.34, 16.20,
16.14.
White solid; Mp: 155–156 8C [18e]. 1H NMR (400 MHz CDCl3)
d
1.11 (t, J = 7.09 Hz, 3H), 1.33 (t, J = 7.09 Hz, 3H), 3.77–3.88 (m, 1H),
3.92–4.02 (m, 1H), 4.12–4.26 (m, 2H), 5.05(br, s, 1H), 6.20 (dd,

J. Tang et al. / Journal of Fluorine Chemistry 132 (2011) 102–106
105
J = 3.8 Hz, J = 22.8 Hz, 1H), 6.71 (d, J = 8 Hz, 2H), 6.76 (t, J = 7.2 Hz,
1H), 7.15–7.19 (m, 2H),7.42–7.46 (m, 1H), 7.57 (t, J = 8 Hz, 1H),
7.76–7.78 (m, 1H), 8.03 (d, J = 8 Hz, 2H); 13C NMR (100 MHz, CDCl3)
3.77 (s, 3H), 3.90–3.99 (m, 1H), 4.04–4.21 (m, 2H) 4.80 (dd,
J = 7.6 Hz, J = 23.2 Hz, 1H), 6.36 (br, s, 1H), 6.63 (d, J = 9.2 Hz, 2H),
6.88 (d, J = 8.4 Hz, 2H), 7.40 (d, 2H), 7.99 (d, J = 9.2 Hz, 2H); 13C
d
149.48, 149.43, 145.46, 145.31, 133.54, 133.51, 131.96, 129.44,
NMR (100 MHz, CDCl3) d 159.67, 152.67, 152.31, 152.18, 138.71,
128.94, 128.79, 128.56, 128.53, 125.27, 118.84, 113.59, 63.93,
63.86, 63.44, 63.33, 50.69, 49.19, 16.40, 16.34, 15.98, 15.92.
129.04, 129.00, 126.40, 126.02, 114.28, 112.38, 63.83, 63.77, 63.30,
63.24, 55.15, 54.55, 22.64, 16.46, 16.40, 16.28, 16.22, 14.11.
4.3.10. Diethyl (3-nitrobenzaldehyde)(phenylamino)
4.3.16. Diethyl (isobutylaldehyde)(phenylamino)methylphosphonate
methylphosphonate (3j)
(3p)
Yellow solid; Mp: 95–97 8C [18e]. 1H NMR (400 MHz CDCl3)
d
Yellow oil [18d]. 1H NMR (400 MHz CDCl3)
d 1.07(t, 6H), 1.18 (t,
1.20 (t, J = 6.8 Hz, 3H), 1.32 (t, J = 6.8 Hz, 3H), 3.87–3.97 (m, 1H),
4.02–4.10 (m, 1H), 4.11–4.26 (m, 2H), 4.90 (d, J = 24.8 Hz, 1H), 4.97
(br, s, 1H), 6.60 (d, J = 7.6 Hz, 2H), 6.75 (t, J = 7.6 Hz, 1H), 7.14 (t,
J = 7.6 Hz, 2H), 7.54 (t, J = 8 Hz, 1H), 7.86 (d, J = 7.6 Hz, 1H), 8.15 (d,
J = 7.2 Hz, 3H), 1.29 (t, J = 7.2 Hz, 3H), 2.27 (t, 1H), 3.66 (dd,
J = 3.2 Hz, J = 18.8 Hz, 1H), 3.94–4.18 (m, 4H), 6.67–6.74 (m, 3H),
7.17 (t, J = 7.6 Hz, 2H); 13C NMR (100 MHz, CDCl3)
d 147.79, 147.74,
129.27, 117.87, 113.30, 62.68, 62.61, 61.85, 61.78, 56.97, 55.46,
29.90, 29.84, 20.75, 20.63, 18.06, 18.01, 16.47, 16.41, 16.35.
J = 8 Hz, 1H), 8.37–8.40 (m, 1H); 13C NMR (100 MHz, CDCl3)
d
148.48, 148.76, 146.64, 138.91, 133.84, 133.79, 129.58, 129.56,
129.36, 122.97, 122.84, 122.79, 119.03, 113.03, 113.82, 63.77,
63.70, 63.46, 63.39, 56.46, 54.93, 16.49, 16.41, 16.27, 16.22.
4.3.17. Diethyl ((cyclohexylamine)phenyl)methylphosphonate (3q)
Yellow oil [18f]. 1H NMR (400 MHz CDCl3)
d
1.01–2.68 (t, 17H),
3.62–3.72 (m, 1H), 3.80–3.89 (m, 1H), 3.97–4.07 (m, 2H), 4.12 (d,
J = 22 Hz, 1H), 7.18–7.33 (m, 5H); 13C NMR (100 MHz, CDCl3)
4.3.11. Diethyl (4-nitrobenzaldehyde)(phenylamino)
d
methylphosphonate (3k)
136.68, 136.66, 128.36, 128.30, 128.25, 127.57, 127.54, 63.06,
62.99, 62.56, 62.49, 58.29, 56.77, 53.44, 53.29, 34.27, 31.90, 25.98,
24.77, 24.30, 16.39, 16.33, 16.13, 16.08.
Yellow solid; Mp: 125–126 8C [11a]. 1H NMR (400 MHz CDCl3)
d
1.21(t, J = 6.8 Hz, 3H), 1.32 (t, J = 6.8 Hz, 3H), 3.85–3.95 (m, 1H),
4.02–4.10 (m, 1H), 4.11–4.26 (m, 2H), 4.88 (d, J = 25.2 Hz, 1H), 6.56
(d, J = 7.6 Hz, 2H), 6.71–6.78 (m, 1H), 7.11–7.15 (m, 2H), 7.68–7.71
(m, 2H), 8.19–8.24 (m, 2H); 13C NMR (100 MHz, CDCl3)
.146.80, 146.66, 144.16, 129.36, 128.73, 123.75, 119.09, 113.82,
63.79, 63.70, 63.46, 63.39, 56.42, 54.49, 16.46, 16.41, 16.29, 16.24.
4.4. Diethyl hydroxy(phenyl)methylphosphonate (4q)
d 147.63,
White solid; Mp: 82–84 8C [18g]. 1H NMR (400 MHz CDCl3)
d
1.22 (t, J = 7 Hz, 3H), 1.27 (t, J = 7 Hz, 3H), 3.94–4.09 (m, 4H), 5.03
(d, J = 10.8 Hz, 1H), 7.29–7.39 (m, 3H), 7.47–7.49 (m, 2H); 13C NMR
4.3.12. Diethyl (4-chlorobenzaldehyde)(phenylamino)
(100 MHz, CDCl3) d 136.50, 128.30, 127.08, 127.02, 71.62, 70.40,
methylphosphonate (3l)
63.40, 63.33, 63.16, 63.09, 16.40, 16.34, 16.30.
White solid; Mp: 75–76 8C [12]. 1H NMR (400 MHz CDCl3)
d
1.21(t, J = 7.2 Hz, 3H), 1.32 (t, J = 7.2 Hz, 3H), 3.85–3.95 (m, 1H),
4.02–4.10 (m, 1H), 4.11–4.26 (m, 2H), 4.80 (d, J = 24.8 Hz, 1H), 5.14
(br, s, 1H), 6.61 (d, J = 8 Hz, 2H), 6.69 (t, J = 7.6 Hz, 1H), 7.09 (t,
J = 7.8 Hz, 2H), 7.29 (d, J = 8 Hz, 2H), 7.43–7.46 (m, 2H); 13C NMR
(100 MHz, CDCl3) d 146.17, 146.03, 134.68, 133.73, 129.24, 129.19,
128.81, 128.79, 118.64, 113.87, 63.53, 63.46, 63.41, 63.34, 56.27,
54.93, 16.46, 16.41, 16.30, 16.24.
Acknowledgements
This research was financially supported by the National Nature
Science Foundation of China (20672035) and Key Laboratory of
Organofluorine Chemistry, Shanghai Institute of Organic Chemis-
try, Chinese Academy of Sciences.
4.3.13. Diethyl (4-methylbenzaldehyde)(phenylamino)
Appendix A. Supplementary data
methylphosphonate (3m)
White solid; Mp: 66–67 8C [11a]. 1H NMR (400 MHz CDCl3)
d
Supplementary data associated with this article can be found, in
the online version, at doi:10.1016/j.jfluchem.2010.12.002.
1.16 (t, J = 6.8 Hz, 3H), 1.31 (t, J = 6.8 Hz, 3H), 2.34 (s, 3H), 3.66–3.77
(m, 1H), 3.91–4.02 (m, 1H), 4.09–4.20 (m, 2H), 4.74–4.84 (m, 2H),
6.63 (d, J = 7.7 Hz, 2H), 6.72 (t, J = 7.2 Hz, 1H), 7.10–7.18 (m, 4H),
7.37–7.40 (m, 2H); 13C NMR (100 MHz, CDCl3)
d 146.50, 146.35,
References
137.61, 137.58, 132.77, 129.34, 129.34, 129.32, 129.22, 129.16,
127.78, 127.72, 118.33, 113.88, 63.29, 63.26, 63.22, 63.19, 56.52,
55.02, 21.16, 16.49, 16.44, 16.28, 16.22.
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