Iron-doped single walled carbon nanotubes as an efficient and reusable heterogeneous catalyst for the synthesis of organophosphorus compounds under solvent-free conditions

Article abstract of DOI:10.1016/j.tet.2013.03.073

Iron-doped single walled carbon nanotubes (Fe/SWCNTs) is an efficient, eco-friendly, and reusable heterogeneous catalyst for the synthesis of diversely decorated α-aminophosphonates via multicomponent reaction of amines, carbonyl compounds, and phosphorus compounds under solvent-free conditions. This methodology illustrates a very simple procedure, with wide applicability, extending the scope to aliphatic and aromatic amines and carbonyl compounds. It also enabled the development of one-pot synthesis of β-phosphonomalonates during the reaction of carbonyl compounds, malononitrile and phosphorus compounds. Excellent results were obtained in each case affording the corresponding organophosphorus adducts in good yields.

Full text of DOI:10.1016/j.tet.2013.03.073

Tetrahedron xxx (2013) 1e17
Contents lists available at SciVerse ScienceDirect
Tetrahedron
journal homepage: www.elsevier.com/locate/tet
Iron-doped single walled carbon nanotubes as an efficient and
reusable heterogeneous catalyst for the synthesis of
organophosphorus compounds under solvent-free conditions
*
Hashem Sharghi , Sakineh Ebrahimpourmoghaddam, Mohammad Mahdi Doroodmand
Department of Chemistry, College of Science, Shiraz University, Shiraz 71454, Iran
a r t i c l e i n f o
a b s t r a c t
Article history:
Iron-doped single walled carbon nanotubes (Fe/SWCNTs) is an efficient, eco-friendly, and reusable
Received 9 December 2012
Received in revised form 24 February 2013
Accepted 18 March 2013
Available online xxx
heterogeneous catalyst for the synthesis of diversely decorated
a-aminophosphonates via multicom-
ponent reaction of amines, carbonyl compounds, and phosphorus compounds under solvent-free con-
ditions. This methodology illustrates a very simple procedure, with wide applicability, extending the
scope to aliphatic and aromatic amines and carbonyl compounds. It also enabled the development of
one-pot synthesis of b-phosphonomalonates during the reaction of carbonyl compounds, malononitrile
and phosphorus compounds. Excellent results were obtained in each case affording the corresponding
organophosphorus adducts in good yields.
Keywords:
a
-Aminophosphonates
Carbon nanotubes
Heterogeneous catalyst
Iron-doped
Ó 2013 Elsevier Ltd. All rights reserved.
Organophosphorus
b
-Phosphonomalonates
Solvent free
1. Introduction
used as standard nucleophilic species for the construction of CeP
bonds, in which various compounds can act as the acceptor, such as
Organophosphorus compounds have been found a wide range
of applications in the areas of industrial, agricultural, and medicinal
chemistry owing to their biological and physical properties as well
as their utility as synthetic intermediates.1 In particular, com-
pounds of tetracoordinated pentavalent phosphorus bearing het-
imines (ketimines),6 carbonyl groups,7 alkylidene malonates,8
a,b-
unsaturated carbonyl compounds,9 nitroalkenes,10 and so on.
Recently, one-pot three-component KabachnikeFields synthesis
-aminophosphonates starting from aldehydes, amines, and
of
a
dialkyl/trialkyl phosphites have been reported using Lewis and
Brønsted acid catalysts, heteropoly acids, heterogeneous catalysts,
and nano catalysts.6 On the other hand, phospha-Michael addition,
that is, the addition of a phosphorous nucleophile to an electron-
deficient alkene has evoked remarkable attention by organic
eroatomic substituents in the a- and b-position to the phosphorus
atom have shown strong activities as antibiotics, anticancer drugs,
antibacterial agents, antiviral agents, enzyme inhibitors, peptide
mimetic, insecticides, herbicides, fungicides, as well as plant
growth regulators.2 They have also become important in the
treatment of bone disorders and in medical decalcification.3 From
their physical properties, phosphonates are used as fire retardants
for materials.4 In this regard, the wide application of phosphonates
has provoked the search for simple, efficient, and cost-effective
procedures for the synthesis of such significant scaffolds in recent
years.2,5
chemists. Synthesis of b-phosphonomalonates by this method is
most commonly promoted by bases, Brønsted/Lewis acids, transi-
tion metals, and radical initiators, such as AIBN or microwaves.8
Although, some of these approaches are effective and for satis-
factory synthesis of phosphonates, many of them cause reactor and
plant corrosion problems, involve tedious separation procedures,
require prolonged reaction times, and need use of toxic organic
solvents and also are expensive. With regard to this, it is of great
practical importance to develop a more efficient, convenient, and
also an environmentally benign method using inexpensive and
readily available reagents for the synthesis of these scaffolds.
Heterogeneous-reagent systems have many advantages, such as
simple experimental procedures, mild reaction conditions, and the
A large number of useful transformations have been achieved
during the past decades, in which dialkyl/trialkyl phosphites were
* Corresponding author. Tel.: þ98 711 646 0724; fax: þ98 711 646 0788; e-mail
addresses: hashemsharghi@gmail.com, shashem@chem.susc.ac.ir (H. Sharghi).
0040-4020/$ e see front matter Ó 2013 Elsevier Ltd. All rights reserved.
http://dx.doi.org/10.1016/j.tet.2013.03.073
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
Table 1
minimization of chemical wastes as compared to their liquid phase
counterparts.11 Catalysis is currently recognized as a potential field
of application for carbon nanotubes (CNTs), and throughout the
past decade the number of publications and patents on this subject
has been increasing exponentially.12
As a part of our program aiming at developing efficient and
environmentally friendly heterogeneous catalysts for organic syn-
thesis, we have developed iron-doped single walled carbon nano-
tubes (Fe/SWCNTs) as an easily prepared, air stable, water tolerated,
and recyclable catalyst in promoting acylation of alcohols, phenols,
acids, and amines with acid chlorides or acid anhydrides under
solvent-free conditions.13 In this paper, we report a practical, facile,
Screening of different catalyst for the synthesis of diethyl (4-methoxybenzaldehyde)
(phenylamino) methylphosphonatea
O
OEt
OEt
NH
H
O
P
H3CO
H
P
neat, 50 ºC
OEt
OEt
O
H3CO
NH2
Entry
Catalyst
Yieldb (%)
and efficient method for the synthesis of
a-aminophosphonates
1
2
3
4
5
6
7
8
dc
25
40
25
35
35
45
30
60
55
80
95
97
97
and -phosphonomalonates via reaction of amines/malononitrile,
b
Pure SWCNTsd
carbonyl compounds and phosphorus compound, promoted by Fe/
SWCNTs under solvent-free conditions (Scheme 1).
Pure MWCNTsd
TiO2/MWCNTs
ZnO/MWCNTs
TiO2/SWCNTs
R3 NH2
OR
O
Nano SnO2
Nano-Fe
Fe/MWCNTs
Fe/SWCNTs
Fe/SWCNTs (5.0 mol %)
Fe/SWCNTs (7.0 mol %)
Fe/SWCNTs (10.0 mol %)
P
R1
R2
OR
H
P
NH
R3
9
OR
OR
O
10
11
12
13
Fe/SWCNTs
O
R1
R2
or
RO
OR
P
OR
OR
O
P
OR
R1
R2
a
p-Methoxy-benzaldehyde (1.0 mmol), aniline (1.0 mmol) and diethyl phosphite
CN
(1.2 mmol), catalyst (2.4 mol %), solvent free, 50 ꢀC, 1 h.
b
NC
CN
CN
Determined by 1H NMR analysis.
In the absence of catalyst.
0.02 g was used.
c
d
Scheme 1.
Table 2
The dependence of yield on the solvent and temperaturea
2. Results and discussion
2.1. Optimization of reaction
Entry
Solvent
Temperature (ꢀC)
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
d
30
50
80
50
50
50
50
3
1
0.8
4
4
60
95
98
10
55
45
60
d
d
In search for an effective catalyst, for our initial screening ex-
periments, the implementation of three-component strategies to
obtain a-aminophosphonates in the presence of different catalysts
H2O
EtOH
CHCl3
Dioxane
4
4
was allowed. 4-Methoxybenzaldehyde and aniline were selected as
model substrates and treated with diethyl phosphite (Table 1).
When reaction was carried out in the absence of catalyst, the
product yield was 25% after 1 h (Table 1, entry 1). The reaction did
not proceed well when single-walled CNTs (SWCNTs) and multi-
walled CNTs (MWCNTs) were employed, (Table 1, entries 2 and
3), whereas the yield of product was higher in the case of SWCNTs.
The use of TiO2-doped MWCNTs, ZnO-doped MWCNTs, TiO2-doped
SWCNTs, and Nano SnO2 did not provide desired product in ac-
ceptable yields (Table 1, entries 4e7). Although, Nano-Fe and Fe-
doped MWCNTs could accelerate the reaction to produce the tar-
get compound diethyl (4-methoxybenzaldehyde) (phenylamino)
methylphosphonate, they could not provide satisfactory yields
(Table 1, entries 8 and 9). We observed an increase in the reaction
yield using Fe/SWCNTs (2.4 mol %). The optimum amount of
nanocatalyst loading in this one-pot and three component reaction,
was found to be 5.0 mol %, (Table 1, entry 11). By lowering the
catalyst loading to 2.4 mol %, the desired product was obtained in
lower yield while increasing of the catalyst loading to 10.0 mol %
has no significant effect on reaction rate and isolated yield of
product (Table 1, entries 10e13).
a
Reaction conditions: p-methoxy-benzaldehyde (1.0 mmol), aniline (1.0 mmol),
and diethyl phosphite (1.2 mmol) with 5.0 mol % of the catalyst.
b
Determined by 1H NMR analysis.
reaction was sluggish in H2O probably due to the poor solubility of
both the catalyst and the substrates (Table 2, entry 4). Other sol-
vents improved yield less than neat condition (Table 2, entries
5e7). The best rate was observed when the reaction was carried out
under neat condition at 50 ꢀC (Table 2, entry 2).
2.2. Characterization of Fe/SWCNTs
The recent studies have shown that, for the efficient use of CNT
structural properties, particularly as catalyst in organic synthesis,
CNT bundles should be activated.14 In this study, oxygen was used
for purification and functionalization of CNT bundles at 500 ꢀC for
about 2 h. To characterize the functionalized CNTs, the same
amounts of each CNT sample was mixed with about 100 equiv KBr
powder. The FT-IR spectrum of CNT sample is shown in Fig. 1.
According to the FT-IR spectrum, the strong peak at around
3440 cmꢁ1 is related to the OeH bond, whereas the peaks at
w1620 cmꢁ1 are related to the carbonyl groups. Based on the back
titration analysis, the amount of functionalization is w7.2% for CVD
process.
In the next step, the effect of solvent and temperature were
surveyed (Table 2, entries 1e7). It was found that the use of 5.0 mol
% of Fe-doped SWCNTs resulted in 60% formation of the corre-
sponding a
-aminophosphonates in solvent-free conditions at 30 ꢀC
within 3 h (Table 2, entry 1). Increase in the reaction temperature to
50 ꢀC led to formation of product in higher yield, in 1 h (Table 2,
entry 2). By increasing the temperature range to 80 ꢀC the yield and
time of reaction did not change significantly (Table 2, entry 3). The
To study the amount of Fe nanoparticles doped on the CNT
bundles TGA was used. The TGA instrument was adapted to study
the thermal stability as well as the purity of CNT bundles. The CNT
samples were analyzed according to a temperature program with
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
3
Fig. 1. FT-IR spectrum of CNTs, synthesized by high pressure CVD method.
Fig. 4. SEM image of Fe-doped CNTs.
a ramp of 2 ꢀC minꢁ1. According to the thermogram (Fig. 2), in-
crease in the weight percentage of the sample at temperature to
w310 ꢀC is related to the oxidation of Fe nanoparticles and for-
mation of iron oxides.
SWCNTs can be reused for 10 successive times in the new experi-
ments without yield loss and generate products with purities
similar to those obtained in the first run (Fig. 5).
Fig. 5. Recyclability of heterogeneous catalyst for the synthesis of diethyl (4-
methoxybenzaldehyde) (phenylamino) methylphosphonate. All reactions were under
the same conditions for 1 h.
Fig. 2. Thermogram of Fe/SWCNTs.
The XRD patterns of different forms of CNTs are compared in
Fig. 3. According to the XRD patterns, the strong peaks of the pu-
rified CNTs correspond to the (002), (100), and (101) planes of
graphite.15 Whereas other peaks with planes of (111) and (220) are
2.4. Comparison of the catalytic efficiency of Fe/SWCNTs with
literature
In order to compare the activity of Fe/SWCNTs with other ef-
fective selected previously known catalysts, a comparison of the
catalytic efficiency of different catalyst is collected in Table 3 to
demonstrate that the present protocol is indeed superior to the
other protocols. 4-Methoxy-benzaldehyde, aniline, and diethyl
phosphite is completely reacted in 1 h at 50 ꢀC in 95% isolated yield
using the present protocol. The use of H-beta zeolite for the prep-
aration of the same product requires reflux condition and a pro-
longed reaction time (Table 3, entry 1). In the presence of TiCl4,
Mg(ClO4)2, Tween-20, and CeO2 the reaction completed in shorter
reaction time, however, they need solvent or external source (e.g.,
ultrasonication) and could not recover for several times (Table 3,
entries 3e6). Reaction of 4-methoxy-benzaldehyde and aniline
with triethyl phosphite afforded 90% yields in 1.5 h under solvent-
free condition in the presence of Fe/SWCNTs. Although, [Cu(3,4-
tmtppa)](MeSO4)4 is equally effective, it requires long time to
complete and the reaction carried out at 80 ꢀC (Table 3, entry 10).
related to
g Fe nanoparticles.
Fig. 3. XRD pattern of CNTs synthesized by CVD process.
2.5. Fe/ASWCNTs catalyzed KabachnikeFields reaction
The SEM image of Fe-doped CNTs is shown in Fig. 4.
Encouraged by our preliminary results with respect to the phos-
phorus compound, 4-methoxybenzaldehyde and aniline were
treated with di/tri substituted phosphites under the catalytic in-
fluence of Fe/SWCNTs (Table 4, entries 1e3). All phosphites with
aliphatic and aromatic substituents worked well, giving high yields
of products.
2.3. Activity and reusability of heterogeneous catalyst
The ability to recycle and reuse of Fe/SWCNTs and the catalytic
activity of Fe/SWCNTs was studied in this system. The catalyst can
be so easily separated by centrifuging the reaction mixture after
dispersing it in acetone. The recyclability of the heterogeneous
catalytic systems was also examined for the model reactions. Fe/
Next, to ensure the efficiency and fidelity of this catalytic system
as a general methodology we subjected a series of amines and
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
Table 3
Comparison of protocols for the synthesis of diethyl (4-methoxybenzaldehyde) (phenylamino) methylphosphonatea
Entry
1
Conditions
Phosphorus compound
HP(O)(OEt)2
Time (h)
2
Yield (%)
90
Reuse
5
References
6a
H-beta zeolite/
acetonitrile/reflux
2
3
4
5
6
7
8
9
TiO2/20 mol %/50 ꢀC
TiCl4/acetonitrile/1 mol %
Mg(ClO4)2/5 mol %/rt
Tween-20/60 ꢀC/water
CeO2/5 mol %/ultrasonication
[Yb(PFO)3]/rt/1 mol %
Fe/SWCNTs
Thiamine hydrochloride (VB1)/5 mol %
[Cu(3,4-tmtppa)](MeSO4)4/0.16 mol %/80 ꢀC
Fe/SWCNTs
HP(O)(OEt)2
HP(O)(OEt)2
HP(O)(OEt)2
HP(O)(OEt)2
HP(O)(OEt)2
HP(O)(OEt)2
HP(O)(OEt)2
P(OEt)3
2.5
0.25
0.08
0.5
0.25
1
1
1
3
1.5
98
90
95
85
91
86
95
76
90
90
5
6b
6c
6d
6e
6f
d
d
d
3
3
6g
10
d
d
10
6h
6i
10
11
P(OEt)3
P(OEt)3
a
Reaction of p-methoxy-benzaldehyde, aniline, and phosphorus compound under different conditions.
aldehydes/ketones to one-pot three component reaction to
obtaine desire -aminophosphonates under the optimized condi-
attention by organic chemists.8 Spurred with the success of
KabachnikeFields reaction, the addition of phosphite to activated
conjugated alkenes that was synthesized via Knoevenagel con-
densation (KC) reaction,16 was studied using this efficient nano-
catalyst (Scheme 2). Previous optimized experimental protocol was
required to verify that, in the presence of Fe/SWCNTs (5.0 mol %), 2-
benzylidenemalononitrile with diethyl phosphite in a 1:1.2 molar
ratio are smoothly converted to diethyl 2,2-dicyano-1-
phenylethylphosphonate in satisfactory yield.
Since the optimal conditions for the efficient catalysis of the
phospha-Michael addition had been determined, to investigate the
generality and versatility of this method, the reaction was extended
to different malonates. A representative selection of compounds
obtained is depicted in Table 5.
As shown in Table 5, malonates with electron-donating and
electron-withdrawing groups underwent successful phospha-
Michael reaction with phosphites (Table 5, entries 1e10). The cat-
alyst was compatible with functional groups, such as methoxy,
halogen, and nitro (Table 5, entries 4e8). Heterocyclic malonates
with furan and thiophene scaffolds underwent smooth reactions
without any decomposition or polymerization under the present
reaction conditions (Table 5, entries 9 and 10).
a
tions with the Fe/SWCNTs catalyst as summarized in Table 4. The
described methodology illustrates a very simple procedure, with
wide applicability, extending the scope to aliphatic and aromatic
amines and carbonyl compounds. Excellent results were obtained
in each case affording the corresponding phosphonate derivatives
in 80e95% yields after 1e7 h at 50 ꢀC under solvent-free condition.
The reactions were clean and the products were isolated mostly in
excellent yields after simple work-up using recrystallization or
plate chromatography to purify.
Several functionalities present in the aromatic amines, such as
alkyl, halogen, methoxy, hydroxyl, and nitro group were tolerated. It
was found that, there was no remarkable electronic and position
effects on the three-component couplings from the aromatic amines,
since anilines with p-, m-, and o-substituents (Table 4, entries 4e14)
resulted in the corresponding
a-aminophosphonates in excellent
yields. Apart from the above amines, aliphatic amines were also se-
lected to carry out the three-component couplings. Primary aliphatic
amines, such as butyl amine and 3-aminopropan-1-ol (Table 4, en-
tries 15 and 16), was effective substrate, while secondary amines,
such as morpholine was ineffective partner for this reaction.
In another attempt, we studied the reaction with substituted
aromatic and aliphatic aldehydes. Various functionalities present in
the aryl aldehydes, such as alkyl, halogen, methoxy, hydroxyl, and
nitro groups (Table 4, entries 17e26) were compatible with the
reaction. In general, aromatic aldehydes with electron-donating
group could be accomplished the one-pot reaction as well as that
with electron-withdrawing groups. Heteroaromatic aldehydes,
such as thiophene-2-carbaldehyde and furan-2-carbaldehyde
(Table 4, entries 27 and 28) were all effective substrates to suc-
cessfully execute the solvent-free reactions by Fe/SWCNTs. An-
thracene-9-carbaldehyde as a polynuclear aromatic aldehyde also
reacted with diethyl phosphite (Table 4, entry 29) to give the de-
sired compound in good yield. Furthermore, in the case of aliphatic
aldehyde (Table 4, entries 30 and 31), the yield was quite reason-
able. In addition to aldehydes, ketones were also screened to carry
out the three-component couplings by Fe/SWCNTs under solvent-
free conditions. Aliphatic ketone (Table 4, entry 32 and 33),
smoothly produced the expected compound in acceptable yields.
However, no products were gained in the case of aromatic ketones
(Table 4, entry 34). The analytical and spectroscopic data for all
compounds described are included in the Experimental section.
As previously demonstrated, the heterogeneous catalyst is re-
cyclable and its activity is retained after 10 reaction cycles. The
conversion yield of the reactions was generally greater than 97%, as
judged by 1H NMR, so the crude needed recrystallization to purify
and compounds that did not reach this level, were purified by plate
chromatography. The analytical and spectroscopic data for all
compounds described are included in the Experimental section.
2.7. Knoevenagel condensation catalyzed by Fe/SWCNTs
The Knoevenagel condensation (KC) has been receiving con-
siderable attention, due to its broad spectrum of uses including
perfume,17 calcium antagonists,18 polymers,19 and pharmaceuticals
applications.20 Commercially this reaction was carried out using
various homogeneous base catalysts, such as piperidine, amines,
ammonia, and ammonium salts, which are corrosive, toxic, non-
reusable, and also produce neutralization waste.21 In last 10 years,
lots of methods to achieve KC are known.22 In general, KC is per-
formed in organic solvents in the presence of the bases or acids.
Recently, some novel heterogeneous catalysts, have been exploited
as catalysts for the KC.22a,23 However these methods are valuable,
some of them suffer from some drawbacks, such as long reaction
time, the use of harmful catalyst, harsh reaction conditions, stoi-
chiometric amount of catalysts, a large amount of organic solvent as
the reaction medium, and energy expenses.
2.6. Fe/SWCNTs catalyzed synthesis of
phosphonomalonates
b-
Amongst the methods for PeC bond formation, phospha-
Michael addition, that is, the addition of a phosphorous nucleo-
phile to an electron-deficient alkene has evoked remarkable
The KC reaction of benzaldehyde and malononitrile as model
substrates was studied at 80 ꢀC under solvent-free condition in the
presence of 5.0 mol % catalyst via 1H NMR spectroscopy (Table 6,
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
5
Table 4
Fe/SWCNTs catalyzed one-pot and three component reaction of amines, carbonyl compounds, and phosphorus compoundsa
Fe/SWCNTs
OR
OR
O
O
P
R3
R2
R1 NH2
50 °C/ Solvent free
R2
R3
NH
R1
H
P
RO
OR
P
OR
OR
or
1
2
3
O
OR
Entry
Amine
Carbonyl compound
Phosphorus compound
Product
Time (h)
Yieldb (%)
OEt
OEt
NH
O
P
O
NH2
H
1
HPO(OEt)2
P(OEt)3
1.0
1.5
95
90
H3CO
H3CO
1a
2a
3a
OMe
OMe
NH
O
P
NH2
2
2a
HPO(OMe)2
P(OMe)3
0.3
1.0
97
95
H3CO
1b
3b
OPh
OPh
NH
O
P
NH2
3
2a
HPO(OPh)2
P(OPh)3
1.5
4.0
95
95
H3CO
1c
3c
OEt
OEt
NH
O
P
NH2
OH
4
2a
HPO(OEt)2
P(OEt)3
3.2
5.0
82
80
OH
H3CO
1d
3d
OEt
O
P
OEt
NH
NH2
5
2a
HPO(OEt)2
1.5
92
H3CO
OCH3
1e
OCH3
3e
OEt
OEt
NH
O
P
NH2
6
2a
HPO(OEt)2
2.0
92
H3CO
CH3
1f
(continued on next page)
CH3
3f
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6
H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
Table 4 (continued )
Entry
Amine
Carbonyl compound
Phosphorus compound
Product
Time (h)
Yieldb (%)
OEt
OEt
NH
O
P
NH2
7
2a
HPO(OEt)2
2.0
90
H3CO
CH3
1g
CH3
3g
OEt
OEt
NH
O
P
NH2
CH3
8
2a
HPO(OEt)2
2.8
90
CH3
H3CO
1h
3h
OEt
O
P
NH2
OEt
NH
9
2a
HPO(OEt)2
P(OEt)3
2.5
3.5
93
93
H3CO
Cl
1i
Cl
3i
OEt
OEt
NH
O
P
NH2
10
2a
HPO(OEt)2
2.0
87
H3CO
Br
1j
Br
3j
OEt
OEt
NH
O
P
NH2
11
2a
HPO(OEt)2
P(OEt)3
2.5
3.0
84
80
H3CO
I
1k
I
3k
OEt
OEt
NH
O
P
NH2
12
2a
HPO(OEt)2
3.0
85
H3CO
NO2
1l
NO2
3l
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
7
Table 4 (continued )
Entry
Amine
Carbonyl compound
Phosphorus compound
Product
Time (h)
Yieldb (%)
OEt
OEt
NH
O
P
NH2
13
14
15
2a
HPO(OEt)2
3.5
85
H3CO
NO2
1m
NO2
3m
OEt
OEt
NH
O
P
NH2
2a
2a
2a
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
3.0
3.8
4.0
90
90
85
H3CO
CN
1n
1o
CN
3n
OEt
O
P
OEt
NH
NH2
H3CO
3o
OEt
O
P
OEt
NH
HO
NH2
16
1q
H3CO
OH
3p
OEt
O
P
OEt
NH
O
H
17
1a
HPO(OEt)2
P(OEt)3
1.0
1.5
95
95
2b
3q
OEt
O
P
O
OEt
NH
H
18
1a
HPO(OEt)2
2.0
88
HO
HO
2c
3r
OEt
OEt
NH
O
P
O
19
1a
HPO(OEt)2
P(OEt)3
1.2
2.0
95
90
H
H3C
H3C
2d
(continued on next page)
3s
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8
H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
Table 4 (continued )
Entry
Amine
Carbonyl compound
Phosphorus compound
Product
Time (h)
Yieldb (%)
OEt
OEt
NH
O
O
P
H
20
21
22
23
1a
1a
1a
1a
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
2.0
90
H3C
H3C
CH3
CH3
2e
3t
OEt
OEt
NH
O
P
O
H
3.0
2.0
3.5
90
94
92
Cl
Cl
2f
3u
OEt
OEt
NH
O
Cl
P
O
H
Cl
2g
3v
OEt
O
Cl
O
Cl
P
OEt
NH
H
O
Cl
Cl
2g
3w
OEt
OEt
NH
O
P
24
1a
HPO(OEt)2
P(OEt)3
3.0
5.0
85
85
H
O2N
O2N
2h
3x
OEt
OEt
NH
O
O
P
H
25
1a
HPO(OEt)2
3.0
90
NO2
NO2
2i
3y
OEt
OEt
NH
O
NO2
P
NO2
O
H
26
1a
HPO(OEt)2
4.0
85
2j
3z
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
9
Table 4 (continued )
Entry
Amine
Carbonyl compound
Phosphorus compound
Product
Time (h)
Yieldb (%)
O
P
OEt
OEt
S
O
H
S
OEt
NH
27
1a
HPO(OEt)2
2.0
92
2k
3aa
O
P
O
O
H
OEt
NH
O
28
1a
HPO(OEt)2
3.5
87
2l
3ab
O
H
EtO
29
1a
HPO(OEt)2
P(OEt)3
4.0
6.5
87
85
P
NH
EtO
O
2m
3ac
OEt
O
P
O
OEt
NH
H
30
31
32
33
1a
1a
1a
1a
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
4.0
5.0
6.0
5.0
85
82
80
85
H3C
H3C
2n
3ad
OEt
O
P
OEt
O
H3C
H3C
NH
H
CH3
CH3
2o
3ae
OEt
O
P
OEt
O
NH
2p
3af
O
OEt
OEt
P
O
NH
2q
(continued on next page)
3ag
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10
H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
Table 4 (continued )
Entry
Amine
Carbonyl compound
Phosphorus compound
Product
Time (h)
10.0
Yieldb (%)
O
34
1a
1a
HPO(OEt)2
Trace
d
CH3
2r
35
2a
HPO(OEt)2
3ac
1.8
90
a
Fe/SWCNTs (5.0 mol %), amine (1.0 mmol), carbonyl compound (1.0 mmol), and phosphorus compound (1.2 mmol) under solvent-free condition at 50 ꢀC.
Isolated yield.
Substrates (20 mmol) have been used.
b
c
synthesis of diversely decorated organophosphorus compounds
by use of a catalytic amount of Fe/SWCNTs as catalyst under sol-
vent-free condition. No competitive side reactions, such as the
H
P
OR
OR
O
OR
OR
P
O
Fe/SWCNTs
CN
CN
or
formation of a-hydroxyphosphonates were observed in these
CN
50 °C / Solvent free
RO
OR
transformations. Furthermore, this catalytic system can promote
Knoevenagel condensation successfully. The significant features of
this method include its ease of operation, high efficiency, chemo-
selectivity, reusability, and avoidance of harmful organic solvents in
the reaction process, which provides a green and efficient method
CN
P
R
R
OR
Scheme 2. Synthesis of
4
5
b
-phosphonomalonates.
for synthesis of
nates. Current efforts in our research group are attempting to ex-
pand the application of Fe/SWCNTs for catalyzed organic reactions.
a-aminophosphonates and b-phosphonomalo-
entry 1). As shown in Table 6, the reaction was completed after 3.5 h
to produce 2-benzylidenemalononitrile in 94% yield. Under the
identical conditions, a variety of aryl aldehydes were reacted with
malononitrile to afford 2-arylmethylidienemalononitrile in high
yields (Table 6, entries 2e10). Both electron-rich and electron-
deficient aldehydes worked well, giving high yields of products.
Electron-deficient aldehydes furnished excellent yields of the cor-
responding arylidenes in a short reaction time, whereas electron-
rich aldehydes resulted in comparatively low yields and required
longer reaction times. The analytical and spectroscopic data for all
compounds described are included in the Experimental section.
4. Experimental section
4.1. Instrumentation, analyses, and starting material
General information: scanning electron micrographs were ob-
served by SEM instrumentation (XL-30 FEG SEM, Philips, at 20 KV).
X-ray diffraction (XRD, D8, Advance, Bruker, axs) and FT-IR spec-
troscopy (Shimadzu FT-IR 8300 spectrophotometer) were
employed for characterization of the heterogeneous catalyst. TGA of
the samples was performed with a laboratory-made TGA in-
strument. NMR spectra were recorded on a Bruker Avance DPX-250
(1H NMR 250 MHz and 13C NMR 62.9 MHz) spectrometer in pure
deuterated solvents with tetramethylsilane as an internal standard.
2.8. One-pot synthesis of
by Fe/SWCNTs
b-phosphonomalonates catalyzed
Since the phospha-Michael addition reaction of 2-
benzylidenemalononitrile with diethyl phosphite using Fe/
SWCNTs has been accomplished at 50 ꢀC under solvent-free con-
dition; we hypothesized that this transformation could be obtained
in the same pot after the initial condensation, which is the Knoe-
venagel condensation of carbonyl compounds with malononitrile,
was completed. So, we have explored the viability of obtaining
Chemical shifts (d) are reported in parts per million, and coupling
constants (J) are in hertz. The following abbreviations were used to
explain the multiplicities: s¼singlet, d¼doublet, t¼triplet,
q¼quartet, m¼multiplet, and br¼broad. Mass spectra were de-
termined on a Shimadzu GCeMS-QP 1000 EX instruments at 70 or
20 ev. Elemental analyses were performed with a Thermo Finnigan
CHNSeO 1112 series analyzer. Melting points were determined in
desired b-phosphonomalonates via a KC reaction from the corre-
sponding carbonyl compounds and malononitrile, followed directly
by coupling with phosphorus compound using catalytically amount
of Fe/SWCNTs.
€
open capillary tubes in a Buchi-535 circulating oil melting point
apparatus. The purity determination of the substrates and reaction
monitoring was accomplished by TLC on silica gel PolyGram SILG/
UV254 plates. Chemical materials were purchased from Fluka,
Aldrich, and Merck Companies.
The condensation of malononitrile and benzaldehyde was car-
ried out at 80 ꢀC in the presence of 5.0 mol % of Fe/SWCNTs and
determined to be complete (by TLC against malononitrile with
CH2Cl2 as eluent and KMnO4 as stain) in 3.5 h. Upon completion of
the first step, diethyl phosphite was added and the intermediate
was converted to product in 95% yield (Table 7, entry 1). In an effort
to determine the scope and limitation of this methodology various
aldehydes were reacted with malononitrile, followed directly by
coupling with phosphorus compound (Table 7). By using this pro-
cess, the reaction times were comparable to the reaction starting
from malonates, however, the yields are higher in almost all entries.
4.2. Synthesis of Fe/SWCNTs
Fe/SWCNTs were synthesized by chemical vapor disposition
(CVD) method inside a quartz tube in a thermal furnace via de-
position of carbon vapors at high temperature (1300 ꢀC) at an inert
atmosphere of argon. The source of SWCNTs was acetylene. Carbon
vapors are then deposited on iron nanoparticles, synthesized with
CVD method24 through the decomposition of ferrocene (w14%
molar percentage). The synthesized Fe/SWCNTs were then purified
from any amorphous carbon or bulky nanomaterials, such as ful-
lerenes, and activated carbon in an on-line system by hydrogen and
oxygen etching process, ultraviolet (UV) and microwave irradiation.
The amounts of iron nanoparticles doped on SWCNTs were
3. Conclusions
In conclusion, we have demonstrated a new, efficient, eco-
friendly, chemoselective, and simple procedure for the one-pot
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
11
Table 5
Fe/SWCNTs catalyzed synthesis of b
-phosphonomalonatesa
Entry
Substrate
Phosphorus compound
Product
Time (h)
Yieldb (%)
EtO
EtO
O
P
CN
CN
1
HPO(OEt)2
P(OEt)3
3.0
6.0
94
90
CN
CN
4a
4b
5a
EtO
EtO
O
P
CN
CN
2
HPO(OEt)2
P(OEt)3
3.0
6.0
95
95
CN
Me
CN
Me
5b
EtO
O
P
CN
EtO
CN
CN
3
HPO(OEt)2
3.5
90
CN
P
Me
Me
4c
5c
EtO
EtO
O
CN
CN
4
HPO(OEt)2
3.5
95
CN
MeO
CN
MeO
4d
5d
EtO
O
P
CN
EtO
CN
5
HPO(OEt)2
3.0
92
CN
Cl
CN
4e
Cl
5e
EtO
O
P
CN
CN
EtO
CN
6
HPO(OEt)2
3.0
90
CN
CN
Cl
CN
4f
Cl
5f
EtO
EtO
O
P
CN
7
HPO(OEt)2
2.5
90
CN
Cl
4g
Cl
5g
EtO
EtO
O
P
CN
8
HPO(OEt)2
P(OEt)3
6.5
9.0
85
78
CN
CN
O2N
CN
O2N
4h
(continued on next page)
5h
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12
H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
Table 5 (continued )
Entry
Substrate
Phosphorus compound
HPO(OEt)2
Product
Time (h)
5.0
Yieldb (%)
EtO
EtO
O
P
CN
CN
O
CN
9
92
CN
O
CN
4i
5i
EtO
EtO
O
10
HPO(OEt)2
4.0
90
P
S
CN
CN
4j
S
CN
5j
a
Fe/SWCNTs (5.0 mol %), malonates (1.0 mmol), and phosphorus compound (1.2 mmol) under solvent-free condition at 50 ꢀC.
Isolated yield.
b
Table 6
controlled by optimization of the concentration of ferrocene and
the flow rate of argon.
Knoevenagel condensation using Fe/SWCNTsa
R
CN
R
CN
CN
Fe/SWCNTs
O
4.3. General procedure
°
neat, 80 C
H
CN
H
4.3.1. Solvent-free synthesis of
a-aminophosphonates catalyzed by
Fe/SWCNTs. The required carbonyl compound (1 mmol), an amine
(1 mmol), and phosphorus compound (1.2 mmol) were added to Fe/
SWCNTs (0.05 g) and the mixture was heated in an oil bath at 50 ꢀC.
The progress of the reaction was monitored by TLC. After the re-
action was complete, acetone (4ꢂ10 mL) was added to the reaction
mixture and the catalyst was separated by centrifuging. The organic
solvent was removed under reduced pressure. After purification by
recrystallization (ethyl acetate/n-hexane 10:90) or plate chroma-
Entry
R
Product
Time (h)
Yieldb (%)
1
2
3
4
5
6
7
8
9
C6H5
4a
4d
4b
4e
4g
4f
4h
4i
4j
3.5
5.0
4.5
2.5
2.5
3.5
1.5
3.5
4.0
2.5
95
80
86
95
95
92
95
82
84
92
o-MeO-C6H4
p-Me-C6H4
p-CleC6H4
m-CleC6H4
o-CleC6H4
p-NO2eC6H4
2-Furyl
2-Thienyl
4-Pyridyl
tography (ethyl acetate/n-hexane 20:80)
were obtained.
a-aminophosphonates
10
4k
a
Fe/SWCNTs (5.0 mol %), aldehyde (1.0 mmol), and malononitrile (1.0 mmol)
under solvent-free condition at 80 ꢀC.
4.3.2. Solvent-free synthesis of b-phosphonomalonates catalyzed by
b
Isolated yield.
Fe/SWCNTs. The required malonates (1 mmol) and phosphorus
compound (1.2 mmol) were added to Fe/SWCNTs (0.05 g) and the
mixture was heated in an oil bath at 50 ꢀC. After the reaction was
complete, EtOAc (4ꢂ10 mL) was added to the reaction mixture and
centrifuged to separate the catalyst. The organic solvent was removed
under reduced pressure. After purification by plate chromatography
(solvent: n-hexane/ethyl acetate, 50:50) the product was obtained.
Table 7
Fe/SWCNTs catalyzed one-pot synthesis of b
-phosphonomalonatesa
OEt
OEt
O
P
CN
R
1) Fe/SWCNTs, CH2(CN)2, neat, 80 °C
2) HP(OEt)2 / P(OEt)3, neat, 50 °C
O
4.3.3. Solvent-free Knoevenagel condensations over Fe/SWCNTs. The
required carbonyl compound (1 mmol) and malononitrile (1 mmol)
were added to Fe/SWCNTs (0.05 g) and the mixture was heated in an
oil bath at 80 ꢀC for a certain period of time as required to complete
the reaction (monitored by TLC against malononitrile with CH2Cl2 as
eluent and KMnO4 as stain). The solid mass was then eluted with
EtOAc (4ꢂ10 mL) and centrifuged to separate the catalyst. Evapora-
tion of solvent furnished the corresponding practically pure product.
CN
H
R
5
Entry
Substrate
Phosphorus
compound
Product
Timeb (h)
Yieldc (%)
1
2
C6H5
HPO(OEt)2
P(OEt)3
HPO(OEt)2
P(OEt)3
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
HPO(OEt)2
P(OEt)3
5a
5b
6.0
9.0
6.0
9.0
6.0
8.5
5.5
5.0
5.0
8.0
9.5
8.0
8.0
95
90
95
95
95
95
92
90
90
88
80
90
95
p-MeeC6H4
4.3.4. Diethyl (4-methoxyphenyl) (phenylamino) methylphosphonate
(3a).25 White crystalline solid, mp 100e102 ꢀC (lit. 101e102); 1H
3
4
5
6
7
8
m-MeeC6H4
p-MeOeC6H4
p-CleC6H4
o-CleC6H4
m-CleC6H4
p-NO2eC6H4
5c
5d
5e
5f
5g
5h
NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.38 (d, 2H, J¼7.5 Hz), 7.09 (t, 2H,
J¼8.0 Hz), 6.86 (d, 2H, J¼7.5 Hz), 6.57e6.60 (m, 3H), 4.76 (d, 1H,
JHP¼25.0 Hz), 4.50 (br s, 1H), 4.08e4.14 (m, 3H), 3.76e3.78 (m, 4H),
1.28 (t, 3H, J¼7.2 Hz), 1.13 (t, 3H, J¼7.2 Hz); 13C NMR (62.9 MHz,
CDCl3, 25 ꢀC)
d
¼159.3, 146.4, 129.1, 129.0, 128.9, 127.6, 118.3, 114.0,
9
10
2-Furyl
2-Thienyl
HPO(OEt)2
HPO(OEt)2
5i
5j
2
2
113.8, 63.3 (d, JCP¼6.9 Hz), 63.0 (d, JCP¼6.9 Hz), 56.5 (d,
JCP¼150.9 Hz), 55.2, 16.5 (d, 3JCP¼5.7 Hz), 16.3 (d, 3JCP¼5.7 Hz).
a
(1) Fe/SWCNTs (5.0 mol %), aldehyde (1.0 mmol), and malononitrile (1.0 mmol)
under solvent-free condition at 80 ꢀC, (2) phosphorus compound (1.2 mmol) under
solvent-free condition at 50 ꢀC.
4.3.5. Dimethyl (4-methoxyphenyl) (phenylamino) methylphosp
honate (3b).6d Greenish semisolid; 1H NMR (250 MHz, CDCl3, 25 ꢀC):
b
Overall one-pot time.
Isolated yield.
c
d¼7.35 (d, 2H, J¼8.8 Hz), 7.05 (t, 2H, J¼7.5 Hz), 6.84 (d, 2H, J¼9.4 Hz),
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
13
6.54e6.67 (m, 3H), 4.70 (d,1H, JHP¼24.0 Hz), 3.68e3.73 (m, 6 H), 3.43
hexane 10:90) 0.30; IR (KBr): 3294, 1596, 1512, 1242, 1180 cmꢁ1; 1H
NMR (250 MHz, CDCl3, 25 ꢀC):
13
(d, 3H, J¼8.8 Hz); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d¼159.4, 146.8,
d
¼7.33 (d, 2H, J¼8.8 Hz), 7.02 (d, 2H,
129.1, 128.8, 127.3, 118.4, 114.2, 114.1, 113.9, 56.1 (d, JCP¼153.0 Hz), 55.1,
J¼8.8 Hz), 6.84 (d, 2H, J¼7.5 Hz), 6.51 (d, 2H, J¼7.5 Hz), 5.18 (br s,
1H), 4.64 (d, 1H, JHP¼23.9 Hz), 4.06e4.13 (m, 2H), 3.75 (s, 3H),
3.61e4.05 (m, 2H), 1.27 (t, 3H, J¼7.1 Hz), 1.11 (t, 3H, J¼7.0 Hz); 13C
53.7.
4.3.6. Diphenyl (4-methoxyphenyl) (phenylamino) methylphosp
NMR (62.9 MHz, CDCl3, 25 ꢀC)
d
¼159.3, 145.0, 144.8, 128.9, 128.8,
honate (3c).6d Greenish semisolid; 1H NMR (250 MHz, DMSO-d6,
2
127.0, 122.9, 122.0, 115.0, 114.1, 63.3 (d, JCP¼6.9 Hz), 63.0 (d,
2JCP¼6.9 Hz), 55.2, 54.2 (d, JCP¼152.8 Hz), 16.4 (d, 3JCP¼5.7 Hz), 16.2
(d, 3JCP¼5.7 Hz); Mass m/z (%): 384 (Mþþ1), 383 (Mþ), 246, 202, 167,
138, 121, 83, 65; Anal. Calcd for C18H23ClNO4P (383): C, 56.33; H,
6.04. Found: C, 56.15; H, 6.30.
25 ꢀC):
d
¼7.48 (d, 2H, J¼7.5 Hz), 6.98e7.31 (m, 7H), 6.85 (d, 2H,
J¼8.5 Hz), 6.75 (d, 2H, J¼7.8 Hz), 6. 53 (t, 2H, J¼7.3 Hz), 4.97 (d, 1H,
JHP¼24.8 Hz), 3.68 (s, 3H); 13C NMR (62.9 MHz, DMSO-d6, 25 ꢀC)
d
¼158.4, 151.0, 146.9, 129.5, 129.4, 128.8, 128.6, 124.1, 120.5, 116.8,
115.2, 113.4, 55.4 (d, JCP¼153.4 Hz), 54.9.
4.3.13. Diethyl (4-bromophenylamino) (4-methoxyphenyl) methyl-
4.3.7. Diethyl (2-hydroxyphenylamino) (4-methoxyphenyl) methyl-
phosphonate (3j).6b White crystalline solid, mp 107e109 ꢀC (lit.
phosphonate (3d).6b Off white crystalline solid, mp 77e78 ꢀC (lit.
105); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.27 (d, 2H, J¼8.0 Hz),
75); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.30 (d, 2H, J¼7.5 Hz), 6.76
6.09 (d, 2H, J¼7.5 Hz), 6.77 (d, 2H, J¼7.5 Hz), 6.41 (d, 2H, J¼7.5 Hz),
4.57 (d, 1H, JHP¼25.0 Hz), 3.79e4.09 (m, 3H), 3.54e3.63 (m, 4H),
1.23 (t, 3H, J¼7.1 Hz), 1.04 (t, 3H, J¼7.0 Hz); 13C NMR (62.9 MHz,
(d, 1H, J¼7.5 Hz), 6.48e6.62 (m, 5H), 4.80 (d, 1H, JHP¼24.5 Hz),
4.22e4.28 (m, 2H), 3.87e3.95 (m, 2H), 3.62 (s, 1H), 1.29 (t, 3H,
13
J¼7.0 Hz), 1.12 (t, 3H, J¼7.1 Hz); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
CDCl3, 25 ꢀC)
d
¼159.4, 145.5, 145.2, 131.8, 128.9, 128.5, 126.9, 115.5,
d
¼159.1, 145.2, 135.1, 134.8, 129.4, 129.2, 127.4, 124.4, 119.7, 118.1,
2
2
110.0, 63.6 (d, JCP¼6.9 Hz), 63.3 (d, JCP¼6.9 Hz), 55.2, 54.0 (d,
114.3,113.9,111.9, 64.1 (d, 2JCP¼6.9 Hz), 63.7 (d, 2JCP¼6.9 Hz), 56.4 (d,
JCP¼153.5 Hz), 16.4 (d, 3JCP¼5.7 Hz), 16.2 (d, 3JCP¼5.7 Hz).
3
JCP¼155.8 Hz), 55.0, 16.4 (d, JCP¼5.7 Hz), 16.2 (d, 3JCP¼5.7 Hz).
4.3.14. Diethyl (4-iodophenylamino) (4-methoxyphenyl) methyl-
phosphonate (3k). Pale yellow crystalline solid, mp 101e103 ꢀC; Rf
(AcOEt/hexane 10:90) 0.31; IR (KBr): 3294, 1612, 1512, 1234,
4.3.8. Diethyl (4-methoxyphenyl) (4-methoxyphenylamino) methyl-
phosphonate (3e).6b White crystalline solid, mp 116e117 ꢀC (lit.
118); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.35 (d, 2H, J¼7.5 Hz),
1172 cmꢁ1; 1H NMR (250 MHz, CDCl3)
d
¼7.23e7.29 (m, 4H), 6.77 (d,
6.84 (d, 2H, J¼9.0 Hz), 6.66 (d, 2H, J¼7.5 Hz), 6.54 (d, 2H, J¼7.5 Hz),
4.65 (d, 1H, JHP¼24.5 Hz), 4.03e4.12 (m, 2H), 3.87e3.92 (m, 1H),
2H, J¼7.5 Hz), 6.31 (d, 2H, J¼8.5 Hz), 5.20 (br s, 1H), 4.57 (d, 1H,
JHP¼23.8 Hz), 4.01e4.07 (m, 2H), 3.68 (s, 3H), 3.66e3.69 (m, 1H),
3.58e3.61 (m, 1H), 1.23 (t, 3H, J¼7.1 Hz), 1.04 (t, 3H, J¼7.0 Hz); 13C
3.62e3.70 (m, 1H), 3.56 (s, 3H), 3.52 (s, 3H), 1.26 (t, 3H, J¼7.0 Hz),
13
1.11 (t, 3H, J¼7.2 Hz); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d¼159.2,
NMR (62.9 MHz, CDCl3, 25 ꢀC)
d
¼159.4, 159.3, 145.1, 145.9, 137.6,
152.5, 140.0, 132.0, 129.0, 128.9, 115.2, 114.6, 113.9, 63.3 (d,
2JCP¼6.9 Hz), 63.0 (d, 2JCP¼6.9 Hz), 57.3 (d, JCP¼152.8 Hz), 55.5, 55.1,
129.1, 128.9, 127.0, 126.9, 118.2, 116.1, 114.1, 113.8, 63.5 (d,
2JCP¼6.9 Hz), 63.2 (d, 2JCP¼6.9 Hz), 55.2, 53.9 (d, JCP¼155.0 Hz), 16.4
3
16.5 (d, 3JCP¼5.7 Hz),16.3 (d, JCP¼5.7 Hz).
3
3
(d, JCP¼5.7 Hz), 16.2 (d, JCP¼5.7 Hz); Mass m/z (%): 476 (Mþþ1),
475 (Mþ), 338, 230, 212, 121; Anal. Calcd for C18H23INO4P (475): C,
45.49; H, 4.88. Found: C, 45.63; H, 4.52.
4.3.9. Diethyl (p-toluidino) (4-methoxyphenyl) methylphosphonate
(3f).6b White crystalline solid, mp 95e97 ꢀC (lit. 96); 1H NMR
(250 MHz, CDCl3, 25 ꢀC):
d
¼7.29 (dd, 2H, J1¼9.5, J2¼2.5 Hz), 6.76e6.85
(m, 4H, J¼8.5 Hz), 6.43 (d, 2H, J¼7.5 Hz), 4.60 (d, 1H, JHP¼24.5 Hz),
4.04e4.11 (m, 2H), 3.79e3.95 (m,1H), 3.70 (s, 3H), 3.55e3.60 (m,1H),
2.10 (s, 3H), 1.20 (t, 3H, J¼7.0 Hz), 1.06 (t, 3H, J¼7.0 Hz); 13C NMR
4.3.15. Diethyl (4-methoxyphenyl) (4-nitrophenylamino) methyl-
phosphonate (3l).6g Yellow crystalline solid, mp 110e112 ꢀC (lit.
107e108); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.90 (d, 2H,
(62.9 MHz, CDCl3, 25 ꢀC)
d
¼159.2, 144.1, 143.8, 129.6, 128.9, 127.9,
J¼9.3 Hz), 7.40 (d, 2H, J¼8.5 Hz), 7.10 (br s, 1H), 6.79 (d, 2H,
J¼8.9 Hz), 6.65 (d, 2H, J¼9.3 Hz), 4.94 (d, 1H, JHP¼23.8 Hz),
4.09e4.19 (m, 2H), 3.83e3.8 (m, 1H), 3.75 (s, 3H), 3.58e3.76 (m,
1H), 1.23 (t, 3H, J¼7.1 Hz), 1.09 (t, 3H, J¼7.0 Hz); 13C NMR (62.9 MHz,
2
2
127.7, 114.0, 63.3 (d, JCP¼6.9 Hz), 63.0 (d, JCP¼6.9 Hz), 56.8 (d,
JCP¼155.3 Hz), 55.2, 20.4, 16.5 (d, 3JCP¼5.7 Hz), 16.3 (d, 3JCP¼5.7 Hz).
CDCl3, 25 ꢀC)
d
¼159.5, 152.9, 138.2, 129.2, 129.1, 126.6, 126.5, 125.8,
4.3.10. Diethyl (m-toluidino) (4-methoxyphenyl) methylphosphonate
(3g).6b Off white crystalline solid, mp 83e84 ꢀC (lit. 86); 1H NMR
2 2
114.1, 114.0, 112.3, 63.7 (d, JCP¼6.9 Hz), 63.3 (d, JCP¼6.9 Hz), 55.1,
53.2 (d, JCP¼154.5 Hz), 16.4 (d, 3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
(250 MHz, CDCl3, 25 ꢀC):
d
¼7.89 (d, 2H, J¼7.5 Hz), 7.16 (t, 1H,
J¼7.8 Hz), 6.67 (d, 2H, J¼7.0 Hz), 6.55e6.58 (m, 3H), 4.65 (br s, 1H),
4.53 (d, 1H, JHP¼24.5 Hz), 3.66e3.91 (m, 4H), 3.40 (s, 3H), 1.91 (s,
3H),1.02 (t, 3H, J¼7.0 Hz), 0.93 (t, 3H, J¼7.0 Hz); 13C NMR (62.9 MHz,
4.3.16. Diethyl (4-methoxyphenyl) (3-nitrophenylamino) methyl-
phosphonate (3m).6b Yellow crystalline solid, mp 148e150 ꢀC (lit.
1
CDCl3, 25 ꢀC)
d
¼159.2, 146.7, 138.6, 128.9, 127.9, 119.0, 114.8, 113.9,
148); H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.47e7.53 (m, 2H), 7.40
2
2
113.5, 110.8, 63.2 (d, JCP¼6.9 Hz), 62.9 (d, JCP¼6.9 Hz), 56.3 (d,
(d, 2H, J¼8.7 Hz), 7.13e7.25 (m, 2H), 7.16 (t, 1H, J¼7.5 Hz), 6.83e6.89
(m, 3H), 5.95 (br s,1H), 4.80 (d,1H, JHP¼24.0 Hz), 4.24e4.08 (m, 2H),
3.89e4.01 (m, 1H), 3.75 (s, 3H), 3.62e3.75 (m, 1H), 1.29 (t, 3H,
JCP¼152.3 Hz), 55.0, 21.5, 16.4 (d, 3JCP¼5.7 Hz), 16.2 (d, 3JCP¼5.7 Hz).
13
J¼7.0 Hz), 1.13 (t, 3H, J¼7.0 Hz); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
4.3.11. Diethyl (o-toluidino) (4-methoxyphenyl) methylphosphonate
(3h).6b White crystalline solid, mp 67e68 ꢀC (lit. 65); 1H NMR
d
¼159.5, 149.1, 147.7, 147.5, 129.5, 129.1, 126.7, 119.9, 114.1, 112.4,
108.2, 63.7 (d, 2JCP¼6.9 Hz), 63.2, 63.2 (d, 2JCP¼6.9 Hz), 55.2, 53.7 (d,
(250 MHz, CDCl3, 25 ꢀC):
d
¼7.29 (dd, 2H, J1¼8.8, J2¼2.3 Hz),
JCP¼154.1 Hz), 16.4 (d, JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
3
6.75e6.97 (m, 4H), 6.54 (t, 1H, J¼7.3 Hz), 6.32 (d, 1H, J¼8.0 Hz), 4.66
(d, 1H, JHP¼24.5 Hz), 4.50 (br s, 1H), 3.86e4.1(m, 3H), 3.69 (s, 3H),
3.56e3.66 (m, 1H), 2.18 (s, 3H), 1.19 (t, 3H, J¼7.1 Hz), 1.06 (t, 3H,
4.3.17. Diethyl (3-cyanophenylamino) (4-methoxyphenyl) methyl-
13
phosphonate (3n).6b White crystalline solid, mp 120e121 ꢀC (lit.
J¼7.1 Hz); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d¼158.2, 143.3, 129.1,
117); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.35 (d, 2H, J¼8.7 Hz), 7.15
127.8, 126.5, 125.8, 121.9, 116.9, 113.0, 112.9, 110.2, 62.3 (d,
2JCP¼6.9 Hz), 62.0 (d, 2JCP¼6.9 Hz), 55.5, 53.1 (d, JCP¼152.3 Hz), 16.5,
(t, 1H, J¼7.5 Hz), 6.78e6.95 (m, 5H), 5.21 (br s, 1H), 6.65 (d, 1H,
JHP¼24.0 Hz), 4.04e4.19 (m, 2H), 3.87e3.97 (m, 1H), 3.87 (s, 3H),
3.57e3.85 (m, 1H), 1.29 (t, 3H, J¼7.0 Hz), 1.12 (t, 3H, J¼7.0 Hz); 13C
15.4, 15.3 (d, 3JCP¼5.7 Hz), 15.1 (d, JCP¼5.7 Hz).
3
NMR (62.9 MHz, CDCl3, 25 ꢀC)
121.6, 119.2, 118.2, 116.1, 114.2, 112.8, 63.6 (d, JCP¼6.9 Hz), 63.2 (d,
d
¼159.5, 146.9, 129.8, 128.9, 126.5,
4.3.12. Diethyl (4-chlorophenylamino) (4-methoxyphenyl) methyl-
phosphonate (3i). White crystalline solid, mp 85e87 ꢀC; Rf (AcOEt/
2
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14
H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
2JCP¼6.9 Hz), 55.2, 53.9 (d, JCP¼153.1 Hz), 16.4 (d, 3JCP¼5.7 Hz), 16.2
(d, 3JCP¼5.7 Hz).
(250 MHz, CDCl3, 25 ꢀC):
d
¼7.35 (d, 2H, J¼8.5 Hz), 7.21 (d, 2H,
J¼8.0 Hz), 7.02 (t, 2H, J¼7.5 Hz), 6.62 (t, 1H, J¼7.5 Hz), 6.48 (d, 2H,
J¼7.7 Hz), 4.65 (d, 1H, JHP¼24.8 Hz), 3.61e4.11 (m, 4H), 1.20 (t, 3H,
J¼7.0 Hz), 1.07 (t, 3H, J¼6.9 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
4.3.18. Diethyl (4-methoxyphenyl) (butylylamino) methylphospho
1
nate (3o).6b Oil; H NMR (250 MHz, CDCl3, 25 ꢀC):
d¼7.32 (d, 2H,
d
¼146.1, 145.9, 134.6, 134.5, 133.7, 133.6, 129.2, 128.8, 128.7, 118.6,
2
2
J¼8.5 Hz), 6.80 (d, 2H, J¼8.5 Hz), 4.85 (d, 1H, JHP¼24.0 Hz),
113.8, 63.4 (d, JCP¼6.9 Hz), 63.3 (d, JCP¼6.9 Hz), 56.7 (d,
3.40e3.71 (m, 4H), 3.71 (s, 3H), 2.28e2.46 (m, 2H), 1.05e1.37 (m,
JCP¼150.2 Hz), 16.4 (d, 3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
10H), 0.77 (t, 3H, J¼7.0 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
2
d
¼159.3, 132.0, 128.5, 113.6, 63.2 (d, JCP¼6.9 Hz), 63.0 (d,
4.3.25. Diethyl (2-chlorophenyl) (phenylamino) methylphosphonate
2JCP¼6.9 Hz), 58.9 (d, JCP¼154.2 Hz), 55.1, 47.6, 31.8, 20.2, 16.4 (d,
(3v). White crystalline solid, mp 99e101 ꢀC; Rf (AcOEt/hexane
3JCP¼5.7 Hz), 16.3 (d, 3JCP¼5.7 Hz), 13.9.
10:90) 0.40; IR (KBr): 3332, 1604, 1434, 1249, 1026 cmꢁ1 1H NMR
;
(250 MHz, CDCl3, 25 ꢀC):
d
¼7.99 (d, 1H, J¼7.9 Hz), 7.76 (d, 1H,
4.3.19. Diethyl (3-hydroxypropylamino) (4-methoxyphenyl) methyl-
J¼7.5 Hz), 7.54 (t, 1H, J¼7.5 Hz), 7.44 (t, 1H, J¼7.8 Hz), 7.14 (t, 2H,
J¼7.5 Hz), 6.69e6.75 (m, 3H), 6.15 (d, 1H, JHP¼24.0 Hz), 5.15 (br s,
phosphonate (3p).6b White solid, mp 114e115 ꢀC (lit. 113); 1H NMR
(250 MHz, CDCl3, 25 ꢀC):
d
¼8.01 (br s, 1H), 7.21 (d, 2H, J¼7.5 Hz),
1H), 4.14e4.20 (m, 2H), 3.79e3.95 (m, 2H), 1.30 (t, 3H, J¼7.0 Hz),
13
6.70 (d, 2H, J¼7.5 Hz), 4.89 (d, 1H, JHP¼24.2 Hz), 3.50e3.85 (m, 4H),
1.09 (t, 3H, J¼7.0 Hz); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d¼149.4,
3.70 (s, 3H), 3.23e3.45 (m, 2H), 2.20e2.43 (m, 2H), 1.05e1.47 (m,
145.4, 133.5, 133.4, 129.4, 129.2, 128.8, 125.2, 118.7, 113.5, 63.7 (d,
2JCP¼6.9 Hz), 63.2 (d, 2JCP¼6.9 Hz), 51.1 (d, JCP¼151.0 Hz), 48.6, 16.3
(d, 3JCP¼5.6 Hz), 16.0 (d, 3JCP¼5.6 Hz); Mass m/z (%):353 (Mþ), 227,
180, 104; Anal. Calcd for C17H21ClNO3P (353): C, 57.71; H, 5.98.
Found: C, 57.99; H, 5.89.
5H), 1.07 (t, 3H, J¼7.0 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
2
d
¼159.5, 132.2, 128.0, 113.8, 63.3 (d, JCP¼6.9 Hz), 62.9 (d,
2JCP¼7.0 Hz), 59.5 (d, JCP¼154.5 Hz), 55.4, 46.6, 30.2, 16.4 (d,
3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
4.3.20. Diethyl
(3q).25 White crystalline solid, mp 92e93 ꢀC (lit. 91e93); 1H NMR
(250 MHz, CDCl3, 25 ꢀC):
phenyl
(phenylamino)
methylphosphonate
4.3.26. Diethyl
(2,6-dichlorophenyl)
(phenylamino)
methyl-
phosphonate (3w).27 (references do not report melting point)
d
¼7.39 (d, 2H, J¼7.6 Hz), 7.17e7.24 (m, 3H),
White crystalline solid, mp 74e76 ꢀC; 1H NMR (250 MHz, CDCl3,
7.01 (t, 2H, J¼8.0 Hz), 6.50e6.62 (m, 3H), 4.73 (br s, 1H), 4.50 (d, 1H,
JHP¼24.6 Hz), 3.99e4.13 (m, 2H), 3.79e3.89 (m, 1H), 3.53e3.60 (m,
1H), 1.19 (t, 3H, J¼7.0 Hz), 1.02 (t, 3H, J¼7.0 Hz); 13C NMR (62.9 MHz,
25 ꢀC):
d
¼7.19 (d, 1H, J¼8.9 Hz), 6.91e7.02 (m, 4H), 6.53e6.56 (m,
3H), 5.85 (d, 1H, JHP¼24.5 Hz), 5.16 (br s, 1H), 4.05e4.14 (m, 2H),
3.92e3.95 (m, 1H), 3.76e3.79 (m, 1H), 1.21 (t, 3H, J¼7.0 Hz), 1.01 (t,
CDCl3, 25 ꢀC)
d
¼146.4, 146.2, 130.2, 129.1, 128.6, 128.5, 127.9, 127.8,
3H, J¼6.9 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼145.8, 145.5,
d
2
2
118.6, 113.3, 63.3 (d, JCP¼6.9 Hz), 63.2 (d, JCP¼6.9 Hz), 57.2 (d,
136.7, 136.6, 134.7, 131.4, 130.3, 129.2, 128.7, 118.7, 113.4, 112.9, 63.3
(d, 2JCP¼6.9 Hz), 63.0 (d, 2JCP¼6.9 Hz), 54.3 (d, JCP¼151.0 Hz), 16.4 (d,
3JCP¼5.6 Hz), 16.1 (d, 3JCP¼5.6 Hz).
JCP¼151.0 Hz), 16.5 (d, 3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
4.3.21. Diethyl
(4-hydroxyphenyl)
(phenylamino)
methyl-
¼7.89
1
phosphonate (3r).25 Oil; H NMR (250 MHz, CDCl3, 25 ꢀC):
d
4.3.27. Diethyl (4-nitrophenyl) (phenylamino) methylphosphonate
(d, 2H, J¼7.5 Hz), 7.16 (t, 1H, J¼7.8 Hz), 6.67 (d, 2H, J¼7.0 Hz),
6.55e6.58 (m, 3H), 4.65 (br s, 1H), 4.53 (d, 1H, JHP¼24.5 Hz),
3.66e3.91 (m, 4H), 3.40 (s, 3H), 1.02 (t, 3H, J¼7.0 Hz), 0.93 (t, 3H,
(3x).25 Yellow crystalline solid, mp 126e127 ꢀC (lit. 125e126); 1H
NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼8.09 (d, 2H, J¼8.8 Hz), 7.55e7.61
(m, 2H), 7.01 (t, 2H, J¼7.5 Hz), 6.62 (t, 1H, J¼7.7 Hz), 6.45 (d, 2H,
J¼7.8 Hz), 4.87 (br s, 1H), 4.80 (d, 1H, JHP¼25.0 Hz), 3.72e4.14 (m,
4H),1.20 (t, 3H, J¼7.0 Hz),1.09 (t, 3H, J¼6.9 Hz); 13C NMR (62.9 MHz,
J¼7.0 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼158.3, 157.2, 146.8,
d
146.2, 131.0, 130.5, 129.0, 127.6, 117.3, 114.0, 113.8, 63.5 (d,
2JCP¼6.9 Hz), 63.2 (d, JCP¼6.9 Hz), 56.2 (d, JCP¼151.5 Hz), 16.5 (d,
CDCl3, 25 ꢀC)
d
¼147.5, 145.8, 144.1, 129.3, 128.7, 128.6, 118.9, 113.7,
2
3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
63.8 (d, JCP¼6.9 Hz), 63.5 (d, JCP¼6.9 Hz), 57.0 (d, JCP¼148.3 Hz),
2
2
16.4 (d, 3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
4.3.22. Diethyl (4-methylphenyl) (phenylamino) methylphosphonate
(3s).25 White crystalline solid, mp 64e65 ꢀC (lit. 66e67); 1H NMR
4.3.28. Diethyl (3-nitrophenyl) (phenylamino) methylphosphonate
1
(250 MHz, CDCl3, 25 ꢀC):
d
¼7.34e7.37 (m, 2H), 7.07e7.13 (m, 4H),
(3y).25 Yellow crystalline solid, mp 98e99 ꢀC (lit. 95e97); H NMR
6.62 (t, 1H, J¼7.2 Hz), 6.58 (d, 2H, J¼7.7 Hz), 4.57 (d, 1H,
JHP¼23.5 Hz), 4.50 (br s, 1H), 4.07e4.15 (m, 2H), 3.91e4.97 (m, 1H),
3.66e3.77 (m, 1H), 2.30 (s, 3H), 1.29 (t, 3H, J¼7.0 Hz), 1.15 (t, 3H,
(250 MHz, CDCl3, 25 ꢀC):
d¼8.29 (s,1H), 8.05 (d,1H, J¼9.5 Hz), 7.76 (d,
1H, J¼7.7 Hz), 7.40 (t, 1H, J¼7.5 Hz), 7.01 (t, 2H, J¼7.8 Hz), 6.48e6.65
(m, 3H), 5.46 (br s, 1H), 4.82 (d, 1H, JHP¼24.8 Hz), 3.73e4.15 (m, 4H),
1.20(t, 3H, J¼7.0 Hz),1.09 (t, 3H, J¼7.0 Hz); 13C NMR (62.9 MHz, CDCl3,
J¼6.9 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼146.7, 146.4, 137.4,
2
d
132.9, 129.3, 129.2, 127.9, 127.8, 118.1, 113.8, 63.2 (d, JCP¼6.9 Hz),
25 ꢀC)
d
¼148.4, 145.8, 145.6, 138.9, 138.8, 133.9, 133.8, 129.2, 122.9,
2
63.1 (d, JCP¼6.9 Hz), 56.9 (d, JCP¼151.0 Hz), 21.1, 16.4 (d,
122.8,118.8,113.7, 63.8 (d, 2JCP¼6.9 Hz), 63.4 (d, 2JCP¼6.9 Hz), 56.7 (d,
3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
JCP¼150.1 Hz), 16.4 (d, 3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
4.3.23. Diethyl (4-isopropylphenyl) (phenylamino) methylphospho
nate (3t).26 (references do not report melting point) White crys-
talline solid, mp 101e102 ꢀC; 1H NMR (250 MHz, CDCl3, 25 ꢀC):
4.3.29. Diethyl (2-nitrophenyl) (phenylamino) methylphosphonate
(3z).25 Yellow crystalline solid, mp 155e157 ꢀC (lit. 155e156); 1H
NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼8.00 (d, 1H, J¼7.7 Hz), 7.70e7.73
d
¼7.38 (d, 2H, J¼7.5 Hz), 7.08e7.28 (m, 4H), 6.60e6.72 (m, 3H), 4.75
(m, 1H), 7.43 (t, 1H, J¼7.9 Hz), 7.13 (t, 2H, J¼7.5 Hz), 6.66e6.75 (m,
3H), 5.27 (d, 1H, JHP¼23.5 Hz), 4.56 (br s, 1H), 4.14e4.20 (m, 2H),
(d, 1H, JHP¼25.0 Hz), 4.07e4.15 (m, 2H), 3.88e3.95 (m, 1H),
3.62e3.72 (m, 1H), 2.82e2.90 (m, 1H), 1.20e1.31 (m, 9H),1.07 (t, 3H,
3.82e3.96 (m, 2H), 1.30 (t, 3H, J¼7.0 Hz), 1.09 (t, 3H, J¼7.0 Hz); 13
C
J¼6.9 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d
¼148.4, 144.1, 129.6,
NMR (62.9 MHz, CDCl3, 25 ꢀC)
d
¼149.3, 145.5, 133.5, 133.4, 131.9,
128.9, 127.8, 127.5, 114.0, 63.2 (d, 2JCP¼6.9 Hz), 63.1 (d, 2JCP¼6.9 Hz),
129.4, 128.8, 125.2, 113.5, 63.7 (d, 2JCP¼6.9 Hz), 63.3 (d, 2JCP¼6.9 Hz),
51.0 (d, JCP¼151.0 Hz), 16.4 (d, 3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
3
56.7 (d, JCP¼152.2 Hz), 33.6, 23.8, 16.4 (d, JCP¼5.6 Hz), 16.2 (d,
3JCP¼5.6 Hz).
4.3.30. Diethyl (phenylamino) (thiophen-2-yl) methylphosphonate
4.3.24. Diethyl (4-chlorophenyl) (phenylamino) methylphosphonate
(3aa).27 Off white semisolid, 1H NMR (250 MHz, CDCl3, 25 ꢀC):
(3u).25 White crystalline solid, mp 77e80 ꢀC (lit. 75e76); 1H NMR
d¼6.98e7.08 (m, 4H), 6.82 (t, 1H, J¼4.5 Hz), 6.55e6.64 (m, 3H), 4.95
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
15
(d, 1H, JHP¼24.8 Hz), 4.72 (br s, 1H), 3.67e4.14 (m, 4H), 1.14 (t, 3H,
J¼7.0 Hz), 1.06 (t, 3H, J¼6.9 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
J¼7.6 Hz), 7.85 (s, 1H), 7.30e7.65 (m, 3H); 13C NMR (62.9 MHz,
CDCl3, 25 ꢀC)
d
¼160.2, 134.8, 130.8, 129.8, 129.0, 113.7, 112.4, 83.0.
d
¼146.3, 139.9, 129.2, 127.1, 126.2, 125.3, 125.2, 118.8, 113.9, 63.6 (d,
2
2JCP¼6.9 Hz), 63.4 (d, JCP¼6.9 Hz), 53.2 (d, JCP¼157.1 Hz), 16.5 (d,
4.3.38. 2-(4-Methylbenzylidene)malononitrile (4b).31 Yellow crys-
talline solid, mp 134e135 C (lit. 131); 1H NMR (250 MHz, CDCl3,
3JCP¼5.6 Hz), 16.3 (d, 3JCP¼5.6 Hz).
25 ꢀC):
d
¼7.79 (d, 2H, J¼8.2 Hz), 7.72 (s, 1H), 7.46 (d, 2H, J¼9.8 Hz),
4.3.31. Diethyl furan-2-yl(phenylamino) methylphosphonate (3ab).27
2.47 (s, 3H), 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
130.1, 113.5, 112.7, 83.5, 22.0.
d
¼159.5, 147.1, 130.7,
1
Off white semisolid; H NMR (250 MHz, CDCl3, 25 ꢀC):
d¼7.28 (s,
1H), 7.05 (t, 2H, J¼7.5 Hz), 6.56e6.68 (m, 3H), 6.21e6.31 (m, 2H),
4.82 (d, 1H, JHP¼24.8 Hz), 4.24 (br s, 1H), 3.72e4.12 (m, 4H), 1.20 (t,
3H, J¼7.0 Hz), 1.11 (t, 3H, J¼6.9 Hz); 13C NMR (62.9 MHz, CDCl3,
4.3.39. 2-(4-Methoxybenzylidene)malononitrile
(4d).30 Yellow
crystalline solid, mp 115e117 C (lit. 119); 1H NMR (250 MHz, CDCl3,
25 ꢀC)
d
¼149.3, 146.1, 145.9, 142.4, 129.1, 118.8, 113.9, 110.8, 110.7,
25 ꢀC):
d¼7.94 (d, 2H, J¼8.8 Hz), 7.57 (s, 1H), 7.03 (d, 2H, J¼8.5 Hz),
2
2
108.2, 108.7, 63.5 (d, JCP¼6.9 Hz), 63.3 (d, JCP¼6.9 Hz), 51.4 (d,
3.88 (s, 3H), 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
115.1, 114.4, 55.8.
d
¼158.8, 133.4, 124.0,
JCP¼159.1 Hz), 16.4 (d, 3JCP¼5.6 Hz), 16.2 (d, 3JCP¼5.6 Hz).
4.3.32. Diethyl anthracen-10-yl (phenylamino) methylphosphonate
(3ac). Pale brown crystalline solid, mp 159e160 ꢀC; Rf (AcOEt/hex-
ane 10:90) 0.35; IR (KBr): 3294,1604,1496,1242,1110 cmꢁ1; 1H NMR
4.3.40. 2-(4-Chlorobenzylidene)malononitrile (4e).30 Pale yellow
crystalline solid, mp 166e167 ꢀC (lit. 165); 1H NMR (250 MHz,
CDCl3, 25 ꢀC):
d
¼7.81 (d, 2H, J¼8.2 Hz), 7.71 (s, 1H), 7.50 (d, 2H,
(250 MHz, CDCl3, 25 ꢀC):
d¼9.11 (d, 1H, J¼9.0 Hz), 8.53 (d, 1H,
J¼8.5 Hz), 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼158.1, 141.3, 131.9,
d
J¼9.2 Hz), 8.43 (s, 1H), 8.05 (d, 1H, J¼8.3 Hz), 7.95 (d, 1H, J¼8.5 Hz),
7.59e7.44 (m, 4H), 6.98 (t, 2H, J¼7.7), 6.53e6.61 (m, 3H), 6.42 (d, 1H,
JHP¼27.0 Hz), 5.21 (br s, 1H), 4.22e4.34 (m, 2H), 3.71e3.80 (m, 1H),
3.28e3.32 (m, 1H), 1.38 (t, 3H, J¼7.0 Hz), 0.69 (t, 3H, J¼7.0 Hz); 13C
130.0, 129.3, 113.3, 112.2, 83.3.
4.3.41. 2-(2-Chlorobenzylidene) malononitrile (4f).32 Pale yellow
crystalline solid, mp 95e96 ꢀC (lit. 95.5); 1H NMR (250 MHz, CDCl3,
NMR (62.9 MHz, CDCl3, 25 ꢀC)
d
¼147.1,146.9,131.9,130.5,129.8,129.1,
25 ꢀC):
d
¼8.26 (s, 1H), 8.19 (d, 1H, J¼7.8 Hz), 7.26e7.59 (m, 3H), 13
C
128.9,127.8,126.7,125.1,124.7,122.7,116.1,113.4, 63.4 (d, 2JCP¼6.9 Hz),
63.0 (d, 2JCP¼6.9 Hz), 54.1 (d, JCP¼152.8 Hz),16.6 (d, 3JCP¼5.6 Hz),15.8
(d, 3JCP¼5.6 Hz); Mass m/z (%): 419 (Mþ), 282,104, 57; Anal. Calcd for
NMR (62.9 MHz, CDCl3, 25 ꢀC)
113.8, 81.2.
d
¼149.6, 148.0, 143.1, 123.7, 114.4,
C25H26NO3P (419): C, 71.59; H, 6.25. Found: C, 71.75; H, 6.17.
4.3.42. 2-(3-Chlorobenzylidene)malononitrile (4g).31 Oil; 1H NMR
(250 MHz, CDCl3, 25 ꢀC):
¼7.75e7.87 (m, 1H), 7.53 (s, 1H),
7.39e7.52 (m, 1H), 7.19 (s, 1H); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼158.3, 134.1, 130.4, 128.3, 112.2, 111.2, 80.0.
d
4.3.33. Diethyl 1-(phenylamino) butylphosphonate (3ad).6b Oil; 1H
NMR (250 MHz, CDCl3, 25 ꢀC):
13
d
¼7.08 (t, 2H, J¼8.5 Hz), 6.56e6.68
d
(m, 3H), 3.87e4.08 (m, 4H), 3.60e3.65 (m, 2H), 1.50e1.93 (m, 4H),
1.08e1.30 (m, 6H), 0.85 (t, 3H, J¼6.9 Hz); 13C NMR (62.9 MHz,
4.3.43. 2-(4-Nitrobenzylidene)malononitrile (4h).33 Yellow solid,
mp 159e160 ꢀC (lit. 158e159), 1H NMR (250 MHz, CDCl3, 25 ꢀC):
CDCl3, 25 ꢀC)
d
¼147.3, 129.2, 117.8, 113.2, 62.7 (d, 2JCP¼6.9 Hz), 61.8
2
(d, JCP¼6.9 Hz), 51.9 (d, JCP¼156.3 Hz), 32.8, 19.3, 19.1, 16.5 (d,
d
¼7.94 (d, 2H, J¼7.8 Hz), 7.71 (s, 1H), 7.00 (d, 2H, J¼7.5 Hz), 13C NMR
3JCP¼5.6 Hz), 16.3 (d, 3JCP¼5.6 Hz), 13.8.
(62.9 MHz, DMSO-d6, 25 ꢀC)
d
¼160.0, 150.0, 136.3, 130.9, 124.6,
112.2, 85.5.
4.3.34. Diethyl (isobutylaldehyde) (phenylamino) methylphospho
1
nate (3ae).25 Oil; H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.72 (t, 2H,
4.3.44. 2-(2-Furylmethylidene)malononitrile (4i).34 Yellow solid,
mp 69e70 ꢀC (lit. 67e68); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
¼7.87
J¼7.5 Hz), 6.56e6.63 (m, 3H), 3.86e4.04 (m, 5H), 3.56 (d, 1H,
d
JHP¼17.8 Hz), 2.12e2.23 (m, 1H), 1.93 (t, 3H, J¼7.0 Hz), 0.97e1.10 (m,
(s, 1H), 7.59 (d, 1H, J¼2.5), 7.35 (d, 1H, J¼3.9 Hz), 6.43 (t, 1H,
13
9H); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d
¼147.7, 129.2, 119.8, 117.7,
J¼3.8 Hz), 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼149.3, 146.1, 144.1,
d
2
2
113.2, 62.7 (d, JCP¼6.9 Hz), 61.8 (d, JCP¼6.9 Hz), 57.3 (d,
122.5, 114.0, 113.2, 111.5, 77.1.
2
3
JCP¼151.3 Hz), 29.8 (d, JCP¼5.8 Hz), 20.7 (d, JCP¼12.3 Hz), 18.0 (d,
3JCP¼4.5 Hz), 16.4 (d, 3JCP¼5.6 Hz), 16.3 (d, 3JCP¼5.6 Hz).
4.3.45. 2-(2-Thienylmethylidene)malononitrile (4j).34 Yellow solid,
mp 90e93 ꢀC (lit. 91e92); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
4.3.35. Diethyl 1-(phenylamino) cyclohexylphosphonate (3af).6b
Colorless crystalline solid, mp 98e99 ꢀC (lit. 104 ꢀC); 1H NMR
d
¼7.77e7.89 (m, 3H), 7.26e7.34 (m,1H); 13C NMR (62.9 MHz, CDCl3,
25 ꢀC)
d
¼150.2, 138.5, 137.0, 128.9, 120.2, 118.3, 81.9.
(250 MHz, CDCl3, 25 ꢀC):
d
¼7.09 (t, 2H, J¼7.5 Hz), 6.96 (d, 2H,
J¼8.6 Hz), 6.72 (t, 1H, J¼7.4 Hz), 3.91e4.02 (m, 4H), 3.38 (br s, 1H),
4.3.46. 2-(4-Pyridylmethylidene)malononitrile (4k).34 Yellow solid,
2.09e2.12 (m, 2H), 1.40e1.75 (m, 8H), 1.14e1.19 (m, 6H); 13C NMR
mp 75e76 ꢀC (lit. 78e80); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d¼8.87
(62.9 MHz, CDCl3, 25 ꢀC)
d
¼145.8, 128.7, 119.3, 118.4, 62.1 (d,
(m, 2H, J¼7.4 Hz), 7.82 (s, 1H), 7.70 (d, 2H, J¼7.3 Hz); 13C NMR
2JCP¼6.9 Hz), 62.0 (d, 2JCP¼6.9 Hz), 58.4 (d, JCP¼161.2 Hz), 30.2, 25.3,
(62.9 MHz, CDCl3, 25 ꢀC)
111.4, 88.3.
d
¼156.1, 157.3, 151.2, 137.2, 122.7, 112.3,
19.9 (d, 2JCP¼11.1 Hz), 16.5 (d, 3JCP¼5.6 Hz), 16.4 (d, 3JCP¼5.6 Hz).
4.3.36. Diethyl 3,3-dimethyl-2-(phenylamino)butan-2-
4.3.47. Diethyl 2,2-dicyano-1-phenylethylphosphonate
ylphosphonate (3ag).6b Colorless oil; 1H NMR (250 MHz, CDCl3,
(5a).28 Yellow solid, mp 53e54 ꢀC (lit. 56e58); 1H NMR
25 ꢀC):
d
¼7.02 (d, 2H, J¼7.5 Hz), 6.81 (t, 2H, J¼7.5 Hz), 6.42 (d, 2H,
(250 MHz, CDCl3, 25 ꢀC):
d
¼7.34e7.40 (m, 5H), 4.60 (t,1H, J¼7.9 Hz),
J¼7.4 Hz), 3.98e4.12 (m, 4H), 3.85 (br s, 1H), 1.89 (d, 3H, J¼10.4 Hz),
4.05e4.12 (m, 4H), 3.87e3.94 (m, 2H), 3.54 (dd, 1H, J1¼7.9,
13
1.23e1.27 (m, 6H), 1.19 (s, 9H); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
J2¼21.5 Hz), 1.29 (t, 3H, J¼7.1 Hz), 1.13 (t, 3H, J¼7.1 Hz); 13C NMR
d
¼149.8, 129.9, 119.5, 117.4, 71.8 (d, JCP¼155.2 Hz), 63.1 (d,
(62.9 MHz, CDCl3, 25 ꢀC)
d
¼130.4, 129.4, 129.2, 128.8, 111.6, 111.4,
2
2
2
2JCP¼6.9 Hz), 62.9 (d, JCP¼6.9 Hz), 30.7, 28.6, 18.5, 16.5 (d,
64.3 (d, JCP¼7.1 Hz), 63.4 (d, JCP¼7.2 Hz), 45.7 (d, JCP¼144.4 Hz),
3JCP¼5.6 Hz), 16.4 (d, 3JCP¼5.6 Hz).
25.6, 16.3 (d, 3JCP¼5.9 Hz), 16.1 (d, JCP¼5.7 Hz).
3
4.3.37. 2-Benzylidenemalononitrile (4a).29 Yellow solid, mp
4.3.48. Diethyl 2,2-dicyano-1-p-tolylethylphosphonate (5b).28
Yellow solid, mp 93e95 ꢀC (lit. 88e90); 1H NMR (250 MHz,
83e85 ꢀC (lit. 83); 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d¼7.89 (d, 2H,
Please cite this article in press as: Sharghi, H.; et al., Tetrahedron (2013), http://dx.doi.org/10.1016/j.tet.2013.03.073

16
H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
13
CDCl3, 25 ꢀC):
d
¼7.26 (d, 2H, J¼8.3 Hz), 7.19 (d, 2H, J¼7.2 Hz), 4.42 (t,
J¼7.1 Hz); C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d
3
¼149.5, 147.9, 123.7,
3
1H, J¼8.4 Hz), 4.05e4.13 (m, 3H), 3.92e3.95 (m, 1H), 3.47 (dd, 1H,
113.7, 112.5, 64.3 (d, JCP¼7.1 Hz), 63.8 (d, JCP¼7.2 Hz), 40.4 (d,
J1¼8.0, J2¼21.5 Hz), 2.29 (s, 3H), 1.28 (t, 3H, J¼7.0 Hz), 1.05 (t, 3H,
JCP¼147.6 Hz), 26.7, 16.4 (d, 3JCP¼5.3 Hz), 16.2 (d, 3JCP¼5.2 Hz).
J¼7.0 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼140.2, 130.2, 129.1,
d
129.0, 126.5, 111.2, 111.0, 64.4 (d, 2JCP¼7.1 Hz), 63.3 (d, 2JCP¼7.2 Hz),
4.3.56. Diethyl 2,2-dicyano-1-(thiophen-2-yl) ethyl phosphonate
3
45.4 (d, JCP¼144.4 Hz), 25.7, 21.2, 16.3 (d, JCP¼5.9 Hz), 16.1 (d,
(5j).8c Brown oil; 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d¼7.25e7.31
3JCP¼5.7 Hz).
(m, 2H), 7.01 (t, 1H, J¼4.5 Hz), 4.44 (t, 1H, J¼8.5 Hz), 4.08e4.16 (m,
4H), 3.91 (dd, 1H, J1¼7.5, J2¼22.3 Hz), 1.28 (t, 1H, J¼7.1 Hz), 1.09 (t,
4.3.49. Diethyl 2,2-dicyano-1-m-tolylethyl phosphonate (5c).28
Yellow solid, mp 55e56 ꢀC (lit. 56e57); 1H NMR (250 MHz,
1H, J¼7.1 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼140.8, 136.6,
d
129.5, 127.7, 111.2, 111.0, 64.6 (d, 2JCP¼7.1 Hz), 63.9 (d, 2JCP¼7.3 Hz),
3
CDCl3, 25 ꢀC):
d
¼7.15e7.39 (m, 4H, J¼8.3 Hz), 4.52 (t, 1H, J¼7.8 Hz),
41.3 (d, JCP¼148.2 Hz), 26.7, 16.3 (d, JCP¼5.1 Hz), 16.1 (d,
4.05e4.12 (m, 2H), 3.69e3.94 (m, 2H), 3.48 (dd, 1H, J1¼8.2,
3JCP¼5.0 Hz).
J2¼21.4 Hz), 2.28 (s, 3H), 1.27 (t, 3H, J¼7.0 Hz), 1.01 (t, 3H, J¼7.0 Hz);
13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d¼139.1,130.3,130.2,129.9,129.2,
126.2, 111.5, 111.4, 64.3 (d, 2JCP¼7.1 Hz), 63.3 (d, 3JCP¼7.2 Hz), 45.6 (d,
Acknowledgements
JCP¼144.9 Hz), 25.5, 21.5, 16.2 (d, 3JCP¼5.9 Hz), 16.0 (d, 3JCP¼5.6 Hz).
We gratefully acknowledge the support of this work by the
Shiraz University Research Council.
4.3.50. Diethyl 2,2-dicyano-1-(4-methoxyphenyl) ethyl phosphonate
(5d).28 Yellow solid, mp 60e62 ꢀC (lit. 57e58); 1H NMR (250 MHz,
DMSO-d6, 25 ꢀC):
d
¼7.13e7.17 (m, 2H), 6.74e6.79 (m, 2H),
3.68e3.82 (m, 5H), 3.67 (s, 1H), 0.96e1.20 (m, 6H); 13C NMR
References and notes
(62.9 MHz, DMSO-d6, 25 ꢀC)
d
¼172.2, 129.9, 129.8, 122.3, 115.9,
1. (a) Schug, K. A.; Lindner, W. Chem. Rev. 2005, 105, 67e114; (b) Moonen, K.;
Lauryn, I.; Stevens, C. V. Chem. Rev. 2004, 104, 6177e6215; (c) Hildebrand, R. L.;
Henderson, T. O. In The Role of Phosphonates in Living Systems; Hilderbrand, R. L.,
Ed.; CRC: Boca Raton, FL, 1983; pp 5e29.
113.3, 58.7 (d, JCP¼144.7 Hz), 55.7, 25.5,16.3 (d, 3JCP¼5.9 Hz), 16.2 (d,
3JCP¼5.7 Hz).
2. Sobhani, S.; Tashrifi, Z. Tetrahedron 2010, 66, 1429e1439.
3. Silvestrini, G.; Zini, N.; Sabatelli, P.; Mocetti, P.; Maraldi, N. M.; Bonucci, E. Bone
1996, 18, 559e565.
4. Allen, D. W.; Anderton, E. C.; Bradley, C.; Shiel, L. E. Polym. Degrad. Stab. 1995, 47,
67e72.
4.3.51. Diethyl 1-(4-chlorophenyl)-2,2-dicyanoethyl phosphonate
(5e).28 Yellow solid, mp 93e95 ꢀC (lit. 94e96); 1H NMR (250 MHz,
CDCl3, 25 ꢀC):
d
¼7.28e7.40 (m, 4H), 4.48 (t,1H, J¼8.0 Hz), 3.93e4.14
(m, 4H), 3.49 (dd, 1H, J1¼7.6, J2¼22.1 Hz), 1.31 (t, 3H, J¼7.0 Hz), 1.13
5. (a) Demmer, C. S.; Krogsgaard-Larsen, N.; Bunch, L. Chem. Rev. 2011, 111,
7981e8006; (b) Orsini, F.; Sello, G.; Sisti, M. Curr. Med. Chem. 2010, 17, 264e289;
(c) Naydenova, E. D.; Todorov, P. T.; Troev, K. D. Amino Acids 2010, 38, 23e30.
6. (a) Tillu, V. H.; Dumbre, D. K.; Wakharkar, R. D.; Choudhary, V. R. Tetrahedron
Lett. 2011, 52, 863e866; (b) Hosseini-Sarvari, M. Tetrahedron 2008, 64,
5459e5466; (c) Thirupathi Reddy, Y.; Narsimha Reddy, P.; Sunil Kumar, B.;
radeep Rajput, P.; Sreenivasulu, N.; Rajitha, B. Phosphorus, Sulfur, and Silicon
2007, 182, 161e165; (d) Bhagat, S.; Chakraborti, A. K. J. Org. Chem. 2007, 72,
1263e1270; (e) Syama Sundar, C.; Srinivasulu, D.; Nayak, S. K.; Suresh Reddy, C.
Phosphorus, Sulfur, and Silicon 2012, 187, 523e534; (f) Agawane, S. M.; Nagarkar,
J. M. Tetrahedron Lett. 2011, 52, 3499e3504; (g) Tang, J.; Wang, L.; Wang, W.;
Zhang, L.; Wu, S.; Mao, D. J. Fluorine Chem. 2011, 132, 102e106; (h) Mandhane,
P. G.; Joshi, R. S.; Nagargoje, D. R.; Gill, C. H. Chin. Chem. Lett. 2011, 22, 563e566;
(i) Sobhani, S.; Safaei, E.; Asadi, M.; Jalili, F. J. Organomet. Chem. 2008, 693,
313e3317; (j) Subba Reddy, B. V.; Siva Krishna, A.; Ganesh, A. V.; Narayana
Kumar, G. G. K. S. Tetrahedron Lett. 2011, 52, 1359e1362; (k) Merino, P.;
(t, 3H, J¼7.0 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼138.7, 130.3,
d
129.8, 128.6, 111.2, 111.0, 64.5 (d, 2JCP¼7.0 Hz), 63.6 (d, 2JCP¼7.1 Hz),
3
45.1 (d, JCP¼144.9 Hz), 25.4, 16.2 (d, JCP¼5.9 Hz), 16.2 (d,
3JCP¼5.6 Hz).
4.3.52. Diethyl 1-(2-chlorophenyl)-2,2-dicyanoethyl phosphonate
(5f).8a Yellow solid, mp 75e77 ꢀC (lit. 77); 1H NMR (250 MHz,
CDCl3, 25 ꢀC):
d
¼7.75 (d, 1H, J¼7.5 Hz), 7.46e7.50 (m, 1H), 7.32e7.36
(m, 2H), 4.63 (t, 1H, J¼8.5 Hz), 4.45 (dd, 1H, J1¼7.5, J2¼22.5 Hz),
4.05e4.28 (m, 2H), 3.89e3.98 (m, 1H), 3.71e3.81 (m, 1H), 1.35 (t,
3H, J¼7.2 Hz), 1.10 (t, 3H, J¼7.2 Hz); 13C NMR (62.9 MHz, CDCl3,
25 ꢀC)
d
¼135.0, 130.5, 130.3, 129.6, 128.6, 127.7, 111.2, 111.0, 64.4 (d,
ꢀ
ꢀ
Marques-Lopez, E.; Herrera, R. P. Adv. Synth. Catal. 2008, 350, 1195e1208; (l)
Quan, Z.; Ren, R. G.; Jia, X. D.; Da, Y. X.; Zang, Z.; Wang, X. C. Tetrahedron 2011,
67, 2462e2467; (m) Gambecka, J.; Kafarski, P. Mini-Rev. Med. Chem. 2001, 1,
133e144.
2JCP¼7.1 Hz), 63.6 (d, 2JCP¼7.2 Hz), 40.5 (d, 2JCP¼144.8 Hz), 24.8, 16.2
(d, 3JCP¼5.9 Hz), 16.0 (d, 3JCP¼5.7 Hz).
€
7. Groger, H.; Hammer, B. Chem.dEur. J. 2000, 6, 943.
4.3.53. Diethyl 1-(3-chlorophenyl)-2,2-dicyano ethyl phosphonate
8. (a) Sobhani, S.; Pakdin Parizi, Z. Tetrahedron 2011, 67, 3540e3545; (b) Kolla, S.
R.; Lee, Y. R. Tetrahedron 2011, 67, 3540e3545; (c) Hosseini-Sarvari, M.; Etemad,
S. Tetrahedron 2008, 64, 5519e5523; (d) Jiang, Z.; Zhang, Y.; Ye, W.; Tan, C.-H.
Tetrahedron Lett. 2007, 48, 51e54; (e) Enders, D.; Saint-Dizier, A.; Lannou, M. I.;
Lenzen, A. Eur. J. Org. Chem. 2006, 29e49; (f) Xu, Q.; Han, L.-B. Org. Lett. 2006, 8,
2099e2101; (g) Han, L. B.; Zhao, C. Q. J. Org. Chem. 2005, 70, 10121e10123; (h)
Stockland, R. A., Jr.; Taylor, R. I.; Thompson, L. E.; Patel, P. B. Org. Lett 2005, 7,
851e853; (i) Shulyupin, M. O.; Kazankova, M. A.; Beletskaya, I. P. Org. Lett. 2002,
4, 761e763; (j) Simoni, D.; Invidiata, F. P.; Manferdini, M.; Lampronti, I.; Ron-
danin, R.; Roberti, M.; Pollini, G. P. Tetrahedron Lett. 1998, 39, 7615e7618; (k)
Semenzin, D.; Etemad-Moghadam, G.; Albouy, D.; Diallo, O.; Koenig, M. J. Org.
Chem. 1997, 62, 2414e2422; (l) Pudovik, A. N.; Konovalova, I. V. Synthesis 1979,
2, 81e96; (m) Bodalski, R.; Pietrusiewicz, K. Tetrahedron Lett. 1972, 13,
4209e4212; (n) Hindersinn, R. R.; Ludington, R. S. J. Org. Chem. 1965, 30,
4020e4025; (o) Miller, R. C.; Bradley, J. S.; Hamilton, L. A. J. Am. Chem. Soc. 1956,
78, 5299e5303.
(5g).8a Yellow oil; 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.77 (s, 1H),
7.19e7.38 (m, 3H), 4.63 (t, 1H, J¼8.5 Hz), 4.05e4.15 (m, 4H), 3.65
(dd, 1H, J1¼7.0, J2¼21.5 Hz), 1.27 (t, 3H, J¼7.1 Hz), 1.09 (t, 3H,
J¼7.1 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
¼139.2, 130.3, 129.9,
d
129.1, 111.5, 111.4, 64.3 (d, 2JCP¼7.1 Hz), 63.3 (d, 2JCP¼7.2 Hz), 45.6 (d,
JCP¼144.4 Hz), 25.5, 16.2 (d, 3JCP¼5.9 Hz), 16.0 (d, 3JCP¼5.6 Hz).
4.3.54. Diethyl 2,2-dicyano-1-(4-nitrophenyl) ethyl phosphonate
(5h).8c (references do not report melting point) Yellow solid, mp
104e105 ꢀC; 1H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼8.59 (d, 2H,
J¼7.0 Hz), 7.66 (d, 2H, J¼7.0 Hz), 4.63 (t, 1H, J¼8.9 Hz), 4.11e4.17 (m,
4H), 3.70 (dd, 1H, J1¼7.5, J2¼22.3 Hz), 1.31 (t, 3H, J¼7.0 Hz), 1.14 (t,
9. Maerten, E.; Cabrera, S.; Kjarsgaard, A.; J4rgensen, K. A. J. Org. Chem. 2007, 72,
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11. (a) Sharghi, H.; Ebrahimpourmoghaddam, S.; Doroodmand, M. M.; Purkhosrow,
A. Asian, J. Org. Chem. 2012, 1, 377e388; (b) Choudhary, D.; Paul, S.; Gupta, R.;
Clark, J. H. Green Chem. 2006, 8, 479e482.
3H, J¼7.0 Hz); 13C NMR (62.9 MHz, CDCl3, 25 ꢀC)
d
¼137.2, 131.4,
2
130.6, 130.5, 124.4, 123.9, 110.4, 64.7 (d, JCP¼7.1 Hz), 64.2 (d,
2JCP¼7.2 Hz), 45.3 (d, 3JCP¼144.2 Hz), 25.4, 16.2 (d, 3JCP¼5.8 Hz), 16.1
(d, 3JCP¼5.6 Hz).
12. Serp, P.; Castillejos, E. ChemCatChem 2010, 2, 41e47.
4.3.55. Diethyl 2,2-dicyano-1-(furan-2-yl) ethyl phosphonate (5i).8a
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Carbon 2004, 42, 1321e1325.
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207e218.
1
Brown oil; H NMR (250 MHz, CDCl3, 25 ꢀC):
d
¼7.74 (s, 1H), 7.29
(s, 1H), 6.65 (s, 1H), 4.63 (t, 1H, J¼8.2 Hz), 4.40 (dd, 1H, J1¼7.5,
J2¼24.5 Hz), 3.74e4.24 (m, 4H), 1.35 (t, 3H, J¼7.0 Hz), 1.10 (t, 3H,
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H. Sharghi et al. / Tetrahedron xxx (2013) 1e17
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