Three-component synthesis of 2-oxoindolin-3-ylphosphonates

Article abstract of DOI:10.1248/cpb.58.896

A one-pot, three-component and catalyst-free method for the efficient and simple synthesis of dialkyl 3-(dicyanomethyl)-2-oxoindolin-3-ylphosphonates at 50 °C under solvent-free conditions is reported. The features of this procedure are mild reaction conditions, high yields of products, and operational simplicity.

Full text of DOI:10.1248/cpb.58.896

896
Regular Article
Chem. Pharm. Bull. 58(7) 896—900 (2010)
Vol. 58, No. 7
Three-Component Synthesis of 2-Oxoindolin-3-ylphosphonates
a
a
b
,a
*
Ghazaleh IMANI SHAKIBAEI, Afsaneh FEIZ, Ramin GHAHREMANZADEH, and Ayoob BAZGIR
a Department of Chemistry, Shahid Beheshti University; General Campus, Tehran 1983963113, Iran: and
b Nanobiotechnology Research Center, Avicenna Research Institute; ACECR, Tehran 1936773493, Iran.
Received January 24, 2010; accepted April 12, 2010; published online April 20, 2010
A one-pot, three-component and catalyst-free method for the efficient and simple synthesis of dialkyl 3-(di-
cyanomethyl)-2-oxoindolin-3-ylphosphonates at 50 °C under solvent-free conditions is reported. The features of
this procedure are mild reaction conditions, high yields of products, and operational simplicity.
Key words isatin; oxindole; dialkyl phosphite; oxoindolin-3-ylphosphonate; acenaphthylen-1,2-dione
Multicomponent reactions (MCRs), in which multiple re-
actions are combined into the synthetic operation have been
used extensively to form carbon-carbon bonds in the syn-
thetic chemistry.1—4) Such reactions offer a wide range of
possibilities for the efficient construction of highly complex
molecules in a single procedural step, thus avoiding the com-
plicated purification operations and allowing savings of both
solvents and reagents. In the past decade, there has been
Chart 1. Synthesis of 2-Oxoindolin-3-ylphosphonates 4
tremendous development in three- and four-component reac- work on the synthesis of heterocyclic compounds,44—58) we
tions, and great efforts continue to be made to develop new are currently investigating the synthesis of various 2-oxoin-
MCRs.5—9) In this context, oxindole derivatives show inter- dolin-3-ylphosphonates via a facile, atom-economical, and
esting features that make them attractive for use in MCRs. one-pot, three-component condensation reaction of isatins 1,
Oxindoles are known to possess antibacterial, antiprotozoal, malononitril 2 and dialkyl phosphites 3 under solvent-free
and anti-inflammatory activities and are also patented as PR conditions at 50 °C (Chart 1).
(progesterone receptors) agonists.10—14) The naturally occur-
ring oxindole derivative convolutamydine has been found to Results and Discussion
exhibit potent activity in the differentiation of HL-60 human
In a pilot experiment, the reaction of isatin 1a, malononi-
plomyelocytic leukemic cells.15) The varied biological activi- tril 2 and diethyl phosphite 3a in the absence of any catalyst
ties of oxindole derivatives have attracted the synthetic proceeds under solvent-free conditions at 50 °C. The
chemists to a number of synthetic strategies.16—20)
progress of the reaction was monitored by TLC. After com-
Pioneering work on P–C bond formation was carried out pletion of the reaction after 2 h, the product diethyl 3-(di-
by Arbusov in the early 20th century, culminating in the cyanomethyl)-2-oxoindolin-3-ylphosphonate 4a was ob-
well-known Michaelis–Arbusov reaction.21) In the following tained in 81% yield.
decades the chemistry of phosphonates developed relatively
Then, to delineate this approach, particularly in regard
slowly because of the difficulty in formation of the C–P to library construction, this methodology was evaluated
bond. Its renaissance came after 1959 with the discovery of by using eight substituted isatins 1a—h, three dialkyl
naturally occurring aminophosphonic acids22) and new bio- phosphates 3a—c and malononitril 2 and corresponding dial-
logically active phosphonates.23) Organophosphorus com- kyl 3-(dicyanomethyl)-2-oxoindolin-3-ylphosphonates 4a—t
pounds have found a wide range of application in the areas of were selectively synthesized by the one-pot, three-component
industrial, agricultural, and medicinal chemistry owing to condensation reaction in good yields under similar condi-
their biological and physical properties as well as their utility tions for 1—8 h (Table 1).
as synthetic intermediates.24—26) a-Functionalized phospho-
To the best of our knowledge, this new procedure provides
nic acids are valuable intermediates for the preparation of the first example of a three-component and catalyst-free syn-
medicinal compounds and synthetic intermediates.27—29) Nat- thesis of dialkyl 3-(dicyanomethyl)-2-oxoindolin-3-ylphos-
ural products containing P–C bonds also show interesting bi- phonates. The reactions under catalyst- and solvent-free con-
ological activities.30,31) Among various methods to generate ditions are considerably safe, nontoxic, environmentally
P–C bonds, the addition of P(O)–H bonds across alkenes is friendly, and inexpensive. The absence of catalyst for the re-
one of the most utilized.32,33) There are three general ap- action allows avoiding the use of moisture sensitive and
proaches: (a) the phospha-Michael reaction of activated heavy metal Lewis acids. This method, based on catalyst-free
alkenes, most commonly promoted by catalyst32—37) or mi- reaction under solvent-free conditions, is the most simple
crowave38); (b) addition to inactivated olefins promoted by and convenient and would be applicable for the synthesis of
radical initiators39); (c) hydrophosphorylation of inactivated different types of dicyanomethyl-oxoindolin-3-ylphospho-
alkenes catalyzed by transition metals.40,41) Recently, three- nates.
component methods have been reported for the synthesis of
1H- and 13C-NMR spectra of the crude products clearly in-
dicated the formation of 2-oxoindolin-3-ylphosphonates 4.
organophosphorus derivatives.42,43)
Considering the above reports, and as a continue of our Compounds 4 are stable solids whose structures were estab-
∗ To whom correspondence should be addressed. e-mail: a_bazgir@sbu.ac.ir
© 2010 Pharmaceutical Society of Japan

July 2010
897
Table 1. 2-Oxoindolin-3-ylphosphonates 4
the first time.
Compound 4
X
R
RЈ
Et
Et
Et
Time (h) Yield (%)a)
Conclusion
In conclusion, an efficient, atom-economical, and simple
method for the preparation of dialkyl 3-(dicyanomethyl)-2-
oxoindolin-3-ylphosphonate and dialkyl 1-(dicyanomethyl)-
2-oxo-1,2-dihydroacenaphthylen-1-ylphosphonates using read-
ily available starting materials under solvent-free conditions
is reported. Prominent among the advantages of this new
catalyst-free method are operational simplicity, good yields
and easy work-up procedures employed.
a
b
c
d
e
f
g
h
i
j
k
l
m
n
o
p
q
r
s
H
H
H
NO2
Br
H
H
H
H
2
3
5
2
1.5
2
1
3
3
2
2
4
8
3
7
8
3
2
6
6
81
82
85
70
83
71
75
70
86
72
88
82
81
76
72
74
71
79
80
81
PhCH2
Me
H
Et
Et
H
H
Me
Me
Me
Me
Me
Me
Me
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
i-Pr
PhCH2
Me
Et
H
NO2
Br
Br
H
H
H
H
H
Experimental
Me
H
PhCH2
Me
Et
General Melting points were measured on an Electrothermal 9100 ap-
paratus and are uncorrected. IR spectra were recorded on a Shimadzu IR-
470 spectrometer. H- and 13C-NMR spectra were recorded on a BRUKER
1
DRX-300 AVANCE spectrometer at 300.13 and 75.47 MHz, respectively.
Elemental analyses were performed using a Heracus CHN-O-Rapid ana-
lyzer.
H
NO2
Br
Br
NO2
H
H
Typical Procedure for Preparation of Diethyl 3-(Dicyanomethyl)-2-ox-
oindolin-3-ylphosphonate 4a A mixture of isatin (0.15 g, 1 mmol), mal-
ononitril (0.66 g, 1 mmol) and diethyl phosphite (0.16 g, 1.1 mmol) was
stirred at 50 °C for 2 h. After completion of the reaction confirmed by TLC
(eluent: EtOAc/n-hexane, 1 : 1), the reaction mixture was washed with di-
ethyl ether (5 ml) and residue recrystallized from MeOH–H2O (1 : 3) to af-
ford the pure product 4a as a cream powder (0.27 g, 81%). mp 168—170 °C.
IR (KBr) (nmax/cmϪ1): 3432, 2249, 1733, 1240. 1H-NMR (DMSO-d6) d:
1.14 (3H, t, 3JHHϭ7.0 Hz, CH3), 1.25 (3H, t, 3JHHϭ7.0 Hz, CH3), 3.98—4.16
Me
Me
t
a) Isolated yields.
3
(4H, m, CH2), 5.90 (1H, d, JHPϭ8.0 Hz, CH(CN)2), 7.00—7.57 (4H, m, H-
Ar), 11.38 (1H, s, NH). 13C-NMR (DMSO-d6) d: 16.3 (d, 3JCPϭ5.7 Hz,
3
1
CH3), 16.4 (d, JCPϭ5.9 Hz, CH3), 27.5, 53.1 (d, JCPϭ137.8 Hz, C–P), 64.7
(d, 2JCPϭ7.2 Hz, OCH2), 65.4 (d, 2JCPϭ6.9 Hz, OCH2), 111.1, 111.6 (d,
3JCPϭ13.7 Hz, CN), 112.0 (d, JCPϭ7.6 Hz, CN), 122.0 (d, JCPϭ5.5 Hz, H-
Ar), 123.1, 126.2, 131.4, 143.4 (d, 3JCPϭ6.8 Hz, H-Ar), 171.0 (d,
2JCPϭ3.1 Hz, CO). 31P-NMR (DMSO-d6) d: 13.01. Anal. Calcd for
C15H16N3O4P: C, 54.06; H, 4.84; N, 12.61%. Found: C, 54.15; H, 4.78; N,
12.53%.
3
2
Chart 2. Possible Mechanism for the Formation of Products 4
Diethyl 1-Benzyl-3-(dicyanomethyl)-2-oxoindolin-3-ylphosphonate 4b
82% yield. Pink powder. mp 177—180 °C. IR (KBr) (nmax/cmϪ1): 2260,
1720, 1229. 1H-NMR (DMSO-d6) d: 1.07 (3H, t, JHHϭ6.9 Hz, CH3), 1.24
(3H, t, JHHϭ6.9 Hz, CH3), 3.89—4.14 (4H, m, CH2), 4.97, 5.06 (2H, ABq,
J
ABϭ15.9 Hz, NCH2), 6.06 (1H, d, JHPϭ8.1 Hz, CH(CN)2), 6.06—7.63 (9H,
m, H-Ar). 13C-NMR (DMSO-d6) d: 16.3 (d, JCPϭ5.5 Hz, CH3), 16.4 (d,
J
J
J
CPϭ5.6 Hz, CH3), 27.4, 43.9, 52.6 (d, JCPϭ137.4 Hz, C–P), 65.0 (d,
CPϭ7.6 Hz, OCH2), 65.6 (d, CPϭ6.8 Hz, OCH2), 110.9, 111.6 (d,
CPϭ12.7 Hz, CN), 111.9 (d, JCPϭ7.9 Hz, CN), 121.2 (d, JCPϭ5.9 Hz, C-Ar),
J
123.9, 126.1 (d, JCPϭ2.9 Hz, C-Ar), 127.7, 128.1, 129.0, 131.5, 135.6, 143.7
(d, JCPϭ6.5 Hz, C-Ar), 169.6 (d, JCPϭ3.5 Hz, CO). 31P-NMR (DMSO-d6) d:
13.02. Anal. Calcd for C22H22N3O4P: C, 62.41; H, 5.24; N, 9.92%. Found: C,
62.33; H, 5.29; N, 9.85%.
Diethyl 3-(Dicyanomethyl)-1-methyl-2-oxoindolin-3-ylphosphonate 4c
85% yield. White powder. mp 100—104 °C. IR (KBr) (nmax/cmϪ1): 2260,
1713, 1256. 1H-NMR (DMSO-d6) d: 1.16 (3H, t, JHHϭ6.9 Hz, CH3), 1.24
(3H, t, JHHϭ6.9 Hz, CH3), 3.23 (3H, s, CH3), 3.96—4.15 (4H, m, CH2), 5.95
(1H, d, JHPϭ8.4 Hz, CH(CN)2), 7.22—7.61 (4H, m, H-Ar). 13C-NMR
(DMSO-d6) d: 16.3 (d, JCPϭ5.7 Hz, CH3), 16.4 (d, JCPϭ5.8 Hz, CH3), 27.4,
27.5, 52.6 (d, JCPϭ137.8 Hz, C–P), 64.8 (d, JCPϭ7.4 Hz, OCH2), 65.5 (d,
Chart 3. Synthesis of 2-Oxo-1,2-dihydroacenaphthylen-1-ylphosphonates
6
1
lished by IR, H-, 31P- and 13C-NMR spectroscopy and ele-
mental analysis.
The formation of products 4 can be rationalized by initial
formation of 2-(2-oxoindolin-3-ylidene)malononitriles 5 by
standard Knoevenagel condensation of isatins 1 and mal-
ononitrile 2. Subsequent Michael-type addition of dialkyl
phosphates 3 to the intermediate 5 afforded the correspon-
ding products 4 (Chart 2).
As expected, when the isatin 1 was replaced by acenaph-
thylene-1,2-dione 6, dialkyl 1-(dicyanomethyl)-2-oxo-1,2-di-
hydroacenaphthylen-1-ylphosphonates 7a—c was obtained
in good yield under the same reaction conditions (Chart 3).
These reactions proceeded very cleanly under mild condi-
tions, and no undesirable side reactions were observed. The
acenaphthylen-1-ylphosphonates 7a—c were synthesized for
JCPϭ8.1 Hz, OCH2), 110.3, 111.5 (d, JCPϭ12.4 Hz, CN), 111.9 (d,
J
CPϭ7.6 Hz, CN), 121.2 (d, JCPϭ5.5 Hz, C-Ar), 123.7, 125.9, 131.5, 144.7
(d, JCPϭ6.5 Hz, C-Ar), 169.4. 31P-NMR (DMSO-d6) d: 12.75. Anal. Calcd
for C16H18N3O4P: C, 55.33; H, 5.22; N, 12.10%. Found: C, 55.27; H, 5.15;
N, 12.17%.
Diethyl 3-(Dicyanomethyl)-5-nitro-2-oxoindolin-3-ylphosphonate 4d
70% yield. Yellow powder. mp 185—190 °C. IR (KBr) (nmax/cmϪ1): 3458,
1
2260, 1742, 1250. H-NMR (DMSO-d6) d: 1.17 (3H, t, JHHϭ6.9 Hz, CH3),
1.27 (3H, t, JHHϭ6.9 Hz CH3), 4.04—4.21 (4H, m, CH2), 6.17 (1H, d,
J
HPϭ8.7 Hz, CH(CN)2), 7.23—8.40 (3H, m, H-Ar), 12.13 (1H, s, NH). 13C-
NMR (DMSO-d6) d: 16.3 (d, JCPϭ2.0 Hz, CH3), 16.4 (d, JCPϭ2.2 Hz, CH3),
26.8, 27.5, 52.8 (d, JCPϭ136.3 Hz, C–P), 65.3 (d, JCPϭ7.5 Hz, OCH2), 66.1
(d, JCPϭ6.9 Hz, OCH2), 111.1, 111.6, 121.9 (d, JCPϭ3.1 Hz, C-Ar), 123.0,
128.5, 143.0 (d, JCPϭ3.0 Hz, C-Ar), 149.5, 149.6, 171.4. 31P-NMR (DMSO-

898
Vol. 58, No. 7
d6) d: 11.60. Anal. Calcd for C15H15N4O6P: C, 47.63; H, 4.00; N, 14.81%.
Found: C, 47.70; H, 3.92; N, 14.72%.
Dimethyl 5-Bromo-3-(dicyanomethyl)-1-methyl-2-oxoindolin-3-ylphos-
phonate 4l 82% yield. Pink powder. mp 168—171 °C. IR (KBr) (nmax
/
1
cmϪ1): 2260, 1724, 1250. H-NMR (DMSO-d6) d: 3.25 (3H, s, CH3), 3.70
Diethyl 5-Bromo-3-(dicyanomethyl)-2-oxoindolin-3-ylphosphonate 4e
83% yield. White powder. mp 182—185 °C. IR (KBr) (nmax/cmϪ1): 3421,
(3H, d, JHPϭ10.8 Hz, OCH3), 3.79 (3H, d, JHPϭ11.1 Hz, OCH3), 7.26 (1H, d,
1
2254, 1723, 1245. H-NMR (DMSO-d6) d: 1.15 (3H, t, JHHϭ6.9 Hz, CH3),
J
HPϭ8.4 Hz, CH(CN)2), 7.68—7.93 (3H, m, H-Ar). 13C-NMR (DMSO-d6)
1.26 (3H, t, JHHϭ6.9 Hz CH3), 3.98—4.19 (4H, m, CH2), 5.99 (1H, d,
d: 27.1, 27.6, 52.5 (d, JCPϭ138.4 Hz, C–P), 55.4 (d, JCPϭ7.3 Hz, OCH3),
55.2 (d, JCPϭ6.6 Hz, OCH3), 111.5, 112.6, 115.3, 123.2, 128.5, 134.5, 144.0
(d, JCPϭ6.6 Hz, C-Ar), 168.9. 31P-NMR (DMSO-d6) d: 14.48. Anal. Calcd
for C14H13BrN3O4P: C, 42.23; H, 3.29; N, 10.55%. Found: C, 42.32; H, 3.23;
N, 10.48%.
J
HPϭ8.4 Hz, CH(CN)2), 6.98—7.63 (3H, m, H-Ar), 11.54 (1H, s, NH). 13C-
NMR (DMSO-d6) d: 16.3 (d, JCPϭ5.1 Hz, CH3), 16.4 (d, JCPϭ5.2 Hz, CH3),
27.1, 52.9 (d, JCPϭ137.1 Hz, C–P), 65.0 (d, JCPϭ7.4 Hz, OCH2), 65.7 (d,
J
CPϭ7.0 Hz, OCH2), 111.3, 111.8 (d, JCPϭ8.4 Hz, CN), 113.1, 114.3, 124.3,
128.8, 134.2, 142.8 (d, JCPϭ6.9 Hz, C-Ar), 170.5. 31P-NMR (DMSO-d6) d:
12.30. Anal. Calcd for C15H15BrN3O4P: C, 43.71; H, 3.67; N, 10.19%.
Found: C, 43.64; H, 3.60; N, 10.11%.
Diisopropyl 3-(Dicyanomethyl)-2-oxoindolin-3-ylphosphonate 4m
81% yield. Cream powder. mp 199 °C dec. IR (KBr) (nmax/cmϪ1): 3185,
2260, 1723, 1219. 1H-NMR (DMSO-d6) d: 1.03—1.29 (12H, m, CH3),
4.40—4.50 (1H, m, OCH), 4.62—4.70 (1H, m, OCH), 5.73 (1H, d,
Dimethyl 3-(Dicyanomethyl)-2-oxoindolin-3-ylphosphonate 4f 71%
yield. White powder. mp 192—194 °C. IR (KBr) (nmax/cmϪ1): 3416, 2260,
1717, 1254. 1H-NMR (DMSO-d6) d: 3.57 (3H, d, JHPϭ11.1 Hz, OCH3), 3.75
(3H, d, JHPϭ11.1 Hz, OCH3), 5.96 (1H, d, JHPϭ8.1 Hz, CH(CN)2), 7.00—
7.54 (4H, m, H-Ar), 11.38 (1H, s, NH). 13C-NMR (DMSO-d6) d: 27.4, 53.2
(d, JCPϭ138.9 Hz, C–P), 55.0 (d, JCPϭ7.5 Hz, OCH3), 55.8 (d, JCPϭ6.7 Hz,
OCH3), 111.2, 111.8, 121.8, 123.1, 126.1, 131.5, 143.3, 143.4, 170.8. 31P-
NMR (DMSO-d6) d: 15.42. Anal. Calcd for C13H12N3O4P: C, 51.16; H,
3.96; N, 13.77%. Found: C, 51.08; H, 3.91; N, 13.70%.
J
HPϭ7.8 Hz, CH(CN)2), 6.98—7.59 (4H, m, H-Ar), 11.32 (1H, s, NH). 13C-
NMR (DMSO-d6) d: 23.0 (d, JCPϭ6.7 Hz, CH3), 23.8 (d, JCPϭ5.2 Hz, CH3),
24.0 (d, JCPϭ4.0 Hz, CH3), 24.4 (d, JCPϭ2.3 Hz, CH3), 27.8, 53.0 (d,
CPϭ138.6 Hz, C–P), 73.8 (d, JCPϭ7.6 Hz, OCH), 74.6 (d, JCPϭ7.1 Hz,
OCH), 111.0, 111.7 (d, JCPϭ14.4 Hz, CN), 112.1 (d, JCPϭ7.1 Hz, CN), 122.2
(d, JCPϭ5.4 Hz, C-Ar), 123.0, 126.3, 131.3, 143.5 (d, JCPϭ6.8 Hz, C-Ar),
171.0 (d, JCPϭ3.4 Hz, CO). 31P-NMR (DMSO-d6) d: 11.30. Anal. Calcd for
C17H20N3O4P: C, 56.51; H, 5.58; N, 11.63%. Found: C, 56.60; H, 5.50; N,
11.74%.
J
Dimethyl 1-Benzyl-3-(dicyanomethyl)-2-oxoindolin-3-ylphosphonate
4g 75% yield. Brown powder. mp 125—130 °C. IR (KBr) (nmax/cmϪ1):
2255, 1719, 1237. 1H-NMR (DMSO-d6) d: 3.66 (3H, d, JHPϭ11.1 Hz,
Diisopropyl
1-Benzyl-3-(dicyanomethyl)-2-oxoindolin-3-ylphospho-
nate 4n 76% yield. Pale orange powder. mp 117—120 °C. IR (KBr)
1
(nmax/cmϪ1): 2260, 1713, 1245. H-NMR (DMSO-d6) d: 0.87—1.30 (12H,
OCH3), 3.75 (3H, d,
JHPϭ11.1 Hz, OCH3), 4.99, 5.08 (2H, ABq,
JABϭ15.6 Hz, NCH2), 6.16 (1H, d, JHPϭ8.1 Hz, CH(CN)2), 7.07—7.63 (9H,
m, CH3), 4.42—4.48 (1H, m, OCH), 4.65—4.71 (1H, m, OCH), 4.95—5.06
m, H-Ar). 13C-NMR (DMSO-d6) d: 27.3, 52.8 (d, JCPϭ138.2 Hz, C–P),
55.3(d, JCPϭ7.6 Hz, OCH3), 56.0 (d, JCPϭ6.7 Hz, OCH3), 111.0, 111.9,
120.9, 124.0, 126.1, 127.5, 128.123, 129.0, 131.6, 135.6, 143.6, 143.7,
169.5. 31P-NMR (DMSO-d6) d: 13.27. Anal. Calcd for C20H18N3O4P: C,
60.76; H, 4.59; N, 10.63%. Found: C, 60.85; H, 4.53; N, 10.70%.
(2H, m, NCH2), 5.92 (1H, d, JHPϭ7.8 Hz, CH(CN)2), 7.06—7.64 (9H, m, H-
Ar). 13C-NMR (DMSO-d6) d: 22.8 (d,
J
CPϭ6.1 Hz, CH3), 23.9 (d,
CPϭ2.2 Hz, CH3), 27.6, 43.9, 52.5 (d,
CPϭ138.2 Hz, C–P), 74.1 (d, JCPϭ7.9 Hz, OCH), 74.9 (d, JCPϭ7.5 Hz,
J
J
CPϭ4.3 Hz, 2CH3), 24.4 (d, J
OCH), 110.8, 111.6, 121.0, 123.8, 126.2, 127.8, 128.1, 129.0, 131.4, 135.7,
143.8, 143.9, 169.7. 31P-NMR (DMSO-d6) d: 11.05. Anal. Calcd for
C24H26N3O4P: C, 63.85; H, 5.80; N, 9.31%. Found: C, 63.97; H, 5.72; N,
9.37%.
Dimethyl 3-(Dicyanomethyl)-1-methyl-2-oxoindolin-3-ylphosphonate
4h 70% yield. Cream powder. mp 148—150 °C. IR (KBr) (nmax/cmϪ1):
2260, 1708, 1266. 1H-NMR (DMSO-d6) d: 3.25 (3H, s, NCH3), 3.68 (3H, d,
J
J
HPϭ11.1 Hz, OCH3), 3.75 (3H, d, JHPϭ11.1 Hz, OCH3), 6.05 (1H, d,
Diisopropyl 3-(Dicyanomethyl)-1-methyl-2-oxoindolin-3-ylphospho-
nate 4o 72% yield. White powder. mp 121—123 °C. IR (KBr)
HPϭ8.7 Hz, CH(CN)2), 7.24—7.61 (4H, m, H-Ar). 13C-NMR (DMSO-d6)
1
(nmax/cmϪ1): 2260, 1718, 1261. H-NMR (DMSO-d6) d: 1.01—1.30 (12H,
d: 27.4, 52.8 (d, JCPϭ138.8 Hz, C–P), 55.2 (d, JCPϭ7.4 Hz, OCH3), 56.0 (d,
CPϭ6.7 Hz, OCH3), 111.4 (d, JCPϭ12.4 Hz, CN), 111.8 (d, JCPϭ8.0 Hz,
J
m, CH3), 3.23 (3H, s, NCH3), 4.38—4.48 (1H, m, OCH), 4.61—4.71 (1H,
m, OCH), 5.82 (1H, d, JHPϭ8.1 Hz, CH(CN)2), 7.23—7.63 (4H, m, H-Ar).
13C-NMR (DMSO-d6) d: 23.0 (d, JCPϭ6.5 Hz, CH3), 23.8 (d, JCPϭ5.1 Hz,
CH3), 24.0 (d, JCPϭ4.1 Hz, CH3), 24.4 (d, JCPϭ2.2 Hz, CH3), 27.3, 27.7, 52.5
(d, JCPϭ138.6 Hz, C–P), 74.0 (d, JCPϭ7.6 Hz, OCH), 74.7 (d, JCPϭ7.0 Hz,
OCH), 110.2, 111.6 (d, JCPϭ13.4 Hz, CN), 112.0, 121.3 (d, JCPϭ5.4 Hz, C-
Ar), 123.7, 126.1, 131.5, 144.7 (d, JCPϭ6.7 Hz, C-Ar), 169.4. 31P-NMR
(DMSO-d6) d: 11.07. Anal. Calcd for C18H22N3O4P: C, 57.60; H, 5.91; N,
11.19%. Found: C, 57.51; H, 5.84; N, 11.11%.
CN), 121.0 (d, JCPϭ7.5 Hz, C-Ar), 124.0, 125.9 (d, JCPϭ3.1 Hz, C-Ar),
131.6, 144.6 (d, JCPϭ6.6 Hz, C-Ar), 169.3 (d, JCPϭ3.1 Hz, CO). 31P-NMR
(DMSO-d6) d: 15.16. Anal. Calcd for C14H14N3O4P: C, 52.67; H, 4.42; N,
13.16%. Found: C, 52.55; H, 4.33; N, 13.09%.
Dimethyl 3-(Dicyanomethyl)-1-ethyl-2-oxoindolin-3-ylphosphonate 4i
86% yield. Cream powder. mp 124—126 °C. IR (KBr) (nmax/cmϪ1): 2254,
1712, 1277. 1H-NMR (DMSO-d6) d: 1.13 (3H, t, JHHϭ6.6 Hz, CH3), 3.65
(3H, d, JHPϭ10.8 Hz, OCH3), 3.74 (3H, d, JHPϭ11.1 Hz, OCH3), 3.80 (2H, q,
J
HHϭ7.2 Hz, NCH2), 6.03 (1H, d, JHPϭ7.8 Hz, CH(CN)2), 7.22—7.61 (4H,
Diisopropyl 3-(Dicyanomethyl)-1-ethyl-2-oxoindolin-3-ylphosphonate
4p 74% yield. White powder. mp 108—112 °C. IR (KBr) (nmax/cmϪ1):
3416, 2260, 1708, 1245. 1H-NMR (DMSO-d6) d: 0.97—0.98 (3H, br s,
CH3), 1.19—1.29 (12H, m, CH3), 3.78—3.80 (2H, m, NCH2), 4.41—4.45
(1H, m, OCH), 4.63—4.69 (1H, m, OCH), 5.79 (1H, d, JHPϭ7.5 Hz,
CH(CN)2), 7.21—7.63 (4H, m, H-Ar). 13C-NMR (DMSO-d6) d: 12.5, 23.0
(d, JCPϭ6.4 Hz, CH3), 23.8 (d, JCPϭ6.2 Hz, CH3), 23.9 (d, JCPϭ4.5 Hz, CH3),
24.4 (d, JCPϭ2.7 Hz, CH3), 27.8, 35.4, 52.3 (d, JCPϭ139.0 Hz, C–P), 74.0 (d,
m, H-Ar). 13C-NMR (DMSO-d6) d: 12.4, 27.5, 35.5, 52.6 (d, JCPϭ138.9 Hz,
C–P), 55.2 (d, JCPϭ7.3 Hz, OCH3), 55.9 (d, JCPϭ6.7 Hz, OCH3), 110.5,
111.3 (d, JCPϭ13.4 Hz, CN), 111.8 (d, JCPϭ7.6 Hz, CN), 121.2, 123.8,
126.2, 131.7, 143.6 (d, JCPϭ6.8 Hz, C-Ar), 169.0. 31P-NMR (DMSO-d6) d:
15.22. Anal. Calcd for C15H16N3O4P: C, 54.06; H, 4.84; N, 12.61%. Found:
C, 54.16; H, 4.77; N, 12.55%.
Dimethyl 3-(Dicyanomethyl)-5-nitro-2-oxoindolin-3-ylphosphonate 4j
72% yield. Orange powder. mp 197—199 °C. IR (KBr) (nmax/cmϪ1): 3111,
2255, 1747, 1257. 1H-NMR (DMSO-d6) d: 3.72 (3H, d, JHPϭ11.1 Hz,
OCH3), 3.81 (3H, d, JHPϭ11.4 Hz, OCH3), 6.25 (1H, d, JHPϭ9.0 Hz,
CH(CN)2), 7.24—8.40 (3H, m, H-Ar), 12.14 (1H, s, NH). 13C-NMR
(DMSO-d6) d: 26.7, 52.9 (d, JCPϭ137.4 Hz, C–P), 55.6 (d, JCPϭ7.3 Hz,
OCH3), 56.3 (d, JCPϭ6.6 Hz, OCH3), 111.5, 111.7, 121.8, 122.8, 128.6,
143.1, 149.4 (d, JCPϭ6.4 Hz, C-Ar), 171.3. 31P-NMR (DMSO-d6) d: 13.81.
Anal. Calcd for C13H11N4O6P: C, 44.58; H, 3.17; N, 16.00%. Found: C,
44.51; H, 3.09; N, 15.93%.
J
CPϭ7.8 Hz, OCH), 74.7 (d, JCPϭ6.7 Hz, OCH), 110.3, 111.4, 111.6, 121.5,
123.5, 126.3, 131.5, 143.7 (d, JCPϭ6.7 Hz, C-Ar), 169.1. 31P-NMR (DMSO-
d6) d: 11.15. Anal. Calcd for C19H24N3O4P: C, 58.61; H, 6.21; N, 10.79%.
Found: C, 58.50; H, 6.29; N, 10.90%.
Diisopropyl 3-(Dicyanomethyl)-5-nitro-2-oxoindolin-3-ylphosphonate
4q 71% yield. Yellow powder. mp 175 °C dec. IR (KBr) (nmax/cmϪ1):
3190, 2265, 1729, 1261. 1H-NMR (DMSO-d6) d: 1.12—1.31 (12H, m,
CH3), 4.52—4.58 (1H, m, OCH), 4.66—4.73 (1H, m, OCH), 6.00 (1H, d,
J
HPϭ8.4 Hz, CH(CN)2), 7.23—8.40 (3H, m, H-Ar), 12.10 (1H, s, NH). 13C-
Dimethyl 5-Bromo-3-(dicyanomethyl)-2-oxoindolin-3-ylphosphonate
4k 88% yield. Pink powder. mp 182—186 °C. IR (KBr) (nmax/cmϪ1):
3432, 2260, 1726, 1251.1H-NMR (DMSO-d6) d: 3.70 (3H, d, JHPϭ10.8 Hz,
OCH3), 3.78 (3H, d, JHPϭ11.1 Hz, OCH3), 6.07 (1H, d, JHPϭ8.4 Hz,
CH(CN)2), 6.98—7.65 (3H, m, H-Ar), 11.58 (1H, s, NH). 13C-NMR
(DMSO-d6) d: 27.1, 53.1 (d, JCPϭ138.3 Hz, C–P), 55.3 (d, JCPϭ7.5 Hz,
OCH3), 56.1 (d, JCPϭ6.8 Hz, OCH3), 111.1, 111.6, 113.3, 114.5, 124.2 (d,
NMR (DMSO-d6) d: 23.1 (d, JCPϭ6.6 Hz, CH3), 23.6 (d, JCPϭ5.4 Hz, CH3),
24.0 (d, JCPϭ3.7 Hz, CH3), 24.4 (d, JCPϭ1.7 Hz, CH3), 27.2, 53.0 (d,
JCPϭ137.2 Hz, C-P), 74.7 (d, JCPϭ7.9 Hz, OCH), 75.4 (d, JCPϭ6.6 Hz,
OCH), 111.5, 122.0, 123.2, 123.3, 128.4, 142.9 (d, JCPϭ3.1 C-Ar), 149.6,
149.7, 171.4. 31P-NMR (DMSO-d6) d: 9.78. Anal. Calcd for C17H19N4O6P:
C, 50.25; H, 4.71; N, 13.79 %. Found: C, 50.19; H, 4.76; N, 13.72%.
Diisopropyl
5-Bromo-3-(dicyanomethyl)-2-oxoindolin-3-ylphospho-
J
CPϭ5.9 Hz, C-Ar), 128.6, 134.4, 142.7 (d, JCPϭ6.8 Hz, C-Ar), 170.4. 31P-
nate 4r 79% yield. White powder. mp 175 °C dec. IR (KBr) (nmax/cmϪ1):
3437, 2260, 1734, 1240. 1H-NMR (DMSO-d6) d: 1.09—1.31 (12H, m,
CH3), 4.46—4.54 (1H, m, OCH), 4.56—4.73 (1H, m, OCH), 4.56—5.06
NMR (DMSO-d6) d: 14.25. Anal. Calcd for C13H11BrN3O4P: C, 40.65; H,
2.89; N, 10.94%. Found: C, 40.53; H, 2.81; N, 10.84%.

July 2010
899
(2H, m, NCH2), 5.83 (1H, d, JHPϭ7.8 Hz, CH(CN)2), 6.98—7.64 (3H, m, H-
Ar), 11.51 (1H, s, NH). 13C-NMR (DMSO-d6) d: 23.1 (d, JCPϭ6.0 Hz, CH3),
23.7 (d, JCPϭ5.1 Hz, CH3), 24.0 (d, JCPϭ3.8 Hz, CH3), 24.4 (d, JCPϭ1.7 Hz,
CH3), 27.4, 53.0 (d, JCPϭ137.5 Hz, C-P), 74.3 (d, JCPϭ7.3 Hz, OCH), 75.0
(d, JCPϭ6.7 Hz, OCH), 111.5, 111.8, 113.1, 114.2, 124.5, 128.9, 134.1,
142.8 (d, JCPϭ6.5 Hz, H-Ar), 170.6. 31P-NMR (DMSO-d6) d: 10.57. Anal.
Calcd for C17H19BrN3O4P: C, 46.38; H, 4.35; N, 9.55%. Found: C, 46.30; H,
4.28; N, 9.46%.
2) Tietze L. F., Modi A., Med. Res. Rev., 20, 304—322 (2000).
3) Dömling A., Ugi I., Angew. Chem. Int. Ed., 39, 3169—3210 (2000).
4) Zhu J., Eur. J. Org. Chem., 2003, 1133—1144 (2003).
5) Nair V., Vinod A. U., Rajesh C., J. Org. Chem., 66, 4427—4429
(2001).
6) List B., Castello C., Synlett, 2001, 1687—1689 (2001).
7) Shestopalov A. M., Emeliyanova Y. M., Shestiopolov A. A., Rodi-
novskaya L. A., Niazimbetova Z. I., Evans D. H., Org. Lett., 4, 423—
425 (2002).
Diisopropyl 5-Bromo-3-(dicyanomethyl)-1-methyl-2-oxoindolin-3-yl-
phosphonate 4s 80% yield. Cream powder. mp 110—112 °C. IR (KBr)
8) Bertozzi F., Gustafsson M., Olsson R., Org. Lett., 4, 3147—3150
(2002).
9) Yuan Y., Li X., Ding K. Org. Lett., 4, 3309—3311 (2002).
1
(nmax/cmϪ1): 2260, 1728, 1261. H-NMR (DMSO-d6) d: 0.84—1.30 (12H,
m, CH3), 3.35 (3H, s, CH3), 4.43—4.53 (1H, m, OCH), 4.62—4.72 (1H, m,
OCH), 5.91 (1H, d, JHPϭ8.4 Hz, CH(CN)2), 7.23—7.77 (3H, m, H-Ar). 13C- 10) Joshi K. C., Pathak V. N., Jain S. K., Pharmazie, 35, 677—679 (1980).
NMR (DMSO-d6) d: 23.1 (d, JCPϭ6.4 Hz, CH3), 23.7 (d, JCPϭ5.2 Hz, CH3), 11) Bolotov V. V., Drugovina V. V., Yakovleva L. V., Bereznyakova A. I.,
23.9 (d, JCPϭ4.1 Hz, CH3), 24.3 (d, JCPϭ2.7 Hz, CH3), 27.4, 27.5, 52.4 (d,
CPϭ137.9 Hz, C–P), 74.4 (d, JCPϭ7.6 Hz, OCH), 75.1 (d, JCPϭ7.2 Hz,
Khim. Farm. Zh., 16, 58—61 (1982).
12) Pajouhesh H., Parsons R., Popp F. D., J. Pharm. Sci., 72, 318—321
J
OCH), 111.4, 111.7, 112.4, 115.0, 123.7 (d, JCPϭ5.9 Hz, C-Ar), 128.7,
(1983).
134.2, 135.7, 144.1 (d, JCPϭ6.2 Hz, C-Ar), 169.0. 31P-NMR (DMSO-d6) d: 13) Popp F. D., J. Heterocycl. Chem., 21, 1367—1368 (1984).
10.35. Anal. Calcd for C18H21BrN3O4P: C, 47.59; H, 4.66; N, 9.25%. Found: 14) Garrido F., Ibannez J., Gonalons E., Giraldez A., Eur. J. Med. Chem.,
C, 47.47; H, 4.57; N, 9.15%.
Diisopropyl 3-(Dicyanomethyl)-1-methyl-5-nitro-2-oxoindolin-3-yl- 15) Kamano Y., Zhang H. P., Ichihara Y., Kizu H., Komiyama K., Itokawa
phosphonate 4t 81% yield. Yellow powder. mp 136—138 °C. IR (KBr)
H., Pettit G. R., Tetrahedron Lett., 36, 2783—2784 (1995).
(nmax/cmϪ1): 2255, 1738, 1256. H-NMR (DMSO-d6) d: 1.03—1.38 (12H, 16) Klumpp D. A., Yeung K. Y., Prakash G. K. S., Olah G. A., J. Org.
m, CH3), 3.32 (3H, s, CH3), 4.46—4.54 (1H, m, OCH), 4.51—4.57 (1H, m,
Chem., 63, 4481—4484 (1998).
10, 143—146 (1975).
1
OCH), 4.67—4.73 (2H, m, NCH2), 6.06 (1H, d, JHPϭ9.3 Hz, CH(CN)2), 17) Jursic B., Stevens E. D., Tetrahedron Lett., 43, 5681—5683 (2002).
7.51—8.53 (3H, m, H-Ar), 11.51 (1H, s, NH). 13C-NMR (DMSO-d6) d: 18) Azizian J., Mohammadi A. A., Karimi N., Mohammadizadeh M. R.,
23.1 (d, JCPϭ6.4 Hz, CH3), 23.7 (d, JCPϭ5.3 Hz, CH3), 24.0 (d, JCPϭ3.7 Hz,
CH3), 24.3 (d, JCPϭ2.2 Hz, CH3), 27.1, 27.9, 52.2 (d, JCPϭ137.2 Hz, C–P),
Karimi A. R., Catal. Commun., 7, 752—755 (2006).
19) Wang S. Y., Ji S. J., Tetrahedron, 62, 1527—1535 (2006).
74.9 (d, JCPϭ7.6 Hz, OCH), 75.2 (d, JCPϭ7.2 Hz, OCH), 110.9, 111.4, 121.6, 20) Yadav J. S., Reddy B. V. S., Gayathri K. U., Meraj S., Prasad A. R.,
122.3, 128.4, 143.5, 150.2, 150.3,171.2. 31P-NMR (DMSO-d6) d: 9.62.
Synthesis, 2006, 4121—4123 (2006).
Anal. Calcd for C18H21N4O6P: C, 51.43; H, 5.04; N, 13.33%. Found: C, 21) Arbusov B. A., Pure Appl. Chem., 9, 307—335 (1964).
51.52; H, 5.01; N, 13.25%.
22) Horiguchi M., Kandatsu M., Nature (London), 184, 901—902 (1959).
Diethyl 1-(Dicyanomethyl)-2-oxo-1,2-dihydroacenaphthylen-1-ylphos- 23) Hildebrand R., “The Role of Phosphonates in Living Systems,” CRC,
phonate 7a 89% yield. Green powder. mp 158—162 °C. IR (KBr)
Boca Raton, FL, 1983.
(nmax/cmϪ1): 2249, 2223, 1723, 1240. 1H-NMR (DMSO-d6) d: 0.095 (3H, t, 24) Engel R., Chem. Rev., 77, 349—367 (1977).
HHϭ6.1 Hz CH3), 1.18 (3H, t, JHHϭ7.0 Hz, CH3), 3.83—4.11 (4H, m, CH2), 25) Schug K. A., Lindner W., Chem. Rev., 105, 67—113 (2005).
6.15 (1H, d, JHPϭ8.6 Hz, CH(CN)2), 7.87—8.48 (6H, m, H-Ar). 13C-NMR 26) Palacios F., Alonso C., de los Santos J. M., Curr. Org. Chem., 8,
(DMSO-d6) d: 16.2 (d, JCPϭ5.5 Hz, CH3), 16.4 (d, JCPϭ5.5 Hz, CH3), 27.0,
1481—1496 (2004).
57.4 (d, JCPϭ135.8 Hz, C–P), 64.7 (d, JCPϭ7.4 Hz, OCH2), 65.2 (d, 27) Dingwall J. G., Campell C. D., Baylis E. K., U.K. Patent 1542938
CPϭ6.7 Hz, OCH2), 111.9, 112.3, 124.4, 124.6, 127.7, 129.5, 129.8, 130.9,
(1979) [Chem. Abstr., 88, 105559j (1979)].
J
J
134.0, 134.2, 142.2, 195.1. 31P-NMR (DMSO-d6) d: 13.47. Anal. Calcd for 28) Kafarski P., Lejczak B., Tyka R., Koba L., Pliszczak E., Wieczorek P.,
C19H17N2O4P: C, 61.96; H, 4.65; N, 7.61%. Found: C, 61.89; H, 4.60; N,
7.55%.
Dimethyl 1-(Dicyanomethyl)-2-oxo-1,2-dihydroacenaphthylen-1-yl-
J. Plant Growth Regul., 14, 199—203 (1995).
29) Ishiguri Y., Yamada Y., Kato T., Sasaki M., Mukai K., Eur. Patent EP
82-301905 (1982) [Chem. Abstr., 98, 102686u (1983)].
phosphonate 7b 80% yield. Green powder. mp 125—130 °C. IR (KBr) 30) Fields S. C., Tetrahedron, 55, 12237—12273 (1999).
1
(nmax/cmϪ1): 2234, 1718, 1251. H-NMR (DMSO-d6) d: 0.62—1.25 (12H, 31) Seto, H., Kuzuyama T., Nat. Prod. Rep., 16, 589—596 (1999).
m, CH3), 3.78—3.80 (2H, m, NCH2), 4.22—4.32 (1H, m, OCH), 4.58—4.68 32) Pudovik A. N., Konovalova I. V., Synthesis, 1979, 81—69 (1979).
(1H, m, OCH), 6.02 (1H, d, JHPϭ8.1 Hz, CH(CN)2), 7.87—8.47 (6H, m, H- 33) Enders D., Saint-Dizier A., Lannou M. I., Lenzen A., Eur. J. Org.
Ar). 13C-NMR (DMSO-d6) d: 27.0, 55.1 (d, JCPϭ7.3 Hz, OCH3), 55.6 (d,
Chem., 2006, 29—49 (2006).
CPϭ6.7 Hz, OCH3), 57.5 (d, JCPϭ136.8 Hz, C–P), 111.7 (d, JCPϭ13.7 Hz, 34) Bodalski R., Pietrusiewicz K., Tetrahedron Lett., 13, 4209—4212
J
CN), 112.2 (d, JCPϭ7.6 Hz, CN), 124.5 (d, JCPϭ2.9 Hz, C-Ar), 124.8, 127.8,
(1972).
129.5, 129.7, 129.9, 130.7 (d, JCPϭ5.0 Hz, C-Ar), 130.9, 134.3, 142.2 (d, 35) Simoni D., Invidiata F. P., Manferdini M., Lampronti I., Rondanin R.,
CPϭ6.1 Hz, C-Ar), 195.0 (d, JCPϭ3.5 Hz, CO). 31P-NMR (DMSO-d6) d:
Roberti M., Pollini G. P., Tetrahedron Lett., 39, 7615—7618 (1998).
15.98. Anal. Calcd for C17H13N2O4P: C, 60.01; H, 3.85; N, 8.23%. Found: C, 36) Green K., Tetrahedron Lett., 30, 4807—4810 (1989).
59.92; H, 3.78; N, 8.14%.
37) Hosseini-Sarvari M., Etemad S., Tetrahedron, 64, 5519—5523 (2008).
Diisopropyl 1-(Dicyanomethyl)-2-oxo-1,2-dihydroacenaphthylen-1-yl- 38) Stockland R. A. Jr., Taylor R. I., Thompson L. E., Patel P. B., Org.
J
phosphonat 7c 92% yield. Green powder. mp 160—162 °C. IR (KBr)
Lett., 7, 851—853 (2005).
1
(nmax/cmϪ1): 2254, 2228, 1734, 1229. H-NMR (DMSO-d6) d: 0.62—1.25 39) Han L.-B., Zhao C.-Q., J. Org. Chem., 70, 10121—10123 (2005).
(12H, m, CH3), 3.78—3.80 (2H, m, NCH2), 4.22—4.32 (1H, m, OCH), 40) Xu Q., Han L.-B., Org. Lett., 10, 2099—2101 (2006).
4.58—4.68 (1H, m, OCH), 6.02 (1H, d, JHPϭ8.1 Hz, CH(CN)2), 7.87—8.47 41) Shulyupin M. O., Kazankova M. A., Beletskaya I. P., Org. Lett., 4,
(6H, m, H-Ar). 13C-NMR (DMSO-d6) d: 22.6 (d, JCPϭ6.7 Hz, CH3), 23.8 (d,
761—763 (2002).
CPϭ5.2 Hz, CH3), 23.9 (d, JCPϭ3.8 Hz, CH3), 24.3 (d, JCPϭ2.4 Hz, CH3), 42) Khidre M. D., Phosphorus, Sulfur and Silicon, 178, 2147—2158
J
27.2, 57.4 (d, JCPϭ136.4 Hz, C–P), 73.9 (d, JCPϭ7.1 Hz, OCH), 74.5 (d,
(2003).
J
CPϭ7.1 Hz, OCH), 111.9, 112.0, 112.3, 112.4, 124.4, 127.6, 129.4, 129.8, 43) Yadav J. S., Reddy B. V. S., Sreedhar P., Adv. Synth. Catal., 345, 564—
130.8, 131.0, 134.1, 142.2 (d, JCPϭ5.8 Hz, C-Ar), 195.0. 31P-NMR (DMSO-
567 (2003).
d6) d: 11.67. Anal. Calcd for C21H21N2O4P: C, 63.63; H, 5.34; N, 7.07%. 44) Bazgir A., Seyyedhamzeh M., Yasaei Z., Mirzaei P., Tetrahedron Lett.,
Found: C, 63.70; H, 5.39; N, 7.01%.
48, 8790—8794 (2007).
45) Sayyafi M., Seyyedhamzeh M., Khavasi H. R., Bazgir A., Tetrahedron,
64, 2375—2378 (2008).
Acknowledgements We gratefully acknowledge financial support from
the Research Council of Shahid Beheshti University.
46) Dabiri M., Arvin-Nezhad H., Khavasi H. R., Bazgir A., J. Heterocycl.
Chem., 44, 1009—1011 (2007).
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