One pot synthesis of biodynamic bisamidothiophosphonates incorporating asymmetric phosphorus atom

Article abstract of DOI:10.1080/10426500601161015

N-alkyl-2-pyridinylidenamido(phenyl)chlorothiophosphonates have been generated in situ by oxidative phosphorylation of N-alkyl-2-aminopyridinium halides through the intermediacy of functionalized halophosphines. As evident from the proton NMR spectroscopy

Full text of DOI:10.1080/10426500601161015

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Phosphorus, Sulfur, and Silicon
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One Pot Synthesis
of Biodynamic
Bisamidothiophosphonates
Incorporating Asymmetric
Phosphorus Atom
Vijaya Kabra a , Priti Kaushik a & Arpana Meel a
a Department of Chemistry , University of
Rajasthan , Jaipur, India
Published online: 29 Aug 2007.
To cite this article: Vijaya Kabra , Priti Kaushik & Arpana Meel (2007) One Pot
Synthesis of Biodynamic Bisamidothiophosphonates Incorporating Asymmetric
Phosphorus Atom, Phosphorus, Sulfur, and Silicon and the Related Elements, 182:6,
1365-1380, DOI: 10.1080/10426500601161015
To link to this article: http://dx.doi.org/10.1080/10426500601161015
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Phosphorus, Sulfur, and Silicon, 182:1365–1380, 2007
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500601161015
One Pot Synthesis of Biodynamic
Bisamidothiophosphonates Incorporating Asymmetric
Phosphorus Atom
Vijaya Kabra
Priti Kaushik
Arpana Meel
Department of Chemistry, University of Rajasthan, Jaipur, India
N-alkyl-2-pyridinylidenamido(phenyl)chlorothiophosphonates have been gener-
ated in situ by oxidative phosphorylation of N-alkyl-2-aminopyridinium halides
through the intermediacy of functionalized halophosphines. As evident from the
proton NMR spectroscopy, the generated chiral system had induced diastereotopic-
ity in the geminal protons attached to a prochiral carbon atom. Due to the presence of
an active chlorine atom, they have been used as precursors for the synthesis of novel
bisamidothiophosphonates. The bioactive nature of these compounds has been es-
tablished after bioassay against the fungi Alternaria alternata, Aspergillus flavus,
Aspergillus niger, and Fusarium oxysporum and the insect Holotrichea Consan-
guinea.
Keywords Bioassay; diastereotopicity; halophosphine; prochirality; thiophosphonate
INTRODUCTION
A novel chiral system incorporating tetracoordinated phosphorus has
been developed in this study, which induced long-range diastereotopic-
ity in the N-methylene protons attached to a prochiral carbon of the
molecules. Such magnetic nonequivalence due to molecular asymmetry
has been reported for a variety of compounds by a number of authors.
Siddall and Prohaska1 observed nonequivalence of the alkoxy group
of a variety of phosphorus esters. Similar findings have been re-
ported by Rowsell2 and Finegold3 in the review of Jennings,4 who
compiled the chemical shift nonequivalence in prochiral groups. Moen
Received September 18, 2006; accepted November 22, 2006.
We are thankful to Dr. Y.S. Mathur and A.R.S., Durgapura, Jaipur, for insecticidal
activity.
Address correspondence to Vijaya Kabra, Department of Chemistry, University of
Rajasthan, Jaipur, India. E-mail: sgkabra@sancharnet.in
1365

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V. Kabra et al.
and Mueller,5 even reported the nonequivalence of a proton sepa-
rated from a chiral carbon by a distance of six bonds. Pedrosa et
al.6 and Afarinkia and Jones7,8 have achieved diastereoselective alky-
lated products by replacing one of such nonequivalent protons and
thus, this has opened the possibility for stereoselective asymmetric
synthesis.
In our previous publications, achiral bioactive amidothiophosphates
from 2-aminocycloiminium salts incorporating different N-heterocycles
have been reported.9−11 The synthesis of analogous achiral thiophosphi-
nates have been reported by Boedeker et al.12
In the present work, using phenyldichlorophosphine as a phospho-
rylating agent, bisamidothiophosphonates have been synthesized in
a one pot synthesis through the intermediacy of chlorothiophospho-
nates. Products incorporated a chiral phosphorus unit attached to an
important heterocyclic nucleus-pyridine. As chirality is related with
bioactivity,13−16 on bioscreening, these molecules, which have been ob-
tained as racemic products, have exhibited strong antifungal and in-
secticidal activities.
This study thus provided a novel class of bioactive amidothiophos-
phonates with the diastereotopic methylene group, thus opening fur-
ther prospects for asymmetric synthesis.
RESULTS AND DISCUSSION
N-alkyl-2-aminopyridinium halides 1 have been phosphorylaed by
PhPCl2 (1 equivalent) and Et3N (2 equivalents) in a 2:1 mixture of
toluene and methylene chloride at 0–5◦C followed by oxidation with el-
emental sulfur under dry nitrogen, on work-up halothiophosphonates 3
were isolated in pure state. This synthetic part of the work was already
communicated.17 In the proposed work, 3, in situ, were converted to
a new series of bisamidothiophosphonates 4–7 in a one pot synthetic
procedure. By subjecting 3 to nucleophilic substitution through a dif-
ferent series of secondary amines in the presence of the weak base
triethylamine (except in 4 where two equivalents of diethylamine have
been used, which has served as a nucleophile as well as a base for
the abstraction of hydrochloric acid) have achieved different series of
(alkyl, alicyclic, and phenyl) asymmetrical amidothiophosphonates 4–7
(Scheme 1).
All of the products, 4–7 were obtained as stable white-to-cream and
light-yellow solids and on recrystallization from methylene chloride
furnished crystalline pure products, which were characterized by el-
1
emental analysis; 31P, H, 13C, and 2D NMR, and mass spectroscopic
techniques.

Biodynamic Bisamidothiophosphonates
1367
SCHEME 1 Scheme 1
31P NMR
Reaction progress has been monitored through 31P NMR spectroscopy of
the reaction mixture. On such monitoring, the 31P signal of the reagent
PhPCl2 at δ161 ppm first changed to tricoordinated halophosphines at
δ 107–123 ppm, which, on the addition of sulfur, converted to tetarco-
ordinated halothiophosphonates with signals at δ 60.1–65.2 ppm. On

1368
V. Kabra et al.
further addition of nucleophile secondary amines, an upfield shift of the
order ꢀδ = 3.9–7.4 ppm was been observed by the amido moiety due to
a replacement of the electronegative chlorine atom, and a signal of the
reaction mixture was obtained at δ 56.2–58.8 ppm, thus confirming the
generation of the amidothiophosphonates. This value is in accordance
with tetracoordinated pentavalent phosphorus.18,19 Similar signals of
31P NMR of the isolated products confirmed their synthesis.
1H NMR
During phosphorylation, one stereogenic phosphorus was generated,
which showed interesting induction of diastereotopicity. Anisochronous
geminal NCH2protons of 4a, 4b, 4d, 4e, 5a, 5b, 5d, 6a, and 7a that were
attached to a pyridine ring five bonds apart from the chiral phosphorus
gave two sets of doublets at δ 4.59–5.29 ppm and 4.72–5.49 ppm with
coupling constant J of the order of 14.6–21.2 Hz displaying a typical
AB pattern,4,20,21 whereas NCH3 protons of 4c and 5c were assigned as
a singlet at δ 3.64 and 3.71 ppm.
Another interesting induced diastereotopicity was also observed in
the amido moiety of 4, where the prochiral moiety was a nitrogen atom,
such anisochronous behavior in aminophosphorus compounds has been
reported in the literature both in 1H NMR22 and 13C NMR23 spec-
troscopy. Methylene protons of the ethylamido group gave two sets of a
doublet of a doublet of a quartet in the range δ 3.03–3.14 ppm and δ 3.21–
3.25 ppm due to three-bond coupling with phosphorus 3 J = 7.0–11.7
PH
Hz in addition to geminal coupling and vicinal coupling with coupling
constant 2 J = 18.4–19.1 Hz and 3 J = 7.0–7.1 Hz, respectively.
HH
HH
Alicyclic ring protons of 5 of N-methylcyclohexylamido moiety were
observed as a complicated multiplet in the most upfield region δ
0.07–1.68 ppm showing again the nonequivalent nature of the methy-
lene protons of a configurationally locked cyclohexyl ring forming the
AB part of an ABX system.20 Equatorial protons were found to be
approximately δ 0.4 ppm more deshielded than the axial protons of the
cyclohexyl ring. The coupling constant for geminal coupling was about
J
= 10.9–12.6 Hz, and vicinal coupling Jax−ax and Jeq−ax were 4.2–4.8
AB
Hz and 2.4–3.5 Hz, respectively.
Aromatic protons of the pyridine and phenyl ring were observed in
the expected aromatic region (Table I).
13C NMR
Further support of the structure of the molecule was given by 13C and
2D NMR of 4 and 5. Carbon phosphorus coupling could be observed with

1369

1370

1371

1372

1373

1374
V. Kabra et al.
TABLE II 13C NMR of 4b, 5b, and 5c
Compound
δ (ppm) J(Hz)
4b
5b
5c
14.2 (PNCH2CH3); 53.9 (PNCH2CH3); 39.7 (OCH2CH3); 61.8
(OCH2CH3); 108.1 (NCH2); 120.4 (d,2 J = 11.4, Cortho); 127.8 (d,
CP
3 J =13.6, Cmeta ); 130.6(Cpara); 139.7 (d, 1 J = 129.5, Cipso);
CP
CP
127.8(C-5); 130.7 (C-3); 138.5 (C-4); 139.1 (C-6); 156.6 (d, 2 J
=
PC
10.6, C-2); 167.4 (C=O)
ꢀ
ꢀ
ꢀ
14.0 (OCH2CH3); 24.3–30.8 (Cβ,β , Cγ ,γ ,Cα of NCH3C6H11); 54.5
(NCH3C6H11); 61.8(Cα of NCH3C6H11); 61.4 (OCH2CH3); 107.9
(NCH2); 120.5 (d, 2JCP = 9.8, Cortho); 130.5(d, 3JCP = 10.6, Cmeta);
130.6 (Cpara); 138.9 (d, 1 J = 129.1, Cipso); 129.8 (C-5); 130.7 (C-3);
CP
138.5 (C-4); 140.2 (C-6) ; 156.5 (d, 2JCP =10.9, C-2); 167.4 (C=O)
ꢀ
ꢀ
ꢀ
27.8–30.8 (Cβ,β , Cγ ,γ ,Cα of NCH3C6H11); 54.5 (NCH3C6H11);
60.8(Cα of NCH3C6H11); 107.9 (NCH3); 120.2 (d, 2JCP =9.8, Cortho);
127.7(d, 3JCP = 10.6, Cmeta); 130.7 (Cpara); 139.6 (d, 1 J = 129.1,
CP
C
ipso); 129.8 (C-5); 130.8 (C-3); 137.9 (C-4); 138.0 (C-6); 207.6 (d,
2JCP = 10.9, C-2)
few carbon atoms of the molecule. In this discussion, special mention of
the ipso-carbon of the phenyl moiety directly attached to the phosphorus
atom should be of interest, it showed doublet at δ 138.9–139.7 ppm
with minimum intensity due to the quaternary nature with coupling
1
constant J = 129.5 Hz. The ipso-carbon of the synthons 3 was also
CP
observed as a doublet but with a higher coupling constant of the order
1 J = 213.7 Hz (Table II). The difference of the coupling constant in
CP
amidothiophosphonates and chlorothiophosphonates 3 (ꢀJ = 84.2 Hz)
was due to the replacement of the electronegative chlorine of 3 by the
amido moiety; this is in accordance with the values reported in the
literature.24
MASS SPECTRUM
In the mass spectrum of 4a, the molecular ion peak together with an
(M+1) peak with 36% and 50% intensity has been observed at m/z
TABLE III Mass Spectrum Data of 4a and 5b (Relative Abundances
Have Been Given in Parentheses)
Compound
m/z (%)
4a
377 (M+, 36); 378 (M+1, 50); 346 (5); 345 (10); 305 (18); 273 (20);
269 (5); 149 (100).
5b
431 (M+, 17%); 432 (M+1, 50); 399 (10); 319 (22); 320 (50); 287 (30);
181 (5); 165 (5); 163 (100); 136 (14); 135 (76); 107 (38).

Biodynamic Bisamidothiophosphonates
1375
377 and 378, respectively. A radical ion at m/z 149 with 100% abun-
dance represented a base peak and other fragmented peaks listed in
Table III. The molecular ion peak in 5b was found at m/z 431 (20%)
together with (M+1) peak m/z 432 (50%) in the spectrum because of
the possible acceptance of one proton by iminium nitrogen. The other
peaks have been recorded at m/z 399, 319, 320, 287, 181, 165, 136, 135,
and 107 with a base peak at m/z 163 with 100% abundance.
BIOACTIVITY
Strong antifungial activity was exhibited by these molecules against
Alternaria alternata, Aspergillus flavus, Aspergillus niger, and Fusar-
ium oxysporum, which we have already reported in our previous
communication.25 The present insecticidal screening was aimed to
test the bioefficacy of few of the synthesized thiophosphonates on
Holotrichea consanguinea Blanch. A dose of 50 ppm v/v was selected
for inoculation. Observations on the mortality of the insect have been
recorded for two, four, seven, and ten days of their introduction to the
toxic soil. The results have been analyzed statistically, and results have
been presented in Table IV and Figure 1.
FIGURE 1 Percent mortality of Holotrichea consanguinea at 2, 4, 7, and 10
days after the treatment.

1376

Biodynamic Bisamidothiophosphonates
1377
CONCLUSION
In the present study a chiral thiophosphonates system was developed
successfully with interesting diastereotopicities. The products exhib-
ited substantial bioactivity against white grub, the most harmful pest
insect of India. The best result with 65.47% mortality was recorded in
4a, 4b, and 6a after final observations. These three compounds struc-
turally incorporate electron-withdrawing (phenyl and ester groups)
and bulky (diethylamido/diphenylamido) substituents, which fulfill the
basic requirement for insecticidal activity.26,27 There was no grub mor-
tality in the untreated control. Test compound 4a with effective insecti-
cidal property was screened in a pot experiment and showed a substan-
tial 70% mortality in the first star grubs of H. consanguinea Blanch in
21 days.
EXPERIMENTAL SECTION
All the commercial reagents and solvents were distilled and dried un-
der a nitrogen atmosphere before use. Reactions were carried out in
dry equipments using Schlenk techinques. The melting points were
determined on an electric tempo instrument by the capillary method.
NMR spectra were recorded on Jeol AL 300 at 121.50 MHz (31P NMR)
and 300.40 MHz (1H NMR), or Jeol FX 90Q at 36.23 MHz (31P NMR),
89.50 MHz (1H NMR), and 75.45 MHz (13C NMR). Elemental analyses
were carried out on a Heraeus Carlo Erba 1108 analyzer. Fast atomic
bombardment (FAB) mass spectrum was recorded on a Jeol SX 102/DA–
6000 mass spectrometer/data system using Argon/Xenon (6 KV, 10 mA)
as the FAB gas.
General Procedure for the N-Alkyl-2-pyridinylidenamido-
(diethylamido)(phenyl)thiophosphonates (4a–f)
Triethylamine (4.5 mL, 32 mmoles) was added to a well-stirred suspen-
sion of N-alkyl-2-aminopyridinium halides (4 g, 16 mmoles) in toluene
(10 mL) at 0–5◦C. Simultaneously, a solution of dichlorophenylphos-
phine (2.2 mL, 16 mmoles) in a 2:1 mixture of toluene and methylene
chloride (30:15 mL) was added dropwise with constant stirring. Sulfur
(0.5 gm, 16 mmoles) was added to the reaction mixture, and stirring
was continued for 2–3 days at room temperature. To this a solution of
diethylamine (3.4 mL, 32 mmoles) in methylene chloride (5 mL) was
added dropwise at 0–5◦C. Here two equivalents of diethylamine have
been used as a nucleophile as well as a base. The resulting mixture
was brought to room temperature and left for stirring for 2 days. The

1378
V. Kabra et al.
reaction was filtered, and solvent was removed under reduced pressure;
residue was extracted with diethyl ether (2 × 50 mL). The combined
ethereal extract was concentrated to one-fourth of its volume and left in
a refrigerator, whereupon a white-to-light-yellow crystalline solid was
deposited. The compound was filtered, recrystallized with methylene
chloride, and dried.
General Procedure for the N-Alkyl-2-pyridinylidenamido-
(N-methylcyclohexylamido)(phenyl)thiophosphonates (5a–d)
To a suspension of N-alkyl-2-aminopyridinium halides (4 g, 16 mmoles)
in toluene (10 mL) was added triethylamine (4.5 mL, 32 mmoles) at
0–5◦C. A solution of dichlorophenylphosphine (2.2 mL, 16 mmoles) in
a 2:1 mixture of toluene and methylene chloride (30:15 mL) was added
dropwise with constant stirring. Stirring of the mixture was continued
for 2 h. To this was added sulfur powder (0.5 g, 16 mmoles). On the
third day, one equivalent amount of triethylamine (2.3 mL, 16 mmoles)
followed by a dropwise addition of N-methylcyclohexylamine (2.1 mL,
16 mmoles) in methylene chloride (5 mL) was done, while maintaining
the temperature at 0–5◦C, and the resulting mixture was stirred for
2 days. The reaction was filtered, solvent was removed under reduced
pressure, and the residue was extracted with diethyl ether (2 × 50 mL).
The combined ethereal extract was concentrated and left in a refrigera-
tor, whereupon a white-to-light-brown solid was separated, which was
filtered, recrystallized with methylene chloride, and dried.
General Procedure for the N-Alkyl-2-pyridinylidenamido-
(diphenylamido)(phenyl)thiophosphonates (6a)
An analogous procedure was carried out for the synthesis of 6a by
a dropwise addition of diphenylamine (2.7 g, 16 mmoles) in methy-
lene chloride (5 mL) in the presence of a base triethylamine (2.3 mL,
16 mmoles) while maintaining the temperature at 0–5◦C, and the re-
sulting mixture was stirred for 2 days. The reaction was filtered, solvent
was removed under reduced pressure, and residue was extracted with
diethyl ether (2 × 50 mL). The combined ethereal extract was concen-
trated and left in a refrigerator, whereupon a white solid was separated,
which was filtered, recrystallized with methylene chloride, and dried.
General Procedure for the N-Alkyl-2-pyridinylidenamido-
(diisopropylamido)(phenyl) thiophosphonates (7a)
A procedure similar to that for 4 was followed using triethylamine (2.3
mL, 16 mmoles) and a solution of diisopropylamine (2.1 mL, 16 mmoles)

Biodynamic Bisamidothiophosphonates
1379
in methylene chloride (5 mL) in place of diethylamine, and the result-
ing mixture was stirred for 2 days. The reaction was filtered, solvent
was removed, and the residue was extracted with diethyl ether (2 ×
50 mL). The combined ethereal extract was concentrated and left in
a refrigerator, whereupon a white solid separated, which was filtered,
recrystallized with methylene chloride, and dried.
Bioactivity
A dose of 5 kg/hectare was computed for soil bioassay. 50 cc (∼ 60 g) of
air-dried soil was taken in each plastic container (length = 8 cm and
diameter = 5 cm) with 12 mL of stock solution (75 mg of compound dis-
solved in a little quantity of acetone and diluted with 180 mL of water).
In these containers, one test grubs was introduced with some millet
roots. For control (soil, water, and acetone mixture) grub and millet
root were taken. Ten such replicates were prepared for each compound;
percent mortality of the insect in each replicate was calculated. The per-
centage figures were then converted to the angular transformed values,
which were subjected to the statistical analysis of Completely Random-
ized Design technique.
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