Synthesis and molluscicidal activity of phosphorus-containing heterocyclic compounds derived from 5,6-bis (4-bromophenyl)-3-hydrazino-1,2,4-triazine

Article abstract of DOI:10.1080/10426500801967864

Novel N1-(phosphoryl moiety)-N2-(1,2,4-triazin-3-yl)hydrazines 4, 6, 8, 9 and 12, iminophosphorane 3, iminophosphane 5, 1,2,4-triazinyldiazaphospholine 7, 1,2,4,3-triazaphospholinotriazines 2, 10, 11, and 1,2,4-triazino[3,2-c][1,2,4, 5] triazaphosphine 13

Full text of DOI:10.1080/10426500801967864

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Synthesis and Molluscicidal
Activity of Phosphorus-
Containing Heterocyclic
Compounds Derived from
5,6-Bis (4-bromophenyl)-3-
hydrazino-1,2,4-triazine
T. E. Ali a , R. M. Abdel-Rahman a , F. I. Hanafy a & S.
M. El-Edfawy a
a Department of Chemistry, Ain Shams University,
Roxy, Cairo, Egypt
Version of record first published: 26 Sep 2008.
To cite this article: T. E. Ali, R. M. Abdel-Rahman, F. I. Hanafy & S. M. El-Edfawy
(2008): Synthesis and Molluscicidal Activity of Phosphorus-Containing Heterocyclic
Compounds Derived from 5,6-Bis (4-bromophenyl)-3-hydrazino-1,2,4-triazine,
Phosphorus, Sulfur, and Silicon and the Related Elements, 183:10, 2565-2577
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Phosphorus, Sulfur, and Silicon, 183:2565–2577, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500801967864
Synthesis and Molluscicidal Activity of
Phosphorus-Containing Heterocyclic Compounds Derived
from 5,6-Bis (4-bromophenyl)-3-hydrazino-1,2,4-triazine
T. E. Ali, R. M. Abdel-Rahman, F. I. Hanafy,
and S. M. El-Edfawy
Department of Chemistry, Ain Shams University, Roxy, Cairo, Egypt
1
Novel N -(phosphoryl moiety)-N2-(1,2,4-triazin-3-yl)hydrazines 4, 6, 8, 9 and
12, iminophosphorane 3, iminophosphane 5, 1,2,4-triazinyldiazaphospholine 7,
1,2,4,3-triazaphospholinotriazines 2, 10, 11, and 1,2,4-triazino[3,2-c][1,2,4,5] tri-
azaphosphine 13 have been obtained via treatment 5,6-bis(4-bromophenyl)-3-
hydrazino-1,2,4-triazine (1) with various polyfunctional phosphorus reagents by
stirring at room temperature or refluxing for long time in tetrahydrofuran. Struc-
tures of these compounds have been deduced upon the basis of elemental and spec-
tral data. Molluscicidal activity of the prepared compounds against Biomphalaria
Alexandrina snails (the intermediate host of Schistosoma mansoni) showed con-
siderable activities.
Keywords Molluscicidal activity; phosphorus; synthesis; 1,2,4-triazine
INTRODUCTION
1,2,4-Triazines have recently been exploited as anti-AIDS,1 anticancer,2
and antimicrobial activities,3 which are attributed to the nature of subs-
tituents in 1,2,4-triazine ring. Furthermore, 5,6-diphenyl-3-hydrazino-
1,2,4-triazine was shown to be useful starting material for synthesis of
great variety of functionalized heteropolycyclic system.4 On the other
hand, it is known that phosphorus containing heterocyclic compounds
are very interesting biologically active.5 Synthesis of several phos-
phono substituted 1,2,4-triazines, triazinylphosphoramidates6,7 and
series of stable phosphorus ylides incorporating 1,2,4-triazine moiety as
Received 6 November 2007; accepted 18 January 2008.
We thank institute of polymers, Bulgarian Academy of Science, for helping to measure
31P NMR spectra. Also, we thank Dr. Mortada El-Sayed for helping in testing the pre-
pared compounds as molluscicidal agents in Theodor Bilharz Research Institute, Giza,
Egypt.
Address correspondence to T. E. Ali, Department of Chemistry, Faculty of Education,
Ain Shams University, Roxy, 11711, Cairo, Egypt. E-mail: tarik elsayed1975@yahoo.com
2565

2566
T. E. Ali et al.
accessible intermediates for preparing new 1,2,4-triazine derivatives of
therapeutically potencies have been reported.8,9 It is conceivable that
molecular modification of 1,2,4-triazine rings introducing organophos-
phorus functionalities might be expected to exhibit the potential
activities, depending on the position of the phosphoryl group to 1,2,4-
triazine ring. The present work describes synthesis of phosphorus con-
taining fused and isolated heterocyclic systems via reaction of 5,6-
bis(4-bromophenyl)-3-hydrazino-1,2,4-triazines (1) with some phospho-
rus reagents in nonpolar solvent under different temperatures. Mol-
luscicidal activity of the prepared compounds against Biomphalaria
Alexandrina snails (the intermediate host of Schistosoma mansoni)
showed considerable activities.
RESULTS AND DISCUSSION
The synthesis of heterocyclic systems containing a 1,2,4-triazine moiety
has gained much attention because of their rapid effect in various
diseases.10 Thus, a facile route to synthesize of 6,7-bis(4-bromophenyl)-
2,3-dihydro-3,3,3-triphenyl-3-λ5-1,2,4,3-triazaphosph-olino[4,5-b][1,2,
SCHEME 1

Molluscicidal Activity of Phosphorus-Containing Heterocyclic Compounds 2567
4]triazine (2) was deduced from stirring 5,6-bis(4-bromophenyl)-3-
hydrazino-1,2,4-triazine (1) with dibromotriphenylphosphorane in
THF containing piperidine at room temperature for 24 hours, while
that reaction when carried out under refluxing conditions yielded
5,6-bis(4-bromophenyl)-3-[2-(triphenylphosphoranylidene)hydrazine]-
1,2,4-triazine (3) (Scheme 1). Formation of 2 may be occurred via
heterocyclization of the intermediate N1, N2-disubstituted hydrazine
through N − 2 of a triazine moiety, while compound 3 is formed via
iminophosphorane mechanism. The 31P NMR spectrum of compound
2 showed singlet signal at δ 29.61 ppm.11 Also, IR spectrum of
–1
iminophosphorane 3 showed N P group as strong band at 1399 cm
while its 31P NMR spectrum appeared at δ 15.87 ppm.12
We note that when phosphorus atom found in trivalent phosphine
behaves as powerful nucleophile. Thus, stirring of 3-hydrazinotriazine
1 with tris(2-chloroethoxy)phosphine in THF containing piperidine
at room temperature gave the corresponding hydrazidophosphite 4
which is formed via attacking of NH2 group at the carbon atom
which carries partial positive charge according to Horner-Emmons
reactions (Scheme 2).13,14 On the other hand, refluxing of 1 with
tris(2-chloroethoxy)phosphine in boiling THF and piperidine resulted
SCHEME 2

2568
T. E. Ali et al.
1
iminophosphane 5 (Scheme 2). The H and 31P NMR spectra of com-
pounds 4 and 5 supported the postulated structures.11
Some five–membered organophosphorus heterocyclic compounds
have been synthesized by Mannich-type reactions of guanidine deriva-
tives with phenyldichlorophsphine and ketones and/or aminohetero-
cyclic with aryl phosphoryl dichloride and aromatic aldehydes.15,16
Similarly, phosphorylation of 3-hydrazinotriazine 1 via treatment with
acetonyltriphenylphosphonium chloride under stirring in THF and
few drops of piperidine for 24 hours at room temperature achieved
1-[{2-[5,6-bis(4-bromophenyl)-1,2,4-triazin-3-yl] hydrazino}(triphenyl-
phosphoranyl)]acetone (6) (Scheme 3). Formation of 6 may due to
that phosphorus reagent such as phosphonium salt in which phos-
phorus atom is more electrophilic than carbon when one of the five
groups is good leaving group. Also, the reaction of 1 with acetonyl-
triphenylphosphonium chloride in boiling THF-piperidine afforded
5,6-bis (4-bromophenyl)-3-[(3,3,3-triphenyl)-5-methyl-3,4-dihydro-2H-
1,2,3-λ5-diazaphosphol-2-yl] -1,2,4-triazine (7) (Scheme 3). Formation
of 7 may be occurred via nucleophilic attack of hydrazine moiety at
carbonyl group to loss molecule of water followed by leaving of HCl.
Abdel-Rahman,3 reported that refluxing of 3-hydrazino-1,2,4-
triazine derivatives with α,β-bifunctional groups especially haloketone
and/or oxoketone produced hydrazone. Thus, one of the most impor-
tant of the present investigation is treatment of 3-hydrazinotriazine 1
with diethyl phosphite and/or 2-chlorophenyldichlorothiophosphate in
SCHEME 3

Molluscicidal Activity of Phosphorus-Containing Heterocyclic Compounds 2569
SCHEME 4

2570
T. E. Ali et al.
THF containing few drops of piperidine at room temperature yielded
phosphonohydrazide 8 and phosphonohydrazidothioic acid 9, respec-
tively (Scheme 4). Also, repeat the same reactions under refluxing led to
the direct formation of the 1,2,4,3-triazaphospholo[4,5-b] [1,2,4]triazine
derivatives 10 and 11, respectively. Formation of 10 and 11 may be oc-
curred via nucleophilic attack of the primary NH2 group of hydrazine on
phosphorus atom to remove ethoxy and/or chlorine atom as good leav-
ing groups followed by heterocyclization by loss one molecule of ethanol
1
and/or HCl. The H NMR spectra of 10 and 11 showed signals of NH
protons at δ 10.92 and 10.34 ppm, respectively, while their 31P NMR
spectra recorded signals at δ 14.52 and 47.72 ppm, respectively.17–19
Phosphorus compounds with a nitrogen or oxygen heteroatom
on the carbon α to phosphorus very often exhibited interesting bio-
logical properties.20 Thus, introducing of P–C–O or P–C–N pattern
into heterocyclic structure was achieved by interaction between 3-
hydrazinotriazine 1 and diphenyl(2,4,6-trimethylbenzoyl)phosphorus
oxide under stirring in THF at room temperature resulting (diphenyl-
phosphoryl){[2-[5,6-bis(4-bromophenyl)-1,2,4-triazin-3-yl]hydrazino}
(2ꢀ,4ꢀ,6ꢀ-trimethoxyphenyl)methanol (12), while on refluxing afforded
7,8-bis(4-bromophenyl)-4,4-diphenyl-3-(2ꢀ,4ꢀ,6ꢀ-trimethylphenyl)-4H-
4λ5-1,2,4-triazino[3,2-c][1,2,4,5]triazaphosphinin-4-ol (13) (Scheme 5).
Due to driving force of P O bond is strong and phenyl groups are bad
leaving groups, the nucleophilic attack of hydrazino moiety may be
carried out at carbonyl group then P O group. Structures of 12 and 13
were determined on basis of elemental analysis and spectral methods.
MOLLUSCICIDAL ACTIVITY
Schistosomiasis (also called Bilharziasis) is the most important trema-
tode disease in human. It is an endemic disease in many tropical and
subtropical regions. The intermediate host of Schistosoma mansoni,
which affects the intestinal system, is Biomphalaria Alexandrina snails
(average shell diameter 6–8 mm) in Giza governorate in Egypt. The
Snails were adapted to laboratory conditions three weeks before being
used in toxicity, tests to be sure that the snails are strong and healthy.
Snails were kept in plastic aguaria filled with dechlorinated tap water
at room temperature 25–27◦C. Dried lettuce leaves were added daily,
and the water was changed weakly. Stock solution of the investigated
compounds (500 ppm) were dissolved in the least amount of ethanol and
diluted with dechlorinated tap water based on weight/volume. Series of
dilutions of each compound were prepared.21–24 Table I indicates that
under the employed experimental conditions the quantitative structure

Molluscicidal Activity of Phosphorus-Containing Heterocyclic Compounds 2571
SCHEME 5
activity relationship studies of these compounds. It is obvious that most
of the prepared compounds on the tested snails depend on the type of
N–P moieties which inter of their structures. Generally, the effect of
the synthesized compounds is attributed to the following.
1. The presence of a phosphorus atom bound to nitrogen, which con-
tains the backbone of the skeleton.
2. The strong effect of the compounds 2, 7, 10, 11, and 13 on the tested
snails appears in the cases of phosphorus heterobicyclic systems,
due to facile donation and back donation in d-orbital of phosphorus
atom.
3. The medial effect of the compounds 4, 6, 8, and 12 on the tested
snail exhibited in the cases, which recorded a conjugation system
created.
4. A lethal effect of the evaluated compounds 3, 5, and 9 on the tested
snail was deduced in the case where weak interactions between N P
were a poor donation and back donation is recorded.
5. In most cases, the total electron barrier of molecular structure of
the evaluated compounds led to inhibition enzymatic effect on living

2572
T. E. Ali et al.
TABLE I The Molluscicidal Activity of the Prepared Compounds
against Biomphalaria Alexandrina Snails
Mortality % of snails at concentration
Compound no.
100 ppm
50 ppm
25 ppm
2
3
100
0
30
0
20
0
4
5
30
0
20
0
10
0
6
7
8
9
10
11
12
13
20
60
30
10
100
100
20
80
100
20
20
20
0
20
30
10
30
100
10
10
10
0
10
30
10
20
100
Baylucide (reference standard)
processes for the tested snail via the contribution between apoen-
zyme and coenzyme, which may be loose that it and can be broken
by a simple process of snails.
CONCLUSION
Synthesis of phosphorus containing fused and isolated heterocyclic sys-
tems as molluscicidal agents against Biomphalaria Alexandrina snails
have been achieved via reaction of 5,6-bis(4-bromophenyl)-3-hydrazino-
1,2,4-triazines (1) with some polyfunctional phosphorus reagents in
tetrahydrofuran under stirring and reflux.
EXPERIMENTAL
Melting points were determined on Boetius apparatus and were un-
corrected. IR spectra in KBr were recorded on a Perkin-Elmer 293 FT
spectrophotometer (λmax cm–1). UV absorption spectra in DMF were
recorded on a Perkin-Elmer, Lambda 4B controller accessory inter-
1
face. UV-VIS spectrophotometer (λmax in nm). H NMR spectra were
recorded on an EM NMR spectrometer 300 MHz PMR using CDCl3
as a solvent and TMS as internal reference (chemical shift in ppm).
31P NMR spectra of were registered on a Varian Inova 500 MHz spec-
trometer at room temperature using TMS as internal standard and

Molluscicidal Activity of Phosphorus-Containing Heterocyclic Compounds 2573
85% H3PO4 as external reference. Mass spectrum recorded on a Gas
Chromatographic GCMSqp 1000 ex Schimadzu instrument at 70 eV.
Elemental analysis was carried out at microanalytical center, Cairo
university. 5,6-Bis(4-bromophenyl)-3-hydrazino-1,2,4-triazine (1) was
prepared according to the published method in literature.25
1,2,4,3-Triazaphospholinotriazine 2, N1-(phosphoryl
moiety)-N2-(1,2,4-triazin-3-yl)hydrazines 4, 6, 8, 9,
and 12—General Method
A mixture of 3-hydrazinotriazine 1 (5 mmol) and phosphorus reag-
ents such as dibromotriphenylphosphorane, tris(2-chloroethoxy)
phosphine, acetonyltriphenyl phosphonium chloride, diethyl phos-
phite, 2-chlorophenyldichlorothiophosphate and/or diphenyl-(2,4,6-
trimethylbenzoyl)phosphorus oxide (5 mmol) in THF (50 ml) containing
few drops of piperidine was stirred at room temperature (25–30◦C) for
24 h. The solid separated was collected, washed with diethyl ether and
crystallized from a suitable solvent affording the corresponding prod-
ucts 2, 4, 6, 8, 9, and 12, respectively.
6,7-Bis(4-bromophenyl)-2,3-dihydro-3,3,3-triphenyl-3-λ5-
1,2,4,3-triazaphospholo [4,5-b][1,2,4]triazine (2)
Brown crystals from ethanol,23% yield, m.p. = 130–131◦C. IR
(υ´/cm–1): 3420 (NH), 1578 (C N). 1H NMR (CDCl3, 300 MHz) δ:
7.26–7.70 (m, 23H, Ar–H), 11.60 (br, 1H, NH). 31P NMR (CDCl3,
101.25 MHz) δ: 29.61 ppm. MS (m/z, %): 681 (M+1, 10.23%), 680
(M+, 11.36), 550 (18.18), 456 (14.77), 388 (15.91), 362 (13.64), 277
(72.73), 183 (100), 157 (59.09), 75 (59.09). Anal. calcd. for C33H24Br2N5P
(681.37): C, 58.17; H, 3.55; P, 4.55%. Found: C, 57.82; H, 3.19; P,
4.32%.
Bis(2-chloroethyl) N-[(5,6-bis(4-bromophenyl)-1,2,4-triazin-
3-yl]hydrazido-phosphite (4)
Yellow crystals from ethanol, 35% yield, m.p. = 170–171◦C. IR
(υ´/cm–1): 3298, 3218 (NHNH), 1582 (C N), 1067, 1006 (P–O–C). H
1
NMR (CDCl3, 300 MHz) δ: 1.56–1.66 (m, 4H, CH2), 1.90 (br, 4H, CH2),
3.13 (br, 4H, CH2Cl), 6.32 (s, 1H, NH), 7.20–7.84 (m, 8H, Ar–H), 9.45
(br, 1H, NH). 31P NMR (CDCl3, 101.25 MHz) δ: 19.50 ppm. MS (m/z, %):
654 (M+, 75%), 313 (75), 185 (87.50), 156 (43.75), 137 (81.26), 74 (100).
Anal. calcd. for C21H22Br2Cl2N5O3P (654.13): C, 38.56; H, 3.39; P, 4.74
%. Found: C, 37.99; H, 3.11; P, 4.66%.

2574
T. E. Ali et al.
1-[{2-[5,6-Bis(4-bromophenyl)-1,2,4-triazin-3-
yl]hydrazino}(triphenylphosphor-anyl)]acetone (6)
Yellow crystals from methanol, 42% yield, m.p. = 220–222◦C. IR
(υ´/cm–1): 3318, 3209 (NHNH), 1685 (C O), 1587 (C N). 1H NMR
(CDCl3, 300 MHz) δ: 1.92 (s, 3H, CH3), 3.35 (br, 2H, CH2), 6.32 (s, 1H,
NH), 7.18–7.89 (m, 23H, Ar–H), 9.62 (br, 1H, NH). 31P NMR (CDCl3,
101.25 MHz) δ: 20.43 ppm. MS (m/z, %): 739 (M+, 55.56%), 616 (55.56),
610 (55.56), 556 (55.56), 536 (55.56), 390 (72.22), 263 (72.22), 196
(61.11), 77 (100). Anal. calcd. for C36H30Br2N5OP (739.46): C, 58.48;
H, 4.09; P, 4.19%. Found: C, 57.94; H, 3.85; P, 3.69%.
Ethyl N-[(5,6-bis(4-bromophenyl)-1,2,4-triazin-3-
yl]phosphonohydrazide (8)
Yellow crystals from ethanol, 25% yield, m.p. = 133–135◦C. UV λmax
(ε): 210 (0.95), 280 (0.80), 320 (1.00), 385 (0.10). IR (υ´/cm–1): 3409 (br,
NHNH), 1585 (C N), 1216 (P O), 1071 (P-O-C). 1H NMR (CDCl3, 300
MHz) δ: 1.32 (t, 3H, J = 6.9 Hz, CH3), 3.82 (q, 2H, J=7 Hz, CH2), 6.5
(br, 1H, P–H), 6.33 (s, 1H, NH), 7.19–7.86 (m, 8H, Ar–H), 9.52 (br, 1H,
NH). 31P NMR (CDCl3, 101.25 MHz) δ: 7.28 ppm. MS (m/z, %): 529
(M+O, 20.41%), 513 (M+, 28.57), 460 (22.45), 453 (24.49), 367 (20.41),
324 (24.49), 257 (34.69), 185 (61.22), 155 (100), 90 (65.31). Anal. calcd.
for C17H16Br2N5O2P (513.13): C, 39.39; H, 3.14; P, 6.04%. Found: C,
38.98; H, 3.02; P, 5.67%.
N-{[5,6-bis(4-bromophenyl)-1,2,4-triazin-3-yl]P-[2-
chlorophenyl]phosphono-hydrazidothioic chloride (9)}
Yellow crystals from benzene, 36% yield, m.p. = >300◦C. IR (υ´/cm–1):
3413, 3278 (NHNH), 1579 (C N), 755 (P S). 1H NMR (CDCl3,
300 MHz) δ: 6.38 (s, 1H, NH), 7.20–7.91 (m, 12H, Ar–H), 9.82 (br, 1H,
NH). 31P NMR (CDCl3, 101.25 MHz) δ: 53.96 ppm. MS (m/z, %): 630
(M+, 70.59), 619 (56.82), 561 (64.71), 471 (58.82), 389 (64.71), 382
(76.47), 282 (58.82), 256 (64.71), 158 (100), 122 (70.59), 800 (70.59).
Anal. calcd. for C21H14Br2Cl2N5PS (630.13): C, 40.03; H, 2.24; P, 4.92%.
Found: C, 39.94; H, 2.15; P, 4.52%.
(Diphenylphosphoryl){[2-[5,6-bis(4-bromophenyl)-1,2,4-
triazin-3-yl]hydrazino} (2,4,6-trimethoxyphenyl)methanol (12)
Yellow crystals from methanol, 33% yield, m.p. = 224–226◦C. UV
λmax (ε): 210–225 (0.95), 275–285 (1.25), 340–360 (0.15), 390 (0.05). IR
(υ´/cm–1): 3143 (br, NH, OH), 1583 (C N), 1211 (P O). 1H NMR (CDCl3,
300 MHz) δ: 1.56 (s, 9H, CH3), 2.12 (br, 1H, OH), 6.25 (br, 1H, NH), 7.08–
7.88 (m, 20H, Ar–H), 9.32 (br, 1H, NH). 31P NMR (CDCl3, 101.25 MHz)

Molluscicidal Activity of Phosphorus-Containing Heterocyclic Compounds 2575
δ: 32.83 ppm. MS (m/z, %): 772 (M+3, 1.66%), 689 (2.15), 622 (1.82),
576 (1.99), 474 (1.99), 406 (2.15), 268 (2.15), 155 (100), 74 (65.23). Anal.
calcd. for C37H32Br2N5O2P (769.48): C, 57.75; H, 4.19; P, 4.03%. Found:
C, 57.94; H, 4.15; P, 3.72%.
Iminophosphorane 3, Iminophosphane 5,
1,2,4-Triazinyldiazaphospholine 7,
1,2,4,3-Triazaphospholinotriazine 10, 11, and
1,2,4,5-Triazaphosphinine 13—General Method
A mixture of 3-hydrazinotriazine 1 (5 mmol) and dibromotripheny-
lphosphorane, tris(2-chloroethoxy)phosphine, acetonyltriphenylphos-
phonium chloride, diethyl phosphite, 2-chlorophenyldichlorothio-
phosphate and/or diphenyl-(2,4,6-trimethylbenzoyl)phosphorus oxide
(5 mmol) in THF (50 ml) containing few drops of piperidine was refluxed
for 12 h. The solvent was removed under vacuum, and the residue was
treated with methanol or ethyl acetate and crystallized from a suit-
able solvent to give the corresponding products3, 5, 7, 10, 11, and 13,
respectively.
5,6-Bis(4-bromophenyl)-3-[2-
(triphenylphosphoranylidene)hydrazino]-1,2,4-triazine (3)
Yellow crystals from ethanol, 88% yield, m.p. = 240–242◦C. IR
(υ´/cm–1): 3408 (br, NH), 1584 (C N), 1399 (N P). H NMR (CDCl3,
1
300 MHz) δ: 8.45 (br, 1H, NH), 7.23–7.73 (m, 23H, Ar–H). 31P NMR
(CDCl3, 101.25 MHz) δ: 15.87 ppm. MS (m/z, %): 683 (M+2, 4.74%),
682 (M+1, 4.01), 681 (M+, 3.28), 586 (5.47), 462 (3.28), 402 (4.72), 292
(7.30), 277 (100), 199 (25.55), 77 (42.34). Anal. calcd. for C33H24Br2N5P
(681.37): C, 58.17; H, 3.55; P, 4.55%. Found: C, 57.94; H, 4.29; P,
4.13%.
2-Chloroethyl{2-[5,6-bis(4-bromophenyl)-1,2,4-triazin-3-
yl]hydrazono} phosphinite (5)
Yellow crystals from toluene, 36% yield, m.p. = 170–171◦C. UV λmax
(ε): 205 (0.9), 245 (1.15), 290(1.00), 320 (0.65), 330 (0.60). IR (υ´/cm–1):
1
3218 (NH), 1583 (C N), 1334 (N P), 1066 (P-O-C). H NMR (CDCl3,
300 MHz) δ: 1.60 (br, 2H, CH2), 3.71 (t, 2H, CH2), 6.33 (s, 1H, NH),
7.19–7.84 (m, 8H, Ar–H). 31P NMR (CDCl3, 101.25 MHz) δ: 14.45 ppm.
MS (m/z, %): 529 (M+, 5.37%), 527 (5.37), 424 (5.37), 382 (15.12), 313
(4.88), 233 (4.88), 199 (98.05), 155 (100), 76 (62.93). Anal. calcd. for
C17H13Br2ClN5OP (529.56): C, 38.56; H, 2.47; P, 5.85%. Found: C, 37.98;
H, 2.31; P, 5.48%.

2576
T. E. Ali et al.
5,6-Bis(4-bromophenyl)-3-[(3,3,3-triphenyl)-5-methyl-3,4-
dihydro-2H-1,2,3-λ5-diazaphosphol-2-yl]-1,2,4-triazine (7)
Brown crystals from methanol, 22% yield, m.p. = 213–214◦C. IR
(υ´/cm–1): 3090 (C-Harom), 2810 (C-Haliph), 1586 (C N). 1H NMR (CDCl3,
300 MHz) δ: 1.54 (s, 3H, CH3), 3.75 (br, 2H, CH2), 7.25–8.00 (m, 23H,
Ar–H). 31P NMR (CDCl3, 101.25 MHz) δ: 25.90 ppm. MS (m/z, %): 723
(M+2, 58.82%), 722 (M+1, 64.71), 567 (64.71), 534 (94.12), 404 (82.35),
348 (70.59), 279 (82.35), 206 (88.24), 103 (100), 55 (94.12). Anal. calcd.
for C36H28Br2N5P (721.44): C, 59.94; H, 3.91; P, 4.29%. Found: C, 57.84;
H, 3.75; P, 3.90%.
6,7-Bis(4-bromophenyl)-2,3-dihydro-1,2,4,3-
triazaphospholo[4,5-b][1,2,4] triazine-3-oxide (10)
Yellow crystals from methanol, 19% yield, m.p. = 198–199◦C. UV
λmax (ε):220 (1.05), 280 (0.70), 330 (0.75), 390 (0.10). IR (υ´/cm–1): 3415
(NH), 1587 (C N), 1218 (P O). 1H NMR (CDCl3, 300 MHz) δ: 6.61
(br, 1H, P–H), 7.18–7.88 (m, 8H, Ar–H), 10.92 (br, 1H, NH).31P NMR
(CDCl3, 101.25 MHz) δ: 14.52 ppm. MS (m/z, %): 467 (M+, 11.96%), 466
(10.87), 419 (11.96), 368 (16.30), 325 (14.13), 269 (16.30), 226 (21.74),
183 (100), 155 (98.91), 76 (75). Anal. calcd. for C15H10Br2N5OP (467.06):
C, 38.57; H, 2.16; P, 6.63%. Found: C, 38.04; H, 1.95; P, 6.80%.
3-(2-Chlorophenyl)-6,7-bis(4-bromophenyl)-2,3-dihydro-
1,2,4,3-triazaphospholo [4,5-b][1,2,4]triazine-3-sulfide (11)
Yellow crystals from methanol, 38% yield, m.p. = 219–220◦C.
IR (υ´/cm–1): 3309 (NH), 1577 (C N), 753 (P S). 1H NMR (CDCl3,
300 MHz) δ: 7.09–7.78 (m, 12H, Ar–H), 10.34 (br, 1H, NH). 31P NMR
(CDCl3, 101.25 MHz) δ: 47.72 ppm. MS (m/z, %): 592 (M-H, 27.50), 460
(25), 37 (35), 292 (37.50), 213 (35), 178 (100), 151 (37.50), 55 (35). Anal.
calcd. for C21H13Br2ClN5PS (593.67): C, 42.49; H, 2.21; P, 5.22%. Found:
C, 42.05; H, 2.15; P, 4.84%.
7,8-Bis(4-bromophenyl)-4,4-diphenyl-3-(2,4,6-trimethylphenyl)-
4H-4λ5-1,2,4-triazino[3,2-c][1,2,4,5]triazaphosphinin-4-ol (13)
Brown crystals from methanol, 27% yield, m. p. = 129–130◦C. UV
λmax (ε): 210 (0.45), 240 (0.95), 280 (1.15), 350 (0.50). IR (υ´/cm–1): 3414
(br, OH), 1581 (C N), 1070 (P–OH). 1H NMR (CDCl3, 300 MHz) δ: 1.57
(s, 9H, CH3), 4.19 (s, 1H, OH), 7.09–7.85 (m, 20H, Ar–H). 31P NMR
(CDCl3, 101.25 MHz) δ: 25.70 ppm. MS (m/z, %): 752.30 (M+1, 2.43),
644 (3.10), 533 (4.87), 441 (3.32), 334 (6.64), 323 (4.65), 173 (7.30), 82
(100). Anal. calcd. for C37H30Br2N5OP (751.47): C, 59.14; H, 4.02; P,
4.12%. Found: C, 58.94; H, 3.88; P, 3.74%.

Molluscicidal Activity of Phosphorus-Containing Heterocyclic Compounds 2577
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