C-phosphorylation of 1,2,4-triazoles with phosphorus(III) halides. Synthesis of 4,5-dihydrobenzo[e][1,2,4]triazolo[5,1-c] [1,4,2] diazaphosphinine derivatives

Article abstract of DOI:10.1002/hc.10010

Phosphorylation of 4- and 1-substituted 1,2,4-triazoles with PCl₃, PhPCl₂, Ph₂PCl, and (Et₂N)₂ PCl was carried out. A novel phosphorus-containing condensed heterocyclic system (18, 23) was constructed by the reactions of 2-(1H-1,2,4-triazol-1-yl)1-(4-chlorophenylcarboxamido)-5-trifluoromethylbenzene with PBr₃ and PhPBr₂. Treatment of the bromophosphonite 18 with an excess of morpholine in the presence of sulfur resulted in a diazaphosphinine ring opening and provided functionalized 1H-1,2,4-triazol-5-ylphosphonic acid derivatives 21 and 22.

Full text of DOI:10.1002/hc.10010

Heteroatom Chemistry
Volume 13, Number 2, 2002
C-Phosphorylation of 1,2,4-Triazoles
with Phosphorus(III) Halides. Synthesis
of 4,5-Dihydrobenzo[e][1,2,4]Triazolo[5,1-c]
[1,4,2]Diazaphosphinine Derivatives
Evgenij V. Zarudnitskii, Vladimir V. Ivanov, Alexandr A. Yurchenko,
Alexandr M. Pinchuk, and Andrej A. Tolmachev
Institute of Organic Chemistry, National Academy of Sciences of Ukraine, Kiev-94, 02094, Ukraine
Received 31 May 2001; revised 15 July 2001
As an extension of our research on the direct C-
ABSTRACT: Phosphorylation of 4- and 1-substituted
phosphorylation of 1,3-azoles with phosphorus(III)
1,2,4-triazoles with PCl3, PhPCl2, Ph2PCl, and (Et2N)2
halides, we studied the 1,2,4-triazole ring system in
PCl was carried out. A novel phosphorus-containing
this reaction. A general approach to C-phosphory-
condensed heterocyclic system (18, 23) was con-
lated heterocycles via their lithiated derivatives
structed by the reactions of 2-(1H-1,2,4-triazol-1-yl)-
has been found suitable for the syntheses of C-
1-(4-chlorophenylcarboxamido)-5-trifluoromethyl-
phosphorylated 1H- as well as 4H-1,2,4-triazoles
benzene with PBr3 and PhPBr2. Treatment of the
[3,4]. However, owing to the low stability of the
bromophosphonite 18 with an excess of morpholine
intermediate organometallic species, only mode-
in the presence of sulfur resulted in a diazaphos-
rate yields of the final products were obtained in
phinine ring opening and provided functionalized
some cases. As demonstrated in our preliminary
1H-1,2,4-triazol-5-ylphosphonic acid derivatives 21
communication [5], introduction of a nitrogen atom
C
and 22. 2002 Wiley Periodicals, Inc. Heteroatom Chem
13:146–152, 2002; Published online in Wiley Interscience
(www.interscience.wiley.com). DOI 10.1002/hc.10010
into the imidazole ring facilitates phosphoryla-
tion. Herein, we report on the extended study of
the phosphorylation of both 4- and 1-substituted
1,2,4-triazoles along with the phosphorylation of
the functionalized triazole 17, which resulted in
the construction of a novel phosphorus-containing
condensed heterocyclic system.
INTRODUCTION
Recently, the 1,3-azoles having two heteroatoms
were shown to react readily with phosphorus(III)
halides to yield the corresponding products of
meso-phosphorylation. The detailed studies on the
phosphorylation of imidazoles and benzimidazoles
[1], thiazoles and benzothiazoles [2] have been
reported.
RESULTS AND DISCUSSION
The 4-substituted 1,2,4-triazoles have two potential
sites (in meso-positions) for the attack by a phos-
phorylating agent. An attempt to introduce one Ph2P
moiety into 1a,b by the treatment with equimolar
quantities of Ph2PCl resulted in nonseparable mix-
tures of mono- and bis-phosphorylated products.
The latter (2a,b) were, however, sole products when
two equivalents of the phosphorylating agent were
Correspondence to: Vladimir V. Ivanov; e-mail: vovch1@yahoo.
com.
c
2002 Wiley Periodicals, Inc.
146

C-Phosphorylation of 1,2,4-Triazoles with Phosphorus(III) Halides 147
SCHEME 1
employed (Scheme 1, Table 1). The phosphine 2a
was converted into the phosphorus(V) derivative 3
upon treatment with hydrogen peroxide. Similarly,
PCl3 reacts with 1b to produce the single product bis-
dichlorophosphinotriazole (4b) when the reagents
are taken in a 2:1 ratio. 4b, without isolation, was
subsequently treated with diethylamine and sulfur
to furnish 5b.
TABLE 1 Experimental Data of the Compounds Prepared
Found (%)
31P a
Compound
Yield (%)
mp/bp ( C)
Formula
C32H25N3P2
(Solvent)
N
P
2a
59
153–155
(benzene)
133–144
(EtOAc)
31.6
8.09
(8.18)b
8.01
(7.97)
7.56
(7.51)
17.06
(17.15)
17.11
(17.15)
12.19
(12.24)
15.61
(15.72)
34.90
(34.81)
41.08
(40.99)
14.37
(13.63)
11.13
(11.10)
14.01
(13.98)
18.19
(18.17)
12.14
(12.06)b
11.63
(11.74)
11.10
(11.07)
10.90
(10.83)
10.94
(10.83)
8.95
(9.02)
11.64
(11.59)
15.44
(15.39)
12.86
(12.95)
5.78
(6.03)
6.00
(6.14)
5.32
(5.15)
6.61
(6.70)
(CH2Cl2)
31.5
(CHCl3)
15.0
(CH2Cl2)
56.0
(CHCl3)
58.2
(toluene)
32.8
(pyridine)
30.8
(CHCl3)
76.5
(benzene)
27.7
(benzene)
42.8
(CDCl3)
40.1
(DMSO)
53.4
(CDCl3)
53.6
(CDCl3)
2b
3
57
81
C33H27N3P2
218
C33H27N3O2P2
C25H47N7P2S2
C25H47N7P2S2
C21H18N3P
5b
5c
8
35–55
57
111–112
(hexane)
110–111
(hexane)
139–140
(EtOH)
89–90
60
10
13
14
19a
19b
21
22
68
C15H14N3P
(EtOAc)
51
79–81(0.04)c
C7H16N5P
26
125–127(0.06)c
C8H14N7P
26
225–226
(benzene/heptane)
215–216
(toluene/heptane)
183–184
(toluene/heptane)
151–152
C20H16ClF3N5O2PS
C22H13ClF3N4OPS
C24H25ClF3N6O3PS
C17H22F3N6O2PS
51
61
93
(EtOH/H2O 1:1)
aSolvent used is given in parentheses.
bValues within parentheses in these columns indicate percent calculated values.
cmm Hg.

148 Zarudnitskii et al.
The high reactivity of 1,2,4-triazole allowed us
to synthesize the phosphamides 5b,c, even using
a phosphorylating agent of such low reactivity as
tetraethyldiamidochlorophosphite. A strong effect
of the nature of an N-substituent on the substrate
reactivity was observed in this case. 4-Benzyl-4H-
1,2,4-triazole (1c) was allowed to react with 2 equiv-
alents of (Et2N)2PCl to yield the phosphamide 6c in
3 days. On the other hand the same reaction of 1b,
having the aryl substituent at the nitrogen, proceeds
extremely slowly and is complete only in 1 year.
The difficulty of preparation of
a mono-
phosphorylated 4-substituted 1,2,4-triazole was re-
solved by blocking one of the reactive sites with an
indifferent substituent, namely the phenyl group, as
in the triazole 7, which was phosphorylated with
diphenylchlorophosphine to produce the phosphine
8 (Scheme 2).
SCHEME 3
that the phosphorus moiety in 21 remained in-
tact under the conditions of basic hydrolysis, the
aniline 22 being produced. Dibromophenylphos-
phine was reacted with the amide 17 to produce the
tricyclic 23, which was characterized in the form of
a phosphorus(V) derivative 19b. A good correlation
between 31P NMR spectral data of the phosphorus
compounds derived from 17 and the analogous imi-
dazole derivatives [6] was observed. It is also worth
noting that the reactivity of the herein-investigated
functionalized triazole 17 is lower than that of the
analogous imidazole derivative. This contrasts with
the above-demonstrated high reactivity of the simple
1,2,4-triazoles. However, the observed phenomenon
is plausibly due to the decreased basicity of the tria-
zole moiety in 17.
1-Methyl-1H-1,2,4-triazole (9), in contrast to the
sym-triazoles 1, has only one potential phosphoryla-
tion site, which is located between nitrogen atoms
of the pyrrole and pyridine types. The reaction of
9 with diphenylchlorophosphine yielded the phos-
phine 10 (Scheme 3). When PCl3 was allowed to react
with the triazole 9, a mixture of chlorophosphines
11 and 12 was obtained. The ratio of products ap-
proaches 1:1 as the temperature of the phosphoryla-
tion is increased. The chlorophosphines 11 and 12
cannot be separated by simple distillation because
of their thermal instability. Treatment of a mixture
of 11 and 12 with dimethylamine afforded the cor-
responding mixture of phosphamides 13 and 14, that
subsequently could be separated by distillation.
Finally, we carried out phosphorylation of the
functionalized triazole 17 in the manner described
previously for the analogous imidazole derivative
[6]. The starting amide 17 was synthesized accord-
ing to Scheme 4. It was treated with PBr3 to afford
the tricyclic compound 18 (Scheme 5). Substitu-
tion of the bromine atom in 18 with morpholine,
followed by sulfur addition, gave rise to the phos-
phorus(V) derivative 19a. When an excess of mor-
pholine was used in the presence of sulfur, the in-
termediately formed phosphamide 20 underwent a
diazaphosphinine ring opening to yield the phos-
phorylated functionalized triazole 21. It was found,
EXPERIMENTAL
All the manipulations with air-sensitive compounds
were performed under an atmosphere of dry argon
by using standard Schlenk techniques. Solvents were
purified by conventional procedures. Melting points
were determined with an electrothermal capillary
melting point apparatus and are uncorrected. The
31P, 1 H, 13C NMR spectra were obtained on a Varian
VXR-300 spectrometer (121, 300, and 75 MHz, re-
spectively). Chemical shifts are reported relative to
internal tetramethylsilane (1H, 13C) and external 85%
H3PO4 (31P).
3,5-Bis-diphenylphosphino-4-phenyl-4H-1,2,
4-triazole (2a) and 3,5-Bis-diphenylphosphino-
4-p-tolyl-4H-1,2,4-triazole (2b)
To a stirred mixture of triazole 1 (20 mmol), Et3N
(40 mmol), and pyridine (25 ml) was added Ph2PCl
(40 mmol). The reaction mixture was kept at room
temperature for 24 h, then evaporated to dryness
SCHEME 2

C-Phosphorylation of 1,2,4-Triazoles with Phosphorus(III) Halides 149
SCHEME 4
under reduced pressure. The residue was extracted
with hot benzene (40 + 20 ml). The extract was evap-
orated to dryness under reduced pressure, and the
residue was recrystallized from benzene.
2H, m-Ph-N), 6.81 (d, J = 8.4 Hz, 2H, o-Ph-N), 2.34
(s, 3H, CH3).
2a: 1H NMR (CDCl3):
(ppm) 7.49 (m, 8H,
3,5-Bis-diphenylphosphinoxido-4-phenyl-4H-
1,2,4-triazole (3)
o-Ph2P), 7.30 (m, 13H, m, p-Ph2P + p-Ph-N), 7.19
(t, J = 7.8 Hz, 2H, m-Ph-N), 6.74 (d, J = 7.7 Hz,
2H, o-Ph-N). 13C NMR (CDCl3): 156.77 ppm (dd,
J = 19.5 Hz and 2.2 Hz, C-3(5)).
To a stirred solution of 2a (10 mmol) in CH2Cl2
(20 ml) was added 2 M of H2O2 (10 ml). After 20 min,
the organic layer was separated, washed with wa-
ter (2 20 ml), dried over Na2SO4, and evaporated
1
2b: H NMR (acetone-d6): (ppm) 7.46 (m, 8H,
o-Ph2P), 7.37 (m, 12H, m,p-Ph2P), 7.11 (d, J = 8.4 Hz,
SCHEME 5

150 Zarudnitskii et al.
to dryness under reduced pressure. The residue was
recrystallized.
under reduced pressure and the residue was recrys-
tallized.
1H NMR (CDCl3): (ppm) 7.70 (m, 8H, o-Ph2PO),
7.50 (m, 4H, p-Ph2PO), 7.38 (m, 8H, m-Ph2PO), 7.19
(t, J = 7.7 Hz, 1H, p-Ph-N), 7.01 (t, J = 7.7 Hz, 2H,
m-Ph-N), 6.87 (d, J = 7.7 Hz, 2H, o-Ph-N). 13C NMR
(CDCl3): 153.60 ppm ( dd, J = 20.9 Hz and 4.7 Hz,
C-3(5)).
1H NMR (CDCl3): (ppm) 7.62 (m, 6H, o-Ph + o-
Ph2P), 7.49 (m, 3H, m,p-Ph), 7.40 (m, 6H, m,p-Ph2P),
3.67 (s, 3H, CH3).
(1-Methyl-1H-1,2,4-triazol-5-yl)diphenylphos-
phine (10)
To a mixture of the triazole 9 (12 mmol), Et3N
(12 mmol), and pyridine (12 ml) was added Ph2PCl
(12 mmol). The reaction mixture was kept at ambient
temperature for 18 h, diluted with benzene (15 ml),
and a precipitate was filtered off. The filtrate was
evaporated to dryness under reduced pressure and
the residue was recrystallized.
3,5-Bis-(tetraethyldiamidothiophosphono)-
4-p-tolyl-4H-1,2,4-triazole (5b)
Method A: To a stirred mixture of 1b (10 mmol),
Et3N (20 mmol), and pyridine (10 ml) was added
PCl3 (30 mmol). After 1 h, the reaction mixture was
treated with Et2NH (0.16 mol) at 0 C and then with
sulfur (30 mmol), stirred for 30 min, and evapo-
rated under reduced pressure to dryness. The residue
was extracted with benzene (30 ml). The extract was
evaporated and the residue was subjected to column
chromatography using hexane/EtOAc 3:1 as eluent.
The product was purified by recrystallization.
Method B: To a stirred mixture of 1b (10 mmol),
Et3N (20 mmol), and pyridine (10 ml) was added
(Et2N)2PCl (20 mmol). After 72 h, the 31P NMR spec-
trum of the reaction mixture revealed only traces of
5b ( 31P 92 ppm). The reaction was complete only in
1 year. The reaction mixture was treated with sulfur
(20 mmol), diluted with benzene (20 ml), and filtered
off. The filtrate was evaporated under reduced pres-
sure to dryness and the residue was recrystallized.
1H NMR (CDCl3): (ppm) 7.17 (s, 4H, Ar), 3.15
(m, 16H, NCH2), 2.41 (s, 3H, CH3), 1.05 (t, J = 6.9 Hz,
24H, NCH2CH3).
1H NMR (CDCl3): (ppm) 8.02 (s, 1H, 3-H), 7.40
(m, 10H, Ph2P), 3.91 (s, 3H, CH3).
(1-Methyl-1,2,4-1H-triazol-5-yl)tetramethyldia-
midophosphonite (13) and Bis-(1-methyl-1,2,4-
1H-triazol-5-yl)dimethylamidophosphonite (14)
To a stirred mixture of 1-methyl-1H-1,2,4-triazole
(0.05 mol), Et3N (0.05 mol), and pyridine (50 ml),
maintained at 40 C, was added PCl3 (0.1 mol). The
reaction mixture was kept for 3 h at this temperature,
then diluted with cold toluene (50 ml), and Me2NH
(0.5 mol) was added dropwise to it, over 20 min. After
1 h, the reaction mixture was filtered, the precipitate
being washed with toluene (30 ml), the filtrate was
evaporated under reduced pressure. Vacuum distil-
lation of the residue afforded the phosphamides 13
and 14.
1
13: H NMR (C6D6): (ppm) 8.05 (s, 1H, 3-H),
3.48 (s, 3H, CH3), 2.65 (d, J = 9.6 Hz, 12H, NCH3).
1
14: H NMR (C6D6): (ppm) 7.98 (s, 2H, 3-H),
3,5-Bis-(tetraethyldiamidothiophosphono)-
4-benzyl-4H-1,2,4-triazole (5c)
3.49 (s, 6H, CH3), 2.69 (d, J = 10.2 Hz, 6H, NCH3).
This compound was prepared analogously to 5b
from 4-benzyl-4H-1,2,4-triazole (1c) and (Et2N)2PCl
(Method B). In this case, the reaction was complete
in 72 h.
1-(2-Nitro-4-trifluoromethylphenyl)-1H-1,2,
4-triazole (15)
To a solution of 1,2,4-triazole (2.5 g, 36.2 mmol)
in DMF (4.5 ml) was added 1-chloro-2-nitro-4-
trifluoromethylbenzene (5 ml, 33.5 mmol). The re-
action mixture was heated to 100–105 C, and freshly
calcined, finely ground K2CO3 (8 g, 58 mmol) was
added portionwise under stirring. Then the reaction
mixture was stirred at 110–115 C for 0.5 h, cooled
to room temperature, and poured into water (60 l).
The crystalline solid that had precipitated was fil-
tered off, washed with water, and recrystallized from
EtOH/H2O with addition of activated charcoal.
1H NMR (DMSO-d6): (ppm) 7.27 (m, 3H, m,p-
Ph), 7.10 (m, 2H, o-Ph), 6.24 (s, 2H, CH2), 2.99 (m,
16H, NCH2), 0.94 (bs, 24H, NCH2CH3).
(4-Methyl-5-phenyl-4H-1,2,4-triazol-3-yl)diphenyl-
phosphine (8)
To a stirred mixture of the triazole 7 (6 mmol), Et3N
(6 mmol), and pyridine (6 ml) was added Ph2PCl
(6 mmol). The reaction mixture was kept for 18 h,
diluted with benzene (10 ml), and a precipitate was
filtered off. The filtrate was evaporated to dryness
1
Yield 5.87 g (68%). mp = 70 C (EtOH/H2O). H
NMR (CDCl3): (ppm) 7.81 (d, J = 8.0 Hz, 1H, H-6),

C-Phosphorylation of 1,2,4-Triazoles with Phosphorus(III) Halides 151
8.05 (dd, J = 8.0 and 1.6 Hz, 1H, H-5), 8.17 (s, 1H,
triazole), 8.29 (d, J = 1.6 Hz, 1H, H-3), 8.49 (s, 1H,
5-(4-Chlorobenzoyl)-4-morpholino-4-thioxo-
7-trifluoromethyl-4,5-dihydrobenzo[e][1,2,4]-
triazolo[5,1-c][1,4,2]diazaphosphinine (19a)
1
triazole). IR (KBr): 3150 (C H), 1640, 1560 cm .
Anal calcd for C9H5F3N4O2: C, 41.87%; H, 1.95%; N,
21.70%. Found: C, 42.10%; H, 1.9%; N, 21.82%.
Phosphorus tribromide (0.3 ml, 3.16 mmol) was
added to a stirred mixture of 17 (1.16 g, 3.16
mmol), triethylamine (0.9 ml, 6.46 mmol) and pyri-
dine (15 ml) at 25 C. The reaction mixture was
stirred for 1 h on a cooling bath, the temperature
being allowed to rise slowly to 0 C, and stirring was
continued for a futher 10 h at room temperature.
To thus prepared solution of 18 ( 31P 36.6 ppm),
were subsequently added triethylamine (0.45 ml,
3.23 mmol), morpholine (0.27 ml, 3.10 mmol), and
sulfur (120 mg, 3.74 mmol). The reaction mixture
was stirred for 6 h at 85 C, cooled to room temper-
ature and diluted with toluene (20 ml). The precipi-
tate of the salts was filtered off, and the filtrate was
evaporated to dryness under reduced pressure. The
residue was triturated with MeOH (5 ml) to yield
crystalline material, which was then filtered off and
washed with cold MeOH (3 ml).
2-(1H-1,2,4-Triazol-1-yl)-5-trifluoromethyl-
aniline (16)
A mixture of the above-prepared nitrocompound 15
(4 g, 15.5 mmol), Fe powder (8 g, 0.143 mol), HOAc
(40 ml), and EtOH (20 ml) was heated in a 0.25-l
round-bottom flask equipped with a condenser un-
til vigorous reaction took place. Then, the heating
bath was removed and the mixture was allowed to
boil. When boiling ceased, the reaction mixture was
refluxed for 0.5 h, cooled to room temperature, and
filtered under an atmosphere of argon. The filtrate
was evaporated under reduced pressure. The dark-
brown oily residue was dissolved in 150 ml of ethanol
and treated with saturated aqueuos K2CO3 under vig-
orous shaking to provide a clear solution with Fe-
containing lower layer. The solution was decanted
and evaporated to dryness under reduced pressure.
The solid residue was dissolved in dilute HCl. The
resulting solution was treated with charcoal and
stirred for 0.5 h, filtered, and basified with aqueous
K2CO3. The crystalline solid that had formed was col-
lected by filtration and washed with water to afford
2.93 g (83%) of the pure product.
1H NMR (CDCl3): (ppm) 2.98 (m, 2H, NCH2),
3.45 (m, 2H, NCH2), 3.68 (m, 2H, OCH2), 3.80 (m, 2H,
OCH2), 7.13 (s, 1H, H-6), 7.40 (d, J = 8.4 Hz, 1H, m-H
COC6H4Cl), 7.58. . .7.63 (m, 3H, o-H COC6H4Cl + H-
8), 8.22 (d, J = 8.4 Hz, 1H, H-9), 8.34 (d, J = 1.2 Hz,
1H, H-2). IR (KBr): 2985, 2940, 2880 (CH2), 1700
1
(C O), 1600 cm .
mp = 122–123 C (heptane/toluene). 1H NMR
4-Chloro-N-[2-{5-[dimorpholinophosphothioyl]-
1H-1,2,4-triazole-1-yl}-5-trifluoromethylphenyl]
benzamide (21)
(CDCl3):
(ppm) 4.88 (bs, 2H, NH2), 7.06 (d,
J = 8.2 Hz, 1H, H-5), 7.11 (s, 1H, H-3), 7.32 (d, J = 8.2
Hz, 1H, H-6), 8.19 (s, 1H, triazole), 8.42 (s, 1H, tri-
1
To a solution of 18 prepared as described above,
were subsequently added morpholine (1.1 ml,
12.64 mmol) and sulfur (110 mg, 3.43 mmol). The
work-up procedure described previously for 19a fol-
lowed, after 10 h stirring of the reaction mixture at
room temperature.
azole). IR (KBr): 3455, 3340 (NH2), 1650 cm . Anal
calcd for C9H7F3N4: C, 47.38%; H, 3.09%; N, 24.55%.
Found: C, 46.99%; H, 4.18%; N, 24.24%.
2-(1H-1,2,4-Triazol-1-yl)-1-(4-chlorophenyl-
carboxamido)-5-trifluoromethylbenzene (17)
1H NMR (CDCl3): (ppm) 3.13 (m, 8H, NCH2),
3.54 (m, 8H, OCH2), 7.46 (d, J = 8.4 Hz, 2H, m-H
COC6H4Cl), 7.57 (1H, dd, J = 8.4 Hz and 1.5 Hz, H-4),
7.70 (d, J = 8.4 Hz, 2H, o-H COC6H4Cl), 8.07 (d,
J = 8.4 Hz, 1H, H-3), 8.31 (s, 1H, triazole), 8.74 (d,
J = 1.5 Hz, 1H, H-6), 8.88 (1H, s, CONH). IR (KBr):
3440 (N H), 2900, 2915, 2875 (CH2), 1700 (C O),
A mixture of the aniline 16 (0.7 g, 3.07 mmol), p-
ClC6H4COCl (0.39 ml, 3.07 mmol), and MeCN (10 ml)
was refluxed for 1 h, and then evaporated to dryness
under reduced pressure. The residue was recrystal-
lized from EtOH/H2O 3:2.
Yield 1.05 g (93%). mp = 178–179 C (EtOH/H2O).
1H NMR (DMSO-d6): (ppm) 7.63 (d, J = 9.0 Hz, 2H,
m-H COC6H4Cl), 7.81 (dd, J = 8.7 Hz and 1.5 Hz,
1H, H-5), 7.89 (d, J = 9.0 Hz, 2H, o-H COC6H4Cl),
7.95 (d, J = 8.7 Hz, 1H, H-6), 8.31 (s, 1H, triazole),
8.34 (bs, 1H, H-3), 9.11 (s, 1H, triazole). IR (KBr):
1
1610 cm .
2-(5-[Dimorpholinophosphotioyl]-1H-1,2,
4-triazole-1-yl)-5-trifluoromethylaniline (22)
1
3340 (N H), 1700 (C O), 1610 cm . Anal calcd
A solution of 19 (0.60 g, 1.0 mmol) and KOH (120 mg,
2.14 mmol) in MeOH (7 ml) was refluxed for 24 h,
cooled to room temperature, and diluted with water
for C16H10ClF3N4O: N, 15.28%; Cl, 9.67%. Found: N,
14.77%; Cl, 9.64%.

152 Zarudnitskii et al.
(70 ml). The precipitate of 21 that had formed was
filtered off and washed with water.
H-6), 7.68. . .7.74 (m, 3H, p-H Ph + o-H COC6H4Cl),
7.85 (d, J = 9.0 Hz, 1H, H-8), 8.19 (dd, J = 7.5 Hz
and 17.1 Hz, 2H, o-H Ph), 8.36 (d, J = 9.0 Hz,
1H, H-9), 8.70 (s, 1H, H-2). IR (KBr): 1700 (C O),
1H NMR (CDCl3): (ppm) 3.17 (m, 8H, N CH2),
3.60 (m, 8H, O CH2), 4.08 (s, 2H, NH2), 7.09. . .7.11
(m, 2H, H-4 + H-6), 7.71 (d, J = 8.4 Hz, 1H, H-3), 8.23
(s, 1H, triazole). IR (KBr): 3450, 3350 (NH2), 2920,
1
1600 cm .
1
2880 (CH2), 1640 cm .
REFERENCES
5-(4-Chlorobenzoyl)-4-phenyl-4-thioxo-7-
trifluromethyl-4,5-dihydrobenzo[e][1,2,4]-
triazole[5,1-c][1,4,2]diazaphosphinine (19b)
[1] (a) Tolmachev, A. A.; Yurchenko, A. A.; Merkulov,
A. S.; Semenova, M. G.; Zarudnitskii, E. V.; Ivanov,
V. V.; Pinchuk, A. M. Heteroatom Chem 1999, 10,
585–597; (b) Komarov, I. V.; Strizhak, A. V.; Kornilov,
M. Yu.; Kostyuk, A. N.; Tolmachev, A. A. Synth Comm
1998, 28, 2355–2370.
[2] Komarov, I. V.; Strizhak, A. V.; Kornilov, M. Yu.;
Zarudnitskii, E. V.; Tolmachev, A. A. Synth Comm
2000, 30, 243–252.
[3] Anderson, D. K.; Sikorski, J. A.; Reitz, D. B.; Pilla,
L. T. J Heterocycl Chem 1986, 23, 1257–1262.
[4] Anderson, D. K.; Deuwer, D. L.; Sikorski, J. A. J Het-
erocycl Chem 1995, 32, 893–898.
[5] Tolmachev, A. A.; Zarudnitskii, E. V.; Dovgopoly, S. I.;
Pushechnikov, A. O.; Yurchenko, A. A.; Pinchuk, A. M.
Chem Hetercycl Compd 1999, 1432–1436.
Dibromophenylphosphine (0.5 ml, 3.50 mmol) was
added to a stirred mixture of 17 (1.28 g, 3.49 mmol),
triethylamine (1.0 ml, 7.2 mmol), and pyridine
(15 ml) at 25 C. The reaction mixture was stirred
for 1 h on a cooling bath, the temperature being al-
lowed to rise slowly to 0 C, and then stirred for an
additional 48 h at room temperature. To thus pre-
pared solution of 23 ( 31P 4.4 ppm) was added sulfur
(120 mg, 3.74 mmol). The reaction mixture was then
stirred for 6 h at 85 C and worked up as described
for 19a.
[6] Ivanov, V. V.; Yurchenko, A. A.; Chernega, A. N.;
Pinchuk, A. M.; Tolmachev, A. A. Heteroatom Chem
2002, 13, 84–92.
1H NMR (DMSO-d6): (ppm) 7.44 (d, J = 8.1 Hz,
2H, m-H COC6H4Cl), 7.56. . .7.63 (m, 3H, m-H Ph +