Facile syntheses and antimicrobial studies of 6-(aryloxy/arylthio/chloroethoxy)-2,10-dichloro- 4,8-dinitro-12-trichloromethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxides

Article abstract of DOI:10.1002/jhet.5570400224

Synthesis of several novel 6-aryloxy/arylthio/chloroethoxy-2,10-dichloro-4,8-dinitro- 12-trichloromethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxides (4a-k) was accomplished by reacting 2,2-bis (2-hydroxy-5-chloro-3-nitrophenyl)-1,1,1-trichloroethane 2

Full text of DOI:10.1002/jhet.5570400224

Mar-Apr 2003
345
Facile Syntheses and Antimicrobial Studies of
6-(aryloxy/arylthio/chloroethoxy)-2,10-Dichloro-4,8-Dinitro-12-
Trichloromethyl-12H-Dibenzo[d,g][1,3,2]dioxaphosphocin 6-Oxides
K. Ananda Kumar, M. Kasthuraiah, C. Suresh Reddy*,
^
C. Devendranath Reddy and K. D. Berlin
*Department of Chemistry, Sri Venkateswara University, Tirupati - 517 502, India
(e-mail: csureshsvu@yahoo.com)
Department of Chemistry, Oklahoma State University, Stillwater, OK 74078, USA
^
Received August 30, 2002
Synthesis of several novel 6-aryloxy/arylthio/chloroethoxy-2,10-dichloro-4,8-dinitro-12-trichloro-
methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-oxides (4a-k) was accomplished by reacting 2,2-bis (2-
hydroxy-5-chloro-3-nitrophenyl)-1,1,1-trichloroethane 2 with different aryl phosphorodichloridates (3a-g)
and O-2-chloroethyl phosphoryldichloride (3h) in the presence of triethylamine in dry toluene at 60-65 °C.
Actually some of these compounds were prepared by reacting monochloride 5 resulting from the condensa-
tion of phosphorus oxychloride with 2 in situ, with different phenols and thiophenols. The chemical struc-
1
13
31
tures were confirmed by elemental, ir and H, C, P nmr and mass spectral data analyses. These com-
pounds were screened for antifungal activity against Aspergillus flavus, Alternaria alternata, Fusarium
solani, Curvularia lunata and Pyricularia oryzae and antibacterial activity on Bacillus subtilis,
Staphylococcus aureus, Escherichia coli, Pseudomonas syringae and Klebsiella pneumoniae. Some of them
possessed significant activity.
J. Heterocyclic Chem., 40, 345 (2003).
Introduction.
The synthesis of organophosphorus compounds contain-
ing the dioxaphosphocin eight membered ring have
acquired much importance recently as these compounds
have been investigated for their insecticidal, bactericidal,
antiviral and anticarcinogenic properties [1-4]. In view of
their possible applications, synthesis of the title com-
pounds (4a-h) was accomplished using two methods. In
the first one various aryl phosphorodichloridates (3a-g)
and O-2-chloroethylphosphoryldichloride (3h) were
reacted with 2 in the presence of triethylamine in dry
toluene. However, introduction of substituted phenols or
thiophenols as bulky substituents in 4 was not always suc-
cessful by this method due to the difficulties in preparation
of the corresponding phosphorodichloridates that are
moisture sensitive, thermally unstable and explosive in
nature. Therefore an alternative method, starting from
phosphorus oxychloride, was used: the monochloride, 5
was first prepared by the standard procedure from 2 and
then various substituted phenols or thiophenols were
added to it in situ in the presence of base.
ring dioxaphosphocin 6-oxides 4a-h. Compounds 4i-k
were prepared through the monochloride, dioxaphospho-
cin 6-oxide 5 obtained by the reaction of 2 with phospho-
rus oxychloride/triethylamine in dry toluene at 55-60 °C
followed by its reaction with corresponding phenols or
thiophenols to give 4 (Scheme II).
The advantages of the second method over the first one
are that it does not require the preparation of sometimes
highly toxic, moisture sensitive or thermally unstable
phosphorodichloridates of corresponding substituted phe-
nol and thiophenols. The isolation and purification of the
intermediate monochloride 5 is not required. The conden-
sation products 4 were easily isolated and purified by
recrystallization.
Results and Discussion.
31
Reaction of 4-chlorophenol with chloral in the presence
of concentrated sulphuric acid gave 2,2-bis(2-hydroxy-5-
chlorophenyl)-1,1,1-trichloroethane 1 [5]. Nitration of 1
using nitric acid in acetic acid afforded 2,2-bis(2-hydroxy-5-
chloro-3-nitrophenyl)-1,1,1-trichloroethane 2 (Scheme I).
Cyclocondensation of this nitro compound 2 with vari-
ous aryl phosphorodichloridates (3a-g) and O-2-chloro-
ethylphosphoryldichloride 3h in the presence of
triethylamine at 60-65 °C yielded the eight membered
The reaction yields, elemental analyses, ir and P nmr
1
data of 4 are given in Table 1. Tables 2, 3 and 4 contain H
13
and C nmr spectral data. The infrared absorption bands
-1
for 4a-k were present in the regions 1241-1320 cm and
-1
1533-1542 & 1319-1356 cm for P=O and Ar-NO [6-8]
2
respectively.
1
H nmr spectra of 4a-k showed complex multiplets for
the aromatic protons of the dibenzodioxaphosphocin moi-
eties at δ 7.50-8.38 [9,10]. The resonance signal for the

346
K. A. Kumar, M. Kasthuraiah, C. S. Reddy, C. D. Reddy and K. D. Berlin
Vol. 40
Compd.
R
Compd
R
Compd
R
4a
4b
4c
4d
OC H
4e
4f
4g
4h
OC H -(CH ) (2',5')
4i
4j
4k
OC H -C(CH ) (4')
6 4 3 3
6
5
6
3
3 2
OC H -CH (2')
OC H -Cl(2')
SC H -Cl(4')
6
4
3
6
4
6 4
OC H -CH (3')
OC H -Cl(4')
SC H -CH (4')
6 4 3
6
4
3
6
4
OC H -CH (4')
OCH CH Cl
6
4
3
2 2
13
bridged methine proton in all the compounds appeared as
singlets in the region δ 6.30-6.68. Similarly, the protons of
aryloxy or arylthio moieties showed signals in the region δ
6.70-7.69. The methyl and tert-butyl protons of the 6-ary-
loxy/arylthio moieties in 4b-e, 4k and 4i appeared as sin-
glets in the range of δ 2.15-2.49 and δ 0.96 respectively.
A rigid boat-boat (BB), boat-chair (BC) and twist-boat
may be more likely conformations considered for the
eight-membered dibenzodioxaphosphocin ring as illus-
trated in Scheme II [9a,b,11]. The structure of the two aro-
matic rings may assist the cyclization reaction.
Similarly, C nmr chemical shifts of the 6-aryloxy
(4a-g) and arylthio (4k) groups are presented in Table 4.
The low intensity signals observed at δ 143.7-152.3 is for
C(1'). C(2') and C(6') resonated in the region δ 119.3-
130.7. Chemical shifts for the C(3'), C(4') and C(5') were
located at δ 130.2-142.9, 123.7-135.2 and 128.5-137.1
respectively on the basis of the nature of substituents at
various positions. The observed upfield shift of about 4
ppm for the methyl carbon attached to C(2') (4b and 4e) is
attributed to its γ-interaction with the exocyclic oxygen
[11b,12c]. In 4h, the signals observed at δ 63.2 and 44.2
are due to C(1') and C(2') respectively.
13
The C nmr chemical shifts of dibenzodioxaphospho-
cin moieties of 4 are given in Table 3 and were interpreted
based on additivity rules and computed chemical shifts of
2, carbon couplings with phosphorus and intensity of sig-
nals. The oxygen-bearing C(4a) and C(7a) signal appeared
in the downfield region at δ 149.4-152.6 [12]. The chemi-
cal shift of the bridged C(11a) and C(12a) appeared at δ
122.8-124.7 [12b]. The nitro-substituted C(4) and C(8)
gave signals at δ 137.2-138.6. The chlorine bearing C(2)
and C(10) resonated in the region δ 129.4-132.5. The
unsubstituted C(1) & C(11) and C(3) & C(9) showed sig-
nals with high intensity in the region δ 133.8-137.2 and
124.6-129.7 respectively. The bridged C(12) and C(13)
resonated at δ 51.5-53.1 and δ 98.0 - 99.9 respectively.
31
The P nmr signals of all dibenzodioxaphosphocin
6-oxides (4a-k) are given in the range of -21.0 to -1.62
31
ppm. Only one P nmr signal is observed in the spectra of
4a, 4f and 4h-k (Table 1). In other compounds of 4, two
distinct signals were observed with varying intensities [13]
and this may be attributable to the presence of two con-
formers in solution.
The Gas-Chromatography Mass Spectrum of 4b is ratio-
nalized in the Scheme III. It did not show the molecular
ion peak. However, the peak at m/z 592 (5.5) represents
+.
[M -HCl] fragment. The base peak ion was observed at
m/z 86(100). The ion at m/z 476(4) might be the result of

Mar-Apr 2003
Facile Syntheses and Antimicrobial Studies
347
+.
Antimicrobial Activity.
the ejection of CCl and Cl as radicals from M [14,11c].
3
Expulsion of CCl and C H O radicals from the parent
2
7 6
The dioxaphosphocin 6-oxides (4a-k) were screened for
antibacterial activity [16] against the growth of Bacillus
subtilis, Staphylococcus aureus (gram +ve) and
Escherichia coli, Klebsiella pneumoniae, Pseudomonas
syringae (gram -ve) at concentrations 250, 500 and 1000
ppm. The results are given in Table 5. Most of these com-
pounds showed good antibacterial activity at all concentra-
tions against the Bacillus subtilis, Staphylococcus aureus
and Escherichia coli when compared to Pseudomonas
syringae and Klebsiella pneumoniae.
+.
M led to the appearance of the ion at m/z 440(3). This ion
on subsequent loss of HCl and H radical gave the ion at
m/z 403(25). The daughter ion at m/z 357(48) might have
formed by the successive loss of NO , two moles of HCl
2
and subsequent abstraction [15] of two hydrogen radicals
from the dibenzodioxaphosphocin system. The other
important major fragment ions are observed at m/z 339
(50), 293 (17), 207 (13), 184 (25), 149 (14), 137 (18), 107
(43), 86 (100), 53 (48).
Scheme III
Table 1
31
Physical, IR and P NMR Spectral Data of 6-Aryloxy/arylthio/chloroethoxy-2,10-dichloro-4,8-dinitro-12-trichloromethyl-12H-
dibenzo[d,g][1,3,2]dioxaphosphocin 6-Oxides (4a-k)
-1
31
Compd. Yield
(%)
Mp
(°C)
Molecular Formula
Elemental Analysis
Found (Calcd) (%)
IR (cm )
P NMR
Data
Ppm
C
H
N
P=O
1244
1243
1244
1247
1248
1248
1241
1312
1315
1312
1320
Ar-NO
1540
1542
1541
1540
1539
1539
1542
1533
1539
1542
1534
2
4a
4b
4c
4d
4e
4f
64 [a]
59 [a]
55 [a]
60 [a]
55 [b]
58 [b]
60 [b]
55 [b]
65 [b]
178-180
103-105
112-115
190-192
191-192
222-224
98-100
C
C
C
C
C
H
Cl N O P•Et N
43.41
(43.63)
44.28
(44.44)
44.24
(44.44)
44.64
(44.44)
45.01
(45.22)
41.40
(41.63)
41.41
(41.63)
37.45
(37.64)
46.43
3.40
(3.52)
3.62
(3.73)
3.60
(3.73)
3.82
(3.73)
3.84
(3.93)
3.15
(3.23)
3.03
(3.23)
3.33
(3.45)
4.20
5.72
(5.87)
5.60
(5.76)
5.58
(5.76)
5.62
(5.76)
5.51
(5.65)
5.42
(5.60)
5.48
(5.60)
5.84
(5.98)
5.28
1326
1354
1356
1321
1319
1320
1354
1351
1348
1352
1326
-14.48
20 10
5
2
8
3
H
Cl N O P•Et N
-15.55, -1.62
-9.86, -9.68
-15.46, -1.62
-14.13, -9.16
-5.98
21 12
5
2
8
3
H
Cl N O P•Et N
5 2 8 3
21 12
H
Cl N O P•Et N
5 2 8 3
21 12
H
Cl N O P•Et N
5 2 8 3
22 14
C
H Cl N O P•Et N
9 6 2 8 3
20
20
16
4g
4h
4i
C
C
H Cl N O P•Et N
-15.97, -9.02
-4.98
9
6
2
8
3
263-265
253-255
H Cl N O P•Et N
9 6 2 8 3
C
H
Cl N O P•Et N
-19.3
24 18
5
2
8
3
(46.68)
40.51
(40.76)
43.28
(4.31)
3.03
(3.16)
3.56
(5.44)
5.28
(5.48)
5.48
4j
62 [a] 280 (Dec) C H Cl N O PS•Et N
-21.0
20
9
6
2
7
3
4k
58 [a]
234-236 C
H
Cl N O PS•Et N
-19.1
21 12
5
2
7
3
(43.48)
(3.65)
(5.63)
[a] Recrystallized from methanol; [b] Recrystallized from ethylacetate-hexane; Et N = Triethylamine.
3

348
K. A. Kumar, M. Kasthuraiah, C. S. Reddy, C. D. Reddy and K. D. Berlin
Vol. 40
Table 2
1
H NMR Chemical Shifts [a] of 6-Aryloxy/arylthio/chloroethoxy-2,10-dichloro-4,8-dinitro-12-trichloromethyl-12H-dibenzo[d,g][1,3,2]dioxaphospho-
cin 6-Oxides (4a-k)
Compd. H(3,9) & H(1,11) H(12)
Ar-H
OAr-CH
-
2.15 (s, 3H, 2 -CH )
2.26 (s, 3H, 3 -CH )
3
4a [b]
4b [c]
4c [b]
7.72-8.20 (m, 4H) 6.44 (s, 1H) 6.80-7.59 (m, 5H)
7.82-8.31 (m, 4H) 6.39 (s, 1H) 6.75-7.65 (m, 4H)
7.84-8.20 (m, 4H) 6.50 (s, 1H) 6.85-7.17 (m, 4H)
3
3
4d [b] 7.68-8.12 (m, 4H) 6.40 (s, 1H) 6.84-7.08 (m, 4H)
2.24 (s, 3H, 4 -CH )
3
4e [c]
7.98-8.21 (m, 4H) 6.51 (s, 1H) 6.97-7.69 (m, 3H)
2.49 (s, 3H, 2 -CH )
3
2.19 (s, 3H, 5 -CH )
3
4f [c]
4g [c]
4h [c]
7.99-8.11 (m, 4H) 6.49 (s, 1H) 6.82-7.67 (m, 4H)
7.83-8.29 (m, 4H) 6.39 (s, 1H) 6.70-7.68 (m, 4H)
-
-
7.69-8.15 (m, 4H) 6.53 (s, 1H)
-
4.01-4.09 (m, 2H, OCH )
2
3.68-3.79 (m, 2H, CH Cl)
2
4i [b]
4j [b]
4k [c]
7.50-8.12 (m, 4H) 6.30 (s, 1H) 6.92-7.25 (m, 4H)
7.98-8.27 (m, 4H) 6.47 (s, 1H) 6.98-7.47 (m, 4H)
7.92-8.38 (m, 4H) 6.68 (s, 1H) 6.88-7.30 (m, 4H)
0.96 (s, 9H, 4 -C(CH ) )
-
3 3
2.24 (s, 3H, 4 -CH )
3
[a] Chemical shifts relative to TMS; [b] Recorded in Deuteriochloroform; [c] Recorded in Dimethylsulphoxide-d .
6
Table 3
13
C NMR Chemical Shifts [a,d] of 2,10-Dichloro-4,8-dinitro-12-trichloromethyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-Oxides 4
Compd.
C(1/11) C(2/10) C(3/9) C(4/8) C(4a/7a)
C(11a/12a) C(12)
C(13)
4a [b]
4b [c]
4c [b]
4d [b]
4e [c]
4f [c]
4g [c]
4h [c]
4k [c]
134.7
137.2
134.3
133.8
135.0
135.1
137.2
134.9
135.3
130.7
132.5
131.2
129.7
130.2
130.5
129.4
130.3
129.6
126.5
129.7
127.2
124.7
124.6
125.0
125.1
124.8
125.1
137.5
138.6
137.2
137.3
136.7
137.4
138.5
137.3
137.9
149.9
152.6
149.4
152.3
150.0
150.0
152.5
149.7
-
123.5
124.7
123.0
124.6
122.8
123.0
124.0
122.8
123.3
51.9
53.1
52.1
52.4
51.6
51.7
53.1
51.5
52.8
98.7
99.2
99.2
98.9
99.6
99.9
99.4
99.7
98.0
[a] Chemical shifts in ppm from TMS; [b] Recorded in Deuteriochloroform; [c] Recorded in Dimethylsulphoxide-d ; [d] 4i & 4j not recorded.
6
Table 4
Pyricularia oryzae at different concentrations (250, 500
13
C NMR Chemical Shifts of 6-Aryloxy/arylthio/chloroethoxy Moieties in 4
and 1000 ppm) [17] (Table 6). Compounds 4b, 4c and
4g showed significant activity against all the fungi at
different concentrations. However, compounds 4a-k
exhibited moderate antifungal activity against Fusarium
solani when compared to their activity on other
organisms.
Compd. C(1) C(2) C(3) C(4) C(5) C(6)
Methyl carbons
4a [b]
4b [c]
4c [b]
148.6 119.3 133.6 125.9 133.6 119.3
-
152.3 129.9 134.1 123.7 128.7 119.7 20.6
148.9 121.4 142.9 126.7 128.5 118.8 20.1
4d [b] 146.2 121.7 130.4 135.2 130.4 121.7 21.4
4e [c]
148.7 130.4 135.9 124.9 137.1 122.7 19.4 (C-2)
20.8 (C-5)
EXPERIMENTAL
4f [c]
4g [c]
148.8 130.7 137.8 125.2 135.9 122.8
143.7 12.13 132.6 130.2 132.6 121.3
-
-
Melting points were determined in open capillary tubes on a
Mel-Temp apparatus and were uncorrected. Elemental analyses
were performed by the Central Drug Research Institute,
Lucknow, India. The ir spectra were recorded as KBr pellets on
(4.6)
-
(4.6)
-
4h [c]
4k [c]
-
-
-
-
63.2 (C-1)
44.2 (C-2)
143.7 121.4 130.2 129.5 130.2 121.4 20.8 (C-4)
1
13
Perkin-Elmer 1000 unit. All H and C nmr spectra were
recorded on a varian XL-300 spectrometer operating at 300 MHz
[a] Chemical shifts in ppm and J (Hz) given in parenthesis; [b] Recorded
in Deuteriochloroform; [c] Recorded in Dimethylsulphoxide-d ; [d] 4i &
4j not recorded.
1
13 31
for H and 75.46 MHz for C. P nmr spectra were recorded on
a Varian XL-400 spectrometer operating at 161.89 MHz. All nmr
6
data were taken in deuteriochloroform or dimethyl-d sulfoxide
6
1
13
solutions and were referenced to tetramethylsilane ( H and C)
or 85% phosphoric acid ( P). The Gas-Chromatography Mass
Similarly, the antifungal activity was evaluated
against the growth of Aspergillus flavus, Alternaria
alternata, Fusarium solani, Curvularia lunata and
31
Spectra (GCMS) were recorded on a Shimadzu QP 5000 instru-
ment using ionization potential at 70 eV.

Mar-Apr 2003
Facile Syntheses and Antimicrobial Studies
349
Table 5
Antibacterial Activity of Compounds 4a-k
Compd. Concentration
n (ppm)
Zone of inhibition (mm)
Bacillus subtilis
Staphylococcus aureus
Escherichia coli
Pseudomonas syringae Klebsiella pneumoniae
4a
4b
4c
4d
4e
4f
250
500
1000
250
500
1000
250
500
1000
250
500
1000
250
500
1000
250
500
1000
250
500
1000
250
500
11
15
23
10
18
24
13
19
27
10
13
16
9
13
16
20
13
18
24
17
20
25
8
8
10
15
7
8
14
8
12
18
7
8
9
-
7
10
-
-
8
7
8
13
-
9
11
14
-
7
8
10
-
7
8
7
9
13
-
-
7
-
-
7
-
7
10
-
-
9
-
-
7
-
-
7
9
11
13
8
10
11
-
-
-
-
-
-
-
-
-
-
-
-
-
9
14
7
13
18
8
8
11
12
16
19
12
18
25
10
13
15
9
11
15
13
18
23
11
14
17
9
4g
4h
4i
-
9
8
1000
250
500
1000
250
11
14
7
11
15
7
9
12
-
-
-
-
-
9
-
4j
500
9
9
7
-
-
1000
250
500
11
7
8
12
10
13
17
9
-
-
8
-
-
-
-
9
-
-
4k
1000
10
8
'-' indicates no activity.
Preparation of 2,2-Bis(2-hydroxy-5-chloro-3-nitrophenyl)-1,1,1-
Anal.Calcd.for C H Cl N O : C 35.27, H 1.48, N 5.88;
14 7 5 2 6
trichloroethane (2).
Found: C 34.99, H 1.34, N 5.67.
Nitric acid (7 ml, 0.1 mole) was added over a period of twenty
minutes to a stirred solution of 2,2-bis(2-hydroxy-5-chlorophenyl)-
1,1,1-trichloroethane 1 (19.3 g, 0.05 mole) in acetic acid (120 ml)
at 14-15 °C. After the addition, the reaction was continued with
stirring at room temperature for 3-4 hours. The crude nitro product
was collected by filtration. It was washed with water, dried and
recrystallized from ethylacetate-hexane (3:1) to yield 17.4 g (73%)
of 2,2-bis(2-hydroxy-5-chloro-3-nitrophenyl)-1,1,1-trichloro-
ethane (2), mp 212-214 °C; ir (potassium bromide): 1539, 1320
6-(4-Methylphenoxy)-2,10-dichloro-4,8-dinitro-12-trichloro-
methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-Oxide (4d).
A solution of 4-methylphenylphosphorodichloridate (3d, 2.25
g. 0.01 mole) in 25 ml of dry toluene was added dropwise over a
period of twenty minutes to a stirred solution of 2,2,-bis(2-
hydroxy-5-chloro-3-nitrophenyl)-1,1,1-trichloroethane (2, 4.76
g, 0.01 mole) and triethylamine (2.02 g, 0.02 mole) in 60 ml of
dry toluene. After completion of the addition, the temperature
was slowly raised to 60-65 °C and stirring was continued for an
additional six hours. Progress of the reaction was monitored by
tlc analysis. Triethylamine hydrochloride was then removed from
the reaction mixture by filtration and the solvent was evaporated
under reduced pressure. The residue was washed with water,
dried and then recrystallized from ethylacetate-hexane (8:2) to
yield pure compound 4d, 3.8 g (60%), mp 190-192 °C. Physical
and spectral data of 4d are given in Tables 1-4.
-1
1
(Ar-NO ), 3259 (Ar-OH) cm ; H nmr (deuteriochloroform): δ
2
11.22 (s, 2H, 2 & 2 -OH), 8.15(d, J = 2.6 Hz, 2H, 4 & 4 -H), 8.01
13
(d, J = 2.6 Hz, 2H, 6 & 6 -H), 6.33 (s, 1H, 2-CH) ; C nmr (deu-
teriochloroform): δ 125.0 (s, 2C, C-1 & 1 ), 152.8 (s, 2C, C-2 & 2),
137.7 (s, 2C, C-3 & 3 ), 125.1 (s, 2C, C-4 & 4 ), 130.1 (s, 2C, C-5
& 5 ), 134.3 (s, 2C, C-6 & 6 ), 99.4 (s, 1C, CCl ), 52.9 (s, 1C, CH)
3
+.
+.
; gcms: m/z (%) 476 [2, (M +2), 474 (1.5, M ), 439 (2), 403 (9),
357 (18.5), 339 (43.5), 295 (14), 220 (18), 207 (26), 186 (18), 173
(25), 150 (21), 137 (27), 121 (57), 117 (94), 63 (100).
Other members of the compounds were prepared by this
procedure.

350
K. A. Kumar, M. Kasthuraiah, C. S. Reddy, C. D. Reddy and K. D. Berlin
Vol. 40
Table 6
Antifungal Activity of Compounds 4a-k
Compd. Concentration
n (ppm)
Zone of inhibition (mm)
Aspergillus flavus
Alternaria alternata
Fusarium solani
Curvularia lunata
Pyricularia oryzae
4a
4b
4c
4d
4e
4f
250
500
1000
250
500
1000
250
500
1000
250
500
1000
250
500
1000
250
8
9
13
7
8
10
7
9
12
7
8
9
-
-
-
-
-
-
8
9
13
7
8
12
-
-
-
-
-
-
-
8
9
11
7
10
12
13
18
22
7
8
11
7
9
13
7
-
7
9
7
9
13
8
9
13
-
-
-
-
-
-
-
8
8
9
12
7
8
11
-
-
-
-
-
-
7
-
-
-
500
1000
250
500
1000
250
7
10
7
8
11
-
-
-
8
11
14
-
-
-
11
15
24
-
8
11
8
10
14
7
-
-
7
8
12
-
4g
4h
4i
500
1000
250
-
7
-
-
-
-
-
-
-
9
10
7
-
-
-
500
-
-
-
8
-
1000
250
-
-
-
-
-
-
10
7
-
-
4j
500
-
-
-
8
-
1000
250
-
-
-
-
-
-
12
7
-
-
4k
500
-
-
-
8
-
1000
8
-
-
10
-
'-' indicates no activity
6-(4-tert-Butylphenoxy)-2,10-dichloro-4,8-dinitro-12-trichloro-
methyl-12H-dibenzo[d,g][1,3,2]dioxaphosphocin 6-Oxide (4i).
4j-k are prepared by this procedure.
Acknowledgements.
The typical procedure using phosphorus oxychloride is illus-
trated in the preparation of 4i. To a cooled (0 °C) and stirred solu-
tion of 2,2-bis(2-hydroxy-5-chloro-3-nitrophenyl)-1,1,1-
trichloroethane (2, 4.76 g, 0.01 mole) and triethylamine (2.02 g,
0.02 mole) in 60 ml of dry toluene, was added dropwise phos-
phorus oxychloride (1.53 g, 0.01 mole) in 25 ml of dry toluene
over a period of twenty minutes. After raising the temperature to
55-60 °C, the reaction mixture was stirred for five hours at this
temperature, tlc analysis (silica gel; ethylacetate-hexane, 3:7)
was used to monitor the formation of monochloride 5. To this
reaction mixture, in the same vessel, at 0-5 °C, was added drop-
wise a solution of 4-tert-butylphenol(1.5 g, 0.01 mole) and tri-
ethylamine (1.01 g, 0.01 mole) in 25 ml dry toluene. The tem-
perature of the reaction was brought to 60-65 °C and the mixture
was stirred for another four hours. Triethylamine hydrochloride
was removed by filtration and evaporation of the solvent under
reduced pressure afforded a solid residue, which after washing
with water, was dried and recrystallized from methanol to give
4.4 g (65%) of 4i, mp 253-255 °C. The physical and spectral data
for 4i-k are given in Tables 1-4.
The authors (KAK and MK) express their thanks to CSIR for
awarding Senior Research Fellowship.
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