Indi an Journal of Chemistry
Vol. 41A. August 2002, pp. 1639- 1642
Synthesis and characterization of some
phthalanilic and maleanilic acid derivatives
of arsenic(III)
H P S Chauh an*, R K Singh, B Porwal & Kavita Kori
School of Chemical Sciences, Devi Ahilya Universi ty,
Takshashila Campus, Khandwa Road, Indore 452017, Indi a
Received 14 Feb/'llary 2001; revised 6 FebruQly 2002
Replacement reaction of arsen ic tri chl oride and 2-chl oro- 1,3dithia-2-arsacyclopen tane with sodium sal ts of phthalanilic and
maleanilic acids (prepared ill situ by the reaction of corresponding
an ili c acids with sodium isopropox ide in the mixture benzene and
isopropanol) in the 1:3 and I: I molar ratios respectively, in
benzene and isopropanol mi xture. yield the arse ni c derivatives of
the type [Lh As and [L) AsSC H1C H2S (where L = phthal anil ate
and mal eani late anions). These deri vatives have been
characteri zed by elemental analysis as well as IR and IH NMR
spectral studies.
Anilic ac ids have been found to be of great utility
from analytica l I and biochemical 2.4 points of view.
Their metal complexes have also been found of great
industri al and biochemical importances. Therefore, it
was thought of interest to make inves tigations on
sy nthetic and structural aspects of arsenic(III)
phthalanilates and mal eanil ates . In continuation of our
earli er
publi cations
on
organotin(IV)6.7
and
antimony(III)8 derivatives of phthalanilic and
maleanilic acids, we are reporting here some
arsenic(III) derivatives of phtha lanilic and maleanilic
ac ids.
Experimental
All the experimental manipul ations were carried
out in the moi sture free conditions. Benzene, diethyl
ether and isopropanol were dried by standard
methods? . Maleic and phthalic anhyd rides (Fluka and
E Merck) were used as such without further
lo
purification. Anilic acids (phtha lanilic acid, mal eanilic acid, chlorophthalanilic acid and chloromalea nilic ac id ) and 2-chloro-I,3-dithia-2-arsacycloII
pentane
were pre pared by reported methods.
Arseni c(III) chl oride was di still ed before use. Arsenic
was est imated iodometricallyl 2. Sulphur was
estimated gravi metricall y as barium sulphate. Carbon,
hydrogen and nitrogen were analysed at RSIC, CDRl,
Lucknow. The IR spectra were recorded as Nujol
mulls on a Perkin-Elmer 557 spectrophotometer in the
l
range 4000-200 cm· . The IH NMR spectra were
recorded in the mixture of DMSO and acetone-d6
solution using TMS as internal standard.
These derivatives have been pre pared by the
following methods:
Method I
Reaction of arsenic(1/1) chloride with sodium salt of
phthalanilic acid in J.' 3 molar ratio
To an excess of isopropanol (-10 ml ) + benzene
(-10 ml) sodium metal (0.18 g; 7.82 mmol ) was
added and a clear solution of sodium isopropoxide
was obtained after ha lf an hour. To thi s was added an
isopropanol (-10 ml) + benzene (-10 ml ) solution of
phthalanilic acid 0.92 g; 7.96 mmol ) and the contents
were refluxed for -I h. After cooling, arsenic
trichloride (0.48 g; 2.64 mmol ) dissol ved in
isopropanol (-10 ml) was added dropwise and the
contents were refluxed for -5 h. The precipitated
sodium chloride (0.45 g) was separated by filtrati on.
Removal of solvent from filtrate under reduced
pressure yielded a white crystalline solid. Yield= 1.98
g, 92%; m.pt. 145°C.
Method 1/
Reaction of 2-chloro-J ,3-dithia-2-arsacyclopentalle
with sodium salt of phthalanilic acid in J.' J lIlolar
ratio
To an excess of isopropanol (-25 ml ), sodium
metal (0.12 g ; 5.22 mmol ) was added and a clear
solution of sodium isopropoxide was obtained after
half an hour. To this was added a benzene (- 10 ml )
solution of phthalanilic acid ( 1.24 g ; 5. 14 mmo l) and
the contents were retlu xed for -1 h. After cooling,
solution of 2-chloro-I,3-dithia-2-arsacyclopentane
(1.04 g; 5.14 mmol ) in benzene (-10 ml ) was added
dropwise and the contents were furth er refluxed for
- 4 h. The precipitated sodium chloride (0.28 g) was
separated by filtration. The filtrate was reduced up to
-10 ml and kept overnight in refrigerator to get white
crystalline solid . Yield = 1.85 g, 88% ; m.pt. 195 °C.
Similarly, other derivat ives li sted in Tabl e I were
synthes ized by adopting either of the above
procedures.
0\
.j::..
o
Tablel-Characterization data of phthalanilic and malcanilic acid derivatives of arsenic(II1)
SI.
No
Reactants(g)
I.
As0 3+
(0.48)
PhNHC(O)CJ4C(O)OH+
(2.08)
2.
AsCI) +
(0.76)
ClPhNHC(O)CJ4C(O)OH +
(3.74)
Found (Calcd.), %
C
H
Molar
Ratio
Product
(% Yield)
M.Pt
°C
Na
(0.18)
1:3:3
PhNHC(O)CJ4C(O)oIJAs
(94)
145
8.99
(9.43)
62.90
(63.39)
3.52
(3.81)
4.95
(5.28)
Na
(0.28)
1:3:3
[OPhNHC(O)CJ4C(O)ohAs
(93)
165
7.56
(8.33)
55.47
(56.11)
3.31
(3.03)
4.60
(4.68)
As
S
N
Z
0
;;
Z
(")
3.
As03+
(0.52)
PhNHC(O)CH=CHC(O) OH+
(1.84)
Na
(0.19)
1:3:3
[PhNHC(O)CH=CHC(O)O)JAs
(88)
180
10.73
(11.61)
54.88
(55.82)
3.04
(3.76)
6 .76
(6.51)
:r:
rn
3::
en
rn
4.
As03+
(0.71)
ClPhNHC(O)CH=CHC(O)OH+
(2.91)
Na
(0.26)
1:3:3
[ClPhNHC(O)CH=CHC(O)OI 3 As
(90)
60
9.59
(10.01)
48.04
(48.12)
2.87
(2.83)
4.97
(5.61)
5.
(CH2ShAsO+
(1.04)
PhNHC(O)CJ4C(O)OH+
(1.35)
Na
(0.13)
1: 1:1
PhNHC(O)CJ4C(O)OAs(SCH2h
(88)
195
17.98
(18.39)
14.1 0
(15.72)
46.82
(47.16)
3.40
(3.43)
3.28
(3.43)
6.
(CH2ShAsCi +
(0.65)
ClPhNHC(O)4lLC(O)O H +
(0.97)
Na
(0.08)
1:1:1
ClPhNHC(O)4lLC(O)OAs(SCH2h
(87)
130
17.08
(16.95)
15.28
(14.49)
42.48
(43.46)
2.98
(3.17)
3.10
(3.17)
7.
(CH2ShAsO+
(0.72)
PhNHC(O)CH=CHC(O) OH+
(0.76)
Na
(0.10)
1: 1:1
PhNHC(O)CH=CHC(O)OAs(SCH2h
(85)
150
18.D3
(20.42)
18.29
(17.87)
40.44
(40.20)
3.47
(3.35)
3.06
(3.90)
8.
(CH2ShAsO+
(0.86)
ClPhNHC(O)CH=CHC(O)OH+
(0.96)
1:1:1
Na
(0.10)_______
OPhNHC(O)CH=CHC(O)OAs(SCH212
(79)
162
20.28
(19.13)
17.02
(16.34)
37.12
(36.77)
2.94
(3.06)
3.41
(3.57)
0
?
»
c:
0
c:
en
-l
tv
0
0
tv
NOTES
Results and discussion
Anilic ac id derivatives of arsenic(III) have been
prepared by the reaction of arsenic trichloride with
sodi um salt of anilic acids in 1:3 molar ratio.
CH 2S
I
A- C(O)NHR
) ASCI +
CH2S
I
+ Na
Isopropa nol + Benzene
~
A-C(O )OH
[
A-C(O)N~R
/ SCH2
I
As ,
I
A-C(O)O'
SCH 2
+ NaCl 1
W
All these tris derivatives are white crystalline solids
and were found to be insoluble in hydrocarbons and
chlorocarbons however, these are soluble in acetone
and alcohols.
A-C(O)NHR
AsCI 3+
31
A-C(O)OH
Isopropanol + Benzene
+ 3Na
...
[ rC(O)~AS
A-C(O)O -13
+3NaCI~
Mixed dithiolatoarsenic derivatives have been
sy nthesized by the reaction of 2-chloro-l,3-dithia-2arsacyclopentane with sodium salt of phthalanilic and
maleanilic acids in 1: 1 molar ratio in the solution of
benzene and isopropanol mixture.
All these deri vatives of phthalanilic ac id are white
crysta lline so lid s and deri vatives of maleanilic acid
are pale ye ll ow crystalli ne solids. These were fou nd to
be insoluble in hydrocarbons and chl orocarbons but
soluble in acetone and alcohols .
The lR spectra of these deri va tives have been
recorded in the range 4000-200 cm· 1 and followin g
tentative ass ignments ha ve been made on the basis of
earli er publications 5.?'}.'5. A broad band due to (N-H )
stretching vibrations present at 3400 cm· 1 in the
spectra of correspondin g anilic ac id s is shifted
towa rds lower frequencies (3250-3300 cm·1 ) which
may be attributed to mass effect of heavy metal ion,
weak ly coordi nated to nitroge n atom5 . The bands due
to carbony l stretching frequencies of secondary amide
group and ca rboxylate group are observed in the
region 1710-1765 and 1610-1655 cm·1 respectively.
The stretchin g bands due to (C-N) are present in the
164 1
region 1405-1465 cm· l . The bands due to (C-O)
stretching vibrations present in the region 1320-1 390
cm· 1 indicate the bonding of the ligands through
carboxylate group. The bands of medium to low
intensity due to (As-O) stretching vibrations are in the
region 520-545 cm· 1 and in the complexes (5-8 in
Table 1) an additional band of medium to low
intensity is present at 315-390 cm· 1 due to (As-S )15
stretching vibrations.
Since most of these compounds were found
insoluble in common organic solvents (hydrocarbons
and chlorocarbons), the IH NMR spectra of these
compounds were recorded in the mixture of DMSO
and acetone-d6 solution using TMS as internal
standard. The spectra of these complexes show
characteristic resonance due to ligand protons and
dithiolate group protons. Multiplets due to phenyl
protons of the ligand have been observed in the region
6.53 to 7.98 8 ppm. A sharp singlet due to (C H ~ S)
protons (complexes 5-8 in Table 1) have been
observed in the region 2.77 to 2.79 8 ppm indicating
that all CH 2S protons are magnetically eq ui va lent '-l· '5 .
The proton resonance due to (CH=CH) protons
(comp lexes 3, 4,7, 8) have been observed as a multiplet in the region 6.15 to 6.33 8 ppm. The proton
resonance due to (N-H) protons have been observed
as a singlet at 10.46 to 10.65 8 ppm, indicating
coordination of ligands through nitrogen also.
On the basis of above IR and 'H NMR spectral
data, it may be concluded that the liga nds are bonded
to arsenic atom through the oxygen of carboxyl ate
group and weakly coordinated through nitrogen atom.
Thus, these liga nd s are acting as bidentate moieties in
these derivatives. Therefore, tris derivatives seem to
ex hibit hexadentate coordination and mixed dithi olato
derivatives exh ibit tetradentate coordinati on with
arsenic. Since most of these derivatives are insolu ble
in common organic solvents, it seems that these deriva tives are polymeric in nature.
References
I
2
3
4
5
6
7
Datta S K , Z allal Chelll, 148 ( 1955) 259; 148 ( 1955 ) 267 : 148
( 1995) 335.
Vonkaulla K N. Bibliolh eca lIaelllalol. 19 ( 1962) 174.
Mal colm S & Pressman D. J Alii chelll Soc. 76 ( 1954) 2863 .
Unger S H & Hanseh C, Proc phys org Chelll. 12 ( 1976) I II .
Sharma C L. Arya R S & Ncrvi S S. J Illdiall cilelll Soc. LX III
( 1986) 267 and references th erei n.
& Rao R J. Snah
Chauhan H P S. Chourasia S. Agrawa l
reaCI ill org lIIel ·org Chelll , 24 ( 1994) 325 .
Tejankar B K , Rao R J & Chauhan H P S. SYlllh reaCI illorg
lII el ·org Ch elll . 2 1 ( 1991 ) 11 79 .
1642
8
INDIAN J CHEM. SEC. A, AUGUST 2002
Chourasia S & Chauhan H P S. Indian J Chern , 35A (1996)
903 .
9 Riddick J A & Bunger W B, Techniques of chemistry, Vol 2,
Organic Solvents (Wiley Interscience, New York), 1970.
10 Cava M p. Deana A, Muth K & Mitchell M J, Org Synth , 5
( 1973) 944.
II Chauhan H P S & Chourasia S, Indian J Chern, 34A (1995)
664 and references therein .
12 Chauhan H P S, Srivastava G & Mehrotra R C, Polyhedrol1,2
(1983) 359.
13 Nakamota K, Infrared and Raman spect.ra of inorganic alld
coordination compounds (John Wiley, New York), 1978.
14 Chauhan H P S & Lunkad S, Main grollp metal Chem. 17
( 1994) 313.
15 Chauhan H P S, Porwal B & Singh R K, Phosphorus, SlIlfllr
and Silicon, 160 (2000) 93 .