Structure, anticorrosion and antibacterial evaluation of 1-(Morpholinomethyl)indoline-2,3-dione

Article abstract of DOI:10.14233/ajchem.2014.17868

In this paper, 3-(4-hydroxyphenylimino)indolin-2-one, was synthesized and analyzed by NMR, MS and X-ray single crystal analysis. The inhibition and the mechanism of the compound on the corrosion of high protective Q235A steel in HCl solution were screened and discussed. The results indicated that it can inhibit the corrosion with moderate inhibition efficiency in different conditions and the inhibition mechanism of the corrosion inhibiting may be mainly contributed to the adsorption. It was screened for antibacterial activity against oilfield water-borne bacteria and it showed good to moderate activity against sulfate reducing bacteria.

Full text of DOI:10.14233/ajchem.2014.17868

Asian Journal of Chemistry; Vol. 26, No. 22 (2014), 7795-7798
ASIAN JOURNAL OF CHEMISTRY
http://dx.doi.org/10.14233/ajchem.2014.17868
Structure, Anticorrosion and Antibacterial Evaluation of 1-(Morpholinomethyl)indoline-2,3-dione
1,*
2
GUO-XIN SUN and YAN-QING MIAO
1
2
Sports Physiology Biochemistry of Laboratory of Physical Education Department, Southwest Jiaotong University, Chengdu 611756, P.R. China
Department of Pharmacology, Xi’an Medical University, Xi’an 710068, P.R. China
*
Corresponding author: Tel./Fax: +86 29 88382693; E-mail: miaoyanqing2006@163.com
Received: 22 April 2014; Accepted: 8 July 2014; Published online: 6 November 2014;
AJC-16238
In this paper, 3-(4-hydroxyphenylimino)indolin-2-one, was synthesized and analyzed by NMR, MS and X-ray single crystal analysis.
The inhibition and the mechanism of the compound on the corrosion of high protective Q235A steel in HCl solution were screened and
discussed. The results indicated that it can inhibit the corrosion with moderate inhibition efficiency in different conditions and the
inhibition mechanism of the corrosion inhibiting may be mainly contributed to the adsorption. It was screened for antibacterial activity
against oilfield water-borne bacteria and it showed good to moderate activity against sulfate reducing bacteria.
Keywords: Indole-2,3-dione, Mannich base, Corrosion inhibition, Adsorption, Microbiologically influenced corrosion.
INTRODUCTION
EXPERIMENTAL
Indole-2,3-dione is a compound found in Strobilanthes
Synthesis of 1-(morpholinomethyl)indoline-2,3-dione:
1-(Morpholinomethyl)indoline-2,3-dione was synthesized
according to published methods (Scheme-I). Indole-2,3-dione
(1 mmol), formaldehyde (1.1 mmol) and mor-pholin (1.1
mmol) were dissolved in methanol (30 mL). The mixture was
refluxed until the disappearance of indole-2,3-dione, as
evidenced by thin-layer chromatography. The solvent was
removed in vacuo and the residue was separated by column
cusia (Nees) Kuntze and many other plants such as genus Isatis,
Calanthe discolour Lindl., Couroupita guianensis Aubl. and
1
in mammalian tissue . It displays versatile bioactivity and it is
used to synthesize a large variety of heterocyclic compounds
2
-4
in preparing drugs . Indole-2,3-dione Mannich bases are
5,6
reported to have antibacterial activities .
Compounds, containing functional electronegative groups
and p and/or π-electron in triple or conjugated double bonds,
chromatography (silica gel, petroleum ether/ethyl acetate =
7,8
1
are found to be efficient as inhibitors against metal corrosion .
It has been commonly recognized that an organic inhibitor
usually promotes formation of a chelate on a metal surface,
by transferring p and/or π-electrons from the organic com-
pounds to the metal and forming a coordinate covalent bond
1:1), giving the title compound. H NMR (D
6
-DMSO, 400
MHz): 7.61 (2H, m), 7.15 (1H, t, J = 7.2 Hz), 7.09 (1H, d, J =
8.0 Hz), 4.45 (2H, s), 3.70 (4H, t, J = 4.8 Hz), 2.63 (4H, t, J =
+
4.8 Hz); MS (EI) m/z: 246 (M ). 20 mg of the title compound
was dissolved in 50 mL methanol and the solution was kept at
room temperature for 7 d, natural evaporation gave orange
single crystals of the title compound suitable for X-ray analysis.
X-ray data collection and structure refinement: Intensity
data for colourless crystals of compound 4 was collected at
9
-11
during the chemical adsorption . Organic compounds, con-
taining heteroatoms, such as sulfur, phosphorus, nitrogen and
oxygen, together with aromatic rings in their structure are the
major adsorption centers and the Schiff bases, a condensation
product of an amine and a ketone/aldehyde, are such typical
150 K on a Bruker SMART 1000 CCD fitted with MoK
α
12-14
molecules . Some polydentate Schiff base compounds have
been reported as effective corrosion inhibitors for various
radiation. The data sets were corrected for absorption based
on multiple scans and reduced using standard methods. The
13,15-17
13
metals in acid media
. Several indole-2,3-dione derivatives
structures was solved by direct-methods and refined by a
1
8-20
2
have been reported as inhibitors in HCl solution . The aim
of this work is to screen the inhibitory action of 1-(morpholino-
methyl)indoline-2,3-dione for the corrosion of mild steel both
in high concentrated HCl solution and microbiologically
influenced corrosion.
full-matrix leastsquares procedure on F with anisotropic
displacement parameters for non-hydrogen atoms, carbon- and
nitrogen bound hydrogen atoms in their calculated positions
2
2
2
and a weighting scheme of the form w = 1/[σ (F
o
) + (αP) + bP]
2
2
where P = (F
o
+ 2F
c
)/3). All hydrogen atoms were positioned

7
796 Sun et al.
Asian J. Chem.
O
O
O
O
O
Microbiological monitoring: Viable counts of SRB, TGB
and FB were determined with the "most probable number"
method, People's Republic of China Standard of Petroleum
and Natural Gas Industry, the national method of the bacte-
ricidal agent's performance, SY/T 5890-1993). The produced
water containing the three kinds of bacteria was gathered from
Zichang Oilfield Factory, Yanchang Oilfield.
+
CH O +
2
N
H
N
H
N
N
O
Scheme-1: Synthesis of 1-(morpholinomethyl)indoline-2,3-dione
RESULTS AND DISCUSSION
geometrically and allowed to ride on their parent atoms, with
d(N-H) = 0.86 Å and Uiso(H) = 1.2 Ueq(N), d(C-H) = 0.93 or
Structure: The X-ray structural analysis confirmed the
assignment of its structure from spectroscopic data. Geometric
parameters of 1-(morpholinomethyl)indoline-2,3-dione are in
the usual ranges. The atomic coordinates are displayed in
Table-2 and the molecular structure is shown in Fig. 1. The
space-group is P 1 21/c 1 with a monoclinic crystal system.
The indol-2-one ring system is substantially planar and the
morpholin ring displays a typical chair conformation, with
the 2,3-dioxoindolin-1-yl)methyl group in equatorial position.
In the crystal structure, molecules are kinked into a three-
dimensional network by C-H…O hydrogen bonds as shown
in Fig. 2 and the hydrogen bonds parameters are included in
Table-3.
0
.96 (CH ) Å and Uiso(H) = 1.2 Ueq(C) or 1.5 Ueq(C). Crystal
3
data and refinement details were given in Table-1.
Gravimetric measurements: The corrosion tests were
performed on Q235A with a composition (in wt. %) C: 0.22,
P: 0.045, Si: 0.35, S: 0.05, Mn: 1.40 and Fe balance. The elec-
trolyte solution was 3M HCl, prepared from analytical grade
3
8 % HCl and distilled water. The concentration range of 3-(4-
hydroxyphenylimino)indolin-2-one was employed as 0.05 and
.10 g/L.All tests have been performed in deaerated solutions
0
and at 60 ± 0.5 ꢀC. The gravimetric tests were carried out
according to the People's Republic of China Standard of
Petroleum and Natural Gas Industry (Evaluation method for
behaviour of corrosion inhibitor for produced water of oilfield,
SY/T5273-2000) with a few modifications. Each test was done
with three specimens at the same time to give reproducible
results.
Inhibitor properties and mechanism: Corrosion can be
defined as the degradation of a material due to a reaction with
its environment. Degradation implies deterioration of physical
properties of the material. This can be a weakening of the
TABLE-1
EXPERIMENTAL DATA OF 1-(MORPHOLINOMETHYL)INDOLINE-2,3-DIONE
Crystal parameter
Data
Crystal parameter
Data
a (Å)
b (Å)
c (Å)
β (º)
Volume
Z
11.608(2)
8.2818(17)
12.595(3)
100.20(3)ꢀ
1191.69(645)
4
1.37251
0.115
166
Index ranges
Reflections collected
Independent reflections
Reflections theta (ꢀ)
-4 ≤ h ≤ 5; -13 ≤ k ≤ 12; -11 ≤ l ≤ 12
3220
2189
2.26 to 28.27
0.9444 to 0.9866
1427
Absorption correction transmission
Reflections with I ≥ 2σ(I)
Number of parameters
3
Density (mg/m )
Absorption coefficient
F (000)
109
1.006
2
Goodness-of-fit on F
Final R indices [I > 2s(I)]
R indices (all data)
Refine different density
R1 = 0.1884; wR2 = 0.1323
R1 = 0.0674; wR2 = 0.1027
-0.224 to 0.176
3
Crystal size (mm )
Theta range for data collection (ꢀ)
0.21 × 0.25 × 0.30
1.9 to 27.3
TABLE-2
2
ATOMIC COORDINATES (IN Å ) OF 1-(MORPHOLINOMETHYL)INDOLINE-2,3-DIONE
Atom
N2
N1
C7
O2
C10
H10A
H10B
O3
O1
C6
H6A
C8
C2
C9
C5
x/a
y/b
z/c
Atom
C1
C3
H3A
C13
H13A
H13B
C4
H4A
C12
H12A
H12B
C11
H11A
H11B
H9A
H9B
x/a
y/b
z/c
0.91766(9)
0.73127(8)
0.68098(9)
0.59676(8)
0.98088(11)
0.95910
0.23385(12)
0.33226(11)
0.48053(14)
0.46330(13)
0.23531(16)
0.33020
0.11391(8)
0.00535(8)
0.03062(9)
-0.24949(7)
0.02322(11)
-0.02090
0.70789(11)
0.56961(11)
0.53110
0.95237(11)
0.91260
0.93030
0.57469(12)
0.54030
1.08328(12)
1.10650
1.10430
1.11103(11)
1.13290
1.15290
0.30626(15)
0.70484(16)
0.75570
0.37262(17)
0.36920
0.47180
0.77531(16)
0.87570
0.3691(2)
0.46160
0.27210
0.23690(17)
0.13850
0.23970
-0.1031(1)
-0.05764(11)
-0.11970
0.18371(11)
0.24520
0.14430
0.04263(12)
0.04810
0.22195(12)
0.26800
0.26420
0.06581(12)
0.10620
0.00570
0.96040
0.14040
-0.02120
1.14402(7)
0.73752(10)
0.68346(10)
0.71920
0.62332(10)
0.63447(10)
0.79252(11)
0.63034(11)
0.63230
0.37200(13)
0.19019(12)
0.54811(15)
0.49570
0.55651(14)
0.45189(15)
0.21364(15)
0.69807(15)
0.74770
0.13337(9)
-0.15122(8)
0.13085(10)
0.19340
-0.06320(9)
-0.15409(10)
0.08256(11)
0.13481(11)
0.20140
0.7745(10)
0.7566(11)
0.1067(17)
0.2191(14)
0.0422(11)
0.1471(11)
H5A

Vol. 26, No. 22 (2014)
Structure, Anticorrosion and Antibacterial Evaluation of 1-(Morpholinomethyl)indoline-2,3-dione 7797
TABLE-3
INTERMOLECULAR HYDROGEN BONDS PARAMETERS OF 1-(MORPHOLINOMETHYL)INDOLINE-2,3-DIONE
D-H···A
C6-H6A-O1
C5-H5A-O2
D-H
0.9300
0.9300
H···A
2.4700
2.5200
D···A
3.349(2)
3.216(2)
D-H···A
158.000
131.000
i
ii
*Symmetry codes: (i) x, 0.5-y, 0.5 + z; (ii) x, 1.5-y, 0.5 + z
material due to a loss of cross-sectional area, it can be the
shattering of a metal due to hydrogen embrittlement, or it can
be the cracking of a polymer due to sunlight exposure. The
use of corrosion inhibitors has been considered as the most
effective method for the protection against such acid attack.
Some inhibitors, such as imidazoline, Mannich base, Schiff
base and some other heterocyclic compounds, have been
employed in this process, but the concentration or the price is
too high to be acceptable.
In the following work, the performance of the title com-
pound as an inhibiter with the concentration from 100 to 1000
mg/L in 1M and 2M HCl under the temperature from 30 to 65 ꢀC
and the results were summarized in Table-4. From the table, it
was found that almost all the inhibition efficiency increases
along with the concentration of inhibitor, but there is difference
in the two concentrations and different temperatures and it
reaches to 81.9 % with the concentration of 1000 mg/L in 1 M
HCl solution, further increase of the inhibitor does not increase
the inhibition efficiency.
Fig. 1. Molecular structure of 1-(morpholinomethyl)indoline-2,3-dione
TABLE-4
CORROSION INHIBITION EFFICIENCY OF
-(MORPHOLINOMETHYL)INDOLINE-2,3-DIONE
1
Concentration HCl Concentration Temperature
mg/L)
Inhibition
Efficiency (%)
(
(M)
1
1
1
2
2
2
1
1
1
2
2
2
1
1
1
2
2
2
1
1
1
2
2
2
(ꢀC)
30
45
60
30
45
60
30
45
60
30
45
60
30
45
60
30
45
60
30
45
60
30
45
60
1
1
1
1
1
1
2
2
2
2
2
2
5
5
5
5
5
5
00
00
00
00
00
00
00
00
00
00
00
00
00
00
00
00
00
00
13.8
27.9
21.3
18.2
19.0
16.7
23.5
27.9
33.3
26.3
23.1
20.8
55.8
69.8
66.7
53.1
63.7
58.8
81.9
77.5
78.0
72.9
71.0
60.0
1000
1000
1000
1000
1000
1000
The inhibition mechanism of the corrosion inhibiting may
be mainly contributed to the adsorption. The process of adsor-
ption is governed by the chemical structure of these inhibitors.
The presence of N, O, S atoms and conjugated bonds in the
structures makes the formation of p-d bonds resulting form
Fig. 2. Packing diagram of 1-(morpholinomethyl)indoline-2,3-dione

7
798 Sun et al.
Asian J. Chem.
the overlap of p electrons to the 3d vacant orbital of Fe atoms,
1-(morpholinomethyl)indoline-2,3-dione is antifungal active
against SRB and IB, but inactive against TGB under both concen-
trations.
which conforms the adsorption of the compounds on the metal
2
1
surface . The inhibitive performance of 1-(morpholino-
methyl)indoline-2,3-dione can be explained on the presence
of polydentate nitrone and indolin which rises the possibility
Conclusion
22
1-(Morpholinomethyl)indoline-2,3-dione was synthesized
and the its anticorrosion characters and the mechanism on the
corrosion of high protective Q235A steel in HCl solution were
screened and discussed. The title compound can inhibit the
corrosion with moderate inhibition efficiency in different
conditions and the highest reaches to 81.9 % in 1M HCl with
the concentration of 1000 mg/L. Besides, it displays potent
activity against the oilfield water-borne bacteria, especially
for SRB and IB.
of transferring the unshared electron of this molecule to iron .
The possible reaction centers are unshared electron pair of
heteroatoms and/or π-electrons of aromatic ring. The schematic
illustration of different modes of adsorption on metal is shown
in Fig. 3.
ACKNOWLEDGEMENTS
This work was financially supported by Scientific Research
Program Funded by Shaanxi Provincial Education Department
(
12JK0589).
Fig. 3. Absorption of 1-(morpholinomethyl)indoline-2,3-dione molecules
on the ion surface
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2
, ClO , formaldehyde,
2
18
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1
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TABLE-5
ANTIFUNGAL ACTIVITY OF 1-(MORPHOLINOMETHYL)-
INDOLINE-2,3-DIONE AGAINST OILFIELD
WATER-BORNE BACTERIA
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Microbiotic concentration/mL
Concentration
SIB
110.0
0.0
IB
110.0
0.0
TGB
110.0
70.0
-
0
0
.20 g/L
.02 g/L
25.0
25.0
110.0