Synthesis diacetylenic ethers with terminal acetylenic bonds and studying them as inhibitors of steel corrosion in hydrochloric acid

Article abstract of DOI:10.1134/S1070427210110121

New diacetylenic ethers with terminal acetylenic bonds were synthesized.

Full text of DOI:10.1134/S1070427210110121

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2010, Vol. 83, No. 11, pp. 1957−1961. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.G. Veliev, N.M. Agaev, M.I. Shatirova, A.Z. Chalabieva, G.D. Geidarova, 2010, published in Zhurnal Prikladnoi Khimii, 2010,
Vol. 83, No. 11, pp. 1825−1829.
APPLIED ELECTROCHEMISTRY
AND CORROSION PROTECTION OF METALS
Synthesis Diacetylenic Ethers with Terminal Acetylenic Bonds
and Studying Them As Inhibitors of Steel Corrosion
in Hydrochloric Acid
M. G. Veliev, N. M. Agaev, M. I. Shatirova,
A. Z. Chalabieva, and G. D. Geidarova
Institute of Polymer Materials, National Academy of Sciences, Sumgait, Azerbaijan
Received January 27, 2010
Abstract—New diacetylenic ethers with terminal acetylenic bonds were synthesized.
DOI: 10.1134/S1070427210110121
Highly hydrocarbon, particular, diacetylene and its
derivatives are very promising in a production of vari-
ous aliphatic, cyclic, heterocyclic and organoelemental
compounds which possess biological and surfactant prop-
erties [1–6]. In addition, it is known that the acetylenic
compounds are applied as inhibitors of acid corrosion
[7–9]. Researches in the field of acetylenic compounds
and their properties are continued in [9–11].
reaction with propargyl bromide results in formation of
ethers with two terminal acetylenic bonds (I)–(VI) while
in the case with 2,3-dichloropropene, in formation of
chlorine-containing non-conjugated allylacetylenic es-
ters (VII)–(XII). Their further dehydrohalogenation on
the presence of potassium hydroxide in solution of ethyl
alcohol (75–80°C) also lead to formation of diacetylenic
ethers (I)–(VI) according to Scheme 1.
In this paper we studied diacetylenic ethers with
terminal acetylenic bonds and their protective prop-
erties under conditions of the steel corrosion in 5 N
hydrochloric acid. An interaction of monosubstituted
acetylenic alcohols (Ia)–(VIa) with propargyl bromide
and 2,3-dichloropropene was studied in the presence
of aqueous solution of sodium hydroxide and triethyl
benzyl ammonium chloride (TEBAC) at 50–60°C. The
We stated that an interaction of monosubstituted
acetylenic alcohols with glycidyl porpargyl ether in the
presence of boron trifluoride etherate at 50°C results in
formation of corresponding non-conjugated ether-alco-
hols with two terminal acetylenic bonds (XIII)–(XVI)
(Scheme 2).
Physicochemical characteristics of the synthesized
Scheme 1.
BrCH2C
CH
CH
CH
CH
CCR2(OX)nOCH2C
I_VI
CH
CCR2(OX)nOH
_HCl
KOH
Ia_VIa
ClCH2CCl
CH2
CH2
CCR2(OX)nOCH2CCl
VI)_XII
n = 0, R = H (Ia), (I), (VII); n = 1, R = H, X = OCH2CH2 (IIa), (II), (VIII); X = OCH2CH2CH2 (IIIa), (III), (IX); n = 0,
R = CH3 (IVa), (IV), (X); n = 1, R = CH3, X = OCH2CH2 (Va), (V), (XI); X = OCH2CH2CH2CH2 (VIa), (VI), (XII).
1957

1958
VELIEV et al.
Scheme 2.
CH
Ia, IIa, IVa, Va
CH2
CHCH2OCH2C
CH
CCR2(OX)nOH
+
O
OEt2
BF3
CH
CH
CCR2(OCH2CH2)nOCH2CHCH2OCH2C
OH
XIII_XVI
n = 0, R = H (XIII), CH3 (XIV); n = 1, R = H (XV), CH3 (XVI).
Table 1. Physochemical characteristics of the synthesized compounds I–XVI
Found, %
Calculated, %
Yield,
%
bp, °C
(Р, mm Hg)
Compd.
nD20
d420
Formula
C
H
Cl
–
76.44
76.57
6.50
6.43
I
75.6
80.2
85.1
72.3
116–117 (740)
87–88 (15)
1.4540
1.4595
1.4620
1.4505
0.9266
0.9502
0.9598
0.9216
C6H6O
69.70
69.54
72.08
72.26
78.72
78.65
72.40
72.26
74.10
74.19
55.31
55.19
55.18
55.02
7.21
7.30
8.56
8.49
8.36
8.25
8.32
8.49
9.22
9.34
5.30
5.41
6.20
6.35
II
–
–
–
–
–
C8H10O2
C10H14O2
C8H10O
III
IV
83.5–84.5 (3)
107–108 (745)
V
76.2
79.5
67.3
69.8
82–83 (15)
80–81 (3)
1.4565
1.4590
1.4685
1.4740
0.9478
0.9548
1.0397
1.0480
C10H14O2
C12H18O2
C6H7ClO
C8H11ClO2
VI
27.31
27.15
20.50
20.30
VII
VIII
119–120 (730)
93–94 (15)
59.15
59.26
7.30
7.46
17.61
17.49
IX
X
72.4
66.7
68.2
70.3
71.6
95–96 (3)
117–118 (740)
89–90 (15)
87–88 (3)
1.4785
1.4640
1.4705
1.4745
1.4785
1.0596
1.0362
1.0441
1.0566
1.0589
C10H15ClO2
C8H11ClO
C10H15ClO2
C12H19ClO2
C9H12O3
60.32
60.57
6.78
6.99
22.50
22.35
59.38
59.26
7.30
7.46
17.58
17.49
XI
62.29
62.46
8.19
8.30
15.52
15.36
XII
XIII
64.12
64.27
7.03
7.19
124.5–125 (7)
–
–
–
–
62.39
62.25
7.75
7.60
XIV
XV
73.2
76.2
78.4
121–122 (7)
128–129 (5)
125–126 (5)
1.4645
1.5017
1.4837
0.0101
1.1165
1.0689
C11H16O4
C11H16O4
C13H20O4
62.14
62.25
7.78
7.60
64.75
64.98
8.53
8.39
XVI
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 11 2010

SYNTHESIS DIACETYLENIC ETHERS WITH TERMINAL ACETYLENIC BONDS
1959
compounds I–XVI are listed in Table 1. The structure and
composition of the synthesized compounds are confirmed
by GLC and TLC, as well as by IR and NMR spectra
(Table 2). In IR spectra of compounds XIII–XVI there
are absorption bands in the ranges of 3400–3600, 3300,
2100–2140 and 1080–1145 cm–1 characteristic of O–H
bond, ≡C–H, and C–O–C bonds, respectively [12].
monitored by TLC on plates of Silufol UV-254 in dif-
ferent solvent systems and by gas chromatography with
LKhM-8 MD-5 chromatograph.
Synthesis of compounds I–XII. A mixture of 10 g
of sodium hydroxide, 0.2 g of TEBAC, 0.05 M of aceth-
ylenic alcohol, and 0.05 M of propargyl bromide (or
2,3-dichloropropene) was heated at 50–60°C with vigor-
ous stirring for 3 h. An organic layer was removed and
dried with potash. After distillation compounds I–XII
were isolated.
EXPERIMENTAL
IR spectra of the synthesized compounds were re-
corded on a UR-20 spectrophotometer in the range 400–
Counter synthesis of compounds I –IV. To a mixture
of 2 g potassium hydroxide in 30 ml of absolute ethyl
alcohol with vigorous stirring in the course of 30 min
0.05 M of compoundsVII–XII was added. After boiling
the reaction mixture for 6 h were processed by water
1
4000 cm–1 in a thin layer; H NMR spectra, on a Tesla
BS-487 B spectrometer (80 MHz) with HMDS as internal
standard. The purity of the synthesized compounds was
Table 2. 1H NMR and IR spectra of the synthesized compounds I–XVI
Compd..
1Н NMR, δ, ppm
IR spectra ν, cm–1
I
II
2.45 t (2 Н, 2 С≡СН, J=2 Hz), 4.18 d (4 Н, 2 СН2О)
2.43 t (2 Н, 2 С≡СН), 4.15 d (4 Н, 2 СН2О), 3.66–3.74 m (4 Н, ОСН2СН2О)
3280, 2100, 1070
3295, 2110, 1085
III
IV
V
2.46 t (2 Н, 2 С≡СН), 4.20 d (4 Н, 2 СН2О), 3.64 m (8 Н, ОСН2СН2СН2СН2О)
1.46 s (6 Н, 2 СН3), 2.4 s (2 Н, 2 С≡СН), 4.10 s (2 Н, СН2О)
3300, 2120, 1075
3300, 2115, 1090
3305, 2120, 1080
3290, 2110, 1086
1.44 s (6 Н, 2 СН3), 2.42 s (2 Н, 2 С≡СН), 4.08 s (2 Н, СН2О), 3.60 m (4 Н, ОСН2СН2О)
VI
1.42 s (6 Н, 2 СН3), 2.41 s (2 Н, 2 С≡СН), 4.12 s (2 Н, СН2О), 3.63 m (8 Н,
ОСН2СН2СН2СН2О)
VII
5.20 s, 5.50 s (2 Н, СН2=С), 3.10 s (2 Н, 2 СН2), 4.15 s (2 Н, СН2О), 2.42 t (1 Н, С≡СН)
3295, 2115, 1645,
1090, 635
VIII
5.16 s, 5.56 s (2 Н, СН2=С), 3.08 s (2 Н, СН2), 3.65 m (4 Н, ОСН2СН2О), 4.10 s (2 Н, СН2О), 3300, 2100, 1650,
2.46 t (1 Н, С≡СН) 1090, 650
IX
X
5.18 s, 5.48 s (2 Н, СН2=С), 3.13 s (2 Н, СН2), 3.66 m (8 Н, ОСН2СН2СН2СН2О), 4.12 s 3280, 2130, 1640,
(2 Н, СН2О), 2.41 t (1 Н, С≡СН) 1075, 655
5.13 s, 5.45 s (2 Н, СН2=С), 3.10 s (2 Н, СН2), 4.13 m (2 Н, СН2О), 1.45 s (6 Н, 2 СН3), 3290, 2125, 1655,
2.41 s (1 Н, С≡СН) 1080, 700
XI
5.18 s, 5.50 s (2 Н, СН2=С), 3.10 s (2 Н, СН2), 4.16 s (2 Н, СН2О), 3.60 m (4 Н, ОСН2СН2О), 3295, 2120, 1655,
1.38 s (6 Н, 2 СН3), 2.43 s (1 Н, С≡СН) 1085, 650
5.21 s, 5.56 s (2 Н, СН2=С), 3.14 s (2 Н, СН2), 4.14 s (2 Н, СН2О), 3.67 m (8 Н, 3300, 2125, 1645,
ОСН2СН2СН2СН2О), 1.39 s (6 Н, 2 СН3), 2.42 t (1 Н, С≡СН) 1085, 700
2.43 t (2 Н, 2 С≡СН), 4.05 s, 4.15 s (4 Н, 2 СН2О), 3.20–3.85 m (5 Н, ОСН2СНСН2О), 2.98 s 3400, 3300, 2120,
(1 Н, ОН) 1090
2.40 t (1 Н, 2 С≡СН), 4.10 s (2 Н, СН2О), 3.18–3.80 m (5 Н, ОСН2СНСН2О), 2.96 s (1 Н, 3450, 3290, 2125,
ОН), 1.35 s (6 Н, 2 СН3), 2.25 s (1 Н, С≡СН) 1085
XII
XIII
XIV
XV
2.42 t (2 Н, 2 С≡СН), 4.04 s, 4.18 s (4 Н, 2 СН2О), 3.15–3.90 m (9 Н, ОСН2СН2О, 3500, 3300, 2115,
ОСН2СНСН2О) 1070
2.43 t (1 Н, С≡СН), 4.12 s (2 Н, СН2О), 3.20–3.86 m (9 Н, ОСН2СН2О, ОСН2СНСН2О), 3460, 3285, 2110,
1.37 s (6 Н, 2 СН3), 2.23 s (1 Н, С≡СН) 1085
XVI
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 11 2010

1960
VELIEV et al.
and ether. The ether extract was dried over MgSO4 and lation and compound XIII was isolated.
compounds I–IV with identical data were separated by
Compounds XIV–XVI were analogously synthesized
from alcohols IIа, IVа, Vа.
distillation.
Synthesis of dioxaundeca-1,10-diyn-6-ol (XIII). To
The synthesized compounds I–VI and XIV–XVI
were studied as inhibitors of steel corrosion in 5 N hy-
drochloric acid.
11.2 g (0.1 M) of 3-glycidylprop-1-yne containing 0.1 ml
of boron trifluoride etherate in the course of cooling (0°C)
and stirring 2.8 g (0.05 M) of propargyl alcohol (Ia) was
gradually added. The mixture was agitated additionally
for 7 h at 30°C and then was subjected to vacuum distil-
The inhibitory effect of the compounds was studied
by gravimetric technique that simulates an effect of
Table 3. Efficiency of diacetylenic compounds in the case of corrosion of steel in 5 N hydrochloric acid
Corrosion rate, g m–2 h–1, at Т, °С
Protection degree Z, %, at Т, °С
Concentration of
inhibitor,
Compound
20
40
60
20
40
60
g l–1
I
0.25
0.5
4.9
4.0
3.1
1.87
1.0
0.4
1.7
0.8
0.2
4.1
3.0
2.6
5.0
3.4
2.9
1.8
0.9
0.6
2.0
1.7
0.9
1.9
0.8
0.6
3.4
2.6
1.2
3.6
2.6
1.6
16.8
13.7
12.5
3.1
2.9
1.7
1.7
1.1
0.9
4.7
4.0
3.1
11.6
9.7
6.1
9.6
7.1
4.3
10.4
8.7
6.0
11.2
7.1
4.2
8.0
7.3
3.9
4.3
2.9
1.4
38.9
7.5
40.75
51.6
62.5
78.2
83.5
95.1
80.6
90.3
97.5
50.4
63.7
68.5
39.5
58.8
64.9
73.2
74.3
76.6
75.8
79.4
89.1
77.0
90.3
92.9
58.9
68.6
85.4
56.4
68.6
80.7
71.62
76.86
78.9
94.7
95.1
97.1
97.1
98.1
98.4
92.0
93.2
94.7
80.4
83.6
89.6
87.2
88.0
92.7
82.4
85.3
89.8
81.0
88.0
92.9
86.4
87.6
93.4
92.7
95.1
99.7
86.4
87.3
98.5
96.7
97.6
99.3
96.1
97.4
99.6
97.0
98.2
98.6
87.9
91.6
96.3
92.7
94.9
96.8
95.0
96.4
98.2
92.5
93.7
98.8
85.2
96.6
98.1
88.0
90.8
96.1
1.0
3.25
9.3
II
III
0.25
0.5
6.7
1.0
2.0
0.25
0.5
11.0
7.4
1.0
1.1
IV
0.25
0.5
8.4
5.1
1.0
3.9
V
0.25
0.5
34.6
25.0
10.4
20.8
14.6
9.0
1.0
VI
0.25
0.5
1.0
XIII
XIV
XV
XVI
0.25
0.5
14.9
10.2
5.2
1.0
0.25
0.5
21.4
18.0
9.3
1.0
0.25
0.5
9.5
6.1
1.0
3.1
0.25
0.5
34.4
26.2
11.0
1.0
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 83 No. 11 2010

SYNTHESIS DIACETYLENIC ETHERS WITH TERMINAL ACETYLENIC BONDS
1961
Table 4. The number of twists that the sample withstands
before fracture after exposure in 5 N HCl containing inhibitor.
Inhibitor concentration of 0.5 mg l–1, t = 20°C
acid etching steel St.3. Before the test steel samples of
30 × 20 × 3 mm size were cleaned out with grinding
machine with rubber circles, degreased with acetone
and kept for 1 day in a desiccator. The concentration of
the inhibitors was selected in the range of 0.25–1.0 g l–1,
temperature of acid media (20–60°C) was thermostated.
Results of the experiments listed in Table 3 show that the
synthesized compounds appear high inhibiting properties
under conditions of the steel corrosion in hydrochloric
acid. A protection degree of steel Z against corrosion
at 20–60°C is 56–99%. The obtained results allows as-
suming that diacetylene compounds I–VI, XIII–XVI
with two terminal acetylene bonds are highly efficient in
reducing the acid corrosion of steel owing to the presence
on the molecular structure of two acetylene π-bonds as
adsorption sites. Increasing the concentration of inhibi-
tors leads to the proportional increase in their protective
properties that presumably is associated with activation
of chemosorption of particles or fragments of molecules
on the surface of the metal.
Number of revolutions vefore the fracture
of the initial wire and after exposition
Compound
in 5 N HCl with
in 5 N HCl
inhibitors
ингибиторами
XIII
XIV
XV
2.0
2.0
2.0
2.0
64
66
64
65
XVI
rosion in 5 N hydrochloric acid. It was stated that their
inhibitory effect mainly depends on the presence in the
molecule of two terminal acetylene bonds.
REFERENCES
The synthesized compounds were also studied as re-
agents that reduce hydrogenation and brittleness of steel
which was indirectly determined from the change in the
material plasticity. The experiments were performed on
test machine K-5 by breaking the tested steel wires after
their exposition in 5 N hydrochloric acid without inhibi-
tors and in their presence (Table 4). The steel St.10 wire
of 2 mm diameter was the tested material. The data of
Table 4 show that the inhibitors under study reduce water
permeability of steel keeping the steel wire plasticity. In
can be assumed that the corrosion of steel and preserva-
tion of its plasticity proceed by various mechanisms.
Presumably a protective film being formed on the metal
surface is not able to completely prevent a migration of
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