Functional derivatives of acetylene as reagents for inhibiting the growth of sulfate-reducing bacteria in oil production

Article abstract of DOI:10.1134/S0965544110060137

The [4+2] and [2+1] cycloaddition reaction of vinylacetylene derivatives with cyclopentadiene (hexachlorocyclopentadiene) and dichlorocarbene was used to prepare the corresponding cyclic derivatives that contain a triple bond and a functional group in the side chain and exhibit bactericidal activity against sulfate-reducing bacteria. It has been found that bacterial growth is suppressed at a reagent concentration of 50-200 mg/l. The introduction of electron-withdrawing chlorine atoms into the cycle is shown to reduce the bactericidal activity of bicyclic ethers and alcohols.

Full text of DOI:10.1134/S0965544110060137

ISSN 0965ꢀ5441, Petroleum Chemistry, 2010, Vol. 50, No. 6, pp. 484–488. © Pleiades Publishing, Ltd., 2010.
Original Russian Text © M.G. Veliev, A.Z. Chalabieva, I.A. Vezirova, M.I. Shatirova, M.I. Gadzhieva, 2010, published in Neftekhimiya, 2010, Vol. 50, No. 6, pp. 492–496.
Functional Derivatives of Acetylene as Reagents for Inhibiting
the Growth of SulfateꢀReducing Bacteria in Oil Production
M. G. Velieva, A. Z. Chalabievaa, I. A. Vezirovab, M. I. Shatirovaa, and M. I. Gadzhievab
a Institute of Polymer Materials, National Academy of Sciences of Azerbaijan, Sumgait, Azerbaijan
b Institute of Microbiology, National Academy of Sciences of Azerbaijan, Baku, Azerbaijan
eꢀmail: mveliyev@mail.ru
Received July 26, 2009
Abstract—The [4+2] and [2+1] cycloaddition reaction of vinylacetylene derivatives with cyclopentadiene
(hexachlorocyclopentadiene) and dichlorocarbene was used to prepare the corresponding cyclic derivatives
that contain a triple bond and a functional group in the side chain and exhibit bactericidal activity against sulꢀ
fateꢀreducing bacteria. It has been found that bacterial growth is suppressed at a reagent concentration of 50–
200 mg/l. The introduction of electronꢀwithdrawing chlorine atoms into the cycle is shown to reduce the bacꢀ
tericidal activity of bicyclic ethers and alcohols.
DOI: 10.1134/S0965544110060137
The success of secondary oil recovery by waterꢀ biocidal activity, which will facilitate a targeted synꢀ
thesis and search for new bactericides.
flooding (injection of natural water into an oil reserꢀ
voir) depends to a great extent on the presence of addiꢀ
tives, such as bactericides and corrosion inhibitors
EXPERIMENTAL
[1⎯5]. According to some data [6], 50 to 80% of all
corrosion damage observed in oil fields is due to bacꢀ
terial corrosion. In addition, the greatest damage to
edge waterflooding systems comes from sulfateꢀreducꢀ
ing bacteria (SRBs), which actively produce hydrogen
sulfide. Along with the generation of hydrogen sulfide,
bacteria and their clusters degrade the quality of oil
and decrease the permeability of productive layers.
The addition of chemical reagents to the water
injected into reservoirs is the most efficient technique
among the great number of known methods for preꢀ
venting the growth of SRBs [1, 5]. In this regard, the
design of highꢀperformance reagents that inhibit the
development of SRBs in oil production is of current
concern.
Preparation procedure for acetylene compounds of
the bicycloheptene series (I–IV). A mixture of 0.1 mol
of CPD and 0.1 mol of vinylacetylene alcohol or ether
thereof was heated for 6 h in the presence of 0.05 g of
hydroquinone in a sealed ampoule at 165–170 C. The
reaction products were subjected to vacuum distillaꢀ
tion (Table 1).
°
Preparation procedure for tetracyclic acetylene
compounds (V–VIII). A mixture of 0.2 mol of CPD
and 0.1 mol of vinylacetylene alcohol or ether thereof
was heated over 12 h in the presence of 0.05 g of hydꢀ
roquinone in a sealed ampoule at 165–170 C. After
°
appropriate treatment, the desired products were
obtained (Table 1).
Acetylene compounds of the polychlorobicyclohepꢀ
tene series (IX–XII). A mixture of 0.1 mol of HCCPD
and 0.1 mol of vinylacetylene alcohol or its ether was
heated for 6 h in the presence of 0.05 g of hydroꢀ
Various classes of compounds that inhibit the
growth of SRBs are known [7, 8]. In this respect, acetꢀ
ylene compounds are of interest as highly reactive subꢀ
stances. They can be used as a base for obtaining bioꢀ
logically active substances, modifiers, corrosion inhibꢀ
itors, oil additives, etc. [9–18]. In this work, we
describe results on the synthesis and study of bacteriꢀ
cidal action against SRBs of cyclic compounds that
contain a triple bond and functional groups in the side
chain. The compounds are synthesized via the [4+2]
and [2+1] cycloaddition reaction of functionalized
vinylacetylene derivatives with cyclopentadiene
(CPD), hexachlorocyclopentadiene (HCCPD), and
dichlorocarbene. In addition, we reveal the correlaꢀ
quinone in a sealed ampoule at 95–100 C (Table 1).
°
Preparation procedure for dichlorocyclopropane
compounds of the acetylene series (XIII–XVI). To a
mixture of 50 ml of 50% aqueous solution of sodium
hydroxide and 0.5 g of triethylbenzyl ammonium
chloride, a solution of 0.03 mol of vinylacetylene alcoꢀ
hol or ether thereof in 70 ml of chloroform was added
over 4 h with stirring. The reaction temperature was
maintained at 25–27
40 for another, diluted with 200 ml of water, and
subjected to ether extraction. The organic layer was
°
C. The mixture was stirred 1 h at
°
C
tion between the structure of the compounds and their separated and dried with MgSO4. The reaction prodꢀ
484

FUNCTIONAL DERIVATIVES OF ACETYLENE AS REAGENTS
Table 1. Constants, yields, and element analysis data for compounds I–XVI
485
Comꢀ
pound Yield, %
no.
Found, %
Cl
Calculated, %
Cl N
n2D0
d240
Empirical formula
Tb
,°C
(p, mm Hg
)
C
H
N
C
H
I
61.4 101–102 (1)
65.6 121–122 (1)
70.1 132–133 (1)
64.2 136–137 (1)
63.7 116–117 (1)
68.1 138–139 (1)
72.5 153–154 (1)
67.4 159–160 (1)
71.4 171–172 (1)
1.4590 1.1562 81.15 8.78
1.4410 1.1702 76.01 7.20
1.4305 1.1890 77.40 7.18
1.4250 1.1786 75.20 8.13
1.4695 1.2685 84.90 8.30
1.4580 1.2714 73.25 7.35
1.4470 1.2905 80.62 7.94
1.4375 1.2833 79.20 8.51
C10H12O
C12H14O2
80.98 8.16
75.76 7.41
73.10 7.08
75.03 8.48
84.07 8.46
79.05 7.86
80.86 7.91
79.03 8.58
II
III
IV
6.83 C13H15ON
C12H16O2
6.56
5.23
V
C15H18O
VI
C17H20O2
VII
VIII
IX
5.28 C18H21ON
C17H22O2
1.5590 1.5620 33.95 1.78 59.90
C10H6Cl6O
C12H8Cl6O2
33.85 1.70 59.94
36.31 2.03 53.59
X
69.5 180–181 (1.5) 1.5360 1.4990 36.42 2.91 53.78
XI
70.1 221–222 (1)
69.0 186–187 (1)
55.3 101–102 (8)
82.5 106–107 (1)
80.1 112–113 (1)
60.2 109–110 (1)
1.5330 1.4410 38.20 2.32 52.20 3.45 C13H9Cl6NO
38.28 2.22 52.15 3.43
36.13 2.52 53.32
XII
XIII
XIV
XV
XVI
1.5385 1.3036 36.80 2.51 53.40
1.4830 1.1330 44.02 3.68 42.80
1.4680 1.1190 46.50 3.70 34.21
C12H10Cl6O2
C6H6Cl2O
43.67 3.66 42.96
C8H8Cl2O2
46.40 3.89 34.24
1.4800 1.1540 49.65 4.23 32.40 6.45 C9H9Cl2NO
1.4750 1.1495 49.30 5.14 36.65 C8H10Cl2O
49.56 4.16 32.50 6.42
49.76 5.22 36.72
ucts (XIII–XVI) were isolated by vacuum distillation changes detected by differential thermal analysis start
(Table 1).
from 220 or above.
°C
The resultant cyclic compounds (I–XIV) were
tested for bactericidal activity against SRB using the
standard technique [16, 20]. SRB enrichment culꢀ
tures, which were based on Desulfovibrio Desulfuricans
bacteria, were isolated from reservoir water, purified
for removal of associated microorganisms by repeated
incubations, and used in the period of the highest
activity (after 3 or 4 days). A Postgate B medium was
used as a culture medium. Test tubes with the subꢀ
stances under study, the culture medium, and the SRB
The structure of products I–XVI was revealed by
IR and H NMR spectroscopy through synthesis of
1
authentic compounds; URꢀ10 and URꢀ20 spectroꢀ
photometers in a range of 600–4000 cm–1 and Teslaꢀ
487B (80 MHz) and Bruker WMꢀ250 (250 MHz)
spectrometers in a solution of CCl4 with hexamethyldꢀ
isiloxane as an internal standard, respectively, were
used. The purity of the synthesized compounds was
controlled using TLC and GLC. The TLC analysis
was carried out on Silufolꢀ254 plates with a fixed silica
gel layer. Benzene–ether (3 : 2) and heptane–ether
(3 : 1) binary systems served an eluent with developꢀ
ment in iodine vapor. The GLC analyses were carried
out on Chromꢀ3 and LKhMꢀ8 MD instruments with
a flame ionization detector and a katharometer. The
stationary liquid phases were SEꢀ30 (5%) and PEGꢀ
4000 (15%) supported on an NꢀAWꢀDMC Chromaꢀ
ton with a particle size of 0.200–0.250 mm. The analꢀ
culture were held in an incubator at 32 C for 10 or
°
12 days. Three parallel experiments were carried out
for each concentration; after that, the amount of
resulting biogenic hydrogen sulfide was determined
using iodometric titration. The bactericidal activity
was estimated according to the degree of inhibition of
C1 – C2
SRB growth by the formula:
z = ꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀꢀ × 100%,
C1
where C1 and C2 are the concentrations of hydrogen
sulfide in controlled and studied samples, respectively
(mg/l). The averaged results for each bactericide conꢀ
centration are listed in Table 2.
ysis temperature range was 30–500 C, the carrier gas
°
was helium, and the flow rate was 40–60 ml/min.
The thermal stability of the synthesized compounds
(I–XVI) was studied using a Paulik–Paulik–Erdey
derivatograph; the sample masses were 200 mg, and
the measuring ranges in the TG, DTA, and DTG
RESULTS AND DISCUSSION
modes were 200
The heating rate was
μ
V, 250
μ
V, and 1 mV, respectively.
5
°
C/min in a flow of air [18]. The
These studies made it possible to reveal the relaꢀ
test compounds are thermally stable; structure tionship between the structure and the biocidal activꢀ
PETROLEUM CHEMISTRY Vol. 50
No. 6
2010

486
VELIEV et al.
Table 2. Degree of inhibition of the SRB growth by cyclic acetylene compounds
Comꢀ Bactericide
pound concentration
Comꢀ
pound concentration
no.
IX
Bactericide
Concentration
of H2S mg/l
Bactericide
activity , %
Concentration
of H2S mg/l
Bactericide
activity , %
,
,
,
,
z
,
, z
no.
mg/l
mg/l
I
0
50
349.01
46.77
16.05
0
–
0
50
201.71
76.25
61.33
19.97
0
–
86.6
95.4
100.0
100.0
62.2
69.6
90.1
100.0
100
200
500
100
200
500
0
II
0
50
349.01
68.76
18.15
0
X
0
50
223.67
95.73
82.09
43.39
0
–
80.3
94.8
57.2
63.3
80.6
98.0
100
200
500
100
200
500
100.0
100.0
0
III
IV
0
50
270.94
–
XI
0
50
270.94
–
0
0
0
0
100.0
100.0
100.0
100.0
33.12
76.3
96.4
97.8
100.0
100
200
500
100
200
500
0
0
0
0
50
223.71
XII
XIII
XIV
XV
XVI
0
50
274.02
81.40
63.04
14.25
0
–
0
0
0
0
100.0
100.0
100.0
100.0
70.3
77.2
94.8
100.0
100
200
500
100
200
500
V
0
50
280.5
42.64
23.85
0
–
0
50
282.96
96.55
78.10
26.40
0
–
84.8
91.5
100.0
100.0
68.1
72.4
93.5
100.0
100
200
500
100
200
500
0
VI
0
50
280.5
68.47
37.49
13.93
0
0
50
273.36
110.17
81.74
23.34
0
–
78.8
90.2
63.2
70.1
90.3
100.0
100
200
500
100
200
500
98.6
100.0
VII
VIII
0
50
271.0
–
0
50
260.50
53.14
19.80
0
–
9.49
96.5
79.6
92.4
100.0
100.0
100
200
500
0
0
0
100.0
100.0
100.0
100
200
500
0
0
50
223.70
12.08
5.59
0
–
0
50
265.40
68.47
43.00
3.16
0
–
94.6
97.5
100.0
100.0
74.2
83.8
98.8
100.0
100
200
500
100
200
500
0
PETROLEUM CHEMISTRY Vol. 50
No. 6
2010

FUNCTIONAL DERIVATIVES OF ACETYLENE AS REAGENTS
487
ity and showed that CPD, taken in a 1 : 1 molar ratio (V–VIII); HCCPD easily enters the diene condensaꢀ
and heated (165–170 ), undergoes diene condensaꢀ tion with vinylacetylene dienophiles at 95–100 and
°C
°C
tion with dienophiles of the acetylene series regioseꢀ forms chlorinated bicyclo[2.2.1]ꢀheptꢀ2ꢀenes of the
lectively across the double bond of the vinyl group and acetylene series (IX–XII) with yields of 65–80%
forms, along with monoꢀadducts (I–IV), bisꢀadducts according to the scheme:
H5
H7
4
7
1
4
6
5
3
2
3
2
C C CH2OR
H8'
C C CH2OR
H8'
11 12
+
H8
10
H8
9
1
V–VII
I–IV
CH2=CH–C≡C–CH2OR⎯
Cl
Cl
Cl
Cl
Cl
Cl
H5
Cl
Cl
C C CH2OR
H6'
Cl
Cl
Cl
H6
Cl
IX–XII
R = H (I, V, IX), COCH3 (II, VI, X), CH2CH2CN (III, VII, XI), CH2CH2OH (IV, VII, XII).
The ratio between the monoꢀ (I–IV) and bisꢀ (geminal J6, 6' = 12.5–12.7 Hz and vicinal J5, 6 = 3.9–
adducts (V–VIII) depends on the chosen reaction 4.0 Hz). This is in complete agreement with the pubꢀ
conditions: for an equimolar ratio of CPD and vinyꢀ lished data [22–25].
lacetylene alcohol or its ethers, within 6 h at 165–
170 , we obtain 75–81% monoꢀ (I–IV) and 6–9%
The set of spectral data confirms that the diene
condensation of vinylacetylene alcohol and its ethers
with CPP and HCCPD occurs regioselectively, i.e.,
exclusively across the double bond of the vinyl group,
and stereoselectively by Alder’s rule with the formaꢀ
tion of adducts I–XII in the endo configuration.
It has been found that dichlorocyclopropanation of
vinylacetylene alcohol and its ethers occurs under the
phaseꢀtransfer catalysis conditions (triethylammoꢀ
°C
bisꢀadducts (V–VIII); when the ratio of CPD to vinyꢀ
lacetylene alcohol or its ethers is 2 : 1, the yield over
12 h at 165–170 C is 15–17% for monoꢀ (I–IV) and
°
64–67% for bisꢀadducts (V–VIII).
The composition and structure of compounds
I⎯XII are proved by the data of elemental analysis as
well as IR and 1H NMR spectroscopy; the identity was
controlled using TLC. The IR spectra of adducts
nium chloride, 50% NaOH, chloroform, 20–25
°C)
I⎯VIII exhibit intense bands at 3400–3440, 2235–
according to the scheme:
2250, 1630–1645, 1710–1730, 1230–1250, and
1130–1160 cm–1, which are characteristic of the
O
⎯
H,
C
≡
C, C=C, C N, C=O, and C–O bonds,
≡
CH2=CH–C≡C–CH2OR
respectively. In the IR spectra of adducts IX–XII, we
revealed intense bands at 3400–3430, 2230–2250,
1620–1640, 2140–2150, 1730–1760, and 660–
•
CCl
•
2
CH2=CH–C≡C–CH2OR
XIII–XVI
CCl2
710 cm–1, which are characteristic of the OH,
C≡
C,
, C=O, and C–Cl bonds, respectively; the
NMR spectra exhibit the chemical shifts ( , ppm)
C=C, C N
≡
R = H(XIII), COCH3(XIV), CH2CH2CN(IXV),
CH2CH2OH(XVI).
δ
2.8–3.0 ppm (Н5), 1.52–1.78 d.d (H6), 2.56–2.60 d.d
(H6'), 4.12–4.65 t (CH2O), 2.40
(OH), and 2.08 s (COCH3) [21].
t (CH2CN), 2.74 s
The yield of compounds XIII–XVI substantially
depends on the nature of the functional group of the
The structure of adducts I–XII is also confirmed by parent vinylacetylene compound. The reaction is the
1H NMR spectroscopy on the basis of values of the least effective for vinylacetylene alcohol (yield is
spin–spin coupling (SSC) constants of homotypic 10%). To synthesize dichlorocyclopropane comꢀ
bicyclic compounds [22, 23]. The found SSC conꢀ pounds with a triple bond and a hydroxyl group in the
6
6'
stants of three interacting protons C Hendo, C Hexo, side chain with high yields, we used the acetate protecꢀ
and C 5H adducts (I–XII) allow us to unambiguously tion of the hydroxy group in vinylacetylene alcohol.
attribute the endo configuration to the substituent The corresponding dichlorocyclopropanated acetyꢀ
PETROLEUM CHEMISTRY Vol. 50
No. 6
2010

488
VELIEV et al.
3. A. K. Talybly, Extended Abstract of Candidate’s Disserꢀ
tation in Biology (Moscow, 1979).
4. E. I. Andreyuk, V. I. Bilai, E. Z. Koval’, and I. A. Kozꢀ
lova, Microbial Corrosion and Its vozbuditeli (Naukova
Dumka, Kiev, 1980) [in Russian].
lenic acetate was obtained with a good yield (~75%),
which forms the desired alcohol (~86%) via hydrolyꢀ
sis, with preservation of the ring:
CH2=CH–C≡C–CH2OH + (CH3CO)2O
CH2=CH–C≡C–CH2OCOCH3
5. J. I. Bregman, Corrosion Inhibitors (Macmillan, New
York, 1963; Khimiya, Moscow, 1966).
6. A. A. Gonik, R. N. Lipovich, and K. R. Nizamov, Korꢀ
roziya Zashchita Neftegaz. Promꢀsti, No. 6, 15 (1977).
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(2008) [Pet. Chem. 48, 314 (2008)].
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A. F. Mamedova, Chemicals, Reagents, and Processes
ofLowꢀVolume Chemistry: Colection of Articles
(Belorusskaya Nauka, Minsk, 2008) [in Russian].
•
CCl
•
2
CH2–CH–C≡C–CH2OCOCH3
CCl2
–
OH
CH2–CH–C≡C–CH2OH.
XIII
CCl2
1
A characteristic feature of the H NMR spectra of
compounds XIII–XVI is the presence of upfield sigꢀ
nals in the form of a doublet, which are due to cycloꢀ
propane protons at
group produces signals in the form of a singlet at
3.90–4.20 ppm, and the acetate group is detected at
δ
= 1.96–2.30 ppm; the CH2О
δ
=
10. N. M. Agaev, M. G. Veliev, G. D. Geidarova, et al.,
Zashch. Met. 32, 101 (1996).
11. M. G. Veliev, A. Z. Chalabieva, N. Ya. Ishchenko, and
E. G. Akperova, Plast. Massy, No. 3, 19 (2004).
δ
= 1.90 (s).
The resulting compounds I–XVI were tested as
bactericides in SRB growth suppression. The test
results show (Table 2) that all of the synthesized agents
at a concentration of 50–100 mg/l offer a high degree
of inhibition of the SRB growth. Compounds III and
IV, which contain cyano ethoxy and hydroxy ethoxy
groups in the side chain, exhibit activity up to 100% at
a concentration of 50 mg/l. On passing from a subꢀ
stance with a bicycloheptene ring (I–IV) to substances
with polychlorobicycloheptene (IX–XII) and dichloꢀ
rocyclopropane rings (XIII–XVI), the activity
decreases to ~68% at a concentration of 50 mg/l.
In terms of the biocidal activity of terminal funcꢀ
tional groups in the side chain on the cycle (bicycloꢀ
heptene, polychlorobicycloheptene, dichlorocycloꢀ
propane, and tetracyclic), the derivatives are arranged
12. M. G. Veliev, N. Ya. Ishchenko, A. Z. Chalabieva, et al.,
Plast. Massy, No. 10, 21 (2007).
13. M. G. Veliev, O. A. Sadygov, N. A. Mamedova, and
S. A. Mustafaev, Neftekhimiya 49, 247 (2009) [Pet.
Chem. 49, 229 (2009)].
14. M. G. Veliev, M. I. Shatirova, N. Ya. Ishchenko, et al.,
Zh. Prikl. Khim. 81, 976 (2008).
15. M. G. Veliev, A. Z. Chalabieva, A. F. Mamedova, and
N. Ya. Ishchenko, Protsessy Neftekhim. Neftepererab.,
No. 1 (2008).
16. A. E. Smorodin, N. M. Agaev, M. M. Guseinov, et al.,
Zashch. Met., 471 (1983).
17. M. G. Veliev, N. M. Agaev, E. G. Akperova, and
A. Z. Chalabieva, in Proceeding of V AllꢀUnion On the
Current Status and Prospects of the Development of the
Theory of Manufacture of Chlornated Organic Products,
Baku, (1991), p. 160 [in Russian].
in the order CH2CH2CN > CH2CH2OH > H > COCH3
.
The bactericidal activity of compounds I–XVI, most
likely, is the result of the combined effect of the acetyꢀ
lene bond and the functional groups. It is noteworthy
that bicyclic compounds I–IV, which contain nonꢀ
conjugated enyne fragments in its molecule, along
with high biocidal properties, reduce the corrosion of
steel in an acid environment [15, 17] exhibiting the
18. M. G. Veliev, N. M. Agaev, M. I. Shatirova, et al., Zh.
Prikl. Khim. 79, 1848 (2006).
19. W. Wendlandt, Thermal Methods of Analysis (Wiley,
New York, 1974; Mir, Moscow, 1978).
20. V. I. Romanenko and S. I. Kuznetsov, Ecology of Freshꢀ
Water Microorganisms (Nauka, Moscow, 1974) [in Rusꢀ
sian].
21. A. J. Gordon and R. A. Ford, The Chemist’s Companion:
A Handbook of Practical Data, Techniques and Referꢀ
ences (Mir, Moscow, 1976; Wiley, New York, 1972).
properties of an inhibitor (z > 96%).
Thus, the resulting functionally substituted acetyꢀ
lene reagents extend the range of SRB growth inhibiꢀ
tors at a concentration of 50–100 mg/l and can be recꢀ
ommended as inhibitors of microbiological corrosion
of metals.
22. M. G. Veliev, A. Z. Chalabieva, M. I. Shatirova, et al.,
Zh. Org. Khim. 39, 874 (2003).
23. M. G. Veliev, A. Z. Chalabieva, M. I. Shatirova, et al.,
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