Biocidal activity of the esterification products of polyfluoroalkyl alcohols and pentafluorophenol with resin acids

Article abstract of DOI:10.1134/S1070363213130203

Esterification products of polyfluoroalkyl alcohols and pentafluorophenol with resin acids were synthesized and tested for bactericidal activity against Bacillus mucilaginosus and Bacillus coagulans and fungicidal activity against Aspergillus niger, Aspergillus terreus, Alternaria alternata, Trichoderma viride, Rhizopus oryzae, Rhizopus nigricans, Mucor mucedo, Penicillium funiculosum, Penicillium ochro-chloron, and Botrytis cinerea.

Full text of DOI:10.1134/S1070363213130203

ISSN 1070-3632, Russian Journal of General Chemistry, 2013, Vol. 83, No. 13, pp. 2738–2744. © Pleiades Publishing, Ltd., 2013.
Original Russian Text © G.G. Nyanikova, L.M. Popova, I.N. Gaidukov, O.P. Shabrina, S.V. Vershilov, 2013, published in Ekologicheskaya Khimiya, 2013,
Vol. 22, No. 2, pp. 99–106.
Biocidal Activity of the Esterification Products
of Polyfluoroalkyl Alcohols and Pentafluorophenol
with Resin Acids
G. G. Nyanikovaa, L. M. Popovab, I. N. Gaidukovb, O. P. Shabrinaa, and S. V. Vershilovc
a St. Petersburg State Institute of Technology, Moskovskii pr. 26, St. Petersburg, 190013 Russia
b St. Petersburg State Technological University of Plant Polymers,
ul. Ivana Chernykh 4, St. Petersburg, 198095 Russia
e-mail: lorapopova@mail.ru
c Lebedev Research Institute of Synthetic Rubber, ul. Gapsal’skaya 1, St. Petersburg, 198035 Russia
Received May 7, 2013
Abstract—Esterification products of polyfluoroalkyl alcohols and pentafluorophenol with resin acids were
synthesized and tested for bactericidal activity against Bacillus mucilaginosus and Bacillus coagulans and
fungicidal activity against Aspergillus niger, Aspergillus terreus, Alternaria alternata, Trichoderma viride,
Rhizopus oryzae, Rhizopus nigricans, Mucor mucedo, Penicillium funiculosum, Penicillium ochro-chloron, and
Botrytis cinerea.
Keywords: Resin acids, polyfluoroalkyl esters, bactericidal activity, fungicidal activity.
DOI: 10.1134/S1070363213130203
INTRODUCTION
various biologically active substances. A number of
pharmacologically active abietane diterpenoids were
synthesized on the basis of resin acids. For example,
dehydroabietic acid and their derivatives were found to
exhibit antiphlogistic, spasmolytic, sedative, antitumor,
immunomodulating, adaptogenic, antiulcer, and anti-
oxidant activity [3–5].
In view of increase in hydrocarbon price, additional
impetus has been given to studies directed toward
integrated utilization of plant raw materials. For
example, wood rosin and tall oil rosin are abundant
sources of tricyclic carboxylic acids and are therefore
promising from the viewpoint of synthesis of new
biologically active compounds.
Many authors have shown that resin acids and their
derivatives are capable of acting as insecticides,
fungicides, and bactericides. Dehydroabietic acid
(DAA) at a concentration of 39.7 μg/mL inhibited the
growth of Aspergillus terreus. Derivatives of dehydro-
abietic acid were active against A. fumigates and
A. niger, the minimum inhibitory concentrations being
50 and 63 μg/mL, respectively [3]. Bardyshev et al. [6]
studied biological properties of resin acid salts with
amines and found that abietic acid diethylammonium
and morpholinium salts exhibited a considerable
stimulating activity and accelerated metabolism.
Abietic acid ammonium salt inhibited the growth of
Botrytis cinereae and Fusarium moniliforme by 67 and
53%, respectively. Resin acids isolated from the bark
of Buddleja globosa were active against the
Esterification is
a
possible way of rosin
modification. Depending on the initial rosin type and
alcohol nature, the esterification products attract
interest as materials for the manufacture of environ-
mentally safe synthetic resins, ester plasticizers, hot
melt adhesives, lacquers, paints, and food container
adhesives [1]. Taking into account that compounds
containing long-chain fluoroalkyl groups possess
surfactant properties [2], esters derived from rosin and
fluorinated alcohols may be expected to act as good
film-forming agents in the manufacture of paint-and-
lacquer materials, as well as adhesive additives.
Specific structure of resin acids makes them
valuable starting compounds for the synthesis of
2738

BIOCIDAL ACTIVITY OF THE ESTERIFICATION PRODUCTS
2739
dermatophytes Trichophyton rubrum and Epider-
mophyton floccosum. 11,12-Dihydroxyabieta-8,11,13-
triene derivatives obtained from dehydroabietic acid
displayed a high activity against Microsporium canis
and Trichophyton mentagrophytes.
tetrachloride placed between KBr plates. The UV
spectra of solutions in ethanol with a concentration of
10–4 M were measured on an SF-2000 spectrophoto-
1
meter (cell path length 1 cm). The H and 19F NMR
spectra were obtained on a Bruker 500 spectrometer at
1
19
500 MHz for H and 470 MHz for F using CDCl3 as
solvent and CCl3F as external reference for 19F. The
progress of reactions and the purity of the initial
compounds and products were monitored by TLC on
Sorbfil plates using hexane–methylene chloride–
acetone (1:1:0.5) as eluent. Solvents were purified
according to standard procedures [8].
Pisiferic acid and its derivatives are active against
Proteus vulgaris, Staphylococcus aureus, and Bacillus
subtilis. Quinones showed a high activity toward
S. aureus. Plants of the genus Salvia (sage) produce
metabolites of the abietane series, some of which were
found to act as antitubercular agents and bactericides
against beta-hemolytic streptococcus.
Isolation of abietic acid (I) from wood rosin [9].
Wood rosin, 25 g, was dissolved in 75 mL of ethanol,
5 mL of concentrated aqueous HCl was added, and the
mixture was heated for 2 h at 80°C. The solvent was
distilled off, the residue was washed with water, and
the isomerized rosin was dissolved in diethyl ether.
The ether extract was dried over MgSO4, 8 mL of
diethylamine was added to the solution, and the
precipitate of abietic acid diethylammonium salt was
filtered off and recrystallized twice from petroleum
ether. The pure salt was treated with acetic acid, and
abietic acid thus formed was recrystallized from
ethanol. Yield 40%, mp 170–172°C. IR spectrum, ν,
cm–1: 1694 (C=O), 2936 (C–H), 3418 (O–H). UV
spectrum: λ 242 nm (logε 4.02). 1H NMR spectrum, δ,
ppm: 0.86 (C20H3), 1.01 and 1.02 (C16H3, C17H3), 1.26
(C19H3), 2.24 m (15-H, J = 6.89 Hz), 5.36 (7-H), 5.78
(14-H). Iodine number 173, acid number 183.
Antimicrobial activity of resin acids originates from
the presence in their molecules of hydroxy, aldehyde,
ketone, and other functional groups and is determined
by their configuration (cis or trans). The presence of
carboxy and hydroxy groups is in important factor
responsible for the activity of resin acids isolated from
cypress against gram positive bacteria. Alkylation of
the phenolic hydroxyl favors enhanced antimicrobial
activity, and its magnitude is related to the alkyl chain
length. However, replacement of the carboxy group by
CH3, CHO, CHOH, or CHOR does not increase
antibacterial activity [3]. Oxidized dehydroabietic acid
showed a stronger antifungal effect as compared to
abietic, levopimaric, and palustric acids.
Various resin acid preparations may find wide
application for protection of commercial products from
biodeterioration, conservation of wood varieties, and
modification of paint-and-lacquer materials [7]. Esters
derived from resin acids and fluorine-containing
alcohols [8–11] may also be valuable products, in
particular as biocides for protection of construction
materials from biodeterioration.
2,2,2-Trifluoroethanol was dried over NaX zeolite
and then distilled. IR spectrum, ν, cm–1: 947–1160 (C–F),
1
2963 (C–H), 3363 (O–H). H NMR spectrum, δ, ppm:
3.4 (OH), 3.92 q (1H, CH2, J = 8.4 Hz), 3.86 q (1H,
CH2, J = 9.2 Hz), 5.16 (OH). 19F NMR spectrum: δF
–76.35 ppm, t (CF3, J = 8.5 Hz).
The goal of the present work was to synthesize
esters from resin acids, on the one hand, and poly-
fluoroalkyl alcohols and pentafluorophenol, on the
other, and test the products for bactericidal and
fungicidal activity.
2,2,3,3-Tetrafluoropropan-1-ol (telomer, n = 1)
was distilled once under atmospheric pressure, a
fraction boiling at 120–121°C being collected. IR spec-
trum, ν, cm–1: 1107 (C–F), 2959 (C–H), 3387 (O–H).
1H NMR spectrum, δ, ppm: 2.59 (OH), 3.98 t.t (1H,
CH2, J = 13.5, 1.6 Hz), 5.93 t.t. (1H, CF2H, J = 53.2,
EXPERIMENTAL
19
4.3 Hz). F NMR spectrum, δF, ppm: –127 t (2-F, J =
As starting compounds we used wood rosin (GOST
18–12345) and telomer alcohols, 2,2,2-trifluoro-
ethanol, 2,2,3,3-tetrafluoropropan-1-ol, 1H,1H,5H-octa-
fluoropentan-1-ol, 1H,1H,7H-dodecafluoroheptan-1-
ol, and 1H,1H,9H-hexadecafluorononan-1-ol.
12.7 Hz), –138.80 d (3-F, J = 53.86 Hz).
1H,1H,5H-Octafluoropentan-1-ol (telomer, n = 2)
was distilled once under atmospheric pressure, a frac-
tion boiling at 140–142°C being collected. IR spec-
trum, ν, cm–1: 1171 (C–F), 2953 (C–H), 3402 (O–H).
1H NMR spectrum, δ, ppm: 3.03 t (CH2, J = 14.28 Hz),
The IR spectra were recorded on a Shimadzu IR
Prestige-2 instrument from solutions in carbon
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 13 2013

2740
NYANIKOVA et al.
16
15
12
11
17
20
13
14
1
RFCH2OH
O
2
CH2=C=O
9
10
8
5
4
6
7
13
−CH3−C
OH
18C=O
C=O
C=O
19
O−H
O−CH2RF
O−C=O
CH3
I
II
RF: CF3 (III)
CF2CF2H (IV)
(CF2CF2)2H (V)
(CF2CF2)3H (VI)
(CF2CF2)4H (VII)
III, RF = CF3; IV, RF = CHF2CF2; V, RF = H(CF2CF2)2; VI, RF = H(CF2CF2)3; VII, RF = H(CF2CF2)4.
3.75 (OH), 4.99 t.t (CF2H, J = 51.69, 4.92 Hz). 19F
NMR spectrum, δF, ppm:–119.09 m (2-F), –122.07
(3-F), –126.83 (4-F), –134.34 d (5-F, J = 53.86 Hz).
ether was cooled with ice, and gaseous ketene was
bubbled through the solution until persistent yellow
color (reaction time ~1 h, TLC). When the reaction
was complete, the solvent was removed under reduced
pressure to isolate anhydride II as a yellow oily
substance (yield quantitative). IR spectrum, ν, cm–1:
1H,1H,7H-Dodecafluoroheptan-1-ol (telomer, n = 3)
was distilled once under reduced pressure, a fraction
boiling at 140–142°C (5 mm) being collected. IR spec-
trum, ν, cm–1: 1200 (C–F), 2951 (C–H), 3388 (O–H).
1H NMR spectrum, δ, ppm: 4.11 t (CH2, J = 14.8 Hz),
5.2 (OH), 6.6 t.t (CF2H, J = 51.2, 5.4 Hz). 19F NMR
spectrum, δF, ppm:–121.5 m (2-F, 3-F), –122.9 and –123
(4-F, 5-F), –129.3 (6-F), –137.75 d (7-F, J = 49.6 Hz).
1
1737 and 1808 (C=O), 2937 (C–H). H NMR spec-
trum, δ, ppm: 0.88 (C20H3), 1.04 and 1.05 (C16H3,
C17H3), 1.32 (C19H3), 2.23 [C(O)CH3], 2.25 m (15-H,
J = 6.9 Hz), 5.37 (7-H), 5.8 (14-H).
Reaction of abietic acetic anhydride with 2,2,2-
trifluoroethanol. Abietic acetic anhydride prepared
from 5.0 g (17 mmol) of abietic acid was dissolved in
30 mL of hexane, 3.43 g (35 mmol) of 2,2,2-trifluoro-
ethanol and a few drops of concentrated sulfuric acid
were added, and the mixture was heated for 6 h under
reflux. When the reaction was complete (TLC), the
mixture was cooled, washed with cold water, a 15%
solution of NaHCO3, and water again to pH 7, dried
over MgSO4, and evaporated under reduced pressure.
The residue was 2,2,2-trifluoroethyl abietate (III) as a
brown transparent tarry material. Yield 75%, softening
point 55°C. IR spectrum, ν, cm–1: 1082–1167 (C–F),
1H,1H,9H-Hexadecafluorononan-1-ol (telomer,
n = 4) was dried in a vacuum desiccator over CaCl2,
IR spectrum, ν, cm–1: 1200 (C–F), 2959 (C–H), 3387
1
(O–H). H NMR spectrum, δ, ppm: 4.17 m (CH2, J =
7.29 Hz), 5.21 t (OH, J = 6.89 Hz), 6.90 t.t (CF2H, J =
19
50.7, 4.92 Hz). F NMR spectrum, δF, ppm: –120.77,
–121.07, –122.29, –122.43, –128.52 (2-F, 3-F, 4-F, 5-F,
6-F, 7-F, 8-F); –137.55 d (9-F, J = 51.5 Hz).
Generation of ketene CH2=C=O [14]. Ketene was
generated according to Williams and Hurd. A still flask
was charged with a required amount of acetone, the
setup was filled with an inert gas (argon), and the still
flask was heated so that to maintain acetone smoothly
boiling. Acetone valor contacted with a red-hot
tungsten filament and underwent pyrolysis to produce
ketene which passed through a reflux condenser into a
reactor. The yield of ketene attained 90%.
1
1692 (C=O), 2917 (C–H). H NMR spectrum, δ, ppm:
0.86 (C20H3), 1.01 and 1.03 (C16H3, C17H3), 1.26
(C19H3), 2.24 (15-H), 4.67 q (OCH2, J = 8.5 Hz), 5.35
(7-H); dehydroabietate: 5.78 (14-H), 6.89 s (14-H),
7.01 d and 7.19 d (11-H, 12-H). 19F NMR spectrum: δF
–72.33 ppm, t (CF3, J = 9.5 Hz).
Compounds IV–VII were synthesized in a similar
Abietic acetic anhydride (II) [10]. A solution of
way.
5.0 g (17 mmol) of abietic acid in 50 mL of diethyl
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BIOCIDAL ACTIVITY OF THE ESTERIFICATION PRODUCTS
2741
2,2,3,3-Tetrafluoropropyl abietate (IV). Yield
80%, yellow amorphous powder. softening point ~70°C.
IR spectrum, ν, cm–1: 1109 (C–F), 1694 (C=O), 2937
method, via reaction of abietic acetic anhydride with
polyfluoroalkanols. Abietic acetic anhydride (II) was
synthesized by treatment of abietic acid (I) with
gasoues ketene under mild conditions (diethyl ether, 0°C)
[14].
1
(C–H). H NMR spectrum, δ, ppm: 0.86 (C20H3), 1.01
and 1.03 (C16H3, C17H3), 1.27 (C19H3), 2.24 (15-H),
4.59 m (OCH2, J = 12.8 Hz), 5.36 (7-H), 5.78 (14-H),
6.39 t.t (CF2H, J = 53.4 Hz); dehydroabietate: 6.89 s
(14-H), 7.01 d and 7.18 d (11-H, 12-H). 19F NMR
spectrum, δF, ppm: –140.02 d (3′-F, J = 53.4 Hz), –
124.5 t (2′-F, J = 12.8 Hz).
The reactions of anhydride II with fluorinated
telomer alcohols CF3CH2OH, H(CF2CF2)n·CH2OH
(n = 1–4) were carried out under acid catalysis (in the
presence of H2SO4) on heating for 6 h in boiling
hexane, and the corresponding polyfluoroalkyl esters
III–VII were isolated in 75–85% yield. The progress
of reactions was monitored by TLC.
1H,1H,5H-Octafluoropentyl abietate (V). Yield
85%, yellow–brown amorphous substance. IR spec-
trum, ν, cm–1: 1173 (C–F), 1693 (C=O), 2941 (C–H).
1H NMR spectrum, δ, ppm: 0.85 (C20H3), 1.01 and
1.02 (C16H3, C17H3), 1.26 (C19H3), 2.23 m (15-H, J =
6.64 Hz), 2.86 (??), 4.12 t and 4.75 t (1H each, OCH2,
J = 14.8 Hz), 5.36 (7-H), 5.77 (14-H), 6.71 t.t and 6.75
t.t (CF2H, J = 51.2, 5.91 Hz); dehydroabietate: 6.88 s
(14-H), 7.01 d and 7.20 d (11-H, 12-H). 19F NMR
spectrum, δF, ppm: –137.56 d (CF2H, J = 45.78 Hz); –
129.62, –129.21, –124.81, –124.37, –121.11 m (J =
12.88 Hz), –118.83.
The reaction of abietic acid with gaseous ketene in
1
diethyl ether gave a compound whose H NMR spec-
trum contained signals typical of methyl protons in the
abietane fragment at δ 0.88 (C20H3), 1.04 and 1.05
(C16H3, C17H3), and 1.32 ppm (C19H3). The 15-H
proton in the isopropyl group resonated as a multiplet
signal at δ 2.25 ppm (J = 6.9 Hz). The presence of
signals at δ 5.37 (7-H) and 5.8 ppm (14-H) indicated
conservation of the number and position of double
bonds. Protons in the acetyl group gave a singlet at δ
2.23 ppm. In the IR spectrum of II we observed
absorption bands at 1737 and 1808 cm–1 typical of
anhydride moiety. These findings allowed us to assign
the structure of abietic acetic anhydride (II) to the
isolated compound.
1H,1H,7H-Dodecafluoroheptyl abietate (VI).
Yield 80%, brown tarry substance. IR spectrum, ν, cm–1:
1
1200 (C–F), 1695 (C=O), 2934 (C–H). H NMR
spectrum, δ, ppm: 0.85 (C20H3), 1.01 and 1.03 (C16H3,
C17H3), 1.20, 1.22, 1.26 (C19H3), 2.24 (15-H), 2.86,
4.79 t (OCH2, J = 14.3 Hz), 5.36 (7-H), 5.78 (14-H),
6.87 t.t (CF2H, J = 50.7, 5.17 Hz); dehydroabietate:
6.89 (14-H), 7.01 and 7.19 (11-H, 12-H). 19F NMR
spectrum, δF, ppm: –137.51 d (J = 49.59 Hz), –128.65,
–122.49, –121.31, –118.53 m (J = 12.86 Hz).
1
Esters III, IV, VI, and VII displayed in the H
NMR spectra multiplet signals from the OCH2 protons
in the fluorinated alkyl groups, δ, ppm: III, 4.67 q (J =
8.5 Hz); IV, 4.59 m (J = 12.8 Hz); VI, 4.79 t (J =
14.3 Hz); VII, 4.80 t (J = 14.3 Hz). It should be noted
that the corresponding protons in V gave rise to two
triplets at δ 4.12 and 4.5 ppm with equal coupling
constants (J = 14.8 Hz).
1H,1H,9H-Hexadecafluorononyl abietate (VII).
Yield 80%, brown tarry substance. IR spectrum, ν, cm–1:
1
1214 (C–F), 1693 (C=O), 2932 (C–H). H NMR
spectrum, δ, ppm: 0.86 (C20H3), 1.01 and 1.03 (C16H3,
C17H3), 1.26 (C19H3), 2.23 (15-H), 2.86, 4.80 t (OCH2,
J = 14.3 Hz), 5.37 (7-H), 5.78 (14-H), 6.91 t.t (CF2H, J
= 50.2, 5.4 Hz); dehydroabietate: 7.02 and 7.19 (11-H,
12-H). 19F NMR spectrum, δF, ppm: –137.55 d (J =
51.5 Hz), –128.5, –122.32, –121.04, –118.48.
Analogous pattern was observed for the terminal
proton in the fluoroalkyl residue. In the 1H NMR spec-
trum of V, the CF2H signal appeared as two triplets at
1
δ 6.71 and 6.75 ppm with equal H–19F coupling
constants through two and three bonds, 51.3 and 5.91 Hz.
In the spectra of IV, VI, and VII, the corresponding
signals were triplets of triplets located at δ 6.39 (J =
53.4 Hz), 6.87 (J = 50.7, 5.17 Hz), and 6.91 ppm
(distorted, J = 50.2, 5.4 Hz), respectively.
We synthesized esters of abietic and dehydroabietic
acids with fluorinated telomer alcohols (n = 1–4) and
pentafluorophenol [11–14]. Polyfluoroalkyl esters
were prepared by reaction of resin acids [8] or acid
chlorides with sodium alkoxides [10], as well as by
reaction of tall oil rosin with telomer alcohols (n = 2–
4; 150°C, 6 h) [10]. Some abietic acid esters with
polyfluoroalkyl alcohols were also obtained by another
The reaction of abietic acetic anhydride with
fluorinated alcohols was accompanied by dispropor-
tionation of the diterpene moiety with formation of the
corresponding dehydroabietic acid esters, as followed
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 13 2013

2742
NYANIKOVA et al.
Tabe 1. Compounds tested for biocidal activity and their concentrations
Run no.
Compound
Concentration, wt % Method of synthesis
SK-1
SK-2
Wood rosin
0.14
0.10
–
–
Tall oil rosin
SK-3
SK-4
SK-5
SK-6
2,2,2-Trifluoroethyl abietate (sort 2)
2,2,2-Trifluoroethyl abietate (sort 1)
2,2,3,3-Tetrafluoropropyl abietate (sort 1)
2,2,3,3-Tetrafluoropropyl abietate (sort 2)
0.08
0.13
0.10
0.12
[10]
This work
This work
[10]
SK-7
1H,1H,5H-Octafluoropentyl abietate
0.11
This work
SK-8
SK-9
1H,1H,5H-Octafluoropentyl dehydroabietate
0.10
0.11
[8]
Abietic acid
This work
IO-1
IO-2
IO-3
Pentafluorophenyl abietate
1.99
1.25
2.47
[9]
[9]
[9]
1H,1H,9H-Hexadecafluorononyl abietate
1H,1H,7H-Dodecafluoroheptyl abietate
IO-4
IO-5
IO-6
IO-7
1H,1H,7H-Dodecafluoroheptyl dehydroabietate
1H,1H,9H-Hexadecafluorononyl dehydroabietate (sort 1)
1H,1H,9H-Hexadecafluorononyl dehydroabietate (sort 2)
Pentafluorophenyl dehydroabietate
2.23
2.59
2.59
1.00
This work
[9]
This work
[9]
from the presence of signals at δ 6.89 (s, 14-H), 7.01
(d), and 7.18 ppm (d) (11-H, 12-H). In the reactions
with 2,2,2-trifluoroethanol and 2,2,3,3-tetrafluoro-
propan-1-ol, the contribution of the disproportionation
process was insignificant (~5%), whereas compounds
VI and VII contained up to 75% of the dehydroabietic
acid derivative.
the collection of microorganisms at the Technology of
Microbiological Synthesis Department of the St.
Petersburg State Institute of Technology.
Samples of SK-1–SK-9 were dissolved in
petroleum ether, and IO-1–IO-7, in ethanol. Fungicidal
activity was assessed by the disk or well diffusion
method in Petri dishes charged with the Czapek-Dox
or wort agar medium. The inhibition zone diameter
was measured after incubation for 7 days at 28°C.
19
The F NMR spectra of compounds III–VII were
consistent with the assumed structures. The products
were isolated as yellow to brown viscous glassy
transparent materials.
To develop recommendations for practical use of
one or another bioactive agent, it is necessary to
known its minimum concentrations at which it exerts
inhibitory or biocide effect. The minimum inhibitory
concentration (MIC) and minimum biocidal concentra-
tions (MBC) of the compounds under study were
determined by serial dilution and subsequent inocula-
tion first in liquid and then in solid nutrient medium.
Biocidal Activity of the Synthesized Compounds
As test cultures for the evaluation of bactericidal
and fungicidal activity of the synthesized compounds
we used bacterial strains Bacillus mucilaginosus and
Bacillus coagulans and micromycetes Aspergillus
niger, Aspergillus terreus, Alternaria alternata,
Trichoderma viride, Rhizopus oryzae, Rhizopus
nigricans, Mucor mucedo, Penicillium funiculosum,
Penicillium ochro-chloron, and Botrytis cinerea from
Antibacterial activity was estimated by the well
diffusion method in a medium containing sprat
hydrolyzate. The inhibition zone was measured after
incubation for 24 h at 28°C.
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BIOCIDAL ACTIVITY OF THE ESTERIFICATION PRODUCTS
2743
Tabe 2. Antibacterial activity of SK-1–SK-9 and IO-1–IO-7 (inhibition zone diameter, mm)
Comp. no.
SK-1
SK-2
SK-3
SK-4
SK-5
SK-6
SK-7
SK-8
SK-9
B. mucilaginosus
19.3±6.3
17.8±5.3
0
Comp. no.
IO-1
B. mucilaginosus
9.8±0.3
B. coagulans
12.5±1.0
12.5±1.5
13.5±1.5
10.9±1.1
12.8±1.8
16.0±2.5
11.3±1.3
IO-2
9.2±0.2
IO-3
9.8±0.3
10.8±2.2
10.5±1.5
9.5±0.5
IO-4
8.9±0.4
IO-5
8.9±0.3
IO-6
10.3±0.3
9.1±0.4
11.7±4.5
20.8±8.7
19.8±10.8
IO-7
As follows from the data in Table 2, all compounds,
except for SK-3, inhibited the growth of B.
mucilaginosus. The highest antibacterial effect was
observed for SK-1 SK-2, SK-8, and SK-9. All
compounds displayed a moderate activity against B.
coagulans.
Among 9 preparations of the SK series, eight showed
bactericidal activity against B. mucilaginosus, and only
one preparation of the IO series (IO-3) turned out to be
inactive.
(3) Preparations of the SK series are inactive
toward the fungi T. viride and B. cinerea. Alternaria
alternata is most sensitive to IO-4, IO-5, and IO-6;
A. terreus is most sensitive to IO-7; R. nigricans is
most sensitive to IO-1 and IO-7; P. ochro-chloron is
most sensitive to IO-2, IO-4, and IO-6; and B. cinerea
is most sensitive to IO-1, IO-2, and IO-6.
None of compounds of the SK series showed
pronounced antifungal effect toward T. viride or B.
cinerea. Such fungal strains as A. niger, A. terreus, R.
oryzae, M. mucedo, and P. funiculosum turned out to
be tolerant to compounds of the IO series. However,
IO-4, IO-5, and IO-6 were active against A. alternata,
IO-7 was active against A. terreus, IO-1 and IO-7 were
active against R. nigricans, IO-2, IO-4, and IO-6 were
active against P. ochro-chloron, and IO-1, IO-2, and
IO-6 were active against B. cinerea. Table 3 contains
the minimum biocidal concentrations of fungicides of
the IO series with respect to the most sensitive test
cultures. These data indicate that IO-5 is the most
active against A. alternata; IO-7 is the most active
against R. nigricans, and IO-2 is the most active
against P. ochro-chloron.
(4) The minimum biocidal concentrations are as
follows: 0.0125% IO-2, 0.1% IO-4, and 0.5% IO-6 for
P. ochro-chloron; 0.5% IO-4, 0.01% IO-5, and 0.5%
IO-6 for A. alternata; and 0.1% IO-5 for T. viride.
Table 3. Minimum fungicidal concentrations of IO-2–IO-7
toward
Comp. no.
IO-2
Fungus
P. ochro-chloron
P. ochro-chloron
A. аlternata
MFC, mg/mL
0.125
CONCLUSIONS
IO-4
1.000
(1) Abietic (dehydroabietic) acid polyfluoroalkyl
esters have been synthesized in 75–85% yield by acid-
catalyzed reaction of abietic acetic anhydride with the
corresponding polyfluorinated telomer alcohols
(n = 1–4).
IO-4
5.000
IO-5
A. аlternata
0.100
IO-5
T. viride
1.000
IO-6
P. ochro-chloron
A. аlternata
5.000
(2) Resin acid preparations (16 samples) have been
tested for fungicidal activity in 10 fungal strains and
for bactericidal activity against two bacterial strains.
IO-6
5.000
IO-7
R. nigricans
0.050
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 83 No. 13 2013

2744
NYANIKOVA et al.
8. Gordon, A.J. and Ford, R.A., The Chemist’s Com-
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