Antimicrobial surfactants based on N,N′-(5-oxanona-2,7-diyne-1,9- diyl)bis[(alkoxycarbonylmethyl)-dimethylammonium] chlorides

Article abstract of DOI:10.1134/S107042720803021X

A series of quaternary bisammonium salts containing the common 5-oxanonane-2,7-diyne-1,9-diyl fragment and different alkoxycarbonylmethyl groups was synthesized. The surfactant properties and antimicrobial activity of these compounds were studied.

Full text of DOI:10.1134/S107042720803021X

ISSN 1070-4272, Russian Journal of Applied Chemistry, 2008, Vol. 81, No. 3, pp. 452 454. Pleiades Publishing, Ltd., 2008.
Original Russian Text A.V. Babakhanyan, M.O. Manukyan, Zh.R. Babayan, R.S. Arutyunyan, 2008, published in Zhurnal Prikladnoi Khimii, 2008,
Vol. 81, No. 3, pp. 467 469.
ORGANIC SYNTHESIS
AND INDUSTRIAL ORGANIC CHEMISTRY
Antimicrobial Surfactants Based on
N,N -(5-Oxanona-2,7-diyne-1,9-diyl)bis[(alkoxycarbonylmethyl)-
dimethylammonium] Chlorides
A. V. Babakhanyan, M. O. Manukyan, Zh. R. Babayan, and R. S. Arutyunyan
Institute of Organic Chemistry, National Academy of Sciences of the Republic of Armenia, Yerevan, Armenia
Abovyan Armenian State Pedagogical University, Yerevan, Armenia
Yerevan State University, Yerevan, Armenia
Received May 15, 2007
Abstract A series of quaternary bisammonium salts containing the common 5-oxanonane-2,7-diyne-1,9-diyl
fragment and different alkoxycarbonylmethyl groups was synthesized. The surfactant properties and anti-
microbial activity of these compounds were studied.
DOI: 10.1134/S107042720803021X
Many practically important properties of surface-
active quaternary bisammonium salts depend on the
structure of the common group binding the terminal
alkylammonium groups. Among these compounds,
functionally substituted derivatives of mono- and
bisammonium salts containing unsaturated bonds are
of particular interest [1 3].
where R = C H (I), C H (II), C H (III), and
4 9 8 17 10 21
12 25
C H (IV).
Both the critical micelle concentration (CMC) of
quaternary ammonium salts (QAS) and the solution|air
interface characteristics of their aqueous solutions
were determined from the surface tension isotherms
obtained at T = 303 0.1 K by the technique reported
in [4].
Taking into account that ammonium salts with the
allyl and propargyl groups exhibit distinct anti-
microbial activity, in this study we synthesized bis-
ammonium salts containing, along with the alkoxy-
carbonylmethyl radicals ensuring surface activity, the
common 5-oxononane-2,7-diyne-1,9-diyl group (see
table).
These experiments showed that the QASs under
consideration are micelle-forming surfactants. As
the alkyl radicals in QAS molecules become longer,
both the critical micelle concentration and the surface
tension decrease, whereas the surface activity G in-
creases. As expected, the dependence of CMC on the
number n of carbon atoms in the alkyl radicals is
described by the well-known equation
These salts were prepared in high yields by the
following reactions:
HOCH C CH
HC CCH2Br +
NaOH
lnCMC = A
Bn,
2
where A and B are constants. These constants were
determined graphically from the equation logCMC =
f(n). Their values were found to be 2.7 and 0.16,
respectively.
HC CCH2OCH2C CH
FeCl , dioxane
(CH ) NH, CH O
3
3 2
2
The surface activity of the compounds under con-
sideration G was determined by the equation
(CH3)2 NCH2 C CCH2OCH2C CCH2N(CH3)2
Ethanol
ROCOCH Cl
2
G = (
CMC)/CMC,
Cl
Cl
0
+
+
(CH ) NCH2 C CCH2 OCH C CCH N(CH3 )2
,
3 2
2
2
where
is the surface tension of water, and
surface tension of aqueous QAS at CMC.
,
CMC
0
CH2 COOR
CH2 COOR
I IV
452

ANTIMICROBIAL SURFACTANTS
453
Characteristics of N,N -(5-oxanonane-2,7-diyne-1,9-diyl)bis[(alkoxycarbonylmethyl)dimethylammonium] chlorides I IV
(the salts are hygroscopic) and their antimicrobial activity*
Found/Calculated, %
Cl
Concen- tdeath, min
tration,
Com-
pound
Yield,
%
CMC
R
Rf
Formula
G
h
104, M
CMC
N
%
M1 M2
I
C4H9
96.7 0.43 5.1/5.5 14.35/13.95 C24H42Cl2N2O5
0.5 4.15/4.5 11.05/11.43 C32H58Cl2N2O5
8.91
4.47
65
54
6.9
0
2
1
10
30
5
25
II
C8H17 98
38.4 0.3
1
0.5
0.1
5
10
30
5
5
25
III
IV
C10H21 98.5 0.4 3.95/4.14 10.75/10.49 C36H66Cl2N2O5 2.29
C12H25 96.5 0.56 3.79/3.82 9.55/9.69 C40H74Cl2N2O5 2.10
47 105.6 0.8
44 129.4 0.9
0.05
0.025
5
25
5
20
0.1
0.05
0.025 >30
10
20
5
15
30
1
* (CMC) Critical micelle concentration; (
) surface tension at CMC, mN m ; (h) froth stability; (G) surface activity,
CMC
2
1
N m kmol ; (t
) time of death of microorganisms, where (M ) Escherichia coli (strain 1257), (M ) Staphylococcus aureus
death
1
2
(strain 906).
We found that variation of G values in the series
of QASs under considerations deviates from the
Duclot Traube rule, which is typical of colloidal
surfactants [5].
QAS purity was tested by thin-layer chromatography
with Silufol UV-254 plates using n-butanol ethanol
water acidic acid mixture (10 : 7 : 6 : 4) as solvent
and iodine vapor as developer.
One of practically important characteristics of sur-
factants is their froth stability [5]. The froth-forming
ability of aqueous QASs was determined as the ratio
of the initial froth column height to that after settling
for 5 min [6]. We found that the froth stability in-
creases with increasing length of radicals R. All QASs
under consideration were found to be efficient froth-
forming aqents.
Quaternary ammonium salts I IV. A mixture of
1,9-dimethylamino-5-oxanonane-2,7-diyne (0.01 mol)
and appropriate alkyl monochloroacetate in absolute
ethanol (5 ml) was kept at room temperature for
5 days. The resulting salt was washed with absolute
diethyl ether and dried in a desiccator over CaCl .
2
The IR spectrum of the final compound contains the
1
following absorption bands, , cm : 1075, 1230,
The antimicrobial activity of QASs I IV was de-
termined by a technique based on disinfection of
cambric test-objects sown with standard strains of
Staphylococcus aureus (strain 906) and Escherichia
1725 (COO), 2240 ( C C ).
1
, mN m
9
coli (strain 1257) containing 2 10 microbial cells
in 1 ml at an exposure time of 5 30 min and solution
temperature of 20 C [7].
Our results show that 0.025 1% aqueous solutions
of the synthesized QASs exhibit bactericidal effect
with respect to the above-noted strains, and this effect
is dependent on the length of hydrophobic radical R.
The maximal bactericidal effect was shown by QAS
III (R = C H ) whose 0.05% aqueous solution elim-
10 21
inates Escherichia coli and Staphylococcus aureus
within 5 min.
c
105, M
EXPERIMENTAL
Fig. 1. Surface tension
in the systems QAS H O at
2
The IR spectra of QASs were recorded on a Spec-
ord IR-75 spectrometer (mulls in mineral oil). The
T = 303 K. (c) QAS concentration. (1) C , (2) C and
8
10
(3) C
.
12
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 81 No. 3 2008

454
BABAKHANYAN et al.
2. Babakhanyan, A.V., Babayan, Zh.R., and Ako-
CONCLUSIONS
pyan, G.S., Biol. Zh. Arm., 1990, vol. 43, no. 2,
pp. 150 152.
(1) Quaternary ammonium salts containing the
common 5-oxanonane-2,7-diyne-1,9-diyl fragment
and different alkoxycarbonylmethyl groups ehhibit
bactericidal effect. Their antimicrobial activity de-
pends on the length of the hydrophobic radical.
3. Ovakimyan, S.A., Babakhanyan, A.V., and Arutyu-
nyan, R.S., Khim. Zh. Arm., 2002, vol. 55, nos. 1 2,
pp. 85 91.
4. Poverkhnostno-aktivnye veshchestva: Spravochnik
(Surfactants: Handbook), Abramzon, A.A. and Gae-
voi, G.M., Eds., Leningrad: Khimiya, 1979.
5. Praktikum po kolloidnoi khimii (Practical Course of
Colloid Chemistry), Neiman, R.E., Ed., Moscow: Vys-
shaya Shkola, 1972.
(2) With an increase in the length of the alkyl
radicals in QAS molecules, both the critical micelle
concentration and the surface tension decrease, where-
as the surface activity increases. The strongest bac-
tericidal effect is exhibited by N,N -(5-oxanonane-
2,7-diyne-1,9-diyl)bis[(decyloxycarbonylmethyl)di-
methylammonium] chloride.
6. Abramzon, A.A., Poverkhnostno-aktivnye veshchestva
(Surfactants), Leningrad: Khimiya, 1981.
7. Lyarskii, P.P. and Sokolova, N.F., Problema dezinfek-
tsii i sterilizatsii: Sbornik nauchnykh trudov VNII
dezinfektsii i sterilizatsii (Problems of Disinfection and
Sterilization: Coll. of Papers of the All-Union Research
Inst. of Disinfection and Sterilization), Moscow, 1971,
issue 2, vol. 2, pp. 186 199.
REFERENCES
1. Babakhanyan, A.V., Kauas, A., and Arutyunyan, R.S.,
Arm. Khim. Zh., 1991, vol. 44, nos. 9 10, pp. 544 547.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 81 No. 3 2008