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Dioctyl Sodium Sulfosuccinate
DIOCTYL SODIUM SULFOSUCCINATE Satinder Ahuja and Jerold Cohen 1. Description
1 . 1 Name, Formula, Molecular Weight, Elemental Composition 2. Physical Properties 2.3 Mass Spectrometry 2.8 Solubilization 2.9 Effect On Surface Tension Of Liquids 6. Methods of Analysis 6.1 Titrimetric Analysis 6 . 2 Colorimetric Analysis 6.4 Turbidimetric Analysis 6.7 Polarographic Analysis 6.8 Miscellaneous References
ANALYTICAL PROFILES OF DRUG SUBSTANCES VOLUME 12
713
714 7 14 714 714 717 718 718 718 718 718 719 719 719
Copyright by the American Pharmaceutlaal Asswiatmn ISBN 0-12-260812-7
SATINDER AHUJA AND JEROLD COHEN
714
The following supplement contains updated information pertaining to the analytical chemistry of dioctyl sodium sulfosuccinate. A literature survey was conducted and is complete up to June, 1982. The numbering system for topics discussed is the same as that in the original profile (Volume 2, pp.199-219). 1.
DESCRIPTION
1.1 Name, Formula, Molecular Weight, Elemental Composition Dioctyl sodium sulfosuccinate is known as docusate sodium (1). It is also known as sulfobutanedioic acid 1 , 4 bis(2-ethylhexyl) ester sodium salt, sulfosuccinic acid 1 , 4 bis(2-ethylhexyl) ester S-sodium salt, Comfolax, Molcer, Soliwax and Valsol OT ( 2 ) . It has a molecular weight of 444.56 (C20H37NaO7S).
C2Il5 I COOCH2CH(CH2) 3CH3
I
CH2 I CH-SO3Na
I
COOCH2CH(CH2) 3CH3 I C2H5
2.
PHYSICAL PROPERTIES
2.3
Mass Spectrometry A chemical ionization mass spectrum (Kratos MS 25 with isobutane as reagent gas) was run on the acid form of dioctyl sodium sulfosuccinate prepared by acidification of a methanolic solution with HC1 gas ( 3 ) . The interpretation of major fragmentation ions (Figure 1) is as follows ( 4 ) :
715
DIOCTYL SODIUM SULFOSUCCINATE
157
113
- r H @ ‘ 0
m/z 4 2 3
HO-!
It0
1~
0:
t
CH3
1-
2
~
I
L99
229 129
5
S02H
‘ZH5
l@
O/\I/\/\CH3
m/z 358
3-0
HO
H
c. 0
-
‘ZH5
1
211
-OH
‘ZH5
3
/\J/\/\CH
O
8
0
W
‘ZH5
‘
H
3
m/z 341
716
SATINDER AHUJA AND JEROLD COHEN
100
-
w m -
m 0 0 -
w -
4 0 -
5 0 -
I
Figure 1.
Chemical Ionization Mass Spectrum of the Acid Form of Dioctyl Sodium Sulfosuccinate. (Drawn to show major fragments)
DIOCTYL SODIUM SULFOSUCCINATE
717
2.8
Solubilization The critical micelle concentration value of 3.0 nmoles/l was determined by plotting desorption potential (d.c. polarography without electrolyte) vs. log concentration (5). The solution states of dioctyl sodium sulfosuccinate were examined by lH NMR (6). Two hydrocarbon chains of its molecules, in the monomeric state, aggregate with each other in water. Addition of aqueous sodium chloride solution to the Aerosol OT-n-octane system showed a peak corresponding to micellarsolubilized water and another peak corresponding to separated water (7). Systems containing aluminum chloride differed from those containing mono or divalent electrolytes. In 0.27M AlC13, the two peaks merged into a single peak, indicating breakdown of the micellar system. The magnitude of cation effect was in the order Na
SATINDER AHUJA AND JEROLD COHEN
718
of the solubilizates as illustrated by the larger equilibrium constants for the binding of 3-H and 5-H of imidazole than for the 2-H. 2.9
Effect On Surface Tension Of Liquids A method to determine the surface compressional modulus by the Fourier transformation of the surface tension relaxation function has been reported. The method can provide rapid measurements for very dilute solutions, in the low frequency range (12).
6.
METHODS OF ANALYSIS
6.1 Titrimetric Analysis The two-phase mixed indicator titration method for the determination of anionic surfactants was extended to include dioctyl sodium sulfosuccinate by using 2:3 (v/v) chloroform: 1-nitropropane as the organic phase and a multiple extraction-titration technique (13).
DSS can also be determined by extractive titration with carbethopendecinium bromide (14). 6.2
Colorimetric Analysis Several methods have been proposed for the analysis of anionic surfactants in trace quantities in water: extraction into toluene from aqueous solution with ethyl violet and spectrophotometric determination at 615 nm (15); extraction into benzene from aqueous solution with bis[2-(2-pyridylazo)5-diethylamino phenolato] cobalt (111) ion as the counter-ion and spectrophotometric determination at 550 nm (16); extraction into chlorobenzene from aqueous solution with 1-(4-nitrobenzyl)-4-(4-diethylamino pheny1azo)-pyridinium bromide and spectrophotometric determination at 573 nm (17); extraction into benzene from aqueous solution with bis[2-(5-chloro-2pyridylazo)-5-diethylamino phenolato] cobalt (111) chloride and spectrophotometric determination at 560 nm (18). 6.4 Turbidimetric Analysis Dioctyl sodium sulfosuccinate was determined after formation and stabilization of a dispersion with barium sulfate in water-alcohol mixture and measurement of turbidity at 650 nm (19). The limit of detection was 100-200 pg/g and reproducibility was %5%.
DIOCTYL SODlUM SULFOSUCCINATE
719
6.7
Polarographic Analysis Dioctyl sodium sulfosuccinate was determined by polarographic desorption potential measurement ( 2 0 ) . It showed a well defined adsorption-desorption wave and a linear relationship was observed between the desorption potential and the logarithm of surfactant concentration. The determination was limited by the critical micelle concentration (CMC), as the desorption potential remained constant above the CMC of the surfactant. The method can be applied for the determination of a few ppm of the surfactant. 6.8
Miscellaneous A nitrogen blowing technique allowed quantitative recovery of surfactants present in solution and can be applied to analysis of surface waters and waste waters (21). Dioctyl sodium sulfosuccinate can be used to form ion pairs with organic bases which are extractable with immiscible organic solvents. This technique has been used for identification and assay of the organic bases by ultraviolet absorption spectrophotometry in dosage forms and biological fluids ( 2 2 ) . REFERENCES
1. "The United States Pharmacopeia - National Formulary" XX/XV Ed., Mack Publishing Co., Easton, Pa. 1 9 8 0 , p. 261. 2. "Merck Index", 9th Ed. , Merck and Go. , Inc. , Rahway, New Jersey, 1 9 7 6 , p. 438-439. 3 . S. Ahiija and G. Thompson, Ciba-Geigy Corp. Suffern, N.Y., l'eKSOna1 Communication, 1 9 8 2 . 4 . M. Stogniew and R. Schiesswohl, Ciba-Geigy Corp. Suffern, N . Y . , Personal Communication, 1 9 8 3 . 5. N. Shinozuka, H. Suzuki and S. Hayano, Kolloid-Z.Z. Polym., 248 ( 1 & 2 ) , 959 ( 1 9 7 1 ) . 6 . M. Ueno, H. Kishimoto and Y. Kyogoku, Chem. Lett., # 6 , 599-602
7.
8.
9. 10.
(1977). Frank, Y.H. Shaw and N.C. Li, J. Phys. Chem., 77 ( Z ) , 238 ( 1 9 7 3 ) . MTUeno, H. Kishimoto and Y. Kyogoku, J. Colloid Interface Sci., 63 (l), 113 ( 1 9 7 8 ) . M. Ueno, H. Kishimoto and Y. Kyogoku, Bull. Chem. SOC. 3 ( 7 ) , 1776 (1976). A . N . Maitra and H.F. Eicke, J. Phys. Chem. 8 5 ( 1 8 ) , 2687 ( 1 9 8 1 ) . S.G.
*.,
SATINDER AHUJA AND JEROLD COHEN
720
13.
A. El Seoud and J. H. Fendler, J. Chem. SOC. Farraday Trans. 1, 7 1 ( 3 ) , 452 ( 1 9 7 5 ) . G. Loglio, U. Tesei a n d R. Cini., Ber. Bunsenges. Phys. Chem., 81 (11), 1154 ( 1 9 7 7 ) . Z. Li and M. J. Rosen, Anal. Chem., 53 (9), 1 5 1 6
14.
J . Blazek, A. Dymes and M. Travnickova, Cesk. Farm.
15.
STMotomizu, S. Fujiwara, A. Fujiwara and K. Anal. Chem., 54 ( 3 ) , 392 ( 1 9 8 2 ) . S. Taguchi and K. Goto, Talanta, 27 ( 3 ) , 289 K. Higuchi, Y. Shimoishi, H. Miyata, K. Toei T. Hayami, Analyst, 1 0 5 , 768 ( 1 9 8 0 ) . S. Taguchi, I. K a s a h a x Y. Fukushima and K. Talanta, 28 ( 8 ) , 616 ( 1 9 8 1 ) . S.M.F. Tavernier and R. Gijbels, Talanta, 28
11. 12.
16. 17. 18.
19. 20. 21.
22.
(1981).
27 ( 9 ) , 379 ( 1 9 7 8 ) .
221 (1981).
Toei, (1980)
and
Goto, (4),
N. Shinozuka, H. Suzuki and S. Hayano, Bunseki Kagaku, 2 ( 4 ) , 517 ( 1 9 7 2 ) . C. Divo, S. Gafa, T. La Noce, A. Paris, C. Ruff0 and M. Sanna, Riv. Ital. Sostanze Grasse, 57 ( 7 ) , 329 ( 1 9 8 0 ) .
F. Pellerin, D. Mancheron and D. Demay, Ann. Pharm. -Fr. 30 ( 6 ) , 429 ( 1 9 7 2 ) .
1 . 1 Name, Formula, Molecular Weight, Elemental Composition 2. Physical Properties 2.3 Mass Spectrometry 2.8 Solubilization 2.9 Effect On Surface Tension Of Liquids 6. Methods of Analysis 6.1 Titrimetric Analysis 6 . 2 Colorimetric Analysis 6.4 Turbidimetric Analysis 6.7 Polarographic Analysis 6.8 Miscellaneous References
ANALYTICAL PROFILES OF DRUG SUBSTANCES VOLUME 12
713
714 7 14 714 714 717 718 718 718 718 718 719 719 719
Copyright by the American Pharmaceutlaal Asswiatmn ISBN 0-12-260812-7
SATINDER AHUJA AND JEROLD COHEN
714
The following supplement contains updated information pertaining to the analytical chemistry of dioctyl sodium sulfosuccinate. A literature survey was conducted and is complete up to June, 1982. The numbering system for topics discussed is the same as that in the original profile (Volume 2, pp.199-219). 1.
DESCRIPTION
1.1 Name, Formula, Molecular Weight, Elemental Composition Dioctyl sodium sulfosuccinate is known as docusate sodium (1). It is also known as sulfobutanedioic acid 1 , 4 bis(2-ethylhexyl) ester sodium salt, sulfosuccinic acid 1 , 4 bis(2-ethylhexyl) ester S-sodium salt, Comfolax, Molcer, Soliwax and Valsol OT ( 2 ) . It has a molecular weight of 444.56 (C20H37NaO7S).
C2Il5 I COOCH2CH(CH2) 3CH3
I
CH2 I CH-SO3Na
I
COOCH2CH(CH2) 3CH3 I C2H5
2.
PHYSICAL PROPERTIES
2.3
Mass Spectrometry A chemical ionization mass spectrum (Kratos MS 25 with isobutane as reagent gas) was run on the acid form of dioctyl sodium sulfosuccinate prepared by acidification of a methanolic solution with HC1 gas ( 3 ) . The interpretation of major fragmentation ions (Figure 1) is as follows ( 4 ) :
715
DIOCTYL SODIUM SULFOSUCCINATE
157
113
- r H @ ‘ 0
m/z 4 2 3
HO-!
It0
1~
0:
t
CH3
1-
2
~
I
L99
229 129
5
S02H
‘ZH5
l@
O/\I/\/\CH3
m/z 358
3-0
HO
H
c. 0
-
‘ZH5
1
211
-OH
‘ZH5
3
/\J/\/\CH
O
8
0
W
‘ZH5
‘
H
3
m/z 341
716
SATINDER AHUJA AND JEROLD COHEN
100
-
w m -
m 0 0 -
w -
4 0 -
5 0 -
I
Figure 1.
Chemical Ionization Mass Spectrum of the Acid Form of Dioctyl Sodium Sulfosuccinate. (Drawn to show major fragments)
DIOCTYL SODIUM SULFOSUCCINATE
717
2.8
Solubilization The critical micelle concentration value of 3.0 nmoles/l was determined by plotting desorption potential (d.c. polarography without electrolyte) vs. log concentration (5). The solution states of dioctyl sodium sulfosuccinate were examined by lH NMR (6). Two hydrocarbon chains of its molecules, in the monomeric state, aggregate with each other in water. Addition of aqueous sodium chloride solution to the Aerosol OT-n-octane system showed a peak corresponding to micellarsolubilized water and another peak corresponding to separated water (7). Systems containing aluminum chloride differed from those containing mono or divalent electrolytes. In 0.27M AlC13, the two peaks merged into a single peak, indicating breakdown of the micellar system. The magnitude of cation effect was in the order Na
SATINDER AHUJA AND JEROLD COHEN
718
of the solubilizates as illustrated by the larger equilibrium constants for the binding of 3-H and 5-H of imidazole than for the 2-H. 2.9
Effect On Surface Tension Of Liquids A method to determine the surface compressional modulus by the Fourier transformation of the surface tension relaxation function has been reported. The method can provide rapid measurements for very dilute solutions, in the low frequency range (12).
6.
METHODS OF ANALYSIS
6.1 Titrimetric Analysis The two-phase mixed indicator titration method for the determination of anionic surfactants was extended to include dioctyl sodium sulfosuccinate by using 2:3 (v/v) chloroform: 1-nitropropane as the organic phase and a multiple extraction-titration technique (13).
DSS can also be determined by extractive titration with carbethopendecinium bromide (14). 6.2
Colorimetric Analysis Several methods have been proposed for the analysis of anionic surfactants in trace quantities in water: extraction into toluene from aqueous solution with ethyl violet and spectrophotometric determination at 615 nm (15); extraction into benzene from aqueous solution with bis[2-(2-pyridylazo)5-diethylamino phenolato] cobalt (111) ion as the counter-ion and spectrophotometric determination at 550 nm (16); extraction into chlorobenzene from aqueous solution with 1-(4-nitrobenzyl)-4-(4-diethylamino pheny1azo)-pyridinium bromide and spectrophotometric determination at 573 nm (17); extraction into benzene from aqueous solution with bis[2-(5-chloro-2pyridylazo)-5-diethylamino phenolato] cobalt (111) chloride and spectrophotometric determination at 560 nm (18). 6.4 Turbidimetric Analysis Dioctyl sodium sulfosuccinate was determined after formation and stabilization of a dispersion with barium sulfate in water-alcohol mixture and measurement of turbidity at 650 nm (19). The limit of detection was 100-200 pg/g and reproducibility was %5%.
DIOCTYL SODlUM SULFOSUCCINATE
719
6.7
Polarographic Analysis Dioctyl sodium sulfosuccinate was determined by polarographic desorption potential measurement ( 2 0 ) . It showed a well defined adsorption-desorption wave and a linear relationship was observed between the desorption potential and the logarithm of surfactant concentration. The determination was limited by the critical micelle concentration (CMC), as the desorption potential remained constant above the CMC of the surfactant. The method can be applied for the determination of a few ppm of the surfactant. 6.8
Miscellaneous A nitrogen blowing technique allowed quantitative recovery of surfactants present in solution and can be applied to analysis of surface waters and waste waters (21). Dioctyl sodium sulfosuccinate can be used to form ion pairs with organic bases which are extractable with immiscible organic solvents. This technique has been used for identification and assay of the organic bases by ultraviolet absorption spectrophotometry in dosage forms and biological fluids ( 2 2 ) . REFERENCES
1. "The United States Pharmacopeia - National Formulary" XX/XV Ed., Mack Publishing Co., Easton, Pa. 1 9 8 0 , p. 261. 2. "Merck Index", 9th Ed. , Merck and Go. , Inc. , Rahway, New Jersey, 1 9 7 6 , p. 438-439. 3 . S. Ahiija and G. Thompson, Ciba-Geigy Corp. Suffern, N.Y., l'eKSOna1 Communication, 1 9 8 2 . 4 . M. Stogniew and R. Schiesswohl, Ciba-Geigy Corp. Suffern, N . Y . , Personal Communication, 1 9 8 3 . 5. N. Shinozuka, H. Suzuki and S. Hayano, Kolloid-Z.Z. Polym., 248 ( 1 & 2 ) , 959 ( 1 9 7 1 ) . 6 . M. Ueno, H. Kishimoto and Y. Kyogoku, Chem. Lett., # 6 , 599-602
7.
8.
9. 10.
(1977). Frank, Y.H. Shaw and N.C. Li, J. Phys. Chem., 77 ( Z ) , 238 ( 1 9 7 3 ) . MTUeno, H. Kishimoto and Y. Kyogoku, J. Colloid Interface Sci., 63 (l), 113 ( 1 9 7 8 ) . M. Ueno, H. Kishimoto and Y. Kyogoku, Bull. Chem. SOC. 3 ( 7 ) , 1776 (1976). A . N . Maitra and H.F. Eicke, J. Phys. Chem. 8 5 ( 1 8 ) , 2687 ( 1 9 8 1 ) . S.G.
*.,
SATINDER AHUJA AND JEROLD COHEN
720
13.
A. El Seoud and J. H. Fendler, J. Chem. SOC. Farraday Trans. 1, 7 1 ( 3 ) , 452 ( 1 9 7 5 ) . G. Loglio, U. Tesei a n d R. Cini., Ber. Bunsenges. Phys. Chem., 81 (11), 1154 ( 1 9 7 7 ) . Z. Li and M. J. Rosen, Anal. Chem., 53 (9), 1 5 1 6
14.
J . Blazek, A. Dymes and M. Travnickova, Cesk. Farm.
15.
STMotomizu, S. Fujiwara, A. Fujiwara and K. Anal. Chem., 54 ( 3 ) , 392 ( 1 9 8 2 ) . S. Taguchi and K. Goto, Talanta, 27 ( 3 ) , 289 K. Higuchi, Y. Shimoishi, H. Miyata, K. Toei T. Hayami, Analyst, 1 0 5 , 768 ( 1 9 8 0 ) . S. Taguchi, I. K a s a h a x Y. Fukushima and K. Talanta, 28 ( 8 ) , 616 ( 1 9 8 1 ) . S.M.F. Tavernier and R. Gijbels, Talanta, 28
11. 12.
16. 17. 18.
19. 20. 21.
22.
(1981).
27 ( 9 ) , 379 ( 1 9 7 8 ) .
221 (1981).
Toei, (1980)
and
Goto, (4),
N. Shinozuka, H. Suzuki and S. Hayano, Bunseki Kagaku, 2 ( 4 ) , 517 ( 1 9 7 2 ) . C. Divo, S. Gafa, T. La Noce, A. Paris, C. Ruff0 and M. Sanna, Riv. Ital. Sostanze Grasse, 57 ( 7 ) , 329 ( 1 9 8 0 ) .
F. Pellerin, D. Mancheron and D. Demay, Ann. Pharm. -Fr. 30 ( 6 ) , 429 ( 1 9 7 2 ) .