Sodium octanol

The by-product of this process, pelargonic acid [112-05-0] is also an item of commerce. The usual source of sebacic acid [111-20-6] for nylon-6,10 [9008-66-6] is also from a natural product, ticinoleic acid [141-22-0] (12-hydroxyoleic acid), isolated from castor oil [8001-79-4]. The acid reacts with excess sodium or potassium hydroxide at high temperatures (250—275°C) to produce sebacic acid and 2-octanol [123-96-6] (166) by cleavage at the 9,10-unsaturated position. The manufacture of dodecanedioic acid [693-23-2] for nylon-6,12 begins with the catalytic trimerization of butadiene to make cyclododecatriene [4904-61-4] followed by reduction to cyclododecane [294-62-2] (see Butadiene). The cyclododecane is oxidatively cleaved to dodecanedioic acid in a process similar to that used in adipic acid production. 

Alkali Fusion. Tha alkaU fusion of castor oil using sodium or potassium hydroxide in the presence of catalysts to spHt the ricinoleate molecule, results in two different products depending on reaction conditions (37,38). At lower (180—200°C) reaction temperatures using one mole of alkah, methylhexyl ketone and 10-hydroxydecanoic acid are prepared. The 10-hydroxydecanoic acid is formed in good yield when either castor oil or methyl ricinoleate [141-24-2] is fused in the presence of a high boiling unhindered primary or secondary alcohol such as 1- or 2-octanol. An increase to two moles of alkali/mole ricinoleate and a temperature of 250—275°C produces capryl alcohol [123-96-6] CgH gO, and sebacic acid [111-20-6] C QH gO, (39—41). Sebacic acid is used in the manufacture of nylon-6,10. 

A solution of 50 g of 1 -azabicyclo[2.2.2] -3-octanol hydrochloride in 30 cc water was made alkaline with 30 g of potassium hydroxide. After the alkali was dissolved 35 g of granular potassium carbonate were added. The free basic alcohol was then extracted from the viscous mixture by shaking with four portions of boiling benzene (300 cc in each portion). The benzene extracts were decanted and filtered over anhydrous sodium sulfate, to remove any suspended alkali. The combined benzene solutions were concentrated in vacuo. The residue was recrystallized from benzene and identified as 1 -azabicyclo[2.2.2] -3-octanol, MP 221°-223°C. The product can also be purified by recrystallization from acetone, or by sublimation in vacuo (120°C/20 mm Hg). The alcohol was reacted with acetic anhydride to give the product ace-clidine. 

The hydrogeh atom bound to the amide nitrogen in 15 is rather acidic and it can be easily removed as a proton in the presence of some competent base. Naturally, such an event would afford a delocalized anion, a nucleophilic species, which could attack the proximal epoxide at position 16 in an intramolecular fashion to give the desired azabicyclo[3.2.1]octanol framework. In the event, when a solution of 15 in benzene is treated with sodium hydride at 100 °C, the processes just outlined do in fact take place and intermediate 14 is obtained after hydrolytic cleavage of the trifluoroacetyl group with potassium hydroxide. The formation of azabi-cyclo[3.2.1]octanol 14 in an overall yield of 43% from enone 16 underscores the efficiency of Overman s route to this heavily functionalized bicycle. 

The influence of the presence of alcohols on the CMC is also well known. In 1943 Miles and Shedlovsky [117] studied the effect of dodecanol on the surface tension of solutions of sodium dodecyl sulfate detecting a significant decrease of the surface tension and a displacement of the CMC toward lower surfactant concentrations. Schwuger studied the influence of different alcohols, such as hexanol, octanol, and decanol, on the surface tension of sodium hexa-decyl sulfate [118]. The effect of dodecyl alcohol on the surface tension, CMC, and adsorption behavior of sodium dodecyl sulfate was studied in detail by Batina et al. [119]. 

Surfactants employed for w/o-ME formation, listed in Table 1, are more lipophilic than those employed in aqueous systems, e.g., for micelles or oil-in-water emulsions, having a hydrophilic-lipophilic balance (HLB) value of around 8-11 [4-40]. The most commonly employed surfactant for w/o-ME formation is Aerosol-OT, or AOT [sodium bis(2-ethylhexyl) sulfosuccinate], containing an anionic sulfonate headgroup and two hydrocarbon tails. Common cationic surfactants, such as cetyl trimethyl ammonium bromide (CTAB) and trioctylmethyl ammonium bromide (TOMAC), have also fulfilled this purpose however, cosurfactants (e.g., fatty alcohols, such as 1-butanol or 1-octanol) must be added for a monophasic w/o-ME (Winsor IV) system to occur. Nonionic and mixed ionic-nonionic surfactant systems have received a great deal of attention recently because they are more biocompatible and they promote less inactivation of biomolecules compared to ionic surfactants. Surfactants with two or more hydrophobic tail groups of different lengths frequently form w/o-MEs more readily than one-tailed surfactants without the requirement of cosurfactant, perhaps because of their wedge-shaped molecular structure [17,41]. 

FIG. 4 Electrical potential oscillation across the octanol membrane of an octanol solution containing 5mM tetrabutylammonium chloride comprising two aqueous solutions, one containing 8mM sodium dodecyl sulfate and 5M ethanol. (Ref 19.)... 

FIG. 6 Electrical potential oscillation across the octanol membrane with sodium dodecyl sulfate as surfactant (A) and between octanol and aqueous phases (B and C). All data were obtained using the inverted U-shaped cell (al) water, (a2) 8mM sodium dodecyl sulfate and 5M ethanol, (b) octanol containing 8mM tetrabutylammonium chloride, (c) Ag/AgCl electrode, (d) KCl salt bridge, and (e) saturated KCl. (Ref. 26.)... 

FIG. 9 Upper potential values, a.sds lower potential values, b.sds of the first oscillation at the interface between phases o and wl of the octanol membrane (A), interfacial potential of a two-phase octanol-water system in the absence of SDS, c.sds (B) and those in the presence of 10 mM SDS (in the case of inorganic electrolyte, 1 mM), d.sds (C)- TMACI tetramethylammonium chloride TEACI tetraethylammonium chloride TPACI tetrapropylammonium chloride TBACI tetra-butylammonium chloride AcNa sodium acetate PrNa sodium propionate, BuNa sodium n-butyrate VaNa sodium w-valerate. (Ref 27.)... 

Figure 7.7 Permeation of anionic warfarin (pH 11) through octanol-soaked (impregnated) microfilter as a function of sodium ion concentration.

Avdeef, A. Takacs-Novak, K. Box, K. J., pH-metric logP. 6. Effects of sodium, potassium, and N-CH3-D-glucamine on the octanol-water partitioning with prostaglandins El and E2, J. Pharm. Sci. 84, 523-529 (1995). 

Cools, A. A. Janssen, L. H. M., Influence of sodium ion-pair formation on transport kinetics of warfarin through octanol-impregnated membranes, J. Pharm. Pharmacol. 35, 689-691 (1983). 

The (7 )-()-2-bromooctane reacts with sodium hydroxide to afford only (5)-(+)-2-octanol. 

Research has also been conducted in which steryl phosphonic acid (SPA) was examined in place of benzyl arsonic acid (BAA), which was used in an operating plant in China [5], In this study, several collectors were examined, including sodium laurate, sodium dodecyl sulphate, amino acids, diphosphonic acid (SPA). It was discovered that SPA was the most effective and that aliphatic alcohol (i.e. octanol) was required to maintain the effectiveness of SPA. The use of emulsifier in the mixture was required to provide a suitable emulsion of the composite collector. 

Linear alkylbenzene sulfonate (LAS) and the sodium salt Na-LAS (P550), alkyl sulfate (AS) Ci2-Ci4, alkylether sulfate (AES), alcohol ethoxylate (AE) 1012/60, methylester sulfonate (MES) Ci6-Ci8, Na-lauryl sulfate, 1-octane sulfate Na, 1-decan sulfonate Na, 1-hexadecan sulfonate Na, Laurie alcohol, 1-octanol (A. Caprilico), 1-nonanol, n-decyl-alcohol, 1-undecanol, 1-tridecanol, miristic alcohol (1-tetradecanol), 1-pentadecanol, cetyl-alcohol (1-hexadecanol), 1-hep-tadecanol, estearil alcohol (1-octadecanol), nonadecanol, araquidil alcohol (1-ecosanol), heneicosanol, behenil alcohol (1-docosanol),... 

Addition of the dicarboxylic acid to a water/ detergent combination prevents (B) the gelling caused by a model dirt (octanol, CgOH) below the cmc (A). A The model dirt octanol (CgOH) forms a liquid crystalline phase with water and sodium octanoiate (CgOOH at pH 10) in area 3 and 4 Partial substitution of the sodium octanoate with the diacid soap (pH 10) leads to an increase of solubilization of the octanol (B). 1 aqueous... 

The host liquid crystalline matrix was composed of water, sodium octanoate and octanol. This combination was chosen in order to create an environment as closely matching the specific requirements of the problem as possible. In the first instance, the surfactant was Identical to the one used for the solubilization determinations (12) and the alcohol was present in order to resemble actual laundering conditions with "oily dirt" molecules present (12). 

In recent studies, Friberg and co-workers (J, 2) showed that the 21 carbon dicarboxylic acid 5(6)-carboxyl-4-hexyl-2-cyclohexene-1-yl octanoic acid (C21-DA, see Figure 1) exhibited hydrotropic or solubilizing properties in the multicomponent system(s) sodium octanoate (decanoate)/n-octanol/C2i-DA aqueous disodium salt solutions. Hydrotropic action was observed in dilute solutions even at concentrations below the critical micelle concentration (CMC) of the alkanoate. Such action was also observed in concentrates containing pure nonionic and anionic surfactants and C21-DA salt. The function of the hydrotrope was to retard formation of a more ordered structure or mesophase (liquid crystalline phase). 

Kralj, F. and Sincic, D. Mutual solubilities of phenol, salicyaldehyde, phenol-salicyaldehyde mixture, and water with and without the presence of sodium chloride and sodium chloride plus sodium sulfate, J. Chem. Eng. Data, 25 (4) 335-338,1980. Kramer, C.R. and Henze, U. Partitioning properties of benzene derivatives. 1. Temperature dependence of the partitioning of monosubstituted benzenes and nitrobenzenes in the n-octanol/water system, Z. Phys. Chem., 271(3) 503-513,1990. Krasnoshchekova, R.Ya. and Gubergrits, M. Solubility of paraffin hydrocarbons in fresh and salt water, Neftekhlmlya, 13(6) 885-888, 1973. 

Figure 4. Octanol/water distribution of sodium salicylate over a range of pH values.

In collaboration with Jon Belisle, octanol pKa values were measured for a series of benzoic acids and phenols. A coupled electrode calibrated in aqueous buffers was used. The haIf-neutralization potential was measured since the Renderson-Hasselbalch equations would not apply. The titrant was 0.1 sodium hydroxide in isopropanol methanol 4 1. The titrant was only 6% of the total volume at half-neutralization, so the medium was essentially octanol-like. The results are listed in Table I and some benzoic acid values are plotted in Figure 6. 

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