Benzene, solubilization

Figure 8.6 shows some data measured for benzene solubilized in hexadecyl pyridinium chloride. The abscissa in the figure shows the extent of solubilization expressed as moles of solubilizate per mole of surfactant. The ordinate values show shifts in the resonance frequencies from water taken as an internal standard. Shifts of peaks arising from protons in the pyridinium ring, in benzene, and in methylene groups in the alkyl tail are shown versus the extent of solubilization. 

Matsumoto and Sherman [190] have obtained an equation which describes the behaviour of benzene/water microemulsions stabilized by Tween 20/Span 20 mixtures with particle diameters in the range 54 to 125 nm. The volume (s) of benzene solubilized in micelles of excess emulsifier is considered and the equation takes the form. 

Calculations usirig this value afford a partition coefficient for 5.2 of 96 and a micellar second-order rate constant of 0.21 M" s" . This partition coefficient is higher than the corresponding values for SDS micelles and CTAB micelles given in Table 5.2. This trend is in agreement with literature data, that indicate that Cu(DS)2 micelles are able to solubilize 1.5 times as much benzene as SDS micelles . Most likely this enhanced solubilisation is a result of the higher counterion binding of Cu(DS)2... 

The covalent character of mercury compounds and the corresponding abiUty to complex with various organic compounds explains the unusually wide solubihty characteristics. Mercury compounds are soluble in alcohols, ethyl ether, benzene, and other organic solvents. Moreover, small amounts of chemicals such as amines, ammonia (qv), and ammonium acetate can have a profound solubilizing effect (see COORDINATION COMPOUNDS). The solubihty of mercury and a wide variety of mercury salts and complexes in water and aqueous electrolyte solutions has been well outlined (5). 

Special additives are often included in a carrier formulation to provide specific properties such as foam control, stabiUty, and fiber lubrication during dyeing. Most important are the solvents used to solubilize the soHd carrier-active chemicals. These often contribute to the general carrier activity of the finished product. For example, chlorinated benzenes and aromatic esters are good solvents for biphenyls and phenylphenols. Flammable compounds (flash point below 60°C) should be avoided. 

At the end of the 1960s, Subba Rao et al. examined the influence of the interface on the CMC values [56]. They found a decrease in the CMC at the oil-water interface compared with the air-water interface. The CMC decreased by about 10% in the presence of heptane and by about 30-40% in the presence of benzene. The solubilization of the hydrocarbon in the micelle interior results in an increase in the micelle size and a slight change in the curvature of the micelle surface. The electrical potential and hence the electrical work of... 

Hexa(oligophenyl)benzenes (e. g. 31 or 33) present one possible approach to the realization of this aim. Two efficient synthetic routes have been elaborated for the preparation of hexa(terphenyl)- and hexa(quaterphenyl)benzene. The first, involving palladium-catalyzed trimerization of diarylacetylenes [54] as the key step, was demonstrated by the synthesis of a hexakis-alkylated hexa(terphenyl)benzene derivative 31 from the corresponding bis(terphenyl) acetylene (32). The peripheral tert-alkyl substituents serve to solubilize the molecule. 

The polymerization of l,4-bis(halomethyl)benzenes to PPVs in the presence of a large excess of potassium f-butoxide is referred as the Gilch route [81]. The method was first described for the synthesis of unsubstituted PPV 60, but -unfortunately - this route produces the PPV as an intractable, insoluble powder. However, the adaptation of the Gilch route to the polymerization of l,4-bis(halo-methyl)benzenes possessing solubilizing side groups gives access to soluble PPV materials. 

For the synthesis of the target structures, it is absolutely necessary to introduce solubilizing substituents in the positions peripheral to the benzoyl substituents. The primary coupling product, 117, a poly(2,5-dibenzoyl-l,4-phenyl-ene) derivative - a poly(para-phenylene) with two benzoyl substituents in each structural unit - is, as expected, very poorly soluble. Highly substituted monomers (2,5-dibromo-l,4-bis(3,4-dihexyloxy-benzoyl)benzene), containing four solubilizing alkoxy groups per monomer unit, allow the synthesis of polymeric materials with M of about 12,000 and M, of about 22,000 [139]. 

For instance, it has been observed that the addition of additives such as cyclohexane, benzene, and nitrobenzene to water/AOT/isoctane systems considerably increases the maximum amount of solubilized water [48]. The same effect has been observed in the presence of finite amounts of cytochrome c [49]. 

Betzemeier et al. (1998) have used f-BuOOH, in the presence of a Pd(II) catalyst bearing perfluorinated ligands using a biphasic system of benzene and bromo perfluoro octane to convert a variety of olefins, such as styrene, p-substituted styrenes, vinyl naphthalene, 1-decene etc. to the corresponding ketone via a Wacker type process. Xia and Fell (1997) have used the Li salt of triphenylphosphine monosulphonic acid, which can be solubilized with methanol. A hydroformylation reaction is conducted and catalyst recovery is facilitated by removal of methanol when filtration or extraction with water can be practised. The aqueous solution can be evaporated and the solid salt can be dissolved in methanol and recycled. 

In some runs, a preliminary benzene wash was necessary to make the MTC sufficiently hydrophilic to allow removal of the ZnCl2 The amount of solubilized material from the wash was added to the benzene Soxhlet yield, to give the total benzene solubility. As seen in Figure 8, relative to water-washed MTC, benzene-washed MTC has higher benzene solubility with the same... 

Extractive solvents reduce the solubilization donor solvents increase it, but involve incorporation. A relation between benzene and pyridine solubility is dependent on wash conditions. Finally, oxygen recovery and corrected solubility are related, the relationship varying with the solvent used. 

Apart from analytical applications, reports of the use of crowns in synthetic organic chemistry have been quite common. Typically, the solubilization of an inorganic reagent (such as potassium permanganate) or the production of a free counter ion (such as the fluoride ion) in an organic solvent such as benzene has formed the basis for many of these reports. 

Using dicyclohexyl-18-crown-6 it is possible to dissolve potassium hydroxide in benzene at a concentration which exceeds 0.15 mol dm-3 (Pedersen, 1967). The free OH- has been shown to be an excellent reagent for ester hydrolysis under such conditions. The related solubilization of potassium permanganate in benzene, to yield purple benzene , enables oxidations to be performed in this solvent (Hiraoka, 1982). Thus, it is possible to oxidize a range of alkenes, alcohols, aldehydes, and alkylbenzenes under mild conditions using this solubilized reagent. For example, purple benzene will oxidize many alkenes or alcohols virtually instantaneously at room temperature to yield the corresponding carboxylic acids in near-quantitative yields (Sam Simmons, 1972). 

Liotta and Grisdale (1975) have reported on the relative nucleophilicities of anions whose potassium salts were solubilized into acetonitrile by 18-crown-6 [3]. The results (Table 28) show the sequence Nj > OAc- > CN- > F- > Cl-x Br- > I- > SCN-, which is very different from the reactivity scale in water CN- > I- >SCN- > Nj > Br- > Cl- > OAc- > F-. Furthermore, the relative nucleophilicities in acetonitrile vary only by a factor of 30, whereas in water they differ by as much as a factor of 1000. The fact that gas-phase nucleophilicities also span a narrow range led the authors to conclude that anion solvation is much less important in acetonitrile than in water. The values recently reported by Lemmetyinen et al. (1978) for the relative nucleophilicities of anions towards methyl methanesulfonate in benzene show the same sequence as in protic solvents, however. The authors offered no explanation for this peculiar behaviour. 

The solubilization of sodium or potassium carbonate into apolar solvents such as benzene or acetonitrile with the aid of 18-crown-6 [3] generates a powerful base that has been used for a variety of preparative transformations (Fedorynski et al., 1978). Mechanistic studies have not been reported thus far. 

Crown ethers have been used successfully as phase-transfer catalysts for liquid-liquid and liquid-solid oxidation reactions. Sam and Simmons (1972) observed that potassium permanganate can be solubilized in benzene by dicyclohexyl-18-crown-6 to yield concentrations as high as 0.06 M. From... 

Valentine and Curtis (1975) extended the synthetic utility of potassium peroxide by reporting the successful solubilization of K02 in dry dimethyl sulfoxide using dicyclohexyl- 18-crown-6 ([20] + [21]). Corey et al. (1975) used 18-crown-6 to solubilize KOz in dimethylformamide, dimethoxyethane and diethyl ether, whilst Johnson and Nidy (1975) reported its solubilization in benzene. A wide variety of chemical transformations have been realized with K02 complexes of crown ethers. With alkyl halides the main reaction products are peroxides, alcohols and olefins (Johnson and Nidy, 1975). Peroxides are... 

Moro-Oka et al. (1976) have reported that the oxidation of 9,10-dihydroanthracene by K02 solubilized in DMSO by 18-crown-6 gives mainly the dehydrogenated product, anthracene. Under the same conditions, 1,4-hexadiene is dehydrogenated to benzene. The authors proposed a mechanism in which the superoxide ion acts as a hydrogen-abstracting agent only. The oxidations of anthrone (to anthraquinone), fluorene (to fluorenone), xanthene (to xanthone) and diphenylmethane (to benzophenone) are also initiated by hydrogen abstraction. 

Although anation and aquation rates of vitamin B12 are not affected appreciably by aqueous micelles, the solubilized water in reversed micelles, in contrast, influences the rate and equilibrium constants for the formation and decomposition of glycine, imidazole, and sodium azide adducts of vitamin Bl2 (Fendler et al., 1974). A vitamin B12 molecule is conceivably shielded from the apolar solvent (benzene) by some 300 surfactant molecules. 

The next step involved cooling the reaction mixture to -196°C, removing the H2 at low pressure, and sealing the tube. This sealed tube was then used in the equilibrium measurements. When it warmed up, a fraction of the hydride complex reacted with benzene, yielding H2 and the phenyl complex, according to equilibrium 14.12. Therefore, the total amount of substance of H2 in equation 14.18 is given by the sum of the initial amount of substance of H2 (no) and the amount of substance of Sc(Cp )2Ph in equilibrium. The latter is easily calculated from the relative concentrations of Sc(Cp )2Ph and Sc(Cp )2H determined by H NMR, and the known initial concentration of Sc(Cp )2H (5.4 x 10-5x 1000/0.5 = 0.108 mol dm-3). To evaluate the initial amount of substance of H2, consider the experimental procedure before and after reaction 14.19 takes place. When this reaction occurs (at 25 °C) a certain amount of H2 remains in solution, and it can be calculated by an equation similar to 14.17. This amount will be equal to no, by assuming that (1) there is no further H2 solubilization when the tube is rapidly cooled to — 196 °C, and (2) only the H2 dissolved in the frozen reaction mixture is not removed by the evacuation procedure. 

The oxidation of organic compounds by water-soluble inorganic oxidants is often made difficult not only by the insolubility of the organic substrate in water, but also by the susceptibility of many of the miscible non-aqueous solvents to oxidation. Solubilization of the ionic oxidant into solvents such as benzene, chloroform, dichloromethane or 1,2-dichlorobenzene, by phase-transfer catalysts obviates these problems, although it has been suggested that dichloromethane should not be used, as it is also susceptible to oxidation [1]. 

Berger and coworkers [17] demonstrated the existence of macrocyclic substances capable of solubilizing alkali metal ions in nonpolar media, and described the formation of sodium and barium salts of a metabolite that had acid properties and was formed in a culture of an unspecified streptomyces. These salts were insoluble in water but dissolved in ether and benzene. The metabolite structure, originally called X 464 [17] and later nigericin [204]... 

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