Anion alcoholic solutions

In aqueous or alcoholic solution, certain alkylazoles react with bases to give traces of anions of type (367). With suitable electrophilic reagents, these anions undergo reasonably rapid and essentially non-reversible reaction. 

Other detection methods are based on optical transmittance [228-231], Alcohol sulfates have been determined by spectrophotometric titration with barium chloride in aqueous acetone at pH 3 and an indicator [232] or by titration with Septonex (carbethoxypentadecyltrimethylammonium bromide) and neutral red as indicator at pH 8.2-8.4 and 540 nm [233]. In a modified two-phase back-titration method, the anionic surfactant solution is treated with hyamine solution, methylene blue, and chloroform and then titrated with standard sodium dodecyl sulfate. The chloroform passing through a porous PTFE membrane is circulated through a spectrometer and the surfactant is analyzed by determining the absorbance at 655 nm [234]. The use of a stirred titration vessel combined with spectrophotometric measurement has also been suggested [235]. Alternative endpoint detections are based on physical methods, such as stalag-mometry [236] and nonfaradaic potentiometry [237]. 

The amount of residual sulfonate ester remaining after hydrolysis can be determined by a procedure proposed by Martinsson and Nilsson [129], similar to that used to determine total residual saponifiables in neutral oils. Neutrals, including alkanes, alkenes, secondary alcohols, and sultones, as well as the sulfonate esters in the AOS, are isolated by extraction from an aqueous alcoholic solution with petroleum ether. The sulfonate esters are separated from the sultones by chromatography on a silica gel column. Each eluent fraction is subjected to saponification and measured as active matter by MBAS determination measuring the extinction of the trichloromethane solution at 642 nra. (a) Sultones. Connor et al. [130] first reported, in 1975, a very small amount of skin sensitizer, l-unsaturated-l,3-sultone, and 2-chloroalkane-l,3-sultone in the anionic surfactant produced by the sulfation of ethoxylated fatty alcohol. These compounds can also be found in some AOS products consequently, methods of detection are essential. 

A warmed alcoholic solution of cobalt(Il) nitrate and 2-formylpyridine S-methyldithiocarbazate, 6, yielded diamagnetic [Co(6-H)2]N03 [126]. However, cobalt(II) chloride, bromide and thiocyanate yielded complexes with cobalt(III) cations and cobalt(II) anions, [Co(9-H)2]2 [C0A4]. 

The electrochemical reduction of aryllead triacetates was smdied by Chobert and Devaud82, as a re-examination of some previous work83 to detect the role of intermediates such as [ArPb(OAc)2]V The reductions were carried out by polarography in acetic acid or acidic alcohol solutions and show three diffusion controlled waves. The first step involves a single electron transfer to produce a radical anion which dimerizes, arylates the electrode or hydrolyzes to phenol ... 

The second-order rate constant for the methylation of sodium 9-fluorenone oximate in 33.5% acetonitrile/66.5% t-butyl alcohol solution was found to decrease with increasing concentration of the salt, suggesting an equilibrium (13) between the reactive free anion [109] and the less reactive ion pair [110]... 

Other techniques, such as C.D. spectral change, have been used to demonstrate the presence of octa coordination for lanthanide ion in a system containing Eu(FOD)3 and alcohols or ketones (28). However, the anionic tetrakis complexes e.g. Eu(acac)i, Eu(benzac)i, Eu(DBM)i, Eu(BTFA)4, tend to dissociate into the tris-complex and L in alcoholic solution. The degree of dissociation depends on the complex as well as the polarity of the medium. In alcohol-DMF medium the dissociation is enhanced compared to the alcoholic solutions (29). The end product of these dissociation reaction may well be an octacoordinated species. Fluorescence emission from the coordinated europium ion was also helpful in estabhshing the nature of the species in solution 29). 

Formylfuran reacts with potassium cyanide in alcohol solution to give a product containing two furan nuclei. What is this product and how does it form Can you suggest an alternative synthesis of the compound from 2-formylfuran using propane-1,3-dithiol as one reagent Hint consider an acyl anion equivalent approach). 

Studies of Solvation Using Electrons and Anions in Alcohol Solutions ... 

In this paper, we will limit ourselves to the discussion of two types of anions in alcohol solutions the benzophenone anion [7-9] and the solvated electron. One can consider that these systems are both measurements of the solvation of an anion, if we consider the electron... 

The more acidic fluorene in tert-butyl alcohol solution, or in DMSO solution, reacts by a process that involves the carbanion in equilibrium with hydrocarbon. Thus, fluorene and 9,9-dideuteriofluorene oxidize at identical rates. We have established that the oxidation of the anion of fluorene can be catalyzed by a variety of electron acceptors (v), including various nitroaromatics (18). The catalyzed oxidation rates were found to follow the rates of electron transfer measured by ESR spectroscopy in the absence of oxygen. These results established the catalyzed reaction as a free radical chain process without shedding light upon the mechanism of the uncatalyzed reaction. 

IL interactions with water are weaker than in many studied alcoholic solutions, especially in the presence of alcohols with the short alkyl chain. The observed inverse dependence on the temperature for aqueous or alcoholic mixtures refers to the special trend of the packing effect of ILs into hydrox-ylic solvents and its strong dependence on the steric hindrance of aliphatic residues in the cation, or anion, or an alcohol (e.g., [C4CiIm][C3SOJ). 

Similar sorts of results may be found with the nitrate anion. In this case, the nitrate ion itself has a characteristic absorption in the ultraviolet. When paired with a transition-element cation, in alcoholic solution, this absorption is markedly altered (2). It also shows alterations with other cations. In certain ketone and ether solutions, it has been possible to demonstrate further that the vibrational spectrum of the nitrate ion has been altered in such a pattern as to be consistent with a binding of one of the nitrate oxygens to the cation (2), so that major vibration now occurs between this oxygen and the rest of the bound nitrate group. 

Uniformly, within this group of cations, perchlorate ion accompanying the transition-element cation is replaced by nitrate (7,31), thiocyanate (7,52), or halide (7,6). Nitrate is probably replaced by thiocyanate, but a secondary change takes place in many systems, which makes direct comparison difficult (see below). If one then makes the further reasonable assumption that solvent interference can be used as an inverse measure of tendency to bind to the central metal cations, thiocyanate, whose competition with alcohol is less efficient (52) than that of chloride (6), should be somewhat replaceable with chloride. Comparisons between chloride and thiocyanate in acetonitrile show also that the formation of a complex with a given anion/cation ratio takes place much more readily with chloride than with thiocyanate (55, 34). By the same criterion, from experiments in alcoholic solution (55), bromide should replace chloride, and an extrapolation of the behavior to iodide seems reasonable. 

In alcoholic solution, carbohydrates possibly complex with undissociated molecules (ion pairs) of salt, as well as with free cations. Data from optical rotation experiments1 suggest that, even in aqueous solution, undissociated molecules of salt may be associated with the carbohydrate (see Section II, 7, p. 230). On the other hand,/ree anions do not appear to complex with carbohydrates in solution (see Section II, 8, p. 234). 

Addition of the desired anion to an aqueous or alcoholic solution of the copper complex. 

An adsorption study on a strong base anion exchange resin from dilute HNO3 and aliphatic alcohols showed [51] that, with the exception of Eu (in CH3OH), the rare earth adsorption from HN03-alcohol solutions decreased with increasing length of the primary carbon chain in the alcohol concerned. 

---