Alkylsulfonation

Polyaniline (PANI) can be formed by electrochemical oxidation of aniline in aqueous acid, or by polymerization of aniline using an aqueous solution of ammonium thiosulfate and hydrochloric acid. This polymer is finding increasing use as a "transparent electrode" in semiconducting devices. To improve processibiHty, a large number of substituted polyanilines have been prepared. The sulfonated form of PANI is water soluble, and can be prepared by treatment of PANI with fuming sulfuric acid (31). A variety of other soluble substituted AJ-alkylsulfonic acid self-doped derivatives have been synthesized that possess moderate conductivity and allow facile preparation of spincoated thin films (32). 

In tanneries, sodium bisulfite is used to accelerate the unhairing action of lime. It is also used as a chemical reagent ia the synthesis of surfactants (qv). Addition to alpha-olefins under radical catalyzed conditions yields sodium alkylsulfonates (wetting agents). The addition of sodium bisulfite under base-catalyzed conditions to dialkyl maleates yields the sulfosucciaates. 

Manufacture of alkylsulfones, important intermediates for metal-complex dyes and for reactive dyes, also depends on O-alkylation. An arylsulphinic acid in an aqueous alkaline medium is treated with an alkylating agent, eg, alkyl haUde or sulfate, by a procedure similar to that used for phenols. In the special case of P-hydroxyethylsulfones (precursors to vinylsulfone reactive dyes) the alkylating agent is ethylene oxide or ethylene chlorohydrin. 

Rawlings and Lingafelter [69] studied the hydrated phases of sodium alcohol sulfates ranging from C6 to C20 and their crystal structures by X rays. The a phase is almost identical to that of the alkylsulfonates but all other phases are different. The crystals of all phases are monoclinic. This work was completed by Prins and Prins [70] who gave more precise details of the polymorphism of sodium alcohol sulfates. 

The flotation of sulfidic, oxidic, and salt-type ores and, in special cases, silicate ores can be improved by the use of ether carboxylates as collectors [221,222]. In particular, the flotation of fluorite, barite, and scheelite is mentioned. Special synergistic combinations of ether carboxylates with fatty acids [223] and with vinyl- or alkylsulfonic acid polymer [224] are described. 

A related reaction reacts the sodium salt of an alkylsulfonic acid with thionyl chloride at 100°C, to give the alkyl chloride. ... 

Figure 4. Chromatogram showing separation of the 3-phenyl-2(lH)pyridone alkylsulfonate sodium salts. Conditions as described in the text under "HPLC Separation Conditions."...

Ammonium salts of alkenyl succinic half-amides have teen described for use as corrosion inhibitors in oil and gas production technology to combat corrosion by media containing CO2, H2S, and elemental sulfur [1366]. The inhibitor composition may contain a dispersing agent, such as a low molecular weight or polymeric anionic surfactant like an alkylsulfonic acid or an alkyl-aryl sulfonic acid. 

Antistatic agents are ionic substances, such as inorganic salts or organic materials, which attract water molecules. Outstanding materials are derived from the fatty amide and amine chemistry, such as ethoxylated alkyl amines, glycerolmonostearate, fatty alkanolamines, and sodium alkylsulfonates (C12-C16 alkyl groups are preferred because of low loss by evaporation). 

There has been significant emphasis on the use of pyrimidine thio ethers for further selective functionalisation by nucleophilic displacements of either the alkylthio or alkylsulfone and general syntheses of pyrimidines often include methylthio as one of the representative substituents. 

The sulfoxidation of aliphatic hydrocarbons is the easiest method for the synthesis of alkylsulfonic acids. Their sodium salts are widely used as surfactive reactants in technology and housekeeping. Platz and Schimmelschmidt [1] were the first to invent this synthetic method. Normal paraffins (Ci4-Cig) are used for the industrial production of alkylsulfonic acids [2-4]. Olefins and alkylaromatic hydrocarbons do not produce sulfonic acids under the action of sulfur dioxide and dioxygen and retard the sulfoxidation of alkanes [5-9],... 

Water retards the sulfoxidation of alkanes [25]. The results of experiments on decane sulfoxidation with addition of water (T=333K, pO2 = 980kPa, [S02]o = 6.2mol L 1, vio=5.0x 10-7 mol L-1 s 1) are given in the following table. The rate of sulfoxidation was observed to increase in time due to the accumulation of alkylsulfonic peracid and, hence, v0 -c vmax. 

OXIDATION BY ALKYLSULFONIC PERACIDS 12.5.1 Oxidation of Aromatic Hydrocarbons... 

Alkylsulfonic acids are active oxidative agents like other organic peracids. Several oxidative reactions of seodecylsulfonic peracid were studied by Safiullin et al. [41]. Peracid was found to oxidize benzene to phenol as the first intermediate product. The formed sulfonic acid accelerates the reaction. Oxidation occurs according to the stoichiometric equation... 

Alkylsulfonic peracids oxidize olefins to epoxides. The formed sulfonic acid reacts with epoxide to form diols and esters. The yields of epoxides in the reactions of oxidation of two cycloolefins are given in Table 12.4. 

The observed rate constant is kohs = kK. Alkylsulfonic peracid was successfully used as an efficient regioselective oxidant of the carbonyl group [25]. 

The answer is b. (Hardmanr p 1241.) Busulfan is an alkylating agent that, in contrast to other alkylators, is an alkylsulfonate. Thioguanine is a purine antimetabolite. Bleomycin is classified as a chemotherapeutic... 

Figure 18. Absorption spectra of C5AzoCioN+Br cast film containing alkylsulfonate.

Spectral experiments on incorporation of sodium alkylsulfonates as guest molecules into the host bilayer assembly strongly suggest formation of the void space expected in the structural model I. Cast films of 1 1 mixture of CsAzoCioN+Br and sodium n-butylsulfonate (kmax = 303 nm) or sodium propylsulfonate (kmax = 302 nm) showed a similar absorption spectrum of pure C5AzoCjoN+Br cast film (kmax = 301 nm). Longer guest molecules sodium n-pentylsulfonate (kmax = 326 nm), n-hexylsulfonate (kmax = 329 nm), and n-heptylsulfonate... 

Figure 19. Absorption maxima of C5AzoCioN+Br cast film (open circle) and CgAzoCioN+Br film (square) incorporating guest alkylsulfonate molecules.

Alkyl-substituted silicon peroxides, 78 444 Alkyl sulfates, 23 537 use in cosmetics, 7 849 Alkylsulfones, O-alkylation and, 9 280 Alkyl sulfoxide, micellization of, 24 132t Alkyl tertiary alkyl ethers, 70 575 Alkylthexylboranes, 73 639 Alkyl-thiols, 77 57 4-Alkylthiosemicarbazides, 73 575 Alkyl-tin catalysts, 20 40 Alkyltitanium halides, 25 108—109 Alkyltitaniums, 25 106 higher, 25 116... 

Poly(3-alkylsulfonate thiophene)s, 23 717 Poly(3-alkylthiophenes) (P3ATs) conducting, 7 517 stability, 7 536... 

A mixture of these fluorinated surfactants was separated according to the method applied by Popenoe et al. [52]. For ionisation and detection, ESI-MS in the negative mode was applied. The result of LC separation is presented in the RIC in Fig. 2.11.26(a). Some of the separated compounds in the TIC and mass traces could be identified as perfluoro alkylsulfonates and perfluoro alkylcarboxylates such as... 

Fig. 2.11.24. General structural formulae of (I) perfluorinated alkylsulfonic acid, (II) partly fluorinated alkylsulfonic acid, and (III) perfluorinated carboxylic acid.

Gotti, R., Andrisano, V, Cavrini, V., Bertucci, C., and Furlanetto, S. (2000). Analysis of ACE-inhibitors by CE using alkylsulfonic additives.. Pharm. Biomed. Anal. 22, 423-431. 

Despite the fact that alkylating agents exhibit a common mechanism of action, their clinical use varies depending on differences in pharmacokinetics, metabolism, hpid solubility, ability to penetrate membranes, and toxicity. They can be classified as nitrogen-containing mustard derivatives (mechorethamine, chlorambucil, melfalan, cyclophosphamide, ifos-famide), derivatives of ethylenimine (thiotepa), nitrosoureas (carmustine, lomustine, strep-tozocin), alkylsulfonates (busulfan), and derivatives of platinum (cwplatin, carboplatin). 

Busulfan is the one drug in the alkylsulfonate series used in medicine. 

The use of amphiphilic ions, such as alkylsulfonate or alkylquaternary ammonium compounds, as hetaerons to augment retention of ionized sample components having charges opposite is quite popular in RPC. By... 

The effect of additives betrays the intricacy of the balance of rate effects even more. The addition of cholesterol to catalytic bilayers has been found to be beneficial for the Kemp eleminiation but to inhibit the decarboxylation of 6-NBIC. In general, the effects of additives on the decarboxylation of 6-NBIC appear to subtly depend on the structure of the hydrophobic tail and hydrophilic headgroup of additives. Similarly subtle effects were found for the Kemp elimination and nucleophilic attack by Br and water on aromatic alkylsulfonates depending on the choice of additive, hydrogen bonding effects, reactivity of partially dehydrated OH , and local water concentrations all played a role and vesicular catalysis could be increased or decreased. 

---