Synthesis from benzene sulfonate

Anthraquinone dyes are derived from several key compounds called dye intermediates, and the methods for preparing these key intermediates can be divided into two types (/) introduction of substituent(s) onto the anthraquinone nucleus, and (2) synthesis of an anthraquinone nucleus having the desired substituents, starting from benzene or naphthalene derivatives (nucleus synthesis). The principal reactions ate nitration and sulfonation, which are very important ia preparing a-substituted anthraquiaones by electrophilic substitution. Nucleus synthesis is important for the production of P-substituted anthraquiaones such as 2-methylanthraquiQone and 2-chloroanthraquiaone. Friedel-Crafts acylation usiag aluminum chloride is appHed for this purpose. Synthesis of quinizatia (1,4-dihydroxyanthraquiQone) is also important. 

Yosida et al. [41] found that p-t< rr-butylcalix[6]ar-ene can extract Cu from the alkaline-ammonia solution to the organic solvent. Nagasaki and Shinkai [42] described the synthesis of carboxyl, derivatives of calix-[n]arenes ( = 4 and 6) and their selective extraction capacity of transition metal cations from aqueous phase to the organic phase. Gutsche and Nam [43] have synthesized various substituted calix[n]arenes and examined the complexes of the p-bromo benzene sulfonate of p-(2-aminoethyl)calix[4]arene with Ni, Cu , Co-, and Fe. ... 

Based on petrochemicals, linear alkyl benzene sulfonates (LAS) are the most important surfactants. First description can be found in patents from the mid-1930s [2] using Fischer-Tropsch synthesis and Friedel-Crafts reactions. With the beginning of the 1950s the importance of the class of surfactants rose. The main use is in household and cleaning products. 

An IL (l-butyl-3-meffiylimidazolium benzene sulfonate [BMIm][PhS03]) has also been used as a reaction medium for the synthesis of a-methylene CCs from C02 and propargyl alcohols, using transition metal salts as the catalyst (Equation 7.23) [217]. 

Cyanoamido-thiocarbamates, from cyan-amide and isothiocyanates, 297 Cyanohydrin, benzene sulfonates, synthesis of, from sodium cyanide and haJo-benzaldehyde, 297... 

Figure 8-15. Synthesis of atracurium besylate (benzene sulfonate salt). (From Stenlake, 1985.)...

Use the methods just presented to devise a synthesis of 4-nitrobenzenesulfonic acid from benzene. [Hint Sulfonation proceeds selectively para to activating groups, because the reagent is sterically hindered and the process reversible (Section 15-10).]... 

The polyaniline nanofibers (PANI-NF) were synthesized by oxidative polymerization of aniline monomer at 0 °C in an ice bath using ammonium persulfate as the oxidant in the presence of surfactant. Aniline, ammonium persulfate, dodecyl benzene sulfonic acid, acrylmethylpropyl sulfonic acid, and camphorsulfonic acid are used as received from Sigma-Aldrich. Sulfonic acid-based surfactants as the dopant and ammonium persulfate as the oxidant were used in the present synthesis of polyaniline nanofibers (see flow charf in Fig. 8.17). Calculated quantities of aniline monomer (0.05 mol) were mixed with 50 mL of distilled water and stirred using magnetic stirrer for 10 min. Meanwhile, calculated quantities of surfactant (0.75 mol) and oxidant (0.05 mol) were dissolved separately in distilled water and stirred for 10 min in an ice bath. The surfactant solution was first added into the aniline monomer aqueous solution and then previously cooled oxidant solution dropwise, and the mixture was allowed to react for 15 h in an ice bath. 

The production of anthraquinone dyes generally proceeds from a few key products generated by electrophilic substitution of unsubstituted anthraquinone or by synthesis of the nucleus. The major methods employed to prepare anthraquinone derivatives substituted in the a-position are sulfonation and nitration. Preparation of b-substituted anthraquinones and of quinizarin (1,4-dihydroxyan-thraquinone) generally is accomplished by synthesis of the nucleus starting from phthalic anhydride and a benzene derivative. 

The raw materials used to synthesize organic dyes are commonly referred to as dye intermediates. Largely, they are derivatives of aromatic compounds obtained from coal tar mixtures. The majority of these derivatives are benzene, naphthalene, and anthracene based compounds. This section provides an overview of the chemical reactions used to prepare the key intermediates employed in dye synthesis. In this regard, emphasis is placed on halogenated, aminated, hydroxy-lated, sulfonated, and alkylated derivatives of benzene, naphthalene, and anthraquinone. 

Oxidation of the cyclic sulfides to cyclic sulfones and subsequent photochemical extrusion of sulfur dioxide from suspensions of the sulfones in benzene [9] this method is only applicable for the synthesis of [2.2] phanes without photolabile functional groups. 

Paquette and coworkers [127], in a synthesis of the complex polyol antibiotic amfidinolu-3, made masterly use of the Julia-Kodenski olefination reaction. Two examples taken from that work are presented below. Reaction of sulfone 285 with aldehyde 284 (Scheme 92) carried out with KHMDS in THF (at - 78 °C to rt) gave the building block 286 with 90% yield but with relatively poor selectivity, EjZ 1>I. Free-radical isomerization of the mixture (benzene, AIBN, reflux) increased the isomer ratio, /2 6/1. 

A low purity (40-80%) divinylbenzene and chloromethylstyrene were used in the presence of a Friedel-Crafts catalyst (AICI3) for the synthesis of a polymeric phenolic antioxidant from p-cresol and l,3-bis(l-hydroxy-l-methylethyl)benzene in the presence of p-toluene sulfonic acid [115]. The obtained product was either used directly as AO for thermosetting resins or was treated consecutively with a-methylstyrene [116] or /ert-butylalcohol [117]. Other polymeric phenolic AO were obtained by reaction of phenol with p-men thane-1,8-diol, l-p-menthen-8-ol or limonene [118] or of p-cresol with 3- or 4-chloromethylstyrene in the presence of BF3-etherate or anhydrous AICI3 [119] the product thus obtained was finally aralkylated by a-methylstyrene. Thermostabilizer and/or LS for PUR was obtained, e.g. 98. 

SYNTHESIS OF <-)-(E,S)-3-(BENZYLOXY)-1-BUTENYL PHENYL SULFONE VIA A HORNER-WADSWORTHEMMONS REACTION OF (.).(S)-2-(BENZYLOXY)PROPANAL (Benzene, [[[1-methyl-3-(phenylsulfonyl)-2-propenyl]oxy]methyl]-, [S-(E)]-) from (Propanal, 2-(phenylmethoxy)-, (S)-)... 

The next objective of the synthesis was the lactone 122, a compound that is also readily available from annotinine (1). Borohydride reduction of the enol acetate 123 derived from 121 yielded a mixture of the hydroxy esters 124 and 125. This mixture was hydrolysed to the corresponding acids, 126 and 127, and the acids treated with p-toluene-sulfonic acid in boiling benzene. The product was a mixture of the desired lactone 122 and the hydroxy acid 127 in approximately equal amounts. Another less attractive method of preparation of 124 was described in the course of the structural study of annotinine (1). 

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