Benzene, alkylation sulfonation

Estimates based on published and industry infomiation sources for production of linear alkyl (C 2) benzene alkylate sulfonic acid andlauryl-3 mol ethoxy... 

Fatty alcohol- (or alkyl-)ethoxylates, CoE, are considered to be better candidates for LLE based on their ability to induce rapid phase separation for Winsor II and III systems. (Winsor III systems consist of excess aqueous and organic phases, and a middle phase containing bicontinuous microemulsions.) However, C,E,-type surfactants alone cannot extract biomolecules, presumably because they have no net negative charge, in contrast to sorbitan esters [24,26,30,31]. But, when combined with an additional anionic surfactant such as AOT or sodium benzene dodecyl sulfonate (SDBS), or affinity surfactant, extraction readily occurs [30,31]. The second surfactant must be present beyond a minimum threshold value so that its interfacial concentration is sufficiently large to be seen by... 

Iron-acyl enolates, such as 2, prepared by x-deprotonation of the corresponding acyl complexes with lithium amides or alkyllithiums, are nearly always generated as fs-enolates which suffer stereoselective alkylation while existing as the crmt-conformer which places the carbon monoxide oxygen anti to the enolate oxygen (see Section 1.1.1.3.4.1.). These enolates react readily with strong electrophiles, such as primary iodoalkanes, primary alkyl sulfonates, 3-bromopropenes, (bromomethyl)benzenes and 3-bromopropynes, a-halo ethers and a-halo carbonyl compounds (Houben-Weyl, Volume 13/9 a, p 413) (see Table 6 for examples). 

Fig. 1. Sulfonated and sulfated acid products viscosities after 98% conversions at varying temperatures where the vertical line indicates the maximum temperature for batch sulfonation using S03 to minimize color deterioration lines A—C represent branched C12 alkyl benzene (BAB) sulfonic acid from S03, oleum (settled), and oleum (whole mixture), respectively lines D and E, lauryl alcohol 3-ethoxylate sulfuric ester (S03) and lauryl alcohol sulfuric ester...

S03), respectively and line F, linear C12 alkyl benzene (LAB) sulfonic acid (S03). 

R = alkyl, aryl R = 1° or 2 alkyl, allyl, benzyl, activated aryl, acyl X - Cl, Br, I, OTs electrophile epoxide, dialkyl sulfate, alkyl sulfonate, alkyl nitrate base = NaOR NaH base = KOf-Bu, cone. NaOEt, NaH solvent = R OH, f-BuOH, benzene, ether, DMF... 

Aryl amine intermediates for azo and triphenylmethane dyes, as well as a number of vat dye (anthraquinone) intermediates, are made from compounds such as benzene, alkyl benzenes (toluene and higher homologues), phenol and naphthalene. A limited number of reactions are used to produce the most important dye intermediates, including nitration, reduction, halogenation, sulfonation, /V-alkylation, /V-acylation and alkali fusion33,34. 

Detergents, which now rival soap in demand, are based largely on petroleum the variety of structures which confer detergent properties have led to some interesting syntheses. Alkyl aryl sulfonates are made by alkylation of benzene either with chlorinated kerosene or with a highly-branched olefin made from propylene. Long chain olefins for secondary sulfates were made from paraffin wax. Secondary alkyl sulfonates were made by direct sulfonation of paraffins with sulfur dioxide and chlorine, a reaction discovered in America in the 193O s. 

Use in Synthesis. Sulfonation-desulfonation is a useful tool for preparing ortho isomer derivatives of benzene. The sulfonic group is introduced to block the 4 position opposite a methyl, hydroxyl, or acetylamino group then a chlorine or alkyl group is introduced ortho to the methyl or hydroxyl group. Finally, the sulfonic group is removed for the case of 2-chlorotol-uene, the reaction is as follows ... 

A wide use of synthetic detergents (SD) began in the forties of the 20" century, after mastering the commercial production of anionics (alkyl sulfonates - Germany alkylbenzene sulfonates -USA, United Kingdom) and nonionics (ethoxylated alkyl benzenes - Germany). 

Electrophilic Aromatic Bromination 673 Nitration of Benzene 675 Sulfonation of Benzene 676 Friedel-Crafts Alkylation 677 Friedel-Crafts Acylation 680 Benzylic Halogenation 701 Birch Reduction 710... 

Anionic antistatic agents include the sodium alkyl sulfonates, e.g., RO(S02)ONa, the sulphonamides, e.g., C12H25-N-SO2NH2 (where N is a benzene ring) and the sodium alkyl phosphates, e.g., (RO)2PONa, where R is a long hydrocarbon chain such as stearate. 

Typically, plants would buy in the alkyl benzene and sulfonate on-site using either oleum or liquid SO3 before neutralizing with caustic solution. The reactions are highly exothermic and can cause the coloration of the product if temperatures are not controlled. Thus, a dominate bath approach was used to control the quality since consumers do not associate a brown-coloured product with good cleaning power ... 

There is a vast literature on the chemistry of ferrocene, but very little use has been made of this substance in organic synthesis. As ferrocene is readily available (Jolly, 1968) and undergoes a great variety of reactions such as acylation, alkylation, sulfonation, and metalation (Perevalova and Nikitina, 1972), a simple means of removing the iron at the end of the reaction sequence would provide a ready route to substituted cyclopentane derivatives. Some typical acylation reactions [which take place 3.3 x 10 times faster than with benzene (Rosenblum et al., 1963b) are illustrated in Eqs. (64) (Hauser and Lindsay, 1957), (65) (Rosenblum and Woodward, 1958), and (66) (Rosenblum et al., 1963a). 

Representative Electrophilic Aromatic Substitution Reactions of Benzene 457 Mechanistic Principles of Electrophilic Aromatic Substitution 458 Nitration of Benzene 459 Sulfonation of Benzene 461 Halogenation of Benzene 462 Biosynthetic Halogenation 464 Friedel-Crafts Alkylation of Benzene Friedel-Crafts Acylation of Benzene Synthesis of Alkylbenzenes by Acylation-Reduction 469 Rate and Regioselectivity in Electrophilic Aromatic Substitution 470 Rate and Regioselectivity in the Nitration ofToluene 472... 

FIGURE 3.17 Surfactants that have been used in household detergent formulations the aUcyl benzene sulfonate surfactant (ABS) originally used did not undergo biodegradation very well and caused problems due to its persistence, which is the result of its branched-chain structure. The ABS was replaced by Unear alkyl sulfonate (LAS), which is biodegradable because of its straight-chain structure. 

Slightly different values can be attained with more or less branched alkyl chains [120-124]. Figure 18 [125] illustrates the variation of optimum formulation, detected by the position of the minimum interfacial tension that is equivalent to the center of the three-phase behavior region for a series of isomers of the sodium n-hexadecyl benzene-para-sulfonate X< )Ci6S03Na, where X indicates the position of attachment of the benzene ring on the hexadecane chain. The correlation for optimum formulation can be written at constant salinity, constant alcohol content, and constant temperatures as... 

Table 10. Transition temperatures for hexakis(alkyl-sulfone) derivatives of benzene (RSO2-).

Alkyloxyl polyether alcohols Dodecyl benzene sodium sulfonate Polyoxy ethylene soibitan monooleate Sodium alkyl benzene sulfonate Sodium dioctylsulfosuccinate Sodium tetradecyl sulfate Acetylenic glycols Tetrasodium pyrophosphate... 

A clever solution makes use of reversible sulfonation (Section 15-10) as a blocking procedure. Both the substituent and the electrophile are sterically bulky hence, (1,1-dimethylethyl)benzene is sulfonated almost entirely para, blocking this carbon from further electrophilic attack. Nitration now can occur only ortho to the alkyl group. Heating in aqueous acid removes the blocking group and completes the synthesis. 

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