Benzyl sulfonic acid

Polymeric electrolytes, polymer-salt complexes, and gelled electrolytes, e.g., benzyl sulfonic acid siloxane, polyethylene oxide (imine, succinate)-LiC104, and PVDF gel in THF containing a mixture of Bu2Mg and AlEtCl2, respectively. 

The reaction of an aromatic compound with chlorosulfonic acid (44) (one molar equivalent) in an inert solvent, e.g. chloroform, can be used to prepare aromatic sulfonic acids (Scheme 23). Chlorosulfonic acid is a powerful sulfonating agent approximately equivalent to fuming sulfuric acid (oleum), and care must be taken with this reagent to avoid the formation of sulfones or sulfonyl chlorides (see p. 103).5 Aliphatic or benzylic sulfonic acids can be obtained in good yields... 

Chem. Descrip. Alkyl benzyl sulfonic acid lenic Nature Anionic Uses Demulsifier Preperties 62.5% act. 

Substitution Reactions on Side Chains. Because the benzyl carbon is the most reactive site on the propanoid side chain, many substitution reactions occur at this position. Typically, substitution reactions occur by attack of a nucleophilic reagent on a benzyl carbon present in the form of a carbonium ion or a methine group in a quinonemethide stmeture. In a reversal of the ether cleavage reactions described, benzyl alcohols and ethers may be transformed to alkyl or aryl ethers by acid-catalyzed etherifications or transetherifications with alcohol or phenol. The conversion of a benzyl alcohol or ether to a sulfonic acid group is among the most important side chain modification reactions because it is essential to the solubilization of lignin in the sulfite pulping process (17). 

SuIfona.tlon, Sulfonation is a common reaction with dialkyl sulfates, either by slow decomposition on heating with the release of SO or by attack at the sulfur end of the O—S bond (63). Reaction products are usually the dimethyl ether, methanol, sulfonic acid, and methyl sulfonates, corresponding to both routes. Reactive aromatics are commonly those with higher reactivity to electrophilic substitution at temperatures > 100° C. Tn phenylamine, diphenylmethylamine, anisole, and diphenyl ether exhibit ring sulfonation at 150—160°C, 140°C, 155—160°C, and 180—190°C, respectively, but diphenyl ketone and benzyl methyl ether do not react up to 190°C. Diphenyl amine methylates and then sulfonates. Catalysis of sulfonation of anthraquinone by dimethyl sulfate occurs with thaHium(III) oxide or mercury(II) oxide at 170°C. Alkyl interchange also gives sulfation. 

The C2-symmetric epoxide 23 (Scheme 7) reacts smoothly with carbon nucleophiles. For example, treatment of 23 with lithium dimethylcuprate proceeds with inversion of configuration, resulting in the formation of alcohol 28. An important consequence of the C2 symmetry of 23 is that the attack of the organometallic reagent upon either one of the two epoxide carbons produces the same product. After simultaneous hydrogenolysis of the two benzyl ethers in 28, protection of the 1,2-diol as an acetonide ring can be easily achieved by the use of 2,2-dimethoxypropane and camphor-sulfonic acid (CSA). It is necessary to briefly expose the crude product from the latter reaction to methanol and CSA so that the mixed acyclic ketal can be cleaved (see 29—>30). Oxidation of alcohol 30 with pyridinium chlorochromate (PCC) provides alde-... 

The procedure described is essentially that of Ballard and Dehn.1 Stilbene has also been prepared by reduction of desoxy-benzoin,20 benzaldehyde,23 and benzil 2o-2c by dehydrogenation of ethyl benzene,30 toluene,30- 33- 3, and bibenzyl 33-3alkaline reduction of phenylnitromethane,40 phenylnitroacetonitrile,40 and desoxybenzoin 43 by distillation of benzyl sulfone,50 benzyl sulfide,60-63 calcium cinnamate,5 cinnamic acid,5d phenyl cinna-mate,6e-6/ and diphenyl fumarate ie by dehydrohalogenation of a,a -dichlorobibenzyl60 and benzyl chloride 63 by dehalogenation of a,a,c/,a -tetrachlorobibenzyl70 and benzal chloride 73 by the coupling of cinnamic acid and phenyldiazonium chloride 8 by de-... 

This mechanism also applies to other CH2-active compounds such as derivatives of aroxyacetic acid and benzylic sulfones, whose methylation reactions with... 

Because carbohydrates are so frequently used as substrates in kinetic studies of enzymes and metabolic pathways, we refer the reader to the following topics in Ro-byt s excellent account of chemical reactions used to modify carbohydrates formation of carbohydrate esters, pp. 77-81 sulfonic acid esters, pp. 81-83 ethers [methyl, p. 83 trityl, pp. 83-84 benzyl, pp. 84-85 trialkyl silyl, p. 85] acetals and ketals, pp. 85-92 modifications at C-1 [reduction of aldehydes and ketones, pp. 92-93 reduction of thioacetals, p. 93 oxidation, pp. 93-94 chain elongation, pp. 94-98 chain length reduction, pp. 98-99 substitution at the reducing carbon atom, pp. 99-103 formation of gycosides, pp. 103-105 formation of glycosidic linkages between monosaccharide residues, 105-108] modifications at C-2, pp. 108-113 modifications at C-3, pp. 113-120 modifications at C-4, pp. 121-124 modifications at C-5, pp. 125-128 modifications at C-6 in hexopy-ranoses, pp. 128-134. 

Tumoko and coworkers [485] showed that polymers based on acrylamide, methyl propane sulfonic acid and butyl methacrylate in conjunction with poly(2 methacryloyloxyethyl phosphorylcholine-co-butyl methacrylate) are capable of suppressing platelet adherence. Similar results [486] were found on poly(gamma benzyl 1 glutamate-co-leucine) neutralized with sodium. 

Compounds, eg, phenacyl halides, benzyl halides, alkyl iodides, or alkyl esters of sulfonic acids, react with DMSO at 100—120°C to give aldehydes (qv) and ketones (qv) in 50—85% yields (eq. 8) (41) ... 

Historically, this represents the first thiophene synthesis, when Laurent obtained tetraphenylthiophene by heating polymeric thiobenzaldehyde in 1844. Almost any aromatic methyl derivative can be converted to tetraphenylthiophene, which is thermodynamically the most stable thiophene, by heating with sulfur. Toluene, phenylacetic acid, benzyl alcohol, benzyl sulfide or disulfide, benzyl sulfonate or even sodium thiobenzoate have been converted to tetraphenylthiophene under these conditions (52HC(3)l). 

Oxidation of 3,5-bis(methylthio)-l,2,4-triazines (81) with potassium permanganate afforded the 3-monosulfones (241) which could be hydrolyzed to 5-methylthio-l,2,4-triazin-3-ones (242) (69BSF3670). 6-Benzyl-3-thioxo-l,2,4-triazin-5-one (243) with potassium permanganate afforded the 6-benzoyl-3-sulfonic acid (244) (67BSF2551). Similarly, 5-amino-... 

Only a few examples of solid-phase syntheses of phosphonic, phosphoric, and sulfonic acids have been reported (Figure 3.16). Benzyl esters of these strong acids can act as alkylating agents, and may therefore be too labile to serve as linkers for long synthetic sequences on solid phase. However, if cross-linked polystyrene is used as the support, the reactivity of, for example, benzyl sulfonates is strongly reduced, and even... 

Ainberlyst-type catalysts were as active as and more selective than the best homogeneous catalyst, II2SO4. Amberlyst 15 and 3G are macroreticular type polystyrene sulfonic acid resins partially cross-linked with divinylbenzene. The absence of the N—benzyl product when solid acid catalysts were employed suggests the possibility that the reaction could be carried out in a single step. It is also expected to provide all the aforementioned advantages of solid catalysts over liquid catalysts. 

There have been a number of reports of improved selectivity with sulfonic acid resin catalysts compared with conventional liquid acid catalysts[6—9]. Various explanations have also been proposed. If mechanisms usually postulated for condensation reactions with liquid Br0nsted acid [10] and solid acid catalysts [11] are adopted, the sequence of steps shown in Fig. 2 could be considered for the condensation of MFC. Both mechanisms incorporate the essential features of known carbenium ion chemistry, i.t., electrophilic attack on the aromatic ring by polar carbenium ion intermediates. Note that MDU is formed by this attack on the benzene ring of MPC, while the N—benzyl compound by the attack on nitrogen atom. 

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