Alkyl carboxylic acids, sulfonation

Two novel monoaminodibenzothiophenes, 9b-amino-l,4,4a,9b-tetra-hydrodibenzothiophene (113) and 9b-amino-l,2,3,4,4a,9b-hexayhydro-dibenzothiophene (114) have been synthesized from the corresponding carboxylic acid sulfones 32 and 33 by treatment with sodium methoxide and bromine followed by reduction of the resultant sulfone carbamates with LAH. A -Alkylation of both 113 and 114 gives compounds which possess CNS depressant activity. ... 

Cation Exchange Extractants. This class of extractants includes phenols, branched alkyl carboxylic acids, alkyl phosphoric acids, diketones, and alkyl-aryl sulfonic acids. The last group listed, sulfonic acids, are analogous to sulfonic-acid cation exchange resins and have very little selectivity. Diketones, alkyl phosphoric acids and carboxylic acids can provide both cation exchange functions and coordination functions. This feature has made bis(2-ethylhexyl)phosphoric acid one of the most versatile and powerful extractants of this type. (5) The nation below illustrates simple cation exchange extraction. 

C6.C12) Alkyl carboxylic acid, trimethylolpropane triester. See Trimethylolpropane tricaprylate/tricaprate (C10-C18) alkylsulfonic acid, sodium salt. See Sodium C10-18 alkyl sulfonate C29-70 carboxylic acids. See C29-70 acid CCA Type C Wood Preservative 50-60%. See Chromate copper arsenate CCC. See Chlormequat chloride Calcium cyanamide Chlorophyllin-copper complex N-(C14-C18) and (C18-C18) unsaturated alkylpropylenediamine C14-C18 and C18-18-unsat. N-(alkyl) propylene diamine. See Tallowaminopropylamine (C18-C18) and (Cl 8) unsaturated alkylcarboxylic acid. See Palmitic/oleic acids (C18-C18) and C18 unsaturated alkyidimethylamine. See Dimethyl oleic-linolenic amine... 

Three generations of latices as characterized by the type of surfactant used in manufacture have been defined (53). The first generation includes latices made with conventional (/) anionic surfactants like fatty acid soaps, alkyl carboxylates, alkyl sulfates, and alkyl sulfonates (54) (2) nonionic surfactants like poly(ethylene oxide) or poly(vinyl alcohol) used to improve freeze—thaw and shear stabiUty and (J) cationic surfactants like amines, nitriles, and other nitrogen bases, rarely used because of incompatibiUty problems. Portiand cement latex modifiers are one example where cationic surfactants are used. Anionic surfactants yield smaller particles than nonionic surfactants (55). Often a combination of anionic surfactants or anionic and nonionic surfactants are used to provide improved stabiUty. The stabilizing abiUty of anionic fatty acid soaps diminishes at lower pH as the soaps revert to their acids. First-generation latices also suffer from the presence of soap on the polymer particles at the end of the polymerization. Steam and vacuum stripping methods are often used to remove the soap and unreacted monomer from the final product (56). 

Reaction conditions depend on the reactants and usually involve acid or base catalysis. Examples of X include sulfate, acid sulfate, alkane- or arenesulfonate, chloride, bromide, hydroxyl, alkoxide, perchlorate, etc. RX can also be an alkyl orthoformate or alkyl carboxylate. The reaction of cycHc alkylating agents, eg, epoxides and a2iridines, with sodium or potassium salts of alkyl hydroperoxides also promotes formation of dialkyl peroxides (44,66). Olefinic alkylating agents include acycHc and cycHc olefinic hydrocarbons, vinyl and isopropenyl ethers, enamines, A[-vinylamides, vinyl sulfonates, divinyl sulfone, and a, P-unsaturated compounds, eg, methyl acrylate, mesityl oxide, acrylamide, and acrylonitrile (44,66). 

Besides the use of anionics such as sulfonates and nonionics such as alkyl-phenol ethoxylates, in 1977 the use of ether carboxylates was also described [183] in terms of its excellent temperature, electrolyte, and hard water stability and low interfacial tension, especially in case of the C12-C14 ether carboxylic acid with 4.5 mol EO. 

Ci2-Ci3 ether carboxylic acid with 4.5-6 mol EO and Ci2-C15 ether carboxylic acid with 9 mol EO as cosurfactant improve the use of alkyl-o-xylene-sulfonate as primary surfactant at different salinity while maintaining good oil solubilization [189]. It is possible to optimize the surfactant system in relation to the crude oil reservoir characteristics. 

Diazoalkanes alkylate acidic and enolic groups rapidly and other groups with replaceable hydrogens slowly. Carboxylic and sulfonic acids, phenols and enols are alkylated virtually instantaneously when treated with this reagent. Lewis acid catalysts (e.g., BF3.Et20) are used to promote the reaction of... 

Two methods for converting carboxylic acids to esters fall into the mechanistic group under discussion the reaction of carboxylic acids with diazo compounds, especially diazomethane and alkylation of carboxylate anions by halides or sulfonates. The esterification of carboxylic acids with diazomethane is a very fast and clean reaction.41 The alkylating agent is the extremely reactive methyldiazonium ion, which is generated by proton transfer from the carboxylic acid to diazomethane. The collapse of the resulting ion pair with loss of nitrogen is extremely rapid. 

As noted in the preceding section, one of the most general methods of synthesis of esters is by reaction of alcohols with an acyl chloride or other activated carboxylic acid derivative. Section 3.2.5 dealt with two other important methods, namely, reactions with diazoalkanes and reactions of carboxylate salts with alkyl halides or sulfonate esters. There is also the acid-catalyzed reaction of carboxylic acids with alcohols, which is called the Fischer esterification. 

Compounds that are even better analogues of carboxylic acids are produced when an alkyl or aryl group replaces one of the hydroxyls in sulfuric acid. This provides compounds called sulfonic acids, which in turn give rise to a range of derivatives exactly comparable to those we have met as carboxylic acid derivatives (Table 7.4). 

Incorporating an electron-donor alkyl group into position 2 of 2 was shown by foe present authors to facilitate S-oxidation thus, 2-efoyl-thieno[3,2-6]thiophene-l,1-dioxide (214) was prepared at40°-45° from 2-ethylthieno[3,2-6]thiophene, hydrogen peroxide and acetic acid. The thieno[3,2-6]thiophene system undergoes oxidation even if foe second a-position is carboxy-substituted oxidation of 5-efoylthieno[3,2-6]-thiophene-2-carboxylic acid furnished foe 4,4-dioxide (215) subsequently decarboxylated to sulfone (214) [Eq. (70)]. The [2,3-6] isomers, 20 and 55, with foe sulfur atoms bound to foe same carbon atom, do not form sulfones under similar conditions. 

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