Salicylic acids, oxidation

Muller R, Naumann E, Detmar M, Orfanos CE. Stabilitat von Cignolin (Dithranol) in teerhaltigen Salben mit und ohne Salicylsaurezusatz. Oxidation in Danthron und Dithranoldimer. [Stability of cignolin (dithranol) in ointments containing tar with and without the addition of salicylic acid. Oxidation to danthron and dithranol dimer.] Hautarzt 1987 38(2) 107-11. 

Slightly bitter, cryst scales or powder, mp 134-135. One gram dissolves In 1310 ml cold water, 82 ml boiling water 15 ml cold alcohol, 2.8 m] boiling alcohol 14 ml chloroform, 90 ml ether sol in glycerol. Gives a pasty mass with phenol, chloral hydrate or pyrocatecho], strong acids or alkalies, salicylic acid, oxidizers, iodine, spirit nitrous ether. LDjq orally in rats 1.65 g/kg (Boyd). 

C7H6O2 Oily liquid of aromatic odour b.p. 196°C. (t is prepared by the action of chloroform and caustic potash on phenol (the Reimer-Tiemann reaction) or by the oxidation of the glucoside salicin. It is easily reduced to salicyl alcohol or oxidized to salicylic acid. 

Oxidation to acids. Varm together in a small conical flask on a water-bath for lo minutes a mixture of 0 5 ml. of benzaldehyde or salicylaldehyde, 15 ml. of saturated KMn04 solution, and 0-5 g. of NajCOj. Then acidify with cone. HCl, and add 25% sodium sulphite solution until the precipitated manganese dioxide has redissolved. On cooling, benzoic or salicylic acid crystallises out. 

Action of sodium hydroxide. Does not undergo the Cannizzaro reaction. It dissolves in dil. NaOH solution, giving a yellow solution from which the aldehyde is precipitated unchanged on acidification. If heated with cone. NaOH solution, salicylaldehyde slowly undergoes atmospheric oxidation to salicylic acid. 

The key compound m the synthesis of aspirin salicylic acid is prepared from phe nol by a process discovered m the nineteenth century by the German chemist Hermann Kolbe In the Kolbe synthesis also known as the Kolbe—Schmitt reaction, sodium phen oxide IS heated with carbon dioxide under pressure and the reaction mixture is subse quently acidified to yield salicylic acid... 

SALICYLIC ACID AND RELATED COMPOUNDS] (Vol 21) -oxidation of fiYDROXYBENZALDEHYDES] (Vol 13)... 

Other routes for hydroxybenzaldehydes are the electrolytic or catalytic reduction of hydroxybenzoic acids (65,66) and the electrolytic or catalytic oxidation of cresols (67,68). (see Salicylic acid and related compounds). Sahcylaldehyde is available in drums and bulk quantities. The normal specification is a freezing point minimum of 1.4°C. 4-Hydroxybenzaldehyde is available in fiber dmms, and has a normal specification requirement of a 114°C initial melting point. More refined analytical methods are used where the appHcation requires more stringent specifications. 

The ormethyl-salicylic acid melting at 99°, whUst the par -compound yields anisic acid melting at 184°. 

The most common NSAID is aspirin, or acctylsalicvlic acid, whose use goes back to the late 1800s. It had been known from before the time of Hippocrates in 400 bc that fevers could be lowered by chewing the bark of willow trees. The active agent in willow bark was found in 1827 to be an aromatic compound called salicin, which could be converted by reaction with water into sal- icy I alcohol and then oxidized to give salicylic acid. Salicylic acid... 

Samarium, tris(triphenylphosphine oxide)bis-(diethyldithiophosphato)-structure, 1,78 Samarium complexes dipositive oxidation state hydrated ions, 3, 1109 Samarium(III) complexes salicylic acid crystal structure, 2, 481 Sampsonite, 3, 265... 

Merola reported the preparation of hydrido(carboxylato)iridium(lll) complexes, mer-[lrCl(0C(0)R)(H)(PMe3)3] (90) (R = Ph, Me), by oxidative addition of acetic acid or benzoic acid to [Ir(cod)(PMe3)3]Cl (67) [46]. The structure of 90 (R = Ph) in which the carboxylato ligand coordinates as an T -ligand, was confirmed by X-ray analysis. The reaction of 67 with salicylic acid yielded the product 91, which resulted from activation of the O-H bond of the carboxylato but not of the hydroxo group (Scheme 6-13). 

Ranjit KT, Willner I, Bossmann SH, Braun AM (2001) Lanthanide oxide doped titanium dioxide photocatalysts Effective photocatalysts for the enhanced degradation of salicylic acid and t-cinnamic acid. J Catal 204 305-313... 

At present, the relevance of these results to photode-gradationl 0f condensates 1 is a matter of speculation. Of particular interest is identification of the photoproduct quencher(s) (PP, Scheme I). Possible candidates are salicylic acid derivatives, which exhibit the requisite absorptivity at about 300 nm, and which may be formed by oxidation of ortho-photo-Fries products (Scheme III), as illustrated in eq. 1. 

The potential of using extrinsic (fluorescent) probes for monitoring the initial stages of oxidation was explored for the photo-oxidation of a UV-cured aliphatic polyurethane-acrylate-based adhesive [68]. The two probes investigated were p-dimethylamino salicylic acid (p-DASA) and 2, 7 -difluorescein (Oregon Green... 

Decomposition of salicin (2-(hydroxymethyl)phenyl-/ -D-glucopyranoside) yields two alcohols glucose (a compound with numerous 1°, 2°, and a 3° hydroxyl functionalities, Fig. 13.4.6) and l-0H-2-CH20H-benzene (a 1° alcohol, Fig. 13.4.7). Further oxidation of l-0H-2-CH20H-benzene leads to the formation of salicylic acid ... 

Haapakka and Kankare have studied this phenomenon and used it to determine various analytes that are active at the electrode surface [44-46], Some metal ions have been shown to catalyze ECL at oxide-covered aluminum electrodes during the reduction of hydrogen peroxide in particular. These include mercu-ry(I), mercury(II), copper(II), silver , and thallium , the latter determined to a detection limit of <10 10 M. The emission is enhanced by organic compounds that are themselves fluorescent or that form fluorescent chelates with the aluminum ion. Both salicylic acid and micelle solubilized polyaromatic hydrocarbons have been determined in this way to a limit of detection in the order of 10 8M. 

Quinoline Salicylic acid Silicon Dinitrogen tetroxide, linseed oil, maleic anhydride, thionyl chloride Iodine, iron salts, lead acetate Alkali carbonates, calcium, chlorine, cobalt(II) fluoride, manganese trifluoride, oxidants, silver fluoride, sodium-potassium alloy... 

Copper complexes were used as efficient catalysts for selective autoxidations of flavonols (HFLA) to the corresponding o-benzoyl salicylic acid (o-BSH) and CO in non-aqueous solvents and at elevated temperatures (124-128). The oxidative cleavage of the pyrazone ring is also catalyzed by some cobalt complexes (129-131). 

Phosphine complexes, osmium, 19 642 Phosphine coordination complexes, of uranium, 25 436 Phosphine derivatives, 19 28 Phosphine oxide(s), 11 495-496 19 66 predicted deviations from Raoult s law based on hydrogen-bonding interactions, 8 814t in salicylic acid manufacture, 22 8 Phosphine oxide diols/triols, 11 501 Phosphine selenides, 22 90 Phosphinic acid, 19 20, 54-55 Phosphinic anhydride, 11 499 Phosphinothricin acetyltransferase (PAT) proteins, 13 360 Phosphite esters, 19 20 Phosphites, in VDC polymer stabilization, 25 720... 

Technically important dyes are salicylic acid derivatives that function as chrome mordant dyes for wool. Thus Cl Mordant Blue 1 (6.187) is made by the aldehyde synthesis from 2,6-dichlorobenzaldehyde and 2-hydroxy-3-methylbenzoic (o-cresotinic) acid in concentrated sulphuric acid. Oxidation of the leuco base is achieved by the addition of sodium nitrite. On wool the product, which is isolated as the sodium salt, is a dull maroon colour, changing to a bright blue on treatment with a chromium salt. Some dyes of this type, such as Cl Mordant Violet 1 (6.188), also contain a basic group. This compound is also prepared by the aldehyde route. 

The primary anion studied in both the titration calorimetry7 and CIR-FTIR experiments reported here was the salicylate (2-hydroxybenzoate) ion (SAL). Acidity constants for salicylic acid are pK = 3.0 and pK = 13 (12), and the aqueous solubility of salicylic acid is 2.4 g/L, while that of NaSAL is 975 g/L. SAL has been shown to adsorb on both iron oxides (13) and aluminum oxides (14). Several other anions were also studied, and results for these anions are given as needed to illuminate certain features of the salicylate-goethite adsorption process. 

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