Aromatic hydroxy acids

Other aliphatic hydroxy acids Aromatic Hydroxy Acids... 

N-Benzylamides are recommended when the corresponding acid is liquid and/or water-soluble so that it cannot itself serve as a derivative. Phe benzylamides derived from the simple fatty acids or their esters are not altogether satisfactory (see Table below) those derived from most hydroxy-acids and from poly basic acids or their esters are formed in good yield and are easily purified. The esters of aromatic acids yield satisfactory derivatives but the method must compete with the equally simple process of hydrolysis and precipitation of the free acid, an obvious derivative when the acid is a solid. The procedure fails with esters of keto, sul phonic, inorganic and some halogenated aliphatic esters. 

Preliminary indication of the presence of a phenol ester may be obtained by heating the compound with soda-lime esters of phenols and also aromatic hydroxy-acids usually give the phenol. (Likewise amides, Imides, nitriles, substituted hydrazines, uretheines, etc. eifiord ammonia.)... 

The term naphthenic acid, as commonly used in the petroleum industry, refers collectively to all of the carboxyUc acids present in cmde oil. Naphthenic acids [1338-24-5] are classified as monobasic carboxyUc acids of the general formula RCOOH, where R represents the naphthene moiety consisting of cyclopentane and cyclohexane derivatives. Naphthenic acids are composed predorninandy of aLkyl-substituted cycloaUphatic carboxyUc acids, with smaller amounts of acycHc aUphatic (paraffinic or fatty) acids. Aromatic, olefinic, hydroxy, and dibasic acids are considered to be minor components. Commercial naphthenic acids also contain varying amounts of unsaponifiable hydrocarbons, phenoHc compounds, sulfur compounds, and water. The complex mixture of acids is derived from straight-mn distillates of petroleum, mosdy from kerosene and diesel fractions (see Petroleum). 

Cyanohydrin Synthesis. Another synthetically useful enzyme that catalyzes carbon—carbon bond formation is oxynitnlase (EC 4.1.2.10). This enzyme catalyzes the addition of cyanides to various aldehydes that may come either in the form of hydrogen cyanide or acetone cyanohydrin (152—158) (Fig. 7). The reaction constitutes a convenient route for the preparation of a-hydroxy acids and P-amino alcohols. Acetone cyanohydrin [75-86-5] can also be used as the cyanide carrier, and is considered to be superior since it does not involve hazardous gaseous HCN and also virtually eliminates the spontaneous nonenzymatic reaction. (R)-oxynitrilase accepts aromatic (97a,b), straight- (97c,e), and branched-chain aUphatic aldehydes, converting them to (R)-cyanohydrins in very good yields and high enantiomeric purity (Table 10). 

Use of the valine derived (4S )-3-acetyl-4-isopropyl-1,3-oxazolidine (8)92, the C2-symmetric reagents (2.5,55)-l-acetyl-2,5-bissubstituted pyrrolidine 994, or the doubly deprotonated acetyl urea /V-acetyl- V..V -bis[(.S)-l-phcnylethyl]urea (10), also does not lead to sufficient induced stereoselectivity combined with acceptable chemical yield. When the acetyl urea enolate is reacted with aliphatic and aromatic aldehydes, the diastereomeric adducts (ratios ranging from 1 1 to 3 1) may be separated by column chromatography to give ultimately both enantiomers of the 3-hydroxy acids in 99% ee110. 

Aromatic-aliphatic hydroxy acids, poly esterification of, 81 Aromatic-aliphatic polyesters, 32-35, 83 melting points of, 36 structure and properties of, 44-47 synthesis of, 69-71, 103-106 unsubstituted and methyl-substituted, 36-38... 

The condensation of aromatic aldehydes with anhydrides is called the Perkin reaction When the anhydride has two a hydrogens (as shown), dehydration always occurs the P-hydroxy acid salt is never isolated. In some cases, anhydrides of the form (R2CHC0)20 have been used, and then the hydroxy compound is the product since dehydration cannot take place. The base in the Perkin reaction is nearly always the salt of the acid corresponding to the anhydride. Although the Na and K salts have been most frequently used, higher yields and shorter reaction times have been reported for the Cs salt. Besides aromatic aldehydes, their vinylogs ArCH=CHCHO also give the reaction. Otherwise, the reaction is not suitable for aliphatic aldehydes. ... 

Frequently, it is the bisulfite addition product that is treated with CN. This method is especially useful for aromatic aldehydes, since it avoids competition from the benzoin condensation. If desired, it is possible to hydrolyze the cyanohydrin in situ to the corresponding a-hydroxy acid. This reaction is important in the Kiliani-Fischer method of extending the carbon chain of a sugar. 

Aromatic 2-hydroxy carboxylic acids are of special interest for applications. Among them, optically active mandelic acids are regarded as most important commercially. The synthetic potential of non-racemic 2-hydroxy acids lies in... 

A variant that eliminates the production of water and that has proved effective for esterification of hydroxy and aromatic amino acids involves the use of thionyl chloride instead of acid. At a low temperature, the alcohol reacts with the chloride, generating methyl sulfinyl chloride, which produces the ester, probably through the mixed carboxylic acid-sulfinic acid anhydride (Figure 3.18, B). p-Toluenesulfonyl chloride added to the acid and benzyl alcohol serves the same purpose in the preparation of benzyl esters. 

A combined -cyclodextrin quatemary ammonium salt catalyst promotes the addition of the trichloromethyl anion to aromatic aldehydes and enhances the yield of the a-hydroxy acid [7],... 

Elforts have been made to characterize the nature and content of individual components that are present in the low-molecular-mass fraction of the total mill effluents, which include the spent chlorination and alkali extraction stage liquors [2,4]. Approximately 456 types of compounds have been detected in the conventional bleach effluents, of which 330 are chlorinated organic compounds [22]. The compounds may be lumped into three main groups, namely, acidic, phenolic, and neutral (Table 2). Acidic compounds are further divided into the five categories of acids fatty, resin, hydroxy, dibasic, and aromatic acids. The most important fatty acids are formic and acetic acids. The dominant resin acids are abietic and dehydroabietic acids. Among the hydroxy acids identified, glyceric acid predominates. Dibasic acids such as oxalic, malonic, succinic, and mafic acids are derived from the lignin and carbohydrate fraction... 

This FMN-dependent enzyme [EC 1.1.3.15], also known as (5)-2-hydroxy-acid oxidase, catalyzes the reaction of a (5)-2-hydroxy acid with dioxygen to produce a 2-oxo acid and hydrogen peroxide. The enzyme exists as two major isoenzymes. The A form of the protein preferentially oxidizes short-chain aliphatic hydroxy acids. The B form preferentially oxidizes long-chain and aromatic hydroxy acids. The rat isoenzyme B form also acts as an L-amino-acid oxidase. 

Another notable new advance is the development of hydroxynitrile lyases for the synthesis of enantiomerically active aromatic and aliphatic cyanohydrins. For instance, an S-specific hydroxynitrile lyase has been obtained from Hevea brasiliensis and the resulting fS)-cyanohydrin can be used to obtain both hydroxy acids and aminoalcohols. 

From aryl halide 110 From alcohol 156 Protection 100, 101, 144 Amino acid from hydroxy acid 40 Amphidinolide synthesis 50,94 Anatoxin synthesis 82 Aromatic ring construction 171,191 Aromatic ring substitution 10,18,19,21, 48, 54, 65,69, 104, 108, 110, 111, 120, 122,138, 149, 164, 171, 174, 175, 190,205... 

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