Phenols from hydroxy acids

How would you prepare the following compounds from the named starting material (a) l-methoxy-.Vnitrobcnzcne from ben-zenesulfonic acid (b) methyl 2-hydroxy benzoate from phenol (c) 2-bromo-4-methvlphcnol from toluene. 

Materials 3-Hydroxy-, 3,5-dihydroxy, 3-amino- and 3,5-diaminobenzoic acid were gifts of BAYER AG (Leverkusen, FRG) and used without further purification. Bisphenol-P and bisaniline-P were purchased from Kennedy and Klim (Little Silver, N.J., USA). Piperazine, l,l,l-tris(4 -hydroxy-phenyl)ethane, phloretic acid tetrahydroxy spirobisindane were purchased from Aldrich Co. (Milwaukee, Wise., USA). All hydroxy acids and phenols were acetylated with an excess of acetic acid and a catalytic amount of pyridine in refluxing toluene. All silylations were conducted with chloro-trimethylsilane and triethylamine in refluxing toluene or dioxane. 

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... 

Raspberry ketone is prepared by alkali-catalyzed condensation of the alkali salt of 4-hydroxybenzaldehyde and acetone, followed by selective hydrogenation of the double bond in the resulting 4-hydroxybenzalacetone. Other syntheses start from phenol which is converted into 4-(4-hydroxyphenyl)-2-butanone with methyl vinyl ketone (e.g., in the presence of phosphoric acid) [179] or with 4-hydroxy-2-butanone in the presence of concentrated sulfuric acid [180]. 

The reaction of 2,2-dimethyl-4,6-dioxo-l,3-dioxane (Meldrum s acid 394) and its analogues with 3-dialkylaminophenols has been used to prepare some fluorescent 7-dialkylamino-4-hydroxycoumarins (Scheme 127) (77M499). The substituted malonic acid (395) or its dehydration product is a possible intermediate, since it is known that diaryl-malonic esters are accessible from phenols and the 1,3-dioxane. 3-Methoxyphenol yields the pyrano[3,2-c]benzopyran-2,5-dione (396) in this reaction, presumably by annelation of another ring on to initially formed 4-hydroxy-7-methoxycoumarin. 

Di-aldehydes can be obtained from some polyhydric phenols. Phenolic-ethers also react, as do hydroxy-aldehydes and hydroxy-acids. 

---