Phenolic acids hydrolysis

Historically, simple Vz-alkyl ethers formed from a phenol and a halide or sulfate were cleaved under rather drastic conditions (e.g., refluxing HBr). New ether protective groups have been developed that are removed under much milder conditions (e.g., via nucleophilic displacement, hydrogenolysis of benzyl ethers, and mild acid hydrolysis of acetal-type ethers) that seldom affect other functional groups in a molecule. 

Dihydrothebainone-A-5 6-methyl enolate, CjaHjjOjN, m.p. 164-165-5°, [a] ° — 115-7° (EtOH). Cold N/HCl converts it into dihydrothebainone hydrochloride. The isomeric dihydrothebainone-J-6 7-methyl enolate is formed on catalytic hydrogenation of phenolic dihydrothebaine. It has m.p. 127-8°, [a] ° — 8° (EtOH) and yields dihydrothebainone on acid hydrolysis. ... 

Acidic hydrolysis of l-(<3-methoxyphenyl)pentafluoropropene gives o-hy-droxy-2,3,3,3-tetrafluoropropiophenone by hydrolysis of vinylic fluonne and cleavage of the ether to the phenol [4] (equation 4). 

Na2C03, H2O, dioxane, warm, 97% yield. Phenols can be protected under similar conditions. Amines are converted by these conditions to carbamates that are stable to alkaline hydrolysis with sodium carbonate. Carbamates are cleaved by acidic hydrolysis (HBr, MeOH, CH2CI2, 8 h), conditions that do not cleave alkyl or aryl vinyl carbonates. 

The hexoses that are the initial products of acid hydrolysis of sucrose (1) react at el vated temperature under the influence of acids to yield furfural derivatives (2). Thed condense, for example, with the phenols to yield triarylmethanes (3), these react furthei by oxidizing to yield colored quinoid derivatives (2, 4). Polyhydric phenols, e. g. resorj cinol, on the other hand, yield condensation products of Types 5 and 6 [2],... 

NUUTILA A M, KAMMioviRTA K and OKSMAN-CALDENTEY K-M (2002) Comparison of methods for the hydrolysis of flavonoids and phenolic acids from onion and spinach for HPLC-analysis, Food Chem, 76, 519-25. 

It was unfortunate that we did not detect any product derived from a diketone in the reaction of w-dimethoxybenzene with tetrafluoroben-zyne. We therefore carried out a reaction of tetrafluorobenzyne with 1,3,5-trimethoxybenzene. The di-enol ether (80) could not be isolated, and after the removal of unreacted 1,3,5-trimethoxybenzene we isolated the phenolic acid (81) in good yield. This compound is undoubtedly formed by the hydrolysis of (80) followed by a retro-Claisen condensation, and aromatisation as shown below. 

RP-HPLC has been employed for the determination of flavonoids and other phenolic compounds in cranberry juice. The neutral and acidic analytes were preconcentrated octadecyl silica SPE cartridges conditioned with distilled water (neutral analytes) or with 0.01 M HC1 (acidic compounds). Hydrolysis of samples was carried out in aqueous methanol solution acidified with 6 M HC1 at 35°C for 16h. Chromatographic separation was performed in an ODS column (150 X 4.6mm i.d. particle size 5/.an). Solvents A and B were water-acetic acid (97 3, v/v) and methanol, respectively. The gradient started with 0 per cent B (flow rate, 0.9 ml/min), reached 10 per cent B in lQmin (flowrate, 1.0 ml/min) and increased to 70 per cent B in 40min (flowrate, 1.0 ml/min). Analytes were detected at 280 and 360 nm. Some typical chromatograms are presented in Fig. 2.71. The concentrations of flavonoids and phenolic acids are compiled in Table 2.69. It was stated that the SPE-HPLC procedure makes possible the simultaneous determination of phenolic compounds and flavonoids, therefore, it can be employed for the measurement of these classes of analytes in other fruit juices [188],... 

More nsnal vegetables were stndied by Nnntila et al. [358] who characterized onions and spinach for the phenolic composition, with and without previous hydrolysis. The authors performed the simultaneous determination of phenolic acids, flavonols, flavones glycosides, and cathechins. Fignre 19.9 reprodnces the separation obtained for the standard mixture in this study. 

The meso-ionic 1,2,3,4-oxatriazoles (286) yield phenol by acidic hydrolysis, phenyl azide by alkaline hydrolysis, and the 5-ethyl 1,2,3,4-oxatriazolium cation with triethyloxonium tetrafluoroborate. The rearrangement 286 -> 288 is achieved with boiling ethanolic ammonia. 

Methylcoumarins bearing hydroxy and other electron-donating groups can be synthesized from the corresponding phenols by reaction with ethyl acetoacetate in the presence of sulfuric acid. Hydrolysis of the ester group in the product then allows the lactone ring of the coumarin to form (Scheme 5.6). 

It seems that overall percentage of absorption, determined by measuring plasma levels of flavonols after enzymatic hydrolysis, does not exceed 2-3% of the ingested dose. It is also likely that, as with other micronutrients, the existence of a steady-state concentration of these compounds could result in diminished absorption. Thus, it is conceivable that the major parts of these flavonoids are either degraded to phenolic acids in the large intestine or excreted in the faeces [72]. 

Dimethoxyfuran is readily available from the enolic dimethyl 3,4-dihydroxyfuran-2,5-dicarboxylate. This intermediate, like a phenol, can be readily O-methylated or O-benzy-lated. Hydrolysis and decarboxylation then furnishes the 3,4-dialkoxy compounds (78HCA430). The dimethoxy compound readily enters into Diels-Alder reactions, the Man-nich reaction, and may be lithiated. On mild acid hydrolysis it supplies, in poor yield, 4-methoxyfuran-3(2/f)-one and not tetrahydrofuran-3,4-dione, which is not produced by attempted hydrogenolysis of 3,4-dibenzyloxyfuran either. The dione, however, is known, and surprisingly exists in the diketo form (60JA3219). 

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