Phenols phosphate derivatives

The effects of glyphosate on phenolic compound production are two-fold 1) accumulation of phenolic compounds that are derivatives of aromatic amino acids is reduced and 2) pools of phenolic compounds derived from constituents of the shikimate pathway prior to 5-enolpyruvylshikimate-3-phosphate become larger. Assays that do not distinguish between effects on these two groups, such as that for hydroxyphenolics of Singleton and Rossi (18), can lead to equivocal and difficult to interpret results (e.g. 3-5). 

Various 1,2-dioxetane derivatives have been synthesized and reported. Among them, AMPPD (Adamantyl Methoxy Phenyl Phosphoryl Dioxetane) is a well known dioxetane bearing a spiroadamantyl group at the 3-position and a phenol phosphate at the 4-position, which is now used for chemiluminescence enzyme immunoassay (CLEIA) using alkaline phosphatase with highly sensitive detection. 

After an extensive study, we realized a new 1,2-dioxetane derivative having a fused furan ring and a bulky substituent, t-butyl group, and a phenol phosphate, 5-t-butyl-... 

Literature proposed CZE methods for phenols and derivatives using test mixtures based on aqueous buffered systems (phosphate-borate and borate " ), volatile electrolytes (ammonium hydrogencarbonate, diethylmalonic acid/dimethylamine in isopropanol and L-cysteic acid, 3-amino-1-propanesulfonic acid, aminomethanesulfonic acid, and diethylmalonic acid ), andnon-aqueous media (ammonium acetate in ACN/acetic acid in MeOH acetate, bromide, chloride, and malonate in ACN and diprotic acids/tetrabutylammonium hydroxide and maleate in MeOH ). 

Cresylic acid n. A term sometimes applied to mixture of 0-, m-, and p-cresol, which are mildly acidic, but also including wider fractions of phenolic compounds derived from coal tar or petroleum that contain xylenols and other higher-boiling phenols in addition to the cresols. It is used in the production of phenolic resins and tricresyl phosphate. 

Phthalates have a strong cost advantage over the competition, and alternatives are used only when phthalates are unsatisfactory. Other plasticisers include the citrates, trimellitates, adipates, sebacates, maleates, gjutarates, palmitates, oleates, stearates, laurates, benzoates, aromatic phosphates, the alkyl sulfonates of phenol, and derivatives of petroleum and of butene. There... 

Alkylated phenol. The most commonly used alkylated phenol ethoxylates (APE) have included octyl phenol ethoxylate and nonylphenol ethoxylates with 3-11 moles of EO, which were produced by alkylation of butylene dimer or propylene trimer onto phenol and subsequent ethoxylation. They had been used extensively in laundry and hard surfacecleaning applications in the nonionic form, and as the sulfated and phosphated derivatives of the low-mole ethoxylates in a variety of industrial applications. Concerns over the environmental impact of the partial metabolites generated during the waste treatment of these surfactants has prompted their elimination from European consumer product formulations, and their deformulation from most consumer products in North America and elsewhere in the world. 

Muscle tissues contain a multi-component antioxidant system consisting of lipid-soluble compounds (a-tocopherol, ubiquinone), water-soluble compounds (ascorbate, histidine-dipeptides) and enzymes (superoxide dismutase, catalase, glutathione peroxidase). Lipid oxidation in meats can be effectively controlled by the use of various phenolic compounds derived from spice extracts, by vitamin E supplementation of animal diets, and by processing of cured meat with sodium nitrite. Various natural antioxidant formulations containing mixtures of tocopherols, ascorbyl palmitate and citric acid show synergistic effects in stabilizing cooked and frozen meat. Synthetic antioxidants, BHA, TBHQ, propyl gallate (see Chapter 9) and combinations with citric acid, ascorbic acid or phosphates are also effective formulations used to retard lipid oxidation in... 

Phenolic compounds derived from a simple unit to a single benzene ring are created from the condensation of erythrose 4-phosphate, an intermediary product of the pentose phosphate cycle, with phosphoenol-pyruvic acid. This biosynthetic pathway, known as the shikimic acid pathway (Figure 10.11), leads to the production of benzoic... 

Triaryl phosphates are produced from the corresponding phenols (usually mixtures) by reaction with phosphoms oxychloride, usually in the presence of a catalyst (94—96). They are subsequently distilled and usually washed with aqueous bases to the desired level of purity. Tricresyl phosphate was originally made from petroleum-derived or coal-tar-derived cresyflc acids, ie, cresols, variously admixed with phenol and xylenols. Discovery of the toxicity of the ortho-cresyl isomers led manufacturers to select cresols having very Httle ortho-isomer. 

Esters of phosphorous acid derived from aUphatic alcohols and unhindered phenols, eg, tris(nonylphenyl)phosphate (24), hydrolyze readily and special care must be taken to minimize decomposition by exposure to water or high humidity. The phosphorous acid formed by hydrolysis is corrosive to processing equipment, particularly at high temperatures. 

The phosphoryl group in phenylphosphate is derived from the -phosphate group of ATP. The free energy of ATP hydrolysis obviously favors the trapping of phenol K, 0.04 mM), even at a low ambient substrate concentration. The reaction is stimulated several fold by another protein, subunit 3 (24kDa). The molecular and catalytic features of phenylphosphate synthase resemble those of phosphoenolpyruvate synthase, albeit with interesting modifications. ... 

The above section already introduced the influence of leaving groups at the benzylic position that eliminate to form and regenerate QM3, and the trend extends beyond adducts formed by the deoxynucleosides as expected. The standard benzylic acetate of QMP4 eliminates completely from the deprotected phenol under neutral aqueous conditions and ambient temperature within approximately 20 h, while an equivalent benzyl bromide eliminates completely within 5 min.48 Benzylic phosphates are also extremely labile, and, if the phosphate backbone of DNA is able to trap QM, the resulting products are likely to be too labile for standard detection.53,54 In contrast, amines and thiols are much less susceptible to elimination from the benzylic position and require forcing conditions to regenerate the parent QM.26,30 The benzylic alcohol derivative also appears stable under almost all thermal conditions and only eliminates routinely to form a QM after photochemical excitation.55... 

Organophosphate Ester Hydraulic Fluids. Organophosphate esters are made by condensing an alcohol (aryl or alkyl) with phosphorus oxychloride in the presence of a metal catalyst (Muir 1984) to produce trialkyl, tri(alkyl/aryl), or triaryl phosphates. For the aryl phosphates, phenol or mixtures of alkylated phenols (e.g., isobutylated phenol, a mixture of several /-butylphenols) are used as the starting alcohols to produce potentially very complex mixtures of organophosphate esters. Some phosphate esters (e.g., tricresyl and trixylyl phosphates) are made from phenolic mixtures such as cresylic acid, which is a complex mixture of many phenolic compounds. The composition of these phenols varies with the source of the cresylic acid, as does the resultant phosphate ester. The phosphate esters manufactured from alkylated phenylated phenols are expected to have less batch-to-batch variations than the cresylic acid derived phosphate esters. The differences in physical properties between different manufacturers of the same phosphate ester are expected to be larger than batch-to-batch variations within one manufacturer. 

CL reaction can be catalyzed by enzymes other than HRP (e.g., microperoxidase and catalase) and by other substances [hemoglobin, cytochrome c, Fe(III), and other metal complexes]. The presence of suitable molecules such as phenols (p-iodophenol), naphthols (l-bromo-2-naphthol), or amines (p-anisidine) increases the light production deriving from the HRP-catalyzed oxidation of luminol and produces glow-type kinetics [6, 7], The use of other enzymes, such as glucose-6-phosphate dehydrogenase [38-41], P-galactosidase [42], and xanthine oxidase [43-46], as CL labels has been reported. 

Fig. 7 Bronsted plot of the log second-order rate constant for La3 + - and 9 Zn2 + ( OCH3)-catalyzed methanolysis of phosphates 20 (including 1) vs. the JpA a values for the corresponding phenols linear regressions through the La3 + and 9 Zn +( OCH3) data (excluding 20b) give gradients of (1.43 0.08) (solid line, ) and —(1.12 0.13) (dashed line, O), respectively. Note that points on lower right for the p-methoxy derivative (20f) are coincident. Reproduced from ref. 17c with permission.

The rate of reaction of phosphorus oxychloride with phenols to produce triaryl phosphates is increased by the addition of quaternary ammonium salts and the reaction temperature can be reduced without loss of overall yield [1,2]. The analogous reaction between phenoxide anions and thiophosphoryl chloride produces aryl phosphoro-dichloridothoates [3]. As with the acylation of enolizable (3-dicarbonyl compounds (3.3.12), phosphorylation leads to the predominant formation of the E-O-phos-phoryiated derivatives [4,5]. 

Fig. 9.8 presents another, more complex type of phosphate prodrugs, namely (phosphoryloxy)methyl carbonates and carbamates (9-26, X = O or NH, resp.) [84], Here, the [(phosphoryloxy)methyl]carbonyl carrier appears quite versatile and of potential interest to prepare prodrugs of alcohols, phenols, and amines. The cascade of reactions leading from prodrug to drug as shown in Fig. 9.8 involves three steps, namely ester hydrolysis, release of formaldehyde, and a final step of carbonate hydrolysis (X = O) or A-decar-boxylation (X = NH). Three model compounds, a secondary alcohol, a primary aliphatic amine, and a primary aromatic amine, were derivatized with the carrier moiety and examined for their rates of breakdown [84], The alcohol, indan-2-ol, yielded a carrier-linked derivative that proved relatively... 

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