Fluorinated Phenols

Hydrofluoric acid selenic acid Alkyl phenols Fluorine chlorine bromine ... 

Ammonia, sodium, calcium sulfides and sulfates, chlorine, phenols, fluorine, water treatment chemicals, trace elements... 

Depending on the ring substituent, trifluoromethoxyben2enes can be made by the sequential chlorination—fluorination of anisole(s) (351—354). A one-step process with commercial potential is the BF (or SbF2)-cataly2ed reaction of phenol with carbon tetrachloride/hydrogen fluoride (355). Aryl trifluoromethyl ethers, which may not be accessible by the above routes,may be made by fluorination of aryl fluoroformates or aryl chlorothioformates with sulfur tetrafluoride (348) or molybdenum hexafluoride (356). 

Miller et al. [9] hypothesized rules on the regioselectivity of addition from the study of the base-catalyzed addition of alcohols to chlorotnfluoroethylene. Attack occurs at the vinylic carbon with most fluorines. Thus, isomers of dichloro-hexafl uorobutene react with methanol and phenol to give the corresponding saturated and vinylic ethers The nucleophiles exclusively attack position 3 of 1,1-dichloro-l,2,3,4,4,4-hexafluoro-2-butene and position I of 4,4-dichloro-l,l,2,3,3,4-hexafluoro-1-butene [10]. In I, l-dichloro-2,3,3,4,4,4-hexafluoro-l-butene, attack on position 2 is favored [J/] (equation 5) Terminal fluoroolefms are almost invariably attacked at tbe difluoromethylene group, as illustrated by the reaction of sodium methoxide with perfluoro-1-heptene in methanol [/2J (equation 6). 

M - 2 Aromatic isocyanates Aromatic phenols Certain butenols Certain fluorinated amines e.g., C8F17CH2CHICH2NH2 or CF3(CF2)7CH2CH2CH2NH2 Possible Precursor Compounds Polynuclear aromatics (e.g., dihydroxyphenanthrene) Ethylsilanes (dimers to heptamers)... 

Zone 4 alkyd, fluorinated ethylene-propylene, melamine-formaldehyde, phenol-furfural, and polysulfone. 

The limitations of the system with regard to substrates and oxidants was attributed to the strong electron-withdrawing character of the perfluorinated chains and the lower steric hindrance in the position adjacent to phenols, in marked contrast to the ferf-butyl groups present in Jacobsen s catalyst, hi view of this, a second generation of fluorinated salen ligands le and If was... 

Fluorinated phenols, 3- and 4-fiuorophenols, and 2,6-difluorophenol, were subjected to peroxidase-catalyzed polymerization in an aqueous organic solvent, yielding fluorine-containing polymers. Elimination of fluorine atom partly took place during the polymerization to give polymers with complicated structures. 

Since the aerobic degradation of halogenated phenols takes place by monooxygenation and is discussed in Part 2 of this chapter, it is not discussed here except to note the production of chlorocat-echols from chlorophenols and chloroanilines. Emphasis is placed on chlorinated substrates, and reference may be made to a review (Allard and Neilson 2003) for details of their brominated and iodinated analogs. The degradation of aromatic fluorinated compounds is discussed in Part 3 of this chapter. 

The aerobic degradation of phenols is initiated by monooxidation with the production of catechols that undergo ring fission. A nnmber of stndies have used various strains of Rhodococcus sp. and Mycobacterium sp. to examine the metabolism of fluorinated phenols, and have illustrated important alternatives ... 

The metabolism of fluorinated phenols has been examined quite extensively in yeasts ... 

The metabolism of a range of fluorophenols containing up to five fluorine substituents was examined using phenol hydroxylase from Trichosporon cutaneum (Peelen et al. 1995). Fluorocatechols were formed, with loss of fluoride for some substrates. 

Fluorinated Muconates Formed from Fluorophenols by Phenol Hydroxylase and Catechol 1,2-Dioxygenase from Exophilia jeanselmei Fluoromuconate Metabolite Phenolic Substrate(s)... 

Genther BRS, GT Townsend, PJ Chapman (1990) Effect of fluorinated analogues of phenol and hydroxyben-zoates on the anaerobic transformation of phenol to benzoate. Biodegradation 1 65-74. 

Phenolic antioxidants in rubber extracts were determined indirectly photometrically after reaction with Fe(III) salts which form a red Fe(II)-dipyridyl compound. The method was applicable to Vulkanox BKF and Vulkanox KB [52]. Similarly, aromatic amines (Vulkanox PBN, 4020, DDA, 4010 NA) were determined photometrically after coupling with Echtrotsalz GG (4-nitrobenzdiazonium fluoroborate). For qualitative analysis of vulcanisation accelerators in extracts of rubbers and elastomers colour reactions with dithio-carbamates (for Vulkacit P, ZP, L, LDA, LDB, WL), thiuram derivatives (for Vulkacit I), zinc 2-mercaptobenzthiazol (for Vulkacit ZM, DM, F, AZ, CZ, MOZ, DZ) and hexamethylene tetramine (for Vulkacit H30), were mentioned as well as PC and TLC analyses (according to DIN 53622) followed by IR identification [52]. 8-Hydroquinoline extraction of interference ions and alizarin-La3+ complexation were utilised for the spectrophotometric determination of fluorine in silica used as an antistatic agent in PE [74], Also Polygard (trisnonylphenylphosphite) in styrene-butadienes has been determined by colorimetric methods [75,76], Most procedures are fairly dated for more detailed descriptions see references [25,42,44],... 

The balance of the compounds in Table VIII support the earlier statement that any compound containing fluorine is toxic to moths. These fluorinated hydrocarbons, phenols, acids, sulfonic acids, and sulfones probably act against moths as stomach poisons. The fluorosulfonic acid derivatives and the sulfone with a fluorinated substituent were key compounds whose toxicity to moths laid the groundwork for the deductions which led to the synthesis and testing of DDT as an insecticide. 

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