Phenoxy halogenation

The halogen displacement polymerization proceeds by a combination of the redistribution steps described for oxidative coupling polymerization and a sequence in which a phenoxide ion couples with a phenoxy radical (eq. 11) and then expels a bromide ion. The resultant phenoxy radical can couple with another phenoxide in a manner that is analogous to equation 11 or it can redistribute with other aryloxy radicals in a process analogous to equations 7 and 8. 

Properties and Applieations. Aryloxyphosphazene elastomers using phenoxy and J-ethylphenoxy substituents have found interest in a number of appHcations involving fire safety. This elastomer has a limiting oxygen index of 28 and contains essentially no halogens. It may be cured using either peroxide or sulfur. Peroxide cures do not require the allyhc cute monomer. Gum physical properties are as follows (17) ... 

Mono-substitution occurs most readily in the stepwise replacement of the halogen substituents of 2,4,6-trichloro-s-triazine with aqueous methanol and sodium bicarbonate (30°, 30 min), the monomethoxy derivative (324) is obtained on heating (65°, 30 min), the disubstitu-ted derivative is formed and on brief heating (65°) with the more basic sodium carbonate or methanolic sodium hydroxide (25°, 3 hr) complete methoxylation (320) occurs. Ethanolic ethoxide (25°, 1 hr) or sodium carbonate (35°) is sufficient to give complete ethoxy-dechlorination. The corresponding phenoxy derivatives are obtained on treatment with one (0°), two (15°, 1 hr), or three equivalents (25-70°, 3 hr) of various sodium phenoxides in aqueous acetone. The stepwise reaction with phenols, alcohols, or thiols proceeds in better yield in organic solvents (acetone or chloroform) with collidine or 2,6-lutidine as acid acceptors than in aqueous sodium bicarbonate. ... 

If we consider the LOI values reported in Table 8, it can be clearly seen that the flame resistance of polyphosphazenes is very high and can reach values above 60 when halogenated phenoxy groups (e.g. 4-bromophenoxy) are attached to the polymer chain. However, enhancement of the carbon content in the materials (i.e. by increasing the percentage of organic substituents in the chain) induces a concurrent decrease in the flame resistance of POPs, which can be depressed to 23.4 in the case of poly[bis(4-/sopropylphenoxy)phos-phazene]. 

Chau and Terry [146] reported the formation of penta-fluorobenzyl derivatives of ten herbicidal acids including 4-chloro-2-methyl-phenoxy acetic acid [145]. They found that 5h was an optimum reaction time at room temperature with pentafluorobenzyl bromide in the presence of potassium carbonate solution. Agemian and Chau [147] studied the residue analysis of 4-chloro-2-methyl phenoxy acetic acid and 4-chloro-2-methyl phenoxy butyric acid from water samples by making the pentafluorobenzyl derivatives. Bromination [148], nitrification [149] and esterification with halogenated alcohol [145] have also been used to study the residue analysis of 4-chloro-2-methyl phenoxy acetic acid and 4-chloro-2-methyl phenoxybutyric acid. Recently pentafluorobenzyl derivatives of phenols and carboxylic acids were prepared for detection by electron capture at very low levels [150, 151]. Pentafluorobenzyl bromide has also been used for the analytical determination of organophosphorus pesticides [152],... 

Rearrangements are less likely when the allene to be formed is highly substituted with either phenoxy [23a], aryl, or halogen groups [23b, 24]. For example,... 

HYDROGEN, HALOGEN, ALKYL, PHENOXY, ARALKYL, -CH2 -C6H4-0 -C6H5... 

Aminative replacement in compounds other than those bearing halogen atoms are uncommon, but 6-aminophenanthridine is easily prepared by heating 6-phenoxyphenanthridine with urea296 and 6-anilinophenanthridine has been obtained by the action of aniline on the 6-phenoxy compound.268 The formation of 6-anilinophenanthridine from phenanthridine iV-oxide and phenyl isocyanate probably proceeds via an initial 1,3-dipolar addition, followed by nucleophilic substitution and decarboxylation (Scheme 4).309... 

Quinclorac heterocyclic nitrogen, quinoline Quinmerac heterocyclic nitrogen, quinoline Quinoclamine quinone Quinomethionate see Chinomethionat Quintozene halogenated aromatic Quizalofop phenoxy carboxylic acid, quinoxaline... 

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