Chlorinated phenyl ethers

Synonyms Chlorinated phenyl ethers mono-chlorodiphenyl oxide, dichlorodiphenyl oxide, etc., through hexachlorodiphenyl oxide... 

The different reactivity of both carbon-chlorine and carbon-oxygen bonds toward arene-catalyzed lithiation (see Scheme 129) was applied to 3-chloropropyl phenyl ether... 

Thus 4-chlorophenyl 2,4,5-trichlorophenyl ether (48, Scheme 7) produced 4% of a mixture of the dibenzofurans 49 and 50. Only in the case of 2,3,4-trichlorophenyl 2,3,4,5,6-pentai hlorophenyl ether was production of dibenzofurans by formal loss of o,o -chlorine detected. Neither product was identified, but one is presumably the expected product, 1,2,3,4,8,9-hexachloro-dibenzofuran, and the other must be due to a rearrangement. Chlorination of diphenyl ether in the gas phase is unusual. At 300°C the major product is 4-chlorophenyl phenyl ether, as in the liquid phase, but as the temperature is increased (400-500°C), the amount of 4-chlorophenyl phenyl ether decreases at the expense of 3-chlorophenyl phenyl ether, and dibenzofuran is also produced. ... 

The role of polychlorinated gem-dichlorocyclohexadienones as reaction intermediates which can then produce desired me/a-chlorinated products or imdesired coupled products has been described.17 Chlorination of phenol and sometimes the ether complicates the hydrolysis of some primary alkyl phenyl ethers in concentrated aqueous perchloric acid solution.18 Unexpected chlorination has also been established in the reaction of 2-amino-5-chlorobenzophenone with HC1 in aqueous methanol (1 1 v/v), 2-amino-3,5-dichlorobenzophenone being amongst the products.19... 

The phenyl ether formation is always one of the last steps of the synthesis, the benzene rings being first subjected to nitration, chlorination, carboxylation, etc. 

Halo ethers are prepared by adding an alcoholic solution of the sodium alkoxide to the polymethylene halide, X(CHj) X, in anhydrous ether or benzene, as illustrated by the preparation of l-bromo-6-methoxyhexane (47%). In a somewhat different manner, an aromatic halo ether such as y-phenoxypropyl bromide is synthesized by the action of phenol and the dihalide in the presence of hot aqueous sodium hydroxide (85%). The syntheses of o- and p-chlorophenyl phenyl ethers have been successfully accomplished by the Ullmann procedure (40-55%), whereas chlorination of diphenyl ether yields an inseparable mixture of isomers. ... 

SYNONYMS benzene, l,l -oxybis, hexachloro, chlorinated diphenyl ether, hexaclorodi-phenyl ether, hexachlorodiphenyl oxide, hexachlorophenyl ether, trichlorodiphenyl ether, tri-chlorodiphenyl oxide. 

Electrophilic Aromatic Substitution. Micellar SDS has been used as a reaction medium for the chlorination and bromlnatlon of alkyl phenyl ethers T gjj(j phenol by several halogenatlng agents (eq 1). Compared to reactions in H2O alone, theparar.ortho product ratio increased for pentyl, nonyl, and dodecyl phenyl ether, and decreased for anlsole. Enhanced ortho relative to para substitution was obtained with phenol. In each case the observed regios-electivity derived at least in part from alignment of the substrate at the micelle-H20 interface and resultant differential steiic shielding of the para and ortho positions by the micelle superstructure. 

In BLM transport, the most common solvents are chlorinated hydrocarbons. These have low dielectric constants and, as a consequence, the transport is described by ion-pairs. Izatt et al. have extensively studied ion-pair transport through BLMs (18), In SLM transport, cyclohexyl phenyl ether is an important non-polar membrane solvent (19). The extraction equilibrium at the interface in a non-polar membrane... 

PMR spectroscopy has been applied to the characterisation of a wide range of homopolymers including PMMA [286-289], PVC [290-294], PS [293, 295, 296], polyvinyl ethers [297-300], polyacrylic acid [301], poly(methyl-a-chloroacrylate) [302], carboxy terminated polybutadiene [303], poly(a-methyl styrene) [304], natural rubber [305-307], chlorinated polyisobutylenes [308], sulfonated PS resins [309, 310], polyvinyl phenyl ether [311], lactone polyester [312], chlorinated PVC [313], PC [314], poly 1,3 butadiene [315], poly-2-allyl phenyl acrylate [316], poly(4-methyl-pentene-1) [317], polymethacrylic acid [318], PP [296], cyclic ethers [319], polymethacrylonitrile [320], poly(a-methyl styrene) tetramer [321], PEG [322], PE [289], polyacrylamide [311], polymethylacrylamide [323], polypyrrolidone [324], polychloroprene [325], phenol formaldehyde resins [326, 327], Nylon 66 [328], polyvinylidene fluoride [329], polyvinyl formate [330], polyacrylonitrile [331], epoxy resins [332], allyl biguanide [333], poly(2-isopropyl-2-oxazollines) [334] and trehalose vinyl benzyl ether [335]. 

Some typical results are shown in Table 1. Polymers are soluble in organic solvents such as benzene, toluene, THF and chlorinated hydrocarbons. The IR spectrum of these polymers displays characteristic absorption bands at 1640 cm (C=C stretching), 1600 and 1500 cm"l (phenyl ring vibrations), 1235 cm" (phenyl ether stretching) and 1015 cm (aliphatic ether stretching). The NMR spectrum of these polyethers recorded in CDCl at room temperature exhibits multiplets between 7.20 and 6.67 ppm (aromatic protons) and peaks at 6.02 ppm (-CH=CH-), at 4.50 ppm (-CH -0) and 1.60 ppm (-CH ). A small peak is observed at 4.05 ppm which can be attributed to the protons of the chloromethyl end groups. This peak is absent in the spectrum of sample 6 (Table 1). 

Anisole (methyl phenyl ether) is extremely reactive towards sulfonation due to the presence of the strongly electron-donating (-fM) methoxy group. It therefore reacts with chlorosulfonic acid (two equivalents) at 0 °C to give mainly p-methoxybenzenesulfonyl chloride. With chlorobenzene, the chlorine atom exerts a strong electron-withdrawing (-1 effect) so sulfonation will be rather less easy than for benzene. Treatment of chlorobenzene with chlorosulfonic acid (four equivalents) at 25 C (3 hours) afforded p-chlorobenzenesulfonyl chloride (84%) and di(/7-chlorophenyl sulfone) (6%)." Chlorobenzene with chlorosulfonic acid (six equivalents) at 150-160 °C (8 hours) gave the 2,4-disulfonyl chloride. 

Chlorine Ammonia, acetylene, alcohols, alkanes, benzene, butadiene, carbon disulflde, dibutyl phthalate, ethers, fluorine, glycerol, hydrocarbons, hydrogen, sodium carbide, flnely divided metals, metal acetylides and carbides, nitrogen compounds, nonmetals, nonmetal hydrides, phosphorus compounds, polychlorobi-phenyl, silicones, steel, sulfldes, synthetic rubber, turpentine... 

This dialkoxydiphenylsulfurane has been prepared by the reaction of diphenyl sulfide, 2,2,2-trifluoro-l-phenyl-l-(trifluoromethyl)ethyl hypochlorite, and potassium l,l,l,3,3,3-hexafluoro-2-phenyl-2-propanolate and by the reaction of diphenyl sulfide with 1 equivalent of chlorine and 2 equivalents of potassium 1,1,1,3,3,3-hexafluoro-2-phenyl-2-propanolate in diethyl ether. ... 

L-Pkenylalanine, reaction with phthalic anhydride to yield N-phthalyl-L-phenylalanine, 40,82 Phenyl terf-BUTYL ether, 41, 91 a-Phenylethylamine, N-chlorination of, 41,82... 

The complexes are soluble in aromatic solvents and in THF. The tri-p-tolyl-phosphine complex has limited solubility in ether, and the tri-phenyl phosphine complex is insoluble in diethyl ether. Both complexes are insoluble in hexane and related solvents and decompose in chlorinated solvents. Limited solubility is achieved inA jV-dimethylformamide, but moderate decomposition occurs. 

The epoxy alcohol 47 is a squalene oxide analog that has been used to examine substrate specificity in enzymatic cyclizations by baker s yeast [85], The epoxy alcohol 48 provided an optically active intermediate used in the synthesis of 3,6-epoxyauraptene and marmine [86], and epoxy alcohol 49 served as an intermediate in the synthesis of the antibiotic virantmycin [87], In the synthesis of the three stilbene oxides 50, 51, and 52, the presence of an o-chloro group in the 2-phenyl ring resulted in a lower enantiomeric purity (70% ee) when compared with the analogs without this chlorine substituent [88a]. The very efficient (80% yield, 96% ee) formation of 52a by asymmetric epoxidation of the allylic alcohol precursor offers a synthetic entry to optically active 11 -deoxyanthracyclinones [88b], whereas epoxy alcohol 52b is one of several examples of asymmetric epoxidation used in the synthesis of brevitoxin precursors [88c]. Diastereomeric epoxy alcohols 54 and 55 are obtained in combined 90% yield (>95% ee each) from epoxidation of the racemic alcohol 53 [89], Diastereomeric epoxy alcohols, 57 and 58, also are obtained with high enantiomeric purity in the epoxidation of 56 [44]. The epoxy alcohol obtained from substrate 59 undergoes further intramolecular cyclization with stereospecific formation of the cyclic ether 60 [90]. 

---