Diphenyl Ether and Derivatives

4 -Di(acylamido) diphenyl ethers are similarly chlorosulfonated by treatment with excess reagent in cold carbon tetrachloride thus 4,4 -diacetamidodiphenyl ether afforded the 3,3 -disulfonyl chloride (85%).  

2 -Chloro- and 2, 6 -dichloro-4-nitrodiphenyl ethers were converted into the corresponding 4 -sulfonyl chlorides by reaction with excess chlorosulfonic acid (five equivalents). The comparatively poor yields of the sulfonyl chlorides obtained may be due to their susceptibility towards hydrolysis, as a result of the presence of the electron-withdrawing groups. Several sulfonyl derivatives of diphenyl ethers, e.g. azides, hydrazides and hydrazones showed pronounced algaecidal activity. 

When diphenyl ether 206 was treated with a very large excess of chlorosulfonic acid (20 equivalents) at room temperature (4 weeks), a low yield (15%) of the 2,4,4 -trisulfonyl chloride 207 was isolated.  

When the same reaction mixture was heated at 100 °C (4 hours), a much improved yield of the trisulfonyl chloride 207 (82%) was obtained. Even more drastic conditions, namely heating the mixture at 150 C for 4 hours, afforded a mixture of phenoxathiin-10,10-dioxa-2,8-disulfonyl chloride 208 and the corresponding 2,4,8-trisulfonyl chloride 209 (Equation 66). 

The cyclization of diphenyl ether 206 to the cyclic sulfone derivatives 208 and 209 achieved by prolonged heating with a large excess of the reagent is analogous to similar reactions observed with biphenyl and the diphenyl alkanes (see Section 2, pp 42 and 40). 4-Bromodiphenyl ether by treatment with excess chlorosulfonic acid (two equivalents) at 25-30 °C afforded the 4-sulfonyl chloride (45%). In this molecule, the other reactive 4-position is blocked by the bromine atom. In contrast, with diphenyl ether 206 all attempts to obtain the monosulfonyl chloride by reaction with chlorosulfonic acid failed, and the only isolated product was the 4,4 -disulfonyl chloride. In the case of 4,4 -dibromodiphenyl ether, in which 

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Schmidt S, R-M Wittich, D Erdmann, H Wilkes, W Erancke, P Eortnagel (1992) Biodegradation of diphenyl ether and its monohalogenated derivatives by Sphingomonas sp. strain SS3. Appl Environ Microbiol 58 2744-2750. 

RhCl(PPh3)3] (23) and [RhCl(CO)(PPh3)2] (71) catalyze the formation of enol silyl ethers and derivatives according to equation (86). Both the (E) and (Z) isomers of the product are obtained.4353 The dinuclear complex [Rh2Cl2(CO)4] (96) catalyzes the reaction of phenylacetylene with carbon monoxide to give 3,6-diphenyl-l-oxabicyclo-[3.3.0]-octa-3,6-diene-2,4-dione (97) (equation 87).435b... 

Commission Recommendation of 16 September 2002 on the results of the risk evaluation and the risk reduction strategy for the substance diphenyl ether, octabromo derivative (notified under document number C(2002) 3394) (Text with EEA relevance) (2002/755/EC), Official Journal, EC, 2002, No.L.249. 

Gevao, B., Al-Omair, A., Sweetman, A., Al-Bahloul, M., Al-Ali, L., Helaleh, M., et al. Passive-sampler derived air concentrations for polybrominated diphenyl ethers and polycyclic aromatic hydrocarbons in Kuwait. Environmental Toxicology and Chemistry, 25(6) 1496-1502 (2006). 

Ethers. The polycondensation of diphenyl ether and furfural (1 1.5mole ratio) in presence of sulfuric acid yields a resin which has been sulfonated by sulfuric acid at 50 °C for 10 h to give a cation-exchange resin The swelling and the exchange capacity of the product increase with the amount of sulfuric acid present during the polycondensation and are higher for a resin obtained by polycondensation in carbon tetrachloride than the one prepared in absence of solvent. The thermal stability of sulfonated diphenyl ether-furfural resin is more than that of KU-1 and comparable to that of KU-2. The sulfonic acid resin derived from the copolymer obtained by the polymerization of diphenyl ether and furfural at a mole ratio of 1 2 in carbon tetrachloride has optimum adsorption and catalytic activity... 

In terms of modified operational procedures for the transformation, in their route to (-)-kainic acid, Ogasawara and co-workers performed a tandem Chugaev elimination-intramolecular ene reaction and found sodium hydrogen carbonate to be a beneficial additive.27 Derivative 35 was heated in refluxing diphenyl ether and in the presence of sodium hydrogen carbonate. This furnished tricyclic system 36, which was converted to (-)-kainic acid. They later extended this procedure for the synthesis of the acromelic acids.28... 

Typical of this work is the rearrangement of phenyl p-toluenesulphonate into 2-hydroxyphenyl and 4-hydroxyphenyl p-tolyl sulphones274. Ogata and coworkers275 have shown that phenyl benzenesulphonate also rearranges on irradiation in ethanol and yields both 2-hydroxyphenyl and 4-hydroxyphenyl phenyl sulphones as well as phenol, small amounts of diphenyl ether and polymer. Interestingly, the tolyl derivative 305 does not rearrange and only o- and p-cresol are isolated. Irradiation (330 nm) of the sulphonates 306 in ethyl acetate affords the hydroxysulphones 307 in 66% yield. The reaction of 306 also... 

The radical anion derived from 2-cyanodiphenyl ether underwent reversible dimerization resulting in a dianion relatively resistant towards further chemical reaction. The products observed after electrolysis were mainly phenol, diphenyl ether and 2, 4-dicyano-3-phenoxy biphenyl. The structure of the isolated biphenyl suggested that the radical anion dimerization had occurred via 2-4 coupling. 

Fig. 117. Temperature-concentration diagram for the system HDPEl-diphenyl ether, as derived from DSC and optical cloud point measurements (V) onset of crystallisation (A) end of melting en-dotherm (O) optical doud point. Reproduced from Makromol Chem [Ref. 328] by the courtesy of the authors and of Huthig We Verlag PuWshers, Zug, Switzerland...

Huntress and Carten studied the action of chlorosulfonic acid on 42 aromatic ethers in order to determine the utility of the reagent for the characterization of aromatic ethers, 36 of the ethers were converted into their monosulfonyl chlorides and these were subsequently reacted with anmionium hydroxide to give the corresponding sulfonamides which were well-defined crystalline solids with sharp melting points suitable for identification of the original aryl ether. Six of the ethers examined failed to yield satisfactory monosulfonyl chlorides namely o-and />-methoxybiphenyl, diphenyl ether and the 4,4 -dibromo derivative as well as methyl and ethyl benzyl ethers. 

European Union (2003a) European Union risk assessment report diphenyl ether, octabromo derivative. CAS No 32536-52-0, EINECS No 251-087-9. http //echa.europa.eu/documents/ 10162/5bl0aa46-9a88-4aed-b338-le06105b924c. Accessed 15 Dec 2012 European Union (2003b) European Commission 2003 WEEE 2002/96/EC (2003) Directive 2002/ 96/EC of the European Parliament and of the Council of January 27, 2003 on waste electrical... 

When the methine base derived from trilobamine diethyl ether ethiodide is oxidised by permanganate it furnishes 2-ethoxydiphenyl ether 5 4 -dicarboxylie acid, identical with that (XXXIV p. 348, R = Et) similarly formed from oxyacanthine (p. 347) or dauricine (p. 353) and in the present case derived from the diphenyl ether residue represented by rings (1) and (2) in formula (A) or (B). This fixes the position of one hydroxyl group at OR in (A) or (B) the position of the second is still undetermined but it may well be OR in ring (3) of (A) or ring (4) of (B). ... 

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