Aryl ethers, cleaving

Allyl aryl ethers are used for allylation under basic conditionsfh], but they can be cleaved under neutral conditions. Formation of the five-membered ring compound 284 based on the cyclization of 283 has been applied to the syntheses of methyl jasmonate (285)[15], and sarkomycin[169]. The trisannulation reagent 286 for steroid synthesis undergoes Pd-catalyzed cyclization and aldol condensation to afford CD rings 287 of steroids with a functionalized 18-methyl group 170]. The 3-vinylcyclopentanonecarboxylate 289, formed from 288, is useful for the synthesis of 18-hydroxyestrone (290)[I7I]. 

Ultraviolet radiation causes cleavage of the aryl ether linkage (23). DMPPO undergoes oxidation when exposed to ultraviolet light and oxygen by direct attack on the aromatic ring to produce a variety of ring-cleaved and quinoidal stmctures (24). 

Me3SiI, CHCI3, 25-50°, 12-140 h. lodotrimethylsilane in quinoline (180°, 70 min) selectively cleaves an aryl methyl group, in 72% yield, in the presence of a methylenedioxy group. Me3SiI cleaves esters more slowly than ethers and cleaves alkyl aryl ethers (48 h, 25°) more slowly than alkyl alkyl ethers (1.3-48 h, 25°), but benzyl, trityl, and /-butyl ethers are cleaved quite rapidly (0.1 h, 25°). ... 

Bromo-9-borabicyclo[3.3.0]nonane (9-Br-BBN), CH2CI2, reflux, 87-100% yield.9-Br-BBN also cleaves dialkyl ethers, allyl aryl ethers, and methylenedioxy groups. 

Methyl aryl ethers, such as anisole, are cleaved to iodomethane and a phen-oxide ion by treatment with Li) in hot DMR Propose a mechanism for this reaction. 

Dialkyl and alkyl aryl ethers can be cleaved with iodotrimethylsilane ROR -bMe3SiI — Rl-bMe3SiOR. A more convenient and less exjjensive alternative, which gives the same products, is a mixture of chlorotrimethylsilane and Nal. Alkyl aryl ethers can also be cleaved with Lil to give alkyl iodides and salts of phenols in a reaction similar to 10-73. Triphenyldibromophosphorane (Ph3PBr2) cleaves dialkyl ethers to give 2mol of alkyl bromide. ... 

The Effect of Phenol. Three types of phenol compounds have been identified in the fractions derived from the product of the phenol ati on reaction (.1,2) alkyl phenols and alkyl-aryl ethers, both formed by combining phenol with alkyl side chains cleaved from the coal molecule, and compounds made up of aromatic fragments attached to phenol by a methylene bridge, formed by... 

In the presence of [BMIM]Br, aryl oxiranes are cleaved by a variety of amines, giving exclusively a regioselective product from benzylic attack. Other epoxides (including glycidyl aryl ethers, glycidyl alkyl ethers, and esters), alkyl oxiranes, and cycloalkyl epoxides are also converted. Remarkably, all the reactions were found to proceed efficiently at ambient temperature with high regioselectivity. The product yields reached 80-90% in a few hours. 

R" may be alkyl or aryl. For dialkyl ethers, the reaction does not end as indicated above, since R OH is rapidly converted to R OR by the sulfonic acid (reaction 0-16), which in turn is further cleaved to R 0S02R" so that the product is a mixture of the two sulfonates. For aryl alkyl ethers, cleavage always takes place to give the phenol, which is not converted to the aryl ether under these conditions. Ethers can also be cleaved in a similar manner by mixed anhydrides of sulfonic and carboxylic acids733 (prepared as in 0-33). p-Hydroxy alkyl perchlorates734 and sulfonates can be obtained from epoxides.735 Epoxides and oxetanes give dinitrates when treated with N2Os,736 e.g.,... 

Selective cleavage of aryI methyl ethers.1 The sodium salt (NaH) of N-melhylaniline in the presence of HMPT cleaves methyl (and benzyl) aryl ethers in... 

Cleavage conditions for alkyl benzyl ethers prepared from acid-labile benzyl alcohols are similar to those for the corresponding benzyl esters (Table 3.30). Aryl benzyl ethers, however, are generally cleaved more easily by acidolysis than esters or alkyl ethers. Phenols etherified with hydroxymethyl polystyrene, for instance, can even be released by treatment with TFA (Entry 1, Table 3.31). It has also been shown that Wang resin derived phenyl ethers are less stable than Wang resin derived esters towards refluxing acetic acid [29]. Alternatively, boron tribromide may be used to cleave aryl ethers from hydroxymethyl polystyrene [573],... 

ArOCH(Rl)OR2 —> ArOH.1 Alkoxymethyl aryl ethers are cleaved by P2I4 in CH2C12 at 25° to phenols in 55-90% yield. This reagent is more useful for cleavage of SEM, MOM, and MEM ethers than Bu4NF, BBr3, or tris(diethylamino)sulfonium difluorotrimethylsilicate (TASF). 

Deprotection of allyl aryl ethers is accomplished by protonolysis with palladium on activated charcoal in methanol solution in the presence of toluene-p-sulphonic acid,42 or by reduction with sodium bis(2-methoxy-ethoxy)aluminium hydride in toluene solution43 (Aldrich). This latter reagent also cleaves aryl benzyl ethers. 

A number of functional group can be converted to phenols, e.g. Sulphonic acids and amino groups which have already been mentioned. Phenyl esters can be hydrolysed (Following fig.). Aryl ethers can be cleaved. The bond between the alkyl group and oxygen is specifically cleaved because the Ar-OH bond is too strong to be cleaved. 

Dialkyl and alkyl aryl ethers are cleaved by Si2I2887, by SiCl/Nal888 or by Me3SiCl/NaI889. The latter afford the functionalized erythro- 1,2-diols via hydroboration of 2-alkyl-4,5-dihydrofurans (equation 129)890. 

Fig. 7-12. Reactions of phenolic /8-aryl ether and a-ether structures (1) during neutral sulfite pulping (Gierer, 1970). R = H, alkyl, or aryl group. The quinone methide intermediate (2) is sulfonated to structure (3). The negative charge of the a-sulfonic acid group facilitates the nucleophilic attack of the sulfite ion, resulting in /8-aryl ether bond cleavage and sulfonation. Structure (4) reacts further with elimination of the sulfonic acid group from a-position to form intermediate (5) which finally after abstraction of proton from /8-position is stabilized to a styrene-/8-sulfonic acid structure (6). Note that only the free phenolic structures are cleaved, whereas the nonphenolic units remain essentially unaffected.

Etherified Phenolic Structures Containing fi-Aryl Ether Bonds In ether-ified p-phenolic structures the/3-aryl ether linkage is cleaved by hydroxide... 

Structures Containing a-Ether Bonds The a-ether bonds in phenolic phenylcoumaran (Fig. 7-27) and pinoresinol structures are readily cleaved by hydroxide ions, usually followed by the release of formaldehyde. Only in the case of open a-aryl ether structures does this reaction result in the fragmentation of lignin. In contrast, the a-ether bonds are stable in all etherified structures. 

Ethers are stable molecules, which do not react with nucleophiles they must be stable because THE and Et20 are used as solvents, But we can make them react by using an acid with a nucleophilic counterion (HBr or HI, for example) and then nucleophilic attack will occur preferentially at the more susceptible carbon atom. Aryl alkyl ethers cleave only on the alkyl side. We shall explain in Chapter 23 why nucleophilic attack does not occur on a benzene ring. 

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