ALCOHOLS, PHENOLS, ETHERS, THIOLS, AND THIOETHERS

For all of these related compounds (alcohols, enols, phenols, ethers, thiols, and thioethers), some properties of which are provided in Table 8.3, it might also be anticipated that the nonbonding electrons (Chapter 1) on oxygen or sulfur could participate in reactions occurring elsewhere in the organic framework, and, indeed, it is common to find that processes taking place remote to the heteroatom are also affected by its presence. 

TABLE 8.3. Some Representative Examples of (a) Alcohols and Phenols, (h) Ethers, and (c) Thiols and Thioethers ... 

Sulfur-containing compounds (thiols and sulfides) are easily recognized from the M -h 2 isotopic peak each sulfur contributes 4.4% to the abundance of the M -I- 2 ion. The fragmentation patterns of thiols (mercaptans) and sulfides (thioethers) parallel the corresponding alcohols and ethers. For example, similar to the alcohol series at m/z 31,45, 59,..., the a-cleavage in thiols produces a series of ions at m/z 47, 61, 75, 89,..., and each ion has a satellite peak 2 u higher, due to In addition, thiols exhibit a characteristic loss of H2S, followed by the elimination of alkene moieties to produce peaks at (M — 34)+, (M — 34 — 2114)+, and so on. In contrast, secondary thiols show a characteristic peak at (M — SH)+. Aromatic thiols also behave similarly to phenols under El conditions. In addition, they show ions at (M — S)+, (M — SH)+, and (M — 2114)+. ... 

This reaction is analogous to 10-7. It may be acid (including Lewis acids ), base, or alumina catalyzed, occur with electrolysis, and may occur by either an SnI or 8 2 mechanism. Catalysts, such as [Rh(CO)2Cl]2, TiCla (OTf), Fe(C104)3, Cu(BF4)2 m H2O, or BiCla, have been used. (3-Cyclodextrin has been used to promote the reaction with phenoxides in aqueous media. Many of the p-hydroxy ethers produced in this way are valuable solvents, for example, diethylene glycol and Cellosolve. Reaction with thiols leads to hydroxy thioethers. The reaction of alcohols with aziridines leads to p-amino ethers, and reaction with thiols gives p-amino thioethers. " It has been shown that ringopening of aziridines by phenols is promoted by tributylphosphine. ... 

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