ALKYLATION OF ALCOHOLS AND PHENOLS

HMPA 1° alkyl bromide and iodide, PhCH2Cl BSCF 1866 (1965) 

(PhCH2NEt3)Cl allylic bromide, benzylic bromide, 1° alkyl tosylate SL 171 (1994) 

cat (tl-BUaNiHSOa 1° alkyl chloride, benzylic chloride, BiCH2C02R TL 3251 (1975) 28 4143 (1987) 

NaCH2SOCH3, DMSO Mel J Biochem (Tokyo) 55 205 (1964) Biochem 5 1508 (1966) Methods Carbohydr Chem 6 361 (1972) 

AgOTf 3° alkyl chloride 3° alkyl bromide JACS 110 1303 (1988) JACS 110 8591 (1988) 

6-di-terf-butylpyridine or 1,2,2,6,6-pentamethyl-piperidine ROTf (1° alkyl) TL 35 5075 (1994) 

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Alternatively, the Sn2 nucleophilic substitution reaction between alcohols (phenols) and organic halides under basic conditions is the classical Williamson ether synthesis. Recently, it was found that water-soluble calix[n]arenes (n = 4, 6, 8) containing trimethylammonium groups on the upper rim (e.g., calix[4]arene 5.2) were inverse phase-transfer catalysts for alkylation of alcohols and phenols with alkyl halides in aqueous NaOH solution to give the corresponding alkylated products in good-to-high yields.56... 

Alkylations, Methylene chloride can be used for alkylation of alcohols and phenols at 20 in the presence of solid, pulverized KOH and a phase-transfer catalyst. Aliquat 336 is more effective than benzyltriethylammonium chloride. ... 

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