Chloromethylmethyl ether (CME) and bis-chloromethyl ether (BCME) are very convenient and efficient chloromethylating reagents, yet they are listed as carcirogens.' BCME is more notorious than CME. Consequently, several attempts have been made to synthesize CME free of BCME,, or iodomethyl-methyl ether free of BCME,3 or to introduce alternative reagents such as methylal/chlorosulfonic acid,4 or to generate incipient halomethyl furonium ion from l-chloro-4-chloro-(bromo)methoxy butane and 1,4-bis-[chloro(bromo)methoxy b~t a n e ] . "~ Short-chain chloromethyl-alkyl ethers were studied in the alkylation of aromatic compounds, but not as chloromethylating reagent^.^ Long chain chloromethylalkyl ethersgJO were described as intermediates on the way to cationic surfactants'J2 or alkoxymethyl sucrose surf act ant^.'^ No attention was given to their use as halomethylating agents or to the generation of BCME during their preparation.
RESULTSWe wish14 to report the BCME-free synthesis of long chain halomethylalkyl ethers, ROCH,X, and their application in halomethylation of aromatic substrates and polymers, according to the following reactions: