由萘酚及2,3,5-三甲基酚合成新型雙烯類化合物

本論文敘述以萘酚為起始物分別合成1-allyloxy-2-(2- methylallyl)naphthalene以及1-allyloxy-2-(2-phenylallyl)naphthalene 等分子內双烯類化合物，另一方面以2,3,5-三甲基酚分別合成3-allyloxy-1,2,5-trimethyl-4-(2-methylallyl)benzene以及3-allyloxy- 1,2,5-trimethyl-4-(2-phenylallyl)benzene等分子內双烯類化合物。將萘酚及三甲基酚溶於丙酮中，分別與1-chloroacetone及2-bromoacetophenone在K2CO3存在下迴流進行SN2取代反應。所得到的酮類化合物分別與methylenetriphenylphosphoran(由methyltri- phenylphosphine bromide與pot. tert-butoxide在THF中製得)作用，進行Wittig反應將酮基轉變為烯類化合物。將所得到的烯類化合物分別進行Claisen轉位，而分別得到鄰位有丙烯基取代的萘酚以及三甲基酚。接著將得到的酚類化合物與allyl bromide反應進行O-allylation而分別得到預期產物。

關鍵字

?酚；新型雙烯類； 2 ； 3 ； 5-三甲基酚

並列摘要

In this master thesis the synthesis of 1-allyloxy-2-(2-methylallyl)- naphthalene and 1-allyloxy-2-(2-phenylallyl)naphthalene from naphthol is described. On the other hand，synthesis of 3-allyloxy-1,2,5-trimethyl-4-(2- methylallyl)benzene and 3-allyloxy-1,2,5-trimethyl-4-(2-phenylallyl) benzene from 2,3,5- trimethylphenol, is also described. Naphthol or 2,3,5- trimethylphenol dissolved in anhydrous acetone was respectively reacted with 1-chloroacetone and 2-bromoacetophenone in refluxing acetone in the presence of K2CO3 to undergo SN2 reaction to give carbonyl compounds. The resulting carbonyl compounds were respectively reacted with methylenetriphenylphosphoran generated from methyltriphenylphosphine bromide and pot. tert-butoxide in situ to undergo Wittig reaction to give alkenes. The giving alkenes were respectively heated to undergo the Claisen rearrangement to produce O-allylnaphthols and O-allylphenols, respectively. Followed by reacting with allyl bromide to undergo O-allylation, the desire intramolecular dienes were obtained, respectively.