4631369649

mil* TYl 0AMINA W SYKI FZIE ORGANICZNEJ

ABSTRACT

This rcvicw shows cxamplcs ofapplication of Et,N in oxidations, eliminations, substitutions, and addition rcactions.

Tricthylaminc (Et₃N) appearc to bc most popular organie aminę base in organie synthetic chcmistry. The popularity comcs from its Iow price along with casiness of removal by distillation. I-Iowcver, Et₃N is a vcry dangerous fire hazard when expo-sed to the beat, flamc, or oxidizcrs. Thcir salts with inorganic acids are somewhat insolublc in most organie solvcnts oflow polarity and for that reason may by remo-ved from the rcaction media by simplc filtration.

Examples ofapplication ol'Ht,N in oxidation rcactions are shown in ozonolysis ofeyeloalkene 1-8 13 5] (figs 1-4- 5), and ilgs 1-6-8 show oxidation of 1-14,1-16, and 1-18 alcohols, employing aclivated DMSO [6-12], Various oxidation processes of hydrazones willi iodidc in the prcsencc of Et₃N are presented in fig. 1-9 [13J. Elimination rcactions, concerned mainly with dchydrohalogcnations, are described in cxamplcs of halogen derivativcs of lactone 2-1 [17], kctonc 2-3 [18,19], sulfone 2-6 [20], and acids 2-9 and 2-11 [21,221 (figs 2-1-5). Dchalogenation of2-13 [23], 2-17 [26 281, and 2-22 [31 371 acid ehlorides are presented in figs 2-6-8, while formation of nitrilc oxidcs in ligs 2-11 13 [38 42J. Competitivc dchydrobromina-tion and dchydrochlorination rcaction occurs in the prcsencc of Et₃N in 1,1,1-tri-chloro-3-bromo-3-fcnyIopropane (2-35) is dcscribcd in fig. 2-15 [44]. Mechanizm and cxamplcs of trans formation of ehlorosulfonyl ehlorides are presented in figs 2-17-20 [47-511, and dimeri/alion of aldiminium salts [63J in fig. 2-25 as well. Applications of Hl,N in earbon-earbon hond formation inan intramoleeular Heckrcaction are shown in fig. 3-1 [70 74J. Hxamplcofu.sc ofKt,N in cnolboronation of carbonyl compounds is dcscrihcil in fig. 3-2 [75 78J, and additionally, in synthesis of silyl cnol ethers can be fouiul in ligs 3-3 6 [89 104|. Application of Et,N as the base in ncutralizing the acids lihcrutcd in preparing diazo ketones and mixcd anhydrides arc indicatcd in fig. 3- 71105 107] and fig. 3-8 [108 117] respeetivcly, while in pro-tccting of hydroxy group in figs 3-9 11 [118 126J. Useof Et₃N as the effcctive catalyst in eyjanoelhylation rcaction of aetive mcthyl group in acetylacctone (4-2) [130] and alkylpyridine methiodides 4-4 5, 4-8 9 [131] arc shown in figs 4-1-3, and in isomeri/ation rcaction of pyrazolines 4-14 [133] and cycloaddition of inda-nc-l,3-dione (4-16) 1134| in figs. 4-5 6.