ALKYLLITHIUM REAGENTS FROM ALKYL-HALIDES AND LITHIUM RADICAL-ANIONS
ALKYLLITHIUM REAGENTS FROM ALKYL-HALIDES AND LITHIUM RADICAL-ANIONS
复制标题
DOI：
10.1021/jo01298a034
复制
发表时间：
1980-01-01
影响因子：
3.6
通讯作者：
HUTCHINSON, LL
中科院分区：
文献类型：
--
作者：
FREEMAN, PK;HUTCHINSON, LL
本文研究了卤代烷与三种不同锂自由基阴离子萘锂（LiN）、二叔丁基萘锂（LiDBN）和二叔丁基联苯锂（LiDBB）的反应。卤代烷与过量的LiN、LiDBN或LiDBB在THF中在-78 ℃下的反应导致还原产物（RH，RLi）的一致高产率（96-100%），在LiDBB的情况下，RLi的形成程度高（阴离子捕获93-95%）。LiDBN始终产生高产率的还原产物（89-99%），具有广泛可变的阴离子捕获量（21-88%），而LiN提供可变的还原产率（39-99%）和阴离子捕获产率（24-65%）。变化的浓度的溴化锂和萘和比例的烷基卤化物萘结合使用氘示踪剂的实验providedicence符合金属化的二氢萘二羧酸锂的烷基锂和碳酸化的烷基锂的碳酸化步骤的分析。
The reaction of alkyl halides with three different lithium radical anions, lithium naphthalene (LiN), lithium di-tert-butylnaphthalene (LiDBN), and lithium di-terf-butylbiphenyl (LiDBB), was studied. The reaction of alkyl halides with an excess of LiN, LiDBN, or LiDBB in THF at-78 C leads to a consistently high yield (96-100%) of reduction products (RH, RLi) with a high degree of formation of RLi (anion trapping 93-95%) in the case of LiDBB. LiDBN consistently produces high yields of reduction products (89-99%) with widelyvariable amounts of anion trapping (21-88%), while LiN provides variable yields of reduction (39-99%) and anion trapping (24-65%). Variation of the concentration of lithium bromideand naphthalene and the ratio of alkyl halide to naphthalene in conjunction with the use of deuterium tracer experiments providedevidence consistent with a competition between metalationof the lithium dihydronaphthalenedicarboxylate by alkyllithium and carbonation of alkyllithium in the carbonation step of the analysis.