METALATIONS WITH ORGANOSODIUM COMPOUNDS
METALATIONS WITH ORGANOSODIUM COMPOUNDS
复制标题
DOI：
10.1021/cr50017a002
复制
发表时间：
1957-01-01
期刊：
影响因子：
62.1
通讯作者：
SAUVE, DM
中科院分区：
文献类型：
--
作者：
BENKESER, RA;FOSTER, DJ;SAUVE, DM
金属化一词曾被提议用于用金属取代氢原子而得到真正的有机金属化合物的反应（26）。由于活性亚甲基的氢被置换成盐，而这些盐通常不被认为是真正的有机金属化合物，因此在本讨论中将不考虑这种类型的置换。与有机钠化合物的金属化反应还没有像与有机锂化合物的相应反应那样得到广泛的研究。然而，从现有的数据可以清楚地看出，有机钠化合物是比锂化合物更有效的金属化剂，并且经常与一些单金属化材料一起沿着产生双金属化产物。取向在许多情况下与有机锂化合物相同。因此，在含有氧、氮和硫等元素的芳香族化合物中，金属化倾向于发生在杂原子的邻位。呋喃（14，26，68）和噻吩（81，89）经金属化分别得到2-呋喃基钠和2-噻吩基钠。同样，二苯并呋喃（20，27，28），二苯硫醚（12），二苯醚（33，34），二苯并噻吩（12），和二甲基苯胺（12，56）产生邻位金属化。
The term metalation has been proposed for reactions which involve replace-ment of a hydrogen atom by a metal to give a true organometallic compound (26). Since the replacement of the hydrogen of active methylene groups results hi salts which are not generally thought of as true organometallics, this type of replacement will not be considered in this discussion. Metalations with organosodium compounds have not been studied as exten-sively as the corresponding reactions with organolithium compounds. From the available data, however, it is clearW seen that organosodium compounds are more potent metalating agents than the lithium compounds and frequently lead to dimetalated products along with some monometalated material. The orienta-tion is the same in many cases as with the organolithium compounds. Thus, in aromatic compounds containing elementssuch as oxygen, nitrogen, and sulfur, metalation tends to occur ortho to the hetero atom. Furan (14, 26, 68) and thio-phene (81, 89) are metalated to give2-furylsodium and 2-thienylsodium, respec-tively. Likewise, dibenzofuran (20, 27, 28), diphenyl sulfide (12), diphenyl ether (33, 34), dibenzothiophene (12), and dimethylaniline (12, 56) give ortho metalation.