An aryl halide such as

2010-02-10 4:28 pm
An aryl halide such as chlorobenzene can undergo a nuclephilic substitution reaction in the presence of a very strong base such as -NH2.
There are two surprising aspects to this reaction:the aryl halide does not have to contain an electron-withdrawing group,and the incoming substituent does not always end up on the carbon vacated by the leaving group.
For example,when chlorobenzene –with the carbon to which the chlorine is attached isotopically labeled with 14c-is reacted with amide ion in liquid ammonia,aniline is obtained as the product .
Half of the product has the amino group attached to the isotopically labeled carbon as expected,but the other half has the amino group attached to the carbon adjacent to the labeled carbon .
(a) Write the meachism for this reaction.
(b) What products will be obtained when chlorobenzene is replaced by o-bromotoluene (without 14C labeling) in this reaction?
更新1:

中譯和詳解

回答 (2)

2010-02-12 8:41 am
✔ 最佳答案
在有如 -NH2(留意這個負數是上標,表示這是個陰離子)的非常強鹼的情況下,如氯苯的芳鹵化物可進行親核取代反應。

這個反應有兩方面令人驚訝:該芳鹵化物不必含有拉電子基團,而新加入的取代基也未必連在騰出離去基團的碳上。

例如,連接氯的碳以14C(14為上標)同位素標識的氯苯,與氨基離子在液態氨中反應時,得到的生成物是苯胺。

在一半的生成物中,胺基如預計般連在以同位素標識的碳上,但另一半的胺基卻連在隔鄰的的碳上。

(a) 寫出這反應的反應機構。

(b) 當該反應以鄰-溴甲苯代替氯苯(沒有14C標識),會得到甚麼生成物?


圖片參考:http://i320.photobucket.com/albums/nn347/old-master/100212_1.jpg?t=1265906322

http://i320.photobucket.com/albums/nn347/old-master/100212_1.jpg?t=1265906322

2010-02-12 00:48:30 補充:
Refer to the mechanism. In addition of NH3, half of the NH3 molecules attack the one of the two bonding carbon atoms of the C≡C triple bond in the benzyne intermediate, and half attack another bonding carbon atom.
參考: 老爺子
2010-02-11 12:32 am
芳香族鹵化物,譬如氯苯,在有強鹼基存在的情況下,如胺基-NH2,就會起親核取代反應。




對於這種反應有兩種令人驚訝的情況:一則該芳香族鹵化物不需含拉電子的基團,一則進來的取代物也不見得總是取代在離開的基團的碳上。



譬如氯苯,將氯原子所連接的碳用同位素碳14標識,當它與液態氨的胺基反應時,得到的產物是苯胺。



其中有一半的胺基團,正如所預計的,是連接到有同位素標識的碳上,但是有一半卻是連接到隔壁的碳上。



(a)寫出此反應之反應機構。

(b)如果用鄰-溴甲苯來替代氯苯,不做碳14標識,那麼這個反應會得到什麼產物?



注: o-bromotoluene 即 1-bromo-2-methyl benzene,
如以上述理論推演,胺基對溴的親核取代反應,在第一個位置,跟在第六個位置,應該機會均等。但由於甲基團立體位置的阻擾,取代第六的位置應該多於第一個位
置。所以m-toluidine為主要產物,o-toluidine為次要產物。


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