- Transition-metal-free mono- or dinitration of protected anilines
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An amide-assisted arene nitration is presented, and both mono- and dinitration of protected anilines could be effected by using NaNO2 and NaNO3 as the mono- and bisnitrating agents, respectively. This divergent synthesis is transition-metal- and acid-free, and features a broad substrate scope, low cost, and ortho–para selectivity.
- Dai, Enrui,Dong, Ying,Dong, Yongrui,Kong, Rui,Liang, Deqiang,Liu, Guangzhang,Ma, Yinhai,Wu, Qiong
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- Studies of Reactions of Amines with Sulfur Trioxide. VI. Thermal Reactions of Anilinium, Dimethylanilinium, and Trimethylanilinium Salts of Butylamidosulfuric Acid
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When the title compounds were heated in an evacuated reaction vessel, both transsulfonation and rearrangement occurred.At lower temperatures (80-120 deg C) the corresponding phenylamidosulfates and sulfophenylamidosulfates (transsulfonation products) were the main products.Increasing temperature led to the formation of ring mono- and disulfonates (rearrangement products) at the expense of the transsulfonation products.The sulfonate group always migrated to the ortho and/or para position(s) to the amino group.In no case was any meta-product detected.There was no significant difference in the ease of transsulfonation among the anilinium salts studied exept 2,6-dimethyl- and 2,4,6-trimethylanilinium salts.On the other hand, the ease of rearrangement and the orientation of ring sulfonation depended strongly on the structure of the substrate anilines.The thermal reactions of 2,4,6-trimethylanilinium butylamidosulfate produced (2,4,6-trimethylphenylimido)bis(sulfate) in addition to (2,4,6-trimethylphenylamido)sulfate.This is the first isolation of an arylimidobis(sulfate) from such reactions.Mechanisms of the transsulfonation and rearrangement have been discussed.
- Kanetani, Fujio,Yamaguchi, Hachiro
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p. 3048 - 3058
(2007/10/02)
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