Potassium Carbonate → 2-(Phenylselanyl)aniline

HRID 2217027

Reaction equation

HRID 2217027 reaction equation
[C:1]1([SeH:7])[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1.I[C:9]1[CH:15]=[CH:14][CH:13]=[CH:12][C:10]=1[NH2:11].[O-]P([O-])([O-])=O.[K+].[K+].[K+].C([O-])([O-])=O.[K+].[K+]>>[NH2:11][C:10]1[CH:12]=[CH:13][CH:14]=[CH:15][C:9]=1[Se:7][C:1]1[CH:6]=[CH:5][CH:4]=[CH:3][CH:2]=1

Participants

5

Reactant 4

HCID 11430Potassium CarbonateHCID 119952-Iodoaniline2×HCID 62657Potassium Phosphate, TribasicHCID 69530Benzeneselenol

Product 1

HCID 219461652-(Phenylselanyl)anilineYield 60%

Procedure

Using this protocol (see example 4 below), phenyl selenol was coupled with electron-rich aryl iodides in very good yields (Table 5). Sterically hindered iodides such as those with ortho-functionalities (entries 3, 5, 7 and 11), were coupled, as well as aryl iodides containing heteroatoms (entry 8 and 10). When o-iodoaniline was used as the aryl halide, in addition to the desired selenide, products were observed arising from the self-coupling of o-iodoaniline. This problem also persisted with K3PO4. However, when K2CO3 was used as the base, 1-amino-2-phenylselanyl-benzene was isolated in 60% yield (entry 12). With electron-poor aryl iodides, in addition to the desired diaryl selenides, diaryl diselenides were observed if NaOt-Bu or K3PO4 was used. In addition, with NaOt-Bu, transesterifcation products were observed when aryl halides with ester groups were used. Such complications can be avoided if K2CO3 is used instead of NaOt-Bu or K3PO4. Using this modified protocol a variety of diaryl selenides were obtained from electron-poor aryl halides (Table 6). The protocol tolerates even base sensitive groups such as esters and ketones (entries 3, 4, and 6).

Workup

  1. customin very good yields (Table 5)

Sources & evidence

ORD record
ord-1995b9f1df3e49c382063fa62af1ffb5
Source dataset
uspto-grants-2006_09
Patent number
US07112697B1

Linked notes

Loading…