1-methyl-2-(tributylstannyl)-1H-pyrrole → HCID 57796676, compound
Reaction equation
Br[C:2]1[CH:14]=[CH:13][C:12]2[C:11]3[C:6](=[CH:7][C:8]([Br:15])=[CH:9][CH:10]=3)[C:5]([CH2:18][CH3:19])([CH2:16][CH3:17])[C:4]=2[CH:3]=1.[CH3:20][N:21]1[CH:25]=[CH:24][CH:23]=[C:22]1[Sn](CCCC)(CCCC)CCCC>>[Br:15][C:8]1[CH:7]=[C:6]2[C:11]([C:12]3[CH:13]=[CH:14][C:2]([C:22]4[N:21]([CH3:20])[CH:25]=[CH:24][CH:23]=4)=[CH:3][C:4]=3[C:5]2([CH2:18][CH3:19])[CH2:16][CH3:17])=[CH:10][CH:9]=1Participants
Procedure
As shown in scheme 2, 2,7-dibromo-9,9-diethyl-9H-fluorene (21) is reacted with 1-methyl-2-(tributylstannyl)-1H-pyrrole by Stille coupling reaction to obtain 2-(7-bromo-9,9-diethyl-9H-fluoren-2-yl)-1-methyl-1H-pyrrole (22). Then, in the presence of sodium tert-butoxide, Pd(dba)2, and tri-tert-butyl phosphine, 2-(7-bromo-9,9-diethyl-9H-fluoren-2-yl)-1-methyl-1H-pyrrole (22) is reacted with diphenylamine to obtain 9,9-diethyl-7-(1-methyl-1H-pyrrol-2-yl)-N,N-diphenyl-9H-fluoren-2-amine (23a). n-butyl lithium is reacted with 9,9-diethyl-7-(1-methyl-1H-pyrrol-2-yl)-N,N-diphenyl-9H-fluoren-2-amine (23a), and then tributylstannylchloride is added thereto to obtain N-methyl-2-(7-diphenyl-amino-9,9-diethyl-9H-fluoren-2-yl)-5-tributylstannylpyrrole (24a). N-methyl-2-(7-diphenylamino-9,9-diethyl-9H-fluoren-2-yl)-5-tributyl-stannylpyrrole (24a) is reacted with 5-bromo-2-thiophene carboxaldehyde by Stille coupling reaction to obtain 5-[N-methyl-2-(7-diphenylamino-9,9-diethyl-9H-fluoren-2-yl)pyrrol-5-yl]thiophene-2-carbaldehyde (25a). Finally, 5-[N-methyl-2-(7-diphenylamino-9,9-diethyl-9H-fluoren-2-yl)pyrrol-5-yl]thiophene-2-carbaldehyde (25a) is reacted with cyanoacetic acid in acetic acid by using ammonium acetate as a catalyst, and (E)-2-cyano-3-[5-(N-methyl-2-(7-diphenylamino-9,9-diethyl-9H-fluoren-2-yl)pyrrol-5-yl)thiophen-2-yl]acrylic acid (26a) is obtained.
Sources & evidence
- ORD record
- ord-5d7e25a49c1b4aae9276847303cfe9ff
- Source dataset
- uspto-grants-2009_08
- Patent number
- US07569704B1
Reaction notes
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