Diphenylamine → HCID 69000985, compound

HRID 2099947Notes

Reaction equation

HRID 2099947 reaction equation
C[C:2]([CH3:5])([O-])[CH3:3].[Na+].[C:7](P(C(C)(C)C)C(C)(C)C)(C)([CH3:9])[CH3:8].BrC1C=C2C([C:25]3[CH:26]=[CH:27][C:28]([C:38]4[N:39]([CH3:43])[CH:40]=[CH:41][CH:42]=4)=[CH:29][C:30]=3[C:31]2([CH2:36][CH3:37])[CH2:34][CH3:35])=CC=1.[C:44]1([NH:50][C:51]2[CH:56]=[CH:55][CH:54]=[CH:53][CH:52]=2)[CH:49]=[CH:48][CH:47]=[CH:46][CH:45]=1>C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.C1C=CC(/C=C/C(/C=C/C2C=CC=CC=2)=O)=CC=1.[Pd]>[CH2:36]([C:31]1([CH2:34][CH3:35])[C:53]2[CH:52]=[C:51]([N:50]([C:3]3[CH:2]=[CH:5][CH:9]=[CH:7][CH:8]=3)[C:44]3[CH:45]=[CH:46][CH:47]=[CH:48][CH:49]=3)[CH:56]=[CH:55][C:54]=2[C:25]2[C:30]1=[CH:29][C:28]([C:38]1[N:39]([CH3:43])[CH:40]=[CH:41][CH:42]=1)=[CH:27][CH:26]=2)[CH3:37]

Participants

6

Reactant 4

HCID 11487DiphenylamineHCID 83681Tris(1,1-dimethylethyl)phosphineHCID 23676156Sodium t-butoxideHCID 57796676HCID 57796676, compound

Product 1

HCID 69000985HCID 69000985, compound

Reagents, catalysts & solvents 1

HCID 6505921(1E,4E)-1,5-diphenylpenta-1,4-dien-3-one; palladiumCatalyst

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-5160e0c492214cad88b0ea515f1962ff
Source dataset
uspto-grants-2009_08
Patent number
US07569704B1

Reaction notes

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