Cyanoacetic acid → HCID 69006466, compound

HRID 2099948Notes

Reaction equation

HRID 2099948 reaction equation
[CH3:1][N:2]1[C:6]([C:7]2[S:11][C:10]([CH:12]=O)=[CH:9][CH:8]=2)=[CH:5][CH:4]=[C:3]1[C:14]1[CH:26]=[CH:25][C:24]2[C:23]3[C:18](=[CH:19][C:20]([N:27]([C:34]4[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=4)[C:28]4[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=4)=[CH:21][CH:22]=3)[C:17]([CH2:42][CH3:43])([CH2:40][CH3:41])[C:16]=2[CH:15]=1.[C:44]([CH2:46][C:47]([OH:49])=[O:48])#[N:45]>C(O)(=O)C.C([O-])(=O)C.[NH4+]>[C:44](/[C:46](=[CH:12]\[C:10]1[S:11][C:7]([C:6]2[N:2]([CH3:1])[C:3]([C:14]3[CH:26]=[CH:25][C:24]4[C:23]5[C:18](=[CH:19][C:20]([N:27]([C:34]6[CH:39]=[CH:38][CH:37]=[CH:36][CH:35]=6)[C:28]6[CH:33]=[CH:32][CH:31]=[CH:30][CH:29]=6)=[CH:21][CH:22]=5)[C:17]([CH2:42][CH3:43])([CH2:40][CH3:41])[C:16]=4[CH:15]=3)=[CH:4][CH:5]=2)=[CH:8][CH:9]=1)/[C:47]([OH:49])=[O:48])#[N:45]

Participants

5

Reactant 2

HCID 9740Cyanoacetic acidHCID 86760929HCID 86760929, compound

Product 1

HCID 69006466HCID 69006466, compound

Reagents, catalysts & solvents 2

HCID 517165Ammonium AcetateCatalystHCID 176Acetic AcidSolvent

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-34953a3cc0504b7bbee7fade20a0f3bf
Source dataset
uspto-grants-2009_08
Patent number
US07569704B1

Reaction notes

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