5-Formyl-2-thiopheneboronic acid → 5-{7-[bis-(9,9-dibutyl-9H-fluoren-2-yl)amino]-9,9-dibutyl-9H-fluoren-2-yl}-thiophene-2-carbaldehyde

HRID 221168Notes

Reaction equation

HRID 221168 reaction equation
Br[C:2]1[CH:14]=[C:13]2[C:5]([C:6]3[CH:7]=[CH:8][C:9]([N:23]([C:45]4[CH:57]=[CH:56][C:55]5[C:54]6[C:49](=[CH:50][CH:51]=[CH:52][CH:53]=6)[C:48]([CH2:62][CH2:63][CH2:64][CH3:65])([CH2:58][CH2:59][CH2:60][CH3:61])[C:47]=5[CH:46]=4)[C:24]4[CH:36]=[CH:35][C:34]5[C:33]6[C:28](=[CH:29][CH:30]=[CH:31][CH:32]=6)[C:27]([CH2:41][CH2:42][CH2:43][CH3:44])([CH2:37][CH2:38][CH2:39][CH3:40])[C:26]=5[CH:25]=4)=[CH:10][C:11]=3[C:12]2([CH2:19][CH2:20][CH2:21][CH3:22])[CH2:15][CH2:16][CH2:17][CH3:18])=[CH:4][CH:3]=1.[CH:66]([C:68]1[S:72][C:71](B(O)O)=[CH:70][CH:69]=1)=[O:67]>>[CH2:37]([C:27]1([CH2:41][CH2:42][CH2:43][CH3:44])[C:26]2[CH:25]=[C:24]([N:23]([C:9]3[CH:8]=[CH:7][C:6]4[C:5]5[C:13](=[CH:14][CH:2]=[CH:3][CH:4]=5)[C:12]([CH2:15][CH2:16][CH2:17][CH3:18])([CH2:19][CH2:20][CH2:21][CH3:22])[C:11]=4[CH:10]=3)[C:45]3[CH:46]=[C:47]4[C:55]([C:54]5[CH:53]=[CH:52][C:51]([C:71]6[S:72][C:68]([CH:66]=[O:67])=[CH:69][CH:70]=6)=[CH:50][C:49]=5[C:48]4([CH2:58][CH2:59][CH2:60][CH3:61])[CH2:62][CH2:63][CH2:64][CH3:65])=[CH:56][CH:57]=3)[CH:36]=[CH:35][C:34]=2[C:33]2[C:28]1=[CH:29][CH:30]=[CH:31][CH:32]=2)[CH2:38][CH2:39][CH3:40]

Participants

3

Reactant 2

HCID 27734305-Formyl-2-thiopheneboronic acidHCID 59325939(7-bromo-9,9-dibutyl-9H-fluoren-2-yl)-bis-(9,9-dibutyl-9H-fluoren-2-yl)amine

Product 1

HCID 866417805-{7-[bis-(9,9-dibutyl-9H-fluoren-2-yl)amino]-9,9-dibutyl-9H-fluoren-2-yl}-thiophene-2-carbaldehyde

Procedure

As shown in Scheme 3, 7-bromo-9H-fluoren-2-ylamine is reacted with 1-iodobutane to form 7-bromo-9,9-dibutyl-9H-fluoren-2-ylamine (31); and 2-Iodo-9H-fluorene is reacted with 1-iodobutane to form 9,9-dibutyl-2-iodo-9H-fluorene (32). Then, 7-bromo-9,9-dibutyl-9H-fluoren-2-ylamine (31) is reacted with 9,9-dibutyl-2-iodo-9H-fluorene (32) by Ullman coupling reaction to obtain (7-bromo-9,9-dibutyl-9H-fluoren-2-yl)-bis-(9,9-dibutyl-9H-fluoren-2-yl)amine (33). Next, (7-bromo-9,9-dibutyl-9H-fluoren-2-yl)-bis-(9,9-dibutyl-9H-fluoren-2-yl)amine (33) is reacted with 5-formyl-2-thiopheneboronic acid by Suzuki coupling reaction to obtain 5-{7-[bis-(9,9-dibutyl-9H-fluoren-2-yl)amino]-9,9-dibutyl-9H-fluoren-2-yl}-thiophene-2-carbaldehyde (34a). Finally, in acetonitrile, 5-{7-[bis-(9,9-dibutyl-9H-fluoren-2-yl)amino]-9,9-dibutyl-9H-fluoren-2-yl}-thiophene-2-carbaldehyde (34a) is reacted with cyanoacetic acid by using piperidine as a catalyst, to obtain 3-(5-{7-[bis-(9,9-dibutyl-9H-fluoren-2-yl)amino]-9,9-dibutyl-9H-fluoren-2-yl}-thiophen-2-yl)-2-cyano-acrylic acid (35a).

Sources & evidence

ORD record
ord-0a0885092b254c4fae97d7534af19b22
Source dataset
uspto-grants-2012_06
Patent number
US08203068B2

Reaction notes

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