Cyanoacetic acid → 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

HRID 221169Notes

Reaction equation

HRID 221169 reaction equation
[CH2:1]([C:5]1([CH2:68][CH2:69][CH2:70][CH3:71])[C:17]2[CH:16]=[C:15]([N:18]([C:47]3[CH:59]=[CH:58][C:57]4[C:56]5[C:51](=[CH:52][CH:53]=[CH:54][CH:55]=5)[C:50]([CH2:64][CH2:65][CH2:66][CH3:67])([CH2:60][CH2:61][CH2:62][CH3:63])[C:49]=4[CH:48]=3)[C:19]3[CH:31]=[C:30]4[C:22]([C:23]5[CH:24]=[CH:25][C:26]([C:40]6[S:44][C:43]([CH:45]=O)=[CH:42][CH:41]=6)=[CH:27][C:28]=5[C:29]4([CH2:36][CH2:37][CH2:38][CH3:39])[CH2:32][CH2:33][CH2:34][CH3:35])=[CH:21][CH:20]=3)[CH:14]=[CH:13][C:12]=2[C:11]2[C:6]1=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH2:2][CH2:3][CH3:4].[C:72]([CH2:74][C:75]([OH:77])=[O:76])#[N:73]>C(#N)C.N1CCCCC1>[CH2:1]([C:5]1([CH2:68][CH2:69][CH2:70][CH3:71])[C:17]2[CH:16]=[C:15]([N:18]([C:47]3[CH:59]=[CH:58][C:57]4[C:56]5[C:51](=[CH:52][CH:53]=[CH:54][CH:55]=5)[C:50]([CH2:60][CH2:61][CH2:62][CH3:63])([CH2:64][CH2:65][CH2:66][CH3:67])[C:49]=4[CH:48]=3)[C:19]3[CH:31]=[C:30]4[C:22]([C:23]5[CH:24]=[CH:25][C:26]([C:40]6[S:44][C:43]([CH:45]=[C:74]([C:72]#[N:73])[C:75]([OH:77])=[O:76])=[CH:42][CH:41]=6)=[CH:27][C:28]=5[C:29]4([CH2:32][CH2:33][CH2:34][CH3:35])[CH2:36][CH2:37][CH2:38][CH3:39])=[CH:21][CH:20]=3)[CH:14]=[CH:13][C:12]=2[C:11]2[C:6]1=[CH:7][CH:8]=[CH:9][CH:10]=2)[CH2:2][CH2:3][CH3:4]

Participants

5

Reactant 2

HCID 9740Cyanoacetic acidHCID 866417805-{7-[bis-(9,9-dibutyl-9H-fluoren-2-yl)amino]-9,9-dibutyl-9H-fluoren-2-yl}-thiophene-2-carbaldehyde

Product 1

HCID 866417813-(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

Reagents, catalysts & solvents 2

HCID 8082PiperidineCatalystHCID 6342AcetonitrileSolvent

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-9992933c8b7a4c89b1cb27da37e92ced
Source dataset
uspto-grants-2012_06
Patent number
US08203068B2

Reaction notes

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