1-Iodo-4-nitrobenzene → HCID 131726905, compound

HRID 2225049Notes

Reaction equation

HRID 2225049 reaction equation
[CH3:1][C:2]1([CH3:40])[C:14]2[CH:13]=[C:12]([C:15]3[CH:27]=[CH:26][C:25]4[C:24]5[C:19](=[CH:20][C:21]([C:28]#[C:29][Si](C)(C)C)=[CH:22][CH:23]=5)[C:18]([CH3:35])([CH3:34])[C:17]=4[CH:16]=3)[CH:11]=[CH:10][C:9]=2[C:8]2[C:3]1=[CH:4][C:5]([NH:36][C:37](=[O:39])[CH3:38])=[CH:6][CH:7]=2.I[C:42]1[CH:47]=[CH:46][C:45]([N+:48]([O-:50])=[O:49])=[CH:44][CH:43]=1>>[CH3:1][C:2]1([CH3:40])[C:14]2[CH:13]=[C:12]([C:15]3[CH:27]=[CH:26][C:25]4[C:24]5[C:19](=[CH:20][C:21]([C:28]#[C:29][C:42]6[CH:47]=[CH:46][C:45]([N+:48]([O-:50])=[O:49])=[CH:44][CH:43]=6)=[CH:22][CH:23]=5)[C:18]([CH3:35])([CH3:34])[C:17]=4[CH:16]=3)[CH:11]=[CH:10][C:9]=2[C:8]2[C:3]1=[CH:4][C:5]([NH:36][C:37](=[O:39])[CH3:38])=[CH:6][CH:7]=2

Participants

3

Reactant 2

HCID 124951-Iodo-4-nitrobenzeneHCID 67036710HCID 67036710, compound

Product 1

HCID 131726905HCID 131726905, compound

Procedure

FIG. 3 shows a synthetic scheme (30) for the production of compound 20 (FIG. 2), where X is hydrogen. Compound 31, 7′-bromo-9,9,9′,9′-tetramethyl-9H,9′H-[2,2′]bifluoreny-7-ylamine, is acetylated and subsequently coupled with trimethylsilylacetylene to provide N-(9,9,9′,9′-tetramethyl-7′-trimethylsilanylethynyl-9H,9′H-[2,2′]bifluorenyl-7-yl)-acetamide 32. Trimethylsilyl derivative 32 is subjected to an organometallic cross-coupling reaction in the presence of 4-iodo-nitrobenzene to afford N-[9,9,9′,9′-tetramethyl-7′-(4-nitro-phenylethynyl)-9H,9′H-[2,2′]bifluoreny-7-yl]-acetamide 33. Acetylene 33 is converted to ketone 34—2-(7′-amino-9,9,9′,9′-tetramethyl)-9H,9′H-[2,2′]bifluoreny-7-yl]-1-(4-nitro-phenyl)-ethanone—through the addition of H2O, which also effects the hydrolysis of the terminal acetamide. Alkylation of 34 provides the desired compound 35, 2-[7′-(2-mercapto-ethylamino)-9,9,9′,9′-tetramethyl-9H,9′H-[2,2′]bifluoreny-7-yl]-1-(4-nitro-phenyl)-ethanone.

Sources & evidence

ORD record
ord-e2bcb236ce1941bab1434ef458fe9150
Source dataset
uspto-grants-2008_05
Patent number
US07378539B2

Reaction notes

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