Lithium diisopropylamide → 2-[(E)-2-(2-chloro-4-nitrophenyl)ethenyl]-5-methoxy-1H-indole

HRID 11082Notes

Reaction equation

HRID 11082 reaction equation
[OH:1][C:2]1[CH:14]=[CH:13][C:12]2[NH:11][C:10]3[CH:9]=C(I)C4C(=O)NC(=O)C=4[C:5]=3[C:4]=2[CH:3]=1.[Br-].[Cl:22][C:23]1[CH:48]=[C:47]([N+:49]([O-:51])=[O:50])[CH:46]=[CH:45][C:24]=1[CH2:25][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1.[Li+].[CH3:53]C([N-]C(C)C)C>>[Cl:22][C:23]1[CH:48]=[C:47]([N+:49]([O-:51])=[O:50])[CH:46]=[CH:45][C:24]=1/[CH:25]=[CH:9]/[C:10]1[NH:11][C:12]2[C:4]([CH:5]=1)=[CH:3][C:2]([O:1][CH3:53])=[CH:14][CH:13]=2

Participants

4

Reactant 3

HCID 2724682Lithium diisopropylamide2×HCID 118428349-hydroxy-4-iodopyrrolo[3,4-c]carbazole-1,3(2H,6H)-dioneHCID 87898987(2-Chloro-4-nitrobenzyl)(triphenyl)phosphonium bromide

Product 1

HCID 219808022-[(E)-2-(2-chloro-4-nitrophenyl)ethenyl]-5-methoxy-1H-indole

Procedure

The 5-methoxy-1H-indole-2-carbaldehyde (1) was reacted with (2-chloro-4-nitrobenzyl)(triphenyl)phosphonium bromide (559) prepared as described in example 148 using the procedure described in example 37, except that the LDA and aldehyde were (sequentially) added at 0° C., the ratio of LDA:aldehyde was 1.5:1 and the reaction time was 5 h, to give (after crystallisation from CH2Cl2/hexane) the diene (560) as a dark red-brown solid (the pure E isomer) (46%), mp 239–241° C. 1H NMR [(CD3)2SO] δ11.57 (br s, 1H), 8.32 (d, J=2.0 Hz, 1H), 8.18 (dd, J=8.8, 2.1 Hz, 1H), 8.15 (d, J=8.9 Hz, 1H), 7.59 (d, J=16.3 Hz, 1H), 7.47 (d, J=16.3 Hz, 1H), 7.29 (d, J=8.9 Hz, 1H), 7.05 (d, J=2.4 Hz, 1H), 6.82 (dd, J=8.7, 2.5 Hz, 1H), 6.70 (s, 1H), 3.76 (s, 3H). Found: C, 62.14; H, 3.91; N, 8.52. C17H13ClN2O3 requires C, 62.11; H, 3.99; N, 8.52.

Workup

  1. customprepared
  2. additionadded at 0° C.
  3. customto give
  4. custom(after crystallisation from CH2Cl2/hexane) the diene (560) as a dark red-brown solid (the pure E isomer) (46%), mp 239–241° C

Sources & evidence

ORD record
ord-d71f862c74a843f7a18c5255b186b546
Source dataset
uspto-grants-2006_08
Patent number
US07094798B1

Reaction notes

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