Lithium diisopropylamide → 5-methoxy-2-[(E)-2-(3-nitrophenyl)ethenyl]-1H-indole

HRID 11078Notes

Reaction equation

HRID 11078 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-].[N+:22]([C:25]1[CH:26]=[C:27]([CH:48]=[CH:49][CH:50]=1)[CH2:28][P+](C1C=CC=CC=1)(C1C=CC=CC=1)C1C=CC=CC=1)([O-:24])=[O:23].[Li+].[CH3:52]C([N-]C(C)C)C>>[CH3:52][O:1][C:2]1[CH:3]=[C:4]2[C:12](=[CH:13][CH:14]=1)[NH:11][C:10](/[CH:9]=[CH:28]/[C:27]1[CH:48]=[CH:49][CH:50]=[C:25]([N+:22]([O-:24])=[O:23])[CH:26]=1)=[CH:5]2

Participants

4

Reactant 3

HCID 2724682Lithium diisopropylamide2×HCID 11454393[(3-Nitrophenyl)methyl](triphenyl)phosphanium bromideHCID 118428349-hydroxy-4-iodopyrrolo[3,4-c]carbazole-1,3(2H,6H)-dione

Product 1

HCID 219803545-methoxy-2-[(E)-2-(3-nitrophenyl)ethenyl]-1H-indole

Procedure

The 5-methoxy-1H-indole-2-carbaldehyde (1) was reacted with (3-nitrobenzyl)(triphenyl)phosphonium bromide 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 MeOH/CH2Cl2/hexane) the diene (551) as an orange-red solid (the pure E isomer) (51%), mp 178–182° C. 1H NMR [(CD3)2SO] δ 11.27 (br s, 1H), 8.34 (t, J=1.9 Hz, 1H), 8.09 (dd, J=8.1, 1.8 Hz, 1H), 7.99 (d, J=7.9 Hz, 1H), 7.67 (t, J=8.0 Hz, 1H), 7.47 (d, J=16.5 Hz, 1H), 7.26 (d, J=8.6 Hz, 1H), 7.25 (d, J=16.6 Hz, 1H), 7.03 (d, J=2.4 Hz, 1H), 6.77 (dd, J=8.8, 2.5 Hz, 1H), 6.61 (d, J=1.6 Hz, 1H), 3.76 (s, 3H). Found: C, 69.36; H, 4.77; N, 9.78. C17H14N2O3 requires C, 69.38; H, 4.79; N, 9.52.

Workup

  1. additionwere sequentially added at 0° C.
  2. customto give
  3. custom(after crystallisation from MeOH/CH2Cl2/hexane) the diene (551) as an orange-red solid (the pure E isomer) (51%), mp 178–182° C

Sources & evidence

ORD record
ord-2712ded50a36435682981de16c8069c0
Source dataset
uspto-grants-2006_08
Patent number
US07094798B1

Reaction notes

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