Lithium diisopropylamide → 2-[(E)-2-(2,6-dichloro-3-methoxyphenyl)ethenyl]-5-methoxy-1H-indole

HRID 11073Notes

Reaction equation

HRID 11073 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[C:48]([O:49][CH3:50])=[CH:47][CH:46]=[C:45]([Cl:51])[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[C:48]([O:49][CH3:50])=[CH:47][CH:46]=[C:45]([Cl:51])[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 diisopropylamideHCID 118428349-hydroxy-4-iodopyrrolo[3,4-c]carbazole-1,3(2H,6H)-dioneHCID 87899066(2,6-Dichloro-3-methoxybenzyl)(triphenyl)phosphonium bromide

Product 1

HCID 219804982-[(E)-2-(2,6-dichloro-3-methoxyphenyl)ethenyl]-5-methoxy-1H-indole

Procedure

The 5-methoxy-1H-indole-2-carbaldehyde (1) was reacted with (2,6-dichloro-3-methoxybenzyl)(triphenyl)phosphonium bromide (526), prepared as described in example 117, using the procedure described in example 37, except that the aldehyde was added at 0° C., the ratio of LDA:aldehyde was 1.55:1 and the reaction time was 5 h, to give (after crystallisation from CH2Cl2/hexane) the diene (527) as a cream solid (the pure E isomer) (76%), mp 138–140° C. 1H NMR (CDCl3) δ 8.21 (br s, 1H), 7.32 (d, J=8.9 Hz, 1H), 7.26 (d, J=8.7 Hz, 1H), 7.22 (d, J=16.8 Hz, 1H), 7.04 (d, J=2.4 Hz, 1H), 6.92 (d, J=16.8 Hz, 1H), 6.87 (dd, J=8.8, 2.5 Hz, 1H), 6.80 (d, J=8.9 Hz, 1H), 6.61 (d, J=1.7 Hz, 1H), 3.92 (s, 3H), 3.85 (s, 3H). Found: C, 61.92; H, 4.52; N, 3.91. C18H15Cl2NO2 requires C, 62.09; H, 4.34; N, 4.02.

Workup

  1. customprepared
  2. additionwas added at 0° C.
  3. customto give
  4. custom(after crystallisation from CH2Cl2/hexane) the diene (527) as a cream solid (the pure E isomer) (76%), mp 138–140° C

Sources & evidence

ORD record
ord-b68878edc0094592bc98e8d4a7c9806f
Source dataset
uspto-grants-2006_08
Patent number
US07094798B1

Reaction notes

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