Methoxyindole compounds

Phytoalexin is also an interesting compound. The plant family, Cruciferae, utilizes 1-methoxyindole compounds as phytoalexins. We expected there was a chance to find new agrochemicals among analogs of l-methoxyindole-3-carbaldehyde [52] (10a, daikon-phytoalexin [53]). So, we have thus far prepared a lot of related compounds. Some of them are 5a,b, 6a-f, 10b, 119, 206a-d, 207a,b, and 208a,b. These are found to have mild activities (Somei and co-workers, personal communication, 2006). 

DMSO, NaCN, 125-180°, 5-48 h, 65-90% yield.This cleavage reaction is successful for aromatic systems containing ketones, amides, and carboxylic acids mixtures are obtained from nitro-substituted aromatic compounds there is no reaction with 5-methoxyindole (180°, 48 h). 

Pedras and co-workers (98P1959) isolated a phytoalexin from Wasabi (Wasabia japonica, syn. Eutrema wasabi) and determined its structure to be methyl l-methoxyindole-3-carboxylate (109) (Scheme 38). Compound 109 had already been synthesized by Acheson and co-workers [78JCS(P1)1117] in ten steps from o-nitroaniline. Pedras and co-workers (98P1959) combined our tungstate method and Acheson s work, and synthesized 109 in 9% overall yield but in an impure state. 

These types of compounds are expected to be produced by utilizing nucleophile substitution reaction at the 2 position of l-methoxyindole-3-carbaldehyde (115a) and 3-acetyl-1-methoxyindole (107). In practice, after conversion of 115a to 195a (53%) as described in Section IV.J, 195a is allowed to react with various amines. Consequently, many derivatives of 271 are obtained. Typical examples (271a-c) are shown in the scheme (99H1157). 

Other indoles that have been prepared using the Sonogashira coupling and cyclization sequence include 5,7-difluoroindole and 5,6,7-trifluoroindole [219], 4-, 5-, and 7-methoxyindoles and 5-, 6-, and 7-(triisopropylsilyl)oxyindoles [220], the 5,6-dichloroindole SB 242784, a compound in development for the treatment of osteoporosis [221], 5-azaindoles [222], 7-azaindoles [160], 2,2-biindolyls [223,176], 2-octylindole for use in a synthesis of carazostatin [224], chiral indole precursors for syntheses of carbazoquinocins A and D [225], a series of 5,7-disubstituted indoles [226], a pyrrolo[2,3-eJindole [226], an indolo[7,6-g]indole [227], pyrrolo[3,2,l-y]quinolines from 4-arylamino-8-iodoquinolines [228], optically active indol-2-ylarylcarbinols [229], 2-alkynylindoles [176], 7-substituted indoles via the lithiation of the intermediate 2-alkynylaniline derivative [230], and a variety of 2,5,6-trisubstituted indoles [231], This latter study employs tetrabutylammonium fluoride, instead of Cul or alkoxide, to effect the final cyclization of 215 to indoles 216 as summarized here. 

With both pyr-T and 4-HO-pyr-T, there are two additional ring analogies that are natural companions to 5-MeO-pyr-T. These are the piperidine and the morpholine counterparts, 5-MeO-mor-T and 5-MeO-pip-T. Both compounds are in the literature, and an entry reference to them can be gotten from the "known tryptamines" appendix. Along with the pyrrolidine material I had made a reasonable supply of the amides for these other two, both by way of the 5-methoxyindole and oxalyl chloride procedure given above. With piperidine, there is 5-... 

Many early claims of having prepared simple 1-hydroxyindoles have proved to be unfounded, although the unusually stable l-hydroxy-2-phenylindole was obtained in 1895.1-Hydroxyindole itself polymerizes on attempted isolation, while O-acylation, O-alkylation, or the presence of substituents greatly stabilizes the molecule. One 1-hydroxyindole antibiotic has been identified and is the only 1-hydroxyindole derivative isolated from natural sources so far. In contrast, a substantial number of 1-methoxyindoles occurs in various plants, and some of these may inhibit tumor formation in mammals. The biochemistry of these compounds, which include 1-methoxy-indoles, -indolines and -2-oxindoles, has not been widely investigated and could be a very fruitful area for new research which might well lead to novel medicinal agents and other useful compounds. 

The l3C-NMR spectra for several indoles and 1-hydroxy-, 1-acetoxy-, and 1-methoxyindoles have been very carefully measured, and selected data is presented in Table V. In the oxygenated compounds, which have quite similar spectra, the 3-carbon atom moves significantly upheld, as does the 7-carbon atom, but to a smaller extent. Detailed correlations between the various substituents and the chemical shifts and coupling... 

Hydrolysis of 1-acetoxy- or l-hydroxy-3-cyanoindole (115) by hydrogen peroxide or 1 M sodium hydroxide gave the corresponding amide, while QM sodium hydroxide gave the 3-carboxylic acid which decomposed rapidly at room temperature with diazomethane, the last compound gave the stable methyl l-methoxyindole-3-carboxylate [78JCS(P1)1117]. 1-... 

Compound 17 was obtained by slow air oxidation from a benzene solution of 16 17 similarly 2-methoxyindole yields indirubine. So far, no mechanism has been suggested for this interesting reaction. 

Aiuline and a range of substituted anilines and other aromatic anilines eg diethylaniline, ethylbenzylaniline, ethyltolylaniline and antinonaphthalene were detected only in the extract from the industrial sludge. These compounds are commonly used intermediates in industrial synthesis and their presence reflects the catchment to this particular treatment works. In contrast, indole and a series of indoles (methylindole, methoxyindole) were detected only in the domestic sludge. Some of these compounds are constituents of human faeces and their presence is presumably due to the high proportion of domestic waste received by this treatment works. 

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