Indole acetate

Another category Ic indole synthesis involves cyclization of a-anilino aldehydes or ketones under the influence of protonic or Lewis acids. This corresponds to retro.synthetic path d in Scheme 4.1. Considerable work on such reactions was done in the early 1960s by Julia and co-workers. The most successful examples involved alkylation of anilines with y-haloacetoacetic esters or amides. For example, heating IV-substituted anilines with ethyl 4-bromoacetoacetate followed by cyclization w ith ZnClj gave indole-3-acetate esterfi]. Additional examples are given in Table 4.3. 

Pyrano[3,4-b]indol-3-ones are the most useful equivalents of the indol-2,3-quinodimethane synthon which are currently available for synthetic application. These compounds can be synthesized readily from indole-3-acetic acids and carboxylic anhydrides[5,6]. On heating with electrophilic alkenes or alkynes, adducts are formed which undergo decarboxylation to 1,2-dihydro-carbazoles or carbazoles, respectively. 

The mode of action is by inhibiting 5-enolpymvyl-shikimate-3-phosphate synthase. Roundup shuts down the production of the aromatic amino acids phenylalanine, tyrosine, and tryptophane (30). Whereas all these amino acids are essential to the survival of the plant, tryptophane is especially important because it is the progenitor for indole-3-acetic acid, or auxin, which plays an important role in growth and development, and controls cell extension and organogenesis. 

Naturally Occurring Compounds. Many derivatives of iadole are found ia plants and animals where they are derived from the amino acid tryptophan. Several of these have important biological function or activity. Serotonin [50-67-9] (12) functions as a neurotransmitter and vasoconstrictor (35). Melatonin [73-31-4] (13) production is controlled daily by the circadian cycle and its physiological level iafluences, and seasonal rhythms ia humans and other species (36). Indole-3-acetic acid [87-51-4] (14) is a plant growth stimulant used ia several horticultural appHcations (37). 

H-Indole, 3,3-dichloro-synthesis, 4, 369 3H-Indole, 3,3-dimethyl-synthesis, 4, 224 3H-Indole, 3-hydroperoxy-autoxidation, 4, 247 rearrangement, 4, 249 3H-Indole, 3-oximino-synthesis, 4, 209, 210 3H-Indole, 3-oximino-2-phenyl Beckmann rearrangement, 4, 210 Indoleacetic acid synthesis, 4, 337 Indole-3-acetic acid as growth regulator, 4, 372 synthesis, 4, 346 Indole alkaloids, 4, 373 synthesis, 4, 276... 

Indole-3-acetic acid [87-51-4] M 175.2, m 167-169 , pK -6.13 (aq H2SO4), pK 4 5 4 (CO2H). Recrystd from EtOH/water [James and Ware J Phys Chem 89 5450 7985]. 

Coupling reactions of indole-3-acetic acid derivatives have also p ovided convenient routes to indolo[2,3-a]carbazoles (Scheme 5). An iodine-p-omoted coupling... 

Hydroxyindoles carrying a side chain containing a free NH2, OH, or COOH functional group are unstable. Therefore, 1-hydroxytryptophan, -tryptamine, and -indole-3-acetic acid have not been prepared yet. 

Tm-mediated-radical cyclizadon of isonitnles provides a usefid strategy for the preparadon of indoles (Tukuyama reacdoni This radical cyclizadon is used for synthesis of 6-hydroxy-indole-3-acetic acid, which is thearomadc subunit of Nephdatoxin The reqidsite isotdtnles are prepared from rdtroarenes via amines fEq 10 66 ... 

The synthesis and metabolism of trace amines and monoamine neurotransmitters largely overlap [1]. The trace amines PEA, TYR and TRP are synthesized in neurons by decarboxylation of precursor amino acids through the enzyme aromatic amino acid decarboxylase (AADC). OCT is derived from TYR. by involvement of the enzyme dopamine (3-hydroxylase (Fig. 1 DBH). The catabolism of trace amines occurs in both glia and neurons and is predominantly mediated by monoamine oxidases (MAO-A and -B). While TYR., TRP and OCT show approximately equal affinities toward MAO-A and MAO-B, PEA serves as preferred substrate for MAO-B. The metabolites phenylacetic acid (PEA), hydroxyphenylacetic acid (TYR.), hydroxymandelic acid (OCT), and indole-3-acetic (TRP) are believed to be pharmacologically inactive. 

Dichlorophenoxy acetic acid (555ng) 12/ Indole-3-acetic acid ethyl ester (445ng)... 

CN I -(4-chlorobenzoyl)-5-methoxy-2-methyl-1 //-indole-3-acetic acid carboxymethyl ester... 

CN ( )-l-(4-chlorobenzoyl)-5-methoxy-2-methyl-lH-indole-3-acetic acid 2-I4-[3-[[4-(benzoylamino)-5-(dipropylamino)-1,5-dioxopentyl]oxy]propyl]-1 -piperazinyl]ethyl ester... 

Kidney tissue, hver tissue, and fecal bacteria all convert tryptophan to tryptamine, then to indole 3-acetate. The principal normal urinary catabohtes of tryptophan are 5-hydroxyindoleacetate and indole 3-acetate. 

In Pseudomonas pyrrocinia, transformation was initiated by oxidation of the side chain to indole-3-acetate that was further degraded to indole-3-carboxylate before decarboxylation to indole (Figure 10.3c) (Liibbe et al. 1983). 

The degradation of indole-3-acetate has been examined in Bradyrhizobium japonicum and was initiated by oxidation to isatin that was hydrolyzed to 2-aminophenylglyoxylate and anthranilic acid (Figure 10.6) (Jensen et al. 1995). 

Jensen JB, H Egsgaard, H van Onckelen, BU Jochknsen (1995) Catabolism of indole-3-acetic acid and 4- and 5-chloroindole-3-acetic acid in Bradyrhizobium japonicum. J Bacterial 111 5762-5766. 

J. E. Loper and M. N. Schroth, Influence of bacterial sources of indole-3-acetic acid on root elongation of sugar beet. Phytopathology 76 386 (1986). 

Kostic el al. discovered that Pd11 complexes, when attached to tryptophan residues, can rapidly cleave peptides in acetone solutions to which a stoichiometric amount of water is added, for hydrolysis.436 The indole tautomer in which a hydrogen has moved from the nitrogen to C(3) is named indolenine. Its palladium(II) complexes that are coordinated via the nitrogen atom have been characterized by X-ray crystallography and spectroscopic methods.451 Binuclear dimeric complexes between palladium(II) and indole-3-acetate involve cyclopalladation.452 Bidentate coordination to palladium(II) through the N(l) and the C(2) atoms occurs in binuclear complexes.453 Reactions of palladium(II) complexes with indole-3-acetamide and its derivatives produced new complexes of unusual structure. Various NMR, UV, IR, and mass spectral analyses have revealed bidentate coordination via the indole carbon C(3) and the amide oxygen.437... 

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