Synthesis indoleacetic acid

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... 

Fig. 2. The pathway for indoleacetic acid synthesis in IP. savastanoi. Control of lAA synthesis occurs in part by inhibition of tryptophan monooxygenase by indoleacetamide. Because the inhibition is competitively reversed by the substrate, tryptophan, tryptophan pool size is important in modulating the inhibition by indoleacetamide.

Tryptophan pool size is regulated by feedback inhibition of anthranilate synthase by tryptophan. Other mechanisms, as yet unidentified, may regulate tryptophan and indoleacetic acid synthesis. 

MOVABLE ELEMENTS INACTIVATE GENES FOR INDOLEACETIC ACID SYNTHESIS... 

A most intriguing aspect of indoleacetaldehyde oxidase in plants is its extreme sensitivity to ionizing radiation. Gordon has shown that it is very likely that a blockage of in situ indoleacetic acid synthesis is brought on by y-irradiation, and that this leads to the characteristic morphological deformations observed in many plants. He was able to demonstrate that a neutral auxin with the properties of indoleacetaldehyde builds up after exposure to radiation, and that the dosage response curves indicate a remarkable radiation sensitivity of the aldehyde oxidase present. 

A 1M p-methoxy-aniline (p-anisidine), 0.5 M ethyl-gamma-Br-acetoacetate (brominate as described above for 1-methyl-DET synthesis) cool and add 250 ml ether. Filter, evaporate in vacuum and reflux residue fifteen hours with 60 g ZnCI2 in 250 ml ethanol. Evaporate in vacuum, wash precipitate with water and dissolve residue in benzene. Wash with 4N HCI and water and dry, evaporate in vacuum. Reflux prcipitate two hours in ethanol-KOH to get about 70% yield of 5-methoxy-indoleacetic acid (I). 

SYNTHESIS (from indoleacetone) To a solution of 1.55 g NaOAc in 5 mL acetic anhydride there was added 2.0 g 3-indoleacetic acid and the mixture was heated at 135-140 °C for 18 h. Removal of all volatiles on the rotary evaporator under vacuum produced a pale yellow residue that was the 1-acetylindole-3-acetone. This was dissolved in MeOH to which 0.93 g MeONa was added, and the solution held a reflux several hours. After removal of the solvent under vacuum, the residue was suspended in H20 and extracted with several portions of Et20. These extracts were pooled, and removal of the solvent under vacuum gave 0.41 g (21%) indole-3-acetone as a white solid, mp 115-117 °C. MS (in m/z) indolemethylene+ 130 (100%) parent ion 173 (16%). IR (in cm-1) 691,753,761,780. 1017, 1110, 1172, and a broad C=0 at 1710. 

Yu and Wang431 considered that indole-3-acetic acid exerts its stimulating effect on expansion growth by inducing the synthesis of the enzyme catalyzing the conversion of S-adenosylmethionine into ACC, a conclusion at variance with the suggestion of Vioque and coworkers432 that indoleacetic acid oxidase and its substrate (IAA) participate in the last reaction in the ethylene biosynthesis pathway, namely, the formation of ethylene from ACC. 

Specific substrates such as diethyl a -acetylglutarate, 2-ethoxycarbonylcyclopentanone and 3-carboxypiperidone are useful for the synthesis of special classes of functionally substituted indoles, as shown in Scheme 10. When cyclization is followed by hydrolytic decarboxylation of the C-2 substituent, these cyclizations provide indoleacetic acids, indolepropionic acids and tryptamines, and 3-(2-aminoethyl)indoles, respectively <72HC(25-1)236). 

Oxidation of DNA, pyrimidines, and purines Inhibition of polysaccharide synthesis Oxidation of indoleacetic acid Inhibition of cellulose synthetase, phospho-glucomutase, UDPG pyrophosphorylase... 

SYNTHESIS (from indoleacetone) To a solution of 1.55 g NaOAc in 5 mL acetic anhydride there was added 2.0 g 3-indoleacetic acid and the mixture was heated at... 

As pointed out previously, most herbicides have been discovered using random screening programs rather than from an applied rational approach to herbicide design, target, and synthesis. A few attempts to rationally design herbicides chose Inhibition of sites of photophosphorylation uncouplers (284). glycol ate oxidase (285). oxidation of Indoleacetic acid (lAA) by peroxidase (286). and secondary plant metabolism, I.e., phenlyalanine ammonia-lyase (2SZ)... 

Results with plants show the azalog of indoleacetic acid to be a powerful auxin in Pisum (pea) and Avena (oat) growth.This and the propionic acid isomer also proved to be effective with Partheno-cissus tricuspidata (Boston ivy) tissue. 7-Azatryptophan was found to inhibit a-amylase synthesis in barley endosperm tissue. 

Phelps, R.H. and L. Sequeira Synthesis of indoleacetic acid via tryptamine by a cell-free system from tobacco terminal buds Plant Physiol. 42 (1967) 1161-1163. Pictet, A. and G. Court Einige neue Pflanzenalkaloide [Some new vegetable alkaloids] Ber. Dtsch. Chem. Ges. 40 (1908) 3771-3783. 

Somei M, Kizu K, Kunimoto M, Yamada F (1985) The Chemistry of Indoles. XXIV. Synthesis of 3-Indoleacetic Acid and 3-Indoleacetonitrile Having a Halogeno Group and a Carbon Functional Group at the 4-Position. Chem Pharm Bull 33 3696... 

Kosuge, T. and M. Sanger, Indoleacetic acid, its synthesis and regulation A basis for tumorigenicity in plant disease, in The Shikimic Acid Pathway (E. E. Conn, ed.). Recent Advances in Phytochemistry Vol. 20 147-161, Plenum Press, New York, 1986. 

Serotonin S-hydroxytryptamine, M, 176.2, a plant and animal hormone. It is produced by hydroxylation of L-tryptophan to 5-hydroxytryptophan, followed by decarboxylation. The synthesis occurs in the central nervous system, lung, spleen and argentaffine light cells of the intestinal mucosa. S. is stored in thrombocytes and mast cells of the blood. It acts as a Neuro-transmitter (see), stimulates peristalsis of the intestine, and causes a dose-dependent constriction of smooth muscle. It stimulates the release from arterial endothelium of a dilator substance which counteracts its primary constricting effect [T.M. Cocks X A. Angus Nature 305 (1983) 627-630]. S. is a precursor of the hormone Melatonin (see). It is inactivated and degraded by monoamine oxidases and aldehyde oxidases to 5-hydroxy-indoleacetic acid. 

In animals hormones are produced either in special glands (cf. Table 64) or are formed in tissues in which the production of hormones is a biochemical side activity only (so-called tissue hormones). In plants and microorganisms, special hormone-producing glands are absent, but also in plants hormone synthesis is unequal in the different types of cells. Cytokinins, for instance, are produced predominantly in roots and 3-indoleacetic acid in apical meristems. 

INDOLEACETIC ACID, ITS SYNTHESIS AND REGULATION FOR TUMORIGENICITY IN PLANT DISEASE... 

The multibranched shikimic acid pathway provides the intermediates for the synthesis of the three amino acids phenylalanine, tyrosine and tryptophan in microorganisms and plants. In plants, these three amino acids are precursors for a variety of secondary metabolites such as alkaloids, coumarins, flavonoids, lignin precursors, indole derivatives and numerous phenolic compounds (Fig. 1). The role of the aromatic amino acids in protein synthesis is well known as is the role of indoleacetic acid in plant development however, the function of the various secondary products is much less clear. Various physiological roles have been proposed including pest resistance, chromagens in flowers and fruits, and precursors for the structural component, lignin. 

Crown gall oncogenesis evidence that a T-DNA gene from the Agrobacterium Ti plasmid pTiA6 encodes an enz3nne that catalyzes synthesis of indoleacetic acid. Proc. Natl. Acad. Sci. USA 81 5071-5075. 

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