Acetonitrile-3-indole

Tryptamines can also be prepared from gramine via indole-3-acetonitriles. This procedure was found advanta ous for C-ha o tryptamines[9]. 

An enantioselective nitrilase from Pseudomonas putida isolated from soil cultured with 2 mM phenylacetonitrile was purified and characterized. This enzyme is comprised of 9-10 identical subunits each of 43 kDa. It exhibits a pH optimum at 7.0 and a temperature optimum at 40 °C (Ty2 = 160 min) and requires a reducing environment for activity. This nitrilase was shown to have an unusually high tolerance for acetone as co-solvent, with >50% activity retained in the presence of 30% acetone. The kinetic profile of this nitrilase reveals KM= 13.4mM, cat/ M = 0-9s 1mM 1 for mandelonitrile, ZfM = 3.6mM, kclJKM 5.2 s him-1 for phenylacetonitrile, and KM = 5.3 mM, kC lt/KM = 2.5 s 1 him 1 for indole 3-acetonitrile. Preliminary analysis of this enzyme with 5 mM mandelonitrile revealed formation of (/t)-mandelic acid with 99.9% ee [59]. 

A systematic study of the substrate specificity profile of this nitrilase (Table 8.6) illustrated that arylacetonitriles, including phenylacetonitrile derivatives indole-3-acetonitrile and... 

Figure 8.4 Glucosinolate and IAA pathways. IAA indole-3-acetic acid IAN indole-3-acetonitrile IAOx indole-3-acetaldoxime. A loss of function of CYP83B drives the IAOx to IAA and an auxin-overproducing phenotype is the result.

Besides its role as an intermediate in indole glucosinolate biosynthesis, it has been suggested that IAOX is involved in IAA biosynthesis.40,41 This has been supported by the biochemical characterization of LAOX-metabolizing enzymes that convert IAOX to either indole-3-acetaldehyde,42,43 indole-3-acetonitrile,42,44 or... 

LUDWIG-MULLER, J., HILGENBERG, W., Conversion of indole-3-acetaldoxime to indole-3-acetonitrile by plasma membranes from Chinese cabbage, Physiol. Plant., 1990, 79,311-318. 

Arabidopsis cytochrome P450 (CYP71A13) Conversion of indole acetaldoxime to indole-3-acetonitrile 121... 

Indole-3-acetaldoxime (30) and 4-hydroxyphenylacetaldoxime were shown to be metabolized by plant and pest fungi to 32 and to other related indole- and 4-hydroxyphenyl carboxylic acids, however, the biochemical transformation differed between the two fungi. These biochemical transformations may be relevant to the ability of certain fungi to cause plant diseases . Compound 30 has been shown to be a key intermediate in the biosynthesis of camalexin, 3-thiazolyl-2 -yl-indole, a member of the family of phytoalexins that are produced in response to pathogen attack. It was demonstrated that CYP71A13 catalyzes the conversion of 30 to indole-3-acetonitrile, which is essential for the biosynthesis of camalexin. Thus, the literature supplies a large body of evidence for the existence of a set of enzymes dedicated to the production of the auxin, 32, from tryptophan via indole-3-acetaldoxime (30). 

A solution of 6.0 g indole-3-acetonitrile in 15 mL anhydrous THF was added dropwise to 160 mL of a 1 M solution of LAH in THF, stirred and held under reflux conditions. After an additional 8 h reflux, the reaction was cooled, and the excess hydride and reaction complex were decomposed by the careful addition of wet THF until the evolution of hydrogen ceased, then 25 mL 5% aqueous NaOH was added, followed by sufficient H20 to leave the inorganic solids with a filterable texture (about 15 mL additional). These solids were removed by filtration, the filter cake washed with THF, the filtrate and washings combined, and the solvent removed under vacuum. The solid residue was recrystallized from CH3CN to provide 5.3 g (86%) tryptamine as a cream colored crystal with a mp 112-114 °C. IR (in cm-1) 751, 811,882, 941, 1014, 1112 and 1128. 

A solution of 6.0 g indole-3-acetonitrile in 15 mL anhydrous THF was added, dropwise, to 160 mL of a 1M solution of LAHin THF, stirred and held under reflux conditions. After an additional 8 h reflux, the reaction was cooled, and the excess hydride and reaction complex were decomposed by the careful addition of... 

Synthesis of radioactively labelled indole-3-acetaldehyde, indole-3-ace-taldoxime and indole-3-acetonitrile... 

Kobayashi, M., Suzuki, T., Fujita, T, et al. 1995. Occurrence of enzymes involved in biosynthesis of indole-3-acetic acid from indole-3-acetonitrile in plant-associated bacteria. Agrobacterium and Rhizobium. Proceedings of the National Academy of Science USA, 92 714-8. 

In the fall army worm, Spodopterafrugiperda, sulfoxidation of phorate requires NADPH. It is inhibited by carbon monoxide and piperonyl butoxide, and induced by cytochrome P450 inducers (e.g., indole 3-carbinol and indole 3-acetonitrile) (Yu, 1985). 

Burow, M., Zhang, Z.-Y., Ober, J.A., Lambrix, V.M., Wittstock, U., Gershenzon, J. and Kliebenstein, D.J. (2008) ESR and ESMl mediate indol-3-acetonitrile production from indol-3-ylmethyl glucosinolate in Arabidopsis. Phytochemistry, 69, 663-71. 

SYNS 3-(CYANOMETHYL)INDOLE 3-IN DOL-ACETONITRILE INDOLEACETONITRILE INDOLE-3-ACETONITRILE lH-INDOLE-3-ACETONITRILE INDOLYLACETONITRILE USAF CB-29... 

P-INDOLEACETIC ACID see ICNOOO P-INDOLE-3-ACETIC ACID see ICNOOO 1H-INDOLE-3-ACETIC ACID, l-(4-CHLOROBENZOYL)-5-METHOXY-2-iMETHYL-, SODIUM SALT, TRIHYDRATE see IDAIOO INDOLEACETONITRILE see ICWOOO INDOLE-3-ACETONITRILE see ICWOOO lH-INDOLE-3-ACETONITRILE see ICWOOO INDOLE-3-ALANINE see TNXOOO INDOLE, 5-BENZYLOXY-3-ISONIPECOTOYL- see BFC200... 

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